Organosolv Extraction Research Articles

Glycerol-Derived Solvents for Tractable Organosolv Extraction of Softwood Lignins

Glycerol-Derived Solvents for Tractable Organosolv Extraction of Softwood Lignins

2G-lactic acid from olive oil supply chain waste: olive leaves upcycling via Lactobacillus casei fermentation

The transition towards a sustainable model, particularly the circular economy, emphasizes the importance of redefining waste as a valuable resource, paving the way for innovative upcycling strategies. The olive oil industry, with its significant output of agricultural waste, offers a promising avenue for high-value biomass conversion into useful products through microbial processes. This study focuses on exploring new, high-value applications for olive leaves waste, utilizing a biotechnological approach with Lactobacillus casei for the production of second-generation lactic acid. Contrary to initial expectations, the inherent high polyphenol content and low fermentable glucose levels in olive leaves posed challenges for fermentation. Addressing this, an enzymatic hydrolysis step, following a preliminary extraction process, was implemented to increase glucose availability. Subsequent small-scale fermentation tests were conducted with and without nutrient supplements, identifying the medium that yielded the highest lactic acid production for scale-up. The scaled-up batch fermentation process achieved an enhanced conversion rate (83.58%) and specific productivity (0.26 g/L·h). This research confirms the feasibility of repurposing olive waste leaves for the production of lactic acid, contributing to the advancement of a greener economy through the valorization of agricultural waste.Key points• Olive leaves slurry as it did not allow L. casei to ferment.• High concentrations of polyphenols inhibit fermentation of L. casei.• Enzymatic hydrolysis combined to organosolv extraction is the best pretreatment for lactic acid production starting from leaves and olive pruning waste.Graphical

Assessing Environmental Impact: Organosolv Extraction of Cellulose Pulp from Wood Waste

In the upcoming years, the paper industry is expected rely on containerboard for packaging, with approximately 80% of it being made from recycled fibers by 2020. Creating a new supply chain for fibers could help mitigate possible shortages. In this context, wood waste emerges as a valuable resource with the potential to serve as a plentiful and cost-effective reservoir for generating new materials, as cellulose fibers. This study presents an assessment of the environmental impact associated with the organosolv extraction of cellulose pulp from wood waste based on a previous in lab study conducted by the authors. The increasing demand for sustainable materials has prompted exploration into alternative methods for cellulose pulp production, with a focus on minimizing environmental footprint. Organosolv extraction, a promising technique, involves the use of organic solvents and acid catalysts to break down lignocellulosic biomass, resulting in high-quality cellulose pulp production. To evaluate the environmental implications of this process, a comprehensive life cycle assessment (LCA) approach was adopted. The LCA framework considers all stages of the organosolv extraction process, from wood waste collection to cellulose pulp manufacture, using a gate-to-gate approach. The functional unit for assessment is set as one ton of cellulose pulp. The dataset utilized for the LCA comprises primary data obtained from laboratory experiments, complemented by secondary data sourced from literature and the Ecoinvent life cycle inventory database. Furthermore, sensitivity analysis was conducted to assess the influence of key parameters on the environmental performance of the organosolv extraction process, with a focus on variations in energy consumption to identify potential areas for optimization and improvement. In summary, this study emphasizes the environmental aspects of utilizing organosolv extraction for cellulose pulp production from wood waste. Further research is warranted to explore energy consumption during the organosolv process for obtaining more precise data and optimizing the process. This could be achieved through pilot-scale experiments or utilizing process simulation software.

Olive leaves upgrading applying a novel two-stage organosolv pretreatment: Techno-economic and environmental assessment

This research study evaluates the techno-economic and environmental performance of an olive leaves based biorefinery to produce antioxidants, bioethanol, and organosolv lignin. The biorefinery comprises processes such as organosolv extraction, organosolv pretreatment and simultaneous saccharification and fermentation, which were simulated in Aspen Plus v9.0. Experimental data were used to simulate the process, assuming a linear up-scaling. The techno-economic evaluation was carried out considering financial indicators such as net present value (NPV) and internal rate of return (IRR). The environmental assessment was done applying the life cycle assessment methodology. The results shows that 100 g olive leaves can produce 16.58 g antioxidant extract, 11.12 g organosolv lignin, and 2.85 g bioethanol. The proposed biorefinery was feasible at a processing scale of 30,000 t/y with a NPV of 47.9 million USD and an internal rate of return of 27.8%. The proposed biorefinery can be implemented in Jaén (Andalusia-Spain) based on the high amount of olive leaves produced in this region. Stillages are the most polluting waste stream of the process. The carbon footprint of the biorefinery was 1.13 kgCO2-eq/kg olive leaves. The application of the biorefinery concept revealed that olive leaves could be transformed into value-added products from a techno-economic and environmental perspective.

