USOO8624054B2

(12) United States Patent (10) Patent No.: US 8,624,054 B2

Hazel et al. (45) Date of Patent: Jan. 7, 2014
(54) CARBONYLATION PROCESS FOR THE (56) References Cited
PRODUCTION OF METHYLACETATE
U.S. PATENT DOCUMENTS
(75) Inventors: Nicholas John Hazel, Beverley (GB);
Lesley Ann Key, Hull (GB); Mark 2006/0252959 A1 1 1/2006 Cheung et al.
Stephen Roberts, Beverley (GB); John 2006/0287551 A1* 12/2006 Cheung et al. ................ 560,232
Glenn Sunley, Cottingham (GB) FOREIGN PATENT DOCUMENTS
(73) Assignee: BP Chemicals Limited, Middlesex (GB) EP O 596 632 5, 1994
EP 2000 433 12/2008
(*) Notice: Subject to any disclaimer, the term of this EP 2O85375 8, 2009
patent is extended or adjusted under 35 WO WOO1,073.93 2, 2001
U.S.C. 154(b) by 364 days. WO WO 2005,105.720 11, 2005

(21) Appl. No.: 12/998,742 OTHER PUBLICATIONS

(22) PCT Fled: Nov. 19, 2009 International Search Report for PCT/GB2009/00002696, mailed Jan.
27, 2010.
(86) PCT NO.: PCT/GB2O09/002696 Written Opinion of the International Searching Authority for PCT/
GB2009/00002696, mailed Jan. 27, 2010.
S371 (c)(1), Cheung, P. et al., “Selective Carbonylation of Dimethyl Ether to
(2), (4) Date: Jul. 5, 2011 Methyl Acetate Catalyzed by Acidic Zeolites'. Angew. Chem. Int.
Ed., vol. 45, (2006), pp. 1617-1620.
(87) PCT Pub. No.: WO2O10/061169 Tartamella, T.L. et al., “Role of Acid Catalysis in Dimethyl Ether
Conversion Processes'. Proceedings of the Annual International
PCT Pub. Date: Jun. 3, 2010 Pittsburgh Coal Conference, vol. 2, (Jan. 1, 1996), pp. 996-1001.
PCT Notification Concerning Transmittal of International Prelimi
(65) Prior Publication Data nary Reporton Patentability; Form PCT/IB/326. International Appli
US 2011 FO319654 A1 Dec. 29, 2011
cation No. PCT/GB2009/002696, filed Nov. 19, 2009 (6 pgs).

Foreign Application Priority Data * cited by examiner

(30)
Nov. 27, 2008 (EP) ..................................... O8253827 Primary Examiner — Johann R Richter
Assistant Examiner — Mark Luderer
(51) Int. C. (74) Attorney, Agent, or Firm — Nixon & Vanderhye
CD7C 67/36 (2006.01)
C07C5L/10 (2006.01) (57) ABSTRACT
C07C 67/37 (2006.01)
CO7C 69/14 (2006.01) A process for the production of methyl acetate by reacting
(52) U.S. C. dimethyl ether with carbon monoxide into a carbonylation
USPC ............ 560/232; 560/129;562/517; 562/519 reactor containing a mordenite catalyst in the presence of
(58) Field of Classification Search added methyl acetate and/or acetic acid.
None
See application file for complete search history. 17 Claims, 5 Drawing Sheets
U.S. Patent US 8,624,054 B2
U.S. Patent Jan. 7, 2014 US 8,624,054 B2
U.S. Patent Jan. 7, 2014 Sheet 5 of 5 US 8,624,054 B2
 US 8,624,054 B2
1. 2
CARBONYLATION PROCESS FOR THE Accordingly, the present invention provides a process for
PRODUCTION OF METHYLACETATE the production of methyl acetate, which process comprises
carbonylating dimethyl ether with carbon monoxide in one or
This application is the U.S. national phase of International more carbonylation reaction Zones in the presence of a
Application No. PCT/GB2009/002696, filed 19 Nov. 2009, mordenite catalyst to produce methyl acetate product charac
which designated the U.S., and claims priority to EP Appli terised in that at least one of methyl acetate and acetic acid is
cation No. 08253827.3, filed 27 Nov. 2008, the entire con added to at least one of said reaction Zone(s).
