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Documenti di Professioni
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, '..'J,
PETROLEUM
REFINERY ENGINEERING
JHcGr~w-H"1
,
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~-
THE SERIES
ANDER8SN ....MD WENorr-lntroouction to Chemical Engineering_
ARIES A~lD N~WTON-CAemical Engineering Cost EslimaJion
BADGER AND DANCHERO'-/71tTOduclion to Chemical Engi~emng
BENNETT AND MYERS-Momentum, Heat, and Mass Transfer
COMINGs-High Preuure TeckTUJiogy
COUGBANOWR AND KOPPJIIL-Proce88 S1lBUm8 Analy," and Clmlrol
DoDGE-Chemical &gimmng Th~ynamics
GRISWoLD-Fuel, Combtt8tion, and FUrnlJC68
GROGGINS-Unit PTOUUe3 in Organic Synthuis
,HARRIOTT-ProteM, Control
,HENI.EY AND BIEBER-Chemical Engineering CaiculaiUm8
HUNTINGTON-NatUral Gas and Natural Gasoline
JOHNSTON. AND THRIN~Pilot PlanU, Mod'e18, and Scaltrup Method, in CMmica~
Engineering
KATz, CORN:ELL, KOBAYASHI, POJ:TTMANN, VARY, ELENBAAS, AND WElNAl1G-Hancl-
EnginetT8
LEV'A' Fluidiultion
LEW\s, ~DA8CBJ
Stoichimnetry
MANTE~ AdBorptiO'11
MA NTELL--Electroche1!\ical Engineering
McADAMs-Heat TraTW1lUsi&n
MCCABE AND BmTH, J. C.-Unit Operations of Chemical Engineeri1t(J
MICKLEY, SHERWOOD, AND REED-Applied Mlllhematic8 in Chemical Engineering
NEL.~ON-Ptlroleum
PERRY
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Refinery Engineerin!1
TBEYBJ..IJ-Liquid Extradi(M
. TRETliAL-M cu3-tramfer OptTatimla
VILBllANDT AND DItTD~N-Ch61nical
, I,
PETROLEUM
REFINERY ENGINEERING
w.
L. Nelson
F ounh Edition
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ST. LOUIS
TORONTO
SAN FRANCISCO
MEXICO
LONDON
SYDNEY
PANAMA
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Lovinvly dedicated to
Marian, my wife
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PREFACE
When first published (1936) a main purpose of this book was the
introduction. of the principles of chemical engineering to the petroleum
refining industry. The situation is now reversed. The chemical indus,try now looks to petroleum refiners for leadership in the development of
many phases of chemical engineering especially those related to the largescale processing of fluids and to the application of catalysts. ," Refinery
engineering organizatioqs made vital contributions in original commercial
preparation of uranium or atomiG fuels.
Although conceived. originally as a. textbook, it rapidly became apparent that industry also wanted or needed the ' book. Accordingly suc-:ceeding editions ha.ve been a~med more and more toward providing a.
survey of the industry's engineering practices. International interest
is being recognized in the Fourth Edjtion by the introduction of more
information on foreign crude oils and more complete information on the
evaluatIon of oils. Crude oil is being shipped in increasing quantities
from Venezuela, the. Middle. East, and Canada, and the refiner must be'
familiar with foreign oils as well as his local variet~es n~t , only because
the properties and specifications of the. products are affected but because
the economy of the enti~e industry is influenced. New Appendix B
of the Fourth Edition introduces the analyses of over 70 'foreign crude
oils as well as about 90 representative United States oils for comparison.
When the First Edition was 'written, much, of -the. information ' on
design computations had not theretofore been published, and such methods were new to much of the industry. This situation has also been
reversed. Computation methods now flow from the industry at a rate
that cannot be accommodated in new ,editions~ .
At least twelve major books or series of books relating to. petroleum
refining were published prior to. 1939, but only a few of these have heen
revised and scarcely any new publications have appeared. Undoubtedly ,
the rapidly growing complexity of the industry and the' eno.rmity of the
\'urrent literature have been a discouragement to authors. To properly
explure the current literature would require the continuous ~rvices of
IX
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PREFACE
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PREFACE
xi
W ilbu~ L. Nelson
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CONTENTS
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Index
lX
1
9
19
79
168
215
226
263
276
293
347
374
395
414
434
465
528
585
626
694
759
819
865
889
905
910
939
...
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CHAPTER
Coal oil and sperm oil were the common burner fuels when the Drake
discovery well was drilled in 1859. It has been estimated that 60 coal
distillation plants operated between 1852 and 1859. Perhaps the first real
petroleum refinery was that of Willi.am Barnsdalland William A~ Apbott,
built,at Titusville, Pa.,in 1860 at a cost of about $15,000; although records
indicate that petroleum was distilled in Russia in 1735. 1
Continuous Distillation. E.a rly refiners employed. batch systems of
separation, but the essentials of continuous operation were being explored
and patents were issued as early as 1860. Developments continued, but
the first widely recognized continuous plants were those of M. J. Trumble
(1912). These plants involved the use of both pipestills and continuous
fractionators. Modern distillation plants are completely continuous,
with the exception of coke stills which are operated either as batch or as
semi continuous operations. In modern plants several distillation units
are often connected so that the hot product from one unit (usually the
residue) is pumped directly to another. Also, several units may have a
common heat-exchange s ystem by which the charge stock for one unit is
heated in other units. In other pha~.es of refining, such .as. treating,
dewaxing, compounding, and packaging, the processing is still partly
batch or seniicontinuolls, but continuous operation is not of great. value
in these op'erations.
..
..
Gracking Thermal Decomposition. Even the phenomenon of cracking is not a modern development. True, the large plants and the wholesale manufacture of decomposition products are new, but thermal decomposition was actually practiced in the distillation of coal and oil shale even
before the days of the oil industry. During the first years of the petroleum industry a U cracking distillation, H in addition to the customary distillation with steam, was practiced. The cracking dist~llation is reported
to have been discovered accidentally in 1861. A distillation in a 16-bbl
still had been half completed, and the stillman had built a strong fire.
The stillman intended to he away an hoUl' but was unable to return until
or
1 Herodotus (450 B.C.) and other bistorians report petroleum and tar (by other
names) at dates betore 1735, but they fail to tell how the oil was refined:
1
~"11:-:" :::~
2 .... ".'
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Refinery statistics
1-1
Jan.,
1931
Jan.,
1941
Jan.,
1951
Jan.,
1956
4,181
6,702
8,381
1,103
1,853
2,777
51.3
60
70.3
20,600 28,200
10,000
420
325
294
2,588
4,300
7,244
attained by the elimination of traces of liquid from the vapor. The liquid
particles had been wetting the walls of the heating tubes where they
decomposed into coke which plugged the tubes. Modern thermal reforming and gas-cracking processes are possible because 'of the discovery of
this principle.
The liquid-phase cracking processes were the first to be commercially
applied, and the Burton process was the first to be practiced on a large
scale. Development began in 1910; a patent was issued in 1912; recognition of Dr. Burton by the Willard Gibbs Medal was given in 1918; and
by 1921 over 800 Burton stills were said to be in operation. Other early
liquid-phase processes were the Fleming, Isom, and Emerson processes.
The importance of cracking in the modern refinery is emphasized by
the statistics shown in Tables 1-1, 6-1, 6-2, and page 759. "
The general scheme of processing is much the same in all modern
thermal cracking plants. The advantage of cracking only those stocks
,
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HISTORY AND DEVELOPMENT OF REFINING
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the sale of burning oils that contained too much gasoline. Laws were
enacted limiting their flash point.
.
1885-1900. Mineral lubricating oils gained favor with the public.
Until this time vegetable oils were considered the best. Paraffin-base
lubricating oils gained a favorable reputation which has been retained to
this day.
1900-1914. Shortly after 1900 gasoline began to be valuable, and
within a few years it had grown to be the most useful refinery product.
The demand became so great that many new oil fields were discovered,
and fundamental improvements in refining methods ensued. The compression process for the recovery of natural gasoline was developed, and
experiments were conducted concerning cracking.
1914--1925. The ever-increasing d.eman9- for gasoline caused the refiner
to turn to methods of recovering more of it from crude oil. The thermal
cracking processes were brought
a high degree of perfection, and the
fundamentals of heating, fractionation, heat transfer J and absorption were
developed and applied commerciaJly. Continuous processing systems
using fractionating towers J pipe-: or tubestill heaters, and heat exchangers
were developed. Structural equipment was developed for high pressures
and high temperatures. In 1920 a marked increase in the use of fuel oil
for the generation of power was noted,. and the tendency has continued
until today.
1925-1929. During 1925-1935, the industry profited greatly by the
~pplication of chemical engineering practices, and .the scarcely recognized
young science of chemical engineering was able to establish itself firmly
. by practice in tbe petroleum industry_ To this day, the petroleum industry is the major outlet for chemical engineers. During this period the
rarge profits from lubricating-oil processing attracted attention, and
vacuum distillation was developed. Until this time vacuum distillation
had not been truly successful, because batch or shellstill heating had to be
used. The newly acquired knowledge of pipestill and fractiona.ting-tower
design made the development of continuous vacuum-distilling systems a
logical step. Low-cold-test oils were produced by direot :expansion of
ammonia rather than by the customary method of circulating brine.
C.ontinuous pipestill equipment was adapted to all distillation operations
including the rerunning of pressure-distillate and lubricating-oil stocks.
The Edeleanu method of solvent treating with sulfur dioxide proved to be
commercially successful.
1929-1935: The demand for highly antiknock gasoline resulted in the
development of vapor-phase cracking plants, gasoline-reforming units J
and an ever-increas~ng use of cracking plants. The hydrogenation process
was developed, but it has not been 'widely used because of' unfavorable
economic conditions. Several successful solvent-dewaxing and solvent-
to
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PETROLEUM
RE~RY
ENGINEERING
in
CHAPTER
COMPOSITION OF PETROLEUM
in
as
to
10
pare those which are isolated from petroleum. Furthermore, -the isolation of pure compounds is extremely difficult because the properties of
adjacent members of a series differ from one another only slightly and
because constant-boiling mixtures, which cannot be separated by. fractionation-, are prevalent: These difficulties and the multitude of hydrocarbons that are present in petroleum 4 have discouraged the study of
petroleum chemistry.
Hydrocarbon Series. Of the many hydrocarbon series present in
petroleum, qnly a few have been studied thoroughly enough to guide com
mercia! development. The best known series are the paraffin, olefin,
naphthene, aromatic, diolefin, and acetylene (Figs. 2-la to f are examples
of the structural formulas of these types of compounds).
The paraffin serus (type fo~m~la C"H 2n+2) is characterized by great
stability. The name of each member ends .in -an e-m ethane, ethane,
hexane~ and hexadecane. At room temperatures the members, with the
exception of those containing a tertiary carbon atom, are not acted upon
by fuming sulfuric acid, concentrated alkalies, nitric acid, or even the
powerful oxidizer chromic acid. They react slowly with chlorine in sunlight and with both chlorine and bromiae if a catalyst is present. S Reaction usually occurs by the substitution of an element or a chemical group
for a hydrogen atom. The lower members have been identified in most
crude petroleums, but Mabery6 reports th~t Mahoning County~ Ohio,
contains no paraffi...ll hydrocarbons. The higher members of the
crude
paraffin series are probably present in most petroleums, although crude
oils tbat are entirely fr~e from wax may contain no high-boiling paraffin
hydrocarbons. Paraffin wa..,,< probably consists of straight- o~ branchedchain paraffin hydrocarboris. 7 Egloff, Schaad, and LowryS have m~e a
_thor~mgh study of the decomposition of paraffin hydrocarbons (Fig. 2-1a
and f).
The olefin or ethylene series (type formula C n H 2n ) is composed of unsatu,.
rated hydrocarbons; i.e., the members of this series are capable of uniting
directly with other materials such as chlorine, bromine, hydrochloric acid,
and sulfuric acid, without displacing a- hydrogen atom. The names of
these hydrocarbon~ end in-ene, as ethene (ethylene)-, propene (propylene),
and butene (butylene). Unsaturated compounds re~ct with and dissolve
in sulfuric acid and_may thus be removed from petroleum oils. The lowboiJing olefins are probably not present in crude petroleum, but they are
oil
Some au thod ties estimate that 3,000 com pounds may be presen t in crude petroleum.
Egloff, Schaad, and Lowry, The Halogenation of the Paraffin Hydrocarbons, Chem.
Rev., 8, (1) (1931).
.
8 Ind. Eng. Chern., 6, 101-107 (1914).
7 Buchler and Graves, The Petroleum Waxes, Ind. Eng. Chem., 19, 718 (1927).
8 The Decomposition of the Para.ffin Hydrocarbons, J. Phys. Chem., 34, 1617 (1930).
4
r;
..
>
.r
r
11
COMPOSITION OF PETROLEUM
~~~~';i~
H-C-C-C-C-C-C"'H
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H-C-C-C-C-C=C
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H H H H
H
(b) Normal Hexene, C6 Hrz .
HHHHHH
(~Normal Hexa n e, C6 H 14
,C,c
c
I
H,
H'
,H
/I '
~y/ 'H
C
H
(d) Benzene) C6 H6
H
I
H-C~H
H, HI H
HI H
H
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C =c-c-c-c=c
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H
H H
H
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~. ~ ~
I~
H-C-C-C-C-C-H
I
HH HH H
2 Meth'ylpent~ne~ ,
C 6 HI4
HI
H-C-H
~ ~
I ~
HH I H
H-C- c- C- C- H
H-C-H
1
H
Z-2 Dime-t-hy'J but0t18
C6 HJ4
pounds can react by direc~ combination with other materials, but saturated compounds can react only by the' displac~ment of hydrogen by
another material. In the older chemistry texts the naphthenes are called
. methylenes, e.g., tetramethylene, pentamethylene,and hexamethylene,
whereas the preferred names are now cyclobutane, cyclopentane, and
cYclohexane. As an example of the relation of this series to other cyclic
series, consider benzene and cyclohexane. Both compounds contain six
carbon atoms per molecule, but six hydrogen atoms must be added to
benzene to produce cyclohexane. , The cyclohexane molecule is saturated,
but the benzene molecule is highly unsaturated because it has three doubly
9
-12
combiiied carbon atoms (Fig. 2-1d). The three doul?le bonds are active so
that benzene. is an active material, but the cyc10hexane contains no double
bonds and does not react readily. However, most of the reactions of
benzene are by substitution rather than combination. The naphthenes,
unlike. their isomers the olefine, are not easily soluble in sulfuric acid.
They have been found In almost all crude oils, but again Mahoning County
crude oil is an exception. II This crude oil contained the hydrocarbons of
the C,.H 2A- 2 and C H 2n-4 series but no paraffins or simple naphthenes.
Egloff, Bollman, and Levinson lO have studied the reactions of the cyolo
.
hydrocarbons (Fig. 2-1c)~":
The aromatic series (type formula C"H 2n- 6), often called the benzene
series, is chemically active. These hydrocarbons are particularly susceptible to oxidation with the formationol organic 'acids. . The aromatics may
form either addition or Bubstitution products, depending upon the conditions of the reaction. Only a few petroleums contain more than a trace of
the low-boiling aromatics such as benzene and toluene. Maberyll found
rela.tively large quantities of aro~tics i n Ventura, Coalinga, and Puente
Hills, Ca.lif., petroleums. Some of the Sumatra and Borneo crude oils are
rich in aromatics. This series is found in catalytically reformed gasoline
and is highly pnzed for its antiknock qualities (Fig~ 2-1d).
.
The diolefin serie8 (type formula C"H 2Ja-2) is similar to the olefin series
except that two hydrogen atoms are missing or ~wo double bonds are
present in each molecule. These .double. b0t:lds cause the series to 'be
extremely active. The. diolefins tend to polymerize or combine with
other unsaturated molecules forming high-molecular-weight gurnlike
solids. T he diolefin~ and the gums from them are found in untreated
cracked gasoline,12 but they are probably not present in crude petroleum.
They are polymerized and removed by sulfuric acid (Fig. 2-le).
The cyclic seties such as those having type formulas 0,,11 2,,-2, C"H 21l - j ,
C"H 21l- SJ etc., are not well known. Nevertheless, the literature indicates
that these series predominate in the higher boiling point oils, su-ch as gas
.oil and lubricating oils. Most of the hydrocarbons in lubricating oil ~re
saturated, but Seyerl! reports that about 20 per cent of a lubricating oil is
soluble in sulfur dioxide. Doubtless the.20 per cent consists largely of
. unsaturated hydrocarbons.
Isomeric Compounds. Confusion often arises because different com, pounds may have the same molecular formula. Isomeric compounds are
those whlch have the same molecular formula but different internal structures. Compounds of the type formula C"H 271 may be either saturated or
R
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COMPOSITION OF PETROLEUM
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Isomers
Ca.rbOn atoms
5
9
18
35
355
15
18
25
7
8
9
12
40
Isomers
4,347
60,523
36,797,588
62,491,178,805,831
14
.:I
=----f-~-4--_+__----460
g.
(\
~--#-~~-4---4---+---+--~70~
m
o
~T---~~~~~~~-+--~---r--~&Oz
(II
",
:n
90M
lJ)
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15
COMPOSITION OF PETROLEUM
Fraction!
2-1.
Arematic
Aromalic
57~F
OF
Arematia
N&pht.hene
Par-
af'ii.n '
NaphLhene
Para.ffin
140-203
!,
Par-
Arc-
affin
matic
--
-25
252-302
3
5
9
302-39~
14
35
29
392-482
18
23
482-572
]7
22
203-252
Napht.hene
30
72
65
56
57
59
61
]3
21
26
35
31
40
52
35
55
24
63
57
11
65
52
Naph-,
thene
Par-
31
65
46
amn
-21
73
28
65
33
29
55
55
52
5
7
12
16
17
17
31
32
51
4
6
11
17
25
29
48
25
64
61
45
ao
40
'31
22
or
Nelson, W. L., Aromatic-base Crude Oils, Oil Gas J., Oct .. 28, 194~, p. 101.
735 (1932); 21, 661 (1935); 21, 701 (1935).
18 Oil Gas J., Jan. 13, 1944, p. 41.
n Petroleu.m Z.) :a6, 867(1929}.
15
16
No. of
carbon
2-2.
Pennsylvania.
Mid Continent
atoms
5
10
15
20
25
30
35
40
CJI 2ft +t
C~1n+2
C"H2ft +,
C"H h
C"H tft and C",H tIt _ 1
C"H 2n a.nd C"H 1,,_4
C"H 2Il _ t and CIlH In _ a
. C~2n_. and C..H",,_I
CnHIfJ+J
C.H 2Il +1 and C.Ht.
C"H2It-1
C",H:b_c
50
CRH~
C"Htn._,
C"H2.II_1
C"Hb_.'and C.. H b - J2
C"H 2ta- 1 and C,JI21l-U
C..Ht.-1 and CJItn.-lI
80
C.H2_a
C..H,_l1
California. and
Gulf Coast
C.RIA and C..Hb!+t
C"Hb..and CftH,_a
CJlt.-t
C...H Ia _ c
CnHt..-4
C..H2JI_8
CttHta - u
C"Hz._ 12 and C.. H"'_lt
C"~IIa-1a
C"HtJa - ,o
.;
q PLATINUW CATALYST
RUORWfl) ~a
.1
~~
FIG. 2-3. Indiea.tion of the chemical composition of gaaoImes, weight per cent."
G~ J.)
.
HYOROc:AR5ONS
(00
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COMPOSITION OF PE':J'ROLEUM
17
Figure 2-3 shows the co~position of several gasolines~ Table 2-2 indicates in a genera] way the series of hydrocarbons that have been found
in Pennsylvania; Mid Continent, and California oils. The C n H 2n - 8,
. C"H2~12" C7lH2n-16, and CnH2n-20 series were taken from Mabery's study
of lubricant and asphaltic hydrocarbons. 20 The tiltimate- composition 21
of a few petroleums is listed in Table 2-3.
TABLE
2-3. ULTIMA'1'II
Sp
gr
Petroleum
I!
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PennSylvania. pipeline ..
Mecook, W.Va ........
Humbolt, Kans .... . ...
Healdton, Okla ........
Coalinga, Calif ........
Beaumont, Tex ........
Mexico ..... . . '........
Baku, U.S.S.R ........
Colombia, South
America. ............
At
Per
cent
(]
0.862
0.897
0.912
15 85.5
0 83.6
.. 85.6
.. 85.0
0.951 15 86.4
0.91 . .. 85.7
0.97
15 83.0
0.897 .. 86.5"
to
0.948
Per
cent
H
14.2
12.9
12.4
12'.9
11.7
11.0
11.0
)2.0
Per
cent
Per
cent
0
...
Per
cent
S
- .. . ...
3.6 '
...
. ...
..
0.37
0.76'
..
0.60
. ..
1.14
2.61
4.30
1.7
...
0.70
Base
Paraffin
Paraffin
"Mixed
.Mixed
Naphthene
Naphthene
Naphthene
1.5
Sulfur Compounds. The common types of sulfur compounds are indicated in Fig. ' 2-4. Difficulties with oils that contain sulfur compounds
arise in only three main ways--corrosioD, odor, and poor explosion characteristics of gasoline fuels. Corrosion by finished products presents little
difficulty because most p~oducts are used at low temperatures, temperatures at which only such compounds as hydrogen sulfide, freesu1fur, and
some of the lowest boiling sulfides, ' disulpdes, and perhaps mercaptan~
are corrosive toward the main commercial met~s. These low-boiling
materials tend to be concentrated into the gasoline by distillation, and
hence inherent corrosiveness is seldom encountered in higher-boiling products except occasionally in kerosene. Thus the main bulk of the corrosive
sulfur compcunds can be removed by treatment. with alkalies or the
"sweetening" treatments. In the presence of air and moisture, the sulfur gases produced during the bunling of oils may cause corrosion, as "in
steel stacks, ducts, and engine exhaust pipes or mufflers. Corrosive or
unstable sulfur derivatives of the sulfuric acid used in treating oils, such
as alkyl sulfatC$ and sulfonic acids, may also be present, but these can
'. usually be eliminated by better plant control of treating. Real difficulties
arise when high-sulfur oils are heated to temperatures of 300F or 'higher
Ind. Eng. Chem., 16. 1233 (1923).
n Int. Crit. Tablcs) 11, 136-162 (1927).
to
18
for copper, or 400F for ' steels. This may be illustrated by dibenzy1
disulfide, a common gear-lube additive, which is noncorrosive to copper
at 2.12F but is' corrosive at 300F-must be corrosive if this type of
lubricant is to function properly. The sUlfides (mono- and di-) are
generally. considered 'to be thermally unstable, whereas cyfic compounds
.such as thiophene are stable. Straight-run gaso1ines cOntain primarily
mercaptans, hydrogen sulfide, and the sulfides, whereas cracked gasoline
usually contains only small amounts of the mono- and disulfides.
R-O
........ /
Alkyl sulfates
Hydrogen sulfide'
R-O
H-S-H
R
Mercaptons:
Methyl
Benzyl .
H-S-R
H":'-S-CHJ
H-S-C s H5 .
Methyl
n~ Buf-yl
Disulfides
Methyl
Cyclic sulf;des
/ '0
H-O
R-----S-R
It
'R-S-R
CH)-S- CH 3
C4 H9- S -C 4 H 9
R-S-S-R
CHJ-S -S-CH 3
"'-'"
S
Sulfonic acids
Sulfox.ides
Sulfides~
Sulfones
"
R-S-R
II
Thiophene
I
\
\
S
/,
H-C C-H
H-C-C--H
II
II
I
\.
FIG. 2-4. Structural formulils of sulfur compounds. The symbol R refers to an alkyl
radica.l, i.e., a group of ca.rbon and hydrogen atoms.
.,
CHAPTER
-3
In general, these tests have been' adopted because they can be (1) performed quickly, (2) easily duplicated by ordinary laboratory technicians,
and (3) interpreted as a function of the performance of-the product while
in use. They are not usually scientifically exact, and hence the proce-:
dures for the tests are .carefully specilied and must be faithfully followed
if the results are to be dependable. 2 . Routine tests are unive~sally used for
controlling refinery operations. Tests may be conducted at 2-hr intervals
during the initial operation of a plant, and very quickly the test results
assume importance as a criterion of plant operation. Not only are the
raw and intermediate plant prod~cts examined, but the finished products
are tested repeatedly as they progress from the unit into run-down storage,
finished storage, tank cars~ trucks, pipelines, ocean tankers, and fillingstation or consumer storage. .
Temperatures at which samples may be opened or poured 3 without
materially altedng the composition of the sample are indicated in Tabl~
3-1. 4 Safe pouring temperatures from the standpoint of fire are even
Report of Committee D-2, ASTM, Phila.delphla, Pa.., yearly.
2 Mapstone, G. E., Pet. Refiner, October, 1950, p. 114.
3 API, New York, Code 50-B.
Nelson, W. L., Oil Gas J., May 20, 1948, p. 239.
19
1
\.
20
lower -than those of Table 3-1, being about 30~F below the flash point.
The term "wide boiling" used in Table 3-1 refers to materials that contain small amounts of relatively low-boiling material, such as natural
gasoline that contains propane, gassy .or unexposed crude oil, unstripped
refinery products, and .asphalts that have been cut back with lighter
materials.
TABLE
3-1.
Reid
v.p.,
psis.
45
40
35
30
25
20
15
10
Fla.sh
point,
DF
Approx.
0-10%
boiling
.range,
of
. .
..
..
.........
.... -...
- ......
..
.....
..
..
80
..
..
Fra.etioned
Nat.
Nat.
Nat.
Nat.
Nat.
. .......
Pouring temp., of
Illustrative materials
gaso.
gaso.
gaso.
gaso.
gaso.
WIde boiling
Wild na.t.
W"tld nat.
Wild nat.
Wild nat.
W"lld nat.
gaso.
gaso.
gaso.
gaso.
gaso.
95
115
Fractiona.ted
Wide
boiling
12
-11
20
28
- 5
2
9
18
38
48-
60
26
77
100
36
48
8
6
4
2
..
..
140
..
160
..
190
125
215
245
275
305
30
50
70
90
335
110
150
.395
200
475
250
550
300
625
350
700
400
500
780
930
1,000
..
.. NelBon, W. L.,
6
"
Stable gaso.
Stable gaso.
Sta.ble ~aso.
Crude oil
Crude oil
Crude oil
123
57
67
140
86
Solvents
Solvents
Solvents
Solvents
Solvents
Unstripped
UnStripped
Unstripped
Unstripped
Unstripped
178
195
225
245
270
125
135
165
185
210
.
Kerosene
Distillates
Distillates
Gas oil
Fuel oil
. Unstripped
Gas oil
Fuel oil
Cutbacks
Asphalts
305
365
240
Lube oil
Lube oil
Lube oil
Asphalts
Cutback asphalts
Cutback aspbalts
Cutback asphalts
Cutback asphalts
112
440
515
585
66()b
6W
66()b
660"
280
330
380
430
490
540
640
66()b
21
API Gravity and Specific Gravity. Specific gravity and API (Ameri..
can Petroleum Institute) gravity are expressions of the density or weight
of a unit volume of material. The specific, gravity is the ratio of the
weight of a unit vol~e of oil to the weight of the same volume of -water
at a standard temperature. Unless otherwise stated, both specific gravity
and API gravity refer to these constants at 60F. An exception is the
use of 77F (25C) in connection with asphalt~ and road oils.
D
or
141.5
sp gr
use
! .
22
j
I
j
,
I
I
J
.
I
(E.P.)~
Virtually no fractionation occurs in this distillation, and the hydro-:carbons in the oil do not distill 'o ne by one in the .order of their boiling
points but as successively higher and higner boiling mixtures. The details
of this . inadequacy will be discussed under vaporiz~tion in Chap. 15.
Actually, the initial boiling point, the end point, and the . intermediate
vapo;r 'ten:tperatures have. little significance except when compared with
corresponding points, from other ASTM distillations (but 'see Fig. 3-3).
'Materials boiling below the initial boiling point and above the end point .
are present in' the oil, although these points are the extreme ends of the
ASTM disti11ation range. In routine plant reports the loss is plotted at,
the' end of the distillation curv.el but for more scientific work it is usually
plotted at 1J11e beginning of the curve. A comparison between ASTM
and true boiling point (T.B.P.) distillations is given in Fig. 4-17.
Flash. and Fire Points. The flash point and the fire point are further
indications of. the range and nature of the boiling-point curve. They
designate, respectively, the temperature at which the vapor above an oil
will momentarily flash or explode when in the presence of a flame and the
temperature at which the vapors are evolved rapidly enough to bum continuously. These tests serve to indicate the temperature below which an
c~~ ,,3-n be handled withoutdanger of fire. Certain high-boiling oils; such,
as'lubricants, cannot 'be distilled at atmospheric pressure without thennal
decomposition, and in such a case the flash point belps to indicate thE'
relative amount of low-boiling oil present in the material.
. I
,
'
23
'
The common flash.:.point instruments are the open CUpl (D92) and
Pen8ky~M artens 1 (D93) closed, tester fo~ heavy oils and the Tag l (D56)
closed tester for light oils. The oil is heated at the rate of lOaF per
minute in the heavy oil testers and at 1.8F in the Tag tester. A test
flame is introduced into the vapor at 30-sec intervals. The flash point by
the Martens tester is about 100 lower 7 than by the open tester; but if the
flash point is above 510F (Martens), a larger difference exists between
flash points by the two instruments. ' The closed instrument is the more
exact of the two, but the open cup is used e~ensively because of its
simplicity.
,Color. The color of an oil serves as an indication of the thoroughness
of the refining process. True, oils of different boiling range and from different crude oils may have different colors; but, other things being comparable, the color indicates the degree of refining that the material has
undergone. Distilled products that are discolored are an indication of
(1) 'thermal decomposition, (2) the entra.inment of dark-colored tarry
material,' or (3) materials that are inherently dark.in color. Discoloration by decomposition is due to the use of too ~igh temperatures, and
discoloration by entrainment is usually due to "throughputs" above the
, maximum 'capacity 'of the equipment. Color is important where staining
of fabrics, etc., may occur.
,
1
The Sayboll ~ chromometer (D156) is used to determine the color of
gasoline ' and :burning oils, and the Union colorimeter! (D155) for lubricating oils, cylinder oils, and petro1atum. Both these instruments have
empirical color scales that bear no direct relation to the Lovibond, colpr
analysis. For lubricating-oil colors, the Tag Robinson color instrumen't
is also r.nding favor. .The S~ybolt chromo.meter col9r scale ranges from
30 for,.fine, gasoline '15 for mi'neral-seal burning oil. Normally,
or
two color disks are us~d, but a half disk is avail~ble for colors from +25'
to +30.' In commercial usage, colors are often described by names, an~ ,
the relationship of the na;rnes'to, the common eo1or numbers is indicated jn
Table 3-2.
'
The :t bloom 1J or "cast" of lubricating oils. observed in reflected light
can be measured by the Bloom Index. 8 It, measures how much the blue
or the yellow predominates in reflected Lovibond colors.
Viscosity. The viscosity of an oil is a measure of its resistance to
internal flow and is an indication of its oiliness in the lubrication
of surfaces. In the centimeter-gram-second (egs) system ,t he unit
of viscosity' is the poise or centipoise (0.01 poise). Viscosity may be
defined as the force in dynes required to move a plane of r sq cm area, at ,
to
,I
one
Nelson, W. L., Flash:.poiIit by Different '[older] Instruments, Oil Gas J. t July 26,.
'1947, p. 254.
7
8
/
,!
24
TABLE
Saybolt
chromometer
number.!!
..
..
24
21
10
.. .
3
3~
:;
10
6
7
8
6
3
1
-2
-:4
:.-11
-16
- ,24
-28
-32
. . . ..
.....
. ......
'
. . ..
.......
...... . .
. . ..
.. .. ..
...... "
........
.....
2~
11
. ,
12
..
..
..
..
.. .
StaDdard "hi~
Standard white
StAndard "hite
.......... . ...................
..
..
..
..
..
..
..
..
...
..
..
. ..
..
..
.. .
...
..
..
Color.nAmes
l~
.................... . ............
Lilly w~~
. ..............................
Cre&D1 white
.. ,
. ................. . ...... .
Extra pale
E:ltra lemon pale
Lemon pale
Extra orange pale
Ol1Ulge pale
Pale
Ligb\ red
' Dark red
Claret red
. . . . . . . . . . . . . . to . . . . . . . . . . . . . .
Extra lightoi
Ligbt.d
Medium4-
cur
COMPARISON
"
30
25
17
16
15
14
InsUtute of
Petroleum
numbenr"
3-2.
ASTM
and
NPA
numbera
..
..
Union
Pel.
Co,
leUers
..
...
COLOR SCALES
Tal
Robinson
Aumben
..
.... ,
. ......
Red
200
aeries
Yellow
Amber
Blue
510
500
1180
..........
0.32
II
...
2.0
..
..
..
. .....
1.02
4.0
. ......
. .... .
1.1
1.1
5.0
.. .....
. ......
1.1
1.0
......
i.2
.. ......
1.1
1.1
0.12
1.1
..
..
..
..
..
..
G
..
H
..
2}S'
3
.K
..
..
..
. .... .
..
..
..
..
1
..
..
,.
.... .
20M
. ......
4.0
6.0
7.0
0.0
14.0
15.0
8~
H.O
4H
L
M
N
531
p
Q
R
,3M
21.0
35.0
60 . .0
60.0
166.0
106.0
64.0
33-{
I
J
A
D
17Ji'
. ......
12M
10
2;5
4.6
6.9
9~
9
9.40
2
1~
, ....
.... ' "
.. " "
0.6
25.5
" "
(1. 4-1. D)
2.4
27.0
8.0
' 27.0
26.0
27.0
32 .. 0
45.0
60.0
56.0
93.0
60.0
IH
&eriee- . aeria
aeries
10.2
20.0
21.0
31.0,
89.0
56.0
(5-7)
.
(~23)
I
1I
(50-63)
(110-125) 0.55.
"
.. ,
0~56
..........
tJ
r
(220-250)
0 ..55
1.8
(300-340)
..............
25
cally equal. Two other common terms are kinematic viscosity, which is
the viscosity in centipoises divided by the specific gravity at the same
temperature, and fluidity, which.is the reciprocal of viscosity. The units
of kinematic viscosity are stokes ~nd centistokes. , The English, unit
5
II reyn" (1 Ib-sec per'sq in.) is' equal to 69 X ,10 centipoises.
The common viscosimeters do not read directly in centipoises. All
employ arbitrary scales , of viscosity. The Saybolt Universal viscosity!
(D88) is the time, measured in seconds, required for the effiux of 60 cc
of oil from a. container tube at a constant teinpemture through a calibrated orifice in the bottom of the tube. The procedure involves strain-:, ing the oil to remove particles that migh~ lodge in .the orifice; bringing the
oil to a. constant temperature by means of a. constant-temperature bath,
and accurately measuring the time for efflux. The Saybolt FUTOl viscosityl
-(D88) is determined exactly as is the' Universal viscosity except that a,
larger orifice'is used . . The ,viscosity of lubricants is usually 'r eported as
Saybolt Universal seconds at 100; 130, or 210F, and of fuel oils as Saybolt
,
Furol seconds ~t 122 or 210F.
Kinematic viscosity may be detemuned directly by means of Ubbe]ohde,
FitzSiIhnions modifica.tion, or modified Ostwald viScosimeter pipettes
(D445). A series of these pipettes which cover the entire useful range
of viscosity may be suspended in a single constant-temperature bath.
Great accuracy is possible with these instruments, and a somewhat
, smaller sample is 'satisfaCtory, but each instrument must be calibrated.
The pipette method must be :used for gasoline, naphthas, or kerosene,
because turbulent rath~r than streamline, flow occurs in the large- orifices
of the Say bolt equipment. The viscosity of. kerosene is sometimes determined in. the Saybolt -thermov~scosimeter, 9 and thermoviscosity (at 60_F)
is related to' the kinematic~ and _Saybolt Universal'viscosity (at 60F)
apprr;omately as folIows: 1()
, ,
\
+'
Thermo. ,= 15
148.5 lci.nematic
_Thenno. = 46 SSU - 1,183
(3-2)
.(3-3)
If t,is
is
TT:_
.n.wema
le VlSCOSl
= 8'Z =
0219
, '
t - ,149.7
t
(3-4)
26
, Cloud and Pour Points. The cloud and 'p our points a.re useful in estimating the relative amount of w~x in an oiL IIowever, all oils will solidify
if cooled to a low enoug.h temperature;. and hence these tests do not.indicate the actual amount of wax or soJid material In the oil. They do iI)d"i- ,
cate tha t most of. the wax, melting above the pour point, has been remov.ed ..\
In the cloud test t (D97) the oil is cooled, from ~t least 25F above thecloud point, in a specified test jar. The cooling bath is held between 15
. and 30F belo\~ the "cloud point of the oil . . At intervals the test jar is
removed hom the brine bath without disturbance to the oil,~nd the
temperature at'. which ~ distinct cloudiness or haziness appears in the
botliom of the j\.r is re~orded as the cloud point. The ~loud point of
dark-colored oils may be estimated by the temperature at.which the vis- '
cosityincreases rapidly.U The pour iest l (D97) iscondticted in much
the same manner.. However, the oil is first heated to 115F, to be sure
that all wax has dissolved) and cooled to 90F before the test. As in the
cloud test, the bath is held 15 to 30F below the estimated pour point.
i
i
.i
I
i
!
j
I
.,
i
27
At interva.ls of 5F, the test jar is remove~ from the ba.th a.nd tilted- to
. ascertain if the oil will flow or move. If it shows no movement when
. the jar is held" horizontal for 5 sec, it' is said to be solid. The pour point
is taken as the temperature 5F above the solid point.
/rirrie~ Engle~ R.edwood. RedwOod Ac:lmit"'f'1,.Soybott Univer:scd; F'urol. e",ybe-j
'-+600800!,OOO 7f/XJ 3.0004.0006.000 10,000 'lO,OOOJO.OOO sapoo
2,000
Degrees Engler
200 300 &100 600 lOOO
30 40 SO 60 80 100
10
Kl
.i
"
!~
~ooo
r. ...
...-c)\~'i VJ
'.e ' ;P
800
-~.
. 600 ~
' 0,:
">~300
..
e200
, \I)
'8
.~
:>-
(!)
"5.
~ tOO
"0 ~ 80
n.
\f)
<
u
~
30
.~
p :IY
7
~
20
l-
\I)
:>
......
Il .
E
,a)
,t::
#-
10
8
6
5
4
. I
h-
II
v:
1/ ,"
,,.,~
' ~[I
I/:J
i.
1
It!J
,.
fJ
1
I
~[
'. r,,
I .
t\
3,000
.-
I.
I
1. '"41 <S'~
: 'l .
~ooo
a
.-
-, '\
t
I
2,000 .
~ .
-i
"
.
. ,:\.
Icrl<en allnesaml' ft'~
~
~ ~sl e YfsfOSlIy ~t'a {h9 ~
lA ' + t1
30 405060 80100 200.300400
.J rl
4,000 ,
!
I
~OOO
.-
800
'Yo1\iO.""
II! .
8.000
.
600
K.:I'U
' .
.+ Data (rom Archbuttand DeeleY.
I I
.J
!J ;1
/.
~&,
1-'-
11
//_~~
(lJ1...L
I
~ r{ '
I KIII'
-" IQOOO
:oo;r. '.
.~ _5".
"
//
) V
~ -Q~~ ~~
"' ,
17
1 ....
I
I
,/
~"
1I - , 7/,,7
V, e~ ~~r() ~ /
(\~:"f-:<"
~o,
~, I \<>' oJ'll,'
es ~ 5
{\;'<\e(
{q;
v,,
~
o . ~\ " fir'
ffi ,/
-rl
IJ'
)'
/ V
c.)
/[1
~[f
,n
vv
50
40
.o~ 'tJ~
~~ St)1 -
~~
ClJ .~
J:l)/)
I""~
J7
.:1.
A 15,000
'",
~\,//
l~
B.~:N\
. ;o~v(U
400
6DOO B.DOO
2POO 3,000
IfG
~V
ao.ooo
c>?tQ.
20
f,OO tO~
2,0003.(0),4D.oO~&OO
Tlme:'Engler, Redwcod,RedwOCld Admu""ltyl S~bolt UnW~I; ruyol, Barbey
t
3 4 5678Ql0
20 30 Sl050W 80 100
200 300400 600000
. ,"Degrees Engler
FIG. 3-1. Comparison of viscosity by different instruments. (The viscosites must h,e
determined a.t the same temperature.) (Th6 TexlU Co.)
.
Years ago the industry. had a specified cold test which indicated the
ca.pacity of the oil to flo:w after Vigorous stirring' at a. ~ow temperature.
This test proved to be inadequate and shOliId.,not be confused with the
cloud or pour tests of today.
---
I
!
28
i
I
I
1
I
I
29
I
3-3.
TA1H.E
Res6!Uoh method
.
StH.ight.
run
Motor
methode
Clear
3 cc
TEL
(cato)
30.~
30.0'
36.0
35.0'
40
42
41.5
4.e.o
46
48
48.0
60.5
40.5
42.5
44 . 5
46 . S
48.5
50
52
48.5
52.5
55.0
50: 5
52.6
57.0
66
58
54.5
59.5 56.5
61.5 58.5
60
62
M.O
60.5
66.0.
62.5
54.5
54
68.5
64
66 '
70 . 5
73.0
68
'67.0
69.0
46.0'
49.0
51.5
54.0
56. 0
58 . 5
Bf.o
80
82
84
86
88
. '" 81.0'
..... 83.0
...... . 85.0
........ .. 87.0
....... 89.0
87.5
90.0
92.S
95.0
97.5
100.0
. - .... 91.0
......
... .
. . . II
...
II
Clear
3 co
TEL
Sec
TEL
--
-.. . ...
63.0
..
62.0'
. ..... . . 65.0'
68.0
70.5
64.0' 70.0
66.0 74.0
73.5
Sg.O 78.0.
78.0
65.5
68.0
.. . ..
78.5 .
72.S 82.0
75 . 5 85.0
78.5 87.0
82.0 Sil.5
73.9
76.5
79.5
86.5
82.0
89.0 . 84.5 92.0' 85.0
81.0
83.5
'7 6.S
79.5
32.0'
91.~
... . .
. . . . .
&
.........
87.5
90.5
93.5
97.0
lOO . ()I>
....... 88.0
. ... ....
......
78.51
81.0
83.5
86.5
89.0
91.5
91.0 94.0
94.0' 96.5
81.0'
81.0 91.0l
86.5 92 . 0
89 '. 0 93.0 93.~
91.5 96.0 95.0
95.0 99.~ 97.0
97.0 . ...... 98.0'
....
o.
Ulled as "clear" Motor method with the "clear" Research ochne numbers, aDd
the "leaded" columns.
. Extrapolat.ed. Such ext.reme ~tane numbers are seldom encountered.
CI
Clear
67.5
6O.S
71.5
74.0
95.5
98.0
~-
3co
TEL
(cat.)
62.5
85.0
87.5
90.0
93.0
Clear
Polymer
OS.O
........
....
3Ce
Cat.
ar&cked
47:5
50. 0
......
Thermal
cracked
TEL
---
75.5
78.0
. 80.0
S2.S
85.0
' 90
~-
... ....
65.5 .........
68.0 .........
70. 5 66.~
73.0 69.0'
75.0 71.0
77.0 73 ~ 0
79.0 75.0
81 . .9 71.0
83 . S 79.0
. . ..
Clear
TEL
63.5
70
72 .
74
76
. 78
3~ '
Clear
-----30
35
Reformed .
(thermal)
Reformed
&8
"leaded" with
30
Octane number
Performance
ReSearch- , Wiese scaleh
81.4
88.0
93.0
,.
number
. .
.. ..
60
70
'
....
..
80
" ,.
....
90
100.0
100.0
102.641
103.3
. 100
104.74
106.7
110.0
113.3
116.7
120.0
96.9
106.44
108.0"
109.4"
110.5"
co TEL plus.
isooctanec
110
0
0.29
120
0 .68
130
140
150
1.27
2.15
3 .50
5.80
160
The presence of corrosive materials such 'as free sulfm and corrosive
sulfur compounds is always objectionable. The test! (D130) consists in
noting the effect of the heated oil on a strip of polished copper. More
than a slight discoloration of the copper after heating for 3 hr indic~tes
that the oil is corrosive.
Tests for Bituminous and Semisolid Materials. ' The most common'
tests . for asphaltic substances are the ductility, penetration, .ring-andball softening pointl' (E28), and specific'-gravity tests. The ductility 18
, (DI13) of an asphalt is a measur~' of its capacity to elongate or stretch
and is an indication ~f .the ability ' of the ma.terial to flow and thereby
mend a rupture in the surface of the material. A briquette of the asphalt
ASTM Sta.nd.a.rds. on BituminoUs Materials for, Highway Construction,' Water~
proofing" B.n.d Roofing, ASTM, Philadelphia, Pa.., yearly .
18
1
I
i
I
.i
J
REFINERY PRODUCTS AND TEST METHODS
31 .
is pulled apart a.t a uniform rate, and the elongation, measured in centi, meters, that occurs before rupture takes place is called the U ductility."
The test is usually conducted at 77F~, and the briquette is pulled apart
at a uniform rate of 5 cm per min. Penetration 18 (D5) allows a needle
or cone to penetrate, the material without mechanical friction and is
arranged to read the depth ,of the penetration in hundredths of ~ centimeter. A' standard' needle is used for asphalt materials 1 (P5), and the
cOmInon test conditions are temperature, 77F (25C); time, 5 sec.; and
load, l()O g; but temperatures of 32 and 115~ are also used.
For greases and petrola.tum 1 (D217) the needle, is replaced with a
standard cone. The procedure is the 's ame as for asphalt materials
, ~xcept that the temperatures of 32 and 115F are seldom used.
Road oils are 'examin~ for flash point, viscosity (Furol) at 77, 122, 140,
or 180F, and by So distillation test~8 (D402). The residue is tested for
penetration, ductility, and solubility in carbon tetrachloride 18 (D4). The
distillation test sometimes ruins the ductility of the asphalt, and henee
. the value of the test is b.eing questioned.
Gum and ,Gasoline. The determination of gum in gasoline has been a
troublesome test. The copper dish method of determining gum has been
replaced by a. method! (DaSI) that ,utilizes a measured and heated stream
of air to assist in the vaporization. ' This test indicates the amount of
gum at the time of test and the amount of deposition that may take place
in service if the 'gasoline is used immediately. .In addition, a. test for
gum stability! (D525) which involves heating, the gasoline at 212F in a '
bomb at a pressure of 100 psi, all in an atmosphere of oxygen, is useful in
estimating the amolint of gum that will ,be formed during storage. In
this test th~ gum stability is indicated by the rate at which the pressure
decreases or the rate at 'which oxygen is consumed.
'~
I'
I
I
I
REFINERY PRODUCTS
Specifications are the result of a compromise between desirable performance characteristics in the product and the abili,ty of the refiner to
make such products from the crude oil at hand. Thus the whole operation of refining must be governed by the performance of the product when
in use. Nevertheless, wide ranges in physical properties 'can be tolerated
or may be advisa.ble for some products. As one exampie, gasoline Dlay
have an end point between 300 and 437F and may vary in gravity from
50 to 70 API, depending upon the sales region, the source, or its use.
In general, finished refinery products may be grouped as
1. Volatile produd8-liquefied gases and natural gasoline.
2. Light tn13-gasolirie8, rocket a.nd jet fuels, solvents, trn.c~r fuel, and kerosene.
32
PETROLEUM
Lubricating
Greases and
engine,
cylindert
wax) microcrystalline wax,
Specialties--medicinal
asphalt, carbon
etc.
hydrocarbons, chemicals,
6.
etc. '
STANDARD GRADES OF
Range
lowable
ci.fic gravity,
CNGAa
grade
PETROLEUM
Approximate composition
60"'Fj60"'F
B
C
80
100
125
D
E
F
a
200
0.586-0.555
O.
O.
.545
.535
O.
.525
0.530-0.510
0.520-0.504
.!
!'
,r
l
to
33
10-34lb
25-85
Not less than 90
Not higher than 375T
Noncorrosive'
Negative, "sweet H
Not less than plus 25 '
85
'4J
L.
~30~--~~~~r-~--~~~~--~--~--~----~--~
~26~--~--~~~~~---=~----------~--------~
Grade 26 -70
'r
~22~~~--,r~r-----~--~~----------~--------~
Grade 22 -10
Q. '
~16r-~~--~--~~~------~-----------+--------~
Grade 18 -55
Grode 18 -70
~14p---~--~--~~----~~;-----------~~--~--~
~
Grade 14 --55
G'rc.de I;;: 70
IO~----------~--------~~-----------L~--~~~
FIG. 3-2.' GradeS of n~tural gasoline with the common grades shown within the block.
I,
,
to
to White No. 2-116; Fuel 72, No. 2-1l4A; All Purpose, No: 2-103B; Grade' 80, ANF24; ,Grade 87, AN-F25j Grade 91/96, AN-F26; Grade 98/130, AN-F27; Grade 130,
AN-F28; and Grade 140,' AN-F29, Superintendent of Documents, Washington, D.C.
_.- . . _ . ,
-- -----
T ..UU.J!I 3-6.
10%
::r:
60%
90%
E.P.
221
212-27
212-207
212-257
212-267
338
338
sa8
338
888
221
221
221
221
284
267
312-257
284
392'
366
' 392
201 -
236
205
191
19B
. 207
194193
207
314
211
Ootane uumber
Gum,ms
243
242
241
246
232
332
246
249
246
Uroerml
"
,.
,.
"
"
.....
. ",," , "
I
"
..
...
to "
.. ai,"
..,.
"
306
322
342'
"
. . . . tI
"
..
"
340'
aMI
861 1
3~7'
....
. ...
I
"
"
0.9
1.2
1.2
1.1
..
.
"
...
,"
, " ....
....
"
"
....
2.1
2.0
2.8-9.6
8.0-8.1
~.2
1.8
6.8
6.li
6.6
6.7
6.4
6.5
6.6
6:6
6.1
6.6
0.9
14:6
267
1928 regular ... ..........
379
426
' 4.03
242 .
864
1934 regular .... , ...... ... .
185
. 225
127
1939 regular .......... , ...
ssa
396
. 338
126
229
896
1946 regular ... . ..........
123
218
326
1946 premium .... , ..... . .. ,
387
144
236
341
39S
1946 (lom\:Ut.LveJ ..............
133
342
1964. regu r. 8ummer . . .... .
407
~g
1954. regular. wint;ar ....... . ..
120
334
40a
ZT. 1954 premium.' ...... . ;' ... . . " .118-1S0 210-221 330-367 401'406
28. ' 1964 premlum. max' ........... 140-147 266-260 '369-884 437-442
116 ,
29. 1956-66 pram um. willt.ar; .....
209
332
403
. 80. 1966-67 premium, winter ........
115
209
330
4.02
,1
20.
21.
22.
23.
24.
26.
26.
9.6-16
9.6-16
9.6-16
5
6
"
Motor
(or lean
ra.ting)"
. '9':5' .
10.6
9.8
10.0
7.6
8.8
10.8
8. 3":"10.8
10.7-18.0
11.0
11.0
87
0.4.7'
,.
... ,. .
.. "
"
"
" ,. "
98.S
"
106.982.0'
93.&
10T.0112.0120.0-
It "
9S.6
alla
None
"
80.6
85.8
88.8-8~
85.6
86.2' .
0.0115
0.018
0 . 016
0.012
0.014
0.016
0.016
0.014
2.8
S.36
0.41
3.72
3.71
2.92
4.48
146.()J
..
..
"
..
..
..
"
..
2.24
1.86
92.~8.6
2.27-2.48
96. 9-97. Il 8.03-3.06
96.6
2.84
98.7
2.38
--
The "lean" and If rioh" rioting methods apJ>..h- j.o aviatlou (uela.
.. Potential gum ,(D873); o\her 1igurea a.ro .A.S'l'1I4 pWormea. \l,ID.,
aooota.ne plWl the ml of TEL ah.own.
.
.
~ Various yearly U.s. Bur. 'Mines Rept.. hJ.veat. Ea~lie.et. figure.: Zioa:eo.h.a.in, W. T Yearly Review. Oil. Gru J., JUAe 8 ... 1939.
PcrfDl'Dl&oee lJumber..
.
.
,
I Estimated from data. ina.dequa.t.e' for Bur. Mines oommitm8.lll.'
~ ~e o( a.V8rage winter aQd average Bummer.
~ MlnimulD./J were: Motor 7~79.6
~ 87.J-81.8.
Bum 10
60% evaporatecL.
.. "
98.S131.0'
136.0'
66
69
73
86
86.S
4.6
88.0'
84.0-84.6
0.05
0.06
0.05
0.06
0.05
S.O
180.9'
76.9
80.9
64
80.8
SO.8
82 or 89
82 or 89
."
80.4
Sulfur
max. %
0.6
2.0
3.0
96
1. 28'
1.681
2.8
100
0.224
..
TEL
fluid.
max ml
per gal
-Research
(or :rich
ratiJlg)
80 .
91 '
7
7
7
7
7
6'
6io
Reid
vapor
preaaure
0.081
0.067
0.09Z '
0.088
0.076-0.085
O.247~.aO'
0.060
0.061
35
140
149
158
13.5 '
11 .5
9 .5
Color, gravity, initial boiling PQi~t, end point~ and 'n'o neorrosive 'sulfur \
are of little importance. Water, sediment, or con-osive sulfur quickly
lead to difficulties in the Ieed system. Gum that has already been formed
. , in the gasoliI?-e, known as " preformed gum'~ (ASTM, :0381),1 can be
. tolerated' in only 'small amoun ts,:
"
.
f- ,
,
i
- 6-10
15-25
, Satisfactory
Only a few hOUI13 'and up to 1,000 'miles
be
be
Nelson, W. L., Allowable 'Gtim in Gasoline, O'i l Ga3 "" Jan, 11, 1946, p. 85. .
II Marley, Martin, and Grose, Moderate Gum Content Gasoline Not Harmful, Oil,
aa, J., Nov. ,10, 1932, p. 12.
21
36
3-7.
----
Polysulfides
Mercap tans
Disulfides
36
33
31
44
50
57
. 37
67
40
45
52
57
60
70
75
68
71
60
65
0.01
0.015
0.02
0.03
0.04
0.05
0.06
0.08
II
62
0.10
...
0.15
0.20
0.30
...
.. .
...
42
48
76
Thiophenes
23
28
20
Under 6
24
10
33
28
33
37
40
43
47
13
23
27
31
38
51
43
57
61
53
60
66
69
40
45
57
48
52
57
61
67
72
77
77
. ..
...
Free
sulfur
53
68
73
. ..
Refill~,
Sulfides
and carbon
dilsulfide
18
a X 100
llo.
in which ao; is the actual concentration (mljgal) 6f TEL in the fuel, and
a is theconcentration needed if the fuel were free of sulfur. Thus, if the
Walters et aJ., Practicsl Test for Estimating Storage Sta.bility ofGasolines, Ind.
Eng. Chern. Anal. Ed.,. 19, 987 (1947); also, Gwn Formation in Cracked Gasolines,
U
sa, 83 (1940).
,.
f
37
value of L is 60, it means that 60 per cent of, say, 2 ml of TEL is used to
overcome sulfur, and only 0.8 ml would be required if the sulfur were
absent. If several types of sulfur compounds are present, the equivalent
of these is stated in terms of disulfides (Example 3-2).
Example 3-2. Effect of Sulfur on TEL Required. In the first column of the tabula.tion is shown the amotmts of sulfur in Foster West Texas gasoline. The second
column shows the equivalent of each of the compounds if it were . disulfides) i.e.,
0.045 per cent mercapta.ns indicates in Table 3-7 a value of L of about 58.5, and if
58.5 is located in the disulfide column, the equivalent amount of disulfide is about
0.055. The other equivalents were obtained in a similar manner from Table 3-7.
Wt %
Merea ptans ............... 0.045
Disulfides. . . . . . . . . . . . . . . . 0;021
E lemental sulfur ............ 0.006
Sulfides ..................... 0.015
Thi.opbene .................. 0.008
Total ....................
.......
Disu16de
.equivalen t %
0.055
0.021
0.002*
0.007
0.000
0.085
A disulfide content of 0.085 indicates (Table 3-7) a loss in lead efficiency.of 66 per
cent. A similar value of L is obtained if mercaptan or sulfide equivalents are used.
If the actual gasoline required 3 cc of TEL, it would require only 0.34 times 3 or
1.02 cc if it were completely desuUurized.
.
i .
38
ESTIMATED
Additive type
1955
Approximate
dosa.ge -
Millions of
pounds
Million~ 0(,
doUars
..
"
40G-450
Q-3 ml/gal
2'-161b/I,OOO bbl
1-31bjl,OOO, bbl
IO-SO ppm
Preignition prevehters .... , .. ~ ........ ,0.01-0.02 %
An ti-icing ..... '.... ~ .............. , ... ' M-l% ,
l1pP8z:-cylinqer)ubes .... , .... : .... '... a. few 310 %
Dy'
es and,decolorizera ........ ': ..... '_.. trace
.
".
., ,,
.~
II
.....
.- . . . . . .
250
7
'6.0
1.5
5
8
190
140
1
776
2
1
3
10
5
I
279
II
~arson,
C4~
C.- 'M., Additives for Fuels and Lubriea.nts, Pet. Engr., March, 1955, p.
Among the latest' additives '(1957) are methyl eyclopentadienyl manganese tricarbonyl of the ,Ethyl Corporation, and an organic boron compound of the S'tandard Oil, Company ot 'Ohio. The boron compound in
Small a.mounts (0.008-0.03 per centY not 'only reduces combustion-zone
deposits and surface igilltio~ but also increases the effectiveness of tetraethyll~a.d. Antiknock effects are greatest with leaded straight-run or
H Actditives' for Fuels ~d Lubricants, Pet. Engr., March, 1956, p.C-44.
.J
39
3S0r----+----~~~~~~~~~----+_--_4~~~~~~~~~
PREVAILING WEATHER
10
<i.
-40
~IOO~~~-~o~~::~~~~~~----t----t----~---L---J
U)
-)0
. ~
EASY. STARTING
MINIMUM WEATHtA TEMP.
~ 5Or----+----~----~--~------~----~~_4~--~----+_--~
;(
~
:i
20
30
40
. PERCENTAGE DISTILLED
About nine
A Refiner's Viewpoint on MotP.r Fuel Quality, Pet Eng,.., Ref. Annual, 1943, p. 251.
.
40
at
Climate,
l:
i'
I]
Ii
r!
AllmDabh maximum
ClimaU,
Allowable maximum
DF
.oF
60
70
80
12.7
11.0
100
110
7.0
6.0
9.4
120
5.3
90
8.0
j'
Ii
.'
I:"
I!
i:
AltitJuU
.1
Relative loa
-j
Sea. level . . . . . . . .
1. 0
1.5
5,OOOt... .....
'10,000 ft... .. .. .
2.3
15,OOOft........
5.~
20,000 ft ........ 111.0
':
I~
I;
Ii
Ii
\:
I~
i
I
i
I
'I
!i
1
"
'I
.;
;,
!:
I!
"
'
. H Brownt G. G., The Volatility of Motor Fuels, Eng. Research Bull. 14, University
..
of Michigan, 1930,. p. 7.
U Good Gasoline, Natl. BUT. Sl.andartU Letter CiTe. 551, Apr. 19, 1939.
ao Nelson, W. L., Evaporation Losses a.t High Altitudes, Oil Ga8 J., Dec. 9, 1944,
p.83.
Jl Midgley, Thomas, Jr., Tetraethyl Lead Poison Hazard, Ind. Eng. Chern., 17~ 827
(1925).
at'Gaylor, P. J., Patent Trends in Petroleum Refining-gasolines, Naa. Pet. News,
Aug. ?, 1946, p. R-584.
II Campbell, Lovell, and Boyd, .Standard Fuel for Anti-knock Quality, Oil Ga:$ J.,
Jan. 23" 1930, p. 42.
o
41
..,
TABLE
Motor
method
octane
number
Approx.
15 mph
Approx.
40 mph
Approx.
60 mph
60
...
80
65
80
54
70
68
50
25
5
30
50
28
8
75 .
80
I
!
85
10
T.ABLE
3-fo.
AND
90
1953
10, 50,
FUJ..l......:aOlLlNG-nANGE GASOLINES
ma.ke
No. cars
tested
1
2
3
28
24
27
. 4
5
24
Car
28
22
88
86
87.5
87.5
84
85
7
8'
30 .
27
83
84
25
78
50% of cars
90% of cars
91.5
96
95
91.5
95
92
88.5
89.5
86
87
94.5
94.5
93
93
85.5
93
91.5
90
42
PETROLEUM
TABLE
3-11.
REF~RY ENG~ERING
ApPROXIMATE
LEAD
SUSCEPTmILlTY OF GASOLlNE8
AND HYDROCARBONSG
Octane
Type of gasoline
number
2 cc
3 cc
27.9
31.8
20
23 .1
25.5
28.9
21.1
24.0
28.2
12
9.7
14.6 - 17.7
19.8
22.9
26
64.0
71.6
65.7
55.9
9.4
8.0
8.4
13.9
11.8
12.4
11.3
16.6
13.8
14.8
18.5
21.1
28
15.3
16.8
15.3
17.4
18.8
12
38
17.7
23
69.9
83.0
57.5
-64.5
71.6
72 .6
8.3
8.1
0.0
10.1
29.1
43.0
straight run If
Catalytically desulfurized
54.5
14.9
21.3
25.2
na.tural d ..
61.6
13.6
19.6
43.4
10.7
16.9
55.9
6 co
....
n.-Heptane& ................
estalytieally desulfurized
4 co-
Number
of tests
7.5
8.1
6.5
4.0
6.2
73.0
75.8
2.5
5.9
78.4
82.5
84.3
100.0
5.0
105.3
2.0
2.2
- 3.8
1.8
10.4
11.6
12.2
9.5
5.8
9:0
9.6
8.5
6.6
13.7
12.6
16.2
13.7
18.4
Be
14.7 - 16.5
18.9
12.6
4
38
16
11.7
14.1
6.9
7.6
14.4
8.6
10.6
12.2
11.6
13.2
9.9
7.5
10.9
11.3
2.9
2.7
6.9
3.4
3.2
3.2-
3.~
8.9 -
...
...
12.4-
..... 9.-5
... . 4,3
... ...
. - . ...
...
,.
to
13
.-
30
38
9
1
1
1
Nelson, W. L., ~ Response, Oil Gas J., Oct. 6J p. 106; Oct. 13, p. 137, 1945..
" Buerstetta a.nd Warren, Oil Gas J., Nov. 21, 1955, p. 142. Numbers -over 100
based on: R.o.n. = 128 - 2,800 -;- P. N. '
o Taken from Oil Gas J., Nov. 27, 1941, p. 70.
d Desulfurized at high temperature ,w ith bauxite or clay. a
[
- I.
The octane number required by cars of even the same make ranges by at
least 7 to 12 Research octane units (see Table 3-10).37 Although additional power can be developed by the use of high-octane fuels in suitable
engines, the extra power or' mileage obtained by the use of high-octane.., CRe Octane Number Requirement Survey, 1953.
43
or
TABLE
3-12.
TYPES
OF
NUMBEB
Reeearch.
Reformed
(thermal)
Reformed
(catalytic)
St.r&ight
run'
Catalytio
cracked
nermal
cracked
Polymer
a8
applicableO
-30
35
4.1)
45
50
56
26.0
25.0
23.5
22.0
21.0
70
20.0
19'. 0
11.5
16.5
75'
15.&
60
65
80
~
_. 90 '.
95
.....
.... .
., .
.......
"
"
"
"
--
26.0
25.0
23.0
..... .....
23.5
21.5
25.0
26.S
21.5
20.0
18.5
17.0
IS.S
14.S
12.5
11.0
23.0
20.0
24.S 19.5
20.0
22.0
18.0
16.0
17.0
16.5
14.0
11.5
15.5
13.5
10.5
7.5
......
' .
. . " ..
11.S
10.0
8.05
7.0. ...
20~O
1.6.5
14.5
11.5
18.0
16.5
. 9.5
12.0
6.~
10.0
8.0 ' . . .
6.0 ........ -
7.0
5.0
.
"
....
23.5
21.0
11.0
15.0
13.0
11.0
8.5
18.0
1~.5
--
..
......
. .
.
15.5
14.0
'8.5
5~5
......
........
. -- ..
.......
....
I"
. .... "
. . ""
.. ......
10.0'
8.5 .....
6.0 10.0
4.0
8.0
. .
6.5
. . ,.
4.0
....
6.&
4.0
2.5'
.. .. "
.. .... "
8.S-
6.5
4.5
. Uao Motor methOd. with Motor octane columna and Re8earch With :Research COhl1nD8.
Gaeolinea tha.t. contain 0.1~.3 % sulf~ are le&s 6usceptible (abo.ut. 4 uniu); Nelson, W. L., 011Ga.! J
Oct. 13, 1945, p. 145. Catalytically deaulfunzed gaaolinea are more susceptible (about 3 units) i Ne18on~ W. L., Oil GCUI J., Oot. 21. 1945. p. 127. . .
.
Extnpola~ed. These are extremes, aeldom eDcountered~'
to
is
Nelson, W .. L., Power versus Octane Number, Oil Gas J., Nov. 16, 1946, p. 317.
ae Van Hartlesveldt and Field, 'Knocking Octanes, Pet. Refiner, June, 1940, p. 93.
~ Nelson, W. L' J ~d ResPonse, Oil Gas J., Oct. 6, p. 106; Oct. 13, p. 137, 1945.
6.0
160
4.0
/
f-I40
/30
I.'20
f lJlCl~e
0.5
110
[.....-1-
100
95
.......
......
--
--
~I--"
V J...--'
I 00
polYJ!ff
.....
:-t-
~r
-I-"
{c C(o eked
.....
90
PlolinurJ'l
reWrne
Thermolly
-- ---
crocked
60
?i0
.--
65
L--"
--
I---
straight
,0
90
cololy /
run
50
.....
":;?"
40
5.5
500
0.5
/.0
/5
2.0
3.0
FIG. 3-4. Ethyl Corporation lead susceptibility cha.rt . . Lines illustrate Research
(F-l) octane numbers of typiqal gasolines.
i .
.1,
;
,
.\
I
,.
'..
l
i't
I
45
, . U
3-13.
TABLB
20
Property
1,
64
62
195
205
.
API gravity ....... . .... 75.1 75.5 74.6 53-70.5 71 ~5
95
105
I.B.P., of ..... . ... ... . '.
145
.160
1~ ,
10 per cent .. '........... ,115 ... .
136 . . . . " .. . . " .180
50 per cent ............. 135 ' 150 ~/162
175
90 per c~t ... ,....... '..,'..
220
156 ......
195
188
E.P., of ................ 186 ,160
210
260
206
-73
.... . -40 . . . . . . . . .....
,Flash (Tag C.C.), OP ....
Kauri butanol No ..... . . . I 30.5 34.5 33'. 5-49
34
II
(high , 80lv~ey)
TABLE
3-14-
4.0
1'19
... . ,," .
. .. - .
200
210
215
210
220
191
245
Z15
240
.. .
..- ...
"
77
~.5
37.5
." .
USES OF
20
REPRESl!lNTA~
Use of solvent
,Boiling
range,
op
fl
~I
3 ' 4.
2
5
8
'95- 145- 125- 160- lOS-:- 179186 160 206 210 260 275
I,
I!
,I
;1
l'
.. ..
.. x
- - --
X
X
. ..
17!)-27~
. ..
:r
.. .. .. .. .
.. ... .,. ,- x
5. 'Rubber cements, .tire manufacture ...... 95-370
x
x
x
x
fas~setting
..
...
- ..
'
95-370
'x
205-300
. ..
125--400 ..
160-370 ...
105-455 ..
160-410 .. .
179--UO
240-340
2O<HIO
200-400
275-370
300-455
357-410
312-650
x
:
.. ..
..
'x
,x
.. . . .. ..
x
.. . .. x
... . .. ..
... . .. x
...
a-
..
..
..
.. ..
x
.. . .. . .. .. .. :r
.. . .. .. . .. .. ..
.. . .. .. .. . .. . .
.. . .. . .. . .. ..... . ..
.. .. . .. . .. . .. ..
.. ... .. ...
..
...
.
.. . ... .. ..
..
.. . . .. .. ...
..
t
I ,.
'
~ I
10
15
16
36-50
303
317
328
---35
275
280
300
.. . 330
340 360
.. 80
73
72
59.5 37-58 46
200 200 225
210 215
. .
242
232
217
58 ' 4.0
220 240
230 ..
250 285
,232
270
..
253
2.7
286
25
25
45
38
..
38.5 39-69
54
14
13
12
11
352
376
99
35-63
17
18
19
20
50
'48
312
322
325
30-50
357
45
350
375
40
320
367
380
397
430
. ..
333
350
370
400
115
410
136
455
142
33
35
31-85
32
337.
368
380
375
485
400
..
650
145
ranges, OF
,
12
13
14
16
11
10
16
17
18
8
9
19
20
220225240275- 300- 312- 325- 357- 350- 320195- 20~ 200- 200215 24' 247 '285 280 300 340 360 370 380 400 410 455 650
7
~-
x ..
..
.. ..
x .
x '. .
.....
--
..
- -- - -
to
..
..
..
..
..
..
..
..
x .
.. .
.. . .
.x ..
..
x
x
. .
. . .. .
.. .. x
.
.
..
..
..
.
.
..
..
.. .
. .
..
..
..
..
x
x
..
..
..
x
x
x
..
.. ..
.. ..
..
..
..
..
..
... -
. .
..
x .. ....
..
x
.. .. .. ..
..
.. .. .. ..
.. .. .. . . ..
.. .. .. .. . .
x
'
47
..
..
x
x
x
x
.. . .. ...
..
x
x
. ..
..
..
..
. ..
. .. . .
'j
x
x
...
;X
...
x
--.
,.
..
"
48
or
j
(
t
,
.
,i
.!
. t
'r
49
3-15.
No.
FUel
of
SarJ1-
pIes
CHARACTERISTICS
0J'
Dist. temp.,
API
gravity
JET FuELS,
o~
1952-1956 11
Reid
Sul-
vapor
f1,lf,
pres- wt
sure %
Gum
Aroexistmatics,
ent
vol. % steam. je.t
42.3
338
368
421
.. 0.057 14.3
52.5
316
433
56.5
55.6
166
160
421-
157
265
272
430
24
23
50.5
222
216
332
319
430
51.5
31
52.4
217
317
409
37.3
39.8
397
392
432
428
37.7
389
418
..
0.167
491
485
468
0.5
3
.1
39.3
386
422
472
0.18.
425
.. 0.26
8,3
12 . 0
10.0
12.8
Bur.
1.5
1.1
0.6
0.8
..
2.0
0.9
1.0
D.5
Mines
TABLE
3-16.
1954
SPECIFICATIONS AND
Grade JP-3
Aver-
Gravity ..........."........................
Distilla.tion temp
10 % evap., of ......... "......... . ........ ".
50 % evap'J of ........................... I
90 % eva.p., !;IF ....................... . .....~
400F point, % evap ......................
End point, !;IF ............................
Reid va.por pressure, pais. ................."...
g Freezing point, OF ..... ; .................
Viscosity, kinematic at -40F ...............
Aniline point, of. , ................ , .........
Aniline gra.vity COIl6ta.nt ................... "..
Bromine "No., wt % Br .....................
Sulfur
Total, wt %............ .. ............. "...
Mercaptan ~ ........................ ; ....
Aromatics, vol. %....................."....
Olefin content ....................... "." .....
Smoke point .. , .......... , ....... "~ .........
Smoke Volatility Index .... ", .... , ........... ".
Gum
Existent .... ". ".... ""...... , .. '... " ........... "
Air-jet. 400"F mg/lOO mI ................
Steam-jet, 450~, mg/lOO mI ...... " .....
a ,. ,.
-.'
... _
.,'':..."V'''~'
...
age
Specification6
66.5
45-63
160
265
421
84
"
Grade JP-4
...
"
" "
" ,
........
age
Speoification/)
51.5
45-57 "
37.8-41
216
319
425
250 max
370 max
-470 max
384-395
418-424
470-480
27.5-16
Aver-
.'....
" "
"
400 max.
"
............. -, 82.5
600 max
5-7
-76 max
, " "
.""
to
.........
"
0.089
0.4 max
0.001 "0.005 niax
10.3
25 max
0.6
29.4
. . . . . . " .. " " a
64.7
. ,. ..... " " . "
...............
I. ...... .
"
1.6
1.5
lOmax
"
....
"
......
,.
..
. ,
... .,
.......
"
..
..
"
.....
"
"
"
..
......
"
....
5,240 min
30 max
..
"
....
".
""
35-50
........
0.080
0.4 max"
0.33--0.075
0.0016 0.005 max
0.001
11.3
25 max
20.3-15.13
5max " 0.9-0.87
1.3
28.7
21
" ... "" .. ", .
63.4
54 min
33-27.7
."
...
1.3
0.6
7 "maX
...
'"''
.....
..... _
DERD"
2482
specification"
Specifica-tionl>
Range'"
550 "max
2-3
-76 max
.........
2.6
, "
5.7 "
<-76
<-76
2.15
3.26
130.5
..... . ........ " 133.8
7,"373 .,," '" " .. I" 6,891
" 1.06
1.59
"30 max
t
Grade JP..5
410 max
MOmax
,
"
...
"
-40 max
20 max
"
572 max
-40 max
6ma~
5-30
0.5 max
0.2 max
0.005 max:
" 25 max "
20lll8.X
10 max
6 max
1.0
-.
... ' . _ _ _ _ . _
r __
. 0 _ ':-- " ,.
TABLE
3-16.
1954
SPECIFICATION,S AND
Grade JP-3
Aver-
age
Accelerated,
........ , . .. , . , ... , ... , . . , . , . . . . . .
20 max
...
Air-jet, 400F mg/lOO rol. . , , , .. : .. , .. , , , 1.8
Steam-jet, 450F, mg/100 :inl, , .. :', ..... . . 1.9 . . . . . . . .. ,
Heat of combustion; net Btu/Jb . . , .... , , .. , .. 18,715 18,400 min
Hydrogen-carbon ratio, ... , . . . , . . . . . . . . . . . , . 0.168
~
Aver-
Specifics.tionll
age
Q'I
Grade JP-4
...
. Specific&tion'
..........
14 max
(Continued)
Gra.de JP-5
Range'
....... . .........
SpecifiC&tionll
DERD"
. 2482
specifioation
20 max
2.5
1.0
18,678 18,400 min 18,391-18 , 569 18,300 min 18,300 min
0,157-0.151
0.1635
I
. . . . .........
..
...............
Blade, O. C., Annual Surveys, U.S. BUT. Minea Rept. Invest. 5132, April, 1956.
6 JP-S and JP-4, MIL-F-5624, 1956; JP-5, MIL-F-7914 (AER), Ma.r. 11, 1952 .
. ~ Only 2 fuels. One fuel is shown 'at left and the other at right.
4 British Ministry of Supply. Kerosene used world wide in civil jet opera.tions (1956).
-At OF.
4
~.~--"
~~~------~--~-------
t
52
,1
:;
API)
N o. = thermoviscosity
R lng
5
- 10 (46'
IUlnus.
The viscosity usually ranges between 325 and 450. IIowever, an oil may
have a proper viscosity and yet fail to burn satisfactorily. Kerosenes
may have a gravity of 39 to 48 API and a flash point (Tag) of 120 to
180F. The initial boiling point is' usUally under 370F, and- the end
point about 500F, although the government at one time allowed an end
. point of 620F. Althoug4 gravity is not important, many refiners strive
to produce a 41.5 to 43 API kerosene, and hence most ~f the kerosene
sold in the United States has this gravity. A small ' amount of 1ight.
material (naphtha) is necessary in order to.produce a hlgh-quality burning oil. For this reason a little heavy gasoline must always be present
in the kerosene, and hence the boiling ranges of kerosene and gasoline
(or naphtha) overlap to some extent. If the gasoline (or naphtha) and
. kerosene are too well fractionated, the flash point and initial boiling point
of the kerosene will be so high that it wilfnot bum properly.
T he color instability -of some keros~nes has at times been a mysterious
difficulty. Several inhibitors and tests for color insta.bility ha.ve been
developed.47 The properties of a few kerosenes and related prod~cts.are
given in Table 3-17. Range oil has no close specifications and is usually
considered as an off-brand kerosene that is too high in sulfur, has a. bad
odor, etc.
. Tractor fuel oil is dis~ussed by A. T. Colwell,4& but the motor fuel tax
limitations, the need for cheapness, and the wide variety of engines ma.ke
clear-cut specifications impossible. In general, the properties of fuels
that have been marketed are somewhat as follows:
.
Flash point, min .... . ............. , .. Low to 115F
10 per cent temperature, min .......... ' 176-422~
95 per cent temperature, min. . . . . . . . .. 437-555F
End point tempera.ture, max .......... , 48D-600F
Sulfur, per cent, max ................. ~.l-O.5
Conu..,
\
t
;.
I
~
I
I,
I
..
'
3-17.
TABLE
Dist. temp, OF
Na.me of product
Kerosene:'
~ecia.l arotic export.
~na.l or long-time
urning oil
Flash,
Gravity,
API
1.0%
I.B.P., recovmin e~ed,
max
OF
min
110-120 300-325
44-48 ' 110-125 300-:-335
,46-49
"
.....
"
44-46
E.P.,
"
..
"
"
..
"
"
......
..
per-
465-490
480-600
0.05-0.1
0.04-,0.1
48G-572
470-572
0.05-0.1
0.03-0.1
25-30
26-32
29-:-34
'
..
..
....
............
..
........
"
"
"
..
"
..
42-45
110
............ 365-410
at 95 % recovered
mAX.
.......
Others
"
"
"
...
"
"
"
" "
"
.......
.... "
...
........
..
24 br
+30
+26 to +30 120 min 10 wick char
(and
14 da.y)
20 wick char
. " . " . +16 t.o +30 24hr
24hr
+30
"
(and
21 day)
24 hr
+16
.. " ... .
+.16 to +25 20 hr
72 hr
+25
"
0.05
----
...
...
, 1" ..
.....
....... . PaBS
.. , ......
,.
..........
..
Pass
. ...................
..
............ Pass
. ..................
.. ..............
.. .........
525
Temperatures
"
..
Burning test,
time
Color,
Saybolt,
min
strip
572
115 " ,. " ..... .. " . " .. " ..
0.13
, ,F.ederal, VV-K-211a.
600-700
300F minera.l..seal ... 36-39 250-260 480-540
515
145 " ... " . " .. .. " '" .. "
Range oiL ..........
43
~aator fuel, ASTM
D1215:
!4ght gra.d(J. '........ . .. .. .. . .. .. ..
1.0
347 465-518"
..
..
,
....
,
.
..
.
.
..
..
..
.
..
..
347-401
1.0
466-518
'~uw fsade .......
lis . a.te,
TM D396:
1955 Grade No.1 .... 35'.2-48.5 114-185 317-396 350--420 487-586 o.01g...{) .51t
...
PRODUCTS
"
...
"
'max
max
105-130 350-370
110-130 3,5Q-370 .........
41-44
Sulfur %,
REUT&>
'28
.. ..
Pass ..
..
.. ..
. ..
...................
-10 to -60
le0ur point .
................
ero to -65
pour point
.. . . ......... Freez~ point
-40 0 .
Aromatics,
, 5% max
I
r
54
i;,.
PETROLEUM
R~F1NERY ENGlNEE~G
as follows:
,
.j
' :~
i:
II
,.r
,
Per cent
distilled
at 44.0F
52.8
52.0
20.1
15.9
Year
API
1938-1941
1942
1944
36.4
35.9
32.6
32.9
43.5
10.5
44.5
13.0
"
I'
Diesel
Index
1945
I'
.~
of burner'
ASTM
gra.de of fuel
Per cent
req~d
of sales
(1947)
... " ..
10.8
i
I .
i
"
"I
'
Vaporuing.t.ype ................. : .
N &tural draft .................
Pot type, forced draft ... ; ........
Vertical rotary, forced draft .........
Vertical rotary, B.tomizin g .............
Atomizing-gun type:
Low preasure ..... . , ....... '. .....
High pressure ....... '.......... : ...
,1
1 or 2
lor 2
lor 2
3 or 2
2' or 3
11.0
6.2
71.7
'The flash point of do~esiic fuels is ~ted bec'a use of safety, ~d an upper
limit ~s imposed to ensure ,easy ignition in vaporizing-type burners. ' Carbon residue on a 10 per' cent .ASTM residue. indicate~ something of . the
tendency to produce coke in vaporizing-type burners, but the 90 per cent
di8till~tion temperature i~ probably equally significant, and a good corre]ation is obtained only upc:m consideration of the carb01lrhydrogen ratio, 4~
DieseJ Index, or aniline. point. Viscosity na.turally falls within proper
liririts, but in- general each atomizing-type burner exhibits a maximum
capa.city at some inteITnediate' viscosity.~o Sulfur is norm~ly .of little
significance; but, for chicken brooder hea.ters, heat-treating, and glass or
cer~mics ware furnaces, it may be specified. ColOr and odor are not vital,
but, purchasers note them. The iI;lcreaSing use of cracked d~tillateB or
cycle stocks- ,dis~illate fuels has help~ the pour point but- has introduced difficulties, with s~bility. . VarioUs additives are employed to
in
n ' Ca~ey and Delgass,. Carbon Hydrogen Ratio of Cata.lytically CraCked Distillate
Fuel Oils, Oil Gtu J., July -27J 1946, p. 166. .
,
.
~(]lendennirig ~d Sullivan, ~terlstics" of 'Fuel On. 'Hall. Pel. NttDB, Aug~ 21,
1936, p. 41.
.
"
-
TABLE
Grade or name
64-70
64-70
.........
..
..
.. .. .. ..
Distillation, ClF
Pour
point, .
Flash
point,
of
API
3-18.
Viecos-
ityat
100F
max
Sulfur
OF
I.B.P.
Max
10%
..
.............. , ..
130
155
............
112
162
Max
90%
E.P.
280
293
350
335
Others
20
.. .. .. .. .. .
26+
100+
675 ............ , . .. .. .. .. .. . . ..
440
40
Ca.rbon res~ a.3&.
4
25.8-44.7 126-230 -60 to +20 300-460 368-491 451-630 487-708 0.03-0.99 1.6-4.3
B .S.W. below 0.01
24.1-47;2 128-230 -45 to 25 312-457 370-498 457-650 49i-714 0.05-1. 4 1.5-4.48d
37
..
"
"
~..
.........
"
..
"
482
518
..
.....
.....
"
max.
..
"
"
-~-
..
....
"
..
..
"
..
"
.....
..
to
"
630
'--
"
..
"
"
........ " . .
--
"
.....
"
..
39
-
--
Demulsibility 9
min
Mol. wt 217
---
3-19"
TABLE
Description of fuel
Fla.sh
point,
of
min
API
grav'ity
..
........
,.
to
II
..
,,"
""
...
II
..
....
......
..... . . . . .
I'
....
,.
II
....
II
..
...
Anilliie
point,
of
..
....
SuI-
p,
.......
01
I,.
1.0
1.0
0-0.7
0.2
0.142
0.128
0.142
0.5
153
151
150.8
160.2
0.326
0.457
0.273
0.285
0.523
1.0
1.0
153
157
150.0
149.0
143.0
0.79 146
0.577 163
0.39 151.0
2.0
57
,f.
!
I'
. Even the small amount of dirt carried iIi dusty air can pollute diesel fuel,
because the plunger -,of the Injection pump is lapped to a tolerance of
0.00001 in. Excessively large amounts of sulfur are thought to contribute
to engine wear, and sulfur obviously can cause muffler and exhaust-pipe
corrosion. Good ignition ' quality; as measured by cetane number or
Diesel Index, assists in easy starting, starting at low temperatures, low
engine pressures, and smooth operation; whereas a fuel with poor ignition
quality promotes misfiring, varnish on pistons, engine dirt or deposits, and
rough operation. Fuel economy is slightly better fox medium- or low- ,
cetane-number fuels, but engine load is much 'more important. Highviscosity, high-boiling-range fuels cause engine deposits, smoke, and odor;
but too Iowa viscosity may lead to a slightly lower efficiency becam~e of
poor lubrication of the injectors, leakage, or the low heating value of such
a fuel.
'
The approximate relationship among ignition quality properties is
indicated in Table 3-20. The most important of these is Diesel Index,
which is defined as the API gravity times the aniline point (in degrees
Fahrenheit) divided by 100. Ignition accelerators, such ~s alkyl nitrates
(especially amyl nitrate) or nitrites, aldehydes, ketones, esters, ethers,
and peroxides" have been investigated. 51 , A' major difficulty has ' been
the incompatibility often encountered when two fuels are mixed. They
tend to produce sediment during storage. Anti-screen-clogging additives
and inhibitors of gum formation now permit renners to blend straight-run
and catalytic cycle stockS 25 into diesel fuels.
Ease of starting, according to Shoemaker and Gadebusch,62 depends
mainly 'upon ignition quality but also upon viscosity and pour point.
Bogan and Wilson, Ignition Accelerators for Compression-ignition Engine Fuels,
Pet. Refiner, July, 1944.
IS Effect of Fuel Properties on Diesel Engine Performance, 'Oil Gas J., Jan. 12, 1946,
p.74.
U
58
Fuels more viscous than 550 sec Saybolt Universal at the starting temperature cannot be handled by some fuel-ignition pumps. Plugging of'
screens or cloth filters tends to occur at the cl~ud or haze point, which is
wma11y about 10~F abo~e the pour point. Finally, the cetane number
3-20.
TABLE
I,
Cetane
number
Diesel
Index
30
35
26
51
,34
43
42
49
.56
35
27
19
11
2
40
45
50
55
60
II
G- B
Blending
Characteroctane numiZ8.tion
ber (Motor
Factor
method)
+ (68 -
64
72
Boilingpoint
gravity
number-
11.05
11.25
201
196 .
191
11.45
11 .6
11.8.
12.0
187
183
180
178
12:2
e, and B
= the
~nstant.
TABLE
3-2L
Air temperature,
OF
!' ,
Maximum
pour point,
OF
-20
42
-10
46
-20
"':"10
0
10
-30
Cetane
number,
mm.
90
83
76
10
50,
57
20
30
65
70
20
56
40
50
98
30
49
...
40
60
160
50
43
36
..
Maximum
viscosity
Saybolt
Universal
a.t lOOF
69
63
must be high enough to permit ignition when the air that is compressed is
cold. The properties required are somewhat as shown in Table 3-21.
Obviously viscosity gives little trouble.
.
.
Lubricating Oils-General . Ther~ are so many uses for min'eral oils
that a formidable array of names, based on uses, has arisen. Several
grades of viscosity are useful for each general type of oil,-but So relatively
few.types of oils will satisfy most of the needs' of industry. Table 3-22
..
TABLE
3-22.
VISWlity &t
Name of oil
,
UIed. for
API
l1>OF
Automotive engine
Automotivo engine
AutomoUve 61lP
. ..
Alrplanea
AirplaAea
Dlcnla
DleMIa
Automobiles
l'r,npm'18lOa
. . 0ilh
. : Automobiles
, ea.VJe.lJt.
CDaiae and machine, spiQdle ...... Tex.tiles, eto.
ilqiue and maclilile, heaviest .. . .. Heavy ma.ahinery
Jold tat, liibt .... '....... , . .... . lWfrige:raLion, etc.
)old 1ie8t, haavy .... . . . Refrigeratioo, et.o.
~linder oils. Wlfiltered:
Light. mineral .... : ............
Heavy mloeral ........ , . . . Engine or aompreaeDr
Licht oampoWlded .. .... oylialiera
aeavy oompoWlded. , .... ,
ladue engine. mineral. ... : .... . Marin.e eIliPneB
{wiDe OJigiae, Dompound ...... Marine engines
'urblne oil. light ......... .. ..... 8\e&m ~urbi.tleB, d)ona'llrbiDe oiL medium. ' " ....... moe, high. apeed, etc.
'urbine ou. beavieat .............
'raDerormer oil . .. .... . .. . .... Eleotrioal trusformera
Flaah.
cCllit.y
IJUieJ.
(Opell
oup)
130'
2l0F
24-30
22-28
20-27
24-26
23-215
9(H'8/i
(H5
10-100
860-400
~OO-650
186-~g3
62-90
...... , "
~100
~riD
... I I ,..,
80-165
40-100
gO-I 00
Com-
Poor paiut
Carbon
pound-
resid.ue
inloiI"
peroent
. . .. ,. .., ..
" ,. '"
110-85
27-32
25-28
2&--28
20-28
.. . . . .
22-25
21-2S
20-22
25-27
21-26
26-28
' 20-26
23-28
23-28.
,.
... I
"" "
.1 1.'.1
~
,.
11.,1 II
"
. . ...
"
.. 1 ,1 . . . . .
..... I
"" ,
""
........ I
II
"
. ....
I
"
...... , ......
136-166
176-220
...........
........ , .... ,
..............
.. , _.t ....
_, I I . " '
, ......
..........
"
29-31
12'0-116
27-30
S6-S8
176-340
476-636
28-30
66-66
I~~ ... ~_ ~
10<>-:145 90-100
...... .
12G-:-186
40-70
.. . .. .. ..., .. 7HO 4G-70
800-1,600 ... , ..
...... , .. , ...,
200
1CXH26
..... " . , .... , ........ .. ,
7OG-8oo' ...... ,' .. .. ............
140-170
. .. . .... .
............
300--326
. .. ..... . . .. , ..... . .. .. , .
23-26
Bpe~ property
. I'.,. .
r::";"""'"
V'II-
--
..
n!i:':"'"-"'r""="
DuoS
.. "
...
"" "
..
"
".
,
I
.
" .. " ,
.... " ..
...... "
.... "
"
.........
" "
"
---
"
" " ..
"
....
"" ""
" ""
UHIO
oto 25
oto 25
400-426
475-S00
-10 to 0
o to 30
880-360
-10 to 10
oto 20
-10 to 10
Oto 80
oto ao
agO-nO
8O<H20
600+
820-360
oto 30
17HOO
31G-350
-20 max
840-400
-10~
4UH40
20 to 60
30 t.o 60
10 ~o 40
620-600
460-610
620-600
860-410
30 to 60
- - -
"
.. , " ,
... I
.. , .
.. ,
..
, ..... . ......
... ....
... ... ,
.. .. ,
.. ,
3.H.O
3.n-4.0
1.0-~ . 0
...
0.1-1).'
. .......... "
Oto 30
II
0.3-0.8
3li IlWt
-60 too -80
"
~
...
,.
O.DH.l
0.06-0.3
." .....
"
' 0 to 35
"
., ...,-,
. .... , .,
"""""
.. .
"
..
"
..
11"1"
4'
",,
II I.'
...
.. .. " , .
... , .
II '"
" ,. ,.
320-UO
:t60-t60
216-826
""
,. '"
1.&-2.0
36 max
Ot.oM
""
,. .,. "
0.~.6
UH.O
. " ........ "
36 W%.
-20 too 0
0.08-0.6
O.HU
0.2-1.8
0.&-l.0
3150-410
31G-360
. . . . . .. ..
, ""
""
""I
..... .
.. .....
...
......
86-75
~80
..... ....... . .
I"
95-110 . , ......
176-220 " . "
.........
'"
-10 La 16
......
VlICoailu'
Low- pour point.
Low pour point
None
emulai.on
...
1 . 1 .. ,
...
t,
.....
,'
....... . . .
I
60
shows the properties of some of the maj or types of oils, and the approximate amounts sold during 1950 are shown in Table 3-23.
In general, oils may be grouped as follo.ws:
L Engine and Machine ~iu. High viscosity Index oils are required for
. aircraft engines and automotive engines operating in temperature and
arctic climatesand for machinery or instruments that are subject to wide
variations in temperature. Viscosity and Viscosity Index (see Fig. 4-2)
are important considerations.
,,.
I,
TABLB
3-23 .
Type of oil
.,
ThoUsand bbl
Percentage
Motor oil:
Premium ....... '.' ....... , .. '.' .......
Heavy duty (2-104 B) ...............
MIL -2104 .. ~ ...... , ..............
Total .....' .......' ....... '...... , ...
Industrial: :
22,000
9,700
2,250
2,250
Premium ...........................
Heavy duty ........ ' . , . ; ~ ....... ' .' ..
R.a.ilro 8.d .dies e1. . . . '.' . . . . . . . . , '. . . . .
Total .... : ... : ...................
Gear oil and grease, .... ~ ... , ... , ......
Total domestic .....................
Total export. .....' ... '; ... ; ........
18.0
12.3
19.6
6.5
56.4
7,000
4,800
7,650
2,550
'150
"
450
14,800
2,200
39,000
14,200
\i
l
r
~
24.8
5.8
5.8
0.4
1.2
38.0
5.6
100.0
Medium Viscosity. Index oils are suitable for almost all industrial
machinery including stationary spark-~gnition engines and automobiles in
temperate or warm climates.
Low Viscosity Index oils are suitable for most industriallubri"cation and
.for diesel engines. Except for poor starting characteristics, these oils are
thought, to be best for general automotive. service (except arctic) because
of their natura!" detergent properties. Others' feel that a chemical detergent .Should be added to the higher-viscosity-index oils to gain detergency
properties.
Obviously the entire range of viscosity of 60 sec at 100F to 250 viscosity at 210F ~us~ be available to provide service for the lightest
spindles (of zero clearance) and the heaviest machinery operating at high
temperatures. In general, the useful life of an oil ishalved by each 15F
increase in operating temperature (above 140F). In connection with
I
I
61
as
j
j
I
I
i'
I
is of
,l
I
"
I
l'
,
~
62
..LAJI:I>.t.I.II.I
3-24. SAE
Univera.l. IIO!I
SA.B
vi8cco-
Redwood
it1
ODF
D.IWIW
oW
lOW
2OW.
20
30
40
lie)
B61Mf4 t ooo
210"1'
O"F
Ou.s
CentlBtoketl
.
O'T
21a'F
O"F
210'"1'
;,
21O":r
Below Bag
Below 3,500 .. ................ Below HI ........... "' ....
* ..
8,OOO...U,000 40mm 5.2.60-10.500 .............. 112-344
1,303-2.006
12.000-48.000 timiD lO.fi4lO-i2.000 ............... Mi-l.r74 ................. 2. fIO&-lO.m
1.7H.U
fI..I8 ....... .. .. .. ....... . . . 4OJHI1.8 ., "''' "' ...... 1.M-l.1
1.8-2.
i2
It 42-12.!K
.
..............
oL
51.
0-61.
t
.. .......... "' ....
Ai., .....
MHO
70-81 ......... "' ...... " , 61.1>-7li. 3
2.12-2.52
*' .. 11/,. ..
12. Of-tit 7'1
a. . . . . . . . . . . .
85-110
It" 75.2-17.& ......... -... 2.,-3.1t . " ................... 1&.77-22.88
.. .. t
...
. . . . . . . . . . ., ,I . . . I' '"
41,.
..
111. . . . . . .
a ..... '",.. . . .
. . . . . . . . '"
..
.... I
Ill . . . . . . . . . . . . . . .
41 .. ",-.
.. . . . . 41 .. II 11; . . . . . . . "
1
!
I
r
,~
f.I
,.
. .A . .'......
41
........
to
.....
\to
....................
til
.,
It. . . . .
As examples, 1042.is SAE lOW oil, and 3050 (or 9170) SAE 20 oil,
Motor Oils. Spark-ignition and diesel-engine oils differ primarily
because the ,diesel oils
exhibit ,i detergency" properties to keep carbon from accumulating in the engine after a few hours of operation.
N aphthene-base
(low Viscosity Index) are somewhat
as
"". . . .,"""'. . oils, but most heavy-duty oils are made by introducing a detergency
additive to an oil manufactured from paraffin or mixed-base crude oils.
Much importance has
attached to Viscosity Indexu because
measqres
suitability of an oil t~o lubricate properly at the elevated
~ N.B.S. 431, Lubricating Oil, Bureau
......uu.y... Navy Department, Washington,
D.C.,
for visoosity-te!p.perature
Figs. 4-l an~
63
temperatures' of the engine and at the same time not W:be too viscous for
operation during starting.
Easy starting is said to occur if the viscosity does not ,exceed 40,000 sec
Saypolt Universal at the starting temperature, U and, of course, the pour
point must be adequately low. Thu~ viscosity, Viscosity Index, and pour
point together govern ease of starting. T~e lowest temperatures at which
easy starting (quick-cranking) can occur are somewhat as follows:
Lowest easy starting temperature, 'T
Kind of oil
100 "
60
Viscosity Index Viscosity Index Viscosity I~ex
40
-23
-l8ta -27
o to -18
-2
13
-25
-19 to -29
o to '-19
-6
9
~34
-20 to -30
o to -20
-12
0
Obviously lOW and 20W oils of any base are satisfactory for Donna! winter
service. Zero Viscosity Index oils are not shown in the tabula.tion,
because such oils are not marketed. So called II multigrade" oils are
being marketed which meet the requirements of several or all SAE grades.
Viscosity in itself appears to be of little direct significance, and such
might be expected because the piston rings scarcely push against the cylinder wall. The oil must be fluid enough during starting 'to flow through
the lubrication systein, but it may be quite. thin (even diluted with
kerosene) at the engine temperature without causing eX,cessive wear.
Thinner
thinner ,oils are being employed. ' "Although thin oils may
contribute to oil consumption, less gasoline is used and the Qver-all 'cost
of operation m~y be less 66 or scarcely different. The factors ' tluii, affect
oil consumption are (1) low-boiling 'or low-flaSh oils, ,(2) low-viscosity oils
that allow blow-by, (3) excessively high' ~ngine temperatures, (4) high
engine ,speed or load, (5) leaks at ,gaskets' or ~otating seals, (6) carbu!etc;>r ou~ of adjustment so QIat crankcase dilution OCC,urs, .and (7) a wom
engine. 57 Of these, a worn engine, a poor c~rburetor adjustment,,, or a.
high speed accounts for most cases of excessive oil consumption.
Flash or fire pOint indicat,es little of engine peri;ormance, but it indicates the source of the oil and whether it is a blend ,of low.:. and high-boiling
and
l'
. :
,n Otto, Miller, Blackwood, and Da.vis, Improved Motor Oils, Ref. Nat. GasD. Mfr.,
November, ,1934, p. 411.
I'iI Nelson,. W. L., Signific~~e of V~cosity . . . , Oil Gaa J .., Nov. 23, 1939, p. 46.
57 Nelson, W. L.~ Co~mption of Engine Oil, Oil Gas J:, Feb. 17, 1944. D. 73.,
i
\
i
i
,
I
64
l
r
Average Rangeo!
Per cent
low~in&
I,
lowering,
of
0.1
0.3
0.5
1.0
11
1-21
22.
5-39
30
38
17-44
2H:I
Wax..naphthalene or w-phenol. condensation products and 'their poly:mers are said to be effective as pour-point reducers. 26 . Viscosity Index
may be improved by the addition of butene polymers or polymers of
methacrylic
esters.. Detergency additives are usually complex
calcium or bari1Illi sulfona.tes or phenates. Such additives tend to keep
carbonaceous sludgelike materials
settling out of the oil and will
engine.
a detergenoy
even
such, materials from a.
_additive is used, the crankcase oil
immediately appears dark and
dirty because
sludge is
suspension. When such an oil is
Iii'I Service Characteristics of Motor Oil, as Related to Chemical Composition, Oi!
Gas J., June
1935, p. 59.
.
ill Livingston and Gruse, Carbon Deposits from Lubricating
Inil. Eng, Ch6m.,
21,904
.
lW
C. W., SubcomnQttee lteport
JlYU:I'1I.al,
1943, p. 52.
Ii Nelson, W.1.., Reducing l'our-Pomt'
Depressants, Oil Ga8 J. t Dec. 30, 1944,
p.269.
"
!,
65
.first used in a. dirty engine, it loosens 80 much material that the oil
should be cha~ged at least two extra times at 300- and 500-mile intervals
~
to remove the debris.
Detergency ' oils are necessary for diesel eYiglnes, although straight
naphthene-base oils are reasonably good., and such oils are advisable for
heavy-duty spark-i.g nition engines. The engine temperatures in sparkignition and diesel engines are somewhat as follows:
Loca.tion
Spark-ignition
Diesel
500-650
650-750
.......
475-500
350
350
170-250
200-325
300-350
160-250
3-2'5.
Kind.
Detergents .........................
An tioxidan ts-coTrosion inhibi tors ....
Viscosity Index improvers ............
Pour point depressants ..............
Extreme pressure agen ts .. '..........
De!oamants ................... , ....
Antirust agents .....................
Odor con trol. ....... '............ '...
Oilin ess -lmparters
.
....................
II
La.~n,
OF ADDITIVES
19550
FOR
Dosage,
per cent
Millions of
pounds
.Millions of
dolla.rs
2-10
0.4-2
0.5-10
0.1-1
5-10
0.0002-0.07
0.1-1
0.001-0.005
0.1
280-300
70-75
57
6o-651J
15
60C
to
......
15
2
14
C. M., Additives for Fuels and Lubricants, Pel. Engr., March, 1955,
p. C-44 .
." Used also 8.8'
depressant.
.'
G 60% automotive &nd 40% industrisl usage.
.
It Fa.ust) J., Asphaltization TestS for Lubricating Oil, Oil Gal J., Jan. 20, 1944, p. 29.
pour
I,
66
67
practice in manufacturing gear "lubes" is to add a specific sulfur compound such as dibenzyl disulfide, which is noncorrosive at room tenlperature but corrosive (to copper) at about 300F.
The general theory regarding sulfur and chloride lubricants is th~t iron
sulfide or iron chloride should be formed on the surfaces o~ the bearing or
shaft arid that the films of these materials are responsible in part for good
lubrication. Thus the extreme-pressure lubricants are somewhat corrosive and probably should not be used on be.arings that contain copper.
Others believe 81i tha.t the high temperature generated at the gear:--tooth
surface causes the rough or high points on the surface to be destroyed 'b y
corrosion so that the surface is smoothed. In addition to customary
tests, gear oils for automotive transmissions are subjected to full-scale
II shock" tests.
In these an automobile is operated at a high speed; the
, clutch and ,transmission !lre disengaged; and then, whlle the vehicle is
still traveling -rapidly, the clutch is engaged. Gear lubricants, transmission oils, and many rear-axle or' steering-kn~ckle applications U - are
furnished in the following grades (with or without extre1p.e-pressure
additives), which are generally simi1ar to the SAE grades:
Use
Grade
75
80
90
140
250
......
................................
.....................................
Most greases are soap-thickened mineral oils. The National Lubricating Grease Institute C!asSmcatiou (1955) based on worked consistency is:
NLGI
number
Consistency
(D217)
355--385
310-340
265--295
1
2
3
4
',5
6
220-250
175-205
130-160
~115
Semifluid
Very soft, grease gun
Soft, grease gun ,
Grease cup
Grea.secup
Grease cup and block
Block type
TABLE
~um (&8DCral)
Soap hue
Buttery
'future
CaJoiwn reaUiate
(aold..at)
3-26.
Ca.\lu.CTERlBTICB OF GBEASES G
Sodium (general)
,libroua or amoot.b
Bul.tery
Hard or briLtla
AJuminum
Lithium
Bu~tery
1400
315
t.o fibrOWI
point, .,
220-~
(approL)
iDa poin~
l'
176
Wuimum temperature, -F (aont.muoua
I
Q)
3Q0-450
276
brous
200
~&O
I No ahaap
No obal1gB if worked
200
300-400
3~GO
Fair \0 poor
Varie&-e,cellont to
yari~Iair
160 or
~h&ps
21>0-
300
300
Variea-txoellent to
Varies-BXce1hn~
lerrice)
QO Softening uPOD.
poor
iq
Eft'eo~ of water
Primary UN
to poor
Fair to poor
ReaiBtant
Susceptible
Susceptible
~tant
Reeistant
Reaiatall"
GeneraJ-PUlp088 lubri Rough heavy belloliDp Ball .Dd roller bea..... Locomotive 4rlviog
AppliDa\loDl raquirmi Aircraft or aervloes
Cl&Dt (or plain bearat. alow lpeecia, -aJao
bea.riDp and speoial
iDiJ up to medium Joumall aDd Iimilar adheai.vanllM or . . dOlfD to -1000F
,poeda and. lip~ to
.moe.
~pliD&1.I0D8 .t. bot.b
.iQp and line ahaft.akida,
OU;n'M.
Ila\ance to oe.utrlluhigh and Itni' temper-gal Coree
mr. PreuurB BUD &Dd ftiOD wheel.. ~vy 1oads, NaO
aDd nter pumps
.tuns
Oil !eld aDd 8iricul"heel bearinga and
~ural maohinery
cbaaai4
DIfficuU.y is 8U81:eP. Does QOt oxidile Dr Ofl'ers poaaibUit.ioa Cor Special ty pea IU'e reaiatSome moisture left Cbea.pn_ i.a major NormallY doea ~
\ibili ty to lfa I.er.
chanw. Bighes~
an~ to oxidation or
iD llMIe. Certa.iD
orust. readily. Good
general purpoeea
Caotor
Smoot.h greaaea uaed
crusting and oaIl be
te.mperai.ure 8eni~
alow flow propert.iea.
~ Il.abilaed
naed Cor eleotric mowith cheml.cala iIlfor a.ut.ifrletion bear
Relatlvely ~penaive
UCIIP~ Itrontium
iDgll. Loog-.6.ber
stead oC water CIUl he
geaae8
tors Dr 88ldom lubrillIed at higher kIDgreuet for obaaaia
cated equipment
per.tuna
lubricatiol1
trw
Motel
to
poor
SUloeptible
All typea ball and roller
poor
..
Taken mainly rom ~ Plirl n, "Lllbricatioa." The Tlus Co., August, 19t6.
a~
~,.. - -( . .
'g':O:-:,".. ~..,..~-~
, . . . . . . . . '"
69
Oil
content ranges from 42 '(waterproof grease) to 93 per cent, oil viscosity
ranges from 90 at 100F (waterproof greases). to 220 at 210F, and
numerous metals and fats are employed. Thin oils are used in greases for
high-speed bearings.
Although soaps of barium, cerium, chromium, cobalt, iron, lead, magnesium, mercury, nickel, manganese, silver, strontium, tin, and zinc 67
have been proposed for grease manufacture, the main 'g reases and their
characteristics are as shown in Table 3-26. 88 Such metallic soaps as
calcium, aluminum, barium, and strontium produce greases resistant to
water; such soaps as those of barium, strontium, and lead are useful for
extreI!lely heavy duty services; and the sodium and calcium (particularly
resin ate) greases are relatively cheap. The National Lubricating Grease
Institute has been active in developing test methods, particularly the
N orman-Hoffman oxidation test,69 and performa.nce . characteristics in
antifriction bearings at elevated temperatures. 69
Waxes. Paraffin and microcrysta1line (petrolatum) waxes are used for
so many widely different services that not many specifications other tha.n
melting point have been adopted. Microcrystalline waxes may contain
natural 'or additive substances that partly inhibit orystalline growth.
This generally tends to increase the flexibility or plasticity 70 of the wax,
and in fact paraffin wax can be .added to some microcrystalline waxes
without destroying the flexibility. A common additive material to
produce plasticity is Vistanex or polybutenes. Paraffin waxes range in
melting point from about 105
155F, and the most common grades
range in melting point from 118 to 132F.. Petrolatum waxes from long. residuum stocks m~y have a 'melting point as low as 106]'. Regular
petro1atum produces microcrystalline waxes melting up
about 180F,
whereas the highest melting point microcrystalline waxes (195F) are
produced from ,', tank bottoms." Some of the petrolatum or microcrystalline waxes on the market are shown in Table 3-27. Color ranges
from black to white in almost ~ grades; and, of course; odor and sometimes taste are important properties.
Waxes are applied in two general ways, as a molten liquid or in the form
of a dispersion or emulsion in water stabilized with dispersing agents.
John C. Dean'll discusses the many uses of waxes. Among these uses are
17 Boner, C. J., Metallic Soaps for Thickening Mineral Oils, Ind. Eng. Chern., 29,
to
to
. 58 (1937).
81 Taken mainly fI'Qm Greases Part II, HLubrication," The Texas Co., August, 1945.
II Tech. Bull. ~ .and 6, NLGI 164 Cha.ndler St., Buffalo, N.Y.
70 Nelson and Stewart, Effect of-Oil on Plastic Properties ' , J Inil. ~ng. Ckem.
41, 2231 (1949).
.
.
71 Petroleum W~eS) Pet. Refiner, MJly, 1946, p. 87; and PJocessing Materials fioDa
Petroleum, Chem. Eng. N BUM, II, 1164 (1945).
'
,
I.
70
TABLE
Wax
Petrolatum .......
Petrolatum .......
Petrola.tum .......
Microcrystalline ...
Microcrystalline ...
Microcrystalline ...
Microcrystalline ...
~icrocrystanrnne ...
~
Varies widely.
3-27.
t
.~
I
Melting
point, of
(DI27) .
Consistency
(D217)
Needle
penetra.tion
(D5)
Flash
point,
of
106-118
112--124
127-137
155+
200-240
......
.......
360--370
160-2()()
170-200
..............
166+
170-175
............
185-190
190--197
..
...........
..............
to
.............
........
25-35
15-25
10-20
5-15
2-10
410-430
360-3.70
460+
460+
460-500
470-500
480--500
Gravity,4I
API
36
36
37
21-22
!
I
i
'~
22_ ... L)
71 .
T.ABLE
3-28.
I'
Oil
Flash
point,
of,
mm
130
1. ASTM No.5 .........
1955 range a 13~306
1956 range ....... , ... 136-300
150
2. Low viscosity, 1933 ...
3. Bunker B, 1933 ....... 150
l
150
4. ASTM No.6 .........
ll
1955 range : 150-430
1956 range ........... 140-420
5. Light dusting oil ...... 305-350
6. Heavy dusting oil ..... 300-365
Water
and
sediment,
max %
Pour
point.
of,
max
Maximum viscosity, .
.see
1
0-0.8
0-0.8
III
....
flo
.......
.....
All the oi1s should be free from rust, grit, acid, or fibrous material
that might clog or injure burner tips, and free from chemical agents
(neutralizers for corrosion) that will flux with the fireclay walls of furna.ce
settings.
.
.
The very sinall amounts ~f vanadium and sodium found in some oils
may lead to extreme corrosion when such fuels are burned in boilers or
are used as gas turbine fuels. This ' difficulty can be almost totally
eliminated by the use of magnesium, calcium, zinc, etc., additives. The
following requirements (1953) of the General Electric Co. U for residual .
gas turbine fuels' illustrate how the additives are applied.
1
'1
1.,
.~
..
1. The amount of sodium should be under 10 ppm (preferably under 5 pp~). It can
be reduced by customary desalting' operations, washings, centrifuging, ete.
2. The weight ratio of sodium to vanadium should be under 0.3. This may necessitate more reduction of sodium, but if the vanadium is under 5'ppm, the :Na/Va
ra.tio requirement may be ignored.
i
3. The' weight ratio of magnesium (a.dditive) to vanadium should be adjusted to .
higher than 3.0. If the vanJidium content is lower than 2 ppm, magnesium is not
needed .
. 4. Calcium should be under 10 ppm.
5. After the a.bove adjustments, the total ash should not exceed 2,000 ppm.
Similar additive formulas are being developed for distillate or jet fuels.
Gravity is of little significance except. that low-API":gravity fuels have
slightly higher heating values. At gravities below 10 API, wa.ter and
,i
.!
:1
72
sediment do not settle out of the oil and such oils cann()t be displaced from
tanks by water. The heating value of residual fuel ranges from about6,260,00() to 6,450,000 Btu per bbl. Its main competitor is bituminous
coal (13)100 Btu per lb). The parity price 0 (dollars per bbl) of Bunker C
fuel oil may be computed from the-cost of delivered coal G ($ per' ton)
by the following formula 75 in which Eo and Ee are the thermal efficiencies
at which oil and coal can be fired, If" and He are the heating values of oil
(Btu per .bbl) and coal (Btu per ton), and x is the ratio of operating costs
for the year under conmderation to the cost during 1951.
(3-5a)
consta~ts:
o=
c + 0.04x
(3-5b)
'Oil can be fired more cheaply than coal (about 16.5 cents per ton during
1951), Sulfur in fuels (oilJ coal, or gas) requires higher cold-end temperatures in the air preheaters or economlzers of boilers78 in order to prevent
corrosion and -fouling ' of the tubes. A 6 per cent sulfur fuel requires ll.
temperature about 60F higher than a 2 per cent fuel.
A high pour or solid point is important in g~avity-feed systems b~~ause
TABLE
3-29. FUEIrO]L
. Firing temperature, OF
. Fuiol _v iscosity
at 122F -
SO .....................
7.
Mechanical
atomization
Steam
atomiza tion
130-182
97-130
103-136
108-143
113-148
123-161
132-171
139-179
145-184
136-191
143-199
148-205
161-216
171-226
17!}-:233
184-239
193-248
200-254
204-259
210-265
154-193
160-200
164-204
170-210
:-
73
it may cause plugging of screens and filters. Viscosity is the single most
important property 77 because of difficulties in the handling and atomizing
of viscous oils ('fable 3-29). Cracked fuel oils are desirable 78 as fuels
because they usuall:y ha.ve a lower pour point, lower viscosity, and a
slightly hlgher heating value than the residues from which' they are produced. However,.certain cracked oils deposit carbonaceous material on
steam heating coils;79 and hence cu~ter stocks having a. high solvent power
such as low-aniline-point extracts or cracked gas oils, rather than straightrun gas oils, should be employed for reducing the viscosity of heavy
cracked fuel oils. The Naval Boiler and Turbine Laboratory heater
test 80 may be used to determine the stability of fuel blends.
Petroleum coke is used commercially as a refinery and commercial fuel
(often powdered); in the manu!actute of 'carbon el~ctrodes, brush~,
plates, etc.; in the ~anufacture of abrasives and artificial graphite; in the
manufacture of calcium carbide; a~ a metallurgical fuel; in paints a.nd
pigments j in' gas manufacture; and in the ceramics industries. The
high heating value and freedom from clinker-forming substances and ,the
small quantity of ash make it a desirable industrial fuel. The hardn,ess
and strength of coke increase as the volatile matter is reduced, but it is
seldom strong el.lough to be used for foundry cupolas. Until 1954,
petroleum coke was ~ade by the delayed coking or chamber processes,
but in the future most coke ,will be made by a continuous process. 81
Such , coke consists of small pellets . which can be handled by fluidizing
techniques or air-activated pneumatic transport systems, and accord41gly
it is called "fluid" coke. ' Table 3-30 indicates the properties of, some
cokes. &2
The '-major uses 83 , of petroleum: asphaltic materials are it:tdicated in
Table 3-31. The properties of typical asphalts are shown in Table 3-32,8'
and a few properties of other asphalts are shown in Table 3-33:
,
Consiste~cy85 (viscosity, penetration, and softening point) determines
the temperature required for use or application and the final hardness and
17 Nelson, W. L., Oil Gas J., Aug. 24, 1946, p. 92; Sept. 14, 1946, p. 95; Jan. 18, 1947,
p. 89; and Feb. 15, 1947, p. 109.
'
"
,
711 Morrell and Egloff, The Congealing Tempera.ture . . . of Cracked Residue,
Ref. Nal. GQ.80. Mfr., Apfil, 1923, p. 17.
71 Batchelder, A. H., The Stability of Residual Fuels, Oil Ga.s J., Nov. 12; 1936,
p. 159.
80 Smith, F. L., Blending Residual Fuel Oil, Pet. Refiner, April, 1945, p. 95.
11 Barr and J&hnig, Fluid Coking and Fluid Coke, Chern. E1UJ. Prog., April, 1955,
p. 167.
at Ne]son, W. L., Oil Gas J., Nov. 28, 1955, p. 117.
, &1 Shearon and Hoiberg, Ind. Eng. Chern., 46, 2122 (1953).
U Petroleum Asphalt, "Lubrication,'-' The Texas Co., June"1946.
81 Roediger, J. C., Asphalts a.nd Their Evaluation for Commercial Uses, ASME
Meeting, Tulsa, 1946.
I
,
..
I,
I:
PETROLEUM
74
T.ABLE 3-30.
~ERYENGINEEBING
ANALYSES AND
PRoPER'J':[ZS
OJ' PETROLBUlt4
":
Cons
Dela.yed
process
.Oven
cokes
Coking
cokes
still
ContinuoUB
or fluid
cokes
,
..
"
....
<II
..
'"
'"
...
..
11<
....
II:
<II
..
Uses
Paving:
Asphalt cements. ~ ...............
Cutbacks and road oils .. ~ ...........
Emulsions .
Total ... : , ....., . , ....... ~ .... ;, ...
RODfing, waterproofing, and mastics:.
Roofing and waterproofing.:. , '.' .....
Flux for roofing .... , ...............
Mastic and mastic cake ..............
Total .... , .......................
Briquetting ....
Specialties:
Blending with rubber ........... , ....
Pipe and metal coatings ............
Molding compounds., ..... '.... , .....
Pain ta, enamels,. ate ........ '.......
Misc. uses ......... ~ ..............
Total . ............... "
Gra.nd total ......................
It
..
...............
..
..............
..
9'
';.,"
..
..
..
'40
...........
"
.......
II
.......
8-18
3.1-5.3
0.5--1.6 0.1-2.8
0.5-4.2 1.4-7.0
. . . . . . . . 55-65
1.28-1.42 1.
.6
14,400- ......... 14,000
14,700
... '" .......... . . . . .. .. 1.6-2.1
........ 88 .3-92.5
It
............
II
............
"
,.
II
4,574,112
4,124,564
216',247
35.6
.......
9'
....
II
_,
2,208,409
882,283
16.508
..
'"
..
:I'
/I;
..........
210,323
21,414
26,273
38,868
69,607
475,469
JII
JII
1I'
....
"
..
"
,.
........
cent
1951
...
"
..
0.6-7.4
0.2-1.8
0.8-1.5
Short tollS
1951
'w "
..
Nil-O
0.3-2
JII
12,864,077
32.0
1.7
69.3
Short. t01,l8
1955&
12)300,000
11.2
6.9
0.1
24
1.6
. I,
l-
3,400,000
200,000
0.2
0:2
0.3
0.5
3.7
4.9
100.0
I
\
400,
16,300,000
75
Roofinc
hvinc
Floor-t.ratiOIl
A.phaltic
mac-
COil-
adam
crete
Use
)
,
\
PUll-
Built-
Shingle
8biq1e
coatiq
...tQran\
I
1
t
rant;
pilla
129
100+
226
148
100
13
33
249
108
25
0.06
18
31
30
65
&70
560
99.8
.. Consistency.
..
..
302
0
2
27
67
92
0.0
0.0
600
0.02
635
90.8
99.8
99.8
MA.TEBUL8
Penetra.Ductility
tion a.t
. at 77"F
77"F.
Melting.
point,
B&R
i
1
:
Pa.ving binders:
Mastic foot pavements and Hoors ..... ~ ......
Aspbalt blocks .............................
Sheet asphalt pavement ............ _.....
Grout filler .... __ ... __ .. _........ _...
Grou~ filler (blown type) . - . '... '.' : . _.
Asphlllt concrete (aggregate sandJ etc.) .. ~ .
Asphal t mac.adam
~
Roofing asphalts:
Saturant for felt or paper ... -... ~ ~ ....... _..
Heavy Baturant for felt and rugs .............
Roof coatings (blown) ......... ~ ....
Sealing:
Pipe sealing {sewers, etc.) ...................
Pipe coatings. _......................
Waterproofing. __ ...... _.
Ul
22
10
645
99.8
ABPHALT
157
12
8
20
0.01
560
99.7
99.8
2.0
0.01
0.03
640
100
2.0
Materials
mop.
utu-
proo.fl.q
up roof
Water- . Mineral
rubber
inK
..
..
.....
.....
10-15
10--25
II
180--220
20+
25-40
40-70
40+
50+
30-50
30--70
70--150
3+
150-230
45+
113-150
75--140
28--32
100SO
40--60
105--140
113-140
90+
104--113
100+
40+
1+
140-150
110-120
160-260
200-225
10-15
1+
1+
200-215
25-50
15+
140-170
11
Il
~
76
PETROLEUM
R~FlNERY
ENGINEERING
3-34.
Rapid
ewing
Medium
curing
RC-3
MC-a
(D597)
(D598)
90
170
Slow
curing
SC-3
(D631)
230
.....
. ,. ..
....
350
350
350
"
Slow setting
emulsion
88-1
70
(D244)
28
60
83
30
75
100
100
74
100
100+
99.7
........
....
42
76
90
200
Soft
58
150
'100+
~OO+
......
99.7
99.7
74-
. ....
98.5
'
I
I
\
\
REF~RY
TABLE
3-35.
77
GAS
Aroma.tics:
Disti.llB.tes and solvents .........
Benzene ....... ,'... , : '.' ........
Cresylic acid, crude .. , .. ; .......
Naphthenic acids ....... , .......
Toluene .......................
Xylenes, mixed .......... '.......
Other ..........................
. Total aroma.tics ...............
Aliphaties: '
Methane .....' ... : ...........
1953
642,649
722,650
404,545
462,105
16,080
23.,123
836,473
749,010
14,355
2,505,691
24,470
16,687
1,038,290
699,455
30,404
3,174,605
131,527
445,214
3,048,225
2,007,140
1,331',475
1,411 ,285
753,461
1,171,596
1,3-Butadiene ..................
11.-Bu tane ..... '......
: ..........
Butylenes .....................
Isobutane ........... '..........
Isobutylene ....................
Other C.s ........... ~ ..........
444 1 532
124,562
663,748
250~752
C, hydrocarbons ................
Diisobutylene ................ ~ .
Dodecene ......................
N onene. : . ~ ........... .' ........
Deriva.tives .... '......... , ......
Other aliphati.cs .... ~ ....... ';. ...
Total aliphatics ...............
Grand total ......................
1955 ..
...
to
II
371 ;948
146,204
8,128
694.,560
13,094,357
16,178,962
144,623}
2,135,740
1,366,175
1,222,622
1,152,197
418,144
906,732
155,589
534,507
122,048
23,157
176,926
60,986
2,681
219,242
8,641,369
11,147,060
1950
72,1)27
16,080
24,684
329,122
449,587
532,571
1,424,961
1,821,893
998,842
694,047
610,056
641,072
20,044
336,625
5,510,100
6,935,061
78
Per unt
Acetic acid. . . . . . . . . . . . . . . .
Acetic anhydride. . . . . . . . .. .. . .
AcetOne. . . . . . . . . . . . . . . . . . . . . .
Acetylene ................ '. . . ..
Acrylic plastics. . . . . . . . . . . . . . . ..
Ammonia ................... '.
Benzene. . . . . . . . . . . . . . . . . . . . ..
Butanols. . . . . . . . . . . . . . . . . . . . ..
Bu.tadiene. . . . . . . . . . . . . . . . . . ..
Epoxi plaatics. . . . . . . . . . . . .... '.
96
96
95
30
100
90
36
53
tOO
95
Ethanol. . . . . . . . . . . . . . . . . . . . . . 83
I,
Ethylene. . . . . . . . . '. . . . . . . . . . . ..
, Ethylene glycol. . . . . . . . . . . . . . ..
Ethylene oxide..... .. . . . .. . .. . .
Formaldehyde. . . .. .. . .. . . .. . ..
Glycerol .........'. . . . . . . ...... ,
99
80
90
90*
40
Per cenl
Isopropanol ... e e ' ,
Methanol .......... , ..... , .
Nylon ................. '.. . . . . .
Phenol ... ~ .... _ . . . . . . . . . . . . . . .
Phenolic plastics ....'.: . , , .. .. ...
Polyethylene ...................
. Polyester plastics. . . . . . . . . . . . . .
, Propylene .... '.. ~ . . . . . . . . . . . . ..
100
8li
60
50
50
100
70
100
Polystyrene ...................
50
Styren.e. . . . . . . . . . . . . . . . . . . . .
Synthetic rubber. . . . . . . . . . . . . . . .
Toluene .. : .................. ;' ..
U~ a.nd melamine plastics.. . . ..
Vinyl plastics. . . . . . . . . . . . . . . ...
Xylenes ....... , ....... , . . . . ..
50
75
77
70
80
89
Estimated.
TABU
3-36.
OBT..umm
Million pounds
Production
1955
Capacity
1955
3,000
1,500
3,200
1,600,
2,000
1,300
1,350
Xylenes .....
1,100
1,100
1,000
1,000
350
400
4,,200
\,
Hydrocarbon intermediates:
a . ,. . . . . . .'
2,200
1,200
750
2,400
1,800
575
6.000
1,200
850
2,600
585
6,800
550
600
800
860
1,500
1,570
, 1,800
2,250
1,.200
450
970
850
200
1,200
400
800
750
ISO
550
800
600
\.
tl
650
900
700
j
t
CHAPTER
I.
i
80
et
ti
~
81 "
K=
,
'
(4-1)
in which TB is the average molal boiling point (OF absolute) and S is the
specific gravity at 60F.. It has since been related to viscosity, aruline
point, molecular weight, critical temperature, percentage of. hydrocarbon,
etc., so that almost any laboratory data can be used to estimate the factor
(see Table 4-1 and Fig. 5-9). Typical Characterization Factors are
indicated in Table 4-2.
N~lson" w. I;.., 'Aromatic Base Crude Oils, Oil Gar J., Oct. 28, 1944, p. 101; also
Dec. 2, 1944, p. 91.
.
-4 Characterization of Petroleum FractiOn!, Ind. E1If/. C1(,m., M, 1400 (1935). '
TABU 4-1.
CBAlU.CT'JIlB 08 BABm OF
CRUDE OI~S
API gravity of
fraGtion.e
vu;.
Correlation
llldex
Anilino point;
oF'
ooaity
Dieael fueY
Xeroaene
bu~
irav~
GND.
Kero.
teriaaUon
1'.0\0,..
Paraffin
bue:
12.9
12.8
12.7
12.6
12.6
12.46
12.4
Ga.
oU
Key
No.1
Key
oon-
No.2
.l.Iiotb
Mid
bp
Mid
236F
~D4J'
7~6F
bp
Mid
Mid
Mid
Mid.
Mid
bp
bp
bp
bp ,
bp ,
493 11 1" 116F SOODF SOOOF 560F
74.45
63.6'
39.4
12.~
63.1
62.0
60.1
'0.2
47.6 '
.e.9
46.2
46.4
44.7
44.1
..a. 4
3S.S
UI.86
12.3
U.2&
73.3
71.8
70.1
68.4
67.7
61.0
66.2
66.2
64.6
U.16
62.9
62.1
61.2
60.3
69.0
68.8
...
"
" ......
36.S
"
36.6
... I.
34..~
0.5
11.0
"
....
12.6
14.0
16.6
'17.0
18.5
4:2.7
88.6
82.8
32.2
31.6 ,
80.9
30.2
29.6
41.9
41.2
28.8
2S.2
21.1
23.3
40.4
27.5
26.0
a9.1
a9.0
26.9
26 .3
26.6
20.1
10.0
13.0 ,
uLO
.....
19.0 . ........
22.0 0.798
23.6 0.802
26.2 0;806
26.9 0.810
28.6 0-.811i
30.3 0..819
32.0 0.824
33.7 0.828
8mok~ RlD&
Mid
bp
Mid
bp
polnt.
Cot.anB
No.
12.06
12. -0
11.96
11.9
28 . 2
36.4
0.833
0.837
38.8' 0.,842
40.6 0.847
42.2 0.862
37.1
- - ". ..
No.
Mid
Mid
bp
bp
4a711:r 437F
6~0F
rat.iol'
80.0
.. " ...
68.0
162
183
"
160
148
146
144
181-
..
76.0
17Q
H.O
177
7~.O
176-
70.0
178
68.0
66.0
54.0
52.6
22.6
37
'
....
.
84.0
"" "
"
, ""
"" "
..........
. ... "
"... .."
"
.. . . . t
. .... "
72.0
"
"
"
...
. ". 42.6
3S.a
.....
83.0
61.:5
60.0
69.0
142
140
137
171
169
l~
167
182 '
164
.~ ~ .~~- .
64.0
62.0
60.0
DUm-
Mid
Ra.w Dewa%ed
luba. +20o F
bp
aOOOF
...
. ......
..
"" . "
". ".
...... "
" .... "
....
" .... "
" "
. .. " .
"
Feed
API
berb
.....
,"".
......
151
1"
..
131
127
. "
28.0
. ......
29.0
..
122
118
113
" " ..
32.6
26. 7
"
U.O '
47
oa
S8
........
..
_<
---~----~--~~~~~
II
..
""""
. ......
"
"
76
70
&c5
61
ti8
76
66
67
,_ . _
...
" .-"
"
.... " ..
98
93
89
-83
78
48.0 30.0
.
36.6
" "
"
. ".
66.6
65.0
"""
,.
..
79
...
34.0
"
108
" "
.""
....
83 '
81
H '
Mid
bp
6SOOF
00t.anB
No.-
- . ..... "
... ...." " " ...
loa
27.6
118
100
10li
101
97
136
80.6
86.5
82.5
Mid
bp
200111'
14ld
bp
Wd
bp
60()0)" ~F
...
" ....
..
... 187
.. . ..
'186
163
lD.1.er-
medla&8
bMe:
, 12.1
DOl
it.7
UOP
Charac~
Carbon~hydroPll
Tberm&l
onckJllC
"
"
"
" "
.....
t ... "
.. "
.......
31.1
aO.4
29.7
. ". "
66.2
66.7
67.2
67.8
..
~~~~--~~~~~~
6.42
6.49
6.66
6.6'
6.69
6.66
6. '60 6.72
6.66 li.79
6.72 6.86
5.78- IS,Q1
6.14. 6.08
6.U
6.20
6.90
6.96
6.03
6.7'
6.82
6.90
6.117
7.06
6.11
6.19
6.06
6.11
6.18
6.24
6.80
--~~~--~
6.28
6.86
S.U
6.40
6.68
6.66
--' ~'-~.--------
Cor'rela.tiol1
Index
UOi>
Kero.
Gas
oil
F.oto~
Key
Key
11.56
11.6
Napht.heDe
bue:
11.45
11.4
11.36
1l.3
11.26
11.2
11.15
11.1
11.06
11.0
10.9
10.8
10.7
}O.6
10.~
Ity
0011.-
Sol-
--
Mid
11.8
11.76
11.7
11.61S
11.6
Dieael fuela
il'&V-
Charac-Guo.
teri&atioD
11.86
Dieael Dieael
luel,a Index~
Ce-
--
taD8
32.5
20.4 ,43.7
60.6
49.9
49.2
48,4
'47.6
46.8
46.0
46.2
44 . .5
42.8
31.9
31.2'
30.6
30.0
29.3
28.6
27.9
27.2
26.4
24.0
41.1
39.4
23.4
19.7
19.0
18.3
17.7
17.0
18.4
115.7
16.1
14.,4
13.0
11. 7
10.4
9.2
7.9
37.8
86.2
22.0
20.4
19.0
45.6
47.3
4{L2
150.1
53,.0
55.0
57.0
59.0
61.0
65.2
69,5
73.7
....
68.7
60.8
62.8
64.8
66.8
68.8
71. 0
78.2
75.6
77.S
79.0
80.5
83.0
~
...
. .. ,
0.897
0.902
0.907
0.913
0.918
0.924
0.929
0.936
0.941
0.947
!).969
0'.972
0.986
0.998
1. 012
102
97
92 '
140
136
132
87
128
81
124
120
76
70
63
056
48
...
.. .
...
116
112
106
100
89
...
. ..
42.0
40.0
38.0
36.0
34.0
32.0
30.0
28.0
26.0
24.0
20.0
16.0
12.0
No.
Thermal
Kliouri VIaaoelty IDdex
oraaidnl
but.a.no1
Smoke Ring Dum-.
Feed
point No.
berb
API
00Raw Dewued
\aDe
lubea +200F
MJd 'MId Mid
Mid
No.'
bp
bp
bp
bp
43roF 437F 300F
680"F
XerOIl6D.8
51.0
60.0
48.5
47.,0
46.0
44.6
43.0
42.0
21.4
20.4
19.6
18.8
18.1
17 . .5
11.0
40.6
39.0
38.0
36.0
36.0
34.0
32.5
a1.0
30.0
16.0
15.6
15.1
H.7
14.4
14.1
28.15
26.0
12.2d
12.0"
1l.Sd
11.&1
88.6
41.0
,24
20
24.8
12.0
24
18
1.5
10
72.5
73.0
23.7
23.0
22.S
21.6
-10
21.0
-18
-18
20.3
"."
I.' ,
.". ,. .. , .
-14
....
-24
43.6
44
-34
37
31
. 29.1
28.4
27 .8
27.1
26."
26.7
26.0
73
68
61
55
49
16.~
....
27
17
7
....
~
. , ,.
-40
46.6
... ,.
..
, ....
"
60.0
'"
M.O
.,,' "
"
'"
.". "
....
.,"
....
" .. I.
...
59.0
I
"
66.0
11
4.
- 7
-60
.,,"
63
49
41
39
84
29
4,
-60
.., ,
....
'''' "
I,.
""" "
Carbon-hydroi\ea
ra.tio~
Mid
Mid
Mld
bp
bp
bp
20oc>F 600F 900"'F
68.3
68.9
69.4
69.9
70.4
70.9
6.24
71.4
6.62
6.70
73.5
6.29
6.35
6.41
6.48
6.li5
6.78
6.85
6.92
74.0
1.00
74.5
75.1
76.8
1.09
7.19
7.28
1.37
7.47
7.68
.". ,
" ...
6.31
6.44
6.61
6.59
6.66
6.14
6.81
6.88
7.14
7.23
7.31
7.40
7.48
7.67
7.66
7.76
6.96 7.84
7.06 7.93
7.13 8.03
7.21 -8.14
7.80 8.24
7.40 8.34
7.60 8.46
7.61 8.69 7.71 8.71
7.82 8.83
23.0
20.0
- -
The variOUI!I CaotOlB or Ptopert.ies should be determined -in terms oC the Cha.raoteriutLOD F&etor because they are not alLog;eth.er COD.lieteD\ with ODe aDO~.
Approximate.
84
4-2.
F'lIw
HYDROCARBONS,
----~------~--------------~----------~--------~------.---------Charaeterisation
'Paotor
U..7
14:.2
13. SIS
13.5-13.6
13.0-13.:Z
12.8
HydrocarboDil
MiaceIla.aeoua product.
Propane
Propylene
Iaobub.ne
12. U
12. 5
guo.
Sa.n
Joaquin (Vena.) wu dlaHl'xene--2, aDd 1.3 butadiene .................
12.7
1:2. tl
ButaDe
Buteu... l and ~peJl'aDe
Hexa.ue and tetradecene.7
\
\
till6~
U.I-U.5
2.2,3,3-tetramet.hyl butane
Pennsylvania.
Rodesa& (L.a.)
J2.2-12.44 2,l1-dimethyl dodecadiene Big Lake (Tu.) .
12.0-12.2 ......................... Lance Creek (W~.)
11.D--12.2 ......... . ....... -. ....... lrfid Contment
Okla. City (Ok1a..)
11.0
11.&-12.1-
M.e. feeda
...
..
11.8&
11. 7-12
Hexylcyclobexane
.i . . . . . . . . . . . . . . . . . . . . . . . . . . . . "
G Venesuela.n wu diatillatea
p~ baoe gaaoliD_
..........................
11.76
mediate feed.
Eut. Te:I:. and La. whito
product.
Tia JUAna (Vena.) white
prodocla
.
Cracked ga.a oil from J)araf-
ruuc '~dll
11.7
ButyleyclobeuDB
ll.e
11.6-11.8
11.5
11.4
11.3-11.4
11.3
..
Cyclobub.ne And 2,6,10,14
11 . ~
teLrametbyl heudien.
-r
i
l
I
l-
-\
-I
\
4-2.
J..
FEw HTDBOC.umONS,
P:J:TROLEUMS, .AND TYPICAL STOcxs. (Contin.ued)
CB.ARAC"l'lClUZATION ' FACTORS OJ' ,
Char&c:ter-
iJatioD
Fador
11.2
Hyd~boDII
, Cyclopen'-be
11.1
11. 0
~laCeIlaD&o\l8
produc'-
*duum
Lowea\ C.F. n&pht.benio
prOduct.
Ca.t. cycle .toeka (high !tOnvenion) from 11.7 C.F./eede
Thermal heaVy coil.feeda
Gu oil :in Jluid oo~ of
11.9 C.F. ~
Tbermal Producw
10.0'
..
10.8
)0.0
)0.1
10.4
10.3
10.1
fuela
10.0
g. 8--0.0
Benseno or 2-ieopropyl
aapMhAleDe
Diphenvlmet.hane
Residuum from
stoch
ca~
cycle
12.88 (raDge 12.1-13.65) c&lcula~ from fac~rJI of raw ILDd dewued lube .toco. '
. ~ From residuum when feeding p8 oil or distilled atocka.
I
I
I
I
.86
UNIV.
SAV80L.T
VISCOSITV
AT 100" F.-SE.C.
t
r
(
I
t
~
RAW PttNNSVl"VANIA
DEWAXE.O FENN.
RA.W 11.7.5
40
.ao
eo
70
UNIV.
FIG.
Relation of
SO
90
SAVSOLT
100
110
VISCOSITV
120
AT
1.30
tttttm
c..F.
tvEOlATI!:. OR
C M.C.
INTEROEWAXEDq;
.
140 I 13O
leo
170
210F.-SEC.
viscosity a.t
V.I. of
lube stocks
Table 4-1). By solvent extraction
lubricating
of Viscosity Index higher than 100 can be produced.
4-1
4-2 indicate
relationship between Viscosity Index
and Saybolt
viscosity
100 and 210F. The Viscositytndex
tabulations of the ASTM (D567) " must be employed (rather than Fig.
4-2) lor accuracy.
Petroleum Produots
yearly.
II
Pa.,
87
Example 4-1. Viscosity IndeI (Fig. 4-2). An oil ha.s a. viscosity of 1,600 sec at
100F and 80 a.t 210~. Reading from 1,600 on the left, to the slanting line marked
80 at the right, the Viscosity Index 011
the bottom scale will be Seen toObe
4-a
about 3.
0
200
400
600
800
',000
1,200
C.I. = 48,640jOK
I--
L.,..- ~
1,800
~
1i2,200
~Z.400
]Z.600 ./
o.~
>
',/'
.....
...V
,/
./
./
r'
/'
70
oQl
1M
90
10
II
/ IZ
:/
/
V
/
V
/
./
/ ;'
iI' I
V /
V
L
-'- 40
V
./
",
./
./
:t'
2,800
3,000
".
-- ---
f-" 60
f-'
..... f--" ~
,/
~1.600
----
~~
,-
/
I
V VI 50
IL J L
V
if
II ifL
V 0/ V
J
V
V
I
3,-400
I
V
3,200
3,600
1
MOO /
V
o 10 20 30
If
'if
040 50 60 7D 80 90 100
Vise os ity In c:iex
+ 47~.7g _ 0456.8
lL , 4{)O
~2,000
1<;/\
(Dean and
(4-3) 0
eC
88
n. I .
(4-4)
100
+ (68 -
O.703B) log T .
V.A.lUOU~ ABE.A.B-CUM.ULA.T~
Below
these API
gravities
10
15
20. .
25
30.
'35
40.
45
Avg API
U.S.
U.S.A
.......
east of
Calif.
....
to
...
Imports
1.01 . .....
9.56
. ...
1.3
4.5 .
23.4
15.6. .
27.7,
..
....
<II
..
,
I
..
..
96.0~
. .
34.7
36.3
Texas
. . .. .
1.0
4.0.
11.3
.......
.......
.. .... ! '
29.6
8.76"
20..4" 24.7"
45.31 47.44
~.511 64.7 4
. .
.. .
.......
. - '...
..
...
........
"
.....
..." ......
83.6 . .......
97.()i . ......
........ 0
(1951)
West
California
U.S.-
6;0.
17.0
24.0
52.0."
83.0 d
PERCENTAGES
26.2" .
10.5.,
38".0.4
65.o.d
81.0."
.. iii ....
. Venesue1a.
Saudi
Arabia"
1.0 '
9 ..1
41.3
47.7
65.8
85.7
97.1
99.8
25.3
35.8
1.5
32.5
on
Rapt. of Committee
Bunker C;Fuel Oil of the Na.U. Pet. Council, Dec. 9; 1952. .
"Nelson, Thery, and Sahagun, "Ven~elan and Other World Crude Oils," Ministerio de Minas 8 Hidrocarburos, CaracaS, Venezuela, 1952.
c Ara.meo Report .
.. Estima.ted. ..
4
.sulfur ranges from 0.03 in high gravity oils from Venezuela, Bolivia, and
Argentina. to as high as 7.31 in 14.4 API Qaiyarah oil from Iraq. when
Compared on a gra.vity basis as when being marketed., the amounts of
sulfur in various crude oils compared with the amount in United States
and Venezuelan oils (basis is 1.0) are as shown in Table 4-4. u
JackBon, E. A., Oil Gaa J., Ma.,. 21, 1935, p. 16.
u ~elson, Thery, and Cordero, RelatioIlBhip between Sulfur Content of Crude Oill
and the Sulfur Content of Conventional Refinery Prodwrta, Proc. Fcna1A W {Wid Pd.
Ccmgr., sec. V lA, Rome, June. 1955.
..
. U
89
Analyses of ,a few typical or unique crude oils (of the thousands known)
are tabulated in Appendix B.
TABLE
4-4.
Crude oil
0.15
0.67
Average
% sullur
22.&
.. .
....
III
0 .26 '
Under 0.4
0.75
38.0
.........
26.2
l.00
34.1
0 :75
1.00 '
25.3
1.36
1-.50
1.75
2.00
26.. Qe
36,oe
3.00
35.0 ,
.......
1.05
.. . .
.. -.
Under 1.0
1.6()c
1.38
1.60
Nelson, Thery. and Cordero, Relationship between Sulfur Content-of Crude Oils
and the SulIur Content of Conventional Refinery Products, Proc. FouriA World I'd.
Congr., sec. VlA, Rome, June, 1955.
'
,
" Comparing oils of the same gravity.
Estimated.
'
d Tait, T . "25 Years of Progress in Petroleum Technology." ACa Meeting, New,
,York, p. 151~ Septeinberr 1951.
much
"classified as II sour."
With the exception of highly naphthenic oils and the very,few oils that
are highly, paraffinic, 'the distilla.tion_curves-of crude-oils are, reaso~'ably
Nelson. W. L~, Oil Gal J. (definition) July 28~ 1952, p. 375,'s.nd Aug. 4. 1952; p.' 103;
(determina.tion of) Oct. 27,.1~52, p, 145; (peDaltY (or) J8.0. '26,- 1953, p. 403;, (fielda')
May 4J 1953, p. 145.
Esao S~dArd Oil Co., '-'Safety Instructions ~ ,. ," Sec. J.
11
1.
, ':
:~
90
consistent with one another. Figure 4-3 represents the average of over
350 distillation curves,17 and if the curve of a particular oil deviates
from the average curves of Fig. 4-3, it may be considered to be abnormal
(or one should examme the laboratory data for their accuracy). Paraffinic
1200r---r---~--T---'---~--
__~~--~--~--__
IOOOr-~--~--~--~--~~~~~-7~~~~~
01
O~~~-~~O~~---4~O--~---6~O--~---8~O~~--~/OO
Percentage distilled
FIG.
Private files and see Nelson, TheryJ Medina,. et aI., ltVenezuelan Crude Oils"
(1951) a.nd Nelson, Tbery, 8Jld &hagun, "Venezuelan a.nd Other World Crude Oils"
(1952). Ministerio de Minas e Hidrocazbtll'OS, Ca.racas:. Venezuela..
17
, 91
I'
1-
~ 900
:>
-g .Boo
r6,
\
13
700
L!"'
...c
~
. 600
V
1/V I
1"'-
IU
Q\500
5"
"- ~
, ~ ~,
10V ~
'\ i'..
,(
100
~'l
"
FJa.5h-vapori"zafion cum
i'-....
70
60~
:>-
SO
~
....
13
40 --:'
a..
30
/'
rY-5
~~
"""'-
80
V '
Iy
~
90
.r6
~V
rf'.
..........
20
1- 2-
10
-"
00
Percentage Disfilled
F.IG. 4-4. True-boiling-point evruuation curves of a 37.3 API
base crude oiL
mterm~diate-paraffin.
'
1,200
:!: 1.100
.&
' ~1.000
~~
~/
g, 900
o
.!2 800
~
cd .
+='
'ID
700
Q\
.. t7
9-...,
~~~~
.s:
IS
u:
500
If)
cu
~ 400
G'
0-
E-
200
~ 100
V
, -'
~<~
~
1 r.
00
u-,..-
to
'j.,
1.
60
'"
~;
r;
, :"((\lB
50';.,
~
">
40~
ID
r--.~ ~_ 30~
.4
300
10
,
.~):t/
~.V
I~G~
. o\~
..... ~O,.IZ
oP
V f I~s t--. r--..
,1
:\
'~~
'~ ,
80
- '
~ 600
:~o
~
.......
.c
~\~
I/)
I'F.
c..1
20
~~~
'~~1~
'/,'IJ
i:J S!Vio ~~er c.tf
-
~I.l
Get'lt
20 .30 40 50 60 70
, Percent~ge Oi~til1ed
80
~'PI
90
~!
~:
'I
I:
'0
"'
...J
.:~
<{
~~
10
VISG
!:
,j
,08
J;
"
.!...~.,. . .
",'"
1-,
. 92
_ ".100 r---ry.--+---+--t---t---t-:---t--t--+---f
"0
~
~lOOOr--r-r--+-+--4-~~~~--+-~
0/
>;
cyl'"./
~
u
900
,.,0'~~: ~=-+-~-,
'/
.58
800
ell ~-r:7"'f--+--+---t-----I
.~\\~V
. 1'00
~O~ ~
r+-e-+-'
600 r -
......
f\~~~~o~~~;---r-~-+-4-~~~~ 60
~'/vP~\~
on 500
300
~
~
200
",<v
~T"I-+----f--+---I--+-~ 50
I~
~j
.0,.
Q)
'--~
~I
~_~
e"",
~ 100
~,-'-.
~~6
...
15
- / - - + - - - 1 30 L.10
_~ ~~:=+~--I---i ~o
ViSCO~1
er'ae~
to
20
Q:
-ci'
1 ~(C\.. ~ -~-~~<'IO~
~
.'
~ 10
OL-~-L_~_~~_~_L-_L_ _~~
I~~~_r-_+-+_~-~ 40~
C"\"/q
i-~----I;~~'oO~
-+---t------1t-------!
30
40
50
60
70 80
90 . 100
Percentage Di5tilled
.
FIG. 4-6. Tru~boiling-point evaluation c~ of a. 20.2 API uphaItic-naphthen~bue
~~~.
The change of viscosity with temperature for more than 80 crude oils
has been reported. 18 For most Oklahoma crude oils and for most Middle
East crude oils, the viscosity curves are a consistent function. of API
graVity, but no such consistency is evident among the oils from other
reg1o~s.
. ,
.
,
T?e amolPlt of gaseou~ hydrocarbons djssolved in: crude -oil ~s almqst
totally a function of the degree of weathering that the oil has undergone
or the pressure 'at which it is collected (see Table 4-5). ' The percentage
involved when the dissolved gases are lost cannot be stated with accuracy
but it is about:
1 01 I
Reid-v. p. - 1
LlqUl"d.-vo.
/0 0S8 =
. 6
If the gases have a molecular weight of 40, the g~s amounts to about
16.1 cu ft for each 1 percent loss of liquid ..
Salt carried into the plant in ' the brine associated with crude oil is a
ma.jor cause of the plugging of exchangers and the coking of pipestill
tubes. The Universal Oil Products Company Method A~22-40 for
detennining salt may be used. I1 Theoretically, the 'amount of salt that
18
Nelson, W. L., Oil amJ., Jan. 5, 1946, p. 10; Jan. 12, 1946, p. 87j and
19,5 4, p. 269.
Nov.
.
15,
I
ri
!
TABLll
4-5.
Mid ContiD~B.t
12 '
3,000
psigQ
...
.... .
"
"
" "
,.
.....
"
"
"
"
"
1-
"
2.4
0.003,0.03
Pro pane. . . . . . . . . . . . . . . . : . . . . . . .
i-Buts.~e ... " ..... . . . ........... }
1&-B1l.tane ..... , ................
3.0
0:26
2.8
7.0
II
..
50 psi ll
"
...
.. ".
..
" "
"
~e a.~
V APOlL, ~asuus
Ras Tanura
Refinery
36.6
6.7
243
shiptUents
36.2
3.5 '
"
,.
"
uaoe
0.05
0.22
0.34
0.05
0.90
3.16
4.07
- 0.21
0.49
0.15
' 0.89
0.12
98.80
7& .50
"
,.
"
......
... " ..
...
"
. . ,. . .
" "
Qa.tif
PegBBU8
27.2
35~5
2.3
11.5
"
weathered
'
52.3
8.0
32.1
641
. 0.03
0.04
0.84 ,
(Tex.)
HeaJdton
. (Okla.)
trace _
. 0.06
0.06 '
0.62
- 0.19
0.27
0.33
1.21
0.0
0.05
0'.66
0.0
0.02 0.21
0.44
' 0.14
1.96
0.78
97.71
96 .89
0.62
l.52
3.02
98.85
0.62
1.08
9tL57
92.25
'
98.84
" -"
, 10' "
CaUDJI OIlOS
'"
, " "
..
0.07
"
hw
, (Sa.udi llD.Btabilised
Off-shore Al'ahia.)
,0 -. 17
"
OlP A
, ,Qatif
6.25
"
' . ,.'
"
..
..
.. .
,.
..
/I
A.ND
3.64
6.29
250 psi
. ..
" .
,.
(Iraq)
(Vene.)
100F
"
"
JU6epm, Kirkuk
psigQ
%)
.J'
98.64
' 0.76 - ,
1.45
99.19
, 0.75
1.25
-
96.33
- 00.35
97.19
1,.62
'
97.87
97.15
94
can be deposited from 10,000 bbl of crude oil is 'a pproximately as follows:
Lb salt
per 1,000 bbl .
P08S'tole ckpo8it;
cu it per day
1',000
100
. 20
29.0
3.0
0.6
Range
1
5
8
11
........
1-13
1-1,085
(.
No. of
samples
6..
8
9
0-63
124
35
9-44
2-70
5
11
65
22-200
12
15
28
7-305
78
200
10-8,250
261'-
4-2,580
14
173
'!
.t
)
95
The highest-boiling fraction's of. a crude oil contain most of the nitrogen,
and this has led some investigators to feel that there is a relatio~ship
between nitrogen and such properties as percentage of sulfur, gravity, '
asphaltenes, or Conradson carbon residue.
LABORATORY EQUIPMENT
ture as the temperature of the vapor within the column, so that no heat
paSses into or out of the fractionating column. The disturbing influence
of changing room
is particularly important in the operation
laboratory equipment) because the heat losses, even though the equip, has been carefully insulated, are often larger than the useful heat
Air
SupplY
====:::::tt
97
...
!'
98
.,
~
,-
:.
.1
;'
. j.
of the valve K, but for large adjustments of the pre~,re, i.e., at presBllreS
abo'va 50 mm, the valve L located near the pump ,may. .1>e ~'Sed. ' A small
amount of noncondensable vapor is always present dUrmg distillation,
and this vapor passes th!ough valve K causing the throttling action
,I :
~
~:
.. ,
' l
J
-100
10
20
30
40
50
eo
P2rcentOlge Distilled
70.
80
90
100
I
J
99
this
f,
I -
~);-~',=
Mil/;volfme:!eror
regulator
~II.! ...
Li id
n/I:~gen.
E:
l..i
.1\
,~
:i
'/
!;;
t:.:
~
BRlTJmehir
lIolf neahr
{)ewt:lr fiask
IlU'JIIooC.1U'''' 6
Ca/dum
ch1o.ride
ror
Vacuum pump
lifltl"d nlfro~"
.'
F;lG. 4-10. Apparatus
fractional
of
gases.
America.)
---,-.~--~---.~~~~--~----~.
Distillate de/iv.ery- ,
lube healer ~ "'.....
101
Rheosfcd
-\
Milfivoltmeier Of'
Poteritiometer
hermas
boffle
Crushed ice
DetC1i1 CoJu~n
POIckirig
,alni-
sfrip
,,
'(
\
. Differential
_mctnomi-fer'
ItO v.A.c.
6rodu~te
102
In analyzing gases (Fig. 4-10) the sample is introduced into the chilled
distilling bulb, and all gas except the air, hydrogen, and methane is condensed. These -permanent gases are collected in an evacuated teceiver,
and the pressure in the receiver is recorded. The condensed hydrocarhons are then allowed to warm, and the components are fractionated and
collected one by one in .evacuated receivers. Heat may be required to
vaporize the highest boiling part of the liquid. When a plateau occurs
in the distillation curve or, in other words, material is collected at a
constant temperature, the reflux is decreased by allowing the component
to escape from the column more rapidly. As the temperature tends to
rise, the reflux is increased by using a slower rate of distiJlation until
finally little or no more material collects. At the same time the pressure
in the equipment tends to drop~indi~ating that the component has been
removed. The pressure in the equipment is held at 760 mnl in removing
methane through isobutane, but pressures of 300 and 200 mm are maintained in separating butane and the pentanes. Components may be
collected in different evacuated receivers, but more often the gases are
collected as a mixture. The volume of each component is measured in
mole or volume percentage by noting the ~hange in pressure in the gas
receiver. The temperature and volume of the receiver remain constant,
and hence the pressure is a direct measure of the moles of gas in the
receiver.
High-hoiling ~aterials. Even though a pressure of 0.5 mm of mercury
is maintained in a true-boiJing-point colum.n, the-highest-boiling oils, such
a~ bright stock and asphalt, cannot be compietely vaporized. The highest vapor temp~rature that- can be obtained in the .tru.e-boiling-point
apparatus is approximately 1000F (when corrected from vacuum to
. atmospheric pressure by Fig. 5-27); and, since lubricating oils boil to
even higher temperatures, recourse ~ust - be had to an equilibrium: or
"flash" type of vaporization. The laboratory operations required to
vaporize hea.vy lubricating oils are
1.. Remove gasoline from crude oil in a. batch still so that gasoline will not enter the
EVALUATION
OF
103
OIL STOCKS
Per cent
API
20
32
73
7
100
25
9
26 -
I
'I
stocks can be distilled up to vapor temperatures of about 1100F (corrected to atmospheric pressure) by
the use of very -low pressure. The
, equipment of Mithoff et al. lZ (Fig.
4-12) is suited for such distillations.
Continuous Vacuum-flash Vaporizer. The vaporizer shown in Fig.
4-13 is a continuous-flow equipme~t
in which the heating is done by a
coil embedded in an aluminum casting (electrical heating elements) and'
the vaporizer is kept hot by condens:ing mercury vapor. Other vaporizers may employ a gas-fired furnace
for the heating coil, and molten
lead 26 or salts may be used for
heating.
FIG,' 4-12. Compact equipment for highThe purpose of the flash vaporizer temperature, high-va.cuum distillation:
is to prepare a lubricating stock for (1) flask. (2) electric heater, (3) short
packed column, and (4) mam vacuum
evaluation purposes, and hence the connection. (Oil Gas J.)
residue of tar shouJd be as small as
possible and should contain no lubricants that can be removed from the
asphalt in a commercial vacuum plant. For this reason the apparatus is
always operated at the maximum allowable temperature 6 about 700F
and at as low a pressure as possible. With an almost leak-free apparatus
ZG Scheumann and Stewa.rt. Labora.tory Apparatus for Evalua.ting Crude, Oil Gas J.~
Ma.y 16, 1935. p. 74.
104
PETROL~UM
ENGINEERING
\
j
Stovepipe flue
Aluminum casting
healet; eleclric
heotfing elelTJenf.s
I
I
Pyocts in \ Thermocouple
ca5tingi~~~.. ___ well""" ~i'1iI'iT'
\.
"
------....
....
Steam~~
Feed tank ,.
&ffoms
FIG. 4-13. Diagram of a continuous vacuum-fla.sh
equipmen~.
fractionation is imperfect, and hence no' more reflux is used than the
small amount that ,is, required to prevent entrainment, of tar into the
distillate.
Equilibrium-flash Vaporizer. When a mixture is heated without allowing the vapor to separate from the remaining liquid, the vapor assists in
causing the high-boiling parts of the mix'ture to vaporize. Thus continuous-:-fiash v~porization used in almost all plant operations. Figure
indicates one such apparatns. 27 Small-capacity equipments are desirable,
hut they ,cannot be easily controUed.
III determining a flash-vaporization curve, a
of runs at different
JTl.eslie and Good,
105
temperatures' are conducted, and each run constitutes one point (of temperature and percentage vaporized) on the flash curve~
Mid Per Cent Curves. The, physical properties of an oil are found to
vary gradually throughout the ,range of compounds that constitute the
oil. Distillation is a. means of arranging these chemical compounds in the
order of their boiling points. 'The properties such as color, specific gravity, and visc'osity are found to be different lor each drop or fraction of the
material distilled. The rate at whic~ these properties change from drop
(~.
iI. Leslie.)
to drop may be plotted as mid per ,cent curves, such as curves 2, 3, 'a nd
4 in Fig. 4-4.
The refinery engineer is most often interested in determining the' prop..erties' o! a commerCial width of fraction. 'In reality, the gravity or viscosity'of a fraction is an average of the. properties of the many drops that
constitutE the fraction~ If each drop is equally qifferent from the last
,drop and from 'the succeeding one, then the drop that distills at, exactly
, half ~f the fracbion has the same property ,as the average of all the drops.
This.would' be the condition for a mid per cent curve that is a straight line.
Mid per cent curves are never exactly st~aight' lines (Fig,. 4-15), ,but they-,
are subs.t antially straight th~ough any short range of percentage . . 'For a
106
PETROLEUM
, short range
percentage the
property is equal
at the mid-point of the fraction.
arithmetical
these small fractions is the property of the total or
or even the entire sample. The mechanism of using
'can be best illustrated by an example:
the property
of the proper- ,
large fraction,
the foregoing
to
0.9
Z'
.,
;>
100.8
I.)
"
I.U
0.
rJ)
0.7
'10
30 40' 50 60
Perc entC4g 9
Gravity mi4
cen~ curve
'20
pe;
10
Example 4-2),
'}
107
In this exa.mple the actual fra.ctions that. were produced in the laboratory were used.
In the usual ea:s~ only the CUl'Ve is a.vailable, and it'is arbitra.rilY broken up into suitable
fractions.
TABLE
4-7.
Range of
percentage
Fra.ction
No.
0-5
5-10
1
2
10-15
4
5
6
15-20
20-25
25-30
3{}-35
35-40
40-45
45-50
7
8
9
10
Fraction
Range of
No:
percentage
0.6506
11
0.6936
0.7227
0.7420
0.7583
0.7720
0.7844
0.7958
0.8067. .
0.8170
12
50-55
55-60
60-65
65-70
70-75
75-80
80-85
85-90
90-100
Sp gr
13
14
15
16
17
18
19
4-15
Sp gr
0.8280
0.8388
0.8498
0.8602
0.8713
0.8827
0.8939
0.9065
0.9340
..
2. API gravity.
3. Color.
4. Flash point.
108
property can be plotted in a mid per cent manner, i.e." at the mid-points
of narrow fractions, it behooves the designer or user of -such curves'Dot to
obtain' average properties of wide-range fractioM from them unless the
property is k~own to be an 'additive one. Although viscosity is not an additive- property, it is 'a fortunate coinci. de~ce that the' viscosity of a wide fraction from a crude
is almost
exactly the same as the viscosity at the mid-point of the fraction. Apparently the curvature exhibited by ~osity mid per cent curves is just
right to compensate for the lowering of viscosity by blending, so that the
mid-point can be used.
.
Mid per cent curves are sometimes described by the following descriptive names':' (1) differential curves, (2) stream curves, or (3) instantaneous
curves. These curves_are drawn by plotting the property of each narrowboili~g fraction at the mid perc'entage point of the fraction. 'If the fractions are sol.arge that the final curve exhibits sharp curvature, the properties should -be plotted not at the mid-point but as horizontal lines
throughout the percentage limits of the fractions as indicated in Fig. 4-15.
As an example, note fraction No. 19 of Fig. 4-15 which is plotted not at
95 per cent but at about 96 per cent or -in such a way that the two triangle
,areas a.bove and below the elirve are of the same area.
'Yield Curves. If a property is not additive, the properties of various
ranges or fractions of material can be de~ermined ~perimentally by
blending fractions together and plotting the property value so obtained
as a function of the yield or amount of blended material. Curves 5 (viscosity yield)' -and 6 (flash vaporization) of Fig. 4-4 -are--eXamples of yield
cUrves. - .The viscosity yield curve is a plot of the-.Viscosity of the bottom
or residue product vs.- the percentage of residue, and' the flash yield: curve
is a plot of temperature vs. percentage distilled. Since the viscosity yield
curve (~ig. ,4-4) describes residue products that terminate at 10.0 per cent
distilled it is called ,a'" re_sidtie yield curve'~; and similarly, since the Bash
yield curve. (Fig. '4-4) describes products that start at zero per cent dis-tilled, 'it is. classed as a "distillate yield curve." Obviously, a yield curve
can be used to describe blends that start (or end) at any desired per~ent
age distilled, such as the viscosity-yield curv~ of Fig. 4-29, wpich describes
oils that termlnate at 91.8 per cent on the crude oil,. but .such ','inter_
mediate yield curves" must be carefully labeled to designate th'e terminal
of the blends.
DB-ta for yield 'curve~ can be obtained.by making a large number of runs
each for a different percentage of residue (or distillate or intermediate)
Pl'oduct) but this is S'o expensive that the common method.is to blend
stttt,90hle fractions together to represent various yields of product. In
o.tqer to have enough oil for several blends, aliquot portions of the frac. tlOnS are used rather than the whole fraction.
'
oil
I
!
109
60
N\
50
x\
~\
s:
'
"
''\
N\
\
."
c: 30
,11.1
~\
\"l
r:
~
u 20
~~\\
,
I~,
~20 ..
\
ly
o
~/
I . '
'\~
\
i.._
/
~, ~
r--...
~-~~
;~
"
CP"I" \ \.
\
~l
~
I
.
I
...........,
V
"'
..
[)7
.
lY
\~
~ lY
\.
10 ~~~
'Is, (~ ~
10
t\
~?~
QJ
~ .
l\.
J.
~,:ot
\."\ ':\
Ocfane . I "
.
'\number.r;-Y- pressure
'\ "'~~\
"' .\ \ 'h
+
0
.....
. . '.'.~/5I
.
/ :f 2~Vapor"
\~J ~-~
~\ ~\
\t-
~~
.\.
.-u 40 I~\;
" ,
a
~
"." J '
~ '\
10
20 .
30
40
50
.
Per Cent 'at 's tart of Fraction
Fro. 4-16. Octane numbers (F-2) and vapor pressures of the gasolines in one Mid
, Continent "rough cut" naphtha. (Oil Gru J.)'
.
Example 4-3. . Construction of (Re"sidue) Visco's ity Yield CUT!e~ T)lls method
applies in general to all residue yield curves.'
.
Consider 19 fractions of oil obtained by a. fractionating type of distil1ation. The
properties such as ~avity and viscosity of the fractions have already been recorded.80
that the fractions c~ be used in the following blends~ Fractions 1 to 18 inclusive ~n:..
sist of 100 cc each, and the last or bottom. fraction (not distilled) amounts to 200 ceo
The fractions can be blended in aliquot parts to make- several bottom products as
follows:
.
.
Per cent
residue
or bottom
\,
..
--
10
20
30
45'
60
.Total
quantity of
blend,
Blend of fra.ctions
No.
No.
No.
No.
No.
cc
75
80
..
90
90
84
.,
~
:I.' ,',
110
i'
~.
.,"
It
+'..
~.;
..~ 1 '
,
"
, PETROLEUM REFINERY
ENG~ERING
de~ined,
~cosity
Yield,
per cent
Vapor
pressure
42--42
40-45
30-45
One drop
'5
15
1.5
1.6
1.8
, .15-47
8-60
32
52.
2.7
3.3
Finally, the yields of gasolines starting at zero per cent (or utilizing all the ]jght con .
stit.uents) are
..
; :-
Octane
number
Range, Vapor
Yield,
per cent per cent pressure
70
15
0-15
15
67
64
26
(}-26
0-46
10
6.6
5
62
46
58
0-58
2i Nelson, W. L., Evaluating Aviation-gasoline Content of Crude Oil, Oil Gas J.,
May 13,. 1943, p. 52.
.
n Correlating and Showing Crude Assay Datri., Oil G(UJ J., Mar. 25, 1937, p. 86.
so Nelson, W. L., Evaluation CurveSy Ol Gas J., Jan. 13, 1945, p. 91.
111
Distillation Curves. In addition "to T.B~P~ or good .fractionation distillations, there are at least three, other major types of distillation curves
or way~ _of. relating vapor temperature and ' percentage vaporized: (a)
equilibrium or flash vaporization, (b) ASTM or nollfractionating distillations, ~d (c} Hempel or semifractionating distillations..
Flash Vaporization. The feed material is he~ted ,as it flo~s contin~
ously through a heating coil. As- vapor is formed it' travels along in the
T.B.P.
~/
800
700
~600
t;!.,"
~500
~
Ilutica/ion 01
LIOUID TEMPERATURES
.'
it
//
200 '-5 i
, ~ ,,"
". kott
~/
,,/so~;o
~.
Equilibrium
flosh
VL' ./ V
~
,,.,;' ,,/'
(liquid andvopor)
I'
~V
/ f7
~/
~\
l4~
V
/
~\J~
/
,:P'h
/:h
~ ~ VAPOR
5/
I~
300
~
..-z
"' It ~
....
H/
100
~/
~ I~ / / , "
T.B.~~I v"" ., ,,:'/"~
./ ~e(11P~
.
TEMPERATURES
,
/,
~Hempel
'T.B.P.
m ~
ro m
00
Percentage vaporized
FIG.
3l)
API erode
oil.
I
j
I
-j
I-
112
II
"
.'
:,
10
, ,,' V
"
//,
A':
,~ '/
,,~_,~
lfj~
VACtJU.,.
ENCLEA,~7
,," /'
~-
"
,,~ ~/ ,/IP'
,,~
, /~~
o~
o '
' v
-cl.s-
aY
eaUIUBRIUW FLUH
VAPOIlIZATION
'
7i
PlR~ AND, B
OM15ftR
.50NtARZDlBEk
'
NE1..SOH-SAYBOl.T
4 ~DOE5
-
, /~
PACkJ&
'
'd' /[/17
NElSO),l
II NE1.3OH AND ttASrJE"1
/ -
-/'
/~ '
V"
/~/~ l/:~
, .
/
;/
./
:~I
~~
'~~I
,
~ ~ 'V I
,
r'
, ""
"hlPEL
"
~
/'
......
"V
.",
I.r'./i ..... ~~_ A~DSA't'acu
N(UON -"'EhlP1.
,
1~~ilEN8i
"
5
7
a
g"
10
SLOPE- TRUE sbtliNG - POINT CURVE. FlPfR'tarr
II
1.2.
t3
L4
' IS
and the c'Ondenser. The best known method is the Hempel distillation
of -t he U.S. Bureau of Mines, 2 and ASTM D-285, for crude' petroleum6
is a similar method. The crude oil cur~e's obtained by these methods
are nearly -the same as from T.B.P. distillations he cause of the tiny differences in .. boiling point between successive hydrocarbons in the :inixture.
Figure 4-17 is a comparison of distillation curves by these various
-methods. ,Although the curves cannot, b~ comput~d With accuracy from
..
IHs
FL.ASH
70
eo
. 0
-I
100
.
.200
.300
400
.!>CO
600
700
SOO
QOO
FIG. 4-19. Relationship between distillation temperatures at 50 per cent vaporized and
the flash (E.F.V.) temperature at 50 p~r cent. (Oil Gas J.)
.
orie another, they can be 'approximated from the relationship of Figs. 4--18
to 4-21 and Table 4-8: 31 .
.
Example 4-6. Estima.te of Flash Vaporization Curve. The T.B.P. curve ot Fig.
