USOO6326515B1

(12) United States Patent (10) Patent No.: US 6,326,515 B1

Clode et al. (45) Date of Patent: Dec. 4, 2001

(54) CARBONYLATION OF METHANOLTO O 573 189 A1 12/1993 (EP).

ACETIC ACID WITH REMOVAL OF O 616 997 A1 9/1994 (EP).
IMPURITIES FROM THE PRODUCT O 618 183 A1 10/1994 (EP).
O 618 184A1 10/1994 (EP).
(75) Inventors: Kirsten Everald Clode; Derrick John O 657 386 6/1995 (EP).
Watson, both of East Yorkshire (GB) O 768 295 A1 4/1997 (EP).
O 849 250 A1 6/1998 (EP).
(73) Assignee: BP Chemicals Limited, London (GB) 1233 121 5/1971 (GB).
1234 641 6/1971 (GB).
95/31426 11/1995 (WO).
(*) Notice: Subject to any disclaimer, the term of this 98/17619 4/1998 (WO).
patent is extended or adjusted under 35
U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS
Howard et al., C to acetyls: catalysis and process.
(21) Appl. No.: 09/391,177
* cited by examiner
(22) Filed: Sep. 8, 1999
Primary Examiner-Gary Geist
(30) Foreign Application Priority Data ASSistant Examiner Robert W. Deemie
Sep. 8, 1998 (GB) .................................................. 98.19606 (74) Attorney, Agent, or Firm Nixon & Vanderhye
(51) Int. Cl." ................................................. C07C 51/42 (57) ABSTRACT
(52) U.S. Cl. ........................... 562/608; 562/519; 562/607 A process for removing higher organic iodides, including
(58) Field of Search ..................................... 562/519, 608, hexyl iodide, from an acetic acid product obtained by
562/607 carbonylating methanol and/or a reactive derivative thereof
(56) References Cited
in the presence of a finite concentration of water, Group VIII
noble metal catalyst, methyl iodide as co-catalyst, and
U.S. PATENT DOCUMENTS optionally a catalyst promoter, which process includes the
Step of Subjecting an aqueous composition comprising acetic
3,769,177 10/1973 Eubanks et al.. acid and at least one higher organic iodide to distillation in
3,772,380 11/1973 Paulik et al., a column, or Section of a column, Separating Water overhead
3,791935 2/1974 Eubanks et al. .
4,008,131 2/1977 Price. from a dry acetic acid fraction, wherein the water concen
5,723,660 * 3/1998 Morimoto et al.. tration on the feed tray of the column, or Section of the
column, is greater than 8% by weight and the water con
FOREIGN PATENT DOCUMENTS centration in the head of the column, and/or Section of the
1767 150 5/1972 (DE). column, is greater than 70% by weight.
O384652 A1 8/1990 (EP).
O 391 680 A1 10/1990 (EP). 10 Claims, No Drawings
 US 6,326,515 B1
1 2
CARBONYLATION OF METHANOLTO there is maintained during the course of the process a
ACETIC ACID WITH REMOVAL OF liquid reaction composition comprising:
IMPURITIES FROM THE PRODUCT (i) an iridium carbonylation catalyst;
(ii) methyl iodide co-catalyst;
The present invention relates in general to a carbonyla (iii) optionally one or more promoters selected from the
tion process for the production of acetic acid and in par group consisting of ruthenium, osmium, rhenium,
ticular to a process for the production of acetic acid by the cadmium, mercury, Zinc, gallium, iridium and tungsten;
carbonylation of methanol and/or a reactive derivative
thereof in the presence of a Group VIII noble metal catalyst, (iv) a finite amount of water at a concentration of less than
methyl iodide as co-catalyst, optionally a promoter, and a about 8% by weight;
finite concentration of water. (v) methyl acetate;
Homogeneous liquid phase processes for the production (vi) acetic acid; and
of acetic acid by the Group VIII noble metal catalysed, alkyl (vii) propionic acid by-product and its precursors;
halide co-catalysed reaction of carbon monoxide with (b) withdrawing liquid reaction composition from the car
methanol and/or a reactive derivative thereof are well 15 bonylation reactor and introducing at least a part of the
known. The proceSS using rhodium as the noble metal withdrawn liquid reaction composition, with or without
catalyst is described in, for example, GB-A-1,233,121; the addition of heat, to a flash Zone to form a vapour
EPA-0384652; and EP-A-0391680. The process using iri fraction comprising water, acetic acid product, propionic
dium as the noble metal catalyst is described in, for example, acid by-product, methyl acetate, methyl iodide and pro
GB-A-1234121, U.S. Pat. No. 3,772.380; DE-A-1767150; pionic acid precursors, and a liquid fraction comprising
EP-AO61997; EP-A-0618184; EP-A-0618183; EP-A- involatile iridium catalyst, involatile optional promoter or
0657386; and WO-A-95/31426. Carbonylation processes for promoters, acetic acid and water;
