Applied Catalysis A: General 221 (2001) 367377

New developments in the production of methyl methacrylate

Koichi Nagai
Basic Chemicals Research Laboratory, Sumitomo Chemical Co. Ltd., 5-1 Sobiraki-Cho, Niihama City, Ehime 792-0001, Japan

Abstract Methyl methacrylate MMA can be produced in different ways based on C2 C4 hydrocarbon feedstocks. In the present review, the recent commercialized and expected MMA technologies will be described and a comparison of these production routes is given. Thereby, the catalyst development will be strongly emphasized. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Methyl methacrylate; Production; Hydrocarbons; Catalyst; Process

1. Introduction Methyl methacrylate (MMA) is an important monomer, which is widely used for producing acrylic plastics (polymethyl methacrylate) or producing polymer dispersions for paints and coatings. The world production capacity has been almost doubled in past 15 years, and reached about 2.2 million tonnes per year. The demand of MMA is still expected steady growth in the future. Methacrylic polymer, which has the characteristics of good transparency and weather resistance, is used in many elds such as signboards, building materials, vehicles and lighting equipments. Methacrylic acid (MAA) and higher esters (such as butyl methacrylate) derived from the acid, have not been produced in a large quantity, but are useful comonomers for various uses. While Rohm & Haas Co. began to industrially produce a methacrylic ester (ethyl methacrylate) rst in 1933, ICI reformed the Rohms method and commercialized MMA in 1937 by the acetone cyanohydrine (ACH) process, which most manufacturers in the
Fax: +81-897-374003. E-mail address: nagaik1@sc.sumitomo-chem.co.jp (K. Nagai).

world adopted even today. Although the ACH method was the only industrial process until 1982 for manufacturing MMA, there are problems of shortage of toxic hydrogen cyanide (HCN) supply and of dealing with the large quantities of ammonium bisulfate waste. Till today, many efforts have been continuously put into the development for placing this ACH process. New commercialized processes have been developed until now, such as (i) the direct oxidation process which consists of catalytic, isobutylene or tert-butanol (TBA) oxidation to methacrylic acid in two steps; (ii) the methacrylonitrile (MAN) route by ammoxidation of TBA; (iii) the BASFs method which employs ethylene, carbon monoxide and formaldehyde as raw materials; (iv) the new ACH process by Mitsubishi Gas Chemical Co. Inc., which does not generate acid waste; and (v) the direct oxidative esterication of methacrolein by Asahi Chemical Co. Ltd. Most of these new processes have been developed for an environmentally friendly production of MMA and thereby the development of the catalysts was the key technology. This review describes the recent commercialized and expected MMA technologies emphasizing catalyst development.

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 8 1 0 - 9

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2. Routes to MMA The C2 C4 hydrocarbons can be thought as raw materials for MMA. Fig. 1 shows many considerable and examined routes to MMA, which includes conventional the ACH process, and the industrialized routes are emphasized by thick lines. 3. C2 routes Ethylene can be used to produce MMA via propionaldehyde, propionic acid, or methyl propionate, as shown in Fig. 1. The key step of this route is the condensation reaction of such an intermediate with formaldehyde to make methacrolein, MAA or MMA. 3.1. BASFs process One of the ethylene routes was developed by BASF, and a 40,000 t per year MMA plant including 5000 t per year MAA was built in Germany in 1989 [1]. In this route, MMA is made from ethylene via propionaldehyde, methacrolein and methacrylic acid as follows: CH2 =CH2 + CO + H2 CH3 CH2 CHO CH3 CH2 CHO + HCHO
(CH3 )2 NH

