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不同拓扑结构分子筛催化1-甲萘异构化-烷基转移耦合反应性能对比

李洪涛 盛路阳 展俊岭 房伟贤 梁翌 张钰

李洪涛, 盛路阳, 展俊岭, 房伟贤, 梁翌, 张钰. 不同拓扑结构分子筛催化1-甲萘异构化-烷基转移耦合反应性能对比[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60035-X
引用本文: 李洪涛, 盛路阳, 展俊岭, 房伟贤, 梁翌, 张钰. 不同拓扑结构分子筛催化1-甲萘异构化-烷基转移耦合反应性能对比[J]. 燃料化学学报. doi: 10.1016/S1872-5813(21)60035-X
Li Hong-tao, Sheng Lu-yang, Zhan Jun-ling, Fang Wei-xian, Liang Yi, Zhang Yu. Comparative study on the catalytic performance of molecular sieve catalysts with different topologies in 1-methylnaphthalene isomerization-transalkylation coupling reaction[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60035-X
Citation: Li Hong-tao, Sheng Lu-yang, Zhan Jun-ling, Fang Wei-xian, Liang Yi, Zhang Yu. Comparative study on the catalytic performance of molecular sieve catalysts with different topologies in 1-methylnaphthalene isomerization-transalkylation coupling reaction[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(21)60035-X

不同拓扑结构分子筛催化1-甲萘异构化-烷基转移耦合反应性能对比

doi: 10.1016/S1872-5813(21)60035-X
基金项目: 吉林省科技发展计划项目(20200401029GX, 20180201101GX)资助
详细信息
    作者简介:

    李洪涛:1445568181@qq.com

    通讯作者:

    Tel:0432-62185139,E-mail:zhang99yu@hotmail.com(ZHANG Yu)

  • 中图分类号: TQ203.2

Comparative study on the catalytic performance of molecular sieve catalysts with different topologies in 1-methylnaphthalene isomerization-transalkylation coupling reaction

Funds: The project was supported by the Science and Technology Development Foundation of Jilin Province (20200401029GX, 20180201101GX)
  • 摘要: 以1-甲萘和均三甲苯为原料经固体酸催化的异构化-烷基转移耦合反应制备2-甲萘及二甲基萘。对MWW、BEA、FAU、MFI拓扑结构分子筛的催化性能进行对比研究,对反应机理进行探讨。采用XRD、BET、SEM、NH3-TPD、Py-FTIR及ICP等方法对催化剂结构物性进行了表征。与具有十元环特征孔道的MFI分子筛相比,具有十二元环特征孔道的MWW、BEA、FAU分子筛表现出更好的催化活性。BEA结构分子筛具有较高的二甲基萘选择性,而MWW结构分子筛具有较高的2-甲萘选择性并表现出优异的催化稳定性。在MWW结构分子筛中,HMCM-22的1-甲萘转化率达到70.27%,2-甲萘收率达到66.69%。而HMCM-56上则同时获得35.74%的2-甲萘收率和19.00%的二甲基萘收率。该研究为以中国丰富的碳十资源为原料制备高端聚酯单体2,6-二甲基萘开辟了颇具潜力的技术路线。
  • 图  1  样品的XRD谱图

    Figure  1.  XRD patterns of the samples

    图  2  样品的氮气吸附-脱附等温线

    Figure  2.  N2 adsorption-desorption isotherms of the samples

    图  3  样品的SEM照片

    Figure  3.  SEM images of the samples

    (a): HZSM-5; (b): HY; (c): HBeta; (d): HMCM-22; (e): HMCM-49; (f): HMCM-56

    图  4  样品的NH3-TPD谱图

    Figure  4.  NH3-TPD spectra of the samples

    图  5  样品的Py-FTIR谱图

    Figure  5.  Py-FTIR spectra of the samples

    图  6  分子筛催化异构化-烷基转移耦合反应催化稳定性

    Figure  6.  The catalytic stability of molecular sieves in the isomerization-transalkylation coupling reaction of 1-methylnaphthalene with 1,3,5-trimethylbenzene

    (Reaction conditions: t = 400 ℃, WHSV1-MN = 0.5 h−1, n1-MN/nTMB = 1/3, p = 0.2 MPa)

