USOO5883295A

United States Patent (19) 11 Patent Number: 5,883,295

Sunley et al. (45) Date of Patent: Mar 16, 1999
54) IRIDIUM CATALYZED CARBONYLATION 1 767 150 5/1972 Germany.
PROCESS FOR THE PRODUCTION OF 96/11179 4/1996 WIPO.
ACETIC ACID
Primary Examiner-Gary Geist
75 Inventors: John G. Sunley, East Yorkshire; Assistant Examiner Rosalynd Keys
Robert J. Watt, Yorkshire, both of Attorney, Agent, or Firm Nixon & Vanderhye
United Kingdom
57 ABSTRACT
73 Assignee: BP Chemicals Limited, London, A process for the production of acetic acid comprising
England
carbonylating with carbon monoxide methanol and/or a
reactive derivative thereof in the Substantial absence of a
21 Appl. No.: 992,104 metal promoter and/or ionic iodide co-promoter in a carbo
22 Filed: Dec. 17, 1997 nylation reactor containing a liquid reaction composition
comprising an iridium carbonylation catalyst, methyl iodide
30 Foreign Application Priority Data co-catalyst, water, acetic acid and methyl acetate wherein
Dec. 19, 1996 GB United Kingdom ................ 9626428.8 there is maintained (i) in the liquid reaction composition:
51 Int. Cl. ............................ C07C 51/12; CO7C 51/10 (a) water at a concentration of less than 5.0% by weight
and
52 U.S. Cl. ............................................. 562/519; 562/520 (b) methyl iodide at a concentration greater than 12% by
58 Field of Search ...................................... 562/519, 520 weight and (ii) in the carbonylation reactor a total
56) References Cited preSSure of less than 50 barg.
FOREIGN PATENT DOCUMENTS
O 616 997 A1 9/1994 European Pat. Off.. 16 Claims, 2 Drawing Sheets
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U.S. Patent 5,883,295

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IRIDIUM CATALYZED CARBONYLATION Methanol and/or a reactive derivative thereof is carbony
PROCESS FOR THE PRODUCTION OF lated in the process of the present invention. Suitable reac
ACETIC ACID tive derivatives of methanol include methyl acetate, dim
ethyl ether and methyl iodide. A mixture of methanol and
The present invention relates to a process for the pro 5 reactive derivatives thereof may be used as reactants in the
duction of acetic acid and, in particular, to a proceSS for the process of the present invention. Preferably, methanol and/or
production of acetic acid by carbonylation in the presence of methyl acetate are used as reactants. At least Some of the
an iridium catalyst and methyl iodide co-catalyst. methanol and/or reactive derivative thereof will be con
The preparation of carboxylic acids by iridium-catalyzed verted to, and hence present as, methyl acetate in the liquid
carbonylation processes is known and is described, for reaction composition by reaction with acetic acid product or
example in GB-A-1234121, U.S. Pat. No. 3,772,380, DE-A- Solvent. In the process of the present invention the concen
1767150, EP-A-0616997, EP-A-0618.184, EP-A-0618183, tration of methyl acetate in the liquid reaction composition
EP-A-0657386 and WO-A-96/11179. is suitably in the range from 1 to 70% by weight, for
GB-A-1234121, U.S. Pat. No. 3,772,380, DE-A- example from 1 to 50% by weight, preferably from 5 to 50%
1767150 and WO-A-96/11179, like the present invention, 15 by weight, more preferably from 10 to 40% by weight.
are concerned with iridium-catalyzed carbonylation pro Using reactive derivatives Such as methyl acetate and dim
ceSSes which do not use promoters. ethyl ether it is necessary to use water as coreactant.
