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PETROLEUM
REFINERY ENGINEERING

JHcGr~w-H"1

Chenaieal Engineer'l ng Series

Editorial Advl.,ry Boar"


Ja.mes J. Carberry, University. oj Notre Da'f1'16

Max S. Peters, rJnivenity of Colorado


William R. Scb~wa.lter t Princeton U7tiversitll
Ja.mes Wei, SotiOny M omZ Oil Compcntf

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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-

book of N mural Gas Engineering


KlRKBRlD:s-CAemital Engineering Fundamentals
KNuDSElf A.ND KATZ-Fluid Dynamics and Heat Transfer
KOBL AND RBsENnLD-Ga& Purification
LA.PrD'~B-DigiUJl Computalian for CMmical

EnginetT8

LEV'A' Fluidiultion

LEW\s, ~DA8CBJ

AND LEWIS-' Industrial

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

(EDITOR)--Chemiall Business Handbook

PERRY (EDITOn)-Chemical Engine~lSJ H anclbook


PETERs-Ekmentary Chemical Engineering
PETERs-Plant Design and Economics for Chemical Engineers
REID AND SllEltWoon--The Properties oj GMU and Liquids
ROBINSON AND GILLILAND-Elements of Fraclicmal Distillation
SCHMIDT AND MARLIES-Pri-nciple3 of Hig~olymer Theory and Pro,cUce
SCHWEYER-PrOCess Engineering EccmomiC3
SBlIiRWOOD AND PlGForu>-Absorplion and Extraction
BS'R EvE-The Chemical PrrKe8s Indmtries
BvtTH, B. D.-Denffl' of EquiU1rn.um StagB PrOCU8es
SIUTH, J. M.-Ghfmiwl Eflgi-neering Kinetics
'
SllITH, J. ~., ANn VA.N NESS--Introduction to Chemical Engineering Thermodynamil--t

TBEYBJ..IJ-Liquid Extradi(M
. TRETliAL-M cu3-tramfer OptTatimla
VILBllANDT AND DItTD~N-Ch61nical

E1lgi'Mering Plant DHign


VOLK-A pplkd ~tati8iiu JUt Engineer! .
W~S-RlactUm Kineti~ fM Chemical Engineer8
WALKER, LJ:WI5, MCADA"~, AND 'GILLJLAND-Prinsiples of Chemical Engimering
WU.LIAY6 AND JOHN80N-Stoiehiometry JOT Clte1ltiClll Enginen-$
WILSON AND RaS-Principlu oj CMmical &gimmitg T1&ermodJIfUJmiu

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PETROLEUM
REFINERY ENGINEERING
w.

L. Nelson

Consulting Petroleum and Chemical Engineer


professor of Petroleum Refining
University of Tulsa

F ounh Edition

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McGRAW-HILL BOOK COMPANY


NEW YORK

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
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PREFACE

an entire staff of engineers and the publishing of editions at two- or


three-year intervals. Important engineering material could not be
included in the First Edition, a.nd the situation has be-come more unsatisfactory with each succeeding edition. Growth during the last decade
has been especially rapid, and in addition an entirely new chemical
industry based upon petroleum as the raw stock is emerging. Chemical
developments have been recognized throughout the entire Fourth
Edition but especially in the chapters pertaining' to proce!Sing~ chemical
_and solvent treatment, thermal decomposition, and, of course, the conversion of gaseous hydrocarbons~ Catalytic" cracking and catalytic
refoiming are now practiced in nearly all refineries. Hydrocracking and
hydrodesulfurization processes have been thoroughly explored, and they,
too, may find extensive application. The sta.tus of atomic treatments
does not, a.t the"moment, warrant incorporation into the Fourth Edition~
The long lists of references at the ends of chapters of earlier "editions
have been deleted in the Fourth Edition.
The following statements from the First Edition are still pertinent:
Engineering involves the practical application of scientific knowledge,
"an~ hence I have made a conscious effort to emphasize the practical
phaseS of engineering work. In so doing it has often been necessary
to resor~ to empirical relationships. No apology is necessary for
such a treatment because engineers must_ build a.nd operate planti
regardless of inadequate information. "I n fact the history of industrial
development shows that commercial P.1a.nts are usually built before the
"theory of the ,Ufocess is fully understood", Scientific study "follows the
empirical development, and science finally administers those fine
improvements- which stamp the new process as truly great. The
process of empirical growth will always" be the lot of the practica.l
~cientist " or engineer.
For the same reasons some handbook information has been introduced. Although such infoFmation is not profound, it is the tool by
which theory can 'be put into action. " Such inionnation is also necessary in tl1e solution of illustrative problems, ,a nd I believe that no
n:tethod of engineering study is more effective tban detailed examples.
Furthermore an engineer must spend more time Applying information
than "deriving or finding itJ and hence handbook information and compre~ensive references are provided. The current literature contains
much that is useful, but the literature is so voluminous that it may be
-ueleless to a busy engineer unless it is presented -in an organized form.
I have attempted to organize this contemporaneous literature, but I
ha.ve refrained as far as possible from tiring the averag~ reader with
too many references and with conflicting opinions.

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PREFACE

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The author is greatly indebted to all of those who have contributed


to the several editions. In connection with the Fourth Edition, A. Paul
Buthod, Chairman of the Department of Refinery and Chemical Engi.":'
neering of the University of Tulsa, has been especially helpful throughout
the entire book, and Chapter 17 on the subject of Heat Transfer is his
particUlar contribution.

W ilbu~ L. Nelson

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CONTENTS

Preface to the Fourth Edition

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1 History and Development of Refining


2 Composition of Petroleum
3 Refinery Products and Test M etholh
4 EvaluJltion of Oil Stocks
5 ,Physical Properties of Petroleum Oil
6 I ntrf)duction.to Processing
7 Reflln,ery and Distillation Processes
8 Auxiliary Processes and Operations
9, Refinery Corrosion and M elals
10 ChemicllZ Treatments
11 Solvent Treating or Extraction Processes
12 Dewaxing
13 Fluid Mechanics
14 Combustion
15 Vaporization and Condensation
16 Fractionation and Towers
17 Heat Transfer and Exchangers
18 Tubestill Heaters
19 Thermal Cracking and Decomposition Processes
20 Rebuilding Hydrocarbons
21 Catalytic Cracking and Reforming
22 Natural and Refinery Gases
23 Economics of Design
24 Typical Design Calculation
A ppendix A
Appendix B

Densities and Specific Volumes


of Oils
Crude-oil Analyses

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

mSTORY AND DEVELOPMENT OF REFINING

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.
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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:
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. PETROLEUM REFINERY ENGINEERING

4 hr later. He found. that a . light-colored distillate of a low specific


gravity was ' being collected. The specific gravity was even lower than
that of the product hefore he left. Upon investigation, it was found
that a heavy oil was condenSing on cooler parts of the equipment and
dropping back into 'parts of the still that were at a temperature sufficient1y
high to cause decomposition of the heavy oil into lower-boiling-point
products. In the early days of the industry, gasoline was of little value,
and cracking was practiced for the purpose of producing more kerosene than could be obtained by steam or simple distillation. The first
attempts to produce gasoline by cracking were by the decomposition of
petroleum vapor. None of the early commercial attempts were s\lccessful until the Gyro process was developed in about 1925. Success was
TABLE

Refinery statistics

1-1
Jan.,

1931

Operating capacity, U.S., 1,000 bbl/dayG ..... 3,707


Cracked-gasoline capacity, U.S., 1,000 bbl/
day" ............ , ......................
~
Cracked gasoline, percentage of total refinery
gasolinel> .................... . : ... " .....
41.0
Average capacity of U.S. refineries., bbl/day .. 10,700
Number of operating refineries (U.S.)4 .......
346
Foreign capacity) excluding U.S.S.R., 1,000
bbl/dayll ...... , ... , .................... 1,577
a

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

U.S. Bur. Mines InjMm. Circs.


Approximate.

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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which contain no cracked tar is recognized by everyone. A .residual


charge stock is often distilled in the cracking unit itself, .and only the
distilled part of the feedstock is exposed to severe cracking conditions.
In most modem plants, residual stocks are introduced into the cracking
plant through a high-temperature cracking coil which greatly increases
the amount of distillable material in the residual feedstock.
Later developments in thermal cracking were "viscosity breaking" and
"reforming." The mild decomposition known as viscosity breaking is
conducted on residual or asphaltic feedstOcks. Originally it was aimed
at a reduction of viscosity and pou~ point, but it was soon learned that a
large amount of partially cracked gas oil, which could then be processed
in a conventional cracking plant, was also produced. Reforming units
are cracking plants that operate on naphtha or low-octane-number
gasoline for the production of a l~l.rge yield of highly antiknock gasoline.
These units were developed in response to the growing demand for antiknock gasoline and for larger and larger amounts of motor fuel.
High-boning reactive polymers are formed during thermal cracking,
and they are curre~tly removed as residual fuel oil by distillation. Reaction or coking of the polymers is also prevented by diluting the material
undergoing cracking with so-called U recycle stock." Difficulties with
reactive polymers do not occur in the modem catalytic cracking processes
because these processes employ adsorptive catalysts, that remove the
polymers in the form of coke on the surface of the catalyst. In , such
processes the cracking reactions can be much more complete, and the
antiknock quality of the product is correspondingly high.
Fractionation. The term Ie fractionation" refers to the separation of a
liquid mixture into sever:al products of shorter boiling .range by means of
vaporization. In early refineries this separation was obtained.by a series
of distillations in which, first, an inaccurate separation was made and t.hen
the partly separated products were redistilled several times, if necessary,
until finally the product met market requirelnents. The next development was to fractionate by partial condensation (i.e., a mixture of vapor
was condensed in portions by successively cooling the vapor to lower and
lower temperatures). An invention of this nature was that of Hugh L.
Allen,2 in which the vapor was successively cooled by means of a series
of air-cooled condensers into several liquid products.
The modern era of refining dates from the adoption of pipestills and
bubble towers. The name ~cbubble tower" has become common because
the vapor in the tower bubbles through the liquid on the plates in the
tower. In bubble-tower fr~ctionation a mixture of ascending vapor is
scrn bbed by a descending flow of oil. Bubble towers have been so universally adopted, all within a few years, that no one can be accredited
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Eng. Pa.t. 117,277 (19.18).

PETROLEUM REFINERY' ENGINEERING

with invention. In fact the fundamentals of fractionation were bor-,


rowed directly from the chemical distillation industries. Today bubble
towers are used in topping plants, rerun plants, vacuum plants, cracking
plants, natural-gasoline stabilizers, absorption plants, and steam strippi~g
operations.
NatUral-gasoline Plants. 'Natural gasoline 'attracted little atten'+.ion
until about 1912, at which time the demand for motor fuels became acute.
Today more than 10 per cent of all gasoline is manufactured from natural
gas. The .first widely 'used method of ~overy was ,the compression process. As gas is compressed, the dew pOInt is raised so that, upon cooling
to the original temperature, a mixture of hydrocarbons condenses. The
condensate contains a large percentage of volatile hydro~arbon's, such as
propane, which must be removed before the gasoline is a suitable motor
fuel. The first method that was used to remove these ~ydr.ocarbons from
the raw gasoline was called Uweathering." Weathering .was accomplished by allowing the H wild" gasoline to stand in an open vessel for a
time. A large part of the gasoline was lost during weathering.
'For a few years following World War I, the adsorption process received
much attention, but since that time it has been almost abandoned. In
. this process the gasoline was adsorbed by charcoal and recovered from the
charcoal by steaming.
In lat~r processes, natural gas was passed through absorption chambers
or packed columns, in which the gasoline was ab'sorbed by ' naphtha.
These, naphtha columns finally developed into the absorption process of
today .. In this process the natural ,gasoline is 'absorbed by' a low-boilingrange gas oil, and the gasoline is recovered from the rich gas.oil by heating it and stripping the gasoline from it with steam. A high pressure
assists absorption, but pressures above about 130 psi have been found
uneconomical unless the gas happens to be available at a high pressure
in t;he field. Weathering has been replaced by the use of high-pressUre
(150 psig) fractionators (stabilizers) which precisely separate the gaseous
hydrocarbons from the sta.ble natural gasoline.'
Dewaxmg. The'filter-press method of dewaxing followed by sweating,
as originally used in Scotland for shale oil before the development of the
oil industry, is still a wIdely used ,method of dewaxing the lighter waxbearing oils. Heavy residual wax-bearing stocks were first dewaxed by
cold-settling. In thls process the oil was chilled and allowed to stand in
insula~ ta'pks. The centrifuge process of dewaxing residual stocks was
studied for many years before it was entirely successful. The difficulties
had been the attainment of sufficiently high centrifuge speeds and the
tendency of the petrolatum wax to stick to the bowl of the machine. In
about 1921 warm water was suggested as a carrying liquid to be injected
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HISTORY AND DEVELOPMENT OF REFINING '

the centrifuge method of toda.y is essentially the same process as was


then used.
Recently, solvent dewaxing methods have becqme important. An
~portant advantage , of these processes is the a:bility to handle both
tight and heavy wax stocks by a sin'gle process. Many different solvent
proce~es are being practiced commercially, but the use of methyl ethyl
ketbne has been accepted almost to the exclusion oi;other solvents. It is
also tised for the deoiling of waxes.
'Chemical Processing. Although Professor B. Silliman" recognized in
his report of Apr~ 16, 1855, the chemical possibilities of petroleum, no'
bblk chemical conversion of petroleum was practiced until cracking was,
introduced in 1912. The removal of small amounts of i.mpurities by
treatment with sulfuric acid~ caustic soda, etc., has been and: continues '
to be practiced. In 1927 the process of hydrogenation as developed, by
the Standard Development Company attracted attention. This process
is ~ssentially a theI'1DB.I decomposition (cracking) process conducted at
high pressures and in the ' presence of hydrogen. Although several large
plants have been operated, the ~c6nomic position of bulk-scale hydrogenation has not yet (1957) been established.
Although the usefulness of adsorptive earths and other materials had
been known for many years, successful comrr,erCial operation of catalytic
cracking processes did not app~ar until about 1937 .with the advent of
the ' Houdry . catalytic cracking proces~. The cataly~t acts primarily in
adsorbing the reactive tarlike materials produced by thermal cracking,
but it may also exert some influence on' the cracking reaction. - Since
World War II some type of catalytic 'cracking plant haS'been employeq'
by all major refiners. ' '
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A multitQ.de of processes for utilizing the ,ole~c hydrocarbons of cracking-still gas have followed the development of polymerization processes in about 1935. Among these are processes of alkylation, hy~rogena
tion of hydrocarbons, dehydrogenation, cat~lytic desulfurization, and the
manufacture of many organic. chemicals. Although, the chemicals 86
manufactured are small in bulk compared with the regular distillation
products of the industry, they are important because they foretell the
cheap large-scale production of ma,ny heretofore somewhat scarce
materials.
Chronology of Development. In the following ou'tline no attempt has
been made to set the date at which new processes were conceived. Developments are not mentioned until the time when they were generally
,
accepted by the industry.
1860 to about 1885. The major refinery product was kerosene or burn~g oil. During this period disfavor was brought lipon the industry by
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PETROLEUM REFINERY ENGINEERrn'G

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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-

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treating methods were developed. High Viscosity Index lubricating. oils


were produced by solvent-treating methods. Vacuum distillation was
widely applied to the manufacture of road oil and asphalt. Tetraethy1lead was adopted as a means of improving the antiknock properties of .
motor fuels.
1935-1941. Propane, butane, and the unsaturated hydrocarbons found
in cracking-still gas were utilized for polymerizati~n, dehydrogenation,
and alkylation processes. Polymerization of olefins into "poly 11 gasoliPle
was practiced at nearly all large cracking plants" The Houdry catalytic
cracking process was introduced. Refiners delayed the formation of gum
in cracked gasoline by the use of oxidation.-inhibiting chemicals; colored
gasolines were generally accepted by the public; and the properties of
lubricating oils .were enhanced by the use of additive agents for lowering
the pour point~ improving the Viscosity Index, and imparting extreme
pressure properties. Ethylene and the gaseous olefins were obtained in
high concentration by the vapor-phase cracking of ethane, propane, and
the butanes. Large amounts of formaldehyde arid alcohol were manufactured from natural gas. Lower-viscosity automotive engine oils were
employed".
1941-1947. Heavy-duty lubricating oils were produced by the introduction of numerous chemical additive agents for improving pour point,
Viscosity Index, detergent and suspensoid properties, oxidation.stability,
tendency to foam, and tendency toward corrosion. Large chemical manufacturers introduced the first nonpetroleum synthetic lubricating oils.
The demand for diesel fuel oil and domestic distillate fuel 011 increased
rapidly. The urgency during World War II hastened the manufacture
of high-melting-point microcrystalline waxes from petrolatum or crudeoil tank bottoms j and numerous chemicals were manufaCtured from
petroleum on a large scale, including toluene, glycerol, butadiene, styrene,
isopentane, and isooctane in the fonn of alkylate for aviation gasoline;
and many petroleum hydrocarbons were separated on a commercial scale
by superfractionation processes. Most syn.thetic tire rubber was derived
from petroleum, and it was found that the coarser carbon black produced
from oil rather than natural gas was superior for compounding with the
new rubber. The Fischer-Tropsch process of producing gasoline, etc.,
from natural gas attracted wide attention. The Houdry, Thermofor,
Fluid, or Hydroforming f!atalytic cracking processes were employed in
all large refineries, and catalytic desulfurization of g'asolines was widely
used. The production of 100 octane aviation gasoline attained 500,000
bbl per day in 1945 but decreased rapidly after the war. Cooperative
associations operated more than 11 refineries, and 2,3271oca1 cooperatives
handled oil products in 1944. Physical methods ofanalyzing the chemical structures of oil molecules were developed whereby chemists for the

PETROLEUM

RE~RY

ENGINEERING

first time were enabled to apply extensively the science of chemistry to


high-boiling oils.
.
.
1947-1957. Petrochemical manufacture increased tremendously, and
synthet.ic rubber w~s more widely used than natural rubl>er. Sulfur from
refinery and natural gases became a significant amount of total sulfu,r
production. Natural gasoline, liquefied petroleum gases, and natural gas
were stored in natural underground reservoirs: The shortage of cooling
water in some areas hastened the deVelopment of air-cooled product
coolers. The development of jet and turbine aircraft engines caUsed So
rapid increase in jet fuel manufacture so that the middle .distillate por. tion .of petroleurQ, was in great deman4 for distillates, diesel fuel, jet fuel,
and rocket fuel. Air or fiue-gas lift -of. . catalyst as developed for the
Tbermofor and.Houdriftow proc~s was the major contribution in catalytic cracking. ' The:first tndy catalytic. proeesses to he applied to the
bulk-scale tr~~ent of pe~rol~l.tin were introduced as Platforming or
similar platin~ cat~lyst reiornring processes. Starting from 1950, e~tBr
lyti~ reforming increased by ~955 to nearly 1 million barrels per day,
and nearly every refiner had ,insta~ed a. plAnt. -Adequa.te supplies of ,
benzene and toluene are nQW assured because the platinum-refined
gasolines are rich in aromatics. Sweetening by mea.ns of inhibitors
rather . than chemical treatment -,was introduced. Improvements in
lubricating-oil manufacture led to the sale of such high Viscosity Index
oils that -a. single grade of oil -could be used dUring all seasons {)f the
year. The contiriual surplus .of residual tu~ oil at iilland points led .
to .8. wider use of co~n,g and the ' development of continuous coking
pro.cesses. Refrigeration was employed rather than pressure in the storage and transportation of volatile products such as propane and even
liquefied natural gas. . The increasing percentage of sulfur
newly
discovered oils led tq the development of several hydrogenation methods
of desulfurizing gas oil and distillate materials. Premiym gasoline of 100
Research octane number was ~st marketed in 1956, and many alkylation
plants were installed in' maintaining the so-called ,tI octane' race." Room
tempera.ture dewaxing was accp~plished on a commercial scale. by the
use of ureaJ which forms a complex with par~ hydrocarbons.

in

CHAPTER

COMPOSITION OF PETROLEUM

Most of the compounds found. in petroleum are composed of hydrogen


3Jld carbon. In addition to these materials, called hydrocarbons, other"
compounds containing small amounts of suJ(ur, oxygen, and nitrogen are
also present. The physical operations of refining, such as vaporization,
"fractionation, and cooling, are governed to ala.rge extent by the properties
of the hydrocarbons because they constitute the bulk of the petroleum,
but the chemical operatio;ns, such as treating and"filtering, :are governed
by the presence of sulfur, oxygen, and nitrogen compounds and, to some
extent, by the small aInounts of reactive hydrocarbons that may be pres-.ent. Russian crude oils I and certain naphthene-base oils contain rela..
tively large amoUnts of oxygen. The oxygen is often combined in the form
of naphthenic acids. Nitrogen is most often found in naphthene-ba~ oils
and is generally supposed to be the form of "basic compounds similar to
the alkyl quinolines. 2 Sulfur may be present
dissolved free sulfur,
hydrogen sulfide, or as organic compounds, a such as the thiophenes, sulfonic acids, mercaptans, alkyl suliates, and alkyl sulfides. Some of these
sulfur c~mpounds~re not found in crude petroleum, but they are produced
from other compounds during distillation and refining. Sulfur compounds
are particularly troublesome because theY are usually foul smelling
and some of them are corrosive. A feW parts per million of metallo~
organic compounds containing iron, nickel, vanadium, arsenic, etc., are
found in some petroleUm, and such amounts are poisonous to some
catalysts.
"
Many series of hydrocarbons are found in crude petroleum, and still
oth~r series are produced by cracking and hydrogenation. " Among the
series that are said
have been identified in petroleum are those having
the type formulas C n H 2n+2, " C"H 2n; C"H 2I1.-t, C"H 2"-,, C"H 2n- 8, C"H 1_ S,
C,JI2_1O, C n H 2_ 14 , and C"H 2n- 20 Inasmuch as most of the higher members of these series have n~ver been produced synthetically or prepared in"
sufficient quantity for study, we have few compounds With which to com-

in

as

to

1,Vuistavkina, T., Nefl1JaTW8 Klun., 18, 1000 (1930),


t Schulze,"King, and ThompsoD, J. Am. Ch~. " Soc., 52, 1239 (1930).
I Egloff a.nd Morrell, Chem. Md. Eng., 28, Q33 (19"
23).
9"

