Microwave assisted acid and alkali pretreatment of <i>Miscanthus </i>biomas<i>s </i>for biorefineries

Zongyuan Zhu; Rachael Simister; Susannah Bird; Simon J. McQueen-Mason; Leonardo D. Gomez; Duncan J. Macquarrie; Zongyuan Zhu; Rachael Simister; Susannah Bird; Simon J. McQueen-Mason; Leonardo D. Gomez; Duncan J. Macquarrie

doi:10.3934/bioeng.2015.4.449

AIMS Bioengineering

2015, Volume 2, Issue 4: 449-468. doi: 10.3934/bioeng.2015.4.449

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Microwave assisted acid and alkali pretreatment of Miscanthus biomass for biorefineries

1.
Green Chemistry Centre of Excellence, Department of Chemistry, University of York, Heslington, York, YO10 5DD, United Kingdom;
2.
Center for Novel Agricultural Products, Department of Biology, University of York, York, Heslington YO10 5DD, United Kingdom

Received: 08 June 2015 Accepted: 12 October 2015 Published: 23 October 2015

Miscanthus is a major bioenergy crop in Europe and a potential feedstock for second generation biofuels. Thermochemical pretreatment is a significant step in the process of converting lignocellulosic biomass into fermentable sugars. In this work, microwave energy was applied to facilitate NaOH and H₂SO₄pretreatments of Miscanthus. This was carried out at 180 ℃ in a monomode microwave cavity at 300 W. Our results show that H₂SO₄ pretreatment contributes to the breakdown of hemicelluloses and cellulose, leading to a high glucose yield. The maximum sugar yield from available carbohydrates during pretreatment is 75.3% (0.2 M H₂SO₄ 20 Min), and glucose yield is 46.7% under these conditions. NaOH and water pretreatments tend to break down only hemicellulose in preference to cellulose, contributing to high xylose yield. Compared to conventional heating NaOH/H₂SO₄ pretreatment, 12 times higher sugar yield was obtained by using microwave assisted pretreatment within half the time. NaOH pretreatments lead to a significantly enhanced digestibility of the residue, because the effective removal of lignin and hemicellulose makes cellulose fibres more accessible to cellulases. Morphological study of biomass shows that the tightly packed fibres in the Miscanthus were dismantled and exposed under NaOH condition. We studied sugar degradation under microwave assisted H₂SO₄ conditions. The results shows that 6-8% biomass was converted into levulinic acid (LA) during pretreatment, showing the possibility of using microwave technology to produce LA from biomass. The outcome of this work shows great potential for using microwave in the thermo-chemical pretreatment for biomass and also selective production of LA from biomass.
- microwave pretreatment,
- temperature dependence,
- Miscanthus,
- NaOH,
- H₂SO₄,
- digestibility,
- levulinic acid
Citation: Zongyuan Zhu, Rachael Simister, Susannah Bird, Simon J. McQueen-Mason, Leonardo D. Gomez, Duncan J. Macquarrie. Microwave assisted acid and alkali pretreatment of Miscanthus biomass for biorefineries[J]. AIMS Bioengineering, 2015, 2(4): 449-468. doi: 10.3934/bioeng.2015.4.449

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Abstract

Miscanthus is a major bioenergy crop in Europe and a potential feedstock for second generation biofuels. Thermochemical pretreatment is a significant step in the process of converting lignocellulosic biomass into fermentable sugars. In this work, microwave energy was applied to facilitate NaOH and H₂SO₄pretreatments of Miscanthus. This was carried out at 180 ℃ in a monomode microwave cavity at 300 W. Our results show that H₂SO₄ pretreatment contributes to the breakdown of hemicelluloses and cellulose, leading to a high glucose yield. The maximum sugar yield from available carbohydrates during pretreatment is 75.3% (0.2 M H₂SO₄ 20 Min), and glucose yield is 46.7% under these conditions. NaOH and water pretreatments tend to break down only hemicellulose in preference to cellulose, contributing to high xylose yield. Compared to conventional heating NaOH/H₂SO₄ pretreatment, 12 times higher sugar yield was obtained by using microwave assisted pretreatment within half the time. NaOH pretreatments lead to a significantly enhanced digestibility of the residue, because the effective removal of lignin and hemicellulose makes cellulose fibres more accessible to cellulases. Morphological study of biomass shows that the tightly packed fibres in the Miscanthus were dismantled and exposed under NaOH condition. We studied sugar degradation under microwave assisted H₂SO₄ conditions. The results shows that 6-8% biomass was converted into levulinic acid (LA) during pretreatment, showing the possibility of using microwave technology to produce LA from biomass. The outcome of this work shows great potential for using microwave in the thermo-chemical pretreatment for biomass and also selective production of LA from biomass.

