Biomass Energy Engineering Research Center, School of Agriculture and Biology,Shanghai Jiao Tong University
Department of ApplicationResearch and Development, Impact Scientific Instrument Co., Ltd.

针对生物油组分复杂、含氧量高等问题,通过使用金属改性催化剂改善生物油的组成,提高生物油中单环芳烃(MonocyclicAromaticsHydrocarbon,MAHs)的选择性,并探讨了生物质催化热裂解反应机理。以硝酸镓、硝酸锌为改性剂,采用离子交换法对不同硅铝比的ZSM-5进行改性,使用Py-GC/MS外标法探究硅铝比(30、40、50和60)和金属元素类型(Ga、Zn)对玉米秸秆催化热裂解产物单环芳烃选择性的影响。结果表明,对于Ga/ZSM-5,硅铝比为30时更有利于单环芳烃的产生,此时玉米秸秆催化热裂解产物单环芳烃的相对含量为19.02%,是在母体ZSM-5(30)催化下的1.38倍;对于Zn/ZSM-5,硅铝比为40时更有利于单环芳烃的产生,此时玉米秸秆催化热裂解产物单环芳烃的相对含量为22.18%,是在母体ZSM-5(40)催化下的1.51倍。硅铝比对二甲苯、萘和二甲基萘的产率影响比改性金属元素影响大,改性金属元素对苯、甲苯和茚的产率影响比硅铝比影响大。从生物油的相对含量、元素组成、芳香烃的相对含量、以及单环芳烃的产率来看,Zn/ZSM-5(40)的催化效果优于Ga/ZSM-5(30)。

In order to solve the existing problem of bio-oil, which contains complex compounds and has a high oxygen content, research was conducted on biomass catalytic pyrolysis and reaction mecha nisms to enhance the quality of bio-oil and improve the selectivity of monocyclic aromatics hydrocarbon (MAHs). Ga-modified ZSM-5 and Zn-modified ZSM-5 catalysts, prepared through the ion exchange method, were used to investigate the influence of SiO2 / Al2O3 ratio and metal element type on the selection of MAHs during corn stalk catalytic pyrolysis. Four different SiO2 / Al2O3 ratios (30, 40, 50, and 60) were used for catalyst preparation. Pyrolysis-gas chromatography / mass spectrometry ( Py -GC / MS) was used to analyze the products. The results indicated that Ga / ZSM-5 with a Si/ Al ratio of 30 achieved the highest relative content of MAHs (19.02%), which was 1.38 times higher than that of the parent ZSM-5 (30). Conversely, Zn / ZSM-5 with a Si/ Al ratio of 40 exhibited the highest relative content of MAHs (22.18%), surpassing that of the parent ZSM-5 (40) by 1.51 times. The SiO2 / Al2O3 ratio significantly influenced the yield of xylene, naphthalene, and dimethylnaphthalene, while the metal element type also affected the yield of benzene, toluene, and indene. Based on the elemental structure of bio-oil, the relative content of aromatics, and the yield of MAHs, Zn / ZSM-5 (40) per formed better than Ga / ZSM-5 (30).

国家自然科学基金资助项目(51776127)

柴美云,刘荣厚.Ga、Zn改性ZSM-5对生物质热裂解产物单环芳烃选择性的影响[J].能源环境保护,2024,38(2):123-135.

CHAI Meiyun, LIU Ronghou. Effect of Ga, Zn modified ZSM-5 catalysts on the biomass catalytic pyrolysis forMAHs production[J]. Energy Environmental Protection, 2024, 38(2): 123-135.