Applied Catalysis A: General 221 (2001) 253265

Recent advances in processes and catalysts

for the production of acetic acid
Noriyuki Yoneda a , Satoru Kusano a, , Makoto Yasui b , Peter Pujado c , Steve Wilcher c
a
b

Chiyoda Corporation, 3-13 Moriya-cho, Kanagawa-ku, Yokohama 221-0022, Japan

Chiyoda Corporation, 2-12-1 Tsurumichuo, Tsurumi-ku, Yokohama 230-8601, Japan
c UOP LLC, 25 East Algonquin Road, Des Plaines, IL 60017-5017, USA

Abstract
Novel acetic acid processes and catalysts have been introduced, commercialized, and improved continuously since the
1950s. The objective of the development of new acetic acid processes has been to reduce raw material consumption, energy
requirements, and investment costs. At present, industrial processes for the production of acetic acid are dominated by
methanol carbonylation and the oxidation of hydrocarbons such as acetaldehyde, ethylene, n-butane, and naphtha. This paper
discusses advances in acetic acid processes and catalysts according to the following routes: (1) methanol carbonylation; (2)
methyl formate isomerization; (3) synthesis gas to acetic acid; (4) vapor phase oxidation of ethylene, and (5) other novel
technologies. 2001 Published by Elsevier Science B.V.
Keywords: Acetic acid; Methanol carbonylation; Hydrocarbon oxidation; Reaction mechanisms

1. Introduction
Acetic acid is an important commodity chemical
used in a broad range of applications. As shown in
Fig. 1, acetic acid is used primarily as a raw material for vinyl acetate monomer (VAM) and acetic
anhydride synthesis, and as a solvent for purified
terephthalic acid (PTA) production. The demand for
acetic acid has increased, especially in southeast Asia,
where several new PTA plants have been built. With
the increased demand and installed capacity for PTA
in southeast Asia, the region has become a major
producer of polyester (PET) fiber, film, and resin.
Although the economic crisis in Asia momentarily
suppressed the demand for acetic acid to less than
expected levels, in the medium and long terms there
Corresponding author. Tel.: +81-45-441-9151;
fax: +81-45-441-1281.

is potentially a great demand for acetic acid in this

market.
The total world capacity of acetic acid has reached
approximately 7.8 million t in 1998 with BP-Amoco
and Celanese accounting for more than 50% of
the worlds capacity [1]. BP-Amoco and Celanese
have installed capacities of 1.5 million t (19%), and
2.0 million t (26%), respectively.

2. Processing routes to acetic acid

Originally, acetic acid was produced by aerobic fermentation of ethanol, which is still the major process
for the production of vinegar. The first major commercial process for the synthetic production of acetic
acid was based on the oxidation of acetaldehyde. In
an early process for the conversion of acetylene to acetaldehyde introduced in 1916 in Germany and used

0926-860X/01/$ see front matter 2001 Published by Elsevier Science B.V.

PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 8 0 0 - 6

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N. Yoneda et al. / Applied Catalysis A: General 221 (2001) 253265

Fig. 1. Use of acetic acid.

in China until recently, an organo-mercury compound

was used as the catalyst. The toxicity of the mercury
catalyst resulted in significant environmental pollution, and as a result, has essentially been phased out.
As the petrochemical industry developed in the 1950s,
the raw material for the production of acetaldehyde
shifted to ethylene. Other processes for the production
of acetic acid introduced in the 1950s and 1960s were
based on the oxidation of n-butane or naphtha. The
major producers of acetic acid via direct oxidation of
hydrocarbons were Celanese (via n-butane) and BP
(via naphtha). However, these reactions also produce
significant amounts of oxidation by-products, as summarized in Table 1, and their separation and recovery
can be very complex and expensive.
The homogeneous methanol carbonylation route to
acetic acid that used a homogeneous Ni catalyst was
first commercialized by BASF in 1955. An improved
process was later disclosed by BASF in 1960. The
process used an iodide-promoted CO catalyst and
operated at elevated temperature (230 C) and pressure (600 atm). The product yields exhibited by this

