Si改性对NiMo/Al2O3催化剂加氢脱硫性能的影响

doi:10.16085/j.issn.1000-6613.2022-0241

摘要/Abstract

摘要：

以中和法合成的不同SiO₂含量的改性氧化铝为载体，本文制备系列Si改性的NiMo/Al₂O₃催化剂，采用X射线衍射（XRD）、N₂物理吸附（BET）、程序升温脱附（NH₃-TPD）、吡啶吸附红外光谱（Py-IR）、程序升温还原（H₂-TPR）、高分辨透射电镜（HRTEM）和X射线光电子能谱（XPS）等分析手段进行详细表征。表征结果显示，引入Si减弱了活性金属与载体之间的相互作用，改善了催化剂的孔结构与表面酸性分布，提高了活性相分散度和金属硫化度，促使形成更多的II类NiMoS活性相。以二苯并噻吩（DBT）为模型化合物，在固定床加氢装置上考察了系列催化剂的加氢脱硫（HDS）性能，结果表明，引入Si可降低DBT的加氢反应活化能，提高反应速率常数，进而提高催化剂的加氢脱硫活性。对比DBT转化率在50%时的脱硫产物分布表明引入Si可影响催化剂的反应路径选择性，直接脱硫路径（DDS）选择性从83.69%增加至92.89%，证实了催化剂的表征规律。

关键词: 催化剂, 二氧化硅, NiMo/Al₂O₃, 二苯并噻吩, 加氢脱硫

Abstract:

A series of modified alumina supports with different SiO₂ contents were prepared by neutralization method. NiMo/Al₂O₃ catalysts were obtained by impregnating the modified Al₂O₃ into nickel-molybdenum precursor solution. The catalysts were characterized by XRD, BET, NH₃-TPD, Py-IR, H₂-TPR, HRTEM and XPS. The results showed that the introduction of silicon weakened the metal-support interaction, changed the porous structure and surface acidity of the catalysts. It also improved the active phase dispersion and metal sulfidation, thereby promoted the formation of more Type II NiMoS active phases. With DBT as a model compound, the hydrodesulfurization (HDS) performance of the catalysts were evaluated on a fixed-bed reactor. The reaction activity evaluation results indicated that the introduction of silicon reduced the reaction activation energy of DBT and increased the reaction rate constant, resulting in the increase of the hydrodesulfurization catalysis activity. The comparison of the desulfurization products distribution at DBT conversion of 50% showed that the introduction of silicon significantly affected the reaction selectivity, and the DDS selectivity increased from 83.69% to 92.89%. The characterization conclusions of the catalysts were confirmed by the evaluation results.

Key words: catalyst, silica, NiMo/Al₂O₃, DBT, HDS

中图分类号:

O643.36

郭振雪, 于海斌, 张国辉, 张景成, 卢雁飞, 何艳贞, 孙彦民, 韩恩山. Si改性对NiMo/Al₂O₃催化剂加氢脱硫性能的影响[J]. 化工进展, 2022, 41(S1): 210-220.

GUO Zhenxue, YU Haibin, ZHANG Guohui, ZHANG Jingcheng, LU Yanfei, HE Yanzhen, SUN Yanmin, HAN Enshan. Effect of silica modification on the performance of NiMo/Al₂O₃ catalyst in hydrodesulfurization[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 210-220.