In particular WO-A-96/11179 discloses a method for The carbon monoxide reactant may be essentially pure or
preparing carboxylic acids having (n+1) carbon atoms, or may contain impurities Such as carbon dioxide, methane,
the related esters, by liquid phase carbonylation of an nitrogen, noble gases, water and C to C paraffinic hydro
alcohol having (n) carbon atoms in the presence of a catalyst carbons. The presence of hydrogen in the carbon monoxide
comprising at least one iridium compound and at least one feed and generated in Situ by the water gas shift reaction is
halogenated co-catalyst characterized in that there is main preferably kept low as its presence may result in the forma
tained in the mixture during the reaction the ester corre tion of hydrogenation products. Thus, the amount of hydro
sponding to the carboxylic acid and the alcohol in an amount 25 gen in the carbon monoxide reactant is preferably less than
between 15 and 35%, the halogenated co-catalyst in an 1 mol %, more preferably less than 0.5 mol % and yet more
amount between 10 and 20% and a partial pressure of carbon preferably less than 0.3 mol % and/or the partial pressure of
monoxide between 40 and 200 bar, which latter pressure hydrogen in the carbonylation reactor is preferably less than
corresponds to a total pressure of from 50 to 250 bar. 1 bar partial pressure, more preferably less than 0.5 bar and
It is known from for example EP-A-0643034 that a yet more preferably less than 0.3 bar. The partial pressure of
promoter Selected from ruthenium and osmium can have a carbon monoxide in the carbonylation reactor is Suitably that
beneficial effect on the carbonylation rate of the iridium preSSure which corresponds to the total pressure being leSS
catalyzed, methyl iodide co-catalyzed carbonylation of than 50 barg, typically less than 40 barg, preferably less than
methanol in the presence of acetic acid, a finite concentra 30 barg. The temperature at which the process is operated is
tion of water and methyl acetate. 35 suitably in the range from 100 to 300° C., preferably in the
Nevertheless there remains a need for an improved range from 150° to 220° C.
iridium-catalyzed carbonylation proceSS in the absence of a In the process of the present invention, the iridium car
metallic promoter, Such as ruthenium and/or osmium, and/or bonylation catalyst is preferably present in the liquid reac
an ionic iodide co-promoter Such as quaternary ammonium tion composition at a concentration in the range from 400 to
and phosphonium iodides. 40 5000 ppm measured as iridium, more preferably in the range
Thus, according to the present invention there is pro from 500 to 3000 ppm measured as iridium. In the process
Vided a process for the production of acetic acid comprising of the present invention, the rate of the carbonylation
carbonylating with carbon monoxide methanol and/or a reaction increaseS as the concentration of iridium is
reactive derivative thereof in the Substantial absence of a increased.
metal promoter and/or ionic iodide co-promoter in a carbo 45 The iridium catalyst in the liquid reaction composition
nylation reactor containing a liquid reaction composition may comprise any iridium containing compound which is
comprising an iridium carbonylation catalyst, methyl iodide Soluble in the liquid reaction composition. The iridium
co-catalyst, water, acetic acid and methyl acetate character catalyst may be added to the liquid reaction composition for
ized in that there is maintained (i) in the liquid reaction the carbonylation reaction in any Suitable form which dis
composition: 50 Solves in the liquid reaction composition or is convertible to
(a) water at a concentration of less than 5.0% by weight a Soluble form. Examples of Suitable iridium-containing
and compounds which may be added to the liquid reaction
(b) methyl iodide at a concentration greater than 12% by composition include IrC1, Irla, IrBr, Ir(CO)I, Ir(CO)
weight and (ii) in the carbonylation reactor a total Cl), Ir(CO), Br, Ir(CO)IH, Ir(CO).Br. H, Ir
preSSure of less than 50 barg. 55 (CO)I.H", Ir(CH)I(CO)H, Ir(CO), IrCl3HO,
The present invention solves the technical problem IrBr.3H2O, Ir(CO), iridium metal, IrO, IrO, Ir(acac)
defined hereinabove by maintaining a liquid reaction com (CO), Ir(acac), iridium acetate, IrO(OAc)(H2O)
position having defined water and methyl iodide concentra OAc), and hexachloroiridic acid HIrCl), preferably,
tions and a defined total pressure in the carbonylation chloride-fee complexes of iridium Such as acetates, oxalates
reactor. This provides Several technical advantages. 60 and acetaoacetates which are Soluble in one or more of the
Thus increasing the methyl iodide concentration at rela carbonylation reaction components Such as water, alcohol
tively low water concentrations has a beneficial effect on the and/or carboxylic acid. Particularly preferred is green iri
carbonylation rate. A further advantage of the use of high dium acetate which may be used in an acetic acid or aqueous
methyl iodide concentrations at relatively low water levels is acetic acid Solution.
