甲烷催化部分氧化制合成气催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2022-1109

摘要/Abstract

摘要：

天然气是一种前景广阔的清洁燃料，甲烷作为天然气的主要成分，其高效利用具有重要的现实意义。在众多甲烷转化途径中，甲烷催化部分氧化（CPOM）具有能耗低、合成气组分适宜、反应迅速等优势。本文简要介绍了CPOM反应机理，即直接氧化机理和燃烧-重整机理；重点综述了过渡金属、贵金属、双金属和钙钛矿这四类CPOM催化剂的研究现状；分析了反应温度、反应气体碳氧比和反应空速对CPOM反应特性的影响；阐述了积炭和烧结这两种催化剂失活的主要原因及应对措施。根据研究结果可知，通过选取合适的催化剂组分、采用优化的制备方法、精确控制催化剂活性组分分布和微观结构等措施，可以保证更多的有效活性位更稳定地暴露在催化剂表面，以此提高催化性能（包括甲烷转化率、合成气选择性、合成气生成率、反应稳定性等）。最后指出了对CPOM催化剂微观结构的合理设计与可控制备以及对CPOM反应机理的深入研究仍将是今后关注的重点。

关键词: 甲烷, 部分氧化, 催化剂, 合成气, 多相反应

Abstract:

Natural gas is a promising clean fuel. The efficient use of methane, the major component of natural gas, is of great practical importance. Among many methane conversion routes, catalytic partial oxidation of methane (CPOM) has the advantages of low energy consumption, suitable syngas fraction and rapid reaction. This paper briefly introduced the CPOM reaction mechanisms (i.e. direct oxidation mechanism and combustion-reforming mechanism), reviewed the current research on four types of CPOM catalysts (i.e. transition metal, noble metal, bimetal and perovskite catalysts), analysed the effects of reaction temperature, carbon to oxygen molar ratio of reactant gas and reaction space velocity on CPOM reaction characteristics, and explained the two main causes of catalyst deactivation (i.e. carbon deposition and sintering) together with their countermeasures. According to the results of the research, the catalytic performance (including methane conversion, syngas selectivity, syngas yield, reaction stability) could be improved by selecting suitable catalyst components, adopting an optimized preparation method and precisely controlling the distribution of active components and microstructure of the catalyst. These method could ensure that more active sites are consistently exposed to the surface of catalyst. Finally, it was pointed out that the rational microstructure design and controlled synthesis of CPOM catalysts and the in-depth study of the CPOM reaction mechanism will remain the focus of future research.

Key words: methane, partial oxidation, catalyst, syngas, multiphase reaction

中图分类号:

TE644

阮鹏, 杨润农, 林梓荣, 孙永明. 甲烷催化部分氧化制合成气催化剂的研究进展[J]. 化工进展, 2023, 42(4): 1832-1846.

RUAN Peng, YANG Runnong, LIN Zirong, SUN Yongming. Advances in catalysts for catalytic partial oxidation of methane to syngas[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1832-1846.

图/表 13

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甲烷转化途径	目标产物	优势	劣势
直接转化	烯烃、烷烃、醇类、醛类、芳香烃等	工艺简单，运输成本低	高温、高压条件下反应，反应转化率低，产物选择性低
间接转化	合成气（CO+H₂）	工艺相对成熟，能源利用率高	工艺较复杂、生产成本较高
水蒸气重整		工艺成熟	强吸热反应、高能耗，对催化剂和反应设备要求高、投资成本高，产物氢碳比较高
二氧化碳重整		以常见的温室气体CO₂为原料、反应绿色环保	强吸热反应、高能耗，产物氢碳比较低，催化剂易积炭
催化部分氧化（CPOM）		弱放热反应、能耗低，产物氢碳比理想，反应迅速	工艺尚不成熟，存在安全隐患
自热重整		自供热、能耗低	控制复杂，对反应设备要求高

甲烷转化途径	目标产物	优势	劣势
直接转化	烯烃、烷烃、醇类、醛类、芳香烃等	工艺简单，运输成本低	高温、高压条件下反应，反应转化率低，产物选择性低
间接转化	合成气（CO+H₂）	工艺相对成熟，能源利用率高	工艺较复杂、生产成本较高
水蒸气重整		工艺成熟	强吸热反应、高能耗，对催化剂和反应设备要求高、投资成本高，产物氢碳比较高
二氧化碳重整		以常见的温室气体CO₂为原料、反应绿色环保	强吸热反应、高能耗，产物氢碳比较低，催化剂易积炭
催化部分氧化（CPOM）		弱放热反应、能耗低，产物氢碳比理想，反应迅速	工艺尚不成熟，存在安全隐患
自热重整		自供热、能耗低	控制复杂，对反应设备要求高

