Search Results (46)

Pelletizing enhances competitiveness of lignocellulosic biomass (LCB) as a fuel by increasing its bulk and energy density. However, LCB pellets are prone to degradation from moisture, have high ash, and pose safety risks due to carbon monoxide (CO) emissions during storage. Hot water extraction (HWE), a mild hydrothermal treatment particularly effective for angiosperms, removes most hemicelluloses (xylans), reduces ash, and increases lignin content in remaining HWE-LCB. Based on the current understanding of CO formation, these changes suggested that HWE could reduce CO emissions. In this study, we evaluated the effects of HWE on pellets made from shrub willow, miscanthus, and wheat straw. A statistical analysis was conducted on ash, energy content, bulk density, durability, pellet length and density, moisture absorption, and CO emissions. All HWE-LCB pellets demonstrated significant increases in energy content (up to 3.54%) and reductions in moisture absorption (up to 23.84%). Although not all effects reached statistical significance, HWE generally had positive effects on ash content, bulk density, durability, and average pellet length and density. Contrary to expectations, HWE-LCB pellets emitted significantly more CO under both ambient and isothermal temperature conditions (up to 4.25 times overall increase), although still less than commercial hardwood/softwood blend pellets (<200 ppm in HWE-LCB vs. >300 ppm). Full article

Bioethanol from sugarcane bagasse is a promising second-generation biofuel due to its abundance as a sugar industry by-product. Herein, enzymatic hydrolysate obtained from sugarcane bagasse pretreated with optimized hydrothermal alkaline sulfite (HAS) was evaluated for its fermentability using Saccharomyces cerevisiae PE-2 and Scheffersomyces stipitis CBS 5773. The HAS pretreatment achieved a high delignification rate (63%), resulting in a cellulose- and hemicellulose-enriched substrate (55% and 27%, respectively). While the cellulose content remained relatively constant, hemicellulose content was reduced by 25%, with significant removal of acetyl groups (80%) and arabinan groups (39%). The pretreated bagasse exhibited high digestibility, applying 10 FPU (filter paper unit) cellulase together with 10 CBU (cellobiose unit) β-glucosidase per gram of dry bagasse in the hydrolysis step, yielding 72% glucan and 66% xylan conversion within 72 h. The resulting hydrolysate was efficiently fermented by S. cerevisiae and S. stipitis, achieving ethanol yields of 0.51 and 0.43 g/g of sugars, respectively. The fermentation kinetics were comparable to those observed in a synthetic medium containing pure sugars, demonstrating the effectiveness of HAS pretreatment in generating readily fermentable, carbohydrate-rich substrates. HAS pretreatment enabled improved conversion of sugarcane bagasse into fermentation-ready sugars, constituting a potential resource for bioethanol synthesis applying both S. cerevisiae and S. stipitis in the future. Full article

Waste wheat straw (WS) is a common agricultural waste with a low acquisition cost and a high annual yield, making it a promising feedstock for a biorefinery. In this work, efficient co-production of reducing sugars and xylo-oligosaccharides (XOSs) from WS was realized through FeCl₃-assisted p-toluene sulfonic acid (PTSA) pretreatment. The effects of reaction conditions (PTSA content, FeCl₃ loading, pretreatment duration, and temperature) on lignin and xylan elimination and enzymolysis were analyzed. The results manifested that the enzymolysis of WS substantially elevated from 22.0% to 79.3% through the treatment with FeCl₃-PTSA/water (120 °C, 60 min). The xylan removal and delignification were 79.7% and 66.6%, respectively. XOSs (4.0 g/L) were acquired in the pretreatment liquor. The linear fitting about LogR₀ with enzymolysis, delignification, xylan elimination and XOSs content was investigated to explain the reasons for the elevated enzymolysis and to clarify the comprehensive understanding of WS enzymolysis through the FeCl₃-PTSA/water treatment. In addition, the recycling test of FeCl₃-PTSA/water manifested a good recycling ability for WS treatment, which would reduce the pretreatment cost and enhance the economic benefit. To sum up, FeCl₃-assisted PTSA treatment of biomass for co-production of reducing sugars and XOSs is an alternative method of waste biomass valorization. Full article

