无机材料学报 ›› 2019, Vol. 34 ›› Issue (8): 811-816.DOI: 10.15541/jim20180356

• 研究论文 • 上一篇    下一篇

铁助剂对乙酸自热重整制氢用CoxAl3FeyOm±δ催化剂的影响

王巧,周庆,安爽,杨浩,黄利宏()   

  1. 成都理工大学 材料与化学化工学院, 成都 610059
  • 收稿日期:2018-08-13 修回日期:2018-11-22 出版日期:2019-08-20 网络出版日期:2019-04-12
  • 作者简介:王 巧(1994-), 女, 硕士研究生. E-mail: <email>17736869331@163.com</email>
  • 基金资助:
    四川省科技计划项目(2019YFH0181);四川省科技计划项目(2015HH0013)

Effect of Fe on CoxAl3FeyOm±δ Catalysts for Hydrogen Production by Auto-thermal Reforming of Acetic Acid

WANG Qiao,ZHOU Qing,AN Shuang,YANG Hao,HUANG Li-Hong()   

  1. College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China
  • Received:2018-08-13 Revised:2018-11-22 Published:2019-08-20 Online:2019-04-12

摘要:

生物质转化获得的生物质油可作为重要的制氢原料, 选取生物质油的主要成分乙酸作为模型化合物, 开展了乙酸自热重整催化制氢研究。采用共沉淀法制备了铁促进的类水滑石型钴基催化剂, 用于乙酸自热重整制氢体系, 并利用XRD、H2-TPR、N2低温物理吸脱附、TG等表征手段对催化剂进行表征测试。结果表明: 通过共沉淀法获得了以类水滑石结构为前驱体的(Co/Fe)xAl2CO3(OH)y·zH2O物相; 该前驱体经焙烧后获得的氧化物, 其主要物相为氧化铝担载的尖晶石结构, 包括CoAl2O4、Co3O4、Fe3O4、FeAl2O4等, BJH模型计算显示CoxAl3FeyOm±δ催化剂形成了介孔结构, 其中Co0.45Al3Fe0.4O5.55±δ孔径分布集中在4 nm左右, H2-TPR及XRD测试显示添加助剂Fe提升了催化剂还原度, 并在还原过程中形成了CoFe合金; 所获催化剂在乙酸自热重整反应中, 氢气产率达到 2.72 mol-H2/mol-HAc, 并保持稳定。表征结果还显示, 该催化剂在反应中结构稳定, CoFe合金稳定存在, 并未出现积炭, 表明催化剂具有抗氧化、抗积碳的特点。

关键词: 钴铁合金, 类水滑石, 钴基催化剂, 氢能

Abstract:

Bio-oil obtained from biomass can be used as an important raw material for hydrogen production. In this work, acetic acid (HAc) from bio-oil was selected as the model compound to produce hydrogen via auto-thermal reforming (ATR). Fe-promoted Co-based hydrotalcite-like CoxAl3FeyOm±δ catalysts were prepared by co-precipitation method and characterized by XRD, N2 physisorption, H2-TPR and TG to study the relationship between the catalytic performance and structure within these catalysts. The characterization results show that hydrotalcite-like structure of (Co/Fe)xAl2CO3(OH)y·zH2O were obtained by co-precipitation, then transformed to alumina supported spinel structures, including CoAl2O4, Co3O4, Fe3O4, and FeAl2O4, after calcination. BJH analysis indicated that within these calcined CoxAl3FeyOm±δ catalysts, there were mesoporous structures, in which the Co0.45Al3Fe0.4O5.55±δ centered structure with pore size distribution 4 nm. As suggested by H2-TPR and XRD, the reducibility of Co metal was enhanced with the Fe promoter, and there were CoFe alloys formed after reduction. In the stability test, the hydrogen yield reached 2.72 mol-H2/mol-HAc and remained stable, meanwhile, the CoFe alloy was also stable and no carbon deposit was detected after reaction, indicating that there was high resistance to oxidation and coking within Fe-promoted CoxAl3FeyOδ catalysts.

Key words: CoFe alloy, hydrotalcite-like material, Co-based catalyst, hydrogen energy

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