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泡沫硅负载钴锰催化剂的制备及其合成气制低碳醇反应性能研究

杜鑫 张明伟 房克功

杜鑫, 张明伟, 房克功. 泡沫硅负载钴锰催化剂的制备及其合成气制低碳醇反应性能研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60444-5
引用本文: 杜鑫, 张明伟, 房克功. 泡沫硅负载钴锰催化剂的制备及其合成气制低碳醇反应性能研究[J]. 燃料化学学报(中英文). doi: 10.1016/S1872-5813(24)60444-5
DU Xin, ZHANG Mingwei, FANG Kegong. Preparation of silicon foam supported CoMn catalysts and their catalytic performances in higher alcohol synthesis via syngas[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60444-5
Citation: DU Xin, ZHANG Mingwei, FANG Kegong. Preparation of silicon foam supported CoMn catalysts and their catalytic performances in higher alcohol synthesis via syngas[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(24)60444-5

泡沫硅负载钴锰催化剂的制备及其合成气制低碳醇反应性能研究

doi: 10.1016/S1872-5813(24)60444-5
基金项目: 国家自然科学基金 (22179137)资助
详细信息
    通讯作者:

    Tel:0351-4064505, Fax: 0351-4041153 , E-mail: kgfang@sxicc.ac.cn

  • 中图分类号: O643

Preparation of silicon foam supported CoMn catalysts and their catalytic performances in higher alcohol synthesis via syngas

Funds: The project was supported by National Natural Science Foundation of China (22179137).
  • 摘要: 本研究采用浸渍法、沉淀法和水热合成法制备了一系列泡沫硅负载CoMn基催化剂,并结合XRD、H2-TPR、N2物理吸附-脱附、TEM和XPS等表征技术考察了制备方法对催化剂在合成气制低碳醇反应中的性能影响。研究表明,催化剂表面存在Co2+(Co2C)、Co0物种,水热合成法制备的催化剂表面Co2C-Co0活性位点存在良好的协同作用有利于醇的生成,较高比例的Co2C也促进了CO的非解离吸附和插入,从而呈现最高的醇选择性。在t=260 ℃,p=5.0 MPa,GHSV=4500 h−1,H2/CO(体积比)=2∶1的反应条件下,该泡沫催化剂可实现CO转化率11.1%,总醇选择性34.7%,C2+OH选择性34.5%的反应性能。
  • 图  1  CoMn/MCF催化剂合成示意图

    Figure  1  Schematic diagram of CoMn/MCF catalyst synthesis

    图  2  CoMn/MCF-IM(a)、(b)、(c)、CoMn/MCF-PM(d)、(e)、(f) 和CoMn/MCF-HM(h)、(i)、(j)的TEM图像

    Figure  2  TEM images of CoMn/MCF-IM (a), (b), (c), CoMn/MCF-PM (d), (e), (f), and CoMn/MCF-HM (h), (i), (j)

    图  3  载体及催化剂的N2吸附-脱附曲线(a)和孔径分布(b)

    Figure  3  N2 adsorption and desorption curves (a) and pore size distribution (b) of carriers and catalysts

    图  4  载体的SAXRD谱图

    Figure  4  SAXRD spectrum of the carrier

    图  5  焙烧后催化剂的XRD谱图

    Figure  5  XRD patterns of catalysts after calcination

    图  6  催化剂的H2-TPR谱图

    Figure  6  H2-TPR diagram of catalyst

    图  7  催化剂(焙烧后)的Co 2p和Mn 2p XPS谱图

    Figure  7  XPS spectra of Co 2p and Mn 2p catalysts (after calcination)

    图  8  催化剂CoMn/MCF-IM(a)、CoMn/MCF-PM(b)、CoMn/MCF-HM(c)的产物分布

    Figure  8  Product distribution diagram of catalysts CoMn/MCF-IM (a), CoMn/MCF-PM (b), and CoMn/MCF-HM (c)

    图  9  反应后催化剂的XRD谱图

    Figure  9  XRD patterns of the catalysts after reaction

    图  10  催化剂(反应后)的 Co 2p和Mn 2p XPS谱图

    Figure  10  XPS spectra of Co 2p and Mn 2p catalysts (after reaction)

    图  11  催化剂的醇选择性与Co2+/Co0比值

    Figure  11  Relationship diagram between alcohol selectivity of catalyst and Co2+/Co0 ratio Reaction conditions: 260 ℃, 5.0 MPa, GHSV=4500 h−1.