of isobutylene, which will be mentioned below. The BASFs catalyst for methacrylic acid may be a similar heteropoly acid to that developed in Japanese companies. Therefore, the improvement of the methacrolein oxidation catalyst has been desired in this process. It is noted that this process seems to meet the special location and the availability of starting materials in house of BASF, and is not thought to become a world general MMA manufacturing method. 3.2. Other C2 routes Propionic acid or methyl propionate routes have been examined in many enterprises for a long time. Propionic acid is produced by Reppes hydrocarbonylation reaction of ethylene for which metal carbonyl is used as a catalyst, or by oxidation of propionaldehyde. MAA or MMA is proposed by condensation reaction with formaldehyde (or its derivatives such as methylal). If one of these methods would be industrialized, it could become a simple and excellent process because of its fewer steps CH3 CH2 COOH + HCHO CH2 =CH(CH3 )COOH + H2 O CH3 CH2 COOCH3 + HCHO CH2 =CH(CH3 )COOCH3 + H2 O There are many reaction examples carried out at 300400 C in vapor phase on a solid catalyst such as a solid base or a solid acid. For example, Amoco shows more than 91% selectivity to MAA with 39% conversion of propionic acid on Cs/SiO2 -SnO2 , which is one of the solid base catalysts [5]. Details of this catalyst were reported [6,7]. Improvement of the catalyst performance is described in a patent [8] by Mitsubishi Rayon Co. Ltd., which shows 40.5% conversion of propionic acid with 98.8% selectivity to MAA on the catalyst Si-Cs-W-Ag-O. As for the solid acid catalysts, Toagosei Co. Ltd., for example, gets 68% conversion of formaldehyde and 66% selectivity to MAA on the catalyst V-P-O/Zr-Al-O [9]. A patent by Daicel Co. [10] demonstrates that this reaction proceeds in the presence of a Lewis acid catalyst in liquid phase. According to that disclosure, equivalent moles of aluminum propionate and 5 mol of formaldehyde, based on propionic anhydride were used. The yield of MAA was 23.5% at 180 C after 1 h.

CH2 =CH(CH3 )CHO + H2 O

O2

CH2 =CH(CH3 )CHO CH2 =CH(CH3 )COOH

CH3 OH

MMA

Before 1989, BASF had already produced propionaldehyde by hydroformylation of ethylene and formaldehyde by using methanol. In addition to these productions, they carried out new steps after methacrolein synthesis to produce MMA. Propionaldehyde reacts with formaldehyde in a pipe type reactor in the presence of a secondary amine and an acid. According to BASF patents [2,3], the yield of methacrolein reaches nearly 99%. Amoco Co. carried out this reaction in vapor phase over molecular sieves [4] and disclosed that conversion of propionaldehide was 57% with 98% selectivity to methacrolein. The process for producing methacrylic acid and MMA is the same process as for direct oxidation

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Fig. 1. Routes to methyl methacrylate (MMA).

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Recently, Research Triangle Institute, Eastman Chemical and Bechtel announced that they collaborated on improving this process. Iodine-promoted molybdenum carbonyl is used for hydrocarbonylation of ethylene under a lower temperature and lower pressure condition than that of the conventional catalyst. A vapor phase condensation reaction is carried out over Nb/SiO2 or Ta/SiO2 catalyst [11,12]. In view of industrialization, the productivity of each reaction based on these C2 routes has not been sufcient yet. The selectivity is fairly high, but the one-pass conversion level is too low, and there is a problem such that, the catalyst life is not so long. Therefore, great improvement in catalyst performance is desirable. 4. C3 routes 4.1. New ACH process The conventional ACH method is based on the C3 route. Acetone is a derivative of propylene, and is being produced large amounts as a co-product with phenol, these days. On the other hand, large amounts of HCN are also obtained as by-product in the production of acrylonitrile. But, the main problems of this ACH method is presently at the supply of HCN and the large amount of ammonium bisulfate waste. Mitsubishi Gas Chemicals has industrialized the new improved ACH process in 1997 to solve these two problems. In this process, rst, acetone cyanohydrin is hydrated to -hydroxy isobutylamide with the manganese oxide catalyst in absence of sulfuric acid, and then is esteried by methylformate to provide methyl -hydroxy isobutylate. Methylformate becomes formamide at this time, and then the formamide is dehydrated to give HCN, which is recycled in the ACH preparation process. Methyl -hydroxy isobutylate is converted to MMA in a dehydration reactions (CH3 )2 C(OH)CN+H2 O(CH3 )2 C(OH)CONH2 (CH3 )2 C(OH)CONH2 + HCOOCH3 (CH3 )2 C(OH)COOCH3 + HCONH2 (CH3 )2 C(OH)COOCH3 CH2 =C(CH3 )COOCH3 + H2 O HCONH2 HCN + H2 O

