High-purity Lignin Research Articles

Utilization of benzoic acid–based green deep eutectic solvents for the fractionation of lignocellulosic biomass

The fractionation of lignocellulose utilizing green solvents is essential for the effective operation of biorefineries. In this study, a deep eutectic solvent (DES) system composed of benzoic acid (BA, hydrogen bond donor) and choline chloride (ChCl, hydrogen bond acceptor) was fabricated and successfully applied to the lignocellulose fractionation. The DES has low toxicity and little pollution. In this system, 67.8 % of lignin and 91.2 % of hemicellulose in poplar were removed, leaving 95.8 % of cellulose intact as solid residue. Due to the removal of the amorphous components, crystallinity of cellulose-rich water-insoluble solid (CIS) substantially increased from 55.6 % to 68.6 %, and CIS was used as feedstock for nanocrystalline cellulose preparation with excellent properties. The results showed that the obtained lignin had similar properties to CEL by GPC, FT-IR, 2D-NMR and TGA. A high-purity lignin rich in G units was recovered with a well-preserved structure, which has β–O–4 linkage content up to 53.01 %, low molecular weight, low polydispersity (1.99). Finally, the hydrolyzate can be used for fermentation. This study demonstrated that BA is suitable for DES design with excellent properties on lignin extraction, and this promising DES enable efficient pretreatment for economically feasible biomass conversion. This ChCl-BA DES facilitates environmentally friendly production of functional materials derived from cellulose and lignin under mild conditions.

Efficient binary diol-based deep eutectic solvent pretreatment for enhancing enzymatic saccharification and lignin fractionation from eucalyptus

An innovative binary biol-based deep eutectic solvent (DES), specifically ethylamine hydrochloride-ethylene glycol (EaCl-EG), was developed for efficient pretreatment of eucalyptus biomass. This DES exhibited superior performance in achieving high delignification (85.0%) and xylan removal (80.0%), while preserving a significant amount of cellulose (94.5%) compared to choline chloride-based DES. Notably, the pretreated eucalyptus residues showed a remarkable glucose yield of over 92.5%, representing a substantial enhancement of up to 15 times compared to untreated eucalyptus. Furthermore, the pretreated liquor yielded high-purity lignin with a yield of 97.8%, characterized by well-preserved β-O-4 structure and nanoscale dimensions. These lignin nanoparticles (LNPs) were subsequently self-assembled into lignin nanobottles (LNBs), adding further value to the pretreatment process. The proposed novel binary EaCl-EG DES presented great potential as an efficient pretreatment solvent for future biomass fractionation processes.

Production of High Purity Lignin from OPEFB: An Overview

Production of High Purity Lignin from OPEFB: An Overview

High extraction and excellent anti-UV and anti-oxidant proprieties of lignin from Reseda Luteola L. waste by organosolv process

Lignin is an abundant natural biopolymer found in plant cell walls. Lignin can come from tinctorial plants, whose residual biomass after dye extraction was typically discarded as waste. The main objective of this study was to extract lignin from the residual biomass of Reseda luteola L. using an organosolv process and to optimize the extraction conditions. The extracted lignin was characterized, and its potential applications as an antimicrobial, anti-oxidant, and anti-UV agent were investigated. Response surface methodology based on a Box-Behnken design was employed to optimize the lignin extraction conditions (organic acid concentration, material-to-liquid ratio, extraction time). The extracted lignin was comprehensively characterized using NMR, FTIR, XRD, SEM-EDX, TGA, DSC, and UV–Vis techniques. The optimal extraction conditions yielded a remarkably high lignin recovery of 62.41 % from the plant waste, which was rarely achieved for non-wood plants in previous works. The extracted lignin exhibited excellent thermal stability and radical scavenging anti-oxidant activity but no significant antimicrobial effects. Treating wool fabrics with lignin nanoparticles substantially enhanced UV protection from the “good” to “excellent” category based on the UPF rating. This sustainable valorization approach converted abundant tinctorial plant waste into high-purity lignin with promising anti-oxidant and UV-blocking properties suitable for various applications.

