MODIFICATION OF NiMo/Al2O3 CATALYSTS BY BORON ADDITION AND THEIR EVALUATION IN HDS OF 4,6-DMDBT AND DBT

  • P. Torres-Mancera
  • J. Ramírez
  • A. Gutiérrez-Alejandre
  • R. Cuevas
Keywords: hydrodesulfurization, 4, 6-Dimethyldibenzothiophene, NiMo/Al2O3-B(X)

Abstract

The modification of acid and hydrodesulfurization catalytic functions due to boron incorporation on NiMo/Al2O3 and its effect on the sulfur removal of 4,6 DMDBT and DBT were studied. The results show that 3.0 wt% B addition to Al2O3 does not diminish the textural properties. In addition, boron enhances both density and strength of the acid sites. By means of UV-vis DRS it was found that for the boron-modified catalyst, the amount of metals in strong interaction with the support, Ni and Mo tetrahedrally coordinated, is lower than for the boron-free catalyst, suggesting an increase in the number of hydrodesulfurization sites. It was shown that boron-modified support and catalyst perform the 4,6-DMDBT isomerization. Besides in the catalyst the hydrogenation function was improved. Therefore it was obtained a catalyst able to remove sulfur from highly refractory compounds like 4,6-DMDBT by the benefit from alternative reaction routes (hydrogenation and isomerization).

References

Bataille, F., Lemberton, J. L., Perot G., Leyrit, P., Cseri, T., Marchall, N. y Kasztelan, S. (2001). Sulfided Mo and CoMo supported on zeolite as hydrodesulfurization catalysts: transformation of dibenzothiophene and 4,6-dimethyldibenzothiophene. Applied Catalysis A: General 220, 191-205.

Curtin, T., McMonagle, J. y Hodnett, B. (1992). Influence of boria loading on the acidity of B2O3/Al2O3 catalysts for the conversion of cyclohexanone oxime to caprolactam. Applied Catalysis A: General 93, 91-101.

Dien, L., Sato, T., Imamura, M., Shimada, H. y Nishijima, A (1997). Spectroscopic Characterization of Ni–Mo/γ-Al2O3–B2O3 Catalysts for Hydrodesulfurization of Dibenzothiophene. Journal. of Catalysis 170, 357-365.

Dien, L., Sato, T., Imamura, M., Shimada, H y Nishijima, A. (1998). The effect of boron on HYD, HC and HDS activities of model compounds over Ni–Mo/γ-Al2O3–B2O3 catalysts. Applied Catalysis B: Environmental 16, 255-260.

Dubois, J. y Fujieda, S. (1996). Effects of boron in Co-Mo/B-Al2O3 hydrotreatment catalysts. Catalysis Today 29, 191-195.

Flego, C., y O’Neil, W. (1999). Characterization of γ-alumina and borated alumina catalysts. Applied Catalysis A: General 185, 137-152.

Forni, L., Fornasari, G., Tosi, C., Trifiro, F., Vaccari, A., Dumeignil, F. y Grimblot, J. (2003). Non-conventional sol–gel synthesis for the production of boronalumina catalyst applied to the vapour phase Beckmann rearrangement. Applied Catalysis A: General 248, 47-57.

Hédoire, C., Louis, C., Davidson, A., Breysse, M., Maugé, F. y Vrinat, M. (2003). Support effect in hydrotreating catalysts: hydrogenation properties of molybdenum sulfide supported on β-zeolites of various acidities. Journal of Catalysis 220, 433-441.

Ho, T. (2004). Deep HDS of diesel fuel: chemistry and catalysis. Catalysis Today 98, 3-18.

Isoda, T., Nagao, S., Ma, X., Korai, Y. y Mochida. I. (1996). Hydrodesulfurization pathway of 4,6-dimethyldibenzothiophene through isomerization over Y-zeolite containing CoMo/Al2O3 catalyst. Energy & Fuels 10, 1078-1082.

Landau, M. V., Berger, D. y Herskowitz, M. (1996). Hydrodesulfurization of methyl-substituted dibenzothiophenes: Fundamental study of routes to deep desulfurization. Journal of Catalysis 159, 236-245.

