成果報告書詳細
管理番号20110000000200
タイトル*平成21年度中間年報 平成21~23年度「グリーン・サステイナブルケミカルプロセス基盤技術開発/副生ガス高効率分離・精製プロセス基盤技術開発/多孔性金属錯体を利用したCO2の高効率分離・精製プロセスの基盤技術開発」
公開日2011/5/3
報告書年度2009 - 2009
委託先名国立大学法人京都大学 大学共同利用機関法人自然科学研究機構分子科学研究所 株式会社クラレ 昭和電工株式会社 東洋紡績株式会社 昭栄化学工業株式会社 財団法人化学技術戦略推進機構
プロジェクト番号P09010
部署名環境技術開発部
和文要約和文要約等以下本編抜粋:1.研究開発の内容及び成果等 1-1.まえがき 本プロジェクト「多孔性金属錯体を利用したCO2の高効率分離・精製プロセスの基盤技術開発(委託)」は、高純度、低コスト、低エネルギーで精製できる革新的な吸着材料(多孔性金属錯体、以下、PCPと略す)の開発と濃縮された副生ガスを有用な化学品に転換できるクリーンなプロセスを確立するための基盤技術の開発を目標とし、国立大学法人京都大学、大学共同利用機関法人自然科学研究機構分子科学研究所、株式会社クラレ、昭和電工株式会社、東洋紡績株式会社、昭栄化学工業株式会社及び財団法人化学技術戦略推進機構とが共同で推進している。
英文要約Regarding to the CO2 separation from N2 gas, we synthesized over 50 kinds of PCP compounds and investigated their gas adsorption property. Single phase gas adsorption isotherm and mixture gas flow measurement elucidated that the two-dimensional flexible PCP frameworks are suitable for capture of CO2 gas from N2 mixture. Especially the framework which represented large structural transformation between closed phase to open phase showed high separation ability. The separation ability was also available for the separation of CO2/CH4. Large transformation of the structure allowed only CO2 to pass into the framework and then we observed high selectivity on CO2/CH4 in both equilibrium and flow adsorption systems. In terms of CO2/C2H4, instead of the flexible type of PCP, the structures containing the open metal site (or unsaturated metal site) were appropriate for selective binding of C2H4 over CO2. The mechanism has not been cleared, the Lewis acidic character of open metal site would contribute to the separation.
For siloxane-D4 capture, we employed various types of PCP frameworks having high surface area and high thermal/chemical stability. We chose five PCP frameworks and checked the siloxane-D4 uptake at room temperature. The frameworks with three-dimensional pore with around 1 nm of pore diameter represented high capacity for siloxane-D4 from low pressure region and pore dimension and high BET surface area would be important for effective adsorption for siloxane-D4. Affinities for water were also studied and two compounds among the five samples had been elucidated to be higher hydrophobicity than typical activated carbon. It is significant for application of capture of siloxane-D4 from high humid combustion gas.
For the project of CO2 conversion by PCP hybridized catalysts, initially we designed and developed an apparatus for a spray thermal reaction in order to synthesize PCP compounds with large scale and low cost performance or PCP-catalytic composites in significant quantities. The powder X-ray diffraction pattern of the sample preliminary obtained using the apparatus represented characteristic pattern for coordination polymer and the TGA measurement suggested the existence of porous framework. The results indicates the possibility of creating the various PCP compounds by use of gas-phase direct reaction.
In order to develop PCP-catalytic composites for a high-efficiency CO2 conversion, it is necessary to prepare a PCP catalyst having high CO2 adsorption capacity, high thermal and electrochemical stabilities. We have prepared a PCP-catalytic composite by liquid phase mixing procedure and performed STEM-EDS mapping to investigate the distribution state of composite in PCP matrix. The mapping images revealed that PCP and the catalysts species are homogeneously dispersed at the molecular scale and the approach is suitable to fabricate the well-dispersed PCP-catalysis composites. The electrochemical stability of several PCPs were investigated and we chose some frameworks having enough stability for hybridization of molecular catalysis.
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