Abstract
An essential feature of proposed fermentation-based lignocellulose to biofuel conversion processes will be the co-production of higher value chemicals from lignin and hemicellulose components. Over the years, many routes for chemical conversion of lignin and hemicelluloses have been developed by the pulp and paper industry and we propose that some of these can be applied for bioproducts manufacturing. For lignin products, thermochemical, chemical pulping, and bleaching methods for production of polymeric and monomeric chemicals are reviewed. We conclude that peroxyacid chemistry for phenol and ring-opened products looks most interesting. For hemicellulose products, preextraction of hemicelluloses from woody biomass is important and influences the mixture of solubilized material obtained. Furfural, xylitol, acetic acid, and lactic acid are possible targets for commercialization, and the latter can be further converted to acrylic acid. Pre-extraction of hemicelluloses can be integrated into most biomass-to-biofuel conversion processes.
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Davin LB, Patten AM, Jourdes M, Lewis NG (2008) Lignins: a twenty first century challenge. In: Himmel ME (ed) Biomass recalcitrance deconstructing the plant cell wall for bioenergy. Blackwell, Oxford, pp 213–305
Fengel D, Wegener G (1984) Wood: chemistry, ultrastructure, reactions. Gruyter, New York
Sjöström E (1993) Wood chemistry: fundamentals and applications, 2nd edn. Academic, San Diego
Pye KE (2006) Biorefineries—industrial processes and products. In: Gruber PR, Kamm M (eds) B Kamm. Wiley, Germany, pp 165–200
Bizzari SN, Janshekar H, Yokose K (2009) Lignosulfonates, CEH Marteking Research Report, SRI Consulting
Holladay JE, Bozell JJ, White JF, Johnson D (2007) Top value-added chemicals from biomass: volume II—results of screening for potential candidates from biorefinery lignin. US Department of Energy, New York
Gargulak JD, Lebo SE (2000) Lignin: historical, biological, and materials perspectives, chapter 15, pp 304–320, ACS symposium series no. 742., In: WG Glasser, RA Northey, and TP Schultz (eds). Washington, D.C.
Otani S, Fukuoka Y, Igarashi B, Sasaki K (1969) Method for producing carbonized lignin fiber, US patent 3461082.
Sudo K, Shimizu K, Nakashima N, Yokoyama A (1993) A new modification method of exploded lignin for the preparation of a carbon-fiber precursor. J Appl Polym Sci 48:1485–1491
Sudo K, Shimizu K (1992) A new carbon-fiber from lignin. J Appl Polym Sci 44:127–134
Pickel JM, Griffith WL, Compere AL (2006) Utilization of lignin in the production of low-cost carbon fiber. Abstracts of Papers of the American Chemical Society, 231–238.
Kubo S, Kadla JF (2005) Lignin-based carbon fibers: effect of synthetic polymer blending on fiber properties. J Polym Environ 13:97–105
Kadla JF, Kubo S, Venditti RA, Gilbert RD, Compere AL, Griffith W (2002) Lignin-based carbon fibers for composite fiber applications. Carbon 40:2913–2920
Gellerstedt G, Sjöholm E, Brodin I (2010) The wood-based biorefinery: a source of carbon fiber? Open Agric J 3:119–124
Hu TQ (2002) Chemical modification, properties, and usage of lignin. Kluwer, New York
Li Y, Sarkanen S (2000) Lignin—historical, biological, and materials perspectives. Glasser WG, Northey RA, Schultz TP (eds). ACS Symp Ser 742:351–366
Gandini A, Belgacem MN (2008) Monomers, polymers and composites from renewable resources. In: MN Belgacem and A Gandini (eds.). Elsevier: New York
Vainio U, Maximova N, Hortling B, Laine J, Stenius P, Simola LK et al (2004) Morphology of dry lignins and size and shape of dissolved kraft lignin particles by X-ray scattering. Langmuir 20:9736–9744
Kozlowski R, Zimniewska M, Batog J (2008) Cellulose fibre textiles containing nanolignins, a method of applying nanolignins onto the textile and the use of nanolignins in textile production. World Patent WO 2008/140337 A1.