图/表 17

参考文献 31

1	WANG H Y, LIU S D, SMITH K J. Understanding selectivity changes during hydrodesulfurization of dibenzothiophene on Mo₂C/carbon catalysts[J]. Journal of Catalysis, 2019, 369: 427-439.
2	ZHOU W W, WEI Q, ZHOU Y S, et al. Hydrodesulfurization of 4,6-dimethyldibenzothiophene over NiMo sulfide catalysts supported on meso-microporous Y zeolite with different mesopore sizes[J]. Applied Catalysis B: Environmental, 2018, 238: 212-224.
3	ZHOU W W, ZHOU A N, ZHANG Y T, et al. Hydrodesulfurization of 4,6-dimethyldibenzothiophene over NiMo supported on Ga-modified Y zeolites catalysts[J]. Journal of Catalysis, 2019, 374: 345-359.
4	WANG X L, MEI J L, ZHAO Z, et al. Restrictive diffusion in the hydrodesulfurization over Ni-MoS₂/Al₂O₃ with different crystal forms[J]. Industrial & Engineering Chemistry Research, 2017, 56(36): 10018-10027.
5	GRØNBORG S S, ŠARIĆ M, MOSES P G, et al. Atomic scale analysis of sterical effects in the adsorption of 4,6-dimethyldibenzothiophene on a CoMoS hydrotreating catalyst[J]. Journal of Catalysis, 2016, 344: 121-128.
6	JAF Z N, ALTARAWNEH M, MIRAN H A, et al. Hydrodesulfurization of thiophene over γ-Mo₂N catalyst[J]. Molecular Catalysis, 2018, 459: 21-30.
7	TOPSØE H, CLAUSEN B S, CANDIA R, et al. In situ Mössbauer emission spectroscopy studies of unsupported and supported sulfided CoMo hydrodesulfurization catalysts: evidence for and nature of a CoMoS phase[J]. Journal of Catalysis, 1981, 68(2): 433-452.
8	YU Q, ZHANG J C, NAN J, et al. Synthesis and hydrodesulfurization performance of NiMo sulfide catalysts supported on an Al-Si mixed oxide[C]//Preceedings of the 2016 International Conference on Civil, Architecture and Environmental Engineering. Taibei, China, 2017: 404-407.
9	RAYO P, TORRES-MANCERA P, CENTENO G, et al. Effect of silicon incorporation method in the supports of NiMo catalysts for hydrotreating reactions[J]. Fuel, 2019, 239: 1293-1303.
10	ROMERO-GALARZA A, RAMíREZ J, GUTIÉRREZ-ALEJANDRE A, et al. Relevant changes in the properties of Co(Ni)Mo/Al₂O₃ HDS catalysts modified by small amounts of SiO₂ [J]. Journal of Materials Research, 2018, 33(21): 3570-3579.
11	ABOUTALEB W A, NAGGER A M A EL, SAYED M A, et al. Influence of CeO₂ loading on the catalytic performance of CoNiMoS/CeO₂-Al₂O₃ toward vacuum gas oil hydrotreatment[J]. Materials Chemistry and Physics, 2022, 276: 125165.
12	WANG S, ZHANG J C, LIU D, et al. Deep insights into enhanced direct-desulfurization selectivity of thiourea-modified CoMoP/ γ-Al₂O₃: an investigation of catalyst microstructures[J]. Fuel, 2020, 267: 116993.
13	张国辉, 张玉婷, 张景成, 等. 制备方法对Ni-Mo/Al₂O₃加氢催化剂性能的影响[J]. 化工进展, 2018, 37(11): 4315-4321.
	ZHANG Guohui, ZHANG Yuting, ZHANG Jingcheng, et al. Influence of preparation method on hydrotreating activity of Ni-Mo/Al₂O₃ [J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4315-4321.
14	汪佩华, 秦志峰, 吴琼笑, 等. 磷添加方式对NiMo/Al₂O₃催化剂加氢脱硫性能的影响[J]. 化工进展, 2021, 40(2): 890-900.
	WANG Peihua, QIN Zhifeng, WU Qiongxiao, et al. Effect of phosphorus adding manners on the performance of NiMo/Al₂O₃catalyst in hydrodesulfurization[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 890-900.
15	ŠARIĆ M, ROSSMEISL J, MOSES P G. Modeling the adsorption of sulfur containing molecules and their hydrodesulfurization intermediates on the Co-promoted MoS₂ catalyst by DFT[J]. Journal of Catalysis, 2018, 358: 131-140.
