United States Patent (19) 11) 4,381,407

Bremus et al. (45) Apr. 26, 1983

54 PROCESS FOR THE CONTINUOUS 56) References Cited
PRODUCTION OF TRACETN U.S. PATENT DOCUMENTS
3,674,839 7/1972 Vogt et al.......... S60/263
75 Inventors: Norbert Bremus, Langenfeld; 3,776,948 12/1973 Kleemann et al................... 560/263
Gerhard Dieckelmann, Hilden; Lutz
Jeromin, Disseldorf-Holthausen; Primary Examiner-Vivian Garner
Wolfgang Rupilius, Attorney, Agent, or Firm-Hammond & Littell,
Disseldorf-Urdenbach; Hartwig Weissenberger and Muserlian
Schitt, Disseldorf-Benrath, all of 57 ABSTRACT
Fed. Rep. of Germany
A process for the continuous production of triacetin
consisting essentially of continuously charging liquid
73 Assignee: Henkel Kommanditgesellschaft auf glycerol into a first liquid reaction area through which
Aktien, Disseldorf-Holthausen, Fed. acetic acid vapors and water vapors flow, said liquid
Rep. of Germany reaction area being divided into a number of separate
individual areas through which liquid glycerol and
21 Appl. No.: 228,452 liquid acetin reaction products flow in one direction and
gaseous acetic acid and water flow in a countercurrent
direction, continuously charging acetic acid vapor to a
(22 Filed: Jan. 26, 1981 separate individual area where said liquid mixture has
an OH number of less than 600, continuously separating
30. Foreign Application Priority Data a liquid mixture of acetins and water having an OH
Feb. 8, 1980 (DE Fed. Rep. of Germany....... 3004660 number of less than 600, continuously passing said liquid
mixture into a second liquid reaction area, continuously
adding thereto liquid acetic acid anhydride in an
51) int. Cl. ...................... CO7C 67/08; CO7C 67/54; amount sufficient to react with water dissolved in said
CO7C 69/18 liquid mixture to form acetic acid and to react with
52 U.S. Cl. .................................... 560/263; 202/158; monoacetin and diacetin present to form triacetin and
203/DIG. 6; 560/248; 562/607; 562/608 continuously recovering triacetin.
58) Field of Search ................ 202/158; 560/263, 248;
562/607, 608; 203/DIG. 6, 16 10 Claims, 7 Drawing Figures
U.S. Patent Apr. 26, 1983 Sheet 1 of 4 4,381,407

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an
U.S. Patent Apr. 26, 1983 Sheet 2 of 4 4,381,407

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U.S. Patent Apr. 26, 1983 Sheet 3 of 4 4,381,407

80CK FLOW DAGRAM

F G. 6
33 K9/h WATER
1 Kg/h ACETIC ACID
.088 Kno/h
100 Kg/h
GLY CERO

ESTERF CAT ON 3.33 Kino/h

O. 433 Knol/h e
26 Kg/h 200 kg/h
ACECACD ACE C A CD

96 Kg/h ACETN (OH- do =549)

88 Kg/h ACETIC ACD
8 kg/h WATER

.42 Knol/h 0.47 kmol/h

45 kg/h FINA ACETYLATION 5 KgAh
ACETIC ACD ACET IC ACID
A NHYDRDE A NHYDROE

237 Kg/h TRACET IN

200 Kg/h ACETIC ACID
15 kg/h ACETIC ACID ANHYDRIDE

RECT F CAT ION

237 kg/h TRIACET IN

.088 Kmol/h
U.S. Patent Apr. 26, 1983 Sheet 4 of 4 4,381,407

BLOCK FOW DAGRAM

F G 7 2.78 Kmol/h = 50Kg/h WATER

0.033 Kmol/h = 2Kg/h ACETIC ACID
.088K mo/h
100 Kq/h
glycero
2.32 Kmol/h ESTERIFICATION
39 Kg/h a
2.5 Kmol/h
29 Kq/h
ACETIC ACD ACETIC ACID

