Abstract
Viscose from dissolving pulp is one of the most used fabrics in the world. However, its production involves a very hazardous compound: CS2. Therefore, reducing its consumption is of utmost importance. In this sense, dissolving pulp can be pretreated, increasing the reactivity of the cellulose and reducing the CS2. Deep eutectic solvents have been used in biomass pretreatment as delignifying agents since their selectivity towards lignin is high. The ones used with lignocellulosic biomass usually comprise a quaternary ammonium and an organic acid. In previous studies, the formed by choline chloride and lactic acid has excellent results among different DES. However, the optimal conditions of the treatment have not been found, which is the aim of this study. This study showed that no harsh conditions are needed to increase reactivity since temperatures below 100 °C and time below 120 min could be used. Additionally, the study of the influence of the operating conditions led to the mathematical model of reactivity to find the optimal conditions. At the best conditions, reactivity increased to 97.97%, with a CS2 consumption reduction of more than 16%.
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References
Abbott AP, Barron JC, Frisch G et al (2011) Double layer effects on metal nucleation in deep eutectic solvents. Phys Chem Chem Phys 13:10224–10231. https://doi.org/10.1039/c0cp02244f
Arce C, Llano T, González S, Coz A (2020a) Use of green solvents as pre-treatment of dissolving pulp to decrease CS<inf>2</inf> consumption from viscose production. Cellulose. https://doi.org/10.1007/s10570-020-03465-3
Arce C, Llano T, González S, Coz A (2020b) Use of green solvents as pre-treatment of dissolving pulp to decrease CS2 consumption from viscose production. Cellulose 27:10313–10325. https://doi.org/10.1007/s10570-020-03465-3
Arnoul-Jarriault B, Lachenal D, Chirat C, Heux L (2015) Upgrading softwood bleached kraft pulp to dissolving pulp by cold caustic treatment and acid-hot caustic treatment. Ind Crops Prod 65:565–571. https://doi.org/10.1016/j.indcrop.2014.09.051
Baruah J, Nath BK, Sharma R et al (2018) Recent trends in the pretreatment of lignocellulosic biomass for value-added products. Front Energy Res 6:1–19. https://doi.org/10.3389/fenrg.2018.00141
Behera S, Arora R, Nandhagopal N, Kumar S (2014) Importance of chemical pretreatment for bioconversion of lignocellulosic biomass. Renew Sustain Energy Rev 36:91–106. https://doi.org/10.1016/j.rser.2014.04.047
Borand MN, Karaosmanoǧlu F (2018) Effects of organosolv pretreatment conditions for lignocellulosic biomass in biorefinery applications: a review. J Renew Sustain Energy. https://doi.org/10.1063/1.5025876
Carvalho MG, Ferreira PJ, Figueiredo MM (2000) Cellulose depolymerisation and paper properties in E. Globulus kraft pulps. Cellulose 7:359–368. https://doi.org/10.1023/A:1009293924205
Chen X, Zhang Q, Yu Q et al (2020) Depolymerization of holocellulose from Chinese herb residues by the mixture of lignin-derived deep eutectic solvent with water. Carbohydr Polym 248:116793. https://doi.org/10.1016/j.carbpol.2020.116793
China National Standard Press (2010) 51001–2009. Pulp and board for viscose fiber-determination for reaction property (2010). China Natl Stand Press
Chotirotsukon C, Raita M, Yamada M et al (2021) Sequential fractionation of sugarcane bagasse using liquid hot water and formic acid-catalyzed glycerol-based organosolv with solvent recycling. Bioenergy Res 14:135–152. https://doi.org/10.1007/s12155-020-10181-0
