Fractionation Of Lignocellulosic Biomass Research Articles

Lignocellulose Treatment Using a Flow-Through Variant of OrganoCat Process.

This study adapts the biphasic OrganoCat system into a flow-through (FT) reactor, using a heated tubular setup where a mixture of oxalic acid and 2-methyltetrahydrofuran (2-MTHF) is pumped through beech wood biomass. This method minimizes solvent-biomass contact time, facilitating rapid product removal and reducing the risk of secondary reactions. A comparative analysis with traditional batch processes reveals that the FT system, especially under severe conditions, significantly enhances extraction efficiency, yielding higher amounts of lignin and sugars with reduced solid residue. Notably, the FT system shows partial hydrolysis of the cellulose, which increases with temperature while not producing significant amounts of furfural or 5-HMF, indicating more efficient depolymerization of polysaccharides without substantial sugar degradation. A statistical design of experiments (DOE) using a Box-Behnken design elucidates the influence of process variables (time, solvent flow rate, temperature) on the yield. Key findings highlight reactor temperature as the dominant factor affecting yields, with process time showing a significant but less pronounced impact. This study demonstrates the potential of the FT OrganoCat system for efficient lignocellulosic biomass fractionation and represents an advancement towards continuous lignocellulose processing, contributing to our knowledge of process optimization for improved biorefinery applications.

Unlocking biomass valorization: Machine Learning insights for Reductive Catalytic Fractionation of cotton stalks

Lignocellulosic biomass valorization has become an intensive area of research due to the importance of renewable nature and availability of biomass. However, biomass fractionation and depolymerization produce numerous datasets, that are difficult to visualise and interpret for the scale-up of the process. Therefore, machine learning algorithms, which can discover hidden patterns in data are applied to these datasets. Reductive Catalytic Fractionation (RCF) of lignocellulosic biomass is an emerging methodology to valorize biomass completely and effectively. Herein, the present work includes the Correlation Analysis and the Principal Component Analysis (PCA) of product distribution obtained from RCF of cotton stalks. Interactions between process variables and delignification (DL), sugar retention (SR), total phenolic monomers (PM), and individual phenolic monomers yield were evaluated. Correlations among DL, SR, and PM yields were also evaluated at different reaction conditions through PCA, which were explained using the reaction mechanism and molecular chemistry of lignin.

Integrated approach for co-production of bioethanol and light aromatics from lignocellulose through polyethylene glycol-aided acidic glycerol pretreatment

Acid-catalyzed glycerol organosolv (GO) pretreatment is a promising method for lignocellulosic biomass (LCB) fractionation. However, this method often leads to lignin repolymerization, intensifying lignin's inhibitory effects on subsequent enzymatic hydrolysis and limiting the production of highly active lignin, thereby hindering its valorization. This study explored incorporating polyethylene glycol (PEG) into acidic-catalyzed GO to improve bioethanol and bio-oil yields, with a focus on improving the yield of light aromatics, from LCB. Optimized PEG-aided GO pretreatment achieved a significantly higher bioethanol yield (23.7 g/L) compared to GO (17 g/L) and dilute acid (DA: 11.3 g/L) pretreatments. This improvement is attributed to the ability of PEG to mitigate lignin inhibition and modify the physicochemical properties of the pretreated substrate. Furthermore, thermal pyrolysis of PEG-aided GO lignin, obtained after the fermentation process, resulted in a substantially increased bio-oil yield (45.5 %) compared to GO (19 %) and DA (12 %). The enhanced bio-oil yield from PEG-aided GO lignin is ascribed to the promotion of β-O-4 linkages and the formation of β-O-4′ linkages. Characterization of the pyrolysis bio-oil revealed that light aromatic compounds were the dominant fraction, with their relative abundance significantly increasing from DA (5.9 %) to GO (9.7 %) and PEG-aided GO lignin (24.9 %). The PEG-aided GO method achieved an energy output of 8.85 MJ/kg, exceeding that of the GO and DA methods by 31 % and 57 %, respectively. The energy conversion efficiency of the PEG-aided GO method was 70 %, demonstrating a significant improvement compared to GO (57 %) and DA (51 %). This approach promotes the circular economy by upcycling LCB for bioethanol and valuable light aromatic compound production.