tents of each of which are hereby incorporated by reference. Advantageously, it has been found that if at least one of
This invention relates to a carbonylation process for the methyl acetate and acetic acid is fed to the carbonylation
production of methyl acetate by reacting dimethyl ether with 10 process, the formation of by-products, and, in particular the
carbon monoxide in the presence of added methyl acetate formation of methane and C2 hydrocarbons by-products is
reduced.
and/or acetic acid and a mordenite catalyst. Furthermore, if methyl acetate is present in the dimethyl
Liquid phase carbonylation processes such as the carbony ether feed introduced into a reaction Zone on start-up of the
lation of methanol and/or reactive derivatives thereof in the 15 carbonylation reaction, it has been found that hydrocarbon
presence of homogeneous catalysts to produce acetic acid are formation is significantly suppressed, thereby allowing an
operated commercially. Gas phase carbonylation processes improved reaction start-up to be achieved.
employing methanol and dimethyl ether using heterogeneous Thus, the present invention further provides for the use of
catalysts are also known. at least one of methyl acetate and acetic acid in a carbonyla
EP-A-0 596 632 describes a vapour phase process for the tion process to reduce the formation of by-products, wherein
carbonylation of methanol to produce acetic acid at high said process comprises carbonylating dimethyl ether with
temperatures and pressures in the presence of a mordenite carbon monoxide in one or more carbonylation reaction
catalyst which has been loaded with copper, nickel, iridium, Zone(s) in the presence of a mordenite catalyst to produce
rhodium or cobalt methyl acetate product, characterised in that at least one of
WO 01/07393 describes a process for the catalytic conver 25 methyl acetate and acetic acid is added to at least one of said
sion of a feedstock comprising carbon monoxide and hydro reaction Zone(s).
gen to produce at least one of an alcohol, ether and mixtures The process of the present invention is a carbonylation
thereof and reacting carbon monoxide with the at least one of process in which dimethyl ether is carbonylated with carbon
an alcohol, ether and mixtures thereof in the presence of a monoxide to produce methyl acetate. The dimethyl ether may
catalyst selected from Solid Super acids, heteropolyacids, 30 be substantially pure or may contain Small quantities of inert
clays, Zeolites and molecular sieves, in the absence of a halide impurities. In commercial practice, dimethyl ether is pro
promoter, under conditions oftemperature and pressure suf duced by the catalytic conversion of synthesis gas (mixtures
ficient to produce at least one of an ester, acid, acid anhydride of hydrogen and carbon monoxide) over methanol synthesis
and mixtures thereof. and methanol dehydration catalysts. This catalytic conver
WO 2005/105720 describes a process for production of a 35 sion results in a product which is predominantly dimethyl
carboxylic acid and/or an ester or anhydride thereof by car ether but it may also contain some methanol. In the process of
bonylating an aliphatic alcohol or reactive derivative thereof the present invention the dimethyl ether feed may addition
with carbon monoxide in the Substantial absence of halogens ally comprise Small amounts of methanol provided that the
at a temperature in the range 250-600° C. and a pressure in the amount of methanol present in the feed is not so great as to
range 10 to 200 bar in the presence of a mordenite catalyst 40 inhibit the carbonylation reaction to methylacetate product. It
which has been modified with copper, nickel, iridium, has been found that 5 wt % or less, such as 1 wt % or less of
rhodium or cobalt and has as framework elements, silicon, methanol may be tolerated in the dimethyl ether feed.
aluminium, and at least one of gallium, boron and iron. Dimethyl ether may also be generated from dimethyl car
WO 2006/121778 describes a process for the production of bonate, for example, by contacting liquid dimethyl carbonate
a lower alkyl ester of a lower aliphatic carboxylic acid by 45 with gamma-alumina to decompose the dimethyl carbonate
carbonylating under Substantially anhydrous conditions a to dimethyl ether and carbon dioxide.