223 Kg/h ACETIN (OH- No = 83)

90 Kg/h ACETIC ACiD
3 kg/h 0

0.49 Kmo/h 0.049 KnO/h

50 kg/h 5 Kq/h
FINAL ACETYLATION
A C E C A CD ACETIC ACD
A NHYDR DE ANHYD RIDE

237 Kg/h TRACET IN

29 Kg/h ACETIC ACID
5 Kg/h ACETIC ACID ANHYDRIDE

RECT FCAT ON

237 kg/h TRACET IN

O88 Kno/h
 4,381,407 2
1.
second liquid reaction area, continuously adding
PROCESS FOR THE CONTINUOUS thereto liquid acetic acid anhydride in an amount suffi.
PRODUCTION OF TRACETIN cient to react with water dissolved in said liquid mixture
to form acetic acid and to react with monoacetin and
BACKGROUND OF THE INVENTION 5 diacetin present to form triacetin, continuously recover
This invention relates to a continuous process for the ing triacetin, continuously passing vaporized acetic acid
preparation of triacetin from glycerol, acetic acid and formed into said separate individual area where said
acetic acid anhydride, liquid mixture has an OH number of less than 600, and
A discontinuous process for the preparation of triace continuously recovering a mixture of water vapors and
O acetic acid vapors having a content after condensation
tin in which glycerol and acetic acid anhydride in a
molar ratio of 1:3 are reacted at 130 C, to 135 C., is of less than 3% by weight of acetic acid.
known from German Patent Specification DE-PS No. These and other objects of the invention will become
347,897. In this reaction, for each mol of reacted glyc more apparent as the description thereof proceeds.
erol, 3 mols of acetic acid are produced for which there 15 THE DRAWINGS
is generally hardly any way of utilization, making this
method unsuitable for the large-scale production of FIG. 1 shows a flow diagram for the continuous
triacetin. production of triacetin;
Also known are discontinuous methods for the prepa FIG. 2 shows a longitudinal section of a plate of a
ration of triacetin from glycerol and acetic acid, as can reactor which can be employed;
be learned from the journal, Seifen-Ole-Fette-Wachse, FIG.3 shows a view from above of one half of a plate
1962, pp. 597-602. Since the reaction equilibrium is on of the reactor;
the side of the starting materials in this reaction, the FIG. 4 shows an enlarged view of a bubble cap with
water produced during the esterification reaction must two alternate gas exit ports;
be removed continuously from the reaction mixture to FIG. 5 shows an enlarged view of a bubble cap with
keep the required acetic acid to a reasonable amount. 25 a diaphragm inserted in the neck of the inner bubble;
These methods require long reaction times and there FIG. 6 shows a block flow diagram of one embodi
fore have a high energy consumption and a poor utiliza ment of the invention;
tion of the reactor capacity. . FIG. 7 shows a block flow diagram of another em
As can be seen from Seifen-Ole-Fette-Wachse, 1962,
p. 598, the esterification reaction can be accelerated, 30 bodiment of the invention.
especially in the low temperature range from 100 to DESCRIPTION OF THE INVENTION
160 C., by acid catalysts. The catalyst must have a The subject of the invention is a continuous process
lower vapor pressure than glycerol to prevent its accu for the preparation of triacetin by the reaction of glyc
mulation in the vapor phase. erol with acetic acid and acetic. acid anhydride at ele
In addition, German Published Application DE-OS 35 vated temperature and, optionally, in the presence of
1905 880 describes the production of triacetin from the catalysts, which is characterized in that the reaction
reaction of allyl acetate with acetic acid and acetic acid partners are reacted with each other in a continuous
anhydride in the presence of a catalyst. Now it was countercurrent process, for which purpose liquid glyc
found that the disadvantages of the known methods can erol is inserted in an ascending stream of superheated
be largely eliminated by using the continuous process
for the preparation of triacetin described below. acetic acid vapor at a pressure of 0.2 to 30 bar and a
temperature of 100' to 250 C. in an esterification col
OBJECTS OF THE INVENTION umn with a number of plates, the reaction time of the
An object of the present invention is the development liquid reaction mixture amounting to at least one hour
of a continuous process for the production of triacetin 45 and acetic acid anhydride is added to the descending
from glycerol, acetic acid and acetic acid anhydride reaction mixture upon reaching an OH-number of less
wherein only small amounts of acetic acid are removed than 600 at the respective plate of the reaction column
unreacted. or in a correspondingly designed second reactor, in an
Another object of the present invention is the devel amount that the water dissolved at this point in the
opment of a process for the continuous production of 50 reaction phase can be converted quantitatively into
triacetin consisting essentially of continuously charging acetic acid and the monoacetin and diacetin present can
liquid glycerol into a first liquid reaction area through be converted into triacetin.
which acetic acid vapors and water vapors flow, said More particularly, the present invention relates to a
liquid reaction area being divided into a number of process for the continuous production of triacetin con
separate individual areas through which liquid glycerol 55 sisting essentially of continuously charging liquid glyc
and liquid acetin reaction products flow in one direction erol into a first liquid reaction area through which
and gaseous acetic acid and water flow in a countercur acetic acid vapors and water vapors flow, said liquid
rent direction, continuously charging acetic acid vapor reaction area being divided into a number of separate
to a separate individual area where said liquid mixture individual areas through which liquid glycerol and
has an OH number of less than 600, said liquid reaction 60 liquid acetin reaction products flow in one direction and
areas being maintained at a pressure of from 0.2 to 30 gaseous acetic acid and water flow in a countercurrent
bar and a temperature of from 100 to 250° C., the num direction, continuously charging acetic acid vapor to a
