Platinum−Bismuth-Catalyzed Oxidation of Glycerol: Kinetics and the Origin of Selective Deactivation

Wörz, Nicolai; Brandner, Armin; Claus, Peter

doi:10.1021/jp909412h

Cited by 98 publications

(98 citation statements)

References 21 publications

(46 reference statements)

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“…The experimentally obtained E A in this work, as shown in Table 1, is in good agreement with the 38 kJ mol À1 value reported by Wörz et al [27] for glycerol oxidation, although their work was based on a Pt-Bi/C catalyst. Demirel et al [28] also reported activation energies of between 40 and 50 kJ mol…”

Section: Advanced Chemical Kinetics 120supporting

confidence: 91%

Oxidation of Glycerol to Lactic Acid by Gold on Acidified Alumina: A Kinetic and DFT Case Study

Ntho¹,

Gqogqa²,

Aluha³

2018

Advanced Chemical Kinetics

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The aim of this chapter is to present proposed kinetic and density functional theory (DFT) models for the selective oxidation of glycerol to various hydroxy-acids over an acidified Au/γ-Al 2 O 3 catalyst. Glycerol oxidation over gold-based catalysts to valueadded chemicals continues to attract attention worldwide. Both the kinetics and theoretical mechanisms of this reaction have been reported in the past. However, some of the reported kinetic data was possibly collected under mass transfer limitations. In this case study we demonstrate that if mass transfer is eliminated, a pseudo zero-order model can be fitted to the experimental data with a high degree of correlation. Furthermore, we propose a plausible mechanism of pyruvaldehyde (PA) isomerisation to lactic acid (LAC) over supported molybdenum Lewis acid sites as investigated with density functional theory (DFT) approach. A proposed DFT model suggested that the rate-limiting step in the isomerisation of PA to LAC, catalysed by a Mo Lewis acid-site, could be the dissociation of a proton from an adsorbed water molecule -the protonation step.

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Section: Advanced Chemical Kinetics 120supporting

confidence: 91%

Oxidation of Glycerol to Lactic Acid by Gold on Acidified Alumina: A Kinetic and DFT Case Study

Ntho¹,

Gqogqa²,

Aluha³

2018

Advanced Chemical Kinetics

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“…Based on the experimental evidence obtained with Pt(3.0 wt.%)/C and Pd(4.0 wt.%)-Pt(1.0 wt.%)-Bi(5.0 wt.%)/C catalysts, and the indications made by Worz et al (2009), a reaction network was assumed (Scheme 1). According to the proposal, the oxidation of the primary OH group of glycerol (GLY) leads mainly to glyceric acid (GLYA), followed by tartronic acid (TTA).…”

Section: Kinetic Modelingmentioning

confidence: 99%

“…Scheme 1: Reaction network of the glycerol oxidation (Worz et al, 2009 Scheme 2: Simplified reaction network for the catalytic oxidation of glycerol in alkaline medium. …”

Section: Kinetic Modelingmentioning

confidence: 99%

“…Glyceric acid and dihydroxyacetone are the main products obtained from glycerol oxidation in the presence of palladium and platinum catalysts (Mallat and Baiker, 1995;Kimura et al, 1993;Kimura, 1993;Fordham et al, 1996). Tartronic acid and oxalic acid are also formed by oxidation of glyceric acid and dihydroxyacetone (Fordham et al, 1996;Worz, 2009). An increasing number of studies on oxidation of glycerol with oxygen in aqueous solution have been conducted with catalysts based on palladium and platinum Kimura, 1993;Fordham et al, 1996).…”

Section: Introductionmentioning

confidence: 99%

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Wet oxidation of glycerol into fine organic acids: catalyst selection and kinetic evaluation

Brainer

Sales

Medeiros

et al. 2014

Braz. J. Chem. Eng.

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-The liquid phase oxidation of glycerol was performed producing fine organic acids. Catalysts based on Pt, Pd and Bi supported on activated carbon were employed to perform the conversion of glycerol into organic acids at 313 K, 323 K and 333 K, under atmospheric pressure (1.0 bar), in a mechanically agitated slurry reactor (MASR). The experimental results indicated glycerol conversions of 98% with production of glyceric, tartronic and glycolic acids, and dihydroxyacetone. A yield of glyceric acid of 69.8%, and a selectivity of this compound of 70.6% were reached after 4 h of operation. Surface mechanisms were proposed and rate equations were formulated to represent the kinetic behavior of the process. Selective formation of glyceric acid was observed, and the kinetic parameter values indicated the lowest activation energy (38.5 kJ/mol) for its production reaction step, and the highest value of the adsorption equilibrium constant of the reactant glycerol (10 -4 dm 3 /mol).

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“…4,[128][129][130][131][132] Some promising derivatives include dihydroxyacetone (DHA), glyceric acid (GLS) and H 2 . Fig.…”

Section: Glycerol Reformingmentioning

confidence: 99%

Recent developments in the production of liquid fuels via catalytic conversion of microalgae: experiments and simulations

et al. 2012

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Due to continuing high demand, depletion of non-renewable resources and increasing concerns about climate change, the use of fossil fuel-derived transportation fuels faces relentless challenges both from a world markets and an environmental perspective. The production of renewable transportation fuel from microalgae continues to attract much attention because of its potential for fast growth rates, high oil content, ability to grow in unconventional scenarios, and inherent carbon neutrality. Moreover, the use of microalgae would minimize ''food versus fuel'' concerns associated with several biomass strategies, as microalgae do not compete with food crops in the food chain. This paper reviews the progress of recent research on the production of transportation fuels via homogeneous and heterogeneous catalytic conversions of microalgae. This review also describes the development of tools that may allow for a more fundamental understanding of catalyst selection and conversion processes using computational modelling. The catalytic conversion reaction pathways that have been investigated are fully discussed based on both experimental and theoretical approaches. Finally, this work makes several projections for the potential of various thermocatalytic pathways to produce alternative transportation fuels from algae, and identifies key areas where the authors feel that computational modelling should be directed to elucidate key information to optimize the process.

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Platinum−Bismuth-Catalyzed Oxidation of Glycerol: Kinetics and the Origin of Selective Deactivation

Cited by 98 publications

References 21 publications

Oxidation of Glycerol to Lactic Acid by Gold on Acidified Alumina: A Kinetic and DFT Case Study

Oxidation of Glycerol to Lactic Acid by Gold on Acidified Alumina: A Kinetic and DFT Case Study

Wet oxidation of glycerol into fine organic acids: catalyst selection and kinetic evaluation

Recent developments in the production of liquid fuels via catalytic conversion of microalgae: experiments and simulations

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