Whiting DA (2001) Natural phenolic compounds 1900–2000: a bird's eye view of a century's chemistry. Nat Prod Rep 18:583–606
Boudet AM (2007) Evolution and current status of research in phenolic compounds. Phytochemistry 68:2722–2735
Nicholson RL, Hammerschmidt R (1992) Phenolic compounds and their role in disease resistance. Annu Rev Phytopathol 30:369–389
Higuchi T (1982) Biodegradation of lignin—biochemistry and potential applications. Experientia 38:159–166
Raja PB, Sethuraman MG (2008) Natural products as corrosion inhibitor for metals in corrosive media—a review. Mater Lett 62:113–116
Meier D, Ante R, Faix O (1992) Catalytic hydropyrolysis of lignin—influence of reaction conditions on the formation and composition of liquid products. Bioresour Technol 40:171–177
Thring RW, Breau J (1996) Hydrocracking of solvolysis lignin in a batch reactor. Fuel 75:795–800
Takeyama H, Sasaya T (1987) Hydrocracking of solvolysis lignin 2. Mokuzai Gakkaishi 33:212–217
Davoudzadeh F, Smith B, Avni E, Coughlin RW (1985) Depolymerization of lignin at low-pressure using Lewis acid catalysts and under high-pressure using hydrogen donor solvents. Holzforschung 39:159–166
Vuori A, Niemela M (1988) Liquefaction of kraft lignin. 2. Reactions with a homogeneous Lewis acid catalyst under mild reaction conditions. Holzforschung 42:327–334
Hepditch MM, Thring RW (2000) Degradation of solvolysis lignin using Lewis acid catalysts. Can J Chem Eng 78:226–231
Kudsy M, Kumazawa H (1999) Pyrolysis of kraft lignin in the presence of molten ZnCl2–KCl mixture. Can J Chem Eng 77:1176–1184
Caballero JA, Font R, Marcilla A (1997) Pyrolysis of kraft lignin: yields and correlations. J Anal Applied Pyrol 39:161–183
Kudsy M, Kumazawa H, Sada E (1995) Pyrolysis of kraft lignin in molten Zncl2–Kcl media with tetralin vapor addition. Can J Chem Eng 73:411–415
Kleinert M, Barth T (2008) Phenols from lignin. Chem Eng Technol 31:736–745
Vigneault A, Johnson DK, Chornet E (2007) Base-catalyzed depolymerization of lignin: separation of monomers. Can J Chem Eng 85:906–916
Shabtai JS, Zmierczak WW, Chornet E (1999) Process for conversion of lignin to reformulated hydrocarbon gasoline. US patent 6172272.
Shabtai JS, Zmierczak WW, Chornet E (2001) Process for conversion of lignin to reformulated, partially oxygenated gasoline. US patent 6172272.
Pye EK, Lora JH (1991) The Alcell process—a proven alternative to kraft pulping. Tappi J 74:113–118
Binder JB, Gray MJ, White JF, Zhang ZC, Holladay JE (2009) Reactions of lignin model compounds in ionic liquids. Biomass Bioenerg 33:1122–1130
Kleinert M, Barth T (2008) Towards a lignincellulosic biorefinery: direct one-step conversion of lignin to hydrogen-enriched biofuel. Energy Fuels 22:1371–1379
Mohan D, Pittman CU, Steele PH (2006) Pyrolysis of wood/biomass for bio-oil: a critical review. Energy Fuels 20:848–889
Ferdous D, Dalai AK, Bej SK, Thring RW, Bakhshi NN (2001) Production of H-2 and medium Btu gas via pyrolysis of lignins in a fixed-bed reactor. Fuel Process Technol 70:9–26
Serrano-Ruiz JC, West RM, Dumesic JA (2010) Catalytic conversion of renewable biomass resources to fuels and chemicals. Ann Rev Chem Biomol Eng 1(1):79–100
Jones S, Zhu Y (2009) Preliminary economics for the production of pyrolysis oil from lignin in a cellulosic ethanol biorefinery. PNNL-18401. Pacific Northwest National Laboratory: Richland, WA.