ber of said separate individual areas and the amount of separate individual area where said liquid mixture has
liquid glycerol and gaseous acetic acid charged being so an OH number of less than 600, said liquid reaction
selected that the total contact time of the reactants is at 65 areas being maintained at a pressure of from 0.2 to 30
least one hour, continuously separating a liquid mixture bar and a temperature of from 100 to 250 C., the num
of acetins and water having an OH number of less than ber of said separate individual areas and the amount of
600, continuously passing said liquid mixture into a liquid glycerol and gaseous acetic acid charged being so
 4,381,4O7 4.
3
selected that the total contact time of the reactants is at for the performing of the esterification. The construc
least one hour, continuously separating a liquid mixture tion and arrangement of the bubbles leads to a uniform
of acetins and water having an OH number of less than distribution of the vapor phase over the effective col
600, continuously passing said liquid mixture into a umn cross-section, reduces pulsating liquid currents and
second liquid reaction area, continuously adding lends a high rate of flow to the vapor upon emergence
thereto liquid acetic acid anhydride in an amount suffi from the bubble. It is recommended that the vapor
cient to react with water dissolved in said liquid mixture penetration area be so selected that when air is passed
to form acetic acid and to react with monoacetin and through, its velocity is about 4 to 30 meters per second,
diacetin present to form triacetin, continuously recover preferably 15 meters per second, in order to facilitate
ing triacetin, continuously passing vaporized acetic acid 10 the mixing of the reaction partners.
formed into said separate individual area where said A suitable construction of the cross-sections for the
liquid mixture has an OH number of less than 600, and penetration of the vapor through the bubbles consists of
continuously recovering a mixture of water vapors and at least 4 vertical slits with a width of 2 to 5 mm and a
acetic acid vapors having a content after condensation height of 5 to 20 mm, arranged in the bubble close to the
of less than 3% by weight of acetic acid. 15 plate, instead of the circular orifices. With the high
When the process takes place in the absence of cata liquid levels on the plates and the low vapor loads, each
lysts, the reaction pressure preferably lies in the range slit is filled with vapor only to a small extent, while the
from 3 to 30 bar and the reaction temperature in the remaining lower part of the slits is closed by the liquid
range from 180' to 250 C. In the presence of catalysts, standing on the plate. The slits have the advantage over
the reaction pressure can be lower and preferably from 20 the orifices in that they clog less easily. In addition, a
0.2 to 3 bar and the reaction temperature is likewise larger penetration area always is automatically available
lower, preferably from 100' to 180 C. when larger amounts of vapor are present, since the
Acid esterification catalysts are suitable for the pro vapor can blow open a larger cross-section, if neces
cess according to the invention, particularly p-toluene sary. It is also advantageous that the intake and outlet
sulfonic acid, concentrated sulfuric acid, trifluoroacetic 25 weirs have at least the height of the outlet tube that
acid, potassium hydrogen sulfate, aluminum sulfate or determines the level of the liquid and that they have slits
zinc acetate. The use of p-toluenesulfonic acid as cata close to the plate, through which the liquid can flow in
lyst is preferred. The amount of catalyst, based on the and drain out. Another suitable part of the construction
amount of glycerol used, is 0.01% to 0.5% by weight. is a diaphragm in the neck of the inner bubble with an
More particularly, therefore, the reaction can be con 30 orifice of 2 to 15 mm.
ducted in the presence of from 0 to 0.5% by weight of For larger column plates (diameter exceeding 300
an acid esterification catalyst, based on the amount of mm), the liquid gradient forming more strongly on the
glycerol charged. The acid esterification catalyst is plate must be taken into consideration for the configura
charged with the glycerol. tion of the bubbles. A uniform distribution of the vapor
Glycerol with an OH number of 1,828 is preferably 35 over all bubbles of the plate is guaranteed only when the
used for the process according to the invention. Acetic so-called dry pressure loss of the plate (which is mea
acid is used in a molar ratio to glycerol of 2.5:1 to 5:1. sured when the plate is penetrated by the vapor and no
The amount of acetic acid anhydride that is added to liquid remains on it) is at least twice as great as the
the reaction mixture in the lower third of the column, or hydrostatic difference in height between intake and
in the second reactor, is 0.1 to 1.5 mol per mol of glyc 40 outlet caused by the liquid gradient. The necessary dry
erol to be converted. pressure loss can be achieved by building a diaphragm
The preparation of triacetin by the process according with an orifice of 2 to 15 mm diameter into the neck of
to the invention takes place advantageously in the the inner bubble. The effectively necessary size of the
equipment for the liquid-vapor reactions described be diaphragm can be determined by a simple experiment.
low. The equipment consists of a reaction column with 45 The dry pressure loss also can be obtained by a suffi
a rectifying column added on the top, heat exchangers, ciently small space between the upper edge of the neck
storage containers, feeding pumps and connecting pipe of the inner bubble and the upper part of the outer
lines. bubble, which then amounts to 1 to 3 mm.
The reaction column is in the form of a bubble plate The process according to the invention and the con
column with at least 20 double bubble plates. The inner 50 struction of the reaction equipment are illustrated in the
bubble is needed for the adjustment of the dry pressure attached figures.
loss and for the immersion of the intake tube of the plate FIG. 1 shows a diagram of the process for the contin
