热处理方式对NiMoAl催化剂结构及加氢脱氮性能的影响

石油炼制与化工 ›› 2020, Vol. 51 ›› Issue (11): 53-58.

热处理方式对NiMoAl催化剂结构及加氢脱氮性能的影响

毋肖卓,涂椿滟,张乾,凌丽霞,黄伟

太原理工大学煤科学与技术教育部和山西省重点实验室

收稿日期:2020-04-23 修回日期:2020-06-13 出版日期:2020-11-12 发布日期:2020-11-24
通讯作者: 涂椿滟 E-mail:tuchunyan@tyut.edu.cn
基金资助:
国家重点研发计划项目;国家自然科学基金项目

EFFECT OF THERMAL TREATMENT METHOD ON STRUCTURE AND HYDRODENITROGENATION PERFORMANCE OF NiMoAl CATALYST

Received:2020-04-23 Revised:2020-06-13 Online:2020-11-12 Published:2020-11-24
Supported by:

摘要/Abstract

摘要： 采用溶胶凝胶法合成NiMoAl催化剂前躯体，分别在空气、氮气和液体石蜡3种环境中对其进行热处理制得3种NiMoAl加氢脱氮催化剂。利用X射线衍射（XRD）、热重-质谱联用仪（TG-MS）、氮气物理吸附、紫外-可见漫反射光谱（UV-Vis DRS）和透射电镜（TEM）对催化剂进行物化性质分析，以喹啉加氢脱氮探针反应，考察前躯体热处理方式对NiMoAl催化剂的加氢脱氮性能的影响。结果表明：与空气气氛焙烧相比，经液相热处理制得的NiMoAl催化剂具有更大的孔体积和更高的活性金属分散度，而采用氮气气氛焙烧使催化剂表面出现了MoS2聚集现象；与其他热处理方法相比，经液相热处理制备的NiMoAl催化剂在喹啉加氢脱氮反应中表现出更高的脱氮产物选择性。

关键词: NiMo催化剂, 加氢脱氮, 热处理, 喹啉

Abstract: The NiMoAl catalyst precursor synthesized by sol-gel method was thermal treated in air, nitrogen and liquid paraffin, respectively, to prepare 3 kinds of NiMoAl catalysts. The physical and chemical properties of these catalysts were analyzed by X-ray diffraction (XRD), thermogravimetry-mass spectrometry (TG-MS), nitrogen adsorption-desorption, ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS) and transmission electron microscopy (TEM). Using quinoline hydrodenitrogenation (HDN) as a reaction probe, the effect of precursor thermal treatment on the catalytic hydrodenitrogenation performance of NiMoAl catalyst samples was investigated. The results showed that the NiMoAl catalyst prepared by liquid-phase thermal treatment had larger pore volume and higher active metal dispersion in comparison with the sample calcinated in air. Besides, the aggregation of MoS2 was found on the surface of the catalyst calcinated in nitrogen. Compared with other two thermal treatment methods, the NiMoAl catalyst obtained through liquid-phase thermal treatment exhibited a higher selectivity for denitrogenation products in the HDN reaction of quinoline.

Key words: NiMo catalyst, hydrodenitrogenation, thermal treatment, quinoline

中图分类号:

毋肖卓涂椿滟张乾凌丽霞黄伟. 热处理方式对NiMoAl催化剂结构及加氢脱氮性能的影响[J]. 石油炼制与化工, 2020, 51(11): 53-58.

