硫氮化合物在磷改性NiW/Al2O3加氢催化剂上的吸附行为研究

doi:10.11949/0438-1157.20200713

摘要/Abstract

摘要：

采用等体积浸渍法制备了一系列以γ-Al₂O₃及磷改性γ-Al₂O₃为载体，Ni、W为活性金属组分的加氢催化剂，以N₂物理吸附-脱附、XRD、NH₃-TPD、Py-IR等技术对Al₂O₃及P/Al₂O₃系列催化剂进行了表征，考察了磷改性对加氢催化剂理化性质的影响，探究了喹啉、吲哚和二苯并噻吩（DBT）吸附行为与催化剂理化性质以及吸附质本身性质的关系。研究发现，喹啉最易于吸附在Al₂O₃及P/Al₂O₃系列催化剂上，吲哚和DBT的吸附能力较为接近；磷的引入会降低催化剂的比表面积和孔体积，但是能够提高喹啉、吲哚及DBT的吸附能力；硫氮化合物在催化剂上的吸附能力随着催化剂表面酸性的增强或酸中心数量的增多、活性金属分散度的增大以及硫氮化合物杂原子电子云密度或分子极性的增大而增大。

关键词: 催化剂, 加氢, 氧化铝, 磷, 硫氮化合物, 吸附

Abstract:

A series of hydrogenation catalysts with γ-Al₂O₃ and phosphorus-modified γ- Al₂O₃ as the carrier and Ni and W as the active metal components were prepared by the equal volume impregnation method. The supports and catalysts were characterized with N₂ adsorption-desorption, XRD, NH₃-TPD and Py- IR. The phosphorus modification effects on the properties of hydrogenation catalysts were examined, and the relationship between adsorption behavior of quinoline, indole, dibenzothiophene(DBT) and the catalysts properties as well as the properties of the adsorbate itself were investigated. The results indicated that quinoline was the most easily adsorbed on Al₂O₃ catalysts and phosphorus-modified Al₂O₃ catalysts, while the adsorption capacity of indole and DBT was almost the same. The catalysts modified by phosphorus showed smaller specific surface area and pore volume, but on which the adsorption capacity of quinoline, indole and DBT was promoted. The adsorption capacity of sulfur and nitrogen compounds on the catalysts increased with the increase of the catalyst surface acidity or the acid site quantities and the increase of the active metal dispersion, as well as the increase of the heteroatom electron cloud density or molecular polarity of the sulfur and nitrogen compounds.

Key words: catalyst, hydrogenation, alumina, phosphorus, sulfur and nitrogen compound, adsorption

中图分类号:

魏强, 黄文斌, 周亚松. 硫氮化合物在磷改性NiW/Al₂O₃加氢催化剂上的吸附行为研究[J]. 化工学报, 2021, 72(3): 1372-1381.

WEI Qiang, HUANG Wenbin, ZHOU Yasong. Research on adsorption behavior of sulfur and nitrogen compounds on P modified NiW/Al₂O₃ catalyst[J]. CIESC Journal, 2021, 72(3): 1372-1381.

图/表 14

图1 Al2O3及P/Al2O3系列催化剂孔径分布曲线

Fig.1 Pore size distribution of Al2O3 catalysts and P/Al2O3 catalysts

表1 Al2O3及P/Al2O3系列催化剂孔结构性质

Table 1 Pore structure of Al2O3 catalysts and P/Al2O3 catalysts

催化剂	比表面积/ (m²·g^-1)	孔体积/ (ml·g^-1)	平均孔径/nm
Al₂O₃	278.9	0.61	6.4
Ni/Al₂O₃	252.8	0.57	6.5
W/Al₂O₃	208.2	0.43	6.0
NiW/Al₂O₃	186.7	0.38	5.9
P/Al₂O₃	251.1	0.60	6.9
Ni/P/Al₂O₃	240.0	0.55	6.8
W/P/Al₂O₃	190.4	0.39	6.8
NiW/P/Al₂O₃	173.0	0.35	6.9

图2 Al2O3及P/Al2O3系列催化剂的XRD谱图

Fig.2 XRD patterns for Al2O3 catalysts and P/Al2O3 catalysts

图3 Al2O3及P/Al2O3系列催化剂的NH3-TPD谱图

Fig.3 NH3-TPD spectra of Al2O3 catalysts and P/Al2O3 catalysts

表2 Al2O3及P/Al2O3系列催化剂的酸性质

Table 2 Acid property of Al2O3 catalysts and P/Al2O3 catalysts

催化剂

200℃脱附

350℃脱附

弱酸中心数量

（L酸）/(μmol·g^-1)