Craveiro R, Neves LA, Duarte ARC, Paiva A (2021) Supported liquid membranes based on deep eutectic solvents for gas separation processes. Sep Purif Technol 254:117593. https://doi.org/10.1016/j.seppur.2020.117593
da Silva LV, López-Sotelo JB, Correa-Guimarães A et al (2015) A kinetic study on microwave-assisted conversion of cellulose and lignocellulosic waste into hydroxymethylfurfural/furfural. Bioresour Technol 180:88–96. https://doi.org/10.1016/j.biortech.2014.12.089
Dornelles LB, Filho RM, Mariano AP (2021) Organosolv fractionation of eucalyptus: economics of cellulosic ethanol and chemicals versus lignin valorization to phenols and polyols. Ind Crops Prod 173:114097. https://doi.org/10.1016/j.indcrop.2021.114097
Duan C, Feng X, Tian C et al (2023a) Acidic deep eutectic solvent treatment for viscosity control and reactivity enhancement of bamboo dissolving pulp. Cellulose. https://doi.org/10.1007/s10570-023-05043-9
Duan C, Tian C, Feng X et al (2023b) Ultrafast process of microwave-assisted deep eutectic solvent to improve properties of bamboo dissolving pulp. Bioresour Technol 370:128543. https://doi.org/10.1016/j.biortech.2022.128543
European Environment Agency, European Environmental Agency (2018) The circular economy and the bioeconomy—partners in sustainability
Fahriye Enda T, Karaosmanoglu F (2021) Supply chain network carbon footprint of forest biomass to biorefinery. J Sustain for 40:124–141. https://doi.org/10.1080/10549811.2020.1746349
Ferdeş M, Dincă MN, Moiceanu G et al (2020) Microorganisms and enzymes used in the biological pretreatment of the substrate to enhance biogas production: a review. Sustainability. https://doi.org/10.3390/su12177205
Francisco M, van den Bruinhorst A, Kroon MC (2012) New natural and renewable low transition temperature mixtures (LTTMs): screening as solvents for lignocellulosic biomass processing. Green Chem. https://doi.org/10.1039/c2gc35660k
García G, Aparicio S, Ullah R, Atilhan M (2015) Deep eutectic solvents: physicochemical properties and gas separation applications. Energy Fuels 29:2616–2644. https://doi.org/10.1021/ef5028873
Geng A, **n F, Ip JY (2012) Ethanol production from horticultural waste treated by a modified organosolv method. Bioresour Technol 104:715–721. https://doi.org/10.1016/j.biortech.2011.10.076
Gil C (2020) Metodología de superficie de respuesta (RSM)-explicación de conceptos teóricos con ejemplos en R
Gondhalekar SC, Pawar PJ, Dhumal SS, Thakre SS (2019) Mechanism of Xanthation reaction in viscose process. Cellulose 26:1595–1604. https://doi.org/10.1007/s10570-018-2213-5
Guo Z, Ling Z, Wang C et al (2018) Integration of facile deep eutectic solvents pretreatment for enhanced enzymatic hydrolysis and lignin valorization from industrial xylose residue. Bioresour Technol 265:334–339. https://doi.org/10.1016/j.biortech.2018.06.027
Husanu E, Mero A, Rivera JG et al (2020) Exploiting deep eutectic solvents and ionic liquids for the valorization of chestnut shell waste. ACS Sustain Chem Eng 8:18386–18399. https://doi.org/10.1021/acssuschemeng.0c04945
ISO 5351 (2010) Pulps—determination of limiting viscosity number in cupri-ethylenediamine (CED) solution. Int Organ Standarization. pp 1–19
Jiang J, Carrillo-Enríquez NC, Oguzlu H et al (2020) Acidic deep eutectic solvent assisted isolation of lignin containing nanocellulose from thermomechanical pulp. Carbohydr Polym 247:116727. https://doi.org/10.1016/j.carbpol.2020.116727
