Design of molybdenum sulfide-based catalyst and its application in hydrodesulfurization reaction

doi:10.16085/j.issn.1000-6613.2024-2030

Abstract

Abstract:

Molybdenum sulfide-based (MoS₂) catalysts play a critical role in hydrodesulfurization (HDS) reactions, particularly as environmental regulations become increasingly stringent. The growing demand for ultra-low sulfur fuels and the tightening of vehicle emission standards have made the development of efficient HDS catalysts a key challenge in the petroleum refining industry. MoS₂ catalysts are particularly notable for their excellent catalytic activity, high resistance to poisoning, and cost-effectiveness. This paper provides an overview of the design principles, reaction mechanisms, and applications of MoS₂ catalysts in HDS, along with the strategies to optimize their performance. First, we analyze the active sites of MoS₂ and explore the reaction mechanisms involved in HDS. We then review the current state of MoS₂ catalysts in HDS and discuss future directions, particularly the development of unsupported catalysts and their applications in HDS. Finally, we address the challenges and opportunities in identifying catalyst active sites, studying reaction mechanisms, and increasing catalyst life and cost efficiency. The paper also emphasizes the importance of in-situ characterization close to industrial reaction conditions.

Key words: hydrodesulfurization (HDS), molybdenum disulfide (MoS₂), active phase, catalyst design, promoting mechanism, high pressure in-situ characterization

摘要：

硫化钼（MoS₂）基催化剂在加氢脱硫（HDS）反应中具有重要的应用价值，特别是在满足日益严格的环境法规要求方面。随着环境立法的趋严，尤其是在汽车排放标准的提升和超低硫燃料需求增长的背景下，开发高效的HDS催化剂成为石油精炼行业面临的关键挑战。MoS₂基催化剂因其出色的催化性能、较高的抗毒性和较低的成本，成为研究的热点。本文综述了MoS₂催化剂的设计理念、反应机制及其在HDS反应中的应用，并探讨了催化剂性能优化的策略，分析了MoS₂的活性位点及其在HDS反应中的反应机制。讨论了MoS₂基催化剂在HDS反应中的应用现状及未来发展方向，其中重点介绍了非负载型催化剂的开发及其在HDS反应中的应用。最后，指出了催化剂活性位点的识别、反应机理的研究、催化剂寿命延长和成本降低的挑战与机遇，强调了开发接近工业反应条件下的原位表征的必要性。

关键词: 加氢脱硫, 硫化钼, 活性相, 催化剂设计, 促进机理, 高压原位表征

CLC Number:

TQ426

GUO Luyao, YAN Siyang, WANG Manyu, YANG Ping, HE Wenhui, LIU Jiaxu. Design of molybdenum sulfide-based catalyst and its application in hydrodesulfurization reaction[J]. Chemical Industry and Engineering Progress, 2025, 44(12): 6920-6943.

郭璐瑶, 闫思杨, 王曼玉, 杨平, 何文会, 刘家旭. 硫化钼基催化剂的设计及其在加氢脱硫反应中的应用[J]. 化工进展, 2025, 44(12): 6920-6943.

Figures/Tables 20

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噻吩环类取代物	电子云密度	假一级反应速率常数/L·g^-1·s^-1
噻吩	5.700	1.38×10^-3
苯并噻吩	5.739	8.11×10^-4
二苯并噻吩	5.758	7.38×10^-5
4-甲基二苯并噻吩	5.759	6.64×10^-6
4,6-二甲基二苯并噻吩	5.760	4.92×10^-6

噻吩环类取代物	电子云密度	假一级反应速率常数/L·g^-1·s^-1
噻吩	5.700	1.38×10^-3
苯并噻吩	5.739	8.11×10^-4
二苯并噻吩	5.758	7.38×10^-5
4-甲基二苯并噻吩	5.759	6.64×10^-6
4,6-二甲基二苯并噻吩	5.760	4.92×10^-6

催化剂	温度/℃	催化剂质量/g	原料	反应速率/10^-6mol·g^-1·s^-1	HYD速率/DDS速率	转化频率/h^-1	参考文献
NiMo/δ-MA	340	0.5	500mg/kg S，4,6-二甲基二苯并噻吩	0.72	3.08	9.5	[46]
NiMo/Al₂O₃-600	340	1	500mg/kg S，4,6-二甲基二苯并噻吩	0.05	0.40	0.01	[47]
NiMo@(1)Ga-A-Al₂O₃	290	0.15	质量分数1.68%二苯并噻吩	0.3	0.65	0.87	[48]
NiMo-80A20Z	300	0.1	摩尔分数8.2%噻吩/H₂	9.5	—	—	[53]
NiMo/Al₂O₃-A	350	0.3	体积分数5.0%二苯并噻吩	3.77	0.26	—	[54]
NiMo/MA-20Ti	320	1	质量分数1.0% 4,6-二甲基二苯并噻吩	0.27	8.96	3.9	[55]
NiMo/1-ZAT	320	2	质量分数1.0%二苯并噻吩	0.38	0.62	6.12	[56]
NiMo/TF-35	360	—	500mg/kg S，二苯并噻吩	0.16	0.58	1.64	[57]
NiMo/HMY-6	290	1	质量分数0.5% 4,6-二甲基二苯并噻吩	0.22	0.58	3.50	[58]
NiMo/TD-Mg(2)	340	1	500mg/kg S，二苯并噻吩	0.34	—	3.40	[59]
NiMo/TD-Mg(2)	340	1	500mg/kg S, 4,6-二甲基二苯并噻吩	0.29	—	2.80	[59]
NiMoO _x /Hol-ZSM-5	330	0.05	500mg/kg S，二苯并噻吩	1.87	0.03	—	[60]
1Ge-NiMoS/Al₂O₃	290	1	质量分数0.5% 4,6-二甲基二苯并噻吩	0.608	2.87	3.27	[61]
NiMoS _x /ZSM-5-100	360	—	500mg/kg S，二苯并噻吩	1.41	0.05	10.69	[62]
NiMoS _x /ZSM-5-100	360	—	250mg/kg S，4,6-二甲基二苯并噻吩	0.27	—	—	[62]
5Mo@NC	320	0.4	质量分数1.0%二苯并噻吩	0.04	0.14	1.8	[63]

