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

Marcotullio, Gianluca; Jong, Wiebren de; Cardoso, Tavares; Verkooijen, A.H.M.

doi:10.2202/1542-6580.1980

Cited by 22 publications

(31 citation statements)

References 19 publications

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“…1 Schematic of the experimental setup L-arabinose, furfural and anhydrous oxalic acid, were obtained commercially, all with a 99 % purity (SigmaAldrich). Their concentrations in the experiments were selected to be in-line with previous studies [5,17,26,28] and indicate attractive economic potential [25]. The seawater was sampled from the North Sea near Scheveningen (The Netherlands) in June 2012.…”

Section: Methodsmentioning

confidence: 99%

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The effects of combined catalysis of oxalic acid and seawater on the kinetics of xylose and arabinose dehydration to furfural

Hongsiri

Danon

Jong

2014

Int J Energy Environ Eng

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It is known that both acids and salts have a positive catalytic effect on the dehydration of pentoses to form furfural, a potentially attractive platform chemical. In this study the effects of the combined usage of an organic acid, instead of stronger mineral acids, and a saline catalyst is investigated. In order to assess these effects, the kinetics of pentose dehydration to furfural are studied using oxalic acid as the primary catalyst and NaCl or seawater as the secondary saline catalyst. The interactions between these two types of catalysts are complex and are, therefore, also assessed thermodynamically. The addition of salts lowers the activity coefficient of the hydronium ions, but simultaneously favours the dissociation of the organic acid. It turned out that these two effects are of similar magnitude, resulting in a fairly constant hydronium ion activity. Because nonetheless higher furfural yields are obtained using the salts as a secondary catalyst, it is concluded that the salts influence the pentose dehydration mechanism directly. The final furfural yields obtained using oxalic acid as the primary catalyst were only slightly lower than those for similar experiments using HCl. The most distinctive difference between the two acids is the lower reaction rate (and thus longer reaction times) when using oxalic acid. Finally, it was observed that if no acidic catalyst is used, the salts tend to catalyse a loss reaction, which is suppressed when an acid is present.

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Section: Methodsmentioning

confidence: 99%

“…4 [11,18,28,37,41]. Most studies use first-order kinetics for both the furfural degradation [5,15,22,26,33,37] and pentose dehydration reactions [6,9,28,38]. Moreover, the reaction scheme for arabinose dehydration is assumed to be analogous to that of xylose.…”

Section: Kineticsmentioning

confidence: 99%

The effects of combined catalysis of oxalic acid and seawater on the kinetics of xylose and arabinose dehydration to furfural

Hongsiri

Danon

Jong

2014

Int J Energy Environ Eng

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“…As imilarb ehaviori se xpected fort he monovalent metal chlorides at prolongedr eaction times. The decreaseo ff urfural yield with af urther increasei nt he reaction time occurs owing to its decomposition [41][42][43] and concomitantp olymerization withc har formation. [10,44] As seen in Figure2,t he highest furfural yield was obtained with FeCl 3 additiont ot he reaction mixture.…”

Section: Effect Of Salts On Decompositionofx Ylosementioning

confidence: 99%

The role of xylulose as an intermediate in xylose conversion to furfural: insights via experiments and kinetic modelling

et al. 2015

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An experimental work has been performed to study the relevance of xylulose as an intermediate in xylose conversion to furfural in aqueous solution. The furfural formation was investigated at the temperature range from 180 to 220 C during non-catalyzed and acid-catalyzed conversion of xylose in a stirred microwaveassisted batch reactor. The separate experiments on xylulose and furfural conversions were carried out under similar conditions. The maximum furfural yields obtained from xylose were 48 mol% and 65 mol% for the non-catalyzed and the acid-catalyzed processes, respectively. It was shown that the furfural yield is significantly lower from xylulose than from xylose. Furthermore, the effects of initial xylose concentration and the formation of xylulose were investigated in a mechanistic modeling study. A new reaction mechanism was developed taking into account the xylulose formation from xylose. Based on the experimental results and the proposed reaction model, it was concluded that xylose isomerization to xylulose with subsequent furfural formation is not a primary reaction pathway. The obtained kinetic parameters were further used for plug flow reactor simulations to evaluate furfural yields achievable by an optimized continuous operation.

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“…For this reason, it is assumed that the xylose intermediate concentration did not significantly influence the reaction rates. 7,21,24 The reaction scheme for arabinose dehydration is assumed to be analogous to that of xylose as presented in Figure 2. Following the reaction scheme for xylose (and arabinose) dehydration the first-order reaction rates can be described by eqs 1 and 2:…”

Section: ■ Kinetic Modelmentioning

confidence: 99%

Kinetic Study on the Dilute Acidic Dehydration of Pentoses toward Furfural in Seawater

Hongsiri

Danon

Jong

2014

Ind. Eng. Chem. Res.

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Furfural promises to be a very important product of the lignocellulosic feedstock biorefinery. In this study the kinetics of both xylose and arabinose dehydration toward furfural is investigated in a dilute acidic medium under three different salt conditions. These comprise no salts, a 500 mM NaCl solution, and seawater. The results demonstrate that the salts catalyze all disappearance reactions of the pentoses, both toward furfural and toward loss products. Especially at higher temperatures, the increase in the reaction rate toward furfural is larger than toward loss products. The values of the reaction rate constants at different salt conditions and temperatures indicate that different ions catalyze specific (temperature dependent) reactions in the dehydration mechanism of a pentose. Furthermore, the increase in the reaction rates is more pronounced with the combined salts naturally present in seawater compared to only NaCl, even at the same salinity and ionic strength. It is shown in additional experiments with no acid added that the observed salt effects are independent of the acidic environment. Furthermore, the effects of the salts are larger for the dehydration of xylose compared to arabinose. Moreover, for all temperatures the molar furfural yield was improved by the addition of the salts. Finally, it is shown that the salts inhibit furfural loss reactions toward formic acid. The presented results further contribute to the understanding of the effects of saline catalysis on the mechanism of pentose dehydration.

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

Cited by 22 publications

References 19 publications

The effects of combined catalysis of oxalic acid and seawater on the kinetics of xylose and arabinose dehydration to furfural

The effects of combined catalysis of oxalic acid and seawater on the kinetics of xylose and arabinose dehydration to furfural

The role of xylulose as an intermediate in xylose conversion to furfural: insights via experiments and kinetic modelling

Kinetic Study on the Dilute Acidic Dehydration of Pentoses toward Furfural in Seawater

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