References

[1]	Kaar WE, Holtzapple MT (2000) Using lime pretreatment to facilitate the enzymic hydrolysis of corn stover. Biomass Bioenerg 18: 189-199. doi: 10.1016/S0961-9534(99)00091-4
[2]	Ju Y-H, Huynh L-H, Kasim NS, et al. (2011) Analysis of soluble and insoluble fractions of alkali and subcritical water treated sugarcane bagasse. Carbohyd Polym 83: 591-599. doi: 10.1016/j.carbpol.2010.08.022
[3]	Han M, Choi GW, Kim Y, et al. (2011) Bioethanol Production by Miscanthus as a Lignocellulosic Biomass: Focus on High Efficiency Conversion to Glucose and Ethanol. Bioresources 6: 1939-1953.
[4]	Lu X, Xi B, Zhang Y, et al. (2011) Microwave pretreatment of rape straw for bioethanol production: Focus on energy efficiency. Bioresource Technol 102: 7937-7940. doi: 10.1016/j.biortech.2011.06.065
[5]	Xu J, Chen HZ, Kadar Z, et al. (2011) Optimization of microwave pretreatment on wheat straw for ethanol production. Biomass Bioenerg 35: 3859-3864. doi: 10.1016/j.biombioe.2011.04.054
[6]	Brosse N, Dufour A, Meng XZ, et al. (2012) Miscanthus: a fast-growing crop for biofuels and chemicals production. Biofuels Bioprod Biorefining 6: 580-598. doi: 10.1002/bbb.1353
[7]	Chen W-H, Tu Y-J, Sheen H-K (2011) Disruption of sugarcane bagasse lignocellulosic structure by means of dilute sulfuric acid pretreatment with microwave-assisted heating. Appl Energ 88: 2726-2734. doi: 10.1016/j.apenergy.2011.02.027
[8]	Sun Y, Cheng JY (2002) Hydrolysis of lignocellulosic materials for ethanol production: a review. Bioresource Technol 83: 1-11. doi: 10.1016/S0960-8524(01)00212-7
[9]	Kovacs K, Macrelli S, Szakacs G, et al. (2009) Enzymatic hydrolysis of steam-pretreated lignocellulosic materials with Trichoderma atroviride enzymes produced in-house. Biotechnol Biofuels 2: 14. doi: 10.1186/1754-6834-2-14
[10]	Balat M, Balat H, Oz C (2008) Progress in bioethanol processing. Prog Energ Combust Sci 34: 551-573. doi: 10.1016/j.pecs.2007.11.001
[11]	Alizadeh H, Teymouri F, Gilbert TI, et al. (2005) Pretreatment of switchgrass by ammonia fiber explosion (AFEX). Appl Biochem Biotech 121: 1133-1141.
[12]	Kim KH, Hong J (2001) Supercritical CO₂ pretreatment of lignocellulose enhances enzymatic cellulose hydrolysis. Bioresource Technol 77: 139-144. doi: 10.1016/S0960-8524(00)00147-4
[13]	Nikolic S, Mojovic L, Rakin M, et al. (2011) Utilization of microwave and ultrasound pretreatments in the production of bioethanol from corn. Clean Technol Environ Policy 13: 587-594. doi: 10.1007/s10098-011-0366-0
[14]	Xu N, Zhang W, Ren SF, et al. (2012) Hemicelluloses negatively affect lignocellulose crystallinity for high biomass digestibility under NaOH and H₂SO₄ pretreatments in Miscanthus. Biotechnol Biofuels 5: 58. doi: 10.1186/1754-6834-5-58
[15]	Canilha L, Santos VTO, Rocha GJM, et al. (2011) A study on the pretreatment of a sugarcane bagasse sample with dilute sulfuric acid. J Ind Microbiol Biot 38: 1467-1475. doi: 10.1007/s10295-010-0931-2
[16]	Rezende CA, de Lima MA, Maziero P, et al. (2011) Chemical and morphological characterization of sugarcane bagasse submitted to a delignification process for enhanced enzymatic digestibility. Biotechnol Biofuels 4: 1-18. doi: 10.1186/1754-6834-4-1
[17]	Macquarrie DJ, Clark JH, Fitzpatrick E (2012) The microwave pyrolysis of biomass. Biofuels Bioprod Biorefining 6: 549-560. doi: 10.1002/bbb.1344
[18]	Hu Z, Wen Z (2008) Enhancing enzymatic digestibility of switchgrass by microwave-assisted alkali pretreatment. Biochem Eng J 38: 369-378.
[19]	Keshwani DR, Cheng JJ (2010) Microwave-based alkali pretreatment of switchgrass and coastal bermudagrass for bioethanol production. Biotechnol Progr 26: 644-652.
[20]	Zhu S, Wu Y, Yu Z, et al. (2006) Microwave-assisted alkali pre-treatment of wheat straw and its enzymatic hydrolysis. Biosyst Eng 94: 437-442. doi: 10.1016/j.biosystemseng.2006.04.002