The sustainable valorization of lignocellulosic biomass into value-added biobased chemicals has gained more and more attention on a large industrial scale. To efficiently utilize the abundant, inexpensive, and renewable biomass, it is necessary to employ an effective biomass pretreatment technology for breaking down hemicellulose and lignin. Hydrothermal pretreatment is an effective way to change the structure of lignocellulose and improve its enzymatic hydrolysis efficiency. The hydrothermal cleaning of waste poplar debris (PD) was conducted when the severity factor (LogR₀) score was 5.49. At 220 °C and a solid–liquid ratio of 1:10 for 90 min, the pretreatment liquor contained 4.90 g/L of xylo-oligosaccharides, 1.23 g/L of furfural, 0.41 g/L of formic acid, 2.42 g/L of acetic acid, and 0.57 g/L of 5-HMF. Additionally, 74.9% xylan and 82.4% lignin were removed. After 72 h of enzymatic saccharification, a high enzymolysis efficiency of PD was obtained. A series of characterizations (such as chemical composition analysis, hydrophobicity, lignin surface area, and cellulase accessibility) indicated that hydrothermal pretreatment destroyed the surface structure of PD, improved cellulose accessibility, decreased lignin surface area and weakened lignin hydrophobicity. In general, hydrothermal pretreatment is a simple, green, and environmentally friendly approach for sustainable pretreatment of PD using water as a solvent. It can efficiently break the surface structure of PD and remove lignin and xylan, acquiring high enzymolysis efficiency and realizing the co-production of 5-HMF, furfural, xylo-oligosaccharides, and organic acids. It provides an innovative idea for the value-added utilization of wood-based and straw-based biomass in a sustainable and cost-effective way, showing high potential in industrial application. Full article

Hemp fibers, recognized for their breathability, specific strength, and ultraviolet resistance, are widely utilized in textile manufacturing and composite materials. Bio-degumming is a promising alternative technology to traditional chemical degumming that can be used to produce hemp fibers due to its eco-friendly nature. However, its lower efficiency has hindered its widespread adoption. The unclear and complex structure of the gums leads to a poor understanding on the enzyme types required for bio-degumming, thereby restricting improvements in its efficiency. In this study, the morphological characteristics, polysaccharide composition, and branched structure of hemp stem, roving fibers, and refined fibers were investigated using scanning electron microscopy and laser scanning confocal microscopy in combination with immunofluorescence techniques, with a view to identify the enzymes necessary for the efficient bio-degumming of hemp. The results revealed that the gums were primarily located in the middle lamella, phloem parenchyma, and certain xylem tissues. These tissues showed chunk-like, fence-like, and plate-like shapes, respectively, and tightly wrapped around the fiber bundles. In these tissues, pectin comprised low-esterified homogalacturonan, along with rhamnogalacturonan carrying galactan and arabinan branches. Xylan exhibited acetyl, arabinose, and glucuronic acid branches, while mannan displayed acetyl and galactose branches. Partial xylan and mannan were masked by pectin, and the branching structures impeded their enzymatic removal. As a consequence, the necessary enzymes and their synergistic effects for effective hemp roving degumming were elucidated. Pectin degradation was facilitated by pectate lyase and rhamnogalacturonan-degrading enzymes. Xylan and mannan were effectively removed by endo-xylanase and endo-mannanase, a process necessitating the synergistic action of branched-chain-degrading enzymes, including the esterase, α-L-arabinofuranosidase, α-galactosidase, and α-glucuronidase. This study provided practical strategies to enhance the efficiency of hemp bio-degumming. Full article