4-17 has a slope (degrees/per cent), between the 10 and 70 p~ cent points of
775 - 210
60.
According to Fig. 4-18, the slope of the flash' vaporiza.tion curve will be 6.5 deg/per
cent, a.nd t.he 50 per cent temperature of the flash curve (Fig. 4-19) will be abOut 64F
below the 50 per cent temperature of the T.B.P. curve:
576 - 64
512F
A straight line flash curve can be drawn through 512F with a. slope of 6.5. ThuB, at
zero per cent the temperature is 512 minus .325 or 187F and at 100 per cent, 837~.
Figure 4-18 may be used to relate the slopes of any of the distillation
curves, and Table 4-8 or Fig. 4-19 relates the 50 per cent temperatures.
.
/.
Nelson, W. L., Oil Gas J. (Hempel). Sept. 1, 1952, p. 117; (Saybolt), Dec. 29,
1952, p. 101; arid Mar; 16, 1953, p. 149.
31
114
These may be used to estimate the central por't ion of the various distillation curves or those ce~tral ranges of percentage which. are substantially
straight lines. Figures 4-20 (Hempel) and, 4-21 (Saybolt) indicate
another method of correla.ting distillation ,ClUves.
750
700
. /V"
a . 6.50
BOILING
b.I
a:
600
t-
a:
laJ
Q.
. '
I'
"./
oe(
.".,,-
::>
or.
700
~ ....
to.:
600
-r.
"
550
....
t-
500
.. '
o::
Q. 4.50
,/
.. ....
,
500
or.
<C(
>
I- 400
~ .............
Q.
I
U
Z'
-...J0
350
300
III
~ .... /'"
I
\oj
~
a:
250
400 OF.
--
r-
"
300 '0F:
....
,---
200
,,~
150
300
:,....--
400
500 '
600
M10BOILING POiNT
700
or
"
800
200 -t:
.Ipoa
900
TB.P. CURVE
1,100
~oo
F.
Note that Fig. 4-18 can be used to relate the slopes of any pair of dis. tillation curves. Thus, an ASTM distillation curve with a slope of 6.32
(reading from left scale) will have the following slopes when distilled by
other methods (reading on vertical line) : ,
T.B.p ............. ~ .. 7.0 (bottom scale)
Flash. '" . " ......... 4.5 (left scale)
Vac. Engler. . . . . . . . .. 6.65 (left seale)
HempeL ....... ; ..... 6.8 (left scale)
r.
115
6~O~--~--~~--~~~------------~~--~--~--~
B.P. ON T.B.P. CURVE
UNDER 5~O _ MID B.P. Of" T.B.P. CURVE:
_~ ,:::~
~~500-700 700-~-1.!
I - - __:-'._"t-----r.... _V
600 oF,
600
-\----1
w
a:
.-~'
:>
I:;
500 or.
550
"'Co.
-...;.---------
800 UP
_ct-----+----+----t-----/-----t-----i-----j-----1
........ ~.
~----~~~-~--_+---4--__L
~ 500~--~--~----+_--_+~----_r----1---~--_;----+_--_i
a-
f-
700 - ~OO
~-
400
300
I-
g
~
>-
or..
350
-I ----'--
--==-
500
300
200 or.
50~-700;.t___- - r -
UN~E.R
8,OJl UP
.;~.
I
700 - 800J.
- r---- _
__
CURVE;'~ .
_ i'800 UP ...;;;;-0----1-..------+-----+-----1
_--~-
J ;-----,io---+__L
!lOO 1
25"'Oj~~~-rU:..:..N:.:D.:;[RT50::0:..:1-=f~--_t
---=-=-*-==-=-~t-~-;;:-=fr-;..;:-:.-=-=-~r-:.-:--~-:::'-f::.-=------i
200~--~~~7~--~--~--~~--~--~~--~--~--~
9 -
to
II
12
r.
13
'4
15
4-8.
RELATION OF
50
(OF).
T.B.P.
VERSUS
T.B.P.
50%
boiling
point, .DF
T.B.P.
-slope
of 1
T.B.P.
. slope
of 3
100
200
300
400
-5
-171:
-2
-1
+1
+2
+4'
- 6
-3
+2
500
600
700
800
.. "
....
900
"
+4
+ 9
+14c
....
. .....
T.B.P.
slope
of 5
T.B.P.
slope
of 7-
-12
- 6
-' 2
+ 2
+6
+15
+21"
-39
T.B.P.
T.B.P.
slope
of 9
slope
of 11
.....
~24"
-16
- 1
- 1
+10
+20
+37 c
---41}:
-30
-18
-10
+ 1
+16
+44
-42'
-30
-21
-10
+10
-11
- 6
- 1
2
+5~
12
(I
&
T.B.P.
50% minuB
.HempeI50%
(all slopes)&
116
T.B.P.,
of
250
...
10
350
...
11
450
500
600
1'"
14
_ .. From vacuum
p241
.L:,I.U.11'io&""
16
distillations.
117
th~
Thus
GI
1D..
"tS
at
I.
]8
~
<
"U
iI:
~7
u
....
"U
1;6
C
a..
0
ViS
:>
u.
IJ.J
~4
p..
....0
Q)
:::J
>
....C
o.at
tr--=~==~---,----t-~j-~~~~~~~~~~-1
}o
.>
l__~__~t===J:===t===1====E:::1:~~~~~~
o
0. 9
Reduced Pressur~, PR1 Computed with FOCd\ Point Pres.5ure
FIG. 4-22. Correction (or the effect of superatmospheric preMure on the slope of equilibrium-flash-vaporization (E;F:V.) curves. (Edmister, Pet. E1I.g.)
OJ
0.2
0..3
0.4
Q5
0.6
0.7
0.&
1,000
I ~
l(L
.(' ",-
900
0'/
ltd!
800
~~I
.,
!
.~~
...c
~700
~J.
t}5
:;,~"!, ~""-iel"
X\,;J
J:
~ 600
"'::1 ~
in
OJ
~ 500
CD
Q)
~400
~
';300
t:s
...
, ....
~~
~
Q)
0..200
E
.
Q)
~~
-~
--
1' 1 ,
,.
..-- 100
. .
~ ~
W W ~
W ~
Percentage
FIG. 4-23. Vaporization curves of a Mid Continent bright.-Btock solution.
500
v
V
..
I4S ~
~V
,/
~ i"'" V
/, -r"': :,. ....
~
......'"
./
V
/
./
.....:
~......
10'.
" :,"
" . :./'
~y
F.v,
~. :?
I....
~ ...
~ ~....
/" V. . .
~~ ... 7
200
~
..........
~ V'"
o
A
Experimental
Computed
V 1/
1
V
100
500
.J
20
. 40
60
80
100
Percenlage vaporized
FIo. 4-24. Curvature in the distillation CW'Ve8 of & pressure-still distilla.te (see Examples
4-6 and 1&-2).
118
119
Example 4-6. Curvature of Flash-vaporization Curve. The expenmental flashvaporization curve and the ASTM distiliation of a. pressure distillate ~ shown in
Fig. 4-24. The computed straight-line curve is shown dotted, the tria.ngular points
a.re computed points, and the circular points 'are experimental ones.
.
430 - 170
Slope of ASTM, 10-70 per cent
60
Slope of flash, lo-7Q per cent (Fig. 4-18)
=
=
4.34
2.8
The 50 per cent point on a stra.ight line eonneeting 430 and 170 on the ASTM curve is:
(170
+ 4.34
= 343F
Computing curvature,
Ratio .of 10-70 slo~es "'"
4~3~ = O.64~
Starting at the 10 per cent point and computing the 5 per cent point as an illustration,
10% on flash curve: 317 - 40 X 2.8 =- 205F
170 - 125
5
= 9.0
Slope of A8TM curve between 5 and 10%:
Slope of Bash curve. between 5 and 10 %: 9 X 0.645 = 5.8
Temperature at 5 % on flash curv~: 205 - 5.8 X 5 = 176"F
Other points are computed in Table 4-9.
TABLE
4-9
Slope of
ASTM curve
Computed slope
Of flash curve
Temperature
increment
5--10
10-30
30-50
50-70
70-90
9.00
5.64
3 . 95
-3.30
3.60
0 .80
3.64
.2.55
2.13
2.32
29
73
Range,
51
43
46
Points on
flash curve
176
205
278
329
372
and 205 .
and278
and 329
and 372
and 418
In thia instance the predicted curve is slightly high, owing mainly to inaccuracy in
determining the 50 per cent temperature. In other instances the predicted curve will
below.
A~TM
End Point of Distillates. End point is an importa.nt specification or way of describing gasolines, naphthas, or middle distillates. The
approximate relationship between the end point of .a fraction and its
T.B.P. (and other) cut point 37 is indicated in Fig. 4-25. The triangle
3'1
120
points represent the a.verage relationships for hundreds. of 300, 400; 450,
and 500F cut-point products 17 from T.B.P. distillations, and the meanings of the other ~urves are:
A-ASTM end point VB. T.B.P. cut tempera.ture for gaso1ine fractions starting at
T.B.P. temperatures of 200F or lower.
B-ASTM end point VS. T.B.P. cut temperature for solvent or n~phtha fractions
at T.B.P. temperatures of about 300F.
C-ASTM end point VB. T.B.P. cut temperature for naphtha or kerosene fractiollB
sta.rting at T.B.P. temperatures of 400 to 450F.
D-ASTM end point VB. T.B.P. cut tempera.ture Ior gas-oil fractions starting at
T.B.P: temperatures of about soooF .
. E, F-ASTM end point VB. T.B.P. cut temperatures for 300-ml standard column
. distillations and for 8. 5-ft packed column. 38
G-ASTM 90 per cent temperature VB. tempera.ture at 90 per cent of T.B.P. cut
for all types of products.
.
.
H-ASTM end point VS. Hempel cut temperature of the standard' 45F Hempel
fractions.
1-.ASTM iri.itial boiling point vs. Hempel starting temperatures of 45F Hempel
'
tractions.
Material
Initial
End point,
boiling point,
OF
OF
437
390
460
Correction
21
18
530
21
26
590
16
True boiling
cut point,
Curve
458
408
481
A
A
B
556
C
D
OF
606
Data. of Good and Connell and of Garton et al., used in the Oil Gas J. t Dec. 30,
1944, p. 277.
It Stanley and Pin grey , Ind. Eng. Chem., 46, 2182 (1954).
21
121
" ,
'f
1I"
"
III
lit
:::l
~
It eo
'"'
Q.
:e....
/,~'....YS.
~D PDI~T
70
~o
~ I'-...
I
,I
1/
"~
..,/
, ..
l-
I-
a:
rai
40
1',
v..-::
,,
K ,... ,
V
fSOLID LINE)
,
V
,.
A.s:t.... -OO PER.CENT POIIliT
V
"
VS.
V.
, 300 j'
T.B, P. - eo PER CENT CUT......
,
,., tID
~
,
,
,. ,I
30
...
It 20
10
, ... ...
"
"
, , " ,,'"
", ...
:::l
III
-~
, ... ' (8
~4.s0
,,
, ~v
,, ,,
~~
I
~.
...
~ ~
,."
;'
,#'
to'
"
"
DASHED LINts
, A.S.T.M. - I\ID POINTS
"S,
T,B.P. - CUT POINTS
,,;
, ....
300
.....
.,~."
-.. - "'"
..,~$~'
,-
It 20
::c
...
ci
W
o
30
,g 4
A.S,tt.L INIT. B. P.
200
250
'
;-(0
~0
-'HMnLVs.
START POINT
300
350
AOO
or.
4!l0
!lOO
~50
500
IJ~
700
FIG. 4-25. Appr.o ximate ASTM distillation characteristics of products in relation to the
cut temperatures of crude-oil distillations. (Oil Ga8 J.)
ducted at first at atmospheric pressure and later at alow pressure,.is necessary. Of course, the fractions from the dis'tillation must be examin~db.Y
routine tests. Table 4-10 is a log sheet of the data obtained in the analySis.
of t~pical paraffin-base crude oil, and Fig. 4-26 is a graphical presentation of the'se data. The vapor-temperature or true-boiling-point curve
. was plotted directly from the data. The gravity c~e was drawn by
plotting the specific gravity oreach fraction as a horizontal line throughout the limits of the fraction and then drawing the 'Curve by balancing
the triangular areas against one another. 'The highest gravity, extend-
122
ing through 90 to 100 per cent, is the gravity of the residue. The
viscosity mid per cent curves were drawn by plotting the viscosity of each
of the fractions at the mid per cent points of the fractions. The highest
viscosity on the 210F curve is the viscosity of the final residue. The viscosity yield curve was plotted directly from the blend data given in Table
4-10 with the final bo~tom from the distillation as the l0 per cent bottom
product.
Rumple 4-8. Evaluation of Paraffin-base Crude Oil. The following sets of yields
of raw stocks can be computed from the property curves of Fig. 4-26:
Per
ceut
Ra.w stocks
Sp gr
API
Notes
Breakup 1:
(1) 409 E.P. gasoline ................. 38.3
(2) 42 API kerosene .................. 23.4
0.753
0.815
56.4
42
0.859
0.892
33.2
27 .1
Breakup 2:
(1) 391 E.P. gasoline .... ~ ............ 36.0
(2) 450 E.P. naphtha. ................. 5.8
(3) Gas oil.(by difference) ............. 42.2
0.751
0.795
0.837
56.9
46.3
37.4
0.89
27.5
unle~
Abbreviated T.B.P. analyses of more than 150 crude oils are tabulated
in Appendix B. Distillation curves may be plotted from the percentages'
given in the tabulation for temperatures of 80,300,400,450, 550, 700, and
900F. Gravity mid per 'cent curves can also be plotted by using the
Characterization Factors with the instantan.eous temperatures just
enumerated.
123
t.l00
-+-
(g 1.000
r c
ridpe.~
,~
> 900
cd
~
800
Q)
...c
c
It/l~
6~~
.
n
~~
~ 700 If
...c
\I)
IlJ
E, 500
400
:;)
~ 300
L
III
~~
{.,
l'
,~
o~
.~
P
~KMF 1JYax.1~tfl(g.~~~
-!\.(
Z ~.
urt
II
0.70 .
CYliniJer
,/
12 ..
~rnder
. E200 ~ ~
~
nr
VBrectk-Up No,1
QJ
o
<If
.~(\'
_.9.j:)Qlkt
-->
)< .3
-.
~ ....
Q)
-60
500
.rr
J
60
rrrrr-r
erlt-
0.90
Br..,k-Up No.1[
~
V}~
100
..
10
~"rve
20 30 40
~
f~d~
e.f u&\~'
~ l" ~
VisCOfi/y..!!:iO
50
60
70
~ ~rf,e J
.Jipr
80- 90
100
Percentage Distilled
FIG. 4-26. Evalua.tion curves from Table 4-10.
The reduced crude is then flashed under vacuum, distilling a clear lubricating oil stock and leaving solid tar. The lubricating oil stock can then b~
evaluated in the true-boiling apparatus. A true-boiling-point analysis
of the crude oil is also peeessary if the light stocks are to be evaluated. .
The curves for such a laboratory procedure are given in Figs. 4-28 and
4-29. The viscosi ty yield curve is plotted separately (Fig. 4-29) because
it was obtained for the hearl-cut lubricating, oil stock which does not
..contain the 8.2 per cent of tar. This viscosity yield curve (Fig. 4-29) is
not generally useful because the plant must operate making exactly
8.2 per cent of tar bottoms or the yields will be inaccurate.
Dependability.of Evaluatipn. As an indication of the dependability of
124
Job nu,_ _ _ _
Fro=m~
_____________
Sample
_ __
n u ' - -_ _ _ _ __
Va.por
Time
temperat.ure at
160 mm,
OF
Cumu-
lative
per C6lI.t
\ic-
Per cent
in
'n,otion
OJl
No.
V18eosity
:Ggr
/60
Notes
100
-I.
2.
3.
4.
5-
6.
7.
8.
9.
10.
11.
12.
9:06
9:15
9:22
9:30
9:38
9:46
9:53
ttl:(\()
10:07
10:13
10:19
10:26
A.M.
13. 10:33
14.
15.
16.
17.
18.
HI.
20.
.21.
22.
28.
24.
25.
26.
27.
28.
29.
10:39
10:45
)0:51
10:57
11:08
11:09
11:16
11:21
11:28
11:36
11:43
11:51
12:01 P.M.
12:10
12:17
12!24
30. 12:30
31. 2;01
32. 2:11
33. 2:19
M. 2-26
S5.. .2:32
,36.. 2:38
S7. 2:4:4
38. 2:50
39. 2:56
40. 3:02
41. 3:08
42. 3:14
43. 3.:21
44. 3:28
45. 3:37
4.6. 3;44
41. 3:51
48. 3;.57
49. 4:03
50. 4:01
51. 4:12
52. 4:20
53. 4:29
M. 4:39
170
210
227
1
3.33
5
248
256
262
6.67
8.33
10
n.61
13.33
288
16.67
297
18.33
20
238
270
279
306
315
327
338
348
359
370
380
393
405
416
480
444-
455
465
4B6
496
S10
523
536
550
562
1)75
590
604
619
633
649
684
682
698
714.
732
750
768
184
812
836
870
903
925
f:l70
1025
..
15
21.67
23.33
25
26.67
...... .....
31.67
33.33
35
36.67
38.33'
40
41.67
0.706
.5
0.728
.5
0.739
'"
.5
0.7.51
li-
0.763
.5
0.715
0.784
.5
0.793
43.33
45
46.67
..
. . .. .. ..
"''''
....
......
0.801
0.809
11 . . .
10
3.33
' 0.815
56.67
..
.... "
3.33
0.820
13
3.33
0.825, .
63.33
65
14
3.33
0.8.29
66.67
16
3.33
0.,835
.50
70
71.67
16
3.83
0.840
59
17
3.33
0.846
72 .
18
3.33
O.85J
p:f
19
3.33
0.857
107
42
3.33
0.865
132
46
3.33
0.875
230
1,33
0.884.
13.33
15
76.67
78.33,
80
81.67
83.33
85
86.67
88.33
90
At-mO&.
Rate slow
Rate alow
11 . . . .
12.
68.33
"
" .........
....
58.33
60
61.67
"
48.83
50
51.67
53.33
55,
..
......
28.33
30
<II
210
20
..21.
22
"
.,
,42
..
o
'.
33
36.5
70
..
Im.m Pl'f!&IIUn!I
FMtmte
Ra.te slow
58..
23'
10
24-
20
25
SO
26
50
'\
\
Blend Dab.
55.
,
I
0.895
.....
..
At
... ... .
ill
..
178
Residue
... ,. ..
100
Blend
..
62
Blend
f2
Blend
'. ill
1-25.;
~-'.
-"..: ..
'
i" ,
": ~ I
.,'.
,".. .'
. :'0'
.'
:.
..
'.
<
.. . .
: .;
: : PEir.ce~tCige/O~~filled .'
.;t.:_1:>." -'d
"\-.:"
.or
'" ~,::'!16' '),~J;<~~,;:; "',:,' "';\; i':;\;~ !;..,;;;c:1!,~~~'<:,71;;,,;.:1;::,; ,"" ~: ~~,j"1 ;"""~'
'"
!,
lzm
~' ,
'r! '
~ '..
Ii: '
.
'
, , :',
,.
..
,:. .:
' "
:',""'.>", I ~,
.- '
. ,
~,;,;.,.- 1
1- ,' ,
,:
.? v~..:
'
,,-::~,.,
.. "~' r! ~i'~~
..\',:
t:"" L. t
' ,o:"t',
-",
r- ~';:
J.'
'.
.~ "50 ~:;,~~, tri ,~, ~\/~, ~:.' ',_ _ -< ;: ;;'::~" ~) " ,'\ : . " :'(::' ,'.':--;:,~Vhtdarger yieldB than iridlca:ted by
-;l)~ ~. - f-' i \ ~.
." . .. .. . the ~va.lu8.tion.'* ; ; :\',~L: : ~~~::..- ~:~S
i:',
, .' - ,
, ',;, < ,::~~~~:: ~;" ', I~,~~~:j., ~;~:;l>..:.,{ :'C' o,:~,.~:.~:~,, .:,, ' ' desigll~d(~\d~ :: ~elessIY op~rated
I.
that may be
lf~t~:~s"If " the' \:r~kn~~ ~pects-'to "get' Su-ch Yields fu ' a co~.ercial
"pi~t~'the plant niust'"b~'p~operiy demgDed .RPd oper~~d. Many poorly
', ' ,
., . . li'oo I,~
.
~.-
r\.
':- ,~,,~.:-:
_' , ,...
:'-
, "'
~ ~': :-:-i:
' .'
~?C? <~~
-, . -;.
, "
-"
:- ~
:.,
, ; ,-'. ~f'''~li'
'cofiatlct~(V.h~df~s ,
fIb
p. a oratory
'>
,:
.:."
::Y)-;\i
~
~:W.Iti~....
...
:
"
~,
:,;,~
.
"i
..
,:
~
,~,,,;,
':
~
~,
;
t,,~llta
.
hllt
..
l1~tally:
.,
tnA'-"results'
Ani,, :.' , _ . __ :~ '~'~'~:~~
.'.
, ,"
"
. ,..:"..... - , ..
,' (' -' , ~V!"f-Jil;'r-"t!f~~,, ~ .~~ " ;'.:""., "A~';:'''~
.M'":;.
, ";Y :.-:--_: ._7/;'r .~~ ,'o~ ~f' ;'" :
f\ ,_;'~. ::':..~ ':, , ..... ~ " . ' ,: .:~.o~_ j1!~Qk-,. ,W'@!~:.Qp'~r~_tioils. The .
,"-\,_. : -_ ::,:-:',:.1i:' '::O{'>:})~" -- tp' ,30;''":::40. '~- ~.O; 69 ,70 80 ~ 9(),' : treatin~bf;lig'-h t ~tillates such as '
- '
' . -. ' "; ' - .'r,"""
Perc.enta~e' &oitDms
0
-'
.
)
<;'--,,\ " _---, ~",\-:,?j;.- :*-~':~f~' Vi
' -' , ( ...~....,,;,~';-'t--d~:<r'~-"--': ' 'li" -~~-.-~ ~ p'r~s~'l~&;&tiiJj'~;l;stUlat,er :and kero<
,A
, , __
. : '_''''';
.~~~~_~G.1
-'
<r- ...'~'~~,-~~.-,,, ~ ;
~-
,u<:,x .....
,. ~
'-' "
over-'-.a.\'- t. " -
period
:of ' ye~, it~..i8 poSsibl~, to - sa.y
".
\
- ~:wH.~~Aer or::: -,ri9ti ,~~ s~Qck.t can: p~~)~ue~e'ssf:ullY.~_ treated, in- thf -p lant, even
"
-"
.0.- -
..
'
f"
'
::>~>:: '.~,~::,~ :' ,:;:' :~1li~~~:: t~~ ]~~~*atQ~ :a,~& p~'ant~' r:~s.-W,tB.: d-~. .RQ:rfpe-c~., \:',,::; ::_-2 ~,,;
"
".
20
-. on'; 's-t':'he' 'Iud ,'" 'is Sllowed
ta. settle for
,-- .--~- ,,- .. ~,' -l::.. :< ,~!",-,.~~ , r:. 'l~"C~}
;~.{J~t<:;~.~?: \,t~x~t~)- ~6.~~ ~~'. i~ .~I?~r.~t_~, ~y: <:lee~nt~~ion: 6r" .~y, ~ea~~ of a_: ~p~~atory .
-' i :"
,..
> .. - . ...
%
1 .. -\ :~
"The ' .~~.ttlifig-:- tl~e" $ " sometime_s" ShtirteD~'- 'by eet?- trif uging the
' " : '~-4~_aCia?:i oil for :' 2' ~r '3-~lhlill1~~a:~pe.M .9 1,5OQ rpm;' ~ The:bU i8Jli~n neutral.... -. " Jze~;With- Caustj~:sod~.::~~d :W~sh~({ with water.:" ~~atedp,re&SUi~ dIstillate
...- :'~ti~i:' be distilled' \vith:: ,st,~ani~-'Ot:jn, 'a- .y~_(mJlnc: - 'The ~ temperature_ is not
. - ;~aUri\-ted t.ri exc~ed , abput~2.5"oF during the_d.i~iill~ti~n.' If. ~ny treats are
.. , co~(l~cted, spe~~i'al'ghiss ii"~n:.s~ill~-:- *,,~Y .~e~:buij't~ TheSe a~e usually of
.;:,.
"~-~ .
..
-~ .
'-
or
' :lh.~~9~tc~,: ty~.:. ,-,~qu!p~~~~.; fo~ ' t~~s,tP.f~~iOil, ~8. di~9-~~~~ b~_ ::gail~y,
- - ,:
, I-~'
\ ..- : '.
.. \'
,
f.~ ~<)~_~ ~.:-~.
":;" ~lTh.ea~tho'r. his seen a m6de~. Vii.eU~'ii:t,l>lant p'roduce 1Sper ce~t of..~QO viscOSity
- atr~~:1{),7 brik4t s~k-J whreas :~Il;lY~- :lQ per.. ~,~t was previou,!,ly mru1ufactured_ J:?y, r.etiidl,lal '~ethods. .~_ yi,eld was ,0.5, per cent more ~ indiG&ted.by
anal;v.siS, ;'.' "~', b~l~~, _Pl~.t fu{d:~~bonitOrY l>ro~ed~~~ for Distilling Acid ~ted ~ked.:
Naphtha, oil 'G~'J:, Ma.y j,' 1934~ ' p>t1. ' .: -, ." ", -, -, ,. ,' .
:'c . /' : --.: '. ;.': > t
,
, U ContinuollB Treating of Oils in the Laborator1', Oil. Gas J., November, 1932.
'f
-~~
.,', ,':
-.> .,'
oJ
', _ .
....
.:
I ":
.;.
( -. ;:
."., '
'.
,:0
the
.;.
I!~i--
.,.
127
-.. -I. '
...
'I
r
.,...
~:;fohl'ihioii~~th~~s;;McrdSdoiili~:~I:i~'tHe.t,~-aa.t~~$n;ru~a:te:tliat,:'niateliAlf:, boiling'
:~,filf: to.; ~ob~t , 650~E: 8.~4(f.',(iilm:;'pressuteJ' ~aJl:;' De suc~eSsfu11y~ ilh}8rpiirated. '
~.: futa{:wu~.~ibckl '(:,:~ :' c6ffispoq;dg:j too2t,'t~:riiperatute': 'ofi a,t)oiit . ,885fF 'at
, 16b.' "'iirih;: pt~k"' itc~. ~J.~,;, i~6fi"l:~:t-i ,', ~~ ~~i;-~:~~1j\' -: ~i:~ ',r;' A ,<i ,":,: f'..h~2';'pi:)~,~";';"~.i.'i ...~ :'.. ,
,,-
t.
..
,.
-l,'
','
r. -..:..... ,<.,...,.
. '1'
.,. '.-.. . ' {. lP~~.~fi1l>~~tifr(f tii~~itf ' ""''', '.~~tH~.~~n.~~~~~'.~~~ o~ers~~~~; measure~ tlie
. . , :'.- :~~61iih1>i~:;'ijt '~ :~liY'dr.cfg~jf,f ~'d(ihf~liJty<li-Otiilon~'J'" '8.~i(Hf-, :Iat, ';:TlUib'
y.
"
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'
..
'
, , : ., . , . " .. .
if '
L,t'; ~l:\~;iiif;f~aij~-~~ii,ji!~i~~ti~~~i~ .
': ': : :,:,:.. ~~:~ ;~~e~IHiiif~$l'Cl1ii~3P~~Ah~f:~~t~~~it~Pte~mb.illa~, BI(tead{~I6riw;~*itli1: the " .
.. ,'ma;'Ta:ble~'4-1}~
.'.,<'" \;~:'.~: : '" '~J',: . h",:,~ "<'~:i;; :,; ,.. ';:, : ,~;: ;: ", ,'. >::
,':
'...~<: , !
:::~.)' :
' .-
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": ;
~;
':
-:
. 0: Y.-( - '" . \
~"" .;~-'
.:
f'
. '
. : ' -
:jf .tcaWdJ/Askevol~" &nd:~~b~~~;j. 0ti'Gu.j~~ ,J~y; :. 20;. i953;. , p. : 1(xi ... ': .',
. -': iI)-iL~:. jo~es; '~d N.;;,"(ili (ifllft/:M~y 26:" 1938~:-- :' ~ ~etiOD,: if J., Pd.
:'Er-');J.,'
D~her
:i9M
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.
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.
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. ,' .,'
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:.
emont Thery~ aDd Corderof'.P~ FUurIA' WorId PeL Congt~. ~. ,V, ,~~et .J.UIl.~
, ., 1955L ~_f~
-
n:.'.. C"-'.)l'j"';~~:~'
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':.:; "
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bfL.;l;~ ~~a-)-_:;'ii; ~. -.
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',
~;~~~~~.:~,,~~::r;;.t~.~i~;/:;~~nUi~\t::*,e:.:
,l~lPl?~~ ' qaljIC?~~. l~~.~,~t, ~,d' .~~~f.1i~~h, ,..j (~r~ ; ~~r:!ff}f.~OJ:!:J~\~~~~J
me.
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v~llies foimd:frorili;tlie.figutei .,', ','" "{'.: .~ j:' '" . >~. ,<'; .: , :,:: /. .~<::/r !~.:~::. "
v.iLikeWisej ,the:,avemg~,:>stiIfUr., conten.t!~ of: .ct4cked,:.pt~ji<;~s;l.~;.J>"e
'-- -
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.} .'
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131
...
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, "
~.
. ' .1 ,
,.
'-,-
'
-+--: ....... ~ .;:. . "'~ ~~:. ;~ ... _" . ~:~ .. , 1--.' '.::;": .
',> . ,"" .c
,.,,:',,, ' .:.l~'r.~<~-';.: ,l ~, .:J. i: :.~" j~'i ' . i,' 3:~" .. .. :. ,: ,.. i~"--'
:
. ;" ..
.'
.' . ..
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... '
~i ~ . .'- "{~'
'
~-
.,
", :.\
,:\,~-(.i.;:'~~"'~-,:.
'
:,:i ~
. ...
,_
~~
The am~unt of ,sulfu~ in p~troleum 'cokes can be judged- from Table' +-11 .
J;;:' ..
, . .'
"
. . :..
. ,:'.
:" ~ ~" .
.,'
',-'.
'.
,~"
.j .: ; (i :i. :.'
. ~'NelsOn, W~ L.; Oil GasJ.'-M8.r~ 2, 1944,'p. 12', and Nov. 17, 1945; p. 284.
. 50' Van Whikle, M.; Pet. Reftnet,: N~)V~b~J; 19.~~,. p. ~ 7.1,~ ;, ."
! . '/ ., . . ,~;
"
....
',,:
,:r .
~
... .
"
....
.. .
.. t:-;:
. . i .. _,:-
"
"
"
" ;...
-
. -,;
' ; :. : . '
:':
'point' (see Fig.' 4~9r ,'-' The'flash'pOln(of blend~ !is ',n.ot a lin~af itinction
of the flash pOInts of the two agents'brlt is' fel~'tea52 as:ihdicated'in Figf.
,+-39,.; The line in ,Fig. ~;l9 for.' mat_eriai~ W~Q~ .- fl~ points are 300F
lines check w~ll wit,h experimental data as well ,a s the .work of Daigle ~d
fiaSJl, .oi," i~fl~nihi~pility 't~mpera'ture the vap~r pressure 'of 'the ma~nal is--aBotlt, ti,s' f6~bWS: '
,trh>l4tgS4
.....
'.
'
,.
I'
' ,
'
. .-.
...
'J)
'
..
... \
'"
,.
UNelson, W.L.) Qil.Q~j.,:.Turie''i.4,: t951J''p'-108.' .'-" '.," ',_ ,:. ,: ,: ,,'" ",'
'U ' Correlati6ri of tll,e FliSh' p-omt.-~ '. :, , ~. 'MMter;~ 'th~ 'uD.ivWtY' of" ~':i949.
54 Evaluating Coastal Type Crudes . ' . ~ , Pet. Proce#ing,' M8.r:cli,"1949. p.-:286". ' ."
"
.133
..
"
I
I
'
,-~
, .. ,Kerosenes,
,',': Lubrica.ting oilil ........ :. : " ." ... . ....... ' ... ,
' .... ~:
_. ' -
.'
A1,ti~.u<!~ ~~
.;,
' ,'.:'
i ._ J;
! ;
1:Dun
'.
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~ . L,.
.' , '.
~, ~ ,
"
~ . : :_ ,
' 1.:
. I
II
j'
(
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.r.
~i
,
"
Elk B~m';
Wyo.~pitch~
..
.. '
"('
3. 5 ~ .
I
I
7.0 :
'IQ.8... _
5-6+',
' . . I) .65..'
4.5
: 4:5:""
Kuwaiv-pitch .... ; ~ '.' ." .. , .. , ..... ~ . :6.0
5.37
Variou&-pitches ... : , . : : . , .. , . , . . '6 ~ 04 ,0
Athabakll (Canada). tar sand oil ...
:7.3,
5.3
West T:e~halt .... ~ ': . ; , :',', ~ : .'. . . . . ' y. 3'.5"
West T~~ra.ck~ fuel ... ...... . 2. 94
Boscan :(Yene~).,.-':-Cru:de, ; .. '........'... .,.' .-. jo.~Q,.;', '. Ii. 0,
Bosean
.; (V~e~)--1sphalt. .. ;.\-'.
{: .:.' ,..
&.j. ~'
.
.
I
-'..
I
.i
. ..~t.83
"6.5".~
/ .J
. 1.55
2'.01
f2-1.5+
. 1.06
.
:
: 1..04
. .~ 1.0.
_ ... . :?f.
,5.0 . :
: 5.0 ;
;.o.ps.
. 5,0 '
~ tL 775
Bosca.n~ (Venei~)--o-a'cked fuel. .........; \ ..~. .. .
6.45
" '.
East T~xas--feduced' eruda,' ~ , ; ,:: ...... ,: ::rio :5"::' ~ :-.1. 26"
".'z.. 51;, .~ .. -i~l2.Q4
East T~~phait., ..... , , .. ', ;' . .. .:ci~',~::~,, :, .I~JJ; . . 1 ;35-1.~ o;.7~i ,03
, 1.4
.
~ 1.,55
. So~th f~Uisiap&. ~lll.'fL,>. ~"" ' \~':: . 1.~;~~... i~_~;~\ .,,_ .....
_.. .. :,.- -_..
1...>
0,6
.:. 1..00
Texas Pa.nh3lidJe-vacuum bOtooms. 18,9 '-. o.~: ~?,
:.<. ...,; .
. "
., .' .. - ..
'~-'"
'/,
.,Y'
~-
! .:~
'
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Ap~
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.,
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..
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.:.0
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. .
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....:
r- ".
'.- :
.
I
..
. ' r'
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'c
.... j .
' !,
,,~~ -
135
"
I'
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...
.::~f~.'
" ~;!...~
.'i~>
:~' .:
; 0{'
-"
.,'
....
'-
t ", '
.... :
..
,~
..., .
/ J
.!~f:.~:
':.; .
.s ~ : '
..
.,''-If
.'
'. ,.. '.':,<... -"-:.,, ~:..:-: .... PER" CtNT:-. SUL:FUR IN ' F'EEQ ;"'s-T6tiKc7:~:;-,~-<. ":
FIG. 4-37:- petcen~ge. of .:~ in:'1atiUytio eraeked gasbliiiea 'ind:~ycl~ ~ci&:Vs,. per..
centage.of '~ur.'h1 v.a.r~oU8feedstocks; , .(Proc':' Fbuith Worl4:pa,:; Co".gi.l. Rome~t
. .'~':'~J~'
"
" .
.~
....
--.-,.
. . : .
-.
,-
'
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...
,,:
.~--}
~.
'I"
'L ,
. The :yap or pressure: of-'mixtures' can-be-.computed accurately. by summing th'~irir-OiIuht of ' i~e mol'e fraction. times. the"tfue, vapdi'-~.pre~tire; ; for
,r-
. ,J f.
4'
' .
::- ,~.
"
..
'
co~.pqn,~iit',. in;. the :~ln.d . .. Howeverr t~,~ -r,~~~~~,(:' ~h,.~h.- ~~~~ ~ap,<?r
pressures must 7.pe. emplox~-, and the accuracy -: of c~on:ela.trb:ti between
the t\vo:~lciI;lds; QjYapbr" p~~res .is' rfot..:. eOOd(~e.::Tbi~;(.,#J#}~.~8 . For
crude- oils,- therelationship is even. inore6. cIT&tic,-the .true.vapor.pressure
each
57 ~ble fma.$:chaideOn~: Ref.. ' Nat . .(la8o .. :/i:.f. Dece:mber,: 1935t-.p. 56~?t ';. '~~!
-"~.~ ~ !N.e:~-ll,. W.. .L~ ..;.Q:il:_~ J.~; J~~.21r..195.4; p,~)19,!: _. -~'.- :;, .::', .;~.. ~} ' .. '- -: . . ;/',,,:: ,'::,
.:''6:, "
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II
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f, i,72
"(40
__~',,-,'',.,-'-,-'-'-'"--......:".;.
... .:....~',. :,;'.;.;.,. -~~~___.:,;..
to.Reid.V.P. ii
,:,",-,
' . . ,'
': . ' .
~:
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. Range '
. Average .
.
10;:
. (1: 611~tO.
0\ .. "~:j ... " : ...
(1. 0; to 3))".,.'. ' '~' : . '.
'(1. 03 to L 45)
',f .C:
-:-:--:,.,:-2-:..:...
.. """,.~",~,.~.~,.....;,;'.;...''~'~~~'"'t''--.....~,""''':.,,',' ',", ,I
=-:-':' ...;
..
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.....
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I
,G ravity. , ':API ' (qr,', sPecific):,gravity ..,is, usually , report~: ~s.:, part;, ,of a
crude"Oil or product~ aila.lYsis; ,aii&'hence"n:o' 'Short-,out' methods of:estima-
.(
-1.37
'.
100
"
......
.\ .
.
: .;
en
t-
:.~~:.
..
"
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, 1)-,
,'.~ ;
. . \ .. , ,. " ,
.' 1 -
99
80
..
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<
..J
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70
....:
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......
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., :
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, -,.. .... ~~
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.-- ~.t~.
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; .. ..
,-,
PETROLEUM
-
... ',
r- ,
'
, ....
'.
,--,-
'
'.......
' .
REfiNERY~. ENGINEERING
...
. . . . . . . . __
. "1
"
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r ..
.-. J
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.... ~, -~
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~:
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L 17
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e.
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: 22.2
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L 088
1.09 , i:
'I! 030 ... .'.:. -{ :.'
':.
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t.
i(s... "}~l},~
f.~ ,
,:~
1}093';
, ~,~ ~
- .~:;.~.,
. , ':~ ",- "i-.. ::~- 'It:o-'' '", 1~' 5.:..~ .... ,. 1.. OS", '-:i.",-,:,. :~~
: . Lfghi ~~iiri~1.... ::: ~ : :::: I~ lS':o",c i 2o"q.t >- . i:~ 11'0 ';.;
L
,. '. " .~atura.;tt~~e:,:--.;~., ...:~ ....,: .jt.~.",:~:~~"a;~~~)~~)~:'.i:1:; ':;~
y~ "."-.., Natumrgasolliie
.. .
-~
. "'ii""
'Nat~; gaso~e ... '~ '.~'.. ~ ~".'..:'" U~'; 0 " , i 17. ~ .' ,",...":'.h~, '
Light, ~lin,e ....... ~ .... '~:. '.. ''16.0 ,- ,.. .},1..8 '
"f;lf6 . .
)Y.! . . . -,("
.'
, ,
- i"'........ . . .
-.
...'::;-"'-' ".cl'gKfgasoIiIfe:: .'.: ~ :; . ':'::':)~>. ".',- :(4;-:0. ' '::':.15 .4.'~, ..... ': l.-:l~'"
'.
NaturaJ' g<aaoi.4le. ;,:.: ~:l., i~~:'~ j ..;: \ f!. t~~. 0 ,~ ,:::, i5). 3 ,;;: ~\~~.: 1.-. ~ ,
,.
'.'
'..,
' ~.
~t;;;,~~.,: . ',; .l(~,:.:::L(~~ . g~~~~~::.!.-::~:: .=E'~,~i ;~'/~' _'!~:iZ:~~':i: :". ~2:t~~ .~\ :~c'.f~o/.+~.,;:':),.: -r. ;; .?~~,~:.
~~P!i~:~~li~~:.: .. ~~.~ "; :-~~. ,;:,; . }\~,~:, ~;. ~~:~ 9::: .,
.'" . ,,'
,il'.:,-_,,:;,;,;,:;::, '.GaB01iiie. '~: ...." .' .:">~'~'-... : :' ~ . :'10 1.0' ". i" iO'~4"" ,u :f.04G' ., ' ", - .
.. .. ' ' :. ~ght-iilligiiaoline-: ........ ~ , g~3 '. ', 9:7
1.1, . ,
" " " ~~: ~';:~~:~(]~l..ine~ :,-o~ ..:f.cu. ', ' :".': ', .:.'..:o.,..:~' ; ; ifti~ . ~L', .g,.-3.~: ~ :, l ' 04.. - '''''':(''~ ,.... ' :." .,
::';':f)~~~~;~.~;~~illi~;:~;.;!~'~ ;x:~f[.\;~:~'~~ ~: ~~~ : ."5 ~,~.O~':; , : , "' 6'~3:(' '\'",:l~ O$.a:,::, f::;~;~; Ji':"'.: .
, ; ..,', .,':' ~finery gasoline. . . , . . . . ""
5,, 9
?' ~
; ;~ ,
. ~;: .:. r . :~):.:9~~~~:: ~'.", ..:~.}. ',." ~.:.. ~ '.;,:; ::,:.S::O"'~' ~.:,": '~.~.~" ;<~~lJ:,,:-:.~: , .-:-. ~:.
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2
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':I:
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, .. - - '...... ..... 3 ' 0 . " 3 -1'" . .,. L 03~ .; ,
' ~" '2:'0
'2 : 1 . ' ~' J.,.055. ,
;", '
'
,"
.
.fARii2,"i'Ev~por3tion ~-otPet.roleriin fro:m Storage.T8.nb/'.... , .
.... . .
'
- -"
'
.'
":~~t repr~'tative~
;.
-'
of aViation 'gBBOliDes.
,~"
.,:'
,,-,~ ~~ ,. , ~
. ...;j'.
'r "
I
139'
ot mixtures "does not behave as an addftive function ' because API graVity
is not a linear function oJ' specific graVity' [see Eq. (3-1)]. ' When adding
very light Ilquid hYdiocarbop.s such as butane to hea'v ier ,oils, a shriDkage 69,60 in volume ocqurs as indicated in Fig.' 4-40. Light liquids are
, ,-FREEZING POINT OR POUR POJNT--F. (b appli,abte)
120
Il7
"
-80~1-~-I, +7~~~~~--~--+-~~--~~-'~~~
11.9
-00
"?
ItS
often, transported in pipelines along with cfQde oil, 80 and t1;le decrease in
volume ,is signjficant.
Pour and Freezing Points. Congealing temperatures cannot ,be esti' mated with accuracy because none of the common methods of classifying
materials such as Characterization Factor, Correlation In<;lex, aniline
5' ReeveS, ,E ; J., Pet.. Processing, April, 1954, p. 478; and Pet. Refiner, June, 1954,
p. 137.
'
,
,sO 'Childress and Grov.:e, Oil' Gaa J., Nov. 21, 1955, p. 178. '
140
point; etc., disclQse whether or not the material consists of the symrpetrlca.l
types (ring or straight .Ch8ln)81 of hydroc'arbons that cause high freeZing
poiJ1ts.. Nevertheless, .'Fig. 4-41 is an. approximation which is usually
accurate within the following limits:,'
.'
' .
.
..,
",
Average deviation,
--_. pl.ilir
Jet
or minus'
Pour points are usu~y lower than freezing points,1.I2 but exceptions
have been encoun~red.. In the _jet fuel range, based mainly on the
work of Frank Tsai~68 ~ Samples out 0(107 devia~ed by more than 60F
(one high and' one low),)l.rid .10 samples deviated by more than 40F.
th~ di'esel iuei r~g~, the aCuract. is better With only 15,in more than
. 300 samples'2 deviating' by mOl,e' than 15F. .LikeWise, in the lube-oil
range, about 13 of 165 san1Pl~s~deviated by more than 40F. .
The pour pointof ,plends-is:,IlptmaJ1y higherthan would be expected
from the .amount.s\.anc\J~our.p~t~~~e materials that are mixed. However, trace amounts Of asphalten,es<or. natural iDhibitive agents found
i:Q cracked residues or highly' Daphthenic crude oil residues sometimes
cause the pour pomt of such :miXtUres to act in, the reyerse manner. GiG
Note that pour points are. lower than: the 'pOur points of either of the base
stocks in several of the following bl~nds:., .'..
.,
>-
'~-
'
.'
0.
15: '.
".~
-40
~.
25
po
".,
.,
60
80
100
\:
Ii
The other
;-'65
.:....40 ':.'
4
.... 126 .
. "60.
3',500
so-:ea.ned
W.
of
. u. Freezing Point Correla.tion of Jet Fuels, Master's thesis, University Tulsa, 1953.
814. Nelson, W.
Oil G(J$ J., No,,"_ 24, 1949, p. 146. .
"EstimatiAg Pour Poin.ts of Petroleum Distillate Blenda, Pel. Refiner, May, 1951,
p.93.
141
EXample 4-9. Findthe Pour Point o(a Blend of the Stocks ShoWn in Table 4-13.
The indices of the three stOcks are read from Fig. '4-42. Mter determining the volumetric average index and boiling point (~ee'J'abi~ 4-13), of the blend, n.amely, 6.8 and
530F,, the pour point is found on Fig;..4-42 'to be about p~us. ~oF. .
.
, -
'
TABLE
4-13.
4-9
ILLUSTRATION G OF ExAMPLE
Slock.
PmT point
ASTM 50%.temp, OF
25
40
+30
0.
-60
550.'
'B
C
35
. .
"
610.
450
.
'
.Fra~tional
Percent
~5 "
" 17
40..' .
35'
- . '_ 5 ..,6
'~:Ls7
'.
,
.;
."
'.
._ .
'
-.- ".
-Per: cent .
25
40.'
35
~.:
'\!-.
~-
: {; .....
'-
: Stock
4_25
2.24
. d 3i
':,
Index of blend , .' 6 . 80
-' -.
'.
i"'&~
i52 '
" 610
~.
. 550
, . 22Cr-
450
~58
"
Reid
...:. ".-, : ~.-, .
,"
"- Vi~cositY~
q( p~~f61e*m~Ri-od u~s is
~ ~d.i~!tt~q' i~. ~~g~ ~ 4--.4~J "~d. t.g,~,.l?r?p.~rti{~~ ~r~~; ':iY~': ~~:.~~~:~1, ,1~~,,~~: ~~.~wn
In Table 4-14.
oil,"and
scale.
all Petroleum Products a.nd Lubricants, D341, ASTM, 1916 Race St., PhiIa.delphla,
Pa. FQur large chartS, low and high range, for Univers8l snd for Kinematic viscosity
may be purchased. The o-:.IOOF pan of the temperature scale is used as 0-100
uer Cent of blending agent.
.
't.,,-
142-
,70
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k! ,
fta ~
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TV'L
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VJ 11/
-
0..3
0"
.'
,-
-"
,'/
~-
,/
,-
-/
.,
'
/'
V
, ~/ /.
'-
/
;
'(
,
1(/
/'
~
- /
/ ' /'
/
~'/ I
- ~
"
- f
-'
~;
/.
:/
/'
'/ L
./
,
:,
- ~ V,' / / /
0."
"
"'-
I(
'
,~
/' /
~
~ /.1 V ~~ L~ / J -/
!t./V'9' ~:tL ~~"i 1 )
O~//~/ 1'hW)fL
~I
ft'..
~/ ~fi, V
'/-,r/~./
:!"
o.~
./ ,L"
/~ L
L~/_', I'~
0.7
l f i ) ~'l
L- ~J ~~ f~~
~ 0 ~ ~J
/~
1/1;
'i
~~ ~
'/ j
I!
~ :
Z
:
)C -
:\
,h~ ~7
~-
"
.//.')
4"
--
'
II
'/
"
'
"
'
"
'
-,
'
'
'
"
/
{-'
..
, I ~I /
(/'-1
0.1
-80
1 -
-10
-60
-so
-10
10
20
30
040
50
eo
(Pet. Refiner.)
-
,-
.;
143
No.
Saybolt viscosity
22
23
.24
ASTM FU'el._6:
1
2
3
5
6
8
9
10
11
12
13
14
19
l6
17
18
19
20
2i
25
at
.,
...-.... _.....
........ , . ..
. , ..... '.' . ...
. , ,,.:
'~J#..'
,.
..
:~...
76.5
. 57 ,0
,10.0
42,.. 0 "
........... ,.35.0
........... , 48.0
. . . . . . . . . . . . 40.0
, ..... , . . . . . 35.6
......... , . . 32.6
. . . . . . . . . .
36.4:
26.0
~ .'.;..... ';'.' ..
15 .0
200
a~
UmoF
320 at 100F
160 at 100F
180 at 100a F
70' at 210F
58
210F
at
31.0
29.0
30.0
27.0
26.0
21.0
800 at 100'"}'
11.0
986 at lOOD)' 25.0
2,115 at 100F 19.0
23.0
..
8.0'
............... .
19.8
at,
API
.-
" Mid COntinent, TIlinoiS, 'Ca.lifornia, 'and 'm'o~t _ ~t~er c~de oils.
/) Example -of several -Wyoming and Texas Crude oils ,w hich have maximum 'change
in viscosity.
:
c Furol viScosity~ others- 8!e Universal.
,
144
I. NATURAL GASOLINE
2. GASOUN[
'.
. 3. WATER
-4. KEROSENE.
.' i
5. OlSTILLATE
Il 48 GRAVlTV CRLiO
." 1 .040 "GRAVITY CRUOE
8, 35.6 GRAVITY CRUDE
:! Q. 32A GRAVITY CRUDE
I 10.. SALT CAE[I< . CRUDE
,; II. . FUEL 3 (MAX.)
14
000 V.1l
17
J~
II
16'
. ,
'i:~.-+--t-.o.tr='--I
lll5
:. 11 III
~ Ai;~
.. /
.."
200
80
II
eo
I "I I
300
100
I .
400
j I~I
'N,
:
~
10
'.
. "
~I
e
~.
/If IN I( ,i/I.-;'
6
2
ID
:2
08
o.a
QJ
100 eo
eo
4-0 30
20
10
TEMPERATURE f.
FIG. 4-43. Approximate relation between viscosity nnd temperature for the typicaJ
products of Table 4-'-14. " (Ch1.Gcu J.)
145
2,000.0'0'0
1,00'0,00'0
2,00p'000
1.000,'0'0'0
.50,'O/)0'0
.....
200,00.",
100,000
50,00'0
SOOp'O'O
200.000
20,00 '0
1'00,000
50,000 '
\
\
1'0,00'0
2'0,000
10,'0'0'0
oro
500'0
'SoOO
.300'0
1\
2000
15'0'0
100'0
750
1'0'0'0
~\
5'00
4f,JO
750
5'0'0
4'0'0
30'0
300
0
1.50
2'0'0
..
I'SO
(r\
1QO
100
1\
80
80
70
','
TO
-1\
6,0
60
55
50
55
5'0
\
"
4S
,\
4'0
'
"
"
4'0 ,
1\ :",
1\
r\ 35
"
33
'0
33
6'0
40
20
Percenloqe of low vis cosily
80
1'0'0
component
FIG., 4-44. ASTM-type visc~sity-blending chart showing one set of experimental blends,
mended by the ASTM'. The viscosity curves of the two oils are plotted
on th~ standard chart by experimental data on the oils at two temperatures or by noting the general Visco's ity Index properties of the oils. Distances along',the horizontal line of 't he same viscosity as'that of the desired
blend are measured and used in the following manner to obtain the percentage of each oil that should
used in the blend. Refer to Fig. 4-45.
be
'
Per cent
o~ oil B
= 100 ~~
r1'\'0 ,
J~,
146
j :,' ,
~:
::
Also, the ViscoSity-temperature line of the blend will lie between the liIles
PR
= PQ
etc.
Example 4-10. BlendhIg Lubricauq Oils. , A 'high-Viscosity oil (B) ' of 100 sec at'
210<>]". Ss.ybolt Universal viscosity is to be blended with a 200 see a.t l00~ oil (A)
to produce a. blend ha.ving a viscosity of 400 sec a.t 100F. ,The curves for oils A and B
can be drawn by knowledge of their Viscosity Indexes (Fig. 4-2). The percentage of
Oil B to use in' the blends is found by measuring distances along the 400-visoosity line
MO
X 0.64 _ 411:'
t
100 .MN = 100 1.04
' .iI per cen
,
'
The limited us'efulness of the ASTM method is CI~rly evidfm;'t f~n1 this exa,mple.
Note tha.t when, the' oils of this exa.mple are blended by ,the use of Fig. 4-44 (ASTM
method), the amounts of low-viscosity component req'un-ed, 't~ther than bemg 58.5 per
cent. are
'
,,
.
lOO~ 50%
Blending at 210F 55%
Blending 'at
to
an
In
Nelson, Thery, and Sahagun, tlVenezuelan and Other World Crude Oils:" Ministerio de Minas e HidrOearburos, Ca.racas. Venezuela, 1952.
68
r,
147
100,000
2qOOO
........
..
i'.
"2 .5,000
.....
.......
c 2.000
!'..
Q)
V)
.....
..,
0
1/000
500
" "M. . .
'c
:::>
200
.0
+'0
>-
100
' 0
80
.........
' .
....
~
0
50
I/)
vI/)
.......
0
t" /Oi/ B
f'..1 64
~ IS4"
..... . t"
.....
~
.....
......
~
/"'T
......
Oil A
"
" "-
" "
P
V)
6~
........
f'.
l"-
i'...
I'...
::>
"
I'
"
I'
40
"-
'" 'Blend
""
35
'I'
i'.
i'
"
33 -20
60 80 100 120 140 ISO 180 200 220 240 -260 260 300
Temperafure,Oeg:f:'.
FIG. 4-45. Viscosity of oil blends a.nd the effect of temperature on viscosity (Wright ll7
0
20
, 40
method)~
relationshi p69.70 is indicated in Table 4-.16 for gasolines from the same
parent crude oil. The same relationship applies when cuts or fractions ofgasolines7o are considered as in Table 4-17, or in the following
tabulation:71
.
M 0107' octan6 number
Jor 36o-400F
cut8 0/ gMoliM
40
12.0
11.3
10.6
10.0
4S
50
55
60
65
8 .0
4.7
,I.
T
- I
148
TABLE
4-10.
CUT POINT
STRAIGHT-RUN GABOLINES
II
400F
Range of ()Ctane
numbers
67
65-68
63-68
11.7
11.8
11.9
12.0
6664.5
62.5
60
55
49
12.1
12.2
12.3
41.5
35.5
31
54-67
60-65
57-67
47-57
tl-52
33-48
-Low-43
Low-41
4-16.
Mid' hp,
OF
75
IOQ
150
200
Straight_-- run
_ThermaJIy-
Catalytic~y
crack~
cracked
81
77
69
250
300
60
52
44.
350
400
...
35
-8278
- 74
70.566.5
-63
....
82
80
78.5
77
7676
75
149
4-17.
ASTM
90% point,
EFFECT OF
OF
Straight
240
280
'320
77
71
64
360
400
49
440
90
run
57
...
83
81
77
73
70
Catalytically
cracked
83
87
90
82
90
19
88
89
77
90
90
...
. ..
89
90
N = Pa(CNa)' + P~(Nb)
100
(4-7)
in which N is the octane number of the blend, P a and P" are the respective
volumetric percentages of-the agent and base stock, and Ng.and Nb are
the respective octane numbers of the blending agent and the base stock.
Variations in the value of C ~re large because of the inherent differences
larger or smaller ' urid~'the
in gasolines, and in 'addition th~ factor~ '
folloWing con~tions:
'.
- ' ,
,
are
numbers.
.
2. Larger when blending cle~r or l~a.d-free components and sma.ller when the com~
ponents are highly leaded .(2 tA:> 3, cc TEL).
Isomate gasoline when blended with catalytic reform ate bas a blending
factor of about 1.09 (Research method).
Example 4-11. Two Component Blends. Forty per cent of -therma.lly cracked
gasoline of 77, octane nu~ber (Research) is to be blended with 60 per cent of 57 octane
straight-run gasoline.
J
According to Fig. 4-46, the blending factor for thermally cr.acked gasoline at a concentration of 40 per cent is 1.033.
0.4 X 1.Q33 X 77
0.6 X
= 31.8
57 = 34.2
~
~
,.
J'
.<
"
"
,
I
j
150
1. ,Most
so that the
susceptibility of such materials CB..ll
2. Part of the highest-blending.:.vaJue stock such 88 (mainly) polymer should
in each blend because of
high-blending value-of such stocks when
amounts.
able in one
are
number of the entire pJant
run gasoline and the butanes
TABLE
4-18.
PllOPERTlES' OF
BLENDING
TABLE
4-19.
8 .0
30.(J
15.0
38 .0 ,
9.0
Research
Mo
95,
91
51
,105,
69
77
91
96
1:I .. ~w:gIUr
STOcxs"
Motor
80
82
octane
Clear octane
Per cent
of total
gasoline
AVail-
, 105:,
75
80
j5
87
85
91
100
19, 1955,
COMPUTATION OF CLEAR OCTANE NUMBER \ ..." ..."'....""".....,t..;u; OJ'
PLANT GASOLINE
Volumetric
pe~ cent
Butanes .......... .
Straigh t-run ...... .
Thermal .......... .
Catalytic .. , ...... .
Clear (Res.)
octane
number
8
30
38
9
Oil
97
57
77
Partial
octane
number
1.0
1.1)
1.06
1.055 (1.0~ and 1.066)
1.055
"
factor
.Lt.n:;.uU.,I.l.lE>
"
"
."
"
"
....
...
.......
7.76
17.10
12.
36.40
9.12
82.63
151
ALKYLATE
CATALYTIC
ST. RUN
PLATFORMAl'!
1.221--~t---\--f-.-\----I-\--\--l----I--
THERUAL.
PLATFORMATE
POLY GASO.
CAT. OR llIERM..
REFORMED CrHER)
ST. RUN
THERMAL
ST. RUN
ST. RUN
1.18
\-----l--+-.,...;r----+-+----\l--~+'_-
THER ......L ,
ST. RUN
ST. RUN
1.14 f----+--\----\~~Jr+"""":-..T_-____w--:llr_-_+--_I_-_+-___1
1.08 r---+-----1f+--\~_;_\
t041---+---+--l
10
; 15
' 20
25' " 30
3S
40 '
PERCENTAGE OF" BLENDING AGENT
' 45"
50
FIG. 4-46. Approximation for obtaining the blending octane numbers of high-oetane
components.
with respect to the butanes and straight-run (53 per cent total), the factor for thermal
, gasoline at 15/53 or 28.3 per cent is about 1.06. Likewise, considering 47 per cent of
ca.talytic and poly gasoline together in the entire plant gasoline (100 per cent), 0. factor of 1.055 is selected (between curves 9 and 10 of Fig, 4-4'6).
By the use of a lead-susceptibility chart (Fig. 3-4) it is possible to a.ssemble the
gasoline 'stocks in various proportions to produce Regular a.nd Premium Grades of
gasoline. 7a Some blending proportions result in lead consumptions that are less than
. half the amounts required by other blending pro'p ortions. 73
I ':
,j
'J
. j'
, l'
," '~
152
70
...
.......
.....
"'-
NUMBER
-
~ -- ....
.... ......... ~
80
.......
......
......
.... ....
~ ......
~ .............
-.............
--- --
150
_.
--.. ~
~
.........
r---.
........
........
r==::
- - ..1---
200
I---I--...............
I---...... r---. ...... .........
~
I---I--- I--~
~
r----
... '-
...
...........
- -- .- ---
rACTOR
.I
1"'-_ .....
..... II
..............
--'.----- -.-
40
"
-..............
CHARACTERIZATfoN
250
---
..............
r---. ~
--;;-a--
-- --
" - -.-
300
----r----
........
-- ---- ------
i--
~--
,350
. I-...
~-
400
450
behaviqr of. the reformate is nearly the opposite, i.e., it bec~mes the
blendIDg agent. .
.
Solvents. Perhaps the single most important property. of a solvent is
its ability to dissolve vari~us reslns1 gum-like materials, oils, nitrocellulose lacquers, etc., and accordingly there are numerous solvency
tests H of which the aniline point and kauri butanol number are the best
.known. The kauri butanol number76 consists of ascerta.ining the volume
of sample that will cause a standard solution of kauri gum in. butyl alcohol
to become so opaque that lO-point type is illegible when view:ed thro~gh
the solution. Similar tests7~ employ nitrocellulose and butyl or ethyl
acetate solvents . .
Although more than 200 sets of data were used in establishing the
relationships711 shown in Figs. 4-47 and 4-48 between kauri butanol
number or aniline point (Fig. 4-48) J Characterization Factor, and mid
14
'11
7.
.,
.1
153
POINT -
:~o
r.
CHARACTE.RI ZATION
FACTOR
\'Z.~
130i----t--=+-'''''------t-
II of---~--+--~..r:::;.....---t-
1.:.;4------j,.C-.---I+---bL---JC------v---+------I
II
I
r
I :'
I!>O
200'
3S0
er.
400
o4.so
FIG. 4-48 . .Aniline point (approximate) or p~troleum naphthas as related to the mid .
boiling, point and type of oil. (Oil Ga3 J.)
,
'.
_.
.' '~,,'
: . , ..
. ;', " ,' ,.: . . ", I:. ":..,, .
:, __'
boiling' point, thErreiationships are noi' ehtire]y ,satisfac,t ory. .Th 'folloWing,equations Buggested by Ha.rvey arid::Mills77 niay be more' accUJ'a~': ' .
".'
"For K.B;N. below 50:
.
K.B.N.. = 99.6 - 0.8060 - 0.177 A
0.0755(340 - ' B) (4-8a)
~
. '
+ 0.10(340 -
B)
(4-8b)
eF)...
boiling point
'The kauri butanol numbers of straight-run solvents seldom exceed .50,
and a number- above 40 is considered as good. However, even a numher
of 50 is not.usually high enough to comm~nd a special price, and accordingly 'one must look to ' highly aromatic solvents .for ~auri h.u tanol numbers approaching 100. . Superior straight-run solvents (K.B.N. of 40)
'are nevertheless useful because when treated by solvent extraction they
7'1
154
yield larger amounts of the aromatic extracts that are suitable for high- ,
.
solvency naphthas.
Jet Fuels. None of the current specifications of jet , or turbine fuels
are troublesome except the freezing point of minus 76F. Inasmuch a s
the freeZing pomts of hydrocarbons or mixtures thereof . vary greatly
depending on the symmetry of the molecules~ a simple method of predictirig the freezing point of jet or other distillate fuels may never be
available. As an illustration, the ranges of freezing points of some of the
hydrocarbons78 found in jet fuels are shown in Table 4-20. Undoubtedly
when inore hydrocarbons are investigated, the range of freezing point
will be even larger.
TABLE
4-20
Average, OF
"
CarbOn a.toms
5
7
9
11
13
15
&iling point
Freezing point
90
190
-135
-115
,- M
- 61
- 18
15
296
384
463
528.
.Range of
freezing point
2
-12
+68
-14
21
50
to -271
-217
-198
- 100
- 58
- 19
to
to
to
to
to
as
Grade JP-l
JP-2
JP-3
JP-4
JP-5
35 API (minimum)
4~63 API
40-58 API
35-40 API
40-58 API
Thus, the jet iuel yield from a crude oil can be estimated by checking
the freezing point on Fig. 4-41, checking the API gravity against current
specifiCations, and starting the fuel at 130 to 150F sO that Its vapor
pressure is adequate. Sulfur is normally well below the 0.5 per cent
specification linut, and the percentage of ai.omatics, bromine number, and
smoke point are satisfactory unless cracked material is incorporated in
the jet fuel. Somewhat ~ore accurate predictions of fr.eezing point may
78
,, .
be made if jet fuels boiling to 500, 550, 600, and 650F are prepared by a
Approx. depOsit,
grams
10
15
20
30
40
8.0+
.4.5 .
2.1
0.5
0.2
= thermo;scosity
(4-9)
F. Tsa.i; Master's thesis, University of Tulsa, 1953, or Nelson, 'V. L., Oil Gas J.:
.Feb. 22, 1954, p. 197. Four sets of jet fuels from each of 17 crude oils were prepared
and examined . .
80 S.V.I. = smoke pointplus 0.42 times volume per cent poiling under 4OO'T.
81 Kuhbach et aI., SAR Journal, August, 1955, p. 64.
82 Nelson, W. L., Oil Gas J., .Sept. 8, 1945, p. 119.
n Nelson, W. L., Oil Gas J., JUDe 14, 1954, p. 151.
N Russell, A. H., Ind. Eng. Chem., 45. 602 (1953).
71
-~
156
l'ETROLEUM
REFl~ERY
ENGINEERING
I
I
~.
Char.
Factor
API
gravity
Ring
Number
11.2
32.8
33.5
...
11.25
11 -.3
11.35
34.2
35.0
11.4
35.7
11.45
. If.5
' 37.2
11.55
37~9
11.6
11.65
38.7
11.7
11:75
11.8
1~ . 85
11.9
" 1~ .95 : '
j
12.0
12.05<
, ;12.1
- :,
12.15
12.2
12.25'
12.3
a
...
- ....
..... I
36 ..4
"
44.1
,44.8
II
'"
..
....
-40
-34
-24
-14
39.4
40.2
41;0
41.8
42.5
43.3
..
7
17
27
.-
37
.47'_'
,57
45.6
:66
4Q,4 ,- ... 75
47:2
81
47.9
......
48.7
.......
49.0
...
Smoke point
IPT
Fe.ctor&
14.1
14.4
14.7
i5.1
17_
18
18
19
15.6
16.0
-16.5
17.0
17.5
18.1
18.8
19.5
20.4
20
' 20
-21
22
23
24
25
26
28
21.4
22.6
30
24.0
36 .
33
25.7
39
- , 27".6
,4.3
. 30.0
32 .5
35.5
48
54
38 '. 5
61
68
42.5
8~
1955, p. 153.
157
4-22.
60F
ALL A.T
Saybolt
thermoviscosity
KineIIia. tie
viscolSi ty -
100
0.57
150
0.91
1.25
200
250
1.58
1.93
2.26
300
350
400
450
32.3
33.5
34 .7
35.7
36.8
2.59
2.92
3.27
3.60
500
550
600
'37.8
38.8
39,9.
. 41.0..
3.93
4.27
.4.60
650
700
~954J
p. 151. .
QJ450
.=o
5%,")'ield~erosene
/~
Ii)
I'
'+-
o .
1A!400
","
"
..
.~ .
P;- '350
......
.,'
",-'
'0
. n.
-0
to
".
:l
.= Z50100
-'
.2'.
..I'
4-
'".~
-,
>
-.......
trl300
- "'-
." . .
t
o
.-s:
../"
if
",if
-.
./
~~
"/
~, </
V/
/" V
~'L
~~
lorD L'"
IJ
.=
"'-
,, '"".," ~5r()
.;, _:.\
'-
'
-'
'",~
'2.(/%-
-'
',;,,,, JO%
. J' - J'
... J'
428
~
38.r~
,
4-
-.-+c
o
. n..
342
I
. "0
'f;:
)(
,n.
300:
,/'
110 _120
high pour poi'nts, and accordingly, pour point usually becomes the factor,
that limits, yield. Pour point may be judged from Fig.' 4-41; but the
relationShips of Figs. 4-50 and 4-51 for commercial diesel fuels are more
!II'
f'.. '.
~30'.L---+---+--
.........r- CHARACTERIZATiON
FACTOR -+--.............--+---1
-4,01----+--..".,
-80.
4 Oil
420
440
460'
480
.sao
VOLUMETRIC AVERAGE
320
~OILING
S40
seo
:.eo
POINT - Y.
800
FIG. 4-50. Approxima.te relationship between mid boiling point, pour point, ,and Chatacterization Factor of commercial dieBel fuels. (Oil GfJ8 J.)
8'l
Oil Ga8 J., June 28, p. 132, and July 12, p. 118, 1954.
Oil OM 'J.) Jan. 18, 1954, p. 111.
159
.,;'"
DIEStL. INDEX-
I ~/
# "/ . ,
~ ~ ..;0,
~--
~'ri
A..
~ -/ /tJ~ ~ '
10
}'
.
~.I' ~~iI
gp~1/
$"Q
: I
. ,
~~
-.
60
50
(.
,.,,0
Do
. ,.
.,
./
./
./ "
;'
~
~~
~V
":JO
40'
/~
'// .
"
"
11.2
tl'
11.3
II A
11.6
11.5
11.7
I~
ILa
12.0
12.1
_ 122
CHARACTERIZATrON f'ACTOR
FIG. 4-51. Effect of volumetric a.vera.ge boiling point on the Diesel Index of diesel or
distillate fuels. (Oil Gas J.)
'TABLE 4-23. -POUR POINTS, OF, 0,. D1STILLATE (OR DIESEL) Ft7:zL OILs OJ'
550 MlD
BOlLING POINT
(400-700F)a
.
straight-run fuels
Charactel"UJa.tion
Cata.lytically
Tbermally
Factor of.
cracked cracked
Cali- - West
Middle cycle
feed stock Misc. Coastdi&Miss. Vene.
Texa.s
al
fomia
U.S.
East
tillates
or crude oil .
stock
-,
11.0
11.2
... .
11 ,4
-10
/3
.10
16
24
11:6
11.8
12.0
12.2
G
-57
-80
-60
.
-35
.. .
...
0
17
.. .
...
2
7
11
31
42
-40
....
..
o6
... .
....
.o606
I"
...
.. .
'.
'o606
-50
-30
-1
7
o6o6o6
....
. ..
. ..
10
18
25
-9
5
11
15
21
-16
-4
17
J
160
TABLE 4-~. APPBOXlMATE EFFECT .01' BOILING RANGE ON TBliI POUll POINT OJ'
Mid
boiling
point
(OF)
450
500
550
600
650
700
750
Straight-run
Degrees
above or
below Pour
point at
550 0 F
midpointe.
MissisVene- SIppI
zuelan (heAVY
oils)
....
. ...
-25
0
21
-26
--I
40
39
54
55
67
.. .
...
36
57
76
20
... .
91
..
103
Cataly tica.lly
cracked
Misc. U.S.
11.6
12.0.
C.F.
e.F.
-60
-23
3
-45
...
. ...
...
-6
16
-34
-4
18.
36
. 12
3S:
54
52
31
7()
85
46
- 58
-14
11
32.
51
66
....
..
-9
78
21
42
61
76
88
Thermally
cracked
-30
-10
4
16
,rJ
Methods .of judging the burning quality of distillate fuel oils have
not been standardized, but the ped'ormance 88 of one type of pot burner
indicates the following g~er~l effect of the Characterization Factor
88 did not state this reJationship):
(WoiTall..
.
Silk deposita,
Si<k depo8iht,
g12.5 gal
. 100
C.F.
g/2.5 gal
11.8
11,6
60
-36
25
11.9
12.0
12.1
10
7
4
2
11.7
16
a.F.
11.1
11.3
11'.5
The relationship is based on all types of stocks (straight-run and catalyticcycle), a.nd W orrall 88 de~cribed a 11.7 Characterization Factor oil as poor
and one. of 11.85 as good. Catalytically desulfurized West Texas distillate (No.1) produces 86 side deposits of only 6 to. 9 grams, which is
superior to most Mid Continent kerosenes or acid-treated West Texas
distillates.
In making-blends, Diesel Index -is an additive property, a.:hd the po.ur
point may be estimated by the use of Fig. 4-42. Cracking stocks and the
yields from them are discussed in connection with Fig. 19-1 and Table 19-7
-
.'--.
,...
161
Range of
lowering,
OF
1-18
1.0
11
18
25
34
38
2.0
43
0.1
0.2
0.4
0.7
3-34
8-42
20-47
24-53
_ 28-
', . .:.:
162
D~SHED
LINE INDICATES,
THE 8EHAVIOR OF ~VERAGE
LU8E STOCKS
*o
~IOO~--~--_+----~--~--_+~~~~~~~~~r__
10
3 sOr---~--~--~----~~~~~~~~~~--~--~
~ IOr---~--_+----r_~~~~~~~~~--~~~~~
III
Q
~
40~--~--_+--~~~~~~--~~--~~_r--~r_~
)(
~ 20r---1---~~~r_1b~--~--~~~~--_r--~r_~
-,
PERCENT YWC (DEWAXINS to oe ".)
-80~--~--~----L-
II
11.2
11.4
IL6
__
11.8
CHARACTERIZATION
__
- 12
__
12.2
12A
12.15
12.8
13
FIG. 4-52. Approximate Viscosity Indexes of dewaxed lube oils (700-900F boiling
range) as a function of the wax content of the raw (waxy) lube stock and its Characterization Factor. (Oil Gas J.)
be
-t
I
4-25
Misc. waxes G
n-Pa.raffins
I
"
~. ~
750
...
.. .
800
850
700
139
1 ..433
.....
143
1.436
1.435
145
145
143'
143
1.442
1.444
at SO.DC
1.422
37
40
124
135
147
1.425
1.427
157
1.432
900
43
43
..
950
980
47
50
53
166
1100
1130+
Refract. Index
112
920
1000
1025
1050
1075
Melting
point, of
Refract. Index
58
63
66
74
80
1.430
..
......
175
1.437
..
....
.....
..
.....
..
..
......
146
148
151
at sooC
1 ..439
1.446
1.449
1.451
1.453
.. Tiedje, J. L., A Laboratory Study of Wax Processing Methods, PrOc. Fourth World
Pet. Congr., sec. VI, Rome, 1955.
.
.
The amount of wax contained in crude oils varies widely. 96 N. W.
Furby 97 :finds that the drY ,wax (called D.W., wt, %) of residua is related
to distillable wax (called H'. W., wt %) by the Holde m"ethod, about as
follows
(4-10)'
D.W. = 2.+ 1.35 H.W.
ii
.\
,A.
.1
.~~
a.le.
(4-11)
I
I
=5+
164
REFINERY ENGINEERING
0.05
W ngM. % wax in
Ria,
10.5
18.2
0.10
0.20
0.30
'0.40
0.50
28.0
C.F.
700-900 Fe.:ut
0.60
0.70
0.80
0.90
47.7
.6
.55.2
58.5
1.00
.5
20
40
60
80
II
Above
3.0
5.0
7.5
10.0
100
13.5: ,
120
17.0
3.5
5.5
8.5
12.0
18.0
23
4.0
6.0
10.0
14.5'
23.0
30.0-
4.5
8.0
12.0 18.0
30-,0
40.0
5.0
10.0
16.0
24.0
40.0
.0
Most
oils contain very lit~le
even tho~e from Pennsylvania or other paraffinic crude oils, but
intermediate or intermediate paraffin-base
of Venezuela and Burma contain even 20 per
as additional wax in residual lube stocks.
cent of paraffin wax 911 as
There is no entirely
way of predicting whether a crude
cqntain low-cold-test
oil (0 to 10 pour
V.I.
above 40), such as those in Tia
102 Venezuelan oil or Raccoon
Bend, Thompsons,' or Sugarland Te.."'{as (Gulf Coast) crude oils. If the
fraction in a
oil that boils at 550F has a very low Characterization
Factor (under 11.15) and at the same time the 750F fraction has a
Factor of 11.4 to 11.5,
chance of encountering a low-cold-test lube'-stock
good, but there
Numerous
oil analyses
are tabulated in Appendix B.
The cast or bloo~ of paraffin
lubricants is yellow, that of . . . . . . . . . . . . .
base greenish-yellow, and of naphthene base, blue.
165
.fr-----PENETRATl.ON
240
I. I
, ( . ) MIDCONTINENT
220
200
o~
180 . .
160
1-
140
1\
p ,~
'20
'\~
.l
I
100
't
(9) VENE~UELAN .
~!
~b "
eo
)~
50
'~,,\ .
...
40
,,(.) MEXICAN
(A')CAUFO'RNIA ' ,.
"
20
CR~CKEO
o
80
100
~
' ~8 ". . .
I " --\
\
II "
\.
\
' ~
o n
~ (Air- o)lidized)
I
n~
.....0
... 0
120
140
1----
160
180
1--
200
220
240
or asphalt base. It has also been ,suggested by Stanfield and Hubbard slI
that the a.pproximate percentage of 100 penetration aspbalt is equal to
4.9 ,times the percentage of carbon residue of the crude oil. Note also
that the approximate percentage distilled at 1100F'is equal to 100 rpinus
Nelson, W. L., Oil Go" J., Feb. 1, 1951, p. 76.
.
81 Asphalts from Rocky Mountain CtUde Oils, U.8. BUT. ' Minea Tech. Papet' 717
II
(1949).
'
166
TABLE
4-27. ApPROXIMATE
Primary relationship
Secondary relationships"
Characterization
Factor of 750F
bp mat.e.riaI
59
48
40
850F
13
890
17
910
,3 0
940
11.56
24
950
9&5
20
24
27
30
11.78
975
'36
11.90
980
41
17
10
5
11 .22
11.32
11.40
11.63
~1~--4---+---~~r-~--~--~~~~~--~
,~
~~--4---~-+--~--~~~~~~~~~
lit
~~--~r---r---+---~--~
10.
20
JO
40
&0
70
eo
to
100
Gas J.)
(Oil
161'
3 times the carbon residue. The quality' of the asphalt is usually, goOd.
if its Characterization Factor is below 11.8, ~nd especially good Or 'excel~ '
lent if the Factor is as low as 11.4.
. .
'. .
The relationshipl~o between the two major properties of asphalts,
namely, U ring .and ha.ll softerungi poiht't 'and.. '~penetration" at . 77.oF~., is.'
indic~ted in Fig.. 4-53. . Natural a~halt8 ' (Trinidad, Bermuciez, e.Jtd.
Alba~)rtisUhlfy.::hii&;yer.y hjgh'sofwniitg:ifOiiifii~nd.:vet.Y' ibw.~.ne~~~:
tiona. Various indexesl0~.101 have been devised' for classifyi~g. asPhalts. .'.
When blending. two asphalts from :t he same crude oil, . or asphalts. of'
milar type. (vacuum with vacuum"blownwith .blown, etc.), the resultmg': blend has a lowet~ p'e netration thAil.;.wbpld: pe' expected1 o~ :.. (se.e;~Fig.
~54). :Oissimil~r~ ~phalt8 ' prod,:!ce .blel].4s>~itt bear ' no clear 'relation~.
;iliip. to' the properties off the:two componentg';of t~e b~end.. ;' . .... ~}J~1.,_,'~{
."~i101
~~;~
~6h1-#~
'ft~, . ~~j-.{~~:
.: 26~ i951/p~t~)l. '~"'d'f ,' ia1i:
~ 1i~ . i9&5.::P~ :','fl~/S~'i,:~~
N lao ;w
'"
r::''';''A
' , .. 1"9"
.:."."'., ..,>., ...
d ...,'t
!! ~'H"'~<"" \
' j
e n, ~ :~
~;~, titJ.8 .l. , '~ ',
pr., 195~'r',." r-;p. :nI~n'
~~':/ ".
1
' .. 10S NelBo :W t}00'Gr 'c f ' sept 21 ' i950j"p'- 3: :""Y'~ '.
J:
;..
'.
. ~;
. :.:
. ,.
. .: . ..:. ;. .' . .
-.
-. ~
'(~
.. <.
s,I;'\~~ :
:.-:. )~~;~,;:w;~..
:~~'"
.~~
.:r: .~' i~
~",; "
, .' -
- .~ !,,:~~:~:;;:,;~';~:~:j~;~':! ~~!-~~~;
: . ~\~.. _.,
r~:
~ (,.'- :y~
.~
,<,
~:,~f"';). ""
,'. '.
.
.
..,': :: ~ ':'" ,': ()-. ~~,
.'
, ,
I
,:
.
.
..
" , ".
'.
:) ....
.,
,"
-.-;
:.
"
r.
.:
. ",
..
. : ",
J:
:.
...
.-
' :,' :.
'-:',
~', ~
' :'!""",- ..
. ..
"
. . .......
.,
.
.. -
. -.,
..
;
'. "
'. - :
~
.. -
. ,.
; -~
'. '
:,,',
'.
i. . ~ -
.- .',
':....
"',
'.
'
,-
.'-
'I
: ':
'
-.1..'
--
- .
~.~:
t.
" _; ,_: -
: ( -:
~,
, .--
'\
.),
'. '
" ,
'
:- -
',," (':
'.,
",
-.
'
_ ,.
'PRYSlcAL,PROPE,R1IIES
,O.F
oiL , :_-;;,:~ . ;:
.
- .
. :PETROLEUM
.
-'
).:
"
i _
,-' : ; '
.,
..
;"
. :m*1~~~~t~~:~~~~~$~p~~f!s~~~~~b::J;,of.:
~8:~O;P!l.de1ined
Specific Heat~ , The specific h~8.t;.of. a .Il1at,~ri8J. ~s .
a.s:,th.e. CI-uantity
of- heat required
r8.ise~ the temperature of a unit weight of ' material
-to'
required to raise tlle tempera_ .' ._ture of 1 lb of oil lOF - -a.1:1~ ~::.~~~ as Btu per pound per degree
Fahrenheit.
.
, The 5peci4c heat of petroleum fractions is a nearly linear function of
temperature.;' It is also dependen't o~_ the specific gravity. - ' ._,Figure',&-1-{ is: ~hart-" of. tHe spe.cific heats:of Mid Contk~nt pe,t roleum
OiiS. 1,2. The'icurves fo~ 70 ~d'-lO APl"materlar
's6:exact as the .
'qther'cur~es',.beeause n6t many blls of the~"giavities' V;~r~. ~~udi~ .
are not
The
crlti~alliri~"iiidicated i~' 'Fig~-; ~f i~" n6t'~~act becaiI~th~, 6rltici1rt,emperature'.is governed more by the boiling: r~nge t1;lan ~y the gra:vity, but it i~
fneluded in' the: figure as-a. wanup.g tl;tat liqUids cannot -exIst' above
eritical point.., . ,
:.', -.,
. : ,-.
,
' .
the
to
Exainple 5-1. ,Heat Required ~se the te.mperatur~ of 00. How m,uch heat is
~equired to raise the-temperature of 1J OOO Ib of a 40 API niixedbase 'oil [raUl 100 to
~~?
.
,Specific heat at 100, : : ;:. O.4~
Specific heat at 600 = . 0.775
. , r 1.255
~ '.
.
1255
Average specific ~ea(Irom 100 to 600 = 0.627
= 0.627
1,000(600 - 100)0.627 - 313,500 Btu
168
,I
I
169
Specific heats .of gases by Holcomb and Brown 3 are shown in Fig. 5-2,
which is said to be' accurate to O.02, Btu per lb per of. Dotted lines
are used above 700F as a warning that thermal decomposition occurs at
such temperatures.
1.0
2fJ 10
11 gravity
AP
50
0.9
C2 H6
V
/
. ~H8
c.,~o
C4~O ~~2
~V /
",
..:.... ~~
p:
1-' "
I-'
.
~ 1-....... ,,'"
ApproxImate
~~ ~ .
~~ ~~ ~::/ L,..oo....
criticaltemperature _
, /I~V /,~~ ~~ ~/
V .~ I' / ~ ~ ~ %0 V
lh 1'/ ~ ~ ~ ~ ~ /'"
1.10
/ / ~ ~~ ~ ~ ~
A ~ ~ ~ V;; ~
I-'
\"
~,.".",
1.05
\=)
.~ 1.00
;.""
-...;:
~ ~0.95
~~~? V
~ ~V
./
a~O.90
./
Q3 ~
'"
II
60
i8n_ -70
30..L
4p...-t"'..(~;:t1f--"
V
OM
.",
/'
./
II
10
",
I-'
12
I..
Cnaroctenzation faclor
J.
200
400
600
1000
, 800
Tempera/ute, DF
FIG. 5-1: Specifio heats of Mid Continent liquid oils with a correctiop factor for other
bases of oil8.
.
, K '=~
8
'
PETROLE~
170
REF1NERY
0.81---+---+---+--1----+--""""1---+-
0.7 1---+---I---+---+----1!---+--~~
u:.
o
;3.
L
O.5J-,--
0..
1-
.,.-....._+----/---+---f
LO t - - -
U.
0.3
~~----~--4----+--~~--~---+---as~--~--~
10
II
12
Chdracrerizanon
-200
FIG, 5-2. Specific
bases of oils.
Factor
200
400
600
8CO
Temperature CE .
of Mid Continent oil vapors with a. correction factor for other
and Brown, Ind. Eng. Ckem..)
OLCLmuJ
in this book.
upper left comer contains a supplemental chart that
correction
the effect of
The heat ii1put between
any two conditions is obtained by ..........."u... "'...,
A folded supplement to, PeL
24(4)J April, 1945.
Watson and Nelson. Inti.
Chem., 26, 880 (1933).
'l Watson and Smith, Ina..
Chem., SQ, 1408 (1937).
i
II
171
Total heats at atmospheric pressure can be computed by determinIng the heat required to heat a pound of liquid to its atmosp~eric boiling
point, vaporizing the liquid at that boiling point, and heating the vapor to
the final high temperatlU'e using the specific heats of vapors, but such a
method cannot be used (except as ~ approximation) for sub- or super..
atmospheric pressure. Total heats 'at high pressure may easily be computed from Fig. 5-3, and it may also be used to compute the specific heats
of vapors at superatmospheric pressur~ (see 'E xample 5-2). The specific
heat of liquids is scarce]y altered by pressure.
Eumple &-2. Total Heat at Elevated Pressure. A very low-boiling 56 API
Coastal gasoline at 60F is to be heated, vaporized, and superheated to 500~ at an
absolute preSsure of 200 psi. Its Characterization Factor is 11.4.
According to Fig. ~3, the heat content at 60F of a pound of gasoline with a. Characterization Factor of 12 is about 28 Btu. Correction Cor a C.F. of 11.4 results in a
liquid heat content o f '
.
28 X '0.968 = 27 Btu/lb
The heat co~tent of a pound of 12 C.F. vapor at 500F is about 397 Btu. The C.F.
correction is almost negligible .(perhaps -4 Btu) making a heat content of about
393 Btu per lb.
The pressure correction (upper left comer of Fig. 5.3) is only about 8 Btu per lb,
.
. making the total heat
393 - 8 = 385 Btujlb .
The heat input is the diiference between the heat of the vapor and the heat of the
liquid, or
385 - 27 = 358 Btu/lb
The specific heat of the vapor at 200 psia may be estimated. as follows. Such 8.
hI' a volumetric mid boiling point o.f about 190F (see Fig. 5-9), and at a.
pressure q 200 psis. the'mid boiliDg point.be~omes (Fig. 5-27) abou't 400F. 'Ole heat
content of vapOrs at 400F and 200 psis. (Fig. 5-3~ is (the C.F. correction is zero);
~8S0line
400 and
500~)
- (500
~ 400)
= 0.59
A simil.a.r computation, but leaving outthe pressure correction, indicates a specific heat
lLt atmospheric pressure of only 0.55, and this checks reasonably well with Fig. 5-2
which shows a.bout 0.553.
172
30
+ 20
1---+---1t--+---+-+---+-t-For
I
vyeighl
I
I
I
average
+i
lL 10
0
~
__ """"
___ ~
Averoge hOiling
0\
al.r
10
~ 20
u
:E
tIf
30
540
....0
50
c 60
0
+=u 70
C\)
l.l.-
~,;-,
80
90
~=~~=~==~==~==:=QverQge
11
""
0'
'"
' ...
Co
r Or mean
__
r--
~~'~~I~~~~4--4 4-a_~~~_rQ_~~-4~~
\.\.\..
f
of
"\
100~~~--L-~~--L-~~--~J-~--L-~-L--~~~--L-~~
2
3
4
5
b
7
S)op~ of En~lu Di~t illation Curvf2 10 % - QO %j
B
F/%
10
FIo. ~. Relationship between molal, volumetric, a.nd other average boiling points as B
function of ASTM slope.
shown in Fig. 5-4 from Watson and Nelson 8 as a function of the slope of
the ASTM distilla.tion curve. However, the uose of this figure is usually
not necessary because the slopes encountered in commercial products are
somewhat fixed. Thus commercial products usually exhibit slopes and
corrections (between volumetric and molal percentages) as shown in
Table 5-1. Throughout this book, the approximate corrections shown in
this table have been used (as auxiliary scales) on-such charta (Figs. 5-5,
5-9, and 5-12) as require the molal average boiling point~
TABLE 5-1. ApPROXIMATE
SLOPES,
(OF)
Material (general)
Solvents .........................
Aviation gasoline a.nd kerosene.
GBJ301ine and diesel fuel. ......
Gas oil and lubes ... _.. . ..
qas oil and reduced crude ......
Cracking stock and crude oils ......
Crude oils ....... -.........
0
ASTM
slope,
deg/per cent
ASTM mid
boiling points,
OF
150-400
8-11
2
3
4
5
8
7
150-450
200-700
17-23
25-36
35-52
53-72
78-102
Correction,
OF
/I
250-900
300-800
350-700
400-700
104-128
173
....oa
CII
80~---+----~----~
:z:
200
~
-8
300
400
500
600
700
800
Molal Averoge Boiling Point Deg.F.
900
1000
,Crude oils
..I?educed crude
:.. Gas 0;1 'K,1uhes
4 ~~-loo,.--'''r--k-~r-'k-4or-~r-''r-~~'''''''''''''Ir-....3o.c-~-..---f---Ligh! luhes
II?
~ 0
~
200
300
400
500
600
700
BOO
900\'Avioliol7tJ0$D.hrn.
<i.
Volumetric Average Boiling Point, Deg. F.
'SolvenlsFIG. &-5. Atmospheric la.tent heat of vaporization as a. fUDction of molecular weight
(preferred) or API gravity. (CouTtesy of Hougen and Watson, U Chem. Process Principles," vol. 1, John Wiley & Sons, Inc., New York.)
gravity. The dotted lines of Fig. 5-5 show that a 30 API gas oil (or
material of slope 4.5) that has an average boiJing point of 525F will have
a latent heat o~ 114 at atmospheric pressure. It also shows that such a
material has a molecular weight of 179 and a molal average boiling point
'
of about 473F.
At other pressures (and temperatures) than atmospheric pressureJ the
data on latent heat are not extensive, an~ hence a general method such as
IS Hougen and Watson, IIChemical Process Principles/' John ,Wiley -& Sons. Inc .
New York. 1947.
-
174
where L .=
of vaporization at absolute temperature T
,La = heat of vaporization at absolute normal boiling point
'Y = a factor obtained from
5-6.
reduced temperature term used Fig. 5-6 is
on page 182.
Latent heat decreases with
perature until it has a value of
zero at .the critical temperature
(Figs.
and 5-8). Furthermore,
the critical temperatures of high
API
are lower
for
low API materials, and
their
c~6~~-4-4~~~~~~~~
o
when plotted as
latent-heat
13
functions of gravity and tempera~OA
ture, cross one .another at some
8
point, as can be seen
Figs. 5-7
a2
and
o'----1.--'-_
0.40.5
0.6
0.7'
as '0.9
LO
Example 5-3. Latent Heat. Ami:xedL..
l'""r~''r'pl,\1''1''
=:
1040
1360 =
T
"f
latent heat at
= 500
from
+ 460 = 0 706
1360
.
5-6 = about 1.16
9S9-{040
= 98
PHYSICAL
L.H. AT./'
~~
~TMOSPHERIC
8. P.
PROP~RT1ES
175
OF PETROLEUM OIL
140
~~
120
CRACKED STOCKS
[\
UJ
a:
100 B
\
\
160
1i)'
:
'\
~~
)40
a
~
1\\ 1\
60
~
:I:
I--
CONTINENl
-MIDSTOC~
1\ 1'\
\ \
1\
20
0
1\
100
200 300
400
\,
,1
\ \
f\
K
\
\ \ 1\ \
1\
lAJ
:s
\ \\
A PI GRAVlT'f. '10\
40
tZ
80 a::
w
"'"
\
L.H. AT
""\
AlWSPHERIC
....
\., '\ ~
B. P.
I\.
!\
'\ \- ~"\\ ~
f5 80
Q..
\" 1\.'\ ~
I',,~\ '\ ~ N
100
lD
\ \ \ \ ,, r\ '\
r\ \ \ \ 1\ 1\ 1\. " \
\ ~\ I~ \40\ "A \20 1\15
,
\ \ \
~- ~ - \
\
\ \
\ \ 1\ \ \ \
\ \ i\ 1 \ \ -\ \ 1 1\
\ 1\' l\
60 ~
[D
I
40
~
1.&.1
~
t-
"
-\ ~
Ii
....J
"
API GRAVITY
120
I'
)-
r\'" t\.'S ~
20
"
I~ ~
~ '\
,,~
I'\ .
500
-600
\ 1
\
700
800
900
1000
lEMPERATURE ~ F.
5-7. Latent heats (Mid Continent and cracked stocks) 8.8 8. function of tempera.ture
(or pressure). (Oil G~ J.)
FIG.
Note that the latent hea.t read from Fig. ~7 is also about 9S Btu per lb, and at
atmospheric pressure (580F) a.bout 92.
Finally, the total heat chart (Fig. ~3) may also be used to obtain latent beats.
The heat contents of 35 API material at 500F are
Heat of vapor = 378 - 1 = 377 Btuflb
Heat of liquid = 282 X 0.995 '"'" 280 Btu/lb
Latent beat = 97
However, Fig. ~3 should not be used in this way except when the vaporization takes
place at temperatures somewhat close to the atmospheric boiling point.
The estimation of latent heats by Eq. (5-1) and Fig. 5-6 or even by
Fig. 5-3 is laborious, and therefore Figs. 5-7 and 5-8 are suggested lO for
1.O
176
-,
1/
v~
140
~
~~
~
I Ui AT
t--
180
'"N'\ '\ ~
~
ATUOSPHERJC
B.p.
I~ ~
i_\\"1\'
:t:
~ 120
..3
a.
80
t-
~t--.
'\
r--... ~.
-~
,,,
API GRAVITY
40
"
~.
50'
"
,
\
20
I!
100
l
200
300
.1 .
,
\
"
40'
SO It\ '
1<
.0
STOCKS
"\-
NAPHTHENE
60
l.&J
:r
'
II
~ ~I
'~
:::)
~~
1\
.n
100
-J
a:
....,
~~
~ 140
\ ~ \60'
~~
'0
1\ 1\ ~ ~
1\, 1\ 1\ '\ r\' ~ !;:o..,.
r---.."I'I!.
160
~ ~ r-....
r \
I
400 500
600
TEMPERATURE - f .
1\
.
1\30 1\25
\ .
\ .
.\
\
700
1\
Ii
800
900
1000
FIG. 5-8. Latent heats (para.ffinic or naphthenic stocks) as a. function of temperature (or
pressure). (Oil Gas J.)
all but the 'm ost detailed work. All three methods of obtaining latent
heat are based on the same basic information and should therefore check
with one another. The Characterization Factors used in preparing
Figs. 5-7 and 5-8 are
Para.ffin base ...... ; .. ; . . . . . . . . . . . . . . . . . . ..
Mid Continent "or intermediate base ....... . "
Naphthene base .. . . . ............. . .. . ..... ,
Cracked (thennal)-60 API. .... .. ..... . .. "
Cracked (therma.l)-50 API. . . . . . . . . . . . . . . ..
Cracked (thermal)-40 API. . . . . . . . . . . . . . . . .
Cracked (thermal)' 30 API. .. .. .. . .. .. . . . . .
Cracked (thermal)-20 API . ..... : . . . . . . . . ..
Cracked (thermal)-15 API ...............
12 . 1
11.8
11.4
H .8
11.5
11.2
11.0
10.5
10.5
177
The heavy line at the top of each figure shows the latent heat at atmospheric pressure (or normal boiling point), such as the latent heats obtained
from Fig. 5-5. The curving lines show latent heat at other pressures
than atmospheric pressure, or stated another way, at various boiling
points.
The a.yerage boiling poi,pt 'of mixtures is defined with difficulty. An
. arithmetic average, from the distillation curve, does not completely
describe the vaporization properties because vapor pressure not directly
proportional to temperature. A logical average boiling point is the
100 per cent point of the flash-vaporization curve because the material
cannot be completely vaporized at any lower temperature. For batch
distillation t.qe arithmetic average temperature shquld be used for computing the latent heat, but for continuous distillation, as in a pipestill, the
100 per cent point on the flash-vaporization curve is most frequently used.
1'he'temperature at the 100 per cent point on the flash-vaporization curve
is approximately the same as the temperature at the 70 per Cnt point of
the material on' the true-boiling.-point curve. For some other purposes;
such as ~stimating the m'olecular weight, gravity, or viseosity, the 50 per
cent boiling point should be used.
Critical Point and Other Properties. Figures 5-9,8 5-10,8 5-11, and
5-12 4 indicate the relationship among boiling point or range, gravity,
molecular weight, Cha.racterization Factor, viscosity, critical tempera-.
ture, and' critical pressure.
~
is
Example &-4. Use of Figs. 3-9 a.nd 5-10. A distillate material of 31.5 API has a
volumetric average boiling point of 533F. Aceo}:ding to Fig. 5-9 (see dotted line),
such Ii material will have a molal average boiling point of about 500F and a. Characteriza.tion Fa.ctor of 11.35. Other propertie3 are
.
is
178
90wr----r-----~--~~--~~--~----~----~----~----~
80~~~r---~-----+-----r~~1-----+-----~----r----1
.....;
~40~~~~~~~~~~~~~~~~~~~~~~
.{
30
'"0L
+u
20 t-----4.----
.{?O
LL
tOt-----4.------4----
~~~~~~~~~~~~~~~
//.$ :;
N
aI
//.0 1;
o~----~----~----+-----~----.
/-SO
~
-tO~----~----~--~~---~~--~----~----~----~----~
100
200
300
- 400
500
600
700
800
900
/QO
1,000
Zs
til
aI
"'t3
tIQ.
u;
ti 0
100
<t
200
Volumetric Average Boiling Point, of.
1i9
..s
10
IS
20
25
30
35
40 4S
50
55
60
65
70
75
DEGREF:S. API
to estimate the pseudo critical temperatures and pressures of higher boiling hydrocarbons or wide boiling range fractions.
Insufficient information concerning the behavior of mixtures requires
that the pseudo critical temperature and pseudo critical pressure be used
for most oil mixtures. The pseudo critical point as developed by W. B.
Kayll may be defined as the molal average critical temperature and pressure'of the several materials that,constitute a mixture. It may be used as
the critical point of a mixture in computing reduced temperatures, pres11
I
:1
Density of Hydrocarbon Gases and Vapors, Ind. Eng. Chem., 28, 1014 (1936).
180
PETROLEUM REFINERY
a/s
I
0.1
00' ....
sures, etc. However, in computing the pressure-volume-temperature relations of mixtures by use of the pseudo critical point, it must
borne in
mihd that the values are not accurate in the region of the critical
and that it cannot be applied to mixtures of gas and liquid (refer to Fig.
15-6).
Example 6-5,
Ethane
Propane
549
715
665
616
values
+ (0.9
+
181
,ExllIilple 3-8. Critical Pr.essure. A gas oil (or material of slc;>pe 4.3) haa a. volumetric average boiling , point of 520F and a pseudo critical temperature of 830F.
According to Fig. 5-12, its molal boiling point is 465F and it will have a pseudo critical
pressure of a.bout 340 psia..
450
T50
J~OO I
.'i50
700
\\
600
\1 \1 700
\\ \ ,\ \ ~ ,\ \ 150
\ 1\ \ \
\' \ \ f~085Q
',\ \ ,~\ \ \\ i\ \ \l\\' " \ftOf 950
~ \\\ \ \,~\ ~ \ \~ \'.\ \ ~ l\ \\ lO~01050
1\ \ \ 1\ \ \
i500
:rl...J
~400
:J
11) ,
II)
-,
(1)
L.
~O 650
~ 300
i1
Cr- i:;:700
,
100
100
200
~~ ~~~~'\~~\~00
300
400 I SOO
600
700
800
900
Molo') Average Boiling Point Deg. F.'
1000
I .
I
g'
I
q8NL~~~~-r~~~~~~~rT~~~~~
QJ
g-6
Crude oils
,Reduced crudes
~-(J05 0//4-1ubes
.k' Gaso. ~ Oistl/loks
.,
v; 4
~2~~~~~~~~~~~~~~~~~~~
V) 0
~via. gaso. ~ kern
<r 100
800 Solvenfs
Volumetric Averoge Boiling Point, Deg. F.
FIG. 5-12. Pseudo critical pressures of hydrocarbons and petroleum fractions. (O~7.
Gas J.)
Example 5-7. Viscosity (Fig. 6-11). A 5,.5 API material h,as a Characterization
Factor of 10.32. What is its viscosity at 2100j? and at 900F?
Located. on Fig. 5-11 by a dot is the 5.5 API, 10.32 C.F. material. Incidentally,
it has an average boiling point of about 750F. The va.llle indicated by the point is
transferred across the chart in the center of the figure to the index line for 10.32 C.F.
This point can be connected to any temperature on the left scale a.nd the corresponding
viscosity may be read from the scale on the right:
Viscosity at 210F
5.68 centistokes
or 44.9 Say bolt Universsl
VJSCOSity at 900F
0.2 centistokes
182
v,R --
d
d
I
_ volume at specified condition _ V
re ilee vo ume "t
- Ve
vo1uroe a' t cn'toleaI ~om
,
absolute temperature
T
TR = reduced temperature
=
bIte
'f
1
t
'
t
=
-T
'
a so u en lea empera ure
c
absolute pressure
P
P R = reduced temperature = a b
I
t
"t'
al
P
so u e en Ie pressure
t:
PV
P'V'
(5-2)
mm
Example 0-8. Volume of Flue Gas. A flue gas consisting of N2J 0" CO 2) and
water vapor bas So molecular weight of 30, What is the volume of 100 lb of this gas at
200F and a barometric pressure of 740 mm '7
Volume at 200 F =
100
760
(460
+ ,200)
1,648 cu it
alSo
= 2,110 eu ft
183 ,
weight vapors such as natural gasf.!line and gasoline vapors may be handled
as perfect gases up to gauge pressures of about 35 psi without introducing
great errors'. For heavi~r vapors the laws are not exact, but they are
widely used because no other eonvenie!lt law's are available. Figure 5-13
was prepared 8 for all gases, and the present state of knowledge concerning
the compressibility of gases does not warrant closer discrimination.
Th.e theorem of corresponding states affords a method of correlating
the scattered data. This theorem postulates that all similar substances
have corresponding volumes at corresponding temperatures and pressures,
if the reference point of correspondence is the critical point.
Tables 5-2 and 5-3 give critical data by which reduced conditions can be
computed: Many of the data were taken from "Physical Constants
of the Principal Hydrocarbons" by the technical staff of The Texas
Company.
,
Perfect 'gases behave as follows:
PV
nRT (ideal)
where R
PV = ZnRT
Values of Z may be obtained from Fig. 5-13.
Example 5-9. Pressure-Volume-Temperature Relations of Gases That Are Not
Ideal. a. One pound-mole of C3HS (44lh) is held in a container having a capacity of
31.2 ell ft. The temperature is 280<>J'. What is the pressur~7 (See Table 5-2.)
= 665 F abs
= 616 psi
V" = 3.12 eu ft
T~
p~
= 460
+ 280 =
665
1 113
.
+ 280)
'
This indicates a reduced press~re of 228 -7 616 "".. 0.37, And according to Fig. 5-13,
the value of Z should be about 0.915 rather than 0.9. Thus, th~ pressure is 232 !"ather
than 228 psis..
By the perfect gas la.ws, the computed pressUre would be:
X 740 _ ' 254 . ,
P- -_ 1 X 10.7
31.2
PSla.
5-2.
TABLE '
Properly
PROPERTIES OF
Methane
EthaJl.e
PAlI.qFlN
"
16.03
2.98
30.05
3.97
0.300
2 . .5
340
Iaobu\aD.e
Plopa.ne
..
HYDROCABBONSQ
.06
4.. '1-6
0.374
0.609
3.12
4.24
0.063
'4.70
1'.7
12.09
68.08
4:.76
6&,.08
4.46
247
IaopeDtaDe
ButAne
4:.96
0.584
0.625
4.86
\20
5.2,0
94.9
111
Vapor gravit.y;
1.037
2.004
Relative to &ir . . . , ............ .- ...
0.669
1.621
2.004
2.4~
Cu rt at 6ooF. per gal liquid ............
39.2
Z7.3
36.5
80.6
59.. 1
31.8
-259
-128
Bolling polDt. of .....................
-44:
81.1
82.2
10.9
Critical temperature. OR .........
3-14
829
733
M9,
66S
766
715
616
543
550
483
Critical pressure, PSLa .
673
,
2.29
3.12
4.14
4.93
Cntice.! volume, au ft. per lb-mole .... : ....
1.59
3.99
~ CriUcal viscosit.y, mioropoiaes .... , .......
228
2io
159
;~O
239
239
Specific heat:
0.410 1'-6
Va.por .... '..........................
0.473 11
0.411101
0.459 11
0.543""
0.462"
,. .......... , .
0.78
Liquid at 60"F .......................
0.6
0..56
0.55
0.li3
. 1',.18
Ratio at 60 DF .....................
1.31
1.10
1.11
1.10
0.002031Q-Il.7
O.Ooa6.ijo-w
0.00324 10 '-&7.7
Coefficien t of expanaion ......... '.........
0.0038
O.oo~ao'lO-U.'
0.00166'-10
,
Infla.mmability limit.a:
5.3
3.2
Low ............................ . ..
1.8
1.9
l.3
12.5
. High .............................
14.a
9.S
8.4
8.0
Heat. of oombuatioJl:
21,690
Grose. Btu per lb ..................... 23.920
22.360
21,340
21,060
21.290
Net. Btu per lb ....................... 21.540
19,960
aO.460
19,660
1Q.1oo
19.470
Oros8, Btu per ou ft .................. 1,011
2,520
1.770
4,004
3.266
3,2.61
),58
210
Latent bea.t, Btu per lb ..................
226
183
146
166
Vapor prellllUt'e, at lOODF, psia ............
221 0
189
73.5
62
20.3'
OotaDe number, Motor method ...........
100+
97
100+
rn
00
9O.~
pl/W1. expa.neion oonetant. .lor liquids" ......
3.679
4.416
4.soa
5.002
....
..
2."
......
.....
---
._-----
--
TABLE
,5-2.
PROPERTIES
o F.-
PAaAFFIN HYDROCAlUIOIllS"
(Continued)
2.2.4
Property
PeDtaDs
....
HeptaDe
Hexane
]00.13
6.21
86.11
5.11
2.976
3.4.59
20.8
25;5
44{}
6.88
2.8
209.2
,-
976
4. OS
6,86
254
0.339
0.531 12
0.335
0.53 11 ,1
1.11
0.00136 0 - 10
1.11
1.2
1.0
0.9
6.0
20.860
20.780
19,340
19,270
6,254
130
0.54
137
1.63
0
6.290
- -
8.943
7.817
10.87
J9.2
210
536
976
397
1,300
.,. ........
222
16.6
0.330
6.9
0,608
0.799
6.65
60.1
71.8
9 . ..517 .
0.00122
4,762
145
5.0
26
5.216
0.696
6.80
3.943
19.6
258
1.022
370
7.86
/
259
1.10
0.00116 0 -
20.970'
19,420
5.30
0.101
5.89
68.6
5.73
74.2
81.6
155.7
914
O.ao
Cetane
226.43
5.6.2
114.14
114.14
0.688
0.664:
5.53
Trimetbyl
penta no
Oota.De
0.492
10
., .
5.34
.. The number8 above SOble of the data. az-e t.eblper:a.turee ill degrees oentigra.de a.t w.bioh the dt.tll. .re ..pplioable.
~ Me&8ured at 6O"F. &Q.d atmOllphJSrio Pre88Ul'6. whiab.;i& hypo.t.)1eUo~ for t~ liquid h)-cboCW'b~.
c See Fig. 6-16.
.
--
."
0.0008
20,560
]9,060
6,190
2Q.360
117
16
1,8.920
1.0
100
--17
-
"" "
D. 4960--10
"
--
'II
"
6.~
TaLi: 5-3.
Property
....
!
Aoet.ylelle
PROPERTIES QF
V ABIOUS
Ethene
Pl'Qpene
26
28
Moleoular weight . ...... . .... . ........
11. 91
5.96
C&rboll-hydrogen ratio . .. ...... '. ' . . .... .
Liquid grant.)":
0.416
Specifio 60/60 .. ....... ........... .
0.351
Density, Ib per gal at 60"F ............
8.4:7
2.82
20G
API a.t GOF .......... . .. . . .. .. . ...
278
Vapor gra.vity:
0.906
0.968
Rel&tive 1.0 air .... . " . . ... . ..... .. ...
eu H a.t 60DF per gal liquid ... . ......
50.6
39.6
-155"
Boiling point, DF ....119
Critioal tempera.tuce, oR ..............
622
610
Critia.,l preaaure, paia. . . . . ...
911
748
Cr'tiaal volume, au ft per.1b-mole .......
1.81
2.04
. :215
237
Critioal vaooai1.y. micropojaee .. ; .........
BpeoiJia heat:
Vapor .. ............. : . .- .. , .
0.407
0.36.5 1'
Liquid ..f. 60"F ..................... ' .'
1.27
Ratio at eO"F .........................
1.24
0.006.8 9- 11 .'-10
Coeffiaient of expana!on .... ... ; .....
0.0037
bliAmma.bllit.y llmlt.a:
Low ............ . .... . .. . ~ . . ' .... : ...
2.5
2.1
High ... . . . ........ . ...... .. .....
SO.O
28.6
Hea.L of combustion:
Ol'08B, Btu per lb . .... . .... . ........ 21,~80
21,650
Net. Btu pel' lb .. ... . ........ ; ... " , 20,850
20,300
Grou, Btu per cu rt~ ............. . .. 1,489
1,601
Latent bea.t, Btu per lb . . ............ . .
2G6
208
Va.por pC9118ur8 a.t lOO"F, p8i& . . ...... -...
105
,3 97'
Octane number, Motor method . .. ......
Bl
..
......
,.
II
,.
HYDROCARBONS
I.obu~ne
ButeD&-1
66.1
5.96
' 6.9&
66.1
6.96
0.622
4.86
0.600
.s.00
104
0.601
6.01
104
2.011
32.6
19.6
762
680
3.84
260
1.937
38'.S '
20.7
42
140
1.463
S9.5
-64
657
660
2.88
233
,0.811 n .1
0.57
' 1.16
0.0017
2.0
11.1
21,060
19,700
.2,386
IS9
226
86
' .
"
20,740
3,066
169
63.4
87
5.26
9a.1
2.004
~.5
33.8
771
619
0.371
... , .
...
0.366
0.00191- 17 ,'-10
0.001818- 17 1 -10
1.7
9.0
"
..... . , ......... ,.
19,380.
0.63
0.08
. 1.11
1.13
II
6.00
620
o.00 187-1"'-ID
66.1
751
0.362 ll .1
0.5,;
,.
Butene-2
, (mix o( cis and traIlS)
20,860
19.600
3.084
168
62.6
80
-
20 ,(80
10.120
173
47.1
83
--
5-3.
TABLE
Property
1,3 Buta.diene
Pentane-l
Cy~lohenne
(Conti1'Ued)
Benzene
1'o11,lene
78
92.1
10.43'
Alpha.
methyl
na.phthalene
Ce~e
ww ...............
,7 0.1
64.09
7.77
6.96
0.627
5.22
0.M7
- 0.40
87
94
1.877
36.4
2.421
29.1
86.2
23.6
78.5
617
845
594
..............
............
0.332
Q.561
1.12
0.0018
...
........
....
. . . . II
..... . , ...
2.0
11.5
...
High .. . .... .. .
Heat. of oombUBtion:
....... , .
.,
..... .. . .
1.6
11.01
0.778
6.48
60.3
7.03
28.8
.....
3.181
29.9
' 231.1
176.2
1.010
703
4.1
312
4.93
284
o. a98~0
1.3
8.3
1.4-
1.3
6 .7
6.7
155
170
----
18,470
11 :640
626.2
,.
0.4723
, :.
.......
..... , ...
20,316
18,957
4.480
155 . 5
1.0
104.2
-
The numbers a.bove some of the data. a.nI temperatursa in degreea oentigrade a.~ whiob. tb.e data are applio..ble~
Meaaured at. 60"F and atmospherio preuure, whiGh is hypothet1oa.l for liQ.uid hydrOO&l'bona.
7.748
11.09
4 . 009
22.85
469.4
0.00106 D-M
3.4
113.6
78.6
48.1
li.06
306
O~00121D-"
4.500
6.2
611
0.001200- 10
18.225
17 .490
3.750
0.788
6.66
1.028
8.56
' 1,068
'0. 4141t
0'.440..
224.42
6. 96
13.11
0.872
86.8
686
142.19
7.27
aO.8
2.696
2.906
29.4
177.4
99S
----a
0.844
3.a
19'
6.Q6
20.290
18,930
20 . 720
19,360
3,829
148
-
84.1
3.0
2,5
~l-l~-+-
~~/:.C>
R~' tfNfIpera h
~hr~O
2.0
I I
1.5
/,15
.;,
..-a:
">"
...
i
20"
1.0
f
D..
L8.
0.9
0.8
0.7
u;
05
0.4
O.l
1.0
0.6
1.2
0.9t---f--
.s
~----;----~---~-+----+----4-~~~4-~~~~~~~~-4~~N
.~
E 0.25
cS
O.8f---+--4--.J.--+-
0.20
. lO-Reduced
0.15 J
0.10
0.1
.j
0.15
-0.2
.-
Q.3
_.
0.4
I I
1 I I I,
OJ,
l~rnDIVlIIUI'II
, 0.9
1.0
I I
0.7'
0.1
Pit low
I I !I I I I I I
1.5
Z 2.5 3
4
Reduced PruSUf'C, PR
10
0.2
Pres~ure
I
15
,_
0.3
Range
0.4
I I I I I
20
30
40
FIG. 6-13. Compressibility (Z) faotors of gases and vapors. (Courtesy Hougen and Watson, "Ckem. Proce88 Pri'fliCiplu," lIol. 1, John.
Wiley & Sonos, Inc., New York.)
-~
.. -
\- '. '
189
b. One thousand cubic feet of methane is to be compressed from 60F and atmospheric pressure to 500 psig and a temperature of 50F. What volume will it occupy
at tllese conditions?
. 1000
Moles CH. = 379 == 2.64
At final conditions)
+
P. = 500 + 14.7 = 0 765
1l
673
.
T
From
Fi~
= 460
50 _ 1 48
344
.
5-13,
Z
=:
0.94
PV = ZnRT
V "'" 0.94 X 2.64 X 10.7 X 510 - 2635
514.7
of expamioo
0- 14.9
15355164-
34.9
50.9
63.9'
78.9
79- 88.9
89- 93.9
94-100
0.00035
0.00040
0.00050
0.00060
0.00070
0.00080
0.00085
0.00090
= 0.9042
The Density of the Liquefied Petroleum Gas Hydrocs.r~IlB, 21st Annual Couvention
of the NOAA.
f
~\'
190
l.
r:
Volume at 400F"'" 1 X
~~~
4)
La
~U8~~~~~~~~~~~~~~
..
e
IU
0...
En7~~~~~~~~~~~
4)
I-
Q6 k3ooor+--~~~~~~~..p
+-
!
\
j
Q1~~~IOO~~2~OO~~30~O~-A~O~O~~5~OO~~~60~O-L~10-0-L-8~OO~--90~O~~~OO
Temperature, Degrees fahrenheit
FIG. 5-14. Approximate change 01 specific gravity of intermediate-base oils with tem
perature. (Oil Gas J.)
sp gr X 8.328
The relation14 among API gravity, specific gravity, and density is given
13
I~
r
I
191
.'
What is the density at 60F, in pounds per cubic feet, of pure methane, and of ~
flue gas having a molecular weight of 30?
Molecular weight of CH. = 16
Density of CH, = 1%79 = 0.0422 lb per cu ft
-D ensity of fiue gas = 3%79 = 0.07921b per cu It
Since 1 eu ft of water at 60F weighs 62.371h,
Sp gr of flue gas r~fe~d to water at 60F =
6~~::
= 0.001271
= a.bout 28.8,
'=
2~~8
-- 1.04
etc.
' in,which p is the density in grams per cubic centimeter and W is a so-called
"expansion factor." Subscript 1 (2, etc.) refers to any defined condition
of temperature and pressure. The known density PI is divided by a value
of &)1 obtained from Fig. 5-15 for the particular conditions of temperature
and pressure which- apply to Pl. When the value of the ratio pI/~l is
determined, values of p at any. other conditions of temperature and pressure can be computed
PI
P =-w
WI
192
&lld
-=
TR =
PB
conditio~SiAre
<t.S7JJ
60
460
1270 = 0.41
~~;
= 0.0467
Pl
0.816
(oJ =
6.2&'
0.14
+ 460
T R = 6501270
and
= 0 874
.
P Il -= 16%11..= 4.75
w """ 0.106 (Fig. 5-15)
p = 6.25 X 0.106 = 0.662
which is quite different from the 0.64 value read from Fig. 5-14.
At
OF
70F
130'T
1oo"F
300F
Sec
20,000
520
102
66
34.7
U Four charts, low and high range, for Universal IUld for
available from the ASTM. 1916 Race St., Philadelphia, Pa.
kineJll8.~ v~c.QBity
a..re
193
If the oil has a. specific gra.vity of 0.85 at 100F the viscosity in centipoiaes at 100F,
according to Eq. (3-4), will be
14~.7
= O.219t _
<114
ar3
~'
" ~~
.......
~',
-~.... ",,".
~f-.'~
'~~
Q.l2
~~
~
a 0.11
~~
~~
~~~
lo...
0
..r-
0.10
tE
c'
....0
Q09
III
~
tJ
~ 0.08
~~ ~
~
p~ ~,
r---.. J
l"'- . . . .
IW\
11J
0.07
a8\~
-tm
0.06
0.05
Crificol poinf""
QM0,4
0.5
0.6
0.8
Temperature
0.7
Reduce~
9
Q
FIG. 5-15. Compressibility of liquids at high pressures and near the critical temperature.
(Courtesy of H O1J.gen and Wal.8on, U Chem. Process PnMples, I ' vol. 1, John Wiley &: Sons,
Inc.)
r
194
I
i
I
VM~
T~
Pc = 7.7
(5-3)
The critical
temper~ture
215F
102
540F
460 psia
(OC) is
(540
+ 40) +
. v'102
X 31.25 0. U7
~ = 7.7
5550.1.81
7.7 X 10.1 X 9.95
=
2.87
= 270
The viscosity of this gasoline at 50 psi& and 450'"F can be estimated from Fig.
as follows:
450 +460
TB ~ 540 + 460 = 0.91
PB = 5%60 0.109 .
JAR = 0.430 (Fig. 5-16)
and
)j "'"' 0.430 X ZlO = 116
or
= 0.0116 centipoises
~16
Had the pressure been 1,380 psis, the gasoline would have been a liquid, and the
reduced pressure, reduced viscosity, and viscosity would have been
PR =
JAB
JJ
or
18
138%60
= 4.0
= 3.0
= -4 X 270 = 1,080
.,.. 0.108 centipoises
A Universal Viscosity Correlation, Natl. Pel. News, Tee"-. Sect., Oct. 4, 1944.
f
I
0.25
0.2
0.4
195
1/1/
196
200
oj
I
i
180
~500
400
JOO
200
I-
80
I
I ~
20~1
100
.-r
-7-;;
v: ----
---I--12
~
I
500
30 o"f
L- [....,/
RICH GAS
V"
36 molecular weight
I~
200
400 .
600
PressureJ PSIA
800
1000
FIG. 5-17. Viscosities of rich gas hydrocarbon.mixtures (36 mol. wt.) (Oil Gru J.)
240~~~~--~~~---r--~--~~A.r~~-'
220~~--++---n--~+-+-~~~~~---+--~
~=I-~~l-----+--REGULAR
GASOLINE----l
IOO-400F
11.8 characterization fae/or
-jIC---f---I----+---
55.0 DAPI
400
IQOO
800
600
PressureJ PSIA
FIG. 5-18. Viscosities of regular-gasoline vapors (100-4007, 55 API, 11.8 Characterization Fa.ctor), (Oil Gcu J.)
200
The use of Fig. 5-16 is so cumbersome that viscosity values have been
computed U for common .refinery vapors (see Figs. 5-17 to 5-20 and
Table 5-4). At very high pressures the vapors begin to partake of the
properties of liquids (see especially the high pressure range of Fig. 5-19).
11 Nelson, W. L., Viscosity of Va.pors, Oil Gas J., Feb. 12, p. 109. and Feb. 26,
p. 147, 1948.
\"
197
OF
~
,\I)
~/6~
....ti
1200
/lOa
E::
1000
900
'11)
::
350-50OCF
------i
42.5 API
50
/00
150 200
300
400
500
Pressure, PSJA
of
.~
RI60
1400
1200
....g
~
~
a/20
GAS OIL
.\1)
s::
450-650~
80
0
.
50
/00
/50 2QO
300
400
500
P~~~~PS~
. FIG. 5-20. Viscosities of gas oil vapors (4So-650F, 35.0 API, 11.8 Characterization
Factor). (Oil G<u J.)
The designer usually knows little about the boiling points or molecular
weight of lubricating oils, but viscosity $lata are usually available. Thus,
molecular weigh ts can be obtained from viscosity by means20 of Fig. 5-21.
Heat of Combustion. The heat of combustion of petroleum oils increases with API gravity (or hydrogen content) as indicated in Fig. 5-22.8
The figure is highly accurate if the percentage of water, ash, and sulfur is
accounted for. Tables 14-3 and 14-4 give analyses
and heating values
.
2D
198
TABLE
5-4.
VISCOSITY OF A
Pressure, psiA
Temp,
of
14.7
I 50 I 100 I
200
600
700
1000
0
100
200
300
400
92
93
110
111
128
129
142 . 142
158
158
111
129
92
143
159
94
112
130
144
160
95
113
132
145
162
97
114
133
147
163
99
116
135
149
165
102
118
137
151
167
105
120
139
153
168
123
134
149
162
174
300
400
500
600
700
80011
900"
1,000
1,200"
0
94
106
120
130
141
98
109
109
122
131
142
125
131
142
166
167
177
198
152
154
163
174
165
176
197
196
114
140
133
134
145
168
169
180
200
147
144
150
164
173
182
208
180
164
159
170
178
187
216
194
176
178
185
193
233
202
189
195
202
202
213
218
224
230
234
221
215
216
257
234
228
280
238
244
400
500
600
700
8004
900"
1,000"
1,3004
99
100,
104
109
118
, 129
140
161
180
120
130
141
162
181
90
113
119
122
125
131 .
143
161
146
139
' 147
165182
186
170
201
170
155
177
190
258
210
172
194
187 ' 200
197
206
199
300
. o/,k;/ / / / /
~~y~~
V
S
/" ~ ') ~~ L
lL
.~
200
t'i1"e
~'2 L
~8i~
-+-
I]
.!2
>
...o
..0
'00
fDrJ;";"'"
. .--=-. r-::-60
40
-""""
-"""""
L..'
.-""""
-"""""
./
-"""""
,/,/
~,.("n/'/
-;;
/V'7
/././
.L./ /
./""'./ /......
/'
V /
/
.);fof.cQ ~
./
. .",
./
-"""" ~
0.63
0.85
0.87
0.91
0.89
nrn
0.93
0.95
Q99
1.01
Specific Grovity &0/60" F
,/
. V
./
7
-""""
Z~I..-"
Z60 ......
MO
103
;;
../
.......
-;;7
JOO
=--
3D
./
./
!7
~_~~~ 'L---~~~__ ~ __ ~
-~
-~__ ~~
_f--
,/
/"
~'/.O
./
~./ V
~OA,Q';)l 1 / . /
r7
/" /"
l,."ol~ . . ) 7 7 . / v./
I-CorJ s ,....,.-""
80
. ~_~ ~
>.
V)
././
u!Clf....;;'7 ././
>..
-+-
.~
'V
V/
//V /
1.05
- -............
--
107
1.09
FIG. 5-21. Saybolt Universal viscosity at 210F, specific grayity, and molecular' weight
of lubricating oils. (Mills el aZ., Ind. Eng. Chem.)
increase the upper limit as indicated here for one gas mixture. 21 - The
explosive limits of mixtures of explosive gases cannot be estimated from
the composition of the ~xture except by a laborious method. 22
Pressure.
psis
Lower
Upper
RAnge
lOa
4.5
4.15 4.3
4.G!}
4.9
200.
350
4.1
8.0t
13.4
13.8
14.0
17.5
22.6
37.5
3.5
9,25
9.5
9.35
12.6
17.7
33.4
1*
3*
10
14.7
4.9
200
- Zq400
/.
- 20J 200
l&
/'
12.0......;
1l9_
Lll8
io"""
.
f-
h ~ ~/~.7
- 20,000
)~ ~ I/.6
I~ ~ /11.5
~
- 19,800
~ ~ ~V11.4 ~
~ ~ / / IL3 ~'
L
- 19,600
':f.::
~ ~ ~ ~'1.2 \~
~'I/'I .
A~v~v
'.L~ ~
'1:S
s:
6-
19,400
0..
:) - IQ/200
~
01
c
.2-19000
4,
I/)
::l
.A
u0 - 18800
J
~
'....,.
III -
18,600
. (1)
III
o
\..
.i.
L
III
~ ~~~~/lO.~
I~ ~ ~V::V 10.9
A~ ~ ~~~ 10.8 t..ti
~ ~ ~ ~v lale!
V V'Q6
~ W~ ~; L
IQS
v~
~ ~ ~ ~V
IQ4
~ ~ ~ ~ f-""""" 1003
~ % V/ /' 10.2
1 ~ ~ ~r-'/ ' lal
ffL @ ~ L:: lao
V
~~ ~ ~
v
~
Z~ V
~~
~~
:z:
'j..'
- 18,400
- 18,000
h vr;IZ
.~
11
- t7,600
- 10
10
20
30
40
50
60
A.P. I. GrovlfY
FIG. 5-22. Gross heat-s of combustion of liquid petrol~um hydrocarbons.
Hougen and Watson, "Chem. Process Principles," vol. 1, John Wiley
&;
70
(ClYUrtesyoJ
80m, Inc.)
201
Explosive limits,
Mater:a.l
Lower
Highet:
12.5
4.1
2.5
4.3
5.3
3.02
3.12
2.0
2.41
2.37
4.8
2.0
1.7
1.8
1.6
1.81
1.22
1.4
1.4
1.31
1.25
74.2
74.2
1.27
1.1
"
1.0
1.0
0.84
0.74
0.67
1.4
1.1
,1.3
1.16
80.0
45.5
13.9
34.0
15.0
11.1
10.3
9.5
13.5
11.5
9.0
8.4
8.5
11.5
8 .0
8.0
8.0
::;.,)5
6.9
7.0
6.1
6.0
5.3
3.2
2.9
2 .6
5.9
6.0
6.0
6.0
.......
. . , ....
.. ...
......
tempera ture,
of
,1204
1076
635
500
999
1009
950
9~1
871
842
806
760
588
1076
477
1026
914
452
924
450
Above SOO
475
450-500
495
490 .
478
783
Solubility .of O;tygen and of Water in Oils. The approximate solubil~ty of water24 in hydrocarbons and oils is indicated in Fig. 5-24. Pressure
ordinarily has little effect on the solubility, but at hlgher temperatures
the solubility increase~ except in the range of the critical temperature.
2~ Nelson, W. L., Oil Gas -J., Apr. 2, ~956, p. 140.
OiZ GfUj J., Sept. 1, 1952, p. 94.
202
1,6
/.
14
.~~% ~
..J:
.2' 12
>.
.0
N
I
0+-
r:
QI
r% ~
r/::: t::/
!1D\I~~
0/' ~ ~ '/" ~
-+-
~~
~~~~~
t7
~~
~~
v
~
~ ~~
~~---~
V
6(,.ot-'\--:,~
af(~~~v~/;,f~
~
8
-1000, f t[~IP ~D~/~
itO Oof tl\~' oC~ 'i,
,0 Oof ~~1\ st.,.
fJC f tA~fJ
17
10
at
Il-
0(""\ I
000
\I
4qO
JO.O
10.5
11.0
115
12.0
,2.5
Characterizotion Foctor 1<
FIG. 5-23. Hydrogen content of hydrocarbons. (Courtesy of Hougen and Watscm,
"Ghem. Proce83 Principlu," vol. 1, John Wil~ and Sons, Inc.)
<<is
.
TABLE
5-6. Hl:.,AT
Material
OF SOLIDIFICATION OJ'
WU
AND
OILS
Heat of Heat of
Range of
fusion Heat of
Pour solidifisolidifipoint, cation of of wax mixing,
.cation,
of
mixture, portioD, Btu/lb
of
Btu/1b
Btu/1b
122
82
90
28
23
23
3
36
-17
75.6
8.1
. 9.Q
2.9
3_6
3.1
3.1
4.3
4 .1
7 ,511
7.511
0.6 4
L5
PROP~RTIES
PHYSICAL
203
OF PETROLEUM OIL
,
'
_/
'/
30
20
l;Y
10
7
~
'//
~ 1.0
I~
0.7
~ , 0.5
,'I
~ 0.3
~ 0.2
.......
0.05
i, '
0.1
0.02
I
"
0.01
0.007
0.005
-50
JY
rf!
; I
..
r'\'
,) ,- J..
r/
YI
It'.
'f. : 71
0.03
'/1
1/1
V~ ~I
IR
0.07
II
s:
.~
-'"
' 1c
'/
3
~
I.
OBen~tI
ond OJ7s
)( PrtJpeM and isobuJoM
C PrDtJtme and bu/rlne
---
---:-
I: f
l{
50
100
150
TemperoltJre, ~
200
250
300
FIG. ~24. Approxima.te solubilities of water in oil at the total pressure of the system.
(Oil Gat1 J.)
21
204
Partial
pressure,
mm
100
400
5-7.
SoLUBILITY OF OxYGEN IN
.'
Transformer
Gas oil
at 77F
380
7,600
. 1,540
53,200
10,780
at 65F .
20.5
82
15
60 .
770
TABLE
156
114
312
780
228
570
..
5-8.
Paraffin oil
oil at 77F
20.3
81
154
760
1,560
3,800
OILs
Kerosene
at 65F
at 77F
20.9
83.7
159
318
795
. ..
....
Pentane
..
oo
76
304
576
1,152
2,880
5,760
.....
2.8
19.2
5.5
14.2 .
24.6
20.3
27
.......
23
24.7
oo
.. ,.
..
I'
,.
.. - ..
...
to
..
.....
..
. " ...
. ..
I
..
.....
....
..
.....
. ... ,
,.,.,. .
...... .
......
.....
..... .
. -.
..
...
9.7
16.2
18.9
20 .. 8
23.8
25.8
27.4
..
I"
.....
oo
....
. ......
.,
..
. ...
....
12.4
15.1
17.2
20.5
22.6
24.4
25.7
21.6
28.7
29.6
30.4
31.0
31.7
100
200
5.2
0.2
2.8
8.4
10.5
14.0
16.5
18.6
20.2
22.5
23.7
24.8
25.8
26.6
27.3
4.5
8.0
10.9
13.1
14.9
17.4
18.9
20.0
21.2
22.1
22.9
OF
300
400
0.1
3.0
5.6
1.6
8.0
9.9
12.6
14.3
15.6
3.6
5 .3
.16.9
17 .9
18.7
205
(5-4)
Here Ilt refers to the correction in degrees Fahrenheit, K refers to Characterization .Factor, and P2 and P 1 to th~ uPI?er and lower li,mita of vapor
pressure. (mm).
Example' 5-15.
Charts~
76%
206
150 '
100
50
760
600
I I
,300
200
I I I I I I I
1/ 1/ / / V 1/
VAPOR PRESSURE OF .
HYDROCARBONS
400
300
~PANY
VV I
19M
;f
t-O~
10
8
6
u.
0
e.
4
3
la.I
III::
CI)
a:
a:
0
0.8
0.6
Q.
>
Q3
0.02
0.01
r~<;
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TEM PERATURE.-F
Co.)
207
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300
/'1
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l/
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600 "
550
500
760
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vv
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vV V V I I VI V / V/ V II 'I VV I V
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0.03 /
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700
vfr
/ lL IV V
800
900
1000
TEMPERATURE,"F.
1/
1/
0.08
0.02
I I"
/ IV :/ / V
/ V /v
KO~CI II ~(I
I
8 0 Ii / / /
I V/ V / / ~ VVi /v ~/~V~6'v I.!V/V VVV / 1/ / V/
I ~ I V / VV
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208
or
3O,OOO~600
t- 500
20.000
400
15,000
300
10.000
200
so
~o,!c.
..-0'.
I~(,
7.000
,~'(~
100
5,000
4,000
ao
3,000
60
.50
40
tP'o.A
"
-JI
~",.
30
<:..
20
,r:P
,~
~~~
DI
:t:
w
a:
::>
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of.~
6- 300
~
400
<II
Q
II::
50
1.0
LU
II::
0 .7 a..
0 .6 a:
500
L&I
II::
600
~
OS 'a"
0
0.4
20
Q,
qOl
700
. c:P0
800
,.
0.3 >
:!
7
0.1
006
O.OS
0.04
\~c:P
,:#
0.2
0.15
250
II::
en
(/)
290
...w
40
30
a..
a::
..r
II::
~ ..
::>
II)
II)
"-
70
15
(16-
""'~
10
100
~~
14.7
8
6
S
4
3
'j.,.~
~
.,,~
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900
0-08
0.03
0.02
I
0 .!.-1-0.01
I
I
I
I
I
I
I
I
VAPOR PRESSURE
.Qf
NORMAL PARA rON
HYDROCARBONS
OJ~
FIG. 5-27. Va.por pressure a.nd boiling-point correctioIlS for normal para.ffin hydroear.
boIlS and petroleum fractions.
209
on
Nelson and: Haltenbergerl Oil Gas J., June 11, p. 38, a.nd June 18, p. 40, 1942.
Equilibrium Vaporiza.tion of Oils s-n d the Carrying Effects of Light Ends, API
BuU. 10, no. 2, sec. II, p. 52, 1929.
31 Equilibrium Fla.sh Vaporiza.tion of Three Petroleum Fra.ctions, Trans. A.I.Ch.E'J
39, 457 (1943).
211
30
210
P1V~
= P 2V; =
a constant
A line is drawn across the reduced. condition scales on the left to locate a. point on the
reference line (8.5). This reference point is connected with 100 on the moleculArweight scale, and Cp/C y is found to be 1.05.
- -T'J -_ (P'I.)!..=....!
'Y
Tl
PI
(5-5)
12
-.5"
~
1O~
r-(Cp/C v>
.:
if2
1t
i
Q::
Q8
QS
:cQI
~ff
'b~CJq,"tt~ ~'-'
~h
f7'- 3 . 4I 2
r
" 153
121}
o L50
~r40
3
Rri
line
US .
00
~'
85Q
1.10
(.0
0.&
900
DI:
L60
1$0
2.0
'~
800
. ....a
lit 750
c .
0
u 700
-;6'0
a
N-H"EXANE
C)
BENZeNE
NPENTANE
ISOPENTANE
WBUTAN!:
BUTENE2
====;;:.1= li8B~1L.~~! .
PROPANE
BROPYLENE
600
'50
ETHANE
.500
Comp.
ETHYLENE
2.5
10
3.5
Prop-
lylene
~
~
t.zJ
DIISOPROPYL
9'0
lOS
~"":I'&
N~HEPTANf
1.05
lOG
t!'/./~
,.
NOCTA~E
1~4
. IP
9..:l~
:::>
DJlS08UTVL.
1.0'
4-50
t1l
I:IJ
~
o
~
c::1=:: .
o
4.5
METHANE
)ZO
(Scheibel and Othmer, Ind. Eng.
t-.:l
,.....
I-'
212
5-9.
Research
Motor
Paraffin hydrocarbons:
Ethane: ................ , ... , ....... , ... .
Propane ... .......
~
~
Butane .. : ..... , ...... , . . . . . . . . . . . . . . .. .
2-Methylpropa.ne ................... , .. : ..
Pentane.' ............................... .
2--Methylbutane .........................
2,2-Dimethylbutane ..................... .
10
..
"
"
... "
Ii
...........
"
..
If
......
..
2-Methylpentane ..................... , .. .
3-Methylpentane ........................ .
2,2-Dimethylbutane ... : ........ , , .... , .. .
2,3-Dimethylbu tane ..... , .............. , .
Heptane (Octane No. standard) ........... .
2-Methylhexane ..... , ..... , ...... , .... , . ,
3-Methylliexane ..... , . , .................. .
2,2-Dimethylpentane .................... .
2,3-Dimethylpen tane .................... ,
2,4-Dimethylpentane, ... , ......... , ... , ..
3,3-Dimetbylpentane .......... ~ . , ... , ... .
2,2,3-Trimethylbutane ......... , ......... .
~Ethylpentane ......... .' ............... .
Octane .................. '. , , " ...... , .... .
2-Methylbeptane .... ', ......... , ........ .
a..Methylheptane ................ , ....... .
4-Methylbeptane ............' , ........... ,
3-Ethylhexane....... , . '........ ; . , . , .... .
2,2-Dimethylhexane. , .... , '.' .... , .... , , ..
2,3-Dimethylhexane .. , ......... , ........ .
2,4-Dimethylhexane ........ '...... , .. '.' , ..
2,5-Dime~hy lhexan e. , .... , ........ , ... , . .
3,3-DimethyIhexane.. ..,.. . .. , ........ .
3,4-Dimethylhexane ...... , ........... " .. .
2-Methyl, 3-ethylpentane .... , .. ," .. ", .. , ... .
3-Methyl, 3-ethylpentane ................. .
2J 2,3-Trimethylpentarie ... , , , ......... , . ".
2,2,4-Trimetbylpentane (Oct. No. stA.udard).
2,3,3-Trimethylpen tane ........... , , , .... .
2,3,4-Trimethylpentane ..... , .. '.. , ...... , "
2,273,3~Tetramethy lbutane ....... , .... , ... .
Nonane, .' ... " . " ....... , ....... " . ; , .... .
2-Methyloctane ...... , .... , ... , .. , .. " ... .
3-IyIethY1octane, ... , , .... , , ..... , . , , .... .
Dee&ne ..... , .... " .. , .... ," ......... , ... .
2-Methylnonane .... " , ....... , ...... , .... .
2,2,6-Trimethylbeptane, ......... , .. , .... .
+6
97
90.1
99
61.9
90.3
83
,73
75
93.4
94.3
+6
1.9
93.6
100
61.9 (6l.or)
92.3 (gg.5r)
- (l1Sr)
24.8 (29r)
73.4 (69r)
74.5 (85, 5r)
91.8 (97r)
101. 7 (96r)
o (0)
93
- (55r)
65 (65r)
- (8Or)
89
88.5 (94r)
82
-' (SOr)
84
+0.7
-17
,23.S
39
.4
77.4
78.9
69.9.7
83,4
81. 7
88.1
.7
99.9
100.0
99.4
95.9
103.0
-45
-4
12
(981')
.83 (112.5)
62 (68r)
-19 (-19r)
21.7
26,8
26.1"(30 5r)
.5
72.5 (67r)
71.3 (70;or)
65.2 (64. 5r)
55.5 (6Dr)
75 ,5 (72. Sr)
76:3 (80m)
87.3 (7Sr)
80.8 (88.5m)
+1.18 (Ill.om)
100.0 (100.0)
+0.61
+0.22
-34 (-34r)
-53 (.-32r)
-16
78.7
213
5-9.
Research
Motor
.
Olefin hydrocarbons:
Propene .................................
Bu tene-I ................................
Butene-2 .................................
2-Methylpropene ........................ ,.
Pentene-I ...............................
Pcntene-2 ...............................
Hexene-I ............. ', ........ -..........
Hexene-2 .. ~ ~ _....... -. ...................
Heptene-I ...............................
Heptene-2 ...'. _....... _.. _....... .. ......
2-Methylhexene-l ... , .. , .................
2-Methylhexene-2 ........................
Oetene-I ................................
Octene-2 ................................
Octene-3 .......... .- .- .....' ...............
Octene-4 ................................
2,4,4-Trimethy1pen tene-l. .. _...............
2,4,4-Trimethylpentene-2 ..................
3,4,4-Trimethylpen ttme-2 ..................
Nonene-l ................................
2-Methyloctene-l .........................
3-Methyloctene-l .......... : ..............
3-Methyloctene-2: ...........' .............
2,6,6-Trimethylheptene-2 .... : .............
Diisoamylene .............................
Triisoamylene .... .- .............. ~ : .......
Hexadiene-l,3 ......... '.' ................
Cyclopentene ............................
Cyclohexene .............................
1,3-Cyclopentadiene ......................
N aphthene hydrocarboDs:
Cyclopentane ...........................
Methylcyclopentane ......................
Cyclohexane .......................... . ..
Ethylcyc1opentane ........................
1,3-Dimethy lcyclopen tane .................
Methylcyclohexane .......................
PropylcyclopeDtane .................... : . '.
Isopropy lcyclopen tane ....................
Ethyleyclohexane ............. _...........
1,2-Dimethyloyclohexane ..................
Propylcyclohexanc ........................
lsopropylcyclohexane .. _...... '." ..........
1,1,3-Trimethy lcyclohexane ................
81
80
(111.5r)
83
87
.............
80
- ...........
78
.........
..........
75
84
34.7
56.5
68.1
74.3
'86
89
85.6
............
98
83.5
94
73.6
75
87
....
.....
.............
92 (98.5r)
98 (I25r)
80 (85r)
89 (loOr)
54 (55r)
70 (71r)
28.7 (25r)
56.3 (74..5r)
72.5
73.3
>100 (t5Or)
- (133m)
(72.5m)
20 (15r)
(69.8m)
(72.2m)
(70in)
84, (79r)
63
86.1
83.9 (137r)
+0.29 (217r)
85
80
78.6
100 (14lr)
91.3 (t'07r)
83 (109.5r)
62 (59r)
72 (5Ir)
74. 8 (lO~r)
31.2 (16r)
8J. .1 (Bar)
45.6 (43r)
&
......
........
73
28.1
76.2
40.8
78.7
'14
61.1
82.6
8Q.9 (85r)
17.8 (20r)
62.8 (62r)
81.3 (92m)
214
PETROL~UM
TABLE
5-9.
REFINERY ENGINEERING
OCTANE NUMBERS4 07
Motor
Aroma.tic hydrocarbons:
Benzene .................................
Toluene .................................
o-Xylene ....... , " . '.' ....................
1n-Xylene ............ , ...... : ...........
p-Xylene ................................
Ethylbeozene ........... '.................
1,3,5-TrimetbyIbenzene ...................
~ropylbenzene ...........................
Isopropylbenzene .........................
I-M ethyl, 4-isopropylbenzene., ............
1,'3-Diethylbenzene ........................
1,4-Diethylbenzene ... ~ ....... .' ,', .... : ....
Bu ty lbenzene ................. , ..........
II
+2.75
+0.27
100
>100
>100
97.9
.......
98.7
99.3
............
...
.II
.......
...
to
...........
Research
>100 (98.Sr)
> 100 (123.5r)
>100 (l20r)
>100 (144.5r)
>100 (145.5r)
+0.8 (124r)
>100 (l6Ir)
+1.52 (127r)
+2.08 (1321)
>100 (136r) ,
>100 (145r)
>100 (15&)
>100 (115r)
has been studied extensively,IiI,U a.nd some of the relationships are evi~
dent in Table 5-9. In general, the octane number is lowest for the
straight-chain hydrocarbons and. highest for the aromatic hydrocarbons,
with the olefins and naphthenes in an intermediate position. However,
the blending octane number of the olefin hydrocarbons is very high; being
almost the equal of the aromatic hydrocarbons. This is offset to some
extent by the poor susceptibility of olefin hydrocarbons to tetraethyllead. For the
hydrocarJ:>ons the tendency to knock is decreased
by
paramn
The tendency
I..
CHAPTER
INTRODUCTION TO PROCESSING
Because of the wide differences in crude oils (see Chap. 4), we find that
processing methods differ. We may safely say that no two plants are
employing exactly the same processing scheme. What may be a perfect
method of handling one oil may be inadequate for another. The refining
of an oil is, of course, an economic problem. (1) What are the value a.nd
the accessibility of the raw stock; ' (2) what are the value of the products
and the possibilities of marketing them; (3) what yields of products are
to be expected; and (4) what will it cost to process the stock? These
. factors promote the use of many different processing plans.
Refinery Products. ,.. A listing of the more important products of refining will help to show why so many different processing methods' are used.
1. Nat:ural and refinery gas-household and industrial fuel.
2. Gasoline---fuel for internal-combustion engines.
3. Naphtha and benzen~leaner's solvents, paint thinners, chemical solvents, and
4.
5.
6.
7.
8.
9.
]0.
11.
12.
13.
14.
216
ENGINEERING
PETROLEUM
1100 ,-Raw
----;;;...~-
ResicluOiL-fuel oil_
~rn-
sene
fOOfD
27%
1000
25%
38% "
I
-r=-
qOO
--------->r..rE----- - ;..--------~
37%
;/
800
u..
\)
l.'S)
.lao,
.;.
600
.-c
~ 500
. III
/
400
./
too
'f'
cI/
.-
I
I
,.
300
200
./
./
/.
'
j
LUBRICATING OIL PROCESSING
RAW
Wax I Cylinder Tar
Ra~ gasoline KE~ODistillcde
eli sti II otte stock 10%
Gasoline
and
_.
10
-20
~ENE
15%
16%
~~)o -<------..;,.. N~--~2.%_--> ~------~ """----;>CAw
eutrol oils Brightstock
kero- DiFtiHOItle
paraffin I
. cmd toss
30
40
50
60
70
Percentage disti Ileo!
sen~.
petrolatum Tar
and loss
SO
90-
100
Fla. 6-1. Boiling range of refinery products (31.1 API Texas mixed-base erude oil).
stocks, and the finished market products. .The dotted lines indic~Jte
products obtained by cracking. The products obtained by distillation
most of them cannot be sold until they
are-caned "raw products,"
have been further refined.
Raw gasoline and raw naphtha are often treated with chemical agents
such as caustic soda, copper chloride, or doctor solution. Much
naphtha is now catalytically reformed into high octa.ne gasoline.
i
t
INTRODUCTION TO PROCESSING
217
sene usually requires only a sweetening treatment ; _but for flne colors,
acid "treatment or filtration is used. Diesel fuels, distillate fuels, gas oil,
and "residual fuel oil are usually sold without treatment. Pressure
distillate o~ cracked gasoline, ohtained by cracking or thermal decompoSition (Fig-~ 6-2), is sweetened, and an inhibitor of gum formation is added.
N aturaI gasoline, obtained from "natural gas, usually requires only a
sweet~ning treatment for the removal of hydrogen sulfide and mercaptan
compounds.
Wax distillate, the raw stock for the manufacture of the light lubri...
eating oils or neutral oil-blending stocks, contains crystalline wax. The
wax is removed by chilling the distillate and filtering the wax from the oil
in :filter presses. Two unfinished stocks, slack "wax and pressed distillate,
are obtained in the pressing operation. Neutral oils are produced from
the pressed distillate by distillation and subsequent filtration through
fuller's earth. Crude scale is produced from slack wax by "sweating"
or, in other words, by s10wly warming the chilled slack wax so that the oil
and low-melting materials, which together are called foots oil, melt and
drain from the slack wax. Crude scale is slightly yellow in color, and this
coloration may be removed by treatment with acid or caustic or by
filtering the melted wax through clay. Cylinder stock is another wax..
bearing product, but the wax is such that it cannot be filtered from the oil
in wax presses. This so-called U amorphous wax" or petrolatum stock
may be removed by dissolving the oil in naphtha, filtering the solution
to a proper color through fuller's earth, and centrifuging the chilled solution in high-speed centrifuges. The products from this separation are "
solutions of bright stock and petrolatum. The' naphtha is removed from
the solutions by distillat~on, leaving finished bright stock and petrolatum.
Since 1935, the dewaxing" processes described above are being replaced
by the use of solvents such as methyl ethyl ketone for dewaxing both "wax
distillate and cy1inder stock. Likewise, lubricating oiis (light or heavy)
are being treated with furfur~l, phenol, etc., for the removal of the low
Viscosity Index portions. " Figure 11-1 shows the relation of solvent rening to the general processing outlined in this chapter.
Cracking. Materials such as cracking-still gas, pressure distillate,
cracked gas oil, and pres8Ur~.till tar are products of cracking. By cracking we refer to the decomposition of hea.vy or high-boiling oils by exposure
to extreme temperature. At temperatures exceeding about 680F materials such as gas oil, fuel oil, and tars are decomposed into (1) gas, (2)
* The neutro.l oils are often referred to as pale or red oils. In the past it was thought
that part of the wax distillate had to be cracked to produce a. press able material, and
the neutrals from the cracked-distillate, being a deep-red color, were called tIred oils."
The terID8 have now lost their original significanoe, and the term I'red oil" is usually
reserved for any neutral oil that is darker than 3NPA..
RAW STOCKS
--
__
D~9~S--------------------==:~~ --~~=
Wetgos------~~~
Stove distillate
NOI+urcd" 90S
'
Cructe oil
t:=
Distillates
QIO
--iL-~~1::;;;;;fHre;~;
U 9 ht
Mealium motor oi j .
HeCi'vy motor oil
Gas oil
Natured asphalt
motor oil
:I
Cylinder
I'
stock I ,
I.
,:
I
\:
Cylinder stack\
/solution
~
I
I
\ I
\
\
Bright stock----'
steam c.ylinder-stock
~trolatum stock
Fuel oil
.
Thermol Cf()cking~---"l
~.:--=---_.______
.
... ..... Craclced---~
-- --_
-------rcsfdve
"-Coking - ...... - ..... _ .
* .Dotted lInes incl/ccrfe producfs oTcrcrcklng
- - --..._
FIG. 6-2. Rela.tionship between finished, intermediate, a.nd raw products.
f'
''
Fuel oil
Coke
219
INTRODUCTION TO PROCESSING
s.1r(Jlghl-rvn
.
Gasoline,diesel,
naphtho,
_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _..... Irerosene,
or
~
burne' fuels
products
~I
C
Catalytic
Ught
1------. Gasoline
crocking
r---"'T"'~ lJisfllJole
Topping
or
Fllel and
liquilied 90s
or otkylote
Ccitolytic
A
0;1
r----'~ . Polymerize
goSOIJ
erode
. High-octane
gosollne
Ir------.--
L...-.ref_Orming
____
fuels
60S 017
skimming
Lube sloclrs------,
Cycle oil
___ t ____ -,
I
I
I
Oewoxing and
L'~~~~~~~
Topped
erode 017
L ___ ~ ?lJbrfcoJing
B
Thermol cracking
(or coking)
1-----------=-1~_ _ _ _ _ _ _ _....:...-+
Aspholl
Gasoline
Blaclt fuel oils
or coke
FIG. 6-3. Basic refinery operations of topping, vacuum distillation, thermal cracking,
catalytic refonning, and catalytic cracking.
Recycle slock or cnicked gas oil, an intermediate between the two foregoing products, is also produced. Recycle stock has about the same boiling range and somewhat the same physical characteristics as gas oil. This
material is normally recycled through the cracking system until it is completely converted to gasoline, but a part is sometimes sold as distillate or
gas oil.
Catalytic cracking, as well as thermal cracking, has been widely used
since 1941. It d~ffers from thermal cracking mainly in the introduction
of an adsorbent-~ype ca~alyst which holds the asphaltic or tarlike products
of cracking on the surface of the catalyst in the form of coke. Only distilled charging stocks are employed. Figure 6-3 indicates the relationship of catalytic cracking to the operations desc.ribed here.
220
Summary. In general the refining of petroleum is conducted as out-lined in this chapter. However, crude oils vary widely their properties,
contain such
and some may not yield all the foregoing products or
small amounts
certain of the products that their m.&nufacture is not
profitable.
.
In general, paraffin-base raw products are the most easily treated, and
the order mixed-base and naphthene-base. This
the others follow
as well as to the heavy
applies to the light distillates such as
lubricating oils. Many naphthene-base oils contain more sulfur than
mixed-base oils, and paraffin-base oils may contain scarcely any sulfur.
Paraffin.. and mixed-base crude oils contain troublesome wax. The fact
that a true naphthene-base oil contains no wax simplifies the manufacture
of lubricants.
These characteristics govern the methods of processing that are used for
the different bases of oils and the products that are manufactured. Paraffin-base oils are particularly suited for the manufacture of lUbricating
oils. However,
gasoline knocks badly in mod(3rn automotive engines.
Lubricating oils are also produced from mixed-:-base oils, but .acid or solvent treatment is usually necessary, and hence the expense of manufacture
greater. Vacuum distillation, or precipitation of asphalt by liquid
propane, is particularly adapted to the processing of mixed- and
thene-base
because" most of the asphalt or tarry material may be
left behind as a residue, and the cleaned lubricating-oil stocks can be
treated more cheaply than asphalt-bearing stocks. Naphtbene-base oils
produce
asphalt and usually
quantities large enough to justify
its manufacture. The gasoline from .naphthene crude oils is usually
highly antiknock and may. often be sold directly as premium-grade motor
fuel. Some residual fuel oil and gas oil of rnixed- and naphthene-base
O~gln . sold direGtly, but most of the residue that remains after
skimming' the gasoline and kerosene is cracked. By cracking, the'
total yield of
may be increased from about 30 per cent by ...........,' . . . .
topping to as much as 70 per cent by topping and cracking.
The f ollo-yving general types of processing are fairly well defined:
Skimming or Topping Processing. By simple' atmospheric-pressure
distillation the crude oil is separated into gasoline, kerosene, fuel oil, or
reduced crude oil, and sometimes reformer charge stock, jet fuel, or gas
oil. Topping in some form must be practiced on all types of crude oils
(Fig. 6-4a).
.
Cracking Processing. This type usually refers to a combined operation
of topping and thermal cracking, and in most refineries the
oil is
catalytically cracked. No lubricating oils are produced in thls type
operation. Catalytic cracking (not shown in Fig. 6-4b) results in smaller
yields of residual fuel oil. Refer to Fig. 6-5. More detail on
recovery
is indicated in Fig. 7-14.
u
221
Lubricating-oil Processing. 'Topping with the . manufacture of lubricants from the residue of the crude oil is implied by this classification.
Paraffin-base crude oils are, always processed for lubricants. , Mixed-base
oils are often processed th~s (Fig. 6-4 c) or by solvent extraction, but
naphthene oils are processed for lubricants only under the most favorable
conditions. The operations of Fig. 6-4c are now becoming obsolete, 'but
it is included here as a means of introducing the numerouB terms used in
refinery processing. Refer to Chaps. 10, 11, and 12 for m'o dem details
and eapecially Figs. 11-1 and 12-7.
Complete Processing. Most large refiners practice topping, viscosity
breaking (thermal cracking), catalytic cracking, catalytic reforming, and
lubricant manufacture simultaneously 7 and this enormously complicated
complete processing cannot be shown on a single diagram. The manu
TABLE
6-1.
1956
99.6
10.5
24 . O'.
4 .0':
39.4
1.6&
2. 8b
3.5
50.0
6-2.
VARlOUS UNITED
DURING 1956
ESTIMATE OF CAPACITIES OF
FACILITIES
Therma.l cracking, %
(28% of crude capacity)
Catalytic reforming, %
Catalytic cracking, %
(10.5% of crude capacity) (39.7% of crude capacIty)
II
STA.TES CRACKING
4.7
4.2
6.2
5.8
0.4
222
RClw gasoline
,.....L
SfraiQhf run
--"
Gasoline
Nalurol 9Qso}ine /
I:
Treatment:
5weehning
Row Iterosenl!
:.;:
Crude oil
.....
.~
Kerosene
--"
Fue/D17
(a)
~aw
Treatment:
Sweetening
SomeHmes acid
gasoliM
~
I:
0
Row ke("oune
+
~
.....,
Crude oil
r-L
.... r-
NaIUraI 9 O$Ol!'!'e'/f
Poly qasoline
Kerosene
Liquetied gas
Crackedgos
....J ~olymerizCJtion L
Goses
Preswre., Treatment:
Sweetening and
vopor phase or
inhibitor
'crClcled IJOsoline
_g" dis/il/afe
~
.';
lIherorholh
"'Drging .hx~. ~
Reduced crude
Gasoline
Treatment-:
Sweetening
Gos oil
i5
Sfraighf'ruf1
Crockedfuelml
(b)
Treatmenb
Sweetening
Some.imes acid
Raw kerosene
-I:
TreatTnenh
. Sweetening
Slrai hlrun
Gasoline
I-----------i~
........br-------;==================;===;;;~==~
..,
Crudeoil -
/)isMled
cylinder
sfocl(
OosOJ1
Nanviscous oils.
Acid treatment
and filtration
or solvent
Oy vacuum
dish11aHon
Reduced./ L.-----i
Kerosene
j--;1-__JL~Mi~e=d.~~ul~h
Cl
Solid asphaH
Wax distil/ole
crude
By r.esidual
Fil~ration
mt>lhod
or solvent
treatment
E
o
III
8righlsfoclr
0I-
l/)
'Brigh!sfocK solufion
L------~Pe'rolalum solulion
(e)
FIG. 6-4. Types of refinery processing. (a) Topping or skimming processing (catalytic
reforming now also widely used); (b) cracking processing (vacuum distillation s.n.d
catalytic cracking DOW widely used); and (c) lubrieating;>il processing (solvent treating
and dewaxing DOW used).
'
.
.
CRUDE
fRACT\ON AT 10 N
I PRODUCT I
I STRIPPING I
DECOMPOSITION
PROCE.S,S[S
CRACKED PRODUCT
FkACTIONATlON
I I,
I
I
I
I
I tl ~
I ~ 5s
,I
.J.
'- ~ I
'K~
.rosene
""
r,....L
I
I
-;
-g
II
I
I
i
Gu
I
I
Crude
I
I
I
RlclUCj crud.
-,
I
I
~~II
chirp
I
II
u~ '
;;:e
-
...
iii .. ~
... .....2:::J
.cl ~
..
(.)~~ -
I
I---I
l
'
L:...
-
I ~~
I
tl
e e :g
I
I
I
I
~ ~~
~ ~ !i
Llihloaphlha
I
I
'0
.c
Blililnu and
~)!'
~
~~ ~
c3 S:Co
Ga$oUn!
butylenn
, Aviation
I f.
I
T
J~
II~ ".iii~ ~'-.q
GIS
'EIuI~nes and
butylcnu
--" Craelltd
~ ~ :a
11
r.
f'uloll
' ~j
~' ~
~
T'
I
",.
1
I'
I4
Propane
II
I
I
Butanes
~t
'
Alkyl,t.
' Gas
Poly psoUnl
sutan
I
I
~-~ '~
I
'--- I
R~tl I
""
I-
I
I
'
Blltanes
Natural &aSolina
Lllh! naphlh,
Cracked'la$Olinl
~'r
Poly psolln.
II
l.oplnlane
Light naphtha
:::::I.-
I
~
3~:o.i
<3 ~
OtyPI
H,awy naphtha
,'u '!
Dry ga$
P,ntan"
I
I
011
gasoline
.~
.!I
I
I
I
I
J;:> ~
L
I
I
I-9~
~
I
~!
I
. . ~oS
et 'i .dl$tlilale
CracKed
~
::I
ban ,tacit
'
I"
~
..!! ~
Baseslock
LPG
Dry glls
1-.:
",
I--
-I
Gn
BLENDING
Propane
Butan
rr-4r . . J l \ - - - - - 4I..
GQohne
I~
I'
,.
I
i!!
U;
1
llahl cycle gil
~~.~
I
I
Dill
.
Hlall)' eyel' oil
Gas
I;;~ ~!
~
,\,I
Olml
I
I
.!.
I:.
c ~ r---+ Penlanu
Proplne
8ulanu
c
.2
Heavy naphtha
I
fI"gJ
I
1. ':,!IB
I'
.b . .
"
Gas
POLYM(RIZATiON
..
ABSORPTION
PLANT
ALK'tLATION AND
I,
'
I I
:0
STABIUZAllON OR
FRACTIONATION
b
071
~I
1""1"I
f+Leln
Av la lion billil
}_.
}
Motor
gllolln.
.
Aviation
guo II",
Alkyl"t.
!(eloslne
Klroun,
Die~1
Dieul fuel
I<e"*",
0'-"1
u~,
""11)' gnoll
Futl
I
I
-,
I
Gas oil or til
I
FIG. 6-5. Schematic dia.gram of a refinery for light oils (mainly gasolines. kerosene, and distillates.)'
011
Ughl
bfum"
Rui6uill
fUll 011
,,
(
224
Type
1951
1953
25.7
24.8
8.9
7.1
28.5
13.8
3.4
76
TABLE
6-4.
25.6
15.2
0.'4
24.6
0.7
34.3
7.1
14.9
9.3
8.5 '
f.2
1.2
6.3
1.3
8.7
7.7
5:0
6.2
4.7
5.0
'88.5
78
90.5
81
93'.5
Months of operation
Units
End of
19M
Average
man-hours per
stream-time
turnaround,
efficiency, %
per 1,000 bpd
Average
Average
Range
9.7
4.3
8.2-13.8
3.3- 5.3
96
92
400
800
95
94
95
94
1,000
1,800
a}600
1,500
9.4
7.8-14 .0
11.6
9.4-13.6
13.3
9.3-16.3
10.3-15.6
12.9
INTRODUCTION TO PROCESSING
225
CHAPTER
j.
1,100
1,000
/.
900
~ 800
I/)
a....
i600
<!
@ 500
-J-
&.4CO
m
t:
'0
[Q
200
10
ZO
30
40 50
60 70
80 90
100
Percentage Distilled
FIG. 7-1. Distillation ranges of typical Mid Continent. stocks.
Between these two extremes are stocks such as crude 'oil, pressure distillate, pressed distillate, bright stock solution, and special naphtha stocks,
which can be distilled' at atmospheric pressure but which may require the
use of some steam. Figure 7-1 indicates t.he relative boiiing ranges of
typical Mid Continent stocks. In distilling vrude oil for gasoline, kerosene, and a part of the gas oil, a pipestill-outlet temperature of about
740 D F may be required. Thus a sma]] amount of steam is normally
required ,to keep the temperature down to 719F. This results in a
vaporizer temperature in the tower of about 660F. For other stocks,
commonly used vaporizer and outlet temperatures are~given in Table 7-1.
228
Sensitive Stocks. Although the boiling range of a stock is an important factor, the sensitiveness of the stock to high temperatures must also
be considered. All stocks start to decompose at about 680F, yielding
lower boiling products, but even lower temperatures may cause discoloration. In distilling crude oil a slight discoloration of the products (except
kerosene) is not important because most of the products receive chemical
treatment before they are sold. , Likewise, discoloration is not important
in the distillation of a reduc'ed crude oil for the production of a gas-oil
cracking stock or for the production of asphalt. However, in distilling
treated pressure distillate, pressed distillate, or bright stock solution, ' a.
dir:~.: )loration,during distillation cannot be allowed because such products.
al ... substantially ready for marketing. If treatment follows these
distillations, then the cost of, the treatment will be increased by '~e
discoloration.
High temperatures also result in a loss of heavy lubricating-oil stock.
The yield of lubricating oils is often decreased by 10 to 15 per cent by the
use of too high temperatures. A mild decomposition takes place in which
light lubricating oil and gas oil are produced from the heavy stocks.
TABLlil
7-1. VAPOruZER
TEMPERATURES
Tempers.ture,
OF
Stock
Products
Vapor- Heate,r
lzer ' outlet
210
2.
3.
4.
5.
660
670
275
670
690
730
775
Pressure,
psi or mm
Steam'
.'
230
325
710
710
120-200
Atmospheric
Atmospheric
Atmospheric
Some
Yes
710
Atmospheric
3{}-80 m~
'30-80 mm
Atmospheric
Yes
Yes
Yes
730
770
&50
No
Yes
Yea
found that 770F was too high. If the stock is held-at 835F for more
than a few minutes, extensive cracking will occur, and the operation will
become a cracking process. Thus the temperature that can be attained
without serious decomposition is dependent to some extent upon the time.
Although a lubricating-oil stock can be heated to 710 or even 740F in a
low-absorption-rate pipestill heater, this same temperature, if maintained
-in a shellstill, will cause serious losses in yield and a discoloration, the
removal. of which may necessitate a costly chemical treatment.
Arrangement of Towers. In separating a series of products from a
charge stock, three main tower arrangements are employed. Heavy-oil
stocks, such as crude oil, are- usually separated in a single tower, as indicated in Fig. 7-7. In such a system the feed enters somewhat low in the
column, the lowes~boiling product issues from. the top as a vapor, and
the ~eavier distilled products are withdrawn from the side of the column.
The small towerlike equipment shown in the center of Fig. 7-7 is not a
fractionating tower. It is a series of three steam strippers set .one above
another. The system of. Fig. 7-7 is unsatisfactory for producing highly
pure products such as pure hydrocarbons because the lighter products
pass the withdrawal trays of the heavier products as they proceed from
the feed plate to the top. F~r precise separations a series of towers
(one tower less than the number of products) as shown in Fig. 7-2a or b
is often employed. In Fig. 7-2a the lowest boiling product 1S vaporized
in tower No. 1 by -reboiler heat at the bottom of tower No.1, and successively higher and h.ig~er boj1ing materials are removed in the remaining
six towers. rhe feed is pumped from tower to tower, each tower is cooled
by refluxirig a part of the overhead -product into the top of the tower, and
the bottom of each tower is heated by 'steam or a hot circulating oil by
means of reboilers. -Successive fractional condensation is practiced in
Fig. 7-2b. Here an almost completely vaporized stock is cooled in tower
No.1 to condense the highest-boiling product, and successively lower-boiling products are condensed in the remaining six towers. -The novel but
little used Brugma 1 arrangement _of towers sbown in Fig. 7-2c employs
only three towers, but the total length of the three towers is about
the same as the length of the seven towers in Fig. 7-2a and b. Obviously,
many combinations -of these tower arrangements are possible, as In
Fig. 7-8.
- More material can be vaporized (at a given temperature) by a -single
flash vaporization than by several flashes, and hence the use of a single
multi draw tower (Fig. 7-7) is better in this respect than the series arrangements of _Fig. 7-2a and b. Refer to qhap. l5 fOf a mathematical discussion of methods of vaporization.
Steam Stripping. Steam is used to raise the flash point -of most of the
hea vy-oil products withdrawn from the side of multidraw towers and for
, 1 '&I. Nat. GaBO. Mfr., $eptember, 1941, p. 86.
,
i
i
. I
229
230
No.1
Products
No.2
No.3
No.5
No.6
No.7 No.8
Feed
Feed
-~
Rehoilers
Products No.6
No.7
No.6
No.5
No.4
No.3 '
(b) Sep.orotion by successive , fracHonal condensation
No.1
'No.1
No.1
No.Z
No.3
reed
......~No.4 ~
"tl
........-P'
No.5 ~
n..
~~No.6
~~N.o.7
.i
ii
--~No.8
Pftmory ,
Intermediate
tower
tower .or towers
(c) The Brugma fractionation pr:-ocess
FIG. 7-2. Basic arrangements of fractionating towers. (a) SeParation by successi'\'e
fiash fractionation; (b) separa.tion by successive fra.etional condensation; and, (c) the
i
)
r,
231
the bottoms product of heavy-oil towers. The hot oil is contacted with
the steam in a so-called" stripping tower" which may be a packed tower
(up to 20 in. diameter) but usually consists of bubble trays or side-to-side
pans. The use of four bubble trays (about seven side-to-side pans) is
common, but in the' extreme ten plates have been used. If as much as
6 to 10 per cent of low-boning material must be removed by stripping, it is
usually more economical to adjust the composition of the product in the
fractionating tower than to steam-strip.
The approximate relation between flash point and (0 to 10 per cent)
boiling range is given in Eq. (4-6a).
