2003 Fiscal Year Annual Research Report

ハロゲンフリープロセスのための触媒反応場設計

Research Project

Project/Area Number	13126213
Research Institution	Tottori University
Principal Investigator	片田直伸鳥取大学, 工学部, 助教授 (00243379)
Co-Investigator(Kenkyū-buntansha)	奥村和鳥取大学, 工学部, 助手 (30294341) 丹羽幹鳥取大学, 工学部, 教授 (10023334)
Keywords	固体酸触媒 / アンモニアIR-TPD / ゼオライト / 水蒸気 / パラフィンクラッキング / NO還元 / Pd / WO_3 / ZrO_2
Research Abstract	アンモニア昇温脱離(TPD)と赤外分光(IR)を組み合わせ、酸点を構造やBronsted・Lewisの種別によって区別した上で酸量・酸強度・酸強度分布を一度に測定する方法を開発した。装置を試作し、いくつかのゼオライトで測定を行った。アンモニアの吸着種にはBronsted酸点上のNH_4^+(1450cm^<-1>)、Lewis酸点上のNH_3(1620)、水素結合したNH_3(1650)に加えて、従来見過ごされてきた1320〜1420cm^<-1>の未同定の種が存在した。モルデナイトなど構造と酸性質の関係が確立されているゼオライトを用いて、骨格内Alによって強いBronsted酸点が発現し、これとは別に弱い水素結合種が見られることを、脱離温度の違いによって明確に区別した。酸性水酸基にも複数種があり、これらを区別して正確に調べると、酸強度と吸収波数には相関があった。このことは、従来のIRと触媒反応の間の矛盾を解き明かす進歩であった。EDTA処理USYなどを用いて、骨格外Alに起因する非常に強い酸点の観察に成功した。非常に強い酸点には複数種があり、強いけれども触媒反応に関与しない酸点は周囲を水酸基で囲まれているようである。一方、アルカン分解などに有用な非常に強い酸点そのものである水酸基や、その上のNH_4^+の観察と定量に成功した。これらによって前年度までに見出したハロゲンフリープロセスに用いる優れた触媒の作用機構を説明できるであろう。一方、このような実験の過程でWO_3/ZrO_2が水蒸気存在下でBronsted酸性を示すことを見出し、NO還元のためのPd触媒の担体として用いたところ、実用条件である水蒸気共存下で優れた性能を示した。また、分子を鋳型とするシリカの化学蒸着(CVD)法を開発し、分子の形の細孔を残したシリカ層で固体酸触媒活性点の周囲を覆うことに成功し、形状選択的な吸着能を得た。

Research Products
(19 results)

All Other

All Publications (19 results)