[21]	Kappe CO (2004) Controlled Microwave Heating in Modern Organic Synthesis. Angew Chem Int Ed 43: 6250-6284. doi: 10.1002/anie.200400655
[22]	Jones L, Milne JL, Ashford D, et al. (2003) Cell wall arabinan is essential for guard cell function. Proc Natl Acad Sci U S A 100: 11783-11788. doi: 10.1073/pnas.1832434100
[23]	Foster CE, Martin TM, Pauly M (2010) Comprehensive Compositional Analysis of Plant Cell Walls (Lignocellulosic biomass) Part II: Carbohydrates. e1837.
[24]	Foster CE, Martin TM, Pauly M (2010) Comprehensive Compositional Analysis of Plant Cell Walls (Lignocellulosic biomass) Part I: Lignin. e1745.
[25]	Gomez LD, Whitehead C, Barakate A, et al. (2010) Automated saccharification assay for determination of digestibility in plant materials. Biotechnol Biofuels 3: 23. doi: 10.1186/1754-6834-3-23
[26]	Wang W, Yuan TQ, Wang K, et al. (2012) Combination of biological pretreatment with liquid hot water pretreatment to enhance enzymatic hydrolysis of Populus tomentosa. Bioresource Technol 107: 282-286. doi: 10.1016/j.biortech.2011.12.116
[27]	Youngmi Kim RH, Nathan S. Mosier,Michael R. Ladisch (2009) Liquid Hot Water Pretreatment of Cellulosic Biomass. Biofuel methods and protocols.Mielenz. JR, editor. New York: Humana Press Inc, 93-102.
[28]	Hendriks ATWM, Zeeman G (2009) Pretreatments to enhance the digestibility of lignocellulosic biomass. Bioresource Technol 100: 10-18. doi: 10.1016/j.biortech.2008.05.027
[29]	Garrote G, Dominguez H, Parajo JC (1999) Hydrothermal processing of lignocellulosic materials. Holz Als Roh-Und Werkstoff 57: 191-202. doi: 10.1007/s001070050039
[30]	Szabolcs A, Molnar M, Dibo G, et al. (2013) Microwave-assisted conversion of carbohydrates to levulinic acid: an essential step in biomass conversion. Green Chem 15: 439-445. doi: 10.1039/C2GC36682G
[31]	Lee YY, Iyer P, Torget RW (1999) Dilute-Acid Hydrolysis of Lignocellulosic Biomass. In: Tsao GT, Brainard AP, Bungay HR et al., editors. Advances in Biochemical Engineering/Biotechnology.: Springer Berlin Heidelberg. 65: 93-115.
[32]	Brosse N, Sannigrahi P, Ragauskas A (2009) Pretreatment of Miscanthus x giganteus Using the Ethanol Organosolv Process for Ethanol Production. Ind Eng Chem Res 48: 8328-8334. doi: 10.1021/ie9006672
[33]	Yu G, Afzal W, Yang F, et al. (2014) Pretreatment of Miscanthus×giganteus using aqueous ammonia with hydrogen peroxide to increase enzymatic hydrolysis to sugars. J Chem Technol Biotechnol 89: 698-706. doi: 10.1002/jctb.4172
[34]	Haverty D, Dussan K, Piterina AV, et al. (2012) Autothermal, single-stage, performic acid pretreatment of Miscanthus x giganteus for the rapid fractionation of its biomass components into a lignin/hemicellulose-rich liquor and a cellulase-digestible pulp. Bioresource Technol 109: 173-177. doi: 10.1016/j.biortech.2012.01.007
[35]	Budarin VL, Clark JH, Lanigan BA, et al. (2010) Microwave assisted decomposition of cellulose: A new thermochemical route for biomass exploitation. Bioresource Technol 101: 3776-3779. doi: 10.1016/j.biortech.2009.12.110
[36]	Mosier N, Wyman C, Dale B, et al. (2005) Features of promising technologies for pretreatment of lignocellulosic biomass. Bioresource Technol 96: 673-686. doi: 10.1016/j.biortech.2004.06.025
[37]	Li JB, Henriksson G, Gellerstedt G (2007) Lignin depolymerization/repolymerization and its critical role for delignification of aspen wood by steam explosion. Bioresource Technol 98: 3061-3068. doi: 10.1016/j.biortech.2006.10.018
[38]	Mittal A, Katahira R, Himmel ME, et al. (2011) Effects of alkaline or liquid-ammonia treatment on crystalline cellulose: changes in crystalline structure and effects on enzymatic digestibility. Biotechnol Biofuels 4: 41. doi: 10.1186/1754-6834-4-41
[39]	Liu CF, Xu F, Sun JX, et al. (2006) Physicochemical characterization of cellulose from perennial ryegrass leaves (Lolium perenne). Carbohydr Res 341: 2677-2687. doi: 10.1016/j.carres.2006.07.008