Quantification of antioxidant and antimicrobial properties of oil palm empty fruit bunch lignin based on organosolv extraction

Quantification of antioxidant and antimicrobial properties of oil palm empty fruit bunch lignin based on organosolv extraction

Effect of solvent and acid catalyst selection on lignin recovery and purity in autoclave-assisted organosolv extraction

This study leverages the autoclave-assisted method to explore a range of acid catalysts (H2SO4, HCl, HNO3, H3PO4) and solvents (methanol, ethanol, acetone, 2-butanol, 2-propanol) for lignin extraction, with a focus on identifying optimal efficiency-enhancing combinations. By contrasting the performance of various acid catalysts and solvents, this work transcends previous efforts in this field. Notably, H2SO4 yields the highest lignin recovery (44.7 %) but with lower purity (78.4 %) compared to HCl (85.7 %) in the same solvent. Methanol yields the highest recovery (45.1 %), yet lower purity (79.2 %) than ethanol (85.7 %) with a similar catalyst. A pivotal improvement lies in the elucidation of structural purity, substantiated by IR and NMR resulting signals, supported by microscale morphology and chemical composition (SEM-EDX). This study extends current understanding, providing profound insights into optimizing extraction procedures for producing lignin with desired attributes.

Environmentally Friendly Extraction from Picea Abies Bark as an Approach to Accessing Valuable Antioxidants in Biorefineries

Every year, the pulp and wood-processing industry produces large side streams of bark, the valorisation of which is desirable for both economic and environmental reasons. We investigated organosolv extraction of antioxidants from Picea abies bark using various ratios of ethanol/water with the goal of obtaining high yields of these desirable compounds. The resulting extracts were analysed (I) for their total contents of phenols (TPC), flavonoids (TFC) and tannins (TTC), and (II) for their antioxidant activity using the DPPH radical scavenging method. The highest total yield of bark extract (14.78%) and the highest concentrations of dry extracts of TPC (324.80 mg g−1), TFC (62.55 mg g−1) and TTC (83.63 mg g−1) were obtained under mild conditions (100 °C extraction temperature and an ethanol/water solvent ratio of 50%, v/v). DPPH antioxidant activity index (AAI) ranged from 0.68 (pure water extract) to 1.31. This antioxidant effect was increased to 1.59 by adding oligolignin from the organosolv process. In the extracts, gas chromatography–mass spectrometry (GC–MS) found nine aromatic carboxylic acids, including phenolic acids and the flavonoid compounds quercetin and (+)-catechin. Our environmentally friendly approach will form the basis for pilot plant and industrial applications.

Lignin Structure and Reactivity in the Organosolv Process Studied by NMR Spectroscopy, Mass Spectrometry, and Density Functional Theory.

There is need for well-defined lignin macromolecules for research related to their use in biomaterial and biochemical applications. Lignin biorefining efforts are therefore under investigation to meet these needs. The detailed knowledge of the molecular structure of the native lignin and of the biorefinery lignins is essential for understanding the extraction mechanisms as well as chemical properties of the molecules. The objective of this work was to study the reactivity of lignin during a cyclic organosolv extraction process adopting physical protection strategies. As references, synthetic lignins obtained by mimicking the chemistry of lignin polymerization were used. State-of-the-art nuclear magnetic resonance (NMR) analysis, a powerful tool for the elucidation of lignin inter-unit linkages and functionalities, is complemented with matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry (MALDI-TOF MS), to gain insights into linkage sequences and structural populations. The study unraveled interesting fundamental aspects on lignin polymerization processes, such as identifications of molecular populations with high degrees of structural homogeneity and the emergence of branching points in lignin structure. Furthermore, a previously proposed intramolecular condensation reaction is substantiated and new insights into the selectivity of this reaction are introduced and supported by density functional theory (DFT) calculations, where the important role of intramolecular π-π stacking is emphasized. The combined NMR and MALDI-TOF MS analytical approach, together with computational modeling, is important for deeper fundamental lignin studies and will be further exploited.

Microwave-assisted organosolv extraction for more native-like lignin and its application as a property-enhancing filler in a light processable biobased resin

The more native-like lignin microwave extracted from spruce wood greatly reinforced digital light processing 3D printed biobased materials already at low concentration.

