Abstract
Furans (furfural and hydroxymethylfurfural) are the results of dehydration of monosaccharides, which can be obtained by acid hydrolysis of wood or other lignocellulosic materials. In this work, Pinus pinaster wood was subjected to aqueous autohydrolysis processing to obtain dissolved hemicellulose-derived polymeric or oligomeric saccharides made up of mannosyl, glucosyl, galactosyl, xylosyl, and arabinosyl structural units. The aqueous liquors were then heated in the presence of sulfuric acid and methyl isobutyl ketone to obtain furans. The effects of selected operational variables, such as the ratio of organic to aqueous phase, temperature, and reaction time, were assessed by empirical modeling in terms of the conversion into furans and levulinic acid. The maximum furfural conversion (71.4%) was predicted to occur operating at 165°C and a ratio of organic to aqueous phase of 2 for 68.5 min. In additional experiments, dimethyl sulfoxide and/or 1-butanol were added to the aqueous phase and the change in furan conversion rates was observed.
The authors are grateful to the Spanish “Ministry of Science and Innovation” for supporting this study, in the framework of the research project “Development and Evaluation of Processing Methods for Biorefineries” (reference CTQ2011-22972), and to Xunta de Galicia (INBIOMED project) for the additional financial support. Both projects were partially funded by the FEDER Program of the European Union (“Unha maneira de facer Europa”). Ms. Sandra Rivas thanks the “Ministry of Science and Innovation” for her predoctoral grant.
References
Blumenkrantz, N., Asboe Hansen, G. (1973) New method for quantitative determination of uronic acids. Anal. Biochem. 54:484–489.Search in Google Scholar
Carvalheiro, F., Duarte, L., Gírio, F. (2008) Hemicellulose biorefineries: a review on biomass pretreatments. J. Sci. Ind. Res. 67:849–864.Search in Google Scholar
Chheda, J.N., Huber, W., Dumesic, J.A. (2007a) Liquid-phase catalytic processing of biomass derived oxygenated hydrocarbons to fuels and chemicals. Angew. Chem. Int. Ed. 46:7164–7183.10.1002/anie.200604274Search in Google Scholar PubMed
Chheda, J.N., Román-Leshkov, Y., Dumesic, J.A. (2007b) Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides. Green Chem. 9:342–350.10.1039/B611568CSearch in Google Scholar
Conde, E., Moure, A., Domínguez, H., Parajó, J.C. (2011) Production of antioxidants by non-isothermal autohydrolysis of lignocellulosic wastes. LWT-Food Sci. Technol. 44:436–442.Search in Google Scholar
Corma, A., Iborra, S., Velty, A. (2007) Chemical routes for the transformation of biomass into chemicals. Chem. Rev. 107:2411–2502.Search in Google Scholar
Ebringerová, A., Hromádková, Z., Heinze, T. (2005) Hemicellulose. Adv. Polym. Sci. 186:1–67.Search in Google Scholar
Galbe, M., Zacchi, G. (2002) A review of the production of ethanol from softwood. Appl. Microbiol. Biotechnol. 59:618–628.Search in Google Scholar
Girisuta, B., Janssen, L.P.B.M., Heeres, H.J. (2006a) A kinetic study on the decomposition of 5-hydroxymethylfurfural into levulinic acid. Green Chem. 8:701–709.10.1039/b518176cSearch in Google Scholar
Girisuta, B., Janssen, L.P.B.M., Heeres, H.J. (2006b) Green chemicals: a kinetic study on the conversion of glucose to levulinic acid. Chem. Eng. Res. Des. 84:339–349.10.1205/cherd05038Search in Google Scholar
González-Muñoz, M., Santos, V., Parajó, J. (2011) Purification of oligosaccharides obtained from Pinus pinaster hemicelluloses by diafiltration. Desalin. Water Treat. 27:48–53.10.5004/dwt.2011.2047Search in Google Scholar
González-Muñoz, M., Alvarez, R., Santos, V., Parajó, J. (2012) Production of hemicellulosic sugars from Pinus pinaster wood by sequential steps of aqueous extraction and acid hydrolysis. Wood Sci. Technol. 46:271–285.Search in Google Scholar