Zakzeski J, Bruijnincx PCA, Jongerius AL, Weckhuysen BM (2010) The catalytic valorization of lignin for the production of renewable chemicals. Chem Rev 110:3552–3599
Chakar FS, Ragauskas AJ (2004) Review of current and future softwood kraft lignin process chemistry. Ind Crop Prod 20:131–141
Gierer J (1985) Chemistry of delignification. 1. General concept and reactions during pulping. Wood Sci Technol 19:289–312
Robert DR, Bardet M, Gellerstedt G, Lindfors EL (1984) Structural changes in lignin during kraft cooking. 3. On the structure of dissolved lignins. J Wood Chem Technol 4:239–263
Baptista C, Robert D, Duarte AP (2008) Relationship between lignin structure and delignification degree in Pinus pinaster kraft pulps. Bioresour Technol 99:2349–2356
Wang PQ, Wang LQ, Quan JY (1999) The application of a new plant growth regulator (ASL) on agriculture and forestry. J Nanjing Forest Univ (Natural Science Edition) 23(4):1–6
Argyropoulos D (2001) Oxidative delignification chemistry: fundamentals and catalysis, ACS Symposium series 785. American Chemical Society.
Dence CW, Reeve DW (1996) Pulp bleaching: principles and practice. Atlanta GA, Tappi
Corma A, Iborra S, Velty A (2007) Chemical routes for the transformation of biomass into chemicals. Chem Rev 107:2411–2502
Draths KM, Frost JW (1994) Environmentally compatible synthesis of adipic acid from d-glucose. J Am Chem Soc 116:399–400
Niu W, Draths KM, Frost JW (2002) Benzene-free synthesis of adipic acid. Biotechnol Prog 18:201–211
She XY, Brown HM, Zhang X, Ahring BK, Wang Y (2011) Selective hydrogenation of trans, trans-muconic acid to adipic acid over a titania-supported rhenium catalyst. Chemsuschem. doi:10.1002/cssc.201100020
Suchy M, Argyropoulos DS (2001) In: Argyropoulos DS (ed) Oxidative delignification chemistry fundamentals and catalysis. Oxford University Press, Washington DC, pp 2–43
Gierer J (1986) Chemistry of delignification. 2. Reactions of lignins during bleaching. Wood Sci Technol 20:1–33
Sundquist J, Poppius-Levlin K (1997) In: Young RA, Akhtar M (eds) Environmentally friendly technologies for the pulp and paper industry. Wiley, New York, pp 157–190
Johnson D (1975) Lignin reactions in delignification with peroxyacetic acid. 1st International Symposium on Delignification with Oxygen, Ozone and Peroxides, pp. 217–228. Raeigh, NC, USA.
Kadla JF, Chang H-M (2001) In: Argyropoulos DS (ed) Oxidative delignification chemistry. Oxford University Press, Washington DC, pp 108–129
Reid I, Bourbonnais R, Paice M (2010) Lignin and lignans—advances in chemistry. In: Heitner C, Dimmel D, Schmidt JA (eds). CRC: Boca Raton, FL. pp. 521–554.
Ezeji T, Qureshi N, Blaschek HP (2007) Butanol production from agricultural residues: impact of degradation products on Clostridium beijerinckii growth and butanol fermentation. Biotechnol Bioeng 97:1460–1469
Qureshi N, Sahaa BC, Hector RE, Hughes SR, Cotta MA (2008) Butanol production from wheat straw by simultaneous saccharification and fermentation using Clostridium beijerinckii: part I—batch fermentation. Biomass Bioenerg 32:168–175
Martinez A, Rodriguez ME, Wells ML, York SW, Preston JF, Ingram LO (2001) Detoxification of dilute acid hydrolysates of lignocellulose with lime. Biotechnol Prog 17:287–293
Yoon SH, Macewan K, Van Heiningen A (2008) Hot-water pre-extraction from loblolly pine (Pinus taeda) in an integrated forest products biorefinery. Tappi J 7:27–32
Kim KH, Tucker MP, Keller FA, Aden A, Nguyen QA (2001) Continuous countercurrent extraction of hemicellulose from pretreated wood residues. Appl Biochem Biotech 91–3:253–267
Sattler C, Labbe N, Harper D, Elder T, Rials T (2008) Effects of hot water extraction on physical and chemical characteristics of oriented strand board (OSB) wood flakes. Clean-Soil Air Water 36:674–681
Al-Dajani WW, Tschirner UW (2008) Pre-extraction of hemicelluloses and subsequent kraft pulping. Part I: alkaline extraction. Tappi J 7:3–8