    图  12  CoMn/MCF催化剂合成气制低碳醇机理示意图

    Figure  12  The schematic mechanism of CoMn/MCF catalyst for higher alcohols synthesis from syngas

    表  1  实验用化学试剂

    Table  1  Experimental chemical reagents

    Chemical reagent Reagent grade Manufacturer
    Co(NO3)2·6H2O AR Sinopharm Chemical Reagent Co., Ltd
    50% Mn(NO3)2 solution AR Sinopharm Chemical Reagent Co., Ltd
    PEG-PPG-PEG, Pluronic®P-123, Average Mn ~5800 AR Sinopharm Chemical Reagent Co., Ltd
    C8H20O4Si AR Sinopharm Chemical Reagent Co., Ltd
    C6H6 AR Sinopharm Chemical Reagent Co., Ltd
    HCl AR Sinopharm Chemical Reagent Co., Ltd
    K2CO3 AR Sinopharm Chemical Reagent Co., Ltd
    CH4N2O AR Sinopharm Chemical Reagent Co., Ltd
    NH4F AR Aladdin
    Experimental water deionized water Laboratory homemade
    下载: 导出CSV

    表  2  样品的织构性质

    Table  2  Texture properties of the samples

    Sample SBET/(m2·g−1) Pore volume/(cm3·g−1) Average pore sizea/nm
    MCF 668 1.3 6.0
    CoMn/MCF-IM 383 0.5 4.5
    CoMn/MCF-PM 159 0.5 10.9
    CoMn/MCF-HM 229 0.6 8.4
    a: Average pore size = 4(pore volume/SBET).
    下载: 导出CSV

    表  3  催化剂的元素含量

    Table  3  The element contents of the catalysts

    Sample Co/% Mn/% Si/%
    CoMn/MCF-IM 12.91 4.65 29.90
    CoMn/MCF-PM 13.36 4.70 30.89
    CoMn/MCF-HM 13.48 4.02 30.82
    下载: 导出CSV

    表  4  催化剂的催化性能

    Table  4  The catalytic performance of catalystsa

    Sample xCO/% Selectivity/% Alcohol distribution STYROH/(g·g−1·h−1)
    ROH CHn CO2 MeOH C2+OH
    CoMn/MCF-IM 36.7 6.9 89.6 3.6 29.1 71.0 0.06
    CoMn/MCF-PM 6.3 26.8 73.3 0.0 54.6 45.4 0.02
    CoMn/MCF-HM 11.1 34.7 65.4 0.0 65.5 34.5 0.04
    a: Reaction conditions: t=260 ℃, p=5.0 MPa, GHSV=4500 h−1, H2/CO=2.0.
    下载: 导出CSV

    表  5  反应后催化剂表面钴元素相对含量

    Table  5  Relative contents of cobalt element on the surface of the catalyst after reactiona

    Catalyst Co2+(area%) Co0(area%) Co2+/Co0
    CoMn/MCF-IM 0.68 0.32 2.13
    CoMn/MCF-PM 0.81 0.19 4.26
    CoMn/MCF-HM 0.89 0.11 8.09
    a: Integrated area based on Co 2p3/2 main peak.
    下载: 导出CSV
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出版历程
  • 收稿日期:  2024-01-23
  • 修回日期:  2024-03-06
  • 录用日期:  2024-03-07
  • 网络出版日期:  2024-04-03

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