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Synthesis of complex metal cluster and creation of new synergy

Research Project

Project/Area Number 06453099
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 触媒・化学プロセス
Research InstitutionTohoku University

Principal Investigator

YAMADA Muneyoshi  Tohoku University, Faculty of Engineering, Professor, 工学部, 教授 (40091764)

Co-Investigator(Kenkyū-buntansha) OMATA Kohji  Tohoku University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (70185669)
Project Period (FY) 1994 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥7,800,000 (Direct Cost: ¥7,800,000)
Fiscal Year 1996: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1995: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1994: ¥5,500,000 (Direct Cost: ¥5,500,000)
KeywordsHydrodesulfurization / Cobalt-Molybdenum Catalyst / CyDTA / Synergy / Chelating Agent / NTA / EDTA / Alumina / ゼオライト / EXAFS / FT-IR / キレート錯体 / 複合金属クラスター / 定比組成 / コバルト-モリブデン触媒 / 相互促進効果
Research Abstract

For the purpose of uncovering the cause of synergy at molecular level, creation of new synergy was attempted using a complex metal cluster synthesized from chelating agent, metal complex and metal ion. We found the promoting effect of nitrilotriacetic acid (NTA)on hydrodesulfrization (HDS) activity of cobalt-molybdenum/alumina (Co-Mo/Al_2O_3) catalyst. Selective synthesis of synergistic site (active site) was enhanced when Co-Mo/Al_2O_3 catalysts were prepared by an impregnation method using NTA as chelating agent. In this study it was found that EDTA and trans-1,2-cyclohexane diamine-N,N,N^1, N^1-tetra-acetic acid (CyDTA) shows higher promoting effect. HDS activity of Cy-DTA-Co-Mo/Al_2O_3 was 70% higher than that of Co-Mo/Al_2O_3. Incorporation of these chelated complex into zeolite cage nor synthesis of complex chelate cluster in the cage was not confirmed.
In order to inverstigate the mechanism of activity promotion, IR spectra were measured to examine the behavior of adsorbed NO on … More the promoter and Mo sites. Mo K-edge EXAFS was also measured for clarify the local structure of active site. While HDS activity per CUS was increased, the effect of chelating agent vary greatly in dispersion of MoS2 cluster which is presumed to support the active site under reaction conditions, and in the number of coordinatively unsaturated site (CUS). It was suggested that highly dispersed cobalt is essential for formation of active site. Thus, it was demonstrated that dispersion of coblat is enhanced by chelating agent without changing local structure of active site.
HDS activity of nickel-molybdenum/alumina (Ni-Mo/Al_2O_3) and nickel-tungsten/alumina (Ni-W/Al_2O_3) was compared with that of Co-Mo/Al_2O_3. While in the case of Ni-Mo/Al_2O_3, HDS activity was not influenced by NTA nor CyDTA addition, that of Cy-DTA-Ni-W/Al_2O_3 was 60% higher than that of Ni-W/Al_2O_3. The result shows that combination of metal ion is one of an important factor for the promotion effect of chelating agent. Less

Report

(4 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • 1994 Annual Research Report
  • Research Products

    (49 results)

All Other

All Publications (49 results)

