Deep Oxidative Desulfurization of Model Fuels Catalyzed by Subnanosized Ti Oxoclusters

Zhang, Tong; Chen, Xuejing; Ding, Bingjie; Ding, Zuoji; Wang, Yajun; Qiu, Hewen; Jiang, Yongjun; Dai, Sheng; Hou, Zhenshan

doi:10.1021/acs.energyfuels.1c03766

Cited by 19 publications

(16 citation statements)

References 78 publications

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“…The increasing consumption of petroleum products for energy production has engendered various concerns. , These concerns include environmental pollution from the release of contaminants and pollutant gases such as SO x and NO x (the cause of acid rain). , Sulfur-containing molecules in the form of hydrogen sulfide bring about corrosion in transmission pipes, tanks, and other pieces of equipment. , To minimize the emission of sulfur oxides, international organizations have enacted regulations to limit the amount of sulfur present in fuels to 15 ppm, which is known as very low sulfur gasoline. − …”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Catalytic Oxidative Desulfurization of Gasoline Using PMnW₁₁@PANI@CS as a New Inorganic–Organic Hybrid Nanocatalyst

2022

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In this manuscript, to obtain a high-purity fuel, a new inorganic–organic hybrid (IOH) nanocomposite (PMnW11@PANI@CS) based on mono-supplanted heteropolyanion (PMnW11), polyaniline (PANI), and chitosan (CS) was synthesized successfully. The synthesized nanocomposite (PMnW11@PANI@CS) was employed as a nanocatalyst in the nanocatalytic oxidative desulfurization (NODS) process. PMnW11@PANI@CS was confirmed by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), UV–vis, Fourier transform infrared spectroscopy (FT-IR), and energy-dispersive X-ray spectroscopy (EDX) analysis. The elimination of hazardous molecules containing sulfur from real and simulated gasoline was done according to the NODS process. The sulfur compounds in gasoline were oxidized and disengaged effectively under a mild reaction. PMnW11@PANI@CS with nanocatalytic activity was used as a recyclable nanocatalyst in this process. PMnW11@PANI@CS was evaluated in the NODS process using a combination of CH3COOH and H2O2 in a 1:2 volume ratio as an oxidant system. The results were compared with the obtained results of a simulated gasoline oxidation process under the same conditions. Furthermore, the effect of the nanocatalyst, types of oxidation system, dosage of the nanocatalyst, temperature, and reaction time on the NODS efficiency were investigated. Experimental results show that owing to the excellent efficiency of the PMnW11@PANI@CS NODS system, it can be a promising method to attain super clean gasoline.

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Section: Introductionmentioning

confidence: 99%

Highly Efficient Catalytic Oxidative Desulfurization of Gasoline Using PMnW₁₁@PANI@CS as a New Inorganic–Organic Hybrid Nanocatalyst

2022

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“…Surprisingly, the chemical states of V species would be adjusted by the molar ratio of the IL and V atoms, and the stabilizing V oxo-clusters were highly active and stable in catalyzing the oxidation of cyclohexane with H 2 O 2 . 51 As a continuation of our efforts to design easily accessible, highly efficient, and stable metal oxo-clusters for catalytic oxidation, 52 in this work, we report the IL consisting of protic N-butyl imidazolium and picolinate anion, which was able to stabilize the oligovanadate species. The as-obtained V oxoclusters were highly active catalysts for oxidative cleavage linkages of β−O−4 lignin model compounds.…”

Section: Introductionmentioning

confidence: 96%

Ionic Liquid-Stabilizing Vanadium Oxo-Cluster Catalysts for One-Step Selective Oxidative Cleavage of β–O–4 Lignin Model Compounds

Wang

Ding

et al. 2023

Energy Fuels

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An easily accessible and efficient catalyst is highly promising for the cleavage of the C–C bond and C–O bond of β–O–4 lignin model compounds. In this work, ionic liquid [Bim][Pic] (Bim = 1-butyl imidazolium, Pic = picolinate anion)-stabilizing vanadium oxo-cluster catalysts were constructed conveniently for selective aerobic oxidation to cleave the β–O–4 linkages into phenols, eaters and acids. The as-synthesized vanadium oxo-cluster catalysts Bim-V-n (n = 1–3) were characterized by Fourier transform infrared (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), electron paramagnetic resonance (EPR), mass spectrometry (MS), and elemental analysis. The vanadium in the catalyst exists stably in a mixed-valence state of V4+ and V5+. Molecular oxygen was activated through the mutual transformation of V4+ and V5+ to form superoxide free radicals, which were captured by the EPR spectrum. Especially, Bim-V-2 afforded superior catalytic activity under aerobic conditions (10 h, 120 °C). The highly reversible interconversion of V4+ and V5+ species in vanadium oxo-cluster allowed the coexistence of the mixed-valence vanadium species, which was responsible for oxidizing β–O–4 alcohols to β–O–4 ketones. Moreover, superoxide free radicals can facilitate the cleavage of C–C and C–O bonds in β–O–4 ketones. Especially, 1-butyl imidazolium also played a positive role in the cleavage of C–O bonds by the action of the cation protons. No appreciable loss of catalytic activity was observed, and the catalyst could be recovered and reused up to five times, reflecting the excellent recyclability of the present vanadium oxo-cluster catalysts. The catalytic system can be extended for the cleavage of the C–C bond and C–O bond of β–O–4 of the other lignin model compounds, and the reaction could still be completed efficiently. This provides a new perspective for the selective aerobic oxidation of β–O–4 lignin without co-catalysts.

