Non-stoichiometric formation of formic and levulinic acids from the hydrolysis of biomass derived hexose carbohydrates

Flannelly, Thomas; Lopes, M.; Kupiainen, Laura; Dooley, Stephen; Leahy, James J.

doi:10.1039/c5ra25172a

Cited by 79 publications

(48 citation statements)

References 32 publications

(43 reference statements)

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“…However, formic acid was also released during heating to 180 • C and 200 • C under hydrothermal conditions, probably coming from the elimination of formyl groups originally linked to hemicellulose xylan [52]. This was especially noticeable for miscanthus, where the formic acid formation was similar to xylose formation, even at 220 • C. However, the formation of formic acid may also occur in different pathways, that is, sugars defragmentation, via (1) furfuryl alcohol, (2) furfural formation (3) pyruvaldehyde, and (4) D-erythrose [53].…”

Section: Dissolved Products Formationmentioning

confidence: 99%

Acid Hydrolysis of Lignocellulosic Biomass: Sugars and Furfurals Formation

et al. 2020

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Hydrolysis of lignocellulosic biomass is a crucial step for the production of sugars and biobased platform chemicals. Pretreatment experiments in a semi-continuous plant with diluted sulphuric acid as catalyst were carried out to measure the time-dependent formation of sugars (glucose, xylose, mannose), furfurals, and organic acids (acetic, formic, and levulinic acid) at different hydrolysis temperatures (180, 200, 220 °C) of one representative of each basic type of lignocellulose: hardwood, softwood, and grass. The addition of the acid catalyst is followed by a sharp increase in the sugar concentration. Xylose and mannose were mainly formed in the initial stages of the process, while glucose was released slowly. Increasing the reaction temperature had a positive effect on the formation of furfurals and organic acids, especially on hydroxymehtylfurfural (HMF) and levulinic acid, regardless of biomass type. In addition, large amounts of formic acid were released during the hydrolysis of miscanthus grass. Structural changes in the solid residue show a complete hydrolysis of hemicellulose at 180 °C and of cellulose at 200 °C after around 120 min reaction time. The results obtained in this study can be used for the optimisation of the hydrolysis conditions and reactor design to maximise the yields of desired products, which might be sugars or furfurals.

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Section: Dissolved Products Formationmentioning

confidence: 99%

Acid Hydrolysis of Lignocellulosic Biomass: Sugars and Furfurals Formation

et al. 2020

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“…Hydration of 5-HMF consists in the addition of a water molecule to the C2-C3 olefinic bond of the furan ring, leading to an unstable tricarbonyl intermediate, which quickly decomposes to LA and formic acid (HCOOH), in stoichiometric amount [22,30]. However, Flannelly et al have recently reported that formic acid is produced even in excess to LA respect to the stoichiometric amount during the acid hydrolysis of hexose carbohydrates, thus highlighting the potentiality of this coproduct coming from LA synthesis [31]. In fact, formic acid is a valuable product in its own right and can be used as a commodity in the chemical and textile industry, as a catalyst, a hydrogen carrier and a road salting component [4,32].…”

Section: Introductionmentioning

confidence: 99%

New Frontiers in the Catalytic Synthesis of Levulinic Acid: From Sugars to Raw and Waste Biomass as Starting Feedstock

et al. 2016

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Levulinic acid (LA) is one of the top bio-based platform molecules that can be converted into many valuable chemicals. It can be produced by acid catalysis from renewable resources, such as sugars, lignocellulosic biomass and waste materials, attractive candidates due to their abundance and environmentally benign nature. The LA transition from niche product to mass-produced chemical, however, requires its production from sustainable biomass feedstocks at low costs, adopting environment-friendly techniques. This review is an up-to-date discussion of the literature on the several catalytic systems that have been developed to produce LA from the different substrates. Special attention has been paid to the recent advancements on starting materials, moving from simple sugars to raw and waste biomasses. This aspect is of paramount importance from a sustainability point of view, transforming wastes needing to be disposed into starting materials for value-added products. This review also discusses the strategies to exploit the solid residues always obtained in the LA production processes, in order to attain a circular economy approach.

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“…Ar ehydration step involving the addition of two water molecules is then neededt oo btain almost equimolar quantities of levulinic acid and formica cid. [45] The acid-catalyzed conversion of carbohydrates into levulinic acid and formic acid, as well as of cellulose into glucose, can be carried out in concentrated solutionso fa cids at moderate temperature ( % 373 K) or in their dilute solutions at elevated temperature (> 433 K). [46] As mentioned above,f ormic acid already decomposes at about room temperature in, for example, concentrated sulfuric acid [7] and this can decrease the yield of acid.…”

Section: Formicacid From Cellulosebyh Ydrolysiswith Acidsmentioning

confidence: 99%

Towards Sustainable Production of Formic Acid

2018

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Formic acid is a widely used commodity chemical. It can be used as a safe, easily handled, and transported source of hydrogen or carbon monoxide for different reactions, including those producing fuels. The review includes historical aspects of formic acid production. It briefly analyzes production based on traditional sources, such as carbon monoxide, methanol, and methane. However, the main emphasis is on the sustainable production of formic acid from biomass and biomass-derived products through hydrolysis and oxidation processes. New strategies of low-temperature synthesis from biomass may lead to the utilization of formic acid for the production of fuel additives, such as methanol; upgraded bio-oil; γ-valerolactone and its derivatives; and synthesis gas used for the Fischer-Tropsch synthesis of hydrocarbons. Some technological aspects are also considered.

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Non-stoichiometric formation of formic and levulinic acids from the hydrolysis of biomass derived hexose carbohydrates

Cited by 79 publications

References 32 publications

Acid Hydrolysis of Lignocellulosic Biomass: Sugars and Furfurals Formation

Acid Hydrolysis of Lignocellulosic Biomass: Sugars and Furfurals Formation

New Frontiers in the Catalytic Synthesis of Levulinic Acid: From Sugars to Raw and Waste Biomass as Starting Feedstock

Towards Sustainable Production of Formic Acid

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