Kinetics and Mechanisms of the Acid Degradation of the Aldopentoses to Furfural

Garrett, Edward R.; Dvorchik, Barry H.

doi:10.1002/jps.2600580703

Cited by 69 publications

(56 citation statements)

References 11 publications

(7 reference statements)

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“…Despite the relative simplicity of current furfural production processes, Zeitsch [2000], there are still some questions that must be addressed concerning the chemistry of C 5 sugars which might lead to significant improvements of furfural production processes. Although it is well known that C 5 sugars like DXylose can be converted quantitatively into furfural under acidic conditions, Dunlop [1948], Garret and Dvorchik [1969], Zeitsch [2000], Root et al [1959], there are many aspects of the reaction that are not totally clear yet, especially concerning the reaction kinetics of both furfural formation and destruction under the same conditions of pH and temperature. The information available covers a wide range of conditions and shows inconsistencies between different works, Root et al [1959], Dunlop [1948], Garret and Dvorchik [1969], Antal Jr et al [1991].…”

Section: Introductionmentioning

confidence: 99%

Bioenergy II: Furfural Destruction Kinetics during Sulphuric Acid-Catalyzed Production from Biomass

Marcotullio¹,

Jong²,

Cardoso³

et al. 2009

International Journal of Chemical Reactor Engineering

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The interest for furfural has increased in the last years due to its potential for competing with oil derivatives as platform chemical. In addition, furfural, derived from C 5 sugars, can play a key role in the valorization of the hemicellulose contained in biomass when considering the development of a modern biorefinery concept. The development of such new and competitive biorefinery processes must be based on accurate kinetic data for the reactions involving furfural in the conditions used for its production.This work addresses the determination of furfural destruction kinetics in aqueous acidic environment, using sulphuric acid as catalyst, in the temperature range 150 -200• C, acid concentration range 36.4 -145.5 mM and furfural initial concentration between 60.4 and 72.5 mM. These studies were carried out using a recently built lab-scale titanium reactor that enables liquid phase reactions in a relatively broad range of conditions.The obtained results show that destruction of furfural follows first-order reaction kinetics within the range of temperature and acid concentration evaluated. Moreover, the proposed kinetic model takes into account the effects of temperature and acid dilution on the ions activity, and thus H 3 O + , by using the electrolyte Non-Random Two-Liquid (eNRTL) model. By using this approach, the rate constant dependence on temperature could be described by the Arrhenius law and thus the activation energy could be estimated as being 125. Contrarily to what is reported in previous works, formic acid formation from furfural under the tested conditions can be regarded as playing a far less pronounced role than suggested before.

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Section: Introductionmentioning

confidence: 99%

Bioenergy II: Furfural Destruction Kinetics during Sulphuric Acid-Catalyzed Production from Biomass

Marcotullio¹,

Jong²,

Cardoso³

et al. 2009

International Journal of Chemical Reactor Engineering

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“…In order to improve the yields of sugar products, particularly during dilute acid prehydrolysis, understanding the sugar degradation pathways at the molecular level is critical. Today, review of the literature reveals numerous studies of sugar degradation mechanisms in acidic media based on experiments, but few using kinetic modeling [Abatzoglou et al 1986, Antal et al 1990a, Antal et al 1990b, Antal et al 1991, Bouchard et al 1992, Garrett et al 1969, Johnson&Davis 2003, Lee et al 2001, McKibbins et al 1962, Mok et al 1992, Parker et al 2000, Torget et al 2000, van Dam et al 1986. It was commonly thought that furfural and hydroxymethylfurfural (HMF) are by far the principal acidic degradation products for xylose and glucose, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…However, the detailed mechanisms for these parasitic reactions are not known. For furfural and HMF formation, some researchers [Garrett et al 1969, Parker et al 2000 have proposed degradation pathways that proceed via a series of open-chain intermediates. In contrast, Antal and coworkers [Antal et al 1991] have proposed a mechanism based on a 2,5-anhydride intermediate for xylose degradation leading to furfural.…”

Section: Introductionmentioning

confidence: 99%

Acidic Sugar Degradation Pathways: An Ab Initio Molecular Dynamics Study

Qian¹,

Nimlos

Johnson

et al. 2005

ABAB

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Ab initio molecular dynamics (MD) simulations were employed to elucidate xylose and glucose degradation pathways. In the case of xylose, a 2,5-anhydride intermediate was observed leading to the formation of furfural through elimination of water. This pathway agrees with one of the mechanism proposed in the literature in that no open chain intermediates were found. In the case of glucose, a series of intermediates were observed before forming the 2,5-anhydride intermediate that eventually leads to hydroxymethylfurfural (HMF). One of these intermediates was a very short-lived open chain form. Furthermore, two novel side-reaction pathways were identified which lead to degradation products other than HMF.

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“…This phenomenon indicates cylcodehydration of xylose to form furfural, i.e., removal of three water molecules from xylose is responsible for the furfural formation (Kamireddy et al 2013). Similarly, arabinose being a geometrical isomer of xylose similar results of furfural formation can be expected (Garrett and Dvorchik 1969). Further, furfural decomposes to form formic acid with an increase in the pretreatment severity (Niu et al 2015) which is shown in Fig.…”

Section: Conversion Of Pentose Sugars and Their Degradation Productsmentioning

confidence: 56%

Dilute acid pretreatment of sorghum biomass to maximize the hemicellulose hydrolysis with minimized levels of fermentative inhibitors for bioethanol production

et al. 2017

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Conversion of lignocellulosic biomass into monomeric carbohydrates is economically beneficial and suitable for sustainable production of biofuels. Hydrolysis of lignocellulosic biomass using high acid concentration results in decomposition of sugars into fermentative inhibitors. Thus, the main aim of this work was to investigate the optimum hydrolysis conditions for sorghum brown midrib IS11861 biomass to maximize the pentose sugars yield with minimized levels of fermentative inhibitors at low acid concentrations. Process parameters investigated include sulfuric acid concentration (0.2-1 M), reaction time (30-120 min) and temperature (80-121°C). At the optimum condition (0.2 M sulfuric acid, 121°C and 120 min), 97.6% of hemicellulose was converted into xylobiose (18.02 mg/g), xylose (225.2 mg/g), arabinose (20.2 mg/g) with low concentration of furfural (4.6 mg/g). Furthermore, the process parameters were statistically optimized using response surface methodology based on central composite design. Due to the presence of low concentration of fermentative inhibitors, 78.6 and 82.8% of theoretical ethanol yield were attained during the fermentation of non-detoxified and detoxified hydrolyzates, respectively, using Pichia stipitis 3498 wild strain, in a techno-economical way.

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Kinetics and Mechanisms of the Acid Degradation of the Aldopentoses to Furfural

Cited by 69 publications

References 11 publications

Bioenergy II: Furfural Destruction Kinetics during Sulphuric Acid-Catalyzed Production from Biomass

Bioenergy II: Furfural Destruction Kinetics during Sulphuric Acid-Catalyzed Production from Biomass

Acidic Sugar Degradation Pathways: An Ab Initio Molecular Dynamics Study

Dilute acid pretreatment of sorghum biomass to maximize the hemicellulose hydrolysis with minimized levels of fermentative inhibitors for bioethanol production

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