Advancing Lignocellulosic Biomass Fractionation through Molten Salt Hydrates: Catalyst-Enhanced Pretreatment for Sustainable Biorefineries.

Developing a process that performs the lignocellulosic biomass fractionation under milder conditions simultaneously with the depolymerization and/or the upgrading of all fractions is fundamental for the economic viability of future lignin-first biorefineries. The molten salt hydrates (MSH) with homogeneous or heterogeneous catalysts are a potential alternative to biomass pretreatment that promotes cellulose's dissolution and its conversion to different platform molecules while keeping the lignin reactivity. This review investigates the fractionation of lignocellulosic biomass using MSH to produce chemicals and fuels. First, the MSH properties and applications are discussed. In particular, the use of MSH in cellulose dissolution and hydrolysis for producing high-value chemicals and fuels is presented. Then, the biomass treatment with MSH is discussed. Different strategies for preventing sugar degradation, such as biphasic media, adsorbents, and precipitation, are contrasted. The potential for valorizing isolated lignin from the pretreatment with MSH is debated. Finally, challenges and limitations in utilizing MSH for biomass valorization are discussed, and future developments are presented. Cellulose Avicel®PH-101 ZnCl2 ⋅ 4H2O, ZnBr2 ⋅ 4H2O, LiCl ⋅ 8H2O, LiBr ⋅ 4H2O H2SO4, (0.2 M); H3PW12O40 (0.067 M); H4SiW12O40 (0.05 M) T (145-175 °C); Time (30-120 min) Organic solvent (MIBK) LA (94 %) and HMF (3.4 %) Dissolution time: ZnBr2 ⋅ 4H2O<>2O<>2 ⋅ 4H2O<>2O; The highest conversion of pretreated cellulose and yield of glucose were obtained with ZnBr2 ⋅ 4H2O (88 % and 80 %, respectively).

Fractionation of orange lignocellulosic biomass and optimization of distinct methods for oil extraction

Abstract Annually, amounts of orange waste are directed into the environment. The orange waste oil is a potential source of compounds of interest and alternatives have been explored to highlight their potential. Appropriately, this study investigated the effects of oil extraction processes involving pressurized liquids (PLE) and supercritical CO2 (SC-CO2) on orange residues. The results were compared with the standard Soxhlet procedure. The optimization of the operational parameters was established based on the adjustment of different process conditions for pressure (150 and 350 bar), extraction time (20 and 60 min), and temperature (40 and 60 °C). The results indicated that the maximum oil yields for orange peel and pomace were 37.76 % and 43.39 %, respectively, for the PLE approach. The SC-CO2 expressed maximum yields of up to 0.50 % and 0.38 % for peel and pomace, respectively. The GC-MS analysis reported the concentration of bioactive compounds after the distinct extraction methods.

Oxidative Catalytic Fractionation of Lignocellulosic Biomass Using a Co-N-P-C Catalyst and One-Step Isolation of Aromatic Monomers via Centrifugal Partition Chromatography

Oxidative Catalytic Fractionation of Lignocellulosic Biomass Using a Co-N-P-C Catalyst and One-Step Isolation of Aromatic Monomers via Centrifugal Partition Chromatography

Isolation of Highly Crystalline Cellulose via Combined Pretreatment/Fractionation and Extraction Procedures within a Biorefinery Concept.

