载体孔径分布集中度对Ni-Mo催化剂上芘加氢反应的影响

摘要/Abstract

摘要： 采用NaAlO₂-Al(SO₄)₃法制备得到拟薄水铝石，通过控制拟薄水铝石的老化时间来调节拟薄水铝石的晶粒尺寸，得到比表面积、孔体积、孔径基本相同，孔集中度有所差异的4种不同孔结构的载体。以芘作为模型化合物在高压微型固定床反应装置上考察了4种载体所制备Ni-Mo催化剂的芳烃加氢饱和性能。采用X射线衍射仪、X射线光电子能谱仪、透射电子显微镜和色谱-质谱联用仪等对拟薄水铝石、载体、催化剂进行表征。结果表明：随着老化时间的增加，拟薄水铝石的结晶度和晶粒尺寸增加；载体的比表面积、孔体积和最可几孔径相近，孔径分布集中度增加；表面总羟基数量和碱性羟基所占比例逐渐降低，氧化态催化剂金属和载体之间相互作用力降低，硫化后催化剂硫化度以及Ⅱ类多层活性相所占比例增加。芘的加氢评价结果表明，随着载体孔径分布集中度的增加，芘加氢转化率提高。说明硫化度和Ⅱ类活性相所占比例增加有利于提高催化剂加氢性能，载体孔径分布集中度提高后，8~10nm孔所占的有效比表面积明显增加，更有利于分子扩散进入孔内接触到有效活性中心。

关键词: 拟薄水铝石, 老化时间, 加氢, 孔径分布集中度, 芘

Abstract: Pseudo-boehmite was prepared by the NaAlO₂-Al(SO₄)₃ method, the grain size of the pseudo-boehmite was adjusted by controlling the aging time of the pseudo-boehmite, and four carriers with different pore structures were obtained with the same specific surface area, pore volume and pore size, but the pore size distribution was different. Pyrene was used as a model compound to investigate the hydrogenation saturation properties of the catalysts prepared by these four carriers on a high-pressure microreaction device. BET, XRD, XPS, TEM and GC-MS were used to characterize the pseudo-boehmite, support and catalyst. The results showed that with the increase of aging time, the crystallinity and grain size of the pseudo-boehmite increased, the specific surface, pore volume and maximum pore size of the support were similar, the pore size distribution concentration increased, the number of total hydroxyl groups on the surface and the proportion of basic hydroxyl groups decreased gradually, the interaction force between the oxidized metal and the support decreased, and the sulfidation degree of the catalyst and the proportion of class Ⅱ multilayer active phases increased after sulfidation. The hydrogenation evaluation results of pyrene displayed that the hydrogenation conversion rate of pyrene increased with the increase of the concentration of carrier pore size distribution. The results also indicated that the increase of sulfidation degree and the proportion of type Ⅱ active phase was conducive to improving the hydrogenation performance of the catalyst. With the increase of the concentration of pore size distribution, the effective specific surface of the 8-10 nm pores was obviously increased, which was more conducive to the molecules diffusion into the pores to contact active site.

Key words: pseudo-boehmite, aging time, hydrogenation, concentration of pore size distribution, pyrene

温昌盛聂红曾双亲郭锦春贾燕子杨清河. 载体孔径分布集中度对Ni-Mo催化剂上芘加氢反应的影响[J]. 石油炼制与化工, 2024, 55(10): 84-93.

