Ni/Mo/P改性双功能生物炭催化低阶煤微波热解定向制备轻质芳烃

Microwave pyrolysis of low rank coal to light aromatics catalyzed by Ni/Mo/P modified bifunctional biochar

  • 摘要: 低阶煤高效热解对于国家实现节能减排至关重要。这一过程不仅提高了能源的绿色利用和转换效率,还为能源结构的优化升级提供强有力的支持。采用浸渍法制备镍、钼和磷改性的兼具化学催化和物理吸波的双功能生物炭(BAC)催化剂,考察了该催化剂、微波和供氢溶剂对低阶煤热解过程中轻质芳烃生成的促进作用。结果表明:通过对传统生物炭进行改性,成功引入含磷基团,不仅增加了催化剂的酸性活性位点,而且在负载镍和钼之后,催化剂能够显著降低低阶煤裂解反应的活化能,有效提高低阶煤的转化率和轻质芳烃的选择性,促进了低阶煤裂化和芳构化反应定向制备轻质芳烃;过渡金属钼的添加不仅提高了镍基催化剂的耐热性,有效防止了催化剂的烧结,还增强了镍和钼与生物炭之间的界面结合强度,显著提高了微波场中的催化剂稳定性和使用寿命;且所制备的Ni/Mo/P-BAC双功能催化剂在具有优良化学催化作用的同时也展现出良好的吸波性能,显著提升反应区内的微波电场强度,从而有效促进低阶煤分子自身的快速极化断键,进而提高低阶煤热解过程中轻质芳烃的选择性,初步实现低阶煤微波热解定向制备轻质芳烃;通过引入供氢溶剂进一步促进低阶煤热解,轻质芳烃产率最高可达58.42%。

     

    Abstract: Efficient pyrolysis of low-rank coal is very important for the country to achieve energy saving and emission reduction. This process not only improves the green utilization and conversion efficiency of energy, but also provides strong support for the optimization and upgrading of energy structure. Bifunctional biochar (BAC) catalyst modified by nickel, molybdenum and phosphorus with both chemical catalysis and physical absorption was prepared by impregnation method. The catalytic effects of BAC catalyst, microwave and hydrogen solvent on the formation of light aromatic hydrocarbons during the pyrolysis of low rank coal were investigated. The results show that the modification of traditional biochar and the successful introduction of phosphate-containing groups not only increase the acidic active site of the catalyst, but also, after loading Ni and Mo, the catalyst can significantly reduce the activation energy of low-rank coal cracking reaction, effectively improve the conversion rate of low-rank coal and the selectivity of light aromatics, and promote the oriented preparation of light aromatics by cracking and aromatization of low-rank coal. The addition of transition metal molybdenum not only improves the heat resistance of nickel-based catalyst, effectively prevents the sintering of catalyst, but also enhances the interface bonding strength between nickel and molybdenum and biochar, and significantly improves the stability and service life of catalyst in microwave field. In addition, the prepared Ni/Mo/P-BAC bifocal catalyst not only has excellent chemical catalysis, but also shows good wave absorption performance, significantly improves the microwave electric field intensity in the reaction zone, and effectively promotes the rapid polarization and bond breaking of low-rank coal molecules themselves, thus improving the selectivity of light aromatic hydrocarbons in the pyrolysis process of low-rank coal. Light aromatic hydrocarbons have been prepared by microwave pyrolysis of low-rank coal. By introducing hydrogen-supplying solvent to further promote the pyrolysis of low-rank coal, the yield of light aromatics can reach 58.42%.

     

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