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甲酸辅助Cu-ZnO-Al2O3催化剂制备及其CO2加氢制甲醇性能研究

姜秀云 杨文兵 宋昊 马清祥 高新华 李鹏 赵天生

姜秀云, 杨文兵, 宋昊, 马清祥, 高新华, 李鹏, 赵天生. 甲酸辅助Cu-ZnO-Al2O3催化剂制备及其CO2加氢制甲醇性能研究[J]. 燃料化学学报(中英文), 2023, 51(1): 120-128. doi: 10.1016/S1872-5813(22)60041-0
引用本文: 姜秀云, 杨文兵, 宋昊, 马清祥, 高新华, 李鹏, 赵天生. 甲酸辅助Cu-ZnO-Al2O3催化剂制备及其CO2加氢制甲醇性能研究[J]. 燃料化学学报(中英文), 2023, 51(1): 120-128. doi: 10.1016/S1872-5813(22)60041-0
JIANG Xiu-yun, YANG Wen-bing, SONG Hao, MA Qing-xiang, GAO Xin-hua, LI Peng, ZHAO Tian-sheng. Formic acid assisted synthesis of Cu-ZnO-Al2O3 catalyst and its performance in CO2 hydrogenation to methanol[J]. Journal of Fuel Chemistry and Technology, 2023, 51(1): 120-128. doi: 10.1016/S1872-5813(22)60041-0
Citation: JIANG Xiu-yun, YANG Wen-bing, SONG Hao, MA Qing-xiang, GAO Xin-hua, LI Peng, ZHAO Tian-sheng. Formic acid assisted synthesis of Cu-ZnO-Al2O3 catalyst and its performance in CO2 hydrogenation to methanol[J]. Journal of Fuel Chemistry and Technology, 2023, 51(1): 120-128. doi: 10.1016/S1872-5813(22)60041-0

甲酸辅助Cu-ZnO-Al2O3催化剂制备及其CO2加氢制甲醇性能研究

doi: 10.1016/S1872-5813(22)60041-0
基金项目: 国家自然科学基金(22169014,21766027) ,宁夏自然科学基金(2022AAC03040, 2021AAC03108)和宁夏大学研究生创新项目(GIP2020053)资助
详细信息
    通讯作者:

    Tel:0951-2062393,E-mail:maqx@nxu.edu.cn

    zhaots@nxu.edu.cn

  • 中图分类号: O643.36

Formic acid assisted synthesis of Cu-ZnO-Al2O3 catalyst and its performance in CO2 hydrogenation to methanol

Funds: The project was supported by National Natural Science Foundation of China (22169014, 21766027), Natural Science Foundation of Ningxia (2022AAC03040, 2021AAC03108) and Graduate Innovation Project of Ningxia University (GIP2020053)
  • 摘要: 采用共沉淀法制备Cu/Zn/Al前驱体,经甲酸处理后N2气氛焙烧得到Cu-ZnO-Al2O3催化剂(CZA)用于CO2加氢制甲醇反应。使用XRD、BET、TG-DSC、SEM、H2-TPR、N2O滴定、XPS-AES、CO2-TPD表征技术对催化剂的物相组成、结构性质以及Cu物种的比表面积、分散度以及价态分布进行分析和讨论。结果表明,甲酸处理调节了催化剂中Cu+与Cu0的比例,同时增加催化剂的中强碱性,并提高甲醇选择性。在W/F(H2/CO2=70/23) = 10 g∙h/mol、t = 200 ℃、p = 3 MPa反应条件下,使用HCOOH/Cu(物质的量比)= 0.8甲酸处理获得的催化剂,CO2转化率6.7%,甲醇选择性达76.3%。
  • 图  1  反应前后xf-CZA催化剂的XRD谱图

    Figure  1  XRD patterns of xf-CZA catalysts

    (a): Before reaction; (b): After reaction

    图  2  前驱体样品的热分析曲线

    Figure  2  Thermal analysis curve of precursor samples

    (a): TG; (b): DSC

    图  3  xf-CZA催化剂的N2吸附-脱附等温线和孔径分布

    Figure  3  N2 adsorption-desorption isotherms and pore diameter distribution of xf-CZA catalysts

