Ni对MoS<sub>2</sub>基催化剂活性相及加氢脱氮脱硫性能的影响

刘娟; 李文英; 冯杰; 高翔

doi:10.1016/S1872-5813(21)60105-6

Ni对MoS₂基催化剂活性相及加氢脱氮脱硫性能的影响

doi: 10.1016/S1872-5813(21)60105-6

刘娟^{1, 2,},
李文英^1, ,,
冯杰¹,
高翔²

1.
太原理工大学省部共建煤基清洁能源利用国家重点实验室，山西太原 030024
2.
浙江大学能源清洁利用国家重点实验室，浙江杭州 310027

基金项目: 国家自然科学基金（22038008）和国家重点研发计划重点专项（2016YFB0600305）资助

详细信息

作者简介:
刘娟：liujuan7078@link.tyut.edu.cn

通讯作者:
Tel：86-0351-6018453，E-mail：ying@tyut.edu.cn

中图分类号: TQ426
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- 文章访问数: 269
- HTML全文浏览量: 76
- PDF下载量: 41
- 被引次数: 0
出版历程
- 收稿日期: 2021-02-23
- 修回日期: 2021-04-30
- 网络出版日期: 2021-06-03
- 刊出日期: 2021-10-30

Influence of Ni on the active phase and hydrodenitrogenation and hydrodesulfurization activities of MoS₂ catalysts

LIU Juan^{1, 2
,},
LI Wen-ying^{1
, ,},
FENG Jie¹,
GAO Xiang²

1.
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China
2.
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China

Funds: The project was supported by National Natural Science Foundation of China (22038008) and National Key Research and Development Plan Projects of China (2016YFB0600305)

摘要

摘要: 为了获得较多高活性II型MoS₂活性相，采用四硫代钼酸铵原位热分解法制备了MoS₂基催化剂，对比分析了Ni源引入方式和热分解气氛对MoS₂活性相微观结构、表面元素化学状态和加氢脱氮脱硫性能等的影响。结果表明，同时引入Mo源和Ni源原位沉淀生成无定形NiMoS₄后，再热分解有利于Ni取代MoS₂片晶边缘的Mo原子，被修饰后的MoS₂片晶保持较高的分散度、适宜的长度（3−5 nm）和堆叠层数（2−4层），从而在边缘暴露较多具有加氢和氢解活性的rim和corner活性位点。热分解气氛H₂比N₂更有利于Ni在热分解过程中取代MoS₂边缘的Mo原子，形成更多II型Ni-Mo-S活性结构，有利于喹啉和二苯并噻吩的吸附活化和加氢反应。当加氢反应温度340 ℃、氢压3 MPa、重时空速23.4 h⁻¹、氢油比为600和使用0.1 g NMS-H₂催化剂时，喹啉加氢脱氮转化率达23.8%，二苯并噻吩加氢脱硫转化率达93.3%。
- NiMo硫化物 /
- 喹啉 /
- 二苯并噻吩 /
- 加氢反应
Abstract: To obtain type II active phase with higher activity, MoS₂-based catalysts were prepared by thermal decomposition of ammonium tetrathiomolybdate. The influence of Ni adding way and decomposition atmosphere on the microstructures of MoS₂ slabs, chemical state of surface elements, as well as hydrodesulfurization and hydrodenitrogenation activities were investigated. Results indicated that simultaneous impregnation of Mo and Ni precursors caused in situ deposition of amorphous NiMoS₄ over the support surface, which subsequently facilitated the substitution of Mo atoms by Ni atoms at MoS₂ edges. Accordingly, these decorated catalysts exhibited higher dispersion of MoS₂ slabs with more suitable slab length (3–5 nm) and stacking number (2–4), which attributed to larger numbers of rim and corner active sites exposed at the edges. These active sites were essential in hydrogenation and hydrogenolysis reactions. In comparison with N₂ atmosphere, thermal decomposition in H₂ atmosphere was more conducive to the substitution of Mo atoms by Ni atoms at MoS₂ edges, which provided more active Ni-Mo-S structures for the adsorption, activation and hydrogenolysis of quinoline and dibenzothiophene molecules. The catalyst prepared by thermal decomposition of NiMoS₄ in H₂ atmosphere showed superior activities in the quinoline hydrodenitrogenation with 23.8% conversion and in the dibenzothiophene hydrodesulfurization with 93.3% conversion, under the conditions of 340 °C, 3 MPa, a weight hourly space velocity of 23.4 h^–1, H₂/oil volume ratio of 600 and 0.1 g of NMS-H₂ catalysts.
- NiMo sulfide /
- quinoline /
- dibenzothiophene /
- hydrogenation reaction

HTML全文

FIG. 970. FIG. 970.