催化剂	温度/℃	催化剂质量/g	原料	反应速率/10^-6mol·g^-1·s^-1	HYD速率/DDS速率	转化频率/h^-1	参考文献
NiMo/δ-MA	340	0.5	500mg/kg S，4,6-二甲基二苯并噻吩	0.72	3.08	9.5	[46]
NiMo/Al₂O₃-600	340	1	500mg/kg S，4,6-二甲基二苯并噻吩	0.05	0.40	0.01	[47]
NiMo@(1)Ga-A-Al₂O₃	290	0.15	质量分数1.68%二苯并噻吩	0.3	0.65	0.87	[48]
NiMo-80A20Z	300	0.1	摩尔分数8.2%噻吩/H₂	9.5	—	—	[53]
NiMo/Al₂O₃-A	350	0.3	体积分数5.0%二苯并噻吩	3.77	0.26	—	[54]
NiMo/MA-20Ti	320	1	质量分数1.0% 4,6-二甲基二苯并噻吩	0.27	8.96	3.9	[55]
NiMo/1-ZAT	320	2	质量分数1.0%二苯并噻吩	0.38	0.62	6.12	[56]
NiMo/TF-35	360	—	500mg/kg S，二苯并噻吩	0.16	0.58	1.64	[57]
NiMo/HMY-6	290	1	质量分数0.5% 4,6-二甲基二苯并噻吩	0.22	0.58	3.50	[58]
NiMo/TD-Mg(2)	340	1	500mg/kg S，二苯并噻吩	0.34	—	3.40	[59]
NiMo/TD-Mg(2)	340	1	500mg/kg S, 4,6-二甲基二苯并噻吩	0.29	—	2.80	[59]
NiMoO _x /Hol-ZSM-5	330	0.05	500mg/kg S，二苯并噻吩	1.87	0.03	—	[60]
1Ge-NiMoS/Al₂O₃	290	1	质量分数0.5% 4,6-二甲基二苯并噻吩	0.608	2.87	3.27	[61]
NiMoS _x /ZSM-5-100	360	—	500mg/kg S，二苯并噻吩	1.41	0.05	10.69	[62]
NiMoS _x /ZSM-5-100	360	—	250mg/kg S，4,6-二甲基二苯并噻吩	0.27	—	—	[62]
5Mo@NC	320	0.4	质量分数1.0%二苯并噻吩	0.04	0.14	1.8	[63]

催化剂	温度/℃	催化剂质量/g	原料	反应速率/10^-6mol·g^-1·s^-1	HYD速率/DDS速率	转化频率/h^-1	参考文献
Co₃S₄@CoMoS	300	0.03	500mg/kg S，二苯并噻吩	5.0	0.26	15.8	[56]
CoMo	260	3 mL	质量分数3.0%二苯并噻吩	0.14	0.41	—	[102]
NiMo	260	3 mL	质量分数3.0%二苯并噻吩	0.13	0.75	—	[102]
MoNi(Co)S	300	0.1	噻吩/四氢萘/正己烷体积比1/9/10	转化率约80%	—	—	[103]
mwnt-MoS₂/Ni	320	0.2	500mg/kg S，二苯并噻吩	0.24	1.3	—	[104]
hnt-MoS₂/Ni	320	0.2	500mg/kg S，二苯并噻吩	1.05	1.8	—	[104]
H-NiMo-150-400	320	0.45	质量分数1.0%二苯并噻吩	转化率约94.7%	0.34	—	[105]
NiYMoS400	320	0.18	500mg/kg S，二苯并噻吩	0.42	—	—	[106]
NiS₂-MoS₂-0.2	290~350	0.3	质量分数0.32%噻吩	0.68	—	6.4	[107]
NiS₂-MoS₂-0.2	290~350	0.3	质量分数0.2% 4,6-二甲基二苯并噻吩	0.54	0.8	4.8	[107]
Co-Mo Sub-microtube	300	0.2	500mg/kg S，二苯并噻吩	4.0	—	—	[108]
Ni_9.5Zn_0.5Mo₁₀	260	0.3	质量分数1.0%二苯并噻吩	0.13	1.8	—	[109]
hp-NiMoS	320	0.18	500mg/kg S，二苯并噻吩	0.99	7.5	—	[110]
lp-NiMoS	320	0.18	500mg/kg S，二苯并噻吩	0.42	2.7	—	[110]
CoMoS-1/1	340	0.015	质量分数2.0%二苯并噻吩	4.1	1.15	118.8	[111]
Co₄Mo₁₂ sulfide	300	—	质量分数2.0%二苯并噻吩	0.72	—	5.3	[112]
MoS₂-OA	320	0.05	330mg/kg S，二苯并噻吩	0.55	3.26	—	[113]
Ni₁Mo₁-200	240	2mL	质量分数1.0%二苯并噻吩	58	—	792	[114]
3DOM CoMo	300	1	质量分数0.5%噻吩	转化率约94%	—	—	[115]