Lecrenay, E., Sakanishi, K. y Mochida, I. (1997). Catalytic hydrodesulfurization of gas oil and model sulfur compounds over commercial and laboratory-made CoMo and NiMo catalysts: Activity and reaction scheme. Catalysis Today 39, 13-20.

Lecrenay, E., Sakanishi, K., Mochida, I. y Suzuka, T. (1998). Hydrodesulfurization activity of CoMo and NiMo catalysts supported on some acidic binary oxides. Applied Catalysis A: General 175, 237-243.

Lewandoski, M. y Sarback, Z. (2000). The effect of boron addition on hydrodesulfurization and hydrodenitrogenation activity of NiMo/Al2O3 catalysts Fuel 79, 487-495.

Li, D., Nishijima, A. y Morris, D. E. (1999). Zeolite-Supported Ni and Mo Catalysts for Hydrotreatments: I. Catalytic Activity and Spectroscopy. Journal of Catalysis 182, 339-348.

Marín, C., Escobar, J., Galván, E., Murrieta, F., Zárate, R. y Vaca, H. (2005). Light straight-run gas oil hydrotreatment over sulfided CoMoP/Al2O3-USY zeolite catalysts. Fuel processing Technology. 86, 391-405.

Muralidhar, G., Massot, F. E. y Shabtai, J. (1984). Catalytic functionalities of supported sulfides : I. Effect of support and additives on the CoMo catalyst. Journal of Catalysis 85, 44-52.

Pérot, G. (2003). Hydrotreating catalysts containing zeolites and related materials – mechanistic aspects related to deep desulfurization. Catalysis Today 86, 111-128.

Poling, B. E., Prausnitz, J. M. y O’Connell, J. P. (2001). The properties of gases and liquids. McGraw-Hill, 5th Edition. Ramírez, J., Castillo, P., Cedeño, L., Cuevas, R., Castillo, M., Palacios, J. y López-Agudo, A. (1995). Effect of boron addition on the activity and selectivity of hydrotreating CoMo/Al2O3 catalysts. Applied Catalysis A: General: 132, 317-334.

Satterfield, C. N (1980). Heterogeneous catalysis in practice. McGraw-Hill. Song, C. (2003). An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel. Catalysis Today 86, 211-263.

Tanabe, K. (1970). Solid Acid and Bases. Academic press, New York.

Torres-Mancera, P., Ramírez, J., Cuevas, R., Gutierrez-Alejandre, A., Murrieta, F. y Luna, R. (2005). Hydrodesulfurization of 4,6-DMDBT on NiMo and CoMo catalysts supported on B2O3-Al2O3. Catalysis Today 107-108, 551-558.

Whitehurst, D., Isoda, T. y Mochida, I. (1998). Present state of the art and future challenges in the hydrodesulfurization of polyaromatic sulfur compounds. Advances in Catalysis 42,345-471.

Wilke, C. R. y Chang, P. (1955). Correlation of diffusion coefficients in dilute solutions. AIChE Journal 1,264-270.

Xu, B., Cheng, S., Jiang, S. y Zhu, Q., (1999). Gas phase beckmann rearrangement of cyclohexanone oxime over zirconia-supported boria catalysts. Applied Catalysis A: General 188, 361-368.

Yumoto, M., Usui, K. Watanabe, K., Idei, K., y Yamazaki, H. (1997). Development of a Cosmo deep HDS catalyst for diesel fuel. Catalysis Today 35, 45-50
Published
2020-08-19
How to Cite
Torres-Mancera, P., Ramírez, J., Gutiérrez-Alejandre, A., & Cuevas, R. (2020). MODIFICATION OF NiMo/Al2O3 CATALYSTS BY BORON ADDITION AND THEIR EVALUATION IN HDS OF 4,6-DMDBT AND DBT. Revista Mexicana De Ingeniería Química, 5(3), 219-226. Retrieved from http://www.rmiq.org/ojs311/index.php/rmiq/article/view/1972