Title of Invention

"A CARBONYLATION PROCESS FOR THE PRODUCTION OF A CARBONYLATION PRODUCT"

Abstract A carbonylation process for the production of a carbonylation product by contacting carbon monoxide with a feed comprising an alcohol or a reactive derivative thereof in the vapour phase using an heterogenous heteropolyacid catalyst comprising one or more metal cations selected from Cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt, characterized in that there is also present in the feed at least 0.5wt% water.
Full Text The present invention relates in general to the production of a carbonylation product by the carbonylation of an alcohol and/or a reactive derivative thereof and, in particular, to the production of a carbonylation product by the vapour phase carbonylation of an alcohol and/or a reactive derivative thereof in the presence of water and a heterogeneous carbonylation catalyst.
Acetic acid may be produced by the rhodium-catalysed, iodide-promoted carbonylation of methanol in a homogeneous liquid-phase reaction medium, such as described, for example in US 3,769,329. The rhodium-catalysed, iodide-promoted liquid phase carbonylation of methanol is a well-known process and is operated on a commercial scale. The desirability of employing heterogeneous carbonylation catalysts for the purpose of facilitating product separation from the catalyst has also been recognised: Heterogeneous carbonylation catalysts and their use are described in a number of patent publications including, for example WO 98/57918, EP 0885870 Al and EP 0353722 A2.
WO 98/57918 describes a process for the production of a carboxylic acid by the carbonylation of an alcohol and/or a reactive derivative thereof in the liquid phase over a heterogeneous carbonylation catalyst comprising a group VIII noble metal species on a polymeric resin having functional groups selected from nitrogen containing heterocycles. Hydrogen is added to the carbonylation to reduce leaching of the active catalytic species from the support material during carbonylation.
EP 0885870 Al describes a process for the production of carboxylic acid and/or carboxylic acid anhydrides which comprises contacting an alcohol and//or a carboxylic acid ester, optionally water, a first hydrocarbyl halide and/or a hydrocarbyl ether