参考文献

[1]Chan Kwak, Jung Joon Lee, Jun Sang Bae, et al.Poisoning effect of nitrogen compounds on the performance of CoMoSAl2O3 catalyst in the hydrodesulfurization of dibenzothiophene,4-methyldibenzothiophene,and 4,6-dimethyldibenzothiophene[J].Applied Catalysis B: Environmental, 2001, 35(1):59-68
[2]Wei Han, Hong Nie, Xiangyun Long, et al.A study on the origin of the active sites of HDN catalysts using alumina-supported MoS3 nanoparticles as a precursor[J].Catalysis Science & Technology, 2016, 6(10):3497-3509
[3]Wenbin Chen, Hong Nie, Dadong Li, et al.Effect of Mg addition on the structure and performance of sulfide Mo/Al2O3 in HDS and HDN reaction[J].Journal of Catalysis, 2016, 344:420-433
[4]户安鹏, 陈文斌, 龙湘云, 等.柠檬酸对 NiMo/γ-Al2O3催化剂中助剂Ni作用的影响[J].石油炼制与化工, 2018, 49(10):52-57
[5]Weikun Lai, Liqing Pang, Jinbao Zheng, et al.Efficient one pot synthesis of mesoporous NiMo–Al2O3 catalysts for dibenzothiophene hydrodesulfurization[J].Fuel Processing Technology, 2013, 110:8-16
[6]Xiaodong Yi, Dongyun Guo, Pengyun Li, et al.One pot synthesis of NiMo–Al2O3 catalysts by solvent-free solid-state method for hydrodesulfurization[J].RSC advances, 2017, 7(86):54468-54474
[7]Huan Liu, Yanpeng Li, Changlong Yin, et al.One-pot synthesis of ordered mesoporous NiMo-Al2O3 catalysts for dibenzothiophene hydrodesulfurization[J]. Applied Catalysis B: Environmental, 2016, 198:493-507
[8]陈文斌, 杨清河, 聂红, 等.制备条件对CoMoP加氢催化剂性质的影响[J].石油炼制与化工, 2013, 44(6):1-5
[9]Yu Pereyma, O. V. Klimov, I. P. Prosvirin, et al..Effect of thermal treatment on morphology and catalytic performance of NiW/Al2O3 catalysts prepared using citric acid as chelating agent[J].Catalysis Today, 2018, 305:162-170
[10]Saheed A Ganiyu, Khalid Alhooshani, Syed Ahmed Ali.Single-pot synthesis of Ti-SBA-15-NiMo hydrodesulfurization catalysts: Role of calcination temperature on dispersion and activity[J].Applied Catalysis B: Environmental, 2017, 203:428-441
[11]王琪, 郝影娟, 陈爱平, 等.热处理对高硫化氢合成气一步法制甲硫醇K2MoO4-NiO/SiO2催化剂结构及性能的影响[J].催化学报, 2010, 31(2):242-247
[12]Zhiwei Liu, Wei Han, Dawei Hu, et al.Effects of Ni-Al2O3 Interaction on NiMo/Al2O3 Hydrodesulfurization Catalyst[J].Journal of Catalysis, 2020, doi: 10.1016/j.jcat.2020.04.008
[13]Mingfeng Li, Huifeng Li, Feng Jiang, et al.The relation between morphology of (Co)MoS2 phases and selective hydrodesulfurization for CoMo catalysts[J].Catalysis Today, 2010, 149(1-2):35-39
[14]宋书征, 黄伟, 张乾, 等.P的添加对柴油超深度加氢脱硫浆状催化剂性能的影响[J].石油学报石油加工, 2017, 33(3):535-542
[15]Abolghasem Shamsi, John P Baltrus, James Spivey.Characterization of coke deposited on Pt/alumina catalyst during reforming of liquid hydrocarbons[J].Applied Catalysis A: General, 2005 , 293:145-152
[16]Alano Viera da Silva Neto, Edson Roberto Leite, Victor Teixeira da Silva, et al.NiMoS HDS catalysts–The effect of the Ti and Zr incorporation into the silica support and of the catalyst preparation methodology on the orientation and activity of the formed MoS2 slabs[J].Applied Catalysis A: General, 2016, 528:74-85
[17]Cen Zhang, Michael Brorson, Ping Li, et al.CoMo/Al2O3 catalysts prepared by tailoring the surface properties of alumina for highly selective hydrodesulfurization of FCC gasoline[J]. [J].Applied Catalysis A: General, 2019, 570:84-95
[18]Oliver Y Gutiérrez, Ana Hrabar, Jennifer Hein, et al.. Ring opening of 1, 2, 3, 4-tetrahydroquinoline and decahydroquinoline on MoS2/γ- Al2O3 and Ni–MoS2/γ- Al2O3[J].Journal of Catalysis, 2012, 295:155-168
[19]S Hatanaka,MYamada,O. Sadakane. .Hydrodesulfurization of Catalytic Cracked Gasoline. 3. Selective Catalytic Cracked Gasoline Hydrodesulfurization on the Co?Moγ-Al2O3 Catalyst Modified by Coking Pretreatment[J].Industrial & Engineering Chemistry Research, 1998, 37(5):1748-1754
[20]Huifeng Li, Mingfeng Li, Yang Chu, et al.Essential role of citric acid in preparation of efficient NiWAl2O3 HDS catalysts[J].Applied Catalysis A: General, 2011, 403(1):75-82