above during the starting of the column. The outer uous preparation of triacetin (glycide triacetate).
bubble serves for the distribution of the vapor in the FIG. 2 shows a longitudinal section of a plate of the
liquid and provides the exchange surface for the sub 55 reactor.
stances. The entire surface of the bubbles on one plate FIG. 3 shows a view from above of of a plate of the
amounts to 10% to 30% of the surface lying between reactor.
the intake and outlet weir. The vapor penetration area FIG. 4 shows an enlarged view of a bubble cap with
through the bubbles set on the plates amounts to 0.3% two alternate gas exit ports.
to 3% of the inside column cross-section. The vapor 60 FIG. 5 shows an enlarged view of a bubble cap with
penetration surface is distributed over at least 4 orifices a diaphragm inserted in the neck of the inner bubble.
per bubble. The orifices have a diameter of 2 to 5 mm FIG. 6 shows a block flow diagram of one embodi
and are located on the periphery of the outer bubbles, 5 ment of the invention.
to 20 mm above the plate. The height of the outlet tube FIG. 7 shows a block flow diagram of another em
is at least 80 mm above the bubble plate. 65 bodiment of the invention.
This construction of the bubble plate column permits As shown in the skeletonized flow diagram of FIG. 1,
an extremely high liquid level on the plates at a low glycerol is pumped from storage container B3 with the
vapor load, resulting in the long contact time required aid of pump P3, via a heat exchanger W 4, where it is
 4,381,407
5 6
heated to the reaction temperature, and transferred formation of acetic acid. The acetic acid formed during
under the desired reaction pressure to the uppermost these two reactions is available for the esterification of
plate of reaction column K 1. Acetic acid is pumped glycerol, monoacetin and diacetin and is taken into
from storage container B 1 with pump P 1, via vapor consideration in the calculation of the amount of acetic
izer W 1 and superheater W 2 to beneath the bottom 5 acid to be added.
plate of reaction column K 1. The head products collecting at the head of column
The glycerol transferred onto the uppermost plate, K1 are removed as superheated vapor and rectified in
which may contain the catalyst, if desired, flows rectifier column K2. The glycerol, monoacetin and
through reaction column K 1 in a counter-current flow possibly diacetin present in the head product are con
to the ascending acetic acid vapor. The acetic acid 10 densed in column K2 and flow back into reactor K 1.
reacts with the glycerol or with already formed mono The head products which distill off and consist of the
acetin or diacetin, in dependence on the solubility of water of reaction and up to 3% by weight of acetic acid
acetic acid in the liquid phase on the individual plates. are condensed and supercooled in heat exchanger W 5,
Water, which is distributed between the liquid and the then reduced to atmospheric pressure via valve X1 and
vapor due to the phase equilibrium, is formed in these 15 drawn off via another heat exchanger W7 into storage
reactions. The water content in the liquid phase on the tank B 4. The amount of acetic acid contained in the
plates decreases with increasing conversion (expressed, distillate corresponds only to a minor part to the ini
for example, by the decrease of the OH number) from tially added molar excess of acetic acid. The runback
the head to the sump of the column K1, but it does not transferred to column K2 for separation is measured so
reach zero and counteracts the course of the various 20 that the superheating energy of the vapor flowing into
esterification reactions, especially the formation of tri column K 2 and the exothermy of the reaction on the
acetin, with water contents of up to 3% by weight in the uppermost plate of column K 1 are adequate for the
liquid reaction mixture found at the bottom of the col vaporizing of the runback.
umn K 1 or in the sump. This water content finally The reaction product is drained continuously from
would bring the esterification to a halt via the adjust- 25 the sump of column K 1 or from the final acetylation
ment of the reaction equilibrium. To prevent this, the reactor, cooled in heat exchanger W 6, its pressure is
invention calls for the feeding of acetic acid anhydride reduced via valve X 2 and it is piped into tank B 5.
from storage container B2 with the aid of pump P2, via Depending on the conversion and the chosen reaction
heat exchanger W 3, where it is heated to the reaction conditions, it contains from 20% to 40% by weight of
temperature, to a plate in the lower third of column K 30 acetic acid and from 1% to 5% by weight of acetic acid
1. This plate is chosen so that the glycerol coming from anhydride from the residue of the excess of acetic acid
above has a total degree of esterification of about 70% and/or acetic acid anhydride employed, in addition to
or more, that is, an OH number of less than 600. The
amount of the added acetic acid anhydride is such that triacetin as the desired product.
the water dissolved at this point in the liquid reaction 35 When the reaction is performed correctly, the reac
phase can be converted quantitatively into acetic acid tion product contains only traces of glycerol, monoace
and the monoacetin and diacetin present can be con tin, diacetin and water, so that the OH number normally
verted into triacetin. Relatively small amounts of acetic lies below 1. Pure triacetin can be obtained readily by
acid anhydride in the range of 0.1 to 1.5 mol per total distillation in a rectification column of the obtained
molar amount of glycerol to be converted are needed 40 crude product, since, at atmospheric pressure, acetic
for this purpose. acid boils at about 118 C., acetic acid anhydride boils at
As an alternative, the final acetylation with acetic about 140 C., and glyceryl triacetate (triacetin) boils at
acid anhydride can be performed in a separate, second about 258 C. Any catalyst that may still be present
reactor. In this case, the sump products from the esteri remains in the distillation residue.
fication column with an OH number of less than 600 are 45 According to the invention, the reaction column K1
