Ce1-xNixOy氧载体在化学链甲烷重整耦合CO2还原中的应用

doi:10.11949/0438-1157.20201787

化工学报 ›› 2021, Vol. 72 ›› Issue (8): 4371-4380.DOI: 10.11949/0438-1157.20201787

Ce_1-_xNi_xO_y氧载体在化学链甲烷重整耦合CO₂还原中的应用

赵林洲¹(),郑燕娥^1,²(),李孔斋^2,³,王亚明¹,蒋丽红¹,范浩熙¹,王雅静¹,祝星^2,³,魏永刚^2,³

^1.昆明理工大学化学工程学院，云南昆明 650093
^2.昆明理工大学，复杂有色金属资源清洁利用国家重点实验室，云南昆明 650093
^3.昆明理工大学冶金与能源工程学院，云南昆明 650093

收稿日期:2020-12-09 修回日期:2021-04-02 出版日期:2021-08-05 发布日期:2021-08-05
通讯作者: 郑燕娥
作者简介:赵林洲（1994—），男，硕士研究生，2099941833@qq.com
基金资助:
国家自然科学基金项目(21706108);云南省应用基础研究项目(2018FD032)

Application of Ce_1-_xNi_xO_y oxygen carriers in chemical-looping reforming of methane coupled with CO₂ reduction

Linzhou ZHAO¹(),Yan'e ZHENG^1,²(),Kongzhai Li^2,³,Yaming WANG¹,Lihong JIANG¹,Haoxi FAN¹,Yajing WANG¹,Xing ZHU^2,³,Yonggang WEI^2,³

^1.Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China
^2.State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan, China
^3.Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China

Received:2020-12-09 Revised:2021-04-02 Online:2021-08-05 Published:2021-08-05
Contact: Yan'e ZHENG

摘要/Abstract

摘要：

化学链甲烷重整耦合CO₂还原技术既能生产合成气还可以还原CO₂生成CO。采用共沉淀法制备不同Ce/Ni摩尔比的系列Ce_1-_xNi_xO_y_{（x = 0,0.2,0.4,0.6,0.8,1）氧载体。通过XRD、BET、XPS及CH₄-TPR等表征对氧载体的理化性质进行了研究。系统考察了Ce_1-_xNi_xO_y氧载体在化学链甲烷重整耦合CO₂还原反应中的反应性能。与单一金属氧化物NiO和CeO₂相比，Ce_1-_xNi_xO_y复合氧载体在该反应中具有更高的活性和热稳定性。在甲烷部分氧化阶段，Ce_0.2Ni_0.8O_y和Ce_0.4Ni_0.6O_y氧载体具有较高的CH₄转化率。经历了20次redox循环实验，Ce_0.2Ni_0.8O_y氧载体的CO₂转化率几乎保持不变，表明Ce_0.2Ni_0.8O_y氧载体具有较高的热稳定性。}

关键词: 化学链, 甲烷重整, CO₂还原, 合成气, Ce_1-_xNi_xO_y氧载体

Abstract:

Chemical-looping reforming of methane coupled with CO₂ reduction technology can not only produce syngas, but also reduce CO₂ to generate CO. In this paper, a series of Ce_1-_xNi_xO_y_{(x = 0, 0.2, 0.4, 0.6, 0.8, 1) oxygen carriers with different Ce/Ni molar ratios were prepared by co-precipitation method. The physical and chemical properties of oxygen carriers were characterized by means of XRD, BET, XPS and CH₄-TPR. The performance of Ce_1-_xNi_xO_y oxygen carriers in chemical-looping reforming of methane coupled with CO₂ reduction reaction was systematically investigated. Compared with single metal oxide NiO and CeO₂, Ce_1-_xNi_xO_y composite oxygen carriers have higher activity and thermal stability in this reaction. During the partial oxidation of methane, Ce_0.2Ni_0.8O_y and Ce_0.4Ni_0.6O_y oxygen carriers have higher CH₄ conversion. After 20 redox cycle experiments, the CO₂ conversion rate of the Ce_0.2Ni_0.8O_y oxygen carrier remained almost unchanged, indicating that the Ce_0.2Ni_0.8O_y oxygen carrier has high thermal stability.}

Key words: chemical-looping, reforming of methane, CO₂ reduction, syngas, Ce_1-_xNi_xO_y oxygen carriers

中图分类号:

TE 665

赵林洲, 郑燕娥, 李孔斋, 王亚明, 蒋丽红, 范浩熙, 王雅静, 祝星, 魏永刚. Ce_1-_xNi_xO_y氧载体在化学链甲烷重整耦合CO₂还原中的应用[J]. 化工学报, 2021, 72(8): 4371-4380.

Linzhou ZHAO, Yan'e ZHENG, Kongzhai Li, Yaming WANG, Lihong JIANG, Haoxi FAN, Yajing WANG, Xing ZHU, Yonggang WEI. Application of Ce_1-_xNi_xO_y oxygen carriers in chemical-looping reforming of methane coupled with CO₂ reduction[J]. CIESC Journal, 2021, 72(8): 4371-4380.