Though the hydration reaction on MnO2 catalyst had been known over many years, there were some problems such as the catalyst life. Mitsubishi Gas Chemicals improved the performance of the catalyst by providing a new preparation method [13] or by adding another catalyst component such as Sn or K [14]. The key point of this process is that, the use of sulfuric acid is avoided and the trans-esterication is done without methanol but with methyl formate. As for the catalyst used in this reaction, various catalysts such as metal carbonyl compounds or alkaline metal alcoholate (e.g. sodium methylate) are proposed. The selectivity of this reaction reaches up to 99%. The last dehydration process is carried out on zeolite catalyst in gas phase. Though there were problems such as a side reaction or a matter as to catalyst life, they were solved by utilizing methanol and by adopting a faujasite zeolite [15]. Formamide produced in the esterication process is also dehydrated to provide HCN on a solid acid catalyst in gas phase. Recently, Mitsubishi Gas Chemicals has proposed a new route in which methyl -hydroxy isobutylate and ammonia are produced from the reaction of -hydroxy isobutylamide with methanol. The ammonia is recycled to produce HCN by reacting with methanol and O2 [16] (CH3 )2 C(OH)CONH2 + CH3 OH (CH3 )2 C(OH)COOCH3 + NH3 CH3 OH + NH3 + O2 HCN + 3H2 O One of disadvantage of the new ACH process is that there are numbers of reaction steps, while the process has many advantages such that the productivity of each step are comparatively high, consumption of HCN is reduced, and sulfuric acid is not used. 4.2. Isobutyric acid process The route, in which MAA is made of propylene via isobutyric acid, has been researched by Atochem and Rhm, separately CH2 =CHCH3 + CO + H2 O(CH3 )2 CHCOOH
HF 1 (CH3 )2 CHCOOH + 2 O2

CH2 =C(CH3 )COOH + H2 O

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Isobutyric acid is synthesized by Koch reaction with hydrogen uoride as catalyst. An example of Koch reaction is commercially realized to produce pivalic acid from isobutylene. Propylene, carbon monoxide, water and large quantities of hydrogen uoride are mixed at low temperature in a pipe reactor, which prevents back mixing under adiabatic condition to obtain isobutyric acid with few impurities. It is said that, the handling problem of dangerous hydrogen uoride and corrosion problem were solved by the process as established. A main problem of this route is present by the yield in the oxidative dehydration reaction of isobutyric acid and a matter as to the catalyst life. Fe-P-O mixed oxides and Mo-P-O heteropoly acid have been examined as catalysts. Mitsubishi Chemical found rst that this reaction proceeds well over a heteropoly acid which consists of Mo-P-V-O [17]. An improvement has been made by adding similar transition metals or alkaline metal as used in catalysts for the methacrolein oxidation. Also, in the catalyst based on Fe-P-O, various improvements were made, and the yield of methacryric acid reached 83.6% as could be demonstrated by Ube Industries Co.a Fe-P-Co-Pb-O catalyst [18]. The separation of isobutyric acid and methacrylic acid (or both esters) is not easy, and therefore, the conversion of isobutyric acid has to be as high as possible for saving energy. For industrialization of this route, a jump is necessary in the catalyst performance concerning productivity and life. Isobutyricaldehyde can be oxidized to methacrylic acid. That has been studied using a large amount of the by-products in an oxo-process for producing n-butric aldehyde. But, due to the improvements of oxo-catalysts, e.g. the replacement of conventional cobalt catalysts by newly developed rhodium catalysts, the amount of iso by-product has been strongly decreased. Therefore, the necessity of establishing this MAA route may be diminished, in our days. 4.3. Methyl acetylene process Shell developed a novel attractive process for producing MMA from methyl acetylene (propyne) in one-step. CH CCH3 + CO + CH3 OH CH2 =C(CH3 )COOCH3

