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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
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 world’s capacity . 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
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. more than 60% of the world acetic acid production employs the methanol carbonylation methods. including BP-Amoco. The process operated at much milder conditions (180–220 ◦ C. by-product formation via the water gas shift reaction is reduced. The toxicity of the mercury catalyst resulted in signiﬁcant environmental pollution. atmospheric pressure 150–160. naphtha: 40% By-product None None Acetaldehyde CO2 Formic acid. CO: 85% CH3 CHO: 95% Ethylene: 87% n-Butane: 50%. and as a result. as shown in Fig. In 1970. The homogeneous methanol carbonylation route to acetic acid that used a homogeneous Ni catalyst was ﬁrst commercialized by BASF in 1955. . propionic acid.76] and Ir [3. as summarized in Table 1. 2. atm) 180–220. At lower water concentrations. 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 [8–15]. Reaction condition (◦ C.254 N.18–24] with other metal additives) have also been investigated. 80 150–230. Ni [16. As the petrochemical industry developed in the 1950s. 1. Other processes for the production of acetic acid introduced in the 1950s and 1960s were based on the oxidation of n-butane or naphtha. An improved process was later disclosed by BASF in 1960. . etc. 50–60 Yield MeOH: 99%. or naphtha oxidation). However. and their separation and recovery can be very complex and expensive. / Applied Catalysis A: General 221 (2001) 253–265 Fig. naphtha) Rhodium complex Manganese acetate or cobalt acetate Palladium/heteropolyacid/ metal Cobalt acetate or manganese acetate process were 90. n-butane. As a result. Yoneda et al. Homogeneous metal catalysts less costly than Rh (for example. has essentially been phased out. and acetaldehyde. respectively. The process used an iodide-promoted CO catalyst and operated at elevated temperature (230 ◦ C) and pressure (600 atm). Compared to other acetic acid synthesis routes (ethanol fermentation. Celanese. these reactions also produce signiﬁcant amounts of oxidation by-products. Until recently. the raw material for the production of acetaldehyde shifted to ethylene. The product yields exhibited by this Table 1 Acetic acid process Catalyst Methanol carbonylation Acetaldehyde oxidation Ethylene direct oxidation Hydrocarbon oxidation (n-butane. respectively. 30–40 atm) than the BASF process and exhibited superior performance: acetic acid yields were 99 and 85% based on methanol and CO consumption. 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. 30–40 50–60. in China until recently. and 70% based on methanol and CO consumption. homogeneous Rh catalyzed methanol carbonylation is an efﬁcient route that exhibits high productivity and yields.75. thus improving raw materials consumption and reducing downstream separation costs. an organo-mercury compound was used as the catalyst. The major producers of acetic acid via direct oxidation of hydrocarbons were Celanese (via n-butane) and BP (via naphtha). . and others. Monsanto commercialized an improved homogeneous methanol carbonylation process using a methyl-iodide-promoted Rh catalyst [3–6].17. Use of acetic acid.
