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 puried 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) ber, lm, 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 rst 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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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 signicant 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 signicant 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 rst 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
Table 1 Acetic acid process Catalyst Methanol carbonylation Acetaldehyde oxidation Ethylene direct oxidation Hydrocarbon oxidation (n-butane, naphtha) Rhodium complex Manganese acetate or cobalt acetate Palladium/heteropolyacid/ metal Cobalt acetate or manganese acetate

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 efcient 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.

Reaction condition ( C, atm) 180220, 3040 5060, atmospheric pressure 150160, 80 150230, 5060

Yield MeOH: 99%, CO: 85% CH3 CHO: 95% Ethylene: 87% n-Butane: 50%, naphtha: 40%

By-product None None Acetaldehyde CO2 Formic acid, propionic acid, etc.

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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

acid process based on butylene feedstock. This process also employs direct oxidation. Its key features are the use of a relatively cheap rafnate-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 rst 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 signicantly 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

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 ash column. A schematic of a conventional methanol carbonylation plant conguration is shown in Fig. 6 [28]. Rhodium catalyst is separated from the product acetic acid by conducting a simple ash; 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 rst distillation column. This column is followed by a drying column and then a column for the removal of heavy

Fig. 4. Mechanism for water gas shift.

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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 identied 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 rst commercialized in the 1980s by Celanese and Daicel. In this process, it is proposed that the addition of a signicant 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 conguration.

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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 ve-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 nal 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 nal 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 identied as part of the early work done by Monsanto [3,18,25], however, the reaction rate exhibited by the

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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 efciency 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

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 signicant 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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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 signicant 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 difculty in product purication. 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 signicantly reduces the loss of expensive Rh metal because the catalyst is conned 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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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, ow up the reactor riser, where the CO is consumed in the reaction. The process ow, 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 ow.

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4. Methyl formate isomerization 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: HCOOCH3 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.

etc.). The reaction is carried out at approximately 220 C and 40 atm: CO + 2H2 CH3 OH 2CH3 OH CH3 OCH3 + H2 O H2 O + CO CO2 + H2 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: CH3 OH + CO CH3 COOH 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 rst commercialized in 1960:
1 CH2 =CH2 + 2 O2 CH3 CHO 1 CH3 CHO + 2 O2 CH3 COOH

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 efcient 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 signicant capital cost reduction relative to the conventional ow scheme. Applying this concept, Haldor Topsoe proposed an integrated process that includes the synthesis of methanol and dimethyl ether (DME) in a rst 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 rst 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,

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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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: 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 rst 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 xed 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
catalyst

7. Other proposed technologies for the production of acetic acid 7.1. Ethane oxidation In the 1980s, an acetic acid route from ethane was introduced. Two reaction mechanisms based on: 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 benecial 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%
catalyst

Scheme 2. Partial oxidation route.

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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-modied 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

acid in the presence of rhodium trichloride dissolved in water [72]:

1 CH4 + CO + 2 O2 CH3 COOH RhCl3

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 signicant and large base capacity. Signicant developments in both process and catalyst technology have supported the growth in this market since the 1950s when the rst 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, signicant 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.

= 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 rst 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

References
[1] Asian Chemical News, 16 November 1998. [2] N. Kutenpov, W. Himmele, H. Hohenshutz, Hydrocarbon Proc. 45 (1966) 141. [3] F.E. Paulik, J.R. Roth, J. Am. Chem. Soc., Chem. Commun. (1968) 1578. [4] H.D. Grove, Hydrocarbon Proc. 51 (1972) 76. [5] US Patent 3769329 (1973) to Monsanto. [6] R.T. Eby, T.C. Singleton, Appl. Indian Catal. 1 (1983) 275. [7] M.J. Howard, M.D. Jones, M.S. Roberts, S.A. Taylor, Catal. Today 18 (1993) 325. [8] M.A. Murphy, B.L. Smith, G.P. Torrence, A. Agulio, J. Organomet. Chem. 303 (1986) 257.