lower alkyl ether, such as dimethyl ether, with carbon mon Suitably, dimethyl ether is introduced into a reaction Zone
oxide in the presence of a mordenite or ferrierite catalyst. at a concentration in the range of at least 1.0 mol% to 20 mol
A disadvantage of conducting carbonylation reactions in %, for example, 1.5 mol % to 10 mol %, such as 2.5 to 5 mol
the presence of a Zeolite catalyst Such as a mordenite is that 50 %, based on the total gaseous feeds (including recycles) to the
selectivity to the carbonylation product methyl acetate is reaction Zone. Where more than one reaction Zone is
decreased owing to the formation of by-products, and, in employed, the concentration of dimethyl ether introduced
particular to the formation of the by-products, methane and into each reaction Zone can be the same or different. The
Chydrocarbons. The Chydrocarbons are typically, C. to dimethyl ether introduced into a reaction Zone may be fresh
Caliphatic hydrocarbons, such as ethane and propane, C to 55 and/or recycle dimethyl ether.
Calkenes, such as ethylene and propylene. Aromatic hydro In addition to dimethyl ether and carbon monoxide, the
carbons may also be formed, such as methylated benzenes, gaseous feeds to a reaction Zone may include methyl acetate,
for example, Xylenes. acetic acid, hydrogen and inert gases, such as nitrogen,
Thus, it would be advantageous if such by-product forma helium and argon.
tion in mordenite catalysed carbonylation processes to pro 60 In the process of the present invention, at least one of
duce methyl acetate could be reduced. methyl acetate and acetic acid is added to at least one reaction
It has now been found that if the carbonylation reaction is Zone. Where more than one reaction Zone is employed,
conducted in the presence of added methyl acetate (that is, methyl acetate and/or acetic acid may be added to some but
methyl acetate which is in addition to that produced as a not necessarily all of the reaction Zones employed.
product of the carbonylation reaction between dimethyl ether 65 Where methyl acetate is added to a reaction Zone, the molar
and carbon monoxide) and/or acetic acid, the formation of ratio of methyl acetate to dimethyl ether is suitably, in the
by-products is reduced. range 1:100 to 5:1, such as 1:10 to 3:1.
 US 8,624,054 B2
3 4
Suitably, methyl acetate may be added to a reaction Zone in preferably used in the H-form or ion-exchanged or otherwise
an amount of 5 mol% or less, based on the total gaseous feeds loaded with one or more metals.
(including recycles). Preferably, methyl acetate is added in an The ammonium form of mordenite may be converted to the
amount in the range 0.05 mol % to 5 mol %, such as 0.5 to 5 H-form by well-known techniques such as calcination at high
mol% based on the total gaseous feeds (including recycles). temperature. The sodium form of mordenite can be converted
Suitably, where dimethyl ether is introduced into a reaction to the acid form (H-form) by converting first to the ammo
Zone in an amount of 5 mol %, methyl acetate is Suitably nium form by ion exchange with ammonium salts such as
ammonium nitrate.
present in an amount of 0.5 to 2.5 mol % based on the total Alternatively, the mordenite may be loaded with at least
gaseous feeds (including recycles).
Where acetic acid is added, it reacts with dimethyl ether 10 one metal, preferably selected from copper, silver, gold,
present in a reaction Zone to generate methyl acetate and nickel, iridium, rhodium, platinum, palladium or cobalt, more
methanol. Suitably, the amount of added acetic acid is in the preferably, selected from at least one of copper and silver.
range (greater than 0) to 1 mol % based on the total gaseous The loading of the mordenite with metals may be carried
feeds (including recycles), for example, in the range 0.1 to 0.8 out by any known method such as the well-known techniques
15 of ion-exchange, wet impregnation and incipient wetness. If
mol%. the mordenite is to be ion-exchanged up to 100% of the
The components of the carbonylation process may be fed cation-exchangable sites on the mordenite may be exchanged
separately to a reaction Zone or may be fed as mixtures of 2 or with metal ions using well known techniques. It is preferred
more components. Thus, the methyl acetate and/or acetic acid that any remaining cations in the exchanged mordenite are
may be fed separately to, or, together with dimethyl ether to a protons hence it is convenient to start the exchange process
reaction Zone. from the ammonium or hydrogen form.