10

PETROLEUM REFINERY ENGINEERING

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

."(Jund in cracked products. Egloff, Schaad, and Lowry 9 have made an


excellent study of the literature of the olefin hydrocarbons (Fig. 2-lb).
The naphth.ene series (type formula Cn H 2n ) has the same type formula as
the olefin series but has greatly different properties. The naphthenes are
ring or cyclic compounds, whereas the olefins are straight-chain compounds
in which a double bond connects two carbon atoms. The napbthenes are
saturated compounds and the olefins are unsaturated~ Unsaturated comt;t~~t;iJ;ft;i

~~~~';i~
H-C-C-C-C-C-C"'H
I
I
t
I
I
I

H-C-C-C-C-C=C
I
I
,I
I

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
I
I
I
C =c-c-c-c=c
I
I
I
I
H
H H
H

,I
I

~. ~ ~

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

(f) Isomeric Isoparaffin Compounds


FIG. 2-1. Structural formulas of hydrocarbons.

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

The Decomposition B..nd Polymerization of the Olefinic Hydrocarbons, J. Phys.

Chem., 36, 1825 (1931).

-12

PETROLEUM REFINERY ENGINEERING

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

Thermal Reactions of Cycloparaffins and Cye1oolefios, J. Phys. Chem., 35. 3489


(1931).
11 PTOC. Am. A cad. Arts Sci., 36, 255 (1901).
12 Bridgeman and Aldricb~ Oil Gas J., Jan. 29, 1931, p. 42.
11 Petroleum Equipment Ezporter, January, 1930, p. 65.
10

".

l;j

COMPOSITION OF PETROLEUM

!
I

I,

'msaturated. The formulas of the saturated compound cyclohexane and


ohe unsaturated compound hexene-l may be compared in Fig. 2-1b and c.
Likewise .the formulas of n-hexane, 2-methylpentane, and 2,2-dimethylbutane, aU having the type formula Cl'IH 2n+2 or C 6H u , inay be compared
in Fig. 2-1a and f. Groups of atoms such as the methyl grQUPS in the
compounds just referred to are called "alkyl groups" or Cl radicals."
These terms refer toa group of carbon and hydrogen atoms that may be
conveniently considered as a tmit because they usually act as a unit in a
chemical reaction. They may be defined 8S a. monovalent hydrocarbon
group having the . general formula CnH2n+~. Common radicals are the
methyl (CH a), etJIyl (C 2H li), and propyl (C aR7) groups. Radicals are not
individual compounds because they must always be attached to other
radicals, elements~ or groups of atoms.
.
Then~ are two possible isomeric butanes, viz., n-butane and 2-methyl
propane; three pentanes; five hexanes; and rune heptanes. The number
of possible isomeric hydrocarbons jncreases rapidly as the number of carbon atoms increases. Compoun4s of the type formula Cl'lH 2n- 4 present
even more possibilities of isomerism than the foregoing. As an example,
the saturated series might consist of three doubly combined rings or combined rings with alkyl side chains; the unsaturated series might consist of
numerous compounds having unsaturated carbon atoms in the ririgs, in
the side chains, or in both; and other series might mast having combinations .of saturated or unsaturated rings with saturated, unsaturated, or
acetylene side chains. Consideration of the series that are even more
deficient in hydrogen than the C"H21l~ series indicates that an enormous
number of isomers is possible. Fortunately the number of unsaturated;
high-molecular-weight hydrocarbons in petroleum are probably few, or
the isolation of these .complex compounds would prove an endless task.
The. number of possible aliphatic (C"H 2n+2) isomeric hydroca~bons is
Carbon atoms

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

.Determination of Series. Although chemists have not yet determined


procedures and reagents for the isolation of each chemical series, a. start
toward this goal has been made. U The proposed methods do not indicate
the exact series of hydrocarbons that are present, but'-" they do indicate
groups of compounds that behave chemically. in the same way as the lower
14 Hill, J. B. Ind. Eng. (]hem., 46, 1398 (1955).
t

14

PETROLEUM REFINERY ENGINEERING

members of the paraffin, olefin, aromatic, or naphthene series. With the


exception of normal paraffins, no individual hydrocarbon beyond C u has
as yet been iso1ated from petroleum and identified. 14 All double-honded
hydrocarbons such as the olefins, diolefins, and double-bonded cyclics are
classed together as one group, c,aUed tl unsaturates." The unsaturated
group may be absorbed or polymerized by sulfuric acid; t.he aromatics
may be nitrated or absorbed ~y fuming sulfuric acid or dissolved by

.:I

=----f-~-4--_+__----460

g.

(\

~--#-~~-4---4---+---+--~70~

m
o

~T---~~~~~~~-+--~---r--~&Oz

(II

",

:n

90M

lJ)

PERCENTAGE OF CRUDE Oil..

FIG. 2-2. Chemical composition of an aromatic-base 'c rude oil.

(Oil Gas J.)

dimethyl sulfate; the naphthenes may be determined by means of the


aniline index; and the paraffins are found by difference. Such an analysis
is perhaps just as valuable to the engineer as' an exact one, because he is
concerned with the retention or elimination of certain properties in the
finished products rather than with a detailed knowledge of exactly what
compounds are present. By means of the foregoing analysis of chemical
properties and the physical consta.nts of each series, a reliable estimate or
check of the physical constants' for any petroleum oil is possible. Such
an analysis, to be of most value, should be made on each of, say, 10 fractions of a crude oil, so that the change in the percentage of each series
can be followed throughout the entire boiling range of the oil. Kurtz
et a1. 15 present a triangular composition chart for percentage of paraffin,
naphthene, and aromatic carbon atoms in lubricating oils. On the same
chart they have plotted the relationship between viscosity-gravity-con16 Kurtz, King, Stout, And Gilbert, Div. Pet. Chem., Am:. Chem. Soc. Meeting,
Minneapolis, Sept. 12, 1955.

-i

15

COMPOSITION OF PETROLEUM

stant and refractivity intercept so that these easily obtainable properties


can be used to estimate chemical composition.
Figure 2-2 shows such an analysis of a Grozny wax-free (Russian) cnide
oil. IS , Vlugter, Waterman, and van Westen 17 were among the first to
actively develop the so-called" ring analysis" whereby the percentage of
aromatic and naphthenic rings per molecule can be determined as well as
the percentage of paraffinic side chains. Chemists are becoming increasTABLE

Fraction!

2-1.

CHEMICAL ANALYSES OF PETROLEUM, PER CENT

1. Groxny (" high


paraffin "), 45.3 per
cent at. 572F

.2. Grozny ( .. paraffin- 3. Oklahoma (Davenfree upperlevel "),


40.9 per eent at. 572"}t'

port), 64 per cent. at

Arematic

Aromalic

57~F

4. California (Buntington BeBch). 34.2


per cent a.t 572"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

ingly aware that the structur~s of large petroleum hydrocarbon molecules


are seldom totally aromatic, naphthenic, or paraffinic.
Physical methods of analyzing for the kinds of molecules in an oil are
.discussed by Schlesman and Hochgesang. lS Among stIch methods are
X-ray and electron, diffraction; electron micrography; mass, emission,
ultraviolet absorption, Raman, and infrared spectroscopy.
Composition of Petroleum. In "he past, petroleum -h as often been
considered as a solution of the paraffin hydrocarbons, but a 's urvey. of the
literature indicates that such ,an assumption is not justified. The paraffins predominate in most gasolines ll 14 and proba~ly in kerosenes from
paraffin- and mixed-base petroleum; the naphthenes predominate in most
gas oils and lubricating oils from all bases of crude oils; and the naphthenes, aromatics, and unsaturated hydrocarbons constitute the bulk of
the highest-boiling
residual products. The only paraffins present :in
the higher-boiling products appear to be those occurring in the wax, and
the amount of wax in even paraffin-base petroleum is relatively small.
Sachanen and Wirabian 19 present analyses of several Russian and American oils (Table 2-1); and refer again to the more complete analysis given in
Fig. 2-2.

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

n J. Inst. Petroleum, 18,

16

PETROLEUM REFINERY ENGINEERING


TABLE

No. of
carbon

2-2.

HYDROCARBON SERIES FOUND IN PETBOLlilUM

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

STRAtGtT- AlRt CASOUNES


H'f'DAOGENl.T!D CMOUNE.
OlHERWAl. &. A CATALYTIC
CRACKED
G.ASOUN[S

.;

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

. !

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!
).

PennSylvania. pipeline ..
Mecook, W.Va ........
Humbolt, Kans .... . ...
Healdton, Okla ........
Coalinga, Calif ........
Beaumont, Tex ........
Mexico ..... . . '........
Baku, U.S.S.R ........
Colombia, South
America. ............

At

CHEMICA.L ANALYSES 01' PETROLEUM

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

20 85.62 11.91 0.54

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

PETROLEUM REFINERY ENGINEERING

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.

Odor is most obnoxious with low-boiling or gaseous sulfur compounds,


as hydrogen sulfide, sulfur dioxide in flue gases, mercaptans up to even
six carbon atoms (boiling point of about 400F), sulfides . up to 'eight
carbon atoms (about 350F), and among disulfides only methyl disulfide
(boiling point 243F). Thus odor is not obnoxious in sweetened products
except in certain extremely high-sulfur. gasolines~
Susceptibility or responsiveness of gasolines to tetraethyllead is greatly
harmed by small amounts of sulfur compounds (Ta.bles 3-7 and 10-1),
and the approximate effect of each type of compound can be estimated
by the met.hod outlined in Example 3-2. The distribution of mercaptans
in typical gasolines is indicated in Table 10-2:
The percentage of sulfur in crude oils ranges from nearly zero for '
certain high-APr-gravity crude oils to as high as 7.5 per cent in a. few
very heavy crude oils (see Appendix :8). Such a high percentage of sulfur means that more than half of the compounds in the crude oil may
contain sulfur,

.,

CHAPTER

-3

REFINERY PRODUCTS AND TEST METHODS

A complete discussion of the large number of routine tests that are


practiced today could easily fill an en tire book, and hence only ~he barest
_mention-of te:st methods will be possible. Details of laboratory manipulation must be obtained from other sources, particularly "Petroleum
Products and. Lubricants,"~ an annual publication of Committee D-2 of
the American Society for Testing Materials.
A voluminous but much less satisfactory literature is available concerning the relation of routine test results and the performance characteristics
of petroleum products. . This' is unfortunate, because to a large extent
refine~ operations should be governed or .r egulated by the performance
of the products.
ROUTINE LABORATORY TESTS

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

PETROLEUM REFINERY ENGrNEERING

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.

APPROXIMATE RELATIONSHIP BETWEEN POURlNG TEMPER4TUllE

AND SUCH PROPERTIES AS VAPOR PRESSURE, _FLASH POINT,

. AND BOILING POIN-r-

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.

Ca-free na.t. g&8O. Contains C a


Crfree Dat. gaso. Contains 0 3
Crfree nat. ga.so.' Contains C J

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

(h1 Gas J' 7

May 20, 1948, p. 239.

Decomposition occurs at higher tempera.tures.

112

440

515
585

66()b
6W
66()b
660"

280
330
380
430
490
540
640
66()b

21

REFINERY PRODUCTS AND TEST METHODS

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

. API = 141.5 - 131.5


eg
sp gr

or

141.5

sp gr

= API + 131.5 (3-~)

Corresponding values of API gravity (0 to 100), specific gravity, and


pounds per gallon are given in Appendix A, as well as pounds per barrel,
barrels or cubic meters per long ton, etc.
The Baume scale of gravity for liquids lighter than water, used previ..
ously by the industry, differs slightly from API gravity by the
of
constants of 140 and 130 rather than 141.5 and 131.5.
Specific gravity or API 'gravity is measured by means of hydrometers 1
(D287), pycnometers 1 (D941 and D121 i), or the chainomatic specificgravity balance if very many small samples (15 cc) must be tested. For
viscous oils or semisolid bitumens, a pycnometer (D70) or weighing bottle
)Ilay be used, for solids an analytical balance (D71) equipped with a. pan
straddle.
'
Most products are sold on a basis of vohlme delivered corrected to
60F by means of standard tables of volume corrections. & Weigh t is
important in determining, freight rates, tanker cargoes, a.nd the power
required in pumping. Gravity or weight determines whether a 'product
will sink or float in water-or will separate from water. I~ other respects
gravity is not of much direct significance, but the test is so simple and so
widely used that it assumes importance as a means of judging-many other
properties and in controlling plant, operations.. Gravity requirements
should usually be avoided in specifications.
.
Vapor Pressure (Reid). ' This test (D323)1 is 'used for volatile nonviscous products such as motor gasoline and, by using a special sampling
,procedure, for natural gasoline of 26 lb or more vapor pressure. A
modified equipment.and procedures is used for liquefied -petroleum gases
(L.P.G.). These tests are conducted at 100F. The ASTM vapor pressure is reported as pounds per square inch absolute pressure, whereas the ,
L.P.G. vapor pressure is gauge pressure. The true vapor pressure "is
higher th~n the Iteid v~por pressure by about 5 to 9 pet cent (page 136)~
but this relationship varies widely.

use

ASTM-IP Petroleum Measurement Tables, 1952;


California N a.turru Gasoline Association, Los Angeles, C&lif., Tentative Sta.ndatti
Methods of Test for Liquefied Petroleum Gases, Bull. T.S. 441, HH5.
I

! .

22

PETROLEUM REFINERY ENGINEE.RING

Vapor pressure is an indication of the pressure that a material will


develop within a closed container and is particularly significant for materials whose boiling points are so low that they cannot be distil1ed at atmospheric pressure without serious loss. The test is import.l.nt with respect
to safe~y in transport, vapor lock in gasoline feed systems, types of storage
tanks e:r:nployed (Fig. 8-7), and the starting characteris.t ics of motor fuels.
ASTM Distillations.' These tests 1 for gasoline, naphtha, and kerosene
(D86) ;.natural gasoline (D216); and gas oil (Dl58) invelve much the same
procedure. A somewhat similar test known as the" Engler distillation'~
.has been used in the past, and often the ASTM distillation i's referred to
a~ "an Engler. JJ
-One hundred cubic centimeters of oil is distilled at a uniform rate of
5 cc per min. The distillate is condensed in a brass tube surrounded by
cracked ice. The temperature of the vapor when the first drop (F.D.) of
condensate drips from the condenser' (in not less than 5 or more than
10 min) is recorded as the Ie initial boiling point JJ (I.B.P.). The vapor
temperature is also recorded as each successive 10 per cent is col1ected.
When 95 per cent has been distilled, .the burner flame may need to be
increased, and the maximum tem~erature is recorded as the" end point"

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

REFINERY PRODUCTS AND TEST METHODS

'

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
/

,!

Kinsel and Phillips, Pet Refiner, May, 1950, p. 93.

24

PETROLEUM REFINERY ENGINEERING

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

Wa.ter wbiteWater white


Water white
SuPerfine whi't e
Prime white
Prime white
Prime white
Standard white
Standard white
StAndard white
StandArd ....hite
St.&ndard white
StaDdard ....hite

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

Lovibond color analyaia (l2-in.


ceU acepi I-in; for a.mber)

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)

..............

Approximate relll~on8hip to Say);,oIt. Color.


~ Na.tional Petroleum A880cl&tiOn.
" Uaed alone without. other color disks.
'II For filtered ey~der stl,)CU:.

a distance of 1 em froIOan~ther plane of 1 sq em area, through a distance


of 1 em in 1 sec.
The relative viscosity is the ratio of the viscosity of the liquid to that of
water at 68F. The viscosity of water at 68F is 1.002 centipoises, and
hence the relative viscosity and ~e viscosity in centipoises are num.eri-

25

REFINERY PRODUCTS AND TEST METHODS

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

the, Saybolt Universal viscosity and z ,and' 8 are the viscosity in


centipoises and -the specilic gravity, respectively, all three -faetors ,t aken
at the same temperature, the relati~n among these variables, according to
the Bureau of Standards,

is

TT:_

.n.wema

le VlSCOSl

= 8'Z =

0219

, '

t - ,149.7
t

(3-4)

The ASTM recommends a. series of conversion factors l (D446) by which


centistokes can be converted into Saybolt Universal viscosity.
N ~ and Rwi8ed Tag Manum , The Refinery Supply Co., Tulsa, Okla..
10 Nelson, W. L., Oil Gtu J'J Nov. ~ 1952, p. 138.

26

PETROLEUM REFINERY ENGINEERING

Figure 3-111 may be used to convert the viscosity by anyone of the


viscosimeters to the viscosity by any of the other common instrument~.
Somewhat more exact comparisons are available in tabulated form. 12
Alt.hough Fig. 3-1 and .the tabulations are useful for approximating the
viscosity for design work or estimates, they shoUld not be used for exact
specifications. If the viscosity of a shipment of oil is specified in particular units, the viscosity should be determined in these units by using the
proper instrument.
. In .using Fig. 3-1, the viscosities by various instruments must be deternuned at the sam~ temperature. If the viscosities are -available at
different temp~rat~s,. then one or the other of the viscosities must be.
corrected for temperature as explained in Example 5-13.
Example 3-1. Use of VIscosity Conversion Chart (Fig. 3-1). The .Saybolt viscosity is 1,000 sec at ~HOQF. What is the Furol viscosity at 210F?
Trace the 1,000 time line to the intersection with the Sa.ybolt Universal line. Follow the horizontal line (kinematic viscosity of approximately 215.0) to the Saybolt
Furol line. Read down from the intersection. The Saybolt Furo! time at 210~ is
approximately 103 sec.
The Engler time corresponding to the foregoing is 1,500 sec. The Engler degrees
(or number) corresponding to the foregoing is 30.
The lower and left scales are used for Sa.y-bolt Universal viscosities up to 8,000. For
higher'vis.cosities the upper and right scales are used.

, 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;e Texas Company, "Lubrication-," May,. 1921.


_
unstau, Nash, Brooks, and Tizard liThe Science of Petroleum" 4 vols
Oxford University Press, New York. 1038; also Nelson, W. L., Refiner 7s 'Notebook~
10~3 and 132, Oil Gcu .J., Aug: 31, 1946, and Feb. 15, 1947.
Young, Y. C., Oil Ga8 J., ~ay31 o.n.d June 7, 1951.
.

i
i

.i

I
i

!
j
I

.,
i

27

REnNERT PRODUCTS ' AND TEST METHODS

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

I .s.pea. f/u: 6:'ravl


.. "Iy
I
I

"

.
. ,:\.
Icrl<en allnesaml' ft'~
~
~ ~sl e YfsfOSlIy ~t'a {h9 ~

lA ' + t1
30 405060 80100 200.300400

.J rl

4,000 ,

, A Di5tilled water at 20 d~. C:


Glyc.~rol mixtur~sCit1 aeg.
. oRe:fined Ca5torolf
I
.Mineral oils
~. Alt-ohol, ~O%.

!
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

PETROLEUM: REFINERY ENGINEERING

Knock. Characteristics. The confusion that has long characterized


methods of knock testing
not abated. u . N orm..al heptane and S,S,4trimethylpentane (so-call~d "moocrone") iw.ere adopted as standards in
1930 along with' a standard CFR (Cooperative Fuel Research) engine.
unit of knock' intensity, known as oclane number,is defined: ~ the
percentage by volume of isooctane that must be
'with normal
order to match the knock intensity of the fuel undergoing
. heptane
testing.
TbeEthyl Series 30
SOB engines were used during 1929-1930, but
in 1930 the CFR engine was developed and. the research method of test
(1931) was recommended. Various
methods were employed in a
continual attempt to duplicate road perfol!Dance
the laboratory1933, ASTM or motor method; 1936-1937, Ethyl. Corp.. 1-3 method;
1939, modernized resea.rch method; 1940--1946, a.viation methods 1-0
(lean) and '3-C (rich); a.nd in 194.8 the present methods of test known as
or Research (D908),1 F-2 or Motor (D357),l F-3 or Aviation (D614),1
'and F-4 or Supercharge (D909)l were adopted.15 The Research method
conducted at an engine speed of 600 rpm and th~ Motor method at
900 rpm. Different oc~ne numbers
obtained by each of the
and the difference in octane number between the Research and Motor
methods is caned the U ~etu1!' or U seruJitivity." Spread is related .to
road performance because the Research method more properly represents
the ,speed generally low and
. performance during city driving
acceleration frequent, whereas the Motor method indicates good .........:".....speed performance on the highway. 18 Likewise, the F-3 or l-C Aviation
~ethods check best with the performance ,during cruising; whereas .the
)?-4 or 3-0 mixture methods are related to the great power required dur-.
ing .fighting maneuverS. In
range of 80 to 100' octane number, the
Aviation method rates a. fuel
about 1 octane number higher than
the
.or Motor method. i1 The approxima.te relationship. between
octane' numbers by the Motor
Research methods is indicated in
Table
U'Atleast eight distinct. methods ha.ve been
Since 1928
none of
prop. represent. road: performance. Agen.cies promoting .cracked gaso~rie, iea.ded
gasoline, and catalytic gasolin.e have vied in
methods of testing. The
.la.test (1956) modifica.tion, the
Wiese scale for octane numbers above 100,
.e. compromise between the desire of engine manufacturers to use the Perfonn.lince
Numbers of aircraft
for automobiles and the refiners'
to have a
tha.t properly r~Bects the
of producing hlgh-octB.ine fuels.
15 NelsoD., W. L., History of. Octane Number
Oil Gas J., Dee. 22,1949 ,
p. 286.
16 Nelson, W. L. t Oil Gall J" May 12, 1949, p. 116.
17
W.
Oil Gas J. t July 13, 1950, p. 98. Range is 0.5 to 1.6 units, decreasing again for
numbers a.bove 100.

i
I

I
1

I
I

29

REFINERY PRODUCTS AND TEST METHODS

I
3-3.

TA1H.E

AVERAGE RELATIol'sBIP BETWEEN MOTOR .AND RESEARCH OCTANE


N UlmEBS (SENSITlVlTT OR SPREAD)

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'

...... . .... . . ..... .


. ...... . ... , . , . 100.0'
-

....

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

Detonation performance of fuels at levels above 100 Research octane


~umber will probably be design~ted by the so-called Wiese scale.. Performance Number, originally developed to show the percentage inc1.'ease
in aircraft engine power for additions of TEL to iSQoctane, is generaliy related to engine output. The relaiiollship between ReSearch octane

30

PETROLEUM REFINERY ENGINEERING

Dumber"Performance Number, tetraethyllead additions, and the Wiese


scale is shown in Table 3-4.
.
Sulfur Tests. The.sulfurl (D90) content of gasoline and burning o~18
is an important specification. About 10 g of oil is burned in a small lamp,
and the products of combustion are "drawn through a. sodium carbonate
absorption solution. The sulfur is determined by titrating the unused
sOdium carbonate solution. Sulfur in residual fuel' oil and crude oil is
determined by the ordinary oxygen-bomb method 1 (D129).

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

.. Ro.n. = 128 - . 2800 '+ .P.N.


O.n. = 100
(p.N. - iOO) + 3. Purely a. compromise, stale.
II Approxima.te.
41, No longer uSed.
See Wiese scale.

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.

3. DUtillales-mnge oil, furnace distillates, di~ fuel, an'd gas oil.

32

PETROLEUM

Lubricating
Greases and

engine,
cylindert
wax) microcrystalline wax,

Specialties--medicinal

asphalt, carbon
etc.
hydrocarbons, chemicals,

6.

etc. '

for the yields of products


The evaluation of crude
........H..'V""" In
Cbap. 4 (also see Appendix
Volatile Products. Liquefied petroleum
are graded
with respect to
presSures and the temperature which 90'
evaporated.
unauthorized
B-95-10 refers
a
Table 3-5) that
a vapor
of' 95 psig
a 90 per cent
3-5.

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

California N atur.o.l Gasoline Associ.o.tion.

evaporation temperature of 10F. Had


number
B-95-M10 it
would
meant
90 per
temperature
10F.
Grades ~,
Fare
The
Board
Underwriters
standards
safe handling of liquefied petroleum
19
in
Pamphlet 58.
specifications (June, 1951)
the NGAA (Natural
Association of
f or commercial propane and commercial bu taue
,(1) a :m.inimum of 95 per cent of propane and/or propylene (or
and/or butylenes) , (2) no hydrogen sulfide, -(3) a
eopperstrip
_~"''"'~ test (3 hr
122F), (4) no water by the
bromide
test,
a. maximum of
grains per 100 eu ft of total sulfur. The
vapor
of propane must
below 215 psi
100F and of butane
below 70 psi.
Natural
are graded by
Association
Natural
as follows:
Standards for Liquefied Petroleum
Underwriters, New York, August,

N BF U Pamphlet 58, N .o.tiona.l

.!

Reid vapor pressure. . . . . . . . . . . . . . . . . . ..


Percentage evaporated at 140'T. . . . . .. ...
Percentage evaporated at 275F .... ~ . . . ..
End point ... , ............. : .... ; ......
Corrosion ...................... : . . . . ..
Doctor test .. ~ .........................
Color ......... ~ ............. ~ .........

!'

,r

l
to

33

REFINERY PRODUCTS AND TEST METHODS

10-34lb
25-85
Not less than 90
Not higher than 375T
Noncorrosive'
Negative, "sweet H
Not less than plus 25 '

In addition, natural gasoline is divided. into 24 possible grades orr a basis


of vapor pressure and percentage evaporated at 140F. These grades
are shQwn ,in Fig. 3-2. Grade 26-70 is the standard grade for account'aney and pricing purposes even though, the average gasoline now has a
vapor pressure of about 18.
Percentorge Evorporated at 140 0 F.
40
55
70

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---~--~--~~----~~;-----------~~--~--~
~

Grode ,14 -40

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,
,

, Gasoiirie . . In an industry of many by-products, gasoline is the major


product. The general properties of gasolines are indicated in Table 3-6.
United States government agencies specified at least 12 gasolines during
World War 11. 20 White Unleaded Undyed gasoline is used for stationary
engine~, cleaning, and as stove gaso]ine~ M olo':' Fuel 72 was used within
the continental limits of the United States for nearly all vehicles-type A
at climates of 50F and up, type B at 25 to 70,oF, and type C up to 45F.
Rei!- All Purpose gasoline was used for all military vehicles-Grade A at
OaF and up in temperature and Grade C for arctic c1imes up to lODF.
Aviation Grades'80, 87, 91/96, and 98/130 were used for training purposes
and Grades 130 and 140 for combat cruising and fighting.
The ASTM specifications are perhaps the 'most comprehensive. In
addition
the three types of gasolines specified in Table 3-6, types A and

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.

_.- . . _ . ,

-- -----

"ABBREVIATED GASOLINE SPJlCD'lCATIONS AND PBOPERTIES

T ..UU.J!I 3-6.

MlIJdmum parccntagea 8V&por&t.ed


rot. temger&tures
ahowu elow. F

Name or' grade

10%

::r:

ABTM. a.viation D91~S3T:1


158
1. Grade 80-87 . .................
_ 2. Grade 91-96, .. , ..... , .. . . , ....
158
168
3. Grade 100-180 ... , ..........
4. Grade 108-135 .. , ...... , . ,
158
6, Gra.de 116-146, .............
158
ASTM &utomotLve D4.39-65T:L
6. Type A. norUlAl ;. ........... 140-108
7. Type B. vola.t.Ue, ', ' .... .. .... , .. 140-168
167
- 8. ~pe OJ nonvolatile . .. . . ..... . ..
Av\ (u a.viatioD.:4
160
. 1940, Grade 91-98 . ... . . , , ....
152
10. 1940. Grade 100-130 .... " . ...
150
11. 1947. Maroh. Gra.d.9 80-87 ......
12. 1947, March. Grado 91-98 .....
148
152
13. 194.7. Maroh. Grado 10D-130
148
. 14. 1966. Grado 80-87 .
141
15. 1966. Grade IH-96 ..............
141
16. 1966. Grad9 100-180 .....
147
17. 1956, Grade 108-135 . .....
146
18. 1966. Grade 116-145 ............

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

Ai\ fuels. automoUve"

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

- ------""""':'-- "7",-- - -_ ...

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

..

..

"

..

..

..

"

..

" " ..... t "

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

REFINERY PRODUCTS AND TEST METHODS

B are further divided accord'i ng t~ volatility' to 'care for seasonal changes,


as indicated in the following tabulation:
10 per cent Vapor
point
pressure
Cold or winter (W) .. ~ . . . . . . . . . . .
Medium (F) ....... '............. '
Warm ' 01' summer (8). .. . . . . . . . . . .

140
149
158

13.5 '
11 .5
9 .5

All parts of the United States have been classified as W, F, or S .areas, a~


used aboye, with regard to climati~ conditions during each month of the
year.
,
The most significant performance characteristics of motor fuels may be,
summarized as follows ' (somewhat in order of importance):
, 1.
2.
3.
,4.
5.

Freedom from wa.ter, gum, and corrosive sUlfur.


Vapor lock.
Warm-up aod acceleratioll.
Anti1plock quality.
Crankcase dilution.

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- ,

" Gum, mg per 100 ~

,
i

- 6-10
15-25

, Satisfactory
Only a few hOUI13 'and up to 1,000 'miles

be

'Potential or ultimate gum tba.t titay in time


foimed in a gasoline is of
little significance except to indicat~ the difficulties that may
encoun~
tered if by accident or error the gasoline is not marketed for many
months. A high manifold temperat~re- increases intake-valve and. chamber deposits,22 and a rich mixture generally causes larger 'engine deposits. 22
Engine deposits inere'ase greatly as the gum content- is increased from
. zero up to,.7 or 10 mg, but ,hi~lier gum' con tent causes s'c arcely more
trouble th~n gUm qontents of :10' mg, . The 'i nduction .period in hours
, (D525) l' is .approXimately equal ' to th~ months -that 'the gasoline can be
stored under .conditions of commerce. .The .rate of gum formation in
storage has b~e~ related to, the time required t~ produ~e 10 mg of gum

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

PETROLEUM REFINERY ENGINEERING

in a laboratory accelerated oxidation test,23 and hence it is possible to


foretell the length of time that a gasoline can be stored.
The amount of sulfur (noncorrosive) .that can be a110wed is probably in
excess of the 0.25 per cent permitted during Worid War II. This quantity led to no serious trouble, and gasolines containing in excess of 0.4
have been marketed in some parts of the United States. High sulfur
causes corrosion in the muffier and tail -pipe of the exhaust system during
cold weather because of the condensation of moisture and formation of
sulfurous and sulfuric acid. Mono- and disulfides and mercaptan sulfur
compounds are ~~tremely harmful to theJ susceptibility of gasolines to
tetraethyllead (see Table 3-:7).
TABLE

3-7.

ApPBOXlMATE EFFECT OF SULFUR ON LEAD SUSCEPTIBILITY 4

(Each compound used alone)


. Percentage of TEL used in overcoming the effect of sulfur (L)
Pe:rcentage
of sulfur
by weight

----

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

...
.. .

...

Mapstone, G. E., Pet.

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

February, 1952, p. 132.

The percentage of TEL ~sed in overcoming the effect of sulfur com...


pounds (Table 3-7) may be defined as L .
.L = a o

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

Ind. Eng. Chem.,

sa, 83 (1940).

,.
f

REFINERY PRODUCTS AND TEST METHODS

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

By extrapolation of Table 3-7.


;

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 .

The color' of gasoline indicates little about its quality, although it is


an indication of the thoroughness of. the refiniIig' operation and . of the
tendency to produce gum. The highly desirable antiknock compounds
are partly removed by treating, and hence the specification of color has
become less and less important. Most refiners resort to the use of oil-
soluble dyes to mask the color of the natural product. Dyes ranging in
color from yellow to dark purple are a.vail able. 2-1 These dyes also serve
(1) to identify a gasoline and thuB promote confidence in its advertised
quality, (2) to preserve the antiknock properties that would be partly
lost during treatments used to improve color, and (3) to reduce the cost
of refining.
Tetraethyllead is the most important additive used in gasoline. It
greatly increases the octane number. Antioxidants are used to inhibit
gum f<?rmation by oxidation and polymerization in storage, and they
prevent potential gum-foTImpg substances from depositing in engine fuel
lines, carburetor jets, and on intake valves. Military specifications for
Eg]o.ff et al.) Dye Saves Dollars in Treating Gasoline, Oil GalJ J., Mar. 5, 1931,
p. 133. Also, Thompson and Johnson, Ind. Eng. Chern., 48, i869 (1956).
24

38

'PETROLEUM REFINERY ENGINEERING

all-purpose gasoline require a minimum of 5 lb per 1,000 bbl of the


following oxidation inhibitors, ,separately or in combination:
N, N' ,~isecondary butylparaphenylenediamine
N, n or isobutyl-p-aminophenol
,Di-:N, N 8eo-hutYl,;.p-ph~nylenediamin.e '
Minute amounts of metal impurities, especially copper, catalyze the oxidation of gasoline components, and 1-3 lb 'p er, 1,000 bbl of metal deactivators such as N, N' disalicyledene, 2 di~minopropane, are used. Rust
or corrosion inhibitors are usually surface-active agents that' coat ferrous
metals and prevent water-metal contact in pipelines, storage tanks, or in
vehicle fuel ~stems. Ammoniuin sulfonates and ,organic phospborus
compounds are examples of rust inhibitors. Variona alcohols are used
as anti-icing, additives to prevent freezing o~ water in gasoline tanks,
, strainer bowls, or 'carburetors. Most recently preignition preventers
,have been developed which tend to prevent spark-plug ,fo~ing and pre, 'ignition. Upper-cylinder 1ubricanta (Jight ]ubricating oils) added tQ
gasoline help in the lubrication of valve stems and the upper ,walls of the
cylinder. C. M. Larson 2li has estimated the annual consumption of these ,
additives during i 955 (Table 3':'8).
'
T.ABLE 3-8.

ESTIMATED

Additive type

1955

CONSUMPTION OF .GASOLINE AnDITl'-1ES 4

Approximate
dosa.ge -

Millions of

pounds

Million~ 0(,

doUars

..

"

Tetraethyllead .. '...... : " .. _,..........


A.i1tioxidants, ... '.:........ '.... '... , ...
Metal dea.ct~vatorS.~; "~" .. ', ',' .. , .......
CorrOSlOn
. ' ' In
. bib'ltom ..... , ........... ;

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
.
".

., ,,

.~

T?tals .., ':' : ~ , ' ..... " , ......' . .......

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

REFINERY PRODUCTS AND TEST METHODS

39

alkylate fuels, causing an increase of 2 to 4 units in octane number,


whereas with highly aromatic fuels (catalytic reformates) the octane number may decrease slightly. The new Ethyl Corporation additive is more
effective than tetraethyllead b~t its cost will probably be so great that
it may be used only for aViation fuels.
. The boiling range 26 governs the ease of starting, rate of acceleration,
loss by crankcase dilution, and tendency toward vapor lock somewhat as
indicated in Fig. 3-3. Holaday and Happe1 27 utilize the percentage dis450'~--~----~---T----~--~----~~~~--------~~-

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

FIG. 3-3. Performance of gasoline in a.verage automotive equipment.


out of ten vehicles behave as indicated. (Oil Ga~ J.)
.

About nine

tilled at 158F and the 90 per cent distillation temperature in ~n ASTM


distillation to judge the time required to warm the engine. Most generally, warm:..up is used.as the mi1es of operation required to allow full
power development without excessive use of the choke, and a 2- to 4-mile
warm-up is generally thougbt to be satisfactory. Thi~ is simi1ar to the
211 Nelson, W. L., Gasoline Performance, Oil Ga3 J., Sept. 29) 1945, p. 139.
t7

A Refiner's Viewpoint on MotP.r Fuel Quality, Pet Eng,.., Ref. Annual, 1943, p. 251.
.

40

PETROLEUM REFINERY ENGINEERING

older usage of the 35 and 65 per cent ASTM temperatures 28 to judge


rate of acceleration and smoothness of perfo~anc~ after the engine is
started. If ~he fuel provides 8.dequ8.~ warm-up and acceleration cha.ra~ .
teristics, it is always sufficiently low-boiling
the 10 per cent point to
allow easy starting (Fig. 3-3). Crankcase dilution loss is related 17 primarily to the temperature at 90 per cent distilled, but it is also affected
by lower-bailing-range material. The crankcase dilution loss for the
gasolines suggested in Fig. 3-3 is below 5 percent.. Agreement on
tendency to vapor lock is not good,27.2t but the general situation is

at

Climate,

l:
i'
I]

Ii
r!

AllmDabh maximum

ClimaU,

Allowable maximum

DF

.Reid vapor preSSUTe

.oF

Reid vapor preuure

60
70
80

12.7
11.0

100
110

7.0
6.0

9.4

120

5.3

90

8.0

Vapor pressure also governs storageand handling losses,30 particularly


at high altitudes. The relative tank-filling losses for an 8.5 R.v.p. (Reid
vapor pressure) gasoline at 80F at different altitudes is somewhat 8.s
follows:

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!
"

'

With the advent of high-compression motors, the tendency of a fuel to


spark-knock .o r detonate violently ha~ "attracted much attention. Knocking is' thought to be due to autoignition of part of the charge in front of
the flame. Mild knocking h.as little effect. on the performance of the
engine, bu~ severe knock may result in loss of power and (damage to
pistons or bearings. Certain substances such as lead tetraethyl,31 iron
pentacarbonyl,12 etc., U tend to prevent knocking. All hydrocarbons have
different
antiknock properties, and certain
of these, such as benzoIn and
.
. '

. 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

REFINERY PRODUCTS AND TEST METHODS

..,

those in -cracked gasoline, are useful in suppressing knocking.. Octane


nwnber is greatly affected by altitude. 34,3& The 'octane number may be
about three units lower for e~ch 1,000 it of elevation at elevations near
sea level (growing to. 7.5 per 1,000 f~ at 12,OOO-ft elevation). Thus, if an
octane .number of 67.5- is necessary at . sea 'level, 50 is satisfactory at
6,OOO-ft elevatIon, and at 12,OOO-ft elevation eyen 20 is 'satisfactory.
Knoclcing occurs 27 ,3e in a.verage cars somewhat as indicated in Table 3-9
for a po.lyiorm gasoline that was rich in olefin and aromatic hydrocarbons.
3-9.

TABLE

OcTANE NUMBER REQUlltED TO PREvENT KNOCKlNG

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
!

Approximate percentage of cars


that knock

85

10

T.ABLE

3-fo.

AND

90

ApPROXlMATE OcrANE NUMBERS REQUIRED TO SATIsri

PER CENT OF NINE

1953

10, 50,

MAKES OF CARS OPERATING ON

FUJ..l......:aOlLlNG-nANGE GASOLINES

ma.ke

No. cars
tested

1
2
3

28
24
27

. 4
5

24

Car

28
22

Research octane number to satisfy


10% of cars

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

a-t MacCoull, 'Hollister, and Crone, Effect of Altitude on Anti-knock . . . , Ref.


.
Nat. Gaso. Mfr., November, 1937, p. 534.
ali Effect of Altitude on Knock Rating in CFR Engines, J. Research Nall. BUT. Slandar.ds, 28, 713 (1942).
36 Offutt, Ostergard, Fogle, and Beuther, Naphtha nefonnjng with OutRide Gas,
26th Ann. Meeting of API, Chicago, Nov. 12, 1946.
.

42

PETROLEUM
TABLE

3-11.

REF~RY ENG~ERING

ApPROXIMATE

LEAD

SUSCEPTmILlTY OF GASOLlNE8

AND HYDROCARBONSG

Octane

Type of gasoline

number

Increase in Motor o.n. with


1 co

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

Straight run, low sulfur, low


octane ...........': ......
Straight run, low sulfur, regu1ar octane ...... -~ .......
Straight run, low sulfur, high
octane ..................
Straight run, low suUur . . . ..
Natural gasoline ...........
Straight run, high sulfur ....
Cat&lytically desulfuriZed
crackedd -.
lsooctane mix~ .... -.......
Cracked, low octane ....... .
-Cracked, regular octa.ne ....
Cra.cked, high octane .......
Aromatic gasolines .........
M ethyley clohexan~ ..... _...
Houdry catalytic ....... .- ..
CatalyticBlly cracked .......

Polymer, catalytic .........


Diisobutyleneb
lsooctane" ........ -.........
Toluene" .................

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

REFINERY 'PRODUCTS AND TEST METHODS

number fuels in current vehicles is not impressive 38 or conClusive. Under


some conditions of operation a 10 per cent increase in mileage 39 appears
to be possible by increasing the octane number from 68 to 83, but ~est&
on some vehicles indicated ~o improvement even a decrease in miieage.
High-octane fuels do provide smoother,. more satisfactory peifor:mance.

or

TABLE

3-12.

APPROXlM.A.TE LEAD SUBCEPTlBILl'I1ES OF VARlOUS

TYPES

OF

NUMBEB

GABOLlNEB .A.8 A FUNC'nON Oll' CLEAR. OCTANE

Inereu8 in octane number with 3 ~.o TEL


Clear
octane
Dumber,
Motor, or

Reeearch.

Reformed
(thermal)

Reformed
(catalytic)

St.r&ight

run'

Catalytio
cracked

nermal
cracked

Polymer

a8

applicableO

Motor Re& Motor Rea.

Motor Rea. Motor . Rea. Motor Rea. Motor Re..

-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

The susceptibility of fuels tetraethyllead not uniform. The octane


number is increased greatly if (1) the clear or unleaded octane number is
low, (2) the sulfur coritel).t- (particularly mercaptans, monosul.fides, and
disulfides) is low, and (3) the perce.ptage of olefin hydrocarbons (cracked
gasolines) is low. . Although va'riations are great, the general situation is
indicated in Table 3-11,4.0 which is an average of about 327 tests. Table
3-12 can be used to estim~te the effect of tetraethyllead on the octane
3~

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.

PETROLEUM REFINERY ENGINEERING

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

4.0 5.0 6.0

Te/roelhy//eocf, ml per go/Ion

FIG. 3-4. Ethyl Corporation lead susceptibility cha.rt . . Lines illustrate Research
(F-l) octane numbers of typiqal gasolines.

RE~RY PRODUCTS AND TEST METHODS

i .

.1,
;

,
.\

I
,.

'..

l
i't
I

45

number of various types of gasoline. A substantially straight line results


when the octane numbers of leaded gasolines are plotted on .charts such as
Fig. 3-4. U The .Performance Number shown on the right-hand scale of
Fig. 3-4 represents the approximate relative amount of power that can be
developed.
In summary, our motor fuels consist of butanes and natural gasoline
for .front-end volatility, cracked or polymer gasolines and antiknock
age~ts for allaying knocking, inhibitors for the delaymg of gum formation, and straight-run gasoline. Thermally cracked gasolines are
desirable in motor fuels because of their good low engine-speed performance. The low-boiling olefin hydrocarbons cause such performance. .At
high speeds the aromatic hydrocarbons found in catalytically cracked
gasolines provide superior performance. Thus a mixture of the two kinds
of fuels is advisable; particularly so that the L-head engines which knock
at high speeds and the valve-in-head engines which laiock at low speeds
.
are both satisfied.
Naphthas or Solvents. The enormous nwnber of uses for specialty
materials intermediate or embracing parts. of the boiling range of gasoline
and kerosene makes for confusion and overlapping of specIDcations.
Tables 3-13 and 3-14 show the average properties and uses for 20 representative naphthas u grouped generally with respect to boiling range.
Straight-run petroleum naphthas contain only small amounts of aromatic
hyd!ocarbons and hence are not good solvents for some materials, notabJy
nitrocellulose lacquers, dry paint, or certain resins. High-solvency n~ph
thas dissolve such materials, and special solveI,lcy tests U such as. aniline
point, kauri butanol number; and dilution ratios of nitrocellulose in ethyl
or butyl acetate are employed. The low-gra.vity naphthas of Tables 3-13
and 3-14, shown in boldface type, are high-solvency naphthas produced
by. special processing methods that increase the percentage of aromatic ,
hydroca.rbons. A 48.4 API naphtha similar to No. 16 of Table 3-13, but
containing 15 per cent of aromatic hydrocarbons, is used to deweed crops
of carrots, parsnips, dill, or caraway. '
Among the special requirements of solvents may be white color; low
ll.nsaturated and aromatic content for stability; high .aromatic content
for solution of lacquers or synthetic resins; or low boiling. for rapid volatilization. In general, however, naphthas should be free from acidity,
noncorrosive by the ~opper-strip test, fre-e from gums or suspended
matter, sweet smelling so that a petroleum odor is not imparted to the
Ethyl Corp. Research Laboratory Chart, Apr. 15, 1949.
U Nelson, W. L., Classifica.tion of Solyents and Naphthas, Oil GQ.8' J., Apr. 15, 1943,p. 134.
.
U Nelson,W. L., Dilution Ratio Tests, Oil Gas J., June 30, 1945, p. 117.
Blade, O. C., Annual Surveys, U.S. Bu.r. Mines Repl. Invest. 5132, April, 1955.

, . U

3-13.

TABLB

ApPROXIMATE PROPERTIES Oll'

20

Key number of solvent

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

Solvents high in aromatic hydrocarbons

(high , 80lv~ey)

TABLE

3-14-

4.0
1'19

... . ,," .

. .. - .

200
210
215

210
220

191

245
Z15

240

.. .

..- ...

"

77

~.5

37.5

." .

a.re shown boldfa.ce.

USES OF

20

REPRESl!lNTA~

Key number of solvent with


;

Use of solvent

,Boiling
range,

op

fl

~I

3 ' 4.
2
5
8
'95- 145- 125- 160- lOS-:- 179186 160 206 210 260 275

1. Perfume' extraction .................... 160'-260 ..


2. Castor oil or lat extraction ............. 125-300 ..
3. Toluene substitute, lacquer formulas,

I,

I!

,I

;1

l'

.. ..
.. x

- - --

X
X

. ..

17!)-27~

. ..

:r

4. Seed extraction ...................... 160-300

.. .. .. .. .
.. ... .,. ,- x
5. 'Rubber cements, .tire manufacture ...... 95-370
x
x
x
x
fas~setting

varn.iahes ............ . ....

..

...

- ..

6. Lacquers, art leather, ' rotogra.vure ink,


adhesive tape ........... : .......... .' ~
7. Rosin extra.ction, shade cloth, rubber dip
goods ..... .- ... ~ .....................
$. Brake linings, leather degreasing, bone
degreasing ............................
9. 'Printer's ink, ceUulose lacquer diluent ..
10. Paints and varnishes, thinners .........
1.1. Textile printing and proofing ..........
12. Paints a.nd coa,tings (aircraft), paint removers and solvents ................. '.
13. Pa.int shop rinsing a.nd cleaning (aircraft)
14. ,Floor covenngs, wax, polish, wash for
printing plates or rolls ............ '.. " .
:15. Diy cleaning, metal and machinery
cleaning ........................ . ...
16. Zylol substitute (in ma.ny instances) ....
17. Flat finishes, rustproof compounds . .. ..
18. Synthetic resin thinner .. . .............
19. :,WQod preservatives .... . . " ...... '" ..
"

'

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

.. Solvents high in aromatic hydrocarbons (high solvency) are shoW'il boldface.


46

REPRESENTATIVE SOLVENTS OR NAPllTHAS CI

(see Table 3-14)

,Key number of solvent

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

280 ' 300

25

25

45
38

..

38.5 39-69

54

NAPHTHAS AND SOLVENTsCl


~iling

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

(see Table 3-13)

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

PETROLEUM REFINERY ENGINEERING

manufactured products, and well fractionated' to eliminate as inuch of


the fire hazard as p'ossible.
There is an increasing tendency to offer extremely narrow-boiling-range
naphthas (under 30F) which are s~perior for some services but which can
often be r~placed by cheaper naphthas of wider or conventional boiling
range. Nearly pure hydrocarbons ranging from. propane through hexane
are 'also being offered.
The mineral-oil solvents should not be considered as sUbstitutes for
other solvents that are now used, because mineral solvents possess properties tha,t are unique and useful, and for many purPoses they can be
selected because 'ot tl1eir own merits~
.
Jet Fuels. The production of military jet fuels reached 95,000 bpd in
1953 and the e~pected demand in 1957 is about 250,000 bpd (2.9 per cent
of crude oil). Although a kerosene-like material (JP-l Grade) was first
. used and a similar high-boiling fuel (JP-5) .'is still supplied in limited
quantities, the main current fuels -(JP-3 and JP-4) are wide-polling-range
materials which extend through gasolin.e and kerosene. Ta.ble a-:15 indicates the kinds of fuels supplied and Table 3-16 shows u in detail the 1954
properties and the specifications of jet fue~s. . Production has beet almost
totally ~raight-run material, but there are indications that small amounts
of cracked materials and heavy alky1a.tes or reformates can be incorporated. In the .event of war, such materials will have to be t0lerated.
The Smoke V.olatility Index of Table 3-16 is the IP smoke point pluB
0.42 times the per cent distilled at 40QoF. Its superiority as a means of
judging deposition tendencies over plain smoke point h~s not been com- .
pletelyestablished. The low freezing point of minus 76F is a difficulty
in.meeting speciiications, and if 'certain naphthenic aromatic crude oils
are processed, the gravity requirement becomes 1imiti~g..
Throughout the world. specification DERD~2482, which is an Eastern
Hemisphere kerosene; is used almost exclusively (1956), but some a,irlines
require a freeze point of -50F rather than -40or.
Burning Oils. These oils, represented by kerosene, long-:-time. burning
oil, lighthouse kerosene, and 300F mineral-seal oil, are used, as their
names imply, in household, marine, passenger-coach, and railroad illumi~ting lamps. Kerosene is the main ' product in the United States but
ASTM No. 1 Distillate has such similar properties that it is increasingly
being sold as kerosene. ' Likewise, Eastern Hemisphere kerosene is ~old
as jet fuel. The 300F mineral-sea.1 oil is a high-grade oil having a
. Clevelan4 open-cup Hash point of not less than 250F. Signal oil for
railroad lamps i~ compounded from 300F mineral-seal oil and lard or
sperm oil. Long-time burning oil is the finest grade, and in the burning
test 650 cc of oil must not be consumed in less than 120 hT-

or

j
(

t
,

.
,i

.!

. t

'r

49

REFINERY PRODUCTS AND TEST METHODS

The valu of kerosene is directly dependent upon its behavior in the


burning or lamp test~ An unsatisfactory burning test is terminated by
smoking, by a white cloud on the chimney, or by a Cltoadstool" formation
on the wick. Smoking is due primarily to aromatic hydrocarbons; a
white .cloud is probably produced by disulfides (over 0.01 per cent); and
toadstools are thought to be related to both aromatics and disulfides.
TABLE

3-15.

No.
FUel

of
SarJ1-

pIes

Avg. Grade JP-l:


1952 ... . ........
Avg: Grade JP-3:
1952 ...........
1954 ............
1956 .... : .......
Avg. Grade JP-4:
1952 ...........
1954 ...........:.
1956 .... : ......
Avg. Grade JP-5:
1953 .. ' " ......
1955 .. . ........
1956": ..........
1956" .. , ........

CHARACTERISTICS

0J'

Dist. temp.,

API
gravity

JET FuELS,
o~

10% 50% 90%


evap. evap. evap.

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

6.0 0.081 14.7


5.7 0.089 10.3
5.6 0.063 . 9.3

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

2.6 0.075 11.9


2.6 0.080 11.3
2.6 0.054 10.5
0.46

.. 0.26

8,3
12 . 0
10.0

12.8

4 Blade, O. C., National Annual Surv:ey of Aviation Fuels, 1956, U.S.


Inform. Circa 7782, March, 1957.
11 Both of two sampleS are shown.

Bur.

1.5
1.1

0.6

0.8

..

2.0
0.9
1.0
D.5

Mines

Although the Institute of Petroleum (British) smoke test'S is not


usually specified in the United States, it is used widely throughout the
world. , The smoke point is the height in millimeters of the flame that
can he. produced in a standard lamp without causing smoking. Mi~
Continent kerosene exhibits a smoke point of 21 to 24, and the smoke
point of these materials is raised to more than 30 by acid treating. 48 A
smoke point of 17 is satisfactory for most world trade.
(6IP 57/55, Standard Methods for Testing Petroleum and Its Products, 26 Portland Place, London, W.C.I, England.
.
n Nelson, W. L., Smoke Point and Ring Number of Kerosenes, Oil Gas .J., June 14,
1954, p. 151.

TABLE

3-16.

1954

SPECIFICATIONS AND

PROPERTIES OF JET FUELS"

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

"
....

"

......

,.

..

a .. " .... " .... " _

' '''''I'~- ~'' -

. ,

... .,

.......

"

..

..

"

.....

"

"

"

..

......

"

....

5,240 min
30 max

..

"

....

".

""

35-50

........

< -40 to -59


12.1-13.36
129-146
4,876-5,986
3.7-0.8

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

" "I"" ." I ..

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.

PBoPERTIES OF JET FUELSo

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

~.~--"

.. .. " ""f'"r_ _ _ _ _. .IiII_


...........------~----

~~~------~--~-------

t
52

PETROLEUM REFINERY ENGINEERING '

The Saybolt thermoviscosity is also used to indicate the behavior of


the oil in a lamp by means of the so-called Ring -Number which is:
- j-

,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

Distillate Fuels. Among these are stove gasoline (torches or lamps),


tractor fuels, domestic fuel oils (stove or furnace), industrial distilled
fuels, spray oils, insecticides, smudge oil, straw oil, absorption oil, and gas
oil. Table 3-18 presents the properties of these not closely specified oils.
In northern New Jersey the average quality of No.2 heating oil has been

Conu..,

j~ Hillman, McHatton, and Moerbeek, PTOC~ WorldPet.roleum


2,704, 70S, 113,
and 721 (1933); 8Jld Rather and Beard, Ref. Nat GaIlD. Mfr., 1&, 217 (1936).
U Fuel Requirements f~r Farm Tractors, Pet. &finer, JanuB.IY, 1945, p. 124.

\
t

;.

I
~

I
I,
I

..

'

3-17.

TABLE

PROPERTIES 07 KEaosENE, TBACTOR FUEL, AND

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

Domestio, 41-43, W.w.


Domestic, 44-46, w.w.

"

.....

"

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

'

..

..

....

............

..

........

"

"

"

..

"

..

ooket fuel, RP-l .. : ..

42-45

110

............ 365-410

at 95 % recovered

Speoial _mees require 0.5

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

.. , ......

,.

..........

..

............. ' 35 min o.n .


.......... , . 35 min o.n

Pass

. ...................

..

............ Pass

. ..................

.. ..............

.. .........

0.01-{) .9& ...... . .... Pass

525

Temperatures

"

..

1956 Grade No.2 .... 34.8-44.9 120-185 312-3S2 360-428 474-620

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

CorSmoke rop.o~t, SlDn,


mm cop-

"

...

"

'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'

.~

Thermally and catalytically cracked distillates have not been entirely


satisfactory for the tYp'es of domestic burners now available, because qf
carbonization. The kinds of domestic 'burners and the fuels required ar~:
Type

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

1. Lighter fluid" .........


2. Stove ga.soline .. , . ' ....
3. ASTM No.1, specifioation .... ,' ....... . .....
1956 range .. '.' .. , . , .
4. ASTM No.2, specification., ............ '....
1955 range ..........
'1956 range ..........
6. ASTM No.4, speoifioa.tion .............:-; ... '....
1955 ra.nge ..........
1956 range ..........
6. Ga.s oil (gas enrichment)
7. Gas oil (industrial fuel)
8. Absorption oil ........'.

9. Absorption oil .........

64-70
64-70

.........
..

..

.. .. .. ..

DISTILLATES AND RELATED FUELS

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

o . .. , . . . .. .. 420 .. . .. , .. . .625 .. .. . .. . .. .. 1.4-2.26 Ca.rbon res~ O~ 1&


35+ . 100+
34.8-44.9 12(}-185 -65 to zero' 312-382 360-428 440-554 474.-620 0.01-0.96 1.38-2.43~

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

..... , ...... -. .. 130+


....... , .. .. .. '" , ...... , . .. . .. .
. 20
.. .. . . . . .. . 125
12.8-35.9 154-240 -45 to 70 351-504 447-544 630-748 686-842 0.1-3.27 5.. 8-254
8.7-36.3 152-230 -30 to 25 ' 37~528 438-620 635-730 655-840 0.23-2.2
35
33
195
. . . . ....... 302
460
00
35
.1 + .
30
210
35
440
475 ......... " .. 800+
70
45
505
. . . . . . ... " " . . . . " 344 386
" ........ " "
..

37

..

"

"

~..

.........

"

..

"

482

518

..

.....

.....

"

Copper dish gum 2 max and Reid vapor pressure 7


Centistokes a.t 77F.
o. On the 10 % residue of an ASTM distilla.tion.
fl .Kinematic .a.t 100F.

max.

..

"

"

-~-

..

....

"

..

..

"

..

"

.....

..

to

"

630
'--

B.S.W. below 0.5

"

..

"

"

........ " . .
--

"

.....

"

..

39
-

--

Demulsibility 9
min
Mol. wt 217
---

~;' - ,,.,- ,-..".-.:' :~ ,~_~' ,~, ;,: ,',:*-e,";'rf}~"':-i;o~~%;?;;;,:~~-~~~-?-:~Et:~4.;~~~;~~:;~;;:";';2-'i~fE\~~~:~," -~~~~~~~~S:":",:.:~~:!\A,, '-

3-19"

TABLE

Description of fuel

Fla.sh
point,
of
min

Pour Disti.llation range, of


point,
DF,
max
I.B.P.
E.P.
90%
10%

API

grav'ity

..

........

,.

to

II

..

,,"

""

...

II

..

....

......

..... . . . . .

I'

....

,.

II

....

II

..

...

On a 10 % ASTM distillation residue .


.. Diesel Index .
.. Centistokes.
It War shortages foroed reduotion to 40 during 1944.
II Minimum, ,not a-yerage.
, On entire material.
It

Anilliie
point,
of

..

....

SuI-

Viscosity Carbon Cetane fur,


at
residue, num%
100F' % maxCl
ber ' max

1940, high quality ............ 170


37
35
0 ... " ..... 440
" .........
645
57"
, 33
1940, medium quality ......... 170
o,
470
700 . " ..........
38
48"
" .... , '" .
1944, a.ll-purpose, Azmy ...... ; .' 140
.........
-10
1.6-4.28- 0.15
700
650
504
1944, arctic grade, Army ...... 110
-50 ......... .. ......... 600
650, 1.D-4.28c: 0.15
45d
1947Mmisc" samples ........... 190-200 32-41 o to ':""35 400-416 453-476 500-680 560-724 34-39 ' 0.03-0.1 44-51
AST Grade 1-D:
1950, avg .................. 159
40
369
417
532
575
33.8
0.053
52
1952, avg Eastern U.S ...... ........... 40.3 .. ........... , 366
409
523
566
33.1
0.064
51.6
1954, avg Eastern, U.S ......
41.3
401
358
518
563
32.7
52.1
0.061
40.5 - -6~
1956, avg Ea.stern U.S ...... 122524
408
364
567
33.0
0.076
5l.3
1956, ASTM, D975 ......... ,100
20
... ,. , . .... ,.. ,. ,. . ,.. .. 625 1.4 min/! 0.15
40
ASTM Gra.de 2-D:
1950, avg zero pour ........ 171
693 ' 652
36.5
380
441
35.8
0.081
50.1
1960, a.vg higher pour ....... 185
34.8 ........ ,. . 396
471
621
677
38.8
0.091
50.3
1956, avg Ea.stern U.S ...... 13S
36.8
15
369
li87
645
431
35.0
0.106
50.3
1956. a.vg CentrSJ U.S ...... : 143- .35.9
375
438
15
590
645
0.100
35.6
49.5
1956, a~Western U.S ...... 15425
387
455
33.5
606
668
0.112
37.0
42>.7
1955,-A ~ D975 ..... ...... 125
....
20
675 ...... ,. .. 32-45
0.35
40
()
Marine (typic ) .............. 150
32.0
0.35
35-40
. , ... ,. . , ........ ...... . .... . , 3040
ASTM Grade 4-D:
1950, avg .................. 199
25.3
41-7
510
695
759
76.8
39.5
1.07'
1955, avg Eastern' U.S ...... 160'
27.3
10
398
500
728
773
81.1
36.0
1.48'
-2(}1
1956, aVIrEastern U.S. , .... 156'
22.5
451
511
720
780
46.5
47~2
0.50'
1955, A 'M, D975 ......... 130
......
20
. ...... .... , . .......
45-125 ...... ,. . 30

p,

PROPERTIES AND SPJ:Clll'ICATIONS OF DIESEL FUELS

.......

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

,R EFINERY PRODUCTS AND TEST METHODS

57

alleviate the clogging of screens, the formation of sediment or gum-like


materials, deterioration in color, and corrosiveness.25
Most middle-boiliJ!g-range material (400-90QF) is cracked into gasoline, ' but in meeting the, specifications of such materials as kerosene,
No; 1 Distillate, diesel fuel, and jet fuel, it is necessary to use mainly
straigh t- run rna terial. '
Diesel Fuels. The major performance characteristics 'of diesel fuels..
somewha.t in the order of importance, are

i. Clean\iness-carbon residue, B.S.W., sulfur, etc.


2. Ignition quality--eetane number or Diesel Index.
3. Fluidity and atomization-viscosity,' pour point, etc.
4. Volatility-flash point, distillation, and carbon residue.

,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

PETROLEuM REFINERY ENGINEERING

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

OMPARISON OJ!" IGNITION QUALITY .AND

OTHER PROPERTIES (ApPRoxnU,TE) -

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

0.703B) log T, in which G = API gravity, T =

e, and B

= the

~nstant.

TABLE

3-2L

PROPERTIES 0-' DIESEL FUELS tOR EASY STARTING

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

Motor, .light;.: .. ; ........... . ....


~otor. medium .. , ',' . . . .. '. . .
!i40t.0r, heavy., ....... ......
Unraft. e.urioe, ll&M ............
Uraralt eolriDe, beavy .. ... ..
OleNl ellgiae, lighteat ...
Olelel eo rioe, b.ea vie-t. ........
l'raaImiasiOIl ou. lightes t . . . . . ...

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

Jack'oll, lummer . .............. Rouch alow.. peed beAr- 20-25 400-600


inia. or\l8hlll"8, Bk. . 20-27 200-300
~tB oil ........ . .... ..... : ..... Food manufa.oturing,
29-32 6&-1~
t.extilai, paper, etc.
-

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'.,. .

\ IIok oil, winter .............. .. .

r::";"""'"

V'II-

--

..

n!i:':"'"-"'r""="

DuoS

RANGE OF PHYSICAL PROPERTIES ' OJ!' LtmRlCATING

.. "

...

"" "

...... " "

..

"

".

,
I

.
" .. " ,

.... " ..

II " " " "

...... "

.... "

"

.........

" "

"

---

"

" " ..

"

....

"" ""
" ""

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'

",,

Deterpnoy aDd Viacaaity W


Set\le uom ...,n.oll1tioll, 60 t
8ettlo from aalt IOJUtJOIl, 60 JI

II I.'

...

.. .. " , .

... , .
II '"

Dekrceoay and Viacceity Ind

.... " Deterpaay.aud V'~iiy :w

" ,. ,.

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 " . "

. .. " .. " ....


" " " .. " ....
.. , , " III "

.........
'"

-10 La 16

......

Pnalpit&tioa number, 0.1 Ina


Preaipil.at.iOD numbu, 0.1 ma
VlIOOIity

VlICoailu'
Low- pour point.
Low pour point

None

NeutiaIiatioD number, '0.16 I


None Neutnlll&tiOll. number, 0.161
9-10 Neutraliut.iollilumber, 1.0 III
Neut.ralisa tiOIl Ilumber, 1.0 .Ill
6-7
None Neut.ralilat.l.oo Dumber, 0.1 DI
16-20 Neutnlintion number, 3.0 til
,,1.1
Bkam
Dumber, de!
libility, aDd. SliP cWdI .tion
number alao .peoiW
"'
DiIJeaW ItrqtJl, l-in. (
o.1-m. rap, 26,000 volta
.... . IueoI.abla per D8Ilt. 0.1

emulai.on

...

1 . 1 .. ,

...

t,

.....

IDIoluble per ooat, 0.1


Colorlau

,'

....... . . .

I
60

PETROLEUM REFINERY ENGINEERING

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

Straight ......... , .................


Rust and oxidation inhibited .. , .......

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

Str.!J.ight ......... '. , .................

'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

REFINERY PRODUCTS AND TEST METHODS

gravity-feed systems, etc." it is useful to recognize that the vlscoSity is


about halved by each 20F increase in temperature.
lard, tallow,
2. Compounded Oils. The addition of fatty oils such
rapeseed, castor," arid sperm causes the oil to spread over and more thoroughly wet a metal surface, an~ they "tend to permit the formation of
emulsions; with water that will stick to the metal surface. Thus com-'
pounding is practiced for steam engine, air compressor, quenching, cutting, marine engine, and tempering oils. Fatty oils also nllldly increase
the film strength. Tests for emulsibility, neutralization number, and
percentage of fatty oil are useful.
'
3. Turbine Oils. High-speed machinery,' such as steam turbines and
dynamos, may cause emulsions with water; and hence the ASTM steam
emulsion number (D157) and demulsibility test of the Federal government
(Method 320.13) are useful. Extreme stability, attained mainly by
iong filtration through fuller's earth, is necessary' b~cause these' oils may
be used for several years.
4. Cold Test Oils; Pour point, vlscosity,., and sotnetimes Viscosity
Index are important for oils used for refrigeration equipment, hydraulic
mechanisms, machine guns, instruments, or any machinery in arctic climates.
_
5. Transformer Oils. These and insulating oils must withstand large
electrical voltages, and hence the dielectric strength (usually l-~n. disks,
O.1-in. gap, 25,000 volts minimum) is important. The .steam emulsion
number is usually specified in order to assure stability dUring several years
of service.
,
-'
6. Color Oils. - Such seririces ,~s food, ' paper' or,'textile manufacture,
and' medicinal uSes require a white or very .light-colored 'oil. Lubricant
quality is destroyed to a large extent, by decolorization. : The-cheap black
oils might also be included here, because color
no signifi,c ance. ,
7. Corrosive Oil8. Several services depend in p~r,t on the corrosiveness
of an oil at least in certain temperature ranges. Such oils as extremepressure lubricants for hypoid' or heavy-duty ge~rs, ' and cutting oils
require the addition of sulfur, chlorine, or compounds of these. Suitable
corrosion tests and special performance tests are reqUired for each
service.
Since nearly all industrial services can be met by the above seven general types of oils, it ia doubtful if an attempt should be made to classify
the many specialties used as putty, leather, quenching, penetrating, preservative, wire rope, chain, harness; floor, furniture polish, shoe polish,
wax mixtur~s, den'a turing, wool, shock absorber, hydraulic, brake band,
etc;, oils.
The SAE viscosity classification of oils shown in Table 3-24 is most'
widely used. The lOW and 20W grades are for winter service. Perhaps

as

j
j

I
I

i'
I

is of

,l

I
"

I
l'

,
~

62
..LAJI:I>.t.I.II.I

3-24. SAE

CLAss.xll'lCATION SYSTEM P'OB. Ciu.m.:CASl!I

Univera.l. IIO!I

SA.B
vi8cco-

Redwood

it1

ODF

D.IWIW

oW
lOW
2OW.
20
30

40
lie)

PETROLEUM REFINERY ENGINEERING

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

<II lito ......... "' ....

...

. . . . . . . . . . ., ,I . . . I' '"

41,.

..

111. . . . . . .

a ..... '",.. . . .

II " ' ' ' ' ' . . .

'" ...... "' .... I

. . . . . . . . '"

..

.... I

Ill . . . . . . . . . . . . . . .

41 .. ",-.

.. . . . . 41 .. II 11; . . . . . . . "

a better (but more complicated) classification system is that of the Bureau


of Ships.1i It consists of-a series of numbers of four 'digits each, and a
detailed tabulation of the properties of the oils that ha.ve tnus far bee~
assigned numbers.
tabulation U of properties
too
for
'kiiid of oil, and
publication here. The first digit designates ,die
the
three digits are used to
the numerical value of
viscosity.
The
or types of oils adopted
the Navy are
Vi.tK:ority
measured at

1
!

I
r

,~
f.I

,.

Forced feed, high Viscosity Index (95.-.100) ........... '. ~UOF


n feed, low Viscosity
..... ". . . . . . . . . . . . . .. 13QoF
3xxx Forced feed,
Viscosity Index (65-75) .......... 210~
4xxx Compounded marine engine ........... _.. ~ _.. ~ .... ". 210"F
'Mineral
........ ~
41.. 210F
Compounded steam cylinder (tallow) .............. 210~F
", Compounded stearn
(lard or tallow) .. ~." .. 2~07
8xxx
" a i r cylinder. . . . . . . . . . . . . . . .. 130F
9xxx
engine (heAvy duty).. . . . . . . . . . . . . . . . . . . 130F
lxxx

. .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

REFINERY PRODUCTS AND TEST METHODS

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

40 Viscosity at 210F ..........


SAE lOW ........... ~ ........
SAE 20W ................ , ...
SAE 20 (thinnest.) ............
SAE 30 (thinnest) ......... : ..

