Oxidation of levulinic acid for the production of maleic anhydride: breathing new life into biochemicals

Chatzidimitriou, Anargyros; Bond, Jesse Q.

doi:10.1039/c5gc01000d

Cited by 69 publications

(61 citation statements)

References 48 publications

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“…Variations in the synthetic methodology used for the preparation of polymeric materials can lead to stark differences in properties at both the molecular and macroscopic levels. [1] In this context, ring-opening metathesis polymerization (ROMP) [2,3] of strained cyclic olefins offers some unique materials can be obtained renewably from the platform molecule furfural [21][22][23] and the reaction is known to give the strained tricyclic lactone adduct 3 (over two synthetic steps), by intramolecular DA cyclization following ring opening of the anhydride by nucleophilic attack of the alcohol group, delivering the product exclusively as the exo,exo isomer. [24] We predicted that, in combination, the lack of endo substituents and the steric asymmetry on 3 (due to the presence of the bridgehead substituent) may lead to rapid, regioselective ring opening during ROMP.…”

Section: Introductionmentioning

confidence: 99%

Rapid, Regioselective Living Ring‐Opening Metathesis Polymerization of Bio‐Derivable Asymmetric Tricyclic Oxanorbornenes

Naguib

Schiller

Keddie

2018

Macromol. Rapid Commun.

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---------The synthesis of a range of alkyl esters (methyl, n-butyl and n-decyl) prepared via Steglich esterification of the thermodynamically-controlled exo,exo Diels-Alder (DA) adduct of furfuryl alcohol and maleic anhydride is reported. Subsequent ring-opening metathesis polymerization (ROMP) of these bio-derivable tricyclic oxanorbornene analogues delivered polymers with targeted molar mass and low molar mass dispersity. The polymerizations are rapid with complete monomer conversion achieved within 15 minutes. Significantly, the presence of the cyclic lactone at the bridgehead of these monomers leads to polymers with high regio-(>85% head-to-tail) and stereoregularity (>75% trans). The resultant polymers display both high thermal stability and high glass transition temperatures. This new class of oxanorbornene monomer, accessed from bio-derivable furfuryl alcohol and maleic anhydride, may be further tailored to incorporate a range of functional moieties. Furthermore, the exceptional properties of the derived polymers indicate potential in range of applications.

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Section: Introductionmentioning

confidence: 99%

Rapid, Regioselective Living Ring‐Opening Metathesis Polymerization of Bio‐Derivable Asymmetric Tricyclic Oxanorbornenes

Naguib

Schiller

Keddie

2018

Macromol. Rapid Commun.

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“…Recently there has been research directed at developing new renewable routes to produce some of these two commodities by oxidation of biomass-derived platforms like butanol [3], levulinic acid [4], hydroxymethylfurfural [5] and furfural [6][7][8][9][10][11][12][13]. MA and MAc can be interconverted into each other, and therefore the production of one of them implies the availability of the other.…”

Section: Introductionmentioning

confidence: 99%

Oxidation of furfural in aqueous H2O2 catalysed by titanium silicalite: Deactivation processes and role of extraframework Ti oxides

Alba

Fierro

León‐Reina

et al. 2017

Applied Catalysis B: Environmental

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2 Graphical abstract Highlights  The use of TS-1 for the oxidation of furfural to maleic acid with H2O2 is reported.  Extraframework TiO2 nanodomains can also be located in the channels and cavities of TS-1.  When present, it blocks the access of reactants to active sites.  Coke deposition and Ti leaching are identified as the main causes of deactivation. AbstractTitanium silicalites (TS-1) with different Ti/Si atomic ratio (0.01-0.08) have been prepared, characterised by different techniques (X-Ray Diffraction, Transmission Electron Microscopy and Raman, Diffuse Reflection Infrared Fourier Transform and XRay Photoelectron spectroscopies), and their catalytic properties were investigated for the liquid phase oxidation of furfural with aqueous H2O2. For samples prepared with an initial Ti/Si > 0.01, extraframework Ti oxide is present and become more important as Ti loading increases. Two types of extraframework Ti have been identified: (i) anatase Ti oxide located at the external surface of zeolite crystals and (ii) Ti oxide nanodomains occluded within the channels and cavities of the zeolite. The latter can block the access of reactants to the active framework Ti(IV) sites for samples prepared with an initial Ti/Si > 0.04 and their removal results in an improvement in the selective oxidation of furfural to valuable products. The fouling by deposition of heavy by-products and Ti leaching were identified as two main causes of catalyst deactivation. The former can be reverted by removal of the deposits through calcination under air at 773 K. Leaching affects both the extraframework Ti and the active framework Ti species. During the first runs of reutilization, the Ti leaching is severe, affecting mainly to extraframework Ti oxide. Initially this leaching may be positive because its removal leads to the 3 elimination of species blocking the access of reactants to the active Ti species; but in the longer term, the continuous leaching of active framework Ti irreversibly deactivates the catalyst.

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“…[7,16] The transformation of LA to GVL and beyond typically involves a series of consecutive catalytic dehydration and reduction steps; although oxidative pathways are also possible. [20] The dehydration step is acid catalysed, while reduction is achieved using a transition metal catalyst with either molecular hydrogen or formic acid as hydrogen source. A number of heterogeneous and homogenous based catalytic systems have been reported for a range of biomass transformations; the area has been reviewed recently.…”

Section: Introductionmentioning

confidence: 99%

Homogeneous Catalyzed Reactions of Levulinic Acid: To γ‐Valerolactone and Beyond

et al. 2016

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Platform chemicals derived from lignocellulousic plant biomass are viewed as a sustainable replacement for crude oil based feed-stocks. Levulinic acid (LA) is one such biomass derived chemical that has been widely studied for further catalytic transformation to γ-valerolactone (GVL), an important 'green' fuel additive, solvent and fine chemical intermediate. Although the transformation of LA to GVL can be achieved using heterogeneous catalysis, homogeneous catalytic systems that operate under milder reactions, give high seletivities and can be recycled continue to attract much attention. A range of new homogeneous catalysts have now been demonstrated to efficiently convert LA to GVL, and to transform LA directly to other value added chemicals such as 1,4-pentanediol (1,4-PDO) and 2-methyltetrahydrofuran (2-MTHF). This mini review covers recent advances in the area of homogeneous catalysis for the conversion of levulinic acid and levulinic ester derivatives to GVL and chemicals beyond GVL.

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Oxidation of levulinic acid for the production of maleic anhydride: breathing new life into biochemicals

Abstract: Advanced biofuels have to date failed to compete with their petrochemical equivalents. Herein, we explore alternative, emerging opportunities in commodity chemical markets by presenting a novel bio-based approach for the production of maleic anhydride.

Cited by 69 publications

References 48 publications

Rapid, Regioselective Living Ring‐Opening Metathesis Polymerization of Bio‐Derivable Asymmetric Tricyclic Oxanorbornenes

Rapid, Regioselective Living Ring‐Opening Metathesis Polymerization of Bio‐Derivable Asymmetric Tricyclic Oxanorbornenes

Oxidation of furfural in aqueous H2O2 catalysed by titanium silicalite: Deactivation processes and role of extraframework Ti oxides

Homogeneous Catalyzed Reactions of Levulinic Acid: To γ‐Valerolactone and Beyond

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