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

Abstract

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.

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

“…In order to perform these calculations, the concentrations of the ions in the NaCl solution and in seawater were determined using ICP-OES elemental analysis. These results have been published previously [17].…”

“…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.…”

“…The seawater was sampled from the North Sea near Scheveningen (The Netherlands) in June 2012. More details regarding the experimental procedure have been presented previously [17].…”

“…5 and in Table 2. Also the results of comparable studies on furfural degradation (using mineral acids [17,32,38] and without any acidic catalyst [18]) are included for comparison purposes.…”

“…Seawater offers a particularly interesting and cheap catalytic reaction medium for biorefinery processes [14,17,21,24,33]. Thus nonpotable water sources can be used at large scale, mainly in coastal localities, and for existing resources, such as macro algae [13].…”