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

PETROLEUM REFlNERY ENGINEERING

oils. Sulfur has little


effect, but Merrill.
and Brayll
inconclusive evidence that high-sulfur oils cause
c,?rrosion-that
the wear may have
caused by
different types of hydrocarbons in
the oils rather than by sulfur.
Oarbon residue is not directly related to carbon formation the engine..
The extremely high-carbon-residue Pennsylvania oils produce only a little
more carhon the engine
do the low-carbon-residue.naphthene-base
paraffin-base carbon is much harder and .attaclied more
oils, but
firmly to
cylinder
r>g
Shprt-time engine tests such as the Lauson, Underwood, and Chevrolet
... .-... tests61J and the Work Factor
of the
of ShipeD,1 are necesmaking
evaluations of oils. However, even such elaborate
test methods sometimes produ,ce confusing results and- they indicate
clearly that
'result~ are a. fmiction of the way the 'engine is operated
as 'well as of the properties of the fuels or hibricants being tested.
Additives are. now widely used to alter the properties of lubricating
oils. Pour-point depressants act differently on each oil, but on
average cause reductions in.pour point~n aboutas follows:

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

REFINERY PltODUCTS AND TEST METHODS

.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

Piston hea.d, of ..............


Top ring, OF .................
Lo wer ring belt, of ...... . ....
Cy linder wa.ll, of.; ...........
Crankcase oil~ ~...... . . . . . . . .

500-650

650-750

.......

475-500
350
350
170-250

200-325
300-350

160-250

These high temperatures tend to cause rapid oxidation of the o~ on the


piston head and top ring,.with the formation of solid asphaltic material
from paraffin-base oils but only sludge82 in the naphthene- or detergencytype oils. Thus, when paraffinic oils are employed, varnish like deposits
.tend to H cook down" on the lower walls of spark-ignition pistons, and coke
deposits are formed around the top ring of diesel-engine pistons. Detp.rgency oils do not assist greatly in removing the varnishlike deposits of
spark-ignition engines, but they do suppress to a large extent th~ coking
of diesel engi~es by keepingJhe carbonaceous material in suspension.
TABLE

3-2'5.

ESTIMATED ANNUAL CoNSUMPTION


(MAlNLY) AUTOMOTIVE LUBRICANTS,

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

PETROLEUM REFINERY ENGINEERING

Antioxidant additives to alleviate oxidation, sludging, or corrosion a.r~


extensively 'used. An enormous number of agents have. been recommended or used; and a few are calcium petroleum sulfonates, sulfurized
terpenes or olefi.ns, metal salts of phenol sulfides, phosphorus pentoxidetreated terpenes, and, zinc m~thylcyclohexylthlopho.spha~e'- Antifoaming agents such as silicone compounds when used in minute amounts
effectively reduce the tendency to foam.
Lubrlcants. This term is applied primarily to greases, semisolid compositions, and gear oils, even though some of the ma.terials are as much
like liquid oils as like solids. Most generally, greases may be grouped into'
three classes. 83
1. Admixtures of mineral oil and solid lubricant . . Some of the common
solid lubricants are graphite, mica, talc, sulfur, and asbestos fiber. These
greases are invaluable in the lubrication of ill-fitting machine parts functioning under heavy or intermittent loads. Examples of this type are
tractor-roller lubricants, lubricants for concrete mixers, ditch-digging
equipment, and railroad-car unloading devices.. '
'
2. Blends of residuum, w~ uncombined fats; rosin oils, and pitcM8.
This group is particularly suited to the lubrication of rock' bits, steel
cables, water pumps, dredges and chains, and gears operating under water
or under exposed weather conditions.
3. Soap-thickened mineral tn"ls. Common thickeners are sodium, calcium, aluminum, lithium, and lead soaps. The soaps of these metals are
prepa.red by saponification of a fatty' glyceride. of either an.im.al or vegetable origin. This group is widely useful because a large variety of.
different-consistency greases can be produced by' selecting various
,
metallic soaps, fat~y' glycerides, and mineral oils.
G4
There are also three general bases used for manufacturing the extremepressure lubricants now used alm~st exclusively for differential, transmission; and general gear lubrication.
1. Blends of saponifiable oil containing chemically combined sulfur
With a suitable lubricating oil-or mineral oils to which Bowers of sulfur
has been added.'
2. Blends of a sulfur chloride-treated saponifia~le oil base and a lubricating oil of suitable viscosity-or chlorine combined. directly with chOSen
mineral-oil fraetions.
3. Lubricants containing lead soaps of fatty or naphthenic acids and
sulfur. These may contain sulfur that has been added or only the sulfur
that Is, naturally present in the mineral oil. However, the most common
USim pson and Welch" Manufa.cture of Greases Ref. Nat. GfUfO. Mfr., March, 1931,
p.77.
'
h Eba.ugh, I. A., Service Tests Must De~e Value of Extreme Pressure Lubricants, phri 2, Natl. Pel. Ne:ws, Jan. 15, 1936, p .. 26.

REFINERY PRODUCTS AND TEST METHODS

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

Saybolt Univ. viscosity

15,000 max a.t OaF


15,000-100,000 at OaF
75-120 at 210 DF
120-200 a.t 210 DF
Highest temperature service 200 min a.t 210F

Extreme low temperat~e


Winter service

......

................................

.....................................

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

Description and use


a.t room t.emperature

Semifluid
Very soft, grease gun
Soft, grease gun ,
Grease cup
Grea.secup
Grease cup and block
Block type

ASTM, Report of C&rn,mittee D-2.


Si Nelson, W. L., Corrosion Tests of Gear Lubes, Oil Gas J., Apr. 7, 1945, p. 97.
, Thompson, J. W., Varied, E. P. Lube Specifications .. , Noll. Pet. News, Sept.
30, 1936, p. 36.

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

Sodium, brick type

Hard or briLtla

AJuminum

Mixed lodium oalaium

Lithium

Bu~tery

1400

315

Bu~tezy, rubbery, Dr Butteq or Itringy

t.o fibrOWI

stringy but, DIver fiDropp~

point, .,

220-~

(approL)

Cooditioo atter hav- Separates


101 heated to meU.-

iDa poin~

l'

176
Wuimum temperature, -F (aont.muoua

I
Q)

3Q0-450

276

Foams at 200"11'. Sop-I No ~g. if'worked


arat.ea UPOA pro- ,
loaied bea.~

brous
200

~&O

Cb&Di- terlure upon I No DhaDp if worked

I No ahaap

No obal1gB if worked

oooliDg bat does DOt


ae~te eve,D above
mel.W1a: paint

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.

work- Fair to poor

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.

___ ., _______ ..- __ . ~.' __ '.-w__

~-"- " ----r-"

a~

~,.. - -( . .

'g':O:-:,".. ~..,..~-~

, . . . . . . . . '"

REFINERY PRODUCTS AND TEST METHODS

69

An enormous number of combinations of oils and soaps is possible.

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.

P~ROLEuM REFINERY ENGINEERING

70
TABLE

Wax

Petrolatum .......
Petrolatum .......
Petrola.tum .......
Microcrystalline ...
Microcrystalline ...
Microcrystalline ...
Microcrystalline ...
~icrocrystanrnne ...
~

Varies widely.

3-27.

t
.~
I

MICROCRYSTALLINE AND PETROLATUM. WAXES

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

Gra.vity is a function of the properties of the parent crude oil.

adhesives; ammunition; banda.ges; burns; belt~gj candles; carbon paper;


cheese wrappers; coatings for drums or cans; cobbler's wax; concrete mixtures; dental cavities; electrical condensers, cables, coils, transformers,
batteries, eto.; electrotyping; emulsions; food sealing; Boor polishes; fuel
briquettes; foil coa.tings; illuminants; ink; insulations; glossing agent in
laundries; lipstick; lubricants; embalming preparations; matches; impregnating cloth and paperj milk and liquid containers; modeling wa.xes; moistureprooling pape~ coatings, candy wraps, laminated paper'- bags, etc.;
paperboard for boxes, cartons, can substitutes, drinking cups, frozen-food
pa.ckages, milk cartons, etc.; pastes; pencils; pipelines for acid; plasticizers; polishes for shoes, leather, or furniture; pyrotechnics; plastic molding;
ropes; roofing; rubber blooming; rust preventatives; salves or ointmen~sj .
ski wax; stencils; stonework; ,surgery cavities or deformities; textiles for
bath curtains, canvas, tarps, felt hats, lubricated threads, shoelaces, yarn
finishes, waterproofing, etc. j toilet creams, pastes, etc.; washers; wire
coatings; and wood fillers.
.
Residues. The residual petroleum )roducts usually do not command
a. high market price. Often they' are merely by-products of the regular
refining operation~ Some of the residual products are residual .fuel oil,
fuel oil for diesel power engines, road oil,. spray oil, coke, and paving,
roofing, or paint asphalts.
.
Typical residual fuel oils and dusting oils exhibit the properties shown
in Table 3-28. Oils 1 and 4 are the 1955 standard (ASTM D396),1 the
older oils (2 and 3 of 1933) are still .representative, 72 and the average
coal-spray oils were taken from Technical Report 6 of Bituminous Coal
Research, Inc. 73
.
~2 Nelson; W. L., BunkerFuel Oil Specifications (1918-1946), Oil Ga. J., July 27,
1946, p. 196.
11 Nelson, W. L., CoaI-apray Oils, Oil Gtu .T Aug. 21, 1941, p. 56.

!
I
i

'~

22_ ... L)

71 .
T.ABLE

3-28.

FuEL AND DUSTING OILS

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

40 Furol a.t 122F


-20 to +60 11-40 Furol at 122DF
-30 to +50 11-40 Furol at 122DF
1
................ 100 Universal at 100F
1
.................. 100 Furol at 122F
2
................... 300 Fum! at 122F
0-1.8 .
51-295 Furol at 122F
5 to 80
0-1.6
o to +60 28-292 Furol at 122F
........
o to -50 111-223 Universal at
100F
-5 to -20 246-599 Universal at
100F

1
0-0.8
0-0.8

III

....

flo

.......

.....

.. U.S. Bu.r. MineIJ Inform. CircA 7730, October, 1955.

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

PETROLEUM REFINERY ENGINEERING

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)

orfor a.verage values.of the

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

TEMPERATUlU!I FOR BURNERS

. Firing temperature, OF
. Fuiol _v iscosity

at 122F -

.30 .......... ..........


35 .. :, .................
.4.0 Fuel 5 max ..........

45 Fuel 6 min ...........


60 . ....... : ...........

SO .....................

100 .............. , ......


120 .... ~ ... ., , ... , .......
160 .....................
200 .. , .. , ... . ...........
2 40. , ...... , . -, ..........
300 Fuel 6 max, .... , , ...
71

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

Nelson, W. L" Oil Gtu J., Dec. 22, 1952, p. 353.


Nelson, W. L., Oil Gas J., Sept. 13, 1954, p. 138.

154-193

160-200
164-204
170-210

:-

REFINERY PRODUCTS AND TEST METHODS

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
":

Early pet. cokes,


1930-1935
Cracking
still

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

Moisture, wt % ............ . 0.15-3.3 0.3-1.8


Volatile combustible matter,
8-18
wt % ................... .
2-13
Aah, wt .................... .
0-1.6 O.
.2
Sulfur, wt % ............... . 0.2 -4.2 O.
.2
Bulk density, Ib per cn n .... .
56-69
...............
True or real
g per mI ..
Btu per lb as rec'd .......... . 15,300- 14,50016,400
15,500
wt %................. .
. ...... " .. "
eMbon, wt % .............. .................

JII

12,864,077

and Hoiberg, Ind. Eng. CIum., 41, 2122 (1953).


" 'Estimated.

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

REFINERY PRODUCTS AND TEST IlETHODS

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+

of ..... ' .... 112

Ductility at 7rF em ... 60+


Penetration ai 3~ .... 4.0
Pelletration 6\ 77"F... : 135.
Soft.
Pelletration a\ 116"1' ...
Evaporation (50 I, 5 hr,
0.01
326F), per cent; ..
JI'1aah, ClevellUld ope.q
oup, of . .: .... 5&0
Solubili~y ill ern., per
oent ........... '99,8

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

80ltening point, BctR,

T ABLJI 3-33. Orlnat

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

pliability of the finished product. Temperature susceptibility measures


the change in penetration (D5) 1 with temperature and also the ability
of the asphalt -to withstand J .lading and shocks. Ductility (Dl13)1.
measures the elongation or ~\i.fetch, suitability for paving purposes, and
ability to resist vibration. Shock tests are also used for vibrational services, and pliability tests 3,re necessary for compositions used for wire coating or for la.minated ph-per. Stain tests are often important. Solubility
(D165)1 in carbon tetrachloride indicates inert material, asphaltenes, and
difficulties caused by overheating during manufacture or application.
TABLE

3-34.

TEsTS ON TYPICAL LIQUID AsnuLT MATER:U.LS4

Rapid

ewing

Flash, OF (Ta'g open cup} ............


Viscosity Saybolt Furol:
At 77~ .........................
At 140F ................... : ....
Distillation (ASTM D402) per cent
diStillate off: ,
At 437F ........................
At 500F ... ~ .......... ; .........
At 600F ........................
At 680F ................' ........
Residue from distillation:
Per cent aspbalt ..................
Penetration at-77F ....... . .......
Ductility at 7ioF . . ~ .............
-Solubility in CCl~J per cent ........
Asphalt, of 100 penetration, per cent ..

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

~ Petroleum Asphalt, IILubrieation," The Texas Co., June, 1946.

The ASTM18 has published at least 30 specifications for the numerous


,types of petroleum asphalts and road oils. The most fluid road oils '
of the RC, Me, or SO grades are designated as No. 0 and the heaviest
as, No.5. The rapid curing (RO) grades contain 8" cutback of kerosene
orJ'distillate.-like material, whereas the slowest' curing (SC) grades may
consist, of asphalt and the heavy distillates that are naturally associated
with asph~lt in orude oil.
' CHEMICALS AND SPECIALTIES

According' to It SyD.thetic Organic Chemicals, U.S. Production and


Sales," which is published yearly by the U.S. Tariff Commission. the
.

'

I
I

\
\

REF~RY

TABLE

3-35.

77

PRODUCTS AND TEST METHODS

CRUDE PRODUCTS FROM PETROLEUM AND NATUlUL

GAS

Thousand pounds per year .

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

Ethane ............... '....... '.


Ethylene ......... , .. '..... , .....
Propane ...... '...... '........
Propylene a.nd C~ mixtures. ......

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

number of oilcompanies that participate in the manufacture of chemicals


has risen from a..few in 1935 to 48 by 1944, and to 63 in 1955. At least
187 chemical, petroleu.m, etc., companies used petroleum or natural gas
as the raw stock for chemical manufacture during 1955, and the petrochemical production amounted to about 25 per cent 8& of all chemical
manufacture. J. C. Reidel&& estimates that basic petrochemica1s appear
finally in the form of 7,000' end-use chemicals. The 1955 production,
according to the U.S. Tariff Commission, is indicated in Table 3-35, and
the production 87 of major chemicals produced largely from petroleum is
shown in Table 3-36. Some important chemicals are produced mainly
from petroleum:
Petrochemicals .. Today a.nd Tomorrow, Oil Ga8 J., Sept. 6, 1954. p, 83.
Katzen, R' I Pel. &fi,Mf', December, 19M, p. 128.

78

PETROLEUM BEFINEBY ENGlNEElUNG

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.

PRODUCTION AND CAPACITY FOB MAJOR CumuC.AL8

OBT..umm

)'ItOM PET:QOCBJ:M1CAL AND NONPETBOLlWK SoURCES

Million pounds
Production
1955

Capacity
1955

Ethylene ...... , ...........


Propylene .................
Butylenes.... ',' ... , .......
B u t.a.diene. . . . . . . . . . .' . . '. . . .
Acetylene. , ........ : " ....
Benzene.............. , .....
Toluene ..... '... ,' ........ '.

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 . ,. . . . . . .'

Styrene .... , ............. '.


Polyethylene ...............
8yn thetic rubbel'. , . , .......
Phenol ..... , ......... ,'....
Am.monia. .............................
Aliphatic chemicals:
Formaldehyde ..... _. " .....
Aee~dehyde ..............
Methanol. ...... , .........
Ethanol ... _... - ..........
Isopropanol. . . . . . . . . . . . . . . .
Butanola..................
,E thylene oxide .............
Ethylene glycol. ..... '......
Acrylonitrile ...............
Acetic acid ....... . ........
Acetic ~ydride. . . . . . . . . . .
Acetone ...................

Katzen, R., Pet.

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

JlBfi:Mr, December, 19M, p. 128

\.

tl

650

900
700

j
t

CHAPTER

EVALUATION OF On. STOCKS

I.
i

Although it is theoretically possible to produce any type of refined


product from any crude oil. it is not usually economically feasible to do
80.
Occasionally the demand for a particular prOduct or the elimination
of a low-vallie one becomes 80 insistent that major conversioDs of 8. chemical nature have been adopted. Among these are thermal or catalytic
cracking for increasing the yie1d of gasoline. from crude oil, catalytic
cracking for reducing ~e yield of residual fuel oil, polymerization for
recovering olCfurlc waste gases, solvent extraction processes by which
unsuitable hydrocarbons are eljminated fromhibricating oils, diesel fuels,
etc.,. and most recently c atalytic refolming for producing motor fuels of .
superior de~onation characteristics. It is the purpose of this chapter to
aid in the selection of the best combination of products that is .possible
from each crude oil, never forgetting that each oil must be processed to
supply its own particular marketing environment.
The routine or control tests mentioned in Chap. 3 are not entirely
~tisfactory for plant design or plant operation, and hence special distill~tions, vaporizations, and equipment have been developed by which. the
yields of the various products .c ontained in a charge stpck can be eval~
uated. Admittedly many evaluation methods are approxiinate. They
must be so because so many combinations of yields are possible and the
market demand varies so rapidly .that more precise methods would lead
to endless testing. Nevertheless, the somewhat grOBS methods outlined
here ~ust always be used with caution, and they should be augmented at
the first opportunity with more complete ~s.
Large refiners usuany obtain more complete data thaIi suggestedhere,
by means of pilot- or semiplant-scaleequipment in which the essential
physical a.nd chemical processes of the operation are duplicated in labor&'
tory equipment: Smaller operators sometimes find that commercial-scale
experiments are cheaper. Although pilot plants can Uf~~ally provide
more complete and accurate operating information than commercial
operations, pilot plant operation is in some ways more, difficult than
commercial operation, and thus carelessness may result in misleading
data.
79

80

PETROLEUM REFINERY ENGINEERING

The refiner desires information of the following types:


1. ,Base and general properties of the crude oil.
2. Presence of impurities sueh as sulfur, salt, and emulsions which cause genera.}
difficulties in processing.
S. Operating or design data. Prima.nly this necessitates curves of temperature and
gra.vity .VB. per cent distilled.
o. Fractionating or true-boiling-point distillation curve.
b. Equilibrium or flash-vaporization curve.
c. API or specific-gravity curve of each fraction distilled.
4. Curves of the properties of the fraction's VB. per cent distilled (mid per cent curves)
or the average properties of a series of fractions va. ~centage yield (yield curves),
by which realizations of yields ca.n. be prepared. Among common property curves
are
a. Viscosity of lubricating-oil fra.ctiohs.
b. Octane number of gasoline fractions.
c. Aniline point of solvent, kerosene, or diesel fractions.
d. PeJletra.tion 'of asphaltic residues.
e. Viscosity of distillat.ion residues.
Large samples (from 2 liters up to pilot sizes) of the feedstock are required in order
to obtain large enough,fractions for the above tests.
5. Finished products. Having established the general properties and yields by means
of distillations and property curves and exploring the economy of the various break. ups of the crude oil, most refiners feel that large samples of the most promising products should be produced. Batch- or semiplant-scale. stills are employed; and such
details as chemical treatment, sulfur content, susceptibility to tetraethyllead, pour
point, etc., may be investigated.
BASE OF CRUDE OIL

The classification of crude oils as Paraffin, Intermediate, or N aphthene


"base" is admittedly inadequate, but long usage has led to concepts that
are valuahle to ~pe~enced technical men. Whcm used or d~fined' with
respect to various properties, indexes, etc., as in Table 4-1, the term
II base" is justified.
The U.S. Bureau of Mines 1 designates eight bases
of crude oi1 according to key' fraction No.1, which boils at 482 to 527F
at atmospheric pressure; and key fraction No. 2 which boils at 527 to
572F 'a t 40-mm pressure (approximately 733 to 779F at 760 mm)
in the standardized Hempel distillation2 of the Bureau of Mines.' The
first word ~f the name of the base (such as II paraffin" in H paraffin jntermediate base ") applies to the gasoline or low-boiling fractions, and the
second word applies to the Jubricant or high-boiling parts of the crude oj}.
Key fraction No. 1 should have a gravity higher than 40 API for paraffin
base crude oils and a gravity below 33 API for naphthene base oils.
Likewise, leey No.2 classifies an oil as paraffin base if the gravity is
Lane and Garton, "Base" of a Crude Oil, U.S. BUT. Minta Rept. hwe8t., 3279,
September, 1935.
2 Smith
al., U.S. Bur. Mines Bull. 490, 1950.
1

et

ti
~

EVALUATION OF OIL STOCKS


,

81 "

above 30 AP~, or as naphthen~ base if its gravity. is below 20 API. In


addition, the presence of wax in key fraction No.2 is noted by means of
the cloud point. If the cloud poip.t is below 5F it indicates lit,tIe wax,
and the name of the base is augmented by the statement "wax-free."
Characterization Fa.ctor is not spe'cified by the Bureau of Mines, but
approximate values are shown in Table 4-1. Finally, other significant
names for paraffin-base crude oil are "Pennsylvania J ' and U green or light
Mid' Continent JJ crude oil; fot intermediate-base, the terms II Mid
Continent" and "-mixed-base"; ' and for na.phthene-baseJ ' the terIrul
"Coastal," II Gulf cOast," If California," or "asphalt-base.~' These
names a.re often misleading" becau,se the base of an 'oil is not necessarily
related to the region of origin, or the' presence of asphalt 01" of paraffin
wax. In addition to the three common designations of base, a few oils'
contain sign.i.ficant amounts of aromatic hydrocarbons, and these' are
called aromatic or benzenoid "base. Such crude oils are' rare in the
.United States but are found if:t $ome regions, _notably Burma and Borneo 3
(see also Fig. 2-2). A maj or danger in a. II base", classification is our
tendency to imbue a ' cru~e oil with ,'all .the attributes of its base. ' Consideration of Table 4-1 .indicates clearly that wide ranges of 'properties
are probable in any base of crrid~ oil.
. .'
,
Although most of the indexes, .factors, etc., used in claSsifying crud'e
oils and their products were originally based on the properties of pure
hydrocarbons, none of them are tru1y successful in indicating chemic~
composition. They fail to distinguish between a mixture and a compound",
of the same physical properties. Even aniline' point,- which has a longestablished reputation as a means of indicating the presence of aromatic
hydrocarbons, is of little value, in judging '~hcinic~L composition unl~8I
, the proportions between 't he other seri~ ' of hydroc~rbon3 are, also known.
Char~cterization Factor. The most widely used index is the Characterization 'F actor of Watson, Nelson,' an~ Murphy~ 4 It was originaHy
, defined as
,

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

AND TXEIB PRODUCTS IN TIIIWS OJ' CIUBACTBlUZATlON FACTOR AND


~R SIGNIFICANT PaOl'EBTIJiS
,

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&

801- Dieael Dieael


vonw f~ela IAdox

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

Kauri VilO_toy Iadu

"

"

"

" "

.....
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

--' ~'-~.--------

TABLE 4-1 Con~inued.


API "ra.vit.y 01
fraction.

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-

No.1 No.2 stant" venta

--

Mid

11.8
11.76
11.7
11.61S
11.6

Dieael fuela

il'&V-

Charac-Guo.
teri&atioD

11.86

Vis- Aoll1ne point.


OF'
o08ity

Dieael Dieael
luel,a Index~

Ce-

--

taD8

Mid Mid Mid Mid Mid Mid 'MId Mid


bp
bp
bp
bp
bp,
bp
bp
bp
bp
ZS5"F 504DF 155F 493"F 716F 800"F 3000F 550F 6S0F
-68.0 38,3 26.7 29.8 43.9 0.857 129
162 58.0
61.2 37.6 26.0 31.7 46.7 0.862 126
160 56.0
156.3 86.Q 24.4 83.3 47.4 0.867
123
54.0
158
6~.4
36.2 23.7 85.0 49.2 .0.872 120
136 52.0
64.7 35.5 23.0 36.7 li1.1 0.871 117
153, '.50.0
54..0 84.8 22.3 38.6 63.1 0.-882 113
160 48.0
6S.1 34.0 21. 7 40.2 55.0 0.887 110
14.7 ,46.0
62.S ' 33.2 21.0 42.0 .56.9 Q.892 106
148 44.0
61. 4-

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.

ASTM Motor method F-2, d6ll. D3~7; &ppronmate.


ct Baaed OD FAr Eut atoob.

84

PETROLEUM REFINERY ENGINEERING


TABLE

4-2.

CHA'lUCTmllIATlON FAOTOBS OJ' A

F'lIw

HYDROCARBONS,

PlrraOLEUlI8, AND -r~ICAL SroCK,s

----~------~--------------~----------~--------~------.---------Charaeterisation
'Paotor

U..7
14:.2
13. SIS
13.5-13.6
13.0-13.:Z
12.8

HydrocarboDil

Typical orodo oils

MiaceIla.aeoua product.

Propane
Propylene
Iaobub.ne

12. U

H..3 API abeorpt.ion guo.


VenesueJan paraffin wuee
Paraffin wu; M. C. 82.2 API
"Datural guo.
2 methylhepb.ne.and tetra.- ......................... . Calif. 81.9 API bAt. guo,
deoane
Pentane-1, haen.l, and
cetene
Deb\l\amsed B. TeL nat..
2,2.4 trimethylJ,entane

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.

Panhandle (TeL) IUMe

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

Middle Eaat. light. produota


er.eked gaao. f!'Om parafIlnIo
feed.
Eaat. Tau gsa oil and lubes
Light. cyclovenion g84M>. from

Hexylcyclobexane
.i . . . . . . . . . . . . . . . . . . . . . . . . . . . . "

G Venesuela.n wu diatillatea
p~ baoe gaaoliD_

:Fullerlou (W. Ta.)


l1liDoie; Midwa.y (Ark.)

..........................

11.76

W. Tex.: J'uaepin (Vene.)

Cowden (W. Tex.)

Middle East gaa oil Uld lube.


Cracked guo. from inter-

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

Ootyl or diamyl benHne

11.6-11.8

11.5

11.4

Et.hylcyclobuane and 0buyl!! methylhepta.diene


-Metbyloyclohexane

11.3-11.4
11.3

..
Cyclobub.ne And 2,6,10,14

11 . ~

teLrametbyl heudien.

Sant& Fe Spga. (Ca.lif.)

CaL. cycle lltocks from p.uaffinio feed.


Slaught.er CW. Ta.); Robbe Cracked peo. from napa(N. Ma.)
t.he1l4 f eed.s
Tia Juau (Vene.) 1M oil and
Colombian
lobee
Headrick aDd Yate8 (W. -N aphthenio guo.; eat.
(~cked) guo.
Tex.)
Cat. cycle atoOQ from M. C;
Elk Baain. heaYy (Wyo.)
leech
Kettleman Hilla (Calif.)
~ked ga.eo. from hJalV
naphthemc feeda
High conversion cat.. cjel.
Smackoy-er (ArL)
.t.oeb from p&t&flimc f~
Typica.rcat. cycle sLoob
LaguniUa.e rv~)
Gulf Coast-light diat.Illatee
Light-cil coil thermal feed.
Cat. cyClQ .tooka from 11.1
C.F. feedl
Guo. from ce.t. l'6forming

-r

i
l

I
l-

-\

-I
\

EVALUATION OF OIL STOCKS


TABLJI

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

1,2,1.4. tetrutbyl bemeM

11. 0

Cyclohepta.n&8 and dicyc1a:huyl

Typieal crude oile

~laCeIlaD&o\l8

Kern River (Calif.)

produc'-

Greta o~ Placedo (Tes.)


8ipal. Hill (Calif.) .

Thermal &&s oil from naph.


~hene leeds
Naphthenic gsa oil and lubea
8.8 API viscosity breaking

'l.oweat C.F. crude oUa

*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

"pbeDyl-4-me~lhu:ene-2;- . _ . . . . . . . . . CaL cycle ak>cb irom ~h


thema feeda
Reeidu~ by aevere vieco-Butylbtmaene
1\1' breaking
,
PropylbeDsena Cd 1,2.3,1 25 APllilJht (Pure) rea,-cle Low~ C.I'. cat. cycle ato. .
8.5 API reaiduum
\etrAmethylbenseDe
17. 5 API flaah diBtillate TIaermal FecyeJe stocks
2-phenylhe:udiene-l.3
hom M.C. residuum
Et.hylbenlene Dr ",%},len6 8.8 AP! vapor phaae residuum
8.5 API ft.ae.h diatUla~
Extract. from cracked dies:el
Ph8Jly laycloheuDe
(nell
5.5 API.fIaah diat.il.la.~
Toluene
ExUacta from crACked dIeeeI

fuela
10.0

g. 8--0.0

Benseno or 2-ieopropyl
aapMhAleDe
Diphenvlmet.hane

Loweet C.F. cycle at.oeh


Loweet O.F. pitohea' , (- 4 08.1 craekinl reiDdutis
API)

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.

Viscosity IndeL This index is a series of numbers ranging from 0 to ,


100 which indicate the rate of change of vIscosity with temperature. & A
Viscosity Index of 100 indicates 'an oil that does not tend to beco~e
viscous at low temperatures or become thin at ebvated temperatures.
Typically paraffin-base lubricating oils exhibit a Viscosity Index of nearly
,100, whereas naphthene-base oils on the market show about 40 Viscosity
Index, and some naphthenic oils have a. Viscosity Index of ze~o or lower.
Paraffin wax has a V.1. of about 200, and hence its removal reduces the
Dean a.nd DAvis, VlBCOsity Variations of Oils with Tempera.ture, Chem. Mel. E-ng..
36, 618 .(1929); Applying VlSCOsity Index to the Solution of Lubricating OJ) Probl~
Oil Gat J., Mar. 31, 1932, p. 9-2.
.
5

I
I

I
I

.86
UNIV.

SAV80L.T

VISCOSITV

AT 100" F.-SE.C.

t
r

(
I

t
~

RAW PttNNSVl"VANIA

'RAW MID-CONT. OFt

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.

Universal viscosity a.t lOOF

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

Lubricants, ASTM. 1916 Race St., Philadelphia.

Pa.,

87

EVALUATION OF OIL STOCKS

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

Viscosity Gravity Constant. This


constant7 involves gravity as well
as viscosity,
VGC = lOG ....:. 1.0752 log (V - 38)
10 - log (V - 38)
(4-2)

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

FIG. 4-2. Viscosity Index.


Davi8~ Chern. Met Eng.)

+ 47~.7g _ 0456.8

lL , 4{)O

~2,000

where G is specific gra.vity at WOF


and V is viscosity at 100F. It is
used mainly for lubricating oils, and
the general relationship of VGC to
Characteriza.tion Factor is indicated
in T able 4-1.
Correlation Index. The Correlation Index, 8 like the Characterization Factor, relates boiling point
and gravity:

1<;/\

(Dean and

(4-3) 0

eC

in which K is absolute boiling point degrees Kelvin


+ 273), and g is
the specific gravity 6%0' It is especially useful in appraising the 3,000
or more Hempel assays9 which have been conducted by the U.S. Burea:u
of Mines (over 200 foreign oils were tested).
Numerous other constants are more limited in usefulness (see Table
4-1) as (1) aniline point (D611),& (2) Parachor,lO which involves surface
tension and gravity, (3) carbon-hydrogen ratio,ll (4) characterization
gravity,12 which, is used in judging stocks for 'thel?llal cracking, (5) Diesel
Kurtz, S. S., Jr., et al., Rela.tionship betweell Carbon-type Composition, "Viscosity-Gravity .. , , Anal. Chern., 28, 1928 (1956).
I Smith, H. M., U.S. Bw-. Mines Tech. Paper, 610, 1940.
t Hughes 8.Ild Blade, U.s. Bur. Mines Inform. Cire. 7470, June, 1948.
10 Heinze and Marder, BrennstoJl-Chem., 16, 286 (1935).
11 Cauley and Delgass, C-H ratio of Catalytically Cracked Distillate Fuel Oils,
Oil Gcu J., July 'l:l, 1946, p. 166.
It Mithoff, MacPherson, and Sipos, 0:1 Gcu .T o Nov. 6, 1941, p.,81.
7

88

PETROLEUM REFINERY ENGINEKRlNG

Index (Ta.ble 3-20),

n. I .

= aniline point (<>F) ~ gra.vity (API)

(4-4)

100

and (6) boiling-point gravity constant,13 which in terms of B; constant,


0, the API gravity, and T, the boiling point (OC), is designated as:
G= B

+ (68 -

O.703B) log T .

TYPICAL CRUDE OILS

. Crude petroleums vary widely in composition from almost gaslike


materials of 65 API graVity to semisolid asphaltic material ha.ving an API
gravity of 10 (see Table 4-3 for average gravities). The percentage of
T.ABLE 4-3. GRAVITY DISTRIBUTION OIP THE CRUDE OILS PRODUCED IN

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

EVALUATION OF OIL STOCKS

Analyses of ,a few typical or unique crude oils (of the thousands known)
are tabulated in Appendix B.
TABLE

4-4.

AVERAGE GRAVITIES AND SULFuR CONTENTS OJ' CRUDE OILS4

Crude oil

Ratio of % sulfur to Avera.ge


% sulfur in U.S. oils}, gravity

Typical Gulf Coast (U.8.) ..... '. . ..... ,


Far East (India, Pakistan, Burma)" ... ,

0.15

East. Texas field. . . . . . . . . . . . . . . . . . . .


U.S.S.R. &: Eastern Europe d :
California. .... , .. , ......... , ... . ... , .

0.67

Average
% sullur

0.19 Under 0.2

22.&
.. .

....

III

0 .26 '
Under 0.4

0.75

38.0
.........
26.2

Average, U.8 ... , ........ '. " .. , , . "

l.00

34.1

0 :75

VenezUela ... .-. " . , ...... , . ..........


Western Eu rope l . . . . . . . . . . . . . . . . . .
Mississippi ...................... _....
West Tex&8 ....... '.......... .- . '......
Ea.stem Te~ (iow.gravit.y) ~ ... '.......
Middle East (Iran, Saudi Ara.bi, Kuwait,
Iraq, B&br$, Egypt) ..............

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.

SO"-called "sour" crude,oils contain-hydrogen sul.6de,15 but many tech-_


nologists carelessly ' refer to II high sulfur" oils as II sour" oils. Crude
as 0.05 eli it ,of dis- ,
oils' are classified as "sour" if they contain as
solved, hydrogen sulfide 'p'er 100 galla because such oils are dimgerously , . .
toxic. Even 0.5 en ft per 100 gal can be present before, severe corrosion
tends to occur. Oils from West Texas and New Mexico are "sour,"
and many fields of ,Kansas, Wyoniing, Arkansas, and the Middle East
produce "sour" oils. The high-sulfur. oils of California., Venezuela.,
and Mexico do not contain hydrogen sulfide and they should never be

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

PETROLEUM REFrNERY ENGINEERING

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~~~~~

API grovity ....... ()/


crude 017 ~

01

O~~~-~~O~~---4~O--~---6~O--~---8~O~~--~/OO

Percentage distilled
FIG.

4-3. Average true-bolling-point distillation curves of crude oils.

crude oils are usually deficient in low..boiling materials,' and highly


naphthenic oils usually have much .flatter distillation curves, often being
deficient in both low- and high-boiling fractions. Examples of distillation and property curves of three different bases of crude oils are shown
in Figs. 4-4, 4-5, and 4-6. The percentage distilled at 1100F is a.pproximately equal to ~OO minus. 3 times the percentage of carbon residu~.
"

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

EVALUATION "OF OIL STOCKS.

I'

1-

,1,100 I - I, Tro~ boiling-point ctlTYt!


Z, 6rayfly mId per cent
)
3, Yixosity mid per cent at I()() deg. F.
l>r,ooo I - -4,. Viscosify mid percent of ZIO i:Ieg. F.
~
2~ ~ I isco5l'ty'yj~/d rrlRIt) ~. F. ,
~i

~ 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

FIG. U. True-boiling-point evaluation curves of a 42.2

80
~'PI

90

~!
~:

'I
I:

'0
"'

...J

.:~

<{

~~

10

VISG

!:

,j

,08

paraffin-base crude oil..

J;

"

.!...~.,. . .

",'"

1-,

PETROLEuM ' REFINERY ENGI~ERING

. 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.

u L8.bol'8.tory Test Methocb, 310 S. Michigan Ave., Chic.a.go, n l.

Nov.
.

15,

I
ri
!

TABLll

4-5.

Mid ContiD~B.t

12 '

3,000
psigQ

API of crw.de oil l ;


~d s,poi plu8ure, pais. .........

...

Hydrogen sulfide, ppm ...........

.... .

2 Methane'... '............... : .. ,..

"

"

" "

,.

.....

"

"

"

"

"

1-

"

2.4

0.003,0.03

Pro pane. . . . . . . . . . . . . . . . : . . . . . . .
i-Buts.~e ... " ..... . . . ........... }
1&-B1l.tane ..... , ................

3.0

0:26

2.8

Pentane pl\Y ....... ~ ............. 84.8


i-P en t.a.n.e . . . . . . . . . . . . . . . . . . . . " " .
~Penila.ne ...................... " " " "
'

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

Huane plU! ...... . ... , . ........

250 psi

. ..
" .
,.

(Iraq)

(Vene.)

100F

"

"

JU6epm, Kirkuk

psigQ

Ethane. : ............ : '....... '. : .

%)

J'UC'!'IONAL fkDROCAr:RBON A)U.LYSEB (WT

wh.iq4 oil wa.s collected.

.J'

98.64
' 0.76 - ,
1.45

99.19

' 0.49 0:99 ',

, 0.75
1.25
-

96.33

- 00.35

97.19

1,.62

'

97.87

97.15

94

PETROLEUM ~E~RY ENG~ERING

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

Refiners endeavor to reduce the salt content of their crude to one-tenth of


that origina.Ily present. Even 20 Jb of salt per 1,000 bbl requires frequent
shutdowns to II wash out" exchangers and pipestills.
Little has been published on the' a.mount of salt contained "in crude
oils, and little consistency is evid~nt because the brine which contains
the salt tends to settle from the crude oil during handling. Thus, the
salt content of oil at the field is higher than the salt content at the pipeline or at the refinery.' Neither crude oil gravity nor- bottom sediment
and water content appear to be re]ated to salt content except when studying a. particular field or' region. Oils from various regions contain
approximately the amounts'of salt shown in Table 4-6.
TABLE 4-6

Lb salt per 1,000 bbl


Region
Average"

Range

1
5
8
11

........

Pennsylvania ....... __ ...........


Wyoming: .... _....... :, .... '.' ..
Middle East ........ ' ....... ' ......
Venezuela. ......... ' ...............
East Texas ............. ............
Gulf Coast ......................
Pipelines (U.S.) ...... : ...........
Okla.homa and Kansas ............
Canada. ........... _..............
West TexflB ..... ; ...............
G

Very high samples omitted from a.verage,

Most samples taken at field.

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

The nitrogen 'comp;>unds in petroleum are not of major importance,


but they do tend to cause a reduction in the activity of the catalYl?ts used
in ' catalytic cracking and they may assist in the formation of so-called
U gum" in distillate or diesel fuel oils,
California. oils contain 20 the largest
amount of nitrogen and, from scant data, the Mississippi oils appear to
contain the least nitrogen. Other crude oils from West Texas, Wyoming,
Middle. East, Venezuela, etc., 'c ontain an intermediate amount of nitrogen.
20

Nelson, W. L., Oil Gal J., Mar. 14, 1955, p. 139.

'!

.t
)

EVALUATION OF OIL STOCKS

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

In the operation of a replica p1ant, only one set of yields, propertie~,


and conditions can be obtained during 8. single tI rUn" or test; and hence
, many of theSe expensive runs must be ~ade in order to judge the economy
of the proposed operation. Most designers therefore rely, upon a more
general type of analysis which involves a true-boiling-point distillation
and a series of curves of the significant properties of the fractions collected.
during the distin~tion.
True-boiling-point Apparatus. This equipment is used to 'obtain a
so-called tt true-boiling-point distillation curve" (see' Figs~ 4-3 and 4-9).
An~ .equipment that accomplishes a good degree of fractionation is
termed "true-boiling-point" equipment.
Technical men trained for handling 2-component mixtures are often
disturbed' by the fact that the number of plates or the amounts of reflux
used' in much T.B.P. equipment are not large or even specified. In
actuality, when dealing with gross mixtures which may contain several
components boiling within less than 2 degrees of each other (or even a
fraction of a degree), the use of 60 pla.tes rather than 5 or the use of infinite
reflux ' rather than a ratio of 5 to 1 causes no significant change in the
shape a.nd poSition of the distillation cl:lrve, or in the properties of the
produc,ts. The best known types of equipment are ,those' of the Peters
type~l for crude oil, gasoline, or'heavier oils, 'a nd the Podbielniak tt fractional distillation equipment used mainly for gaseous. or low-boiling
hydrocarbon mixtures, but numerous designs of, .equipment have been ,
developed .12. n. 24
An apparatus of the Peters type built during 1934 is shown in Fig. 4-7.
The fractiona.ting column differs fr9m moSt laboratory columns be~ause
it is completely insulated from the surroundings. The outer jacket A,
through which hea.ted air flows, is kept at 's ubstantially the same temperaPeters and Baker,"Ind. Eng: Chem., '18, 69 (1926). '
n Apparatus and Methods for Precise Fractional Distillation Analysis, Ind. Eng.
, Chem., Anal. Ed.) 3, 177 (1931); also for heavier oils, Ind. Eng. Chem., Anal. Ed., 6,
119 (1933).
'il Beiswenger and Child, True Boiling Crude An8.Iysis,' Ind; Eng. C'Mm. Anal. Ed.,
2, 284 (1930).
,
U Taylor and Patten, Analyses of Texas Crude Oils, Railroad Commission 'of Texas,
Oct. 25, 1940.
t1

PETROLEUM REFINERY ENGINEERING

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

Diagram of a true-bOlling-point apparatus.

The true-boiling:-point still consists of a'flask D


4:"7,4-8) ranging
in capacity from 1,000 to 5,000 cc.
still advisable for the'
,eTaluation of heavy stocks, because.fractions of 100 cc are required fo:r the
determination of gravity, viscosity, Bash point, etc. However, obtaining
very low pressures is difficult in the larger 8til~ unless a
vacuum
pump is available. A vacuum pump having a displacement of 2 to 3 cu
ft of air
.rpinute is large enough for the 1)000-cc still, but the larger
requires a pump having a displacement of at least 6 cu ft
minute.
Heat supplied throughout the entire apPl!ratus by electrical resistance
~oils. At
top of
column the vapor is cooled by the
air jacket
(J so that most of
and returned to the column as reflux.
The purified vapor passes
thermocouple E in the column head and
eondensed in the water- or air-cooled condenser F.
The temporary receiver is for operat~on at reduc~ pressure. During

97

EVALUATION 'OF On.. STOCKS

Left: enca.s&1 still wlth jacketed Co]~mn; center:


control board with condenser across top; right: sample collection. (Bocany-MobilOil

FIG. 4-8: True-boiling-point still.


Company.) - "

...

vacuum distillation the product normally ,drips through the receiver G


into 'the graduate H. When the graduate is full, the stopcock -h and the
cock g are closed, and the graduate is remoVed by venting to the atmosphere through cock i., After an empty graduate is in position', the cock j
is slowly opened so that the
, vacuum on the main system is not violently
disturbed. An auxiliary vacuum PUIIlp may also be used to evacuate
the graduate.- Mter the graduate has been evacuated, cock j is closed
B.n~- the cocks g-and h may be opened again. Throughout the entire
operation: of, changin'g the graduate, the pressure-regula.tion valy~ Kneed
not be touched. Fine regulation of the presSure is obtained by; means

!'

98
.,
~

,-

:.

.1

;'

. j.

