ABSTRACT
A novel biphasic system containing water-soluble deep eutectic solvent (DES) and cyclopentyl methyl ether (CPME) was developed to treat Eucalyptus for furfural production, extracting lignin and enhancing cellulose enzymatic hydrolysis. Herein effect of DES type, water content in DES, temperature and time on furfural yield in water-soluble DES/CPME pretreatment process was firstly evaluated. A maximum furfural yield of 80.6 % was attained in 10 min at 150 °C with choline chloride (ChCl)/citric acid monohydrate (CAM)/CPME system containing 30 wt% water and 2.5 wt% SnCl4·5H2O, which was higher than that obtained from ChCl/CAM/CPME system without water (55.5 %) and H2O/CPME system (49.7 %). These results demonstrated that the water-soluble DES/CPME system was a powerful method enhancing the furfural production. Under the optimal pretreatment conditions, the delignification and glucose yield were reached to 72.7 % and 94.3 %, respectively. The extracted lignin showed low molecular weight and ß-aryl-ether was obviously cleaved. Additionally, water-soluble DES/CPME pretreatment led to a significant removal of hemicelluloses (100.0 %) and lignin (72.7 %) and introduced morphological changes on cell walls, especially from the cell corner (CC) and secondary wall (SW) layers. Overall, this work proposed a practical one-step fractionation strategy for co-producing furfural, lignin and fermentable sugar, providing a way to biorefinery.
ABSTRACT
A facile biphasic system composed of choline chloride (ChCl)-based deep eutectic solvent (DES) and methyl isobutyl ketone (MIBK) was developed to realize the furfural production, lignin separation and preparation of fermentable glucose from Eucalyptus in one-pot. Results showed that the ChCl/1,2-propanediol/MIBK system owned the best property to convert hemicelluloses into furfural. Under the optimal conditions (MRChCl:1,2-propanediol = 1:2, raw materials:DES:MIBK ratio = 1:4:8 g/g/mL, 0.075 mol/L AlCl3·6H2O, 140 °C, and 90 min), the furfural yield and glucose yield reached 65.0 and 92.2 %, respectively. Meanwhile, the lignin with low molecular weight (1250-1930 g/mol), low polydispersity (DM = 1.25-1.53) and high purity (only 0.08-2.59 % carbohydrate content) was regenerated from the biphasic system. With the increase of pretreatment temperature, the ß-O-4, ß-ß and ß-5 linkages in the regenerated lignin were gradually broken, and the content of phenolic hydroxyl groups increased, but the content of aliphatic hydroxyl groups decreased. This research provides a new strategy for the comprehensive utilization of lignocellulose in biorefinery process.
Subject(s)
Cellulose , Eucalyptus , Furaldehyde , Lignin , Eucalyptus/chemistry , Eucalyptus/metabolism , Lignin/chemistry , Furaldehyde/chemistry , Furaldehyde/analogs & derivatives , Furaldehyde/metabolism , Cellulose/chemistry , Methyl n-Butyl Ketone/chemistry , Methyl n-Butyl Ketone/metabolism , Choline/chemistry , Propylene Glycol/chemistry , Glucose/metabolism , Glucose/chemistry , Fermentation , Solvents/chemistryABSTRACT
An effective approach for glucose and furfural production by converting cellulose and hemicelluloses from corn stalk in a biphasic system of molten salt hydrate (MSH) and organic solvent using H2SO4 as catalyst was reported. Results showed that the system with LiBr·3H2O and dichloromethane (DCM) had excellent performance in cellulose and hemicelluloses conversion. Under the optimal reaction conditions (corn stalk:LiBr·3H2O:DCM ratio = 0.35:10:20 g/mL/mL, 0.05 mol/L H2SO4, 120 °C, 90 min), 58.9% glucose and 72.5% furfural were yielded. Meanwhile, lignin was obviously depolymerized by the cleavage of ß-O-4' linkages and fractionated with high purity and low molecular weight for potential coproducts. Fluorescence microscopy and confocal Raman microscope displayed that the LiBr·3H2O/DCM treatment caused decreasing intensities in carbohydrate and lignin, suggesting the degradation of the main components of biomass. This research provided a promising biorefinery technology for the comprehensive utilization of corn stalk.
