Synthesis and catalytic evaluation of CoMo/SBA-15 catalysts for oxidative removal of dibenzothiophene from a model diesel

Ramos, J.M.; Wang, Jinan; Chen, L.F.; Arellano, U.; Ramı́rez, S.; Sotelo, Rogelio; Schachat, Persi

doi:10.1016/j.catcom.2015.09.007

Cited by 25 publications

(10 citation statements)

References 28 publications

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“…The SBA-15 has proven to be a suitable support to immobilize POMs when functionalized with appropriate functional groups [ 44 , 51 , 60 , 61 ]. In addition, this support has demonstrated that it can be used efficiently in oxidative desulfurization processes [ 51 , 54 , 62 , 63 , 64 , 65 , 66 , 67 ]. In this work, the trimethylammonium functional group was strategically selected to immobilize effectively the anionic PW 12 by ionic interaction.…”

Section: Resultsmentioning

confidence: 99%

Improving the Catalytic Performance of Keggin [PW12O40]3− for Oxidative Desulfurization: Ionic Liquids versus SBA-15 Composite

et al. 2018

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Different methodologies were used to increase the oxidative desulfurization efficiency of the Keggin phosphotungstate [PW12O40]3− (PW12). One possibility was to replace the acid proton by three different ionic liquid cations, forming the novel hybrid polyoxometalates: [BMIM]3PW12 (BMIM as 1-butyl-3-methylimidazolium), [BPy]3PW12 (BPy as 1-butylpyridinium) and [HDPy]3PW12 (HDPy as hexadecylpyridinium. These hybrid Keggin compounds showed high oxidative desulfurization efficiency in the presence of [BMIM]PF6 solvent, achieving complete desulfurization of multicomponent model diesel (2000 ppm of S) after only 1 h, using a low excess of oxidant (H2O2/S = 8) at 70 °C. However, their stability and activity showed some weakness in continuous reused oxidative desulfurization cycles. An improvement of stability in continuous reused cycles was reached by the immobilization of the Keggin polyanion in a strategic positively-charged functionalized-SBA-15 support. The PW12@TM–SBA-15 composite (TM is the trimethylammonium functional group) presented similar oxidative desulfurization efficiency to the homogeneous IL–PW12 compounds, having the advantage of a high recycling capability in continuous cycles, increasing its activity from the first to the consecutive cycles. Therefore, the oxidative desulfurization system catalyzed by the Keggin-type composite has high performance under sustainable operational conditions, avoids waste production during recycling and allows catalyst recovery.

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Section: Resultsmentioning

confidence: 99%

Improving the Catalytic Performance of Keggin [PW12O40]3− for Oxidative Desulfurization: Ionic Liquids versus SBA-15 Composite

et al. 2018

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“…The activity of MoO 3 /SiO 2 further increased after the introduction of different alkaline earth metals (Ca, Ba, Sr and Mg) in the silica phase [121], highlighting the key role played by the Lewis and Bronsted acid sites in the behavior of the oxidation [122]. In order to prepare molybdenum ODS catalysts with larger surface area and larger pore diameter, CoMo/SBA-15 compounds were obtained by impregnating the SBA- 15 [123]. The XRD analysis confirmed the retention of the mesoporous structure after the impregnation procedure with a slight alteration of the loop shape and pore distribution with respect to original SBA-15, due to percolation of Co and Mo oxides within mesopores, associated with a high dispersion of the metal oxides on the surface of the catalyst.…”

Section: Molybdenum Oxidesmentioning

confidence: 99%

SBA-15 Anchored Metal Containing Catalysts in the Oxidative Desulfurization Process

2019

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Recalcitrant sulfur compounds are common impurities in crude oil. During combustion they produce SOx derivatives that are able to affect the atmospheric ozone layer, increasing the formation of acid rains, and reducing the life of the engine due to corrosion. In the last twenty years, many efforts have been devoted to develop conventional hydrodesulfurization (HDS) procedures, as well as alternative methods, such as selective adsorption, bio-desulfurization, oxidative desulfurization (ODS) under extractive conditions (ECODS), and others. Among them, the oxidative procedures have been usually accomplished by the use of toxic stoichiometric oxidants, namely potassium permanganate, sodium bromate and carboxylic and sulfonic peracids. As an alternative, increasing interest is devoted to selective and economical procedures based upon catalytic methods. Heterogeneous catalysis is of relevance in industrial ODS processes, since it reduces the leaching of active species and favors the recovery and reuse of the catalyst for successive transformations. The heterogenization of different types of high-valent metal transition-based organometallic complexes, able to promote the activation of stoichiometric benign oxidants like peroxides, can be achieved using various solid supports. Many successful cases have been frequently associated with the use of mesoporous silicas that have the advantage of easy surface modification by reaction with organosilanes, facilitating the immobilization of homogeneous catalysts. In this manuscript the application of SBA-15 as efficient support for different active metal species, able to promote the catalytic ODS of either model or real fuels is reviewed, highlighting its beneficial properties such as high surface area, narrow pore size distribution and tunable pore diameter dimensions. Related to this topic, the most relevant advances recently published, will be discussed and critically described.