. PETROLEUM REFINERY ENGINEERING

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

FIG. 4-9. TrUe-bolling-point distillation curves.

that is necessary for .regul~tio~ of the pressure. M,aDometers are used


to measure the pressure in the equipment and in the graduate while it is
being evacuated. When the 'equipment is operated .at atmospheric
pressure, the first product may be volatile, and, if so, the graduate should
be immersed 'in tJ:1e removable ice bath J. Many materials have been
used for sealing the corks.c, etc., but LePage's glue, although it must be
frequently applied, a.ppears to be most satisfactory. ' Ground-glassjoints
are excellent"up to temperatures of about 450~.
'

I
J

EVALUATION OF OIL STOCKS

99

The distillation may be conducted in two ways, viz., at a constant or at


a variable rate of distillation. The more c'ommon method of operation is
to collect the distillate at a constant rate. The cu~e obtained by this
manner of operation ,is smooth, with the exception- of slight irregularities,
and is more convenient for design purposes than one that shows flat st,eps
for each component. The method -does not accomplish such good fractionation as the second method of operation in .which the rate of distillatiOl:t is governed by the-amount of material that boils at each temperature.
The curves in Fig. 4-9 by the Podbielniak equipment were obtained by
the s~cond method of operation. ' At present, our knowledge of the theoretical behavior -of complex mixture's and of the individual components
that constitute complex oils is so meager- that the more ex~ct curve,
obtained by the variable rate of distillation, is almost useiesS except in the
preparation of pure compounds.
When the column is operated_by the constant-rate method, the rate' of
heating should be such that distillate is collected at the rate of 1 per cent
in 2 min.for atmospheric distillations and 1 per cent in 3 to ,5 min for
vacuum distillations. The temperature of the air that enters the bottom
of the column jacket should be about 5F below the flask temperature, and
the temperature of the air leaving the jacket should be about 5F higher
than the vapor temperature in the column head. ' If the air-loses heat too
rapidly in the jacket, more air may be used; and if
fails to sustain the
temperature, the resistance wir~s, strung within the jacket, may be heated.
The quantity of cooling material 'or reflux that -is used should always be
the maximum' amount that the capacity of the column will permit. At,
all-times the packing in the column should. be wet with liquid. How-:
ever, i( too much reflux is used, the column will a flood" or "prime/'
arid reflux will accumulate in it to such an e~tent that vapor cannot pass
upward without carrying the liquid with it.
Fractional Analysis. Equipments for obtaining true-boiling-point
analyses of somewhat simple mixtures are shown in Figs. 4-10 25 and 4-11.22
Exceedingly.low temperatures are ,maintained in the gas-analysis equip:.
ment (Fig. 4-10) by means of 1iquid ethylene, ethane, air, nitrogen, etc., in
the dewar flask at the base of the column. In theory, pure hydr0carbons
are separated one by one, but in practice great difficulty is encountere~ in
deciding when a compound has been completely separated, particularly in
splitting ISO and normal compounds. Gas samples of 2,000 cc are
advisable, although samples of only 100 cc have been successfully analyzed by the use of a microfractionating tube. Liquid samples (Fig. 4-11)
of 50 cc are desirable. The high-temperature equipment may be obtained
-witii flasks havin~ capacities from 250 t.o 2,000 ce.

this

f,

I -

NGAA Publication 1146, . . . . Analysis of Saturated Hydrocarbon Gases by


~w Temperature Fractional Distillation, NGAA, Tulsa, Ok,la.., 1916.
25

" ... ~."~.:-~_~ ...-::--.:-~_,~,::,:,;-:-""'~-:--;--:-."l:"_.:':-';:;:--

~);-~',=

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.

(NaJ.uroJ. GaloliM A88ociation

America.)

---,-.~--~---.~~~~--~----~.

EVALUATION OIl OIL STOCKS

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.

Doub/f] ,inefal.. reflector '

6rodu~te

FIG. 4-11. Podbielniak high-temperature precision fractional-distillation apparatus.

102

PETROLEUM REFINERY ENGINEERING

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

vacuum still next described.


2. Distill the gasoline-free residue in a. continuous vacuum Bash equipment, lea.ving a
residue of asphalt. and collecting all the useful lubricating oils as distillates.
3. Distill the lubricating-oil distillate in a true-boiling-point equipment so that il'.dividual fractions of oil are a.vailable for tests.

Such a procedure has the advantage of eliminating- asphaltic mater~als


that cannot easily be removed from the lubricating oils by laboratory
treating operations.
As an example, we may wish to evaluate the lubricants in a Mid Continent reduced or topped crude oil of 26 API gravity. By a steam-atmospheric distillation in &_ small shell still a23 API red.ueed crude-oil and a

EVALUATION

OF

103

OIL STOCKS

32 API gas-oil distilla~e may be produced. The 23 API reduced crude


oil is then distilled jn the vacuum-flash vaporizer (Figs. 4-13,4-14), leaving
as a residue a 9 API tar and obtaining, as a distillate a 25 API heart-cut
lubricating-oil stock which is suitable- for evaluation in the true-boilingpoint column. The percentage" breakup" would be approximately as
follows:
Ma.terial

Per cent

API

Gas oil ............................... .


L ube stock (heart-cut) ....... " . : ... : .....
T 8.1......... . ............. . . . . . . . . . . . . . . . . . . . .
Reduced crude (charge stock) ........ , ..

20

32

73
7
100

25
9
26 -

Such an oper~tion is also indicated in Fig. 4-27.


As an alternate to the above procedure, residuums or asphaltic charge

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

HJ;ld with a. vacuum pump ha.ving a capacity of approximately 9 cu ft per


'rriinute the apparatus can b~ operated at a. pressure of 1 mm. Superheated steam. may also be used to assist the vacuum 'in ~ausing vaporization, but this, necessitates the use of a water-cooled jet (contact) conden'ser
for the st~a.m. The capacity of the equipment ranges between 1 and
4 gal per hrdepending upon the character of the charging stock. The aim
is to vaporize as large a percentage of oil as possible, even though the

\
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,

Vaporiza.tion of Petroleum) Ind. Eng.

ehem., U~t 453 (1927).

105

EVALUATION OF OIL STOCKS,

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

FIG. 4-14. EquilibriUlIl-flash vaporizer.

(~.

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

Eumple 4-2. Use of Gravity Mid Per Cent


Compute 'the specific
of a 41.4
(0.8183, sp gr) mixed-base crude -'oil from the specific-gravity
Per cent curve. Figure ,4-15 is the
mid per cent curve as determined in
la.boratory

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),

Assume that the curve is


up into 19
as indicatM in
The
gravities the 19 materia..ls are indicated by the 19
horizontal lines.
curve
is sUbstantially straight through
5 to 18$
and the horizontal
pass through the centers of these
The horizontal
(average gravities)
for the other
(1 to 4 and 19) do
pass through
mid-point but are so
arranged that the triangular areas above
below the curve are
The graviof the 19 fractions are tabulated in Table
. The gravity of the
equal to five ,times that of each of the
1 to 18
........ JLUAl'
plua ten times the gra.vity of fraction 1~,
divided by 100. The computed
'0.8171, and the
gravity of the crude oil was 0.8183. This a. reasonsufficiently accurate for most engineering design work.
15 per cent
oil,
oil contains 40 per
15 per cent
and 30 per
reduced crude oil.
gravity of the gasoline equals five times
gra.vity of
1 to 8 inclusive
by 40 and numerically '0.7399 (59.8 API)_
In a si:rnilar manner
gravity of the
is equal to
the gravity
fractions 9, 10, and 11 divided by 15 and is 0.8172 (41.6 API).
the gravities
.l~a8 oil and reduced
oil are
0.8496 (35 API)
0,9037 {2S.1

'}

107

EVALUATION OF OIL STOCKS

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.

TABULATION OJ" THE FRACTIONS OF FIG.

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

..

By inspecting the specific gravities computed in Example 4-2, it will be


noted that the gravities of the kerosene and gas oil are the same as the
gravities at the mid boiling points of these fractions, namely 47.5 per cent
'and 62.5 per cent. Such might have been expected because the curve
is nearly a straight line throughout these materials. Following this
reasoning we may state that, if the property curve is nearly a straight line
between the limits of the fraction, the average property of the fraction is
equal~o the. value of the property at the mid per cent point of the fraction, and the laborious method of integral-a.veraging by graphical metp.ods, as in Example ~2, need not be used except thrQughout sha~ply
curving ~ections of the curve. .
Integral..:averaging by adding together the properties of a series of short
fractions and dividing by the number of fractions cannot be used on
properties that are not additive. .Specific gravity (not API gravity) is
an example of an additive property, e.g., 10 volumes of an oil of specific
gravity 0.8 when mixed with an equal volume of 0.9 specific gravity oil
yields a mixture -that has a specific gravity 0.85. Among the properties
that are not additive are
1; Viscosity (Fig. 4-44).

2. API gravity.

3. Color.
4. Flash point.

Boiling points taken from a true-boiling-point distillation are additive,


and vapor pressures when based on molal percentages are additive
(Raoult's ]aw)~ Common additive properties are specific gravity, aniline
point, per cent sulfur, hydrogen-carbon ' ratioJ etc~ Howeve~J since any

108

PETROLEUM REFINERY ENGINEERING

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

EVALUATION OF OIL STOCKS

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.

19, 75 ec (residue from the distillation)


19, 40 ec; No. U~ and 17, 20 cc each
19, 30 CC; No. 18, 17, 16, and 15, 15 co each
19, 20 co; No. 18 to 12 incl., 10 cc each
19, 14 co; No. 18 to 9 incl., 7 cc each

cc

75

80
..

90
90
84

.,
~

:I.' ,',

110

i'

'The viscosity of each blend is


19, constitute five points 'on the

~.

.,"
It
+'..
~.;

..~ 1 '
,

"

, PETROLEUM REFINERY

ENG~ERING

de~ined,
~cosity

and the four blends, along with fraction


yield curve; also refer to Table 4-10.

Contour Charts. If enough data are' available, the- most suitable


method of showing yield data (both mid per cent, and yield) is by means
of a contour chart. The bottom scale of such a chart shows the percenta,ge distilled at the start or beginning of the fraction, and the vertical
scale shows the percentage at the end ,of the fraction .. Figure 4-16 shows
such a chart 28 for the octane, number and vapor pressure of the gasolines
contained in 'a tlrough-cut" naphtha.. The lines across the chart are
lines of. constant octane number. Thus points along the 45-:-deg line
are mid per cent points (of differentially small fractions), and points
along the vertical axis are distillate yield curve points. Turner and
Canant2~ first , utilized contour charts, and now several such analyses
appear in the literature. 12,28,20 Any kind of data may be plotted in this
mat::mer:
Example 4-4. Use of Contour Chart (Fig.' 4-18). The droplet of material that
starts and end's At 2t5 per cent has an octane number of 60, and its vapor pressure is
just. under 2.0. Likewise a fraction extending from 23.5 to 35per. cent (a yield of
11.5 per cent) also has an octane number of.60 but a vaPor pressure of a.bout 2.1.
Note that there are two lines of 60 octane number. On the other line.yields are
as follows:.
Range.
per cent

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

EVALUATION OF OIL STOCKS

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.

4-17. Typical liquid- a.nd vapor-temperature distilla.tion curves ora.

3l)

API erode

oil.

I
j

I
-j
I-

tube with the remaining liquid lll1til separation is permitted in a vapor


separator or' vaporizer. By conducting the operation at a series of
outlet temperatures"a curve of percentage vaporized VB. temperature may
be' plotted.
'
.
N onfractionating. ASTM -designation D-86 applied to gaso1in.~, naphtha, kerosene, etc.,6 is the hest known nonfrnctionating distillati~ and it
is frequently called simply an "ASTM" ' and so~etimes an "Englt!r"
because a similar Engler distillation was once widely used. Likewise, the
older Say bolt distillation for crude oil has DOW been standardized 6

112

PETROLEUM REFlN,ERY : ENGINEERING

as ASTM 1)-158. It involves distilling ' 200 ml of oil at 'a rate of 8 to


10 ml -per min. -I n distilling the highest ,boiling materials8 a vacuum is '
e'm ployed, as in ASTM 1):.116 or various modific.ations such as the equipment12 of Fig. 4-12.
In these distillatioIl:B there is no deliberate attempt to fractionate, and
accordingly the vapor temperature does not represent the true or- actual
bolling point of the material situated at' that-percentage in the crude oil. , Semifractionating. In these distillations a mild degree of fractionation
is attain8d by the use of a section of packed column between the flask
12

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

10 #!A CDIT CI.IM.S

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

FIG. 4-18. Relationships'between the slope8 (degrees/~r cent) of various distillation or


vaporization curves. (Ol Gal J.)

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

EVALUATION OF OIL ' STOCKS


DISTILLATION ~o PER CENT POINT MINUS
!!oO PER CENT POINT

FL.ASH

70

eo

. 0

-I

100
.

.200

.300

400

.!>CO

600

700

SOO

QOO

30 PEA CENT BOIUNG POINT(1:ap. OR A.S.T.M.)

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.

= 9.4 deg/per cent

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

PETROLEUM REFINERY ENGINEERING

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(

POINT ON HEMPEL CURVE)

.".,,-

::>

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.

FIG. 4-20. Correlation of Hempel and true-boiling-point distillation curves (based


mainly on crude oils). (Oil Gas J.)

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)

EVALUATION OF OIL STOCKS

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

(MIO, B.P. OJ" T.B.P.

300

200 or.

50~-700;.t___- - r -

UN~E.R

8,OJl UP
.;~.

I
700 - 800J.

--.- - - - - - -:..:,_ -'"


..,/ V

- 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

T.B.P. SLOPL, 400 -700

r.

13

'4

15

FIG. 4-21. A correlation of true-bolling-point and Saybolt distillation curves (based


mainly on crude oils). (O{l Gt13 J.)
TABLE

4-8.

RELATION OF

50

PER CENT BOILING POINTS

(OF).

T.B.P.

VERSUS

OTHER DISTILLATION CURVES

T.B.P. 50% boiling point minus ASTM&


50% boiling point

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

Includes ASTM, Saybolt, and so-called 10 pcr cent distillations.


Slope is also a factor but not to a significant-degree.
c: Doubtful, but useful in interpolations.

(I

&

T.B.P.
50% minuB
.HempeI50%
(all slopes)&

116

PETROLEUM REFINERY ENGINEERING

Finally, somewhat more detail is useful in correlating the. ASTM and


T.B.P. curves of narrow-boiling-range products such as gasoline and
data, at' the 80, 90 and 99 per cent points of the"
kerosene. From
two curves are related somewhat as follows:

T.B.P.,
of

Add these number of degrees to- obtain ASTM" of


at 80%

a.\ 90 and 95%

250

...

10

350

...

11

450
500
600

1'"

14

_ .. From vacuum

p241

.L:,I.U.11'io&""

16

distillations.

No entirely adequate method of correlating the low-boiling ends of such


curves has been developed, although approximate results can be obtained
by. a method suggested by Hansburg. 32 A complete study of this relationship has' been published by Geddesu and still another by Edmister u
but ,none of these attempts is entirely sUccessful.
The various curves may be corrected for pressure or vacuum by means
of vapor pressures (Figs.
5-26, 5-27) applied at the 50 per cent
point of the c:urves wi,th .the T.B.P. curve. Howpoint or at the
ever, the flash vaporization curve tends to become hori.zontal at the'
critical point or range. (Fig. 15-13) and' accordingly, Edmister3$ suggests
an approximate correction based on Fig.
The method is termed
phase diagrams
approximate because the II focal point~' pressures of
of petroleum mixtures are not ,known "with accuracy. The estimation
of focal points and phase diagrams is discussed on pages 456 to 460..
Curvature of Flash-vapor,ization CurVes. The foregoing correlation
method (Figs. 4-18 and 4-19) results in a straight-line flash curve. If the
distillation curve of the material is substantiruly a straight line, the'n the
flash curve is also nearly straight. If curvature
then the flash
curve also exhibits a curvature but to a lesser degree. The approximate
d~viation from the 10-70 per cent slope that any particular section of,
. the distillation curve may exhibit is d'ireetly proportional to the deviation
M., Ma.ster's thesis, University of Tulsa, 1939, or Nelson and HanS-:
Oil Gas J., Aug. :l,.1939, p. 45; and 8chwarzenbek et al., Third Warld Pet. Congr.,
The Hague, sec. IV, p. 166, 1951.
'
U Geddes, R. L'I Ind. Eng. Chem.., 33 t 795 (1941).
III Edmister and Pollock, Chem: Eng.;,Prog., 44, 905 (1948) ..
'811
Pet.. Eng., August, 1947, p. 49.

117

EVALUATION OF OIL STOCKS

of the actual flash curve from

th~

straight-line flash curve.

Thus

Slope of dist. curve, 10-70%


Slope of flash curve, 1<>-'70 %
slope of. mst. curve "through short range . (4-5)
= slope of flash curve through short range
A somewhat similar method has been described by J. W. Packie. 38
In applying curvature corrections by the use of Eq. (4-5), .difficulty
is ~ncountered in selecting a. 50 per cent point. The proper 50 per cent
~IO
I/)
I/)

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.&

temperature is intermediate between the temperature on the distillation


curve and the temperature on a straight line connecting the 10 and 70 per
cent points, and usually about halfway between.
.
The flash cUrves of extreme materials su~h as bright stock solution
(Fig. 4-23) or rich absorption oils cannot be determined by these methods,
nor have any methods been suggested .
.. Distillation Equipment in the Oil Refining Industry, p. 60, Tr'lm. A.I.Ch.E., 37.
51 (1941),

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

EVALUATION OF OIL STOCKS

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

X 40) or (430 - 4.34 X 20)

whereas it is about 365 on the ASTM curve.


between, i.e., 354F, is selected

= 343F

A compromise temperature halfway

50% on the flash curve (Fig. 4-19) 354 - 37 = 317~


100 % o~ the flash curve 317 + 50 ' X 2.8
456F
. 0 % on the flash curve 317 - 50 X 2.8 = 176F
::2

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

Nelson, W. L., Oil GaB J., Oct. 18, 1954, p. 127 .

120

PETROLEUM REFINERY ENGINEERING

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.

. It must be noted that the relationships are only approximate because


each type of laboratory equipment exhibits a different relationship
. between cut point and ASTM end point.
The end point of a. blend is much higher than one would expect from
the end points of the two components that are blended~9. and occasionally
is even higher than the end point of either component. In adding
butanes (0-15 per c~mt)J 1 per cent butane~ capse. a decreaSe .in the . ~nd
point of about 0.25F, and pentanes cause O.2aoF for each per cent.added.
Example 4-7. ASTM End Point and T.B.P. Cut Point. It is desired to.determine .
the cut point on 8. true:-:boiling-point a.nalysis curve that will give a. product having an
ASTM end.point of 437F. At an end point 01 437 (c~rve A; Fig. 4-25) the true-boiling-point cut point is 21F higher thAn the ASTM end point. The cut point is 437
plus 21, or 458F. The following tabula.tion indicates approximate end points..as well
as cut points for other distillates:
.
J.

Material

Initial
End point,
boiling point,
OF

OF

Gasoline ......... Leas than 200


Gasoline . ........ LeM than 200
Naphtha .........
300
Keroaene ... : , ...
450
Distillate ........
500

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

EVALUATION OF OIL STOCKS

True-boiling-point Analysis of Crude Oil. The property curves that


have been discussed heretofore are of general usefulness. In the following
pages the necessary laboratory procedure, the construction .of the curves,
and the evaluations of several stocks will be discussed.
The evaluation of a paraffin-base crude oil is particularly simple because
the oil contains no asphalt. Only a true-boiling-point distillation, con-

" ,

'f

1I"

"

III

lit

:::l

~
It eo

'"'

Q.

:e....

/,~'....YS.
~D PDI~T

70

~o

~ I'-...

I
,I
1/

"~

HMPn. CUT pOINT -

..,/

, ..

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

, ... ...

' ... ...... ,


,,"
,'-~OO/.,'"

"

"
, , " ,,'"
", ...

:::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

T.e.p. CUT POINT -

AOO

or.

4!l0

!lOO

~50

500

IJ~

700

(-OR HEMPEL CUT POINT) '

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

PETROLEUM REFINERY ENGINEERING

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

(3) 85 viScosity at 100 wax distillate .. 26.0


(4) 150 viscosity a.t 210 cyL stock .. , ... 12.3

0.859
0.892

33.2
27 .1

430F cut point


Mid-point 50 per
cent
Mid-point 74.7
Viscosity yield
curve

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

(4) 120 viscosity at 210 cyl. stock ...... 16.0

Will not be a pressahle ,stock

unle~

410F cut point


458F cut point
Mid-point 62.9
per cent
Viscosity yield
curve

some of the hea.vy materia.l is removed.

In obtaining br~up 1 the percentage of 409~ end-point gasoline was obtained by


referring to Fig. 4-25, which indicates that the true-boiling-point cut point is 21F
higher than the ASTM end point. The 42 API kerosene was evaluated by noting
that the mid per cent point of 0.815 (or 42 API) gravity occurs at 50 per cent on the
distilJation curve. Since the kerosene starts at 38.3 per cent, the end point must be a.t
61.7 and the total yield is 23.4 per cent. The cylinder stock of 12.3 per cent was
obtained directly from the viscosity yield curve. Twenty-six per cent of material
rema.ins, and this material is the wax distillate. The gravities of the gasoline and
cylinder stock were obtained by integral-averaging, but the other gravities were
obtained. by noting the gravity at the mid per cent points 'of the cut or at 50 per cent
and at 74.7 per cent respectively. The mid Per c~t viscosity at 74.7 per cent is
85 sec at 100F.

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

EVALUATION .OF OIL STOCKS

Evaluation of Dark-colored Stocks for Lubricants~ The evaluation of


stocks that contain asphalt demands a more elaborate laboratory procedUre. Such a stock must be subjected to preliminary distillations. The
stock is first reduced by a steam distillation at atmospheric pressure to
approximately 26 API "(Fig. 4-27)~ The removal of gasoline and kerosene
is necessary because. these materials cannot be condensed in the subsequent vacuum-flash distillation that is necessary for the removal of tar.
t,200
~

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

_._.-. _> _ rg,%IL>


~ .-'~~:-f7L ~~ rl~~-- . _ ._.~~1jil
2. i%

. 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

PETROLEUM REFINERY ENGINEERING

Job nu,_ _ _ _
Fro=m~

_____________

Sample

_ __

n u ' - -_ _ _ _ __

'Qus..ntity of Cha.rge--3,OOO co at 60"'11', API-48

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

..

.... "

10. mm' pressure

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

(36'~.;. 'No: ~23;

~~:';;'ch N~. '2i.


21, and 20) .... , . , .. '22-57. (21 eel No. 23: 7 co, e9CD No_
11, lucl.} .. ,............. .
,58. (15 CC, No . 2~; 5 ce. ~eh N:o.
11, incl.) .. , . , , .

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'

.'

:.

..

, r'''},!~j ~~~~~;\~~,~~;-{'O ~~:(O '~: :' .-::.~"


'. ;" . i... ! . ;:l.;:.,;:~a . . ~~.:.J< ,';.,q:;..::.: .'-0
., ~Q ~, .~.O~. \40.;;. 5~).:~6~l
,"_

'.

<

.. . .

: .;

'}-~?,~:.j ~;\O;C~~, i: .(. ~~.<-

",7Q..::. 80-...,,\ ~Q.., JOQ ...;,~..>..

: : PEir.ce~tCige/O~~filled .'

.;t.:_1:>." -'d

"\-.:"

,.~~~ ~' , , .:.:."

"'~l J,:"!'!::: " ,. :J ..'.,... :. ~.~ .... ,.'!.. .

"',Vi8'J~~fNW~~ (6":' ~~~tfug, l*hfiJ1tJit8~iJ ti>(tfrit~()idfed' stock '(~: '~gt~iY:t~


7;iS 0'.r'~F::~:.l, } ')'.f!>{g t q/ \-~<:~( B'~~/;~~ 't~!...;;:!.}<i:J;DI~~rlj:b'~. -!~::!~i.

i'.;lJE.d,.:.: ;'i~;)dh)'. ~;H.i::;~

.~c~Jabbnu.Q~... d~W~ 'Q~id~ :~Q~:'Yi~19~,.QP~~: frQ~.:.~h.e otc.ruq~t 9~


shQ~Jn~, F.1~. 4-ZS' a.n~ .~29... : ~~ual yiel~~ .w.ere,. 3i).5 .::p~~.lx~!\t, ..9.~
~9}1~c9.~~~:a~ 1 ~~F..v.:ax: ~~t.il1ate, ..Q~.~6.~,: gra:,yiJY;".~~ 1. Q~Q': p.eA"i_ ~Il'~
~4li-aYi~e~~t~.:a.~21.Q~:F1'. .cy~~~~~p;q~;.9i~?~f; ~~vl~~'-" :: G~~ut~. p.-Illlr
f.h~f~ef:F th:~ Yi~lds; ;a,t~ 4()..2~ pev~ cent.-,.: 'an4 i: 10~li ~ cent.'respectiv-elYf.

.or

~l~rm,~ia~~(;~:~~i:.~Ji~,~:~~~e.:::~v,JW~?I.~Y .a~i~~, t~~e5tcep.~.i~~_~~:~~ejpj.

I(""":t1i~~e~uation. methOd&'are~"~d~'\~ h~iSI~' ~_ r Ii&f~< hffi'~' :::::': r .

'" ~,::'!16' '),~J;<~~,;:; "',:,' "';\; i':;\;~ !;..,;;;c:1!,~~~'<:,71;;,,;.:1;::,; ,"" ~: ~~,j"1 ;"""~'
'"

!,

..... . . -:- .. . ' , -'"

lzm

~' ,

'r! '

~ '..

PETltOLEUM;\ REFINER"'( ' El'{GIN~RING

~.fne precEillng metlioo.~!f~vcl.uati<in i8 ~nd~cted 'lrith a minimum of

. :':d'~~Iripo~iiijri~,'.'arid;li~~~~,.}Jie Yiel.~8'-: '~e ',tJie.~!:n~um

Ii: '
.

'

, , :',

,.

..

,:. .:

' "

:',""'.>", I ~,

:. ~it~1 ~'t ;. "f~~

.- '

. ,

~,;,;.,.- 1

1- ,' ,

,:

.? v~..:

'

,,-::~,.,

.. "~' r! ~i'~~

..\',:

plants fail, .to gIve the' maJpIDUIn


' ':.', vields' b
'. ut other' p'lants pr'oduce
' ~. ':' 'f ~:,' :"-~ ~~
; ,

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

:', : ' ' '


I
I

', ' ,

., . . li'oo I,~
.

~.-

:. -Treating and ']~~wa xl-ng. ,/~~'!t,ese

r\.

~'" ~!~ -",,-

':- ,~,,~.:-:

_' , ,...

:'-

, "'

~ ~': :-:-i:

' .'

~?C? <~~

-, . -;.

, "

r--...'-~ ~ ,,:y ,--., '

: op~rati'o~$ _, are a1waYiftroublesome.

-"

:- ~
:.,

M~$L>:~efinerY ~ i~boratories, have

, ; ,-'. ~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

-'

lSCoSlfjl;Ylel, cmye ,f qr,.eart- '.

<r- ...'~'~~,-~~.-,,, ~ ;

~-

'i~ , .'>_. ; ": ~:::-'~4.~~~~#! :- ~Cksi,!m~h~t:~~P,~f-.e'!~t~J:~~:: '$eJ!e,)~j~1~ .. sUC9~~~W; but even


" "-:" ' -~-'<,,:' ;: ~;een~:-of : .the, - charge; stock sbown.lm , "'ll't't,liese: ,tIle c:olor: sefdbm checks
,'," -;-'. --. c;;:/;:~~~~f~ , .;:~--~ ~,:..,! ..-~ ,
, ~ ~ , ~ r'widr:_t~J.~I()1"-of~e:pI~i product

,u<:,x .....

,. ~

~~'if>~e 1o~~: J:n . t~~t~~~.t_o~.ar~ ~g~~ , .~ How~te!J-bYt~~QPdu~ting a

'-' "

' . :,rat'~_)luDiPer:_)f~ tatS)

:-. " ::'

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
"

. - ; ) ' ' '/ r -.''-.,.-

-"

.0.- -

..

'

f"

'

::>~>:: '.~,~::,~ :' ,:;:' :~1li~~~:: t~~ ]~~~*atQ~ :a,~& p~'ant~' r:~s.-W,tB.: d-~. .RQ:rfpe-c~., \:',,::; ::_-2 ~,,;

"

".

?{i;,;'~,:t~\:{;'ir:-~ ~1Jl.~:oils".s~c~ as g~~)iile;a;nd(p4l?swe; distillate,_ R.re_ u$uall~ treR~ in


~}:,, ,:Jr~~f'~!~~,:~~~i~.tofj!:'~y,.'p1'~~i~if; tqL-~PI~~~n:'~~b~tti~ -or iu~: ' ~n:tl ~.~taiing' ~t

:,''7"(:/,-"':', , ,'.'::X:: :~Jit'tix-';;';lru'iic


il.ci<liQ~':1
O~ to
'J).~1:-~ ,. . ''''.."i;?~. _
- --_, ,"
;- ,~,'"'t:.~: ' , -

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 .. -\ :~

,>-:''- .".~: flll~k

"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~~r, and ~.haffer, ~o _an~ ~. comp~rison of laboratory and plant results is

. gi'Ve-n.;,'A'contfriucnis.:-treating 'apparatllil tOlHi-ght distillates ,is:described


'y':
'~'u
blinU
L
A'.'l
'
)1~~

- - ,:

, 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

',d~t~atiob;:, of:tlii~~.cokii:y, aji~1'60~Fr~iifa1r. ex:ahllriA~6n; of~ the: crystal

.,...

~:;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 ...~ :'.. ,

':, ~ q~_~!~rij.. :~'~\lJft#::.~Q~~~d~~~dt@t.,:o~ H.~ti~ a~e ;~;;~j~.~' ~~fu.~~s


oft- cOfl()S1oIr~,nt:tefih6jdti;~ltJtoup.fKi~tew~r8.fure.; 6jjdit.iim.~ ilfd> :the:

'. 18~t~m~~~i~~'of(itO~r8HoJSlJfi.jfieati~i5': T6ttif:,~urfiS [- :Of'


. '~S(s~e:ti~d'&tt~;-,btit ~~brr~ liirBlJeent~licountered~. with}crude
::-l~U1ti. tm~> co~~\diilY.. (lilli. t()t Q~~Y peD'1'h6ilt~iuIfut~~~~ AbIidsti"umi;erS8.lly-;

."':: oiliftbat: arE!'hl~~' a.s"",~80~.'~ (~.9ntliiDiijg:,dissolved:hydroge~:"sW1ide) ~,~,


.~~eft&~b~?;~briMlte~d :-liktIiiilp\v~~stlsfiitiif (6~1,. to :.(}~2!per:; cent); ';l'sottr"
: '. '..':.:" ~:1tQ~~~jf~~i~~ti'9~oft.~irft onJ;Y:Lra~thlyi severe:<~ Lik"e~" some,
:

,,-

t.

..

,.

-l,'

: .:::; ~;'.~ i': ':< '''~:~J'~~'~~i*'~~4it~i(04~:~ ;(f~~t~4t~~o~miIdl)f!~ooff~

: -::..' ":' '.~ ~":f:,.' 'g~.lR~,


Bf~~";:;,
\):N;~~~if~l~~d:tt t~&(!f ~liti~~&ifi:"tll~t1~c.oiit8hi
; 'v:~"-:~ Q:5' '''. .
.~,,~,,:: JI . ",~. ~~~ .. ,' -~ " __ , y~ 8,. __ .. . " .
.
..
. ,0 s~ . . ~ per.
'C'.', '", ,

','

i'. ': ' ,' . ~ ~il~r:~r~ji_~~~~~,t6:U61~ij}~{,ooff6SiOrii~~:. Sev~t~~llabor.8.toJY

."~':;~': " : - : .{i~~tm~th'Od'si lfAV~ b'e~hJ~V1setl!!~1~ iditjudgutli? the!. ~66.osi'Ve~:riiittif.e~ or:'i


,": " ".' - "."
,:>.~f1tq~~~oii.~/~i-QIi*;:ffigtIi$!~~~8~ II{St~r ~';" ecrrnenEt6jilie>~i-ucrt}oil atf. 8i ' .
'.
,\~...... '!t....~.> .; . .(.~.
~~:t.-;S:Y
. ,. ',,-rt'J"~ "v
.'~ , '.:'&'1 " p ,"
"
. . '
"'I"

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.

"

".

.', ..

" ~li<.Jk.:i.~~,t.bl):i;'':';;i' ''''' ' ' :~ - " h


.t.... , .~; ~ ~ " ~ """.J.. ','.'.,'.' ~
:< LCwpen:l.lIu:.&- es! ,f . ::'irI~ "I.;- ~'Y"" " ;V~~~f1'(''- !-!t''t'J'lJ~'' f'ilif:!'"

'"-.:. .... ...... '

J ' ..

'i:~4" ';l: '" ::-';" ;J

'

..

'

, , : ., . , . " .. .

, . ,", "r:'l T r'-~-; ", . ,. ~ .~ ;

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 " .

,',i,' '.:':'.: . , : ,;,i/:~tal:~~~;!~ai~ ,-r611bW~~~U.~:,:tll~'8~~e!trdI&;{ a.nddp,~rl()wa.n~

.~: :;~ .'.....:''; :~:e~~~~#s.ti~<~9#.P.~~~~.l~~lf~W.~!~~s:f~,ftapp~6*tmtitihgiilie." .


1.,' '.' . ... ',:~,:pr.gp~i~,:' 6f,1>r~tlc~~J~v~.~c~s~[.~n~r'hltli~~gh . ~lfes~ me.tli6ds' ~ie : .
, ',iiob~ jjreC~t they~ perliiit): tli~'~'d~sigrier '; to'{"jtidge.<tn-e~:, etfectiveheSs~ ': 6 .a
:,;;'; p,f6ftoSd' ! 'opet~tioil:.~ o~rSitnpl~ 'd~~~ Before'large,lab8tatorY"e~penSes , are
;fii1i!iifMib:':;;:":~:: \~~.)t,~:\ i'/:j'~" '::;'j f: ' ;::J:; 'i~~4;,;.=..,.t-~:i'; F;T ",:".'> ':. '::,:';-=: '-.:j_:>~;' >.~:~" r: '~': .:;~ ~,,:-, ,,';.
" .f- ,;th,:~dditioh~' vety: Inan:f ~c:: }:>roperties ~ can.be:',deterrtiil1'ed:' from., the
,~ CH,arit<fjz2i.tion::FaCtohJ:arid\oo~g : pd~ts' :of.-t4e p~OdUCt6 (see Fig. ~,9

.. ,'ma;'Ta:ble~'4-1}~

.'.,<'" \;~:'.~: : '" '~J',: . h",:,~ "<'~:i;; :,; ,.. ';:, : ,~;: ;: ", ,'. >::

,':

'...~<: , !

:::~.)' :

:-.:', ~'. ; ,,:,:, ' . __

'''~bi sii1m'f: > lli ~ Pi-oducts.;i)IThe . -'aver4ge'.'aJiioliht 0 of;:: sulfur in straiglit-IWl


.:rp#~ucts is"felatOO to' the;a:nidti'riiv.of:;siIlfUt iii: the parent crude oil as indi~
',, ~te<i~. ~iri": Figs~ [WO to4-34.fOf, crhd~~Qils of ih~ Uhited. ~tateB" Calif.ornia,.
T

J~_f~.'~~;3 f J"t ,~/J." ~i -~ -:.. ~ _"


0

' .-

;. -~:

": ;

~;

':

-:

ri.S .;.' .~~~f"', . ,~ .

. 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
.7'fJ.T." ,
.
J ...

".

.i~ .':N

::

'

.. ;" .,, :

' ..

..:' ....
.
.....

. ,' .,'
.-
:

:.

emont Thery~ aDd Corderof'.P~ FUurIA' WorId PeL Congt~. ~. ,V, ,~~et .J.UIl.~

, ., 1955L ~_f~
-

n:.'.. C"-'.)l'j"';~~:~'
"';' 'J " ': , ", ',("
-.:.:;.,~ ....... _~-.'
i,ot, . "- . . . . " " ,

I ~ ~. ""~ '.,

"~ -'"~:' .

:~ ~

- ( .... .

-., ./~ -j '~ ~~ : '~ '~

' ..:(

':.:; "

.~ " r '"

. ~:'\;~ _ ~;_.<,

~~; " .:. ~

" . _~

,....:.~ :
'" ,

..

,-129 .

. EVALUATION; 'OF' OIL STOCKS, :,.-,:",-

w,~st _.t~~aS, _Ven~iUe1.8., .arid th~J' Middle East.

47

Conventional oils from


Kana.a8, .._ Ok!8;hoIj1a;~ ,i:r.ex~~.:..,WinoiS, Colorado, Kentucky, Ohio, and
PEmDsylv~nja: ~ are' shtlwn m 'Fig. '4-3()' ~heJeas the'~' higb.~SUlfUr- Uiilt~
-.

I ~., ,,i'.

'.

")

....

~\

"

. ~. ~~~::,: }~.".

.::..

;:.: .l ::", . . . : _.~-..

. ~.
'

.;

--"",

, \-

'.

,
I

...
:.

'~J '

..." ,"
,

;,',:'f;- ~

:'. :

f :'," ,

.~ . :

..

' , .~.

1 ,- -. ,;. .

. -0":: . :..:>-. Q',


.

"

. ~'

;;.

! ;"

...2, .

-4. ..

, ~., " ,~,., . . JP.~ ::'i ~~ ,~1'1~;L.~; .,:,~,,_~~:r:..~. .':i~:~~f1 :," .. ':
bfL.;l;~ ~~a-)-_:;'ii; ~. -.

PER. COO :.SltFUR . IN 'CRlJDE'

." .

',

~;~~~~~.:~,,~~::r;;.t~.~i~;/:;~~nUi~\t::*,e:.:
,l~lPl?~~ ' qaljIC?~~. l~~.~,~t, ~,d' .~~~f.1i~~h, ,..j (~r~ ; ~~r:!ff}f.~OJ:!:J~\~~~~J
me.

. " " .'

States,' oils i are shown:in


-

'.

" ,,' '(i:;.:.~~; ;l' Ji.,' ~j:\; <{if

:"

Figs~ :4-31':"and' ~2~:, , ;y~~tio~, m,th~ ~g~~,

" . -

':

;.

1,"

..... : .

'

"- .-

, -

'

., -

.. "~ r. '"

da~~: :ar~, large~t.b~~ the);!illur ~: co~tent ~ally , agr~~ ,.~.th .tP:~.~~y~:r~~~

v~llies foimd:frorili;tlie.figutei .,', ','" "{'.: .~ j:' '" . >~. ,<'; .: , :,:: /. .~<::/r !~.:~::. "
v.iLikeWisej ,the:,avemg~,:>stiIfUr., conten.t!~ of: .ct4cked,:.pt~ji<;~s;l.~;.J>"e

es~~~fr6in .Fi~~' 4-35 ~o,' ~...:.;S~~~~9~~~~t?~.,~9.~:~ ,t!}~~~~~~

'-- -

-.!.-

\" :

47 OVer 1,80(fse~ 6tda~ :were cotre1at~:,~g ov~t~. l~..~e~t:k~.,r: .. :,:},!":'i ):.;

.} .'

:.- .

131
...

. .~:." ~

'

. ,i;".

~ ~~ ' .'

. .. .

II'~' 1

__

'

. I /:'

. ... ~.

. ,.

"

"

~7;
,~.
,

,:':,. --r~ ;~:.,

'

"

~~

"'~~ :~.

;';

,.

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.<:
.

.
:1 -.. '

~.',

'

__ "

", ~ ' : <' ,

'
(".

..

.. '

""" "

..

-'.

..'",:~,,\

'-: .-, ' \'

, "

~.

. ' .1 ,

,.

'-,-

'

-+--: ....... ~ .;:. . "'~ ~~:. ;~ ... _" . ~:~ .. , 1--.' '.::;": .

:.t~~'{~ .-1'/: ~~r', ::-~_ _~.:':~' :~~:'

',> . ,"" .c

,.,,:',,, ' .:.l~'r.~<~-';.: ,l ~, .:J. i: :.~" j~'i ' . i,' 3:~" .. .. :. ,: ,.. i~"--'
:

. ;" ..

.'

, ~__ :,~~~, IN" ' CRt..pi!t OIL

.' . ..

~., , .

... '

FIG. 4-33. P,ercentage o.t~~~str~ih~run'Venezu~la.n' products as a function of


th& per~etita~' of. &ul{~ , ~,, th~{pAtent crud~" oih-, ,(Pr~,..F~tA .WQr.Zd;. f~:~, ,Qorr-ur.j
.;

~f118.) .- \\.~,-' ~~>.".: ""~: ~>"'':'I,{~~\I:~''~ ~'11 ':': ~.


. , .~- .
.

~i ~ . .'- "{~'

~:. t:, .:, '.

'

~-

.,

", :.\

,:\,~-(.i.;:'~~"'~-,:.

'

:,:i ~
. ...

,_

~~

The am~unt of ,sulfu~ in p~troleum 'cokes can be judged- from Table' +-11 .

,. '":F~~~~ ~oin~~ "''I'b~,.ftPproi:iJD.~~~' r~~l;\ti.o~~p bei,!"~~:~' p~in~ ,~<i


9;tp .~ p,p~~; C~?t, g~ilip.~ ;ra~~e (~E): ~~:~;~:.J ' .: -,:' :,.' : : i~, :.:'''f ''-' f " .:.~ .. :.': ~ , :; .';'
" .... <'1.:: ".
" "::~ For;distilied fra;~tibns~ ' O.MT -./ioo- I~
(.t:.6a)
~: ::i "'.;,
l::', f!':'!' ;'Jr .FOr chId6olls ":""'O~57T """-, I'tO'" .,:, '; ,.I ;,-f.;. (4.-6b)
'Mori~: pr~~e ' b~'t:'~\i'ch; :'ni~re cioiripli~~ted , relationships' hli~k been
<l'JVised)o,6f'' Wi~th~'- '~f- 'l?9mDg'rfk '.haa 8JSQ ,-kfu~" ~ffee('on-~tli~' fi~sli .
', '

J;;:' ..

, . .'

"

. . :..

~;'.;'\.\t' , ....:,.;:., . ,'" : ~ ;

. ,:'.

:" ~ ~" .
.,'

',-'.

'.

,~"

.. '.U,':; ..G ';;.' ::;.

.j .: ; (i :i. :.'

0;~~:; 'd?~ '<

. ~'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,~ ;, ."
! . '/ ., . . ,~;

"

'A~$.B~tl~r~ ~~ a!J}J?-~~lij~ep,p~ ,.or.,. ~~.~h P~~~~pf~ Mjd~e pjSt.il\at~~':.~cinnati


,.'. , ~P.lgJ.A1?r. ,~7n~Q.~! , . :. ; . ~, '.. ,
';\ " '." , '--.' .. .
... :" ". ::. ' .

....

',,:

,: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

,'ap~t is ,the experimental/' result~f , ~~~ar ',4li Ahmed,&i and the"other

lines check w~ll wit,h experimental data as well ,a s the .work of Daigle ~d

on iubri~ating oils~ ,'

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'

' ,

'

A't ' the


,w

. .-.

...

'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

'

,-~

Very volatile rna. teria.ls. '.... '. : . . . . . . .. . . . . . . . .. 20 mm

-, " H8.So1irie8;'-.'~ . >..'. ~':..~

... :'." . ~ . ; .;..' ~ "~ : ..:.. ~ ... ,.' .. ;14', mm:,


dis~illates~ and r.esidual fuels ... _... "" , .5 mlu .. _'~ . '.,., .

, .. ,Kerosenes,
,',': Lubrica.ting oilil ........ :. : " ." ... . ....... ' ... ,

' .... ~:
_. ' -

- " ' '' . -

.'

A1,ti~.u<!~ ~~

. :;, '; ~.,- .I,

.;,

' ,'.:'

i ._ J;

! ;

1:Dun

'.

'

the effect of; mildly reduCIng the flash poiritUarid'conversely,


pr~~~e ~p;c~~ase,~ _t~e' f!4~.l?~~.t.1iI
, ~o

..

- '"

-:-;---. ~

;-.'

,'/

"

.'
(

"
: J

, I
i

::)-

I).
.

~''' }' '

..::.~;& '

.~

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;lo ,.. '


,

l34i

,"

'

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':

, ,~--- \

'.

- , ~ ',

"

<

PETROLEUM' RE~INERY ' EN-GINEERiNG


"

. _, _

'

.f

-.-

~ . L,.

.' , '.

~, ~ ,

"

. F~w: ~rlU)!.E.t1.JL . qotis

TULE :' 4-11. SUl3UR': Co'NTENT:.OF..'A

~ . : :_ ,

' 1.:

. I

II

j'

(
"

.r.

~i

,
"

Elk B~m';

Wyo.~pitch~

..

....~. :. .... '. . . .

,2.5" ' "

.. '

"('

3. 5 ~ .

Hawkins, Te:L-pitc.h ... ........ .... .

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

,:". /3;Ot( ,.'" j. -\:0.875


3.06 '

.
:

: 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'

~-

! .:~

'

'"

' . ~_

"

Ap~
,

.,

.'

.:.. '"-' ....~ ~ . .

:"

'

~... ..

..

"

.:.0

~t

1_,

. .

'.

,....

....:

r- ".
'.- :

.
I

..

. ' r'

'\. ' . . , ..

'c

.... j .
' !,

,,~~ -

135
"

I'
"

...

.::~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~'

"

" .

.~

....

:,~., ,:.: '~ ....


..

--.-,.
. . : .

-.

,-

'

".'"

...

,,:

.~--}

~.

'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:, "

"

"

.'

,"

'~-:'"

,'it:
I

~~ . . ~
!,'

, ',

"

~r':~ , ~

.1 .

, ' j 'e._, ' .

'.

, . . . . _ ... :

.'

~" :."' ,.'

'(".)..':...'\' .:,

...

I. ~ . ~

';. . . . . . . . ~

''''

.... Ra.tio of true

, ;-'. ~:

.' ,~:) ( ...

,:'

:"

"

" ,

'".'

..

: . ., ..

,:,

,~

' .'

. ' . ' . '

~ . } . ..

"

'. '

, . . , ", "

... '::, ,l .

I . .

'

~,:,{;~~:~ ,'~d~~'~'~, ~ .',i~~::r~~':' ;~.; ,: .- ,".~.'. ~ ;:"::~' ~:~,;..,.,'.'. ~;' ,' ~:,~~;

II

~
.:,I"

j,

ii

" / .,,,-- Grudeo~-l~ ,v.p .... :' .... ".... ..~." ..


