触媒技術の動向と展望創刊 20 周年記念企画別冊英語版 Special Edition for the 20 th Anniversary of Publication of Annual Survey of Catalytic Science and Technologies by the Catalysis Society of Japan のご案内 触媒学会では 1993 年度から事業の一環として 触媒技術の動向と展望 と題した年鑑の出版を行っております 創刊 20 周年記念号の 2012 年度版では 金属触媒 酸化物触媒 生体 錯体触媒 重合触媒 キャラクタリゼーション 光触媒 石油化学 高分子合成 バイオベース化学の九つの触媒分野における研究開発の歴史と将来展望をまとめた特集を掲載しております この特集の英語版ならびに大学 高専 国公立研究機関における研究活動 ( 研究者総覧 ) の英語版を別冊として製本し 販売いたします この別冊は海外の触媒研究者に日本における触媒の研究動向 研究者を紹介する際にもお役立ていただける内容となっています また 大学院にて触媒研究を行っている院生等にとりましても必読の書となっています つきましては本別冊の有用性をご賢察の上 ぜひご購入いただきますようにご案内申し上げます なお 5 冊以上まとめてご購入いただけます場合は割引価格を準備いたしていますので事務局までお問い合わせください 創刊 20 周年記念企画別冊英語版 (379 頁 ) 価格 6,000 円 ( 消費税込 ) ご購入は 住所 会社名及び部署名 お名前 電話番号 FAX 番号 E-mail アドレス を明記のうえ 触媒学会事務局まで E-Mail(catsj@pb3.so-net.ne.jp) または FAX (03-3291-8225) にてお申し込みください Special Edition for the 20 th Anniversary of Publication of Annual Survey of Catalytic Science and Technologies by the Catalysis Society of Japan 1. Contributions to the Special Edition 1.1 Prosperous future of catalysis: Greetings from the President Tokyo Metropolitan University Masatake Haruta 3 1.2 A submission to the 20 th anniversary commemorative edition The Catalyst Manufacturers Association, Japan Yujiro Saito 5 1.3 The history and development of metallic catalysts Industrial Catalyst Laboratory Takashiro Muroi 8 1.4 Complication towards evolution in the history of oxide catalysts for selective oxidation Catalyst Research Center, Hokkaido University Wataru Ueda 18 1.5 Development of homogeneous catalysis and biocatalysis over past two decades Chemical Resources Laboratory, Tokyo Institute of Technology Munetaka Akita 26 1.6 Recent trends in olefin polymerization catalyst development Mitsui Chemicals Singapore R&D Center Pte.Ltd. Haruyuki Makio, Terunori Fujita 38
1.7 Past, present and future of catalyst characterization Catalyst Research Center, Hokkaido University Kiyotaka Asakura 51 1.8 History and outlook of photocatalyst research The University of Tokyo Kazuhiko Maeda, Kazunari Domen 60 1.9 Development of the Japanese chemical industry over past decades and prospect6s for research in the 21 st century Mitsubishi Chemical Group Science and Technology Research Center Corp. Tohru Setoyama 72 1.10 Historical Stream, Trends and Outlook for Polymerization Catalysts Tokyo Metropolitan University Kotohiro Nomura 80 1.11Bio-based chemicals towards green innovation Kyoto Gakuen University Sakayu Shimizu 92 2. Recent activities of Japanese academic organizations Aichi University of Technology 107 Akita University 107 Asahikawa National College of Technology 109 Central Research Institute of Electric Power Industry 110 Chiba Institute of Technology 111 Chiba University 112 Chuo University 115 Doshisha University 117 Ehime University 119 The University of Electro-Communications 121 Gifu University 122 Gunma University 125 Hakodate National College of Technology 126 Hirosaki University 126 Hiroshima University 127 Hokkaido University 130 Hokkaido University of Education 144 University of Hyogo 146 Ibaraki National College of Technology147 Ichinoseki National College of Technology 147 International Christian University 148 Ishinomaki Senshu University 149 Japan Advanced Institute of Science and Technology 150 Kagoshima University 152 Kanagawa University 153 Kansai University 156 Keio University 159 Kinki University 160 The University of Kitakyushu 161 Kitami Institute of Technology 162 Kobe University 166 Kochi National College of Technology 169 Kochi University 169 Kogakuin University 170 Kyoto Institute of Technology 171 Kyoto University 172 Kyushu Institute of Technology 184 Kyushu University 186 Kumamoto University 198 Meiji University 199 Meisei University 200 Mie University 200 University of Miyazaki 201 Muroran Institute of Technology 203 Nagaoka University of Technology 204 Nagasaki University 205 Nagoya Industrial Science Research Institute 208 Nagoya Institute of Technology 208 Nagoya Municipal Industrial Research Institute 209 Nagoya University 210 Nara Institute of Science and Technology 219 Nara Women s University 220 National Defense Academy 221 National Institute of Advanced Industrial Science and Technology 222 National Institutes of Natural Sciences 237 Nihon University 239 Numazu National College of Technology 241 Okayama Ceramics Research Foundation 242