that there can be achieved a reduction in the rate of produc 65 It is a feature of the process of the present invention that
tion of one or more of the by-products propionic acid, the methyl iodide concentration in the liquid reaction com
methane, hydrogen and carbon dioxide. position is greater than 12% by weight. Preferably the
 5,883,295
3 4
methyl iodide concentration is greater than 14% by weight. The acetic acid product may be recovered from the liquid
The upper limit of the methyl iodide concentration may be reaction composition by withdrawing vapour and/or liquid
as high as 20% by weight, typically as high as 18% by from the carbonylation reactor and recovering acetic acid
weight. from the withdrawn material. Preferably, acetic acid is
Another feature of the process of the present invention is recovered from the liquid reaction composition by continu
that the water concentration is less than 5% by weight. ously withdrawing liquid reaction composition from the
Water may be formed in situ in the liquid reaction carbonylation reactor and recovering acetic acid from the
composition, for example, by the esterification reaction withdrawn liquid reaction composition by one or more flash
between methanol reactant and acetic acid product. Small and/or fractional distillation Stages in which the acetic acid
amounts of water may also be produced by hydrogenation of is Separated from the other components of the liquid reaction
methanol to produce methane and water. Water may be composition Such as iridium catalyst, methyl iodide
introduced to the carbonylation reactor together with or co-catalyst, methyl acetate, unreacted methanol, water and
Separately from other components of the liquid reaction acetic acid Solvent which may be recycled to the reactor to
composition. Water may be separated from other compo maintain their concentrations in the liquid reaction compo
nents of reaction composition withdrawn from the reactor 15 Sition. To maintain Stability of the iridium catalyst during the
and may be recycled in controlled amounts to maintain the acetic acid product recovery stage, water in process Streams
required concentration of water in the liquid reaction com containing iridium carbonylation catalyst for recycle to the
position. carbonylation reactor should be maintained at a concentra
The water concentration in the liquid reaction composi tion of at least 0.5% by weight.
tion is less than 5% by weight, preferably less than 4% by The process of the present invention will now be illus
weight. trated by reference to the following Examples and FIGS. 1
The process of the present invention is operated in the & 2 which represent in graph form, reaction rates verSuS
Substantial absence of metallic promoterS Such as for water concentration at different methyl iodide concentra
example, ruthenium and osmium and/or ionic iodide tions. In the Examples the following experimental procedure
co-promoterS Such as for example quaternary ammonium 25
was employed.
and phosphonium iodides. For the avoidance of doubt the EXPERIMENTAL PROCEDURE
term 'Substantial absence of metallic promoters and/or ionic General Description of the Carbonylation Experiments
iodide co-promoters means the absence of deliberately All experiments were performed using a 300 ml Zirco
added metallic promoters and/or ionic iodide co-promoters, nium autoclave equipped with a magnetically driven Stirrer
for it is possible that there may inadvertently be present by, with gas dispersion impellers, liquid catalyst injection facil
for example corrosion of the carbonylation reactor, metals ity and cooling coils. A gas Supply to the autoclave was
which if deliberately added may function as promoters. provided from a ballast vessel, feed gas being provided to
A particularly preferred liquid reaction composition com maintain the autoclave at a constant pressure. The rate of gas
prises about from 1 to 5% by weight water, from 14 to 18% uptake at a certain point in a reaction run was used to
by weight methyl iodide co-catalyst, from 14 to 31% by 35 calculate the carbonylation rate, as number of moles of
weight methyl acetate, iridium catalyst at a concentration in reactant consumed per liter of cold degassed reactor com
the range from 400 to 3000 ppm measured as iridium and the position per hour mol/l /hr, at a particular reactor com
balance of the composition comprising Substantially acetic position (reactor composition based on a cold degassed
acid, and preferred reaction conditions are a carbonylation Volume).
