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ZnAlOx/ZSM-5复合催化剂用于苯与合成气一步制备烷基苯

韩腾飞 刘建超 杜明仙 徐红 董晋湘 李学宽 葛晖

韩腾飞, 刘建超, 杜明仙, 徐红, 董晋湘, 李学宽, 葛晖. ZnAlOx/ZSM-5复合催化剂用于苯与合成气一步制备烷基苯[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60123-8
引用本文: 韩腾飞, 刘建超, 杜明仙, 徐红, 董晋湘, 李学宽, 葛晖. ZnAlOx/ZSM-5复合催化剂用于苯与合成气一步制备烷基苯[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60123-8
HAN Teng-fei, LIU Jian-chao, DU Ming-xian, XU Hong, DONG Jin-xiang, LI Xue-kuan, GE Hui. One-pass conversion of benzene and syngas to alkylbenzenes by ZnAlOx/ZSM-5 composite catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60123-8
Citation: HAN Teng-fei, LIU Jian-chao, DU Ming-xian, XU Hong, DONG Jin-xiang, LI Xue-kuan, GE Hui. One-pass conversion of benzene and syngas to alkylbenzenes by ZnAlOx/ZSM-5 composite catalyst[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60123-8

ZnAlOx/ZSM-5复合催化剂用于苯与合成气一步制备烷基苯

doi: 10.1016/S1872-5813(21)60123-8
基金项目: 国家自然科学基金面上项目(22078351)资助
详细信息
    作者简介:

    韩腾飞,男,1994.07,山西晋中,硕士,工业催化

    通讯作者:

    Tel: 13613519362,E-mail: gehui@sxicc.ac.cn

  • 中图分类号: TQ536.9

One-pass conversion of benzene and syngas to alkylbenzenes by ZnAlOx/ZSM-5 composite catalyst

Funds: The project was supported by the National Natural Science Foundation of China (22078351)
  • 摘要: 烷基苯是一类重要的有机化工基础原料,通过煤化工路线的苯合成气烷基化技术生产烷基苯,减轻中国对石油的过度依赖。本研究通过机械混合制备了ZnAlOx/ZSM-5复合催化剂用于苯与合成气的烷基化反应,复合催化剂两组分的最佳质量比为1∶1,复合氧化物的锌铝最佳物质的量比为2∶1,苯与合成气串联反应中间体为甲醇/二甲醚,甲醇合成催化中心是ZnO组分上的氧空位,甲醇在Al2O3上可脱水为二甲醚,甲醇/二甲醚进而在ZSM-5上与苯发生烷基化反应。由于ZnAlOx的高温甲醇或二甲醚合成特征,与ZSM-5的苯烷基化反应能够有效匹配,实现了高的反应活性和选择性。
  • 图  1  (a):ZnAlOx和ZSM-5的XRD谱图,(b):不同质量比的ZnAlOx/ZSM-5(锌铝比为2)复合催化剂的XRD谱图,(c):不同锌铝比的ZnAlOx/ZSM-5(质量比为1)复合催化剂的XRD谱图

    Figure  1  XRD patterns of (a): ZnAlOx and ZSM-5, (b): ZnAlOx/ZSM-5 (Zn/Al = 2) with different mass ratio, (c): ZnAlOx/ZSM-5 (mass ratio is 1) with different Zn/Al ratio

    图  2  不同锌铝比的ZnAlOx的氢气程序升温还原图

    Figure  2  H2-TPR of ZnAlOx catalysts with different Zn/Al

    图  3  (a): Zn/Al = 1的ZnAlOx,(b): Zn/Al = 2的ZnAlOx,(c): Zn/Al = 3的ZnAlOx,(d): ZSM-5, (e): ZnAlOx/ZSM-5(Zn/Al = 2)复合催化剂的扫描电镜照片

    Figure  3  SEM of (a): ZnAlOx of Zn/Al = 1, (b): ZnAlOx of Zn/Al = 2, (c): ZnAlOx of Zn/Al = 3, (d): ZSM-5, (e): ZnAlOx/ZSM-5(Zn/Al = 2) composite catalyst

    图  4  反应温度对(a):液相产物选择性,(b):C7和C8总收率,(c):气相产物选择性的影响

    Figure  4  Effect of temperature on (a) the liquid products selectivities; (b) the total yield of C7 and C8; (c) the gaseous products selectivities

    4.0 MPa, GHSV = 4800 mL/(h·gcat), WHSV = 2.6 g/(h·gcat), Zn/Al = 2, mass ratio is 1∶1

    图  5  合成气空速对(a):液相产物选择性,(b):C7和C8总收率,(c):气相产物选择性的影响

    Figure  5  Effect of GHSV on (a) the liquid products selectivities; (b) the total yield of C7 and C8; (c) the gaseous products selectivities

    400 ℃, 4.0 MPa, WHSV = 2.6 g/(h·gcat), Zn/Al = 2, mass ratio is 1∶1

    图  6  两组分质量比对(a):液相产物选择性,(b):C7和C8总收率,(c):气相产物选择性的影响

    Figure  6  Effect of mass ratio on (a) the liquid products selectivities; (b) the total yield of C7 and C8; (c) the gaseous products selectivities

    450 ℃, 4.0 MPa, GHSV = 4800 mL/(h·gcat), WHSV = 2.6 g/(h·gcat), Zn/Al = 2

    图  7  Zn/Al对(a):液相产物选择性,(b):C7和C8总收率,(c):气相产物选择性的影响

    Figure  7  Effect of Zn/Al on (a) the liquid products selectivities; (b) the total yield of C7 and C8; (c) the gaseous products selectivities

    450 ℃, 4.0 MPa, GHSV = 4800 mL/(h·gcat), WHSV = 2.6 g/(h·gcat), mass ratio is 1:1

    图  8  (a):不同温度反应后的ZnAlOx/ZSM-5复合催化剂,(b):反应后不同质量比的ZnAlOx/ZSM-5复合催化剂,(c):反应后不同锌铝比的ZnAlOx/ZSM-5复合催化剂的XRD谱图

    Figure  8  XRD patterns of (a): used samples at different reaction temperatures, (b): used samples with different mass ratios, (c): used samples with different Zn/Al

    图  9  反应后ZnAlOx/ZSM-5复合催化剂的扫描电镜图

    Figure  9  SEM image of used ZnAlOx/ZSM-5 Catalyst

    图  10  反应路径示意图

    Figure  10  Graph of reaction path

    表  1  ZnAlOx和ZSM-5的元素组成

    Table  1  Elemental composition of ZnAlOx and ZSM-5

    CatalyZn/Ala/ratioZn/Alb/ratioA/(m2·g−1)
    ZnAlOx Zn/Al=1 Zn/Al=0.69 137.25
    ZnAlOx Zn/Al=2 Zn/Al=1.47 108.65
    ZnAlOx Zn/Al=3 Zn/Al=2.34 91.89
    ZSM-5 SiO2/Al2O3 = 200 Si/Al=86 370.52
    ZSM-5 Na 0.43/%  a:     ; b:    
    下载: 导出CSV
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  • 收稿日期:  2021-04-26
  • 修回日期:  2021-05-30
  • 网络出版日期:  2021-06-29

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