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浙江大学学报(工学版)
化学工程     
煤焦油中芳烃(萘)的加氢饱和试验
夏良燕,夏芝香,方梦祥,唐巍,王勤辉,骆仲泱
浙江大学 能源清洁利用国家重点实验室,浙江 杭州 310027
Hydrogenation saturation of  aromatic compounds (naphthalene) in coal tar
XIA Liang-yan, XIA Zhi-xiang, FANG Meng-xiang, TANG Wei, WANG Qin-hui, LUO Zhong-yang
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China
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摘要:

为了优化煤焦油加氢制取燃料油过程中芳烃的加氢饱和反应工艺,选取萘作为煤焦油中芳烃的模型化合物,在固定床加氢反应器上,使用MoNiWP/γ-Al2O3催化剂,探究反应温度、压力、体积空速及氢油体积比对萘的转化率以及四氢萘和十氢萘选择性的影响.研究煤焦油中不同质量分数的二苯并噻吩(S)、喹啉(N)和邻甲酚(O)杂原子的存在对芳烃化合物加氢饱和的影响,并初步考察多种芳烃化合物加氢饱和的效果.结果表明:MoNiWP/γ-Al2O3催化剂在萘的加氢饱和反应中表现出良好的催化活性;反应温度和体积空速对萘加氢反应的影响比较明显,且萘加氢饱和的最佳反应条件为温度320 ℃,压力4 MPa,氢油体积比600∶1以及体积空速2 h-1;微量质量分数的S和N对萘的加氢饱和影响不大,但是当S、N质量分数高于015%,O质量分数高于030%时,萘加氢反应,尤其是第二个苯环的加氢饱和反应都受到明显的抑制;不同种类的芳烃类化合物的加氢饱和反应存在相互影响的现象.因此,建议在煤焦油加氢精制工艺中使用两步加氢,并对原料进行脱酚处理.

Abstract:

Naphthalene was chosen as the model compound of aromatics in coal tar  to improve the aromatics hydrogenation process in coal tar hydrogenation. The influence of temperature, pressure, volume space velocity and hydrogen to oil volume ratio on  conversion of naphthalene, accompany with the selectivity of tetralin and decalin, was investigated over MoNiWP/γ-Al2O3 catalyst in a fixed bed reactor. The effect of heteroatoms was studied by adding different mass fractions of S (dibenzothiophene), N (quinoline) and O (o-cresol), respectively. And the hydrogenation of multiple aromatic compounds was primarily investigated. The results reveal that: MoNiWP/γ-Al2O3 catalyst shows great activity on the hydrogenation of naphthalene. Reaction temperature and volume space velocity have more obvious effect on  reaction. The optimized process conditions of hydrodearo-matization was at 320 ℃, 4 MPa, hydrogen to oil volume ratio of 600∶1 and volume space velocity of 2 h-1. Trace mass fraction of S and N hardly worked on naphthalene hydrogenation. When the mass fraction of S, N was over 015% and that of O was higher than 030%, the hydrogenation reaction, especially  saturation of the second benzene ring of naphthalene, was inhabited. Hydrogenation saturation reactions of different kinds of aromatic compounds influence mutually. Therefore, two step hydrogenation of coal tar is recommended and removing the phenols in coal tar in advance is also important.

出版日期: 2015-08-28
:  TQ 530.2  
基金资助:

国家“863”高技术研究发展计划资助项目(2013AA051203);浙江省自然科学基金资助项目(R1080101);国际合作项目(2011DFR60190)

通讯作者: 方梦祥,男,教授,博导     E-mail: mxfang@zju.edu.cn
作者简介: 夏良燕(1990-),女,硕士生,从事煤焦油催化加氢研究.E-mail: xialiangyan1990@163.com
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引用本文:

夏良燕,夏芝香,方梦祥,唐巍,王勤辉,骆仲泱. 煤焦油中芳烃(萘)的加氢饱和试验[J]. 浙江大学学报(工学版), 10.3785/j.issn.1008-973X.2015.03.025.

XIA Liang-yan, XIA Zhi-xiang, FANG Meng-xiang, TANG Wei, WANG Qin-hui, LUO Zhong-yang. Hydrogenation saturation of  aromatic compounds (naphthalene) in coal tar. JOURNAL OF ZHEJIANG UNIVERSITY (ENGINEERING SCIENCE), 10.3785/j.issn.1008-973X.2015.03.025.

链接本文:

http://www.zjujournals.com/eng/CN/10.3785/j.issn.1008-973X.2015.03.025        http://www.zjujournals.com/eng/CN/Y2015/V49/I3/578

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