the production of acetic acid in the presence of either a (c) recycling the liquid fraction from the flash Zone to the
rhodium or an iridium carbonylation catalyst are operated on carbonylation reactor;
a commercial Scale at Several locations worldwide. 25 (d) introducing the vapour fraction from the flash Zone into
Howard et al in Catalysis Today, 18 (1993), 325–354 a first distillation Zone,
describe rhodium and iridium-catalysed carbonylation of (e) removing from the first distillation Zone at a point above
methanol to acetic acid. The continuous rhodium-catalysed, the introduction point of the flash Zone vapour fraction a
homogeneous methanol carbonylation proceSS is said to light ends recycle Stream comprising water, methyl
consist of three basic Sections, reaction, purification and acetate, methyl iodide, acetic acid and propionic acid
off-gas treatment. The reaction Section comprises an agitated precursors which Stream is recycled in whole or in part to
reactor, operated at elevated temperature and pressure, and the carbonylation reactor, and
a flash vessel. Liquid reaction composition is withdrawn (f) removing from the first distillation Zone at a point below
from the reactor and is passed through a flashing valve to a the introduction point of the flash Zone vapour fraction, a
flash tank where the majority of the lighter components of 35 proceSS Stream comprising acetic acid product, propionic
the liquid reaction composition (methyl iodide, methyl acid by-product, and less than 1500 ppm water and,
acetate and water) together with product acetic acid are (g) if the process stream removed in Step (f) comprises
Vaporised. The vapour fraction is then passed to the purifi greater than 400 ppm propionic acid introducing Said
cation Section whilst the liquid fraction (comprising the Stream into a Second distillation column, removing from
rhodium catalyst in acetic acid) is recycled to the reactor (cf 40 a point below the introduction point of the stream from (f)
FIG. 2 of Howard et al). The purification section is said to propionic acid by-product and from a point above the
comprise a first distillation column (the light ends column), introduction point of the stream from (f) an acetic acid
a second distillation column (the drying column) and a third proceSS Stream containing less than 400 ppm propionic
distillation column (the heavy ends column) (cf FIG. 3 of acid and less than 1500 ppm water.
Howard et al). In the light ends column methyl iodide and 45 In addition to propionic acid impurity, the Group VIII
methyl acetate are removed overhead along with Some water noble metal catalysed, methyl iodide co-catalysed carbony
and acetic acid. The vapour is condensed and allowed to lation of methanol and/or a reactive derivative thereof also
Separate into two phases in a decanter, both phases being produces as impurities higher organic iodides, especially
returned to the reactor. Wet acetic acid is removed from the organic iodides in the C-C, range, chief amongst which is
light ends column as a sidedraw and is fed to the drying 50 hexyl iodide. HeXyl iodide forms a constant boiling azeo
column where water is removed overhead and an essentially trope with acetic acid and hence is difficult to remove from
dry acetic acid stream is removed from the base of the acetic acid proceSS Streams by distillation. Unless additional
distillation Zone. From FIG.3 of Howard et all it can be seen non-distillative Steps are taken for its removal, Such as
that the overhead water Stream from the drying column is contact with a Silver or mercury loaded cation exchange
recycled to the reaction Section. Heavy liquid by-products 55 resin, or other adsorbent, hexyl iodide can therefore be
are removed from the base of the heavy ends column with found in Significant amounts in the purified acetic acid
product acetic acid being taken as a SideStream. Simplifica product. This is undesirable because its presence therein can
tion of the purification Section by elimination of one or more render the acetic acid unsuitable for use in certain down
distillation columns thereby economising on capital expen Stream applications. Treatment with an adsorbent, for
diture and/or operating costs of a plant has been proposed. 60 example, a metal loaded ion exchange resin carries with it an
Thus, for example our EP-A-0849250 (BP Case No. 8644) economic penalty. It would therefore be desirable to remove
discloses a process for the production of an acetic acid higher organic iodides during the distillative purification of
proceSS Stream comprising less than 400 ppm propionic acid crude acetic acid.
