Ni/CeO<sub>2</sub>前驱体分解方法对CO甲烷化活性的影响

引用本文: 张晓珊, 芮宁, 贾忻宇, 胡雪, 刘昌俊. Ni/CeO₂前驱体分解方法对CO甲烷化活性的影响[J]. 催化学报, 2019, 40(4): 495-503. doi: S1872-2067(19)63289-4 shu

Citation: Xiaoshan Zhang, Ning Rui, Xinyu Jia, Xue Hu, Chang-jun Liu. Effect of decomposition of catalyst precursor on Ni/CeO₂ activity for CO methanation[J]. Chinese Journal of Catalysis, 2019, 40(4): 495-503. doi: S1872-2067(19)63289-4 shu

Ni/CeO₂前驱体分解方法对CO甲烷化活性的影响

天津大学化工学院天津化学化工协同创新中心, 天津 300072
基金项目:
国家自然科学基金（21476157，21536008，21621004）；国家重点研发计划（2016YFB0600902）.

摘要: CO甲烷化制备合成天然气是煤化工的重要过程之一，也是合成氨过程和燃料电池除去痕量CO的重要反应.CO甲烷化催化剂包括贵金属催化剂和镍基催化剂.其中，镍基催化剂由于具有较好的活性以及较低的成本受到广泛的重视.目前，镍基CO甲烷化催化剂仍需解决的问题是提高低温活性以及抗积碳性能.目前的改进方法主要包括：（1）控制催化剂尺寸；（2）控制催化剂结构；（3）提高Ni-载体的相互作用；（4）使用结构可控的载体；（5）改进载体性质.其中，通过控制催化剂尺寸来控制催化剂结构是一种有效的改进方式.使用冷等离子体来分解镍前驱体是一种快速有效的制备尺寸小、分散度好的镍基催化剂的方法.
本文使用常压介质阻挡放电等离子体（150℃左右）分解硝酸镍前驱体，得到的催化剂再经过500℃氢气还原得到高分散Ni/CeO₂催化剂.作为对比，同时采用常规热焙烧方法分解硝酸镍制备了催化剂.对催化剂进行了X射线衍射（XRD）、CO脉冲化学吸附、CO程序升温脱附（CO-TPD）、CO红外漫反射光谱（CO-DFTIR）及X射线光电子能谱（XPS）等分析，同时进行了CO甲烷化反应活性和300℃下稳定性测试，发现等离子体分解制备得到的催化剂具有更好的CO低温甲烷化性能、更高的CH₄选择性、更好的低温稳定性和抗积碳性能.在250℃时，等离子体分解法制备的催化剂上的CO转化率能达到96.8%，CH₄选择性接近100%，但是热焙烧分解制备的催化剂上却只有14.7%的CO转化率.在低温（300℃）稳定性测试中，等离子体分解制备的催化剂具有优异的稳定性.与常规热焙烧方法得到的催化剂相比，等离子体制备得到的催化剂具有高的Ni分散度、更高的CO吸附性能以及更强的金属-载体相互作用.由于金属-载体相互作用被加强，部分电子由载体转移到金属Ni上，增强了金属与CO反键π轨道之间的电子密度，C-O键更易断裂，有利于甲烷化的发生.此外，XPS分析表明等离子体制备的催化剂表面有更多的Ce³⁺，证明了更多氧空位的存在.在Ni-载体界面上CO的O原子更容易被CeO₂的氧空位捕获而解离.更高的分散度提供了更多的Ni比表面积，也有利于加氢过程的进行，从而提高甲烷化活性.CO甲烷化稳定性测试之后催化剂的TG-DSC表征结果表明，等离子体分解制备的催化剂具有更少的积碳及更多的活性镍组分，同时催化剂上积碳的氧化温度更低，表明积碳具有更好的反应活性.
综上所述，等离子体低温分解制备的Ni/CeO₂表现出了更大的比表面积、更高的Ni分散度、增强的CO吸附性能和更多的氧空位，促进了CO甲烷化活性的提高.与文献数据相比，该催化剂具有更高的CO转化速率.

关键词:

English

Effect of decomposition of catalyst precursor on Ni/CeO₂ activity for CO methanation

Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
Received Date: 20 October 2018
Revised Date: 25 December 2018
Fund Project:
This work was supported by the National Natural Science Foundation of China (21476157, 21536008 and 21621004), and the National Key R&D Program of China (2016YFB0600902).

Abstract: CO methanation on Ni/CeO₂ has recently received increasing attention. However, the low-temperature activity and carbon resistance of Ni/CeO₂ still need to be improved. In this study, plasma decomposition of nickel nitrate was performed at ca. 150℃ and atmospheric pressure. This was followed by hydrogen reduction at 500℃ in the absence of plasma, and a highly dispersed Ni/CeO₂ catalyst was obtained with improved CO adsorption and enhanced metal-support interaction. The plasma-decomposed catalyst showed significantly improved low-temperature activity with high methane selectivity (up to 100%) and enhanced carbon resistance for CO methanation. For example, at 250℃, the plasma-decomposed catalyst showed a CO conversion of 96.8% with high methane selectivity (almost 100%), whereas the CO conversion was only 14.7% for a thermally decomposed catalyst.

Key words:

Nickel
/ CeO₂
/ Carbon monoxide
/ Syngas
/ Methanation
/ Plasma

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Ni/CeO₂前驱体分解方法对CO甲烷化活性的影响

English

Effect of decomposition of catalyst precursor on Ni/CeO₂ activity for CO methanation

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Ni/CeO2前驱体分解方法对CO甲烷化活性的影响

English

Effect of decomposition of catalyst precursor on Ni/CeO2 activity for CO methanation

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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Effect of decomposition of catalyst precursor on Ni/CeO₂ activity for CO methanation

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