fed into the acetylation reactor together with acetic is designed in such a manner that the acetic acid formed
acid anhydride. The acetic acid formed during the acet in the final acetylation is converted during the esterifi
ylation is pumped into tank B 1 in this case, for further cation so that no excess of acetic acid is formed during
esterification. Suitable as secondary acetylation reactors the entire process. The water of reaction formed during
are, for example, shorter bubble cap reactors compara- 50 the reaction is drawn off at the head of the column, and
ble to K 1 or tube reactors filled with packing or cas the column has the proper dimensions so that the acetic
cades of agitator vessels. acid vapor rising in the column reacts with the OH
The amount of acetic acid anhydride to be added in groups of the glycerol and the water of reaction above
the individual case depends, on the one hand, on the the uppermost plate contains only from 1% to 3% by
degree of esterification which, in turn, depends on the 55 weight of acetic acid. After a neutralization, the head
contact time and thus on the dimensions of the utilized products can be transferred to a biologic clarifying
reaction column K 1 and on the other hand, on the vessel without any prior, expensive separation of the
amount of the molar ratio of the added acetic acid to acetic acid from the water, which is necessary when
glycerol. higher concentrations of acetic acid are present in the
The acetic acid anhydride fed into the lower third of 60 head products.
reaction column K1 or a second reactor of correspond There exist physico-chemical interrelations between
ing dimensions reacts with the water present in the the distribution of the reaction over the esterification
liquid reaction phase and the water forming during the and final acetylation phases that are presented schemati
subsequent course of the esterification reactions and cally as follows. The block flow diagrams 1 and 2
removes this from the equilibrium with the simulta- 65 (FIGS. 6 and 7) show the interrelations for a conversion
neous formation of acetic acid. Part of the added acetic of 70%, up to an OH number of 549 (FIG. 6), and a
acid anhydride also reacts directly with the OH groups conversion of 90%, to an OH number of 183 (FIG. 7),
of the glycerol that are still not esterified, with the in the esterification step.
 1,407
7 8
Block flow diagrain (FIG. 5): 70% conversion in The respective total flow balance for the process at a
the esterification, 90% conversion in the esterification column can be seen
The given amounts are based on a feed of 100 kg/hr. in the block flow diagram 2 (FIG. 7). At otherwise
of glycerol (OH number= 1,828) and production of 237 identical reaction conditions, the reaction column must
kg/hr. of triacetin. In the esterification column, the 5 be extended by at least 10 plates to obtain the higher
glycerol, introduced at the top, is esterified with 26 conversion while keeping the low acetic acid concen
kg/hr. of fresh acetic acid and 200 kg/hr. of acetic acid tration in the head products. In contrast to the 70%
formed from acetic acid anhydride during the final conversion, the consumption of fresh acetic acid for the
acetylation, to an esterification degree of 70% and an esterification now is 139 kg/hr., while only 129 kg/hr.
OH number of 549, based on the pure glycerol with a O are now produced via the anhydride; therefore, the
molar excess of 0.46 mol of acetic acid. According to esterification proceeds at an excess of 1.i mol of acetic
the invention, the column is proportioned in such a acid per mol of glycerol. In addition, less anhydride is
manner that the water of reaction can be drawn off at used for the final acetylation, and the sump product of
the head of the column with a 3% by weight content of the esterification column contains only about 1% of
acetic acid maximum at a 70% conversion level. After 15 water at a conversion of 90%, so that a considerably
neutralization, these head products then may be piped smaller amount of water has to be converted to acetic
into a biologic clarifying vessel, for example, without acid in the final acetylation phase.
the need for an expensive separation of the acetic acid Corresponding to the higher conversion rate in the
from the water, which would be absolutely necessary at esterification reaction, the contact time in the final acet
relatively high concentrations of acetic acid in the head ylation phase is shorter, at otherwise identical reaction
products. conditions, in comparison to a 70% conversion. This
A 70% conversion in the esterification column with means that now only at least three reaction plates are
simultaneous maintaining of an acetic acid concentra needed for the acetylation reaction integrated into the
tion of less than three percent in the head products at esterification column or a correspondingly propor
the reaction conditions that apply here, with tempera 25 tioned second reactor.
tures between 180° and 250° C. and pressures of 3 to 30 How the conversion is divided between the esterifica
bar in the absence of catalysts, or temperatures between tion and final acetylation is a matter of economics. A
100 and 180° C. and pressures of 0.5 to 3 bar in the conversion rate below 65% to 70% in the esterification
presence of catalysts, requires a contact time of the reaction is reconomical since then more acetic acid is
reactants on the column plates of at least one hour, produced in the final acetylation phase than is used up
distributed over at least 20 plates of special construc in the esterification reaction. Therefore, conversions of
tion. Depending on the selected reaction conditions, the at least 70% are to be attempted in the esterification
sump product of the esterification column still contains reaction. Higher conversions can be achieved only by a
from 20% to 40% of acetic acid and 2% to 3% of water, corresponding extension of the contact time, such as, by
in addition to the acetin (mono, di and tri) with an OH 35 more reaction plates. An increase in the excess acetic
number of 549. This mixture is transferred to the finai acid at the same contact time, that is, with the same