The methyl acetate may be introduced into a reaction Zone As an alternative to ion-exchange, the ammonium or
as fresh methyl acetate and/or as recycle methyl acetate. hydrogen form of the mordenite can be impregnated with a
Alternatively or additionally, methyl acetate product from Solution of metal salts and Subsequently dried. If the ammo
one reaction Zone may be added to a successive reaction Zone. 25 nium form is used, it is preferred to calcine the mordenite after
The methyl acetate and acetic acid may be fed to a reaction the loading or ion-exchange with the metals has been com
Zone as a vapour or they can be fed as a liquid to a pre pleted.
vapourisation Zone, where they are vaporised prior to contact The metal loading in the mordenite can be expressed in
with the catalyst. terms of the fractional loading of the metal as gram atoms of
In a preferred embodiment, at least 2 reaction Zones con 30 metal per gram atom of aluminium in the mordenite. The
nected in series, such as 2 to 30 reaction Zones, are employed metal loading can also be expressed as a mole percentage
and dimethyl ether is introduced into one or more of these loading relative to aluminium in the mordenite through the
reaction Zones as fresh dimethyl ether together with at least relationship:
one of fresh and/or recycle methyl acetate and acetic acid.
The carbon monoxide may be substantially pure carbon 35 mol % Metal (gram atoms Metal gram atoms alu
monoxide, for example, carbon monoxide typically provided minium)x100
by Suppliers of industrial gases, or it may contain impurities Thus, for example, a loading of 0.55 gram atom of copper
that do not interfere with the conversion of the dimethyl ether per aluminium in the mordenite equates to a 55 mol% loading
to methyl acetate. Such as nitrogen, helium, argon, methane of copper relative to aluminium in the mordenite.
and/or carbon dioxide. 40 A metal may be loaded in an amount in the range of 1 to 200
The process of the present invention may be carried out in mol % relative to aluminium, for example, 50 to 120 mol %,
the presence of hydrogen. Suitably, carbon monoxide and such as 50 to 110 mol% relative to aluminium in the morden
hydrogen may be fed to a reaction Zone as a mixture. Mixtures ite.
of hydrogen and carbon monoxide are commercially pro Suitably, the mordenite catalyst for use in the present
duced by the steam reforming of hydrocarbons and by the 45 invention is selected from a H-mordenite, a copper mordenite
partial oxidation of hydrocarbons. Such mixtures are com and a silver mordenite.
monly referred to as synthesis gas. Synthesis gas comprises For use in the process of the present invention it is preferred
mainly carbon monoxide and hydrogen but may also contain that the mordenite has a silicato aluminaratio of at least 5 but,
Smaller quantities of carbon dioxide. preferably less than or equal to 100, such as in the range 6 to
Suitably, the molar ratio of carbon monoxide:hydrogen 50 90, for example 10 to 40.
may be in the range 1:3 to 15:1, such as 1:1 to 10:1, for The process of the present invention is preferably carried
example, 1:1 to 4:1. out under Substantially anhydrous conditions, i.e in the Sub
Where hydrogen is present in the process, it may be present stantial absence of water. The carbonylation of dimethyl ether
at a partial pressure of at least 0.1 barg, Such as 1 to 30 barg. to methyl acetate does not generate water in-situ. Water has
The molar ratio of carbon monoxide to dimethyl ether is 55 been found to inhibit the carbonylation of dimethyl ether to
suitably in the range 1:1 to 99:1, such as 2:1 to 60:1. form methyl acetate. Thus, in the process of the present inven
The catalyst used in the process of the present invention is tion, wateris kept as low as is feasible. To accomplish this, the
a mordenite Zeolite. The structure of mordenite is well known dimethyl ether and carbon monoxide reactants (and morden
and defined, for example, in The Atlas of Zeolite Framework ite catalyst) are preferably dried prior to introduction into the
Tipes (C. Baerlocher, W. M. Meier, D. H. Olson, 5" ed. 60 process. However, Small amounts of water may be tolerated
Elsevier, Amsterdam, 2001). The web-based version (http:// without adversely affecting the formation of methyl acetate.
www.iza-structure.org/databases/) is a compendium oftopo Suitably, water may be present in the dimethyl ether feed in an
logical and structural details about Zeolites including amount of 2.5 wt % or less, such as 0.5 wt % or less.
mordenite. The process of the present invention may suitably be car
Mordenite is commercially available as Na-mordenite, 65 ried out at a temperature in the range of 100° C. to 350° C.
