中文摘要：

首先采用柠檬酸络法制备了系列MxOy／CeO2-ZrO2（M=Cu，Ba和Al）固溶体载体，然后浸渍活性组分Ni，制得系列Ni／MxOy／CeO2-ZrO2复合催化剂。考察了掺杂助剂元素（Cu，Ba和Al）对CeO2-ZrO2固溶体结构和负载Ni催化剂的甲烷部分氧化生成合成气催化性能的影响。采用氮气物理吸附，X射线粉末衍射（XRD），氢-程序升温还原（H2-TPR），扫描电子显微镜（SEM），氨-程序升温脱附（NH3-TPD）和热重（TG）等技术对反应前后催化剂的理化性质进行表征。甲烷部分催化氧化表明，催化剂的活性顺序为Ni／Al203／CeO2-ZrO2〉Ni／BaO／CeO2-ZrO2〉Ni／CeO2-ZrO2〉Ni／CuO／CeO2-ZrO2。催化剂表征结果表明，掺杂助剂元素后复合载体的主要结构仍然为CeO2-ZrO2固溶体；掺杂的助剂Ba和Al能和CeO2-ZrO2固溶体产生较强的相互作用，生成MxOy／CeO2-ZrO2三元复合固溶体载体，并使复合载体的比表面积增大，其中掺杂Al的效果最为明显，能使CeO2-ZrO2固溶体载体颗粒细化，表面结构更丰富，从而有利于活性组分Ni的分散；虽然掺杂Al使载体的表面酸性略有增强，但是Ni／Al203／CeO2-ZrO2复合催化剂仍表现了最高的活性和良好的稳定性。掺杂助剂Cu后，Cu与活性组分Ni之间的“氢溢流”效应增强了催化剂中Ni的还原性，生成的Cu^0与Ni^0之间产生的相互作用导致CuNi合金的生成，减少了NiU活性中心的数目，导致该催化剂对甲烷部分氧化的活性下降。

英文摘要：

A series of MxOy/CeO2-ZrO2 （ M = Cu, Ba and Al） solid solution composite supports were prepared by citric acid complex method, and Ni active component was loaded over the obtained supports by impregnating method to produce Ni/MxOy/CeOE-ZrO2 composite catalysts. The effects of promoter elements （ Cu, Ba and Al） doped into CeO2-ZrO2 solid solution on its texture structure and the catalytic performance of supported Ni catalysts in methane partial oxidation to syngas were investigated. N2 physical adsorption, X-ray powder diffraction （XRD）, hydrogen temperature-programmed reduction （H2-TPR） , scanning electron microscopy （SEM）, ammonia temperature-programmed desorption （NH3-TPD） and thermogravimetry （TG） analysis were used to characterize the physicochemical properties of the fresh and reacted catalysts. The methane partial oxidation test showed that the activity of the catalysts followed the or- der of Ni/AI203/CeO2-ZrO2 〉 Ni/BaO/CeO2-ZrO2 〉 Ni./CeO2-ZrO2 〉 Ni./CnO/CeO2-ZrO2. The characterisation results revealed that after the doping of promoters, the composite supports still kept the structure of CeO2-ZrO2 solid solution. The doping of Ba and Al pro- duced strong interactions between the promoter and CeO2 -2O2 solid solution to generate the ternary composite solid solution support and increase the surface area of the composite support. Al doping produced more obvious effects on the increase of surface area and decreased the particle size of the support, which benefited the dispersion of active component Ni. Although, Al doping slightly increased the surface acidity of the support, Ni/Al203/CeOE-ZrO2 exhibited the highest activity and good stability. Cu doping produced H2 spillover which promoted the reduction of Ni. The interaction between the produced Cu^0 and Ni^0 could generate coppernickel alloy. The formation of copper-nickel alloy decreased the number of Ni^0 active sites, thus reduced the activity in catalytic methane partial oxidation.