Development and application of ex-situ presulfurization technology for hydrotreating catalysts in China

doi:10.1007/s11705-010-0529-2

Front Chem Sci Eng

2011, Vol. 5

Issue (3) : 287-296 https://doi.org/10.1007/s11705-010-0529-2

REVIEW ARTICLE

Development and application of ex-situ presulfurization technology for hydrotreating catalysts in China

Yulan GAO^1,2(

), Xiangchen FANG^1,2, Zhenmin CHENG¹

1. School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China; 2. Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, Fushun 113001, China

Download: PDF(502 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

The development and application of ex-situ presulfurization (EPRES) technology for hydrotreating catalysts has been reviewed in the present article. The studies in laboratory scale and commercial practice indicated that the adoption of the EPRES catalyst in industrial application can significantly enhance the degree of presulfurization of metal oxide components, shorten the start-up period, and effectively reduce the environmental impact as well as the danger of start-up procedure in industrial hydrotreating unit. This catalyst has been proved to be versatile for different types of hydrogenation reactions. Different types of active site models are also discussed for better understanding the nature of presulfurized catalysts.

Keywords ex-situ presulfurization in situ presulfurization hydrotreating catalyst sulfur utilization ratio

Corresponding Author(s): GAO Yulan,Email:gaoyulan.fshy@sinopec.com

Issue Date: 05 September 2011

Cite this article:

Xiangchen FANG,Zhenmin CHENG,Yulan GAO. Development and application of ex-situ presulfurization technology for hydrotreating catalysts in China[J]. Front Chem Sci Eng, 2011, 5(3): 287-296.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-010-0529-2
https://academic.hep.com.cn/fcse/EN/Y2011/V5/I3/287

Features of EPRES	Features of IPRES
i. Avoid using poisonous sulfurizing agent, safer for start-up process in the refinery unit and more environmentally friendly.	i. Using hazardous sulfurizing agent, unsafe and not environmentally friendly to operators and units.
ii. Active component is already presulfurized and transformed into oxo-sulfide, avoiding deep reduction of active species by hydrogen at high temperature during start-up procedure.	ii. Metal oxide(s) can be deeply reduced by hydrogen at high temperature, and cannot be further sulfurized by sulfurizing agent, causing low catalyst activity.
iii. Presulfurization can reduce the diffusion limitation, leading to a higher degree of sulfurization and utilization of active metals.	iii. In situ sulfurization requires the addition of sulfurizing agent at the start-up step, and the effect of sulfurization is determined by multi- factors such as the diffusion and distribution of sulfur-containing species and the related decomposition rate.
iv. Unnecessary to supply pumps, tanks, and pups, and reduce pollution and apparatus investment.	iv. Hydrotreating unit needs the presulfurization apparatus, higher equipment investment.
v. Direct and rapid temperature rise, shorter start-up procedure, and higher production efficiency, better economical profit.	v. Slow and multi-range temperature increment is required, and the start-up procedure is longer (around one week).
vi. Easy operation of unit, superior sulfurization performance can be achieved even in the conditions of lower operation pressure, uneven distribution of reactant(s), etc.	vi. In situ sulfurization and following start-up procedure involve many steps, highly demand for the reactor and related equipments, leading to insufficient sulfurization and low catalyst activity.
vii. Rapid temperature increase, minor impact on reactor and other apparatuses.	vii. Repeated temperature increment and decline, and frequent expansion and contraction of the equipments may easily result in leakage issue of high temperature units.
viii. In the cases of initial discard and partial replacement, more convenient for start-up process.	viii. For initial discard and partial replacement, the fully controlled in situ sulfurization is still essential.

Tab.1 Comparison of EPRES with conventional IPRES [-]

Tab.2 Comparison of the start-up of EPRES and IPRES technologies

Tab.3 Analysis data of the used water for the application of EPRES catalyst

Fig.1 Comparison of the exothermic effect over the EPRES and reference catalysts

Fig.2 Temperature profiles at the inlet and outlet of the catalyst bed of a diesel hydrogenation unit during activation

Tab.4 Hydrodesulfurization (HDS) and Hydrodenitrogenation (HDN) activities of the EPRES and IPRES catalysts under the same operating conditions and feedstock

Tab.5 Comparison of the EPRES and other ex suit presulfurization technologies

Fig.3 Three Ni forms of the sulfurized Ni-Mo/AlO catalyst: the MoS crystal in the Ni-Mo-S phase, the aggregated NiS and the isolated Ni in the support []

Fig.4 Vertical or parallel crystalline growth of MoS over the γ-AlO planes of (a) (111) and (b) (100) []

Fig.5 The model of Super type II active reaction sites []. (a) Mo and Ni (or Co) are in oxidized state; (b) Ni (or Co) is partially sulfurized; (c) Ni (or Co) and Mo are partially sulfurized; (d) Small MoS slabs decorated with Ni (or Co) formed, and these slabs are still anchored to A1O; (e) Mo gets completely sulfided so that MoS slabs decorated with sulfidic Ni (or Co) become mobile

Fig.6 STM image and ball model of a single-layer Co-Mo-S nanocluster

Fig.7 The CENTERA catalyst reveals improved MoS dispersion compared with the early generation of catalysts