NH-mordenite or H-mordenite. For use as the catalyst in the The process of the present invention may be carried out at
carbonylation process of the present invention, mordenite is a pressure in the range 1 to 100 Barg, such as 10 to 100 barg.
 US 8,624,054 B2
5 6
The Gas Hourly Space Velocity (GHSV) is suitably in the the feed to the carbonylation of dimethyl ether with carbon
range 500 to 40,000 h", such as 4000 to 10,000 h. monoxide in the presence of hydrogen.
Because the process of the present invention is preferably Each carbonylation reaction was carried out in a pressure
carried out in the substantial absence of water, it is preferred flow reactor unit consisting of a single hastelloy reactor. The
that the mordenite catalyst is dried prior to use. The catalyst reactor contained 55 ml glass beads, 10 ml gamma alumina
may be dried, for example by heating to a temperature of 400 and 5 ml catalyst all separated by glass wool. The catalyst
to SOO C. consisted of a mordenite (Zeolyst CBV21A) loaded with 55
It is preferred that the mordenite catalyst is activated imme mol % copper. Prior to use the catalyst was compacted at 12
diately before use by heating the catalyst at elevated tempera tonnes in a 26 mm die set using a pneumatic press, crushed
ture for at least one hour under flowing nitrogen, carbon 10 and sieved to a pellet size fraction of 500-1000 microns. The
monoxide, hydrogen or mixtures thereof. catalyst was pressurised with helium at a flow rate of 13.2 l/h.
Preferably, the process of the present invention is carried to a reaction pressure of 30 bar and then heated to 100° C.
out substantially in the absence of halides, such as iodide. By where it was held for 17 hours. Subsequently the temperature
the term substantially is meant that the halide, for example, was ramped to 300° C. at 3 deg. C./minat which point helium,
iodide content of the reactant gases and catalyst is less than 15 carbon monoxide and hydrogen were introduced at a molar
500 ppm, preferably less than 100 ppm. ratio of 1:4:1 (He:CO:H) to maintain a GHSV of 4000/h for
The process of the present invention is suitably carried out 2 hours. After 2 hours, an amount of liquid dimethyl carbon
using a fixed bed, fluidised bed or moving bed of the morden ate was introduced into the reactor to generate 5 mol %
ite catalyst. dimethyl ether. Where used, methyl acetate, dissolved in the
The process of the present invention may be carried out in dimethyl carbonate to the required amount, was also intro
a single reaction Zone or in at least 2 reaction Zones connected duced into the reactor with the amount of liquid fed adjusted
in series, such as 2 to 30 reaction Zones. One or more reaction to maintain 5 mol % dimethyl ether. The flow rates of the
Zones may be housed in a single reaction vessel. If desired, helium, carbon monoxide, hydrogen, dimethyl ether and
cooling or additional heating means may be applied between methyl acetate were sufficient to maintain a GHSV of 4000/h.
reaction Zones. 25 Where methyl acetate was used, the helium flow was reduced
The primary product of the process of the present invention to maintain the GHSV at 4000/h. The exit stream from the
is methyl acetate but Small amounts of acetic acid may also be reactor was passed to a liquid collection vessel maintained at
produced. Methyl acetate product may be removed in the 20°C. which condensed the liquid products. These products
form of a vapour and thereafter condensed to a liquid. were analysed at regular intervals by gas chromatography to
The methyl acetate may be recovered and sold as such or it 30 determine the concentration of liquid reactants and liquid
may be forwarded to other chemical processes. Where the carbonylation reaction products. The remaining vapour
methyl acetate is recovered from the carbonylation reaction stream was analysed by online GC to determine the concen
products, some or all of it may be hydrolysed to form acetic tration of reactants and carbonylation reaction products. The
acid. Alternatively, the entire carbonylation reaction product reaction was allowed to continue up to 160 hours under con
may be passed to a hydrolysis stage and acetic acid separated 35 ditions of 300° C., 30 bar, and a gas hourly space velocity
thereafter. The hydrolysis may be carried out by known tech (GHSV) of 4000/h.
niques such as reactive distillation in the presence of an acid The results of the STY (space time yield) to methane by
catalyst. product are shown in FIG. 1. As FIG. 1 clearly shows, the
The process may be operated as either a continuous or a presence of methyl acetate in the feed to the reaction, signifi
batch process, preferably as a continuous process. 40 cantly reduces the production of methane.
