US00839.

9700B2

(12) United States Patent (10) Patent No.: US 8,399,700 B2

Salisbury et al. (45) Date of Patent: Mar. 19, 2013
(54) VINYLACETATE PRODUCTION PROCESS FOREIGN PATENT DOCUMENTS
DE 100 30 040 C1 10, 2001
(75) Inventors: Brian Salisbury, Oxford, PA (US); WO WO2011/043798 A1 4, 2011
Michael E. Fitzpatrick, League City,
TX (US); Wayne Joseph Brtko, Glen OTHER PUBLICATIONS
Mills R S; N el C. Hallinan, PCT International Search Report and Written Opinion Mailed Sep.
oveland, OH (US) 11, 2012, for PCT application No. PCT/US/2012/033621.
(73) Assignee: isode systs Technology, L.P., * cited by examiner
(*) Notice: Subject to any disclaimer, the term of this Primary Examiner — Paul A Zucker
patent is extended or adjusted under 35
U.S.C. 154(b) by 165 days. (57) ABSTRACT
(21) Appl. No.: 13/087,785 A process is disclosed for the production of vinyl acetate
where a mixture of ethylene, acetic acid, and oxygen is
(22) Filed: Apr. 15, 2011 reacted in the presence of a catalyst to produce a product
mixture of vinyl acetate, ethylene, carbon dioxide, acetic
(65) Prior Publication Data acid, water, ethyl acetate, and ethylene glycol diacetate. The
US 2012/O26497OA1 Oct. 18, 2012 product mixture contains both a gaseous phase and a liquid
• Y-s phase, which are separated. The gas phase contains at least
(51) Int. Cl. carbon dioxide, which is removed via gas stream. The crude
C07C 67/28 (2006.01) vinyl acetate stream is removed via a liquid stream. The crude
(52) U.S. Cl. ....................................................... 560243 vinyl acetate is then further separated to isolate a stream
(58) Field of Classification Search None containing at the majority of the ethylene glycol diacetate.
See application file for com lete search history The ethylene glycol diacetate stream is then methanolyzed in
pp p ry. the presence of a methanolyzing catalyst, to recover methyl
(56) References Cited acetate, which can be optionally recycled as a feed stock to an
acetic acid plant.
U.S. PATENT DOCUMENTS
6,420,595 B1* 7/2002 Hallinan et al. .............. 560.245 11 Claims, 5 Drawing Sheets
U.S. Patent Mar. 19, 2013 Sheet 1 of 5 US 8,399,700 B2

109

1800 1600 1400 1200 1000

Wavenumbers (cm-1)
Hydrolysis
FIG. 2
U.S. Patent Mar. 19, 2013 Sheet 2 of 5 US 8,399,700 B2

1200 1000 8OO

Wavenumbers (cm-1)

FIG. 3
Comparison of Rate of EGDA Hydrolysis & Methanolysis
120
60C, 6:1 Molar ratio of MeOH or H2O to EGDA, 5wt%PTSA
100
8O

6O
-Hydrolysis

24.O : -Methanolysis
O
O 20 40 60 80 100 120 140 160
Time (minutes)
FIG. 4
U.S. Patent Mar. 19, 2013 Sheet 3 of 5 US 8,399,700 B2

2:2:1 MeOH:EGDA 22.5C With PTSA

12
Start: 9.9M MeCH, 4.5M EGDA
1O

50 100 150 200 250 300 350 400 450 500

Time, mins
F.G. 5

Effect of PTSA Concentration on Methanolysis Rate

O.5. Wit' PTSA

/
O 10 20 30 40 50 60 70 80 90
Time (minutes)

FIG. 6
U.S. Patent Mar. 19, 2013 Sheet 4 of 5 US 8,399,700 B2

2:1 MeOHEGDA With PT SA

O 100 2OO 300 4OO 500

Time, mins

O.5

0.4
s MeOAC EGDA
s
?
a 0.3
O
O
C O.2

0.1

O.O
1300 1250 1200 1150
Wavenumbers (cm-1)
2:1 Moral ratio MeOH: EGDA22.5°C. Timespan: 6.5 hours

