络合剂添加对CoMo催化剂加氢脱硫选择性的影响

石油炼制与化工 ›› 2020, Vol. 51 ›› Issue (8): 62-69.

络合剂添加对CoMo催化剂加氢脱硫选择性的影响

靳凤英^1,2,范景新²,郭春垒²,刘航²,臧甲忠²,于海斌²,王祥生¹,王亚权³

1. 天津大学化工学院
2. 中海油天津化工研究设计院有限公司
3. 大连理工大学化工与环境生命学部
5. 天津大学化工学院

收稿日期:2019-12-31 修回日期:2020-04-13 出版日期:2020-08-12 发布日期:2020-08-27
通讯作者: 靳凤英 E-mail:xiaoyingjin09@163.com
基金资助:

EFFECT OF CHELATING AGENT ON HDS SELECTIVITY OF CoMo CATALYST

Received:2019-12-31 Revised:2020-04-13 Online:2020-08-12 Published:2020-08-27
Supported by:

摘要/Abstract

摘要： 以ZSM-5-Al2O3复合物为载体制备了系列添加络合剂柠檬酸、氮川三乙酸、乙二胺四乙酸和环己二胺四乙酸的CoMo负载型催化剂，考察络合剂对CoMo催化剂加氢脱硫选择性的影响，并采用N2吸附-脱附、X射线衍射、傅里叶变换红外光谱、H2-程序升温还原、NH3-程序升温脱附、高分辨透射电镜、27Al固体高分辨核磁共振及X射线光电子能谱等手段进行表征。结果表明：催化剂制备过程中添加的络合剂优先与Co及载体中的Al络合，该络合作用可降低金属组分的还原温度，提高Mo的硫化度，增加催化剂活性中心数目。将络合剂引入催化剂后，MoS2片晶堆垛层数和MoS2片晶长度均增加，但 MoS2片晶堆垛层数对脱硫的促进作用占据主导地位，致使络合剂改性催化剂的脱硫活性增加幅度大于烯烃饱和活性增加幅度。

关键词: 络合剂, CoMo催化剂, 烯烃加氢, 加氢脱硫, 选择性

Abstract: A series of CoMo/ZSM-5-Al2O3 HDS catalysts was prepared with different chelating agents, such as citric acid, nitrilotriacetic acid, ethylene diamine tetraacetic acid and trans-1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid and characterized by FT-IR, H2-TPR, HRTEM, 27Al NMR and XPS techniques. The effect of the chelating agents on the HDS selectivity was investigated. The results showed that the agents preferentially complexed with Co and Al in the carrier and reduce the reduction temperature of metal components, improve the sulfurization degree of Mo, and increase the number of active center of the catalyst. The use of chelating agent increases the number of stacking layer and the length of MoS2 lamella. The number of stacking layer played a dominant role in promoting desulfurization, resulting in a greater increase in desulfurization activity of the modified catalyst than that in olefin saturation.

Key words: chelating agent, CoMo catalyst, olefin hydrogenation, hydrodesulfurization, selectivity

中图分类号:

靳凤英范景新郭春垒刘航臧甲忠于海斌王祥生王亚权. 络合剂添加对CoMo催化剂加氢脱硫选择性的影响[J]. 石油炼制与化工, 2020, 51(8): 62-69.

