School of Chemical Engineering, International Science and Technology Cooperation Base for Clean Utilization of National Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of Education for Advanced Use Technology of Shanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Northwest University
The Department of Science, Xijing University
Key Laboratory of Coal Exploration and Comprehensive Utilization, Ministry of Land and Resources, Shaanxi Coal Geology Group CompanyLimited

煤油共炼技术为煤炭和重质油清洁高效利用开辟了新途径,但其产品单一,附加值低。为实现煤油共炼液体产物的高值化利用,本研究以煤油共炼重油(H-CT)为原料,利用热裂解-气相色谱质谱联用仪(Py-GC/MS),通过单、双金属改性的HZSM-5对H-CT催化转化制苯、甲苯、乙苯、二甲苯和萘(BTEXN,B—苯,T—甲苯,E—乙苯,X—二甲苯,N—萘)的性能进行了考察,探究了裂解温度、升温速率和催化剂与原料的质量比对BTEXN峰面积和选择性的影响,利用红外快速加热炉对H-CT的Py-GC/MS结果进行了校正。结果表明:单、双金属负载使HZSM-5的强酸酸性减弱,中强酸酸性增强;Mo,Fe及双金属Mo-Fe的负载增大了HZSM-5介孔比表面积;H-CT裂解的最佳条件为温度700℃、升温速率5℃/ms,催化剂与原料的质量比8∶1,在此最优条件下,催化剂按转化效果由大到小依次为Mo-Fe,Mo-Ni,Mo,Ni,Fe,HZSM-5;HZSM-5和Mo-Fe/HZSM-5催化转化制备BTEXN的总选择性分别为39.78%和60.30%,修正后的BTEXN产率分别为197.3mg/g与339.0mg/g。过渡金属改性HZSM-5促进了BTEXN的生成,金属与HZSM-5的结合加速了催化转化过程中氢转移、脱羟基、开环、脱烷基和其他反应。

Coal-oil co-refining technology has opened up a new way for the clean and effi-cient utilization of coal and heavy oil, but its products are single and low value-added. In order to achieve the high-value utilization of liquid products from coal-oil co-refining, the coal-oil co-refi-ning heavy oil (H-CT) was selected as the raw material to examine the performance of the cata-lytic conversion of H-CT into benzene, toluene, ethylbenzene, xylene and naphthalene (BTEXN) by single-bimetallic-modified HZSM-5 using the fast pyrolysis-gas chromatography/mass spec-trometry (Py-GC/MS) in this work. The effects of pyrolysis temperature, heating rate and the mass ratio of H-CT to catalyst on the peak area and selectivity of BTEXN were explored. The Py-GC/MS results of H-CT were calibrated using an infrared fast heating furnace. The results show that the single and bimetal loading weakens the strong acidity of HZSM-5 and increases the moderate acidity. The loading of Mo, Fe and bimetallic Mo-Fe increases the mesoporous specific surface area of HZSM-5. The optimal temperature for H-CT cracking is 700 ℃, the heating rate is 5 ℃/ms, and the mass ratio of H-CT to catalyst is 8∶1. Under the optimal conditions, the or-der of catalyst conversion effect from the largest to the smallest is Mo-Fe, Mo-Ni, Mo, Ni, Fe, HZSM-5. The total selectivity of BTEXN prepared by catalytic conversion of HZSM-5 and Mo-Fe/HZSM-5 are 39.78% and 60.30%, respectively. The total selectivity of BTEXN are 197.3 mg/g and 339.0 mg/g, respectively. The transition metal modified HZSM-5 promotes the for-mation of BTEXN. The combination of metal and HZSM-5 accelerates the hydrogen transfer, de-hydroxylation, ring opening, dealkylation and other reactions in the catalytic conversion process.

国 家 自 然 科 学 基 金 项 目 (21908180,22178289,22278338)、国 家 重 点 研 发 计 划 项 目 (2018YFB0604603)、陕 西 省 重 点 研 发 计 划 项 目(2020ZDLGY11-02,2021GY-136)和西京学院高层次人才专项资金项目(XJ21B10).

姚昕壮,么秋香,何 磊,等.过渡金属改性 HZSM-5催化转化煤油共炼重油制轻质芳烃的研究[J].煤炭转化,2023,46(5):53-63

YAO Xinzhuang,YAO Qiuxiang,HE Lei,et al.Study on catalytic conversion of coal-oil co-refining heavy oil to light aromatic hydrocar-bons with HZSM-5 modified by transition metal[J].Coal Conversion,2023,46(5):53-63