Oct. 27, 1953 A. P.

GRATIS ET AL 2,657,243
ISOPROPYL ALCOHOL PROCESS

CZZbert 1-2 Gz. Sir2 Wenators

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>§-Z??4 duvorres
 Patented Oct. 27, 1953 2,657,243

UNITED STATES PATENT OFFICE

2,657,243
ISOPROPYL ALCOHOL PROCESS
Albert P. Giraitis and Mack C. Fuqua, Baton
Rouge, La., assignors to Standard Oil Develop
ment Company, a corporation of Delaware
Application September 15, 1948, Serial No. 49,450
5 Clairns. (C. 260-641)
1. 2
The quality of isopropyl alcohol is improved boiling impurities and some alcohol overhead and
economically by this invention through an in and alcohol-Water mixture With some impurities
dustrially feasible method of purifying refinery boiling higher than the alcohol as bottoms. The
propylene fractions. overhead stream is washed with water and the
The production of a high quality isopropyl in Soluble portion consisting primarily of isopropyl
alcohol product, from the standpoint of purity ether and high boiling impurities soluble in the
and odor, made by the hydration of propylene ether is sent to storage. The Water alcohol layer
with sulfuric acid as catalyst, is achieved by re from this ether Washer is returned to the above
moving C4 hydrocarbons from a propylene frac mentioned column for recovery of the alcohol.
tion prior to absorption in the acid; also, by re 0 The bottoms fron the above mentioned tower are
moving simultaneously the highly unsaturated fed to a Second distillation tower for concentra
C3 hydrocarbons, methylacetylene and propa tion and purification of the alcohol. A portion
diene from the fraction. of the lower boiling constituents from the column
The production of a chemically pure isopropa are recycled to the first Column. This stream is
no is desirable when the alcohol is to be used for referred to as recycle stock.
preparing other chemicals, for use in cosmetics An isopropyl Sulfate, Sulfuric acid mixture of
and toilet goods, for rubbing alcohol, or for use the usual Strength made in the alcohol plants was
as a sterilizing agent. prepared by adding Sulfuric acid and water to
The commercial propylene fraction is general isopropyl alcohol of high grade with no odor.
ly a cracked hydrocarbon product obtained by 20 C4 hydrocarbons of different types were then ab
close fractionation which leaves the propylene Sorbed in Separate portions of the isopropyl sul
contaminated by other C3 hydrocarbons and fate-Sulfuric acid mixtures to the extent of ap
Small amounts of C4 hydrocarbons. proximately 1 mole percent of propylene (or iso
The removal of the contaminants that cause propyl alcohol) in the extract. The absorption
degrading of the isopropyl alcohol product is effi 25 was carried out by passing each of the gaseous
ciently accomplished by a method which Will be C4 hydrocarbons through a separate sample of
further described in detail. the extract at 80° C. and atmospheric pressure
Earlier studies did not show any certain corre until a predetermined amount was absorbed. One
lation between C4 components in the propylene Sample was allowed to absorb a large amount of
feed stream to the acid absorber and the finished 30 One of the C4 hydrocarbons. Two control
alcohol product. Now the failure to learn about Samples containing no C4 were prepared, one
this correlation can be ascribed to the rather long heated at 80° C. and the other at 100° C. for the
hold-up of impurities in the conventional alcohol Same length of time and finished in the same way
plant Operations. as the other samples. The finished alcohol prod
Work has now been carried out to determine 35 luct was prepared from this steam distillate by
Which, if any, of the C4 and C3 hydrocarbons, distillation in the usual manner. The products
difficult to remove, produce the undesirable odor of the samples were classified according to odor
that often degraded the ispropyl alcohol product as follows:
requiring an expensive Washing and finishing
treatment for removal. 40
TABLE
În Order to make the terms used underStand
able, a brief description of the process for iso hydrocarbon Added Alcol????duct
propanol manufacture is given herewith. The
propylene feed Stock is fed at a suitable pressure Butadiene------------------------ - heavy.
to an absorber containing sulfuric acid of suitable
Isobutylene------
45 Butylene - Moderately heavy.
strength and temperature and the sulfuric acid Butylene 2.
1----- - D0.
D0.
reacts with the propylene to form an isopropyl Isobutane--- Slight.
