Abstract
Herein, we report about existing and novel dissolving pulp processes providing the basis for an advanced biorefinery. The SO2–ethanol–water (SEW) process has the potential to replace the acid sulphite process for the production of rayon-grade pulps owing to a higher flexibility in the selection of the raw material source, substantially lower cooking times, and the near absence of sugar degradation products. Special attention is paid to developments that target toward the selective and quantitative fractionation of paper-grade pulps into hemicelluloses and cellulose of highest purity. This target has been accomplished by the IONCELL process where the entire hemicellulose fraction is selectively dissolved in an ionic liquid in which the H-bond basicity and acidity are adequately adjusted by the addition of a co-solvent. At the same time, pure hemicellulose can be recovered by further addition of the co-solvent, which then acts as a non-solvent. The residual pure cellulose fraction may then enter a Lyocell process for the production of regenerated cellulose products.
Similar content being viewed by others
References
Alekhina M, Mikkonen KS, Alen R, Tenkanen M, Sixta H (2013) Preparation and characterization of biodegradable carboxymethyl xylan based film. Carbohydr Polym (in press). doi:101016/jcarbpol201303048
Berggren R, Berthold F, Sjöholm E, Lindström M (2003) Improved methods for evaluating the molar mass distributions of cellulose in kraft pulp. J Appl Polym Sci 88:1170–1179
Borrega M, Nieminen K, Sixta H (2011) Degradation kinetics of the main carbohydrates in birch wood during hot water extraction in a batch reactor at elevated temperatures. Bioresour Technol 6:1890–1903
Borrega M, Tolonen LK, Bardot F, Testova L, Sixta H (2013) Potential of hot water extraction of birch wood to produce high-purity dissolving pulp after alkaline pulping. Bioresour Technol 135:665–671
Brice R (2012) High purity cellulose through 2020. In: The cellulose gap Monte Carlo. http://csales.ch/cellulosegap2012_lineup.php
Doherty TV, Mora-Pale M, Foley SE, Linhardt RJ, Dordick JS (2010) Ionic liquid solvent properties as predictors of lignocellulose pretreatment efficacy. Green Chem 11:1967–1975
Fasching M, Griebl A, Kandioller G, Zieher A, Weber H, Sixta H (2005) Prehydrolysis sulfite revisited. Macromol Symp 223:225–238
Froschauer C, Hummel M, Iakovlev M, Roselli A, Schottenberger H, Sixta H (2013) Fractionation of hemicellulose-rich pulp into hemicellulose and cellulose by means of ionic liquid/cosolvent mixtures. Biomacromolecules. doi:10.1021/bm400106h
Gehmayr V, Schild G, Sixta H (2011) A precise study on the feasibility of enzyme treatments of a kraft pulp for viscose application. Cellulose 18:479–491
Guetsch J, Sixta H (2012) Regeneration of spent activated charcoals used for lignin removal from prehydrolysis-kraft prehydrolysates. Ind Eng Chem Res 51:8624–8630
Guetsch J, Leschinsky M, Sixta H (2011) Process for improved processability of hydrothermolyzates of lignocellulosic material by hydrolysis and adsorption. WO 2011150436 A1 20111208: WO 2011150436 A1 20111208
Haemmerle FM (2011) The cellulose gap. Lenzinger Berichte 89:12–21
Hauru LKJ, Hummel M, King AWT, Kilpeläinen I, Sixta H (2012) Role of solvent parameters in the regeneration of cellulose from ionic liquid solutions. Biomacromolecules 13:2896–2905
Heikkila H, Kuisma J, Lindroos M, Puuppo O, Eroma O-P (1999) Method of producing xylose by chromatographic separation of xylose from sulfite cooking liquors. WO 9934021 A1 19990708
Hinck JF, Casebier RL, Hamilton JK (1985) Dissolving pulp manufacturing. In: Ingruber OV, Kocurek MJ, Wong A (eds) Sulfite science and technology. TAPPI, Atlanta, pp 213–243
Huepfl J, Zauner J (1966) Pruefung von Chemiefaserzellstoffen an einer Viskose-Kleinstanlage. Das Papier 20:125–132
Iakovlev M, Heiningen A (2012) Efficient fractionation of spruce by SO2-ethanol-water treatment: closed mass balances for carbohydrates and sulfur. ChemSusChem 5:1625–1637