Johansson D, Germgård U (2008) Carbohydrate degradation during softwood kraft cooking—influence on cellulose viscosity, carbohydrate composition and hexenuronic acid content. Nord Pulp Pap Res J 23:292–298. https://doi.org/10.3183/npprj-2008-23-03-p292-298
Kalhor P, Ghandi K (2019) Deep eutectic solvents for pretreatment, extraction, and catalysis of biomass and food waste. Molecules 24(22):4012
Kumar H, Christopher LP (2017) Recent trends and developments in dissolving pulp production and application. Cellulose. https://doi.org/10.1007/s10570-017-1285-y
Kumar AK, Sharma S (2017) Recent updates on different methods of pretreatment of lignocellulosic feedstocks: a review. Bioresour Bioprocess 4:7. https://doi.org/10.1186/s40643-017-0137-9
Kumar AK, Parikh BS, Pravakar M (2016) Natural deep eutectic solvent mediated pretreatment of rice straw: bioanalytical characterization of lignin extract and enzymatic hydrolysis of pretreated biomass residue. Environ Sci Pollut Res 23:9265–9275. https://doi.org/10.1007/s11356-015-4780-4
Lee SH, Doherty TV, Linhardt RJ, Dordick JS (2009) Ionic liquid-mediated selective extraction of lignin from wood leading to enhanced enzymatic cellulose hydrolysis. Biotechnol Bioeng 102:1368–1376. https://doi.org/10.1002/bit.22179
Liu X, Wei W, Wu S (2019) Synergism of organic acid and deep eutectic solvents pretreatment for the co-production of oligosaccharides and enhancing enzymatic saccharification. Bioresour Technol. https://doi.org/10.1016/j.biortech.2019.121775
Liu S, Zhang Q, Gou S et al (2021) Esterification of cellulose using carboxylic acid-based deep eutectic solvents to produce high-yield cellulose nanofibers. Carbohydr Polym 251:117018. https://doi.org/10.1016/j.carbpol.2020.117018
Llano T, Quijorna N, Coz A (2017) Detoxification of a lignocellulosic waste from a pulp mill to enhance its fermentation prospects. Energies. https://doi.org/10.3390/en10030348
Llano T, Arce C, Ruiz G, et al (2018) Modelling and optimization of the last two stages of an environmentallycompatible TCF bleaching sequence. BioResources 13:6642–6662
Lynam JG, Kumar N, Wong MJ (2017) Deep eutectic solvents’ ability to solubilize lignin, cellulose, and hemicellulose; thermal stability; and density. Bioresour Technol 238:684–689. https://doi.org/10.1016/j.biortech.2017.04.079
Majová V, Horanová S, Škulcová A, Šima J, Jablonský M (2017) Deep eutectic solvent delignification: impact of initial lignin. BioResources 12:7301–7310
Mao Y, Gerrow A, Ray E et al (2023) Lignin recovery from cocoa bean shell using microwave-assisted extraction and deep eutectic solvents. Bioresour Technol 372:128680. https://doi.org/10.1016/j.biortech.2023.128680
Meeuwes T (2020) Ionic liquid as a tool for cost-effective fractionation of biomass to obtain lignin with high β-O-4-content
Mnasri A, Dhaouadi H, Khiari R et al (2022) Effects of deep eutectic solvents on cellulosic fibres and paper properties: green “chemical” refining. Carbohydr Polym 292:119606. https://doi.org/10.1016/j.carbpol.2022.119606
Mora-Pale M, Meli L, Doherty TV et al (2011) Room temperature ionic liquids as emerging solvents for the pretreatment of lignocellulosic biomass. Biotechnol Bioeng 108:1229–1245. https://doi.org/10.1002/bit.23108
Muley PD, Mobley JK, Tong X et al (2019) Rapid microwave-assisted biomass delignification and lignin depolymerization in deep eutectic solvents. Energy Convers Manag 196:1080–1088. https://doi.org/10.1016/j.enconman.2019.06.070