Sulfate-sulfuric acid mixture also containing i
utadiene (large amoun t) (??????;
ery heavy.
Some free alcohol and isopropyl ether. This mix Controli (80°C.)------- -- ?ó' y
ture is fed to a stripper where dilution water isControl (100° C.)------------------------------ Do.
added and steam introduced to remove all alco 50
hol and other volatile components from the di Each of the Samples, including even the con
luted acid. After caustic scrubbing for removal trol, produced a recycle stock that had odor, the
of acidic components from the crude alcohol, the recycle Stock being the usual fractional conden
alcohol is sent to storage from which it is fed to 55 Sate that is condensed from the overhead iso
the finishing section. The isopropanol finishing propyl alcohol vapors of the finishing still.
Section Consists of a column for removing low As shown by the foregoing experiments, the
 2,657,248
3 4.
absorption of the butylenes and of butadiene in A satisfactory method for removing the harm
the extract produced characteristic undesirable ful C3 and C4 hydrocarbon impurities of the pro
Odor. The absorbed isobutane produced Some pylene fraction will be described with reference
odor. The strongest odors were approximately to the accompanying flow diagram.
as strong as those obtained in plant production. In the drawing, the unit shown has two frac
It was not found how to isolate the odoriferous tionating towers, low pressure tower T-f and
compound or compounds. In studies made for high pressure tower T-2. it he crude propylene
the purpose of concentrating and possibly isolat fraction containing excessive amounts of the
ing the odoriferous products from the isopropyl harmful C3 and C4 hydrocarbons, such as pres
alcohol product, isopropyl alcohol having odor was 0 sentina. Cracked hydrocarbon propane-propylene
carefully fractionated and separate Small frac Cut, is passed by line 3 into an intermediate part
tions were examined. It was found-that the odor of the fractional distillation zone in T-l. An
components were both somewhat higher and - Overhead Vapor comprising the propylene and a
Somewhat lower boiling than theisopropyl alco Small proportion of the C4 impurities that enter
? itself and could not be removed by fractiona 5 T-is. Withdrawn by line 4. A bottoms product
10.
comprising the C4 impurities is withdrawn from
The adverse effect of the C4 hydrocarbons on T--by line 5.
odor is also usually accompanied by other un The overhead vapor from T- is cooled and
desired manifestations such as, acetone build up, condensed by indirect heat exchange; with Water
increase of high boiling compounds that accumu in condenser 6. A portion of the overhead Vapor
late in the fractionating tower plates above the condensate is returned as reflux by line to the
feed plate in the alcohol finishing still, and low top of T- and the remaining sportion of: Con
ered finishing rates. densate is passed by pump 8. through line 9 into
A plant. Scale study which shows the necessity an interimediate part of the fractionating: zone
for making the propylene feed free of C3 acet 2 5 of T-2.
ylenes to produce a high quality isopropyl alco In T–2, the;temperature-andpressure condi
hol product is furnished by the following tabu tions are controlled to make the liquid bottoms
lated: data of Table II: contain a substantial amount of C3: hydrocarbons
with the liquid C4 impurities, so that vapors that
TABLE 30 pass "overhead.from T-2, through-line : ) are es
sentially free of C3 acetylene and C4 hydrocar
Acetone in
Eigh Boiling bons. The overhead vapors from T-2-are ipar
Acetylenes Alçohol Compounds tially condensed in water cooled condenser f.
in Feed, in Ether
p.p.m. heads, Wit. Product, Wt.
Percent
The condensate; collects in receiver; 2 and is re
Percent 35 turned by pump 3 and line it -as reflux to the
top of T-2. Purified propylene productis. With
396
550
drawn from receiver 42 by line - 5 to be passed
585 to an alcohol producing unit, -e.g., into a Sul
744
,744
furic acid absorption tower. The bottons With
865 40 drawn from T-2 are recycled by pump S
510 through line to the low pressure tower T-.
The towers T- and T-2 are equipped with
The effects of C4 hydrocarbons in the propylene Vapor-liquid contacting means, . e. g., plates (8
feed on product quality and formation of unde and 9, reboiling heat eXchangers 20 and 2 and
sired acetone and high boiling by-productS is other usual fractionating tower equipment.
Shown by data on typical plant runs presented For the type of operation, described, suitable
in Table IIT.