process were 90, and 70% based on methanol and CO

consumption, respectively, [2]. In 1970, Monsanto
commercialized an improved homogeneous methanol
carbonylation process using a methyl-iodide-promoted
Rh catalyst [36]. Compared to other acetic acid synthesis routes (ethanol fermentation, and acetaldehyde,
n-butane, or naphtha oxidation), homogeneous Rh
catalyzed methanol carbonylation is an efficient route
that exhibits high productivity and yields. The process operated at much milder conditions (180220 C,
3040 atm) than the BASF process and exhibited superior performance: acetic acid yields were 99 and
85% based on methanol and CO consumption, respectively, [7]. Celanese and Daicel further improved
the Monsanto process during the 1980s by adding
a lithium or sodium iodide promoter to enable the
operation in a reduced water environment [815]. At
lower water concentrations, by-product formation via
the water gas shift reaction is reduced, thus improving
raw materials consumption and reducing downstream
separation costs.
Homogeneous metal catalysts less costly than Rh
(for example, Ni [16,17,75,76] and Ir [3,1824] with
other metal additives) have also been investigated.
The Ir-based process allows operation at reactor water
levels comparable to those of the improved Celanese
process and was commercialized by BP Chemicals in
1996.
Until recently, virtually all new acetic acid capacity has made use of the homogeneous methanol
carbonylation technology developed by Monsanto
and practiced commercially by all major acetic acid
manufacturers, including BP-Amoco, Celanese, and
others. As a result, more than 60% of the world acetic
acid production employs the methanol carbonylation
methods, as shown in Fig. 2.

Table 1
Acetic acid process

Methanol carbonylation
Acetaldehyde oxidation
Ethylene direct oxidation
Hydrocarbon oxidation
(n-butane, naphtha)

Catalyst

Reaction condition
( C, atm)

Yield

By-product

Rhodium complex
Manganese acetate
or cobalt acetate
Palladium/heteropolyacid/
metal
Cobalt acetate or
manganese acetate

180220, 3040
5060, atmospheric
pressure
150160, 80

MeOH: 99%, CO: 85%

CH3 CHO: 95%

None
None

Ethylene: 87%

Acetaldehyde CO2

n-Butane: 50%,
naphtha: 40%

Formic acid,
propionic acid, etc.

150230, 5060

N. Yoneda et al. / Applied Catalysis A: General 221 (2001) 253265

Fig. 2. Acetic acid process routes.

Inherent to the homogeneous system, however, are

drawbacks relating to catalyst solubility limitations
and the loss of expensive Rh metal due to precipitation in the separation sections. Accordingly, immobilization of the Rh complex on a support has been
the subject of considerable investigation. Chiyoda and
UOP have jointly developed an improved methanol
carbonylation process for the production of acetic acid
based using a heterogeneous Rh catalyst system [25].
A direct oxidation process for the production of
acetic acid starting from ethylene was commercialized
by Denko in 1997. While the raw material, ethylene,
is more expensive than in the methanol carbonylation
route, the investment cost is reported to be lower and
competitive for small or medium-size capacity plants.
Wacker-Chemie plans to commercialize a new acetic

255

acid process based on butylene feedstock. This process

also employs direct oxidation. Its key features are the
use of a relatively cheap raffinate-2 feedstock and competitive economics in medium size plants. Recently,
Poulenc and others have disclosed the direct production of acetic acid from ethane; there are no indications of impending commercialization for this route.
Generally, the production cost of commodity chemicals such as acetic acid is dominated by the raw material costs, and methanol carbonylation is still regarded
as the preferred route to produce acetic acid. Table 1
summarizes reaction conditions, catalysts and yields
for the major processes used to produce acetic acid. A
number of reviews on production of acetic acid have
been published and are referred [7,29,73,74].

3. Methanol carbonylation
3.1. Rhodium catalyzed methanol carbonylation
The methanol carbonylation process, Monsanto process, is operated under mild conditions
(180220 C, 3040 atm) and exhibits high selectivity
to acetic acid based on methanol (99%) and carbon
monoxide (85%) [7]. While the reaction, as shown
below, can be carried out in a variety of rhodium
(I) or rhodium (III) complexes [6,18], under reaction
conditions they are almost invariably converted to the
active catalyst [RhI2 (CO)2 ]1 . As shown in Fig. 3,

Fig. 3. Catalytic cycle for rhodium carbonylation.