Fig.8 EXAFS derived structural model for the CENTERA catalyst

Fig.9 Ni-promoted CENTERA and CENTINEL catalysts: the former shows improved promoter edge decoration- presence of coordinatively unsaturated Ni centers and absence of less active unsaturated Mo-based edge structures

Tab.6 Application of the EPRES catalysts in China refinery

1	Wilson J H, Berrebi G. Sulficat^?: off-site presulfiding of hydroprocessing catalyst from Eurecat.Studies in Surface Science and Catalysis , 1988, 38: 393-398 doi: 10.1016/S0167-2991(09)60672-8
2	De Wind M, Heinerman J J L, Lee S L, Plantenga F L, Johnson C C, Woodward D C. Air quality and economics spur use of presulfided catalysts.Oil & Gas Journal , 1992, 90: 49-53
3	Blashka S, Bond G, Ward D. New presulfurized catalyst reduces exotherm potential in hydrocrackers.Oil & Gas Journal , 1998, 96: 36-40
4	Berrebi G. Process of presulfurizing catalysts for hydrocarbons treatment.US Patent, 4530917, 1985
5	Dufresne P, Labruyere F. Ex-situ presulfuration in the presence of hydrocarbon molecule. US Patent, 6417134, 2002
6	Seamans J D, Welch J G, Gasser N G. Method of presulfiding a hydrotreating catalyst. US Patent, 4943547, 1990
7	Seamans J D, Adams C T, Dominguez W B, Chen A A. Method of presulfurizing a hydrotreating, hydrocracking or tail gas treating catalyst.US Patent, 5215954, 1993
8	Neuman D J, Semper G K, Creager T. Method of presulfiding and passivating a hydrocarbon conversion catalyst. US Patent, 5958816, 1999
9	Berrebi G. Process for presulfurizing with phosphorous and/or halogen additive.US Patent, 4983559, 1991
10	Wang Y X. Ex-situ presulfurization technology for hydrotreating catalyst.Petroleum Refinery Engineering, 2000, 30: 57-58 (in Chinese)
11	Seamans J D, Adams C T, Dominguez W B, Chen A A. Method of presulfurizing a hydrotreating: hydrocracking or tail gas treating catalyst. US Patent, 5688736, 1997
12	Gao Y, Fang X. Study on hydrogenation catalyst with ex-situ presulfurization technology.Petroleum Processing and Petrochemicals , 2005, 36(7): 1-4 (in Chinese)
13	Gao Y, Fang X, Wang G, Cao F, Li C. Pilot plant test of ex-situ presulfurization hydrotreating catalyst.Petroleum Refinery Engineering , 2005, 35(4): 34-35 (in Chinese)
14	Gao Y, Wang A, Fang X, Hu Y. Development and application of EPRES ex-situ presulfiding technology.Industrial Catalysis , 2007, 15(2): 33-35
15	Gao Y, Fang X, Cheng Z. A comparative study on the ex-situ and in-situ presulfurization of hydrotreating catalysts.Catalysis Today , 2010, 158(3-4): 496-503
16	Schuit G C A, Gates B C. Chemistry and engineering of catalytic hydrodesulfurization.AIChE Journal , 1973, 19(3): 417-4 3 8 doi: 10.1016/j.cattod.2010.07.024
17	Wivel C, Clausen B S, Candia R, M?rup S, Tops?e H. M?ssbauer emission studies of calcined Co-Mo/Al₂O₃ catalysts: catalytic significance of Co precursors.Journal of Catalysis , 1984, 87(2): 497-513 doi: 10.1002/aic.690190303
18	Sakashita Y, Yoneda T. Orientation of MoS₂ clusters supported on two kinds of γ-Al₂O₃ single crystal surfaces with different indices.Journal of Catalysis , 1999, 185(2): 487-495 doi: 10.1016/0021-9517(84)90210-0
19	Tops?e H, Clausen B S, Candia R, Wivel C, M?rup S. In situ M?ssbauer emission spectroscopy studies of unsupported and supported sulfided Co-Mo hydrodesulfurization catalysts: evidence for and nature of a Co-Mo-S phase.Journal of Catalysis , 1981, 68(2): 433-452 doi: 10.1006/jcat.1999.2504
20	Grange P, Vanhaeren X. Hydrotreating catalysts: an old story with new challenges.Catalysis Today , 1997, 36(4): 375-391 doi: 10.1016/0021-9517(81)90114-7
21	Eijsbouts S. On the flexibility of the active phase in hydrotreating catalyst.pplied Catalysis A: General , 1997, 158(1-2): 53-92 doi: 10.1016/S0920-5861(96)00232-5
22	Lauritsen J V, Helveg S, L?gsgaard E, Stensgaard I, Clausen B S, Tops?e H, Besenbacher F. Atomic-scale structure of Co-Mo-S nanoclusters in hydrotreating catalysts.Journal of Catalysis , 2001, 197(1): 1-5 doi: 10.1016/S0926-860X(97)00035-5
23	Raybaud P, Hafner J, Kresse G, Kasztelan S, Toulhoat H. Ab initio study of the H₂-H₂S/MoS₂ gas-solid interface: the nature of the catalytically active sites.Journal of Catalysis , 2000, 189(1): 129-146 doi: 10.1006/jcat.2000.3088

Viewed

Full text

Abstract

Cited

Shared

Discussed