Cu/ZnO/SBA-15催化剂的制备及碳酸酯加氢性能研究
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摘要
以Cu(NO_3)_2·3H_2O、Zn (NO_3)_2·6H_2O及SBA-15分子筛制备碳酸乙烯酯加氢制乙二醇和甲醇的Cu/ZnO/SBA-15催化剂,考察了制备方法(过量浸渍法、等体积浸渍法、旋转蒸发法和氨蒸法)对催化剂Cu/ZnO/SBA-15的影响及不同Cu/ZnO比对反应性能影响。研究发现,氨蒸法制备的催化剂负载量大,且分散性好,Cu、ZnO总负载量为20%,铜锌比为2∶1,反应性能最优,此时碳酸乙烯酯的转化率100%,甲醇的选择性69. 7%,乙二醇的选择性100%。
Cu( NO3)_2·3 H_2 O,Zn( NO_3)_2·6 H_2 O and SBA-15 molecular sieve to prepare the ethylene carbonate hydrogenation to make ethylene glycol and Cu/ZnO/SBA-15 catalysts. The influence of four catalyst preparation methods including impregnation,incipient wetness impregnation,rotary evaporation and ammonia evaporation on Cu/ZnO/SBA-15 catalysts and Cu/ZnO were investigated. The results shows that with ammonia evaporation method,the loading amount of copper on the supporter was large and the dispersion was good. The catalyst,with a total supporting amount of Cu and ZnO of 20%,Cu/ZnO ratio of2,shows best activity and selectivity. And the conversion of EC was 100% and the selectivity of methanol and ethylene glycol are 69. 7% and 100%,respectively.
Cu( NO3)_2·3 H_2 O,Zn( NO_3)_2·6 H_2 O and SBA-15 molecular sieve to prepare the ethylene carbonate hydrogenation to make ethylene glycol and Cu/ZnO/SBA-15 catalysts. The influence of four catalyst preparation methods including impregnation,incipient wetness impregnation,rotary evaporation and ammonia evaporation on Cu/ZnO/SBA-15 catalysts and Cu/ZnO were investigated. The results shows that with ammonia evaporation method,the loading amount of copper on the supporter was large and the dispersion was good. The catalyst,with a total supporting amount of Cu and ZnO of 20%,Cu/ZnO ratio of2,shows best activity and selectivity. And the conversion of EC was 100% and the selectivity of methanol and ethylene glycol are 69. 7% and 100%,respectively.
引文
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[4] Sakakura T,Choi J-C,Yasuda H. Transformation of carbon dioxide[J]. Chemical Reviews,2007,107(6):2365-2387.
[5] Han Z,Rong L,Wu J,et al. Catalytic hydrogenation of cyclic carbonates:a practical approach from CO2and epoxides to methanol and diols[J]. Angewandte Chemie International Edition,2012,51(52):13041-13045.
[6] Lian C,Ren F,Liu Y,et al. Heterogeneous selective hydrogenation of ethylene carbonate to methanol and ethylene glycol over a copper chromite nanocatalyst[J]. Chemical Communications,2015,51(7):1252-1254.
[7] Liu H,Huang Z,Han Z,et al. Efficient production of methanol and diols via the hydrogenation of cyclic carbonates using copper-silica nanocomposite catalysts[J].Green Chemistry,2015,17(8):4281-4290.
[8] Chen X,Cui Y,Wen C,et al. Continuous synthesis of methanol:heterogeneous hydrogenation of ethylene carbonate over Cu/HMS catalyst in fixed bed reactor system[J].Chemical Communications,2015,51(72):13776-13778.
[9] Yue H,Zhao Y,Zhao S,et al. A copper-phyllosilicate core-sheath nanoreactor for carbon-oxygen hydrogenolysis reactions[J]. Nature Communications,2013,4(9):2339-2346.
[10] Deng F,Li N,Tang S,et al. Evolution of active sites and catalytic consequence of mesoporous MCM-41 supported copper catalysts for the hydrogenation of ethylene carbonate[J]. Chemical Engineering Journal,2017,334:1943-1953.
[11] Zhou M,Shi Y,Ma K,et al. Nanoarray Cu/Si O2catalysts embedded in monolithic channels for the stable and efficient hydrogenation of CO2-derived ethylene carbonate[J]. Industrial&Engineering Chemistry Research,2018,57(6):1924-1934.
[12] An X,Ren F,Li J,et al. A highly active Cu/Zn O/Al2O3nanofiber catalyst for methanol synthesis through CO2and CO hydrogenation[J]. Chinese Journal of Catalysis,2005,26(9):729-730.
[13] Klier K. Methanol synthesis[J]. Advances in Catalysis,1982,31(10):243-313.
[14] Bulko J B,Herman R G,Klier K,et al. Optical properties and electronic interactions of microcrystalline copper/zinc oxide(Cu/Zn O)catalysts[J]. Journal of Physical Chemistry,2002,83(24):3118-3122.
[15] Frost J C. Junction effect interactions in methanol synthesis catalysts[J]. Nature,1988,334(6183):577-580.
[16] Idriss H,Hindermann J P,Kieffer R,et al. Characterization of dioxymethylene species over Cu-Zn catalysts[J].Journal of Molecular Catalysis,1987,42(2):205-213.
[17] Kiennemann A,Idriss H,Kieffer R,et al. Study of the mechanism of higher alcohol synthesis on copper-zinc oxide-aluminum oxide catalysts by catalytic tests,probe molecules,and temperature programmed desorption studies[J]. Industrial&Engineering Chemistry Research,1991,30(6):1130-1138.
[18] Ma X,Chi H,Yue H,et al. Hydrogenation of dimethyl oxalate to ethylene glycol over mesoporous Cu-MCM-41 catalysts[J]. AICh E Journal,2013,59(7):2530-2539.
[19] Robert Burch,Stanislaw E Golunski. The role of copper and zinc oxide in methanol synthesis catalysts[J]. Journal of the Chemical Society,Faraday Transactions,1990,86(15):2683-2691.
[20] Sebastian Kuld,Max Thorhauge,Hanne Falsig. Quantifying the promotion of Cu catalysts by Zn O for methanol synthesis[J]. Science,2016,352(6):969-974.
[21] Gong J,Yue H,Zhao Y,et al. Synthesis of ethanol via syngas on Cu/Si O2catalysts with balanced Cu0-Cu+sites[J]. Journal of the American Chemical Society,2012,134(34):13922-13925.
[22] Li F,Wang L,Han X,et al. Selective hydrogenation of ethylene carbonate to methanol and ethylene glycol over Cu/Si O2catalysts prepared by ammonia evaporation method[J]. International Journal of Hydrogen Energy,2017,42(4):2144-2156.
[23] Liang Fengchen,Ping Junguo,Ming Huaqiao,et al. Cu/Si O2catalysts prepared by the ammonia-evaporation method:Texture,structure,and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol[J]. Journal of Catalysis,2008,257(8):172-180.