reaction temperature of from 185 to 200 C., a carbonyla 40 The methyl acetate concentration was calculated during
tion reaction total preSSure of up to 40 barg and a carbon the course of the reaction from the Starting composition,
monoxide partial pressure of from 1 to 12 bar. assuming that one mole of methyl acetate is consumed for
Ionic contaminants Such as, for example, (a) corrosion every mole of carbon monoxide that is consumed. No
metals, particularly nickel, iron and chromium and (b) allowance was made for organic components in the auto
phosphines or nitrogen-containing compounds or ligands 45 clave headspace.
which may quaternize in situ; should be kept to a minimum For each batch carbonylation experiment the catalyst,
in the liquid reaction composition as these may generally H-IrCle, dissolved in a portion of the acetic acid/water liquid
have an adverse effect on the reaction by generating IT in the reactor charge, was charged to the liquid injection facility.
liquid reaction composition which may have an adverse The reactor was then pressure tested with nitrogen, Vented
effect on the reaction rate. Some corrosion metal contami 50 via a gas Sampling System, and flushed with carbon mon
nants Such as for example molybdenum have been found to oxide several times (3x3-10 barg). The remaining liquid
be leSS Susceptible to the generation of I. Corrosion metals components of the reaction composition were charged to the
which have an adverse effect on the reaction rate may be autoclave via a liquid addition port. The autoclave was
minimized by using Suitable corrosion resistant materials of optionally flushed once more with carbon moxide (1xca. 5
construction. Similarly, contaminants Such as alkali metal 55 barg). The autoclave was then pressurized with carbon
iodides, for example lithium iodide, may be kept to a monoxide (typically 6 barg) and heated with stirring (1500
minimum. Corrosion metal and other ionic impurities may rpm) to reaction temperature, 190° C. The total pressure was
be reduced by the use of a Suitable ion exchange resin bed then raised to approximately 3 barg below the desired
to treat the reaction composition, or preferably a catalyst operating pressure by feeding forward carbon monoxide
recycle stream. Such a process is described in U.S. Pat. No. 60 from the ballast vessel. Once stable attemperature (about 15
4,007,130. Ionic contaminants may be kept below a con minutes) the catalyst was injected using an over pressure of
centration at which they would generate 500 ppm I, pref carbon monoxide. The catalyst injection facility has an
erably less than 250 ppm I in the liquid reaction compo efficiency of >90%. The reactor pressure was maintained at
Sition. a constant value (t0.5 barg) by feeding gas from the ballast
The process of the invention is preferably operated as a 65 vessel throughout the experiment. Gas uptake from the
continuous process but may be operated as a batch proceSS ballast vessel was measured using datalogging, facilities
if desired. throughout the course of the experiment. The reaction tem
 5,883,295
S 6
perature was maintained within +1 C. of the desired reac A-J(a), A to F(b), A-E(c), A and B(cd), (e) and (f) and A(g).
tion temperature by means of a heating mantle connected to They are included for the purpose of comparison only.
a Eurotherm (Trade Mark) control system. In addition,
exceSS heat of reaction was removed by means of cooling BRIEF DESCRIPTION OF DRAWINGS
coils. Each run was conducted until the -as uptake had 5
ceased (i.e. less than 0.1 bar per minute of gas consumed The results are illustrated in graph form in FIGS. 1 & 2.
