NiMo/Al2O3催化剂性质与加氢脱硫转化率的定量关系模型

石油炼制与化工 ›› 2018, Vol. 49 ›› Issue (1): 54-59.

NiMo/Al2O3催化剂性质与加氢脱硫转化率的定量关系模型

蒋绍洋¹,刘秀娜²,刘志坚¹,方维平²

1. 中国石化催化剂有限公司
2. 厦门大学化学化工学院

收稿日期:2017-07-03 修回日期:2017-07-18 出版日期:2018-01-12 发布日期:2018-01-24
通讯作者: 蒋绍洋 E-mail:jiangshaoyang@sinopec.com
基金资助:

QUANTITATIVE RELATIONSHIP BETWEEN CATALYST PROPERTIES AND HYDRODESULFURIZATION CONVERSION OVER NiMo/Al2O3

Received:2017-07-03 Revised:2017-07-18 Online:2018-01-12 Published:2018-01-24
Supported by:

摘要/Abstract

摘要： 通过改变金属负载量得到一系列不同性质的NiMo/Al2O3催化剂，定量研究NiO负载量、MoO3负载量和MoS2晶簇表面有效Mo原子分散度3个变量对加氢脱硫(HDS)活性的影响规律。运用“动态超几何平均”的方法对已提出的模型进行修正，建立了二苯并噻吩HDS转化率与催化剂性质的定量关系模型。结果表明：所提出的模型对实验数据拟合的平均相对偏差仅为1.13%；用所建立的模型计算得到最佳的NiO负载量（w）为3%~4%，MoO3负载量（w）为12%~14%；Mo原子分散度对催化剂的活性具有正面影响；催化剂HDS活性对NiO含量更敏感。

关键词: NiMo/Al2O3催化剂, 数学模型, 金属负载量, 分散度, 加氢脱硫活性

Abstract: A series of NiMo/Al2O3 catalysts with different properties was obtained by controlling the metal loading. NiO loading, MoO3 loading and the MoS2 dispersion of the catalysts were considered and a “changing super geometric average” was applied to revise the existing model to establish a quantitative relationship between the catalyst properties and the HDS conversion. The results indicated that the average relative deviation for the modified model is only 1.13%. The optimum MoO3 and NiO loadings are 12%-14% and 3%-4%, respectively, as analyzed by the established model. The results also showed that hydrodesulfurization activity is more sensitive to the content of NiO loading.

Key words: NiMo/Al2O3 catalyst, mathematic model, metal loading, dispersion, hydrodesulfurization activity

中图分类号:

蒋绍洋刘秀娜刘志坚方维平. NiMo/Al2O3催化剂性质与加氢脱硫转化率的定量关系模型[J]. 石油炼制与化工, 2018, 49(1): 54-59.

参考文献

[1]Rashidi F, Sasaki T, Rashidi A M, et al.. Ultradeep hydrodesulfurization of diesel fuels using highly efficient nanoalumina-supported catalysts: Impact of support, phosphorus, and/or boron on the structure and catalytic activity [J]. [J].Journal of Catalysis, 2013, 299(299):321-335
[2]Hao L, Xiong G, Liu L, et al.Preparation of highly dispersed desulfurization catalysts and their catalytic performance in hydrodesulfurization of dibenzothiophene[J].Chinese Journal of Catalysis, 2016, 37(3):412-419
[3] Afanasiev P, Bezverkhyy I.Ternary transition metals sulfides in hydrotreating catalysis [J]. Applied Catalysis a-General, 2007, 322:129-141.[J].Applied Catalysis a-General, 2007, 322(322):129-141
[4]Usman, Kubota T, Hiromitsu I, et al.Effect of boron addition on the surface structure of Co-MoAl2O3 catalysts[J].Journal of Catalysis, 2007, 247(1):78-85
[5]王洋, 王鼎聪.活性金属浸渍方式对渣油加氢催化剂金属分散态的影响[J].石油炼制与化工, 2013, 44(8):8-12
[6]Guo R, Shen B X, Fang X C, et al.Study on Relationship between microstructure of active phase and HDS performance of sulfided Ni-Mo catalysts: effect of metal loading[J].China Petroleum Processing & Petrochemical Technology, 2014, 16(2):12-19
[7]Kumaran G M, Garg S, Soni K, et al.Effect of Al-SBA-15 support on catalytic functionalities of hydrotreating catalystsII. Effect of variation of molybdenum and promoter contents on catalytic functionalities[J].Industrial & Engineering Chemistry Research, 2007, 46(14):4485-4496
[8]Garg S, Soni K, Prasad V V D N, et al.Effect of method of preparation on hydrodesulphurization activity of Co- or Ni-promoted MoS2SBA-15 catalysts[J].Journal of Chemical Sciences, 2014, 126(2):437-444
[9]Veen J A R V, Colijn H A.On the formation of type I and type II NiMoS phases in NiMoAl2O3 hydrotreating catalysts and its catalytic implications[J].Fuel Processing Technology, 1993, 35(1-2):137-157
[10]Hensen E J M, Beer V H J D, Veen J A R V, et al.A refinement on the notion of type I and II (Co)MoS phases in hydrotreating catalysts[J].Catalysis Letters, 2002, 84(1):59-67
[11]Kibsgaard J, Tuxen A, Knudsen K G, et al.Comparative atomic-scale analysis of promotional effects by late 3d-transition metals in MoS2 hydrotreating catalysts[J].J Catal, 2010, 272(2):195-203
[12]王永刚, 张海永, 张培忠等.NiW/γ- Al2O3催化剂的低温煤焦油加氢性能研究[J].燃料化学学报, 2012, 12(12):1492-1497
[13]Garg S, Soni K, Prabhu T A, et al.Effect of ordered mesoporous Zr SBA-15 support on catalytic functionalities of hydrotreating catalysts 2. Variation of molybdenum and promoter loadings [J]. Catalysis Today, 2016, 261: 128-136.[J].Catalysis Today, 2016, 261(261):128-136
[14]Boahene P E, Soni K K, Dalai A K, et al.Hydroprocessing of heavy gas oils using FeW/SBA-15 catalysts: Experimentals, optimization of metals loading, and kinetics study [J]. Catalysis Today, 2013, 207: 101-111.[J].Catalysis Today, 2013, 207(207):101-111
[15]Zuo D, Li D, Nie H, et al.Acid–base properties of NiWAl2O3 sulfided catalysts: relationship with hydrogenation,isomerization and hydrodesulfurization reactions[J].Journal of Molecular Catalysis A: Chemical, 2004, 211(1–2):179-189
[16]Fan Y, Xiao H, Shi G, et al.Citric acid-assisted hydrothermal method for preparing NiWUSY–Al2O3 ultradeep hydrodesulfurization catalysts[J].Journal of Catalysis, 2011, 279(1):27-35
[17]Liu X, Jiang S, Lai W, et al.Quantitative relationship model between support properties and dibenzothiophene hydrodesulfurization conversion over NiMo/Al2O3 [J]. Reaction Kinetics Mechanisms & Catalysis, 2017, 1-15.[J].Reaction Kinetics Mechanisms & Catalysis,, 2017, 2017(2017):1-15