May 30, 1950 L. A.

NICOLAI ETAL 2,509,877

PROCESS FOR PREPARING ACETIC ANHYDRIDE
Filed June 20, 1947
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Patented May 30, 1950 2,509,877
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UNITED STATES PATENT OFFICE

2,509,877
PRocess FoR PREPARING ACETIC
ANY ORDE
Lloyd A. Nicolai and William G. Daroux, Baton
Rouge, La., assignors to Standard Oil Develop
ment Company, a corporation of Delaware
Application June 20, 1947, Serial No. 755,868
3 Cains. (C. 260-546)

This invention relates to improvements in the The preheater is connected by conduit 5 to

production of organic compounds of the type of pyrolysis chamber 6 which may be a single tube or
ketene (CH2:CO) and its homologs and to the coil or other type of enclosed chamber. The coil
production of acid anhydrides, such as acetic may be copper or other desired alloy, such as
anhydride, therefrom. stainless steel containing a large amount of
Warious methods for the production of ketene chromium. Chamber 6 is connected by line 7 to
or its homologs are known. In general, these absorption tower 8 which may be of any con
methods comprise cracking ketones, organic acid venient contruction.
or acid anhydrides. For example, acetone may Tower 8 is provided with conduit means 9 for
be cracked at high temperatures to yield ketene introducing acetic acid to be reacted with the
itself and methyl ethyl ketone may be so treated ketene and with draw-off means 0 at the base of
to yield a mixture of methyl ketene and ketene. the column connected with fractionator . The
The ketenes are highly reactive compounds and upper part of the absorber is provided with vapor
are used as intermediates in the production of a take-off means 2 connecting with condenser 3.
large number of organic compounds. For ex Fractionator is provided with bottom draw-off
ample, they may be reacted with acids to yield means 4 and vapor-take-off conduit 5 which
anhydrides, with alcohols to yield esters, etc. passes through condenser 6 to the top of ab
A particularly valuable reaction is that of sorber 8. Condenser 3 is connected by line
ketene itself with acetic acid to yield acetic an 20 to Scrubber 8 which is provided at its top with
hydride which is useful in the preparation of cel means f for introducing scrubbing liquid and
lulose esters. In this process acetone is cracked with vent line 20 for removing gases and connects
at high temperatures and at short contact times at its bottom with line 9 into the absorber 8.
to produce ketene which is then passed counter Means are provided in absorber 8 and fractionator
currently to acetic acid in a tower to produce 25 22.f3 for supplying heat, such as steam coils 2 and
acetic anhydride. Unreacted acetone and Some
acetic acid are removed overhead and acetic an The invention may be further understood by
hydride-acetic acid mixture is taken off the bot consideration of the following more detailed de
to. The overhead is condensed to Separate ace Scription. This description is set forth for the
tone which may contain acetic acid from fixed purpose of illustrating the invention; hence it is
gases and the acetone is recycled. However, to be understood that the specific values and
under normal conditions of operation the yield materials described are not to be construed as
of permanent gases (CO, CO2, CH4 and Caha) limiting the invention.
Referring, therefore, again to the drawing,
and the vapor pressure of acetone are such that acetone is vaporized and preheated to 1150° F. in
about 7.5% of the total acetone feed to the fur 35 preheater 4 and then passed to pyrolyzer 6 where
nace is lost with the effluent gases when the ace it is heated to a temperature of 1300° F. with a
tone is condensed at 80° F. with cooling water. mass velocity of 25 lbs. of acetone per second per
It is, therefore, the main object of this inven Square foot to give a contact time of 0.3 to 0.5 of a
tion to provide a process in which the loss of Second. Under these conditions, about 15% of the
acetone in the effluent gases is minimized or en 40 acetone is converted with about 80% selectivity
tirely avoided. to ketene. In order to prevent polymerization of
Further objects of this invention will be ap ketene, the effluent gases from the pyrolysis
parent to those skilled in the art from the follow chamber are immediately introduced by line T.
ing description taken in connection with the into the bottom of absorber 8, where they are
drawing, which is a diagrammatic side elevation 45 passed countercurrent to glacial acetic acid in
view in the nature of a flow sheet showing one troduced through line 9. The bottom of the ab
form of apparatus arrangement which might be Sorber acts also as a soaker for the completion of
employed in carrying out this invention. the reaction between the ketene and the acetic
Referring more specifically to the drawing, acid, because, while ketene readily reacts. With
numeral 2 represents vaporizer means for the 5) acetic acid to form the anhydride, a definite time
acetone, which may be a simple coil as shown or is required before the partial pressure of the
a metal still pot or the like. The vaporizer is ketene above the Solution is reduced to zero. The
connected by line 3 to preheater which likewise a absorption tower also acts as a heat exchanger
may be of simple construction, Comprising with the cold fresh acid entering through line 9
merely an S-coil or the like. and the recycle acid from the condenser 16, ab
 2,509,877
3 4.
sorbing the heat of reaction and further cooling ture of at least --80 F. wherein only a portion
the ketene vapors entering through line . As a of the ketone is condensed, recycling said con
result the effluent vapors in the top of the tower densed ketone to the pyrolysis step, passing a