from the ballast vessel). The ballast vessel was then isolated
and the reactor crash cooled by use of the cooling coils. FIG. 1 illustrates the beneficial effect of increasing the
HIrCl (22.2% w/w or 10.6% w/w Iraqueous solution) MeI concentration from 8.4% w/w to 16.9% w/w at 30%
was supplied by Johnson Matthey. The acetic acid was 10 w/w MeOAc and a water concentration less than 5% w/w at
obtained from carbonylation of a mixed methanol/methyl a total pressure of 28 barg.
acetate feedstock and contained very low amounts of pro- FIG. 2 illustrates the beneficial effect of increasing the
pionic acid and its precursors. Methyl acetate (29, 699-6), MeI concentration from 8.0% w/w to 16.0% w/w at 15%
Water (32, 007-2) and methyl iodide (I-850-7) were supplied w/w MeOAc and a water concentration less than 5% w/w at
by Aldrich. 15 a total pressure of 28 barg.
EXAMPLES Based on FIGS. 1 and 2, increasing the methyl iodide
Experiments 1 to 9 demonstrate the effect of water concentration to greater than 12% W/w is particularly ben
concentration, eXpressed in % W/w, on carbonylation activ- eficial when, at 12% w/w methyl iodide, the reaction rate is
ity using an iridium catalyst at 190° C. and 28 barg total 20 declining With reducing Water concentration at any particu
pressure for reactions which pass through 16.9% w/w MeI lar methyl acetate concentration, total pressure and carbon
at 30% w/w MeOAc. Charge compositions are given in monoxide partial pressure.
Table 1. Rate data, at 30%, 25%, 20%, 15%, 10%, 7.5% and
5% w/w MeOAc, are given in Table 2. TABLE 1.
Experiments 1–6(a), 1–5(b), 1-4(c) and 1 and 2(d) (e) and 25 Charge composition for iridium catalyzed reactions in a 300 ml
(f) and 1(g) are not according to the present invention Zirconium batch autoclave.
because the water concentration is not less than 5.0% by
weight. They are included for the purpose of comparison Run
only. Experiment No. MeOAc/g AcOH/g MeI/g Water/g HIrClfg
Experiments A to N demonstrate the effect of water 30 1. 684 60.02 34.07 27.03 28.26 O.643
concentration, eXpressed in % W/w, on carbonylation activ- 2. 25. i.S. 2. 9.
ity using an iridium catalyst at 190° C. and 28 barg total 4 702 6007 47.4s 3704 1488 0.644
pressure for reactions which pass through 8.4% w/w MeI at 5 696 60.00 48.74 27.05 13.56 0.641
30% w/w MeOAc. Charge compositions are given in Table 6 614 60.02 50.43. 27.01 11.90 0.642
3. Rate data, at 30%, 25%, 20%, 15%, 10%, 7.5% and 5% 35 2. S. 2. 2. 9.
w/w MeOAC, are given in Table 4. 9 6s 60.03 5592 57.03 640 0.641
Experiments. A to N are not according to the present
invention because the methyl iodide concentration is not ) Weight expressed as pure HIrCl
greater than 12% by weight. Moreover the water concen
TABLE 2
Rate data for iridium catalyzed reactions in 300 ml autoclave; effect of water
concentration on rate at various MeOAC concentrations at ca. 16% WW MeI.
- (a) - - (b) - - - - (- - - - - - (s-
Ratef Rate? Rate? Rate?