Subject(s)
Furaldehyde , Lignin , Zea mays , Glucose , Solvents , Cellulose , Sodium Chloride , BiomassABSTRACT
The developing of pretreatment method to break the biomass barrier of lignocellulosic is a challenging task for achieve high value utilization. A fast microwave-assisted choline chloride/1,2-propanediol/methyl isobutyl ketone biphasic system was constructed for pretreating Eucalyptus to the production of furfural and cellulose-rich residues and the extraction of lignin. Results showed that the combination of AlCl3·6H2O and HCl had the best catalytic ability for furfural production among the examined catalysts. Under the optimal conditions (140 °C, 15 min, 0.075 M AlCl3·6H2O, 0.05 M HCl), the furfural yield of 55.4 %, the glucose yield of 90.3 % and the delignification rate of 92.4 % could be achieved. Moreover, the extracted lignin samples with a low polydispersity (1.55-1.73) and molecular weight (1380-2040 g/mol) are promising to act as precursor for the value-add products processing. These findings demonstrated an ultrafast pretreatment process with excellent results in biomass fractionation and comprehensive utilization of biomass components.
Subject(s)
Eucalyptus , Lignin , Lignin/chemistry , Propylene Glycol , Furaldehyde , Biomass , Choline/chemistry , Microwaves , Solvents/chemistry , HydrolysisABSTRACT
Deep eutectic solvents (DESs) have unique advantages in biomass conversion. However, the migration and transformation mechanism of lignin in the cell wall during the DES pretreatment is still elusive. In this work, Eucalyptus blocks were pretreated in choline chloride/lactic acid DES to reveal the lignin migration. Meanwhile, the remaining lignin in the pretreated residue, the regenerated DES lignin, and the solubilized degraded lignin in the recovered DES were investigated to decipher the lignin transformation. Results showed that the DES pretreatment resulted in the penetration of DES from the cell lumen to the cell wall, and lignin in the secondary wall was more easily dissolved than that in the cell corner middle lamella. The syringyl unit of lignin was better stabilized in the DES than the guaiacyl unit of lignin. The condensed lignin fraction mainly remained in the pretreated residue, while the solubilized degraded lignin fraction was monomeric aromatic ketone compounds. This study elucidates the fate of lignin during the DES pretreatment, which could also promote the development of a modern lignocellulosic pretreatment technique.
Subject(s)
Eucalyptus , Lignin , Biomass , Deep Eutectic Solvents , Hydrolysis , Lignin/chemistry , Solvents/chemistryABSTRACT
Understanding of the morphological changes at different growth stages and lignin accumulation pattern for pine biomass plays the key role in facilitating the further development of value-added utilization and downstream conversion processes. This work systematically revealed the morphological change and lignin accumulation pattern in Chinese pine branches cell walls via confocal Raman microscopy (CRM) technology. Meanwhile, the structural characteristics of isolated lignin samples from different growth stages were synthetically characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC) techniques. The results indicated that the content of pith in adult pine new branch was bigger than juvenile trees. With the increase of physiological age, the branches in adult pine could accumulate more lignin both in overall content and the concentration of cell corner middle layer. Moreover, the significantly increases of molecular weights and the ß-O-4, ß-ß linkages content revealed that the lignin macromolecule of pine would polymerize faster in the adult stage (14, 35 years). The panorama generated from the structural and chemical features of pine native lignin not only benefited to understand the biosynthetic pathways and lignin macromolecules structural variation in plant cell walls from different growth stages but also contributed to the valorization and deconstruction of biomass.