[Publications] Naonobu Katada, Miki Niwaら: "Acidic Property of Modified Ultra Stable Y Zeolite : Increase in Catalytic Activity for Alkane Cracking by Treatment with Ethylenediaminetetraacetic Acid Salt"J.Mol.Catal., A : Chemical. 211, 1-2. 119-130 (2004)
[Publications] Hiroto Matsuura, Naonobu Katada, Miki Niwa: "Additional Acid Site on the HZSM-5 Treated with Basic and Acidic Solutions as Detected by Temperature Programmed Desorption of Ammonia"Micro-.Mesoporous Mater.. 66, 2-3. 283-296 (2003)
[Publications] Naonobu Katada, Sachiko Akazawa, Miki Niwa: "Improvement of Selectivity in Specific Adsorption by Addition of Acetic Acid during Chemical Vapor Deposition of Silicon Alkoxide to Form a Silica Overlayer with Molecular Sieving Property."Adv.Mater., Chem.Vap.Deposition. 印刷中.
[Publications] Ryosuke Nakao, Yoshihiro Kuhnta, Naonobu Katadaら: "Highly active BEA catalyst for catalytic cracking of n-heptane"Catal.Lett.. 89(1-2). 153-157 (2003)
[Publications] Toshiyuki Itoh, Naonobu Katada: "Novel Supporting Materials of Lipase PS Suitable for Use in an Ionic Liquid Solvent System"Green Chemistry. 5(5). 494-496 (2003)
[Publications] Naonobu Katada, Yusuke Ii, Munekazu Nakamura, Miki Niwa: "Oxidation of Sulfur Dioxide to Sulfuric Acid over Activated Carbon Catalyst Produced from Wood"J.Jpn.Petroleum Inst.. 46(6). 392-395 (2003)
[Publications] 片田直伸, 池田恵俊ら: "木材の簡便な水蒸気処理による活性炭の製造"化学工学論文集. 29(4). 488-492 (2003)
[Publications] Yuko Habuta, Naoaki Narishige, Kazu Okumura, Naonobu Katada, Miki Niwa: "Catalytic Activity and Solid Acidity of Vanadium Oxide Thin Layer Loaded on TiO_2, ZrO_2, and SnO_2"Catal.Today. 78(1-4). 131-138 (2003)
[Publications] Tetsuro Shigeno, Koji Inoue, Tatsuo Kimura, Naonobu Katada, Miki Niwa, Kazuyuki Kuroda: "Synthesis of Al-containing mesoporous silica (KSW-2) with semi-squared channels by incorporation of Al into the framework of kanemite."J.Mater.Chem.. 13(4). 883-887 (2003)
[Publications] Naonobu Katada, Tokuko Doi, Tatsuro Shinmura, Shuji Kuroda, Miki Niwa: "Catalytic Activity of Gallium-Loaded ZSM-5 Zeolite for Synthesis of Aniline from Phenol and Ammonia"Stud.Surf.Sci.Catal.. 145. 197-200 (2003)
[Publications] 丹羽幹, 片田直伸: "アンモニア昇温脱離法によるゼオライトと金属酸化物薄層の固体酸性質"表面科学. 24(10). 635-641 (2003)
[Publications] K.Okumura, R.Yoshimoto, S.Yokota, Kazuo Kato, Hajime Tanida, Tomnva Uruga, Miki Niwa: "Spontaneous Dispersion of PdO and Generation of Metal Pd cluster in Zeolites Studied by Means of in situ DXAFS"Physica Scripta. 印刷中.
[Publications] K.Okumura, T.Kusakabe, S.Yokota, K.Kato, H.Tanida, T.Uruga, M.Niwa: "Spontaneous Dispersion of PdO onto acid sites of zeolites Studied by in situ DXAFS"Chem.Lett.. 2003(32). 636-637 (2003)
[Publications] K.Okumura, H.Tanaka, T.Kobayashi, M.Niwa: "Toluene Combustion over Supported Palladium Catalysts"Appl.Catal.B. 44. 325-331 (2003)
[Publications] R.Yoshimoto, K.Okumura, M.Niwa: "Catalytic Activity of Pd Loaded on WO3/Al2O3 for NO-CH4-O2 in the Presence of Water Vapor"Catal.Today. 84. 159-164 (2003)
[Publications] K.Okumura, T.Kusakabe, M.Niwa: "Durable and Selective Activity of Pd Loaded on WO3/ZrO2 for NO-CH4-O2 in the Presence of Water Vapor"Appl.Catal.B. 41. 137-142 (2003)
[Publications] K.Okumura, S.Matsumoto, N.Nishiaki, M.Niwa: "Support Effect of Zeolite on the Methane Combustion Activity of Palladium"Appl.Catal.B. 40. 151-159 (2003)
[Publications] D.Lu, J.N.Kondo, K.Domen, H.A.Begum, M.Niwa: "Ultra-fine Tuning of Microporous Opening Size in Zeolite by CVD"J.Phys.Chem.. 印刷中.
[Publications] Naonobu Katada, Miki Niwaら(分担執筆): "Molecular Imprinting of Polymers"Bioscience/Eurekah. Com.(印刷中).

2003 Fiscal Year Annual Research Report

ハロゲンフリープロセスのための触媒反応場設計

Principal Investigator

片田 直伸 鳥取大学, 工学部, 助教授 (00243379)

Research Products

[Publications] Naonobu Katada, Miki Niwaら: "Acidic Property of Modified Ultra Stable Y Zeolite : Increase in Catalytic Activity for Alkane Cracking by Treatment with Ethylenediaminetetraacetic Acid Salt"J.Mol.Catal., A : Chemical. 211, 1-2. 119-130 (2004)

[Publications] Hiroto Matsuura, Naonobu Katada, Miki Niwa: "Additional Acid Site on the HZSM-5 Treated with Basic and Acidic Solutions as Detected by Temperature Programmed Desorption of Ammonia"Micro-.Mesoporous Mater.. 66, 2-3. 283-296 (2003)

[Publications] Naonobu Katada, Sachiko Akazawa, Miki Niwa: "Improvement of Selectivity in Specific Adsorption by Addition of Acetic Acid during Chemical Vapor Deposition of Silicon Alkoxide to Form a Silica Overlayer with Molecular Sieving Property."Adv.Mater., Chem.Vap.Deposition. 印刷中.