molffhr molffhr molffhr molffhr molffhr molffhr molffhr
Experi- Water? (Q 30% Water? G 25% Water? (Q) 20% Waterf (Q) 15% Water? G 10% Water? (Q) 7.5% Water? (Q) 5%
ment % w/w MeOAc % w/w MeOAc % w/w MeOAc % w/w MeOAc % w/w MeOAc % w/w MeOAc % w/w MeOAc
1. 16.1 4.9 14.7 5.5 13.4 6.1 12.0 6.2 10.6 5.3 9.9 4.5 9.3 3.2
2 10.9 11.8 9.7 13.1 8.4 13.7 7.1 11.6 5.8 8.5 5.2 6.4 4.5 NA
3 8.2 20.1 7.0 18.6 5.7 16.6 4.5 14.3 3.3 10.6 2.7 8.3 2.1 6.4
4 7.5 20.4 6.3 18.3 5.1 16.1 3.8 13.6 2.6 10.3 2.O 8.6 1.4 6.5
5 6.6 22.4 5.4 20.4 4.2 17.7 3.0 14.7 18 11.5 1.2 9.2 O6 5.9
6 5.6 23.2 4.4 21.2 3.2 18.8 2.0 15.8 O.8 10.1 O.2 5.1
7 4.0 27.4 2.8 22.6 1.7 17.0 0.5 9.4
8 3.0 26.9 18 2O2 O.7 12.4
9 2.O 21.8 O.9 1.O.O

*All reactions at 28 barg total pressure and 190° C. with a stirrer speed of 1500 rpm.
ca. 16.9% MeI at 30% MeOAc
ca. 16.0% MeI at 15% MeOAc
MeI concentration is adjusted slightly downwards based upon the approximation that each mole of iridium can consume a maximum of 4 moles of methyl
iodide to give Ir(CO)2.I.
N/A - not available, reaction terminated too early.
65

tration is not less than 5.0% by weight in Experiments

 5,883,295
7 8
3. A process according to claim 1 wherein the concentra
TABLE 3 tion of methyl acetate in the liquid reaction composition is
in the range from 1 to 50% by weight.
Charge compositions for reactions in a 300 ml zirconium batch autoclave. 4. A process according to claim 3 wherein the concentra
5 tion of methyl acetate in the liquid reaction composition is
Run : in the range from 10 to 40% by weight.
Experiment No. MeOAc/g AcOH/g MeI/g Water/g HIrClfg 5. A process according to claim 1 wherein the methyl
A. 63O 6O.O7 47.13 13.96 28.3O O.639 iodide concentration in the liquid reaction composition is
B 609 S9.99 55.32 13.97 2011 O.640 greater than 14% by weight.
C 641 6O.O1 59.40 13.96 16.06 0.641 6. A process according to claim 5 wherein the upper limit
D 653 60.02 59.52 13.97 16.00 0.643 10 of the methyl iodide concentration is 20% by weight.
E 675 6.O.O2 59.42 13.96 15.99 O.643 7. A process according to claim 1 wherein the water
F 731 [Link] 61.89 13.97 13.71 O.643 tration in the liquid ti ition is less th
G 598 59.99 63.54 13.97 11.94 O.641 concentration in the liquid reaction composition is less unan
H 615 60.02 63.51 13.96 11.96 0.640 4% by weight.
I 621 59.99 63.49 13.96 11.96 O.640 8. A process according to claim 1 wherein the concentra
J 634 60.05 63.49 13.96 11.98 0.649 15 tion of the iridium catalyst in the liquid reaction composition
KL 64O
643
6O.O3
60.01
65.95
66.15
13.97
13.96
9.51
9.52
O.644
0.646
is in the range from 400 to 5000 ppm measured as iridium.
M 763 [Link] 67.51. 13.96 7.91 O.634 9. A proceSS
- according to claim 8 wherein the concentra
N 642 6O.O2 68.99 13.96 6.46 0.642 tion of iridium catalyst is from 500 to 3000 ppm measured
as iridium.
*Weight expressed as pure H-IrCls. 10. A process according to claim 1 wherein the total
preSSure in the carbonylation reactor is less than 40 barg.

TABLE 4
Rate data for iridium catalyzed reactions in 300 ml autoclave; effect of water
concentration on rate at various MeOAC concentrations at ca. 8% WW MeI.
