Hydrotreatment of Light Cycle Oil Over a Dispersed MoS2 Catalyst
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Haiping Zhang
Abstract
Examination of the hydrotreatment of light cycle oil over a dispersed MoS2 catalyst was conducted in a batch reactor at 375 °C and 1,500 psi. Hydrodesulfurization, hydrodenitrogenation, hydrogenation of aromatics, and hydrocracking activity were all analyzed. Diaromatics are more reactive than monoaromatics. Different sulfur compounds have experimental rates of elimination following the trend of BT>1MBT>> 2MBT>3MBT>4MBT>>DBT≈1MDBT≈2MDBT≈3MDBT. BT and its derivatives are very reactive and easy to eliminate, but become harder to convert as they gain methyl groups. DBTs are harder to eliminate than BTs, and don’t experience significant changes in reactivity as they gain methyl groups. This difference indicates that steric hindrance is more significant in supported catalysts than in unsupported catalysts. Different nitrogen compounds have experimental rates of elimination following the trend of Anilines> Indoles> Carbazoles.
Funding source: Natural Sciences and Engineering Research Council of Canada
Award Identifier / Grant number: 463140 - 14
Funding source: Canada Foundation for Innovation
Award Identifier / Grant number: #31983
Funding statement: The authors gratefully acknowledge the financial assistance from Canada Research Chairs program, Natural Sciences and Engineering Research Council of Canada (STPGP 463140 - 14) and Canada Foundation for Innovation (#31983).
References
1. Ancheyta-Juárez, J., Aguilar-Rodrı́guez, E., Salazar-Sotelo, D., Betancourt-Rivera, G., Leiva-Nuncio, M., 1999. Hydrotreating of straight run gas oil–light cycle oil blends. Applied Catalysis A: General 180, 195–205.10.1016/S0926-860X(98)00351-2Search in Google Scholar
2. Azizi, N., Ali, S.A., Alhooshani, K., Kim, T., Lee, Y., Park, J.I., Miyawaki, J., Yoon, S.H., Mochida, I., 2013. Hydrotreating of light cycle oil over NiMo and CoMo catalysts with different supports. Fuel Processing Technology 109, 172–178.10.1016/j.fuproc.2012.11.001Search in Google Scholar
3. Đukanović, Z., Glišić, S.B., Čobanin, V.J., Nićiforović, M., Georgiou, C.A., Orlović, A.M., 2013. Hydrotreating of straight-run gas oil blended with FCC naphtha and light cycle oil. Fuel Processing Technology 106, 160–165.10.1016/j.fuproc.2012.07.018Search in Google Scholar
4. Egorova, M., Prins, R., 2004. Competitive hydrodesulfurization of 4,6-dimethyldibenzothiophene, hydrodenitrogenation of 2-methylpyridine, and hydrogenation of naphthalene over sulfided NiMo/gamma-Al2O3. Journal of Catalysis 224, 278–287.10.1016/j.jcat.2004.03.005Search in Google Scholar
5. Eijsbouts, S., Mayo, S.W., Fujita, K., 2007. A unsupported transition metal sulfide catalysts: From fundamentals to industrial application. Applied Catalysis A: General 322, 58.10.1016/j.apcata.2007.01.008Search in Google Scholar
6. Farag, H., Mochida, I., 2012. A comparative kinetic study on ultra-deep hydrodesulfurization of pre-treated gas oil over nanosized MoS2, CoMo-sulfide, and commercial CoMo/Al2O3 catalysts. Journal of Colloid and Interface Science 372, 121–129.10.1016/j.jcis.2012.01.019Search in Google Scholar
7. Farag, H., Sakanishi, K., 2004. Investigation of 4,6-dimethyldibenzothiophene hydrodesulfurization over a highly active bulk MoS2 catalyst. Journal of Catalysis 225, 531–535.10.1016/j.jcat.2004.05.001Search in Google Scholar
8. Farag, H., Sakanishi, K., Kouzu, M., Matsumura, A., Sugimoto, Y., Saito, I., 2003. Investigation of the influence of H2S on hydrodesulfurization of dibenzothiophene over a bulk MoS2 catalyst. Industrial & Engineering Chemistry Research 42, 306–310.10.1021/ie020404vSearch in Google Scholar
9. García-Cruz, I., Valencia, D., Klimova T., Oviedo-Roa, R., Manuel Martínez-Magadán, J., Gómez-Balderas R., Illas F., 2008. Proton affinity of S-containing aromatic compounds: Implications for crude oil hydrodesulfurization. Journal of Molecular Catalysis A: Chemical 281, 79–84.10.1016/j.molcata.2007.08.031Search in Google Scholar