Wacker-Chemie plans to commercialize a new acetic acid process based on butylene feedstock. Generally.18]. Poulenc and others have disclosed the direct production of acetic acid from ethane. Catalytic cycle for rhodium carbonylation.29. A number of reviews on production of acetic acid have been published and are referred [7. there are no indications of impending commercialization for this route. While the reaction.N. 3. 30–40 atm) and exhibits high selectivity to acetic acid based on methanol (99%) and carbon monoxide (85%) . “Monsanto process”.1. 2. This process also employs direct oxidation. Yoneda et al. and methanol carbonylation is still regarded as the preferred route to produce acetic acid. Accordingly. 3. are drawbacks relating to catalyst solubility limitations and the loss of expensive Rh metal due to precipitation in the separation sections. ethylene.74]. the production cost of commodity chemicals such as acetic acid is dominated by the raw material costs. Acetic acid process routes. as shown below. Inherent to the homogeneous system. however. Recently. the investment cost is reported to be lower and competitive for small or medium-size capacity plants. Table 1 summarizes reaction conditions. catalysts and yields for the major processes used to produce acetic acid. can be carried out in a variety of rhodium (I) or rhodium (III) complexes [6. .73. / Applied Catalysis A: General 221 (2001) 253–265 255 Fig. As shown in Fig. under reaction conditions they are almost invariably converted to the active catalyst [RhI2 (CO)2 ]−1 . Fig. is operated under mild conditions (180–220 ◦ C. 3. A direct oxidation process for the production of acetic acid starting from ethylene was commercialized by Denko in 1997. Methanol carbonylation 3. is more expensive than in the methanol carbonylation route. Rhodium catalyzed methanol carbonylation The methanol carbonylation process. Its key features are the use of a relatively cheap rafﬁnate-2 feedstock and competitive economics in medium size plants. Chiyoda and UOP have jointly developed an improved methanol carbonylation process for the production of acetic acid based using a heterogeneous Rh catalyst system . While the raw material. immobilization of the Rh complex on a support has been the subject of considerable investigation.
A schematic of a conventional methanol carbonylation plant conﬁguration is shown in Fig. The presence of the unsaturates. Reductive elimination of acetyl iodide (CH3 COI) can then liberate the original rhodium complex (A).256 N. Mechanism for water gas shift. are very similar to that of acetic acid.12–14]. 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 . other routes are active since more propionic acid is observed than can be accounted for by only this mechanism.27]. This rhodium–methyl 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 rhodium–acetyl complex (D). as rhodium also catalyzes the water gas shift reaction (Fig. such as methyl iodide and methyl acetate. as shown in the following mechanism : [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 . may be carried out in the ﬁrst distillation column.9. Furthermore. 6 . however. 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. even at low parts per million concentrations can cause problems with product stability. Acetaldehyde undergoes self-condensation or aldol condensation and yields butenal and higher aldehydes. however. Particular problems are encountered with the C6 species present. The boiling points of the unsaturated compounds. / Applied Catalysis A: General 221 (2001) 253–265 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– dicarbonyl–diiodide complex [RhI2 (CO)2 ]−1 (A) to generate a rhodium–methyl complex (B). Separation of pure acetic acid product from the reaction medium presents few problems. 4. including hexanal and some of its isomers. The reaction rate is independent of methanol concentration and carbon monoxide pressure. The rhodium catalyst system can generate acetaldehyde. Rhodium catalyst is separated from the product acetic acid by conducting a simple ﬂash. These can undergo further reactions to alcohols and carboxylic acids as summarized in the network of Fig. The rate-determining step is believed to be the oxidative addition of methyl iodide to the rhodium center of the rhodium complex (A). and long chain carboxylic acids with an odd number of carbon atoms. The separation of light compounds. the expensive Rh metal can be lost due to its precipitation and vaporization in the ﬂash column. Yoneda et al.%) is required to achieve high catalyst activity and also to maintain good catalyst stability [8. This column is followed by a drying column and then a column for the removal of heavy Fig. and it is proposed that this acetaldehyde is reduced by hydrogen in the system to give ethanol which subsequently yields propionic acid. hexyl iodide is observed to form a constant boiling azeotropic mixture with acetic acid. This is produced by the carbonylation of ethanol that is often present as a minor impurity in the methanol feed. It would be expected that the homologation observed would result in unsaturates and iodides having an even number of carbon atoms. the side reaction forming CO2 and H2 from CO is signiﬁcantly affected by water and hydrogen iodide concentration in the reaction liquid [26. 5 . . One possible precursor for the generation of acetaldehyde is the rhodium–acetyl species. the catalyst remains in the liquor and can be recycled to the reactor. 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 (14–15 wt. However. 4). In this process. Propionic acid is observed as the major liquid by-product in this process.