and less than 1500 ppm water which process comprises the We have found that higher organic iodides, and in par
Steps: 65 ticular hexyl iodide, can be removed from their admixture
(a) feeding methanol and/or a reactive derivative thereof and with acetic acid obtained by carbonylation in a distillation
carbon monoxide to a carbonylation reactor in which column by controlling the water concentration profile in the
 US 6,326,515 B1
3 4
column Such that the concentrations of water on the feed tray (c) recycling the liquid fraction from the flash Zone to the
in the column and in the head of the column are within carbonylation reactor;
defined limits. The excess water (over the levels previously (d) introducing the vapour fraction from the flash Zone into
employed) functions to azeotrope out the higher organic a first distillation Zone,
iodides and drive them up the column, where they are 5 (e) removing from the first distillation Zone at a point above
removeable overhead. the introduction point of the flash Zone vapour fraction a
Accordingly the present invention provides a process for light ends recycle Stream comprising water, methyl
removing higher organic iodides, including hexyl iodide, acetate, methyl iodide, acetic acid and propionic acid
from an acetic acid product obtained by carbonylating precursors which Stream is recycled in whole or in part to
methanol and/or a reactive derivative thereof in the presence the carbonylation reactor;
of a finite concentration of water, a Group VIII noble metal (f) removing from the first distillation Zone as a sidedraw at
catalyst, methyl iodide as co-catalyst, and optionally a a point below the introduction point of the flash Zone
catalyst promoter, which process includes the Step of Sub Vapour fraction, a stream comprising acetic acid, water,
jecting an aqueous composition comprising acetic acid and propionic acid by-product, and higher organic iodides
at least one higher organic iodide to distillation in a column, 15 by-product;
or Section of a column, Separating water overhead from a dry (g) feeding the sidedraw stream from (f) to an intermediate
acetic acid fraction, wherein the water concentration on the point in a Second distillation Zone wherein the water
feed tray of the column, or Section of the column, is greater concentration on the feed tray to the column is greater
than 8% by weight and/or the water concentration in the than 8% by weight, and/or the water concentration at the
head of the column, or Section of the column, is greater than head of the column is greater than 70% by weight;
70% by weight. (h) removing from the Second distillation Zone an overhead
The water concentration on the feed tray of the column, fraction comprising water and higher organic iodides and
or Section of the column, is greater than 8%, preferably from a point below the feed point a fraction comprising
greater than 10% by weight, typically from 8 to 14%, for acetic acid product and propionic acid by-product with
example 10 to 14% by weight. The water concentration at 25 Significantly reduced amounts of higher organic iodides.
the head of the column, or Section of the column is greater In this embodiment the water concentration on the feed
than 70%, preferably greater than 75% by weight, typically tray of the column is maintained at greater than 8% by
from 70 to 85% by weight. weight Suitably by controlling the amount of the overhead
An advantage of controlling the water concentration pro fraction removed from the second distillation Zone which,
file in the distillation column, or part thereof, in the manner after condensing, is returned to the column as reflux. The
according to the invention is that hexyl iodide, for example, water concentration at the head of the column is in part
concentrations of typically about 120 ppb in the acetic acid maintained at greater than 70% by weight in the same
before distillation can be reduced to 5 ppb, or less. Since .
pushing water up the column, or Section thereof, represents The overhead fraction removed from the second distilla
an economic operating penalty the less that can be employed 35 tion Zone in step (h) comprising water and higher organic
to achieve the desired result, the better the economics of the iodides is Suitably recycled as a liquid to the carbonylation
Separation. reactor. In the reactor hexyl iodide is converted to heptanoic
The process of the present invention may be operated in acid which presents no problems as an impurity in acetic
for example the drying column of Howard et al. In one acid at part per billion levels. Optionally, this overhead
embodiment the present invention provides a proceSS for the 40 Stream may be Subjected to further distillative processes in
production of acetic acid which process comprises the Steps: order to remove the organic iodides.