reactant and a second hydrocarbyl halide promoter, with carbon monoxide in the
presence of a catalyst comprising an insoluble imidazole-containing resin supporting a
Group VIII metal species. The process may be performed in the liquid or the vapour
phase.
EP 0353722 A2 describes a process for the vapour phase carbonylation of one or
more alcohols, ethers or ether alcohols to esters and, optionally, to carboxylic acids over
a solid catalyst comprising a polyoxometalate anion in which the metal is at least one
taken from Group V and VI of the periodic table, such as Mo, W, V, Nb, Cr and Ta,
complexed with at least one Group VIIIA cation, such as Fe, Ru, Os, Co, Rh, Ir, Ni, Pd
and Pt.
US 6,127,432 describes processes for the conversion of a feedstock comprising
carbon monoxide and hydrogen to a product stream comprising at least one of an ester,
acid, acid anhydride and mixtures thereof. US 6,127,432 also describes a process for
converting.an alcohol, ether and/or ether alcohol to oxygentated products such as esters,
acids, acid anhydrides and mixtures thereof, which process may be conducted in the
vapour phase over a heterogeneous alcohol carbonylation catalyst selected from a solid
superacid, clay, zeolite or molecular sieve. The alcohol carbonylation catalysts include
heteropolyacids comprising a polyoxometalate anion in which a metal, or mixture of
metals, selected from Groups 4, 5,6 and 7 metals is complexed with a cation from a
member of Group 7, 8,9 10 and/or 11 metals, such as Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and
Pt. A preferred heteropolyacid comprises M W P O , wherein M is Ir, Ru, Rh, Pd and
combinations thereof. US 6,127,432 states that the stability of the heterogeneous alcohol
carbonylation catalyst is improved by use of hydrogen or a feedstock containing
hydrogen in the carbonylation process.
We have now found that addition of water to the feed in a vapour phase,
heterogeneous carbonylation process utilising an heteropolyacid catalyst comprising one
or more metal cations gives improved catalyst activity.
Accordingly, the present invention provides a carbonylation process for the
production of a carbonylation product by contacting carbon monoxide with a feed
comprising an alcohol and/or a reactive derivative thereof in the vapour phase using an
heterogeneous heteropolyacid catalyst comprising one or more metal cations selected
from Cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt, characterised in that there is also present
in the feed at least 0.5wt% water.
The present invention also provides for the use of water at a concentration of at
least 0.5wt% in the feed to a carbonylation process to increase the activity of an
heterogeneous heteropolyacid catalyst comprising one or more metal cations selected
from Cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt in the production of a carbonylation
product by contacting carbon monoxide with an alcohol and/or reactive derivative
thereof in the vapour phase over said catalyst.
The water may be fresh water and/or recycled water.
Preferably, the water (fresh and/or recycle) in the feed to the carbonylation
process is present at a concentration of at least lwt%, such as at least 2wt%. More
preferably, the water in the feed to the carbonylation process is present at a
concentration of at least 5wt%.
Preferably, the water (fresh and/or recycle) in the feed to the carbonylation
process is present at a concentration of up to 20wt% water, such as up to 15wt% water.
Most preferably, the water in the feed to the carbonylation process is present at a
concentration of 5 to 15wt%.
By "heteropolyacid catalyst comprising one or more metal cations selected from
Cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt", as used herein, is meant an heteropolyacid in
which one or more of the hydrogen ions of the free heteropolyacid has been substituted
by at least one of the described cations (hereinafter a substituted heteropolyacid). In
addition to the one or more metal cations selected from Cu, Fe, Ru, Os, Co, Rh, Ir, Ni,
Pd and Pt, the heteropolyacid may comprise further cations, such as "residual" hydrogen
ions and/or alkali metal cations selected from Li, Na, Rb and Cs.
Typically, the heteropolyacid anion comprises 2-18 oxygen-linked polyvalent
metal atoms^ which are known in the art as peripheral atoms. These peripheral atoms
surround one or more central atoms in a symmetrical manner. The peripheral atoms are
usually one or more of molybdenum, tungsten, vanadium, niobium, chromium and
tantalum, but may be or may include other metals. The central atoms are usually silicon
or phosphorus but can comprise any one of a large variety of atoms from Groups I-VIII
in the Periodic Table of elements. These include, for instance, cupric ions; divalent
beryllium, zinc, cobalt or nickel ions; trivalent boron, aluminium, gallium, iron, cerium,
arsenic, antimony, phosphorus, bismuth, chromium or rhodium ions; tetravalent silicon,
germanium, tin, titanium, zirconium, vanadium, sulphur, tellurium, manganese nickel,
platinum, thorium, hafnium, cerium ions and other rare earth ions; pentavalent
phosphorus, arsenic, vanadium, antimony ions; hexavalent tellurium ions; and
heptavalent iodine ions. Such heteropolyacids are also known as "polyoxoanions",
"polyoxometallates" or "metal oxide clusters". The structures of some of the well known
anions are named after the original researchers in this field such as, for example, the
structures known as Keggin, Wells-Dawson and Anderson-Evans-Perloff structures.
The preferred heteropolyacids for use in the process according to the present
invention comprise one or more of molybdenum, tungsten, vanadium, niobium,
chromium and tantalum as the peripheral atoms and silicon or phosphorus as the central
atoms.Typically the substituted heteropolyacid will comprise 1 to 6 % by weight of the
substituent metal cation, preferably 3 to 5% by weight. The substituted heteropolyacids
usually have a high molecular weight, for example, in the range from 2000 to 8000,
preferably in the range 2000 to 4000, and can include dimeric complexes.
Preferably, the substituted heteropolyacid is selected from substituted
silicotungstic acids, silicomolybdic acids, phosphotungstic acids, phosphomolybdic
acids, such as substituted heteropolyacids of the following free acids:
12-tungstophosphoric acid H3[PWi2O/)o].xH20
12-molybdophosphoric acid H3[PMoi2O4o].xH2O
12-tungstosilicic acid
12-molybdosilicic acid
Preferably, the metal cation is selected from one or more of rhodium, iridium
and copper, and in particular is rhodium or iridium. Rhodium is the most preferred
metal cation.
The substituted heteropolyacid is preferably supported. Suitably, the support
may be selected from oxide supports such as silica, silica /aluminas, zeolites, clays,
diatomaceous earths, titania and alumina. Other non-oxide supports that can be used
include silicon carbide, organic polymers such as crosslinked polystyrenes and carbons.
The support, such as a siliceous support, is suitably in the form of granules, beads,
globules, extrudates or pellets.
Where the substituted heteropolyacid is supported the substituted heteropolyacid
is typically present at a loading of 20-70% by weight of the total weight of the
supported substituted heteropolyacid, that is, the substituted heteropolyacid forms 20-
70% by weight of the total weight of the substituted heteropolyacid and the support.
Preferably, where the substituted heteropolyacid is supported, the substituted
heteropolyacid is present at a loading of 30-65% by weight of the total weight of the
supported substituted heteropolyacid.
Preferably, the alcohol is an aliphatic alcohol having 1 to 12 carbon atoms,
preferably 1 to 6 carbon atoms, including methanol, ethanol, propanol, isopropanol, the