参考文献

[1]李明丰, 习远兵, 潘光成, 等.催化裂化汽油选择性加氢脱硫工艺流程选择[J].石油炼制与化工, 2010, 41(5):1-6 [2]李大东.支撑未来炼油工业发展的若干关键技术[J].催化学报, 2013, 34(1):48-60 [3] Thomson M S.Preparation of high activity silica-supported hydrotreating catalysts and catalysts thus prepared[J].EP, 0181035A2, 1986-05-14, :- [4] Nicosia D, Prins R..The effect of glycol on phosphate-doped CoMo/Al2O3 hydrotreating catalysts[J]. J. Catal., 2005, 229(2):424-438 [5] Shimizu T, Hiroshima K., Honma T., et al.. Highly active hydrotreatment catalysts prepared with chelating agents[J].Catal. Today, 1998, 45(1-4):271-276 [6] Ohta Y, Shimizu T., Honma T., et al.. Effectof chelating agents on HDS and aromatic hydrogenation over CoMo- and NiW/Al2O3[J].Stud. Surf. Sci. Catal., 1999, 0( 127):161-168 [7] Hiroshima K, Mochizuki T., Honma T., et al..High HDS activity of CoMo/Al2O3 modified by some chelates and their surface fine structures[J].Appl. Surf. Sci., 1997, 0(121/122):433-436 [8] Rana MS., Ramírez J., Gutiérrez-Alejandre A., et al. .Support effects in CoMo hydrodesulfurization catalysts prepared with EDTA as a chelating agent[J].J. Catal., 2007, 246(1):100-108 [9] 靳凤英，郭新闻，王祥生.乙二胺四乙酸改性对NiMo/nano-HZSM-5催化剂脱硫性能的影响[J].高等学校化学学报, 2011, 32(1):113-117 [10] 王学勤, 王祥生, 郭新闻.超细颗粒五元环型沸石[J].中国, 1240193[P], 2006-06-21, :- [11]Vradman L.Landau MV.,Kantorovich D.,et al. Evaluation of metal oxide phase assembling mode inside the nanotubular pores of mesostructure silica[J].Microporous Mesoporous Mater., 2005, 79(1-3):307-318 [12] 陈文斌, 杨清河, 赵新强, 等.加氢脱硫催化剂活性组分的分散与其催化性能[J].石油学报(石油加工), ,2013, .29(5):752-756 [13] Zhao Hongbin, Zhang Zisheng, Shemshaki Farzaneh, et al.Aqueous Interfacial Chemistry in the Catalyst Preparation of NiMo/Al2O3 System by EDTA-Containing Impregnation[J]. Energy & Fuels, 2006, 2(5):1822-1827 [14] Mackenzie K J. D., Smith M. E..Multinuclear solid-state NMR of inorganic materials[J].Amsterdan: Pergamon press, 2002, :307-308 [15] Gandubert AD., Legens C., Guillaume D., et al..X-ray photoelectron spectroscopy surface quantification of sulfided CoMoP catalysts - Relation between activity and promoted sites - PartⅠ: Influence of the Co/Mo ratio[J].Oil Gas Sci. Technol.-Rev. IFP, 2007, 62(1):79-89 [16] Damyanova S, Petrov L., Grange P..XPS characterization of zirconium-promoted CoMo hydrodesulfurization catalysts[J].Appl. Catal. A: Gen., 2003, 239(1-2):241-252 [17] Portela L, Grange P., Delmon B..XPS and NO adsorption studies on alumina-supported Co-Mo catalysts sulfided by different procedures [J]. J. Catal., 995, 156(2):243-254 [18] Damyanova S, Petrov L., Grange P..XPS characterization of zirconium-promoted CoMo hydrodesulfurization catalysts[J].2003, 2003, 239(1-2):241-252 [19] Saih Y, Nagata M., Funamoto T., et al..Ultra deep hydrodesulfurizatin of dibenzothiophene derivatives over NiMo/TiO2-Al2O3 catalysts[J].Appl. Catal. A: Gen., 2005, 295(1):11-22 [20] Chen W B., Maugé F., van Gestel J., et al.. Effect of modification of the alumina acidity on the properties of supported Mo and CoMo sulfide catalysts [J].J. Catal., 2013, 0(304):47-62 [21]卢安鹏, 聂红, 陈文斌, 等.柠檬酸对催化剂中助剂作用的影响[J].石油炼制与化工, 2015, 46(9):1-6 [22]卢安鹏, 陈文斌, 聂红, 等.柠檬酸对γ-催化剂中助剂作用的影响[J].石油炼制与化工, 2018, 49(10):52-57 [23]聂红, 李会峰, 龙湘云, 等.络合技术在加氢催化剂中的应用[J].石油学报石油加工, 2015, 31(2):250-258