Ni、Ce、Zn和Cu修饰Fe2O3/Al2O3载氧体的甲烷化学链制氢特性

doi:10.16085/j.issn.1000-6613.2023-1258

摘要/Abstract

摘要：

以甲烷为燃料的化学链制氢是一种耦合CO₂捕集的高效制氢技术。在Fe₂O₃/Al₂O₃载氧体的基础上，通过浸渍法分别添加Ni、Ce、Zn和Cu形成双金属载氧体，以提高其晶格氧传递性能、制氢性能和抗积炭性能。本文通过热力学计算、材料表征和实验研究，研究了不同双金属载氧体还原阶段和制氢阶段的反应性能，获得了不同双金属载氧体晶相结构与反应活性、制氢性能间的构效关系；并针对筛选出的最佳载氧体，进一步研究了其循环反应稳定性。研究表明，Cu是最合适的金属添加剂。Cu在Fe₂O₃/Al₂O₃双金属载氧体中形成了结构稳定的尖晶石相CuFe₂O₄，提高了晶格氧活性，促进了载氧体中Fe₂O₃的深度还原，同时有效抑制积炭的生成，显著提高氢气产量和纯度，其中氢气产量由245mmol/100g载氧体提高到288mmol/100g载氧体，氢气纯度由88.3%提高到95.7%。Cu修饰Fe₂O₃/Al₂O₃载氧体在循环中表现出良好的稳定性，Fe³⁺和Cu²⁺的迁移使其微观结构得到改善，循环反应性能得到提高。研究验证了双金属载氧体在甲烷化学链制氢反应中的可行性，研究结果为铁基载氧体的设计和筛选提供了理论和实验依据。

关键词: 化学链制氢, 载氧体, 金属添加剂, 氧传递, 积炭

Abstract:

Methane-fueled chemical looping hydrogen generation is an efficient hydrogen production technology coupled with CO₂ capture. On the basis of Fe₂O₃/Al₂O₃oxygen carrier, Ni, Ce, Zn and Cu were added to form bimetallic oxygen carriers by impregnation method to improve the oxygen transfer performance, hydrogen production performance and carbon deposition resistance. Through thermodynamic calculation, material characterization and experimental study, the reaction properties of different bimetallic oxygen carriers in reduction stage and hydrogen production stage were studied, and the structure-activity relationship between crystal phase structure, reaction activity and hydrogen production performance of different bimetallic oxygen carriers was obtained. The stability of the cyclic reaction was further studied for the optimal oxygen carrier. Studies showed that Cu was the most suitable metal additive. CuFe₂O₄, a spinel phase with stable structure, was formed in Cu-modified Fe₂O₃/Al₂O₃ oxygen carriers, improving lattice oxygen activity, promoting the deep reduction of Fe₂O₃, and effectively inhibiting carbon deposition. The yield of hydrogen increased from 245mmol/100g oxygen carriers to 288mmol/100g oxygen carriers, and the purity of hydrogen increased from 88.3% to 95.7%. The migration of Fe³⁺and Cu²⁺ ions improved the microstructure and cyclic reaction performance. The feasibility of bimetallic oxygen carriers in methane-fueled chemical looping hydrogen generation was verified. The results provided theoretical and experimental basis for the design and screening of iron-based oxygen carriers.

Key words: chemical looping hydrogen generation, oxygen carrier, metal additives, oxygen transport, carbon deposition

中图分类号:

TK91

向浩寅, 陈良勇. Ni、Ce、Zn和Cu修饰Fe₂O₃/Al₂O₃载氧体的甲烷化学链制氢特性[J]. 化工进展, 2024, 43(8): 4320-4332.

XIANG Haoyin, CHEN Liangyong. Evaluation of Ni, Ce, Zn and Cu modified Fe₂O₃/Al₂O₃oxygen carriers for methane-fueled chemical looping hydrogen generation process[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4320-4332.

图/表 18

图1 以CH4为燃料的三反应器化学链制氢工艺原理 [5]

表1 载氧体化学组分分析

载氧体	Fe₂O₃质量分数/%	NiO质量分数/%	CeO₂质量分数/%	ZnO质量分数/%	CuO质量分数/%	Al₂O₃质量分数/%	其他（质量分数）/%
Fe15Al	16.44	—	—	—	—	82.71	0.85
Fe15Ni5Al	16.39	5.53	—	—	—	77.35	0.73
Fe15Ce5Al	16.00	—	5.18	—	—	78.07	0.75
Fe15Zn5Al	16.67	—	—	5.32	—	77.32	0.69
Fe15Cu5Al	15.90	—	—	—	5.89	77.48	0.73

图2 固定床反应器实验装置图MFC—质量流量控制计；FT—流量变送器；FV—流量控制阀

图3 还原阶段和制氢阶段的热力学计算

图4 新鲜载氧体的XRD图谱

图5 新鲜载氧体的XPS图谱

图6 不同载氧体的反应器出口气体成分变化规律图

图7 不同载氧体还原阶段失氧量

图8 不同载氧体制氢阶段得氧量

图9 不同载氧体制氢阶段H2产量和纯度

图10 不同载氧体还原阶段总积炭量及制氢阶段积炭去除量

图11 载氧体表面的积炭形貌

图12 Fe15Al、Fe15Cu5Al载氧体表面积炭的O2-TPO曲线

图13 循环实验中总H2产量和H2纯度

图14 循环前后载氧体的扫描电子显微镜（SEM）图

图15 循环前后载氧体表面Fe、Cu元素的能量色散X射线谱（EDS）图

表2 循环前后载氧体表面的元素质量分数

载氧体	Fe质量分数/%	Cu质量分数/%
新鲜Fe15Al	21.8	—
新鲜Fe15Cu5Al	17.0	6.4
10次循环后Fe15Al	27.8	—
10次循环后Fe15Cu5Al	24.6	14.9

图16 循环实验中还原阶段的总积炭量和制氢阶段的积炭去除量

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Ni、Ce、Zn和Cu修饰Fe₂O₃/Al₂O₃载氧体的甲烷化学链制氢特性

Evaluation of Ni, Ce, Zn and Cu modified Fe₂O₃/Al₂O₃oxygen carriers for methane-fueled chemical looping hydrogen generation process

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