催化剂组成	反应条件	不同CH₄转化率下的温度/℃		不同CO选择性下的温度/℃		不同H₂选择性下的温度/℃		参考文献
催化剂组成	反应条件	T₅₀	T₉₀	T₅₀	T₉₀	T₅₀	T₉₀	参考文献
Ni(7.7)/Al₂O₃	C/O比例为1.0 WHSV=157500mL/(g·h)	600	—	600	800	<600	780	[48]
Ni(2.8)Co(2.6)/Al₂O₃		755	—	763	—	765	—
Co(6.8)/Al₂O₃		—	—	—	—	—	—
Ni(2.5)/La-CeO_x	C/O比例为1.0	<500	625	<550	700	*	*	[62]
Ni(5)/La-CeO_x		<500	625	<550	—	*	*
Ni(10)/La-CeO_x		618	645	630	—	*	*
Ni/MgO	C/O比例为1.0 WHSV=520000mL/(g·h)	503	625	503	510	*	*	[63]
La-Ni@SiO₂	C/O比例为1.0 WHSV=72000mL/(g·h)	<650	738	<650	712	<650	730	[64]
Rh(0.5)/Al₂O₃	C/O比例为1.0 GHSV=6000h^-1	525	765	535	730	<500	560	[65]
Rh(1)/γ-Al₂O₃	C/O比例为1.0 WHSV=48000mL/(g·h)	478	765	588	800	—	—	[44]
Rh(1)/γ-Al₂O₃-W	C/O比例为1.0 WHSV=48000mL/(g·h)	470	765	580	800	—	—	[44]
Rh(0.5)/HAP	C/O比例为1.0 GHSV=192000h^-1	613	—	685	—	680	—	[45]
Rh(1)/HAP		587	—	667	—	662	—
Rh(2)/HAP		637	—	677	—	677	—
Pt(0.5)-Ru(0.5)/CeZrO _x -Al₂O₃	C/O比例为1.0 GHSV=53000h^-1	565	785	670	—	550	610	[43]
Pt(0.5)-Ru(0.5)/CeZrO _x -Al₂O₃	C/O比例为0.75 GHSV=26000h^-1	570	780	640	—	578	595	[41]
La(0.5)Ca(0.5)Co(1)O_3-_δ	C/O比例为1.0 GHSV=12200h^-1	800	860	765	853	760	850	[60]
LaNiO₃	C/O比例为1.0 WHSV=216000 mL/(g·h)	350	—	525	—	430	—	[66]
有序介孔LaNiO₃	C/O比例为1.0 WHSV=216000 mL/(g·h)	<300	740	490	—	<300	—	[66]

催化剂组成	反应条件	不同CH₄转化率下的温度/℃		不同CO选择性下的温度/℃		不同H₂选择性下的温度/℃		参考文献
催化剂组成	反应条件	T₅₀	T₉₀	T₅₀	T₉₀	T₅₀	T₉₀	参考文献
Ni(7.7)/Al₂O₃	C/O比例为1.0 WHSV=157500mL/(g·h)	600	—	600	800	<600	780	[48]
Ni(2.8)Co(2.6)/Al₂O₃		755	—	763	—	765	—
Co(6.8)/Al₂O₃		—	—	—	—	—	—
Ni(2.5)/La-CeO_x	C/O比例为1.0	<500	625	<550	700	*	*	[62]
Ni(5)/La-CeO_x		<500	625	<550	—	*	*
Ni(10)/La-CeO_x		618	645	630	—	*	*
Ni/MgO	C/O比例为1.0 WHSV=520000mL/(g·h)	503	625	503	510	*	*	[63]
La-Ni@SiO₂	C/O比例为1.0 WHSV=72000mL/(g·h)	<650	738	<650	712	<650	730	[64]
Rh(0.5)/Al₂O₃	C/O比例为1.0 GHSV=6000h^-1	525	765	535	730	<500	560	[65]
Rh(1)/γ-Al₂O₃	C/O比例为1.0 WHSV=48000mL/(g·h)	478	765	588	800	—	—	[44]
Rh(1)/γ-Al₂O₃-W	C/O比例为1.0 WHSV=48000mL/(g·h)	470	765	580	800	—	—	[44]
Rh(0.5)/HAP	C/O比例为1.0 GHSV=192000h^-1	613	—	685	—	680	—	[45]
Rh(1)/HAP		587	—	667	—	662	—
Rh(2)/HAP		637	—	677	—	677	—
Pt(0.5)-Ru(0.5)/CeZrO _x -Al₂O₃	C/O比例为1.0 GHSV=53000h^-1	565	785	670	—	550	610	[43]
Pt(0.5)-Ru(0.5)/CeZrO _x -Al₂O₃	C/O比例为0.75 GHSV=26000h^-1	570	780	640	—	578	595	[41]
La(0.5)Ca(0.5)Co(1)O_3-_δ	C/O比例为1.0 GHSV=12200h^-1	800	860	765	853	760	850	[60]
LaNiO₃	C/O比例为1.0 WHSV=216000 mL/(g·h)	350	—	525	—	430	—	[66]
有序介孔LaNiO₃	C/O比例为1.0 WHSV=216000 mL/(g·h)	<300	740	490	—	<300	—	[66]

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