Sustainable production of bio-based materials and chemicals requires integrated approaches which utilize all fractions of lignocellulosic biomass. In this work, highly crystalline cellulose was isolated via combined pretreatment/fractionation and extraction processes from beechwood sawdust. The proposed approach was based on the selective recovery of hemicellulose components in the first step, followed by enhanced delignification in the second step, permitting the efficient recovery of the remaining cellulose via bleaching in the final step. Hydrothermal pretreatment under tailored conditions in neat water or dilute acid resulted in almost complete hemicellulose removal (80-96 wt %) in the liquid fraction. In the second step, the formed surface lignin was isolated via mild extraction while enhanced removal of both native/structural and surface lignin (71 wt %) was achieved by applying the organosolv treatment using dilute sulfuric acid as catalyst. Dilute sulfuric acid pretreatment followed by acid catalyzed organosolv pretreatment proved to be the most efficient combined approach, leading to 80 wt % hemicellulose removal as xylose monomer, and 71 wt % delignification. High crystallinity cellulose (<88%), with an overall cellulose recovery of 68-91 wt % based on native cellulose in parent biomass was isolated in the last step via bleaching of all pretreated biomass solids. The proposed integrated biorefinery procedures that aim to whole "waste" biomass valorization, replacing fossil resources, with the use of green solvents (water, ethanol) at relatively mild temperature/pressure conditions, are in line with the scope of several United Nations Sustainable Development Goals, such as UN SDG 8, 11, 12, and 13.

Ionic liquid screening for lignocellulosic biomass fractionation: COSMO–RS prediction and experimental verification

The fractionation of lignocellulosic biomass is vital for advancing its applications, particularly in the extraction of high-demand cellulose. In this study, 378 ionic liquids (ILs), comprising of 18 anions and 21 cations, were selected to predict lignocellulosic biomass fractionation using COSMO–RS. The selectivity of the cellulose model to the lignin model in the prediction indicates that the dissolution and separation of lignocellulosic biomass are primarily governed by the anion, and the carboxylate and amino acid anions present the most effective separation effect among the ILs. Moreover, the pretreatment and composition analysis of cornstalk using five representative ILs indicated consistency with the predicted selectivity. The higher calculated excess enthalpy between cellulose and the IL, compared to that between lignin and the IL, led to increased cellulose dissolution by the IL, ultimately resulting in the separation of lignocellulose. This study provides a new paradigm for directly predicting the selectivity of IL to cellulose and lignin and designing ILs capable of achieving lignocellulosic biomass fractionation through COSMO–RS simulation.

Alkali-based lignin extraction from lignocellulosic material and upgradation of residual pulp as bio-packaging material towards sustainable biomass utilization

The current study explored the extraction of lignin from paddy straw and kans grass, while focusing on the yield and physico-chemical properties of lignin. Alkali-based lignin extraction from lignocellulosic biomass indicated a positive correlation between NaOH concentration and lignin yield. An increase in NaOH concentration from 0.50 % to 2.00 % resulted in increased yield of lignin from 129.16 to 447.07 mg/g and 222.79 to 551.37 mg/g of lignin from paddy straw and kans grass, respectively. The extracted lignin was characterized by FTIR and XRD, showed its chemical structure homogeneity with commercial lignin. Bio-packaging specimens were created using residual pulp and characterized for their physical and mechanical properties. The specimens of both the biomass were found to effectively withstand a load of 7.36 kg and 11.17 kg, respectively before crumpling. Further, the mass balance of the optimized process showed its industrial applicability for the fractionation and utilization of lignocellulosic biomass.

Reactive Eutectic Media for Lignocellulosic Biomass Fractionation.

This study introduces an alternative approach towards lignocellulosic biomass fractionation. For this purpose, reactive eutectic media (REM) based on ammonium formate and different organic acids are investigated, possible products are identified, and the REM are employed for lignin extraction and terminal isolation of cellulose pulp from beech wood. The method promises a considerable process intensification by simultaneous separation of high purity cellulose pulp, lignin isolation as a cationically modified species, and production of value-added chemicals from reaction products of the REM. This study puts a further focus on the generated cellulose pulp and investigates it with respect to surface charge and fiber length.

Fumaric acid production by Rhizopus species from acid hydrolysate of oil palm empty fruit bunches.