A facile and novel lignin isolation procedure – Methanolic hydrochloric acid treatment at ambient temperature

Lignin is the most naturally abundant source of aromatics for phenolic chemicals, bioenergy sources, and functional materials. Recent works are devoted to the acid-catalyzed organosolv extraction for improving the lignin valorization. However, β–aryl ethers are mostly cleaved to form carbon–carbon bonds under the acidic condition. In this work, lignin isolated with methanolic hydrochloric acid (MHL) was compared with conventional milled wood lignin (MWL). The methanol incorporated into lignin as α–OCH3 to prevent the cleavage of β–aryl ethers. As a result, the yield of MHL was over 12 times that of MWL. The MHL appeared a regular granular structure with an average diameter of 100 nm. Analysis of 13C–1H HSQC NMR spectra showed that MHL contained 42.6 % β–O–4 linkages whereas 35.9 % for the MWL, as well as 6.5 % β–5 and 3.2 % β–β, which was less than MWL. Moreover, 13C NMR spectroscopy confirmed that MHL was mainly isolated by the cleavage of the associated carbohydrates rather than the degradation of β–aryl ether bonds. Therefore, MHL can be utilized more as a native lignin representative than MWL for studying the physicochemical properties and the interior structures of the protolignin.

Fundamental Insights on the Physical and Chemical Properties of Organosolv Lignin from Norway Spruce Bark.

The interest in the bark and the attempt to add value to its utilization have increased over the last decade. By applying an integrated bark biorefinery approach, it is possible to investigate the recovery of compounds that can be used to develop green and sustainable alternatives to fossil-based materials. In this work, the focus is on extracting Norway spruce (Picea abies) bark lignin via organosolv extraction. Following the removal of the extractives and the subcritical water extraction to remove the polysaccharides, a novel cyclic organosolv extraction procedure was applied, which enabled the recovery of lignin with high quality and preserved structure. Main indicators for low degradation and preservation of the lignin structure were a high β-O-4′ content and low amounts of condensed structures. Furthermore, high purity and low polydispersity of the lignin were observed. Thus, the obtained lignin exhibits high potential for use in the direct development of polymer precursors and other bio-based materials. During the extraction sequence, around 70% of the bark was extracted. Besides the lignin, the extractives as well as pectic polysaccharides and hemicelluloses were recovered with only minor degradation, which could potentially be used for the production of biofuel or other high-value products such as emulsifiers or adhesives.

Organosolv Lignin from European Tree Bark: Influence of Bark Pretreatment.

As lignin is becoming more and more attractive to industry and the circular economy continues to grow, the utilization of a byproduct that, to date, has been underrated by the wood industry is investigated as an abundantly available source of lignin. Bark from spruce, larch and beech tress is extracted using the organosolv process with and without prior hot water extraction. The influence of the treatment on chemical properties of the lignin was determined by spectrophotometric, chromatographic, and vibrational spectroscopy. It was found that hot water extraction prior to organosolv extraction influences the chemical composition, antioxidative properties and molecular weight distribution of the obtained extracts. While hot water extracts are rich in flavonoids, organosolv fractions can contain high amounts of organic acids depending on whether they are from a hardwood or softwood source. This investigation lays the foundation for further research into the utilization of byproducts to generate high-value resources.

Mesoporous Manganese Oxide/Lignin-Derived Carbon for High Performance of Supercapacitor Electrodes

This study explores the modification of lignin with surfactants, which can be used as a template to make mesoporous structures, and can also be used in combination with manganese oxide to produce manganese oxide/lignin-derived carbon. Organosolv extraction, using ethanol (70%) at 150 °C, was carried out to extract lignin from oil palm wood. Lignin was then mixed with Pluronic F-127, with and without Mn(NO3)2, and then crosslinked with acidic formaldehyde, resulting in a carbon precursor-based modified lignin. Carbonization was carried out at 900 °C to produce lignin-derived carbon and manganese oxide/lignin-derived carbon. The characterization materials included Fourier transform infrared (FTIR) spectroscopy, scanning electron microscope-energy dispersive X-ray (SEM-EDX) mapping, X-ray diffraction (XRD), and N2-sorption analysis. FTIR curves displayed the vibration bands of lignin and manganese oxide. SEM images exhibited the different morphological characteristics of carbon from LS120% (lignin with a Pluronic surfactant of 120%) and LS120%Mn20% (lignin with a Pluronic of 120% and Mn oxide of 20%). Carbon LS120% (C-LS120%) showed the highest specific surface area of 1425 m2/g with a mean pore size of 3.14 nm. The largest mean pore size of 5.23 nm with a specific surface area of 922 m2/g was exhibited by carbon LS120%-Mn20% (C-LS120%-Mn20%). C-LS120%Mn20% features two phases of Mn oxide crystals. The highest specific capacitance of 345 F/g was exhibited by C-LS120%-Mn20%.

