Acid-insoluble Lignin Research Articles

Structural and Chemical Analysis of Three Regions of Bamboo (Phyllostachys Edulis)

This study focuses on three different regions of moso bamboo (Phyllostachys edulis): an inner layer (IB), middle layer (MB), and outer layer (OB), to comprehensively characterize the structural features, chemical composition (ash, extractives and lignin contents), and the lignin monomeric composition as determined by analytical pyrolysis. The results show that bamboo presents a gradient structure. From the IB to OB, the vascular bundle density and fiber sheath ratio increase, the porosity decreases (from 45.92% to 18.14%), and the vascular bundle diameter–chord ratio increases (from 0.85 to 1.48). In terms of chemical composition, the ash, extractives, and acid-soluble lignin content gradually decrease from IB to OB. The holocellulose content follows the trend: MB (66.3%) > OB (65.9%) > IB (62.8%), while the acid-insoluble lignin content exhibits the opposite trend: IB (22.6%) > OB (17.8%) > MB (17.7%). Pyrolysis products reveal the diversity of carbohydrates and lignin derivatives, with a lignin monomeric composition rich in syringyl and guaiacyl units and lower amounts of H-units: the IB has an H:G:S relation of 18:26:55, while 15:27:58 is the ratio for the MB and 15:40:45 for the OB; S/G ratio values were, respectively, 1.22, 1.46, and 0.99. A comprehensive analysis highlights significant gradient variations in the structure and chemistry of bamboo, providing robust support for the classification and refinement methods of bamboo residues for potential applications.

Cellulose extraction from Cladophora rupestris for extraction of nanomaterials

Abstract Cellulose from macroalgae is potential for the extraction of nanomaterials due to its availability and its great fraction in the biomass. Cladophora rupestris is a macroalgae and is a good material to which a cellulose may be extracted. The said macroalgae has no value-added products or uses yet. It has a lignocellulosic profile of: alpha-cellulose, 33.43 %; hemicellulose, 15.48%; holocellulose, 48.93; acid soluble lignin, 2.22%; acid insoluble lignin, 22.33%, extractives, 5.67% and total ash, 39.65%. Identifying the best method and conditions for the extraction of cellulose from the said material is a challenge that needs to be addressed. The process for the cellulose extraction considered variations on drying (oven, air, and sun drying), defatting (using solvents: methanol and hexane; and extraction time: 8 hrs and 4 days), solvent drying (oven and air drying), alkaline pre-treatment (0.1, 0.5, and 1M NaOH), fixed conditions on bleaching, bleached biomass oven drying. The biomass weight losses were monitored for some steps, attributing this on the removal of the lignin and extractives. The lignocellulosic profile of the crude cellulose extracted from the macroalgae using the best conditions was determined indicating an increased fraction of the cellulose components in the biomass and a transformation of the rigid biomass into a soft and paper-like texture. The functional groups present on the cellulose was determined. The extracted cellulose was used to produced cellulose nanofibril (CNF) with fiber diameter of the CNF ranges on 14.29 – 37.50 nm and crystallinity index of 92.48%. Attempts were done on extraction of cellulose nanocrystal (CNC) utilizing microwave-assisted acid hydrolysis (MAAH) and semi-batch acid hydrolysis (SBAH); and variation on the acid used (sulfuric acid, and oxalic acid), concentration of the acid, and the temperature conditions.