The hemicellulosic fraction of lignocellulosic biomass is a very important material, due to the significant concentration of pentoses present in its composition and that can be used sustainably in biotechnological processes such as the production of fumaric acid. Research efforts are currently being promoted for the proper disposal and valorization of empty fruit bunches (EFB) from oil palm. In this work, seventeen Rhizopus species were evaluated in a fermentation medium with EFB hydrolyzate, without detoxification, as a carbon source for fumaric acid production. Rhizopus circicans 1475 and Rhizopus 3271 achieved productions of 5.65g.L-1 and 5.25g.L-1 of fumaric acid at 30°C, 120rpm for 96h, respectively. The percentage of consumed sugars, mainly pentoses, was 24.88% and 34.02% for R. circicans 1475 and R 3271, respectively. Soy peptone and ammonium sulfate were evaluated as nitrogen sources, where soy peptone stimulated the formation of biomass pellets while ammonium sulfate produced mycelia and clamps.

Bioconversion of hemicellulosic fraction of wheat straw biomass to bioethanol by Scheffersomyces stipitis: A kLa-based scale-up study

The potent utilization of hemicellulosic fraction, which comprises one-third of carbohydrates in lignocellulosic biomass (LCB), is vital to strengthen the bioethanol production from it. Most studies on bioethanol production from LCB focused on cellulosic fraction only, or very low ethanol productivity is reported from hemicellulosic fraction. The present study investigated a process to convert the hemicellulosic fraction of wheat straw biomass to bioethanol effectively using Scheffersomyces stipitis. This work aimed to develop and demonstrate a systematic approach for scaling up the fermentation process, keeping the volumetric oxygen transfer coefficient (kLa) nearly constant in different scale bioreactors. It was found that 99.11±0.13% of synthetic xylose and 99.04±0.10% of lignocellulosic xylose were converted to bioethanol with a yield and productivity of 0.4706±0.0022 g/g and 1.5325±0.0020 g/Lh; 0.4290±0.0030 g/g and 0.7399±0.0043 g/Lh, respectively at an optimum kLa of 0.5776 (0.5735, 0.5817) min−1 and 0.6924 (0.6887, 0.6961) min−1, respectively in a 0.5 L bioreactor. After that, these optimum kLa were validated in 1 L and 5 L bioreactors. The successful kLa validation revealed that the hemicellulosic fraction of lignocellulosic biomass could also be well utilized for bioethanol production.

Combination of microwave with acid deep eutectic solvent pretreatment for reed (Phragmites australis) fractionation

The cost-effective and low-carbon fractionation of lignocellulosic biomass will enhance the economic viability of bio-refining. To achieve efficient reed fractionation under favorable conditions, microwave-assisted choline chloride and p-toluene sulfonic acid (M-ChCl/p-TsOH) pretreatment was employed. The fractionation of reed components demonstrated higher effectiveness with M-ChCl/p-TsOH pretreatment compared to conventional DES pretreatment. Under M-ChCl/p-TsOH conditions, a high hemicellulose removal rate (∼90%) and delignification rate (∼65%) were achieved while achieving a saccharification rate of 88% during cellulase hydrolysis. Microwave assistance not only significantly reduced reaction time to less than 60 s but also enhanced the pretreatment efficacy. Furthermore, the obtained lignin products consisted of low-polymerization lignin (MW < 800 g/mol) and acid-soluble lignin, providing a solid foundation for subsequent high-value utilization of lignin. This study provides a promising strategy for the low carbon fractionation of reed using DES, aiming to simultaneously achieve efficient cellulose hydrolysis and obtain tractable lignin.

Innovative flow-through reaction system for the sustainable production of phenolic monomers from lignocellulose catalyzed by supported Mo2C.

