γ-Valerolactone/CuCl₂ biphasic system for high total monosaccharides recovery from pretreatment and enzymatic hydrolysis processes of eucalyptus

Abstract

The efficient fractionation and recovery of monosaccharides (xylose and glucose) from lignocellulosic biomass facilitates subsequent sugar-based derivative production. This study introduces a one-pot γ-valerolactone/CuCl₂ biphasic pretreatment system (100-mmol·L^–1 CuCl₂, 180 °C, 60 min) capable of achieving removal rates of 92.25% and 90.64% for xylan and lignin, respectively, while retaining 83.88% of cellulose. Compared to other metal chlorides (NaCl, LiCl, FeCl₃, and AlCl₃), the γ-valerolactone/CuCl₂ system recovered 121.2 mg·(g eucalyptus)^–1 of xylose and 55.96 mg·(g eucalyptus)^–1 of glucose during the pretreatment stage and 339.2 mg·(g eucalyptus)^–1 of glucose during the enzymatic hydrolysis stage (90.78% of glucose yield), achieving a total monosaccharide recovery of 86.31%. In addition, the recovery of γ-valerolactone was 79.33%, exhibiting minimal changes relative to the pretreatment performance. The method proposed in this study allows a high total monosaccharides recovery and a circular economy-oriented pretreatment approach, offering a viable pathway for biorefinery.

Graphical abstract

Keywords

lignocellulose / biorefinery / total monosaccharides recovery / γ-valerolactone

References

[1] Nie S X , Chen C J , Zhu C J . Advanced biomass materials: progress in the applications for energy, environmental, and emerging fields. Frontiers of Chemical Science and Engineering, 2023, 17(7): 795–797

[2] Wu M , Liu J K , Yan Z Y , Wang B , Zhang X M , Xu F , Sun R C . Efficient recovery and structural characterization of lignin from cotton stalk based on a biorefinery process using a γ-valerolactone/water system. RSC Advances, 2016, 6(8): 6196–6204

[3] Nguyen T Y , Cai C M , Kumar R , Wyman C E . Co-solvent pretreatment reduces costly enzyme requirements for high sugar and ethanol yields from lignocellulosic biomass. ChemSusChem, 2015, 8(10): 1716–1725

[4] Satari B , Karimi K , Kumar R . Cellulose solvent-based pretreatment for enhanced second-generation biofuel production: a review. Sustainable Energy & Fuels, 2019, 3(1): 11–62

[5] Patri A S , Mohan R , Pu Y Q , Yoo C G , Ragauskas A J , Kumar R , Kisailus D , Cai C M , Wyman C E . THF co-solvent pretreatment prevents lignin redeposition from interfering with enzymes yielding prolonged cellulase activity. Biotechnology for Biofuels, 2021, 14(1): 63

[6] Cheng J Y , Huang C , Zhan Y N , Liu X Z , Wang J , Meng X Z , Yoo C G , Fang G G , Ragauskas A J . A high-solid DES pretreatment using never-dried biomass as the starting material: towards high-quality lignin fractionation. Green Chemistry, 2023, 25(4): 1571–1581

[7] Xu H , Mo S H , Peng Q , Lu M S . One-pot lignocellulose fractionation using lewis acid-catalyzed GVL/H₂O system toward complete exploitation of eucalyptus. Industrial Crops and Products, 2023, 202: 117026

[8] Song G , Madadi M , Sun C , Shao L , Tu M , Abdulkhani A , Zhou Q , Lu X , Hu J , Sun F . Surfactants facilitated glycerol organosolv pretreatment of lignocellulosic biomass by structural modification for co-production of fermentable sugars and highly reactive lignin. Bioresource Technology, 2023, 383: 129178

[9] Li W H , Tan X S , Miao C L , Zhang Z Y , Wang Y X , Ragauskas A J , Zhuang X S . Mild organosolv pretreatment of sugarcane bagasse with acetone/phenoxyethanol/water for enhanced sugar production. Green Chemistry, 2023, 25(3): 1169–1178

[10] Le H Q , Zaitseva A , Pokki J P , Stahl M , Alopaeus V , Sixta H . Solubility of organosolv lignin in γ-valerolactone/water binary mixtures. ChemSusChem, 2016, 9(20): 2939–2947

[11] Luterbacher J S , Rand J M , Alonso D M , Han J , Youngquist J T , Maravelias C T , Pfleger B F , Dumesic J A . Nonenzymatic sugar production from biomass using biomass-derived gamma-valerolactone. Science, 2014, 343(6168): 277–280

[12] Wu Y , Ji H R , Ji X X . Biomass pretreatment using biomass-derived organic solvents facilitates the extraction of lignin and enzymatic hydrolysis of glucan. Cellulose, 2023, 30(5): 2859–2872

[13] Sun S N , Chen X , Tao Y H , Cao X F , Li M F , Wen J L , Nie S X , Sun R C . Pretreatment of eucalyptus urophylla in gamma-valerolactone/dilute acid system for removal of non-cellulosic components and acceleration of enzymatic hydrolysis. Industrial Crops and Products, 2019, 132: 21–28