Photosynthesis and Latex Burst Characteristics in Different Varieties of Rubber Trees (Hevea brasiliensis) under Chilling Stress, Combing Bark Tensile Property and Chemical Component Analysis

Rubber trees (Hevea brasiliensis) serve as the primary source of natural rubber. Their native habitat is characterized by warm and humid conditions, so they are particularly sensitive to low temperatures. Under such stress, latex burst can cause severe damage to rubber trees, which is due to the uniqueness of their economically productive parts. In order to establish a correlation between young and mature rubber trees and provide a novel prospective for investigating the mechanisms of latex burst and chilling resistance in rubber trees, the chlorophyll contents, photosynthesis, and chlorophyll fluorescence parameters in four varieties of one-year-old rubber tree seedlings were analyzed under artificially simulated chilling stress. The latex burst characteristics were subsequently recorded. A comprehensive statistical analysis of the chilling-resistance rank was conducted using the membership function method and the combination weighting method. Meanwhile, chemical compositions and tensile properties of barks from two-year-old twigs of mature rubber trees were ascertained. A correlation analysis between chilling resistance, chemical compositions, and tensile properties was performed to identify any interrelationships among them. The results showed that the number and the total area of latex-burst positions in variety Reken628 seedlings were greater than those in other varieties, and the lowest number and total area of latex-burst positions were observed in variety RRIM600 and variety PR107, respectively. With the exception of variety GT1, nectar secretion was noted in all other varieties of rubber tree seedlings under chilling stress. The chilling resistance of the four varieties decreased in the following order: variety GT1 > variety RRIM600 > variety PR107 > variety Reken628. The chilling resistance was strongly (p < 0.001) negatively correlated with cellulose content and acid-insoluble lignin content, respectively. The total area of latex burst was significantly (p < 0.001) and positively correlated with holocellulose content and maximum load, respectively. Furthermore, this study also provides new insights into the mechanism of nectar secretion induced by low temperatures and its association with the chilling resistance of rubber trees.

Enhanced Saccharification Yield of Alkali Pretreated Sugarcane Bagasse Utilizing Customized Cellulase Cocktail from Trichoderma harzianum and Trichoderma viride

The experiment was conducted during 2023 at Bioenergy Laboratory, Department of RBEE, College of Agricultural Engineering and Technology, CCSHAU, Hisar, Haryana, India. Compositional changes in sugarcane bagasse subjected to varying concentrations of sodium hydroxide (0.3% to 1.2%), revealing significant increases in glucan content (from 37.13% to 53.81%) alongside decreases in xylan, acid-insoluble lignin, acid-soluble lignin, ash, and other extractives. These changes were validated using microscopic technique SEM, confirming the efficacy of the pretreatment process. The utilization of a customized cellulase cocktail derived from Trichoderma harzianum and Trichoderma viride holds significant promise in enhancing the saccharification from alkali-pretreated sugarcane bagasse. This study investigates the synergistic effects of cellulase enzymes produced by these fungi on the hydrolysis of lignocellulosic biomass. The enzymatic hydrolysis process is optimized by varying enzyme dosages, reaction conditions, and incubation times to maximize the release of fermentable sugars. Results indicate a substantial improvement in saccharification efficiency with the customized cellulase cocktail, highlighting its potential for sustainable biofuel production. The pretreated sugarcane bagasse, when saccharified with Trichoderma harzianum and Trichoderma viride individually, released 254.43 mg g-1 and 325.53 mg g-1 of reducing sugars, respectively, after 40 h of incubation. In contrast, the combined enzymatic cocktail achieved a substantial increase in glucose yields (345.12 mg g-1) at 40 h, showcasing the synergistic effect of the combined enzymatic activity. This research contributes to advancing bioconversion technologies for utilizing lignocellulosic biomass resources efficiently and economically, thus addressing key challenges in sustainable energy production.