Okayama University 243 Oita University 247 Osaka University 249 Osaka Prefecture University 267 Research Institute of Innovative Technology for the Earth 272 RIKEN 273 Ritsumeikan University 274 Ryukoku University 275 Sagami Chemical Research Institute 276 Saitama University 278 Seikei University 279 Industrial Research Center of Shiga Prefecture 280 Shimane Institute for Industrial Technology 281 Shimane University 282 Shinshu University 283 Shizuoka University 285 Sophia University 288 Tohoku University 290 Tokai University 297 The University of Tokushima 299 The University of Tokyo 301 Tokyo Institute of Technology 309 Tokyo Metropolitan University 323 Tokyo University of Agriculture and Technology 325 Tokyo University of Science 327 Tokyo University of Science Yamaguchi 329 Tottori University 330 University of Toyama 332 Toyama Industrial Technology Center 336 Toyohashi University of Technology 336 Toyota Technological Institute 339 University of Tsukuba 339 Ube National Collage of Technology 341 Utsunomiya University 341 Waseda University 344 Yamaguchi University 350 University of Yamanashi 351 Yokohama National University 353 INDEX 356
Special Edition of the 20 th Anniversary of CATSJ survey The history and development of metallic catalysts Takashiro Muroi 1900 1950 1960 1970 1980 1990 2000 2010 Transition metal catalysts Fischer-Tropsch catalyst Franz Fischer, Hans Tropsch (developed in 1920's, Max Planck Institite) ZnO/Cr 2 O 3 Methanol catalyst Alwin Mittasch, Mathias Pier (BASF, 1923) Ni for Hydrogenation Paul Sabatier Jean B Senderens (1897) Pt-group metals PtO 2 H 2 O Adams' Catalyst Roger Adams (1922) Ammonia synthesis catalys Fe/K/Al 2 O 3 (BASF, 1920) (Fritz Haber, Carl Bosch) [Nobel prize] (1918, 1931) Coal to Hydrogen, WGS & Reforming catalyst (BASF, 1923) Sasol Fe-Coal-to- FT oil Sasol 1 Arge 1955 Sasol 2 Synthol, 1976 Sasol 3, 1995 150,000bpd (in 2011,Coal/Natural gas mix) CuO/ZnO Low Pressure Methanol catalyst (ICI, 1960's) CuO/CuCr 2 O 4 Adkins-Lazier catalyst (1937) Raney Ni Hydrogenation catalyst W R Grace (1924) Supported Ag Ethylene-to-EO catalyst (1937) Methane to Hydrogen, SMR Ni Refroming catalyst Pt Reforming UOP (1948) Auto emission Pd catalyst (1975) Urushibara Ni Hydrogenation catalyst (1952) Ethylene-to-EO Shell, Davy process (1956) Pt-Re Reforming Chevron (1968) Auto emission 3-way Catalyst PtRhPd (1977) Ammonia catalyst Ru/ K or Cs/Carbon (A Ozaki-K Aika, 1980's) Methane to Syngas POx Refroming catalyst (1970's) Shell GTL Co/SiO 2 Fixed bed 12,500bpd Bintulu, Malaysia (1993) NOx storage reduction Pt /M/Al 2 O 3 (1995) Ammonia catalyst Ru/Cs/Graphite Carbon (BP-KBR, 1995) Organometallic complex catalysts for Ammonia synthesis (Hidai, Nishibayashi 1980s-) CO 2 to Methanol RITE, Japan (2000) Oryx GTL Co/SiO 2 slurry 34,000bpd Sasol/ Qatar QP (2006) PAFC, PEFC, PAFC Pt anode, MCFC Ni anode (1970's) SOFC Ni/YSZ cathode- YSZ electrolyte-lsm/ysz anode system (1980's) Sample Formulated Raney Ni W R Grace (1990s) Ethylene-to-EO, MEG Alpha processt Mitsubishi, Shell (199x) Pd Perovskite Intelligent DeNOx Catalyst Daihatsu Motors (2002) Pearl GTL Co/SiO 2 Fixed bed 140,000bpd Shell/ Qatar (2011) Kerosene Steam Reforming Ru/ZrO 2 catalyst Idemitsu Kosan (2005) Pt/CeO 2 Heat resistant Catalyst Toyota Motors (2008) Ancher Catalyst Nissan Motors (2008) Pt /Asbestos catalyst Sulfuric acid (P Phillips, 1831) Ammonia oxidation for Nitric acid F Kuhlmann (Pt) (1838) W Ostwald (Pt Strips) (1908) K Kaiser (Pt gauze) (1909) Wilhelm Ostwald [Nobel prize] (1909) Methanation Ru/Al 2 O 3 Osaka Gas (1970s) Ozone decomp Pd/Al 2 O 3 Engelhard (1980s) HCl to Cl 2 Oxychlorination RuO 2 /TiO 2 Sumitomo Chemical (2003) Vinyl acetate PdAu alloy catalyst Bayer (1972) Butadiene diacetoxylation PdTe alloy (1982) Mitsubishi Chemical Allyl acetate PdCu/SiO 2 catalyst Showa Denko (1994) Methacrolein-to-MMA-1 Catalyst Direct Metha process Asahi Chemical, PdPb alloy (1998) Paul Sabatier [Nobel prize] (1912) PEFC Cathode/Anode Pt (1970's) Au nanosize Catalyst M Haruta (1987) PROX Ru/TiO 2 (1990's) Methacrolein-to-MMA-2 Catalyst Asahi Chemical, Au/Ni (2008) Pd-Ag alloy film High Purity H 2 (1950's) Pd alloy membrane reactor for H 2 (1980's) 121212 Industrial Catalysts Laboratory, 5-8-5 Kariya, Ushiku, 300-1235 Ibaraki, Japan
