酸-金属改性HZSM-5甲醇芳构化催化剂OA
Acid-metal modified HZSM-5 catalyst for methanol aromatization
采用乙酰丙酸(LA)和Zn对HZSM-5进行协同改性,得到L/Zn0.2-ZSM5.利用XRD、N2吸附-脱附、NH3-TPD、Py-FTIR、Raman、XPS和TGA等对其表征,研究协同改性对其结构、性质、催化性能及积炭行为的影响.结果表明,L/Zn0.2-ZSM5的比表面积与HZSM-5相当,孔体积和平均孔径显著大于HZSM-5及单一改性样品(L-ZSM5、Zn0.2-ZSM5).同时,协同改性显著降低了催化剂的总酸量和酸强度,并构建了适中的B/L酸比.L/Zn0.2-ZSM5结构及性质的改变,使其BTX催化选择性和催化寿命,分别达到58.75%和128 h,均优于单一改性样品及其他Zn负载量的样品.L/Zn0.2-ZSM5的内积炭比例和容炭能力也显著高于未改性和单一改性的样品.这是因为协同改性通过扩孔减弱了积炭前驱体的扩散阻力,有效抑制了积炭的石墨化进程.同时LA增强了Zn与载体的相互作用,促进Zn物种的分散,显著提高了[ZnOH]+的比例(达 61.36%).
The HZSM-5 zeolite was co-modified with levulinic acid(LA)and Zn to obtain L/Zn0.2-ZSM5.Comprehensive characterization was conducted using XRD,N2 adsorption-desorption,NH3-TPD,Py-FTIR,Raman,XPS and TGA to investigate the effects of co-modification on the catalyst's structure,physicochemical properties,catalytic performance,and coke-deposition behavior.The results indicate that L/Zn0.2-ZSM5 possesses a specific surface area comparable to that of HZSM-5,while exhibiting significantly larger pore volume and average pore size than HZSM-5 and the singly modified catalysts(L-ZSM5 and Zn0.2-ZSM5).In addition,co-modification markedly decreases the total acid amount and acid strength,while establishing a moderate Brønsted-to-Lewis(B/L)acid ratio.These structural and acidic modifications endow L/Zn0.2-ZSM5 with a BTX(benzene,toluene,xylene)selectivity of 58.75%and a catalytic lifetime of 128 h,both of which surpass those of the singly modified catalysts and those with different Zn loadings.The enhanced catalytic performance of L/Zn0.2-ZSM5 correlates with its significantly lower proportion of internal coke and greater coke storage capacity compared with the unmodified and singly modified catalysts.This behavior is attributed to the co-modification-induced pore enlargement,which effectively reduces the diffusion resistance of coke precursors and suppresses the graphitization process of coke.Furthermore,LA strengthens the interaction between Zn species and the zeolite framework,promotes Zn dispersion,and substantially increases the proportion of[ZnOH]+species to 61.36%.
李剑;朱海山;乔永伟;张家申;杨丽娜
辽宁石油化工大学石油化工学院,辽宁抚顺 113001辽宁石油化工大学石油化工学院,辽宁抚顺 113001浙江石油化工有限公司,浙江舟山 316200中国石油抚顺石化分公司,辽宁抚顺 113000辽宁石油化工大学石油化工学院,辽宁抚顺 113001
生物科学
HZSM-5乙酰丙酸Zn协同改性MTA选择性积炭
HZSM-5levulinic acidZnsynergistic modificationMTA selectivitycoke
《燃料化学学报(中英文)》 2026 (9)
64-77,14
Supported by Science and Technology Project of Liaoning Province(20170540585).
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