Catalytic performance of La-modified HZSM-5 catalysts for methanol to gasoline reaction
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摘要: 采用浸渍法制备了La改性HZSM-5分子筛催化剂，利用X射线衍射（XRD）、氮气吸附-脱附、氨气程序升温脱附（NH3-TPD）以及吡啶吸附红外光谱（Py-FTIR）技术对催化剂进行表征，并在固定床微型反应评价装置上，在反应温度350℃，系统压力0.1 MPa，甲醇质量空速4.74 h-1的条件下，考察La改性HZSM-5分子筛催化剂的甲醇转化制汽油反应性能。结果表明，La改性HZSM-5分子筛催化剂的酸量降低，比表面积和孔容减小。La负载量为4%时，其MTG反应性能最佳，催化剂的寿命和汽油收率分别由改性前的12 h和52.69%增加到16 h和59.28%。此外，随着La负载量的增加，汽油中芳烃含量显著降低，降幅达18%。Abstract: La-modified HZSM-5 catalysts were prepared by impregnation method, and characterized by XRD, NH3-TPD, Py-FTIR and N2 adsorption/desorption techniques. Their catalytic performance in methanol to gasoline (MTG) reaction was evaluated in a fixed-bed tubular reactor at 350℃ and WHSV of 4.74 h-1 under ambient pressure. The results show that the introduction of La decreased the amount of acid sites, specific surface area and pore volume of HZSM-5 catalyst. The catalyst with La loading of 4% exhibited the best catalytic performance in MTG reaction, over which the lifetime and gasoline yield increased from 12 h and 52.69% to 16 h and 59.28%, respectively. In addition, the selectivity to aromatics in gasoline decreased markedly by 18% with increasing La content.
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Key words:
- methanol to gasoline /
- HZSM-5 zeolite /
- La
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图 1 不同La负载量HZSM-5催化剂的XRD谱图
Figure 1 XRD patterns of HZSM-5 catalysts with different La contents
图 2 不同La负载量HZSM-5催化剂的吡啶吸附红外光谱谱图
Figure 2 Py-FTIR spectra of HZSM-5 catalysts with different La contents
图 3 不同La负载量HZSM-5催化剂的NH3-TPD谱图
Figure 3 NH3-TPD patterns of HZSM-5 catalysts with different La contents
图 4 不同La负载量HZSM-5催化剂上甲醇转化率随时间的变化
Figure 4 Methanol conversion as a function of time on stream over HZSM-5 catalysts
图 5 不同La负载量HZSM-5催化剂上汽油收率随时间的变化
Figure 5 Changes of gasoline yield with reaction time over HZSM-5 catalysts with different La contents
图 6 不同La负载量HZSM-5催化剂的汽油组分对比
Figure 6 Product distribution of gasoline over HZSM-5 catalysts with different La contents
图 7 La负载量为4%的催化剂上汽油组分随时间变化
Figure 7 Product distribution in gasoline as a function of time on stream over HZSM-5 catalyst with 4% La contents
表 1 不同La负载量HZSM-5催化剂的结构性质和酸性质
Table 1 Textural properties and acid properties of HZSM-5 catalysts with different La contents
Catalyst ABET/(m2·g-1) Amicro/(m2·g-1) vtotal/(cm3·g-1) vmicro/(cm3·g-1) L/B HZ5-0 372.5 350.1 0.23 0.15 0.450 HZ5-1 343.4 331.3 0.21 0.13 0.483 HZ5-2 341.6 323.6 0.20 0.12 0.528 HZ5-4 338.2 311.5 0.19 0.12 0.574 HZ5-6 331.1 308.9 0.19 0.11 0.755 
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