Conditions in the fractionating Zones. are:
TABLE III TABLE; IV
Effects of C4 hydrocarbon in propylene feed 50 Tower T?1
Highboilers odor of Top Tenperature, F------------------ 130
*C, in Feed, Acetone,
?Wt? Wt?
inProduct,
Ether Alcohol Bottom Temperature, E 240
Percent Perçent Wit. Product Pressure, p. S. i...g------------------------- -330
Percent
55
0.0 Good
The temperatuires. and pressures, given are close
0.01 Good approximations but may vary slightly with the
0.04
0.
Fair
Poor
feed composition. In general, the top tempera
0.34 Poor ture of both towers is held preferably at about
1.0 Poor 60 130 F.; the preSSurefori- is in the range of
300 to 330 p. S. i. g. With a T- bottom tem
The data in Tables III and III indicate that perature in the grange of 240 to .255.F.; and the
the tolerable limit for both the C4 Compounds preSSure for T-2 is in the range of 330 to 350
and acetylenes in the C3 feed is not more than p. S. i.g. With a T-2 bottom temperature in the
0.10% and 0.05%, respectively, if a high quality 65 range of 180 to 220 F.
alcohol is to be obtained. They also show how In operating the tower's at the higher part of
the acetone and high boiling by-products in their preSSure.i.anges, the bottoms liquid recycled
crease as these impurities in the feed increase. from the pressure tower T-2 to T- will contain
Thus it can be fully appreciated that an ef 30 to 80% by Weight of liquid C3 hydrocarbons
ficient method of reducing the C3 acetylene con 70 (propylene and propane). In operating the
tent, preferably to less than 0.05%, while reduc tOWei's in the lower part of their pressure ranges
ing the C4 content of the C3 propylene feed to the bottons liquid recycled from T-2 to T- Will
less than 0.10% is a very important asset for contain i0 to 30% by weight of these liquid C3
producing high quality isopropyl alcohol eco hydrocarbons.
nomically. 75 The Operation in the lower part of the pres
 5 2,657,248
sure ranges is permitted when the initial feed 6
has a low content of the C3 acetylenes and C4 and propane vapors from said higher pressure
hydrocarbons, e. g., 0.1 to 0.2 weight per cent, fractional distillation zone, partially condensing
and such a feed may be supplied to the unit overhead vapors from Said higher pressure frac
through line 22 so as to enter the high pressure tional distillation zone into condensate, separat
tower T-2 first. ing uncondensed propylene and propane Wapors
In the operations described the C3 acetylenes from said condensate, refluxing said condensate
are present in the C4 bottoms withdrawn from to an upper part of said higher pressure frac
the low pressure tower T ——l, but if desired a, por tional distillation Zone, passing bottoms liquid
tion of the bottoms liquid passed from T-2 to from the higher pressure fractional distillation
O zone
T-I may be purged or treated to obtain a selec into said first mentioned fractional distilla