.to
I
I
fkERo.iENE
With this relationship it is possible
GAS Ol~/
i-'
I--"
I
-;:;
~NAPHTHA
...
to estimate the amount of material
v~
V/
./
that should he removed by strip- ~ 8
v
v
0:
.0V
ping in order to obtain a satisfactory cr: 7
./
'
TOPPED CRUD OIL
~
flash . point. Figures 7-3 and 7-4
/
~
indicate the approximate amounts o~ 6
w
of steam required in stripping o> 5
:::i:
I THEOREnC~L PLATE
naphtha, kerosene, distillate, gas w
"
!r
oil, topped crude oil, and similar 1--4
V
.~
J
products. 2 Figure 4-49 indicates 03
the wide range of kerosenes (or a.ffi
2
similar products) that can be produced by adjustment of the frac}
tionating tower and degree of
,0
2345678
stripping. The dotted lines (Fig.
La. STEAM PER GAL.
7-4) are examples of the effect of FIG. 7-3. Approximate stearn required to
infinite plates on. gas oil and on strip when using only a. bath of liquid,
i.e., only one theoretical plate.
topped crude oil. Stocks such as
topped crude oil (which are wide-boiling or have been disengaged fro~
a wide-boiling material (such as crude oil) require large amounts of
stripping steam.
Vi
1# V
No. of plates
1 (Fig. 7-3)
4 (Fig. 7-4)
10 (Reference 2)
1.0
0.45
0.40
2 Nelson, W. L., Oil Gas J., Mar. 2, 1944, p. 72; July 2l, 1945, p. 128; and Ma.y 12,
1945, p. 51.
232
PETROLEUM
conditions
ENGINEERING
.......................
or
fuel ............
oil. . . . . . . . . . . . . . . . . . . . . . .. .
oils. . . . . . . . .. ..........
Topped crude oiL. . . . .. .........
Residual cylinder
'" . . . . ..
0
.5
O.
.6
O.
.5
0.4-0.9
0.4-1.2
1.0 up
/~
~d) PLATES
lOPPED CRUce:
l!)
Z
Q.
0.-
cr.
t~ 6~----~-*~------~------~~------~---------+--------~
>co
Q
OJ
o>
2
~ 4~--~+--4------~~--------+-------~---------+--------~
IZ
w
(4 ACJUAL PLATES)
U
0::
.4
FIG.
7-4.
.8
1.2
LB. STEAM PER GAL.
wi~h
1.6
2.0
,2..4
valuable in separating
hydroca'rbons which
many other hydrocarbons.
constant-boiling mix
as aniline} furfural,
nitrobenzene, or chlorex are
uced at the top of
fractionating column and withdrawn at
The solvent is
from the bottoms
by means
It is parti
tend to
(1946).
233
Naphfhene
Aromafic
Aroma/ic
_L_~
, ___~=_=_=!::_==_~_~
So/vgnf mokeup
feed
____
---~
... -1- - - -
0 . . . . - _...
JSolvenf
Nophthene-aromatk
Solvent
Products
' towel'"
recovery
FIG. 7-5. Simplified flow diagram of the Distex or extractive distiIlatjon proceSs .
tower
i,
234
"""'1:---,
I
I
I
I
Sfeam~
...
I
BIO~
r
... Gels
!-w- mOKe-up
--Moisf
liquki
Cooling
wofer
"Slugs"ofwofer
or causfic
feed
liquid
Separator
Wafer
Adsorption chlltnbers
FIG.
Cooler
Separator
Proauct
and heater
~s
Fractionation is also mdely used for drying liquids that are substantially i~miscible with water, as propane or the hydrocarbon oils. The
low-boIlIng product of such a system is a constant-boiling mixture of
..
235
water and the hydrocarbon (in proportion to their vapor pressures) which
upon condensation separates into a hydrocarbon layer and a water layer.
The hydrocarbon layer, along with fresh feed, constitutes the feed to the
fractionator. The solubility of water-in various hydrocarbons is indi- .
cated in Fig. 5-24.
The general effect of mesh size on the drying capacity& of bauxite is:
-MesA size
Rela.l:ive capacity, %
Likewise the effects of air velocity 8 and relative humidity!!' 'of air- on
bauxite drying 'are:
A iT velocity,
CUjt/hT/lb
Rel.
capacity, %
10 ............... 100
15. . . . . . . . . . . . . .. 97
20. . . . . . . . . . . . . .. 85
25. . . . . . . . . . . . . .. 69
Rel. capacity, %
97 .................... , 100
75. . . . . . . . . . . . . . . . . . . .. 85
50. . . . . . . . . . . . . . . . . . . .. 68
10. . . . . .. . . . . . . . . . . . . . . . 39
236
The remaining pages of the c~apter are devoted to the common processing systems. The systems thati.;are presented are not necessarily the best
for all conditions. In fact, in some cases they are presented merely
because they are novel or because they illustrate principles that would
otherwise be neglected.
The operating conditions are likewise of a general nature, although in
most cases they are conditions that have been recorded in plant operation.
The evaluation curves that are shown with the processes are discussed in
Chap. 4 ..
A survey of the processing methods used in refineries appears to show
that there are as ma.ny methods as there are refineries. Nevertheless,
upon close inspection these many methods are found "to be essentially the
same, and the major differences aTe in the arrangement and shape of the
equipments rather than in the manner of operation. In most refineries
the proc.essing methods are the result of years of development; and
although the processing methods may be modern, the equipment that is
used may appear to be obsolete. This is often the result of the use of
existing shellstills, towers; chambers, coolers, etc., from antiquated
equipment. They appear obsolete; but if they are properly utilized, they
may perform as satisfactorily as new equipment.
Topping or Skimming Crude Oil. In many ways the initial breakup of
crude oil into raw products is the most simple distillation process. Certainly it js the most widely known operation.
In the topping unit shown in Fig. 7-7, oil is pumped .continuously
through the heat-exchange system at a pump pressure of 125 to 200 psi,
through the tubestill, and into the vaporizer section of the multiple-draw
fractionating tower. At this point the temperature must be sufficiently
high to cause vaporization of all the products that are collected at points
above the vaporizer, and the temperature may be a little higher, so that
about 20 per cent of the bottoms stock is also vaporized. The purpose of
the additional vaporization is to provide better fractionation 'on the plates
that are situated just above the vaporizer. Without excess yaporization,
very little reflux will exist at these plates and no reflux will flow from the
. plate abovethe vaporizer into the vaporizer section. Reflux is circulated
through the top of the column. The hot reflux material is drawn from
the tower, cooled by a heat.exchanger and a water cooJer, and returned to
the tower. It serves to cool and condense the V'apors that arise from the
vaporizer. The recirculating type of reflux shown in Fig. 7-7 is not the
most common method 'or removing reflux heat, but it is an excellent
method for certain conditions. Various means of removing reflux heat
.,
237
are shoWIi in Fig. 16-3. The plates above the vaporizer or feed plate
act as rectifying plates, but the plates below the feed are steam-stripping
plates. Steam is admitted below or on the bottom tray, and the lowboiling materials in the vaporizer residue are removed so that a high-flashpoint bottoms product is produced. The steam ascends the tower, and
at the vaporizer it is effective in lowering the vaporizer temperature.
The system as shown in Fig. 7-7 is not limited to the production" of four
overhead products. As many as eight products have been withdrawn
from a single tower. Furthermore, by the use of a large amount of steam,
sucl;l,h~avy stocks as wax distillate and even .cylinder stock may be vaporized from crude oil.. However, the vaporizer temperature must be high
OP~ssureSi in, Hg
Temperaff,l~s '1: t=:jI:~=~ ...r--.&.L--J.----4~~=-'
~~-4~~~11~dS8%
,
"
238
TOPPED CRUO[
(a)
LICHT GASOLINE
O.GASOUNE
CRUDE'
TOPPED CRUDE
GAS OIL
NAPHTHA
(b)
11
1945, p. 81.
H
Nelson, W. L., Oil GM J., July 21, 1945, p. 128, e.nd July 20, 1946, p. 123.
239
expected to pay for themselves in 2 years but the general situation js presented in Fig. 23-5. In complete plants, which conduct vacuum and
cracking operations as well as the topping of crude oil, the crude oil may
be advantageously heated by products from these other units because
they are at a relatively high temperature. For example (Fig. 7-10), the
crude oil may be pumped through the condenser exchangers of the topping
plant, through the condenser: exchangers and side-product exchangers of a
vacuum plant, through the bottoms exchangers of a cracking plant, and
9PO'~~~----~~--~--~--
__
__
____
__
800'~--~----~----~---+-c~~--~~~-r--~
~ 700~---4----~~~~--~~~+---~
t
Q:
J!
b.I
~ 6901~--T7~--~~~r----+--~~--~~--~--~
cc
o
n..
.(
~.5001~~~~--~----~~-+----;---~~--~--~
~
I
I
It)
;:)
It)
"I
~ Ol~~~--~~~--r----+~~~--~~--~--~
Il.
ffi
i
3001~--~~--~----~---+----+---~~--~--~
U)
~ 200~--~----~----~---+~--+---~-----r---1
IOOr----;----~----~--_+----+_--~----_r--~
O~--~IO~--20~---3~O~--~40~--~50~---ro~--~M~--_~OO
PERCENTAGE DISTILLED
FlO. 7-9. True-boiling-point and ASTM (dotled) distilla.tion curves of topped crude
oils produced by flashing at 400, 550, Rnd 650 F. (Oil"Ga& J.)
D
finally back to the topping tower. In some plants a crude-oil tempera.ture of 600 to 650F is attained by heat exchange alone. Figure7-10 1Fi
is an attempt to indicate the main sources of heat in an exchanger system.
In isolated topping plants, exchangers are also used on the side-draw
products of the topping plant. In general, it is usually economical to
bring the crude oil to within 40F of the temperature of the hottest heatexchange stock that is available. In deciding which stocks to employ
15
240
COASts OR
WN.D AVI""ON
GASOUNt
1-
fW)~NG
TOW!Il
OR i-VACUUM .OWER
UlUC[ STABILIZATION
OA PFiE-Fl.ASH lOWER
TO P PING
I AtOUCING lOWER
OR 2-1/ACUUoI TOWER
OR ;) -CAAOQNG FRACTlDNA1CR
1-RDUClNCO TOWER
OR :i-VACUUM TOWDl
OR 3-CAACKlNG nA5H TOWDI
,
I
I
OR POS.SIBlV
OIolIT PIP UTIL L [TC.
I
be a source of great expense unless they are wisely chosen and the stocks
are clean and noncorrosive.
In .the extreme, exchangers could be utilized on every tray of a fractionating tower as well as on each of the products and perhaps succeed in
attaining a thermal efficiency of 60 to 80 per cent. One such system 17
succeeded in operating without condensers. The real merit of such ~
system, however, depends upon the cost ot installing and maintaining the
heat exchangers, and it is doubtful if such ~ jsy~tem is e~onomically
fea~ible in view of the low cost of heat in most refineries.' Extra. trays
would also be required in a fractionating tower employing such a large
amount of heat exchange because the tower would operate with very
little reflux ..
Nelson, W. L., Oil Gas J., Nov. 24, 1945, p. 147.
liZiegellhain, W. T., No Condensers Used in Topping Unit, Oil Gas J., Dec. 18,
1930, p. 30.
16
'!
241
Even after a complete use of heat exchange some products will go to the
water coolers at 250 to 400F. These stocks along with the hot fiue gases
from a pipestlll or other heater may be used to generate steam in what is
known as a ."waste-heat boiler." Such an installation 18 is generalized in
Fig. 7-11. Feed water that has already been preheated with exhaust
steam in an "economizer" is heated further by any suitable hot oil stock
that is on the way to' storage (or water coolers) a.nd is introduced into a
steam drum. Meanwhile, hot water is circulated from the drum through
tubes that are heated by flue gases. High-temperature gases from a
cracking still, thermal polymerization stiU, catalyst burn-off still, gas
reversion still, etc., are suitable. Waste-heat boilers would appear to be
FtOSTOCK
TO
PIPE STILL
HOT OR HOTT.EST
PRODUCT
FROM PROCESS
~~
.~
.
).
SATURATED
STEAM TO
SUPERHEATtR OR PLAJIIT'
SYSTEM.
GASES TO STACK
FEEO'WATER
FROM EXHAU ST
STEAM HEATER
HEAVY STOCK
TO WATER
COOLERS
. MANIFOLDED
CIRC.PUMP STEAM EXCHANGERS FEED
STEAM TUBES
DRUM
OR HEATERS
Flo; 7-11. General arrangement of waste:heat boilers. (Oil Gaa J.)
PRODUCTS
a source of free steam. Actually they require two or three times as much
surface as a regular boiler, and hence they are seldom economically
feasible.
Pressure-still Distillate. In. thermally cracking stocks froID highsulfur crude oils, the cracked distillate contains large amounts of sulfur
and no means of significantly reducing the sulfur 'c ontent except acid
treating has been devised (but catalytic hydrogenation may soon be
used). After acid treatment, the distillate is still a bright-yelJow-colored
material. . Although part of the coloring material is high boiling and may
be separated by distillation, some of it decomposes if a high temperature
is used and causes discoloration of the distillate. Gumlike materi.als are
also produced at high temperatures. These difficulties are apparently
caused by the decomposition and hydrolysis of alkyl sulfates which are
18
242
Color
5
20
22
25
18
TABLE
API .........................
Methane ....................
..
AI
.......
II
.... "
..
..
..
..
..
II>
..
..
...
Propane ......................
Butanes ......................
Pentanes .....................
Hexanes and heavier ...........
CI
14.7
30
40
165
52.6
58.2
0.02
0.24
1.63
9.39
13.
75.61
00.3
0.00
0.69
3.22
9.
12.05
74.65
61.3
0.33
3.4
8.
10.93
76.91
0.47
2.
5.67
10.31
11.
70.07
243
1 211.2"
2130
Stable Gasoline
CJ QIO
i C.. 0.10
C.32.6
l Cs fir.2
80 9
C,
0.08
C2
1.51
iCs
481
FIG. 7-12. Natural-gasoline stabilizer.
the stabilized gasoline, the feed need not be otherwise h~ated. An effective separation of propane requires the use of a large numb~r of fractionating plates (Fig. 7-12 show~ more plates than necessary) and a somewhat
high refluxratio.
The fractionation of pressure distillate is conducted in a manner similar
SI
13
244
as
Proppne
IOOORPa~
a.96%iCt.
~open~ne
o%~~~P.ll flPg
Deproponizer
,
r--~;---:-------'--r--~,
Q7%Ct.
Isobu fane IJOOB.P.11
Reflux
Reflux
raiio%IQJ
45 trays
ratio~155
50 trays
Debutonizer lsopentone tower
Butane tower
Casilu:J..head
feedilock
14500 B.P.D.
o ~oC.r
?
I
"'P'
o.2%l Cs
0.3%1. f4
Normal pen lane
0.4%C5
2400B.RD. and heavier
Normal bulane
I",,,,
0% C4 '
Bufane:fn:e
gasolme '
1600 BP.ll
6000 B.P.D. t---'
':-.--+-Nafura/j;qsoJine
3600B.P.D.
4000BP.D.
9200-B.RD.
FIG. 7-13. Fractionatjon system for separating pure hydrocarbons (see Table 7-3).
(Turner and Rubey.)
.
most of the conv~rsion processe~ it is necessary to produce pure hydrocarbons, and hence such elaborate systems as that shown in Fig. 7-13 are
widely used. 24 This pf.ant was used primarily for making an isobutanebutane feed for po1ymerization units, but during World War II all the
products became useful.. In the separation ' of pure hydrocarbons the
stabilizers or fractionators are referr(;ld to as deethanizers, debutanizers,
deisobutanizers, etc., depending upon the hydrocarbon that is being
removed.
The gas recovery and stabilization operations of a refinery may be centralized 25 into a single system, as indicated in ~ig. ,7-14. The stabilization
of cracked gasoline is' not shown because cracked and straight-run gasolines are not usually mixeq. during processing.
Reboilers .. In fractionating two-component feed stocks a part or sometimes all of the heat input is supplied at the bottom of the fractionator.
24. Turner a.nd RUbey, Light Hydrocarbons . . . , Ref. Nat. Gaso. Mfr., September,
1938, p. 423.
Iii Nelson, W. L., (HZ Ga8 J., Aug. 5, 1944, p. 75.
;
-!
!
I
245
7-3.
Col. I,
depropanizer
Col. 2J
debu- .
tanizer
10,450
O.96C.
10,160
O.DCa
..... -.
Number of trays . _.. _......... . ... - ...
45
Height, ft .......... . ...... _.......... 111
Diameter, ft ....... , .. . ........... . ...
8 ..0
Sa.fe working preSsure J psi. ..... , ..... . . 275
12.8
Reflux ratio (design figure) .............
Impurities, in bottoms, per cent ... " ... {
7-13
Col. 3,
isopentane
3 .5C 6
O.OC a
2,266
O.OnCr.
O.OC 4
0.OC 4
O.2iC 5
... . .
4-0
103
10.5
100
2.6
&
50
120
7 .0
50
15.5
Col. 4J
butanes
2,900
O.7nC 4
O.OCI
O.3iC4
O.4C 6
45
111
8;5
120
10.3
.In stich systems the part of. the column below the feed,' viz., the exhausting
sec~i6n,
~GA5
'AOM rlUD
NATII."L GA.5-
(II'"
St~A~~A$
________________________________~____~~____________________________________-4____________----~
"1[1.D GASU
,'-.-HI()
PUR""U,C.IU --------------..
.1
22
32
,"-~I"
..
.'C1l1lOC
UIk.
TO
~rJ
P'LNlT
'
I
I
I
I
!CAT ocw.wGt
~
~ ,
"~T ItXCHANCOC
ZSUMot
HC;AT IN F1a.D
M4'nJ1VoI.
(;AS,
8.
9.
10.
11.
12.
, .,
I ~'
."
......
'
247
the color must be excellent and stable with respect to light. Only
straight-run or highly treated stocks can be used for the manufacture of
solvents.
In small" re.fin~rieg in which the shipmen~s of solvents may not exceed a
tank' car per month, a common method of processing is to withdra"Y'l a
small quantity of roughly cut m~terial from the main distillation process
and rerun this cut in a shel'l still an<I tower, using a large quantity of reflux
and 'conducting the distillation very slowly.
REMNANT RETURN
GASOLINE
LIGHT
REMNANTS
SOLVENT
CHARGE
--- --,.,.
I
NAPHTHA
SPECIAL
'1:iOLVENT
I .
TOPPED
1.....-_ _ _ _- '--'"-
CRUCE
HEAvY' REMNANTS
REMNANT RE.TURN
248
solvent tower is an exhausting system for rejecting parts of tIre stock that
are too low- or too high-boiling. It may be fed -with any suitable charge
stock. Reboiler heat is supplied by circulating some of the bottoms
product through a pipestill coil so that bottom temperatures higher thari
those possible with steam or oil-heated reboilers can be attained.
Pressed Distillate and Bright Stock S~lution. The redistillation of
pressed distillate in the manufacture of neutral oils must be conducted
under vacuum or with the use of large amounts of steam. In other
respects the equipment and method of operation are similar to those used
in topping crude oil. Discoloration will result in a high treating cost, and
hence the pipestill must be built with a large amount of radiant surface
and for high oil velocities. Figure 7-16 shows a typical steam-atmospheric
pressur&-distillate
plant, ~d Fig. 7-17 the evaluation curves of the
stock.
The same equipment may be used to redistill bright stock solution, but,
of course, a different quantity of material will be processed. The unit is
operated for several weeks on one of the stock~ while the other stock is
bei,ng accumulated in storage tanks. One small Pennsylvania refiner
stored bright stock solution for a.bout 3 weeks out of a month and proc. eased it during the fourth week in the topping plant. It was reported that
only 1 hr vias required to switch from the crude oil charging stock to bright
stock solution as the charging stock.
Bright stock solution, like pressed distillate,- must be distilled with as
little discoloration as possible. Several twO-flash systems have been
built. In the .first flash, the na.phtha is removed. The residue is then
further heated in a part of the pipestill, and gas oil and a neutral oil are
vaporized inthe second flaSh. . The two-flash system holds no important
advantages over the single-flash system, but as an illustration the twoflash method of operation is shown in Fig. 7-18. Evaluation curves are
shown in Fig. 7-19-~ The steam required in a pipes till rerun system is
often less. than one-fifth the amount required by shellstill redistillation.
Modern practice is tending toward single- rather than two-flash systems.
Reducing Operations. Reducing IS, a term used to describe those distillation operations by which a topped crude oil is further distilled to leave
behind a very high-boiling residue or to produce additional distilled
products.
_
Steam reduction involves heating to 550 to 660F in the presence of
large amounts of steam. In early refinery practice cylinder stock was
exposed to steam in shellstills for many hours. Modern pr~ctice simply
involves the use of steam in large amounts in a. continuous distillation
system. The effect of steam in reducing the boiling point is discussed in
connection with Eq. -(15-8) and Example 15-2.
D~TUCtivc distillation involves hea.ting to 650 to 75QoF with or without
!
j
I
I
iI
rerun
I
)
,
':
249
er
Pre.s5u res
~ Te~peratures
viscous neulrqJ
. 59%
32 A.P.L .
140 vi5(.tilIOO
-410 deg.llash
FIG. 7-16. Diagram of B. steam-atmospheric pressed-distillate rerun plant. (A stripper
.is usually employed for the side--draw produet.) (Smith Engineering Co.)
I
.!
I ~
900
\6Tavify
~800
~
..s::
700
v'
... / V
Q) .
~
t!l
Q)
0.
Q) 600
'-
+-
,I.
Q.l
0-
E 500
~
4000
V"
k::/Qsh
l~
&
10
V-
""
!'..
"""'-..
ViscositY. /
./
1\
U}
T. p. 8. diSfiJklliou'
20
>
37
36
~5
I~A
'/
.
~ -~
r---.....
"-..
172
<i
:-
i'.. ..
40
50
60
Percentage
70
BO
90
ts
.p
100 .iii
o
u
III
31
.... 0
30
-I-
100
5
50
250
190fb.
1G.!b.
\
-"'---
~~p~,,--
NaehthOf
7&6 %
--~=
.:.
1st f.lash
95
6as oil
0.4%
180"
~-----?r--------.~1_r
J6Ib.,670r' ~~
2d flClsn
38lb.0
1
500 3.000 I
....-----t+---;.
lh/hr. ,j
-1287 ~ .
260~
, .~.
---
---
:::
Si'etm ~~
900
~e
600
..c
J! Q700
,I
/
CD
"
"-
0600
~o
00
~@500
-+-~
~._ 400
E 0
~ ~300
u-
~~200
~~
Ii....
I.
.....
100
-~
[....../
~o
Lr;sc.tmJOO~
J
-.........
N
1
/\
.-= :>
............. G'
Q.II)
a.
If)
"v: -C
1\
","1
~o
ro ~ ~ ~ ~
60
leo
.... '
40
0.:
,
30
' 2.0
~ ~
Percentage
FIG. 7-19. Evaluation curves of & bright-stoek solution.
Armistea.d, G., Jr., The Coking of Hydrocarbon Oils, Oil Gas J., Mar. 16, 1946,
,
p.103.
'251
Fresh teed
-,..,.;... ~
-,
-,f..*/
... 1
~,-,-
.;~.~.
,
,.
t..... ''''''_'~_'I
_J
.
Fr~sh feed
Recirculofion
Products
t-------+--.\
r---------------------------------~2
~---------------+J
Feed
Pipestill
Products
Tower
Ex.chO"gers
FIG. 7-20. The Carrier distilla.tion process.
Based OIl
pipes till
cha.rge
25
45
70.5
84.0
94.0
Based on
feed stock
25
45
56
68
83.0
252
Although the extra vaporization permi tted by the carrier process is attractive, the pumping, heatiDg, fractionating, and condensing of large
amounts of recirculated material are expensive, and the plant equipments
mU'st be large.
.>An outstanding application of the Carrier principle is the reduction
system used ih Thermofor or Houdriflow 'catalytic cracking. In these
900
ru
800
::J
./
."
II')
r!
n..
700
CI
,.....
U)
u.:
tf\
Q)
o
..
600
/ l ./
~"
1'/
'// V
/,
/
ft) ~
~
I
300
I...-- ~
I-""'"
'2
~
~'/
V. i' "/ /
I.
V
V
V Vi
)
.,.
~~
V.
'
V
"
..
.
'2.0
30
processes (Fig. 21-7) topped crude oil is heated along with cycle stock to
7'90 to 860F and released in a vaporizer or tar separator. The somewhat
low-boiling cycle stock, when used in ratios larger than 1: 1, is so effective
in removing gas oil from the topped crude oil that further reduction by
means of vacuum distillation is ofte~ unnecessary. The vaporized
.catalytic 'feed and cycle stock -is then fed directly to the catalytic plant
reactor as a vapor.
Vacuum Producing .Systems. The common method in the petroleum
industry of maintaining a vacuum is the use of a barometric condenser
253
waler
,
I
Incoming.
nOl1condensobles
and process
steam
2d
stage
I
I
To atmosphere
tir 10 a
condeneT lor
Baromelric
leg
jet s7eom
...t
254
Jet steam
Condenser water
t---------------,,
,
0'
I
I
--j
I
t
Booster ejeclor
13d
go~~
L._
1\
'r'
I
I
I
I
J
J
I
Incominq
noncondensobJes
and process steam
To almosphere
or a condenser
or 10 olner
noncandensinq
sloqes
Barometric
/0 7
FIa. 7-23. Booster ejector, barometric condenSer. and two or more ejector stages for
low-vacuum systems.
1,
I
10
20.30
4O.!!oO
eo 100
200
300 400
(s~
:t
;~
255
7:-4.
760
200
100
60
50
'40
35
30
25
..
j
--------------
Temp at vaporizer, if no
950 830 780 750 735 725 715 708 700
process steam is used, "F.
Process steam,4 Ib, for;
Vaporizer at 720"F .. ' . . , 10,300 2,490 1,070 460 325 190 122, 54
Vaporizer at 6,80 OF . . ..... 24,000 6,220 3,020 1,800 1,340 1,040 885 733 580
Jet steam, Ib, for:
150 232 378 492 830 1,600
80F cooling water ...... .......
70F cooling water ...... . ...... 146 222 312 368 480 600 857 2,01 o
Total steam required, Ib:
680F-800]' water ...... 24,000 6',370 3,252 2,178 V,832 1,870 2,485
6807-70F water . . .... 24,000,6,366 3,342 2,112 1,708 1,520 1,485 1,590 2,590
720 F-80" water ....... 10,3002,640 1,302 838 817 1,020 1,722
720F-70"F water . .. . .. 10) 300 2 J 636 1,292 772 693 670 722 911 2 ', 010
D
In addition, 1l. pressure drop of about 10 mm to the vaporizer for the lower pressurcs, and a larger pressure. drop at higher pressures .
Q
.\
TABLE
...
f.
t
,
J
7-5.
OF
55
mm
11
60
65
13
15.7
18 .8
22.2
70
75
OF
mm
80
85
26.1
90
95
100
30.8
36
49
56.7
256
TABLE
7-6.
Pressure,
mm
System
100
Lb steam per lb
of total mixture
lJ
41
Noncondensab~es
200
100
70
50
40
30
20
10
7
2-stage
2-stage
2-stage
2-stage
2-stage
2-stage
3-stage
3-stage
3-stage
5
4
3-stage
3-stage
4.3 (2.5--11)
6.0 (3--17)
7.0 (4-23)
8.2 (4.5-27)
9.0 (5-30)
10.2 (6-35)
12.3 (7-40)
16.8 (10-50)
20.0 (l2-58)
23 .0 (14-64)
25.5 (16-70)
are very low ones that can be attained only under the most favorable
conditions.
E%ample 7-2. Water Vapor Assoc~ted with Noncondensable Gases. A vacuum
system with outgoing cooling water a.t 82F is to remove 30 pounds per hour of noncondensables at a pressure of 45 mm.
Some of the water is at 85F before it becomes fully mixed with the rest of the water
(8. 5F difference rather than 3F is sometimes allowed) and this water exerts a. vapor
pressure of 30.8 mm (Table 7-5). Accordingly, the partial pressure of the water
vapor in the gas phase is 30.8 mm and the test of the pressure, i.e., 45 - 30.8 or 14.2
m~; represents the 'oil vapor. The pounds of water vapor associated with the noncondi;msables (use 60 molecular weight as illustration) is:
.
30.8 X 18 X
14.2
60
:-
PSIG STEAM
30 = 1961b
.
Thus, the total gases to be handled by the ejectors will be 30 + 19.6 = 49.6 lb.
At a. pressure of 32 rather than 45 mm, the total gases rises to 261lb and at 30.8 mm
or lower, an infinite a.mount of water vapor must be handled, and a. booster ejector
must be employed to ralse the pressure to higher than 30.8 mm.
r
I
\
,
! -
'.
;
,t
,
.,
,
,!
257
258
,0
O
Crude oJI
Temperature
'QlJcmtity
D Pre5sur~
Holtrvdelo
shell stills
FIG. 7-25. Vacuum distilla.tion p1a.nt using a booster ejector.
~- lank
I--O+---!Surg{'
::1\'00
N
~ 1000
o
o
-
~y
900
~800
",",of'
.~ cJ. '
';tj
~ 700
:>
cd 600
./
\)9
1/
,--
40
A . . l 6ro".Iitl/
r--
~ -.......
30~
.~
_Vi5~V~
1
\0 , 20
.30
40
50
60
70
20j)'
~
'
80
, i
\oQ'/ ~\.~/ 0
"
::-
qO
"
--
I 0~
tOO
Percentotge Distilfeol
FrG. 7-26. 'Evaluation curves of the reduced crude oil charged ,to the plant shown in
Fig., 7-25,
f
259
slots of the caps as po~sible, and sometimes the customary bubble caps
are discarded entirely for baffle or sphish types bf plates. In some installations the vapor line has been eliminated by doing .the condensing in the
top of t?-e tower. In this arrangement the barometric and-jet equipment
is situated along the side of the vacuum tower (Fig. 7-27). The processing of a reduced crude oil in a vacuum unit for the production of distilled
cylinder stock is illustrated in Figs. 7-25 and 7-26: In this plant a reflux
condenser is placed in the top of the tower arid the partial condensers for
gas oil and 'wax distillate are outside the tower but not at a great distance~
One of the difficulties with the arrangement shown in Fig. 7-25 is the
weight of the large condensers. They are so heavy for a large installation
that they cannot be supported by the .tower. This necessitates independent structural supports and an elaborate expansion'joint between the
tower and condensers. Vacuum steam strippers are sometimes used on
.vacuUm systems.
Although fractionation is more effective at low temperatures. or in
vacuum than at high temperatures (Table 7-7), this behavior is not usually
TABLE
7-7.
Low
PRESSURE
+50~
700F
600F
800F
.
52.5
4,395
350
. .......
..........
12.5
.
110
22
5.0
.425
1,450
115
465
3.7
..
3.12
260
Condens~'s and
e~ch0hge,s
28mm
Walei' .....-+-t_....I
~sump
Cold circuil 10
1051 traces
, Bubble plole
cond~nse
Mesh blankel
Troy-no copS
lor a balHe)
}---l.--~
Ugh! g05017
3%
J-r--~
30mm
700790 DF
Colalytit:
chDf'ge stock
75%
Wush oil
.. -- ---,.----------..,
I
I
J,. , cliculalions
Allemole
~
..;..
I
I
'--flf---.L---'V\f\/V\J\A,---"--.,.-----...
Cooler
FIG.
IOOpene.
osp!JaH
22%
entrainment ma.y discolor the products and increase treating costs, a.nd poorly frac
tionated' wax distilla.te or cylinder st<?ck may result in trouble with dewaxing.
Some asphalt or feed -preparation towers employ only one or two bubble plates in
addition to a mist separator (Fig. 7-27)., More detail on vacuum-tower construction is presented in Chap. 16.
'
2. Higher va.porizer temperatures can be maintained. Whereas vaporizer tempe~
tures in lube towers are usua.lly limited .to a maximum of about 710F, the vapor
izer temperature in asphalt towers sometimes exceeds 780F. However, vacuurri.
decomposition, which causes violent foaming, begins to occur at about 800F, and
at such 8. temperature the material in the bottom of the tower must be removed
quickly. Means-of ra.pid cooling by recirculation have been employed.
3. Only one product need -be taken oV,erhead. This elimina.tes the extra pla.tes that
are required for a side-draw -cut or the partial condensers for two overhead ,cuts
4
261
(Fig. 7-27). If two overhead cuts are taken, the separation is not difficult becau..,e
both cuts are gas oils and they need not be well fractionated.
4. Tar stocks are usua.lly available at a high temper-a.ture. A small heater is usually
required, but in some cases a sufficient amount of vaporization: occurs by simply
red~cing the pressure without the "addition of he~t.
BLOWING
TOWER
BLOWER
OR "
COMPRESSOR
AIR
CONTACT
CONOENSR
BLANKET STEAM
"\
ll!sEWER
fLUX
STORAGE
PIPE STILL
'"
..
t
ASPHALT TO"
CARS, DRUMS, "
OR
A
point (see Fig. 4-53), and th~e are obtained"by air blowing. Even higher
ratios of penetra"tion to softerung point are obtained by"the use of catalysts
such as ferric chloride or phosphorus pentoxide. u Batch systems "(Fig.
7-28) are most widely employed. Heavy topped crude oil or vacuumreduced residue is heated to within 50F of its flash point and blown with
30 to 50 cu ft p.er minute of -air for each ton of asphalt. 3-4 One "and onehalf to twenty-four hours of b1owing, depending the amount of mechanical agitation and catalysts used, is required to"cause hardening. Fumes
can be burned or they can be scrubbed with water to remove obnoxious
gases or odors and to recover small amounts of oiL
on
1'1
262
7-8.
Distance, ft'b
unit.
'
CHAPTER
Many auxiliary operations were. neglected in Chap. 7, and space is available here for discussions of only instrument control, crude oil desalting, waste-water disposal, water cooling, storage tanks and blowdown
systems. Refinery practice in the operation of boiler plants, generators,
water treating, and pumping does not differ greatly from other standard
practice.
Instrument Control. The full usefulneSs of refinery equipment can be
attained only by the use of automatic control instruments, and the use of
instruments has contributed much to the productivity of refinery workDlen (see Table 23-1). The handling of 10,000 bpd of capacity required
262 men during 1925 and 158 men in 1956. An attempt to discuss the
merits of each individual instrument or type of instrument' would be
unsatisfactory because there are several different types of satisfactory
instruments for each purpose and because significant improvements are
being made each year.,
Figure 8-1 indicates the location of the various control instruments
that may be used in a topping plant. Among th,e most important are
(1) top temperature controller; (2) recording pyrometer at vaporizer
and at inlet and outlet of pipestill; (3) pressure at inl~t and outlet of
pipestill, at charge pump, and in tower; (4) rate of flow of crude oil; and
(5) level controls at bottom of tower and the side-draw plates. Control
instruments are extensively used in natural gasoline plants (Fig. 8-2) . .
Finally, Figs. 12-6 and 12-7 on dewaxing, and Fig. 20-11 on alkylation,
show instrumentation.
In the .control of a continuously operating system, certain variables
must be fixed or the control of others is almost impossible. Of prime
importance are (1) the rate of feed, (2) the temperatur~ ,of feed, and (3)
the t<;>p temperatures of the'towers. With these variables fixed, the controlof the others is well ~thin the capability of a competent operator.
Even an expert operator is almost helpless if these three variables are not
fixed. ~ plant can be operated with these controls alone, but the operation will be much more efficient if other controls are utilized. The rate
of feed may be controlled by manual operation with the help. of stroke
263
TOWER,-
Stack
FURNACE
N
M
--_ ..
..,
I I
[ I J
_ ,.
..
HorO
I Ll_l
"
j I
L-D7~"9:
-J
Fueloil . ." : :
Sfeam-.. _ .. _ .. i - .. -L .. _
.
i .J Products
I
K
:
1,
Wafer
_______
JI
.. _-r-
FIG. 8-1. Instruments that may be used in a. topping plant. The letters refer to the
following instrument.s: A, tempera.ture-recorder controller; B, recording pyrometer;
0, recording pressure gauge; D, indiea.ting pressure gauge; E, rate-of-flow controller;
F, pressure regulatOr; 0, draft gauge; H, hand-control'valve; I, safety valve; M,
liquid-level control.
Optional instruments: J, industnal thermometers or thermocouple wells; K, flow
meterj'L, stroke regulator and counter; N, indica.t.ing thermocouples or connections
for them; 0, bypass adjustment valves or proportional draw-off devices.
Tempt!rulure
recorder
conlrol
Tempen:/llI~
Temperatun
~
recorder ~~N
W
recorder
centrol,.
~...........l....l
Kaw .
gas
!?alio
control---
......c~~!::::lP
leon oil
t t
st~~_ .....L .. L- __ Sfeqm
"-Reflvx
.~...L:.._
____ S!e.qm.
___ __
265
regulators and stroke cOUnte~J but How regulators or indicators are now
widely used. The effect of a variable feed.rate can be minimized by the
use of proportional draw-off weirs. l The. temperature of the feed
normally gives little trouble, and several types of satiSfactory top temperature controllers for towers are available.
The principle of trend analyzing has ,been one of the notable improvements in instrument design. A trend-analyzing instrument will begin
to stop the actuatirig mechanism before the condition (temperature,
pre~sure, or rate of flow) has been brought back to the desired condition.
, In this way the tendency to overco~trol, o~ "hunt," has been corrected.
Such instrum~ntB apply a large correction if the condition is far from the
control point and a. small correction (or non~ at all) if the condition is
.
_
. nearly at the control point.
A central control room has become an integral- part of .all modem
petroleum units. The gro'Qping 'of recording and controlling instruments
facilitates the work of the operator and concentrates responsibility for
the operation of the plailt~, Although the first cost is high, it' ~duces the
number of operators required to man the plant and provides an appreciable saving in operating cost. In dealing with emergency shutdowns,
such as th'ose 'arising fro~ explosions and fires, the facility afforded by
centralized control is vital.
On the other" hand, control instruments and the lines between the control room and the equipment are costly. For this reason the less ,important measurements should be ~aken at the equipment, and indicating
instnunents should be given preference over recording instrunlents ."
except where a record of the operating conditions is of definite serVice~
A large number of instruments divides .the attention of the operator~ a.nd
hence careful thought should be given to th~ selection of- truly useful
operating data. Figure 8-3 shows the instrument room and boards of a
-catalytic cracking unit.
Des41ting of Crude Oil. The small,amo~nt of brine that is associated
with crude oil is far more important than its quantity would indicate. In
addition to the mechanical accumulation of debris in the processing
equipment, the chloride salts (particularly magnesium chloride) liberate
hydrochloric acid that causes corrosion during processing. This causes
a decrease in heat-transfer r~tes by fouling and promotes the formation
of 'coke in the pipestill tubes. The removal of the brine often results in
increasing the length of the operating cycle tenfold or more. Even a few
parts per billion of arsenic will quickly poison platinum ca.talysts.
Brine is associated with :crude oil both as a fine suspension of droplets
and as more permanent emulsions. The demarcation line between these
two types is not always clear; but the less stable mixtures can be separated
"
"
266
by simple settling methods, and the more permanent mixtures must 'be
:handled, by chemic81 or electrical methods of separation. Long standing'
in storage tanks results in some settling-in one instance the salt content
was decreased from 25 to 18.5 g per gal by standing for 4 days. A high
temperature is also useful, and the most common settling system consists simply of a horizontal tank operating at 200 to 300 D F (an oil visQosity
of 2 centipoises) and at sufficient pressure to suppress violent vaporization
(50 to 250 psi). The coalescence of particles is hastened also by the use
So
(Minne-
of towers packed with sand (or gravel) or excelsior, 2 either before or after 3
the settling vessel. The time of settling may be ~ut in half by the use of a
packed column of excelsior. 2 The use-of Fiberglas has been thoroughly
studied by Burtis. and Kirkbride," and reduction of salt content to 5Ib per
1,000 bbl appears possible. Packiogs greatly assist settling, but they
become plugged th debris and must
replaced. Water is usually
w:i
'be
Hawthorne and Bedell, The Removal of Inorganjc Salts' from Crude Petroleum,
API, 8th Midyear Meeting, Wichita., Kans., Ma.y 24, 1938.
3 Blair, C. M., Jr., Removal of Inorganio Salts from Petrol~um, Oil Gas J., Apr. 4,
1940, p. 52.
Desalting of Petroleum with Fiberglas Pa.cking, TraM. A.I.Ch.E., XLII, 413
(1946).
2
267
ID:ixed with the incoming crude oil to produce a brine containing 2,to 5Ib
of salt per'bbL Union of the water with brine droplets is reported to be
75 per' cent or more complete, Ii and hence the brine droplets that remain
in the crude oil after settling contain little salt. The pressure drop
through the water mixers ranges from 12 to 40 psi.
, Settling times of 1 hI are common, but 2 hr is sometimes employed.
Caustic soda is often added' in amounts large enough'to produce a pH of
8 to 9 in the brine. The oil is passed upward through a 10- to 25-ft bath
PESALTED
CRUDE OIL
CHEMICAL AGENT
15-20 FT.
'lOPPING PLANT
EXCHANGE~
SETTLER
, SYSTE~
-.
TO
'----.......... BRINE
SEWER
.QB ELECTRICAL
SYSTEM
EXHAUST STEAM
~J:ATER OR COILS,
BRINE
19
SEWER
268
ENGINEERING
PETROLEUM
potential ~]ectric field (16,500 to 33,000 volts) across the settling vessel to
cause more rapid coalescence of droplets. By these methods the salt content
usually be reduced by 90 per cent o~ more, and the time of
settling may be reduced in Borne instances to only 20 mm. Among the
ingredients' of treating compounds are the following:
can
cent
Modified tatty acids partly or wholly saponified with ammoWs. .. ',',' 35-48
Oil-ooluble sodium petroleum sulfonate ......................... :'. 13--31
Wa.ter-soluble solvents, dilute alcohol (10-14 per cent), ete ........ 10-20
Oil-aoluble
oil, naphthas, cresol. etc: . . . . .. 4-25
Inorganic sulfates. sodium sulfate, sodium sulfite ... , ........... :. 1-2
Few directions c~n be given for the selection of tt~ating agents, 'but
general, for alkaline brines. of hlgh pH value the neutral soaps' of oleic
'aCid; solid' fatty acids, liquid-saturated fatty acids, linoleic acid, 'etc.,
should be used; for aJkaline brines of lower pH ordinary turkey-red oil,
with the sulfona.te group esterified and loosely linked, may be successful;
and finally, for more acid brines "one should consider the'soaps of naphthenic acids; preferably having a low sulfate content, and the more stable
fatty acid, aleoholic, or aromatic sulfonates, having a higher sulfate content, provided these are ad2ipted to the pH of the water~ and do not contain: antagonistic constituents" (ones that cause pr~cipitation)
The
use of small amounts of very dilute caustic soda (3 per cent of a 0.3 per
cent solution) Qr phenol-saturate~ spent caustic solution is found to be
,
'
" , ,_
' ,I ~,;;
, beneficial in some instances.
Waste:"water Disposal
pollution of streams
harbors by was,te,
water from refineries is a problem that must be met by all refiners.lO~ll
Simple gravity~type settlers are widely used. These iunction accordi!tg
to the basic law of Stokes which for spheric~l particles is
1)
(g.:.} )
269
1\
:
.
\ Oil refainer oarlJe---.
(PQlh
\,
or fluid flow
,.- Liquid level
I
I
I
I
I
\
Oullef_ ..
.
----Slurry co/leeling chamber
1
r:/oc/fwise)
",
S ~cond stage
First stage
FlO. 8-5. Vertical section of a waste-water .separator.
270
one of these emulsions will have a specific gravity that is the same as that
of water, and it will not ,settle. All these special cases should be met by
corrections in the general processing scheme of the refinery rather than in
the waste separator. BurroughsI' recommends methods of disposing of
emulsions from traps, separators, yard tanks, and treating plants, and
the disposal of tank bottoms, spent caustic solutions, and obnoxious gases.
Water is becoming so valuable that it, too, is being recovered for reuse. l6
I
I~
firesleam
175Ft
Blowdown
FumClces
Towers ,
o
~1Q--~-+--------------~-------,
ReHef valves
Jt
AIm
~sieam
Fire
wafer
Liquid filled
vessels
Towers end
'd rums
".----'
Slowdown,
stack- '
of hot oiL
(Pet. Refiner.) ,
loS
271
TABLE
IN SMALL
TANKS
. Temperature,
"F
20 .... , .......
40 ............
100 ......... . ..
Standing loss,
% per year
1.65
2.5
5.0
6.8
9.6
14.5
25.0
Working 108s,
% per filling
0.09
0.14
0.20
0.25
0.30
0.35
0.41
Nelson, W. L., Natumi Gas to Move by Barge, Oil GaB J., Mar. 22, 1954.
Instructions for Measuring, Sampling a.nd Testing Petroleum Shipments, Standard Inspection Laboratory, Standard Oil Development Co-., New York.
U Nelson, W. L., Oil Gat J., Sept. 23, 1944, p. 203.
1'1
18
.'
zoo
-""
100
ell 80
. Q..
cd
...J
,I
6~
.
~
._
a:
CL.
a::
Q.
W
I-
:>
...J
o
V)
en
<
,..
,..
,....
c;,;,
p..~~
............. "...,.
--
i,...--'"
.,."."
~I...,.
~.~~i--' ""'" ~~
e
6
~...
..
......
,....
,. ~ V l '
. / ....\
........ ""........
~/""'V
P-: \
....
-"'"
.,..
V
V
Vv
.......
.... ~
".......... "
"""
............
.....
ZO
030
. /io""
v\,~..........
.. .
vrr,..~
.p'
...........
..,~
.....
!)O
-'
/?[;:""
V~v~.,
"
V " , , - ~~f"""~
-"'" .............
..... I""'.,..
~.L'''''
'L
lo""".......
v:.,......./..V
I""
."V'
V'
70
--I-.+
,n
.. ,
CI)
\.
0l&J
~X
~
90
BALLOON OR HOLD~A
FOR VAPORS
F L.OATlHG, PISTON
OR EXPANSION
ROOF
VENTED OR
FIXED ROOF
~ STORAGE
100 UO 'ZO 130 1040 ISO 160 170 leo 190 ZOO
SMALL
SPHERES
56
AND
46 HORIZONTAL.
36 CYLINDRICAL
~6
TANKS
IJ SPHERICAL
II SHAPES AND
6 VERTICAL CYL.
TANKS WITH
DOM! ENDS
C)
. .
ao
'
....... /~
.......
.. r
.
60
-'
.D~
D-,
136 SMALL KORlZ.
III CYL. TANKS
100
..,
...
..
40
7'
I""
~~Vc:,O~~V~
I~~~
10
/ 1 ....... ~~0;;
.,........
3V~~~~~~l/
z./~~~~//
~~~~v .
.
o
....r': $~-'t"l-
............::~-""~
.-
~io""
:;,
~,
~~
::t PR~~S.AND~YUN
L.,..oo"
~ .... I..... """" 6&
,....
kilo..\..
236
j,..
6/~~ . . ,.. /~ . .V
"'"
IF.....
~.:.......
..
~~,;
...,.,.I ..........,.....~
\~~ ........
\'2.~O~~~VVP
.........I,... .,r- 0"
........ .....-..........
Z" v...... ..... .,
/~ ~
~S
~ ~ ~~r- ~ ,f> :;;;;V .,,"
-
,,~
.....................
....,.......
V
.........
. . . -.. . . . .
--,.............. / V V / ................ V V V
7". . . . . ~ /~. . . . . . . . . ~~/~~~~V. . . . v"..v
~......,
.,.....
1.0>
".......c,.......-:~/ ~~,.,,.,
./ .-- ..... ~
.....
.....
"""
___ . ~,~
...... ""-~~ , 1,..00
IO~"
"..
.....
./"'l/"'"'~ . /. ~,.,
2!)~O~ ~ .:..'0,....7
BU,T ANto
... - -
.. ~
"\.
BUTADIENE,
"~V~%V ~"':;!::,",...
,,"'\ ""'.- -"""p...... p '..... rf "'!~~ I ' .. "
_~ -
'" '\
ISO
ffi
ISOSUTAN!,
PROPANE,
z~O
8-7. Type 9f stora.ge ta.nk as a. function of va.por pressure of the stored liquid.
273
o
10
59
67
90
Approx. relative
breathing loSs
1.25
1.25
1.00
0.80
0.75
Losses are also smaller in large tanks 21 being about 80 per cent as large
in a 60~OOO-bbl tank as in ~ 5,OOO-bbl tank, and only 50 per cent in a
FIG. 8-8. Spherical storage tn.nkS-2,500 and 1,500 bbl. (Photographer E. M. Payne,'
HoU8Wn, Texas, and Chicago Bridge and hon Company.)
274
T,uu.JD
12
10
8
6
4:
2
OJ
6.0
4.8
8.6
4.1
67
33
19
1:J
1.6
0.9
0.611
1.Smm4
0.5 mm a
..
..
..
125
100
76
98
8.2
..
True at 60F
Loss relative to
loss of 10 R.v.p.
0.6
. 0.2
manifolding several tanks ~ one floating roof tank) are much smaller,
and the use of a blanket of tiny plastic balloons is -said to decrease losses
by 40 to 90 per cent. U
a50
.().$5
1.75
.. a60
~u
a70
1,5
0.80
~1.25
~ 0.65
,G
~a90
~
~
0
I..
1.1
1.2
.~
1.0
d!
.1.4
1.6
12
74
76
78
80
82
84
275
but it usually ranges from 2 Btu per sq ft per hr per deg difference in air
and water temperatures in winter, to about 4 Btu during the summer. 27
More detai~ is given by Langhaar. 28 If the warm water is sprayed
through nozzles at a pressure of 7 to 10 pounds, a much smaller. area of
pQnd may be used. Each square foot of surface can handle 150 to 250
pounds of water per hr. The temperature attained in the pond when the
hot water is at 110F is usually within 10 to 20F of the wet-bulb temperature. Even better control of losses apd contamination is possible
with atmospheric or induced-draft cooling towers. The approximate
relative cap~cities of induced-draft or atmospheric towers are indicated
in Fig. 8-9, and the reciprocals of the same factors may be considered as
the relative costs of such towers. Thus, a tow~r operating at a 6F
approach to a wet-bulb temperature of 65F (cooling to 71F) will handle only 57 per cent as much as when it operates for 75.6F water (an
approach <;>f 10.6F). Note also that the capacity is about 33 per cent
more if an outgoing water temperature of 79F is adequate.
Figure 8-9 can only be an approximation becauseit neglects the sensible
heat introduced by the dry-bulb temperature and by the inlet water
temperature. However, it (Fig. 8-9) was based on a water-cooling range
of about 2OF, and the effect of & cooling range of 30F is to increase the
capacity by about 17 per cent whereas a cooling range of only 15F
decreases the capacity by about 15 per cent.
The amount of evaporation loss ranges from.O.B5 to 1.25 per' cent of the
circulation over the tower for each lOF of temperature drop through the
tower. Windage loss for induced-draft towers usually ranges from 0.1 to
0.3 per cent of the circulation but may be 0.8 to 1.3 per cent for atJpospheric-type towers. The make-up water continually brings salts or
solids in to the system, and although the windage loss removes salt; an
equilibrium in salt concentration is established which eventually 'require3
that water be discarded from the system.
%7
CHAPTER
pp.
Nelson} W.
SU]fUf Crudes, Oil Gas J.,
Cost of
p.150.
1 Nelson, W.
Oil Gas J., Aug. 1, 1955, p. 117.
W.
Oil Gas J., Creep Strengths of
Mar. 30, 1953, p.
Apr.
1953, p. 291; Applications
"....u """'" Steel, Aug. 17, 1953, p. 156;
Low Temperatures, Apr.
. Where to Use Aluminum Alloys,
3D, 1954, p. 103; Application of
Alloys . . . ,Sept. 27, 1954, through
18, 1955; and Alphabetical List
. . . , Sept. 14, 1953, through
1
1954.
277
9-1.
1956 a
All
High
sulfur
alone
cor-
rosion
High
sulfur
with
sourness
7.6
2.0
1.6
12.3
0.3
10. I
5.3
1.1
1.0
6.9
1.4
1.3
2.3
2.0
0.4
2.6
0.5
2.9
3.8
12.7
16.5
0.2
12.1
0.61
Nil
1 '6
0:8
0.3
0.5
0.1
17.9
f
I
All costs converted to 1956 by Nelson Refinery Construction Cost Index, Oil
Gcu J., July 27, 1952, p. 105. The Index is published in the first issue each month of
the Oil and Gas Journal. '
.
~ What Does Corrosion Cost You, Pet. PTocessing, November, 1953, p. 1625.
'Guthrie, V. B., Pel. Processing, Ma.Y, 1954, p. 708. Estimate of total was 19.4
cents per bbl.
<I
'
278
9-2
TABLE
Max temp,
Pipestill tubes
or hangers
or
450- 550
450- 800
700- 950
None
1
5-13 linings
13-184 linings
184 -27'" linings
900-1,000
1,000-1,300
1,300-1,600
1,750
....
"
.......
'*
"
to
"
~.III
...
..............
<II
Expensive
equipment
1-3
5
7-12
12-16'"
2-9
12-27'"
251'1-27G
181.\-27
18(1-274
20
.........."........ 9-3.
ExTBA.
less active
this temperature.
Number
of
times
cost
1.3
1.5
2.0
3.0
4.0
6.0
8.0
10.0
12.0
.0
16.0
18.0
20.0
.0
Number
Strength
alonea.
Sulfide
Oxidation
corrosion
aloneb
alone'"
1.5
1.6"
1.5
1.14:
1.6
2.7
1.8
2.0
2.6
4.9
9.4
1.~
1.5
6.8
9.7
18.4
13.7
18.1
22.7
.0
74.0
100.0
17jl
High
23.0
. . .. .
:it
4.5
..
L3c
1.5
2.0
2.8
3.2
4.4
6.8
7.4
9.5
11.8
.3
16.8
19.4
23.0
by
Using twice
strength of carbon steel
Oxidation
1.38
1.5
1.87
3.7
7.05
14.1
22.0
30.6
40.5
High
Sulfide
1.62
1.87
2.5
3.8
4.6
6.6
9.3
12.5
16.9
22.0
27.2
32.2
1.15
1.6~
2.19
3.8
5.8
10.3
15.6
.2
28.6
55
High
High
cause little trouble by sulfide corrosion have been reported, but others
containing less than 0.7 per cent have destroyed distillation equipment in
less .than 6 ~onths. As a further example, the su.J.fur content of gasoline
marketed in the United States has been limited .to less. than 0.1 per cent,
but at one time fuels were
marketed
jn Germany that contained as much
.
.
as 1.5 per -cent sulfur and no serious engine corrosion has been reported.
. Chromium steel is the standard material for withstanding sulfide corro-sion. Resistance becomes noticeable at about 1 per cent chromium; but
in most instances the use of more than 13 per cent is not justified. The
high-chromium (13 per cent up) steels tend to lose ductility, particularly
if used at high temperatures, and hence nickel is employed with the
chromium
assist in avoiding ]os.s of ductility.
The additional cost of high-tempetatUI'e or resistant a lloy steels as
compared with carbon steel must be justified qy such factors as (1) oxidation resistance, (2) strength at elevated temperatures, (3) .sulfide resistance, (4) great cost of replacing complicated equipment, (5) ~aintenance
.labor and warehouse inventory~ and .(6) avoidance of shutdowns. The
. app~oximate relationship between some of these variables is indicated in
Table 9-.3 for the tubes and tube hangers used in refinery p,ipestills, a and
the general relationship is u.ndoubtedly valid for many other applications..
It is clearly evident that the extra cost of-alloy" steels cannot be justified
by 'consideration of str~ngth alone or sulfide resistance alo~e. Th.e
increase in cost is nearly always greater than the increase in strength.
or the increase in sulfide resistance. Oxidation helps to justify the use of
alloy steels, and strength indirectly alters the situation because moremetal thickness becomes available -ror destruction by corrosion if the
alloy steel has a high strength. Thus, a I-in. thick carbon-steel tube,
which mUst be only ~ in. thick for strength, .provides only a ~-in. thickness for corrosion whereas a I-in. thick 2 per cent chromium steel of
50 per cent greater strength provides % in. of material which can be
destroyed by corrosion before the tube must b~ retired from ~ervice.
Neutralizing chemicals, particularly lime, are widely used to combat
sulfide corrosion. The effect of ammonia is not entirely known,7 but
caustic soda causes troublesome scaling or clogging of tubes and evaporator surfaces.
Processing Sour Crudes. Points of corrosive attack are marked on the
Bow diagramS of Fig. 9-1 by letters, and the letters are used as paragraph
headings in the following discussion.
A. Poi8on Hazard. Hydrogen sulfide is one of the most poisonous
gases. Percentages of 0.1 per cent in air are fatal in les~ than 30 min, and
to
280
C"'~G"s
A
,.,~
.~
oz,p
I\~
IO~P
-.(
,.....__ ~. . . r\
I
STABlllZATIO
t
I
FAG
I
,
/v1
L,'
I.
I
--Kero.
Ipress.
0';.slillo';8
g
...
REDUCING . L _
C I
s'll naphfha
~/
'Soil for or
aspholf
Topped crude
, -
Reslduum
HoI- crude
FIo. 0-1. Corrosion of equipment when handling sour crude oils.
letters.
REFINERY ENGINEERING
uum
; to 9
18 per cent chromium for the line from the reaction
chamber to the flash chamber.
J. Still-tubes and transfer-line materials are indicated
Table 9-2.
K. Crude towers suffer little loss except below the
tray when the
feed is at 600 to 700F (use 12 per cent chromium lining), and on the top
tray if ammonia and desalting are unsuccessful (use Monel-metal liner).
Cracking towers and chambers are lost 6 to 12 months unless lined
,with 12 per cent chromium (aleo trays
caps), but one .refiner finds
cent liners on inlet nozzles or openings all that is required.
5 to 12
Gunite used successfully for some soakers) reaction chambers, and flash
chambers.
M. Pumps for topping may require no special materials,
12 per cent chromium and 18-8 chromium-nickel liners, rods, valves, and
are sometimes used. Centrifugal pumps may require
per cent
impeller wear
and
sleeves. Napntha reflux pumps may
require Monel metal.
N. Pumps
cracking must utilize 5
cent chromium blocks,
liners ranging from 12
cent chromium to 25-12 chromium nickel as
well' as 12 per cent chromium rods, valves, and seats. Centrifugal pumps
may be' 12 per cent chromium throughout with Stellited impeller
and
shaft sleeves.
O. Exchanger hibea are usually steel for oil-to-oil or admiralty for oil-towater, but 5 to 7
cent chromium tubes are used for cracked residuum.
P. Condensers may require Monel-metal shells or lining, but admlralty
metal is usually satisfactory for tubes.
Acid Corrosion. Hydrochloric acid is not present in
oil, but it
may
produced
distillation by
hydrolysis 'of chloride salts,
particularly magnesium chloride, that are present in the brine found in
crude oils. Sulfuric acid is probably produced by the oxidation of hydrosulfide in the presence of moisture, but only small amounts sulfuric
have been detected. These
constitute the "acid"
that occurs in
linea, condensers, coolers, and rundown lines and
particularly at points in which water accumulates, such as
valves in
horizontal lines.
The corrosive action of dilute hydrochloric
at the temperatures
encountered in distillation equipment cannot be satisfactorily withstood
by
common materials.' However, the copper-base alloys have been
widely
for hydrochloric acid and brine corrosion. Although conditio,ns- are not the same in aU plants,
use of copper-base,alloy tubes for
to be increasing.
and water-cooled exchangers
10
been using the following kinds of tubes:
refiner
,
10
143.
283
Percentage of tubes
in service
1930
1933
1936 .
18.0
60.3
21.7
16.3
14.9
68.8
12.0
5.6
82.4
Appro".
relative
costs
1.0
4.8
1.2
or
n Pew, A. E., Minimizing Corrosion in Condensers, Oil Ga8.J., Apr. 16, 1931, p. 112.
Mitchell, N:. W., A Study of the Corrosion of Copper Alloy Condenser Tubes,
Tram. ASME, 1946.
,
13 Strauss, Jerome, Tram .Am. Boc. Steel Treating, 16. 191- (1929).
11
I .
L.
TABLE
9-4.
Admiralty,
71 Cu,
1 Sn,
28 Zil
admiral~,
b,
~
....
,tt&ck predominantly
sulfur:
.
""montbs ill vapor 11ne, top of vaouum t.ower., ... , .... , .
4 mon~bl in vapor to oil 8.'I'.cha.nger ....... .. .. , .........
4 months in gaaoline va.por line .. . . . . , .. , ..............
3 months in va.por stre&m, top of bubble t.ower . . . , .......
5 mOD ths in vapor side, orude still partial cond enaer .... , .
6 months in oil vapor strea.m 1eadiSi to Clondeneer .........
1 month in bubble tower vapors, 3 of ........ , ... . ....
4 months in stabilizer reboiler vapors, 386F ...........
4 month8 in .stabilizer overhead vapors 180F .. ,., .......
3 montha in ga.aolliLe vapor line to can cl enser ... . .........
8 months in V&1lor 8ide, unit oondensiD8 ~asoline ... , ......
11 mont.hs in umt conden8in~ heavy gasolme vapors .......
19 mont.hs in vapor aide, Baa tower overhead oondensel' ...
6 months in oondenser shell, water and g&80line condensed.
6 roOlltha 8ubmerged \n water-gallolitie condensa.t.e . .......
6 mont.hs in OB.UBtic side of stream t.o cauatic exohanger .. ,
3 mont.hs in treated iaBOUne vapora, 300F ... . ........ . ..
9 months in exgeriment.a.l oondel1881', guolwe va(Jor .......
8 mOAt.ha in re ux conde.nsor .... , . ..... . .. . .. . .........
6 months in vapor line to condenser ... , .. , , ......... , ...
3 months in high sta.ge aonde.neer--bottom center . .......
3 mont-h. in hl&'h sta.ge condenser-top cent.er.' ............
High-pressure fraotioDa.tjn~ column, Dubbs uDit:
. 1.4 per cent 8ulfur, 121 ays a.t 69S"F ... " .. ............
1.4 per ~ent lulfur, 115 daY8 at. 680F .... , .............
1.4 per cent sulfur, 26 da.Y8 at 599F ...................
1.4 per oent lulfw-. 21 days a.t 54soF . ..... . .... _.....
1.4 per oent 8ulfur, 27 da.ys at 491F ...................
Atuck predominantly by water:
38 daya, vapor from alUDl eVloporator ..................
15 months, corrosive water ... . . , ........................
6 monthe, cooling water to condenaer .. , .. . .............
4: months, cOlldenaer-box wa.t.er, 12lioF ......... , ... . ...
3 months in cooling wa.t.er to oondenaer ................ .
o months in condeDler-box water ........................
12 montha, waLer aide, flash tower overhead oondenser ......
Speelal case, benzol, chlorinated hydrocarbon, and Iteam a.t.
160F. , . ... . .... . . . . . ........ . ........ , ...... , ......
Speoial case, speoimens immersed in carbon-bl&ek paste 20
days ... ' .............. _ , . .. . ..... " . .... , " .... . .....
72 Cu, 1 n,
0.05 Sb,
26.95 Zn
2
19
7
62
I)
38
4
4
5
2
17
8
17
6
31
4
4
5
10
3
14
S
13
39
48
16
(;
16
11
"
6li
12
11
26
20
22
17
16
13
7
63
27
66
88
7
79
27
62
7
33
16
60 '
5
10
14.
3
23
39
11
63
10
44
44
. ..
63
100
100
57
7
16
10
44
....
3
4
30
12
7
1
.)
0
4-
3
0
..
39
&3
34
..
. ..
..
.. .
50
36
45
48
14.
...
..
12
..
. ..
4
3;i
...
...
4.
10
3
13
..
..
..
...
..
22
0
2
3
iii
/;
8
15
2
79
..
44
19
-4
16
27
7
10
13
...
...
20
100
1
43
Muntz metal,
Copper
60 Cu,
40 Zo
...
96
,0
5
1
..
...
...
Aluminum
bn.aa,
76-Cu,
2 AI,
22 Zn
49
47
SO per cent.
cupfonickel,
70 Cu,
30 Ni
'23
...8
10
100
44
22
10
29
23
100
100
100
100
100
6
4
20 per oenL
oupronicke1,
80 Cu,
20 Ni
8
8
I)
Red
brass,
85 Cu,
15 Zn
Mltcbell, N. W., A Study ,of t-he Corrosion of Copper Alloy Conden.llor Tubes. Trana. ABM E, 1946,
., .
48
9
285
as the pounds per square inch that will not cause an elongation of more
than 1 per cent in 10,000 hr. A creep of 1 per cent in 100,000 hr has also
been used in many tests. Table 9-5 shows pertinent properties of several
common tube steels. The economic usefulness of various tube materials
was indicated in Table 9-3.
High temperature (above about 1200F) steel castings are usually
classified with respect to their resistance to (1) oxidizing atmospheres, (2)
oxidizing atmospheres in the presence of sulfur, and (3) reducing atmospheres. Most refinery or power plant furnaces operate in an oxidizing
atmosphere, or sulfidizing if the sulfur content of the fuel is abnormally
high. Gases that contain more than 100 grains of sulfur dioxide per
70,000- .--o;:::::-r--r--~-,-~---,--""""",-----,r---'-~-r-----'
..s::::
60,000
1---+---t--~-t~-+---+----1I....---I--~-4-----l
.~
~
50,000 1----+---+--+---;-----'......
0-
~ 40,000 l----t----j--..:~l--__1_-4-~~
~
0..
c::
30,000 t----F-od-~t---~--r--+
:>
&..20.000
(/J
t----+-~,---:;~~~ ~~~=__-+--+_--+-_I
~ U)~OOO 1----1---+
700
8QO
900
1.000
I,lOO
\lOO
(ASTM.)
"
Natural gas and manufactured gases can be easily desulfurized to below 5 to 10 grains sul!1l!, but
many crude oils a.nd coals produce sulfidizing furnace atmospheres (see
Table 14-7)~ Oxidizing atmospheres are best handl~" by: chromiumnickel steels (18-8 to.<..25--20)..; ~ucing atmosphere by nickel-chr~me
steels (65-15, 35-15, and 25--20), and sulfidizing atmospheres may be
handled witb strnight-chrornium Steels because of their cheapness. These
relationships are indicaled in Table 9-6. .
End supports for tubes in pipestil1s are usually protected from the hot
gases by insulation so .that plain cast iron or very low alloy irons (1 per
cent chromium) may be used. In the hotter regions of conve"ction sections or economizer sections of steam plants, higher alloy irons are useful.
At 1500F gray iron oxidizes about 16 ~imes moro rapidly than the
Ni-resist iron of Table 9-6.
Low-temperature Services. With the advent of solvent dewaxing
processes and ethylene manufacture, the lack of impact or shock resistance
of metals became an important consideration. Three general types of
286
9-5.
Approximate
com position
Kb;ld of steel
%
Or
Killed ea.rbon ...............
Carbon molybdenum .........
Silicon molybdenum .........
1 chromium, silicon, molybdenlUn. ....... ....... ,. . ,. ..
II
..
&.
....
I>
.....
0
0
0.5
6,500
12,000
1.
0
0
0
0.2
1.0
Relative
cost"
9~500
1.0
1.13
0.73
1.0
1.35
1.55
.0.5
12,000
0.84
1.9
1.25 0.75
2.0 0.5 ID1qt
0.5
0.5
18,000
10,000
0.77
0.70
1.87
2.1
2.0
1.25
0..,5
7.500
0.29
2.5
0.75
0.5
13,000
0.55
0.3
1.5
3.0 1.
3.0 . 0.5 m.ax
5.0 0.2
%
Mo
% 8i
Relative
penetrastrength,
tion by
PSI
scaling
Designll
1.5
0.75
....
!II.
...
!II.
(8 Ni)
0.5
9,000
1.0
lJ.OOO
2
~.35
. . ..
2.5
O.4a
2.6
0.5
Q,OOO
OA8
3.25
0.5
9,000
0.06
3.5
0.5
1.5
0
7,600
11,000
17.500
0.03
0.06
0.01
3.6
6.0
11.2
Based on
at lOOOF allowing 1 per cent creep in 10,()(X)
" About 0.7 per cent aluminum.
.
" Based on 1955 prices, but ratios have not cha.nged much since 1040.
4
i .
T~Lm
9-6.
ScaJing temp. OF
Name
Type 01
ma.teri8.1
Design
strength,
Chro-
Carbon
&ilicon
3.2
1.5-2 .0
}4e~te ...........
3.0
1.0-1.4 0 .5-1.0
3.2
1:2-2.7 0~H.75
Alloy iron
lfium
"
......
Nickel
..
.....
..
.......
600
..
900
........
..........
iOOO
.......
............
1300
.....
... ,
6.30u
1400
.....
..
..
""" ........
1400
1100
......
250 d
....
. ............
1500
1300
1300
350d
0.5 Mo
2100
1700
1700
90 5
" .. ,
..
It
..
.........
II
.....
"
....
......
.. "
....
..
...
"
2.6-3.0 1.2~-2. 2 .
1.4
. . . . . . ..
12-16
14 .3
3.0
1.6
3.3
0.10
o .:l~
11.5-14
..
" "
0.6
17
....
"
0.9
26-30
..
..
l.S
18-23
1.8
1.8
1.8
2.3
24-28
26-30
24-28
2.3
13-17
15-19
",
..
8-12 O.li
11-14 0 .5
8-11 0.6
18-22 0.5
64-68 0.5
33-37 O.li
Mo ,1600
Mo 2000
Mo 2100
Mo 2100
Mo 1800
Mo 1900
..
..
..
..
1300 1600'
1900 ' 2000
2000
2000
2100
2100
2000
...
1900
., .
N.otes
psj~
200
300
Insulated end
supports
Insulated end
supports
Convection tube
sheets
Conveotion tube
sheets
300
3000
-620"
470 cl
660"
2000
1200d
Conveotion tube
sheets
Hottest convection supports
Hottest conveotion supports
Hottest convection supports
Radiant supports
Radiant supports
Radiant supports
Radiant supports
Radiant supports
Radia'nt supports
'c
--------~--~=-~----------------------------------~----------~---------
288
9-1.
MATERlALS SHOWN IN
Per
cent
C
Curve
Dum- Material (met urue.l!8 deaignated)
bel'
1
2
3
4
5
6
7
8
I)
10
11
12
0.11
FIG. 9-3
5 er
0.04
............ .
0.15 .............. .
0.15 0.46 Va
0.32 L 11 Mn average
0.16 0.89 Si, 1.12 Mn
0.19 0.6 Cu, 1.00 Mn
0.16 O.66Zr
0.15 0.85
0.51 Cr
0.2
2.1 Ni average
(Average of many kind&")
Normalized
About 300 Brinell
nickel ....................... .
13
Notes
....
Temperoture,Olfq.F.
FIG. 9-3. Relative impact strengths of metallic materials at variOtiS t.emperatures.
shows the kinds of m a t e r i a l s . '
.
Table
289
290
TABLE
PETROLE~M
9-8.
Numbers
OF ALLOY
REJ'INlNGi'l
parentheses indicate
oP1POS:U;c page
Service or Equipment
Acid sludge-lines and pumps (l~ 5)
Acid sludge-pumps (8, 11, 14, 16, 17)
Alkylation-hydrofluoric acid "(8, 39)
Antimony chloride &; hydrochloric acid
(10)
Bolts or bolting-low temperature (20)
or bolting--submerged condensers
(8)
Carbon bls.ck paste (13,23,
Catalytic cracking-elevator
(4)
Catalytic cracking-linings or cladding
(23, 24, 27)
"
Coke handling pulverizing (4, 37)
Con~eD.sers-topping (8~ 13, 28, 33)
Condensers--vacuum. (25, 28, 29)
."''''',. . .''' .. chlonde---i3OlutioD.8 (16, 17, 38)
Ethylene-reaction tubes (11, 23)
ans-Dl3.Qte9 (24, 25)
cloth (8, 10, 11,
Furfunl-condensers or
(28,
29)
_Furfural-regenerator tower (3 1 8, 101 26)
Hydrochloric
(2, 7, 35, 36)
Hydrochloric
dilute (1:. 10, 14 J
17, 3S)
Hydrochloric
dilute and
(3, -8, 12, 13, 33)
acid-boiling 48% (7, 9)
Hydrofluoric aeid-60% a.t
(7, 9,
13)
Hydrofluoric acid-l00% cold (39)
Instrument
eoe! expansion
(19)
67%
(8,
Sodium
boiling with
H,8 (9, 11)
Bolu war solutions,
etc. (8, 10,
21)
Sulfur, molten or vapor (8,
acid-25% boiling (5,
7)
Sulfuric
at 275F, 96% at
176~ (7,
16, 18)
Sulfuric
96 % cold (1, 39)
Sulfuric acid--over
cold, pumps &;
valves (23, 24)
Sulfuric acid---all cone &:
(11 7, 16)
acid-fuming (17)
Water-corrosive (13, 29,30,
34)
Water-salt, centrifugal pumps
bolts (8, 31)
(30)
9-8.
291
(Continued)
Materials
1 High silica irons-Duriron, TantiroD,
Corrosiron, etc.
2 Silicon molybdenum irons-Dutiehlor, etc.
3 Ni-resiat iron
4 Ni-ba.rd iron
5 Chemicallea.d or linings
6 Chemical tile
7 Carbon (Karbate)
~ Monel
9 Monel H or S
10 Nickel or linings or cladding
11 Inconel
12 Nickel silver
13 Cupro nickel
14 Worthite
15 Hastelloy A
16 Hastelloy B
17 Hastelloy C
18 Hastelloy D
19 Nickel iron, 36-50 Ni
" InaSmuch as only slight differences in the service may cause a.n alloy to be unsatUr
factory, thiB list is only fill indication of the types of materiala that should be explored.
eral,. these chemicals are introduced into the vapor lines ' of distillation
units. Ammonia is hitroduced as a gas, and the other materials as dilute
solutions, although lime is preferably added as a slurry. Lime is often
used in cracking plants by injecting it with the charge to the pipestill,
and it serves partly to reduce 'acid corrosion as weH as sulfide corrosion.
Brandt17 explains the use and application of ammonia. Polyaromatic
amines having large oxyethylated side chains are widely used as inhibitors to U acid" corrosion, and similar inhibitors are put into the hydrochloric acid used in cleaning refinery equipment.
The solutions are usually injected into the system by direct-acting
pumps. A fine dispersion of the chemi~l in the oil is essential,.and hence
the solutions are often 'mixed with a part Qf the oil by means of mixing
columns before they are injected into the system. These COhllllDB consist
of a pipe containing bafHe plates. From 0.15 to 0.3 per cent by volume of
caustic soda. solution (about lOOBtS) or 0.3 to 1.0 Ib of lime per bbl of
17 Brandt, L. H., Ammonia. for Corrosion Control, Ref. Nat. Gaso. Mfr., August,
1937, p. 382.
292'
ana
CHAPTER
to
CHEMICAL TREATMENTS
Impurities that are present in crude oils and those prQduced during
refinery distillation and cracking operations must be removed from nearly
all c~mmercial products. Improvements in color, stability to 1ight, odor,
sUlfur content, amount of gumlike or asphaltic substances, corrosiveness.
and composition are accomplished by treating. Sulfuric acid was once
widely used because it partly removes sulfur, precipitates asph~ltic or
gumlike materials, improves color and stability, and to some extent
improves the odor. Sweetening of "sourH distillates is always necessary.
,but the long dominant ," doctor process" is being supplanted by mercaptan-removal Sweetening processes. Acid and adsorbent clays are ,
still used to improve the color of lubricating oils, but the solvent-extraction processes of Chap. 11 are now standard lubricating-oil practice.
Desulfurization processes whereby sulfur is eliminated in the fc:>rm of
hydrogen sulfide are becoming significant.
SULFUlUC ACID TREATMENT
.
,
Brandt, Lee, and Wadsworth, . . . ' Toluene Treating, Ind. Eng. Chem., 39, 1010
(1947).
293
294
fates are dissolved by caustic soda, but the neutral esters are not; and at
temperatures over about 285F they decompose, causing discoloration
and tar or gumlike materials in the distillate. 2
Sulfuric acid also removes or dissolves resinous or asphaltic substance!I
that may be_present because of poor fractionation, entrainment, or cracking. These materials tend inhibit the crystallization of wax, and hence
acid trea.tment often raises the pour point. Oxygen compounds, such as
naphthenic acids and ketones, and substances such as alcohols and aldehydes -that are formed by high-temperature oxidation are dissolved by
sulfuric acid, but when diluted with oil th~r removal is never complete.
Nitrogen bases similar to quinoline or pyridine, which are produced in
small quantities during distillation, are easily dissolved in dilute ,acid.
Strong acid (93 per cent or stronger) is necessary to remove mercaptans, but such l~rge quantities are required that tt sweetening" is seldom
practiced in this manner. Alkyl sulfides, disulfides 'and sulfates, and
most sulfur compounds are removed by 93 per cent or stronger acid, but
the acid alkyl sulfates dissolve, to some extent in the oil.
The rate ofl a.ction of suHuric acid on the various inipurities appears to
be somewhat as follows:' (1) nitrogen compounds such as amines, amides,
and amino acids; (2) asphaltic substances; (3) olefins; (4) aromaticsj arid
(5) naphthenio acids .
.The-loss in octane number of cracked gasoline is not large for normal
quantities of ~cid. ~.6 .
Concentration of Acid. Sixty-six Baume 2 .or '93 per cent acid finds
most general use. However, for treating light distillates to color only, a
more dilute acid may-be advantageous. 6 For most other purposes, such
as removing combiped sulfur, improving the burning qualities of kerosene,
and .removing tar from lubricating oils, a 93 per cent or stronger acid
should be used. - For lubricating oil, 98 per cent acid is also widely used.
The weakest suitable acid is employed because sludge losses are higher .
with strong acid. In treating pressure distillate PotthofF finds that
sludge and polymerization losses are almost twice as large when using
s~ong acid. . Total losses ranged from 1.6 per cent when using 5 Ib acid
per bbl, up to 11.3 per cent for 20lb acid per bbl. Weir, Houghton, and
. Majewski 8 find somewhat the same for a 289 viscosity at IOOF lubri~at-
to
295
ing oil. In the concentration range of 75 to 98 per cent acid, the sludge
loss increased 0.002 to 0.0125 per cent for each mcrease of 1 per cent of
acid concentration. Losses ranged up to 4.15 per cent for 31.31b acid per
bbl when using 98 per cent acid.
Strong acid (93 to 103 per cent) used at low temperatures (25 to 50F) removes sulfur from gasolines, and aromatic hydrocarbons from burning
oils or tranSformer oils, but the color is generally poorer when using fuming acid. Cooke and Hayford, 9 in treating pressure distillate by the
Stratford centrifuge process, found that 80 per cent acid produced a
0.2 per cent sulfur distillate whereas 104 p~r cent acid reduced the sulfur
content to 0.07 per cent.
For improvement of color, an acid of 93 per cent strength is recommended; but if the combined sulfur. is low, an acid of only 85 per cent
strength may be advantageous. Weak acid is a180 useful in removing
nitrogen bases and for improving the color Without removing unsaturated
_compounds.
A large amount. of spent alkylation acid is becoming available to the
industry and it has a. strength of 90 to 93 per cent because of inactive.
hydrocarbons and certain oxidation products contained in it. It haa
been found satisfactorylO for the treating of naphthas, furnace oils, and
lUbricating oils (if. a. subsequent rerunning operation is c<?nducted).
Results with wax and other special uses have not been conSistent, but
ways of utilizing the acid have been devised by most refiners.
Quantity of Acid. Too much acid may result in a poorer color and
a loss-of arom~tic and unsaturated hydrocarbons. If acid is applied to
lu bricating oils in too -large doses, the oil may be" discolored by l' burning."
The remedy is to use the acid in small charges and keep the Qil cool. . The
treatment of spray oils, medicinal oils, and sometimes wax is accomplished
by adding fuming acid in 25 or 30 lb per .bbl charges and using as much,in some cases, as 200 Ib of acid per bbl.
The quantity of acid that is commonly used is about as follows:
N alural ga8oline-~sually none but occasionally 2 lb per bbl.
Straight-run ga8olin~usually none but may require 5 lb per bbl f~r
_sulfur removal.
Pressure distillate-usually none but for high-sulfur oils and oils from
naphthene-base crude oils even 8 Ib per bbl may be required.
Solvents--O to 5 Ib per bbl if high-sulfur stocks must be processed.
Kerosene-l to 15 Ib but as much as 75 lb per bbl for the kerosene
from some naphthene-base crude oils. Sulfur dioxide extraction is more
feasible for such kerosenes.
Lubricating oil~ to 60 lb per bbl. Pennsylvanian oils usually require.
a Distilla.te Trea.ting, Part II, Ref. Nat. GaBO. Mfr., April, 1934, p. 130.
10 Bland, W. F., How to Conserve SulIurie Acid, Pel. Processing, August, 1951, p. 865.
- 296
297
CHEMICAL TREATMENTS
S2,83 (1940).
:10
Rogers and Voorhees, Gum Formation in Gasoline II, Ind. Eng. Chern., 26, 520
(1933)..
298
extent
this is counteracted by a cost that inversely proportional to effectiveness. Minute amounts of heavy metals such as copper or vanadium act
as, catalysts in producing gum, and certain compounds have been developed for counteractingU this effect.
SWEETBNllfG TREATMENTS
C~ICAL
299
TREATMENTS
au
+(E -
1)(8 - Sb)K,
(Em - 1)(8 - ~)KfJ.
(10-1)
300
"
where 8
= WK
.Dctane-number'
of stock
Chemical processea!'
,
CAtalytic on only
8t~ght.-nm
gasoline- .
Straight.-run and .
low-sulfur gasoline!
Cracked gaooUnes
..
40'
45
50
55
60
65
70
75
65.4-73.4
68.6-76.6
71.5-79
14.6-82.6
71.7-Bli.7
80.9-88.9
60.4-70.4
63.9-73.9
65.4-75.4
71.1-81.1
74.9--84.9
78.8-88
84.3-92.3
87.5
86.3
8~
73.0-79.0
75.5-81.5
77.3'-83.3
n NelsOn. W. L., Lead Response. Oil Gu J., Oct. 6, p.lM, and Oct. 13, p. 137, 1945.
J8 Berger, C. W., Practical Aspects of Sun Stability, Ref. NaL Ocuo. Mfr., 115. 411
(1936).
U Ridgway, C. M., Improving Gasoline by Caustio Washing, Oil Gtu J., 'Mar. 31,
1938, p. sa.
0 Anon . Lime Wash ~ . Sulfide Removal, Ref. HaL Gaso. Mfr., April, 1940, p. 81.
TABLE 10--2.
'.
-,. .-. -
21
(M.C.)
()J.e.)
"
W.e.}
(M.e.)
MEBC.A.PTAH
DISTIUBUTIOK
IN
80M];
TYPIC.A.L G.A.s.oLlNES"
.f
10
11
13
14
ul'
16
(M.c.)
(~.e.)
(M.e.)
(Kaua.)
(](au.)
(W.C.)
(W.C.)
(M.C.)
(M.e.)
(M.C.)
(11. "l"n.)
CILTu.)
JIou4ry
&.aIaht. HOIIdr7
Blnighi
. pM.
Yapell'
Soadry
Straigh'
100-400
100-400
100-400
1()(HOO
Btnd&bi
run
!;
....
Per cent
or
1~6
Patpbill
lOC>-4QO
Cokq
1YIii.
100-4W
rWl
I"IIR
rim
8)-DUle~ip'
Cnui.
Crud.
obarp
dwp
1~
100-400
100-400
lQ(}-.O)
18.0
17.0
8.'
6.7
I.'
)l .a
U.O
6.1
T.1
U.l
11.6
17.7
66.11
'.a
1.1
11.0
11..
II.'
6.8
10.6
. UI
7.4
1.1
~. 7
14.4
20.1
100-300
100-400
Thermal Tbermal
ora.obd acacbd
llXHOO
llXHOO
V~
pbue
100-400
mMCIIp\aR
IIOGklDt!
':9
Me&h)'l. ......
Et.byl. ........
16.7
aD.6
411.2
Propyl. ........
Butyl. ....... ,
Amyl. .....
Tbio~ ....
. U.,,1 aIld
heaYier ........
ToLtl .
'4.8
".""")
18.11
13.4
6.4
la.l
10.8
!g.0
U.O
10.~
~1.9
' . 1
20.0
J..6.6
JO.i
Il.l
B.O
6.
14.1
8.0
11.8
8.0
18.'
";;:J
".0
11."
14.'0
9.6
IU
21.6
16.6
4.7
1.8
.'
'!:!)
100.0
100.0
100.0
43.7
100.0
. 0.009
0.080
O.OQO
0.006
100.0
WO.O
lOQ.O
O.02,P
0.0108
O.OOW
.....
. .....
811)
7.Q
68.l
'.1
18.6
l~.l
&.a
1.1.4
33.7
11.3
10.0
16.0
11.1
10.11
14.8
-9 .5
1,s.8
19.7
13.4
19.8
14.11
11).4
6.11
8.8
12.'
27.~
28.2
100.0-
100.0
100.0
0.000
0.035
0.020
100.0
100.0
100.0
100.0
46.1
100.0
O.oogg .
O.Ml1
0.0093
0.0114
0.009II
0.0078
Mercaptaa sulfur
maample.
1IC cent. bJ
-".i.........
.. '}
13.8
100.0
L...-
~ eaq,y. aod KeUq. CiiI.Ica1 ~ 01 i.~ Pro..aes aI1d lI.eroapt.lwl Remo....J. OilGGl J., )lDf'.1l, 1~42, p. 116.
302
removal of hydrogen sulfide and mercaptans, are fea~ible for some gasolines' because of the improvement in lead 'susceptibility and the saving in
chemicals in subsequent treatments. Caustic ~olutions ranging from,
5 t,o 15 per cent are employed. Caustic washing is becoming important
again as a means of removing dissolved hydrogen sulfide from the products of ca.talytic desulfurization processes. A recent modification U
involves regeneration of the caustic along with oxygen in electrolytic cells. '
100
....c
'-0
'0
Q\
:=
I:
2.0
'0
....Il
II)
....
,I:I:
.! 0
u._+
!+-:J
't-IU 0
01.1)
' O\~
I: ~
.- :J
0.,
~D
.u
~
+'+-
V)O
./
10
'L
/"
,I
.",
........ 10 % NaOH
...........
~
- .... .........
~
........
'"
I!"'Shell $OlufizB~ K2
0,2
nl
(. C2 C3 C. (5 C6 ' 1
Number of Carbon Ato'l ns
in Normo\ Mercaptcm
,
'
FIG. 10-1. Stripping coefficient VB. 'number of carbon atoms (in 'the normal mercaptan)
for some treating solutiOll8.
Puff, Dahl M., Mercaptan Removal Ups Octa.ne, 011 Gas J., July 19,1954, p. 115;
,
f
303
CHEMICAL TREATMENTS
Q)
.E
001)
a
\!)
1.000
500
\\
.,
lit
..r:
100
50
Do.
G'!
'-...
1 ............
: .
\70
%
20
10
-r-- .
No OH conioinlng
....c
1\
.!!
u
~Q)
0
(..)
J:
..
!
:;:
(.J
0
L.
0+-
0.1
0.05
not I
I--
% lIorganic acids II
LL:
0-
"'r\...
C,
c2 C3 C.
IO~oNaOH
I
(5
I .
C6 C7
2RBH
NaJlb0 2 == (RShPb
2NaOH
(RS)J>b
8 = R~2
PbS
J.
as
2RSH
+ 2N'aOH -+ R$:s
Na~
2H:sO
305 .
CHEMICAL TREATMENTS
+ 4CuC1
-+
2RJh.+ACuCl
+ 4HCI
In the sJurry
Tw.o general methods -.of reducing the amount .of sulfur have been
devel.oped, th.ose- which involve solvent 'extraction .of the su1fur c.omP.ounds and those by whic.h m.ost of the sulfur compounds are decomposed
by the use of a .catalyst into hydrogen sulfide and' hydrocarbon remnants
of the .original sulfur c.ompounds. The solvent extracti.on processes are
not as cheap Dr effective as the catalytic pr.ocesses in the removal ' of
sulfur because they remove the entire sulfur~bearing m.olecule and at the
same time certain hydrocarbons, particularly those with aromatic ~gs.
Thus, when the removal .of aromatic hydrocarbons as well as sulfur is
desirable, the solvent processes may be superior. -Sulfuric acid has long
been used in dissolving or rem.oving sulfur, and hydroflu.oric acid is also
an effective solvent, but sulfur dioxide and furfural ~re mentioned more
frequently. When _applied to catalytic cycle oil to produce diesel fuel,
the effectiveness 45 of the several solvents is about as shown in Table 10-3.
Hydrogen fluoride is effective, but- its effectiveness decreases with
TABLE
Solvent
vol., %
Solvent
Sulfur dioxide (llt 68F) ...... . ......
Furfural ..... ",' ....................
Hydrogen fluoride ..... " ............
Hydrogen fluoride ... " ....... ' .' . . . . .
Hydrogen fluoride. " .... . ..........
Las~lo,
10-3
100
100
20'
50
100
Extract,
RAffinate
Sulfur
sulfur, % removed, % wt, %
0 .30
0.47
0.34
0.20
0.13
73
56
69
82
85
35
25
14
16
17
.
T. S., How to Desulfume Diesel Fuel, Pet. Refiner, January, 1955, p" 115.
306
of
.. Lien and .Evering, Hydrogen Fluoride Extraction . , lnd. Eng. Chem., 44,
814 (1952).
n Brooner and Conn, Recent Advances in Perco Catalytic DesulIw-ization, Oil
Gal J., Oct. 26, 1946, p. 96; also Ma.rtin and Carlson, Catalytic Desulfurization by
Use of the Gray Process, Oiz"Gas J., Mar. 26, 1942, p. 138; and Amero and Wood,
Ca.talytic Desuifurization of Cracked and Straightrun Gasolines, Ot Gas J.~ Ma.y 24,
1947, p. 82.
.
,. Berg et aI., Ca.talytic Desulfurization '. . . , Cobalt Molybda.te Process, Trans.
A.I:Ch.E., 43, 1 (1947).
.
Hyde and Porter, The _Autofining Process .. . ,sec. III, Proc. Fourth World Pet.
C011gr., Rome, 1955.
50 Hoog, Klinkert, and Schaafsma, Hydrodesulfurization . . . , Oil Gas J.,. June 8,
1955, p. 92.
51 Eckhouse, Gerald, and de Rosset t Unifining Upgrades Distillate Fuels, Oil Gas J.,
Aug. 30, 1954, p. 81.
6S Pa.tterson and Jones, Hydrofining's Use in Product Improvement, Oil Gas J.,
Oct. 18, 1954, p. 92.
.
51 Odasz and Sheffield (Diesulformer), Oil GD..8 J. t Ja.n. 23, 1956, p. 64.
i f McMee et al., Gulf HDS Process Upgrades crudes, Pet. Refiner, May, 1955,
p.156.
CHEMICAL TREATMENTS
. 307
on
Jones, W. A., Hydrofining Improves Low-cost Lube Qua.lity, Oil Gas J., Nov. I,
1954, p. 81.
IS McMee and Horne, Hydrogen Trea.ting, Pet. ProceJJs1.ng, April, 1956, p. 47.
57 Achieving Ca.talytic Desulfurization . . . , Oil Ga4 J., Dec. 20, 1954, p~ 78.
5&
308
REFINING BY ADSORPTION
x'
-'
or in logarithmic form
, ! ,'
iLCn
Xl '
log M
= ~og
+; log C
.... ,""-
TABLE
10-4.
Cslcination or
aotivaLion
temp, OF
Absorbent
otiva.ted ~lum.ioa:
.
Grade F-l.'.... . .... .. ..... . .. , . ...... ' . ... . . .. ...
Grade H-llll ...... . ..... .. .... . . . . .. .... . . . ..... .
9.uxite:
ArkAnsas .... . .. . ... . ........ .. . . ........... ; .....
400
400
DB buI'k '
DA.,
'.
' meroury
dewnty,
d
'I;
/
Em81 y,
'
900
1100
100
900
1800
'.
.88
1.58
'3.23
. ..
~
.95
.94
.96
.78
\\00
400 '
400 ,
400
g/eD
900
1300
600 -
g/oo
1.33
.97.
400
00
450
700
900
400
Dr,
helium
density,
.82
.64
. ..
~
2.02
1.68
1.63
1. En -
1.51
1.82
72
2.64
44
43
42
42
20
21
236
76
64
49
34
41
54
38
178
151
187
602
3 . 18
3.21
. 3.26
3.25
2.12
36
2.2.5
41
89
374
34
58
312
2.31
2.88
36
80
34
.' 52
280
\ 420
126
2.56-
.97
2.66
2.66
2.69
2.65
2.66
2.66
44
...
118
119
67
57
260
236
208
'48
6500
1397
660
110
' 32
.75
1.89
44
.36
.73
2.09
51
47
....
.68
. ..
2.8
95-
124
64
.42
16
33 .
16
22
64
....
43
38
10
~3
400
2.27
60
. ..
83 '
42
41
41
41
49
.67
.67
.32
.63
02
2.37
1.01
1.140 .
1.130
1.120
pore
radius. AO-
200
300-a50
.li6
.68
ml/g
Average
51
, ..
.65
.64
.56
.96
44:
Surfaoo
are&,
.. .
. 79
.92
Per cent
pores"
.. . .
1.38
.97
1.66
1.14
1.00
Per cent
voida
56
44
60
66
46
110
109
38
43
12
= l/D.,.
310
10-5.
Hea.t of
Thermal
wetting
Specifio
Bulk weight, conductivity J
of water,
heat,
cal/g at
Ibleu ft
Btu/sq ft/hr/
Btu/lbrF
about
"F lin.
Adsorbent
70~
38-40
48-52
50
61
34
45
38-42
0.22
29.1
1.5
14.14
19-21
...
0 .25
0.25
0.25
0.25
0.1
0.24
...
0.4
. ..
25
23.7
15.9
9.5
Grade xF-21.
TABLE
10-6.
HEAT
0:"
WE"rl'IN'G OF .An80RBENTS
eal/g
Adsorbent
Activated
(7007)
bauxite,
(Ark.)
21.8
16.2
12.8
12.6
12.3
11.0
9.1
10 . 1
36.5
Activa.ted
(550F)
Activated
carbon
fuller's
earth
23.2
20.6
15.0
25.7
27.0
26.5
13..4
27.0
12.1
6.5
17.9
22.1
23.0
20.2
17.1
.
5,4
4.3
7.4
9.3
11.9
11.0
3.0
9.7
.. ...
..... .
4.5
9.5
to
....
41
..
....
"
...
...
..........
......
....
.-
Silica.
gel
29.1
34.9
Activated
AhOJ
(xF-~l)
18.0
31.7
29.2
28.5
25.5
21.9
....
...
4.7
a ......
4.1
.....
2.7
2.6
'J
311
CHEMICAL TREATMENTS
-M'
a'
a _C
= -
(~-!)
7l
11
or
In the selection 6 & of a clay, examinations of the clays' that are available in
the vicinity should be made in the laboratory.
an indication of the
difference in c]ays note Table 10-8 by Dunstan. 66 He examined the
decolorizing power of the adsorbents using a 0.25 per cent solution of
crude asphal tic oil in benzene.
As
TABLE
10-7.
COMPARISON OF CLAYS
Tag
Robinson
color
Riverside,
Tex.,
funer's earth
100
100
l~
100
100
Na.tUral,
Utah
120
130
140 .
150
Treated
German day,
dry {ann
Treated
Tex. clay,
pulp ~orm
120
133
140
150
170
235
240
285
400
245
5()()
Trea.ted
Calif. clay,
pulp form
465
G'
312
10-8.
Material
Cc of colored
solution
decolorized by
1 g of clay
Approxima.te
bbl per ton .
60
30
30
342
25
142
20 '
15
14
114
85
80
68
Alumina. ................
12
10
10
8
8.5
4
2
2
171
171
57
57
45
47
23
11.5
11.5
313
CHEMICAL THEATMENTS
TABLE
10-9.
OIL"
PROPERTIES OF A LUlIIUC.ATlNG
Material
Unfiltered stock .....
Stream after oil yield
Gravity.
API
Viscosity) SUS
at 210F
41.6
0.134
2.25
156
48.3
46.2
0.02
0.05
0.08
0.13
0.13
0.13
0.027
0.115
87
0.546
125
135
of:
10 bbl. ..........
25 bbl ...........
75 bbl. ..........
150 bbl. ......... ~
300 bbl. ..........
500 bbl ....... ' ....
600 bbl. ........ .- .
43.2
42.4
41.9
4l.8
41.5 .
0.13
0.932
1.49
1.61
1.79
95
140
140
140
will b~ of a much lower gravity and viscosity69 than the parent stock
(Table 10-9). Resinous and asphaltic substances are actively adsorbed.
Little of the sulfur is adsorbed, and hence clay-treating methods are
seldom used for desulfurization. 70
TREATING EQUIPMENT
70
314
bar and its.bolts, so that no steel is exposed. Hard lead (94 Pb-6Sb) and
tellurium lead are gaining in favor because their greater strength.
Conlinu0'U8 treaters involve many arrangements of mixers and settlers,
. but in principle they are much alike. The most simple arrangement is a
mete~g and mixing system such as would be employed in adding tetraethyl. fluid or inhlbitors to gasoline or demulsifying agents to crude oil.
Although injection can be controlled by hand, the best methods ~mploy
proportioning pumps actua.ted by the main tf~e!" pump, proportioning
orifice Bow controllers, or similar automa.tic ptoportioning methods~ 72
Such systems are illustrated irt: Fig. ~0-3 for introducing an inhibitor into
of
i...
Inhibitor
feed, .
Ven!
"',___
Three alternateS
....r--,
C BA
-Gageg/ass
A-,----I
I
~w gCJSOline
In
Three alternate
ways
inhibitor
b1owcose
Synchronized
pumps--- .... N
A
Proportioning pumps
Or-ratio flow
controller
FIG.
Inhibrred gasoline
10-3. Three methods of adding inh.ibitor to gasoline.
or Injecting
-315
CHEMICAL TREATMENTS
t-"-p6asollne
oul
Settler
Row
ga.soline
Wo+er
wosh
In
Fresh
cClpshc
In
'-t~~
'-~---.....".,--..
Reclrculof/on
FIG. 10-4. Caustic washing with recircula.tion of
Tci Drainer
R e.,overy
caus~ic.
316
Bbl per hr
17.8Dz yAh
(10-2)
or
Psi
.
PSI
(10-3)
at
r
i
31'7
If a longer time of contact is desirable, so--called contact column8 or time
columns may be used. These are attached after the mixing columns as
shown in Fig. 10-8. Time columns may consist. of large pipe with halfmoon baffles or orifice plates having large holes. In arranging tnixing
equipment, no low points,in' which the chemical may collect should exist,
because the liquid tends to sUrge in slugs into the settling equipment.
If ,the chemical is injected by gravity feed or from a pressure feed tank,
the rate of feed can be controlled with a valve and no metering device is
necessary. If blow . cases or eductors are UBed, the chemical must be
measured as it is added. The most common method of metering is by
orifice meters. Morrell and Bergman 78 pre~ent orifice meter charts.
The treater often estimates the material handled by a blow case by noting
the time and the pressure during the admission of chemical.
TABLE
10-10.
ORincE
MIXERS
PressUI~
Bbl
per hr
10
20
40
60
100
150
200
o:~ .1
0.6
0.8
1.0
3.0
6.0
10.0
1.2
0.54
0.52
4.7
2.15 I 1.11
18.8
8.6
4.45 ' 2.08
42.2 . 19.3 110.0 " 4.67
53:7 , 27.7 ' 113,.0 :
62.5
29.2
52.0
300
500
0.35
0.8,
2.22
5.0
"8.9
20.0
0..57
1.29 '
2.3
5.2
14.2
0.45
0.79
1.78
4.95
,f ;rample 10-1.. Design of Orifice Mixer. Acid is to be mixed with 8,OOO'bbl per
day of 53 API pressUre distilla.te. A pressure drop' of 25 psi is permissible.
, '
Bbl per hr
8000
24
= -'- =
334
pSI
Number of plates
25
5.5
+ 0.01623(53)
1.83 = abo':lt'14
"'" 1.
83
318
Use a pipe having about five times the orifice area, or 30 sq in. Use sta.ndard or extra
hea.vy
~in.
8qin.
Sqin.
Approximate la.yout of pla.tes:
Six IX-in. holes or
6 X 1.227 = about 7.37
Twelve ~-in. holes
12 X 0.601 = about. . . .
7 .22
X 6-in. clearance around one side of plate ............... , -= 0.42
0.42
TotAl opening, sq in.
""" 7.79 or 7.64
The plate will be 6.07 in. in diameter with a M6-in. recess around half of the circumference.
H the plates are spa.ced 1 it a.part, the tota.llengthof the mixing column will be a.bout
16 ft.
In rare instances the time of contact must be very short, and for such
situations mecharn.cal mixers like thos~ employed in the centrifuge treating systems?' may be employed. Continuous contacting with acid has
also been accomp1ished so by means of a . horizontal mixer in which a
shaft, equipped with blades, rota.tes at 900 rpm.
Settlers or Separators.. Although A. C. Ingersoll 81 completely pre...
sents the theory of settling, the exact settling time that is required must
be determined for each treating operation. In genera]J caustic and water
mixtures settle more rapidly than acid sludge or" pepper. U Ten or fifteen
minutes often suffices for caustic or doctor settlers, but an hour may be
required for settling acid sludge. The settlers are usually about 40 It high
and range in diameter from 2 to 10 ft. In large-diameter tanks, a gentle
circulation takes place and tends to spoil the separation. The sprays for
water-wash tanks are usually of welded pipe in the form of a cross or a.
six-legged star with ~-in. holes drilled on the same side of each pipe in the
star. These sprays, all . pointed in the same direction, give a gentle rotating motion to the oil in the tank. They are placed several feet below the
oil outlet. Horizontal settling tanks are more effective than vertical
settlers of the same capacity. This is due to the lower vertical velocity
in the horizontal settler. The velocity of the fluid in the settler should
not exceed about 3 ft per minute . . A higher velocity will require a greater
time for settJing. Stokes's law [Eq. (~l)] governs the rate of settling.
Example 10-2. Design of Settlers. A tank. (or settling caustic from 12,000 bbl of
oil per day ma.y be designed as follows:
Caustic or doctor settler:
..
Allow 30 mill of time, a.nd use a vertical tank 40 ft high.
Trivals, H., Ref. Nat. Gaso. Mfr., Ma.y, 1932) p. 312.
30 Morrison, J. D., Continuous Acid Treating Heavy Lubricating Oil) Oil Gila J.,
Oct. 14, 1948, p. 87; or Petroi.eo In~americano, December, 1949, p. 42.
81 Fundamentals and Performance of Gravity Separation, Pet. &ftner, June, 1951,
p. 106.
71
319
CHEMICAL TREATMENTS
.
12000
42
Volume of oil per hr.X 7.5
24
One-balf of this =
2,~OO
2,800 eu ft
1,:go = 35 sq it
320
I
i
I,
only major use of filters is in removing finely divided clay from treated
cylinder stock in the clay-contact process and in dewaxing. The Sweetland press, a picture ~f which is shown in Fig. 10-5, is widely used, and
more recently the Oliver precoat cont.inuous rotary filter has been adopted
by many refiners. In addition the Kelly pressure filter 88 is used for
removing carbon,. lime, ' and other solids from cracking-still residuum,'
or to remove a large bulk of solid ahead of other filters. Pressure filters
are also used to remove Clay from pressure distillate. 79
Be Willson, C. 0., Oil Gas J., Dec. 18, 1930, p. 38.
Vespp..r, H. G., Oil Gas J., Mar. 30, 1933, p. 44.
88 Badger and McCabe, "Elements of Chemical Engineering," 2d ed., McGra.w
JIill Book Company, Inc., New York, 1936.
'
87
1
I
I
\
I
,
I
321
CHEMICAL TREATMENTS
10-11.
10
12
25
25
31
37
86H
3
25
37
61
82
109
145
18
18
30
41
54
72
111
185
1,004
175
252
239
523
105
500
965
11
22
42
20
27
36
4.8
166
158
349
333
670
14.
28
56
20
Z1
36
123
il7
262
250
502
15
33
63
2A
16
19
10
20>i
2
16
23
7.5
21
46
42
0.3
....
12
&
..
,.
4.8
12
642
483
9,350
16,500 29,600
7,900
13.500 24,000
16,500 29,000
~,300
The Olive; precoat filter is a modification of the regular Oliver ill ter, 88 It
consists of a horizontal cylindrical drum, the outside Qf which is made up
of separate segments
compartments. The entire outside of the
.cylinder is covered with a filtering medium such as fine mesh wire or cloth.
Each segment is connected to a discharge line, under vacuum, by a special
valve on the end of the drum in such a way that suction is maintained
while the drum rotates. A deposit (or precoat) of diatomaceous earth or
or
Ie
322
similar porous medium is deposited on the drum by rotating the drum for
about 30 min in a vat conta.ining a slurry of the precoat filtering medium.
The vat is then filled with the oil-clay mixture; and as oil passes through
the filter surlace, a thin film of clay is deposited on the surface of the precoat. The thin layer of clay is continuously shaved from the surface by
means of a knife-edge until the precoat is consumed. The pre coat lasts
from several hours to as long 88 several days, depending upon conditions.
The coating of clay may be washed with naphtha. and dried with air or
stea.m as the drum revolves.
Several derivations of the performance of rotary filters have been presented. 9o ,91,92 If the effect of the depth of submergence and the resistance
of the filter cloth and connecting lines is neglected, ,r otary filter performance is described by Holland and Woodham~o as:
F
where ka
= ka V(-APo)a9 T
(10-4)
- Dh Ir(I - X)p, kl
\j
rp
of
Example 10-3. Rotary Filter Performanc~ A vacuum rotary 1ter -is a.ble to
deliver 50 gal of ~trate per min. The depth of submergence is one-fifth' the diameter
eo Holla.nd and Woodham, Exact Calculation Methods ..
,i, .
, 323
CHEMICAL TREATMENTS
of the drum and the spe~d of rotation is 5 rpm. If the resistance of.the cloth and lines
and the variation in pressure drop due to hydrostatic head are neglected, what is the
effect on the delivery of doubling (1) the depth of submergence, (2) the area of submergence, (3) the speed of rotation, or (4) the pressure drop?
The final delivery rate, F 2, is related to the ~itia.l delivery rate, F I , as follows [see
Eq. (10-4):
a~l =
(1 - ~)' or
= (1 97'1
COS-l
aTt
are:
(1 - ~)
%) = %
= 53.1330
aTI
(1 _D2d) 1_~5 = !5
=
= (2
Therefore,
F2
Doubling of the area. of sub~ergeneeJ speed of rotation, or pressure drop, 0.11 have the
same effect [see Eq. (l0-4)J:
F2
= 50
~-2a2'1 =
aTt
50 ~al
al
= 50 ~2AP
-dPo
0
"'" 50 v_ rn2
= 70.7 gpm
Clay Burners.
324
Flue-qos
q"
E/evotors
IIII!
PRACTICE OF TREATING
The ioregoing discussion of the chemistry, fundamentals, and equipment of treating was so involved that the manner of conducting these
processes could not be discusSed. Many arrangements of equipment
Myers and Owen, Economic Survey of Thermofor lnBta.llations , Oil Gal J.:;'
Apg. 4, 1945, p. 93.
"
II.
325
CHEMICAL TREATMENTS
have been successfully used as well as the particular operations. or diagrams shown here.
Natural Gasoline. Even though gas desulfurization as by the use of
monoethanolamine or other agents (see Table 22-4 and Fig. 20-18) is
practiced for the removal and/or recovery of hydrogen sulfide from the
gas, it is still necessary to sweeten the liquid products and to dry the
propane. With especially sour products, the system indicated by M. H .
Rahmes gS (see Fig. 10-7) is extensively used. 97 If the mercaptan content
Mercaptan removal
Coustic
contoclor
Selfler
Mercoplons
10 vent
Depropanize,
bottoms
Propane
to storage
Oebulanizer bottoms
Gasoline'
to storage
(Pet. Refiner.)
326
necessary, but a simple caustic wash suffices for either butane or propane
(see Fig. 10-4). In very large plants the distillation method of dehydrating propane may be used (see pages 234 and 235) ..
Gasoline. Straight-run gasolines normally require only a caustic wash
or a simple sweetening treatment. In caustic washing (Fig. 10-4) the
settler tank can be charged daily (or less often) with fresh caustic and
circulated until it is spent. More often the caustic is regenerated by
removing mercaptans by steaming until finally the caustic is destroyed
by reaction with hydrogen sulfide. Cra.cked gasolines are always sweetened although simple inhibitor sweetening may be all that is required for
catalytic cracked gasolines. If the. sulfur content must be further reduced
Wafer
Sulphur
chamber
,
.'
Raw disfillale
Acid
Sludge
Mixer.
Settler
I - -_ _
~-+-
Plumhite
Con/act column
FIG. 10-8. Continuous acid treating and doctor sweetening of raw cracked gasoline.
D.73.
00.80.
CHEMICAL TREATMENTS
327
gai
One refiner uses this amountl ofor each 1,000 bbl of capacity; The slurry
is prepared in a mix pot or blow case near the reactor. The clay is poured
directly from kraft paper bags into a blow case, followed by the cupric
chloride and then water. The volume of air required 100 by the process is
about 0.5 eu ft per bbl of raw distillate for each 0.01 weight per cent of
mercaptan sulfur. The process is suitable for most straight-run and
cracked gasolines up to a mercaptan content of 0.04 per cent.
The Solutizer process JO 42 "(page" 302). h~ the advantage of removing
sulfur and hence may result in a product having a higher octane number,
an increased susceptibility to the effect of .tetraethyllead, and more color
Etability. The steps in the process (Fig. IO-IOa) are caustic washing,
solutizer washing to dissolve mercaptans, and stripping of the solutizer
solution by means of steam. Contacting is effected by means of a
countercurrent tower packed with carbon ~chig rings, and the process
is completely continuous. It may be applied for the sweetening of any"
type of distillate including cracked, reforme~ or poly distillates. The
ratio of solution to gasoline in commercial plants ranges from 0.1 to 0.2.
The equivalent of three theoretical p1ates is ' used in the" extraction
column and ten theoretical plates in the regenerator. Steam consumption ranges from J.O to 30 Ib per bbl of gasoline [see Eq. (10-:1)].
The Tannin-Solutizer process 33 is almost identical with the Solu" tizer process except that air regeneration as indicated in Fig. lO-lOb is
employed. The fat solution is heated "to 110 to 150F and blown with
gg Schulze and Duell, Control of Copper Sweetening ..
1937, "p. 56.
100 Anon., Oil GfUf "J., Dec. 14, 1950~ p . 107.
oa Gas J.,
Nov. 25,
"
From lurbirle
Live s/f1am ----i--l
ii
~
~'~
15ps/
.--
5
-o!::
~
No.21 O)'6-PO/
I~
..J
Malle-Up
Oroin
Chof'ge
woW
{JfJmp
Needle
. control valve
.Orgln
f
.4J
Orain
Ak "~ter -
''\...Ak chamber
.~-------~
..-
~If'- --~--_
-----------.--,-.
- . --
-IS/on
No.? soil
651bsr'
~.
-------------------------------------------------- _..
"
. .. , .
--------
""'-------- ..
...
Pocked
eolumn
I
I
:;:;:.:>
~
....
\I
~
/\
,Sour
:.gasoline
f
Caustic
:
~pretreater
Sp6 n-htl,.
Distllf"ide oi{s
Con den sa fe
~Ref7w.
Fa"
soluf;on
.. tf
fo'sfor~e
~
i
t:b
.~
0()
c::
o
.;:
settler and
,urqe .rcmk
...
.k
~~---I,J...
:o:t
...
5'" No OH
e~
SolutizeJ"
elC.troctor
Gasoline
separotor
'Heat
(a)
FIG. 10-10. Solutizer and Tannin 'S olutizer sweetening.
system. (Shell Development Company.)
Regenerator
coclliesceJ"
column
(b)
(a) Solutizer process with steam generation and (b) Tannin regeneration
_-_..,"'"-.--
330
air (3 eu it per min for 1,000 bbl per day gasoline) which has been scrubbec'
with caustic soda. The disulfides produced by the oxidation of the mercaptans in the regenerator are separated by passage through steel wool
.a nd by settling. The mercaptan content of the solution must not be
reduced to lower than 0.2 per cent because the tannin must be protected
from oxidation. The cost of tannin solutizer treatment is less than half
the cost of doctor treating, and the main saving is in chemical costs and
steam.
The Mercapsol32.35 and Unisol S I.S5.101 processes are so similar to the
Solutizer process that flow diagrams are not shown (see also page 299).
These processes are especially useful in handling materials of excessively
high mercaptan content but they seldom reduce the mercaptan content
to less than 0.0007 to 0.001 per cent. Accordingly, a sweetening aftertreatment is required to attain 0.0004 per cent (doctor sweet) . . Duruayer
op~rations3. (page 299) may result in doctor sweet products by the
so]utizer-type processes.
Inhibitor sweetening of catalytically cracked gasoline is successful and
economical for mercaptan contents up to 0.02 to 0.03 per cent.n About
5 lb of inhibitor is required per thousand bbl. The final mercaptan
content is usually below 0.0015 weight per cent.
In the removal of. gum from cracked gasolines, sulfuric acid treatment
and vapor phase clay. treatment .were once widely used, but gum inhibitors are now used ahJ~ost exclusively. Only when acid is useful in several
ways, as in desu1furi2._~l.ion plus gum removal plus the gaining of stability,
is acid-treating usef1-Ji. Vapor phase and acid processes have been almost
totally replaced by l';ataly.~ic -desulfurization.
Gasolines, kerosehes~ etc., are sometimes contacted with clay, particularly after acid-treat1rtg 79 for removal of . the last traces of treating
agents, to dry the ~terial" <?r to neutralize the acid (see Fig. 10-11).
The day.is removed - in pressure leaf-type filters. About 1 to 5 lb of
2QO-mesh clay per bbl is required to neutralize the acid.
K~rosene. The quantity of kerosene manufactured in most refineries
is relatively small, and he..'1ce batch agitators are still used by small
refiners.
The batch treatment 'of kerosene varies greatly depending upon the
characteristics of the raw stock. Many kerosenes need only be sweetened; but s.Ome require 3 to 61b acid per bbl, and kerosenes that are rich in
aromatics may require 30 lb per bbl, part of which may be fuming acid.
A typical batch acid treatment for kerosene follows:
1. Agitate with acid 30 min. Often the acid is split into a. small dose of "wa.ter acid,"
and after this is drained, the main acid is admitted.
101
Lyles, H. R.,J . . . New Design Unisol stripping tower . . . ,Oil Gas J., Mar. 7,
1955, p. 126.
331
CHEMICAL TREATMENTS
SUReE
SULrUR
PAUt.4
.3Pv. CENT
.sULFURIC
TANK
DOCTOR
StTTL[AS
ACID
RAW
, I(EROSENt
MlxtA
CLAY
ACID OIL
S'UAC.C
CONTACT
DRUM
AC.ID
SETTL.ERS
nNIS":IED t<EROSEN
tu:Ro. ..
CLAY
TO STORAGe
SPENT CLAY TO
BURNINC PitS
FIG. 10-11. Continuous kerosene treating with doctor solution, acid, and clay.
Gas J.)
2.
3.
4.
5.
Settle ~~ to IH hr.
Spray with water for two IS-min periods, and drain.
Spray with soda and wash with water, 15 to 30 min.
Wash with water 15 min at about 100F.
(Oil
Drain.
naphthene-b~e
crude oils
2.
3.
4.
5.
6.
7.
8.
9.
Settle. Drain.
Three treats of 8 lb each of fuming RtSO.; settle and drain' after each.
3 Ib treat with 66Be acid. Drain.
Three washes with wa.ter, agitating during wash, 15 min each.
Neutralize with 6 Ib of 12BtS caustic.
Settle and drain.
Two washes with water, 15 min each.
II color is. not satisfactory, filter through fuller's earth or agita.te with about 0.4 lb
'of earth.
Sierra., A. V., Better Caustic Utilization, Oil GaS J., June 22, 1953, p. 252.
332
....----!I-I
F'tesh
cousli'C
500;
llnisol
tJl'Ji'1
Phenol
caus/it:
Tonk COl
soles
of all gasoline streams to the Unisol and regenerative caustic units for
remoyal of hydrogen sulfide; caustic washing ~f furnace oil; and a clean-up
treatment at the
treating unit (Girbotol). Fresh caustic
10-12)
is used at the Unisol, furnace oil. and kerosene 'units, but all of the other
needs for caustic are met by the reuse of partially spent ca.ustics.
Cata1yti'cDesu1furizatio~ The development of. these processes is
occurring so rapidly that only a. general discussion of the/three major
modifications discUssed on pages 305 to 307 can be mentioned.
1.
10-1Sa-no hydrogen recycle or make-up (Pereo U and .Gray4'!' processes).
2. Fig. 10-1Sr,..:....hydrogen recycling but no make-up of hydrogen, illustrated by the
Cobalt Molybdate 48 and Autofining 4g processes.
as
the
3. Fig. 1001Sb-hydrogen recycling with hydrogen from outside
Shell HydrosulIurizationl>ll.!OI, Unifining, i!o1 Hydrofinin&, 62,U,104,l0& DiesuUorming, IiJ
a.nd Gulf HDS64 pro-ces:ses.
CBEMITCAL
333
TREATME~TS
The Gulf HDS process employs such high temperatures and low space
velocities that it may be more a cracking or hydrogenation 66 ' process
than the others, and thus fractionation recovery equipment should be
added to Fig. lO-13b when practicing Gulf HDS.
Heater
Feed
lollle/
or
sulfide recovery
60S
...----....
.Gas
separator
(0)
Producl 10 callStic
wash
a slabl7ization
BrNrnv
Healer
I
I
t
I
I
Feed
regeneralion
\:?",
I
I
L_~~~:tases
Recycle
Gas 10 fuel
or
sulfide recov.ery
~~~~------~~---------r-------~
hydtOr;en gas
Compressor
___ .J
I
Hydrogen
make-up
Gas
separator
Product to caustic
wash
froclionation
(b)
FIG. 10-13. Schematic indication of the practice of ca.talytic desu1furization (a) witho)lt
gas recycle and (b) with hydrogen recycle or addition.
Abbott et nl., Shell Upgrades Stock by Hydrodesulfurization, Oil Gas J., July 18,
.
104 Morbeck, R. C., Hydrofining of Middle Distilla.tes, Oil Gas J., Jan. 3, 1955, p. 94.
106 Baeder and Siegmund, Hydrofining Is a Na.tural for Naphtha.s, Oil Gas J., Feb.
21, 1955, p. 122; aJso Zimmerschied et a1., Improving Distillate Fuels . . . , OilGcuJ..,
May 23, 1955, p. 113.
103
1955, p. 92.
334
Ma.terial treated
API
gravity
in crease
tI
Zero
Vi8broken, cracked, OT
coker naphthas
Catalytic naphthas ......
1-4
0.3-1.4 (0.8)
14-27
()-3.5 (2.2)
0.6-6.0 (3,3)
9-11
Per cent
sulfur
reduction"
Notes
90-99 (94)
will be desulfurized or treated in a single operation, followed by fractionation into suitable fractions .. Desuliurization is _so relatively expensive
that it must rely upon additional product improvements as well as
desulfurization, except of course, in upgrading very bigh sulfur otherwise
unsalable oils. In the case of certain gasolines, lead susceptibility and
octane number can be the main advantag~ (Table 10-1). With kerosene
and distillate fuels, the 'advant~ge may be the reduction in sulfur plus
Weber, George, Better Sulfur Removal (Au to fining of 212--662F fraclion), Oil
Gas J., Mar. 17, 1952, p. 169.
10&
CHEMICAL TREATMENTS
335
...-.'
,
336
Refiner ....................
Pounds water acid, 66Be,
a.gi ta. te ~ hr. . . . . . . . .. . . . . .
Hours of settle and draw .....
Pounds acting a.cid 66"B~,
agita.te ~-l hr .............
Hours of settle and dra.w .....
Water wash .................
Neutralized' by .......... : ...
10-13
Distilled
cylinder
stock
Residual
cylinder
stock
I
4
6
8
5
.....
Clay
contact
225
neutral
Pale
oils
Average
oils
II
In
32
4
4
4
2-12
.....
. ....
,
'''Y
contact
4
10-1S"
12-20
9
(150 gal per 1,000
bbl)
Clay
Caustic
2-31
20-60
2-8
Yes
Caustic
contact
is
Sager and Palmquist, Lube Oil Acid' Treatment .. for Italian Refuieries,
Pel.. IUji:ner, June, 1952, p. 139.
108
I
I,
I
1
I
\
r
CHEMICAL TREATMENTS
337
Per cent
treating lou
None
31
25
23
50
14
14
75
110 Contact Filtration, Oil Gas J., Mar. 25, 1943, p. 116.
m New Lubricating-oil-decolorizing and Clay-reactiva.ting Process, Ref. Nat. Gaso.
Mfr., November, 1941, p. 93.
I
r
338-- --
Acid Stortlge
Agitator
"'l
Sludge
to fuel
\System
Contact Sti II
Sweetland
Press
Filtered
Solution
~pentClay
OIL FROM
HEATER
HEATER
KNOCKOUT
DRUM
PRECOAT
frED
CLAY OIL
STORAGE
PRECOAnNG
AND SLUICING
FIG. lO-15. Arrangement of equipment for the Oliver precoat metho4 of contact
filtration. (Oliver United Filters, Inc.)
339
CHEMICAL TREATMENTS
The decrease in loss is doubtless due to the fact that less oil is con tained in
the sludge if the stock is dilu ted. N eu tral oils are usually con tacted wit~
out diluting them, but they must be heated to a sufficiently high temperatun~ to cause them to be :fluid.
The pipestill and vent chamber (Fig. 10-14) of the contact proQess are.
increasingly llO.lll.1l2 being replaced by a vacuum rerun distillation that
light lubricating oils leave the contact process as distilled cla.y-free stocks
and only the heavie~t stock contains clay. Such operations are particula.rly suited to the rerunning of solvent-treated oils which are so free from
asphaltic material that they need not be acid treated but must be further
decolorized. The use of vacuum during the con tacting step is helpful. 1l2
Two manufacturers of microcrystalline waxes from tank bottoms
treated the bottoms with acid, contacted the acid-stage wax with clay by
heating to 700F, and distill~d the oil portions of the stock by vacuum.
The residue after removal of the clay by filtration is a light-colored wax,
but it is not oil-free. Percolation through clay is also used to improve the
color of microcrystalline wa~es. rhe solvent dewaxing (or deoiling) processes of Chap. 12 are necessary in producing high-quality oil-free microcrystalline waxes:
Although the contact process yields excellent products, it may be more
expensive 1l3 than percolation, particula.rly if an efficient clay-burning 8y~
tern is available. However, the cost of installing a complete percolation
system is great, and contacting is probably the cheaper method for a new
instal1ation. In the contact process, the amount of clay that is required
ranges from 5 to 25 per (:ent of the weight of the. oil or Ii? to 80 Ib per bbl.
At leaSt one refiner lH uses spent contact clay as catalyst for catalytic
cracking.
Percola~on. Percolation was the original method of decolorizing
lubricating oils) and until about 1927 no other method of using clay was
widely employed (see also pages 308 to 313). Gurwitsch 115 says,
so
The advantage of filtration consists in the better utilization a.nd smaller expenditure of the adsorbent to produce a given degree of decolorization . . . the oB
comes successively into contact with a great number of very thin Jayers of the
340
In general, for gravity flow, the longer the packed column the greater
the bleaching action, the coarser the earth the less the bleaching, and the
higher the temperature the less the bleaching (other conditions being comparable), Activated bauxite generally has a better decolorizing power 117
on a weight basis, and bauxite has good mechanical properties. The effi..
ci~ncy as a function of particle size
somewhat as follows:
Per cent
Mesh
efficiency
60-90
30-S0
16-30
100
87
CHEMICAL TREATMENTS
TABLE
10-14.
o.PERATION OF FILTERS
Rate of
filtration, Pressur~
bbl per hr fi] tration, 0
for a 1,000psi
eu ft filter
Temp of
filtration,
of
Saybolt
viscosity
Stock
341
"
i
"
. ,~
,
,!
...........
..
S{)-I00
100-140
5-25
5-15
{)-25
0-25
160-200
2-10
15-50
100-130
25 above mp"
25 above mph
30--50
5-20
5-20
~15
5-15
0-15
Pressures in the higher range are required where 60-90 mesh earths are used.
" Melting point.
Proceu of manufacture
342
decolorized by this same clay after it becomes unfit for decolorizing light
oils. Thus the various used clays progress through the plant in a countercurrent maMer 80 that the new earth meets light-colored stocks and the
nearly spent earth meets dark-colored stocks.
Grease Manufacture. In the past, greases were compounded by batch
operations involving inixing and saponifying measured quantities of fat,
alkali, water, and some oil in an open kettle at about 300F. The neutrality was adjusted, and the main oil was -added to ~ut back to the proper
consistency. Now continuous processes 123 124 such as that shown in
Fig. 10-16 are being employed. ln About 1,300 It of fat is charged to
scale tank 1 and pumped to retort 3. About 600 lb of lime slurry containing some lubricating oil, catalyst, and the exact amount of water
desired in the -final grease is mixed in tank 4 by recycling through an
orifice mixer. The slurry is also charged .to retort 3 and the whole mixture is saponified for 30 to 45 min by recycling through pump 7 and
exchanger 8 while being kept at 300 to 325F. .M eanwhile ret~rt 9 is
being charged and retort 10 is being u~d as a charging tank for grease
blending .through the Lancaster mixer 12. After saponification is
completed in retort 3 (30 01' 45 min), soap concentrate is pumped continuously from it and mixed continuously with a. measured quantity of
lubricating oil from tank 13 by ~eaDB of pump 14. The mixture is
blended in the Lancaster dispenser or mixer 12, whIch ope.r~tes at a. ~peed
of 3,600 rpm, and passes continuously to packaging through a filter.
Obviously, other operating conditions are employed for other greaseSj
e.g., sodium soap saponification is conducted at 500F. In manufacturing aluminum greases,124 gel tanks are provided for the blended grease.
Adsorption Processes. At least two of these have attained commercial
significance: (1) ethylene or olefin recoveryl1li12S from cracked gases, and
(2) aromatics recovery by silica gel. 121.128 The use of fluidized adsorbent
charcoal has also been mentioned. 129 It is to be used as a downward
moving bed in which adsorption of the desired olefins occurs in the top
of the column, demethanization of the char occurs as the char moves
113 Houlton, Calkins, _and Beerbower, Continuous Process for Lubricating Greases,
Chern. Eng. Prog., 48, 399 (1947).
uc Houlton, Sutton, and Bevarly, Continuous Process for Aluminum Greases, Oil
Gas J., Oct. 19, 1946, p. 127.
m Berg and Bradley, Hypersorption-New Fractionating Process, Pet Enur., May,
1947, p. 115; Berg, C., Pet. Refiner, September, 1951, p. 241. ..
us Kehde et al., Ethylene Recovery .. , ehem. Eng. PrOfIT., 44. 575 (1948); also
Berg, C., Pet Refiner, September, 1951, p. 241.
127 Davis et al., The Arosorb Process . . . New Refining Tool, Oil Gas J., May 19,
1952, p. 112.
m Anon., Cyclic Adsorption, Pet. Processing, August, 1955, p. 1202.
itt Anon., Gas Separation Turns to Fluidization, Chem. Eng., MlU'ch, 1955, p. 120.
.j
------.
Shurn
I+H.UTW
vl$CO$I-
~Iw"""
1$ hp.J6a1 ~, ..
\.
"
Soap nw/Ukrg
,,
Lmr.
mmr
grwINlo
pi!ld<og.
.\
pump, """lab!.
r.IrWe
.'
~\'F'lhir.
\
\
8tKIt~AUn
.,,~@
all
E-
R.cyeJ.
$tHIp
c;oglc.,.-
15 gal. /img
.fUrry m./)(sr_J~\
riJ'ulr7p
Orlficll
mbtr
\\
\\
(i) Stvam~
~Q(Jd
holding ~ .
In.ultded a ~
6'.1(6'1(1$"' .
pump
150 gpm
4200 gal.
Soap
""'~
()//
hlMtDng kmk
FIG.
10-16. Continuous
m~ufaoture o~
....
OJ/lleat
-.w:irtmgV----:
lime-base greaaes.
\ ,.
Tflmperrrn,q.
rONllng
CiI'Ifrohr
344
PETROLEUM
ENGINEERING
345
CHEMICAL TREATMENTS
TABLE
10-15.
Composition
Hydrogen ......
Methane .... . , .
Ethylene .. .. ...
Ethane .........
Propylene ......
2.23
51 . 55
3.92
Propane ........
11.94
1.60
C.
Ref. ga.s,
mole %
+..........
11.91
25.40
35.46
73.92
.....
0.54
13.24.
0.35
0.33
1.79
3.44
4.42
8.32
... . .
1.47
.....
' 29.35
54.30
39.32
59 .84
0.16
0 . 14
25.18
22.58
61.8
flo
Ethylene
fractionator
overhead,
mole %
1.35
97.11
1.54
11.12
COOLER
SECTION
.i
7(
"rrH~NE
'
ADSORPTION
SECTION
........
.1
~ECTIFYING
SECTION
,,
..,
......
_-
-PUT'
FEED GAS
...
I,.
~)
WNR>
.
r,r---- ---
~,.../
~,/
~--
BOTTOMS
,/
PRODUCT
OUT
~ ...
....:.: r:-:-l
",
..
\,
,
I
1"--8IJrANE
,,
PROPANC--\
1\
STRIPPING
SECTION
:.
'!.
:(
'""-.
~,~- ~~
STEAMING
SECTION
..
PRODUCT
'-.\,
.,,
t
I
OVERHEAD
Q2
0.4
0.6
08
I.D
COMPOSmON, MOl 1,
FIG. 10-18. Composition distnoution in Hypersorber while ~par8ting natural-gas
hydrocarbons. (Pet Refiner.)
346
or
CHAPTER
11
p.44.
347
348
11-1.
ProceSses
Finished lubricating oil:
Conventional treating ...........
Solvent treating .. : .. : ..........
Propane deasphalting . ... . ...... . . .
Solvent extraction processes:
Phenol . . .. , ............. . .....
Furfural ..... . ... . .............
Duo-Sol ........... . ...........
Sulfur dioxide ..................
Others .........................
Dewaxing proe~es:
Methyl ethyl ketone (MEK) .....
Propane .......................
Older eonventional operations ....
19550
Percentage
(approx.)
100
9.5
90.5
175,785
16,600
159,185
.... . .
100.0
36.9
27.7
21.3
5 .8
8.3
100.0
61.5
24.7
13.8-
Number of plants"
(approx.)
Bpd
11
23
45 c
60,4ood
17
199,200
a
.. .. . .
.......
I
14
13
9
3
6
168,OO(
......... .
........
)
........
19
11
41 c
,
t
'
349
l
I
I
I
VACUUM I ~ IDWPHAlT'1
FRACTlONA J ~ ~
INa
T,ION
~~
I~::I
Iffi~ I
I ~g I
Q.
BLENDING
IDewaxed
oil
~ Iught!
DECOlORIZIHG
SOLVENT, ,I
DtwAXING
I 1;..
D
t!
1.x
Reduced crude
".
350
General Processing. ,The position 20. 21 of solvent .processing with relation to the entire refining operation may be seen by comparing Fig. 11_122
with Figs. 6-3, 6-4, and 6-5. Note that rerunning for the separation of
neutral oils, etc., may be eliminated by producing lubricating-oil stocks
of the proper viscosity in the primary vacuum distillation. To some
extent propane deasphalting is being used as an adjunct to vacuum distillation because of the very low pressure required in a vacuum system
to vaporize high-boiling cylinder stock. Yields of 85 to 95 per cent are
common in deasphalting; yields of 95 Viscosity Index oil by single solvent extraction processes are 70 to 80 per cent for Mid Continent stocks,
55 to 70 per cent for East Texas stocks, and even higher for Pennsylvania
stocks. 'The increase in Viscosity Index of the desired oil for the production of 1 per cent of reject oil is much the same 23 for all commercial
solvents except propane. The increase in Viscosity Index for a 1 per
cent rejection ranges from about, 0.4 for high Viscosity Index charge
stocks to about 1.8 for stocks of zero Viscosity Index. The Duo-Sol
process may be considered as a combination of propane deasphalting and
solvent extraction, and hence this process may. be applied directly to
reduced crude oil.
'
The extraction operation proper consists of a series of countercurrent
contacts between oil and solvent as in Figs. 11-8 and 11-9; however, vertical packed towers are more widely used than settling tanks.
The physical proper~ies of the solvent govern to a large extent the general type of processing that must be employed. _ Thus, low temperatures
and high pressures are advisable in handling such solvents as Hquid propane and liqUId sulfur dioxide; the partial solubility and the formation of
a constant-boiling mixture in the furfurat-water system require an intricate distillation system; and the high boiling points of nitrobenzene, furfural" and cresylic acid necessitate the use of a vacuum in the distillation
6f these materials from oil. ,Properties of the principal solvents are given
in Table 11-2.
Only a minor part of the total equipment in a solvent treating plant is
devoted to the extraction operation. Elaborate equipment is required to
distill the solvent (or oil) from the extract and raffinate solutions, to separate the last traces of solvent from the finished oils, and finally to recover
H Armistead, G., Jr., Better Technology Equals Better Lube Oils, Oil Gas J., Ma.y 4,
1946, p. 115.
Sl Smoley and Fulton, Modem Manufacture of Lubrica.ting Oils, Pet. PTocessing,
August, 1947, p. 594.
22 Buthod a.nd Nelson. Encyclopedia of Chern. Technology, vol. 10, p .. 109, Interscience Encyclopedia, Inc., New York, 1953.
U Nelson, W. L., Comparison of Solvent Treating Processes, Oil Gas J., Feb. 10,
, 1945, p. 113.
351
11-2.
HeAt
Boiling
point,
of
SpecHic
Melting
point,
.oF
grav-
ity_
Specific
heat,
Btu/lb
of va. porization,
Btu
per Ib
Solubility in
water,
per cent at
lOOoP
77 F
- - --Furfural (furfuraldehyde)
323
175
-34
1.162
0.416
193.5
. .. . . . .
106
1.045
1.072
1.45
0.53
0.56
0.32
0.37
180
-105
-61
1.222
206
167
116
42.5
-310
1.207
0.51
42
0.844
0.34
0.6
0.47 yap.
0.41
1~
8.5
9.0
(4.0 water in
fur.)
13.1
'2.5
9( co at 151F)
(19 at 32F) 5
1.1 (1.7 at
194F)
183
0.2 10.25
Slight
170
0.07
the solvent from many sources and purify it. Thus, the design of solvent
treating equipment resolves itself to a large extent into the design of
'equipment for the common operations of fractionation, absorption, stripping, etc., by methods tha.t Will be discu.ssed in other chapters. Several
general processing steps are used:
1. Drying or deaeration of the charge stock. Water hinders the action
of phenol, and air is troublesome with gaseous solvents such as sulfur
dioxide.
2. Extraction with solvent. T~e countercurrent method of contacting is
used Universally except for such special cases as the single contact sometimes used in propane deasphalting.
3. Separation of bulk of solvent from oil. This is.accomplished by heating and fractionating or eva.porating. This is usually a simple operation
because the 'Oil. and solvent have greatly different boiling. pOints, but the
separation ot" gaSoline and sulfur dioxide is an exceptio!). ~ vacuum is
used for the highest-boiling solvents, but a simple atmospheric flash suffices for propane.
4. Purification of cn:Z. The oil is freed from last traces of the solvent
by steam stripping or, if water is troublesome, by vacuum ~hing.
5. Purijicatioo oj 8olvent. This may involve the removal of water a.s in
the case of furfural, the separation of solvents from one. another in case
352
several solvents are used, or the separation of tars, etc., as in the Duo-Sol
process.
A discussion of solvent processes is not complete or of much value without illustrations of the properties of the oils that are produced. Nevertheless, space does not permit such a discussion in this book, and hence
the reader must resort to the cur~ent literature and the references given
here.
The maintenance of a higher temperature at the raffinate outlet than
at the extract outlet of an extraction column is useful in propane de asphalting and phenol treating, but the situation with respect to other solvents is not clear. However, in furfural ext'raction little benefit OCCU~S24
(the raffinate has a higher Viscosity Index, but the yield is smaller).
Edeleanu Process. This pioneer (1907) solvent process is the only one
that has been .applied widely to light distillates such as heavy naphtha,
kerosene, and diesel fuel. 26 At the boiling point of sulfur dioxide (14F)J
aromatic and unsaturated hydrocarbons are completely miscible with
liquid sulfur dioxide but the paraffin and naphthene hydrocarbons are
not. The process is used as a means of treating light distillates, but it
cannot be utilized rurectly for high-boiling oils because their solubility in
sulfur dioxide is too low. Lubricating oils can be treated, however, by
using a mixed solvent of benzene and sulfur dioxide. Sulfur dioxide also
extracts cyclic sulfur compounds and nitrogen compounds, a behavior
that makes the process useful in handling certain high-sulfur kerosenes.
The process has been appljed to kerosene to improve the smoke point
and for desulfurization. 26 It is applied to selected naphthas for the recovery of high-octane-number blending stocks and for the recovery of lacquer
diluents (aromatic hydrocarbons).ll Diesel fuels of high Diesel Index
and ignition quality can be made from selected gas oils.
In treating kerosene the stock is first deaerated by exposure to a
vacuum. The kerosene and liquid sulfur dioxide are then cooled by
exchangers and coolers to 5 to 20F 'a nd contacted by coun tercurren t
flow througha tower pa.cked with rings. The cold raffinate and the cold
extract are each passed through their respective exchanger and multipleeffect evaporator systems for the recovery of gaseous sulfur dioxide. The
first stage of the evaporators operates at about 200 psi and at 230 to
270FJ but the last stage is maintained at about 190 mm pressure. The
gaseous sulfur dioxide is compressed and condensed to a liquid.
The amount of solvent used depends upon the stock being handled, but
in general it is about equal to or a little larger than the charge stock.
Reeves and Hardin, Tempera.ture Gradient in Solvent Extra.ction . ' ,' J Pet.
Refiner, January, 1950, p. 8 9 .
.
II Dunstan et &l., "Science of Petroleum," vol. I1I J Oxford University Press, New
Yor~ 1938.
2-'
353
11-3.
FIa. 11-2
FOR
50
Property
Charge
Extract
Raffinate
100.0
25.0
75.0
.......
50 .0
35
35
-15
0.09
0.02
3
169.5
38.2
......
1.25
0.22
78
13.9 4
20 .7
396
394-
444
446
491
493
564
567
614
628
.. Calculated.
The sulfur dioxide-benzene!) process derives much of its value from the
ease with which the solvent caD be recovered and purified. 'The process. ,ing is generally similar to that described for the liquid sulfur dioxide
. process. Sulfur dioxide-benzene may also be employed for dewaxing. 28
Furfural Process. The use of furfural for lubricating-oil manufacture
has been gaining in comparison with most other solvents. The yield of
high Viscosity Index raffinate va.Mes with the stocks being treated but is
about 70 per cent for intermediate-base stocks and 95 per cent for par21
1'1
Dickey, S. W., Edeleanu Process Plant, Pet. Refiner, June, 1948, p. 75.
Wilkinson et al., AromiLtics by S02 Extraction, Pet. Engr. Ref. Annual. 1953,
p.0-3.
sa Anon., Oil Gaa J.,
Deo~
~
...-
._,.
~
dMf01f;Jr
1::
r:=::
" . - cfIOitk
,-..
~~
....
MJOO btId
diN )11
~r
w,.IlI"
75"F
(RalfkIQrr"]
---
-'
l'-l
f- ~
~J~J
f.--,h
I
9t"FI.M"
\)
II
~O.r
lJoIlrclrlr
~SOi'.1 ,-....
H'\.-'h"{
~
'LJ"U
so,
~pumps
F'i
CCIIJcWn$~
208- r _
?rnllrf
woptNV or
.,
------
1
~~
'--
Ft&.
..I'! :\
4:
.......
- .-
pr.SSIIr~
J~I I ~. 1:Z
. ge"~
1"8"~OPl"
~Ior
~I
Il,. ~
~1'
-fttIIw
FIN'*' UItWI
dr
~~ ... ~1'
~~~~~a~~
Jf.
So,.
eo~
:5... 1\1
~~!
I ),,....-----1
LP.
I'roptUfW
I .
.~
'"
..
~~.
~
Wtlpwator
200pllg
FlnWl,tI ro"''''
RAFFfNATF REC()(RY
.
710.
C~
H.p.
3piig
'tJl~U
1~
Y1I
l,,~
60",,,, h9 cIs
~ ,
Wl1fK1'tJiOr .
~
.
r
80p"Q
I'
.......so.-..--,.r------t------.1
c':,
'"":'r: t:...
(I
'_8"Y~
':._ ______
13p,19:--:,1
~I
1. ~
.5""V
--....-~
hl-'-1
l--c ~
l~
{[ Extract 11
roo
SS"F
r
:-2~piIO-': ~j
CINY~t chllI~
--,
~U ~ ~ ~
6790 Wd S'lo
ZI-F
CotrdIItwn
:;'J:;-'~::::;:+;:=:;:::t:;:==l-.
810fl
~olp:
F-'
I---l
l:f
l--c
_ .
~II
F-'
TrrrJfIteg
AIr
SIaJtJt
ItI:IM
lMi-F
IJ
~Co/~frJr
)(1'R,4CT REC{}.IRY
.. ---- ---------~-----------------~
355
affin-base stocks. Yields from naphthene-base stocks are lower (65 per
cent), and the Viscosity Index is necessarily low. 2,26 The general equilibrium relation between furfural and oil is indicated in Fig. 11-10. Tem_peratures of 150 to 250F are employed, but most plants are operating
at about 200F. The amount of solvent employed also varies, but two
parts of solvent per part of oil have been used in many operations.
In Fig. 11-3 contacting is effected in a countercurrent-flow tower, which
lnay be packed with wood slats. A higher temperature is more usually
maintained at the top tha.n at the bottom of the tower, but only a slight.
enhancement of solvent fractionation is attained thereby. 2. The refined
oil mix (raffinate solution) contains so little solvent that it can often be
purified by heat exchange and steam stripping~ but the extract solution
requires a pipestill and atmospheric flashing as well as steam stripping.
The furfural-water equilibrium system involves partial insolubility and
the formation of a constant-composition constant-boiling-point mixture
at 97.9C. The mixture contains 34 per cent furfural by weight. At
room temperature this mixture separates into a furfural-rich solution containing 96 per cent furfural and a water-rich solution containing 8 per
cent furfural. Thus, the constant-boiling mixture automatically separates into ' two solutions a.t the top of the furfural fractionator of Fig.
11-3-and the furfural-rich solution is freed from water in a separate
stripper that receives heat from the hot furfural vapor produced in the
extract distillation.
The use of rotating-disk conta.ctors 29 in commercial operations has been
highly successful not only because of superior contacting and larger capacities but because very quick change-overs of feedstock are possible.
Furfural extraction h~ also been UBed 18,30 for the refining of straight~ gas oil and light and heavy catalytic cycle oils in the plant shown in
Fig. 11-4, and it was used extensively during World War II in the separation of butadiene.31 Solvent treating of cycle oils greatly reduces the
percentage of sulfur and metal contaminants, and produces a high yield
of treated oil which when catalytically cracked gives yields comparable
with those obtained from virgin stocks of the same gravity. The proplerties of taffinates from various high-sulfur or naphthenic oils are indicated in Tab1e 11-4. The extracts have gravities in the range of 4 to
13 API, slightly higher .boiling ranges than the raffinates., and they contain very much more sulfur.
Extraction is accomplished by the use of about an equal volume of furReman a.nd Van de Vusae, Applying RDC to Lube Extraction, Pet. R8fm~T,
Septembe.r , 1955, p. 129.
10 Shelley and Rackley, Better Yields from Cat Cracking, Pet Proceuing, December, 1952, p. 1772.
11 Seymour, H., Furfural in Refining and Purification, Petroleum, Ma.y, 1948, p. 104.
18
.-~IU,"",
Settlin 9
drum
_
...
Furfural-
from water
,~"''''steQm
stnpper
Reffned oil
[x
heater
~
If
-----
_~nlu.""t
Wah.rnr stearn
nIV'"U'\T.
refining
(Te:caco Development
TABLE
11-4.
..
Light cycleCi
Charge
Heavy-cycle
Heavy oycle
Raff. Charge
Raff.
Arabian
cycle oil.
Charge
Raff.
Charge
Raff.
Veneliuelan
cycle oil
Oha.rge
Californian
cycle oil
Raff.
Charge
Raff.
...
42.5
~I .................
31.4
Color, NPA ............. ~ ..... . ,. , .....
Sulfur, wt %................ ~ .
1.10
Ceta.ne number ................
~ Gaavity,
~
Distillation,
73.9
61 .8
40.6
. . ,. ..
" ,.
0.25
......
'"
.........
72.4
.
..........
...
...
66.0
..
...
......
60.0
61.0
37.7 20.2
38.1
24.5
40.4
......
,.
.
.
. .. " ... 2H
I>}
..... '" ... "
" ..... "
1.48 - 0 .49
1. 70
0:45 1.705 0.451
27.3
'"
..
...
"
..
33.6
24.5
7
0.58
60.5
63.0
33.6
1
0.09
.....
I"
37.7
29.7
0.50
65.5
65.1
38.8
0.06
I.B.P ......................
10 %.......................
50 %.......................
90 %.......................
484
605
528
567
E.P ........................ 595
Pour point, ~ .. '.............. +5
Aniline point, C .............. 59.i
460
497
525
';>66
592
+15
79.6
482
506
536
671
478
504
538
725
61.4
484
454
488
544
521
,. . .. " . " . 586
... , ..... . ....... ,. ,. ......... 642
+10
+60
SO.O
60.7
82.5
.....
480
506
557
749
504
454
490
530
590
652
634
716
418
457
543
452
477
561
666
718
436
470
510
580
646
416
458
506
- 580
638
....
a.
r
i
. \
rl
~Jft1~
I I I
i
I
~.
.~
~
:~
,~
,.1_-,
L 1-. ..
.J
~
.~
~
..-:::
'Water
discatrl
Solvent
ext. mix_~.
surge
~"fJ
"8" lowers
decanter
surge drum
'WoII!r
~-.-
Finishedextrocr
.~0Il.
,'\
~ES~E8
359
1D weds,. separator
/
St>1edo
Propans
tJ"'!'1r. ~wyporQIor
",'
Paraif";;lIG
layer
.f~kclo
CO()lel'
Paraflin/c. fo/vent
(propane)
Nap/1lnerlJG SD/lltnl
"(se/eclo)
.
Duo-Sol Solvtlnt
EXtYaction Pro~5~
distill with the furfural. The oil-rich phase (Fig, 114) contains approximately 5 per cent furfural. The water-rich and furfural-rich phases a.re
separated into furfural and water somewhat as indicated in the discus.
.
sion of lubricating-oil treating (Fig. 11-3).
Duo-Sol Process. This is the only double-solvent process that has
been used extensively. One solvent (propane) dissolves paraffinic hydrtr
carbons, and the .other (cresylic acid or "Selecto") dissolves naphthenic
hydroCarbons. The two solvents a.re used in a ~untercurrent system of
Bow, and the feed is introduced at an intermediate point in the How system (see Fig. 11-5). In one end of the extra'ction system the outgoing
cresylic acid solution is stripped of paraffinic material by pure propane,
360
and in the other end the outgoing propane solution is stripped of naph
thenic material.by pure cresylic acid. Thus, a true countercurrent strip.ping operatiQD is maintained, although the extraction is conducted as a
series of countercurrent batch contacting and settling operations. The
extractor is not shown in detail. It consists of nine settlers or compartments. The heavy cresylic acid solution is pumped from one compartment to the next, and the propane solution is also pumped, but in a
countercurrent manner. The feed is introduced in compartment 3 nea.r.
est the end at which propane is introduced.
From 125 to 400 per cent "Selecto(, (based on charge stock) is employed, depending upon the stock, and 150 to 400 per cent pr9pane. In
general, the naphthenic stocks require more propane, and the paraffinic
stocks require more .1' Selecto."2.o Contacting is accomplished at about
85F.
Phenol Extraction. Interest appears to be returning to this process U 33
because of the low loss of solvent that occurs and because of certain
improvements in the processing. The newest3 2 plants employ countercurrent extraction towers, and much of the troublesome constant-boiling
water-phenol mixture is eliminated by contacting the phenolic steam
strippings with the incoming charge stock. Thus, in Fig. 11-6 extract
stripper steam and some other vapors (enough to eliminate currently all
water from the system) are sent through an absorber held at 225 to 245]' "
wherein the incoming charge absorbs phenol from the stripping steam.
Total losses of phenol are said to be under 0.04 per cent of the phenol
circulated. The amount of phenol circulated ranges from about 1 part of
phenol per 1 part stock, up to a ratio of 2.5 for naphthenic stocks. An
increase of 1 in the Viscosity Index requires the production of about 1 per
cent of extract material. At the extremes, a 2 per cent loss to extract for
an increase of 1 in the Viscosity Index of the finished oil occurs when handling high Viscosity Index charge stocks, 1.5 to 1.6 for Arabian stocks,
about 1.0 for waxy California or Mid Continent stocks, and only. 0.5
per cent for naphthenic stocks. Steps in the operations (Fig. 11-6):
1. Heated lubricating-oil stock absorbs phenol from steam, etc. (mainly extract and
raffinate stripping steam) at about" 235F. .
. 2. Stock is cooled and contacted with phenol in a countercurrent extractioll tower.
The bottom of the tower is cooled to about HOF with phenolic water for distillate
stocks or 155F for residual stocks, a.nd the top is kept warm (l50F for distillate
and 230F for residual stocks) by hot phenol.
3. The valuable raffinate (about 20 per cent phenol) is heated to about 550F and
flashed at atmospheric pressure, and it then flows downward into a vacuum fractionn Kenny and McCluer, Refining Pennsylvania Lube Oils by Phenol Extraction,
Oil Gas J., Jan. 16, 1941, p. 48.
33 Nelson, 'V. L. t Oil Gas J., Feb. 10, p. 113, and Mar. 10, p. 78, 1945.
r---------~-l----------------~---~----~~-l
I
Water vapor
oC
fo wash
i.
It
l.'
...
--,
-->I
- ..Ji'- -
_-JI\- _ _ _ , .
I
I
..
I
I
I
.1I
I ,
I
I
L_-+@D-
I
I
r
;=r-s
W~
G-.Jk, . J
I
Phenol
,
Raf'rlnak
mcth-up
Absorber.
wofer elimination
Feed
Phenol Treofin9
Roflinate 2.~coil
sforage towe rtower
still
FIG. 11-6. Phenol solvent-extraction prooess.
Phenolic water
Water and
phe"ol tower
(Oil Gaa J.)
Produm
E~tract
stripper
362
ation tJld 8tesm~ping tower (22 in. mercury vacuum) for the removal of phenol
down ).0 about 0.001 per cent.
4. The low Viscosity Index extract when operating on a Pennaylvani& stock contains
about 85 per eent phenol and 8 per cent water. Phenolic water is removed from it
by heating to about. 6500J' and fractionating in the sma.ll tower situated above the
phenolio wa.ter tower. It passes to stora.ge through a steam stripper which reduces
the phenol to about 0.005 per cent.
Residuum
storage
tanK
tAixer
L.steam
Mixer
Asphglt settleI'
Water
!t ~1rrlJ
l~ I II I 'f
93~
" aaa
Mixer {
Caustic .
1>\ As~halt
pre eater
Gas oil
w
~
..
To Qcld works
deasp~lt.iDg
Fi nished oil
Causficseltler
Caustic
Old
procedure
Fuel oil, gal .......... . ..... :
Steam (live), Jb .. . .......... .
Steam (exhaust), lb ..... , .... .
Electric power, kw-hr ........ .
Acid, lb ................ . ... .
Caustio, lb . ......... . ...... .Acid sludge, gal ............. .
Asphalt, gal ................ .
Slop oil, gal .................
.
......
{.oss, gal . . ................. .
20
2,845
. 395
12
New
procedure
None
1,040
365
None
420
1.5
40
111
21
20
o
1
7.5
TBEA"nNG
4.2
. Ii
365
11-6.
Texas
Reduced crude:
Volume per cent crude .......
Gravity) API ...............
Conra.dson carbon, wt %.....
22.2
11.1
11.3
15.0
, 5.3
21.5
32.3
10.1
20.0
6.3
16.0
22.2
Iron .....................
Copper ...................
489
Vanadium ................
Nickel ..... . .............
Iron .................... ,
Copper ....... ; ...........
Decarbonized oil:
Volume per cent charge ......
Gravity, API. ....... . ......
Conradson carbon, wt % .....
162
237
350
23.1
14.2
18.2
772
.....
62.9
19.0
4.2
294
9.2
1.23
1.10
0.49
............ . .
990
848
84 .1
27.6
13 .2
3.7
61..6
19.9
6.7
0.8
136.0,
139.0
93.0
0.04
35.0
19.3
47.0
20.3
2.6
52.8
18.3
5.3
251
25.5
4.3
193
8.8
..........
7.6
0.73
0.38
1.70
1.88
0.92
0.96
0.03
2.3
8.1
3.5
0.03
0,04
Asphalt:
Volume per cent charge .... . .
Specific gravity ........' .....
B & R soft. point, ~ .. . .....
Per cent of metals rejected to
u.spho.1 t fraction ...........
37.1
1.076
188
97.1
65.0
1.087
142
99.1
53.0
1.059
132
98.6
47 .2
1.119
246
98.2
lation, and (3) solvent extraction with sulfur dioxide or diethylene glycol
(Udex Process)~ The extractive process 19 ,38 most widely used today
employs phenol. A substantially"l--oIe6:n-free concentrate of benzene (or
toluene), obtained by acid treating ~d fractionation, is, distilled in an
extractive distillation column in the presence of downBowing phenol.
Saturated hydrocarbons are distilled, and the aromatic hydrocarbon
remains with the phenol. The aromatic hydrocarbon is ,easily distilled
from phenol, but a solvent cleanup still must be used to eliminate phenoldiolefin reaction products. Each aromatic hydrocarbon must be
extracted one at a time. Mixed cresylic acids rather than phenol are
used for the recovery of xylenes.
aa Anon., Extractive Distillation (Shell D.evelopment
1955, p. 1199.
August,
366
Although theoretical considerations based on pure components are teasonably successful, the application of such generalizations to complex
mixtures is primarily empirical. Extraction . involves two main operations, viz., the obtainment of' equilibrium and a separation of the contacted. materials. Separation is somewhat simple in the countercurrent
vapor-liquid operations of stripp~g, absorption, and fractionation; but
_. _..... ~....extr~_t~Q.lJ. Q~.t~ ~phases are liquids and the d#ference. in liquid ' densities is relatively small. '--.'-. _......
. ..
The general situation is governed by the distribution law, which states
that the ratio of the concentrations of a component distributed between
two mutually insoluble phases is a. constant.
C1 =K
Ct
(11-1)
367
If the solute is 'a mixture, the law holds for each material in the mixture.
Exfrachd
.----Jt'oll-'+-. oil
-c OIIf
SeHling
, fotnk
_.~~...t+I
~xfracf~-
ouf
I
I
IL_______ ..JI
__ - _____ J
! . ./
IL _____ J1/rI'Ktr
or
Yr.'
,
I
I
I
I
I
I
So/yenf
-.
1I
-So/venf
L..f.c,sh
MJlvwnf
YI in
confador
~ers
and settlers .
. solution is called 'the :." extr~~t. ~', ~Jution,- and- the- oil 'or component::rrch' -- -- ..'3olution is the tt raffinate" solution. In Fig. 11-9 the raffinate or oilrich layer is shown as the bottom or, heavy solution. In all common
petroleum-extraction systems the solvent is heavier than the oil and the
solvent-rich extract solution settles to the bottom.
If W represents the pounds of stock to be treated, S the pounds of pure
solvent, x the pounds of component to be extracted per pound of stock,
and y the pounds of component per pound of solvent (Fig. 11-8),
and
The subscript 1 refers to the incoming liquids, and 2 to the outgoing
liquids.
With materials and conditions for which Eq. (11-1) is valid, the equi\ibrium relation in terms of ;c and y may be formulated as follows:
368
K = C1
C2
(11-3)
Y .= K+xK-x
When plotting y VS. x, Eq. (11-3) is an equilibrium curve and Eq. (11-2)
is an operating line. The number of theoretical contacts can be deter~
mined by a stepwise method such as that used for absorption and stripping processes (Figs. 22-9 and 22-10). However, the mjnjmum amount
Solven'" recycle
Solvenf
removal ...........
Extract
produc
Ex/rod-reflux
.
)(".)I)r
X 1001)(
'Of)( >el(
~}C
lOO(
Feed
1(ItX)(J(
Solvent
removal,
I
x,,~
~------'I~--------
)CI(J<J()(
)(11(1("1(
X"lI)(X
)()()(;(l(
1(J(J(K.
OOODO
Solven!
mUKe-up
Roff/nofe
reFlux
I?offinale producl
FIG. 11-9. Countercurrent extraction tower using extract and raffinate reftuxes.
369
used for the design of sett1ers, etc.; but inasmuch as the particle size cannot be estimated without empirical. tests, the theoretical relationship is
of little value~ Horizontal settlers are more effective than vertical settlers
because the velocity is lower.
Extraction of Oils. In most practical extraction systems the several
components are mutually soluble, and hence recourse must be had to triangular coordinate diagrams such as Fig.- 11-10 to show the relation
between phases. Such a diagram has three percentage scales, each of
which reads from 0 per cent on one side of the diagram to 100 per cent
at the apex which is directly opposite. Thus, any point on the diagram
represen ts the percentages of each of the three components of the system.
The phase relationship that is most common for petroleum-oil systems
is also indicated in Fig. 11-10. When furfural (or other common solvent)
is added to a heavy lubricating-oil stock, two liquid phases (or layers)
are produced: one which (extract) contains a relatively large amount
of furfural with some asphaltic material dissolved in it, and one which is
lean in furfural (raffinate) but rich in high Viscosity Index oil. In Fig.
11-10, mixtures of oil and furfural whose compositions fall within the
two-phase region bounded by abc will separate into two layers whose
compositions are shown by the ends of the tie lines labeled i, 2, 3, and
4; but for all other mixtures the three components are mutually soluble,
and no separation occurs. The four tie lines represent experimental data,
but additional tie lines can be estimated as necessary.
In all complex mixtures, such as petroleum, it is difficult to define what
is meant by pure raffinate (R) and pure extract (E), and hence the RE
scale is not read directly in percentages of Rand E but by some significant property such as specific gravity or Viscosity Index. Experimental
data are necessary in order to draw the diagrams.
The diagrams are useful in studying single-contact or concurrent multiple-contact operations (Example 11-1) but are not well suited to the study
of countercurrent multiple-contact extractions.
Example 11-1. Solvent Extraction Diagram. a. Additi~n or removal of solvent
involves travel along a line connecting the pure solvent point S and a solvent-free oil
situa.ted on the base line. Thus, by adding 49 parts of solvent to 51 parts of feedstock, two Jayers will separa.te (see Fig. 11-10) which contain solvent-free oils having
specific gravities of 1.047 (extract) and 0.931 (raffino.te).
b. Quantities may be computed by roaterin.l balances involving either the percenta.ge
c.ompositions or t.he properties of the solvent-free oils contained in the mixtures or may
be estimated graphically by the dista.nces along a line connecting the three materialt
under consideration. Thus, the amounts of the two solutions produced in the ~pa.ra.
tion mentioned above would be sbout equal beeause point e nearly bisects line def,
Point e falls somewhat closer to point!, and hence the raffinate solution designated by
point d is smaller than solution!, amounting by careful measurements or computations
to 48 per cent of the total. Likewise, the amounts of solvent-free raffioate a.nd extract
370
.-0
k-~~~~~--~~60 ~
~
k--J~.-t--.---~~~--~ 0 "'".....A\
~
k-~~~~~~~~-~~~~
Raffinates
Extracts
<19545
L047
Raffinafe . Feed
Extract
FIG. 11-10. Three-oomponent phase diagram a.t 200'T for a mixed-base oil and
fural. (API.)
a.9~1
fui-
be estima.ted by distances along the base line. By inspection it appears thAt the
raffina.te will amount to about 80 per cent of the feed, or more exactly
.
C8Jl
+ 1.047(100 -
R)
Countercurrent multiple-stage extractions u can also be studied by triangular ooordinate diagrams (Fig. 11-11), but apparently an empirical
correction U is necessary when applying the method to oils. In Fig. 11-11,
,which shows the same oil as Fig. 11-10, F indicates the f~ed composition
i.1) terms of various raflinates and extracts. Adding solvent to the feed
traces .the line FJS, and the point J represents 56 per cent solvent. If
the ra.ffinate solution Ra is desired, a line connecting Ra and J shows that
the composition of the extract solution must be E 1 Lines connecting
the raffinate solution that enters any stage with the extract solution leavPerry, J. H. (ed.), "Chemical Engineers' H8.Ddbook," 2d ed., p. 1236, McGr&VtHill Book Comps.ny, Inc., New York, 1941.
"Skogan and Rogers, Stage Estimation in Lubricating Distillate Extraction, Os1
Gtu I., Aug. 2, 1947. p. 70.
41
37J
I\
./
./
.;~
",
""
I \
I r
\
\\
\
\
\
0.94 F. 0.% 0. 98
LO
L02
L04 W6
LOS
.FIG. 11-11. Use of triangular diagram for oountercurrent mUltistage extraotion.
ing
Hunter and Nash, .T, S;Jc. Chem. Ind. (London), 63. 95T (1934).
372
373
used for contacting. Fuqua49 reports that the Kaskade tray has a contacting efficiency about 35 per cent greater .than a bubble tray, and is the
equivalent of about 4 ft of carbon-ring packing. At the same time the
capa~ty is more than 60 per cent greater. Naphtha velocities of 2.5 ft
per min and higher are feasible. Somewhat the same rates of chemical
flow are also possible.
Improved Efficiency in Mercaptan Extraction Using
Trays, Pet. Processing, November, 1948.
4i
Cascade-typ~
Ft-actionating
CHAPTER
12
DEWAXING
by Dr. Paul Zurcher, retired
School of Petroleum Sciences, University of Tulsa
874
. !
. 375
DEWAXlNG
There, is evidence that the distillation range of the ~terial and the
degree of fractionation of the stock influence the type of wax crystals
develolled upon chilling. Davis and Campbell 3 have studied the crystalline structure of 13 fractions of wax oil. The fractions were obtained by
a. true-boiling-point distillation of a Mid Contment wax distillate. The
properties of the fractions are given in Table 12-1. The clean-cut crys-:.
tals appearing in fraction 13 were probably due to decomposition during
the distillation of the last fraction. .
TABLE l~l. FluCTlONS OF WAX
Per
UniFraccent of versal
tion
crude
""t visnumend of cosity
ber
fraction at 100
Temperature,
of, at cut
point, approx.
At3
mm
At 760
mm
Pour
point,
OF
On.
Per
cent
wax by
weight
58.2
40
358
680
60.4 .
51
377 .
62.6
402
420
7.2
9.1
64.8
66
75
89
35
53
4
5
700 .
727
752
77a
789
813
58
9.3
66
76
7.4
10.8
10.1
7
8
67.0
69.2
71.4
73.6
75.8
78.0
9
10
11
80.2
12
13
82.4
84.6
115
152
200
258
330
400
480
470
442
460
478
499
520
541
567
598
625
832
862
886
915
950
978
85
89
95
98
102 .
105
108
9.7
9.2
8.7
9.5
6.8
5.2
Crystalline
structure
of
wax,
'T
Melting
point.
...
None
Few plates
Plates
112 Plates
124 Plates
128 Plates
132 Partly malform
137 Partly ma.lon:D.
Malform
142
145 Maliorm
145 . Malform
145 Malform
149 Plates
96
106.
p .. 49.
376
More recent studies 6 relate crystal structure to such properties as tensile strength,4 hardness,4. gloss,4 and blocking temperature. li Plate crystals have low tensile strengths and needle crystals high, and the strength
of plate wax can be increased by the addition of small amounts of microcrystall11e wax or even plate wax of much higher melting point. 4.
Naturally occurring impurities such as asphaltic matter, as well as
synthetic compounds (Parafiow, etc.), influence the crystal form of the
wax. Some refiners have used additives in order to control the pressibility and sweat ability of waxes. Plate crystals are desirable for the pressing operation, but the needle form is best for sweating.
Pressed disfillcrle-,~
r<'--"""""
nIIJI11!111911111111111111I1UIIIII1--------1:----i'-T-_ _- . . , . . - I.....-
Oil
Ul.'?til~C~f,~f.;,
frough-- ~A~.J
.J-.
---"'---"'1
'f I
r'lax frau
SI"c.f WZ1..r , - - + - - -
1--_ :
'- --"
~J-J--
Swef,T/ pans
Fools O/'l
I.
"-
-_-_J
---E-..::_... -__
- - - --.....,
. I
ReFrtgeraltonr -_ ...
Fi/fer
Petra!ltn wax
Crudesca/e
FIG. 12-1. Old conventional opera.tions of pressing (or double pressing) and swea.ting.
Pressing and Sweating. Although losing in importance, the old pressing and sweating process for the separation of the wax from wax distillate
is still in use. The wax is crystallized by chj))ing of the oil and is removed
in presses as slack wax. The latter is melted, chilled intp large cakes, and
heated slowly. In this operation, called 't sweating," the oil that adheres
to the wax drains from the cake (see ~ig. 12-1).
The double-pipe chiller has been adopted almost exclusively for chilling
wax distillate. This machine is similar to a double-pipe cooler, except
that it is provided with a revolving screw or ribbon-type conveyor in the
Lund, H. A" Meeting Product QuAlity in Wa.x Crystallization, Pet. ProceBBin:u,
Much, 1952, p. 326.
II
Pet.
Tiecije, J. L., A Labora.tory Study of Wax Processing Methods, Proc. Fourth World
C~"
377
inner pipe. T. E. Schley 6 describes a spring-loaded scraper. The purpose of a conveyor is to scrape the wax crystals from the walls and move
them forward. The common size of chil1er has 6-in.-diameter insid~ pipe
and 8-1n. outside pipe. It consists of a series of heavily insulated horizontal double pipes, assembled into stacks through which the oil flows in
series. The conveyors rotate by a chain drive from one motor. Twentyfour sections of chillers up to 40 ft long can be arranged in four stacks,
six sections high, with two chain drives.
Chilling is usually accompli~hed by exchange with the cold dewa.xed
oil, followed by direct expansion of ammonia. Animonia expansion is
cheaper and permits lower temperatures than the previously used chilled
brine. The rate of cooling depends much on the effectiveness of the
scra.pers. If they fit poorly, the rate of heat transfer drops to the low
value of 2 or 3 Btu per sq ft per deg Fahrenheit per hr. With closely
fitting scrapers that remove the wax effectively from the chilled surface,
rates of 16 Btu have been obtained (Table 12-2).
TABLE
12-2. TRANSFER
RATES
, . ' IN CruLLERS
Transfer rate,
Btu/eF, diff.)
(sq ft) (hr)
Type conveyor
Cooling conditioflB
Screw ...........
Screw ...........
Ribbon .. ' .' .....
Ribbon ..........
Brine circulation
Direct expansion
Direct expansion, nonturbulent flow
Direct expansion, turbulent flow, and recirculation
4-5
7-10
8-12
.
15
378
of the press. The wax remains in the space between the blankets, causing an increase in pump pressure until~n'ally a maximum pressure of
about 350 psi is attained. The press is then opened, and the wax cakes
are pushed off of each plate dropping into a conveyor under the 'press.
'The chunks of slack wax then move to a melting tank and are pumped
in liquid form to the sweat pan~ A typical press cycle including charging, emptying, and reassembling",'the press requires approximately 44 hr.
