Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter April 15, 2016

Statistical modeling of pressurized hot-water batch extraction (PHWE) to produce hemicelluloses with desired properties

Marjatta Kleen, Andrey Pranovich and Stefan Willför
From the journal Holzforschung


The pressurized hot-water extraction (PHWE) process of Norway spruce sawdust has been optimized aiming at the production of a hemicellulose-rich fraction consisting mainly of galactoglucomannans (GGM). The independent process parameters temperature, reaction time, and liquid-to-wood (L/W) ratio were in focus of the statistical modeling. The main target product properties were the average molecular mass (Mw) and the GGM content of the dissolved solids in the extracts and the yield of polymeric hemicelluloses with Mw larger than 4 kDa in the ethanol-water precipitate. According to the model, the highest Mw (>30 kDa) of the total dissolved solids in the extract can be obtained at a low extraction temperature (ET), a short extraction time (Et), and a low L/W ratio. The best result was 37 kDa, corresponding to a degree of polymerization (DP) about 230. The highest GGM content of the extract (>11% of the sawdust, which is about 70% of the GGM in sawdust) can be obtained with a high ET, a long Et and a high L/W ratio. According to the model, the PHWE process gives rise to the largest possible amount of polymeric hemicelluloses at 170°C, 11 min reaction time, and at L/W 5. Provided that a large-scale extraction apparatus works under these conditions with the same efficiency, it should be possible to produce around 60 g polymeric hemicelluloses (mainly GGM) with a Mw around 15 kDa from 1 kg spruce sawdust, which is roughly 25% of the original hemicelluloses in the sawdust.


Financial support from the Finnish Bioeconomy Cluster (FIBIC), the Finnish Funding Agency for Technology and Innovation (Tekes), and several industrial companies is acknowledged.


Casebier, R.L., Hamilton, J.K., Hergert, H.L. (1969) Chemistry and mechanism of water prehydrolysis on Southern pine wood. Tappi 52:2369–2377.Search in Google Scholar

Doliška, A., Willför, S., Strnad, S., Ribitsch, V., Kleinschek, K.S., Eklund, P., Xu, C. (2012) Antithrombotic properties of sulfated wood-derived galactoglucomannans. Holzforschung 66: 149–154.10.1515/HF.2011.136Search in Google Scholar

Ebringerová, E., Hromádková, Z., Heinze, T. (2005) Hemicellulose. In: Advances in Polymer Science (Polysaccharides I). Ed. Heinze, T. Springer-Verlag, Heidelberg, pp. 1–67.10.1007/b136816Search in Google Scholar

Feria, M.J., Lopez, F., Carcia, J.C., Perez. A., Zamudio, M.A.M. (2010) Autohydrolysis of Leucaena Leucocephala: Study optimizing for saccharides production. 11th European Workshop for Lignocellulosics and Pulp (EWLP), Hamburg, Germany, August 16-19, Vol. 1, pp. 271–274.Search in Google Scholar

Karlsson, P., Roubroeks, J.P., Glasser, W.G., Gatenholm, P. (2006) Optimization of the process conditions for the extraction of heteropolysaccharides from birch (Betula pendula). Eds. Bozell, J.J., Patel, M.K. Feedstocks for the future Chapter 23, ACS Symposium Series Vol. 921, American Chemical Society, Washington, DC, pp. 321–333. ISBN13: 9780841239340, eISBN: 9780841220393, DOI: 10.1021/bk-2006-0921.10.1021/bk-2006-0921Search in Google Scholar

Kilpeläinen, P., Kitunen, V., Pranovich, A., Ilvesniemi, H., Willför, S. (2013) Pressurized hot water flow-through extraction of birch sawdust with acetate pH buffer. BioRes. 8:5202–5218.10.15376/biores.8.4.5202-5218Search in Google Scholar

Kilpeläinen, P., Hautala, S., Byman, O., Tanner J., Korpinen, R., Lillandt, M., Pranovich, A., Kitunen, V., Willför, S., Ilvesniemi, H. (2014) Pressurized hot water flow-through extraction system scale up from laboratory to pilot scale. Green Chemistry 16:3186–3194.10.1039/C4GC00274ASearch in Google Scholar

Kleen, M., Määttänen, M., Asikainen, S., Liitiä, T., Tehomaa, M. (2011a) Stepwise hot water and alkali extraction of birch sawdust to produce xylan and cellulose. 16th Int. Symp. Wood, Fiber and Pulp Chem. (ISWFPC), Tianjin, China, June 8–10, Vol. 1, pp. 666–671.Search in Google Scholar

Kleen, M., Liitiä, T., Tehomaa, M. (2011b) The effect of the physical form and size of raw materials in pressurized hot water extraction of birch. 16th Int. Symp. Wood, Fiber and Pulp Chem. (ISWFPC), Tianjin, China, June 8–10, Vol. 2, pp. 1015–1020.Search in Google Scholar

