Ni/Sm2O3-CeO2/Al2O3催化剂氧空位对二氧化碳低温甲烷化的影响

doi:10.16085/j.issn.1000-6613.2023-0571

摘要/Abstract

摘要：

通过水热合成法将Mn、Sm和Ce作为助剂，掺入水滑石（LDHs）前体后经焙烧-还原分别得到Ni/Sm₂O₃-CeO₂/Al₂O₃和Ni/MnO _x -Sm₂O₃-CeO₂/Al₂O₃催化剂，研究了两种结构催化剂的二氧化碳低温甲烷化反应。研究结果表明，相较于Ni/Sm₂O₃-CeO₂/Al₂O₃，MnO _x 的引入使Ni/MnO _x -Sm₂O₃-CeO₂/Al₂O₃在225℃以下表现出优异的性能，CO₂转化率达到68%，CH₄选择性达到100%，且在100h内具有良好的稳定性，150℃时TOF为0.087s^-1，大于Ni/Sm₂O₃-CeO₂/Al₂O₃（0.013s^-1）。这主要是由于引入MnO _x，在保持金属颗粒高度分散的同时，借助MnO _x 在催化剂表面连续还原，提高了Ni/MnO _x -Sm₂O₃-CeO₂/Al₂O₃表面氧空位浓度且增加了催化剂的碱性位点，促进了二氧化碳的吸附和活化。原位红外结果进一步表明，低温下催化剂表面氧空位促进甲酸盐和甲氧基中间物种的生成，进而提高了二氧化碳甲烷化活性。

关键词: 二氧化碳, 加氢, 甲烷, 催化剂, 催化（作用）

Abstract:

Ni/Sm₂O₃-CeO₂/Al₂O₃ and Ni/MnO _x -Sm₂O₃-CeO₂/Al₂O₃ catalysts were obtained by using Mn, Sm and Ce sources in the form of LDHs precursor by hydrothermal synthesis after a standard calcination and reduction treatment. Subsequently, the catalytic performance of the two catalysts were investigated at low temperature in CO₂ methanation. Compared to Ni/Sm₂O₃-CeO₂/Al₂O₃, Ni/MnO _x -Sm₂O₃-CeO₂/Al₂O₃ with the introduction of MnO _x showed an excellent performance below 225℃, with 68% of CO₂ conversion and 100% of CH₄ selectivity, and 0.087s^-1 of TOF, which was higher than that of Ni/Sm₂O₃-CeO₂/Al₂O₃ (0.013s^-1). Meanwhile, Ni/MnO _x -Sm₂O₃-CeO₂/Al₂O₃ maintained stable CO₂ conversion and CH₄ selectivity in long-term test for 100h. This was mainly due to the fact that the introduction of MnO _x increased the oxygen vacancies on Ni/MnO _x -Sm₂O₃-CeO₂/Al₂O₃ with a high degree of Ni particle dispersion. Meanwhile, MnO _x could also increase the basic sites of the resultant catalyst, which promoted CO₂adsorption and activation. In situ DRIFTS analysis further revealed that oxygen vacancies on Ni/MnO _x -Sm₂O₃-CeO₂/Al₂O₃ promoted the formation of formate and methoxy intermediates at low temperatures, leading to an enhanced catalytic properties in CO₂ methanation.

Key words: carbon dioxide, hydrogenation, methane, catalyst, catalysis

中图分类号:

TQ032.4

郭潇东, 毛玉娇, 刘相洋, 邱丽, 于峰, 闫晓亮. Ni/Sm₂O₃-CeO₂/Al₂O₃催化剂氧空位对二氧化碳低温甲烷化的影响[J]. 化工进展, 2024, 43(4): 1840-1850.

GUO Xiaodong, MAO Yujiao, LIU Xiangyang, QIU Li, YU Feng, YAN Xiaoliang. Effect of oxygen vacancies in Ni/Sm₂O₃-CeO₂/Al₂O₃ catalyst on CO₂ methanation at low temperature[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 1840-1850.