New insights into kinetics and mechanisms of acid sulphite delignification of Eucalyptus globulus wood

The kinetics of Eucalyptus globulus wood delignification in Mg-base acid sulphite pulping of dissolving pulp was studied using a pilot-scale batch digester simulating the industrial process. The behavior of lignin during impregnation, heating-up and bulk delignification at the final temperature was evaluated by the analysis of acid-insoluble lignin in wood and wood residue after pulping. The dynamics of lignin dissolution was followed by its structural analysis in solid residues and in solution by wet chemistry and 1D and 2D nuclear magnetic resonance (NMR) spectroscopy. About 30 % and 20 % of the lignin were removed in the impregnation and heating-up pulping steps, respectively. About 45 % of the lignin was removed at the final pulping temperature in bulk and 3 % in the residual delignification stages. The kinetics of bulk delignification followed a pseudo-first-order kinetics with an effective activation energy of 138.4 kJ/mol in the temperature range of 140–148 °C. Bulk delignification follows an undefined overall order in the hydrogen and bisulfite ions and depended on the partial pressure of SO2 at ca. 0.60 order within the range of combined SO2 in pulping acid of 1.14–1.66 % and total SO2 loads of 6.2–7.0 %. Minimum degree of lignin sulphonation to be dissolved in the pulping liquor was suggested to be about 0.35 sulphonic groups per one phenyl propane unit. Lignin removal during pulping showed dependence on its location in different morphological parts of the fibers and related structural characteristics, which were discussed accordingly. A role of the polysaccharide complex in the accessibility of lignin was highlighted. A noticeable cleavage of β-O-4 linkages occurred in lignin already dissolved in pulping liquor at the end of cooking.

INFLUENCE OF GROWING CONDITIONS AND PRIMARY PROCESSING OF TECHNICAL HEMP ON ITS POLYMER COMPOSITION

The article proposes a methodology for experimental monitoring of a set of parameters of the chemical state of a biopolymer system of technical cannabis. Using sequential extraction techniques, the content of alpha-cellulose, pectin substances, hemicelluloses, acid insoluble lignin and other related compounds, including heavy metal ions, extraction substances, silicon oxide, in bast, bonfire and undirected hemp obtained from technical hemp trusts grown in Ivanovo Region, was determined. The influence of the soil factor on the biosynthesis of polymers and related substances of the bast and woody parts of the stem and on the destruction of plant tissues of hemp in the conditions of meadow vegetation has been traced. It has been established that the composition of hemp raw materials is influenced not only by the genetic nature of the plant, but also by the natural conditions of its cultivation and the peculiarities of the action of soil microflora in the processes of primary processing of the stem.

Rapid and high-throughput determination of sorghum (Sorghum bicolor) biomass composition using near infrared spectroscopy and chemometrics

Compositional characterization of biomass is vital for the biofuel industry. Traditional wet chemistry-based methods for analyzing biomass composition are laborious, time-consuming, and require extensive use of chemical reagents as well as highly skilled personnel. In this study, near-infrared (NIR) spectroscopy was used to quickly assess the composition of above-ground vegetative biomass from 113 diverse, photoperiod-sensitive, biomass-type sorghum (Sorghum bicolor) accessions cultivated under field conditions in Central Illinois. Biomass samples were analyzed using NIR spectra collected in the spectral range of 867–2536 nm, with their chemical compositions determined following the National Renewable Energy Laboratory (NREL) protocol. Advanced spectral pre-treatment and band selection techniques were utilized to develop calibration models using partial least squares regression (PLSR). The models' effectiveness was assessed through cross-validation and independent data tests. The predictions for moisture, ash, extractives, glucan, xylan, acid-soluble lignin (ASL), acid-insoluble lignin (AIL), and total lignin were accurate and reliable, demonstrating the capability of NIR spectroscopy to provide rapid and precise characterization of sorghum biomass. The results demonstrated that NIR spectroscopy is an efficient tool for rapidly characterizing sorghum biomass, making it a sustainable option for screening desirable feedstock for biofuel or bioproduct production.