Springer EL, Harris JF (1982) Prehydrolysis of aspen wood with water and with dilute aqueous sulfuric acid. Svensk Papperstidning 85:152–154
Conner AH (1984) Kinetic modeling of hardwood prehydrolysis. 1. Xylan removal by water prehydrolysis. Wood Fiber Sci 16:268–277
Conner AH, Libkie K, Springer EL (1985) kinetic modeling of hardwood prehydrolysis. 2. Xylan removal by dilute hydrochloric acid prehydrolysis. Wood and Fiber Science 17:540–548
Conner AH, Lorenz LF (1986) kinetic modeling of hardwood prehydrolysis. 3. Water and dilute acetic-acid prehydrolysis of Southern Red Oak. Wood and Fiber Science 18:248–263
Nguyen QA, Tucker MP, Keller FA, Eddy FP (2000) Two-stage dilute-acid pretreatment of softwoods. Appl Biochem Biotechnol 84–6:561–576
Lundqvist J, Teleman A, Junel L, Zacchi G, Dahlman O, Tjerneld F et al (2002) Isolation and characterization of galactoglucomannan from spruce (Picea abies ). Carbohydr Polym 48:29–39
Lundqvist J, Jacobs A, Palm M, Zacchi G, Dahlman O, Stalbrand H (2003) Characterization of galactoglucomannan extracted from spruce (Picea abies) by heat-fractionation at different conditions. Carbohydr Polym 51:203–211
Radiotis T, Zhang X, Paice M, Byrne V (2010) Optimizing production of xylose and xylooligomers from wood chips (in press). FPInnovations Research Report PRR 1929, October 2010
Yoon SH, Cullinan HT, Krishnagopalan GA (2010) Reductive modification of alkaline pulping of southern pine, integrated with hydrothermal pre-extraction of hemicelluloses. Ind Eng Chem Res 49:5969–5976
Walton SL, Hutto D, Genco JM, van Walsum GP, van Heiningen ARP (2010) Pre-extraction of hemicelluloses from hardwood chips using an alkaline wood pulping solution followed by kraft pulping of the extracted wood chips. Ind Eng Chem Res 49:12638–12645
Bozell JJ, Petersen GR (2010) Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy's "Top 10" revisited. Green Chem 12:539–554
Werpy T, Petersen G (2007) Top value added chemicals from biomass volume i: results of screening for potential candidates from sugars and synthesis gas. Pacific Northwest National Laboratory (PNNL) and National Renewable Energy Laboratory (NREL).
Chheda JN, Roman-Leshkov Y, Dumesic JA (2007) Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides. Green Chem 9:342–350
Tong X, Ma Y, Li Y (2010) Biomass into chemicals: conversion of sugars to furan derivatives by catalytic processescess. Appl Catal a-Gen 385:1–13
Zeitsch KJ (2000) The chemistry and technology of furfural and its many by-products. ISBN 9780444503510 ed. New York: Elsevier
Sain B, Chaudhuri A, Borgohain JN, Baruah BP, Ghose JL (1982) Furfural and furfural-based industrial chemicals. J Sci Ind Res 41:431–438
Hoydonckx HE, Van Rhijn WM, Van Rhijn W, De Vos DE, Jacobs PA (2007) Ullmann's encyclopedia of industrial chemistry. Wiley, New York
Win DT (2005) Furfural-gold from garbage. AU J Technol 8:185–190
Marinova M, Mateos-Espejel E, Paris J (2010) From kraft mill to forest biorefinery: an energy and water perspective. II. Case study. Cellul Chem Technol 44:21–26
D'Amico E (2009) Danisco issues profit warning; curtails xylitol production. Chemical Week, March 9
Aachary AA, Prapulla SG (2011) Xylooligosaccharides (XOS) as an emerging prebiotic: microbial synthesis, utilization, structural characterization, bioactive properties, and applications. Compr Rev Food Sci Food Saf 10:2–16
Bozell JJ (2008) Feedstocks for the future—biorefinery production of chemicals from renewable carbon. Clean-Soil Air Water 36:641–647
Hermann BG, Patel M (2007) Today's and tomorrow's bio-based bulk chemicals from white biotechnology—a techno-economic analysis. Appl Biochem Biotechnol 136:361–388
Manzer, LE (2006) Biomass derivatives: a sustainable source of chemicals. In: Feedstocks for the future: renewables for the production of chemicals and materials, 921. pp 40–51.