contact the cold product liquor entirely free of gaseous stream containing fixed gases and re
acetone and acetone will tend to concentrate maining uncondensed ketone vapor from the
somewhere in the middle Section of the tower, but cooling zone to a scrubbing zone maintained at
by reboiling any acetone that reaches the bottom a pressure of from atmospheric to 10 psig, and a
of the tower by means of steam coil 2, eventually temperature of from 60° to 100° F. wherein said
all of the acetone must leave in the top gases. A gaseous stream is contacted with liquid acetic
mixture of acetic acid and product acetic anhy O acid introduced thereto to remove the ketone
dride is removed from the bottom of the absorber substantially completely, removing fixed gases
through line O and passed to fractionator substantially free of ketone from said scrubbing
where separation is effected between the acetic zone, removing a ketone enriched acetic acid
acid and the acetic anhydride, the former being stream from the bottom of the scrubbing zone,
recycled to the absorber through line 5 and con 15 and passing said ketone enriched acetic acid
denser 6 and the latter withdrawn as product. stream to the absorption zone.
Part of the condensate from condenser 6 is re 2. In a process for preparation of acetic an
turned to fractionator through line 5A for hydride by pyrolyzing acetone to ketene, imme
reflux. diately passing the total hot gaseous pyrolyzed
Unconverted acetone, Some acetic acid and 20 products including the ketene, unreacted acetone,
fixed gases (largely methane, carbon monoxide and fixed gases into an absorption zone wherein
and ethylene) are passed overhead from absorber Said products are contacted countercurrent with
8 through line 2 to condenser 3 where the bulk acetic acid, and removing a mixture of acetic an
of the acetone is condensed and recycled through hydride and acetic acid from the bottom of the
line 23. However, under the cracking conditions 25 absorption zone, the improvement which com
cited above giving a 15% conversion of acetone prises passing a vapor stream of unreacted ace
with 80% selectivity to ketene, the yield of fixed tone and fixed gases substantially free of ketene,
gases and the vapor pressure of acetone are such from the absorption zone to a cooling zone main
that about 7.5% of the total acetOne feed to the tained at a temperature of at least --80° F. where
furnace is lost with the effluent gases in the usual 30 in only a major portion of the ketone is liquefied,
method of water cooling. Accordingly, it is a recycling said liquefied acetone to the pyrolysis
particular feature of this invention to pass the step, passing a gaseous stream containing said
mixture of fixed gases and acetone from the fixed gases and remaining uncondensed acetone
condenser by line 7 to scrubber 8 where they vapor from the cooling zone to a scrubbing zone
are contacted countercurrently with glacial acetic maintained at a pressure of from atmospheric
acid introduced by line 9. The temperature in to 10 psig, and a temperature of from 60° to 100°
this scrubber should be maintained as low as poS F. wherein said gaseous stream is contacted
sible without refrigeration down to the freezing Countercurrently with a stream of acetic acid to
point of the acid (60° F.). While it is possible remove the acetone substantially completely, re
to reduce the loss of acetic acid to a minimum 4) moving fixed gases Substantially free of acetone
by increasing the pressure, other considerations, from the top of said scrubbing zone, removing
such as the optimum cracking pressure, limit the an acetone enriched acetic acid stream from the
pressure to atmospheric. In any case, regard bottom of the scrubbing zone, and passing said
less of the pressure and at temperatures between acetone enriched acetic acid stream to an upper
60° F. and 190° F., the loss of acetic acid will be part of the absorption zone.
less than the loss of acetone at 80° F. Thus, the 3. A process such as that defined in claim 2
practical limits of pressure and temperature in in which, as an additional improvement, the
the scrubber are atmospheric to 10 lbs./sq. in. mixture of acetic anhydride and acetic acid from
gauge, and 60° to 100° F. In order to effect the the bottom of the absorption zone is passed to
Same net recovery of valuable product by re 50 a fractionating zone wherein the acetic acid is
frigeration, the effluent gases would have to be separated from the acetic anhydride and at least
chilled to -5° F. a part of said acetic acid is returned to an upper
The nature and objects of the present inven part of the absorption zone.
tion having been thus described and illustrated, LLOYD A. NICOLA.
what is claimed as new and useful and is desired 55
to be secured by Letters Patent is: WILLIAM G. DAROUX.
1. In a process for preparing an aliphatic acid
anhydride by pyrolyzing a ketOne to the corre REFERENCES CTED
sponding ketene, immediately passing the hot The following references are of record in the
gaseous pyrolyzed products including the ketene, 60 file of this patent:
unreacted ketOne, and fixed gases into an ab UNITED STATES PATENTS
sorption zone wherein said products are con
tacted with acetic acid, and removing a liquid Number Name Date
mixture of acetic acid anhydride and acetic acid 1,898,687 Rice --------------- Feb. 21, 1933
from the bottom of the absorption zone, the im 85 1942,110 Law ---------------- Jan. 2, 1934
provement which comprises passing a vapor 2,099,909 Steik -------------- Nov. 23, 1937
stream of the unreacted ketone and fixed gases 2,178,752 Gleason ------------ Nov. 7, 1939
substantially free of ketene, from the absorption 2,232,705 Hull --------------- Feb. 25, 1941
Zone to a cooling Zone maintained at a tempera 2,235,561 Nadeau et al. ------- Mar. 18, 1941