(a) feeding methanol and/or a reactive derivative thereof and Alternatively, the process of the present invention may be
carbon monoxide to a carbonylation reactor in which operated in a Section of a column in which other distillative
there is maintained during the course of the process a Separations are also occurring, Such as for example in a
liquid reaction composition comprising (i) a Group VIII 45 combined light ends/drying column or a combined light
noble metal carbonylation catalyst, (ii) methyl iodide ends/drying/heavy ends column as described in the aforesaid
co-catalyst, (iii) (a) in the case of the Group VIII noble EP-A-08492.50.
metal catalyst being rhodium, optionally one or more Thus, in an alternative embodiment the present invention
promoters of a type forming an iodide Salt, e.g. lithium provides a process for the production of acetic acid which
iodide, (b) in the case of the Group VIII noble metal 50 process comprises the Steps:
catalyst being iridium, optionally one or more promoters (a) to (c) as hereinbefore described;
Selected from the group consisting of ruthenium, osmium, (d) introducing the vapour fraction from the flash Zone into
rhenium, cadmium, mercury, Zinc, gallium, indium and a first distillation Zone, which first distillation Zone incor
tungsten, (iv) a finite amount of water (V) methyl acetate, porates an upper Section wherein an aqueous composition
(vi) acetic acid, (vii) higher organic iodides, including 55 comprising acetic acid and at least one higher organic
hexyl iodide, by-product, and propionic acid by-product iodide is separated into water overhead from a dry acetic
and its precursors, acid fraction, the water concentration on the feed tray
(b) withdrawing liquid reaction composition from the car being greater than 8% by weight and the water concen
bonylation reactor and introducing at least part of the tration at the head of the section being greater than 70%
withdrawn liquid reaction composition, with or without 60 by weight;
the addition of heat, to a flash Zone to form a vapour (e) removing from the first distillation Zone an overhead
fraction comprising water, acetic acid product, higher Vapour fraction comprising water, higher organic iodides,
organic iodides by-product, methyl acetate, methyl methyl acetate, methyl iodide, propionic acid precursors
iodide, propionic acid by-product and propionic acid and acetic acid;
precursors, and a liquid fraction comprising involatile 65 (f) condensing the overhead vapour fraction from (e), pass
Group VIII noble metal catalyst, involatile optional pro ing the condensate to a decanter wherein it is separated
moter or promoters, acetic acid and water, into a methyl iodide-rich phase and an aqueous phase, the
 US 6,326,515 B1
S 6
methyl iodide-rich phase being recycled to the carbony Some extent depend upon the nature of the catalytic metal.
lation reactor and the aqueous phase being divided, part Using iridium as catalyst the use of metal promoters is
being returned to the first distillation Zone as reflux and preferred. The metal promoter may Suitably be one or more
the remainder being recycled to the carbonylation reactor; of OSmium, rhenium, ruthenium, cadmium, mercury, Zinc,
(g) removing from the first distillation Zone at a point below 5 gallium, iridium and tungsten. Preferably the promoter is
the introduction point of the flash Zone vapour fraction, a Selected from ruthenium and OSmium and most preferably is
process Stream comprising dry acetic acid and propionic ruthenium. The promoter may comprise any promoter
acid by-product; and metal-containing compound which is Soluble in the liquid
(h) optionally introducing the aforesaid stream into a second reaction composition. The promoter may be added to the
distillation Zone; liquid reaction composition in any Suitable form which
(i) removing from the Second distillation Zone a bottom dissolves in the liquid reaction composition or is convertible
fraction comprising propionic acid; and to soluble form. Examples of suitable promoter metal
(j) removing from the Second distillation Zone a sidedraw containing compounds include carboxylate Salts, for
fraction comprising dry acetic acid product containing example acetates and carbonyl complexes. Preferably
less than 250 ppm propionic acid. 15 chloride-free compounds are employed. Preferably the pro
Methanol and/or a reactive derivative thereof, for moter metal compounds are free of impurities which provide
example methyl acetate, dimethyl ether or methyl iodide, is or generate in-situ ionic iodides which may inhibit the
fed to the carbonylation reactor. reaction in the presence of iridium catalysts, for example
A finite concentration of water typically from 0.1 to 30, alkali or alkaline earth metal or other metal Salts.
