Co-Mo水素化脱硫モデル硫化物触媒の調製とキャラクタリゼーション Preparation and Characterization of Co-Mo Model Sulfide Catalysts for Hydrodesulfurization

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Abstract

高活性水素化脱硫 (HDS) 触媒の開発は石油工業における喫緊の課題の一つである。高活性HDS触媒の合理的開発のためには, 分子レベルでのHDS触媒の本質に関するより深いキャラクタリゼーションと理解が重要である。その目的のための我々の手法は, 実用触媒につきものの不均一性に基づく困難を克服するため, 金属カルボニルを用いてモデル触媒を構築することにある。新しい手法の一つは, ゼオライト細孔内に構造の規定された均一なMo, Co, Co-Mo硫化物クラスターの合成である。ゼオライト細孔内Mo硫化物ダイマークラスターMo<SUB>2</SUB>S<SUB>4</SUB>が生成し, その局所構造はホストゼオライトの組成に依存する。チオフェンのHDS反応に対しCo-Mo間に複合効果の発現を示す, 熱的に安定なCo<SUB>2</SUB>Mo<SUB>2</SUB>S<SUB>6</SUB>二元系硫化物クラスターはキュバン型構造を持つ。Co硫化物クラスターの比活性はゼオライトに依存する。Mo<SUB>2</SUB>S<SUB>4</SUB>やMoS<SUB>2</SUB>クラスター上でのセレノフェンの脱セレン反応は, EXAFSの結果と合わせ, HDS反応の微視的反応機構を示唆する。実用HDS触媒の本質を理解するため, Co-Mo硫化物触媒のさらに実際的なモデル化, すなわち酸化物上にCoMoS相の選択的な調製法を確立した。Al<SUB>2</SUB>O<SUB>3</SUB>, TiO<SUB>2</SUB>, ZrO<SUB>2</SUB>担持のCoMoS相間には担体の効果は見られないが, SiO<SUB>2</SUB>担持のCoMoS相は高い比活性を示す。モデル触媒でのCoMoS相の量から, NOを吸着するCoMoS相の割合を決定し, CoMoS相の新しい構造モデルを提案した。Co(Ni)-Mo(W) 触媒の最大潜在HDS活性についてCo(CO)<SUB>3</SUB>NOをプローブ分子として評価した。モデル触媒は, 触媒調製や添加物効果, 触媒構造, および微視的反応機構や構造と活性の関係のようなHDS触媒の基礎的側面について重要な情報を与える。

Development of highly active hydrodesulfurization (HDS) catalysts is one of the most urgent problems in the petroleum industry. Better characterization and understanding of the nature of HDS catalysts on the molecular scale are of great importance for the rational design of highly active HDS catalysts. Our approaches for this purpose involve the fabrication of model catalysts using metal carbonyls to overcome the difficulties caused by the heterogeneity of practical catalysts. One of our new approaches uses the synthesis of intrazeolite homogeneous Mo, Co and Co-Mo sulfide clusters with well defined structures. The local structure of intrazeolite Mo sulfide dimer clusters, Mo<SUB>2</SUB>S<SUB>4</SUB>, depends on the composition of the host zeolite. Thermally stabilized Co<SUB>2</SUB>Mo<SUB>2</SUB>S<SUB>6</SUB> binary sulfide clusters, which show catalytic synergies between Co and Mo for thiophene HDS, with a thiocubane type structure are formed in zeolite. The intrinsic HDS activity of Co sulfide clusters depends on the host zeolite. The hydrode-selenium reaction of selenophene, combined with an extended X-ray absorption fine structure (EXAFS) study, over Mo<SUB>2</SUB>S<SUB>4</SUB> and MoS<SUB>2</SUB> clusters suggests a microscopic HDS reaction mechanism. More practical modeling of Co-Mo sulfide catalysts using a selective preparation method of CoMoS phases supported on refractory oxides is established to understand the nature of practical HDS catalysts. No effects of the support are found with the CoMoS phase supported on Al<SUB>2</SUB>O<SUB>3</SUB>, TiO<SUB>2</SUB> and ZrO<SUB>2</SUB>, whereas the CoMoS phase supported on SiO<SUB>2</SUB> shows a higher intrinsic activity. The fraction of the CoMoS phase accessible to NO adsorption is elucidated, based on the number of the CoMoS phase in the model catalyst, suggesting a new model of the CoMoS structure. The maximum potential HDS activity of Co(Ni)-Mo(W) catalysts is evaluated by using Co(CO)<SUB>3</SUB>NO as a probe molecule. Such model catalysts provide important information about the effects of the catalyst preparation and additives, the catalyst structure and the fundamental aspects of HDS catalysts such as microscopic reaction mechanisms and structure-reactivity relationship.

Journal

  • Journal of the Japan Petroleum Institute

    Journal of the Japan Petroleum Institute 46(6), 343-358, 2003-11-01

    The Japan Petroleum Institute

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Codes

  • NII Article ID (NAID)
    130000066050
  • NII NACSIS-CAT ID (NCID)
    AA11590615
  • Text Lang
    ENG
  • Article Type
    REV
  • ISSN
    13468804
  • Data Source
    CJP  J-STAGE 
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