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  

Study on catalytic conversion of coal-oil co-refining heavy oil to light aromatic hydrocarbons with HZSM-5 modified by transition metal

作　　者：姚昕壮 么秋香 何磊 刘永琦 马丽 孙鸣[1] 马晓迅[1] YAO Xinzhuang;YAO Qiuxiang;HE Lei;LIU Yongqi;MA Li;SUN Ming;MA Xiaoxun(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,710069 Xi’an,China;The Department of Science,Xijing University,710123 Xi’an,China;Key Laboratory of Coal Exploration and Comprehensive Utilization,Ministry of Land and Resources,Shaanxi Coal Geology Group Company Limited,710021 Xi’an,China)

机构地区：[1]西北大学化工学院,国家碳氢资源清洁利用国际科技合作基地,陕北能源先进化工利用技术教育部工程研究中心,陕西省洁净煤转化工程技术中心,西安710069 [2]西京学院理学院,西安710123 [3]陕西省煤田地质集团有限公司,自然资源部煤炭资源勘查与综合利用重点实验室,西安710021

出　　处：《煤炭转化》2023年第5期53-63,共11页Coal Conversion

基　　金：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);西京学院高层次人才专项资金项目(XJ21B10).

摘　　要：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197.3 mg/g与339.0 mg/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 efficient 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-refining heavy oil(H-CT)was selected as the raw material to examine the performance of the catalytic 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 spectrometry(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 order 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 formation of BTEXN.The combination of metal and HZSM-5 accelerates the hydrogen transfer,dehydroxylation,ring opening,dealkylation and other reactions in the catalytic conversion process.

关 键 词：煤油共炼 Py-GC/MS 过渡金属 HZSM-5 BTEXN 

分 类 号：TQ524[化学工程—煤化学工程]