For a normal stock that contains 5 to 8 per cent wax and for single-pres~
ing operation, one or two 48-in. plates are required for each barrel of
Pennsylvania oil that is pressed per day and 2 or 3 plates for a Mid Continent oil. The amount of slack wax that is obtained from the presses
is far greater than the 5 to 8 per cent finished wax and may iJl some cases
amount to 30 per cent of the wax distillate. Oils of two differep.t pour,
points are made by double pressing, which consists of cooling to 35 to
40F and filtering for a high-pour-point oil, and then chilling part of the
oil to -10 to OF for a lower-pour-point oil. In general, the stock should
be chilled to 5 to 10F below the desired pour point for a single-pressing
operation, but for a double-pressing operation the stock need not be
chilled to such a low temperature.
The operation of 8weating consists of cooling the slack wax to a congealed mass and slowly heating it to temperatures of 100 to 140F.
Practice is totally empirical, but a theoretical analysis has been made. 1
T~e wax is heated in long shallow pans, 10 ft or more wide, 40 or 50 It
long,- and sufficiently deep to hold a 5- to 7-in. cake of wax. A flat 'perforated metal 'sheet or a. 5O-mesh screen lies across the bottom of the pan,
-and a pipe coil for cooling and heating Hes just above the screen. The
pans are arranged, one above another, in stacks of about eight and housed
in a buH,d ing or oven. The oven has steam coils and water sprs.ys along
the walls to aid in maintaining uniform temperature condit~ons.
In conducting a sweating operationJ cold water is turned into the pans
up to the screen and circulated through the coils above it, and slack wa.x
is pumped into the pan. Mter the wax solidifies into a cake, the water
under the screen is withdrawn .' and the temperature of the wax cake is
raised at the rate of 2 to 3F an hour by increasing the water temperature. If the wax is in the proper condition, it gathers into well-defined
needle crystals, and the oil sweats or drips from the wax cake. The oil
that collects up to about 100F is called "foots oil," and it may be
resweated along with fresh slack wax. The jntermediate wax oil that is
collected at higher temperatures may contain 50 per cent of slack wax,
and it is often resweated for waxes of intermediate melting point; or it
too may be recycled with the' fresh charge. The melting point of the
crude scale wax is about the same as the maximum temperature attained
7
Bowmap and Burk; Sweating of Paraffin Wax,' Ind. Eng. Chem. 41, 2008 (1949).
DEWAXING
!
1
379
Separa.tion of Wax from Distilla.te, Oil Ga8 J., Oct. 2, 1924, 'po 224. '
P New Sweater. Iml?roves Yields, Lowers Cost, Oil Gtl8 J., July 22, 1943, p. 28.
10 Experimental Control . . . Sweating, Ref. NaI.. Gaao. Mfr., November, 1938, p.
603.
.
11 Dunmire, H. J., Naa. Pet. News, Apr. 23, 1930, p. 38.
8
380
the pressing rate greatly. A poorly fractionated stock may press more
slowly than a well-fractionated product that has a much higher end point
beca.use of the presence of minute quantities of very high-boiling material. Fractionation also affects the centrifuging properties of cylinder
stock. For this reason refiners have sometimes found it necessary to
take a "slop,i wax cut between the wax distillate and the cylinder stock.
TABI.J!l 12-3. PRESSING TESTS
PMssing stock number
31 .2
'iIO
63
66
32
170
366
70
68
450
256
895
81
31.4
31.0
31. 7
280
320
315
IJ4
66
74
42
tiS
50
80
100
75
of:
40 ..... . , ...... . . . .. .
60 ..... . .. . . .. . . . .
60 . ........ ,. .. .....
.... ..
466
416
494
~'13
493
609
394
426
436
4.53
511
498
518
626
461
479
491
541
003
ssg
661
585
1i57
li73
593
490
li24
657
600
611
63~
611i
637
643
844
849
5'l7
li44
70..... .. . . ........... . S64
80 ........... . ...... . .
90 . . ........ ...... .
306
416
SI2
2.56
312
350
344
688
622
648
862
8.75
.'
476
&.76
7.66
118
128
60
48
123
50
-18
-8
-10
63
70
55
57
70
76
9468
Fractionation ........... . .
.... - ...
Crystal formatiOXl . . . . .. . .
Good
',100
859
1.68
119 .
523
513
533
543
562
5M
1180
590
625
618
652 .
835
ri.77
870
4.8
123
39
124
51
33
-6
-8
+8
-5
16
66
68
75
68
74
75
76
66
63
66
68
82
69
100
100
114
1,350
1,380
1,800
1,200
1.400
1,800
0.41
0.43
. ... ...
Good
62:;
US
489
.. . . . . . a
..
Good
0.31
Poor
0.35
... .. ....
Fair
Poorly
Very small
0.4
0 .3
0.45
Poor
formed
DEWAXING
381
FIG.
12-2. Photomicrographs of wax: (a) very good, (b) typical, (c) high end point,
Magnifica.tion X 350. (Courtesy
wax content of distillates is about 6 per cent; but some stocks contain as
little as 1 per cent wax, and others contain as much as 25 per cent.
. Crystal Structure. This is probably the most important factor, but it is
related and dependent on the several other factors that are discussed. A
stock 3 having very good pressing properties is shown in Fig. 12-2a; a.
382
typical stock in b; a stock with too high an end point in C; and one indi"l'
cating that a small amount of crude oil had leaked into the stock dllIinl '
heat exchange, in d.
In the control of plant- pressing operations, the wax oil sh~uld be
examined for at least the following characteristics: (1) viscosity, (2) ,boiling range at 40 mm pressure, and (3) crystal structure.
Centrifuging. Although the 'centrifuge process (Fig. 12-3) was the
exclusive means of dewaxing bright stock for m~i years, it is ra.pidly
being displaced by solvent processes. PeIWlated or acid-treated and
---~
'jji~~i
"
Warm Brine
fa sloragt'
, warm :solution
'
\, Filtered cylinolef'L
5to~k soTufkm
09
-_._---- -
Solvfion
I:: l;
~... .....~1i
,!~\ ~ !t-t-~.
Bri:Jj:J
cooli~!
I ..:/.
,....
___ -- ~--+-r-t
C)
\ ' ~ ~~
r----------------------------~
Q.
I.
p;;;:pr:
.__ :-_~--.J
...
C">
-.35 0
liqt.JidAmmonia
Carrie
, liquid
-25 0
:...15 0
R~pid chillers
'
-5
--.ioO
'"
~ /'E;::: "
T'
....
S ~~
~::"C:
~~ll C~
~~ l
Wafer overf/J
Steam
t~
'~g~ ~~
,
Cij~'"
contacted cylinder stock, diluted with 65 :to 80 per cent naphtha, is continuously chilled in large insulated vertical tanks provided with cooling
coils. W ax-free ~il solution is used for initial heat ex~angeJ followed by
either brine or direct-expansion ammonia chilling. Doubts have been
expressed regarding the established idea that very. slow chilling is 'necessary for successful dew axing, and at least one refiner has disregarded such
precautions with the result that throughputs ate greatly increased. Agi- '
tation of the oil solution during the precipitation of the petrolatum should
be very moderate, since the churning of the solution tends to gelatinize
the petrolatum. This tendency is evidenced by an increased pour test
for slightly excessive or prolonged agitation, and by complete jelling by
very long or very vigorous stirring.
383
DEWA.XlNG
210F.
'
384
The use of two dewaxing methods, i.e., pressing and centrifuging, has
been a source of great expense to refiners. Almost all new plants employ
solvents (Table 11-1). The Weir filter-aid processlll (patented in 1924)
was the first commercial solvent dewaxing process. It involved the filtration of chilled naphtha-oil solution mixed with about 15 per cent of
filter aid (fuller's or diatomaceous earth). Modern solvent processes
employ special solvents, such as acetone-benzene,13 trichlorethylene, 14
ethylene dichloride-benzol (Barisol),lfi and particularly propane 16 and
methyl ethyl ketone-benzol. 17
.
Methyl ethyl ketone (MEK), the most widely used solvent, is used 88
a mixture with up to 70 per cent toluene to improve the rate of filtration
and to ~aise the temperature required in dewaxing. Two solvents (or
three if benzol is also used) are troublesome, and hence the use of largermolecule ketones is being developed.18 Methyl n-propyl ketone appears
to be superior to toluene-MEK solutions, but several other ketones are
also being investigated.
Most recentlylSa urea has been employed. in room-temperature dewaxing.operations. Straight-chain hydrocarbons react completely with urea
forming a large-volume crystal complex which after separation by filtration can be easily decomposed by heating or by the addition of water.
Wax is so completely removed that pour points of minus 70F can be
attained from ordinary lubricating oil stocks .. In the plant of Deutsche
Erdoel A.G., equal volumes of oil, aqueous urea (saturated at 160F),
and methylene chloride (for temperature control) are vigorously agitated.
Heat of crystalliza.tion boils the methylene chloride which is conden~ed
and returned to the reactor to maintain a temperature of 95 to 115F.
The mixture is filtered and the urea-paraffin complex is decomposed at
about 170F by agitation with live steam yielding aqueous urea and
molten wax. Methylene chloride is recovered from both the oil and the
wax by distillation, and the urea is concentrated for reuse. The Standard Oil Co. of Indiana installed a 700-bpd plant in 1956 for the production of transformer oils, refrigerator oils, and special oils for arctic services.
Gee, W. P., Ref. Nat. G~o. Mfr., June, 1933, p. 238.
Gover and Bryant, -Ref. Nat. Gaso. Mfr., June, 1933, p. 222.
14. Pester, C. F., Oil Ga8 J., May 25, 1933, p. 52.
15 Albright, J. C., Ref. Nat. Gmo . Mfr., August, 1936, p . 287.
18 Wilson, Keith, and Baylett, Ind. Eng. Chem' J S8 t 1065 (1936).
11 Porkorny and Stratford, Oil Gas J., Mar. 31, 1938, p. 96.
18 Tiedje and MacLeod, Higher Ketones as Dewaxing Solvents, Pet. Refiner, February, 1955, p. 150.
18G Anon., Urea-adduct Process Gains Ground in Lube-oil Dewaxing, Chern. Eng.,
November, 1956, p. 114.
12
U
DEWAXING
Flue gas
blow
Solvenl
HO~ 1r1t--~~~
filtrate
Wax
coKe
Waxy
Oil
solvenl
mix
Oil-rich
li/lrole
Wox
b:~----~~~~~~-----=:d mscho~~
Chorge
FIG. 12-4. Diagram of a Conkey 8olvent-<iew8.xing drum filter.
of
386
crack easily and are difficult to wash. 'Wilson, Keith, and Haylett 18 overcome this defect by the addition of 0.3 per cent petrolatum which changes
the structure of the cake so that it can be effectively washed. The petrolatum, if undesirable, can be separated from the paraffin wax in a subsequent distillation. Anderson and Talley 19 show that in propane dewaxing
25 to 15 gallons
15 to 10 gallons
10 to 5 gallons
5 to 0 gallons
FIG. 12-5. Effect of wax struQture on filtering rate in propane dewaxing (X 120).
" Rates are gallons per square foot per hour. (Shell Oil Co.)
the mos~ ,easily filtered wax consists of clusters of small grains cern en ted
together by naturally occurring aromatic resins. With this structur'e
-(Fig. 12-5), filtering rates exceeding 5 gal per sq it per hr can be attained.
laboratory rates shown in Fig. 12-5 are about five times as large as
, plant rates. Very fine crystals, forming clouds, may reduce the filtering
.rate to zero. Needles, free or interlaced, are undesirable. The form of
the crystals depends on precipitating conditions, mixing temperature,
The
III
~9,
432 (1937).
DEWAXING
387
F/we
1.. __ _
~
~
~
Col)
;://.
aid.
I
W~beQr;'fg
i:/tRrgtJ
propa e
FIG. 12-6.
Low pres.s(J1"e
causfic
scrtJbber
propane
opane dewaxing.
Slop
Jet
Pefrolf;(lilm
condenser
DEWAXlNG.
389
which is passed to and held in filter feed tanks. The filters are of the rotatingdrum type, in which suctiQn is maintained inside the drum while it dips below the
level of the wax-solution slurry in the filter case.
As the drum rotates slowly the cake forming thereon is washed with cold propane in a. stream of jets. The surface of the wax cake is cut continuotlBly from
the blanket by 8. knife as the drum rotates, the crude wax being conveyed to the
wax tank. Filter pressures range from 3 to 10 psig. If stock is to be deresined
the dewaxed solution is diluted with ODe to five volumes of warm propane, hea.ted
to 140 to 180F, and the resins settled. They are washed with one or two
volumes of propane, .and the solution is depropanized at an elevated condenser
pressUl'e a.nd later a.t atmospheric pressure, A typical dewaxing-deresining 1088 is
about 14 per cent of the charge.
Product improvement is shown for one Bradford residuum in which carbon
residue was decreased from 2.33 to 2J9; color determined by optical density
measurements 28 dropped from I;t.n O.D, of 3,250 to 2,093; most of this color loss
was concentrated in the wax, which showed an O.D. of 11,970. By dereaining,
. the color was reduced to 750, carbon residue to 1.73, and viscosity from 165 S8U
at 210F to 148.
Over-all solvent loss is reported to ra.nge from 0.2 to 1 per cent of that used in
the process which, at the low cost of the solvent, makes this expense nominal.
Control methods are relatively simple and include liquid levels, proportioning .
equipment, a.nd pressure and tempera.ture controls,
The wax con tRins from 6 to 8 per cent oil and is converted into a marketable product by sweating, yielding from 50 to 60 per cent scale wax,
depending on the me1.ting point. In most re.cent practice, the slack wax
is r:epulped at the filtering temperature with cold propan~ and filtered 8.
second time, yielding a wax of the desired low oil content.
Ketone Dewaxing. This process is a development of the benzene-acetone process13 by the use of various mixed s~lvents consisting of benzene,
toluene, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl
ketone, or mixtures of these ketones. 17 The advantages of the lower
molecular-weight ketones are high filter rates and low solubility of wax,
but they have higher vapor pressures and are somewhat soluble in water.
Ketones have very low solvent power for wax but will not hold oils in
solution, For this reason benzol and toluol, which are very good solvents for oils, are added in amounts of up to 70 per cent of the total solvent. For each oil a special blend which possesses a low solvent power
for wax and a high solvent power for oil must be found. A typical mixture for low-viscosity oils is 55 per cent MEK, 35 per cent benzol, and
10 per cent toluol. The heavier the stock the mor.e benzol and toluol
are required. Wax-bearing oils from all sources can be treated.
Weir, Houghton, and Majewski, Ref. Nat. Gaso. Mfr., December, 1930, p. 89.
The O.D. color scale is directly proportional to depth of colo)'. For undiluted stocks,
NPA color equals 1.08(O.D.)o.aa..
18
390
12-4.
DEWAXING PLANT
Paraffin
distillate
InterLight
mediate
motor oil '
motor oil
Heavy
motor oil
Viscosity, Saybolt Universal. ....... 150 at-lOO 250 .a t 100 77 at 210 205 at 210'
Ratio, solvent to oil ....... . .......
1.9: 1
1.7: 1
2.2: 1
3.2: 1
Filtering:
Tempera.ture, of .. , ............ . 20
12
16
25
4.2
Gal dew axed oil per sq ft per lu . . .
6.0
6.3
2.8
Dewaxed oil:
91
92
Yield, per cent ......... . . .- ...... 89
90
Viscosity, ...... , ....... . .... , .. 170 at 100 30.5 a.t 100 86 at 210 230 at 210
Pour point, of''. , , .............. 20
0
5
25
0,001
0.003
Ketone, per cent ...... '. . . . . . . . . .
6.002 .
0.003
Wax:
Yield, per cent . ................. 11"
;
10 '
9
8
Oil, per cent, .... , ............. ;
8
5
12
7
Ketone, per cent ........ . ... , ._.. .
0.001
0
0
0.001
II
The solid point was 5F lower than the pour. point in each of these operations. ' - '
, I
, I
)r
a
~-
~="
U' _
-.
~
~.....
($
'-'
.~
~
!
~
~
~
~
391
1"""1
392
A diagram of the MEI{ process u is indicated in Fig. 12-7. The waxbearing oil and the solvent streams are mixed under control of a ratio
Solvent separation
I
FIG.
8
,9
10
6
7
5
DIILJtion ratio Isolv.: oil)
12-8. Borderline miscibility curves in dewaxing.
DEWAXING
393
394
PETROLEUM
REF~ERY
ENGINEERING
. -c ally- measuring molten wax into pans which pass through a cooling
-chamber on a. conveyor belt to a demolding operation. The other
_. ffi:ethod 30 which can be applied to petrolatum as well B.8 para.ffin wax,
involves a, combination crystallization and extruding machine. The waX
ribbon (1~ in. X '12 in.) is brought to just the right ~emperature for
shearing it into slabs.
CHAPTER
13
FLUID MECHANICS
'
and
":
(13-1)
where API
p
= , pressure
loss, psi
,
= density, lb per ell ft; and 8 = sp_ gr referred to water at
60F
u = a.verage velocity; it per sec (cu ft per sec + cross section
of pipe, sq ft)
L = equivalent length of pipe and fittings, it '
g = "32.2 (lb)(ft)/(lb force) (secP
D = diameter of pipe, ft; and d = diameter,: in.
395
396
J ==
G
1lP, = O.08075fsu 2L
m
(13-2a)
.% IN.
(LARGEST EQUIVALENT
12 IN.
Equipment
Gate valve:
~ closed, .", .. , .......... .
~ closed .................. .
~ closed ............... , .
Open ............... '." .. .
Globe valve, open .......... .
Angle valve, open .......... .
Return bends:
Close ......... " ......... .
Medium radius .......... .
Pipeatill-square ........ .
Pipestill-streamline ..... .
Tee, standard:
Side outlet .............. .
Straight through ... : ..... .
M reduced ....
~ reduced .............. .
Entrance connection ....... .
Couplings or unions ........ .
<
D:i.a.meters
of straight
pipe
8OG-l,100
190-290
39-56
7-10
330--480
165-220
73-104
,39-56
120
.60
66-94
31-44
27-39
18-26
neg.
to
Equipment
Elbows:
Standard .............. .
Medium sweep ......... .
........... .
Long
45 deg ................ .
Square ............ " ... .
Enlargement. sudden: 4
dID %............... .
diD ~ ............... .
dID ~............... .
Contract.ion, audden:4
dID ~ ............... .
dID ~ ............... .
dID %............... .
Welded 90 deg bends:"
RID O.S ............. ..
RID 1.0 ............ , ..
RID
or 5.0 ......... .
RID 2.0 at 4.0 ......... .
RID 3.0 ............. ..
Diameters
of straight
pIpe
31-44
27-39
20--29
15-21
66-94
31-44
22-21
7-10
12-17
7-10
38-54
12-17
1(}-14
9-13
01
at
397
FLUID MECHANICS
Dea""ptlon of fitting
24
20
_n
12
10
en
-.
-
.c
u
c
l&.
17
<:>
t&..
II:
1&1
19 Foot valve
18
c.:
l-
t-
12 Basket strainer
.A:
-z
t . line flow
-..
c:
10 Squaro-edged Inlet
16 Screwed
t.....
:::E
..:
,! ...J/
I
c(
Ik"'~
~
z
15 /
G /
12 /
II
18
3ef
/ e 19
/
13
0 0
20
0.8
0.6
10
1.0
14
0
2
8
<:>
7
'0
21
<:>
e
0.3
FIG. 13-1. Frictional resistance coefficients of pipe fittings [see Eq. (l3-2b)J.
Proce88ing. )
0.1
(Chem.
Van D even ter 1 states that for flanged fittings the equivalent lengths
should be decreased by factors of 0.75 to 0.96. Equivalent lengths for
viscous or streamline flow are so small th~t they are usually neglected. 2
I
I
-I
J
398
PETROLEUM REFiNERY
ENG~EERING
Fanning's equation isnot valid for the flow of gases if the pressure drop
is more than 10 per cent of the downstream pressure.
Another means of determining the friction loss through fittings is indicated 3 in Fig. 13-1.
u2
(13-2b)
11, = K 64.4
in which h is the pressure drop in feet of fluid and K is 3. resistance coefficient (Fig. 13-1) which .depends upon the kind of fitting and its diameter.
The relationship between friction factor and the Reynolds number
DG/~ for isothermal systems is shown in Fig. 13-2. and Keevil and
,,,
r JI I I
t:.A= 21 ~
I
144qOp
.llf} =~'SSure /0
I
= O.32Jlsu-t
EQ.(30)
~~
I=:;Friclion Ioclor
.,
~ PSI
f--
g=32.2
L=quivoJen/ /eng/h,
D=DiomeJer, II
d=[)iome/er, in.
q=Disc/JoJge., 901 per hr
p=Viscosi/y, english 'um7s
Z =ViscosJiy, cenlipois~5
I".;
"
II
I'-':.~
,...
Commercial steel
Ot' iron pipe
"T"n-Y--
r--
r-
4
_l ~
J
2
Zero--. Always
0.001 ~
10 .
Slre{JITIJi()~
I ItilillIcY
J"
T-urbulelll Hoit
J
2
o
copper, bross,
polye/hylene, eIC. lubing-
n;c1te~
,"-
11 11
4 5
'10"
n'Byno ciS
IJQllfU
4 5
10.5
4 5
10~
5.2..7705
iI
I
McAdal,llS4 have determined the effect of heating or cooling on the friction factor. The relationship has been repeatedly checked using a wide
variety of materials, including water, air, natural gas, steam, oils, and
solutions, and even the many empirical formulas of flow, yielding friction
factors that are in close agreement with those of Fig. 13-2. The value
of DG/ ~ when pumping natural gas in commercial lines is so high ~ that
the friction factor (O.0033-{).0045) cannot be read from Fig. 13-2.
Condition of Pipe Surface. The friction factors shown in Fig. 13-2 are
for commercially clean new pipe .and are smaller than those usually
a Coefficients of The Hydraulic Institute, Pipe Friction Manual, New York, 1954j
and Nomograph by D. S. Davis, Chern. ProcesSing, November, 1955, p. 226.
4 Chem. Met. Eng., 38, 484 (1929).
I. Berwald and Johnson, Factors Influencing Flow of Na.tural Gas . , U.8. Bur.
Mim8 R~pt. Inve8t. ;il53, 1931.
. \
399
FLUID MECHANICS
obtained in practice. The smaller the pipe the .greater is the effect of
the surface in increasing the friction loss. For very large pipe the condition of the surface may be neglected entirely. The friction loss in old
or corroded small pipes may be twice as grea.t as for new clean pipe.
The factors shown in the following tabulation were published by F. L.
Snyder. 6
Correction factor for
condition oj surface
r-/.'
400 r--
~- -
.~
-I f-
01100
t-200
~ 200 ~
-<:::
~
70 I---
40 r--
f----,-
~
~
~
~
.<::!
~
_.
stG ~ I-- -
""
r:--.,~
l1*
..........
==
~r-.
7 I---
r-t4 r--
f--
J:I~
f--
<J<l
I--- f'L
~ ~~
..
f'a
10
"- -.............
50
t-..
t--
~,
20
'"
100
~
-
2.5
,.
k::! f-~_-'OOO
1000
~ 700 t:;;;-2= t--500
'G
r-
.t:)o
0.9
1.0
1 .2
1.4
1.6
2.0
2
I
Zero
""
(rOle
I
104
r-.,
sere fel~
2
10 2
"1.0
pipe.
400
bulent flow. The left scale of Fig. 13-3 designated as APTP / llP L - is the
ratio of the pressure drop for two-phase flow to the pressure drop that
would occur if only a liquid were being handled. H;owever, the It all1iquid" pressure drop is hypothetical because it is based on the total mass
flow (liquid and gas) rather than that of the liquid portion, but on a friction factor based on the physical properties of the liquid alone.
TABLE 13-2.
PIPE,
INCHES
Outaide
dia.m.
Sched. Sched. Sched. Sched. Sched. Sohed. Sched. Sohed. 8ched. Sehed.
20
30
40
100
10
60
120
160
140
80
---.........
3).2
0.405_
0.540
0.675
0.840
1.050
1.815
1.660
1.900
2.375
2.875
3.5
4.0
4 ...........
5 ...........
6 .........
8 ...........
10 ..........
12 ..........
14 o.d ..... _.
16 o.d .......
16 o.d ..... _.
20 o.d .......
24 o.d .... , ..
30 o.d .......
5.563
6.625
8.625
10.75
12.75
14.0 16.0
18.0
20.0
24.0
30.0
3-;l ........ ,
!J9. , ....
.........
~ ....... -..
1 ...........
1~ ...... ,
1~ ........
2 .. , .
2~ ....
3 ... "",,1',,,
4.5
II
III
...
til
..
II
..
....
....
....
'I
...
...
II
"
..
..."
......
........
.........
-{). 250
0,250
0.250
0.250
0.250
0.312
0.250
0.250
0.250
0.812
0..312
0.312
0.375
0.375
0.500
0.1" O.82J
0.307 0.8811
0.330 0.406
0.375 0.427
0.375 0.500
0.437 0.562
0.500 0.593
0.562 0.687
0.625
..
....
0.406
O. SOO
0.562
0.593
0.656
0.718
0.812
0.937
--
0.09S
0.119
0.128
0.14.7
0.1U
0.179
0.191
0.100
0.218
0.2'18
0.300
0.318
0.337
. .....
....
. . . .. . . ....
. ....
. ...... ..... . . ......
. . . . . ..... .
.., "'"
. .....
. .......
... . .
....... ....... . ........
0.187
0.218
0.250
0.250
0.281
0.343
0.375
0.4&7
0.487 . ....
0.500 ......
0.562 . ........
0.718 0.812
0.843 1.000
1.000 1.125
1.062 1.250
1.218 1.437
1.343 1.562
1.500 1.750
1.750 2.062
0.531
0.625
0.718
0.906
1.125
1.812
1.406
1.562
1.750
1.937
2.312
......
. ......
. . " ....
..
.. .
......
0.3'15 .......
0-.'82 . . " ..
0.500 0.593
0.593
0.687
0.750
0.843
0.937
1.031
1.218
a"
0.718
0.843
0.937
1.031
1.155
1.250
1.500
.....
......
Thioknesses shown in boldfa.oe type in Schedules 30 imd 40 a.re identioal wit.h thicknesses for Standard
pipe in for.mer lists: tholle in Schedules 60 a.nd 80 a.re identical with thicknee!1e8 for Extra Strong pipe in
fonner list8.
The decimal thiokneasea listed for the respective pipe eizes represent their nominal or average wall
dimen91ons. For tolerancea on wall thicitneMeB, see a.ppropriate material specification.
The effect of the amount of vapor and the effect of the physical properties of the vapor (and liquid) are introduced by means of the parameter
PL +0-/ PGW"Y in which PL and po are the densities of the liquid and vapor,
and wG. and '.ItL. are friction factor functions described by:
and'lrGa =
JG-L/ D + T.K
401
FLUID MEC1iA.NICS
isks a.re used on the fTietion factors f Land fG to indicate that they are
based on the total mass (liquid and vapor) How but on the physical properties of the liquid (or of the gas). Moody friction factors are used, and
these are ,four times larger than the factors of Fig. 13-2. Note especially
that Fig. 13-3 applies only to isothermal systems, and it therefore doe~
not apply rurectly to a system, such as a pipestill heater, in which a change
of phase occurs.
TABLE 13-3. STANDARD CONDENSER TtmE DATA
'.
O.d. of
tube. in.
No.
gauge,
BwS
18
20
0.238
14
16
18
0.64
0'.514
0.396
12
14
1.12
0.88
0.700
0.540
18
1M
per
linear
ft,lb
0.520
0.421
0.326
14
16
16
l}i
Weight
10
12
14
1'6
18
10
12
14
ThickDeM,
in.
Surface outalde,
eq It
I.d.,
. in.
Per
linH
Per
liD in.
Surfaoe
inaide
per
linear ft,
sqrt
Velocity
Inside
(pr 1
sectional
gal per
a.rea
per tube, min, it
Bq in.
per sec
0.088
0.065 '
0.049
0.085
0.459
0.495
0.527
0.555
0.16362
0.16862
0.16362
0.16362
0.01364
0.01364
0.01364
0.01364
0.1205
0.1299
0.1382
0.1455
0.165
0.193,
0.218
0.24.2
1.98
0.083
0.584
0.620
0.652
0.1008&
0.19635
0.19630
0.01687
0.01637
0.01637
0.1530
0.1627
0.1706
0.268
0.302
0.334
1.20
1.069
0.9617
0.782
0.884
0.870
0.902
0.26180
0.26180
0.26180
0.26180
0.02179
0.02179
0.02179
0.02179
0.205
0.2183
0.479
0.5463
0.595
0.638
0.67
0.586
0.540
0.503
0.982
1.032
1.120
1.162
0.82108
0.32708
0.32708
0.32708
0.32708
0.02725
0.02725
0.02725
0.02725
0.02725
0.258
0.271
0.284
0.2935
0.3020
0.757
,0.680
0.134
0.109
0.083
0.065
0.04.9
1.045
0.424
0.385
0.347
0.3262
0.3075
2.110
1.75
1.36
0.184
0.109
0.083
1.232
1.282
1.834
0.3925
0.3925
0.3926
0.03275
0.03275
0.03275
0.8287
0.3382
0.3500
1.195
1.292
1.400
0.2688
0.24.88
0.2298
1.73
1.44
1.12
0.S90
O.oas
0.049
0.109
0.083
0.065
0.049
1.084
0.2279
0.2360
0.838
0.923
0.985
1.633
1.472
1.328
402
PETROLEUM REFINERY
ENG~ERrNG
Strong pipe which have long been used. Ten schedules or weights are
available (Table 13-2); the boldface numbers indicate the old Standard
pipe (Schedules 30 and 40) and the old Extra Strong (Schedules 60 and
80). Double Extra Strong classification has been dropped completely.
The schedule numbers are approximately equal to 1,000 times the internal
pressure (pounds per square inch gauge) divided by the allowable fiber
stress (pounds per square inch). An enormous number of sizes of pipe,
tubing, casing, line pipe, etc., as well as Standard pipe are available.
Some of the more common tubing sizes are shown in Table 13-3.
Example 1S-1. Friction Loss in an OU Line. One thoUSB.Ild six hundred gallons
per hour of 8. 15 API (3 - 0.966) fuel oil at a temperature of 200F is to be pumped
through 8. distance of 1,700 ft in a 3-in. (Schedule 40) well-insulated pipeline. Two
open gate valves and six elbows are in the line, and the oil enters a tank through a
sharp-edge entry flush with the side of the t&nk. The Saybolt viscosity of the oil is
300 at 210DF. What is the tota.l friction lOBS .i n the line? Assume no change in
temperature.
The viscosity of the oil at 200F (Fig. 4-43) is approximately 80 centipoises. The
specine gravity a.t 200F (Fig. 5-14) is 0.916. The 1,600 gal is the volume at 60F.
.
0.966
Volume at 200crp = 1,600 X 0.916 = 1,688 gal per hr
1,688 X 231
Velocity"'"
(3.0:)~~ 3.14 X 1~ =
4.6
6.14
7,738du8
= 7,738
::z
329
o,c J
p81
403
FLUID MECHANICS
EX8IDple 13-2. Friction Loss in Vapor Line. Fourthousand pounds per hour of 8
55 API naphtha vapor at a temperature of 300F passes through a. 4-in. (Schedule
40) vapor line that is 130 ft long. The molecular weight is 110J and the pressure is
5 psig. Wha.t is the pressure drop't
Volume of vapor
\~
X 379 X
~:
!!:;
=r
15,000 en ft per hr
Then
. 300
460
Reduced temperature - 675 + 460 = 0.735
Reduced pressure = 20/415 = 0.048 spprox.
Reduced viscosity (Fig. 5-16) = 0.34 approx.
Viscosity = 0.34 X 276 = 93.5 micropoises or 0.00935 centipoiBes
Speeific gra.vity
= 15,~O~ 62.4
= 0.00427
=8
15,000
144
u = 3,600. X 12.73 - 47 ft per sec
7,738dus = 7,738 X 4.03 X 47 X 0.00427 = 640000
Z
0.00935
J
J = 0.0044 (Fig. 13-2)
.. D
""" 0.323 X 0.0044 X 0.00427 X (47)2 X 130 = 0 A'>
.Ll.l J
4.03
."2:\J pSI
where llh.
llP.
8
(Ull - "Ut)2
~---:::--~
2g
or
(13-3)
"U2
Ul
AP.
= O.OO673ksu:
(13-4)
:404
motion.
u2
2g
or
0.OO673su J
(13-5)
1""-
~.
"
'"
.3
'"
.2
Q.1
1\\
r\
subtracting the energy of the low-velocity stream from that of the stream
at a higher velocity; and, i( the specific gravity does not changeJ
IlP
= O.00673s(u~
- u~)
Ratio
APe
~f ~:
~:~:
= 0.116
;;a
0.299 psi
b. The oil then .flows back to a. 3-in. pipe from the i-in. pipe. What is the loss in
pressure?
. :> U,2 - 9.95 (upstream)
Ul = 0.116 X 9.95 - 1.15 ft per sec (downstream)
AP. =0.00673(9.95 - 1.15)1 X 0.966 = 0.503 ~
FLUID MECllANICS
405
Weirs. In refinery design the two most important weirs are the rectangular or suppressed weir and the V-notch weir. Both are used in the
design of the overflow dams in bubble towers. The formula for flow over
a rectangular weir is
Q = 3L(h)~'
\
(13-6)
= 1.155L(h)%
(13-7)
.+ 2; (velocity head)
u:l
(13-8)
Each item in Eq. (13-8) must be expressed in the same units, Le. ; feet of
head or pounds per square inch, etc. The relationship among pressure,
feet of head, and specific gravity (or API) is given in Eq. (10-3) .. The
hydraulics of withdrawing side-draw products from fractionating towers
is discussed by Nelson. 10
E%ample 13-4. Hydraulic Energy Balance. A tank of water at 150F (specific
gravity 0.980 1 viscosity 0.433 centipoise) is discharging through a standa.rd 2-in. pipe
system a.t the rate of 120 gal per min by its own hydrostatic head. Figure 13-5 indica.tes the pipe system. What is the height of the wBtter above the discharge point?
In this problem the only energy input to the system is the difference in the static
head (X 4 - Xli). This energy is dissipated as friction losses in the pipe and fittings,
in the entrance to the line from the tank, and 88 ~tic energy iIi the fluid as it flows
from the end of the p i p e . '
.
sO,Tower Hydraulics, Oil Gaa J., Sept. 15, 1945, p. 119.
406
/ooor----------------------T
5=0. '5
!i!~ 0.433
----------------r!
~J he valve
::
aiO
'
1-
~1
~
k---". ----------------------- 60
J -- -- - -- -- - - - - - - - --- - ---- -- -
:I
--~
~-1..
150~
120 X 144
7.48(1.035)2 X 60 X 3.1416 = 11.5 ft per sec
164.7 ft
Friction factor for new, clean :pipe - 0.0046 (see Fig. 13-2):
6;~43 xXO~::5
.
PSl
+ 1.025 + 36.1
= 39.2 ft
Hy~raulics
PLUID MECHANICS
REFINERY APPLICATIONS
/
If
6.0
!).o
~ ...
Ii
g
~
~I
D-
o0:
a
UJ
0.9
0.8
0.6
O~
0.3
:l
0:,
IL
0.2
O.lll
1/
II I/J /
jf
'f
JVj
,'1/1r[,
~
11../
I
L '- '-~
I ~
~
I[I
0.7
0.4-
/ I
1.0
a:
'-
/, J
I I 11--' I
l; ~~{~V
z . I.,!,
ffi
If I
/1 'I IJ 'I~'[ 1/
If /
/
/
V V II I, 'Ii f J
I
2,~
1~
/ LI I / II V
I
'I
.3.'"
L lL
All
a:
J '
7."
1.
'- / -'-
/ /
1,
11/
1/ JIJ
1
/
I IL L
I II
V II/~ I}
/ L Vi I Vj VV
V VVI
j
/ I ~~V
1'-
VI
/ I II VI VI/ V,'/
II
IA~I~
EQUIVALENT LENGTH 100 FT.
CASC. -59A.P.I.
TEMP.-300F.
18 LB. ASS. PRESS. WE.)
'5
20
30
40 .50 flO 70
1)0
I!O
2 00
300 4 )0
600
BOO!I)CO
FIG. 13-6. Pressure drop through 100 it (equivalent length) of va.por line.
59 API ga.soline at 300F and 18 pam. (Oil Om J.)
Based on
etc., of the fluid. The pressure drops through exchangers and pipestills
are,so specialized that they will be discussed in Chaps. 17 and 18.
Vapor Lines. Approximate pressure drops through topping plant gasoline vapor lines are given in Fig. 13-6, and the same data have been published l! as a function of the number of pounds Howing. They niay be
Nelson, W. L.) Oil Gas J., Mar. 30, 1944, p. 90; Nov. 4, 1944, p. 73; and Dee. I,
1945. 1'. 75.
11
408
applied to other vapors by multiplying the pressure drops from. Fig. 13-6,
by the following factor:lt
. Ii' '. 0 4 MP
M u 1tIP
(13-9)
er = . T
The general formula u for all kinds of vapors at any
sure 18
temperatur~
or pres(13-10)
..
'
Vel OClty
-~ v ..
".
: ~.'
..
_~
47 ft
15,000
144
= 3 60Q X (4.03)2 X 0.785 =
per see
j
.,
According to Fig. 13-6 the pressure <hop per 100' ft is 0.295 psi
Jli' ""'" 0.295 X
13 ~ 00 ""'"
0.383 pai-
58.5
TW.t
58.5 X (300 + 460) X 4,000 X 130
.
108 X 110 X (5 + 14.7) X 4.03' ""'" 0.396 pm
AP = 108 X MPd' =
These values cheek reasonably well with the 0.43 psi of Example 13-2.
Enur.,
409
FLUID MECHANICS ,
a number of branches from the main vapor line. The fluid splits itself
into the several branches, and the pressure drop for the entire box is the
same as through anyone of the branches.
Line Sizes. Refinery 8team lines are relatively small and flow rates are
Dot uniform, and hence lower steam velocities (larger pipe) are used than
in power plants. It is poor practice to use velocities in excess of 800 to
11900 it per min for- each inch of diameter,16 although for short lines
-, (Under 300 it) values of 1,000 to 1,200 may be used. Velocities in re~ery
steam lines are shown in Table 13-4.
TABLE 13-4. VELOCITY IN REnNERY &rEAM LINES,
Very
long lines
Regular or
short lines
2~
1.500
1,900
2,200
3 '
4
3,600
1,800
2,300
2,700
3,400
4,400
Nominal
pIpe BlZe
"
13-2
2
III
2,800
FT
PEB MING'
In sizing water lines the head loss is usually limited to 2.5 it of head per
100 ft of pipe,la which means velocities of about 1.5 ft per sec in' I-in.
pipe, 4 It per sec in 5-in. tubing, and 5 ft per sec in 14-in. pipe. There
is also a, t.endency to limit the velocity in larger lines (4 in. and up) to 4
or 5 ft per sec.
TABLE
13-5.
ApPROXIlIATE
SloS
OF
ao
Centistokes
l~
10-30
300
500
108
........
1,000
1,500
216
324
100
II.
..
......
...
.....
..
to
..
2 in.
in.
2
8
20
65
50
LINES (LIQUID)
Oli
to
..
........
2~
2(}-50
40-80
15-40
30-60
20-55
5-35
. To 25
II
......
to
. .......
.......
3 in.
4 in.
60-140
50-120
40-100
35-80
30-70
To 4
140-260
in. ,
15-40
10-30
..
.....
......
II
...1
..
..
100-240
80-200
70-180
60-160
40-120
To 80
'Table IJ-:5 indicates coJIUi:ton ' r~finery line sizes based on heads of 1 to
4. ft per 100 ft of equivale~t line length (0.025 to 0.12 psi per 100 it).
Obviously, this table does not apply to long lines such as crude or prod-
410
uct pipelines,17 not does it apply to pump-suction lines 18 or to main process lines. Customary velocities in pipes till tubes are shown in Table
18-5, and velocities through exchangers are discussed in connection with
Figs. 17-11 and 17-12.
Very viscous or low gravity crude oils cannot be economically handled
by pressure alone, they must be heate~ and sometimes diluted. lD The
maximum feasible viscosities for handling viscOUB oils at room temperature are about: u
Line size
SUS at l00F
4 in.
6 in.
.10 in.
20 in.
400
1,000
2,000
0,000
13-6.
API
gravity
With ease
100 SUS&
/I
500 SUSb
2,000
SU8~
3,300 SU&
10
300F
215 F
168<>]'
11
12
285
270
255
240
225
200
155
141
185
173
140
128
115
127
13
14
15
16
160
146
135
214
17
18
19
202
190
20
162
On..sra
155~
115
103
104
125
112
176
Nelson, W. L.,
~mping
Punip Selection. Space does not permit a discussion of pumps or. even
a complete discussion of their service cbaracteristics. 20 Asphalts or 8emiNelson, W. L., Sizing of Refinery Oil Lines, Oil Gas J., Oct. 18, 1947.
18 Nelson, W. L., Oil Gas J., Aug. 2, 1947, p. 93, a.nd Aug. 30, 1947, p. 103.
10 Nelson, W. L., Pumping of Cold Viscous Crude . . . , Oil GlU J., June 6, 1955,
p. 143; and Nov. 15, 1954, p. 269.
~ Nelson, W. L., Oil Gaa J.: (selection) July 26, 1947, p. 287; (suction lift) Aug. ~,
1'f
FLUID MECHANICS
411
solids are handled with reciprocating steam pumps because they CWl, up
to their limit, develop full pressure and can sometimes dislodge even solid
material from the line. In handling large amounts of medium...viscosity
oils, centrifugal pumps may be used. Centrifugal pumps are widely used
for boiler feed because of the smooth flow, ease of automatic regulation,
simplicity, ,and small space required. Ie Blowing" or II puffing" of burners
is avoided by the use of rotary pumps for circulating fuel oil. Cargo loading of nonviscous :fluids is handled largely by centrifugal pumps because
of their inherent high-capacity low-head characteristics, but more viscous
materials may be handled with rotaries. Circulation systems such as those
used in blending of ethyl fluid into gasoline or certain treating plant operations are powered with centrifugal pumps, although asphalt requires
rotary or reciprocating circulation pumps. Rotary and very small
plunger pumps are used for chemical feeds. Spray pond water, coolingbox water, cold-oil charge stock8, and reflux are examples of cold generalservice operations that are usua.lly handled with centrifugal pumps.
Centrifugals are safer th~ positive-displacement pumps because the discharge line can be c.losed wiih'out bursting valve boxes, blowing gaskets,
etc. j ,they can be repacked while operating (on cold materials) j and their.
ca.pacity or speed can be regulated by the use of steam turbine drives.
Multistage centrifugal pumps are .widely used for hot-oil high-pressure
low-capacity services such as charging cracking plant pipestills, because
of their relatively low cost, low space requirement, light foundations, and
a nonpulsating flow that simplifies the maintenance of instruments,
valves, lines, and fittings. Two centrifugals, one for acid and the other
for soda, driven by a common prime mover, are now used almost exclusively for fQamite fire 'smothering. Centrifugals fill the lines quickly, and
they can be built cheaply of cast iron ~d can easily be flushed with water
to remove the chemicals. FuUer's earth, clay, etc., slurries are handled
by centrifugal pumps by feeding wash oil to the stuffing boxes, but
reciprocating pumps or very cheap rotary pumps are employed for the
worst combinations of temperature and abrasion so that worn parts can
be replaced at little cost. Volatile fluids are handled by submerged-type
centrifugalB, but largest suction lilts are obtained with close-clearance
reciprocating pumps. The reciprocating, or plunger pump is standard
for extreme high pre8sure, although small rotary purp.ps can provide 2,500
psi in some services, and multistage centrifugal pumps are occasionally
used at 1,000 psi. Centrifugal pumps are widely used on loading rack8, .
in bulk stations, and in small blending operations because the discharge
line can be closed while it is being transferred from one container to
another. Remote' push-button control can be employed. H In-line"
1947) p. 93; (priming) Aug. 9, 1947, p. 111; (serVices) Aug. ~, 1947, p. 133; (vacuum)
Aug. 30, 1947, p. 103; and (viscosity) Oct. 25,. 1947
412
' ..
centrifugal pumps are available which can be set directly in the line
avoiding loops, bends, and pipe ~ration.
Suction Lift of Pumps. Figure 13-7 serves "to illustrate pump suction
conditions. The maximum lift that a pump can produce is equal to barometric pressure less the vapor pressure of the liquid. The customary Reid
vapor pressure is not usually satisfactory because the small amount of air
or gas dissolved in oils often causes the true vapor pressure to be 3 to 60
per cent higher (Table 4-12) than the Reid vapor pressure. In addition,
the pump must lift the suction valve against its spring, which seldom
ljiijr-Suclion valve
Atmospheric .
pressure
!~!!!+
atmospheric pressure
In handling. volatile liquids, or liquids tha.t are boiling, the f9110wing low
. piston .speeds are recommended :21
21
Nelson, W. L., Vacuum and CloSe Clea.H.nee Pumps, 'Oil Ga.a J., Aug. 30, 1947,
p.l03.
I
I
413
FLUID MECHANICS
Stroke, in.
6
10
25-40
32-57
35-63
45-80
12
1,
f
I
i
18-24
The net Buction lift possible with a pump 'amounts to the barometric
pressure less ,t he following items: (1) true vapor pressure of liquid at the
pumping temperature, (2) pressure caused by weight and spring of suction valve, and (3) entry friction losses. Should this computation come
out to be negative it means that a net positive Buction head is necessary, .
that the pump can produce no lift. Centrifugal pumps should always be
provided with a ;'flooded suction" (positive head), because there is' no
convenient way to prime or fill them with liquid and they c8JlI;l.0t op~r
ate without liquid in the case. .
~ample
114~
X:.!
= 4.05 ft
If ttlls liquid is heated to its boiling point, whereat its vapor pressure is 14.7 "psis. and
its specific gravity is 0.62, a suction head (not lift) of about 15 (t is required.
(O.05SC
steam~actu
l.O)(P - p)
(13-11)
to
Kind
0/ pu.mp
Kind oJ sttam
0 .9
1.0
1.02
1 .05
1.14
1 .1-1 .2
l00~
superhea.t 0.90
40F superheat 0.96
100 psi sa.tura.ted 0.99
126 psi saturated 1.00
200 psi saturated 1.02
300 psi sa.turated L04
98% quality
1.10
CHAPTER
14
COMBUSTION
+ 20 2
COs
+ 2HsO
The gross
:3
= 1010 -
Ht
+ ~02
= H 20
The molecula.r weight of hydrogen is 2 and of water 18. Two pounds of hydrogen
burna, yielding 18lb of water.
Wa.ter produced per Ib of fuel..,. 0.12 X
1%
= l.08lb
I.
415
COMBUSTION
TABLE
C.F.
Per
cent
sulfur
10 . 2
4.8
17,500
6,33 X 10 8
10.4
2.7
17,950
6.4
10.6
0.85
18,350
6.45 X 10'
10 .8
2.95
18,200
6.26 X lOs
11.45
2.2
18,900
6.43 X
API
gravity
5
7
9
12
14
14-1
Btu
per Ib a
Btu
per bbl a
X 10'
loa
,
Corrected for sulfur and for minor amounts of oxygen and nitrogen, and 1.5 % of
B.S.W.
II
TAllLE
14-2.
40.0
40.6
38.5
22,64
92,000
107,000
103,500
100,500
109,000
108,500
110,500
108<,500
112,000
110,500
119,000
122,000
122,000
119,000
52,6()(ju .
table the heating value, pounds air per pound fuel, and the percentage of
carbon dioxide (Orsat analysis) were computed on the U as fired" basis.
Typical residual fuel oils l have about the properties and gross heating
values shown in Table 14-L
1 Nelson, W. L., Maximum Variations in Heating Value.
1954, p. 299.
416
Natural gas and cracked gas are the major refinery fuels. Gas is more
easily fired than solid or liquid fuels, but it has the minor disadvantage
of producing a long flame and a flame that is often deficient in its ability
to radiate heat. Some of the charactenstics and combustion constants
Jor- gaseous fuels are given in Table 14-4. Note that- inert gases 1n
TABLE
14-3.
API
Fuel
Ht<>
Und&C
HJ
termined
and ash
22.
23.
24..
25.
28.
&
"
II
...... ..
_4
.... , ..
Heating value,
B~u
&
.. .. 86.0 14.0 . .. ,
.. . . 87.0 13.0
0.89 85.8 12.09 1.19
. . . , 86.1 12.0 0.35
0.33 86.2 12.39 0.39
or
'
.....
.....
.....
21.850
20,240
15.42
12.0
20,400
]9,000
18,450'
14.76
18,001
18,241
18,076
17,723
17,351
17,479
17,787
17.128
17,3M
17,345
17,212
17,179
17,075
16,800
17,030
13,543
"1'4.12
14:17
13.1
13 .5
" 15.8
16.7
15.6
L3,098
9.7
19,6&0
19.053
0.04
' 0.45 _ 19.376
19,256 '.
0.89
1.03 18,778
1.14 18,3111
1.38 18,454
0.10 18.710
1.67 18,088
0.81 18,274
0.74 18,277
1.51 18.077
0.96 IS,OM
1. 65 17,970
17,600
0.3
0.50 17,837
13,997
1.3.7
. 17.4
13,m
....
II
0. .29
.
..
....
"
..
7.7
'
13.932
13,969
15.241 llS,040
10 , 2()()11 9,7007,4QOa 7,()OO<I
14.341"
14.47 .
14.J
If .O
13.7
13.7
13.4
13.:)
13.7
13.7
13.4
J3.5
13.4
16.0
16.4
]6.4
18.2
16 .
16.6
16.6
]6.9
18.7
16.8
13.4
17. )
10.4
18.6
18.8
14,000
14,000
11.9
J8.9
Oa I. as fired ,. basis.
SpeciBo If8.vity at &n.
c .Also COIltaiu 1.1 per oen t oxygen aDd nitrogen.
II
Drybuis.
G~es,
TABLE
. , ..
~-
14-4.
,-
Matcial
Malec-
ular
weight
Denelty,
Ib~r
cu tat
6O"'F
Ht
~OgllD
2.0
ethane ..... ... ...... , ... '.............. 16.0
3. Ethane ................................. 30.0
4. Ethylme ................ .. .. , .. ...... _ 28.0
6. Propane ................. _. , ..... , . 44.0
8. Propyleoe ......... _............ 42.0
7. But.ane ............................. .. .. 68.0
8. D!pro~er overhead ... , ............... 81.2
U. Craokid
dry ..... , , , , . . 21.7
~ 10. Cokicg,.
............ ................ 28.8
11. RefOl'mlJ)g,~...................... 30.2
~
12. Craoked gu,
................ , ....... ZS.6
13. NB~I pa, dry ... . ... _............ 18.6
14. Cracked g1L8, wet ......................... 30.6
11;' Coking,K1U!l, wet ....... . ............. 23.7
16. Reortlllng gaB. WIlt .... .. ......... 29.8
17. Cracked IU. we~ ....................... 30.0
18. Natural gu, dry .. , ................... 17.9
19. Fluid o&t., dry ................. . ...... 21:1.4
20; Houdry cat... dry ........................ 26.0
21. T.O.C. dry ................... ' ...... , . 26.2
22. Refinary laa. dry ...................... 28.0
23. RefiDery gas, dry .... ....... , .......... , . 24.6
24. Wet 'herma.l gas .......................
26. Avg. Fluid, butan~fret! ................... 30.8
28. Avg. Ho~ and T.C.C .. butane-free ....... 88.4
27. Ayg. cat. r ormer ....... . _...............
8.0
28. Avg. Flui1iB-B cuL.. .................... 67 . 2
29,. AVg. T.O. ,B-B out ..................... 57.3
C;'
0.0053
O.042Z
0.0792
0.074&
0.1162
0.1110
0.153
0.0823
0.0572
0.0628
0.0795
0.0755
0.04Vl
0.0806
0 .0626
0.0787
0.0923
0.0471
0.0776
0.0588
0.0663
0.07010
0.0650
O . O8~5
0.101 .
0.021
0.151
0.151
eH,
I~,H1O
C.Hw+ Inert
HeaLing valne.
Btll per
au if, at BOor
Grou
Net
I.
2.
'
cell\. Heat.iDt;
ou t Per
value,
C~'at
fuel at aero per Btu ,per
HI'O per
Ib Dat
oed u- 6O
F.
oent.~cu air
grOllS
, celli &II'
""'"""-----
ea
'"
4.3
64.11
44.6
Z7.6
82.7
16.D
24.3
"
...
..,
...
. ..
...
. ..
...
...
n.o .... .
......
6.7 1.3
2.9
1.9
3.6
1.11 14.0 . . ..
2.5
9.6
7.2
7.4 27.6
4.9
8.0 22.4 .... .
1.1 23.8
8.3 21.2
30.8 40.2
... e.6
3.9 .... . 0. 7
86.6 .... .
8.6
lUi
5.9
5.1 19.1 10.6 16.11
6.4 30.6
3.2
6.6 .....
3.7 11.3
9.8 45.9 19.5
1.0
6.7 18.7 14.2 23.7 .....
6.2 29.6
..... 34.6 1.7 21.8 4.7 17.4 8.0 7.5
1.0
2.1 .....
90.1 .... . 6.2
0.4
8.7 15.1 24.7 .... .
7.0
6.6 31.7
0.4
9.8
9.8 19.8 .....
6. 6
11.8 36.2
8.2
9.6 10.0 20.6 .....
19.6 24.6
1.9
6.4 18.2
7.5 19.7 .....
3.3 36.0
0. 7
Ii.l 13.6 .....
2.6 53.3
1.9 19.0
6.4
4.7 32.7 2.0 21.6 7.4 17.2 6.6
7.9
7.1 38.4 19.2 ..... . ....
13.3 16.1
6.8
8.0 31.2 H .3 . . . . ......
0.6
9.4
9.3 .... .
5.0 .. ...
4.9 . .....
80.8
..... .... . .... ..... . .... ..... '36.2 &8.8~
...... ... .. .... . ..... ..... ..... 31.1~ BS.9
.....
au fI, air
per
I"
0,6
...
...
0.2
.. '
.. '
.. .
...
. 9.3
. ..
...
6.5
7.1
7.6
11.0
...
...
. ..
:1.8
2.11
...
. ..
...
. ..
...
...
...,
,.
..
...
'
. IDcIua.1so c:ompoUZlda.
'.
2.38
9.67
10.76
14.29
~.90
21.44
81.10
17.37
12.34
14.00
16.90
15.2
10.95
11.8
13.1
16'. 0
13.7
16.0
14.0
13.0
1,865
1,316
1,463
1,746
1,617
1,160
1,786
1,426
1,714
2,MB
1,112
1,609
1,481
1,384
1,140
1,43.5
1,710
1.200
1,804
2,214
641
1,621
1,953
569
.....
. ...
.....
. ....
.....
. ....
'.'
6.47
. ....
. ....
. ....
. ....
. ....
l,:WO
1,&92
1',475
1,0&0
1,64a
1,302
1,666
1.892
1,005
1,470
1,353
1,2S4
1,407
1,310
..
. ....
16.72
IS.10
16.20
19.38
10.68
111.9
14.6
13.7
15.7
13.\
61,400
28,920
22,350
21,650
21,6110
21.060
111,340
22.650
lUi
..'
..
. ....
22.930
11 . 89
13.SO
23.6GO
22,150
. ....
12.91
11.81
~
.a
7.02
..".-
23.300
21.900
21.0100
22.800
21,800
22,250
23,500
20,700
ZI,BOO
20.900
20.800
22,080
21.922
21.907
30,400
21,069
21.101
418
PETROLEUM
RE~RY ENGINEE~G
made. Table 14-2 shows the cubic feet of gas consumed and the decrease
in gross heating value for each gallon of liquid produced. 'The table
may be used ill studying the economy' of such processes as gasoline
recovery, polymeri~ationJ Codimer manufacture, alkylation, or bottle-gas
production. .
Example 14-9. Value of Refinery Gas for Liquid.Extraction. Gas 14 of Table 14-4
is thought to have a. value of 30 cents per thousand cubic feet because of its heating
v.uue compared with the market price of fuel oil. If the gas is processed for poly
gasoline the amount produced will be (see Table 14-2)
10.6
. ( 53.2
+ 40.0
5.9) 1,000 3
al
h
d
ft
100 "'" .46 g per t ousan eu
At 11 cents per gal the poly gasoline is worth 38 cents, a.nd the value of
eubie feet of the gas has become
30
120,000)
+ 3.46 ( 11 -
1,786 X 1,000 X 30
8.
thousand
:::z
The 120,000 is the average per gallon heatmg value of the liquid product, and the 1,786
is the heating value of gas No. 14. Of course, money must be spent to build and operate the plant out of the extra. 17.2.cents per thousand eu ft.
Combustion Reactions. The fundamental reactions involved in combustion are shown in Table 14-5. If the ultimate analysis of the fuel is
TABLE
14-5.
COMBUSTION REACTIONS
Fuel name
Reaction
1.' HI
+ }102 =
+
+
+
+
+
+
H 20 ............... Hydrogen
C
Ot = CO 2
C
%011 = CO .................
CO
~02 = CO 2 . . . . . . . . . . . . . . .
S
O! = S02 ...................
6. CH 4 + 20 2 = CO 2 + 2H20 .......
7. C2H 4
30! = 2C0 2 2H 20 .....
8. CIIB, 3~02 = 2C0 2 3H 20 ...
2.
3.
4.
5.
Carbon
Carbon
Carbon monoxide
Sulfur
Methane
Ethylene
Ethane
Mol.
wt
2
12
12
28
32
16
28
30
Heating Lb air
value, . per Ib
fuel, no
Btu
per Ib
excess
61,400
14,600
4,440
4,050
10,160
23,920
21,650
22,350
34.8
11.6
5.8
2.48
4.35
17.28
14.81
16.13
available, these equations are all that are required to solve many com..
bustion calculations.
An examination of these chemical equations yields information concerning (1) the weights of materials that react and (2) the volumes of
gases that react. For example, reaction 1 indicates that 1 cu it of hydrogen reaets with one-half of 1 en ft of oxygen to produce 1 cu it of water
vapor. Likewise reaction 6 shows that. one volume ,of methane requires
419
COMBUSTION
+
+
.';
',.
.'.I
420
fiue gas from oil stills because at least 30 pet: cent excess air is normally
used in order to keep a low furnace temperature, and no carbon monoxide
is produced under these conditions if effective burners are used.
The amount of excess air employed ranges from 10 to 75 per cent, the
low value "for large installations completely automatically controlled and
operating on low-beating-value gaseous fuels. Oil requires more excess
air, as indicated in Table 14-6. .In comparison with coal, oil can be
fired at higher" thermal- efficiencies of 2 to 35 per cent, 6 but in modept
large power plants the superiority of oil probably does not exceed 3 per
cent.
. TABLE 14-6. USUAL
AMOUNTS
OF
ExcESS
Pipestills
AIR, PER
CENT
Boilers
Minimum
Usual
Large
Small
1~20
35
50
lQ..;-15
15
15-25
20-25
25-35
+ 0.4
X 14.12
+ 1.0 = 20.8
I1 the ~taclt tempera.ture is 600F, the volume of flue gas per pound of fuel will be
~o8
421
. COMBUSTION
modO
20
.30 40
60 80 100
~
600
500
400
J I
. j/
:i
I
3-~
r.:-.,.
Ij
5 IO~
a..
9
IW
~ 70
:) 60
...,:
cri 50
40
V.I ~
h~/
..
~ ~V
V
V
j /
30
//
'l V
/
40000
V'
20000_
~v
-.3
o
~
I
5
~ggg i
10000 &
V
US~
1000
..
SC()(/es
c.
6000 ~
5QOO a:i
Righf-hcmr.J anri
lower
4000
-.
,30-00
-'
~~
200
30000
1// /
I~
50000
.I~V
I'
..... 200
:100
100000
,,/
I/
- 0
10
600 8001000
4=(:02 .')02
fV
. upper :scales
300
20
300 400
BOO
200
JLL ./.
2--7'1.: ~-f-
~ooo
1000
?>OO 400 600 Baa 1000
2000 .30004000 6000'8000 10000'
Tempernture, Degrees FGllhrenheit
-Figure 14-1 is' plotted on a mole basis because the diatornic g~a
oxygen, nitrogen, carbon monoxide, air, etc.-can be representm by a
single curve. The same applies to other groups of gases. The figure
giv~ the number of Btu required to raise the temperature of lIb-mole
of gas from 32F to the desired temperature. The upper and left BC~~
a-re for temperatures up to about 150F, and the lower and right scales
are for higher temperatures.
Examllie 14-4. Use of Sensible Heat Chart for Gases (fig. ~1). Qne thousand
cubic feet of 8. flue p8 is ~led from 1000 to lOO'T. Analysis of gas: CO" 10 per
422
PETROLEUM REFINERYENGINEEBlNG
cent; RtO va.pOr, 12 per cent; 0" 3.7 per cent; and Nat 74.3 per cent. How much
heat must be removed? (Note that 1 lb mole of gas occupies 379 cu ft at 60F and
14.7 psia.)
1000 X 0.10
=
-= 0.264
Moles CO 2
379
1000 X 0.12
= 0.316
=
379
= 1000 X 0.743
1000 X 0.037 = 2057
M oIes di a to lIUCS
379
379
.
Material
At 100OF
At lOOF
CO 2 ,
H 20 ....... , ....... ,
Diatomics ...........
9850
8650
7000
580
610
47.8
- 0.264(9,850 - 580) =
Heat removed from CO 2
Heat removed from H:aO
= 0.316(8,650 - 610).,.
Heat removed from diatomics = 2.057(7,000 - 478) Total heat removed =
2,445 Btu
2,540
13,400
18,385 Btu
The lower the stack temperature, the lower the heat loss to the stack
(or atmosphere), but the most economical stack temperature for pipestill
heaters is about 300F higher than the temperature of the incoming pipestill feed (see Fig. 23-6). Even closer approaches are economieal in
boilers, but at very low 8~k ~mperatures severe corrosion and fouling
423
COMBUSTION
00
./
,00
80
./ ./ / .
~/
/ /1 't'/
0
0
30
L eo
SO
LL Vrh
40
IVh
IV/
30
I
V
/
~
I 1/ '/
-_
...
10
, 1/ ./
~
/
V
6
&
~
~
./"
/~
~
,~
~
~V
[/
ao
le.3
I~.a
WAS MADE
~r ZHJ>UeENrDUSS l
tI'".
EXCESS
CO~
AIR
...
5
4-
J I 1 11
300
IS.C,
&
1 I
PER La.
~
H.\L
---
~.f!:~"
NET LB.GAS
CARBON DIOXIDE
AND "~R CENT JrtE~.1
.d' /~ '~'f'
FUEL
I~
1 1
150
12,'
SO
10. ,
1.9
100
3
20003000
1000
!tOO
.-
.-
L L 100
1 . / ./ ,
......
1/ / '/ /
81'<
L // '/
."
/ /V/
.u'I
.....
I
/ II
_.
"YO
/
/ /
10
.~ ~ ~
./
V~
'//
',/~
100
200
~V
40
10.
./
500
SO
/ //
300
CUFT.
FUEL.S NET. ~
H.y.
_ _ FUEL+
60
20
VI
.. .,-\;.r~
V PER CENT EXCESS AIR
.4
80
iwET CR.
WET REF:
WET NAT.
12.3
IO.~
~.?
MOI~T-
URC.
Excess AIR.
CAP80N DIOXIDE
AND PElf CENT EXCCSl.
AIR.
)(CESS ~:z_
-AIR
WET
DRY
111
12
15
II.~
10
2S
10
so
II.
7.8
100
. 1
Ail
1200
t 200
1 o~o
19. "'
17.8
lZ.l
_SIfOULD ALLOW
1000
111)00
1700
or:! /,1/
j .
30
V-'- L V
l}.)G.
V / / '/
D,
20003000
--r
424
PETROLEUM REFINERY
~NGINEERING
occur in the air heaters and economizers of boilers due mainly to the
, sulfur' dioxide .(or trioxide) in the flue gases. Table 14-7 indicates the
sulfur content of typical fuels and the furnace atmospheres produced by
the,m r S as well as minimum metal temperatures (related to dew points)
fot air heaters or economizers. Significant amounts of sodium sulfate,
and vanadium in the fuel require even lower II end" temperatures,' but
14-7.
TABLE
Gra.ins S02
per 100 eu ft.
Per
cent
Type of fuel
Coal"
sulfur
Coal
Oil
Oil"
1.0
. . .. . . . . .. . . . . , . .
2.0
2.4
3.0
. . . . . . ........................
4.0
.. .
.. ,
18()e
180"
18t}:
180"
200
205
220
16()e
.160"
16()c
16&
222
239
116c
244
259
193c
235
'258
276
20&
287
270
~
,
217
62
76
49
60
124
148
, 118
186
248
147
196
310
371
98
180C
fuel
5.0
6.0
8.0
..
..
..
..
...
496
I
I
,.
I
difficulties with such fuels are being cured by the use of additive). In '
'burning acid sludge or hydrogen sulfide, the minimum metal temperature
at the air preheater may be limited to 300 to 400F,7 and a coa.ting of
milk of lime is sometimes applied to the p~eheater tubes after their usual
washing.
Metal temperatures in the economizer section can be raised by recirculation of hot air or by heating of the inlet air, with steam h~aters, but
both. of these remedieg result in higher costs or constitute a penalty
against high sulfur fuels.
The Burning of Oil Fuels. Although steam-atomizing burners are
Nelson, W. L., Oil Ga8 J' I Dec. 22, 1952, p . 353; Mar. 9, 1953, p. 126; e.nd Sept. 1~,
1954, p. 138.
7 Robinson and Gurney, Steam a.nd Power Economy . . . , ASME Meeting,
Sept. 25-28, 1950; or see Pet. Procusing, June, 1952, p. 806. Also Andrea., K. S., Oil
GaB J' I Jan. 4, 1954, p. 66.
I
425
COMBUSTION
expensive to operate (see Table 14-8 8) they are used widely in refineries
because they can handle almost any fuel and because steam is universally
availa.ble. Burners are of two main designs:
1. Outside-mix burners by which the oil is released into a high-velocity
sheet of steam. Oil and steam issue from the burner through separate
openings. Much of the energY-in the steam is wasted, and the steam consumption is relatively high.
TABLE 14-8. ApPBOXIlI.ATE DIRECT OPERATING COST OF BURNING
100
GAL OF
FUEL OIL
Cent3
Oil-pressure atomizing ................ -......' . 5.0
Low-presaure air-a.tomizing. . . . . . . . . . . . . . . . . .. 7 .5_
Intermediate-pressure air-a.tomizing. . . . . . . . . .. 10-25
Steam-atomaing. . . . . . . . . . . . . . . . . . . . . . . . . . .. ~30
High-pressure air-a.totpuing . ................. . 60
2. I nside-mix burners are most widely used. In these the st~~m and
oil are mixed in a chamber within the burner, and they issue togetl).er from
the burner as a single stream. Foam formed in the mixing chamber is
directed by the shape and direction of the burner tip so that the flame
of proper shape and size for the furnace box. As foam issues from the
tip, it bursts into a. fine mist of oil pa.rticles.
Residual fuels have better atomizing or foaming properties. . Gas oils' or
distillate fuels do not atomize e~ily unless they are mixed with residual
fuels, bu~ naphthas can be burned satisfactorily if a suitable burner tip
is employed. Air-atomizing burners using low-pressure compressed air
are sometimes lLSed for asphaltic residues, acid sludge mixtures, oJ." ditty
residues. Acid sludge tends to cause corrosion in steam-atoinizing bume~,
and hence high-pressure spray nozzles are sometimes employed. _Excessive mineral matter ca.uses deposits of glazed solids on heating surfaces.
Viscous fuels should be heated to such a temperature that the Saybolt
Universal.viscosity is 130 to 250. Table 3-29 shows preheatjng temperature vs. FUlol viscosity. The higher the temperature the better tl)e performance unless vaporization occurs or unless the water content of the
fuel is high. At temperatures past the flash point, operation n;lay be
erratic and the flame may splutter. Highly superheated ~rn may
cause excessive coking within the burner tip if the oil temperature is
high. About 0.1 sq ft of heating surface (steam coils) is required. for
each barrel of insulated fuel-oil storage. Heating coils for iUll~ulated
tanksare discussed in connection with Fig. 17'-9 and Example 17-7.
Rotary pumps are pr~ferable b~ause of the steady ,P~.S&.Q~ they produce. The pulsation in oil pressure and the. " breat~g" oJ burners,
caused by reciproca.ting pumps, can be eliminated by an air surge cham-
is
MeO~w-Hill
, .
BOok
426
PETROLEUM
REF~Y
ENG~EERlNG
her at the pump, but air must be added to the chamber with each work
shift. Although the fuel may be fed by gravity at a head of only 10 to
15 ft, a pressure of 40 to 60 psig is often employed. To obtain satisfactory a.tomization of light gas oil a pressure of 125 psig may be required.
The amount of atomizing steam for inside burners ranges from 0.2 to
0.5 lb per pound oil (1.6 to 4 lb steam per gallon) and may reach 10lb
per gallon for outside-mix burners. In general the higher the pressure
and temperature of the oil, the lower the steam consumption. Moisture
in the steam causes spluttering or sparks in the Harne and if excessive
may put out the Harne. Steam may be superheated at the burner by a
short length of steam line leading into and out of the furnace.
Robert Reed 9 analyzes oil-burner troubles somewhat as follows:
Spluttery or Sparky
Flame. This in general may be caused by (1) wet
I
steam, (2) suspended solids in the oil, (3) improper dE?sign of burner tips
for the oil and the duty handled, or (4) foreign matter inside the b~~r
or in the tip.
. Long Smoky Flame. The cause may be (1) Jmproper design of burner
tip, (2) insufficient air for.combustion, or (3) insufficient atomizing steam.
Failure of Ignition. This may be caused by (1) too much steam for
atomization, (2) fuel pressure low, (3) fuel valve plugged, (4) improper
design of tip or too small an included angle on. the flame, or (5) wet steam
or slugs of water from the steam line.
A dazzling white flame indicates too much excess air. A properly
operated oil burner produces a. perfectly stable yellow-white flame. A
fluttery flame indicates that too n;luch atomizing steam is being used ..
Puffing in the furnace may be caused by poor tip design, insufficient
excess air, or-parti~ stOppage of burner tip.
Mechanical-atomizing burners have not heeD: generally used. in the oil
industry. However, a mechanical burner or a combination steam- and
mechanical-atOmizing burner is useful when firing inferior fuels, such as
cracked residues that contain suspended carbon or acid sludges from lub.ricating-oil treating. These inferior fuels are supplied to the burner at
200 to 3000 P 'and at a pressure of 100 to 200 psi. Acid sludge, without
any treatment, can be burned in some mechanic~l burners, but more often
the sludge is hydrolized with water and allowed to settle. Sludge may
also be mixed with fuel oil and burned. The mixing is facilita~d by
heating to a temperature not exceeding 155F. Gentle rolling with compressed air and recirculation by means of a pump (through filter screens)
are the methods usually employed. Heat~ng is usually done with steam
jets because carbonaceous deposits tAmd to accumulate 6n heating surfaces. . Sludges or sludge mixtures must be completely mixed at all times,
and one re.finer_4as foud 10 that a homogenizing mill in the fuel circuit,
8
L1)
~o),!J.ltonJ
COMl3USTION
427
for grinding particles of gritty sludge, is highly useful. The use of sludge
as a fuel is not very profitable but other means of disposal are also
expenSIve.
Extremely high-melting-point residues or fuels tend to congeal into
particles (black smoke) which cannot be completely burned when the fueJ
meets large amounts of "cold air at the burner. Such behavior can be
alleviated by the use of short-Hame combustion, substantial amounts 01
refractory at the mouth of the burner, preheating of the combustion ~
to the melting point of the fuel, or preheating of the fuel to 500 to 600F.ll
In large power installations, oil can be fired more cheaply than coal
[see Eqs. (3-5a) and (3-5b)]. This is due to the greater thermal efficiency
(2 to 35 per cent) Ii when firing oil, to the lower cost of operation, and to
the smaller investment in storage and firing facilities. 11 During 1951, the
advantage of firing oil rather than a ton of coal was about 16.5 cents, and
this does not include a charge for the large cost of stoker equipment for
coal because most large plants are already equipped to fire either coal
or oil. ~
Firing Systems. The liquid fuels tha.t are burned in refineries are often
hardly more than waste products. Tars that are almost solid are common. Such fuels must be heated, and they must be circulated continuously past the burner to prevent solidification in the line (Fig. 14-4).
The amount of circulation is 1.5 to 2.0 times as much as the oil burned.
In large plants the circuit may be so long that a system of parallel flow
must be used. The lines should be insulated, and a pair of strainers
must be used with residual fuels. Pressure gauges on each side of the
strainers will indicate plugging, and one strainer can filter the oil "while
the other is being cleaned.
"
Individual circulation systems are often maintained for 'each pipestil1.
With such an arrangement the ra.te of firing may be controlled by regulating the pressure in the fuel line without visiting the burner. The pressure may be conveniently regulated at a central control board . . Such a
system is not satisfactory unless clean, fluid fuels are available and unlesa
minor adjustments of the firing rate are all that are necessary.
A method' of maintaining a constant-pressure fuel gas of uniform. calorific value is indicated in Fig. i4-5. Liquid p~opane or butane may be
fed into the system (sometimes actuated by an automatic calorimeter) to
main tain the heating value, and natural gas is adIDitted to carry the main
heating load if process gases are insum-cient. When sufficient process gas
is produced to maintain well over 30 lb pressure in the palance tank, all
Palchik, E. R.) How to Use"Resid as Furnace Fuel, Pet. Refiner') NoVember, 1955,
p. 161.
n Nelson, W. L., Oil Go" J' I July 12, 1931, p. 106; July 19, 1951, p. 114j Sept. 20,
1951, p. 329; Dec. 22, 1%2, p. 3M; May 251 1953, p. 260; JUIle 1, 1953, p. 118; June 8,
1953, p. 141; a.nd Sept. 13, 1954, p. laB.
11
428
Shell
Boilers
Siroiners
'"
\.
\.
'"
Conlrol/
.~
pressuh
gage
Fue/-oJ7 sforage
FIG. 14-4. Cireulp.tion system for firing fuel oil.
,-28ps;
N~~~.ff~~, .
RerinerYF
from und'S
_ _L-_-L.._......
-----JOps/
lo-DlQ----..
Flrsl
pn'orify
+---+-....ot>':::J~..
---15 psi
I.Inik
Torch
Secqnd
priorify . .----+-....~i_'_-1
uni'k
ThIrd
priority +----t-~:;Qoo--f
.u nifs
FIG. 1~5 . .:Arr~ngement of a. refinery gasoous-fuel system.
(Pet. Refiner.)
three pri~rities of service receive gas. However, AS the "make" of process gas decreases and the balance tank. pressure falls below 25 Ib, oil
burners must be lighted on the third-priority units and finally on the
second-priority units. The system should be so balanced that the firs1r
priority u,uts" alw~ys receive gas.
.
Example 14-6. Analysis of Flue Gas from Fuel Analy$. Fu(}i 5 in Table 14-3 is .
burned with 60 per cen~ excess B.i.r. Compute the Orsat an~~ of the flue gas and
tp.~ a~a.lysis of the flue gas incl1i~g WB.ter vapor.
I
I
429
COMBUS,}:,ION
Basis: 1 lb of Fuel 5.
-Mol~ C
= ' 0.::1
Moles Hi _ 0.;2
MoleiJ
' N'2 . SDd
M
. 0 '1:es
s = 0_.~~35
1'"\
V1'"
0.011
-ao-
- 0.0717
= 0..0600
.... 0.0001
00004 (a.ssume 1lAU
L_I~ and hAll'\I
=.
cu.&
Less
oxy~ in fuel:
o.~
= -0.0002
volu~e
Mole
0.07i7
0.0300.
0.0001
0.1018
0.1016
0.0508
0.1524
Mole
Nitrogen with this oxygen: 0.1524 X
~~:~ =
0.0004
2
Nitrogen in fuel:
0.577
0.0002
0.5772
ORSAT ANALYSIS
Material
Number of moles
10.25
7.26
O 2 (eXcess) ............
N 2
Total ...............
82.49
100.00
Ma.terial
Number of moles
0.0718
0.0508
0.5772
0.0600
9.4
6.7
76.0
7.9
. , ....
100.0
O 2
N J , .
H 20 .................. '.
Total .. , ..............
Ta.ble 14-5.
430
Enmple 14-'1. Heat Balance ~f a Furnace. FUel 9 (Table 14-3) is fired at 200~
using OAlb (280~) of steam per pound of fuel. The flue gas has an Orsat analysis of
13.0 per cent COl, 4.25 per cent O2 , and 82.75 per "cent N 20 The heat gainfully used
to heat oil amounts to 1,367,000 Btu. The stack temperature is 800F. The a.ir is
at 807 and has a. relative humidity of 50 per cent. '.!'he :vapor pressure of water at
80F is 26.6 mm. The still is operating in a. continuous ma.nner.
Basis: 100 Ib of oil 9, 60F temperature datum.
The ultimate constituents in the fuel undergo the following chemical reactions:
C + O2
== CO 2
Hs + ~OJ = H 20
8 + O2
""" 80,
HsO (liquid) == HaO (vapor)
~:26 = 7.3
Sulfur, . . . . . . . . . . . . ..
~;
:II
Water.. . .. . .. . .. .. ..
i~5 = O.ooa
Undetermined ... , . . . .
lila:
(neglect)
""
7.32 X
4i~5
""" 2.39
= 460475 X
Moles air"
= 46.475
= 46.475
1
X 0.791
= 58.7
O 2 required
.... ,.,.,.... 0 f excess "0 I or 8J.T
.
P ercen~
431
COMBUSTION
Moles
Atomizing steam
= 100 X 0.4
"
18
... 2.22
= 5.14
= 1.04"
1:8 7
From 8.U'
= (760 13.3
_ 13.3) u .'
Fre'a moisture in fuel (negligible)
Total
= 0.00
- 8.40
The water va.por leaving the system in the ftue gas must equal the"water coming into
the system, or 8.4 moles.
Heat balance:
Btu
1,766,61Q
Q
All this heat will be recovered from the system if the flue gas"is cooled to 6O F.
Hea.t LeAving System
Btu
SensibJe heat content (see Fig. 14-1) a.t 800F.
COt ........... " ................................ ".7.32(7,600 - 245) - 53,900
Water vapor . . .. , .................................. 8.4(6,800 - 260) = 64,900
Di8.tom.i~ gases (N t a.nd excess O 2 ) . . . . . . . . . . . . . . ..... 48.89(5,500 - 200) , = 259,000
367,800
Summary of heat ba.la.nce:
Hea.t
Btu
1 ,7~.610
Per cent
1,367,000
367,800
31,810
1,766,610
~OO\O
'">77~
20.85
1.8
100.0
Stack Draft. The draft13 that stacks or chimneys will produce is discussed iri all boiler and combustion textbooks.' A draft of 0.5 to 0.7" in.
water is adequate for 'nearly all refinery stills. The draft at the burner
11 Nelson, W. L., Oil GiuJ., Mar. 15, 1947, p. 101; Mar. 29, 1947, p. 177; Api-. 12,
1947, p. 103; and Apr. 19, 1947, p. 135.
,
"
"
, I;
,~
- 432
Ga8 temptrq;..
ture, OF
400
800
1200
1800
2000
If the draft (or pressure) at any point in the still ranges much from atmospheric pressure, air will leak in causing large losses of heat up the stack,
or flue gas willleak out (pressure in still) heating the walls and weakening
the structure.
Steel stacks are used extensively in the petroleum industry. In these,
the loss in gas temperature, particularly during a rainstorm, greatly
reduces the stack draft,15 and hence special tabulations of stack draft
and stack capacity corrected for various weather conditions and fric~
tiOIl losses due to the velocity of the stack gases have been published. 11
According to the Universal Oil Products Company,!11 the effective temperature in unlined steel stacks and the draft produced by them is indicated by Fi~, 14-6 for an atmospheric temperature of 80F. At lower
atmospheric temperatures and during rainstorms, very much greater
decreases in temperature are encountered. 13 15 Altitude affects the
height and diameter of a stack by the following factors:18
Elevation, it
Height
Dia.meter
2,000
4,000
1.16
1.36
1.58
1.84
1.03
6',000
8,000
1.06
1.10
1.13
At a mass velocity of about 0.6 lb per sq ft per sec (cold velocity 60F of
7.5 It per sec) friction losses are almost negligible but at 0.8 to 1.2 (the
common design range) friction loss consumes 20 to 30 per cent of the
static draft.16
Rickerman, J. H., Heater Designs for the Petroleum Industry, TraM. ASME, &7
531 (1945).
11 Nelson, W. L., Loss in Temperature of Stack Gases, Oil Gaa J., Sept. 30, 1943,
p. 56.
11 Melder, L. A" Pet. Engr., June, 1956, p. C-26.
14
433
COMBUSTION
200
180
160
r ~ rr I 7
~\ ~ \ '\ I'" r}. ~}
I j
"'~\ \
~~
7fJ:..
rL 7' N
r\ ~ '" "t'- r "" ~ J 7 IJ ~
~\ \
""
"~ '"I""fF hJ
""1 ' j '\
T'.
....~
140
I\.
r-\ ''\
f-
1\
1\
""
"-
1-
"
~
"-
'"
, ~r ~I
~r
.......
""'-
"- II
~ :1
r-......... "-
~ 1.4
rr--- rJ: I I
J~
r~
II
~J
1.5
t'---:
1.3
I~ FFR
1.2
I{: 1]-
/.1
V - /.0
TN
I ....... 1/'f--.It-I-- Ir-J I -I
'~
"a9 ~
r
IJJ
7
rf-.
11
~ I
........
" 7'
N
1
r-- I II rr- ~ 0.8 c::
" -ItL II
aT
~
r-..
W
J
"k '
I
r-r--...
---- f-- IJ- '1 f / 7 I 7 -J. 0.6
60
7
~
f-\
1,.-....."
r-., ~
......
f-
:r:.,o..
'-....,
:--.......
-..;:
K
f-
40
~r-.
"""L-J.
~f
It
400
500
"
600
I
~
7 7as
I
/ - 0.4
'T
..,
0.3
-f
7 0.2
I 1
:I I I I 7 / / 7 I- 0.1
II II ~
VI 1/ V 1/ I VI IJ _
I
20 ..... JI
I
I JI
W.
,
III I
I II
~--f-..
Ir- ,I
II
-.;:;
700
I I
800
900
/000
//00
A 120-ft unlined steel stack receives gases a.t 800F. The atmospheric tempera.ture is gooF. Follow the vertica.lSOOF line to intersection with the 120-ft line. The
effective or average stack temperature 'can be read by following the sla.nting straight
lines downward to read 680F on the tempera.ture scale, and the draft is found by
following the sloping lines to the right (0.95 in. draft).
CHAPTER
15
,"
" "'"
~
'-
"'"
434
I
I
1I
435
These generalizations are equally valid whether. the vappr is removedcontinuously or remains in contact with the liquid. Nevertheless, the
manner of separation of the vapor has a quantitative effect on the composition of the distillate and of the remaining liqUid.
Condensa.tion is essentially the inverse of vaporization. It follows,
therefore, that the condensate will be richer in higher-boiling and poorer
in lower-boiling components than the original vapor and that the remaining vapor will be richer in lower-boiling components than the condensate.
Mechanism of Vaporization. The most common method of vapor formation is batch vaporization as conducted in the ASTM distillatio:n or as
practiced in early shellStill distillation or in small scale chemical plant
operations. The mechanism is differential because, as the temperature
is raised a small amount, a corresponding evolution of vapor takes p]ace.
. As this vapor is removed and the temperature is again raised, another
evolution of vapor occurs. In distilling a liquid mixture each component
in the liquid exerts a partial vapor pressure or a part of the total vapor
pressure, and every component tends to leave the mixture in proportion
to its partial vapor pressure at that temperature, The lower boiling
components, those with high vapor pressures, compose the most of the
first vapors, but Bome remain in the liquid and are distilled later with
other components whose boiling points are much higher. This behavior
may be most easily pictured by conceivblg that the high-velocity lowboiling molecules bump into slower moving molecules and lose the energy
content that would normally cause them to leave the liquid and enter the
vapor, Some of the slower moving molecules may receive enough energy
by these impacts to leave the liquid, and this occurs because we find t~.at
high-boiling components a~ present in the first vapor even though the
temperature is much lower-than their boiling points,
Differential or batch vaporization may be mathematically formulated 88 follows.
If L represents the liquid, z the percentage of a. component in the liquid, and y the
percentage of the component in the va.por, a. material balance with respect to the component is
xL ",,; (x - dx)(L - dL)
y dL
xL =- xL -:taL - Ld:t +thdL
ydL
(:t - y) dL = -L ck
dL
dz
-Y;=y-:e
The quantity that must be distilled in order to cause
436
.\
I
,J
!
VAPORIZATION AND CONDENSATION
437
CONDENSATION
438
vaporization and the equilibrium-condensation curves are identical if intimate physical contacting is maintained during both operations.
In large condensers of the tubular type the condenser usually consists
of several separate condensing units and liquid is withdrawn from each.
Each of these units is referred to as a partial condenser. However, partial condensation does not give an effective separation between products,
and hence it is not generally used as a method of fractionation. The partial condensers that are used in a modern vacuum plant for the separation
of gas oil and wax distillate may be an exception. . This separation need
not be exact, and hence partial condensers are satisfactory (Fig. 7-25).
In the past, dephlegmator8~ or partial-condensation towers, cooled either
by air or water, were extensively used.
In certain plant eqpment the vapor is suddenly cooled under equilibrium conditions, and such a. process may be called quench condensation.
Jet condensers embody this method, but they are not widely used. However, barometric condensers, in which steam is condensed with waterJ are
common. Of more importance is the condensation of vapor on each plate
of a fractionating tower by reflux. In this case, the condensation may
take place in the presence of other vapor that does not condense. As an
example, kerosene is condensed on a uside-draw" plate of a bubble tower.
Gasoline vapor is also present at the plate, but it does not condense.
The details of the application of this phase of condensation will be disc~ssed in Chap. ,16.
. EQUILffiRIUM
439
must necessarily change along the liquid curve with the production of
increasing quantities of vapor, the composition of which {ollows the vapor
curve. The change in liquid and vapor compositions 'w ill continue -thus
until the total vapor has the composition of the original liquid and the
liquid is completely vaporized. Further heating will, merely superheat
the vapor without changing its composition.
'
Partial Pressures of'Vapor Components. In a mixture of gases, each
gas exerts a pressure equal to the pressure tha.t it woUld exert if it'occupied
the entire volume by itself, and the total pressure of the mixture ~ equal
to the BUDi of the partial pressures of the component gases (Dalton's law).
The pressure exerted by each component is called the "partial pressure'"
of the component~' and is dependent on the total pressure and,the volume
or number of molecules of that component in the gas.
'
In the gas phase if 1f' is the total pressure and y is the volume or mole
fraction of an individual component in the mixture, the la.w of partial
pressures may be expressed as
p
or
= Px
11"
11"
The term
'4
440
= 1r1!.
= P x (Raoult's law)
(15-1)
1r'
'trY1 = PIX!
ry" = P2Z2
1I'(Yl
Y2) = P1Xl + P2Z2
= 1 - Xl and YI y"
but
X2
r -
Xl
= PI
Yl
Pi
_ p"
= -PI
Xl
r
and
11" -
and
X2
= P'J. _
Y2
P"
= -X2
11'
1
PI
(15-2)
P~
Example 16-1. boult's Law. A liquid consists of 42.5 per cent butane by volume
and 57.5 per cent penta.ne by volume at 60F (see Fig. 15-1). If the liquid is heated
to its boiling point of 180F at 100 peia, what will be t.he composition of the vapor that
is produced? (See Example 5-15, or Fig. 5-25 or 5-27.)
Vapor pressure of C"H 10 at 180F ::a 152 psi
Vapor pressure of e,H u a.t 180F - 56 psi
Sp gr at 60F of C,H lO ~ 0.585, and C,Hu = 0.631
Basis: 100 gal of the mixture.
;:~~
.- 0.54 or (1 - 0.48)
= 157!oo 0.46
69{ 00
0.70
0.54 = 0.30
.=
Thus a. liquid containing 46 per cent butane a.nd 54 per cent pentane. (mole per oont)
at 180F and 100 psi is in equilibrium with vapor containing 70 per cent butane &Jld
30 per cent pentane (see Example 15-3 and also Fig. 15-1) .
. General Vapor-Liquid Relationship. When applied to complex mixtures the general relationship for a. system that contains no inert componen'ta (those which do not occur in significant aJnounts in one of the
pha.ses) and in which aJ.l components form an ideal solution in the liquid
pha.se is
.
+ +
= P1:th + P"X3 + P3Xa + etc.
441
Pressure = 1rY1
1rY'J 1rYa
etc.
(partial pressures, gaseous phase)
vapor pressure
(partial vapor pressures, liquid phase)
(15-3)
The symbols are the same as those used on the preceding pages. In addition to this general relationship the partial pressure of each component is
independently equal to its partial vapor pressure in the liquid, as indi..
cated in Eq. (15-1) or Eq. (15-4).
Unfortunately, the ra.tio of vapor pressure P to the total pressure 1r.
used in Eqs. (15-1) and (15-3) is not a constant. It is a.ltered by the total
pressure a.nd to some extent by the kind of materials associated with it in
the mixture, particularly those far removed in boiling point. For this
reason, the ratio y/x must be determined experimentally.
K =
y = p approx.
:.c
1r
(15-4)
(16-5)
+ 'Ir(Y2 + y, + etc.)
= 1rY1
_
(15-6)
In this equation (15-6) the vapor pressur~ of the liquid is less than the
total pressure to the extent of the partial pressure of the inert gas.
11'
= 7r'Ul
(15-7)
442
-=--=---=
0+8
0+8=;:S
= P,
.P.
S = 0 P.
or
po
but
and
p~
and
Dividing,
= -r
po
+ Po =
0 7r
po
po
'71"
= 0 p.
po
(15-8)
The steam need not be bubbled through the oil, although more effective mixing results by so doing. The derivation of Eq. (15-1) shows that
"if the partial pressure in the gas phase is reduced, the partial vapOr pressure in the liquid must decrease. Thus the use of steam causes vaporization to proceed until the partial vapor pressure in the liquid is equal to
the partial pressure in the gas phase. Gurwitsch and Moore 1 have
reported that steam is more effective in reducing the boiling point than
D<on's law indicates. Nevertheless, the error that is introduced by
the use of Dalton's law in design work is probably not important.
The foregoing discussion applies primarily to the gaseous phase. The
situation in the liquid phase is different from any situation discussed heretofore, because oil and water are not soluble in each other. In the liquid
phase the water exerts its full vapor pressure, but each of the mutually
soluble constituents exerts only its partial vapor pressure as shown in
Eq. (15-7). If the temp.erature is high, the vapor pressure of water is so
great that no liquid water roasts, but at low temperatures or high pressures
an ins,?luble water-oil system must be handled~ In most instances, trialand-error computations are necessary.
Example 16-2. Steam Required for DistillatioIL A temperature of 370F is
required to vaporize 66.5 per cent of the pressure distilla.te (Fig. 4-24) by flash va.poriza.tion. It is desired to reduce the tempera.ture to 340F by means of steam. Vaporization takes place at atmospheric pressure.
1 Gurwitsch, L., and H. Moore, "Scientific Principles of Petroleum Technology,"
2d ed., D. Van Nostrand Company, Inc.) Princeton, N.J., 1932.
443
In order to reduce the boiling point from '!i70 to 340f, the vaporization must be
conducted a.t 490 mm pressure (Fig. 5-27). Enough steam to reduce the' partial
preBBUre in the gB8 phase to 490 mm will b~ used [see Eq. (15-8) J. '
-10-0 =
(760 - 490)
~-4=-=9'::""O~
8 = 55 moles
'= 55 X 18 - "990 Ib
or
10 psig,
- 1.277 mm
(1 277 - 490)
J
490
100 = 158.5
~oles
,
or 2,860 lb
444
10.0
5.0
' ..
'" , "
....
"~
......
"
'-
"
'-'- '"
...
r",,"
r-.. ~
,~
'4!b
"
"
....
~...
"
...
"
."
!o. ...
"
",,"0'
""'..
>1X
"
-",
~.
' ."
'\
......
c
~ 0.5
en
c
0
"
",
'
L.
:3
tr
", ,
d":'~
' .....
'~ol
r....
'\
,,~
...
IS"-
~ol
I"
I'~Q ~1"
~,
,~
-...:: I:l'o
'""'-
'~
"
.... '
"""'".... r,--'"
~
'~ ~~
"",
'"
-,
. ~.
...
I.....
LJ..
....
'l
~~
~ fJ..
~-
'/
.~
L4
"
~.
"
I"~
-.
,.
>~
."
r--
\Do
~ I.....
...
'~
Mi)(tur~
A
0.05
Mixture B
A Vohor pressure
- 0 Bu ane at 300 0 F.
- - - Estimated idQal K's
0
1' ....
i'
fl(
-""
0.1
~,
~
~
~.
.....
r,
"~
L
rl
"
'. I'~o ..., 1'","- '~ r-......... . /" "' .....
',..-('0.
~
~ ~ 1'.
...,
" '. ~. '~ ..Q.... ~
.... ~
'\.~
,
,, " , ~. ~ " , ~ ~L ~,I .... .....
.....
1',
" ""', tic ....
~.
0.2
.-<'0 .
...('l
....
"
hO
"-.
~
2.0
!oo...
1'-
~. ~~ I''''~:~~~
,
~
~~ ~ ~~ .... ~
" ' .", ," "', ~~ .',~,,~
,
"I,r-,~", .J>,',"~ ,
"
,
~ ~0.A.
~
" " '" , "
,, r-, " ,~~~ "~ ~
~ t'-.
~
~
~"
"
"
'" ' . -,
.
'"
~,
-,
...
''''',
..........
., -
""
.....
'"
.....
"'-
' ....
~
~ ::J.
..... ,
......,; ..I
,./"
....
/"
"
~,
""
to-..
-,
.....
....
i' ......
..... ,
"
......
"',
I'
i'.
I' i'
500'
100
200
~ooo
Pr~ssure. Ib./ sq. In. abs.
FIG. 15-2. Equilibrium consta.nts (or ratios) at 660c F for the components contained in
two complex mixtures plotted as a. function of pressure. (White and Brown. Ind.
Eng. Chem.)
20
50
from one another. If the point of convergence (Fig. 15-2) can be determined for a particular mixture, then the pattern of the equilibrium ratio
diagram can be approximated with fair accuracy. The convergence pressure is a known point, and the equilibrium ratios at low pressure where
Raoult's Law is applicable constitute a series of lines. Accordingly.
attention is centering on methods of determining or estimating the con-
TABLE
1.5-1.
,
At 160F for less-volatile
constituents of these
molecular wBightsG
Pressure,
pais.
60
75
100
200
300
14.7
20.0
40.0
60.0
100.0
... .
150.0
200 :0
300.0
400.0
500.0
....
11e:
8e:
2211
1711
12
9
6.6
7.2
750.0
4.5
1,000.0 ,
3,000.0
3.4
5.0
3.9
1.2
--
25
19
13
203
149
75
50
31
259
190
96
64
39
20
21
16
13
11
26
60
...
.. .
...
~.7
4.8 4.6
3.9 3.6
1.8 ...
.5
1.7 2.1
300
60
..
..
8
..
6.8 6.8
4.3
200
'
10
10
7.9 8.2
5.5
100
75
25
18
13
10
21
28
21
14
11
14
11
28
23
17
12
9
..
...
..
...
7.7
8.7
8.9
7.4 7.1
5.3
4.1
5.9
4.5
6.2
4.8
5.2 4.9
4.1 3.7
1.7
2.1
1.9
"
. ..
25
19
13
10
8.0
5.5
4.2
......
29
22
29
22
15
23
18
15
12
11
11
9
8.9 9.1 7.5
6.1
4.6
1.7
6.3
4.9
2.1
5.3
4.2
2'. 0
292
220
110
75
46
30
23
15
11
.9 .4
6.4
5.1
II Only for a system whose less-volatile constituent has a viscosity-gra.vity factor of 0.82.
Data from Sage, Hicks, and Laoey, Tenta.tive Equilibrium Constants for Light Hydrocarbons, API Meeting, Wichita, Kans., June, 1938.
"At tempera.tures above 220'"F, G. 'G. Brown, Pet. Engr., April, 1943.
Figures rounded out to whole numbers, here and in many other instances.
;...;-:
., ~
I ,
-'": : : :
~ 't-: _;
446
Pressure.
peia
15-2.
200
100
300
100
200
300
100
300
200
28(0)'
840F
41KtF
46O"F
92.0
67.6
103.0
76.0
34.0
22.9
14.0
88.2
113.0
83.0
42.0
28.8
122.0
90.0
46.0
31.0
19.3
- - -- - - - - - - -- -14..7
37.1 38.1
27.S 28.5
20.0
40.0 . 13.8 14.4
9.2 9.7
60.0
3.6 6.9
100.0
20.9
14..0
8.5
5.90 . &.00
4.49 4.62
3.09 3.15
2.96
2.30
2.41
1.38
1.50
1.90
1.0t
1.~
1.16
......
0.93
1.08
0.74
0.98
8.08
2.13
400.0
2.93
2.05
1.61
600.0
1.35
760.0
1.000.0
3,000.0
16.3
10.3
6.3
56 .9 75.6
41.9 55.6
21.1 21.8
14..2 18.6
8.7 11 .2
M.7
42 .3
21.4
14.:1
8.7
1.66
8.Q9
300.0
66.6
41.6
4.28
8.2&
2.27
1.79
3.M
150.0
200.0
n.2
30.3
.. . ..
77 .2 73.'1
56.9 64 .2
28.6 27.3
19.2 18.4
11.7 11.2
26.0
litO
17.9
7.56
7.88
7.61
9.50
5.72
6.M
5.90
7.25
8.40
5.05
6.90
2.U
4.60
3.80
5.20
4.30
6.76
2.07
3.23
2.71
3.9l;
2.00
4.13
3.22
2.68
4.13
2.46
8.89
2.96
9040
6.60
1.36
1.46
2.36
2.80
1.22
1.56
1.83
2.02
1.09
1.3.'i
1.89
1.91
2.24
3.50
2.77
.......
8.11i
2.63
0.83
0.91
5.73
4.35
1.70
.......
1.93
1.59
0.94
10.9
3.30
13.4
10.3
12.2
7.2
4.80
1.06
The Je...volatile eoDBtitnmt hu a vlsoosily~ COMtani of 0.82. Data from Sap, Hicb, aDd Lacey, Teotative
Equilibrium CODBtants (Dr Light Hydrocarboos, API Meeting, Wiohit&, KAns., JUDe, 1938.
6 For temperatmes above 220"F, O. G. Brown. Pd. B1IQ7., April. 1943.,
Source
Symbol
M/xfure
0
Kay
Ethane and BuJone
Methone and Butone
Sage, Hiclrs~ Locey 6.
0
Webber
NohJrol gas, B.uJane and Absorption oil
1.0
1
J
,,
'~ ~
'" ,
" ,~
"
"" ,
.........
~,
0.1
100
J.
V
!
~~
.'
1,000
10,000
Pressure,. PSJA
FIo. 15-3. EqUilibrium ra.ti08 of n-butane a.t lOOF in mixtures with ethane, methane,
and with na.tura.l ga.B in absorption oil. (Pet. Refin.er.)
.-;OV
. AOOor '.
"
#~
.rj)of
fP00f
erftof rJif
I~V Itt'rl~tU11Y;YJt2gf_1111
I I I I 111111
II/TIT
TIm
6
,5.
"
fl'
2~
"11
.,
I
\
If7rrlT
l'
1 -.\
\1 \1 \
1.
l1
.
1 \ \
t /' \
!~ A \ \
I
~~~~KNru
'"
'1 I
T/T
li
I III KIH'
.l,. '\\
[f\~
f\'~
~~
~ ~L\.1..~ ~~~~\~~\~~
I" l--1/2.~
I
\\ '\ \1.\RKN1\J'f\~'K\I\~~
_ ,N ~rd'k/'k'~,'-~
T'
.j ~I ~ .II E'illllkl
\J
\1 \1'"1'
1\ I ' I \1 1,\ I I'll I 't\ "\ I\, \.=-X N N N " " l\: '" ,,"\.~"i... ~
~~~,,~
lJ
C/lOraclenzoh'on foclor 1 I. 1 H
.
10.5
---11.5
u.~-.l ~A
I~I\!H\
.T
, f/
"'l\.
l\.
4DU~~~~~~~~~~~
r:Sl~~:j~t=~~tT~~~~~~~~pt~~~~~~~~~~~~~~~~~~~~~~~OO~
~~~~fEE~!E~~~~~~~~~~~~~~~~~~~~~~~~~~900~
cIOOI
'2
3"
S Ii ,. fJ 0.01
~ - 4~6
,. 8
0.1
3"
5 6 ,. 8
"1.0
2:1.,
J.
S 6 ,. 8
~o
448
449
were based on the assumption-that Raoult's la.w-w8.8 valid. The composition of the
mixture tha.t boils at 180F can be found from the following expression, which is the
Same as Eq. (15-2).but stated in terms of K's:
2:1
1 - XI
KJ - -,K.
~~:i-
:1:1'
C2
Z2
= 0.495
Note that neither the liquid nor the vapor composition is the same as in Example 15-1.
+ F2 + Fa + .. .
+V +V + ...
+ L2"'+ L3 + . . .
2
La
L' etc.
Furthermore, for the total material or for any component; material balance equations of this nature may be written
F=L+V
and
450
. PETROLEUM
~omponerit
or
VI
ENGINEERING
B~ERY
= K 1 LI
is
VA
and
= KILl];
= K AL
L"
V
Va
VI
~olving
V
VI) L' etc.
= KI(F I -
V1
KIFl
(L/V)
+ Kl'
etc.
Since the sum of volumes or moles is the total moles _of vapor,
KIFI
"(L/V) + Kl
K2F'I.
KaF3
. " . , etc. = V
(15-9)
A similar statement :~uming Raoult's law but stated for the liquid residue is as follows:
.
.r
F11t'
+ P1(V/L)
Ft:r
+ P'I.(V/L)
.' 1r
FaT
+ .f3(V/L)
= L (15-10)
.
In this equation 1(" refers to the total pressure, and PI, P2, etc., to the
va.por pressure of each component. The feed F may be totally a liquid,
a vapor, or a mixture of liquid and vapor. .
In solving these equati'ons it is necessary to assume a value of L (or V);
. and by 8ub'stituting this value, a value of L canbe computed. If the computed value is not the same as the assUmed value, other aSsuInptions must
be made until finally the assumption checks the computed value. By
solving the equation for several temperatures; an equilibrium-flash-vaporization (E.F.V.) curve may be drawn, but such curves are usually not so
accurate as the empirical curves described on pages 112 to 119 unless
precise equilibrium ratios for the system are available. The partition
between liquid and vapor will occur at or near the component whose
vapor pressure is equal to the pressure of the system (or K = 1.0).
Graphical methods l l of conducting. the trial-and-error solution are useful if numerous oomputations must be made, but they are of little assist..ance in occasional computations.
Example lG-4. Equllibrium'Vaporiution of Complex Mixtures. A wild gasoline
eonta.ins 15 per cent CH., 10 per cent CJI" 30 per cent CaR., 5 per cent iC4H 1 G, 10 per
cent C.H 10, 15 per cent CaHu, and 15 per cent C,H u and heavier materials. Vaporization is conducted at 232 psia and at a temperature of lOOF. What is the composi11 Nelson, W. L., Oil Gas J., June 22, 1937, p. 63; Scheibel, E. G., Pet. R6finer, July,
1948, p. 136; Reilly, P. -M., Pet. ~efiner, July,. 1951, p' , 132; and Wilson, C. L. t Pd.
Refiner. June, 1952, p. 131.
451
tion of the residue gasoline and of the gas that is va.porized? Basis: lOO moles (or
100 volumes) of. gas.
Since Eq. (15.10), which assumes Raoult'slaw, is the more complicated, this eqmv
tion will be used .. Note, however, tha.t Raoult's law is not valid a.t these conditions
and that more exact results would be obtained by using Eq. (15-9).
Inasmuch 8.8 the vapor pressures of CaR. and CsHs are 194 and 750 psi, respectively,
and the vaporization pressure is 232, the split will occur between these components, or
the amount of vapor will be something larger than 25 per cent. Assume L = 70 (see
Table 15-3, column 5)
. For L = 70,
= 100 .;... 70 = 0 At)9
L
70
.~.
La = r
The values of L 1, Lt,
= 194 psi
30 X 232
= 22.0
L4J
TABLE 1~
(1)
(2)
(3)
(4)
Material
Value
of F's,
moles
Value
of P's,
Fsr
CR.......
..
,
C2H II
CaHa ........
iCJllO .......
C~IO .......
CaHu .......
C~H14+ .....
Total ......
15
10
30
5
10
15
15
...
(5) .-
PS
psi
4,100
750
194
78
56
19
4
I
...
(5)
3,480 1,755.0
2,320
321.0
6,950
83.1
1,160
33.4
2,320
24.0
3,480
8.1
3,480
1.7
.......
..,
+ 21'
1,987.0
. 553.0
315.1
265.4
256.0
240.1
233.7
....
to
(8)
(7)
(6)
1.75
4.2
22.0
4.38
9.06
14~ 5
14.9
70.79
13.25
5.8
8.0
0.62
.0.94
0.50
. 0.10
29.21
Table 15-3 shows that the assumption of 30 moles vaporized was not exactly correct
but the check was close (29.21). About 29 per cent will be vaporized at 100F.
The mole composition of the equilibrium vapor and liquid may be computed by
dividing the moles of each component by the total moles:
Component
Vapor
Residue liquid
CR" ................
CiR, ...............
CsH ...............
iCJilO .... : .. . .......
CCH ID
C aR I2 .
CeHu+ .............
Total .............
2.47
5.93
31.08
6.18
12.80
20.49
21.05
100.0
45.37
19.85
27.39
2 .12
3.22
1.71
0.34
100.0
.!
452
PETROLEUM
RE~RY ENGINEE~G
453
Temperature
FIG. 15-6. Liquid-vapor phase relationships at- extreme temperatures and pressures.
I
J-----J~~-+--+_+.~"7f_---'7_#_
2
3
4
J.---~"""""'OIC--"F-.,,~~--+-. 5
6
1
,0
100
'.88
19.82.
49.8.5
70.46
90~26
100.00
200
300
Temp~rature,
Deg.F.
FIG. 1~7. Pressure-temperature phase diagrams a.t constant composition for mixtures
of ethane a.nd n-butane. (Kay, Ind.. Eng~ CMm.)
. 'eooo
eooo
1/
DJO
Io--r-
f.
2000
8
S
~
;)0
fC
III.
iI"
1000
-I--
i""
..... ~
~
600 r-~
&00
cj
~3
\
~~
..c.1C: ~.~
J
II
1\
~ r... ~!"
I,
I[
I\. I"'- ~
. . . i\ r\
1/
ace
--.J
[\
~K ~ ~ ~
ej ~
i""'4 I""
i'
...
:""i"l.
1'\
~;,. ..-:~
r\
re- i'"
i"'-
aoo
400
r-- r--. ~
i/I..oo' ~r-
~ rV ~ ....
~Io-""
r-- ~i"--
!/
4000
If
.... ,....~
~ ~ i""'
IC,
II
,...~
II
100
200
!OO
400
TIftIPIra ture.
fICO
I""-a..
i......
c.,-e,.
""f\
e.,
1\
II I
2DO
.\
I,;"
,e.,
r-- c,-c u
800
1'00
800
i'oc..
900
..,.
(Pet. Reft'Mf'.)
100
. 200
300
roO
800
900 .
/IX'il'VYII
Y~D(I/[/['VIAK,[JX V1
12<1 1/1
I)(
100
200
300
600
500
400
ASTM volumetric average boiling po/nt, OF
',~ ~-!
BOO
700
,- ~ ;;u~:-~ .::.,.: . :':.:.~~:" ,::":,,,~~.::s;u..""." .1..:'.;:-.-;:,:,~- -," "----=-:--' -:' : ': ' . ; :;" ~':-.... ~ :;. __ ::; _ _' : ; j~.""'11
_._
" , . _ '"
,_.
"':
. .;
:.=.....:.=-~
456
Figure 15-86 shows the loci of critical states of 'some of the many systems
that have been studied.
Although the pseudo critical temperatures and pressures introduced in
Figs. 5-9 and 5-.12 are thought to be best 'for the computation of the compressibility behavior of gases and vapors, they do not represent the true
critical point which is necessary in studying phase "behavior. The true
critical pressure 18 and the true critical temperature U can be estimated
CRITICAl. TEMPERATURES Of' PETROLEUM FRACTIONS
m .
.,."
42~
==
I:::
I~
5)0
, 600
700
from Figs. 15-9 and 15-10 as a function of ASTM boiling range and API
gravity. Edmister and Pollock 13 have also devised a method of estimating the phase diagram of heavy 011 mixtures by loca.tion of the focal
point (see Fig. 15-13) of such a diagram. In plotting such a diagram, the
pressure scale is logarithmic but the temperature scale is a Cox-type H
scale which is usually proportional to 1/(382 + t) where t is degrees
Fahrenheit. The focal pressure (Fig. 15-11) and focal temperature (Fig.
15-12 are determined 13 as a function of the true critical pressure and temla
qlLem.
Eng. Progr.,
,
I,'
I.
457
-Q.U
~
E
Ii
tC 30e
y.
"I~"
!,,-
- -Q.t
.f
1:-:
::-::m::
:;;1::: .,;,
:;;
100
3()O
400
;;~
700
800
,;;
gOO
-F
(Edmister and
15-10) lie much to the left and outside of the phase envelope.lIi Thus,
either (1) our methods of estimating the critical and focal points are in
error, or (2) the lines of the phase envelope are not straight but tend to
be more horizontal at low pressures or steeper 'a t high pressures, or (3)
some mechanical difference exists between the behavior of equilibrium
equipment operating at a pressure and under vacuum. Little experimental data are available, and the construction of phase diagrams is now
Okamoto 8.Dd Van Winkle, EquiL Flash Vaporization .. Reduced PressuresJ
Ind. Eng. CMm., 46, 429 (1953).
11
458
-~
PHASE DIAGRAM
tJ'
FOCAL TEMPERATURE
of
PE1ROLEW FRACTIONS
180
140
LIND
IO' .~ 80\
1'2 0
SLOp., "/l
a: 100
U
80
ILl
A.
800
BOtL,NG
POINT
-.=-
(Edmister
only an approximation. . Flash temperatures under vacuum can probably be computed most accurately16
by the methods outlined in Chap.
4.
,
.
Rumple 15-6. Construction of Phase Diagram (Fig. 15-13).
. cycle stock has the following distillation
.
. curve:
T.B.P.
ASTM
5
10
30
50
70
428
468
447
494
549
488
590
90
672
573
635
. Per cent
A 28 API ca.talytic
515
548
The phase diagram will be computed 8.S if only the T.B.P. distilla.tion were availa.ble
because this is most often the situation. The (10-90) T.B.P. slope is (672 - 447) +
80 = 2:82 deg/per cent. According to Fig. 4-18 the ASTM slope should be about
1.97 (the actual ASTM slope, see above, was 1.84.). The average volumetric true
. boiling point is 550~ and according to Table 4-8, the ASTM average volumetric
18
Fi4t.k et aJ., Heav Fraction Vacuum Flashing, Pet. ProCt!6sing, May, 1955, p. 651.
459
boiling point will usually be about 57 lower (a.ctually 2F higher, for this sample) or
545F. In examining Figs.,15-9 to 15-12, it is obvious ths.t the errors found here in
converting from T.B.P. to ASTM curves are not signmca.nt.
The fiash:"vaporization curve at atmospheric preSBUre will lie across the phase diagram on a constant-pressure line at 14.7 psia. The slope of the straight-line fia.sh.
vaporization curve (Fig. 4-18) will be a.bout 1.03, and its ,50 per cent tempera.ture
600
500
fpcol poinf-...
400
Crilico} fJOii!l:::::.
300
Pseuda cr/~icoI
200
'/
-a 100
'~
~ ' 70
,e///V/~~
.~~~JiJ
SO
40
or crillcq/
, condefJS(llion
temperature
,J ,
~.
~:~~ / / II I~~
J I:.~
0// /
30
// / L
20
10
450
VCricondenJherm
'~f~
Ci;:
/5
I ~~ poIit'A
/ '1/
-i//~ Iil
~v/ '/.
~~7/ LL,
Q.
,L/ / I/{
V/ ~/ / I,AI1oSPlleriC
-
E.F.Y. line
7-7 -77
SOO
550
diagra.~
/QOO
of
0
20
50
80
494
514
100
900
545
.576
596
The critical pressure is read from Fig. 15-9 starting at the bottom a.t 545F, reading
up to 28 API, then to the left to a slope line of 1.97, and finally at the top we read
315 'psia. Likewise, the critical temperature from 'Fig. 15-\0 is found to be 365~
above the average boiling point, or 910F.
460
The foca.l point determined from Figs. 15-11 and 15-12 is found to be:
.Pre881J.fe, pBia.
Temp, OF
315
80
910
48
958
395
It will be noted that the pseudo critical point is di1Terent from the actual critical point
or the foca.l point. The pseudo critiool temperature (Fig. 5-9) is about 890F. and
the pseudo critical pressure (Fig. 5-12) is s.bout 290 psia. If all of the correlation
methods had been perfect, the pseudo. oritical point would have fallen within the
phase envelope.
Separation Obtained in Flash Vaporization. Equilibrium flash vaporization produces the poorest separation between the components of the
feed, and in theory some of each component should appear in both the
600
I
of vapor and
IjqJJid froclions from flash voporirofion .
of typical pettOleum /rocflOn
I--
CIJIlIeS
/. Vj}
v:
500
r ce.
/
"/
I{ V
300
200
. 0\
/
.
III I
L j/
V
o
.~ ~ee~ ~ ~
~\O~
'2
\(~
e' (j~/
~ o(
~o~
/V
~9 ~
A"J;?'
tt~./
Of
~o~
L'/
of
3~
If V
'II
I 11/ /
k-"
./
/ ./
IiI
100
pe 6~ ~i:::J.4'e~
lL"
t
,\~V
2' ~/
./. v
/V
tJ,r
/ V. /
' / Y'
eQ
./ / '
II
. {IOSl'le
'/
1/ .
~/
.,,-V V ~ V
!'led ~.,.,.. . / V ~ V
I
,
flaS
~/.
i-':,r
'/
fI
/. :-/.
"
I I
~
V I
,/ I
I
/
...6
rf:>o/
~
if
, rI-~\'/
'to~",
r""
".,
",
ro
ro
ro
djsli~/ed
FIG. 15-14. Typical true:-boiling-point distillation curves of vapor and liquid products
(rom three equilibrium flash vs.porjzs.tions of a petroleum fraction. (Pet. Refiner.)
461
= 457 ~ 315
= 2.37
th~
The third flash (material from 60 to 100 per cent) curve is computed in a. similAr
manner. Note the circle points for the 10 and 70 per cent points.
The disadva.ntage of successive flashing is apparent. For example, to vaporize 80
per cent requires temperatures of approximately 405, 435, and 455F respectively'by
single, double, and triple flash.
1'1 Edmister, W. d., App1ication of Thermodynamics . . . , Pet. Refiner, December, 1949, p. 140.
' ,
18 Obryadchikov, S. N., Ind. Eng. Chem., 24, 1155 (1932); and Katz & Brown, Ind . .
Eng. Chern., 2G, 1373 (1943).
.
IS Vaswani, N. R., Oil Gall J., Oot. 3, p. 149; Oct. 17, p. 141; Oct. 31, p. 132; Dec. 5,
p. 143; and Dec. 12, 1955, p. 117. Or see master's thesis, Effect of Pressure on
Separa.tion by Flash Vaporization, University of Tulsa) 1955.
20 Equilibrium Vaporiza.tion of Oils and Carrying Effect of Light Encla, API BuU.
10, No.2, aee. II, p. 52, 1929.
"
462
? V- '"
q.~-
"':;
40a
,.....
~~
/'
/ ,,"
300
~'"/
I,...
... ~/
/'
/'"
/
//
1.0-
V" ....
~ I,...-
2.00
100
o
o
FIG.
~
V
J
40 50
60 " 70
80
90
100
Percentcge
15-15. Successive flash va.porization (see Example 15-6).
10
20
30
product through an externally fired heating coil and back to the bottom
of the tower. Such recirculation scarcely alters the vaporization conditions at the bottom of. the tower, but if the bottom material is cycled
back to the vaporizer section of the tower or is used to raise the tempera- "
ture of some lower boiling material it tends to suppress vaporization of
the low-boiling material. Recircul~tion back through "the feed plate
decreases the proportion of low-boiling material present at the feed plate.
The suppression of vaporization tnat occurs with one crude oil is indicated in Fig. 15-16)1
"
21
Nelson, W. L., Reboiling by Circulating a Residue, Oil Gas J., Aug. 3, 1946, p. 96.
463
IOO~--~--~--~--~----~--~--~--~--~--~
10
20
30
40
eo
VAPORIZED
50
70'
eo
80
100
PE.R C~NT
FIG. 15-16. Temperatures required to vaporize 25 per cent of a 42 API crude oil when
circulating various amounts of the topped crude oil (75 per cent of the erode oil)
through the ieed pla.te of a tower. .(Oil Gas J.)
and the .pure substance that is present in excess as the other component.
In such equations as (15-2), (15-3), (15-5), etc., the components would
not act according to their vapor pressures but at volatilities that are
relative only to one another. Constant-boiling or very close-boiling mixtures can also be separated by the addition of a new substance that will
alter the relative volatilities of the components of the mixture. In 8.zeo-tropic distillation the entraining agent forms a new cODBtant-boili?g mix..
464
PETROLEUM REFINERY
E~GINEEruNG
ture (of far-removed boiling point) with one of the substances of the
, original mixture, whereas in Distex distillation 22 the extractive agent
alters only the relative volatility of the components. Griswold defines
relative volatility in terms of x mole fraction in the liquid and y mole
fraction in the vapor as
y(l - x)
a =
x(l - y)
--:---~
Griswold et al.,
Ind~
CHAPTER
16
466
Gaso/lne
Cold
reflux
Cold reflux
---
ide reflux ~
- .:.;0- 'k~
---~--<J
Kerosene .~
Gas oil
"IJotfoms
). proclvct
"
16-1. The dotted Jines refer to the removal of heat at some plate on the
side of the column.
Example 18-1. Heat Balance of a Fractionating Tower. A heat balance of the
simple- tower system shown in Fig. I&-2 will be computed to determine the amount of
refltpt heat that must be removed to keep the tower in thermal balance. The capacity
, is 1,200 bbl per day (2,100 gal per hour) of a 12.1 to 12.2 Cha.racterization Footo? erude
oil At 576F the gaaoline, naphtha, kerosene, and gas oil are vapors and the red\lced
erude oil is A liquid. A sufficient quantity of heat must be removed from the va.pors
TABLlI
16-1.
Vol-
ume, .
per cent
API
U>
Ga.l
per
gal
per
Lb
-per
hr
hr
50 per
cent
bp
16-1
Mol. Latent
wt
hea~
110
155
120
113
185
100
240
90
'.
G880line........... . 26.8
Naphtha. " .. : ....
5 ,63
19.8
10 .6
36.97
:Loss ............
0.2
Crude .......... . . 100.00
1Cerosene .....
Gas oil .. . ........
Reduced erude ... ,
Fig.
62.8
52.8
45.6
39.4
31-.2
to
43.0
6.06
6.39
6.65
6.89
7.24
563
6.75
2,100
....
118
416
222
776
......
3,415
754
2,765
1,530
5,610
96
14,170
260
370
460
585
467
AP.I.
-Hot reflux'
---F~=:t~-.-J~+'.I<erosene /9.8%
45.6 A.P.l
r-----q.._ _ _+--~(Jtl5 oil 10. 6 %
erode oil
39.4 A.PI
600 0
t200 BRD.
.5/8gmS3S0
~+-..-.,;..;~-+-__ Reducecl
crude 36.91%
3/.2 A.P.l
--I &9
1~).
to cool ~hem 8.S vapors to the temperatures a.t which they are withdrawn from the
tower and to condense the naphtha, kerosene, and gas oil at their withdrawal temperatures. Specific heats were taken from Figs. 5-1 and 5-2.
Btu
Sensible hea.t:
Gasoline ................ 3,415(576
Naphtha ........ , .. '. ' .... 754(576
Kerosene ............... 2,765(576
Gas oil ................. 1,530(576
Reduced crude ........ ; .5,610(576
589,000
106,000
261,000
63,000
276,000
1,295,000
Steam ........................... 567(535 - 286)0.5 =
70,600
1,365,600
-
286)0.56
335)0.55
420)0.57
510)0.59
510)0.72
X 1.06 =
X 1.06 X .1.06 =
X 1.06 =
X 1.03 =
Latent hea.t:
N a.phtha. ................ '......... . ...... 7M X 113
Kerosene .. , ......................... , .2,765 X 100
Gas oil ................................. 1,530 X 90
Total heat to be removed. . . . . . . . .. . . . . . . . . . . . . ..
=- . 85,100
276,500
=
138,000
=
.- 1,865,200
468
latent heat and the sensible heat required to raise its temperature from
the storage tank temperature to the temperature at the top of the tower.
. A constant quantity of reflux is recirculated. from the product storage
tank into the top of the tower. It is vaporized and condensed and returns
in like quantity to the product storage tank.
Hot reflux is reflux that IS adinitted to the tower at the same temperature as that maintained at the top of the tower. Obviously, the reflux or
overflow from plate to plate in the tower is essentially hot reflux because
it is always substantially at its boiling point. For convenience, the overflow reflux or reflux in the tower is referred ..to as internal reflUX. Both
hot and internal reflux are capable of removing only the latent heat,
because no difference U1 temperature is involved.
If':::
Char,g<' -
I'
--
~
I
--.
t ::::::)
srocr----; .
I
I
"-:iIT'
Circulating reflux
Hot ~r/lJx
Cold reFlux
- FIG. 16-3. Methods of reInov~g reflux hea.t.
469
1. Hot Rejf:uz.
2'~3000
= 16,2501b per hr
Gal h o t 1'efIUX
16,250
6.22
2. Cold Rej1:uz.
.. ,
2,000,000
-8400
Lb cold r eftux ....... , ... 123 + (300
- 100)0.575- - ,
8,400
Gal cold reflux ...... '.' .. 6.22
= 1,350
3. Circulating Reftuz.
. u1.
fI
2,000,000
- 33 100
Lb Cl1'C
atmg re ux.......... (300 _ 200)0.605 ,
n_1
\..nU.
! ___ I _ '
CU'-'WAting
33,100
refl ux.........
6.22
1)
= ,
310
The
470
TOWER TEMPERATURES
100
ISO
200
2.SO
300
50
350
, 400
4~O
~O
or
~~
WO
6!tO
700
FIG. 1~. Range of top and side-draw temperatures in a topping (or atmOBpheriopressure) tower. (Oil Gas J.)
,
large amounts of steam are employed. With respect to the range of top,
temperatures shown in Fig. 16-4, the extreme high temperatures shown
are for
1. A high tower pressure (15 psig).
2. Minimum amount of steam or gas product.
3. Wide.-boiling-range top products.
Nelson. W. L'J Tower Temperatures, Oil Gu J., June 30, 1945, p. 129.
471
3. Narrow-boiling-range products.
4. Small a.mounts of reflux.
= about 120
= 1,865,200
120
""" 15500
'
1,865,200
=
120 X no
3415
.
Moles gasolme =
10
Moles reflux
'i
=
=
141
31
172
31.5
203.5
a Nelson, W. L., The Estimation of Tower Temperatures, Natl. Pet. News, Dec. 14,
1932, p. 25.
.1
:.
ii
I.;
I:
..
;.
472
Q)
70'0'
'
..r:
t
L
600
..r:
l>-
IL.
II)
500
/445"
~400
Cl
I~
.-
~200
laO 0
Naphf'hcx
"""""'""
.t
--
1--':: ~
1/
l/
-.I-lJ- .- --- --V
.----1"'----Kerosene
300
--
---
1>---
I:i
--
~---- ...
CIJ
CIJ
IV'"
L
:::>
.- ---
V
.2!!~
-
601s
6(; soline
t---I--
/-f
296 0
10
20
3D
40'
50
60
Perce.n +C(ge
70
80
90
100
FIG. 16-5. ASTM distillation a.nd .flash-vaporization curves of the products used in
Examples 16-3 and 16-4.
b. Circulating Reflux. When circulating reflux was used, the top temperature was
244"F. The reflux circulated between 264 and 166F. The circulating reflux does not
vaporize, and hence only the gasoline vapor and the steam need be considered.
Although the reflux heat is increased by the lower top temperature of 244~F, it does
not affect the computations because no reflux passes overhead.
Moles gasoline. . . . . . . . . . . .. 31
Moles steam ...... .. ...... ' 31 .5
Total moles. . . . . . . . . . . .. 62.5
Partial pressure """
6~~5
X 780 = 387 mm
473
Corrections to hea.t balance given in Example 16-1 for a. top temperature of 280F.
Btu
Gasoline ............ 3,415(286 - 280)0.485 X 1.06 = 10,500 ,
Steam ............. ' ........ ',' .567 (286 - 280)0.5 "'" 1 , 700
Correction. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . .. = 12, 200
Reflux heat = 1,865,200
+ 12,200
.. 1,877,400 Btu
= 120 + 1(~J':?,~0)0.58
= 7i~~O =
= 7,950
72~3
Moles gasoline. . . . . . . . . . . . . .. 31
Moles vapor .... '. . . . . . . . . . . .. 103.3
Moles steam ...... : . . . . . . . . .. 31.5
Total moles ............ : . .. 134.8
~~!:~
..1,
X 780 = 600 mm
, I,
;,
,
'I
Side-draw Temperature. The method of calculating side-draw temperatures is much the same as the calculation of the top temperature
except ,that complications arise because of the presence of the low-boiling
materials that pass the draw plate. Furthermore, the equilibrium condensation curve, and particularly the point on thls curve that denotes
complete condensation, is the basis for computing these temperatures.
At the zero per cent point on the fl.ash curve the side-draw product can
be completely condensed at 760 mm pressure if no lighter' products or
steam are present at the plate.
In practice, steam and vapor of lighter products are usually present,
and hence the 'effect of these vapors on the final condensation temperature
must be estimated. The lighter vapors extend from materials boiling at
almost the same temperature as the side-draw product to materials that
are substantially fixed gases. Those vapor materials which 'a re far above
their boiling point behave as fixed gases and lower the condensation point
by Dalton's law of partial pressures just as steam doe,S, but those vapor
materials which are at or near their boiling point are not effective in
reducing the partial pressure. Arbitrarily, the vapors of materials that
will be condensed at the s~cond or higher draw plate above the plate
under consideration may b~ considered to act as fixed gases. AlBo, 'the
,'vapors constituting the m(terial that is withdrawn from the draw plate
above the one under consideration are assumed to have no effect at all
on the partial pressure. Thus in a tower producing gasoline, kerosene,
'and gas oil, at the gas oil draw plate the gasoline vapor would be considered as a fixed' gas, whereas kerosene vapor would be assumed to have
;'-
e:
'1
1
., ,;
474-
420)0.58
420)0.57
(20)0.57
510)0.58
510)0.72
1.0:6
X 1.06
X 1.06 X 1.06 =
X 1.03=
MI'
a.l __ ll
1,454,500
oesmtern ceaUX . 185 X 100
327,000
71,000
260,000
62,000
276,000
996,000
44,000
138,000
276,500
1,454,500
= 78.6
The internal reflux con'tains the kerosene, and hence the kerosene need not te added
88 a. ma.terial whose pa.rtial pressure must be reduced.
Moles of materiAls tha.t act as fixed g_SSe8:
Stea.m. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 3'1 . 5
, GasolinE! .................................. 31
+ 62.5
62.5
=
141.1
= 1:~~
X 950 -= 530 m~
The atmospheric complete condensation point is 445F (Fig. 16-5). Correcting this
temperature to 530 mm gives 415F. The actual temperature was 4~0F.
The gas-oil plate temperature can be computed in 8. similar manner except tha.t kerosene is considered as an inert ~a.terial and the gasoline and naphtha both act a.s fixed
gases.
'!
475
method until all the plate temperatures and the top temperature have
been -computed.
Bottom and Stripper Temperatures. In those few towerS which a~e
heated at the bottom by. means of a reboiler, the bottom temperature is
the bubble point of the bottoms product, and except for corrections for
tower pressure and for process steam, the bottom temperature may be
read directly at the zero per cent point of the flash curve of the bottoms
product.
With ,few exceptions, all other bottom temperatures are the result of
hot material being stripped by steam and are dependent on such factors
as (1) inlet temperature to stripper, or feed-plate temperature of a fractionating tower, (2) cooling by self-evaporation, (3) heat losses through
insulation, a.nd (4) cooling or heating by steam. The inlet temperature
presents little difficulty because it is either the vaporizer temperature or
side-draw inlet temperature. Equations (16-1) and (16-2) summarize G
the situation:
at
PL
100h
+ H A (T -
= approx. L2P
Ta)
Bh
+ 0.658 (T
B
D
35 B (T - Ta)
_ T )
8
S
0.65 B (T - Ts)
(16-1)
' .1
I'
I'j '
/1
'j
(16-2)
','
Te~pera.tures,
, :,
:I ;
:: \
, ,l
;1
r. ~
'
.,.:
476
a little extra reflux and indirectly allowing a small amount ofexcess vaporization to occur. Bottom temperatures by Eq. (16-1) are generally higher
than those found in plant opera.tions. Apparently, the liquid leaves the
vaporizer at a temperature lower than that of the vapor or of the mixtme
in the vaporize.r. '
To use Eq. (16-1) or similar methods 6 the amount of stripping or processing 'steam and the percentage stripped must be known. The amount
of steam can be estimated from figs. 7-3 and 7-4.
Example 18-&. Computation of Botto~ Temperature. The tower of Examples
16.1
16-4 is 4 ft in diameter, the space'below the bottom tray is 10 ft, ,the airtemperature is 76F, about 8 per cent of the originAl reduced crude oil is removed bysti-ipPing, the latent heat of the strippings is about 83, and 567 lb per hr of steam (at 2S6F
rather than' 535~) is used.
.
and
/:J. =
8 X 83
100 X 0.73
+ 0.75(10
=-
9.1
+ 12.7 +
or by Eq. (16-2)
+ 35 5610 (500) +
9.6 + 12.5 + 19. = 41.1F
at = 1.2 X 8
0.65 X 567
5610
(576 - 286)
TOWER OPERATION
To increase the E.P. without altering the I.B.P., open the side-draw
valve (or increase the speed of the withdrawal pump) and close the draw
"valve of the next lower product by a corresponding amount.
To increa8e the I.B.P. without altering the E.P., close the side-draw
valve and open the draw valve of the hext higher product by a similar
amount. The I.B.P. is finally regulated by steam stripping.
For narrow-boiling cuts use more steam for strippipg and employ as
many plates ,as possible above ~d below the fraction.
7,
Nelson, W. L., Regulation of I.B.P. and E.P., Oil Gas J., Aug. 25, 1945, p. 143.
477
.'
'.
,.,
n
j)
:iI'
'
..
478
PETROLEUM'REFINERY ENGINEERING
if means are provided for redistribution of'the liquid at frequent intervals (it tends to channel to the sides of the. tower) . .Packing materials
are usually so expensive and so heavy that p~cked towers a.re employed
only for very small columns such as the smalleSt steam strippers. One
of the most successful applications of packing involves the use l i of multilayer expanded metal lath in the form. of 80 corrugated sheet so that the
ridges of one sheet and the valleys of the next higher sheet ate in contact. Pressure drops are very low, the HETP (height equivalent of a.
theoretical perfect plate) is half or less than half the .tray spacing of conventional bubble towers, and capacities are high.
Many early towers consisted of only baffle plates for directnig the
liquid back and forth across the tower, and so-called side-to-side pallB
are still widely used for such services as:
1. Fractionating very high-temperature va.por which tends to deposit coke.
.
2. Contacting hot vapor and cold oil for the purpose of pure heat exchangeJ or when
the effectivenesa of the separation or fractionation is not important, and for steam
stripping. The lower parts of most cra.cking plant fia.ctionators employ this type
of plate. II
.
3. For certain vacuum fractionn.tion systems in which only an extremely small pressure drop is" permissible.
4. F ractionating materia.ls iha.t contain suspended solid ma.tter, such as lime or coke.
Holes are sometimes drilled in side-to-side baffle trays, and the extreme
in such a trend results in perforated trays,14 sieve plates,tli Tlirbogrid
trays, U and Ripple trays. Ua In these, both the down-flowing liquid and
the rising vapor pass through the same openings.
.
More elaborate arrangements are the familia.r bubble-plate (Fig. 16-6)
and such modifications 14 as tunnel trays (vapor slots 'and vapor troughs
extend across the plate) and Uniflux trays, Hoat-va.lve bubble tra.ys, perforated trays with downcomers for. the liquid, and Kaskade-type (Benturi
and FIexi tray) trays.
Bubble Plates. In the conventional bubble-cap type of tray, the vapor
travels up the column by bubbling through a bath of. reflux liquid thAt
is contained on each plate (Fig. 16-6). If plate steel is employ~ the
plates are welded to the shell of the tower, but cast-iron trays must be
sealed into the tower shell by means of packing. Ca?iron is more resistaJ,1t to corr-osion, or at least is thicker than s~l; but the major corrosive
8.ction takes place at the liquid-vapor contact l?-ne, and hence the superior
12 Scofield, R. C., Industrial Fra.ctionating Tower Packing, CMm. Eng. Progr., 48,
405 (1950); a..lBo see similar British development, Chern. EftI)., August, 1955, p. 234.
11 Houghland et a.l., Perfonnance Checked, Baffle Loading Improved, O~l Ga8 J.,
July 26, 1954, p. 198.
14 Symposium Fractiona.ting-Absorption Tray Design, Oil Gas J., Apr. 26, 19M,
pp. 152-194.
1411 Anon., Ripple Trays Boost Ca.pa.city, Oil Gas J., Dec. 17, 1958, p. 91.
479
1- OR UClA(. so THAT
LIQUID CAr.K)T FLOW
. \ll.POR uPTAKE
BU881.. CAS>
UQUIO LEVEL
- {..
In ~ ~"O ~ ~ III
VAPOR
SLOTS
(Oft
MOllE
, LIQUID SVlL
\ OvtAf\.OW
'4,
\ WDR
Wo . . . . . . . . . .. . ,. . .\.
At.II'U ClAIVoNC E
50 THAT' DE8Ar~
t'
VAPOR Uf'TAKf:
011 R I S E R '
VAPOR FROM
-mAY
ea..ow
~DAL \ . \
WttP ttOt.ES
.!O TMAT OIL CAN
ORAl'" rRON TRAY
~=e~1O
The exact shape 'of the bubble cap is probably of little importance
except from the standpoint of cost. Sroan caps are best for large liquid
loads (see Fig. 16-12), and large' caps for large vapor loads. However,
some designers utilize small caps for s~ll towers and large caps (6 in.
or larger) for towers of 10 to 20 it in diameter. TlJ.e shape of the slots
appears to have little or no effect. 18 The same shl:Lpe of bubble is produced regardless of the shape of the slot. At low velocities 18 fiat disksbaped bubbles are produced; and at high velocities a channeling appears
to Occur, and 3. continuous elongated bubble space extends through the"
liquid. Exceedingly small caps (I-in. diameter) and tray spacings of
only 4 in. have been installed 11 for very low temperature operations in
which the a.rea for heat loss'must be kept to the minimum.
The bubbles extend out from the slots by not much more than 1 in., 18
11 Nelson, W. L., Tray DetAils-Bubble Ca.ps, Oil Gaa J Aug. 11, 1945, p. 125; also
see- Bolles, Wm. L., Pet. Procunng, Ma.rch, 1956, p. 82.
tt Kallam, F. L., Notes on Absorber Design NO.1, Pet: Engr., April, 1934, p. 33.
u Anon., Tr~y Design Saves Space, Chern. Eng., Mareh, 1956, p. 132.
18 Kirschbaum, E., Distillation and Fractionation 1:echnology, Edwards Bros.,
Ann Arbor, Mich. , 1948.
480
Outside
diameter, in.
16-2.
4 . . ...... . .. .
0 .0085
0.0232
0.0142
0.0204
0.034
0.0208
0.031
0.029
4~
..........
0 .0204
5 .. , . .........
6 ... . . . ......
0.031
0.0745
0.042
0.0156
0.0165
0.0167
0.0372
0.065
0.0396
0.040
0.045
0.0348
0.0356
0.055
0.0496
0.1001
0.0921
4 ........... .
4 hexagonal . . .
4 .. . ... . . . .. .
4 .. . ....... . .
6~
. . .. . .....
Uptake area
over
column area
0.048
0.257
0.130
0.079
0.122
0.078
0.135
0.148
Slot area.
over
column area
4
O.i.
Steel
Steel
C.L
C,i.
O.i.
O.i.
Steel
0.183
.......
0.144
, ......
0 .150
. . . .. .
. . . . .
Ma.teria.l
&
0.066'
0 .100
0.148
. 0.123
0.145
C.i .
C.i.
0.175
0.161
C.i.
0 .112
0.115
. . . .
CJ.
C.L
3 X 10 rectangular .. . .
and the caps are spaced 1 to 3 in. apart. In clean service the clearance
between the cap skirt and the plate can be only % in., but when material may be deposited on the tray, a clearance of 13-1 in. is helpful. The
liquid actually moves across the tray as a foam or froth, and hence the
concept of a static slot seal is only hypothetical and the actual dynamic
seal cannot be computed wi~h accuracy. Nevertheless, some method of
comparison must be used, and the following have been suggested:
Pressure of opera.tion
Sta.tic
seal l8
zero
in.
1 in.
1~ in.
~
Dynamic
sea.1 20
~-1~
in.
1-2 in.
1~-3 in.
2-4 in.
and
Da.vies, J. A., Bubble Trays . . . ,Part II, Pet. RefilMr, September, 1950, p. 121.
Geddes, R. L., Local Efficiencies of Bubble Plate Fra.ctionators, Trans. A.I.Ch.E.,
42, 79 (1946).
.
19
20
481
has been reported. Uniflux trays21 a.re a recent tunnel-type development which involves a single S-shape member (set on its side) which,
when interlocked with a second such member, constitutes both the liquid
trough and the vapor tunnel. I t is a highly practical construction
because of its simplicity.
. Th~ downpipes or downspouts (Table 16-3) for conducting liquid (or
froth) down the tower must be large enough to allow disengagement of
vapor from the liquid. The froth is about half liquid. A residence time
3 to 5 19 sec (velocity of 0.2 to 0.33 ft per sec) is recommended, which
means that the fr,Oth travels at about 0.4 to 0.67 ft per sec. Although
downc~ are frequently the bottleneck in a tower, Borne authorities 22 23
.
'
. ./
TABLE
Plate
num-
PERP'ORMANCE OF DOWNSPOUTS
.-..,........... .
Arrangement'"
ber
1
16-3.
Downspout
area, sq ffi.
. Downspout
periphery,
in.
Approximate/) Allowable
vapor
effective downspout periphery, velocitYt
ft per min
in.
1.48
4.32
3.0
.~
7.35
6.5
6.5
1.33
6.5
5.0
31.5
J
38.5
34.0
/<
>,
7.85
13.8
6.5
37 .5
5.31
13.8
5,5
34.0
suggest and report actual liquid velocities (no froth) of 0.56 to even 1.7 It
per sec. Kallam 16 has studied the performance of several downspout
Arrangements installed in a single tower. At an oil-to-gas -ratio of 30 gal
oil per 1,000 ell ft gas, the plates performed as shown in Table 16-3.
This indicates that both area and perimeter are involved in the performance of a downspout. A study of the fall distance and the interference
of several streams flowing into the same downspout is also discussed.
C. G. Kirkbride 24 suggests that vapor disengaging space should be provided between the last row of caps and the overflow weir (Fig. 16-6)-a
time of 1 sec for each foot of froth depth on the tray.
Bowles, V. 0., Socony Uniflux, Oil Gas J., Apr. 26, 1954, p. 176; and Here's How
TTniflux .. Behaving, Oil Gas J., June 20, 1955, p. 100.
n Atkins, G. T., Chem. Eng. Progr., 60, 116 (1954).
13 Kelley et a.1., How to Test Fractionators, Pel. Refiner, February, 1955, p. 159.
24 Pet. Refiner, 23, 32 (1944).
21
482
The weir perimeters of Table 16-3 are not equally effective because part
of the weir .length lies too close to the tower wall. Only plate 2 has.s
totally effective weir, and even it is somewhat impeded at the ends. The
weir formulas [Eqs. (13-6) and (13-7)J of Chap. 13 or other similar formulas 25 can be used for computing the height or crest of liquid over the
weir. Methods of correction for the constricting effect of the column
waH on wedge-type or chord-type weirs have been presented. 25 26 The
overflow weir or dam is usually designed to hold a liquid level (no froth)
of 0.5 to 1.5 in. above the top of the slots of the caps19 but an adjustable
(1 to 2 in.) weir has been 8Uggested. 27 The downcomer should be
. sealed 19 21 with liquid at its outlet by a (static) depth of 0.5 in. (4-ft diameter towers) to 1.5 in. (12-ft and larger diameters), and although a veloc.ity of 0.7 ft per sec can be tolerated 22 under the downpipe, more space if
available should be allowed so that an accumulation of debris does not
hamper the flow. Peavy and Baker 28 found that the height of the overflow weir had little effect on the liquid level in theirequipment---the level
being lower than the weir owing to surging and splashing of liquid at the
last row of caps. In general, the plate efficiency was greater at deep
liquid seals, but the efficiency was lower (for deep seals) at high vapor
velocities. The liquid may tend to short-cut across the plate and cause
some of the caps to be ineffective. This tendency can be corrected to
some extent by means of another weir or dam which is used to distribute
the liquid as it flows from the downspout into the tray (Fig. 16-6) .. For
large plates, over 5-ft diameter, special baffles (Fig. 16-7) must be used
to direct the flow of the liquid so that all the caps are effective. Doublepass. trays (not shoWn) are ones in which one tray has two chord-type
downspouts and the next tray has a downspout across the diameter of
the tower, so that the liquid travels back and forth from the center to
the side of the tower. The parts of the plate that the liquid tends to
bypass are shown (Fig. 16-7) as shaded areas. The passage for the liquid
must not be greatly constricted at any point, or the liquid level on part
of the plate may become so great that vapor Will fail to bub.bIe through
some of the caps (see Figs. 16-8 and 16-9). The caps that are marked on
band c (Fig. 16-7) may act as dams to the How of liquid. In experiments
with the type of plate shown as b, the liquid level was 1 in. higher on the
upstream side when the air velocity was 0.5 ft per sec and the water
White, R. R., Bubble Plate Column Design, Pet. Processing, February, 1947,
p. 147.
28 Bolles, W. L., . . . Estimating Tower Diameter and Tra.y Spacing . . , Pel.
Refiner,. December, 1946, p. 103.
27 Bolles, W. L., Optimum Bubble-ca.p Tray Design, Part II, Pet. Proce8sing, March,
1956, p. 82.
t8 Efficiency and Capacity of Column, Ind. Eng. Chern., 29, 1056 (1937).
U
483
rate exceeded 40 gal per min. The removal of the cap at the end of the
baffle greatly improved the level gradient. Likewise in pla.te d the caps
nearest the center often fail to function because of a high liquid level. In
large towers it is sometimes necessary to arrange the plate as a series of
cascades, each deck of caps being separated by dams so that the level on
each deck will be independent of the level on the deck before it. In this
manner, the submergence at each part of the plate can be kept about the
same. Plate c indicates four such cascade decks.
(a)Small Diameter
Liquid flows across the plate as froth and stands in the downcomer to a
height (inches), in the case of the Koch Engineering Company Kaskade
tray,14,29 which is double the pressure drop (also stated in inches of
liquid) across the plate. Perhaps this is a coincidence, but Souders et al. 10
report the same general relationship. At high rates of liquid flow the
froth may not have time to separate as it flows through the down comer,
and hence the computed liquid height (no froth) in the down comer must
be about doubled. Kirkbride 24 also recommends that the height of liquid
be multiplied by 2 when computed by his approximate formula [Eq.
n Litwin, H., Cascade-type Tray Introduces New Fractionating Principle, Oil (ku
J., Mar. 22, 1947, p. 237.
.
10 Souders, Huntington, Comeil, and Emert, Ind. Eng. Chem., 30, 86 (1938).
484
+ hinD) + ha + hro
2 [II,. + 30
+ O6ul +
H = 2(hw
or
H =
(;.)'""J
u::
. (16-3)
1!
How through downspout, and hn = head for friction loss through risers
and caps, all expressed in inches fluid. Referring to other symbols, Lis
liquid How over weir, cu it per sec; WI is effective 24 weir length, in.; 1.td
is liquid velocity at restriction of downspouts, ft per sec; u,. is vapor
velocity.through risers, ft per sec; and PfJ and PL are density, Ib per ell ft
of vapor and liquid, respectively. This equation outlines the significant
factors, although eXperimental results fail to indicate the square function
485 -
'.'
.,
(Koch
above unless the plates are far apart, and Kallam 16 finds that mixing may
not be effective at high velocities because the gas tends to channel through
the liquid. Many petrole~-oil columns a.re designed for slot velocities
of 9 to 14 ft per sec, but in reality the slot velocity iB a.~tomatically
governed to.,a large extent by the number of caps that Cal). be put on the
tray (see Table 16-2).
W eep ho1~ (Fig. 16-6) of a diameter of % to % in. are needed to drain
. the tower in a reasonable length of time prior to steamout. Four sq in.
ot holes per 100 sq it plate area has been suggested. 27
The results of very high ra.tes. of liquid How through trays are indicated
486
in Fig. 16-8 and in Fig. 16-9 wruch shows a newly developed cascadetype tray.U.31 The cascade tray (Kaskade, Benturi, and Flexitray
designs) apparently exhibits a higher efficiency and greater capacity
(about 35 per cent) than conventional 'trays, but it is more complicated.
The' single enlarged Kaskade unit indicated in Fig. 16-9 is too small for
most commercial operations, and hence several of them are lined up
across the tower with each adjacent pair of units dumping into a common down comer as indicated around the enlargement of Fig. 16-9. The
, exaggerated crossBow of vapor indicated in the bubble-cap tray of Fig.
16-8 is not troublesome in small towers; but in large towers,29 particularly if I-beam tray supports extend into the path of vapor crossflow, the
operation of the trays may be completely upset.
Davies 32 has derived Eq. (16-4) for the liquid gradient across trays of
caps spaced in an equilaterial triangle arrangement.
1ll} -
;'~d~
(16-4)
do
I"")
total flowing clear liquid depth adjacent to' overflow weir, in.
11 = total free space between caps normal to liquid fI~w (average
of various rows), in.
l2 = total free space between risers normal to liquid Bow (average
of various rows), in. '
-'
Q = clear liquid flow, gal pe'r min
Pfl = vapor density, Ib per Cll ft
r = number of rows of caps perpendicular to liquid Bow
8 = cap skirt clearance (distance of bottom edge of cap above
tray floor), inches
u = superficial tower vapor velocity (using total tower area), it
per sec
In solving the equation, Cd obtained from Fig. 16-10 is inserted in Eq.
(16-4) along with other variables to solve for .:::11.1. The value of u v'f';;
is computed, and then by the use of Fig. 16-10, the actual A,.; can be
determined.
Tray Perlormance. The over-all performa.nce of a bubble tray can be ,
outlined or defined as in Fig. 16-11 27 or 16-12.13 At -minimum vapor
at Harrington et al., No Peace for Fra.ctionators, Oil GaB J'J Nov. 24, 1945, p. 135.
"Davies, J. A., Ind. Eng. Chem., 39, 774 (1947). See Rodriguez, F., Chem. Eng.,
November, 1956, p. 230, for a direct nomographic eolution~ .
H Munk, P., New Approach to Tray Design, Pst. Rejifltf', July, 1950, p. 104.
...
,' .
,487
120
40
20
qpm(lJot)
60
2.0
1.0
0.9
07
~
~~
.---- --
---~-----
.~
~--
'
' /
7
J
as
Q3
Q6
0.4
"
V~
,,,., '"
as
"to
~
Holddown bars below
I, ' \
.-
vIP =
I
20
40
60
80
qpm(hot)
fI (overage overall flow width)
100
120
140
rates the caps pass vapor only intermittently, and this is called pulsation,
and between burps liquid tends to overflow through the vapor risers. At
the other extreme of vapor velocity, excessive entrainment occurs by
spouting or jetting of liquid to the tray above, and in the extreme the
cap slots may be 80 overloaded as to cause excessive pressure drop,
spouting, or coning. At extremes in liquid flow, liquid or froth backs
up in the downpipe (down8pout buildup) into the tray above ahd may
.i
488
PETROLEUM REFINERY
ENG~EERING
finally appear at the top of the column by what is called flooding. Likewise, at the highest liquid loads, liquid may dump or drain to the nextlower tray through caps that pass no vapor (Fig. 16-8), but it is.. com..
man practice to design for such a liquid gradient and vapor velocity that
all of the caps are working, and this results in what is called 8tability. A
series of charts similar to Fig. 16-12 for various cap arra.ngements, spac-
600
800
1000
1200
"
Liqujd load, gpm
FIG. 16-i 1. Qualita.tive effect of liquid and vapor loads on bubble-ca.p-tray perfortnAIlce. (Ptt. Proceuing.)
vitally affects the stability of the tray, and- from Fig. It>-12 it appears
that the use of several tray levels (casca.ding) should he practiced more
frequently than in the past.
Pressure Drop and Downspout Backup. Pressure drop through the
caps can be a little larger than the hydraulic gradient computed by the
Davies equation [Eq. (16-4)] for tray stability.33 .At the same time, pressure drop causes liquid to back up into the downcomer. Pressure drops,
by the study of T.": G. Dauphineu for three sizes of caps, based on the
U
489
200
Rows ofcops
86
Downspoul
buildup
1201---+-
: 120
80
40
160
QjL
fiG. 16-12. Operating limits of bubble trays (4-in. cap diameter, 2ain. cap spacing,
and 4..6 caps per sq it). (pet. Refi~)
8SS11mption II that the annular area, nser area, slot area., and reversal
a.rea. a.re all equal, and equal to one-half ()f the 4tside area of the cap, are:
For a-in. caps:
Ho
= 1.939
[U(d.)0.5
(d L
6 ]0.84
(d,,) 6.
2.234 [ (d L _ d.,)o.~u -
u(d,,)tt.15
2.768 [ (d L _ d.,)o.u
1.
]0.82
d.)O.Sl -
]0.88
(16-5)
(16-6)
(16-7)
490
The total buildup in the downcomer in terms of clear liquid heads above
the lowest point (the overflow weir) is (1) wet-cap pressure drop, (2)
crest above overftow weir, (3) hali of hydraulic gradient across plate, (4)
height to distribution weir and its crest if such a weir is used, and (5)
pressure drops for flow or contraction through the downspout [see (Eq.
16-3)]. For low liquid flows the backed-up height may approach twothirds l l of the tray spacing, but at higher rates, lower backups are necessary because of the need of time for the disengaging of vapor from the
froth. Mubk 31 suggests decr~sing the allowable backup by 1 inch for
every 10 gpm per it of weir length above a liquid rate of 65 gpm .
.Pressure drop in vacuum towers is vitally important, as well as the
pressure drop through any condensing equipment and the vapor line.
The drop through pressed-steel caps installed in vacuum towers operating at ahout 40-mm pressure and with a Slot submergence of M6 in.
ranges from about 0.7 mm per plate at a superficial velocity of 7 ft per
sec to about 1.2 mm at a velocity of 13 ft per sec.
Plate Spacing and Entrainment. The obtainment of equilibrium on a
bubble pla.te is governed by two opposing factors~ One of these, the
intimacy of vapor-liquid contact, tends to produce equilibrium; but if the
contacting or bubbling is too violent, liquid particles will be carried from
one plate to the next by the vapor and will tend to destroy the separation
that has been obtained. One kind of entrainment is a distinct splashing,
spraying, or spouting of liquid particles. The particles are thrown
upward by the 'velocity they attain at the ~lot of the cap, and they will
fall back into the liquidif they expend their energy content before they
reach the next plate. The liquid particles are relatively large, and a
relatively high velocity is necessary to cause them to be thrown to a
height of 18 in. This kind of entrainment can be eli"mjnated almost
entirely by placing the trays far apart.
.
Another kind of entrainment might be referred to as "carrying." Very
small particles of liquid do not fall through the vapQr as fast 8.8 the vapor
rises, and they are carried by the vapor stream to the plate above. At a
given velocity, all particles smaller than a certain size will be carried by
the vapor to the plate above and the larger particles will fall slowly back
to_the parent plate. At ordinary vapor velocities, the size of the particle
that c~ be carried from plate to plate by the vapor appears to be between
0.1 and 0.2 mm in diameter.
Chillas and Weir 31i report that entrainment is negligible at a velocity of
2 ft per sec but that it amounts to 7 and 20.5 per cent at 4 and 5.5 it
pet:. sec. In commercial columns, having trays spaced at 22 in., the
entrainment36 is approximately as shown in Table 16-4.
III
1
I
FRACTIONATION
TABLE
Material
Pressure
Gasoline ...........
Gasoline .......... .
088 oil ............
JUr-1V&ter ..........
'JUr-1Vater ..........
Atmospheric
Atmospheric
20mm
Atmospheric
Atmospheric
.A.Nn
491
TOWERS
16-4
Linear velocity I
Ib per sec
Per cent
entrainment
1.4
0.25
39
0.8
10.0
0.3
2.2
1.8
0 .04
0.7
Atkins U suggests the entrainments of Table 16-5. The a/A designation refers to the ratio of the required cap-covered a.rea to satisfy the
widely used Brown and Souders 37 vapor-velocity formula [Eq. (16-8),
curve ,4], to the actual area provided. Inasmuch as the Brown and
Souders formula is conservative and is based on the ,total cross sectional area, a ratio of a/A ,= 1.0 is thought to be~~ a good basis for design.,
TABLE
16-5.
ENTRAINMENT AS A FuNCTION OF
VUOR
LOADmG/J
Va.por loa.ding,
a/A
0.4
0.6
0.8
1.0
1.1
0.03'
0.1
0.3
1
1.2
1.25
1.3
10
,25
492
man
11
= K[ (PL
- prJ) / prJ]o'r,
in which K ranges from 0.12 to 0.43 and PL and prJ are densities (lb per
eu ft) of the liquid and the vapor. Under many conditions the amount
of entrained liquid that is removed is 90 to 99 per cent. In vacuum
tower or jug operations 42 it is possible to attain the vapor capacities of
Fig. 16-13 and curve 4, without 'contaminating the gas--oil product with
the metal contaminants that are so harmful to catalytic cracking catalysts, and in many instances it has been possible to produce penetratiot:l
asphalt as the bottom product while a.t the same time producing a satisfactory cats.lytic feedstock. The mesh blankets (4 to 8 in. thick) must
be continuously washed with a small amount of liquid to prevent the
accumulation of coke or debris. Blankets are being used by some
refiners below each draw plate and a.t the top of the column, but the
point of major usefulness is between the feed plate arid the lowest Sidedraw plate.
Many years ago, a device ca.lled the Centrifix38 was found to be effective in removing colored material (Table 16-6) from a lubricating-oil
stock that was withdra.wn above the vaporizer and in reducing the
amount of acid that was required to treat the product. A 9-in. layer of
steel wool's was able to reduce the color to about one-twentieth of the
color when no wool was used. Chillas and Weir 3i have also studied the
effect of a special baffle, similar to venetian blinds, on entrainment.
Anon., Prevention of Entrainment . . . ,Ref. Nat. Ga80. Mfr., Februa.ry, 1934,
p.70.
U Chillaa and Weir, Ind. Eng. Chem., 22, 206 (1930).
4D Reynolds, S~ C., Oil Gas J., Aug. 10, 1953, p. 117; a.nd Anon., Pet. PrOCeBftng,
February, 1954, p. Z27.
41 Campbell, J. M., Knitted-wire-mist Extractors . . . , Oil Gas J., Mar. 5: 1956,
p. 115.
n Nebon. W. L'J Capacity of Vacuum Towers, Oil Gag J., Apr. 9, 1956, p. 131.
IS
493
Diamet~
16-6.
Vis-
Per
cosity
cent of
a.t
crude
210F
Crude
Reagan. _.
East Texas ..........
Little Panhandle ... . .
Barbers Hill .........
a _
Hivis produot
It
.......
140
6
6
5
8
O.D.G color
without
Centrifix
1,550
140
125
5,SOO
11,900
13,400
1,650
4.,000
145
3,600
1,500
27.0
13.8
30.0
42.0
The optical density (O.D.) color scale of the Atla.ntic Refining Company is directlJ
proportional to the depth of color. See page 389.
/I
(16-8)
(16-9)
The symbol w refers to pounds per hour, and a to the area of the entire
tower in square feet. The constant K is dependent primarily on the tray
spacing (Fig. 16-13) but also on the type of tra.y and the kind of service.
The various general types of services are:
494
1. Maximum rates with perforated, sieve-type, Turbogrid, and Kaskade trays. 14,fM4,411
2. Maximum for perfectly designed bubble trays operating a.t most favorable liquid
loads,n,aa Also, normal performance of Kaskade, Turbogrid, perforated, and '
similar plate constructions. H n - 46 Also, liquid':'washed side-to-side pans.
1100
--
.~
g900~--~---+----~--~--~r-~~~~~
~
~
Cl
~700
~
:!I.
S
~
~ 500~-,H-~~~~~~~~~
~.
IOO~'~~-~--~--~-~--~--~--~--~--~
10
15
20
25
Tray spaclng in.
30
35
FIG. 16-13. Effect of tray spacing and type of service on allowable vapor load of
fractionators [see Eq. (16-8)1.
3. Normal performance of bubble plates through normal range of liquid load.s 2233 S
at atmospheric and higher pressures. The lowest values of K apply to high liquid
loads and wide cap spacings.
Thronton, D. P., Pet. Processing, May, 1952, p. 263; Kellogg, R. G., Oil Gas J.,
Apr. 18, 1955, p. 128; Duren and Buck, Oil Gas J., Feb. 28, 1955, p. 122; a.nd Mayfield
et 81., Ind. Eng. Chem., 44, 2238 (1952).
.
H Fractionator Plate Symposium, Pel. Engr., May, 1954, pp. C-17 to C-31.
4i Barnes, K. B., Oil Gas J., Sept. 15, 1952, p. 72; Shell Develop. Co., Chern. Eng.
Progr., February, 1954, p. 57; and Pet. Refiner, November, 1952, p. 105. .
" Strang, L. C., J. In:st. Pet .. Tech., 22. 166 (1936).
(3
495
4. Original Brown and Souders a7 values for K dating from 1934 when tower- design
was not fully understood. Also vacuum-jug or dry-vacuum service using washed
wire-mesh mist extractors. 4t Also, crude Bash ,section of atmospheric topping
towers. 22
5. Stripping stills in absorption plants, a.nd wet-vacuum refinery services.
6. Absorption towers. SM7
7. Foaming due to excessively high temperatures (vacuum decomposition) in vacuum
service,42 or very 'high-viscosity liquids in vacuum service,22 or high-boiling aromatic fractions used as absorption oils in absorbers. 48 Mist extractors are not of
much help for these services.
j
All of the allowable vapor velocity rates [Fig. 16-13 and Eq. (16-8)1 produce about the same degree of fractionation. Note also that the rates
are based on the total free cross-sectional area of the tower and that
actual velocities in the immediate region of the.part of the plate covered
with caps is therefore higher. Linear velocity is altered so greatly by
various conditions of temperature and pressure that it is not of much use
for purposes of comparison. However, for estimating 'purposes Table
16-7 is helpful.
TABLE
16-7.
Operation
Topping ................. . ..
Cra.cking . . ............. . ....
Pressure dist. rerun ..........
Solu tion remn.-..............
Pressed dist. rerun ...........
Pressed dist. rerun ...........
Vacuum ................. ~ ..
Vaecum ....................
Stabilizer .... : ..............
N a.t. gaso. absorber ..........
Nat. gaso. absorber ..........
C7
Pressure,
psis or
rom
Tray
spacing,
I1Jb
40lb
20lb
251b
25lb
60mm
22
22
22
22
22
24
30
24
18
14
18
30mm
90mm
160lb
50 lb
4001b
in.
Su perficial
tower velocity,
ft per see
2.6-3 .3
1.5--2.2
2.8-3.7 G
2.8-3.5
2 . 8--3 . {}<a
fL0-9.0
9.0-12.0
5.0-8.0
2.2-2.8
1.0-1.3
0.5--0.8
Example 16-6. Diameter of Topping Tower. See Examples 16-1, 16-3, and 16-4.
The quantities and conditions will be taken frOID these examples. Density of vapor
a.t top of column (the reflux in the column is always hot reflux):
496
203.5 X 379 X
.
D enBlty. . . . . . . . . . . . . . . . . . . . . . . . . . . ..
287
p.
+ j60 760
520) X 7SO - 107,600
lb'
= .eli ft
19,~
= 107,600
= 0.18 1
w/a
P,(PL - p,)
= 0.181(42.7
-' 0.181)
'=
7.7
'.
Di
ameter
~ J 9.55
= -V 0.785
35f
.
The a.ctual tower (Examples 16-1 and 16-3) was 4 ft 6 in. in diameter (a. factor of
safety of a.bout 66 per cent), but it may never have worked a.t full ca.pacity (date
1930).
Lb
Moles
106,000
331.0
49.6
12,000
1,400
119,400
78.0
459.0
760
490 + 460
520
- 8,050,000 eu It per hr
Approx. volume 459 X 379 X 30 X
119,400 = O. 01 48 ==
D enSl'ty 0 f vapor 8,050,000
Assume PL
p.,
= 0.0148(50
- 0.0148)
= 0.74
The constant K for curve 5 of Fig. 16-13 is a.bout 600. The allowa.ble mass velocity
'to/a = 516.
.
119400
Cross-sectIonal area. of tower = 516 == 231 sq ft
The dia.meter is 17.25 it with no factor of saiety. (The actual tower tha.t was used
during 1929 for these conditions was 17 ft in diameter.) The linear velocity corresponding to the foregoing is 9.7 ft per sec.
497
498
commercial operations.
Efficiency
= 0.17
(16-10)
- 0.616 loglo JJ
IOcR I
8
.....
~
..
8 10
.,
8 10
of
6' 100
r
T
~
:-
Legend:
FRACTIONATORS
~e~
~;je
r--.
--.J _
r--.
~
r+
Q=
Relative YOlohlily
of key COIT/pOIIenJs
/It -Viscosilf oIl~
in CMtipoises
~-
ABSORBERS ............
use
,
Legend:
H-.(Henry Low constant for system)
leu fl) (ATM) per Ib inoI.
P"",TolWI' P'esstJrl>. ATM
p=VtSccsily 01 so/ilenl, ~
M=Mol weigII/ of sokmt
~ - Densify 01 solven/, I/) pe C/J
1.0
QI
~-r~iDr'1JnUm
.,
6},
1.0
......:
""\
'\
,0t iii I
.,
Vohes
.........
6},
'1\
10
oI!(#OF 7ti
. "
6},
100
..
"1000
6},
FIG. 16--14. Average over-all plate efficiencies of fra.ctionators and abSorbers as funcof relative volatility (or solubility) or viscosity. (O'CooneU, Tram. A .I.Ch.E.)
~~ns
16-8.
HExANE
Vapor pressure"
Tem.
pera-ture, of C 2 H 12,
P1mm
97
100
105
110
120
130
135
140
145
150
154.4
156
G
760
800
895
960
1,160
1,350
1,460
C2 H u ,
Plmm
238
255
280
325
396
478
1,600
530
580
1,750
1,900
2,010
2,150
638
700
740
760
760
-PI
522
504
480
435
364
282
230
180
122
60
20
0
PI - P s
522
545
615
635
764
872
930
1,020
1,112
1)200
1,270
1,300
3:1 mole
fraction
1.0
0.925
0.78
0.685'
0.477
0.323
0.248
0.176
0.-109
0.050
0.0157
0.0
Pl~l
760
740
698
657
554
436
359
282
191
95
31A
0.0
Yl mole
fraction
1.0
0.975
0.92
0.865
0.73
0.575
0.476
0.371
.0.252
0.125
0.0414
0.0
"
r
.,
the vapor is progressively cooled,' and successively lower and lower boiling cOndensates are collected. The condensate is relatively rich in high-boiling components. -At one time the term "dephlegmator" was used to designate any sort
of fractionating tower, but today the meaning of the term is usually restricted to
the use herein given. In a more restricted usage the term fractionaUon is used in
referring to a countercurrent operation in which a vapor mixture is repeatedly
brought in contact with liquids having nearly the same composition as the
respective vapors: The liquids are at their boiling p()ints, and hence-part of the
vapor is condensed and part of the liquid is vaporized during each contact. By
a series of contact treatments the vapor finally becomes rich in low-boiling components and the liquid becomes rich in high-boiling components. The terms
rectification and fractionation are used synonymously. Stabilization is a fractionation operation conducted for the purpose of removing high-vapor-pressure
components. The plates above the fOOd point are called "rectifying plates,,'and all of them together are classified as the rectifying section of the column.
The plates below the feed are called the exhausting section. The plates below the
.[
. 500
150 ~ ~ .........
."
+CD
140
..c
c
.............
f 30
.r: l
.:s .
~icl
r....,
liquid
et3)IIO
"'N....... A
~(lp'ora:
u:;.
:l 120
Vapor
~ "-
---~~
-~
...........
Cb
0,
100
"6
....
0.3
0.4 0.5 Q6 0.7 0.8 0.9
Mol Fraction of Pentane
FIG. 16-15. EquilibrillIll between pentane a.nd. hexane at atmospheric pressure (see
Table 16-8 and Fig. 16-16).
.
. 900
0.1"
0.1.
1.0
":0.9
&..
~O.a
c
Q)
c
~
0.7
~O.6
.'-/
]0.4
o
'~03
0.1
VB
AV
......
'to.5
~O.2
~ l.b
s.
v
V
o
l~
. -feed do not function as exhausting plates unless heat is added to the oil at the base
of the column. Hence most petroleum-oil columns do not have exha.usting
s,ectioI).8. The plates below the feed in petroleum columns are usually stripping
pla~B. An exception is the na.tural-gasoline stabilizer in which the stable gasoline in the base of the column is heated by a steam (or hot oil) reb-oiler .
. Mec.hantstn of llractionatlon. In computing the degree of fractionation that is
. - accomplished in a partioular equipment, the relation between the composition of
the liquid and the vapor a.t equilibrium must be used. Either experimental
501
aquilibrium data must be available, or the engineer must compute such data from
known laws. Although 'Raoult's law is valid for only certain conditions J it is
, about the only general relationship by which equilibrium data can be computed.
Thus, Eqs. (15-1) and (15-2) were used to compute the equilibrium data of '
Table 16-8.
Two common forms 01 ,equilibrium diagrams are ' shown in Figs . .16-15 and '
16-16. As an example, the vapor from a liquid having a composition of 0 ..3 mole
fraction of pentane contains 0.546 mole frae~on of pentane. However, only So
o ~~;l'
B 116S'f.
r-0._18_2_ _-F~ I05.6DF,
(0)
0.782
A 1315F.
0.546
r-----+--_
116.5" f.
0.546
Heat--~;;;; 131.5F.
0]
Bottom
, product
(b)
Battoms product,
0.3
FIG.
16-17. Fundamentals
1o;;;:::I!::::::7
very smaU quantity of this composition of vapor can be produced, because the
liquid becomes less rich in ~entane as vapor is formed. It the heating is continued, the liquid becomes Jess and less rich in pentane and finally, a.fter all the
liquid is completely vaporized, the composition of the total vapor is the same as
that of the original liquid, or 0.3 mole fraction.
