硫酸根对Ni/γ-Al2O3催化剂加氢脱硫选择性的影响

摘要/Abstract

摘要： 以γ-Al2O3为载体，采用等体积浸渍法分别制备了H2SO4，Ni(NO3)2，Ni(NO3)2-H2SO4，NiSO4改性的加氢脱硫催化剂。采用X射线衍射、N2吸附-脱附、H2-程序升温还原、紫外-拉曼光谱、X射线光电子能谱和反应性能评价等方法研究了硫酸根对Ni/γ-Al2O3催化剂的物性和催化噻吩加氢脱硫选择性的影响。结果表明：含硫酸根前躯体制备的Ni/γ-Al2O3催化剂的加氢脱硫活性和选择性高于Ni(NO3)2前躯体制备的催化剂；NiSO4前躯体制备催化剂的加氢脱硫活性和选择性最高，较Ni(NO3)2制备的催化剂分别提高了19百分点和78%。催化活性的差异与催化剂中Ni的形态相关，硫酸根的存在一方面减弱了Ni与载体间的相互作用，另一方面提供了镍原位自硫化的硫化剂，形成的硫化镍物种与NiSO4是催化剂的活性中心，其脱硫活性和选择性明显高于引入硫化剂硫化的催化剂。

关键词: 硫酸根, 硫酸镍, 硝酸镍, 加氢脱硫, 氧化铝, 选择性

Abstract: A series of hydrodesulfurization catalysts modified by H2SO4, Ni (NO3)2, Ni (NO3)2-H2SO4, NiSO4, respectively were prepared by the incipient wet impregnation method with γ-Al2O3 as carrier. The effects of sulfate radical on the physicochemical properties and thiophene selective HDS performance were studied by XRD, BET, H2-TPR, FT-IR, XPS and UV Raman spectroscopy. The HDS performance was tested in a small fixed bed using cyclohexane solution containing thiophene and isopentene as feedstock. The results showed that the hydrodesulfurization activity and selectivity of Ni/γ-Al2O3 modified with sulfate radical was better than the one modified with Ni(NO3)2; the catalyst prepared with nickel sulfate showed the highest activity and selectivity, 19 percentage points and 78% higher than the catalyst from nickel nitrate, respectively. The differences in catalytic activity were associated with the form of Ni in the catalyst, the presence of sulfate radical, on the one hand, weakens the interaction between the Ni and carrier, on the other hand, provides the sulfide agent for sulfidation of Ni in situ to form nickel sulfide. Both nickel sulfide and NiSO4 form the reactive center of catalysts, its activity and selectivity for HDS is significantly higher than the catalyst sulfided by introduction of sulfidation agent.

Key words: sulfate radical, Nickel sulfate, nickel nitrate, hydrodesulfurization, alumina, selectivity

中图分类号:

靳凤英于海斌臧甲忠王亚权郭春垒刘航马明超范景新. 硫酸根对Ni/γ-Al2O3催化剂加氢脱硫选择性的影响[J]. 石油炼制与化工, 2020, 51(11): 46-52.

