Cu/SBA-15催化剂的改性及其催化酯加氢反应
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摘要
制备了不同助剂修饰改性的Cu/SBA-15催化剂,利用FTIR,XRD,H_2-TPR和XPS等表征手段对改性的催化剂进行了表征,并考察了催化剂在其他酯加氢反应中的性能。表征结果显示,B和Fe助剂可以增强Cu/SBA-15催化剂在酯加氢反应中的催化选择性,B改性的Cu/SBA-15催化剂可以降低其铜活性中心粒径,提高还原之后的Cu~+含量,从而有利于提高催化反应选择性,而Fe改性的Cu/SBA-15催化剂降低Cu粒径的同时,增加了Cu~0含量,并且对酯类也具有活化作用,从而提高了催化选择性。实验结果表明,B和Fe能够加强Cu/SBA-15催化剂的性能,并且Cu-Fe/SBA-15催化剂可广泛应用于丙二酸二乙酯,草酸二甲(乙)酯和乙酸乙酯加氢反应中。
Cu/SBA-15 catalysts were modified by adding different promoters.The catalysts were systematical characterized by FTIR,XRD,H_2-TPR and XPS methods,and their catalytic performances were tested in ester hydrogenation reactions.The results suggested the B and Fe-doped Cu/SBA-15 exhibit enhanced catalytic selectivity in ester hydrogenation reactions.Specifically,the B-doped Cu/SBA-15 catalyst can reduce the particle size of copper active center and increase the content of Cu~+ after reduction,which is beneficial to improve the selectivity of catalytic reaction However,the Fe-doped Cu/SBA-15 catalyst can reduce the particle size of copper,increase the content of Cu~0,and activate the esters,thereby improving the catalytic selectivity.The results sugges that modified Cu/SBA-15 catalysts show a better catalytic performance and can be wildly used in diethyl malonate,dimethyl/diethyl oxalate and ethyl acetate hydrogenation processes.
Cu/SBA-15 catalysts were modified by adding different promoters.The catalysts were systematical characterized by FTIR,XRD,H_2-TPR and XPS methods,and their catalytic performances were tested in ester hydrogenation reactions.The results suggested the B and Fe-doped Cu/SBA-15 exhibit enhanced catalytic selectivity in ester hydrogenation reactions.Specifically,the B-doped Cu/SBA-15 catalyst can reduce the particle size of copper active center and increase the content of Cu~+ after reduction,which is beneficial to improve the selectivity of catalytic reaction However,the Fe-doped Cu/SBA-15 catalyst can reduce the particle size of copper,increase the content of Cu~0,and activate the esters,thereby improving the catalytic selectivity.The results sugges that modified Cu/SBA-15 catalysts show a better catalytic performance and can be wildly used in diethyl malonate,dimethyl/diethyl oxalate and ethyl acetate hydrogenation processes.
引文
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[2]Bahmani M,Vasheghani Farahani B,Sahebdelfar S.Preparation of high performance nano-sized Cu/ZnO/Al2O3 methanol synthesis catalyst via aluminum hydrous oxide sol[J].Appl Catal,A,2016,520(12):178-187.
[3]Zhu Yifeng,Xiao Kong,Zhu Shanhui,et al.Construction of Cu/ZrO2/Al2O3 composites for ethanol synthesis:Synergies of ternary sites for cascade reaction[J].Appl Catal,B,2015,166/167(5):551-559.
[4]Chen C S,Lai Y T,Lai T W,et al.Formation of Cu nanoparticles in SBA-15 functionalized with carboxylic acid groups and their application in the water-gas shift reaction[J].ACSCatal,2013,3(4):667-677.
[5]Zhu Shanhui,Gao Xiaoqing,Zhu Yulei,et al.A highly efficient and robust Cu/SiO2 catalyst prepared by the ammonia evaporation hydrothermal method for glycerol hydrogenolysis to 1,2-propanediol[J].Catal Sci Technol,2015,5(2):1169-1180.