  • [Publications] 山田 宗慶: "深度脱硫を目指して" 触媒. 40. 34-35 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Hatanaka: "Hydrodesulfurization of Catalytic Cracked Gasoline.2.The Difference between HDS Active Site and Oefin Hydrogenation Active Site" Ind.Eng.Chem.Res.36. 5110-5117 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Koizumi: "Effect of sulfiding pressure on the formation of the Ni site on Ni-Mo/Al_2O_3 and Ni-W/Al_2O_3" Applied Surface Science. 121/122. 429-432 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Hiroshima: "High HDS activity of Co-Mo/Al_2O_3 modified by some chelates and their surface fine structures" Applied Surface Science. 121/122. 433-436 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Kasahara: "Relationship between HDS Activity and Mo Site Fine Structure of Variously Pretreated Co-Mo/Al_2O_3 and Mo/Al_2O_3" Applied Catalysis,B.Enviromental. 12. 225-235 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Kasahara: "Inhibiting Effect of H_2S on HDS Activity of CoMo-,NiMo-,andMo/Al_2O_3" Catalysis Today. 35. 59-64 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Koizumi: "In-situ FT-IR study of NO absorbed on Co-Mo/Al_2O_3 sulfided at high pressure(≦5.1MPa)" Studies in Surface Science and Catalysis. 106. 293-302 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 飯島 稔: "Co-Mo/Al_2O_3の水素化脱硫活性と表面構造に及ぼすV,Fe,Ni,Zn添加の影響" 石油学会誌. 40. 401-407 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 廣島 一崇: "硫化Co-Mo/Al_2O_3の脱硫活性と微細構造に及ぼすEDTAの添加効果" 石油学会誌. 40. 35-38 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 山田 宗慶: "クリーンフューエルを目指して-水素化精製触媒表面研究の最前線-" 表面. 35. 4-12 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] G.-Z.Bian: "Reaction stability and structure studies of sulfided K-MoO_3/γ-Al_2O_3 catalyst for the synthesis of mixed alcohol" Appled Catalysis,A:General. 144. 79-91 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Koizumi: "Effective Dispersion of Co in Co-Mo/Al_2O_3 Induced by High Pressure Sulfiding by Means of FT-IR Using NO as Surface Probe Molecule" Chemistry Letters. 815-816 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 清水 健博: "CoMo系脱硫触媒調整時におけるキレート剤の添加効果(第2報)-表面構造に対するNTA(ニトリロ三酢酸)の添加効果-" 石油学会誌. 39. 158-165 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 清水 健博: "Co-Mo系脱硫触媒調整時におけるキレート剤の添加効果-脱硫活性と表面組成に対するNTA(ニトリロ三酢酸)の添加効果" 石油学会誌. 38. 384-389 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 笠原 清司: "硫化Mo/Al_2O_3の水素化脱硫活性に及ぼすFe,Co,Niの添加効果(第2報)表面構造の変化と助触媒効果" 石油学会誌. 38. 439-446 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 笠原 清司: "硫化Mo/Al_2O_3の水素化脱硫活性に及ぼすFe,Co,Niの添加効果(第1報)硫化水素の抑制作用と助触媒効果" 石油学会誌. 38. 345-352 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 笠原 清司: "Co-Mo/Al_2O_3の水素化脱硫活性および表面構造に及ぼす各種前処理の影響" 石油学会誌. 38. 81-87 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M,Yamada: "Toward Deep Hydrodesulfrization" Shokubai. 40. 34-35 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Hatanaka: "Hydrodesulfurization of Catalytic Cracked Gasoline.2. The Difference between HDS Active Site and Oefin Hydrogenation Active Site" Ind.Eng.Chem.Res.36. 5110-5117 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Koizumi: "Effect of sulfiding pressure on the formation of the Ni site on Ni-Mo/Al_2O_3 and Ni-W/Al_2O_3" Applied Surface Science. 121/122. 429-432 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Hiroshima: "High HDS activity of Co-Mo/Al_2O_3 modified by some chelates and their surface fine structures" Applied Surface Science. 121/122. 433-436 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Kasahara: "Relationship between HDS Activity and Mo Site Fine Structure of Variously Pretreated Co-Mo/Al_2O_3 and Mo/Al_2O_3" Applied Catalysis, B.Enviromental. 12. 225-235 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Kasahara: "Inhibiting Effect of H_2S on HDS Activity of CoMo-, NiMo-, and Mo/Al_2O_3" Catalysis Today. 35. 59-64 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Koizumi: "In-situ FT-IR study of NO adsorbed on Co-Mo/Al_2O_3 sulfided at high pressure (*5.1MPa)" Studies in Surface Sci.and Cat.106. 293-302 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Iijima: "The Effects of V,Fe, Ni, Zn on Hydrodesulfurization (HDS) Activity and Surface Structure of Co-Mo/Al_2O_3" Sekiyu Gakkaishi. 40. 401-407 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K.Hiroshima: "Effects of EDTA on Hydrodesulfurization Activity and Fine Structure of Sulfided Co-Mo/AlX_2OX_3" Sekiyu Gakkaishi. 40. 35-38 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] M.Yamada: "Toward Clean Fuel-surface Science Frontier of Hydrotreating Catyalyst" Surface. 35. 4-12 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] G.-Z.Bian: "Reaction stability and structure studies of sulfided K-MoO_3/gamma-Al_2O_3 catalyst for the synthesis of mixed alcohol" Appled Catalysis, A : General. 144. 79-91 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] N.Koizumi: "Effective Dispersion of Co in Co-Mo/Al_2O_3 Induced by High Pressure Sulfiding by Means of FT-IR Using NO as Surface Probe Molecule" Chemistry Letters. 815-816 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Shimizu: "Effects of Chelating Agents as Additives on Preparation of Co-Mo Hydrodesulfurization Catalysts (Part2) Effect of Nitrilotriacetic Acid Addition on Surface Structure" Sekiyu Gakkaishi. 39. 158-165 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Shimizu: "Effects of Chelating Agents as Additives on Preparation of Co-Mo Hydrodesulfurization Catalysts-The Effect of NTA (nitrilotriacetic acid) Addition on Hydrodesulfurization Activity and Surface Composition" Sekiyu Gakkaishi. 38. 384-389 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Kasahara: "Effects of Fe, Co, Ni on Hydrodesulfurization Activity of Sulfided Mo/Al_2O_3 (Part2) Relationship between Change of Surface Structure and Promoting Effect" Sekiyu Gakkaishi. 38. 439-446 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Kasahara: "Effects of Fe, Co, Ni on Hydrodesulfurization Activity of Sulfided Mo/Al_2O_3 (Part1) Relationship between Inhibiting Effect of HX_2S and Promoting Effect" Sekiyu Gakkaishi. 38. 345-352 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Kasahara: "Effects of Catalyst Pretreatments on Hydrodesulfurization Activity and Surface Structure of Co-Mo/Al_2O_3" Sekiyu Gakkaishi. 38. 81-87 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] K. Hiroshima: "High HDS Activity of Co-Mo/Al2O3 Modified by Some Chelates and Their Surface Fine Structures" Applied Surface Science. in press.