[40]	Chen W-H, Ye S-C, Sheen H-K (2012) Hydrolysis characteristics of sugarcane bagasse pretreated by dilute acid solution in a microwave irradiation environment. Appl Energ 93: 237-244. doi: 10.1016/j.apenergy.2011.12.014
[41]	Kaparaju P, Felby C (2010) Characterization of lignin during oxidative and hydrothermal pre-treatment processes of wheat straw and corn stover. Bioresource Technol 101: 3175-3181. doi: 10.1016/j.biortech.2009.12.008
[42]	Corredor DY, Salazar JM, Hohn KL, et al. (2009) Evaluation and Characterization of Forage Sorghum as Feedstock for Fermentable Sugar Production. Appl Biochem Biotechnol 158: 164-179. doi: 10.1007/s12010-008-8340-y
[43]	Stewart D, Wilson HM, Hendra PJ, et al. (1995) Fourier-Transform Infrared and Raman-Spectroscopic Study of Biochemical and Chemical Treatments of Oak Wood (Quercus-Rubra) and Barley (Hordeum-Vulgare) Straw. J Agric Food Chem 43: 2219-2225. doi: 10.1021/jf00056a047
[44]	Kumar R, Mago G, Balan V, et al. (2009) Physical and chemical characterizations of corn stover and poplar solids resulting from leading pretreatment technologies. Bioresource Technol 100: 3948-3962. doi: 10.1016/j.biortech.2009.01.075
[45]	Sun JX, Sun XF, Sun RC, et al. (2003) Inhomogeneities in the chemical structure of sugarcane bagasse lignin. J Agric Food Chem 51: 6719-6725. doi: 10.1021/jf034633j
[46]	Guo GL, Hsu DC, Chen WH, et al. (2009) Characterization of enzymatic saccharification for acid-pretreated lignocellulosic materials with different lignin composition. Enzyme Microb Technol 45: 80-87. doi: 10.1016/j.enzmictec.2009.05.012
[47]	Mizi Fan DD, Biao Huang (2012) Fourier Transform Infrared Spectroscopy for Natural Fibres In: Salih DS, editor. Fourier Transform - Materials Analysis: InTech, 45-52.
[48]	Li CL, Knierim B, Manisseri C, et al. (2010) Comparison of dilute acid and ionic liquid pretreatment of switchgrass: Biomass recalcitrance, delignification and enzymatic saccharification. Bioresource Technol 101: 4900-4906. doi: 10.1016/j.biortech.2009.10.066
[49]	Boonmanumsin P, Treeboobpha S, Jeamjumnunja K, et al. (2012) Release of monomeric sugars from Miscanthus sinensis by microwave-assisted ammonia and phosphoric acid treatments. Bioresource Technol 103: 425-431. doi: 10.1016/j.biortech.2011.09.136
[50]	Ju YH, Huynh LH, Kasim NS, et al. (2011) Analysis of soluble and insoluble fractions of alkali and subcritical water treated sugarcane bagasse. Carbohyd Polym 83: 591-599. doi: 10.1016/j.carbpol.2010.08.022
[51]	Li HJ, Lu JR, Mo JC (2012) Physiochemical lignocellulose modification by the formosan subterranean termite Coptotermes Formosanus Shiraki (Isoptera: Rhinotermitidae) and its potential uses in the production of biofuels. Bioresources 7: 675-685.
[52]	Titirici M-M, Antonietti M, Baccile N (2008) Hydrothermal carbon from biomass: a comparison of the local structure from poly- to monosaccharides and pentoses/hexoses. Green Chemistry 10: 1204-1212. doi: 10.1039/b807009a
[53]	Lima MA, Lavorente GB, da Silva HKP, et al. (2013) Effects of pretreatment on morphology, chemical composition and enzymatic digestibility of eucalyptus bark: a potentially valuable source of fermentable sugars for biofuel production - part 1. Biotechnol Biofuels 6: 75. doi: 10.1186/1754-6834-6-75
[54]	Heiss-Blanquet S, Zheng D, Ferreira NL, et al. (2011) Effect of pretreatment and enzymatic hydrolysis of wheat straw on cell wall composition, hydrophobicity and cellulase adsorption. Bioresource Technol 102: 5938-5946. doi: 10.1016/j.biortech.2011.03.011
[55]	Palmqvist E, Hahn-Hägerdal B (2000) Fermentation of lignocellulosic hydrolysates. II: inhibitors and mechanisms of inhibition. Bioresource Technol 74: 25-33.

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