图/表 15

图1 Ce1-xNixOy氧载体的XRD谱图

Fig.1 XRD patterns of Ce1-xNixOyoxygen carriers

图2 Ce1-xNixOy氧载体的N2吸附-脱附曲线（a）和孔径分布图（b）

Fig.2 Nitrogen adsorption-desorption isotherms (a) and pore-size distributions (b) of Ce1-xNixOy oxygen carriers

表1 氧载体的孔体积、平均孔径和比表面积

Table 1 The pore volumes， average pore diameter and BET surface areas of oxygen carriers

样品	孔体积/(cm³/g)	平均孔径/nm	比表面积/(m²/g)
NiO	0.031	10.725	11.45
Ce_0.2Ni_0.8O_y	0.120	16.092	29.59
Ce_0.4Ni_0.6O_y	0.079	13.857	22.74
Ce_0.6Ni_0.4O_y	0.070	13.726	20.25
Ce_0.8Ni_0.2O_y	0.054	9.989	21.53
CeO₂	0.056	16.015	13.97

图3 Ce0.2Ni0.8Oy和Ce0.4Ni0.6Oy氧载体的XPS谱图

Fig.3 XPS spectra of Ce0.2Ni0.8Oy and Ce0.4Ni0.6Oy oxygen carriers

表2 Ce0.2Ni0.8Oy和Ce0.4Ni0.6Oy氧载体的相关XPS参数

Table 2 The relevant XPS parameters of Ce0.2Ni0.8Oyand Ce0.4Ni0.6Oy oxygen carriers

Ce³⁺/

Ce⁴⁺

Ni²⁺/Ni³⁺

Ce³⁺

Ce⁴⁺

Ni²⁺

Ni³⁺

图4 Ce1-xNixOy氧载体的CH4-TPR曲线

Fig.4 CH4-TPR profiles of Ce1-xNixOyoxygen carriers

图5 Ce1-xNixOy氧载体在800℃下甲烷恒温反应中气体含量变化

Fig.5 The gas content change of Ce1-xNixOy oxygen carriers in the CH4 isothermal reaction at 800℃

图6 Ce1-xNixOy氧载体在800℃下CO2还原反应中气体含量变化

Fig.6 The gas content change of Ce1-xNixOy oxygen carriers in the CO2 reduction reaction at 800℃

图7 Ce0.2Ni0.8Oy(a)和Ce0.4Ni0.6Oy(b)氧载体在20次redox循环中CH4氧化阶段H2和CO含量变化

Fig.7 H2 and CO contents change of Ce0.2Ni0.8Oy(a) and Ce0.4Ni0.6Oy(b) oxygen carriers in CH4 oxidation stage in 20 redox cycles

图8 Ce0.2Ni0.8Oy(a)和Ce0.4Ni0.6Oy(b)氧载体在20次redox循环中CO2还原阶段CO含量变化

Fig.8 CO contents change of Ce0.2Ni0.8Oy(a) and Ce0.4Ni0.6Oy(b) oxygen carriers in CO2 reduction stage in 20 redox cycles

图9 经过20次redox循环后氧载体的XRD谱图

Fig.9 XRD patterns of oxygen carriers after 20 redox cycles

图10 20次redox循环后Ce0.2Ni0.8Oy和Ce0.4Ni0.6Oy氧载体的N2吸附-解吸曲线（a）和孔径分布图（b）

Fig.10 Nitrogen adsorption-desorption isotherms (a) and pore-size distributions (b) of Ce0.2Ni0.8Oy and Ce0.4Ni0.6Oy oxygen carriers after 20 redox cycles

表3 经过20次redox循环后Ce0.2Ni0.8Oy和Ce0.4Ni0.6Oy氧载体的孔体积、平均孔径和比表面积

Table 3 The pore volumes， average pore diameter and BET surface areas of Ce0.2Ni0.8Oy and Ce0.4Ni0.6Oy oxygen carriers after 20 redox cycles

样品	孔体积/(cm³/g)	平均孔径/nm	比表面积/(m²/g)
Ce_0.2Ni_0.8O_y	0.038	11.525	10.09
Ce_0.4Ni_0.6O_y	0.028	11.531	7.24

图11 经过20次redox循环后Ce0.2Ni0.8Oy和Ce0.4Ni0.6Oy氧载体的XPS谱图

Fig.11 XPS spectra of Ce0.2Ni0.8Oy and Ce0.4Ni0.6Oy oxygen carriers after 20 redox cycles

表4 经过20次redox循环的Ce0.2Ni0.8Oy和Ce0.4Ni0.6Oy氧载体的相关XPS参数

Table 4 The relevant XPS parameters of Ce0.2Ni0.8Oy and Ce0.4Ni0.6Oy oxygen carriers after 20 redox cycles

氧载体	氧百分比			O_surf/O_latt	Ce百分比		Ce³⁺/Ce⁴⁺	Ni百分比		Ni²⁺/Ni³⁺
氧载体	OⅠ	OⅡ	OⅢ	O_surf/O_latt	Ce³⁺	Ce⁴⁺	Ce³⁺/Ce⁴⁺	Ni²⁺	Ni³⁺	Ni²⁺/Ni³⁺
Ce_0.2Ni_0.8O_y	23.45	39.03	37.53	1.66	10.65	89.35	0.12	39.28	60.72	0.65
Ce_0.4Ni_0.6O_y	14.35	27.01	58.64	0.70	7.89	92.11	0.08	34.28	65.72	0.52

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Ce_1-_xNi_xO_y氧载体在化学链甲烷重整耦合CO₂还原中的应用

Application of Ce_1-_xNi_xO_y oxygen carriers in chemical-looping reforming of methane coupled with CO₂ reduction

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