[14] Jonsson L J , Martin C . Pretreatment of lignocellulose: formation of inhibitory by-products and strategies for minimizing their effects. Bioresource Technology, 2016, 199: 103–112

[15] Moodley P , Kana E B G . Microwave-assisted inorganic salt pretreatment of sugarcane leaf waste: effect on physiochemical structure and enzymatic saccharification. Bioresource Technology, 2017, 235: 35–42

[16] Hou Y J , Wang S S , Deng B J , Ma Y , Long X , Qin C R , Liang C , Huang C X , Yao S Q . Selective separation of hemicellulose from poplar by hydrothermal pretreatment with ferric chloride and pH buffer. International Journal of Biological Macromolecules, 2023, 251: 126374

[17] Romero I , Lopez-Linares J C , Moya M , Castro E . Optimization of sugar recovery from rapeseed straw pretreated with FeCl₃. Bioresource Technology, 2018, 268: 204–211

[18] Lee C , Wu T Y , Yong K J , Cheng C K , Siow L F , Jahim J M . Investigation into lewis and bronsted acid interactions between metal chloride and aqueous choline chloride-oxalic acid for enhanced furfural production from lignocellulosic biomass. Science of the Total Environment, 2022, 827: 10

[19] Wang N , Zhang J , Wang H H , Li Q , Wei S A , Wang D . Effects of metal ions on the hydrolysis of bamboo biomass in 1-butyl-3-methylimidazolium chloride with dilute acid as catalyst. Bioresource Technology, 2014, 173: 399–405

[20] New E K , Wu T Y , Tnah S K , Procentese A , Cheng C K . Pretreatment and sugar recovery of oil palm fronds using choline chloride: calcium chloride hexahydrate integrated with metal chloride. Energy, 2023, 277: 127486

[21] Han X Y , Zhang X B , Dai T , Xie J , Zhang H D . Enhancing the co-production of sugars from sugarcane bagasse via CuCl₂-catalyzed organosolv pretreatment and additives. Fuel Processing Technology, 2023, 241: 107629

[22] Bradford M M . A rapid and sensitive method for the quantitation of microgram quantities of protein utilizing the principle of protein-dye binding. Analytical Biochemistry, 1976, 72(1-2): 248–254

[23] Ying W J , Xu Y , Zhang J H . Effect of sulfuric acid on production of xylooligosaccharides and monosaccharides from hydrogen peroxide-acetic acid-pretreated poplar. Bioresource Technology, 2021, 321: 9

[24] Jiang Z C , Budarin V L , Fan J J , Remón J , Li T Z , Hu C W , Clark J H . Sodium chloride-assisted depolymerization of xylo-oligomers to xylose. ACS Sustainable Chemistry & Engineering, 2018, 6(3): 4098–4104

[25] Yao S Q , Nie S X , Yuan Y , Wang S F , Qin C R . Efficient extraction of bagasse hemicelluloses and characterization of solid remainder. Bioresource Technology, 2015, 185: 21–27

[26] Yang M Y , Rehman M S U , Yan T X , Khan A U , Oleskowicz-Popiel P , Xu X , Cui P , Xu J . Treatment of different parts of corn stover for high yield and lower polydispersity lignin extraction with high-boiling alkaline solvent. Bioresource Technology, 2018, 249: 737–743

[27] Wu R J , Wang X D , Zhang Y C , Fu Y J , Qin M H . Efficient removal of surface-deposited pseudo-lignin and lignin droplets by isothermal phase separation during hydrolysis. Bioresource Technology, 2022, 345: 5

[28] Shinde S D , Meng X Z , Kumar R , Ragauskas A J . Recent advances in understanding the pseudo-lignin formation in a lignocellulosic biorefinery. Green Chemistry, 2018, 20(10): 2192–2205

[29] Kumar R , Bhagia S , Smith M D , Petridis L , Ong R G , Cai C M , Mittal A , Himmel M H , Balan V , Dale B E , Ragauskas A J , Smith J C , Wyman C E . Cellulose-hemicellulose interactions at elevated temperatures increase cellulose recalcitrance to biological conversion. Green Chemistry, 2018, 20(4): 921–934

[30] Kumar R , Hu F , Sannigrahi P , Jung S , Ragauskas A J , Wyman C E . Carbohydrate derived-pseudo-lignin can retard cellulose biological conversion. Biotechnology and Bioengineering, 2013, 110(3): 737–753

[31] Kamireddy S R , Li J B , Tucker M , Degenstein J , Ji Y . Effects and mechanism of metal chloride salts on pretreatment and enzymatic digestibility of corn stover. Industrial & Engineering Chemistry Research, 2013, 52(5): 1775–1782