Subject(s)
Lignin , Pinus , Biomass , Cell Wall/chemistry , China , Lignin/chemistryABSTRACT
The alkali-soluble hemicelluloses extracted with 10% KOH solution from corn bran were further isolated with different concentrations of aqueous ethanol solutions. Herein 92.2% of the original hemicelluloses can be obtained and the cellulase enzymatic hydrolysis rate of the alkali treated corn bran can reach to 97.2%. The corn bran hemicelluloses were mainly glucuronoarabinoxylan, in which xylose (48.4-53.8%) and arabinose (27.8-33.2%) were the main components. More linear hemicelluloses with high molecular weight tended to be precipitated in low concentration aqueous ethanol solutions. Furthermore, the relationship between the structural features of these alkali-soluble corn bran hemicelluloses and their furfural yield was investigated in MIBK (methyl isobutyl ketone)/H2O biphasic system. Results showed that the hemicelluloses with high xylose content are benefit to the furfural production, and the highest furfural yield of 67.7% was obtained.
Subject(s)
Furaldehyde , Xylose , Alkalies/chemistry , Ethanol/chemistry , Furaldehyde/chemistry , Hydrolysis , Water/chemistry , Zea mays/chemistryABSTRACT
Developing a biorefinery process for a highly integrated valorization and fractionation of lignocellulose is crucial for its utilization. Herein, a biphasic system comprising choline chloride/lactic acid and 2-methyltetrahydrofuran with Al2(SO4)3 and H2SO4 as catalysts was applied to pretreat Eucalyptus. Results showed that under the optimized conditions (150 °C, 30 min, 0.2 M Al2(SO4)3, 0.075 M H2SO4), the furfural yield and enzymatic hydrolysis efficiency could reach 54.7% and 97.0%, respectively. The efficient cellulose conversion was attributed to remarkable removal of lignin (91.0%) and hemicelluloses (100.0%), thereby causing the disruption of cell wall structure and enhancement of cellulose accessibility. Meanwhile, confocal Raman microscope and atomic force microscope displayed that the pretreatment resulted in the decreasing intensities of carbohydrates and lignin different regions of cell walls, and exposing of the embedded microfibers from noncellulosic polymers. Overall, the deep eutectic solvent-based biphasic system displayed high performance for effective utilization of carbohydrate components in lignocellulose.
Subject(s)
Furaldehyde , Lignin , Biomass , Carbohydrates , Cellulose , Deep Eutectic Solvents , Hydrolysis , Lignin/chemistry , SolventsABSTRACT
An aspirational pretreatment method for efficient fractionation and tailored valorization of large industrial biomass can ensure the realizability of sustainable biorefinery strategies. In this study, an ultrafast alkaline deep eutectic solvents (DES) pretreatment strategy was developed to efficiently extract the lignin nanoparticles and retain cellulose residues that could be readily enzymatic saccharified to obtain fermentative glucose for the bioenergy production from industrial xylose residue. Results showed that the DES pretreatment had excellent delignification performance and the regenerated DES lignin nanoparticles exhibited well-preserved structures and excellent antioxidant activity, as well as low molecular weights and relatively uniform size distribution, which could facilitate downstream catalytic degradation for production of chemicals and preparation of lignin-based materials. Under the optimal condition (DES pretreatment: 80 °C, 10 min; saccharification: 10 FPU/g, 5 wt%, 100 mg/g Tween 80), the glucose yield of 90.12% could be achieved, which was dramatically increased compared to raw materials.
Subject(s)
Lignin , Xylose , Biomass , Deep Eutectic Solvents , Glucose , Hydrolysis , Lignin/chemistry , Solvents/chemistryABSTRACT
Exploration of lignocellulosic biomass provides a sustainable and eco-friendly route for producing liquid fuels, materials, and chemicals. However, direct utilization of lignocelluloses is limited by the stable and complicated cross-linking structure of the plant cell wall. Hydrothermal pretreatment (HTP) is a green and cost-effective technology because it can disrupt lignin-carbohydrate complex (LCC) linkages, dissolve hemicelluloses and lignin, and redistribute lignin in the cell wall layers without utilization of any chemicals. Thus, HTP is expected to achieve industrial scale in second-generation biorefineries and circular bioeconomies. This review analyzed the deconstruction of lignocelluloses by HTP, with particular emphasis on the formation mechanism of hemicellulose degradation products and the structural evolution of hemicelluloses and lignin accompanying HTP. Meanwhile, the formation mechanism of pseudolignin and its effect on the enzymatic hydrolysis of cellulose as well as strategies for inhibiting lignin recondensation were discussed.
