铁助剂对乙酸自热重整制氢用CoxAl3FeyOm±δ催化剂的影响

doi:10.15541/jim20180356

摘要/Abstract

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Co_xAl₃Fe_yO_m_±_δ催化剂形成了介孔结构, 其中Co_0.45Al₃Fe_0.4O_5.55±_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 Co_xAl₃Fe_yO_m_±_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 Co_xAl₃Fe_yO_m_±_δ catalysts, there were mesoporous structures, in which the Co_0.45Al₃Fe_0.4O_5.55±_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 Co_xAl₃Fe_yO_m±_δ catalysts.

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

中图分类号:

TQ13

王巧, 周庆, 安爽, 杨浩, 黄利宏. 铁助剂对乙酸自热重整制氢用Co_xAl₃Fe_yO_m±δ催化剂的影响[J]. 无机材料学报, 2019, 34(8): 811-816.

WANG Qiao, ZHOU Qing, AN Shuang, YANG Hao, HUANG Li-Hong. Effect of Fe on Co_xAl₃Fe_yO_m_±_δ Catalysts for Hydrogen Production by Auto-thermal Reforming of Acetic Acid[J]. Journal of Inorganic Materials, 2019, 34(8): 811-816.

图/表 7

图1 Co基催化剂的乙酸自热重整制氢活性测试结果

Fig. 1 Catalytic performance for hydrogen production via ATR of HAc (A) CAF-0; (B) CAF-10; (C) CAF-15; (D) CAF-20

图2 Co基催化剂前驱体(A)和氧化物(B)的XRD图谱

Fig. 2 XRD patterns of Co-based catalysts (A) precursors and (B) oxides

图3 Co基催化剂氧化物的低温氮气吸脱附曲线(A)和孔径分布图(B)

Fig. 3 N2 adsorption-desorption isotherms (A) and Barrett- Joyner-Halenda pore size distribution curves (B) of the calcined catalysts

表1 催化剂氮吸附测试数据

Table 1 Data of N2 adsorption-desorption tests

Catalysts	S_BET/(m²·g^-1)	V_BJH/(cm³·g^-1)	D_BJH/nm
CAF-0	143.7	0.36	10.0
CAF-10	182.8	0.38	8.3
CAF-15	142.6	0.57	16.0
CAF-20	132.5	0.46	13.8

图4 还原后催化剂的XRD图谱(A)和催化剂氧化物的H2-TPR曲线(B)

Fig. 4 XRD patterns of the reduced catalysts (A) and H2-TPR profiles of the calcined catalysts(B)

图5 Co基催化剂乙酸自热重整反应10 h后产物的XRD图谱

Fig. 5 XRD patterns of the spent catalysts after 10 h ATR of HAc

图6 Co基催化剂经乙酸自热重整反应10 h后的TG-DTA曲线

Fig. 6 TG-DTA profiles of the spent catalysts after 10 h ATR of HAc (A) CAF-0; (B) CAF-10; (C) CAF-15; (D) CAF-20

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铁助剂对乙酸自热重整制氢用Co_xAl₃Fe_yO_m±δ催化剂的影响

Effect of Fe on Co_xAl₃Fe_yO_m_±_δ Catalysts for Hydrogen Production by Auto-thermal Reforming of Acetic Acid

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