CeO2/CuFe2O4氧载体CH4化学链重整耦合CO2热催化还原研究

doi:10.11949/0438-1157.20221139

化工学报 ›› 2022, Vol. 73 ›› Issue (12): 5414-5426.DOI: 10.11949/0438-1157.20221139

• 催化、动力学与反应器 • 上一篇下一篇

CeO₂/CuFe₂O₄氧载体CH₄化学链重整耦合CO₂热催化还原研究

王保文¹(), 张港¹, 刘同庆¹, 李炜光¹, 王梦家¹, 林德顺¹, 马晶晶²

^1.华北水利水电大学能源与动力工程学院，河南郑州 450045
^2.宁夏大学省部共建煤炭高效利用与绿色化工国家重点实验室，宁夏银川 750021

收稿日期:2022-08-15 修回日期:2022-11-07 出版日期:2022-12-05 发布日期:2023-01-17
通讯作者: 王保文
作者简介:王保文（1975—），男，博士，副教授，david-wn@163.com
基金资助:
国家自然科学基金项目(51776073);河南省科技攻关项目(162102210233);省部共建煤炭高效利用与绿色化工国家重点实验室项目(2021-KF 42)

Research on chemical looping reforming of CH₄ by CeO₂doped CuFe₂O₄oxygen carrier coupled with CO₂ thermocatalytic reduction

Baowen WANG¹(), Gang ZHANG¹, Tongqing LIU¹, Weiguang LI¹, Mengjia WANG¹, Deshun LIN¹, Jingjing MA²

^1.School of Energy and Power Engineering, North China University of Water Resources and Electric Power, Zhengzhou 450045, Henan, China
^2.State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China

Received:2022-08-15 Revised:2022-11-07 Online:2022-12-05 Published:2023-01-17
Contact: Baowen WANG

摘要/Abstract

摘要：

CH₄化学链重整耦合CO₂热催化还原，既能灵活调控所制备合成气的H₂/CO比，又能实现两种温室气体的高值化利用，具有极大的应用前景。采用溶胶-凝胶燃烧合成法制备不同质量掺杂比的CeO₂/CuFe₂O₄氧载体，在自制多功能固定床反应器中，系统考察了改性氧载体与CH₄部分氧化以及还原氧载体对CO₂的热催化还原性能，并通过连续氧化还原实验发现，与单一氧化物组分相比，CeO₂掺杂强化的CuFe₂O₄复合氧载体对CH₄和CO₂具有更高的反应活性。其中30% CeO₂掺杂量的混合氧载体具有最高的CH₄转化率，且在多次氧化还原循环反应中保持较高且稳定的CO₂转化率，表明其良好的反应性能和循环稳定性。

关键词: 甲烷, 二氧化碳, 化学链重整, 热催化还原, 合成气, CeO₂/CuFe₂O₄氧载体

Abstract:

The CH₄chemical chain reforming coupled with CO₂ thermal catalytic reduction can not only flexibly adjust the H₂/CO ratio of the prepared syngas, but also realize the high-value utilization of the two greenhouse gases, which has great application prospects. Mixed oxygen carriers of CuFe₂O₄ doped with CeO₂ of different mass contents were prepared by using a sol-gel combustion synthesis (SGCS) method. In a self-made multifunctional fixed-bed reactor, the thermal catalytic reduction performance of modified oxygen carrier and CH₄ for partial oxidation and reduced oxygen carrier for CO₂ was systematically investigated. And through continuous redox experiments, it was found that the CuFe₂O₄composite oxygen carrier enhanced by CeO₂ doping has higher reactivity towards CH₄ and CO₂ than the single oxide component. Furthermore, CuFe₂O₄ doped with 30%(mass) CeO₂ was found to have the highest CH₄ conversion, and during the cyclic reaction processes, high conversions of both CH₄ and CO₂ were sustained, as thus demonstrating its desired reaction performance and cyclic stability.