Lignin Purification from Mild Alkaline Sugarcane Extract via Membrane Filtration

In this study, the separation of lignin from a mild alkaline sugarcane bagasse extract was studied, and the impacts of different parameters on the filtration performance were evaluated. The tested parameters included transmembrane pressure (0.5–3.0 bar), shear rates (2831–22,696 s−1), temperature (20 and 40 °C), membrane molecular weight cut-off (5 and 10 kDa), and membrane material (polyethersulfone and polysulfone). During the filtration process, the permeate flux and all the main components of the extract were analyzed, including lignins (acid insoluble lignin and acid soluble lignin), sugars (xylose, arabinose, glucose, and galactose), total phenolic compounds, and phenolic acids (p-coumaric acid, ferulic acid, vanillin, and 4-hydroxybenzaldehyde). It was proved that the tested conditions had a great impact on the permeate flux and molecule retention rate. Increasing the temperature from 20 to 40 °C resulted in a much higher permeate flux for the 5 kDa PES membrane, and the impact of shear rate was greater at 40 °C for this membrane. Although the 5 kDa PES membrane could retain slightly more large molecules, i.e., acid-insoluble lignin and xylose, the 10 kDa membrane afforded greater phenolic acid removal capacity, leading to higher purity. For the 10 kDa PS membrane, the polarization layer began to form at TMP below 0.5 bar. This membrane had a lower retention rate for all molecules than the 10 kDa PES membrane.

Industrial Two-Phase Olive Pomace Slurry-Derived Hydrochar Fuel for Energy Applications.

The present study aims to resolve the existing research gaps on olive pomace (OP) hydrochars application as a fuel by evaluating its molecular structures (FTIR and solid NMR analysis), identifying influential characteristics (Pearson correlation analysis), process optimization (response surface methodology), slagging-fouling risks (empirical indices), and combustion performance (TG-DSC analysis). The response surfaces plot for hydrothermal carbonization (HTC) of OP slurry performed in a pressure reactor under varied temperatures (180-250 °C) and residence times (2-30 min) revealed 250 °C for 30 min to be optimal conditions for producing hydrochar fuel with a higher heating value (32.20 MJ·Kg-1) and energy densification ratio (1.40). However, in terms of process efficiency and cost-effectiveness, the optimal HTC conditions for producing the hydrochar with the highest energy yield of 87.9% were 202.7 °C and 2.0 min. The molecular structure of hydrochar was mainly comprised of aromatic rings with methyl groups, alpha-C atoms of esters, and ether bond linkages of lignin fractions. The slagging and fouling risks of hydrochars were comparatively lower than those of raw OP, as indicated by low slagging and fouling indices. The Pearson correlation analysis emphasized that the enrichment of acid-insoluble lignin and extractive contents, carbon densification, and reduced ash content were the main pivotal factors for hydrochar to exhibit better biofuel characteristics for energy applications.

Purification of soda lignin

Purity of technical lignin is one of the main obstacles in the utilization of lignin to value-added chemicals, products, and materials. The objective of this study was to investigate and compare single and two stage purification methods for obtaining soda lignin with high purity. Extensive washing and extraction with water was found effective, increasing the abundance of acid insoluble lignin while reducing its ash content. Extraction with organic solvents was conducted with 2-propanol or blends of n-heptane/1-butanol or cyclohexane/acetone. These solvents were shown to have little effect on the total lignin content, as determined by wet-chemical methods. Two-stage treatments (washing with water followed by solvent extraction) were hence not better than single stage water extraction in terms of the lignin purity. Still, selective removal of low molecular weight components after solvent extraction was noted, reducing the overall polydispersity of the lignin. Evaporation at 40 °C also showed little effect, whereas calcination at 150 °C significantly increased the molecular weight of the soda lignin. The latter effect was explained by thermally induced cross-linking. In addition, the UV absorbance of the calcinated lignin increased, which is likely related to changes in the aromatic structure. Such effect also entailed that UV/vis spectrophotometry was found less reliable in determining the total lignin content. At last, a mathematical model was adapted to predict the total lignin content from FTIR spectrometry. In conclusion, the tested procedures can be used to purify soda lignin and adjust its molecular weight.