the separation of water from the acetic acid product is a major energy consumer and can limit the unit capacity. especially lithium iodide in combination with methyl iodide. These features reportedly allow existing plants to expand their capacity for little incremental capital cost. depending on the concentration of water and impurities such as propionic acid. Energy usage in this fractionation train can be high. 5.%). / Applied Catalysis A: General 221 (2001) 253–265 257 Fig. In this process. were identiﬁed early as a good agent for enhancing the stability of the rhodium catalyst at low reactor water concentrations (4–5 wt. Group I metal iodides. 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 . excess water causes carbon monoxide yield loss due to the water gas shift reaction. Schematic of a acetic acid plant conﬁguration.N. and also for decreasing liquid by-product formation [12–14]. because of the high water concentration in the reactor (14–15 wt. and increases the formation of by-products such as propionic acid. heavy unsaturates. In addition. effected by adding group I metal iodides to the Monsanto process was ﬁrst commercialized in the 1980s by Celanese and Daicel.%) [8–11]. the rhodium complex stability at low water concentrations has been extensively investigated. by-products. “low water process”.%) of group I metal iodides also enhanced the reactor productivity even at quite low water concentrations (2 wt. thus lowering the acetic acid quality. . and hexyl iodide present. Yoneda et al. In the Monsanto process. As a result.%). Network of liquid by-products. The improved methanol carbonylation process. Further work in this area revealed that the addition of a substantial quantity (16–20 wt. 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.
The main advantages of the low water process relative to the conventional Monsanto process are reduced raw materials consumption.75.3 M. commercialization has not proceeded. and molybdenum [16. and its concentration was reduced by strongly coordinating ligands and enhanced by weakly coordinating ligands .32]. and higher residual iodide in the ﬁnal product. 7). and extra distillation [33. 70 atm) with the addition of methyl iodide as a co-promoter . lower utility requirements. 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.34] have been proposed. treatment by active carbon . [MeOAc] = 0. increased productivity. Although nickel catalysts have the advantage of being much cheaper than rhodium.29]. To overcome the problems associated with high iodide concentration in the ﬁnal product. High iodide concentration in acetic acid leads to catalyst poisoning problems in some downstream applications. For phosphine-promoted catalyst. 7 and 8 shows the effect of the addition of lithium iodide on the reaction rate.25. Reaction condition: [CH3 ] = 1. and lower capital costs per unit of product. hydrogenation [31. To date. 7. Ni(CO)4 was observed in all cases. / Applied Catalysis A: General 221 (2001) 253–265 Fig. the reaction rate exhibited by the . Yoneda et al. The active catalysts are thought to be Ni(0) complexes. increases the rate of oxidative insertion of methyl iodide (the rate determining step).258 N. in addition.3. [H2 O] = 1. OAc− ) which is more active toward oxidative addition of methyl iodide [8–11. alkali metals. 8. thus promoting the primary carbonylation reaction (Fig.25]. as opposed to 20 ppb more normally achieved by conventional methods. Ni(PR3 )2 is considered an active form of catalyst and.17. such as in the manufacture of VAM.76]. As Figs.18. Recent work on nickel catalyst systems shows that reaction rates and selectivities can approach those achieved in the rhodium catalyst system. 3. temperature = 190 ◦ C. thus avoiding the need for additional distillation and recovery. total pressure = 400 psig. [Ni(CO)4 ] is known to be a very toxic and volatile compound. Iridium catalyzed methanol carbonylation Fig. and are easy to stabilize at low reactor water concentrations. The potential use of iridium instead of rhodium was identiﬁed as part of the early work done by Monsanto [3. however. However. One particular advantage of this system is the ability to effectively remove the halide impurity in a single step. 3. 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− .2. Effect of Li salt addition.0 M.0 M. low water operation with alkali-iodide promoters results in a higher iodide environment. Celanese disclosed the “silver-guard process” for the removal of very low levels of iodide impurities from acetic acid in their patent . tin. Reaction acceleration mechanism by iodide salt. Nickel catalyzed methanol carbonylation Recent studies have shown that nickel catalysts can operate under mild conditions (190 ◦ C. The use of silver metal on an ion exchange resin such as Amberlyst-15 reduces the iodide level to below 1 ppb.