Advances in lignin valorization from a biorefinery concept

Lignin valorization for fuels and value-added products is essential to enhance the profitability and sustainability of biorefineries. Due to the complex and heterogeneous structure of lignin, technical barriers hinder the implementation of economic lignin utilization. Here, we summarize the major challenges facing lignin valorization processes. Different pretreatment methods, especially emerging combinatorial pretreatment approaches for isolating and tailoring lignin are introduced. To overcome the heterogeneity of lignin structure and improve lignin processability, advances in fractionation approaches including organosolv extraction, membrane technology, and gradient precipitation are analyzed and presented. Furthermore, progress in lignin valorization by thermochemical and biological conversion coupling with pretreatment and fractionation are systematically reviewed. Finally, we discuss advanced strategies and perspectives for future research involving biomass pretreatment, lignin fractionation and conversion processes.

Effect of organosolv extraction on the structure and antioxidant activity of eucalyptus kraft lignin

In this study, three lignin fractions F1, F2, and F3 were obtained from eucalyptus kraft lignin (EKL) by solvent extraction with ethyl acetate, acetone, and acetone/water. The antioxidant activity of these lignin fractions were measured and evaluated by using the DPPH radical scavenging activity, ABTS radical cation scavenging activity and ferric reducing antioxidant power analysis. These lignin fractions were also characterized by applying Gel permeation chromatography, Fourier transform infrared, 31P NMR and 2D HSQC NMR techniques. The three different lignin fractions had rather different average molecular sizes, as well as different phenolic and methoxy functional contents. The ethyl acetate fraction (F1) with the lowest average molecular weight (2342 g/mol) and the highest phenolic hydroxyl content (4.2457 mmol/g) and methoxy groups (6.2714 mmol/g) showed high homogeneity and the highest antioxidant activity. Its DPPH scavenging activity, ABTS+ scavenging activity, and ferric reducing the antioxidant power were 68.67%, 75.57%, and 91.89 μmol/g, respectively. Moreover, the antioxidant activity of F1 and F2 was found to be higher than that of butylated hydroxytoluene. Therefore, solvent extraction was shown to be an effective way to separate lignin fractions with high homogeneity, high antioxidant activity, which could lead to application of lignin with higher value.

Highly Efficient Semi-Continuous Extraction and In-Line Purification of High β-O-4 Butanosolv Lignin.

Innovative biomass fractionation is of major importance for economically competitive biorefineries. Lignin is currently severely underutilized due to the use of high severity fractionation methodologies that yield complex condensed lignin that limits high-value applicability. Mild lignin fractionation conditions can lead to lignin with a more regular C-O bonded structure that has increased potential for higher value applications. Nevertheless, such extraction methodologies typically suffer from inadequate lignin extraction efficiencies and yield. (Semi)-continuous flow extractions are a promising method to achieve improved extraction efficiency of such C-O linked lignin. Here we show that optimized organosolv extraction in a flow-through setup resulted in 93–96% delignification of 40 g walnut shells (40 wt% lignin content) by applying mild organosolv extraction conditions with a 2 g/min flowrate of a 9:1 n-butanol/water mixture with 0.18 M H2SO4 at 120°C in 2.5 h. 85 wt% of the lignin (corrected for alcohol incorporation, moisture content and carbohydrate impurities) was isolated as a powder with a high retention of the β-aryl ether (β-O-4) content of 63 linking motifs per 100 C9 units. Close examination of the isolated lignin showed that the main carbohydrate contamination in the recovered lignin was butyl-xyloside and other butoxylate carbohydrates. The work-up and purification procedure were investigated and improved by the implementation of a caustic soda treatment step and phase separation with a continuous integrated mixer/separator (CINC). This led to a combined 75 wt% yield of the lignin in 3 separate fractions with 3% carbohydrate impurities and a very high β-O-4 content of 67 linking motifs per 100 C9 units. Analysis of all the mass flows showed that 98% of the carbohydrate content was removed with the inline purification step, which is a significant improvement to the 88% carbohydrate removal for the traditional lignin precipitation work-up procedure. Overall we show a convenient method for inline extraction and purification to obtain high β-O-4 butanosolv lignin in excellent yields.