, ',, ';' : ,. ,Hy<h9'~rboQs; bottle g~ etC'....... ".
,

') !

~,:~'.- "e,

f, i,72
"(40

>:/' .::, ;:,,:J!:,'0S5

'~.":'" ,,~tu~~~(~;~,~e,:.~~..!,: ,. ~.:? ',":';::~':',: ~

soltnes ........ . '...... '.. '......... . . -, 1.07

__~',,-,'',.,-'-,-'-'-'"--......:".;.
... .:....~',. :,;'.;.;.,. -~~~___.:,;..

to.Reid.V.P. ii

,:,",-,

' . . ,'

': . ' .

~:

..

. Range '

. Average .
.

:. :':'. '. , ..:

'~:"'''}:'''J; ;:-,~ . ... }d~<

10;:

. (1: 611~tO.
0\ .. "~:j ... " : ...
(1. 0; to 3))".,.'. ' '~' : . '.

(1.17 'to i .-6)"' ~

(1:03 t,O t".:14Y ~.. , ' -'!,)

'(1. 03 to L 45)

',f .C:

-:-:--:,.,:-2-:..:...
.. """,.~",~,.~.~,.....;,;'.;...''~'~~~'"'t''--.....~,""''':.,,',' ',", ,I

=-:-':' ...;
..

, "

J , ",

.....

"

' ,.

,~;
"
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-

.(

:: EVALUATION :-oH.':' O~ STOCKS. "J:{:;,

-1.37

'.
100
"

......
.\ .
.
: .;

en
t-

:.~~:.

..

"
~,I

, 1)-,

,'.~ ;

. . \ .. , ,. " ,

.' 1 -

99

80

..
-.- .1

-~

.-'!

<
..J
~

70

....:

"

0Q..

"

.
......
;" , ;., ' ,
"

~' ~

' .....

-~ .~

.' ~;:~~':- '

',:

. t ..

., :

. ~.

I'

~,

'.t

:;~ .

~'

..-

.
"

. -: .

,,~

, -,.. .... ~~
"

1"

,~'

.:. :.' ' .~.;

Ii.' '

, j .!
.-- ~.t~.

,- -

1.. ::,:, \~~. ..t.li-"

;'~:'- ~~~ .': .9.~ ~r:!.: ~~~.;-~J~.~~{.i :;.:{~~~. /-/-:r. ~~ -:-~.


-

<

; .. ..

,-,

PETROLEUM
-

~:: , ... :_~_-

... ',

r- ,

'

, ....

'.

,--,-

'

'.......

' .

REfiNERY~. ENGINEERING
...

. . . . . . . . __

. "1

"

': .

"

__ o w '

'.

,,~

"'"

r ..

.-. J

r~r~~~,' 4-12; AJtp~xUU~ RELATtON:8HIP .B~mj~ TREi TRm( ~D'

~ " REm VAPOR ~8URE8 OF Ml'scm.UNEOU8 VOLATILE PRODUCTS '.

l\\!::::~~ ~';;.':" vl~rp~~:~ : ~. . . '"

f-' f.;-"u_ .~ -' ~~;},":" PiodU"dt-'-


::,: '" : " . \ .; .'\.. '. .
:.~t
\". : . . \ . ".~~.. .
-~~.~.

,.

.... ~, -~

'i~,

. ~-.., '

~""

.:'\ .._

.'

-.~

"~" '"

..._. ". _ ~' u

'. .

Re.I'd ' .

Ratio. Re~d~' '.

Trn
,'
.

'"

~.

. '.:

. ' ~.-

: -_.' , :'' '

~. 7.

";..
r

" .:- -/ ",," ,- .... ~,. - ..... . :/.

-'I

'

4.-

r.09
1'.075

23.8 _

Naturat gaaoune.. ':,~" .."-'.>' '," ,: 20'.4

~:

1 '.60
L 17

~a.t~ .~~e; .. ...' . ~ ':' .: g:,: ' . .22.0.

:-;

{t

e.

~UIe ~""'.:' '.,'.........:.~:' .~ ..~2:0 ::' .- ~ ~ 1-,:,


Bottle gas~ .... '.,.... ~ ...... ~ '.. ." (51.'0' e. 59;7 '
~ . - ,'NatUrafgasoliDe ..... : >...... ~ . 24'.0,.
, 26 Jl'
;,
NatuiBl:gasollne.'-~ ....... ~. 22;5'." 24.2
1.

,:.'

.,,'

: 22.2

,: ~

, 1.08 _' "

L 088

:~\ ' Natu~ : g~e .... ~\,:; .....:;' ., ~9..0 ; 21 JJ :


'H"';-~ -N~ '~-t'::-:;t;'---:-'I~m'"' .... : -.' ,... ~ -:,' ,,:,., .~. ::\'lrt,I" 1' .. :: . ~-,,:.fv. .. .,. 1
,q
"fl uraq~aso. ,~ .........~. ;" r--. ''-~' "
' ~. 07';

1.09 , i:
'I! 030 ... .'.:. -{ :.'
':.

?t

i~

~flt~.:!~lme'~'..l.~ .. '~:-~'" )~,.~" "\ ', 19.7 ~


1:.048'; ':,;'
i'I ... .~~tulD,l!gasoline~~~".:i;.: ~ ". .. ~., I.'i" 18~4: ." \: 20:..1 .>- __1.;,,002, ..~ ..;'"
t '1, Natur~.l gssolfue ......
" i8,.
;'.)'20.1 :' '}'. 098 ;
'~"

a<

>:<... :

t.

\.N:at~; g~~e . ~' . ~ ~ .... :'.-;,..

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::: .,

.'" . ,,'

.',1.',.,97 ' "

':': '~"~\ ~? i~i ':' "

,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

' . 7. 2 . .'. ' 1. 16......

?' ~

; ;~ ,

. ~;: .:. r . :~):.:9~~~~:: ~'.", ..:~.}. ',." ~.:.. ~ '.;,:; ::,:.S::O"'~' ~.:,": '~.~.~" ;<~~lJ:,,:-:.~: , .-:-. ~:.

.,i.( ',"', ..:' XYI.&~on gasolin.;~ .... ~ . ~. ~ . ..


, ' t ,
';'~', 'Ii"";
.',
.,: .:. .;. 'G'a.so
)le ..., ' . . . . . . . . . . . ' ~.
;=.
"

-".J-

.. '

>'

'''!';~:

....

Gasolme: '.., '

, ~,2 .. ~.. .~'~J,'~

.' <, ..

t.1~.:,,

4: .0' ._ .- "j"
2
.. 1" '05"II ' '.
':I:
"
.
...
' _-" .
, .. - - '...... ..... 3 ' 0 . " 3 -1'" . .,. L 03~ .; ,
' ~" '2:'0
'2 : 1 . ' ~' J.,.055. ,
;", '

'

,"

:..,' ".- G8SQlin~:,::


:.:::: :.: :::.:.: ::::: "...

.
.fARii2,"i'Ev~por3tion ~-otPet.roleriin fro:m Storage.T8.nb/'.... , .
.... . .

'

- -"

'

.'

~'' ~------------~"--~----~----~~>-' ----'-"--

":~~t repr~'tative~

;.

, .:.: .. .... \00-

-'

of aViation 'gBBOliDes.

,~"

'-: . . ,', . , . ' .

.,:'

,,-,~ ~~ ,. , ~

tion,a~ ~~e~.' However, if only.the Characteriza.tio~'Fii~'tor' 6~ g~fteral .

type"';r Ii)~teiial is known, the ,specific '(or API) gravitycan:ooc6inputed,

:froJP: ~q. (471). . ' ,


/'::. " ":. :." , " ,
. '. '
Iii'~~g ':oila heaVier tham"the low~st-b6iliIig naplit1i~, ri~VSign1cant .
'Change in the total arithmetic volume of the two components. occUrs, and"
the: specific gravity of the, mixtures, is. exacily what, would , be expected '
fro,m ~lie'- proportions used in the mixtures. However, the ,API gravity

. ...;j'.

'r "
I

139'

'EVALUATION OF OIL STOCKS

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

"?

Mid B.P. 'of Jet Fuel,


\that extend to 550 oF.

ItS

.. MID BOILING POINT--F.


,
FIG. 4-41. Indication of the effect of boiling rang~ on the POur pOint .6r the fr~z,ing
' point. (Oil Ga$ J.)
,

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

PETROLEUM REFINERY ENGINEERING

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'

fuels, , , .............' ...... , '. 20F

-Diesel or distill.a.te fuels ........ .' .. ;~ lO"'F


Lube oils (800'T mid bp) ...... ', ,. 2lrF

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

stock was thermal er.acked

'stot1ks behave ~ ihdic~ted.by.Fig ... 4427sUggestedby Reid and


Allen:64 In their method a
II Blending Index" .is' employed
(see Example 4..9).

so-:ea.ned

Oil Gas J., Ma.y Ii, 1953. p. 141.


82 NelsoD, W. L., Ot"Z Gas J., Jan. 31, 1955, p. 269.
,.
81

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

EVALUATION OF OIL STOCKS

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.

' .% in blend '

PmT point

ASTM 50%.temp, OF

25
40

+30
0.
-60

550.'

'B
C

35
. .

"

610.
450
.

'

The index of the' blend is found as follows: .


8wck
. ,A

.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
-' -.

,T he ~O% t~mperature of th.e bl~~.d, js:.-- ,." '

'.

i"'&~

. 5Q%,,~mpj .0F .' ;-'f.ractiOnal:50%: ~p, OF

i52 '

" 610
~.

. 550

, . 22Cr-

450

~58

50% blend tempera.tur~

' 530 '


-.

"

Reid
...:. ".-, : ~.-, .

,"

and Allen; Estimating Pou.Points. :;'. ... ~;'Pei.-&~;~May,-i951, . p.9.3 .


~.- ..- .....:. .... _... ,... ~ "'--. ~~~~ .......... ~., .. -"' .:.

"- Vi~cositY~

:....... .....:.~.:.~.~, .-;. -.-.~~-:.,.:-.....;:.~~~.-: . . . ,. ... -~;:,~ . . ~ . ..:I;- . -':-. ,

The ,Sgeneral .. range~. of 0~co~ty>

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

The .p~re . must Qe used Wlt~ cautio!!> beca,u,s_~. t.h'e slope of


the lines is a functIon of the':. Viscosity-Index o(the
tllus~'s~veral
lines' can 'occur' for oils:: that, hav~ th~ same viscos!ty' at ' s'ome:" ref~rence
temperat~re such as ~OOF or:'210F;
:'
.
Viscosity.is not an additive property. When miXing one :'volume ~f
,500-viscosity oi( with' one voillme of fOO-Viscosity (at the same 'temperar. ture) oil, the resultant blend d~ not have a viscosity of ?OO,:but about
.200 (imaiine 'lIne- cQnn~cting'~ pOO on'tb~ lett
of'Fig~ :4-44 With
100 on the right scale an~, r~~.at 50 per- ~ent).: ,:' The' commonly accepted
method of predicting\riscosities' is that of the ASTM6~ and the pse of the
method is almost self-evident in Fig. 4-44 which shows' a line of the
viscosities of mixtures of a 200,OOO-viscosity pitch and a 34-viscosity .
cutter or dilution' stock. The viscosities of the two blending stocks

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-

,PETROLEUM REFINERY ENGINE:&RING

,70
"
~,

*-

--. ..
_.
...""!'

~ ~

/h

"

----

;
\' ,

./J

,
'

j"

II

./

"

~~

/
k! ,
fta ~

.p',/'/'/ /

TV'L
/'
~

,, '

VJ 11/
-

0..3

0"

.'

,-

-"
,'/

~-

,/

,-

-/

.,
'

/'

V
, ~/ /.

'-

/
;

'(
,

1(/

/'
~

- /

/ ' /'
/

~'/ I

- ~

"

- f

-'
~;

/.

:/

/'

'/ L
./
,

:,

~,~ 1/ / , ' /~'f_


L' VI / II /,

- ~ 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

(DISTIUATE BLENDS ONLY)

~-

"

.//.')

POUR-POINT BLENI>lNG CHART

4"

--

'

II

'/

"

'

"

'

"

'

-,

'

'

'

"

/
{-'

..

, I ~I /
(/'-1

0.1
-80

1 -

-10

-60

-so

-4G -30 -20

-10

10

20

30

040

50

eo

POOR-POINT TEMPERATURE _oF


FIG. 4-42. Pour-point blending chart 'for distillate materials.

(Pet. Refiner.)
-

,-

.;

143

EVALUATION OF OIL STOCKS

TABu!" ~14. OILS USED IN ~.AtUNG FIG. 4-43

No.

Saybolt viscosity

Kind or type of oil

22
23

Natural gasoline, ...... , ....... , .' .. ........ ,. .. .


Gasoline. '.' , " , .. , . , , .. ~ , , , . , .. .
Water:, ...... , , ..... , . , .', , , , , . , .......... -, ;. . Kerosene ......' ~:: , ......... - . .. .~ :,.......... :~.
Distilla.te ...' ...... : ........ , ... ',
37 at 100F
Average' light crude oil~ .... , . . . . .
33 at lOOo}f'
Average crude oil a . . . , " . , , ' ; , ,
40 a.t 100F
Avera.ge crude oil"., ... ,' ... , '. ... . .
50 at 100F
Average heavy crude. olla, , ... ' . . .
60 a.t 100F
_lt Cree,
k Wyo,. ern d eo
. il~ , .:".
. 40 at 100F
SlIo1
ASTM Fu~ 3 (max :viscosity) . . . .
45 a.t l00~
ASTM Fu'ei 5 (min v~Sity):. '.' ~
. 50 at 'l00'T
SAE 10W ,iube .. : ... ~': . , ....... ~ '.-. ' 10,000 at O~
SAE 20W lube, ..... ; ' .' .. , , , -.",-" 40,000 at OaF
Thin $AE 10 lube, (109 V.I.). : . ~ .90 at 130F '
Thin SAE -10 lube (0. V.I.) .. , .."'. ,
90 at 130F
Thin SAE 30 lube (100 V.t). , ... '~
; 255 a.t 130~F
Thin SAN 30 l~be (0 V.I.),.; .. ', '; :.
2M at 1307
ASTM Fuel'5 .(max viscosity) or
Fuel 6' (min viscosity) .. , , .....
40.at 122"FAverage SAE 50 lube (100 V.I.), ' ,'
90
210~
Averilge SAE 50 lube '(0. V.I.): ... .
90 at 210 a F
150 at 210F
Thick SAE 70 lube (100 -Y.I.). , . , .
Thick;, SAE '70 lube (0 V ,I,) . : .... -. . ' 150 at' 210~

.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

.,

Bunker' C--(ma) . ~'-.:" . ~\'.' ; ': .'.:"

...-.... _.....
........ , . ..
. , ..... '.' . ...

. , ,,.:

'~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
..

"., <3Oo-at.:'122;;]--1: :. ,-, . , . ,

8.0'

............... .

19.8

at,

M~C~ residuu~ ,~-. '... ~ ,': .~ .."; ,. 300 21()~F '


~phalt, . , . ~ .'.:, .. ; ~ ~"... " ; . .- . '. ;. -. 59 p~netration:, .~

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.
,

mUst be at, the same temperature. . However, -the AsTM method. is


accurate only when ,blending oils that have similar Viscosity Indexes.
M. Rahmes, 66 af~r having blended 30 widely vaiying sets of components
in several proportions, and after having examined 12 prediction methods,
concluded that the Wright method S7 was the most dependable.
The Wright method, as illustrated in Fig. 4-45, utilizes the standard
ASTM viscosity chart 66 but in a way different from the method recom81 Rahmes and Nelson, Anal'- Chern.; 20, 912 (1948); also Master's thesis, University
' of Tulsa., 1947.
.
57 Prediction of Oil Viscosity ,Pet. Division, ACS Meeting, AtlJmtic ,City,
A.pr. 8-12, 1946, p. 7 1 . '
"

144

PETROLEUM REFINERY ENGINEERING


.1

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

.12. FUEL 5 <MIN.)


"i3. SA lOW LU8E
14.. SAE 20N WBE
15. SAE 10 UJ8E

000 V.1l

17

J~

II

16. SAE JO WBE (P \(1.)


It SA. 30 WBE (100 \LIJ

16'

. ,

'i:~.-+--t-.o.tr='--I

"18. SAE 30 LU8E (0 V.O


1-+-f-'-i-+-f-f-fl--+-Hl21 J.'otIj....J-II-+-I.f+,~-+-"
~.f--....,
19.' FUt.L 5 (MAX) OR
. 1-+-+-I-+~--I-.JII--+-lt-l-J~I-fI..fI-I.---f,H+--t,t;-+----1
fUEl. IS (MIN.)
0...
If
I
", 2Q. SAE.. 50 LUBE 000 V. L) "
II
11
A
21. SAE 50 lUBE (b V . I J I
II
II ~.J~~I--~
22. SAE 70 LUBE Goo 't( L)
U
. " 2). SAE 70 WBE (b 'It L)
II
I . -/
,.
.' 34. BUNKER C FUEl. ~ I-++-IH---I-f--II-......IH.fHH'-;H',:.t]f-'+HI--t---1

lll5

.. 'a ~~<:r RE$IOUUM


, -

:. 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

EVALUATION OF OIL STOCKS

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 :,' ,

~:

PETROLEUM REFINERY ENGINEERING

::

Also, the ViscoSity-temperature line of the blend will lie between the liIles

for the two blending stocks in such a way that


MO
MN

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

The viscosity of an ,oil at various te:r,nperatures, can be determined by


plotting a line on ASTM ~scosity paper. 86 Exp~rim,ental deterrrunations
at two temperatures serve
d~ne ' th~ , straight line, o't,if the Visc~sity
Index is known, the ,visco~ty at 'one te~pera.tme Suffic~s. Figure 4-45
shows two such visco&ity-t~rripeiaitiIe' liii'~s." ': .. c ~ .', : '
,
Viscosity Index is 'n ot
'a dditive' 'pi"operly~, and th~ Index','of mixtures
can be estimated'by plotting.'tIle temperature Imes'of:the two ,coniponerits
Example 4-10, the
as in F'ig. 4-45 and drawing the line for. the blend.
Viscosity Index of-Oil A is'73.3, Oil B is 113, and the 41.5, per cent blend
has an Index of 97 rather than the 89.8 that is obtained by assuming that
Viscosity Index is an additive property.
Gasolines or Naphthas. The approximate ASTM'end points of T.B.P.
cuts or fractions of gasolines can be estimated from Fig. 4-25, percentage
of sulfur can be estimated from Figs. 4-30 to 4-38, and vapor pressures
may be computed using Table 4-12.
'The octane number (Motor method) of straight-run gasolines is related
to C~aracterization Factpr 68 ' somewhat as indicated in Table 4-15, but,
'note particularly the wide variation in octane number. Boiling' range
and particularly the cut point also affect the octane number (see Tables
4-16 and 4-17). ,Each gasoline differs ~n its, behavior, but the general

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

EVALUATION OF OIL STOCKS

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

Change in ~l.ane number


per lOOQF change
in the 90% point

40

12.0
11.3
10.6
10.0

4S
50

55
60

65

8 .0
4.7

The average relationship between the Research and Motor method


octane numbers is indicated in Table 3-3 7 and the lead susceptibilities of
various 'types of gasolines are shown in Tables 3-11 and 3-12.
,~

Moxey, J. G., Pet. Processing, February, 1947, p. 92.


70 Holaday and Heath, SAE QitaTt. Trans., July, 1951, p. 429.
71 Nel5on, W. L., Oil Gal J.~ Nov. 8, 1951, p. "332.

,I.
T

- I

148

PETROLEUM REFINERY - ENGINEERING

TABLE

4-10.

ApPROxi!.UTE RELATIONSmp BJITWEEN CHARACTERIZATION FACTOR

AND THE MOTOR METnOD" OCTANE NUMBlilB OJ'

CUT POINT

STRAIGHT-RUN GABOLINES

Characterization Octane number


Factor of gasoline (M.M. clear)
11.4
11 .5
-11.6

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

Slightly lower than Research method numbers (see Table 3-3).


TABLE

4-16.

MOTOR M.zTHOD OCTANE NUMBERS AS A FuNcTION 01"

MiD BOILING POINT

Representative mid per cent curves


Octane number, Motor -method

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

When two materials are mixed, the high-octane material usually


behaves as if it had a higher octane' number than obtained by laboratory
tests of the material. The higher octane number is referred to as the
"blending octane number." Blending octane numbers are apparently a
function of the difference in olefinic content of the two stocks,72 but since
the. olefinic content is not ordinarilY available, a possibly less accurate
'
Jllethod 73 is illustrated herein.
Schoen and Mrstik, Ind. Eng. Chern., 47, 1740 (1955).
73 Nelson, W . L. t Oil Gll8 J., Sept. 19, 1955, p. 135.
72

149

EVALUATION OF OIL STOCKS


TABLE

4-17.

ASTM
90% point,

EFFECT OF

PER CENT POINT ON RESEARCH OCTANE NUMBER

Octa.ne number; Research method

OF

Straight

240
280
'320

77
71
64

360
400

49

440

90

run

57

...

Thermally Thermally -Catalytically


cracked
refornied
reformed '

83
81
77
73
70

Catalytically
cracked

83

87

90

82

90

19

88
89

77

90

90

...

. ..

89

90

The blending octane number of the high-octane component or:'blending


agent is ,defined as' CNG (~lear or:leaded) in which C is,S factor (Fig. 4-46)
for ea'eh particUlar pair of compon~ntsJ and Nfl. is the octane number
(Motor or 'Research) of the high":octane blending agent. The' blending
octane number is then used in a regular additive-type equation ,

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

1. SIigbtlY lar.ger for Research octane 'numberS and slightly

low~r for Motot method

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

Research octane blend 66.0


The octa.nl;} number of the blend might be slightly lower (65.8) because the Research '
method of test was used.

~
~

,.

J'

.<

"

"

,
I
j

"""",.,.,."',Oc.. "" .... -v ENGINEERING,

150

In making up two plant blends from CO>,,'n.po components, two general


are fonowed which tend to result in
octane numbers or the
use of smaller amounts of tetraethyllead:
JU.JI. ...............

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.

method for three or,m'ore com.


the blending factors of pairs
'can be best illustrated by an

Difficulty is encountered in the use of


because it is necessary
of
not shown in Fig. 4-46.
example.
Enmple 4-12.

Octane Number of Entire Plant Gasoline..

able in one
are
number of the entire pJant
run gasoline and the butanes
TABLE

4-18.

PllOPERTlES' OF

BLENDING

Bu iran,e. . . . . . '.. " . . . . ... . . .


Straight-run, .. ' , ... , . . . . .. .
Thermal cracked. :',." ... , . .
Catalytic
,., .. .. . . .
Poly (catalytic) ...... ,......

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

3ce TEL octane


numher'

Clear octane

Per cent
of total
gasoline

.. Oil Ga3 J.,

AVail-

Table 4-18. The


shown in Table 4-19. The factors for
the thermal ga.soline (15

, 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

'Plant gasoline ...


'4

Oil

97

57
77

Partial
octane
number

1.0
1.1)
1.06
1.055 (1.0~ and 1.066)
1.055
"

19, 1955. p. 135.

factor

.Lt.n:;.uU.,I.l.lE>

"

"

."

"

"

....

...

.......

7.76
17.10

12.
36.40
9.12
82.63

151

EVALUATION OF OIL STOCKS


LEGtND- BLENDINGAGNT BASESTOCK

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--~+'_-

9 CAT. oR WITH POL't

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

'* By research method, and bose slack becomes'


blending agenl when using molor method.

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

Platinum-catalyst-reformed gasoline exhibits a strange behavior. It


the Research method of test is used, it behaves as a base stock as shown
in curves 3 and 4 of Fig. 4-46, but if the Motor method is used, the

I ':

,j
'J
. j'

, l'
," '~

152

PETROLEUM ' REFINERY ENGINEERING

r;=. KAURI BUTANOL.


...

70

...

.......

.....

"'-

NUMBER
-

~ -- ....

.... ......... ~

80

.......

......

......

.... ....

~ ......

~ .............

-.............

--- --

150

_.
--.. ~
~

.........

r---.

........

........

r==::

- - ..1---

200

I---I--...............
I---...... r---. ...... .........
~
I---I--- I--~
~
r----

r--- r-----. r--

... '-

...

...........

- -- .- ---

rACTOR
.I

.. ~ ~ ~-- ~ ~ -............. ~ .......


.........
...............
...............
1'--.....
~
-.............
r--............
~
-.............

1"'-_ .....

..... II

..............

--'.----- -.-

40

"

-..............

CHARACTERIZATfoN

250

---

..............

r-- r--- --..... ~ '-

r---. ~

--;;-a--

-- --

" - -.-

300

----r----

........

...... ..... "-

-- ---- ------

i--

~--

,350

. I-...

~-

400

450

MIDBOILING POINT -. OF. .

FIG. 4-47. Kauri butanol number (approx~ate) ~


'a nd Ch~rActeriz~tion FactOr~ (OiZ"Giu J:Y ' . .

a{unction of the mid boiling point

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.

.,

Nelson, W. L., Oil GlU J., June 30, 1945, p. 117.


Baldeschwieler et :&1., Ind. Eng. Chem., Anal. Ed., 7, 373 (1937).
N~sonJ ' W. L., Oil Gas J., Ma.y 24, 19M. p. 271.

.1

153

EV AL U ATION O}l' OIL STOCKS


r-ANILINE

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

,MIDBOIL IN,a . POINT -

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)
~

. '

For K.B.N. above 50:


K.B.N. = 117.7 - l.06G - 0.249A

+ 0.10(340 -

B)

(4-8b)

In these, G refers to API gravity, A to ariilfue point (OF), and B to mid

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

Anal. Chern., 20, 207 (1948).

154

, PETROLEUM REFINERY ENGINEERING

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

Freezing. points may be estimated from Fig. 4-41 within an average


accu racy of plus or minus 20.F, although vaJiati~ns:
great as' 60F
were e.ncount~red in. ~ . of the 107: sample~ examin~. 83 . Altb:ough low
Characterization Factor jet, fuels ..have low' freezing points, they are so
viscous at low temperatures that they are not satisfactory as fuels. This
is cared for, however, by the following gra.vity limitations of jet fuels:

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

Nelson, W. L., Oil Ga8 J., May 11, 1953, p. 141.

,, .

EVALUATION OF OIL STOCKS

be made if jet fuels boiling to 500, 550, 600, and 650F are prepared by a

Hempel distillation, n but if such complete information is obtained there


is little need of short-cut evaluation methods.
Smoke Volatility Index 80 is thought to be significant but it has not
b~n completely inveStigated. &l Th~ relationship between smoke point
and Characterization Factor appears to be much the same (slightly lower
smoke points) as that shown for ker()Sene in Table 4-21, but the .v ariations
are larger. Scant information on the weight of carbon deposits in one
type of reactor indicates the following :81
Ip smoke point,
mm

Approx. depOsit,
grams

10
15
20
30
40

8.0+
.4.5 .
2.1
0.5
0.2

Kerosene and Illuminating Oils., The general characteristics of such


oils may be estimated from Table 4-1, tp'e ASTM boiling range by means
of Fig. 4-25, and. th~ percentage of sulfur from Figs. 4-30 to 4-34. Flash
point is of .major importance, and hence Fig. 4-49 is offered as an approximation and as an indication of the general effect of boiling range on flash
point. 82 Here it is noted that the flash point 'of kerosenes taken after a
362F end point gasoline ranges from about.146F for a 10 per cent cut
to even 180F f Of a 30 per cen t g~s-oil cut.: The kerosenes of Fig. 4-49
are mor~ completely s~ripped than most commercial. ke.fosenes or distillates, and the yields are therefore slightly high. Furthermore, it is
advisable p~osely to leave some low-boiling material in' kerosene so
that the wick. of the lamp can be easily lighted .
. Smoke point is an important property, and it may be estjmate~8S from
such properties as Characteriza~ion Factor, gr~vitYJ or even viscosity by .
means of l'ables 4-21 and 4-22 or from hydrocarbon structure. 84 Viscosity assumes importance mainly . because it is used in determining the
so-called "Ring N urn ber" :
rung No.

= thermo;scosity

- 10(46 - API gravity)

(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

Catalytically- desulfurized distillates or kerosene from West Texas raw


~tockS81i h~ve ,smoke points :tha.t 'a re a direct. function of per cent hydrogen
(smoke point = 25.5H - 317), and 'severe treatment results in a smoke
p.oint .of 48.
TABLE 4-21. AWROXBlATE SMOXE 'POINTS .AS A. FUNCTION 07OTHER COMMON TESTS all PROPERTIES FOR KEROSENE
STOCXS fuVING A MID {BOlLING POINT OJ' 437Fo

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~

Nelson, W. L., Oil Ga8 J., June 14, 1954, p. 151. _


Smoke points by the Factor lamp are nearly the same as by the Indiana lamp.

Distillate and Diesel Fuels. Boiling range (Fig. 4-25), percentage of


sulfur (Fig~. 4-30 to 4-34), and Bash point (Eq. 4.-:6a) may be estimated
by conventional methods. Although distillates and diesel fuels (as well
as cracking stocks) have much the same boiling range (400 up to even
700.F), aromatic and naphthenic hydrocarbons are 't olerated in most
distillate dUrlls but are a. detriment in diesel fuels. However, the paraffinic hydrocarbon~ of high Diesel Index (or cetane num~r) also have
BI

Zimmerschied et aI., Improving Distillates by Hydro1ining, Pet Refiner, May,

1955, p. 153.

157

EVALUATION OJ' OlL STOCKS


TABLE

4-22.

RE~TIONS_mp BETWEEN SA.YEOLT THERMOVlSCOSlTY,

S.A.YBOLT UNIVERSAL VISCOSITY, AND KlNEMATlC VISCOSITY,

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

NelsOn, W. L., Oil Gas J., Julie 14,

~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:

Sa.ybolt Universal viscosity

../"

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:

,/'

130 140 150 160 110


180 190
Flash Point (Tag.) Deg.f.
'FIG. 4-49. Rel&ti~n of Tag flash point of kerOBeIleB to T.B.P. cut point of gasolines' and.
the yield'. ~f kerosene. (01,1. Gas J.)
.

110 _120

PETROLEUM REFINERY ENGINEEBING

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

dependable. I I . Width of boiling range about ~ fixed ,~d boiling, point


has litUe effect on the pour point and no appreciable effect88 on the Diesel
Index, but lower-boiling fuels have lower pour points (Fig. 4-50) and
higher Di~l Indexes (Fig. 4-51).
POUR POIN'J ...

!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.)

Somewhat the same information is summarized in Tables 4-23 and


4-24 for world-competitive crude oils and for comparison with thermal
and catalytic distilhltes. &1 Cracked stocks are mixed with straigh t-nm
stocks in as large proportions as possible without causing an unsatisfactory Diesel Index. The pour points of cracked distilla.tes will be
even lower than, those of Tables 4-23 and 4-24 if they have been severely
cracked. Additional information on the properties of catalytic cycle
stocks is given in Tables
and 21-8.
.. Nelson, W.
Nelson. W.

8'l

Oil Ga8 J., June 28, p. 132, and July 12, p. 118, 1954.
Oil OM 'J.) Jan. 18, 1954, p. 111.

159

EVALUATION OF OIL STOCKS


~

.,;'"

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"

Oil Ga, I., Jan. 18. 1954, p. 117.

...

.. .
'.

'o606

-50
-30
-1

7
o6o6o6

....

. ..
. ..
10
18
25

-9
5
11
15
21

-16
-4

17

J
160

PETROLEUM REFINERY ENGINEERlNG-

TABLE 4-~. APPBOXlMATE EFFECT .01' BOILING RANGE ON TBliI POUll POINT OJ'

DISTILLATE OR DIESEL FuELS

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

11.4 11.8 12.2


C.F. e.F. . C.F.
of feed of feed of feed

...

. ...

...

-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

Oil Ga3 J'J- Jan. 18, 1954, p. 117.


b This a.pproximate relationship appeared independently from studies of both
straight-run and catalytically cracked stocks, but the pour pomt of thermally cracked
stocks appears to be less affected by boiling range.
G

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
-

.. Worr.a.1l, G. I., "Ind. E.ng. CMm., 46: 2180 (1954).

.'--.

,...

161

EVALUATION OF OIL STOCKS


,

(thermal cracking and coking) and Figs. 21-3 to 21-6 (catalytic-cracking


and refotming).
Lubricating Oils and Waxes. When produced by the conventional
pressing and centrifuge methods, the cut point between ' wax distillate
and cylinder stock should preferabl y 43 be 835F,' but pressible distillate
can usuaiIy be produced up to cut points of 870 to 875F if the viscosity
of the most viscous material does not exceed 600 sec. 811
Pour point cannot be predicted with accuracy nor can the reduction
in pour point that may be expected with coDl1i1.~rcial ' depressants be predicted eXcept within the following wide ranges:
Average
Per cent
'lowering,
depressant

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-

A method of evaluation of lubricating-oil stocks involving precipitation


of asphaltenes with petroleum ether, a fuller's, earth petroleum ether
fractionation to isolate resins, dewaxing with methyl ethyl ketone and
-benzene to separate wax, and an adsorptioIj' fractionation to provide
cuts .for' detennining' 'die -Viscosity ind'ex-yield f'elaiionship -has been
developed by N. W. Furby.9,o The results of such a- study have been
successfully correla.ted with plant performahce. '
A highly'satista.ctory propane deasphaltlng bomb for laboratory evaluations is described by Ditman and Mertens.91
Although the Viscosity Index of raw, lubricating-oil stocks may be
'estimated from Table 4-1, various amoun'ts of wax are associated with the
oil. Wax has' a Viscosity Index of about 200 (125 to 288) and a Characterization Factor of a.bout 12.88 (12 to 13.65),92 values derived from a
study by F~ TuWu of the lube stocks (700 to 900F) contained in 13 Venezuelan crude oils. Re~oval of wax greatly reduces 92 the Viscosity Index
Beiswenger and Child. True Boiling Crude ADalysis, Pet. Division, ACS, Atlan ts.
Meeting (not for publication).
90 Anal. Chcm., 22, 876 (1950); also Gester, G. C., "Progress in Petroleum Technology," p. 177, ACS Meeting, New York, September, 1951.
- tl Pet. Procuring, November, 1952, p. 1628.
~2 Nelson, W. L., Oil Gas J., Mar.-29, 1954, p. 131. '
, n" A Study of High Viscosity Index Oils," master's'thesis, University of Tulsa,
1953.
at

', . .:.:

162

PETROLEUM REFINERY ENGINEERING

and the Characterization, Factor of the raw lube. stock as indicated in


Fig. 4-52. In Fig. '4-52, zero per cent wax means the removal of 9nough
wax to r~duce the pour point to zero of. The dashed line is data of
J. B. Maxwell;94 and the circle points are data taken from the liter~ture.
60r---,----.----r---.---~----._--~--~-

WT. PERceNT WAA 140r---T---~--~~--~,__+----~--~--~~~~~

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

__

~L__ _~_ _~_ _ _ _~~

12.2

12A

12.15

12.8

13

fACTOR OF NARROW WAXY STOCK

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.)

Maxwell's line is probably a good average becaUse the results published


ill the literature often-pertain to oils of unusually high wax content.
Boiling point and melting .point are not directly ~elated except for
,the normal paraffin hydrocarbons. However, viscosity appears to
reasonably consi~tent~5 for all petroleum waxes. The approximate rela-

be

u IIData Book of Hydrocarbons,H Esso Rese&reh and Engineering Co., D. Van


Nostrand Company, Inc., Pnnceton, N.J., 1950.
.
011 Tiedje, J. L., A Laboratory Study of Wax Processing Methods, Proc. Fourth World
, Pet. Congr'J sec. VI, Rome, 1955.

-t
I

EVALUATION OF OIL STOCKS

tionshipbetween these properties is shown in Table 4-25 (see also Table


12-1).
TABLE

4-25
Misc. waxes G

n-Pa.raffins

I
"

~. ~

Mid boiling Viscosity,G


point, of SSU a.t 2100]' Melting
point, of

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

Likewise, the asphalt (A., wt %) in a residue may be estimated 97 from


the Conradson carbon (C., wt %), within plus or minus 10 per cent, from

.\

,A.

.1

.~~

a.le.

(4-11)

The yield of ~nished lubricating oil is then estimated by subtracting the


amounts of wax and asphalt.
The a.mount of wax contained in a raw distilled 'lube stock (700 to
900F) may be estimated with fair accuracy from the Characterization
Factors of the materials that boil at 550 and at 750F .(or 800) in the
Nelson, W. L., 011 Gcu J., Feb. 7, p. 127, a.nd Feb. 14, p. ]29, 1955. Ta.bula.tions
.
of dozens' of crude oils.
. lIT A Survey of Petroleum Resi'dua 88 Sources otLubricating Oil, Div. Pet. Chem.,
I
ACS Meeting, Kans&9 City, Mo., Mar. 29, 1954.
'.
.
,
III

I
I

=5+

164

REFINERY ENGINEERING

crude oil. The presence of wax


a. lube stock is associated with a
Charactetization Factor throughout the 550F and- 800F boiling
Weight % WtU in
70o-900"F em

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

'fhe relationship cannot be used when


Characterization Factor at
750F is
11.6 bf3cause such
are
solids or waxes.
Fina.lly, the
point and Characterization Factor 700 to900F lube
stocks seem to be related to weight per cent -wax, somewhat as shown in
Table 4-26.

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

in zero 'pQUr point ma.terial.

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

EVALUATION OF OlL STOCKS

Asphalts. The amount of asphalt (100 penetration) contained in crude


oils is related to the boiling range 98 somewhat as indicated in Table 4-27.
Apparently the bulk of very hard material in high-boiling crude oils
permits the incoip'oration of additional low-boiling material in the
asphalt. In addition, the high-boiling crude oils Do~~aIiy are .naphthenic
77/100 I 5

.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 "

\.
\

~(Y) VARIOUS . B~OWN

' ~

o n

~ (Air- o)lidized)
I

n~

.....0
... 0

120

140

1----

160

180

1--

200

220

240

SOFTENING POINT - .F;

FIG. 4-53. Relationship between softening point and penetration of vaCuum-refined


asphs.lts.

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

PETROLEUM REFINERY ENGINEERING

4-27. ApPROXIMATE

AMOUNT OF V ACUUK AsPHALTIC MATElUALA .AS A.


FuNCTION OF BOlLIN,G RANGE

Primary relationship

Secondary relationships"

Per cent 100


Asphalt fraction API gravity
penetration
starts to boil at of crude oil
aaphalt

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

Hard material but not neceasarily suitable for use 88 aspbalt.


"Approxima.te, and the two functions are related to the "primary relationship"
not to each other.
A

~1~--4---+---~~r-~--~--~~~~~--~

,~

~~--4---~-+--~--~~~~~~~~~

lit

~~--~r---r---+---~--~

10.

20

JO

40

&0

70

eo

to

100

BLENQ- PER CENT OF HlGH- PENtTRATION ASPHALT

FIG. 4-54. Estimating the approximate penetration of blends of similar asphalts.

Gas J.)

(Oil

. EVALUATION 0.J' OIL . STOCKS

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:

:.~):':: ;, <.. "'~:., :. :,'I:~[.~: .:~')',~ '.:' :. ~'. :~


.

;..

'.

. ~;

. :.:

. ,.

. .: . ..:. ;. .' . .

-.

-. ~

'(~

.. <.

s,I;'\~~ :

'. ~ " } .... ?'~

:.-:. )~~;~,;:w;~..

:. ~. '~~:' ~;. <~~:;L;~\; . ': ': ..~ ::~'-; , ;.,.:~j:~: '~i:i~~~~r?q~ .


J ,-.

:~~'"

',-,' :.i ~:;~j

.~~

.:r: .~' i~

~",; "

, .' -

- .~ !,,:~~:~:;;:,;~';~:~:j~;~':! ~~!-~~~;

: . ~\~.. _.,

r~:

~ (,.'- :y~

.~

~:,. '~~: .. ;.:.:""<",';):!;;',.". . ...':,.


!....

,<,

~:,~f"';). ""

,'. '.

.
.
..,': :: ~ ':'" ,': ()-. ~~,

.'

, ,

'0 ' : '

I
,:

.
.

..

" , ".

'.

:) ....

.,

,"

-.-;

:.

"

r.

.:

. ",

..

. : ",

J:

:.
...

.-

' :,' :.

'-:',

~', ~

' :'!""",- ..

. ..

"

. . .......
.,
.
.. -

. -.,

..
;

'. "

'. - :
~

.. -

. ,.

; -~

'. '

:,,',

'.

i. . ~ -

.- .',

':....

"',

'.

'

,-

.'-

'I

: ':

'

-.1..'

--

- .

~.~:

t.

' __ .~ ,', ,_ ..: ~ ;..

" _; ,_: -

: ( -:

'\ : _.' '

CHAPtt.R, S' ' ,',


"

~,

, .--

'\

,::" .' !,' ",


:- ,t~',; -- :' .. :

._! : . ,. :~(~ - .J:

.),

'. '

" ,

'

:- -

',," (':

'.,

",

-.

'

_ ,.

'PRYSlcAL,PROPE,R1IIES
,O.F
oiL , :_-;;,:~ . ;:
.
- .
. :PETROLEUM
.
-'

).:

"

.-. --- ... ':

i _

,-' : ; '

.,

..

;"

-, Chapters 2, ,3, and 4 indicated that petroleUm: and petroleum products


are _complex, ,l1'lB.terials. . At' present the chemical a~d ph~cal laws .that
govern the beb:avioF ,.of ,ri:tbtim:.e$, Qr~hydt()carbOris , are' nqf adequate:ior

. :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'

t~o~AA~~:''.t.~riipe~~t~r~ :::4iff:~h~~c~:: 0! ~~~. d~.. _. Unive~~y the --~il


ind'u:strYji~~~,tpe EngIish-'sy:stem' iri wPieh the specIfic hei\t is defined as'

the' numbe~ 'or-British thermal units '(Btu)

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

Also note the specific heat at 350

Specifio Heats of Oils, liul. Erig. chtni., 18, 795 (1926).


t Heat Content of ' Petroleum Oil Fractions at Elevated TemperatUres, lnd. Eng.
Chetn., 24, 210 (1932).
1

168

,I
I

169

PHYSICAL PROPERTIES OF PETROLEUM OIL

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

V d t/:: ~ ~ ~ t::/ /'

/ / ~ ~~ ~ ~ ~

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.
.

The Characterization.Factor 4 found to be so useful in cataloguing crude


oils (Table 4-1) is of even greater value in accounting for the degree of
paraffinicity of individual fractions.

, K '=~
8

'where K = U.D.P. Characterization Factor


T B = average boiling point, OR = (OF + 460)
8 = specific gravity at 60F
The factor has been useful in correlating many properties, among which
are hydrogen content, ani1ine point, thermal expansion, and Viscosity
Index, as well as the relationships employed in 'this chapter. '
'Total Heat Content and the Effect of Pressure. The heat content or
enthalpy of petroleum liquids and gases can be obtained most convenThermodynamic Properties of Light Hydrocarbons, Ind. Eng. Chern., 84, 590
(1942).
4 Egloff et aI., The Modern Crn.ckin~ PrOC~B8, Oil Ga8 J.~ July 2, 1936, p. 34. '
3

'

PETROLE~

170

REF1NERY

from Fig. 5-3, which was compiled by


Shell Development
Company6 a.nd is based on data.
et al. s.r Note that the U~.Il""
temperature is OaF and that the
lines of the chart are based on $.
(Characterization) Factor of 12 rather than 11.8, which is used

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

PHYSICAL PROPERTIES OF PETROLEUM OIL

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

338 - 0 - 12 = 326 Btu/lb

Heat conteJ;lt at 500F and 200 psis. """ 385 Btu/lb


Hea.t content at 400F and 200 psia. = 326 Btu/lb
Change in heat content
59
Specific

~eat of VB.po~ at 200 psia. (between

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.

Molal Average Boiling Point. Ordinarily the distillation data obtained


. from the laboratory are on a liquid-volume-percentage basis, meaning that
vapor temperature is plotted against percentage of liquid distilled. The
molal average boiling point of the material is sometimes more satisfactory
for purposes of correlation than the volumetric percentage. The relation~
"'~1!, between these two bases of percentage (as well as other bases) is
,

172
30

+ 20

PETROLEUM REFINERY ENGINEERING

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

For true molal

~=~~=~==~==~==:=QverQge
11

""

0'

" , _ it- _....

'"

' ...

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.

(Ind. Eng. Ch.em.)

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,

BOILING RANGES, AND CoRRECTIONS

(OF)

TO CONVERT VOLUMETRIC TO MOLAL AVERAGE BOILING POINT

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

.. To be subtracted from the volumetric average boiling point.

104-128

173

PHYSICAL PROPERTIES OF PETROLEUM OIL

Latent Heat. The heat of vaporization, commonly referred to as the


latent heat, is usually defined in terms of Btu required to vaporize lIb of a
liquid at its atmospheric boiling point. If vaporization takes place at
another pressure (or temperature), the latent heat should be ,specified as
such.. The latent heat varies with the temperature (or pressure) at which
vaporization occurs and with the type of hydrocarbon.
Latent heats 8 at atmospheric pressure for petroleum fractions are given
in Fig. 5-5 as a function of boiling point and molecular weight or API
180.-~~----~----.----,----~----~---.----~--~~--~

....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

~~)(joso. ggos 011


\~,'Oislillale.s

~
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.
-

PETROLEUM REFINERY ENGINEERING

174

tha.t outlined by Watson 9 must


employed.
temperature is
in terms of the latent heat
point, as follows:

latent heat at any


the normal
.
(5-1)

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..