In the Figures, FIG. 1 depicts the space time yield (STY) to
methane in g/1/h versus time on stream for carbonylation EXAMPLE 2
carried out with Omol %, 0.05% mol%, 0.625 mol% and 2.5
mol % methyl acetate. Carbonylation of Dimethyl Ether with 1 mol % Methyl
FIG. 2 depicts the space time yield (STY) to methane in 45 Acetate
g/l/h versus time on stream for carbonylation carried out with The carbonylation of dimethyl ether in the presence of a
Omol % and 1 mol % methyl acetate and 2.5 mol% dimethyl catalyst consisting of mordenite (Zeolyst CBV21A) loaded
ether. with 55 mol % copper was carried out in a pressure flow
FIG.3 depicts the selectivity to methyl acetate versus time reactor unit consisting of 16 identical reactors of the type
on stream for carbonylation carried out with Omol % and 1 50 described in WO 2005063372. Reactors with an internal
mol % methyl acetate and 2.5 mol % dimethyl ether. diameter of 9.2 mm were employed. The centre of each reac
FIG.4 depicts the spacetime yield (STY) to Chydrocar tor was fitted with internal tube of diameter 3.2 mm into
bons in g/l/h versus time on stream for carbonylation carried which a thermocouple was placed. Prior to the loading of the
out with 0 and 1 mol % methyl acetate and 2.5 mol % dim catalyst into each reactor, a ca. 10 cm bed of corundum of
ethyl ether. 55 sieve fraction of 125-160 um was placed in the catalyst
FIG. 5 depicts the space time yield (STY) to methane in holder. On a dry mass basis (determined by loss on ignition of
g/1/hr versus time on stream for carbonylation carried out with the catalyst measured by heating the catalyst from room tem
the addition of Omol %, 0.3 mol % and 0.625 mol % acetic perature to 600° C. at a ramp rate of ca. 30° C. per minute)
acid. 1.948 g of catalyst (pellet size 125 to 160 microns) diluted
The invention is now illustrated with reference to the fol 60 with 3 ml of corundum (pellet size 125 to 160 microns) was
lowing Examples. placed on top of the corundum bed. Each of the Zones above
was concreted via hitting or vibrating to get a stable bed and
EXAMPLE1 a defined starting height of the catalyst Zone. The diluted
catalyst was covered by a ca. 13 cm corundum bed of a
Carbonylation of Dimethyl Ether 65 particle size of 125-160 um. The catalyst was pressurised to a
This Example demonstrates the effect of employing O mol reaction pressure of 70 bar using a 2:1 CO:H mixture at a
%, 0.05 mol%, 0.625 mol% and 2.5 mol% methylacetate in flow rate of 12 1/h. The catalyst was then heated at 0.5 deg.