butanols, pentanols and hexanols. A preferred alcohol is methanol.
Reactive derivatives of the alcohol which may be used as an alternative to, or in
addition to, the alcohol include one or more dialkyl ethers, esters of the alcohol and
alkyl halides. Suitable reactive derivatives of methanol, for example, include methyl
acetate, dimethyl ether and methyl iodide. A mixture of an alcohol and a reactive
derivative thereof, for example a mixture of methanol and methyl acetate, may also be
employed.
Where a reactive derivative such as an ether or an ester of an alcohol is
employed together with an alcohol, the ether and/or ester is present in an amount up to
equimolar to the amount of water present in the feed.
The reactive derivative such as an ether or an ester of an alcohol may be
employed as a fresh feed and/or obtained from a recycle stream.
The carbonylation product is a carboxylic acid and/or the corresponding
carboxylic ester. Thus, where methanol is employed as the alcohol feed, the
carbonylation product comprises acetic acid and/or methyl acetate.
Water may be produced during the carbonylation process as a by-product of
esteriflcation. This water may be recycled to the reactor. It may be necessary to add
"fresh" water to the carbonylation reaction feed in addition to any water that may be
recycled in order to maintain the desired concentration of water in the feed to the
reactor.
The carbon monoxide reactant may be essentially pure or may contain impurities
such as carbon dioxide, methane, nitrogen, noble gases and C1 to C4 paraffinic
hydrocarbons.
The carbon monoxide (CO) may be present in the reaction at any suitable partial
pressure, such as a partial pressure of at least 0.1 bar. More particularly, the CO may be
fed to the reactor in a suitable molar ratio, to the alcohol feed (and/or reactive
derivative), preferably at a CO to alcohol molar ratio of at least 1:1, such as at least 5:1,
and/or up to 20:1, most preferably in the range 5:1 to 15:1.
In a preferred embodiment of the present invention, the carbonylation reaction
may be performed in the presence of hydrogen. The hydrogen reactant may be fed to the
reactor as an essentially pure hydrogen feed or the hydrogen feed stream may contain
impurities, such as carbon oxides and nitrogen. Where hydrogen is used in the process
of the present invention, it is especially desirable to use synthesis gas as a source of both
the hydrogen and the carbon monoxide.
The hydrogen, when present, may be present in the reaction at any suitable
hydrogen concentration, such as at a partial pressure of at least 0.1 bar, and is especially
fed, either separately from or combined with carbon monoxide, such that the hydrogen
to carbon monoxide molar ratio in the reactor is at least 1:20, such as 1:20 to 20:1, most
preferably in the range 1:10 to 10:1.
The process of the invention may be operated at below atmospheric pressure, but
is preferably operated at a total pressure in the range from 1 to 100 barg, preferably
from 1 to 20 barg.
The process is suitably performed at a temperature in the range from 100 to
300°C, the practical upper operating temperature being dependant on the thermal
stability of the catalyst. Preferably the temperature is in the range 150 to 250°C, most
preferably in the range 200 to 250°C.
The process is suitably performed by contacting the reactants with the catalyst at
a gas hourly space velocity (GHSV) in the range from 100 to 10000 h"1, Preferably the
GHSV is in the range 500 to 5000 h"1.
The process may be operated as a batch or continuous process, preferably as a
continuous process.
The invention will now be illustrated by reference to the following examples.
Examples
Catalyst A preparation
A rhodium-substituted heteropolyacid catalyst was prepared as follows.
RhCl3.H2O (Aldrich, FW=209.26,0.774 g) was dissolved in methanol (ca 200ml) with
stirring for 30 minutes. After stirring of the rhodium mixture, 12-tungstophosphoric acid
(H3[PW12O40].xH20, Aldrich, FW 2280 g/mol, 10.657 g) was added with stirring for 1
hour. 6.416g of silica (Grace, grade G57, FW=60 g/mol, 1-2 mm particle size) was
then added. The solution was then stirred for 4 hours. After 4 hours the flask was
transferred to a rotary evaporator and the methanol removed under reduced pressure of
337 mbar for 1 hour to yield a red/orange solid. This solid was crushed using a mortar
and pestle and then sieved to give a catalyst of particle size 0.5-1.0 mm.
Catalyst testing procedure
A number of experiments were carried out at varying water concentrations in the
feed and at two different gas hourly space velocities (GHSV).
Examples 1 to 3
5 ml (approx. 5g) of catalyst A was charged to a quartz tube reactor with a
supportive frit positioned in the middle of the tube. The reactor was then further filled
with borosilicate glass beads above the catalyst. The reactor was positioned in the
middle of a vertical furnace with insulating lagging at the top and bottom of the furnace.
Carbon monoxide and methanol were fed to the quartz reactor in a molar ratio of CO :
MeOH of 9 : 1. Carbon monoxide at a gas flow rate of 150 ml/min was fed into the top
of the reactor via a flow meter. Once stable flow was achieved after 2-3 minutes, the
furnace was heated gradually (5°C/min) to 100°C. The furnace remained at 100°C for
20 min to remove the majority of the water from the catalyst after which time the
furnace was heated gradually (5°C/min) to 230°C. The system was left at temperature
for 15 min to fully equilibrate and then liquid methanol and water (where used) (see
Table 1 below for liquid feed flow parameters) were fed to the top of the reactor via a
syringe pump. The liquid and gaseous reactants passed down through the reactor and
into a liquid trap. The liquid trap comprised a coil condenser immersed in an ice-bath,
where the liquid products were isolated. The gaseous products were vented via a Tpiece
containing a septum for taking gas samples via a gas syringe. Typically, the liquid
trap was changed every hour and a gas sample was taken during the middle of each time
segment. Liquid samples were analysed on a gas chromatograph equipped with a
boiling point column and a TCD detector. Gas samples were analysed on a four-column
gas chromatograph. Post-reaction the system was completely purged with nitrogen
before removing the reactor from the rig. The GHSV was 1800/h. Acetic acid and
methyl acetate were products of the reaction.
The results of Examples 1 to 3 are given in Table 2 below.
Experiment A
The catalyst testing procedure was repeated as for Examples 1 to 3 except that
no water was added to the carbonylation reaction feed. The results of Experiment A are
given in Table 2 below.
Examples 4 to 5
The catalyst testing procedure was repeated as for Examples 1 to 3 except that a
GHSV of 900/h and 10 ml of catalyst A was used. The results of Examples 4 to 6 are
given in Table 3 below.
Experiment B
The catalyst testing procedure was repeated as for Examples 4 to 5 except that
no water was added to the carbonylation reaction feed. The results of Experiment B are
given in Table 3 below.
(Table Removed)
The results shown in Tables 2 and 3 demonstrate that by increasing the amount of water
in the feed to the carbonylation reaction improved methanol conversion may be
achieved. An increase in product selectivity is also observed in the presence of water
co-feed compared to its absence. The increases in activity and selectivity are also more
pronounced in the Experiments at higher space velocities in the reactor. Thus, in
Example 2, for example, shows that the methanol conversion is increased from 17.8
wt% with no water co-feed to 32.8wt% at a 10wt% water co-feed, whilst the
corresponding product selectivity increases from 94.0% to 95.9%.



