Catalyst particle shapes and pore structure engineering for hydrodesulfurization and hydrodenitrogenation reactions

doi:10.1007/s11705-021-2127-x

Front. Chem. Sci. Eng.

2022, Vol. 16

Issue (6) : 897-908 https://doi.org/10.1007/s11705-021-2127-x

RESEARCH ARTICLE

Catalyst particle shapes and pore structure engineering for hydrodesulfurization and hydrodenitrogenation reactions

Yao Shi¹, Zhao Li¹, Changfeng Yang¹, Zhanlin Yang², Zhenhui Lv², Chong Peng², Bao-Lian Su³, Weikang Yuan¹, Xinggui Zhou¹, Xuezhi Duan¹(

)

¹. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
². Dalian Research Institute of Petroleum and Petrochemicals, SINOPEC, Dalian 116045, China
³. Laboratory of Inorganic Materials Chemistry, University of Namur, B-5000 Namur, Belgium

Download: PDF(2705 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

Catalyst particle shapes and pore structure engineering are crucial for alleviating internal diffusion limitations in the hydrodesulfurization (HDS)/hydrodenitrogenation (HDN) of gas oil. The effects of catalyst particle shapes (sphere, cylinder, trilobe, and tetralobe) and pore structures (pore diameter and porosity) on HDS/HDN performance at the particle scale are investigated via mathematical modeling. The relationship between particle shape and effectiveness factor is first established, and the specific surface areas of different catalyst particles show a positive correlation with the average HDS/HDN reaction rates. The catalyst particle shapes primarily alter the average HDS/HDN reaction rate to adjust the HDS/HDN effectiveness factor. An optimal average HDS/HDN reaction rate exists as the catalyst pore diameter and porosity increase, and this optimum value indicates a tradeoff between diffusion and reaction. In contrast to catalyst particle shapes, the catalyst pore diameter and the porosity of catalyst particles primarily alter the surface HDS/HDN reaction rate to adjust the HDS/HDN effectiveness factor. This study provides insights into the engineering of catalyst particle shapes and pore structures for improving HDS/HDN catalyst particle efficiency.

Keywords hydrodesulfurization hydrodenitrogenation particle shape pore structure

Corresponding Author(s): Xuezhi Duan

Online First Date: 08 April 2022 Issue Date: 28 June 2022

Cite this article:

Yao Shi,Zhao Li,Changfeng Yang, et al. Catalyst particle shapes and pore structure engineering for hydrodesulfurization and hydrodenitrogenation reactions[J]. Front. Chem. Sci. Eng., 2022, 16(6): 897-908.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-021-2127-x
https://academic.hep.com.cn/fcse/EN/Y2022/V16/I6/897

Fig.1 Schematic diagram of HDS and HDN single-particle model for four different shapes.

Tab.1 Geometrical parameters of four different particles

Position	Temperature	Concentration
Reactor inlet (z= 0)	T = T₀	c_i = c_i_,0
Reactor outlet (z= L_R)	$∂ T ∂ z = 0$	$∂ c i ∂ z = 0$
Particle center (r= 0)	$∂ T ∂ r = 0$	$∂ c i ∂ r = 0$
Particle external surface (r= R_P)	T = T_s	c_i = c_i_,s

Tab.2 Boundary conditions for solving Eqs. (13), (14), (16) and (17)^a)

Tab.3 Parameters for simulation of HDS and HDN

Fig.2 Comparison of outlet (a) sulfur and (b) nitrogen concentrations between experimental [24] and simulated results (T = 340 °C, P = 5.3 MPa, LHSV = 2.5 h^–1, z_L = 25.2 cm, u_L= 0.0181 cm?s^–1, ρ_B = 0.9943).

Tab.4 Operational conditions and properties of catalyst particle

Fig.3 (a) Concentration distribution of sulfur-containing compounds in catalyst particles of different shapes; (b) average and surface HDS reaction rates of different catalyst particles; (c) HDS effectiveness factors of different catalyst particles.

Fig.4 (a) Concentration distribution of nitrogen-containing compounds in catalyst particles of different shapes; (b) average and surface HDN reactions rate of different catalyst particles; (c) HDN effectiveness factors of different catalyst particles.

Fig.5 (a) Average and surface HDS reaction rates; (b) HDS effectiveness factor as a function of particle specific surface area; (c) average and surface HDN reaction rates; (d) HDN effectiveness factor as a function of particle specific surface area.

Fig.6 Average HDS and HDN reaction rate as a function of (a) catalyst pore diameter and (b) catalyst porosity; (c) catalyst pore diameter as a function of porosity and surface area; (d) catalyst porosity as a function of pore diameter and surface area; (e) schematic diagram showing effect of catalyst pore diameter and catalyst porosity on reaction rate.

Fig.7 HDS and HDN effectiveness factor as a function of (a) catalyst pore diameter and (b) catalyst porosity.