Olugbemide AD, Oberlintner A, Novak U, Likozar B (2021) Lignocellulosic corn stover biomass pre-treatment by deep eutectic solvents (Des) for biomethane production process by bioresource anaerobic digestion. Sustainability. https://doi.org/10.3390/su131910504
Pascal K, Ren H, Sun FF et al (2019) Mild acid-catalyzed atmospheric glycerol organosolv pretreatment effectively improves enzymatic hydrolyzability of lignocellulosic biomass. ACS Omega 4:20015–20023. https://doi.org/10.1021/acsomega.9b02993
Raghuwanshi VS, Ochmann M, Polzer F et al (2014) Self-assembly of gold nanoparticles on deep eutectic solvent (DES) surfaces. Chem Commun 50:8693–8696. https://doi.org/10.1039/c4cc02588a
Rios-González LJ, Morales-Martínez TK, Rodríguez-Flores MF et al (2017) Autohydrolysis pretreatment assessment in ethanol production from agave bagasse. Bioresour Technol 242:184–190. https://doi.org/10.1016/j.biortech.2017.03.039
Ruesgas-Ramón M, Figueroa-Espinoza MC, Durand E (2017) Application of deep eutectic solvents (DES) for phenolic compounds extraction: overview, challenges, and opportunities. J Agric Food Chem 65:3591–3601. https://doi.org/10.1021/acs.jafc.7b01054
Salapa I, Katsimpouras C, Topakas E, Sidiras D (2017) Organosolv pretreatment of wheat straw for efficient ethanol production using various solvents. Biomass Bioenerg 100:10–16. https://doi.org/10.1016/j.biombioe.2017.03.011
Skarpalezos D, Detsi A (2019) Deep eutectic solvents as extraction media for valuable flavonoids from natural sources. Appl Sci. https://doi.org/10.3390/app9194169
Socha AM, Parthasarathi R, Shi J et al (2014) Efficient biomass pretreatment using ionic liquids derived from lignin and hemicellulose. Proc Natl Acad Sci USA 111:3587–3595. https://doi.org/10.1073/pnas.1405685111
Song W, Li Z, Liu F et al (2018) Effective removal of ammonia nitrogen from waste seawater using crystal seed enhanced struvite precipitation technology with response surface methodology for process optimization. Environ Sci Pollut Res 25:628–638. https://doi.org/10.1007/s11356-017-0441-0
Tan YT, Ngoh GC, Chua ASM (2018) Evaluation of fractionation and delignification efficiencies of deep eutectic solvents on oil palm empty fruit bunch. Ind Crops Prod 123:271–277. https://doi.org/10.1016/j.indcrop.2018.06.091
TAPPI (1999) T 203 cm-99. Alpha-, beta- and gamma-cellulose in pulp. TAPPI test methods TAPPI press atlanta 1–5
Teramura H, Sasaki K, Oshima T et al (2016) Organosolv pretreatment of sorghum bagasse using a low concentration of hydrophobic solvents such as 1-butanol or 1-pentanol. Biotechnol Biofuels 9:1–11. https://doi.org/10.1186/s13068-016-0427-z
Tian C, Zheng L, Miao Q et al (2014) Improving the reactivity of kraft-based dissolving pulp for viscose rayon production by mechanical treatments. Cellulose 21:3647–3654. https://doi.org/10.1007/s10570-014-0332-1
van Osch DJGP, Kollau LJBM, van den Bruinhorst A et al (2017) Ionic liquids and deep eutectic solvents for lignocellulosic biomass fractionation. Phys Chem Chem Phys 19:2636–2665. https://doi.org/10.1039/C6CP07499E
Wahlström R, Hiltunen J, De Souza P, Nascente Sirkka M et al (2016) Comparison of three deep eutectic solvents and 1-ethyl-3-methylimidazolium acetate in the pretreatment of lignocellulose: effect on enzyme stability, lignocellulose digestibility and one-pot hydrolysis. RSC Adv 6:68100–68110. https://doi.org/10.1039/c6ra11719h