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methyl iodide is provided by the reaction of feed

methanol with hydrogen iodide:
CH3 OH + CO

Rh complex

CH3 COOH

Methyl iodide is oxidatively added to the rhodium

dicarbonyldiiodide complex [RhI2 (CO)2 ]1 (A)
to generate a rhodiummethyl complex (B). This
rhodiummethyl complex can rapidly undergo a
methyl migration to a neighboring carbonyl group in
the acetyl form (CH3 CO) and react with CO (C) to
generate the rhodiumacetyl complex (D). Reductive
elimination of acetyl iodide (CH3 COI) can then liberate the original rhodium complex (A). Hydration of
acetyl iodide is very rapid in the presence of excess
water and will result in the formation of acetic acid
and hydrogen iodide to complete the cycle.
The reaction rate is independent of methanol
concentration and carbon monoxide pressure. The
rate-determining step is believed to be the oxidative
addition of methyl iodide to the rhodium center of the
rhodium complex (A), and the reaction rate is essentially of first order in both catalyst and methyl iodide
concentrations under normal reaction conditions:
reaction rate [catalyst][CH3 I]
A substantial quantity of water (1415 wt.%) is required to achieve high catalyst activity and also to
maintain good catalyst stability [8,9,1214]. However,
as rhodium also catalyzes the water gas shift reaction
(Fig. 4), the side reaction forming CO2 and H2 from
CO is significantly affected by water and hydrogen
iodide concentration in the reaction liquid [26,27].
Propionic acid is observed as the major liquid
by-product in this process. This is produced by the
carbonylation of ethanol that is often present as a
minor impurity in the methanol feed; however, other

Fig. 4. Mechanism for water gas shift.

routes are active since more propionic acid is observed

than can be accounted for by only this mechanism.
The rhodium catalyst system can generate acetaldehyde, and it is proposed that this acetaldehyde is
reduced by hydrogen in the system to give ethanol
which subsequently yields propionic acid. One possible precursor for the generation of acetaldehyde is the
rhodiumacetyl species, as shown in the following
mechanism [28]:
[RhI3 (CO)(COCH3 )] + HI
[RhI4 (CO)] + CH3 CHO
[RhI4 (CO)] RhI3 + I + CO
Reaction of this species with hydrogen iodide would
yield acetaldehyde and [RhI4 (CO)]1 . The latter
species is well known in this system and is postulated
as the principal cause of catalyst loss by precipitation
of inactive rhodium tri-iodide [28].
Acetaldehyde undergoes self-condensation or aldol
condensation and yields butenal and higher aldehydes. These can undergo further reactions to alcohols
and carboxylic acids as summarized in the network of
Fig. 5 [28]. It would be expected that the homologation observed would result in unsaturates and iodides
having an even number of carbon atoms, and long
chain carboxylic acids with an odd number of carbon
atoms. Particular problems are encountered with the
C6 species present. The boiling points of the unsaturated compounds, including hexanal and some of its
isomers, are very similar to that of acetic acid. Furthermore, hexyl iodide is observed to form a constant boiling azeotropic mixture with acetic acid. The presence
of the unsaturates, even at low parts per million concentrations can cause problems with product stability.
Separation of pure acetic acid product from the reaction medium presents few problems. In this process,
however, the expensive Rh metal can be lost due to its
precipitation and vaporization in the flash column. A
schematic of a conventional methanol carbonylation
plant configuration is shown in Fig. 6 [28]. Rhodium
catalyst is separated from the product acetic acid by
conducting a simple flash; the catalyst remains in the
liquor and can be recycled to the reactor. The separation of light compounds, such as methyl iodide and
methyl acetate, may be carried out in the first distillation column. This column is followed by a drying
column and then a column for the removal of heavy

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257

Fig. 5. Network of liquid by-products.

by-products. Energy usage in this fractionation train

can be high, depending on the concentration of water
and impurities such as propionic acid, heavy unsaturates, and hexyl iodide present.
In the Monsanto process, because of the high water
concentration in the reactor (1415 wt.%), the separation of water from the acetic acid product is a major
energy consumer and can limit the unit capacity. In
addition, excess water causes carbon monoxide yield
loss due to the water gas shift reaction, and increases
the formation of by-products such as propionic acid,
thus lowering the acetic acid quality. Considerable savings in operating costs can be realized by operating
at low water concentration if a way can be found to
compensate for the consequent decrease in the reaction rate and catalyst stability [29]. As a result, the
rhodium complex stability at low water concentrations
has been extensively investigated.