16	CAO Z K, ZHANG X, GUO R, et al. Synergistic effect of acidity and active phases for NiMo catalysts on dibenzothiophene hydrodesulfurization performance[J]. Chemical Engineering Journal, 2020, 400: 125886.
17	LIU B, LIU L, WANG Z, et al. Effect of hydrogen spillover in selective hydrodesulfurization of FCC gasoline over the CoMo catalyst[J]. Catalysis Today, 2017, 282: 214-221.
18	HENKER M, WENDLANDT K P, VALYON J, et al. Structure of MoO₃/Al₂O₃-SiO₂ catalysts[J]. Applied Catalysis, 1991, 69(1): 205-220.
19	ARNOLDY P, JONGE J D, MOULIJN J. Temperature-programed reduction of molybdenum (Ⅵ) oxide and molybdenum (Ⅳ) oxide[J]. The Journal of Physical Chemistry, 1985, 89(21): 4517-4526.
20	岳凡, 李蒙, 杨祝红, 等. 介孔TiO₂晶须-γ-Al₂O₃复合载体催化剂的制备及对二苯并噻吩的加氢脱硫性能[J]. 石油学报(石油加工), 2020, 36(4): 667-676.
	YUE Fan, LI Meng, YANG Zhuhong, et al. Preparation of mesoporous TiO₂ whisker-γ-Al₂O₃ composite supported catalyst and its catalytic performance in dibenzothiophene hydrodesulfurization[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2020, 36(4): 667-676.
21	RAJAGOPAL S, MARINI H, MARZARI J, et al. Silica-alumina-supported acidic molybdenum catalysts-TPR and XRD characterization[J]. Journal of Catalysis, 1994, 147(2): 417-428.
22	XU J, HUANG T, FAN Y. Highly efficient NiMo/SiO₂-Al₂O₃ hydrodesulfurization catalyst prepared from gemini surfactant-dispersed Mo precursor[J]. Applied Catalysis B: Environmental, 2017, 203: 839-850.
23	HAO L, XIONG G, LIU L P, 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.
24	GLOTOV A P, VUTOLKINA A V, VINOGRADOV N A, et al. Enhanced HDS and HYD activity of sulfide Co-PMo catalyst supported on alumina and structured mesoporous silica composite[J]. Catalysis Today, 2021, 377: 82-91.
25	HARRIS S, CHINANELLI R R. Catalysis by transition metal sulfides: the relation between calculated electronic trends and HDS activity[J]. Journal of Catalysis, 1984, 86(2): 400-412.
26	SÁNCHEZ-MINERO F, RAMÍIREZ J, NCHEZ-MINERO F, et al. Analysis of the HDS of 4,6-DMDBT in the presence of naphthalene and carbazole over NiMo/Al₂O₃-SiO₂(x) catalysts[J]. Catalysis Today, 2008, 133: 267-276.
27	PRINS R, EGOROVA M, RÖTHLISBERGER A, et al. Mechanisms of hydrodesulfurization and hydrodenitrogenation[J]. Catalysis Today, 2006, 111(1-2): 84-93.
28	赵瑞玉, 曹东炜, 曾令有, 等. 助剂Ni与载体的相互作用及其对NiMo/γ-Al₂O₃催化剂加氢脱硫性能的影响[J]. 燃料化学学报, 2016, 44(5): 564-569.
	ZHAO Ruiyu, CAO Dongwei, ZENG Lingyou, et al. Interaction between Ni promoter and Al₂O₃support and its effect on the performance of NiMo/γ-Al₂O₃ catalyst in hydrodesulphurization[J]. Journal of Fuel Chemistry and Technology, 2016, 44(5): 564-569.
29	LÓPEZ-BENÍTEZ A, BERHAULT G, GUEVARA-LARA.A. Addition of manganese to alumina and its influence on the formation of supported NiMo catalysts for dibenzothiophene hydrodesulfurization application[J]. Journal of Catalysis, 2016, 344: 59-76.
30	LEBEAU B, BONNE M, COMPAROT J D, et al. HDS of 4,6-dimethyldibenzothiophene over CoMoS supported mesoporous SiO₂-TiO₂ materials[J]. Catalysis Today, 2020: 675-683.
31	李翔, 王安杰, 柳广厦, 等. 芳香杂环含硫化合物C—S键断裂方式[J]. 石油学报(石油加工), 2017, 33(6): 1039-1052.
	LI Xiang, WANG Anjie, LIU Guangxia, et al. Mechanisms of the cleavage of C—S Bonds in polyaromatic sulfur-containing compounds[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2017, 33(6): 1039-1052.