    (a): N2 adsorption-desorption isotherm; (b): Pore diameter distribution

    图  4  xf-CZA催化剂的SEM照片

    Figure  4  SEM images of xf-CZA catalysts

    (a): 0f-CZA; (b): 0.4f-CZA; (c): 0.8f-CZA; (d): 1.2f-CZA; (e): 2.4f-CZA

    图  5  xf-CZA催化剂的H2-TPR谱图

    Figure  5  H2-TPR profiles of xf-CZA catalysts

    图  6  xf-CZA催化剂的XPS谱图

    Figure  6  XPS patterns of xf-CZA catalysts

    (a): Cu 2p XPS of fresh xf-CZA; (b): Cu 2p XPS of spent xf-CZA; (c): Auger Cu LMM of fresh xf-CZA; (d): Auger Cu LMM of spent xf-CZA

    图  7  xf-CZA催化剂的CO2-TPD谱图

    Figure  7  CO2-TPD profiles of the xf-CZA catalysts

    图  8  xf-CZA催化剂的催化性能随反应时间的变化

    Figure  8  Relationship between the catalytic performance of xf-CZA catalyst and reaction time

    Reaction conditions: H2/CO2/Ar = 70/23/7, W/F = 10 g·h/mol, p = 3.0 MPa, t = 200 ℃, TOS = 48 h

    表  1  催化剂样品的织构性质参数

    Table  1  Texture property parameters of catalysts

    CatalystSBET/(m2·g−1)DCu/% aSCu/(cm2·g−1) a
    0f-CZA66.98.557.7
    0.4f-CZA59.36.745.5
    0.8f-CZA47.15.839.4
    1.2f-CZA38.54.933.6
    2.4f-CZA13.12.516.8
    a: Calculated by N2O titration; DCu: Dispersion of Cu;
    SCu: Specific surface area of Cu particle
    下载: 导出CSV

    表  2  催化剂表面Cu组分分析

    Table  2  Copper component analysis on catalyst surface

    Fresh catalystKinetic energy /eV Cu0/(Cu+ + Cu0)Spent catalystKinetic energy /eVCu0/(Cu+ + Cu0)
    Cu+Cu0Cu+Cu0
    0f-CZA 916.9 919.1 0.20 0f-CZA 916.9 918.9 0.41
    0.4f-CZA 916.9 919.0 0.31 0.4f-CZA 916.6 918.3 0.59
    0.8f-CZA 916.7 918.6 0.40 0.8f-CZA 916.6 918.5 0.63
    1.2f-CZA 916.8 918.8 0.44 1.2f-CZA 916.6 918.7 0.67
    2.4f-CZA 916.7 918.6 0.62 2.4f-CZA 916.9 918.9 0.65
    下载: 导出CSV

    表  3  xf-CZA催化剂活性评价

    Table  3  Activity evaluation of xf-CZA catalyst

    Catalyst${ {x} }_{ {\rm{CO} }_{{2} } }/\text{%}$${ {s} }_{ {\rm{CH} }_{3}\rm{OH} }/\text{%}$${ {s} }_{\rm{CO} }/\text{%}$${ {w} }_{ {\rm{CH} }_{3 }\rm{OH} }/\text{%}$
    0f-CZA 7.6 60.2 39.8 4.5
    0.4f-CZA 7.2 64.8 35.2 4.7
    0.8f-CZA 6.7 76.3 23.7 5.1
    1.2f-CZA 6.1 77.9 22.1 4.7
    2.4f-CZA 2.8 80.2 19.8 2.2
    Reaction conditions: H2/CO2/Ar = 70/23/7, W/F = 10 g·h/mol,
    p = 3.0 MPa, t = 200 ℃, TOS = 48 h
    下载: 导出CSV
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  • 收稿日期:  2022-04-02
  • 修回日期:  2022-05-20
  • 录用日期:  2022-06-10
  • 网络出版日期:  2022-06-23
  • 刊出日期:  2023-01-10

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