Chemical composition and structural features of cellolignin from steam explosion followed by enzymatic hydrolysis of Eucalyptus globulus bark

Bark is one of the main wastes of the chemical and mechanical processing of Eucalyptus globulus wood. The proposed biochemical processing of bark via saccharification pathway involves steam explosion (SE) pretreatment (severity factor log R0 of 4.22) followed by enzymatic hydrolysis using an enzymatic cocktail composed of cellulolytic and xylanolytic enzymes. Almost 70% cellulose saccharification was achieved. The remaining cellolignin residue (CLEZ) was analysed for its chemical composition and structural features by conventional wet chemistry methods and a series of spectroscopic tools (FTIR-ATR, solid-state CP/MAS 13C NMR spectroscopy and wide-angle X-ray scattering (WAXS)). The main CLEZ component (about 51%) is acid-insoluble lignin, the chemical composition of which in terms of the ratio of syringyl (S), guaiacyl (G) and p-hydroxyphenyl (H) units (70:28:2) is very close to that in the initial bark. This lignin is highly condensed and structurally associated with condensed tannins, which makes CLEZ recalcitrant to delignification by common methods. About one third of cellulose in eucalyptus bark after SE was inaccessible to enzymatic hydrolysis and remained in the CLEZ. This cellulose, structurally similar to microcrystalline cellulose, is imbedded into the lignin-tannins condensed matrix and extremely difficult to purify. In contrast to cellulose, bark hemicelluloses were effectively removed in enzymatic hydrolysis, with only small amounts (<2%) remaining in CLEZ. Among other CLEZ ingredients, proteins and inorganic/organic salts were the most abundant. The latter includes noticeable amounts of calcium oxalate phytoliths (up to 9%), Fe and Si salts. The eventual application areas of CLEZ are discussed.

Acid insoluble lignin material production by chemical activation of olive endocarps for an efficient furfural adsorption-removal from aqueous solutions

The present work describes a protocol of chemical activation, with acid catalyst, of olive endocarps to obtain acid insoluble lignin-rich materials with high capacities for the adsorption of furfural present in aqueous media. During biomass activation, factors such as acid concentration, reaction time and temperature, solid/liquid ratio and the presence of water extractives strongly affected both the surface characteristics of the treated bioadsorbents and their capacities for furfural retention (percentage increase close to 600% with respect to the crude biomass). Once a treated solid with good adsorbent properties was obtained, the optimal conditions for adsorption were found: stirring speed 80 rpm, temperature 303 K and adsorbent load 7.5 g solid/50 cm3. Kinetic study indicated the pseudo-second order model provided the best fit of the experimental data. At 303 K, the equilibrium adsorption capacities values ranged from 2.27 mg g−1 to 29.29 mg g−1, for initial furfural concentrations between 0.49 g dm−3 and 12.88 g dm−3. Freundlich model presented the best isotherm (R2 = 0.996 and SE = 4.7%) providing KF and n values of 0.115 (mg g−1) (mg dm−3)−n and 0.610, respectively. Since physical interactions predominate in the adsorption of furfural on chemically activated olive endocarps, the furfural removal process could have occurred reversibly on the heterogeneous surface of the bioadsorbents.

Influence of Thermal Pretreatment on Lignin Destabilization in Harvest Residues: An Ensemble Machine Learning Approach

The research on lignocellulose pretreatments is generally performed through experiments that require substantial resources, are often time-consuming and are not always environmentally friendly. Therefore, researchers are developing computational methods which can minimize experimental procedures and save money. In this research, three machine learning methods, including Random Forest (RF), Extreme Gradient Boosting (XGB) and Support Vector Machine (SVM), as well as their ensembles were evaluated to predict acid-insoluble detergent lignin (AIDL) content in lignocellulose biomass. Three different types of harvest residue (maize stover, soybean straw and sunflower stalk) were first pretreated in a laboratory oven with hot air under two different temperatures (121 and 175 °C) at different duration (30 and 90 min) with the aim of disintegration of the lignocellulosic structure, i.e., delignification. Based on the leave-one-out cross-validation, the XGB resulted in the highest accuracy for all individual harvest residues, achieving the coefficient of determination (R2) in the range of 0.756–0.980. The relative variable importances for all individual harvest residues strongly suggested the dominant impact of pretreatment temperature in comparison to its duration. These findings proved the effectiveness of machine learning prediction in the optimization of lignocellulose pretreatment, leading to a more efficient lignin destabilization approach.