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“…Because heterocyclic sulfur compounds are relatively large molecules, catalyst pore diameter and surface area must be considered as part of catalyst design. Many previous investigations have focused on the transition metals oxides supported on oxide solids including titania, alumina, ceria, niobia, silica, and zirconia. ,, Activated carbon materials are also reported as adsorbents and catalyst support for ODS reactions. − ,,, Some porous materials, including especially mesoporous materials or metal doped MCM-41 and SBA-15 have been used as catalyst supports due to their uniform structure consisting of large pores and possessing high surface areas. − …”

Section: Introductionmentioning

confidence: 99%

“…Fe, Co, Ni, Cu, V, Mo, W oxides based catalysts have been proven to be active for sulfur compound oxidation. and their catalytic activities greatly depend on the support, preparation method, and oxidizing agent used. ,,,, Due to the high activity of V 2 O 5 for SO 2 oxidation to produce sulfuric acid, and MoO 3 or WO 3 as precursors of the active phase for HDS process, these three oxides received much attention in the ODS reactions. − In comparison with WO 3 and MoO 3 , vanadia is a cheaper oxide. From the practical and economical points of view, V 2 O 5 has a greater potential to be applied as catalyst active phase for ODS treatment.…”

Section: Introductionmentioning

confidence: 99%

“…and their catalytic activities greatly depend on the support, preparation method, and oxidizing agent used. 23,24,31,34,36 Due to the high activity of V 2 O 5 for SO 2 oxidation to produce sulfuric acid, and MoO 3 or WO 3 as precursors of the active phase for HDS process, these three oxides received much attention in the ODS reactions. 37−39 In comparison with WO 3 and MoO 3 , vanadia is a cheaper oxide.…”

Section: Introductionmentioning

confidence: 99%

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VO_x Core–Shell Catalysts for One-Pot Oxidation and Separation of Refractory Multiaromatic Sulfur Compounds in a Model Diesel

Arellano

Wang

Chen

et al. 2017

Ind. Eng. Chem. Res.

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Ti-MCM-41 supported vanadia core−shell catalysts were prepared and their catalytic activity was evaluated in a biphasic reactor for simultaneous oxidation/separation of refractory organosulfur compounds (dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT)) in a model diesel fuel. Formation of core−shell structure in the catalyst nanoparticles resulted from the surface diffusion of the vanadium ion in semimelted state of vanadia during the calcination process. It was found that both the value of V 5+ /(V 4+ + V 5+ ) and the surface acidity of the catalysts generally increased as the content of V content increased to 15 wt % of vanadium and correlated well with variations in catalytic activity, indicating that the surface V 5+ and surface acid sites were chiefly responsible for the oxidation of sulfur compounds. The reactivity of organosulfur compounds was influenced by their steric hindrance. Addition of carboxylic acid (acetic acid or formic acid) promoted the sulfur oxidation efficiency via formation of more stable and active oxygen species like peroxometallic and superoxometallic species on the catalyst surface. Approximately 99% of the sulfur compounds were removed with the best catalysts containing 15 wt % V at a reaction temperature of 60 °C and within 60 min. This one-pot organosulfur oxidation and separation method was proven to be efficient, economical, and practical for deep desulfurization of diesel fuels containing refractory organosulfur compounds.

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Synthesis and catalytic evaluation of CoMo/SBA-15 catalysts for oxidative removal of dibenzothiophene from a model diesel

Cited by 25 publications

References 28 publications

Improving the Catalytic Performance of Keggin [PW12O40]3− for Oxidative Desulfurization: Ionic Liquids versus SBA-15 Composite

Improving the Catalytic Performance of Keggin [PW12O40]3− for Oxidative Desulfurization: Ionic Liquids versus SBA-15 Composite

SBA-15 Anchored Metal Containing Catalysts in the Oxidative Desulfurization Process

VO_x Core–Shell Catalysts for One-Pot Oxidation and Separation of Refractory Multiaromatic Sulfur Compounds in a Model Diesel

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Synthesis and catalytic evaluation of CoMo/SBA-15 catalysts for oxidative removal of dibenzothiophene from a model diesel

Cited by 25 publications

References 28 publications

Improving the Catalytic Performance of Keggin [PW12O40]3− for Oxidative Desulfurization: Ionic Liquids versus SBA-15 Composite

Improving the Catalytic Performance of Keggin [PW12O40]3− for Oxidative Desulfurization: Ionic Liquids versus SBA-15 Composite

SBA-15 Anchored Metal Containing Catalysts in the Oxidative Desulfurization Process

VOx Core–Shell Catalysts for One-Pot Oxidation and Separation of Refractory Multiaromatic Sulfur Compounds in a Model Diesel

Contact Info

Product

Resources

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VO_x Core–Shell Catalysts for One-Pot Oxidation and Separation of Refractory Multiaromatic Sulfur Compounds in a Model Diesel