CeO2-Al2O3复合载体负载Ni基催化剂催化CO x 共甲烷化性能

doi:10.16085/j.issn.1000-6613.2022-1260

化工进展 ›› 2023, Vol. 42 ›› Issue (5): 2421-2428.DOI: 10.16085/j.issn.1000-6613.2022-1260

CeO₂-Al₂O₃复合载体负载Ni基催化剂催化CO _x 共甲烷化性能

马源¹^,²(), 肖晴月¹^,³, 岳君容¹, 崔彦斌¹, 刘姣¹(), 许光文³

^1.中国科学院过程工程研究所多相复杂系统国家重点实验室，北京 100190
^2.中南大学化学化工学院，湖南长沙 410083
^3.沈阳化工大学能源与化工产业技术研究院，辽宁沈阳 110142

收稿日期:2022-07-05 修回日期:2022-10-15 出版日期:2023-05-10 发布日期:2023-06-02
通讯作者: 刘姣
作者简介:马源（1995—），女，博士研究生，研究方向为纳米材料的制备与表征。E-mail：mayuan95mvp@163.com。
基金资助:
国家重点研发计划(2019YFC1906802)

CO _xco-methanation over a Ni-based catalyst supported on CeO₂-Al₂O₃ composite

MA Yuan¹^,²(), XIAO Qingyue¹^,³, YUE Junrong¹, CUI Yanbin¹, LIU Jiao¹(), XU Guangwen³

^1.State Key Laboratory of Muti-Phase Complex System, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^2.College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, Hunan, China
^3.Institute of Industrial Chemistry and Energy Technology, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China

Received:2022-07-05 Revised:2022-10-15 Online:2023-05-10 Published:2023-06-02
Contact: LIU Jiao

摘要/Abstract

摘要：

通过浸渍沉淀法分别制备Ni/Al₂O₃、Ni/CeO₂和Ni/CeO₂-Al₂O₃催化剂，并对其分别进行不同CO/CO₂比例下CO _x 共甲烷化性能评价。发现Ni/Al₂O₃催化剂催化CO转化为CH₄的能力明显高于Ni/CeO₂，而催化CO₂甲烷化的性能则相反。采用Ni/CeO₂-Al₂O₃催化剂，可以在提高CO转化率的同时而不降低CO₂转化率。结合BET、XRD、TPR、TPD和原位红外等各种表征手段，发现CeO₂掺杂虽然降低了催化剂的比表面积和金属Ni的分散度，但却可明显提高其吸附活化CO₂的能力，这主要是由于具有较高含量氧空位的CeO₂的掺杂可以提高载体表面碱性位，促使共甲烷过程中CO₂吸附活化并形成单齿碳酸盐，通过快速加氢反应生成目标产物甲烷；而Ni/Al₂O₃受限于其对CO₂的吸附容量和活化产物双齿碳酸盐的活性，在催化共甲烷化体系中只能获得较低的CO₂转化率，但CO转化率不受影响。

关键词: 二氧化碳, 一氧化碳, 甲烷化, 催化剂载体, 镍, 碱性位

Abstract:

Ni/Al₂O₃, Ni/CeO₂ and Ni/CeO₂-Al₂O₃catalysts were prepared by impregnation-precipitation method and applied for CO _xco-methanation with different ratios of CO/CO₂. It was found that the conversion of CO to CH₄ was higher over Ni/Al₂O₃than that_{over Ni/CeO₂, while CO₂ methanation gave reverse order. Adopting Ni/CeO₂-Al₂O₃ as CO _xco-methanation catalyst improved the CO conversion without lessening CO₂ conversion. BET, XRD, TPR, TPD and in-situ FTIR characterizations showed that the surface area and dispersion degree of metallic nickel decreased after CeO₂ was dopped in Al₂O₃. However, the CO₂ adsorption and activation capacity were increased, because the rich oxygen vacancies on CeO₂ would increase the basic sites on the support which activated CO₂ to monodentate carbonate, and then be hydrogenated to methane quickly. Limited by the CO₂ adsorption capacity and the activity of the medium product-bidentate carbonate, the CO₂ conversion over Ni/Al₂O₃ catalyst was lower than that over Ni/CeO₂-Al₂O₃catalyst while CO conversion was unaffected during CO _xco-methanation.}

Key words: carbon dioxide, carbon monoxide, methanation, catalyst support, nickel (Ni), basic site

中图分类号:

TQ032.4

马源, 肖晴月, 岳君容, 崔彦斌, 刘姣, 许光文. CeO₂-Al₂O₃复合载体负载Ni基催化剂催化CO _x 共甲烷化性能[J]. 化工进展, 2023, 42(5): 2421-2428.

MA Yuan, XIAO Qingyue, YUE Junrong, CUI Yanbin, LIU Jiao, XU Guangwen. CO _xco-methanation over a Ni-based catalyst supported on CeO₂-Al₂O₃ composite[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2421-2428.

图/表 8

图1 Ni/CeO2和Ni/Al2O3催化剂在共甲烷化反应中的催化性能

图2 共甲烷化反应在不同Ni基催化剂及不同催化体系作用下的催化活性

表1 不同Ni基催化剂的结构和物理性质

催化剂

比表面积^①

/m²·g^-1

孔容^②

/cm³·g^-1

平均孔径^③

/nm

Ni负载量^④

Ni/Al₂O₃

Ni/CeO₂

Ni/CeO₂-Al₂O₃

图3 不同载体Ni基催化剂的XRD谱图

图4 不同载体Ni基催化剂的H2-TPR曲线

图5 不同载体Ni基催化剂的H2-TPD和CO2-TPD曲线

表2 不同载体Ni基催化剂的化学吸附计算结果

催化剂

H₂吸附量

/μmol·g_cat^-1

CO₂吸附量

/μmol·g_cat^-1

D_Ni/%

A_Ni

/m²·g_Ni^-1

Ni/Al₂O₃

Ni/CeO₂

Ni/CeO₂-Al₂O₃

图6 不同载体Ni基催化剂吸附CO2后的原位红外图谱

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CeO₂-Al₂O₃复合载体负载Ni基催化剂催化CO _x 共甲烷化性能

CO _xco-methanation over a Ni-based catalyst supported on CeO₂-Al₂O₃ composite

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