In this method, methyl acetylene is used, while acetylene is used for production of acrylic acid by Reppes carbonylation. For manufacturing acrylic acid, BASF has shut down their last Reppe acrylic acid plant, and the direct oxidation method of propylene completely takes the place of it. In so many years, the effort has been made to get MMA from methyl acetylene in the same way as acrylic acid, but the yield of MMA was very low in case it has based on the same catalyst and same condition. Palladium catalyst was also known for this reaction, but its application for MMA did not work sufciently [19]. Shell found that this reaction proceeds with a good yield in the presence of palladium acetate, organic phosphine and protonic acids [20]. But the activity of such catalysts was not sufcient. Then, Shell made a great effort to improve the catalyst system, and as a result, the yield reached 99.9%, in which 100,000 mol of MMA were produced for 1 mol Pd per hour. This is achieved by using, e.g. 2,6-bis-(biphenyl phosphino) pyridine under mild non-corrosive condition at approx. 50 C, and a CO pressure of about 1 MPa [21,22]. Concerning this procedure, a detailed report was published [23,24]. Methyl acetylene as the raw material for producing MMA could be obtained in an ethylene plant. In a C3 stream from a naphtha cracker, a few percents of methyl acetylene and alene (propadiene) exist as by-products, and one million tonnes per year of ethylene capacity is necessary for producing 40,00050,000 t per year of MMA. Methyl acetylene could be separated from the C3 stream by extraction and distillation with DMF, and alene is isomerized to methyl acetylene with K2 O/Al2 O3 catalyst [25]. Because of the few steps and extremely high catalyst performance, this process would have many advantages at a place close to a big ethylene production plant. It was reported that ICI paid a fee to Shell for utilizing this technology.

5. C4 routes In all of the C2 and C3 routes described above, a methallyl carbon frame has to be formed by adding of one or two carbon atoms using C1 compounds such as CO, HCHO or HCN. In contrast, in C4 routes, the isobutylene or tert-butanol carbon skeleton is used as

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it is. The C4 routes have been commercially established by Japanese companies where a new supply of HCN could not be expected, and only low amounts of isobutylene had been demanded, whereas western countries have a great demand for it as a gasoline additive. Therefore, some Japanese companies have made an effort to develop new processes. The key factors of these routes were the development of excellent catalysts. Today in Japan, more than half of MMA production capacity comes from C4 routes. Now, in addition to Japan direct oxidation plants are operating in Korea, Singapore and Thailand. 5.1. Escambia process A process using isobutylene as a raw material has been commercially employed by Escambia Co. for a short period of time. Isobutylene is oxidized to provide -hydroxy isobutyric acid by using N2 O4 and nitric acid at a low temperature of 510 C in liquid phase. After esterication and dehydration MMA is obtained. However, this process does not seem to be economical by favorable because the yield is not sufcient and there are some problems such that large amounts of nitric acid and NOx should be handled. In addition, an explosion accident happened during the operation in the plant. Therefore, this production was stopped in 1965. 5.2. C4 direct oxidation process Realization of a direct gas phase oxidation process starting from isobutylene for producing methacrylic acid was delayed until 1982, i.e. about 10 years after acrylic acid by direct oxidation of propylene. The basis of three processes, which were developed exclusively in Japan and proposed by Mitsubishi Rayon, Japan Methacrylic Monomer (Sumitomo Chemical and Nippon Shokubai) and Kyodo Monomer (Kuraray & Mitsui Chemical) seems to be similar to one another. The necessity of separation of isobutylene or tert-butanol (TBA) from C4 stream of an ethylene cracker or a FCC-unit, needed the development of new catalyst technologies. Sumitomo Chemical obtains high purity isobutylene via methyl tert-butylether (MTBE) with a novel acid catalyst. The process of Mitsubishi Rayon and Asahi Chemical produces TBA

from a C4 mixture in which a ion-exchange resin or heteropoly acid solution is adopted as a catalyst. Because MTBE is used today worldwide in large quantities as a gasoline additive, the supply of isobutylene from ethylene and FCC plants, or TBA as a by-product in Oxiran process (propyleneoxide) is not sufcient. Therefore, the dehydrogenation process of isobutane has been conducted on a large scale, and the oxidehydrogenation of isobutane or isomerization of n-butenes have to be studied extensively. No matter how large quantities of MTBE are available in the world, it seems too expensive to be used as a raw material of MMA, because the price is based on a rather expensive gasoline price. For this reason, the C4 direct oxidation process might not be so popular worldwide. The reactions by the direct oxidation method consist of two-step oxidation of isobutylene or TBA with air to produce methacrylic acid and esterication by methanol to produce MMA CH2 =C(CH3 )2 (or (CH3 )3 COH) + O2 CH2 =C(CH3 )CHO + H2 O
1 CH2 =C(CH3 )CHO+ 2 O2 CH2 =C(CH3 )COOH