NiW/Al₂O₃

NiW/P/Al₂O₃

图4 喹啉和吲哚在Al2O3及P/Al2O3系列催化剂上的动态吸附

Fig.4 Dynamic adsorption of quinoline and indole on Al2O3 catalysts and P/Al2O3 catalysts

表3 喹啉和吲哚在Al2O3及P/Al2O3系列催化剂的平衡吸附量

Table 3 Equilibrium adsorption capacity of quinoline and indole on Al2O3 catalysts and P/Al2O3 catalysts

催化剂	比表面积/ (m²·g^-1)	喹啉平衡吸附量/(μg·m^-2)	吲哚平衡吸附量/(μg·m^-2)
Al₂O₃	278.9	10.43	6.42
Ni/Al₂O₃	252.8	9.57	6.32
W/Al₂O₃	208.2	16.09	9.60
NiW/Al₂O₃	186.7	18.69	11.78
P/Al₂O₃	251.1	11.83	7.17
Ni/P/Al₂O₃	240.0	11.67	6.67
W/P/Al₂O₃	190.4	20.17	11.03
NiW/P/Al₂O₃	173.0	25.16	13.87

图5 DBT在Al2O3及P/Al2O3系列催化剂上的动态吸附

Fig.5 Dynamic adsorption of DBT on Al2O3 catalysts and P/Al2O3 catalysts

表4 DBT在Al2O3及P/Al2O3系列催化剂的平衡吸附量

Table 4 Equilibrium adsorption capacity of DBT on Al2O3 catalysts and P/Al2O3 catalysts

催化剂	比表面积/ (m²·g^-1)	DBT平衡吸附量/(μg·m^-2)	DBT饱和吸附量/(mg·g^-1)
Al₂O₃	278.9	7.35	2.05
Ni/Al₂O₃	252.8	7.31	1.85
W/Al₂O₃	208.2	11.71	2.33
NiW/Al₂O₃	186.7	11.42	2.13
P/Al₂O₃	251.1	8.36	2.10
Ni/P/Al₂O₃	240.0	7.79	1.87
W/P/Al₂O₃	190.4	11.82	2.25
NiW/P/Al₂O₃	173.0	13.35	2.31

图6 喹啉、吲哚及DBT在NiW/Al2O3及NiW/P/Al2O3催化剂上的动态吸附

Fig.6 Dynamic adsorption of quinoline, indole and DBT on NiW/Al2O3 catalysts and NiW/P/Al2O3 catalysts

表5 喹啉、吲哚及DBT在NiW/Al2O3及NiW/P/Al2O3催化剂上的平衡吸附量

Table 5 Equilibrium adsorption capacity of quinoline, indole and DBT on NiW/Al2O3 catalysts and NiW/P/Al2O3 catalysts

催化剂

比表面积/(m²·g^-1)

喹啉平衡吸附量/

(μg·m^-2)

吲哚平衡吸附量/

(μg·m^-2)

DBT平衡吸附量/

(μg·m^-2)

NiW/Al₂O₃

NiW/P/Al₂O₃

图7 喹啉、吲哚及DBT电荷分布示意图

Fig.7 Scheme of charge distribution of quinoline, indole and DBT

图8 喹啉、吲哚及DBT分子偶极矩示意图

Fig.8 Scheme of dipole moments of quinoline, indole and DBT

表6 喹啉、吲哚及DBT的分子结构特点

Table 6 Structural characteristics of quinoline, indole and DBT

吸附质	喹啉	吲哚	DBT
分子偶极矩/Debye	1.869	1.886	0.475
HOMO轨道特征值/eV	-5.856	-4.972	-5.179
C—N/C—S键键长/?	1.374	1.388	1.765

