Methane chemical looping reforming over cordierite-loaded Fe/Ce oxygen carriers prepared by ball milling

doi:10.16085/j.issn.1000-6613.2023-2062

Abstract

Abstract:

In this paper, a series of cordierite-loaded Fe/Ce composite oxygen carriers were prepared by ball milling method and the performance of the composite oxygen carriers for methane chemical looping reforming was evaluated on a fixed-bed reactor. The effects of cordierite mass fraction, Fe/Ce molar ratio, coconut shells addition and ball milling parameters on the redox properties of the composite oxygen carriers were systematically investigated and corresponding characterizations (XRD, H₂-TPR, BET, SEM, XPS) were performed. It was found that the composite oxygen carrier with 30% cordierite that loaded Fe/Ce at a molar ratio of 1∶9 and prepared under the ball milling parameters of ball material ratio of 10∶1, rotational speed of 500r/min, and time of 1h, had superior redox properties. The addition of 15% coconut shell carbon increased the actual oxygen output of the composite oxygen carrier by 38.7%, and also demonstrated a good reaction stability and oxygen release capability in the reduction-oxidation cycle reactions.

Key words: chemical looping reforming, oxygen carriers, ball milling method, cordierite, coconut shells

摘要：

通过球磨法制备一系列堇青石负载Fe/Ce的复合载氧体，并在固定床装置上评价复合载氧体的甲烷化学链重整的反应性能。系统考察了堇青石质量分数、Fe/Ce摩尔比、椰壳添加量以及球磨参数对复合载氧体的氧化还原性能的影响，并进行了一系列表征（XRD、H₂-TPR、BET、SEM、XPS）。研究发现，在球料比10∶1、转速500r/min、时间1h的球磨参数下制备质量分数30%堇青石负载Fe/Ce摩尔比为1∶9的复合载氧体具有较优的氧化还原性能。质量分数15%椰壳炭的添加使复合载氧体的实际出氧量提升了38.7%，并且在还原氧化循环反应中表现出良好的稳定性和氧释放能力。

关键词: 化学链重整, 载氧体, 球磨法, 堇青石, 椰壳

CLC Number:

TQ426.82

DENG Yao, ZHAO Qingpeng, XU Jin, LIU Dawei, MA Xiaoxun, XU Long. Methane chemical looping reforming over cordierite-loaded Fe/Ce oxygen carriers prepared by ball milling[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2396-2408.

邓耀, 赵青鹏, 徐瑾, 刘大伟, 马晓迅, 徐龙. 球磨法制备堇青石负载Fe/Ce载氧体的甲烷化学链重整性能[J]. 化工进展, 2024, 43(5): 2396-2408.

Figures/Tables 22

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载氧体	晶粒尺寸/nm	晶格常数/nm
70CeO₂/30Cord	84.3	0.541
0.5Fe/9.5Ce(70CeO₂/30Cord)	75.9	0.5408
1Fe/9Ce(70CeO₂/30Cord)	74.3	0.5407
1.5Fe/8.5Ce(70CeO₂/30Cord)	73.9	0.5406
2Fe/8Ce(70CeO₂/30Cord)	70.3	0.5406

载氧体	晶粒尺寸/nm	晶格常数/nm
70CeO₂/30Cord	84.3	0.541
0.5Fe/9.5Ce(70CeO₂/30Cord)	75.9	0.5408
1Fe/9Ce(70CeO₂/30Cord)	74.3	0.5407
1.5Fe/8.5Ce(70CeO₂/30Cord)	73.9	0.5406
2Fe/8Ce(70CeO₂/30Cord)	70.3	0.5406

载氧体	微孔比表面积/m²·g^-1	介孔比表面积/m²·g^-1	总比表面积/m²·g^-1	介孔比例/%	平均孔径/nm	孔容/cm³·g^-1
70CeO₂/30Cord	0.3	5.3	5.6	94.3	31.6	0.049
1Fe/9Ce(70CeO₂/30Cord)	0.4	4.4	4.8	92.0	32.5	0.044

载氧体	微孔比表面积/m²·g^-1	介孔比表面积/m²·g^-1	总比表面积/m²·g^-1	介孔比例/%	平均孔径/nm	孔容/cm³·g^-1
70CeO₂/30Cord	0.3	5.3	5.6	94.3	31.6	0.049
1Fe/9Ce(70CeO₂/30Cord)	0.4	4.4	4.8	92.0	32.5	0.044

椰壳添加量（质量分数）/%	晶粒尺寸/nm	晶格常数/nm
0	74.3	0.5407
5	61.1	0.5411
10	59.7	0.5410
15	54.8	0.5407