Group I metal iodides, especially lithium iodide in

combination with methyl iodide, were identified early
as a good agent for enhancing the stability of the
rhodium catalyst at low reactor water concentrations
(45 wt.%), and also for decreasing liquid by-product
formation [1214]. Further work in this area revealed
that the addition of a substantial quantity (1620 wt.%)
of group I metal iodides also enhanced the reactor
productivity even at quite low water concentrations
(2 wt.%) [811]. These features reportedly allow existing plants to expand their capacity for little incremental capital cost. The improved methanol carbonylation
process, low water process, effected by adding
group I metal iodides to the Monsanto process was first
commercialized in the 1980s by Celanese and Daicel.
In this process, it is proposed that the addition of
a significant quantity of group I metal causes the Rh
complex to be more coordinated by CH3 COO and

Fig. 6. Schematic of a acetic acid plant configuration.

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Fig. 7. Reaction acceleration mechanism by iodide salt.

increases the rate of oxidative insertion of methyl iodide (the rate determining step), thus promoting the
primary carbonylation reaction (Fig. 7). As Figs. 7 and
8 shows the effect of the addition of lithium iodide
on the reaction rate, the overall carbonylation rate increase is presumably due in part to the formation of
a strong nucleophilic five-coordinate dianionic intermediate [Rh(CO2 )2 I2 L]2 (L = I , OAc ) which
is more active toward oxidative addition of methyl iodide [811,29].
The main advantages of the low water process relative to the conventional Monsanto process are reduced
raw materials consumption, increased productivity,
lower utility requirements, and lower capital costs
per unit of product. However, low water operation

with alkali-iodide promoters results in a higher iodide

environment, and higher residual iodide in the final
product. High iodide concentration in acetic acid leads
to catalyst poisoning problems in some downstream
applications, such as in the manufacture of VAM. To
overcome the problems associated with high iodide
concentration in the final product, treatment by active
carbon [30], hydrogenation [31,32], and extra distillation [33,34] have been proposed. Celanese disclosed
the silver-guard process for the removal of very low
levels of iodide impurities from acetic acid in their
patent [35]. The use of silver metal on an ion exchange
resin such as Amberlyst-15 reduces the iodide level
to below 1 ppb, as opposed to 20 ppb more normally
achieved by conventional methods. One particular
advantage of this system is the ability to effectively
remove the halide impurity in a single step, thus avoiding the need for additional distillation and recovery.
3.2. Nickel catalyzed methanol carbonylation
Recent studies have shown that nickel catalysts
can operate under mild conditions (190 C, 70 atm)
with the addition of methyl iodide as a co-promoter
[16]. The activity of nickel catalyst systems can be
increased and the volatility of nickel carbonyl compounds lowered by the introduction of stabilizers such
as phosphines, alkali metals, tin, and molybdenum
[16,17,25,75,76]. The active catalysts are thought to
be Ni(0) complexes. For phosphine-promoted catalyst, Ni(PR3 )2 is considered an active form of catalyst
and, in addition, Ni(CO)4 was observed in all cases,
and its concentration was reduced by strongly coordinating ligands and enhanced by weakly coordinating
ligands [76]. Recent work on nickel catalyst systems
shows that reaction rates and selectivities can approach those achieved in the rhodium catalyst system.
Although nickel catalysts have the advantage of being
much cheaper than rhodium, and are easy to stabilize at low reactor water concentrations, [Ni(CO)4 ] is
known to be a very toxic and volatile compound. To
date, commercialization has not proceeded.
3.3. Iridium catalyzed methanol carbonylation

Fig. 8. Effect of Li salt addition. Reaction condition:

[CH3 ] = 1.0 M, [MeOAc] = 0.3 M, [H2 O] = 1.0 M, temperature
= 190 C, total pressure = 400 psig.

The potential use of iridium instead of rhodium was

identified as part of the early work done by Monsanto
[3,18,25], however, the reaction rate exhibited by the

N. Yoneda et al. / Applied Catalysis A: General 221 (2001) 253265

rhodium catalyst system was superior to that of iridium. Recently, it was disclosed that an improved iridium catalyst, in combination with a promoter metal
such as ruthenium, has higher activity and results in
lower product impurity levels than reported in previous iridium systems [19]. The production of acetic
acid using the iridium catalyst system has been commercialized by BP-Amoco in two world scale plants to
date, and has received wide publicity as the Cativa
process. Although much iridium is required to achieve
an activity comparable to the rhodium catalyst-based
processes, the catalyst system is able to operate at reduced water levels (less than 8 wt.% for the Cativa
process versus 1415 wt.% for the conventional Monsanto process). Thus, lower by-product formation and
improved carbon monoxide efficiency are achieved,
and steam consumption is decreased. Until the early
1990s, the difference in the prices of rhodium (US$
500/oz) and iridium (US$ 60/oz) was the driving force
for replacing rhodium with iridium. However, current
price increases for iridium (US$ 450/oz) negate the
advantage in catalyst price.
The unique differences between the rhodium catalytic cycle and that of iridium in methanol carbonylation have been investigated [36]. The anionic
iridium cycle shown in Fig. 9, is similar to that shown
earlier for rhodium. Model studies have demonstrated

