催化剂结构与焦油模型化合物裂解行为的关联性

doi:10.16085/j.issn.1000-6613.2017-1123

化工进展 ›› 2018, Vol. 37 ›› Issue (04): 1451-1459.DOI: 10.16085/j.issn.1000-6613.2017-1123

催化剂结构与焦油模型化合物裂解行为的关联性

张艳敏¹, 孔令涛¹, 刘景梅¹, 钟梅¹, 李显^1,2

1 新疆大学化学化工学院, 煤炭清洁转化与化工过程自治区重点实验室, 新疆乌鲁木齐 830046;
2 华中科技大学煤燃烧国家重点实验室, 湖北武汉 430074

收稿日期:2017-06-08 修回日期:2017-11-20 出版日期:2018-04-05 发布日期:2018-04-05
通讯作者: 钟梅,副教授,硕士生导师;李显,副教授,博士生导师。
作者简介:张艳敏(1988-),女,硕士研究生。
基金资助:
新疆维吾尔自治区重点实验室开放课题项目（2016D03009）、国家自然科学基金（21606187）、国家重点研发计划（2016YFF0102602）及自治区科技人才培养项目（QN2016BS0152）。

On the relation between the structure of catalysts and the cracking behavior of tar model compound

ZHANG Yanmin¹, KONG Lingtao¹, LIU Jingmei¹, ZHONG Mei¹, LI Xian^1,2

1 Key Laboratory of Coal Clean Conversion & Chemical Engineering Process(Xinjiang Uyghur Autonomous Region), College of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, Xinjiang, China;
2 State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China

Received:2017-06-08 Revised:2017-11-20 Online:2018-04-05 Published:2018-04-05

摘要/Abstract

摘要： 以Ni（NO₃）₂·6H₂O为镍源，分别以HZSM-5（Si/Al=25）、HZSM-5（Si/Al=50）、HZSM-5（Si/Al=200）、USY、Al₂O₃为载体制备了5种镍基催化剂，采用XRD、H₂-TPR、BET、NH₃-TPD等方法对其进行了表征，在固定床反应器中考察了上述催化剂对煤焦油模型化合物甲苯+芘的催化裂解性能。结果表明，相比惰性载体石英砂，在催化剂作用下，液相产物中轻质芳烃种类明显增多。3种Ni/HZSM-5催化剂的比表面积和平均孔径较为接近，然而酸性中心数量最多的Ni/HZSM-5（Si/Al=25），对甲苯+芘的裂解能力最强，体现为液体产物收率最低（仅为15.95%），气产率和析碳率均最高，分别达16.73%和67.32%。在酸性中心数量相近的Ni/HZSM-5（Si/Al=200）与Ni/Al₂O₃作用下，液体产物收率差别较小，但后者的芘裂解率比前者高41.47%，主要是由于后者的平均孔径比前者高1.64倍，说明平均孔径大有利于重质组分芘的裂解。综合考虑液体产物收率、气产率、析碳率和芘的裂解率，Ni/Al₂O₃更适合甲苯+芘裂解反应体系。

关键词: 催化剂载体, 模型, 固定床, 酸强度, 裂解性能

Abstract: Five kinds of Ni-based catalysts were prepared using HZSM-5(Si/Al=25),HZSM-5(Si/Al=50),HZSM-5(Si/Al=200),USY and Al₂O₃ as the carriers and Ni(NO₃) ₂·6H₂O as the nickel resource. All the catalysts were characterized by XRD,H₂-TPR,BET and NH₃-TPD. Then the performance of catalysts for cracking coal tar model compounds of toluene and pyrene were investigated in a fixed-bed reactor. The experimental results showed that the species of light aromatics in the liquid product increased obviously with catalysts compared to that with silica sand. Though the three kinds of Ni/HZSM-5 had similar specific surface area and average pore diameter,Ni/HZSM-5 (Si/Al=25) showed the highest gas yield and carbon deposition of 16.73% and 67.32%,respectively and the lowest liquid product yield of 15.95% due to the highest acidity. For Ni/HZSM-5(Si/Al=200) and Ni/Al₂O₃ samples,the liquid product yields were almost the same,owing to their similar acidity,however,the latter had a higher pyrene cracking efficiency of 41.47%,about 1.64 times higher than the Ni/HZSM-5(Si/Al=200),indicating that the larger pore size was beneficial to the pyrene cracking. Through comprehensive consideration of the pyrene cracking efficiency and the yield of liquid,gas and carbon deposition,we think Ni/Al₂O₃ is more suitable for the cracking of toluene and pyrene.

Key words: catalyst support, model, fixed-bed, acidity, cracking performance

中图分类号:

TQ241.5

张艳敏, 孔令涛, 刘景梅, 钟梅, 李显. 催化剂结构与焦油模型化合物裂解行为的关联性[J]. 化工进展, 2018, 37(04): 1451-1459.

ZHANG Yanmin, KONG Lingtao, LIU Jingmei, ZHONG Mei, LI Xian. On the relation between the structure of catalysts and the cracking behavior of tar model compound[J]. Chemical Industry and Engineering Progress, 2018, 37(04): 1451-1459.

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催化剂结构与焦油模型化合物裂解行为的关联性

On the relation between the structure of catalysts and the cracking behavior of tar model compound

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