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图 1 两种MoS₂活性相结构示意图

Figure 1 Schematic of two types of MoS₂ structure

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图 2 载体和催化剂的XRD谱图

Figure 2 XRD patterns of support and catalysts

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图 3 催化剂NMS-N₂（a）、NMS-H₂（b）和NMS-T-N₂（c）表面MoS₂的HRTEM照片

Figure 3 HRTEM images of MoS₂ over NMS-N₂ (a), NMS-H₂ (b) and NMS-T-N₂ (c) catalysts

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图 4 硫化物催化剂表面MoS₂片晶长度（a）和堆叠层数（b）的统计分析

Figure 4 Histograms of slab length (a) and stack number (b) of MoS₂ over the sulfide catalyst

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图 5 硫化物催化剂的H₂-TPR谱图

Figure 5 H₂-TPR profiles of the sulfide catalysts

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图 6 载体和催化剂的NH₃-TPD谱图

Figure 6 NH₃-TPD profiles of the support and sulfide catalysts

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图 7 Mo 3d(a)和Ni 2p(b)的XPS谱图

Figure 7 XPS spectra of Mo 3d (a) and Ni 2p (b)

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表 1 样品的物理结构性质

Table 1 Physical structure properties of sample

Sample	Specific surface area/(m²·g⁻¹)	Total pore volume/(cm³·g⁻¹)	Most probable pore size/nm
γ-Al₂O₃	288	1.03	14.3
NMS-N₂	204	0.57	11.3
NMS-H₂	206	0.60	11.7
NMS-T-N₂	198	0.62	12.6

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表 2 MoS₂片晶平均长度L_A、平均堆叠层数N_A、分散度f_Mo和不同活性位点的比例

Table 2 Average length L_A, stack number N_A, Mo atoms dispersion and fraction of different active sites

Catalyst	L_A/nm	N_A	f_Mo	R	f_e	f_r	f_c
NMS-N₂	3.9	4.2	0.28	1.09	0.248	0.228	0.059
NMS-H₂	3.7	3.4	0.29	0.58	0.257	0.443	0.073
NMS-T-N₂	4.9	6.6	0.23	1.33	0.213	0.160	0.038

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表 3 Mo 3d和Ni 2p信号的分峰拟合

Table 3 Deconvolution results of Mo 3d and Ni 2p signals

Sample	Mo_sulf/ %	Mo distribution/ %			Ni_sulf/ %	Ni distribution/ %
Sample	Mo_sulf/ %	Mo⁴⁺	Mo⁵⁺	Mo⁶⁺	Ni_sulf/ %	NiS_x	NiMoS	Ni²⁺
NMS-N₂	40	40	13	47	71	15	56	29
NMS-H₂	47	47	14	39	87	16	71	13
NMS-T-N₂	39	39	17	44	66	11	55	34

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表 4 不同催化剂的喹啉HDN性能和选择性

Table 4 Quinoline HDN activity and selectivity over different catalysts

Catalyst	x_HDN/%	Product selectivity/%							Route ratio
Catalyst	x_HDN/%	PCH	PCHE	PB	DHQ	58THQ	OPA	14THQ	(PCH + PCHE)/PB
NMS-N₂	12.8	9.7	1.4	3.8	9.6	25.7	3.5	46.2	2.92
NMS-H₂	23.8	17.8	2.2	6.5	10.3	24.9	4.7	33.4	3.07
NMS-T-N₂	8.6	6.3	1.3	2.9	8.2	20.4	3.3	57.5	2.62

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表 5 不同催化剂的二苯并噻吩HDS性能和选择性

Table 5 Dibenzothiophene HDS activity and selectivity over different catalyst

Catalyst	x_HDS/%	Product selectivity/%			Route ratio
Catalyst	x_HDS/%	BP	CHB	BCH	BP/(CHB + BCH)
NMS-N₂	91.6	74.8	24.0	1.2	2.96
NMS-H₂	93.3	65.3	30.8	3.9	1.88
NMS-T-N₂	81.9	80.5	19.1	0.4	4.12

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