We Claim:
1. A carbonylation process for the production of a carbonylation product by contacting carbon monoxide with a feed comprising an alcohol or a reactive derivative thereof in the vapour phase using an heterogenous heteropolyacid catalyst comprising one or more metal cations selected from Cu, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt, characterized in that there is also present in the feed at least 0.5wt% water.
2. A process as claimed in claim 1 wherein the feed comprises at least lwt%, such as at least 2 wt%, preferably at least 5wt% water.
3. A process as claimed in claim 1 or claim 2 wherein the feed comprises up to 20 wt%, such as up to 15 wt% water.
4. A process as claimed in any one of the preceding claims wherein the feed comprises 5 to 15 wt% water.
5. A process as claimed in any one of the preceding claims wherein the water in the feed is fresh and/or recycle water.
6. A process as claimed in any one of the preceding claims wherein the heteropolyacid comprises 1 to 6 wt% metal cation(s).
7. A process as claimed in any one of the preceding claims wherein the heteropolyacid catalyst comprises a metal cation selected from rhodium, iridium and copper.
8. A process as claimed in claim 7 wherein the metal cation is rhodium.
9. A process as claimed in any one of the preceding claims wherein the heteropolyacid comprises a peripheral atom selected from the group consisting of molybdenum, tungsten, vanadium, niobium, chromium and tantalum and a central atom selected from silicon and phosphorus.

