Abstract
Hydrothermal liquefaction is one of the most promising technologies to convert high moisture biomass into biofuels. However, understanding the liquefaction mechanism of different biomass fractions is still a challenge. The liquefaction of both lignin and cellulose is frequently studied, but the high diversity of biomass and processes used to generate these fractions makes the direct comparison difficult. In this work, one studies the liquefaction of lignin which has been generated in the process of lignocellulosic ethanol production employing acidic steam explosion. Results are compared with the liquefaction of commercial cellulose. The results have shown that this kind of lignin could produce higher amounts of bio-oil. Moreover, a model to quantify the contribution of the main kinds of reactions to the liquefaction mechanism was proposed. Dehydration was the main reaction observed for both raw materials, however decarboxylation plays a more relevant role in lignin liquefaction, accounting for near 37% of reactions in liquefaction pathway, whereas for cellulose it represents only 13% of reactions.
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Akhtar J, Amin N (2011) A review on process conditions for optimum bio-oil yield in hydrothermal liquefaction of biomass. Renew Sustain Energy Rev 15:1615–1624. https://doi.org/10.1016/j.rser.2010.11.054
Alcarde A (2019) Outros produtos. Embrapa. http://www.agencia.cnptia.embrapa.br/gestor/cana-de-acucar/arvore/CONTAG01_108_22122006154841.html. Accessed 28 Jun 2019
Arturi R, Strandgaard M, Nielsen R, Søgaard E, Maschietti M (2017) Hydrothermal liquefaction of lignin in near-critical water in a new batch reactor: influence of phenol and temperature. J Supercrit Fluids 123:28–39. https://doi.org/10.1016/j.supflu.2016.12.015
Auxenfans T, Crônier D, Chabbert B, Paës G (2017) Understanding the structural and chemical changes of plant biomass following steam explosion pretreatment. Biotechnol Biofuels 10:1–16. https://doi.org/10.1186/s13068-017-0718-z
Biller P, Ross A (2016) Production of biofuels via hydrothermal conversion. In: Luque R, Lin C, Wilson K, Clark J (eds) Handbook of biofuels production, 2nd edn. Woodhead Publishing, Cambridge, pp 509–547
Brebu M, Vasile C (2010) Thermal degradation of lignin—a review. Cellulose Chem Technol 9:353–363
Brebu M, Cazacu G, Chirila O (2011) Pyrolysis of lignin—a potential method for obtaining chemicals and/or fuels. Cellulose Chem Technol 45:43–50
Bridgwater A (2012) Review of fast pyrolysis of biomass and product upgrading. Biomass Bioenergy 38:68–94. https://doi.org/10.1016/j.biombioe.2011.01.048
Brunner G (2014) Processing of biomass with hydrothermal and supercritical water. Supercrit Fluid Sci Technol 5:395–509. https://doi.org/10.1016/B978-0-444-59413-6.00008-X
Casoni A, Nievas ML, Moyano EL, Álvarez M, Diez A, Dennehy M, Volpe M (2016) Catalytic pyrolysis of cellulose using MCM-41 type catalysts. Appl Catal A 514:235–240. https://doi.org/10.1016/j.apcata.2016.01.017
Chan Y, Yusup S, Quitain A, Tan R, Sasaki M, Loong H, Uemura Y (2015) Effect of process parameters on hydrothermal liquefaction of oil palm biomass for bio-oil production and its life cycle assessment. Energy Convers Manag 104:180–188. https://doi.org/10.1016/j.enconman.2015.03.075
Chedda J, Dumesic J (2007) An overview of dehydration, aldol-condensation and hydrogenation processes for production of liquid alkanes from biomass-derived carbohydrates. Catal Today 123:59–70. https://doi.org/10.1016/j.cattod.2006.12.006
Demirbas A (2000) Effect of lignin content on aqueous liquefaction products of biomass. Energy Convers Manag 41:1601–1607. https://doi.org/10.1016/S0196-8904(00)00013-3