FIG. 8
U.S. Patent Mar. 19, 2013 Sheet 5 of 5 US 8,399,700 B2

9
s
O
O
c
o
C

1300 1250 1200 1150

Wavenumbers (cm-1)
2:1 Moral ratio MeCH: EGDA 0.0°C. Timespan: 6.5 hours

0.5

0.4 EGDA

is 0.3 MeOAC
CO O.2

0.1

1300 1250 1200 1150

Wavenumbers (cm-1)
2:1 Moral ratio MeOH: EGDA22.5°C. No PTSA Timespan: 6.5 hours

FIG 10
 US 8,399,700 B2
1. 2
VNYLACETATE PRODUCTION PROCESS acetate stream comprising vinyl acetate, acetic acid, water,
ethyl acetate and ethylene glycol diacetate. An ethylene gly
FIELD OF THE DISCLOSURE col diacetate stream is isolated from the crude vinyl acetate
stream and Subjected to a reactive distillation involving
The disclosure relates to the preparation of vinyl acetate. 5 methanolysis to recover methyl acetate, which is preferably
More particularly, the disclosure relates to improving the recycled to an acetic acid plant as a feedstock, thereby
overall yield of acetic acid and vinyl acetate processes by improving the overall yield of the overall process.
recovering methyl acetate from a reaction waste stream that
comprises ethylene glycol diacetate. BRIEF DESCRIPTION OF THE DRAWINGS
10
BACKGROUND OF THE DISCLOSURE In order to describe the manner in which the above-recited
and other advantages and features of the present disclosure
Vinyl acetate is commonly produced by the reaction of can be obtained, a more particular description of the various
ethylene, oxygen and acetic acid in the presence of a palla embodiments briefly described above will be rendered by
dium-gold catalyst. See, for example, U.S. Pat. No. 3,743, 15 reference to the appended drawings. Understanding that these
607. Palladium and gold are expensive precious metals. drawings depict only exemplary embodiments and are not
Therefore, many efforts have been made to increase the cata therefore to be considered to be limiting of its scope, and will
lytic activity and reduce the amount of catalyst needed. For be described and explained with additional specificity and
example, U.S. Pat. No. 6,022,823 teaches calcining the Sup detail through the use of the accompanying drawings in
port impregnated with palladium and gold salts prior to reduc- 20 which:
ing the metals. The catalyst shows improved activity. These FIG. 1 is a schematic representation of an example system
prior patents are herein incorporated by reference in their embodiment according to the present disclosure;
entirety. FIG. 2 is a graphic illustration of the overlaid infrared
The acetoxylation of ethylene to vinyl acetate is commonly spectra obtained during the course of a reaction using a
performed in a gas phase, fixed bed tubular reactor. Vinyl 25 hydrolysis pathway;
acetate is recovered by condensation and scrubbing, and puri FIG. 3 is a graphic illustration of the overlaid infrared
fied by distillation. Unreacted ethylene, oxygen and acetic spectra obtained during the course of a reaction of 2:1 Molar
acid are recovered by distillation and recycled to the acetoxy ratio MeOH:EGDA at 22.5 degrees Celsius over a time span
lation. of 6.5 hours;
In addition to vinyl acetate, the acetoxylation produces a 30 FIG. 4 is a graphic illustration of the relative reaction rates
number of byproducts, including carbon dioxide, water, ethyl of hydrolysis versus methanolysis;
acetate and ethylene glycol diacetate. Carbon dioxide is pri FIG. 5 is a graphic illustration of the products produced by
marily produced by the combustion of ethylene and vinyl a reaction of 2:1 Molar ratio MeOH:EGDA at 22.5 degrees
acetate. Carbon dioxide is removed from the reaction product Celsius in the presence of a catalyst;
mixture by distillation and absorption with a potassium car- 35 FIG. 6 is a graphic illustration of the effect of catalyst
bonate solution. concentration on methanolysis rate;
Copending U.S. patent application Ser. Nos. 12/587,580, FIG. 7 is a graphic illustration of the effect of temperature
filed on Oct. 9, 2009, and 127653,144 filed on Mar. 8, 2010 on methanolysis rate;
disclose a process for the production of vinyl acetate. The FIG. 8 is a graphic illustration of a narrower spectrum of
processes comprise reacting ethylene, acetic acid, and oxy- 40 the reaction detailed in FIG. 2;
gen in the presence of a catalyst to produce a reaction mixture FIG. 9 is a graphic illustration of the overlaid infrared
comprising vinyl acetate, ethylene, carbon dioxide, acetic spectra obtained during the course of a reaction of 2:1 Molar
acid, water and ethylene glycol diacetate. The reaction mix ratio MeOH:EGDA at 0.0 degrees Celsius over a time span of