CH2 =C(CH3 )COOH + CH3 OH CH2 =C(CH3 )COOCH3 + H2 O There are two processes. One process (Mitsubishi Rayon) consists of the separation of methacrolein from the rst-step oxidation gas, and another one (Japan Methacrylic Monomer) consists of the direct introduction of the rst efuent gas to the second reactor [26]. The ow diagram of the latter process is shown in Fig. 2 [27]. The second reactor efuent, containing MAA and unreacted methacrolein, is condensed to recover MAA as an aqueous solution. Methacrolein is recovered and is recycled to the second oxidation reactor. MAA is extracted from the solution with a solvent and then is esteried to MMA with sulfuric acid or an ion exchange resin as a catalyst. In this process, MAA can be obtained also as an end product. The key of the C4 direct oxidation process was the development of high performance oxidation catalysts. Concerning those catalysts, results of fundamental scientic research and an enormous number of patents are published. As in acrylic acid processes via direct oxidation of propylene, two kinds of catalysts are used

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Fig. 2. C4 Direct oxidation process (Japan methacrylic monomer) [27].

in this oxidation process, which consists of two steps: the rst-step is a catalytic oxidation of olens and the second-step is an oxidation of aldehydes. A catalyst utilized in the rst-step is a multicomponent oxide catalyst of Mo-Bi, which seems to be one for propylene oxidization, and the second step catalyst is a P-Mo heteropoly acid structure catalyst that is different from the Mo-V catalyst for acrolein oxidization. The reaction mechanism of isobutylene oxidation is thought to be the same as that of propylene oxidation, in which -allyl adsorption species and the role of lattice oxygen are employed. Most of the rst step catalysts developed for isobutylene oxidation are based on the modication of the famous SOHIO Mo-Bi catalyst. The important improvements of SOHIO catalyst were achieved in Japan [2830]. Even though the acrolein yield was about 40% in an early stage, the activity of such catalysts and the selectivity thereby

were improved greatly resulting in a yield of more than 90% as obtained in the case of C3 route for acrylic acid today. The basic catalyst components are Mo-Bi-Fe-Co/Ni-A (A: an alkaline metal, an alkaline earth and Tl), the same as in a propylene oxidation catalyst, although the reactions differ in easiness. When the propylene oxidation catalyst was used for oxidizing isobutylene, the activity tended to be too high, and therefore, the yield of methacrolein was lowered. The catalyst for oxidizing isobutylene has been optimized by increasing the alkaline metal ratio in the catalyst, and so on. The byproducts are CO, CO2 , formaldehyde, acetone, acetoaldehyde, formic acid, acetic acid and many other oxygenated compounds. Total yield of methacrolein plus methacrylic acid is a little lower than that of acrolein plus acrylic acid. In the propylene oxidation, a considerable quantity of acrylic acid is formed even in the rst reaction, while in the isobutylene oxidation, rather a few amount of

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methacrylic acid is formed. Because methacrolein has an extra methyl group, the selectivity to MAA from methacrolein would be worse and the produced MAA will be easily burned out on the rst-step catalyst. But, the yield of methacrolein reached over 80%, which is almost as the same level as that of acrolein. Recent patents for the rst oxidation step disclose methods of catalyst preparation or methods by using catalyst having a specic shape such as a ring type shape or a convex shape [31,32], a reactivation method of deteriorated catalyst [33], or a method of lling different catalysts into an inlet from an outlet of a reactor tube for controlling a hot spot temperature [34]. The industrialization of C4 direct oxidation was delayed for a long period in comparison with that of C3 oxidation in acrylic acid, because the catalyst performance of the second step was not sufcient. The catalyst for acrolein oxidization (Mo-V multi-component oxide) shows more than 95% of yield, which had also been developed by the Japanese company Riken [35]. Even when this catalyst is used for the oxidization of methacrolein as it is, the yield of MAA is very low. The trial to improve the performance based on this catalyst for methacrolein oxidization was not successfully. SOHIO had already showed in 1957 that Mo-P heteropoly acid is effective for this reaction. After that (in the 1970s) a lot of patents to improve the heteropoly acid catalysts performance were published by many companies [36,37]. The heteropoly acids used here has a Keggin structure [PMo12 O40 ]3 for its anion, and has different physico-chemical properties from those of usual complex oxides. It has a strong Brnsted acidity originated by a proton as counter cation, and can moderate an oxidizing power by Mo. The free 12-molybdo-phosphoric acid (H3 PMo12 O40 nH2 O) does not give such high yield, and its fatal fault is the catalyst life time due to its structure instability at the reaction temperature. The substitution of a part of Mo with V, and the formation of acidic salt with alkaline metals, are effective on both the yield and the catalyst life. For the practical use of this heteropoly acid catalyst, the addition of small quantity of other elements, or the control of surface area and pore distribution of the catalyst by various means in preparation methods have been adopted. Still, the performance level of this second step catalyst is not sufcient. Selectivity is not high enough. A