Dence C (1992) Determination of carboxyl groups. In: Lin S, Dence C (eds) Methods in lignin chemistry, vol 7, 1st edn. Springer, Heidelberg, pp 458–464. https://doi.org/10.1007/978-3-642-74065-731
Doherty W, Mousavioun P, Fellows C (2011) Value-adding to cellulosic ethanol: lignin polymers. Ind Crops Prod 33:259–276. https://doi.org/10.1016/j.indcrop.2010.10.022
García T, Veses A, López J, Puértolas B, Pérez-Ramírez J, Callén M (2017) Determining bio-oil composition via chemometric tools based on infrared spectroscopy. ACS Sustain Chem Eng 10:8710–8719. https://doi.org/10.1021/acssuschemeng.7b01483
Glasser W, Selina J, Wu F (1983) Synthesis, structure and some properties of hydroxypropyl lignins. In: Soltes E (ed) Wood and agricultural residues: research on use for feed, fuels and chemicals, vol 8, 1st edn. Academic Press, New York, pp 149–166
Goudriaan F, Van de Beld B (2000) Thermal efficiency of the HTU process for biomass liquefaction. Presented in part at progress in thermochemical biomass conversion conference, Tyrol, Austria
Gunnarsson H (2017) Impact of steam explosion on spruce lignin structure and pyrolyzates. Dissertation, Norwegian University of Life Sciences
Heikkinen H, Elder T, Maaheimo H, Rovio S, Rahikainen J, Kruus K, Tamminen T (2014) Impact of steam explosion on the wheat straw lignin structure studied by solution-state nuclear magnetic resonance and density functional methods. J Agric Food Chem 62:10437–10444. https://doi.org/10.1021/jf504622j
Hou S, Huang W, Rizal F, Lin T (2016) Co-firing of fast pyrolysis bio-oil and heavy fuel oil in a 300-kWth furnace. Appl Sci 6:326. https://doi.org/10.3390/app6110326
Jin F, Wang Y, Zeng X, Shen Z, Yao G (2014) Water under high temperature and pressure conditions and its applications to develop green technologies for biomass conversion. In: Jin F (ed) Application of hydrothermal reactions to biomass conversion, 1st edn. Springer, Heidelberg, pp 3–28. https://doi.org/10.1007/978-3-642-54458-3_1
Karagöz S, Bhaskar T, Muto A, Sakata Y (2005) Comparative studies of oil compositions produced from sawdust, rice husk, lignin and cellulose by hydrothermal treatment. Fuel 84:875–884. https://doi.org/10.1016/j.fuel.2005.01.004
Karnjanakom S, Guan G, Asep B, Du X, Hao X, Yang J, Samartd C, Abudula A (2015) A green method to increase yield and quality of bio-oil: ultrasonic pretreatment of biomass and catalytic upgrading of bio-oil over metal (Cu, Fe and/or Zn)/-Al2O3. RSC Adv 5:83494–83503. https://doi.org/10.1039/C5RA14609G
Kersten S, Van Swaaij W, Lefferts L, Seshan K (2007) Options for catalysis in the thermochemical conversion of biomass into fuels. In: Centi G, Van Santem R (eds) Catalysis for renewables: from feedstock to energy production, 6th edn. Wiley, Weinheim, pp 119–145. https://doi.org/10.1002/9783527621118.ch6
Kruse A, Dahmen N (2015) Water—a magic solvent for biomass conversion. J Supercrit Fluids 96:36–45. https://doi.org/10.1016/j.supflu.2014.09.038
Li C, Yang X, Zhang Z, Zhou D, Zhang L, Zhang S, Chen J (2013) Hydrothermal liquefaction of desert shrub salix psammophilato high value-added chemicals and hydrochar with recycled processing water. BioResources 8:2981–2997. https://doi.org/10.15376/biores.8.2.2981-2997
Li M, Pu Y, Ragauskas A (2016) Current understanding of the correlation of lignin structure with biomass recalcitrance. Front Chem. https://doi.org/10.3389/fchem.2016.00045
Li Y, Cai Z, Liao M, Long J, Zhao W, Chen Y, Li X (2017) Catalytic depolymerization of organosolv sugarcane bagasse lignin in cooperative ionic liquid pairs. Catal Today 298:168–174. https://doi.org/10.1016/j.cattod.2017.04.059