参考文献

[1]路军晓.DCC工艺与FCC工艺的区别[J].化工管理, 2021, 34(34):165-167
[2]Oh S K, Ku H, Han G B, et al.Hydrogenation of polycyclic aromatic hydrocarbons over Pt/γ-Al2O3 catalysts in a trickle bed reactor[J].Catalysis Today, 2023, Vol.411(0920-5861):1-9
[3]李大东.加氢处理工艺与工程 [M]. 北京：中国石化出版社.2004.
[4]Korre S C, Neurock M, Klein M T, et al.Hydrogenation of polynuclear aromatic hydrocarbons2. quantitative structurereactivity correlations[J].Chemical Engineering Science, 1994, 49(24):4191-210
[5]Korre S C, Klein M T, Quann R J.Polynuclear Aromatic Hydrocarbons Hydrogenation1. Experimental Reaction Pathways and Kinetics[J].Industrial & Engineering Chemistry Research, 2002, 34(1):101-17
[6]Minabe M, Nakada K.Hydrogenation of Pyrene and Catalytic Interconversion of Hydropyrenes[J].Bulletin of the Chemical Society of Japan, 1985, 58(7):1962-6
[7]刘锋, 李会峰, 刘泽龙, 等.芘在不同加氢催化剂上反应性能的比较[J].石油学报石油加工, 2011, 27(03):343-7
[8]Antwi Peprah B, Brown O, Stryker J M, et al.Sulfided Homogeneous Iron Precatalyst for Partial Hydrogenation and Hydrodesulfurization of Polycyclic Aromatic Model Asphaltenes[J].Energy & Fuels, 2020, 34(12):16532-41
[9]Lin Q, Shimizu K-i, Satsuma A.Hydrogenation of pyrene using Pd catalysts supported on tungstated metal oxides[J].Applied Catalysis A: General, 2010, 387(1-2):166-72
[10]Nie Hong, Li Huifeng, Yang Qinghe, et al.Effect of structure and stability of active phase on catalytic performance of hydrotreating catalysts[J].Catalysis Today, 2018, Vol.316(No.0):13-20
[11]杨翠定.石油化工分析方法（RIPP实验方法）[M], RIPP139-90.
[12]曾双亲, 杨清河, 肖成武, 等.干燥方式及老化条件对拟薄水铝石性质的影响[J].石油炼制与化工, 2012, 43(06):53-7
[13]Xue, Lijun; Zhang, Di; Xu, Yongqiang et al.Adsorption of thiophene compounds on MoO3/γ-Al2O3 catalysts with different mesopore sizes[J].Microporous and Mesoporous Materials, 2017, Vol.238(No.0):46-55
[14]Zhang, Di; Liu, Xinmei; Liu, Yuxiang; et al.Impact of γ-alumina pore structure on structure and performance of Ni–Mo/γ-Al2O3 catalyst for 4, 6-dimethyldibenzothiophene desulfurization[J].Microporous and Mesoporous Materials,, 2021, Vol.310(No.0):110637-110645
[15]Badoga S, Sharma R V, Dalai A K, et al.Synthesis and characterization of mesoporous aluminas with different pore sizes: Application in NiMo supported catalyst for hydrotreating of heavy gas oil[J].APPLIED CATALYSIS A-GENERAL, 2015, Vol.489(No.0):86-97
[16]Li M, Li H, Jiang F, et al.Effect of surface characteristics of different alumina on metal–support interaction and hydrodesulfurization activity[J].Fuel, 2009, 88(7):1281-5
[17]Borowiecki T, Gac W, Denis A.Effects of small MoO3 additions on the properties of nickel catalysts for the steam reforming of hydrocarbons[J].Applied Catalysis A: General, 2004, 270(1-2):27-36
[18]袁蕙, 徐广通, 齐和日玛, 等.激光拉曼光谱在加氢脱硫催化剂-中的应用研究[J].光谱学与光谱分析, 2014, 34(02):435-8
[19]邱丽美, 齐和日玛, 刘清河, 等.射线光电子能谱法研究加氢脱硫催化剂中活性元素的化学态[J].石油学报石油加工, 2011, 27(04):638-42
[20]Yanzi Jia , Huifeng Li , Qinghe Yang , et al.Design of active phase structure with high activity and stability in residue hydrotreating reactions[J].Fuel, 2024, Vol.360(No.0):130288-130294
[21]Topsoe H.In situ Mssbauer emission spectroscopy studies of unsupported and supported sulfided Co$zsbnd;Mo hydrodesulfurization catalysts: Evidence for and nature of a Co$z.sbnd;Mo$z.sbnd;S phase[J].Journal of Catalysis, 1981, 68(2):433-52
[22]Henrik Topsoe, Berit Hinnemann, Jens K.Norskov, et al.The role of reaction pathways and support interactions in the development of high activity hydrotreating catalysts[J].Catalysis Today, 2005, Vol.107-108(No.107-108):11-22