Reduced Temperature TRIO+,


c

base, narrow-'boiling-range fraction


a. gra.vity of
API. The latent heat.
5-6. Temperature correction to heat
of vaporization.'
.
of this fraction at atmospheric pressure
.
also at 5QOF desired.
A mixed-base stock will have a Characterization Factor of
11.9. The
ing properties were read (rom Fig. 5-9:
Atmospherio boiling point. . . . . . . . . .. 580"F (10400R)
Molecular weight. . . . . . . . . . .. . . . . . .. 250
temperature ................ 900e F (13W R)
Q

these data, the la.tent. heat at


found to be a.bout 92 by
to Fig.
In order to estimate
latent heat at 500F, additionsl factors must be set

l'""r~''r'pl,\1''1''

=:

1040
1360 =

T
"f

latent heat at

= 500

from

+ 460 = 0 706

1360
.
5-6 = about 1.16

from Eq. (5-1) is


L "'" 1.16 X

9S9-{040

= 98

Heats of Vaporization, Ind.


Clum' j

PHYSICAL

L.H. AT./'

~~

~TMOSPHERIC

8. P.

PROP~RT1ES

175

OF PETROLEUM OIL

140

~~

\s-,-" K' ~""',\

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 ~

,\ ,'"\l'\\'" r-...'" " '"r'., ~


1\ 1\\ \'1'\\ 1'\ r\" l'( ~

20

"

I~ ~

~ '\

,,~

\60, 1\50 \ \ 140 1\ \ 30


\ \ \ 1\ \ 1\
\ \ \ 1\ -\
,\ \ \ \ ~

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

Nelson, W. L., Oil Gas J., May 26, 1945, p. 163.

176

PETROLEUM REFINERY ENGINEERING

-,

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

1 1\ ' \ \ \ f\. , r--.....


\ \ 1\ \ \ ~\ r\ 1\ 1\ 1'"
\ \, \ 1\ . \ \ \ \ \ \

"\-

NAPHTHENE

60

l.&J

:r

1\ \ \ '\ '-.; "


\ \ \ 1\ \ , f\,
\
\ \
\\
~
\. \\
~\ \
.~, \

'

II

~ ~I

'~

, \. ~\' t\\ ,"... ~~ ~ L LH. AT 1 1\


1\ \ \ I\'~ :\ r-\.\ ''\ ~ ATUOSPHERIC
,,,\ 1'\ ~
B.P. -t--

:::)

~~

1\

.n
100
-J
a:
....,

~~

~ 140

\ ~ \60'

~~

'0

PARAffiN BASE STOCKS

1\ 1\ ~ ~
1\, 1\ 1\ '\ r\' ~ !;:o..,.

.'. API GRAVITY

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

PHYSICAL PROPERTIES OF PETROLEUM OIL

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
.

Molecular weight ... .s . .'. . . . . . . . 195 (Fig. 5-9)


Critical temperature ...... _...... : ...... ' 845F (Fig. ~9)
Viscosity at 122F,. centistokes ........... 2.1 (Fig. 5-10)
Note thilt f if any two properties ~l.fe knolfd; all the other prope;ties can be estimated.

is

When a pure compound heated' at atmospheric pressure, it eventually


reaches its boiling point and is completely vaporized at a constant temperature unless the .pressUre is increased. If the pressure is increased, the
compound is completely condensed and cannot be vaporized a.gain unless
the tempera.ture is also increase~. This mechanism, alternately increasing the pressure and temperature, functions until at some hlgh temperature and pressure it is found that the material cannot be condensed
regardless of the amount of pressure applied. This' point is called the
"critical point," and the tempera.ture and pressure at' the critical point
are called the It critical temperature" and U critical pressure," respectively. The liquid phase and vapor phase merge at the critical point

178

PETROLEUM REFINERY ENGINEERING

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

Molal ,Average BOiling Point, of.

Zs
til
aI

"'t3

tIQ.

u;

ti 0
100

<t

200
Volumetric Average Boiling Point, of.

FIG. 5-9. Molecular weights, pseudo critical tempera.tures, Characterization Factors,


and gravities of petroleum fractions. (CbUriesy of Hou.genand Watson, "Chem. ProcesB
Principle8,'t vol. 1, John Wiley & Sons, Inc., New York.)

1i9

PHYSICAL PROPERTIES OF PETROLEUM OIL

so that one phase cannot be distinguished from the other. No volume


change occurs when a liquid is vaporized at the critical point, and no
heat is required for vaporization, but the coefficient of expansion has
become large (Fig. 5-14).
- The critical temperatl:lres and pressures of some pure compounds are
given in Tables 5-2 and 5-3. In addition, Figs. 5-9 and 5-12 may be used

..s

10

IS

20

25

30

35

40 4S

50

55

60

65

70

75

DEGREF:S. API

FIG. 5-10. Relation of viscosity at 122F to Chara.cteriza.tion Factor.

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' ....

FIG. 5-11. Reln.tion of Characterization Factor Lo viscosity at any tempemture.

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,

Pseudo Critical Point.

Critical va.lues for ethane and propane are

Critical temperature, oR ...... \


Critical pressure. . . . . . . . . . . . . .

Ethane

Propane

549
715

665
616

For a 90 mole per cent propane mixture of these


Pseudo critical temperature .......... (0.1 X 549)
critica.l
............. (0.1 X 715)

values

be used to compute volumes

+ (0.9
+

X 665) "'" 653.4"R


(0.9 X 616) "'" 625.9

etc., of such a mixture.

rHYSICAL PROPERTIEs OF PETROLEUM OIL

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

450\\\\1\\ \\\~ \ \~~\ ~\~ \~\ '\ 'U~O 1150


--so'rtK\ \.\ \\\\~\,I\\'~,\\l\\\~\i\\'\ \ ~20qZ50

ssq~ \~~\' ~r\\\l\~\\\~~~,\~<\l~~O

i1
Cr- i:;:700

,
100
100

200

~~ ~~~~'\~~\~00

~P"'t?e,..o 008~ '~~~~~~~


: flJre, D~ 9s~~~~~ ~ 1300
!
J9W ro~l~ ~ f250 .

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

PETROLEUM REFINERY ENGINEERING

In the correJation of many properties, reduced properties are useful.


Reduced properties 'a re defined 'as the ratio ,~f the actual value of the
property to its ,c ritical value. Thus for volume, temperature, or pressure

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:

Specific Volume. The volume occupied by 1 Ib of vapor is called the


specific volume. ,Accordin'g to the laws governing the behavior of perfect
gases, the volume varies inyersely as the pressure (Boylejs law) 'and
directly as the absolute temperature (Gay-Lussac's or, Charles'law) or

PV

P'V'

= ---;p- = R (the gas-law constant)

(5-2)

where P and P~ = psia (14.7


gauge pressure)
V and V' = volume, cu ft
T and T' = absolute temperature or' (OF + 460)
R = 10.7 when considering lIb-mole of gas
At standard conditions of 32F and !1 pressure of 1 atm or 760 mm, the
volume of lIb-mole of a perfect gas is 359 Cll ft. At 60F and 760
the volume is 379.4 ell ft (379 is commonly 'used).
The volume of 1 lb-mole of a perfect gas, viz., 359 eu ft, is the factor
that relates the volume of a gas to its weight. ,The fQregoing laws are
sufficiently exact for engineering calculations involving such gases as air,
nitrogen, oxygen, flue gas, and 'n atural gas, unless the pressure exceeds
about 200 psi. For high pressures and for the vapors handled in the
refinery the laws are not exact but they are used extensively.

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)

30 X 379 X 740 X (460 + 60)

1,648 cu it

WhB.t is the volume of 100 Ib a.t 1000F and 10 psig?


,,100
14.7 (460 + 1,000)
60)
Volume at 1000 F = , 30 X 379 X 24.7 (460

alSo

= 2,110 eu ft

X 10.7 X 1,460 "'" 2 110


v:o1ume == 100
30
24.7
'

Pressure-Volume-Temperature Relations of ,Vapors. Petroleum


vapors do not obey the perfect gas laws. In general, low-molecular-

PHYSICAL PROPERTIES'_OF PETROLEUM OIL

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)

gas constant = 10.7 for the following units: 1 mole of gas,


volume, en ft; pressure, psia; and temperature, OF abs
n = number of moles of gas
Other 'gases deviate from the foregoing by the factor Z;

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
.

A tria.l-and-error solution is necessary because the compressibility factor Z is


funotion of the unknown pressure. Assume Z = 0.9.
P X 31.2 = 0.9 X 1.0 X 10.7 X (460
P = 228 psis.

+ 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

"

API a.t 60F ..........................

16.03
2.98

30.05
3.97

0.300
2 . .5
340

Iaobu\aD.e

Plopa.ne

..

Moleoular weigbt .......................


Carbon-hydrogen ratio .................
Liquid gra.vity:
Specific 60/60 ........................
De~ty. Ib per gal at 60F .............

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

Molenula.r weight ......................


72.09
4,96
Carbon-hydrogen r:a.tio ..... , ....
Liquid gravlt.y:
0.631
Speoific 60/60 .............................
5.2,6
DeOllity. Ib per gal at 6O"F ..........
API at 60F ....................................
92'.7
Vapor gn.vit.y:
Relative to air. . . . . . . . . . . . . . . . . . . . . . . . . . ,
2.4.91
2.7./)
Cu ft at 60"F per gal liquid ... ' ..........
Boiling 'point, of ........... _ ..........
96.9
Critical temperature, oR ................ , ...
846
Critical pres, u re. paia. . ,..... . . . . . . . .
4S4
Critiaal volume. ou ft per Ib-mole .. , ........
4.97
Criua&l viBooaity, mi(lX'OpO~e8 ...................
238
~ Speolfio heat:
V ..por ............................
,p.409U
Liquid at 60F .... , . , . .-............... !.'O.64 l1
Ratio ..t 60F ......................
1;.120
Coeflioieot. of e:.::pa.ll8i.on ......._................'
0.0011i4o- ao
In Ba.mm.a bili toy lJ.mi."kI:
Low ................................
1.46
High ..........................................
7.8
Hea.t 'of aombuatioo:
Groaa. Btu per lb ......... , ... , .............. 21,120
Net., Btu per lb ...................... '.. 19.640
Gr088, Btu per nu ft~ ...................
4.016
L ..~nt heat. Btu per lb .............. , ..........
154
.vapor presaure ...t lOOoF, psi&.
15.6
Oota.ne Dumber, Motor method ....... , .........
61.9
6.128
PI/WI. e~paDaiOD. ClOD8~ant for liquLd............ '.'

....

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

PaOPEBTIES OF VA1UOUS HYDROCA.RBONS"

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

Moleoular weight .... . ... .. ...... . .


C ..tbon-hydrogen ratio . .... . .. . ........
Liquid gra.Yity:
Speoifio 60/60 .................. " ..
DeQl!lW, lb ' per gal a.-t. 60F ........ . .
API. at 6O"F ............ . ......
Va.por gl'lLvit.y:
Rel&ti ve to air . ........ . ........
Cu ft at 60"F per geJ. liquid . . .........
Boiling point, OF . . .
Critical t.emperlLture. oR', .. '.... . ... , ..
Crit.ioal preNure~ palA .......... . , .. , .. ,
Critioal volume. ou 1. per Ib-mole ... . .. , .
Crltioal viaOOSlty, mioropolaea ... . ......
Speoifio heAt.:
Vapor ............ , ..... . .. . ...
Liquid at 6ooF ....... . .......
Ratio at 600F ..... . ... , . : ..... ' ..
Coemoien~ of expaaaion . . ...........
Inflammability limita: .

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

OrDaB, Btu pet lb .......... 20,230


Net, Btu per lb .. . ......... . ... 19,180
, Gro.a, Btu per ClU fV ..... . .....
2,968
Latent heat. Btu 'per lb ....... . .........
177
Vapor proaawe at. lOO"F, P8ia. .. , . .. . .
64.7
Ootane numb8l', Motor metbod ........

...

........

....

. . . . 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

PHYSICAL PROPERTIES OF PETROLEUM OIL


,

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

. CoefJiclent 'of Expansion. Government bulletins and other agencies 12


present volume-correction tables for (1) four-carbon-atom hydrocarbon
mixtures, (2) straight-run 'products (10 to 95 API), (3) volatile products
(95 to 150 API), (4) asphalt and fluxes (0 to 15 API), (5) m,ixtures of
gasoline and benzol (0 to 50 per cent), and (6) cracked gasoline. The
mean coefficients of expansion for different gravity materiald up to about
400F are a.pproximately as follows:
Meon coefficient
Gravity range

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

The coefficient of expansion may be defined as the fraction of unit volume


that a unit of material will expand if it is heated through one degree.
Example 6-10. Coefiic.ient of Expansion and Fig. 5-14. One barrel of &19 API oil
is to be heated from 60 to 40QoF. What volume will it occupy?
C.IOefficient of expansion = 0.0004 approximately
Increase in volume""" 1(400 ~ 60)0.0004 = 0.136 bbl
Total volume == 1.136 bbl
Using Fig. 5-14J

Sp gr at 607 (19 API)


11

= 0.9042

ASTM-IP Petroleum Measurement Tables. p. 101, 1952j and Carney, 13. k,

The Density of the Liquefied Petroleum Gas Hydrocs.r~IlB, 21st Annual Couvention
of the NOAA.

f
~\'
190

PETROLEUM REFINER'! ENGINEERING .

l.

r:

Follow 0.94 line to 400F


Sp gr at 400F = 0.83

Volume at 400F"'" 1 X

~~~

.",. 1.13 bbl

The volume by Fig. 5-14 is ~robably the more accurate.

Density and Specific Gravity. The approximate density of petroleum


products at elevated temperatures U can be obtained from Fig. 5-14 (see
Example 5-10). The figure relates the specific gravity at 60F with the

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.)

specific gravity at other temperatures. The number accompanying each


iine indicates the gravity of the material at 60F.
Density is defined as weight per unit of volume. In the petroleum
industry, density is usually expressed as pounds per gaHon. Since 1 gal
of water at 60F weighs 8.3281b, the density is
Density, Ib per gal

sp gr X 8.328

The relation14 among API gravity, specific gravity, and density is given
13

Nelson, W. L., Determining Densities . . . at High Ternperatu.rea, Oil Gag J.,

Jan. 27, 1938, p. 184.


1.

ASTM.IP Petroleum Measurement Tables, 1952.

I~

r
I

191

PHYSIOAL PROPERTIES OF PETROLEUM OIL

in tables in Appendix A. The density of gases can be computed by the


mole volume relationship of Eq. 5-2.
Example 6-11. Density and Specific Gravity. Wbat is the density of a 29.3 API
material at 60 and at 600~?
At 60F
_Sp gr = 0.88; density 7.328
.

.'

Refer' to Fig. 5-14, a.nd follow 0.88 line to 600F.


,

Sp gr a.t 600F = 0.678


Density at 600~ - 0.678 X 8.328 - 5.65 lb per .gal

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 =

Since molecular weight of air

6~~::

= 0.001271

= a.bout 28.8,

Sp gr of flue gas at 60F referred to air

'=

2~~8

-- 1.04

FigUres such as 5-14 can only be approximations because hydrocarbons


of the same density at OOF may have different critical temperatures
and thus must trace different curves. In addition, pressure greatly
affects density at high temperatures. Watson and Gamson 16 provide
Fig. &-15 by which the density of any material at any temperature or
pressure can be estimated if one experimental measurement of de'nsity
is available.

-&)P = ,W-PI1 = -&)P22 =

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

Values of PI/WI for a few hydrocarbons are shown in Table 5-2.


Thermodynamics of the Liquid State, Ind. Eng. Chem., 36,398 (1943); and Vapor
_ Pressur~ , and Critical Properties of Organic Compounds, NaIl. Pet. News, Tech. Sect.,
MAy 3. 1944.
15

192

PETROLEUM REFINERY ENGINEERING

Example 6-12. Liquid Density at Any Pressure or Temperature. A wide-boiling.


range distillate material bas a.n average boiling point of 500F "nd a gravity of 30
API. According to Figs. 5-9 and 5-12, such a material has critical properties as
follows:
Tc = 810F or 12700R
p" =; 315 psia
At 60F

&lld

14.7 psia the density and the reduced


111

-=

TR =
PB

conditio~SiAre

<t.S7JJ
60

460
1270 = 0.41

~~;

= 0.0467

According to Fig. ~15 the value of W1 is 0.14.


Other densities can then be computed from
p

Pl

0.816
(oJ =
6.2&'
0.14

= -"- '" = - "'1

Thus, at such conditions as 650F and 1,500 psis.,

+ 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.

Change of Viscosity with. Temperature and Pressure. The engineel


frequc~tly must estimate the viscosity of an oil at other than the cus-:.
. tomary testing temperatures. Tbis may be d~one by Fig. 4-43, but
greater accuracy is possible by use of ASTM viscosity-temperature
charts 16 (see Fig. 4-45). However, in order to use these .charts it is
necessary to know the viscosity at two temperatures, or to know one
viscosity and the Viscosity Index .. Kinematic viscosity (or centipoises)
can be obtained. by the us.e of Eqs. (32), (3-3), and (3-4) on page 25.
Example 6-13. Viscosity at Different Temperatures. on A of Fig. 4-45, has a
Saybolt Universal viscosity of 200 sec at lOOF and 45 sec at 210F. A 1ine connecting
these points on ASTM viscosity paper (see Fig. 4-45-) gives the vi$cosities at other
tem pera.tures.

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

PHYSICAL PROPERTIES OF PETROLEUM OIL

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 _

~ == 0219 X 200 _ 149.7


0.85'
200
Z = 43.05 X 0.85 "'" 36.6
As a comparison (line 13 of Fig. 4-43), the centipoise viscosity at 100F is about 32.0.

<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.)

It has now become common practice to measure the rate at which


viscosi~y changes with. temperatu:re by' means of the Viscosity Index.
This relation is discussed on page 85 (see also Figs. 4-1, 4-2).
The effect of pressure upon the viscosity of liquids is not great at normal
operating pressures, -but at a pressure of 1,000 psi and upward its effect is
astoundingly great.17 AE a general indication of the effect of pressure, the
Dow, Fenske, and Morgan, Effect of Fressure on Viscosity of Oils a.nd Chlori-nated Dip~ny19, Ind. Eng. Chem., 29, 1078 {1937).
11

r
194

I
i
I

PETROLEU1d REFINERY ENGINEERING

viscosity is increased about .1 5 per cent at 1,000 Ib, three- to eightfold at


10,000 Ib, and upon exceedi~gly 55,000 psi most oils begin to solidify.
Viscosity of Hydroca,rbons. Altho\.\gh Fig. 5-16, taken from Uyehara
and Watson,18 is based primarily upon light hydrocarbons and organic
compounds, it is probably the best method available for estimating the
viscosities of heavy refinery vapors. Critical viscosities of such vapors
can be estimated 18 from

VM~

T~

Pc = 7.7

(5-3)

where J.Lt: is the critical viscosity in micropoises, M is molecular weight,


Tt; is the critical temperature in OK, and Pc is the critical pressure in
atmospheres.
Example 0-14. Viscosity of Vapors. A 60 API gasoline has an average boiling
point of 250F. According to Figs. 5-9 and 5-12, it haa the following properties:
Molal average bp .... . .. . .. . ..
MolecUlar weig.h~ ............. ,
Critical tempera.ture. . . . . . . . . ..
Critical pressure. . . . . . . . . . . . ..

The critical

temper~ture

215F
102
540F
460 psia

(OC) is

(540

+ 40) +

1.8 - 40 = 282C""", 5550}{

and the critical pressure in atmospheres


460 + 14.7 = 31.25

USing Eq. (5-3),

. 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

PHYSICAL PROPERTIES OF PETROLEUM OIL

0.25
0.2
0.4

195

1/1/

05 .0.& 0.1 0.80.91.0


1.5
2.0 2.5 1
4
5 6 7 8 9 '0
Reduced Temperature Tr=T/Tc
FIG. &-16. Genera.lized reduced viscosities of hydrocarbons. (Courugy of Hougen and
Watson, "Chem. Procea8 Principles," vol. 1, John Wiley &: Sons, Inc., New York.)

196

PETROLEUM REFINERY ENGINEERING

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

PHYSICAL PROPERTIES OF PETROLEUM OIL

OF

~
,\I)

~/6~
....ti

1200
/lOa

E::

1000

900

~ 120 ~~;;::=J!!:;1---t---~ KEROSENE

'11)

::

350-50OCF

~~9---+---;--- 18 characterizatIon factor

------i

42.5 API
50

/00

150 200

300

400

500

Pressure, PSJA

FIG. 5-19. Viscosities of kerosenevapora (3So-S00"F, 42.5 API, 11.8 Characteriza.tion


Factor). (Oil GD.$ J.)

of

.~

RI60

1400

1200

....g
~
~

a/20

GAS OIL

.\1)

s::

450-650~

11.8 characlerlzatlon foctor


35 API

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

Mills .e t a.l., Ind. Eng. Ckem., 38, 442 (1946).

198

PETROLEUM REFINERY ENGINEERING

TABLE

5-4.

VISCOSITY OF A

FEw PETROLEUM VAPORS'" (see also Figs. 5-17 to


5-20), MICROP018ESll
'

Pressure, psiA

Temp,
of

14.7

I 50 I 100 I

200

I 300 I 400 I 500 I

600

700

1000

Lean gas (18 mol. wt)

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

Light gasoline (lOo-a40F, 61 API)

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

Naphtha.' (300-450F, 46 API)

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

.. Note that cra.cking or decomposition will change the composition at lemperaturcE


a.bove abou t 700F unless the time is very short.
" One-millionth of a poise or 1/10,000 centipoise.

of various refinery fuels. The hydrogen content of p~troleum fuels may


be estimated from Fig. 5-23.
Net heating value 'may be computed from th-e gross heating value
and the pei'~entage of. hydrogen, by subtracting the latent heat of condensation (at calorimeter-bomb temperature) of the water produced dur,"
ing combustion of the hydrogen.
Explosive Limits. The beha.vior of some materials is indicated in
Table 5-5. Pressure has little effect on the lower limit but it tends to

199

PHYSICAL PROPERTIES OF PETROLEUM OlL

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 ~

./

...........- ~ .........-:- V"............... '../ . . . ~............

. .",

./

-"""" ~

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

Inflammability limits. vol. %

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

* Read from a graph.

Many sca.ttered points.

Heat of Fusion. The heat of fusion of paraffin wax, as reported by


various investigators, ranges from 63 to 78.5 Btu per Ib, an average
value of about 72.5. 'The data of A. Bondi2i on the heat of solidification
and of mixing of wax' and oil are shown in Table 5-6. The paraffin wax
completely solidified, but the oils were coole~ only through the ranges at
which the wax solidified.
Jones and Kennedy, U.S. Bur. Mines Rept. Invest., 3798, February, 1945; also
Nelson, W. L., Oil Ga8 J., Mar. 3, 1949, p. 92.
n Handbook a.nd Catalogue No. P-7 of Va.por Recovery Systems Company (Varco);
also Nelson, W. L.} Oil Gas J.} Jan. 13, 1949, p. 66.
2a Physical Chemistcr of Lubricating Oils, VI, Phase.Equilibria, Pet. Refiner, June,
1947, p. 116.
21

200

PETROLEUM REF1NERY ENGINEERING

- 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

PJI'YSICAL PROPERTIES OF PETROLEUM OIL


TABLE &-5. AUTOIGNlTJON TEMPERATURES AND ExPLOSIVE LIlIrIlTS

Explosive limits,

% by volume in air Autoignition

Mater:a.l

Carbon monoxide ................


Hydrogen ...................... ,
Acetylene .......................
Hydrogen sulJide ............. , ...
Methane ................... . . .
Ethylene ....................... ~
Ethane ........... . .... , ........
Pro)ylene .......................
Cyclopropane ............ -. ......
Propane . .......................
N a.tural gas .....................
Butadiene 1-3 ...................
n-Butylene ......................
i-Butane ........................
n-Butane .......................
Methyl ethyl ketone .... , ........
Methyl n-butyl ketone ...........
n-Pentane .......................
Benzol ..........................
Cyclohexane ....................
n-Hexane .................. -. ....
Toluene ........................
Styrene ....... , .................
n-Heptane ......................
o-Xylene ......... ~ ..............
n-Octane ........................
n-Nona.oe .......................
n-Decane ...... , ............ ~ ...
Petrolewn ,ether .................
Stoddard's solvent. , .............
Gasoline.' ................ _..... ;
Kerosene ......... . ... _..........
Lubricating oil, .spindle ...........
Lubricating oil, cylinder ......... :
~

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.

Also see Dougherty, R. P.,

202

PETROLEUM REFINERY ENGINEERING

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

100 0 f \~?; SD~"


fbOO af 5~1.
qOO of ~

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

Paraffin wax .... , ... . . , . , . . ...... 124-118


10 per cent No. 1 in 500 pnle oil .... 95--61
10 per cent No.1 in 300 white oil .... 104-59
Pa. bright stock .. ~ ............... 59--36
Pa. 150 neutral ................... 45-18
Pa. SAE 30 oil ................ . .. 46--19
No. 6 plus 0.5 per cen t Para.Bow .... 46-14
Waxy 300 pale oil. . . . . . . . . . . . . . . . . 59-36
No.8 plus 0.5 per cent Parafiow .... 55-32

122
82
90
28
23
23
3
36
-17

These are based on' the entire wax-oil mixture.

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
,

'

where the solubility decreases. No simple relationship is available for


the solubility of oils in ' water, but at the boiling point of water, the
solubility of lubricating oil is about lo-ri to 10-4 mole per cent oil, depending on the molecular weight of the 'oil.
50

_/

'/

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

GosoJi~,;e fuel, Irerosen.

ond OJ7s
)( PrtJpeM and isobuJoM
C PrDtJtme and bu/rlne

---

Porollinic aviolion I}OsoJine

---:-

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.)

The solubility of oxygen (and perhaps air) in oils is indicated in Table


5-7. 26
Sudace Tension of Hydrocarbons. Table 5-8 indicates .the effect of
temperature on the surface tension of hydrocarbons,21 and the general
26

21

Nelson, W. L., Oil Gas J'J JUDe II, 1942, p. 48.


Katz and Saltman, Ind. Eng, Chem., al, 91 (1939). ,

204

PETROLEUM REFINERY ENGINEERING


TABLE

Partial
pressure,
mm

100
400

5-7.

SoLUBILITY OF OxYGEN IN

Solubility of oxygen, co per liter

.'

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

.....

SURFA.CE TENSION OF HYDROCARBONS

Dynes per centimeter


Surface tension a.t these temperatures,

Methane ............' ...


Ethane .................
Propane ................
lsobutane. .............
Butane .................
Pentane ................
Hexa.ne .................
Heptane ...........: .......
Octa.ne .... :.............
140 mol. wt .............
160 mol. wt .. . .. . .......
180 mol. wt ........... . .
200 mol. wt .. '...........
220 mol. wt .............
240 mol. wt .............

-150 -100 -50

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

effect of temperature may be computed from this equation.

in which T is the absolute teinperature (OR), Te is the absolute critica1


temperatu~, and V is the tension in dynes. per centimeter.
,. ' Vapor Pressure and.Boiling Point Corrections. The vapor pressure or
tendency of a liquid to vaporize is involved in condensation, vaporiza,.tion, fractionation, etc., computations as well as ' the correction of boiling
points from 'one pressure to another. Figs. 5-25 and 5-26 are the result

PHYSICAL PROPERTIES OF PETROLEUM OIL

205

of an. exhaustive study of all available information27 including Fig. 5-27


also shown here. They (Figs. 5-25 and 5-26) should be' used when great
accuracy is required and for the correction of the boiling points recorded
in vacuum distillations. The Esso Engineering and Research Company
has. pUblished a series of standard tabulations U based on these figures
by which recorded distillation temperatures may be converted to their
normal (760 nun) boiling points. A more convenient but less accurate
method of presenting vapor pressures.is shown in Fig. 5-27 and it may be
used -for most engineering computations.
Charts of the vapor pressures of paraffin, olefin, and naphthene hydrocarbons exhibit a consistent pattern, but the lines for low-boning aromatic
hydrocarbons are quite erratic even showing curvature. Nevertheless;
the effect of the kind of hydrocarbon series or Characterization Factor
is very small,. and need not be considered except when the range of va.por
pressure is very great (tenfold or more). Maximum corrections for
Characterization Factor are only about plus or .minus loaF when correcting. conventional materials from 0.1 mm up tp"atmospheric pressure.
Figs. 5-25. and 5-26 are based on R. 'Characteriza~ion Factor of 12.0, and
corrections may be c<)mputed 27 from;
At

= -2.5(K - 12) X }OglO(P2/P l)

(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.

Use of Vapor Pressure

Charts~

A. What is the vapor pressure of n-butane at 77F (25C)?


By means of 's , thread or ride, align on Fig. 5-?:l the ' temperature of 77"F on the
right-band scale with the point for' n-butane (30+ GF)' on the center scale and reaq
1,800 mm or 34.7 psis. on the left scale.
B. What is the boiling point of n-butane at 1,000 mm?
Align 1,000 mm on the left scale of Fig. 5-27 with the n-bu.tane point on the center
scale' and read 44 or 45 G F on the right scale.
C. An oil is boiling at 300F in' a vacuum still at 9 mID pressure. What is the
atmospheric boiling point?
On Fig. 5-25 read upward from 300c F to 9 mm. This indicates an atmospheric
boiling point of 556GF. Likewise, Fig. 5--27 shows an atmospheric boiling point of
-.about 557 c F.
D. If the oil of part C bas a Characterization Factor of 11.3 rather than 12 (the
basis . of Figs. 5-25 and 5-26), the atmospheric boiling point is. 559.4F rather tha.n
556F. This was obtained by using Eq. (5-4):

at = -2.5(11.3 - 12) X loglD

76%

= - .2.5( -0.7) X 1.927


= . 3.37F

Thus, '556 plus 3.37 = 559.4~


n Maxwell and Bonnell, Derivation and Precision of a New Vapor Pressure Corre1&tion . . . , Ind. Eng. Chem., 49, 1187 (1957).
18 Vapor Pressure 9hs.rts for Petroleum Hydrocarbons, April, 1955.

206

PETROLEUM .REFINERY ENGINEERING

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

ESSO AESEAROf AND ENGINEERING

~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~<;

VJ L /

I / IV
I I / VI

I f I

/ II /

/ /

,t.

, , ,I'

II

1I

V '/ ) / / 1/
I~
V; j V/,~ / ~/ ~ I/"~VI I / V
I

1/

f
/.

I/~t

;J, I
/ / I I I I , I / II 1/
.
/ If
I
~O~ 1 '4, 'I J / / 'I L L /
/ ~:' / If IJ'( & ~I I I / / L / 1/1 / / II II III
1/

~_P~~I

./ '/

V/ /

II

VI

II

II

/
J

1/

II

V /

II

'I

V/

~ / V~
IJ

1/

lL ~

0.08
0.04
0.03

II

0.06

I I II

,/ V J / V
V V J / ./ VlL V V ol~i~'
JJ / V 'L 1/ VI /
V V V / V Vv /V~~/V~;OI/ /1/ / V/
V 1/11
V
II /
~~,
II

0.2

1 .I .I f Ilf
I V
I

/
I

V ' / L lL~ , I / V I J / I If .
J
If
V V I I VII VI VI I / j / j VVJj
L/ VV

lL

0.4

0.1

f
If

0/

VI I / V
/
.~"~J) II V 1I

LaI
Q.

1/

:l

Ul

f
1/

If

~ j V~ I / j I V/ V~ I VI

V
J

'(

I / / / V I
1/ / / / VJ I / / / / V/
VI VI
/ V/
/ /
V

/I

20

I / / / / I

30

.1/ 1/

40

::l
U
D:
LU

II

80
60

VJ

~V
I ~ / I / / V/
I
/ /
////
V
V
V
I
j~ /I ~ I II / V/ / / /

100

>-

1/

VV V V I I VI

This chort applies to stocks having a


chor9cterlzation foctor IIKllof 12.0

200

500

400

1/

II
j

I /
If

(l

""7

11

II

-"

I ~

, 'I

II

I I 1/

/ tEl I II I / II / /11
II
/ /
/ Ii II 1 tl~' II 1/ If J
I I

I, I / 11 :;I / i/~I/ V ref.. IfV


V V I VI
V
V
V
/ V I / / I / j V/ VI VI ~ II / VI/;V I~~ VIf 'IL
V

/ VI

V/

'I

VJ /

50

100

150

200

300

400

TEM PERATURE.-F

Fro. 5--25. Vapor pressure of hydrocarb.on oils (low range).

Co.)

(E8$O Ruearch and Eng.

207

PHYSICAL PROPERTIES OF PETROLEUM OIL

400
300

/'1

/'

./

V ,,- ./
l/

,/

600 "

550

500

760
600

L.(

./

./ ~ ~

,/

./

,;'

/'

I'

./

" /

,fI\

650
1/

V
,/ V
,/

700
L

I'

I'

~9~

'/

vVv

80
60
40

l/

/'

./

./

IL

1/

'/

'" /

./ V

"

/'

,I

~~ ~

1/

'/

/
,/

/
V
/
/

V /,/
/

V /

IL

>-

a:

;:,

/
/

./

./

'/

'/

~ / / / II / V
/ ~ / ~ I Ii I

~/

~/

/ / V

'/

....

O\. ,/

IL

/\OL 1/
/ / L

V V V 1/
/ V V V II /
V
V
/ /" ./ V- V V II I / // // V
./
/
V I V
/ ~Ii 1/
./
./
20
'I'
V
/
/
V
V./
/
V
V / / / / V / V I VV- II IV / I
II
V
/ ./ / '/ l/ I '/ / 1 / V /
I
10 V
/
/
L
L
L
/
8
V
V
/
/
/ !/
L

30

V '/ 1/

~L

."

,/

./ /

1000

Vv / I V V I / VII V/ I
Ii I
~L
/ ~ / V ~ ~ ~ ~/ IiI :/
O
I
h
qv.J'
/

V
~

L / /

/V 1/V / V V /

./
V V V y
v" ./ :/ ./I/'
/'
V /I/ l / v I
200 k" V /' ./ / ./ V/
V
o~ '/ /
V ./ ./ / / V- ./ VVv /
./ v~7v '/
V
/
V / ' ./ ./ / V V ./VV / V
100
/'
V

,;'

v v

900

IL L / / / / / / /
V V/ / L / / / / ,/ / / / / I / V

V- i/' V

././

/'

v~

800

/1/ 1/ 1/
J /
V

/L lLo
a'Y /

ILL
J j

'/

I I II I V

/~/ I ~(p LLlL


vl/V ~1 / VV

V
V
/ V / (I // /I
V
VI; ~~ V/ / ~V/ V

u
a:

lIJ
;OS
~

./

L L

'/

1/

/ 1/ L IlL JIL

/ :/

/ / I
I / I I II' II / II IV
V VI
/
II
V
V
j
I / / L L 1 i LlL
V
/
1/ V
/
/
3 /
,/
V
V / / V I 1/ Vv V v(
I) VJ I I I I I I I II LII
/
/
/
'/
L
2
V/
/
I VI
I V '/ V V 1,1
/
V
/
/
/
/
// I
lj
V / VI /v I V
V
/
/
/
/'
/
/
/
1/
/
/ / I / /
I

4 .L

po

lIJ

a:
en

;:,

1/ V

tal
II:
Q..

II:

0.8

0.6

ct

>

./

Ii V /

V 4'oJ?,J

/J

1/

V /

I V

I 1/ 1/ f I
/ I -f
V I V

L I I II

I//

I I II I V

I II

/ I / I /
L

1/

V
~

II

./

II

IV v

II V
II / /

II

~r

;. .Jj I

/ II

o~ I
I

1/

" 0.01
500

"

600

"

650

I II II I

f /
/

/1/ / V&/

vv

550

"01

II / I I /
~I
II
V
V
/ I II / I V V J / V / / / I
vV V V I I VI V / V/ V II 'I VV I V
I
I I V/ V V ) V J /

0.03 /

I /

0.06

700

vfr

/ lL IV V
800

900

1000

TEMPERATURE,"F.

FIG. 5-26. Vapor pressure of hydrocarbon oils (high range).


~o.)

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
V I ~ / / ~o~~)"~ / / I J / / V/ II
V

0.2 /

0.04

V V.

I /

1/
/

1/

1/4.0C

/
0.4
V~~/
/
0.3
/ V;' /

0.1

1/

I
" VI
/
V
/
V
~~/

j,

I)

~.

/ VV

(ES80 Research and ~ng.

208

PETROLEUM REFINERY ENGINEERING


-50

or

ABOVE: CRITICAL POINTS


PUR[ COMPOUNDS

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:

::>

yP~

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.,.~
~

.,,~

~.

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.

PHYSICAL PROPERTIES OF PETROLEUM OIL

209

Width of boiling range as in a petroleum fraction appears to have


little effect on the change of boiling point with pressure.l!g ' Inherently,
the true-boiling-point ' type of distillation curve should correlate most
exactly because it consists of the boiling points of nearly pure materials as
they distill one by one. - Th,e equilibrium flash vaporization curves
illustrate the other extreme type of distillation curve, and corrections of
this curve from one pressure to another should not be exactly the same
as the correction for fractionating disti1lations. Nevertheless, a large
difference does not seem to exist between these two extremes of boilingpoint corrections, nor does the slope of the distillation curve seem to alter
the vapor-pressure or boiling-point corrections to a great extent .
.J>iromoov and Beiswenger 30 find that the slopes of flash-vaporization
curves are practically independent of pressure, so that the correction of
the boiling point or flash-vaporization point is a constant number of
degrees throughout the entire curve. They suggest that the correction
should be deterrmned by correcting the intersection point ' between the
true-boiling-point curve and the flash-vaporization curve by the vaporpressure data of the paraffin hydrocarbons. The intersection point is
used because the true-bailing-point curve and the flash-vaporization
curve intersect a~ approximately the same percentage point regardless of
pressure.
Ed rrUster, Reidel, and Mervin 81 have determined flash":vaporization
curves on three oils up to pressures of 200 psia. They find that the higher
the pressure the flatter the vaporization curve, and hen~e the curves at
high pressures should not be drawn parallel to the atmospheric-pressure
curve. Obviously, the flash curve should be horitontal at the critical
pressure, and hence the slope of the flash curve will be fla~ter and flatter
as the pressure is increased. They find that the 50 per cent atmospheric
boiling point should be corrected to the new pressure by using the vaporpressure relationship of the paraffin hydrocarbons (Fig. 5-27). In practical design computations it is common practice to convert to the new
pressure ,by using 'any convenient point the atmospheric flash-vaporization curve. Refer also to Figs. 4-22 and 15-13.
Ccmpression or Expansion. When gases or vapors are expanded or
compressed under adiabatic conditions, the amount of work Jone and the
amount of heat required are dependent upon the ratio of the specific heat
at constant pressure to the specific heat at constant volume. The expansion of a gas can always be expressed by an equati?n of the forin

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

PETROLEUM REFINERY ENGINEERING

P1V~

= P 2V; =

a constant

At adiabatic conditions the exponent n is referred to as gamma ("y) and is


equal to the ratio of the specific heats as'mentioned above. Scheibel and
Othmer 32 developed Fig. 5-28, which may be used tq estimate the ratio of
specific heats of petroleum fractions by using the molecular-weight scale
on the right. The scales of critical tempera.ture and pressure also shown
at the right are provided ..only for convenience in estimating these .constants. The chart (and molecular-weight scale) was developed for the
normal paraffin hydrocarbons, and hence the position of the olefin, etc.,
hydrocarbons on the right scale is empirical and does not correspond to
their molecular weights.
Example G-16. Ratio of Specific Heats (Fig. 5-28). A 100-molecular-weight gasoline is maintained at 500F And at 60 psia.. In determining Cp/C y from Fig. 5-28,
the critico.l conditions and reduced conditions are
Po = 395 psis
T" = 970"R
P Il = 6%95 = 0.152
T = 500
460 = 0 99
c
970
.

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.

In solving for the temperature change during adiabatic expansion or


contraction, the following relationship is convenient:

- -T'J -_ (P'I.)!..=....!
'Y
Tl
PI

(5-5)

where T represents temperature, P represents pressure, and."Y is the


.
ratio eplCv .
The ratio CplCv is small for heavy vapors such as gasoline a.nd kerosene, and it is also lower at high temperatures. Thus little change: in
temperature occurs when such vapors are expanded or compressed.
Detonation Characteristics. The octane numbers of many hydrocarbons are shown in Table 5-9. Many of the data were taken from the
excellent ." Physical Constants of the Principle Hydrocarbons," compiled
by the Technical and Research Division of The Texas Company (1942).
In parentheses are shown blending octane numbers, and in general, the
blending octane numbers by the Research method are higher than by the
Motor method of test.
The effect, of various arrangements or attachments to the molecule
n Hydrocarbon Gases ... ,Specific Heats and Power Requirements for Compression, Ind. Eng. Chem., 36,580 (1944).

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

FIG. 5-28. Ratios of constant-presaure to constant-volume specjfio heats of hydrocarbon gases.


ahem.)

)ZO
(Scheibel and Othmer, Ind. Eng.

t-.:l

,.....
I-'

212

PETROLEUM REFINERY ENGINEERING

5-9.

OCTANE NU'MllERS'" OF SOME HYDROCARBONSi'.

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

PHYSICAL PROPERTIES ,OF PETROLEUM- OIL


TADLE

5-9.

OCTANE NUMBERS" OF SOME HYDROCARBONSb (Continued)

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 ................

> 100 (85.5r)

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)

> 100 (14Or)

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

~. OMl!l HYDROCARBONs" (Continued)

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)

Blending octane numbers in parentheses.


A plus sign (+) indicates number of cc of TEL a.dded to isooctane .

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

1. Shortening the main ch.a.in.


2. Introducing side--cha.in groups such as methyl groups.
3. Centrafuing the molecule by addiDg methyl groups about the center of the main
chain.

The tendency of the olefin hydrocarbons to knock is decreased by


1. The same three factors 88 for the paraffin hydrocarbons.
2. Moving the double bond toward the center of the chain.

The tendency

of the naph thenes to knock is decreased by

1. Decreasing the size of the ring.


2.. Decreasing the length of the longest unbranched side chain .
. 3, Distnbuting the carbon atoms in the side chains into many short chains rather than
one long cha.in.
4. Centralization of the side chains.
II Lovell, Campbell and Boyd, Ind. Eng. Ckem., 23, 26 (1931) ; olefins, 23,555 (193l);
and naphthenesJ 261 1107 (1933).
U Kettering, C. F., Ind. Eng. Chem., 36. 1079 (1944).

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.

stocks for the blending of molor fuels.


.let fuel-fuel for jet or ga.s turbine engines,"1l.nd for rockets.
Kerosene-burning oil for househo1d lamps.
Distillates, die$el fuel, and gas oil (distilled products)-fuels for industrial and
household furna.ces, enriching agents in gas mariufacture, absorbents for hydro
ca.rbon gases, and fuels for diesel engines.
Neutral oils-light or 10w-voscosity lubricating-oil stocks for. the compounding of
motor oils and light machine oils . .
Bright stock-heavy or high-viscosity lubricating-oil stocks for the compounding
of motor oils.
Cylinder oils-unfinished heavy-oil stocks used directly as lubricants for steamengine cylinders or for the manufacture of bright stock. Usually filtered but not
dewaxed.
Paraffin wax-used for the manufacture of wax paper, insulating material, package
sealing, etc.
.
Petrolatum (microcrystalline wax)-base material in the compounding of greases,
Salves, ointments, a.nd pa.ckage sealing.
Fuel oil (residual product)-industrial fuel.
.
Tar and asphalt-asphalt, road oil, roofing materials, and protective coatings.
Petroleum coke-solid industrial fuel.

See Chap. 3 for details.


215

216

ENGINEERING

PETROLEUM

General Processing. The most important method of -separating


petroleum products distillation, and hence the products should be com- _
A mixed-base
pared with one another in the order of their boiling
oil might yield products as indicated
Fig. 6-1. Figure 6-2 likewise
indicates the relation among the raw materials, the intermediate refinery
~---

1100 ,-Raw

TOPPING OR SKIMMING OPERATION

----;;;...~-

ResicluOiL-fuel oil_

~rn-

sene
fOOfD

27%
1000

25%

38% "
I

-r=-

.......e-.- f-Jet fuel J

qOO

--------->r..rE----- - ;..--------~

gOlsoline_ Raw__ Gas oil

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%

i ____ ]._7'!? ___ ~


o

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

--

INTERMEDIATE PRODUCTS - - - - - - - - - - - - M A R K E T PRODUCTS

__

D~9~S--------------------==:~~ --~~=
Wetgos------~~~

Stove distillate

NOI+urcd" 90S

'

Cructe oil

t:=

Tractor and diesel


fuel oil
~-~~-/--+~~~_:=_~--Ar Gas oil

Distillates

QIO

--iL-~~1::;;;;;fHre;~;

U 9 ht

Mealium motor oi j .
HeCi'vy motor oil

Gas oil

Natured asphalt

motor oil

---~~- Ex,+roc-neOlvy motor oi I

POt rOiffi n wax


I

:I

Cylinder

I'
stock I ,
I.

,:
I

\:

Cylinder stack\
/solution
~

I
I

\ I
\
\

Bright stock----'

steam c.ylinder-stock

~trolatum stock

PetrolCf urn wax

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'

''

Grectses and sOIlves

Fuel oil

AsphOllt OInoi tar"

Coke

219

INTRODUCTION TO PROCESSING

volatile materials (pressure distillate) having the same boiling range as


gasoline, and (3) a residue of heavy material (cracked fuel oil) or- coke.
Pressure distillate receives its name by reason of the high pressures that
are usually maintained in the cracking equipment. Cracked gasoline
from pressure distil1ate is valuabl~ as an ingredient of the superior antiknock motor fuels. Likewise the cracked residue, if cracking is not conducted to the ultimate formation of coke, is called 14 pressure-still tar."

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~_ _ _ _ _ _ _ _....:...-+

o#s and wom

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

PETROLEUM REFINERY ENGINEERING

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

INTRODUCTION .TO PROCESSING

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.

TYPES OF REFINERY OPERATIONS DUruNG

1956

Per cent of crude


oil capacity
Topping. . . . . . . . . . . . . . . . . . . . . . ..
Catalytic reforming ..... , ........ ,
Thermal cracking ...... : ......... ,
Thermal reforming. . . . . . . . . . . . . . . .
Catalytic crocking. . . . . . . . . . . . . . ..
Polymerization of gases ........ .' .. ,
Alkyla.tion of gases ........... , . . ..
Lube manufacture. . . . . . . . . . . . . . . .
Treating ........ ; ............. ,.

99.6
10.5
24 . O'.
4 .0':
39.4
1.6&

2. 8b
3.5

50.0

.. Not including gas or hydrocarbon cracking.


b Based on product rather than feed.
TABLE

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)

. Retorming, .......... 14.3 PlatIorming .... , ...


Crude cracked ........ 1.2 Hydroform ing" ......
Coking .............. 5.5 Ultraforming .......
V'lSooSlty
. breakin gb .... 10.0 Houdriforming . . ...
SOya!onning .......
Cracking:
Catforming ... . ....
Heavy oil coile ...... 39 .0 Thermofor .. : ......
Gas oil coil ...... . .. 30.0 Others ....... '......
Both fixed-bed and' fluid.
" Separate coil.
~ Essentially viscosity breaking.

II

STA.TES CRACKING

51.9 Fluid .............. 70.9


11.5 T.C.C ........ , . . .. 19.2
10.2 Houdry ............ 3.7

6.2 Houdriflow . .. . .....


5.1 Cycloversion .. , .....

4.7
4.2
6.2

5.8
0.4

222

PETROLEUM REFINERY ENGINEERING


Treatment:'
Sweetening
Sometimes acid

RClw gasoline

,.....L

SfraiQhf run

--"

Gasoline

Nalurol 9Qso}ine /

I:

Treatment:
5weehning

Row Iterosenl!

:.;:

Crude oil

.....

.~

Kerosene

~-------~~-------------~---~ Oislil/ales or gos oil

Reduced cruc/e oil

--"

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~. ~

Croeled dish1Jofe fuel

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

Viscous neul: 0;/$

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

Skam reF/ned cylinder slod

(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

Light, ria Phthl

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

Ulht illS oil

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

PETROLEUM REFINERY ENGINEERING

facture of chemicals is not ordinarily included, -but the relationshlp of


petrochemicals to the entire processing is evident in Fig. 20-3.
The materials and methods outlined in this chapter constitute the most
important ones. Many of the productsfound on the market are made by
blending these stocks together to meet particular industrial requirements.
As an example, the various grades of motor oil and machine oil are prepared by compounding different amounts and ' grades of the 'neutral oils
and bright stock. Very heavy aero oils, etc., consist mainly of bright
stock, but sewing-machine oil consists mainly of- nonviscous neutral oil.
Details of processing operations and processing equipment will be
enlarged upon in Chaps. 8 to 12 and 19 to 22~
The extent to' which the various operations are conducted can be
judged from plant capacities. During 1956., the crude oil capacity
TABLE ~3. ESTIMA.TED COMPOSITION OF UNITED STATES GASOLINE POOL

Type

1951

1953

Light straight-run naphtha. ..........


Heavy straight-run naphtha. .........
Ca.talytic cracked ................ '. '.
Thermal cracked ...................
Catalytic reformate ................
Thermal reformate .................
Polymer ..........................
Natural gasoline ........ ~ ..... .- ....
Butanes, ... .' .. '................. ~ .

25.7

24.8

8.9

7.1
28.5
13.8
3.4

Pool R.o.n., clear ..................


Pool, R.o.n., +3 ml TEL ...........

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

SHUTDOWN TIME A.ND INSPECTIONS

Months of operation

Units

Crude and vacuum ....... .-.


T hermal cra.cking ..... , .....
Cat. polymeri~ation and reforming. , . . ......... . ...
Catalytic cracking ..........
Alkylation ................ .
Solvent extraction ...... . ...

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

exceeded 8,300,000 bpd and the average relative amounts processed by


cracking, etc." were about as shown in Table 6-1. Thus, ' an average
refinery would have a pumping capacity for all of its various units at
least twice as large as its crude oil capacity. ' Even more, by recycling or
rerunning, treating, etc., the total amount of oil handled would be threefold or more compared with the crude oil capacity. The various ,kjnds of
cracking and reforming operations can be judged from Table 6-2 and by
the United States gaso1ine pool estimate 1 for early 1955 (Table 6-3).
The length of runs, cyCle-time efficiency, and man-hours' of labor
required for inspecting and repairing various units are indicated! in
Table 6-4.
1

Weper; George, Oil Gas J., Aug. _9, 1954, p. 62.


Shannon, R., Pet. Refiner, March, 1955, p. 131.

CHAPTER

REFlNERY AND DISTILLATION PROCESSES

All petroleum distillation processes are fundamentally the same. The


process engineer can make no headway in initiating new processes or in
truly understanding the flow diagrams of processes until this fact is clearly
understood. In the main, all distillation processes require the following
essential units of equipment: (1) pipestills or other heaters, (2) fractionating towers, (3) steam-stripping columns, (4) heat exchangers, (5) condensers and coolers, (6) pumps and connecting li!les, (7) storage and
accumulator tanks, and (8) instrumentation. However, in adapting
these units of equipment to the processing of a particular stock, many
factors must be considered. Among the most important of these are
1. The boiling range of the stock.
2; The stability of the stock with respect to bea.t.
3. The specifications of the products to be produced.

Phases of processing other than. heavy-oil distillation processes are


discussed in many chapters, particularly under treating (Chaps. 10-11),
dewaxing (Chap. 12), thermal cracking (Chap. 19), chemical manufacture
(Chap. 20), catalytic cracking and reforrrring (Chap. 21), and natural
gasoline (Chap. 22).
Boiling Range of Stock. Some stocks. boil at such a high temperature
that they cannot be vaporized at atmospheric pressure without decomposing them, and other stocks must be kept under pressure or they will
vaporize at room temperature. Raw natural gasoline contains relatively
large amounts of gaseous hydrocarbons and is an example of a stock that
must be distilled under pressure. Although gaseous hydrocarbons are the
overhead product from the column, a liquid reflux of propane and butane
must be condensed, and thls requires a pressure of 125 ~o 300 psia. Of
course, the top of the column could be kept at a low ~emperature by
refrigeration, but such methods have not proved practical. The temperatu~e in the reflux condensers is governed by the temperature of the
cooling water. The .pressure that is used is dependent on the vapor
pressure of the reflux material at the temperature that exists in the
condenser.

j.

REFINERY AND DISTILLATION PROCESSES

With high-boiling stocks the opposite difficulty arises. Vigorous


decomposition starts to take place at temperatures exceeding about,710F,
and for this reason many stocks such as reduced or topped cTtlde oil, tars,
and heavy crude oils cannot be distilled at atmospheric pressure. These
stocks have such high boiling ranges that they must be distilled in a
vacuum or by the use of large amounts of steam. Some cannot be distilled unless both steam and vacuum are employed.
I

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

PETROLEUM REFINERY ENGINEERING

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

1. Natural gasoline .. Gas

210

2.
3.
4.
5.

660
670

Pressure wstilla.te , GasOline


Crude oil ......... Light oils
Pressed distillate .. Neutral oils

Bright stock ,solution .............


6. Reduced crude ....
7. Fuel oil or tar ....
8. Fuel oil or tar. , ..

Naphtha and neutral


Lube oils
Asphalt residue
Distilled cracking
stock

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

Treated pressure distillate is particularly sensitive to high temperatures.


Redistillation should not be conducted at temperatures exceeding 375F,
and l!lBny refiners find that a m~ximum temperature of 275F is econo~
cal because of the reduction in treating costs.
In the manufacture of asphalt most refiners limit the temperature to
770F. Nevertheless, the temperature that may be used without'ruining
the ductility of the product is greatly dependent upon the characteristics
of the stock' and upon the manner of heating. One refiner has successfully
used a temperature of 835F at the pipestill outlet, but others have

REFINERY AND DISTILLATION PROCESSES

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

PETROLEUM REFINERY ENGINEERING

No.1

Products

No.2

No.3

No.5

No.6

No.7 No.8

Feed

(a) Seporation by 'successive flash frocfionaHon

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

Brugma fractionation process.

REFINERY AND DISTILLATION PROCESSES

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

Example 1-1. Amount of Stripping Steam. An unstripped kerosene has an initial


boiling point of 200F, a 5 per cent point of 31OoF, and a 10 per cent point of 3SS F,
which is an average temperature 'o f about 288F. Its flash point is about 90F.
According to Eq. (4-6a), n. 0 to 10 per cent front boiling range of 344F will be
required to obtain a flash point of 120F. Six or seven per cent of the material
must be removed to produce a 344F front end; and, according to Figs. 7-3 and 7-4,
Il

No. of plates

Lb sleam per gal

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

following amounts of steam are

.......................
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

Distillation with Extractive Solvenfs. Hydrocarbons of nearly the


same boiling point (1 to
cannot readily
separated by plain
and hence a combination of fractiona3
tion and solvent extraction known as the II Distex
11 is employed.
IO~--~--~r---~--~---'----~---r--~----~'-~----~--~

/~

~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.

steam required to strip

wi~h

1.6

2.0

,2..4

three theoretical plates.

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

Griswold, Andres) V1l.n

Ka.seh, Ind. Eng. Chem.) 38,

(1946).

233

REFINERY AND DISTILLATION PROCESSES

of subsequent distillationsJ as shown in Fig. 7-5. 4 The solvent must be,


higher boiling than the highest boiling product,. but it should not be so
high-boiling that immiscibility (as in solvent extraction) occurs at the
temperatures existing in the main fractionating tower. In associat.ion
with the solvent, the vapor-pressure characteristics (or activities) of the
hydrocarbons are anered so that their boiling points are spread apa.rt. In
general, the paraffinic hydrocarbons distill overhead to a greater ,degree
than their regular boiling points indicateJ and the naphthenes and particularly the aromatics tend to associate themselves with the solvent.
ParafFin.s and ;soparoFFlns

Norrow bolling Feed


Paroffin
Isoparorf~n

Naphfhene
Aromafic

Aroma/ic

_L_~
, ___~=_=_=!::_==_~_~
So/vgnf mokeup
feed

____
---~

... -1- - - -

0 . . . . - _...

JSolvenf

Solvent recovery Poraffin

Nophthene-aromatk
Solvent
Products
' towel'"
recovery
FIG. 7-5. Simplified flow diagram of the Distex or extractive distiIlatjon proceSs .
tower

i,

The separation of butylene from butane by extractive distillation in


the presence of acetone or acetonitrile is illustrated in the central part of
Fig. 20-16.
Azeotropic d~stillation!i is a somewhat similar process. It involves the
formation of an azeotropic or constant-boiling mixture wit.h one or part of
the components of a mixture. The azeotropic mixture , can then be separated by distillation, but it must subsequently be resolved by solvent
extraction or other processes for recovery of the solvent.
Drying.' The drying of hydrocarbon liquids and vapors is important in
the ' use of anhydrous catalysts. Although the drying' of gases can be
'NelsoD, W. L., Oil Gas J., June 22, 1946, p. 127.
5 Hartley, F. L., Synthesis of Toluene by Hydroforming and Recovery b)' Azootropic Distillation, Pet. Eng., December, 1945, p. 156'.

234

PETROLEUM REFINERY ENGINEERING

accomplished by compression, cooling, and refrigeration; by contac~ing


with hygroscopic chemicals; or by absorption of moisture into diethylene glycol-the common method for both gases and liquids is adsorption of
the moist_u re by activated alumina, silica gel, or fuller's earth: In the
drying of -liquids (Fig. 7-6), the wet liquid is passed through one chamber
while another is being dried and a third chamber may be nearly spent or
may be in- process of draining. The feed is usually passed upward
through the-chambers so that slugs of water- or chemical- (caustic) laden
liquid may settle before it contacts the adsorbent. The spent adsorbent
Dry liquid

"""'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

7-6. Drying of liquids with solid adsorbents.

~s

regenerated by dr~ning the liquid, or steaming it from the adsorbent


. if it is particularly valuable, and passing hot flue gas or superheated
steam at 300 to 400F through the adsorbent. Water vapor in the hot
gas may be removed by cooling the gas in a water cooler. The rate of
liquid flow is 14 to 16 gal per hr for each pound of clay, The clay is support~d at several points to prevent channeling and to allow settling of
impurities. Gasoline and kerosene, etc., can easily be dehydrated to
less than 30 ppm; and, if frequent regeneration is practiced, the following
low values can be obtained: naphtha, 2-4 ppm; toluene, 10 ppm; and
benzene, 4 ppm.

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

REFINERY AND DISTILLATION PROCESSES

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, %

10-20; 20-35 ................... , 100


6-14 .. . .............. , . . . . . . . .. 94
6-10. . . . . . . . . . . . . . . . . . . . . . . . . .. 90
4-8. . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

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

lUZ. humidity (80F), %

Rel. capacity, %

97 .................... , 100
75. . . . . . . . . . . . . . . . . . . .. 85
50. . . . . . . . . . . . . . . . . . . .. 68
10. . . . . .. . . . . . . . . . . . . . . . 39

The drying of gases is similar to the drying of liquids. Plants are


designed for moisture contents in the clay of 4 to 7 per cent, but new clay
will hold 12 to 25 per cent. Hydrogen sulfide in the presence of oxygen
causes the deposition of free sulfur, particularly if the clay contains irpn
compounds. Caustic soda, alkaline materials, and cracked gases cause
rapid plugging of the c1ay or alumina. With regular sweet natural gas
hydrocarbons the adsorbent lasts for many years. Two chambers are
usually adequate. While one of these is being used, a portion (10 to
15 per cent) of .the feed gas is bypassed through a heater (300 to 400F)
and through the spent chamber as a drying agent. The hot moist gas is
cooled to condense the moisture from it, and it may be cycled back
through the system so that all the outgoing gas is dry. 7 Capell and.
Amero 8 provide an It onstream" cycle of 12 to 24 hr and employ a gas
velocity based on an empty tower of 0.33 to 1.0 ft per sec.
Senatoroff has published 9 a complete discussion of the principles apd
plant design details of the diethylene glycol dehydration process.
t; Heinemann and Heinemann, Adsorbents and Catalysts, Pet. Refiner, June, 1954,
p. 159.
7 Nelson, W. L., Oil Gas J., Mar. 30, 1946, p. 27-3.
8 Dehydrating Liquids and Gases with Granular Adsorbents, Oil GCUl J., June 18,
1942, p. 37.
.
- t Application Of Diethylene Glycol-water Solution for Dehydration of N: atural Gas,
oa Gas J., Dee. 15, 1945, p. 98.

236

PETROLEUM REFINERY ENGINEERING

FLOW DIAGRAMS AND OPERATING CONDITIONS

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

.,

REFINERY A~D DISTILLATION PROCESSES

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%

FIG. 7-7. Continuous pipes till topping plant. "

(800 to "870F), 10 and such temperatures result in discoloration and losses


by decom"position. The difficulties with dewaxing are also troublesome.
Plants operating at atmospheric pressure for the manufacture of distilled
cylinder stocks have never been entirely successful, but many refiners
distill \Vax distillate at atmospheric pressure.
In existing refineries, nearly every possible combination of flow or of
towers may be found. Figure 7-8 illustrates ll two of these (also see
Fig. 7-7 again)) and nearly all refiners employ a crude preflash tower to
One plant "operated at 870F, distilling "a 160 viscosity at 210 cylinder stock, but
the color was so poor and the loss of heavy stock was 80 great that the operation was
discon tinu ed.
11 Nelson, W. L., Topping Plant Flow, Oil Gas J., Nov. 25, 1944) p. 103.
10

,
"

238

PETROLEUM REFINERY ENGINEERING

stabilize12 the crude oil or to produce a high-octane or aviation gasoline. 11


The aim in Fig. 7-8 is to show tower arrangements, and hence condensers;
coolers, exchangers, etc., are not shown.
Topper crude oil must always be stripped with steam to improve its
flash point or to recover the last portions of gas oil. The composition of
the ~opped crude oil is primarily a function of the flash or vaporizer temperature, and hence Fig. 7-9 is a good approximation of topped ,crude oils
LIGHT

TOPPED CRUO[

(a)
LICHT GASOLINE

O.GASOUNE

CRUDE'

TOPPED CRUDE

GAS OIL

NAPHTHA

(b)

FIG. 7-8. Arrangements of topping towers.

from all normal-boiling-range crude oils.14 The distillation curves are


entirely adequate' for computing the amount of stripping steam required.
Heat-exchange and Combination Plants. The number of heat
exchangers that may be wisely utilized depends upon the quantities and
temperatures of the several products. Heat exchangers are often
Nelson, W. L., CombiDation Topping Plants, Oil Gag J.~ Dec. 23, 1944, p. 10l.
13 Nelson, W'-L., Straightrun Avia.tion Gasoline Manufacture, Oil Gas J., Jan. 6,

11

1945, p. 81.
H

Nelson, W. L., Oil GM J., July 21, 1945, p. 128, e.nd July 20, 1946, p. 123.

239

REFINERY AND DISTJLLATION PROCESSES

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

Nelson, W~ L'J Oil Gas J.,-Dec. 23, 1944, p. 101.

240

PE'l'ROLEUM REFINERY ENGINEERING

for heat exchange the product of the percentage of material based on


crude oil times its temperature 16 may be computed; and, if this index is
larger than about 5,000, the exchanger is economical. In applying this '
method the quantity of stocks that condense should be multiplied by
about 2; and, if the stock is associated with reflux, it should be multiplied '
again by 2 (or more)_
Although such an extensive use of heat exchange appears to be advantageous, such systems are not without disadvantages_ The dependency
of several units upon one another is a serious complication. Thus if one
unit must be shut down, the other unit or units must be shut down or operated in a crippled condition. Sometimes. these plants are constructed
with extra heating equip.m ent so that anyone of the plants can be operated
independently, but the extra heaters cost almost as much as if they had
been originally provided instea~ of exchangers. Exchangers ma.y also
'GAS Oil

COASts OR
WN.D AVI""ON

GASOUNt

2-GAS OIL OR w.o.lI DISTILLATE


:J - PRE.S5UA! DISTILLAT[

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

HOT lOl'PED CJ\\JDE:


TO SO'-4E OPEAATIOll
1- fIDUCED CAUDt;

FIG. 7-10. Sources of heat for heat exchange.

(Oil Gas J.)

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

REFINERY AND DISTILLATION PROCESSES

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

~~

PLANT FEED STOCK


ALREADY HEATED
ay EXCHANGERS

.~

.
).

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

Nelson, W. L., Oil Gal J., Oct. 26, 1946, p. 129.

242

PETROLEUM REFINERY ENGINEERING

produced during acid treatment. The exact temperature below which


discoloration and the formation of
occur depends upon the chemical
distillate, the manner in which the chemical treatment was
conducted, and the way in which heat is applied. With one particular
distillate,19 the effect of increasing the steam20 which used to reduce the
temperature, other conditions and operations being the same, was as
follows:
Per cent steam
in lW6TMad
./ 0

Color

5
20

22
25

18

Refiners. usually limit the temperature of redistillation in continuous


pipestiU and fractionator plants to 325F by t~e use of steam, although
375F. The tendency has been to
some plants have been operated
decrease the temperature because the treating operation much ---'-rr-tied the temperature is low. Several companies have installed vacuum
which the temperature is limited to 275F. The vacuum
systemstl
redistillation
are usua.lly of the two-stage type,
which part
.of the distilla~6\.is distilled at atmospheric pressure and the heavier part is
vaporized in l:iecond fracti on at or 'which operates at a reduced pressure.
7-2.

TABLE

ANALYSES OF UNSTABILIZED PRESSURE DISTILLATES dI

Volume percentage analyses


pressure distillates '
collected .at pressures of psi

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

The distillates were not from the same charging stock.

Stabilization. Cracked gasoline, crude oil, wild natural gasoline, and


similar stocks contain dissolved gaseous hydrocarbons that tend to escape
..................... fi> storage.
Analysis of crude oils were shown in Table
and
It Trusty, A. W., Acid Trea.tmentE>f Cracked Distillates . , Ref. Nat. GlUO. Mfr.,
August, 1932, p. 455.
211 The sUlfur content of the distillate was lower when more steam was used.
II Noll, H.
Oil Gw J., Mar. 31.. 1932, p. 66.

REFINERY AND DISTILLATION PROCESSES

243

Table 7-2 by BUTket~U indicates the composition of cracked distillates.


The equipments used for the removal of gaseous or very low-boiling materials are all fundamental1y similar to the natural-gasoline stabilizer23
shown in Fig. 7-12. Heat is supplied at the bottom of the tower by means
of a steam-heated reboiler; and, if the feed is heated by heat exchange with
Gas
C.77.9
~ 10.04
C3 B.61_
iC" 2.60
C" 0.85

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

C1 12.12 Raw- Gasoline


i c. 8.76
Feed
C.. '29.33

iCs

481
FIG. 7-12. Natural-gasoline stabilizer.

(Burdick, Oil Gas J.)

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

P.D. Stabiliza.tion . . . ,&f. Nat. Gaso. Mfr . Ma.rch, 1931, p. 75.


Burdick) G., Oil-Gas J.) Apr. 9, 1931, p. 26.

244

PETROLEUM REFINERY ENGINEERING

in all respects to the stabi~ization of raw natural gasoline (Fig. 7-12).


However, pressure distillate contains less propane and butane than raw
natural gasolin,e, and hence the feed must be heated to a higher tempera":
ture. Pressure distillate is often It deep-stabilized" for the removal of
substantially all the four-carban-atom and lighter hydrocarbons so' that
the stabilizer overhead will contain all the ole11ns that are suitable' for
polymerization. The propane rejected from the polymerization unit may
be collected
bottle gas, and the butanes are collected and returned to
the plant gasoline for increasing its vapor pressure. ,
Recent developments of polymerization, dehydrogenation, alkylation,
etc., processes, which are now practiced primarily on gaseous hydrocarbons, all require high-pressure fractionators similar to stabilizers. In

as

Proppne
IOOORPa~

a.96%iCt.

~open~ne

o%~~~P.ll flPg

'J500 ,3 1!a 1470(5


Reflux
Reflux
raf/o= 128
rafio: 2.6
45 trays
40 trays

Deproponizer
,

Poly plan! feed


5500 ap.D.

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

REFINERY AND DISTILLATION PROCESSES


TABLE

7-3.

DATA CONCERNING THE FOUR COLUMNS OF FIG.

Ca.pacity, bbl/day .......... . ..... - ....


Impurities, in overhead, per cent ....... {

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,

effects some separation. The lower part of most petroleum oil


columns does not function as a. fractionator but as a simple steam-strip...
ping section. In practicing reboiling on heavy-oil towers, oil is circulated
from the hottom of the tower, through a" few tubes in the pipestill or other
heating equipment, and back into one of the lower plates of the towerJ as
in Fig . . 7-15. Reboilers do increase the efficiency of fractionation, but
a; satisfactory degree of separation can usu'ally be obtained more cheaply
by the use of a stripping section. The use of two coils in a pipestill is
difficult' because the exact heat input .in each coil cannot be accurately
determined except by experiments with the pipestill d~ring operation. '
Occasionally the temperature attained by heat exchange is not high
enough to vaporize the desired amount in a crude preflash tower, and
hence hot topped crude oil is cycled from the topping still to increase the
prefIash vaporizer temperature. This practice is generally not good 26
because the high-bC?iling topped crude oil suppresses vaporization (see
Fig. 15-16).
Reboilers heated by steam are used in stabilizer towers for natural gasoline, pressure clistillate, butane-propane mixtures, and some solvents. In
these cases the bottoms product must be well fractionated, whereas in
most of the processes that have been discussed heretofore the fractionation
of the o'verhead product was most important. Fractionators for the
production of special cuts, such as solvents, are frequently operated with
reboilers or with fired shells. at the bottom of the towers. ~
Naphthas and Specialty Products. The manufacture of solvents is an
exacting operation not only because of the short boiling range but because
28

Nelson, W. L., Oil Gas J.J Aug. 3, 1946, p. 96.

~GA5

'AOM rlUD

NATII."L GA.5-

(II'"

St~A~~A$

________________________________~____~~____________________________________-4____________----~
"1[1.D GASU

,'-.-HI()

PUR""U,C.IU --------------..

.1

J!-. allY ,.ueL. CAl

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,

FIG. 7-14. Combina.tion gas-recovery and sta.bilization system.


1. Wild' crude oil
2. Water for deaa.1tlng
8. Crude pump
t. Crude to crude exohanger
I). Heat from refinery or
ateam if in field
6. Small bubble tower
7. Crude to refinery without
u.obaDge

8.
9.
10.
11.
12.

Crude to tank farm


Condenser for wild gasoline
Preliaab re8ux
Gas separa.tor
Wild gaaoline (rom crude
oil
13. Unat&ble DAt.ura! ,aaowe
U needed
'

14. Wild. gasoline from strip..


PiDg atill
15. H~h-pre&8ure 8trabUbar
16. Reflux condenser
17. Ricb gas from orude
18. Riab atabilil8l ga.a
19. Reboller exob&Dgel'
20. He&.$ exohaoger
21. Gaa aapa.rator

(Oil gas J).


22. Riob Itripper saa
23. Condenser for stea.m and
gaaoline
24. Stripper re1lux
25. StrippiDg ateam
26. Stdppi~.till
:no Rieh.oll bea_
28. Hest exohange
29. Le&Q-oll ooolel'

, .,

I ~'

."

30. Gaa abaorber


31. Gu GOmpreaaora
32. Ricb paea from all pointa
33. FIeld 1;&888 from lep&ratora
34. Craolring-atilJ galDli
35. Ta.nk gases '
,
86. :Dry gu to fuel 8yst.em
87. Vapor reoovery' from storage . ..

......

'

247

REFINERY AND DISTILLATION PROCESSES

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

FIG. 7-15. A universal flow diagram for the prodllction of solvents.

(Oil Gas J.)

A product that is withdrawn from the side of a' multiple-draw column


can never be well fractionated. It will always contain some low-boiling
material because the vapor that passes the draw plate always contains the
Hghter products of the process. The end point can be regulated to some
extent by the use of many plates.and large amounts of reflux, but a satisfactory initial boiling point cannot be obtained by these methods. Regulation of the initial boiling point is usually accomplished by the use of a
steam stripper. However, these common methods are ordinarily not
satisfactory for the manufacture of solvents, and it is usually necessary to
withdraw a partly fractionated material from the main tower and redistill
thi.s material under controlled conditions. Figure 7-15 indicates some of
the principles involved in the manufacture of sp~cialty products. 27 The
U

Nelson, W. L., Oil Gas J., Mar. 10, 1945, p. 83.

248

PETROLEUM REFINERY ENGINEERING

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

REFINERY AND l>l8TlLtATIO"N' PROCESSES

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

FIG. 7-17. Evaluation curves of a pressed distillate.

5
50

PETROLEUM REFINERY ENGINEERING

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~
, .~.

---

---

:::

120 Bri9.hfsf ock


12.Z%'
154 Visco fa) 210

Si'etm ~~

FIG. 7-18. Diagram of a. two-flash solution-rerun unit.

900

~e

600

..c

J! Q700

,I
/

CD

"

"-

0600
~o

00

~@500
-+-~
~._ 400
E 0
~ ~300
u-

~~200

~~

Ii....

I.

"- lL Vise. (il} 2/0"F.


~

.....

100

-~

[....../

~o

Lr;sc.tmJOO~
J
-.........
N
1
/\

fla5/r vje/~ f"""


~:r"'p.
~ ~~.~.

.-= :>

............. 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.

steam, and it should not be employed if cracking, discoloration, or


viscosity breB:-king are detrimental.
, Coking is an extreme case of destructive distillation which produces
large amounts of thermal or catalytic cracking stock. 28,
2B

Armistea.d, G., Jr., The Coking of Hydrocarbon Oils, Oil Gas J., Mar. 16, 1946,
,

p.103.

'251

REFINERY AND ,DISTILLATION PROCESSES

--'-g-- -- -- -,-- --- -- i

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.

Vacuum distillation for the production of lubricants or asphalt will be


discussed later in this chapter.
Carrier distillation involves the recycling of the overhead product so
that its II carrying 7729 or partial-pressure effect can reduce :t he vaporization
temperature. The process bas been developed by the Lummus Company. Figure 7-20 30 shows features of the process, and Fig. 7-21 indicates
the reduction in boiling point that may occur. According to Fig. 7-21,
the amounts of material vaporized at 700F are
Percenta.ge vaporized
Operation

T.B.P. distillation ......................


Fla.sh vaporiza.tion ......................
With 50 per cent recirculation ........ .-. .
With 100 per cen t recirculation ..........
With 200 per cent recirculation ..........

Based OIl
pipes till
cha.rge

25
45
70.5
84.0
94.0

Based on
feed stock

25
45
56

68
83.0

PiromoQv and Beiswt:nger, Equilibrium Vaporization of Oils a.nd the 'Carrying


Effect of Light Ends, API Bull. 10, no. 2, sec II, p. 52, 1929.