Ibarra D, Koepcke V, Ek M (2009) Exploring enzymatic treatments for the production of dissolving grade pulp from different wood and non-wood paper grade pulps. Holzforschung 63:721–730
Ibarra D, Koepcke V, Ek M (2010a) Behavior of different monocomponent endoglucanases on the accessibility and reactivity of dissolving-grade pulps for viscose process. Enzym Microb Technol 47:355–362
Ibarra D, Koepcke V, Larsson PT, Jaeaeskelaeinen A-S, Ek M (2010b) Combination of alkaline and enzymatic treatments as a process for upgrading sisal paper-grade pulp to dissolving-grade pulp. Bioresour Technol 101:7416–7423
Janson J (1974) Analytik der Polysaccharide in Holz und Zellstoff. Faserforschung und Textiltechnik 25:375–382
Janzon R, Puls J, Saake B (2006) Upgrading of paper-grade pulps to dissolving pulps by nitren extraction: optimisation of extraction parameters and application to different pulps. Holzforschung 60:347–354
Janzon R, Puls J, Bohn A, Potthast A, Saake B (2008) Upgrading of paper-grade pulps to dissolving pulps by nitren extraction: yields, molecular and supramolecular structures of nitren extracted pulps. Cellulose 15:739–750
Kettenbach G, Stein A (2002) Process for separating hemicellulose from biomass, and the resulting biomass and hemicellulose. DE 10109502 A1 20020912: Ger. Offen
Koepcke V, Ibarra D, Ek M (2008) Increasing accessibility and reactivity of paper grade pulp by enzymatic treatment for use as dissolving pulp. Nord Pulp Pap Res J 23:363–368
Koepcke V, Ibarra D, Larsson PT, Ek M (2010a) Optimization of treatment sequences for the production of dissolving pulp from birch kraft pulp. Nord Pulp Pap Res J 25:31–38
Koepcke V, Ibarra D, Larsson PT, Ek M (2010b) Optimization of treatments for the conversion of eucalyptus kraft pulp to dissolving pulp. Polym Renew Resour 1:17–34
Leschinsky M, Sixta H, Patt R (2009) Detailed mass balances of the autohydrolysis of Eucalyptus globulus at 170 °C. Bioresources 4:687–703
Li J, Gellerstedt G, Lutnaes B (2008) Tetraethylammonium salt preparation and sulphonate group NMR quantification of industrial lignosulphonates. In: 10th European Workshop on Lignocellulosics and Pulp Stockholm, Sweden
Penttilae PA, Várnai A, Leppaenen K, Peura M, Kallonen A, Jaeaeskelaeinen P, Lucenius J, Ruokolainen J, Siika-aho M, Viikari L, Serimaa R (2010) Changes in submicrometer structure of enzymatically hydrolyzed microcrystalline cellulose. Biomacromolecules 11:1111–1117
Puls J, Janzon R, Saake B (2006) Comparative removal of hemicelluloses from paper pulps using nitren, cuen, NaOH and KOH. Lenzinger Berichte 86:63–70
Rauhala T, King A, Zuckerstaetter G, Suuronen S, Sixta H (2011) Effect of autohydrolysis on the lignin structure and the kinetics of delignification of birch wood. Nord Pulp Pap Res J 26:386–391
Roeder T, Moosbauer J, Fasching M, Bohn A, Fink H-P, Baldinger T, Sixta H (2006) Crystallinity determination of man-made cellulose fibers—a comparison of analytical methods. Lenzinger Berichte 86:132–136
Rydholm SA (1965) Cold caustic extraction. In: Pulping processes, pp 994–1001: Robert E. Krieger
Schild G, Sixta H (2010) Multifunctional alkaline pulping, delignification and hemicellulose extraction. Cellul Chem Technol 44:35–45
Schild G, Sixta H (2011) Sulfur-free dissolving pulps and their application for viscose and lyocell. Cellulose 18:1113–1128
Schild G, Mueller W, Sixta H (1996) Prehydrolysis kraft and ASAM paper grade pulping of eucalypt wood. A kinetic study. Das Papier 50:10–22
Shen L, Patel MK (2010) Life cycle assessment of man-made cellulose fibers. Lenzinger Berichte 88:1–59
Sixta H (1986) Cellulose preparation and recycling of raw materials and auxiliaries by the Lenzinger magnesium bisulfite process. Lenzinger Berichte 61:5–11
Sixta H (2000) Comparative evaluation of TCF bleached hardwood dissolving pulps. Lenzinger Berichte 79:119–128
Sixta H (ed) (2006a) Multistage kraft pulping. In: Handbook of pulp, vol 1. Wiley-VCH, New York, pp 325–365
Sixta H (ed) (2006b) Pulp properties and applications. In: Handbook of pulp, vol 2. Wiley-VCH, New York, pp 1009–1067
Sixta H (ed) (2006c) Pulp purification. In: Handbook of pulp, vol 2. Wiley-VCH, New York, pp 933–965
