乙醇催化重整产氢催化剂及催化反应机制

doi:10.16085/j.issn.1000-6613.2018-2339

化工进展 ›› 2019, Vol. 38 ›› Issue (05): 2320-2328.DOI: 10.16085/j.issn.1000-6613.2018-2339

乙醇催化重整产氢催化剂及催化反应机制

陈俊¹(),舒红飞¹,阮祝华¹,倪嘉琪¹,鲁礼林^1,²(),刘义¹

1. 武汉科技大学化学与化工学院，煤转化与新型炭材料湖北省重点实验室，湖北武汉 430081
2. 武汉科技大学省部共建耐火材料与冶金国家重点实验室，湖北武汉 430081

收稿日期:2018-11-30 修回日期:2019-02-15 出版日期:2019-05-05 发布日期:2019-05-05
通讯作者: 鲁礼林
作者简介:<named-content content-type="corresp-name">陈俊</named-content>（1996—），男，硕士研究生，研究方向为能源催化。E-mail：<email>ylsn99866@sina.com</email>。
基金资助:
国家自然科学基金(21671154，U1732147)

Catalysts and catalytic mechanism for hydrogen production from ethanol steam reforming (ESR)

Jun CHEN¹(),Hongfei SHU¹,Zhuhua RUAN¹,Jiaqi NI¹,Lilin LU^1,²(),Yi LIU¹

1. Hubei Province Key Laboratory of Coal Conversion and New Carbon Materials, School of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China
2. State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China

Received:2018-11-30 Revised:2019-02-15 Online:2019-05-05 Published:2019-05-05
Contact: Lilin LU

摘要/Abstract

摘要：

以乙醇为原料催化乙醇重整反应产氢由于具有效率高、毒性低以及乙醇可持续性生产等优点，被认为是一种极具工业化应用前景的制氢方法，但现存的乙醇重整反应催化剂存在催化效率和产氢选择性低、稳定性差等缺点，阻碍了乙醇重整制氢技术的广泛应用。本文主要综述了乙醇重整制氢金属催化剂的研究进展，着重阐述了金属元素种类、催化剂载体、反应温度和原料水醇比等对乙醇转化率和产物选择性的影响，归纳分析了乙醇重整过程中催化剂稳定性的影响因素和提高催化剂稳定性的方法和措施，并对乙醇重整制氢反应机制的研究工作进行了总结。基于乙醇重整产氢催化剂的研究现状，提出开发高效稳定催化剂的关键在于系统研究催化乙醇重整反应机制以及催化反应过程中催化剂与载体的协同效应对催化剂性能的影响。

关键词: 制氢, 醇, 重整, 催化剂, 催化机制

Abstract:

Hydrogen production by catalytic ethanol steam reforming (ESR) is deemed to be a highly promising hydrogen-production pathway due to its high efficiency, sustainable ethanol source and low toxicity. The deficiencies in efficiency, selectivity and stability of existing catalysts have hindered the extensive application of hydrogen production from ESR. Herein, recent progress in the studies of metallic catalysts for ESR reaction were reviewed, especially on the effects of elemental composition of active species and support on the performance of catalysts. The influence of catalysts, reaction temperature and water/ethanol ratio on the product selectivity of ESR, the mechanism of coke formation during the ESR reaction, and the strategies of removal of carbon coke to improve the durability of catalysts were systematically reviewed and analyzed. Experimental and theoretical insights into the mechanism of catalytic ESR reaction in literature were also summarized. In summary, ESR reaction mechanism and the synergistic effect between metallic catalyst and the catalyst support are proposed to be the focus in the development of catalysts of high-efficiency and high-selectivity in future.

Key words: hydrogen production, alcohol, reforming, catalyst, catalytic mechanism

中图分类号:

TK91

陈俊, 舒红飞, 阮祝华, 倪嘉琪, 鲁礼林, 刘义. 乙醇催化重整产氢催化剂及催化反应机制[J]. 化工进展, 2019, 38(05): 2320-2328.

Jun CHEN, Hongfei SHU, Zhuhua RUAN, Jiaqi NI, Lilin LU, Yi LIU. Catalysts and catalytic mechanism for hydrogen production from ethanol steam reforming (ESR)[J]. Chemical Industry and Engineering Progress, 2019, 38(05): 2320-2328.

图/表 6

图1 反应温度对γ-Al2O3负载贵金属催化剂催化乙醇重整反应产物选择性的影响[9]

图2 MgO负载金属（Pd、Rh、Ni、Co）催化乙醇重整反应的乙醇转化率和氢气选择性[15]

图3 催化剂载体对Rh催化剂(1.0%)催化产氢速率(反应气空速69600h-1)和催化剂稳定性(反应温度700℃)的影响[24]

图4 反应温度和原料气中水醇比对乙醇重整反应产物分布的影响(K掺杂Ni/ZrO2催化剂)[34]

图5 催化剂Ni/CeO2和PtNi/CeO2中含Ni物相在催化剂活化和乙醇重整过程中的动态转变示意图[52]

图6 钴金属催化剂[Co(0001)晶面]催化乙醇重整反应路径和能垒最低反应通道势能面图[65]

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乙醇催化重整产氢催化剂及催化反应机制

Catalysts and catalytic mechanism for hydrogen production from ethanol steam reforming (ESR)

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