259

that the oxidative addition of methyl iodide to the

iridium center is of the order of 150 times faster
than the equivalent reaction with rhodium [36]. This
represents a possible improvement in the available
reaction rates, as methyl iodide addition is not the
rate determining step. The slowest step in this cycle is
the insertion of carbon monoxide to form the iridium
acetyl species, that involves the elimination of ionic
iodides and the coordination of an additional carbon
monoxide ligand. This would suggest the following
expression. The dependence on ionic iodide:
reaction rate [catalyst]

[CO]
[I ]

suggests that high reaction rates should be achievable by operating at low iodide concentrations. It
also suggests that the inclusion of species capable of
assisting in the abstraction of iodide should promote
the rate-limiting step. The patent would suggest that
ruthenium, or rhenium are the preferred promoters
[20,21]. In effect, a proprietary blend of promoters
has been found to increase reaction rate. The above
expression does not imply any effect from the water
present in the matrix, but water is found to have a
significant effect on rate [22].
In the improved iridium system, low water concentration in the reactor results in the formation of fewer

Fig. 9. Catalytic cycle for iridium carbonylation.

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N. Yoneda et al. / Applied Catalysis A: General 221 (2001) 253265

by-products such as propionic acid than in the original

Monsanto rhodium system, and no addition of lithium
iodide is required. Consequently, the iridium catalyst
system is also characterized by the formation of fewer
higher alkyl-iodide species than in the conventional
low water process.
3.4. Heterogeneous rhodium catalyzed
methanol carbonylation
In order to overcome the limitations of the homogeneous catalyst system (e.g. Rh precipitation
and catalyst solubility limitations), the immobilization of the Rh complex on a support has been the
subject of considerable investigation. Active carbon
was investigated as a possible support and proposed
for vapor-phase operation [7,37,38]. However, the
reaction rate was 1/10001/10 that of Monsantos homogeneous process and selectivity was also poorer.
Inorganic oxides and zeolites were also investigated
for use in vapor-phase operation [39,40]. For example, attaching the Rhphosphine ligand complex to
alumina by silylation was attempted [41,42]. The
resultant reaction rates for these catalysts were also
found to be poor relative to those observed for the
homogeneous system. To increase catalyst activity
for operation in the liquid phase, ion exchange resins
based on cross-linked polystyrene and incorporating
pendant phosphines, or vinyl pyridine copolymers
have been evaluated [4345]. Although the activity of
these catalysts in the liquid phase was comparable to
Monsantos homogeneous catalyst, there were problems with rhodium metal leaching from the resins
and the decomposition of the resins during operation at elevated temperature. Vinyl pyridine resin was
known to be more robust and more tolerant of operation at elevated temperature relative to polystyrene
resins. It was disclosed that catalysts using pyridine
resins exhibited high tolerance to operation at elevated temperature and pressure, and higher reaction
rate than Monsantos rhodium system [46]. Furthermore, Chiyoda introduced novel pyridine resins and
catalysts that exhibited high activity, long catalyst
life, and no significant rhodium loss [4749]. Based
on this heterogeneous Rh catalyst, Chiyoda and
UOP have jointly developed an improved methanol
carbonylation process, called the acetica process,
for the production of acetic acid. Until the recent

development of a commercial heterogeneous Rh catalyst system by Chiyoda, no successful demonstration

