基于甲烷脉冲法的Fe2O3-Al2O3载氧体还原特性研究

doi:10.11949/0438-1157.20230254

摘要/Abstract

摘要：

开发高效廉价铁基载氧体是天然气化学链重整制氢技术走向应用的关键。为探究高效铁基载氧体设计的基本依据，利用自行设计的脉冲反应器和气体产物全量同步在线分析系统，在800℃和无内外扩散影响的条件下研究了不同Fe₂O₃质量分数的Fe₂O₃-Al₂O₃载氧体的甲烷脉冲法还原特性。结果表明：Fe₂O₃的还原反应依两段机理进行，随载氧体颗粒内Fe₂O₃含量的多少可停止于Fe₃O₄，也可完全进行至FeO；气相产物中CO₂与CO的摩尔比随CH₄脉冲次数的变化规律也与Fe₂O₃含量密切相关。对用α-Al₂O₃粉末稀释高Fe₂O₃质量分数载氧体粉末的方法制备的低Fe₂O₃质量分数颗粒进行的脉冲还原实验结果，进一步揭示单位时间进入单个载氧体颗粒内的CH₄量与其Fe₂O₃含量的摩尔比决定单个颗粒以及整个床层的Fe₂O₃还原度。最后对还原度和CH₄转化率以及CO₂选择性数据进行关联分析，发现只有将载氧体的还原过程止于生成Fe₃O₄阶段才能得到较高的CO₂选择性，从而达到低成本回收高纯CO₂的目的。

关键词: 甲烷, 脉冲, 化学链, 制氢, 载氧体, 反应器

Abstract:

Developing a highly efficient and low-priced iron-based oxygen carrier is the key to the application of chemical looping reforming of natural gas for hydrogen production. In order to explore the basic principle of designing such an oxygen carrier, the methane-pulsing reduction characteristics of Fe₂O₃-Al₂O₃ oxygen carriers with different Fe₂O₃ contents were studied at 800℃ and without the influence of external and internal diffusion by using a self-designed reactor system capable of on-line methane pulsing and synchronized analysis of gaseous reaction products. The results show that the reduction reaction of Fe₂O₃ proceeds according to a two-stage mechanism, which can stop at Fe₂O₃ or completely proceed to FeO with the content of Fe₂O₃ in the oxygen carrier particles. The variation pattern of the molar ratio of CO₂ to CO in the gas phase product with the number of CH₄ pulses is also closely related to the content of Fe₂O₃. Pulse reduction results of particles prepared from a mixture of α-Al₂O₃ powder and powdery 80% (mass) Fe₂O₃-Al₂O₃ oxygen carrier further reveal that the reduction degree of Fe₂O₃ in a single particle as well as in the whole bed is determined by the molar ratio of CH₄ entering the particle per unit time to the absolute amount of Fe₂O₃ in the particle. At last analysis on the correlations of the reduction degree of Fe₂O₃ and CH₄ conversion and CO₂ selectivity leads to a conclusion that only limiting the reduction process of Fe₂O₃ oxygen carries to the stage of Fe₃O₄ formation could yield a reacted stream of a sufficiently high CO₂ concentration for low-cost recovery of high purity CO₂.

Key words: methane, pulse reaction, chemical looping, hydrogen production, oxygen carrier, reactor

中图分类号:

O 643.13⁺4

周小文, 杜杰, 张战国, 许光文. 基于甲烷脉冲法的Fe₂O₃-Al₂O₃载氧体还原特性研究[J]. 化工学报, 2023, 74(6): 2611-2623.

Xiaowen ZHOU, Jie DU, Zhanguo ZHANG, Guangwen XU. Study on the methane-pulsing reduction characteristics of Fe₂O₃-Al₂O₃ oxygen carrier[J]. CIESC Journal, 2023, 74(6): 2611-2623.

