A scalable carboxylation route to furan-2,5-dicarboxylic acid

Dick, Graham R.; Frankhouser, Amy; Banerjee, Aanindeeta; Kanan, Matthew W.

doi:10.1039/c7gc01059a

Cited by 114 publications

(94 citation statements)

References 18 publications

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“…In this regard, the concept of integrated biorefineries encompassing green chemistry principles for production, enhanced energy and material efficiency, reduced waste generation and toxicity, and the increased reusability of the products at the end of their lives, has drawn particular interests and discussion (Clark et al, 2009 ; De Bhowmick et al, 2017 ). Greener processes incorporating concepts such as use of heterogeneous catalysis, water-based reactions, environmentally-friendly oxidants substituting for less efficient processes using volatile organic solvents and materials with high environmental burden (Dick et al, 2017 ; Pelckmas et al, 2017 ). Similarly, alternative activation methods such as microwave (MW) and ultrasound technologies should replace energy-intensive heating to facilitate efficient chemical reactions.…”

Section: Introductionmentioning

confidence: 99%

Lignocellulosic Biomass Transformations via Greener Oxidative Pretreatment Processes: Access to Energy and Value-Added Chemicals

et al. 2018

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Anthropogenic climate change, principally induced by the large volume of carbon dioxide emission from the global economy driven by fossil fuels, has been observed and scientifically proven as a major threat to civilization. Meanwhile, fossil fuel depletion has been identified as a future challenge. Lignocellulosic biomass in the form of organic residues appears to be the most promising option as renewable feedstock for the generation of energy and platform chemicals. As of today, relatively little bioenergy comes from lignocellulosic biomass as compared to feedstock such as starch and sugarcane, primarily due to high cost of production involving pretreatment steps required to fragment biomass components via disruption of the natural recalcitrant structure of these rigid polymers; low efficiency of enzymatic hydrolysis of refractory feedstock presents a major challenge. The valorization of lignin and cellulose into energy products or chemical products is contingent on the effectiveness of selective depolymerization of the pretreatment regime which typically involve harsh pyrolytic and solvothermal processes assisted by corrosive acids or alkaline reagents. These unselective methods decompose lignin into many products that may not be energetically or chemically valuable, or even biologically inhibitory. Exploring milder, selective and greener processes, therefore, has become a critical subject of study for the valorization of these materials in the last decade. Efficient alternative activation processes such as microwave- and ultrasound irradiation are being explored as replacements for pyrolysis and hydrothermolysis, while milder options such as advanced oxidative and catalytic processes should be considered as choices to harsher acid and alkaline processes. Herein, we critically abridge the research on chemical oxidative techniques for the pretreatment of lignocellulosics with the explicit aim to rationalize the objectives of the biomass pretreatment step and the problems associated with the conventional processes. The mechanisms of reaction pathways, selectivity and efficiency of end-products obtained using greener processes such as ozonolysis, photocatalysis, oxidative catalysis, electrochemical oxidation, and Fenton or Fenton-like reactions, as applied to depolymerization of lignocellulosic biomass are summarized with deliberation on future prospects of biorefineries with greener pretreatment processes in the context of the life cycle assessment.

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Section: Introductionmentioning

confidence: 99%

Lignocellulosic Biomass Transformations via Greener Oxidative Pretreatment Processes: Access to Energy and Value-Added Chemicals

et al. 2018

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“…Anhydrous potassium carbonate (99.8%) was purchased from Fisher Chemical, cesium carbonate (99.9%) was purchased from Chem Impex International, and 2-furoic acid (98%) was purchased from Acros Organics. Furan-2,5-dicarboxylic acid was synthesized and isolated according to a previously reported procedure, 1 and its purity was verified by 1 H and 13 C NMR prior to use. Anhydrous diethyl ether (99%) and methanol (99.9%) were purchased from Fisher Chemical and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

Phase Behavior that Enables Solvent-Free Carbonate-Promoted Furoate Carboxylation

Frankhouser¹,

Kanan²

2020

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“…Unfortunately, this is a low efficient pathway that resulted in poor FDCA yield and selectivity with many intermediate products. Contrastingly, carboxylation reaction pathway of furfural to FDCA has gained much attention because furfural can be readily oxidized to furoic acid under mild conditions (Taarning et al, 2008 ; Gupta et al, 2017a ) and subsequent carboxylation can be achieved without any solvent or transition metal catalysts (Dick et al, 2017 ). Consequently, Zhang et al ( 2018a ) was able to demonstrate that 5-bromo-furoic acid, obtained by the bromination of furfural-derived furoic acid, can effectively undergo aqueous phase carbonylation to produce high yield (98%) of FDCA and facilely separated through a simple acidification of the reaction medium.…”

Section: Past and Current Industrial Fdca Productionmentioning

confidence: 99%

Heterogeneous Catalytic Conversion of Sugars Into 2,5-Furandicarboxylic Acid

et al. 2020

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Achieving the goal of living in a sustainable and greener society, will need the chemical industry to move away from petroleum-based refineries to bio-refineries. This aim can be achieved by using biomass as the feedstock to produce platform chemicals. A platform chemical, 2,5-furandicarboxylic acid (FDCA) has gained much attention in recent years because of its chemical attributes as it can be used to produce green polymers such polyethylene 2,5-furandicarboxylate (PEF) that is an alternative to polyethylene terephthalate (PET) produced from fossil fuel. Typically, 5-(hydroxymethyl)furfural (HMF), an intermediate product of the acid dehydration of sugars, can be used as a precursor for the production of FDCA, and this transformation reaction has been extensively studied using both homogeneous and heterogeneous catalysts in different reaction media such as basic, neutral, and acidic media. In addition to the use of catalysts, conversion of HMF to FDCA occurs in the presence of oxidants such as air, O 2 , H 2 O 2 , and t-BuOOH. Among them, O 2 has been the preferred oxidant due to its low cost and availability. However, due to the low stability of HMF and high processing cost to convert HMF to FDCA, researchers are studying the direct conversion of carbohydrates and biomass using both a single-and multi-phase approach for FDCA production. As there are issues arising from FDCA purification, much attention is now being paid to produce FDCA derivatives such as 2, 5-furandicarboxylic acid dimethyl ester (FDCDM) to circumvent these problems. Despite these technical barriers, what is pivotal to achieve in a cost-effective manner high yields of FDCA and derivatives, is the design of highly efficient, stable, and selective multi-functional catalysts. In this review, we summarize in detail the advances in the reaction chemistry, catalysts, and operating conditions for FDCA production from sugars and carbohydrates.

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A scalable carboxylation route to furan-2,5-dicarboxylic acid

Abstract: 2-Furoic acid is converted to furan-2,5-dicarboxylic acid in high yield on a mole scale using carbonate-promoted C–H carboxylation.

Cited by 114 publications

References 18 publications

Lignocellulosic Biomass Transformations via Greener Oxidative Pretreatment Processes: Access to Energy and Value-Added Chemicals

Lignocellulosic Biomass Transformations via Greener Oxidative Pretreatment Processes: Access to Energy and Value-Added Chemicals

Phase Behavior that Enables Solvent-Free Carbonate-Promoted Furoate Carboxylation

Heterogeneous Catalytic Conversion of Sugars Into 2,5-Furandicarboxylic Acid

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