30 Nelson, W. L., Oil Gas J., June 29, 1946, p. 103.
29

252

PETROLEUM REFINERY ENGINEERING '

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
/,
/

} J/ .-/ ' V' ~

ft) ~
~
I

300

I...-- ~

I-""'"

'2
~

~'/

V. i' "/ /

I.

V
V

V Vi
)

.,.

~~

V.
'

V
"

..
.

40 50 6.0 .70 80 90 100


'. . Per CeMt Vaporfzed
FIG. 7-21. Carrier distillation curves of a crude oil. Dotted curve shows the vapor
tempera.tures in a T.B.P. distillation of the feedstock; curve 1, liquid temperatures
in a. T.B.P. distillation; 2, flash-vaporization curve of the feedstock; 3, fuLsh-vaporization curve of feed plus 50 per cent recircula.tion; 4, 1la.sh-vaporization curve of fe~d
plus 100 per cent recirculationj and .5, fia.sh-vaporization curve of feed phlS 200 per
een t recirculation.
10

'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

REFINERY AND DISTILLATION PROCESSES

253

for condensing process steam followed by two stages of steam-jet ejectors


as shown in Fig. 7-22. If pressures lower than 20 to 25 mm arl'} needed
at the vaporizer, .a booster ejector and two or three stages of steam-jet
ejectors, as indicated in Figs. 7-23 and 7-25, are usually reqwred. The
booster ejector of Fig. 7-23 is !imply a large steam jet that is used to
compress both the process steam and nop-condensable gas'es into the
barometric condenser, whereas the ~ustomary smaller steam ejectors are
used to remove only noncondensable gases from the barometric condenser.
Condenser~---.. _ _ _ _........

waler

___... ___ Jet


I
steam

,
I

Incoming.
nOl1condensobles
and process
steam

2d
stage

I
I

To atmosphere

tir 10 a

condeneT lor
Baromelric
leg

jet s7eom

FIG. 7-22. Two stag'es of ejectors with' B. barometric condenser.

Vaporiz'ation is accomplished by ~ducing the partial pressure ~f the


oil vapors at the vaporizer, first by the use of vacuum but also by the use
of process steam. At some pressure the sum of the jet steam and process
steam is a minimum. Table 7-4 and Fig. 7-24 illustrate how the total
steam consumption is a function of vaporizer temperature, cooling water
temperature, and absolute pressure. They are based on the processing
of 1,000 bpd of a conventional Mid Continent topped crude oil for the
vap.orization of material distilling up to about 950F.
Barring leaks, the amount of noncondensable gases that must be
removed per 1,000 bpd of charge stock ranges from 15 to 50 pounds. 31
It consists primarily of the (1) tail of lower-boiling material almost
necessarily associated with any feedstock (0.2 per cent represents about
25 Ib of gas), (2) gases produced by cracking or overheating of the feed3.1

Ne]soD, W. L., Oil Ga3 J., April 5, 1951, p. 100.

...t
254

PETROLEUM REFINERY ENGINEoE RING

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

600 BOO 1000

AS SOLUTE PRESSURE (MM) IN VAPOR UNE.

FIG. 7-24. Examples of most economical pressure tor va.cuum-tower operation


Table 7-4). (Oil Ga$ J.)

(s~

:t

;~

255

REFINERY AND DISTILLATION PROCESSES

stock (2 per cent decomposition results in about 10 lb of gaseous tail),


and (3) air dissolved in the charge stock and in the water used in generating steam (usually under 2 to 3Ib). 31 The noncondensable gases are contacted with water in the barometric condenser, and hence the total
pressure must be well above (5 to 15 mm) the vapor pressure of the hottest
wa.ter in the barometric system. The vapor pressure of water is indicated in Table 7-5.
TABLE

7:-4.

TOTAL STEAM REQUIRED (ApPRoX.) IN VACUUM DISTILLATION

for 1,000 barrels per day topped crude'


Pressure (mm Hg) produced
by the vacuum' system
Q

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.

VAPOR PRESSURES 0'" WATER

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

The total pounds of noncondensables plus water vapor for saturation


must be ejected from the system by means of the steam jets, and the
approximate amount of steam required to operate the jets is indicated in
Table 7-6. The steam required to operate the booster ejector is included
in the values shown in Table 7-6 in the pressure range of 4 to 20 mm. The
wide range evident in Table 7-6 is due primarily to the various cooJing
water temperatures encountered, and the average values of the table

256

PETROLEUM REFINERY ENGINEERING

TABLE

7-6.

ApPROXIMATE STEAM CONSUMPTION OJ' CONDENSING STEAM JET


EJECTORS OPERATING WITH

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)

and water vapor.

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.

A booster ej ector is necessary if the pressure of the. system must be


below the ,v apor pressure of the water that is available. A booster
ejector enormously increases the amount of jet steam required because
the booster must handle process steam as well as noncondensables.
A large amount of water must be used in the barometric condenser
because the hlghest water temperature (plus 3 to 5F for inadequate
mixing) determines the amount of water vapor that will saturate the
Doncondensable gases, and baye to be removed by the jets.

r
I

\
,

REFINERY AND DISTILLATION PROCESSES

! -

Vacuum Distillation. Vacuum distillation ma.y be employed for the


redistillation of pressure distillate, pressed distillate, or bright stock
solution. It may be used for distilling topped crude oils for the production of wax distillate and cylinder stock, or it may be used to reduce a
residual stock to asphalt or pitch. Vacuum systems are widely used to
produce catalytic cracking plant feed stocks of low carbon content.
The advantages of vacuum distillation for producing lubricants from
topped crude oils are obvious, because the asphalt in such stocks makes the
cost of acid treatment almost prohibitive. In the caSe of paraffin-base
oils the advantages are Dot so obvious. The advantage with such oils
lies in the larger recovery of the va1uable heavy stocks, which in the
case of residual ~team operation are partly decomposed into lowerboiling, less Viscous oils.
.
Although the wax distillate and the .cylinder stocks from. vacuum units
are usually dewaxed without difficulty, some refiners have found that an
intermediate heavy wax distillate cut must be produced to -the amount of
3 to 6 per cent if the wax distillate and the cylinder stock are to have goOd
dewaxing characteristics. ' The use of solvent dewaxmg processes has
eliminated most of these difficulties.
Becau~e of the high boiling points of lubricating-oil stocks the use of
vacuum alone is seldom sufficient. Process steam must also be used and
sometimes in such quantities as 1 Ib of steam for
each gal of reduced
.
crude oil that is processed. Of course, the exact. amount of steam to be
. used is dependent upon the boiling range of the stock and the quantity
vaporized. Many plants have operated with process steam not exceeding
0.3 Ib per gal. The .dry process of vacuum distillation, which utilizes
no steam, has many theoretical advantages. Most important among
these are the much smaller. tower and condensing equipment .required.
Nevertheless, the absolute'pressure that is required for the.dry processing
of most petroleum oils amounts to less than 10 mm, and such a vacuu~
cannot be produced at a reasonable cost in most large-scale vacuu~
equipment.
The pressure drop that occurs between the barometric condenser and
the vaporizer section of the tower (Fig. 7-25) is of great importance. The
purpose of vacuum. operation is to produce a low effective pressure at the
vaporizer, and hence the' vacuum must not be lost by excessive friction .
loss through the vapor line, cond~nsers, and tower plates. The avoidance of a few millimeters of pressure drop, from the barometric to the
vaporizer, is worth many pounds of process steam (see Table 7-4). The
saving in. the qu'antity of steam is important, but the reduction in tower
d.iameter and quantity of cooling water are also significant. From Fig.
7-24 it might be assumed that economical pressures range from 30 to 60
Qlm, but such is not the case. Although it is seldom feasible to operate

'.
;

,t
,

.,

,
,!

257

258

PETROLEUM REFINERY ENGINEERING

,0
O

Crude oJI

Temperature

'QlJcmtity

D Pre5sur~

Reduced cTude from


.shellslills 6r.:lS.~

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
-

(Smith Engineering Co.) ,

~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,

below about 25 rom, many systems operate most e~onomically at 100 to


140 mm.
.
'In an effort to obtain a minimum pressure drop, many novel arrangements and designs of vacuum towers and condensing equipment have been
developed. The pl~teB a~ designed for as Iowa liquid head above the -

f
259

REFINERY AND DISTILLATION PROCESSES

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.

RELATIVE VOLAT1LlTlES AT HIGH AND AT

Low

PRESSURE

Vapor pressures, mm, at


-50F

+50~

700F

600F

800F
.

Propane ............ ',' ........... 630


Pentane ......... . ........ ' ........ 12

Lube fraction-bp of 750F ........ . . . .


Lube. fraction~bp of 850F ........ . . . .. .
Relative volatility ....... ; . . ..... .

52.5

4,395
350

. .......

..........
12.5

.
110
22

5.0

.425

1,450

115

465

3.7

..

3.12

an adequate reason for operation at .low pressures. It does account in


part, however, for the relatively small number of plates used in vacuum
towers.
.
Apractical w~y to increase the efficiency of fractionation or the quality
of products is to employ wire-mesh mist extractors below the points
at which products are withdrawn. In the production of an asphalt
bottom product and at the same time a gas-oil catalytic feedstock that is
free from entrained asphalt or metal contaminants that tend to poison the
catalyst, Wire-mesh has resulte~ 32 in phenomenal increases in capacity
or in large reductions in .contaminants.
.
Symposium (Case Histories) . . . Use of Wire-Mesh Sections . . . , Oil Gas J.,
Nov. 2, p. 82; Nov. 23, p. 94; and Dec. 28, p. 70, 1953.
12

260

, PETROLEUM REFINERY ENGINEERING

The distillation of tarry :' ,_dues in a vacuum for the production


of either catalytic ' cracking plant feedstock -or asphalt differs little
in principle from .the operations already described except that the
vacuum tower 'can be much simplified (Fig. 7-27) because of the follow-ing consider~tions.
Feed-20API
10pplJd crude oil

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%

7-27. Vacuum distilla.tion for catalytie feedstock or for asphalt.

1. Elaborate fractiona.tion is not necessa.ry. ,In the case oC lubricating-oil diStillation,

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

REFINERY AND DISTILLATION PROCESSES

(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.

Air-blown Asphalt. Most asphalt used for paving- is produced "by


vacuum or steam distillation. Such asphalt has a relatively high ductility. Shingle saturants or coatings, roofing saturants, and laminating
asphalts require a material of lower penetration and higher softening
WAiER

BLOWING
TOWER

BLOWER
OR "
COMPRESSOR

AIR

CONTACT
CONOENSR

BLANKET STEAM

"\

ll!sEWER

fLUX
STORAGE

PIPE STILL

'"

..
t

ASPHALT TO"
CARS, DRUMS, "
OR
A

FIG. 7-28. Vertical-tower batch ~pbalt oxidizing system.

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

Shearon and Hoiberg, Ind. Eng. Chem., 46,2122 (1953).


Nelson, W. h, Oil Gas J'J Aug. 23, 1954, p. 156.

262

PETROLEUM REFINERY ENGINEERING


TABLE

7-8.

SPACING OF REFINERY UNITS"

From one item or unit-to another item or unit

Distance, ft'b

Cracking unit (low pressure)c.-cracking unit (setting to setting) ....


25-50
Cracking unit (high pressure)d-cracking unit (battery to battery.) ..
75-150
Cracking unit (either)-pipestill unit ........................... . Separate block
Cracking unit (either )--a.ny other process unit .. .- ..... ,-.......... . Separate block
Pipestill unit-pipestill unit (setting to setting) .... . ............. .
25-50
Pipestill unit-any other process unit ........ . .................. .
100
Sbellstill unit---sllellstill unit (battery to battery) .. , .............. .
25-50
Steam still battery (shell type)-any other process Unit ........... .
100
Condenser box-shellstill unit ....... . ........ .- .. ~ ............... .
15-20
Receiving house-:---running-tank fire wall: ......... _............... .
20
Treating unit (agitn.tor)-treating-plant pump house .............. .
50--100
Boiler a.nd power house---anyprocess unit ........... . ........... .
100--200
5(}-IOO
Oil-tra.nsfer pump house-any process unit ...................... .
Foam pump house--any process uDit ........... . ............... .
100-200
Main water pump house-a.ny process unit ...................... .
100-200
Warehouse (oil storage)'-any process uDit .......... ~ ....... '.... .
50-100
Treating plant-any process unit ......... . _....... . ............. .
100--200
Gas plantsl----any process unit ........ : ...... ~ . ~ . : ............. .
150-200
Gas holders-a.ny process unit ... ; .... '...................... ~ .. .
150-200
-Main sep&ra.tor (oovered)--any process unit ......... -.. . ; ......... '
50-100
Main -separator (uncovered}---a.ny process unit ............ . ~ .. : .. .
100-150
.. "Fire Protection in Refineries," 3d ed., API, 1941.
Pi In ease there is a. conflict between spacings as shown b~ow, the greater of the two
dist!l.Ilces applies.
c Units opera.ting at 350 psi or less.
Ii Units oPet:ating at over 350 psi._
This is meant to cover fireproof structures used for storing low-Hash products,
a.nd includes sample stora.ge and can-filling buildings_..
I This is intended to ~clude such pI ants_ as gasoline-reeovery; debutanization,
stabilization, and absorption pl!l.Ilts, when they Rre not an integral part-of any process

unit.

Spacing of Refinery .Units. Units ha.ving the-same general function


are usually kept together in one -ge'1eral area. Within the area, th~
separate units are spaced apart 36 iJt5 as indicated in Table 7-8. Lik,ewise,
the entire block is separat~ and protected from other similar areas.
"Fire Protection in Refineries," 3d ed., API, 1941. .
at Attaway, DOD, Natura.l Gasoline Plants, Pet Eng., January, 1956, p. C-16.
35

'

CHAPTER

AUXILIARY PROCESSES AND OPERATIONS

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

PETROLEUM REFINERY ENGINEERING

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.

___ __

FIG. 8-2. An extensive control system for a natural-gasoline plant.

AUXILIARY PROCESSES AND OPERATIONS

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
"

Chillas and WeirJ Ind. Eng.

ehem., 22t 206 (1930).

"

266

PETROLEUM REFINERY ENGINEERING

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

FiG. 8-3. Instrument lloards and COI).trol room for


,apolis-H oneywell.)

So

catalytic cracking unit..

(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

AUXILIARY PROCESSES AND OPERATIONS

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

FIG. 8-4. Salt-settling systems.

(O-a Ga8 J.)

of brine and then through 15 to 20 ft' of oil. Apcumulations of debris aT


the interface should - be drained at frequent intervals. The genera
arrangement is indicated in Fig. ' 8-4, and it also shows the now widel)
used electrical process. 7
In handling more stable mixtures, the aforementioned simple heat- an(
water-diluent system may be assisted by the use of chemicals or a high'
'Egloff, Nelson, Maxutov, and Wirth, III, Crude Oil Desaltin~ AIME Meet
ing, Oklahoma City, Oct. 8, 1937.
6 Nelson, W. L., 01,1. Gas J., Feb. 17, 1945, p. 121,7 St. Hill a.nd Hanson, Extraction of Salts from Refinery Stocks by the Eler.trics
. Process, Ref. Nat. Gaso. Mfr., October, 1937.

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.:.} )

in which V is the maximum velocity of settling, D is the diameter of the


spherical particles; ,P, and PI are the, densities of the soiid and liquid, 'and
# is the viscosity, all ~n cgs units. Commercial settlers deviate from the
theoretical be~avior, but Eq. (8-1) constitutes a guide, by which com8 Bennett, H., uThe Chemical Formulary," vol. 2, p. ,179 (Tretolites), D. Van
_
,
Nostrand Company, Inc., Princeton, N.J., 1935.
8 Van Dedem J G. W., Chemical .Methods for Separating Petroleum EmulsionS, Oil
Gas J.,
12, 1937, p. 65.
III Hart, W. B., Elements of Waste-water Separator Design, API, 8th Midyear
Meeting, Wichita, Kans., May 24, 1938.
11
Disposal of Refinery Wastes. sec. I, 5th ed., 1'953.

269

AUXILIARY PROCESSES AND OPERATIONS

mercial relatioilships can be correlated. A complete review of settling


h~ been made by A. C. Ingersoll.~2
Somewhat the same layout of settler as that developed by API studies l l
is shoWn in Fig. 8-5. Tl:le flight scraper serves to move sediment out
of the box in a continuous manner. A :6Jterll that utilizes cloth as the
filter medium may be used after the settler for removing the last traces
of iridescent oil film. . Settlers ar.e usually constructed of concrete,and
have a depth of 6 to 8 'ft. Other dimensions are not of great signjficance,
provided that the retention time is adeqW).tely long and provided that
the incoming waste water is evenly distributed across the settler. Many
settlers are producing waste water that contain.s only 5 ppm of oil. A
film of oil ranging from 0.000006 to 0.000012 in. thick on the surface of
Manifold .inlef
. .

,Oil co/leeler (adju:sluhle heigh!)

1\
:

.
\ Oil refainer oarlJe---.

(PQlh

\,

or fluid flow
,.- Liquid level

I
I

I
I

I
\

Oullef_ ..
.
----Slurry co/leeling chamber
1

lFllghf scraper for


: cleanfng (moves counler
J

r:/oc/fwise)

'Inlefs poinfed down

",

S ~cond stage

First stage
FlO. 8-5. Vertical section of a waste-water .separator.

,vater will produce an iridescent coloration. W ~ B. HartJlI has published


11 umerous articles on nearly evel'y feature of refinery waste disposal.
Separators cannot be expected to handle. waters more highly acid than
a pH of 4.5 or more alkaline than a pH of 10 or to handle true emulsions of
oil in water such as so-called U white water." In such an emulsion the oil
is dispersed -through a continuous water .phase and is carried through the
separator. Later the emulsion may be destroyed by dilution or other
effects. that will liberate the oil. Emulsions of wa.ter-in-oil which may
contain asphalt, clay, dirt, alkaline earth soaps, lead sulfide, or coke as the
emulsifying agent are not usually troublesome. Occasionally, however,
:12 Fundamentals and Performance of Gravity Separation, Pet. Refi'M1', June, 1951,
p. 106,
13 Disposal of Refinery Wastes, a series of 20 articles, Naa. Pet. News, Tech. Set.,
Jan. 2, 1946; Feb. 6, 1946; Mar . .6, 1946; Apr. 3, 1946; Ma.y I, 1946; June 5, 1946; July
3, 1946; Aug. 71 1946; and continued in monthly issues of Pet. Processing throughout
September-December, 1946, a.nn January-Sept.emb~r, 1947."

270

PETROLEUM REFINERY ENGINEERING

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- '

5! Air motor operated. valves.


Exchonger5 Pump ~111
FIG. 8-6. Emergency disposal

of hot oiL

(Pet. Refiner.) ,

Emergency Drains and Vents. This important and complicated topic


c~n only be mentioned. In case of fire or similar emergency three methods of blowdown are emp]oyed: (1) hot oils of- low vapor pressure are
released into a blowdown stack as in Fig. 8-6. 16 where they are quenched
with water, the liquid is releas'ed to the sewer, and the vapor is vented to
the atmosphere; (2) gases and cold oils of high vapor pressure are released'
into a. drum which is vented to a flare stack where the gases burn at the
top of the stack, and the liquid in the drum is pumped to storage tanks;
and (3) cold oils of low vapor pressure are pumped directly to storage
tanks. Figure 8-6 is typical of most hot-oil disposal systems. All airDisposal of Refinery Wastes, Pet. Refiner, July, 1946, p. 8l.
Pursell and Ferguson, Oil Gas J., Aug. 16, 1944, p. 114.
1& Johnson, J. H., Funda.mental Requirements for Safe Arra.ngement of Drains and
Vents, Pet. &ji'l'l1', June, 1947, p. 91.
U

loS

AUXILIARY PROCESSES AND OPERATIONS

271

motor-operated valves are operated from a central control station locate<l


to .give maximum safety and accessibility. Several other blowdown di~
grams are given by Johnson. u
Storage. The types of storage required for volatile and other types of
liquids are indicated in Fig.. 8-7 as a function of vapor pre~sure and tern.,.
perature (also see Fig. 8-8). Thus, spherical shapes may be used to store
. gaso1ines and low-vapor-pres$llre natural gasoline, and if the temperature
never exceeds about 80F, as in some arctic climeS, even hlgh-v.apor~
pressure natural gasoline may be kept in such storage. Of course, if
.crufficiently refrigerated, any material can be stored at atmospheric
prp.ssure in simple insulated tanks connected to a compressor which is
used to Jiquefy and return to the tank the small amount of material that evaporates. Liquefied methane (natural gas) has been transported in
thi~ way in specially insulated barges and tankers. 17 A common method
of gauging .sealed storage tanks involves the difference "in pressure in the
vapor space and in the. bottom of a gas-filled tube which extends nearly
\to the bottom of the tank.: In caiibratingl~ or "strapping" horizont8.I
. jcylindrical tanks, tables of ibe segments of circles appearing in handbooks are useful, but special ~onsideratiOIi must be given to the voluTIles
. contained in various types Qf heads. 19
Evaporation losses .are a function of so many variables such as .(1)
liquid or surface te~perature, (2) variation i~ atmospheric tell!perature,
(3) true vapor pressure of liquid, (4) volume of vapor space (how full),
(5) color or reflectiveness of surface, (6) frequency of filling,. (7) construction of tank, (8) degree of saturation attained in gas space, etc., that only
the gross appro:xim~tion indicated in Tabie 8-1 for a 10 R.v.p: gasoline
I

TABLE

8-1. INDICATION OF EvAPORATION LOSSES FOR 10-La R.v.p. GA.SOLINE

(5,000 BBL) CONE ROOF


Aluminum paint, balf full'

IN SMALL

TANKS

. Temperature,
"F

20 .... , .......
40 ............

. 60 ... '.' .......


70 ............
80 ............
90 ............

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...,.

20 ............. &,0"....- ...............

~.~~i--' ""'" ~~

e
6

~...

..

......

,....

.............. ~~ ....... ~,or


"""
V

,. ~ 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)

\.

REID VAP. PRESS. .


I I
1 I

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

TEMPERATURE - DEC. FAH R.


FIG.

SMALL
SPHERES

56
AND
46 HORIZONTAL.
36 CYLINDRICAL
~6
TANKS
IJ SPHERICAL
II SHAPES AND
6 VERTICAL CYL.
TANKS WITH
DOM! ENDS

C)

. .
ao

'

....... /~

.......

.......... ./.. 1"".,

.. 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&

~ .~;..... ~........ ~ ~,A /~~~~V~

,....

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

e\l:'~V"'. . . . VV~~~S~~ .: I--"

5 .;._ ..... " ,d!o


40
L......,., ~ ~ \,~ -.... L,/" ~
30 Oill.'~ ~ ............. Q~~......~ :,.. . ,.......

IO~"
"..

.....

./"'l/"'"'~ . /. ~,.,

2!)~O~ ~ .:..'0,....7

BU,T ANto

........ ~~~C}~ .. '~"

... - -

:> . V" 'bO~~ ~ ""'" "'"


.""
~ - rV"....... .. . .
.", 14.7 ~
. ~caO-i"i""-

.. ~

"\.

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.

AUXILIARY PROCESSES AND OPERATIONS

273

can be given. 20 . The effectiveness of various colors of paintS in reflecting


light, based on w~t.e as 90 and black as zero, iS U 22 about as follows:
Reflection of
heat
Black .... , ............... '.
No paint ......... " .... , ..
Alumin~m, old ............ .
Aluminum, new ........... .
White .. , ......... , ; ...... .

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.)

120,OOO-bbl tank. Filially, vapor pressure is vitally effective in changing


the losses~l3 (see Table 8-2). All of these data are most general (Tables
8-1, 8-2, etc.) and accordingly, computations22.24.26 ar~ necessary for each
situation. The losses from floating roof types of tanks (or their use by
to Nelson, W. L., Oil Gas J., Feb. 22, 1951 l p. 202, and Mar. 1, 1951, p. 78.
21 N~lson, W. L., Oil Gas J., Nov. 2, 1953, p. 130; also Symposium, Eva.poration
Loss of Petroleum, Oil Gas. J., Nov. 17, 1952, pp.'266-298.
22 API Evaporation Loss of Petroleum from Storage Tanks, Symposium 32d Ann.
Meetin'g, Chicago, Ill., Nov. 10, 1952; or Oil Ga8 J., Nov. 17, 1952, pp. 266-298.
'" Nelson, W. L., Oil Gas J., Apr. 26, 1954, p. 254.
U Nelson, W. L., Oil Ga8 J., June 23, 1952, p. 111.
n Prater, N. H., Pet. Processing, April, 1954, p. 537.

274

PETROLEUM REnNERT ENGINEERING

T,uu.JD

8-2~ APPBOXlVATB EI'I'lIlCT OF V.!.POR PUSS'O"R.E ON EVAPORATION LoSSES

Vapor pressure, psia


Reid at 100F

12
10
8
6
4:
2

Light gn.soline ... .' ........


Gasoline (the baais) . ......

Heavy gasoline ...........


Crude oil ................
Crude oil ...............
Crude oil ................
200-300 IJOlvent ... , ......
3()().-.tOOo solvent ......
120 flash, kerosene .......
150" flash, dis~t& .......
,

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

Based on vapor pressure required to cause the Ba.sh point.

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

Dullel waler temperalure', 'f


FrG. 8-9. Approximate
capacities of induced-dralt and atmospheric wa.ter.:.cooling towers 88 a. funetion of operating conditions.

Water Cooling.. .Waterbecoming so scarce that cooling by means


of ponds, spray ponds) or cooling towers must be practiced in nearly aU
refineries. Heat dissipation from ponds is affected by the. air temperature
and its humidity, by the amount ot sunshine, and by the wind velocity,
til EUerbr&ke &nd Veatch, Oil Gu J., Nov. 16, 1953, p. 223; and. Oil GaB J., Oct. 10,
19M, p. 248.

AUXILIARY PROCESSES AND OPERATIONS

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

Hicks, T. G" Pet. Refiner, April, 1952, p. 164.


Langhaar, J. yv., CMm. Eng.J August, 1953, p. 194.

CHAPTER

CORROSION AND METALS

Corrosion cost refiners


$560,000,000 during 1956 (Table
and if the cost of
production, transportation,
ing divisions added to this, the levy exceeds 2 cents per
of gasoline.
Those refiners
escape sulfi9.e and acid corrosion by processing selected
pils still
contend with soil corrosion, atmospheric oxidation, naph
thenic
high temperature
Chemical analyses of the
oil are
but it is also rtecessary determine corrosiveness by plant
and by special laboratory \ests
to Chap. 2,
17-18,
4, pp. 89 and 128). The
of
due to high sulfur
and accordingly, the cost
shown in Table 9-1 is an
of sourness ~rom as low as 2
per bb1 fvr
amoun t of sulfur ~nd
only 0.5 per cent
(plus 2.7 cents if it is
a crude oil that
to as high as 28 cents for an' unstable
of oil that contains
2
Extensive tabulations 3
of sulfur (plus 8 cents if it
.of
high-temperature strengths, applications, aI;ld analyses qf
alloys
steels used for
have been published.
Sulfide Corrosion.
is often found in natural
dissolved in crude oil, and
it may be formed by the
tion of organic sulfur compounds at rugh temperatures. It ra.pidly
attacks steel
that are exposed to the gas. Equipment that suffers
by this
comprises storage tanks and
tempera400F, pipestill tubes,
and fractionators.
650 to 700F, but
of hydrogen sulfide is
temperatures hlgher than 900F
liberation appears to
decrease. The presence of moisture facilitates the action of

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

REFINERY CORROSION AND METALS


TABLE

9-1.

ESTIMATES OF COST OF CORROSION TO THE REFINING INDUSTRY,

1956 a

(Cents per barrel)

All

High
sulfur
alone

cor-

rosion

High
sulfur
with
sourness

1. Maintenance (about 70 % of total maintenance) ....

2. Lost production (5 days per year) ................

3. Depreciation more ra.pid ........... _...... ~ .....


Total8tat~d by F. N. Speller (1927)1I.6 ........
4. Material and labor Jor corrosion repair .. _........' .
Total of items 1, 3, and 4 stated~ in 1953/1 ....
5. Built-in resistance (13% of plant cost) .... ', ' " :'"
6. Inspection Cost of tools, workmen, and inventory ...
Total by, API, items I, 2, 5, and 6 (1954)c .....
7. Neutralizing chemicals (incl. half of desalting cost).
8. Cathodic protection of lines ......... '.............
9. ,Unscheduled shutdown time .....................
10. Product loss by leaks or contamination ........ '. " ..
11. Fires, accidents, and insurance ..................
12. Over-design of equipment, ........ .' .............
13. Waste disposal ........................ : ........
Total of alle . . . . . . . . . . . . .

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

'

sulfide, and the concentration of oxygen in the gaseous mixture is of great


importance. "
In handlingS high-sulfur crude oils, chromium steels are employed
(Table 9-2). The cost of expensive equipment lS due mainly ~o labor
costs and the intricacy of design, and hence higher chromium contents
are justified for vessel linings, bubble caps and trays, centrifugal pumps,
pump liners, wear rings, pump rods, connections to vessels, pi pes till
bends, etc. The relative prices, strengths, and protection afforded by
chromium steels show that their use is usually justified (se~ Table 9-3).
The corrosiveness of sulfur-bearing oils is not directly proportional to
the sulfur content. Crude
oils ,that contain 2 per cent sulfur and that
I
4Devine et 901., Oxygen Effect on Hydrogen Sulfide Ga.s Corrosion, Oil Gas J., Apr.
7, 1932, p. 16.
'Nelson, W. L., Applications of Stainless Steel, Oil Gas J., Aug. '17, 1953, p. 156.

278

PETROLEUM REFINERY ENGINEERING

9-2

TABLE

Per cent chromium

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

Usually with about half as much nickel.


" Inconel. About 32 % Ni and 44 %
(. Applies pnly to tubes . Sulfide corrosion
4

.........."........ 9-3.

ExTRA COST VlmSUS

ExTBA.

less active

this temperature.

PERFOltMANCE (ApPROXIMATE) FOB

ALLOY STEELS USED IN REFINERY PJPESTILLS

Applies primarily to chromium and chrome-nickel steels, some with molybdenum

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.

times better peIionna.nee (than for carbon steel)

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

Oxid. and sulfide

1.15

1.6~

2.19
3.8
5.8
10.3
15.6

.2
28.6
55
High

High

At customary temperatures, 9OQ-1200F.


b No credit for strength.
c Bold face indicates that the extra c~st of a.lloy steel is not justified by the .per.
{ormlIDP,e.
Il

REFINERY CORROSION - AND METALS

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

'Nelson, W. L., Oil Gas J., May 25, 1953, p. 267.


7 Puckett, R. E., Preventing Corrosion, Oil Gas J., Sept. 23, 1937, p. 44.
Nelson, W. L., Hazards and Corrosion with Sour Crudes, Oil Gall J., pee. 16l 1944.
p.107.

280

PETROLEUM REFINERY ENGINEERING

lower percentages are also dangerous. Warning signs should be posted


at dangerous spots such as sewer openings and tank hatches. It is a
heavy gas and therefore tends to coUect on the ground at low points.
B. Fire Hazard. Fresh sulfide corrosion scale may burst into flame
spontaneously upon exposure to
9
Most difficulty encountered with
exchanger-tube bundles and with the scale in naphtha-rundown tanks.
Upon shutdown,. the lines and vessels should be flushed with "o/ater and
left full until the equipment is opened. Tube bundles should
sprayed
with water while being withdrawn, and a11 scaled surfaces should be kept
moist. The scrapings are kept moist until they are buried.
C. Elimination of Sulfide Gas. Dangers can he minimized by early
elimination of the hydrogen sulfide by burning it under boilers, by stabilization of the incoming crude oil, and by washing straight-run products
with caustic soda. Sulfur is recovered from hydrogen sulfide in many
plants .
. D. Desalting. True is particularly important because a combination of
sulfide and hydrochloric acid' corrosion is exceedingly troublesome.
Reduction of the salt content to 5 to 10 ]b per 1,000 bbl crude oil greatly
reduces the sulfide corrosion. Ganister linings may be used in the settler
vessels. Injection of caustic ahead of settlers to a pH of 8 to 9 helps
corrosion and aids settling.
E. A mmonia and lime are used the naphtha-rundown and cracking
systems, respectively .. Ammonia, used in amounts (often 0.01 to 0.031b .
per bbl) to give a pH in the condensed water of 7., introduced into the
top tray or vapor line of naphtha towers along with enc;mgh steam to
wash ammonium chloride out of the condenser system. Unsuccessful
,desalting may require .the use of Monel metal in the naphtha condenser
system. At temperatures past 700F, lime in amounts of 0.3 to 1.0 lb
per bbl is'said to decrease corrosion by 75 to 85 per cen~.
F. Field lines may be cement-lined if corrosion is severe.
G. Tank corrosion'
usually not serious except for crude oil (6 to
8 years), and naphtha-rundown tanks (4 to 7 years) if the naphtha not,
be injected in the vapor 'space, or the roof
caustic-washed. Steam
rafters and the bottom may be covered with gunite.
H. Topping piping. Corrosion is not severe except at points where the
temperature exceeds 500F as in transfer lines (use 5 per cen~ chromium).
Occasionally Monel metal required in naphtha-rundown lines if desalt.
ing and ammonia are not successfuL
I. Cracking piping requirements range from plain steel for feed, pressure distillate vapOf, and coke transfer linea; 5 to 9 per cent chromium fOf
flash or coke chamber vapor lines l still transfer lines} recycle, and reside Anon., Ferro Sulfide.Source of Unexplained Tank Fires, Oil Gas J., Feb. 4, 1943,
p.33.

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.

(Oil Gaa J.)

See pages 279-282 for the meaning of the

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

Wilten, H. M., Mining Met., March, 1937,

143.

283

REFINERY CORROSION AND METALS

Percentage of tubes
in service

Steel ................. ,...................


Stainless steel (18-8) ......................
Admira.lty metal or other copper-base alloys.

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

Ammonia is .unsuitable as a neutralizer if copper-base alloys are used,


because if used in excess it may destroy the metal faster than acid corrO:sion. The other neutralizers appear to produce protective films so that
corrosion halts :;titer an initial action. If scale-forming water is used,
admiralty-metal tubes must be cleaned frequently" because corrosion
occurs mainly beneath breaks or porous spots in the scale. The zinc in
the brass is dissolved and is replaced by spongy copper. 11
Corrosion due to acid and that due to sulfide can never be completely
segregated. Thus Table 9-4 on the corrosion of copper-base alloys12
shows" attack by sulfur" as well as "attack by water," meaning that
copper-base alloys were used at points where acid -or brine corrosion
required their use but that failure occurred mainly by sulfide corrosion.
Oxidation and High-temperature Strength. Iron and steel oxidize
rust in the presence of air ,or moisture.- At high temperatures such as
those encountered in boilers and furnaces, oxidation or scaling occurs very
rapidly. The chromiJIm and chrome-nickel steels (usually With molybdenum and limited silicon) are excellent resistors to high-temperature
oxidation, and at the same time they retain their strength and toughness
at elevated temperatures. For these reasons they are admirably suited
for boiler and furnace parts that are exposed to high temperatures and to
furnace gases.
The common method of measuring the strength of metals at high temperatures is by long-time heating tests. Short-time tests are unsuccessful
because in a furnace the metal stretches or creeps as time progresses and
will fail under a load that appears to be safe by short-time tests. The
effect of time on the strength of cast' carbon steel is shown in Fig. 9-2.13
The creep strength of creep limit may be defined as the load (pounds per
s.quare inch) that a. material can withstand at a. high temperature without
exceeding a. given rate of stretch. Cre'ep strengths are frequently given

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.

CORROSION 011' COPPER ALLOY CONDENSER TUBES"

Per CBIlt. of original1.eD8ile st.rengt.h lost duo t.o oorroalon


Antimonial

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

REFINERY CORROSION AN'D METALS

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

Tempctrcrlure, Degrees Fahrenheit

.FIG. 9-2. Rate. of Bow of cast carbon steel at eleva.ted tempera.tures.


.

\lOO
(ASTM.)

"

100 cu ft are a source ~f sulfide corrosiqn.

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

PETROLEUM: REFINERY ENGINEERING


TABLE

9-5.

PROPERTIES OF TrmE STEELS .

Approximate
com position
Kb;ld of steel

%
Or
Killed ea.rbon ...............
Carbon molybdenum .........
Silicon molybdenum .........
1 chromium, silicon, molybdenlUn. ....... ....... ,. . ,. ..

II

..

&.

....

I>

.....

1.25 chromium, silicoD,molybdenum ...... , ............


2 chromium, molybden~ ....
2 cbromilUn., silicon, molybdenum .....................
2.5 chromium, silicon, molybdenum ..... : ..............
3 chromium, silicon, molybde.num .....................
3 chromium, molybdenum ....
5 chromium, molybdenum ....
5 chromium, silicon, molybde-

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

num ..................... 5.0


5 chromium, silieoD, ruuminum,l. molybdenum ........ 5.0
9 chromium molybdenum .... 9.0
18-8 chromium nickeL: ...... 18.0

%
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

materials are. suitable: (1) solid-solution alloys such as Monel metal,


. In conel , ~nd the austenitic stainless steels, a.long with .low-alloy steelsr'
that are low in carbon and contain an alloy element soluble in iron, (2)
certain elementS such as copper, nickel, and lead, and (3) alloy cast irons.
The low-alloy steels, particularly the nickel steels; are cheaper and are
widely used down to temperatures of minus 100F. Figure 9-3 indicatesU
the impact strengths of various materials relative to their impact strengths
at higher (often room) temperatures, and Table 9-7 indicates the kinds
of materials shown in Fig. 9-3. Note that curves I, 2, and 3 for chromium
and plain carbon steels show almost a complete loss of impact strength
at minus 50F.
.
14 Nelson, W. L. J Low Temperature Services, Oil Gd$; J., Allg. 7, 1941, p. 43; and
Apr. 12, 1954, p. 163.

i .

T~Lm

9-6.

MAmlUALS POR HIGH~ATUU TtTBE SUPPORTS

ScaJing temp. OF

Approxima.ta composition, per Qeni

Name

Type 01
ma.teri8.1

Design
strength,
Chro-

Carbon

&ilicon

Gray' trOD Cast iron

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
"

......

'OxiRe- SulfiOthers dizing" ducing dizing

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

.....

"

....

......

.. "

....

..

...

"

Nickel chromium iron. Alloy iron


Saale resisting iron. . . . Alloy iron

2.6-3.0 1.2~-2. 2 .

1.4

. . . . . . ..

12-16
14 .3

Ni-resist iron . ........ Alloy iron

3.0

1.6

3.3

Type 410 steel~ .. . .... Steel ,'

0.10

o .:l~

11.5-14

..

" "

0.6

17

....

"

0.9

26-30

17 Chromium ......... Steel,

..

..

HC casting' .......... Steel ca.sting , 0.4

HF 18-S' ............ Steel casting 0.36


HB 24--1.2C ........... Steel casting 0.35
BE 28-10' ........... Steel oa.ating 0.35
EX 25-20-.......... . Steel casting 004 '
HX 65-15~ ....... . ... Steel casting 0.55
HT 35-11)'. . . . . . . . . .. Steel oaating 0.55 '
.. With modera.te amount of sulfur dio;ide.

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

Based OD creep strength at oxi<::fu;ing scaling temperatu.re.


"Types" of the AmeriCAIi Iron & ' Steel Instituta; and the HO, HHj etc., desig.oations ~ those of the Alloy Casting I~titute.
d Estimated.
'
,

'c

--------~--~=-~----------------------------------~----------~---------

288

. PETROLEUM REFINERY ENGINEERING


TABLE

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

4-6 chromium .............. , , ..


Carbon (b8.!ic bel\8&mer) ......
Carbon (open-hearth) ........... .
Va.nadium ..................,',.
Ma.ngane8e va.nadium (caatingli) ..
Silioon manga.nese ...........
Copper manganese. . .......... .
Zirconium. . . . . .. . ... ' ........
Copper chromium ..............
Nickel ................. , ...... .
Molybdenum nickel ............ .
Aust.enit..ic IiIt.eelS. monel metoJ, and
the elements lead, copper, and

0.11

FIG. 9-3

Per cent others

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&")

Nickel-rich cast iroIlll. ....... ..

After high-tempera.ture aervice


Nearly pure iron
Regula.r carbon ateel
NorD'LlLlized and tempered

Normalized
About 300 Brinell

Solutions or pure metah

nickel ....................... .

13

Notes

....

3-30 Ni, 0.5-5 Cr

" SAE 4130, 4615, 4140, 4815, 4340, and 4640.

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

REFINERY CORROSION AND METALS

289

Metals for Refinery Chemicals. The universal materials for handling


sulfuric acid are steel and 1ead. Ordinary mild steel withstands concentrated acid, but chemica1 lead must be used for dilute acid. Lead is such
a ductile material that it presents many stnlctural difficulties. For this
reason, lead-lined rather than solid lead equipments, such as pipelines,
agitators, and pumps, are gaining in favor. Recently some success has
been attained in spraying steel with lead. A number of other materials,
including tin, zinc, aluminum, copper, brass, nickel silver, Monel metal,
and stainless steel, are also being sprayed. The coating16 is app1ied by
roughening the surface by a sandblast and spraying the surfacing meta]
from an oxyacetylene gun. Several coats 'm ust be applied. Metallizing
is also used to build up worn pump rods, to hard-face cylinder liners, 'etc.
Certain alloy cast irons such as Duriron (14.5 silicon) and the high-silica
irons are usaul for lines, valves, pump~, etc., for handling su1furic add
and acid sludge. In factO
, ordinary cast iron is used for many corrosive
conditions because of its cheapness. Wilkinson 18 presents an excellent
summary of the, 'resistance of alloys to sulfuric acid used in treating,
alkylation, reclamation, and ~oncentration processes.
P]ain steel and cast iron are the common metals for handling caustic
soda or sodium hydroxide, a.lthough under certain conditions nickel or
Monel metal is superior. Likewise plain steel is the common material
for handling anhydrous hydrofluoric acid.
Hydrochloric acid and even brines are so troublesome that scarcely any
entirely satisfactory materials are available. Among the best materials
are metallic silver or tantalum and glass or ceramics ware. For dilute
acid or brines, the standard materials are the copper-base alloys or
nickel alloys (see Table 9-4).
Table 9-8 indicates some of the sernces 3 that have not been discussed
in this chapter. .Note especialJy that slight differences in the service
may cause an alloy to be unsatisfactory and ~ccordingly Table 9-8 is
only an indication of the types of resistant materials that should be
explored.
Nonsparking Metals. Certain Jow-melting metals such -as aluminum,
copper, tin, and lead are conipl~tely nonsparking. Copper-base alloys
such as beryllium copper and aluminum bronze are classed as nonsparking, and Monel metal produces such low-temperature sparks that gunpowder, gasoline, or explosive gas mixtures are not easily ignited.
Neutralizing Chemicals. Few materials are satisfactory resistors to
"ii.cid" -corrosion, and hence neutraHzing chemicals such as ammonia,
sodium hydroxide, sodium carbonate, and lime ar~ widely used. In genu Rice, H. B., Metal Spraying . . . ,Ref. Nat. G~o. Mfr.) April, 1933) p. 148.
111 Mechanical and Metallurgical Control of Sulfuric Acid Corrosion in Petroleum

Processes. Trans. ASME, 1946.

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

Isomerization-pump parts &: hot


(3, 16, 17, 18)
Me.-captans (28)

Monoethylene amines--ooolers, exchangers, etc. (7,


29)
N aphthenic acids-550"'F (n, 22", 24)
Phosphoric acid-liq blowback in poly

(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)

lsomerization-dilute HOI or with SbCh


(10, 16)
18Qmerization-200Of
saturator, Hel reboiler, etc. (8)
Isomerization-194F. catalyst contactor
(10)

Phosphoric acid-low conc,


(22, 24)
Pbosphoric a.cid-:- high conc.
(7, 16, 17)
Phosphoric
75-85% at
150F (8)

Phenol, wet vapor (10, 15, 16, 17)


YroP8JJl6 chillers (28)
ta.Cit':-tlA.re tip (11)
Sodium hypochlorite (7,30)
I:SO<llwn hydrox{de-lO% at
at 251F; or 80% at 275F (7)
Sodium hydrox:ide-3o-S0 % at

67%
(8,

10, 12, 39)

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)

REFINERY CORROSION AND METALS


TABLE

9-8.

291

INDICATION OF ALLOY MATERIALS USED IN PETROLEUM REFINING"

(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

20 Nickel steel, 3~-8 Ni


21 Nickel sted, SAE 2512
22 Soo.in1ess ,steel, 3 % Mo
23 Stainless steel, Type 304
24 Stainless steel, Type 316 or 317
25 Stainless steel, Type 405 or 410
26 Stainless steel, Type 502
2.7 11-13 chromium steel
. 28 Aluminum alloys
29 Alcla.d steel
30 Aluminum bronze
31 Everdur bra.ss
32 Copper silicon mang8.nese alloys
33 Admira.lty (or antimonial) brass
34 Red brass
35 Silver metal
36' Tantalum metal
37 11-14 manganese steel
38 Haveg
39 Carbon steel or cast iron

" 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'

PETROLEUM REFINERY ENGINEERING

charging stock is usually sufficient, although the exact amount must be


determined by plant experiments. Obviously, an excess of the neutralizer
creates 'alkaline corrosion, which may be more severe than the original
acid corrosion, and hence the chemicals are not added in large enough
quantities to neutralize the acid or sulfide materials completely. The
corrosion can often be reduced' to half by adding much less chemical
than the amount required for' complete neutralization.
Ammonia rapidly attacks admiralty metal, and hence ammonia should
not be used in a system ha.ving brass condenser tubes or parts. In some
instances ammonia has been successfully used with admiralty-metal condensers but under careful supervision so that no large excess was ever
present. If the equipment is constructed of iron alone the pH of the rundown water is h:eld between 7 and 7.7, but if copper-base alloys are pres'ent the pH is held betwee~ 5.8 and 7.2. One refiner reports a decrease in
the iron content of the rundown water from ,456 to only 45 parts per
million when the pH was increased from 4.8 to 6.6. Ammonium chloride
gradually accumulates in the lines and condensers, and it must be '
uflushed out" with water or steam during cleaning periods. Caustic soda
also causes deposits, and these deposits are so difficult to remove that the
use of caustic has been gradually abandoned. Caustic deposita are particularly troublesome within fractionating towers so that, if acid corrosion
oc~urB within a tower, ammonia has usually been adopted as the neutralizing agent. Caustic sO,da also causes caustic embrittlement of the steel
shells of evaporators, towers, etc., and is Bai~ to promote coking in furnace
tubes. Two
'one-half to twenty pounds of anhydrous ammonia is
used for 1,000 bbl of ,crude oil, depending upon, the amount of ~cid that is
produced. Some refiners have reported a decrease of 97 pe.r cent in th~
exten t of acid corrosion by the ,use of ammonia.

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
.
,

P8l'affin and' naphthene hydrocarbons are only slightly attacked , by


, -93 per cent (66 0 B~) acid at room temperature. Higher temperatures
and cOncentrations cause attack, particularly upon isomers having several
$ide chains. Benzene is only slightly attacked by 93 per cent acid, but
toluene l and xylene are more readily attacked. Thus 66 Be and stronger
acid (and also sulfur dioxide) is used to remove the aromatics that ca~se a
smoky flame in kerosenes.
Olefins, diolefins, and acetylenes are attacked by even 75 per cent acid.
Blgh temperatures and acid concentrations favor polymerization of olefins, and low temperatures and acid concentrations favor"the formation
of alkyl acid sulfates, neutral esters, and sec. and tert. alcohols. Higher
alcohols, dipolymers, and to some extent acid alkyl sulfates dissolve in
cracked distillate; and upon redistillation the acid alkyl sulfates decompose, yielding alcohols, sulfur dioxide, and colored materials. These sulI

Brandt, Lee, and Wadsworth, . . . ' Toluene Treating, Ind. Eng. Chem., 39, 1010

(1947).
293

294

PETROLEUM REFINERY ENGINEERING

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

Brooks and Humphrey, J. Am. Chern. Soc., 40, 822 (1918).


Pyho.la, E., Petroleum, 9, 1506 (1928).
- Born and-Wilson, Natl. Pet. New8, Apr. 5, 1933, p. 23.
I Wirth, Kanholer, and MurphYJ Control of Color . . . Treating, Ref. Hall. Gasa . .
Mfr., December, 1930, p. 89.
a Kalichevsky and Stagner, It Chemical Refining of Petroleum," p. 51, Chemical
Catalog Company, ~nc., New YorkJ 1933.
7 Purification of Pressure Distillate, Oil Gas J., Mar. 5, 1931, p. 141.
Control of Color . . . Treating. &f. NaJ.. Oaso. Mfr., December, 1930, p. 89.
~

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

PETROLEUM REFINERY ENGINEERING

no acid treatment; mixed-base oils more; and asphalt-base oils the


higher figure. Vacuum-distilled or solvent extra~ted stocks require much
less acid.
Cooke and Hayford 9 find tha.t the desulfumation is directly prQportional to the amount of acid that is used.
Temperature of Treatment. Polymerization losSes are greater at
higher temperatures, so that unless polymerization is desired, _as in rare
cases when the sludge is to be utilized, lower temperatures are desirable.
High temperatures favor the removal of aromatic and unsaturated hydrocarbons and of resinous asphaltic materials. ,Thus naphthenic kerosenes
and solvents are usually refined at a relatively hlgh temperature unless
the removal of sulfur is also necessary.
Lower temperatures produce a better color in the product and 'are favor- '
able for the removal of sulfur compounds. In treating lubricating oils at
low temperatures the viscosity ,of the oil-ma.y be so great that settling is
slo\Y and the separation imperfect. This results in too long a contact time
and a loss in color, and hence lubricating oils are usually treated at relatively high temperatures. The Union Oil Company of California hag
studied the effect of temperature, acid concentration, and amount of acid
on the .removal of suHur from cracked distillates.ll
The temperatures that are commonly used for various treating operations are as follows:
Straight-run gasoZine-70 to gOF. If large quantities of acid are
reqlJired, it may be practical to go to lower temperatures.
Cracked gasoline-60 to gOF. If heavy treats-are required, temperatures of 25 to 30F are -recommended, although temperatures, of 40 to
'50 may be more economical.
Keros~90 to 130F. If the oil is to be redistilled, a higher temperature may be economical. Robinson 12 finds that low temperatures are
better.
_Lubricating-oil stocks--Customary tern perature~ 13 (11 D-180F) for
various stocks are indicated in earlier editions of this book.
Cylinder stock-130 to 170Fu and 150' to 180F if treating is conducted
before dewaxing.
The cold-treating methods have many advantages from a treating
standpoint, but the refrigeration requireinents are enormous.
Contact Time. Two factors are involved in considering the contact
tIme. Prolonged contact of acid sludge and oil results in a poorer color
and less stability, but too short a time may prevent complete utilization
Ta.ble 93, 2d ed. this book; also Kalichevsky and Sta.gner, /I Chemica.l Refining
of Petroleum," p. 51, Chemical Catalog Company, Inc., New York, 1933.
12 Robinson, C. L., U.S. Pa.t. 910,584 (Jan. 26, 1909).
13 Kauffman, H. L., Ref. Nat. Ga80. Mfr., May.-1927, p. 59.
11

297

CHEMICAL TREATMENTS

of the acid. Furthermore, the time of contact is intimately associated


with the fineness of dispersion of the acid throughout the oil and the time
required to separate the sludge.
Straight-run and cracked gasolines are contacted with acid for less than
a. mlnute in continuous-treating systems. A short contact time is particularly .advantageous for cracked gasolines to minimize polymerization and
sulfation of the oil.. The time of contact is sometimes held to only a few
seconds by mechanical contactors,14 and the s ettling time is eliininated
ahnost altogether by centrifugal means. Continuous processes for treating lubricating oils have been investigated,16.l&r17 and a short time ..of
contact (10 min) is found to be advantageous.
In conventional batch agitation, the time of contact 18 much longer.
For light dis.tillates the time of air agitation ranges from 15 to 40 min.
Kerosene normally requires 30 or 40 min, and for lubricating oils the time
may be 90 min. The time required to settle the sludge in an agitator .
ranges from a few minutes for gaso~e to as long as 15 hr for very viscous
stocks.
Inhibitors of. GUIlL During cracking, unsaturated hydrocarbons are
produc~d that upon exposure to air during storage produce so-called
tt gum" in the gasoline.
Gum may be removed by treatment with sulfuric acid or by vapor-phase treatment with ful1~r's earth (Gray process),
hut the use of antioxidants or inhibitors has bec~me standard practice.
Inhibitors delay the formation of gum; but if sufficient time elapses, they
do not prevent its formation. Exposure to sunlight, elevated storage
tempera.tures, or a high percentage of sulfur contributes 18 to more rapid
gUm formation. The stability of gasoline u is approximately proportional
to the induction period'in oxidat~on bomb tests for gum.
.
Among inhibitor agents' are such synthetic materials as dibenzylpara-aminophenol, monobenzyl-para-aminophenol, para-hydroxypheny1-
morpholine, tributylamine, alpha-naphthol, and catechol; in coal-tar
distillates, creso]s and xylenols; and in wood-tar .distillates, creosote,
catechol, ethyl guaiacol, mono ethers of pyrogallol, ~d the xylenols. 20
Stratford, C. W., NatZ. Pel. New8, Ma.r. 12, 1930, p. 32F.
15 ~ones, L. D., Use of Centrifuge in Acid Treating Petroleum Stocks, Ref. Nat.
Ga8o. Mfr., June, 1934, p. 224.
U Walker, R. C., Continuous . . . Centrifugal Separation . . . J Ref. Na!.. Gaia.
Mfr., June, 1934, p. 228.
17 Trescott, L. C., Sludge, Ref. Nat. G(l8o. MfT., May, 1934, p. 1.72.
11 McNamara, T. L.,.... Gu~ Stabilities of Gasoline,.. &f. Nat. Ga$o. Mfr.,
October, 1934, p. 381.
it Yabroff and Walters, Gum Formation in Cracked Gasolines, Ind .. Eng. Chern.,
It

S2,83 (1940).
:10

Rogers and Voorhees, Gum Formation in Gasoline II, Ind. Eng. Chern., 26, 520

(1933)..

298

PETROLEU REFiNERY ENGINEEBING

The. amount of each inhibitor required varies widely, but to

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

Mercaptans, hydrogen sulfide, and elementary sulfur are removed' (or


converted) from light distilla.tes by the so-called U sweetening processes."
Mercaptans impart a foul odor, and they seriously decrease the octane
susceptibility to tetraethyllead. Elementary
number by 'reducing
sulfur (in the presence of mereaptans) causes corrosion.
major ways of attaining sweetening: (1)
that
There are
oxidize mercaptans to disulfides, (2) processes that remove the mercaptans, and (3) processes that destroy and remove other sulfur compounds '
................"'"" with mercaptans, hydrogen sulfide, and suHur. The last of these
methods usually considered as a " desulfUrization" process. Walker
discussion of the vario:us treating
and Kenneyn present a
processes. '
. '
,
Oxidation Processes. These processes convert mereaptans into -less
odoriferous clisulfides by such processes as the docwr,2s copper chloride,'u,
the
hypochlorite?5 and
sulfide, processes." Since disulfides
lead .sQsceptibility
gasoline and since ~he
of reduction
cap tans to U doctor sweet~' (0.0004
cen~)
being questioned, 2~ -theseprocesses are being gradually abandoned. However, catalysts or inhllr
, itors 28 of the p-phenylenediamine. ~ype, which in the presence of 'air cause
cauStic-washed gasolines to be converted during 8.
mercaptans .in
few days into disulfides (so-called inhibitor sweetening), continue 'to be
used because of the cheapness of such a. process. Small amounts of.
,

U Downing, cb.rksonJ and Pedersen, . . . Metal Catalysts in


Gum Formation, Oil GaB J., July Z'lt 1939, p. 97.
n Removing and Convening Mereaptans,
Prouuinfh April, 1956, pp. 58-66.
13 Lowry, C. D., Jr., The Plumbite Sweetening of Gasoline,
Oil' Products
Co. (Chicago), Bookkt 242, May, 1940.
2t Conn, M. W.,
Copper Sweetening, &j. Nal.Oaso. Mfr., March, 1941, p.
and Sc~eman, C. T., Jr., Linde Copper Sweetening Process, Pet. Engr'j May, '1947J
p.I84.
U Anon.,
Natural Gasoline .. i
Nat. GMt), MfT., July, 1933, 278.
III HAppel and Robertson, Lead Sulfide . . . Dry Sweetening
Oil GaB. J.)
Mar. aI, 1938,
125.
iT Happel
Ca.uley, Significance of the Doctor Test for Gasoline, PrOl!. API,
21M (3), 96 (1940).
til Moriarity and
Developments Petroleum. Treating .t"rclce<lures
presented before Nat. Pet. AsBoc., Cha.rleston, W.Va . May 5, 1949; a.hID Jones,
M. C.
&daBning, Oil GGI J., Apr.
1951. p. 88.

C~ICAL

299

TREATMENTS

metals (lead, bismuth" thallium, etc.), in the caustic used in iIihlbitor


sweetening hasten the sweetening reaction and help in reducing peroxide
or gum formation.
Mercaptan Dissolving Processes. These processes, such as caustic
washing,29 Shell Solutizer,30 Atlantic Unisol,31 Pure Oil 'Mercapsol, at and
Tannin Solutizer, 33 are still in very common use. All of these except
caustic washing employ solubility ~promoters -such as salts of isobutyric
acid,30 alkyl ,phenols, 30 methanol, 31 cresols,32 and naphthenic acids, n along
with caustic soda. Natural promoters are also present in most naphthas,84 and these, wiU accumula.te in the caustic during washing and
regeneration. The solutions ar,e regenerated by heating and stea.m
stripping, except in the Tannin Solutizer process in 'Yhich
blowing is
employed. '
More recently34 it has been learned tbat the use or'more concentrated '
sohitions of caustic and solutizer, which causes two phases of treating '
'solution to appear" may result in much more complete mercaptan removal.
The oxidation processes are being abandoned mainly because of 'the
reduction in octane number that occurs. The many processes have been
compared by Happel, Cauley" and Kelley,3Ii and although the improvement U by various processes' is dependent' upon the pa.rticular, situation,
the general improvement is, as indicated in Table 10-1. The catalytic
processes give the best octane number, but they are more expensive; ~nd
when applied to cracked gasolines the cost mounts rapidly , beca~ the
catalyst must h.e regenerated frequently.' "
' ,
The distribution 36 of mercaptan sulfur compounds in gasolines is indiCated i~ Table 1~2. , The removal of ~ercaptan8 by the solution,
processes is governed by the following equation, U which is,applied to eac.h
mercapt~n present in the gasoline.
'

au

RSH left (per cent) _ (1 - S)(Eq, - E)Y.


100'
- (1 - S)(Ea - E)V

+(E -

1)(8 - Sb)K,
(Em - 1)(8 - ~)KfJ.

(10-1)

n, Henderson, Ross, and Ridgway, The TEL Susceptibilities of Gasoline . . .


Caustic W RShing, Ind. Eng. eMm., 31, 27' (1939).
&0 Yabroff and Border, The Solutizer PrOOO88 for the Extraction of Mercaptana"
Proc. APIJ 20M , (3), 95 (1939).
It Field, H. W., The Caustie-methanol Mercaptan Extracti()n Process, Oil Ga., J.,
Sept. 25, 1941, p. 40.
12 Ma.cKusick aDd Alves, Mercapsol Process for Gasoline Trea.ting, Oil Ga3 J., Apr.
13, 1944, p .. I26.
U O'Donnell, J. P., Tannin Solutizer Process Practically Automa.tic . J Oil Gas
J., July 1, 1944, p. 45.
U Duval Rnd Klilichevsky, Dualayer Process, Oil Gas J., Apr. 12, 1954, p. 122.
, iii Critical AnalySis of Sweetening Processes and MereaptM Removal, (h1, Gas J.,
Nov. 12, 1942, p. 136.
II Nelson, W. L., Oil Gas I., Mar. 2, 1946, p. 85; also Oct. 3, p. 137" ADd Dee. 22,
p.75, 1945.

300

"

PETROLEUM REFXNEBT ENGINEERING

where 8

= WK

stripping factor; where W = volume ratio, steam to


caustic (steam volume equal~ condensate volume), K. = stripcoefficient (Fig. H)-I)
Il ,

extraction factor; where K f = extraction coefficient (Fig.


10-2), V = volume ratio, gasoline to caustic, a = number of
theoretical extraction stages' p]us one", b "'" number of theoretical regeneration stages plus on~
The K-2 solution of Figs. 10-1 and 10-2 is aN pOtassium hydroxide and. aN
potassium isobutyrate, and the 20 per cent of "organic acids" are natural
ones dissolved from Mid Continent cracked and straight-run gasolines..
Basic or average susceptibilities of various gasolines to tetraethyllead
are" shown in Table 3-11, which is based'l on the behavior of about
321 samples... The color stability of some gasolines is also closely related
to sulfUl' content, to the methods
conducting sweetening, and to
.certain methods of Iriech&n:ical separation. I i
Camtic wlUhing methods) which involve bringing the gasoline in contact
with sodium, at calcium, to or magnesium (brucite) hydroxides lor the

Octane number of desuUurised stock with 3 cc TEL

.Dctane-number'
of stock

Chemical processea!'
,

CAtalytic on only
8t~ght.-nm

gasoline- .

Straight.-run and .
low-sulfur gasoline!

Cracked gaooUn