煅烧还原一步制备Ni基催化剂及在CH_4-CO_2重整反应中的应用  

Preparation of Ni-based catalysts by one step of calcination and reduction and its application in CH_4-CO_2 reforming reaction

作　　者：李航杰 申东明[1] 何英洛 吕佩倚 徐钉[1] 盖希坤[1] 吕鹏[1] 吕成学[1] 杨瑞芹[1] 

机构地区：[1]浙江科技学院生物与化学工程学院 [2]日本国立富山大学应用化学科

出　　处：《石油与天然气化工》2016年第3期36-43,共8页Chemical engineering of oil & gas

基　　金：浙江省自然科学基金"室温固相研磨法制备铜基催化剂及其用于CO2低温合成甲醇新工艺中的研究"(LY14B030004);国家自然科学基金项目"合成气一段法制备LPG的新型双层核壳结构胶囊催化剂的构建与性能调控"(21528302);浙江省公益技术应用研究计划项目"农业固废新型炭化技术及土壤水体修复剂研发在土壤修复中的应用"(2015C33006);浙江省公益技术应用研究计划项目"新型双提升管沼气自热重整制生物质基合成气工艺关键技术研究"(2015C32019);2015年浙江省新苗人才计划项目"CH4-CO2重整催化剂的研究"(2015R415037)

摘　　要：采用大豆油研磨法制备了Ni/C-SiO_2系列催化剂,并用于CH_4-CO_2重整反应。通过XRD、TG-DTG、BET、H_2-TPR、CO_2-TPD等对催化剂进行了物理性能表征,利用固定床连续反应对催化剂进行了催化性能测试。结果表明,研磨法制得的催化剂前驱体在惰性气氛N2中煅烧后,催化剂上的镍元素全部转变成了Ni^0,实现了煅烧还原一步制备中孔Ni基催化剂。CH_4-CO_2重整反应后的催化剂上存在两种炭,一种是催化剂制备时残留的碳源炭,另一种是重整反应过程中产生的可致催化剂失活的积炭。考察了助剂CeO_2、ZrO_2、La_2O_3对催化剂性能的影响,结果表明,与Ni/C-SiO_2催化剂相比,Ni-CeO_2/C-SiO_2、Ni-ZrO_2/C-SiO_2、Ni-La_2O_3/C-SiO_2催化剂中Ni^0的粒径降低了,Ni-CeO_2/C-SiO_2、Ni-La_2O_3/C-SiO_2催化剂的反应活性提高了,反应后Ni-ZrO_2/C-SiO_2、Ni-La_2O_3/C-SiO_2催化剂上的积炭减少了。助剂La_2O_3不仅提高了催化剂活性,而且降低了催化剂上的积炭量,使用Ni-La_2O_3/C-SiO_2催化剂进行CH_4-CO_2重整反应,总碳转化率达到了52%。The Ni/C-SiO_2 series catalysts were prepared by the method of soybean oil grinding,and were applied in the CH_4-CO_2 reforming reactions.These catalysts were characterized by the XRD,TG-DTG,BET,H_2-TPR,CO_2-TPD and chemical properties of the catalysts were measured by the fixed bed continuous reactions.The results showed that the nickel elements in the catalyst were fully transformed into Ni^0 after calcining in inert atmosphere N2 for catalyst precursor prepared by grinding method,thus realizing the preparation of the mesoporous Ni-based catalysts by one-step of the calcination and the reduction.There were two types of carbon on the catalyst after the CH_4-CO_2 reforming reactions,one was the residual carbon source in the prepared catalyst,and another causing catalyst deactivation was the carbon deposition produced in the process of the reforming reaction.The influences of the promoters,such as CeO_2,ZrO_2 and La_2O_3 on the catalyst properties were investigated.The results indicated that the particle diameter of the Ni^0 in the Ni-CeO_2/C-SiO_2,NiZrO_2/C-SiO_2 and Ni-La_2O_3/C-SiO_2 catalysts was decreased,the reaction activity of the Ni-CeO_2/CSiO_2 and Ni-La_2O_3/C-SiO_2 catalysts was enhanced,and the carbon deposition on the Ni-ZrO_2/C-SiO_2 and Ni-La_2O_3/C-SiO_2 was reduced after the reaction compared to these of the Ni/C-SiO_2 catalyst.The promoter La_2O_3 not only improved the activity of the catalyst,but also reduced the amount of the carbon deposition on the catalyst.The total carbon conversion reached 52% for the CH_4-CO_2 reforming reaction using the Ni-La_2O_3/C-SiO_2 catalyst.

关 键 词：研磨 NI基催化剂 助剂 CH4-CO2重整 积炭 

分 类 号：TE624[石油与天然气工程—油气加工工程]