of such a catalyst had been known [7].
The heterogeneous catalyst commercialized for the
acetica process consists of Rh complexed on a novel
poly-vinyl pyridine resin [50], which is tolerant of
elevated temperatures and pressures. Under reaction
conditions, the Rh is converted to its catalytically
active anion form [Rh(CO)2 I2 ]1 . Furthermore, the
nitrogen atoms of the resin pyridine groups become
positively charged after quaternization with methyl
iodide. Thus, the strong ionic association between the
pyridine nitrogen groups and the Rh complex causes
the immobilization (Fig. 10). The concentration of Rh
on the solid phase is determined by the ion exchange
equilibrium. Because equilibrium strongly favors the
solid phase, virtually all the Rh in the reaction mixture
is immobilized.
In the acetica process, the methanol carbonylation reaction is conducted at moderate temperature
(160200 C) and pressure (3060 atm) and at low
water concentration without any additives present.
Catalyst stability has been demonstrated in both oncethrough and continuous-recycle pilot plant testing at
process conditions, low water content, and no Rh or
resin makeup. The catalyst exhibited no deactivation
after continuous operation for more than 7000 h [50].
With homogeneous methanol carbonylation routes,
acetic acid productivity is directly proportional to
catalyst concentration in the reaction liquid, and as
a result, acetic acid production is restricted by the
solubility of the active metal. Limited success has
been achieved in improving catalyst solubility in
these systems by increasing the reaction-mixture water concentration or by adding iodide salt stabilizers
[8,9,1214]. Both additives, however, result in increased recycle and separation costs, higher corrosion
rates, and difficulty in product purification.
With the heterogeneous catalyst system, catalyst
solubility limitations no longer govern reactor capacity since catalyst concentrations several times greater
than those achievable in the homogeneous systems
are possible. Immobilization also significantly reduces the loss of expensive Rh metal because the
catalyst is confined to the reactor rather than circulating downstream, where reduced pressures may cause
precipitation of rhodium and vaporization losses of
metal carbonyl compounds. The lower water content

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261

Fig. 10. Rhodium immobilization.

of 37 wt.% typical of the acetica process results

in reduced production of CO2 , and hydrogenated
by-products via the water gas shift reaction. Also,
because of the lower water content, less hydrogen
iodide is present in the system, and consequently the
process environment is less corrosive.
While the continuously stirred tank reactors (CSTR)
used in the conventional homogeneous processes
can be limited by gas solution rates to liquid and
are often prone to mechanical problems, the bubble
column, or gas lift reactor employed with the heterogeneous catalyst process does not suffer from such
problems and limitations. The acetica three-phase
gas lift reactor has no moving parts or mechanical

seals and was designed to maximize the performance

of its unique heterogeneous catalyst system without
any rotating equipment (Fig. 11). Methanol and CO
feeds are introduced at the reactor bottom, where the
compressed CO gas is distributed through a sparger.
Both of these feeds, along with the recycle liquid
and catalyst, flow up the reactor riser, where the
CO is consumed in the reaction. The process flow,
which is similar to that of a conventional homogeneous process is shown in Fig. 11. In cases where the
acetic acid product will be used for VAM production,
novel iodide removal technology is available to reduce the iodide in the acetic acid product to less than
3 ppb [51].

Fig. 11. Bubble column reactor and acetica process flow.

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4. Methyl formate isomerization

etc.). The reaction is carried out at approximately

220 C and 40 atm:

It has been proposed that acetic acid can be produced by isomerization of methyl formate in the presence of a homogeneous rhodium catalyst together with
other metal additives [52,53]. Heterogeneous rhodium
catalysts supported on poly-vinyl pyridine resin have
also been proposed for this application [54]. This catalyst has the same chemical morphology as a methanol
carbonylation catalyst. Methyl formate is produced by
dehydrogenation of methanol [55] or by methanol carbonylation under high pressure in the presence of:

CO + 2H2 CH3 OH

In the acetic acid synthesis step, carbonylation of

DME and methanol to acetic acid is carried out by
the rhodium carbonyl complex catalyst with carbon
monoxide being supplied from the synthesis gas
process unit:

HCOOCH3 CH3 COOH

CH3 OH + CO CH3 COOH

copper oxide and alkali catalyst. It is noted that

acetic acid production via methanol dehydrogenation followed by methyl formate isomerization requires only methanol and no carbon monoxide
plant:CH3 OHHCHOHCOOCH3 CH3 COOHAcetic acid can be produced from only methanol using a Ru-Sn catalyst according to the following steps
[56,57]. Ru-Sn bimetallic complexes are proposed to
be the active species.

