Catalytic hydrodesulfurization (HDS) technique is widely used for clean gasoline production. However, traditional HDS catalyst (CoMo/γ-Al2O3) exhibits high hydrogenation performance of olefins (HYDO), resulting in the loss of gasoline octane number. To achieve high HDS/HYDO ratio, the key issue is to reduce the interaction between active metals and the support, therefore, in this research, the modified CoMo/γ-Al2O3 catalysts with various boron amounts were investigated under traditional or microwave heating. The effects of preparing methods as well as boron amounts on the active phase, acidic properties and HDS catalytic activities were examined. Results show that the modification, especially under microwave treatment, can significantly weaken the interaction between the active component and the support by enlarging the surface area and pore diameter, and reducing the acidity of the support. As a result, the stacking numbers of MoS2 slabs were obviously improved by the modification and microwave treatment, contributing to higher edge/rim ratio, and resulting in higher HDS performance and selectivity to olefin.
. [J]. Frontiers of Chemical Science and Engineering, 2021, 15(5): 1088-1098.
Hui Shang, Chong Guo, Pengfei Ye, Wenhui Zhang. Synthesis of boron modified CoMo/Al2O3 catalyst under different heating methods and its gasoline hydrodesulfurization performance. Front. Chem. Sci. Eng., 2021, 15(5): 1088-1098.
C S Song, X L Ma. Ultra-clean diesel fuels by deep desulfurization and deep dearomatization of middle distillates. Journal of Biomechanics, 2006, 43(3): 579–582
2
R Singh, D Kunzru, S Sivakumar. Monodispersed ultrasmall NiMo metal oxide nanoclusters as hydrodesulfurization catalyst. Applied Catalysis B: Environmental, 2016, 185: 163–173 https://doi.org/10.1016/j.apcatb.2015.12.013
3
C S Song. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel. Catalysis Today, 2003, 86(1): 211–263 https://doi.org/10.1016/S0920-5861(03)00412-7
4
A J Duan, T S Li, Z Zhao, B J Liu, X F Zhou, G Y Jiang, J Liu, Y C Wei, H F Pan. Synthesis of hierarchically porous L-KIT-6 silica-alumina material and the super catalytic performances for hydrodesulfurization of benzothiophene. Applied Catalysis B: Environmental, 2015, 165: 763–773 https://doi.org/10.1016/j.apcatb.2014.10.078
5
M F Li, H F Li, F Jiang, Y Chu, H Nie. The relation between morphology of (Co)MoS2 phases and selective hydrodesulfurization for CoMo catalysts. Catalysis Today, 2010, 149(1-2): 35–39 https://doi.org/10.1016/j.cattod.2009.03.017
6
H Topsøie, R Candia, N Y Topsøe, B Clausen, H Topsøe. On the state of the Co-Mo-S model. Bulletin des Sociétés Chimiques Belges, 1984, 93(8-9): 783–806 https://doi.org/10.1002/bscb.19840930820
7
H Topsøie , B S Clausen, N Y Topsøe, E Pedersen. Recent basic research in hydrodesulfurization catalysis. Industrial & Engineering Chemistry Fundamentals, 1986, 25(1): 25–36 https://doi.org/10.1021/i100021a004
8
H Topsøe, B S Clausen, F E Massoth. Hydrotreating Catalysis.Berlin: Springer, 1996, 116–118
9
W B Chen, F Maugé, J van Gestel, H Nie, D D Li, X Y Long. Effect of modification of the alumina acidity on the properties of supported Mo and CoMo sulfide catalysts. Journal of Catalysis, 2013, 304: 47–62 https://doi.org/10.1016/j.jcat.2013.03.004
10
Y V Vatutina, O V Klimov, K A Nadeina, I G Danilova, E Y Gerasimov, I P Prosvirin, A S Noskov. Influence of boron addition to alumina support by kneading on morphology and activity of HDS catalysts. Applied Catalysis B: Environmental, 2016, 199: 23–32 https://doi.org/10.1016/j.apcatb.2016.06.018
11
F M Bautista, J M Campelo, A Garcia, D Luna, J M Marinas, M C Moreno, A A Romero, J A Navio, M Macias. Structural and textural characterization of AlPO4-B2O3 and Al2O3-B2O3(5–30 wt-% B2O3) systems obtained by boric acid impregnation. Journal of Catalysis, 1998, 173(2): 333–344 https://doi.org/10.1006/jcat.1997.1905
12