Integrated application of morphological, anatomical, biochemical and physico-chemical methods to identify superior, lignocellulosic grass feedstocks for bioenergy purposes

Grasses have sufficient potential to be used in the biofuel industry due to many reasons. Hence, systematic assessments of the lignocellulosic biomass obtained from six grasses namely Arundo donax, Chrysopogon zizanioides, Coix lacryma-jobi, Pennisetum purpureum, Saccharum spontaneum, and Sorghum bicolor have been performed to assess their potential for bioethanol production. Selected morphological (height, internode diameter, number of internodes, fresh biomass, dry biomass, total volatile matter), anatomical (vascular bundle, stain intensity), analytical (crystallinity index of cellulose, thermal stability, hemicellulose, moisture content) and biochemical (α-cellulose, acid insoluble lignin) parameters were investigated and statistically analysed to detect the superior grass species. The study indicates that S. spontaneum harbours promising biofuel potential by having high dry biomass (56.33 g), α-cellulose (55.88–67.76%), but lower thermal stability (Tmax: 344.37 °C). Comparable ligno-cellulose properties with respect to dry biomass (54.60 g), α-cellulose content (45.95–64.14%), Tmax (360.51 °C) have been observed for A. donax. However, relatively higher lignin contents (∼17–23%) and crystalline cellulose (43.63%–46.96%) in S. spontaneum and A. donax might have resulted into lesser saccharification yield (216.04–230.08 mg/g). On that aspect, S. bicolor and C. lacryma-jobi might be useful since they possessed lower lignin (14.03–16.56%) and crystalline cellulose (32.51–33.02%) leading to higher glucose yield (263–420.06 mg/g). Taken together, this study indicates that integration of morphological, biochemical, and analytical properties of biomasses are complex, yet useful to predict a ‘superior donor plant’ for bioenergy purposes.

Thermo‐economic assessment of a bench‐scale pyrolysis unit through a process simulator

AbstractThis article focuses on the holistic appraisal of a pilot‐scale updraft reactor (E1) powered by the processed residue of forest waste (W1) and hog fuel (W2). The detailed analysis of the up‐draft unit includes the availability of energy, economic evaluation, and the determination of the lignocellulose content of the pine waste. The reformed structure of the pine pellet was used for gas, bio‐oil, and char generation. The Aspen HYSYS process simulator was used for simulation purposes and the results were validated with the solution obtained experimentally. For the measurement of the constituent contents of the pine needles, the National Renewable Energy Laboratory (NREL) procedure was adopted. To investigate the similitude of the packed bed reactor, the Soave–Redlich–Kwong model was considered. For comparison of the given prototype, five different reactor types – conversion (R1), equilibrium (R2), Gibbs (R3), continuous stir tank (CST) (R4) and plug flow (R5) – were juxtaposed and their thermodynamic behavior was evaluated. From structural composition, it was noticed that the cellulose and hemicellulose(s) content dropped by 24.95% and 37.37%, respectively, whereas a rise of 23.33% was seen in the acid‐insoluble lignin (AIL) fraction of forest waste after the torrefaction process. Irrespective of the fuel type, the unconsumed fuel percentage was the same for both wood and processed residue pellets for R5. The relative percentage of methane increased by 1% for processed forest residue. The CO2 emission was estimated to be maximum for reactors R3 and R4. The O2 gain was absent in the R2 reactor. Concomitantly, it gained momentum in R1, R3, and R4. The simulated polytropic equations of state for W1 and W2 were PV1.083 = C and PV1.092 = C, respectively. The levelized cost of energy dropped by 12.50% while scaling up a pyrolysis unit.