acetylation phase, which may be constructed as an ex number of plates, for example, results in an only insig
tension of the esterification column or as a separate nificant increase of the conversion but lowers primarily
reactO. the quality of the headproducts by an increase in the
An extension of the esterification column has the acetic acid concentration. On the other hand, the reac
advantage that the acetic acid formed during the final tion rate of the final acetylation is considerably higher
acetylation by reaction of the acid anhydride with the than that of the esterification, so that less reaction space
remaining OH groups and with the reaction water con is needed for the acetylation, which means fewer plates.
tained in the sump product of the esterification column Another consideration is the fact that acetic acid anhy
passes without working up into the esterification co 45 dride is more expensive than acetic acid. In the final
umn. However, that final acetylation part of the esterifi analysis, the lowest possible production costs, including
cation column has to be provided with a heating means the costs of raw materials and investment, are a matter
for evaporation of a part of the acetic acid, as the reac of optimal operating conditions.
tion enthalpy of the exothermal final acetylation alone is The esterification according to the invention prefera
not sufficient to evaporate the acetic acid. 50 bly takes place in a special bubble plate column K 1. A
During the final acetylation, the reaction mixture perfect functioning of the bubble plate at the high liquid
from the esterification phase is reacted with 145 kg/hr. levels necessary in the reaction column for obtaining
(1.31 mol of anhydride per mol of glycerol) of fresh the required contact time at simultaneously low vapor
acetic acid anhydride to be converted and with 15 loads is produced by the construction, thanks to the
kg/hr. of acetic acid anhydride to be circulated as ex 55 double bubble principle. The double bubble consists of
cess to form triacetin, that is, 1.44 mol of anhydride per an inner bubble 23 (FIG. 4) for the adjustment of the
mol of glycerol. The triacetin leaving the concurrent dry pressure loss and an outer bubble 1 (FIG. 4) that
acetylation phase still contains acetic acid and anhy takes care of the distribution of the vapor in the liquid.
dride that are separated in the separation step, fron The inner bubble is also needed for the starting of the
which the acetic acid is returned into the esterification column so that the minimura liquid level on the plate
and the excess anhydride into the final acetylation. can be adjusted in such a manner that the intake tube 25
The final acetylation requires a contact time of at (see FIG. 2) of the plate lying above is immersed in the
least 15 minutes, depending on the choice of reaction liquid so that the vapor can only flow through the bub
conditions of between 100 to 250 C. and 0.5 to 30 bar. bles and not through the intake and outlet tubes of the
This requires at least 5 additional reaction plates for the 65 plates when the column operation is started.
acetylation reaction integrated into the esterification in a bubble late column particularly suitable for the
column or a correspondingly proportioned reactor, that process according to the invention, as described with
is, a cascade of agitator vessels or a tube reactor. reference to FIG. 6, with at least 20 plates, the total area
 4,381,407
9 10
13 occupied by the bubbles 11 (FIGS. 2, 3, 4, 5) on the of acetic acid vapor heated to 250 C. (purity: 99.5% by
plate 12 is 10% to 30% of the plate area lying between weight acetic acid) were fed in. The molar ratio of
the intake weir 14 and the outlet weir 15, depending on acetic acid to glycerol thus was 2.83:1. An amount of
the vapor charge. The ratio of height 16 of the bubbles 387 kg/hr. of reaction product consisting of 75% by
11 to the diameter 17 of the bubbles 11 is 0.5:1 to 3:1. In 5 weight of a mixture of monoacetin, diacetin and triace
the bubbles 11, 4 to 12 orifices 18 with diameters of 2 to tin and containing 22% by weight of acetic acid and 3%
6 mm are uniformly distributed along the periphery of by weight of water was removed from the sump of
the bubbles 11. These orifices 18 are located 5 to 10 mm reaction column K 1.
above the plate 12. The penetration area through the A mean contact time of approximately one hour for
orifices. 18 for the vapor is 0.3% to 3% of the inside 10
the liquid reaction mixture is obtained with the given
column cross-section. The height 20 of outlet tube 19 throughput rates.
exceeds 80 mm. The height 22 of the inner bubble 23 is The OH-number of the reaction product obtained
at least 20 mm greater than the distance 27 of the intake was 549. The conversion, based on the amount of glyc
tube 25 from plate 12. erol added, was thus 70%. This reaction product was
In an alternate construction of the bubbles 11 (FIG. 15
acetylated with acetic acid anhydride to an OH-number
4), 4 to 12 vertical slits 18a with a width of 2 to 5 mm
and a height of 5 to 15 mm are located close to plate 12 of less than 0.1 in a second reactor.
in bubble 11, instead of the orifices 18. The distillate draining from the condenser of rectify
The height 24 of the intake and outlet weirs 14, 15 ing column K2 at a rate of 40 kg/hr. contained 98% by
weight of water and 2% by weight of acetic acid. Only
(FIG. 2) exceeds the height 20 of the outlet tube 19that 20 traces
regulates the liquid level on plate 12. The weirs 14, 15 of glycerol and acetin were present.
also have slits 21 close to plate 12. When the plate diam Example 2
eter 10 exceeds 300mm, a reduced orifice 26 with a 3 to
15 mm diameter is provided in the neck of the inner Analogous to Example 1, but in a column with 48
bubble 23 (FIG. 5). The dry pressure loss due to this is 25 bubble plates, a sump product with an OH-number of
at least twice the hydrostatic difference of the level of 91.5 was obtained, i.e., a conversion of 95%. Again, 176
the liquid between intake and outlet and is at least 15 to kg/hr. of glycerol were transferred to the top plate of