    图  7  1-MN与1,3,5-TMB异构化-烷基转移耦合反应产物的质谱图

    Figure  7.  Mass Spectrometric Analysis of the Coupling Reaction of 1-MN and 1,3,5-TMB Isomerization-Transalkylation

    1.Benzene; 2. Toluene; 3–4. Dimethylbenzene; 5. 1–ethyl–2–Methylbenzene; 6. 1,3,5–Trimethylbenzene; 7. 1,2,3–TMB (1,2,3–trimethylbenzene);8. 1,2,4–TMB (1,2,4–trimethylbenzene; 9–12. Tetramethylbenzene; 13. Naphthalene; 14. 2–Methylnaphthalene; 15. 1–Methylnaphthalene;16. Dimethylnaphthalene; 17. Trimethylnaphthalene; 18. Polymethyl naphthalene

    图  8  1-甲萘与均三甲苯异构化-烷基转移耦合反应机理

    Figure  8.  Mechanism diagram of the isomerization-transalkylation coupling reaction of 1-methylnaphthalene with 1,3,5-trimethylbenzene

    表  1  样品的孔结构参数

    Table  1.   Pore structure parameter of the samples

    SampleABET/
    (m2∙g−1)
    Aext /
    (m2∙g−1)
    vtotal/
    (cm3∙g−1)
    vmic/
    (cm3∙g−1)
    vmes/
    (cm3∙g−1)
    Ratio Aext/
    ABET
    HZSM-5326870.240.090.100.48
    HBeta5801600.500.190.320.27
    HY6351380.470.400.080.21
    HMCM-224441060.680.140.560.24
    HMCM-49447860.760.150.640.19
    HMCM-564991771.320.131.230.36
    下载: 导出CSV

    表  2  元素组成、NH3-TPD和Py-FTIR测试结果

    Table  2.   Element composition,NH3-TPD and Py-FTIR results

    SampleSiO2/Al2O3a Desorption peak area of NH3-TPDb RcAcidity/ (umol∙g−1)Brønsted/Lewis
    A1(100−250 ℃)A2(250−400 ℃)A3(400−550 ℃)BrønstedLewis
    HZSM-524.2134557010390.5
    HY5.188613836000.7
    HBeta17.880516920.7631180.5
    HMCM-2213.13689060.7124612.0
    HMCM-499.695816730.62871032.8
    HMCM-5611.8122712300.5209673.1
    a. measured by ICP method;b. calculated by Gaussian fitting method; c. (A2 + A3) to (A1 + A2 + A3) Ratio
    下载: 导出CSV

    表  3  分子筛催化异构化-烷基转移耦合反应催化性能a

    Table  3.   Catalytic performance of isomerization-transalkylation of 1-MN with 1,3,5-TMB over molecular sieves a

    CatalystsHZSM-5HMCM-22HMCM-49HMCM-56HBetaHY
    Conversion, x/%
    1-MN77.5670.2778.0480.7093.3489.71
    1,3,5-TMB28.1463.5369.5876.8880.6350.93
    Distributionb, s/%
    2-MN91.1694.4689.2855.5413.7429.00
    DMNs5.562.535.2829.5242.7635.95
    TMNs1.202.141.857.3932.5315.63
    NP2.080.873.597.5510.9719.42
    Yield, cw/%
    2-MN37.0566.3457.6635.747.5316.70
    DMNs2.261.823.4119.0023.4120.69
    2,6-DMN/DMNs0.550.370.410.350.380.34
    Yieldd, w/%
    2-MN5.5866.6955.9552.6953.1852.29
    DMNs2.040.932.469.235.326.15
    2,6-DMN/DMNs0.500.460.380.360.410.37
    a. t = 400 ℃, WHSV1-MN = 0.5 h−1, n1-MN/nTMB = 1/3, p = 0.2 MPa, T.O.S = 1 h
    b. Mole of specific product×100/mole of 1-MN derivatives, including NP (Naphthalene), 2-MN (2-methylnaphthalene), DMNs (Dimethyl naphthalene) and TMNs (Trimethyl naphthalene).
    c. Mole of 2-MN (or DMNs) in product×100/mole of 1-MN in raw materials,T.O.S = 1 h
    d. T.O.S = 6 h
    下载: 导出CSV
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