 US 8,624,054 B2
7 8
C./min to 220° C., where it was held for 3 hours. Subse CO:H mixture at a flow rate of 4.275 l/h. The catalyst was
quently the temperature was ramped to 300° C. at 0.5 deg. then heated at 0.5°C/min to a holding temperature of 220
C./min, followed by a dwell time of 3 hours. The carbon C., where it was held for 3 hours. Subsequently the tempera
monoxide and hydrogen feed was then Switched to a mixture ture was ramped to 300° C. at 0.5 deg. C./min, followed by a
of carbon monoxide, hydrogen, dimethyl ether, methyl dwell time of 3 hours. The carbon monoxide and hydrogen
acetate, argon and nitrogen with a CO/H/dimethyl ether/Art feed was then changed to a CO/H/dimethyl ether feed of
methyl acetate/N molar ratio of 54/29/2.5/5/1/8.5 at a flow molar ratio 72/18/10 at a flow rate of 4.275 l/h, with a dim
rate of 12 1/h, with both dimethylether, at 0.301/h, and methyl ethyl ether vapour feed rate of 0.4275 l/h. Nitrogen gas was
acetate, at 0.12 1/h, fed as a vapour, to obtain a CO/H/methyl also introduced at a variable rate of 0-50 ml/min to equalise
acetate/dimethyl ether ratio in the total feed of 54/29/1/2.5 on 10 the pressure Swings between the 16 reactor exits. The exit
a molar basis. In addition, nitrogen gas was introduced at a stream from a reactor was passed to a gas chromatograph to
variable rate of 0-150 ml/min to equalise the pressure swings determine the concentration of reactants and carbonylation
between the 16 reactor exits. The exit stream from the test reaction products. The reaction was allowed to continue for
reactor was passed to a gas chromatograph to determine the 148 hours under conditions of 300° C., 70 bar, a gas hourly
concentration of reactants and carbonylation products. The 15 space velocity (GHSV) of 4275/h with a CO/H/dimethyl
reaction was allowed to continue for 150 hours under condi ether molar ratio in the total feed of 72/18/10. After 148 hours
tions of 300° C., 70 bar, a gas hourly space velocity (GHSV) total reaction time the feed was switched to CO/H/dimethyl
relative to the catalyst of 4000/h with a CO/H/dimethyl ether with a molar ratio of 76/1975 and the reactionallowed to
ether/Ar/methyl acetate/N molar ratio of 54/29/2.5/5/1/8.5 continue for a further 49 hours. After 197 hours total reaction
in the total feed. time, a co-feed of methyl acetate was introduced to the car
Experiment A Carbonylation of Dimethyl Ether in the bonylation reactor, the reactor being fed with CO/H/dim
Absence of Methyl Acetate Feed ethylether/methylacetate atamolar ratio of 72/18/5/5 at 300°
Example 2 was repeated, except that methyl acetate was C., 70 bar, and gas hourly space velocity (GHSV) of 4275/h.
not present in the feed to the carbonylation reaction. The The reaction was allowed to continue for a further 45 hours.
carbonylation feed consisted of a mixture of carbon monox 25 After 242 hours total reaction time the methyl acetate co-feed
ide, hydrogen, dimethyl ether, argon and nitrogen with a was ceased, and the feed to the reactor changed to CO/H/
CO/H/DME/Ar/N molar ratio of 54/29/2.5/5/9.5 at a flow dimethylether with amolar ratio of76/19/5 at 300° C., 70 bar,
rate of 12 1/h. and gas hourly space velocity (GHSV) of 4275/h. The reac
The results of the carbonylation reactions of Example 2 and tion was allowed to continue for a further 74 hours. The
Experiment A are shown in FIGS. 2 to 4. The space time yield 30 results of the carbonylation reaction are given in Table 1
(STY) to the by-products methane and C. hydrocarbons are below.
shown in FIGS. 2 and 4 respectively. The selectivity to methyl
acetate product is shown in FIG. 3. TABLE 1
As can clearly be seen from FIGS. 2 and 4 the presence of Time? DME feed MeOAc feed STY Methane,
methyl acetate in the feed to the carbonylation reaction 35
hours mol % mol % gll h
reduces the amount of methane and C. hydrocarbons pro
duced compared to the amount produced in the absence of 194
223
5
5
O
5
6
<2
methyl acetate in the reaction feed. 288 5 O 6
As can be seen from FIG. 3 the presence of methyl acetate
in the feed to the carbonylation reaction provides an improved 40
selectivity to methyl acetate product over that achieved in the Table 1 shows the results of the impact of the presence and
absence of methyl acetate in the reaction feed. absence of a methyl acetate co-feed on the production of
methane by-product. As can clearly be seen, the presence of
EXAMPLE 3 methyl acetate in the carbonylation feed Suppresses the for
45 mation of methane and that in the absence of methylacetate in
Carbonylation of Dimethyl Ether with 5 mol % Methyl the carbonylation feed, the production of methane increases.
