Hydrodesulfurization of Diesel Oils by MoS2 Catalyst Prepared by in situ Decomposition of Ammonium Thiomolybdate
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ammonium thiomolybdate diesel oils hydrodesulfurization
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Abstract
An unsupported MoS2 catalyst was prepared by in situ decomposition of ammonium thiomolybdate (ATM)in the presence of water. The catalyst was characterized by XRD, scanning electron microscopy (SEM) andspecific surface area measurements (BET, BJH). Its catalytic activity was evaluated for the hydrodesulfurization(HDS) of diesel oils (straight run gas oil, SRGO and light cycle oil, LCO). Selected refractory sulfur compounds:benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) in oils wereinvestigated. The high catalytic activity resulted from the large surface area of the catalyst due to water addition.Reactivity order of the sulfur compounds were determined. The results showed that the reactivity order in SRGOwhich contains nitrogen content is different from that in LCO. This reveals that matrix effect of the oil has someinfluences on the reactivity of the sulfur compounds.
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Trakarnpruk, W., Seentrakoon, B., & Porntangjitlikit, S. (2013). Hydrodesulfurization of Diesel Oils by MoS2 Catalyst Prepared by in situ Decomposition of Ammonium Thiomolybdate. Science, Engineering and Health Studies, 2(1), 7–13. https://doi.org/10.14456/sustj.2008.1
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Research Articles
References
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Candia, R., Clausen, B. S., and Topsoe, H. (1982). The origin of catalytic synergy in unsupported Co-Mo HDS catalysts. Journal of Catalysis, 77: 564-566.
Chianelli, R. R. (1984). Fundamental studies of transition metal sulfide hydrodesulfurization catalysts. Catalysis Review Engineering, 26: 361-393.
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Laredo, G. C. and Cortes, C. M. (2003). Kinetics of hydrodesulfurization of dimethyl dibenzothiophenes in a gas oil narrow-cut fraction and solvent effects. Applied Catalysis A: General, 252: 295-304.
Ma, X., Sakanishi, K., and Mochida, I. (1996). Hydrodesulfurization reactivities of various sulfur compounds in vacuum gas oil. Industrial & Engineering Chemistry Research, 35: 2487-2494.
Pecoraro, T. A., Russell, R., and Chianelli, R. R. (1985). Hydrogenation processes using carbon-containing molybdenum and tungsten sulfide catalysts. US Patent No. 4528089.
Sano, Y., Choi, K. H., Korai, Y., and Mochida, I. (2004). Effects of nitrogen and refractory sulfur species removal on the deep HDS of gas oil. Applied Catalysis B: Environmental, 53: 169-174.
Soled, S., Miseo, S., Krycak, R., Vroman, H., Ho, T.C., and Riley, K. Nickel molybdo tungstate hydrotreating catalysts. U.S. Patent No. 6299760 to Exxonmobil.
Song, C. (2000). in: Proceedings of Fifth International Conference on Refinery Processing. Held in Conjunction with AIChE Spring National Meeting, New Orleans, 11-14 March, 2002: 3-12.
Song, C. and Saini, A. K. (1995). Strong synergistic effect between dispersed Mo catalyst and H2O for low-severity coal hydroliquefaction. Energy& Fuels, 9: 188-189.
Song, C., Yoneyama, Y., and Kondam, M. R. (2000). Method for preparing a highly active, unsupported high-surface-area MoS2 catalyst. U.S. Patent No. 6156693.
Trakarnpruk, W. and Seentrakoon, B. (2007). Hydrodesulfurization activity of MoS2 and bimetallic catalysts prepared by in situ decomposition of thiosalt. Industrial &Engineering Chemistry Research, 46: 1874-1882.
Yang, H., Chen, J., Briker, Y., Szynkarczuk, R., and Ring, Z. (2005). Effect of nitrogen removal from light cycle oil on the hydrodesulfurization of dibenzo-thiophene, 4-methyldibenzothiophene and 4, 6-dimethyldibenzothiophene. Catalysis Today, 109: 16-23.
Zdrazil, M. (1988). Recent advances in catalysis over sulphides. Catalysis Today, 3: 269-365.
