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高导热SiO2@Al载体的制备及其在费托合成中的应用

张天鹏 王俊刚 章日光 陈从标 贾丽涛 李德宝 侯博

张天鹏, 王俊刚, 章日光, 陈从标, 贾丽涛, 李德宝, 侯博. 高导热SiO2@Al载体的制备及其在费托合成中的应用[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2021050
引用本文: 张天鹏, 王俊刚, 章日光, 陈从标, 贾丽涛, 李德宝, 侯博. 高导热SiO2@Al载体的制备及其在费托合成中的应用[J]. 燃料化学学报. doi: 10.19906/j.cnki.JFCT.2021050
ZHANG Tian-peng, WANG Jun-gang, ZHANG Ri-guang, CHEN Cong-biao, JIA Li-tao, LI De-bao, HOU Bo. Preparation of high thermal conductivity SiO2@Al support and its application in Fischer-Tropsch synthesis[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2021050
Citation: ZHANG Tian-peng, WANG Jun-gang, ZHANG Ri-guang, CHEN Cong-biao, JIA Li-tao, LI De-bao, HOU Bo. Preparation of high thermal conductivity SiO2@Al support and its application in Fischer-Tropsch synthesis[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2021050

高导热SiO2@Al载体的制备及其在费托合成中的应用

doi: 10.19906/j.cnki.JFCT.2021050
基金项目: 国家自然科学基金(21872162, 21902170),山西省重点研发计划(201903D121033)和煤科学与技术省部共建国家重点实验室培育基地开放课题基金资助项目(MKX201902)资助
详细信息
    通讯作者:

    E-mail: houbo@sxicc.ac.cn

  • 中图分类号: O643

Preparation of high thermal conductivity SiO2@Al support and its application in Fischer-Tropsch synthesis

Funds: The project was supported by the National Natural Science Foundation of China (21872162, 21902170), the Key Research Project of Shanxi Province (201903D121033) and the Key Laboratory of Coal Science and Technology, Taiyuan University of Technology (MKX201902)
  • 摘要: 通过在弱碱性条件下水解正硅酸乙酯(TEOS),以六烷基三甲基溴化铵(CTAB)为模板剂成功制备了SiO2@Al核壳结构高导热载体,并采用过量浸渍法负载15%(质量分数)钴物种,进行了费托合成反应性能考察。结果表明,制备得到的核壳结构载体既保留了高金属铝含量,又具有高比表面壳层,孔径较为均一,约为2.6−2.8 nm。通过改变正硅酸乙酯的添加量可以调节载体中二氧化硅的含量,进而控制壳层厚度。随着二氧化硅壳层厚度的增加,载体的比表面积逐渐增大,催化剂还原度降低。二氧化硅壳层增强了金属钴的分散,避免金属钴在铝颗粒上的团聚失活。在相近转化率条件下,壳层厚度较薄的15Co/5-SiO2@Al催化剂显示出最好的费托反应性能,这主要归因于较薄的二氧化硅壳层和金属钴颗粒之间具有适中的金属-载体相互作用,在起到锚定分散钴物种的同时提高了钴物种的还原度。
  • 图  1  载体(a)和催化剂(b)的XRD谱图

    a: 0-SiO2@Al; b: 5-SiO2@Al; c: 10-SiO2@Al; d: 20-SiO2@Al; e: 15Co/0-SiO2@Al; f: 15Co/5-SiO2@Al; g: 15Co/10-SiO2@Al; h: 15Co/20-SiO2@Al

    Figure  1.  The XRD patterns of the supports (a) and catalysts (b)

    图  2  样品的N2吸脱附曲线和孔径分布

    (a), (c) for supports; (b), (d) for catalysts; a: 0-SiO2@Al; b: 5-SiO2@Al; c: 10-SiO2@Al; d: 20-SiO2@Al; e: 15Co/0-SiO2@Al; f: 15Co/5-SiO2@Al; g: 15Co/10-SiO2@Al; h: 15Co/20-SiO2@Al

    Figure  2.  N2 adsorption-desorption isotherms and pore size distribution of the samples

    图  3  载体和催化剂的SEM照片

    a: 0-SiO2@Al; b: 5-SiO2@Al; c: 10-SiO2@Al; d: 20-SiO2@Al; e: 15Co/0-SiO2@Al; f: 15Co/5-SiO2@Al; g: 15Co/10-SiO2@Al; h: 15Co/20-SiO2@Al; i: used-15Co/0-SiO2@Al; j: used-15Co/5-SiO2@Al; k: used-15Co/10-SiO2@Al; l: used-15Co/20-SiO2@Al

    Figure  3.  SEM images of the supports and catalysts

    图  4  催化剂的H2-TPR曲线

    a: 15Co/0-SiO2@Al; b: 15Co/5-SiO2@Al; c: 15Co/10-SiO2@Al; d: 15Co/20-SiO2@Al

    Figure  4.  H2-TPR profiles of the catalysts

    图  5  二氧化硅含量对催化剂的选择性和TOF的影响

    (a): Selectivity; (b): TOF

    Figure  5.  The effect of silica content on the selectivity and TOF of catalysts

    表  1  载体和催化剂的物化性质

    Table  1.   Physico-chemical properties of the supports and the catalysts

    SamplesABET/(m2·g−1)vp/(cm3·g-1)dp/nmAla/wt%d(Co)b/nmReducibilityc/%Dispersiond/%ds(Co)e/nm
    0-SiO2@Al0.1898.6
    5-SiO2@Al74.270.04062.893.7
    10-SiO2@Al115.870.06402.690.4
    20-SiO2@Al197.680.10142.882.8
    15Co/0-SiO2@Al6.700.054934.317.1568.724.123.49
    15Co/5-SiO2@Al45.130.05655.016.7067.964.322.50
    15Co/10-SiO2@Al65.160.06103.716.5257.505.019.34
    15Co/20-SiO2@Al130.090.08473.314.9338.525.318.08
    ABET: BET surface area; vp: BJH pore volume; dp: average pore diameter; a: calculated by ICP-OES; b: calculated by Scherrer equation according to the 2θ = 36.9° diffraction peak of Co3O4, d(Co) = 0.75d(Co3O4); c: calculated by H2-TPR; d : calculated by Dispersion = 96/d s(Co) e: calculated from H2 chemisorption
    下载: 导出CSV

    表  2  催化剂的费托反应性能

    Table  2.   Performance of different catalysts on Fischer-Tropsch synthesis

    Catalystst/
    °C
    xCO /
    %
    Selectivity s/%TOF/
    (10−3·s−1)
    Criterions a
    CH4C2−4C5+
    15Co/0-SiO2@Al1856.1816.2012.3071.51
    15Co/5-SiO2@Al20527.969.6611.8678.4823.741.03E-4
    15Co/10-SiO2@Al21527.1819.6318.2162.1619.751.00E-4
    15Co/20-SiO2@Al20530.6121.7128.5749.7119.211.05E-4
    a: Mears Criterions, calculated by the formula (1); Reaction conditions: H2/CO (molar ratio) = 2.0,GHSV = 1000 h-1p = 2.0 MPa,Time on stream = 48 h
    下载: 导出CSV
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  • 网络出版日期:  2021-03-29

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