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

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

化工进展 ›› 2024, Vol. 43 ›› Issue (5): 2396-2408.DOI: 10.16085/j.issn.1000-6613.2023-2062

• 化石能源的清洁高效转化利用 • 上一篇

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

邓耀(), 赵青鹏, 徐瑾, 刘大伟(), 马晓迅, 徐龙()

西北大学化工学院，碳氢资源清洁利用国际科技合作基地，陕北能源先进化工利用技术教育部工程研究中心，陕西省洁净煤转化工程技术研究中心，陕北能源化工产业发展协同创新中心，陕西西安 710127

收稿日期:2023-11-28 修回日期:2024-01-11 出版日期:2024-05-15 发布日期:2024-06-15
通讯作者: 刘大伟,徐龙
作者简介:邓耀（1997—），男，硕士研究生，研究方向为化学链重整。E-mail：dengyao1997yxj@163.com。
基金资助:
国家自然科学基金(22008197);陕西省重点研发计划(2022QCY-LL-69);陕西省创新能力支撑计划(2024RS-CXTD-53);西安市科技计划(22GXFW0132);咸阳市科技计划(2021ZDYF-NY-0017);榆林市科技计划(CXY-2021-129)

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

DENG Yao(), ZHAO Qingpeng, XU Jin, LIU Dawei(), MA Xiaoxun, XU Long()

International Science & Technology Cooperation Base of MOST for Clean Utilization of Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of Education for Advanced Use Technology of Shanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Collaborative Innovation Center for Development of Energy and Chemical Industry in Northern Shaanxi, School of Chemical Engineering, Northwest University, Xi’an 710127, Shaanxi, China

Received:2023-11-28 Revised:2024-01-11 Online:2024-05-15 Published:2024-06-15
Contact: LIU Dawei, XU Long

摘要/Abstract

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

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

中图分类号:

TQ426.82

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.

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.

图/表 22

图1 甲烷化学链重整反应流程示意图

图2 不同Fe/Ce的载氧体XRD谱图

表1 不同Fe/Ce的载氧体微观参数

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

图3 不同Fe/Ce载氧体的H2-TPR谱图

图4 不同载氧体的N2吸附-解吸曲线及孔径分布

表2 不同载氧体的物理结构参数

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

图5 载氧体的SEM图

图6 不同椰壳添加量下复合载氧体的XRD谱图（图中百分数均为质量分数）

表3 不同椰壳添加量下复合载氧体的晶体微观参数

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

图7 不同椰壳添加量下复合载氧体的N2吸附-解吸等温线及孔径分布（图中百分数均为质量分数）

表4 不同椰壳添加量下复合载氧体的平均孔径、孔容和比表面积

椰壳添加量（质量分数）/%	微孔比表面积/m²·g^-1	介孔比表面积/m²·g^-1	比表面积/m²·g^-1	介孔比例/%	平均孔径/nm	孔容/cm³·g^-1
5	0.3	4.0	4.2	93.18	29.1	0.030
10	0.3	4.7	5.0	94.22	27.5	0.035
15	0.3	4.2	4.5	92.80	22.9	0.035

图8 不同椰壳炭添加量下复合载氧体的SEM图（图中百分数均为质量分数）

图9 复合载氧体XPS谱图（图中百分数均为质量分数）

表5 复合载氧体XPS分析数据

复合载氧体	Ce 3d			O 1s	Fe 2p
复合载氧体	Ce³⁺/%	Ce⁴⁺/%	Ce³⁺/Ce⁴⁺	O_Ⅱ/（O_Ⅰ+O_Ⅱ）	Fe²⁺/%	Fe³⁺/%	Fe²⁺/Fe³⁺
70CeO₂/30Cord	17.30	82.70	0.21	0.439	—	—	—
1Fe/9Ce(70CeO₂/30Cord)	14.67	85.33	0.17	0.448	3.43	96.56	0.035
15%椰壳+1Fe/9Ce(70CeO₂/30Cord)	23.91	76.09	0.31	0.496	3.27	96.72	0.034

图10 不同堇青石添加量的载氧体甲烷化学链重整反应性能

图11 不同Fe/Ce下复合载氧体的甲烷化学链重整反应性能

图12 不同椰壳添加量下复合载氧体甲烷化学链重整反应性能

图13 不同球磨时间下复合载氧体甲烷化学链重整反应性能

图14 不同球磨转速下复合载氧体甲烷化学链重整反应性能

图15 不同球料比下复合载氧体甲烷化学链重整反应性能

图16 不同循环次数下复合载氧体甲烷化学链重整反应性能

图17 新鲜复合载氧体及其经过2次和8次还原氧化循环之后的XRD谱图

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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

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

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