10. Gates, B.C., Topsøe, H., 1997. Reactivities in deep catalytic hydrodesulfurization: challenges, opportunities, and the importance of 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. Polyhedron 16, 3213–3217.10.1016/S0277-5387(97)00074-0Search in Google Scholar
11. Isoda, T., Nagao, S., Ma, X., Korai, Y., Mochida, I. 1997. Catalytic activities of NiMo and CoMoAl2O3 of variable Ni and Co contents for the hydrodesulfurization of 4,6-dimethyldibenzothiophene in the presence of naphthalene. Applied Catalysis A: General 150, 1–11.10.1016/S0926-860X(96)00299-2Search in Google Scholar
12. Jansen, T., Guerry, D., Gotteland, D., Bacaud, R., Lacroix, M., Ropars, M., Lorentz, C., Geantet, C., TayakoutFayolle, M., 2014. Characterization of a continuous microscale pilot unit for petroleum residue hydroconversion with dispersed catalysts: Hydrodynamics and performances in once through and recycling mode. Chemical Engineering Journal 253, 493–501.10.1016/j.cej.2014.05.032Search in Google Scholar
13. Koltai, T., Macaud, M., Guevara, A., Schulz, E., Lemaire, M., Bacaud, R., Vrinat, M., 2002. Comparative inhibiting effect of polycondensed aromatics and nitrogen compounds on the hydrodesulfurization of alkyldibenzothiophenes. Applied Catalysis A-General 231, 253–261.10.1016/S0926-860X(02)00063-7Search in Google Scholar
14. Landau, M.V., 1997. Deep hydrotreating of middle distillates from crude and shale oils. Catalysis Today 36, 393–429.10.1016/S0920-5861(96)00233-7Search in Google Scholar
15. Liu, K., Ng, F., 2010. Effect of the nitrogen heterocyclic compounds on hydrodesulfurization using in situ hydrogen and a dispersed Mo catalyst. Catalysis Today 149, 28–34.10.1016/j.cattod.2009.05.008Search in Google Scholar
16. Liu, Z., Zheng, Y., Wang, W., Zhang, Q., Jia, L., 2008. Simulation of hydrotreating of light cycle oil with a system dynamics model. Applied Catalysis A: General 339, 209–220.10.1016/j.apcata.2008.01.018Search in Google Scholar
17. Nylén, U., Delgado, J.F., Järås, S., Boutonnet, M., 2004. Characterization of alkylated aromatic sulphur compounds in light cycle oil from hydrotreated vacuum gas oil using GC-SCD, Fuel Processing Technology 86, 223–234.10.1016/j.fuproc.2004.03.001Search in Google Scholar
18. Saih, Y., Segawa, K., 2003. Ultradeep hydrodesulfurization of dibenzothiophene (DBT) derivatives over Mo-sulfide catalysts supported on TiO2-coated alumina composite. Catalysis Surveys from Asia 7, 235–249.10.1023/B:CATS.0000008163.06816.b7Search in Google Scholar
19. Shafi, R., Hutchings, G.J., 2000. Hydrodesulfurization of hindered dibenzothiophenes: an overview. Catalysis Today 59, 423–442.10.1016/S0920-5861(00)00308-4Search in Google Scholar
20. Snare, M., Kubickova, I., Maki-Arvela, P., Eranen, K., Warna, J., Murzin, D.Y., 2007. Production of diesel fuel from renewable feeds: Kinetics of ethyl stearate decarboxylation. Chemical Engineering Journal 134, 29–34.10.1016/j.cej.2007.03.064Search in Google Scholar
21. Song, T., Zhang, Z., Chen, J., Ring, Z., Yang, H., Zheng, Y., 2006. Effect of aromatics on deep hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene over NiMo/Al2O3 catalyst. Energy and Fuels 20, 2344–2349.10.1021/ef060199mSearch in Google Scholar
22. Vassilaros, D.L., Kong, R.C., Later, D.W., Lee, M.L., 1982. Linear retention index system for polycylic aromatic-compounds – Critical-evaluation and additional Indexes. Journal of Chromatography 252, 1–20.10.1016/S0021-9673(01)88394-1Search in Google Scholar
23. Vradman, L., Landau, M.V., Herskowitz, M., 1999. Deep desulfurization of diesel fuels: kinetic modeling of model compounds in trickle-bed. Catalysis Today 48, 41–48.10.1016/S0920-5861(98)00356-3Search in Google Scholar
24. Yang, H., Chen, J., Fairbridge, C., Briker, Y., Zhu, Y.J., Ring, Z., 2004. Inhibition of nitrogen compounds on the hydrodesulfurization of substituted dibenzothiophenes in light cycle oil. Fuel Processing Technology 85, 1415–1429.10.1016/j.fuproc.2003.09.008Search in Google Scholar
25. Yang, H., Chen, J.W., Briker, Y., Szynkarczuk, R., Ring, Z., 2005. Effect of nitrogen removal from light cycle oil on the hydrodesulphurization of dibenzothiophene, 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene. Catalysis Today 109, 16–23.10.1016/j.cattod.2005.08.028Search in Google Scholar