space time yield is not satisfactory, and thereby the service problem in the catalyst remains. This may be the main reason why the C4 direct oxidation method could not take a world decisive position in MMA processes like C3 oxidation in acrylic acid. Therefore, many efforts to improve the catalyst performance have been continued. As for the components, almost all elements in the periodic table are claimed in patents. Many examinations on raw materials of the catalyst, molding methods, calcining procedures and so on are being carried out, for example, a method of spray-drying after fast mixing solutions [38], hydrothermal treating of mixed slurry [39], a method of molding by the addion of alcohols [40] and so on. The performance of the heteropoly acid catalysts has been improved by these steady efforts little by little. A superior catalyst that would exceed the heteropoly acid catalyst now in use, has not been found at present. For example, the modied V-P-O catalyst known for producing maleic anhydride, can get only about 45% yield [41]. Considering the fact that even in the case of acrylonitrile or ethylene oxide processes which had already been established, many efforts of catalyst improvement are being continued still now and steady progress has been made, these efforts to improve the catalyst performance are indispensable in the C4 direct oxidation process. 5.3. Methacrylonitrile (MAN) process Asahi Chemical Co. developed and commercialized a route via methacrylonitrile (MAN) for MMA production in 1982
3 (CH3 )3 COH + NH3 + 2 O2

CH2 =C(CH3 )CN + 4H2 O CH2 =C(CH3 )CN + H2 SO4 + H2 O CH2 =C(CH3 )CONH2 H2 SO4 CH2 =C(CH3 )CONH H2 SO4 + CH3 OH CH2 =C(CH3 )COOCH3 + NH4 HSO4 MAN can be produced by ammoxidation almost in the same step as acrylonitrile, which is produced in large quantities. Afterwards MAN has been hydrated

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by sulic acid to methacrylamide, the same process as in conventional ACH was adopted. Because the yield of MAN can be equal to that of acrylonitrile [42], the total yield is superior to the above-described two-step oxidation method. But, problems such as the formation of the ammonium bisulfate waste and the use of ammonia, which should not be contained in the end product still remain. Asahi Chemical seemed to adopt this process mainly because of the small investment cost by diversion in their acrylonitrile and ACH plants. Asahi gave up the MAN based MMA process in 1998, and switched over an oxidative esterication process described below. Mitsubishi Gas Chemicals proposed another improved MAN route [43]. MAN is hydrated to methacrylamide without using sulfuric acid and is then esteried to obtain MMA by methylformate in the same way as the new ACH process CH2 =C(CH3 )CN + H2 O CH2 =C(CH3 )CONH2 CH2 =C(CH3 )CONH2 + HCOOCH3 CH2 =C(CH3 )COOCH3 + HCONH2 HCONH2 NH3 + CO In this process, the produced formamide is decomposed to ammonia and carbon monoxide, and the ammonia and the carbon monoxide are recycled to MAN step and methylformate step, respectively. This decomposition can be carried out without catalyst or with a solid base catalyst at high temperatures. Furthermore, Mitsui Toatsu investigated the reaction to get MMA or MAA from -hydroxy isobutylamide or methacrylamide on a solid acid catalyst of phosphoric acid salt in gas phase [44,45]. 5.4. Direct oxidative esterication process Asahi Chemical established and started in 1998 a new process based on direct oxidative esterication of methacrolein, which does not produce by-products such as ammonium bisulfate. The raw material is the same tert-butanol as in the direct oxidation method. In contrast with the direct oxidation process, this new Asahi process has only two steps. Methacrolein produced in the same way as in the direct oxidation

process by gas phase catalytic oxidation, is simultaneously oxidized and is esteried in liquid methanol to get MMA directly. This process seems to be very attractive and get much attention, because it has fewer steps and gives better yield than that of the direct oxidation process
1 CH2 =C(CH3 )CHO + CH3 OH + 2 O2