The history and development of metallic catalysts 1. Introduction The fundamentals of industrial catalysts used in modern chemical and environmental processes were discovered by the middle of the 20th century. In these first-generation processes, severe reaction conditions were applied, resulting in high construction and utility costs and performance that was inferior to that found in modern chemical plants. The second generation catalysts developed in the latter half of the 20th century were more sophisticated. They not only extended the variety of usable feedstocks and products manufactured, but also reduced the consumption of material and energy inputs, thus achieving higher profitability and lower environmental emissions. These catalysts were developed primarily for continuous and commercial-scale processes, and contributed to the establishment of a modern and prosperous chemical industry. Even in ammonia synthesis, the highest pressure and high temperature process in the chemical industry, Japanese chemists discovered a Ru/Cs-based high-performance catalyst in the 1980s that can function at much lower pressure and temperature. The first commercial use of this Ru/Cs-based catalyst was by BP-KBR in 1996. Further progress and enhanced contributions from catalysts is expected moving forward in order to combat global warming and an anticipated shortage of fossil fuel resources in the near future. 1) 2. The history of metallic catalysts 2.1 1831-1900 (In the beginning) Metallic catalysts were already utilized in the nascent stages of the chemical industrial revolution in the 19th century in Europe. An asbestos-supported Pt (P. Phillips, 1831) was the first catalyst that appeared in industry for the commercial production of sulfuric acid, an important material for producing sodium carbonate by the Leblanc process (N. Leblanc, 1791). The chamber process (introduced in 1746), or NO 2 -catalysed SO 2 oxidation process, was gradually switched to the new catalytic process. In 1913, F. Slama and H. Wolf patented, a catalyst made of a salt of vanadic acid with alkali promotors on a porous support for this process. The V 2 O 5 -alkali catalyst became popular soon after this finding, replacing all the Pt-catalysed processes. Nitric acid, another basic material in the chemical industry, was produced by acidolysis of KNO 3 with sulfuric acid when Alfred Nobel developed dynamite in 1866. The concept of vapor phase oxidation of ammonia to nitric acid was proposed by F. Kuhlmann in 1838, but the first industrial process was only developed in the 1920s, when an ample supply of gunpowder was required and the Pt gauze (multiple layers of a fine wire mesh) catalyst was invented. The activity of various finely-dispersed metallic hydrogenation catalysts was studied by Paul Sabatier, who together with Jean B. Senderens in France discovered the Ni catalyst for hydrogenation of unsaturated compounds in 1897. In the same year Joseph Crosfield & Sons succeeded in producing hardened (or hydrogenated) oil via Ni catalyzed hydrogenation of fish and vegetable oils in the UK. 2.2 1900-1960 (Rise of metallic catalysts and coal era) Many new catalytic processes were developed during the golden era of 1900 to the 1920s. Production of nitric acid was started via catalytic oxidation of ammonia with a coil of Pt strips by Wilhelm Ostwald in 1906, and soon after with a Pt gauze catalyst developed by K Kaiser in 1909. Further, ammonia was produced via the calcium cyanamide process from calcium carbide.