Low-temperature and low-concentration sodium hydroxide pretreatment for enhanced enzyme hydrolysis rate from Quercus variabilis Blume

A surface response design was employed to develop a sodium hydroxide (NaOH) pretreatment method for Quercus variabilis Blume using low NaOH concentration at low temperature. Nevertheless, the persistent issues associated with alkaline pretreatment of lignocellulose, namely high-water consumption and wastewater generation, remain prevalent in this pretreatment process. To address these challenges, this study aimed to conduct enzymatic hydrolysis of NaOH-treated Q. variabilis Blume without the intermediary washing steps. The results revealed that, following pretreatment and solid-liquid separation, NaOH-treated Q. variabilis Blume could be directly subjected to cellulase-mediated hydrolysis with pH adjustment, eliminating the need for washing steps. The maximum enzymatic hydrolysis efficiency reached 95.9% under specific conditions (1.2% NaOH, 8.9 °C, 32.1 h). This approach offers a promising avenue to enhance the enzyme hydrolysis rate of NaOH-treated lignocellulose. Notably, the low-temperature and low-concentration NaOH treatment effectively removed a substantial portion of lignin and hemicelluloses, resulting in a higher crystallinity index of the cellulose-rich residue compared to substrates treated solely with steam explosion. The integration of direct pretreatment and alkaline treatment emerges as an environmentally friendly and economically viable method for producing glucose and high-purity lignin. The obtained lignin can be further transformed into high-value products within the biorefinery framework.

Easy hydrogel preparation with high-purity lignin separated from DES pretreatment with excellent performance for moisture-electric generators and motion sensors

This study presents a rapid and straightforward method to prepare a multifunctional hydrogel using deep eutectic solvent-pretreated lignin (DESL), aluminum ions (Al3+), and polyacrylic acid (PAA) in an aqueous system.

Sugarcane Light-Colored Lignin: A Renewable Resource for Sustainable Beauty.

Lignin has emerged as a promising eco-friendly multifunctional ingredient for cosmetic applications, due to its ability to protect against ultraviolet radiation and its antioxidant and antimicrobial properties. However, its typical dark color and low water solubility limit its application in cosmetics. This study presents a simple process for obtaining light-colored lignin (LCLig) from sugarcane bagasse (SCB) alkaline black liquor, involving an oxidation treatment with hydrogen peroxide, followed by precipitation with sulfuric acid. The physico-chemical characterization, antioxidant and emulsifying potential of LCLig, and determination of its safety and stability in an oil-in-water emulsion were performed. A high-purity lignin (81.6%) with improved water solubility was obtained, as a result of the balance between the total aromatic phenolic units and the carboxylic acids. In addition, the antioxidant and emulsifying capacities of the obtained LCLig were demonstrated. The color reduction treatment did not compromise the safety of lignin for topical cosmetic applications. The emulsion was stable in terms of organoleptic properties (color, pH, and viscosity) and antioxidant activity over 3 months at 4, 25, and 40 °C.

Innovative parallel synthesis of 5-nonanone and furfural from lignocellulosic biomass accompanied by deep economic analysis

An integrated strategy is developed to utilize all three primary components (cellulose, hemicellulose, and lignin) of lignocellulosic biomass for the coproduction of hydrocarbon fuel (5-nonanone) and bio-chemicals (furfural and high purity lignin). After biomass fractionation, (1) 5-nonanone is produced with high yield of 89% using cellulose-derived γ-valerolactone (GVL), which can potentially serve as a platform molecule for the production of liquid hydrocarbon fuels for the transportation sector; (2) furfural, a valuable platform chemical, is produced using hemicellulose; and (3) production of high-purity lignin, which can be used to produce carbon foams or battery anodes. Separation subsystems are designed to effectively recover the solvents for reuse in the conversion processes, which ultimately improves the economic feasibility of the integrated process, resulting in achieving lower minimum selling price (MSP) of $5.47 GGE-1 for 5-nonanone compared to market price. Heat pump is introduced to perform heat integration, which reduces utility requirements more than 85%. Finally, a wide range of techno-economic analysis is performed to highlight the major cost and technological drivers of the integrated process.

Green and sustainable production of high-purity lignin microparticles with well-preserved substructure and enhanced anti-UV/oxidant activity using peroxide-promoted alkaline deep eutectic solvent

Deep eutectic solvents (DESs) have emerged as promising and eco-friendly solvents for the efficient extraction of lignin from biomass due to their low cost and environmental benefits. Nevertheless, the prevalent use of acidic DESs in lignin extraction often results in excessive depolymerization and recondensation of lignin, thereby impeding its downstream applications. In this study, we developed a range of alkaline DESs (ADESs), both pure and peroxide-containing, for the extraction of high-quality lignin from bamboo. Moreover, carbon dioxide (CO2) was employed for the precipitation and regeneration of the extracted lignin. The obtained lignin fractions were comprehensively characterized in terms of yield, purity, morphology, solubility, structural features, and anti-UV/oxidant activity. The results showed that the monoethanolamine-based ADES demonstrated superior performance among the pure ADESs. Structural analysis confirmed the well-preserved substructures of lignin fractions obtained using ADESs, with β-O-4 bond retention ranging from 49.8 % to 68.4 %. The incorporation of a suitable amount of peroxide improved lignin yield, morphology, solubility, and anti-UV/oxidant activity. Additionally, the anti-UV/oxidant activity of lignin exhibited a positive correlation with its phenolic hydroxyl content. This study provides a valuable reference for the green and sustainable production and valorization of lignin within the existing biorefinery framework.