As an illustration, the hypothetical case of the fractionation 01 an infinitely
large quantity of liquid by a series of redistillations will be useful. Consider the
series of stills shown in Fig. 16-17a, and compare the compositions with the dotted
lines on Fig. J6-15. An infinite amount of liquid containing 0.3 mole fraction of
, pentane is heated 8. fraction of a. degree, and a smaJ! amo~t of s. vapor containjng
'
502
503
. SUbscripts!
P = product from top
b = residue product
,-
,I
J .... feed
n = any plate in rectifying section
n + 1 = plate above the nth plate
n - 1 = plate below the nth pla.te
t = top pla.te
t - 1 == pla.te below the top plate
m = any plate in the exhausting section
i = still
-----
J
I
,
J
t-I
n+1
0-1
f+1
F-+---~trtr
f
m.1
m
m-I
s+J
F=B+P
And for the low~boiling component: .
FXJ
= Bx"
+ PX
'lJoHom
proclvcf
r------~B
V=P+R
and
(16-11)
V' = R' - B
and
VYn
+ Rx,. =
Vy .. _l
+ RXR+l
. also
Yft-l =
R _ Yn V - X"i-I
R
V (x" -
Yn-l
-
Xl l+1)
:en
(16-12)
+ y"
VYI
RXJ+l
P:r;p
004
But at minimum vaporization an infinite number "of plates are used and the
" "change in composition from plate to plate is very small. Hence 3;1+1 is equal to %/.
V IfUnYJ
= RmiuxJ +Pz,
R~ = Vmln - "P
V mlnYl = (V ~ln - P)xJ
But
= P(xp -
V miD
+ PX
ll
xJ) "
(16-13)
y! - x/
RrnizJ = P(x
or
y,)
fj " -
111 -
(16-14)
%/
XI nnd YI can be found by the equilibrium relation for the compounds that are
being separated.
computations:
~xa.mpJe 16-8. Number of Perfect Plates by Mathematical Method.
A mixture of
pentane and hexane containing 0.6 mole fraction of pen tane is to be fractionated at
atmospheric pressure to produce a product containing 0.95 mole fra.ction of pentane.
The feed is 8.t its ooiling point. Usc twice t.he minimum reflux.
How many theoretically perfect plates ore required to get the separation?
Basis: 1 mole of product {see Eq. (16-14).
YI
" RJD.l.n
-
XI' - '11/
0.95 - 0.82 ..:... 05"9
=
111 - $/
0.82 - 0.60 - .
Aotual reflux:
2.18
y, - Y'-l
"V = x, -
X.
"Also
:r;,
in equilibrium with y,
(~.95)
$fj
the' - 1 pla.te.
1/1-1':""
= :It -
YI-I
Zi_1
!Ii-I
= 0.901
Xi_l -
Y,-2 = 0.839
The liquid flowing from this plate has a. oomposition of 0.625. Obviously only a.
part of another perieet plate is required to complete the rectifying section, because
the feed composition is 0.6.
"
505
==- %n+2, etc. At each plate the composition of the vapor and that of the
liquid are related to each other by the equilibrium relation shown in Fig,. 16-16.
The equilibrium relation is plotted in Fig. 16-19 and also a 45-deg line whose equa-,
tion is :s; = y. The 45.deg line is the operating line for the' condition of infinite
reflux. The operating line relates the composition of the vapor leaving the plate
a.nd the composition of the liquid entering the plate. For conditiODB other than,
infinite reflux, the liquid composition x does' not equal y and the operating line is
less steep than a 46-deg line. The equation of t,he operating line may be fdrmu- '
lated as follows: At the top plate when producing 1 mole of product,
, Yn+l
R
V
,But y,
Y'-l ...... y,
= x, -
::t1' ,
= XI'
,
R 'YI-l - Xp
V = x. -,:l: p
1/;-1 - z;,
= v(li'
, Ii
1/t-l ....
Xj,)
,,'V,
+,V xp
V=R+P
But
Y~l
R(x, -
X-p )
+'
(R + P)xp
V
,R
=
V x,
+ :P',.V
X1'
or
..
(16-1~)
:(16-15b)
, This ,is an equation of So straight line having a slope of R/V and h~ving an inter-
cept on the y axis of (P /V)x". Since the operating line extends from (x", ,Y1J) to
the intercept, the line can also be drawn without u$lg the slope.
Example 18~9. Number of Plates by Graphical Metbad. &a.mple l.~ will be
'repeated, using the graphical method.,
,
The y intercept oC the operating line is
"
p,
,V
Xp
==\
1
2.18 X 0.95 = 0.435
'The operating line is drawn through the intercept y == 0.435, x """ 0, and through'
the point %1', !It (0.95) (Fig. 16-19). The number of plates can then be ascertained by
drawing horizontal and verticollines as shown in Fig. 16-19. Each point on the equilibrium curve indicates one theoretical plate. Thus about 3% perfect plates are
required (see Example 16-8) for the rectifying section.
The dotted lines indicate the number of plat~ required at i.n.finite refiux. The oper'ating line lor infinite reflux is the 45-deg line. Only a little more than. two plates are
required if infinite reflux is used.
'
'
, I
j'
506
1.0
(Xt-I,Yt-t,h . 2 ./ V
0.9
,.,
3.L
(Xt-2,Yt-2)
0.8
'1L
~A
.F
L.
15 :/ ,.
0.7
0-
....t:
. a 0.5
6V
"
,o'
1/
0.4- -' V
l.L..
0.2
O.t
.7 /
I V
il
. Ii'
i0A35 r-'pxp
~ 0.3
,.1--
;, r7
~ 0.6
,,~
t., ~ ~
tx~
V iX
,/ 1/ 1
Yr-Xt'yt':'t)
I: /\
11 (x t -l.Yt-2)
/'
LL
vV
L AY
If
8
~
~
o 0.050.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Xf
)(.b
The exhausting operating line is drawn as indicated above. The stepwise procedure
is continued past the feed composition until the liquid has a composition of 0.05 or less
(see Fig. 16-19). About nine perfect platc.s are required.
If the plate efficiency is 60 per. cent,
Actual plates
= ~:: = 14.7
Ponchon Method. ~ weakness of the McCabe-Thiele method, as out-lined heretofore, is the fact that the transfer of heat is not directly introduced. Ijeat must be transferred on each plate, reboiler heat must be
supplied at the base of the fractionator, and cooling by reflux must be
accomplished at the top. The method deVised by Ponchon!ili does not
ignore these relationships, and although space is not available for an
explanation of the Ponchon method, Example 16-11 will indicate its general usefulness.
56
507
Hexane ............
Pentane ............
15S .7QF
96.7F
Vapor Liquid
325
305
180
150
The enthalpies of hydrocarbon mixtures are usually straight lines as ShO.W D in Fig.
16-20, but for ~onidea.1 systems the lines ma.y be curved.
Dn.shed lines connecting vapor and liquid are the equilibrium compositions of
Fig. 16-15 or 16-16. For the condition of minimum reflux, the composition of the
vapor leaving the feed pla.te is in equilibrium with the feed liquid which contains
0.6 mole fraction pentane, i.e.) 0.817. This is shown as a dotted line leading to an
overhee.d (z; or yJ) composition of 0.95, a.n.d this indicates that 405 to 305 Btu per lb
of product must be withdrawn as (minjmum) reflux heat. Twice the minimum is
actually employed, and hence heat is present in the refiux in the am:ount of 505 Btu
per lb (point marked Y~A). A total of 200 Btu per lb of product must be removed
at the top of the tower, a.nd the condenser must also handle the product making a.
total of 355 Btu per lb. A line leading from this point (500 Btu per lb) tll1'ough the
saturated liquid feed composition of 0.6 and on to Z611 (located a.t the bottoms.composition) indicates the le.ck of heat at the. reboiler or base of the fractionator. This is
negative to the extent of 380 Btu per lb of bottom product and accordingly, 380 plus
178 or 558 Btu per lb must be introduced into the bottom product to heat and reboil
. the bottom of the column.
The number of plates required, or the heat exchanged on each plate, is obtained by
8. step-wise operation. The liquid composition (0.86 from Fig. 16-16) in equilibrium
with the composition of the top product (0.95) is connected with a. de.shed line. This
point is then connected with the Y'1111 point ohtaining the va.por composition 1/'1'-1 at
the (T - 1) pla.te. Such operations are continued until the feed composition is
pused) whereupon the other or X6A turning point is used. Continuing as before, it
appears thAt 8.9 theoretical trays are adequa.te.
1,1'
.,
.,
508
400
'".
/
9/ 8/
i
200
.J
7J1
I
I
""-5
J.
A.
lif 7~ // / r;1
..!.
I~/
"
"- "
/~ (h'~J
./~I 7/'
l ....
.~~
l~
I~
Iq:
i
J
~
"5
I
~
!
'I
~"
l
I .1 / V
1/1/
I /I
/~ ~:l'
k
I'";
i /); ~'/3l
11'
J/
t~
II
"'b
~-
YT-4
It
If
AI1
,1
~
.xT~ ~"'T
~'P
I I VI
I Iiv
If//
-5
.-100 ~
il
Cl:
. -200
-300
/hV
'f/
'I,'f/
'JJ
-400o
~~~Ab'
0.4
0.6
Qe
1.0
MoIlrocIIqn pentone
FIG. 16..20. Fractionation by the Ponchon method (see Examples 16-11 and 16-9).
0.2
509
computations it is found that the split oj each component between the top
and bottoms products is incorrect, a. new assumption as to terminal compositions must be ma.de and the entire computa.tion must be repeated
almost ad infin{tum.. .
Each component in the mixture behaves independently of the others
except as the equfolibrium constants may be altered by the presence of
other components, and for a known reflux ratio an operating equation
[Eqs. (16-15a) and (16-16)) can be computed for each component. A
plate-by-plate computation .can then be undertaken starting at the bottom by assuming a. pla.te temperature and checking by new assumptio~s
until the summation of K:ts [Eq. (15-5)1 equals 1.0. The value of :c for
each component on the next tray can then be computed by use of the
operating-line equations [Eqs. (16-100) and (16-16)J. Similarly, a plateby-plate computa.tion starting i\t the top and summing y's!K's is conducted until at some plate the composition found is t!he same as one
found when starting from the bottom. If the assumed terminal compositions are not perfect, a. perfect ma.tching of composition at some intermediate plate is never found and new terminal compositions must be
assumed.
Example 16-12.. Three-component Fractionation. A feedstock cont~ 50, 30,
and 20 mole per cent of pentane (A), hp.xane (B), and heptane (C). It is desn-ed to
produce s.n overhead product that cont~in8 only 0.5 mole per cent hexane and a. bottoms product tha.t contit.iDs only 1 per cent pentane. The reflux ratio is to be 4 and
the pressure 1 a.tm. The feed is preheated to its bubble point, and it is introduced at
a. plate which is a.t the same temperature.
By a. penta.ne material balance based on 100 moles feed, P molee of overhead:and B
moles of bottoms a.re produced.
50 "'" P.~A
B~u
0.995
= 99.5 - O.nSB B - 50.25
P = 100 - 50.25 = 49.75
At .xPA
50
= (100
- B)ZPA
+ O.OlB
=0
Feed,
moles
Overhead
Moles
Fraction
Bottoms
Moles
Fraction
0.010
0.592
0.398
1.000
50
49.50
0.995
30
0.25
0.005
0.50
29.75
20
0.0
49.75
1.000
2Q.O
50.25
100
.....
The computations must. be started at the bottom because only the bottoms product
shows heptane, whereas it wa.s assumed tha.t heptane in t.he overhead was negligible.
The overhead a.ct11ally contains about 0.0000001 mole fraction heptaPe," and no one
!.
;,
.i
~ :.
510
could estimate this composition accura.tely enough on the first trw to a.rrive finally
a.t a reasonable_bottom composition.
.
= 4 X 49.7~ = 199
V = VI ""' 49.75 + J.99 = 248.75
and for plates below the feed when the feed is at its bubble point
R' == 199
The operating-line equa.tion [Eq. (16-16)] for plates below the feed is
R'
y",
=V
Z",+1 -
B
V x"
299
"'" 248.75
Zm-l -
SO.25
248.75
Zb
For pentane, the composition of the vapor from a tray (yA) is related to the liquid
on the tray above (3:.&) as follows:
For hexane
YB = 1.202xB - 0.1195
For heptane
yo = 1.202%0 - 0.0805
The composition of the vapor leaving the bottom of the column is computed [Eq . .
(15-5)1 from the composition of the bottoms product by 88SUming a tempera.ture,
obtaining values of K's (or vapor pressures), and computing the l:Kz. At the right
temperature (169F) the summation is equal to 1.0.
(1)
(2)
x,
(3)
0.010
3.4
Cra
0.592
C7
0 .398
1.28
0.51
C"
(4)
0.034
0.759
0.203
0.996
(6)
(5)
y.
%.+1
or
%1
0.034
0 .030
0.762
0.204
1.000
0.7315
0.2365
In column (5) the summation of column (4) was made to equa.ll.O by inspection. The
X'+I terms in column (6) were computed from the values of y. in column (5) using the
three exhausting operating-line equations as indicated here for heptane:
yc = 1.202xc - 0.0805
0.204 = 1.202%0 - ' 0.0805
0.2845
Xc = X'+l = Xl = 1.202 - 0.2365
.
511
on the plates below the feed plate when the Cractionator is first operated. This
brings the composition closer to %. or X&, in fact close enough to permit the lower trays
to produce the bottom composition x.. All avaiJa.ble jnformation indicates that the
disturbance caused by introduction of the feed ma.terial does not significantly change
the number of plates required.
TABLE
Temp,
"F
169
16-9.
153 .
160
16-12
143
132
109
121
102
98
99
fJ7
:co
%1
~I
:.
:c.
s,
%,
-- -- --
%10
~-
0.010 0.031 0.076 0.170 0.322 0.501 0.713 0.868 0.942 0.076
0.692 0.732 0.772 0.716 0.582 0.414 0.268 0.134 0.058 Q.024
. 0.898 0.237 0.152 0.114 0.096 0.085 0.019 0.003 .......
01
c.
07
fl.
III
Vl
ItI
114
111
1/1
1/&
II'
-_. - - - O.
&
....
1It
0,
0.9924918
0.0075000
0.0000082
IflO
..
0.034 0.090 0.208 0:386 0.601 0.770 0.889 0.952 0.980 0.993
0.762 0.808 0.741 0 . .579 0.371 0.2J5 0.108 0.048 0.020 0.007
0.204 0.102 .0.056 0.085 0.022 O.OUJ 0.003
, .... ,.
o.
Za
Z1
%7
.....
......
0.997639)7
0.00236000
0.000000S3
Y1
lOOC - wz
+ K lK'l hJ
9
... K"
or
Yl =
loDe -
U+ 1{lK
wz
~------=----
(16-17)
K",
Fra.ctiona.tion~plant
'
512
Using true
Actual
C~ ..............
re1lUx
2.58
13.35
C!Ha .. ...........
CaBI! ....... , .....
iC,H 1Q ,
C"H 10 . ,
2-.58
13.68
79.20
4.40
0.14
2.56
13.,34
78.46
5.45
0.19
Trace
78.20
5.27
0.35
0.25*
iC,H 12
Assuming
CIO reflux
Trace "
Analysis in error.
400
In a
u.:
~~
..
~ 200
Q..
...
c&. 100
.
::>
/,
~,
~iOo'"
~300
of~.5J5 &.5.2/
4--plate lower,
Reflwces
10
20
...V
40 50 60 70
Percentage Distilled
30
80
90
100
. ,
I
The separation of hydrocarbons from one another to produce commercial purities of 95 per cent or more requires many plates. Table 16-10
indicates the app.roximate reflux ratios required with 20J 30, 50, and 00
pla.tes.
U
Nelson, W. L., Effect of Fractionation on Yield, Oil Gas J., Oct. 6, 1938, p. 56.
"\
.1
513
RAnos
Relative
volatility
2.5
2.8
2.0
1.3
1.2
30
50
2.5
2.0
1.6
1.8
....
1.2
3,8
2.5
2.0
6.3
23.0
4.0
6.0
...
...
. ..
. ..
. , ..
aa
1.0
1.6
N/N ..
V/V m
N/N __
1.3
1.4
1.5
2.15
1.90
1.66
2.0
2.5
1.20
1.07
3.0
1.6
1.50
5.0
1.7
1.8
1.38 -
7.0
1.03
1.001
1.000
1 .000
1.3
00
V/V~
Donpell and Cooper. Plates vs. Vapor Rates .. , Chem. Eng., June, 1950, p. 121
Thus, one has only to compute these two extreme conditions and by working with the ratios of actual vapor (V) to minimum vapor (V",) and the
corresponding ratio for number of plates (Table 16-11), the entire economic
range of reflux and plates can be explored in a, few hours. E:lch system
behaves a little differently, but Table 16-11 enables the establishment
Donnell and Cooper, Pla.tes vs. Vapor Rates . . . , Chem. Eng., June, 1950,
p. 121.
Ii
,'
514
V/V",
2.15
. 1.9
1.66
L8
1.07
1.001
1.0
Actual vaporiza.tion
No. of plates
Number oj plates has a vital effect on the end point of the product,
but at 4 or more plates (topping plant) the difference in end point is only
about 10F if normal reflux ratios are employed. More than 10 plates
(topping plants) have little effect on the/degree of fractionation. 60
In gasoline stabilizers the situation is net clear. Ten plates fail to separate propane from the gasoline or recover all isopentane, even at infinite
reflux, but the use of more tha.n 40 plates does not appear to be justified
for any regular operations. 81
Experience of the Standard Oil Development Company in its commer-cial multidr~w towers is disclosed by J. W. Packie6 as shown in Fig. 16-22
for overhead and highest side-stream products. Dotted lines indicate
the separation when using maXimum amounts of steam. Degree of fractionation is indicated by the gapping 'or overlapping of the 95 per cent
- point (ASTM) of the low-boiling product and the 5 per cent point of the
eo Nelson, W. L., Effect of Varying Number of Plates, Oil Gas J., Sept. 15, 1938,
p.46.
&l
Nelson, W. L., General Applica.tion and Summary, Oil Ga& J., Dee. 15, 1938, p. 46.
\
,,
I
:.
515
higher~boiling product.
for the limited ranges of reflux ratio and of numbers of plates encountered
in heavy-oil towers, it is satisfactory.
Since Packie's 1941 work,." the behavipr of catalytic cracking unit fractionators has been studied in the same manner.62 Only the dashed steamstripped lines of Fig. 16-~ could be compared, but it
found that the
was
100
80
I
I
60
40
0
L
"
20,
;Z
*:;
0
0
DC
10
8
' L-'
'/
.::J
)(
-'-
II
",
~/
11"
.'
./
./
./
/
~
I.L
-.l.
Cli
~I
I ~
t!.
J.
f\;
VL
0'
",L
J
I
.L
'-
~i ..fl..r.~~~~o/I
>I
IL
1/
. I
11 "
0/ ,r:s'l~' \'>~
ii: 30
'+-
.&J
,1
II
I/)
.e0
I
~
~~~
IJ'
If'
.'
II(
::J
t;:
III
ex
4
'3
'.
FIG. 16-22. Gap and overlap of top and side-stream produots from topping towers.
(Packie, Trans. A.I.Ch.E.) See discussion for. a.pplication to cracking-plant iractionators. 1. For overhead and top ' strea.m only. 2. Solid curves for no 8te~m.
Dotted curves for the maximum stripping stee.m genere.lly used. 3. 'Numbers on
curves represent degrees Fa.hrenheit differenoe in 50 per cent distillation points of the
overhea.d and top side-stream products.
100 and 150F (difference in ASTM 50 per cent points) lines were the
same as shown in Fig. 16-22, whereas the lines for differences of 200 and
250F were located to the left (Fig. 16-22) by about 8 to 20F, indicating
poorer fractionation in cracking plant fractionators. Houghland 62 found
it necessary to work with butane-free products because of the very large
amounts of butane and gases associated with the overhead product.
81
516
40
r!.
~t~
i/ ~
t.~oo
30
1_
II ! J !j V 1/
I
J
'I
)
V
/J
if
~~~G~
V
Ij
I~~t!~/;~V ,,' VI
I~ ~~~ I~ 0
II /
~~~vj I
/'
~ .~e"() ' /
r-- ~~ ~
/.
9,/
I~ ~/
II
/
[~
,,\g
lL
L'-
// vI V// /
i
~ ~/ / ~ l~1 ~1
I
rt
,/
/~
~.
.1
2
Less than 0.1 pounds of steam per
gallon of heavy product
or greater, pounds of sleom per
~- gQ'Ion of heavy product
.
J
I
I
I
I
t I
I
I
J
-60
-40
-20
0
20
40
60
ASTM 5%-95% gop, "F
FIG. 16-23. Appro:<ims.te gap and overla.p between eide-stream produots of topping
to wen I (but see discussion), and between heavy gas--oil and the combined product of
cracking-pla.nt ractiona.tora.4~ (Oil Gtu J.)
0'1
The term II combined product" used in Fig. 16-23 means all of the products lighter (except butane) than the.heavy (or heavy gas-oil) product.
This is the material that passes through the top tra.y of the section~
HoweverJ when applying Fig. 16-23 to topping tower side-stream products, the difference between the plain 50 per cent boiling points of the
two side-stream products is used rather than
those of .the It combined
.
product" and heavy gas oil.
517
When using reflux ratios of 4 or 5, the ga.pping or overlapping of solvent or na.phtha products is about as shown&l in -Fig. 16-24. The production_ of only one-finished product per tower (or one tower less than
the total number of products) is contemplated in u~ng Fig. 16-24.
~
~
IL
40
30
.,
II
./
cy'-
,~Ll---+---t--4~---1
~tOO-
201---+-----I7'I/~-+--~~~=--_+-- I --- - - -
15($
II
-101--~,0i>
~ 60
V
I
t..-;:::Io=::~
1 ,~~-. :-- ~---'
~~~... - 1---: ,,- ,-
./
V
i/i7/
I
10
l/""
__
.... 1- ...
"",
"/
E~./
~
I-
~,
",
"
Ar;PROXIMATE ~ OR
Jv,' / -/' '" -<",OVERLAP
'Or A.S.T.M.I
-20r-_+r__~/~'-T;~~~y~~__+L_~_p.~&~~_e__+-__~__-+__~
6~
.f
I'
~-JO
Q.
<
.J
~-40
~
I .:,'
' " ,,
I,
I .
.,'
,/'
III.' ,
II" ,
I,
J
30~,,~I~/--~~~--~~--~--4---~---4--~
150, I I
I'
,,
-50~--~I~r'f~--~---+--~~~--~---+-----~~
6d:
-60~--~-T~--~----~--~--~----+----~---~--~
I I
.
or.
-700~------~5~------~,k-O-------~t~5--~---~20~--~---d25
NUMBER OF THEOP.ETICAL PLATES
6-&
12-16
' J9-~
~-35
APPROX. NUMBER OF AC'l"OAL Pt,ATES
3l-4S .
FIG. 16-24. Gap and overlap of JlI:Oducts from solvent fracticnatom whon only top
and bottom. products are produced. (Oil Gaa J.) _
or
great care. 81
51
Nelson, W. L.) Fractionation fOr Solvent~ Oil GaB J., Oct. 20, 1945, p. 16.1.
518
PETRO.LEUM REFINERY
ENGINEERI~G
or
Theory
Fractionation. The complicated beha.vio~ of complex mixtures
requires the use of many symbols and several new concepts (see Fig. 16-25).84
R .= moles internal (or hot) reflux act top, bas~d on a heat balance and
including no reflux for the plates below the first side-draw plate
eR = moles actual reflux as a fraction of R, includes excess reflux that flows
from the base of the column to other plates that lie below the first sidedraw plate
n = plate number, counting from top
a = total number of plates between two products being s eparated
D = moles overhead product
b = reflux ratio = eR/ D
o = ~oles overflow liquid or reflux at any point
V = moles vapor at any point
z = mole percentage of fraction being considered, liquids
y = moles percentage of fraction being considered, vapors
P = vapor pressure of fraction
11" = total pressure (abs) of system, same units as P
K = y/x = P /T = equilibrium constant
m -:- molecular weight of fraction
mp =r molecular weight of overhead or top product
mA+l = molecular weight of pottoms .product (n + 1 plate) of tower section
studied
d = density of fractiori (liquid at 60F)
d p = density of overhead product (liquid at 60F)
~l = density of (n + 1) material
YI = mole percentage of fraction in overhead product
. y 1 = .liquid volume percentage of fraction in overhead product
. y. . . . ~ = mol~ percentage of fraction in bottoms product of tower section studied
Y"+1 =- liquid volume perCentage of fraction in bottoms product of tower section studied
J = a constant by which the ratio of mole percentages is multiplied to CODvert the ratio to a basis of liquid volume percentage
J = m,tl,a+t!mn+ 1dp
C =- liquid volume percentage of fmetior in feedstock
g = percentage of top product based on feedstock
h = percentage of bottoms product based on feedstock
W~ = product of percentage and composition of fractions that leave a multiproduct tow~ system in other products than the two that are being
studied ,
. ..
Each pair of two products with .the plates between them is considered as a separate fraction~ting tower or section and will be so handled throughout thia entire
discussion. Reflux in a complex-mixture column decreases from plate to plate
by an amount equal to R divided by a, as indicated in Fig. 16-25. Thus, the reflux .
consists of two parts, .a quantity R, which disappears entirely in the column, and
U
.S
. 519
On
~n
eR -
bD
(1 - :)
(16-18)
reflux
Top
column .
.,
t-'t--~~-'"- (e-I) R.
tT''''--~-''lst side
_,-1st side
prQducf "
prodqcr
Refiuxror
lower column
FIG.
'
.
.
16-25. Reflux conditions in the top section of a multIproduct fractionating tower.
relating vapor concentrations at the top and bottom of,a tower section, the relation is'
.
'
.
.
YJt4-'l
(J) , Y+I ..
y,
Yl
(16-19),
'whereas 'for' relating a vapor at the top to the liqujd flowing from the base of th~
tower section
Yfl+l
Yl
(~). =
K~,
Xn+l
. Yl
(J) = X,,+l
.
Y1
(16-20)
Or for an intermediate tow'er section in which both the top and bottpm products
are withdrawn as liquids (as in separating kerosene froni gas oil in a topping
tower), the relation is
Y,,-+l (
Yl
Kr
Kn+l
J)
= Xn+l
Xl
(J) = X ~l
Xl
(16-21)
The composition of the feed is' related to the composition or'the products by' a
materia.l balance. For a tower section producing a ~apor product at the top a.n d
'
a liquid product at the bottom:
loDe
" The sum' of the W~Zl,
= gY l
W2Z2,
.(16-22)
Nelson, W. L., Oil Gas J., July 21, 1938, p. 41; Aug. 4, 1938, 'p. 44; Oct. 27, 1938,
p. 178; and Nov. 10, 1938, p. 44.
.
6~ Nelson, W. L., Intermediate Towers; Oil. Gas J., Dec. I, 1938, p. 40.
!IIi
"
.,
520
looe -
Y
I :=
1M
(hJ /Kr.+l)(Ya+l!r/l)
+g
(16-23)
The mole percentage ratio (Yn+dYl) shown below the line is related to reflux, number of-plates, temperature, and pressure (equilibrium constants) as indicated in
Eqs. (16-24) to (16-29), which could have been written as a general but very
complicated form. Rather than confuse the presentation, it appeared best to
let th_e reader devise additional equations by inspection of those given a.nd not
present 0. confusing general equation.
Overhead produd
Intermediate towers, which are defined as
r~""--"'-+
those from which both bottom and top prodI
--'-:::.:.,.
ucts are withdrawn as liquids, are indicated in
Fig. 1()'26. The study of such towers ~ comI
~---l-----~
plicated by the fact that the reflux (X R ) does
I
I
L ..-.-..J
not have the same composition as the overhead
(liquid) product amd in f&C~ is intermediate in
composition between Y1 and Xl' , Perhaps the
.'
best a.pproach is to u..~ the equations that
XRJ:k
have alrea.dy been given, which 3Ssume that
XI ,
X B = Y I, because these equations are more
Topprodu,
simple than others; but as an illustration of the
(kerosene
2
relationship if Xa is assumed to be equal to Xl,
Eq. (16-29) for 0. three-plate tower is also pre.
3
sented. Note that this is far more complicated than Eq. (16-25). which is also for a
X... ~
4
three-plate tower. Additional relations for
~wo- and four-plate towers, are given in the
Bollomprodvrl
I
(gosOIl)
original references. 66
I
L-.l
All the preceding equations are very comrr-- .. I
plicated, and hence iIi many instances the use
i-----~
I
of Eq. (16-17) for infinite reflux may be justified reed" I
f----.
-----~
___l:
I '
t------1
(16-17)
The use of 'this equt1tion gives nearly the same results as th~ more complicated
equations ie the reflux quantity"is as large as that norma.lly used commercially a.nd
if a normGl number of tra.ys is employed. Another powerful reason for using
Eq. (16-17) is the fact that equilibrium constants (K's) are not dependable when
applied to complex mixtures and hence great expenditure of energy in using the
more rigorous equations may not be justified. The infinite reflux equation should
not be used for those intermediate towers which lie just above the feed plate,
, because such towers operate with very little reflux.
In two-component fractionation studies the term. "minimum reflux" is employed as the amount of reflux 'below which no increase in the number of plates
(even to infinity) will cause the separation of the desired product. Although
such 8. situation also exisf.8 for complex mixtures, in that a pa.rti~ular boiling Ta.nge
'"
Two-plate tower:
YJ _
(I
CD 1tJ
100e
ii + ',-
KtB
10_
I}
[D + RCe -
1)-]-
(l6-2-t) '
KI
Three-plate tower:
Y. _
1000 -
11+
.
KaB (2
.
~21tJ
~ 2e _ 1)1 [(D
D 2 Ii + 2e -- 1) + ~ (2. - 2) + R~~:i::)I]
(16-25) .
Four-plate tower:
Y ...,
g+
K,B
[- (D
(a. ~au
+ Ie _ 1)' D 3R + 3e - 1)
l00e - '111.
+ ~. (811 -
B) (
3~
B
+ 311 -
1) + ~
(3e _
K,K,
(16--26)
8KaKrK.
is Five-pla.te tower:
....
100e
Yt-
11+
X.R
(~hJ
48 + ~ -
)' [D(4i+u
- 1)'. + K, (41 1
.
D
4:)
-"6
' i +.w -
)1 + KJC,
D
.
(411 -
4)' 4R'
+. ok -
R(4. - 4)' ]
+ K.KaK,
(~- 4)' + 4KJKJC.K4
(16-27)
Six-pla.te tower:
l00e
-",6
y.-------~~-----~~~~----~~~~~~~----~~~~~~~~--~~~~~~~~----~~~--~---~~--~~
5hJ
11+
. KcR(5~+6e-l)1
~-
.4
C1
KI
1aJ -
K,
Ii +
1'.,
- K D
.
~+ _1
I'B + ., - 1
1
K.
;:00- ~ tD~+
2R
Jj
D
(Ii + - 1) (2 Ii + 2. - I)
+ ElK,
(2., _ 8) .
(2ii + 28 - 2) (2 Ii + 2. - 1)
(16-29).
522
.\
81
..
523
are
= 0648
.
H we are interested only in getting the composition of the ga.soline a.nd of the front end ,
o(the kerosene, the wz term (or terms) can be neglected because essentially none of the
hydrocarboll8 in the gasoline and low kerosene will be lost into heavier produots such . '
,
as gas oil. By inserting known values, the eqnation simplifies to .
,'
Y1
"..
26
moe -
+ 23.5 X 0.648
KJ{J1aK.
l00e
26 +
15.2
= ----,....-::--
, ' K 1KJ(aK
524
The remaining variAbles) ie., the eqw1ibrium CO!lStant.! eX's) end 0, are dependent
upon the composition of the feed alld the plate temperatures. Values of C are "def.er..
mined by reading ftom Fig. 16-27 and are smoothed by inspection as shown in column
(3) of Table 16--12. The values of K) as shown
columns (6), (6), (7), and (8) of
>......
8W 900
.!!!
>
'15
800
0100
,
1
".,.q~
~~J'i't,
- 500
~ 400
~
./:
...5 200
IS
~ 100
"V
I/'
00
10
l\""
r-..
r---...
"- ..........
\.1
~Vi$cQS/~
yield 210
0-
~ ()?J!).
80
~~~t. ,
[): K
u..
l300
V '1-.6tiD!'
.. \
~ 600
:t;
90
r-t
Visccllly........
@ZIO '"
i,. J
V
..J---t::
]
i
10
40 SO 60 70 80 '10 too
W
Percentage Disti II ed
FIG. 16-27. Typieal para.ffin-base crude oil.
10
Table 16--12, can be read from Figs. 5-27 or 16-4 and 1~5, but it is first necessa.ry to
estima.te the plate temperatures. By means of the approximate boiling ra.nges of the
products taken from Fig. 16-27 9Jld the methods. outlined in Examples 16-3 and 16-4
of this chapter, the plate temperatures are foun~ to be about ns follows:
Pla.te number
Gasoline. . . .. . .
Kerosene. .. . . . . . . .
:la~
{TOP
3"
4
a:F
- 310
360
400
425
i
In Table 16-12, eolumn (12) should total to 100 pOt cent if the assumed yielda of
gasoline a.nd kerosene designated as 0 and la, respectively, are correct. The total of
column (12) was 100.52; and hAd nelY values of g - 26.2 and h CI 23.3 been used, the
total would ha.ve been almost exactly 100. The enor so introduced oecurs prims.ri1y
in the first two fractions, and hence the error of 0.52 per cent was corrected in column
(13) in the first two numbers, i.e., 27.3 and 35.3.
One other check on the accuracy must be ma.de before the computations can be dismissed as correct. This ehec~ consists of determining the tower temperatures from
the computed dist.illation ourv&i shown in columns (13) and (17) of Table 16-12 and on
Fig. 16-28. The checks on the assumption of 810 and 425 G F were found to be satisfactory. ASTM curves estimated by means ot Fig. 4-18 and Tru>le 4-8 are also shown
fu~l6-a
.
\
\
I
I
II
-~
TABLE
(l)
J'nCotlon
nw:r1
ber
1
2
3
...
8,
0
10
11
t1
12
IS
14
1a
10
17
18
19
20
21
Z2
28
24
(2)
Bo~
~r
~220
240-260
2f}Q-210
270-280
280-2130
290-300
1.22
1.23
1.22
1.22
1.22
35~60
720
210
216
220
122
122
122
122
2.2
32o-:J30
34.0-360
l~!
1.22
122
122
1~
1.22.
1.22
1.22
390-400
400-410
41D-420
42()-4';0
44D-460
460-480
480-400
1.22
1.22
1.22
1.22
2.44
2.44
2.40
2.10
o.oa
U.B3
0.72
0.62
O.OS4
122
0.210
122
13:1
' 122
122
244
244
244
244
2.44
1."
1.3.t"J
1.10
2.40
122
122
2.44
1.80
11.00
G.SO
4.20
8.20
6.50
3.00
0.67
0.40
0.246
0.296
lU
300-310 "1.22
3r0-3SO 1.22
aso-agO
(11)
21.800
1.370
0.6
183
8.S
6.'
4.9
3.&
2.S
2.4
2.2
1.96
1.70
LM
1.86
1.0
1."
1.32
1.1
0.90
0.%8
0.21
..
O.4~
.......
"
O.08ao
0.232
0.476
0.136
1.~
2.12
8.40
6.89
0.000
0.608
0.312
0.168
O.OOla
1.01
O.gO
0.74
0.&1
O.1a
0.179
:1.68
1.61
1.80
1.13
0.82
0.73
O.IW 0.52
0.40
0.1
0.41
86
20.7
n.s
1.18
4.35
:.1
2.1
$16
32.0
3 .. 8_
3.3
3.1
19f
0.0001
0.0111
0.0294
00.4
4.2
3.0
2.7
0.71
0.16
.. ...... "
8.0
8.4
4.9
4.1
3.8
O.D'1
0.83
0.36
10.0
10.6
1.86
1.40
1.2'
1.06
0.162
0.140
16.0
1.60
O.2~O
0.008
425F
2.0:;
0.62
0.64
0.118
0.Q86
.aooF
1~.~
O.D~90
9.4.4
18.8
30.0
48.7
90.6
16G.O
81U.0
0.021)0
5~001.0
0.0.''21
11~'O
0.OOU2 3.
.0
0.00107 14.200.0
"
.......
II
....
. . . . . . . " I"
,,
(10)
+ 26
26.0
20.01
26.03
26.08
2G.18
2U.2U
26.41
26.13
27.29
28.12
29.40
31.89
35.44
42.80
66.0
74.1
llB.6
192.
836.
560.
1,226.
3,726.
14~~
Tot;{
(12)
(13)
(14)
Y.y
Ouc>UQe,
"Yl
100C
(11)
rt. '10
8.08
8.86
8.44
4.00
4.05
4.01
4.57
4,.4;
4.35
4.14
a.ss
3.46
2.8&
2.18
1.113J.O~
per-
. COAt.
86.8
43.0
52.1
GG.1
01.4
66.0
70.~
75.0
70.4
BS.G
87.8
OO.S-
. lODe
26X
(12)
age
27.3
(11)
120
III
107.3
~."
90.0
1 .... 1
91.40
"'2.4
21.8
16.11
98.~
09.1
0.040
0.30
99.6
0 . .0
99.7
' 0.20
99.9
0.06
0.02
0.00 - . "
... 100.52
ioo:o
..
~
58.6
9.t
1.1
6.2
1.6
D.li
0.0
(U)+
23.t
0
0
0
0.02
0.04
0.04
0.09
0.13
0.2e
0,38
121
121
120
110
116
U3
X I
(H)
.....
......
219.4 "0:0
93.6
95.8
- flY'
(40) -
(16)
1
1
2
0
g
14.4
22.6
0.62
0.96
(11)
KercJ..
.ene.
p~
oent.qe
0.1
0.2
0.3
0.6
1.0
1.6
2.~
1.36 . S.Q
5.9
2.03
41.S
2.18
05.40
8.7
11).6
3.30 12.1
4.08 16.1
94.1
40.49 20:6
105.4
112.6
4.79 ~.4
4.85 30.3
116.3
288.8 1'0.18 40.4
242.4 "10.32 50.8
32.0"
:43.5
244.0
10.3'1
10.38
61.1
11.6
column he.diDa:
It Number a.eeigned
(10)
K,KJC.K4
i
EX~D&1.loJA of
(9)
(8)
1Iot.
310F ,360F
2.1
2.16
1.22
3S0-:t40
(7) - .
(6)
looe
SOO-'10
810-:120
I I
TABULATED COMPt1'l'ATlONS
-.,'lOO
- -7.2
22t>-UO
(15)
(4.)
(3)
16-12.
rOt
identl6oa.ticm.
11
12
13
14
15
16
1
526
PETROLEUM
REFlNER~
ENGINEERING
The separation found in Fig. 16-28 checks reasonably- well with Fig. 16-22 for five
plates and a reflux of 6.6 (see below).
Equaliun for Actual Reft,u:t. Had Eq. (16-26) been used, it would have been necessary to mo.k:e 8. heat balance such as that illustrated in Example 16-1. According to
such B. heat balance (using 100 gal as a haBiB), the actual hot reflux or eR = 6.6 moles.
-" -
~~
500
Kerosene
A.S.T. M. _" ~
-~
--1;"""-
"
",,'"
"/
,.,,-- ~-
/computed frue
"
i>()llin~ curve
If
/J
~."
., V
~ AS:r.M.
.J
,~
... / """
100
Gasoline
1/
30 40 50 60" 70 80 90 100
Percentage Distilled
"Fm. 16-28. Composition of the produc.t s determined in Example. 16-14.
The heat-balance
10
20
e=
0~8:3
= 7.93
D = 19X1S - 1.69
. b = eR = 6.6 = 3 9
.D
1.69
.
D
1.69"
"
R = 0.833 = 2.03
J := 0.648
"
By inSerting these values in Eq. (16-26) the following simplified equation results:
y _
.
1 -
+ h (0.1360 +
K.
100e
~
0.0701
"K.K.
KJ(.K.
0.241
K1KJ{.K.
527
rrhe computations are conducted in the same manner as fo~ infiriite reflux. Note,
however. that the top temperature will be slightly lower and that the yields will be
slightly different.
'
fra~tionators
,
Plates between
fractions
Operation
Materials separated
..
Cracking
Vacuum
Litera- Recom
ture 4 mendation
3-8
3-6
6-8
4-7
4-5
3-4
4-6
4-5
10-12
4-5
3-5
5-6
4-5
4-5
2-4
4-5
:h5
7-9
10-12
6-8
10-12
4-5
8--11
4-6
2-4
4-5
3-5
2-3"
2-3"
3-4
3-4
3-5"
2-4'
241:
CHAPTER
17
(T2 - T 1).
6.T
A = -L/k =
528
IlT
(17-2)
529
Material
Customary
Aluminum ..................... .
Asbestos cement board ........... .
Aabeatoa felt ..................
Asbeato& wooL .... " .... . ..... , .
Asphalt ......................
Aaphalt, road ................... .
Braaa ....................... '..
Boiler scale ..................... .
Brick, fireclay .............."... .
Brick, diAtomaceous (Qatural)" ... .
Brick, dlatom~ou. (molded) .... .
Brick, magnesite ...... " ....... , .
Brick, red or common ... '........ .
Brick, sD.-o-c.el insulation .........
Calcium c&I'bonate scale ......... .
Coke ............... . .......... .
Copper or silver. ~ ...............
Concrete wall ...................
Cork ....................... , .. .
Cracking-coO. coke ............... .
Hi-Temp No. 12~ .............. "
Iron aulftde ....................
Jute fibera .... , .................
Kapok ............ , .......... . .
Lamp black .................... .
MagD.eBium 85 %, insulation. ".....
Mineral wool, insulating cement- .. .
Paraffin wu .................... .
Rock wool blanket- .............
Soil, aandy, dry, 24-in. cover" ..... .
son, 88lldy. moist, 24-in. cover" ... .
Soil. sandy, ao&ke~ 24-in. coveri .. .
Soil. under river" ............. . .. .
Soil, sandy. dry, 8-in. oover<' ...... .
Soil, 8ILDdy, moist., 8-in. cover' .... .
Soil, cla.:F, dry, 24-in. cover' ...... .
Soll, clay, moist, 24-in. GOver<'. " .. .
Soil. cla,y, wet, 24-in. cover" ...... .
Steel. 0.06 carbon and pure iron .. .
Steel, 0.3 oarbon aDd cast iron .... .
Steel, 18-8 ohrome nickel ........ .
Steel, all kinds .... . ........... .. .
Superex' ....................... .
Unibtlsto8, Standard/ ............ .
UllibeatOtl, Super/ ... . ........... .
Vermiculite .....................
Wood pulp .............. . ...... .
800
400
200
115
As noted
140
.. ..... 0.23 at. 212
.. ..... 0.12 at 21~
130
0.036
0.10
0.42
....... .......
60
80
0.&-1.48
....................
0.05 ..............
0.12 ..............
3.0 ..............
...... ,
0.4
........
0.34
0.125 (at. 7(}-lSOO)
. . . . ... . ......
~
&
O. 9 at 2000
0.08 at 2000
O.19at.2000
2.0 to 2200
0.7 at 1800
.......
0.5-1.6 at 70
I'"
0.7 At 1800
0.48
216
230
0.44
0.03
a.2/s
... ....
0.0
0.061
0.056
0.037
0.058
0.048
0.061
0.034
4.10
0.027
0.023
0.04
0.14
0.24-0.4
0.S-O.6
1.1-1.3
2.0-2.5
0.6--0.7
1. 2-2.4
0.2-0.3
0.4-0.6
0.6-0.9
38
30
9
~ ....... .
I ' .'
.......
18
0.025
Perpendicular to strata.
Philip Ce.rey.
e CommeTcial Standards CS-117-44 Classes C and E
Nelson, W. L., Oil O(J8 J. t Sept. 15, 1945, p. 110. Not for 1 ft thicknesa (eee oover:illglllndioated).
Johns-Manville.
I UOiOD Asbestos Company.
II
.
'17-2. TBERM..u.
.
CONDUCTIVITY OF PETROLEUM PRODUCTS AND WATER 4
(MULTIPLIED BY 100)
100 times Btu/(OF difI.)(hr)(sq ft) for 1 ft thickness
, Temperatue.
6,
Temperatura, "F
Material
Materia.l
200
400
-100
80C),
600
100
200
1.67
1.99
1.30
1.4.1'
1.78
1.47
8.83
8.4.2
6.00
~.a8
7.85
7.83
8.16
8.33
8.76
6.91
8.42
6.00
7:35
7.0
7.83
8.23
8.75
6.91
7.20
7.M
6.42
6.72
30 API oil....
TEMA .......
40 API oil .....
&I API oil ......
60 API oi!. . ....
9.~6
7.75
8.16
9.69
10.20
D.W
1O.Mb
9.86"
10.98
12.59
10.30'
11.80'
P.W
5.23
5.58
6.91
6.23
0.61
0.87 ,
1.13
. ...
0.80
0.71
0.09'
0.61'
0.53'
1.08"
6.83
8.33'
7.25
7.115'
8.63&
6.76i
"",lilDiane (pa) ..
..... .
. .. . .
......
..... ,
......
10 "
...
.. .....
O.~
....
10
10
......
. ....
0.95'
0.84
0.81
0.73'
1.13'
1.16'
I.~
33 .()01
Water (liq) ...... ..
36.S
40.5
jUJpbtJt ......... (10 flom 32F to melUn" point)
PamftI.n wa:J: . . (18.3 from 32"F ~ meltiq poiot)
.. Mainly from Gpagoe. C. 8., Nat. Blat. Sbularda 1118'" hb. 97, 1929; and Neboa.. W. L., Oil Got J.,. Ocl.l2, 1948, p.81:
bid other reCere.ocea abo ued.
Edrapolated.
Tubular Eze~npr MaDufactann A!BI!oatatioll reeommeodl cm1y tIl_ vau COl' petroJeam oila, 0dtJber. lG&4
'Ai 32"1'.
Several materials usually compose the vessel or wall through which heat
is being conducted, and hence conduction problems involve the conduction of heat through a. series of resi~tances. ' The quality of heat Q tha.t
passes through each material is the same, but th.e temperature difference
across each material will be different for each material. Suppose a wall
is composed of three materials having conductivities of klJ k 2, and k a,
having thicknesses of ~l, L 2, and L,&, and having temperature differences
of AT I , AT!, and AT a
also
The temperature difference across the three materials- is the sum of the
three individual differences.
and
(17-3)
531
17-3.
ConditJona
200"F
4QOOF
600 Cl F
540
210
1010
0
1620
700
1560
990
2540
1710
4120
2760
3120
2250
4680
3500
7440
6650
54
28
59
30
61
31
108
164
83
inaulat.iOD
10
10
40
40
mph wind,
mph wind.
mph,wind,
mph wind,
O"F ...
lOO"F ......
OClF
lOOOF ......
8000F
220
192
230
210
246
215
89
137
178
149
122
92
183
153
5~
160"
71-
232-
270"
417590"
207335"
135 0
207 4
322-
118
325115"
186"
11140"
64"
2411
40"
75"
116"
44Q"
620330497"
200"
Temperature
Wall
Conditiona
4000F
6000F
BOOOF'
10000F
12000F
62
93
77
124
108
ISS
186
139
170
46
Conditions
l000"F
12000F
15000}'
18000F
No iDsulation brick ..
2}(-in. insulation .. ~ ..
647
310
800
380
1010
500
1220
4~-in.
230
,
'J:l2
352
630
448
48:5
570
693
190
2~-ln.lDSUl&tiOD .....
4~-in. insulation ...
276
206
328
247
400
467
359
....
..
..
..
..
...
2100"F
2S000F
Furua.ce
4~-in.
firebrick
insulation ...
20 mph wind)
640
Furnace
O-in.. firebrick
4-in. red. brick
(lOOOF air ADd
20 mph wind)
Fum&ce
13~-in. firebrick
4-in. red brick
(IOODF air and
20 mph
wl..nd)
No in.ulation brick
2}i-in. inaulation ....
ra~her
..
306
.583
869
276
198
668
42S
814
2SO
gaS
1527
409
715
475
383
.2M.
60'1
470
793
541
44S
288
532
~T
Q_
Ll
Ail
L'J
+ kl .
1800 - 200
4.5
4
0.25
+ 12 X 0.125+ 12 X 0.52 + 12 X 0.23
1600
=
.
=1600
-0.915 + 3.0 + 0.641 + 0.0905
4.646
= 344 Btu per sq ft
= 3440 Btu through the 10 sq It
9
12 X 0.82
Tempera.ture
difference
Tem perature,
'T
1485
452
231
200
7.~
" ..
533
be used with an error of only 4 per cent for all cylindrical vessels and for
pipe sizes-down to about 2 in. if standard insulation is used. If the thickness is great compared with the diameter, the logarithmic mean area must
be Used in the qenominator of the resistance term.
_ A2 (large) - Ai (small)
. 'thmi
Logan
c area . A 2 (large)
log, A 1 (small)
(17-5)
"-fat--- --'4T,3--
--'-
Ka
L~
11_-
l!
452 '
Firebdck
--- 4'! -1
B.
AT
Ao=~xAo+~xAo,+lxAo+RAo~~AA:
ho
Ao
k.
Alii
""
Ai
(I
Ao
(17-6)
534
In this equation, ~ and ~ represent the outside and inside film coefficients of heat transfer ,of the two fluids; LIJJ and kw the thickness and con-
ductivity of the partition wall; RD and Ri the resistances due to corrosion,
dirt, or roughness of the surfaces; and A o, ' Ai, and A1D represent the areas
of the wall at the outside, at the inside, and at about the mean of the
two (AIJJ)' Two fouling resistances are used throughout this book, but
most of the literature fails to indica.te whether one or both factors are
being reported. Accordingly, a single fouling tesistance R D , which is the
sum of Ro and Rt , will be used in this derivation and no correction for outside and inside surfaces will be made except in such necessary cases as
fin-tube resistances (see Example 17-8).
The resistance in the denominator may, for convenience, he added and
the total equals IIHtJ or liB" in which Ho is the over-all transfer rate
based on outside surface.
(17-7)
(17-8a)
or on inside area:
H _
i.-
Thus~
~ + L~i
Ui k~"
(17-8b)
+ ' Ai + Rn
h~tJ
(17-ia)
If one film qoefficient is sm~n compared with the other .coeffi.cien~, the
resistance 11k' which corresponds to it will be proportionally large. In
auch a. ca.se the value of the over-all coefficient will be nearly the same as
the small film coefficient corrected to the reference surface. For the sa.me
reason the resistance of the metal waJI may often be neglected.
Example 17-2. Over-all Coefficient of Beat Transfer. Heat is being transferred
from a gas through the walls of-a sta.ndil.rd 2-in. pipe B.Dd into water that is flowing on
the inside of tlul pipe. ha "'"" 6, h. ... "'" 500, and k for the pipe wall is 25 [see Eq. (17 Sa)J.
w
H
oa -
1
' .
Aoa + L.. X Aoa + All - 1
h~oa
kv
A..
haAi
1
+ 0.104 X 2.375
6 12 X 25 2.221
2.375
500 X 2.067
HI! = 0.1667
+ 0.00055 + 0.0023
= 5.9
Thus, the 'resistance of the metal wo.ll and the water film could be neglected with an
error' of only 1.66 per cent.
.
535
. Likewise, the pipe could be made of copper, which is an excellent conductor of heai
(k - 220), and the over-all coefficient would be scarcely ch&~:
H. ~ 0.1667
.,
~
~ :;
Oislon~e
(0)
1M
(d)
(e)
(e)
. MMe
(I)
FIG. 17-2. Common arrangements of Bow: (a) countercurrent, two-pass ~hell, 2 tube
passes; (b) ,parallel flow, two-p~ shell, two tube passes; (c) Ip.ixed flow, single-pass
ahell, two tube passes; (d) constant.teml>era.ture cooling medium; (e) consta.nttemperature heating medium, a.Dd (j) combination condensing and aubcOQIing.
constant
,J, -
......
'1
536
- -- ~ .--
a.t
120
Iog. 40
80
1.1
= 72.SoF
40
80F
temper~ture
G'I"J'D. L11'D
Lo9.
100
80
70
G'I"J'D
t-#'
UTD
<b
/q,
~ 'b
60
4J
50
~...
40 !
/:
+. .
~
'V
30
&
20
Ji
'=
ii
.!!!
-"' .
1\
/1'
1\
LI"l 1\
I'
<II
t \ 1\
10
OlIO
......I
B
1
6
'"
20
10
30
4{)
50 60
80 100
200
300
5
8001000
(Griacom-R1L8sell Co.)
-'
~~~~~~~::::F,::::::::t=::r~~IT~---rlrO
"",1
II I
\ _1\
\ 1
)
":
,4
")<".
1+"'< lI'w" "'< 1 '~ v.rc:.
'-<:
~<
....
~1
I """"
..... .,J'"
'<:
1'~
1>',
IQ.9
- ,~
~.
~ 0.8'
!b
LI
II
'\1
'"
UPPER-I SHELL
lO
~ss
I'
\1'"
"
"
I'
I''"
'as
~ I ~~t==Cj
0.91
,t
II I
I'
J----I1,~1~_Ii5-1Q)-+-I0\
08'
at
1
l..r.J
\ 1
'\
'k:
't
"-l
"
.OJ
0.4
(
C
UPPER
. . - UPPER
I shell poss, 2 or
fI10fP ItJbe posses
j ::
p=1-t,
,-I,
!72
,; ; ----- --
:"".
n.
. I'
I)
0.5
p"~mpero/ur~
!r,
't: ''\:
'I
',1_
'.
"I
'\
IQ9
_\
I J
0.2
\:1"
'
0.6
"
I )
efficiency
LOWER-
LOWER
Z shell POSSe's, 4 or
more tube posses
I~
7;-'2
/?---
~-'I
single-~
r;
I ~ ~:
172
..,j
0.9 I
L)
I I
I I
'"
~I~ Ig I~ I ~ I [~
I \
'". I "
....
'"
"
"'=1
I ""
I:::J
0.91
I I
0.81o
19)~I~I()I~
0.1
"
l'
0.2
7j
I~
o.~
I'L..
~----~ . ~ ~
~~
.',
~ /
IGI.~
0.4
~UPPER
3 shell posses, 6 or
more IuIJe pusses
P.
t-f,
1i~
/\
\~I
a5
1,\
1\
"'
\J rl0.6 '\
/.
"'",
lfl
a,
"" I,
as
\~O.9
Uo.B
~I
~"Q~
1,0
,,,
lIO.9
LOWER-...
4- shell posse~ iJ or
more ftJbe posses
"
R- f-7g
T-~
FIG. 17-5. Correotion factors for mean temperature difference for 3-psas
four-pass shells with eight or more tube passes (below),
j"...----- --- -
'...
"'"
UPPER-3SHELL PASSES
u~ 1.0,
--,.0
1
C3:::t I _I E I +==l.
1'1 1'\
sh~
It
.539
of Rand P.
EQUIPMENT
The ultimate source of heat in the refinery is the steam boiler and the
petroleum shell or pipestill. Indi,rectly, heat is obtained or saved from
the va.rious petroleum products by cooling them with the raw charging
stock. If the two materials that exchange heat are liqUids, the equipment is referred to as a heat exchanger. If the hot material is a va.por
and is cooled without much condensation, the equipment is called a vapor
heat exchanger. If the vapor is condensed, the equipment is called a conden&er exchanger, and the equipment subsequently used to co<?l the can...
. densate with water is usually referre.d to as a cooler or after-cooler. Equipment for heating
bottom of a fractionator with steam or hot oil is
known as a. rOOoiler. These cooling and condensing operations may be
conducted in so-called coil-in-box or 8Ubmerged equipments, although many
refiners have discarded the coil-in-box arrangement except ~or particular
services. Sprayed coils or tube units mounted in cooling towers are
replacing coil-in-box equipment because of the. higher transfer rate~
obtained in them.
The large amount of water that is contained in coil-in-box equipment
is often an advantage. Thus, if the water supply should fail, the ru~
down house will not be filled with uncondensed vapors with the attendant danger of a serious fire. In large refineries the water supply is unfailing and tubular equipment can be used with safety. During the last
few years the design has been so improved that tubular equipment
can h.e built as cheaply or even more cheaply than coil-in-box arrangements. Owing to higher velocities and the relative ea.se of cleaning, the
heat-transfer r~tes in tubular equipment are usually more than twice as
great as in coil-in-box equipment.
H the cooling water very bard or dirty or if severe corrosive conditions exist, tubular equipment may not be satisfactory. Tubular equip-
the
is
540
,.
..
The foregoing items are standard equipment. In addition, the jet type
of cOndenser has been finding some application. The barometric jet-type
condenser is now universally used in vacuum distillation to condense
steam and at th~ same time create part of the vacuum. In this type of
condenser, the vapor and the cooling medium are intimately mixed by
high-pressure jets, and heat is exchanged by pure mixing or conduction.
Theoretically, heat transfer by mixing is 100 per cent perfect and is the
cheapest means of transferring heat. For ordinary condensation, jets
have not been used extensively, perhaps because of the tendency of water
to form emulsions with oil and because the water must be clean.
The UBe of partial condensers for the separation of products tha.t have
different boiling ranges is no longer practiced. An exception is the use of
partial c.onrlensers for the separation of wax distillate and gas oil in a. few
vacuum plants. Partial condensers can easily be placed near the tower,
and the more quickly the large volume of the vapor can be eliminated the
less is the pressure drop in the vapor line.
Extremely small (1.~ to 100 sq ft) inexpensive fixed tube-sheet exchangers are used extensively for the cooling of engines, compressors,
b.ydraulic presses, machine tools, etc.
Heat exchangers are built in such a multitude of structural-types4./i,6
that they cannot be discussed here. The primary aim in all these designs
a Dems.rest, K. D., ~etroleum Industry Uses of Air Cooling, Pet Engr., Janus.ry,
1946, p. 145.
.t Rubin, F.-L., Shell and Tube Heat Exchangers, Buffalo, N.Y., Meeting kI.Ch.E.,
Sept. 30, 1947.
.
'Blaylock, P. W., Heat, TraIlBfer Equipment, TTam. A.l.Ch.E., 40, 593 (lC44).
Nelson, W. L., Shell and Tube Bundle (Types), Oil Gas J., Feb. 9, 1946, p. 111;
and Double .Pipe (and' Fins), Oil GaB J., Feb. 16, 1946, p. 129.
541
2. Cleaning is facilitated because one unit at a. time can be removed from the system
and cleaned without markedly interrupting continuouB opera.tion or changing the
operating conditions.
3. F~r the same rea.son the repair of leaky tubes is fa.cili tated.
4. Small tube bundles can be more easily removed and more easily flushed or cleaned.
5. Large multiple-pass units are bulky and -cannot be easily ,installed ~nd removed.
In the ease of vacuum partial, condensers, the weight of the several units of eonden,. TTam.
.,
.,
ser often amounts to over 50 tons. This great bulk at a height of 40 It or more is
indeed awkward.
6. H many units (double-pipe or fin-tube) are in service (some refinerS have .hUIi~
of units), they may be disconnected and reassembled to meet changes that are
constantly oecwring in s~ces or operating conditions.
543
noW- use<f almost exclusively for refinery services. The fluid is caused to
flow back and forth across the tubes (Fig. 17-6). .Poor heat transfer
occurs in the dead space behind the baffles, and corrosion is also most
active in these 'areas. 9 bead space can be e1im..inated to a large extent
by window-type 9 baffles which consist of baffles that extend entirely
across the shell but have several stagge red ports for liquid Bow. These
partially ~eviate the disadvantages of crossfiow. baffles, i.e.,
are said
high pressure drop, low transfer rates, and high maintenance costs.
The closer the baffies are spaced the greater the turbulence and heat
transfer. The pressure drop increases at close spacings but not in proportion to the increased transfer rate. However, spacings of less tha~
6 in. are seldom used because of the difficulty en~ountered in cleaning
the outside of the tubes. ExchaI;lgers in use today have spacings of 2 to
to
(~
~)
ii
.,
i
30 in. Since the clearance between the baffle p1ate and the shell is onll
~2 to %6 in. (even 7llJ to %2 in. if the shell is "bored"), corrosion ,or
dirt tends to "freeze" the bundle into the shell.
"Impingement .baffles are placed at points that may be eroded by the
velocity of the fluid. Usually these batHes are used only at the fluid
entrance point, but they may be used at any point where the fluid suddenly changes direction. Tubes in vapor condensers have been entirely
severed by erosion in a few months of operation.
Longitudinal baffles are used as indicated in Figs. 17-2 and 17-6, to
direct the flow from one end of the exchanger to the other. In another
common arrangement (split flow) the longitudinal baffle is open at both
ends of the exchanger so that a shell fluid introduced at the center of the
shell passes to both ends and then back to the center. This results in
both countercurrent and cocurrent flowin various regions, but when used
with two or more tube passes, it is considered to be the same as the mixed
flow of Fig. 17-2c. Several longitudinal ba.ffles are sometimes used in
Gilmour, C. H.~ Chem. Eng, News, Apr. 23, 1966, p. 2062.
,.,I
.',
.j
544
%
1
Square
~
1;t6
1%6
and 1
lX
Dia.mond
1~6
and 1
1~
1
l~
545
where C = a constant (0.75 for square pitch and 0.86 for triangular pitch)
P = tube spacing, in.
L = the" outer tube limit," in.
The outer tube limit is about IJ2 in. less than the inside diameter of the
shell of floating-head exchangers, or % in. less than the shell diameter of
fixed-head or U-tube constructions.
Exchangers built with closer tube spacing are not accessible for cle~n
ing. Later in the Ghapter the importance of frequent tube cleaning will
be discussed. For severe fouling conditions, a square or diamond-pitch
arrangement with wide spacing is suggested, although for regular service
the equilateral-triangle arrangement is a]most standard. Square-pitch
arran gem en ts can be brushed~
Carbon-steel tubes and cast-iron shells are least expensive, but highsu1fur crude oils may justify the use of 5 per cent chromium or even 18-8.
chrome nickel tubes l1 particularly in cracking serVice. Refer to Chap.
9, pages 276 to 284. For the "acid" corrosion produced by salt brine,
admiralty metal or occasionally cupronickel tubes are justified. Ammonia is often used as a neutralizer for" acid" corrosion, and it attacks
admiralty metal so rapidly that admiralty m~tal cannot be used for such
a situation. The mechanical properties of this alloy are also impaired by
temperatures above 500F, although under favorable conditions it can be
used up to tube-wall temperatures of 600F. Recommendations are as
follows:
Material
Highest working
tube temp, OF
Admiralty ...........
450
145
Steel .............. . .
Steel . . ........ . .....
500
130
800
95
a.~. _~changer
~ell
...
Oul/ef
ChanneJ
spocers--
flrxdIng
Ivhe
;sheeI--
';routing , /
head CDYN
lJiu/n
)
~.
.,'
G~ts;"
Outlet
I
.,," .-
SkI halts
CrOdle
Inlet
547
some transfer-rate formulas ,of chemical engineering textbooks'and literature lose much of their importance. In addition, the design of an
exchanger involves many tedious trial-and-error operations in adopting
(1) the most economical size (or approach temperature, Fig. 23-5), (2)
the most economical tube length, (3) the most econoniical velocity, and
(4) the number of passes to employ, as well as requiring a consideration
of a multitude of mechanical features. Most ,of these factors are more
important than the slightly greater accuraey that accrues by the use of
complicated film-transfer-rate formulas, and hence in this chapter every
effort has been made to indicate practical and simple methods of estimating film-transfer rates. Buthod and Whiteley 12 have approached this
situation by an extensive use of charts.
It must always be remembered that the film-transfer rates given here
and elsewhere are far higher than the rates obtained in commercial equipment, that fouling or dirtiness factors must always be used. They are so
vital that they are presented ahead of all other heat-transfer data.
Fouling Factors. The great lowering of clean film rates by fouling has
often led plant engineers to believe tha.t something must be wrong with
, the film rates that have been published. As an example, two exchangers ,
operate under such conditions that the over-all rates computed by the film
coefficients are 125 and 25. If both exchangers become fouled by the
same amount, i.e., a fouling resi,stance of, say, 0.02, the over-all rates d~op
to 36 and 17, respectively.
The resistance due to'fouliD.g is often so small that the position of the
decimal point may become confusing. Hence the use of the term" fouling
factor" h,as become common. The/ouling factor is obtained by multiplying the fouling resistance by 1,000. ThUB, if the fouling resistance is
0.005, the fouling factor is 5.
Although there are many individual conditions of fouling, most of them
can be generally classified 8B follows:
1. Hard Deposits. Examples of this type of fouling are water scale,
corrosion Beales, rust, and hard coke. In general, the thickness and resist,.
ance of these deposits increase with t4ne and nearly directly proportional
to time. They cannot be effectively removed by blowing with steam or
by Bushing with hot water, but some 6f them can be removed by the use of
chepllcals. The chemical solution may be p:umped through the equipment, but sometimes the tube bundle is removed and dipped into a vat
that contains the chemical:l I The usual manner of removing hard
,deposits is by the use of dry sandblasting, U cleaning tools, and brushes.
Heat Transfer. A Manual for'Refinery Technologists, Oil Gal"., 17 issues between
17 and Oct. 21, 1944.
'
11 Anon., Cleaning Exchangers, Pet. P1'OC6Bsi.7l{J, April, 1951, P ,I 370. .,
If Fitzpa.trick, J. H., Hea.t-exc'hanger Maintenance .. , Oil Gas J., Jan. 28,
1952. p. 372.'
11
JUDe
0,
, I
',
: 'i
I"
,i
I :
I
:~
;:
, :,
548
J.
549
8 '---~--~--~----~--~---T----r------------'
1 ~--~--~~~----r---~---+--~
g ~I--~~---+-=-~I----+-.....;.::I,,"+-::---+----I
~
i.I--~I--_""""'~"""____i---~"-'Ir=-~
:J
:lI
e
r---+---~--~~~----r---T---~~~
T--~-_+_-..L" 10 3Dlf"F
30
~\
: 1'. \~
\
20
~NATU~ CONVECTION
BEI.OW I n. PER SEC.
\
\ \ II
ti2!l !4u1tidm
~,
I
, L
\ ~
I
I
\\
~t
,~
"'"
~
"
~ ~ ....
~
i'.
............
CANAL.
SAN I. CANAL
BQB.ER N OWQQWN
~ _UR.w egrm
..HARD
(OIER ~ GRAINS PEA CAL.)
~.-
UiIY.B - AVERAGE
[7;
~
RInIl-MINIMW
n r: "'N-~- QR TIDIED
GREAT LAKES
ENGINE JACKET
COIL-IN-8OX
MIRRA ...
CH~
l"C""'
...... t----'"
~-U
JJ-IQ
"~
\~ "
"
.FIG.
~-400P:
.tOO AI) UP
i\
a
BY l2S
2.1,. OTHER FLUIO IS VDI'I
HOT. UUl.T1PLY BY:
1~"'lJ- CHAHGS
'{
;,
EXCEEDS ~ r. WULT1PI..Y
"- I
10
QlSrtLl.ED
550
composing the depoSits but rather upon the liquid that is trapped within
them. Thus with respect to heat transfe!, loose deposits may be more
troublesome than other types. Hard scales and some porous deposits are
so tightly fastened to the surface that they are affected little by a. high
velocity, but many loose deposits can be currently eliminated by maintaining a. veJoci ty higher than 4 ft per sec. In handling CR talyst laden
10
\
\
t3
~
\
\\\
C)
:z
-J
.:;:,
t.&..
'"
1\\
f'LASH
"-"!
~ ~ ....
............
............ "-
...............
POT,
\N3ORATOA.
Q1AMBEA, ETC.
,OVERHEADS .
~~IDU PRODUCTS
II=:LLD
rEEDS AND
~ PAOOUCTS
f
lL.
II-.
lCMER
ovtRHAD VA~
--
A.P.L GRAVITY
FIG. 17-9. Fouling factors of petrol.e um and naturai-gas products (topping, vs.euum,
treating, cracking, etc.). (Oil GaB J.)
I
J
551
17-4.
0-0.5
3..,.6
2-3'
2
10
10
3
1
1
2-3
3
1
Absorption oil. . . . . . . . . . . . . . . ..
Solvent plant feeds (treating or
dewaxing). . . . . . . . . . . . . . . . . ..
Solvents .... ,. . . . . . . . . . . . . . . . ..
Gums, ~h.alts, a.nd resins ..... ,
Oil-wax cooling ............... '.
Refrigerating liquids, brines, eto..
Fuel oil. . . . . . . . . . . . . . . . . . . . . ..
Chlorinated hydrocarbons .......
Hydrochloric acid. . . . . . . . . . . . ..
Quenching oils. . . . . . . . . . . . . . . ..
Quench (1000F) excha.nger. . . ..
Ca.talyst slurry oil ........ '..... ,
1-5
1-3
1-2
5-10
3-20
1
5
1-2
None
~
0.5-2"
8-17-
Based on Standards of Tubular Excha.nger Manufacturers Association, 366 Macli"son Ave., New York, 1954; Nelson, W. L., Fouling of Heat Exchangers, Ref. Nat. Gaso.
Mfr., July, 1934, p. 271, and Fouling Factors in Heat Transfer Equipment, Ref. Nat.
Gaso. Mfr., August,' 1934, p. 292; also Breidenbach and O'Connell, Predicting Commercial . . . Coefficients, Tram. A.I.Ch.E:, 42, 761 (1946).
~ Thermal poly plant pipes till effluent; Smith, J. H. (pipestill transfer line
. '
exchangers), Oil Ga8 J., Aug. 3, 1950, p. 45.
"Higher factors (20 to 68) are shown by , Weiland, McCay, and Barnes, Rates of
Fouling . . . , Oil Gas 'J ., Dec. 23, 1948, p. 64i and Cla.rke, J. S., Oil Gas J., July 23,
1956j p. 76.
'
G
Although ljnes are used on the figures to designate various conditions, ,the
lines are really the average of a range of situations. Thus, the "Residue
Products" line of Fig. 17-9 represents an average residual product. If a
particular residue contains suspended lime (for neutralizing hydrogen
sulfide), or if it is a cracked (rather than a straight-run) material, it will
have somewhat higher fouling factors than those shown. This is somewhat, but not entirely, cared for by differences in A;PI gravity. Likewise, 'distilled stocks or fractionator: overheads (Fig. 17-9) normally have
low fouling factors; but, if the stock contains corrosive materials, larger
U Nelson, W. L:, Fouling of Heat Exchangers, Ref. NaI.. Gaao. Mfr., July, 193~
p. 271; and Fouling Factors in Heat Traer' Equipment. Ref: Nat. Gluo. Mfr.,
August, 1934, p. 292.
.,
; .r
,
j.
..
,
552
The preferred method of cleaning exchangers is the use of alkaline chemicals such as Oakite for removing oil films, and phosphate-type clea.ners
such as Ca.lgon for removing water scale. Inhibited dilute hydrochloric
2' Weiland) McCay,
Rates of Fouling . . . I Oil Gas J' I Dee.
1948,
p. 64; also Clarke, J. 8;) Oil
J., July 23, 1056, p.
n Weiland, McCay, and Barnes, Rates of Fouling and Cleaning of Unfired Heat
Exchanger Equipment, Annual Meeting ASME, New York. Nov.
to Dec. 3, 1948.
U Katz
al., Pet. Refiner, August, 1954,
55~
II
~
I
u.:
~ .....
rlL..
d
~.
::
tm
~ ....
10.0
~
aD
<
15.0
lL..
u..
f;::: V
v
lIJ
5.0
v
~
Q
I-~.
:z
4 .0
:z
Q
'1--
3.0
......
""
1,'
.;?/l
........
V
~
;.....- ........
-- --
I.-'
........ I""
.;0
........ io"'"
l.,....-- ~
......
i.-'
~
:..,.......
~
...
...... ~
V-I-"
v
~
l...---'
;;;.--
...., ........
...... ~
~~
",....
I---
:.--
I--W
... -:
~ ...
~J;: ~
~
I.-'
[.......-
L,....- ~
i--""'"
V
.....
.,. ......... ~
1'\\Po.
-"
~ "--
~~
;;;;;"
I--' I.-
~ I---""
t.- ~
~
w
:>
2D
,...
........
l...---' i'""
a:::
-~~
71)
I-
I"
J"
0::
......
....J
,....
~ ....
9.0
:!
lL..
,
.....
I'
lL..
.....
......
1.0
100
200
400
Water at 1,000 to 1,200 psig may be forced between the tubes by means
of a fishtail-type nozzle!!) for removing coke and other deposits. Brushing with a stiff wire brush will remove some deposits. Scraper bars
may be inserted between the tubes to knock off hard scales,28 and special
tools are available for scraping scale from the fins of fin-tube equipment.
An Effective Method for C~ning Heat-exchange~ Bundles, Oil Gas J.J Feb. 3,
1945, p. 65.
26
554
80ft lime deposits.in straight tubes may be removed by driving rubbermetal .composition plugs through the tubes by air or water pressure.
Straight tubes are also cleaned mechanically with rotary tube cleaners.2~
After and during such cleaning, .the tubes are usually blown with air.
There are such an enormous number of situations and so many methods of
cleaning that the current literature must be examined. Note especially
the survey of chemical cleaning methods by J. C. Reidel. 26
Gases-Natural Convection and Radiation Combined. Convection is
always accompanied by radiation, and hence the most convenient method
of computing heat losses from an exposed surface to air is by a coefficient
tha.t represents both the convection and radiation transfer of heat. A.
study of the literature on this subject shows that the 'coe'fficient .is substantially the same for vertical brick, asbestos, metal, canvas, an~ wood
surfaces. These eoefficientsmust not be confused with the pure convection coefficients found in chemical engineering textbooks. Figure 17-10'
indicates the magnitude of these coefficients and the effect of wind velocity.27 The position of the surface alters the coefficients somewhat as
follows:
Vertical ...................... .
Horizontal, underside .......... .
Horizontal pipe ............... .
45-deg slope, underside ........ .
1.00
0.70
0 .80
0.85
Vertioal pipe. .. . . . . . . . . . . .
45-deg slope, uppera.ide ....... .
Horizontal, upperside . ... . ... .
0.95
1.15
1.30
Had a. 20-mph wind been blowing, the tempera.ture of the.wa.ll would have been l()wer
(perhaps 140"F) and the value of 11. would be about 5.3. A trial-and-error computation is required to obtain the exaCt wall temperature or exact value' of h.
.i
555
k
or
= 1.86 P:kL
h;Di _
-
(4 WC)o.aa (;:_)_0.14,.
- 1.86 - 'lrkL
(17-11a)
(17-11b)
h.D, _
(DlJ)O.8 (Cp.)o.n
G:)D.U
-k -
(17-12)
,
')
, I
556
15
2O.JO
50
100
200 JOO .500
Moss veloci/~ Ib per SQ II-sec
FIG. 17-11. Film-transfer coefficients for fluids inside tubes. Properties a.re determined a.t the average fluid temperature, a.nd for very viscous oils a. viscosity gradient
factor should be a.pplied.
3
10
'1.
,
\
557
-k- - 0.22
(DIlB)O.6
(CJ.l)o.u(\p:-p.) o.u
._p.k
(17-13)
O.04w
MB
in which w is the flow rate, lb per hr, M is the net free distance (or sum)
of spaces between tubes from wall to wall at the center of the shell circle
in inches, and B is the batHe spacing in inches.
The net free distance M may be determined by making a layout of the
tube bundle and actually measuring the sum of the spaces between tubes
(including space between tube and shell) at the row of tubes nearest the
center line. Inasmuch as a layout is not always available except by
trial-and-error computations, the following empirical equations may be
used
approximations:
.
as
Pitch, in.
Approx. equations
1%6
~
1
Fixed tube sheet bundle:
%
1
triangular}
1 ~ triangular
1 square
IX square
I ~ 6 triangular}
1~ triangular
M
M
o. 25L + ~. 0
= O.28L + 2.0
= 0.25L + 1.7
=
M = O. 25L
+ 1. 0
558_
10
20
30
50
100
Only when. the .film resistance is large or the oil is very viscous need the
coefficients be multiplied by the viscosity gradient factor (fl./~) 0,14.
Properties are taken at the average fluid tempera.ture.
Reboiler Film-transfer Rates. Heat is transferred by a 'boiling film
in such equipment as reboilers, refrigerator evaporators, and waste-heat
'boilers. As the rate of heat transfer is increased, vapor tends to blanket
the surface and the rate is sharply retarded. This UBually occurs at a
temperature difference of 120 to 150F, and the maximum heat density
or heat that can be transferred per square foot-hour about as indicated
in Table 17-5.
The two most common reb oilers are the kettle and circulation types.
The kettle type consists of a large-diameter horizontal shell with a tube
bundle situated in the lower half or two-thirds of the shell. Heat is
559
17-5.
Temperature
rise, OF
Service
Boiling rum
coefficient,
Btu/(hr) (sq ft)("F)
Maximum heat'
density,
Btu/(hr)(sq ft)
300
12,000
250
500
12,000
15,000-20,000
applied through the tubes .either by steam or hot circulating oil, and the
tower bot,t oms or reboiler feed enter the shell at the bottom. Disengaging space is provided so that substantially dry vapor leaves the top of the
kettle' or shell. ,A n overflow weir or liquid-level control is used to with- draw the product, and this also serves to keep the bundle submerged. .
Liquid is caused to move in recirculation-type reboilers either by
forced circulation (a pump) or by thermosyphon action.' Boiling may
take place either in the shell or more often in the tubes of a standard
exchanger set in a vertical position. A mixture of vapor and liquid
discharges from the top of the reboiler and back into the bottom of the
tower or other disengaging space. In the common vertical single-tubepass reb'oiler exchanger, boiling occurs in the tubes, and the difference in
weight of the dense liquid in the base of the fractionator and the 10wdensity vapor-liquid,' mixture ill the tubes causes a natural circulation
to be established through the reboiler. Surging tends to occur in thermosyphon reboilers when the effluent stream consists of more than about
35 per cent by weight of vapor.
.
.
Miscellaneous Film-transfer Rates. Film rates for water flowing in
exchangers were given in Figs. 17-11 and 17-12, but lower rates are
obtained in coil-in-box equipment because circulation occurs only by
convection currents and because countercurrent flow is seldom attained.
Velocity
Ft/seo
Lb/sq ft-sec
0.2
12.5
25
50
O.Ii
1.0
2.0
100
Film-transfer
rate
(coil-in-box)
80
140
220
280
560
In small eq.pment operating at small temperature differences, the velocity may not exceed 0.2 ft per sec but in full-scale commercial boxes, a
velocity of 2 it per sec or more is attained when the temperature difference
is great.
F. L. Kallam 3a has studied the film-transfer rate on the outside of tubes
that are being cooled with water when the water drips or is sprayed on
the tubes. He recommends the following equation for the water film
coefficient for the outside of tubes:
(17-14)
in
TABLE
17-6.
5
10
30
50
Horizontal tubes
Vertical tubes
3 J 000--4 , 000
1,000-1,700
800-1,400
600-1,100
550-1,000
2,500-3,300
1,800-2,500
1,600-2 I 200
/I When condensing stea.m- in the presence of even small a.mounts of oil va.pors 8.8 in
gasoline, etc., condensers, conde~a.tion rates are only about 400 ra.ther than t1ie high
values shown here.
The Open-type Cboler, Ref. Nat. Gaso. Mfr., October, 1940, p. 5!).
561
PETROLEUM REFINERY
CONDENSING
TABLE
ft)(hr)
Btu/C'F
MAterial
No steam
210-250
170-210
180-220
130-170
100-120
130-1SQa
Wax distillate. . . .. .. . . . . . .
110- H;;OI1
70-704
50--60'"
........... "....
'" J.\.t;Yll.\t.ie
developed by
investigators but '~ly the work of
A. Donohue ll6
a.ppea.rs to apply to practical refinery design. His formula for
film
condensing coefficient of hydrocarbon vapor mixtures on the outside of
horizontal tubes in tubular equipment is:
h=
C(wr'
Gasoline. . . . . . . . . . . . . .
775
775
ero,sen,e ........
Decane ............. .
720
700
Tetradecane __ ....... .
II
........
III
.....
680
675
Experimental
on the
coefficients for cooling (not condensing)
types of co:mpetroleum vapors are not available, but valu'es for
37
for gases
tubes
17-11
for gases flowing
31
32
across
tubes
Fig.
Rates for gases
across
staggered tubes in a
may
obtained
, Eq. (18-7.)
Fin-tube Film Rates. The film-transfer
for either side of -the
fin tube can be read from Fig.
1, but a special heat-transfer equation,
Eq. (17-15), must
used and an equivalent fin-side area (Fig. 17-13)
be computed. as It
be expected that the
area could
Transfer . . LiOllQe:nsulg Hydrocarbon Vapors,
Eng. Chem.,
62
(1947).
563
'"
~
..... ~
'""I'-....."
-.........
i'-..
~
~
~
.............
......
--..... h
'"
......
" '"
~
i'.
I,
~
~ r-....
~
"......
r-. r.....
r--..... ~
r- I-
r-.. .....
[".
i'o..,r-..,.
roo:.......,
t'.
r-....
..
r--. t--
'"
""~I"
b.
I"
I"
r--.
"'r--...
,...",1"r""" to--
1\
"'i'..
I'
...............
~ ~ r-....
t' t--..
~ f....:
........
r--- r.....
r-
i" ~
~
~ "- "6
r--
~-~4
,;
I/O
30 40 50 60 70 ao IO~
ISO. 200
300 400 500 600 800 1000
fiLM TRANSFER RATE ON FIN-SIOE-B.T.U./SQ FT." 'f'-HOUR
FIG. 17-13. Chart for determining the equivalent fin-side area. in fin-tube equipment.
(Oil Gas J.)
15
20
+-A
Ah
J I
I
+].
I",
The equivalent
(17..15)
+Ri
in which the subscript f refers to the fin-side transfer rate, fouling fa.ctor,
and area. Example 17-8 indicates how to compute the equivalent area
of fin-tube equipment.
. Ordinarily, the fins ~xtend out from the diameter of the tube, and
although such tubes can be installed and removed from double-pipe
exchangers (Griscom-Russell and Brown ' constructions), "they are not
entirely satisfactory in ~undles because replacement tubes cannot be
slipped through .the holes in the tube sheet. In meeting this difficulty
j ',
PETROLEUM REFINERY
ENGlNEE~G
a .tube has been devised (Wolverine) which has such short fins that t~e
diameter at the fins is no greater than the (expanded) diameter of the
tube at the ends, thus pet:mitting the replacement of tubes in a bundle.
Example 17-6. ' Transfer Rate for Exchanger. Kerosene is to be cooled from 400
00 300F by means of 35 API crude oil. The crude oil rises in temperature from
;70 to 285F. The exchanger has ;i-in. tubes. The crude oil has been desalted,
and the exchanger will be blown with steam each month. The conditions are as
~~:
Average
fluid temp
Viscosity,
centipoises
(Fig. 4-43)
278
1.0
350
0.3
Ma.terial
Velocity
Passes
Lb/sq
ft-s~
Ft/sec ,
72
140
1.5
3.2
2
4
The film-transfer rates 127 for the crude oil (Fig. 17-12) and 270 for the kerosene
(Fig. 17-11) in this instance need not be corrected by (y./J.'m)O,U beca.use the film a.nd
wall tempm:atures are nearly the same. The fouling factors are about:
2 .5
1.6
4.1
The inside area. of one foot of lS-gauge. %-in. tube is 0~1299 sq It (Table 13-3) and the
outside area, 0.1636 sq ft. Thus. the over-aIr transfer rate based on the inside area.
but neglecting the will ~tance [Eq. (17-Sb)1, is:
H,= 1
.
h,
A,
+ AvA .. + RD
1
1
0.1299
270 + 127 X 0.1636
1
0.01405 = 71
-~----~~~-----------
+ 0.0041
1
= 0.0037 + .0.00625
+ 0.0041
~~~-=~~~~~~
HD
0.1636
270 X 0.1299
1
127.+ 0.0041
= 60.5
.
Hi - '0.0037
+ 0.0062:) + 0.009 =
1
0.01895
= 52.3
550,000
X 63 ... 1-44 sq ft
= 60.5
A 2-shell, 4-tube pass exchanger tends away from eountercurrent flow (Fig. 17-4) but
~.
', '
.'
,"
565.
in thls instance to only a small degree because the two outlet temperatures are lolatively far apart.
Bxample 17-7. Transfer Rate in a Steam Heater. A tank of fuel oil, 13 API 60
a steam coil. The
viscosity at 210F, is to be heated from 60 to HOF by means
oil has a pour point below 60F. The oil stands in the .tank and circulates only by
natural convection. Exhaust steam- is used. and it leaves the coil at atmospheric pressure but not cooled below 212F.
The situation is complicat~d. because the velocity of the oil must be estimated and
because the operation is not continuous.
Average temperature of oil. a.pproximate: (60 + 110) + 2 == 85F'.
The oil-film resistance c~nstitutes most of the resistance (it can be checked later).
and thus the approximate temperature at the fouling of the metal wa.n is (the-0.S5 is an
estimate):
, 0.85(212 - 85)
85 = 193F
of
The viscosity of the fuei oil (curves 18 or 19 of Fig. 4-43) is about ~25 centipoises
at 85F and about 13 a.t 193F.
(p./IJ.rt,)o.u = (22~ s)o.i.f = 1.492 _
less
The surface correction was made by meaDS , of diameters rather tha.n areas. The
steam film could have been neglected without introducing error.
If the heater is to heat the oil in one hour and the duty is 29<)700Q Btu, the SQrface is:
A /I
200,000
=<
120
13.33 X 125 = .
sq
ft'-
The temperature differences at the two ends of the tube or coil were so nearly the same
(152 and 102F) that the logarithmic MTD was simply estimated as 125.
Example 17-8. Transfer Rate in a Fin-tube Heater. A common type of 24-fui
tube has 50.5 sq ft of external finned surface and an internal surface of 8.4 sq ft. The
actual ratio of surfaces is
50.5 _ 60
8.4 - .
566
Crude oil (viscosity of 1.3 a.t an average fluid temperature of 230F) flows at 4, ft
per sec ~hro~gh the tube, nnd kerosene (viscosity of 0.3 centipoises ~t 340F) flows at
1.0 ft per sec arou"nd the fins.
Film I:ate
Fouling
factor
2 .5
1.5
MllSS
Material
velocity
220
43.3
According to Fig. 17-13, the equivalent fin-side tlIea. is 3.83 and the transfer rate
based. on inside surface is [Eq. (17-15)J:
H~=
1
10.0015
3.83 X 115 -I- 3.83
1
225
+ 0.0025
= 104
This same rete based on fin-side surfn.ce is only 104 -:- 6 = 17.3, but something is
gruned by the use of finned surfp.ce because the rate in a plain double-pipe exchanger
would have been only ~bout 63, and thus a.bout
replo.ce one fin-tube unit.
EXCHANGER DESIGN
IiP h = 0.00032 ng
p
(17-16)
507
fll>L
= -0.00022 gL
p
(17-17)
The pressure drop across the tube bundle cannot be calculated with
precision, but the situation has been studied by numerous investigators 80 ,39,4D,41.42 and the following formula is suggested:
(17-18)
psi
15
where
f'
0.75
(p;Dr(n;r
\
I
\
,;
"
\.
"
f
<
The actual pressure drop for crossflow may be as low as 50 per cent of that
calculated by Eq. "(17-18) because of leakage and poor bundle penetra,
tion. Theoretically, the pressure drop across the bundle, t:.P:z:, should
be multiplied by the viscosity gradient term (f.'/Ilw) 0. 1.4,.
, The total shell-side pressure drop is the sum of t:.PL and ilP:e.
Seider and Scott, ASME unpublished papers, no. 83 (1932).
40 Huge, E. C., Tram. ASME, 69, 573 (1937).
41 Pierson, O. L., Trans. ASME, 69, 563 (1937).
42 Chilton and Genereaux, Trans. A.l.Ch.E., 29, 161 (1933).
39
",,'
~;..
1f..
"
~r
,I;
~)
'J
11
.~~
;,
t~
r.
,.
"
l'
i'
k,.
"
568
PETROLEUM
= Lu
569
resistances to obtain an over-all coefficient {Eq. (17-8a)]. The approximate surface" can be computed from the exchanger duty,. oorrectyd mean
temperature difference, and over-all ,coefficient by means of Eq."~(17-1a),
page 534. A .final coefficient will be determined in later calculatIonS".
Size of Units. The number of tubes can be computed from the tube
size, exchanger length, and estimated surface. They may fit into a single
maximum-size bundle, but it may be necessary to use several smaller
bundles or shells, A tube layout may be prepared, or Eq. (17-10) may
b~ used in approximating the size of the bundle.
Tube~ Pre88Ure Drop. The number of tube passes per exchanger
is selected by trial and eiTor, to stay within the allowable pressure drop,
In making trials, note that the pressure drop varies approximately as the
cube of the numbu ,of tube passes.
Tube-side Film Coe:lficient. Mtet selecting the shell size and number
of tube passes, the:film coefficient may be calculated using the methods
outlined in this cha.pter [Eqs. (17-11a) and (17-12), Fig. 17-11, etc.J.
Shell-&ide Pressure Drop, The baffle pitch and window fraction may
be chosen by trial and error to give the allowable pressure drop [Eqs.
(17-17) and (17-18)),
Shellr-side Film Coefficient. Mter the baffi.e pitch and window fraction
ha.ve been selected, the crossBow and longitudinal mass velocities, and
the mean mass velocity, may be computed; and the shell-side coefficient
may then be calculated from Eq. (17-13) or less accurately from Fig. 17-12.
Over-all CoejJicient. It is now possible to ' compute the over-all coefficient with more accuracy. If the coefficient is larger than the one
, assumed in the surface estim~te, a check should be made to see if a. smaller
exchanger will be adequate, whereas if the coefficient is smaller than the
assumed coefficient, it is pecessary to repeat all computa.tions for a larger
exchanger.
Q
materials are:
Rich oil
(tubes)
, 11.8
Amount, gpm ............ ', : ... '.... ; , 695
Gravity, API ............... ', ~ : ... .
44
6.713
Gra.vity, lb per gal ................ .
10.0
Allowable pressure drop, psi .... :" .. .
Characterization' Factor ............ .
Lea.ri oil
(shell)
11.8
600
,: 40
6.87
16.5
" Steel tub"es (~ in. o.d., 14 Bwg, 20 it long) 'will be used at a 1 %a-in. tnangular ,p itch
. and the rich oil is sent through the tubes. No vaporization oc~.
' I'
,,; '
.r
"
.;
if
".
!,
"
570
247,000 lb per br
280,000 lb per hr
For 8. ratio of fluids of about 1.0 Fig. 23-5 indicates that the lean-oil (smallest quantity) outlet temperature should approach to within about 50F of the iplet rich-oil
4/0F-~ ,
lj=90F
60
MTO=67.5
(correcled 56)
FIG. 17-14. Terminal tempera.tures in Example 17-9. There are four shell and two
tube passes but no longitudinal baffle to produce the pure countercurrent flow indi-
a~h~.
24 7,000(410 -
150)0.585
This same amount of heat goes into the rich oil 130 tha.t its outlet temperature must
be:
'
goOF
37,600,000
= 334 F
280,000 X 0.55
-
T1
T2
t2 _ tl
P = t. - tl
TJ .:.... tl
90 - 334
150 _ 410 "'" 0.94
= 150
- 410 = 0.812
90 - 410
Examination of Figs. 17-4 and' 17-5 shows that one, two, or three shell passes cannot
be used. but a correction factor of 0.83 can be read for four shell passes (Fig. 17-5).
ai.
571
Longitudinal bafHes could be used to attain true countercurrent flow and thus raise
the 0.83 to 1.0, but in this "design no longitudinal baffles will be used.
Corrected mean-temperature difference = 67.5 X 0.83
= 56F
Estimate of rur/ace.
212
0.5
'120
210 (Fig. 17-11)
1.5
280
0.5
150
235 (Fig. 17-12)
1.5
The inside diameter of %-in. tubes is 0.584 in .. (Table 13-3). An approximate over-all
rate can be computed from Eq. (17-Sa).
H;:,-
0.75
235 X 0.584
.,1
., .
~:!
:~
+ 210 + 0.003
= 75.5
A o =. 37,600,000
56 X 75.5
Size of unit.
shell will be
8900
=,
f
sq t
With four shells, each shell must house 2,225 sq ft, and the tubes per
According to Eq. (17-10) the outer tube limit of the bundle will be about
565 = 0.86
(1 ~ 6) 2
i~5
24 in.
X 2D-n- = 9,600 sq it
" i
:,~ .
,
. .j
1-
'j
'I.
.I
, .
J
(O.5:~~0~O 0.785
MB8Svelocity =
3,600 X
Reynolds No. =
DG
144
"2
0.584 X 138
X 0.000672 - 19,900
p = 12 X 0.5
. ; :1
. .i ';'
,572
For
= 0.00032 X 8 X (138)2/(62.4
Total pressure drop .." 3.69 + 1.04 = 4.73 psi
I1P
X 0.75)
= 1.04 psi
This is below the allowable pressure drop of 10 pounds but it is obvious 'that four
tube' passes ra.ther tha.n two posses per sheU would. ccrtuinly [4.73 X (~)3 =- 37.9
psi1 produce too much friction.
Tube-~e film coejfici'e.nt. Using the maf!i velocity of 188 ~d a. viscosity of 0.5
centipoises indicates (Fig. 17-11) that h, =- 225.
Shell-8irk prU8W"8 drop. The bafIle spacing a.nd window area must be seleoted by,
a trial-and-error computa.tion. Assume, 0. 20--ib. bafHe ~s.cing and a 20 per e~t window fractiOn.
Net free distance (p. 557)
= O.25L + 2
I:
0.26 X 25
+ 2 = 8.25 in.
'
8.25 X 20
Isq
sec
,
.
21-7,000 X 0.04
gz, = O.785(26.5t _ 610 X 0.751)0.2 = 116
(Is
At the,bafile spacing of 20 in., the number of spaces between ba.1Hes a.nd the number
of ba1Res are:
Spaces 20 ~ 12 ~ 12 (48 total)
0.75 X 60
i2 X 0.5 X 0.000672 ... 11,200
1...;_' 1
h
42.5 X 0.75
170, the Bow 18
. tur bulen t' a.nd
Smee
t.LWII 18 arget't an 0,9375 _ 0.75 or
/' =
'
0.75
_
0.75
= 0.153
0.9375 - 0.76)0.t (11,2OO)D.2
0.758 X 6.45
,(
0.75,
The number of rows crossed and the ero:l'Jfio\'l ,~re'l:.lr~ drop :U'6:
25
'
Thus, the total pressure drop is 17 psi, which is nearly low enough to meet the require- '
ment of 16.5 psi,. and it may possibly be satisfactory beca.use oomputed pressure drops'
are u'sua.lJy somewhat 'high.
573
-Shell-side coefficient. The geometric mass velocity and shell-side film coefficient
are:
GB = 3,600 Y60.2 X 176 = 370,800 Ib/sq ft-soo, or 103 Ib/sq ft-see
no = 190 (Fig. 17-12)
Ovef'-(.Jll coefficient and siu.
Ho {Eq. (l7-Sa)]' =
1
190
1
0.75
0.584 X 220
+ 0.003
= 71.5
The resi8ts.nce of the metal wall a.nd the viscosity gradient correction are, in this
i.nBtance, negligible ..
. d
9-400
ft' Surla.ce reqUlre
= A ,,= 37,600,000
56 X 71.5 =,
sq
The design was be.sed o'n a surface 01 9,600 sq ft which means that about 2 per cent
,extra surface is being supplied. The design-is almost in balance, and if a little largE.u'
window fraction is provided, or the ba.fB.e spacing is increased slightly, the shellside pressure drop will be satisfactory. A check might be made to see if a. smaller
exchanger is satisfactory, but in this instance a. sma.ller exchanger probably would
not be adequate. '
TUBULAR VAPOR COOLERS AND CONDENSERS
~ondensate.
,iJ
574
an
305
.zone 2
___.....,'20
89 M. T.1l140
195
l95
. Zone .3
74 M.T.1l1l3 .
Btu perm
Cool vapor or condensate .. , .......
63,OOO(3~
- 195) 0.60
~ 0 ..46
..", 3,670,000
575
Btu per hr
63,000(195 - 180) X 0.565 = 532,000
6,000(195 - 180) X 1.0 = 90,000
== 15,000
2,000(195 - 180) X 0.5
637,000
The percentage of hea.t that is absorbed in each zone and the rise in water temper&ture in each zone, for countercurrent flow, are
Btu
Per cent
12,343,000
5,890,000
637,000
18,870,000
65.4
31.2
3.4
100.0
Zone
Rise in water
temperature
(total 48F)
2
3
4
TotaL .......
31
15
2
48
Zone
!\leu
temp
Duty
\.,
A"
R,*
h ..
Ht
Note.
diff.
.....
..
..
&
...
18.810.000
...
143
118
114
.. .
...... .
350
0.006
0.007
0.009
.,
150
400 . 350
45 350
-. . -...
. ......
.. . ........
64
81
-.29..
No suoh sone
1,850 Table 11-7
643 Table 17-6
19.2 Page 561
2,185
See Fig. 17-9. A water factor of 5, and different facton for each of the o\ber conditiODs.
t Should be correoted to a common surface buis such as out.lIide- 8Urfa.oe.
As a comparison, the over-all transfer rate that corr.esponds to the (our zones is
18,870,000
2,185 X 144
= 60 0
.
.'
.
,
576
21
The approximate condensation and true-boiling-point distillation curves of the products s.re shown in Fig. 17-16, and a diagram of the system is shown in Fig. 17-17.
Since this example is aimed a.t an illustration of principles, the molecular weights,
specific heats, and latent heats ha.ve not been corrected to the latest values shown in
this edition.
.
577
~GOIS
qoo
.1
oil
1\%
89.%
800
700
:t
til
c(\I
(j)
600"
(2)
Q)
~ l---
--
@'1dJ
500
400
300
200
ill
652
lJ..
til
6J
L(5)
~~
15
II)
~j
I-"'"
394 ~ F"-
~
305
--.:,. .,.:::.-
456 r-'
~~ ~
~~
100
Unit4
to
U7it '3
'20
~"if I
U,it 2
30
40
50
60
70
PercentOlge
. FIG.
80
QO
100
The data given in curVes 1 and 2 (Fig. 17-16) apply to condensation at atmospheric
pressure, and hence curve 5 for vacuum conditions must be computed . .'
.
The total pressure at the inlet to condenser 1 is 30 mm, but at the end 'I t is' (30 - 3),
or 27 mm. Furthermore, steam is presentJ and it further reduces the pa-l'tial pressure
of the oil vapor and decrea.ses the temperature of condensa.tion.
Moles W.D.
:=:
1O:2~OO = 331.0
12,000
~2
= 381.0
Moles vapor
Moles steam
= . 49.6
.1,400
18
=--
78.0
459.0
X 38~S9 = 24.9 mm
578
outl~t
the par-
These tem
, 70F.
CooJi'1!?l worier
No.1' ,456'F. N
27m.en.
~lg0F.
Hofrefiux
24
mm.
,,'
nrie '
Ytipof
30m~m~.~~
70 barometric.
211'(1m.
.
(jotS
ai/
II
i
1
.L
579
iO
~2~
25 X
12%07
= 15.5 mm
ColTecting 6351) to 15.5 mm gives 394F. Partial condenser unit 3 was computed in
a. 'similar manner.
Partial Condenser Unit 4. By the time unit 4 is reached. the amount of nonconden-,
sable gases (steam) has become relatively so large that a more detailed analysis i8
necessary. The following tabula.tion was computed (curve 4, Fig. 17-16) by using
the same general principies that were used in stud~g units 1 and 2.
The pressure drop is very small (1 mm), and hence a. <;onstant pressure of 23.5 mm
was used throughout the entire unit. ,Likewise the flash curve 4 is so flat that 'a. tel)1perature .of 563I)F was used to represent the entire curve.
Partial pressureJ mm
Condensation
points, OF
.'
50 "
33
8.6
6.5
4.8
3.5
22
16
1.5
11
1.0
11.0
7.5
5.0
305
296
283
274
264
3.8
2.7
1A
241
,
The sharply curving tail on the front of the condensation curve shows that all the
vapor can never be completely condensed until the stea.m is condensed. Refiners find
that the wa.ter leg of the barometric condenser always conta.ins oil a.nd wa.x stocks, and
tra.ps or skimming devices must b~ insta11ed.
Thermal Duties of the Units. Unit 1 (47.000 Lb Condensed). Condensing zone
throughout
"
Btu perhr
, Cool vaPor ..... " ... 71,000(490 - 456) X 0:58 ==1,350,000
Cool stea.m ... , ........ 1.400(490 - 456) X 0.5 =
23,800
CooL ....... .47,000(490 - 456)
(0.68 ; o.~),~
~83JOOO
3S
follows:
duti~,
Cendenser
Lb
unit
condensed
1
2
47,000
490--456
6.676,800
39,000
20,000
12,000
. . .... . . .
456-394
394-323
323-220
7,213,000
3
4
Temperature
range
. ... . ...
"
Approx.
Btu per hr
4,058,000
2,856 J Ooo
20,803 J 800
'580
Transfer Rates. Surfaces, and Temperature DiBerences. Crude oil is heated from , ,
140 to 300F in the first three unita, and wa.ter is heated from 70 to 120F mthe fourth
unit. The crude oil velocity is 3 ft per SOO, and the water 1~ It per sec. The temperature ranges are shown in Fig. 17-18. One-inch tubes were used throughout.
The vapor film fa.tes were considered 8.8 consisting of two parts. i.e., condensing and
vapor cooling. The vapor-cQOling film rates were obtained by extrapolation of the
Unit 1
Un;'" oJ
___-
J75
Un/f2
Unit
COMPUTA.TlONS
Duty
~ll SURFAcEs
Logarithmic
mean-temp
difference
IN ExAMPLE
17-11
M888
velocity,
lb/ft-see
11.0
A, Rt)
1P
A"
I. Condensing:....
. Vapor coolinge ..
Over-a.ll .....
2. Condensing ....
Vapor cooling': ..
. Over-all. . . . . . .
3. Condensing ...
Va.por cooling" ..
Over-all .....
1, 2, & 3
over-all ..
5,303,000
1.373,800
6,676.800
5,730,000
1,483,000
7,213,000
3,136,000 .
922,000
4,058,000
17,947,800
4. Condensing .... 2,135,000
,721,000
Vapor cooliDge ..
Over-a.lI ..... 2,856,000
204
20.4
.....
1.0
25
14
.. .
...
.. .
21,9
219
0.8
27d
12
219
.. .
204
...
..
to
..
--
..
196
196
196
...
29 4
0.5
...
.. .
243
.. .
...
187 '
187
187
0.2
.. .
Dependent on velocity on the shell side. The lIb per' sec per sq it corresponds to
-a linear velocity of about 50 it per sec.
l) Should be brought to a common basis of surface such as outside surface.
C Some liquid cooling also included.
*' Condensing coefficients are halved for vacuum service. See pages 560 and 561.
G
I
I
.l
I""
I
"
581
lines of Fig. 17-12 (by almost two logarithmic cycles). and it is believed that somewhat
higher rates result from other equations. However. experimental. data for .highmolec~weight petroleum vapors are not available. Condensing rates are halved
for high-vacuum service. Table 17-8 shows the complete computations.
Note that the logarithmic mean-tempel'8.ture difference gives confusing results if it
. is used for the three units together. Its use in this mapner shows an over-all rate of
heat tr8.n.sfer (12.4) tha.t is lower tbau. the transfer rates in ap.y of the three ~t8.
HEATING COn,S FOR TANKS
Storage tanks, tank cars, vessels, and fuel-oil tanks are often equipped '
with steam coils. The approximate amount of exhaust steam required to'
heat or inaintain temperature in such tanks is approximately .
Lb atJm per hr per 1,000
:,
f
<.
Time of heating
(no
"
Wind)
. The amount of exhaust-steam-heating surface reqmred for tan"ks containing semisolid oils such as heavy fuel oil, residuum, heavy topped crude)
and heavy asph~t crude oils but not asphalt or. waxes is indicated in
Fig. 17-19. Similar charts for regular 'c rude oils and lubricating-oil stocks
are a.vaila.ble. 44 Less surface, by the folloWing percentages, is required if
live steam is use<t.
Preuu.re,
psig
ill
:~
PucenUig~
Exhaust
21
100 -
63
50
33
67
138
Emmple 17~12. Heating Surface for 260..bbl Puel-oil Tank. A tank of fuel oil is
et the air temperatUre of 50F. and it is d~ to able to heat it in 7 hr to a temper.;
ature of 120"F.
Referring to Fig. 17-19, note the dotted line. Move upward to the capacity (250
bbl), across to the reference line of 50F, and then follow upward to a. temperature
ditierence (oil at 1207 minus a.ir a t roOF) of 70F and read 520 sq ft 81ll'face at the
right.
.
The other dotted line indicates the amount of surface required (225 sq ft) 1f the
tank temperatUl'e is to be 80 rather than 120'T.
U Nelson, W. L., Heating Coils for Tapks, Oil Gal J., Oct. 7,. 1944, p. 103. '
be
I~
."{
582
PETROLEIDil
REFINERY ENGINEERING
. ,.f
<,'
~~
~~ '\
'/
>-.
""
z
!oj
..lJ!, I
II;
YOO~
...9J
...~ ,I
I
'~\\\
'\ \
~ ~~
~~
~I
'
"
""
G'" , '\\: \ ~
"-
\\\
\'\ ~
~O ~'\
/
\
I
I
/'
!oJ
100000
101
0/1
150000
....
~ ~~~~~
.~
",
:3
,"'~'''<.I
,,7
t-z
V1/
V/ ///
""
50000
","
'"
",,,,/
~
",
%
~
\ ~ . ' ~V
I\'i{! Y ,
~\
~ '\ '\ ~ . ''t!11 ~ /
1/
!S'~
r\. :
0
I,
"
I ,
,,
,,;
d
I/)
10000
'"" , i'v'Re
11
'" "'.
--- -L
' "",
'" ~~
r--
"-
'\
"
~ ..... ,
0/1
.
C.
'!J..
~
7000
a::
2000
. r-- __
700
'"
I
' I .J
I I
iI
500
, ,'"
"
IL
V;
, 'I
1000
VI ".
L_ 4-
I~'1
' ...
'"!I L
....
200
,,'"
a:
5
a
5000 ....
/'"
/ =~
,., '-l- 74 .--.-
',-
'"'
~/~r ..........
v'
II
-... , ,V
~ .
a:
:l
en
u
...<z .
w
J:
i---w
~
.(
10Q
L.,I
I-
en
70
50
"
I I:
30
I,
" ........ ,
~~
Af~
'-
~,
.-'
, I,
bJ
"
'\
.........
~,,/
"
'II
il
20000
","
\f I/; // ,,/
,,'
I
70000
o 50' 00 I30-F
OIL, T~MP. LESS,
AJR TE .... P.
48 1296
10
10
24
HOURS TO HEAT TANK
FIG. 17-19. Heating surface (eXhaust steam) required for heating semisolid oils in
COIL-IN-BOX
CONDENSER~
AND COOLERS.
In the past these equipments have been standard, and even today they
a.re used extensively for final cooling before.storage. Heairtransfer ra.tes
are low in this type of equipm:ent owing (1) to the low velocities that must
be used and the low natural-convection rate and (2) to the gradual a.cCU"
I
1
583
mulation of pipe scale and fouled surfaces on the water side. Special r,astiron condenser sections with ribbed outside surfaces, such as the Stirling
section--of the. American Radiator Company, are sometimes used. The
main advJintage of. ~his condenser section is the large v~por space afforded
and the compact arrangement. that is possible. To allow for the rapid
decrease iIi vapor volume" coil-in-box condenser coils are usually built as
a series of large-diameter pipes connected in parallel to a header, and
smaller pipe sizes are used on each of the parallel branches in the liquid '
cooling zoJie. For simple cooling, the coils are usually connected in series
throughout the entire cooler. The usual inlet vapor velocity is approximately 50 ft per sec, and the outlet liquid velocity is between 0.5 and ,
2.0 ft per' sec. The higher liquid velocity is used for light materials such,
as gasoline, and the 0.5 velocity for cold tar, wax distillate, etc. In beSt
.
practice the coils are built in pairs with a.bout 15 in. between pairs to
facilitate cleaning and repairs. Using flanged pipe facilitates the removal
of pipe, but the coils are not 80 compact. The Griscom-Russell Company
manufactures a "bent-tube" section for coil-ill-box service or for cooling,
by means of water sprays in a cooling tower. These section's consist of
two headers with a large number of. small tubes between them. The
tubes are bowed slightly during manufacture so that by expa~sion and
. contraQtion .the accumulation of sca1~, etc., on the outside of the tubes
will be dislodged. For certain scales, the bent-tube section functions
properly, but for others the tubes must be .cleaned by the usual hand
methods.
Coils of . standard or extrar-heavy steel pipe with double-extra-heavy
malleable fittings are used for normal conditions. For hard water, many
refiners req'uire the use of genuine wrought-iron pipe. Best practice for
long service requires the use of Classes Band C flanged cast-iron pipe with
Class D fittings. .
The transfer rate inside normal-size pipe cannot be given as for tubular
equipments because fouling factors are not available. Owing to the many
variables in the design and use of coil-in-box equipment and particularly
the wide range of velocity and surface conditions, the rates are not so
consistent as for tubular equipment. For natural convection on the outside of pipe coils, the water film rates given on page 559 aresuggested, but
they must be used with fouling factors in the magnitude of 20 to 30. , .
Although the water flow in boxes from the bottom to the top.is usually
consfdered to be countercurrent with respe<?t to the hot fluid, unsuspected up-currents usually occur at several points46 so that no clear
pattern of fiow can be defIDed. However, the very large fouling factors
for such equipments tend to erase any practical effect of type of flow .
INelson, W. L., Waterflow in Coil-in-box Equipment, Oil Gaa J., Dec. 7, 1946,
p. 112.
.
"
'584' .
PET~OLEUM
REFINERY ENGINEERING
is
Although the use of over-all rates not recommended, I,l.t ti~es the
engineer has reason to make very approximate estimations ' of surfaces,
etc. Table 17-9 is a tabulation of over-all rates that were obtained from
various authorities in refinery positions and with engineering companies.
The discrepancies in the values indicate clearly the difficulties involved in
attempting to use over-all rates and why the use. of over-all heat-transfer
rates is being abandoned.
1-'.A.BLE
17-9.
Authority number
l?uty
~-
COil-in-box equipment:
Vapor cooling .................
Condensing and cooling .naph th.a.
Cooling naphtha ..............
Cooling kerosene or gas oil. ....
Cooling wax distillate, .........
Cool~ng lubes .......... '.' .....
Cooling t8.l'8. bottoms, etc .....
Condensing kerosene ..... . ....
Condensing gas oil ............
Condensing fuel oil and lubes ...
Tubular equipment:
Condensing naphtha.:
Wa.ter ..... , .......... , ..
Oil .................... ~ .. :
Condensing kerosene:
W ~ter. , ....... ; ..........
..
..
15
2()
11
..
..
, .
15 15-18
, . ..
..
....
12
13
..
, .
.. -
..
..
..
52
26
39
25
.
.. ..
.. ..
.. ..
..
40
..
--
18
18
16
32
20
17
14
11
18
16
20
12
12
10
23 ..
7
26
27. 24
36 ..
23
18
..
13
, ..
55
48
. 62
60
..
37
27
27
65
31
25
,
..
' .
47
.. ..
28
, .
..
..
25
..
14
..
..
27
.,
..
..
..
..
45
6
7
- - --
Range
. . . .. ... .. . ,
12
14
10
..
, . ,
..
I-
28
12
7
26 17 11-32
15 .. 15-20
21 .. 15--21
10 . . 10-14
11 13 11-14
.. 10 7-13
20 15 15--26
13 l~ 12-27
.. '10 10-36
70 50 3~70
30 27 25-37
48 .. ..
24 .. ..
54
70
50 31-65
27 24-27
70
..
47~70
20 ..
.. . .
36 35
18 ..
20 20-45
.. .. 18-28
35
24 .. ..
16 . , . .
19
9
20
25
20
25 14-25
.. 16-27
20 .. 19-20
25 .. 9-25
-,
.I
CHAPTER
.18
When pipe- or tubestills were first built, the important part that radiation plays in any open-fired heater was not appreciated, and the first
stills were purely convection types, consisting of a, bank of closely spaced
tubes witb a combustion space below or to the 'side. Coke deposited in
the tube~ that were exposed to radiation and the remaining tubes absorbed
, little heat. When overheated tubes were removed from the still, 'other
tubes began to overheat, and as the number of radiant tubes was reduced,
the , situation was aggravated. Finally, designers realized that the
radiation from the flame cloud must be distributed over a large surface,
and the modern radiant type of still has been the result. If exceedingly
mild rates of h~ating are required, the still may consist almost entirely of
tubes that are exposed to radiation.
Shell
batch stills are no longer used except when a single,still may be
used to rerun or distill several small stocks such as 'lslops," speciaJ
naphthas, petrolatum solutions, etc.
Types of StiUs. Most modem stills are built" with two distinct heating
sections: a radiant section which can receive h.eat directly from 't he flame.
and a convection'section which recovers heat from the hot gases traveling
to the stack. Figure 18-1 indicates diagrammatically the arrangement
of , tubes and the direction of liquid flow. Names are not standardized
but the several stills of Fig. 18-1 might be c~lled:
or
(a)
(b)
(c)
(d)
(e)
(f)
Large box-type
(g) Large isoflow (Petrochem)
Separate-convection (Lummus) , '(h) Small isoflow (Petrochem)
Down-convection
(i) Equiflux (UOP)
Straight-up (Born)
(f) Double-upfired (UOP)
A-frame (Kellogg}
(k) Radiant wall (Selas)
Circular (DeFlorez)
, Although all ' of the sti11s of Fig. 18-1 are useful for many services, there'
are certain features in which each excels or may be deficient. .
..
1. Flame In:r,pingement. Too large a flame can cause impingement, or
overheating of certain tubes in nearly aU of the stills, but tubes that are
vulnerable are those just above the bridgewall in (c) down~convectionJ
585
.~
586
and the lowest tubes of (J) double-upfired or (tl) straight-up. The difficulty disappears in stills (d) and (;) when the capacity is large, i.e., the
stills can be wider. Note the black tubes in Fig. 18-1.
2. Hot Tubes. The rate of heat absorption tends to be high at the
entrance to the convection section because heat is delivered by both
radiation a.nd convection [black tubes in types (a), (c), (d), (e), and (j)J.
The feed. because it is cooler, is sometimes introduced through these
tubes (a screen bank), and in some instances steam is superheated or water
is heated in the screen bank. Likewise, the tubes situated closest to the
flame receive the largest amount of heat [black tubes in (d), (f), (g.), (h),
and (j)].
.
3. Oil Firing. Oil fuel tends to produce larger flames especially
because larger burners are used. Stills (a), (b), (c), and (e) are .b est
suited for oil firing a.lthough the larger sizes of the other stills encounter
little difficulty.
-- 4. Heat Di8tnOution. One phase of poor heat distribution has been
mentioned in item (2) above; but in addition the rate of heating varies
widely in different parts of the boxes or cavities of such stills as (a) and
(c), although most of the other vertical stills c.m attain a fairly uniform
.
distribution of heat:
5. Two-coil Heating . . Still (e) is riot suited for two-coil How although
by experiment it is possible to use it for two streams. Symmetrical
two-coil arrangements can be devised for' most of the other stills, but
if a different rate of heat input is needed in. each .C9il, t~e stills with a
center bridgewall are most effective.
6. Control of Rates. ~tills .(t) and (k) are emine:ntly suitable for precise
control of the rate of heat -input and for operation at excee<J41gly high
(1000. to 1500F) temperatures. . Very low rates of heat absorption can
be attained in the circular types (I), (g), and (h), and in other types if
enough radiant surface is provided.
7. Capacity. Stills (c), (il), . (h), (i), .and (k) can be built for the
lowest capacities, and types (a), (b), (e), and (j) are best suited for large
capacities..
.
8. Stacks. Stills (a), (b), (c), and (i) require tall stacks, but scarcely
any stack (except to release the gas at a high level) is needed with the
other stills because the hot furnace itself produces a draft.
9. Cost. The roof constructions of types (a), (b), and (c) are expensive.
Walls not covered With tubes [see (a), (b), (c), a,nd (e)] tend to overheat
and must be of heavier construction. Suspended panel wa~ .a re usually
cheaper than brick walls, but suspended tile walls are very expensive.
The large framework of still (i) is expensive, and the numerous burners
of tyPe (k) add to its .cost. The A-frame still (e) conserves on structural
steel.
.
.
587
To sJoelt
In
In
To s/oclr
Out
~Burners
(0)
,t
DQ OOOOOOIlIllD 00 0
//
Ij
/
-"
""_
Burners
.
0
Gaoe
DO
.g
00
GoOOO
: \.0 '0
Aa0"
,
o
To
stock
sled
OG
,.~
To
0000
0,,0.""00
"8
DDDDO
000
In
/-
70-
lock
(C)
(d)
(e)
,
I
+
+
d U
BurfllJrs
(I)
t~t
.....-
....J
(g).
fh)
Burners
(I)
(jl
(It)
FIG. 1"8-1. BaSic types of pipestill heaters (see' text for meaning of letterS). ,
588
In the isoBow stills (g) and (h), finned tubes are used in the convection
secti~n. This greatly reduces the amount of tubing required and resuita.: in rates of heat transfer in the convection section as large as or sometimes
larger than in the _radiant section. In still (h) the upper ends of the tubes
are finned and thus there is no distinct convection section. The Belas
still (k) employs ceramic burner cups,! spaced at about 30 in., which cover
both walls.
,Gases are cooled by tubes on the walls, and this tends to cause a downward gas flow behind the tubes~ Velocities as high as 10 ft per sec have
been recorded,la and it is becoming evident that much heat is transferred
in the radiant section by convection as well as by radiation. The optimum space between the wall and-the tube is about one tube diameter.lG '
In Petrochem heaters (Fig. 18-1g and h) about 13 per cent of the heat absorbed by the radiant tubes is delivered by convection an~ by internal
recirculation.
The actual heat intensity CUl'ves for several heaters are presented
by H. C. Schutt, 2 when applied to cracking for the production of ethylene.
Air preheat is indicated in Fig. 18-1f (DeFlorez), andit can be employed
in any still that is mechanically tight from gas leakage. The recirculation
of flue gas through the combustion chamber by means of a. fan is not indicated in any of the stills. The flue gas is reheated by the flame, causi~g a.
low~r flame temperature and thus 'a milder radiation rate. At the same
time the convection-section duty is increased, and a larger convection
section must be provided. ThusJ ' flue-gas recirculation is' particularly
suited to the older convection-type stills. When it is necessary to alter
or regulate the rate of radiant absorption, no method other than fiue-gas
recirculation is available except such expensive methods as the use of
large amounts of excess air; a reduction in capacity"or possibly to obtain a fuel which radiates less. Flue-gas-recirculation stills we~e widely used
during the development of thermal ,cracking processes; but, now that
engineers know how to design st~lls for specific radiant-absorption rates,'
- recirculation stills are no longer installed.
,The advantages of a symmetrical arrangement of radiant.:.heat-absorb- ing surface are a.pparent in the stills of Fig. 18-1. The,ideal still will be
'one in which the rate of heat absorption is the maximum (at all points)
that can be tranSferred to the oil without causing coking, discoloration, or
decomposition. If two coils are to be hea.ted and properly controlled in a1 Tate, C. C., A New Development in Radiant Heating, Oil GQ8 J.J Ma.y 10, 1951.
p. 106.
111 Reed, R. D., Radiant Heat Transfer versus Wa.ll-to-tube Spacing, Western Pet.
Ref. Assoc., Chicago ,Meeting, June 18, 1953.
~ Schutt and Zdonik, Deaigning _a. Tubula.r PYl'olyrsis Furnace, Oil Oaa J., ' May 1~
1956, p. 149.
'
TUBESTILL HEATERS
589 .
5ingle still, some partition arrangement as in Fig. IS-la, b, .d; 8,.or j must
provided. I t desirable to fire with gas because fuel-oil flames radiate
'intensely and thus tend to "bum out" or cause local overheating of
certain tubes. Part of the advantage of gas lies in the fact that gas
burners are relatively cheap and thus several gas burnerS can be afforded.
be
is
FIG. 18-2. A-fra.me furnace under constniction. Open header boxes show radiant
return bends and welded convection bend$.
590
oil to coke or decompose at the wall of the heated tube. This limits the
rate of radiant-heat absorption to 6000 to 20,000 Btu per sq it of outside
atea, depending on -the operation, because if coke is formed the tube-wall
temperature rises and the tube softens and fails. An equipment that
somewhat overcomes this difficulty is the pebble heater. 3,4 It consists
essentially of two vertical cylindrical chambers .mounted one above the
other. Ceramic-ware pebbles are heated in the upper chamber by direct
contact with burning fuel, and the fiue gases pass upward in oountercurren.t flow to the incoming pebbles. The .hot pebbles flow downward
to the lower chamber where they are used to heat air Qr steam, crack ,
ethane or possibly oil or hydrocar~on gases. The cooled or spent pebbles,
- along with any accumulation of carbon, are lifted by an elevator or airlift
to the heating chamber. An advantage of such a heater is the fact that
coke, etc., . is deposited on the moving stream -of pebbles rather than
, attaching itself to a direct-fired ,heating surface.
The efficiency of a process can be increased in two main ways. The loss
through the walls and in the stack gas from tbe furnace can be decreased.
or heat can be saved from the products of the process. The use of aircooled walls, aside from the preservation of brickwork, has often been
referred to as an economy but since hot air ' raises the flame and stack
temperature, it is necessary also to add convection surface, or no economy
is effected.' .
The heat that is absorbed by he~t exchangers is often credited as a
direct saving in heat. Such is not always the ,case because the efficiency
of the still decreases as the temperature of the charge stock i~ increased by
exchangers. As an example, consider a pipestill distillation unit that
operates with no evt>l}angers and at a stack gas temperatme of 350F.
The stack 108S is only about 8.4 per cent (Fig. 14-2). If the charge stock
is then heated by exchangers to 300F, the stack temperature win be about
550F and the stack loss 14 per cent. In such a case the saving'of heat by
raising the temperature of the charge stock from 100 to 300 Illust more
than compensate for the decrease in the efficiency of the still. A study
of the economics of the complete unit, including both the pipestill and the
exchangers, is the only way to determine the amount of heat that is actually saved.
RADIATION
591'
TUBESTrLL HEATERS
Q == bAT'
. where A = area of radiating surface, sq It
T = absolute temperatW'e of the surface, of
Q = Btu transferred per hr
b = 1.72 X 10-9 ~tu/(OF diff.)(sq ft)(hr) at black-body conditions
But a surface cannot radiate all this heat to another surface because the
cooler surface also radiates beat. For a small body completely surrounded .by a hotter body the foregoing statement simplifies to
Q
Q2 -
Ql
= bA (T: - Tt)
(18-1)
This expression involves the assumption that all the energy emitted by
the hot body is absorbed by the cooler body and that all the energy
emitted from the cooler body is absorbed by the hotter body. In practice
most materials fail to absorb all the radiant energy that falls upon them,
and hence the constant b is different for all material~. (Table 18-1).
TABLE
18-1.
Material
RADIATION CONSTANTS
b X 10-11
1. 72
0.374
1.57
0.65
0.278
1.34
0.63
0.745
1.56
1.51
1.55
O. 466
,;
592
"
PETROLY.~UM
Hl';F1NERY ENGINEEHING
--
-~." .
TUBESTILL HEATERS
593
and the conditions within the flame are so difficult to evaluate that empirical relationships have been adopted. The' most important factors that
affect radiation from Barnes are (1) percentage of total heat that is
absorbed as radia.nt heat, (2) ratio of air to fuel, (3) arrangement and
spacing of absorbing surface, and (4) kind of fuel.
Regarding the :first of "these, consider a flame burning wi thin a furnac'e
whose wa.lls consist entirely of absorbing surface. Rays of radiation proceea in all directions from the fiame; and with the exception of the small
amount of heat that is used in heating the intervening gas, all the heat
from the flame is absorbed ,:>y the cool surface. In this case, a large percentage of the heat is transferred by radiation, although the rate of heat
absorption per square foot of surface is low. If all the absorbing surface,
except a single tube, is removed from such a furnace, the radiation strikes
the refractory walls and is reflected or reradiated about the .furnace interior so that the single tube receives a relatively larger amount of radiation
per unit of surface. Although the single tube absorbs heat at a high rate,
it ab~orj;)s a relatively small percentage of the total heat liberation.
The ratio of air to f~el is important mainly b~cause it affects the flame
temperature. The larger the quantity of air (or products of combustion)
that must b~ heated in the flame the lower will be the resultant flame'
temperature and the lower the rate of radiation. Thus large quantities of
excess air reduce the radiant absorption. For the same reason the recirculation of flue gas reduces the flame temperature, but air preheat increases
'it. The arrangement of the cooling surfaces also affects the rate of radiant
absorption. The closer the surface is to the flam.e the greater the amount
of radiation that falls upon it. Thus corners and ends of furnaces receive
less radiation than other surfaces (pages 609 and 611).
These factors have been related by Wilson, Lobo, and Hqttel:,7
R =
1
1 + G vQ/aAcp
(18-2)
4,200
where R
= fraction
594
0.5 1---+--+--+---;----""......,
~ 0.4 i---+--+----:I-
0.3 1-----4--
0.2
23456
Ratio Center-to-Center OiSttotnc.e
Tube DiDlme+'er
FlO. 18-3. Distribution of radiation to tubes suspended in front of a. wall.
Mech~ Eng.)
(Hottel,
The area described by Aep or aAcp is not convenient because the designer
or operator is primarily interested in the area of the tubes that transfer
the radiant heat. The wall area (Aep) in terms of length (L, it), center-tocenter spacing (e, in.), and number .of tubes per row (N) is
Acp
C
L X N X 12
(18-3)
and the projected area of the tubes (A) in terms of tube diameter (D in.)
and number of rows (n) is
D
A=LXnXNX12
or
or
A = nAil" C
Acp
n X D
595
TUBESTlLL HEATERS
In terms of q, defined as the rate of heat absorption per square foot of projected tube area,
RQ = Aq
Q = Aq = nAcp(DIC)q
and
When these terms are introduced into Eq. (18-2), the following forms
obtained:
1
. ,-.
G
,
"\jR
~XD
a
4200
,
D X
and
1+
I.!
(
qc
a.re
(18-4)
(18-5)
-,
'
The special q' of Fig. 18-4 can be corrected to the general q which applies
to any number of rows of tubes and any tube spacing, as follows:
~ X~) q = feR)
or
1.014q'
(g X ;) q'
q = 1.014
(18-6)
Common center-to-center spacings9 for tubes and the approximate equivalent lengths of bends (for friction-loss calculations) are indicated in
Table 18-2.
TAStE 18-2.
Box type
Streamline
Approx. equivalent
length of bends, ft
Lightest
Heaviest
Lightest
Heaviest
Box type
Streamlin~
4.87
6.37
7.75
4.50
5.75
13.3
20.0
26.7
10.0
9.25
8.25
5.87
6.75
8.25
9.75
. ....
3.75
5.00
4
5
6.00
7.12
8.25
10.50
6.75
t
.....
6.7
33.3
13.3
16.7
40.0
20.0
Nelson, W. L.) Retum Bends, Oil Gas J., Sept. 7, 1946, p. 107.
596
6QOOO
5'0,000 \
tJ
41
1\
\
~
<
"'tS
cu
]4qOOO
'\
L-
0-
'S
~\ ,
1) '3qooo
~
t!
a
(]"
\\
.'\,
\ \\
1\
'"~\ ~\\ \
\'
\\
."
~
I'...
'\ \. \
'" ~. ~
~
'"
L-
---a-
.=- - -
"
'"~ ~ ~
..... .......
1"-_.......
pj
.1
"
C
...Q
"
'"U
\ ~
\, \
Q..
'j'
.po:
\\
Q)
\\
2qoOO
llqooo
\\.
cenf excess
~\ '0'0'" i\Pe:
,"r
X 60% Xi.
\901'\
.~
'.
\\
\\ \ \
L..
"~.
a"
20
30
40
50
60
70
Percentage of Net Heat Developed That is Absorbed in
.
the Rodj~nt Secnot'"!
FIG. 18-4. Rate of radia.nt absorption (Btu. per square foot of proJected area.) for 8
. center-to~enter tube spacing that is double the tube diameter, and for two rows of
(l~)
J..
~tes
Hottel, H. 'C., Radi8.nt Heat TrMsmission, Mech. Eng. 651, 699 (1930).
597
TUBESTILL HEATERS
cent excess air) and heavy fuel, are shown for 0 to 90 per cent excess air.
Other fuels can be represented by lines between,. these two extremes by
referring to Table 18-3. This chart may be used 'd irectly in the design of
simple furnaces, but it should not be used for furnaces ~sing air preheat or
flue-gas recirculation. ' Note also that it is based on a center-to-center
tube spacing that is twice the tube diam,e ter [Eq. (18-5) Jand on the use of
two rows of tubes. ' It ma.y be applied to other situations- by means of
Eq. (18-6). With proper burners and don experienced fireman, it is possible to fire with less than 25 per cent excess ail=-, but the average amounts
TABLE
18-3.
Heating value
Fuel
Gross
1.
2.
3.
4.
6.
6.
7.
8.
9.
641
1,009
1,160
2,058
1,360
19,358
18~274
17,970
13,533
Lb Hue
Net
gas per
Ib hiel
569
909
1,051
1;893
1,239
18,168
17 ,324
17,075
13,098
26.6
23.6
23.2
22.0
21'.0
'19.7
18 .8
18.4
13.6
Btu
absorbed
per sq It
(proj.)
13,200
17,100
17,700
19,700
21,600
24,800
27 ,400 '
28,600
54,700"
used are about 35 per cent for gaseous fuels and 50 per cent for oil fuels
(Table 14-6).
, If a low rate of absorption is not necessary but gas is available and must
be burned, a ,mixture of oil and gas m~y be fired tog'ether. The luminosity
or radiating power of such Barnes appears to be almost as good as for pure
oil flames. Hence for such mix,ed flames the curves' in Fig. 18-4 for oil
flames may be used. The radiating power of these mixed flames may be
explained by ,considering the carbon particles in an oil flame as radiators.
These partieles 'also exist in the mixed flame.
Lobo and Evans 8 have made a complete study of petroleum heaters
and the Wilson, Lobo, and Hottel radiation equation [Eq. (18-2)]. They
also present a theoretical equation that appear~ to check well with all
types and arrangements of heaters. With regard to Eq. (18-2), they c,onelude that it may be used for designing the older conventional box-type
heaters (Fig. IS-la, b, c) or other very large stills but subject to the following qualifications:
598
Ib
T
eli
of
m
ti
8.1
a
3
elevator
(
(
(
(
, ....: ~
-:
599
TUBE8TILL HEATERS
EXample 18-1. Rate of Absorption in the Radiant Section. Apipeatill uses 7,110
Ib per hr of a. cracked gaB '(net heating value 20,560 Btu per Ib or 190Q Btu per eu ft}.
The ra.diant se.ction contains 1,500 sq It of projected area., and the tubes (5 in. outside
dia.meter) are sPaced at a center-to-center distance of 10 in. There is only one row
of radiaIi.t tubes, and they are 40 ft long. The ratio of air to fuel is 21.0 (30 per ceni
excess air). What peroentage of the heat liberation is absorbed in the radiant section and how many Btu are absorbed per hour through each square foot of projected
area?
.
Q = 7,110 X 20,560 """ 146,000,000 (heat liberation)
a co 0.88 (Fig. 18-3)
.
1500
N. ~ number of tubes = 40 ~2 = 90
..4..", = 40 X 90 X
aAIl1'
It
= 0.88
(1s-3)]
1
.=
21 0 ~!46 X loa
2,640
4,.200
+'
1
+ 1.18
:II
Q~58
.
Btu a.bsorbed per sq ft projected area. = g
= 66900000
'1,500
= 44,500
Btu per hr
The results ma.y be checked by means of Fig. 18-4. It applies to two rows of tubes
and a. spacing of tubes tha.t is twice the dia.meter of the tubes. At an R va.lue of 0.458,
30 per .cent excess air, and 8JJ. average gas fuel (G """ 21.5),
q
= 1.014
X 24,000 X
10
"5
0.88
1.0
= 42,800
Note, however, that the gas of Fig. 18-4 has a. G of 21.5, whereas the fuel used herein
bas a G of 21. Thus,
line for the particular ;gas .fired in this el:ample should lie
about one-eighth of the distance between the gas and the fuel-oil lines, or at about
the
42,800
+ 1,500 -
44,300
Lobo-Evans Method. The theoretical fumace-design method. developed by Lobo and Evans S involves so many relationships that a. theoretical
development cannot be attempted here, but it can be presented by means
of a series of charls (Figs. 18-3 and 18-6 to 18-11). It can be applied
only to already designed or completed furnaces.to see how they behave.
It involves a determination of the following factors or rela.tionships:
. 1
600
18-4.
VAlUOUS GAS
SRAPES
Di~
rati08 (length,
width, height in any order)
or diameter (d), it
Rectangula.r fur~es:
1-1-1 to 1-1-3 and 1-2-1.to 1-24 ~ '\!Ifurnaee volume
1.0 times sma.llest dime~on
1-1-:4.00 I-J::~.
1-2-5 to 1-2-8' -" ,~ . , &...--~.,.'-:' """'"l.:i tmle;Bmanest dim~naion"
1-3-3 to 1-110- ao
1.8 times smallest dimension
Cylindrical furnaces:
dXd
d X 2d, to d X ao d
7i times diameter
1.0 times ~meter
7. Rate of Heat Absorption Factor C!~4>)- In this term, Qis the total
heat liberation per hour and R is the fraction of this heat that is absorbed
by the radiant surface. Thus RQ is the Btu absorbed per hour in the
radiant section. The term can be evaluated directly by adopting the
desired value of RQ or a. suitable value of the rate of radiant absorption
such as the q value of Eq. (18-5) or Table 18-5.
8. Check oj Gas Temperature (t g). At this stage the assumed gas
temperature (lg) of item 4 above can be checked by Fig. 18-6 using.
(RQ/aAcp<p) on the right scale. If t{1 is in error by more than 100F,
the values of P F and tj) ,(items 4 and 6 above) must be revised.
Perry, J. H. (ed.), "Chemical Engineers' Handbook," 2d ed., p. 1015, MoGra.w
HilI Book Company, Ino., New York, 1941.
11
- i:! .....
~QQ ~
g-[r~
~.
t='
....
130
30
120
20 I++=
tr 110
10 ~
t.:
a-
'tt:
~
L,;
~ 100
00
";j
<:
' ::J
of.!
cd
+=
..,m
90
90'2 '
80
80 CI
70
70
60
60 ~
52
co t
eJl'
0-
Q!
cj 0
c
0
+a
L.
co
L..
so
50 ]
40
40
.~ 3D
IU
30
'"
20
20
10
10
GI
..Q
..
..t-
o
X
....t
<
....a
0' ,
060
, ~!..t"":
400
800
1,200
..
\600
'2,000
Temperatur8, 0 F.
FIG. 1s.:6. Theoretical radiant equation (high range).
'0
.~
2,~O
2,800
3.200
3.600
....
::r:
'+-- '
0
....ocu
Q!
602
9. Pseudo Fla'lne ,Temperature (t~). This temperature can be computed from Fig. 18-7 or 18-8 by usfug the per cent excess air. Note that
if the air is preheated COF a.bove 60F) a further correction is necessary on , '
Fig. 18-7 or 18-8.
I
ISO
~~
140
130
120
110
.<L.
100
II)
90
U)
......
70
---
50
o~\(
()~9
40 "-30
o~
~~I ~
-.
60
; .
1',
\:.'~go"
Q~
~~
V~
v/ /
"/
V/ V/ /
1L~~~-- --
~~
!~ ~
~oo
--r-----
--=
~~ ~
~---"'"
I~ ~
Ii
J No Qir preheaf
1.000
/ /V/ ./
f~//V" I
I
/ /
~~ L /
~-.
/"/
20 r--'\.CS ~/
o1,6OQ .
VL V/ /
V/V/
.;i: / V~~V
"-bt\l~//
I ~o
10
L V/
-~
-c:g.
C!
8I..
If
~~r
~.. ~~~
~80
I~\"\
"
v:
V/
/
~~
~
~
r
~OOO
,
3500
(~1!~).
~~~
"\000.
ua.ted. from Fig. 18-6 by connecting the t~ with the tube skin temperature'
(t~) and reading the rate of heat liberation on the left scale. .Since all '
factors are already known, t he value of Q can be computed.
Example 18-2. ~te of Absorption by Lobo-Evans. What is the total heat input
required and the radiant a.bsorption for the following still a.o.d operating ~C?nditions?
603
TUBESTlLL HEATERS
150'
4,500
J40
130
120
4,000
flO
100
3,500
<90
I/)
CII
~ 80
)(
ti=
UJ
1:III 10
~OOO
tf 60
50
2,500
40
20
-~:"""-*---I--t-+--+---+--+-~~~-+--+-___f---+-~~OOD
fO
o~~~--~~~~~~--~~~~~~~~~~oo
I~OO
2,500'
3,000
3,500
4.000
4,400
Pseudo- Flame Temperature t'F of.
FIG. IS-B. Pseudo flame temperatures for oil fields. (Lobo and Evans, Trans. A.I. Ch.E.)
2POO
. StiU data:
Dimensions of "ombustion chamber .......................
Tube. outside diaril.eter. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
Center-to-center spacing ................................
Number of tubes (arranged in a. Bingle row). . . . . . . . . . . . . ..
Tube area, outside .....................................
Total wall area., AT (the opening jnto the convection section
is 200 SQ it). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
Operating
15 it X 30 ft X 40 ft
5 in.
10 in.
90
4,710 sq ft
4,300 sq ft
conditi0n8:
604
Aep = LNC _ 40 X 90 X
aAr:p
::=I
~~
.=
L (Table 18-4) ==
1.915
X a9i's X 4918
31 "'' 15 X 30 X
:::II
1-2-2.67
40 "'" 17.5 ft
----i---+--i---+--+--I----I--+-.........jO.6
o.
0
FIG. 18-9. Flame emissivity.
(Lobo
Flam43. emi88iuity:
so
0.30
Itt
cu L-
QI
0.28
0.
10
40
00.26
-<
00.24c-I '
:r:
+
",,0.22-
30.
8
~
.........
L.
wt
'~" 0.18
"
2.0
~
~
QI6
cE
0.14
10
O/II'"~el
rq,d_I ..1_
~
0.12
0-10
:1
~Q20
-.-t
-.r
4-0
F.,../
180
160
60
WO
140
120
Per Cen't Exce&s Air in Flue Gas
FIG. 18-10. Combustion data on oracked-gas and oil fuels. (Lobo and Evcm87 Trans. A.I.Ch.E.)
20
200
:i
606
aA.,,,
According to Fig. 18-11, for
8.
2,640
Pp of 0.495,
is 0.56.
7~~~--~~~~~~--~~/~I/~~{~f~r~'~~
6 ~--+---+---+-----+--+--+--+--+-f---f+-/I---1+7--+--1/---+-4+H-H
r-t---+--+---+--+----+--+---+-I/~f_+/l__4J
Il/L_..I_4
j
J V
v~V:~~~~~v
_I___I_I_I_H
1/
~~~-A__~~~~~~~~~~~~__~__~~__-L__~~
"'"
0.3
0.4
0.5
0.6
0.7
0.8
Exchange Foetor - til
FIG. 18-11. Over-all excha.nge factor. (Lobo and Evans, Trans. A.l.Ch.E.)
0.9
70.65 X lOs
aA"1"t/> = 2,640 X 0.li6 - 47,900 Btu per hr-aA.,,.,,,
Chuk gas temperature (t,). Using 47,900 on the right scale of Fig. 18-6, the flue ga.s
temperature is found to be 1850"F rather tha.n 1800F assumed. This is satisfactory.
PBeudo fla/7M temp81'ature (t~). Moving from 30 per cent excess o.ir on the left of
Fig. 18-7 to 1850F and then upward to an air prehes.t of 400F (460 - 60), the
pseudo flame temperature is 36000]!.
607
TUBEBTILL REATERS
temp~&ture of
0.9,SQ = 97000
aAer:'~
Note that the less exact method of Eq. "(lS-2) and Example 18-1, which a.ppIres to the
same still (except with no air preheat) gives the '[ollowing results: R = 0.458 and
q - 44,500. Had the a.ir preheat been a.ceounted for, the agreement would have
been even better.
Commercial Radiant Rates. Although the starting point in any pipestill desigll is the radiant rate that can be attained with various feed
materials or in various processes, the literature is almost silent on this
important matter. A few rates are given by J. H. Rickerman,12 by
H. C. Schutt,2 and the author has recorded lS many rates, bu.t it is necessary ~o infer rates from the rest of the. literature. H.16.18,17.18,19,20,U,22
This easily understood because precise rates cannot be given beca.use
of the many fa.ctors tha.t appear in commercial operation. Among these
are the wide variety of stocks, the variation in the liquid velocity, and
the different temperatures that are used for the different stocks. However, Table 18-5 presents rates that have been used in comniercial plants.
Doubtless many stills deviate from the recommendations "in the table,
and the rates C&nllot be maintained if local overheating occurs. The
firing of 'powdered coke l2 does not seem to alter materially the radiant
absorption rate.
.
Velocity is important' primarily because of the pressure drop created by
it. In fact, a high cold (60F) velocity in most instances causes a low
.velocity in the vaporization zone because it tends to suppress vaporization
at the outlet of the. still.
is
Heater Designs for the Petroleum Industry, Tram. ABME, 67, 531 (1945).
Nelson, W. L., Allowable Radiation Rates (First Edition of this book and Oil Gas
J'J Sept. 21, 1946, p. 305..
14 McCullo~h, C. E., 011. Gas J., May 10, 1934, p. 92.
U Leach, T. B., WPRA Meeting, Shreveport,. La., Nov. 6, 1936.
11 Jamison, J. A., Proc. API, 19 (III), 1938.
17 Rickerman et al., Oil Gag J., May 5, 1938, p. 50.
U Ca.mpbell, O. F., Pet. RefimT, January, 1950, p. 109.
18 Bom and Rose, Oil Gas J., Mar.'9, 1953, p. 101.
. to Naugle, J. M., Pet. PToce8lJing, December, 1949, p. 1346.
11 Morrow, R., Oil Gtl8 J., Jan.. 21, 1957, p. 88..
H Foster Wheeler Corp., Direct Fired Oil Heatet'8, Heat EngineeringJ NovemberDecember, 1956, p. 212.
11
11
, 1!
608
18
servlces
................. .
Heating to 750'T (cracking
still with convection
On projected
area
On outside
area
63,000
47,000
20,000
. 15,000
34,600
11,000
vaporlZa
. .........
..
28,000
Heating to 950~ (catalytic
8.000-16,000
Velocity based ,
011 volume a.t
60F, ft per see
7-10
10,000-15,000
5-8
2-5
9,000
3-4
1-2
0.&-4
7
2-6
5-8
4.7-7.6
5.6-7.0
3-4
.~1
TUBESTILL BEATERS
609
610
(~.-:--~-:'--~.~2c:I~C~.O~jl='=..~.-~.-.~"-;;~~lk~--~".~.--~..~"..~.-.5-.~~~1iS:::;;;:;J]
.L
e ..
)( eo
0)(
..
- - - - -_ _
f-o::;;;;;;;::::,:_. --~
Initial radiation _
Refer to Example
1~.
The 35 lines or rays were completed as for the 9 shown in Fig. 1&-:12. Upon the first
coil fall 9 rays of initial mdiationj 8 rays of onee-reflected radiation; 3 rays of twicereHected radiation; and 3 of thrice-reIl~cted radiation. The total radiation (comparative units only) that is absorbed by the first coil is
80
1~9 _ 0.1695 .
'rhe average relAtive ra.te per square foot for all of the radiant surface was 0.126 (see
. accompanying ta.ble), and the actual average absorption rate was 11,000 Btu per sq It
of projeeted area per hr. Hence the rate in the first coil is
.
611
TUBESTILL HEATERS
First
coil
Initial radiation (No. rays X 0.75) ................ 6
Once reflected (No. rays X 0.68) .................. 5.44
Twice reflected (No. rays X 0.61) ................. 1.83
Thrice reflected (No. rays X 0.54) ................ 1.62
Total heat units for each coil. .................. 14.89
Surface in each coil (sq It) ....................... 88.0
Relative absorption rate, heat units per sq ft ....... 0.1695
, Second
coil
Superheater'
2.25
1.36
0.61
0
4.22
71.0
0.0595
1.5
0,68
0.61
1.08
3.87
23.0
0.168
++
.
b'
14.89
4.22
3.78
0 126
R eIatIve
avg a 59rption rate =
88 + 71
23
=.
Actual avg a.bsorption rate = 11,000 Btu per sq ft
Actual rates:
Firat coil ............. . 11 000 X 0.1695 """ 14 BOO
, ,
0.126
'
Second coil ..... '..... . 11000 X 0.0595 , = 5100
,
0.126
'
0.168
Superheater ......... . 11,000 X 0.126 = 14,750
:' 1
'; I,
1 ,
The acCUrACY of the method can be improved by repeating the foregoing' computatioJUi
for several planes ~nd for several point SOUl'ces of radiation.
L
q
I
<
f1
'j '
,I "
'i
:' i
CONVECTION
.1
I '
612
where hG = pure convection film-transfer rate for flue gas flowing at right
angles to staggered tubes (no radiation)
G -:- mass velocity of gas at minimum cross section, lb per sec per
~ft
j'
"
where h,.b
= radiation
(h,
+ h,,)
(18-8)
613
TUBESTILL HEATERS
TABLE
Velocity,
ft pel' sec
4
4
4
8
8
8
12
12
12
18-6. ApPROXIMATE
CoNVECTION COEFFICIENTS
Temperature,
of
800
1100
1400
4 .7
4.4
4.1
3.9
5.3
6.0
5 .0
4.7
5.7
5.3
4.6
5 .Z
3.8
4.6
800
1100
5.8
5.4
1400
6.3
6.8
7.3
6.3
7.0
6.5
800
1100
1400
7.9
8.3
8.7
7.3
7 .7,
8.2
6.0
6.7
7.2
7 .7
5.2
5.1
5.8
6.3
4.9
5.6
6 .3
6.9
6.0
6.6
7.1
7.5
6.1
air preheaters are available, but the rates are low because two gas films
are present and' because little radiation occurs.
Pipestill Losses. The heat losses in pipestills, when based on the net
heating value, consist mainly of two items: (1) the sensible heat content
of the stack gases above 60F and (2) the losses through the furnace walls,
header boxes, roof, floor, etc. Pipestills are usually fired with 25 per cent
or more excess air, and hence carbon monoxide is seldom reported in the
flue gas, and no loss occurs by incomplete combustion of the fuel. No loss
due to the heat contained in the cinder or combustible in the cinder is
necessary unless coal is fired.
The brickwork of pipestills and boilers is not usually airtight: The following tabulation shows the flue-gas analysis at two points in a commercial still. Air leaked into the still in the radiant and convection sections
Flue gas
Radiant section
Breeching
13.5
0.7
0.3
7.6
9.4
0.0
'.
,;
614
Actual heat losses (5.3 per cep.t) through the walls of one still are
reported in the Second Edition of this book. For modern brickwork
constructions that are in good condition, the loss from the radiant section
is only 2 .to 3 per cent and from the convection section about 1 per cent.
With some panel or steel-encased designs, the total loss may not exceed
1.to 2 per cent.
PIPESTILL DESIGN
an4 ea.ch of the stocks (that are vaporized) will be vaporized at 695F.
This requires
Thus, the total heat
the total latent heat shown in the last column of Table 18-7.
duty or heat absorbed is 15,454,000 Btu per hr.
In actuality, vaporization te.kes place throughout a ra.nge of temperature near the
outlet of the still, but according to the lo.w of conservation of energy, the heat duty as
computed a.bove is almost exacUy the same as that computed by following the actual
mechanism of heating and vaporization that occurs in the still.21
. Heat .Balance. Dry cracked gas (No. 12 of 'rable 14-4) which bas a net heating
value of 1475 Btu per cu ft will be used, and 30 per cent of excess air can be used. .
II ~elson. W. L., Pipe--etill Duty, Oil Gtu J., Aug. 17. 1946, p. 117.
615
TUBESTlLL HEATERS
TABLE
Ma.terial
Per
cent
18-7.
1M
Gal
Lb
per API per
hr
gal
Mol
wt
Lb
- - - - -Loss ..............
1
87-octane ga.so ..... 12
3rd gra.de gaso .....
16
Kerosene . .........
6
Diesel fuel. . . . . . . . 16
Gas oil . ........... "12
Topped crude ..... 37
Crude oil .......... 100
TotaJs .... "......
4
. ....
....
245
35
7.0
56.0
58.0
17.0
36."0
19.0
0
0
42
68
73
"72
0
304,000
142,000
571,OQO
437,000
193.0
According to Fig. 23:-6, a stack temperature of 6007 will be economical. This "correspOnds to a stack loss of about 15 to 16 per cent (Fig. 14-3). Wall losses for a. straightup-type still (Fig. IS-Id) will be only about 4 per cent (2 per cent in the radiant and
2 per cent in the convection section). In the topping of crude oil, a. rad.ia.nt-absorption ra.te or q Of 351 000 Btu per sq ft of projected area. (Table 1~5) is we, and a
velocity of 3 It per sec will not give a. prohibitive pressure drop. According to Fig.
18-4, the percentage of the heat liberation tha.t is absorbed in the radiant section is"
about 39.4, but since the gas fuel used here is different from the one of Fig. 18-4, an
R of 41 will be used. Note that this applies only to radiant sections in which two
rows of tubes are used, and for center-to-center spacings that are twice the tube diameter. The heat balance is
Heat absorbed:
15,454,000 Btu p~ hr
Heat developed (eft'. = 100 - 15 - 4 == 81): 19,100;000 Btu per hr
. 1
Per cent
Btu per hr
41
2
40
2
15
" 7,840.000
380,000
7,640,000
380,000
2,860,000
7,84.0,000
224
f
. t..:....l
35 000 - " sq t proJec 'I:ru area.
1
Tubes:
"12
224
4.75 X 19
~" 30
As the gases enter the convection section they contain 100 - 41 - 2 per cent of the
616
+ 48,9007,640,000
X 0.64. X 1.02
5400F
'""
In 1,310/300
The average fiue-gas velocity in such a still is only about 4 It per aec, and the average
gas temperature is about 1225"F. Accordingly, the convection coefficient is about
4.8 (Table 18-6), and the sunace required is
Surface:
7,640,000
2325
It
'd
684 X 4.8 =,
sq outsi e area.
Tubes:
12
2,325
4.75 X 3.14 X 1"9"" = 99(98.5)
COllBidering the distribution of tubes between the radiant and convection sections, it
would probably cost little more if more tubes were put in the radiant section, and thlB
would be highly advisable because it would reduce the radiant-absorption rate to
such low values that no danger of overheating would exist. In addition, the radiant
section is 80 small that only one row of radiant tubes (rather than two) would allow a
better arrangement of surface.
(10
= 19.1 psia
According to Fig. 5-,27, the temperature required to vaporize 63 per cent at 19.1 psis. is
663F. This was obtained by rai&ing 645F to 19.1 psia. (Fig. 5-27).
617
TUBESTILL HEATERS
Vaporization by Flashing. However, the pressure a.t the end of the tra.nsfer line,
but before coming in contact with the steam, is 24.7 psia (10 psig), and vaporization,
therefore, occurs as the material spews into the tower. The amount of vaporization
caD. be computed by a trial-and-error solution.
Ii 3 per cent vaporization occurs the temperature drop will be a.bout
0.03 X 7,000 X 7.18 X 78
48,900 X 0.71
340F
.
In- this multiplication the 7,000 is the gallons per hour of stock, 7.18 is the pounds per
gallon of the 3 per cent of ma.terial being vaporized (33 API), the 78 is its latent heat
at about 664F, and the 0.71 is an a.verage specific heat of the stream of vapor and
liquid.
This means tha.t the temperature of the materia.lleaving the trans.fer line is about
(663 plus 3.4) or 666.4 of. If our assumption of 3 per cent vaporization is correct, the
atmospberic flash temperature of 622F at (63 - 3) or 60 per cent vaporized when
raised to 24.7 psia will be 666..4F. Our assumption is substantially correct beca.use
622 raised to 24.7 psm (by Fig. ~27) is about 666F. A larger Beale figure than
Fig. 5-27 is necessary if it is to be read with sufficient accuracy for such probleh1B as .
this.
VaporizalWn in Transfer Line. A direct WAy of solving for this vaporization is to
adopt a percentage vaporized, determine the drop in temperature that must occur to
supply the latent heat for such a. va.porization, compute that pressure which must exist
at the inlet of such a. vaporization zone, and compute the length o( the zone from the
pressure drop as follows:
Consider a zone in which 10 per cent vaporization occurs. Thus, 50 per cent is in
the vapor state at the inlet to the zone and 60 per cent at the outlet (or entra.n.ce to
tower). Such a material ha.s 8. gravity of about 34 API (Fig. 4-4) and a latent heat
a.t about 671F of 77.
48,900 X 0.72AT
= 10.9 F
D
For most mixed-phase systems the value of f is about 0.005, and if the inside diameter
of the transfer line is 3.5 in.
AP = 0.323 X O.006su 2L = miL
3.5
2,170
In this instance the volume of the liquid will be neglected, but at small percentages
vaporized, it becomes an importsnt part of the total volume. The average percentage vaporized (based on crude) is 55, the moles of vapor about 180 (see Ta.ble 18-7 or
Fig. 4-4), and the average temperature and pressure 42 (41.8) psia. and 672F (671.8).
Volume ....... 180 X 379 X
48,900
15~2
1127
3,ioo
a.nd
ui
= 47,300
618
PETROLEUM REFINERY
ENGINEERI~G
In addition, the pr~re drop caused by the change in kinetic energy content of the
stream of Buid [Eq. (13-5)] must be computed. The change in momentum from the
entrance to the- 'zone, where the velocity is 218 ft per ~, to the tower vaporizer where
the velocity is substantiaJIy zero is
IlP = 0.00673au J
= 0.00673 X 0.0151 X 47,300
= 4.8 psi
Thus, the pressure drop that is available for
frictio~ 1088
is
Tabulations of transfer-line temperature drop, pressure drop, and percentage vaporized have been published 211 for the sp~cial case of pipestills
discharging at substantially atmospheric pressure.
Pressure Drop in Pipestills. The application of flash-vaporization
data to the problem of computing the vaporization ' that occUrs within
pipestill tubes is complicated by the constantly changing pressure
throughout the entire length of pipestill tubing. However, vaporization
occurs mainly throughout the fuml tubes of the still, because as soon as
vaporization starts, the frictioll .lossand the pressure become so high that
vaporization tends to be suppressed. In fact a large part of the pressure
drop through a pipestill often occurs in the transfer line from the still to
the.fractionating tower. To shorten this line does little good because the
vaporization is simply pushed back into the still. Likewise a larger transfer line deereases the pressure at the outlet of the still so that more vaporization occurs in the tubes.
PressUre drops through stills can be computed in much the same manner as for transfer lines (Example 18-5) except that length affects not only
the pressure drop but also the temperature (and indirectly vaporization)
of the stock because heat flows through the walls of the tubes. Thus a
trial-and-error computation is required for each zone of vaporization.
The operations involve
1. .Adoption oi a. zone in which the a.mount of vaporiza.tion is fixed.
2. Aatrumption of a. l~gth for the zone and computa.t.ion of the amount of heat that
enters the oil in this zone.
a.. ,Computation similar to that illustrated in Example 18-5 to determine the length of
the zone.
H
Nelson, W. L., Oil GCUl J., Jan. 25, p. 285; Feb. 22, p. 171; and Mar. 8, 1947, p. ~Ol.
....
619
TUBESTILL HEATERS
4. If the computed length differs (rom the assumed length, the entire opera.tion must
be repeated.
Rickerman l l suggestS a. modification of Eq. (13-1) for pipestill pressuredrop computations. It includes a correction for the kinetic eDergy of
motion.
dE'
= O.OO5185fG2vL [
1 - (Gtv/4,637P)
120
"'"~ ~
110
100
"
"-... "
~
.........
90
80
....a
70
..........
I/)
... 60
0..
"-
'-
SO
41)
L.
40
Vaporizolion_
~~7/
.........
"*
I~
" X_ -- ~7
)~
o
I
I.
I
Siorl of frons fer line .,..,.~
30
.........
"-
,I
End of convection
s~cfion
0..
to
;~
~-
)C
'~
(18-9)
Percenfoge voporizef/
in fower
I
~~
o ,
.... 'l
,..~"
20
o.
10
200
in which the symbols are the same as in Eq. (13-1), page 395, and v is
specific volume, cu ft per lb.
Figures 18-13 and 18-14 show the relationship among such variables as
eqUivalent length, perce~t.age vaporized at tower (or still outlet), pressure
drop, temperature, and percentage vaporized in one still design. There
are so many variables that not many such studies27 have been made. The
0
27
Nelson, W. L., Oil Ga8 J. t Aug. 31, 1946, p. 91; July 5, 1947, p. 93.; and Nov. 29,
1947, p. 89.
620
'}
..
600
Pipestm outlet
Voporizatiol"l starts
....
.560
oL
~".
e
QJ
480
460
/v
"
420
400
.! II
...
/K
,;'
'
IJ'
,,/ 4/
[j
/
,/
-;
17
/(
'P0nzer '
J
mperofure
and vopor- ../
izaflon '" ./
n / V' ... L/
~;
lransf"er line oLllle~--~
500
11\\0
i4S /
W
J.L:
~
~
,-
of lower
sso
~ 520
Percenh:1 ge - ...
voporized
"\\_
.,
60
l./
.,. ""
-; / 50
./
I.-
~/
,,'
,/
",/
I /
4I:
20H
cf
10
0
200 400 600 800 1000 1200 1400 1600 l800
Equivalent length, feet
4F/per cent
37 API
600F
2)000 bbl per day
4.2 ft per sec
2.0 in.
ft
15 ft
100 ft
400F
6 psig
25,000 Btu per
77 per cent
TUBESTILL HEATERS
TABLE
18-8.
Actual
Computed
198
124
192
115
197
209
85
605
103
394
663
362
.238
275
31
33
Ma.them~tical
622
often impossible to maintain a single phase, and in such situations, stratification can be a voided in Bome degree by the use of a high pressure. At
pressures approaching or above the critical pressure, the density of the
vapor tends to approach that of the hot low-density liquid. Thus, the
larger of the two phases tends to contain enough kinetic energy of motion to move the other phase along at nearly the same velocity as that of the
main stream. This is the primary reason for the use of 'a back pressure
in conventional thermal cracking or reforming processes.
Tube Design. The temperature difference that always. exists when
heat is delivered through a series of resistances is of great importance in
the selection of still tubes. Nearly all the radiation that falls upon
a tube must be absorbed, regardless of the transfer rate on the inside of
the tube. Thus the temperature in the film and tube is higher than in the
fluid.
AB coke is deposited in the oil film, the temperature in the tube rises, and
it continues to rise as coke is deposited until finally the tube attains the
temperature of the furnace or it bursts. For normal thicknesses of coke,
the amount of heat absorption is not decreased greatly. Partridge and
White 32 fuld that a normal thickness of boiler scale does not decrease the
rate of radiant-heat absOrption by more than about 3 per cent. In
general, coke deposits act in the same manner.
Pipestill tubes often receive radiation at the rate of about 5500 Btu
per sq ft per hr of outside surface or a rate of about 9500 Btu per
sq ft of inside surface, and the oil film-transfer rate may be 600 Btu
per sq ft per hr per deg of temperature di~eTence. Obviously the
temperature difference through the oil film, if the tube is clean, is only
9~O =
15.80 F
If the oil temperature is 9000 , the temperature at the inside of the wall
is (900 + 15.8) or 9I5.SoF. If the wall is % in. thick, the temperature
drop in the wall will be
'
= 9,~O
~.: ,= 15.SOF
and the (,)utside of the metal tube is at (900 + 15.8 + 15.8), or 931.6F
~ (Fig. 18-15),
H a ~-in. coke deposit having a conductivity of 0.5 is produced, the
tube temperature is incre~sed by
9,500 X 0.125
0.5
12
~d
= 198 F
(Fig~
18-15-}
+ 198 + 15.8 =
1129.6F
The Effect of Boiler Seale, Inti Eng. Chem., Jl, 839 (1929).
TUBESTILL HEATERS
623
A temperature of 1130F (red heat) is too high for a carbon steel tube
because the strength drops to about 1,000 psi (creep strength) and the
tube will fail. However, if the pressure is very low sothat the coke can be
deposited to thicknesses greater than % in., the tube wall temperature
continues to rise. with increase in coke thickness and eventually the tube
will att~n the temperature of the furnace.
The rate of coke deposition is not greatly dependent on the amount of
coke already deposited., but the rate can be retarded by increasing the
velocity and therefore the tra.nsfer rate through. the oil film. The rate of
950
931.6
900
--l15
~
: Moin body
~ of fluid
of
,1150
1129.6
1100
Q)
g
~
.-.
11/3.8
1050
~ 1000
:;:
'l) .
"
-...;:
915.8
-900
Moinbody
of fluid
624
II)
:t:
3.5 i------<>-L.OOOO R,de of Heat Ab50rption f-------/-----1
11).
15000
Throu'3h Inside Film
0
\
\
a.
QI
.3.0
.~
82.5
~
(.J
1:
;: 2.0
.....
"is
4b
~ I.S
~
Q)
>
~ 1.0
"'ii
0:::
O.S
200
250
300
350
Tronsfer- ROIte
t4
18.5
400
450
22 Approximorre Hot
Velocity
FIG. 18-16. Approximate relative ra.tes of coke forma.tion.
RP
= 1.28
625
TUBESTILL HEATERS
8 to 15 ft.as
17
Nelson, W. L., Modem PipestiU Heater Design, Recircula.tion, Pel. Engr., June"
1933, p. 23.
38
rn,
1946, p. 213.
CHAPTER
19
.1
..
OiUo~ine
+ CuHu:CH, +
+
recycu .weI"
C.Hu: OR,
+ galoZinlt(antiknou)'
1
.
gtU
(ItUOlin;
f}tJm-/onni1l.{J materialt
QCUJDl"'It
CuHu
+ tar
0,. T4e1Iclit
626
+ CaB:.
+
~ I1tU
OCUJ
627
Although these exa.ct reactions probably do not take place, they are representative of the over-all reaction that occurs during cracking.
Thus two general types of reactions take place: (1) primary reactions in
which decomposition of large ' molecules into small molecules takes place
and (2) secondary reactions by which active products polymerize to form
heavy tarry materials_ At the same time the products of polymerization
may be again decomposed into ' smaller molecules. The nature of the
primary reactions may be illustrated by the experimental work of Hurd
and Spence' on the decomposition of n-butane at 600C (1112F).
and
"At GOO'degrees the first of these appears to proceed to the extent of about
55 per cent and the -second to '40 per cent. Dehydrogenation reactions
into butene 'or butadiene appear to represent less than 5 per cent of the
total." The dehydrogenation reactions referred to are
and
and
+ CH 2: CR'CH: CH
+ CH 'CH "CH:CHa
2
+
+
Frolich and Fulton li conclude that the paraffin hydrocarbons are ' least
J, Am, Ch6m, Soc" 61, 3353 (1929),
The Theory of Cracking, ltScience of Petroleum," vol. III, p. 2104, Oxford Univer.
sity Press, New York, 1938,
4
628
stable and that others follow in the order olefins, diolefins, naphthenes ~six
carbon ring), naphthenes (five carbon ring), and aromatics.. This applies
to .cracking temperatures of 750 to 1100C F and to compounds of the ~aIIie
molecular weight. At higher temperatures the diolefins become more
stable than the naphthen'es, and hence the diolefins and their condensation products can be produced at high temperatures. 8
Properties of Cracked Materials. The properties of the products tha.t
are produced by cracking depend greatly upon the extent of crackingthat
is practiced. Sachanen and Tilicheyev 7 have studied the mecha~sm of
cracking by producing recycle stocks that had been cracked once, twice,
and several times. In each cracking test the oil was cracked at 450C.
The fraction boiling between 200 and 350C was separated by distillation
and subjected to another cracking operation at 450C. The extent of
cracking was not exactly the same for each recy~le oil, but the qualitative
comparison (Table 19-1) is useful. Note the 30.6 API 392F gasoline'
that was produced from the sixth recycle stock.
The most useful means of estimating the physical properties of cracked
l~aterials is the UOP Characterization Factor (pages 81 to 85, Fig. 5-9, and
Table 4-2). In most cases, Characterization Factors are somewhat as
follows:
Cracked gasoline (Mid Continent charge) ........
Cra.cked gasoline (general) .. , , , .. . . , ... ' .' .. , ... ,
Pipes till feed (charge and recycle)", .. ",." .. "
Recycle stocks (general), ..... ,.".,., ,'" ...... ,
,Recycle stocks (light) ... , . , , , .. , ...... , ... , , . '.
Recycle stocb (heavy), .... ,., ..... . .. , " ., ,. "
Cracked gas oil (paraffin charge). , .. , , ,. , . , . , . "
Cracked gas oil (naphthenic charge).', . , , . , .... "
Residuum (3-12 API) .. . , ..... , . , . , , ., , ..... ,.
Residuum (under 3 API) .... , , , .......... , , .. "
Distillates trom residuum (i2-20 API) ....... , .. ,
Distillates from residuum (2:-9 API) ...... , . . . . ..
11.7-12.0
11.5-12.0
10.5-U.5
10.0-11,0
10.5-11,0
10.0-10.5
11.6-11.9
11.0-11,3
10,5-11.0
9,5-10.5
10.~ 10,7
9,9-10.3
...
629
Sydnor and Patterson 8 have studied a Mid Continent gas oil and the
cycle oils produced from it in a manner similar to that used by Tilicheyev. 7
The chemical composition of cracked and other gasolines is indicated in
.Fig. 2-3. Although the residues of cracking are frequently considered as
being highly condensed a.romatic st!Uctures, they must also be highly
unsaturated 9 because they exhibit lower Characterization Factors than.
those of aromatics. However, nearly pure. aromatic residlle products
are produced 10 when cracking saturated gaseous hydrocarbons a.t very
TABLE
19-1.
GAS
OIL
No. 01
opera. tion
Time,
min at
450C
Below
200C
(392F)
API gravities
Approximate
Characteriza.tion
Factor
Cracking
Above . stock
Below
350C
and
392F
(6720]') recycle
oils
Above
672F
Recycle
oils
Gasolines
.,,
I
.l'
2
3
4
5
6
42
52
75
101
.101
160
28.7
21.3
16.3
12.1
3.9
8.0
10.5
8.6
7.9
10 .3
12.4
19.0
30.8"
28.2
23.8
19.2
15.4
14.5
58'. 2
52.5
46.0
38.4
37.1
30.6
10.6
l.O5~
1.11& .
1.171"
1.157"
1.243"
11.44
11.2
10.9
10.5
10.3
10 .2
11.9
11.6
11.2
10.8
10.6
10.3
II
.
.
high temperatures. The residue consists almost totally of such condensed aromatic and fluorene structures as phenanthrene (3 rings) ~
pyrene, tryphenyleneJ 1:2 benzanthracene and chrysene (4 rings);
fluoranthene, 1:2 and 2:3 benzfluorene;. and naphtho anthracene, picfme,
and 1: 12 benzpyrene. Several of these compounds tend to produce
cancer when applied to living animal cells.' Likewise, the lighter liquid
products 'of ethane or propane cracking consist almost totally of (monocyclic) aromatics.
Cracked gasolines have higher octane numbers than straight-run gaso. lines from the same parent crude oil (Tables 4-1 and 4-15). The Research
Ind. Eng. Chem., 22, 1231 (1930).
e Nelson, W. L., High-boiling Hydrocarbon Analysis, Oil Ga8 J., July 27, 1953,
p.369.