New biobased processes and products are emerging to replace conventional ones in the search for sustainable development. Xylitol is one of the most commercially valuable products from xylan-rich lignocellulosic biomass. Xylitol has multiple applications in the pharmaceutical, food, nutraceutical, and beverage industries. Recent research focuses on obtaining xylose from low-cost lignocellulosic materials through the biological route, optimizing xylitol conversion, improving byproduct removal, and increasing crystallization speed. The biological route can be an environmentally friendly alternative due to the possibility of lower energy demand and utilizing renewable feedstocks which are key factors to reach sustainability. Several integration strategies are being evaluated and are critical to developing a commercial platform. Process integration can considerably reduce the demand for energy and reagents. Also, the value-added products produced alongside xylitol are crucial, and these products are usually energy generation and bioethanol. Further, new value-added products show promising results and are relevant to improving the economic performance of the processes. The market trends of xylitol are expected to reach close to USD 1.5 billion in 2030. In addition, the improvement needed in the conversion steps and obtained yields, producing commercial-scale xylitol through the biological route, is a promising alternative to finding a more sustainable way to produce xylitol. Full article

Lignin, a natural pol2ymer with a complex structure that is difficult to separate, is prone to C-C bond condensation during the separation process. To reduce the condensation of lignin, here, a novel method is proposed for separating the components by using a combination of maleic acid (MA)/ozone (O₃) to co-treat wheat straw. The removal of lignin, glucan, and xylan was 38.07 ± 0.2%, 31.44 ± 0.1%, and 71.98 ± 0.1%, respectively, under the conditions of ball-milling of wheat straw for 6 h, reaction temperature of 60 °C, and O₃ holding time of 9 min. Lignin-rich solutions were collected to extract the dissolved lignin (DL) after washing the treated samples. The DL obtained under MA/O₃ conditions had a carboxyl group (-COOH) content of 2.96 mmol/g. The carboxyl group of MA underwent esterification with the hydroxyl group (-OH) at the γ position of lignin and O₃ reacted on the positions of the lignin side chain or the phenolic ring, resulting in a break in the side chain and the opening of the phenolic ring to introduce the carboxyl group. The 2D-HSQC-NMR results revealed that the phenolic ring-opening reaction of lignin in the presence of O₃ was essentially free of β-β and β-5 condensation bonds. Full article

The current study deals with an examination of strategies for the sequential treatment of corn stalks (CSs) in an integrated manner aiming to obtain papermaking fibers and to recover both lignin and hemicelluloses (HCs). Several pathways of valorization were experimentally trialed, focusing on getting information from mass balance analysis in an attempt to reveal the potential outcomes in terms of pulp yield, chemical composition, and papermaking properties such as tensile and burst strength. The raw lignin amounts and purity as well as separated hemicelluloses were also characterized. In this work, pulp yields in the range of 44–50% were obtained from CSs, while lignin and hemicelluloses yielded maximum values of 10 g/100 g of CS and 6.2 g/100 g of CS, respectively. Other findings of mass balance analysis evidenced that besides the papermaking pulp, the lignin and HCs also have interesting output values. The recovered lignin yield values were shown to be less than 50% in general, meaning that even if 67 to 90% of it is removed from CSs, only about half is recovered. The removal rates of hemicelluloses were found to be in the range of approx. 30 to 60%. About 15 to 25% of the original HCs could be recovered, and polysaccharides-based products with 67 to 75% xylan content could be obtained. Some key opinions were developed regarding how the mass balance could turn as a result of the chosen CS valorization set-up. The determined antioxidant activity showed that both lignin and hemicelluloses had interesting values for IC₅₀. Full article

Sugarcane bagasse (SCB), an agro-industrial byproduct generated by a sugar mill, holds a substantial carbohydrate content of around 70 wt.%, comprising cellulose and hemicellulose. Saccharification plays a pivotal role in the conversion of SCB into second-generation (2G)-ethanol and valuable compounds, which is significantly aided by thermochemical pretreatments. In this study, SCB underwent diluted sulfuric acid pretreatment (2% H₂SO₄, 80 rpm, 200 °C, 20 min), resulting in the removal of 77.3% of the xylan. The hemicellulosic hydrolysate was analyzed to identify the sugars and degraded products acting as microbial inhibitors. The acid hydrolysate showed a xylose yield of 68.0% (16.4 g/L) and a yield of 3.8 g/L of acetic acid. Afterward, the hemicellulosic hydrolysate was concentrated 2.37 times to obtain a xylose-rich stream (39.87 g/L). The sequential detoxification, employing calcium oxide and activated carbon, removed the inhibitory compounds, including acetic acid, while preserving the xylose at 38.10 g/L. The enzymatic saccharification of cellulignin at 5% and 10% of the total solids (TSs) yielded comparable reducing sugar (RS) yields of 47.3% (15.2 g/L) and 47.4% (30.4 g/L), respectively, after 96 h, employing a 10 FPU/g enzyme loading of Cellic^® CTec3 (Novozymes Inc. Parana, Brazil). In summary, these findings outline an integrated green chemistry approach aimed at addressing the key challenges associated with pretreatment, concentration, detoxification, and enzymatic hydrolysis to produce fermentable sugars. Full article

