低温等离子体构筑高效Ni基催化剂进展

doi:10.16085/j.issn.1000-6613.2021-0221

摘要/Abstract

摘要：

Ni基催化剂价格低廉、资源丰富、活性出色，但其抗积炭能力差、易因严重积炭而失活的问题始终是限制其应用的瓶颈，如何提升Ni基催化剂抗积炭能力是学术界和工业界极为关注的问题。低温等离子体因宏观低温、粒子高能的特点而被广泛用于构筑高抗积炭Ni基催化剂。本文介绍了低温等离子体构筑高效Ni基催化剂领域的最新进展，讨论了低温等离子体较低的宏观温度和丰富的高能粒子对载体性质、Ni-载体作用和Ni颗粒特性的影响，分析了低温等离子体所构筑Ni基催化剂具有优异抗积炭能力的原因，提出增加Ni基催化剂制备量、降低低温等离子体耗电量和将低温等离子体与人工智能等技术结合是未来低温等离子体构筑Ni基催化剂领域的主要研究方向。

关键词: 催化剂, 积炭, 低温等离子体, 载体, 界面, 镍

Abstract:

Ni-based catalysts have advantages of low cost, rich resource and high catalytic activity. However, Ni-based catalyst has a poor resistance to carbon deposition, and thus can be easily deactivated due to serious carbon deposition. How to improve the resistance of Ni-based catalyst to carbon deposition is a focus of both academia and industry. Cold plasma has been widely used in fabricating coke-resistant Ni-based catalysts, due to its low operation temperature and abundant high-energy species. In the present paper, recent progresses in fabricating coke-resistant Ni-based catalysts by cold plasma are reviewed. The influences of the low operation temperature and high-energy species of cold plasma on the properties of supports, Ni-support interactions and Ni nanoparticles are discussed. The origins for the enhanced carbon deposition resistance of the Ni-based catalysts prepared by cold plasma are analyzed. Finally, we propose that increasing the yield of Ni-based catalysts, decreasing the power consumption and combining cold plasma with other techniques like artificial intelligence are the main research directions in the field of preparing coke-resistant Ni-based catalysts by cold plasma.

Key words: catalyst, carbon deposition, cold plasma, support, interface, nickel

中图分类号:

TQ032

彭冲, 刘鹏, 胡永康, 肖文德, 潘云翔. 低温等离子体构筑高效Ni基催化剂进展[J]. 化工进展, 2021, 40(7): 3553-3563.

PENG Chong, LIU Peng, HU Yongkang, XIAO Wende, PAN Yunxiang. Recent progress in fabricating efficient Ni-based catalysts by cold plasma[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3553-3563.

图/表 8

图1 Ni基催化剂的传统构筑过程和低温等离子体构筑过程

图2 低温等离子体装置示意图

图3 Ni/γ-Al2O3上CO2加氢生成HCOOδ-和CO的活化能与反应热[25]

图4 高温焙烧和辉光放电等离子体所制备Ni/SiO2[22]

图5 高温焙烧和辉光放电等离子体所制备Ni/SiO2的积炭[22]

图6 Ni/CeO2-SiO2-C和Ni/CeO2-SiO2-P表面积炭的程序升温氧化反应曲线[30]

图7 NiCo/SiO2-U和NiCo/SiO2-H表面CO加氢反应路径[38]

