Research progress of oxygen carriers in chemical looping reforming reaction of methane

doi:10.16085/j.issn.1000-6613.2023-2104

Abstract

Abstract:

The chemical looping reforming reaction of methane (CLRM) employs a solid oxygen carrier material as an intermediate to split the traditional methane reforming reaction into two reactions, reduction and oxidation, in which the oxygen carrier is continuously oxidized and reduced, forming a cyclic reaction and realizing the continuous production of syngas or hydrogen. More importantly, the CLRM reaction delivers a high purity product without the requirement of a costly air separation unit compared to conventional reforming reactions. And the key to the research of CLRM reaction lies on the design and selection of oxygen carriers. This paper summarized the recent research progress of metal-based oxygen carriers (Ni, Fe, Cu, Co, Mn, Ce-based) and composite oxygen carriers (including calixarenes and hexaaluminates) in recent years, focusing on the effects of the composition and structure of these oxygen carriers on the reactivity, and concluded the strategy of design and optimization of these oxygen carriers. Furthermore, the methods for the synthesis of the oxygen carriers were summarized and discussed. In addition, the current status of reactor process design was reviewed and potential issues were proposed in terms of the industrialization of CLRM. Finally, some existing challenges and future perspectives on the current studies of oxygen carriers for CLRM reactions were presented.

Key words: methane, chemical looping reforming, oxygen carrier, syngas, hydrogen

摘要：

甲烷化学链重整（CLRM）反应利用固体载氧体材料作为中间体，将传统甲烷重整反应分成还原和氧化两个反应，载氧体在这个过程中不断地被氧化还原，形成链式循环反应，实现了合成气或氢气的连续生产。相比传统重整反应而言，CLRM反应无须高成本的空分装置即可得到高纯度的产物。CLRM反应研究的关键在于载氧体的设计与选择，本文总结了近年来金属基载氧体（Ni、Fe、Cu、Co、Mn、Ce基）、复合型载氧体（包括钙钛矿和六铝酸盐）的最新研究进展，重点讨论了这些载氧体的组成、结构对反应性能的影响以及材料的设计与优化策略。进一步地，对载氧体的合成方法也做了总结和论述。此外，在甲烷化学链重整的工业化方面，探讨了反应器工艺流程设计的相关内容并提出了潜在问题。最后，对CLRM反应载氧体的研究现状提出了一些存在的挑战和未来的展望。

关键词: 甲烷, 化学链重整, 载氧体, 合成气, 氢气

CLC Number:

TQ426

WANG Jiarui, LIU Dawei, DENG Yao, XU Jin, MA Xiaoxun, XU Long. Research progress of oxygen carriers in chemical looping reforming reaction of methane[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2235-2253.

王嘉锐, 刘大伟, 邓耀, 徐瑾, 马晓迅, 徐龙. 载氧体在甲烷化学链重整反应中的研究进展[J]. 化工进展, 2024, 43(5): 2235-2253.

Figures/Tables 15

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金属	主要氧化物形式	氧转移能力排序	熔点/℃
Ni	NiO	―	NiO：1987；Ni：1453
Fe	FeO、Fe₂O₃和Fe₃O₄	FeO＞Fe₃O₄＞Fe₂O₃	FeO：1370；Fe₃O₄：1565；Fe₂O₃：1594
Cu	CuO和Cu₂O	CuO＞Cu₂O	CuO：1446；Cu₂O：1232
Co	CoO和Co₃O₄	Co₃O₄＞CoO	Co₃O₄：895；CoO：1935
Mn	MnO、Mn₃O₄、Mn₂O₃和MnO₂	MnO＞MnO₂＞Mn₃O₄＞Mn₂O₃	MnO：1650；MnO₂：535；Mn₃O₄：1567；Mn₂O₃：1080
Ce	CeO₂和Ce₂O₃	CeO₂＞Ce₂O₃	CeO₂：1950；Ce₂O₃：2177

金属	主要氧化物形式	氧转移能力排序	熔点/℃
Ni	NiO	―	NiO：1987；Ni：1453
Fe	FeO、Fe₂O₃和Fe₃O₄	FeO＞Fe₃O₄＞Fe₂O₃	FeO：1370；Fe₃O₄：1565；Fe₂O₃：1594
Cu	CuO和Cu₂O	CuO＞Cu₂O	CuO：1446；Cu₂O：1232
Co	CoO和Co₃O₄	Co₃O₄＞CoO	Co₃O₄：895；CoO：1935
Mn	MnO、Mn₃O₄、Mn₂O₃和MnO₂	MnO＞MnO₂＞Mn₃O₄＞Mn₂O₃	MnO：1650；MnO₂：535；Mn₃O₄：1567；Mn₂O₃：1080
Ce	CeO₂和Ce₂O₃	CeO₂＞Ce₂O₃	CeO₂：1950；Ce₂O₃：2177