β-xylosidases (4-β-d-xylan xylohydrolase, E.C. 3.2.1.37) are glycoside hydrolases (GH) catalyzing the hydrolysis of (1→4)-β-d-xylans, allowing for the removal of β-d-xylose residues from its non-reducing termini. Together with other xylan-degrading enzymes, β-xylosidases are involved in the enzymatic hydrolysis of lignocellulosic biomass, making them highly valuable in the biotechnological field. Whereas different GH families are deeply characterized from a structural point of view, the GH52 family has been barely described. In this work, we report the 2.25 Å resolution structure of Geobacillus stearothermophilus CECT43 XynB2, providing the second structural characterization for this GH family. A plausible dynamic loop closing the entrance of the catalytic cleft is proposed based on the comparison of the available GH52 structures, suggesting the relevance of a dimeric structure for members of this family. The glycone specificity at the −1 site for GH52 and GH116 members is also explained by our structural studies. Full article

The present study deals with the valorization of corn stalks in an integrated processing strategy targeting two products: extracted hemicelluloses (HC) and papermaking fibers. Preliminary trials were conducted to assess the individual or the combined effects of biomass treatment on the quality of the obtained hemicelluloses and papermaking fibers. Depending on the hot alkaline extraction (HAE) conditions, the extracted HC had a xylan content between 44–63%. The xylan removal yield ranged between 19–35%. The recovery of HC from the extraction liquor and final black liquor was significantly affected by process conditions. The experimental approach continued with the study of HAE conditions on the obtained paper’s mechanical properties. The optimization approach considered conserving paper strength properties while achieving an equilibrium with the highest possible HC extraction yield. The optimal values are sodium hydroxide concentration (1%), process time (33 min), and temperature (100 °C). The xylan content in the separated HC sample was ~55%. An extended extraction of HC from the resulting pulp under hot alkaline conditions with 5% NaOH was performed to prove the HC influence on paper strength. The xylan content in HC samples was 65%. The consequence of xylan content reduction in pulp leads to 30–50% mechanical strength loss. Full article

Deep eutectic solvents (DESs) with a hydrophobic aromatic ring structure offer a promising pretreatment method for the selective delignification of lignocellulosic biomass, thereby enhancing enzymatic hydrolysis. Further investigation is needed to determine whether the increased presence of aromatic rings in hydrogen bond receptors leads to a more pronounced enhancement of lignin removal. In this study, six DES systems were prepared using lactic acid (LA)/acetic acid (AA)/levulinic acid (LEA) as hydrogen bond donors (HBD), along with two independent hydrogen bond acceptors (HBA) (benzyl triethyl ammonium chloride (TEBAC)/benzyl triphenyl phosphonium chloride (BPP)) to evaluate their ability to break down sugarcane bagasse (SCB). The pretreatment of the SCB (raw material) was carried out with the above DESs at 120 °C for 90 min with a solid–liquid ratio of 1:15. The results indicated that an increase in the number of aromatic rings may result in steric hindrance during DES pretreatment, potentially diminishing the efficacy of delignification. Notably, the use of the TEBAC:LA-based DES under mild operating conditions proved highly efficient in lignin removal, achieving 85.33 ± 0.52% for lignin removal and 98.67 ± 2.84% for cellulose recovery, respectively. The maximum digestibilities of glucan (56.85 ± 0.73%) and xylan (66.41 ± 3.06%) were attained after TEBAC:LA pretreatment. Furthermore, the maximum ethanol concentration and productivity attained from TEBAC:LA-based DES-pretreated SCB were 24.50 g/L and 0.68 g/(L·h), respectively. Finally, the comprehensive structural analyses of SCB, employing X-rays, FT-IR, and SEM techniques, provided valuable insights into the deconstruction process facilitated by different combinations of HBDs and HBAs within the DES pretreatment. Full article