[Publications] Ryosuke Nakao, Yoshihiro Kuhnta, Naonobu Katadaら: "Highly active BEA catalyst for catalytic cracking of n-heptane"Catal.Lett.. 89(1-2). 153-157 (2003)

[Publications] Toshiyuki Itoh, Naonobu Katada: "Novel Supporting Materials of Lipase PS Suitable for Use in an Ionic Liquid Solvent System"Green Chemistry. 5(5). 494-496 (2003)

[Publications] Naonobu Katada, Yusuke Ii, Munekazu Nakamura, Miki Niwa: "Oxidation of Sulfur Dioxide to Sulfuric Acid over Activated Carbon Catalyst Produced from Wood"J.Jpn.Petroleum Inst.. 46(6). 392-395 (2003)

[Publications] 片田直伸, 池田恵俊ら: "木材の簡便な水蒸気処理による活性炭の製造"化学工学論文集. 29(4). 488-492 (2003)

[Publications] Yuko Habuta, Naoaki Narishige, Kazu Okumura, Naonobu Katada, Miki Niwa: "Catalytic Activity and Solid Acidity of Vanadium Oxide Thin Layer Loaded on TiO_2, ZrO_2, and SnO_2"Catal.Today. 78(1-4). 131-138 (2003)

[Publications] Tetsuro Shigeno, Koji Inoue, Tatsuo Kimura, Naonobu Katada, Miki Niwa, Kazuyuki Kuroda: "Synthesis of Al-containing mesoporous silica (KSW-2) with semi-squared channels by incorporation of Al into the framework of kanemite."J.Mater.Chem.. 13(4). 883-887 (2003)

[Publications] Naonobu Katada, Tokuko Doi, Tatsuro Shinmura, Shuji Kuroda, Miki Niwa: "Catalytic Activity of Gallium-Loaded ZSM-5 Zeolite for Synthesis of Aniline from Phenol and Ammonia"Stud.Surf.Sci.Catal.. 145. 197-200 (2003)

[Publications] 丹羽幹, 片田直伸: "アンモニア昇温脱離法によるゼオライトと金属酸化物薄層の固体酸性質"表面科学. 24(10). 635-641 (2003)

[Publications] K.Okumura, R.Yoshimoto, S.Yokota, Kazuo Kato, Hajime Tanida, Tomnva Uruga, Miki Niwa: "Spontaneous Dispersion of PdO and Generation of Metal Pd cluster in Zeolites Studied by Means of in situ DXAFS"Physica Scripta. 印刷中.

[Publications] K.Okumura, T.Kusakabe, S.Yokota, K.Kato, H.Tanida, T.Uruga, M.Niwa: "Spontaneous Dispersion of PdO onto acid sites of zeolites Studied by in situ DXAFS"Chem.Lett.. 2003(32). 636-637 (2003)

[Publications] K.Okumura, H.Tanaka, T.Kobayashi, M.Niwa: "Toluene Combustion over Supported Palladium Catalysts"Appl.Catal.B. 44. 325-331 (2003)

[Publications] R.Yoshimoto, K.Okumura, M.Niwa: "Catalytic Activity of Pd Loaded on WO3/Al2O3 for NO-CH4-O2 in the Presence of Water Vapor"Catal.Today. 84. 159-164 (2003)

[Publications] K.Okumura, T.Kusakabe, M.Niwa: "Durable and Selective Activity of Pd Loaded on WO3/ZrO2 for NO-CH4-O2 in the Presence of Water Vapor"Appl.Catal.B. 41. 137-142 (2003)

[Publications] K.Okumura, S.Matsumoto, N.Nishiaki, M.Niwa: "Support Effect of Zeolite on the Methane Combustion Activity of Palladium"Appl.Catal.B. 40. 151-159 (2003)

[Publications] D.Lu, J.N.Kondo, K.Domen, H.A.Begum, M.Niwa: "Ultra-fine Tuning of Microporous Opening Size in Zeolite by CVD"J.Phys.Chem.. 印刷中.

[Publications] Naonobu Katada, Miki Niwaら(分担執筆): "Molecular Imprinting of Polymers"Bioscience/Eurekah. Com.(印刷中).

片田直伸鳥取大学, 工学部, 助教授 (00243379)