it was disclosed that an improved iridium catalyst.N. Thus. However. Yoneda et al. The production of acetic acid using the iridium catalyst system has been commercialized by BP-Amoco in two world scale plants to date. This would suggest the following expression.21]. The anionic iridium cycle shown in Fig. low water concentration in the reactor results in the formation of fewer Fig. has higher activity and results in lower product impurity levels than reported in previous iridium systems . and steam consumption is decreased. It also suggests that the inclusion of species capable of assisting in the abstraction of iodide should promote the rate-limiting step.% for the conventional Monsanto process). current price increases for iridium (US$ 450/oz) negate the advantage in catalyst price. 9.% for the Cativa process versus 14–15 wt. Although much iridium is required to achieve an activity comparable to the rhodium catalyst-based processes. . in combination with a promoter metal such as ruthenium. or rhenium are the preferred promoters [20. 9. In the improved iridium system. as methyl iodide addition is not the rate determining step. / Applied Catalysis A: General 221 (2001) 253–265 259 rhodium catalyst system was superior to that of iridium. that involves the elimination of ionic iodides and the coordination of an additional carbon monoxide ligand. The patent would suggest that ruthenium. Recently. The above expression does not imply any effect from the water present in the matrix. This represents a possible improvement in the available reaction rates. In effect. The dependence on ionic iodide: reaction rate ∝ [catalyst] [CO] [I− ] suggests that high reaction rates should be achievable by operating at low iodide concentrations. Catalytic cycle for iridium carbonylation. and has received wide publicity as the “Cativa” process. The slowest step in this cycle is the insertion of carbon monoxide to form the iridium acetyl species. is similar to that shown earlier for rhodium. a proprietary blend of promoters has been found to increase reaction rate. 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 . but water is found to have a signiﬁcant effect on rate . the catalyst system is able to operate at reduced water levels (less than 8 wt. Until the early 1990s. The unique differences between the rhodium catalytic cycle and that of iridium in methanol carbonylation have been investigated . lower by-product formation and improved carbon monoxide efﬁciency are achieved. the difference in the prices of rhodium (US$ 500/oz) and iridium (US$ 60/oz) was the driving force for replacing rhodium with iridium.
37. long catalyst life. the methanol carbonylation reaction is conducted at moderate temperature (160–200 ◦ C) and pressure (30–60 atm) and at low water concentration without any additives present. In the acetica process. The heterogeneous catalyst commercialized for the acetica process consists of Rh complexed on a novel poly-vinyl pyridine resin . 10). result in increased recycle and separation costs. For example. for the production of acetic acid. attaching the Rh–phosphine ligand complex to alumina by silylation was attempted [41. and no signiﬁcant rhodium loss [47–49]. With homogeneous methanol carbonylation routes. the nitrogen atoms of the resin pyridine groups become positively charged after quaternization with methyl iodide. low water content. and no addition of lithium iodide is required. acetic acid production is restricted by the solubility of the active metal. catalyst solubility limitations no longer govern reactor capacity since catalyst concentrations several times greater than those achievable in the homogeneous systems are possible. With the heterogeneous catalyst system.38].4. However. 