suitably from 0.1 to 15, preferably from 0.5 to 10, more Preferably, the promoter is present in an effective amount
preferably from 1 to 6% by weight is present in the liquid up to the limit of its Solubility in the liquid reaction com
reaction composition. position. The promoter is Suitably present in the liquid
Water may be formed in situ in the carbonylation reaction, reaction composition at a molar ratio of each promoter
for example by the esterification reaction between methanol (when present): iridium in the range 0.1 to 100:1, prefer
and/or reactive derivative thereof reactant and carboxylic 25 ably greater than 0.5:1, more preferably greater than 1:1
acid product. Water may be introduced to the carbonylation and up to 20:1, more preferably up to 15:1 and yet more
reactor together with or separately from the other liquid preferably up to 10: 1. The beneficial effect of a promoter
reactants. Water may be separated from reaction composi Such as ruthenium has been found to be greatest at the water
tion withdrawn from the reactor and recycled in controlled concentration which gives the maximum carbonylation rate
amounts to maintain the required concentration in the car at any defined methyl acetate and methyl iodide concentra
bonylation reaction composition. tion. A suitable promoter concentration is from 400 to 5000
Of the Group VIII noble metals, rhodium and iridium are ppm.
preferred. The Group VIII noble metal may be present in the Using rhodium as the carbonylation catalyst the use of
liquid reaction composition in any form which is Soluble in iodide promoters is preferred. Both inorganic and organic
the composition. It may be added to the liquid reaction 35 iodides may be employed. Suitable inorganic iodides
composition in any form which is Soluble in the composition include alkali metal and alkaline earth metal iodides. A
or is convertible to soluble form. Examples of suitable preferred metal iodide is lithium iodide. The iodides may be
rhodium-containing compounds which may be added to the added as Such or in the form of Salts, for example carboxy
liquid reaction composition include Rh(CO)2Cl2, late Salts, Such as acetates, which are convertible to iodides
(Rh(CO)I), Rh(Cod)Cl), rhodium(III) chloride, rhodium 40 under the carbonylation conditions. Alternatively organic
(III) iodide, rhodium (III) acetate, rhodium iodides, Suitably Selected from quaternary ammonium,
dicarbonylacetylacetone, RhCl(PPh) and RhCl(CO) pyridinium, picolinium or phosphonium iodides may be
(PPh3). Iridium is preferably used as a chloride-free com employed.
pound Such as a carboxylate Salt, e.g. the acetate, which is The carbon monoxide feed to the carbonylation process
Soluble in one or more of the liquid reaction components, 45 may be essentially pure or may contain impurities Such as
e.g. water and/or acetic acid, and So may be added as a carbon dioxide, methane, nitrogen, noble gases, water and
Solution therein. Examples of Suitable iridium-containing C to C paraffinic hydrocarbons. The presence of hydrogen
compounds which may be added to the liquid reaction in the carbon monoxide is generally not desirable. The
composition include IrC1, Ir, IrBr, Ir(CO)I, partial pressure of carbon monoxide in the carbonylation
Ir(CO)Cl], Ir(CO), Br, Ir(CO), IH", Ir(CO).Br. 50 reaction vessel may Suitably be in the range 1 to 70 barg,
H, Ir(CO).I., Ir(CH.)I,(CO), H, Ir(CO), preferably 1 to 35 barg, more preferably 1 to 15 barg.
IrCl3.4H2O, IrBr.4 H2O, Ira(CO)12, iridium metal, IrO, The total preSSure of the carbonylation proceSS is Suitably
IrO2, Ir(acac)(CO), Ir(acac), iridium acetate, in the range 10 to 100 barg. The temperature at which the
IrO(OAc)(HO)IOAc) and hexachloroiridic acid carbonylation proceSS is operated is Suitably in the range 100
HIrCl), preferably chloride-free complexes of iridium 55 to 300° C., preferably in the range from 150 to 220° C. The
Such as acetates, oxalates and acetoacetates. process of the present invention will now be illustrated by
Preferably the concentration of the catalyst in the liquid reference to the following Example and comparison test.