Xylan is a macromolecule of industrial interest that can be solubilized from lignocellulosic materials, such as sugarcane bagasse, which is a renewable source. However, the solubilization methods of xylan need to be better developed for use in industrial applications. The main objective of this study was to evaluate xylan solubilization methods with higher yields and purity by using biomasses/fractions of sugarcane: leaf and stem, internode, node, and external fraction. Two strategies were evaluated by applying diluted sodium chlorite, sodium sulfite, and hydrogen peroxide: a delignification of the biomass before xylan solubilization; and the delignification of the solubilized xylan for residual lignin removal. The delignification of the biomass before the xylan solubilization enabled to identify material and specific conditions for yields higher than 90%. Residual lignin varied from 3.14 to 18.06%, with hydrogen peroxide in alkaline medium partial delignification shown to be effective. The delignification of xylan presented better results using diluted hydrogen peroxide, with a reduction of 58.44% of the initial lignin content. The solubilized xylans were used as a substrate for xylanase activities, resulting in higher activity than commercial xylan. In the delignification of the biomasses, hydrogen peroxide was the reagent with better results concerning the yield, purity, and solubility of the xylan. This reagent (diluted) was also better in the delignification of the solubilized xylan, resulting in lower residual lignin content. The solubility and purity tests (low salt content) indicated that the solubilized xylan presented characteristics that were similar to or even better than commercial xylan. Full article

Lignocellulose, composed of cellulose, hemicellulose, and lignin, holds immense promise as a renewable resource for the production of sustainable chemicals and fuels. Unlocking the full potential of lignocellulose requires efficient pretreatment strategies. In this comprehensive review, efforts were taken to survey the latest developments in polyoxometalates (POMs)-assisted pretreatment and conversion of lignocellulosic biomass. An outstanding finding highlighted in this review is that the deformation of the cellulose structure from I to II accompanied by the removal of xylan/lignin through the synergistic effect of ionic liquids (ILs) and POMs resulted in a significant increase in glucose yield and improved cellulose digestibility. Furthermore, successful integration of POMs with deep eutectic solvents (DES) or γ-valerolactone/water (GVL/water) systems has demonstrated efficient lignin removal, opening avenues for advanced biomass utilization. This review not only presents the key findings and novel approaches in POMs-based pretreatment but also addresses the current challenges and prospects for large-scale industrial implementation. By offering a comprehensive assessment of the progress in this field, this review serves as a valuable resource for researchers and industry professionals aiming to harness the potential of lignocellulosic biomass for sustainable chemical and fuel production. Full article

In this work, we develop chitosan/xylan-coated magnetite (CsXM) nanoparticles as eco-friendly efficient adsorbents for the facile removal of contaminants from water. Characterization of CsXM using Fourier Transform Infra-Red (FTIR) Spectroscopy, Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Thermogravimetric Analysis (TGA), Transmission Electron Microscopy (TEM), Zeta potential measurements, and Brunauer-Emmet-Teller (BET) analysis, confirmed the successful preparation of a chitosan/xylan complex coated over magnetite, which is characterized by being mesoporous, thermally stable and of neutral charge. Three contaminants, Pb(II), salicylic acid (SA), and congo red (CR), were chosen as representative pollutants from three major classes of contaminants of emerging concern: heavy metals, pharmaceuticals, and azo dyes. Pb(II), SA, and CR at initial concentrations of 50 ppm were removed by 64.49, 62.90, and 70.35%, respectively, on applying 6 g/L of CsXM. The contaminants were successfully removed in ternary systems, with Pb (II) and SA being more competitive in their adsorption than CR. Adsorption followed the Freundlich isotherm model and the pseudo-second order kinetic model, while the binding was suggested to occur mainly via chemical chelation for Pb(II) and physical interaction for SA and CR, which demonstrates the multifunctional potential of the nanoparticles to capture different contaminants regardless of their charge. Full article