Long Y, Yu Y, Chua Y, Wu H (2017) Acid-catalysed cellulose pyrolysis at low temperatures. Fuel 193:460–466. https://doi.org/10.1016/j.fuel.2016.12.067
Luijkx GC, Rantwijk FV, Bekkum HV (1993) Hydrothermal formation of 1,2,4-benzenetriol from 5-hydroxymethyl-2-furaldehyde and d-fructose. Carbohydr Res 242:131–139. https://doi.org/10.1016/0008-6215(93)80027-C
Lyckeskog H (2016) Hydrothermal liquefaction of lignin in to bio-oil. Dissertation, Chamlers University of Technology
Mark H (2013) Encyclopedia of polymer science and technology, 4th edn. Wiley, Hoboken. https://doi.org/10.1002/0471440264
Minowa T, Kondo T, Sudirjo S (1998) Thermochemical liquefaction of indonesian biomass residues. Biomass Bioenergy 14:517–524. https://doi.org/10.1016/S0961-9534(98)00006-3
NABC (2019) Advanced biofuels processing and integration. National Advanced Biofuels Consortium. http://www.nabcprojects.org/biofuels.html. Accessed 15 May 2019
Nakagame S (2010) The influence of lignin on the enzymatic hydrolysis of pretreated biomass substrates. Dissertation, University of British Columbia. https://doi.org/10.14288/1.0071453
Nazari L, Zhongshun Y, Souzanchi S, Madhumita R, Xu C (2015) Hydrothermal liquefaction of woody biomass in hot-compressed water: catalyst screening and comprehensive characterization of bio-crude oil. Fuel 162:74–83. https://doi.org/10.1016/j.fuel.2015.08.055
Neumann G, Pimentel B, Rensel D, Hicks J (2014) Correlating lignin structure to aromatic products in the catalytic fast pyrolysis of lignin model compounds containing β-O-4 linkages. Catal Sci Technol 4:3953–3963. https://doi.org/10.1039/C4CY00569D
Njoku S, Uellendahl H, Ahring B (2013) Comparing oxidative and dilute acid wet explosion pretreatment of Cocksfoot grass at high dry matter concentration for cellulosic ethanol production. Energy Sci Eng 1:89–98. https://doi.org/10.1002/ese3.11
Nunes KS, Pardini L (2019) Purification and characterization methods for lignin biomass as a potential precursor for carbon materials. Cellulose Chem Technol 53:227–242. https://doi.org/10.35812/CelluloseChemTechnol.2019.53.23
Patil R, Genco J, Pendse H, Van Heiningen A (2013) Cleavage of acetyl groups from northeast hardwood for acetic acid production in kraft pulp mills. Tappi J 12:57–67. https://doi.org/10.32964/TJ12.2.57
Patwardhan P, Brown R, Shanks B (2017) Understanding the fast pyrolysis of lignin. Chemsuschem 10:2140–2144. https://doi.org/10.1002/cssc.201100133
Pedersen T (2016) Hydrothermal liquefaction of biomass and model compounds. Dissertation, Aalborg Universitet. https://doi.org/10.5278/vbn.phd.engsci.00050
Peng X, Masai E, Kasai D, Miyauchi K, Katayama Y, Fukuda M (2005) A second 5-carboxyvanillate decarboxylase gene, ligW2, is important for lignin-related biphenyl catabolism in Sphingomonas paucimobilis SYK-6. Appl Environ Microbiol 71:5014–5021. https://doi.org/10.1128/AEM.71.9.5014-5021.2005
Peterson A, Vogel F, Lachance R, Fröling M, Antal M, Tester J (2008) Thermochemical biofuel production in hydrothermal media: a review of sub- and supercritical water technologies. Energy Environ Sci 1:32–65. https://doi.org/10.1039/B810100K
Pinho A, Almeida M, Mendes F, Ximenes V, Casavechia L (2015) Fast pyrolysis oil from pinewood chips co-processing with vacuum gas oil in an FCC unit for second generation fuel production. Fuel Process Technol 131:59–166. https://doi.org/10.1016/j.fuel.2016.10.032
Pu Y, Hu F, Huang F, Ragauskas A (2015) Lignin structural alterations in thermochemical pretreatments with limited delignification. Bioenergy Res 8:992–1003. https://doi.org/10.1007/s12155-015-9655-5