10. A process as claimed in any one of the preceding claims wherein the heteropolyacid is selected from the group consisting of substituted silicotungstic acids, silicomolybdic acids, phosphotungstic acids and phosphomolybdic acids.
11. A process as claimed in any one of the preceding claims wherein the heteropolyacid comprises one or more further cations selected from residual hydrogen ions and alkali metal cations.
12. A process as claimed in any one of the preceding claims wherein the heteropolyacid catalyst is supported on a support.
13. A process as claimed in claim 12 wherein the support is selected from an oxide support and a non-oxide support.
14. A process as claimed in claim 13 wherein the oxide support is selected from the group consisting of silica, alumina, silica-aluminas, zeolites, clays, diatomaceous earths and titania.
15. A process as claimed in claim 13 wherein the non-oxide support is selected from the group consisting of silicon carbide, carbons and organic polymer.
16. A process as claimed in any one of claims 12 to 15 wherein the heteropolyacid comprises 20 to 70% by weight based on the total weight of heteropolyacid and support.
17. A process as claimed in any one of the preceding claims wherein the alcohol is a Ci to C12 aliphatic alcohol.
18. A process as claimed in claim 17 wherein the alcohol is selected from methanol, ethanol, propanol, isopropanol, the butanols, the pentanols and the hexanols.

