Trends and Future of Sumitomo Chemical Co., Ltd. Basic Chemicals Research Laboratory Monomer-MMA Technologies Koichi NAGAI Toshiaki UI MMA production is one of the core businesses of the Basic Chemicals Sector of Sumitomo Chemical, and its demand and capacity is continuously going to be expanded, mainly in Asia. Now five technologies for monomer- MMA production coexist in the world, and none of them is the predominant process. Among those technologies, the C4 methods are going to be adopted in many production plants. Sumitomo Chemical also selected this tech- nology for its MMA production. In this paper, the current processes, mainly for C4 methods, and the next genera- tion of potential technologies will be reviewed. This paper is translated from R&D Report, “SUMITOMO KAGAKU”, vol. 2004-II. Introduction Asia 2000 N. America Europe 3500 Polymethyl methacrylate (PMMA) can be consid- Other Total Demand ered the queen of resins, because it is the most beauti- –1 Total Supply 1500 t y –1 ful of synthetic resins. Making use of its superior trans- 3000 3 t y parency, weather resistance and other characteristics, 3 the demand for its use in signboards and displays, 1000 2500 lighting equipments, automotive parts, construction related materials and the like has increased. Recently, we have seen a rapid expansion in new fields related to 500 2000 Regional Demand/10 IT, making even greater use of its optical characteris- Total Demand & Supply/10 tics, for example in light-guiding plates and light diffu- sion plates for flat panel displays. Not only are there 0 1500 uses for methyl methacrylate (MMA), in the form of 2003 2004 2005 2006 2007 monomers of these resins, but also there is a demand Fig. 1 Forecast world MMA demand and supply (estimated by Sumitomo Chemical Metha- for comonomers in fields such as coatings, adhesives crylates Division). and plastic modifiers. In addition, higher esters like butyl-ester produced by esterification of methacrylic acid (MAA), which is an intermediate in MMA synthe- Asia, especially in China. sis, or by transesterification of MMA, are used in a vari- In this article, we will comment on the trends in ety of applications. MMA production technologies. It is usual in bulk MMA production is one of the core businesses of the chemicals production that the one or two most compet- Basic Chemicals Sector of Sumitomo Chemical Co., itive methods will survive, but there is a special situa- Ltd., and we are actively expanding these operations in tion in MMA production, where five methods currently Asia, where the demand for monomers and polymers is coexist. Furthermore, in contrast to the fact that in increasing rapidly. The world demand for MMA is Europe and the U.S. the most extended method is the growing steadily, and it exceeded 2.3 million tons in traditional acetone cyanohydrin (ACH) process as 2003. Fig. 1 shows the demand and supply predictions shown in Fig. 2, other methods are already dominant estimated by the Sumitomo Chemical Methacrylates in Japan and Asia. Most of these new methods have Division. A great amount of growth will be expected in been developed in Japan. SUMITOMO KAGAKU 2004-II 1 Trends and Future of Monomer-MMA Technologies C4 Direct Oxdn developed and commercialized the ACH process in C4 DOE 1937. In Japan, Asahi Glass Co., Ltd. and Fujikura C2 BASF 1200 New ACH Kasei Co., Ltd. started production in 1938. After that, ACH the ACH method was actually the only industrial pro- 1000 DOE: Direct Oxidative Esterification duction method for MMA for 45 years until Mitsubishi 1 – 800 Rayon Co., Ltd. and Nippon Shokubai independently t y 3 commercialized the direct oxidation method in 1982. 600 The raw materials for the ACH process are acetone and hydrogen cyanide. With the sudden rise and develop- Capacity/10 400 ment of petrochemistry following World War II, it was possible to obtain acetone as a byproduct of phenol and 200 hydrogen cyanide as well as from acrylonitrile produc- 0 tion. In this way, there is an aspect of concerted devel- Japan Other Europe opment along with these products. Sumitomo Chemi- Asia 2004 Asia 2007 N. America cal also entered the MMA business after introduction Fig. 2 World MMA capacity and technologies of the Sohio acrylonitrile process. (2004). However, with the increase in demand for MMA and with the changes in the world’s way of looking at indus- Sumitomo Chemical has commercialized a direct trial activity in terms of pollution problems and the like, isobutylene oxidation method in cooperation with Nip- important weaknesses in the conventional ACH pon Shokubai Co., Ltd. This was introduced in the method were revealed, and there was a strong demand journal SUMITOMO KAGAKU in 1992,1) and this arti- for changing the production method. The first weak- cle is