G M Dhar, B N Srinivas, M S Rana, M Kumar, S K Maity. Mixed oxide supported hydrodesulfurization catalysts—a review. Catalysis Today, 2003, 86(1): 45–60 https://doi.org/10.1016/S0920-5861(03)00403-6
13
A M D de Farias, A M L Esteves, F Ziarelli, S Caldarelli, M A Fraga, L G Appel. Boria modified alumina probed by methanol dehydration and IR spectroscopy. Applied Surface Science, 2004, 227(1): 132–138 https://doi.org/10.1016/j.apsusc.2003.11.052
14
P Torres-Mancera, J Ramírez, R Cuevas, A Gutiérrez-Alejandre, F Murrieta, R Luna. Hydrodesulfurization of 4,6-DMDBT on NiMo and CoMo catalysts supported on B2O3-Al2O3. Catalysis Today, 2005, 107-108: 551–558 https://doi.org/10.1016/j.cattod.2005.07.072
15
L H Ding, Z S Zhang, Y Zheng, Z Ring, J W Chen. Effect of fluorine and boron modification on the HDS, HDN and HDA activity of hydrotreating catalysts. Applied Catalysis A, General, 2006, 301(2): 241–250 https://doi.org/10.1016/j.apcata.2005.12.014
16
Usman, T Kubota, I Hiromitsu, Y Okamoto. Effect of boron addition on the surface structure of Co-Mo/Al2O3 catalysts. Journal of Catalysis, 2007, 247(1): 78–85 https://doi.org/10.1016/j.jcat.2007.01.010
17
R Palcheva, L Kaluza, A Spojakina, K Jiratova, G Tyuliev. NiMo/g-Al2O3 catalysts from Ni heteropolyoxomolybdate and effect of alumina modification by B, Co, or Ni. Chinese Journal of Catalysis, 2012, 33(6): 952–961 https://doi.org/10.1016/S1872-2067(11)60376-8
18
K P Peil, L G Galya, G Marcelin. Acid and catalytic properties of nonstoichiometric aluminum borates. Journal of Catalysis, 1989, 115(2): 441–451 https://doi.org/10.1016/0021-9517(89)90048-1
19
D J Pérez-Martínez, P Eloy, E M A Gaigneaux, S Giraldo, A Centeno. Study of the selectivity in FCC naphtha hydrotreating by modifying the acid–base balance of CoMo/g-Al2O3 catalysts. Applied Catalysis A, General, 2010, 390(1): 59–70 https://doi.org/10.1016/j.apcata.2010.09.028
20
M Houalla, B Delmon. Joint use of xps and diffuse reflectance spectroscopy for the study of cobalt oxide supported on boron modified alumina. Applied Catalysis, 1981, 1(5): 285–289 https://doi.org/10.1016/0166-9834(81)80034-6
21
H Morishige, Y Akai. Effect of boron addition on the state and dispersion of Mo supported on alumina. Bulletin des Sociétés Chimiques Belges, 1995, 104(4-5): 253–257 https://doi.org/10.1002/bscb.19951040412
22
M Lewandowski, Z Sarbak. Acid-base properties and the hydrofining activity of NiMo catalysts incorporated on alumina modified with F− and Cl−. Applied Catalysis A, General, 1997, 156(2): 181–192 https://doi.org/10.1016/S0926-860X(96)00341-9
23
M Lewandowski, Z Sarbak. The effect of boron addition on hydrodesulfurization and hydrodenitrogenation activity of NiMo/Al2O3 catalysts. Fuel, 2000, 79(5): 487–495 https://doi.org/10.1016/S0016-2361(99)00151-9
24
F Rashidi, T Sasaki, A M Rashidi, A N Kharat, K J Jozani. Ultradeep hydrodesulfurization of diesel fuels using highly efficient nanoalumina-supported catalysts: impact of support, phosphorus, and/or boron on the structure and catalytic activity. Journal of Catalysis, 2013, 299: 321–335 https://doi.org/10.1016/j.jcat.2012.11.012
25
O V Klimov, K A Nadeina, Y V Vatutina, E A Stolyarova, I G Danilova, E Y Gerasimov, I P Prosvirin, A S Noskov. CoMo/Al2O3 hydrotreating catalysts of diesel fuel with improved hydrodenitrogenation activity. Catalysis Today, 2018, 307: 73–83 https://doi.org/10.1016/j.cattod.2017.02.032
26
H Shang, H C Zhang, W Du, Z C Liu. Development of microwave assisted oxidative desulfurization of petroleum oils: a review. Journal of Industrial and Engineering Chemistry, 2013, 19(5): 1426–1432 https://doi.org/10.1016/j.jiec.2013.01.015
27
H Wang, Y Wu, Z W Liu, L He, Z Y Yao, W Y Zhao. Deposition of WO3 on Al2O3 via a microwave hydrothermal method to prepare highly dispersed W/Al2O3 hydrodesulfurization catalyst. Fuel, 2014, 136: 185–193 https://doi.org/10.1016/j.fuel.2014.07.034
28