reaction composition is in the range from 50 to 5000 ppm by COMPARISON TEST
weight of the metal, preferably 100 to 2500 ppm by weight
of the metal. 60 There was fed to a drying column a fraction comprising
There is employed as co-catalyst in the liquid reaction acetic acid, water and hexyl iodide obtained as a sidedraw
composition methyl iodide. A Suitable methyl iodide con from a light ends column Separating overhead a light ends
centration in the liquid reaction composition is in the range recycle Stream comprising water, methyl acetate, methyl
from 1 to 30% by weight, more preferably 1 to 20% by iodide, acetic acid and propionic acid precursors, there being
weight, for example 1 to 10% by weight. 65 fed to the light ends column the Volatile fraction comprising
Optionally one or more promoters may be present in the acetic acid product, water, higher organic iodides, methyl
liquid reaction composition. The choice of promoter will to acetate, methyl iodide, propionic acid by-product and pro
 US 6,326,515 B1
7 8
pionic acid precursors separated from a liquid fraction Group VIII noble metal catalyst being rhodium, option
comprising involatile rhodium catalyst, acetic acid and ally one or more promoters of a type forming an iodide
water in a flash vessel to which was fed the liquid product Salt, e.g. lithium iodide, (b) in the case of the Group
obtained from the rhodium-catalysed methyl iodide VIII noble metal catalyst being iridium, optionally one
co-catalysed, carbonylation of methanol in the presence of or more promoters Selected from the group consisting
Water. of ruthenium, osmium, rhenium, cadmium, mercury,
Over a period of Seven calendar months the concentration Zinc, gallium, indium and tungsten, (iv) a finite amount
of water on the feed tray of the drying column was in the of water (v) methyl acetate, (vi) acetic acid, (vii) higher
organic iodides, including hexyl iodide, by-product,
range from 9 to 14% by weight and the water concentration and propionic acid by-product and its precursors,
in the heads water was within the range from about 35 to (b) withdrawing liquid reaction composition from the
68% by weight. Over this period the concentration of hexyl carbonylation reactor and introducing at least part of
iodide in the acetic acid removed from the base of the the withdrawn liquid reaction composition, with or
column was in the range on average from about 20 to 120 without the addition of heat, to a flash Zone to form a
ppb. Vapour fraction comprising water, acetic acid product,
15
EXAMPLE higher organic iodides by-product, methyl acetate,
methyl iodide, propionic acid by-product and propionic
The Comparison Test was continued for a period of over acid precursors, and a liquid fraction comprising
12 months in identical fashion except that the concentration involatile Group VIII noble metal catalyst, involatile
of water on the feed tray of the drying column was main optional promoter or promoters, acetic acid and water;
tained within the range from 10 to 14%, principally 10 to (c) recycling the liquid fraction from the flash Zone to the
12%, by weight and the concentration of water in the heads carbonylation reactor;
was maintained on average in the range 70 to 85%, princi (d) introducing the vapour fraction from the flash Zone
pally from 75 to 85% by weight. Over this period the into a first distillation Zone;
concentration of hexyl iodide in the acetic acid removed (e) removing from the first distillation Zone at a point
from the base was on average less than 5 ppb. 25
above the introduction point of the flash Zone vapour
We claim:
1. A process for removing higher organic iodides, includ fraction a light ends recycle Stream comprising water,
ing hexyl iodide, from an acetic acid product obtained by methyl acetate, methyl iodide, acetic acid and propionic
carbonylating methanol and/or a reactive derivative thereof acid precursors which Stream is recycled in whole or in
in the presence of a finite concentration of water, Group VIII part to the carbonylation reactor;
noble metal catalyst, methyl iodide as co-catalyst, and (f) removing from the first distillation Zone as a sidedraw
optionally a catalyst promoter, which process includes the at a point below the introduction point of the flash Zone
Step of Subjecting an aqueous composition comprising acetic Vapour fraction, a stream comprising acetic acid, water,
acid and at least one higher organic iodide to distillation in propionic acid by-product, and higher organic iodides
a column, or Section of a column, Separating water overhead 35
by-product;
from a dry acetic acid fraction, wherein the water concen (g) feeding the sidedraw stream from (f) to an interme
tration on the feed tray of the column, or Section of the diate point in a Second distillation Zone wherein the
column, is greater than 8% by weight and the water con water concentration on the feed tray to the column is
centration in the head of the column, or Section of the greater than 8% by weight, and the water concentration
column, is greater than 70% by weight. 40 at the head of the column is greater than 70% by
2. A proceSS as claimed in claim 1 wherein the water weight;
concentration on the feed tray of the column is from 8 to (h) removing from the Second distillation Zone an over
14%. head fraction comprising water and higher organic
3. A process as claimed in claim 1 wherein the concen iodides and from a point below the feed point a fraction
tration of water at the head of the column is from 70 to 85% 45 comprising acetic acid product and propionic acid