3. The concentration of Rh on the solid phase is determined by the ion exchange equilibrium. Yoneda et al.260 N. the iridium catalyst system is also characterized by the formation of fewer higher alkyl-iodide species than in the conventional low water process. / Applied Catalysis A: General 221 (2001) 253–265 by-products such as propionic acid than in the original Monsanto rhodium system. higher corrosion rates. no successful demonstration of such a catalyst had been known .9. Inorganic oxides and zeolites were also investigated for use in vapor-phase operation [39. The lower water content . Thus. and higher reaction rate than Monsanto’s rhodium system . Immobilization also signiﬁcantly reduces the loss of expensive Rh metal because the catalyst is conﬁned to the reactor rather than circulating downstream. Rh precipitation and catalyst solubility limitations). and no Rh or resin makeup. The catalyst exhibited no deactivation after continuous operation for more than 7000 h . Active carbon was investigated as a possible support and proposed for vapor-phase operation [7.42]. the reaction rate was 1/1000–1/10 that of Monsanto’s homogeneous process and selectivity was also poorer.g. there were problems with rhodium metal leaching from the resins and the decomposition of the resins during operation at elevated temperature. virtually all the Rh in the reaction mixture is immobilized. acetic acid productivity is directly proportional to catalyst concentration in the reaction liquid. and difﬁculty in product puriﬁcation. Although the activity of these catalysts in the liquid phase was comparable to Monsanto’s homogeneous catalyst.12–14]. the strong ionic association between the pyridine nitrogen groups and the Rh complex causes the immobilization (Fig. Furthermore. Both additives. and as a result. or vinyl pyridine copolymers have been evaluated [43–45]. Chiyoda introduced novel pyridine resins and catalysts that exhibited high activity. however. the immobilization of the Rh complex on a support has been the subject of considerable investigation. which is tolerant of elevated temperatures and pressures. Heterogeneous rhodium catalyzed methanol carbonylation In order to overcome the limitations of the homogeneous catalyst system (e. Until the recent development of a commercial heterogeneous Rh catalyst system by Chiyoda. The resultant reaction rates for these catalysts were also found to be poor relative to those observed for the homogeneous system. 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. Based on this heterogeneous Rh catalyst. 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. Chiyoda and UOP have jointly developed an improved methanol carbonylation process. where reduced pressures may cause precipitation of rhodium and vaporization losses of metal carbonyl compounds. the Rh is converted to its catalytically active anion form [Rh(CO)2 I2 ]−1 . Catalyst stability has been demonstrated in both oncethrough and continuous-recycle pilot plant testing at process conditions.40]. called “the acetica process”. Consequently. ion exchange resins based on cross-linked polystyrene and incorporating pendant phosphines. Because equilibrium strongly favors the solid phase. To increase catalyst activity for operation in the liquid phase. Furthermore. Under reaction conditions.
Methanol and CO feeds are introduced at the reactor bottom. of 3–7 wt. 11). 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. Both of these feeds. Also. The process ﬂow. where the CO is consumed in the reaction. less hydrogen iodide is present in the system. or gas lift reactor employed with the heterogeneous catalyst process does not suffer from such problems and limitations. Rhodium immobilization. / Applied Catalysis A: General 221 (2001) 253–265 261 Fig. Yoneda et al. In cases where the acetic acid product will be used for VAM production. the bubble column.% typical of the acetica process results in reduced production of CO2 . ﬂow up the reactor riser. 11. 11. 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. because of the lower water content. . novel iodide removal technology is available to reduce the iodide in the acetic acid product to less than 3 ppb . Fig. where the compressed CO gas is distributed through a sparger. 10. and hydrogenated by-products via the water gas shift reaction. which is similar to that of a conventional homogeneous process is shown in Fig. and consequently the process environment is less corrosive.N. Bubble column reactor and acetica process ﬂow. along with the recycle liquid and catalyst.