CH2 =C(CH3 )COOCH3 + H2 O The attempts for oxidation or oxidative esterication of methacrolein in liquid phase had been made for a long time. The method using hydrogen peroxide or peracetic acid had been known. As for the oxidation with molecular oxygen, catalysts containing Pd were known, but the yield obtained was not sufcient. Asahi Chemical has developed a new solid catalyst, which consists of Pd-Pb, and got a high yield of 93% of MMA [46]. They studied the role of Pb, and revealed that the catalytic active structure is in the Pd-Pb metal compound. The reaction is done in a three-phase system, in which air or oxygen is blown through the excess of methanol in liquid phase in the presence of solid catalyst in a slurry. The excess of methanol and the unreacted methacrolein have to be recycled. A small amount of propylene, methylformate, methacrylic acid, methylisobutylate, methoxy-isobutylaldehyde and so on, are formed as undesirable by-products. Many patents about the recycle system and the purication process of MMA were published. They admitted that in the early stage of development, there were some difculties in the productivity and the catalyst life. A detailed study to improve the catalyst, for example, a study of a catalyst carrier has been done, and has established an excellent industrial catalyst system [4749]. 5.5. Isobutane direct oxidation method Though all processes as described above use alkenes as raw materials, the usage of alkane is expected for a next generation process. The raw materials for producing maleic anhydride has been changing from benzene or butenes to n-butane. BP America, Mitsubishi Chemical and Asahi Chemical have announced a propane route for producing acrylonitrile on a pilot stage.

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Table 1 Effect of total pressure and space velocity on oxidation of isobutanea Temperature ( C) 330 354 329 332 355
a

piC4 (kPa) 37 37 74 100 137

SV (h1 ) 1025 2059 2041 2744 7605

ptot (kPa) 100 100 200 270 370

Conversion iC4 (%) 7.6 8.3 7.1 9.0 12.0

Selectivity MAA (%) 57.4 50.4 55.5 51.9 43.8

Yield MAA (%) 4.4 4.2 3.9 4.7 5.3

Productivity MAA (mmol h1 g cat1 ) 0.74 1.41 1.33 2.65 6.60

Conversions of isobutane, selectivities MAA and productivity to MAA at different space velocities and different total pressures. Reaction conditions: iC4 = 37%, O2 = 37%, H2 O = 15%, N2 = balance, cat.: Mo12 V0.5 P1.5 As0.4 Cu0.3 Cs1.4 Ox .

Isobutane is now utilized in large quantities for making MTBE by dehydration to isobutylene, but if it could be used for being oxidized directly in one-step to obtain methacrylic acid, the process would be very attractive (CH3 )3 CH + 2O2 CH2 =C(CH3 )COOH + 2H2 O Rohm & Haas discovered at an early time that isobutane can be oxidized to methacrylic acid with a heteropoly acid catalyst which consists of Mo-P-Sb-O. After that, Asahi Chemical, Sumitomo Chemical and others showed that similar Mo-V-P heteropoly acid catalysts to that used for methacrolein oxidation in the isobutylene oxidation process, have a relatively good performance [50,51]. The selectivity to MAA plus methacroleine reaches more than 70%. But, when isobutane conversion is increased, the selectivity falls fairly linear. This is because the consecutive oxidation rate of the produced MAA is much larger than the rate of isobutane conversion. Though the conversion is around 10%, a comparatively high productivity can be attained. Table 1 shows the productivity enhancement by increasing pressure and space velocity [52]. For industrialization, a short catalyst life would be a big problem, and a development of high performance catalyst would be a key factor. In this reaction, one of three equivalent methyl group of isobutane remains, another one is dehydrated for providing a double bond and the other one of these is converted for providing a carboxyl group, using the same catalyst under same conditions. This kind of catalysis is very interesting and challenging for catalyst researchers, although it would be highly difcult.

6. Outlook Many bulk-chemicals changed their manufacturing processes into methods utilizing alkenes as a raw material due to the appearance of petrochemicals in the 1950s. The development of the MMA process is a rare case in which the rst process developed in the 1930s dominates its world production even today. But now, several new methods have been realized mainly by Japanese companies. The various processes described above had to or will have to make jumps in catalysts performances in order to rise up to an industrial economically favorable level, though the reactions themselves have been studied for a long period. It will be interesting to see which process will be the main stream of the MMA manufacturing from now on. Catalyst researchers all over the world are expected to develop new catalysts for such a process and then the commercialization will be veried.

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