Key words: methane, carbon dioxide, chemical looping reforming, thermocatalytic reduction, syngas, CeO₂/CuFe₂O₄oxygen carrier

中图分类号:

TQ 028.8

王保文, 张港, 刘同庆, 李炜光, 王梦家, 林德顺, 马晶晶. CeO₂/CuFe₂O₄氧载体CH₄化学链重整耦合CO₂热催化还原研究[J]. 化工学报, 2022, 73(12): 5414-5426.

Baowen WANG, Gang ZHANG, Tongqing LIU, Weiguang LI, Mengjia WANG, Deshun LIN, Jingjing MA. Research on chemical looping reforming of CH₄ by CeO₂doped CuFe₂O₄oxygen carrier coupled with CO₂ thermocatalytic reduction[J]. CIESC Journal, 2022, 73(12): 5414-5426.

图/表 14

图1 甲烷化学链干重整制合成气工艺

Fig.1 Chemical looping dry reforming (CLDR) of methane technology for syngas

图2 固定床示意图

Fig.2 Schematic diagram of fixed-bed reactor

图3 自制氧载体的XRD谱图

Fig.3 XRD patterns of the freshly prepared oxygen carriers

表1 氧载体物理结构参数

Table 1 Physical structure parameters of oxygen carrier

样品	比表面积/(m²/g)	孔体积/(cm³/g)	孔径/nm	平均晶粒/nm
样品	比表面积/(m²/g)	孔体积/(cm³/g)	孔径/nm	CuFe₂O₄	CeO₂
100CF	1.166	0.004	13.845	54.33	—
10Ce90CF	2.933	0.011	11.288	32.76	29.58
20Ce80CF	4.328	0.012	12.397	32.28	43.22
30Ce70CF	4.799	0.016	13.251	29.93	39.06
40Ce60CF	5.820	0.020	13.882	24.41	49.80
100Ce	2.262	0.016	27.987	—	51.15

图4 氧载体N2吸附-脱附曲线（a）和孔径分布（b）

Fig.4 N2 adsorption-desorption curves of oxygen carriers (a) and pore size distribution (b)

图5 自制氧载体H2-TPR谱图

Fig.5 H2-TPR profiles of the prepared oxygen carriers

图6 氧载体表面SEM-EDX图像

Fig.6 SEM-EDX images of oxygen carrier surface

图7 CuFe2O4-CeO2氧载体900℃下与CH4部分氧化气体产物分布

Fig.7 Gas products distribution of methane partial oxidation with CuFe2O4-CeO2 at 900℃

图8 CuFe2O4-CeO2与甲烷部分氧化不同阶段气体产量

Fig.8 Gas yields of chemical looping partial oxidation of methane with CuFe2O4-CeO2 at different periods

图9 CuFe2O4-CeO2与甲烷在900℃下恒温反应性能

Fig.9 Reaction performance of methane with CuFe2O4-CeO2 oxygen carriers at 900℃

图10 不同氧载体在900℃下与CO2还原性能

Fig.10 Reduction performance of reduced CuFe2O4-CeO2 oxygen carriers with CO2 at 900℃

图11 氧载体30Ce70CF循环反应

Fig.11 Cyclic reactions of 30Ce70CF oxygen carrier

图12 30Ce70CF氧载体不同循环反应阶段XRD谱图

Fig.12 XRD patterns of 30Ce70CF oxygen carrier at the different cyclic reaction stages

图13 氧载体30Ce70CF在CH4还原和CO2氧化过程中XPS谱图

Fig.13 XPS maps of 30Ce70CF oxygen carrier in the CH4 reduction and CO2 catalytic oxidation stages

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CeO₂/CuFe₂O₄氧载体CH₄化学链重整耦合CO₂热催化还原研究

Research on chemical looping reforming of CH₄ by CeO₂doped CuFe₂O₄oxygen carrier coupled with CO₂ thermocatalytic reduction

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