This route involves the liquid phase oxidation of acetaldehyde using air and typically a manganese acetate catalyst operating at 50–60 ◦ C. Yoneda et al.57]. 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. Ru-Sn bimetallic complexes are proposed to be the active species. 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. Vapor phase oxidation of ethylene The two-step oxidation process for the production of acetic acid. etc.). Although this process features high yield (approximately 90%) and a relatively low capital investment cost. 6. was ﬁrst commercialized in 1960: 1 CH2 =CH2 + 2 O2 → CH3 CHO 1 CH3 CHO + 2 O2 → CH3 COOH 5. Methyl formate is produced by dehydrogenation of methanol  or by methanol carbonylation under high pressure in the presence of: HCOOCH3 → CH3 COOH copper oxide and alkali catalyst. This catalyst has the same chemical morphology as a methanol carbonylation catalyst. Although the reaction pressure required for methanol synthesis is higher than the pressure used in acetic acid synthesis.53]. Many plants utilizing this technology have been shut down over the last 20 years. the combination of methanol synthesis with dimethyl ether synthesis can reduce the pressure of the ﬁrst reaction step.) and a dehydration catalyst (H-ZSM-5. 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. It is noted that acetic acid production via methanol dehydrogenation followed by methyl formate isomerization requires only methanol and no carbon monoxide plant:CH3 OH→HCHO→HCOOCH3 →CH3 COOHAcetic acid can be produced from only methanol using a Ru-Sn catalyst according to the following steps [56. etc. Applying this concept.59]. / Applied Catalysis A: General 221 (2001) 253–265 4. The catalyst consists of a mixture of the catalyst for methanol synthesis (Cu-Zn-Al oxide. 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. 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 170–250 ◦ C and 25–50 atm. Heterogeneous rhodium catalysts supported on poly-vinyl pyridine resin have also been proposed for this application . On the contrary. it suffers from high acetaldehyde feedstock cost and a very corrosive catalyst system. There is also an older process that entails liquid phase free radical oxidation of n-butane or naphtha in the C4 –C8 range. starting from ethylene through acetaldehyde. can be used to obtain acceptable reaction rates in the liquid phase. 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 . The reaction is based on a free radical mechanism. This integrated process could achieve a signiﬁcant capital cost reduction relative to the conventional ﬂow scheme.262 N. 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.
N. and 75. an acetic acid route from ethane was introduced. antimony. bismuth. Other proposed technologies for the production of acetic acid 7. The presence of steam is required to catalyst 7. Scheme 1. or mixtures of ethane and ethylene with oxygen over a catalyst containing molybdenum. or ethylene to acetaldehyde. The ﬁrst component is palladium supported on a carrier. The third component is copper. vanadium. Ethane oxidation In the 1980s. and copper. Partial oxidation route. Yoneda et al. These catalysts have acetic acid selectivities in the range of 60–90% based on ethylene. Catalyst systems consisting of palladium chloride and V2 O5 supported on Al2 O3 . 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. The oxidation catalyst catalyzes the reaction of ethylene to acetic acid and other oxidation products that are converted to acetic acid (Scheme 2). 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. Tests showed that complete substitution of molybdenum by rhenium (Rex Vy Zz ) is beneﬁcial in the reaction of ethane to ethylene. Tests were not performed on ethylene feed.1–2% range. / Applied Catalysis A: General 221 (2001) 253–265 263 enhance the activity and selectivity of the process for the production of acetic acid. 3. In another catalyst system. Denko has developed a direct oxidation process for the production of acetic acid based on the hydration route [63–65] and has commercialized this technology in late 1997. In one example. and combinations of Pd (2%) and H3 PO4 (25%) on SiO2 . niobium. preferably in the range of 0. tin. Two reaction mechanisms based on: CH3 CH3 + O2 → CH3 COOH + by-product different catalyst systems were proposed: (1) partial oxidation of the methyl group. which is then converted to acetic acid (Scheme 1). and one other metal (Z) in the general formula Mox Vy Zz . The reaction takes place in a ﬁxed bed reactor at operating temperatures and pressures of 150–160 ◦ C. whereas partial substitution can increase the selectivity to acetic acid. since it appears that acetaldehyde and carbon dioxide are necessarily formed in this type of process. but tests on ethane (21% ethane. The selectivity to acetic acid is approximately 86%. and (2) ethane oxidation to ethylene followed by ethylene hydration to ethanol. the hydration catalyst further catalyzes the hydration of ethylene to ethanol. A patent refers to the production of acetic acid by reacting ethane. and up to 8 atm. or Pd (1%) on V2 O5  have been proposed. silver. preferably phosphotungstic acid salts of lithium. and 14% selectivity to ethylene at 3% ethane conversion. ethylene. Pd-V2 O5 -Sb2 O3 on Al2 O3 . . rhenium or a combination of rhenium and tungsten are introduced to replace the molybdenum in the dehydrogenation catalyst . selenium. and calcium supported on an LZ-105 molecular sieve to yield 63% selectivity to acetic acid. sodium. Much work has been undertaken to develop a simpler. The second component is a heteropoly acid and their salts. antimony.1. In the combined ethane/ethylene feed case. The gases fed to the reactor are ethylene. respectively. route that has yet to be developed.8% oxygen. and nitrogen that is used as a diluent. lead. steam. The catalyst consists of either two or three components. The routes have been proposed according to the different catalyst systems in Schemes 1 and 2. or tellurium. Hydration route.2% catalyst Scheme 2. oxygen.