20 mm Water Column. the esterification column. Below the 48th plate, 463
Another possibility to effect the required dry pres kg/hr. (7.72 kmol/hr) of superheated acetic acid vapor
sure loss is shown in FIG. 4. There the distance 28 30 with a temperature of 250 C. was fed in. The molar
between the upper edge of the neck of the inner bubble ratio of acetic acid to glycerol was 4.01:1. The pressure
23 and the outer bubble 11 is 2 to 6 mm. in the column was again 7.5 bar, the reaction tempera
The reaction can perhaps be better understood by ture was 250 C. ..
consideration of the relative boiling points of the vari A sump product which consisted of 69.3% by weight
ous ingredients as given in the following Table: 35 of a mixture of diacetin and triacetin and contained 30%
by weight of acetic acid and 0.7% by weight of water
B. P. at 760 mm unless other was drawn off from the sump of the esterification col
Compound wise indicated umn at a rate of 442 kg/hr. This mixture was acetylated
acetic acid 18 to an OH-number of <0.1 with acetic acid anhydride in
acetic acid anhydride 140 40 a second reactor. * . . .
glycerol 290 The distillate drawn off the column K 2 at a rate of
triacetin 258
diacetin 175 40 mm 101 kg/hr. consisted mainly of water and contained
monoacetin 158 165mm about 3% by weight of acetic acid and traces of glyc
erol and acetin.
s 45
The following examples are illustrative of the prac Example 3
tice of the invention without being limitative. The esterification was performed as in Example 1 in a
EXAMPLES column with 32 bubble plates, at a pressure of 7.5 bar
Example 1 50 and a reaction temperature of 250 C. The top plate was
A reaction column according to FIG. 1 with an inside charged with 176 kg/hr. (1.92 kmol/hr.) of glycerol,
diameter of 350 mm and 32 bubble plates corresponding while 326 kg/hr. (5.43 kmol/hr) of superheated acetic
to FIGS. 2, 3 and 4 were used to carry out the process. acid vapor at 250 C. were fed in below the bottom
The volume available for the liquid reaction phase, plate and 166kg/hr. (1.62 kmol/hr) of acetic acid anhy
based on the liquid without, gas, was 400 liters. 55 dride were fed in on the bottom plate. Besides this, 100
A rectifying column K2 was connected to the top of kg/hr. (0.97 kmol/hr) of acetic acid anhydride were
reaction column K 1, which was used to separate the fed into a second reactor unconnected to the esterifica
glycerol and acetin from the vapor rising from the top tion column. The amount of acetic acid anhydride
plate of the reaction column K 1. The rectifying column added per unit of time was such that the total amount of
K2 was operated with a reflux ratio of approximately 60 the water that was dissolved in the sump product at the
0.2 so that the condensate from rectifying column K2 70% conversion according to Example 1 as well as the
contained only water of reaction and approximately 2% water that was to be expected from the esterification of
by weight of acetic acid. - - the free OH-groups of the glycerol still present, could
The top plate of reaction column K 1 was charged react quantitatively to form acetic acid. In addition, an
with 176 kg/hr. (1.92 kmol/hr.) of glycerol of the qual- 65. excess of 10% is included in the share of acetic acid
ity DAB VII (OH-number 1,828) at a temperature of anhydride, which is returned either directly or after a
250.C. and under a pressure of 7.5 bar. Below the 32nd separation from the acetic acid in a separating appara
plate of reaction column K1,326 kg/hr. (5.43 kmol/hr.) tus. .
 4,381,407
11 12
The molar ratio of acetic acid to glycerol was 2.83:1, tion, an excess of 10% is included in the amount of
the corresponding ratio of acetic acid anhydride to acetic acid anhydride, which is returned into the pro
glycerol was 1.35:1. cess either directly or after a separation of the acetic
The reaction mixture drawn off from the sump of the acid in a separating apparatus.
reaction column has an OH number of 74, that is, a 5 A reaction mixture that contained triacetin with an
conversion of 96%, based on the glycerol, was ob OH number of <0.1 as well as acetic acid and acetic
tained. This reaction mixture was mixed with 100 acid anhydride was drawn off from the sump of the
kg/hr. of acetic acid anhydride and fed into a tube column. The sump of the column was constructed as an
reactor as second reactor in which the reaction contin evaporator that evaporated part of the acetic acid dis
ued to an OH number of <0.1. 10 solved in the sump, which then rose upward in the
At the head of column K2, the water of reaction was column and took care of the necessary mixing on plates
drawn off that still contained 2.5% by weight of acetic 54 to 49.
acid and was transferred into a biologic clarifying vessel The water of reaction, which still contained 2.5% by
after neutralization. weight of acetic acid, was drawn off at the head of
EXAMPLE 4
15 column K 2. After neutralization, the head products
were piped into a biologic clarifying vessel.
In a reaction column as in Example 1, but with 42 Example 6
plates, operating at a pressure of 7.5 bar and a reaction
temperature of 250 C., the top plate was charged with Analogous to Example 1 and operating under a pres
176 kg/hr. (1.92 kmol/hr.) of glycerol, which reacted sure of 1.5 bar, 167 kg/hr. (1.92 kmol/hr) of glycerol of
with the 326 kg/hr. (5.43 kmol/hr.) of superheated the quality DAB VII (OH number 1,828) and a temper
acetic acid vapor fed in below the 32nd plate and the ature of 150' C. were fed into the top plate of reaction
266 kg/hr. (2.59 kmol/hr) of acetic acid anhydride column K 1. The glycerol contained 0.5% by weight of
preheated to the reaction temperature fed into the 32nd p-toluene-sulfonic acid as catalyst. Below the 32nd plate
plate. The molar ratio of acetic acid to glycerol was 25 of reaction column K 1, 326 kg/hr. (6.43 kmol/hr.) of
2.83:1, the corresponding ratio of acetic acid anhydride acetic acid vapor heated to 150° C. (purity 99.5% by
to glycerol was 1.35:1. weight of acetic acid) were fed in. The molar ratio of
The amount of acetic acid anhydride that was added acetic acid to glycerol was therefore 2.83:1. Crude ace