Subject(s)
Lignin , Polysaccharides , Biomass , Hydrolysis , Lignin/chemistry , SolubilityABSTRACT
Hydrothermal processes are an attractive clean technology and cost-effective engineering platform for biorefineries based in the conversion of biomass to biofuels and high-value bioproducts under the basis of sustainability and circular bioeconomy. The deep and detailed knowledge of the structural changes by the severity of biomasses hydrothermal fractionation is scientifically and technological needed in order to improve processes effectiveness, reactors designs, and industrial application of the multi-scale target compounds obtained by steam explosion and liquid hot water systems. The concept of the severity factor [log10 (Ro)] established>30 years ago, continues to be a useful index that can provide a simple descriptor of the relationship between the operational conditions for biomass fractionation in second generation of biorefineries. This review develops a deep explanation of the hydrothermal severity factor based in lignocellulosic biomass fractionation with emphasis in research advances, pretreatment operations and the applications of severity factor kinetic model.
Subject(s)
Biofuels , Steam , Biomass , Chemical Fractionation , Lignin , WaterABSTRACT
BACKGROUND: In view of the natural resistance of hemicelluloses in lignocellulosic biomass on bioconversion of cellulose into fermentable sugars, alkali extraction is considered as an effective method for gradually fractionating hemicelluloses and increasing the bioconversion efficiency of cellulose. In the present study, sequential alkaline extractions were performed on the delignified ryegrass material to achieve high bioconversion efficiency of cellulose and comprehensively investigated the structural features of hemicellulosic fractions for further applications. RESULTS: Sequential alkaline extractions removed hemicelluloses from cellulose-rich substrates and degraded part of amorphous cellulose, reducing yields of cellulose-rich substrates from 73.0 to 27.7% and increasing crystallinity indexes from 31.7 to 41.0%. Alkaline extraction enhanced bioconversion of cellulose by removal of hemicelluloses and swelling of cellulose, increasing of enzymatic hydrolysis from 72.3 to 95.3%. In addition, alkaline extraction gradually fractionated hemicelluloses into six fractions, containing arabinoxylans as the main polysaccharides and part of ß-glucans. Simultaneously, increasing of alkaline concentration degraded hemicellulosic polysaccharides, which resulted in a decreasing their molecular weights from 67,510 to 50,720 g/mol. CONCLUSIONS: The present study demonstrated that the sequential alkaline extraction conditions had significant effects on the enzymatic hydrolysis efficiency of cellulose and the investigation of the physicochemical properties of hemicellulose. Overall, the investigation the enzymatic hydrolysis efficiency of cellulose-rich substrates and the structural features of hemicelluloses from ryegrass will provide useful information for the efficient utilization of cellulose and hemicelluloses in biorefineries.
ABSTRACT
Herein, a two-step hydrothermal pretreatment combined with alkali extraction method was applied to deconstruct the poplar cell walls for enzymatic hydrolysis. Results revealed that 88.1 % of hemicelluloses and 77.6 % of lignin were removed during the integrated treatment performed at 180 °C and a maximum enzymatic hydrolysis efficiency of 96.1 % was achieved. Confocal Raman microscopy suggested that the removal of hemicelluloses from cell walls was inhomogeneous, and most hemicelluloses were released from the secondary wall. In addition, 35.2-56.8 % of hemicelluloses were isolated from the integrated treatment. Detailed structural analysis revealed that the water-soluble hemicelluloses possessed more branched structure than the alkali-soluble hemicelluloses and the hemicelluloses isolated from the poplar were mainly composed of a linear backbone of (1â4)-ß-d-Xylp with 4-O-Me-α-d-GlcpA attached as side chains. This work provides an efficient pathway to transform poplar into fermentable sugars and hemicelluloses with considerable yield.