Leppänen, K., Spetz, P., Pranovich, A., Hartonen, K., Kutinen V., Ilvesniemi, H. (2011) Pressurized hot water extraction of Norway spruce hemicelluloses using a flow-through system. Wood. Sci. Technol. 45:223–236.10.1007/s00226-010-0320-zSearch in Google Scholar

Liu, J., Willför, S., Xu, C. (2015). A review of bioactive polysaccharides: biological activities, functionalization, and biomedical applications. Bioact. Carbohydr. Dietary Fibre 5: 31–61.10.1016/j.bcdf.2014.12.001Search in Google Scholar

Michielsen, S. (1999) Specific refractive index increments of polymers in dilute solution. In: Polymer Handbook, 4th Ed. Eds. Brandrup, J., Immergut, E.H., Grulke, E.A. Wiley, NY, USA. pp. 547–627.10.1002/0471532053.bra057Search in Google Scholar

Mikkonen, K.S., Yadav, M.P., Cooke, P., Willför, S., Hicks, K.B., Tenkanen, M. (2008) Films from spruce galactogluccomannan blended with poly (vinyl alcohol), corn arabonoxylan, and konjac glucomannans. BioRes. 3:178–191.Search in Google Scholar

Nebreda, A.P., Grénman, H., Mäki-Arvela, P., Eränen, K., Hemming, J., Willför, S., Murzin, D.Y., Salmi, T. (2016) Acid hydrolysis of O-acetyl-galactoglucomannan in a continuous tube reactor: a new approach to sugar monomer production. Holzforschung 70:187–194.10.1515/hf-2014-0314Search in Google Scholar

Ragauskas, A.J., Nagy, M., Kim, D.H., Eckert, C.A., Hallett, J.P., Liotta, C.L. (2006) From wood to fuels: Integrating biofuels and pulp production. Ind. Biotechnol. 2:55–65.10.1089/ind.2006.2.55Search in Google Scholar

Reyes, P., Ferraz, A., Pereira, M., Rodríguez, J., Mendonça, R.T. (2015) Chemithermomechanical and kraft pulping of Pinus radiata wood chips after the hydrothermal extraction of hemicelluloses. Holzforschung 69:33–40.10.1515/hf-2013-0235Search 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

Song, T., Pranovich, A., Sumerskiy, I., Holmbom, B. (2008) Extraction of galactoglucomannan from spruce wood with pressurized hot water. Holzforschung 62:659–666.10.1515/HF.2008.131Search in Google Scholar

Song, T., Pranovich, A., Holmbom, B. (2011) Characterisation of Norway spruce hemicelluloses extracted by pressurised hot-water extraction (ASE) in presence of sodium bicarbonate. Holzforschung 65:35–42.10.1515/hf.2011.015Search in Google Scholar

Sundberg, A., Sundberg, K., Lillandt, C., Holmbom, B. (1996) Determination of hemicelluloses and pectins in wood and pulp fibres by acid methanolysis and gas chromatography, Nord. Pulp Paper Res. J. 11:216–219, 226.10.3183/npprj-1996-11-04-p216-219Search in Google Scholar

Tunc, M.S., van Heiningen, A.R.P. (2008a) Hemicellulose extraction of mixed southern hardwood with water at 150°C: effect of time. Ind. Eng. Chem. Res. 47:7031–7037.10.1021/ie8007105Search in Google Scholar

Tunc, M.S., van Heiningen, A.R.P. (2008b) Hydrothermal dissolution of mixed southern hardwoods. Holzforschung 62:539–545.10.1515/HF.2008.100Search in Google Scholar

van Heiningen, A.R.P. (2006) Converting a kraft pulp mill into an integrated forest biorefinery. Pulp Pap. Can. 107:38–43.Search in Google Scholar

Vena, P.F., Brienzo, M., del Prado García-Aparicio, M., Görgens, J.F., Rypstra, T. (2013) Hemicelluloses extraction from giant bamboo (Bambusa balcooa Roxburgh) prior to kraft or soda-AQ pulping and its effect on pulp physical properties. Holzforschung 67:863–870.10.1515/hf-2012-0197Search in Google Scholar

Vila, C., Francisco, J.L., Santos, V., Parajó, J.C. (2013) Effects of hydrothermal processing on the cellulosic fraction of Eucalyptus globulus wood. Holzforschung 67:33–40.10.1515/hf-2012-0046Search 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. 72:197–210.10.1016/j.carbpol.2007.08.006Search in Google Scholar

Yoon, S.-H., Macewan, K., van Heiningen, A. (2008) Hot-water pre-extraction from loblolly pine (Pinus taeda) in an integrated forest products biorefinery. Tappi J. 2008:27–31.Search in Google Scholar

Yu, Y., Lou, X., Wu, H. (2008) Some recent advances in hydrolysis of biomass in hot-compressed water and its comparisons with other hydrolysis methods. Energy and Fuels 22: 46–60.10.1021/ef700292pSearch in Google Scholar

Received: 2015-2-20
Accepted: 2015-11-17
Published Online: 2016-4-15
Published in Print: 2016-7-1

©2016 by De Gruyter