Lignin extraction and fractionation from rice straw biorefinery residues

Crops straw contains many valuable natural compounds. Cellulose and hemicellulose in agricultural wastes have been widely used in biofuel production. However, the large-scale application of residue lignin from biorefinery is still an unsolved problem. Various impurities and heterogeneous lignin with a very complicated molecular weight distribution were generally found in the recovered raw solid products. In this study, brown solid residue from rice straw biorefinery was processed using membrane separation in combination with the soda-ethylene glycol (Soda-EG) process to extract high-purity lignin. At first, wet brown solid was mixed into an aqueous solution of sodium hydroxide and ethylene glycol for lignin fragmentation, depolymerization, and solubilization at elevated temperatures. Afterwards, microfiltration (MF) was applied to recover the dissolved lignin in the filtrate from the extracts. As high as 90% of the lignin in the brown solid could be recovered after acid precipitation of the filtrate. The highest lignin content in the precipitate product could be 90% (dry basis). The precipitate was re-dissolved at high pH aqueous solutions for further molecular weight fractionation by ultrafiltration (UF). The best rejection of high-molecular-weight (>1 × 105 g/mol) lignin was 77%, while low-molecular-weight (<3 × 103 g/mol) lignin was <13% with a MWCO of 10 kDa polysulfone UF membrane in a dead-end filtration system. The cross-flow operation with the same UF membrane showed that >80% lignin could be recovered from the retentate and the flux of permeate could be maintained after three operation-cleaning cycles. Overall, the combined MF-UF operation could be a viable method for obtaining high-value-added lignin products with a specific molecular weight range.

Maximizing the utilization of lignocellulosic biomass: Process development and analysis

Herein, an innovative strategy is proposed for the manufacture of biochemicals (dissolving pulp, furfural, high-purity lignin, and acetic acid) from lignocellulosic biomass. Utilizing sulfuric acid as the catalyst and a mixture of water and γ-valerolactone (GVL) as the solvent, the biomass was successfully fractionated into four major components: 1) cellulose, which was converted into dissolving pulp for fiber production; 2) hemicellulose, which was decomposed into furfural, a valuable platform chemical; 3) lignin, which was purified intensively for the production of carbon foams or battery anodes; and 4) acetate, which was converted into acetic acid, a chemical that is potentially useful as a H2 carrier and in H2 production. Separation subsystems were developed to recover the water and GVL mixture effectively for reuse in biomass fractionation and to separate cellulose, hemicellulose, lignin, and acetate for further treatment. To reduce the energy requirements, a heat pump was introduced and heat integration was conducted. The integrated process achieved a positive NPV ($19.9 million), making our process economically viable against initial uncertainties and high risks related to the project. Furthermore, dissolving pulp production was found to be the major environmental contributor accounting for 47.1% of fossil depletion and 36.4% of climate change.

Development of a biorefinery from olive mill leaves: Comparison of different process configurations

In this work, three process configurations were studied to advance the biorefinery of olive oil mill leaves (OL), whose main products comprise natural antioxidants, lignin and bioethanol, so far never studied. Configuration 1 includes an organosolvent pretreatment, followed by a simultaneous saccharification and fermentation (SSF). This process scheme is the simplest but it resulted in a poor fractionation of the biomass. In configuration 2, a previous extraction with ethanol is included in the process, to boost the recovery of natural antioxidants (45 mg/g OL expressed as gallic acid equivalent). Configuration 3 consists of an acid extraction, organosolv pretreatment, SSF and co-fermentation stages, which achieved a better fractionation, presenting the highest bioethanol production with a yield of 71% of the theoretical yield (with respect to the sugars in raw material, 102 mg/g OL). This configuration generated a liquid stream from the organosolv pretreatment, with a higher lignin content (70 mg/g OL), and this makes it easier to obtain high purity lignin.

Exploring the Potential of Vine Shoots as a Source of Valuable Extracts and Stable Lignin Nanoparticles for Multiple Applications.