    • Related Report
      1996 Annual Research Report
  • [Publications] Seiji Kasahara: "Relationship between HDS Activity and Mo Site Fine Structure of Variously Pretreated Co-Mo/Al_2O_3 and Mo/Al_2O_3" Applied Catalysis, B. Enviromental. in press.

    • Related Report
      1996 Annual Research Report
  • [Publications] 廣島一崇: "硫化Co-Mo/Al_2O_3の脱硫活性と微細構造に及ぼすEDTAの添加効果" 石油学会誌. 40(1). 35-38 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Naoto Koizumi: "Effective Dispersion of Co in Co-Mo/Al_2O_3 Induced by High Pressure Sulfiding by Means of FT-IR Using NO as Surface Probe Molecule" Chemistry Letters. 815-816 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Seiji Kasahara: "Inhibiting Effect of H_2S on HDS Activity of CoMo-,NiMo-, and Mo/Al_2O_3" Catalysis Today. (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 清水健博: "CoMo系脱硫触媒調製時におけるキレート剤の添加効果(第2報)-表面構造に対するNTA(ニトリロ三酢酸)の添加効果-" 石油学会誌. 39(2). 158-165 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Naoto Koizumi: "In-situ FT-IR/DRA study of NO adsorbed on Co-Mo/Al_2O_3 sulfided at high pressure (≦5.1MPa)" Elsevier, Studies in surface science and catalysis volume 106 HYDROTREATMENT AND HYDROCRACKING OF OIL FRACTIONS, 10 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] 山田 宗慶: "クリーンフューエルを目指して-水素化精製触媒表面研究の最前線-" 表面, 9 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] 笠原 清司: "Co-Mo/Al_2O_3の水素化脱硫活性および表面構造に及ぼす各種前処理の影響" 石油学会誌. 38. 81-87 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 笠原 清司: "硫化Mo/Al_2O_3の水素化脱硫活性に及ぼすFe,Co,Niの添加効果(第1報)硫化水素の抑制作用と助触媒効果" 石油学会誌. 38. 345-352 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 清水 健博: "Co-Mo系脱硫触媒調製時におけるキレート剤の添加効果-脱硫活性と表面組成に対するNTA(ニトリロ三酢酸)の添加効果" 石油学会誌. 38. 384-389 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 笠原 清司: "硫化Mo/Al_2O_3の水素化脱硫活性に及ぼすFe,Co,Niの添加効果(第2報)表面構造の変化と助触媒効果" 石油学会誌. 38. 439-446 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 笠原 清司: "Co-Mo/Al_2O_3の水素化脱硫活性および表面構造に及ぼす各種前処理の影響" 石油学会誌. 38. 81-87 (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] 高田 岳志: "コバルト系酸化物を用いるCOとH_2混合ガスの触媒酸化" 日本化学会誌. (9). 793-799 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] 佐藤 康之: "6族金属超微粒炭化物の調製と触媒作用(第1報)" 石油学会誌. 37. 514-521 (1994)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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