Nikolau BJ, Perera MADN, Brachova L, Shanks B (2008) Platform biochemicals for a biorenewable chemical industry. Plant J 54:536–545
Patel M, Ou M, Ingram LO, Shanmugam KT (2004) Fermentation of sugar cane bagasse hemicellulose hydrolysate to L(+)-lactic acid by a thermotolerant acidophilic Bacillus sp. Biotechnol Lett 26:865–868
Moldes AB, Torrado A, Converti A, Dominguez JM (2006) Complete bioconversion of hemicellulosic sugars from agricultural residues into lactic acid by Lactobacillus pentosus. Appl Biochem Biotech 135:219–227
Iyer PV, Thomas S, Lee YY (2000) High-yield fermentation of pentoses into lactic acid. Appl Biochem Biotech 84–6:665–677
Huang JR, Li WS, Zhou XP (2010) Preparation of lactic acid from glucose in ionic liquid solvent system. J Cent South Univ T 17:45–49
Onda A, Ochi T, Kajiyoshi K, Yanagisawa K (2008) A new chemical process for catalytic conversion Of D-glucose into lactic acid and gluconic acid. Appl Catal a-Gen 343:49–54
Holm MS, Saravanamurugan S, Taarning E (2010) Conversion of sugars to lactic acid derivatives using heterogeneous zeotype catalysts. Science 328:602–605
Onda A, Ochi T, Kajiyoshi K, Yanagisawa K (2008) Lactic acid production from glucose over activated hydrotalcites as solid base catalysts in water. Catal Commun 9:1050–1053
West RM, Holm MS, Saravanamurugan S, Xiong JM, Beversdorf Z, Taarning E et al (2010) Zeolite H-USY for the production of lactic acid and methyl lactate from C-3-sugars. J Catal 269:122–130
Holmen RE (1958) Production of acrylates by catalytic dehydration of lactic acid and alkyl lactates. US Patent 2,959,240
Sawicki RA (1998) Catalyst for dehydration of lactic acid to acrylic acid. US Patent 4,729,978.
Varadarajan S, Miller DJ (1999) Catalytic upgrading of fermentation-derived organic acids. Biotechnol Progr 15:845–854
Aida TM, Ikarashi A, Saito Y, Watanabe M, Smith RL, Arai K (2009) Dehydration of lactic acid to acrylic acid in high temperature water at high pressures. J Supercrit Fluid 50:257–264
Paparizos CD, Serge R, Shaw WG (1988) Catalytic conversion of lactic acid and ammonium lactate to acrylic acid. US Patent 4,786,756.
Walkup PCR, Charles A, Hellen, Richard T, Eakin, David E. (1991) Production of esters of lactic acid, esters of acrylic acid, lactic acid, and acrylic acid. US Patent 5,071,754.
Lilga MAW, Todd A, Holladay, Johnathan E (2006) Methods of forming alpha, beta-unsaturated acids and esters. US Patent 6,992,209.
Ratchford WP, Fisher CH (1945) Methyl acrylate by pyrolysis of methyl acetoxypropionate—effect of pressures of 1 to 67 atmospheres. Ind Eng Chem 37:382–387
Scholze B, Meier D (2001) Characterization of the water-insoluble fraction from pyrolysis oil (pyrolytic lignin). Part I. PY-GC/MS, FTIR, and functional groups. J Anal Applied Pyrol 60:41–54
Mosier N, Wyman C, Dale B, Elander R, Lee YY, Holtzapple M et al (2005) Features of promising technologies for pretreatment of lignocellulosic biomass. Bioresour Technol 96:673–686
Wyman CE, Dale BE, Elander RT, Holtzapple M, Ladisch MR, Lee YY (2005) Coordinated development of leading biomass pretreatment technologies. Bioresour Technol 96:1959–1966
Pan XJ, Arato C, Gilkes N, Gregg D, Mabee W, Pye K et al (2005) Biorefining of softwoods using ethanol organosolv pulping: preliminary evaluation of process streams for manufacture of fuel-grade ethanol and co-products. Biotechnol Bioeng 90:473–481
Arato C, Pye EK, Gjennestad G (2005) The lignol approach to biorefining of woody biomass to produce ethanol and chemicals. Appl Biochem Biotechnol 121:871–882
Chang VS, Nagwani M, Holtzapple MT (1998) Lime pretreatment of crop residues bagasse and wheat straw. Appl Biochem Biotechnol 74:135–159
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Zhang, X., Tu, M. & Paice, M.G. Routes to Potential Bioproducts from Lignocellulosic Biomass Lignin and Hemicelluloses. Bioenerg. Res. 4, 246–257 (2011). https://doi.org/10.1007/s12155-011-9147-1
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DOI: https://doi.org/10.1007/s12155-011-9147-1