Acetate
The carbonylation of dimethyl ether in the presence of a EXAMPLE 4
catalyst consisting of mordenite (Zeolyst CBV21A) loaded
with 55 mol % copper was carried out in a pressure flow 50 This Example demonstrates the effect of employing O mol
reactor unit consisting of 16 identical reactors of the type %, 0.3 mol % and 0.625 mol% acetic acid in the carbonyla
described in WO 2005063372. Each reactor had an internal tion of dimethyl ether. The procedure used in Example 1 was
diameter of 3.6 mm. Prior to the loading of the catalyst into a repeated except that methyl acetate was replaced by 0.3 mol
reactor, a ca. 5 cm bed of steatite of sieve fraction of 100-350 % or 0.625 mol % acetic acid.
um was placed in the respective catalyst holder. A ca. 5 cm 55 The results of the STY (space time yield) to methane by
Zone of corundum of sieve fraction of 125-160 um was placed product are shown in FIG. 5. As FIG. 5 clearly shows, the
on top of the steatite bed. On a dry mass basis (determined by addition of acetic acid to the reaction, significantly reduces
loss on ignition of the catalyst measured by heating the cata the production of methane.
lyst from room temperature to 600° C. at a ramp rate of ca. 30° The invention claimed is:
C. per minute). 0.625 g of catalyst (pellet size 125 to 160 60 1. A process for the production of methyl acetate, which
microns) was placed on top of the corundum bed. The catalyst process comprises carbonylating dimethyl ether with carbon
was covered by a ca. 5 cm corundum bed of a particle size of monoxide in one or more carbonylation reaction Zones in the
125-160 p.m. A ca. 5 cm Zone of steatite of sieve fraction of presence of a mordenite catalyst to produce methyl acetate
100-350 um was placed on top of the corundum bed. Each product wherein at least one of acetic acid and additional
Zone was concreted via hitting or vibrating to get a stable bed 65 methyl acetate is added to at least one of said reaction Zone(s).
and a defined starting height of the catalyst Zone. The catalyst 2. A process according to claim 1 wherein the process is
was pressurised to a reaction pressure of 70 bar using a 4:1 carried out in the presence of hydrogen.
 US 8,624,054 B2
10
3. A process according to claim 1 wherein the molar ratio of 10. A process according to claim 9 wherein acetic acid is
the additional methyl acetate to dimethyl ether is in the range added to a reaction Zone in an amount in the range 0.1 mol%
1:100 to 5:1. to 0.8 mol % based on the total gaseous feeds (including
4. A process according to claim3 wherein the molar ratio of recycles).
the additional methyl acetate to dimethyl ether is in the range 5 11. A process according to claim 1 wherein the mordenite
1:10 to 3:1. catalyst is selected from H-mordenite, a copper mordenite
and a silver mordenite.
5. A process according to claim 1 wherein the additional 12. A process according to claim 1 wherein the process is
methyl acetate is added to a reaction Zone in an amount in the carried out in 2 to 30 reaction Zones connected in series.
range 0.05 mol% to 5 mol% based on the total gaseous feeds, 10 13. A process according to claim 12 wherein dimethyl ether
including recycles. is introduced into a reaction Zone as fresh and/or recycle
6. A process according to claim 5 wherein the additional dimethyl ether.
methyl acetate is added to a reaction Zone in an amount in the 14. A process according to claim 13 wherein dimethyl ether
range 0.5 mol % to 5 mol% based on the total gaseous feeds, is introduced to a reaction Zone as fresh dimethyl ether
including recycles. 15
together with at least one of fresh and/or recycle methyl
7. A process according to claim 1 wherein the additional acetate and acetic acid.
methyl acetate is added to a reaction Zone as fresh and/or 15. A process according to claim 1 wherein methyl acetate
recycle methyl acetate and/or as product methyl acetate. product is hydrolysed to acetic acid.
8. A process according to claim 1 wherein the additional 16. A process according to claim 1 wherein the carbon
monoxide
methyl acetate is introduced to the reaction Zone on start-up of 20 gen. is fed into a reaction Zone as a mixture with hydro
the carbonylation process.
9. A process according to claim 1 wherein acetic acid is 17. A process according to claim 16 wherein the carbon
added to a reaction Zone in an amount in the range (greater monoxide and hydrogen are present in the mixture in a molar
ratio of 1:3 to 15:1.
than 0) mol % to 1 mol % based on the total gaseous feeds,
including recycles.