Fig.8 (a) Concentration distribution of sulfur-containing compounds in trilobe catalyst particle of different pore diameters; (b) average and surface HDS reaction rate; (c) HDS effectiveness factor and diffusion coefficient with respect to pore diameter; (d) concentration distribution of nitrogen-containing compounds in trilobe catalyst particle of different pore diameters; (e) average and surface HDN reaction rate; (f) HDN effectiveness factor and diffusion coefficient with respect to pore diameter.

1	J Ancheyta-Juárez, E Aguilar-Rodríguez, D Salazar-Sotelo, G Betancourt-Rivera, M Leiva-Nuncio. Hydrotreating of straight run gas oil light cycle oil blends. Applied Catalysis A, General, 1999, 180(1–2): 195–205 https://doi.org/10.1016/S0926-860X(98)00351-2
2	G Marroquín-Sánchez, J Ancheyta-Juárez. Catalytic hydrotreating of middle distillates blends in a fixed-bed pilot reactor. Applied Catalysis A, General, 2001, 207(1–2): 407–420 https://doi.org/10.1016/S0926-860X(00)00683-9
3	C Schmitz, L Datsevitch, A Jess. Deep desulfurization of diesel oil: kinetic studies and process-improvement by the use of a two-phase reactor with pre-saturator. Chemical Engineering Science, 2004, 59(14): 2821–2829 https://doi.org/10.1016/j.ces.2004.03.015
4	L da R Novaes, N S de Resende, V M M Salim, A R Secchi. Modeling, simulation and kinetic parameter estimation for diesel hydrotreatin. Fuel, 2017, 209: 184–193 https://doi.org/10.1016/j.fuel.2017.07.092
5	A Stanislaus, A Marafi, M S Rana. Recent advances in the science and technology of ultra low sulfur diesel (ULSD) production. Catalysis Today, 2010, 153(1–2): 1–68 https://doi.org/10.1016/j.cattod.2010.05.011
6	F S Mjalli, O U Ahmed, T Al-Wahaibi, Y Al-Wahaibi, I M Al Nashef. Deep oxidative desulfurization of liquid fuels. Reviews in Chemical Engineering, 2014, 30(4): 337–378 https://doi.org/10.1515/revce-2014-0001
7	M Breysse, G Djega-Mariadassou, S Pessayre, C Geantet, M Vrinat, G Pérot, M Lemaire. Deep desulfurization: reactions, catalysts and technological challenges. Catalysis Today, 2003, 84(3–4): 129–138 https://doi.org/10.1016/S0920-5861(03)00266-9
8	I V Babich, J A Moulijn. Science and technology of novel processes for deep desulfurization of oil refinery streams: a review. Fuel and Energy Abstracts, 2003, 82(6): 607–631
9	S K Bej. Performance evaluation of hydroprocessing catalysts—a review of experimental techniques. Energy & Fuels, 2002, 16(3): 774–784 https://doi.org/10.1021/ef010254l
10	A De Bruljn, I Naka, J W M Sonnemans. Effect of the noncylindrical shape of extrudates on the hydrodesulfurization of oil fractions. Industrial & Engineering Chemistry Process Design and Development, 1981, 20(1): 40–45 https://doi.org/10.1021/i200012a005
11	A T Jarullah, I M Mujtaba, A S Wood. Kinetic parameter estimation and simulation of trickle-bed reactor for hydrodesulfurization of crude oil. Chemical Engineering Science, 2011, 66(5): 859–871 https://doi.org/10.1016/j.ces.2010.11.016
12	P Mann, F V Diez, S Ordonez. Fixed bed membrane reactors for WGSR-based hydrogen production: optimization of modelling approaches and reactor performance. International Journal of Hydrogen Energy, 2012, 37(6): 4997–5010 https://doi.org/10.1016/j.ijhydene.2011.12.027
13	H F Farahani, S Shahhosseini. Simulation of hydrodesulfurization trickle bed reactor. Chemical Product and Process Modeling, 2011, 6(1): 1–19 https://doi.org/10.2202/1934-2659.1487
14	J Ancheyta, J A D Muñoz, M J Macías. Experimental and theoretical determination of the particle size of hydrotreating catalysts of different shapes. Catalysis Today, 2005, 109(1–4): 120–127 https://doi.org/10.1016/j.cattod.2005.08.009
15	M J Macías, J Ancheyta. Simulation of an isothermal hydrodesulfurization small reactor with different catalyst particle shapes. Catalysis Today, 2004, 98(1–2): 243–252 https://doi.org/10.1016/j.cattod.2004.07.038
16	M J Macías Hernández, R D Morales, A Ramírez-Lopez. Simulation of the effectiveness factor for a tri-lobular catalyst on the hydrodesulfurization of diesel. International Journal of Chemical Reactor Engineering, 2009, 7(1): 91–97 https://doi.org/10.2202/1542-6580.1806
