MxOy/USY双功能催化剂对神东煤的快速热解产物的调控

doi:10.16085/j.issn.1000-6613.2017-1849

化工进展 ›› 2018, Vol. 37 ›› Issue (08): 3029-3037.DOI: 10.16085/j.issn.1000-6613.2017-1849

M_xO_y/USY双功能催化剂对神东煤的快速热解产物的调控

张穗穗¹, 李刚¹, 闵小建², 郑化安², 樊英杰², 张妮娜¹, 安璞¹, 马晓迅¹

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, 陕北能源化工产业发展协同创新中心, 陕西西安 710069;
2 陕西煤业化工技术研究院有限责任公司, 陕西西安 710070

收稿日期:2017-09-04 修回日期:2018-01-30 出版日期:2018-08-05 发布日期:2018-08-05
通讯作者: 马晓迅,教授,研究方向为化石燃料(煤、石油、天然气)和生物质资源的高效清洁转化利用、粉-粒气固流化床/喷动床的基础和开发应用性研究、过程优化与模拟。
作者简介:张穗穗(1992-),女,博士研究生,研究方向为煤热解。E-mail:ss_nwu@163.com。
基金资助:
国家自然科学基金重点项目（21536009）、陕西省科技计划（2017ZDCXL-GY-10-03）及西北大学研究生创新人才培训项目（YZZ15033）。

Regulation of the rapid pyrolysis products of Shendong coal by M_xO_y/USY bifunctional catalyst

ZHANG Suisui¹, LI Gang¹, MIN Xiaojian², ZHENG Hua'an², FAN Yingjie², ZHANG Nina¹, AN Pu¹, MA Xiaoxun¹

1 International Science and Technology Cooperation Base of MOST for Clean Utilization of Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of Education for Advanced Use Technology of Shaanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Collaborative Innovation Center for Development of Energy and Chemical Industry in Northern Shaanxi, School of Chemical Engineering, Northwest University, Xi'an 710069, Shaanxi, China;
2 Shaanxi Coal Chemical Industry Technology Research Institute Co., Ltd., Xi'an 710070, Shaanxi, China

Received:2017-09-04 Revised:2018-01-30 Online:2018-08-05 Published:2018-08-05

摘要/Abstract

摘要： 以USY分子筛为载体，采用等体积浸渍法分别制备了NiO、Fe₂O₃、Co₃O₄、MoO₃负载量均为9%的M_xO_y/USY双功能催化剂，并借助ICP、XRD、BET、TEM、NH₃-TPD、TG等分析手段对催化剂进行表征。使用自建的粉-粒流化床对神东煤进行快速催化热解实验，结果表明：①M_xO_y/USY使气体产物收率提高，液体产物收率降低，催化剂的积炭量增加，对半焦的产率基本没有影响；②M_xO_y/USY使CH₄、CO的收率均不同程度地提高，但H₂、C₂的收率皆有所降低；焦油中脂肪烃、单环芳烃、酚类化合物、含氧化合物的含量大幅增加，萘类化合物、联（多）苯的含量显著减少；③M_xO_y/USY的调控作用存在差异性。其中，Fe₂O₃/USY、Co₃O₄/USY的产物调控作用相似，但Fe₂O₃/USY的气体选择性更高，气体总收率提高23%；NiO/USY使C₃收率提高79%，CO₂收率降低91%，使焦油中脂肪烃、酚类、含氧化合物的含量分别增加1555%、739%、412%，萘类化合物的含量减少46%；MoO₃/USY使稠环芳烃的含量增加8%。

关键词: 流化床, 分子筛, 过渡金属氧化物, 快速热解, 催化作用, 产物调控

Abstract: Four transition metal oxides of NiO, Fe₂O₃, Co₃O₄ and MoO₃, were respectively supported on USY molecular sieves by equal volume impregnation to prepare M_xO_y/USY bifunctional catalysts. The catalysts, all with 9% transition metal oxides, were characterized by ICP, XRD, BET, TEM, NH₃-TPD, and TG. The rapid pyrolysis experiments of shendong coal were conducted on a self-built powder-particle fluidized bed. The results showed:① M_xO_y/USY bifunctional catalysts increased the yield of the gas product and the amount of carbon deposition, and decreased the yield of the liquid product, but had no effect on the yield of the char. ② M_xO_y/USY increased the production of CH₄ and CO, but decreased the yield of H₂ and C₂. The bifunctional catalysts significantly reduced the content of naphthalene compound and biphenyl (poly) benzene in the tar, while increased the content of aliphatic hydrocarbons,monocyclic aromatic hydrocarbons,phenolic compounds and oxygen compounds. ③ The four M_xO_y/USY bifunctional catalysts showed differences in the regulation of the product and its composition. In addition,Fe₂O₃/USY and Co₃O₄/USY had similar regulatory effect on products and their composition. But Fe₂O₃/USY had a higher gas selectivity,and the total gas yield for Fe₂O₃/USY was as high as 23%. NiO/USY increased both the C₃ yield by 79% and the content of aliphatic hydrocarbons,phenols and oxygen compounds in the tar by 1555%,739%,412%, respectively,but decreased the CO₂ yield by 91% and the content of naphthalenes by 46%. MoO₃/USY increased the content of polycyclic aromatic hydrocarbons by 8%.

Key words: fluidized bed, molecular sieves, transition metals oxide, fast pyrolysis, catalysis, product regulation

中图分类号:

TQ53

张穗穗, 李刚, 闵小建, 郑化安, 樊英杰, 张妮娜, 安璞, 马晓迅. M_xO_y/USY双功能催化剂对神东煤的快速热解产物的调控[J]. 化工进展, 2018, 37(08): 3029-3037.

ZHANG Suisui, LI Gang, MIN Xiaojian, ZHENG Hua'an, FAN Yingjie, ZHANG Nina, AN Pu, MA Xiaoxun. Regulation of the rapid pyrolysis products of Shendong coal by M_xO_y/USY bifunctional catalyst[J]. Chemical Industry and Engineering Progress, 2018, 37(08): 3029-3037.

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M_xO_y/USY双功能催化剂对神东煤的快速热解产物的调控

Regulation of the rapid pyrolysis products of Shendong coal by M_xO_y/USY bifunctional catalyst

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MxOy/USY双功能催化剂对神东煤的快速热解产物的调控

Regulation of the rapid pyrolysis products of Shendong coal by MxOy/USY bifunctional catalyst

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M_xO_y/USY双功能催化剂对神东煤的快速热解产物的调控

Regulation of the rapid pyrolysis products of Shendong coal by M_xO_y/USY bifunctional catalyst