Large amounts of vine shoots are generated every year during vine pruning. This residue still presents many of the compounds found in the original plant, including low molecular weight phenolic compounds and structural compounds such as cellulose, hemicellulose, and lignin. For wine-producing regions, the challenge is to develop alternatives that will increase the value of this residue. This work proposes the full valorization of vine shoots, focusing on the extraction of lignin by mild acidolysis for the preparation of nanoparticles. The effect of the pretreatment solvents (ethanol/toluene, E/T, and water/ethanol, W/E), on the chemical and structural features of lignin, was evaluated. The chemical analysis suggests similar composition and structure regardless of the pretreatment solvent, although lignin isolated after pretreatment of biomass with E/T showed a higher content of proanthocyanidins (11%) compared with W/E (5%). Lignin nanoparticles (LNPs) presented an average size ranging from 130-200 nm and showed good stability for 30 days. Lignin and LNPs showed excellent antioxidant properties (half maximal inhibitory concentration, IC50 0.016-0.031 mg/mL) when compared to commercial antioxidants. In addition, extracts resulting from biomass pretreatment showed antioxidant activity, with W/E presenting a lower IC50 (0.170 mg/mL) than E/T (0.270 mg/mL), correlated with the higher polyphenol content of W/E, with (+)-catechin and (-)-epicatechin being the main compounds detected. Overall, this work shows that the pre-treatment of vine shoots with green solvents can yield (i) the production of high-purity lignin samples with antioxidant properties and (ii) phenolic-rich extracts, promoting the integral reuse of this byproduct and contributing to sustainability.

Technical kraft lignin from coffee parchment

Abstract The biomass deconstructed by kraft process and the lignin dissolved in the black liquor are burned to generate energy in a pulp mill. This study used the black liquor from coffee parchment cooking, a residue from the coffee industry, to isolate kraft technical lignin. The parchment was subjected to the kraft pulping process to obtain pulps of kappa number 60 and 25, and the resulting black liquors were used for lignin extraction. Chemical characterization, elemental analysis and heating value of liquors and lignins were performed, as well as FTIR and Py-CG-MS analysis of lignins. The cooking provided liquors with similar characteristics, with lignin content of 31.67 and 32.63% for kappa 60 and 25 liquors, respectively. The extractions resulted in high purity lignin (92.35% for K#60 lignin and 93.96% for K#25 lignin). The higher heating values were 23.8 and 25.4 MJ/kg for K#25 and K#60 lignins, respectively. FTIR analysis showed characteristic peaks of lignin. Through Py-GC-MS, it was possible to observe the slight predominance of guaiacyl-type lignin, which can be an advantage depending on the application. It is possible to extract lignin from the black liquor obtained from the coffee parchment pulping to generate products with high-added value.

High-purity lignin from selective biomass fractionation with ternary deep eutectic solvents

Green and recyclable ternary deep eutectic solvent was developed to selectively extract lignin of high purity, desirable molecular weight and monomeric yield for applications in reinforcement materials and bio-oil was produced from biomass.

Laboratory- to Pilot-Scale Fractionation of Lignocellulosic Biomass Using an Acetone Organosolv Process

Acetone organosolv fractionation of beech and birch wood at the lab-scale results in high sugar yields from the (hemi)cellulose and the isolation of a high-purity lignin. In this study, the process is scaled up to validate the technology at the pilot scale using industrial-size beech and birch wood chips and low liquid-to-solid ratios as a next step toward commercialization. Translation of the fractionation process to the pilot-scale showed a similar performance as compared to the lab-scale processing with a good conversion of the wood polymeric pentoses to mostly monomeric sugars and a high delignification. Continuous lignin precipitation by solvent evaporation using the LigniSep process resulted in the formation of nonsticky lignin aggregates with a good filterability. The improved lignin yields and advanced process design as compared to the traditional dilutive lignin precipitation approaches are likely to translate to a better process economy. The pulp washing efficiency and the recovery of (nonprecipitable) lignin from the aqueous hemicellulose stream still need to be improved for an efficient process design. However, the fractionation performance and high product concentrations in the spent liquor provide an excellent start position for improved process design at the commercial scale.