Sixta H (ed) (2006d) Sulfite chemical pulping. In: Handbook of pulp, vol 1. Wiley-VCH, New York, pp 392–509
Sixta H, Schild G (2009) New generation kraft process. In: 2nd Nordic Wood Biorefinery Conference Helsinki
Sixta H, Promberger A, Koch G, Gradinger C, Messner K (2004) Influence of beech wood quality on bisulfite dissolving pulp manufacture. Part 1: influence of log storage on pulping and bleaching. Holzforschung 58:14–21
Sixta H, Borrega M, Testova L, Costabel L, Alekhina M, Guetsch J (2011a) Progress and challenges in the separation and purification of xylan from hardwood. In: 3rd nordic wood and biorefinery conference (NWBC) Stockholm, March 22–24
Sixta H, Guetsch J, Nousiainen T, Wollboldt P (2011b) Progress and challenges in the isolation of xylan from Eucalyptus Wood. In: 5th international colloquium on eucalyptus pulp porto seguro, May 8–11
Sixta H, Hummel M, Michud A, Hauru LKJ, Froschauer C, Schottenberger H (2012) Progress in processing lignocellulose with ionic liquids. In: 3rd international cellulose conference (ICC2012) Sapporo, Japan
Sjoestroem E (1993) Wood chemistry: fundamentals and applications. Academic Press, New York
Sklavounos E, Iakovlev M, Heiningen A (2013) Study on conditioning of SO2-ethanol-water spent liquor from spruce chips/softwood biomass for ABE fermentation. Ind Eng Chem Res 52(11):4351–4359
Swan B (1965) Isolation of acid-soluble lignin from the Klason lignin determination. Svenska Papperstidning 68:791–795
Swatlowski RP, Scott K, Hilbrey JD, Rogers RD (2002) Dissolution of cellulose with ionic liquids. J Am Chem Soc 124:4974–4975
Temming H, Grunert H (1973) Temming linters. Peter Temming AG, Glueckstadt
Testova L, Sixta H (2013) Development of an alkali-borax refining treatment for the conversion of a commercial pine paper pulp to an acetate-grade dissolving pulp. In: WOBAMA progress report. doi:10.1016/j.carbpol.2013.01.093
Testova L, Nieminen K, Penttilae PA, Serimaa R, Potthast A, Sixta H (2013) Cellulose degradation in alkaline media upon acidic pretreatment and stabilization. Carbohydr Polym (accepted)
Treiber E, Rehnstroem J, Ameen C, Kolos F (1962) A small scale laboratory viscose plant for testing rayon grade pulps. Das Papier 16:85–94
Vaaler DAG (2008) Yield-increasing additives in kraft pulping: effect on carbohydrate retention, composition and handsheet properties. In: Department of Chemical Engineering, PhD thesis Trondheim: Norwegian University of Science and Technology
Wedzicha BL, Goddard SJ (1991) The state of sulfur dioxide at high concentration and low water activity. Food Chem 40:119–136
Wiley E (2011) The practicalities of converting to DP technology. Andritz Pulp&Paper
Wilson JD, Tabke RS (1974) Influence of hemicelluloses on acetate processing in high catalyst systems. Tappi 57:77–80
Wizani W, Krotscheck A, Schuster J, Lackner K (1994) Visose production process. WO 9412719 A1 19940609
Wollboldt P (2011) Lignosulfonate characterization. Wood KPlus
Wollboldt P, Zuckerstaetter G, Weber H, Larsson PT, Sixta H (2010) Accessibility, reactivity and supramolecular structure of E. globulus pulps with reduced xylan content. Wood Sci Technol 44:533–546
Xing R, Qi W, Huber GW (2011) Production of furfural and carboxylic acids from waste aqueous hemicellulose solutions from the pulp and paper and cellulosic ethanol industries. Energy Environ Sci 4:2193–2205
Zaranyika MF, Madimu M (1989) Heterogeneous dilute acid hydrolysis of cellulose: a kinetic model for the hydrolysis of the difficultly accessible portion of cellulose based on Donnan’s theory of membrane equilibria. J Polym Sci Part A Polym Chem 6:1863–1872
Acknowledgments
Funding from Finnish Funding Agency for Technology and Innovation (Tekes) and FiBiC (former Forestcluster Ltd.) as a part of the Future Biorefinery programme is gratefully acknowledged.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Sixta, H., Iakovlev, M., Testova, L. et al. Novel concepts of dissolving pulp production. Cellulose 20, 1547–1561 (2013). https://doi.org/10.1007/s10570-013-9943-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-013-9943-1