H Wang, Z Y Yao, X C Zhan, Y Wu, M Li. Preparation of highly dispersed W/ZrO2-Al2O3 hydrodesulfurization catalysts at high WO3 loading via a microwave hydrothermal method. Fuel, 2015, 158: 918–926 https://doi.org/10.1016/j.fuel.2015.06.053
29
H Wang, Z W Liu, Y Wu, Z Y Yao, W Y Zhao, W Z Duan, K Guo. Preparation of highly dispersed W/Al2O3 hydrodesulfurization catalysts via a microwave hydrothermal method: effect of oxalic acid. Arabian Journal of Chemistry, 2016, 9(1): 18–24 https://doi.org/10.1016/j.arabjc.2014.11.023
30
X F Liu, L Zhang, Y H Shi, H Nie, X Y Long. Preparation of NiW/Al2O3 hydrodesulfurization catalyst by ultrasound-microwave treatment. Chinese Journal of Catalysis, 2004, 25(9): 748–752
31
B J Liu, X J Zha, Q M Meng, H J Hou, S S Gao, J X Zhang, S S Sheng, W S Yang. Preparation of NiW/TiO2-Al2O3 hydrodesulfurization catalyst with microwave technique. Chinese Journal of Catalysis, 2005, 26(6): 458–462
32
R Meredith. Engineers Handbook of Industrial Microwave Heating. London: Institute of Electrical Engineers, 1998, 19–20
33
S Badoga, R V Sharma, A K Dalai, J Adjaye. Synthesis and characterization of mesoporous aluminas with different pore sizes: application in NiMo supported catalyst for hydrotreating of heavy gas oil. Applied Catalysis A, General, 2015, 489: 86–97 https://doi.org/10.1016/j.apcata.2014.10.008
34
C Zhang, X Y Liu, T F Liu, Z X Jiang, C Li. Optimizing both the CoMo/Al2O3 catalyst and the technology for selectivity enhancement in the hydrodesulfurization of FCC gasoline. Applied Catalysis A, General, 2019, 575: 187–197 https://doi.org/10.1016/j.apcata.2019.02.025
35
W W Zhou, L Yang, L Liu, Z P Chen, A N Zhou, Y T Zhang, X F He, F X Shi, Z G Zhao. Synthesis of novel NiMo catalysts supported on highly ordered TiO2-Al2O3 composites and their superior catalytic performance for 4,6-dimethyldibenzothiophene hydrodesulfurization. Applied Catalysis B: Environmental, 2020, 268: 118428 https://doi.org/10.1016/j.apcatb.2019.118428
36
S F Shan, P Yuan, W Han, G Shi, X J Bao. Supported NiW catalysts with tunable size and morphology of active phases for highly selective hydrodesulfurization of fluid catalytic cracking naphtha. Journal of Catalysis, 2015, 330: 288–301 https://doi.org/10.1016/j.jcat.2015.06.019
37
X Wang, Z Zhao, P Zheng, Z Chen, A Duan, C Xu, J Jiao, H Zhang, Z Cao, B Ge. Synthesis of NiMo catalysts supported on mesoporous Al2O3 with different crystal forms and superior catalytic performance for the hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene. Journal of Catalysis, 2016, 344: 680–691 https://doi.org/10.1016/j.jcat.2016.10.016
38
J L Brito, A L Barbosa. Effect of phase composition of the oxidic precursor on the HDS activity of the sulfided molybdates of Fe(II), Co(II), and Ni(II). Journal of Catalysis, 1997, 171(2): 467–475 https://doi.org/10.1006/jcat.1997.1796
39
L Lizama, T Klimova. Highly active deep HDS catalysts prepared using Mo and W heteropolyacids supported on SBA-15. Applied Catalysis B: Environmental, 2008, 82(3-4): 139–150 https://doi.org/10.1016/j.apcatb.2008.01.018
40
C Zhang, M Brorson, P Li, X Liu, T Liu, Z Jiang, C Li. CoMo/Al2O3 catalysts prepared by tailoring the surface properties of alumina for highly selective hydrodesulfurization of FCC gasoline. Applied Catalysis A, General, 2019, 570: 84–95 https://doi.org/10.1016/j.apcata.2018.10.039
41
B T Xia, L Y Cao, K W Luo, L Zhao, X Q Wang, J S Gao, C M Xu. Effects of the active phase of CoMo/g-Al2O3 catalysts modified using cerium and phosphorus on the HDS performance for FCC gasoline. Energy & Fuels, 2019, 33(5): 4462–4473 https://doi.org/10.1021/acs.energyfuels.8b04332
42
T T Huang, J D Xu, Y Fan. Effects of concentration and microstructure of active phases on the selective hydrodesulfurization performance of sulfided CoMo/Al2O3 catalysts. Applied Catalysis B: Environmental, 2018, 220: 42–56 https://doi.org/10.1016/j.apcatb.2017.08.029
