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Патент USA US2509881

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May 30, 1950
l.. A. NlcoLAl ErAL
Filed June 20, 1947
E35 ...1147 ß
Patented May 30, 1950
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 Claims. (Cl. 2611-546)
This invention relates to improvements in the
The preheater is connected by conduit 5 to
pyrolysis chamber 6 which may be a. single tube or
coil or other type of enclosed chamber. The coil
may be copper or other desired alloy, such as
stainless steel containing a large amount of
chromium. Chamber 8 is connected by line ‘I to
vproduction of organic compounds of the type of
ketone fcnozco) and its homologs and to the
production of acid anhydrides, such as acetic
anhydride, therefrom.
Various methods for the production of ketene
absorption tower 8 which may be of any con
venient contruction.
Tower 8 is provided with conduit means 8 for
or' acid anhydrides. For example, acetone may
introducing acetic acid to be reacted with the
be cracked at high temperatures to yield ketene
ketene and with draw-off means I0 at the base of
itself and methyl ethyl ketone may be so treated
the column connected with fractionator II. The
to yield a mixture of methyl ketene and ketene.
upper part of the absorber is provided with vapor
The ketenes are highly reactive compounds and
take-off means I2 connecting with condenser I3.
are used as intermediates in the production of a.
Fractionator II is provided with bottom draw-off
large number of organic compounds. For ex
means I4 and vapor-take-off conduit I5 which
ample, they may be reacted with acids to yield
passes through condenser I6 to the top of ab
anhydrides, with alcohols to yield esters, etc.
sorber 8. Condenser I3 is connected by line Il
A particularly valuable reaction is that of
ketene itself with acetic acid to yield acetic an 20 to scrubber I8 which is provided at its top with
means I9 for introducing scrubbing liquid and.
hydride which is useful in the preparation of cel
with vent line 20 for removing gases and connects
lulose esters. In this process acetone is cracked
at its bottom with line 9 into the absorber 8.
at high temperatures and at short contact times
Means are provided In absorber 8 and fractionator
to produce ketene which is then passed counter
I3 for supplying heat, such as steam coils 2I and
currently to acetic acid ina tower to produce
acetic anhydride. Unreacted acetone and some 252 2
may be further understood by
acetic acid are removed overhead and acetic an
consideration of the following more detailed de
hydride-acetic acid mixture is taken oil' the bot
scription. This description is set forth for the
tom. The overhead is condensed to separate ace
of illustrating the invention; hence it is
tone which may contain acetic acid from ñxed
to be understoodthat the specific values and
gases and the acetone is recycled. However,
materials described `are not to be construed as
under normal conditions of operation the yield
limiting the invention.
or its homologs are known.
In general, these
methods comprise cracking ketones, organic acid
of permanent gases (CO, CO2, CH4 and C2114)
and the vapor pressure of acetone are such that
about 7.5% of the total acetone feed to the fur
nace is lost with the eiiiuent gases when the ace
Referring, therefore, again to the drawing,
acetone is vaporized and preheated to 1150° F. in
35 preheater l and then passed to pyrolyzer 6 where
it is heated to a temperature of 1300° F. with a
mass velocity of 25 lbs. of acetone per second per
square foot to give a contact time of 0.3 to 0.5 of a
tone is condensed at 80° F. with cooling water.
It is, therefore, the main object of this inven
tion to provide a process in which the loss of
acetone in the eiiluent gases is minimized or en
tirely avoided.
second. Under these conditions, about 15% of the
40 acetone is converted with `about 80% selectivity
Further objects of this invention will be ap
parent to those skilled in the art from the follow
ing description taken in connection with the
drawing, which is a diagrammatic side elevation 45
view in the nature of a iiow sheet showing one
form of apparatus arrangement which might be
employed in carrying out this invention.
Referring more specifically to the drawing,
numeral 2 represents vaporizer means for the 50
to ketene. In order to prevent polymerization of
ketene, the eilluent gases from the pyrolysis
chamber are immediately introduced by line ‘I
into the bottom of absorber 8 where they are
passed countercurrent to glacial acetic acidin
troduced through line 9. The bottom ofthe ab
sorber acts also as a soaker for the completionof
the reaction between the ketene andtheïacetic
acetone, which may be a simple coil as shown or
acid, because, while ketene readily reacts with
acetic acid to form the anhydride, a deñnite time
is required before the partial pressure of the
a metal still pot or the like. The vaporizer is
connected by line 3 to preheater l which likewise
ketene above the solution is'reduced to zero. ‘I‘he
absorption tower also acts as a heat exchanger
may be of simple ` construction,
merely an `s-coil or the like.
with the cold fresh acid entering through line 3
and the recycle acid from the condenser I8, ab
sorbing the heat of reaction and further cooling
the ketene vapors entering through line 1. As a
result the effluent vapors in the top of the tower
ture of at least +80° F. wherein only a portion
oi' the ketone is condensed. recycling said con
densed ketone to the pyrolysis step, passing a
gaseous stream containing fixed 'gases and re
maining uncondensed ketone vapor from the
cooling zone to a scrubbing zone maintained at
contact the cold product liquor entirely free of
acetone and acetone will tend to concentrate
somewhere in the middle section of the tower, but
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 I, 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 10 acid introduced thereto to remove the ketone
dride is removed from the bottom of the absorber
substantially completely, removing fixed gases
through line I0 and passed to fractionator II
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 I5 and con 15 and passing said ketone enriched acetic acidy
denser I6 and the latter withdrawn as product.
stream to the absorption zone. '
Part of the condensate from ~condenser I6 is re
2. In a process for preparation of acetic an
turned to fractionator II through line I5A for
hydride by pyrolyzing acetone to ketene, imme
diately passing the total hot gaseous pyrolyzed
Unconverted acetone, some acetic acid and 20 products including the ketene, unreacted acetone,
ñxed gases (largely methane, carbon monoxide
and fixed gases into an absorption zone wherein
and ethylene) are passed overhead from absorbery
said products are contacted countercurrent with
8 through line I2 to condenser I3 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 ei'iiuent 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 I1 to scrubber I8 where they
vapor from the cooling zone to a scrubbing zone
are contacted countercurrently with glacial acetic 35 maintained at a pressure of from atmospheric
acid introduced by line I9. The temperature in
to 10 psig. and a temperature of from 60° to 100°
this scrubber should be maintained as 10W 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 40 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
frigeration, the eiiluent gases would have to be
chilled to -5° F.
The nature and objects of the present inven
tion having been thus described and illustrated,
50 a fractionating zone wherein the acetic acid is
separated from the acetic anhydride and at least
a part of said acetic acid is returned to an upper
part of the absorption zone.
what is claimed as new and useful and is desired 55
to be secured by Letters Patent is:
1. In a process for preparing an aliphatic acid "
anhydride by pyrolyzing a ketone to the corre
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
sorption zone wherein said products are con
tacted with acetic acid, and removing a liquid
mixture of acetic acid anhydride and acetic acid
from the bottom of the absorption zone, the im
provement which comprises passing a vapor
stream of the unreacted ketone and fixed gases
substantially free of ketene, from the absorption
zone to a cooling zone maintained at a tempera
Rice _____________ __ Feb. 21, 1933
Law ______________ __ Jan. 2, 1934
Steik ____________ __ Nov. 23, 1937
Gleason __________ __ Nov. 7, 1939
-Hull _____________ _.. Feb. 25, 1941
Nadeau et al ...... __ Mar. 18, 1941
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