19. A process as claimed in any one of the preceding claims wherein the reactive derivative of the alcohol is selected from at least one of a dialkyl ether, an ester of the alcohol and an alkyl halide.
20. A process as claimed in claim 19 wherein the reactive derivative is selected from at least one of methyl acetate, dimethyl ether and methyl iodide.
21. A process as claimed in any one of the preceding claims wherein the feed comprises an alcohol and a reactive derivative thereof.
22. A process as claimed in claim 21 wherein the reactive derivative is an ether or an ester of the alcohol.
23. A process as claimed in claim 22 wherein the ether or the ester is present in an amount up to equimolar to the amount of water in the feed.
24. A process as claimed in any one of the preceding claims wherein the carbonylation product is selected from at least one of a carboxylic and a carboxylic acid ester.
25. A process as claimed in claim 24 wherein the carbonylation product is selected from at least one of acetic acid and methyl acetate.
26. A process as claimed in any one of the preceding claims wherein the carbon monoxide to alcohol molar ratio is in the range 5:1 to 15:1.
27. A process as claimed in any one of the preceding claims wherein the feed also comprises hydrogen.
28. A process as claimed in claim 27 wherein the hydrogen to carbon monoxide molar ratio is in the range 1:20 to 20:1.

29. A process as claimed in any one of the preceding claims wherein the carbon monoxide is used in the form of synthesis gas.
30. A process as claimed in any one of the preceding claims wherein the process is carried out at a temperature in the range 100 to 300°C.
31. A process as claimed in any one of the preceding claims wherein the process is carried out at a pressure in the range 1 to 100 barg.
32. A process as claimed in any one of the preceding claims wherein the gas hourly space velocity is in the range 100 to 10000 h'1.
33. A process as claimed in any one of the preceding claims wherein the process is carried out as a continuous process.

Documents:

4857-DELNP-2006-Claims-(07-08-2009).pdf

4857-DELNP-2006-Correspondence-Others-(03-01-2011).pdf

4857-DELNP-2006-Correspondence-Others-(07-08-2009).pdf

4857-DELNP-2006-Correspondence-Others-(16-04-2010).pdf

4857-DELNP-2006-Correspondence-Others-(22-04-2010).pdf

4857-delnp-2006-correspondence-others-1.pdf

4857-delnp-2006-correspondence-others.pdf

4857-DELNP-2006-Description (Complete)-(07-08-2009).pdf

4857-delnp-2006-description (complete).pdf

4857-DELNP-2006-Form-1-(07-08-2009).pdf

4857-delnp-2006-form-1.pdf

4857-delnp-2006-form-18.pdf

4857-DELNP-2006-Form-2-(07-08-2009).pdf

4857-delnp-2006-form-2.pdf

4857-DELNP-2006-Form-3-(03-01-2011).pdf

4857-DELNP-2006-Form-3-(07-08-2009).pdf

4857-DELNP-2006-Form-3-(16-04-2010).pdf

4857-delnp-2006-form-3.pdf

4857-delnp-2006-form-5.pdf

4857-DELNP-2006-GPA-(07-08-2009).pdf

4857-delnp-2006-gpa.pdf

4857-delnp-2006-pct-101.pdf

4857-delnp-2006-pct-210.pdf

4857-delnp-2006-pct-220.pdf

4857-delnp-2006-pct-237.pdf

4857-delnp-2006-pct-304.pdf

4857-delnp-2006-pct-311.pdf

4857-delnp-2006-pct-332.pdf

4857-delnp-2006-pct-401.pdf

4857-delnp-2006-pct-402.pdf

4857-delnp-2006-pct-409.pdf

4857-delnp-2006-pct-416.pdf

4857-DELNP-2006-Petition-138-(07-08-2009).pdf


Patent Number 249277
Indian Patent Application Number 4857/DELNP/2006
PG Journal Number 42/2011
Publication Date 21-Oct-2011
Grant Date 14-Oct-2011
Date of Filing 24-Aug-2006
Name of Patentee BP CHEMICALS LIMITED
Applicant Address CHERTSEY ROAD, SUNBURY ON THAMES, MIDDLESEX TW16 7BP, ENGLAND
Inventors:
# Inventor's Name Inventor's Address
1 WARREN JOHN SMITH ENDFIELD HOUSE, SUNK ISLAND ROAD, OTTRINGHAM, EAST RIDING HU 12 0DX, ENGLAND.
PCT International Classification Number C07C 51/12
PCT International Application Number PCT/GB2005/000438
PCT International Filing date 2005-02-09
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 0404793.2 2004-03-03 U.K.