图/表 19

图1 甲烷化学链重整制氢原理

Fig.1 The concept of three-step chemical looping methane reforming for hydrogen production

图2 Fe2O3-Al2O3载氧体的制备

Fig.2 Preparation of Fe2O3-Al2O3 oxygen carrier samples

图3 在线甲烷脉冲还原载氧体反应分析系统

Fig.3 Reaction analysis system for online methane-pulsing reduction of oxygen carrier

表1 不同Fe2O3质量分数Fe2O3-Al2O3载氧体的BET比表面积

Table 1 BET surface area of Fe2O3-Al2O3 oxygen carriers with different Fe2O3 contents

Fe₂O₃质量分数/%	比表面积/（m²/g）
0	131.9
10	118.2
20	104.7
40	67.8
60	47.7
80	17.4

图4 不同Fe2O3质量分数Fe2O3-Al2O3载氧体的XRD谱图

Fig.4 XRD patterns of Fe2O3-Al2O3 oxygen carriers with different Fe2O3 contents

表2 不同质量分数Fe2O3在Fe2O3-Al2O3载氧体中的晶粒尺寸

Table 2 Crystallite size of Fe2O3 in different Fe2O3-Al2O3 oxygen carriers

Fe₂O₃质量分数/%	晶粒尺寸/nm
10	<5
20	20
40	21
60	21
80	21

图5 三次重复脉冲实验中单一脉冲反应的碳平衡

Fig.5 Carbon mass balance of each single pulse of three repeated pulsing reaction tests

图6 床层高度对甲烷脉冲还原实验结果的影响

Fig.6 Effect of bed height on the result of CH4-pulsing reduction experiments

图7 反应管内径对CH4转化率的影响

Fig.7 Effect of the reactor inner diameter on CH4 conversion

图8 Fe2O3-Al2O3载氧体粒径大小对CH4转化率的影响

Fig.8 Effect of the particle size of the Fe2O3-Al2O3 oxygen carrier on CH4 conversion

图9 Fe2O3质量分数对其晶格氧累积去除率的影响

Fig.9 Effect of Fe2O3 content in Fe2O3-Al2O3 oxygen carrier on removal of its lattice oxygen

图10 40%（质量）Fe2O3-Al2O3和80%（质量）Fe2O3-Al2O3经不同次数脉冲反应后的XRD谱图

Fig.10 XRD patterns of 40%(mass) Fe2O3-Al2O3 and 80%(mass) Fe2O3-Al2O3 oxygen carriers recovered after different number of pulse injection

图11 10%（质量）Fe2O3-Al2O3和20%（质量）Fe2O3-Al2O3经第1次和第9次脉冲反应后的XRD谱图

Fig.11 XRD patterns of 10%(mass) Fe2O3-Al2O3 and 20%(mass) Fe2O3-Al2O3 oxygen carriers recovered after the 1st and 9th pulse injections

图12 不同稀释方法对Fe2O3晶格氧累积去除率的影响

Fig.12 Effect of different dilution methods on the cumnlative removal of lattice oxygen in Fe2O3-Al2O3

图13 M1和M2载氧体经第1、2和9次脉冲反应后的XRD谱图

Fig.13 XRD patterns of M1 and M2 oxygen carriers recovered after the 1st, 2nd and 9th pulse injections

图14 高Fe2O3质量分数Fe2O3-Al2O3载氧体的两段还原特性（图中各组数据分别对应Fe2O3≥40%（质量）的不同载氧体的还原实验）3 Fe3O4 + CH4̿ 9 FeO + CO + 2 H2O（13）4 Fe3O4 + CH4̿ 12 FeO + CO2 + 2 H2O（14）

Fig.14 Two-step reduction behavior of the Fe2O3-Al2O3 oxygen carriers with high Fe2O3 contents

图15 甲烷累积脉冲量与载氧体床层氧化铁含量的摩尔比和甲烷转化率的关联（图中数据源自所有Fe2O3≥40%（质量）的不同载氧体的还原实验）

Fig.15 Correlation of the molar ratio of cumulatively pulsed CH4 to Fe2O3 contained in bed of Fe2O3-Al2O3 with CH4 conversion

图16 甲烷转化率和CO2选择性的关联（图中数据源自所有Fe2O3≥40%（质量）的不同载氧体的还原实验）

Fig.16 Correlation of CH4 conversion with CO2 selectivity

图17 四步反应法甲烷化学链重整制氢工艺流程图

Fig.17 The flowsheet of four-step chemical looping methane reforming for hydrogen production

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基于甲烷脉冲法的Fe₂O₃-Al₂O₃载氧体还原特性研究

Study on the methane-pulsing reduction characteristics of Fe₂O₃-Al₂O₃ oxygen carrier

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