ture is separated to a gas stream comprising ethylene, oxygen, 6.5 hours; and
and carbon dioxide and a crude vinyl acetate stream compris- 45 FIG. 10 is a graphic illustration of the overlaid infrared
ing vinyl acetate, acetic acid and ethylene glycol diacetate. An spectra obtained during the course of a reaction of 2:1 Molar
ethylene glycol diacetate stream is isolated from the crude ratio MeOH:EGDA at 22.5 degrees Celsius over a time span
vinyl acetate stream and hydrolyzed prior to or in the waste of 6.5 hours with no catalyst present.
acid stripper column of an acetic acid plant, to recover the
acetate content of the stream as acetic acid. 50 DETAILED DESCRIPTION OF THE
However, the hydrolysis pathway provides a number of DISCLOSURE
logistical complexities that can be improved. These include
maintaining a proper flow rate to a waste acid stripper, energy Several embodiments of the process disclosed herein
intensive separation of acetic acid from water, and a less than includes reacting ethylene, acetic acid, and oxygen in the
desirable equilibrium yield. 55 presence of a catalyst. The acetoxylation can be performed in
Accordingly, a new method for recovering acetic value a gas phase, fixed bed tubular reactor using a Supported cata
from the vinyl acetate production is needed. lyst. The acetoxylation can be performed at a temperature
within the range of 150 degrees Celsius to 250 degrees Cel
SUMMARY OF THE DISCLOSURE sius, or preferably within the range of 175 degrees Celsius to
60 200 degrees Celsius. The acetoxylation can be performed
Disclosed herein is a process for the production of vinyl under a pressure within the range of 50 psia to 150 psia, or
acetate. The process comprises reacting ethylene, acetic acid preferably within the range of 70 psia to 140 psia.
and oxygen in the presence of a catalyst to produce a reaction The amount of oxygen in the combined feed can be within
mixture comprising vinyl acetate, ethylene, oxygen, carbon the range of 5 mol% to 15 mol%, preferably within the range
dioxide, acetic acid, water, ethyl acetate, and ethylene glycol 65 of 5 mol% to 12 mol%. Acetic acid can be introduced into the
diacetate. The reaction mixture is separated to a gas stream reactor in vapor form. The amount of acetic acid in the com
comprising ethylene and carbon dioxide and a crude vinyl bined feed can be within the range of 10 mol % to 25 mol%.
 US 8,399,700 B2
3 4
The amount of ethylene in the combined feed can be within glycol that are then further separated by distillation. These
the range of 65 mol % to 80 mol%. Ethylene, oxygen and products from the reaction are then fed into a distillation
acetic acid can be mixed and the mixture can then be fed into column 150 to separate the desired products, in particular
the reactor as a gas. methyl acetate.
Suitable catalysts include those known to the vinyl acetate The distillation column 150 can typically operate with a
industry. The catalyst can be a palladium-gold catalyst. Meth distillate stream 114 between about 50 degrees Celsius and
ods for preparing palladium-gold catalysts are known. For about 70 degrees Celsius. Specifically, the distillate stream
instance, U.S. Pat. No. 6,022,823, the teachings of which are can be within the range having a lower limit and/or an upper
incorporated herein by reference, teaches how to prepare a limit, each expressed in degrees Celsius. The range can
palladium-gold catalyst that has high activity and selectivity. 10 include or exclude the lower limit and/or the upper limit. For
The palladium-gold catalyst can be supported on an inorganic example, the temperature lower limit and/or upper limit can
oxide. The inorganic oxide can be selected from the group be: 40, 45, 50, 51, 52,53,54, 55,56, 57,58, 59, 60, 61, 62,63,
consisting of alumina, silica, titania, and the like, and mix 64, 65, 66, 67, 68, 69, 70, 75, and 80 degrees Celsius. The
tures thereof. bottoms stream of distillation column 150 can typically oper
The Supported catalysts can have palladium contents from 15 ate between about 140 degrees Celsius and about 160 degrees
0.1 wt % to 10 wt % and gold contents from 0.1 wt % to 3 wt Celsius. Specifically, the bottoms stream can be within the
%. Preferred catalysts can contain from 0.5 wt % to 1.5 wt % range having a lower limit and/or an upper limit, each
of palladium; and from 0.25 wt % to 0.75 wt % of gold. The expressed in degrees Celsius. The range can include or
