复合催化剂Ni-Cu/ZnO-TiO_2催化乙醇水蒸气重整制氢  

Hydrogen Production by Ethanol Steam Reforming over Ni-Cu/ZnO-TiO_2 Composite Catalyst

作　　者：刘利平[1] 李静[1] 马晓建[1] 陈俊英[1] 

机构地区：[1]郑州大学化工与能源学院,河南郑州450001

出　　处：《石油化工》2012年第11期1245-1252,共8页Petrochemical Technology

基　　金：国家十一五科技支撑计划项目(2007BAD66B04);河南省自然科学基础研究资助项目(2010A480005)

摘　　要：利用共沉淀法制备了Ni/TiO2,Ni/ZnO,Ni/ZnO-TiO2,Ni-Cu/ZnO-TiO2催化剂,活性组分Ni及Cu含量均为2%(w);对催化剂进行了BET,H2-TPR,XRD,SEM-EDS表征及乙醇水蒸气重整制氢性能评价。实验结果表明,在水与醇摩尔比13、反应温度300～550℃、液态空速23.8 h-1的反应条件下,ZnO及ZnO-TiO2负载的Ni催化剂有较好的催化性能,当反应温度高于450℃时,乙醇转化率均达90%以上。在450～550℃,Ni-Cu/ZnO-TiO2催化剂的氢产率最高、CO选择性较低且稳定性良好,550℃时Ni-Cu/ZnO-TiO2催化剂上最大氢产率为3.49 mol/mol(每mol反应乙醇生产的H2的物质的量)。表征结果显示,Ni/ZnO,Ni/ZnO-TiO2,Ni-Cu/ZnO-TiO2催化剂的活性组分分散良好;采用复合载体ZnO-TiO2及添加第二种活性组分Cu,改善了Ni-Cu/ZnO-TiO2催化剂的性能;反应后4种催化剂上均有丝状炭生成,但未出现明显的烧结与团聚现象。Ni/TiO2, Ni/ZnO, Ni/ZnO-TiO2 and Ni-Cu/ZnO-TiO2 catalysts with 2%（w） of Ni and 2%（w） of Cu were prepared by a co-precipitation method, and characterized by means of BET, H2-TPR, XRD and SEM-EDS. The catalytic performances of the catalysts in the steam reforming of ethanol（EtOH） for hydrogen production were evaluated. ZnO and ZnO-TiO2 supported Ni-based catalysts exhibited good catalytic performances under the conditions of n（H20） ： n（EtOH） 13, reaction temperature 300-500℃ and LHSV 23.8 h-1, the ethanol conversion can reach more than 90% at temperature highter than 450℃. The performance of Ni-Cu/ZnO-TiO2 catalyst is the best among the prepared catalysts, with low selectivity to CO, high hydrogen yield（H2 amount produced from 1 tool reacted EtOH） and stability in the temperature range of 450-550℃. The maximum hydrogen yield of 3.49 mol/mol can be achieved over the Ni-Cu/ZnO-Ti02 catalyst at 550℃. The active species on Ni/ ZnO, Ni/ZnO-TiO2 and Ni-Cu/ZnO-TiO2 catalysts disperse well, and the application of the composite support and the addition of Cu active species can improve the catalytic performance of Ni-Cu/ZnO- TiO2. Whisker carbon deposition on the used catalysts was observed without obvious sintering.

关 键 词：乙醇 水蒸气重整 制氢 镍基 复合催化剂 

分 类 号：TQ116.2[化学工程—无机化工]