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绿色合成介孔碳负载(Ni)MoS2加氢脱硫催化剂

梁吉雷 吴雯洁 吴萌萌 花加伟 柳云骐 刘晨光

梁吉雷, 吴雯洁, 吴萌萌, 花加伟, 柳云骐, 刘晨光. 绿色合成介孔碳负载(Ni)MoS2加氢脱硫催化剂[J]. 燃料化学学报(中英文), 2023, 51(12): 1761-1771. doi: 10.19906/j.cnki.JFCT.2023033
引用本文: 梁吉雷, 吴雯洁, 吴萌萌, 花加伟, 柳云骐, 刘晨光. 绿色合成介孔碳负载(Ni)MoS2加氢脱硫催化剂[J]. 燃料化学学报(中英文), 2023, 51(12): 1761-1771. doi: 10.19906/j.cnki.JFCT.2023033
LIANG Ji-lei, WU Wen-jie, WU Meng-meng, HUA Jia-wei, LIU Yun-qi, LIU Chen-guang. Green synthesis of mesoporous carbon supported (Ni)MoS2 as efficient hydrodesulfurization catalyst[J]. Journal of Fuel Chemistry and Technology, 2023, 51(12): 1761-1771. doi: 10.19906/j.cnki.JFCT.2023033
Citation: LIANG Ji-lei, WU Wen-jie, WU Meng-meng, HUA Jia-wei, LIU Yun-qi, LIU Chen-guang. Green synthesis of mesoporous carbon supported (Ni)MoS2 as efficient hydrodesulfurization catalyst[J]. Journal of Fuel Chemistry and Technology, 2023, 51(12): 1761-1771. doi: 10.19906/j.cnki.JFCT.2023033

绿色合成介孔碳负载(Ni)MoS2加氢脱硫催化剂

doi: 10.19906/j.cnki.JFCT.2023033
基金项目: 国家自然科学基金(22078227),江苏省高校“青蓝工程”,重质油国家重点实验室开放课题(SKLOP201902005),江苏省高校自然科学基金面上项目(22KJB150040)和江苏省大学生创新创业训练计划(202212917019Z)资助
详细信息
    通讯作者:

    E-mail: liangjilei_httplan@126.com

  • 中图分类号: TQ426.95

Green synthesis of mesoporous carbon supported (Ni)MoS2 as efficient hydrodesulfurization catalyst

Funds: The project was supported by the National Natural Science Foundation of China (22078227), Qing Lan Project of Jiangsu Province, State Key Laboratory of Heavy Oil Processing (SKLOP201902005), Natural Science Foundation of Jiangsu Higher Education Institutions of China (22KJB150040), and Undergraduate Training Program for Innovation and Entrepreneurship of Jiangsu Province (202212917019Z).
  • 摘要: 以Anderson结构Ni-Mo杂多酸簇(NH4)4[NiMo6O24H6]·5H2O、硫脲、柠檬酸、氯化钠为原料,采用冻干法得到前驱体后焙烧、洗涤得到介孔碳骨架负载(Ni)MoS2纳米颗粒的加氢脱硫催化剂,考察了其对二苯并噻吩的加氢脱硫活性,并采用X射线衍射、N2低温吸附-脱附、拉曼光谱、X光电子能谱、扫描电子显微镜、高分辨透射电镜、程序升温还原等表征手段对催化剂进行了分析。结果表明,介孔碳骨架负载(Ni)MoS2纳米颗粒催化剂具有较弱的载体-金属相互作用,MoS2纳米颗粒平均长度较短(4.9 nm),层数适宜(4.8),NiMoS活性相含量较高,二苯并噻吩的转化率可达94.1%,反应速率常数及活性位转换频率分别可达1.7 × 10–6 mol/(g·s)和2.8 × 10–3 s–1。该方法利用原位生成的氯化钠晶体及硫化氢气体分别作为介孔模板剂和硫化剂,实现了介孔碳载体与(Ni)MoS2纳米颗粒的同步合成及锚定,并为加氢脱硫催化剂的绿色制备提供了新的思路。
  • FIG. 2803.  FIG. 2803.

    FIG. 2803.  FIG. 2803.

    图  1  催化剂的制备流程示意图

    Figure  1  Schematic illustration of the catalyst preparation

    图  2  Ni3Mo6S/C、NiMo6S/C催化剂及其未洗涤中间产物的XRD谱图

    Figure  2  XRD patterns of Ni3Mo6S/C, NiMo6S/C and intermediate products

    图  3  Ni3Mo6S/C((a)、(b))和NiMo6S/C((c)、(d))催化剂洗涤前后的SEM照片

    Figure  3  SEM images of Ni3Mo6S/C ((a), (b)) and NiMo6S/C ((c), (d))

    图  4  Ni3Mo6S/C(a)和NiMo6S/C(b)催化剂的元素分布

    Figure  4  Element mapping images of Ni3Mo6S/C (a) and NiMo6S/C (b)

    图  5  样品的N2吸附-脱附等温线(a)和孔径分布(b)

    Figure  5  N2 adsorption-desorption isotherms (a) and pore diameter distributions (b) of samples

    图  6  Ni3Mo6S/C和NiMo6S/C催化剂的拉曼光谱谱图

    Figure  6  Raman spectra of Ni3Mo6S/C and NiMo6S/C

    图  7  Ni3Mo6S/C(a)和NiMo6S/C(b)催化剂的HRTEM照片

    Figure  7  HRTEM images of Ni3Mo6S/C (a) and NiMo6S/C (b)

    图  8  两种催化剂表面MoS2纳米颗粒长度(a)和堆垛层数(b)统计

    Figure  8  Distributions of slab length (a) and stacking number (b) of MoS2 slabs over the catalysts

    图  9  Ni3Mo6S/C和NiMo6S/C催化剂的XPS谱图

    Figure  9  XPS spectra of Ni3Mo6S/C and NiMo6S/C

    图  10  Ni3Mo6S/C和NiMo6S/C催化剂的TPR谱图

    Figure  10  TPR profiles of Ni3Mo6S/C and NiMo6S/C

    表  1  Ni3Mo6S/C和NiMo6S/C催化剂的HRTEM及XPS分析

    Table  1  Characteristics of Ni3Mo6S/C and NiMo6S/C calculated by HRTEM and XPS

    CatalystL /nmNMoSulf /%NiMoS /%S2–/%
    NiMo6S/C5.44.280.447.187.7
    Ni3Mo6S/C4.94.886.252.891.2
    下载: 导出CSV

    表  2  不同催化剂的DBT加氢脱硫反应

    Table  2  HDS activity of DBT over different catalysts

    CatalystxDBT /%kHDS /(10–6 mol·g–1·s–1)TOF* /(10–3·s–1)Product selectivity* /%
    HHBDT +
    THDBT
    BPCHBBP/CHB
    NiMo6S/C82.31.02.420.271.48.48.5
    NiMo6/Al2O363.20.61.219.266.414.44.6
    Ni3Mo6S/C94.11.72.810.282.67.211.5
    Ni3Mo6/Al2O371.60.81.817.872.49.87.4
    * Determined by controlling the LHSV to reach the xDBT of 50%
    下载: 导出CSV
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  • 收稿日期:  2023-02-15
  • 修回日期:  2023-04-03
  • 录用日期:  2023-04-14
  • 网络出版日期:  2023-04-25
  • 刊出日期:  2023-12-05

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