表1 低温等离子体制备的高抗积炭Ni基催化剂

催化剂	低温等离子体	制备方法（图1）	反应	结构特征和表面性质	文献
Ni/SiO₂	辉光放电介质阻挡放电介质阻挡放电	方法2 方法2 方法2	CH₄-CO₂重整 CH₄-H₂O重整 CO甲烷化	Ni-SiO₂作增强，Ni颗粒尺寸小、晶型好 Ni颗粒尺寸5.5nm，小于传统催化剂（15.3nm） Ni颗粒缺陷位少	［22］［20］［39］
Ni/Ga₂O₃/SiO₂	介质阻挡放电	方法2	CH₄-CO₂重整	具有较强的吸附和活化CO₂的能力	［24］
Ni/CeO₂/SiO₂	介质阻挡放电	方法2	CH₄-CO₂重整	Ni-SiO₂作用增强、表面具有大量活性氧物种	［30］
Ni/γ-Al₂O₃	辉光放电	方法2	CH₄-CO₂重整	Ni-载体作用强，Ni颗粒尺度小，Ni（111）面多	［23］
Ni/CeO₂	介质阻挡放电	方法1	CO₂甲烷化 CO甲烷化	Ni-CeO₂作用强，Ni颗粒尺寸小具有较多Ni-CeO₂界面位置	［40］［41］
Ni/ZrO₂	介质阻挡放电	方法1	CO₂甲烷化 CH₄-CO₂重整	Ni颗粒尺寸小，Ni（111）面多 ZrO₂表面具有丰富氧缺陷位	［19］［27］
Ni/TiO₂	介质阻挡放电	方法1	CO₂甲烷化	Ni（111）面多	［32］
Ni/MgO	介质阻挡放电	方法2	CO分解	Ni颗粒缺陷位少，具有更多Ni（111）面	［21］
Ni/MgAl₂O₄	介质阻挡放电	方法1	CH₄分解 CO₂甲烷化	Ni颗粒缺陷位少，具有更多Ni（111）面具有高品质Ni-MgAl₂O₄界面	［31］［42］
Ni-Co/SiO₂	介质阻挡放电	方法2	CO甲烷化	形成均质Ni-Co颗粒	［38］
Ni/Y₂Ti₂O₇	介质阻挡放电	方法2/方法3	CH₄-H₂O重整	Ni-载体作用强，表面具有大量活性 $O 2 -$ 位	［43］
Ni-Fe/Al₂O₃	介质阻挡放电	方法1	CO₂甲烷化	Ni-Fe合金颗粒	［44］
Ni-Ce/SBA-15	介质阻挡放电	方法1	CO甲烷化	Ni颗粒尺寸小	［45］
Ni/LaFeO₃	介质阻挡放电	方法2	CH₄-H₂O重整	Ni-载体作用强，Ni颗粒分散性好	［46］
Ni-Co/Al₂O₃-ZrO₂	辉光放电	方法2	CH₄-CO₂重整	金属-载体作用强，金属颗粒尺寸小	［47］

表1 低温等离子体制备的高抗积炭Ni基催化剂

催化剂	低温等离子体	制备方法（图1）	反应	结构特征和表面性质	文献
Ni/SiO₂	辉光放电介质阻挡放电介质阻挡放电	方法2 方法2 方法2	CH₄-CO₂重整 CH₄-H₂O重整 CO甲烷化	Ni-SiO₂作增强，Ni颗粒尺寸小、晶型好 Ni颗粒尺寸5.5nm，小于传统催化剂（15.3nm） Ni颗粒缺陷位少	［22］［20］［39］
Ni/Ga₂O₃/SiO₂	介质阻挡放电	方法2	CH₄-CO₂重整	具有较强的吸附和活化CO₂的能力	［24］
Ni/CeO₂/SiO₂	介质阻挡放电	方法2	CH₄-CO₂重整	Ni-SiO₂作用增强、表面具有大量活性氧物种	［30］
Ni/γ-Al₂O₃	辉光放电	方法2	CH₄-CO₂重整	Ni-载体作用强，Ni颗粒尺度小，Ni（111）面多	［23］
Ni/CeO₂	介质阻挡放电	方法1	CO₂甲烷化 CO甲烷化	Ni-CeO₂作用强，Ni颗粒尺寸小具有较多Ni-CeO₂界面位置	［40］［41］
Ni/ZrO₂	介质阻挡放电	方法1	CO₂甲烷化 CH₄-CO₂重整	Ni颗粒尺寸小，Ni（111）面多 ZrO₂表面具有丰富氧缺陷位	［19］［27］
Ni/TiO₂	介质阻挡放电	方法1	CO₂甲烷化	Ni（111）面多	［32］
Ni/MgO	介质阻挡放电	方法2	CO分解	Ni颗粒缺陷位少，具有更多Ni（111）面	［21］
Ni/MgAl₂O₄	介质阻挡放电	方法1	CH₄分解 CO₂甲烷化	Ni颗粒缺陷位少，具有更多Ni（111）面具有高品质Ni-MgAl₂O₄界面	［31］［42］
Ni-Co/SiO₂	介质阻挡放电	方法2	CO甲烷化	形成均质Ni-Co颗粒	［38］
Ni/Y₂Ti₂O₇	介质阻挡放电	方法2/方法3	CH₄-H₂O重整	Ni-载体作用强，表面具有大量活性 $O 2 -$ 位	［43］
Ni-Fe/Al₂O₃	介质阻挡放电	方法1	CO₂甲烷化	Ni-Fe合金颗粒	［44］
Ni-Ce/SBA-15	介质阻挡放电	方法1	CO甲烷化	Ni颗粒尺寸小	［45］
Ni/LaFeO₃	介质阻挡放电	方法2	CH₄-H₂O重整	Ni-载体作用强，Ni颗粒分散性好	［46］
Ni-Co/Al₂O₃-ZrO₂	辉光放电	方法2	CH₄-CO₂重整	金属-载体作用强，金属颗粒尺寸小	［47］

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