Effect of alkaline and deep eutectic solvents pretreatments on the recovery of lignin with antioxidant activity from grape stalks

Grape stalks are lignocellulosic residues that can be valorized through the extraction of lignin - an underutilized biopolymer with high potential. Two lignin extraction methods, alkaline and deep eutectic solvents (DES), were studied, and experimental designs were carried out to obtain the best extraction conditions. The defined parameters for alkaline extraction allowed the recovery of ~48 % of lignin with low purity that was further improved with an autohydrolysis pretreatment (~79 % purity; ~32 % yield). Optimum parameters of DES method rendered high purity lignin (~90 %) without the need of a pretreatment and with a better yield (50.2 % (±2.3)) than the alkaline method. Both lignin fractions presented high antioxidant activities, being close to the antioxidant capacity of BHT for DPPH scavenging. Structural analysis proved the presence of lignin in both alkaline and DES samples with similar morphology. Overall, DES method was more efficient in the extraction of lignin from grape stalks besides its greener and sustainable nature. This work uses DES to extract lignin from this biomass while comparing it with a commonly classical method, proving that grape stalks can be used to extract lignin with a sustainable and efficient method rendering a final ingredient with value-added properties.

High-purity lignin fractions and nanospheres rich in phenolic hydroxyl and carboxyl groups isolated with alkaline deep eutectic solvent from wheat straw

A combined pretreatment based on alkaline deep eutectic solvent (DES) of K2CO3 and glycerol and sequential acid fractionation was developed to extract reactive lignin from wheat straw biomass. This process exhibited excellent purification performance in lignin isolation, and the lignin fractionated at low pH displayed high reactivity, having hydroxyl and carboxyl groups up to 9.60 and 2.52 mmol/g, respectively. Silica was selectively separated and removed during the precipitation stage, avoiding the “silica interference”. Moreover, DES-lignin nanospheres created by self-assembly using lignin fractions obtained by acid precipitation possessed a high zeta potential, large particle size and high content of hydrophilic groups. Overall, the findings related to the dissociation mechanism and fractionation of reactive lignin during alkaline DES pretreatment and the acid sequence precipitation are crucial for facilitating lignin valorization in high-added value products.

Effect of structural changes of lignin during the microwave-assisted alkaline/ethanol pretreatment on cotton stalk for an effective enzymatic hydrolysis

Effective delignification of lignocellulosic biomass is an important factor to improve the efficiency of enzymatic hydrolysis and ensure the economic feasibility of bio-refining. Cotton stalk (CS) was treated by a microwave-assisted alkaline/ethanol pretreatment (MAAP) (at 160 °C for 15 min) process to separate high-purity lignin and digestible cellulose-rich residue. Results showed that the MAAP process resulted in homogeneous lignin fractions with narrow polydispersity index (PI), and the isolated lignin fragments exhibited relatively smaller molecular weights and numerous phenolic OH groups than those in MWL. The crystallization index of cellulose-rich substrates was increased after the MAAP integrated process. Meanwhile, the glucose yield of the integrated residue reached the maximum (82.41%) after enzymatic hydrolysis. The utilization of MAAP process was a beneficial and promising scheme for the generation of lignin fractions with satisfactory purity and chemical reactivity, which will facilitate the value-added application of CS in the future biorefinery.

Influence of Lignin Content and Pressing Time on Plywood Properties Bonded with Cold-Setting Adhesive Based on Poly (Vinyl Alcohol), Lignin, and Hexamine

The sustainability, performance, and cost of production in the plywood industry depend on wood adhesives and the hot-pressing process. In this study, a cold-setting plywood adhesive was developed based on polyvinyl alcohol (PVOH), high-purity lignin, and hexamine. The influence of lignin content (10%, 15%, and 20%) and cold-pressing time (3, 6, 12, and 24 h) on cohesion, adhesion, and formaldehyde emission of plywood were investigated through physical, chemical, thermal, and mechanical analyses. The increased lignin addition level lowered the solids content, which resulted in reduced average viscosity of the adhesive. As a result, the cohesion strength of the adhesive formulation with 10% lignin addition was greater than those of 15% and 20% lignin content. Markedly, the adhesive formulation containing a 15% lignin addition level exhibited superior thermo-mechanical properties than the blends with 10% and 20% lignin content. This study showed that 10% and 15% lignin content in the adhesive resulted in better cohesion strength than that with 20% lignin content. However, statistical analysis revealed that the addition of 20% lignin in the adhesive and using a cold-pressing time of 24 h could produce plywood that was comparable to the control polyurethane resins, i.e., dry tensile shear strength (TSS) value of 0.95 MPa, modulus of rupture (MOR) ranging from 35.8 MPa, modulus of elasticity (MOE) values varying from 3980 MPa, and close-to-zero formaldehyde emission (FE) of 0.1 mg/L, which meets the strictest emission standards. This study demonstrated the feasibility of fabricating eco-friendly plywood bonded with PVOH–lignin–hexamine-based adhesive using cold pressing as an alternative to conventional plywood.