during a unit of time was such that, on the one hand, the tin with an OH number of 311, corresponding to a
total amount of the water that was dissolved in the 30 conversion of 83%, based on the glycerol, was removed
reaction mixture on the 32nd plate, and that which was from the sump of K1. The sump product still contained
to be expected from the esterification of the free OH about 1% of water in addition to 24% of acetic acid.
groups of the glycerol still present, on the other hand, The sump product from K1 was acetylated to an OH
could be converted quantitatively into acetic acid. In number of <0.1 with acetic acid anhydride in a second
addition, the amount of acetic acid anhydride included 35 reactor.
an excess of 10%, which was returned to the process The distillate draining from the condenser of the
directly or after separation of the acetic acid in a prepa rectifying column K 2 contained 98% by weight of
ration plant. water and 2% by weight of acetic acid. Traces of glyc
From the sump of the column was withdrawn a reac erol and acetin could be identified as well.
tion mixture which contained, in addition to acetic acid The preceding specific embodiments are illustrative
and acetic acid anhydride, triacetin with an OH number of the practice of the invention. It is to be understood,
of <0.1. The sump of the column was designed as an however, that other expedients known to those skilled
evaporator, so that a part of the acetic acid dissolved in in the art or disclosed herein, may be employed without
the sump was evaporated, which then rose in the col departing from the spirit of the invention or the scope of
umn, effecting the necessary mixing on the bottom bub 45 the appended claims.
ble plates 42 to 33. We claim:
The reaction water which still contained 2.5% by 1. A process for the continuous production of triace
weight of acetic acid was withdrawn at the head of tin consisting essentially of continuousy charging liquid
column K2. After neutralization, the head product was glycerol into a first liquid reaction area through which
conducted to a biological clarification plant. 50 acetic acid vapors and water vapors flow, said liquid
Example 5 reaction area being divided into a number of separate
individual areas through which liquid glycerol and
In a reaction column, as in Examples 1 and 4, but with liquid acetin reaction products flow in one direction and
54 reaction bubble plates, 176 kg/hr. (1.92 kmol/hr.) of gaseous acetic acid and water flow in a countercurrent
glycerol were charged in at the top plate. Under the 55 direction, continuously charging acetic acid vapor to a
48th plate, 463 kg/hr. (7.72 kmol/hr.) of superheated separate individual area where said liquid mixture has
acetic acid vapor were fed. On the 48th plate 41 kg/hr. an OH number of less than 600, said liquid reaction
(0.40 kmol/hr) of acetic acid anhydride, preheated to areas being maintained at a pressure of from 0.2 to 30
the reaction temperature, were added to the reaction bar and a temperature of from 100' to 250 C., the num
mixture. The molar ratio acetic acid: glycerol was 60 ber of said separate individual areas and the amount of
4.02:1, the corresponding ratio of acetic acid anhydride: liquid glycerol and gaseous acetic acid charged being so
glycerin=0.21:1. The amount of acetic acid anhydride selected that the total contact time of the reactants is at
fed per unit of time was so selected that, on the one least one hour, continuously separating a liquid mixture
hand, the total amount of water which was dissolved in of acetins and water having an OH number of less than
the reaction mixture on the 48th plate could be reacted 65 600, continuously passing said liquid mixture into a
quantitatively to give acetic acid and which, on the second liquid reaction area, continuously adding
other hand, could be required for the esterification of thereto liquid acetic acid anhydride in an amount suffi
the still present free OH groups of the glycerol. In addi cient to react with water dissolved in said liquid mixture
 4,381,407 14
13
to form acetic acid and to react with monoacetin and 6. The process of claim 1 or 2 or 3 or 4 wherein said
diacetin present to form triacetin, continuously reco second liquid reaction area is divided into a number of
vering triacetin, continuously passing vaporized acetic separate individual areas and is a continuation of said
acid formed into said separate individual area where first liquid reaction area.
said liquid mixture has an OH number of less than 600, 5 7. The process of claim 6 wherein said second liquid
and continuously recovering a mixture of water vapors reaction area is charged with said liquid acetic acid
and acetic acid vapors having a content after condensa anhydride in the lower third of the total first and second
tion of less than 3% by weight of acetic acid. liquid reaction areas, said liquid acetic acid anhydride
2. The process of claim 1 wherein said continuous and said liquid mixture of acetins and water having an
production of triacetin occurs in the absence of a cata 10 OH number of less than 600 flowing concurrently
lyst at a pressure of from 3 to 30 bar and a temperature through said number of separate individual areas in said
of 180 to 250 C. second liquid reaction area.
3. The process of claim 1 wherein said continuous 8. The process of claim 1 wherein said second liquid
production of triacetin occurs in the presence of an acid reaction area is separate from said first liquid reaction
esterification catalyst at a pressure of from 0.2 to 3 bar 15 202.
and a temperature of from 100 to 180 C. 9. The process of claim 1 or 2 or 3 or 4 wherein the
4. The process of claim 3 wherein said acid esterifica molar ratio of acetic acid to glycerol charged is 2.5:1 to
tion catalyst is employed in an amount of from 0.01% to 5:1.
0.5% by weight, based on the amount of glycerol 10. The process of claim 1 or 2 or 3 or 4 wherein the
charged. 20 molar ratio of acetic acid anhydride to glycerol charged
5. The process of claim3 or 4 wherein said acid esteri is 0.1:1 to 1.5:1.
k . . k sk
fication catalyst is p-toluene sulfonic acid.

30

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50

55

65