weight ratio of palladium to gold can be within the range of exclude the lower limit and/or the upper limit. For example,
5:1 to 1:3, preferably within the range of 2.5:1 to 1:1.5. the temperature lower limit and/or upper limit can be 130,
The reaction mixture can be withdrawn from the reactor 135, 140, 141, 142, 143, 144, 145, 146, 147,148, 149, 150,
and separated into a gas stream and a crude vinyl acetate 151,152, 153,154, 155, 156,157,158,159, 160, 165, and 170
stream. The gas stream comprises ethylene and carbon diox degrees Celsius.
ide. The crude vinyl acetate stream comprises vinyl acetate, The resultant methyl acetate is removed from the system
acetic acid, water, ethyl acetate, and ethylene glycol diac 25 via the distillate stream 114 and recycled to an acetic acid
etate. Carbon dioxide is separated by distillation or absorp plant as a feedstock, the ethylene glycol is isolated as a
tion from ethylene, which is then preferably recycled to the byproduct. While a boiling pot reactor is described as facili
acetoxylation reactor. The crude vinyl acetate stream is sepa tating the reaction, other vessels can be used, non-limiting
rated by distillation into an ethylene glycol diacetate stream examples include, any known continuous or batch type reac
which comprises ethylene glycol diacetate, acetic acid and 30 tors, including fluidized bed reactors or reactive distillation.
water and a vinyl acetate product stream which comprises Optionally, additional amounts of water can be fed together
vinyl acetate and ethyl acetate. The vinyl acetate product with the ethylene glycol diacetate stream. Alternatively, addi
stream can be subjected to further purification to produce tional water can be fed separately into the reaction section.
vinyl acetate with a desired purity. The boiling pot reactor is connected to distillation column
The ethylene glycol diacetate stream may also comprise 35 150.
other components, for example, ethylidene diacetate, ethyl The overhead stream comprises methyl acetate and any
ene glycol, and polyvinyl acetate. The ethylene glycol diac excess methanol and it is preferably recycled to an acetic acid
etate stream preferably comprises at least 50 wt % of ethylene plant for recovery or reuse of the acetic value. The bottoms
glycol diacetate. More preferably, the ethylene glycol diac stream comprises ethylene glycol, the methanolysis catalyst,
etate stream comprises from 50 wt % to 95 wt % of ethylene 40 and all other heavy byproducts. The bottoms stream can be
glycol diacetate. Most preferably, the ethylene glycol diac Subjected to further separation or disposed of as waste.
etate stream comprises from 70 wt % to 80 wt % of ethylene One advantage of using the herein described methanolysis
glycol diacetate and from 20 wt % to 30 wt % acetic acid. pathway is that the rate of methanolysis is at least four times
The ethylene glycol diacetate stream undergoes a reaction greater than the rate of hydrolysis, see for example, FIG. 4.
in a boiling pot reactor 140 using a methanolysis pathway, as 45 Below Equation 1 represents one possible methanolysis pro
seen in FIG. 1. FIG. 1 shows that the bottoms 104 of ARU CSS
Tower B 120 and bottoms 108 of ARU Tower C130 are fed
via line 110 into methanolysis reactor 140. Methanolysis
reactor 140 is also fed with methanol via line 111. The reac
tion in methanolysis reactor 140 typically takes place within 50
the range of about 60 degrees Celsius up to about 80 degrees (Ethylene Glycol Diacetate)+(Methanol)->(Ethylene
Glycol)+(Acetic Acid) Equation 1
Celsius. Furthermore, the methanolysis reactor can operate
within a range having a lower limit and/oran upper limit, each A further advantage is that the reaction produces methyl
expressed in degrees Celsius. The range can include or acetate from which the acetic value of ethylene glycol diac
exclude the lower limit and/or the upper limit. For example, 55 etate can be recovered. Because neither water or acetic acid
the temperature lower limit and/or upper limit can be: 50, 55. are used in the reaction or produced by the reaction, the
60, 61, 62,63, 64, 65, 66, 67,68, 69,70, 71,72, 73,74, 75,76, methanolysis pathway does not require the energy intensive
77,78, 79,80, 85,90 degrees Celsius. separation of acetic acid and water. Rather, methyl acetate is
The reaction in the boiling pot reactor takes place in the produced which can be returned as feed to an acetic reactor.