Hörhammer, H., Walton, S., van Heiningen, A. (2011) A larch based biorefinery: pre-extraction and extract fermentation to lactic acid. Holzforschung 65:491–496.10.1515/hf.2011.085Search in Google Scholar
Kenne, L., Rosell, K.G., Svensson, S. (1975) Studies on the distribution of the O-acetyl groups in pine glucomannan. Carbohydr. Res. 44:69–76.Search in Google Scholar
Lange, J.P., van der Heide, E., van Buijtenen, J., Price, R. (2012) Furfural – a promising platform for lignocellulosic biofuels. Chem. Sus. Chem. 5:150–166.Search in Google Scholar
Leschinsky, M., Zuckerstätter, G., Weber, H.K., Patt, R., Sixta, H. (2008a) Effect of autohydrolysis of Eucalyptus globulus wood on lignin structure. Part 1: comparison of different lignin fractions formed during water prehydrolysis. Holzforschung 62:645–652.10.1515/HF.2008.117Search in Google Scholar
Leschinsky, M., Zuckerstätter, G., Weber, H.K., Patt, R., Sixta, H. (2008b) Effect of autohydrolysis of Eucalyptus globulus wood on lignin structure. Part 2: influence of autohydrolysis intensity. Holzforschung 62:653–658.10.1515/HF.2008.133Search in Google Scholar
Lü, X., Shaka, S. (2012) New insights on monosaccharides isomerization, dehydration and fragmentation in hot-compressed water. J. Supercrit. Fluids 61:146–156.Search in Google Scholar
Mendes, C., Teixeira, V., Baptista, C.M.S.G., Rocha, J.M.S., Carvalho, M.G.V.S. (2009) Prehydrolysis of Eucalyptus globulus Labill. hemicelluloses prior to pulping and fermentation of the hydrolysates with the yeast Pichia stipitis. 10th EWLP, Stockholm, Sweden, August 25–28, 2008. Holzforschung 63:737–743.10.1515/HF.2009.106Search in Google Scholar
Pagán-Torres, Y.J., Wang, T., Gallo, J.M.R., Shanks, B.H., Dumesic, J.A. (2012) Production of 5-hydroxymethylfurfural from glucose using a combination of Lewis and Brönsted acid catalysts in water in a biphasic reactor with an alkylphenol solvent. ACS Catal. 2:930–934.10.1021/cs300192zSearch in Google Scholar
Rackemann, D.W., Doherty, W.O. (2011) The conversion of lignocellulosics to levulinic acid. Biofuels Bioprod. Bior. 5:198–214.10.1002/bbb.267Search in Google Scholar
Rodríguez-López, J., Romaní, A., González-Muñoz, M.J., Garrote, G., Parajó, J.C. (2012) Extracting value-added products before pulping: hemicellulosic ethanol from Eucalyptus globulus wood. Holzforschung 66:591–599.10.1515/hf-2011-0204Search in Google Scholar
Román-Leshkov, Y., Chheda, J.N., Dumesic, J.A. (2006) Phase modifiers promote efficient production of hydroxymethylfurfural from fructose. Science 312:1933–1937.10.1126/science.1126337Search in Google Scholar PubMed
Saukkonen, E., Kautto, J., Rauvanto, I., Backfolk, K. (2012) Characteristics of prehydrolysis-kraft pulp fibers from Scots pine. Holzforschung 66:801–808.10.1515/hf-2011-0158Search in Google Scholar
Song, T., Pranovich, A., Holmbom, B. (2011) Characterisation of Norway spruce hemicelluloses extracted by pressurised hot-water extraction (ASE) in the presence of sodium bicarbonate. Holzforschung 65:35–42.10.1515/hf.2011.015Search in Google Scholar
Weingarten, R., Cho, J., Curtis Conner, W., Huber, W. (2010) Kinetics of furfural production by dehydration of xylose in a biphasic reactor with microwave heating. Green Chem. 12:1423–1429.10.1039/c003459bSearch in Google Scholar
Willför, S., Sundberg, K., Tenkanen, M., Holmbom, B. (2008) Spruce-derived mannans – a potential raw material for hydrocolloids and novel advanced natural materials. Carbohydr. Polym. 72:197–210.Search in Google Scholar
Zhang, J., Lin, L., Liu, S. (2012) Efficient production of furan derivatives from a sugar mixture by catalytic process. Energy Fuels 26:4560–4567.10.1021/ef300606vSearch in Google Scholar
©2013 by Walter de Gruyter Berlin Boston