Deep oxidative desulfurization of diesel fuels using homogeneous and SBA-15-supported peroxophosphotungstate catalysts

Julião, Diana; Mirante, Fátima; Ribeiro, Susana; Gomes, Ana C.; Valença, Rita; Ribeiro, Jorge C.; Pillinger, Martyn; Castro, Balt­azar de; Gonçalves, Isabel S.; Balula, Salete S.

doi:10.1016/j.fuel.2018.11.095

Cited by 116 publications

(59 citation statements)

References 45 publications

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Section: Phosphotungstic Containing Pomsmentioning

confidence: 99%

“…No relevant differences, on the catalytic activity, have been detected for the two different polyoxotungstates containing Bi III or Sb III , respectively. In a recent paper, a contribution based on the use of a composite material formed by a phosphorous-containing tetranuclear peroxotungstate {PO 4 [WO 2 (O 2 ) 2 ] 4 } 3 Venturello anion symbolized as PW 4 , immobilized on trimethylammonium functionalized SBA-15 (PW 4 /tma-SBA-15) through an impregnation method, employed as catalyst for the ODS of model and real fuels, has been published [206]. Impressive data concerning activity and stability of heterogenized POM, have been reported by authors; moreover, carefully investigations on the fresh heterogeneous catalyst and on the material recovered after the successive recycling steps, showed that during the heterogenization and oxidation experiments an equilibrium between the two species PW 4 and the α-Keggin heteropolyanion [PW 12 O 40 ] 3− (PW 12 ), cannot be ruled out.…”

Section: Phosphotungstic Containing Pomsmentioning

confidence: 99%

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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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Section: Phosphotungstic Containing Pomsmentioning

confidence: 99%

Section: Phosphotungstic Containing Pomsmentioning

confidence: 99%

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

2019

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“…Therefore, the Venturello structure contains already active peroxo groups that can easily promote sulfur oxidation. In fact, the Venturello peroxotungstate, PW 4 , has been successfully used as a highly active catalyst in different oxidative reactions [15,[24][25][26][27][28][29]. However, most of these studies use the Venturello compound as a homogeneous catalyst, which is difficult to recover and reuse [30].…”

Section: Introductionmentioning

confidence: 99%

An Effective Hybrid Heterogeneous Catalyst to Desulfurize Diesel: Peroxotungstate@Metal–Organic Framework

et al. 2020

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A peroxotungstate composite comprising the chromium terephthalate metal–organic framework MIL-101(Cr) and the Venturello peroxotungstate [PO4{WO(O2)2}4]3− (PW4) has been prepared by the impregnation method. The PW4@MIL-101(Cr) composite presents high catalytic efficiency for oxidative desulfurization of a multicomponent model diesel containing the most refractory sulfur compounds present in real fuels (2000 ppm of total S). The catalytic performance of this heterogeneous catalyst is similar to the corresponding homogeneous PW4 active center. Desulfurization efficiency of 99.7% was achieved after only 40 min at 70 °C using H2O2 as an oxidant and an ionic liquid as an extraction solvent ([BMIM]PF6, 2:1 model diesel/[BMIM]PF6). High recycling and reusing capacity was also found for PW4@MIL-101(Cr), maintaining its activity for consecutive oxidative desulfurization cycles. A comparison of the catalytic performance of this peroxotungstate composite with others previously reported tungstate@MIL-101(Cr) catalysts indicates that the presence of active oxygen atoms from the peroxo groups promotes a higher oxidative catalytic efficiency in a shorter reaction time.

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“…Many different types of transition metal catalysts have been explored for ODS . The first organometallic complexes to be reported for ODS were the cyclopentadienyl molybdenum tricarbonyl complexes [ η 5 ‐CpMo(CO) 3 R] (R = Me, CH 2 ‐ p C 6 H 4 ‐CO 2 Me, CH 2 COOH) .…”

Section: Introductionmentioning

confidence: 99%

Desulfurization of model and real fuels by extraction and oxidation processes using an indenylmolybdenum tricarbonyl pre‐catalyst

Julião

Gomes

Pillinger

et al. 2020

Applied Organom Chemis

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Regulations on the permissible levels of sulfur in transportation fuels are becoming ever more strict, with a global shift towards “zero sulfur” fuels, and the revamp of existing hydrodesulfurization (HDS) facilities to meet these lower caps is cost‐prohibitive. Metal‐catalyzed sulfoxidation chemistry is viewed as an economically viable desulfurization strategy that could complement conventional HDS technology. In the present work, the complex [η5‐IndMo(CO)3Me] (1) (Ind = indenyl) was employed in the catalytic oxidative desulfurization (CODS) of model and real liquid fuels, using aqueous hydrogen peroxide (H2O2) as oxidant. After optimization of the CODS reaction parameters (diesel/H2O2 ratio, catalyst amount, temperature), a high‐sulfur (2000 ppm) model diesel containing benzothiophene, dibenzothiophene, 4‐methyldibenzothiophene and 4,6‐dimethyldibenzothiophene could be completely desulfurized within 2 hr under solvent‐free conditions or in the presence of the ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([BMIM]PF6) as extraction solvent. The catalyst formed under solvent‐free conditions could be recycled without a significant decrease in desulfurization activity. The high performance of the CODS system was verified in the sulfur removal from a commercial untreated diesel fuel with a sulfur content of 2300 ppm, and a jet fuel with a sulfur content of 1100 ppm. Solvent‐free CODS in combination with initial/final extraction gave desulfurization efficiencies of 70% for the diesel fuel and 55% for the jet fuel. CODS with [BMIM]PF6 in combination with initial/final extraction led to a sulfur removal of 95.9% for the diesel fuel, which is one of the best results yet reported for ODS of commercial diesels.

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Deep oxidative desulfurization of diesel fuels using homogeneous and SBA-15-supported peroxophosphotungstate catalysts

Cited by 116 publications

References 45 publications

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

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

An Effective Hybrid Heterogeneous Catalyst to Desulfurize Diesel: Peroxotungstate@Metal–Organic Framework

Desulfurization of model and real fuels by extraction and oxidation processes using an indenylmolybdenum tricarbonyl pre‐catalyst

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