化学链燃烧过程Fe2O3/Al2O3载氧体表面CH4反应：ReaxFF-MD模拟

doi:10.11949/0438-1157.20220686

化工学报 ›› 2022, Vol. 73 ›› Issue (9): 4054-4061.DOI: 10.11949/0438-1157.20220686

化学链燃烧过程Fe₂O₃/Al₂O₃载氧体表面CH₄反应：ReaxFF-MD模拟

袁妮妮(), 郭拓, 白红存, 何育荣, 袁永宁, 马晶晶, 郭庆杰()

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，化学化工学院，宁夏银川 750021

收稿日期:2022-05-12 修回日期:2022-06-02 出版日期:2022-09-05 发布日期:2022-10-09
通讯作者: 郭庆杰
作者简介:袁妮妮(1986—)，女，博士研究生，讲师，yuannini727@163.com
基金资助:
国家自然科学基金区域创新发展联合基金项目(U20A20124);国家自然科学基金项目(21868025);宁夏回族自治区重点研发计划项目(重大科技项目)(2018BCE01002);宁夏自然科学基金项目(2022A0887);宁夏高等学校一流学科建设项目(NXYLXK2017A04)

Reaction process of CH₄ on the surface of Fe₂O₃/Al₂O₃ oxygen carrier in chemical looping combustion: ReaxFF-MD simulation

Nini YUAN(), Tuo GUO, Hongcun BAI, Yurong HE, Yongning YUAN, Jingjing MA, Qingjie GUO()

State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, Ningxia, China

Received:2022-05-12 Revised:2022-06-02 Online:2022-09-05 Published:2022-10-09
Contact: Qingjie GUO

摘要/Abstract

摘要：

借助ReaxFF-MD方法，对化学链燃烧过程Al₂O₃负载Fe₂O₃载氧体（Fe₂O₃/Al₂O₃）表面CH₄反应过程模拟，探究Al₂O₃惰性载体对Fe₂O₃-CH₄体系燃烧过程的调控机制。研究发现添加Al₂O₃惰性载体改变了化学链燃烧过程中Fe₂O₃载氧体反应性和Fe₂O₃/Al₂O₃-CH₄反应体系的热力学和动力学行为。主要是促进了Fe₂O₃载氧体表面CH₄氧化，并对CH₄反应过程、中间体、产物及其反应速率和放热量等均具有显著促进和调控作用。原因在于Al₂O₃惰性载体对Fe₂O₃活性相中晶格氧的活化作用促进了晶格氧的迁移-扩散-释放。添加惰性载体增强了Fe₂O₃载氧体在化学链燃烧过程晶格氧释放速率和释放量，有利于CH₄氧化燃烧向合成气的高效、清洁转化，强化了化学链燃烧过程，满足当前能源高效转化和碳减排目标。

关键词: 化学链燃烧, Fe基载氧体, 反应分子动力学, 氧化铝, 计算机模拟, 天然气

Abstract:

This work simulated the reaction process of CH₄ on the surface of Al₂O₃ supported Fe₂O₃ oxygen carrier (denoted as: Fe₂O₃/Al₂O₃) in chemical looping combustion (CLC) by using ReaxFF-MD method, and explored the regulation mechanism of Al₂O₃ inert support on the combustion process of Fe₂O₃/Al₂O₃-CH₄ system. It was found that the addition of Al₂O₃ inert carrier changed the reactivity of Fe₂O₃ oxygen carrier and the thermodynamic and kinetic behaviors of Fe₂O₃/Al₂O₃-CH₄ reaction system during CLC. The main purpose is to promote the oxidation of CH₄ on the surface of Fe₂O₃ oxygen carrier, and to significantly promote and regulate the CH₄ reaction process, intermediates, products and their reaction rates and heat release. ReaxFF-MD simulation showed that the activation effects of Al₂O₃ inert support on the lattice oxygen in Fe₂O₃ active phase facilitated the migration-diffusion-release of the lattice oxygen. These findings show that the addition of inert support can enhance the lattice oxygen release of the Fe₂O₃ oxygen carriers in CLC, and favor the efficient and clean conversion of CH₄ to the syngas, and strengthen the CLC process, as well as satisfy the goals of the current energy efficient conversion and carbon emission reduction targets.

Key words: chemical looping combustion, Fe-based oxygen carriers, reactive molecular dynamics, alumina, computer simulation, natural gas

中图分类号:

TQ 530.11

袁妮妮, 郭拓, 白红存, 何育荣, 袁永宁, 马晶晶, 郭庆杰. 化学链燃烧过程Fe₂O₃/Al₂O₃载氧体表面CH₄反应：ReaxFF-MD模拟[J]. 化工学报, 2022, 73(9): 4054-4061.

Nini YUAN, Tuo GUO, Hongcun BAI, Yurong HE, Yongning YUAN, Jingjing MA, Qingjie GUO. Reaction process of CH₄ on the surface of Fe₂O₃/Al₂O₃ oxygen carrier in chemical looping combustion: ReaxFF-MD simulation[J]. CIESC Journal, 2022, 73(9): 4054-4061.

图/表 7

图1 Fe2O3/Al2O3 载氧体与CH4反应模型

Fig.1 The model of Fe2O3/Al2O3 oxygen carrier reacted with CH4

图2 化学链燃烧过程CH4在Fe2O3/Al2O3载氧体表面不同温度氧化势能曲线 (a) 和CH4分子数目变化趋势 (b) (1 kcal=4.18 kJ)

Fig.2 Potential energy curves (a) and the number of CH4 molecules (b) of the oxidation of CH4 on the surface of Fe2O3/Al2O3 oxygen carriersin chemical looping combustion at various temperature

图3 3000 K化学链燃烧过程CH4分子在载氧体表面反应过程产物分布及其分子数目

Fig.3 Production distribution and their molecule number of the reaction process of CH4 on thesurface of oxygen carriers during chemical looping combustion at 3000 K

图4 化学链燃烧过程CH4在Fe2O3/Al2O3载氧体表面反应过程及产物示意图

Fig.4 Schematic of the reaction process and production distribution of CH4 on the surface of Fe2O3/Al2O3oxygen carrier during chemical looping combustion

图5 化学链燃烧过程CH4在Fe2O3载氧体表面氧化过程及产物示意图

Fig.5 Schematic of the oxidation process and production distribution of CH4 on the surface of Fe2O3 oxygencarrier during chemical looping combustion

图6 3000 K时CH4分别在Fe2O3和Fe2O3/Al2O3载氧体表面氧化反应势能曲线

Fig.6 Potential energy curves of the reaction process of CH4 on the surface of Fe2O3 and Fe2O3/Al2O3 oxygen carrier at 3000 K, respectively

图7 化学链燃烧过程Fe2O3/Al2O3-CH4体系(a)和Fe2O3-CH4体系(b)作用机制示意图

Fig.7 Schematic of the interaction mechanism of Fe2O3/Al2O3-CH4 system (a) and Fe2O3-CH4 system (b) during chemical looping combustion process

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化学链燃烧过程Fe₂O₃/Al₂O₃载氧体表面CH₄反应：ReaxFF-MD模拟

Reaction process of CH₄ on the surface of Fe₂O₃/Al₂O₃ oxygen carrier in chemical looping combustion: ReaxFF-MD simulation

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