[32] Jasiukaityte-Grojzdek E , Hus M , Grilc M , Likozar B . Acid-catalyzed α-O-4 aryl-ether cleavage mechanisms in (aqueous) γ-valerolactone: catalytic depolymerization reactions of lignin model compound during organosolv pretreatment. ACS Sustainable Chemistry & Engineering, 2020, 8(47): 17475–17486

[33] Santo M C E , Fockink D H , Pellegrini V O A , Guimaraes F E G , deAzevedo E R , Ramos L P , Polikarpov I . Physical techniques shed light on the differences in sugarcane bagasse structure subjected to steam explosion pretreatments at equivalent combined severity factors. Industrial Crops and Products, 2020, 158: 113003

[34] Yu J , Paterson N , Blamey J , Millan M . Cellulose, xylan and lignin interactions during pyrolysis of lignocellulosic biomass. Fuel, 2017, 191: 140–149

[35] Liu Y C , Xie J , Wu N , Ma Y H , Menon C , Tong J . Characterization of natural cellulose fiber from corn stalk waste subjected to different surface treatments. Cellulose, 2019, 26(8): 4707–4719

[36] De S , Mishra S , Poonguzhali E , Rajesh M , Tamilarasan K . Fractionation and characterization of lignin from waste rice straw: biomass surface chemical composition analysis. International Journal of Biological Macromolecules, 2020, 145: 795–803

[37] Luterbacher J S , Parlange J Y , Walker L P . A pore-hindered diffusion and reaction model can help explain the importance of pore size distribution in enzymatic hydrolysis of biomass. Biotechnology and Bioengineering, 2013, 110(1): 127–136

[38] Mou H Y , Wu S B . Comparison of organosolv and hydrotropic pretreatments of eucalyptus for enhancing enzymatic saccharification. Bioresource Technology, 2016, 220: 637–640

[39] Chu Q L , Song K , Wang J , Hu J G , Chen X Y . Improving enzymatic saccharification of hardwood through lignin modification by carbocation scavengers and the underlying mechanisms. Bioresource Technology, 2019, 294: 9

[40] Wang P , Su Y , Tang W , Huang C X , Lai C H , Ling Z , Yong Q . Revealing enzymatic digestibility of kraft pretreated larch based on a comprehensive analysis of substrate-related factors. Renewable Energy, 2022, 199: 1461–1468

[41] Ruiz H A , Conrad M , Sun S N , Sanchez A , Rocha G J M , Romaní A , Castro E , Torres A , Rodríguez-Jasso R M , Andrade L P , Smirnova I , Sun R C , Meyer A S . Engineering aspects of hydrothermal pretreatment: from batch to continuous operation, scale-up and pilot reactor under biorefinery concept. Bioresource Technology, 2020, 299: 122685

[42] Yang L , Xu L Q , Yang H Y , Shi Z J , Zhao P , Yang J . Effect of different washing methods on reducing the inhibition of surface lignin in the tetraethylammonium chloride/oxalic acid-based deep eutectic solvent pretreatment. Industrial Crops and Products, 2022, 188: 115728

[43] Cui M J , Li X Y . Additives enhancing enzymatic hydrolysis of wheat straw to obtain fermentable sugar. Applied Biochemistry and Biotechnology, 2023, 195(2): 1059–1071

[44] Loow Y L , Wu T Y , Tan K A , Lim Y S , Siow L F , Jahim J M , Mohammad A W , Teoh W H . Recent advances in the application of inorganic salt pretreatment for transforming lignocellulosic biomass into reducing sugars. Journal of Agricultural and Food Chemistry, 2015, 63(38): 8349–8363

[45] Chen L H , Chen R , Fu S Y . Preliminary exploration on pretreatment with metal chlorides and enzymatic hydrolysis of bagasse. Biomass and Bioenergy, 2014, 71: 311–317

[46] Zhang H Y , Xu Y , Yu S Y . Co-production of functional xylooligosaccharides and fermentable sugars from corncob with effective acetic acid prehydrolysis. Bioresource Technology, 2017, 234: 343–349

[47] Yang Q Z , Tang W , Ma C L , He Y C . Efficient co-production of xylooligosaccharides, furfural and reducing sugars from yellow bamboo via the pretreatment with biochar-based catalyst. Bioresource Technology, 2023, 387: 129637

[48] Moodley P , Sewsynker-Sukai Y , Kana E B G . Progress in the development of alkali and metal salt catalysed lignocellulosic pretreatment regimes: potential for bioethanol production. Bioresource Technology, 2020, 310: 123372

[49] Zhang C , Ma C Y , Xu L H , Wu Y Y , Wen J L . The effects of mild lewis acids-catalyzed ethanol pretreatment on the structural variations of lignin and cellulose conversion in balsa wood. International Journal of Biological Macromolecules, 2021, 183: 1362–1370

[50] Chen X , Li H Y , Sun S N , Cao X F , Sun R C . Effect of hydrothermal pretreatment on the structural changes of alkaline ethanol lignin from wheat straw. Scientific Reports, 2016, 6(1): 39354

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