钴源对Co/SBA-15催化乙醇水蒸气重整反应的影响
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摘要
以介孔分子筛SBA-15为载体,分别以硝酸钴、乙酸钴、硫酸钴和氯化钴为钴源,采用浸渍法合成了4种催化剂。采用XRD、N_2物理吸附-脱附等技术对催化剂的物相和结构进行表征,并研究了其在乙醇水蒸气重整反应中的催化特性。结果表明,以醋酸钴为钴源制备的催化剂经过焙烧后有C生成,以硫酸钴为钴源制备的催化剂经焙烧后很难生成钴的氧化物且较难还原,这都对催化剂的活性产生了一定的影响。另外,在反应温度为550℃、水醇体积比为10∶1的条件下对比发现,以硝酸钴为钴源制备的催化剂的催化效果最好,氢气选择性可达68.4%,乙醇转化率可达93.49%。
Four catalysts were synthesized by impregnation method using SBA-15 as carrier and cobalt dioxide,cobalt acetate,cobalt sulfate and cobalt chloride as cobalt sources,respectively.The phase and structure property of the catalysts were characterized by means of XRD and N_2 adsorption-desorption.The catalytic properties were studied by ethanol steam reforming reaction.Results show that after calcination the catalyst prepared with cobalt acetate has carbon deposition,while there is almost no cobalt oxide found in the catalyst prepared with cobalt sulfate after roasting and reducing,which has impact on the activity of catalysts.In addition,under the reaction conditions of 550 ℃ and the volume ratio of water to alcohol of 10∶1,cobalt nitrate is the best cobalt source,from the viewpoint of catalytic efficiency,showing hydrogen selectivity of 68.4% and ethanol conversion of 93.49%.
Four catalysts were synthesized by impregnation method using SBA-15 as carrier and cobalt dioxide,cobalt acetate,cobalt sulfate and cobalt chloride as cobalt sources,respectively.The phase and structure property of the catalysts were characterized by means of XRD and N_2 adsorption-desorption.The catalytic properties were studied by ethanol steam reforming reaction.Results show that after calcination the catalyst prepared with cobalt acetate has carbon deposition,while there is almost no cobalt oxide found in the catalyst prepared with cobalt sulfate after roasting and reducing,which has impact on the activity of catalysts.In addition,under the reaction conditions of 550 ℃ and the volume ratio of water to alcohol of 10∶1,cobalt nitrate is the best cobalt source,from the viewpoint of catalytic efficiency,showing hydrogen selectivity of 68.4% and ethanol conversion of 93.49%.
引文
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[5]刘利平,李静,马晓健,等.复合催化剂Ni-Cu/ZnO-TiO2催化乙醇水蒸气重整制氢[J].石油化工,2012,41(11):1245-1252.(LIU Liping,LI Jing,MA Xiaojian,et al.Hydrogen production by ethanol steam reforming over Ni-Cu/ZnO-TiO2composite catalyst[J].Petrochemical Technology,2012,41(11):1245-1252.)
[6]王晖,贺德华,董国利.Cu/ZrO2催化剂上乙醇水蒸气重整反应的研究Ⅰ催化剂性能及其制备参数的影响[J].燃料化学学报,2005,33(3):344-350.(WANGHui,HE Dehua,DONG Guoli.Steam reforming of ethanol over Cu/ZrO2catalystsⅠEffects of the preparation parameters of the catalysts[J].Journal of Fuel Chemistry and Technology,2005,33(3):344-350.)
[7]张利峰,王一平,黄群武.Ni-La/y-A12O3·SiO2催化剂上乙醇水蒸气重整制氢[J].化工进展,2008,27(10):1605-1623.(ZHANG Lifeng,WANG Yiping,HUANG Qunwu.Hydrogen production via ethanol steam reforming reaction over Ni-La/y-A12O3·SiO2catalysts[J].Chemical Industry and Engineering Progress,2008,27(10):1605-1623.)
[8]LLORCA,DE LA PISCINA P R,DALMON J A,et al.CO-free hydrogen from steam-reforming of bioethanol over ZnO-supported cobalt catalysts:Effect of the metallic precursor[J].Applied Catalysis B:Environmental,2003,43(4):355-369.
[9]胡伟涛,蔺丹丹,安霞.酸的种类和浓度对有序介孔二氧化硅形貌和孔结构的影响[J].材料导报,2015,29(8):33-37.(HU Weitao,LIN Dandan,AN Xia.Influences of sort and concentration of acid on morphology and pore structure of ordered mesoporous silica[J].Materials Review,2015,29(8):33-37.
[10]VILA-NETO C N,LIBERATORI J W C,DA SILVA A M,et al.Understanding the stability of Co-supported catalysts during ethanol reforming as addressed by in situ temperature and spatial resolved XAFS analysis[J].Journal of Catalysis,2012,287(3):124-137.
[11]詹金友,张耀兵,张璐璐,等.SbCl3/SBA-15的制备及催化合成二苯甲烷性能[J].石油学报(石油加工),2016,32(4):780-786.(ZHAN Jinyou,ZHANGYaobing,ZHANG Lulu,et al.Preparation and catalytic benzylation performance of SbCl3/SBA-15[J].Acta Petrolei Sinica(Petroleum Processing Section),2016,32(4):780-786.)
[12]WANG Yishuang,CHEN Mingqiang,YANG Zhonglian,et al.Bimetallic Ni-M(M=Co,Cu and Zn)supported on attapulgite as catalysts for hydrogen production from glycerol steam reforming[J].Applied Catalysis A,General,2018,550:214-227.