甲醇重整制氢催化剂耐久性评价和寿命预测方法

doi:10.16085/j.issn.1000-6613.2024-0446

摘要/Abstract

摘要：

甲醇重整制氢是实现氢能产业化应用的重要发展方向，催化剂作为甲醇重整制氢系统的核心材料，其性能和寿命至关重要。本文选用商业Cu/ZnO/Al₂O₃催化剂为研究对象，研究了Cu基催化剂反应10h、100h、1000h后的性能，分析了甲醇在不同催化温度下的反应速率，并创新性地提出催化剂寿命的评价和预测方法。系统研究高温失活对Cu基催化剂性能的影响分析，通过对催化剂比表面积、Cu晶粒分散度以及热重（TG-DTG）表征分析，发现高温烧结和积炭是甲醇水蒸气重整反应中导致Cu基催化剂失活的主要原因。该研究对开发设计长寿命甲醇重整制氢系统具有重要意义。

关键词: 甲醇, 制氢, 催化剂, 寿命

Abstract:

Methanol reforming for hydrogen production is an important development direction to realize the industrial application of hydrogen energy. As catalyst is the core material of methanol reforming, it's performance and life are very important. In this paper, the performance of Cu-based catalysts of commercial Cu/ZnO/Al₂O₃ were studied with reaction for 10h, 100h, 1000h, the reaction rates of methanol at different catalytic temperatures were analyzed, and the evaluation and prediction methods of catalyst life were innovatively proposed. The influence of high temperature deactivation on the performance of the Cu-based catalyst was systematically studied. Through the characterization of catalyst's specific surface area, Cu grain dispersion and TG-DTG, we found that high temperature sintering and carbon deposition were the main reasons for the deactivation. This research held significant importance for the development and design of long-life methanol reforming system for hydrogen production.

Key words: methanol, hydrogen production, catalysts, life

中图分类号:

TQ116.2

朱国瑜, 葛棋, 付名利. 甲醇重整制氢催化剂耐久性评价和寿命预测方法[J]. 化工进展, 2025, 44(3): 1338-1346.

ZHU Guoyu, GE Qi, FU Mingli. Durability testing and life prediction of methanol reforming catalysts for hydrogen production[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1338-1346.

图/表 20

参考文献 17

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试剂/仪器	型号/规格	品牌/生产厂家
甲醇	分析纯	阿拉丁试剂有限公司
氮气	高纯氮99.99%	液化空气工业气体有限公司
甲醇重整催化剂	Cu/ZnO/Al₂O₃	四川蜀泰化工科技有限公司
气体质量流量控制器	N₂-5L/min	北京七星华创流量计有限公司
流量计	0~100L/h	重庆三协益新仪表有限公司
压力传感器	0~50kPa	北京华控兴业仪表有限公司
温控仪表	DSN-800D	东莞市德欣电子科技有限公司
针阀	0~3mm可调节	世伟洛克流体科技有限公司
冷凝器	DLSB-20L-10	郑州世联良工仪器设备有限公司
电磁阀	VXE2350L-02-5DL1	SMC中国有限公司
气体分析仪	Gas-3800P	武汉锐意自控系统有限公司
气相色谱仪	GC-9790PNS	浙江福立分析仪器股份有限公司
微型进液计量泵	AP0010	上海三为科学仪器有限公司

试剂/仪器	型号/规格	品牌/生产厂家
甲醇	分析纯	阿拉丁试剂有限公司
氮气	高纯氮99.99%	液化空气工业气体有限公司
甲醇重整催化剂	Cu/ZnO/Al₂O₃	四川蜀泰化工科技有限公司
气体质量流量控制器	N₂-5L/min	北京七星华创流量计有限公司
流量计	0~100L/h	重庆三协益新仪表有限公司
压力传感器	0~50kPa	北京华控兴业仪表有限公司
温控仪表	DSN-800D	东莞市德欣电子科技有限公司
针阀	0~3mm可调节	世伟洛克流体科技有限公司
冷凝器	DLSB-20L-10	郑州世联良工仪器设备有限公司
电磁阀	VXE2350L-02-5DL1	SMC中国有限公司
气体分析仪	Gas-3800P	武汉锐意自控系统有限公司
气相色谱仪	GC-9790PNS	浙江福立分析仪器股份有限公司
微型进液计量泵	AP0010	上海三为科学仪器有限公司

物性	Cu/ZnO/Al₂O₃
形状	黑色圆柱体
粒径大小	Φ3mm×(2.5~3)mm
堆密度	1.5kg/L
压力	常压约3MPa
温度	160~280℃
甲醇LHSV	<1.5h^-1

物性	Cu/ZnO/Al₂O₃
形状	黑色圆柱体
粒径大小	Φ3mm×(2.5~3)mm
堆密度	1.5kg/L
压力	常压约3MPa
温度	160~280℃
甲醇LHSV	<1.5h^-1

催化剂反应温度/℃	催化剂反应时间/h	LHSV/h^-1	压力/kPa	甲醇水流量/g·min^-1	密度/g·cm^-3
250	10	1.5	50	0.75	0.915
350	10	1.5	50	0.75	0.915
450	10	1.5	50	0.75	0.915