Alonso, G., Petranovskii, V., Del Valle, M., Cruz-Reyes, J., Licea-Claverie, A., and Fuentes, S. (2000). Preparation of WS2 catalysts by in situ decomposition of tetraalkylammonium thiotungstates. Applied Catalysis A: General, 197: 87-97.
Alvarez, L., Espino, J., Ornelas, C., Rico, J. L., Cortez, M. T., Berhault, G., and Alonso, G. (2004). Comparative study of MoS2 and Co/MoS2 catalysts prepared by ex situ/in situ activation of ammonium and tetraalkylammonium thiomolybdates. Journal of Molecular Catalysis. Part A: Chemical 210: 105-117.
Candia, R., Clausen, B. S., and Topsoe, H. (1982). The origin of catalytic synergy in unsupported Co-Mo HDS catalysts. Journal of Catalysis, 77: 564-566.
Chianelli, R. R. (1984). Fundamental studies of transition metal sulfide hydrodesulfurization catalysts. Catalysis Review Engineering, 26: 361-393.
Hagenbach, G., Courty, Ph., and Delmon, B. (1973). Physicochemical investigations and catalytic activity measurements on crystallized molydbenum sulfide-cobalt sulfide mixed catalysts. Journal of Catalysis, 31: 264-273.
Kabe, T., Ishihara, A., and Qian, W. (1999). Hydrodesulfurization and hydro-denitrogenation, Kodansha, Tokyo.
Kalthod, D. G. and Weller, S. (1985). Studies of molybdenum sulfide catalysts: Effects of pretreatment on sintering, stoichiometry, and oxygen chemisorption. Journal of Catalysis, 95: 455-464.
Laredo, G. C. and Cortes, C. M. (2003). Kinetics of hydrodesulfurization of dimethyl dibenzothiophenes in a gas oil narrow-cut fraction and solvent effects. Applied Catalysis A: General, 252: 295-304.
Ma, X., Sakanishi, K., and Mochida, I. (1996). Hydrodesulfurization reactivities of various sulfur compounds in vacuum gas oil. Industrial & Engineering Chemistry Research, 35: 2487-2494.
Pecoraro, T. A., Russell, R., and Chianelli, R. R. (1985). Hydrogenation processes using carbon-containing molybdenum and tungsten sulfide catalysts. US Patent No. 4528089.
Sano, Y., Choi, K. H., Korai, Y., and Mochida, I. (2004). Effects of nitrogen and refractory sulfur species removal on the deep HDS of gas oil. Applied Catalysis B: Environmental, 53: 169-174.
Soled, S., Miseo, S., Krycak, R., Vroman, H., Ho, T.C., and Riley, K. Nickel molybdo tungstate hydrotreating catalysts. U.S. Patent No. 6299760 to Exxonmobil.
Song, C. (2000). in: Proceedings of Fifth International Conference on Refinery Processing. Held in Conjunction with AIChE Spring National Meeting, New Orleans, 11-14 March, 2002: 3-12.
Song, C. and Saini, A. K. (1995). Strong synergistic effect between dispersed Mo catalyst and H2O for low-severity coal hydroliquefaction. Energy& Fuels, 9: 188-189.
Song, C., Yoneyama, Y., and Kondam, M. R. (2000). Method for preparing a highly active, unsupported high-surface-area MoS2 catalyst. U.S. Patent No. 6156693.
Trakarnpruk, W. and Seentrakoon, B. (2007). Hydrodesulfurization activity of MoS2 and bimetallic catalysts prepared by in situ decomposition of thiosalt. Industrial &Engineering Chemistry Research, 46: 1874-1882.
Yang, H., Chen, J., Briker, Y., Szynkarczuk, R., and Ring, Z. (2005). Effect of nitrogen removal from light cycle oil on the hydrodesulfurization of dibenzo-thiophene, 4-methyldibenzothiophene and 4, 6-dimethyldibenzothiophene. Catalysis Today, 109: 16-23.
Zdrazil, M. (1988). Recent advances in catalysis over sulphides. Catalysis Today, 3: 269-365.