presence of a methanolysis catalyst. Suitable methanolysis 60 Finally, even though both the hydrolysis and the methanolysis
catalysts include base and acid catalysts. Examples of base pathways are in equilibrium, lying at about 80-90% to the
catalysts include ammonia, organic amines, metal hydrox right, if the methyl acetate is vented, the methanolysis path
ides, basic ion-exchange resins, and the like, and mixtures way can achieve about 100% completion.
thereof. Examples of acid catalysts can include any strong To further explain the process of the present disclosure,
acid, for example Sulfuric acid, Sulfonic acids, acidic ion 65 experiments were conducted. As described below with
exchange resins, and the like, and mixtures thereof. The respect to experiments, Experiments 1 and 2 describe one
methanolysis product comprises methyl acetate and ethylene embodiment of the herein described methanolysis reaction.
 US 8,399,700 B2
5 6
Further, a hydrolysis reaction was also carried out under an infrared spectrum is obtained, the concentration of
similar conditions to the methanolysis reaction described in MeOAc should be (EGDA initial-EGDA time point)*2
Examples 1 and 2 to facilitate comparison between the two where the EGDA time point concentration is determined from
reactions. The spectra from the hydrolysis runs are included infrared. Based on this logic, the MeOAc time point concen
in FIG. 2, showing the production of acetic acid (“HOAc) as tration determined from infrared should match the value
the ethylene glycol diacetate (“EGDA) concentrations determined in the MeOAc concentration definition above.
decrease. Based on the close overlap between the measured and
Based on the observations from methanolysis experiments calculated values for MeOAc and EG, the methanolysis reac
described in Experiments 1 and 2, along with the hydrolysis tion described by this embodiment produces very low, if any,
reaction carried out under similar reaction conditions, several 10
steady state concentrations of the monoacetate. Furthermore,
dozen multi-component calibration standards were prepared this quantitative analysis shows that the reaction reaches at
and calibration models were constructed. Those skilled in the least 90% completion, and can reach 100% completion.
art of infrared spectroscopy and chemometric modeling as Based on the quantitative analysis, the kinetics of the
described in U.S. Pat. No. 6,552.221 will recognize from FIG. methanolysis reaction can be determined. Initially, the overall
3 that the concentrations of the ethylene glycol diacetate, 15
methanolysis reaction can be predicted to be 4" order with 1
methanol, methyl acetate, and ethylene glycol can be deter order dependence on EGDA and the acid catalyst, and 2"
mined from the spectra. order dependence on MeCH. As acid catalyst concentration
Based on these calibration models, the reactions can be will be relatively invariant in an industrial process, the reac
properly monitored and the relative rates of hydrolysis and tion at constant acid catalyst concentration can be considered
methanolysis can be determined and compared. As shown in to be pseudo 3" order. To confirm that the reaction does have
FIG. 4, the data indicate that at 60 degrees Celsius and with 5 a 1" order dependence on catalyst concentration, several reac
wt % acid catalyst, methanolysis has a half-life of about 7-8 tions were carried out at 49 degrees Celsius in which a starting
minutes, making it about 4.5 times faster than hydrolysis. MeOH:EGDA molar ratio of 6:1 was maintained and in
Further, products formed by methanolysis include methyl which para-toluenesulfonic acid (“PTSA) concentration
acetate, which is an easier product to separate than the prod 25
was varied from 0.5 to 5.0 wt %. Reaction profiles in terms of
ucts of hydrolysis, namely acetic acid and water. Therefore, disappearance of EGDA are shown in FIG. 6 and 1' order
the methanolysis process has rates that are substantially faster dependence was confirmed.
and products that are easier to isolate, than the hydrolysis FIG. 7 shows some reaction profiles for temperatures rang
pathway. ing from 0 to 49 degrees Celsius. Generally speaking, dupli
The calibration models available were also used to provide 30 cate runs were carried out. Rate constants associated with
a material balance during a methanolysis reaction. The mate runs at select temperatures are shown in Table 2.
rial balance shows that EGDA is methanolyzed to about
100% ethylene glycol (“EG'), rather than methanolyzed at a TABLE 2