Molybdenum carbide supported on activated carbon (β-Mo2C/AC) has been tested as catalyst in the reductive catalytic fractionation (RCF) of lignocellulosic biomass both in batch and in Flow-Through (FT) reaction systems. High phenolic monomer yields (34 wt.%) and selectivity to monomers with reduced side alkyl chains (up to 80 wt.%) could be achieved in batch in the presence of hydrogen. FT-RCF were made with no hydrogen feed, thus via transfer hydrogenation from ethanol. Similar selectivity could be attained in FT-RCF using high catalyst/biomass ratios (0.6) and high molybdenum loading (35 wt.%) in the catalyst, although selectivity decreased with lower catalyst/biomass ratios or molybdenum contents. Regardless of these parameters, high delignification of the lignocellulosic biomass and similar monomer yields were observed in the FT mode (13-15 wt.%) while preserving the holocellulose fractions in the delignified pulp. FT-RCF system outperforms the batch reaction mode in the absence of hydrogen, both in terms of activity and selectivity to reduced monomers that is attributed to the two-step non-equilibrium processes and the removal of diffusional limitations that occur in the FT mode. Even though some molybdenum leaching was detected, the catalytic performance could be maintained with negligible loss of activity or selectivity for 15 consecutive runs.

Unraveling the mechanisms underlying lignin and xylan dissolution in recyclable biphasic catalytic systems

Despite the exceptional performance of recyclable biphasic pretreatment systems (i.e., p-toluenesulfonic acid (TsOH)/pentanol, H2SO4/butanol, and AlCl3/MTHF) in the holistic fractionation of lignocellulosic biomass (LCB), there remains a significant gap in understanding of the intricate mechanisms governing the rapid dissolution of lignin and xylan from LCB. This study conducts comparative analyses using laboratory experiments and computational simulations to gain insights into the mechanism behind removing lignin and xylan in these systems. Under identical pretreatment conditions (140 °C, 45 min), three systems exhibited distinct levels of delignification and xylan removal. TsOH/pentanol showcased the highest levels of both delignification (83.3%) and xylan removal (98.1%), followed by H2SO4/butanol (77.9% delignification and 83.0% xylan removal), and AlCl3/MTHF (73.5% delignification and 97.2% xylan removal). Lignin characterization revealed that TsOH/pentanol and AlCl3/MTHF lignin samples boasted well-preserved β-O-4 bonds (42.4/100 Ar, 40.4/100 Ar, respectively), uniform molecular weights, and <1% sugar content. This led to high yields of phenolic monomers (TsOH/pentanol, 33.9%; AlCl3/MTHF, 33.7%) after catalytic hydrogenolysis of lignin. Furthermore, mechanistic analyses revealed that the TsOH/pentanol and AlCl3/MTHF systems exhibited the most significant interaction energy formation with the lignin model (veratrylglycerol-b-guaiacyl ether) and D-xylan model due to robust hydrogen bonding interactions, yielding energy values of −2460 kJ/mol and −2385 kJ/mol, respectively. These interactions could play pivotal roles in accomplishing notable lignin and xylan extraction.

Lignocellulosic biomass pretreatment with a lignin stabilization strategy and valorization toward multipurpose fractionation

Lignocellulosic biomass has emerged as a promising alternative with sustainable advantages for the production of a wide range of renewable products and value-added chemicals. In this study, a pretreatment strategy that use a fully recyclable acid hydrotrope (p-TsOH aqueous solution) to extract lignin and employ glyoxylic acid (GA) to stabilize lignin was proposed for biomass valorization toward multipurpose fractionation. 83.0 % of lignin was dissolved out by p-TsOH hydrotrope (80 wt%) with GA addition to form GA-stabilized product at 80 o C for 15 min. The stabilized lignin was subsequently used as an additive in the preparation of lignin-based suncream. Notably, the incorporation of 4 wt% lignin nanospheres into an SPF15 sunscreen yielded a measured SPF of 59.94. Furthermore, the depolymerization of uncondensed lignin into aromatic monomers yielded a high lignin-oil yield of 84.2 %. Additionally, direct heating of the pretreatment liquor facilitated the conversion of monosaccharides into furfural, achieving a desired yield of 53.7 % without the addition of any acid catalyst. The pretreatment also enhanced the enzymatic hydrolysis of glucan, resulting in a saccharification yield of 98.4 %. Moreover, short-term ultrasonication of the pretreated substrate yielded pulp suitable for papermaking. Incorporating 15 wt% fibers into the produced paper sheets led to a 5.3 % increase in tear index and a 25.4 % increase in tensile index. This study presents a viable pretreatment strategy for the multipurpose fractionation of lignocellulosic biomass, offering potential avenues for biomass valorization.