10 Borrows et al., Composition . . . Polycyclic Aromatics.
. J Proc. Third
World Pet. Congr., sec. V, The Ha.gue, 1951.
I:
1
'
I 1
630
method octane number usually ranges from ,72 to 82, but from naphthenic
charge stocks, such as some from the Gulf Coast, California,. the Far
'East, artd Venezuela, the octane number may exceed 86. The corresponding Motor method octane numbers can be estimated from Table
3-3. By high-temperature (1080 to 1250F) low-pressure vapor phase
cracking, octane numbers of 95 or higiler (Research) are obtained. The
effect of tetraethyllead on octane number can be estimated from Table
3-12, and the behavior of cracked gasoline in blends from Fig. 4-46. The
effect of 'gasoline boiling range on octane number is indicated in Tables
4-16 and 4-17, and the effect of time of cracking in Table 19-13.
.t
TABLE
19-2.
i '
:, !
, Yield,"
, per cent
35
72.5
69
80
68
85" '- " 67
'90
65
95
,. ...
60
75
I'
'
.I ' :
'I;
, '::;
1" .
:;, ! '
~ ~:
'I(Ii
~ :;;
,
, I:
~ :
~,.
II', ;
:L
) ,
i,
I ; ,
t1 ,
Ii
, I
il
I~
I,
",
'~
l' ,'.
' ,
40
73.5
' 70.5
69.5
,68
66.5
.. . .
45
50
55
76
77
72
73
75
70
71.5
73
72
70
67.5
" ~ 69---
67
...
, ' 70
68.5
66
631
larger th~ when handling straight-run stocks by a once-through operation . . Reforming to the extent of producing 90' to 95 per cent yields
may be profitable, but greater degrees of reforming probably are not
useful unless olefinic gases are desired. Higher yields of a given octanenumber product are obtained at higher pressures.. An increase of 10 ,p er
cent in , yield is obtained when the pressure is increased from 250 to
800 psi. 1i
Alhright14 shows tha.t an increase in temperature increases the octane
number of the gasoline, if other conditions are kept the same. The
Motor method octane number was increased fr~m 69 to 72 by increasing
the temperature in a 'commercial unit from 997 to l010F. Turner and
LeRoi1' find that the octane number of reformed naphtha can be computed as a function of the equivalent time ~t OOOF (see page 6Q3).
Polyforming is a modification of the thermal reforming'process whicp
involves the recycling of p;ropane and butane gases.18 Although the
'process requires the use of a 1,000 to 1 t500 psig prel:!sure on the reaction
coil, 17.18 it produces yields about 5 per cent larger (a nomographic chart17)
than pla~n reforming (see Table 19-2).
The ever increasing demand for higher octane 'numbers has led to the
thermal reforming , of already catalytically reformed gaso1ine. 19 When
reforming 84 to 89 R esearch octane catalytic reformates, yields of 75 to
93 per cent of 93 to 100 octane finished gasoline are produced.
Sulfur in Products. The distribution of sulfur in cracked products is
indicated in Figs. 4-35 and 4-36, Table 4-11 (coke), and on page 130.
Typical suliur balance~ are indicated 20 in Table 19-3. Most generally, the,
sulfur compounds in Venezuelan, Californian, and Mexican stocks appear'
to be most stable, whereas they are least stable in cracking stocks from
the Middle East and from the Mid Continent (Oklahoma, lllinois,
Kansas, North Texas, Pennsylvania, Texas, and Turner Valley, Canada).
Cracked distillates or dies~l fuels have lower pour points (Tables 4-23
and 4-24) than straight-run or catalytically cracked distillates. The
14 Influence of Temperature in Refo:rming Naphtha t Ref. Nat. Gaso. Mfr., January,
1933, p. 2. .
15 Octane-number Improvement in Naphtha Reforming, Ind. Eng. Chem., 27,' l347
(1935).
1& Ostergaard and SmoleYt . .. High Gasoline Yield by Polyform Process, Ch1. Gas
J., Sept. 12, 1940, p. 52.
' 17 Offutt et al.) 2 articles, Naphtha. Polyformmg and Naptha Polyforming with OUtside Gas, Pet. Refiner, November, 1946, pp. 120 and 129.
18 Hirsch t Osterg&ard, and Offutt, . . . Operating Variablea in the Polyform
Process, Pel. Refiner, November, 1946; p. 136.
l ' Heinemann et a.l., High Octanes. from "Iso-PlusH Via. the Thermal Reforming
Route, Pet. Processing, October, 19~5t p. 157Q.
20 Nelson, Thery, and Cordero. Proc. Fourth World Pet. Congr., sec. V, Rome, 1955.
632
west Texas
Stock
I Venezuela
I .Middle East
IMid Continent
. .
1.0
3.0
0.8
2.4
1.5
4.5
0.5
1.5
7.9
4.0
39.0
57.0
3 .8
38.9
57.3
6.6
20.4
73.0
5.4
20.4
74 .2
6.9
57.0
36.1
3.4
50.6
46.0
3.4
50.6
.46.0
5.6
26.6
4.7
26.7
67.8
68.6
6.6
62.5
30.9
3.3
.5 5.5
3.2
55.5
41.2
41.3
5.4
29.2
65.4
4.5
29.2
66.3
4.6
90.9
4.5
2.3
SO.6
17.1
2.3
3.8
3.2
80.6
42.5
53.7
42.3
. i
gas~il feeds
a.nd 6 API fuel
oils (severe cra.cking):
Gasoline ....... ; . . . .
Fuel oil ............
Gas ................
26 0 API ga.B-:-oil feeds
and 5 API fuel
oils:
Gasoline ............
Fuel oil ............
Gas . . . . ........... .
26 API reduced crude
feeds and ~a API
fuel oils:
Gasoline ..... . ......
Fuel oil .......... . .
Gas . .. . . , ......... ,
20 API reduced crude
feeds and 10 0 API
..
fuel oils (mild
cracking):
Gasoline ............
Fuel oil ..... '.......
32 API
Gas ............. . ..
'.
13.6
46 .6
39.8
8.0
33.0
59.0
11.8
60.9
27.3
7.0
43.2
49.8
13.6
6.7
66.6 47.3
46.0
-
19.8
10.0
90.5
....
5.8
64.0
30.2
8.1
43.7 43 .8
48.2 '48.3
7.1
57.0
35.9
6.8
62.5
30~8
4.7
90.6
4 .6
17.1
54.5
clearly that if large amounts of gas are produced, the heat of decomposition is relatively high, and if a process could be operated so tha.t no
gas was produced, the cracking reaction would generate rather than
require the addition of heat. The methods also ,show that the heM of .
decomposition for heavy-fuel oils is higher than for gas-oil or naphtha
stocks. The general situation is indicated by Fig. 20-2.
b
633
19-4.
HEAT OF DECOMPOSITION
.'
Reference
Btu per
Ib gaso.
Method of determination
1206 (1930).
634
API
11.8
37
.. . .
...
11.8
10.8'
59
10
Energy in stock:
Cracking stock:
l00( -19,600)
-1,960,000 :atu
Energy in products:
17.1( -22,250) = - 380,475
Heat in P.D.: 57.5( -20,13~ = -1,157,475
Heat in fuel:
25.4 ( -18,45Oj = - 468,630
Subtracting
- 2,006,580
Difference in energy:
Heat in gas;
- ( - 2,006,580) ,
+ 46,580
= 810
Heat of decomposition at 900~ (the sensible heat contents were computed from Figs
5-1 and 5-2):
Cool stock from ~OO
to 60F:
100(-580)
. = + 46,580
17.1(655). = + 11,200
57.5(642) . = + 36,900
25.4(492)
"""
+ 1'2,650
+107,330
+ 49,330
= 4:?~O
- 58,000
+107,330
... 858
Although the method outlined in Example 19-1 is- correct from the
standpoint of theory, it is not satisfactory for practical -work unless great
care is used. Very small errors in the heats of combustion or in the' yields
of products that arc assumed will introduce great e~rore in the computed
heat of. decomposition. However, many useful generalizations such as
the following tabulation of S. N. ObryadchikovM can be computed.
The first col~ is the yield of gasoline in a single cracking operation (or
the crack per pass), and the second column shows the heat required to
produce a pound of gasoline.
U
- 't
Yield ,
Heat oj deromposition
per lb gasoline, Btu
5
10
15
20
2,700
1,710
'1,170
900
25
865
35
790
635
Mithoff et, aL, Characteristics of CalifOnlla. Crude Oils, Oil Gas J., Nov. 6, 1941,
p.81.
21 Nelson, W. L., DUGas J., June 29, 1950, p. 88; Apr. 13, 1953, p. 143; and Apr. 20J
1953, p. 167.
iii
636
ponents differ greatly (Table 19-5), and the condensation ta.rs usually
contain little material boiling, higher than 850F, whereas the bulk of
straight-run tar boils above 900F. Altho~gh very low-gravity fuel ~il8
(below zero
can be produced from cycle stocks, most refiners choose
to operate for gravities of 2 to 7 API because further degradation leads
'
mainly to the production of gas.
APn
TABLE
API
gravity
-5
-2.5
0-
2.5
5
7.0
Condensation products
Straight
run
From S.R.
feeds
])'om cat.
cycle stock
..
..
..
..
100
"
..
..
100
..
65
29
..
12
14
800"
24()a
16
774
60
40
. I
,'
Nelson, W. L., Cracking-stock Control, Ch.'Z Gas J., Nov. 23, 1946, p. 74.
637
and allowing to settle for 1~ hr. Another refiner uses a 100-ml pearshaped centrifuge tube and settles by U spinning" at 1,500 rpm for 20 min.
Tar number is the milliliters of tar less 10 (for the acid). Asphaltic
materials may be diluted 50: 50 with kerosene. A. W. Trusty28 showe
the following tar numbers:
. Tar
number
Kerosene, ., . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
0
Cracked gas oil (30-36 API) ....... , ..... " 2-4
Straight-run gas oil (30-:36 API). . . . . . . . . . .. 2-6
Topped crude (26 API, East Texas). . . . . . . .. 26
East Texas crude ...... , ........... , . . . . . . . 16
Fuel oil (14 API) ........ , , ......... ', ..... , 100
One refiner 27 keeps his cycling stock to a tar number under 5.0 and the
overhead from the flash chamber to less than about 11.0. Carbon residue
is also used 28 as a measure of coking tendency.
Gasoline yields (400' E.P.,.10 R.v.p.) can be obtained from Fig. 19-129
or Eqs. (19-1) to (19-3)80 which apply to somewhat special feedstocks or
operations. The symbols refer to the API gravities of the distillate
feeds AD and cracked fuel-oil products A" and the gasoline yields are
volume per cent. Fig. 19-1 applies to straight-run 'residual or distilled
Feeds
Thermal distillates:
Catalytic cycle stocks:
Vapor-phase cr~king of
distilled S.R. stocks:
gaso. %
gaao. %
=
=
4
8
+ 2(AD .- AI')
+ 1.7(AD -
A,)
(19-1)
(19-2) .
(19-3)
f~eds.
638
90
.~ 80
..:::::
~70
60
<t: 50
~
CII
~40
~
to..
~ 20
~
:s; 10
cracking
(I 9-4) 1
vapor-phase
(19-4) becomes 1.15 rather thf:JJ1 0.5].
. Liquid volume loss == O.5(AD - Alii')
(19-4)
= 45 - 1.62 100
(19-5)
639
Eq. (19-5) applies particularly to "black-circulation" single-coil operations in whioh r~action chambers are used. Yields decrease sharply if
-thinner cracked fuels are produced .
Character.
6 to 12 API 12 to 14. API 14 to 18 API 18 to 26 API Higher gravity
Factor
feedstocks
feedstocks
feedstocks
feedstocks
feedstocks
of feed
11.2
11.3
11.4
11.5
11.6
11.7
11.8
11.9
12.0
12.1
12.2
12.3
12..4.
4-7
5-8
6-9
7-10
9-11
...
. .
....
...
"
2.0-4.0
2.5-4.5
3.0--5.0
4.0-6.0-5.0--6.5
6.0-7.0
7.0-8.0
8'.0-9.0
9.0-10.0
10.5-11.0
"
........
...... . .
"
(}-2.0
3.0-4.0
-2.O-Zero
-1.0 to 1.0
o to 1.5
1.0-3.0
3.5-5.0
5.(}-6.0
6.0-7.0
7.0-8.0
8.5-9.0
9.5-10.0
11.0-11. 5
12.0-13.0
13.0-13.5
2.0-3.5
3.0-5.0
4.5-6.0
5.5-7.0
7.0-8.5
8.0-9.5
9.0-11.0
10.5-12.0
11.5-13.0
1.0--3.0.
1.5-3.5
-1.0 to 1.0
0-2.0
1.0-3.0
2.5-4.5
3.5-5'-5
4.5-7.0
6.0-8.0
7.0-9.0
8.D-10.5
9.0-12.0'
Not much can be done about the yield of gasoline except to change the
gravity of the cracked fuel oil. However, the following conditions are
said to slightly affect gasoline yield:
1: A low crack per pass or a. high recycle ratio.
2. A relatively low pressure (200 to 300 lb).
3. A rela.tively low cracking temperature (860 to 900F), which means a. low octane
number.
Example 19-2.. A 24 API Mid Continent reduced crude oil of 11.9 Characterization Fa.ctor is to be cracked. According to Ta.ble 19-6, it is possible by the most
severe cracking to produce a 6 API fuel oil.
The degradation in gravity is (24 - 6) or 18 units API, and Fig. 19-1 indicates 8.
gasoline yield of 52 per cent. In summary:
= 39 per cent
If the 24 API feed. were a ca.talytic cycle stock, a fuel gravity of 2 or lower is poSsible, but most existing plants do not operate for a gra.vity lower than about 6 IEq.
(19-2)].
Ga.soline = 8 + 1.7(24 - 6) - 38.6 per cent
640
PETROLEUM REFiNERY
ENG~EERlNG
60~'~~~TTTT--'-'--'--rl-rrrnr--r-r--r-.-r-'~'-/7IL-'
40r
A
-
100
150200
300400
600
IpOO
2POO
JPOO
!tPOO ~oo
10,000
zopoo
20POO
40POO
100,000
200,000
40,000
r VISCOSITY LINES
FIG. 19-2. Relation between Saybolt UniverSal viscosities determined at 100, 210, and
122F. (Oil Gas J.)
SPECIAL SCALE ,.OA EXTENDED 210
+ 1.4(24 -
4)
1.15(24 - 4)
.
= 51.4
= 23.0
= 25.6
., ..1
641
results in almost no yield (Fig. 19-1) of gasoIfue (perha.ps a per cent), it mea.ns no
unaecounted~for 1088 [see Eq. (19-4)J, and in fact a. slight increase in the tota.lUquid
yield to perhaps 100.5 per cen~. A material bala.nee on a basis of 100 gal feed shows
tha.t a. small amount (10 per cent) of cracked gas oil will be produced when producing
300 sec Furol fuel oil.
Feed (7 API):
100 X 8.509 :=
850.9Ib
Gaso. (56 API):
3 X 6.283 = 18.8
Gas 1088 (2.5 wt %): 0.025 X 850.9 = 21.2
40.0 40.0
Weight of fuel oil and gas oil (if any)
810.91b
The a.mount of excess gas oil above that required to reduce the viscosity of the fuel
oil will be x pet' cent of, sa.y, 20 API materia.l.
810.9 = 7.77& + 8.388(100.5 - 3 - x)
-O.6u = 810.9 - 817
z = 10 per oent
Thus, the yieldS are:
3 per cent
Gasoline. . . . . . . . . . . . . . . . . .
Gas oil (20 API). . . . . . . . .. 10 per cent
Fuel oil (9 API). . . . . . . . . . . 87.5 per cent
Total liquids ........... , 100.5 per cent
= 303 - 250d
= 331 - 300d
(19-6)
(19-7)
The gasoline is 400 E.P., 10 R.v.p. material, and the symbol d refers to
the specifi,P gravity of the charge stock. In such an operation the amount
of coke produced (0 tons per 1,000 bbl feed) in terms of the API gravity
of the feed (A B ) is:
(19-8)
(Jag
PETROLEUM
642
REF~Y ENG~ERING
for B large gas-oil yield ranges from 15 to 25 liquid volume per cent
depending upon the amount of recycling that is conducted. Tables-or
.
charts could be presented U but there are so many vp,riables that numerous charts would be required.
~
,.
19-7.
TAB.LE
Carbon
residue,
per cent
Intermediate Naphthenic
and cracked
base
..
..
..
II
flo
...
26
22
-10
15
16
14
8
10
20
25
3.5
30
..
II
High temp
oven coke
..
II
....
..
..
It
3
11.5
17
15
21
26
4.5
2
0
-2.5
40
~
8.5
18
37
27.5
40
22
23
35.5
45
42
48
31
29
34.5
41
46
!I No gas oil.
0
0
Delayed
Ultimate
0.27
0:335
0.37
.....
II
0.20
10
0.43
0.185
0.27
12
0.48
0.21
15
20
25
0.56
0.265
0.32
00405
0.725
0.415
* Nelson,
.0.95
0.61
0.585
0.800
w.
Nelao,n,
L.~ Oil Gas J., Feb. 15, 1954, p. l81; and July 7, 1952, p. 103.
a~ Sabott, F. K.,
.. Methods of Removing Sulfur from Petroleum Coke, ~
terly of the COUwatro SCMol of Minu, vol. 47, no. 3, July, 1952.
12
643
Example 19-4.
will be explored.
By ultimate coking,
t~e
Weight
per cent
16
18.6
29.8
41.2
57.1
66.4
106.5
147.0
Tons per
1,000 bbl
28.5
33.2
53.2
73.0
Gasoline
= 303
The 8Jl,lount of gas per barrel would be (about 20 per cent of the coke ';Veight)
35~.5 X ' 0.412 X 0.2
2: 5
357.~
8.8
Ib
loo.5Ib
18.1
124.6 Ib
124.6
232.9Ib
0.20 X 42 X 6.385 "'" 53.5 '
179.41b
If the gas oil has a. gravity of 20 API, the per,centage of gas oil will be
179.4
1
7.778 X 42 = 55 per cent
The amount of gas will be abOut
1~i1
X 379
The yield of gas oil will be changed slightly if & different gas-oil gravity is aasumed,
and even larger differences will arise if recycling is practiced to the extent 01 producing
25 per cent of gasoline.
By the Fluid process the gas yield would be slightly larger:
357.5 X 0.186 X 0.37 X 379
22 '
422
II:
eu
ft
644
PETROLEUM
R~FINERY
ENGINEERING
Reaction
100
I,
I
CtHo- C2 H,
+ H,
CJHa- CIH,
CaH.- CaRs
+ CH.
+ HI
'
l,
63.5'
30.0
6.5
j .
I'
1I :'
,
.
1
,;
'r 1i'
Ir '
II,
I~ ,
! j'
;:
I'
+ 2CJi.
30H 2
'
(19-10)
~/OO~------~------~--------~------~------~
~
If
a 90r-------~-------+--------~------~------~
-c::
I'ij. ,
- if' ;
:!i '
2C aHa -+ C 2H.
(19-9)
'r,
~
f
80
~ 70r-------~--~--~--------+_------~~--~~
'il. '
.....
~ 60
Ii
Ii'
~ 50~------1_------_+--~~--~~--~~--------~
~
'"'
.~
~~ 40~------~------~----~~~~----~~----~
~ 3 0 1------t------t-7,L---7'~__t__==~-~
1
~
20
t---------+---~'_'~------+_-
~ IO~~~~~~~~~
o~
20
40
60
80
100
This co~templates decomposition of all of the propane feed, and in prac. tiee .this is accomplished by recycling any undecomposed propane. 'The
common and economical conversion per pass for propane is about 85 per
cent, and accordingly the single pass yields would be about 85 per 'cent
of Eq. (19-10) plus 15 moles of unreacted propane. According to Eq.
11
645
(19-10) the ultimate yield of ethylene from propane is 66.75 per cent on a
mole basis, or 42.5 weight per cent.
H. C. Schutt 33 also states that the ultimate decomposition (including
unavoidable polymerization) of propylene gives the following yields:
100C3HS ~ 17H2
(19-11)
5 aH7.lIi
Fl-om
From
From
From
From
eth ane, . . . . . . . . , . . . . . . . . . . . . .
propane ........................
propylene .... . ..................
butane ........... . ........... . .
kerosene or gas oil .'... . ..... . .. : .
Weight, %
Conversion, % per.DfU1lJ
74:-15
42-43
26-27
60
85
38-39-
..
..
85-90
58t
22-23
Somewhat higher once-through and ultimate yields are said"6 to be possible with special heaters such as the pebble heater,U and it is evident ,
that heaters must be designed to eliminate, insofar as possible, undesirable side reactions leading to coke or polymerization products.
The general effect of conversion per pass is illustrated in Fig. 19-3
for the high-temperature (1350 to 1400F) low-pressure (0 to 20 psi g)
cracking of normal butane in tubular heaters.38 Dehydrogenation equiU
Schutt and Zdonik 1 Making Ethylene . . . Part I. Oil Gaa J., Feb. 13, 1956.
~~
-- --
-' ~ '
--
~- .-- :
,
T.ALE 19-8. TYPICAL ONOE-THBOUGB YIELDS W'BEN CBACXING PlwuluLY FOR ETHYLENE~
Ethane
1438-1460
7.5-10
1472-1486
31-32
1415-1448
1410
6.8
11.6
0.3-1.1
0.8lH>.4
88-87.7
1. 7~1.76
1-1.15
Sl-82b
1.62--1.64
0.28-0.36
12.1-13.0
11.9-13.3
30.3-31.4
11-.2-12.6
6B.8-{l2.6
1. 5-1.68
81.1-85.6
3.H.6
0.2
31-33.1
22.6-26.7
0.&-1.~
Butadiene }
Butene
... , .' ........ : ......
32.4-84
O.I~.2
0.2-0.3
20.4-25.7 24.9-25.6
7.9-10.3 ' 4.7-6.0
8.2-8.7
-14.1
1.9-8.3
6,Q-9.7
0,2-0.4
.. ,,", ..... ,
} 0.9-1.1
...........
, . " ,
....
.,
"
to
......
....
...........
"
t ' .. "
........ , ,. .
"
................
..
1.3-1.9
I
(89-215F)~
13M-HID,
12.5-15.3
3'.06-7.5
2.7.5
B.R. Daphtba
(215-430F)
52.2 API
36-38 API"
1340-1405
13.6-15
1335-1375
6.5-8.5
Gas oil
3.6-8.2
4-7.9
74.8-90.6
1.9-2.17 ,
14.5
28.6
29.5-83.6
0.2-0.4
', 18.4-24.4
5.1-.5.7
n.5-14,1
1. 8-2. D
1-1 . .4
: ,1.~2.0
4->12.2
10.5-15,6
28.3-28.7
0.1-0.6
26.7-82.4
11.2-14.6
29 . .5-31. 4
0.2
27.6
0.1
4.&-5.6
3.H.8
13.2-15.6
28.5-29.6
0-0.2
26.9-32.4
2.9-7.9
11.3-14
0.6-1. 2
2.1-3.8
3,4-6.9
0.2
0.~.3
O.z-.<),3
100 (oG.&-59.6)2.8-4.8'
}25.2-33
12.0
1.1
' 2.8
6.1
6.7-8.0
3.4-9.1
10.5-14.3
0,7-1. 2
2.6
11. 7-16.1
0.4-1.1
2.4--3.2
S.1
.......
- - - -
. .. . ..
....
.................
.. ..
..
..
..
.........
..
........
"
"
..........
.. " ......
2.4-3'.6
................
..
......... ,
2.&-3 . 3
..................
........
.. ,
...............
-
100 (13. 0)
I
......
..
...........
21.0. .. .. . . .
..
5.~
-
Schutt. and Zdonik, Making Ethylene . Part I, Oil Ga. J Feb0'3. 1956. p. 9S.
18.8 to 24.1 per cent propylene in feed. The propylene converaiJ6 ranpd from 40 to 48 per oent.
73.2 API.
Cha.raoterisation Factor of 11.85.
Except Uquid pJ'Oduota which are weight per aent.
II
distillate
0.~.6
0.1-1.3
,
}0.H.7
Light S.R.
Na.t. gMO.
Grade 2&-70
Butane
1516-1525
3-81
;::!~r,,
Propane
propyLeneb
Propane
100 (70.3-73.8)
100 (61.5-59)'
. ......... , ................
.. .......................
17.8-24.1
.............................
D.&-8.
- -
16,5-lS.a19.6-22.~
'-----
647
librium constants 37 ,a's .39 for ethane, propane, and butane are shown in
. Fig. 19-4.
The principal reactions in the thermal decomposition , of butane and
i~obutane are:
nC~HIO ~ nC~H8
nC.HIO~ , CSH6
nC.H 10 ~ CtH.
2nC,H 10 ~ nC 4H g
2nC.H 10 ~ nGJIs
'+ H2
(19...12)
+ CIl.
+ C He
2
+ CaHs + CH~
(19-13)
+ 2CtHs
(19-14)
iC,H 10 ~ iCJIs + Hi
iC 4H 10 ~ CaH8 + CH 4
iC.H 10 -4 C2H 4
2iC 4H 1o ~
(l9-i5)
+ C2Hs
iC~Hs '
+-CaHs + CH(
(19-16)
/ If
VL
/I
V
V
P(t;,~~
frt4JW
1~fC:rH.~) V '
/ / - (C"HIJ I
L If
/
If
II
/
02
Vi
OJ 1000
l- P(CzP',xH,J
V
I
tt;~.1
:;
1200
-~
pTINrJI jn$IIn
1400
1600
TemperaiUTt. F
aU
648
,I
!
'c .
i. I,
,, .
, .
I.
Crac~ng
1000. . . . . . . . ..
1080 ..........
1160 ..........
1240 ..........
I:
:.
,j . .
;'
1.
I
'.
16mp, OF % Butadiene
0.4
1.06
1.73
2.4
.Cracking temp,
of
% Butadiens
1320. . . . . . . .. 3.07
1400.: ..... . . 3.75
1740 ... "...... 6.6
649
Prebenzene. . . . . . . . . . . . . . . . . . . . . ..
Benzene. . . . . . . . . . . . . . . . . . . . . . . . ..
Nonaromatics ill benzene range .... ,
Toluene ......................... ,
NonaromaticB in toluene range ......
m- s.nd p-xylene ...................
o-xylene s.nd styrene .............. ,
Alkyl benzene. . . . . . . . . . . . . . . . . . . ..
PrenaphthaJene ......
Refined naphthalene ..............
Alkyl naphthalenes.. .. . . . .. . . . . . ..
Antbra.cene cut ...................
Pyrene-chrysene cut ...............
Hard pitch, mp 203-338F .........
1.8
5.3
0.4
6.0
0.3
3.0
2.5
7.1
1.2
1.0
S. 2
3.4,
3.4
4.8
19-9.
Stock
Sp gr'
Kel'OBene .. . ...................
Solar oil ......................
Para.ffin oil. . . . . . . . . . . . . . . . . . . . .
Spindle oil .....................
~ cylinder oils ..............
P8l'8.ffin. . . . . . . . . . . . . . . . . . . . . . . .
I.
......
0.833
0.904
0.93\
,
....
Reaction~
392GF distillate
per cent by weight velocity conStant
4.9
18.6
26-30
28.2
29.5- '3 0.5
31,2
0.0000672
0.000288
0.000457
0.-000461
0.000498
0.000518
Sachanen and Tilicheyev, Ch'l Gas J., June 23, 1927, p. 144.
Computed by author by Eq. (19-19).
Sachanen and Tilicheyev 48,49 indicates the relation of the rate of cracking
, to the proPerties of the cracking stock.
Sung, Brown, and White 60 have studied the rates at which products
(including gas) of differ~nt end point are produced. Their approximate
results for 900F tabulated here do not check the rates shown in Fig. 19-5,
which may! be due in part to the fact that they extrapolate their experimental ~ta to zero per cent conversion in determining the equilibrium
constant, but since scarcely any other such data are available, their study
is extremely valuable.
Reactionvelocr
p~~
uyoomrom
1"
0.0039
0.0063
0.0105
0.0160
0.0205
0 . 0270
4a
41
650
Most approximately, their results indicate that the rate of gas formation
is 15 to 25 per cent of the rate of gasoline formation.
'
. Thus the lighter the cra.cking stock the longer the time required. In .
commercial practice the yield from light stocks is obtained not by using
& long length of time but by using a. higher temperature.
As will be
shown later, an increase in temperature is very effective in decr~asing the
time required. Stocks that have already been cracked, such as recycle
stock, also require a longer time. In general, stocks that require a
relatively long time for a given yield are termed tc refractory stocks."
Recycle stock, kerosene, naphtha, and gasoline are classed as refractory
stocks.
The cracking reaction may be described in a general way as a firstorder reaction if the decomposition is limited as in conventional cra.cking
operations to a low conversion per pass (20 .to 25 per cent):
Kl
where Kl
a
= -1t I n
-a - x
or often
. :. !
In
100
100 - x
(19-19)
651
rill' I T
11/7' II '{
rJl!
I
!J /
LEGEND:'
0.6
/V-..lln
~
- I
10-.z
0.5
0.4
I-Hmt! (sec)
x-percenlagfJ decomposed
a2
0.03
I
I
7 I
I
~'
II ~il
l~ '1
1.0
0.8
0.6
0:5
0.4
OJ
0.2'
al
o.oa
a06
0.05
004
0.03
0.02
0.02
~ 10
lie'"
.....I
ao'l
0.006
0.005
0.004
....~
~
11 25
0.003
\i
In
~I
II.L
W,.II
7
Ij
IIi
--
~t=
Jf
~=
f;j,11
J it....J
/
I
'<:i'
0.006
0.005
0,004
aoo)
aO{J2
~/!
0.001
0.0008
0.0006
o.ooos
0.0004
(s"i
'/111 II
0.0001
0.00008
o.o(}(x)G
(11//!J I
0.0002
~/j
rIT
",
0.0003
II
~
,i
'7 rT
~,,""rf[7
...."!flrl T
0.00001 700
a008
4.
\'1//
V
I'
IT,
" / lL~
" 1
1
Ii, 1
aOI
I
J
ll
TI,
-, I.,
Jo///!J. ,'ll,/// !
0..0002
'I A I
II H ./
I I ~l,' II VII.
, 'r7i;r--+
j,."
rll /I
IT
1
I
v '11/ i
II I I I I I, /I rl
,r
OJ
1
Till II
77, rlTf7T
.L
'/
'/1
0.0006
0.0005
0.0004
. 0.0003
0.00002
f-~
r"4 'j~1
~,' '"11
0.001
aOO08
0.00006
0.00005
0.00004
0.00003
f:=~()'"
VIA ~ZWI/
It~ "d
0.002
\;
API grO'll"/y,
uf produd
0.008
5
~
li:
1// ,
'I
....
{;
a06
0.1)5
a04
I! / fl ,II
0.1
0.08
...
-,
OJ
-"~
.1/
0.00005
a 00004
0.00003
I
1000
1100
Temperalure, "F:
0.00002
1200
1400
0.00001
1600
FIG.
652
In Kl = -E
653
place is more rapid than the rate of decomposition, and the yield becomes
less. As the yield becomes less, large amounts of tar are produced and
coke may be formed. Hence commercial processes are never operated at
times that are greater than the time at the maximum point in the timeyield curve. If recycling is practiced, the conversion per pass must be
well below the maximum point of the fresh charge. stock, but for oncethrough operation the conversion per pass may approach the maximum
point closely.
Temperature affoots the general shape of-the time-yield curve. The
. maXImum percentage point is lower for high cracking temperatures
16,000
Crocking
.
km&:g.nrfvnt,
842.
F.-~---
_::J
14.000
1\
~ IZ,OOO
'\,
" 1'>",
S10,000
a.
If)
.. 8,000
E
.- 6000
I- '
./
2,000
.-~ ~
5
FIG. 19~6.
Pet. Tech.)
10
15
l...--
?J)
25
30
35
40
45
and also lower for stocks that have already been cracked. Thus at
bigh temperatures the rate of polymerization is relatively faster than at
low temperatures. The maximum points and times for several sets of
data are shown in Table 19-10.
The use of reaction chambers and soaking drums is to some extent
being abandoned, except when coke is desired, because of the decreased
yields at a long length of time. However, in some modern plants, the use
. of reaction chambers for soaking of only the vapor has resulted in both
increased capacity and an increased yield. 68 The maximum points are
also the governing factor in determining the recycle ratio that is possible.
58 Mithoff and Schima.nskY, Reaction Chambers on Thermal-cra.cking Units, Oil .
Gas J., Nov. 6, 1941, p. 135.
8M
-Temperature, OF
700
844
894
800
842
850
900
932
1076
1184
19.10. Tm:E
40
48&
35
36
31
26
23
20,000+
5,200
420
14,000
7,500
3)500
1,215
1,000
30
3
ReIerence
Phase
Stock
Liquid
Liquid
Liquid
Liquid
Liquid
Liquid
?
Vapor
Vapor
Vapor
Recycle
Recycle a.nd gas oil
Recycle and gaS. oil
G88 oil
Paraffin wax
Light gas oil
Gas oil
Gas oil
Gas oil
Gas oil
59
50
50
60
57
50
50
61
61
61
Yield decreases with time for recycle stock probably because of polymeriza.tion.
b Either poor data, or paraffin wax beha.ves differently from oils.
69 Leslie and Potthoff, Ind. Eng. Chern.-, 1.8 , 776 (1926).
eo Cross, uILmdbook of Petroleum, Asphalt, and Natural Gae," Bull. 25, p. 287,
1928.
. 61 Geniesse and Reuter, Ind. Eng. Chem.; 24, 219 (1932).
4
Time, sec
380
300
170
150
130
40
3
1
0.3
Recycle stocks require more time for a given yield than straight-run
~tocks. Table 19-11 indicates the refractive nature of these stocks. The
figures refer to the ratio of the yield from recycle stock to the yield from
fresh stock, if the two are cracked under the same conditions of time,
temperature, and pressure.
Recycle stock, regardless of recycle ratio,. will consist almost entirely of
material that has been cra.cked once and twice. Hence the currently
recycled stock will crack about half as readily as fresh stock..
Although cracking is usually considered to be a decomposition process,
maillly because of th~ interest in producing lower-boiling materials such
655
19-11. IUTE
Once
cracked
Twice
c racked
0.6
0.79
0 .795
0.318
. . . .
.. . ..
.
.
. . .. .
0.69
. . . .
... I .' ..
Current
recycling
STOcxs
Thrice
cracked
...........
0.175
..............
. .......
. .. .. .
. ..
.. . .. .
0.4-0.47
0.43
..........
.
........
Reference
7
7
8
21
Fig. 19-5
yield, based on the mixture, of 20 per cent, or 0.2 X 3 = 0.6 parts of distillate. Based on the one part of fresh stock, which is all that COD1es into
the plant, the yield of pressure distillate is 0.6 X 100 + 1 = 60 per cent.
Recycling is necessary because coke is deposited and a large gas loss
occurs if high yields per pass are produced. The tarry material and the
reactive materials that are produced during cracking seem to be the source
of coke. If the yield is great, the maximum point shown in Fig. 19-6 is
approached, and polymerization takes place with the formation of tar and
coke. These products are always produced to some extent, but in the
recycling operation they are currently eliminated before they attain
reactive concentrations. The co.m.mon arrangement is to cycle the
era:eked material that issues from the pipestill, through a fractionating
system. In the fractionating system the tarry ma.terials are eliminated
into the craeked fuel oil; the gas and cracked naphtha pass overhead;
and a hea.rt-:cut material consisting of fresh gas oil and recycle is withdrawn as a clean -distillate which is continuously pumped into the pipestill. Thus the same quantity of reCycle stock and of fresh gas oil or"
656
reduced crude oil is charged to the pipestill each hourJ and constant
quantities of reQycle, gas, distillate, and 'cracked tar issue from the
outlet of the still each hour.
The relative quantities handled at various points in a particular type of
cracking system are illustrated in Fig. 19-7. The quantities in the figure
are given in barrels and are based on a charge of 100 bbl of a fuel oil
charging stock. The char~g stock consists of 80 bbl of gas oil and 20 bbl
of straight-run tar. The charge is heated by exchangers and a heater, if
necessary, and is then mixed with the hot cracked material that issues
from the pip estill. In evaporator A everything except the straight-run
tar and the cracked tar is vaporized. In the fractionatQr B the pressure
distillate and gas are eliminated, and the gas oil and recycle stock are
separated and returned to the pipes till.
The recycle ratio is defined as the barrels of recycle stock per barrel of
fresh gas oil. The recycle ratio for this operation is 175/80, or 2.28, and
the crack per pass is 48.5/255, or 19 per cent. The recycle ratio is sometimes used as the barrels of recycle divided by the plant charge (100 bbl in
this case). Such a definition of recycle ratio is not logical in the system
illustrated because the entire 100 bbl is not exposed to cracking conditions.
The general effect of increasing the crack or conversion per pass is as
follows:
1. Lower ultimate gasoline yield.
2.
3.
4.
5.
1"""7'
. " 657
gas oil.
Thus the gas oil is being cracked at a yield that is closed to the
maximu~ poin~, but the recycle stock is being cracked for a yield" that is
less than the average crack per pass (Example 19-6). At very high cracks .
. per pass the gas oil. will be cracked for a time greater than that for the
maximum yi~ldJ and coke will be formed.
. 1.
Reduced crude
t;harl)e stock 100 gal
Gos 011. 80
Recycle. 175
Slroight-run
lor, 20 (101
r---''-----,
.D
90lb
Recycle, 175
600 0
CrocKed
ndphlho
. 48.5 ga/
400lb
915 0
.Straight-run
tor, 20
Croclred lor, 24
Tolol lor, 44
Gas
OIl.
80
"
"Recycle,
175
Furnace charge, 255
Process
Per cent
:, !:
r
3--12
10-17
15-21
18-26
PETROLEUM
658
n~!~'~~D~
ENGINEERING
crude oil by exposure to the oonditions in vessel A of Fig. 19-7. Material balances
to determine the quantities at all points will be madeJ and the recycle ratio and crack
per pass will be estimated.
:'
'
Basis: 100 gal topped crude oil.
According to Table 19-6, a fuel-oil gravity of ) or 6 is possible if the entire residual
material ,is ormed.' In this instance the asphaltic part of the topped crude oil
escapes' 'from the system through vessel
without undergoing much cracking or
viscosity
and a gravity of only about 9 is feasible. The ultimate yields
[Fig. 19-1 and Eq. (19-4)J based
the 24 API topped crude oil will be:
on
cent
This may be checked by oonsidering that only the 80 gal of ga.s oil is vigorously
cracked, and thus nea.rly all of the cracked gasoline comes from the gas oil. The gas
oil can be degraded to a. 6 API fuel oil
the yields are:
, Gasoline (27-6 APl) ............. 58 X 0.8 = 46.5 per cent
Unaccounted-Cor loss. . . . . ... . . .. 10.5 X 0.8 """ 8.4
Cracked fuel oil ........... 31.5 X 0.8 + 20 - 45.2
This is not a good check but it is reasonably good compared :wit~ variations sometimes
cent
encountered.8lI In addition, a. small &mount of viscosity breaking of the 20
of straight-rUn fuel oil oceurs and this contributes to the gasoline yield. The production of more gas when cracking distilled feeds, as indicated a.bove, is & common. plant
. experience.
Per cent
or gal
API
Lb per
gal
100
24
Z1;
80
...
20
Total '
lb
7.58
7.434
. .....
758
595
163
Lb per
gal
Total
Ib
8.388
8.15
369
.;,
or plant tar:
Plant
Total tar .............. ~ .....
Straight-run tar........... ',' .
Cracked tar. . . . . . . . . ". . . . . . . .
Per eent
or gal
44
20
24
9.0
13.1
~
. '"
........
'"
163
206
659
Recycle ratio:
When cracking at ~H5F the allowable crack per pass is about, 36 divided J>y 2
(Table 19-10), or 18 per cent. In general, a. little higher value than this is p.ossible,
and hence 19 per cent will be used 8.S the crack per pass. The total 48.5 gal of naphtha
is 19 per cent of the eharge to the furna.ce. Furoace charge:
48.5
=0
255 gal
0.19
Material
API
80
175
255 ,
27
17
.. .
Lb per
gal
Tota.l
Ib
7.43
7.935
595
1,390
1,985
The API of recycle stock will be over half 88 much as the API of the gas oil, or
abou t 17 API.
Lb per gal oC-furnace charge:
l;~
Recycle 'ra.tio:
176/80
or gal
API ,
Lb per
gal
Total
Ib
48.5
59.0 ,
17.0
5.8
6.18
7.93
8.58
299
1,390
Per cent
Ma.terial
Cra.cked naphtha .............
Recycle .......-....... '.......
Polymer tar .................
Fixed gas (by difference) ......
Furnace charge ...............
175.0
24.0
. ... .
255.0
....
20.0
7.78
206
90 '
1,985
The
660
In the butane plant the product is separated as a liquid in the fractionat: ing system (or subjected directly to. some process such as polymerization
forutili~ation of the olefins) and the excess butane and propane are sep- .
arated. from the gaseous product to be employed as a recycle stock.
Thus, butane plants require fractionating equipment similar to those
used in ~atural gasoline plants arid gas recovery systems, whereas separa tion systems operating at only a few pounds above atmospheric pressure
are suitable for cracking plants. The butane decomposition plant shown
in Fig. 19-8 should be compared directly with the cracking system shown
in Fig. i9-7.
.
The system shown in Fig. 19.-8 is usu~lIy employed with other systems
such as polymerizatio?, alkylation, etc.,. ~nd such processes are inferred-in
Gas product16 Propane(mols)
84gases
r-~
(offen sent
to absorption
or refri~mtion
~stemto recover last of
. Butanes)
__----~H~~l~~----~
----J---- .
r.:--- -
- ---'"\
':' __ JI __ -,
8i Olefins
114 Butanes
102 Propane
84 Gases
'.
.Ftocessing
or; separating
'Olefins J I
>'; ___ , __
. I
r.--t---,
~--~Hoot~chtmn~J
600 0 F
...
---TO'~~ri
Propane 86
.
200 Rec.Yge
product82mols
250F.
\00 Feed
300 furnace
charge
the dotted-line operations indicated iIi the center of the diagram. High
temperatures and pressures are necessary in the decomposition zone in
order to. care for the relatively large volume that is occupied by gaslike
materials such as butane' 1 . If thermal polymerization is the process contemplated in the center of the diagram, the whole flow diagram is the
same as a cracking process except that a long time element is required in
the polymerization zone whereas in cracking plants the polymerization of
tars, etc., is avoided in every way possible and particularly by cutting the
time to a minimum.
The design of coils for the cracking of propane and ethane into ethylene
is completely outlined by Schutt. 33
Effect of Temperature. The temperature at which .cracking starts to
take place is between 680 and 7QOF. . This appears to be true even for
'
661
CBAClUNG
TO DOUELE .
Dec omp'osition
temperature,
of
Decomposition
Rate
Rate
doubles
doubles
temperature,
of
for each---:.
for 'eaeh-
700
34.5F .
800
20.0F
22.0DF
1100
1200
900 .
25.7~
1300
44.0~
30.0F
1700
67.0F
1000
39.0F
The general relation among temperature, time, an.d Yield is ' given by
Eq. (19-19) and Fig. 19-5. ' It must always be recalled that these data do
not apply to large yields or to situations in which polymerizatio,n, ' (or
secondary) reactions occur to such a.n extent that they undo the results
of the primary decomposition reactions., For the usual situation, however, in which temperature varies, equations such as- (19...20), (19-21),
and (19-22) may be ~mployed or the Soaking Factor method of pages 674 .
to 678 may be used.
Example 19-6. Temperature, Time, and Yield. The cracking opera.tion preSented
in Example 19-5 will be continued. Cracking is to occur at about 915F. ,
How much time is required to give a crack per pass of 19 per cent?
Ba.sis: 255 gal of furnace charge (or 100 gal of redu~ed crude).
The recycle stock (155 gal) will produce only 43 per cent as m~ch, gasoline &8 tha.~ ,
which accrues from the fresh stock (gas oil). (Table 19-11.)
Rate of cracking gas oil (let:t - yield from gas oil):
255(0.19) = SOx + .0.43 X 155:t
:t =r 33.1 "
\
= 0.00296 In 100
100
Note also tha.t based on recycle stock, or on the mixture, the .time is .
t
. or
100
, == O.OO165 ln 100 _ 19
=0:
662
For
cra~king
T,-To)
(19-20)
or
(19-21)
O2 = 0 02 ( -a:-
. dO
'di
= Co2
(T-:-To)
:
T = To
+ kt
2(kt+T:-TD) dt ==
-0
= Co
(J
= 1.44 Ct (i~)
o In 2 k
Co ft
}o
2(;) dt
.
In 2
(19-22)
Turner and LeRoPo conclude -from reforming tests that the octane
number of the product is purely a function of time, as shown in Table
19-13.
Times of reaction are so short at 900 to 1300F that the furnace effluent
in commercial pIants must be cooled rapidly (quenched). Crack~d fuel
663
oil, fresh <;harge stock, or recycle stock is mixed in the pipestill ,transfer
line with the hot cracked stock, or the cooling agent is introduced into the
flash chamber marked' A in Fig. 19-7.
Although cracking, in the normal sense; occurs at temperatures exceeding 680F, other less vital changes take place when oils are heated to
lower temperatures. Many untreated lubricating-oil stocks are discolored if they are heated even to 300F in the prese~ce of air. H they are .
TABLE
19-13. EFFECT
(45
Equivalent time
at 900F, sec
OCTANE NAPHTHA)
Octa.ne number,
Motor method
45.0
55.5
60.0
100
200
300
400
500
600
700
68.5
70.5
72.0
63.5
900
66.5
1,200
73.5
75.0'
heated to higher temperatures for a long time, the viscosity and the gravity are also lowered. In the author's laboratory a paraffin-base lubricating oil was redistilled three times for the purposes of separating the oil
into well-fractionated products of short boiling range. During these
distillations the temperature in the main body of liquid never exceeded
620F and the pressure was kept at less than 10 rom. The oil was heated
for.a total time of 22 hr at 300 to 620F. The viscosity and gravity
dropped as follows:
30F fractions boiling at these average
atmospheric boiling
points
700
800
900
1000
Sp gr
Viscosity at lOOF
Before
Mter
57
56
104
99
245
229
350
415
Before
0.8484
0.8636
0.8742
0.8825
Mter
0.8471.
0.8616
0.8729
0.8794
664
---.
it
665
is slightly less at high pressures. This may be explained by the decomposition of part of the gasollne into fixed gas by the prolonged time of cracking. 65 However, Keith, Ward, and Rubin 86 and LeRoi and Ferguson 12
report just the opposite effect of pressure. Keith finds that the gas loss is
three times ru3 much at 100 as at 1,000 psi. Commercial practice also indi;ates that the gas loss is less at high pressures. Most experimenters 12 68
find that the octane number decreases as the pressure is increased if the
tiRme amount of crRckirig is practiced.
Liquid-phase and Vapor-phase Operation. In general, three phase
conditions are recognized in commercial processes. If the pressure is
",elatIVely .lOW, so that a pure vapor phase can be produced at the cracking
temperat1 ue, the process may be classed as vapor phase. Vapo~-phase
processe~ are not successful unless a vapor that is free from liquid is produced, because coke will be deposited in .the tubes. At higher pressures
and lower crapking temperatures a mixed phase results.
T~LE
Run
number
1
2'
3
4
19-14.
di~ti1late
5.3
63
65
69
72
in
The bomb equipment that Sachanen and Tilicheyev used promoted the cracking
of gasoline by allowing part of it to condense and drip back into the cracking vessel.
In some tests they kept the products of cracking in the cracking still until the test was
comp1eted.
66 The Cracking of M. C. Virgin Gas Oil . . . Range of Temperature and Pressure,
Proc. API, Refining DiviBion, 1933.
Sft
666
coils of mixed-phase processes. Nearly all modern processes are mixedphase processes. In vapor-phase processes the pressure is normally less
than 100 psig and often only 15 or 35 psig.
Volume at Decomposition Conditions. No single factor is of greater
pract~cal importance in cracking-plant design than the computation of
volumes of liquids and vapors at cracking-zone conditions. Volume is
directly related to time in the cracking zone and to the friction loss.
Volumes may be computed with reasonable accuracy by the use of
Figs. 5-9, 5-12, 5-13, and 5-15, bl,lt careful consideration must be given to
TABLE
19-15.
Curve
API
1
2
24.1
24.1
25.6
20.0"
19.0"
CharaeterRecycle
ization
ratio
Factor
..
..
... ..
2.4"
1.76
2.0-
. .
..
..
920
930
10.9
3.0
11.2
10.721
..
..
. , ..
24.5
18.71
31.4
..
... .
66
21.8
21.5
10.7
10.6
11.051
56
1,070
1 ,097
1,100
..
. . ..
20.8~
11.05
11.2
11.2
10.75"
10.6"
10.85e
24.8
8
91
10
11
12
13'
41J
5"
&
.. ,
Aniline Cracking
point,
temp,
of
of
30.61
10.65
"
...
I
.. .
,.
,
I
4.1
3.3
2.58
..
..
to
..
67
.....
....
.....
..
o.o.
"
19-9
Source
Wagner"
Wagner li
Wagner lJ
3 plant tests, author
2 plant tests, author
Commercial vapor phase
author
Huntington & Brown 4
Allen & Duckwall"
Allen & Duckwall"
3 vapor phase tests, author
5 vapor phase tests, author
2 vapor phase tests, autllor
Naphtha reforming
Cracking Recycle Stock, Oil Gas J., Sept. 30, 1943, p. 45.
~ 745F evaporator temperature, and pressure distillate end points of 440 to 445F.
"Recycle 2 parts and Mid Continent reduced crude 1 part, a black feed.
4 Ind. Eng. Chern., 27, 699 (1935).
Pet. Refiner, February, 1945, p. 89.
J Pure recycle stock rather than furnace charge.
Ii
the physical properties of the stocks. For example, should the gravity of
the recycle stock be assumed to be 15 API, whereas the actual vallie is 17,
the results may be somewhat misleading. Small errors become very
important, because the stocks are at or near their critical points and a
small misjudgment may shift the behavior of the material from that of a
vapor to that of a liquid.
The extent of vaporization may be estimated by drawing flash-vaporization curves of the stocks (Figs. 4-18 and 4-19) and correcting these
curves for pressure by means of Fig. 5-27, but more precise r~sults can be
obtained by drawing the phase envelopes of the outlet material and also
667
I
I
COKING
780~820
WITH
REDUCLD CRUDL
aooIr-_____r-___~--~~__~~DRECYCL fEED
VACUUM
flASH
~
0
740 - 820
laS
EVAPORATOR
a:
::l
700
Q: .
1&1
0-
EVAPORATOR
2:
laS
....
a:
0
Q.
600
H VOROCARBON
< PRE:SSUR[
> DI5T.
!>OO
~~-----~--~~~~~~~~~~~~~~~-+~
rEED
STOCKS
~~~~~~~~~~~~~~~~JJ~~~~-t-1CRAC~rNG
ro
------t~.
GASE5
HYDROCARBON
~r-~~~~~~~---~----~----+----~---~----~~RECVCLES
300~-----~--~--~------L----L---~~---~--~-----L~---
10
20
30
40
50
60
70
80
SO
100
p~
45.
668
,The front end of the distillation curves is fairly well defined by the
end point of the light product, and the high-boiling end by the extent to
which recycle stock is vaporized from tbe cracked fuel oil (or coke).
However, if the furnace charge stock contains residual material (topped
or reduced crude oil, etc.) the high-boiling end of the distillation curve
depends entirely on the distillation curve of the residue material (see
curve 6, Fig. 19-9). Inasmuch as high-boiling materials decompose most
readily (see Fig. 19-5), such materials are eliminated more completely
from the recycle stock (and the furnace charge). Recycle stocks (low
-Characterization Factor) usually have lower boiling ranges than the
parent feed (but see curve 13 of Fig. 19-9). This results in relatiyely
large amounts of low-boiling material in the recycle stock and in the
furnace charge stock (Fig. 19-9). The higher the cracking temperature,
the lower the boiling range of the furnace charge stock and the lower
the Characterization Factor of the'recycle stock. Extensive recycling
tends to lower the boiling range of the furnace charge stock. Only
curves 9 and 13 are pure recycle stocks, nor were the data adequate for
an estimation of the distillation curves of other pure recycle stocks.
Example 19-'1. Increase in Volume during Cracking. ExAmple 19-5 provides da.ta.
by which the volu-me increase can be computed. In this example the weight of fixed
gas per 100 gal of charging stock was 90 lb. The density of cracked gas, if liquefied
and measured. at 60 0 F t would be approximately 3lb per gal.
The volume of fixed gas (liquid) =
Th~
,9%
, Gal
PresSure distillate ... '......... , 48.5,
Fuel oil (cracked) .. . ........ " 44.0
Fixed gas .......... . . .-. . . . . .. ' 30.0
122.5
Thus the charge increased by 22.5 per cent in volume durmg ct:o.cking.
Although 'the gas cannot be liquefied at 60F, it may be dissolved in the other parts
of the furnace ' stock at high pressures, and hence the volume as computed above
becomes v~lullble fo! computing the volume of the cracking stock while it is in the
furnace tubes. '
'
Example 19-8. Cracking Still Design. The coil conditions necessary to crack the
materials studied in Examples 19--5 to 19-7 wiH be investigated. Cracking will be
conducted in the radiant section of a still which delivers 12,000 Btu per sq'it of projeeted area, and an actual capacity of 3,000 bpd of reduced crude oil rather than
100 gal (Exa.mples 19-5 to 19-7) will be considered . . Such a basis 'is 52.5 times larger.
3,000 X '%4
100
Ba.sis: 3,000 bpd reduced crude oil.
properties of the materials.
= 52 5
.
tl69
The distillation and flash vaporization curves were computed for the furnace feed,
the effluent, and for the material when it was half cracked, as indicated in Fig. 19-10.
In estimating the distilJation curves, the mid bojling points of Table 19-16 were
used, along with a terminal temperature of 770F for the recycle stock (see Fig. 19.9),
and an initial boiling point of 590F for the gas oil. It was judged that material
boiling up to 1000F could be vaporized (into the gas oil) by exposure of the reduced
crude oil in vessel A of Fig. 19-7.
Phase envelopes were also computed for the feed, the effluent, and the material
after the reaction was half complete, as indicated in Figs. 19-11 and 19-12. They
are not .o f much use except in a general way in judging the situation in the coil at various degrees of reaction. However, they were used to raise the a.tmospheric E.F.V.
curvei to various coil pressures as indicated for the etHuent at 415 psia in Fig. 19-10.
TABLE
19-16.
Per ceht
by volume
50% bp
Gph
In
Fixed gas .........
Cracked naphtha .
Cra.ckeq tar... . . . . .
Gas oil ..... , . ....
Recycle stock. . . . .
Furnace charge ....
Furnace effluent ...
Lb per C.F.
API
hr
(UOP)
Mo~al
Out
-- - -'-
.' .
Mol.
wt
Liq.
vol.
--
19-8
-~
. ....
. ..
...
11.7
10 .6
200
840
720
575
220
860 350
780 330
610 210
...
...
. ..
.. .
11.8
10.6
11.0
....
33
90
..
...
Mo~e
per
hr
-143
l7.t
31
. 94
348
442
696
Figure 4-22 was actually used in raising the E.F.V. curves to various pressures because
the scales that are necessary in such figures as 19-11 a.nd 19-12 cannot be precise.
Zone 1. Consider the last tubes of the still. ' The outlet pressure is 400 psig
(415 psia), and a temperature, after much trial and error, of 912F was selected.
According to Fig. 19-10 and the 'p hase envelopes, about 76 per cent is vaporized at
the outlet of the still. Abou t half of the eracking will be ~one in this zone and the
pressure drop will be about 190 psi. This indicates scarcely any ma.terial will be
vaporized at the inlet to the zone. Note that all of these conclusions must. he checked
by the trialand-error computations which follow.
The a.verage amount of vaporization is (76 + 0) -;-- 2 = about 38%
At 75% cracked, the gas and naphtha constitute 0.75 X 28.3 = 21.2%
Moles at (100
50) -:-- 2 or 75% cracked are: .
= 107 moles
= 131
"'" 89
327 moles
At an average pressure of 510 psia and at 902F, the compressibility factor is about
0.37, but note that an a.verage (rather than the 50 per cent) boiling point must be
used for such a wide-boiling mixture and also that the pseudo critical point of Figs. 5-9
670
1000
~L
--- -- (}i
7
9()O
,.,.
800
~/
I'
2 __
~
~~
'.--7 t I
I ~
V V
_
......
500
V
V, if,; L-V
v ..
f---
~- ...
~~~
:-...-:: ~
./
,.,.-
'S1s_
~ W'
/' i
~~
700
600
--1---
--~
...
~-,.,.
~-
_/
f//
_/
!b"
400
0/Vs
~ 300
I
I
4;, '3
I I
200
I
I
-/00
'/
/ 1/ '/
/'/
-200
100
//
V
10
1- Furnace feed-l8.P.
2- Furno~ f~-F.v.
.J - Furnace effluent-r.ep
4- Furnoc(! el/luent-E.F.lI.
5 - AI 50% of reocliol'l comp/ele - r.B. P.
6 - AI 50% of reaction complele- E. F. V.
7 - Furnace elf/u(!flJ-.F.V. 01 415 psio
20
30
40
50
60 10 80
90 100
Percentage dis1J~/ed
FIG. 19-10. Estimates of distillation and atmoBpheric.fl~h cu,rveB of furnace feed and
effiuent of Example 19-8, and the equilibrium-flash-vaporization cUrve of the effluent
at 415 psia.
379
14.7
1362
Cu ft per sec 0.37 X 327 X 3600 X 510 X 520 = 0.961
"tT
.vO
ume
f I"
'd 0.61
5250
0.934
3600 X 7.48 X (f.6"
= 0.185
lqUl
. 104,200
1
D enslty
3,600 X 1.156
= 25 lb per en tt
104,200
1
3,600 X 0.0575
G2
253,000
::It
671
This is a higher cold velocity (8.4 ft per sec) than thoBe clliItomarily employed (5 to
8 ft per sec), and accordingly, the pressure drop will be rela.tively high in this design.
Velocity: 1.156 + 0.0575 = 20.1 ft per sec
Time of cracking at 904F = In
(_a_)
+ K
a-x
-1
90.5
. 000 2 - 0.111 - 890
t - , n 90.5 _ 9.5 - r . 1 5 - 0.00125 . see
Reaction length: 20.1 X 89 = 1,785 ft
Heated length, approx.: 1,785 X 2%0 = 1,670 ft
Equivalent length, approx. (incl. bends): 1,785 X 1.3 = 2,320 ft
10OO~=t==~===~cjl~tt~==~====j~t=ij~j==~~~==~JOOO
800 t - - - t - - - - + - FlIfnoce -+-O.:H---jL----4---+-+-+--+++++--+--I--+-1r++-----i800
~-+---+--effiuent~~~-4---4-
600
50 % of ~hU-4-I~ Furnace - 600
V 'IIJ
reoel/on is
feed
500 1---+----4--+---IV......-rl~)-#-iIlJB-I--~--4- complete
- 500
400r--+--4--+-~j~~J**~--~-+-~~+_~~~-4_~~~~--~400
II
~JIHI
JOL-~-~-~~~~~~--L---~~~~~uwwu--~~~~~/O
50 100
200
1000
FIG. 19-11. Phase diagrams of the feed, efRuent, and half-cracked material of Example
19-8 (also see Fig. 19-12).
At a. heat input of 12,000 Btu per hr per sq ft of projected area, the duty of the zone
1.9:
less
1,970,000
- 23 5F
T emp rIse
approx .. 104,200 X 0.84 X 0.96 .
672
. '
= 912 - ~ = 888F
= 415 + 187 '"" 602 psi&
1,980,000
2210F
T amp rIse,
approx: 104,200 X 0.9 X 0.96 =
.
This nearly checks the assumed temperature range of 24"F.
L
1850
.
PSl
67~~
900
800
<-
~~
"'""
'"
t
I
500
450
.
400
.:0
.~ 350
'l,f;
~"300 I"-
.~Io~03/d'
r-~
\~e
L
V
V'
,()
~
.r;\j
I/
a'i
~
I
I I
I II
tA
-..;
600
I
I
I.
~{
I
I
/1
II
I~ ~
S?
J
I
I
I
350
I;
40~
100 300
"
1/'
,/
I.
'I
JI
. d'
!
V
~ul/et- J
ryO\:Y
If
It) ,
~IA
L Zone! _
~ ~~
./10
~I
250 1/
1/
.1/ /'1~ ~J
:,
V'
k'.
i1
inlet
~ )1\
~
\ V ' / zone~f::.
V
600
550
150
EFFLUENT
700
~
~
0.:
95%1
vaporized
FEED
Temperolure~ of
FIG. H~-12. EnlargemenL of the pha.se diagrams of Fig. 19-11 (Example 19-8) showing
. .
conditions at the inlet and outlet of zone 1.
Time:
Velocity:
100
In 100 _ 3.2 + 0.00028
0.0315
0.00028 = 112 sec
104)200
1
3,600 X 4i:1 X 0.0575 = 12.25 ft per sec
Travel:
12.25 X 112 = 1,385 ft
Heated length, approx.: 1,385 X 2%'0 = 1,295 ft
Equivalent length, a.pprox.:
, = - 1,800 ft
Heat input: 1,295 X ~ 2 X 12,000 = 5,180,000 Btu per hr
Less IlH D:
15,700 X 0.167 X 670 = 1,750,000 Btu per hr
3,430,000 Btu per hr
674
ENGINEERING
PETROLEUM
3,430 000
1
~~~~~--~
X 12
= 75.7 psi
Psia.
eoil length, it
888-912
866-888
415-602
1,7M
1,423
826-866
703-779
779-947
1 ..... ~ ....
Zone
Zone
Zone 4 .........
'"
.....
..
.I;
"
II<
......
"
"
"
"
....
602-703
700-826
1,385 .
2,740
Examination of the computations of Example 19-8 snows that vaporization is a function almost entirely of the amount of cracking that
occurred, and that Pre&llrC drop4a.s little effect on the vaporization.
It also clearly indica.te~
the densities of the vapors are not greatly
depreciates the effect
different from those of the liquids, and this
of vaporization on the velocity
time in the reaction zones.
Soaking Factor. If the temperature and pressure curVes a,re available,
as in an existing plant or in experimental operation, the so-called U Soak. ing Factor H may be used to compare the effect of various temperatures
and capacities (or velocities) on
extent of the cracking. It is of
little use in the design of stiUs, but it is valuable during oper~tions.
(S.F.)-r50 =
R
f. v R
I)
k"T dV
F
(19 ..23)
675
19-18.
kT/kaoo
EQ. (19-23))
'.
1.03
20
30
40
1.00
1.35
1.87
2 .57
3.47
1.09
1.49
2.06
2 .82
3.78
50
4.61
..-60
70
6.00
7.83
9.92
12.5
16.0
'2 0.3
25.3
31.4
39.2
48.5
58.8
70.3
83.3
97.3
1.06
1.44
2.00
2.73
3 .68
4.87
6.33
8.23
Temp of
800
10
80
90
900
10
20
30
40
50
60
70
80
90
1000
10
20
30'
40
50
60
70
80
90
1100
112
127
144
161
179
198
217
237
258
280
303
lAO
1.94
2.65
3.57
4.74
6.17
8.03
10.15
12.8
16.4
20.8
25.9
32.1
40.0
lOA
13 .1
16.8
21.3
26.4
3'2 .8
40 .9
SO.5
60.8
72.8
49.5
59.8
71.6
84.6 85.~
98.8 100
114
113
130
129
146
148
163
165
183
181
201
199
220
218
241'
239
262
260
282
285
308
305
1.12
1.53
2.13
2.90
I- -
1.16
1.58
2.20
2.9n
4 .01
5 ,)6 .87
1.19
1.23
1. 6-1
1.69
1.26
1.75
1.31
1.81
2.49
3 .37
4.49
5 .84
7.63
9.70
12.2
15.6
2.35 2.12
3.18 3 .27
4.12 4 .25 4.37
3 . 90
5.41 5 .55 5.69
5.00 5.13
7 .04 7.24 7.44
6.50 6.68
9
.04 9.25 9.48
8
.64
8.8-1
8.43
10.6 10.0 11.1 11.4 11.7 11 .9
13.5 13.8 14 . 1 14 . 5 14 .9 15 .2
17.3 17.7 18. .1 18 .5 19 .0 19 .4 19.9
21.8 22.3 22.8 23 .3 23.8 24.3 24.8
27 .0 27 .5 28.1 28 .8 29.4 30 .0 30.6
33.5 34.3 35.0 35 .8 36.6 37.5 38.4
41.8 42 .7 43 .6 44 .5 45.4 46'.4 47.4
51.6 52.6 53.6 54.6 55 .6 56 .6 57.6
61.9 63.1 64.2 65.4 66 .6 67.8 69.0
74.0 75.3 76.6 77.9 79 .2 80.5 81.'8
87.3 88.7 90.1 91.5 92.9 94.4 95.9
110
109
106
108
104
101
103
125
124.
122
121
119
116
118
142
140
139
137
135
134
132
160
158
156
155
153
151
149
178
176
174
172
170
169
167
196
194
192
190
188
187
185
215
213
211
209
207
205
203
235
233
230
228
226
222
224
256
253
251
249
247
245
243
278
275
273
271
267
269
264
301
298
296
294
292
287
289
324
321
319
317
312
315
310
2 .27
3 .08
. ~{
cracking of distillate or gas-oil stocks, and this implies that the material
is in the form of a vapor during the reaction.
Note that k/ksoo is not simply the ratio of the J( values read from
Fig. 19-5 because it contains a correction for the effect of temperature
on the volume of the reacting material. The ratio of k/k'soo must be
read from Tal)}e 19-18. Derivation71 of the Soaking Factor relationship
for gases indicates the following:
= [-ox - (1
~) In (1 - x)]zs
('SF)
'1IiD
14KsoovM
71
119-24)
University of Tulsa.
676
where
~ =
ct
~ 1.0
~ 0.8
~
1/
0.5
a Q4
\.;
lb.
~ 0.3
II)
. ~
~0.2
'='
~ 0.1
a08 7
ao6'
~ a6'
~
100
200 .300
2000
3000
.
PreS'StJ'~ psi '
FIG. 19-13. Stapdard pressure-correction ratios for the thermal cracking of distillate
f~.
'
light gaB oil. The plant studied in Example 19-8 requires a Soaking
Factor of about 0.70 (Example 19-9) and this is representative of values'
for heavy gas-oil cracking. 'There is some doubt about whether or not
the pressure correction factor should be applied to sections of the coil
in whieh nothing but liquid is present (or to viscosity-breaking operations). However, some type . of correction ' is necessary in viscosity
breaking if the pressure is very low (100 to 150 psia).
,
'
E:umple 19-9. Soaking Factor. The coil operating conditions of Example 19-8
will be exa.mined to determine the Soaking Factor. Fig~e 19-14 is a. plot of the coil
volume versus temperature and pressure for the ra.nge above 800~. The integration
ill accomplished in Table 19-19 by the graphical or finite increment method. Columns (1) and (2) show increments of coil volume per-daily barrel throughput. The
a.v~age temperatures are shown in column (3) and the values of k/kaoofrom Table 19-18
677 .
19-19.
(1)
(2)
(3)
(4)
Coil
AV
Temp,
of
/c/kBoo
increments
(5)
(7)
'(6)
Pressure
Pressure,
correction R'X~ X AV
psia
kaoo
F
(R)
"
0.00-0.01
0.01-{).02
0.02-{).03
O.03-{).04
0.04-0.05
0.O5-{).06
0.06-0.07
0.07-0.08
0.01
0.01
0.01
0.01
0'.01
0.01
0.01
0.01
0.01
O.O~.09
- 0.09-0.098
1.64
3.5.7
790
5.69
720
8.03
9.92
' .12.2
640
816
841
858
871
880
889
896
902
907
0.008
911
755
683
605
565
524
480
435
14.5
16.8
19.0
20.8
0.0175
0.0361
0.0540
0.0715
0 .0823.
0.0878
0.0941
- 0.0957
0.0950
0.0700
0.7040
1.07
1.01
0.95
0.89
0.83
0.72
0.65
0.57
0.50
0.42
~aking
Factor
920
910
900
-Temperature
890
' 880
,
~!a)" 870
"
"
~Ib 860
'
~
840
830
820
810
8000
/
/
/
V
.01
800
'-'
./
~850
~.
'"V
/
I ~ "-
"
.......
~ressure ---fP
.02
-" 900
.03
.04 .05
.06 .07
500 '
'~
"
.08 .09
400
.10
Fm. 19--14. Temperature and pressure curves for the graphical integration of Exam..
pIe 19-9.
678
in column (4). Likewise, column (5) shows average pressures for each of the coil
increments and column (6) the pressure correction factors from Fig. 19-13. The last
column shows the integral (area under the temperature curve of Fig. 19-14).
The application of Eq. (19-24)" is confusing on one point, namely, the selection of
an a.verage compressibility factor z. Ho~ever, the results a.re as follows:
8 (Table 19-16) = (696 - 442)/442 = 0.575
x for the mixture of recycle and gas oil = 0.19 (Example 19-6)
" = 1 (usually)
K for the mixture at 800F = about 0.00007
The value of z was 0.37 for zone 1 of Example 19-8, but the material was a liquid in
the other zones. Thus, an equivalent :2 might rlll1ge from 0.6 to 0.9.
(8 F)
754
= [-~x - (I .
+ ~) In (1
14KBOOJl M
_-
X)]Z8
0.85z
z
0.37
0.6
0.825
0.9
S.F.
0.314
0.51
0.70
0.765
PRACTICE OF CRACKING
679
3. Reforming. A high-temperature cracking process that utilizes straight-run gasoline or naphtha as a. charging stock. The cracked distillate has 8. much higher
octane number than the charging stock. The feasibility of the -process depends
upon the market demand for high--octane fuel.
4. Selective Cracking. A process in which the charge 8to~k is separated into several
parts, each part being c~acked separately und~r the most favorable conditions for
that part. Many plants now utilizGJour cra.cking coils: one f01" viscosity breaking,
another for reforming, and two other coils to handle light and hQa.vy charge stocks.
5. Combination Cracking. A process involving the four proe~"CS enlLrnerat'3d above
and one that in the extreme might also involve ~opping of crude coil, ges recovery,
and even coking (see Fig. 19-21).
6. Vapor-pha86 Cracking. These processes s...""e usually more: c){pensivo than the liquidphase processes, and although the gasolin~ hl!S t!. high Od!1!l9 numbar it also contains
large amounts of gum. No proccsecs fol' Pl"OUUClllg gP.soli!Hl r.rQ in operation today.
7. Coking. The operation of coking involves nothing more UUl,n a cracking process in
which the time of cracking is 80 long that coke is produced as the bottoms product.
Special mean~ of collecting and removing the coke -must be provided a.nd a market
must be available for the coke.
J
Smith, J. H.,
Tra.ru;economj~ers,
681l
~-- .-
rn . s ...... - :
681
,j
.
.
.
.
87G-890
920-960
950-990
975--1000
1000-1125
230-250
'300-500
500-700
650-800
1,000-2,000
La.rger yields are obtained in this manner, and for very large plants the
UBe of selective cracking is always justified. In smaller plants the erection
of several pipestills is costly, or the operation of several coils in one fur,usee is difficult, and hence the position of selective cracking is not clear.
Separate evaporators may be Used for each stock, but common practice
is to use a single evaporator into which all stocks are led (Fig. 19-21).
In wide-bailing-range stocks the refractory low-boiling parts are insufficiently cracked at low temperatures, with the result that they accumulate
in the recycle stock-or at high temperatures the high-boiling' parts are
... cracked so violently that coke formation takes place.
Tubestill Processes. Nearly all processes, particularly ' the Donnelly)
the Winkler-Koch, and the Dubbs, discovered at much the same time the
possibilities of conducting cracking in the tubes of a pipestill, and hence
the general process so evolved is referred to as the tubestill process. Practically all the cracking takes place within the furnace 'tubes so that no
reaction chamber~ are required. The success of the process is largely due
,to the production of a clean cracking stock which can be cracked wiih the
production of little or no coke. A small amount of decomposition also
takes place in the evaporator (Fig. 19-15) or flash drum, but this decomposition is not important, except as it aids in' reducing the viscosity of the
pressure-still tar and in producing additional clean recycle stock. The
vapor heat exchangers shown in Fig. 19-15 are a source of difficulty, and
the use of an additional pipestilI heater is a better arrangement.
In order to crack the oil ill the short length of time during which it
passes through the tubes, a high temperature is necessary. The pipestill.
outlet temperature is about 890 to 975F depending on the stock, and.
, the time for cracking is only 2 or 3 min. At these rapid rates of cracking
it is.necessary to lower the temperature quickly. This is accomplished at
"the point marked." quench" in Fig. 19-15 J:>y mixing the charging stock
with the cracked material from the pressure still. Mixing in this manner
is a perfect means of heat exchange, and hence the maximum amount of
h.eat contained in the pressure-stilt product is recovered and utilized" in
vaporizing the .charging stock.
682
PETROLEUM
REFINEl~Y
ENG!NEERING
r~d'rC'Ck'cd
crode
Vapor exchang.!rs or
analhrlr pipe 05;/1/
,
I
r---___.. ,.
Pr~ssure-redLJcing
vo/ve,_
'.. [vapored-or"
Separator
Stove dishl/ale
------+-
or saved far
r~form;ng run
~--Cr.::tcl<ed
fuel oil
FIG. 19-15. Simplified flow diagram of tho tubcslill ctatking Pl"CCcss.
683
ranges from 930 to 970F and the light-oil outlet from 900 to 1050F.
Pressures of 175 to 350 psi are maintained in the reaction chamber and
60 to 130 psi in the evaporator and fractionating tower.
Since about 1935, reaction chambers have been abandoned in all processes except as indicated in Fig. 19-16; and, of course, coke (or reaction)
chambers ftre necessary in coking plants (Fig. 19-19). Vapor reaction
Gas
rracHono+inq
+ower,,-..,
Vopcr
readion
c.hamber
ReskJ wall-wash
and quench
\
Feed
Topped crude
Disfil/ale
fuel oil
Cracked rue/oil
Hecrvy
oil
llghl
oil
_~_.J
Reborler oil
chambers (Fig. 19-16) increase the capacity,!lS octane number, and gasoline yield of black-feed units 38 shown in Table 19-20. Inasmuch as
reaction chambers are cheaper than cracking plants, the use .of 300 to
400 cu ft of reaction space for each 1,000 bbl of feed is economically sound.
TABLE
19-20.
50
100
150
200
8.5
15.5
20.5
250
24.0
300
26.5
29.0
350
a
-~
0
19.0
29.5
36.0
41.0
6.5
0
2 .5
0
2.5
11.0
4 .5
13.0
(i . 0
15 .0
45.0 .
lG.5
47.0
17.5
7.0
8.0
8.5
4.0
5.0
5.5
~I
6.0
6.5
!
01/ !emir ,mel cooler
FIG. 19~17. Twelve-stB.ge hot-oil centrifugal pump for oil a.t a. temperature of 850F and a preasure of 1,500 paL . (Byron Jackwn.
Pump Co.)
685'
, Outlet pressures ,of 350 to 700 psi are maintained at the outlet of the
pipestill. Lower pressures result in the formation of coke; and though we
know little of the phase condition at such temperatures and pressures, it
is apparent that a large generation of vapor takes place even at a pressure
of. 700 psi because vaporization is primarily a function of the critical
temperature rather than the pressure. A pressure drop of 300 to 800 psi
occurs through the pressure still, so that inlet pressures of 600 to 1,200 psi
(as coking occurs) are common. Twin-simplex, compound steam cylinder
, pumps or crank-and-fiywheel steam-engine pumps were once widely used,
but multistage centrifugal pumps are, now standard practice (Fig. 19-17).
The tubesti)l process has been used for vapor-phase cracking without
fundamentally changing the process. However, the qutlet temperature is
much higher (1050 to 1250F), and the outlet pressure must be reduced
to 30 to 50 psi so that substantially a pure vapor phase exists in the
'cr~cking tubes. Likewise the best known continuous coking processes are
like the tubestill process except that coke drums are introduced before
.the evaporator vessel of the tubestill process (Fig. 19-15).
In processing topped or reduced crude oil, the maximum yield of ga.so. line is l~rge]y dependent upon the properties of the pressure-still tar. If
. too higb an evaporator. or vaporizer temperature is used or if the time in
the evaporator is too short, the tar may be a solid asphaltic material, .
which is awkward to handle and cannot be marketed. In processing. gas
.oil, this difficulty seldom arises because the tar consists almost entirely
of cracked tar which has a lower viscosity. However, an evaporator
temperature of about 820F cannot be exceeded because coke will ' be
deposited in the evaporator. It is now almost universal practice to avoid
these difficul.ties by flashing the cracked ~uel oil or residuum at atmospheric or subatmospheric pressure (Fig. 19-21). This produces an almost
solid, very low gravity residuum, which is diluted or cut back with a small
amount of light cracked distillate to produce a black fuel oil of. suitable
viscosity (300 Furol sec at 122F). The flash characteristics of one
14 API residuum when being adiabatically flashed from,820F (in eyaporator) are indicated in Fig. 19-18. 74 The heavy dashed line shows the
percentage of residuum that will be vaporized as the temperature is
reduced to various temperatures lower than 820F. Obviously, the
pressure must be reduced to 10 psig to vaporize 45 per cent, or to 200 mm
vaporize 77 per cent. At the evaporator pressure of 65 psig none
.of the residuu_~ is vaporized. In computing the curve for an adiabatic
vaporization (Fig. 19-18), the following operations are necessary:
to
686
3. By a heat ba.lance compute the decrease in temperature from 820F that will occur
in vaporizing the 45 per cent. This temperature is 774F.
4. A temperature of only 731F at atmospheric pressure is required to vaporize 45 per
cent, and hence a pressure of 10 psig (Fig. 5-27) is required to raise 731 to 774F.
5. Repeat for other percentages vaporized.
20
I...
900
"-- ><
.........
.,.-
......
...
~- "
..,(jDIABA'rIC PERCENT
TEMP. & PRESS:
- ----,-
---
--'"' -- ;//
,. ~-
. ":><..:'
~
600
II
"
500()
.., ~
./
-"
.,~
10
-"
-"
."
16
FLASH VAP.
AT 10 P.S.I,G.
f"'~
~
/'
, L __ ;; .
. .;.-'"
--.,.
,,"
12
<ASHVAF
AT 760MM .
......
."
14
'"
' .. ~
~
A.s.T.M. CURVE
< ~-
.,. ,,-"
r--
1--
18
~,.x
-"
-...
,,
fLASH vAp.
AT 200 MM
.,B
,,
20
30
70
40
60
50
PERCENTAGE VAPORIZED
80
90
FIG. 19-18. Adiabatic va.poriza.tion curve of one 140 API cracked residuum, and the
ClOnstruction curves used in computing the amounts of vaporization.
Yields are so similar from all the processes that Fig. 19-1 and Eqs.
(19-1) to (19-8) should be employed rather than scattered data. on the
various processes.
Coking. The production of coke is accomplished by lengthening the .
tIme of liquid-phase cracking (Fig, 19-6) so that polymerization or condensation products are produced. However, only the most degraded
carbonaceous high-boiling parts of the cracking reaction are exposed to
687
n8.
Court, 'V. F., Hydraulic Dccoking of Coke Cha.mber, Proc. API, Refining Diviai.{Jn, Chicago Moo(;inK, 1938j a100 'Vntson, K. M., Cracking Fuel Oil to Coke, Ref.
Nat. Ga&o. J.ljT., Dec. 1, 1038, p. C52.
il
I85,SOOI/Ylv
820"F
ComiJlnollon
lower
40psiq
40psiq
..'
..'
~n/
150~F
II
..
'I
411!
920"F
l25"F
:Jpsig
L----------"1
WcIfer
Wafey
I
I
I
I
I
I
I
J
~iI6S'F
I
I
I
,
I
ft!1:!t"~
woIer .
I
I
I
Colre
J3,3()()~
tf(}Ol/d
"F'
Redwed
crIIf/e
Z4,!KJOMxI
.J.J4pX) fib
GC:zs oil
1.9,!JOO I;fod
~600*
!IO.I"IJPI
2f.6"AP{
'=
'.05OIi'bd
JJ,UglMlt
!J8.YAP.l
(Pet. Ihfiner.)
We/gas
20,..
f5,,561""
JO. 8 111."-
689
and broken from the walls and falls into a sluice system for dewatering,
drying, and storage. 78
The Knowles or similar coking ovens that have been used in the coal
industry have been used also for petroleum. They involve increased
flexibility in operation and produce a uniform bigh-quaHty coke. 79 A
cracked fuel oil, which has been flashed down to. a gravity of 1 to 2 API,
is introduced slowly into the oven for about 100 min or until a 10-in. layer
of coke is produced. The coke bed is qried by heating for about 3 hr,
reaching So final temperature of 1200F, and is then removed by opening
doors at both ends of the oven and ramming the hot coke into a quench car
by means of a large mechanical ram.
Almost pure carbon or artificial graphite, which is suitable for carbon
electrodes, motor brushes, dry ceBs, etc., can be made by calcining petroleum coke. 80. In this process, the refinery coke is passed through a 100- to
125-ft cylindrical rotating kiln by which it is heated to a bright red heat.
Completely continuous coking systems (Continuous Contact81 and Fluid
Coking 8Z ) were developed during 1949 to 1955, and these promise to
revolutionize the coking art (over 500,000 bpd capacity, 1956)83 and
possibly the economics of residual fuel production. In these processes,
coke is built up on pellets 81 or on fluidized coke particles 82 until a size
suitable for removal is attained. Meanwhile, the smaller particles are
retained within the system. In the Fluidprocess 82 shown in Fig. 19-20,
abc;mt 5 per cent of the coke yield (on feed) is burned in a fluidized coke
bed to dry the coke particles and to heat them (1100 to 1200F) for the
reaction chamber which is also rp.aintained in a fluidized state. The
reactor operates at 900 to 1050F, and the pitch-type feed is also introduced and, heated in the reactor. Reaction products are separated in a
fractionator system situated just above the reactor. Fluidized coke has a
gross heating value of about 14,300 Btu per Ib and its size distribution 84 is:
Screen size
8
35
5.2
11.1
65
48.6
100
200
80.1
95.8
Breese, F., Drier, Cleaner Petroleum Coke, Pet. Processino, August, 1953, p. 1170.
Foster, A. L., Lubritc Converts Fuel Oil into More Profitable Products, Natl. Pet.
News, May 6, 1936, p. 33.
80 Stockman, L. P., Fir8t California Calcining Unit . . . , Oil Gas J., July 4, 1940,
p.36.
81 Mekler et al., Oil Gas J., Nov. 16, 1953, p. 200.
n Anon., Coke' and Lighter Products, Pet. Processing, March, 1956, p. 135. .
as Weber, G., Oil Gas J., Aug. 8, 1955, p. 62.
atCornforth and Lee, Fluidized Coke Tested in Rotary Kiln, Oil Gas J., Sept. 12,
1955, p. 137.
18
1S
fUflGA$"
GAS OIL
COKD.
GASOliNE
flUID!IN>
COICElfD
TOTAl. GASOlNt
c:.
)
o
(CAr .. COI:EIl
SLURI... nevaE
PITCH
... faD
IUCfOI
(Pet. Processing.)
691
'.~'
------
----Ar--~-
~------------------------~B~u~m-n-e~
propane
stabUiiter
Cracked'
. , .stripping
I stllt gases
gas
(Oletina)
Wnd
... rdaft,f .. _ ..
I
I
t
t
r~
All
I
I
I
I
rc.ft;;;ch'7
I
stock
lI ,
Additional
woIing
quench
,,
I
J Return ofcold
t.,!ablHzerand stripper
or fuel oil orc;asphalt
Lighj
premIum
gasoline
------.
I
PO
illustration of
th~
interrelationship between
many opera.tions
Premium craCked
ana
Polymer 901soUne
can'be conducted
------------'---- .
.Dry gas
to
fuel line
a combina-
693
East.Ten.
M.O.
erud8
crud~
a4l.9
API
-.-,.,-... ..
,
\
I
--
Mlch-iran
erud&
API
~-
28.9
18.6
10.6
.... .
7.7
12.4
69.2
S3
36
None
26
20
42
N~e
63.0
12.0
20.0
67.S
68.3
64.2
09
None
68
5.0
JO.2
.. "
24.2
C.!
26.1
10.7
9.6
63.0
25.0
8.0
63.0
66.0
....
70.6
.......
API
89;9
43.7
83.4
. ....
....
4.3
.. .
68.0
70.0
9.2
66.0
66
70.0
CHAPTER
20
REBUILDING HYDROCARBONS
695
REBUILDING HYDROCARBONS
heat
CH aCH 2 CH 2 CH a ----+ CH 4
n--butane
+ CHs'CH: CH
metha.ne .
propene
II Lane and Weil, The Synthine Process, 4 parts, Pet. Refi?UT, August, p. 87 j September, p. 97; October, p. 109; and November, 1946, p. 153.
10 Keith, P. C., Gasoline from Na.tural Gas, Oil GM .J., June 15, 1946, p. 102.
11 Roberts and Phinney, . . . Synthetic Gasoline Nearing Commercial Application
in U.S., Oil Gas J., Mar. 15, 1947, p. 72.
12 Rushton and Stevenson, Developments in Oxygen Production, Chern. Eng. Progr.,
43, 61 (1947).
18 Linden a.nd Reid, Pet. Refiner, June, 1956, p. 189.
696
t-
MEtlCAPTANS
HYDkOGEN "
UREA
JunUlU5
AUINOPlASU
llHANOLAt.4INl
RESINS
AlCOI-tOU
AlDlI-tYOU
KUONES
GIIA RUUU
OUON
e.HfMStIlANO
WEED
I(llltlt~
SOlV~NTS
NEoPUNE
POt. YETHYlEN
SUlfUR
SULFURIC ACID
ETHYI..lNl & YCOl
AClYlATE PlASlICS
AeErle ACID
NATURAL GAS
Acnae AHHYDRIOE
LIQUIDS
REANEIlY
LPG
VINYL lE51NS
SOLVENTS
TETJlAITH't'l llAO
RF lUGE tAHTl
AUOSOU
NAPHTHENIC ACIDS
OIESVlIC ACID
SULPIfONA.lfS
SARAt.i
ACITONE
EXPLOSlYlS
DETERGaoITS
5YNDflS
aUJYL IUllO
POL YSTYltiNi'
NYLON
AOHlSt~ES
RESlHS
PETROLEUM
ASIDUAL OILS
L~~~.J"',=--TUEtH'HALIC ACID-----"'~~-_y
~~~~~~~P:H:Tli~AL~IC~AN~HY~D.~r~~~::~~~'AINfS
INSECT'CIDU
LACQUERS
INUCT WllUNtS
FUNGICIDU
.__f[~PfTCH~!}~_-================CARION
ELECUODS
'IICH lUINS
FrG. 20-1. Some of the petrochemicals that can be produced from na.tural gas, na.tural"
gas liquids, a.nd petroleum. (Pd. Refiner.)
\
697
'REBUI{,DING lIYDROCAlmONS
CHsCH~CH2CI-Ill'CH3 ~
catalyst
CH lI CH 2 CH 2 CH :'CH2
n-pentane
pentene-l
H2
hydrogen
nrhepta.ne
toluene
hydrogen
butene-l
h~tm
cata.lys:
eRa
Such reactions permit the manufacture of liquid gasoline from gases and
in special instances the production of tetramer (dodecene), non ene, polyethylene, and polybutenes.
Likewise, some unsaturated hydrocarbons may be depolymerized. 16 18
Thus, during World War II, isobutene. was polyme,rized to isooctene
Archibald and GreensIelder, Promoted Chromia-alumina. Catalyst . . . n--Heptane to TolueneJ Ind. Eng. Chern., 31, 356 (1945).
15 Doumani, Deering, and McKinnis, Depolymerization df Butadiene Dimer, Ind.
Eng. CMm., 39, 89 (1947).
.
14 Reid and Bailey, Thermal Depolymerlzation of V18COUS Isobutylene Polymer,
Ind. Eng. Chem., 40, 349 (1948).
14
698
which can be ship-ped in regular tank cars because it has a low vapor
pressure and then depoiymerized 17 to isobutene again at destination.
Depolymerization
2,2,4 trimethylpentene
isobutene
6Ha
ethene
6H3
i-butane
2,2 dimethylbutane
H2
H2
CHa
H'('6H
HOH. alumi.um
H
H1
H 2--H 2
Ht
cyc10bexane
methylcyelopentane
Not many commercial processes of this type are available, but such reactions probably occur along with other reactions such as cracking, poly-'
merization, and alkylation but canno.t be recognized because of the other
reactions and because
the difficulty in identifying the hydrocarbon
products.
17 Murphree, Brown, and Gohr, Hydrogenation of Petroleum, Ind. Bna. Ckem..,
32. 1203 (1940).
18 Kutz and
Dealkylation of Dialkylben.zenes, Ind. Eng, Onem.} 38, 761
(1946).
699
REBUILDING HYDROCARBONS
HaC CR 3
HsC CHa
I I
I
CHa'C'CH'CH:CH Il
lybd '
roo
10)
oxide
H2
I I
I
CH3.C'CH.CH~!,CH3
HaC
HaC
2,2,3 trimethylpentene-4
hydrogen
2,2,3 trimelhylpentane
It has already been used in connection with thermal decomposition (cracking) as a means of adding hydrogen to the residue of tar that is produced
in cracking so that greater yields are possible. When used in this way
it is referred to as destruCtive hydrogenation.
Many reactions of hydrocarbons with other agents such as oxygen,
water, halogens, nitric acid, etc., are practiced commercially .but can
hardly be claimed as petroleum refinery operations even though the hydrocarbons came originally from petroleum. Direct oxidation has been practiced for many years 19 in the production of aldehydes, ketones, alcohols,
and acids. Direct oxidation processes usually produce several products
.a t the .s ame time,20 but the reaction shown here serves as an illustration.
Oxidation
heat
B.Dd
catalyst.
methane
formaldehyde
oxygen
water'
The hydration of oletins has long been practiced for the manufacture of
amyl21 and isopropyl alcohol,22 and more recently for ethyl alcohol.!!
Hydration is usually accomplished by a series of reactions involving the
chlorides or alkyl sulfates, rather than the direct hydration reaction indicated here.
Hydration
ethylene
water
ethyl a1cohol
700
Kind of pbyaical or
chemical ebaqe
Moleeuw
change
(3)
(~)
ED ergiw,
catalytic
(6)
or
tbermal
Disintegration
(breaking in to
Desulfuti..ution and
{'A/ota!yst
hydrog&natiOD
DehydrogAnatiOD
Catalyst
Deoompooition
Catalyat
Jl8lts)
in,
Cataly.t
Cyc.1overalOQ
Gas oil
Thermal
ThermAl
Thermal
Thermal cracldac
R.eforming ,
Coking
Polytocming
Destructive hydrolenatio.ll
integration and
8)'Dtbeaia)
Many Itocb
~t.ioD
Deeompoeition, hydro-
Catalyat
Hydrodellulfuriutlo.ll
Catalyal
Thermal
Th~
Catalyst
Thermal
HF alkylation
Sulfuric acid alkylation
(No common name)
(No common name)
Thermal alkylation
Catalyst
Cataly3t
Catalya~
Cabl,v!t
Catalys~
Alkylation
Catalyst
Ca~'8t
Synthesis
(uniting)
Hydrogenation
polymerizatiol1 .
aso.
Han
l.earrangement
(of mole
laomeriHtion
structure)
ID main reaction.
Catalyn Iaomate
180bnbme
Napht.ha, pentabb, 01' hllDDI
Catalyst
Butano ilomerization
~ubDe
Cat.a.\ya\
(Several namea)
PenlaDe or Ileune
'
701
REBUILDING HYDROCARBONS
MODERN REFlNING PROCESSES
(8)
(8)
(7)
(9)
(10)
OpemUng oonditiooB"
General purpose
Main product
Illustrative reaatioo
Pai,
Remove aultur
Remove sulfur
Mike olefin
DiBl.ill&te
Gasoline
R(SH).., R + Uta
ButeDlI or but.diene
Fuel oil
+ HI -
c..H2,,+t = C../tH.....r
800-700
40-70
Low
760-780
700-800
236-2~
866-890
20-60
8Il0-860
_ Catalytio gaao.
2-15
880-950
line
Cobalt molybdenum
Bauxite or clay
~H60
Cbromlll oxide
bal1lite
OD
+ c.."H"
Tamp, OF
Catalytic pao-
minum bydrosili
oatM, bauxite,
line
Catalytic p&O-
16-15
160-900
liDe
Cataly& gaao-
60-100
900-1100
300-700 6
400-800
88().-95()
96(H020
89tH180
eta.
line
Make gasoline
Elimimte fuel oil
Cracked p.soline
Cracked gasoline
Chcked gasoline
GasoJioe
Aromatics
Aromaticl
Bo!veotll
GaaoIiDe
Pamftinii:: atoeb
MIUlJ'
MabpadiGe
300-500 b
I,OOO-2,OOO~
100-300
~750
eIlH,,, +'J
+ Ht ""
GaBon
Aromatlo h)'drocarboDs
Toluene
Recover gases
Poly P801ine
Hlght&ne psoJiue
Bigb-oetane guo.ljne
Bigb.t:lne psoiI.M
Needed lor It:yrene IUId
Alkyla&e
Alkylate
'100-1.000
EtbylbenseDe
Recover paes
Neohexane
Hilbtunc blendiug
ISQocl.alle
CaRu + Ht - c.H1I
Recover pses
Poly gasoli II e
2.3(CIlHtoo.) = Ct.a..H.....
Recover paM
Poly gasoline
z{C,.Ha..} - C_Hb ..
Codimer
synt.hetie rubber
Btock
imoe~De
BiKh~e
gaeoline
BraDched-cbain hydM.
carboni
Bigh-octaDe II*8OIiDe
Mo~
890-1020
86G-970
Platinum
8OII-D50
Molybdic trioxide
750-800
Cobalt molybdenum
1020
Chromic, molybdic,
etc., oxide.
,
Produee gas oil
Curnene
3,000
102<>-1120
Low
1,500--2,000
900-1025
1000lliO
76-11&
1~
3~O
~O
15
150-210
8,001>-8,000
900--1000
16-60
320-400
Nickel
300--600
3OCHSO
Phosphoric: acid
7G-190
35O-MO
Hydrofiuoric acid
Sulfuric acid
Phosphoric acid
AlumiullDl chloride
Sulfurie acid
350-500
Phosphoria acid
12~200
1~220
200-350
HIO-210
Aluminum chloride
Aluminum chloride
nC~u"" iC~Jt
lfllh
800-900
Platinum, eta.
Isomate
702
C1 2
chlorine
CH:rCH 2 CH 2 CH 2 CH 2Cl
HCI
hydrochloric acid
amyl chloride
nitric acid
nitromethane
water
REBUILDIN,G HYDROCARBONS
703
for constant-volume reactions (nearly true for liquids), but they become
cumbersome and nearly useless as a means of correlating data if the
volume is not constant, as is the case for, many gaseous reactions. Fortunately, most reactions are not conducted to completion, and hence
at yields' per pass of 25 or 50 per cent the failure of the volume to remain
constant does not introduce serious errors. In all the derivations that
follow, the reaction is assumed to be taking place at a constant temperature. Perhaps the greatest usefulness of the following derivations is to
point out the general mathematical fonns to use in developing empirical
formulas of the rate of reaction.
Rates at Constant Volume. For a unimolecular reaction of which pure
decomposition is an example, the rate of reaction is directly dependent on
the amount of re~ctant material that is left at any time during the
reaction.
The rate at which ,the concentration of A decreases with time is a constant
function of the concentration' designated as CA =
-dCA
dt
k1cA
and by integration
1
a
kl = - I n - t
a - x
(20-1)
When possible it is best to use the concentration in moles, but liquid volume or weight per cent can be used with fair accuracy (see Fig. 19-5) for
first-order, or unimolecular, reactions.
Similarly for bimolecular (second-order) reactions at constant volume,
pressure, and temperature
A+B~D+E+
dx
-dt
= k 2(a
and
k2 =
x)(b - x)
1
t(a - x)
In b(a - x)
a(b - x)
(20-2)
in which a and b are the initial concentrations of A and B in moles per unit
volume and x is the number of moles of A and B that react with one
704
another during a. time t. In the special case in which A and B are present
in stoichiometric proportions or if two molecules of the same material
react with one another (polymerization), the second-or~er equation
simplifies to
2A ~ D + E + .
dx
-dt = k2(a
'
X)2
1
X
k2 = - ---:-----:-
and
t a(a - x)
(20-3)
Note that pressure enters into the reaction velocity constant. for gaseous
reactions as an inverse functJon because tl;le units of a, b, and x are moles
per unit volume (or density).
The order of a reaction may be determined by inserting experimental
data in the. equations and noting which equation gives the most constant
value of k. A discussion of other methods of determining reaction order
and a discussion of the kinetics of higher order reactions are given in the
"Chemical Engineers' Handbook."27
Rates at Varying Conditions. In most gaseous reactions the volwne
does not remain constant and modified equations are required. Note,
however, that, if the conversion per pass is low or the system is diluted
with some unreactive material such as a recycle stock, the volume change
may be 80 small that the reaction behaves essentially as a. constantvolume
one.
.
In the case of a unimolecular reaction at a varying volume 27 the constant is
vV
1
V
'(20-4)
kl = -V In 'l
- -V (v - 1)x
,
It
T
2T
o"
IDle -:
reaction space
1
volume feed per unit time - space velocity
Perry, J. H. (ed.), 3d ed., McGraw-Hill Book Company, Inc., New York, 1949.
REBUILDING HYDROCARBONS
705
However, many different units of time, etc., are employed, and hence,
whenever space velocity is mentioned, the particular units must be noted.
If the volume or temperature (absolute) is assumed to vary according to
a linear function, the time can be approximated by using the average of
the inlet and outlet voiumes rather than the volume of feed.
In systems in which the temperature varies, the rate can be described
approximately by equations such
Eq. (20-3), but the situation can
, usually be handled more accurately by means of a series of computations
each of which embraces a short range of temperature. Each short
range of temperature can be handled at a weighted average temperature
(refer to Example 19-9).
Effect of Temperature on Rate. The effect of temperature is to double
the rate for a rise in temperature of about IOoe. The influence of temperature is, however, a function of the particular reaction. The change
in reaction' velocity with temperature can usually be described by the '.
Arrhenius equation:
as
dInk
dT
= RTZ
-A
In k = RT
+B
(20-5)
-A
or
k = BeRT
where A = a characteristic constant (- 53,500 cal per g mole for gas oil)
referred to as the "energy of activation"
T = absolute temperature, C
R = the gas law constant (1.987)
B = a constant (about 28.8 for gas oil)
A convenient way of correlating data is to plot the logarithm of the
reaction velocity constant va. the reciprocal of absolute temperature.
This yields a substantially straight line (Fig. 19-5) having a slope of
-A/2.303R.
M: D. TiJicheyev and others 28 ha.ve determined the rates of reaction of
many hydrocarbons when they are heated. This work has been digested
by R. Rosen,2I and he presents tabulated rates for normal paraffin, olefin,
diolefin, indene, styrene, aroma.tic, alkyl benzene, alkylated polycyclic,
and naphthene hydrocarbons.
.
Anon., Kinetios and Chemistry of Cra.cking Hydrocarbons. OilGa8 J., Feb. 13 a.nd
Feb. 20, 1941.
lIa
706
THERMODYNAMICS OF REACTIONS
Many of the hydrocarbon-conversion processes are still in the development stage, and this is particularly true of the higher-molecular-weight
. materials, which constitute the bulk of petroleum. For these reasons, it
is of primary importance to be able to judge the feasibility of proposed
reactions or processes and to compute (or estimate) other thermal factors
such as the heat of reaction. These fa.ctors can be evaluated by means of
thermodynamics, and in time it may be possible to develop processes by
which whole series of hydrocarbons can be converted into other series of
hydrocarbon~ in a selective manner or by a number of consecutive processes to convert one series of hydrocarbons after another, until the entire
mixture is converted into a single type of material.
Feasibility of a Reaction. The possibility that a reaction may occur
can be judged by means of the free energy of the materials that are
involved in the reaction. The free energy change may be considered as a
measure of the tendency of a reaction to occur. The standard free
energy change designated as M'0 may be defined as the free energy change
of the reaction if e~ch of the materials involved in the re~ction is assumed
to be at unit activity. Mathematically the free energy, mass-law
equilibrium constant, and thermodynamic constants are related by
Mi'0
where
RT ln K = flH - T flS
(20-6)
T = absolute temperature
K = equilibrium constant (mass law)
R ' gas constant = 1.987 ca1 per mole-deg
If the value of ilFo is found to be negative, the value of K will be relatively
large and the yield will also be large when and if equilibrium is established.
A.s M'0 approaches zero or becomes positive, the value of K and of the
yield at equilibrium becomes smaller and smaller. If flFo is negative, the
reaction is a promising one; if M'0 is zero, the usefulness of the reaction is
doubtful but may justify further study; but if the value of I1FO is greater
than 10,000, in most instances such a process would not be feasible. It
will also be noted that temperature exerts an important influence on the
value of t:Jj'0, and hence the foregoing situations may be altered by the
use of another temperature.
.
No idea of the rate at which the reaction will occur is possible from a
consideration of free energies, and hence many of the reactions that are
found to be thermodynamically feasible do not occur at a practical rate or
they may require the Use of catalysts or an activating influence in order to
~-.:-.-~~
707
REBUILDING HYDROCARBONS
+ bB + .. . . = cC + dD +
c
K =
(20-7)
aCaD
b
aaa
AB
+ 25.2nT
- 2.2T
5,835n
+ 24.52nT
- 33.26T
= 10,375 - 8,633n
+ 26.09nT -
15.9T
70,425 - 8,633n
+ 26.09nT
- 67.5T
"Chemical Process Principles," part 2, John Wiley & Sons, Inc., New York, 1947.
Thomas, Egloff, and Morrell, Thermodynamics in Hydrocarbon Research, Ind.
Eng. Chem., 29, 1260 (1937).
al Francis and Kleinschmidt, Application of Thermodynamics to Chemical Reactions of Petrolel1m Products, Proc. API December Meeting, 1929.
29
10
!
\
= 10,550 - 5,890n
~ = 20,321 -
I
1
!
I
708
A somewhat more useful type of approach 32 involves the use of the free
energy change required to produce various bondages (even branch-chain)
such as those given in Eqs. (20-8) to (20-11). In all these equations n
refers to the number of carbon atoms and T to the temperature in oK.
C-H bonds u
~p;.
= -
3,344.5
+ 2.97T In T
C-C bonds u
~
4,437
- 0.0023T2
+ 0.OOOOOOI88T' - 13.6ST
...
~.
+ 0.421 T In T + O.0017T2 -
O.OOOOO062T'
+ 9.53T
C=c bonds:J2
~
(20-8)
= 28,024
+ 2.75T In T
C-CH a bonds
- O.0014T2 - 0.00000080T3
- 24.86T
(20-9)
(20-10)
32
a?;. = -7,62,4
+ 10.42T In T
- 0.0057T2 - O.OOOOOO15T3 - 36.12T
(20-11)
CHa
6Ha
bHa '
31 Bruins and Czarnecki, F~tion between Structure and Free Energy ot Organio
Molecules, Ind. Eng. CJ..em., a8, 2G1 (1941).
aa Pitzer, K. S., Chemical Equilibria., Free Energies and Hea.t Cont.ents for Gaseous
Hydrocarbons, Symposium on Fundamental Chemicru Thermodynamics,. ACS Cincinnati Meeting, April, 1940.
U Parks, G. S., Some Free Energy Data for TypiceJ Hydrocarbons . . . , Symposium on Fundamental Chemical Thermodynamics, ACS Cincinnati Meeting, April.
1940.
31 Thacker, Folkins, and Miller, Free Energies of Formation of Gaseous Hydrocarbons . . . J IntL Eng. Chmn., S3, 584 (1941).
~. API Research Project 44 of the National Bureau of Standards pertains to nearly
all important physical and thennodynamic data. on hydreca.rbOllB suoh sa boiling point,
va-por pressure, critical Qonst~nts. viscosity, entropy, he.a.t of OO.mbustion, etc.
REBUILD~G
TABLE
2()..2. FREE
709
HYDROCARBONS
Substance
Formula.
ARC,
(heat.
or orma.tion,
29SOK)
flFO a. t. l0000K
- -,
Methane ...... , ......... CR,
CtHt
CIH.
C2H.
CsHt
CaR.
C.H.
C,H.
C,Ha
C.H.
CtH.
C4HIO
C.HIO
C6H.
CSHll
Cr.HI!
n- ent&De ........... e~HII
Tetramethyl-met.h.ano . , " e,HII
Benr:ene .............. " C,HG
~elohenne .......... '... C.Hla
exene:-l. ............... CoB.,
~clohexane ... " ......... CoB.,
et.bylcr,dopent.ane ..... , CeRl1
2-~etby pentane ........ C.Hu
ft- BeXJUle ................ CJlu
2,2-Dimethylbutane ....... CaB"
Toluelle .. ; .... , ........ CTHs
H~teDe-1. ... , ........... CTHu
E
1~e1~ntue .... C,Hu
Met y
ohexane .... C,H"
2-Metby henne ........ C,Hn
3-Methylhexane ......... , eTHI.
3-Et.~lpent.a.De .......... C,H ..
2,2Dlmethylpentane ...... C,H'8
2,3-Dimethylpent.ane ..... CTHu
2,4-Dimet.hylpcot.aD6 .... C,Hlf
-1.3-Dimethylpent.ane .... C,B,.
2.i,3- TrimetJiylbutane ... - CTH"
n-BeR,t&ne ............. C,Hu
E~ ~De ......... CaHill
~ ylene ................ CUI10
DllsobutMe
bp) ....... CIH
Diiaobut.ene hifth bp)'. , \ CaH,.
2,2.4-Trimetby ptmtane .. , . Cill ..
~OCt.e.n8 ...... , .... CaHu
n-Nonane .......... C.Hto
n-DecaDe. '" ....... C.oHu
2-Methylnonane ...... ClGH ..
D~lene-2 ....... CloHto
~Bu t.yloye1ohezane .... C.oHIO
n-ButylbeJlJl8n8 . CIOHI.
Naphthalene ... , .. _ C,oH.
Undeeane ....... ClIHu
Dodeeane ... , ...... C,JiH
n-Heptylc:yolohuane ; CuHu
An thi-aeene ......... CHH.6
llexade~e .. , .. , CuHu
I>otriacoD~e ...... Cal H n
Acetylene ...............
Ethylene ................
Ethane ........... , ..
Propene ......... '........
Propane .. " ., .... , ..
Butadiene 1-8 .... , . '.
Iliobu tene . .-........
Butene-I. ...-.........
Butene-2 ~ci8) .............
Butene-2 trana) . , ..
Isobutane ........... , ..
""Butane .... , ...........
Pent.&diene 1-4 ............
Pentene-l. ..............
I 8~en t.a.ne. . . . . . ~ . . . .
Qt
90w
-17.860
58,228
12,55G
-20.191
' 4,956
-24,750
26,865
-3.205
aS3
-1,388
-2,338
-31,350
-29,715
25.&M
-4,044
-3Ii,G71
-34,739
-39,410
........
.......
I
........
........
"
-41,800
-40,010
-44.400
.......
.......
.........
47: ioo
::.........
::49:800
.........
..........
a
It ,
10
-45,350
.......
......
...........
...........
-56,200
-50,700
..........
........
.
,
......
........
'"
..........
.........
........
.......
...........
, .........
It
It . . . . . .
.. I
......
-12,300( ~ 12,OBS)
5O,840(50.oa,}
15,820(16,279)
-8,260(-7,'787)
14,820(14,730)
- 6, 220( - 5,5-50)
(33,960)
lU40)
24
'4.
16,780
16,810)
14,860 15.5iO~
14,460 14,800
-4,900 -4,IGO~
-5.000 -3.630
40,220
17,800
- 4,230~ - 3, 190~
- 2,570 -1,(;20
-4,500 -a.alO}
30.340
19,400
19.200 '
8,030
3,700
(-1,000)
-1,500(80)
(-2,800)
28.400
20,720
8,000
4.280~~
-1,300 00)
-930
-130
-130(-300)
-480 370
-730
870
190(1,750)
28,090(l)
29,660
),,,or
21,530
22.260
O)
1,520 3.400)
2.280 l)
3,490 ~
-8.0501
~ ',""0)
48.100 4'1,160)
18,520 18.830)
1,960 -W)
22.510 20,930)
'7,540(5,640)
(40,000)
2O,9iO(2lt,WO)
~,440~27,OOO)
27.440 26.~U}
27 ,390rS,(40)
14,670 11,440)
13,500 11,070)
57,000
36.000
19,850
21,040
21,180(11.760)
38,700
3,450~3,450)
41,300 40,850)
27,670(20,700}
25,790(21,190)
43,3S0( 4O,340}
46,200( 41,300)
(OO,DOO)
62,780(68.720)
62,960~58,230~
60.800 58.590
61.650(58,240~
67,350{60,680
63,170(58,300)
so. 000
85,300
85,670
9O,950(84,O20}
09,600
32.100
42.000
34,600
21,500
99,100
103,500
28,000
108,000
41,200
48,720
74,200
118,400
35.700
36,350
37,050
38,300
37,100
38,500'
37,300
40.000
35,000
122,500
47,300
66,090
9'2,800
146,700
150,200
58,450
46,000
40,000
141.600
2,000 I
24, lOO U>
7,000
2{).670~1
41,430 4)(50,4.00)
4.310(1)
62,000
93,500
89,200
135,000
n,580~
9,530
64,100 (72,400)
lO, 710
31,300 I
710
14,820
-4,900
-130
C aH6(g)
iC,H1oCg)
C 7H I6
For the entire reaction:
LlF~98 =
AF~oo =
-10,050
-RT
-10,050
17
-= -1.987 X 298 =
Ln Kr.oo =
K"oo
Let
x = moles of C (or C 7 Ha) in reaction products per mole A introduced
Moles A = 1 - x = moles B
At equilibrium and for a pressure of P = 1 atm:
0.3236
= (1 -
:z; =
x/(2 - x)
:z;)2/(2 - xp p
x(2 - x)
(l - x)'l P
0.131 moles
Percentages of C 7H 16 in products:
Total moles after reaction = (1 -:z;) + (1 - x) + x = 2 - x
0.131 X 100
Percentage = , 2 _ 0.131 = 7.0 per cent C,H 16
This is not an economical yield in most instances.
Values at other temperatures may be estimated by assuming that. flFo is a linear
function of temperature; i.e., 1JJI o """ aT + b. The constants a and b in such a.n equa.tion may be evaluated thus:
at 298 0
at 5000
subtracting
and
- 10,050 = 298a + b
1,120 = 500a + b
-11,170 = -202a
a = 55.3
and
b
llF o = 55.3T - 26,530
= -26,530
711
REBUILDING HYDROCARBONS
if in this instance a
yield of 30 per cent is feasible by practicing recycling, the temperature a.t which the process can operate can be estimated as follows:
Moles of C , H l6 produced when 1 mole of A is processed:
lOOx
30 per cent = 2 _ ~
x = 0.4615 moles of C7 Hu
'l'b'
K = 0.4615(2
- 0.4615)
E qUll
rlUm constant =
(1 _ 0.4615)2
Also
1 K
n
= 09
.
2 46
=.
-RT
-1.987T
and
Thus it would appear tha.t the alkylation of propene by isobutane is thermodynamically possible in the temperature range of about 200C and lm.ver. The ultimate yield
at 200C is not large; but since the rate or velocity of the reaction increases rapidly
with temperature, it will probably be best to operate at as high a temperature as possible. Should the rate be too slow at 20QoC, a catalyst must be found.
From a purely thermodynamic standpoint it might also be possible to make 2,3dimethyl pentane, 2,4--dimethylpentane, 3,3-dimethylpentane, or even 2,2,3-trimethylbutane from propene and isobutane. The values of the free energies for these reactions (computed in the same manner) are
2,3-Dimethylpentane .. , ...... .
3,3-Dimethylpentane. , , .... , ..
2,2-Dimethylpentane ... '0 ' , ,
2,4-Dimethylpentane ......... ,
2,2,3-Trimethylbutane .. '" ... .
-10,350
-10,650
-10,050
-9,550
-9,050
-80
120
1,120
1,320
2,820
Thus it appears that several ractions might take place simultaneously but that the
amounts of each of the isomers (at 500 0 K) would be somewhat in the decreasing order
shown in the foregoing tabulation, Even this does not include all the thermodynamic
posSibilities, because there are many other iaomeric seven-carbon-atom hydrocarbons.
712
300
400
500
Molecular Wei9ht of Charge '
FIG. 2()"2. Approximate endothermic heats of reaction.
100
200-'
600
700
is endothermic) and vice versa. Data for heats of combustion (or formation) may be obtained from the National Bureau of Standards 36 (API
Research Project 44); or from U Physical Constants of the Principal
Hydrocarbons."u The use of generalizations for beating values such as
Fig. 5-22 can be misleading 3; if large amounts of aromatic hydrocarbons
"Free Energies of Some Organic Compounds/I Reinhold Publishing Corporation,
New York) 1932; alao R. H. Ewell, Ind. Eng. Chern., 82, 778 (1940).
as Technical and Research Division of the Texas Company, 3d cd.) 1942.
III Gornowaki and Feldbauer, A. Method of Estimating Hea.t Rea.ction in Catalytic
Reforming, ACS Meeting, Dalla.8, Apr. 8, 1956.
17
REBUILDING HYDROCARBONS
713
are present, because common criteria such as Correlation Index, Characterization Factor, aniline point, etc., fail to differentiate between aromati~
hydrocarbons and mixtures of other hydrocarbons. W. C. Edmister 40
has published Fig. 20-2 by which endothermic heats of reaction can be
estimated from the average molecular weights of the feed and the
products. Typical heats of reaction are given for particular ~eactions
in the remaining parts of thls chapter.
THERMAL CRACKING
714
TABLE
20-3.
Feed
Propane Butane
12-1b R.v.p.
natural
gasoline
Reduced
crude
oil
Operating conditions:
Cracking temperature, of ..........
1400
1500
1.00
1.02
Total pressure, atm ...... . .. . ......
Residence time, sec ....... . ........
4.5
10.9
Steam-hydrocarbon feed ratio, Ib lIb .
0
0
Product distribution, wt % of feed:
Methane ..... . ....... . ... . .. . .... 36.15
28.70
Ethane .................. . ... .. .. .
3.70
6.80
0.42
... ..
Propa.ne ...... ~ ...................
lsobutane .. .......... . .. . ........ . . .. . .. . . . ...
n-Butane ... . ............ . ........
0.28
0.68
Ethylene ................ , ........ 28.44
30.11
Propylene ... . ............. . .. . ...
4.92
1.99
0.27
0.44
Butenes .. . . . .....................
1.79
1,3-Butadiene . ................ . ...
1.48
0.27
Cyclopen tadiene . ............... , ..
0 .31
Hydrogen ....... , ... , ............
2.26
1.15
Acetylene .......... , .... , , .......
0.10
0.49
1.42
Inerts .. . .... . ... , , .... , ... . ......
1.93
Benzene ................. , ........
7.71
12.57
Toluene ......... , , ...... . ........
1.08
1.91
0.38
0.06
Xylenes ...... . ...................
0.29
Ethylbenzene ........... , .........
0.29
Styrene ... . .......... . ... . ... .. ..
0.66
0.71
C g + aromatics in 32-392F distillate
0.96
0.86
Olefins in 32-392F distillate .. .. ...
1.40
0.83
Paraffins in 32-392F distillate ......
0.10
0 .67
Distillate 392-572F . . ......... . ...
3.70
1.48
Distillate 572-670F ...............
1.22
0.49
Pitch ...... . .. . ...... . ......... . .
3.82
3.79
Carbon ... . ...... . .......... , .... .
0.27
0.75
Total .. _ ...................... , 100.00 100.00
1400
1.00
9.6
0
5.18
15 11
3.62
0.78
0.21
28.28
1470
1.02
2.5
0.15
0.20
.....
24.08
3.41
0.39
1.33
0 .24
1.13
.....
0 .25
9.04
1.87
0 . 14
17.88
5.86
1.06
2.43
0.62
0.79
0.18
0.21
.....
0.64
0.82
1.60
10.01
1.12
1.05
5.77
2 . 14
10.03
0.65
100.00
8.63
5.07
20.79
7.39
..
100.00
~o
Air
::llIII
.m
l!Il
Acetylene
plont
Oxygen
plant
~
J
r---------------r ____ ...:. ___ . . :. __ :.. . . ___NH3
-..J..
H.
naphtha
VAPOR PHASE
CRACKING PLANT
11I
C2 =
r---
(FOR UNSATURATES)
Tl ___L_L Aromatics
Aro.t
r r 1 '
i
Cumene
plont
I
f
\
Phenol
.
plont
..
Styrene
plant
I
~ .
Synthetic
rubber
C4=i and
LC.,H6
Cata.
desulfurization
plant
C3=
I'sopropanol\- ..
I ~---J.~
plant
Acetic
aCid
c3 =
Catalytic
reforming
plant
Nap{7lha
CH4
LJ
L ___ ~~
Acetone
plant
L___
Acetaldehyde
plcnt
H2
}-.
plont
CJ ==
c2 =
--'"
Glycerol
plant
Butadiene
plant
1
T
\-oII-_.J
Ethylene
oxide
Ethylene
dichloride
plant
l+-
Nat. gas
~
IH2 5
r-t ..
'2-
n2
.I
i
'"""
en
C. -
(,=
'2\
.~
Polyethylene
plcnt
Sulfide
extraction
plant
--
~.
Alcohol ~_-'
plant
so.
'2":
H.
___ J
I
I
Ammonia
plant
~
2!!!'.- gas 011, or
Sulfuric m
acid
plant
AmmonIum
sulfate
plont
Nat. gas
AIr
plant
Ethylene
1-+
Corbon bloc/(
Not. gas
FJO. 20-3. The by-product nature of the petrochemical industry (also Bee text).
glycol
plant
iIIII( Distillates
I
716
Ethylene Plants. Of the 10 million pounds per day of ethylene produced in the United States during 1956, about half came from the vaporphase cracking of natural gas hydrocarbons, 15 per cent from the vaporphase cracking of naphtha or distillates, and less than 35 per cent by
extraction from refinery cracking-plant gases. The ethylene in vanous
refinery gases (Table 14-4) is recovered in an ethylene recovery s~temJ
and the other gases that are useful as a cra.cking stock for ethylene manufacture are present in the following. amounts:
Etha.ne ............. .
Ethylene ........... .
Propane. '" ., ...... .
Propylene .......... .
Mole %t range
Average
5.0-28.0
3.3- 8.2
7.0-44.0
1.0-36.0
12
5
14
19
Of course, richer gases could be made available or, if the refiner chose to
recover the propylene as tetraIner or as bottle gas along with propa.ne,
the gas would be lea.ner. Note that a separate feed prepara.tion system
is not necessary (Fig. 20-4) because the products of cracking contain the
same gases as the feed, and thus both the feed and the products can be
processed in a single product recovery system. It is necessary, however, .
to remove hydrogen sulfide from the incoming gaseous feed.
TABLE
20-4. HEAT
Differential
0
20
46
60
70
80
90
Propane~
Etha.ne
Percentage
convE'mon
.\
Cumulative
59
M.5
59
52
49.5
53
51.5
60.5
48
47.6
....
....
....
.....
Differential
41
37
Cumubtive
41
38.6
32.5
36.5
28.5
35
33.5
25
20.5
low
32
30
\
I
717
REBUILDING HYDROCARBONS
outlet. A sharp increase at the outlet means too high a rate of heat input
with high film temperatures and excessive secondary reactions leading to
coke, whereas a drop in temperature allows too close an approach to
equilibrium and thus a long time for condensation reactions to occur
among the heavy products leading to the formation of heavy liquids,
tars, and coke. The production of ethylene is primarily a reaction of
dehydrogenation J and the equilibrium constants for dehydrogenation are
given in Fig. 19-4. Low pressures cause the reaction to go more completely toward dehydrogenation and thps pressures und~r 50 P$g are used
a.t the outlet of the coil, and steam is often introduced to further reduce
the partial pressure. The amount of steam ranges from 0.3 mole steam
per mole ethAne to as high a ratio as 8 when cracking heavy oils (see
Ta.ble 19-8). Commonly used heat transfer rates and velocities41 are
indicated in Table 20-5.
TABLE
20-5.
Inside tube
dia.meter,
in.
Cracking
stook
Etha.ne
4
4
Propane
Butane
Naphtha.
4.5
Range of
conversion,
per centb
Raqiant heating
rate, :Btu per
sq ft projected a.rea.1I
23-26
26-28
28-32
24-26
50-60
70-85
75-90
50-58"
23,600-28,250
14,100-17,300
11,000-14,100
11 ,000-14,100
The radian t, absorption rate must be larger (sometimes double) in the earlier
rea.ction zones in order to maintain a coIlBtantly rising tempera.ture.
II The range in the high-conversion zone.
e In terms of weight per cent butanes and lighter.
II
In Fig. 20-4, refinery gas is treated with diethanol~ne for the removal
of hydrogen sulfide, and it then joins the reaction products for a wash with
caustic for the removal of the last traces (below 10 ppm) of hydrogen sulfide, carbon dioxide, or any acidic materials. The reaction products
contain small amounts of acetylene (0.2 to 0.5 mole per cent based on C 4
a.nd lighter) especially if the reaction temperature is high and the amount
of steam used for partial pressure reduction is large. U This must be
reduced to 10 ppm to meet ethylene purity specifications. Selective
hydrogenation at 50 to 350 psig is the common method of removing
acetylene. The gas is then compressed and cooled to as Iowa tempera.ture as possible without hydrate formation (see Table 22-3) and dried
using a solid desicca.nt such as alumina. The gas is then passed through
a. series of fractionating towers for the reeovery of ethylene and propylene,
U Sohutt and Zdonik, Compression and Pretreatment of Pyrolysis Produot, Oil GaB
J" June 25, 1956, p. 92.
718
the elimination of methane and hydrogen, and the separation of feedstocks (ethane, propane, and small amounts of the butanes) for the
vapor-phase cracking coils. Refrigeration for cooling the feeds and
re.fluxes of the dernethanizer and ethylene towers is usually provided by
a cascade refrigeration system operating on ammonia and ethylene which
FEED-STOCK PREPARATION SECTION
Couslfl:
Amine
wosh lOW6/'
absorber
f/ETINRY
GAS
/,,~
lOwer
~iNl
Propylene
lower
RSJDUE
GAS
1
I,
AROMAr.C
UOlJ1()
fJOscom~
(J>et. Proces8ing.)
REBUILDING HYDROCARBONS
TABLE
20-6.
SYSTEMS (SEE
FIG. 20-4)
Demethanizer
Dcethanizer
Ethylene
tower
Depropa.nizer
--425-500
Pressure, psia ... ~ . . ..
Top temp, of. .. . .. . -100 to -1S0r.
Reboiler temp, o~ .. . .
35-65
20-30
Plates .... . .. , ..... , .
Low
Reflux ratio ...... . ...
325-450
10-30
165-190
30-40
0.8-2.0
150-225
275-360
-20
10-40
225--275
50-65
3.5-5.2
1.0
o to
75-110
Basically the same conditions as those of Gyro Vapor Phase designs of 1932 and
used in plants of 1935-1938.
TI Feed to tower at about -70QF to save refrigeration at top of tower.
a
....
...
16 .6-17.3
7.7-8.9
20 .2-29.7
Weight
per cent
11-17
10.2-10.7
5.7-6.6
25.4-30.9
.. .......
8.9--13.6
The same tempera.ture and method used in the arrestor of the. original Gyro
Vapor Phase Process in 1928 and thereafter.
H Wagner, C. R., Vapor Phase Cracking, Pet. Engr., November, 1929; also see page
487 of the First Edition of this book.
4. Anon., Steam Cra.cking Extended to Ethane, Propane Feed Stocks, OU Gas J.,
Ja.n. 2, 1956, p. 113; also Pet. PToussiny, February, 1956, p. 87.
4a
720
20-7.
COMPOSITlON 4 OF VAPOR-PlUSE
B-B
B-B
Gas cra.ekinge
Butadiene .........
38-56
~u~l:nes
........ }
80 U eL.e
39-53
~~~~e }
2.2-6.7}
Others (a.cetylenes).
2.1-4.2
44-52
12-24
23-37
Heavy stocks
cracked for
Gases
Gasoline
10-46
37
7-40
13
60
25
1-2.5 }
0.5
T.e.C ..
process" processb
Fluid
None
25.6
10.6
10.7
53.1
None
18.9
12.7
12.2
56.2
Wagner, C. R., Ind. Eng. Chern., 27, 933 (1935); Poffenberger et aI., TraM.
A.I.Ch.E., 42, 815 (1946); and private communicatio~s to the a.uthor.
/) Nelson, W. L., Oil Gas J., Sept. 22, 1949, p. 297.
Two different operators.
CI
&)
normal butane, they are said 48 to produce 50 per cent more ethylene
than tubular stills. The use of "highly superheated stea.m (1700 to
1900F) as the main heating medium 49 is a means of avoiding coking on
the surface of tubes, and thus reaction temperatures of 1700 to 1880F
become feasible. Likewise, oxygen or air introduced into the hot (1100 to
1500F) stream of feed material has been suggested as a. means of heating
(by combustion) during the rea'ction, in the auto thermic process. 50
Finally, various regenerative methods of heating similar to those used in
gas manufacture have been used. 51
Wagner, C. R., Ind. Eng. Chem~, 27, 933 (1935) relates va.por-phase BB cut produced in 1929i also Poffenberger et al., Trans. A.l.Ch.E., 4~, 815 (1946); and private
communications to the author.
47 Ralph, H. D., Oil Gas J., Dec. 15, 1945, p. 70.
48 Kilpatrick et al., Phillips Pebble Heater . . . , Oil Gcu J., May 10, 1954, p. 162.
4Q King and Warburton J Oil Ga8 J., Dec. 8, 1950, p. 92; also Pet. Processing. November, 1952, p. 1644.
50 Dea.nes1y and Walkins, Chem. Eng. P,ogr., March, 1951, p. 134.
U Schutt a.nd Zdonik, Proceeing Scheme-Pyrolysis Methods, Oil Ga.a J. t Apr. 2.
1956, p. 99.
48
~. - ~ -= .~ . -
....--, .. -"
721
REBUILDING HYDROCARBONS
"UHAIt
COLUMN
UKYLENJ
COLUfIU(
.-rO GA
ETHYLENE
eoWPRESSOR
(Schute, Oil
722
POLYMERIZATION
This reaction occurs in several ways, i.e., as bimolecular or polymolecular react.ions, or as successive reactions that produce dimer, trimer, or
polymer products:
and
!
I
!.
i
2C 2H 4 ~ C4 Ha
3C aHe ~ CDR 18
C4Hs + C9H18 ~ C 13H 26
723
REBUILDING HYDROCARBONS
P =
where K dP
= reaction
tP a(l - x)
20-8)
t = time, min
p = pressure, pSla
x = fraction of olefins reacting during time t
a = fraction of oletins contained in feedstock
The values of K dP of Table 20-8 6l cover experimental ranges of pressure
up to 3,000 pounds and temperatures 'of 650 to 850F and 1400 to 1500F
when handling ethene~ propene, and the butenes. According to H. C.
Schutt,69 the preferred range of time for the polymerization zone in commercial thermal polymerization is 50 to 100 seconds.
TAllLE
20-8.
Temp, OF
1,000 K1/P
Temp, OF
650
0.0048
0.013
1,000"
0.029
l,20Qb
0.063
1,300
0.135
0.29
1,400
1,500
700 750
800
850
900"
950b
1,1O()b
b
1,000 K 2 /P
0.95
2.9
7.5
17.0
35.0
68.0
0.56
See p. 640 of the Third Edition of this book for plotted experimental points.
to
'recovery .
sYstem
to
recovery
Feed
Furnace
Coo Ii
t-o-( }
FIG.
'iiIIaIiiiI---_.-
Typical
:UitlrW\PU
(and decomposition.)
oil arid
725
REBUILDING HYDROCARBONS
The flow diagram shown in Fig. 20-6 shows the essential features of the
Baytown plant of the Humble Oil & Refining CO,liS Analyses of the feed
and several stocks are shown in Tabl~ 20-9, The capacity of the plant is
10,OOQ bbl daily, but the amount of material charged to th~ furnace is
TABLE ~9, STOCKS AND PRODUCTS OF It. THERMAL POLY PLANT4
Stock
Reaidue
Fresh
feed,
mole
Furna.oe
feed,
mole
mole
.. .
.
...
........
1.5
10.5
6LO
28_0
19.6
' 20
80
ao.o}
1.5
Methane .....
BthAne .......
Prop&ne ......
lsobutane ....
n-Butanc .....
Tota1. .....
Unn.turat.ea ..
"
58.0
100
15
Properties of stock
g&8.
Li&ht Heavy
poly Gas oil and tar
poly
gaBO.
i&80.
75
90
44
195
450
100. 0
100.0
14.0
12.0
Grayity, API
I.B:P., aF
F.B.P. of
Per cent at 15SOF
Per cent at 212F
Reid v.p., pili
Octane No. (CFR Motor
method)
Octane No. (blendin, value)
24~
58
95
13
20
370
(00. % at 66O"F).
2-3
2-3 ,
77.5
75
87.0
PrQpane.
Butane .. . ..
A
5 % conversion
10% conversion
15 % cOllversion
51.7
71.6
47.5
64.4
56.7
Note that the conversion per pass applies to both the decomposition and
polymerization parts of the still. These yields apply to a specific plant,
and the method of H. C. Schutt9 is probably more dependable when
considering various operating conditions. Complete operating conditions
are given by Ridgway arid Maschwitz,68 and their data on the effect of
pressure and recycle ratio on the yields of one plant are indica'~ed in
Table 20-10. Yields increase up to even 2,500 psig, but such an operation
is not economical. Based on propane and butanes, the ultimate yields of
poly gasoline are 62 to 72 per cent by weight, and the tar or residue 5 to 10
per cent.
Feed Preparation. Although propane, butane, etc., may be decomposed
or dehydrogenated to produce propylene and bu~ne8 (pages 644 to 652),
this method is not followed except in thermal polymerization pr~esses
726
20-10.
Pressure,
pSlg
Percentage
based on
Percentage
Qased on
500 psig
349,000
387,000
414,000
110
122
130
500 paig
318,000
358,000
500
1,000
1,500
383 ,000
100
113
121
41 Turner and Ruby, Ref. Nat. Gcuo. Mfr., September, 1938, p. 423; and Ridgway
a.nd Ma.schwitz, Oil0J.8 J., Oct. 30, 1941, p. 30.
The olefins in the cracked gases are handled or concentrated ill several
ways, depending on the pressure at which the gas is available and how
much can be afforded in recovering the olefins'. It is seldom economically
feasible to recover or process ethylene for polymer gasoline, and hence
the preparation of the feed pertains mainly to the retention of propene
and the butenes, or to the segregation of them for selective polymerization
or alkylation.
"
1. Complete. The entire cracked gas is compressed and is sent to the
poly plant along with the overhead liquid from the cracked gasoline stabilizer (or debutanizer). Hydrogen sulfide must be removed before
the feed enters the poly plant. The product from the" catalyst chambers
contains much gas (and some olefins), and hence this gas is sent through
an absorber wherein lean absorption oil from the cracking unit is used to
deliver propene and heavier hydrocarbons back to the cracking plant and
eventually to the gas separator of the cracking plant. This is the desired
"method if the gas pressure is high (50 to 125 psi), and it is always desirable
except for the cost of compression.
2. Low-pressure Separator. With low-pressure gas (as in a catalytic
cracking unit) less compressor capacity is required if the separator gas is
compressed and sent to a high-pressure absorber in which some of the
cracked gasoline is used to absorb the propene and heavier hydrocarbons
...J. . "r:
-:-E ~ -= -c5t
- -ct __ . . .
, " -:
_ _ __
' n~
I"
727
REBUILDING HYDROCARBONS
as shown in Fig. 20-7. The flashing of the gasoJine to produce a lowvapor-pressure absorption oil, as shown in Fig. 20-7, is relatively expensive.
3. Deep Stabilization. This simplest and widely used method requires
no compression because the olefinic feed is only the liquid overhead of the
cracked gasoline stabilizer. The cracked gasoline is stabilized as deeply
as possible (4 to 7 Reid vapor pressure) without driving pentenes into the
stabilizer overhead, Under proper conditions pentenes can be polymerized, but the dienes associated with them harm the catalyst. Since
little ethene and only part of the propene are held in the cracked gasoline
in the gas separator, some of the olefins never enter the stabilizer, and the
yields of poly gasoline are somewhat low.
,r
L-I: gasollne
fo sforage
Absorber
Poly plant
Stabilizer"
feedfo
!}--_
sulfide
removal
Gasoline and
gas From
cr.unif
Wakr
Oehulonized
crocked goso me
Heaf
FIG. 20-7. Poly plant feed preparation if the gas pressure is low.
tion employs- only the butenes or in some cases only isobutene. The
gasoline from selective operation is primarily 2,2,4-trimethylpentene or
similar branched hydrocarbons (Codimer) which have a high octane number (92 to 103). The Codimer may be hydrogenated to make isooctane.
Obviously, special methods of feed preparation or fractionation must be
employed for selective operation, and the same applies to alkylation which
is frequently applied to only the butylenes and isobutane.
Phosphoric Acid Polymerization. At least three modifications in the
use of phosphoric acid as a catalyst are widely used: (1) quartz wetted
with liquid acid,82 (2) acid-impregnated pellets (solid phosphoric acid)
n
728
20-11.
l-'~ ....
Mixture
Mixture
Mixture
Butanes
ButeDes' ButeDeB
Product .. . . . ... Motor fuel Motor fuel Motor' fuel Mowr fuel Codimere Codimer
OpemtiOIl ....... NOJllleleetive Nonaeleotive Nonselective Nonselective Selective Selective
102
127
Chamber
500
61.3
90
143
226
226
372
~86
367
422
10
11
Tubular
900
66.6
110
146
228
330
~OO
10.9.
Reactm
Reactor
1,000
900
61.3210
64.3
78
162
258
379
416
11.0
.. Dimei' from nearly eqaal amounta of i.. and Il-but.ene in feed. About
434 F, also produced.
b Some motor fuelllod heavy polymer alSo produced.
223
228
234
257
..... .. .
~fo
PropeDe
PropeDe
MotorCuei Tetramer b
Nonselee-
Se~t.ive
Reactor
Reactor
Reactor
1,000
1,000
900
51.0'
353
383
371
66.4
136
207
eve
62.4
144
210
230
266
276
330
402
4
400
3.2
397
4liO
0
729
REBUILDING HYDROCAnBONS
used solid-acid process, space veloci~ies of 0.15 to 0.4 have been used.
The activity of the catalyst is gradually destroyed and hence extreme
catalytic activity occurs during early stages of operation. Low feed temperatures are used during the stage of high catalyst activity, inert gas
(butanes) may be recycled, or in the reactor-type process the temperature
may be reduced by cooling with water. Inert liquid is also sprayed into
the chambers as a means of temperature control. The general effect of
I
TOTAL SPACE
VELOCity
gph 10101 feedjlb cola/yst
t
I
IOOH
}
CATALYST AqTlVlTY
~ ~
I~~
~~
l;.-
a~ ~
~~,
95 .~'
..,
90 ~
ti~
l
~~~~~~~'~~~-4--+-~~~~~~~~~~~480 ~
~ ~ 201---+--4-+lor~~~~~-~4-.-f-~~~~~~"""'~>--4-~75 ~
J~~~~~~~+-~-4~?O
'6
IO~~~--~~~--~~~~~ ~~~~~~~~--~~~&5 ~
1 .~ ~
~
FIG. 20-8. Chart for predicting the conversion of total feed in ca.talytic polymerization when using copper pyrophospha.te as the catalyst. (Chern. Eng. Progress.)
-reaction temperature on conversion is indicated in Table 20-12. Likewise, the effect of space velocity on olefin conversion in chamber-type
solid acid plants,66 when charging a feed: of 35 to 40 per cent olefins, and
for pyrophosphate plants64 is indicated in Table 20-13.
Orthophosphoric acid is ~he kind of acid desired in the phosphoric
acid process. I t tends to lose water and "form. inactive metaphosphoric
acid at temperatures above about 450F. Vaporization of water may
be suppressed somewhat by the use of 2 to 10 per cent steam or water
in the olefin feedstock, but larger amounts will cause the formation of
BI Shanley a.nd Egloff, Ref, Nat. Gaso. Mfr., June, 1939, p. 227.
730
as
TABLE
20-12.
Catalyst,
temp of
Copper
pyrophosphate"
330
350
70.5
75.5
81.0
86.5
370
390
410
420
430
450
77.0
79.5
90.5
91.0
""
......
Solid
acidlo
.
I'
95.0
......
20-13.
0.1
0.15
0.2
0.4
0.6
97.5
92.5
88.0
,
...
93
86
77
17
ed.~
. .... ..,.. .
731
REBUILDING HYDROCARBONS
20-14
Ch~mber
type
Reactor type
Low pressure
regenerative"
High
pressure
Nonselective
Selective
250
500
900
900
Selective
Nonselective
400
475
80
75-80
50
375
450
85-90
340
310
380
92
350
82-83
82-84
75+
120-150
90-95
93-95
130-150
Higher temperatures dry and reduce the activity of the catalyst and promote the formation of cokelike deposits. Water in the amount of about
5 per cent by volume of the feed keeps the catalyst in the form of orthophosphoric ~cid. Larger amounts of water may cause the catalyst to
cake into a mud and become highly corrosive. Pressures of 500 psig are
advantageous becaus~ such a pressure reduces the volume of gas that must
be handled, increases the rate of reaction, and provides sufficient pressure
in the depropanizer to easily condense propane reflux. The reaction
. vessels 6s are of two general types. They may be constructed 1ike a
heat exchanger with the catalyst packed inside of large tubes, or they may
be a plain chamber having several spiders for introducing inert gas. Thus
cooling can be accompJished by passing water through the shell as indicated in the auxiliary steam generation system of Fig. 20-9, or by inert gas.
Some recirculation of butanes (handled as a liquid) is practiced, particularly if the chambers are not water-cooled, so that the general reaction
rate can be regulated. In some plants the catalyst is washed and somewhat cooled by the introduction of poly gasoline or butanes.
Catalyst life is greatly reduced by even 0.002 mole per cent oxygen in
the feed, by the formation of varnlshlike substances. Likewise, nitrogen
&8 Armistead, G., Jr., Nonselective Cata1yt.ic Polymerization . . . ,Oil Gas J., Apr.
6, 1946, p. 131.
732 .
PETROLEUM
RE~ERY
ENGINEERING
compounds (0.5 per cent ammonia) rapidly destroy the catalyst. A wash
with water removes most undesirable nitrogen compounds. At reaction
temperatures. exceeding about 500F water must be continuously added,
whereas at temperatures below 300F moisture must be eliminated from
the feed.
Armistead 68 indicates the production of olefins by thermal and catalytic
cracking operations, and the approximate yields of 10-1b poly gasoline'
obtained with average Mid Continent crude oil, as in Table 20-15. The
steO)"TI
di$engaging
drum
.r.---.,
Fe
~
.1 ':
c
Trea+ed
c]- C.. feed
II~"
90 9 in 9
tanJc
~4
steom CO"~
Depl'"Oponiz,ecl
boiler: house
line
733
REBUILDING HYDROCARBONS
TABLE
20-15.
Self-contained processing of
Mid Continent crude
Type of operation
All t.herma.1b
Catalytic cracking-plan t conditions:
Temperature, of .. ... . ............
Conversion, per cent . .. .
Yields, volume per cent basis crude:
Propylene ....... . ........................
Propylene polymer a.t 65 per cent recovery (Hl
lb R.v.p.) ........ , .....
Butylene d '.' .
Butylene polymer at 90 per cent recovery (10
lb R.v.p.).
Total 10-1b polymer ........... . .........
0
.
...
"
900
850
55
"
Catalytic thennal c
.65
2 .1
2.9
4.3
1.1
3.1
1.4
3.4
2.1
2 .5
3.6
2.8
4.2
3.2
4.0
5.3
,
G Armistead,
G., Jr., Nonselective Catalytjc . Po1ymerization . . . , Oil GaB J.,
Apr. 6, 1946, p. 13l.
b Reforming heavy straight-run naphtha, thermal cracking of 56 per cent reduced
crude to ultimate yield of gasoline.
C Reforming heavy 8traight-run naphtha, Bingle-pass ca.talytic cracking of virgin
gas oil (40 per cent of crude), and thermal cracking of virgin residuum (16 per cent of
crude) and catalytic cycle oil to ultimate yield of gasoline.
d Total production.
734
During operation, a small amount of acid may 'drip into the catch-pot
where it can be periodically drained to the acid-storage drum. Acid
consumption usually amounts to less than a pound (75 per cent acid) per
140 gal 62 of polymer product. Loss in acid arises mainly by carry-over
into the knockout drum which contains limestone for neutralization. of
Coolescer
Sulfide-free feed
"---....-J'
Wasil water
Wafer
wash
drum
Temperature and
reaction control
...
To slabilizer
Catalysl
knock-oul
drum
Regeneration
syslem
Calch
pol
Acid slorage
the acid. The moisture content of the feed is adjusted py the temperature (about lOOF) in a water-wash drum which is also needed for dissolving nitrogen compounds from the feed. The process is said to be
more economical than the solid-acid process.
Other Processes. Numerous catalysts have been employed for polymerization, including highly stable silica-alumina (Phillips Pet. Co.),
aluminum chloride, G9 boron trifluoride, and activated bauxite.70
The hot and the cold sulfuric acid polymerization processes were once
Waterman et al., Ret. trav. chim., 63, 699 (1934).
70 HeID(;IDann et al., Ind. Eng. Chem., 40, 1224 (1948).
ag
REBUILDING HYDROCARBONS
735
736
Alkylation is the umon of an olefin with an aromatic or paraffinic hydrocarbon. Common operations are
737
REBUILDING HYDROCARBONS
about 18 per cent of the alkylation capacity is handled by the HF process (1955).
The acid alkylation process works most successfully on the higher
molecular weight olefins(t:;;uch as the butenes), whereas thermal alkylation
attacks ethene most readily. Acid alkylation is limited to the isoparaffin
hydrocarbons (isobutane and isopentane), but the therm~l process
handles either the iso or the normal compounds.
The composition of depentanized alkylate from mixed butenes was
determined 82 in API Project 6, and although the HF alkyl ate contains
more 2,2,4-trimethylpentane both of the alkyla.tes have much the s&me
octane number:
Hexanes ................... .
Heptanes ..... , ............ .
2,2,4-Trimethylpen tane. . . . . .
2,2,3-TrimetbyIpen ts.ne . .... .
2,3,3-Trimethylpentane ..... .
2,3,4-Trimethylpentane ..... .
Dimethylhexanes ........... .
Nonanes ................... .
Heavier. " ........ . .... '... .
HJ)O. process
BF process
6.8 vol. %
7.0
26.7
1.3
13.5
14.3
11 .2
6.4
12.8
2.1 vol. %
4.5
41.7
2.9
10.0
9.4
19 .6
3.4
6.4
The heat
Hydrofluoric Acid Process (HF). This hlghly successful proce88 7 ,84,85,86,87 for combining isobutaneand isobutene, as shown in Fig. 20-11,
involves the recirculation of about 6 parts of isobutane to 1 part of isobutene. A temperature of 75 to 105F and a pressure of 100 to 150 psig is
maintained on the reaction co~tractors. Th~ acid is currently dried (kept
Lhaeger et al., Pet. Refiner, August, 1951, p. 71.
sa Mrstik et ai., Commercial Alkylation of 180butane, "Progress in Petroleum
Technology," ACS Meeting, New York, September, 1951.
114 Benson, R., Sa.fety in . . . Hydroge~ Fluoride Alkylation Plants, Pet. Refimr,
December, 1943, p. 116.
U Shanley and N ebeck, Numerous Improvements in HF Alkylation . . . , Oil Gas
J., Deo. 1, 1945, p. 94.
86 Kunkel, J. H., HF Alkylation Unit.on Stream in Record Time, Pet. Engr., Sep
tember, 1944, p. SO.
111 Scott and Cooper, Economic . . . Operation at HF Alkylation Plant, Oil Gas J.,
Mar. 30, 1946, p. 204.
81
738
20-16.
"
~
Propylenc
feed
Butene
feed
Penilenes
feed
Hydrofluorie acid
50:.50
propene- Aviation
bat.enes
feed
~e
E.P.,
or ....... ....
1.5
73
5.8
114
69.7
4
125
177
108-143
110-1%
124
158-197
227
195-196
213-224
247
239-246
338-360
258-261
335-360
281
251
236
360
340
320
84-140
25-40
90-91
161
206
110
103-107 103.6
127
catalyst
Propcne-
Butene
feed
butenepentene
ret<!
72.8
70 .2
.... ...
2.0
Light
--
163-179
Octane ratinl!8! ,
F-l clear- ... . ... 88.2-91 91 .8-96
F-3 with 4. Cjl TEL 102.2-106 10.5-108
122
Foi with 4. c:c TEL
151
Performance No.:
F-3 .. ........... .. .. .... . . . . .... .. ,
F..L .. ... .. .. .. 135-145 153-161
Yield, % on olefin
cOllSUllied. . . . . . . 17D-17S 16.5-172
\At. ooosumption,
Ib per bbJ . ......
66.5
PropeneHeavy
butene
feed
all
+2.0~
.. . ... . ... .. .
145-150 . .....
52.3
.... .
8b3
360
374
483
579
212
210
182
239
238
334-
+0.56~
. . . ....
+1.15 b
+0 .79"
+2.2"
+3.2
+'2.4"
.. ...
117
128
... . .
140
148
122
142
98
212
13D
181
204
327
.....
239
98
. .. .
. .....
136
94
138
215
71.0
3.0
138
309
.. , . .
... . .
. . ..
74.0
8.6
.....
237
au
II
...
.... " .
92
119-120
HG-I42
155-172
42-80
at 2 per cent moisture or less), about 6 per cent of heavy oil or tarlike
material is removed, and 0.3 to 0.8 Ib acid per barrel of alkylate is con.sumed or lost. The octane number of the alkylate depends m'ainly upon
the kind of olefin involved
.
iC.H 10
iC 4H 8 ~ isooctanes (92-94 Oct. No.)
iC.H 1D + iC 6H 10 -+ isononanes (90-92 Oct. No.)
iC.H 10 CaHa -+ isoheptanes (89-91 Oct. No.)
Plain carbon steel is used throughout except that some rundown lines are
constructed of Monel metal. All lines are jacketed and connected to a
II blowdown'" or water spray pump so that the gaseous acid will be caught
if a break occurs. Much of the operation is by remote control; and, when
the operator must approach the unit, face masks and rubberized clothing
are worn. The cycle time efficiency is said to be 96 per cent.
Sulfuric Acid Process. This process has been applied primarily to
isobutane and butenes. The absorption of the olefin hydrocarbon occurs
at'a rate several hundred times as fast as'the absorption of paraffins, and
hence in order to maintain the proper concentration of the two hydrocarbons in the acid it is necessary to recycle a large excess of the saturated
I
I\
, !
I
739
REBUILDING HYDROCARBONS
Dry butone
butyl.nll!
Dilute
f""d
To..
N buione
coustic
AII1Ofion
ollty!,,'"
A!lty1ote
boHoms
Rellwc condens.er
.nd dlum
tower
Depropartiu:r
ReflUli cOfIdRnur
end d,um
I-butane
Acid free
Debulanizer
Rellul condtn~ef
and drum
Bullnt
J..---- p,odut\
R~fI\II
condenser
~nd
Propane
product
drum
Aviition
alkylltl
Emulsion
circul~lor$
HNVY
0....-.._-+ .'kyl~t.
Spenllcid
740
water. Thus, the spent acid that is currenUy removed from the process is
not destroyed chemically and may be recovered by standard methods or
may be used in acid treating other refinery stocks such as lubricating oils.
The make-up aciQ amounts to 1 to 3 lb of acid per gal of product, but if 8.
recovery plant is available, only 0.1 to OAlh acid is lost per gal of alkylate.
From one to two parts of acid are circulated per part of hydrocarbon.
Agitation is accomplished by means of Jets or baffles. Temperatures of
32 to 50C are employed, and a temperature above 7GoC results in excessive acid replacement and a decreased yield of gasoline .
. TABLE
20-17.
EQ. (20-13)
20
40
89.6
89.1
91.6
95.3
90.3
92.0
94.2
88.8
88.0
90.7
94.8
90.4
92.'5
95.8
93.0
94.4
97.0
102.6
102.0
105.4
103.0
102.5
105.8
103.2
110
118
-4
88.0
89.6
112
118
126
149
131
151
200
102.9
.106.2
103.5 . 104.2
103.3 104.3
106.4 107.0
123
1,24
135
153
129
130
138
155
141
144
147
158
, F = IE(ljO),
100 (SV)o
where IE
(I/O) II
(20-13)
= liquid
741
REBUILDING HYDROCARBONS
the mixture is kept below about 30 per cent, little if any increase in acid
consumption is noted. 90 Alkylation of -pentenes requires slightly more
acid than butenes. Low acid consumption is attained 90 by keeping the
propylene below 30 per cent in the mixture, using a high ratio (6: 1 or
more) of isobutane to olefin, low space velocities, and low reaction temperatures (40F).
Thermal Alkylation. Whereas sulfuric acid alkylation operates most
successfully on isobutylene, the butenes, and propylene, thermal alkylation acts most readily on ethylene followed by propylene, butenes, and
and methane
t /,ffyriroaen
slripped C/TlcKed ,gas
Isobu/cme feed
Isobulane os
ab""rpfion liquid-
Isobufane------
Vrzikfng teed
Efhane
--
;sobutane
feed
gasoline from
cracking step
,'/sobufeme
.. Prop;;;;;and
Propane
Re~~8utoneor
mi;durBs
Mqy confain .some m~lhane
( elhcme riis-
charged
Charge. -""C:J--f::=:J
I]'iomo'l'b,''''.
.sq.m.
","vi
pr;1crico/(y n-o
methane fbrmed
--
/.
~.",.......=--'
0
Crackin9 step
Low pressure 1,400
_~
Neohexane fP.SOline
to fracfionafors
I
s. sq. In.
20-13. Thermal alkylation (neohexane pilot plant). (Oil Gas J.)
742
efhyh~nzenes
Vent
cibsorber
. E-Ihylene
Polye+hyl still
HCL
L - _........._ _ I _
BenZ9ne
Complex
1st sta ge
settling
L . . . - _....
Caustic
scrubber
cumene. The regular solid phosphoric acid polymerization plant equipment (Fig. 20-9) may be used,91 and much cumene was made in this way in
petroleum polymerization plants early in World War II. A large ratio
(6 or more) of benzene to propylene is maintained, and yields of 96
volume per cent of cumene are common 91 (the.remaining 4 per cent being
heavier alkylated aromatics).
The alkylation of benzene with ethylene to produce ethyl benzene is
. widely practiced in the manufacture of styrene. The ethyl benzene is
subsequently dehydrogenated to styrene. Aluminum chloride in the
presence of anhydrous hydrochloric acid is the catalyst. The reaction is
conducted 4 at the boiling point of the alkylate (about 105C), and evaporation of benzene from the reactor removes the heat of reaction. Granu81 Universal Oil Products Co,} Phosphoric Acid Condensation, Oil Gas J., Ma.r. 19,
1956, p. 172.
'~'." . -=-----
, ..
_ . - -- .
743
REBUILDING HYDROCARBONS
!
\
20-18.
AT EQUILIBRIUM
Temperature, OF
801 (4270)
932 (500 0 0)
t112 (600 0 e)
1341 (727C)
Propane
n-Butane
lsobutane
1.6
5.4
6.4
18.6
11.0
29.2
31.9
19.5
57.5
53 .6
89.8
95.2
Etha.ne
69.8
12.2
72.1
95 .2
Note that a dehydrogenation of 95 per cent as shown for 1341F does not
mean an olefin yield of 95 per cent. According to the dehydrogenation
reaction the analysis of product gas would be 5 per cent unreacted
paraffin hydrocarbon and 47.5 per cent each of the olefin and the hydrogen gases.
Catalytic methods of dehydrogenation have received attention because
92
744
of the extremely high temperatures required for plain thermal decompoSition (see Fig. 19-5) and because undesirable reactions also occur [see Eqs.
(19-12) to (19-16)] when propane or larger molecules are cracked. Two
general types of catalysts have been employed: (1) ferric oxide supported
on magnesia with potassium oxide (carbonate) as a promotor for the
elimination by the water gas reaction 98 of carbon deposition, and (2)
chromia-alumina u modified with alkali, zinc compounds, or beryllia.
The first type was used extensively during World War II (Type 1707
composition) for the dehydrogenation of ethyl benzene to styrene,
2-methyl 2-butene to isoprene, and butene to butadiene, and these are
stated in the decreasing order of reactiveness. Kearby 9a finds that the
best promotors are potassium, cesiul!l, and,rubidium carbonates or oxides,
the best dehydrogenators are iron and chromium oxides, and the best
support materials are magnesium, iron, zinc, copper, or beryllium oxides.
TABLE
20-19.
Alumina-chromia type
MgO ...............
80
72.4
. .. .. .
18.4
Cr 20' ..............
...
4.6
20
K:lO ...............
CuO ...............
Others .. '...........
,4.'6
....
.....
4
...5
.....
,.
...
.... ,. . .
59.25
,
20
.......
5
40
50
80
4'0
20
0.75
I)
80 ZnO
. ....
10 BeO
.. Kearby, K. K., Ca.talytic Dehydrogenation of Butenes, Ind. Eng. Chern., 42, 295
(1950), and Pitzer et a1., Improved Butane Dehydrogenation Cata.lysts, Ind. Eng.
Chern., 48, 1541 (1954).
-
Several analyses are indicated in Table 20-19. The other type of catalyst,94. Le.) chromia-alumina, appears to be most useful for the dehydrogena.tion of propane and the butanes. Alumina prepared by calcining
specially crystallized alumina trihydrate is used at 600 to 6500 for propane or isobutane. Chromium oxide in the form of its active gel is highly
selective in its action but is destroyed by temperatures exceeding 500C.
If alumina is used as the carrier for 10 to 20 per cent chromium oxide, the
dehydrogenation reaction proceeds at even 50 to 700 but the life of the
catalyst is short. Both the activated alumina and the alumina-chrome
catalysts may be regenerated by careful oxidation of the impurities in a
98 Kearby, K. K., Ca.talytic Dehydrogenation cd Butenes, Ind. Eng. Chem., 42, 295
(1950).
94 Pitzer et al., Improved Butane Dehydrogenation Catalysts, Ind. Eng. Chem., 46,
1541 (1954).
.. - ...
, -'
..
- -~-
. .
---_.._--
.......-
745
REBUILDING HYDROCARBONS
stream of air (diluted with nitrogen) for as many as 200 regenerations. ifi
The life of the catalyst is greatly improved by introducing small amounts
of water vapor. For the dehydroge~ation of isobutane using alumina,
0.1 mole per cent of water vapor is the optimum. Iron, cobalt, nickel, and
some other metals promote the formation of carbon and hydrogen at
temperatures of 300 to 700C, but these metals are being used in commer:cial cracking equipment, etc., without causing destructive decomposition.
Bteam is used with either type of catalyst to decrease the rate of carbon
formation.
Complete thermodynamic data on t~e dehydrogenation of ethyl benzene to styrene have been obtained by Wenner -and Dybda1 96 for two
catalysts. The average heat of dehydrogenation (for the several reactions) is about 60,000 Btu per Ib-mole of styrene. Temperatures of
1000 to llOOF with very large amounts of steam are used. Flow diagrams of these operations are presented by Smith.4 Isopropyl benzene
(cumene) is dehydrogenated to methyl styrene in much the same manner.97 These reactions, J?ot being limited by the low equilibrium concentrations of the lower olefins, take place readily at 1000 to l050F with
large conversions per pass (about 45 per cent for styrene a,nd 60 to 65 per
cent for methyl styrene).
Butadiene and Butylenes. Although the first commercial butadiene
'was obtained as a by-product -in the manufacture of ethylene (Tables
20-3 and 20-7) and much of the butadiene produced during the rubber
crisis of World War II was obtained in this manner or from alcohol, later
in the war butadiene was made by the catalytic dehydrogenation of
butenes.
The dehydrogenation of butane to butene and of butene to butadiene
are similar operations:
Butane to
butylene
Temperature ........................
Pressure .... '" .....................
Partial pressure (using steam) .... .- ....
Con~ersion, per cent .. . ..............
Ultimate yield ......................
.
.
.
.
.
11 00--1125 of
10-20 psig
low
30--40
70--80
Butylene to
.butadiene
1125-1250"F
5 in. Hg to atmospher,ic
0.1 atm
11*-28
60-80
FtlEL CAS
r-__________________~.~RCENERATION GASES
TO VENT
OIL
QUE'NCH
TOWER
BUTAQIN
RICH STReA~
STEAM
GENERATORS
To fig. 20-16
~---,
POLYMER
....:s
STEAM
'
---------------------~-------------~
'~
:::>
FRESH N. BUTENE
'Cl
N. SUTENE
FROM EXTRACrlON
r-l
~~~~~~J
LEAN OIL
STEAM
SUPERHEATER
PREHEAT
CIRCUIT
2-REACTORS
I-O""ATING
'RIGENt:RA'nNG'
- - - -- - - -------------- - --- ..
I,
I
I
IS08UTYLENE ELIMINATION BY
SULFURIC ACID POLYMERIZATION
1
I
,,
BUTADIENE PURIFrCATION
OY SOLVENT EXTRACTION
I
I
Crrus*
I
I
I'
rr
BUTANE
BUTADIENE
BUTANE
BUTYL-ENE----.i-l.......'
FEED
L ' ""
H,.
Wattv
IrQSfI
AoetrJne
IOOpsig
H~ po~ ~
ond SfH'" Ct1lISIIc
FIG.
rCf~
4-1
'
AmDne
1"'---------,
FIfJ.. 20-"
I
Buf)fflle
IDEHYDROGENATION:
rL _________
Iobflh1tfi_
I~
WaIH.--J
20-16. Feed prepara.tion a.nd product pmifica.tion in buta.diene manufacture (see Fig. 20-15).
748
The only extensive use of hydrogenation in the industry is in connection with the desulfurization of naphthas, distillates, and most recently
residual materials (see Fig. 10-13). These processes employ cobalt
molybdenum catalysts supported on bauxite. ' Dozens of plants have
been installed since 1953. During this same period, large amounts of
by-product hydrogen became available from catalytic reforming processes.
The hydrogenation of animal and vegetable oils at relatively low pressures by the use of activated nickel, platinum, or palladium catalysts
involves direct union with hydrogen. In the case of mineral oils or coal,
it is also usually advisable to decompose or crack the oil to some extent as
Ha.tch, L. F., Pet. Refiner, Saptember, 1954, p. 311.
99 Anon.} How to Make Butadiene, CMm. Eng., September, 1954, p. 306, a.nd
February, 1957, p. 146.
96
REBUILDING HYDROCARBONS
749
p.50.
750
sulfur must be handled, recourse must be had to such catalysts as molybdic trioxide, molybdic acid, or chromium oxides supported on charcoal or
pumice. loa Catalysts of this nature are said to be used in the destructive
hydrogenation of crude petroleum stocks.
Thermodynamic relationships17 favor a low temperature, hut at 0 ,to
150C the reaction rate is low. Commercial operations have been conducted at 180 to 190C and at 1 to 4 atmospheres pressure 104 using a
nickel catalyst. Sulfide-resistant catalysts require higher temperatures,
and at such temperatures depolymerization of diisobutylene to isobutene
occurs rapidly unless the pressure is high. 17
Catalytically cracked gasolines contain more olefinic hydrocarbons than
are desirable, and hence methodslOf> of hydrogenating the olefins without
hydrogenating the aromatics are being studied.
Supported nickel sulfide catalysts are remarkably selective in the range
of 200 to 300C in hydrogenating diolefins to monoolefins without hydrogenating monoolefins to paraffins. 1011 Diolefin removal is necessary when
al~ylating B-B (four-carbon-atom) cuts from vapor-phase or thermal
cracking operations.
In the manufacture of ethylene small amounts of acetylene are produced
(Table 19-8) and the specifications for ethylene allow only. 10 ppm.
Larger amounts are produced if regenerative type refractory furnaces are
used. 42 Selective catalytic hydrogenation is used (Fig. 20-4) to eliminate
the acetylene. 107 Temperatures of 400 to 550F, pressures of 50 to
350 psig, and space velocities of 500 t~ 1,000 may be used. Enough
hydrogen for the reaction is usually pres"ent in ,the ethylene stream. In
connection with Fig. 20-4, it is necessary to provide an auxiliary pipestill
for regeneration of the catalyst with air, hydrogen, and steam.
ISOMERIZATION
ed., vol. I, p. 337, John Wiley & Sons, Inc., New York, 1938.
10.10 Edlund, K. R., Proc. 8th Midyear Meeting API sec. 3, 87 1 1938.
1811 Voorhies, Smith, and Hemminger, Hydrogenation of Catalytically Cracked
Naphthas . . . , Ind. Eng. Chem., 39, 1104 (1947).
104 Anderson et al., Conversion of Diolefins in Alkylation Feedstocks . . . , ACS
Meeting, Chicago, Apr. 19, 1948.
107 Fleming et al., Selective Hydrogenation, Pet. Refiner, September, 1953, p. 138.
REBUILDING HYDROCARBONS
751
752
TABLE
20-20.
Vapor-phase proeessll8
Shell
bauxite
AIOCJersey
Liquid-phase proces8CS
IndianaTexas
UOP
Sublimed on Complex on
Liquid
bauxite
quarts ohips
complex
Shell
Dill80lved
iu SbCh
50-120
200
2-14
200
40
85
210-300
200
0.5-1.0
270
235
0.6-1.0
Carbon llbeel
5{}-120
4
li
38
8S
lio-l20
5
45
200
205
180
235
365
300
0.5
1.0
Haatelloy B or
gunit.e Obment
3
14
2.5
Niokel
(Pet. Refiner.)
753
REBUILDING HYDROCARBONS
catalyst-scrubber into the contactor. The valuable active catalyst introduced in the scrubber passes back with the butane into the contactor,
whereas an inactive AlCl a hydrocarbon complex formed by side reactions
collects at the bottom of the scrubber for periodic removal. Time in the
contactor is 10 to 15 minutes and this effects a conversion of 50 per cent
or more for butane 123 and 55 to 60 per cent for pentane. Catalyst is
recovered from the isomerized stream by fractionation, and the condensed product is stripped of hydrochlo:fic acid. The final product is
caustic washed.
In isomerizing butane with aluminum chloride, only a small amount of
catalyst-hydrocarbon complex is formed, but pentane and especially
hexane produce more complex. Both pentane and hexane tend to crack
during treatment and this is the cause of the extensive side reactions. 124
The formation of sludge is inhibited in pentane isomerization by the use o~
0.3 to 1.3 weight per cent benzene, and in hexane isomerization, hydrogen
is used as an inhihitor.
In the isomerization of naphth a 119 using aluminum chloride, the
Research octane number in a once-through operation is increased from
65 to SO. Further increase in octane number occurs with recycling '(91 at
2: 1 recycle ratio), but the economy of recycling is doubtful because of
difficulties with fractionation. When processing mixed hexanes 125 operating conditions are
Reactor temperature .................... . ........... "
Reactor pres~ure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
Space velocity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . ..
Catalyst depth '. . .... . . '. .......... . ...... , . . . . . . . . . . . ..
Hydrogen added, .std. eu ft per bbll'eactor charge . . .......
HCl weight per cent of reactor charge . ... . ........ '..... ,
AlOh injection rate per bbl reactor charge. . . . . . . . . . . . . . ..
240--250F
700-850 psig
1-2
20-25 ft
50-180
4-8
0.5-1.0
tntimate yields are almost 100 per cent, and the conversion to isoparaffins
is 50 to 60 per cent on a once-through basis.
Th~ use of hydrogenation cracking catalysts lO 6-113 for isomerization,is
so new that processes cannot be described here. However, it is probable
that such processes will displace the aluminum chloride processes except
for the isomeriza.tion of butane. The platinum catalyst reforming
processes cause some isomerization of straight-chain paraffins, and continued developments .may lead to cheap means of isolating straight-chain
materials for recycling through such processes. It is obvious that isoShell Development Co., Pet. Refiner, September, 1954, p. 205.
m Evering et al., Ind. Eng. Chem., 46, 582 (1953).
126 Armistead, G., Jr., Isomeriza.tion . . . Hexa.ne, Oil Gas J., Sept. 28, 1946, p. 43.
123
754
spiCy
II
co/7Gt'nSer-I
Flow recordin9
Absorber
Hose
conneclJ~
a:~ter1
In
.LI__
FIG. 20-18. Desulfurization of gal!
755
REBUILDING HYDROCARBONS
P.G,
)'
Exnaust steam
Scale
poc/(el
Mad
Live steam
Exllousl
steOf/l
-:-f------J---
xl1ausl
5team
Rotameter
Condensole a
'Xhousl steam
10 feed-water
~~--~~~~~
lon*
I
\
Byposs
,
t
- 1
Mo/reup
drom
To sewer
Cooling waferWoler 10 exhaust
sleom condenser
Ins/rumenl
(lOS
meIer
Coolin water
return 10 lower
SI1uI-ofL9=l~Fuel gas 10 boIler
valve
generolors 8 camp
P.G.
1~19 t t
DisPlocemen/~
Waler inlellrorn
coolin tower
756 .
Total
1~d)
Ca~alytie
reforming
(Platforming)
per cent
Ca.talytic reforming .
plus isomerization
(Penex)
!
I
I
!
I
93.5
81.5
84.5
76.6
85.5
84.5
QS.O
96.5
96.5
86.5
91.0
91.5
100
100
100
I .
\. \
:
!I
I
I
i
II
1,
.j
.i
!I
The recovery of hydrogen sulfide from natural and refinery gases, and
its conversion into sulfur or.s~lfuric acid, is being conducted extensively.
In Wyoming oil and gas fields alone, the available sulfur is estimated 128
to be 5,678,400 long tons (1950), in Arkansas sour gas .fields (1942) at
least 1,500,000 long tons, and in the Permian Basin of West Texas and
southeastern New Mexico a daily production of at least 400 long tons 12 &
(1950).
Hydrogen sulfide is first removed from the gas by one of the many
conventional regenerative gas desuliurization processes. Amine solu- '
tions are the most widely used desulfurization agent. They remove
carbondiqxide as well as hydrogen sulfide:
or
RNH2 + H 2S ~ RNHaHS
RNH2 + Co, + H 20 ~ RNHa H C0 3
(20-14)
LI:G:ND
p'RISaURt, P$IA
CJ
CJ
TI::W-PERAT UAE.,.
'LOW, L8 /"R
CJ
U(1-1
'LOW,
s.c. r. H.
FLOW, G RM
-of
!l
~IQUID
SULfUR
,
TO STORACe.
-_..
I
..... ~-.-.I'':' :_~!)
...... - _- - - _.l
. : : ..... "L.-_-.:.-.;
~
.j. - - - - - - - - '
<m6
(()(Z OM J.)
758
(MDEA) 127 are selective in absorbing hydrogen sulfide rather than carbon
dioxide. Consumption of amine ranges from 0.5 to 2 lb per million
cubic feet of gas depending mainly on the pressure. Most of the loss
occurs by' entrainment, but in addition small amounts of thiosulfates are
formed by reactions with oxygen. These can be converted to sodium
thiosulfate by the addition of soda ash, but eventually the concentration
becomes so hlgh that a current elimination of the thiosulfates is necessary. This is usually done by rejecting a portion of the solution after
steaming it for the recovery of. useful amine.