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“…Other methods for the removal of sulfur are the use of Ti oxoclusters in ionic liquids with an extractant, such as alcohols and glycol derivatives, or the application of heterogeneous nanohybrid POMs with magnetic properties to ease the purification of the reaction medium. , While the removal of sulfuric compounds is achieved to a high degree and under mild conditions, the synthesis strategies are far more complex and money-consuming than the comparably simple and cheap HPA-5 Keggin-type synthesis . The desulfurization of fuels with Lindqvist-type HPAs has also been conducted and is slightly faster than the desulfurization with Keggin-type HPAs.…”

Section: Introductionmentioning

confidence: 99%

“…16,17 An efficient recycling of the catalyst has already been established via membrane filtration. 23 Other methods for the removal of sulfur are the use of Ti oxoclusters in ionic liquids with an extractant, such as alcohols and glycol derivatives, 24 or the application of heterogeneous nanohybrid POMs with magnetic properties to ease the purification of the reaction medium. 21,22 While the removal of sulfuric compounds is achieved to a high degree and under mild conditions, the synthesis strategies are far more complex and money-consuming than the comparably simple and cheap HPA-5 Keggin-type synthesis.…”

Section: ■ Introductionmentioning

confidence: 99%

Extractive Catalytic Oxidative Deoxygenation of Model Fuels Catalyzed by a Vanadium-Substituted Heteropolyacid and Molecular Oxygen

et al. 2023

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Extractive catalytic oxidative deoxygenation (ECODO) completes extractive catalytic oxidative desulfurization (ECODS) and extractive catalytic oxidative denitrogenation by removing organic oxygen from fuels. This is particularly necessary for renewable fuels to make them more stable and efficient. In ECODO, compounds such as cresol, furan, and their derivatives could be completely oxidized under oxygen at 20 bar and 120 °C using an aqueous heteropolyacid catalyst solution. The oxidation products were separated in situ in the three-phase process, either as CO 2 or CO in the gas phase or as water-soluble organic acids like formic and acetic acid as well as acetone. In the case of stable dibenzofuran (DBF), the conversion could be drastically increased from only 27% to above 50% by tuning the reaction conditions and optimizing the catalyst loading by a design of experiment. Moreover, the amount of oxygen in the gas phase could be drastically reduced from 20 to 4 bar operating in 20 bar of synthetic air without limiting the performance of the catalyst. Furthermore, it could be shown that the parallel ECODS in the presence of an oxygenate like DBF leads to better desulfurization of model gasoline than without. The ECODO therefore offers a potential alternative to the classical hydrodeoxygenation, which is not only more energy-efficient but also replaces the expensive hydrogen with cheap air and avoids additional unit operations for fuel cleaning.

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Deep Oxidative Desulfurization of Model Fuels Catalyzed by Subnanosized Ti Oxoclusters

Cited by 19 publications

References 78 publications

Highly Efficient Catalytic Oxidative Desulfurization of Gasoline Using PMnW₁₁@PANI@CS as a New Inorganic–Organic Hybrid Nanocatalyst

Highly Efficient Catalytic Oxidative Desulfurization of Gasoline Using PMnW₁₁@PANI@CS as a New Inorganic–Organic Hybrid Nanocatalyst

Ionic Liquid-Stabilizing Vanadium Oxo-Cluster Catalysts for One-Step Selective Oxidative Cleavage of β–O–4 Lignin Model Compounds

Extractive Catalytic Oxidative Deoxygenation of Model Fuels Catalyzed by a Vanadium-Substituted Heteropolyacid and Molecular Oxygen

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Deep Oxidative Desulfurization of Model Fuels Catalyzed by Subnanosized Ti Oxoclusters

Cited by 19 publications

References 78 publications

Highly Efficient Catalytic Oxidative Desulfurization of Gasoline Using PMnW11@PANI@CS as a New Inorganic–Organic Hybrid Nanocatalyst

Highly Efficient Catalytic Oxidative Desulfurization of Gasoline Using PMnW11@PANI@CS as a New Inorganic–Organic Hybrid Nanocatalyst

Ionic Liquid-Stabilizing Vanadium Oxo-Cluster Catalysts for One-Step Selective Oxidative Cleavage of β–O–4 Lignin Model Compounds

Extractive Catalytic Oxidative Deoxygenation of Model Fuels Catalyzed by a Vanadium-Substituted Heteropolyacid and Molecular Oxygen

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Highly Efficient Catalytic Oxidative Desulfurization of Gasoline Using PMnW₁₁@PANI@CS as a New Inorganic–Organic Hybrid Nanocatalyst

Highly Efficient Catalytic Oxidative Desulfurization of Gasoline Using PMnW₁₁@PANI@CS as a New Inorganic–Organic Hybrid Nanocatalyst