17	S Kolitcheff, E Jolimate, A Hugon, J Verstraete, M Rivallan, P L Carrette, F Couenne, M Tayakout-Fayolle. Tortuosity and mass transfer limitations in industrial hydrotreating catalysts: effect of particle shape and size distribution. Catalysis Science & Technology, 2018, 8(10): 4537–4549 https://doi.org/10.1039/C8CY00831K
18	Y Shi, C F Yang, X Q Zhao, Y Q Cao, G Qian, M K Lu, G H Ye, C Peng, B K Sui, Z H Lv, et al.. Engineering the hierarchical pore structures and geometries of hydrodemetallization catalyst pellets. Industrial & Engineering Chemistry Research, 2019, 58(23): 9829–9837 https://doi.org/10.1021/acs.iecr.9b01174
19	L Yang, J F Lu, H Y Chen, E Ruckenstein, Y H Qin, T L Wang, W Sun, C W Wang. Screening and improving porous materials for ultradeep desulfurization of gasoline. Industrial & Engineering Chemistry Research, 2020, 60(1): 604–613 https://doi.org/10.1021/acs.iecr.0c04836
20	T Klimova, L Peña, L Lizama, C Salcedo, O Y Gutiérrez. Modification of activity and selectivity of NiMo/SBA-15 HDS catalysts by grafting of different metal oxides on the support surface. Industrial & Engineering Chemistry Research, 2009, 48(3): 1126–1133 https://doi.org/10.1021/ie800626k
21	C E Salmas, G P Androutsopoulos. A novel pore structure tortuosity concept based on nitrogen sorption hysteresis data. Industrial & Engineering Chemistry Research, 2011, 40(2): 721–730 https://doi.org/10.1021/ie000626y
22	Z Zhou, S L Chen, D Hua, J H Zhang. Preparation and evaluation of a well-ordered mesoporous nickel-molybdenum/silica opal hydrodesulfurization model catalyst. Transition Metal Chemistry, 2011, 37(1): 25–30 https://doi.org/10.1007/s11243-011-9552-5
23	Y P Lv, X L Wang, D W Gao, X L Ma, S N Li, Y Wang, G L Song, A J Duan, G Z Chen. Hierarchically porous ZSM-5/SBA-15 zeolite: tuning pore structure and acidity for enhanced hydro-upgrading of FCC gasoline. Industrial & Engineering Chemistry Research, 2018, 57(42): 14031–14043 https://doi.org/10.1021/acs.iecr.8b02952
24	F S Mederos, J Ancheyta, I Elizalde. Dynamic modeling and simulation of hydrotreating of gas oil obtained from heavy crude oil. Applied Catalysis A, General, 2012, 425–426: 13–27 https://doi.org/10.1016/j.apcata.2012.02.034
25	O Macé, J Wei. Diffusion in random particle models for hydrodemetalation catalysts. Industrial & Engineering Chemistry Research, 1991, 30(5): 909–918 https://doi.org/10.1021/ie00053a013
26	S M Rao, M O Coppens. Increasing robustness against deactivation of nanoporous catalysts by introducing an optimized hierarchical pore network—application to hydrodemetalation. Chemical Engineering Science, 2012, 83: 66–76 https://doi.org/10.1016/j.ces.2011.11.044
27	P J Topalian, D R Liyanage, S J Danforth, A I Aquino, S L Brock, M E Bussell. Effect of particle size on the deep HDS properties of Ni2P catalysts. Journal of Physical Chemistry C, 2019, 123(42): 25701–25711 https://doi.org/10.1021/acs.jpcc.9b07034
28	P E Boahene, K Soni, A K Dalai, J Adjaye. Application of different pore diameter SBA-15 supports for heavy gas oil hydrotreatment using FeW catalyst. Applied Catalysis A, General, 2011, 402(1–2): 31–40 https://doi.org/10.1016/j.apcata.2011.05.005
29	K C Mouli, K K Soni, A K Dalai, J Adjaye. Effect of pore diameter of Ni-Mo/Al-SBA-15 catalysts on the hydrotreating of heavy gas oil. Applied Catalysis A, General, 2011, 404(1–2): 21–29 https://doi.org/10.1016/j.apcata.2011.07.001

[1]

FCE-21061-OF-SY_suppl_1

Download

[1]	Hui Shang, Chong Guo, Pengfei Ye, Wenhui Zhang. Synthesis of boron modified CoMo/Al₂O₃ catalyst under different heating methods and its gasoline hydrodesulfurization performance[J]. Front. Chem. Sci. Eng., 2021, 15(5): 1088-1098.
[2]	Hui Shang, Pengfei Ye, Yude Yue, Tianye Wang, Wenhui Zhang, Sainab Omar, Jiawei Wang. Experimental and theoretical study of microwave enhanced catalytic hydrodesulfurization of thiophene in a continuous-flow reactor[J]. Front. Chem. Sci. Eng., 2019, 13(4): 744-758.
[3]	Haiding XIANG, Tiefeng WANG. Kinetic study of hydrodesulfurization of coker gas oil in a slurry reactor[J]. Front Chem Sci Eng, 2013, 7(2): 139-144.
[4]	SUN Guida, LI Cuiqing, ZHOU Zhijun, LI Fengyan. Synthesis, characterization and hydrotreating performance of supported tungsten phosphide catalysts[J]. Front. Chem. Sci. Eng., 2008, 2(2): 155-164.

Viewed

Full text

Abstract

Cited

Shared

Discussed