Pre-pasteurization enhances the fermentation of wheat straw by Irpex lacteus: Chemical composition, enzymatic hydrolysis, and microbial community

Pasteurization is an economical and convenient method to eliminate harmful microorganisms in raw materials for fermentation. However, the surviving species in pasteurized wheat straw and their potential effects on white rot fungi fermentation remain unclear. In this study, wheat straw was pasteurized at different temperatures (60–85 ℃) and fermented with Irpex lacteus for 28 days. At the end of fermentation, the acid-insoluble lignin (ADL) content decreased significantly in all pasteurized samples (P < 0.05). We found a negative correlation between ADL content and pasteurization temperature (R =0.992, P < 0.001). In enzymatic hydrolysis, the sugar yield of samples pasteurized at 80 ℃ (T80) was higher 39.9% than that at 60 ℃. Regarding microbial community, I. lacteus was the dominant fungus in T80 at an abundance of 93.4%, whereas the abundance of other fungi, such as Chaetomium and Aspergillus, was below 1.60%. Three bacteria, including Bacillus, Lysinibacillus, and Paenibacillus, had a combined abundance of 80.5% in T80, which could be attributed to their high-temperature tolerance and symbiosis with I. lacteus. Bacterial functions, such as nitrogen cycling, cellulolysis, chitinolysis, and methylotrophy, were enriched in T60 samples, but the functions and those related to human and animal pathogen reduced in T80 samples, which promoted the growth and degradation of I. lacteus. Overall, thermotolerant fungi and spore-forming bacterial species are the dominant microorganisms in wheat straw pasteurized above 80 ℃, which promotes the colonization and degradation of I. lacteus and improves the biosafety of treated wheat straw.

Toward a hydrogen-free reductive catalytic fractionation of wheat straw biomass.

The reductive catalytic fractionation (RCF) of lignocellulosic biomass is an attractive method for the conversion of lignin toward valuable low-molecular weight aromatics. A limitation to the upscaling of such technology is represented by the use of pressurized hydrogen gas. Here, the role of hydrogen gas within the RCF of wheat straw biomass is investigated. The use of H2 is shown to enhance lignin depolymerization, by virtue of an improved hydrogenolysis and hydrogenation of lignin fragments, with a yield of phenolic monomers that increased from ~12 wt% of acid-insoluble lignin in the initial biomass under inert atmosphere, up to ~25 wt% under H2 (in methanol, at 250 °C, with Ru/C). The adoption of methanol, ethanol or isopropanol as hydrogen-donor solvents was also investigated in the absence of H2. Ethanol was found to give the highest yield of monophenolics (up to ~20 wt%) owing to a better balance between solvolysis, hydrogenolysis, and hydrogenation of lignin. Nevertheless, a substantial loss of the carbohydrate fraction was observed. The use of a lower temperature (200 °C) in combination with H3PO4 resulted in an improved recovery of cellulose in the pulp and in the solubilization of hemicellulose and lignin, with the formation of monosaccharides (~14 wt% of polysaccharides in the initial biomass) and phenolic monomers (up to 18 wt%, in the absence of H2). Overall, a tradeoff exists between the removal of H2 from the process and the production of low-MW phenolics during RCF.