催化剂	比表面积 /m²·g^-1	孔体积 /cm³·g^-1	孔径比例/%
催化剂	比表面积 /m²·g^-1	孔体积 /cm³·g^-1	<4nm	4~10nm	>10nm
NiMo/Al-0Si	225	0.51	8.6	73.8	17.6
NiMo/Al-2Si	228	0.53	6.4	75.9	17.7
NiMo/Al-4Si	241	0.54	5.5	76.5	18.0
NiMo/Al-6Si	255	0.58	4.4	77.3	18.3
NiMo/Al-8Si	256	0.59	2.8	78.4	18.8

催化剂	比表面积 /m²·g^-1	孔体积 /cm³·g^-1	孔径比例/%
催化剂	比表面积 /m²·g^-1	孔体积 /cm³·g^-1	<4nm	4~10nm	>10nm
NiMo/Al-0Si	225	0.51	8.6	73.8	17.6
NiMo/Al-2Si	228	0.53	6.4	75.9	17.7
NiMo/Al-4Si	241	0.54	5.5	76.5	18.0
NiMo/Al-6Si	255	0.58	4.4	77.3	18.3
NiMo/Al-8Si	256	0.59	2.8	78.4	18.8

催化剂	B酸量 /mmol·g^-1	L酸量 /mmol·g^-1	总酸量 /mmol·g^-1	B/L
NiMoS/Al-0Si	—	0.102	0.102	—
NiMoS/Al-2Si	0.012	0.113	0.125	0.106
NiMoS/Al-4Si	0.015	0.120	0.135	0.125
NiMoS/Al-6Si	0.018	0.130	0.148	0.138
NiMoS/Al-8Si	0.020	0.133	0.153	0.150

催化剂	B酸量 /mmol·g^-1	L酸量 /mmol·g^-1	总酸量 /mmol·g^-1	B/L
NiMoS/Al-0Si	—	0.102	0.102	—
NiMoS/Al-2Si	0.012	0.113	0.125	0.106
NiMoS/Al-4Si	0.015	0.120	0.135	0.125
NiMoS/Al-6Si	0.018	0.130	0.148	0.138
NiMoS/Al-8Si	0.020	0.133	0.153	0.150

催化剂	平均长度/nm	平均堆垛层数	f_Mo
NiMoS/Al-0Si	3.91	2.81	0.30
NiMoS/Al-2Si	3.84	3.15	0.33
NiMoS/Al-4Si	3.73	3.18	0.34
NiMoS/Al-6Si	3.51	3.23	0.38
NiMoS/Al-8Si	3.67	3.33	0.35

Si改性对NiMo/Al₂O₃催化剂加氢脱硫性能的影响

Effect of silica modification on the performance of NiMo/Al₂O₃ catalyst in hydrodesulfurization

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参考文献 31

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催化剂	Mo⁴⁺/%	Mo⁵⁺/%	Mo⁶⁺/%	NiS _x /%	NiMoS/%	NiO/%
NiMoS/Al-0Si	47.13	15.44	37.43	21.70	38.30	40.00
NiMoS/Al-2Si	51.02	15.28	33.70	16.94	39.31	43.75
NiMoS/Al-4Si	54.41	8.77	36.82	19.72	47.02	33.26
NiMoS/Al-6Si	55.43	13.57	31.00	16.94	48.97	34.09
NiMoS/Al-8Si	53.46	10.98	35.56	24.87	45.80	29.33

催化剂	E_a /kJ·mol^-1	E_aDDS /kJ·mol^-1	E_aHYD /kJ·mol^-1	K_HDS /10^-4mol·g^-1·h^-1
NiMo/Al-0Si	105.5	96.4	106.9	3.37
NiMo/Al-2Si	98.5	92.5	102.2	3.80
NiMo/Al-4Si	93.0	90.7	97.8	4.21
NiMo/Al-6Si	91.4	88.8	93.7	5.25
NiMo/Al-8Si	92.4	86.7	98.3	4.67

催化剂	DDS（BP^①）/%	HYD/%				转化率（DBT）/%
催化剂	DDS（BP^①）/%	THDBT^②	HHDBT^③	CHB^④	DCH^⑤	转化率（DBT）/%
NiMo/Al-0Si	83.69	0.33	13.13	0.52	2.33	49.59
NiMo/Al-2Si	89.35	0.14	7.94	0.42	2.15	49.63
NiMo/Al-4Si	91.20	0.13	6.46	0.27	1.94	50.25
NiMo/Al-6Si	92.07	0.20	5.74	0.09	1.90	50.00
NiMo/Al-8Si	92.89	0.13	4.75	0.28	1.95	49.70

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