| 摘要: |
| 采用大豆油研磨法制备了Ni/C-SiO2系列催化剂,并用于CH4-CO2重整反应。通过XRD、TG-DTG、BET、H2-TPR、CO2-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Ni0,实现了煅烧还原一步制备中孔Ni基催化剂。CH4-CO2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CeO2、ZrO2、La2O3对催化剂性能的影响,结果表明,与Ni/C-SiO2催化剂相比,Ni-CeO2/C-SiO2、Ni-ZrO2/C-SiO2、Ni-La2O3/C-SiO2催化剂中Ni0的粒径降低了,Ni-CeO2/C-SiO2、Ni-La2O3/C-SiO2催化剂的反应活性提高了,反应后Ni-ZrO2/C-SiO2、Ni-La2O3/C-SiO2催化剂上的积炭减少了。助剂La2O3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-La2O3/C-SiO2催化剂进行CH4-CO2重整反应,总碳转化率达到了52%。 |
| 关键词: 研磨 Ni基催化剂 助剂 CH4-CO2重整 积炭 |
| DOI：10.3969/j.issn.1007-3426.2016.03.008 |
| 分类号:TE624.4+2 |
| 基金项目: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)。 |
|
| Preparation of Ni-based catalysts by one step of calcination and reduction and its application in CH4-CO2 reforming reaction |
|
Li Hangjie1, Shen Dongming1, He Yingluo2, Lyu Peiyi1, Xu Ding1, Gai Xikun1, Lyu Peng1, Lyu Chengxue1, Yang Ruiqin1
|
|
(1. School of Biological and Chemical Engineering, Zhejiang University of Science & Technology, Hangzhou 310023, China;2. Department of Applied Chemistry, University of Toyama, Toyama 930-8555, Japan)
|
| Abstract: |
| The Ni/C-SiO2 series catalysts were prepared by the method of soybean oil grinding, and were applied in the CH4-CO2 reforming reactions. These catalysts were characterized by the XRD, TG-DTG, BET, H2-TPR, CO2-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 Ni0 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 CH4-CO2 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 CeO2, ZrO2 and La2O3 on the catalyst properties were investigated. The results indicated that the particle diameter of the Ni0 in the Ni-CeO2/C-SiO2, Ni-ZrO2/C-SiO2 and Ni-La2O3/C-SiO2 catalysts was decreased, the reaction activity of the Ni-CeO2/C-SiO2 and Ni-La2O3/C-SiO2 catalysts was enhanced, and the carbon deposition on the Ni-ZrO2/C-SiO2 and Ni-La2O3/C-SiO2 was reduced after the reaction compared to these of the Ni/C-SiO2 catalyst. The promoter La2O3 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 CH4-CO2 reforming reaction using the Ni-La2O3/C-SiO2 catalyst. |
| Key words: grinding Ni-based catalyst promoter CH4-CO2 reforming carbon deposition |