by weight. by-product with Significantly reduced amounts of
4. A proceSS as claimed in claim 1 wherein the finite higher organic iodides.
concentration of water is from 0.1 to 30% by weight in the 10. A process as claimed in claim 1 which comprises the
liquid reaction composition. Steps of
5. A process as claimed in claim 1 wherein the Group VIII 50 (a) feeding methanol and/or a reactive derivative thereof
noble metal catalyst is rhodium or iridium. and carbon monoxide to a carbonylation reactor in
6. A process as claimed in claim 5 wherein the catalyst is which there is maintained during the course of the
present in the liquid reaction composition in the range of process a liquid reaction composition comprising (i) a
from 50 to 5000 ppm by weight of metal. Group VIII noble metal carbonylation catalyst, (ii)
7. A proceSS as claimed in claim 1 wherein the promoter 55 methyl iodide co-catalyst, (iii) (a) in the case of the
is a metal promoter, a inorganic iodide or organic iodide. Group VIII noble metal catalyst being rhodium, option
8. A process as claimed in claim 1 carried out under a ally one or more promoters of a type forming an iodide
pressure of 10 to 100 barg and a temperature of 100 to 300 Salt, e.g. lithium iodide, (b) in the case of the Group
C. VIII noble metal catalyst being iridium, optionally one
9. A proceSS as claimed in claim 1 which comprises the 60 or more promoters Selected from the group consisting
Steps: of ruthenium, osmium, rhenium, cadmium, mercury,
(a) feeding methanol and/or a reactive derivative thereof Zinc, gallium, indium and tungsten, (iv) a finite amount
and carbon monoxide to a carbonylation reactor in of water (v) methyl acetate, (vi) acetic acid, (vii) higher
which there is maintained during the course of the organic iodides, including hexyl iodide, by-product,
process a liquid reaction composition comprising (i) a 65 and propionic acid by-product and its precursors,
Group VIII noble metal carbonylation catalyst, (ii) (b) withdrawing liquid reaction composition from the
methyl iodide co-catalyst, (iii) (a) in the case of the carbonylation reactor and introducing at least part of
 US 6,326,515 B1
10
the withdrawn liquid reaction composition, with or (f) condensing the overhead vapour fraction from (e),
without the addition of heat, to a flash Zone to form a passing the condensate to a decanter wherein it is
Vapour fraction comprising water, acetic acid product, Separated into a methyl iodide-rich phase and an aque
higher organic iodides by-product, methyl acetate, OuS phase, the methyl iodide-rich phase being recycled
methyl iodide, propionic acid by-product and propionic to the carbonylation reactor and the aqueous phase
acid precursors, and a liquid fraction comprising being divided, part being returned to the first distilla
involatile Group VIII noble metal catalyst, involatile tion Zone as reflux and the remainder being recycled to
optional promoter or promoters, acetic acid and water;
(c) recycling the liquid fraction from the flash Zone to the the carbonylation reactor;
carbonylation reactor; 1O (g) removing from the first distillation Zone at a point
(d) introducing the vapour fraction from the flash Zone below the introduction point of the flash Zone vapour
into a first distillation Zone, which first distillation Zone fraction, a proceSS Stream comprising dry acetic acid
incorporates an upper Section wherein an aqueous and propionic acid by-product; and
composition comprising acetic acid and at least one 15 (h) optionally introducing the aforesaid stream into a
higher organic iodide is separated into water overhead Second distillation Zone;
from a dry acetic acid fraction, the water concentration (i) removing from the Second distillation Zone a bottom
on the feed tray being greater than 8% by weight and
the water concentration at the head of the Section being fraction comprising propionic acid; and
greater than 70% by weight; (j) removing from the Second distillation Zone a sidedraw
(e) removing from the first distillation Zone an overhead fraction comprising dry acetic acid product containing
Vapour fraction comprising water, higher organic less than 250 ppm propionic acid.
iodides, methyl acetate, methyl iodide, propionic acid
precursors and acetic acid;