26. Yao, S., Zheng, Y., Ding, L., Ng, S., Yang, H., 2012. Co-promotion of fluorine and boron on NiMo/Al2O3 for hydrotreating light cycle oil. Catalysis Science & Technology 2, 1925–1932.10.1039/c2cy20042bSearch in Google Scholar
27. Yoosuk, B., Song, C., Kim, J.H., Ngamcharussrivichai, C., Prasassarakich, P., 2010. Effects of preparation conditions in hydrothermal synthesis of highly active unsupported NiMo sulfide catalysts for simultaneous hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene. Catalysis Today 149, 52–61.10.1016/j.cattod.2009.05.001Search in Google Scholar
28. Zhang, H., Lin, H., Zheng, Y., Hu, Y.F., MacLennan, A., 2015. Understanding of the effect of synthesis temperature on the crystallization and activity of nanoMoS2 catalyst. Applied Catalysis B: Environmental 165, 537–546.10.1016/j.apcatb.2014.10.046Search in Google Scholar
©2016 by De Gruyter
Articles in the same Issue
- Frontmatter
- Editorial
- In Honour of Professor Serge Kaliaguine
- Research Articles
- Core/Shell Nanostructured Materials for Sustainable Processes
- Photodegradation Efficiencies in a Photo-CREC Water-II Reactor Using Several TiO2 Based Catalysts
- Hydrotreatment of Light Cycle Oil Over a Dispersed MoS2 Catalyst
- Hybrid Ionic Liquid-Chitosan Membranes for CO2 Separation: Mechanical and Thermal Behavior
- Photo-oxidation of Tributyltin, Dibutyltin and Monobutyltin in Water and Marine Sediments
- Contribution of Pd Membrane to Dehydrogenation of Isobutane Over a New Mesoporous Cr/MCM-41 Catalyst
- Self Diffusivity of n-Dodecane and Benzothiophene in ZSM-5 Zeolites. Its Significance for a New Catalytic Light Diesel Desulfurization Process
- Staggered Grid Finite Volume Approach for Modeling Single Particle Char Gasification
- High Efficiency CeCu Composite Oxide Catalysts Improved via Preparation Methods for Propyl Acetate Catalytic Combustion in Air
- Hydrodesulfurization of Dibenzothiophene in a Micro Trickle Bed Catalytic Reactor under Operating Conditions from Reactive Distillation
- Surface Modification of the ZnO Nanoparticles with γ-Aminopropyltriethoxysilane and Study of Their Photocatalytic Activity, Optical Properties and Antibacterial Activities
- One-Pot Isomerization of n-Alkanes by Super Acidic Solids: Sulfated Aluminum-Zirconium Binary Oxides
- Photocatalytic Decomposition of Metoprolol and Its Intermediate Organic Reaction Products: Kinetics and Degradation Pathway
Articles in the same Issue
- Frontmatter
- Editorial
- In Honour of Professor Serge Kaliaguine
- Research Articles
- Core/Shell Nanostructured Materials for Sustainable Processes
- Photodegradation Efficiencies in a Photo-CREC Water-II Reactor Using Several TiO2 Based Catalysts
- Hydrotreatment of Light Cycle Oil Over a Dispersed MoS2 Catalyst
- Hybrid Ionic Liquid-Chitosan Membranes for CO2 Separation: Mechanical and Thermal Behavior
- Photo-oxidation of Tributyltin, Dibutyltin and Monobutyltin in Water and Marine Sediments
- Contribution of Pd Membrane to Dehydrogenation of Isobutane Over a New Mesoporous Cr/MCM-41 Catalyst
- Self Diffusivity of n-Dodecane and Benzothiophene in ZSM-5 Zeolites. Its Significance for a New Catalytic Light Diesel Desulfurization Process
- Staggered Grid Finite Volume Approach for Modeling Single Particle Char Gasification
- High Efficiency CeCu Composite Oxide Catalysts Improved via Preparation Methods for Propyl Acetate Catalytic Combustion in Air
- Hydrodesulfurization of Dibenzothiophene in a Micro Trickle Bed Catalytic Reactor under Operating Conditions from Reactive Distillation
- Surface Modification of the ZnO Nanoparticles with γ-Aminopropyltriethoxysilane and Study of Their Photocatalytic Activity, Optical Properties and Antibacterial Activities
- One-Pot Isomerization of n-Alkanes by Super Acidic Solids: Sulfated Aluminum-Zirconium Binary Oxides
- Photocatalytic Decomposition of Metoprolol and Its Intermediate Organic Reaction Products: Kinetics and Degradation Pathway