参考文献 28

1	徐春明, 杨朝合. 石油炼制工程[M]. 4版. 北京: 石油工业出版社, 2009: 277-280.
	Xu C M, Yang C H. Petroleum Refining Engineering[M]. 4th ed. Beijing: Petroleum Industry Press, 2009: 277-280.
2	Han W, Nie H, Long X Y, et al. Preparation of F-doped MoS₂/Al₂O₃ catalysts as a way to understand the electronic effects of the support Brønsted acidity on HDN activity[J]. Journal of Catalysis, 2016, 339: 135-142.
3	Wei Q, Wen S C, Tao X J, et al. Hydrodenitrogenation of basic and non-basic nitrogen-containing compounds in coker gas oil[J]. Fuel Processing Technology, 2015, 129: 76-84.
4	Yik E, Iglesia E. Mechanism and site requirements for thiophene hydrodesulfurization on supported Re domains in metal or sulfide form[J]. Journal of Catalysis, 2018, 368: 411-426.
5	Zhou W W, Zhang Y N, Tao X J, et al. Effects of gallium addition to mesoporous alumina by impregnation on dibenzothiophene hydrodesulfurization performances of the corresponding NiMo supported catalysts[J]. Fuel, 2018, 228: 152-163.
6	Vázquez-Garrido I, López-Benítez A, Berhault G, et al. Effect of support on the acidity of NiMo/Al₂O₃-MgO and NiMo/TiO₂-Al₂O₃ catalysts and on the resulting competitive hydrodesulfurization/hydrodenitrogenation reactions[J]. Fuel, 2019, 236: 55-64.
7	Prado G H C, Rao Y, de Klerk A. Nitrogen removal from oil: a review[J]. Energy & Fuels, 2017, 31(1): 14-36.
8	Bachrach M, Marks T J, Notestein J M. Understanding the hydrodenitrogenation of heteroaromatics on a molecular level[J]. ACS Catalysis, 2016, 6(3): 1455-1476.
9	Gutiérrez O Y, Singh S, Schachtl E, et al. Effects of the support on the performance and promotion of (Ni)MoS₂ catalysts for simultaneous hydrodenitrogenation and hydrodesulfurization[J]. ACS Catalysis, 2014, 4(5): 1487-1499.
10	Guo K, Ding Y, Yu Z X. One-step synthesis of ultrafine MoNiS and MoCoS monolayers as high-performance catalysts for hydrodesulfurization and hydrodenitrogenation[J]. Applied Catalysis B: Environmental, 2018, 239: 433-440.
11	Albersberger S, Shi H, Wagenhofer M, et al. On the enhanced catalytic activity of acid-treated, trimetallic Ni-Mo-W sulfides for quinoline hydrodenitrogenation[J]. Journal of Catalysis, 2019, 380: 332-342.
12	Pereyma V Y, Klimov O V, Prosvirin I P, 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.
13	Dorneles de Mello M, de Almeida-Braggio F, da Costa-Magalhães B, et al. Effects of phosphorus content on simultaneous ultradeep HDS and HDN reactions over NiMoP/Alumina catalysts[J]. Industrial & Engineering Chemistry Research, 2017, 56: 10287-10299.
14	Tong R L, Wang Y G, Zhang X, et al. Effect of phosphorus modification on the catalytic properties of NiW/γ-Al₂O₃ in the hydrogenation of aromatics from coal tar[J]. Journal of Fuel Chemistry and Technology, 2015, 43(12): 1461-1469.
15	Tao X J, Zhou Y S, Wei Q, et al. Inhibiting effects of nitrogen compounds on deep hydrodesulfurization of straight-run gas oil over a NiW/Al₂O₃ catalyst[J]. Fuel, 2017, 188: 401-407.
16	王倩, 龙湘云, 聂红. 氮化物对NiW/Al₂O₃上DBT和4, 6-DMDBT加氢脱硫反应活性的影响[J]. 石油炼制与化工, 2011, 42(4): 30-34.
	Wang Q, Long X Y, Nie H. Effect of nitrogen compounds on the hydrodesulfurization of dibenzothiophene and 4, 6-dimethyldibenzothiophene over alumina-supported NiW catalyst[J]. Petroleum Processing and Petrochemicals, 2011, 42(4): 30-34.
17	Zhang H, Li G, Jia Y H, et al. Adsorptive removal of nitrogen-containing compounds from fuel[J]. Journal of Chemical & Engineering Data, 2010, 55(1): 173-177.
18	Xiang C E, Chai Y M, Fan J, et al. Effect of phosphorus on the hydrodesulfurization and hydrodenitrogenation performance of presulfided NiMo/Al₂O₃ catalyst[J]. Journal of Fuel Chemistry and Technology, 2011, 39(5): 355-360.
19	Reinhoudt H R, Troost R, van Langeveld A D, et al. The nature of the active phase in sulfided NiW/γ-Al₂O₃ in relation to its catalytic performance in hydrodesulfurization reactions[J]. Journal of Catalysis, 2001, 203(2): 509-515.
20	Yu G L, Zhou Y S, Wei Q, et al. A novel method for preparing well dispersed and highly sulfided NiW hydrodenitrogenation catalyst[J]. Catalysis Communications, 2012, 23: 48-53.
21	Wang H, Fan Y, Shi G, et al. Highly dispersed NiW/γ-Al₂O₃ catalyst prepared by hydrothermal deposition method[J]. Catalysis Today, 2007, 125(3/4): 149-154.
22	Fang M X, Ma S, Wang T, et al. Hydrotreatment of model compounds with catalysts of NiW/Al₂O₃ and NiWP/Al₂O₃ to simulate low temperature coal tar oil[J]. RSC Advances, 2017, 7(86): 54512-54521.
23	罗怡, 周亚松, 魏强, 等. 磷、柠檬酸改性对MoW/Ni/Al₂O₃催化剂性质及加氢脱氮性能的影响[J]. 化工学报, 2014, 65(10): 3916-3923.
	Luo Y, Zhou Y S, Wei Q, et al. Effect of citric acid and phosphorus on properties and hydrodenitrogenation performance of MoW/Ni/Al₂O₃ catalysts[J]. CIESC Journal, 2014, 65(10): 3916-3923.
24	Ding S J, Jiang S J, Zhou Y S, et al. Oxygen effects on the structure and hydrogenation activity of the MoS₂ active site: a mechanism study by DFT calculation[J]. Fuel, 2017, 194: 63-74.
25	López-Benítez A, Guevara-Lara A, Berhault G. Nickel-containing polyoxotungstates based on [PW₉O₃₄]^9- and [PW₁₀O₃₉]^13- keggin lacunary anions supported on Al₂O₃ for dibenzothiophene hydrodesulfurization application[J]. ACS Catalysis, 2019, 9(8): 6711-6727.
26	Wei Z Z, Chen Y Q, Wang J, et al. Cobalt encapsulated in N-doped graphene layers: an efficient and stable catalyst for hydrogenation of quinoline compounds[J]. ACS Catalysis, 2016, 6(9): 5816-5822.
27	徐永强, 董晓芳, 赵会吉, 等. 二苯并噻吩在γ-Al₂O₃上分散状态及吸附状态的研究[J]. 石油学报(石油加工), 2003, (1): 12-16.
	Xu Y Q, Dong X F, Zhao H J, et al. Studies on dispersion and adsorption states of dibenzothiophene on γ-Al₂O₃[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2003, (1): 12-16.
28	Braggio F A, Mello M D, Magalhaes B C, et al. Effects of citric acid addition method on the activity of NiMo/γ-Al₂O₃ catalysts in simultaneous hydrodesulfurization and hydrodenitrogenation reactions[J]. Energy & Fuels, 2019, 33(2): 1450-1457.