lower rate, which leads to a mixture of the glycol and monoac
etate. As shown in FIG. 5, the reaction produces glycol almost 35 Temp, C. k, M's
exclusively, i.e., it is about 100% methanolyzed. The molar 19 2.66E-05
disappearance of EGDA is matched by a corresponding molar 19 2.49E-05
appearance of EG and a two-fold molar appearance of 34 S. 67E-OS
MeOAc. The calibration models were applied to the spectro 34
49
6.33E-OS
195E-04
scopic data for a room temperature methanolysis reaction and 40
the corresponding quantitative data are shown in FIG. 5.
In addition to the quantitative data obtained from the cali In an effort to simulate industrial conditions where tem
bration models, FIG. 5 also contains dashed line curves for peratures in excess of 60 degrees Celsius will be used to allow
MeOAc and EG that were calculated on the assumption that MeOAc evaporation, thus driving the equilibrium to comple
the measured EGDA disappearance can be attributed solely to 45 tion, several runs in the 60-65 degrees Celsius range were
complete methanolysis to two moles of MeOAc and one mole carried out with a water cooled condenser. It was indeed
of EG per mole of EGDA. Specifically, the methanolysis observed over the course of a high temperature run that mea
pathway comprises at least the following stepwise reactions: sured MeOAc concentrations did not achieve material bal
ance relative to disappearance of EGDA. It was found that
50 these high temperature runs showed complete disappearance
of EGDA, complete formation of ethylene glycol and about
(Ethylene Glycol Diacetate)+(Methanol)->(Ethylene 70% of expected MeOAc concentration. These data suggest
Glycol Monoacetate)+(Methyl Acetate) Equation 2 that an equilibrium position close to 100% can be expected
using temperatures in excess of 60 degrees Celsius.
CHC(O)OCH2CH2OH+CH-OH->HOCH2CH2OH+ 55 The following examples are merely illustrative. Those
CHCOOCH skilled in the art will recognize many variations that are
(Ethylene Glycol Monoacetate)+(Methanol)->(Ethyl
within the spirit and scope of the disclosure.
ene Glycol)+(Methyl Acetate) Equation 3 EXAMPLES
With regard to FIG. 5, if the ethylene glycol monoacetate 60
formed in Equation 2 immediately reacts with another The following examples were carried out to test the prop
CHOHas shown in Equation3, it will not be observed on the erties of the reaction under multiple different reaction condi
infrared timescale and 2:1 molar relationship between disap tions. Reaction runs were carried out using a 50 mL Schlenk
pearance of EGDA and appearance of MeCAc would be flask equipped with a condenser, with 20 mLs oftotal solution
expected and so would a 1:1 molar relationship between 65 used per run. The Schlenk flask containing the required Vol
disappearance of EGDA and appearance of E.G. Using these ume of MeCH and required weight of PTSA was heated to
assumptions, at any time point during a methanolysis where desired temperature in a water bath. Simultaneously, the
 US 8,399,700 B2
7 8
required volume of EGDA, contained in a vial, was also Example 5
heated in the water bath. Once solutions had reached desired
temperature, EGDA was rapidly syringed from the vial and The reaction of Example 1 was carried out at 60 degrees
via a one foot long needle was added to the Schlenk flask Celsius with a 6:1 MeOH:EGDA molar ratio and 5 wt %
through the condenser. PTSA catalyst. Data for this run are shown in FIG. 4.
Subsequently the Solution was monitored on a periodic Example 6
basis, the frequency of which depended on the rapidity of the
reaction. Aliquots of 0.1 mL were removed by a disposable The reaction of Example 1 was carried out at 60 degrees
Syringe equipped with a one foot long needle which could be Celsius with a 6:1 HOAc:EGDA ratio and 5 wt % PTSA
inserted through the side arm of the Schlenk flaskand into the 10
catalyst. Data for this run are shown in FIG. 4. Overlaid
solution and analyzed by ATR-FTIR. The lowest achievable infrared spectra associated with this run are shown in FIG. 2.
frequency of analysis was 2 minutes.
Example 7
Example 1 15 The reaction of Example 1 was carried out at multiple
temperatures with a 6:1 MeOH:EGDA ratio and 0.5 wt %
A methanolysis run was carried out at 22.5 degrees Celsius PTSA catalyst. Specifically, the temperatures were measured
with a solution comprising 2.2:1 molar ratio of MeOH:EGDA at 19 degrees Celsius, 34 degrees Celsius, and 49 degrees
with 5 wt % PTSA catalyst. FIG. 8 contains overlaid spectra Celsius. The results of these experiments are presented in