a continuation of that one. The Sumitomo Chemi- ness of the ACH method is the difficulty of acquiring cal / Nippon Shokubai technology has expanded to the cyanide. In Japan in particular, almost all of the five plants, including plants in Korea and Singapore, cyanide raw material for ACH is the byproduct of the and another plant is being constructed. Moreover, Sohio acrylonitrile process, and for conventional Japan- plans for further expansion are also progressing. ese makers who produced only several ten thousands Table 1 shows the history of Sumitomo Chemical’s of tons MMA per year, cyanide synthesis on purpose MMA operations. could not be feasible. The second weakness of the ACH method is processing the waste acid originated from the use of sulfuric acid. The ACH process pro- Table 1 History of MMA in Sumitomo Chemical. duces a large volume of ammonium bisulfate contami- nated with organic materials as a byproduct. At one 1962 Start to research on C4 direct oxidation 1964 Introduction of SOHIO acrylonitrile (Niihama) time, there were cases of this waste acid being dis- 1967 Introduction of MMA polymer (Sumipex) from ICI posed of in the ocean. In addition, it is said that deep 1967 Start production of monomer-MMA (ACH process) well processing, the name for disposing of something 1982 Semicommercial C4 Direct Oxidation by Nippon Shokubai (Himeji) deep in the earth without processing it, has been adopt- 1982 Foundation of Japan Methacryl Monomer (J/V with Nippon Shokubai) 1984 Start JMM Niihama plant ed in the U.S. and other places. Since these methods 1889 Start JMM Himeji plant are no longer permissible, recovery as ammonium sul- 1993 Start LGMMA plant (Korea) fate with addition of ammonia, or recovery as sulfuric 1998 Start SMM plant (Singapore) acid by investing in facilities for super corrosion resis- 2002 Business exchange Acrylic acid and MMA with Nippon Shokubai tant materials, as well as a need for large amounts of 2003 Start LGMMA 2nd plant 2005 Scheduled start SMM 2nd plant energy, is becoming a large financial burden. In Europe and the U.S., it can be assumed that there has been little progress in changing the production History of MMA Production method because there are large plants for which the costs are feasible even if hydrogen cyanide is produced Methacrylic resin is old, having been introduced to by synthesis, and since the pressure on waste acid the world by Rohm & Haas in the 1930’s. Then, ICI treatment has not been intense. However, the situation SUMITOMO KAGAKU 2004-II 2 Trends and Future of Monomer-MMA Technologies in Japan is as described above, thus all MMA makers ICI DuPont Rohm & Haas(DE) Rohm & Haas(US) Orkem have converted to their own new methods, even business exchange though there are some companies retaining some ACH Degussa Rohm & Haas(US) Atochem processing. ICI monomer polymer polymer monomer Table 2 lists the capacities and production methods purchase merger of polymer for six Japanese MMA producers. In addition, there Ineos Cytex AtoHaas have been repeated alliances and ruptures among 100% name change R & H withdrawal Western MMA makers, and now there are four groups. 50% The history of their rearrangements and capacities is Lucite Roehm R & H Atofina 100% shown in Fig. 3.2) 560kt/y50% 360kt/y 250kt/y Cyro Atoglas (polymer) 375kt/y Table 2 Japanese MMA makers. Fig. 3 Relations between Western MMA makers. Capacity Company, Group Technology Remarks 103 t/y MMA Synthesis Routes Mitsubishi Rayon ACH 107 C4 DO* 110 Methyl methacrylate or methacrylic acid are simple Thai MMA (MRC45%) C4 DO 70 2004 +15 debottleneck molecules, but many routes have actually been thought China C4 DO (90) 2006 start Sumitomo Chemical (Nippon Shokubai) C4 DO 90 (NS 18) up for making them from even simpler molecules, and Korea, LGMMA (SC25%, NS25%) C4 DO 100 a variety of raw materials, C1 through C4, are used. Singapore, SMM (SC100%) C4 DO 53 2005 +80 increase Besides the routes described below, there are many for Asahi Kasei C4 DOE** 100 which patent applications have been made as variations Kuraray ACH 65 20 and possible routes. We will describe the routes that C4 DO Kyodo Momomer Mitsui Chemical 20 ) are already commercialized and those that were once Korea, Honam Petrochemical (licence) C4 DO 40 commercialized. We will also discuss processes for Mitsubishi Gas Chemical New ACH 51 which there have been announcements of future com- *C4DO: Isobutylene Direct Oxidation mercialization and the isobutane process, which has **C4DOE: Isobutylene Direct Oxidative Esterification Table 3 MMA production technologies. Raw materials Process Feature, Issue Important catalytic reaction Maker Industrialized (without methanol) Acetone Supply of HCN ACH 1937– HCN, H2SO4 Waste treatment Mitsubishi Rayon C4 Direct Isobutylene