ABSTRACT
Different pretreatments strategies have been developed over the years mainly to enhance enzymatic cellulose degradation. In the new biorefinery era, a more holistic view on pretreatment is required to secure optimal use of the whole biomass. Hydrothermal pretreatment technology is regarded as very promising for lignocellulose biomass fractionation biorefinery and to be implemented at the industrial scale for biorefineries of second generation and circular bioeconomy, since it does not require no chemical inputs other than liquid water or steam and heat. This review focuses on the fundamentals of hydrothermal pretreatment, structure changes of biomass during this pretreatment, multiproduct strategies in terms of biorefinery, reactor technology and engineering aspects from batch to continuous operation. The treatise includes a case study of hydrothermal biomass pretreatment at pilot plant scale and integrated process design.
Subject(s)
Lignin , Steam , Biomass , Cellulose , Chemical Fractionation , Engineering , HydrolysisABSTRACT
Hereon, tobacco stalk was deconstructed by lyophilization, ball-milling, ultrasound-assisted alkali extraction, hydrothermal pretreatment (HTP), and alkali presoaking, respectively, followed by dilute alkali cooking to both improve its enzymatic digestibility and isolate the hemicellulosic streams. It was found that a maximum cellulose saccharification rate of 93.5% was achieved from the integrated substrate by ball-milling and dilute alkali cooking, which was 4.4-fold higher than that from the raw material. Interestingly, in this case, 76.9% of hemicelluloses were simultaneously recovered during the integrated treatment. Structural determination indicated that the hemicelluloses released from tobacco stalk by dilute alkali cooking were mixed polysaccharides, and the (1 â 4)-linked ß-D-Xylp backbone branched with L-Araf units at O-2/O-3 and 4-O-Me-α-D-GlcpA units at O-2 of the xylose residues was the main structure. In comparison, ultrasound-assisted alkali extraction, ball-milling, and HTP favored the extraction of hemicelluloses with less branched structure and lower molecular weights in the following alkali cooking.
Subject(s)
Cellulose , Nicotiana , Hydrolysis , Molecular Weight , PolysaccharidesABSTRACT
A biphasic pretreatment was adopted to disturb the recalcitrant structure of bamboo for further enzymatic hydrolysis and to obtain easily valorized lignin by-product. The biphasic system consisted of biomass-derived chemicals-2-methyltetrahydrofuran and oxalic acid as well as water, and the reactions were conducted at 120-180°C for 20min. The treatment resulted in notable removal of hemicelluloses and lignin. After the pretreatment, the cellulose conversion rate during enzymatic hydrolysis was enhanced by 6.7-fold as compared to the unpretreated raw material. Comprehensive analysis of the lignin product indicated that it exhibited representative structure (such as ß-O-4, ß-ß linkages) as compared to native lignin, contained a very low amount of contaminated sugars (0.67-2.39%), and had a relatively medium molecular weight (Mw 2240-3730g/mol) and good solubility in many organic solvents. This indicated that the lignin showed great potential application in conversion into materials and liquid fuels.
Subject(s)
Furans , Lignin , Oxalic Acid , Cellulose , Hydrolysis , WaterABSTRACT
An integrated process based on ionic liquids ([Bmim]Cl and [Bmim]OAc) pretreatment and successive alkali post-treatments (0.5, 2.0, and 4.0% NaOH at 90°C for 2h) was performed to isolate lignins from Eucalyptus. The structural features and spatial distribution of lignin in the Eucalyptus cell wall were investigated thoroughly. Results revealed that the ionic liquids pretreatment promoted the isolation of alkaline lignin from the pretreated samples without obvious structural changes. Additionally, the integrated process resulted in syringyl-rich lignin macromolecules with more ß-O-4' linkages and less phenolic hydroxyl groups. Confocal Raman microscopy analysis showed that the dissolution behavior of lignin was varied in the morphologically distinct regions during the successive alkali treatments, and lignin dissolved was mainly stemmed from the secondary wall regions. These results provided some useful information for understanding the mechanisms of delignification during the integrated process and enhancing the potential utilizations of lignin in future biorefineries.