Wang X, Duan C, Zhao C et al (2018) Heteropoly acid catalytic treatment for reactivity enhancement and viscosity control of dissolving pulp. Bioresour Technol 253:182–187. https://doi.org/10.1016/j.biortech.2018.01.022
Wang X, Lu X, Zhao H et al (2022) Dissolution and degradation of cellulosic fiber in carboxylic acid choline chloride-based deep eutectic solvents. Wood Sci Technol 56:1475–1486. https://doi.org/10.1007/s00226-022-01406-w
Weerasai K, Laosiripojana N, Imman S, Kreetachat T, Suriyachai N (2021) Reusable alkaline catalyzed organosolv pretreatment and delignification of bagasse for sugar platform biorefinery. Biomass Conv Bioref 13:1751–1761. https://doi.org/10.1007/s13399-020-01269-w
Wei Kit Chin D, Lim S, Pang YL, Lam MK (2020) Fundamental review of organosolv pretreatment and its challenges in emerging consolidated bioprocessing. Biofuels, Bioprod Bioref 14:808–829. https://doi.org/10.1002/bbb.2096
**e J, Chen J, Cheng Z et al (2021) Pretreatment of pine lignocelluloses by recyclable deep eutectic solvent for elevated enzymatic saccharification and lignin nanoparticles extraction. Carbohydr Polym 269:118321. https://doi.org/10.1016/j.carbpol.2021.118321
Yawalata D, Paszner L (2006) Characteristics of NAEM salt-catalyzed alcohol organosolv pul** as a biorefinery. Holzforschung 60:239–244. https://doi.org/10.1515/HF.2006.039
Yiin CL, Yap KL, Fui Chin BL, Mun Lock SS (2023) Insights into the lignin dissolution mechanism of water content tailored-choline chloride (ChCl) based green solvents for biomass pretreatment. Phys Chem Res 11:605–614. https://doi.org/10.22036/pcr.2022.350557.2131
Zdanowicz M, Wilpiszewska K, Spychaj T (2018) Deep eutectic solvents for polysaccharides processing: a review. Carbohydr Polym 200:361–380. https://doi.org/10.1016/j.carbpol.2018.07.078
Zhang C, Guo KN, Ma CY et al (2023) Assessing the availability of bamboo (phyllostachys pubescens) fibers and parenchyma cells for producing lignin nanoparticles and fermentable sugars by rapid carboxylic acid-based deep eutectic solvents pretreatment. Ind Crops Prod 193:116204. https://doi.org/10.1016/j.indcrop.2022.116204
Zhao X, Cheng K, Liu D (2009) Organosolv pretreatment of lignocellulosic biomass for enzymatic hydrolysis. Appl Microbiol Biotechnol 82:815–827. https://doi.org/10.1007/s00253-009-1883-1
Zhong L, Wang C, Xu M et al (2021) Alkali-catalyzed organosolv pretreatment of lignocellulose enhances enzymatic hydrolysis and results in highly antioxidative lignin. Energy Fuels 35:5039–5048. https://doi.org/10.1021/acs.energyfuels.1c00320
Zhou S, Li Y, Huang L et al (2019) Ultrasonic treatment for enhancing the accessibility and reactivity of softwood rayon-grade kraft-based dissolving pulp. Cellulose 26:9287–9294. https://doi.org/10.1007/s10570-019-02719-z
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The authors acknowledge the pulp mill Sniace for providing the pulp needed for the experiments and analyses. Also, the authors would like to acknowledge CELISE project under the Marie Sklodowska-Curie grant agreement No 101007733.
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Arce, C., Llano, T., Mowinckel, Á. et al. Deep eutectic solvents as pretreatment to increase Fock’s reactivity under optimum conditions. Cellulose 31, 247–261 (2024). https://doi.org/10.1007/s10570-023-05628-4
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DOI: https://doi.org/10.1007/s10570-023-05628-4