Modulation of NiMo-based catalysts by Fe species and its effect on catalytic hydrodesulfurization performance

doi:10.16085/j.issn.1000-6613.2024-0160

Abstract

Abstract:

Y zeolites were modified by different concentrations of iron nitrate solutions. Catalysts were prepared by incipient wetness impregnation method using nickel nitrate and ammonium molybdate as active metal precursors. The physical and chemical properties of the zeolites and catalysts were characterized by X-ray diffraction (XRD), low-temperature nitrogen adsorption (BET), scanning electron microscopy (SEM), NH₃-temperature programmed desorption (NH₃-TPD), hydrogen-temperature programmed reduction (H₂-TPR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and other analytical methods. The hydrodesulfurization (HDS) performance of the catalysts was evaluated on a fixed-bed reactor using dibenzothiophene as a probe. The experimental results showed that the introduction of Fe species increased the specific surface areas and pore volumes of Y zeolite, modulated the acidity of Y zeolite, weakened the interactions between NiMo metals and supports, and modulated the electronic structure of NiMo. The introduction of Fe species also resulted in a shorter MoS₂ average slab length of the sulfide catalysts, a higher average number of stacked layers, higher metal Ni and Mo sulfidation degrees and higher NiMoS active phase ratios, which significantly improved the hydrodesulfurization activity of the catalyst. The NiMo/0.12MFe-Y catalyst showed 81% HDS conversion at 260℃, 18 percentage points higher than that of NiMo/USY catalyst, and also a higher direct desulfurization path selectivity.

Key words: molecular sieves, catalyst, electron transfer, active phase, hydrodesulfurization

摘要：

以不同浓度的硝酸铁溶液处理的Y分子筛作为载体，以硝酸镍和钼酸铵为活性金属前体，采用等体积浸渍法制备催化剂。利用X射线衍射（XRD）、低温氮气吸附（BET）、扫描电子显微镜（SEM）、氨气程序升温脱附（NH₃-TPD）、氢气程序升温还原（H₂-TPR）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）等分析方法对Y分子筛及催化剂进行了物化性质表征。以二苯并噻吩为探针在固定床反应器上评价催化剂的加氢脱硫（HDS）性能。结果表明，Fe物种的引入提高了Y分子筛比表面积和孔体积，改善了Y分子筛的酸性，减弱了NiMo金属和载体间的相互作用，调变了NiMo的电子结构，从而使硫化态催化剂具有更短的MoS₂平均片晶长度和更高的平均堆垛层数、更高的金属Ni和Mo硫化度及NiMoS活性相比例，显著提高了催化剂的加氢脱硫活性。NiMo/0.12MFe-Y催化剂在260℃时的加氢脱硫转化率达81%，比NiMo/USY催化剂提高了18百分点，并且具有更高的直接脱硫路径选择性。

关键词: 分子筛, 催化剂, 电子转移, 活性相, 加氢脱硫

CLC Number:

O643.32

LI Xiaoqian, REN Shenyong, LIU Lu, YANG Chi, SHEN Baojian, XU Chunming. Modulation of NiMo-based catalysts by Fe species and its effect on catalytic hydrodesulfurization performance[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 867-878.

李晓倩, 任申勇, 刘璐, 杨驰, 申宝剑, 徐春明. Fe物种对NiMo基催化剂的调控及加氢脱硫性能的影响[J]. 化工进展, 2025, 44(2): 867-878.

Figures/Tables 17

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样品	相对结晶度/%	Fe₂O₃质量分数/%	BET比表面积 /m²·g^-1	微孔比表面积 /m²·g^-1	介孔比表面积 /m²·g^-1	总孔体积 /cm³·g^-1	微孔体积 /cm³·g^-1	介孔体积 /cm³·g^-1
USY	84	—	586	509	77	0.39	0.249	0.141
0.02MFe-Y	64	4.28	564	455	109	0.392	0.222	0.170
0.06MFe-Y	47	11.01	603	469	134	0.464	0.229	0.235
0.12MFe-Y	52	9.46	613	467	146	0.448	0.223	0.225

样品	相对结晶度/%	Fe₂O₃质量分数/%	BET比表面积 /m²·g^-1	微孔比表面积 /m²·g^-1	介孔比表面积 /m²·g^-1	总孔体积 /cm³·g^-1	微孔体积 /cm³·g^-1	介孔体积 /cm³·g^-1
USY	84	—	586	509	77	0.39	0.249	0.141
0.02MFe-Y	64	4.28	564	455	109	0.392	0.222	0.170
0.06MFe-Y	47	11.01	603	469	134	0.464	0.229	0.235
0.12MFe-Y	52	9.46	613	467	146	0.448	0.223	0.225

样品	弱酸位点/µmol·g^-1			强酸位点/µmol·g^-1			总酸位点/µmol·g^-1
样品	B	L	B+L	B	L	B+L	总酸位点/µmol·g^-1
USY	88	177	265	74	92	166	431
0.02MFe-Y	125	97	222	101	106	207	429
0.06MFe-Y	124	126	250	93	101	194	444
0.12MFe-Y	79	105	184	43	166	209	393

样品	弱酸位点/µmol·g^-1			强酸位点/µmol·g^-1			总酸位点/µmol·g^-1
样品	B	L	B+L	B	L	B+L	总酸位点/µmol·g^-1
USY	88	177	265	74	92	166	431
0.02MFe-Y	125	97	222	101	106	207	429
0.06MFe-Y	124	126	250	93	101	194	444
0.12MFe-Y	79	105	184	43	166	209	393

催化剂	平均片晶长度/nm	平均堆垛层数	f_Mo
NiMo/USY	2.93	1.97	0.32
NiMo/0.02MFe-Y	3.31	2.02	0.31
NiMo/0.06MFe-Y	2.68	2.86	0.35
NiMo/0.12MFe-Y	2.42	3.42	0.39