Subject(s)
Cell Wall/chemistry , Eucalyptus/chemistry , Lignin/isolation & purification , Alkalies/analysis , Ionic Liquids/chemistry , Plant Stems/chemistryABSTRACT
BACKGROUND: The biomass recalcitrance resulting from its chemical compositions and physical structures impedes the conversion of biomass into fermentable sugars. Pretreatment is a necessary procedure to increase the cellulase accessibility for bioconversion of lignocelluloses into bioethanol. Alternatively, ionic liquids, a series of promising solvents, provide unique opportunities for pretreating a wide range of lignocellulosic materials. In this study, a two-step treatment including ionic liquids pretreatment and successive alkali fractionations was performed on Eucalyptus to achieve a high enzymatic digestibility. The compositional and structural changes of Eucalyptus cell walls and their possible effect on saccharification ratio were comprehensively investigated. RESULTS: After the ionic liquids pretreatment, the cell walls became loose and even swelled, accompanying with the decrease of cellulose crystallinity. As compared to the simplex ionic liquids pretreatment, the integrated process resulted in the significant removal of hemicelluloses and lignin, enhancing the disruption of the cell walls and increasing the exposure of cellulose, which led to a higher conversion of cellulose to glucose. The glucose yield of Eucalyptus underwent the combination of [Bmim]OAc and alkali treatments reached the maximum (90.53 %), which was 6.6 times higher than that of the untreated Eucalyptus. The combination of chemical compositions and physical structure of Eucalyptus affected the efficiency of cellulose enzymatic hydrolysis. Especially, the changes of cellulose crystallinity played a major role in enhancing the enzymatic digestibility of Eucalyptus in this study. CONCLUSIONS: The two-step treatment with ionic liquids pretreatment and successive alkali fractionation can be considered as a promising method to improve the conversion of cellulose to glucose. The detailed information obtained about chemical and anatomical changes was helpful to understand the underlying mechanism of the integrated treatment process acting on Eucalyptus for enhancing enzymatic digestibility.
ABSTRACT
Eucalyptus was sequentially extracted with 70% ethanol containing 0.4, 1.0, 2.0, 3.0, and 5.0% NaOH for 2h at 80°C. The chemical composition and structural features of the hemicellulosic fractions obtained were comparatively characterized by the combination of high-performance anion-exchange chromatography, gel permeation chromatography, Fourier transform infrared, and nuclear magnetic resonance spectroscopies. Furthermore, the main component distribution and their changes in cell wall were investigated by confocal Raman microscopy. Based on the Fourier transform infrared and nuclear magnetic resonance analyses, the hemicelluloses extracted from Eucalyptus mainly have a linear backbone of (1â4)-linked-ß-d-xylopyranosyl residues decorated with branch at O-2 of 4-O-methyl-α-glucuronic acid unit. Raman analysis revealed that the dissolution of hemicelluloses was different in the morphological regions, and the hemicelluloses released mainly originated from the secondary wall. The information obtained from the study conducted by combining chemical characterization with ultrastructure provides important basis for studying the mechanism of the alkali treatment.
Subject(s)
Ethanol/chemistry , Eucalyptus/chemistry , Polysaccharides/chemistry , Sodium Hydroxide/chemistry , Cell Wall/chemistry , Magnetic Resonance Spectroscopy , Molecular Weight , Solubility , Spectroscopy, Fourier Transform Infrared , Spectrum Analysis, Raman , Wood/chemistryABSTRACT
In this study, sweet sorghum stem was subjected to hydrothermal pretreatment (HTP) and alkaline post-treatment to enhance its saccharification ratio by reducing its recalcitrance. The results showed that the HTP (110-210°C, 0.5-2.0h) significantly degraded hemicelluloses, and the pretreatment at the temperature higher than 190°C led to the partial degradation of the cellulose. As compared to the sole HTP, the integrated process removed most of lignin and hemicelluloses, which incurred a higher cellulose saccharification ratio. Under an optimum condition evaluated (HTP at 170°C for 0.5h and subsequent 2% NaOH treatment), 77.5% saccharification ratio was achieved, which was 1.8, 2.0 and 5.5 times as compared to the only HTP pretreated substrates, alkaline treated substrates alone and the raw material without pretreatment, respectively. Clearly, the integrated process can be considered as a promising approach to achieve an efficient conversion of lignocellulose to fermentable glucose.