Membrane Filtration Applied to the Purification of Sugarcane Bagasse Mild Alkaline Extracts

Sugarcane bagasse (SCB), a by-product of the sugar industry, is composed mainly of cellulose, hemicelluloses, and lignin, and can be used to replace petrochemical polymers in various applications. In this work, SCB was treated under mild alkaline conditions with 1.5% NaOH (m:v) and a solid:liquid ratio of 1:20 (m:v) at 60 °C, during 6 h. A 10 kDa polysulfone hollow fiber membrane was used for the purification of the extract in different filtration modes, namely concentration and diafiltration, and a combination of both modes. Permeate fluxes and rejection rates were evaluated at different transmembrane pressure (TMP) at the shear rate of 10,187 s–1, at 40 °C. In concentration mode, increasing the volume reduction factor up to 6.1 led to a significant increase in the retention rates of acid-soluble lignin (ASL) and xylan, and a decrease in inorganic salt content in the retentate. In diafiltration mode, after 2.9 diavolumes, the acid-insoluble lignin (AIL) and xylan rejection rates drastically increased, as did the rejection rates of ash.

Follow-up of solid-state fungal wood pretreatment by a novel near-infrared spectroscopy-based lignin calibration model

Lignin removal plays a crucial role in the efficient bioconversion of lignocellulose to fermentable sugars. As a delignification process, fungal pretreatment has gained great interest due to its environmental friendliness and low energy consumption. In our previous study, a positive linear correlation between acid-insoluble lignin degradation and the achievable enzymatic saccharification yield has been found, hereby highlighting the importance of the close follow-up of lignin degradation during the solid-state fungal pretreatment process.However, the standard quantification of lignin, which relies on the two-step acid hydrolysis of the biomass, is highly laborious and time-consuming. Vibrational spectroscopy has been proven as a fast and easy alternative; however, it has not been extensively researched on lignocellulose subjected to solid-state fungal pretreatment. Therefore, the present study examined the suitability of near-infrared spectroscopy (NIR) for the rapid and easy assessment of lignin content in poplar wood pretreated with Phanerochaete chrysosporium. Furthermore, the predictive power of the obtained calibration model and the recently published ATR-FTIR spectroscopy-based model were compared for the first time using the same fungus-treated wood data set.PLSR was used to correlate the NIR spectra to the acid-insoluble lignin contents (19.9%–27.1%) of pretreated wood. After normalization and second derivation, a PLSR model with a good coefficient of determination (RCV2 = 0.89) and a low root mean square error (RMSECV = 0.55%) were obtained despite the heterogeneous nature of the fungal solid-state fermentation. The performance of this PLSR model was comparably good to the one obtained by ATR-FTIR (RCV2 = 0.87) while it required more extensive spectral pre-processing. In conclusion, both methods will be highly useful for the high-throughput and user-friendly monitoring of lignin degradation in a solid-state fungal pretreatment-based biorefinery concept.

Effects of enzymatic hydrolysis and physicochemical properties of lignocellulose waste through different choline based deep eutectic solvents (DESs) pretreatment

DESs are promising green solvents in lignocellulose pretreatment. In this work, four choline chloride based DESs were synthesized and their physicochemical properties were evaluated. Herbaceous lignocellulose (wheat straw, sorghum straw) and woody lignocellulose biomass (poplar wood, pine wood) were selected as pretreated substrates. In order to reveal the mechanism that pretreatment can improve the efficiency of enzymatic hydrolysis, the pretreated lignocellulose and lignin were analyzed. SEM, FT-IR and XRD characterization revealed the microstructural changes of pretreated lignocellulose, including the increase of surface roughness and pore erosion, changes of polysaccharide/lignin chemical groups, the increase of CrI. The efficient delignification increased the accessibility of enzyme to cellulose, the lignin content negatively affected enzymatic hydrolysis conversion. Furthermore, GPC analysis showed that the polydispersity of sulfonated lignin was reduced after pretreatment, lignin had more homogeneous molecular structures. The degree of unsaturation was calculated according to the elemental composition of sorghum straw and lignin. The unsaturation of pretreated sorghum straw decreased, that may be due to the removal of partial lignin. The elemental composition of acid insoluble lignin (separated from sorghum straw) reflects the increase of unsaturation of lignin after pretreatment.