化学链制氢系统中磁铁矿氧载体的CO还原特性研究

doi:10.11949/0438-1157.20241408

摘要/Abstract

摘要：

磁铁矿作为化学链制氢系统的氧载体，具有低成本和环境友好的显著优势。然而，其在CO还原过程中的反应速率受控机制仍不完全明晰。采用热重分析方法探讨了650~900℃条件下20%CO等温还原磁铁矿的反应特征和多步反应动力学。XRD半定量分析结果表明，Fe₃O₄→FeO和FeO→Fe两步反应的耦合关系是温度依赖的。在650~750℃温度区间，两步反应高度重叠；在800~900℃温度区间，两步反应串联发生。在此基础上采用基于JMA模型的方法进行动力学分析，第一步反应受化学反应模型或三维成核模型（Avrami-Erofe’ev模型）控制，第二步反应则受扩散模型控制。

关键词: 化学链, 一氧化碳, 化学分析, 还原, 动力学模型

Abstract:

Magnetite has the significant advantages of low cost and environmental friendliness as an oxygen carrier in chemical looping hydrogen production system. However, the controlled mechanisms of its reaction rate during CO reduction remain are not fully understood. In this study, thermogravimetric analysis was used to investigate the reaction characteristics and multi-step reaction kinetics of 20%CO isothermal reduction of magnetite under conditions ranging from 650℃ to 900℃. The semi-quantitative analysis results indicate that the coupling relationship between the two-step reactions Fe₃O₄→FeO and FeO→Fe is temperature-dependent. In the temperature range of 650—750℃, the two-step reactions are highly overlapped, whereas in the temperature range of 800—900℃, the two steps occur in a sequential manner. Based on this, kinetic analysis was performed using the JMA model approach. The first step reaction is controlled by the chemical reaction model or three-dimensional nucleation model (Avrami-Erofe’ev model), while the second step reaction is controlled by the diffusion model.

Key words: chemical looping, carbon monoxide, chemical analysis, reduction, kinetic modeling

中图分类号:

TK 91

卢煦旸, 徐强, 康浩鹏, 史健, 曹泽水, 郭烈锦. 化学链制氢系统中磁铁矿氧载体的CO还原特性研究[J]. 化工学报, 2025, 76(7): 3286-3294.

Xuyang LU, Qiang XU, Haopeng KANG, Jian SHI, Zeshui CAO, Liejin GUO. The CO reduction characteristics of magnetite oxygen carriers in chemical looping hydrogen production systems[J]. CIESC Journal, 2025, 76(7): 3286-3294.

图/表 12

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No.	Kinetic model	f(α)	g(α)
1	one-dimensional diffusion	1/(2α)	α²
2	two-dimensional diffusion	-[1/ln(1-α)]	(1-α)ln(1-α)+α
3	3D-diffusion (Jander equation)	(3/2)(1-α)^2/3(1-(1-α)^1/3)^-1	(1-(1-α)^1/3)²
4	Avrami-Erofe’ev	(3/2) (1-α)(-ln(1-α))^1/3	(-ln(1-α))^2/3
5	Avrami-Erofe’ev	2(1-α)(-ln(1-α))^1/2	(-ln(1-α))^1/2
6	Avrami-Erofe’ev	3(1-α)(-ln(1-α))^2/3	(-ln(1-α))^1/3
7	contracting cylinder	2(1-α)^1/2	1-(1-α)^1/2
8	contracting sphere	3(1-α)^2/3	1-(1-α)^1/3
9	first-order	1-α	-ln(1-α)
10	second-order	(1-α)²	(1-α)^-1-1

No.	Kinetic model	f(α)	g(α)
1	one-dimensional diffusion	1/(2α)	α²
2	two-dimensional diffusion	-[1/ln(1-α)]	(1-α)ln(1-α)+α
3	3D-diffusion (Jander equation)	(3/2)(1-α)^2/3(1-(1-α)^1/3)^-1	(1-(1-α)^1/3)²
4	Avrami-Erofe’ev	(3/2) (1-α)(-ln(1-α))^1/3	(-ln(1-α))^2/3
5	Avrami-Erofe’ev	2(1-α)(-ln(1-α))^1/2	(-ln(1-α))^1/2
6	Avrami-Erofe’ev	3(1-α)(-ln(1-α))^2/3	(-ln(1-α))^1/3
7	contracting cylinder	2(1-α)^1/2	1-(1-α)^1/2
8	contracting sphere	3(1-α)^2/3	1-(1-α)^1/3
9	first-order	1-α	-ln(1-α)
10	second-order	(1-α)²	(1-α)^-1-1

参数	反应温度/℃	参数数值	标准差
a₁	650	0.1674	0.007
	700	0.2083	0.009
	750	0.2831	0.013
a₂	650	0.1164	0.005
	700	0.0872	0.002
	750	0.0820	0.003
n₁	650	0.9081	0.027
	700	1.1132	0.040
	750	1.1257	0.052
n₂	650	0.5120	0.009
	700	0.6398	0.008
	750	0.7077	0.011

参数	反应温度/℃	参数数值	标准差
a₁	650	0.1674	0.007
	700	0.2083	0.009
	750	0.2831	0.013
a₂	650	0.1164	0.005
	700	0.0872	0.002
	750	0.0820	0.003
n₁	650	0.9081	0.027
	700	1.1132	0.040
	750	1.1257	0.052
n₂	650	0.5120	0.009
	700	0.6398	0.008
	750	0.7077	0.011

参数	反应温度/℃	参数数值	标准差
a₁	800	0.4351	0.020
	850	0.4610	0.014
	900	0.6107	0.013
a₂	800	0.1006	0.002
	850	0.1262	0.002
	900	0.1180	0.001
n₁	800	2.6962	0.138
	850	3.0448	0.109
	900	3.2218	0.097
n₂	800	0.7582	0.007
	850	0.7761	0.006
	900	0.9502	0.005