One-step oxidehydration of glycerol to acrylic acid using ETS-10-like vanadosilicates

Paula, Alex Silva; Possato, Luiz G.; Ratero, Davi Rubinho; Contro, Janine; Keinan‐Adamsky, Keren; Soares, Ricardo R.; Goobes, Gil; Martins, Leandro; Nery, José Geraldo

doi:10.1016/j.micromeso.2016.05.014

Cited by 32 publications

(22 citation statements)

References 43 publications

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“…In the first step, glycerol is dehydrated to acrolein on acid sites [2][3][4][5][6][7][8][9][10][11][12][13]. The second step is the selective oxidation of acrolein to acrylic acid, catalyzed by redox sites [14][15][16][17][18][19][20][21][22][23][24]. The combination of these two reaction steps using a single bifunctional catalytic bed (the oxydehydration reaction) offers advantages including the ideal thermal balance provided by coupling the exothermic oxidation reaction with the endothermic dehydration reaction [2,25,26].…”

Section: Introductionmentioning

confidence: 99%

Thermal treatments of precursors of molybdenum and vanadium oxides and the formed Mo x V y O z phases active in the oxydehydration of glycerol

Possato

Cassinelli

Meyer

et al. 2017

Applied Catalysis A: General

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This paper presents an in situ study of the crystallographic phases formed during the thermal treatment of precursors of vanadium and molybdenum oxides, measured under synchrotron X-ray diffraction. The interest in the speciation of Mo x V y O z mixed oxides lies in the excellent catalytic performance of these materials for the selective conversion of glycerol to acrylic acid employing the oxydehydration reaction. The crystallographic structure of the active phases of Mo x V y O z directly influences on the nearby metal valence and, therefore, on the dynamic changes in metal oxidation states during the catalytic reaction. In the present study, the thermal treatment of a mixture of the precursors of Mo and V under oxidizing or inert atmospheres revealed the major formation of 61% of MoV 2 O 8 or 29% of Mo 4 V 6 O 25 , respectively, at a final temperature of 500 • C. The most active phase for acrylic acid formation was MoV 2 O 8 (3.5 times more active than the separate metal oxides), due to the instability of the phase with respect to framework oxygen at the reaction temperature. The cycle of reduction and oxidation of the vanadium in MoV 2 O 8 during the reaction caused pronounced dynamic formation of oxygen vacancies, resulting in 97% conversion of glycerol and 32% selectivity towards acrylic acid.

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Section: Introductionmentioning

confidence: 99%

Thermal treatments of precursors of molybdenum and vanadium oxides and the formed Mo x V y O z phases active in the oxydehydration of glycerol

Possato

Cassinelli

Meyer

et al. 2017

Applied Catalysis A: General

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View full text Add to dashboard Cite

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“…Direct oxydehydration of glycerol to acrylic acid as a one‐step process has attracted particular attention in the past years. A suitable bifunctional catalyst should possess surface acidity to trigger glycerol dehydration to acrolein as well as adequate redox properties for the subsequent oxidation of acrolein to acrylic acid [89] . Multinary metal oxides containing vanadium, molybdenum, and tungsten have proved to fulfill these requirements.…”

Section: Thermal Catalysismentioning

confidence: 99%

A Perspective on Heterogeneous Catalysts for the Selective Oxidation of Alcohols

Najafishirtari

Ortega

Douthwaite

et al. 2021

Chemistry A European J

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Selective oxidation of higher alcohols using heterogeneous catalysts is an important reaction in the synthesis of fine chemicals with added value. Though the process for primary alcohol oxidation is industrially established, there is still a lack of fundamental understanding considering the complexity of the catalysts and their dynamics under reaction conditions, especially when higher alcohols and liquid-phase reaction media are involved. Additionally, new materials should be developed offering higher activity, selectivity, and stability. This can be achieved by unraveling the structure-performance correlations of these catalysts under reaction conditions. In this regard, researchers are encouraged to develop more advanced characterization techniques to address the complex interplay between the solid surface, the dissolved reactants, and the solvent. In this mini-review, we report some of the most important approaches taken in the field and give a perspective on how to tackle the complex challenges for different approaches in alcohol oxidation while providing insight into the remaining challenges.

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“…Another example is the complex catalyst H 0.1 Cs 2.5 (VO) 0.2 (PMo 12 O 40 ) 0.25 (PW 12 O 40 ) 0.75 , which is a vanadium‐doped cesium salt of a Keggin‐type heteropolyacid, yielding 60 % of AA acid . Up to now, the best results showing 85 % of AA at 94 % of glycerol conversion was obtained over vanadosilicate at 320 °C in oxygen atmosphere with acrolein and acetaldehyde as main by‐products …”

Section: Chemical Routes Of Acrylic Acidmentioning

confidence: 99%

Bio‐Acrylates Production: Recent Catalytic Advances and Perspectives of the Use of Lactic Acid and Their Derivates

et al. 2018

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The production of drop‐in chemicals from bio‐based renewable sources is gaining a lot of momentum due to proven negative impact of fossil‐based economy on environment and society. In this Review, various bio‐derived platform molecules are assessed as renewable alternatives to fossil resources for the catalytic production of acrylates. Acrylic acid and its esters are key building blocks of a large number of high‐value oligomers and polymers in the current industry. In spite of the encouraging successes reported on gram or lab‐scale, real implementation of bio‐based examples remain scarce mainly due to the current high cost and limited availability of the bio‐based substrates. As lactic acid and their derivatives are one of the most promising feedstocks for bio‐acrylate production, they are the main focus of this Review.

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One-step oxidehydration of glycerol to acrylic acid using ETS-10-like vanadosilicates

Cited by 32 publications

References 43 publications

Thermal treatments of precursors of molybdenum and vanadium oxides and the formed Mo x V y O z phases active in the oxydehydration of glycerol

Thermal treatments of precursors of molybdenum and vanadium oxides and the formed Mo x V y O z phases active in the oxydehydration of glycerol

A Perspective on Heterogeneous Catalysts for the Selective Oxidation of Alcohols

Bio‐Acrylates Production: Recent Catalytic Advances and Perspectives of the Use of Lactic Acid and Their Derivates

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