The plant equipment is basically simple, only an absorber (usually
20 plates), a rectifier or regenerator (a]so 20 plates), exchangers, a cooler
for the amine solution, and a reboiler at the base of the rectifier for supplying heat to the process. Thus, this is an opportunity to introduce the
. details that are necessary in actual plant operations (Fig. 20-18),128 by
showing a more complete type of flow diagram.
The sulfide-rich gas is then processed for sulfur as indicated in Fig.
20-19 which is a somewhat Itpackage-type plant. 129 In the presence of
bauxite (and many surface active materials) hydrogen sulfide burns
directly to sulfur and water. However, this reaction is so highly exothermic that sulfur is usually produced in. two steps as follows:
3H,S<
H 2S
"
+ 17202 ~ S02 + H 0
)2H 2S
+ S02 ~ 38 + 2H,O
(20-15)
(20-16)
127 Miller and Kohl, Selective Absorption of Hydrogen Sulfide, Oil GM J'J Apr. 21,
1953, p. 175.
124 Anon., Oil GM J., May 19, 1945, p. 123.
Ui Vlcek a.nd Graff, Globe Solves Pressing Air-.p ollution Problem . . . J Oil Ga8 J: ,
July 6, 1953, p. 64.
CHAPTER
21
Since 1938, the development of methods of applying or handling catalysts in the production of gasoline has become fundamentally important
to all chemical industry as well as to the petroleum industry. The
approximate capacities of such plants during 1955 were: l
Cracking bpd
De8Ulfuruation or
bpd
hydrogenA~ion.
Fluid (F.C.C.). . . . . .. 2,621,000 Plat.inum cat .. . ... . . 748,000 UJ;lifining. ~ . .. ........ . 192,000
Thermofor (T.C.C.)...
730,000 Hydro! orming. . . . . .. 105.000 Hydrofining ... .' ...... . 114.000
Boudriftow. . . . . . . . . . .
186, 000 Houdruorming. . . . . . 41,000 Hydrotreating ... . .... . 16,000
~oud.ry . . . . . . .. . . . .
55 I 000 Thermofor ..... ' . . .. 24 ,000 Hydrodeaullurisa.tion .. . 97,000.
Cyeloveraion. . . . . . . . .
28 , 000 Others..............
9,000 Dieaulforming .........
1.000
Turner, LaWanda, Refining Capacity Presses 9 Million Barre1B, Oil Ga8 J., Mar.
760
761
pentenes in the eli cut 20 to 30 per cent. 5 The higher the temperature the
greater the olefin production. ~ Figure 2-3 shows the general composition
of catalytic gasolines. They contain less olefins than thermally cracked
or Fischer-Tropsch gasolines.
Catalyst Handling. Four main ways of using catalysts have been explored (Fig. 21-1):
1. Fixed-bed: Houdry and Cycloversion catalytio cracking) platinum catalyst reforming, t):Le original Hydroforming installations, a.nd the desulfurization processes are
examples.
2. Moving-bed: Thermofor cracking with bucket elevators, and the Thermofor
Catalytic cracking (T.C.C.) and Houdriflow air-lift processe8 are examples.
3. Fluidized-bed: the Fluid and recent Hydroforming plants are examples as well as
many (at least 20) chemical applications. &
4. Once-through: the SuspeIlBoid catalytic cracking process once attracted attention. 7.8
'"---fj'/MeJ'i!
Iud
(a)
ProduCIS
Flue
r--~...,gas
Air
(c)
r\~
Vap0rJz r
Crocking still
combustion 01,
(b)
Litloi,
calalysl
10 fillers. e/~
(d)
FIG. 21-1. Basie ways of ha.ndling catalysts. (a) Fluidized catalyst; (b) airlift (T.e.C.
and Houdriflow); (c) fixed bed (Houdry and Cycloversion); and (~) suspended in oil
(SuspeDBoid) .
762
763
21-1.
11.8
WREN CRACKING
TO
12.0
Space
velocity
Cat.
temp
Reactor
temp"
760F
800 F
Inlet
Oil-inlet temperature
Cat.joil
ratio 3
3 .5
2.1
1.0
1020
1080
860-920 To 31.5c
930-960
29-33
960
1020
1080
850-880
875-920
930-960
32-40
36-44
960
1020
1080
860-875
870-955
940-955
&
29-37
.............
............
40-48
oooo
....
.....
.,
...
. . . I'
880F
Inlet
33-42
36-45
36-45
40-48
41 ....49
.......
41-49
45-54
44-51
47-55
48-56
42-53
43-55
49-56
52-56
55-62
. ....
....
..
..
..
oo
..
59-65
58-65
60-67
Obviously, the large amount of heat contained in the hot flue gases
(1000 to 1200F) from the regeneration operation must be recovered by
heat exchange or the use of waste-heat boilers. In addition, the Houdry
process employs these gases to drive the air turbine.
Only one once-through process (Fig. 21-1d), the Suspensoid process, has
been applied commercially. The catalyst (spent lubricating-oil clay)
passes through the cracking furnace along with the oil and is removed from
the fuel oil by ~n Oliver precoat filter. 8
Yields. The accurate prediction of yields is difficult not only because
764
of the effect of legitimate operating-,variab.les,-but also because of great variations in the unsaturation 'and cleanliness of charge stocks. Entrainment of asphaltic material into the charge stock during preparation of the
feed, contnbutes almost quantitatively to coke deposition and at the same
time has little direct effect on the yields of gasoline and other products.
Likewise, sulfur, nitrogen, etc., act mildly as inhibitors to the cracking
reaction. These factors cannot be easily assessed, and they lead to variations in yield, especially in the percentage of coke.
Yields depend more directly on "percentage conversion JJ than on any
other common factor. Percentage conversion is defined as 100 minus the
amount of catalytic distillate or cycle stock, but corrected for any gasoline
co~tained in the feed material. The gravity of the cycle stock is usually
almost the same as that of the charge stock, and hence the conversion is
almost the same on either a liquid volume or a weight basis. In tum, the
percentage conversion is a function of at least the type of feed material,
reaction temperature, catalyst-to-oil ratio, space velocity,. and catalyst
activity .. Table 21-1 indicates the ranges of these variables for the T.C.C.
process. Increasing severity is encountered as-one moves to the right and
downward in the table toward higher temperatures, higher ratios of
catalyst to oil, a.nd lower space velocities. The catalyst-to-oil ratio is on a.
volume basis, i.e., eu it catalyst (about 45 lb per cu ft) per Cll ft of liquid
oil (60F), and the space velocity is the volume per hour of liquid oil (60F)
per volwne of catalyst bed. The activity index used in Table 21-1 is the
standard Cat. A method used in testing T.e.C. catalyst. 1I Table. 21-1
also appears to represent fa.irly accurately the behavior of the Houdritlow
process. lO The effect of recycling is somewhat a.s follows:
.
Single-pass
conversIon
0.5
'50
55
60
47.5
53
59
64
56.0
61.5
67.5
73
88
70
79
94.0t
65
75.5
85.5
40
45-
1.0
1.5
2.0
67 .0
75.0
83
84.0
73
80.5
91.5
91.5
99.0t
-
purpo8~s.
10
765
't _
cat.joil ratio, Ib/lb
even y - space velocity, Ib oil per hrjlb cat. in bed
(21-1)
Various exponents (from 0.5 to 1.5) for the space-velocity term ha.ve been
proposed, but since agreement has not been reached, an exponent of 1.0 is
used herein. At the somewhat standardized conditions of a reactor temperature of 900F, a carbon content on the regenerated catalyst of 0.5 per
~ j -.: ~L _ ~I
.,.,.
6.u
5.0
40
~ ~~.
I-----+--ft~
~/
-' ,
~~'O
3
~
.'
-I
,
./
f,lilJ..---+-V-l----i
r7
"
/1 / /
r:v7
t .5/ / /
rt.,7
"II
\) I
~'i
-/
---+-/----'-/-+-----1
~I
(01 '
f:,O-j / /'
~ . 1.0 II
~, 0.8
ji
i90S 0115 1
11-
'~I
0/
~"/
(;) .~
~/
'rol
~I
I /Low-bqiling s!roilhto-run /
"/
~I
~ 25
c~ockinq
by
II
/I#- -1------.(
I
fJ ~_--II---_-j
I~
r~/--~---J~---/+---.....,/~--~/~~----~--~
~ Q6 V
~' Q5
,/
7
!
/
/ Conventional
1
i----f1'_ +---1-_--1---.
' ' - a heavy
---+-',_ --'-_ _-+-_ _~
0.4
/
I
straight-run
/
/
gas o';s
a3~v/+----i,+(~--;l-~1
02~---~~---~~
10
20
30
/J~~/---;r-~~-'v~---~~----~----~
___~-L__~~_____~_______L -___~
40
50
60
10
80
Percentaqe conversion
FIG. 21-2. Indico.tion of single-pass severity factors [Eq. (21-1)] for 900F reaction,
0.5 weight per cent co.rbon on catalyst, and a Jersey II D + L" activity of 30.0. (See
Ta.ble 21-2 for effect of operating variables.)
11 OdeD. and Granberry, Propane Deasphalted Gas Oil Cracking Feed Stock,
Ind. Eng, Chem., 44,896 (1952).
766
cent, and a Jersey" D + L" activity12 of 30, severity is related to conversion somewhat as indicated in Fig. 21-2. Il,J20 The lines on Fig.
21-2 have various Characterization Factors depending on the kind of
feedstock. Characterization Factor of the feed, is basic, but in addition
higher conversions are obtained with straight-run materials, and lower
conversions with low-boiling (below 600F) materials. Solvent refined
feeds occupy an intermediate position and the lowest conversions of all
are obtained with light low Characterization Factor cycle stocks. The
general effect l l on conversion, of reaction temperature,. carbon on catalyst, and catalyst activity or poisoning is indicated in Table 21-2~ Three
separate corrections can be read from this table.
TABLE
21-2.
V AIUABLE8 ON
FIG. 21-2"
(Read 3 separate corrections)
EFFECT OF OPERATING
THE PERCENTAGE
CONVERSION OF
Catalyst
activityb
15
20
25
27.5
28.5
Reactor
temperature
..
..
..
Carbon on
regenerated
catalyst
..
..
..
..
....
875
885
892
900
907
0.8
0.6
0.5
32
33
915
925
0.3
. 0.2
36
950
975
..
.
..
. . ..
30
38
40
45
..
..
0.4
..
Correction to
conversion of
Fig. 21-2, %
-18
-11
- &
- 2.8
- 1.6
- 0.7
0
+ 0.7
,+ 1.&
+ 2.6
+ 6.2
+ .8.0
+10.0
+14.0
II
767
21-3.
Cat./oil
ratio
Severity4
Coke
(wt)
C 2's
Methane
Hydrogen
Nat. Syn. Na.t. Syn. Nat. Syn. Nat. Syn. Nat. Syn. Nat. Syn.
- - - - - - - -- - - - - - - - - - - - - 5
7.5
10
15
25b
0.9 '0.72
85
84
0.96 0.88 94
1
100
1
1.08 1.21 111
1.17 1.55 127
93
100
llO
126
105
107
116
115
128
...
100
100
...
106
100
93
95
92
107
100
93
84
111
100
88
74
...
..
84
120
100
187
130
100
90
70
79
80
45
59
108
150
118
100
4 Note tha.t the space velocity as well as the cat./oil ratio was changed to obtain
these severities.
b Extrapolated.
over fresh feed). Thus, a plant which is able to accomplish only a 47 per
cent single-pass conversion does not respond as well to recycling as a
plant that can crack to a 62 per cent single-pass conversion. The average
amount of recycling in United States plants during 1956 was about 18 per
cent in Fluid process plants, and 25 per cent in moving-bed plants.
Recycling is not entirely effective because coke and gas production
increase more rapidly than gasoline production. In total recycling,
yields appear to approach 61 per cent gasoline, 27 per cent B-B cut (less
by the Fluid process), 12 to 14 per cent coke, and 13 to 15 per cent dry
gas. Cycle oil is rich in aromatics and hence higher operating temper~
Cures are required when recycling is practiced. Much cycle oil is therSchall et a!., Chem. Eng. Progr., December, 1949, p. 746.
14 Schwarzenbek et al., Fa.ctors Affecting Octa.ne Number, Proc. Third World Pet.
Congr., sec. IV, The Hague, 1951.
16 Nelson, W. L. (many references given), Oil Ga8 J., Jan. 14, 1957, p. 126.
u Oden and Perry, Oil Gas J., Mar. 22, 1954, p. 164.
17 See page 672 of the Third EdiL,ion of this book for additional references.
13
768
__1-----
I---Single-poss ---l~_
.
....,j
..
).'t'CycIie rotlOI .
24
1\
~ 18
:t:s
~
.~
-..;::
........ 16
~
11)"\
tj
th
1./V&i
o.5~ ~
GASOLINE
.......
convers/on"""\
(IpoCJ/Y ~b?'
t
DEBUTANIZED
20
./
/'
12
10 '// '
<ts
a~
V"
/
~
~
.-
v....
po
/"
./
.//
~/ V
lighter}
4S
. ct
408
"i:t-
-;/
v/
./
V
~ DRY GASES \
{Proponl' ond
($
Single -poss
conversion
COPOCit
./
55 ~
'7
.~
/'
60
SO~..
\
BB cuI (totol4 -
/'
,/
--</
//
/'
'G
J/
/"
../
~
_
.....
~~
~/
;'/
I:~V
.J
Single-pass
22
~ 14
\:l
g
Recycling ---....:.;.~~
35
.~
30~
/ / 25
J~//~
;7
. /~ / / /
~ ~ V' !;~
./~~v / '
/
\
~ 41
1-1.0- ti
'
_J
.-/
c'1..,lt r(J
( :.5<Re ~--= ICOKE
V"
ro
00
amounts of B-B cut and more coke and gas than the moving-bed proce&Ses. Figure 21-3 is an average for the major processes. A method of
comparing the efficiency of .catalytic cracking is
.
ffi mency
E
X 100
769
In general, the moving-bed processes, at a particular conversion, produce less coke (7 to 10 per cent), and the Fluid process&.1D-17.18.19 more coke
(11 to 14 per cent) than the values indicated in Fig. 21-3. Nearly the
same amount of gasoline is produced by all processes, but the FIuidprocess gasoline has a slightly higher octane num1?er (mainly because of
the higher reaction temperature). Likewise the amount of dry gas
(propane and lighter) in the moving-bed processes is "lower than indicated in Fig. 21-3 by about 6 to 9 per cent (and by the Fluid process the
same amount higher).6,1()-..19 The Fluid process produces a B-B cut (all
4-carbon-atom materials) that is richer in olefins, but 7 to 14 per cent
less B-B is produced, wherea.s in the moving-bed processes 7 to 12 per
cent more B-B i s produced. ~.lo-19 The cost of catalyst or its -replacement
is usually larger for the moving-bed processes. All of these comparisons
are for the same percentage conversion. In practice, a-(iifferent conversion or severity is used in each process, and after such adjustments 'and
after having utilized the gases, the total liquid yield by all of the processes
is about the same. The composition of the dry gas and B-B cut can be
estimated from Table 21-4. The higher the reaction temperatur~, the
larger the unsaturation of the gases.
~
T.ABLE 21-4.
CoMPOSITION OF
CATALYTIC GASES
Range
B-B cut:
Butenes, vol. %",."" .. " . " " .
IsObu tane, vol. %........ .
Propane-propene cut:
wt % of dry gas .. : ....... .
40
35
52
51
(Fluid)
(T.O.C.)
(Fluid)
(T.e.C.)
68
66
68
71
62
(Fluid)
(T,O.C.)
(Houdriflow)
(Fluid)
(T.C.C.)
. 21-49
17-42
42-68
61-85
62-76
65-78
60-76
54-65
Example 21-1. Yield from 30 API East Texas Gas Oil. In a Fluid-process plant,
the space velocity is 3 and the catalYBt-to~il ratio is 8. This is a. severity factor of
8 + 3 or 2.67. According to Fig. 21-2, the standard conversion for a. conventional
11.9 Characterization Factor feed is about 63 per cent, and this applies to operations
Moorman, J. W., How Conversion Level Affects Product Distribution, Oil Ga8 J.,
Jan. 4, 1954, p. 76.
.
It Nelson, W. L., p. 673 of the Third Edition of this book and Oil Om J., Aug. 30,
1947, p. 67.
18
770
at 900F, a residual carbon of 0.5 on the catalyst, and a catalyst activity of 30. The
plant is actually operating at 925F, the catalyst has an activity of only 25, and it
bears 0.7 per cent carbon. According to Table 21-2, the conversion will be lower by
l) per cent because of the low activity, the reactor temperature increases the conversion by about 2.5 per cent, and the high carbon reduces the conversion by about 1.1
per cent, so that the actual conversion is about 63 - 5 2.5 - 1.1, or 59.4 per cent.
Figure 21-3 indicates the following average or basic yields and, in the second column
of the tabulation, the somewhat different yields of the Fluid process at this conversion
(note that this does not necessarily mean that the Fluid process is inferior).
Basic yields
Vol. %
..
....
15.5
41.7
40.6
Fluid yields
Wt %
4.6
7.3
..
..
..
Vol. %
...
&
Wt %
5.15
7.9
14 .0
41.7
40.6
The amounts of various gaseous components (Table 21-4) for the Fluid yields of 7.9
per cent dry gas and 14 per cent B-B cut are about:
Propane-propylene .......
Vol . % Wt%
Ethane and lighter ....... 7.9-5,4
Propylene .... . .......... 5.4XO.71
Propane .............. . . 5.4 - 3.8
Isobutane ..... .. ..... , .. 14 X 0.52
Butylenes . . '. . ... . ....... 14 X 0.40
Butane ................ . 14 X 0 .08
=
=
2.5
3.8
1.6
7.3
== 5.6
= 1.1
14.0
7.9
If this plant (59.4 pel' cent conversion) were used by recycling 0.5 of cycle stock to 1.0
of fresh feed, the conversion would be raised (Fig. 21-3) to about 70. This wa.s
obtained from the dashed line for 0.5 recycle ratio and among the 3 lines at 59.4 per
cent conversion.
771
Yields by the Fluid process would be smaller than these average yields.
These low yields compa.red with the results of Example 21-1 leave the impression
tha.t the viscosity broken stock is very inferior, whereas in aCtuality, a greater severity
and a higher temperature could be used to crack the stock more thoroughly. However, these changes in condit.ions are expensive, or !"esult in reduced capacity.
Another way to compare the two stocks is to burn the same amount of carbon, i.e.,
4.6 per cent as in Exa.mple 21-1. This would require a. greater conversion (see Fig.
20 Ardern et 8.1., Ca.ta.lytic Cracking in Fixed and Moving Bed Processes, "Progress
in Pet. Technology," ACB Meeting, New York, September, 1951.
21 Bergstrom et al., Recent Developments in T.C.C. Cra.cking, Proc. Fourth World
Pet. Gongr., Sec. III, Rome, 1955.
22 Hamilton et aJ., Catalytic Cracking in Airlift T.O.C. Units, Pet. Engr., August,
1952, p. C-5.
23 Noll and Luntz, T.O.C. Processing . . . , Oil Gas J., Jan. 15, 1948, p. 81.
2" Shelley and Rackley, Better Yields from Ca.t. Cracking, Pet. Processing, December, 1952, p . .1772.
26 Duval and Holmes, How Charge Stock Properties Affect . . . I Pet. Reji:ner,
\ugust, 1952, p. 109.
772
PETROLEUM REFINERY
ENGINE~G
60
---- '---...--
60'-
50- ~ ~
40-
.. ...--
---
70
~~
-2...0
I
,---
r----.. --.20
_40
-- '--~20
30
302020-
--
/0
--ZP'
1-_
}-Percentage converSion:'; .
ror
10
-~
60
~~~
""-
40
~s~
# 3n
r-40.;:..,.
~
.",.,
. ~
'-
"
"-
2 #-=:::'
~
::.e
"- ~ f\
~ " . ." "
""'r--......
"'- ....
-............:: , - "'-
----- ---
20
Il
60
....
"-~.
'80
"'-6Cr
-sq_.
40
-~
2:1-4) i.e., about 50 per cent, but the gasoline yield would rise to about 35 per cent.
Such a change would, of course, :r:equire 8. large adjustment in the severity.
In catalytic reforming, only the platinum catalyst processes (Platforming,26 Catforming,27 Sinclair Baker,28 Ultraforming,29 Powerforming,30 Sovaforming,31 etc. 82) are sufficiently well defined to allow the
prediction of yields u (see Table 21-24). The approximate maximum
Haensel, Vladimir, Oil Gas J., Mar. 30, 1950, p. 82.
I ' Fowle et a1., Oil Gas J., May 26, 1952, p . 181.
t8 Decker and Stewart, Oil Gas J., July 4, 1955, p. 80.
U Gumaer and Raiford, Oil Gas J., Aug. 8, 1955, p. 119.
30 Anon. (Std. Oil N.J.), Oil Gas J., Mar. 5, 1956) p. 62.
al Backensto et aI., Pet. Refiner, August, 1956, p. 165.
"Sittig a.nd Warren, Pet. Refiner, September, 1955, pp. 230-280.
25
773
20
'.
Single-pass
// ~
1.0
conversion ~ ~-
~ /8
't'"
"/
/t/W
~
12
V~
V VO:5
recycle ralio
..
./
35
so
45
40
55
68
'9
II
12
Coke. wI %
88
ing conditions, but Fig. 21-6 "is based on the optimum or best operating
conditions for each feed materia.L The effect of boiling range on the
octane number of reformer charge stocks (see Fig. 21-6) has recently been
published. 38a About 12 to 17 per cent of butane can be added to the
debutanized ~aterial to produce 10 R.v.p. motor gasolines, making total
yields of about;
n Nelson, W. L., Yields by Platinum Ca.talyst Reforming, Oil ~ J., Jan. 3, 1955,
p. 117; also Oil Gas J., Nov. 12, 1956, p. 211.
aa.. Nelson, W. L. t Oil Gas J. t Nov. 18, 1957, p. 246.
774
Approx. percentage
Charac teriza tion
Factor
11 . 6
11 .7
Pentane
plW!
10 R.v.p.,
90.7
104 . 3
89.1
102.5
101.0
99.4
97.7
11.8
87.7
11.9
86.4
85 .0
83 .3
12.0
12.1
95.8
Illustra.tion of
charge stock
Coa.sta.l
Venezuela
Texas
Mid Continent
Pennsylvania
Middle East
Yields of propane (including propene) are about the same by all of the
platinum reforming processes (Fig. 21-6) but the Sinclair-Baker ll8 and
Powerforming 30 processes appear to produce less butanes (and butylenes)
than the Atlantic 27 process, and the Powerforming,30 Platforming, and
Ultraforming 29 processes produce an intermediate amount. The ratio of
iso to normal compounds for butanes produced by the Catforming process
is 1.1 (only 0.71 by Platforming), and for the pentanes the ratios are 1.7
and 1. 94. Debutanized reforrnate usually has a Characterization Factor
of 11.35-11.50.
Products. The major products of catalytic cracking are (1) olefinic
gases that are useful for polymerization or alkylation, (2) cracked gasoline, and (3) catalytic cycle oil. ' The latter is produced in amounts' about
equal to the amount of residual fuel oil produced in thermal cracking,
and its disposal is requiring a revision' of the specifications of distillate
and diesel fuel oils to accommodate such materials.
Catalytic 390 'e nd point debutanized gasoline has a Characterization
Factor of about 11.5 regardless of the Characterization Factor of the
feedstock or the percentage conversion. Apparently the cracking reaction produces the same type of organic molecules from any charge stock.
Thus, the gravity of debutanized gasoline is 51 to 53 API, and with
butanes to 10 Reid vapor pressure, 55 to 57.5 API. " Heavy naphthas
(300 to 400F) or gasolines have Characterization Factors of about 11.3
from highly paraffinic charge stocks down to about 10.8 from naphthenic
feeds.
, The octane number of the gasoline is affected by the reactor temperature (Table 21-5) but scarcely at all by other operating conditions. It
increases only 0.5 to 1.0 units (sometimes none) for an increase in the
conversion of 10 per cent (in the range of 50 to 80 per cent) and it increases
only slightly with catalyst-to-oil ratio., However, low Characterization
Factor feeds produce gasolines of slightly higher (1 to 3 units) octane
numbers, and Table 21-5 is based primarily on Mid Continent feeds such
775
100
..
t:-.. .
...
:~~
~,
.....
'r'::
~~ I'-....
'""'~IV
c~roclerizolion,
fOClol
PROPERTIES
: \ " ""'l6
"
r'\.
OF
Il8\ \ t\ CHARGE
STOCK
11.7\.
~'\ ~ ~.II.~
12.0
r-...
}2.1 ' \
t\
~ 1\\~'\ ~esllCh
oelone -
rNJmber
30
1\ \
\ \
\
',-
75
I.........
..-
~i'--...
PROPAN~
.S?"
...J
"-
~
f
'K
+
BUTANES
...............
\ \\
,,
,
....... ....
~
., ........ ""
"'
...............
1', \
\
\
15
\
\
10
~
".
'"
,,
.............
r--
~,
t-_~
"'"--
80
85
90
95
%yield-.deMonized reformole
FIG. 21-6. Approximate relation of octane number to yield of reform ate by platinumcatalyst reforming of 200-400 F naphthas (also yields of propane and butane). See
reference 33a for the effect of boiling ra.nge on the octane number of charge stocks.
70
75
Vol
776
Mm
'21--5.
800
8-50
900
950
3 co TEL
Clear
Syn.
Clear
Nat.
Syn.
Nat.
Syn.
Nat.
Syn.
Nat.
76
86
86.5
86.5
86.5
86
86
88
92
87
95
81
87
92
87
96
94
95
96.5
98.5
99
92
95
98
99
79
80
77
81.5
80
.82
82
available in Table 21-7, and Schall, Dart, and Kirkbride 18 indicate the
following gravities for Houdriflow cycle oil from East Texas gas oil (these
gravities are lower than those found in most of the literature):
Conversion
API
Conversion
17.9
API
80
75
'60
24.3
20
50
70
21.7
65
23.2
40
0
26.6
28
28.9
Range OF
ASTM-I.B.P. . . . . . . . . . ..
10~ .............
50% ............ ,
90% .............
E.P .............
400-450
445-520
515-635
580-70
630-820
Nelson, W. L., Properties of Cata.lytic Cycle Stocks, Oil Gas J., Dec. 14, 1953,
p. 157.
U
777
21-7.
Characterization
Factor of feed
11.2
11.4
11.5
11.6
11.7
11.8
11.9
12.0
12.2
CI
40%
50%
60%
10.7 a
11 .0
11.2
10.5 cJ
10.85
11.05
lO.l cJ
11.35
11.45
11.25
11.4
11.6
11.7
11.75
11.8
11.5
11.55
11.6
11.7
70%
80%
10.la
10.3
10.65
10.6
10.8
11.05
11.2
11.3
11.4
11.5
11.55
10.9
10.2
11.1
11.2
11.3
11.35
10.85
11.0
11.1
10.6
Extrapolation of data.
TABLE
21-8.
40%
50%
60%
70%
80%
CI
11.4
11.5
42
46
31 .
26.5
23
33.5
31
27
...
.....
'"'
11.6
49
11.7
53
44
40.5
36
.- ....
38.5
35.5
31.5
25
. ...
. . ..
29 . 5
...
11.8
.57
49.6
45
39.5
34
23.5
C.F.'a
11.9
61
53.5
50
43
37.5
27.5
and D.L's
12.0
65
12.1
68
12.2
72
52
45.5
39.5
30.5cJ
47.5
41
32.5 cJ
49
42
33.5cJ
778
API
Coke ....... . . " .... . .......
Ethane and ligh ter ....... . ..
Propylene . . ... . ............
Propane . .... . .......... .. . .
Butylenes . .................
lsohuta.ne ........ ',' ........
Butane .. " .. . ..............
Gasoline . .... . ..............
Cycle stock .................
Feed gas oil. ........... . .. . .
II
II
gal
...
,. . . .
. . . .. .
...
4.35
4.24
5.00
4.7
4.86
6.402
7 . 38
7.296
. ......
., .
. , .
....
. ..
~
52.5
28.1
30.0
Wt per Volume
Wt %" Vol. %r>
100 gal
%
5.15
2.5
3.8
1.6
. ,. ... .
.. .....
......
........
41.gb
100
..
.. .
,
....
...
5.6
7.3
1.1
41.7
40.6
....
37.6
18.2
27.6
11.7
28
34.2
5 .3
267.0
300 .0 b
729 . 6
6.30
2.72
5.60
7.30
1.10
41.70
40.6
100.0
Information is not complete enough for the use of the polymerization chart (Fig.
20-8), but for an olefin composition ratio of 2.0, a reactor tempera.ture of 380F, an
olefin space velocity of 0.08, a total space velocity of 0.18, and a catalyst activity of
50, the total conversion of oletins by weight will be about 90 per cent (this is a high
tota.l conversion). On such a. basis, and if 90 per cent of the olefins are exposed to
polymerization, the yield of polymer gasoline per 100 gal will be about:
0.9 X 0.9(27.6 + 28.0) - 733 a.1 (
t)
6.151b/gat
- . g
or per cen
The .6.rul.1 gasoline, a. debutanized total of 41.7 + 7.33 or 49.0 per cent, will have 8.
vapor pressure of only about 5 psis.. Butane will be added to produce a. total gasoline of 10 R .v.p. Most approximately ~he amount of mixed butanes required wiU be
a little more tha.n the difference in vapor pressures, namely, 5 to 6 per centl'but'more
specifically, using the true vapor pressures of Table 4-12, and a mole basis:
a,
6.5 X 58 X 100
4.77
93.2 X 100 6.5 X
6,249
50
58 = .
per cen
4.77
The percentage of sulfur in catalytically cracked products can be estimated from Figs. 4-37 and 4-38. Material balances indicate that very
much of the feed sulfur appears in the flue gases and cracked gases.
779
780
TO moving-bed
croclring unit
VaptJr feed
Pn'mory flash
Hot
topped
crude
oil
L l'quid feed
-Sleam
I
r"""-.J
Tor
Separafo,
Flash
I
I
I
I
Pilch
, . - - - - - _ _ _ _ _ _ _ .JI
lI
ViscosifY
breaking ('Ilfernote)
I
I
,.
Gosoline
,!,
I
I
I
Gos oil
- ___ -J
~-----------------~------------
crackin~
processes.
781
21-10.
Approx.
Characteriza.tion Factor
,
12.0
11.6
11.2
10.9
Percentage gasoline
-~-
20
30
40
0:9
0.5
2.0
1.5
0.9
2,7
...
...
1.2
, ,
50
.----
4.0
1.7
4.1
2.15
II Ardem et aI., Catalytio Cracking in Fixed and Moving Bed Processes, Progress in
Pet. Teohnology, ACS Meeting, New York, September, 1951.
-layer is then distilled to recover the boron compound (bp 258F). The
metals content of the crude oil is reduced by about half and the percentage of carbon residue by about 30 per cent.
Carbon burn off is of vital importance to the economics of catalytic
cr.acking. This explains the superiority and need for low-boiling, lightcolored (under 5 NPA), low-carhon-residue, metal-free distilled ' stocks.
Material balances or the yields of Figs. 21-3 to 21-5 indicate clearly that
high API gravity stocks yield more gasoline by being able to conduct
operations at larger percentage conversions. However, for a fixed gasoline yield, the somewhat low-gravity naphtheruc stocks produce less
carbon on the catalyst than paraffinic stocks 20 (Table 21-10), at least
by the Houdry process. Figure 21-4 indicates the opposite relationship.
In the extreme, kerosene, naphtha., or even gasoline may be cracked by
the catalytic processes. "'.48 The Houdry<l7 and particularly the CycloAnon. (C. D. Smah), Pet. Processing, October, 1956, p. 55.
41 Saegebarth, E. 0., Catalytic Reforming Process of . . . , Pet. Engr., May, 1946,
p.95.
48 Greensfelder, Archibald, and Fuller, Ca.talytic Reforming . . . Molybdenumalumina and Chromia.-a.lumina Ca.talysts, ChBm. Eng. Progr., 48, 561 (1947).
47 Peterkin, Bates, and Broom, Catalytic Reforming for . . . Aviation Gasoline,
R~. Nat. Ga8o. Mfr., November, 1939, p. 126.
'
.ioN
782
3.1
8.0
48
1.6
to 5.9%
to 10 . 6%
to 28.5%
to 0.56
Only 0.18 per cent copper had much the same effect on the coke yield but a
lesser effect on the other yields.
If the sum in the feedstock of the parts-per-million of iron and vanadium, plus ten times the ppm of nickel and copper, is above 5 to 10,
rapid replacement of catalyst (in the Fluid process) will be necessary,
Thus, a gas oil that contains 0.5 ppm V, 1:0 ppm Fe, 0.3 ppm Ni, and
0.1 ppm Cu results in a sum of 5.5, and rapid contamination of the
catalyst will occur. Another authority!>5 has mentioned the following
limits for a satisfactory feed: Fe, 1.0; V, 0.4; Ni, 0.15; and Cu, 0.1 ppm.
Although thls is a fairly good feed according to the formulation given just
above (total = 3.9, which is under 5), it would be classified as bad by the
Daniels and Conn, Pereo Cycloversion, Pet. Processing, May, 1947) p. 391.
Swift et aL, Aromatics Recovery by Hydroforming . . . ,Pel. Processing, January, 1953, p. 81.
;;0 Schall and Dart, Cat. Cracking of High Nitrogen Charge Stock, Pet. Refiner,
March and April, 1952.
61 Thomas, E, J., Fluid . . . High Sulfur Stocks with Natural Catalysts, Oil Gas J.,
Ma.r. 23,1950, p. 221; also Carney et 801., Oil Gas J., Nov. 4, 1948, p. 49.
51. Duffy and Hart, Metal Poisoning . . . 1 Chem. Eng. Progr., July, 1952, p. 344.
68 Rothrock et 801., Fluid Cracking Catalyst Contamination, ACS Meeting, Dallas,
Apr . 8, 1956.
H Mills, G. A'J Aging of Cracking Ca.talysts, Ind. Eng. Chem., 42, 182 (1950).
66 Eckhouse and Keightley, Pet. Engr., April, 1954, p. C-96.
48
49
783
contamination index of still another authority which states that the sum
of the Fe, V, and Cu plus 5 times the Ni (all in ppm) should not exceed
about 1.0. Finally, the American Cyanamid Co. once used a contamination index based on the catalyst (weight per cent), which is:
784
Particle
size,
microns"
G-1O
0-20
0-40
0-80
G-125
0-180
0--500
A and
21-11.
F.e.
CATALYSTS4
A
75
95
100
--' 60
85
95
100
F
~-
0
0
50
100
5
15
25
75
..
.
.
.
.
..
.. ..
. 100
.. ..
.
.
. . ..
.. ..
"
12.
22
41
71
1
5
30
75
93
(j
-1
.3
17
56
93
9.9
...
95
100
100
100
84
it
~-
..
-.. .
..
13
10
12
24
50
48
71
86
100
40
100
..
L
~
25
..
K
4
15
33
65.8
6
19
44
71
.. . ... ..
.. . .... ..
100 . ... ..
~ommercially
L-used natural.
Nelson, W. L., What Is a. Good Ca.talyst, OuGas J., Apr. 28, 1949, p. 120; see also
Mar. 17, 1949, p. 162.
" 1,000 microns = 1 mm.
IS
In general a good catalyst should not lose its activity during operation, .
and the loss by attrition should be small. Natural catalysts are softer
and are therefore destroyed more rapidly than most synthetic catalysts.
Obviously, the catalyst for the Fluid process must exhibit such a size
distribution that it fluidizes properly. For a natural catalyst, the percentage of 0 to 80 microns material should be kept above 50 (preferably
75) and the 0 to 40 microns mat~rial above 15 per cent (preferably 25).
Cyclone separators often behave erratically, but will usually retain particles larger than 10 microns in both reactor and regenerator service.
Natural :fluid catalyst contains some particles that are oblong rather
II Thornton, D. P., Jr., F'luid Ca.t .. Use New MS Catalyst, Pet. Proce88ing,
March, 1947, p. 173.
12 Nelson, W. L'J What Is a Good Catalyst, Oil Gtu J., Apr. 28, 1949, p. 120; see.
also Mar. 17, 1949, p. 162.
014 Bey-ler et al., Oil G(J8 J'l June 3, 1957, p. 95.
785
than round, and he~ce the average-size particle that passes through a
screen has an a.verage diameter that is about 20 per cent larger than t~e
screen opening.
New catalyst IS offered in various grades, depending on particle size, as
50/60 (light) or 75/85. Catalytic activity is vital, but in addition all
cracking catalysts are strongly adsorptive. Tables 10-4 to 10-6 show
the physical properties of common catalytic .and adsorptive materials.
Catalytic activity is measured by determining the behavior of the
catalyst in laboratory-scale equipment at standardized conditions for
each test ' method, meaSuring especially the prod uctfon of gas and distillate, although carbon deposition and other results are also noted in most
methods. Of the numerous methods 63 (at least 14), the Houdry Cat. A,
Jersey D
L, and UOP activity rating are probably the most widely
used. The approximat.e relation between these is indicated in Table
21-12 .
or
786
particle sizes that are retained, effect of velocity, and. gas and solid
densities. . Percentage efficiency curves (percentage of each particle size
retained) :vary widely because of the many operating variables such as
size distribution, velocity, etc., but behavior is somewhat as shown in
Table 21-13. Regenerator cyclones behave less well than reactor cyclones
because of the lower density of the gases.. Thus with coarse catalyst
TABLE
21-12.
10
--
- - -60-
77
86
100
...... 116
.. ...... 128
150
107
.....
..
158
28.
33
37.5 42
20
23
25.5 27.5
46.5 - 55.~ 65
29.5 33
35.5
29.5 33 3Q.5
25.5 27
42
31
35
33
39
29
47
32.5 35.5 38.5 40.5 44
29.5 32.5 36
38
40
43
0.26 0.34 0.42 0.505 0.59 0.77 0.97
46
50
54
57.5 60.5 65.5 69
20.5 23
25
28
22
34
45
63
26
40
53
67.5
30
45
60
71.5
34
50
37
56
67
74
74.5
77
44
67
89
82
52
78
The letters AGC of the American Cyanamid Co. mea.n "activity, gas, and coke."
,. Mainly from American Cyanamid Co. release of May, 1957, entitled H Activity of
Synthetic Fluid Cra.cking Catalyst,,' but other sources used for Cat. A Houdry
method.
e Volume activity "'" 2 times UOP wt activity times bulk density.
II
(65 per cent over 40 microns) a. reactor cyclone may recover 99 per cent
of the catalyst, whereas a regenerator cyclone only 57 per cent (and with
fine catalyst containing 95 per cent under 20 microns, the recoveries are
only 63 and 51 per cent). Saving of catalyst is important, but cyclones
and precipitators should also retain a distributionof catalyst that fluidi~e8
properly, and this means mainly the retention of so-called fines. Thus,
an effort is made to retain catalyst even if some is later discarded in-order
to maintain catalyst activity. In a few plants, elutriation methods have
been used to eliminate too coarse particles, and in at least one plant!8 the
Vila.nd, C. K., Gravity Separation of Inactive Catalyst, Oil Gas J., Nov. 30, 1950,
ll. 74.
16
787
21-13.
Percentage efficiency
Particle
SIZe,
microns
5
10
20
30
CI
"Electrical
precipita.tor
Single-stage cyclones
Design
Up to 8-2
99.5
77-93
99.2
99.45
97-99
I
Comm~rcialCi
2-stage cyclone
(design)
49-66
72-85 "
93-99
99-100
92
99,
99+
788
beca~e
the 'metals are found in the outermost layer' of the bea.d. Thus
much of the contaminated catalyst is eliminated as dust. During early
development of .t he Fluid process, elaborate equipment was installed to
ensure a small loss to the regenerator flue gas. Mo~ plants now employ
only cyclon_es -but in two and sometimes more stages. _ Losses in the
Fluid process are not as vital as once thought because a 'makeup of
().3 to 0.& Ib per bbl fresh feed is usually necessary for maintenance of
-activity. Loss -of fine catalyst from the reactor appears in the small
TABLE
Na.tural
Synthetic
Silica.
Activated Silica
alumina .- natural ma.gnesia.
..
. Silica. Grade
13%
S.R.
aluminA magnesIA 53
60
975
~12
60
. 975
7-10
95
81.6
60
930
60
975
6-10
,'.
47,8
3.1
8.74.8
56.2
2.9
9.'
6.4
93.6
79 .8
91.5
6.2 .
3.6
79.2..
60
930
46.9
3.4
57.2
6.4
-5.0
5.1
4.9
9.0
7.0
93.. 7
81.0
3.4
' 90.3
78.6
60
80
930
930
49.3 49.0
3.6 3.4
7.0 6.8
6<.9
7.1
7.8
6.3
89.9 92.8
79.2 80.5
~ Gohr, ~. J., Advances in Fluid Cat. Cracking, Prot. Fou.rth World Pet. Congr.,
sec. III, Rome, 1955j and E. V. Murphree, Fluid Cat. Cracking Process, "Progress
in Pet. Technology,." ACS Meeting, New York, September t 1951. '
. z. FeedBtock 29-29.4 API, ASTM 50% at 701~.
.
heavy portion of cycle oil known as slurry oil. n This is often returned
to the reactor because the- fine catalyst is valuahle, but the low-gravity
slurry oil tends to ca.use a larger carbon deposition. The fixed-bed ,
processes' cali operate with extremely low physical losses of catalyst
(under 0.11b per bbl), the circulation processes lose more catalyst (0.15 to
'0.7 lb), and, of course, all of ~he catalyst in the Suspensoid process is
rejected (2 to 3 Ib).7
Natural catalysts are the cheapest (under 8100 per ton, as against $300
or more for synt~etic types), they cause a slightly larger carbon deposit,n
and the gasoline produced by . them has a lower octane number (1 to
4 units). Yields are, however, slightly. larger ~th natural cataIy~.
72
Moorman, J. H., Slurry Recycle and Slurry Settling, 01.1 Gas J., Aug. 22, 1955,
- ~1~ '
....
...:...
- ~-----
------=-----=
-, ~-~~
= ... , ' -
---
789
. (21-2)
The HIC ratio is the atomic ratio (12 times the weight ratio), and the CO 2
and CO refer to the relative volumes of these gases in the flue gas. Equation (21-2) was obtained from experimental heat balance data and it does
not check precisely with the following computed net heating .va1l:les :89. n
COl/CO
mole ratio
0
1
"2
4
10
8"
.
..
7,200
12,450
14,000
!2"
12,440
13,840*
14,140
15,480*
.15,300
16,350
Eng. Progr.,
790
+ CO)
C0 3 /(C0 2
0.5
,j
)
\'I
and '
+ CO)
1.0
0.334
0.5
2.0
3.0
0.667
0.75
4.0
0.80
6.0
10.0
0.856
0.91
I,
ture
800
900
1000
1100
0.685
0.679
0.672
0.665
0.670
0.647
0.624
0.600
0.645
0.615
(l.585
0.555
12
0.635
0.630
0.567
0.504
0.440
0.590
0.545
0.500
,
(
791
21-16.
Ratio
CO 2 /(C0 2 + CO)
. Hydrogen in deposit
60
50.
50
65
65
65
HIe
Combustion
air, Ib per lb
deposit
10.92
4
S
0.50
1.04
12.05
12
1.63
13.18
0.50
11.82
8
12
1.04
12.92
14.02
1.63
Avg diameter~
microns
25
40
60
80
2.0
1.5
22
28
35
41
15
19
24
27
7T Brown and Wainright, Synthetie Fluid Cracking Catalyst, Oil Gas J., Dec~ 1,
1952, p. 133.
792
Percentage
Cycloversiona.
conversion
40
50
Fluid
Houdryll
Moving-bed
2.5
3.7
5.3
.7.2
4.0
2.2
3.1
4.3
1.0
1.2
1.9
3.3
60
70
...
80
10.0
4.8
5.5
6.2'
5.9
7.7
40 Nelson, W. L., p. 673 of the Third Edition of this book, and Oil Gas J. t Aug.
30, 1947, p. 67.
'
b Extrapolated beyond da.ta.
=:
13,650 .
5.15 X 13,650
'18
= 70,300 Btu
_=-"=-"""-.........,;-..........
-- _
- IiIi_ _ _ _----'-'--=::~
--;=-- - ':':::"= --'
,,~ - ~'-'-'
793
H the air is not preheated (60F)', rea.ction is conducted a.t 925F, and regeneration
at
1160~:
11-993(n~~3~925)O.25
= 16,000
= 54,300 Btu
(Fig, 14-1)
This is a. cat./oil ratio of 9.18, and the tota.l weight of carbon (inoluding the
residual carbon) on the equilibrium or carbon-laden catalyst is:
o.i% of
The circulation of pure catalyst is l~wer than 9.18 by the amount of carbon recycled
on the catalyst or 9.18 - (0.007 X 9.2) = 9.12
.
';I'he hea.t of desorption of steam was neglected in this bala.nce.
same.
Campbell and Pennels, CO Boiler . . . J Oil GfU J., Feb. 22, 1944, p. 132.
80 Noll et aI., Thermofor. Ca.t. Cracking, OJ? Ga8 J., May '10, 1947, p" 64.
"It
794
process at 900 to 960F, the T.O.C. processes at 830 to 930F, and the
Cycloversion process at 980 to 1020F. The yield of 10 Reid vapor pressure gasoline is not greatly altered by reactor temperature BO because the
yield of propylene and butylenes increases rapidly thus increasing the
yield of poly gasoline, but at about 875F th~ T.O.C. process is most
economical. so
The effect of percentage conversion on yields has .already been mentioned under the heading of Yields. In addition, octane number~ are
higher by one or two units when raising the once-through conversion from
55 to 65 per cent. Schulze and Helma.rs81 discuss the effect of percentage
conversion on the Cycloversion process:
Computed heats of reaction are not adequate because of the great
accuracy required in yields and in the properties of the products. Thus,
in Example 2f-5 the computed heat of decomposition is 623 Btu per lb
of gasoline and lighter materials, a. value apparently 100 per cent high.
Furthermore, had the Characterization Factor of the gasoline been'
assumed as 11.7 and the heat of combUBtion of the feedstock 19,450, .the
computed heat of reaction would then have been the impossibly high
value of 825. It is therefore necessary to rely on approximations from
the literature and especially the carefully conducted experiments of Dart
and Obladu on the Houdriflow process. Their smoothed ,data and a. few
suggestions and computations82 from the literature are shown in Table
21-18. However, it must be mentioned that commercial T.e.C., operations appear to substantiate lower heats of reaction than those of" Dart
and Oblad. If computations of heats of reaction are undert~ken, the
following average heats of combustion (Btu per lb) ma.y be useful: s8
Etha.ne and
lighter
Propane and
lighter
B-B cut
24,130
...........
21,922
21,912
22,112
21,940
21,069
21,186
21,101
21,140
..........
..........
,,-
-..
~ ---.'='.-,. -:-
795
Dart and
Oblo.d Cl
35
40
300
50
250
222
~ghter
materialS
Others
285
245ft
56
59.1
60
205
200
70
135
80
65
....
95c and 1~
90--120d
221--399 d
112"
Example 21-5. Heat of Reaction. The charge stock and yields of Examples 21~3
and 21-1 will be Used to compute the heat of reaction (at OOF).
The Characterization Factor of the gasoline will be 11.5 and of the cycle oil, 11.4
(see Table 21-7). Heats of combustion may then be read from Fig. 5-22, which possibly gives too high values became Characterization Factor does not properly account for
the aromatic hydrocarbons in these materials. Other heats of combuation may be
read from the tabu\ation on page 794 or Tables 5-2 and 5-3. The heat of combustion
of the coke deposit can be computed from Table 14-5. The energy contents of the
feed and the products are computed in Table 21-19.
Thus, the products contain about 330 more Btu of energy than the .feed, leading to
a heat of reaction based on gasoline and lighter materials of:
330 -;- 0.53 = 623 Btu per lb gasoline and lighter
This is apparently over twice 8.B large as it should be (see Table 21-18), and the error
arises because the properties (and yields) of the products are not precise.
Fluid reactor beds' operate much as regenerator .beds. The linear gas
velocity is 1 to 2 ft per sec with a .critical velocity past which large
amounts of dust escape to the cyclones. The density of the fluidized
bed ranges from 20 to 40 lb per cu ft and depths up to about 30 -it are
maintained. A disengaging space of about 15 it is employed.
The hot catalyst furnishes some heat to the oil charge; but unless the
796
21-19.
Weight
per cent
Material
API
UOP
factor
Coke ................
5.1
.....
2.5
3.8
1.6
7.9
.....
Butylenes ..........
Isobutane ..........
Butane ............
B-Bcut . ............ :
3.8
4.7
0.7
9.2
....
.....
....
..
....
Gaaoline .............
Cycle stock ..........
Total products ...
Feed .... , .... ..... ' .' .
,.,.
...
Gross heat of
combustion,
Btu per lb
...
.....
,.
....
. ,. ..
983
983
24,130
21,060
21,690
21,922
603
800
347
-1,750
1,732
786
1,001
149
1,936
1,945
7,119
8,049
19,837
7,119
8,049
19,828
..
...
41.9
52.5
28.1
11.5
11.4
19,830
19,210
. . .. .
100.0
., .
.. ..
,.
.."
30.0
..
....
11.9
Gross H.V.,
Btu per Ib feed-
19,270
20,690
21,290
21,340
21,140
35.9
..
21....5.
.........
19,500
Example 21-6. Reactor Heat llalance. The stock of Examples 21-3 and 21-1 will
be cracked. The amo'unt of recirculation was found to be 9.18 in Example 21-4 and
this is different from the original assumption of 8 which was used in ~ple 21-1 in
determining yields. A heat of l'eaet~on of 200 (Table 21-18) will be used. The Size
of the reactor will not be computed, and the heat 1088 through the wa.lls (under 0.5 per
cent) will be neglected. .
Basis: 100 Ib feed.
~i: = (665
- x)
= 231
Btu .~1 Ib
at
797
21-20. FLow
Location
Density,
Gas velocity,
lb per cu ft
ft per sec
13-40'"
1-2
15-30
2-7
15r.-40
30-40
90-115
1.5-5
0.2-1.0
The catalyst is saturated with ,oil. during the reaction, and this must be'
removed by stripping with superheated steam or hot flue gas. Little'
specific information on stripping appears In the literature, but it is vital)
particularly in the Fluid process.
.
86
The rate of carbon formation is somewhat less rapid in Fluid catalyst
cracking than in fixed-bed cracking, and the rate with synthetic catalyst
is slower than with' natural catalyst. During 10 min Fluid catalyst,
accumulated 0.8 to 1.3 per cent carbon whereas fixed-bed catalyst accumu-- lated 1.7 to 2.2 per cent carbon.
Fluidization Mechanics. Regenerators and reactors behave very
much the same, and common How rates and densities are indicated in
Table 21-20. Fluidization may be maintained (see Fig. 21-1) at veloci...
ties of 1 to 2 ft per sec, but at Borne limiting velocity (1.5 to 2.2) fine
catalyst tends suddenly to be carried upwards out of the bed to the
cyclones. If downward movement is desired as in standpipes, a higher
gas velocity is maintained (2 to 7) so that packing of the catalyst does
86
ae Voorhies., A., Carbon FOl'IIlAtion in Catalytic Cracking} Ind. Eng. Chern., April,
1945.
798
not occur, and to care for the greater pressure toward the foot of the
standpipe. If the downward movement is appreciable (2 ft per sec) the
aeration medium tends to move downward with the catalyst and be
compressed. 87 This is offset by aeration at several levels to maintain a
fluidized 'state even though the gas is constantly shrinking in volume.
At very low rates of downward flow, the gas tends to pass upward, through
the catalyst giving variations in density. Aeration is, however, held to
a minimum because erosion in the standpipe and slide valves is thought to
increase in proportion to the third power of velocity.
The lowest point in the standpipe-riser system is the point of greatest
pressure (or tendency toward movement). Referring to Fig. 21-1a the
dense phase in the regenerator standpipe stands at such a level that it
more than balances the weight of the dilute phase in the riser, the part of
the reactor bed above the riser outlet, and the greater pressure (usually)
in the reactor vapor _space. Flow is permitted by opening' or closing of
the slide valve, while alwa.ys maintaining by aeration the proper densities
in each part of the system. In the riser, a high aeration velocity (15 to
40 ft per sec) must he maintained so that no parts of the catalyst can fall
back through the gas stream. The minimum velocity to avoid slump
back, slugging, or even plugging is about 15 ft per sec. A pressure
differential of 3 to 6 psi (or more) is maintained across the slide valve, and
two valves are usually installed so that operation can be continued after
one valve becomes worn.
_The carrier medium moves at a higher velocity than the catalyst
particles and thus a slip factor that cannot easily be evaluated must be
introduced~ Some allowance in the , density must be made, and usual
design practi'ce IS to set the slip at 2: 1, Le., -double the density calculated
from the amount of gas and catalyst flowing. Densities in the carrier
or riser lines are usually held under 5 lb per eu ft (neglecting slip). '
PROCESSES
Only the barest process information can be given here bec'Ruse of the
numerous improvements tha.t are still occurring. The Fluid process
dominates the domestic installed capacity, but the T.C.C. process is used
almost as much as the Fluid process in foreign plants. Thermal cracking
has rapidly been relegated to the position of 'a secondary process used for
the viscosity breaking and c<?k.ing of residual materials, and to some
extent the cracking of catalytic cycle stocks. Approximate operating
conditions for the major processes are indicated in Table 21-21 (see
Table 21-24 for reforming proce~ses).
87
Nelson, W. L., Circulation Control in Fluid ProceBB, Oil Gas J., Apr. 14, 1949,
p. 120.
~.-
799 '
21-21.
Houdry
T.C.C.
Cyolovendon
HoudriBow
Fluiii
SS(}-925
885-975
,i
Reactor temp, of ............ '. . .......
Reactor (top) pre.I.UlUl'e, psig .... ,'........
Cat. to oil 111. tio .......................
Spa.ce velocity, V/V.hr .................
Average recyole ra.tio, (1955) ..... . ....
Regenera.tor, temp. of ........... , . . , ..
Regenerator, pre9S0re, psig ..............
Regenerator, 8ir temp, of ............ ' ...
Onatre.am time .. . ..... , ............. , .
Catalyst shape ... . .. : ........... . ....
84()-gOO
7-30'
780-950
1(}-15
.........
'S5o-go0
2O-S0
1-3.S
0.25
960-1080
Atm. to 1
10 min
Beads
8-1
~6
<I
0.75-1.5
~10
Continuoull
Beada
2-1
2.5-8
Hydroa-en, % of coke . . ............. . .
Catalyst roplacement and 1088, Ib per bbl
prooeSsed ......... . ........... , .... 0.3-0.5 0.15-0.5
1.&-4
. .........
700-1100
Atm.
9-18
8-20
1-8
0.18
1050-1150
5-10
980-1050
35-100
2-4
1200
powder
7-15
0.2-0.5
0.2-0.6
Nil
Vapor
4:~~
exchg.
heat
Gaspurg!ng
Esystem
' ,~I
Cooling medium
....
~~~-;::;~-
Ak
heater
Vent
Gasoline
Air
mlet
it
stack
Hearer
Oi I se~rator
Red. crude
~----~----~~~~--~~
c.harge
Tar
Vapor from the tar separator or a vaporizer is mixed with ~team and is
admitted to the reaction chambers at 840 to 860F~ Passage through
the chamber is continued for about 10 minutes. By this time the pores
and surfaces of the catalyst have been covered with a thin film of carbon,
PETROLEUM
800
REF~ERY
ENGINEERING
88
1. Onstrea.m-lO min.
2. Oil and va.por purge by venting to a condellSer and steam-jet evacuation system5 min.
3. Regeneration with preheated air-lO min.
4. Air purge by steam-jet ejootore-5 min.
All operations are automatic, even to the opening and closing of valves. 88
Air is supplied by a centrifugal multistage compressor directly coupled to
a gas turbine. 89 Compressed air (350F) at 50 lb gauge, preSSUIe is preheated to 700 to 800F and admitted to the chambers. The flue gases
issue from the 'chamber at 850 to
Ali" Inlrd
and '
950D F, having absorbed enough
heat energy to operate the gas turbine used in compressing the air.
During this cycle the heat of
reaction must be provided during
the onstream phase and the heat
------ --8T futM
generation during,regeneration or
burning with air must be removed.
These conditions are met by recycling a mixture of molten salts
which tends to keep the reaction
temperature up to about 850F and
-S;:::ea the regeneration temperature down
j;mI:ll!tI!b:I~....,..q Air ouII",
to 950F. The net resu! t is an exoniI
cess of heat which may be used to
oil InIef
produce high-pressure superheated
steam. 'rhe chamber or case 90
indicated in Fig. 21-9 contains
bayonet-type salt tubes (K.T.) and
SaH inlet
regenerating tubes (C.T.), and B.T.
FIG. 21-9. Longitudinal section of a modi- tubes for conducting air into the
fied design of Houdry reactor. (Oil
bed or delivering cracked vapors
GfUJ J.)
to the outlet. Holes are provided
in the outer C.T. and B.T. tubes for distributing air or oil throughout the
length of the case. Catalyst surrounds the tubes, and metal fins on the
of any part of the
K.T. and C.T. tubes extend to within a:bout ~
in.
Tuttle, R. B., Houdry Cycle-timing System, Oil Gas J., Feb. 24, 1945, p. 12Q.
Be Eva.ns a.nd wsia.t, Combustion-gas Turbine . . . ,Pet. &finer, November, 1945,
88
p. 135.
.
80 Lassiat a.nd Thayer, Improved Design of H~udry Reactor . . . , Oil Gas J., Aug.
3, 1946, p. 84.
"'- -
- -- - - - - - - ,
'
.'
801
catalyst mass. Ca.ses hold about 34,000 liters of catalyst weighing about
21 tons.
Regular Houdry day pellets have lasted more than 18 months. 9D Newer
catalysts80 contain some high-thermal-conductivity material to assist in
heat flow, and T.C.C. beads are being used because of their mechanical
stability. Catalyst costs are less than 2 cents-per barrel processed. New
catalyst is very active, and hence process steam is introduced and then
red uced in amount as the run proceeds. Increase in pressure .from the
usual 10 psig to 70 psig increases the gasoline yield, but the yields of gas
and coke increase even more rapidly.
Yields are generally in agreement with Figs. 21-3 to 21-5, being similar
to those of the moving-bed processes, i.e., lower coke deposits (8 to 11 per
cent) and more gasoline (1 to 4 per cent) than shown in Fig. 21-3. The
process was also used during World War II for the dehydrogenation of
butane, isobutane, and butene. 91
Fluid Ca~ytic Cracking (F.e.c.). The Model IV d~sign of Fig. 21-1a
is used for most large plants; but Fig. 21-10 which is discussed here, illustrates the smaller Orthoflow92 ,!lS type. It was designed to charge 8,350
bpd of 30 API West Kansas gas oil plus 31 per cent (2,589 bpd) of recycle,
giving the following yields:
Weight, % Volume
Dry gas ........ , ....... , , ... , , .
Coke ........ , , .. , ..............
Debutanized gasoline .. , ...... , ..
Naphtha,............. , .........
Cycle and decantea. oil. : ... : .....
7.8
8.5
..
.t
,.
..
36.4
13.6
30.0
15.6
In a.ctual operations9-4 the gas and B-B production were closer to those of
Fig. 21-3 than the design yields tabulated above. Some design operating
condi tions were:
Cata1ys~ to oil ratio, lb jlb ....... .
Catalyst holdup, tons:
16.7
Space velocity ................. .
In reactor .................. .
,1.35
In stripper ......... , ... '.... .
Catalyst circul~tion rate, tons ... .
14.8
In regenerator ....... -. . '..... ,
Settled slurry oil, bpd ........... .
250
Steam-to cat. stripper, lb per br ..
8,900 Carbon on regenerated ca.talyst ..
Stea.m-to reactor, lb per hr ..... .
1,400 ..Conversion, vol. % .......... , ..
Stea.m-generated, lb per hr ..... . 27,260 Catalyst in slurry, % ......... .
Total blower air, Ib per hr ....... . 114,900
44.2
14.4
96.4
0.5
67
0.5
Lassiat and Parker, Butane Dehydro~na.tion . . . ' Houdry Process, Oil~8 J.,
Nov. 18, 1944, p. 229.
U Reidel, J. C., First Orthofiow . . . in U.S.A., Oil Gas J., Mar. 24, 1952, p. 200.
i3 Degnen and Skelly, Design and Operation . . . I Pet. Engr. Ref. Annual, 1953,
p. C-7.
.'
.
94 McGrath,. R. V., Pet. Engr. December, 1953, 't). C-5.
91
.J
!J
li
I
LEGEND
c::=i ...... OF
c=I~'y
~,
OPS!
;,
~l-17fwo~ J
-<I>- M7<W p~_
SItt#11
1f'/1/H
:1
..t--.,
! '
~
,
,
I
,
I
.:,
___ ~------J
Ai
s.r.rrMr
'-'i..eL
LI!
~tN1
or~king
(F.e.c.)
= _1_.
~
Cwstk
803
to
Fresh feed (often heated 600 to 700F) lifts hot regenerated catalyst
into the reactor as the feed vaporizes. Cracked material leaves the reactor
through cyclone separators and is fractionated into products. ' Clay fines
accumulate in small amounts CO.5Ib per gal) at the bottom of the fractionator, and they (as slurry oil amounting to 3 to 10 per cent of feed charge)
are usually returned to the reactor. Spent catalyst overflows into the
stripper where it is stripped by steam. The spent catalyst is lifted into
the regenerator by preheated air. Catalyst -(above about 10 microns) is
held in the system by cyclone separators (and sometimes Cottrell precipitators), but scrubbers utilizing the incoming fresh feed -have been used
in one plant. 95 Heat may be removed from the regenerator catalyst by
T .ABLE 21-22.
Carbon or
fuel burned,
weight per
cent of feed
-3
915
5
6
995
400F
100F
SOO
..
..
..
800
905
980
. ..
825
925
804
21-23.
950F
REACTOR T~ERATURE
Catalyst to
oil weight
ratio
5
10
20
30
40
A
1125
1190<'
1080
1040
995
1015
9950-
......
.....
..
. .. .
1115
1035
1005
1150
. ...
1055
1020
1000 .
Extrapolated.
destroyed. This has been cured in part by: the development of a twostage systemlOl which produces less coke. and more gasoline (tending to
approach the yields of Fig. 21-3). The feed is first contacted with hot
regenerated catalyst for a few seconds in an upflow riser reactor at a high
temperature (IOOOF). The partially cracked material is separated from
the catalyst, and the gasoline is removed in a fractionator. The remaining partially cracked feed, along with recycle, is then cracked in a conveI).tionaI bed type reactor for a longer period, using the still hot catalyst
(Without regeneration) from the first or riser reactor stage.
.
Thermofor (T.C.C..) and Houdri.fiow Processes. These processes2(}-24l
during early sta-ges were developed jointly by the Socony Mobil Oil
Company and the Houdry Process Corporation. 102 In many respects
Fo~er,
A. L., Maintena.nce of Fluid Cat. Cracker, Oil Gas J., Oct. 25,1947, p. 86.
tI MacDonAld, M" Automatic Control of a Fluid Catalytic . . . , Pet. Refiner,
oetober, 1946, p. 87.
100 Anon., Instrumenting the Fractionator . . . , Pet. Pr0c.e8Mng, September, 1946,
p .. 52.
101 Heldman et aI., TwCHItage Fluid Cat. Cracking, Oil Gas J'., May 21, 1956, p. 230.
101 Now that differences of opinion over the ownership of certain features have been
settled (Pet. Week, Dec. 23, 1955, p. 21) the processes are rapidly assuming a greater
importance.
98
..
0 ....
.,
they are similar but each has its own features of reactor and kiln design.
Figure 21-1b is based on the T.e.C. process and Fig. 21-11 shows the
Houdriflow process.l03.104 Before 1951, the bucket elevator rather than
the air-lift method of lifting catalyst (as in Fig. 21-12) was used. 106 .Bot
regenerated catalyst beads are.Iifted with hot air or elevators to the reaction zone where the major amount of the feed a.nd recycle jn the form of a.
va.por is introduced. In addition, a small amount (10 ,to 20 per cent) of
feed may be introduced as a liquid38 .88 at the top of the reactor, but th~
Conradson Carbon test of the feed should be' kept below about 4 per cent.
Most plants do not superheat: the vapor feed as shown in Fig. 21-12.
Ratios by volume of catalyst to oil, up to 7, are employed but commonly
range from 3 to 5. '.Steam or flue gas is employed at a slight pressure to
sweep hydrocarbon vapor from the spent catalyst a.s it flows to the lift
mechanism. Regeneration of the catalyst occurs as it lows downward
through the regenerator countercurrent to preheated air (400 to ,900F).
The pressur.e is substantially atmospheric in the kiln. Flue gas is circulated through cooling coils in the kiln to control the rate of combustion
of thecoke89 and to provide a means of saving excess heat from the process
by means of a waste-heat boiler. Additional heat is usually recovered at
the base of the main fractionator by a. waste-heat boiler, although Fig.
21-12 shows this heat being.used to heat crude oil. A part of the regenerated catalyst is c,u rrently cleaned of U fines U and small particles by
means of a stream of air in what is called an elutriator. Much of the
catalyst that is poisoned by metal contaminants is found on the surface of
. the beads, and thus much of the deactivated catalyst leaves the system as
. dust (about 4 times as much metal in the dust as in the be~s21.71).
Catalyst loss by attrition is usually under 0.6 per cent of the circulation
although values up to 2.5 per cent have been mentioned for clay
beads.loa.IM Little catalyst need be added to maintain catalyst activity_
Recycling is advantageous not only because of the increase in yields
but also because it assists in the vaporization of a.dditional fresh feed from
the primary residual feed (see Fig. 21-7). Nearly all plants conduct
some recycling (average ratio is 0.25), and many plants operate at a
ratio of recycle to fresh feed of 0.5 (severa) plants at 1.2). Yields may be
estimated from Table ' 21-1 and Figs. 21-3 to 21-5, but smaller yields of
coke and dry gas are produced than indicated in the figures, and the yield
of B-B cut is-.larger .
.
The superiority of the moving-bed sys'tems in tolerating metal con.tamination has been 'put to test in the installation of a. commercial plant
108 Barton, P. D., Sun's New Houdriflow Unit, Oil Gas J., Mar. 29, 19tH, p. 232104'Noll et al., The HoudrUlow Catalytic Process Today, PrOf!. Fourth. World Pel.
emgr., sec. III, Rome, 1955.
IOri Socony Vac. Oil Co., Test Run " .. T.e.C. Commercial Plant, Pet. Refiner,
September, 1950, p. 115.
806
Oil inlet
Oil outlet
Slack
Seal steam
. Air oullet
Air inlet
Blower
~.-.
A1s9
'0
3161 BID
25.4 API
231 BID
40.4 API
OIABOTOL
e
~
CH .... GE
AGCUIiIUL A TOil
CAT.
POLY FEED
989B/0
l~o.BAPI
"
...
2...
3
i'..
C
II
~91ol ,
. --
,.,::1 e r.
Allit '1Iit0JI
LE'GEt.,ID
"'.'1111
C PRESSURE', "slll
349810
74.0 API
D'rEMPERATURE, -F
FIG. 21-12. 01der buckeklevator type of Thermofor cata.lytic cracking (T.O.C.) plant.
(Pet. Refiner.)
808
..
Wt %
47 .0
10.5
11.5
13.9
9.6
7.5
100.0
..-;-
. ~
-.
~ -- ~ -
.- - - -
. ..-
~---
.. :. -
- ':'"- - ~- ;'::--"-~~
809
are somewhat larger than by all but the Fluid process. The catalyst,
bauxite, is mechanically strong l08 and may be regenerated at 1275F
(even. 1400F) rather than the customary 1050 to 1125F used for other
catalysts. The catalyst does not appear to lose its activity,109 but about
15 per cent is lost per inspection. Cracking cycles of 2 to 10 hr are possible before regeneration is necessary and even 24 to 36 hr when reforming
naphthas. The octane number of the gasoline from Texas Panhandle gas
oil is 76 to 77 ASTM (86 Research),109 but with 3 c.c TEL, octane numbers of only 81 to 82 ASTM are obtained because of the high olefinic content. The charge stock is heated48 to 980 to l020F (even 1050F in
reforming) and admitted to one of the two catalyst chambers at 70 to 90
psig (200 psig in reforming). Meanwhile the spent-catalyst chamber is
purged with steaJ;ll, and the carbon is.burned by a mixture of superheated
steam and air.
The same process and equipment are widely used for straight-run
gasoline reforming (980 to 1050F)1l0 and for catalytic desulfurization
(650 to 850F). When employed for desulfurization, 5,000 to 15,000 bbl
can be processed per ton of catalyst,4S and hence the catalyst may be
discarded.
A flow diagra.m of the Suspensoid process7 is not shown here (except see
Fig. 21-1cl) be~ause the process consists simply of introducing a slurry of
catalyst in cycle oil into the cracking stock, and then removing the spent
catalyst from the residual fuel by means of an Oliver Precoat Rotary
filter. s The oil and catalyst are heated to about 1050F and an outlet
pressure of 400 pSig is maintained. The main effect of the clay catalyst is
to allow a higher cracking temperature and to assist, perhaps mechanically, in ke~pingcoke from accumulating on the walls of the tubes.
Temperatures up to 1105F increase the yields qf excess butanes and gas at
the expense of heating and fuel oils, III but erosion becomes severe.
Although gas-oil charge stocks can be employed, a mixture of heavy
straight-run naphtha and gas oil is advantageous because the lowoctane naphtha can be refprmed along with the cracking of the gas oil
with total yields that are greater than when each operation is conducted
separately.7 New or synthetic catalyst produces slightly larger gasoline
yields (but of lower octane number) than the used Super Filtrol (from
lubricating-oil contact treating) now employed, but since only 2 lb usedcatalyst per barrel of oil is required, the use of expensive catalyst is not
Buell and Waddill, Cyc1oversion Process, Pet. Refiner, October, 1944, p. 83.
1011 Buell and Skinner, Cracking Texas Panha~dle Gas Oil . . . Cycloversion, Oil
Ga8 J., May 5, 19451 p. 87.
.
no Goldtrap and Skinner, Refinery Conversion for Premium Fuels, Pet. Engr., April,
1945, p. 174.
m Burk, C. F., Suspensoid Catalytic Cracking, Oil Gas J., Oct. 12, 1946, p. 100.
loa
810
CATALYTIC REFORMING
. H2
H20H2
.
H2
H2
H2
cyclohexane
HOB +
H
(21-3)
3H 2
#H
benzene
'CH a
HO~H + 3H
. ;::!. .
H
l,2-dimethylcyclopentane
methylcyclohexane
(21-4)
..1H
H
toluene
Eckhouse, J. G., Pet. Engr., April, 1954, p. C-26. (The average Pla.tformer
throughput up to 1954, including the early plants and the many which had only been
started, was 65 bbl.)
III
Molybdenum catalysts
P,rOOe88
Hydroforming
Thermal
reforming
Fluidized
Fixed-bed.
M. W,. Kellogg bed, E88a
Co.
and Std. Ind.
Ca.pacity, bpd, Jo.n., 196& ........ " ... ,
Refineries conducting" , ............. , .
Catalyst:
Composition ........................
394,000
57
..........
....
Q-12 months
. .........
........
Cont~ct
10-20
..........
.............
NODe
..
.........
'
...............
................
-
Ocoa.aionally
regenerative<>
Cyclically
regen.era-
1,000
1
,600,000
76
93.000
IS
141,000
11
0.1
~b/bbl
...........
Pt plus
heJogen
On AhOI
60-2.50 bbl
/lb
Reaotion:
Temp, of .................... . .... '.. 970-1060
Pre6ll, psi ................ , . . . . . . . 250-900
Space vel.. lb /lb-br .. , ....... . .......
Cobalt
molybdate
00
I-'
69,000
6
None
41,000
4
$0.60
950-1020
150-200
0.5-0.6
15
S9 ()-94
100-aOO
0.3-1.0
85D-960
200-700
1-4
..
0,06
3600 .
Cyolic .
1050--1100
170
4-16 hr
Sepa.ra.te
1100
200
Continuous
Separa.te
950
O'
.......
2~100
bbl
415
Continuous
876-950
200-600
1-6
..............
... . . .
None
.........
..
... ..........
'
Years
OooasionBl
1050
250-300
2-0 months
Th8rmofor
IQovmgbed,
Sooony
CyaloverSLan tlxedbed.
Phillips
24,000
2
8,200
P1;on
AhO.
Chromia
and
alumina
4(}-200 bbl Ii bbl/Lb
/lb
870
400
1.0
0.5-1.0
400HOOO
..
0.5% Pt.on
Al,O,'
tive~
/lb
$0.90-1.50 (19.00-14.00 but M.OO repla.oem.ent)
SO.90
200()-4000
..
Otoor oatalysts
850-070
200-400
1-5
...
"
Bauxite
. .............
$0.08-0.11
950-1000
100-200
(l.7
950-1000
50-57
1-2
............
.............
None
Oyolio
Se})ara.te
800-1000
. Cyolie
.............
. ............
.... . . . ....
.. Ca.tforming (Atlantio ReI. CD.), lfoudriforming (Ho)J.dry Prooess Corp.), Powedorming (E880 Rellearch & Eng.), Bnd Sova.forming (SoooDy-Mobil).
b Ultraforming (Std. Oil Ind.) and Sinda.ir-Baker-Kellogg.
c Turner, L., Oil Gaa J Mar. 19, 1956, p. 213.
.
d Not units or planta becauee some refineries hAve several units of the same prOOea8.
CBtrorming U&e8 SiD." AltO., 8Jl.d platinum.
I Rich in hydrogen (50-95 %).
15
18-36 hr
812
3. Paraffin Dehydrocyclization
(21-5)
n-hexane
benzene
4. Paraffin Isomerization
Hs H2 H2 H2 H2
I -I
/ I
(21-6)
H2 H2 H t
CloHn
H2 CHa
I I' I
I I
+ Hll ~ HaC-C-C-C-CH. + HaC-C-C-CHa
pentane
n-deca.ne
(21-7)
isopenta.ne
6. Olefin H ydrogenatian
C 6H 10
+ H2 ~
pentenes
C/iH 12
(21-8)
penta.ne.s
7. H ydTodesulJurizatian
H
,H
H(Ja
thiophene
+ 4H.->
CJI
+H.s
(21-9)
butanes
is
813
814
former feed because it alteadi has a relatively high octane number and
because it contains only a small amount of the hydrocarpons that can be
converted (see Table 21-25). Material boiling above about 400F 18
TABLE 21-25.
PER
COMPOSITIONS (VOLUME
CENT) OF A
FEw
STRAIGH~RUN NAPHTHAS
Ponca, East.
Okla. Texas
13
60
16
15
-62
- -78
-
20
23
16
12
4
36
1
35
9
12
1
21
18
..
77
10
I)
..
..
11
3
20
10
-78
15
6
1
.87
21
-4412- -314934
21
21
1
55
31
9
52
Feed, per
~nt
naphtha b ..
, . . .
23
47
2
15
5
21
3
7
46
~I
38
16
6
27
4
7
55
24
23
52
2
66
2
6
6
3
1
24
18
3
6
42
7
27
20
15
--...
20
34
65
27
4
10
8
10
1
2
33
...
.
..
...
.,
...
4:
62
26
10
30
5
36
5
27
74
50
815
The lead susceptibility of reformates is shown in Table 3-12, the relationship (spread or sensitivity) between Research and Motor method
octane numbers in Table 3-3, and the blending octane number in Fig. 4-46.
Aromatics and Hydrogen. During 1955, reformer capacity devoted
(in part) to aromatics production1l8 was 181,200 bpd, of which 148,000
employed platinum catalyst processes. The aromatic production of
such plants if fully utilized would, however, probably not exceed 80,000
bpd. Over half of the nation's need for benzene and toluene was produced from such plants, and much more can be produced as the need
arises. In aromatics production the most useful feed hydrocarbons are
su~h naphthenes as methylcyc1opentane, cyclohexane, dimethylcyclope~tanes, etc. (see Table 21-25), but aromatics are also produced in
smailer amounts'by cyclization [Eq. (21-5)] of paraffins. Higher-boiling
aromatics such as 1,2,4- and 1, 3, 5-trimethylbenzene, and 1,2,4,5- and
1,2,3,5-tetramethylbenzene are also produced by reforming, but there has
thus far been no need of recovering them as pure products. About
90 per cent of the possible yield of aromatics (based on naphtbenes) can be
readily accomplished by operations at low pressure (200 to 400 psi), low
space velocity (2 to' 4), and moderate temperatures.
Narrow-boiling-range feeds (150 to 225F, see Table 21-25) are p~oc
essed, and the reformate seldom contains more than 5.0 per cent of aromatics. The aromatics are recovered and purified by processes of adsorption (Arosorb or silica gel), extractive distillation (phenol), azeotropic
distillation, or solvent extraction (Udex, diethylene' glycol, or sulfur
dioxide).
The reforming processes are a valuable source of by-product hydrogen,
and the availability of this hydrogen has been a great incentive in the development of the hydrodesulfurization processes. The amount of hydrogen produced is so much a function of the feed conlposition that no means
of approximation is possible. However, the amount is substantial (400 to
1,200 ell it per bbl), and quite large (1,500 to 2,200 cu ft) from special
naphthene-rich stocks used for the production of aromatic hydrocarbons.
Platinum Reforming. The regenerative processes 27 - 81 differ from the
nonregenerative 26 113 ,116 Platforming process mainly by the addition ofregenerative equipment (and usually an extra reactor). Thus, it is possible to show a single basic diagram (Fig. 21-13) for all processes. The
fixed-bed Hydroforming process is also basically the same except that
regeneration must be practiced so frequently (about 8 hr) that the use of
a waste-heat boiler is justified. In some plants, a single still with several
coils is used rather than the 3 heater stills shown in Fig. 21-13. A prefractionator is not required if the regular topping equipment of the refinery
can separate a large well-fractionated (200 to 400F) Platformer feed. A
118
816
I.
small high-pressure (600 psi) drum is used to store hydrogen for startup.
When the catalyst is new and active, the first of the three reactors is held
at a temperature about 5F higher than the second, etc., bu~ as the
catalyst becomes deactivated all of the reactors are allowed to come up to
full temperature.
Naphthas have been encountered which contain as much as 350 parts
per billion of arsenic, and this must be removed because it quantitatively
unites with the platinum causing deactivation of the catalyst. Most
feeds (over 80 per cent) contain little or -no arsenic, and need not be
treated. Filtration through fuller's earth is highly successful in reducing
Ughl naphtha
10 storage
,,. ... I
I
I
I
I
I
I
I
I
I
Produci
siobilizer
Gas'separalor
I
To
and from
reboJ~ers and
exchangers
Hydrogen recycle,
Healer
the arsenic to below 10 ppb and usually 5 ppb. Little clay is used (6,000
28,000 bbl per ton) unless the naphtha contains abnormal amounts of
water which is also adsorbed. A relatively simple method of determining
these trace amounts of arsenic has been devisecl,119 and it is mentioned
that about 90 per cent of the arsenic, during a distillation, stays with the
residue. Clay filtration also removes traces of lead.
Large amounts of sulfm tend to deactivate the catalyst temporarily
or to utilize the' active surface. Many plants desulfurize the feedstock,
and catalytic desulfurizati~n (hydrogenation) not only removes all arsenic
but upgrades cracked materials so that they can be reformed. Sulfide
corrosion is normally severe, necessitating the use of 12 and 16 per cent
chromium steels (18-8 chrome'nickel is even better).u
Three to five pounds of catalyst per barrel charge stock is required
to fill the_ reactors, and a fresh charge of catalyst must be readily availabl~.
to
817
Th,e service charge for replacing spent catalyst with new is about 34.00
(1956), and the cost of new catalyst ranges from $9.00 to $14.00 per lb.
Yields were indicated in Fig. 21-6.
In an effort to obtain ev.en higher octane numbers, the Universal Oil
Products Co.120 bas devised a combination solvent extraction (aqueous
diethylene glycol) and Platforming system which permits the recycling of
fCP11J..'~_,
mDke-up
I
I
I
I
+
Prelrocfiotlofor
cotloct
htpper
r-.,
:
I
I
I
C/Il1rge
a.-_-.. . .
Lt. naphtha _
I.o.....!~
Nophtha
heater
~
Recycle ({as
from frocftonator
Recyclo gos
healer
(pet~ Refinef,'.)
D.
106.
8.18
to
CHAPTER 22
I
820
but pressure tanks are the common metho~of storage. Although enormous ainounts of butane, propane, and ethane are available and very
cheap (butane valued at only 1 cent per gal when sold as part of natural
gasoline),5 the lack of a cheap method of accumulating and transporting
these high-vapor-pressure materials"has been a great deterrent to widespread use or the development of chemical projects. Underground
storage in natural or man-built caverns (1.8 trillion cu ft of gas, a and
over 16 milJion "bbl liquefied gases') is aiding in stabilizing winter and
I
I
I
I
I
1-
r
I
TABLE
Year
Total
sales
Domestic
and"
motor fuel&
Industrial
and
mise. 1I
2,600
57,832
1,473,289
2,636,736
3,174,012
4,068,000
400
62,694
275,883
338,959
."
401,615
614,000
Gas
manufacture
Chemical
ms.nu" facture
Rubber
components
32,299
524,350
870,990
1,050,239
1,642,000
225.,641
370,997
307,735
439,000
""
"1922
1928
1938
1948
1952
19M
1956
233"
4,523
165,201
2,736,801
4~477,379
5,125,533
6,997,000
1,500
~2,386
237,638
259,697
191,932
234,"000
, summer operations, but only a few (5) major L.P.G. (liquefied ~nd petroleum gas) lines, all in Texas, have been proposed or built. " Chemical
developments at distant points are usually situated on a major naturalgas pipeline~ and the ethane, prc:>pane, etc., are separated at the point of
use.
The lighter hydrocarbollB~ such as propane, isobutane, butane, and the
corresponding olefins, removed from ~tural "gasoline and refinery gases,
are widely used as so-called "bottle gas" (Table 3-5). The enormous
growth 7 of the liquefied petroleum gas (L.P.G.) industry is indicated in
Table 22-1.
"Nelson, W. L., Relative Prices of Various Grades of Natural Gasoline, Oil Gas J.,
Sept. 28, 1953, p. 149.
II Underground Gas Storage Still Rising, OilGaa J., Apr. 23, 1956, p. 68; and L.P.G.
Storage Hits New Peak, Oil Gaa J., Aug. 1, 1955, p. 60.
7 L. P. G. Cbalk.s Up Record Gs.in in '55, Oil Gas J., Jan. 21, 1956, p. 52.
" i
821.
The use ofL.P.G. for chemical manufacture grew rapidly between 1938
and 1948, but since 1950 the ~ost rapid_gain has occurroo in its use as-an"
engine fuel for busses, trucks, tractors, diesel-electric locomotives, tankers,
and barges. As much as 15 per oont propylene does not harm propane
fuels for bus services. 8 Propane (and propene) constitutes nearly 70:
per cent of the total L.P.G. marketed.. During 1956 the demand for
.
L.P.G. (excluding that .used in gasoline) was:
Millions
bbl
Propa.ne (incl. CaB.). : ...... ~ .....'
Butanes (inel. C,H a) . ~ . , .. ;
Bu tane-propane ~ ........ '. .Other mixes ........-..... -. ... .
90.6
Per
cent
29 ..7,
56.2
18.4
17.5
iO.8
23.4
14.6
*' Proba.bly
Natural gas is still the major source of carbon black (Ta.ble 22-2), but
-increasing amounts of oil are being utilized . . About 94 per cent of ~e
carbon black used in the .United States is compounded into rubber goods.
Synthetic rubber requires much more black (Table 22-2) than natural
rubber. Most of the rest of t~e black ia used for printer's ink ~nd paint~~
TABLE
22-2.
MillionS Ib by
. raw material source
Year
1925
1935
1945
1950
1953
Lb per
loolh
rubber'>
Total
productiol!
Channel
Furnace
Gas
Oil"
178353
1,053
1,382
1;611
-144
316
539
617
454
34
37
514
765
1,157
178
353
...
...
12
18
70
340
673
37
33
35
983
1,042
938
The drying of gases and volatile liquids was discussed briefly on pages
233 to 235, the solubility of water in liquids is indicated in Fig. 5-24, and
the properties of .the adsorbents used in drying are indicated in Tables
8 Ebinger et at, Propane Motor Fuel with 15% Propylene . . . J SAE Journal,
January, 1955, p. 34.
822
10-4 to 10-6. The formation of hydrates with carbon dioxide and- with
hydrocarbons such as: 9
C3H s ,18H 20
Propane
Carbon Dioxide CO 27H20
CH"7H 20
C 2H s ,8H 20
Methane
Ethane
is troublesome in high-pressure gas lines and particularly in low-temperature fractionating equipment, The temperatures and pressures for
hydrate formation 10 are indicated in Table 22-3.
TABLE
22-3.
OF
0.55
(methane)
0.7
0.8
35
430
120
100
40
45
50
600
165
230
14.0
SOO
1,100
1,500
55
60
65
75
"
110
150
1,000
192
265
380
580
890
500
780
3,100
2,600
2,200
,.
320
450
2,100
2.950
0.9
680
230
330
22-4.
Reaction
Name
H~
Regeneration
+ 2H 20
+
+ H 2S ~ NaHCO a + NaHS
Na.4As~r.02 + H S -+ Na As, z8 0 + H
Girbotol. . . . . . ..
-phosphate .......
'Phenolate ......
Vacuum ca.rbonate., ..... . ..
+ H 2S ~ (RNH ):S
KaPO. + H~ ~ KHS + KJIP0
Na.OC~H& + HtS ~ NaHS + C H 0H
NazCO, + HtS ~ NaHCOa + NaHS
2NaOH
-) NatS
Ca(OHh + H 2S -) CaS
2H zO
FeO + H~ -} FeB + H20
Partly' by air
NaiCO a
2RNHII
Air blowing
N a~AszS60
+ ~02-)
N a4As~502
Steaming
Steaming
Steaming
+S
Vacuum steaming
and Deaton, Gas Hydrate Compositions and Equilibrium Data, Oil Gas J.,
July 27, 1946, p. 170.
1 .Schutt and Zdonik, Compression a.nd P~treatment of Pyrolysis Products, Oi~
Gas J'J June 25, 1956, p. 92.
G Frost
=...",..,..,.
- ;--.-
,-,- ,-;,_"\.~.
: '--; ..:,;;..3
823
~- ' ,
1-
!
{
,,
I
!
'1
I,
-
824
WeI gas
Ct ''\
23
Ci 24
.~
~ 12
AbsOrber
SlrippingSliI/
f'racliona/or
4 .4
_
., <;'+ I
Recovery..fJ<Skm gas 0 Tempera/ures
~ !J1illion pertlcry
PresslJres (6a)
FIG. 22-1. Simple absorption, stripping, and stabilization plant.
are used to create the pressure in the absorption tower are not shown.
~igure 8-2 presents much the same arrangement except that control
11lstruments are shown. The wet gas is compressed and admitted to
an absorber column. This column and also the stripper and stabilizer
are of the bubble-plate or other conventional type of construction,
.alth~ugh the tray spacing is usually not over 18 in. In the absorber the
wet gas flows countercunently to an absorption oil and.leaves the top as a
dry natural or refinery gas. The rich absorption oil flows through
exchangers in which heat is exchanged with the hot lea.n absorption oil,
t?rough a steam heater, and into the stripping column. Some fractiona.tion as well as stripping may be accomplished in the stripper or still, and .
hence hea~ ' is supplied at the bottom by a steam reboiler and reflux is
used at the top. Wild, or raw~ natural gasoline and steam pass overhead,
.and some of the light constituents cannot ordinarily be condensed. These
~ cycled back into the absorber. The wild gasoline is pumped through
heat exchangers t.() the stabilizer (fractionator or rectiner) , and stable
na.tural gasoline and dry gas are produced. The stabilizer is a typical
fractionating column with a steam reboiler. Sometimes it is more
economical to allow some gasoline hydrocarbons to escape in the residue
gas from the st~bilizer and cycle this gas through theabsorber than to do
an exac~ job of fractionation in the stabilizer.
When handling large a.mounts of gas, exceedingly elaborate plants such
as the 350,000,000 ell it plant14 shown in Fig., 22-2 are justified. This
plant handles the six gases shown in Table22-5. The absorbers operate
at 2,250, 1~250, 500, 150, and 50 :psig; the rich absorption oil is stage
207
2,250
100
1,250
12
500
22-2
20
150
50
Vacuum
68.51
13.73
10.20
2.21
56.43
8.90
0.807
91.27
.4.96
1.80
0.43
91.81
4:50
0.57
0.18
0.19
0.60
0.52
0.20
0.21
0.39
0.700
0.636
1.86
0.50
89.33
5.52
2.46
0.59
0.60
0.36
0:23
0.91
{).OO9
15.35
2.52
1.00
0.63
6.48
5.60
3.76
1.98
1.20
l.M
5.598
6.570
I
I
stripped 1& at pressures of 185, '50, and 5 psig; the rich oil is heated -in
direct-fired pipestill heaters; and the liquid product is fractionated into
deisopentanized gasoline, kerosene, propane, isobutane, butane, and
isopentane. Stage stripping or stage separation is the same general
operation as the successive flashing shown in Fig. 15-15 except that vaporization is accomplished by reduction in pressure ra.ther thah increase in
temperature. Such'an operation assists in holding gaseous or low-boiling
materials in the liquid, and hence this operation is also useful in the separa tion of gas from crude oil. 18,17
.
Although steam is used for heat in many small and o~der plants, directAnon., Process Improv.ements Mark Design and Operation . . . , Oil ~ J.,
Dec. 15, 1945, p. 88.
Hi Wade,. H. N' J Multistage Wea.thering of Satura.ted Absorption Oil, Oil Gas J., M~
1O~ 1945, p. 57.
.
1& Kimmel et al., Sta.g~ Separation of Oil-ga.s Mixtures, Oil Weekly. Oct. 17: 1938..
17 Huntington a.nd Schmidt, Problems in Condensate Type Production, ~t. Engr.,
February, 1941.
14
,;"
A.: Ory
.,'
9as fQ
-A
..... A
compressors
Rawaas
Raw gas
~Rawqas
Raw gas
H;Qh ;n;"';,,! lean 011
!iawga,r
Low ;nifial lean 0;1
Rich.oil"
l-
0/$0-
of-
~l;ufan6
:l
.0
e~
-~
~
~.
Reboiler
furnace,
INch
Dei,roeenfanized
o;r
gasoline
Hi9h in;Hol
leon oil
sur-ge d
c
..
~ Low in!!";".
lean 0'\
5~rqe drum
. - _. -- -fie
___ 0._-- -. . . . . .. _ w
Normal
bufQne
----- -- - ..
~-
---------~
.-~
,.- --- .
..
.-..-
827
fired pipestill heaters are being more and more widely used. 18 These
are used not only to heat the rich oil but to produce a stream of the hot oil
which is used to heat all of the reboilers a~d sometimes to generate
enough steam for stripping. Some plants are so completely automatic
that they shut themselves down in an emergency. IS Water is often scarce
and in such plants air-cooled condensers are used.19 One operator find s19
that plants opera.ted entirely without water (or steam) cost only slightly
more than conventional plants. In the extreme; gas can be used to
drive reciprocatjng pumps or by means of gas engines, and the stripping
of rich oil can be accomplished with gas,20 or high-pressure fractionation
can be used rather than a steam-stripping still. carryover of absorption
oil is expensive and it .tends to befoul the beds of desiccant type driers.
It may be alleviated 20 by (1) admitting the oil two or three trays from the
top of the absorQer, (2) using higher-molecular-weight (210 to 230)
absorption oil of a nonaromatic type, and (3) using various types of mist
extractors in the top of the absorber and in the dry-gas line, especially
the wire-mesh type of extractor. Small plants [2 to 5 million standard
cu ft per day (MMscfd) l are becoming economically feasible,21 and some
small plants complete with drying and treating equipment are mounted on
skids 80 that they can easily be set at a. new location.
Distillate Plants. The gas ih some fields is at such extremely high
pressures (2,000 to 6,000 psia) that it dissolves some of the heavy liquids
with which it is associa,ted. It is so dense that it behaves somewhat
as a liquid. Note in Table 2.2-5 that the hexane-plus content of the gases
is large in the 2,250-1b gas, that it decreases down to 500 lb, and then
increases again at low pressure. Thus the highest-pressure gases dissolve
hexane somewhat as if the gas is a liquid . whereas the hexane gets into
.t he lowest-pressure gases simply by exerting its vapor pressure. Upon
reducing the pressure of high-pressure gases, a region of liquid formation
is encountered as indicated by the isothermal line of Fig. 15-6 (see also
Fig. 15-8) and then upon further reduction in pressure the material
becomes ~tally gaseous again. This type of condeILSation is referred to
as retrograde condensation. For this reason, distillate gases are usually
processed by reducing the pressure to 1,500 to 2,250 psm and passing them
through a separator for the removal of some liquid. The gas may then
be forced back into the field by compressors, or it may be sent through
high-pressure absorbers before being sent back to the field. Each gas
Sutherland and Swindell, One-man Operation . . . ,.Oil Gas J., Apr, 18, 1955,
p. 180,
.
.
19 Lane, R. L., Dry Distillation, Two-still System, Oil Gas J., Jan. 2, 1956, p. BO.
to Lane and Thompson, Hydrocarbon Stripping, Oil Ga8 J., Ma.y 5, 1952, p. 174.
21 Symposium. Midget Pla.nts-and How They Grew, Pet. Refiner, June, 1956,
.pp. 145-156.
18
j
I
I
f
I
"
,j
1
828
behaves-differently, so that experimental tests are still nec~ry. However, progress is being made on determining the equilibrium ratioS (or constants). of hydrocarbons at high pressures an4 in various mixtures. Obviously it behooves the producer to maintain a high field pressure beca.use
reduction of the pressure to 2,500 Ib or lower will ca.use the 1I distillate"
(hexane-plus hydrocarbons) to be_lost as &' liquid in the gas sand. Almost
any flow diagram would b~ misleading, because distillate plants are so
~e and elaborate that no two are alike. -Figure 22-2 at least ,the part
pertaining to high-pressure absorption
the general recovery and
separation BYstem, is typical of many recycling or distilla.te plants.
Examples are available of plants that utilize (1) the retrograde condeD.S8r ,
_ tion mentioned above,2t (2) simple cooling and pressure nwntenance with
comp~ors, (3) stage separation, U (4) high-pressure absorption somewhat 8.8 in Fig. 22-2, and particularly combinations of these operations.
Reftnery and Chemical Plant Gas Recovery. It is becoming increasingly useful to recover substantially all of the propane and even ethane
(or ethylene). Higher absorber pressures and larger circulations of oil
may be used to capture the propane or ethane, but it is also necessary to
tlse refrigeration if ethane is to be recovered. The Tennessee Gas Tra~
mission Co.n cools the entire gas stream (750 MMscf) to minus 96F with
temperatures of minus 121F at some pointa. The plant can be operated
so that SUbstantially only methane is returned to the company pipeline.
A somewhat similar operation is shown in the gas recovery part. of Figs. ,
20-4 a.nd 20-5 ' under-the discussion of Ethylene Plants (Chap. 20). Although true gases such as propane and ethane can be captured in
absorption oil or into a liquid by refrigeration; the retention of them in the
li'quidState so that they can be purifiedby fractionation requires the use of
high pressures and low temperatures. As a compromise, one method of
deethanization and retention of propane involves elimination 'of the main
-bulk of methane and ethane by means of a primary absorber. Dissolved
et~ne iB then completely flashed from the rich oil, carrying with it much
:l>ropane which ia captured again at high oil-circulation rates in a smaller
teabsorber. . Much the same is accomplished in the catalytic cracking
l>lant gas-recovery system 2 of Fig. 22-3. This. involves use of the gasoline
product itself as part of the absorption liquid (it is' able to hold additional
gas because of the higher pressure in the absorber) but at the very top
\
I
\
t
\,
\
\
~
ana
\
\
\
\
\I
829
of the absorber, a heavy gasoline recycle oil is used to absorb the last of
the propane (up to about 90 per cent). The highlY ,wild gasoline is then
processed'in a combination fractionator-absorber (rich oil deethanizer of
Fig. 22-3) which vaporizes unwanted methane and ethane~to the upper
absorber part where it is me~ with heavy gasoline absorption oil~ . .
About the simplest system for the recovery of large amounts (60 to 75
per cent) of propane and propene is a plain fractionator operated at a pressure so high (300 to 360 psis. with catalytic cracking gases) that the entire
Dry gas
Gas
Main ~-..a......,.
froclionfifor
OH
occum.
Oebufon;zer
..
Rich oil
ds-efhonizer
"
Kl1oCkOUf
drum .,--1-...1-..
lSOpslg
Heavy
Ilne
rich~il
cracking-plant gas and gasoline stream can be admitted at the top without
losing significant amounts of butane. Dissolved ethane and ethylene are
eliminated from the bottom product by heating the bottom of the fraetionator with a reboiler. If the recovery of even more propane is feasible
an absorber operating on light cycle oil from the cracking-plant fractionator (and returning to it) can be used on the gases from the fractionator.
The disadvantage of such a simple system is the cost of compression_
A small amount of refrigeration (water refrigeration to about 55F ot
propane, etc., refrigeration to 0 to 10F) is sometimes economical in
recovering propane (Fig. 21-10), and in the case of ethane or ethylene
830
Carbon blocK
sfDrage fank
Hoppercqr
Burner wildings
.... Elevafors-'
of.importance are the Furnace 26 (Fig. 22-4b), Channe1 27 (Fig. 22-4a) , and
Therma1 28 (Fig. 22-4c) processes. In the Channel process incomplete
combustion occurs in the presence of steel channels that chill the gas
flame. - The Furnace process also involves incomplete combustion, but
mixture~ of ga~ and oil are burned (gas furnace process) and more recently
oil alone. The Thermal 'process is a cyclic process in which hot checker- brick is used to deoompo~e the gas thermally. Yields are large by the
Thermal process, but the carbon-black particles are too large for many
applications. The carbon and gases are C0.91ed with water (no. cooling
is needed in the Channel process); and the carbon is separated-by Cottrell
Nelson, W. L., all in Oil Gas J., Furnace, May 11, 1946; Thermal, June 8, 1946,
p. 95; and Channe~ July 20, 1946" p. 123.
IISSwaminathan, V. S., Britain. Gets lISc,otless" . . . Pla.nt, Oil Ga8 J., Jan. 11,
1951, p. 75.
t? Kiddoo, G., Carbon Black . . . Natural Gasoline Industry, Oil Gas J., Apr. 5,
1951, p. 81.
18 Paulsen, D. C., Cyclic, Yet Continuous. Instrumentation (Minneapolis-Honeywell Regulator ,Co.), ~oL 6, no. 6, p. 35 (1952).
26
- . -~---
TIRTIA~V CYCLONE
$(CONOARV C.'fCLONE
ELEe.TAOSTATIC.
PRICLPITATOAS
SHAa(~R
CVCl.ONI
~/I
'
GONVEVOR
.j
8UUc
STORAGE
"ELLEnEEO
w.
gj
SoCAllN
RE.CO\(l:A"i" SYSTEM
BLACK.
...
Go
w.o.T'.
8UCICT
El.E.VATOR
DRYER
r ......_...:;:..'~ .. ,
c=n
~ .......-' ~:=:-,-1
~;.--ORVER-~~RNAC
--- '"
.......
FVRNACU
FIG.
"'--
..",.
BULK
TRAHSPORr VA.N
BAG
PACKU"
. _ .- - . . _ _
_ .- .
'0:"-
IFJ(
r
l i
1\
'~!
I
I
,./
.~
"t
1
)
Cooling
Gener.ator
water
belng healed
t
R
conveyor.
,
~ ---.. Thermal
black
product
833
, I
Almost all field and refinery gases are of such a composition that they
can be profitably processed lor the manufacture of natural gasoline. Prior
to 1915 a gas containing less than 7 gal of stable Mtural gasoline per thousand cubic feet was called a It dry gas" and in general wris not considered
suitable. Since that time the value of natural gaspline has increased and
the methods of recovering the gasoline have been sO"improved that almost
all natural gas containing more than 2 gal of gasoline per thousand cubic
feet is being processed and gases that contain only 0.3 gal per thousand
cubic feet may be economically handled. Tables ~2-5, 22-6, 14-4, and
19-8 show analyses of variou~ natural and refinery gases.
In estimating the gasoline or liquid content of a wet gas (Example 22-1),
Table 22-7 will be useful. In general, the ,olefin hydrocarbons produce
less liquid by about 7 per cent, but exact values can be computed from the
specific gravities of Tables 5-2 and 5-3.
Liquids. The general composition of raw and stabilized gasolines,
'? ottle gases, and distillates (or condensates) is shown in Table 22-6 and of
pressure distillates in Table 7-2. Similar information about crude oils
is shown in Table 4-5. The compositions of distillates or condensates
from cycling plants (items. 21 to 25, Table 22-6) are of little significanee
because of the wide range of pressure and temperature maintained, and
because the liquid recovery is often reported as several produ<?ts such as
hydrocarbon liqUids, distillate, and even kerosene.
.
The specifications of natural gasoline and the system by which it is
graded are given in Fig. 3-2, and the sOmewhat standard grades of liquefied petroleum gases are shown in Table 3-5. The approximate relationship among the composition, properties, and grades of natural gasolines
is given in Fig. 22-5. I t is not generally applicable to the olefin-bearing
liquids produced in refineries, but it may be used as an approximation.
The butane content of many gasolinelike products is closely related to
their vapo~ pressures (Table 22-8). In natural gas, the butanes fraction
contains about 31.9 per cent (22 to 49) of isobutane, and the pentane fraction 53.7 per cent (19 to 70) of isopentane.
For statistical purposes, the U.S. Bureau of Mines and the Natural
Gasoline Association of America (NGAA)3 use the following factors
(multipliers) to obtain the equivalent volume of Grade 26-70 natural gaso28 Strasser, D. M., From Hydrocarbons to Carbon Black, Pet Refiner, December,
1954, p. 177.
30 Nelson, W. L., Volume Equivalent . . . , Oil Gas J., July 13, 1953, p. 149; and
Relative Prices' . . . , Oil Gall J., Sept. 28, 1953, p. 149.
.
I :
I ,
! '
r'f :
il .
;1
~"
..j
. 1 1"
r':
::1)
\ 11
'T ABLE
22-6.
*" I;\.~l
~.l1!
i~
Gaso. ...
Mat.erial
,I
From
gal
per Maer
.~
:.
:.
.
..
.n~
R.f
20
2
2
2
24
2.
Dry
Dry
Dry
Dry
Dry
Dry
Stabilizer
440-1b absorber
52-1b absorber
1S-1b absorber
A verags of 45 c
Gyro plant.
Gyro absorber
Raw gaso. tanks
2.400-1b well
Average of 45Abaorber
High pre88. aba
High preas. aba
High Pre4lS. sba
150-200 Ib aeparator
25-1b sep.
Stabilizer
175-1b sta.biliaer .
245-lb stabilizer
440-1b stabilizer
622-lb aepara.tor
Stabilizer
l,250-1b. zero OF
.400-1b, -12'"'F
-50F
94.5
92.2
92.2
91.8
.. ...
... .
. , ..
'" .
... .
... .
....
60.0
60.0
51.0
....
.. , .
.....
........
18.7
77.0
17.2
18.4
63.7
62.01
216.01
. , .....
8.9
.. ..
.... ,
.. , .
. ., .
. ....
......
.........
, .. . ...
..........
......
........
.....
......
... " ,
. . .. . ..
... .
..... .
..
. ... , ..
... , .
..
........
.. . . ..
..
....
... .
..
..... ,
..
..
.,
.,
.......
1.78
. , ...
4.87
2.13
..
pei&
... ...
... . .
--
g~s
volume)
V.l>"
gravity
0.0
0.13
0.06
0.0
0.10
1.48
Reid
API
CHi' CIH,
C.Ha
rodilO
C,H1O
iC,Hu
10.0
8.7
19.8
27.2
6.3
13.2
10.3
15 .2
4.8
6.5
1.5
2.8
1.8
1.9
8.1
0.7
8.61
2.60
0.86
1.21
6.00
0.78
0.86
0.47
0.97
8.00
0.69
6.43
0.10
77.9
86.4
60.8
18.7
84.8
38.S
44.4
7.2
88.6
79.8
0.1
0.1
0.1
....
0.9
. ...
.., .
.. ..
'"
' "
15.3
4
.....
43.7
16.7
1.6
.. .
,
...
0.2
..
9.4
12.0
2.5
-~------
..
..
10.88
0.61
1.35
8.76
9.38
8.81
10.23
3.58
0.13
11.55
17.10
8.90
2.81
3.80
5.80
3.94
I
1 1.55
2.56
2.97
48.2
47.1
2.33
29.33
23.33
26.95
5. 54 1 12 . 24
. .... {5.25
8.36
6.36
l1.58 11g .3a
18.80 13.21
0.60
25.54
28.61
72.2
83.6Q
51 . 23
46.09
0.40
99.. 4
5.63
0.2
4.291 8. 02
0.49 . 0.24
28.16
0.63
8.74
0.16
2.47
6.06
16.18
1. 73
2.67 19.17
58.20 41.20
. ....
. .....
4.6
."
.. ..
3.16
. ...
8.92
17.12
45 . 10
7.74
3.68
2.95
34.72
2.11
6.22
12.12
17.29
16.03
11.08
6.71
C,Hu+
C,Rn
5.74
4.4.5
10.30
16.85
14.81
-
6.42
6.72
3.68
4.38
2.45
3.90
5.90
3.75
7.16
-
--
8.80
-~
54.94"
81.45
a.85
22.90
52.80
. .. -
'- "'_.
835
line, and the price factors (multipliers) used by industry during 1933-1956
are also shown:
I,
.j
'1
l;,
22-7.
Volume
Price
1.470
1.362
1.258
1.129
1.000
0.896
Standard
Gal liquid
eu ft pure
per 1,000
component
standard
per gal
ell ft pure
liquid
component
. Gal liquid
Standard
per 1,000
en ft pure
standard component
eu ft pure
per gal
component
liquid
Methane .......
Etha.ne ........
Propa.ne .......
lsobutane ......
ButaJle ........
Pentane3 ......
16.94
59.14
25.2
27.4
39.7
36.5
30.9
31.6
27.5
32.4
31.6
,
36.~
Hexane ..... , .
Heptane ......
Pentanes and
heavier .....
Hexanes and
heavier .....
41.1
46.4
24_3
21.6
41:5
24.1
45.0
22.2
Reid 'Yapor
pressure
8
10
12
14
18
22
26
30
22-8.
V A.POR PRESSURE
Material
6.6
10.0
14.0
14.0
18.0
15--24
24-33
33-42
Natural gasoline prior to 1931 usually fell in Grade 26-70, and such a
basis is still retained in statistics, but shortly after 1931 during the development of the Oklahoma City field, great surpluses led to the sale of
mainly Grade 22-70, and most gasoline during 1956 had a vapor pressure
<. r.
i ;
I "!
836'
"
of only about 18 pounds. The volume factors tabula.ted above are simply
the ratios of the butane-free parts of the gasolines (see Fig. 22-5). Thus
if butanes had no value at all, the volume factors could be used as price
factors (actually so used during 1931), but the price factors in use during
1956 imply a butane value (when sold in natural gasoline) of about one
cent per, gal and lower.
Example 22-1. Gasoline Content of Natural Gas. A wet gas contains 30 per cent
butanes, 5 per cent pentanes, and 2 per cent hexanes and heavier.
Basis: 1,000 eu it of the natural gas.
30 X 1,000 X 1,000
31.9 = 0.3 X 31.9 = 9.57 'g a1
G aBO' I'me from butanes;a 100
, Gasoline from pentanes
= 0.05 X 36.4 ' """ 1.82 gal
Gasoline from hexane plus =- 0.02 X 45.0 = " .90 gal
. Pentanes plus = 2.7'l. gal
The percentage of butanes in 26-70 grade gasoline is about 32 (Fig. 22-5).
Yield of 26-70
~ ::
Example 22-2. Relation of Composition and Physical Properties of N a~a1 GasoUne (Fig. ,22-5). .A natural gasoline has a Reid vapor pressure of 16; it conta.in.a no
propane; and 50 per cent of it diatills at 140F. What are its approximate composi'
tion, its gravity, and the percentage evaporated at 100F?
The percentage evaporated a.t 140 deg is located along the base line, and the vapor, .
pressure is located among the Reid vapor pressure axes on the right, using the 0 per
cent propane axis. These two lines cross at the circle point on the diagram. ' This
intersection point is then located with respect to the other axes in the .figure, giving
properties' as follows:
1
:
:II
:_
~ade gasoline
lI '
'
i '
I
"
j
1
~.:r"' -
.... . , _ ... : -
~ ' '~~~~'-!:'<":--'--r'ic>?&""'I~"---~fi)Q
3 ...
Th. bulo ....'IDMhip .~","I ill tllia eN" .. bftw_ ",.. rOllr 'allow,nl ..... :
GRAPHICAL ANALYSIS
DtNrip~1Dn
OP
n1l.
Cocmllula
A.8.T.M. EballI'dltillIaUoD
lIP'"
("ohll8e'
Pen'na ratiD
hr cm~ penlADea
(vDlwne) In p..tanea
and "uvier
Pent(;lll1e Ratio
NATURAL GASOLINE
c"tva
Tb.I~lioD. of the lines repftlleMiDJ 'he known ~ i81\r.u an InleJlOtl.lon of ,he linn
",p,..nUnc die data \0 btl es1.IIIl&Lcd. ThUi Ule Inter.Klion 0140 . "4 .... porat..a al 100 ......
wiih 61 "~ evaporated at. l4O'"F." Ie .Ito \be i\lullleo~" nf 2tI.' .. '7. but.~ .nd llahtct''' an4
42.& .. palla "'liD."
In ..wiUo1i to th.il bNia leIationlkip, ,be Iolll.wini 'aelon m.,- be .. \i_ted. prIIrerab'r
willi \he baaie ralAtionlllip u Ulr ..tanl", poill~:
Tll'e
o-tipl.;"',
COOnli....koo
Solid
A..P.( ravl,}'
Raid ftpor
p~
For (1103.0%
'!';, propebe
(b~ voIlIDtel
~.
propAJl"
prop"....
'he.. tho, p-
12
FIG.
,,,x., ---
14~
..... -. ,
..
~ .,.; ,
. ..... .
~
g8~line.
50
."1M
60
.-838
field, and after passing through desulfurizers and gasoline plants, contained the following grains of sulfur per 100 cu ft: Mid Continent"
At field
3~650
1. 5-7.0
0.1-0.4
Finished
California
Finished
0.25
0.30
0.5-1.0
Under 0.1
None
Nonet
, 1
I
. .,
i
1':
I '
.t_1'
t
I'"
Air introduced into the line (within 100 miles of destination) quantitatively
oxidizes the mercaptans to disulfides. 31 However, the disulfides will be
reduced again to mercaptans after the oxygen is used up, in passing
through additional line in which the scale is wet with slightly acid water.
Natural gas and bottle gases are odorized with such sten?hes as ethyl
mercaptan, amyl mercaptan, etc., so that gas leaks can be quickly detected.
Methods of introducing stenches are discussed completely by Roy W.
Parker. 82 The NGAA 33 has Tentative Standards for Liquefied Petroleum
Gas, Specifications and Test Methods, and Standard Factors for Volume
Correction and Specific Gravity Conversion of LPG Gases and Volatile
Gasolines. The hazards of handling volatile liquids are emphasized by
, Pamphlet 58 of the National Board of Fire Underwriters. U
Conventional low-temperature analyses methods are too complicated
for plant control purposes, and hence numerous approximate tests have
been developed .such as the absorption and weathering test of the California National Gasoline Association,35 which is primarily for detecting
losses of isobutane and heavier hydrocarbons in absorber residue gases.
Generally, the test consists of passing a measured quantity of gas through
a standard hydrocarbon solvent at -44F (for pentanes plus) or -110F
(for isobutane plus), and then weathering the contacted solvent to a prescribed end point temperature. If the absorption factor for the commercial absorber and the composition of the inlet gas are known, the split
between iso and normal butane may be estimated. Empirical boil-away
Survey of Odorizing Practice in Gas Transmission, Pet. Engr., Midyear, 1941,
p. 114; also Anon., Inexpensive Burette Dispenses LPG Odorant, Nall. Pet. New8,
July 3, 1946, p. R-498.
13 Kennedy Building, Tulsa, Okla.
u 85 John St., New York.
ali Liljenstein and Schaufelberger, A Rapid Test for Isobutane (+) Fractions . . . ,
Pet. Refiner, April, 1946, p. 129; and CNGA Tent. Standard Methods of Test for L.P.
Gases, BuU. T.S. 441 (1945), Los Ang~les, Calif.
at
839
or controlled evaporation tests for the purity of isopentaneU and of isobut'a ne H have also been devised. One refiner uses the following boil-away
test for estimating the composition of mixed butanes (B-B cut): 100 ml
of sample is run "into a IOO-rol graduate containing a thermometer (- 20
to 120F), everything being chilled to a temperature below the boiling
point of the sample. This specimen is rejected, and the graduate is imm&diately refilled to 100 mI. Evaporation occurs at room temperature, and
for control purposes the evaporation to 0 to 5F is taken as propane, that
T.A1lLE
' 22-9.
(F-l)a
OF NATURAL GA.SOLINES~
Average
Reid vapor pressure,
pSla
Lowest,
clear
Clear
With 3 cc
TEL
Highest,
clear
."
I.B.P. of
160~ ..........
16
35
56
60
62
63.5
65
18
66.5
20
67.5
69
22e
26e
30~
70.5
73.0
44
62
66.5
68.5
70
71.5
72.5
73.5
74
75.5
77
67 . 5
. 80.3
83.3
84.3
85.1
85.8
86.3
86.7
86.8
87.2
57
69
13.5
74.5
76
77.5
78
78.5
79 .0
80.5
' 86.3
between 5 and' 40F as B-B cut, and the remaining material as pentane.
No claims of accuracy are made, but similar split temperatures may be
developed that will reasonably duplicate the performance of any com..
mercial plant.
Natural gasoline usually has a higher octa.ne number than norma.l
straight-run gasoline, primarily because of the high butane content.
Table 22-9 shows the approximate relationship between octane number
and Reid vapor pressure for Mid Continent and Texas natural gasolines..
The lowest octane numbers are associated with the highest Characterization Factor stocks, and the low values for gasolines with many side-chain
as Hachmuth and Tooke, Determination of the Composition of Commercial Isopentane, NaiL Pet. News, May 1, 1940.
n Tooke and Roberts, Determination of the Composition of Commercial Isobuto.ne,
o,il Ga8 J., Ap~. 7, 1945, p. 98.
840
g 6 I---"",--+illl--+-
(1)1:
CDR
~E
~85~++
o..c
.J::O'I
-t- ::i
+4- 4 ~-----+--,,~+--
co
~c:
&;g
E a 3 ~~=+----~--+--+---f
8~
~L
.~<2
>~ 2~---4--~~----+---~~---+--~
~lU
::t::~
~:i.:
Bufane-lsobufane
VI+-
c:V)
! .:
0..0
-;:)
l.
a~
,I
I
.
s
s
.Q.
841
or
T.he vapor pressure of blends can be estimated in much the same manner
except that mole percentages rather than volume percentages must be
used. The method is accurate when true vapor pressures are used, but it
is not exa.,et when using the Reid vapor pressure. The Reid vapor pressure
is lower than the true vapor pressure because evaporation of light components from the liquid takes place during the Reid test. 39 The kinds of
products prod.uced irr'1928 showed 4 that.the true vapor pressure was 5 to
~ per cent higher than the Reid vapor pressure. However, the range of
liquid .compositions now being produced is so great that there is little
Nelson, W. L., Relation of Reid to True Vapor-pressure, Oil Gas J., May 10, t"947,
p. 84; Recording Vapor-pressure, Sept. 27, 1947, p. 92; and June 21, 1954, p. 179.
4Oberfell, Alden, and Hepp, Comparison of Va.por-p~ssure Testing Methods, 8th
Ann. Meeting API, 192~.
U
842
relation between true and Reid vapor pressures (Table 4-12).89 The
inconsistencies of Table 4-12 indicate clearly that Reid vapor pressures
cannot be accurately computed.
In computing vapor pressures, the vapor pressure of the heaviest or
hexane plus fraction is always troublesome. In estimating its vapor pressure, boiling point is the most accurate basis, specific gravity is frurly
accurate, and molecular weight means little. . The approximate relation~
ship between the true vapor pressure and the specific gravity of It hexane
plus" fractions is
Specific gravity
API gra.vity
Vspor pressure
0.66
0.68
0.70
83.0
76.6
70.6
3.0
6 .5
1.6
Stock
Reid
vapor
pressure
API
Lb per
gal
Molecular
weight
Naphtha. ................
Na.tural gasoline . . , .......
6
18
57
72
6.25
5.79
119
90
76.5
23.5
Note in pumping the material tha.t the true vapor pressure of 9.51 psia must be
used in computing suction conditions.
843
smaller volume (see Fig. 4-40). This l'P..sults in slightly smaller total volumes and slightly higher densities than those obtained by plain weighted
averages. When two similar materials such as natural gasoline and
straight-run gasoline are blended, the octane number of the blend is the
weighted arithmetic average, but when blending with cracked or most
other high-octane materials the resultant octane number is higher than
one would expect (Fig. 4-46).
Car.b on Black. All blacks consist of minute carbon particles having
hydrogen adsorbed on the surface, and the channel blacks are also thought
TABLE
22-10.
Main
base
Channel:
HCC, high color . . . , , . . Gas
MOO, medium color ... Gas
LCe, low color: ....... . GaB
MPC, medium procea- Gas
sing (rubber)
EPC, easy processing Gas
(rubber)
Furnace (rubber):
HAF, high abrasion. , .. Oil
FEF, fast extruding .... Oil
HMF, high modulus . . . Gaa
SRF, semireinforcing .. Gas
Thermal: FT, fine ........ , ', , ... Gas
MT, medium ..... . .... . Gas
Lamp black . ............ Oil
KINDS OF CARBON
BLACK
Average
Percentage
particle
of U.S.
diameter,
production
millimicrons
(1953)
5-10
9-17
17-25 I
25-30
Yield,
Price,
per centoi
relative to
ca.rbon in
channel
main fuel
Q
To 2211
1.()4
1-6
0.7-1.85
20-65
0,6-0.9
1{}-30
6.6
0.5-0.75
20-40
. ,. ...
1.5-6.0
20-60
28.2
.30-33
33-35
45
55-65
70-90
150-200}
250-500
70-200
28.6}
13.2
6.S}
16.8
,;
Carload lots, f.o.b, pla.nt, are cheaper by 0.25-0.4 centS per lb.
b Up to 22 times or about S1.60 per lb.
e Similar to HPC, hard processing (rubber) black.
d About 7.25 (7.1-7.4) cents per lb., 1954.
,', 'J,
-844
has a. fair tinting power. EPC black for many years was the main black
for compounding with natural rubber. During World War II the high
modulus furnace (HMF) black was found to be' superior for use in synthetic (Buna S) rubber, and this accounts for t4e large increase in the
use of furnace blacks in recent years (Table 22-2Y~
To obtain good yields; the Characterization Factor of the oils used in
carbon black manufacture should be at least as low as 10.8 and a really
r-
\
I;
\
\
130
>
"
"
trO-
IOQ
..
~
\\
b.
120
.~
....
,..,..
''\
: .~
80
60
(>
60
'i
!:
1\\
70
"
.-
.0
0
102
10.4
10.6
lOB '
110
1\.2.
IL4
_.
\~
"40
10
IL6
11.9
12..0
CHARActERlZAnON FACTOR
FIG. 22-7 General effect of Characterization Factor on yield of furn.a.ce 'black (in
one plant).
superior oil will have a factor of 10.1 d (Fig. 22-7) .. Such oils are scarce (in
large quantity) and refiners cannot always afford to separate such small
and necessarily uniform-quality stocks. The oil furnace processes require
that the oil vaporize completely in a fraction of a. second, and although
temperatures of 2200 to 3000F are attained, the oils cannot have a final
boiling point much above 750F. Common mid boiling points are 550F
max if fed as a vapor to the carbon black furnace or burner, and 675F if
the oil is only partially vaporized before the burner. The yields of Fig.
22-7 apply to a furnace in which the oil is completely vaporized before
it is burned}!
Nelson, W. L., Chemical Composition of Oils Used in Carbon Black. Manufacture,
0..1 Gas J., Mar. 28, 1955, p. 145; and June 20, 1955, p. 117.
., Nelson, W. L. t Ce.rbon Black Yields .. (h,1 Gas J. t Dec. 13, 1954, p. 148.
U
NATURAL AND
REF~RY
GASES
845
46
Beede and Stokes, Carbon Black, Pet. Proce8sing, September, 1954, p. 1410. '
Whistler, A. M'I Fat-oil Peethanin,tion, Of,l GlU J., Oct., 26, .1946, p. 105.
846
Raoult's and Dalton's laws (pages 439 and 441 and Example 15-1) are
the basis for most absorption and stripping computations. At high pressures Raoult's law is not valid, and the equilibrium constants of Fig. 15-4,
etc., must be used.
Basic Absorption and Stripping. The process of absorbing parts of a
gas into a substantially nonvolatile liquid is in many respects similar 'to
-fractionation. Like fractionation, it depends upon obtaining equilibrium
between a liquid and a gas [Eq. (15-1), page 440]. Hence it can also be
practiced in a countercurrent manner in bubble towers or packed columns.
It differs from, fractionation because the temperature is substantially
constant and because the liquid and gas do not exchange places. Only
the component in which we are interested is transferred from one medium
to the other.
In the petroleum industry, absorption processes are usually conducted
in a bubble column, and hence the discussion that
follows will be limited to this type of equipment.
Envelope I (Fig. 22-8) gives the following materialbah,nce equation:
G(y~ - y~) = L(x~ - x~'
y'1 - y'2
G - x; - x~
where L
are
847
operating line for this condition would intersect the equilibrium line at y~.
Such conditions would require an infinite number of plates but a minimum
amount of oil. In Fig. 22-9 and in commercial practice more than the
minimum amount. of oil is utilized. The number of perfect plates ' is
determined by the stepwise process as indicated in Fig. 22-9.
I I
':I:
(x'2, y/~
)8
1
0.0 2
0.01 8
~:
~ OD! 6
\t-
.~Q.'
,~~
0.014
i~
~~ZI
(Y
~
~
nOI 2
IS
"E
VI
V
/
0.006
II
->,
./~b(\
\1' .
~
,/2
0.004
~~~
.. f/'I
0.002
~y
v.~ \In
1/
If)
QOI
~
~ QOO 8
"0
~J "/
o
/'
./
/' 3
o.o~
0.04 nOG
008
0.1
0.r2
QI4
0.16
0.18
-x'2
,
.
X = Mars of Pentane per Mol of Oil
FIG. 22-9. Absorption diagram for Example 22-5.
x'I
Exainple 22-6. Absorption of Pentane in Gas On. Air from a. solvent plant contains 2 per cent n-pentane. The pentane concentra.tion is to be reduced to 0.1 per
cent by contacting the gas, a.t 80F and 147 paia, with 6,950 Ib per hr of an absorption
oil that contains 0.05 per cent pentane by weight; 100,000 cu it of the gas, measured
at 60F, is handled per hour. The molecular weight of the oil is 220. Raoult's law
and Dalton's la.w a.re assumed to be valid a.t these conditions.
111
5.28
259
= 0.0204
848
Gas leaving:
Moles pentane
= 259 9~~
- Y2 ""
0.26
= 0.26
= 0.001
Liquid entering:
, Moles oil ==
--"--~=--
:x 0.0~5
'"'" 0.05
0.05
= 31.6 = O.OO15~
Liquid leaving:
Moles
p~ntane =
"
XI
(5.28 - 0.26)
= 5.07
+- .05
== 5:07
= 0.161
=-::r;
1r
Xl
'""'~-
and
-1/
:&'
0.01! _ 0 0101
.
, -
.~ - 1 - 0.01 -
0.0007
y'''''
= 0.0007
Zl
y'
0
0.01
0.02
0.03
0.04
0.05
0.07
0.09
0.10
0.15
0.20
0
0.0007
0.0014
0.0021
0.0028
0:0035
0.0049
0.0063
0.0070
0.0105
0 ..0140
0
0.0101
0.0204
0.031'
0.0416
0.0525
0.0752
0.099
0.111
0.177
0.25
0
0.0007
0.0014
0.0021
0.0028
0.ro351
0.00492
0.00635
0.00705
0.0106
0.0142
..
849
The number of plates can be computed by the stepwise method (Fig. 22-9).
\1
I
About
,0
yl US
-- -- - - ---
k-=+=-
px2.yf)
f-- f--l
I
II
/
.I
E Q4
0
6)
.....
CJ:)
~~,I
~7,
CL
I-
,
I
~t\~
61 _
~C'JqQ;
V'
4-
o QI5
"0
L
1/
CI)
t'/
Ql0
I
I
/yl:'
Q'2
I
J
I
V\\<,QI
.~
'/
S~J
,&(f.. /
\\)
J-
.~ rj
US
1.-
.....0c
1/
III
'0
"0
l/
xl
,I
f--1L V
005
fz3)V
x..y~
Y2C IW'
A a02
,
I
:
I
004
0.16
0.18
X2
5.07
..
1.
!-
850
B.
Partial pressure = p == pz
Xl
x=l+r'
.
z'
Partial pressure hexane = PI' = 3,800 1 + xl
Partial pressure steam = P.
= 812
- 3,800 1
x'
+
x/
x'
.
3,800 1
z'
1/' = p" = ----.:..-...-...,-p.
8
:r!
12 - 3.800 1
xl
x'
11 - 0.214 - O.786x 1
! .
About
7~
Multicomponent Absorbers and Strippers. The performance of absorbers can be most easily understood by means of a mathematical study_ 46
In an equilibrium plate the relation between the composition of the vapor
leaving the plate and the liquid overflowing from the plate may be
expressed as follows:
(15-4)
where y,., is t~e mole fraction of a particular component in the vapor leaving any pla.te or the nth plate; x,., is the mole fraction in the overflow
-liquid; and. K is an equilibrium ratio that may be determined from Fig.
15-4 or if necessary from Raoult's law.
By a material balance around any tray
(22-1)
where L is the total moles of pure absorber oil; V is the total moles of dry
gas; the subscript n - 1 refers to the plate above the nth plate; and
n + 1 to the plate below.
1..~!t
S.-Umnoll
utlng Yn
K f or
Xn ,
..- l rand yK
or
XIl-t,
L
KV (Yrl - Yn-l)
= Yw.+l
y,.,
(22-2)
Let
A =
ott Souders
;v =
a.bsorption fa.ctor
(22-3)
851
Yn
+ AYn._l
Yn.+l
+A
(22-4)
+ Ayo
+A
(22-5)
where Yl is the mole fraction of the component in, the gas that leaves the
top plate of the absorber and Yo is the mole fraction of the component in
the gas that is in equilibrium with the entering oil (or the oil flowing from
the hypothetical zero plate which is above the top plate),
-,
..
Ii
j,
+ Ay~
_ ya
1
+A
+ 1) + A 2yo
- ys(A
AI + A
Y2 =
+1
+ A + 1) +,Alyo
A '+ A + A + 1
(A a_I)
(A _ 1) Y4 + A yo
Y4(A2
Ys =
or
Y3 =
or
Y. =
1)
A-I
(All - 1)Y4 + A3(A - l)yo
(A 4
A4 - 1
Yn+l(A
Yn = ,
and because Yn
11
1)
A fl(A - l)yo
A n+I - 1
: 'i.
(22-6)
','r '
"
= Kx",
Xn
, Yn+l(it,n - 1)
A fl(A - l)yo
=
K(An+l - 1)
(22-7)
= y,.+l
(22-8)
- Yt '
, Solving Eq. (22-8) for Yn and setting it equal to Yn from Eq. (22-6),
_ (A-I) + yo (AfI+l_A)
(A
Yl - Yn+l
AfI+l _ 1
n+l -
1)
'
i-
II , .,
(22-9)
852
in which
An+} - 1
=1-
An+l -
Y,,+l - Yl _ A,,+l - A
Ytt.+l - Yo - A ,,+1 - 1
or
(22-10)
x"
8-+1
(22-11)
.
~,
KV
= 3.156dG
KM
(22-14)
I.
.. . .
. ..
.-
.....
~-
853
A _ 3.156dG1r
(22-15)
PM
s = 1:
A
KV = KWM
L
150d
or
PWM
15Od1r
(22-16)
(22-17)
After the A for the governing or key component is determined, the values
of A and the amount of absorption of each of the other components can be
obtained from Eq. (22-17). The reverse is true of stripping; i.e., the
amount of stripping is directly proportional to the vapor pressure of the
component in question. For an absorption factor of 1 (A = 1) for normal
butane, the factors for other components in a low-pressure absorber are
about as follows:
Component
Absorption factor A
C 3Ha ........... ,
iCtH IO ,
C 4 H lD .
iCr;H.,. , ........ ,
ii
'\
854
PETROLEUM
RE~RY ~NGINEERrNG
ence between the concentration in the incoming and outgoing gas. 48 The
expression in the denominator, YJ&+l - Yo, represents the maximum
amount of compone;nt that could be removed if the outgoing gas were in
equilibrium with the incoming lean oil. If the absorption oil contains
1.0
, ~ r:::-~~
0.9
~~
+
C c 01
)()(
.
1-
Q.I
Q)
)( ><
I...
0.6
~~
0.5
ill v V
J~
If/
~ ~ 0.3
0.2
I.
0.1
- ,;
'.
'"
//
/~
-f,cfFe
~I
t-
--
1"""-
,/
>->-
,..
hC2
~/7
.-1--'
~
~L..--:"--~~~~
.
0.&
V::~t-
r;
jV
o
o
0.2 0.4
2.8
3.0
is not exactly equal to the amount of component removed because the total
number of moles of gas cha.nges as it pa.sses through the absorber. If the compositions were given as moles of component per mole of dry gas) then the expression would
exactly represent the moles of component removed per mole of dry gas.
--
- ---
NATURAL AND
REF~ERY
GASES
855
An examination of Fig. 22-11 also shows the relation between absorption factor and the percentage of component that is absorbed. Consider
the line for five theoretical plates. This line approaches the line for
infinite plates as the absorption factor is decreased, until at 50 per cent
absorption, or (Y~l - VI) I (Yn+l - Yo), the value of A is nearly 0.5
(about 0.505). The number of plates that are used also affect the location of the point at which A is substantially equal to the percentage
a.bsorbed. Likewise the number of plates is related to the absorption
factor that must be used to absorb substantially all of a component.
The optimum value of the absorption factor A for any particular plant
is primarily a function of the value of-gasoline and the cost of recirculating
oil. The absorption factor (or oil recirculation) increases rapidly as large ,
percentages of the key component are absorbed. In most situations tb:e
economical amount of key ~omponent to absorb in gasoline plarits is
between 90 and 95 per cent 49 r:ather than the 99 per cent value .that is so
frequent1yemployed. The economical recovery of key component may
be as low as 60 to 70 per cent in small refinery installations, if the price of
gasoline is low J or if the co~t of oil recircuhttion eJ.(ceeds about 4 cents.
(See page 885.)
Example 22-7. Oil Rate for Low-pressure Absorber. A 26-70 grade of finished
gasoline is to be produced 'from a gas of the following composition:
, Volume
:,ComPDnent
per cent
7.15
1. 39
2.55
1.341.98
Th'e absorber is to operate at 90F and at a. pressure Of 50 psia. The absorption oil
has a. specific gravity of 0.83 and a molecular weight of lBO.The oil is completely
. stripped of isopentane, but it contains 0.0005 mole fraction of pentane plus. The
absorber has 16 actual plates.
How much oil should be recirculated, and what will be the approximate composition
of the raw gasoline?
A 26-70 grade of gasoline will contain a.bout 33 per cent butanes and lighter. If
99 per cent of the isopentane is a.bsorbed, enough butanes will be absOl'bed to provide
the 33 per cent that is r,equired-in the finished gasoline (Fig. 22-5).
Con's idering isopentane (key component)J
. d
1/1 = mo1e I ractIon m reSl ue gas
1/"+1 - 1/1 =
1/.. +1
41
Yo
=' (1
0.01 X 0.0134
_ 0.0134) + 0.01 X 0.0134
= 0 .000136
Nelson, W. L'J Economy in Na.tural Gasoline Plant Operation, Re/. Nal. Gaso.
MaYJ 1936J p. 167.
Mir.,
856
For practical calculations it is customa.ry to use the value of (Y"+l - Yl)/(Y"+l - Yo)
as the percentage absorbed, or in this CAse 99 per cent.
If the plate efficiency is 50 per cent, the column will behave as if it consisted of eight
theoretical plates. The absorption faetor, to recover 99 per cent of a component,
when eight plates are used, is about 1.5 (Fig. 22-11). The equilibrium cOnstant for
isopentane at 90F and 60 Ib is about 0.37 (Fig. 1~).
AKM
3.156 X-0.83
= 33.8
The equilibrium constant for butane is about 0.9 (Fig. 15-4), and hence the absorption factor for but1Ule is
AboWIe
All the components were studied in the same manner, as shol,VD. in Table 22-11.
TABLE
Component
CaRa.
iC 4H IO
C4Hu ...........
iC/iH u ..........
C 1H 12 + ........
22-11
Gal
Percentage
PerGal
Equi.
abof each
centage
AbMole
per constant sorp- component sorbed compoper
fraction 1,000 at 90F
tion- .
that is
sition
eu ftll and 50lh factor
1,000 of raw
absorbed
(Fig. 22-11) cu it ga.soline
0.0715
0.0139
0.0255
0.0134
0.0198
1.96
2.8
1.2
0.45
0.8
0.5
0.9
0.37
0.82
0.24
0.2
0.46
0.615
1.5
2.3
20
46
61
99
0.39
0.21
0.4.9
8.7
20.4
0.49
20.4
100
0.82
34.3
100.0
2.40
16.2
-Table 22-7.
The analysis of the ra.w gas.oline is not exact becs,\U!e some of the propane a.nd
butanes will be lost in the stripper and a little ethane (neglected) will be pl'esen~ in the
ra.w gasoline.
The approximate analysis of the finished stable gasoline can be estimated sa follows:
Gal of penta.nes and heavier ........... 0.49
+ 0.82
= 1.31
..
.,
~ -
NATURAL AND
REFINE~Y
'GASES
857
Component
Gal
Percentage,
liq vol.
0.645
0.490
33.0
25.1
0.820
41.9
1.955
100.0
I!
.. I,
,I
,!
h
'.;
,
~'.; :
.'
"
.:
("
I :
858
C,H 1o . 2.3
iC.B u ............ 1.6
"J
!
\
:1.
859
t~e
amount of conden-
~te?
V = 96
0.0416
L
V
KIFl
(L/V)
+ Kl
CH
512.2
,uncon ense
(1)
...
22-12.
. ..(2)
22-8
(3)
..
(4)
.(7)
.L
V = Q.0416
Component
Values of
Values
Kat SOQ lb
of F,
and at
moles
sooFo
CH, .. ... . . , . . .
CtH e.........
C3Hs. . .........
78 . 8
6.5
6.2
iC~H'D .........
1.4
C 4 HI0 ...........
iC 6 H u . . .......
C 6H12+ ..... . . ~
Total. .......
2.3
(J
(6)
L+K
Values
of V,
.
6.5
1.6
0,46
0.22
0.16
0.011
3.2
0.052
512.2
7.8
2.85
0.31
0.368
0.114
0.166
....
... .
.........
1.2
..
(5)
KXF,
(2) X (3)
(4)
7-
Moles
gaso.
(2) - (6)
(5)
6 . 542
1.242
0.502
0.262
0.202
78.29
8.27
5.68
1.18
1.82
O.SI
0.23
0.52
0.22
0,48
0.113
0.094
1.01
0.59
1.77
. ....
96.02
1.43'
3.98
Read from another source than Fig. 15-4, hence slightly different values.
860
Upon totaling toe volumes of each of the hydrocarbons, column (6), the total is 96.02
ra.ther than 96 as MSumed. A second solution would have been necessary h.ad the
sum been in error by more tha.n about 0.1 per cent.
The compositions of the residue gas and the condensa.te are as follows:
Moles, or volume per cent
Component
CH ..............
C1H s ...........
CaRs ............ .
iC,H 10
CcRu ............ .
iC 6H u ........... .
CaHu+ ... . ...... .
Residue gas
Condensate gasoline
81.53
12.80
6.53
5.91
5.78
1.05
13.08
5.53
12.06
-14.82
1.84
35.93
1.23
1.91
The residue gu, as shown above, is the mAterial that would be processed in a 500-lb
absorber.
,'
,
:
';
i
'
;
861
temperature fractionator (deethanizer) because ethane will be the overhead product (and reflux) of thefractionator (Fig. 20-4). The retention of
propane is somewhat more effective if two or more stages of pressure
reduction are used in the stripper system, as indicated in Fig. 22-2. This
permits a relatively lean stripping-still gas to be sent back to the absorber; .
and the smaller quantities of gases produced from the lower pressure
stages can be compressed) refrigerated, or handled by any of the methods
suggested above.
Finally, the propane can be recovered by adsorption (Hypersorption) as
discussed on pages 342 to 346 J and Fig. 10-17.
Stabilizer or Fractionator Design. Entirely satisfactory methods of
determining the number of plates in a stabilizer or fractionator are not
available. However, Chap. 16 discusses the general theory, and Examples 16-9 to 16-1.2 explain the behavior of two-component and threecomponent systems. Commercial reflux ratios and the corresponding
number of plates for separations between common pairs of components
(propane-isobutane J etc.) are indicated in Table 16-10. All methods
involve trial-and-error computations (Example 16-12 p. 509), and to a.
large extent they are mathematical exercises because of doubtful assumptions that must be made and especially because of the inadequacy of
equilibrium ratios. Perhaps the safest way to approach the design is to
employ reflux ratios and numbers of plates that have been used commercially, relying, of course, upon a knowledge of the basic relationships .
.An illustration of one of the proposed methods of design would consume
20 pages of this book and would arrive at an approximation of the minimum reflu~ and minimum number of plates but no answer for a practica1
reflux ratio.
In designing a. stabilizer, the conditions at the top (Example 22-9) and .
at the bottom are computed, the number of plates and reflux ratio are
adopted from examining commercial operations (Table 16-10); and meanS'
are provided to condense the reflux at the top and to supply reboiler heat
at the bottom.
Example 22-9. Stabilizer Pressure and Composition of Reflux.
has the following composition:
CH ....... " . . .. 0.03
C 2H e........ 2.27
C3 H 8 . 17.29
A 26-70 grade of gasoline is to be produced.
A raw gasolin.e
iC.H I0 . . . . . . . . . 9.38
C,H lo .... . , 23.3a.
iC,H 12+ . . . . . . . 47.77
The temperature of the cooling water
What is the approx-
862
fractjons of the components in the residue gas are about a.s follows:
(
Component.
Moles
0.03
2.27
17.29
12 .3
31.89
C 2H ........... : ..... .
C.H .... . ..... . , ..... .
i a.nd n C,H IO
Total . ... . ...........
i and n CeRio =
,,
(9.~8
0.09
7.1
54.21
38 . 6
100.0
- (47.7 X 89-10).
If the top reflux ratio is 4 to I, the total ma.terial which comes to the gas separator
is 5 parts, and the composition of the 4 parts of reflux must be assumed. As a first
approximation, the composition of the dew point liquid can be used. The dew
point of the gas occurs when summation of the y/K's for each component (i.e., x's)
equals 1.0 [Eqs. (15-3) to (15-7), page 4411. The temperature is fixed but the
pressure can be altered as indica.ted in Table 22--13.
TABLE
22-13.
(1)
Coml?onent
t
I
I:
CB, ............ .. ...
(2)
22-9
Assume 65 psi a
Vapor
(3)
(5)
(6)
fI
Kat 90
K s.t 90F
(2) + (5)
0.0009
CtR a.. , 0.0710
CIR e.. : . 0.5421
C,H 10 0.3860
Total. ... _ .... . ....
', 1
+ 23.33)
(4)
(2)
+ (3)
30
5
1.5
0.5
0.0142
0.361
0.773
1.1482
2.3
0.71
0.009
0.236
0.544
0.789
. .., .. . .
- -- ~ .,:
TABLE
(1)
(2)
Component
Gas com-
position
(1)
22-14.
REFLUX COMPOSITION AT
(5) .
Reflux
(4)
(3)
Assumed 4 X (3)
Separator
feed
(2) + (4)
(6)
65
(7)
(8)
Mole
Kat L/V +K
gooF,
fraction
4
(7)
(5) + 5.0 65 psis.
22-9
(9)
(10)
Kx
L/V+K L/V+K
(7) + (8) (6) X (9)
0)
Reflux
(11)
(12)
Mole
Mole
(6) - (10) fractiQn
CI:J
CR, ........
C 2 H G. . . . . . .
CaBs .......
C,H lO ,
TotaL ....
0.0009
0.0710
0.5421
0 .3860
1.0000
.......
0.01
0.31
0.68
1.00
....
0.04
.
1.24
2.72
4.00
0.0009
0.111
1.782
3.106
5.000
0.0002
0.0222
0.3564
0.6212
1.0000
46
8
2 ..3
0.71
49
12
6.3
4.71
0.92
0.667
0.366
0.151
0.00018
0.0148
0.1305
0.0940
0.2395
0.0074
0.2259
0.5272
0.7605
0.0097
0.2970
0.6933
1.0000
864
The bottozn t
8Ur!
(1)
(2)
Component
1(3)
CH 4
CalI ......
C.H lO
Total ....
4
900r
and 80
l{
4+K
Separa.tor
feed, mole
fra,ction 4
-----.
40
6.3
1.9
0.91
0.612
0.322
0.60 0.130
11---
t th
(5)
Kat
psia
CJI .. . . '.
(4)
0.0002
0.0222
0.3564.
0.6212
Kz
L/V+K
(3) X (4)
0.00018
0.0136
' 0.1150
0.0810
0.20978
(6)
Reflux
(7)
(8)
Mole
Mole
Assllmed
(4) - (5) fraction
0.00002
0.0086
0.2414
0.5402
0.79022
0.0109
0.3050
0.6841
1.0000
0.100
0.310
0.680
.Ii :::".
CHAPTER
23
1.- _
Engineers tend to become businessmen because of their constant association with economic problems, and this association accounts for the
,large proportion of engineers found in executive positions. Engineers are
also called upon 'to make decisions and to act, even though technical
information iB lacking or inadequate . . In this respe'c t they differ from
pure scientists whose interest usually pertains to the obtainment of
scientific facts regardless of the immediate need. Economic considerations pervade every detail of engineering design, and hence only & few
illustrations can be introduced here.
,
COSTS OF PROCESSING
a.
no.
866
23-1.
Basis
l~46"
Nelson
Year
ENR
construction"
refinery construction
Productivity
(bbl per
Refinery
wages"
man)'"
,[
1926
. 1932
1939
,\
.'
133
138
147
88
68
83
86
100
122
139
144
149
54
157
164
173
181
164
164
172
175
55
191
176
19.0
60
45
68
80
100
1942
1946
47
48
1-
,.
'.,
119
49
50
1951
52
53
I
~
56
'.
57
~t.
200
209
202
72
57
77
84
100
117
132
140
146
61
49
73
82
100
113
128
137 .
'144
152
168
174
183
190
198
209
71
82
100
109
126
133
138
149
155
165
170
121
138
140
125
100
105
109
125
125
Refinery"'"
69.
38.5"
65:.5 '
74_5'
100
122 .5
149
156.5
170.5
164
174
180
184
195
i77
126
132
135
142
149
.192
145
180
185.5
160
149.5
176.5
184.5
206
198
149
191
157
57
49
Operating cost
Plants 4
86 .5
47
74
80.5
100
115.5
138
141
152
163
169143.5
187
142
172
181
II!
" 1946 basic values are-Nelson index, common labor $1.033 per hr, 8~illed $1.80
per hr; refinery wages $56.75 per week; productivity 26.7 bpd per employee (total);
Estimated.
.;
-.
:.,--
(A corree-
867
ECONOMICS OF DESIGN
Topping ............................................
Topping and thermal cracking .........................
Cat. a.nd thermal cracking, polymeriza.tion, etc ...........
Cat. cracking, coking, polymerization, etc. . . . . . . . . . . . . ..
Complete processing ..................................
35 (13-58)
56 (23-95)
70 (40--105)
78 (52--110)
95 (68-135)
Costs may be stated in three ma.jor ways: (1) in terms' of the labor, utilities, nL and chemicals, etc. (Table 23-2), (2) in terms of departments or
units (Table 23-3), or (3) in terms of the properties of crude" oil that affect
TABLE
23-2.
Cracking
Topping
10,0006
2.6-6.0
0.2-0.8
14-48
1.2-3.8
0.6-1. 4
11-39
1.8-6.2
2.8-7.1
0.4-4.5
0.2-9.3
To 3.0
0.5-4.9
0.1--12 .8
0.1-4.8
0.1-4.9
Total.; ..............
0.2-10.1
To 3.0
2.&-8.2
1.0-6.4
0.7-2.0
0.3
2.8--15.4
0;5---1.4
0.4-6.7
0.2-11.0
Toi.8
3.0-10.0
1.0-5.0
2.8--14 .0
O.S-lotl
0.1-1.7
~
2.8-14.4
0.4-1.0
0.5-4.4
0.2-10.4
To 1.8
1. 3-5. 2
0.6-4.6
2.8--14.0
. ....
3,OO()b
1O,OOOb
1.1-7.0
0.4
0.5-2.0
0.3-1.6
1.7-5.1
0.:1-1.8
0.7-5.0
0.4-0.8
0.&-2.6
1.6-4.2
0.6-1.3
7-17
3.~.6
0.2
11-28
I~O
1.6-5.4
15,OOOb
1,000&
Water .................-.
(1945)0
2.000&
15--:10
Nelson, W. L., Profit per Barrel of "Extra II Tbroughpui, 0,1 Ga, J., May 5, 1945, p. 113.
barrels per day.
& Ca.PMity,
'868
operating costs (Table 23-4). The operating costs for a few crude oils,
using the same method as that used in Table 23-4, are plotted in Fig. 23-1.
. Gulf Coast plants of an average capacity of 30,000 bpd (12,000 bpd .
for small refiners and 200,000 bpd for major refiners), which conduct
both thermal and catalytic cracking, are examined in Table 23-4
TABLE
23-3.
5,000
(1946)0
COMBINATION UNITS
Thermal
Crud~
distilla.tion .. . ............
Vacuum reduc.t ion . ......... '....
T .C.C. oracking . . ...... . .......
6.0
... .
.....
3.4
8.0
0.3
2.3
0.1
Percentage
T.C.C. T.C.C.
(vis.
(vachr.)
uum)
. 6.0
. ....
13.4
2.9
6.0
1.8
12.2
2.9
.....
Thermal
16 . 9
.....
.. ,. ..
9.6
0.4
3. 1
0.1
0.4
0.1
22.7
0.8
6.5
0.3
0.4
2.7
3.1
.......
2.4
1.7
0.4
12.8
35.4
67.0
......
0.7
..
&
T.C.C. T.C.C.
(vis.
(vachr.)
uum)
15.0
. .....
33.5
7 .2
1.0
14.8
4.3
30.1
7.1
0.2
1.0
7.6
0.2
1.1
6.7
7.6
2.5
......
6.0
6.1
..
4.8
1.7
21.0
36.2
100.0 . 100.0
1.7
3.1
7.7
Royalty:
T.O.C .......................
Thermal .....................
Poly" ..... ,; ....
TEL to 79 (F-2) ...............
Total (194.6) ..........
Total (1956), approx ..........
I
..
..............
<
8.4
40.1
74.0
""
0.7
7 .9
40.7
75.0
1.1
19.5
100.0
Noll, Bergstrom, and .Holdom, New Integral T.O.C. Unit Makes Catalytic
Cracking Available to Small Refiners, Oil Gas J., Apr. 6, 1946, p. 110.
o
and Fig 23-l. 4 The product yields are based on the ~eeds of world
trade, which means that the operating costs should be larger (5 to 8
per cent) in supplying the la.rge gasoline needs of the United States or
Cana.dian market. The solid points of Fig. 23-1 indicate the production
of modest amounts of lubricating oil or wax (10 to 50 per cent of the
potential yield).
The operating cost items of Table 23-4 are aimed at distinguishing
between the various types of crude oils. Basic investment does ' not
include the eost of most of the processing equipment such as that required
'Nelson, W. L., EHeet of Gravity on Refinery Operating Cost, O~l GfJS J., Nov. 26,
1956, p. 99.
869
"
WEST TEXAS
-+ CALtFORNIA
x MIDDLE EAST
o VENEZUELA
-CANADA
o FAR EAST
a GULF COAST
e OTHERS
JloJ-=====::r;;~~~~~~---,----L~-.......-L--..;,o.-.-.I
'j
I
' I
'.~.
.,
p
:.
,
I,
";1
~~~------~--------~----------~--------~--------,~
10
20
30
40
50
60
A.P.I. (;RAVITY OF CRUDE OrL
"FIG. 23-1. Variations in refinery operating costs (1956) as a. function of crudH>i1
gravity, sulfur, sourness, octane number, and amount of Cl'8.(:king. Gulf Coast
30,000 bpd refineries. (Solid points indica.te the production of lubricants or wax.)
{Oil Gas J.) "
",
870
of- the operating cost items except the basic investment is related to the
properties of the crude oil, i.e., its Characterization Factor, the amount
. of cracking stock available for processing, the octane number of the
TABLE
23-4.
FOR A
FEw
1956)
Crude Oila
.Ba.ehaquero,
Vene.
16.4
2:02
64
HendMiddle
rick,
East'
W. Texaa
29.7
1.49
31.6
2.52
Tis
JUILIl8.
102,
Vene.
25.~
1.65
55
E8Jlt
Texas
38.5
0.33
57
12.0
29.8
Wax
crude,
Vene.
Southeru
Okla.
41.8
32.0
0.2
PeDDsylvania
43.9
0.82
0.1
46
11.2
11.5
41.li
11.8
31.6
33.~
28.4
8.0 ,
25.8,
3.5
0.9
3.2
3.0
i.6
27.7
20.2
8a.~
25.5
,1.5
35
20
17
2.8
18.8
13.6
40
17.1
11.2
. .......
4.7
12.7
2.4
7.8
18.6
... . . .
&
52
. .
.. . .
.....
2.5 .~.5
.
15.9
13.2
6.6
....... .
.'S.9
5.0
........
.. .
.. . . .
..
........
.......
.. . .
.....
....
JO.8
. .
11.6
.......
......
.........
......
~
......
0.9
.. . . .
.....
68
12."2
39
H.9
27.6
18.7
.. . ..
.
.......
5.1
5.2
.......
15.6
.......
........
30
... t ....
4.8
3.3
1.4
. .....
30.2
15."
28.4
9.7
4.8
4:8
15.9
13.7
4.8
17.2
.....
&.0
14.8
11.8
16.8
12.6
15.8
8.Q
3.4
30.8
4.8
3 :. 9
10
.......
12.45
7.9
. 'r
~
...... .
. .. . , .
.. . ......
54.9
29.4
33'.6
39:7
4.8
4.8
4.8
4.8
11.4
10.1
3.3
18.1
"
8.5
13.3
12.6
13.4
12.3
16.8
.......
6.1
7.9
13.5
12.4
14.4-
2.0
13 . 3
3.8
7.1
2. 5
5.9
58.5
.....
87.S
.. ..
~
11.6
12.2
16.9
3.7
6.9
85.5
.....
4.8
15.5
.... ..
10.5
2.1
12.8
8.7
19.0
2.4
6.7
3.3
7.8
77 . .rid
86.5
56.7d
81.7
14.3
8.1,
3.2
8.2
75.5 d
91.5
2. u
8:.6
6.5
(}l.3
..
10.8
85.9"
176.4
.. Devised by author for use in compuing the value of world Clompetitive crude oi..l.s.
& Part of these coats is included in other itema.
Half thermal and half catalytic
.. Add coat of producing lubrica.ting oUa or W&Ye8.
,
I
871
ECONOMICS OF DESIGN
TABLE
23-5.
STANDARD REALIZATIONS
OF A: FEW CRUDE OILS BASED ON GULF
.
.
Oils
Value of
products,
$ per bbl
Opera.ting
,. cost,lI.
S per hbl
:
API
Name
2.97
3.53
.().585
0.875
4.14'
3.54
0.929 1
0 . 613
3 . 34'"
0.567"
0.832
0.775(1
0.775(1
0.79"
0 .859
32.0
25.8
37.0
38.5
41.8
43.3
43 .9
4.03
3.89(1
4.12"
3.94
. 5.47
11
11
Posted
price of
crude oil,
$ per bbl
1.90
2.55
1. 72
2.56
2.62
2.60
2:90
3.04
2.90
4;50
Delivery
of crude Net profit;
oil to
or 1088,
$ per bbl
Gulf/
S per bbI
0 .05 4
0 .24
1.91'
0.44
..... O.13IJ
-0.421
.0.10 4
~.34
0.05
-1.74
0.16
0 . 10d
0.24
0:06
0.22
0.0l
,
...
a Cost of manufacturing waxes and lubricating oils already deducted from the value
of the product. "The low of Gulf Cargo prices for 90-0ct1Lne gasoline, 48-52 D.l.
:diesel fuel, and conventional products of Table 23-4.
" See Table 23-4 for product yields.
-41 Gathering, pipeline, ocea.n transport, import duty, etc., to the Gulf or Caribbean
area as applicable. USMC tanker rates used, although actual rates were higher
during August 1956 by plus 25 to plus 45 per cent and although breakeven rates ate
lWaUS 25 to minus 40 per cent.
If Sold in Caribbea,n ra.ther than at U.S. Gulf ports, but import duty (as crude oil)
to U.S, included.
Profitable when purchased as pa.rt of a mIxture of 33 or 36 API oils.
. 1 Product prices, operating costs, and delivery costs (or New York harbol".
MISCELLANEOUS OPERATING COSTS A~D FACTORS
* ,Can be estimated for other years by ~he operating cost indQx of Table 23-1:
.,
'.,
872
(Continued)
(19~1).
t Large credit for other products can be subtracted from this cost .
. t 5,000 bpd and larger. '
Approximate royalties:
Alkylation ...................... " 20 cents per bbl aIkylate (1956)
Benzene recovery from refor~ate ... 1 cent per, gal (1955)
Cracking, catalytic .......... ',' .. " 5 cents per bbl charge (1955)
Cracking, thermal ................. , 3 cents per bbl charge (1955)
Reforming, catalytic .............. , 5--7 cents per bbl charge (1956)
Polymerization, catalytic ........... 0.5 cent per gal product (1955)
Sweetening, tannin solutizer ........ 0.3-0.5 cent per bbl product (1947)
Paid-up royalty is often three years' worth of unit royalty.
Treating light oils:
Acid treating, complete., ..........
Sweetening, doctor ............. , ..
Sweetening, copper ... , .......... ,'
Clay, vapor-phase .. ,'......... , .
(1940)
(1951) ,
(1950)
(1940)
873
ECONOMICS OF DESIGN
MISCELLANEOUS OPERATING COSTS AND FACTORS
(Ctmtin1Ud)
:j l
I
'
"
"
:;
For regular chemicals see Chem. Eng. News Quarterly Report on Current Prius.
t 500-800 bbl per gal.
The costs for processing heavy oils such as neutral oils and cylinder
stock are even less consistent. The great variation in' these costs is due to
the inherent differences in lubricating-oil stocks and the variety of treating and dewaxing operations that may be used.
Heavy oils:
:,
',"
Percolation (1932):
7.2-36.2 cents per bbl
15.4--48 cents per bbl
19.4-36.4 cents per bbl
44-90 cents per bbl (1953)
27-75 cents per bbl of stock
52-100 cents per bbl charge (1953)
10 cents per bbf plus clay (1943)
Clay:
Steaming, discharge, ,a nd loading. . ..
Burning} wedge-type burner ........
Burning, rotary-type burn~. . . . . . ..
'Loss during burning .............. ,
. :
j' '
': I
~74
(Continued)
Dew-axing:
Pressing and sweating .... '.' ..... ,.
Sweating ...... , ., ......... , ... '"
Barreling and molding wax ...... , .,
Centrifuging ....... , . , , .......... ,
Refrigeration" . . . . . . . . . . . . . . . . . . ..
Propane dewaxing and deresining ...
MEK dewaxing ...... , .. , ...... '"
i.
I
,
875
ECONOMICS OF DESIGN
MISCELLANEOUS OPERATING COSTS AND FACTORS
(Continued)
Power:
Gas engine (20 cents per Mef) ......
Electric motors (1 cent per kw). . . ..
Diesel engine (14 cents per gal). . . ..
Gasoline engine (20 cents per gal) ...
Steam pumps, sma11 (W-cent gas) .. ,
Steam pumps, small ($2.25 fuel oil) ..
,A mmonia refrigeration, 150-ton plant
Ammonia. refrigera.tion, 1,0000ton
plant ........... . ...... . ..... ,.
Electric power .. . ................
Electrical requirements:
Alkylation (HF) ....... , ... . ...... .
Coking, delayed .. . , ...............
Cracking, catalytic . . .. . ...........
Cracking, thermal (also reforming) ..
Distil!ation, 2-stage .. . ...... . ..... ,
. Dewaxing, solvent .......... . ..... ,
Dewn.xing, centrifuging ........... ,
Deaspho.lting, propane. . . . . . . . . . . ..
Illumina.tion, buildings ..... . .... .' "
TIlumination, process ... . ...... .- ...
Illumination, yard .... . ... . . . . . ....
Polymer gasoline .. . .... . ... . .... "
Refinery.; topping ......... '. ' ......
876
(Continued)
.LOW COLD
I TrplT
~
,-..
GUlf JoAST
..---;
J
2 OT.I-API
~~ l
00
~
~o
00
...
~
-V
W.GUARA
0
.-TII-
,-...
00
LUBE CRUCES~
..
~o
IP~
10
,.,. ~
MIODLE EA:ir
r3.e CT. / API
~~ WESTT2AS
3.3& CT./OAPI
~
~~N[ZUELA
ANxto
.
.- 1
.3.38 CT./-API
~.
o PEOE,RNAL,S
~CAN
1.$0
10
20
30
API GRAV1TY 0' CRUDE OIL
eo
FIG. 23-2. Crude-oil value VB. gravity for various types of erude oils, based on Gulf
Coast cargo produ~t prices of June 23, 1954. (Oil Gaa J.) -
ECONOMICS OF DESIGN
877
Table 23-5 shows the realizations of a. few important and widely different (see Table 23-4) crude oils. In marketing crude oils, the price
is usually increased by 2 cents for an increase of 1.0 in the API gravity,
but the true or correct difierential in price based on product value during
recent years should have been 3 to 4 cents per degree API (see Fig.
23-2). Ii The proper differential per degree API is a function primarily
of the relative prices of gasoline and residual fuel oil, and it may be.
esthnated from Eq. (23-1) in which G, D, and B are the prices respectively
of gasoline, distillate, and Bunker C fuel oil, a.nd C is the opera.ting cost,
all on a. barrel basis. 6
!
~1
Different ~ -
2G + D - 3B - 3C
150
,;
(23-1)
.'
:"
"
,
'.
.. '
878
200
,l
150
,,18
~
20
E::
15
/
'/.
/
..V
10
,."
5
4
.~
./
/
b
)/
~/
~ 1.0
i;' ..... '" ~/
, , ./ ,
f-- 15"
/' ././
0.8 14/ 1/
.....
0.6 r-lY'
,/1' 7"
6/{& .
0.5
4/
0.4
0.3
O.~
k"
'. 0.15 ,,'
"
400 600
......
.....
~I'
. ;;- ~/
./
"' / /
./
II'"
~f-
10
/'
". ,,'
,....
V4 .3
/..,
./
/.~
/'
'./7
../
i"l
./
' / 1./"
/5
/
.r
/'
f-
./ ,/. ~; -
~/V
io'i""
'1
l~
,/~
L ZL It'
/ / ,,' /-1
......
~/ V
""
~
..J
//
.I. ~
fI'
,,"
1"91I ~ .....
:r
./
;I'
././
.11j ~ ~~ ....
/ ...- A.'~/s.o
/"7.,6
//
~ .....
/6/
/
r :/ 15~ r.-
I"
//
~~
:.A "/2
1.5
)17
.I
,,/
/7
/ .
, 13814
./
/
"
18'
~
0)
I&}~
'Ci 30
.~
L
./
40
~.
I'
60
50
~
~
-.;:;:
100
80
,.l
...-
./
..
""10"
/ 'r'/
7' 'v.; V V
'" ~~ lY
~
~/
. .
1000
2000
4000
40,000
100.000
.f
Capocity) i?PI/doy
FIG. 23-3~ Approximate construction costs of refineries and procesa units' (19S6).
' T~e 'Nelson Index for 1956 is 195.3 (based on 1946).
Pr0"Ce88 unit8:
15. Solvent dewaxing
1. Vacuum 1ia.shing
*17. Benzene and toluene recovery
2. Topping Bnd atmospheric ,distillaOarge plants)
tion
18. Lubricating-oil manufacture (complete)
. '
.
3. Desulfunzation of gasoline (cata.lytic)
Complete refi:neries:
.
4. Vacuum distilla.tion (lubes)
9. Topping and asphalt manufacture
5. Cracking (thermal)
11. Topping, thermal cracking, cata6. Coking (Delayed or Fluid)
lytic reforming, and polymeriza..7. Sol~~nt extracti.<;>n-9r deasphalting
tion
8. Reforming (P1a.tinum .catalyst)
12. Topping, catalytic cracking, cata10. Ca.ta1ytjc craclciJlg-iD..Cluding feed
lytic reforming, and polymerizaprepa.r~tiQn, gas recovery J and
tion
pblymerization .
16. Complete for all products
13. Polymerization (catalytic)
Per barrel finished product ra.ther
14. .Alkylation
than feed~
r'l
ECONOMICS OF DESIGN
879
(23-2)
Thus, some of the lines of Fig. 23-3 consist actually of two lines each
having expqnents near 0.6, but the line for large plants built by major
refiners tends to lie above the li~e for small plants built by small operators.
The approximate costs of other types of plants or equipments are
indicated in Table 23-6. Such general costs as these must be used with
extreme care. The higher of the two costs is due mainly to the small
size of the plant rather than to other factors. In prosperous tim"es the
costs ~ill all be hlgher, and during times of business depression U sacrifice"
prices may prevail.
Financial Charges. At one time the concept of depreciation was a
simple one; it referred to funds laid aside for replacement of equipment
because in time it would be worn out. More recently it has come to
mean little more than a percentage of total investment that can by
Federal tax regulations l l be withheld each year from income. Taxation
and inflation are requiring a completely new concept of financial charges.
Financial charges (as percentage of investment) may be considered
under four general classifications: .
1. Interest on investment or borrowingst or dividends pa.id to stockholders.
2. Depreciation, maintenance, and equipment insura.nce. Depreciation in the sense
of wearing out is of little significance, because a. refinery t.ha.t is kept in proper
working order by maintenance or replacement of dangerous equipment is sub-.
stant.ially as useful aft.er 10 to 15 years a9 when new. Thus mai.n tenance and
insurance against disaster- are the real 'costs of preserving an operable plant.
3. Retirement or obsolescence, and inflation. Replacement of a plant or the complete retirement of a.n lnvestment at t.he present rates of inflat.ion is never necessary
unless the process equipment becomes totally obsolete or the plant environment
becomes unsntisIactory. However, obsolescence is not usually a large cost because
most of the advances o( the last 30 years ha.ve requjred additions to the refinery
rather t.han replacement, and almost all discarded equipment can be utilized for
new services. To further confuse the situation, inflation during the decade 1946.1956 has averaged 9 per cent per year, so that properly maintained equipment pur':'
chased in 1946 would be worth more during 1956 than its original purchase price.
Thus, a proper fina:ncial charge ~rl(ier t.hese conditions would be one that cares for additions rather than the retirement'of invest-ment. Only jf inflation should halt,'
would retirement or repayment of debt be necessary.
4. Taxes and profits. Corporat.e taxes in t-he United Sta.tes during recent years have
amount-ed to about 40 per cent of the gross profit before taxes. Thus, after hayjng
laid aside fund::! for about 9. to 14 per cent of investment (depcndip.g on the degree
11 Income Tax Depreciation and Obsolescence . . . , Bur. Internal Revenue Bull. F t
January, 1942; a.lso see Nelson, W. L., OZ Gas J. t Apr. 23, 1956, p. 141.
880
of inflation) for items 1 to 3, a.bove, a. gross profit befor~ taxeS of 5 to,,10-per cent
must be earned to show a. real profit of 3 to 6 per cent on investment.
a
11
I
1:
t
(
TABLE
23-6.
TYPe of plant
Acid-treating equipment ..................
Acid-treating and P .D. rerun .............
Ammonia plants, anhydrou8 ...............
Ammonia plants. iDe!. HNO. or urea ....
Asphalt, loa.ding and storage ...............
Asphalt proeeeaing ....................
Buta.diene manufacture ...................
Carbon bla.ck ........... : .............
Clay burning ..........................
Clay trea.tiDI (percola.tion) .............
Cla.y treating (contact) ....... ~ ............
Coal (hydrogenation) .....................
Coal (qntbetlc gasoline) ..........
Copper sweetening, liquid .......... , .....
CumeDe manufacture ................... ,.
Dehydration of gues .....................
Deaa.lting of crude oil ...... ',' ..........
Deaulfuruation of gases ....................
Deaulfurisanon of pa oil ...... "...........
Dewuing (filter press) .......... ; .........
Dry-fce ma.nufaeture ......................
Ethylene wuf&eture .....................
Ext.ractiv8 distillation ......................
Fiacher-Trop8ch for gasoline .. , ..........
Oaeoline (natural) pla.ntae ................
GB.60line a.nd kerosene treating ............
Gray vapol'-pha.se treating .................
lIyclrogen Enanufaoture ..............
Hydrogen eul.fide remova.l ..............
Hypersorption ............. . ............
Inhibitor injection .....................
L.P.O. bottling ....................
L.P.G. reeovery .........................
Lube oil (aolution rerun) .. ... ..............
O.r.ygen separation .................... ;
Polymerisation (thermal) .................
Shale oil (foreign) ......................
Sulfur or sulfuric a.eid b . . . . . . . . . . . ; . . . . . . . .
Synthetic rubber ....................... .
Tetraethyllead blending ..................
Ca.paeity
....................
1-
881
ECONOMICS OF DESIGN
Fra.nklin, W. B., Storage of Light Ends, Rtf. Nat. Gll8O. MfT., June, 1937, p. 277. '
13 Cha.mberlain, N. F., Ref. Nat. Gaso. Mfr., Deoember, 1937, p. 571. .
14 Niss9.:D, A. H., J. Inst. Pet. Tech., M, 69 (1938).
11 Nelson, W. L., Oil Gas J., Apr. 6, 1939, p. 55.
IS Colquette and Peters, To Coke or Not to Coke . . . , Oil Gcu J., Apr. 14, 1952,
p. 156.
17 Gertz, M. H., Pet. Processing, January, 1948, p. 41.
18 Stewart, L. D., Oil G~ J., July 13, 1950, p~ 70.
19 Nelson, W. L., Oil Ga8 J., Dec. 17, 1956, p. 146.
U
882
170
150
-.;;;;.
""
~ 120
80
90
120
In selecting
exchangers an important consideration
the most
economical H approach" or difference in temperature between the incoming large medium and the outgoing small medium. The maximum recovery of heat occurs if these two strealIlB are at the same temperature, but in
temperature !!lUst
practical' heat-exchange equipment a difference
exist.
