Preparation and Characterization of MoO3/Al2O3 Catalyst for Oxidative Desulfurization of Diesel using H2O2: Effect of Drying Method and Mo Loading

The mesoporous MoO3/γ-Al2O3 catalyst was prepared by incipient wetness impregnation method aiming to investigate the effect of drying method and molybdenum content on the catalyst property and performance towards the oxidation of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyle dibenzothiophene (4,6-DMDBT) with H2O2 for deep oxidative desulfurization of diesel fuel. The catalyst was characterized by XRD, BET, BJH and SEM method. The catalyst with 10wt.% and 15wt.% Mo content represent same optimum performance for DBT and 4,6-DMDBT removal, but a catalyst with 10wt.% Mo has higher efficiency than 15wt.% Mo for BT conversion. The SEM images show that use of rotary evaporator in drying step reaches a more homogenous impregnation. The oxidation reactivity of different sulfur compounds was studied which followed the order of DBT>4,6-DMDBT>>BT.




References:
[1] C. Song, X. Ma, "New design approaches to ultra-clean diesel fuels by
deep desulfurization and deep dearomatization," Appl. Catal. B, vol. 41,
2003, pp. 207-238.
[2] R. Wang, G. Zhang, H. Zhao, "Polyoxometalate as effective catalyst for
the deep desulfurization of diesel oil," Catal. Today, vol. 149, 2010, pp.
117-121.
[3] P.D. Filippis, M. Scarsella, N. Verdone, "Oxidative desulfurization I:
Peroxiformic acid oxidation of benzothiophene and dibenzothiophene,"
Ind. Eng. Chem. Res., vol. 49, 2010, pp. 4594-4600.
[4] S. Otsuki, T. Nonaka, N. Takashima, W. Qian, A. Ishihara, T. Imai, T.
Kabe, "Oxidative Desulfurization of Light Gas Oil and Vacuum Gas Oil
by Oxidation and Solvent Extraction," Energy Fuels, vol. 14, 2000, pp.
1232-1239.
[5] S. Murata, K. Murata, K. Kidena, M. Nomura, "A Novel Oxidative
Desulfurization System for Diesel Fuels with Molecular Oxygen in the
Presence of Cobalt Catalysts and Aldehydes," Energy Fuels, vol. 18,
2004, pp. 116-121.
[6] D. Wang, E.W. Qian, H. Amano, K. Okata, A. Ishihara, T. Kabe,
"Oxidative desulfurization of fuel oil Part I. Oxidation of
dibenzothiophenes using tert-butyl hydroperoxide," Appl. Catal. A, vol.
253, 2003, pp. 91-99.
[7] A. Ishihara, D. Wang, F. Dumeignil, H. Amano, E.W. Qian, T. Kabe,
"Oxidative desulfurization and denitrogenation of a light gas oil using
an oxidation/adsorption continuous flow process," Appl. Catal. A, vol.
279, 2005, pp. 279-287.
[8] P.D. Filippis, M. Scarsella, "Oxidative Desulfurization: Oxidation
Reactivity of Sulfur Compounds in Different Organic Matrixes," Energy
Fuels, vol. 17, 2003, pp. 1452-1455.
[9] W. Trakarnpruk, K. Rujiraworawut, "Oxidative desulfurization of Gas
oil by polyoxometalates catalyst," Fuel Process Technol, vol. 90 ,2009,
pp. 411-414.
[10] V. Hulea, F. Fajula, J. Bousquet, "Mild Oxidation with H2O2 over Ti-
Containing Molecular Sieves, A very Efficient Method for Removing
Aromatic Sulfur Compounds from Fuels," J. Catal. Vol. 198 ,2001, pp.
179-186.
[11] A. Chica, A. Corma, M.E. Domine, "Catalytic oxidative desulfurization
(ODS) of diesel fuel on a continuous fixed-bed reactor," J. Catal., vol.
242 2006, pp. 299-308.
[12] Ch. Jin, G. Li, X. Wang, Y. Wang, L. Zhao, D. Sun, "A titanium
containing micro/mesoporous composite and its catalytic performance
in oxidative desulfurization," Microporous and Mesoporous Materials,
vol. 111, 2008, pp. 236-242.
[13] Y. Wang, G. Li, X. Wang, Ch. Jin, Oxidative Desulphurization of 4,6-
Dimethyldibenzothiophene with Hydrogen Peroxide over Ti-HMS,
Energy Fuels 21 (2007) 1415-1419.
[14] V.V.D.N. Prasad, K.E. Jeong, H.G. Chae, C.U. Kim, S.Y. Jeong,
"Oxidative desulfurization of 4,6-dimethyl dibenzothiophene and light
cycle oil over supported molybdenum oxide catalysts," Catal. Commun.
Vol. 9, 2008, pp. 1966-1969.
[15] L.C. Caero, E. Hernandez, F. Pedraza, F. Murrieta, Oxidative
desulfurization of synthetic diesel using supported catalysts Part I. Study
of the operation conditions with a vanadium oxide based catalyst, Catal.
Today, vol. 107-108, 2005, pp. 564-569.
[16] X.M. Yan, J.H. Lei, D. Liu, Y.Ch. Wu, L.P. Guo, "Oxidative
Desulfurization of Diesel Oil Using Mesoporous Phosphotungstic
Acid/SiO2 as Catalyst," J. Chine. Chem. Soc., vol. 54, 2007, pp. 911-
916.
[17] J.L. Garcia-Gutierrez, G.A. Fuentes, M.E. Hernandez-Teran, P. Garcia,
F. Murrieta Guevara, F. Jimenez-Cruz, "Ultra-deep oxidative
desulfurization of diesel fuel by the Mo/Al2O3-H2O2 system: The effect
of system parameters on catalytic activity," Appl. Catal. A. vol. 334,
2008, pp. 366-373.
[18] J.L. Garcia-Gutierrez, G.A. Fuentes, M.E. Hernandez-Teran, "Ultradeep
oxidative desulfurization of diesel fuel with H2O2 catalyzed under
mild conditions by polymolybdates supported on Al2O3," Appl. Catal.
A, vol. 305, 2006, pp. 15-20.
[19] Y. Jia, G. Li, G. Ning," Efficient oxidative desulfurization (ODS) of
model fuel with H2O2 catalyzed by MoO3/Al2O3 under mild and solvent
free conditions," Fuel Process. Technol., vol. 92, 2011, pp. 106-111.