参考文献

[1]韩贺，刘民，吴宏宇，等.镍盐前驱体对改性-择形催化甲苯与甲醇合成对二甲苯反应性能的影响[J].石油学报石油加工, 2014, 30(4):611-619 [2] 任世彪，邱金恒，王春燕，等.镍盐前体对Ni/γ-Al2O3催化剂催化加氢活性的影响[J].催化学报, 2007, 28(7):651-656 [3]白振江，王亚萍，殷长龙，等.镍前驱体对非负载型--柴油加氢催化剂结构和性能的影响[J].石油炼制与化工, 2015, 46(4):40-45 [4]王文寿，郭洪臣，刘海鸥，等.或改性的纳米-催化剂的加氢脱硫活性[J].催化学报, 2008, 29(8):705-709 [5]Ciambelli P, Fortuna M E, Sannino D, et al.The influence of sulphate on the catalytic properties of V2O5-TiO2 and WO3-TiO2 in the reduction of nitric oxide with ammonia[J].Catalysis Today, 1996, 29(1-4):161-164 [6]Khodayri R, Odenbrand CU. I.Regenaration of commercial SCR catalysts by washing and sulphation: effect of sulphata groups on the activity[J].Applied Catalysis B: Environmental, 2001, 33(4):277-291 [7] Xu T F, Wu X D, Liu X S, et al.Effect of barium sulfate modification on the SO2 tolerance of V2O5/TiO2 catalyst for NH3-SCR reaction[J].Journal of Environment Sciences, 2017, 57(0):110-117 [8] Jin T, Yamaguchi T., Tanabe K. .Mechanism of acidity generation on sulfur-promoted metal oxides [J].The Journal of Physical Chemistry, 1986, 90(20):4794-4796 [9]李瑞勇, 李晓杰, 文继明, 等.温度对爆轰法合成纳米氧化铝晶型及晶粒度的影响[J].材料开发与应用, 2005, 20(5):5-7 [10]张成喜，彭凯，李永祥.负载型催化剂性能与结构研究[J].石油炼制与化工, 2016, 47(2):38-41 [11]Wang S B, Lu G Q.Reforming of methane with carbon dioxide over NiAl2O3 catalysts: Effect of nickel precursor[J].Applied Catalysis A: General, 1998, 169(2):271-280 [12]Yang RC.,Li XG.,Wu J. S.,et al. .Hydrotreating of crude 2-ethylhhexanol over NiAl2O3 catalysts: Surface Ni species-catalytic activity correlation[J].Applied Catalysis, A, 2009, 368(2):105-112 [13]王丹，周清华，王冰，等.制备方法对镍系催化剂的影响[J].石油化工, 2015, 44(10):1193-1198 [14] 王文寿.FCC汽油中硫化物在改性纳米HZSM-5催化剂上的脱除[J].大连：大连理工大学, ,2009, :- [15]Wang F，Zhang YH.,Li S. H.,et al.. A strategy for single supersaturated droplet analysis: confocal Raman investigations on the complicated hygroscopic properties of individual MgSO4 droplets on the quartz substrate[J].Analytical Chemistry, 2005, 77(22):7148-7155 [16] Wang AL., Freeman J. J., Jolliff B. L., et al.. Sulfates on Mars: A systematic Raman spectroscopic study of hydration states of magnesium sulfates[J].Geochimica et Cosmochimica Acta, 2006, 70(24): 6118-6135 [17]Zhang YH.,Chan C K.Study of contact ion pairs of supersaturated magnesium sulfate solutions using Raman scattering of levitated single droplets[J].Journal of Physical Chemistry A, 2000, 104(40):9191-9196 [18]Zhang YH.,Chan C K.Understanding the hygroscopic properties of supersaturated droplets of metal and ammonium sulfate solutions using Raman spectroscopy[J].Journal of Physical Chemistry A, 2002, 106(2):285-292 [19]Chan SS.,Wachs IE.. In situ laser Raman spectroscopy of nickel oxide supported on γ-Al2O3[J].Journal Catalysis, 1987, 103(1):224-227 [20]Liu F.Xu SP.,Cao L.,et al. A comparison of NiMoAl2O3 catalysts prepared by impregnation and coprecipitation methods for hydrodesulfurization of dibenzothiophene[J].Journal of Physical Chemistry C, 2007, 111(20):7396-7402 [21]Shalvoy RB.,Reucroft PJ.. Characterization of a sulfur-resistant methanation catalyst by XPS[J].Journal of Vacuum Science and Technology, 1979, 16(2):567-569 [22]Nefedov VI.,Salyn YaV.,Leonhardt G.,et al. .A comparison of different spectrometers and charge corrections used in X-ray photoelectron spectroscopy[J].Journal of Electron Spectroscopy and Related Phenomena, 1977, 10(2):121-124 [23]Matienzo JYin LoI.,Grim Samue O.,et al.. X-ray photoelectron spectroscopy of nickel compounds[J].Inorganic Chemistry, 1973, 12(12):2762-2769 [24]Sohn JR.,Park WC.,Kim H. W.. Characterization of nickel sulfate supported on γ-Al2O3 for ethylene dimerization and its relationship to acidic properties[J].Journal of Catalysis, 2002, 209(1):69-74 [25] Arata K, Hino M. .Solid catalyst treated with anion: XVIII. Benzoylation of toluene with [J]. Applied Catalysis, 1990, 59(1):197-204 [26]Zhang B.Ye XC.,Dai W.,et al.. Biomolecule-assisted synthesis and electrochemical hydrogen storage of porous spongelike Ni3S2 nanostructures grown directly on nickel foils[J].Chemistry A European Journal, 2006, 12(8):2337-2342 [27]Uzkan, US.,Zhang,LP.,Ni,S. Y.,et al.. Investigation of the role of nickel and the effect of gas phase sulfur compounds on the performance of Ni-Moγ-Al2O3 hydrodenitrogenation catalysts[J].Journal of Catalysis, 1994, 148(1):181-193 [28] Jin FY., Long H. Y., Song W. C., et al.. Active phase of a NiSO4 catalyst supported on γ-Al2O3 during in situ self-sulfidation for selective hydrodesulfurization[J]. Energy& Fuels, 2013, 27(6):3394-3399 [29]Struis RP. WJ.,Schildhauer T. J.,Czekaj I.,et al.. Sulfur poisoning of Ni catalysts in the SNG production from biomass: A TPOXPSXAS study[J].Applied Catalysis A: General, 2009, 362(1-2):121-128