Examination of how variations in lignin properties from Kraft and organosolv extraction influence the physicochemical characteristics of hydrothermal carbon

Seven different lignin samples, three from Kraft extraction and four from organosolv extraction, were subjected to hydrothermal treatment at 260℃ for four hours to assess the impact of lignin type on the physicochemical properties of the hydrothermal material. The 13C Solid state NMR, XPS, FTIR and SEM analysis revealed that the different sources of lignin and the extraction conditions created variations in the degree of syringyl and guaiacyl subunits, inter-unit bonding arrangements, morphology and surface composition. Hydrothermal carbonization appeared to “normalize” the differences between each of the lignin samples, via breaking β-O-4 or α-O-4 linkages, removal of methoxy and syringyl subunits, and creation of CC and 4-O-5 linkages to polymerization into large 100−200 μm amorphous carbon particles. Overall, this study indicates that the source and extraction type have minimal influence on the physicochemical structure and morphology of the final hydrothermal product.

Amphiphilic Copolymers Derived from Butanosolv Lignin and Acrylamide: Synthesis, Properties in Water Solution, and Potential Applications

In this work, a series of amphiphilic lignin-acrylamide copolymers was synthetized via a grafting fromapproach using α-butoxylated organosolv lignin. This lignin is obtained in high yield via a mild organosolv extraction with butanol and contains a well-defined modified β-O-4 structure that allows for site-selective modification of the primary alcohol in the γ-position. The modified lignin was then used as a precursor of amphiphilic copolymers by reaction with acrylamide, either via free radical polymerization or via atom transfer radical polymerization after converting the lignin into a suitable macroinitiator. The effect of the synthetic method and acrylamide/lignin ratio on the final properties was studied and compared. Relevant solution properties, in particular, shear viscosity and interfacial and surface tension, showed that different synthetic methods and polymer compositions allow a tuning of the solution behavior toward specific potential applications, such as emulsion stabilization or enhanced oil recovery. Furthermore, it was preliminarily shown that the obtained polymers may potentially display low cytotoxicity, further increasing the possibilities for applications.

Kinetics of Secondary Reactions Affecting the Organosolv Lignin Structure.

Many valorization approaches for lignin rely on its organic solvent (organosolv) extraction. However, the severity of the extraction conditions required to obtain high lignin extraction generally results in low-quality lignin for downstream processing. To better understand the secondary reaction pathways and kinetics related to molecular alterations that result from organosolv extraction under extreme conditions, extractions were conducted at temperatures of 150, 180, and 210 °C. Lignin was collected at residence times between 0.25 and 18 h and analyzed by NMR techniques to quantify the concentrations of key chemical moieties that appear or disappear upon reactions of lignin molecules during and after their fractionation from biomass. The kinetics of chemical moiety evolution was modeled as processes in-series. In these models, pseudo first-order kinetics were used to describe the change in concentration of chemical moieties on extracted lignin as a function of residence time.

A simple fractionation method and GPC analysis of organosolv extracts obtained from lignocellulosic materials

The elucidation of lignin structural features is necessary for the efficient application of this polymer. Fractionation is an effective technique to achieve homogeneous lignin fractions, helping to better understand its composition and structure, and improving its use as source of phenolic compounds. This work develops a new and simple fractionation method of organosolv extracts obtained from lignocellulosic materials that enables the selective separation of lignin (from complex macromolecules to low molecular weight aromatic compounds originated from their degradation) from saccharides derived from hemicelluloses and cellulose. For this purpose, the non-catalytic organosolv extraction of lignin from almond shells was performed with dioxane/water mixtures and then the successful fractionation of the organosolv extracts with anhydrous tetrahydrofuran was achieved, resulting in the selective separation of lignin (lignin fraction) from saccharides (saccharide fraction). Gel permeation chromatography (GPC), thioacidolysis, and GC-MS were used as analytical methods to qualitatively determine the purity of both fractions. In addition, GPC was also used to quantify the content of lignin monomers and furfural in the organosolv extracts, thus allowing valuable information on the state of degradation of the lignin and hemicelluloses extracted to be obtained, respectively. The application of the GPC method also enabled the determination of the molecular weight distribution of the extracted lignin in the same analysis.