图/表 15

图1 前体及焙烧后催化剂XRD谱图

图2 NiO/Sm2O3-CeO2/Al2O3和NiO/MnO x -Sm2O3-CeO2/Al2O3催化剂的XPS谱图

图3 NiO/Sm2O3-CeO2/Al2O3和NiO/MnO x -Sm2O3-CeO2/Al2O3催化剂的H2-TPR谱图

表1 NiO/Sm2O3-CeO2/Al2O3和NiO/MnO x -Sm2O3-CeO2/Al2O3催化剂还原温度

催化剂	H₂消耗峰/℃
催化剂	ε₁	ε₂	α	β₁	β₂	γ
NiO/Sm₂O₃-CeO₂/Al₂O₃	—	—	356	468	560	632
NiO/MnO _x -Sm₂O₃-CeO₂/Al₂O₃	192	262	360	470	570	642

图4 还原后催化剂的XRD与Mn 2p XPS谱图

图5 Ni/Sm2O3-CeO2/Al2O3和Ni/MnO x -Sm2O3-CeO2/Al2O3催化剂的TEM及相关EDS元素分布

图6 Ni/Sm2O3-CeO2/Al2O3和Ni/MnO x -Sm2O3-CeO2/Al2O3催化剂活性和稳定性评价

表2 不同催化剂在甲烷化反应中的催化性能

催化剂	反应温度/℃	空速/h^-1	CO₂转化率/%	CH₄选择性/%	参考文献
Ni/MnO _x -Sm₂O₃-CeO₂/Al₂O₃	225	15000	68	100	本工作
Ni/MnO _x -Sm₂O₃-CeO₂/Al₂O₃	250	15000	87.8	100	本工作
Ni/CeO₂-SGM	250	40000	80.5	95.8	[5]
NiCeAl-RMO	250	15000	78.6	100%	[13]
Ni/Pr-Ce	350	25000	54.5	100%	[17]
Ni/CeO₂-Co₃O₄	300	3600	85.4	>80%	[24]
Ni/ZrO₂-Al₂O₃-0.1	280	48000	84.4	99.4	[29]
1%Ru/CeO₂	300	1800	86	100	[30]
Co-Al-O	250	5000	74	99	[31]
Ni-Mn/γ-Al₂O₃	280	12000	85	99	[32]
Ni/La-Sm-Ce	350	25000	53	100	[33]
10Ni/CeO₂-La-600	300	30000	88.6	99%	[34]

图7 100h稳定性测试后Ni/MnO x -Sm2O3-CeO2/Al2O3催化剂结构分析

图8 焙烧后及还原后催化剂的O 1s XPS谱图

图9 Ni/Sm2O3-CeO2/Al2O3和Ni/MnO x -Sm2O3-CeO2/Al2O3催化剂拉曼谱图

图10 Ni/Sm2O3-CeO2/Al2O3和Ni/MnO x -Sm2O3-CeO2/Al2O3催化剂的CO2-TPD谱图

表3 Ni/Sm2O3-CeO2/Al2O3和Ni/MnO x -Sm2O3-CeO2/Al2O3催化剂的CO2-TPD定量计算结果

催化剂

弱碱性位点

/mmol·g^-1

中等碱性位点

/mmol·g^-1

强碱性位点

/mmol·g^-1

总碱度

/mmol·g^-1

Ni/Sm₂O₃-CeO₂/Al₂O₃

Ni/MnO _x -Sm₂O₃-CeO₂/Al₂O₃

图11 Ni/Sm2O3-CeO2/Al2O3和Ni/MnO x -Sm2O3-CeO2/Al2O3催化剂原位红外谱图♣羟基；♠CH4；∇甲氧基；♥CO；♦单齿碳酸盐；◇甲酸盐；+单齿碳酸盐；●碳酸氢盐

图12 Ni/Sm2O3-CeO2/Al2O3和Ni/MnO x -Sm2O3-CeO2/Al2O3催化剂反应过程中单齿碳酸盐、甲酸盐和甲氧基中间物种相对浓度的变化

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Ni/Sm₂O₃-CeO₂/Al₂O₃催化剂氧空位对二氧化碳低温甲烷化的影响

Effect of oxygen vacancies in Ni/Sm₂O₃-CeO₂/Al₂O₃ catalyst on CO₂ methanation at low temperature

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