- (a) - - (b) - - - - - - - - - - (s-
Ratef Ratef Rate? Rate? Ratef Ratef Rate?
molffhr molffhr molffhr molffhr molffhr molffhr molffhr
Experi- Water? (Q 30% Water? G 25% Water? (Q) 20% Water? G 15% Water? G 10% Water? (Q) 7.5% Water? (Q) 5%
ment % w/w MeOAc % w/w MeOAc % w/w MeOAc % w/w MeOAc % w/w MeOAc % w/w MeOAc % w/w MeOAc
A. 16.1 7.1 14.8 7.5 13.4 8.0 12.0 7.7 10.7 6.9 1O.O 6.O 9.3 4.8
B 10.9 14.9 9.6 14.6 8.3 13.5 7.0 11.2 5.8 7.1 5.1 5.4 4.5 3.9
C 8.2 17.7 7.0 15.7 5.8 13.4 4.5 10.5 3.3 8.4 2.7 6.O 2.1 4.5
D 8.2 18.2 7.0 17.0 5.7 15.1 4.5 11.7 3.3 8.7 2.7 6.9 2.0 5.4
E 8.2 18.6 7.0 16.7 5.7 14.4 4.5 11.8 3.3 8.7 2.7 6.9 2.0 5.1
F 6.7 19.6 5.5 17.4 4.3 14.9 3.1 12.0 1.9 8.7 1.3 6.5 O.7 3.4
G 5.6 20.4 4.4 17.0 3.2 13.8 2.O 9.5 O.8 4.9
H 5.6 19.7 4.4 17.6 3.2 14.3 2.O 9.9 O.9 5.0
I 5.6 20.5 4.4 17.4 3.2 14.O 2.O 10.5 O.9 5.5
J 5.6 21.1 4.4 17.9 3.2 14.8 2.O 11.1 O.9 6.O
K 4.0 19.7 2.9 15.5 1.7 10.8 0.5 N/A
L 4.0 22.0 2.9 16.1 1.7 9.9 O6 4.4
M 3.0 20.4 1.9 14.1 O.7 6.9
N 2.1 12.1 O.9 5.9

* All reactions at 28 barg total pressure and 190° C. with a stirrer speed of 1500 rpm.
ca. 8.4%. Meat 30% MeOAC
ca. 8.0% MeI at 15% MeOAC
MeI concentration is adjusted slightly downwards based upon the approximation that each mole of iridium can consume a maximum of 4 moles of methyl
iodide to give Ir(CO)2.I.
N/A = reaction terminated too early to allow calculation of the rate at this point.
50
We claim: 11. A process according to claim 10 wherein the total
1. A proceSS for the production of acetic acid comprising preSSure is less than 30 barg.
carbonylating with carbon monoxide methanol and/or a 12. A process according to claim 1 wherein the tempera
reactive derivative thereof in the Substantial absence of a ture at which the proceSS is operated is in the range from
metal promoter and/or ionic iodide co-promoter in a carbo 55 150° to 220 C.
nylation reactor containing a liquid reaction composition 13. A process according to claim 1 wherein the amount of
comprising an iridium carbonylation catalyst, methyl iodide hydrogen in the carbon monoxide reactant is less than 0.3
co-catalyst, water, acetic acid and methyl acetate character mol %.
ized in that there is maintained (i) in the liquid reaction 14. A process according to claim 1 wherein the partial
composition: preSSure of hydrogen in the carbonylation reactor is less than
(a) water at a concentration of less than 5.0% by weight 60 0.3 bar.
and 15. A process according to claim 1 wherein the liquid
(b) methyl iodide at a concentration greater than 12% by reaction composition comprises:
weight and from 1 to 5% by weight water,
(ii) in the carbonylation reactor a total pressure of less from 14 to 18% by weight methyl iodide,
than 50 barg. 65 from 14 to 31% by weight methyl acetate,
2. A process according to claim 1 wherein methanol from 400 to 3000 ppm iridium catalyst measured as
and/or methyl acetate are carbonylated. iridium, and
 5,883,295
9 10
the balance comprising Substantially acetic acid, 16. A process according to claim 1 when operated con
and the reaction conditions are a carbonylation reaction tinuously.
temperature of 185 to 200 C., a carbonylation reaction
total pressure of up to 40 barg and a carbon monoxide partial
pressure of from 1 to 12 bar.