[1]	杨欣, 王文, 徐凯, 马凡华. 高压氢气加注过程中温度特征仿真分析[J]. 化工学报, 2023, 74(S1): 280-286.
[2]	晁京伟, 许嘉兴, 李廷贤. 基于无管束蒸发换热强化策略的吸附热池的供热性能研究[J]. 化工学报, 2023, 74(S1): 302-310.
[3]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[4]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[5]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[6]	曹跃, 余冲, 李智, 杨明磊. 工业数据驱动的加氢裂化装置多工况切换过渡状态检测[J]. 化工学报, 2023, 74(9): 3841-3854.
[7]	杨绍旗, 赵淑蘅, 陈伦刚, 王晨光, 胡建军, 周清, 马隆龙. Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃[J]. 化工学报, 2023, 74(9): 3697-3707.
[8]	盛冰纯, 于建国, 林森. 铝基锂吸附剂分离高钠型地下卤水锂资源过程研究[J]. 化工学报, 2023, 74(8): 3375-3385.
[9]	张瑞航, 曹潘, 杨锋, 李昆, 肖朋, 邓春, 刘蓓, 孙长宇, 陈光进. ZIF-8纳米流体天然气乙烷回收工艺的产品纯度关键影响因素分析[J]. 化工学报, 2023, 74(8): 3386-3393.
[10]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[11]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[12]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[13]	高燕, 伍鹏, 尚超, 胡泽君, 陈晓东. 基于双流体喷嘴的磁性琼脂糖微球的制备及其蛋白吸附性能探究[J]. 化工学报, 2023, 74(8): 3457-3471.
[14]	陈吉, 洪泽, 雷昭, 凌强, 赵志刚, 彭陈辉, 崔平. 基于分子动力学的焦炭溶损反应及其机理研究[J]. 化工学报, 2023, 74(7): 2935-2946.
[15]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.

硫氮化合物在磷改性NiW/Al₂O₃加氢催化剂上的吸附行为研究

Research on adsorption behavior of sulfur and nitrogen compounds on P modified NiW/Al₂O₃ catalyst

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 14

参考文献 28

相关文章 15

编辑推荐

Metrics

本文评价