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

doi:10.11949/0438-1157.20220686

Abstract

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

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

CLC Number:

TQ 530.11

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.

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.

Figures/Tables 7

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

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

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

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

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

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

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

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

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