For liquid-to liquid'exchangers, the relationship among the value of heat,
~ost of surface, magnitude of the heat-transfer rate, and the several'other
variables that govern the most ~conomicaI approach is extremely complicated-but for a particular refinery situation all the variables have fixed
values and the relationship reasonably simple. ]for the following valu;;:~
883
ECONOMICS OF DESIGN
200F
$2.66 per sq It"
6 per ee:pt
$160 per year
17 cents"
25
.. Corresponding 1956 costs are, $7.50 per sq ft surfacej $450 upkeep; and 48 cents
per MM Btu.
In this figure, the most economical approach is given in degree~ Fahrenheit,and'the factor labeled R is the ratio of the weight,of the sniallerof the
two fluids to the weight of the larger quantity fluid. Similar studies hav~
been made for water coolers21 and condensers. 22
ISO
140
130
u.;. 120
t:J)
~ 110
or:u 100
,
15
90
80
Q..
. 70
':~
60
c:
8, 50
uJ
"t;
40
- ~
30
.\
\\
\\
~ ~\ \.
\\\ ~
~\ \ ~
\\ ~' r\. "\ \\ "-
.........
:-........
"
,
T
i-....
r': ~
20
- ---
r- -...
,:
o.
.;- '
"' ..
=7
~
(Ref. Nat.
Gaso. Mfr.)
,.
"
884
Pipes till
I,.j
(, I
" I
:,',
.~
."
:~
,-
Sa.ving, dollars
per year
'f
66.5
. , 49.3
39.9
41.6
20,600
39,400
37,600'
885
ECONOMICS OF DESIGN
0.6-4
~
p~/~I ~onomic irm{/6
O.SO
~ 056
--
c:
~ Q52
0.48
-' , 0.44
840000
..Q
t5 Q40
",
~ Q36
~. 0.32
--
forflJ.4-
--
~~
---
(J
Costof ~
~20.000 -conv4'd/,n "-
sectIon
rl')Sror~ ~
~/J7~
alO
1I
/'
+-
ro.r .
"'--h.L
t-
~ ....
aZ4
\~ ,in1uf,/
"-
~ D.l8
_\
]
o
01)
~
o
-,-
10
15
20 25 30 35
of nue Gas, Feet per Se>eond
Most economical fiu&-gas
~elociiy
0. I 60
100
200
300
400
fDO
Difference in Stack and Charge Temperature
FIG. 23-7.
velocity in convection section of pipestill
(if such a velocity is geometrically
feasible.)
23-7. Loss
Pressure,
psi
BY OPERATION AT
Pentane . Grade of
pluB,
gasoline
per cent
99
PER CENT
REcOVEllY OF PEN'l'A.N'I
GasoliDe
Most
pneeJ
economiea.l
recovery,
cents
per gal
per cent
5()l>
50
7
3
50
50
50
'3
5tJ
9
3
3
9
400
400
400
22-70
30-70
30-70
14-55
3
9
14-55
3(}--70
14-55
30-70
3(}--70
4
2
94.25
89.8
4
4
94
92
4
4
96.2
97.4
96.4
97.5
4.
4.
98.9
1. 281~
0.821
0.577
0.455
0.286
0.227
0.117
0 .068
Nil
Although based on 1936 prices and conditions) the conclusions will be the atUne ~or
1957.
lJ Refinery conditions, oil recirculation cost or 0.1 cent per ga.L
fa
ThusJ designers have tended to build plants that would recover 99 per cent
of the pentane contained in the gas. This practice, however, is not usu...
ally economical, because the cost of operation mounts rapidly as more than
85 per cent of the pentane is recovered, so that in general it may cost twice
as much to recover 99 per cent as to recover 85 per cent of the pentane.
886
The vari~bles-8uch -as, co~t ~f oil recirculatipn, vahJ.e of the gas6li~e prod...
uct, and cost of stabilizing the gasoline are related u such a way t~t'the
loss'involved. in :recovering ~9 per cent of the pep-tane is s'omewhat 'as
shp':Vn in Tab~e 23-7. Note that the most ecol!omical recovery is also
given: in the table. In c9mputing Table 23~7, the cost of oil circulation
was used S.B' 0.05 cents per gal oil, and
cost of stabIlization 0.13 cents
per gal.
, The same basic economic situation ~ arise with ~espect to other key
components, .such as butane or propane, as wel,l as pentane.
Octane Improvem.ent. The extremely complicated problem of 'octane
number improvement is a constantly ch~nging' situation, and it. is ~ti'20
~ mately related to the particular
environment ;of each refhiery operation. However, the, situation
during 1956 _ was somewhat
indicated u in Fig. 23-8. The
base scale shows the octane number
of the original material or gasoline
upool" of the refinery; -and the
ordinate (cents per R.o.n:-'per bbl)
defined as .the cost of the
improvement divided by u the volume of improved-quality gasoline
times the difference
the octane
numberS of the, original and the
improved material. "24 On such
a basis,. cracking, pcilymerizationt
Research' oclOPe mmber of refinery
and alkylation ~re not solely
paoI of gosoIine
FIG. 23-8. illustration of approximate improvement, because
cost of octa:ne improvement by var- they ,produce gasoI,ine from non~
ious methods. (l) Catalytic reforming
(mild); (2) alkylation; (3) po}ymeriza- gasoline, feedstocks, but they can
tion; (p) market values {January, 1956) be compare~ on a U cents per R.o.n.
of various-octane gasolines; (4) ca talytio per bbl H basis by assuming a value
reforming, aromatics extraatioJ,1,. and
for t~e, feedstock. (In Fig. 23-8,
reforming of faffinate---or -catalytic
reforming plUs thermal reforming plus the value of feed for polYJ?1erizapolymerization or isomerizationj (5) tion and alkylation was assumed
severe catalytic rerorming~
to .be: 2 ce~t8, per_J~,allon above a
breakeven. v~lu.e.) The dashed line of Fig. 23-8 indicates the
values placed on octane number by the Gult Coast market for the
date of January, 1956. At Hpool" octane :r;tumbers below about 95 it
not profitable to- raise the octane number by isomerization or the
U Nelson, W. L., Ref. Nat. GlUO. Mfr., MaYl 1936, p. 167.
as
14
,887
C!l
a::
II''/
so
o
x
In
'
/. ri\
L~
/ / /V
j ' / '/
/~
(3)
30
'0
. .J
...J
1.
:::I
~20
!J /
~~ /
10
~
<
:: 10
JO
~~ /
W/
:::)
/
~
'/
:20
30
I :
40
~o
eo
70,
ao
eo
100
FIG. 23-9. Most, economical tube lengths for Borne common a.rrangements of pipestills.
I"
gal for the 88 R.o.n. pool). At these high levels of octane number and
with 2 or more ml of TEL already present, the use of additional TEL is
not usually profitable.
Dimensions of Pipestills. Immature designers are usually confused in
deciding what should be the dimensions of a pipestill, whereas experienced
designers have become accustomed to using certain arrangements that in
some instances may be needlessly expensive. The economic relationship
among the costs of tubes, bends, tube supports, roof, walls, etc., is exceedingly complicated. Nevertheless, cost equations can be derived for any
conventional type of still such as down-convection, A-frame, etc., stills.
Figure 23-9 shows the most economical tube length 21i ,28 VS. the total cost
I.
U
Nelson, W. L., Oil GaB J., May 11, 1939, p. 63; and June 1, 1939, p. 34Nelson, W. L., Oil Gaa J., Nov. '2, 1946, p. 91.
,t ~
of pipestiHs. In general, the high cost of return bends as against the cost
of tubing, supports, walls1etc., callsfo:r-longer tubes than have commonly
been used. This tendency is becom.i.h:g, evident in stills designed during
the last few years.
. The types of stills shown Fig. 23-9 and the major dimensions of the.
stills are
L Down convection aa in Fig. 18-1e but with two rows of tubes on the roof, and with
tubes on the floor. (Applies only to large still.s.)
2. Down convection with only roof tubes and for smaller stills.
3. Down convection as in Fig. IS-Ie.
4. Straight-up (Fig. IS-let) with haJ.fthe tubes the convection section, with two rows
of tubes on each wall (large stills), and with a width that is one-fourth the length.
5. Straight-up (Fig. 18-1d) with one row of ra.diant wall tubes and a width of 10 centerto-center tube spacings. Two-thirds of the tubes are in the convection section.
6. Overhead convection with two rows of radia.nt tubes.
"0
. I
CHAPTER
24
24-1.
Material
Per cent
API
LOssli ..............
Ga.soline ............
0.5
31.0
'10.0
26.0
60.2
43.0
34.9
Kerosene ...........
Ga.a oil ......... '....
Reduced crude ......,
Crude ......... . ....
II
32.5
100.0
Notes
...
890
..
7:B.RI
1000
@ 760mm.-
V .
900
400
350
~
~ BOO
o
,e 700
\,
'b
"'\
- 250 .. 500
Q'\
..
Q)
L-
Vol
LQ)
"200 ~ 400
o
~ 150 O-Joo
>
100
50
~,
",
200
100
~V
............
\.
I'
10
20
.r
/~
",
~/
./
/'"
voporlzaHon -
'30
'-......
60
~
50'S;
~
40~
~
~ ~mid percenl
~
"'-
.- 80
70
;,/".rlash
K ,,'"
l300 ~600
o
I'-.
':--..
30
"
<i.
20
r,scoffy YIeld
40 50 60 70
Percentage Oistilled
80
90
100
3.
4.
5.
6.
7.
8.
891:
9. Strippers are designed next because the steam further reduces the temperatures of
the side-draw products to the exchangers, and the steam becomes B. part of the
overhead product.
10. Such exchangers as are needed for heating the crude oil to a proper salt-settling
temperature are designed. No salt settler is shown in Fig. 24-~, but one should, be
mgtalled after the crude oil attains 260F in the gasoline condensers, or if the crude
oil is corrosive or dirty the settling might be done after a te~perature of 200~
is attained.
11. Design hea.t-exchange system by an economic study of each exchanger (Fig. 23-5),
Compute the temperature of the stock as it arrives a.t the pipestill.
'
12. Design the pipestiU.
13. ' Design the condensers, coolers, stripper, etc.
14. Estimate stealll, water, and power requirements.
Material
Per
cent
API
Lb
per
gal
Gal
per
hr
Lb
per
hr
50 per Molal"
cent average Molecboiling boiling
ular
point,
point, weightll
~
:Loss ........ , , .
0.5
Gasoline ......... 31.0
Kerosene., ...... 10.0
Gas oil .......... 26.0
Reduced crude ... 32.5
.Crude ........... 100.0
Q
II
......
60.2
43.0
34.9
22,5
38.6
0.U9t
6.14
6 .75
7.08
7.65
6.93
3504
5,425 . 33,300
1,750 11,800
4,550 32.250
5,690 43,550
17,500 121.250
85
0]'
. ..
. ..
45
258
218
101
460
450
635
615
185
270
892
FRACTIONATOll SYSnM
24-3.
STEAM
roll
Ma.terial
Lb steam
per gal
Kerosene ............
Gas oil ..............
Reduced crude .......
Total ..............
0.3
0.5
0.5
...
STRIPPING
Gal pe~
Lb steam
hr of
perhr
material
1,750
4,550
5,690
. ....
'"
"
525
2,275
,,845
5,64..5
"
The number of plates can be estimated from Table 16-13. The following Dumber of plates w~n be used:
TI: 1
TYPIC~
.893
DESIGN CALCULATION
No. of
plates
Gasoline to kerosene. . . . . . . . . . . . . . . . . . .. 6
Kerosene to gas oil. . . . . . . . . . . . . . . . . . . .. 5
Gas oil to vaporizer. . . . . . . . . . . . . . . . . . .. 3
No. of pla.tes above vaporizer . . .. . . . . . . .. 14
Stripping plates. . . . . . . . . . . . . . . . . . . . . . .. 4
Total no. of plates. . . . . . . . . . . . . . . . . . .. 18
The pressure at the top of the topping tower is seldom more than 4 psig.
The pressure drop per plate is discussed on page 448. The pressuresin the
JIOF
41b./sq. In.
t----f
5 Ib./sq./n.- r:~=~~
5.7lb./~q.ln;-- !-='-~_-r
650F.\.)---~
6.11b sq.ln.
I--~
~-,-",el.47 gal/h.
s+ecrm
'-----Fuel oil
FIG. 24-2. Simple diagrlUll of topping plJ!,nt.
Position
At top plate .............. .
At kerosene plate ......... .
At gas oil pla.te .......... ..
At vaporizer .............. .
5,645
5
5.7
6.1
5,120
2,845
2,845
894
+ 1~.17
X 760 = 1,075 mm
.
33300
Moles of gasolme (Table 24-2): iOl = 330.0
Moles of kerosene:
l~~O
3~:go
63.8
119.5
513.3
= 158.0
671.3
=
OF
Top tern perat ure . ...... , .... '.'
Kerosene draw plate ...... .. ...
Gas-oil draw pla.te .............
Bottoms product .... . .........
31~
4]0
546
630
Latent heat ..
120
108
95
Estimated from Fig. 5-7. La.tent hea.t can be computed from Figs. 5-6 and 5-6.
& Assumed temperature.
The temperature is checked 011 p. 89.6.
895
the reduced crude (see Fig. 7-9) will have a 0 to lO per cent boiling range
of about 230 to 620F, and after stripping the average boiling point
of the 0 to 10 per cent range will be about 530F. Equation (4-6a)J
page- 131, indicates an approximate open-cup flash point of
Flash- point
= 0.64
X 530 -
Joo = 240F
a7'
+ 0.65 BS (T -
Ts)
For an -estimated tower diameter D of about 9 It, ari air temperat~re 7'a of
40F, and a. steam: temperature Ts of 366F,
aT
9
+ 35 43,550
-(650 = 3.6 + 4.4 + 12.1 = 20.1F
1.2 X 3
40)
2,845
+ 0.65 4~J550
(650 -
366)
Top
PLATE
Temperature :datum, vaporizer temperature or 650F (see Figs. 5-1 a.nd 5-2)
Btu per hr
Cooling gasOline (vapor)".. , .. . ...... 33,300(650 - 310)0.57 =
Cooling kerosene (vapor).... . . . . . . .. 11,800(650 - 410)0.58 =
Cooling gas oil (vapor) .. , ........ : .. 32,250(650 - 546)0.61 =
Cooling reduced crude (liq) ... -.... .. 43,550(650 - 630)0.76 =
Cooling steam *. . . . . . . . . . . . . . . . . . .. 5,645(366 - 310)0.5 Total sensible heat. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
Condense kerosene ..... -. ........ " 11,800 X 108 = I J 275,000
Condense'gas oil. ... -' ............. 32,250 X 95 = 3,065,000
4,340,000
-6,450,000
1,640,000
2,050,000
665,000
158,000
10,963,000
4,340,000
15,303,000
* Actually, these hea.ts have in part been accounted for in the computation of the
bottoms temperature, but most textbooks and designers include them as a factor of
B8.fety.
~ld
reflux:
15,303,000
(294 - 50)
= 62700 Ib per hr
I
..
"
896
PETROLEUM
REF~RY ENG~EEBING
.
62 700
33 300
Moles lDternal reflux ,and product: '
101'
,..
5,645
Moles steam:
313
18=
Total moles:
Partial pressure:
950
1,263
950 (760
1,263
+ 4 14.7
X 7~0)
727 mm
1'he 100 per cent or dew point on the flash-vaporization curve of the gasoline is approximately 324F. When corrected to 727 mm (Fig. 5-27)
the temperature is about 318F. However, the computed top temPerature is usually about 3 per cent too high (page 471), resulting in
an actual top temperature of about 0.97 X 318 = 309F. This' checks
With the assumed temperature of 310F. The temperature in the liquid
of the plate is, theoretically, slightly higher because a larger amount of
internal reflux is present, but in practice it is lower because of the large
amount of cold reflux.
Diameter of Tower. The allowable mass velocity of the vapors at
the top of the tower can be computed from Eq. (16-8). The constant
l( can be obtained from Fig. 16-13. At a tray spacing of 22 in. ,and when
llsing conventional bubble plates (curve 3), the value of K is 730 or
higher.
The density PL of the ga,soline at 310F can be obtained from Fig. 5-14:
Sp gr at 6OF
0.738
and
at 310F = 0.615
PL = 0.615 X 62.4 = 38.4 lb per Cll ft
:=0:
Lb
~ 1 fi
15,303,000
263
Internru.
re ux......... 120 X 101 "'" 1,
Ts
127,700
330
33,300
313
6,645
166,645 '
840,000 = O.I981b per cu ft
.-
897
HEAT-EXCHANGE SYSTEM
Th~
The tempe!atures in these exchangers will be developed during the COIDput~tions and are shown in Fig. 24-3.
Gasoline Condensing Exchanger. The pounds of reflux and gasoli,ne
are 33,300 plus 62,700 or 96)000 lb, and 5,645 Ib of steam must also be
handled. Using an approach of 50F on the hot end of the exchanger,
the heat absorbed by the crude oil between 90 and , 260F (Fig. 5-3) is:
121,250(130 . .,. . 42) = 10,680,000 Btu per hr
This amount of heat will condense about 60 per cent of the gasoline and
reflux, and require an outlet temperature, for the gasoline, of about 245F.
Cool 60 per cent of vapor 8Jld the condensate from it:
0.6 X 96,000(310 _ 2(5) (0.64
~ 0049)" = 2,115,000
Cool vapor that does not condense: 0.4 X 96,000(310 - 245)0.48 = 1,013,000.
Cool steam:
5,645(310 - 245)0.5 =
155,000
Condense 60 per cent of vapor:
0.6 X 96,000 X 128t = 7,370,000
10,653,000'
:41 Average sped fic heat of vapor and liquid.
t Higher boiling than the entire gasoline.
898
Transfer Coefficients. The crude oil will pass through the tubes, and a mass velocity of 210 Ib per sq ft-sec (about 4.5 ft per sec) will be possible
because of the pressure that is available.
The average temperature of the crude -oil will be about 175F and its
viscosity at this temperature is about 2.4 (Fig. 4-43). Film-transfer
r~teJor crude oil according to Fig. 17-11 is about 160.
6io
192
RedA:ed-crude
exchanger
418
330
20-310
H=535
e=76
520
199
Gos-oil
exchanger
321
280
3250
H= 52.4
(}::: 89
310 50
260
245
Gosoline
condenser'
155
90
FIG.
The gasoline, reflux, and steam will be cooled on the outside of the
tubes, and the condensing coefficient will be about 140 (Table 17-7).
The approximate fouling conditions are as follows:
Crude in tubes (wet) ............ 4.0 (Fig. 17-8)
Gasoline in shell ............. _.. 1.0 (Fig. 17-9)
Total fouling factor. . . . . . . .. 5.0
~60
1
+ 7140
+ 0.005
Su rf ace
10,680,000 2 110
f
93 X 54.4 =,
sq t
899
Approx. temp
after stripper, etc.
Lb
Gas oil .. , , , . , , . .
Crude. ' ... , . .. . .
32) 250
620
121,250
250
Oil
* Fig. 4-43.
t Figs. 17-11 and 17-12.
t Low velocity because no
0.6
,1.0
Side
Shell
Tube
Film
Mas.s
velocity , ratet
50~
160
Fouling
factors
120
210
pump is used.
}l20
'
5,000,000
1 072
ft
,Surface = 89 + 52.4 =,
sq
Bottoms Exchanger
Oil
Lb
43,550
121,250
Approx.
temp
610
310
2
4
!
f
900
Oil
v
470
364
Vis-
Side
cosity
1.5
0.55
Shell
Tube
Mass
velocity
Film
ra.te
.Fouling
factors
100
130
135
235
If =
+ ~35 + 0.007 =
7185
53.5
If the reduced crude oil were not handled 'by a pump, the over-all rate
would be only about 40~
,
, Surf
8,180,000
~ 015'
f
ace = 76 X 53.5 = ~,
sq t
be
W = lb water
Gal water
'=
2,560,000 Btu
85,500
85500
Fluid
temp
ViBeosity
206
2.8
...
. ..
Side
Shell
Tube
Mass
velocity
Film
rate
48
77
260
1,100
Fouling
factor
3
3t
,i
I
901
H = Y17
'
!:{
"
j
!
2,560,000
630
ft
50.3 X 81 =
sq
PIPESTILL HEATER
oil.
Btu per hr
Heat gas .......................... '. 350(650 - 410)0.655* =
Heat and vaporize gasoline...... ,,' .. .- ... 33,300(498 - 238)""
Heat and vaporize kerosene ........ , . . .. 11,800(481 - 228) =
Heat and vaporize gas oil ... , ........... 32,250(472 -:- 220) =
Hea.t reduced crude oil ................ , 43,550(376 - 210) =
Pipestil~ duty
=
55,000
8,650,000
2,985,000
8,130,000
7,220,000
27,040,000
902
REFIN:E!RY ENGINEERING
heating operation is
a difficult one, and .....
the radiant section can
designed for a radiant-absorption
of about 35,000 Btu
sq ft of projected area per hr (Table 18-5).
which applies to
use of two
of tubes in
According to Fig.
the radiant section
a center-to-center spacing of
tubes of 2.0, the
percentage of the beat liberation that is absorbed in.
radiant section
with 40 per
excess air is about 44 per cent. Should other tube
arrangements
used, Eq. (18-6), page
can be employed;
'if the
arrangement of the
not normal, the Lobo-Evans method
Example 18..2 (page 602) can be used.
The
through
walls,
the still amount to about 3
cent from the radiant section and 2
cent
the convection section.
The efficiency of the still is 100 - 18 - 5 = 77 per cent.
The
balance of the furnace is about as fonows:
v ..... v'U
quantity
Heat input 27,040,000 + 0.77 .......... .
Wall losses. . . . . . . . . . . . . . . . . . . . . . . . . . '.
Stack 10BB
Ra.diBnt absorption ................... .
Convection absorption (by
........ .
Per cent of
net H.V.
Hea.t,
Btu per hr
100
35,150,000
1,760,000
6,320,000
15,450,000
11,620,000
5
18
44
33
flue gas that enters the convection section still contains 100 -- 44
- 3, or 53 per
of the
heating value 'of the fuel. Figure
shows
that the temperature of the gas at the bridge wall will be approximately
is recorded in plant operation is
1800F. The furnace temperature
lower than this, but it usually measured at another point.
Larger temp cliff. = 1800 -- 548 =
Smaller temp cliff. = 700 - 410 = 290
--
290 = 667F
In 290
The convection section win be
for an average flue-gas velocity
of 8 ft per sec. With tubing tha.t ~.as an outside diameter of 6 in. and
903
with an average flue-gas temperature of about 1250F, the over-all convection coefficient is about 5.9 (Table 18-6).
.
ConvectIOn surface
Radiant Section.
.
RadIant surface
11 620000
.
5.9
X 667 = 2,955 sq It outsIde surface
15450000
35000
.
441 sq ft projected area
35i~5~~OO
=
,
1975 lb per hr
. 1975
7.65 = 258 gal per hr
Two burners could be uSed, but six small ones would be more satisfactory.
Steam for a.tomizing (page 426),
1,975 X 0.3
= 593 lb per hr
WATER REQUIRED'
The several products leave the coolers at almost the same temperature
as the crude oil enters the plant, and hence the heat tha.t must be removed
by cooling water is almost equal to the heat added to the oil in the pipe-
~ater. = (1;:,~4~~:'33 =
This is a maximum figure because some of ,the heat is lost through the
insulation of the equipment.
STEAM REQUIRED
Reciprocating steam pumps would be lliied for the charge stock and the
reduced crude oil. The steam required for these pumps would be guaranteed by the pump manufacturers, but simple approximations can be had,
as follows:
The charge pump will operate at a pressure sufficiently high to fo(ce the
'lil through the exchangers and the pipestill and into the fractionating
~ower. The charge pressure will be about 160 psig. If a conventional
luplex pump is used, its steam consumption according to Eq. (13-11),
904
PETROLEUM
RE~ERY
ENGINEERING
= (0.058 C + l)(P -
zero)
= 2,860 lb per hr
In a similar manner the steam required for the bottoms pump when
pumping at 40 psig is about:
S = (0.058 5:0
+ 1) (40 -
I
!
p)
3,120 lb per hr
5,645
593
9,358
Misc., contingencies, etc .... -. ........ . 3,120
12,4781b per hr
With feedwater at 130F and with saturated 150 psig steam, the boiler
horsepower corresponding to 12,478 lb per hr is abo~t 410.
Summary. The design as herein presented is inadequate in many
respects. However, each design depends greatly upon the particular plant
conditions that are encountered and upon a multitude of practical details.
Refer particularly to Chap. 23 on Economics. These details cannot be
presented without becoming in valved in a hopelessly tedious discussion.
I
APPENDIX A
Material
or API
GO/60 DF
Ethene
Eths.ne
Propl!ne
Propane
i-Butene
n-Butene-l
i-Butane
n-Buta.ne
i-Pentllne
n-PentanB
-10.0
- 0.5
- 9.0
- 8.S
- 8.0
7.5
- 1.0
6.5
- 6.0
5.5
5.0
4.S
- 4.0
- 3.5
- 3.0
2.5
- 2.0
1.5
- 1.0
0.5
0.5
1.0
1.5
2.0
2.5
3.0
Sp gr
Lb/gal
60/60 DF
0.388
0.374
0.522
0.509
0.600
0.601
0.668
0.084
0.625
0.631
1.1646
1.1600
1.1558
1.1507
1.1461
1.1414
1.1368
1.1322
1.1276
1.1229
1.1183
1.1141
1.1098
1.1056
1.1014
1.0971
1.0929
1.0887
1.0845
1.0802
1.0760
1.0720
1.0679
1.0639
1.0599
1.0560
1.0520
2.8149
8.1147
4.3472
4.2390
4.9068
5.0mH
Lb/bbl
l18.23
5.2550
130.82
182.68
178.04
209.87
210.21
196.03
204.27
218.61
220.71
0.6988
0.6602
9.6217
9.5831
9.6446
9.5060
9.4674
9.4289
9.3903
9.3518
9.3123
9.2779
9.2427
9.2075
9.1723
0.1370
9.1018
9;0666
9.0314
407.35
405.73
404.11
402.49
400.87
399.25
397.68
396.01
394.39
392.77
391.15
389.68
388.20
386.72
385.24
383.76
382.28
380.80
379.32
4 . 6887
4.8686
6.2050
8.9962 '377.84
8.962
8.928
8.8.95
8.861
8.828
8.795
8.762
Lb/
ou it
Lb/hr
Bbl/
for 1,000
long ton
bpd
21.10
23.35
32.59
81. 78
37.46
37.52
35.15
36.46
39.02
39.39
4,926
5,451
-1,608
7,418
8,744
8,769
8,205
8,551
9,100
9,196
18.95
17.12
12.27
12.58
10.68
10.66
11.43
10.97
72.71
72.42
72.13
16.973
16,90416.834
16.766
16,698
16,631
16,564
16,498
16.482
16,367
16.902
16,238
16,174
16,111
16,048
15,986
15,924
15,863
15,802
15,742'
5.50
5.62
5.54
5.57
5.59
5.61
5 . 63
5.66
5.68
6.70
71.84
71.55
71.26
70.97
70.68
70.39
70.10
69.82
69.55
69.29
69.02
68.76
68.50
68.28
67.97
67.70
61.44
876.40
67.18
376.00
873.60
372.20
370.79
369 .39
368 .04
66.98
66.68
66.48
66.18
65.93
65.68
15,682
15,623
15.564
16,506
1.6.447
15,390
15,333
005
10.25
10.15
5.73
5.75
5.77
5.79
5 . 81
5 . 84
5.86
5.88
5.91
5.93
5.9S
5.97
6.00
6.02
6.04
6.06
6.09
Bbl/
Cubio
metrio
ton
meters/
long ton
Cubic
meters/
metric
ton
906
Material
or API
60/60oF
Sp gr
60/60 oF
Lb/gal
Lb/bbl
Lb/hr
for 1,000
U/
em
{~
bpd
Bbl/
metric
t.on
Cubic
meters/
long toll
6.4041
6.3030
,6.4265
6 .4490
6.4717
6.4946
6.5176
6.3250
1.01729
1.02085
1.02448
1.02803
1.03160
1.03532
Bbl/
lona ton
Cubic
metera/
metric
ton
.
3.5
4 .0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
10 .5
11 . 0
ILlS
12.0
12.5
13.0
13.5
14.0
14 . 5
15 . 0
15.5
16.0
16.6
17.0
17.5 '
18.0
18.5
19.. 0
19 .5
20 .0
20.5
21.0
21.5
22.0
22.5
23.0
23.5
24.0
24.5
25.0
25.5
26.0
26'. 5
27.0
27.5
28.0
28.5
29.0
29.5
,30.0
80.5
1.0481
1.0443
1.0404
1.0366
1.0328
1.0291
1.0254
1. 0217
1.0180
1.0143
1.0107
1 . 0071
1.0035
1.0000
0.9965
0.9930
0.9895
0.9861
0.9826
0.9792
0.9759
0.9725
0.9692
0.9659
0.0626
0.9593
0.9561
0.9529
0.9497
0.9465
0.9433
0.9402
0.9371
0.9340
0.9309
0 . 9279
0.9248
0.9218
0.9188
0 . 9159
0.9129
0.9100
0.9071 '
0.9042
0.9013
0.8984
0.8956
0.8927
0 . 8899
0.8871
0.8844
0.8816
0.8789
0.8762
0.8735
8.730
8.698
8. 666
8 . 634
8.602
8.~71
366.68
365.83
363.08
362.63
361.32
360 .01
358.70
357 . 39
356.08
354.82
353.56
352.30
351.04
349.78
348.66
347.34
346.12
S.54O
8.509
8.478
8.448
8.418
8.388
8 .358
8.328
8.299
8.270
8.241
8.212 344.90
8 . 183 343.69
8 . 155 342.52
8.-127 341.35
8 .099 340.18
8.071 339.02
8.044 337.85
8.016 336.71
7.989 335 . 58
7.962 334.45
7 . 935 833.31
7.909 332.18
1.882 331.08
7.856 329.98
7 . 830 328.88
7.804 327.78
7.778 326. 68
7 . 752 325.61
7.727 824 . 64:
7.701 323.48
7.876 322.41
7.851 321.34
7.627 320.32
7.602 319.29
7.578 318 . 27
7.554 ' 317 . 24
7.529 318.22
7.505 315.22
7 . 481 314.22
7.458 313.22
7.434 312.22
7 . 410 311.22
7.387 310 . 26
7 .364 309 . 30
7 .341 308.35
7 . 318 307.39
7 . 296 306.43
7.273 305.49
65.44
65.20
64.96
64.12
64.4.8
64.25
64.02
63.7Q
63.55
63.33
63 . 11
62.88
62.66
62.43
62.21
62.00
61.78
61.66
61.34
61.14
60.93
60 .72
GO.51
60.30
60.10
59.90
59.70
69 .50
59.2f}
59.10
58.90
58.71
58.51
58.31
58.12
57.93
57.74
67.55
57.38
57.18
57.00
56.82
15,276
15.219
16.163
15.108
15,053
14.0OS
14,944
14;890
14.886
14 , 783
14.730
14.678
14.626
14,574
14 . 523
14.472
14.42.2
14,871
14 .321
14.271
14.222
14,173
14,125
14.077
14.028
13,981
13.984
13.887
13 ,841
13,794
13,748
13.703
13.657
13,612
13.566
13.522
13 ,477
13,433
13.389
13.347
13.304
13.262
56.63
i3.220
56.45
56 ,27
56_09
55.91
55.73
55 .55
13.1'77
55 . 38
55.21
55.04
54.87
54 .70
54.53
13,134
13,092
13.052
13.010
12.968
12.927
12.887
12,847
12.807
12,768
12,728
6 . 11
6.13
6.U
6 . 18
6.20
6 . 22
6.25
6.27
6.29
6.31
.6 . S4
6.36
6.38
6.5400
6 .5626
6.5852
8 . 6080
6.6302
6.6534
6.6758
6.6985
6.7213
6.7434
6.7605
6.7889
6 . 8114
6.8341
6.8h69
6.8799
6.9022
6.9255
6.M81
6.9708
8. 9927
1 .0157
7.0379
7.0603
7.0837
7.1064
7.1292
7 . 1512
7 .1742
7.1975
7 . 2199
7.2424
7.2651
7.2880
7 .3099
7.3331
8.3472
6.3695
6.3920
6.4146
6.4367
6.4588
6.4812
6.5037
6.5255
6.5483
1.03887
1.04245
1.04600
1.04969
1.05321
1.05689
1.06046 .
1.06406
1.06768
6.5704
6 . 6927
6.6151
6.6369 1.07119
6 . 6596 1.07486
6.6816 1.07841
6.7038 ) .08199
6 .7262 1.08560
6. 74~7 1. 08923
6.7712 1.09288
6.7932 1.00642
6.8161
1.10012
6 . 8&,83 1. 10370
6.8607 1.10731
6.8823 1.11079
6.9048 1.11445
8 . 9268 1.11797
6.9488 1.12158
6.9718 1.12525
6.9941 1 . 12885
7.0166 ' 1.13247
7.0382 1 . 13598
7.0609 1 . 13963
7.0838 1.14332
7.1059 1.14688
7.1281 1.15046
7.1604 1 . 15407
7 . 1729 1.15770
7.1945 1.16119
7.2172 1.16486
1.00123
1.00412
1.00825
1.01180
1.01537
1. 01897
1.02.24.6
1.02599
1.02954
1.08311
1.03607
1.04020
1.04371
1.04725
1.05081
1. 05427
1.05788
1.06138
1.06490
1.06845
1.07202
1.07562
1.07910
1.08274
1.08627
1.08982
1.09325
1. 09G84
1.10032
1.10381
1 .10748
1.11102
1.11458
1.11802
1. 12163
1. 12526
1.12877
1.132.29
1.13584
1.13941
1.14285
1 . 14646
, 907
APPENDIX A
Material
or API
GO/GODF
Sp IT
Lb/gal
60/60F
Lb/bbl
Lb/
eu ft
Lb/br
for 1,000
,b"d'
Bbl/
long tOll
Bbl/
me trio
ton
Cubio
met.en/
long ton
~ubiQ
meten/
D,letri(l
ton
,
31.0
31.5
32 . 0
32.6
33.0
33.S
84.0
34.5
35.0
35.5
36 .0
36.6
37.0
37.5
88.0
38.5
39.0
39.5
40.0
40.5
41.0
41.5
42 . 0
42.5
43.0
43.6
44.0
44.S
45.0
45.5
46.0
418 . 5
47.0
47.5
48.0
48.5
49.0
49.5
60.0
50.5
51.0
51.5
52.0
52.5
63.0
53.5
501.0
54.5
55.0
55.5
66.0
56.6
57 . 0
57.5
58..0
0.8708
0.8681
0.8654
0.8628
0 . 8602
0.8576
0.8650
0.8524
0 . 8498
0.8473
0.8448
0.8423
0.8398
0.8373
0.8348
0.8324
0 . 8299
0 . 8275
0 .8251
0.8227
0.8203
0.8179
0 . 8155
0.8132
0.8109
7.251
7.228
7.206
7.184
7.163
7.141
7.119
7 . 098
7.076
7 . 055
7.034
7.013
6.993
6.972
0.8086
6.132
0.8063
0 .8040
0.8017
0.7994
0.7972
0'.7949
0.7927
0.7905
0.7883
0.7861
0.7839
0.7818
0 .7796
0.7775
0.7753
0.7732
0.7711
0.7690
0.7669
0.7649
0.7628
0.7608
0.7587
0.7567
0 .7647
0.7527
0.1507
0.74$7
0.7467
6.713
6.694
6.675
6.656
6.637
6 . 618
6.600
6.582
6.563
6.545
6.526
6.509
6.490
6.473
6.455
6.437
6 .420
6.402
6 .385
6.368
6.350
6.051
6.930
6.910
6.890
6.870
6.850
6.830
6.810
6.790
6 . 771
6 .152
6 . 334
6.316
6 .300
6 . 283
6 . 266
6.249
&.233
6.216
54 . 36 12.689 ,1.3553
7.2391
303.61 64.20 12,650
7.3787
7.2622
302.67 54.03 12.611
7.4012
7 . 2848
301.73 03.86 12,573
7.4239
7.3067
7.4457
300.82 53.70 12,635
7.3281
299.91 ' 53.54 12,497
7.4686
7.3507
209.01 53.37 12,4.59
7,.3134
7.4917
298.10 53.21 12,422
7.5139
7.8962
297.19 53.05 12.384
7.5372
7.4182
7.5597 ' 7.4403
296.32 52.89 12,347
295.44 52.74 12,310
7.5822
7.4625
294.57 52 . 58 12.273
7.6049
7.4848
293 . 70 52.43 12.237
7.6266
7.5062
292.82 52.27 12.201
7.6496
7.6288
21)1.97 62.12 12,164
7.61.28
7.5516
291.11 51.96 12,128
7.6900
7.5745
290 :25 51.81 12,093
1.7183
7.6964
289.40 51.66 12,058
7.7407
7.6184
288.54 51.51 12,023
7.1632
7.6406
287 .71 51.36 11.988
7.7859
1 .6629
286.88 51.21 11,953
7.8087
7~68.54
286.04 51.06 11.918
7.8316
7.7079
285 . 21 SO.91 11.883
7 . 8547
7.7306
284 ,. 38 SO.76 11.849
7.8767
7 . 7523
283.58 50 .62 . 11.815
7.8989
7.7741
282.77 50.48 11,781
7.9224
7.7972
281. 96 50 . 33 11.748
7.9448
7 .8193
281.16 50.19
11 .715
7.9678
7.8415
280.35 50 . 05 11,681
7.9900
7.8638
279 . 57 49.91 11,648
8.0128
7.8863
278.79 49.77 11.615
8.0358
7.9088
278.01 49.63 11.582
8.0588
7.9316
277 .23 49.49 11,550
8 . 0808
7.9532
276.44 49.35 11 ,518
8 . 1029
7.9749
275 . 67 49 . 21 11.485
8.1264
7.9980
274.90 49 .08 ' 11.453
8.1487
8 . 0200
274.1a 48 .94 11.421
8.0434
8.1724
273.85 48.81 11,.390
8.1938
8.0644
272.58 48.67 11,358
8.2118
8.0880
271.84 4.8.54 11,327
8.2394
8.1092
271.10 4,8.40 11,296
8.26238.1318
270.36 48.27. 11.2&5
8.]546
8. 2~54
269.26 48.14 . 11,235
8 . 3074
8.1762
268.88 48.01 11,204 ' 8 . 3a07
8.1992
268.16 47.88 1110 174
8.3529
8.2210 .
267.44 47.75 '11,1
8.3752
8.2429
266.72 47.62 11.114
8.3990
8.2863
265 .99 ' 47.49 11.084 . 8.4202
8.2872
265.27 41.96 11,064
8.4442
8.3108
264.57 47.24 11 ,025
8.3319
8.4656
263.88 47.12 10,995
8.4885
8.354'
263.18 46.99 ]0,966
8.8771
8.6115
262.48 46.87 ]0,937
8.3999
.8 .5341
'8 .5566
8.4215
261.79 46.74 10,908
261.10 ' 46.62 10.878
8.5800 ' , 8.4445
304 .ob
1.16839
1.17211
1.17569
' 1.17929
1.18276
1.18639
1.19006
1.19359
1.19729
1:20085
1.20444
1.20804
1.~1l5Q
1.21515
1. 21882
1.14994
1.15360
1.U712
,1.,6066
1.16407
,1.16765
1. ],7126
1.17478
1.17838
1.18189
1.18541
1.18896
1.:19237
1.10596
1.10957
1.22251 1.20320
1.22605 1.20669
1.22961 1.21019
1. 2S8.19 1. 21311
1.23679 1.21726
1.24041 1.22082
1 . 24405 1.22441
1.24772 '1.22801
1.25122 1.23146
1. 20474 1.23492
'1 .. 2.5847 1.23~9
1.26208 1.24210
1.28561 1.24.062
',1.26921
1. 24917
1.27284 1.25274
1.27648 1.25632
1.28015 1.25993
1 . 28364 1.26336
1.28715 1.26682
1.29087 1.27049
1.29443 1.27398
1.29819 1. 27769
1.30158 1.28103
1.30539 1. 28478
1.30882 1.28816
1.31247 1.29174
1.31614 1.29536
1.31963 1 . 29819
1.32334 1.30244
1.82886 1,30591
1.33040 1.30989
1.33418 1.31810
1.33756 1.31642
1.34136 1.32017
1 .34476 1. 32363
'1.34840 1.32711
1.36206 1.33071
1.35574 1.33433
1.35922 1.83775
1; 36294 1.34141
908
Mat.erial
or API
60/60C'F
68.5
59.0
59.6
60.0
60.5
61.0
61.5
62.0
62.5
63.0
63.5
64.0
64.5
M.O
65.6
68.0
66.5
67.0
67.6
68.0
68.5
69.0
69.5
10.0
10.5
71.0
71.5
72.0
72.5
73.0
13.5
74.0
74.5
75.0
75.5
76.0
76.5
71.0
77.5
78.0
78.5
79.0
79.5
BO.O
80:5
81.0
81.5
82.0
82.5
83.0
83.5
84.0
84.5
~.O
85.5
Sp gr
60/60F
Lb/gal
0.7447 6.199
0.7428 6.1840.7408 6.167
0.7389 6.151
0.7370 6.135
0.73.51 6.119
0.7332 6.103
0.7813 6.087
0.7294 6.072
0.7215 6.056
0.7256 6.040
0.7238 :-6,025
0.72i9 6.010
0.7201 5.994
0.7183 5.979
0.7165 5.964
0.7146 5.949
0.7128 5.934
0.1111 5.919
0.7093 5.904
0.7075 5.889
0.7057 5.874
0.7040 5.860
0.7022 5.845
0.7005 5.831
0.6988 5.817
0.6970 5.S02
0.6953 5.788
0.6936 5.713
0.6919 5.759
0.6902 5.745
0.6886 5.731
0.6869 5.718
0.6852 5.703
0.6836 5.690
0.6819 5.676
0.6803 .5.662
0.6787 5.649
0.6770 5.635
0.67M 5.622
0.6738 5.608
0.6722 5.595
0.6706 5.582
0.6690 5.568
0_6675 5.556
0.6659 0.M2
0.6648 5.529
0.6628 5.516
0.6612 5.508
0.6597 5.491
(l.M81 5.477
0.6566 5,465
0.6551 :h. 453
0.6536 5.440
0.6521 5:427
Lb/bbl
Lb/
cu It
260.41
269:72
259.03
46.&0
46.37
4.6.25
258.34-
46.18
257.-68
257.01
256.85
255.69
255.02
254.37
253.71
253.06
252.40
251.75
251.12
250.49
249.86
249.23
248.60
247.98
247.85
246.73
24S.1i
245.49
244.89
244.28
243.68
243.07
242.47
241.88
241.29
240.70
240.11
239.68'
238.96
238.38
237.81
237.24
236.67
236.11
235.54
234.98
234.42
233.86
233.31
232.76
232.22
231.67
231.13
230.60
230.07
229.54
229.01
228.48
227.95
46.01
4.5.89
~.77
45.66
45.64
45.42
45.30
45.19
45.07
44.96
44.84
44.73
44.62
44.61
44.39
44.28
44.17
44.06
Lb/hr
Bbl/
for l,Oo(~
long ton
bpd
10,849
10,821
10,792
"10,764
10,736
10,708
)0,680
10,653
10,626
10,598
10.571
10.544
10,517
10.490
10,463
10,437
10,411
10,885
10.358
10,332
10.300
10,280
43.9~
10,235
43.84
43.73
43.68
43.52
43.41
43.30
43.20
43.09
42.99
42.88
42.78
42.68
42.S7
42.47
42.37
42.27
42.17
42.07
41.97
41.87
41.77
41.67
41.57
41.48
41.38
41.28
41.19
10,229
10,204
10,179
10,154
10.129
10,103
10,018
10,054
10,030
10.006
9.982
9,958
9,933
9,909
9,886
9,862
9.838
9,814
9.791
9,768
9,744
9,722
9.699
41.09
41.00
40.90
40.81
40.71
9,6~6
9.653
9,630
9,608
9,586
9 .564
9,542
8.6035
8.6244
8.6482
8.6707
8.6933
8~ 7160
8~1389
8.7618
8.7835
8.8067
8.8300
8.8520
8.8741
8.8978
8.9201
8.9425
8.9651
8.9878
9.0105
9.0334
9.0564
9.0796
9.1013
9.1246
9.1465
9.1685
9.1922
9~ 2145
9.2384
9.2600
9.2834.
.9.3061
9.3273
9.3518
9.3732
9.3963
9.4195
9.4412
9.4647
9.4865
9.5102
9.5323
9.5545
9.5785
9.5992
9.6285
9.6461
9 . 6688
9.6917
9.7129
9.7317
9.7591
9.780~
9,520
9.8039
9,498
9.8274
ton
Cubic
meters/
lona ton
8.4677
8.4882
1.36667
1.36999
8.5116
1:37377
Bbl/
m!'!trio
Cubio
met.era/
me trio
ton
1.34509
1.34835
1.35207
1.35559
8.5338 1.37734
8.6S60 1.88093 1.85~n~
8.5784 1.38454 1.36288
8.6009 1.38817 1.36625
8.62SS 1.39182 1.36984
8.6448 1.39526 1.37322
8.6616 1.89895 1.87685
8.6906 1.40265 1.38050
8.7122 1.40614 1.38394
8.7389 1.40965 1.38739
8.7573 1.41342 1.39109
8.7792 1.41696 1.39458
8.8013 1.42053 1.39809
8.8235 1. 42411 1.40162
8.8458 1.42171 1.40616
8.8682 1.48182 1.40872
8.8908 1.43496 1.41230
8.9134 1.43861 1.41590
8.9362 1.229 1.41951
8.9575 1."44574 1.42290
8.9805 1.44945 1.426515
9.0021 1.45293 1.42998
9.0237 1.45642 1.43342
9.0471 1.46019 1.43713
9.0689 1.46372 1.44060
9.0925 1.46752 1,..44435
9.1146 1.47109 ~44786
9.1368 1.47468 1.45139
9.1591 1.47828 1.45493
9.1S00 1.48164 1.45824
9.2041 . 1.48554 1.46201
9.2251 1.48893 1.46541
9.24.79 1.49260 1.46903
9.2708 1.4D529 . 1.47266
9.2921 1.49974 1.47605
9.3152 1.50346 1.47972
9.3367 1.50694 1,48314
9.3600 1.51070 1.48684
9.3818 1. 51421 1.49030
9,4036 1.51774 1.49377
9.4273 1..52155 1.49752
9.4476 1.52484 1.50076
9.4715 1.52869 1.50456
9.4938 1.53229 1.50809
9.5161 1.53590 1.51164
9.5386 1.53953 1.51521
9.5595 1.54289 1.51852
9.5839 1.54683 1.62240
9.6049 1.55023 1.52575
9.6261 1.65364 1.52910
9.6491 1.55736 1.53276
9.6722 1.56109 1:53643
909
APPENDIX A
Ma\erial
or API
Sp gr
'6O/6o.oF Lb/gal
60/6o.oF
0..6506
0.6491
0.6476
86.0.
86.5
87.0
87.5
88.0.
88.5
89.0.
0..64.61
0..6446
0..6432
o..M17
0.6403
0.6888
0.6374
0.6360
0.6345
89.5
90.0
90 . 5
91.0
91.5
92.0
92.5
0.6331
0..6817
0..6303
0.6289
0.6276
0..6261
0.6247
0..6233
0.6220
0.6206
0.6198
0.6179
0.6166
0.6152
93.0
93.5
94.0
94.5
95.0
91S.5
96.0
96.5
97.0
97~6
98.0
98.6
99.0
0.6139
99.5
100.0
0..6126
0.6112
I
Lb/bbl
5.415 227.42
5.40.2 226.89
5.390 226.36
6.877 225.83
6.365 225.32
5.358 224.81
5.341 224.30.
6.329 223.78
6.316 223 . 27
6.30.5 222.78
5.293 -222.28
5.281 221.79
5.269 221.29
220.79
~.~7
5.246 220.31
5.234 219.82
5.222 219.33
5.210 218.85
5.199 218.36
5.187 217.87
5.176 217.40
5.164 216.92
6.154' 216.44
5.142 216.96
5.131 215.49
5.120 215.02
5.109 214.55
5.098 214.08
5.086 213.61
Lb/
cu ft
Lb/hr
Bbl/
for 1,000
long ton
bpd
40..62
9,476
40..53
40..43
9,454
40.34
40..25
40..16
40.07
39.98
39.88
39.79
39.71
39.62
89.63
39.44
39.36
39.26
39.18
39.09
89.00
38.92
38.88
38.76
38.66
38.58
88.49
88.41
38.S3
38.24
38.16
9,432
9,410.
9,889
9,368
9,347
9,326
9,805
9,284
9.263
9,242
9,221
9,200
9,180
9.8492
9.8729
9.8949
9.9188
9.9410.
9.9633
9.9856
10..0.081
10..0.826
)0..0684
10..0.762
10.0991
10..1221
10.1452
10.166~
'10.1898
10.2132
9,U8- 10.2367
9,098 10..2584
9,077 10.2821
9,058 10 .3040
9,037 10..3279
9,018 10.3479
8.999 10.8721
8,979_ ' 10.3943
8,960 10.41'67
8,941 10.4391
8,921 10.4616
8,901 10.4863
'9,160
9,139
BbI!
Cubic
metric
meter./
long ton
ton
Cubic
meter&/
metric
ton
9.6936
1.56455
9.7170.
1.56831
1.57180
1.57560.
1.57913
1.68267
1.58622
1 . .58979
1 . 59368
1.59699
1.800tH
1.60424
1 . 60790
1.61157 1.61495
1.61865
1.62237
1.62611
1.62956
1.63332
1.63679
1.640.59
1.64377
1.64761
9.7386
9.7621
9.7840
9.8069
9.8279
9.8501
9.8742
9.8946
9.9171
9.9896
9.9622
9.9850.
10..0059
10..0.289
10..0619
10..0750
10.0964
10.1197
10..1412
10.1648
10.1845
10.2088
10.2302
10.2521
10.274-2
10..2964
10.3207
1.65114
1.65469
1.65825
1.66183
1.66575
1.63984
1.54354
1.54698
1.550.72
1.:s5419
1.55767
1.66n7
1.56469
L.56851
1. 57176
- r.57633
1.67891
1.58250.
1.58612
1.58944
l:.59309
1. 59675
1.60042
1.60381
1.60762
1.61094
1.61468
1.fH781
1. 621~9
, 1.62506
1.62856
,1.63206
1.63558
1.63944
"
,,-
..
I,
:i
'I,
I:
I,
\,
I
i
.j
. !
APPENDlX B
Yields.
Boiling range, of
Below 80
80-300
-80-400
80-450
80-550
375-500
400-700
400-900
550 and up
700-900
Above 900
Notes
MairJ.ly gas
ASTM end point about 307F
ASTM end point 382-391 OJ'
ASTM end point about 427F
275-450F mid boiling point
ASTM end point about 480F
Mid boiling point about 550F
Also other boiling ranges
Usually low-penetration aspb8.It
Quality. The full boiling ranges indicated above must have superior
properties if the quality is to be good or excellent, and the percentage
yield must be normal. Good products can also be obtained from crude
oils not designated as containing superior products but at a sacrifice in
yield or by expensive treatment. To be classified as go~d, the properties
must be:
0
911
APPENDIX D
Boecan,
Zulia,
Ven&Bum
ootin~
Kern
River,
Calif.,
Quitmall,
Min..
U.S.
u.s.
Gato
Ridge,
Calif .
U.S.
Tia
Juana.,
Zulia,
Venezuela'
Baohaquero.
Zulia.
Venezuela
1
II
.1
Gravity, API .................
Sullur, % ...... .. .....
Visoosity, SSU at lOODF
Date ............ . . , .... , .
...
....
3-3-48
Characterization Jactar:
at 2500F ........... , .......
at 450"F ...................
at S50DF ......... . ....
at 750"F ...............
Average ...... . .......
Bue ......................
10'.7
9.5
5.2S 4
1.23
.......
11~9
4-12-48
12.20
.......... ...
11.60
11.40
11.13
11.16
11.40
11.65
I
11.15
N
11.9
12.1
11.8h
11.55
11.85
I
.... ... .
1.6
.........
.......... ..
a.8
42.0
. ........
1.211
9.4"
..........
........ .
5.2
Jet stock:
% to 5500F ...............
API aravity ................
Quality ................
10.0
6.1-
44.511
Good
29.0&
.......... ..
.........
..
0.4
1.4
11.3"
62.0~
67.0~
. ......
8O.0~
11.4"
2.9
17.0~l.O
~
.....
11.15
11.30
11.40
N
o.
....
2.4
72.4
6.3"
............
86.5
5.0
68.0
83.0
....... .
~
7.5
14.2"
.....
o.
Good
....
20.7'"
37.5
8.7
40.0
15.0
a9.5
Good
Ker08eDe-dfstillate:
%
37~OOQF . ......
4.1
2.7-
39.2
19.24
3.0&
32.5
13.0~
0.38
5.911
45.0
29.0"
0.75
1.511
4.2
36.2
15.7"
0.56
1.0
35.0
33.9
14.5b
16.0
2.25b
0.56&
20. ()II
32.0"
-30.0
22.5
33.0
-35.0
1.3~
3.1
1.1
% 400-7000F ..............
16.0
19.1-
21.00
21.3
26.0
30.0"
-30.0"
48.Oa
3.Oa
39.0"
-35.0
3.3'
1.7
0.8/1
28.8
73.0"
21.0
..........
26.5
44.5
78.5
22.5
84.So
75.1"
20.4
41.So
38.6"
75.6"
71.010
20.0
41.5'
75 .o~
21.5
Good
~king
90.0
93.9 4
82. I"
91.3
77.8 0
6.5
9.1
6.5
11.3
7.0
.......
'"
.o
...
.......
...... .
12.8
55.0
25.0"
4.3"
67.4
Excell.
...... , ...
.. . .
..
......
....... ..
........
.. ....
22.2-
17.6.a
.. ..
a. a .
..
... ..
...... .
.o. ..
37.0
l.t)Io
2.65
57.0 11
Excell.
52.0"
Good
4.6
26.0
'23.7
23.2
-5.0~
-20.0
~.3()a
63.6
Excell.
..
..
.o
85.0
10.0
6.6
. . ........
..... . ...
14.8"
. . . .....
-19.0"
4.5
52.5Exull.
"i
.(
11.40
1.5
. . ........
............
11.75
..........
.. . . . .
1942-11)50
..
11.20
11.32
..... ..
2.64
11.62
11.28
11.20
&
11.40
11.30
11.40"
42.S
..
.... ..
11.40
14.0
6,000+
. ...........
.............
............ ..
or.
2.ZO
....... . . ......
66.
..
6.0-
0
I
2.66
......
.o
13.8
5.21
13.3
6.000+
12.1
3.85
19.8
16.8
HLO
-10.0
-17.0
2.25
53.5
ExceU.
.'
912
Vermillon.
Canada
Santa.
Qajyar&h.
Iraq
Marl&,
Calif.
U.S.
14.0
2.03
14 .
7.86
15.4
4.63
9-19-42
1-28-81
8-2-54
CharacteriZAtion fa.ot.or:
at 250F .. . .............
Bot. 450F ...... . .... , ..
11.27
.....
.. , ..
Base .......................
12.10
11.75
.........
11.40
11. 71IN
'Lon. % ....... .,
........
at 5liOOF ...
at 750F .........
0
..............
Average ...............
Gasoline:
% to 3000F ...............
Oct.. No., clear ....... .
Oot. No., a co TEL .... .
% to 400F .......... . , ..
Oct. No., clear . .. , .... . ..
Oct. No . 3 cc TEL .......
% to 450F., ... '....... . ..
Quality ......... , .....
Jet stock:
% to 550F ...............
API gravity ...............
Quality; .
0
. .. I " .
11.28
11.42
........
4.0&
1.8
.......
48.0 11
70.()b
12.1
38.0
..........
61.S'
........
....... .
4.0
.... . . .
.... . ...
. ......
14.2
31.8
.' I.
.... . .
...
Tis. Juana
(heavy),
Zulia.
Venezuela.
16.1
2.21
Lagunillaa
(heavy),
Zulia.
VenMuela.
IS.a
2.22
Tuoupita.
D. Ama.auro,
Vene.zuela.
16.0
1.01
358
1937-1950
11.42
11.66
11.30
11.29
11.90
193&-1950
19015-1947
11.38
11.55
11.35
11.30
11.11
11.40
11.48
11.51
11.48
11.45
11.42
11.47
N
IN
11.66
11.40
n.SEi
7.0
..
..
II
..
..
. . ... . .
13.2
59 . SIr
70.S.
17.0
6
25.0
43.0
Good
1.1
66.0
85.0
4.0'
4.0
2.0
70.9
84.7
62.0'
81.0 1
8.li
5.0
61.6
81.0
6:5.8
52.0
76.8
7.0
Good
10.0
Good
18.4
17.9
38.0
38.8
SO.6
7.2
14'. 0
88.8
KerO$ene-diatlUate :
7.8
33.8
12.8
42.6
14.5b
19.~
High
1.6
29.9
35.0 b
. .....
......
........
Low
High
53.0
73.0 b
23 . 5
..... .
11.3
6.1
23 .7
20.3
23.1
0
35.0
High
Lube
45.0
Excell.
as.8
..
&
...
.......
.......
.......
. .....
. . ....
.......
8.5
6.2
34.5
35.2
.. . .
16.0 b
38.0"
.
1.80
15.0
0.41
23.8
33.0
-3.0
2.50
25.5
87.0
-80.0JI
1.09
24.2
38.0
-25.0"
1.04
39.8
75.6 4
22 .8
43.0
73.3"
23.0
Good
44.3
74.5 b
24 . 2
Good
80.5
26.2
55 .0
17.0
1.02
.. " ,.,
..
. " ,,_.
76.0
8.0
8.0
!lLO
86.6
13.1
4.4
33.0
11.0
28.6
82.1
12.4
6.5
29.7
24.4
16.0
17.5
-5.0
15.0
2.10
20.1
9.0
17.0
1.98
.... . .
t
.....
......
..... .
.... .
..... .
.....
GoOO ll
6;5
36.4
8.0
35.0
17.0
0.41
... , . .
' ''' .'' .
. ......
47 .0
Excell.
53.0
Excell.
47.2
Ex cell.
0.18
25.0
-4O.0 b
0.45 b
46.6
72.5"
~.O
Ex cell.
86.0
12.7
5.6
21.6
48.4
Excell.
913
APPENDIX B
Baxterville,
Mise"
U.s.
16.2
2.82
2.661
9--27-50
Characterization futor:
at 2S00F .... " ...........
at 46ooF ..............
at 550F ...............
at 750F ..........
Average .............
Base~
LoS8. % ....
11.40
11.30
1].30
11.89
........
11.7
4.6
2.1
65.0
81.0
9.3
36.So
14.4411
67 .O~
22.7
Good
Good
6.2
39.6
8.0
33.8
15.0~
2.09
46,4
Good
20.0
47.4
11.1
8.1
40.8
24.6
39.0
-40.QAo
High
38.9
30.0
35.0
0.67
oo
..
oo
oo
.-
43.3
22.4
91.0
59.0'
21.3
36.7
14.0
0.23
74.9"
22.8
21.7
12.3
High
47.6
84.7
12.0
6.3
25.8
S.2
Good
32.4
70.9
. ... . .
oo
..
10.06
11.0
10.S-
0.6-
- .........
26:5
.
11.60
11.10
11.10
11.10
11.20
N
1956
4.7
..........
...
.....
1.0
70.5
85.0
...........
14.9
0.20
oo
. ...........
18.S'
11.68
..
7.0
.
.
12.22
11.76
500
;
0.8
42.0
Good
11.30
18.0
0.13
1.8
43.3
-6.0"
0.88
11.40&
1.527
6-29-51
18.4
0.99
11.60
11.81
PI
16.2
25.2
62.0&
8.1
.........
463
17.8
2.09
11.08
11.10
11.22
N
11.s.;
N
40.0 0
Kerosene-distillate:
% 87 5-500oF .............
API gra.vity ........... ;
Smok.e point. ..........
Sulfur. % ........ .'....
Quality .....................
....
...........
5.9
.............
1'.33
9-8-48
2.3
......
17.2
........
0.1
Jet stock:
% to 5600F ........ : .......
API gravity ..
QuAlity .......... . .......
II
16.2
3.6
Tarakan,
Kaliman tan ,
Indonesia
Lost
Hilb,
Calif.,
U,S.
MiB8.
Mixture,
Monagas,
Mm.,
U.S.
Venezuela
Quiriquire,
,
12.02
11.70
11.68
11.58
11.75
I
.............
Gaao]ioe:
% to 300"F .................
Oct. No. ' olear ..........
Oct. No . 3 00 TEL .
.,. to 4000 F. . . . . . . . . . . . . . .
Oet. No., clear .........
Oct. No . 3 co TEL .........
% to 450F ...............
Quality ..................
Lloydminater,
Canad..
oo
77.3
10.0
7.0
18.5
14.3
18.7
30.0
0
High
45.()"
Good
.....
.....
..
........
19.8~
0.23
25.3
32.0b
S.OO
1.06
19.aGood
S:1
29.1"
32.7
86.1
28.0
12.3"
31.3"
17.6"
0.28"
19.0
29.0
17.0
0.02
63.6
28.6 4
28.011
-3iLO"
0.61"
28.0
-5.0 .
45.075.5'
20.0
E.%een.
87.7
78-79
17.6
EzcelL
70.9
67.3
13.3
Zero"
0.06
Good
59.1
76.9
19.5
Ex cell.
46.7
70.S
77."
79.2
10.8
11.2
4.8
31.5
24.4
66.5&
25.8
. ..... .
7.7
20.2
12.2
2.4
34.5
46.0-
16.0
29.4
30.2-
20.2
011
21.4
66.0'
16.4-
24..1411
-60.0
43.~
-60.0"
1.32 b
Low
1.4&
2.S8
36.0
Excell.
43.2
Good
40.6Excell.
..
10.2-
E:l.oell.
1
I
914
_.-
K:lamOllO,
Na.me, atate, and
~unt.17
New
Guinea
V:uwosity,
Oat,., ... , . ,
.....
...
..
..
Characterililation factor:
at 250"F .... -... , .........
18.0
'0.93
...
..
1956
.... -
Placenta,
Calif.
Olll~'
U.s.
Caaabe.
Antioquia,
Colombia
20,8
2-50
11-49
......... ,
12.60
11.41
11.42
11.90
11.3:.1
11.85
11.16
1.25
243
11-28-51
dale,
Mia.,
U.S.
20.5
1.06
660
19.8
11.41
La.ngll-
Coa.J.igna.
(East),
CaJ!f....
U.S:
20.1.
0.51
178
4.1
883
11.3
11.23
11.2
11.1"
11.55
11.53
I
11.41
ll.2
N
11.25
11.27
11.30
N
PN
0.6
0.8
0.8
a.D
1.0
7.8
1.211
76.2
6.0
13.2"
9, I'"
82.01
89.S-
at .550o F .................
Avera.ge ..................
B~ .............
LON,
..... . ..
% .............
Gasoline:
~ to SOOoF .... ' ........
Oct. No . clear ..........
Oct. No., :3 ce TEL .......
% to (OGoF ................
clear ..
Oct.
Oct, No., 8 cc TEL, ......
% to 450"11' .............
Quality ................
~
II
..
.....
Jet. stock:
% to 55O"F;', ..........
API gravity .. ~ ...........
Quality ................
Xeroaene-di"tW!l. te:
% a7.5--5QOOF .. '.
API iI'&vity...... '....
Smok$ point. ............
Sulfur, % ...................
Qua.U ty . ;. . . . . . . . . . . . .
..
81.5
89. ()01
8.0
IS.7
69.(}g
74.2
82.2
G8.~
20.4
14.4
82.09
IS.3
FBir
...........
Excell.
. . . . .,
a ...
14.3
If.o
34.2
32.8
19.0
19.0
0.10
Fair
II'
0.40
"
......
Goodt.
41.9
Good
9.5
38.0
16.01>
0.29'"
..
.....
20.3
31.6
9.8
34.9
15.96
0.26
16.3"
.....
55.4"
41.0-
73.0
25.'1
.. '" .. " ...
23.2
Excell .
13.56
24.5
70.0
12.6
3,8
34.0
76.D
18.9
15.8
23.8
27.0
04.1
74.1&
21.0
E:x,ecl!.
16.034.0-
11.0"
48.2
71.4'
65.5 0
0.82&
36.9
88.5
22.0t.
0.65
0"
0.61
29.3-
29.S<>
45.5
26.S"
0.62
15.611
Good~
.0
25.0
.29--.2
48.0t.
9.6"
67.06
38.0"
62.020.S"
40.0
-30.01
0.41"
29.7
33.0
Low
16.0r.
21.0
Excell.
.. .
47.0 0
81.9
42~2
33.2
0
7.4
66.0"
10.5
24.1
39. Ii
~
3.3
... . ..
11.0
29.'
27.6
34.7
.. .. "
n.4Sa
lJ .2M
11.20
11.23
14.56
0.1411
38.4'"
33.0&
-25.0'
0.351'
2.28
Ii
...
59.4111
22.8
Exc.elL
stock (residual):
12.4
12.6
3.2
38.0
21.5
14.7
4.8
2.8
40.8
35.5
6.5
32.1
21.6
15.0
"
28.301
......
Low
'" I
"
..
II
26.5Excell.
25.0
10.0
19.0
23 . .5"
14.2"
69.0-
87.06
2.4511
20.0b
11. 0 6
1.211
3.46
36.4E:x:eell.
Exee1l.
1.3'1
29.0
Excell.
40.8
Good"
67.74
11.0
69.4"
10.'8
4~.0<2
..
4.2
27.5
18.6
13.00.61"
28.0"
ExcaU.
915
APPENDIX B
..
Name, sta.te, and oountry
21.0
Gravity. API. . .. . .. . ......
1.95
SuHur, % .... . ......... .. .
Vi8cosity, SSU at lOOF . . .. . ........
Da.te . ... . .... . .. ... ..... 1941-1950
21.0
2.72
. ....
1938-1950
21.7
3.92
478
1.67
. .....
. ....
11.81
11.58
11.50
11.90
11.60
11.60
. ...... . .
410
9-27-50
12.27
11.87
1938-1947
-
..
'
,"
11 . 80
11.69
11.65
11.65
11.40
11.40
11.~2
11.54
11.50
I
11.63
I
11.60
11.70
I
11.83
11.58
11.89
PI
0.1
0.5
0.8
6.5
64.0
10 , 1
12 , 2
8.6"
54.0"
... . .
7.0
59.0
84.0
75.0
.......
13.5
56.0
16.7
51.0
67.0
20.2
78,9'"
18.8
43.0"
72 . 0
86.2
15.462.011
13.5
66.0
81.0
]8.0
11.62
Guoline:
% to aOOOF ........ ,
Oet. No., clea.r ... , ..
Oct. No., S co TEL ....
% to 400F , . . . . ......
Oct. No., elear ... . .....
Oct. No., 3 ee TEL . . ..
% to 4sooF . . . ......... .
Quality .... . . . .. ... , .
Fair
Jet stock:
% to 550F . ....... '"
24.0
77.0
15.7
...
~
22 . 1
.....
43.0
Good
28.0
43.8
Good
28 . 9
56.7
9.0
3S. 0
8.7
39.2
8.4
42.9
19.0
0.33
18.0
0.61'
21.5
0,29
23 . 5 .
44.0
-22.0
1.00
23.0
48.0
10.0
1.70
22.7
57.0"
18.0"
. .....
11.69
1.7
...
.-
19.3'"
.......
Good
15.S
14.1
5.1
32.9
.24..8
42.5
71.5"
27. 6
o..o.o.
35.5
71.0
27 .2
~
.....
1.42
Good
39.5
70.4"
27.S
o.
71.5
70.3
13.3
0.8
6.3
30.5
21.8
... ..
"
o.
.....
. . ....
10.0
15.0
39.0
2.05
I
48.3
Good
12.5
75.0
40.0
2.35
. ....
47.3
Excell.
16.8
81.0
...
&
Good
27.3"
52.0
30.0
41.0
Good
Good
9.7"
40.0
18 . .5"
12.0
86.0
16.0
0.34"
24.150.0
0"
0.71"
Good
11. 90"
I-
1.0
5.3
56~O
76.5
12.0
38.,6
64.8
16.7
26 . 2
06.1
H.8
45.5
28.0'
0.58
0.22
27.3
58 . 8
9.0
1.5
38.4
48.0
- 40. ().\
0.35
,
42.1
69.5
41.9-
54.4
70.7"
27.8
72.2"
26.0
Excel.L
71.Qa
It.2
7.8
22.5
16.0
70.0
72.8
14.9
4.6
11.2
86.2
22.8
. . " ..
17.2,
..
..
~.6
16.2
21.0
14.84
10.0
30.0
46 .0"
. . , ., "
0 . 90
Lube
.4 0.9
41.0 4
32.1
Good
Good
1.7b
31.1
25.4
49.0 b
a.57
.....
. ....
. . ..
12.10
11 . 79
11.68
...
. ......
Kerosene-distillate:
21.6
3 '. 37
462
1953
21.9
0.84
22.1
53.0~
44.9Good
~l
I
91.6
.....
Lome.
Novia,
.i .......
ton,
Calif.
U.S.
.
.. .... ..
Da.te ...........
AVeTall:e .
Ii
..
!II
..
"
It
"
..
~ ~
..
<II""
"
Il
% to
SOOOF
Oct. No.,
Oe-t.. No., 3 co TEL ......
'" to 4000F ..............
Dot. No.. clear ......
Oot. No., 3 eo TEL .....
% to 4.5O"F ..............
Quality ............... " ,
........
!II"
!II
"
110
..
'" ,.
"
,.,,,
11.62
11.51
11.44
11.07
11.02
..
..
II
.....
'"
..
1l.15
1.2
0.2
8.5
0
7S.0li
89.0 11
5.2
.....
,.
65.0"
79.0"
16.8
58.0
68.0"
'"
Excell.'
21.7
~~.~~.~
M.O"
82.4:
43.0
Good
28.4
..
8.14
31.0
48.5
Good
..
22.5
0.25
M
19M
11.86
68.0
87.01>
20.04
80.0
22.5
Good
U.S.
22.8
0.2
11'7
...........
67.5"
86.a
12.4
. " ...
~
. ..........
. .............
.
,.
'"
......
'1.6
...... " ..
.....
Kalimantan
(non waxy).
KalimAD.t.a.D,
IndoneaSa.
11.64
. . . . . . . .,
18.6
65.6
Mirnnda,'
11.67
I
73.0~
'" I '
Goo.
Creek,
T~ .
U.S.
11.10
11.20
11.08
11.13
N
.. .
......
.... '"
"-
11.05
10.964
n.10"
11.0
,
...
....... . ,.
0.5
..
Jet stock:
% to 550'"J". . . . . . . . . . .
API gravity ..........
Qualit.y ..............
44.0
22.5
4.17'
0.10
11.58
n.38
11.40
11.48
11.46
lor IN
1..0. . % .....
Gasoline:
21.6
1.48
Charaet.ema.tion factor:
at 250F ...............
a.i 450"F ................
at MOGF . _ ..
a.t 750o P ...........
U.S.
21.7
Fuhrman
MMCho.
....
28.0
0.07
1956
11.4
10.96
10.S
10.S11,0
N
0.1
11.0
11511
85 . .521.0
11'
82.81
36
11.4
Good
FdceU.
3.5.1
30.0
20.8
65.3
29.1
82.0
20.1
12.0
80.1
23.3
Kerosen&-dil!ltilla.te:
% 375-5000F.........
API gravity ..........
Smoke point ......
Sulfu.r, % .............. ,.
10.0
36.0"
29.0
35.5
12.3
38.0
16.00
1.35'IJ
29.0
30.8
Low
Low
.....
42.0b
-'10.01>
Low
53.8
24.0
-28.0
2.1
Low
.........
81.9"
16.0"
24.0
Ex cell.
54.2
71.0'
74.4
74.0b
76+~
2tU.I
21.5
Excell.
23.0
,Excell.
12.51>
18.0
0.32
Low
0.08
11.0
0.02
1")1, <.:11.
or diea.el Cue!:
% 400-700o F .............
Diesel mdes: ..............
Pour pain' ...... : ......
2'1.3
..
;&
33.2
70.9'"
23.01>
89.0
....
0.8.5
Quality ...............
12.041
23.5
Quality .............
Good
46.8
68.6
13,3
4.5
,. "
45.04
17.8
64.4
2.0~
48.412LSl.
6.3
28.0
18.6
BUS
n.O"
21.0
....
64.S
19.2
1.0
12.7
32.5
22.3
49.0
31.4
5O.JS
JS2.3
'"
21.4
-66.OA
Low
Zero'
0.07
SO.O
67.0"
78+"
16.3
74.0
19.2
Zero
51.5
88.1
Excell.
44.6
12.8
Zero"
I
\
43,()4
19.2
\
"
"
Ii;
"'
'"
II
..
..
..
Low
. " ....
34.2
Excell.
..
Negative
Low
II
II
to. 0"
0
II
II
..
II
........
... "."
....
...
"
.,
.. " '"
2'1.8
Good
"
~
20.6
Low
Fair
27.'1
Zero
16.5'"
-1504
Low
. '"
Low
0.9"
..
Lube
20.4Good
12.8
Exoell.
Excell ..
917
APPENDIX B
Wafl'&,
Tbomp-
TelL,
Talco,
Tex.,
Neutral
8011.1.
U.S.
U.S.
Zone,
Tex.,
Middle East
U.s.
24.2
312'
25.3
8-54
0.32
85
1954,
Refugio,
Nama, state, and country
Placedo,
Tex.,
U.S.
Santa
Barbara.
Monag&8,
Vene.ue1a
23.6
0.22
58
10-4-51
24.4
2.82
657
4-1-49
11.09
12.10
11.16
11.16
11.92
12.06
11.78
11.28
11.63
11.87
11.94
I
11 . 58
11.22
11.60
Average ................
Baae ............. .... ..
11.24
11.16
N
.........
.. . .... ..
11.2~
11.82
11.14
11.30
11.88
Lou. % ................
0.2
0.4
. ......
Guoline:
% to SOO"F ...............
Oct. No., clear ...........
Oct. No., 3 eo TEL .......
70.()t
88.0-
400"F ...............
6.8
Characterization I a.ctor:
at 2500F ..... " ...........
at 46QOF ..................
at 550F ..................
% to
2.1
15.1
Ex cell.'"
.. ......
81.5
....
21.6
...... ..
0.4.
1.0
7.4
69.2
8.5"
6'.0
84.0"
83.0
..........
H.9
Excell.
. 0.92
3-42
11.~
l1.j8a
1.470.0"
88.0 0
61.0
14.0
16.5
........
...........
..........
18.5
19.0
48.0
... , ...
11.37
NI
24.6
50
....... , . .
8.0
68.0
12.0
..... ...
65.7
SO.2-
.......
U.2
0.14
19.6"
Excell.
4.0
66.0'
M.O'
12.8
62.0 6
79.0&
17.0
Good &
Jet stock:
% to &54)F ..............
API gravit.y ...........
Quality ....... . ...........
o.
48.7
29.0
31.0
54.3
.......
oo
..
24.5
50.1
oo.oo
54.()a
30.4
32.4
.....
oo.
........
33.5
oo
oo
28.6
40.0
GOod
KeTOae.ne-disillla t.e:
37&-6OO"F.: ............
26.8
31.0
7.4
4.3.8
18.6~
23.0"
0.05
0.28
8.5
14.1
33.411
42.3
32.3
17.0
33.0
15.0
Low
Low
oooooo
0.414
12.3
34.7
15.0
0.165&
,.
67.1
30.S)
-85.0~
0.13
oo
.......
23.3
58.0
17.0
0.90
68.0"
32.2
39.0 6
-40,0&
-80.0/10
1:6
Low
Low
12.2
71.0 b
25.7
SO.O"
24.2
26.5
Excell.
Exoell.
Excell.
75.5
69.2
21.5
45.0"
14.7
2.0
71.5
16.1
4.6
36.5
27.5
Good
...
oooo
.....
too.
O.44b
'.
86.2
74.8 b
47.2
34.1
24.5
50.2
10.0
25.5
Excell.
51.1
16.9
2.0)
47.0r.
24.011
39.0
67.9A
24.3
......
oo
70.6
14.3
8.0
29.6
20.9
45.0
69.0
25.1
"
......
74.6 6
3.0
50.0
54:.072.011
19.4
3.7
42,4&
46.7
34.5
19.1&
33.4
25.0
-15.0
25.0
..........
......
12.0"
21.8"
40. Or.
44.0&
Low
Low
19.1
0
ll.()b
0.25
.......
6.8
.......
15.7
78.0
108.0
2.65
. .....
41.6
Good
20.5
.........
..
........ .
......
. .....
41.5
..... .
1.1~
Lube
10.Qa
20.0
...... .
t'_
33.()a
Ex cell.
i.
918
1,.
'
.... .
5-20-42
...
IG35-1942
25.8
1.65
. ......
1947-1950
11.93
12.00
11.60
11.60
11.02
11.50
at 760"F .................
Average ................
11.70
11.69
11.63
11.57
11. 70
11.70
'I
LoBS, %, ..
. ....
. ....
10.6
64.0&
Jet stock:
% to 550D F ..............
API gnLvity ...........
'''
1.24
11.85
Quality .. . ...............
25.3
1. 76
24.7
Zulia,
Venezuela.
Guoline:
% to 3000F ..............
Oct: No., clear ..........
Oct. No., 3 co TEL ......
% to 4QODF ...... ,." ....
Oct. No., clear ....... ' ..
Oct. No., 3 cc TEL .. , ...
% to 450I)F. " ..... , ., ..
(102),
at.
:.
Tia Juana
La. Rosa
(Cabim 116) ,
Anzoa.t.,
Zulia,
Venezuala Venezuela
i'I :
Leona.
(Tigre),
S4 . 0~
)9,4
55.01>
79.0&
24.3
30.2
17.9
'
12.05
11.65
11.50
11.70
11.72
11-49
1956
12.1
11.57
11.4
11.73
11.75
11. 91
11.89
11.4
11. 60
0.8
0.2
8.0
69.00
89.5Q
15.0
59.5 Q
13.7
6.24
63.0
81.5
65.0-
20.2
55 .0
21.5
52.0
72.0~
75.0
24.5
75.0
23.0"
.,
.. . .... .
.. ...
.......
33.0
45.2
34.0
Good
Good '
46,9
,
'"
,!
0.22~
10.0
'39.9
18.6b
0.32L
10 . 3
39.6
20.0
0.33"
25.4"
43.0
34.0
37.0
% 40D-900oF ......... , ..
Oct. No. (thermeJ) ...... , .
API gravity .. , ...........
Quality ... . .. '" .... , .. , .
Cra.oking stock (residual):
% a.bove 550D F ........ , , .
API gravity .... , . . , ., ., ..
API cracked fuel ...... ' ...
% gasoline (OD stock) .....
% gasoline (on crude oil) ..
28.8
SO.06
5.0 b
0 ,57&
25.0
49.0
25 .5
46.0
01.
- 20. O
Good
Good
51.0a
70.4 6
28.0
70.6~
Good
66.7
16.1
5.5
37.3
24.9
0.73
43.0
27.8
0 .85
Good
40.6
71.3
27 . 2
25.0
39.256 . 0
35.0"
0.31
-25.0
0.78
40.0
1.65
Lube
63.5 a
72.0
Excell.
29.0
~--
crmrn
.. . .
25.7
65.8
20.6
3.0
48.8
24.9
73.8 0
19.4
6.6
42.8
31. 6
32.1
15.0
21,0
22.1"
79.0 b
0.75
Low
1.6
28 . 2"
21.8 0
38,1
----68.0
65.0
31.7
39.3
37.8
Good
Good
Good
\
1 -. rt5Riiffin
0.06
60.28
65.3
16.4
5.2
15.0
35.0
68.5"
29 . 5
67.0
18 :0
-15.0
41.4
41.8
40.0
68.0
17.3
5.2
40.2
27 . 4
18.0
71. o~
Good
80 .0
53.0
1.75 11
13.8
34.3
13.0
0.02
Excell.
19.0 6
0.03
51.0
Good
4 .3
42.9
28 ,7
8.5
0.21
....
41.0
Good
Distillate or dleselluel:
9.7
40 . 3
19.0
21. 2
Excell.
Good'
'
79 . 6Q
.. ...
11.7
11.5
11.84
56 .0&
74.2"
13.6
26.0
26 . 0
0.12
159
1942-1951
11.63
11.69
I
Limau,
Sumatra,
Indoneaia
0.61
1.55
12.0
84 . 0
82.3
32.0
46.1
Good
Keroaene-diatilIate:
% 375-500D F .............
API gravity . ............
Smoke point .............
SuUur. % ................
Quality .... , ......... , ...
269
U.S.
11.9
59.1
78.0 b
19.3
4G.l
33.3
Good
26.3
Misa.,
0.7
. .......
Brookhaven,
.....
Good~
46.0
Tia Juana.
(medium),
Zulia.,
Venezuela
919
APPENDIX B
'.
Qatif,
S. Arabia
27.4
2.54i
75
'.
t,1~
Morel,
}{an.,
U.S.
Lake.
Tex.,
U.S. .
27.3
0.67
180
27.1
0 . 17
67
....
. ... ......
11.88
11.83
11.33
11.35
4-23--52
Steamboat
Talang
. ~utte. ...; Djimar,
Wyo.,
Suma.t.ra,
U.S.
Indonesia.
28.0
2.15
76
5-5-52 .
28.0
0.08
54
19S6
Amelia
(low cold),
Te1l:.,
U.S.
28.2
0.28
56
1954
Characterizat.ion factor:
a.t 250F . . .............. .
at 450"F ........ : .. .. . : ...
at 5500F ....... ... ...... .
at 750"F .................
Average ........ " ..... . ..
Base ............ ; .... . .....
12.18
11.95
11.66
11.67
11.82
11.82
1l.71
11.92
II . liS
to 300F ............. .
Jet stock:
% to 550D F . . ...... .. ... .
API gravity ..............
Quality ........... " .. " .
11.47
11.34
11.63
11.61
11.76
11.4
11.3-
11.44
11.80
~l.4a
IN
11. 51
Nl
0 '.9
0.3
11.76
I
11.52
I
0.7
0.8
0.6
1.3
9.7
45.0 4
.......
9.0-
4.44
69.5-
12.0
11.2
8.0
53.5"
..,
70.085. fig
20.3
62.01f
80.9"
27.1
17.0
70.0
83.2
22.8
Gasoline:
.Oct. No., clear ........ "
Oct. N"o., 3 rc TEL ......
% to 400"F ....... . ......
Oct. No., clea.r ..........
Oct. No., 3 co TEL ......
% to 4sooF ..............
Quality ....... '.' .........
11..64
11.4
PI
Loa, % ...................
%
12.00
11.78
......
....
88.0'
20.8
3i.S llo
18.24
25.6
23.3 4
12.44
63.5
84.0-
59.0~
... , ..
55.511 .
~
. ..
~
73.621.7
45.0 4
. . .....
. ....
18.3Good ll
27.0
36.24
38.5
38.0
.50.0
Good
43.8
38.0
36.3
37.0
13.4
41.3
19.8"
0 . 50
17 .8
35.7
~4.0
33.9
49.1
3.Q4
1.70
44.5
36.4
50.9
33 . 3"
47.5
. ... .
Good
. ......
375-500D F .............
13.4
4.4 . 3
21.9"
42.3
18.0"
17.3 4
33.8
15.0'
0.13
Good
Low
~xceU.
Excell
Keroeene-diatil1ate :
%
23.6 6
0.30
....
14.8
14
0.02
0.10
32.4
56 . 2
30:6"
51.0'
15.0
17.0"
1.59
48.1"
38.0A
-45.0"
0.2811
Low
40.7
44.4
30.0
0.04
-SO.OA .
Low
65.(}a
.67.0
69.0
29.5
53.7
69.5 11
29.5
....
49.1<>
70.24
69.4 6
29 . 6
Good
nOl>
52.S"
71.0
26.0
28.5
.....
73.S6
23.6
Excell.
63 ..24
60.7
55.3
20.3
15.2
3.2
48.9
30.9
4.6
19.5
0.5
36.3
50.0
22.0
27.6
18.9
88.0
60.5
2.61
. ........
24.1
Good
20.S"
26.8
Low
. ......
-25.0
40.0
Low
Ex cell.
ExeelL
I.
I
I
5.5
35.9
22.6
65.9 4
17.7
6.3
39.3
25.9
21.3
18.5"
62.9
15.6
63.4
24.6
4.5
54.2
34.3
90.0
56.0
3.05
......
2.5.3
.........
.....
69.0&
21.5"
. . . . .. .
41.0
Low
O.Sl b
. ......
3i.9"
.
......
. . .. . . .
27.8"
Good
.......
. .......
13.S4
Good.
Lube
15.7
920
Poza
Rica.,
u.s.
Gravit.y. API. ............. ,
Sulfur, % ...............
Viscosity. SSU at. 10OOF ....... .
Date ......................
{a.ctor:
s.t 250F .................. .
s.t 450F .... " ........... .
at 560F .................
at 7SO F . " .........
Average ..............
BII.E ..................
G
LOlliS,
% ...........
GuoIine:
to 300F .............. .
clear ........... .
29.1
1.64"
65
11.54
11.58
11.70
%
%
...... ..
1I'I.tU!:OUIU'
11.84
11 .27
11.24
11.52
11.47
15
.95
11.85
2.0
0.6
0.9
14..14
9.1
68.0"
82.0"
70.5"
12.7
56.5
76.0
22.0
44.0
65.5
27.0
22.4'"
57.0
72.0
27.0Good"
37.0"
19.5"
105
NI
Good
29.5
2.0
Quality ...................
0.31
11.98
11.08
PI
50.6
28.6
1942-1950
Jet stock:
% to 550F ............... .
API IiP"llvity ............... .
point. ............... .
Sulfur. % .................
Quality ........ ' .... " .... .
Mexico
38.0
17.0b
O.IW>
30.44
48.00
-6.0
1.1511
88.5~
19.1
64.0&
84.S1>
25.8
Excell.'
43.1
30.6
0.9
31.5
1.72'
64
47
6-2Q..S2
7-22-54
12.20
11.S7
It.S7
n.58
11.92
11.81
11.88
PI
11.66
I
11.64
I
0.4
1.3
11.95
.4
.6<1
71.6<1
22.8
08.2
86.7
25.2
33.5
29.1"
40.0a
61.2
61.0 11
ao.o
38.0
Good
79.3
89.5
47.5
54.8
50.2
11.7
12.1
11.0
48.7
23.0
0.46
22.Sb
37 . .5
18.0
0.28
28.0
58.0
28.6
06.01l
12.0"
1.11
21.8
4:9.0
Hi.Ob
46.0
69.0
46.5
71.Q"
26.0
Good
l.15
47.6-
65.9
47.0
72.0~
28.0
24.0
68.0b
34.3
61 0'"
15.8
5.6
68.3
0.29
a1.2
62.6
18.1
8_1
38.2
88.8
23.9
23.0
Low
19.0
85.0
11.4
90.0
Fair
90.0
77.()1>
21.3
1.9
53.0
29.8
21.4
1.95
Lube
HLI
Good
30.1
11.63
11.60
11.60
44.0
5.0
11.82
n.lI8
18,2
33.9
15.01>
Low
44.5
U.S.
1.67
81.9
36.5
50.7
33.0!.
Low
Elk
Basin,
Wyo.,
30.1
40.6
69.4"
36.3
22.2
VentllI'B.
Avenne,
Calif.,
U.S.
60.1
11.6
7.0
0.65
52.5
16.5
3.8
40.2
21.1
12.0d
39.5
18.0b
0.64"
30.6d
48.511
5.0&
1.16"
60.0"
7l.4~
25.9
Good
54.14
17.8
8.4
44 2
24.2
18.7
1.10
28.4
20.0
Good
19.0"
Good
921
APPENDIX B
Coaligna,
Calif.,
U.S.
31.1
West Teua
KuwAit,
KuwAit
31.~
2.59 1
0.31
48
.....
10-52
Charaoterization factor:
at 250F .................
at. 4MJOF .... , ..... :
at. 650F ...............
at 7600F .................
Average ................
B&ee ............
11.5
11.63
11.59
11.72
11.58
I
12.80
11. 92
11.78
11.70
1}.93
PI
Lou, % ................. .
1.1
Gasoline:
% to 300F. , ...........
Oct. No clear ..........
Oct. No., 3 co TEL .... , .
% to 400F. , ............
Oct.. No., cleD.!' .... : .....
Oct No., 3 ec TEL ......
% to 460F ...... , ......
Quality .......... , .......
Juaepm.
(eompoaite),
Monl\.&&8.
Ventuuela
Tex.,
U.s.
Lalo Mar,
Zulia,
Venezuela
32.4
1.03
32.5
1.721
46
1-80-42
........
1940-1948
31.5
31.5
1.41
67.4
19,56
58
11.70
n.SS
11.75
I
11.80
I
12.1
11.94
12.00
12.16
12.00
I
1.6
0.5
1.1
1.1
21.6 11
16.1.
72.0
52.6
75.8
26.8
40.8
20.7
65.1
76.0
31.7
64:4
67.0
87.1
15.7
64.5
83.4
......
31.6"
66.7 6
..... -.
35.6-
Ex~1.6
Jet atock:
% to 55<JOF .............
48.2"
API gravit.y .............. . 46.0"
Quality ................ _.
Good
...
31.6
........
41.3
65.9
.. ...
11.90
11.91
11.72
11.65
.....
11.fID.
11.70
17.9
58.~
26.0
61.0
77.5
31.0
Big
Valley.
Alberta,
Canada
O.99~
7-17-62
11.98
11.73
J1. 79
11.86
11.84
I
0.9
17.0
62.2"
78.51>
78.S-
26.9
26.6
43.0~
31.2
63.24
69.4"
31.2
40.2
55.0.
40.9
li1.4
66.0'
Good
45.0
4.2.0
48.1
Good
47.7
Good
..
&
.......
Good
Kerosene-dietillate :
% 375-5000F .............
11.0"
37.S
API gravity ....... .. .....
17.01>
Smoke point. ..............
Sulfur, % .... . ........... . . 0.06&
Quality ..................
12.l
18.2
43.7
22.511
0.35
40.6
19.0
0.~9
% 400-700 0 F .............
28.0"
48.56
11.1
43.9
24.06
0.2Sb
1l.7
40.6
19.1"
0.32
.-
]2.5
40.3
20.0
0.18
20.0~
0.27 6
. . ..
45.6
28.0
57.0
18.0"
1.36
'
30.5
50.0
5.0
1.17
......
30.0
63.0
-10.0
0.55
Z'l.7
64.0a
10.0'
0.6)b
Es.cell.
Exeell.
29.5
~5.74
12.oa
'0.67
Good
44.3
48.6
46.0
50.4
69.8b
30.8
69.0 6
33.0
34.5
68.3 6
30.1
57.4
M.t;
56.9
16.2
20.8
5.0
0.6
4.0
21.1
5.8
42.2
38.9
47 .9
22.2
22.3
26.1
17.611
14.6
. ....
58.0 b
0.431>
55.0~
13.8
80.0
73.0
1.87
42.6
69.4"
10.46
28.0
Good
30.7
52.7"
18.2
Low
58.7
16.9
58.2
46.7
26.6
10.5
33.0
19.4
6.4
41.8
24.0
18.6
95.0
. .....
18.3
20.9
~~.O
105.0'
74.0~
18.8
70o-900F~ ............
.....
.....
21.7a
Good
3.0
.... . .
29.0
........
...... .
23.S
Good
1.25
. .........
24.S
. ... ..
95.0~
1.06
Good
26.0
22.1
922
Name.
Suta
Barbara;
Monagaa,
Vimeauela
Southern
Oklahoma,
Old&.,
U.8.
Monu,ment,.
N.M.,
U.S.
KalimantaD
So. CUya.ma
Valley,
Calif.,
KaUm&ntlUl,
IDdoneei.a.
U.S.
(waxy),
,
82.0
Gravity, API ..........
0.0
8ulfur, % .................
Viaoo.iity, 8SU at l00D F," .. '...
Date .. ; ... , .. , .................. 1942-1960
......
Charaeten.at.ioD factor:
a.t 25OOF .... ~ .
at 4SOOF ..............
at D500F . ; ...
at 750F .....
11.88
11.63
11.66
32.0
22.1
0.82
........
1.801
64
1956
2-20-53
11.M
11.88
11.M
11.3
11.1
11 . 85
11.78
11.56
11.90
I
% . ...........................
0.8
1.0
Oaaolioe:
% t.o 8000F .................
Oct. No., elea.r ..............
, Oct. No., 3 co TEL . ........
18.6
64.7
83.6'
23.9
25.5
58.0
SO.D
39.0
60.0
30.1
Lou.
......................
"
...
Ii ...... ,
.....
a co TEL .....
11:86
11.93
NI
11.67
11.62
11.66
I
1.7
-0.2
1.0
16.0
63.0
20.068.01
22.5
2t.2
70. Of
79.0
81.5'
31.161 . .,.
75.Ot
36.1-
% to 45O'"F . . ................
28.6
Quality .............. .
Good
.......
Jel etoclt:
% to .6S00F. ...........
40.2
40.7
~.9
Quality ................
Good
M.9
Good
Keroeene-diatillate:
% 375-500"P . . ......... . ....
AP~ IrIlvity .... ; ......
SmOKe point .. , ............
Sulfur, % ...... : ...............
Quality ....... . ...........
13.5
30.5
18.D
0.18
11.9
34.0
52.0
12.0
0.65
Good
30.0
58.06
30. Sol
10.0'
-40.06
53.5
48.76'1.4
31.0
...
......... .
69.06
82.1
Good
42.9
22.46
D.H'
0:37'
Good
I'
..
59.0
mI .e
22.1
4.8
17.6
7.6
'-31 .'1
22.0
49.1
29~4
19.5
' 73.0
70.0
1.1
..
.... .
21.8
.... .
0.44
.6
.....
............
32."
1952
11.51
llA
11.49
11.56
I
li.?8
11.76
32.0
0.07
..
18.1......
82.0'
0.90
. -.. .
........
24:.8-
..
11.35
83.7'
36.0
61.3
37.4
62. ()t
'19. ()t
SO.6
39.0
43.6
Exce1l
....
'6.8
48.3-
n.65-
Good
1'2.7'38.0
16.6'
0.0511
4O.OA
0.9~
59.4
38.5
.... . ,
Good
"0.0
50.2
Good
18.7
32.4
13.0
0.02
12.0
38.5
42.1
37.8
30.0
0.06
29.0
49.0
15:0'
0.31
18.0
0.17
57.~
46.6
26.5
72.0'
25.7
70.7"
Good
Excell.
25.0
Good
52.~
40.4
60.0
17. 1
22.5
8.5
8.1
16.5
4.2
42.9
22 .8
62.0
21.0
39.3
10.8
14.0High
Low
17.1
45.7 0
72.26
16.2.......
88.0'
1.55'
. .. _ ...
Wu
21.0Good
15.401
a
1'1.15
Good
APPENDIX
923
l
:"'
El Cubo
Name, 8t&te, and country
(LaM Manuelea).
Zulia.
Vene.uela.
32.7
0.86
Kerosene-distills.te:
% 375-500"F .......... , ... . ....
API gravity ........ , ..... . .. . ...
Smoke point .... . , ....... , ......
Sulfur, % .. '" ... . ...... . ... .
Qualit.y . ......................
Distilla t.e or d ieBei fuel:
% 40D-700F. , .. . .......... " . .
Diesel index .......... '. , ........
Pour pomt.. '" ...... , ... . ......
Sulfur, % ............. .
Quality ........ " . .. , ............
CrackiDg stock (distilled) :
% 400-900 D F .......... , ... .. ...
Oct. No. (thermal) ......... ' .
API gravity ......... . ...........
Quality . .... " . . .. . .. . ... , ... . ..
% gaaoline
IOD
(OD
11.62
11.60
II.Sl
11.98
11.87
11.78
11.67
I
......
1.2
1.2
0,5
17.1
63.0
18.0
57.0
20.0
65.0
83.7
31.2
10.6
61.0'
70.0-
82.6'
83 .7 4
20 .8
34,3
56.8
77 .0
36.1
Good
51.8'"
74.0
21.2
..... . .
61.2
SO.S'"
89.0
12.25
11.85
11.85
11.80
11.95
12.10
12.00
PI
Sl,OI
......
27.6
50.0
73.0'
28.6
4.6.0
68.S
32.5
33.6
.... .
. .....
40.3
SO.5
11.9
42.9
22.6
0.15 6
Good
26.1
57.0
5 .0
0.38/0
....
12.6
44 .0
13.7
16,",
38.4
40.8
19.5 b
0.04
Good
18.0
24.0
0.21
.... .
0.11
&
30.6
28 .1
56.0
10.0
1.1
0.08
Excell.
52.0"
46. 0
48.3'
68.9 6
32 . 3
70.0
59 .7
22.0
8.7
....
55.4
.17 .7
6.2
47.2
28.2
39.5
25.9"
105.0t.
100.0
17.3
1.05'
Lube
20.0,
.....
&
21.9
&
4"
. ....
24.2
Good
Good
Good
S.O
0.62
67.0~
4.7.0
41.3
56.51
....
88.S
41.3
SO .O
Excell.
&
33,3
46.3
46.2
Good
43.4
51.5
Good
noek) .. . .. . .. .. ...
11.93
11.77
....
11.00
.or. g&80line
11.78
11.57
12.20
11.85
Jet st.ook:
% to ~500F .... , .. , .... , ......
API gravity ............ .' .... . ....
Quality ................... . .. , ,
C&lif
U.B.
0.32
o..o.
1-953
o.
La.,
U.B.
0.26
49 . 2
4-24-.'S1
82.9
2.08
2-12-46
South
8&n Joaquin
Louisiana,
Valley,
33.0
0.95
49.2
194.0-1950
Charaeterization faotor:
at 250F ........ , ....... , ......
at 450F ........................
at 5fiOOF .............. , ....
at 750F ........... " .........
Average . ....................
Baae .........................
G&80line:
% to 300F . . , ...... , ..... ' ....
Oct. No . clear ..................
Oct. No., 3 co TEL ..............
% to 400F ....... , ..........
Oct. No., olear ............... ,
Oct. No., 3 Co TEL ..............
% to 450DF., ............ , ... ~.,
Quality ...... . ............ . .....
Oficina,
Bahrein Anzoat.,
VeBeJluela
5.04
64 . 7
67.2.
33.6
11 . 53
11.64
11.83
11.66
24.0
EJ:cell .
49.6
49.5
Good
12.0
88.0
23.0
0.05
32.0
48.6
25.0'
0.18
48.0
69.0
31.5
Good
32.3
. ....
Good
52.5
21.3
50.4
20.5
3.3
48.6
26.5
58.2
24.0
6. 9
51.3
-l6.~
29.8
U.4
18.0
100.0
23.4
16.0
85 . 0
87.Ob
0.26
100.0
82.00.88
14.0
18.5
64.0
1.2
... . . .
19,4
.....
31.2
4.8
Fair
924
Barco
Paconaib.
Name,
8~te,
and country
Zulia,
(heavy).
Venezuela Colombia
33.5
Date ......................
1~5
Characteri..tJOD fACtor:
at 2SOOF .............
at. froOF ..................
12.1
12.0
33.S
0.89
.1.2
......
Mulata,
M;onagaa,
VeDeJluela
M.O
11.88
11.80
12.25
11.M
11.60
11. '10'
11.83
11.78
12.M
11.08
11.92
11.70
11. '10
1~.03
11.88
PI
11.78
I
1.3
0.1
0.9
Baae ........................
LON, % ............
1.0
0.6
1.1
H.5
52.0
72.6
20.5
41.0
18.9
17.2
67.3
82.8
28.2
58.6
Jei stock:
% to 55()OF .......
API gravity ..............
Quality ...................
31.0
.......
43.0
58.0
.....
M.4
0.21'
4.4
1-10-46
...... .
11.95
% to 4QOOF ...
Quality ....................
33.7
0.18
.......
0-66
12.0
12.01
PI
64.0
U.s.
1942-1930
07.3
6SC)OF .......
84.1
rado,
Kan.,
1.6'
at 75lY"F ..................
Average ....................
GaaoliDe:
% to 3000F ..............
U.S.
El D4)-
0.76
11.9
12.0
12.03
11.06
I
a~
Coaatal
B-2.
Ain Dar,
S. Arabia
6~2
86.5
27.8
49.0
69.9
31.8
I
77.6
33.8
... I
40.8
53.0
Good
44
o.""
1l.8Q
10.9
UUi
42.0
63.6-
64.0
28.0
34.0
84.021.3
50.278.5b
58.0
33.0
12.12
11.86
If. 78
11.78
PI
15 .
64.5"
28~2-
46.0
28.8
M.a-
50.3
44.3
48.051.0
Good
Good
Good
43.2
52.6
~.1
46.8
Good
. .......
13.5
39.0
13.0
43.2
20.0
Xeroeene-diat.illate :
% 37 6-S000F ................
API gravity ....... . ........
Smoke point .............
Sulfur, % ......... , ........
o
Quality ................
DiBiillate or djeael fuel:
% 4DO-'100"F ........
DleaeJ indes ...............
0
. . . .
',"
Sullur. % .........
Quality ................
13.8
12.~
4S.0
28.0
43.8
30.0
0.18
18.0
0.086
0.15
21.9
17.7-
'39.0
43.0
21.56
18.8'
0,26
0.035
0.086
......
Exce1l.
.....
. .......
Good
Good
32.0
26.8
62.0
30.0
58.0
25.0
48.4
54.9
..........
84.3
58.0
10.0
0.68
38.7
51LOb
15.0b
. . .
Good
63.0
5.0
O.ats
Excell.
~.O
.. ,
LOS
. ......
-3.00.11/0
Excell .
O.ID~
Good
51.0
45.8
50.~
~6.0
65.1
56.2a
67.0
34:6
66 .:5 6
6~LOb
32.8
68.2b
33.0
68.!)b
32.5
67.5
31.6
.........
. ..........
. .....
53.8
23.0
6.8
SO.9
27.4
65.5
49.0
50.2-
20.0
7.0
22 .7
6.0
19.0
43.2
49.8
48.1
24.0
24.4
21.6
16.5
92.0
16,,0
85.0
...........
73.0
BO.O
16.7
78.0
71.0
17.5'"
High
0,
00
Vjacosity index . .
56.0
22.0
7.5
08.1
46.6
47.1
27.6
26.1
19 .0
95.0
97.0
1.28
22.5
....
82.0
Good
22.3
7.4
19.0
.... .
~
26.7
1.12
20.2
. ..
2.15
. ... .
65.0'
0.39
12.9
Good
5.5
Low
24.2
..
. . .....
14.7
Fair
925
APPENDIX B
HeaJdton,
Okla.,
'Weld Texas.
U.s.
(oompoaite),
Tex.,
U.S.
38.6
84.2
0.77
58
BnlfUl'. % ............. . .
Characterisation factor:
at 2600F .... .... ...........
at 4DO"F ....... . . . . ....
Alberta,
Canada
34.S
44 .8
0.54'
48.1
~lM7
9--20-50
1.76'
... ..
RedwAter,
Hobbs,
N.M.,
U.S.
84.6
1.40'
42
H.BO
..11.70
11.68
I
11.74
I
12.0
11.94
I
1.8
1.9
Stab.
lIa.962.5'
63.011
M.o
85.a 4
51.0
72 .5
80.6
41.0
66.0
1.4
1.4
2.0
16. JoI
60.06
20.6
SS.i-
26.2"
31.6
36.111
58.0'
67.311
82.2
49.a-
63.'"
M.4-
. #.
64.~
70.8 4
30.7-
37.3
36.S
65 .0
69.Qt
.0 .2<-
Jet stook:
% to 51500F .. .. ... .. ........
API gravity .. ............
40 . .550.0
Good
48.8
62.5
GOod
48.2
53.3
Good
Lo-.
'}I, ..
GaeoliDe:
% to 300"F .. . ..... .. . .. ..
Oat. No., olear ......... . ..
Oct. No., S CCI TEL ...... . ..
% lo 4O()OF .......... . .
Oct.. No., clear ... ...........
Oct. No., 3 co TEL .........
% to 450oF .. . ...... .
QualIty ................
.....
1.41
11.81
11.80
I
Baae ........... . .
84.9
11.83
I
11.71
11.74
1.66'
4.2
11.82
11.73
11.71
11.96
11.72
11.70
11.80
35.0
Dammam.
S. Arabia
11.88
11.66
11.68
11.90
11.77
11.84
12.02
11.88
I
Cowden
North,
Tex.,
U.S.
12.06
20.2
78.'
. .....
60.1-
40.0
Good
24.1-
78 . .511
66.5 11
40.1-
49.449.0
Good
12.03
11.00
11.83
18.0
3.7 .0
47.4
M.8
Keroaen~dinillate:
11.9-
14.6
12.3
41.3
20.Ob
O.l'P
40 . 8
~. 3
19.2
19.1'
0.53
0.18
28.758.0
20.0'
0.34 6
Good
12.840.0
18.oa
0.56'
1I.S
41.0
19.0'
0.64 6
21.0
34.3
69 .0
35.0
30.2
29.7
28.9-.
28.~
53.0"
-6.00.7()6
Euell.
54.51>
48.0
13.0"
-3.06
53.0"
5 .0
0.39
. ....
0.98'
14.7
43.1
1.126
0.15
1.13
Good
46.~
46.3
47.7
42.8-
43.3-
67.26
32.0
69.16
30 . 7
68.S6
70 . 9
70 .0'
31.3
Good
.....
. .....
30.6
Good
5S.121.6
7.8
49.S
17.1
51.'S
17.3
6.2
45.8
88.2
19 .0
6.8
88.5
26.6
91.Ot
0.926
Quality ............... . .
Reaidue, % over goooF .......
26.8 0
18.0"
16. 1
.... .
. -. "
19.9
79.0
68.0'
. .... .
20.1
l
18.0
90.0
6S .0
0.62
18.7
Fair
28.2
48.1
48 .7"
19.8
4.4
61.0
67.66
32.8
62 : 6
23 .0
7.3
49.0
U .8
19.4
3.7
46.7
22 . 5
46 . 1
22.S
14.94
15.3"
.....
SO.O
43.0"
55.0 b
1.951>
85.0
19.5Good
IS.6
. ... . ,
1.68&
19.a ..
Good
16.7
2.1
.926
Seria
Golden
(wa.xy),
Spike,
Brunei,
Borneo
Alberta,
Canada.
Agba
Jan,
Khuziatan,
Iran
.'
35.4
1.11'
% ..... .. ...............
Viacoait.y, SSU at 10OOF ...........
Date ..........................
42.1
3-24-4.9
Chara.otenzation (actor:
a.t 250"F ....... ..... ,. ...... ,. ,
a.t 450F ..... .
,.
.....
,.
at 550"F ................
at 75O"F ......... , .......
3.5.8
0.21
48
36.0
0.05
35.6
0.2
1956
1956
12.03
11.6
.....
.., ..
..II
11.90
11.97
11.74
11.99
11.92
11.70
11. 71
11.19
11.83
11.86
11.48
11.91
. . ...
I
Loss, % ..........
0.05
35.5
0.79"42.5
7-16-52
. ....
36.0
1.36 i
4-5
2-50
11.82
11.86
11.82
11.75
11.78
11.4
11.4
11.5
11. 74
12.00
11.91
11.81
I
1.4
0.7
1.4
0.9
4.7
26.0
. . .. .
. ....
~
Gasoline:
% to aOOOF ..........
Jet stock:
% to 5.50D F ....... . ... _..
API gravity ...................
1&.411
40.0l
14.3"
. . .. .
SO.3 4
. ....
28.0"
29.7
54.7
34.7
32.4
26. I).
41.6
53.3 4
69.9"
38.0
48.5~
56.0~
60,5
38.0 b
74.2~
61.0 b
32.6"
... .
. .....
49.6
Good
70.7
40.2
.......
......
65.0a
..
..
81.9a
48.2"
62.8
....
48.9
44.3"
66.5
52.0
43.0
Good
50.4
Good
16.7 4
43.0 4
26.0
0.16 41
14.1
40.0
18.8"
0.28
14.5"
42.0
21.0 6
0.08 b
...
Quality .......................
20.0
50.0&
24.2
67.0
78.7
35.1
21.1
63.4"
50.2
51.4
Good
Good
70.0~
3004
35.0
44.3
1>7.0
Good
Kerosene-distillate :
%
875-500F ..................
0.02
12.9
38.5
23.0
0.04
Good
Fa.ir
Fair
32.0
35. ;24
53.0t.
59.0 6
2Q.a
65.0
17.0"
0.62
High
43.4
42.3
25.0
0.06
......
400-700o F ..................
36.2"
58.7
30.0
1.04
."....
..... .
.-
O.15~
. . " ..
21.1
86.1
17.0
SO.6
66.7&
5.5.4"
69.3b
33.0'"
... " .
30.1
67.5 6
32.2
54.8 41
73.0b
24.4
Good
. ....
Excell .
51.8"
21.7
7.3
44.4
23,0
49.7
19.8
5.4
44.6
22.2
55.0"
24.6
7.0
52.2
32.1
28.7
16.1
18.6
20.24
97.0
66.0 6
0.95
&.'.o
.....
2.16
..... .
18.6
..o
...
8it .6~
0.37 6
20.2
1.0
-50.2
44.0
.o
0.24
27.8
55.3
15.0"
0.826
Good
44.20
69.4 6
81.6
30.3
48.9
20.5
51.0
.....
......
, .. ' .
14.7
6.2
32.7
16.7
11.411
14.7
16.4-A-"
.o
85-.0-
.....
Low
,.o ..
.o
. ....
Lube
15.6
Fa.ir
IS.0"
2.2"
I,
Good
.o'.o
0.13
Fair
. .....
53.5 4
17.34
15.0
11.6
42.2
21.3 6
80.9
0.35
61.0 b
2.02b
20.0
20.7"
. .....
Good
927
APPENDIX B
,
New
Norway,
Alberta,
Canada
West
Texas,
Tex.,
Salt
Creek,
Wyo.,
U.S.
U.S.
36.4
0.82'
42.7
7-16-52
86.3
1.81'
36.2
0.17
46
36.5
1.36';
3-25-41
. ....
11.97
11 .M
11.74
11.73
11.87
11.86
11.85
11.88
11.76'
11.73
11.81
12.02
11.83
I
11.86
I
1.8
41.4
......
Abqaiq,
8. Arabia
.....
36.5
0.10
45.5
1937-1953
~.3
0.11"
1114-29
Cha.raet.eri21ation facior:
at. 250 D F, .......... , .... ' ,
at 450D F ...... , ........ ,
Ga.soline:
% to 800F ...............
Oct. No., clea.r ..........
Oct.. No., 8 co TEL .....
% to 400"F .... " ........
. Oct. No . clea.r ........ . .
Oct. No . 3 co TEL .... .
% to 4SOOF .......... .
QuaJity .................
Jet. stock:
% to 5SO"F ............
API gravit.y ...............
Quality . ................ ..
Kerosene-distillate :
% 375-500oF ............. .
API gravity ..... . .........
Smoke point ....... . ..... . .
Sulfur, % ..............
Quality ......... ' ........ ,
Distillate or diesel fuel:
% 4QO-7000F ...... . ...... .
Diesel index ...............
Pour point .. '........ , .....
Sulfur, % .................
Quality ... . ..... ' .........
Cracking st.ock (dist.illed):
% 400-900 D F . . .. . . . .. . ... .
Oct. No. (thermBl) . ........
API gravity ...... , ........
QuaJity .................. ,
12.30
12,01
11.91
11.71
11. 7
11.83
12.32
12.05
11.97
12.02
12.22
11.83'
I
11.80
12.00
PI
11.89
I
12.06
0.9
1.2
2.0
La
22.8
62.0"
78.2"
22.S
55.2"
19.14
17.0
65.7"
.. ...
19.7
44.5
20.7
66.6 b
84.0
52.2"
33.S
45.4"
29.8 4
68.6
31.8
80.8
.68.00
26.3
44.0b
37.8
" ...
35.8
Good
81.3
49.9
64.2
46.0
61.8
Good
42.8
55.6
12.8
40.2
19.0"
Low
Good
G9.5"
M.O"
39.3
89.5
....
t"
50.6
52 . .5
Good
.....
60.5"
r
..
....
35.111
,
. ....
51.8
4S.7"
53.3
Good
49.6
Good
36.0
63.2
.....
13.5
14.7
13.3"
15.3
40.6
19.1'
~2.5
41.0
44.9
21.5~
24.0
0.16
30.'1"
34.3
60.0
25.0
IP
13.3
44.0
24.0 11
.... .
. . .. .
19.06
Low
Good
30.9
52.7
33.7
58.011
57.0 6
15.0 11
0.71
3.Da
.....
Low
1.16
High
Low
High
0.39
Excell.
49.7
50.2
67.gb
32.S
47.5
63.0'"
35.7
52.9
30.5
49.5
68.4&
32.6
66.0 b
34.0
47.'1
47.3
50.1
21.7
5.1
57.2
19.2
6.6
21.9
11.3
26.7
9.3
42.2
20.1
42.1
19.9
53.1a
24.4
7.2
61.8
27.5
62.0
H'k2 6.S
48 . 6
42. S
22.2
64.2
31.0
19 .0 a
15.9
85.0
65.0
High
17.5
19.9
Wax
110.0b
0.26
Good
18.0
19.7
19.8
0.37
. ....
50.0
68.46
0.27
~
67.S11
32.0
... ' .
30.0
62.Q4
0.03
Excell.
33.0
.68.0 b
0.15
'.
19.1
15.8
96.0
84.0
7(}.0~
77.0b
91.0 b
1.01
1.52
' ..' .
16.1
Low
. .....
14.2
. - ...
. .....
19.3"
24.3
. ....
High
928
P~TROLEUM
REFINERY ENGINEERING
Bprayberry,
W.TBL,
U.S.
Gra.ha.m.
KIlD.,
U.s.
Mem,
Kirkuk,
Kirkuk,
Iraq
Tex.,
U.S.
Malmo,
Alberta,
Canada
36.8
1.93;
42
2-50
37.0
37.4
O.lS"
37.2
0.58'
44
37.6
0.22
43.3
1937
7-16-S2
1-1-52
11-1-49
12.00
11.98
... . .
11.96
11.88
11.95
19.02
11.92
11.12
11.80
11.78
11 . 72
11.93
11.79
11.92
I
I1.S8
11.88
12.00
11.98
I
11.95
11.86
I
12.00
11.85
I
12.10
11.84
11.82
12.01
11.94
PI
0.2
2.0
1.2
1.5
1.6
1.0
24.2
23 .
28.2
61.3"
26.2
21.1
64.4-
57 . 284.533.7
Cba.ra.ete:risation factor:
at 250"F ..... . . . ... .... _......
at 4SO"F . ...... .... ... ......
-at-l>500F ...................
at 75(1'F ............... " .
Average ......................
Base ..... . ..
................... .
5O.0~
a.ui
.... .
47
.....
.......
2()..6
......
.. I
62. ()6
.....
42 . 3
39.0-
......
....
... " .
. ......
39.1
. .....
52.1
48.8
58.6
62.0
72.0&
......
38.1
39.0
34.~
.... .
o.
_.
"
33.3
46:6'
. .....
76.7-
58.4"
79.6-
61.2-
40.2
. - ...
40.7
Good
40.0
50.8
61.4
sa.S
Good
52.1
60.6
63.0
(]()od
Good
13.1
407
)9.1
15.3
43.0
4.2.9
14..0
41.0
23.1'
21 . 5~
21.5'
19.06
0.12,
Good
Low
Good
0.28
.o.o.
29.3
.60.8
20.0
0.00'
44.7
46.0-
52.5
69.01>
67.2'
32.S
86.7
33.4
61.86
31.3
49.24
49.2
.27.3
47.1
20.7
6.7
F&.ir
~.1
High
O.21b
... _.
47.1
16.7
6.1
36.2
17.1
7.6
45.0
22.2
13 .4
17.0-
.. .. .
66.~
2,47'
...
o.
17.0Good
34.:;
62.011
. High
Low
29.0-
. .....
21.1
o.o.
..
89. ()la
0.6
,
....
18.0G
88.7"
85.8
67.6-
12.4"
60.0'
n.S8
34.6
61.9-
14.3
. ......
0.18i
40.1
43.3
0.32'
37.2
Illinoia,
Ill .
U.S.
32.4
56.4
16. ()4
0.47
Good
48.5
o.
0.03
Good
Ml.7
B3.7
15.4
42.5
21.1'
0.07
Good
28.2
liS.3
0"
0.07
Excell.
30.6
40.4
67.2
34.0
44.8
57.01>
11.00.13
Good
67.2~
33.1
48.3
56.8
7.1
44.5
48.0
20.9
7.7
44.S
28.0
21.0
21.3
22.0
18.0
..o. .
15.1
95.0
84.0
0.71
12.2
87.0
14.2
SO.O
76.0
S9.0
0.35
91.0 b
Low
Lube
13.0
15.5
0.24
22.8
21.5
7.7
45.~
20.6
929
APPENDIX B
COUDtry
East.
Conroe,
Tex.,
Char&oterizatioD lactor:
at. 250'"F ...................
at 45WF .............. _..
at 15500F ..................
at. 750F .......... _........
Average ....................
Texa8,
U.S.
Tex.,
U.S.
37.8
38.4
0.-12
85
0.33
40
3-a-42
. . .....
..... .
...........
..o. ...
1946-1948
38.0
0.04
42
S-2-51
38.6
1.4'
12.04
12.04
11.97
11.67
I
1"1. 75
I
0.2
0.9
1.2
1.2
1.9
5.3
28.5"
71.3
24.1
28.8
64.5
.o.
25.0
66.0
83.0
20.7
M.O-69.S-
39.6
85.8
40.0
36.5
22.4
58.178.2"83.3
59.0
-80.5"
57.0
78.0
58.0~
48.4
40.5
Good
58.0
78.0
44.3
Good
64.B
56.0
47.2
Good
48.7
Good
12.0
40.0
15.5
12.3
1-4.7
89.5
43.6
22.0
421.0
......
.. , ..
Excell.&
44.2
SO.8
50.0
Good
Good
22.4"
86.0
15.61>
Low
12.5
40.7
20.0
60.8"
O.Ga
.. .....
Good
45.2d
47.0b
-10.0~
M.a
o.
.......
45.8
18.5&
0.00Good
28.5
33.5
53.0
-4.0
0.19
52.0
44.5
ExcelL
67.010
40.8
68.6
31.8
35.6
aO.8
34.026.0
6.8
5lLO
IB.1
10.la
89.0
Low
Wax'
4.9"
Good
48.8
26.1
7.3
M.7
28.4
44.0
42.4
25.0
3.2
56.0
24.1
22.7
5.2
...
49.00
69.0r.
82.8
. .....
.II
...
........
. to
-10.0
0.35
ElI'ceIl.
. ......
15.0
80.0
...........
18.0
0.12
Good
58.0
67.8&
.........
11.82
29.5
15.0
0.19
Good
Low
Good
0.54
12.05
11.89
I
11.85
88.~
37:'7
11,98
11.89
11.04
1.2.01
11.96
I
Loss, % ......................
0.32
U.8.
Qat.if,
Zone D,
S. Arabia
11.90
11.60
11.70
37.5
Anzoat.,
Veneluelll
Buckeye
Pipeline,
Ohio.
11.70
11.61
11.68
11.70
11.92
11.72
Jet. stock:
% to 5S0F_ ...............
API gTavity ................
Quality ..................
U.S.
Guara.
(1ight.),
11.25
11.40
11.56
12.00
11.55
Nl
Gasoline:
% ~ SOooF ................
Oot. No., clear ............
Oot.. No., 8 ce TEL.
% t.o 400F ....... _........
Oct. No., clear ............
Oct. No., 3 110 TEL ........
% to 450F ........ ~ .......
Quality ..................
Kettleman,
Calif.,
12.3
95.0
102.0
0.36
Lube
18.8
....... .
,.
Good
- .. ,
18.0
50.4
21.3
15.5
100.0
72.0
0.8
........
13.3
5O.a"
72.0"
88.S
..
o.
t".
48.6
54.5
Good
0.12
Good
31.1
60.5
12.{)oa
0.3a
11.97
12.0
PI
31.9
44.8
62.6
37.2
. -.o. .
47.7
152.9
~.O
()'..80
30.4
6p.O
!$:.O
l.1S-
Good
47.2
66. Or.
34.9
45.1
61.3
83.8
45 ..1
47.0
20.4
7.5
43.7
22.3
20.6
1&.1
87.0
89.0"
1.08
Lube
17.6
14.7
&.0
49.5
21 .3
7.8
~2.0
2.2
17.7
930
Louden,
Ill,
U.S.
OkllL.,
U.S.
Mid
Couto
PlpeliDe,
U.S.
3S.8
0.26
46
39.0
0.18
42
38.4
0.37
40
0.29'
37.8
3~9-50
Fitts.
.....
. .....
11.94
11.80
11.72
11.90
11.86
11.96
12.13
11.84
11.92
Loss, % ....
2.1
Gasoline:
% to 300G F ... . ... , ... .
Oct. No., clear .. . : .
Oct. No., 3 co TEL ....
~ to 400F .... . ...... . ...
Oct. No., clear ... . ... . .
Oct. No., 3 co TEL ..........
% to 4500F . . ....... . .......
QuAlity .... . ... '.. . " ....
Jet stock:
% to 550G F . . ...... ...
A.PI gravity .. . ...............
Quality ........ .......
11.86
I
24..~
60.081.0b
35.761.6)
t
40.7"
.... .
39.9
0.78;
40
2-15-tH
1951
~20-49
11.94.
11.76
11.69
11.97
11.86
12.08
11.88
11. 94:
I
11.84
2.9
22.8-
... ,. ..
...... .
34.066. or.
. .....
39.16
..... ,. ...
60.0"
60.6
49.150.6
Oood
Good
Panh&ndle
Gu6re,
Fullerton,
An.oa.t.,
Tex.,
Venezuela
U.s.
.
38.1
0046
40.4
11.76
11.79
....
.-
11.95
11.85
Leduo,
Alberta,
Canada
11.76
12.03
11.81
I
11.92
12.02
12.22
12.03
IP
2.0
3'.8
2.3
1.8'
23.9
67.541
24.9
25 .0
68.6&
85.0'
78.335.2
66.083.0"
51.6-
72.439.7
75.60
43.6
58.0'
77.5'
39.9
Good
....
71.0
35.2
46.8
64.5
40.2
35.0
37.9
55.S-
. ....
23.0
55.2
53.1
01.7
Good.
04.6
49.6
49,4
63.9
Good
65.0
Good
54.3
14 . 4
41.1
U1.6'
12.3
40 .0
12.6
43.7
18.5b
2.2.0-
Good
Keroaene-diatillate:
12.6-
12. !}41
42.0
20.0"
42.3
15.0
42.0
0.06
Good
21.0'
Low
21.2'
0.15
Good
Good
Good
28 . S-
60.3
20.0"
0.181!
30.463.06
26.6
31.7
56.5'
Distillate
01"
0.07
0.21
0.08'
dieael fuel:
25.0) '
0.14)
60 '-~
17.0-
18.Oc
0.33
29.8
28.5
55.0'
8.DA .
0.22'
Good
62.5
12.00.8
Good
Good-
. . .....
Good
0.27
Good
43.S"
67.8'
32.2
47.466.2"
43.0
67.0'
34.9
48.1
68.3'
31.7
47.3
67.5'
31.0
44.3
67.61
U.7
44..9
21.5
41.6
48.1
48.8
8.6
19.0
6.7
20. 4
8.2
50.3
44.8
41.6
42.9
24.1
20.1
17.3
20.6
2l.2
8.8
52.0
25.4
17.0-
16.4
96.0
97.01>
0.73
Lube
19.8
18.4
17.~
4'1.9 11
24.6
5.8
53.3
25.5
34.2
48.0
24.2
8.7
11
(undewaxed):
14.84
..... .
78.0"
. . . ,. ,
101.0'
.... a
. , , ..
... a
Lube
18.9-
16.7'"
97.0
76.0)
0.47
&
10.2
16:8
.....
83.0
91.0&
93;00.4D .
Good
IS.7
......
Wax
15,4
'\
931
APPENDIX B
c.oun~ry
Gwinville,
Mise.,
U.S.
Santa
Elena,
etc.,
EouadoJ'
Michigan,
Mich.,
U.S.
MId
Continent,
Okla.,
U.B.
Sweden,
Tex.,
U.S.
Tez.,
U.S.
41.2
0.10
37
1-18-51
11.70
I
11.84
11.81
11.78
12.32
11.94
IP
1.1
44.2
2-10-45
.....
38
.. I
, .....
1937
1-10-37
11-8-29
i1.0
0.11
32
7-12-D2
Character1.zatJon faotor:
at 250F ................
at 450F ..............
at 55()OF ...........
at 76()OF .....................
Average .................
Base .......................
11.99
12.00
12.27
11.95
11.76
12.14
12.18
12.56
12.22
IP
.11.83
11.95
11.66
11.82
11.98
11.91
I
12.05
12.28
12.05
12.16
P
11.98
12.13
12.00
I
lL68
11.67
LoM, % ................
0.7
2.0
0.4
2.9
40.0
25.6
65.0
19.5
2:5.1
35.5
64.0~
26.1
66.6"
7.0
27.00
41.0
54.0
10.7
48.2
Gasoline:
% to 8000F ...............
Oot.. No., olear .............
Oct. No., 8 co TEL ........
% to 40ooF ...............
Oot. No., clear.: ............
Oct. No 3 00 TEL ...
% to 45(}"F .............
Quality ..............
Je1. stock:
% to oCOoE .............
API aravi~ ...........
Qua.lit.y ............
Keroaen&-diatilla.t,o :
% 37;5-500"F ................
APt gravity ..............
Smoke point .........
Sulfur, 'ro ....
Quality ...............
Distillate or dieaelluel:
% 4O~700oF ................
Diesel iDdex ...........
Pour poiDt. ............
. Sulfur, % ...........
Quality ......................
a9.9
0.14
...........
......
f
"
0.20
. ....
~
33.0
22.0
..
......
. ....
. .....
iO.9
... , ...
86.84
37.8
46.0
44.8
53.S"
44.1
79.0"
54.0
. ......
39.5
I'"
26.1
60. go.
84.7"
36.8
54.3"
81.06
42.9
Good"
Good"
61.0
56.0
72.9
67.6
......
.o.
58.5
Good
.o..o. .
53.6
Good.
47.2
Good
51. 7
Good
10.6
46.7
29.4'
0.02
Excell.
18.0
42.1
21.0&
0.03
16.6
43.8
23.0'
23.4
39.7
15.7
41.3
18.5~
20.5~
0.02
Good
Good
66.3
74.0'
39.00
38.0
Low
. . . o.o. . . .
- Qu&lity ....................
Reeidu.,. % over 900C'F ..... " ..
Asphalt qualit.y ........ , ......
.. ,. ..
40.~
61.6
25.3
48.6
"41.0
0.05
New
IDm.
57.0r.
High
...
o.
o.o.
..
........
61.5 b
67.01>
38.5
.......
74.0
36.3
88.6
.........
" ".'
66.3
49.0
..........
19.7
.....
......
..
82.0
140.0"
......
Good
&
o.
......
a'
.,.' ,
.... .
. ....
0.821>
.......
46.2
52.01>
00.06
Good
63.0 6
25.0"
,
......
..
47.0
20.7
8.~
43.7
20.5
18.0
36.0
57.4
3. (}<II
0.05
Ezoell.
57.6
M.S"
S5.0
68.2"
33.0
44.0
26.7
41..2
27.1
S.2
55.8
24.0
3.0
&4.6
25.6
10.8
24.6
14.6
17.0
8.8"
96.0
52.0'
0.23
a .
102.0~
0.02
66.2'
35.0
49.2
39.0
19.0
32.2
46.0
6.5.0'
68.0
93.0
0.3811
Good
Good
33.0
17.011
High
Low
86.0
11.4
Good
16.0
45.0
27.011
O.21b
Good
Good
18.0
......
a4.S
51.3
21.2
21.6-
Wax
932
Rincon
SIUI.
S&Il
Cran-
Largo.
U.S.
Anlloat.,
Venezuela
Joaquin,
AllIOai
Venuuela
Roque.
Aluoat.,
Veneaue1a
Miaa.,
U.B.
41.4
O.ISS
40.6
0.10
40.6
4LO
field,
w t
.......
. . . . . . . . . "-
'~''''''~''.~''''''~~4~p
..
..
.. ... .,A.
80.2
1942-1950
1940-1949
8--15-49
3--7-4.5
lL72
n.68
11.12
11.70
12.40
11.85
12.30-
11.88
n.92
12.00
12.18
11.88
11.99
IP
IP
n .... I>
...
1955
... '''''''
II-
Cb!Ll'1l.ci;erization factor:
at 250F .............. : .....
at 4.50o F .............
at MOOF ................
12,18
11.'15
12.02
11.85
n.70
at 1aOll'....................
A.vera.ge.. . . . . . . . . . . . . . . . . . .
12.35
12.12
&.ae ...
~ ~ ~
Loae. % ........
Q
...
..
'"
QA
...
..
......
.......
"
..
..
~,.~~
..
11
..
..
......
Ir
..
...
QUality ................
,
Distillate or die8el fuel:
% 400-700"F .... ' ................
Diesel index .................
Pour
SuUur. % .............. . .
Quality ......................
..
if'
........
... . .
25.2
66.0
84.0
....
. ..
24.1
68. or.
88.0
34,.,
11.70
n.8O
"
84.011
40.3
72.9
8S.S
78.5
60.6
80.6
42.1
Good
39.4
Good
Good'
61.4
'"
....
M.a-
66.~
87.0
..,
20.8
30.0
30.6
49.6'
i6.0
1.1
....
88.011
31.6
SS.O&
50.7"
80.0l
44.7
31.1
47.2
53.6
51.4
00.6
Fair
49.1
60.8
to.&
53.a
Good
Good
Good
Good
13.5
43.5
13.1
13.0
38.7
12.9
40.0
40.'1
43.5
16.5
Low
19.5'
Low
22.5
48.8
% 37i-:liOQ"F . : ..........
API gravity ..... "........
Smoke point ..............
Sulfur, % .............. ~ .
l~
'"
20.2
...... , ....
.....
11.00
IP
1.5
....ei stock:
% to MooF ................
API lU&riQ .......
-KeroaeDe-di8tilla\e.:
12.4<5-
"'Q~ ....
Gasoline:
':!J, to aOOoF .....
Oot. No., elea.r .......
Oot. No., 3 ce TEL.............
Sf, t.o 400F ...... , ........ "
Oct. No.. olear .................
Oct.. No. 3 co TEL ..........
llIjj, to 450F ... , . , .........
~~y .... ., ........ ., .... ~ .......... '" . , ~ ......
n.M
..
40.6
O.Hi
0.01
O.lD
'"
.....
,.
....
..
..
..
24.~
'"
to
....
19.0
Low
EJI;ceU.
Good
33.0
65.5)
High
Low
61.5'
...
31.3
5.01
0.1
..
Ii
'"
'"
...
31.7
51.5
32.0
0.14
14.0
0.02
Good
Good
29.3
88.1
M.O"
M.CV-
20.01>
0.0li1i
21.00.04
.. "' ......
Good
51.O<i
63.01>
49.0.s
66.0'
52.~
46.2-
66.21
66.21>
34.3
3&.0
35.6
36.5
14:.6
51.8
31.6
10.2
60.4
46.5
32.1
U.O
61.7
28.7
48.6
31.'1
10.6
61.5
42.6
50.0
30.1
21.1
8.6
00.2
27.6
.
61.0
65.6
Qualit;,v ............
.,
...
"
II
..
II . . . . . II . . . . . III
II
31.0
29.9
HOLO'
17.5
20.7
110.0121.0"
130.01>
182. ()!I
1.25.0
...
'"
.....
Good
17.O<i
0.25'
Wax
14.0"
9.6
S9.5
25.8
Wu
16.9"
116.011
118.0"
0.15/1
Wa.%
12.9
14.04
121.0
0.23
20~9
96.0
104.0b
O,26!1
Good
9.8
"
."
'I
933
APPENDIX B
COUDU'7
7000F .....................
Turner
Edmond
Valley,
Alberta,
Canada
Williston
(Madison),
OltlL.
Southwest
Oklahoma,
Okla.,
41.7
0.33
33.7
200M-51
'1.5
42.0
42.0
11.88
11.92
11.87
11.92
11.76
11.71
(w.> ,
U.s.
0.14
89
.......
11.97
11.82
,I
12.10
Average'................. . ...
Baae .......... , . .
Lo
2.1
28.8
24.1-
59.1
15.S43.0
56.~
at.
11,95
I
U.s.
0.22
N.D.,
U.8. ,
0.3~
8euml
Co.
Tex .
U.s.
42.0
0.33 4
..... .
......
1952
1965
9-14-S0
11.96
11.85
11.83
11. 76
11.80
11. 73
11.86
1l.7U
I
2.0
1.~
3.1
26.0
61.6
SO.li
40.2
28:&
80.1
64.0
n.88
l~.OO
11.9~
40
11.67
11.82
12.07
11.85
Guolin.:
" to 3000F .. , ...............
oa. No. clear ........
4JIi
Jet at.ook:
'" to 650"F .......... . ........
API gravity .......... . . " .
Qualit.y ............... .
51.1-
69.449.3
. - .....
62.1
52.0
Good
. .....
M.34.7.0
.....
40.~
....
.......
. ......
43.0
53.g.
'73.8
~.O
68.0
4.6.2
49,5
..... .
. .....
50 .053.0
Good
67.1
M.2
Good
63.0
49.8
' Good
13 .743.0
21.5'
16.2
42.4
17.0
41.4
-82.8
41.0
155.6
75.2
47.5
Good
liT. 8
M.8
Good
Keroaen&-~illate:
% 87S-S000F ................
API gravity, .................
Smoke poiut. ......... . . ,.
Sulfur, % ........ "
Quality ...................
Diatillate or dieae1 fuel:
% 400-7000F .... "...... , . ...
D ieae.l. ind e:I:.
Pour paiD' ..................
Sulfur, % ............
Quelit.y ...............
Craoking Hook (diatilled):
% ~QDF ... . ............. .
Oct. No. (tbermal) ..........
API gravity . .. . . . ........ , ...
Quality ..... : ... ~ ..... , ...
CraokiDI stock (residual):
% above 5WF ........ , .... ,
API gravity ......... , ... .....
API cracked fuel ........... ..
% gasoline (on nook) ...........
" guolin. (on o:rude oil) .....
Lube dist.illat.e (undewaJ:ed~:
% 700-goooF.. . .............
Pour point. ... . .... . .. . .. ; :
Viacoait.y iDdez ........... . .....
Sulfur, % .. '.... . .....
Quality ........... . ........
Residue, % over OOOOF ........
Aapbalt. qualiV ....... .. .
16.1
22.2'
0.08
20 .0
Low
Good
Good
........
14.0
40.5
22.0 .
0.07
Good
JUce1l.
Oood
36.2
63.0'
14.00.26
30.9
61.0' ,
31.0
84.0
53.5'
56.1i
2li.O'
Low
50.0
12.0
0.11
.oo .....
..
Good
..
52.0
47.9 4
66.2'
33.3
~.6e
4B.04
68.0'
48.0
66.li
34.0
30.7
33.2
36.6
27.0
39.1
2O.S
41.1
19.70.11
68.2'
31.4
.......
......
....... .
..... .
29.0
2 .0
0.29
Exaell.
66.~
36.9
47.0-
4.0.0
23.3
6.9
26.7
22,4
7.9
8.5
4 ,9
8.2
49.9
18.4
65.3
26.0
46.7
57.8
21.1
43.0
15.8
95.0
17.0-
14.6-
14.0"
ffI .O
86. Or.
98.0
14.0
83.0
65.0-
0.56
Low
Lube
14.7-
.........
4.0
....... .
19.1
.........
97.06
0.3e&
7'0 .0'
. ........
12.211
8 . QII
16.8
O.~
12.0
934
Fa.rmen
Valley
(composite),
Pa., U.S.
Gravity, API. .................
SulIur, % ............
Viscosity, SSU at lOOGF .... " .
DILte ............... .
Charac\erUat.ion faator:
rot 250"F ................. - .
at 450"F ................ : ..
at. S500F .................
at 7600F .... .........
Average ....... , ....... .. .
Baseat ........ , .......................
lao e.,
Chile
EI Cubo
(W. Tarra).
Zulia.
Venezuela
41.9
42.S
Maga!-
42.4
0.09
40
10-31-49 .
0.04
37.4
12-55
12.04
12.12
12.20
12.45
12.20
P
1.72
11.82
12.00
11.85
11.92
12.80
11.96
12.06
12.21
12.22
12.40
12.22
P
11.99
12.05
12.22
12.60
1.2 .19
P
0.3
1.41
19.2
24.79
SS.64
12.0
IP
1.0
.......
28.0
68.0 6
85.0
88.0
49.0
78.0'
47.0
Good
23.8
69.0
85.0
35.1
43.0
65.0
40.1
Jet atack:
% to SSOOF , ........
API gravity ...........
Quality ...............
Kerosene-diatilla.te:
% 875-5000F .................
API gravity ........
Smoke point. ........ . ...
Sulfur. % .........
Quality ........ , ....
Diatillate or diesel fuel:
% 400-700"F ................
Dieae1 index ..........
Pour point ...........
Sulfur, % ..... " .............. a
Qua.lity .......... , . ,
........
49.08
S6.1
......
12.7
46.1
29.0
0.06
Excell.
..
.......
51.3
~2.8
14.0
43.8
32.0
0.005
Excell.
29.9
32.9
60.0
Good
. 20.0
0.013
Good
46.2
48.9
63.3~
6.... 0"
34.6
37.6
..
.....
...... '.,.
..... ...
32.7
76.6"
37.49
36.5
45.8
89.7
42.59
58.0
64.0
63.0
56.5
52.49
57.0
18.7
44.4
17.2
J~~7
47.2
45.9
25.4"
33.0"
Excell.
Low
Excell.
29.0
0.07
"
........
66.0
Good
72.1
15.0-
0.08
. . ... . .
12.00
12.30
12.06
IP
21.28
67.7"
38.98
0.06
43.9
1952
M.l"
74.7"
42.8
0.28
1948
aooop ..................
38.98
44.S-
La.
U.S.
Seneca.
Pipeline.
Olean. N.Y.,
U.S.
0.10
40
11-29-49
% to
Rodesaa,
. ......
37.4
Excell.
33.0
67.0
10.011
0.07
Good
.........
45.0
.........
...........
Go~.
49.06.5.3
52.5
63.0'
46.0
37.~
4.0.8
37.9
42.0
28. 4
46.7
28.9
28.9
70.6
15.0<0
0.08
63.2~
Quality ...............
49.2
47.7
28.4:
38.a
9.2
64.2
11.8
55.1
27.1
30.6
10.0
11.2
46.1
28.S
11.9
66.6
23.7
56.5
26.4
55.4
20.4
15.1
.108.0
17 :1
% ~~ ................
J6.3
.95.0
8u1Iur. % ....
Quality, ...............
Reeidue, % over 900"F ...........
Aaphal' quality .......
16.0
H.igh
15.5115.0'
87.0
106.0'
125~O<t
'110.0
107.0~
0.10
Esctill.
18.1
118.0'
0.16
.. . . . . .
Lube
13.0"
Excell
0.14
Excell.
. ...........
.
15.0
.........
14.6
UP-I
935
APPENDIX B
Cha.re.oterization faotor:
at 25O"F ......................
Loa,
Gasoline:
,;, to 300D F ..... ', .........
Oct. No;, clear .. : ......
Oot.. No., S co TEL ...........
% to 4001" ........... ' .......
Oct. No.1. clear ........... ' ...
Oct. No., a co TEL.; .........
~ to "4S0Cl F ...... '........
Quality . , ................
Jet etock:
% to 560F ..................
API gravity .... : : .............
Qualit.y ..... '.............
Kerosene-distillate :
% 375-J500F ..............
API gravity .... : ...........
Smoke point ..................
Sulfur, % i ;.........
Quality ...... , ...' ..........
Atlanta.
(limestone),
Ark-.
U.8.
Dj&mbi
(NIAM).
Sumatra.
lndoneaia
Gr&S8
Creek,
Wyo..
U.S.
43.7
0.08
44.5
4S.0
0.03
45.8
0.10
1945-19S0
.......
Ii. 70
11.65
11.82
12.06
11.65
11.S11.8
I
2.9
Santa
,A.Daco
(wa.x blend),
Rosa.
Anzoat.
A.n.zoa.t .
Venezue1& Veneauel&
..... .
11.70"
11.6'2
11.70
12.35-
0.48'
35
IP
'IP
1.2.08
12.26
12.05
IP
. .... .
. .....
).5
35.8
69.0
86-.7
46.0
60.6
SO.O
34:.4
66.0
88.0
48.6
60.0
82.5
51.8
Good
54.0
Excell.
63.4
48.6
Good
13.4
12.20
11.76
11.84
25.2-
. ....
11.96
11.58
11.9
~.6
45,3 0
61.61
81.S.
61.2
61.511
. 74.7'
68.4
64.5
66.8<-
79.9
48.5
Good
57.4
......
49.3
Good
14.5
3B.4
11.8'
15.0-
39.4
18.21'1
46.0
Low
Good
Low
18.2
39.5
18.0
0.02
Good
....
I.
'1.
.......
89.248 .61
......
21.0'
0.06'
Excell.
34
1966
11.62
11. 72
11.81
12.08
11.81
I
1.6-
38. 7-
. ....
~2.1a
69.0'
57.1"
68 "
51.'
Good
13.9"
40.4
19.QI'I
Low
Good
% 4:00-7000P . ..... . ..
- ..
28 . 8
52.3
3.0'
0.07
Good
35.5
52.0'
10.011
O.OS'
Good
36.076.01
High
0.151'1
.'
....
80.0
57.8
25.0
0.04
28.366.0110
20.0'
. ....
Low
Good
:Sl. 441
3S.9-
M.51'1
68.310
38.S67.811
.3.5.0
43.5
67.2
84.0
35.5
30.4:
34.0
36.6
35.5
36.S
35.2
9.1
68.1
24.9
7.4
61.4.
24.0
42.227.1
9.6
&4.9
23.2
17 . .2
24.6
5.2
54.2
9.3
. 80. ()ca
29.7
7.1
60.1
18.0
41.4
67.01'1
, ........
12.6
8.0
16..4:-
115.0
111.0 1
108.0"
0.251'1
Wax
.......
7(Jo-9000]'~ ........
135.0
0.16
Was:
12.6
8.0
5.4
10.5-
113.0"
Low
97.0'
O.S&
... I.
Low
Lube
Excell.
7.9-
.......
II
....
7.5
936
at.a~
Cumarebo.
Falc6.n.
u.d country
47.7
0.01
48.1
...
Average ................
BaM ..... ~ ~
~
~
~ ~
~
$
..
"
....
..
'
G8.IIoline:
% to 3000.11' .....
Oct. No., clea:r ........
Oct. No., 3 co TEL ............
" to 4000.11' ..........
Oct.
elea.r ........
Oct.. No 3 eo TEL ............
% to 450F..................
Quality ....................
11.91
3.4
..
40.6-
49.~
15.9
57.4
56.9"
"'
Ke.roaene-diatilla. is:
% 315-500 oF ................
'"
...
51.&!
....
......
.'lO~Q
67.411
64'. '1
M.O"
.........
Good
---
U.S.
49.7
0.8Qi
37
11.88
12.1
12.08
12.1
12.04
12.12
12.2'8
12.22
12.80
12.25
2.9
3.0
2.9
4:1.7"
36.0
64.0
83.1
28.S-
62.0'
84.51'
59 . .5"
.53.0
76.0 411
66.S'"
Good"
18.S61.8
5LO
55.a
28.011
77.0
57.0
81.S-
66.5
66.3
67.3"
44.1"
65.10
GOod
Good
13.6
45.0
80.0
0.02
49.0
40.011
0.1511
Excell.
Good.
25.6
67.0
20.0
0.076
33.&0
78.0"
35.0b
0.266
31.0
66.0'
34.0
64.5'
39.0
32.OC
28.8
13.So
18.34
41.(1
.21.0
Low
Excell.
Low
Good
Low
Good
58. oro
27.34
2'9.64
&2.071
15.0'
Low
Low
44.3
r.".,..1 ........
,
'--',
5-S6
11.68
43.1
23.00
15.8
.. * "
ai.9
.....
11.73
11.77
I
0.10
It
11.92
...
48.1
., .
'"
12.20
12.06
84.9
S2.4
61.3
56.5
'"
..
11.91
H.14
n.86
Ba.rCD
(light.) ,
Colombia
48.8
0.10
11.92
U.94
..
U.s.
.....
" "
87.1i
Jet atook:
% to S5oaF .......... ', ... "
API gravity ........ :
Quality .....................
01'
34
........
Luby.
Tex
12.10
11.95
12.00
..
LO.II8. % ...........
DiaWlate
0.26<
1944
7600P' ...................
.,
KAD.,
U.B.
CbarActel"ba.tion factor:
lILt 250F ...................
at (50011' ..
At 5600.11' ........
Cha.se,.
Ve08lme1a.
lILt
19.5"
18.80
diesel fual:
% 40G-1000F ................
Diesel iDdeJ& . : ..
Pour point ..... , ......
Sulfur, %".
........ " ..
II. II . . . . . .,
Quality . ... a. ..
&
IJ
....
....
...
OnaJitv ..............
....
........
Good.
Good
.........
"' ................
34.4
66.0
20.0
0.09
43.3
M.O
.......... ..
~
"
"
......
II
3'1.167.S"
34.0
......
35.60
'10.0
33.2
Good
18.36
24.6
3.1
55.1
30.5
26.6
65 .. 9
29.24
25.S
5.9
55.4
19.8
16.2
10 1
30.0
34.0
1.7
9.84
85.0
100.0+
0.23
Excell.
5.4
.. " '"
"''''
81.0
. .. ..
. ...
'"
'"
~
"
7.9-
4.5.0'"
6.0 a
.......
1.9
10.0
6.5.1 -
16.8
67.1
18.3
ll.a
12.0-
59.0'
"""
.. ..........
Low
.. .. .. .. ..
.. " ,. ......
2.0-
9.0
HS.O
0.866
E%OOIl
1.5<11
937
APPENDIX B
Caico
8eoo,
Anzoa.t..
Vellelluela.
I,
Jet stook:
% to 550"F ......... ' .... , ....
API gl-avity .......... .. ....... ;
Quality ............. , ..........
KerOllene-distillate:
% 375-S000F ........ . .... , ..
API &l1'vity ...................
Smoke point ...................
Sulfur, % ............
U.S.
Camiri,
Bolivia
El Roble,
Anzoat.,
Venezuela
52.8
iO':1~46
3-15-50
12.05
12.10
12.10
12.20
12. 11
p
12.34
12.41
12.34
12.47
12.89
12.35
... .
2.9
O.li
. .....
31.1
36.6'"
61.94
46.2
12.8'"
44.7
58.1
66.6
60.1
86.5
Gasoline: D
% to 300 F ....... " ...........
Oct. No., clear ....... ... .....
Oct. No., 3 oc TEL ...........
'lIi to 400F ........... .... .....
Oct.. No., clear- ...............
Oct. No. a ell TEL ...........
% to 460 oF ....................
Qu.tity ............... ... ......
CS.,
49.7
0 . 13
Character-DatioD factor-:
at 250"F ......................
at; 450"F ......................
at.. 550GF ......................
At 75O"F ..................
Average ........ .. ...........
Loaa. % ...... . .............
P?,uus,
. .
34.3
M.O'
83.0'
55.3
52.Qt
0.04
33
54..7
0.02
. .
.
1941
12.04
11.08
12.18
12.14
PI
.......
64.6
44.8
54.6
0.09
. ......
1945-1950
11.75
11.55
11.80
12.25'"
11.86IP
Sa.nta
Anita.,
Bolivia
57.0
0.02
80.2 at 70""
195&
12.10
12.06
12.02
12.16
12.08
PI
2.8
50.9
52.0
76.6
69.6
69.2
64.2
39.2
00.0
76.6
......
83.2
73.7
Excell.
68.2
61.0
. ..........
83.8
... - .
81.0
56.8
Good
87.5
58.4
49.0
19.0
18.7
45.4
38.2
10.4
17.7
46.7
Excell.
Exoell.
0.02
Ezcall.
. ......
41.5
87.0
28.8
20.5
53.0
74.0
68.0
.........
91.0
56.2
.
... , .
30.5
46.0
33.2
0.04
68.0
20.011
0.11~
46.0'
53.8
45.2'
0.03
81.5
28.0
0 . 04
72.3
. ...... .
59.4
.
High
lligh
25.0
0.04
17.0 11
Low
15.0
0.17
80.0
0.021
Excell.
23.6
70,0
10.0
O.O!U
E:&cell.
Good
......
42.2
41.5
62.S'
83.4
44.9
65.5
38.1
26.8
66.510
37.5
28.9
26.7
12.4
1.5.7
31.0
45.7
32.3
15.2
9.7
6.2
80.3
15.3
64.3
6.2
65.0'
38.0
2.5
.....
......
......
.....
0.7
110.0b
110.011
0.30
Excell."
Trace
52.5
10.6
68.0
115.0
Low
Ex cell.
3.4
..
4.6
lIigh
High
1.6
19.0
8.0
62.0
....
..,.
6.3
120.0
1l8.0~
0.24
~
Wa.x
4 .0
26.6
65.0'
31.0
9.7
7.4
2.9
98.0
111.0
0.09
Good
0.1'"
,
I
'I
INDEX
Absorber-fractionatof, 721, 829, 845, 860
Absorbers, 823-827, 846-848, 850-861,
'885
diameter, 494, 495
Absorption of gases, 494, 498, 692, 721,
727,823-827,846,850,885
Absorption oil, 55, 551, 827, 828, 853,857,
860
.
Acceleration, engine, 39, 40
Acid corrosion, 282-284; 289-291
Acid sludge, 289-291, 313, 319, 331, 336,
364, 416, ~26, 740
.
1088 by, 295, 337, 364, 871
l\.cid treatment (see Sulfuric acid and
treatment) .
Activity of catalyst, 729, 764, 766, 782787, 808, 809, 816
Additives, 7, 18, 36-38, 54, 57, 62, 6467, 71, 873
,
Admiralty met~l, 283, 284, 290-292,
545
Adsorption, for color, 293, 308-313, 330,
331, 33~342
fractional, 342-346, 880 .
Agitators or agitation, 289, 297, 313,
335-339
Air, 419, 420, 4,23, 426, 597, 602, 827,
876
Air cooling, 8, 540, 827
Airlift, 8, 761, 762, 804-808
Air preheat, 588, 589, 602, 791,803
Airblown asphalt, 165, 261
Alkylate, 698, 700, 737, 738, 740
Alkylation processes, 222-224, 698, 700,
735-743
co~,872-875, 878, 886
hydrofluoric acid, 700, 737-739
auHurie acid, 295, 700, 738-741
thermal, 700, 741
,
Alloys and a.lloy steels, 276-292, 313,
319,' 545, 816
. :1
i
r~
,,'"
['
153
Anti-icing agents, ~
Antiknock properties (866 Octane num..
ber)
of hydroca.rbons, 184-187, 210-214, .
738
Antioxida.nt additives, 7, 38, 65, 66,
873
API (Bee America.n Petroleum Institute)
Approach temperature, 882, 883
Aroma.tic hydrocarbons, 11, 12', 77, 78.
81, 156, 387, 629, 649, 714, 722, 767.
814
939
.1
940
PETROLEUM
.
RE~RY ENG~EBrNG
-l-~'
941
INDEX
341
Brine in crude oil, 92, 94, 265-268, 280,
549
hydrogenation, 748-750
isomerization. 751-753
polymerization, 727-734
reforming, 811, 818
regeneration (ue Regeneration of
catalysts)
(See also Catalytic cracking, ca.t;8...
lyst handling)
Ca.talytic-cra.c~ed products, 135, 136,
156-160, 7.59, 763-778
distillate fuel or cycle stock, 135, 136,
156-160, 775-777
gas, 760, 76l~ 767-769, 773, 782
gasoline, 16, 29, 42-44, 135, 136, 767,
768~ 772~774, 776.788
~talytic cra.ckfug, 7, 219. 222-224, 700,
759-809,872-875,878
B-B cut by, 417, 720, 768, 769, 773.
a.fter burriing, 793
carbon burnoff in, 364, 768, 772, 781,
789-793, 800, 803
ca.talyst for, 783-789, 801, 808, .809,
811
cat,alyst handling, 761-763, 785, 787,
789-793, 795, 797, 798, 800~ 803,
805,809
catalyst-to-oil ratio, 763-767, 799
cha.rge stocks for, 257-260, 335, 349,
355, 357, 358, 364, 365, 764-766.
771. 772,779-783, 804, 808
coke loss, 364, 768, 772, 781, 789-793.
803
contaminant metals, 9, 71, 259, 265,
298, 355, 364, 365, 781-783. 787,
805, 808
942
Catalytic
heat of reaction,
712, 794-796
1088 of catalYst, 783, 787) 788, 799, 801,
805,818
rate, 760, 797, 803
reactor opera-tion, 761-763, 793-798
recyCling, 760, 764, 768, 773, 776, 779,
780, 799
reforming by, 222-224, 779, 781, 782,
809,811
'lepJleration, 761-763, 784, 787,; 789793,799-801,804,805
severity factor, 765-767, 769' '
slurry oil, 560, 551, 788, 801, 808
!u1fur in, 135, 136, 764, 782, 787
temperature, 763, 766, 769, 776, 793,
794, 799
yields by, 764-773, 777, 778, 781,782,
788
Catalytic-eracking proceaseB, 700, 759,
761-763, 798-809
Cyeloversion, 222, 700, 759, 761, ,762,
, 792, 799, 808, 809
Houtt~d,779J808
806,382, 38a
325-830,335,346
Centrifuge dewaxing, 4, 217, 221, 374,
380,382,383,874,875
Centrifuge trea.ting, 297,' 336
Cetane number, 56--58, 156
CFR (Cooperative Fuel Resea.reh), 28
Cha.nnel black, 821, 830, 843
Chara.cter.bul.tion Fa.ctor, 58, 81-86, 161164,169,178,205,447,628,765-767,
770, 774, 775, 777, "781, 844, 845,
910-987
ChemicaJ. manuf&ct'l.U"e~ 5, 7, 8, 76-78,
244,410,418,659,694-758,819-821,
828
alkylation, 222-224, 698, 700, 735-743,
872-875,878,886
butadiene, 648, 719, 720, 745-748
costs, 871-875, 878, 880
'decomposition, 626-628, 633, 644-654,
659, 692, 695,.700,113-725
dehydrogenaUon, 7,644-648, 669, 700,
743-748, 810, 812
ethylene, 644-602, 716-'121
proeessing costs; 872, 880
heat of re&etion, 632-635, 712, 716,
722,737,745,748; 758
hydrogenation, 6,8,699,700, 712, 748750,810, 812, 814, 816-818
isomerization, 698, 700, 711, 750-756,
810, 812, ssg
poly~eri.zation, 222-224,244,415,418,
60~ 655, 692, 697, 700, 722-735
cos~J872,873,878J880,886
INDEX
/
582-584
Coke, 8, 73, 74, 134, 218,' 416,529, 641,
687-691
ca.talytic, 76&-769, 772, 780, i8l, 789793,803
Coking of tubes, 590, 622-6Z5, 652-657,
665,670-685,717,720 '
(See alBa Delayed Coking)
Coking processes, 222, 608, 642, 679, 686692, 700
costs, 872, 874, 875, 878
.Cold-eettling, 4
Cold test, 27
Color, 37, 52, 59, 61, 123, 22&-228, 241,
808
test methods, 23, 24, 389
by treating, 294-296, 331, 335, ,337342
411,425-427,565,581,592,596
ca.talyst (lee Catalyst regeneration)
cost of fuel e.nd power, 72,425, '874-
876,884
581
re~e,452,827
944
~B,27~278,
286, 865-8&1
Crack per pa.ss (see ConveI'!rion per pa.ss)
Cracked:prpducts; 82-85, _ .217-21~, 628632,. 774-777
.632,
63~,
834
gas oil, 54, 73, 84, 85, 134-136, 158,
217-219, 221, 626,628,629,687
(See also Recycle oil or recycling)
gasoline, 11, 12, 16, 29, 42-45, 84, 85,
133-136, 148-151, 217-219, 221224, 241, 297, 300, 301, 326, 330,
626, 628-632, 637-641, 761, 768,
772, 774, 7.7 6, 788
Craeking, thermal, 217-224, 262, 608,
. 626-693, 872-875, 878
butane, 608, 627, 644-649, 651, 654,
659, 713-:-721
c~ocksfor, 608, 635-642, ~
667,678-681,691,910
clean circulation in, 655-657, 679,
680, 682, 687
coking of tubes, 622-624, 653, 656,
665, 679-685, 717, 720
(See also Cracking processes)
conversion-pet-pass and recycle
ratio, 626, 652-660, 668, 680, 681,
691
cyclertime effieiency,-224, 678, 682
effect on, of :Pressure, 631, 663-666,
671-673, 67.6, 683
of temperature, 64H52, 660-663,
671-673,' 680. .
ofthne, 652-666, 666, 673-678,
680, 714
furnaces,
608~
668-678, 680,687
718,720
reaction chambers,,63.8, 653j 683, 687
872-875,878
catalytic (8~ Catalytic-cracking
processes)
874, 878
gas crack:ing, 608, 629, 644-649
Houdresid, 779, 808
Houdriflow, 8, 222, 759, 761, 762, 784,
792, 799, 804-808
Houciry,. 6, 7, 222, 700, 759, 761-763,
787, 792: 799-801
Hydroforming, 7,222,' 700, 759,.761,
762,810,811,817
Hyperforming, 811
liquid or mixed phase, 665, 678
Polyforming, 630, 631, 681, 700
reforming, thermal, 8, 222, 608, 630,
631, 638, 679, 691, 692, 700, 759
. I
INDEX
945
urea, 8, 384
Diesel fuel, 56-58, 156-161, 215,348, ,353,
354, 357,358, 910
Diesel Index, 57, 58, 82, 83, 88, )59, 776,
777, 910
Diethylene glycol extraction, 366
Dilution-ratio tests, 45, 152
Diolefin hydrocarbons, 11, 12, 77, 293,
297, 366, 627, 628, 648, 714. 745,
750
(Bee also Butadiene)
Disposal, of hot oilj 270
of water, 268-270
1
j
I
II
.t
i
"
946
PETRO~EUM REFiNEKY.ENGINEE~G
~ononrlcalapproachJ
882-883
Qe8ign,
865-888
Economies
of
219,22~22SJ416J628,641,642,774777
Economy of fuels, 72, 884-886
Distilla.ti~)D, 22, 9(}-126, 226-262, 434Edeleanu treating, 6, 300, 348, 352-354,
873
.
--527
ABTM, 22, 119-121
.
EfficiencyJ bubble plates, 482, 497J 498,
venms"T.B.P., 'UI, .112, U5, 116
517
a.zeotropic, 233, 463
stream-time, 224,678, 682, 733,.738
Ejectors, 253-256
batch, ;108-115, 435-437
brigh~k, 228, 248, 250, 608
Electrical desalting, 267, 872
Canier, 25l; 462, 779
Emulsions in crude oil, 265-268
of Crude oil, 90-92, 98, 218, 220 i 236End-Point, 22, 34, 46,53,55,56, 119-121,
238, 248-252, 871, 872, 874-876,
375t 476
878
versus T.B.P. ~l1t point, 119-121
Engine acceleration, 39, 40
destructive, 248, 608
extra.ctiorl, 282, 463, 880
Engine or machine oils, 5~6
. iractioiiaI, 99-102, 465-527
Engler distillation, 22
Enthalpy, 169-1'11
Hempel, l11-U5, 120, 121
bigh-tempen:ture. 1()2-,-104, 248,
Entrainment in bubble plates, 477, 487608'
.
493
Equilibrium, in extra.otion, 366-373 .
na.tural gasoline, 242-244, 264, 512liquid-liquid, 299-302, 366-373
514, 823-828, 861-864
Sa.ybolt, Ill, 112, 115
in vacuum, 259; 527
8~, 226-228, 242, 248, 2Da-256,
vapor-liquid, 434,438-441, 443-451,
441-443j 874
49g...OO1~ 507-509
BUccesaive-fts.sh, 436, 461
Equilibrium oondensation, 437, 573-580
true-boiling:"pOint, '80, 90-92, 95-l02,
Equilibrium ooDBtants or ratios, 441, 443-'
111-122, 124, 221
449, 706-712, 743. 749
vacuum (888 Vacuum distillation)
Equilibrium vapori.zati~nJ 80, 103-105,
(See also Fractio:n.ation)
111-114, 116-119, 450j 459
Disti;l1ation curves, 90-92) 9S, f11-126,
curve, 111-113, 116-119, 459
227
Equipment costsj 277, 278, 286; 877-880
Distilla.tion, processes.. 226-262, 435-438,
Equivalent length, 396, 397, 402, 595
. 499, 608
Ethyl benzene, 736, 742' .'
Distillation tests, 22, 95-104
Ethylene manma.cture, 77, 78, 342-346,
-"Doctor" treating, 298, 304, 326, 331,
608, 644-652, 716-721, 723, -872,.. 880
Evaluation of stocks, 79-167
~72
Domestio fuel
(ste Distillate fuel
asphalt, 102-105, 128-132, 165-167
oil)
brightstow, 118, 248, 250Double-pipe exchAnger, 040
for corrosiveness, 128
DOWl)Spouta downpipes, 47H83
cracking st.ock, catalytic, 764-766, 771,
in stack, 431-433
772, 779-183, 80~ 808
Drip or epr&y-type condenser, 539, 560
the~ 608, 635-642, 644, 667 J 678Drying, "233, 234, 718, 756, 821) 822, 872. 681, 691, 910
crude oil, 79-167, 867-811, 876, 910
880
Dubbs process, 626. 682, 683
diesel or distilla.te fuel, 52-58;' 82, 83,
128-132, 1.56-160
~~ 4lBo Cracking)
#
or
INDEX
581
947'
948
687
combustion charts, 421-423,596,601607
heat balances, 422, 430, 615
losses from, 531, 532, 554, 613
Fusion, heat ofl 199, 202
834
sulfur content, 32, 838
sulfur removal, 764-756, 822, 823, 838
viscosity, 184;-187, 192-198
~line, 33-45, 146-151, 224, 833-84&
910
a.viation, 33, 34, 223, 700, 73S-:741
blending, 45, 148-151, 751, 840--843
chemical analyses, 16, 301, 711, 722,
834,837
cracked (866, Cracked products)
end point, 22, 34, 119-121, 417
evaluation (Bee Evaluation of stocks)
guIn in, 12,31,34,35,294,297,330
nat.ural (aee Na.tural gas)
octane number (aee Octane number)
by polymerization, 410, 418, 691, 722,
728, 731-734
properties, 33-45, 109, 146-151, 628631
straight-run, 16, 29, 42-44, 216, 218,
326,334
INDEX
949
950
PETROLEUM REFINERY
ENG~E~G
Ignition accelera'tors, 57
Ignition quality, 57, 58
Indexes of costs, 865-867
Induction period, 35, 297
Inflammability limits, 184-187, 201, 312
Inhibitor sweetening, 8, 298, 330
Inhibitors, 297, 314, 873, 880
for rust, 38, 873
Initial boiling point., 22, 476
Instrumentation, 263- 265, 270, '314,343,
388, 391, 732, 739, 754
.
Insulation, 528-533
Intercoolers, 829, 858
Inte.rmediat&-base crude oil, 80-83, 86,
91, 910-937
Isomers and isomerization, 13-15, 698,
700, 711, 750-756, 810, 812, 886
Isooctane or 2,2,4-trimethylpentane, 28,
42, 212, 694, 709, 735-737
Isoparaffin hydrocarbons. 10-13
153
Kerosene, 5, 48-52, 82, 155, 910
aroma.tica in, 49, 293, 295, 330, 352
951
INDEX
664
'
952
PETROLEUM
REFINERY ENGINEERING
84,98,218,224,325, B19,
~3-843
953
INDEX
954
37~382,
608
(See
876,880
Products; 31-78, 215-224, 628-632,
~44-649, 774-778, 813-815
boiling range, 331 34, 39, 46, 49, 50,
53, 55, 56,. 91-126; 216, 227
cracked (B~ Cracked products)
.
eva.hiAtmg (see EValua.tion of stocks)
~rke~ demands for, 5-8
.
phYsical properties (uePhysical pro~
erties, of stocks)
properties (see Specifications or properties of products)
l>loperty curves, SO, 10~126, 24s-.
250,258
testing, 19-76
.,
Propa.ne, 32, 77, 170, 184, 212, 326, 417,
'030, 651, 709, 820-822, 835
reco~er,y, 242-244, 345
.
. use, 348, 362-365, 386-:-389, 644; 716719
"
.
Propane deasphalting, 348, 362-365,
780, 781, 874, 878
Propane dewaxing, 386-:389, 874
Pseudo critic~l point, 177-181, 456
Pump!!, zn, 282, 289-291,410-413, 684,
685' .
.
steam for, 413, 903
. 870, 872-815
crude oil, 215-222, 226-262, 265-269,
279-282,.347-,.349, 410, 608, 865878,889
reduced or topped, 248-252, 608,
779, 808
sour, 89, 277, 279-282, 937
cylinder stock solution, 59, 217, 218,
. 2211 248, 335-341,38~, 3~, 608
drying, 233-235
367, 369
INDEX.
955
956
PETROLEUM REFINERY
60, 65,
Statistics of industry I 2, 38,
74, 77,88,89, 22~J 224, 277,348,
759, 811, 819-821
Steam, 229-232, 253-256, 441-443, 853,
874
for
426
distillation, 226-228, 242, 248, 253256, 441-443
409
partial presaure,
441-443, 470.
475
pumping, 413, 903
pumps, 410-413
in v&Cuum distillation, 253-256, 575581
Steam atomizing burners, 424-426
Steam coils for tanks,
ejectors, ~:l.i$-::l;nn
Steam refined cylinder stock, 59, 215218, 221, 871
L:)1.!1I;:1:Idll stripping or strippers, 229-232,
465, 470, 473, 477, 515,
302,
516,527,824-827,852-854,860,
861
Steel, chromium (8ee Stainless _V_'~A
creep strength, 283-286
low-temperature, 285-288
Stenches, 838 .
Storage loss, 40, 271-274:
Storage
271-274, 581
Stove diStillate or gasoline, 52, 54,
416
Cl.il:ea:m-llilIIllC efficiency, 224, 678, 682,
738
Stripper-fractionator, 845, 8571 860
Stripping, 229-232, 802, 844, 465-477,
515, 516, 527, 763, 797, 803, 824827, 853, 860, 861
Stripping factOrs, 302, 852-854
Styrene, 894, 700,
Suction
of pumps, 412
Sulfide corrosion, 276-282
Sulfide removal
Sweetening f:1"'PM.T_
menta)
Sulfides, organic, 17,
36, 37,
293-295,
Sulfur compounds, 17, 18, 36, 293-295,
298-303, 306,
ga.soline, 17,
42, 128-136,
293-298, 632
lubricants. 81, 641 66, 67, 128-132
material ba.l&ncea, 631, 632
INDEX
957
958
PETROLEUM REFINERY
ENGIN~ERING
959
INDEX
Unss.t~rated
622
in piping, 409-411
in stacks, 432
in vapor lines, 407-409
Venezuela.n oils, 84, 88, 89, 94, 131-135,
159~ .. 160, 357,415, 424, 630, 632,
774, 870, 876, 910-937
Vents, emergency, 270, 73S
Visoosity, 23-26, 179, 180, 192-198,''640
of blends. 108, 141-146
376,378,393,394
hea.t of-fusion, 199, 201
microcrystalline, 7, 69, 70, 215-218,
221,339,341,374,376,382
pressing, 4, 217, 218. 221. 248, 249.
376-382, 608
specifications, 69, 70, 530
properties
mack, 217, 21~221,376-379
treating, 295, a39-342, 379, 390. 393,
or
394,
873~814
960
!-
:I
I
,. :-
\,
.\.
-- - -