N. Yoneda et al. / Applied Catalysis A: General 221 (2001) 253265 [9] B.L. Smith, G.P. Torrence, M.A. Murphy, A. Agulio, J. Mol. Catal. 39 (1987) 115. [10] European Patent Application 0161874 (1985). [11] Japanese Patent Koukai 60-239434 (1985) to Celanese. [12] Japanese Patent Koukoku 04-69136 (1992) to Daicel. [13] Japanese Patent Koukoku 03-38256 (1991) to Daicel. [14] Japanese Patent Koukoku 07-23337 (1995) to Daicel. [15] R.F. Heck, J. Am. Chem. Soc. 85 (1963) 2013. [16] N. Ritzkalla, Industrial chemicals via C1 processes, Am. Chem. Soc. (1987) 61. [17] US Patent 4133963 (1979) to Eastman. [18] D. Foster, Adv. Organomet. Chem. 17 (1979) 255. [19] Japanese Patent Koukai 06-340573 (1994) to Poulenc. [20] European Patent Publication 643034 (1994) to BP. [21] European Patent Publication 728726 (1994) to BP. [22] European Patent Publication 752406 (1995) to BP. [23] Kagakukougyou Nippou, 12 July 1996. [24] T.W. Dekleva, D. Forster, Adv. Catal. 34 (1986) 81. [25] European Chemical News, 26 May1 June 1997. [26] D. Forster, T.C. Singleton, J. Mol. Catal. 17 (1982) 299. [27] D. Forster, T.W. Dekleva, J. Chem. Edu. 63 (3) (1986) 204. [28] D.J. Watson, Catalysis of Organic reactions, Marcel Dekker, New York, 1998, p. 369. [29] M. Gauss, A. Seidel, P. Torrence, P. Heymanns, Applied Homogeneous: Catalysis with Organometallic Compounds, Vol. 1, VHC, New York, 1996, p. 104. [30] Japanese Patent Koukai 7-503489 (1995) to Bohan Iron. [31] Japanese Patent Koukoku 5-28212 (1993) to Hoechst. [32] Japanese Patent Koukai 62-72636 (1987) to Hoechst. [33] Japanese Patent Koukai 46-5367 (1971) to Monsanto. [34] Japanese Patent Koukoku 60-54294 (1985) to Monsanto. [35] US Patent 4615806 (1986) to Celanese. [36] P.M. Maitlis, A. Haynes, G.J. Sunley, M.J. Howard, J. Chem. Soc., Dalton Trans. (1996) 2187. [37] R.G. Schultz, P.D. Montgromerry, J. Catal. 13 (1969) 105. [38] US Patent 3717670 (1973) to Monsanto. [39] A. Krzywicki, M. Marczewski, J. Mol. Catal. 6 (1979) 431. [40] M.S. Scurrell, R.F. Howe, J. Mol. Catal. 7 (1980) 535. [41] US Patent 4657884 (1987) to Hoechst. [42] US Patent 4776987 (1988) to Hoechst. [43] R.S. Drago, E.D. Nyberg, A.E. Amma, A. Zombeck, Inorg. Chem. 20 (1981) 641. [44] M.S. Jarrel, B.C. Gates, J. Catal. 40 (1975) 255.

265

[45] J. Hjortkjaer, Y. Chen, B. Heinrich, Appl. Catal. 67 (1991) 269. [46] European Patent 277824 (1988) to Reilly. [47] US Patent 5334755 (1994) to Chiyoda. [48] US Patent 5364963 (1994) to Chiyoda. [49] US Patent 5576458 (1996) to Chiyoda. [50] N. Yoneda, T. Minami, J. Weiszmann, B. Spehlmann, Science and technology in catalysis, in: Proceedings of the Third Tokyo Conference on Advanced Catalytic Science and Technology, 1998, p. 93. [51] US Patent 5962735 (1999) to UOP. [52] D.J. Schreck, D.C. Busby, R.W. Wegman, J. Mol. Catal. 47 (1988) 117. [53] G. Bud, H.U. Hog, J. Mol. Catal. A: Chem. 95 (1995) 1134. [54] Japanese Patent Koukai 7-60130 (1995) to Chiyoda. [55] M. Komatsu, M. Yoneoka, Kagaku Kougyo 43 (1988) 1134. [56] S. Shinoda, T. Yamakawa, J. Chem. Soc., Chem. Comun. (1990) 1151. [57] T. Yamakawa, P. Tsai, S. Shinoda, Appl. Catal. A L1 (1992) 92. [58] European Patent Application 801050 (1997). [59] US Patent 5728871 (1998) to Topsoe. [60] British Patent 1020068 (1965) to Halcon. [61] Japanese Patent Koukai 47-13221 (1971) to National Distillers. [62] FR 1568742 (1967) IFP. [63] Japanese Patent Koukai 7-89896 (1995) to Denko. [64] Japanese Patent Koukai 9-67298 (1995) to Denko. [65] K. Sano, H. Uchida, Shokubai 41 (4) (1999) 290. [66] European Patent Application 294845 (1988) to UCC. [67] European Patent Application 407091 (1991) to BP. [68] European Chemical News, 29 March4 April 1999, p. 28. [69] World Patent 9805619 (1998) to Hoechst. [70] US Patent 5907056 (1999) to Sabic. [71] T. Nishiguch, et al., Chem. Lett. 20 (1992) 1141. [72] Chem. Week 20 (1994). [73] V.H. Agreda, J.R. Zoeller, Acetic Acid and Its Derivatives, Marcel Dekker, New York, 1993, Chapters 16, p. 3. [74] F.S.Wagner, Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 1, 1991, p. 121. [75] W.R. Moser, B.J. Marshik-Guerts, S.J. Okrasinski, J. Mol. Catal. A: Chem. 143 (1999) 57. [76] W.R. Moser, B.J. Marshik-Guerts, S.J. Okrasinski, J. Mol. Catal. A: Chem. 143 (1999) 71.