载氧体	合成方法	实验条件	用途	参考文献
La_0.9Sr_0.1FeO₃/YSZ	球磨法	反应温度850℃	甲烷化学链干重整，固定床反应器	[100]
Ce-Fe-Zr-O/MgO	机械混合	反应温度800℃，原料气为5%（体积分数）CH₄/N₂	甲烷化学链蒸汽重整，固定床反应器	[101]
5NiO-RM	浸渍法	反应温度900℃，CO选择性可达94.1%	甲烷化学链蒸汽重整，固定床反应器	[52]
Cu-Al₂O₃	浸渍法	反应温度950℃，CH₄转化率为96%	甲烷自热化学链重整，流化床反应器	[64]
CeZr_0.5GdO₄	溶胶凝胶法	反应温度800~850℃，CH₄转化率和（H₂+CO）的摩尔比的均值在90%左右	甲烷化学链部分氧化重整，固定床反应器	[102]
Mg_0.1(Cu_0.3Ni_0.3Mn_0.4)_0.9Fe₂O₄	共沉淀法	反应温度500~750℃	甲烷化学链蒸汽重整，固定床反应器	[103]
Mg改性的Fe₂O₃/Al₂O₃	共沉淀法	反应温度900℃，在15次循环后，CO选择性和CH₄转化率分别保持在96%和82%	甲烷化学链蒸汽重整，流化床反应器	[104]
核壳型Fe₂O₃/MgO	水热沉淀法	反应温度800℃	甲烷化学链干重整，流化床反应器	[105]
Ce₉Co₁O _δ -10CS	溶液燃烧法	反应温度700℃	甲烷化学链干重整，固定床反应器	[76]

载氧体	合成方法	实验条件	用途	参考文献
La_0.9Sr_0.1FeO₃/YSZ	球磨法	反应温度850℃	甲烷化学链干重整，固定床反应器	[100]
Ce-Fe-Zr-O/MgO	机械混合	反应温度800℃，原料气为5%（体积分数）CH₄/N₂	甲烷化学链蒸汽重整，固定床反应器	[101]
5NiO-RM	浸渍法	反应温度900℃，CO选择性可达94.1%	甲烷化学链蒸汽重整，固定床反应器	[52]
Cu-Al₂O₃	浸渍法	反应温度950℃，CH₄转化率为96%	甲烷自热化学链重整，流化床反应器	[64]
CeZr_0.5GdO₄	溶胶凝胶法	反应温度800~850℃，CH₄转化率和（H₂+CO）的摩尔比的均值在90%左右	甲烷化学链部分氧化重整，固定床反应器	[102]
Mg_0.1(Cu_0.3Ni_0.3Mn_0.4)_0.9Fe₂O₄	共沉淀法	反应温度500~750℃	甲烷化学链蒸汽重整，固定床反应器	[103]
Mg改性的Fe₂O₃/Al₂O₃	共沉淀法	反应温度900℃，在15次循环后，CO选择性和CH₄转化率分别保持在96%和82%	甲烷化学链蒸汽重整，流化床反应器	[104]
核壳型Fe₂O₃/MgO	水热沉淀法	反应温度800℃	甲烷化学链干重整，流化床反应器	[105]
Ce₉Co₁O _δ -10CS	溶液燃烧法	反应温度700℃	甲烷化学链干重整，固定床反应器	[76]

合成方法	优点	缺点	参考文献
球磨法	简单的机械混合，适合大规模生产，过程简单易于控制，目标产物的产率高	物理方法的混合导致材料的均匀性较差，产物易出现团聚现象等	[106]
共沉淀法	将原料配成混合溶液，加入氨水搅拌沉淀得到样品。该方法所需实验设备简单，载氧体颗粒小且活性高，容易在实验室制备得到	该方法的缺点在于组分之间容易出现偏析，造成分布不均	[107]
水热沉淀法	将固体原料在水溶液中混合并在高压釜上加热，随后过滤分离高压釜得到的沉淀并干燥。该方法的组分间混合均匀，得到的样品颗粒小且活性好	步骤较为烦琐，需较多的热量输入	[105]
浸渍法	浸渍法常用于活性物质在载体上的负载过程。它的优点是制备工艺简单，操作方便	两相的直接混合过程导致其负载的活性组分的量较少且分布不均	[108]
溶液燃烧法	通常在含有金属硝酸盐和燃料的水溶液中发生一系列自持续的还原-氧化反应，将初始反应溶液预热至150∼200℃，水分被蒸干且反应物被燃料迅速点燃，从而形成纳米级的粉末材料。它的优点是反应时间短，生成大量气态产物，抑制了颗粒的生长，有利于合成具有高比表面积的纳米晶体	缺乏对粉末形态的控制会产生粉末团聚等问题，此外不完全燃烧也会产生残留有机杂质（来源于燃料，如柠檬酸和甘氨酸等）	[109]
溶胶凝胶法	溶胶凝胶法需要将原料的水溶液加入胶凝剂中，经水解缩合形成溶胶，最后通过缩聚陈化反应得到凝胶。该方法成本低且操作简单，所得到的样品纯度高且热处理温度较低等	由于所用到的胶凝剂如金属醇盐等成本高且有毒害，难以大规模商业化应用	[110]