Ragauskas A (2020) Biorefinery site. Department of Chemical and Biomolecular Engineering http://biorefinery.utk.edu/technical_reviews/Lignin%20to%20biofuels-97.pdf. Accessed 15 Jan 2020
Ramirez J, Brown R, Rainey T (2015) A review of hydrothermal liquefaction bio-crude properties. Energies 8:6765–6794. https://doi.org/10.3390/en8076765
Ramos L (2003) The chemistry involved in the steam treatment of lignocellulosic materials. Quim Nova 26:863–871. https://doi.org/10.1590/S0100-40422003000600015
Singh R, Krishna B, Bhaskar T (2017) Hydrothermal liquefaction of lignocellulosic biomass components: effect of alkaline catalyst. In: Kumar A, Avinash R, Gupta T, Gurjar B (eds) Biofuels: technology, challenges and prospects, 1st edn. Springer, Singapore, pp 69–84. https://doi.org/10.1007/978-981-10-3791-7_5
Souza-Aguiar E, Appel L, Zoentti P, Fraga A, Bicudo A, Fonseca I (2014) Some importante catalytic challenges in the bioethanol integrated biorefinery. Catal Today 234:13–23. https://doi.org/10.1016/j.cattod.2014.02.016
Telkin K, Karagöz S (2013) Non-catalytic and catalytic hydrothermal liquefaction. Res Chem Intermed 39:485–498. https://doi.org/10.1007/s11164-012-0572-3
Tolbert A, Akinosho H, Khunsupat R, Naskar A, Ragauskas A (2014) Characterization and analysis of the molecular weight of lignin for biorefining studies. Biofuels Bioprod Biorefin 8:836–856. https://doi.org/10.1002/bbb.1500
Toor S, Rosendahl L, Rudolf A (2011) Hydrothermal liquefaction of biomass: a review of subcritical water technologies. Energy 36:2328–2342. https://doi.org/10.1016/j.energy.2011.03.013
Van Krevelen D (1950) Graphical-statistical method for the study of structure and reaction processes of coal. Fuel 29:269–228
Wikberg H, Grönber V, Jermakka J, Kemppainen K, Kleen M, Laine C, Paasikallio V, Oasmaa A (2015) Hydrothermal refining of biomass—an overview and future perspectives. Tappi J 14:195–207. https://doi.org/10.32964/TJ14.3.195
Wyman C (2013) Aqueous pretreatment of plant biomass for biological and chemical conversion to fuels and chemicals. Wiley, Chichester. https://doi.org/10.1002/9780470975831
Yang H, Li J, Xu J, Mo L (2017) The critical analysis of catalytic steam explosion pretreatment of corn stalk, lignin degradation, recovery, and characteristic variations. BioResources 12:344–361. https://doi.org/10.15376/biores.12.1.344-361
Zabaleta A (2012) Lignin extraction, purification and depolymerization study. Dissertation, University of the Basque Country. https://doi.org/10.4061/2011/787532
Zhang Y (2010) Hydrothermal liquefaction to convert biomass into crude oil. In: Blaschek H, Ezeji T, Scheffran J (eds) Biofuels from agricultural wastes and byproducts, 1st edn. Blackwell Publishing, Ames, pp 201–232
Zhong C, Wei X (2004) A comparative experimental study on the liquefaction of wood. Energy 29:1731–1741. https://doi.org/10.1016/j.energy.2004.03.096
Zhou C, Xia X, Lin C, Tong DS, Beltramini J (2011) Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels. Chem Soc Rev 40:5588–5617. https://doi.org/10.1039/C1CS15124J
Zhu Z, Rosendahl L, Toor S, Yu D, Chen G (2015) Hydrothermal liquefaction of barley straw to bio-crude oil: effects of reaction temperature and aqueous phase recirculation. Appl Energy 137:183–192. https://doi.org/10.1016/j.apenergy.2014.10.005
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do Couto Fraga, A., de Almeida, M.B.B. & Sousa-Aguiar, E.F. Hydrothermal liquefaction of cellulose and lignin: a new approach on the investigation of chemical reaction networks. Cellulose 28, 2003–2020 (2021). https://doi.org/10.1007/s10570-020-03658-w
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DOI: https://doi.org/10.1007/s10570-020-03658-w