[6]Zhao Yujun,Li Siming,Wang Yue,et al.Efficient tuning of surface copper species of Cu/SiO2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol[J].Chem Eng J,2017,313(8):759-768.
[7]季东,李强,曾晓亮,等.草酸二甲酯气相选择性加氢铜基催化剂研究进展[J].工业催化,2017,25(7):1-8.
[8]李建辉,段新平,林海强,等.草酸二甲酯选择性加氢催化剂的研究进展[J].石油化工,2014,43(9):985-994.
[9]Zheng Jianwei,Zhou Junfu,Lin Haiqiang,et al.CO-mediated deactivation mechanism of SiO2-supported copper catalysts during dimethyl oxalate hydrogenation to ethylene glycol[J].JPhys Chem C,2015,119(24):13758-13766.
[10]穆仕芳,尚如静,穆士留,等,草酸二甲酯加氢制乙二醇铜基催化剂失活原因分析[J].工业催化,2015,23(2):98-102.
[11]Long Jinlong,Yue Hairong,Zhao Yujun,et al.Synthesis of ethanol via syngas on Cu/SiO2 catalysts with balanced Cu0-Cu+sites[J].J Am Chem Soc,2012,134(34):13922-13925.
[12]Wu Liubi,Li Bolong,Zhao Chen.Direct synthesis of hydrogen and dimethoxylmethane from methanol on Cu/SiO2 catalysts with optimal Cu+/Cu0 sites[J].ChemCatChem,2018,10(5):1140-1147.
[13]Wen Chao,Cui Yuanyuan,Yin Anyuan,et al.Remarkable improvement of catalytic performance for a new cobalt-decorated Cu/HMS catalyst in the hydrogenation of dimethyloxalate[J].ChemCatChem,2013,5(1):138-141.
[14]Ma Xinbin,Chi Hanwen,Yue Hairong,et al.Hydrogenation of dimethyl oxalate to ethylene glycol over mesoporous Cu-MCM-41 catalysts[J].AlChE J,2013,59(7):2530-2539.
[15]Yu Jintao,Cao Jingshun,Du Lihui,et al.Enhancement of diethyl malonate hydrogenation to 1,3-propanediol using mesoporous Cu/SBA-15 as catalyst[J].Appl Catal,A,2018,555(7):161-170.
[16]Zheng Xinlei,Lin Haiqiang,Zheng Jianwei,et al.Lanthanum oxide-modified Cu/SiO2 as a high-performance catalyst for chemoselective hydrogenation of dimethyl oxalate to ethylene glycol[J].ACS Catal,2013,3(3):2738-2749.
[17]Huang Ying,Ariga H,Zheng Xinlei,et al.Silver-modulated SiO2-supported copper catalysts for selective hydrogenation of dimethyl oxalate to ethylene glycol[J].J Catal,2013,307:74-83.
[18]Ding Tongmei,Tian Hengshui,Liu Jichang,et al.Highly active Cu/SiO2 catalysts for hydrogenation of diethyl malonate to1,3-propanediol[J].Chin J Catal,2016,37(4):484-493.
[19]Zheng Sainan,Zhu Kake,Li Wei,et al.Hydrogenation of dimethyl malonate to 1,3-propanediol catalyzed by a Cu/SiO2catalyst:The reaction network and the effect of Cu+/Cu0 on selectivity[J].New J Chem,2017,41(13):5752-5763.
[20]He Limin,Li Xiaoru,Lin Weiwei,et al.The selective hydrogenation of ethyl stearate to stearyl alcohol over Cu/Fe bimetallic catalysts[J].J Mole Catal A,2014,392(19):143-149.
[21]Neri G,Visco A M,Galvagno S,et al.Au/iron oxide catalysts:Temperature programmed reduction and X-ray diffraction characterization[J].Thermochim Acta,1999,329(1):39-46.
[22]Kohler M,Curry-Hyde H,Hughes A,et al.The structure of CuSiO2 catalysts prepared by the ion-exchange technique[J].JCatal,1987,108(2):323-333.