tive removal of acetylenes. tion Zone and Withdrawing liquid bottoms con
The invention claimed is: taining Separated C4 hydrocarbons and C3 acety
1. The process of separating C4 hydrocarbons lenes therefrom.
and C3 acetylene contaminants from a C3 hydro 4. In a production of high quality isopropyl
carbon propylene fraction to obtain purified pro alcohol from propylene in the presence of Sul
pylene suitable for producing high quality is0 furic acid, the steps of pretreating a propylene
propyl alcohol, which comprises distilling sub fraction that contains small amounts of C4 hy
stantially all propylene and propane from Said drocarbons and C3 acetylenes as impurities which
fraction together with a minor portion of the comprises distilling the propylene from said frac
C4 hydrocarbons in a fractional distillation Zone, tion. With a minor portion of said impurities in a
passing thus distilled hydrocarbons into a higher relatively lower pressure fractional distillation
pressure fractional distillation Zone, condensing ZOne under a pressure Which maintains the major
substantially all C4 hydrocarbons and acetylenes portion of the C4 hydrocarbons and the C3 acet
with a substantial portion of C3 hydrocarbons in ylenes in liquid phase, passing the distilled pro
said higher pressure fractional distillation zone, pylene With Said distilled inpurities into a higher
withdrawing overhead from Said higher pressure preSSure fractional distillation Zone, maintaining
fractional distillation Zone propylene vapors Sub a Substantial portion of the propylene in liquid
stantially free of acetylenes and C4 hydrocarbon phase with said impurities in said higher pres
impurities, returning to the first mentioned frac 30 Sure fractional distillation zone, withdrawing
tional distillation Zone liquid bottoms from the overhead from said higher pressure fractional dis
higher pressure fractional distillation Zone, and tillation zone a propylene-rich fraction substan
removing separated C4 hydrocarbons and C3 tially free of said impurities for hydration to
acetylenes in liquid bottoms withdrawn from the the alcohol, withdrawing from said higher pres
first mentioned fractional distillation zone. Sure fractional distillation Zone a liquid residue
2. In the preparation of a propylene feed suit 35 containing liquid propylene with said impurities,
able for hydration to odorless isopropyl alcohol, passing said liquid residue from said higher pres
the steps of Separating C4 hydrocarbon impuri Sure to said relatively lower pressure fractional
ties from a C3 hydrocarbon fraction of propyl distillation Zone, and withdrawing said impuri
ene and propane, Which Comprises distilling from 40 ties in liquid phase from said relatively lower
said C3 hydrocarbon fraction substantially all its pressure fractional distillation zone.
propylene and propane Components. With a minor 5. In the production of high quality isopropyl
amount of the C4 hydrocarbons under a pressure alcohol by hydration of propylene in the pres
in the range of 300 to 330 pounds per Square inch ence of sulfuric acid, the steps of separating by
gauge, passing resulting distillate from said frac 45 distillation a propylene-rich fraction containing
tional to a higher pressure fractional distilla between 0.1 and 1% by Weight of C4 hydrocar
tion Zone, distilling propylene and propane sub bons and from 0.05 to 0.15% C3 acetylenes from
stantially free of C4 hydrocarbons from the dis a commercial propylene fraction, partially con
tillate in Said higher pressure fractional distilla densing under increased pressure from said pro
tion Zone at a pressure in the range of 330 to 350 O pylene-rich fraction a condensate containing 10
pounds per Square inch gauge, passing bottoms to 60 Weight per cent of C3 hydrocarbons with a
liquid containing a substantial amount of C3 hy portion of the C4 hydrocarbons and C3 acetylenes
drocarbons from said higher pressure fractional So as to leave the remaining propylene-rich vapor
distillation Zone to the first mentioned fractional fraction. With a C4 hydrocarbon content of less
distillation zone, and withdrawing bottoms liquid than 0.1 Weight per cent and a C3 acetylene con
COntaining Separated C4 hydrocarbons from said 55 tent of less than 0.05 weight per cent.
first mentioned fractional distillation zone.
3. The process of Separating C3 acetylenes and ALBERT. P. GIIRAITIS.
C4 hydrocarbon impurities from a C3 hydro MACK C. FUQUA.
carbon fraction of propylene and propane, which 60 References Cited in the file of this patent
comprises fractionally distilling propylene and
propane With a minor portion of said impurities UNITED STATES PATENTS
under a pressure in the range of about 300 to 330 Number Name Date
pounds per Square inch gauge in a fractional dis 1,465,600 Eldred ------------ Aug. 21, 1923
tillation Zone having a top temperature of 130° 65 1,957,818 Carney ------------------ May 8, 1934
F. and a bottoms temperature in the range of 2,055,720 Francis ------------ Jan. 9, 1940
240 to 255 F., refluxing a portion of the result 2,222,276 Babcock ---------- ???. 19, 1940
ing distillate in the upper part of said fractional 2,370,948 Gadwa ------------- Mar. 6, 1945
distillation Zone, passing a remaining portion of 2,409,773 I?UItem --------------------- Oct. 22, 1946
the resulting distillate into an intermediate part 2,431,685 Cade -------------- Dec. 2, 1947
of a higher pressure fractional distillation zone 2,514,294 Fupp -------------- July 4, 1950
in which a pressure of 330 to 350 pounds per FOREIGN PATENTS
Square inch gauge is maintained with top tem Number Country Date
perature of 130 F. and a bottom temperature in
the range of 180° to 220 F., removing propylene 75 297,842 Great Britain ------ Aug. 1, 1929
586,831 Great Britain ------ Apr. 2, 1947