5. Synthesis gas route to acetic acid

A nearby synthesis gas plant to produce CO is normally required to provide feed to an acetic acid plant.
On the contrary, an efficient integrated synthesis
gas and methanol synthesis plant and acetic acid plant
are available by combination of current technology at
the natural gas source. This integrated process could
achieve a significant capital cost reduction relative to
the conventional flow scheme.
Applying this concept, Haldor Topsoe proposed
an integrated process that includes the synthesis of
methanol and dimethyl ether (DME) in a first catalytic
reaction stage and the subsequent carbonylation of
methanol and DME into acetic acid [58,59]. Although
the reaction pressure required for methanol synthesis
is higher than the pressure used in acetic acid synthesis, the combination of methanol synthesis with
dimethyl ether synthesis can reduce the pressure of
the first reaction step. The catalyst consists of a mixture of the catalyst for methanol synthesis (Cu-Zn-Al
oxide, etc.) and a dehydration catalyst (H-ZSM-5,

2CH3 OH CH3 OCH3 + H2 O

H2 O + CO CO2 + H2

CH3 OCH3 + 2CO + H2 O 2CH3 COOH

Carbonylation reaction conditions of 170250 C and
2550 atm, can be used to obtain acceptable reaction
rates in the liquid phase.

6. Vapor phase oxidation of ethylene

The two-step oxidation process for the production
of acetic acid, starting from ethylene through acetaldehyde, was first commercialized in 1960:
CH2 =CH2 + 21 O2 CH3 CHO
CH3 CHO + 21 O2 CH3 COOH
This route involves the liquid phase oxidation of acetaldehyde using air and typically a manganese acetate catalyst operating at 5060 C. The reaction is
based on a free radical mechanism. Although this process features high yield (approximately 90%) and a
relatively low capital investment cost, it suffers from
high acetaldehyde feedstock cost and a very corrosive
catalyst system. Many plants utilizing this technology
have been shut down over the last 20 years.
There is also an older process that entails liquid
phase free radical oxidation of n-butane or naphtha
in the C4 C8 range. These reactions produce a wide
spectrum of oxidation by-products such as formic acid
and propionic acid:
CH3 CH2 CH2 CH3 +O2 CH3 COOH + by-products
The direct production of acetic acid from ethylene via
an acetaldehyde intermediate is a desirable synthesis

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263

enhance the activity and selectivity of the process for

the production of acetic acid. The selectivity to acetic
acid is approximately 86%, since it appears that acetaldehyde and carbon dioxide are necessarily formed
in this type of process.
Scheme 1. Hydration route.

route that has yet to be developed. Much work has been

undertaken to develop a simpler, single stage process
for producing acetic acid directly from ethylene:

7. Other proposed technologies for the

production of acetic acid
7.1. Ethane oxidation

catalyst

CH2 =CH2 + O2 CH3 COOH

Various groups have carried out extensive research and
development in the area of direct vapor phase oxidation of ethylene to acetic acid. Catalyst systems consisting of palladium chloride and V2 O5 supported on
Al2 O3 [60], and combinations of Pd (2%) and H3 PO4
(25%) on SiO2 , Pd-V2 O5 -Sb2 O3 on Al2 O3 [61], or
Pd (1%) on V2 O5 [62] have been proposed. These
catalysts have acetic acid selectivities in the range of
6090% based on ethylene. The routes have been proposed according to the different catalyst systems in
Schemes 1 and 2.
Denko has developed a direct oxidation process for
the production of acetic acid based on the hydration
route [6365] and has commercialized this technology in late 1997. The catalyst consists of either two
or three components. The first component is palladium supported on a carrier, preferably in the range of
0.12% range. The second component is a heteropoly
acid and their salts, preferably phosphotungstic acid
salts of lithium, sodium, and copper. The third component is copper, silver, tin, lead, antimony, bismuth,
selenium, or tellurium.
The reaction takes place in a fixed bed reactor at
operating temperatures and pressures of 150160 C,
and up to 8 atm, respectively. The gases fed to the reactor are ethylene, oxygen, steam, and nitrogen that is
used as a diluent. The presence of steam is required to

Scheme 2. Partial oxidation route.