H. many attempts have been disclosed regarding the use of ethane as feedstock. Roth. Secondly. M.  N.5%. Sb. Although ethane is a relatively inexpensive and attractive raw material for producing acetic acid. (1968) 1578. The reaction rates are reported to be too slow for an economically viable industrial process. there is a marked increase in ethylene production with a corresponding decline in acetic acid.  H. 303 (1986) 257. Chem. At phosphorus levels greater than 0. at 53. Methane carbonylation Novel methods for producing acetic acid directly from methane under relatively mild conditions have been reported.2.69]. respectively. J.5% per year from a signiﬁcant and large base capacity. Hydrocarbon Proc. 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. Appl. Ca. Indian Catal. 1 (1983) 275. at a temperature and pressure of 250–280 ◦ C and 15 atm. 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.C. It consists of phosphorus-modiﬁed molybdenum-niobium vanadate of formula Mo2. 16 November 1998. Catal.J. or ethylene was disclosed [68. Recently. Agulio. However. but this novel process route has the potential to reduce the cost of acetic acid production.A. Himmele. Jones. respectively. Eby.  M.5 V1. 8. the oxidation processes produce a variety of co-products.5–4.  F.S. a catalyst for the co-production of ethylene and acetic acid from ethane was disclosed . Smith.D. carbon monoxide and oxygen formed acetic References  Asian Chemical News. and selectivity at milder operating conditions and lower cost of production. Chem. signiﬁcant catalyst innovation has occurred even within this production route resulting in greatly improved yield.  M.L. M. Organomet. Soc. Howard. A new molybdenum vanadate catalyst system promoted with Nb. The patent discloses the production of acetic acid with 86% selectivity and 11% ethane conversion per pass.9. 45 (1966) 141. Taylor. Torrence. Yoneda et al.T.P. More recently in 1998.A.3% conversion.0 Nb0. G. = → 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 = 0.264 N.E. Murphy. another oxidative process and catalyst for the production of acetic acid from ethane. and Pd allows the gas phase oxidation of ethane and/or ethylene to acetic acid.32 Px in which the optimum range for the phosphorus (x) is 0. Conclusions Acetic acid represents a commodity chemical growing at 3.  US Patent 3769329 (1973) to Monsanto. A. it was reported that the mixture of methane. the disposition of which needs to be considered in any business plan. J. Chem.042) to produce acetic acid and ethylene with selectivities of 49. 7. B. 51 (1972) 76. Grove.D. and 10. W. Am. S. T.. with high yield and higher selectivity under milder operating conditions than previously achieved. 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. Today 18 (1993) 325. Hohenshutz. In 1999. Hydrocarbon Proc. / Applied Catalysis A: General 221 (2001) 253–265 nitrogen) resulted in acetic acid selectivity as high as 78% at an ethane conversion of 14. Commun. Singleton.  R.06: CH3 CH3 + O2 catalyst acid in the presence of rhodium trichloride dissolved in water : 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. 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 . Kutenpov. J.3%. .R. Paulik.01–0. Roberts.06%.
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