obtained over a period of 6.5 hours. Reactions were carried Table 2.
out for both methanolysis and hydrolysis and analysis by GC The various embodiments, figures, and examples
at run termination indicated that rates were sufficiently slow described above are provided by way of illustration only and
to allow monitoring by periodic FTIR analysis. In order to should not be construed to limit the disclosure. Those skilled
identify spectroscopic features and as a guide to aid in gen in the art will readily recognize various modifications and
eration of the multicomponent calibration models required 25 changes that may be made to the present disclosure without
for data analysis, a few methanolysis runs were carried out in following the example embodiments and applications illus
which the solutions were periodically monitored by removal trated and described herein, and without departing from the
of aliquots for FTIR analysis. true spirit and scope of the present disclosure.
We claim:
The methyl acetate peak, the left most peak labeled 1. A process for the production of vinyl acetate comprising:
MeOAC, rises as the ethylene glycol diacetate peak, the right 30
reacting ethylene, acetic acid, and oxygen in the presence
most peak labeled EGDA, falls. This indicates that the methyl of a catalyst to produce a reaction mixture comprising
acetate is formed by the disappearance of EGDA, as predicted vinyl acetate and ethylene glycol diacetate;
by Equation 1. Furthermore, the reaction appears to consume separating the reaction mixture to form a gas stream and a
most of the EGDA present at the beginning of the reaction, as crude vinyl acetate stream comprising vinyl acetate, and
indicated by the lack of absorbance at about 1220 cm. 35 ethylene glycol diacetate;
separating the ethylene glycol diacetate from said crude
Example 2 vinyl acetate stream; and
methanolyzing the separated ethylene glycol diacetate in
the presence of a methanolyzing catalyst and recovering
As can be seen in FIG.9, the reaction takes place at a much 40 methyl acetate.
slower rate and the formation of MeOAc is substantially 2. The process of claim 1 wherein the ethylene glycol
inhibited at the lower reaction temperature 0 degrees Celsius. diacetate stream comprises at least 50 wt % ethylene glycol
Moreover, the EGDA remains largely present after a 6.5 hour diacetate.
run of the experiment. 3. The process of claim 1 wherein the methanolyzing of the
45 ethylene glycol diacetate reaches an equilibrium of greater
Example 3 than about 95% completion.
4. The process of claim 1 wherein the methanolyzing of the
ethylene glycol diacetate reaches an equilibrium of about
The reaction of Example 1 was also carried out without the 100% completion.
aid of a catalyst. As can be seen, by inspection of FIG. 10, 50
5. The process of claim 1 wherein the methanolyzing step
there is no MeOAc peak, thereby indicating that no reaction further comprises methanolyzing the ethylene glycol diac
has taken place in the absence of the acid catalyst. etate stream in a boiling pot reactor.
6. The process of claim 5, wherein the boiling pot reactor
Example 4 operates within the temperature range from about 60 degrees
55 Celsius to about 80 degrees Celsius.
The reaction of Example 1 was carried out at 49 degrees 7. The process of claim 1 further comprising the step of
Celsius with multiple concentrations of PTSA catalyst. Spe recycling the methyl acetate to an acetic acid reactor.
cifically, there are four separate experiments, the data from 8. The process of claim 1, the reaction mixture further
those experiments are presented in FIG. 6. Specifically, the comprising carbon dioxide, acetic acid, water, and ethyl
acetate.
four runs are at 0.5 wt %, 1.5 wt %, 3 wt %, and 5 wt % PTSA 60
9. The process of claim 1 the gas stream further comprising
catalyst. As can be seen by inspection of FIG. 6, the rate ethylene and carbon dioxide.
increased with increasing catalyst concentration, with the 5 10. The process of claim 1 the crude vinyl acetate stream
wt % PTSA catalyst having the fastest reaction rate while the further comprising acetic acid, water, and ethyl acetate.
reaction with 0.5 wt % PTSA is the slowest reaction rate.
Therefore, FIG. 6 supports the above disclosure that PTSA 65
11. The process of claim 1 wherein the methyl acetate is
recovered in a distillation tower.
catalyst concentration can be used to affect the rate of metha
nolysis. k k k k k