In the 1980s, an acetic acid route from ethane was

introduced. Two reaction mechanisms based on:
catalyst

CH3 CH3 + O2 CH3 COOH + by-product

different catalyst systems were proposed: (1) partial
oxidation of the methyl group, and (2) ethane oxidation to ethylene followed by ethylene hydration to
ethanol, or ethylene to acetaldehyde.
A patent refers to the production of acetic acid
by reacting ethane, ethylene, or mixtures of ethane
and ethylene with oxygen over a catalyst containing
molybdenum, vanadium, and one other metal (Z) in
the general formula Mox Vy Zz [66]. In one example,
the patent describes the gas phase oxidation of a 1/10
mixture of ethane and ethylene at 255 C over a vanadium catalyst containing lesser amounts of molybdenum, niobium, antimony, and calcium supported on
an LZ-105 molecular sieve to yield 63% selectivity
to acetic acid, and 14% selectivity to ethylene at 3%
ethane conversion. In the combined ethane/ethylene
feed case, the hydration catalyst further catalyzes the
hydration of ethylene to ethanol, which is then converted to acetic acid (Scheme 1). The oxidation catalyst catalyzes the reaction of ethylene to acetic acid
and other oxidation products that are converted to
acetic acid (Scheme 2).
In another catalyst system, rhenium or a combination of rhenium and tungsten are introduced to
replace the molybdenum in the dehydrogenation catalyst [67]. Tests showed that complete substitution
of molybdenum by rhenium (Rex Vy Zz ) is beneficial
in the reaction of ethane to ethylene, whereas partial
substitution can increase the selectivity to acetic acid.
Tests were not performed on ethylene feed, but tests
on ethane (21% ethane, 3.8% oxygen, and 75.2%

264

N. Yoneda et al. / Applied Catalysis A: General 221 (2001) 253265

nitrogen) resulted in acetic acid selectivity as high as

78% at an ethane conversion of 14.3%.
More recently in 1998, another oxidative process
and catalyst for the production of acetic acid from
ethane, or ethylene was disclosed [68,69]. A new
molybdenum vanadate catalyst system promoted with
Nb, Sb, Ca, and Pd allows the gas phase oxidation of
ethane and/or ethylene to acetic acid, with high yield
and higher selectivity under milder operating conditions than previously achieved. The patent discloses
the production of acetic acid with 86% selectivity and
11% ethane conversion per pass, at a temperature and
pressure of 250280 C and 15 atm, respectively.
In 1999, a catalyst for the co-production of ethylene
and acetic acid from ethane was disclosed [70]. It consists of phosphorus-modified molybdenum-niobium
vanadate of formula Mo2.5 V1.0 Nb0.32 Px in which the
optimum range for the phosphorus (x) is 0.010.06:
CH3 CH3 + O2
catalyst

CH2 ==CH2 + CH3 COOH + H2 O

Ethane and air (15:85 (v/v)) at 260 C and 200 psig

(1100/h GHSV) reacted over the above catalyst system
(x = 0.042) to produce acetic acid and ethylene with
selectivities of 49.9, and 10.5%, respectively, at 53.3%
conversion. At phosphorus levels greater than 0.06%,
there is a marked increase in ethylene production with
a corresponding decline in acetic acid.
Recently, many attempts have been disclosed regarding the use of ethane as feedstock. Although
ethane is a relatively inexpensive and attractive raw
material for producing acetic acid, the oxidation processes produce a variety of co-products, the disposition of which needs to be considered in any business
plan.
7.2. Methane carbonylation
Novel methods for producing acetic acid directly
from methane under relatively mild conditions have
been reported. It was first disclosed that acetic acid
can be produced from methane and carbon monoxide in the presence of: Pd(OCOCH3 )2 /Cu(OCOCH3 )2 /
K2 S2 O8 /CF3 COOH [71].
Secondly, it was reported that the mixture of
methane, carbon monoxide and oxygen formed acetic

acid in the presence of rhodium trichloride dissolved

in water [72]:
RhCl3

CH4 + CO + 21 O2 CH3 COOH

This reaction proceeds in an aqueous medium at a
temperature of approximately 100 C and gives a high
yield of acetic acid. The reaction rates are reported
to be too slow for an economically viable industrial
process, but this novel process route has the potential
to reduce the cost of acetic acid production.

8. Conclusions
Acetic acid represents a commodity chemical
growing at 3.54.5% per year from a significant
and large base capacity. Significant developments in
both process and catalyst technology have supported
the growth in this market since the 1950s when the
first commercial synthetic process was introduced.
Methanol carbonylation has emerged as the dominant route to this product and currently over 60% of
the world acetic acid is produced using this route.
However, significant catalyst innovation has occurred
even within this production route resulting in greatly
improved yield, and selectivity at milder operating
conditions and lower cost of production. The lucrative nature of this market and the need for the major
producers to continually protect their market position
and investments is expected to drive further innovation within methanol carbonylation and the other
promising technology options looming on the horizon
that have been discussed in this paper.

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