Integrated acetic acid and deep eutectic solvent pretreatment on poplar for co-production of xylo-oligosaccharides, fermentable sugars and lignin antioxidants/adsorbents

Efficient fractionation of lignocellulosic biomass in usable forms of hemicellulose, cellulose and lignin is very important for the sustainable lignocellulosic biorefinery. Herein, poplar sawdust was pretreated with an integrated process composed of acetic acid pre-hydrolysis (170 °C, 60 min) for xylo-oligosaccharides (XOS) production and mild deep eutectic solvent (90–130 °C, 60 min) post-delignification for recovering lignin fractions, resulting in easily hydrolyzed cellulose fraction. Results showed that, after integrated pretreatment and enzymatic hydrolysis, 51 % of xylan and 92 % of glucan in raw biomass could be converted to XOS (DP 2–6) and glucose, respectively, while 71 % of the original lignin could be recovered in DES solvent. The resulting XOS were proven to ensure the growth of probiotics, Bifidobacterium adolescentis. Besides, the lignin macromolecules recovered from DES solvent showed high-purity (around 95 %), low-molecular weight (Mw around 2000), small particle size (270–170 nm) and high-PhOH (3.08 mmol/g) content, which were likely relevant to the excellent antioxidant activity (RSI = 15.16) and adsorbent activity (Pb(II) 461.89 mg/g lignin). Finally, mass balance and energy analysis revealed that the integrated pretreatment could be used as a promising approach for the production of bio-based chemicals and materials from woody biomass.

Counter-current chromatography for lignin monomer–monomer and monomer–oligomer separations from reductive catalytic fractionation oil

Counter-current chromatography is an effective unit operation for simultaneous aromatic monomer–monomer and monomer–oligomer separations from oil derived from reductive catalytic fractionation of lignocellulosic biomass.

A powerful two-dimensional chromatography method for the non-target analysis of depolymerised lignin

BackgroundLignin is an abundant natural polymer obtained as a by-product from the fractionation of lignocellulosic biomass. In the name of a circular economy, lignin should be valorised into valuable chemicals or biomaterials and utilised instead of petrochemicals. For the development of efficient valorisation processes, the structural characterisation of lignin can be highly beneficial. However, this is an arduous task, as the isolated (and sometimes processed) lignin mainly consists of various neutral monomers but also oligomers. In addition, the material contains isomers, which can be especially problematic to separate and identify. ResultsWe present a powerful off-line comprehensive two-dimensional (2D) chromatography method combining liquid chromatography (LC), supercritical fluid chromatography (SFC), and high-resolution mass spectrometry for the non-target analysis of depolymerised lignin. The implementation of a 1-aminoanthracene column in the second dimension enabled a class separation of potential lignin monomers, dimers, trimers, and tetramers with an additional separation based on the number of hydroxyl groups and steric effects. The pentafluorophenyl column in the first dimension additionally improved the separation based on hydrophobicity. The comparison of off-line 2D LC × SFC to 1D SFC showed that besides the overall improved performance, the first method is also superior for the separation of isomers. Advanced data analysis methods (MS-DIAL, SIRIUS, and Feature-Based Molecular Network) were integrated into the non-target workflow to rapidly visualise and study the detected compounds, which proved to be especially beneficial for the characterisation of the separated isomers. SignificanceThe method yielded the first 2D LC plot demonstrating a classification of lignin compounds, which can be applied to compare various lignin sources and processing methods. In addition, the technique demonstrated improved separation of compounds, including isomers, which was especially beneficial as 77 % of the detected compounds had at least one isomer in the same lignin sample.

Fully utilizing the organic and inorganic fractions in rice husk for electrode materials towards an excellent asymmetric solid-state supercapacitor

Rice husk is selected as the feedstock for the production of activated carbons (RHAC). The desilication process is performed to enhance its potential application in supercapacitors, meanwhile, cobalt silicates (Co/Si-x) are synthesized from recycled waste silica. To explain the effect of desilication processes on the characteristics of derived activated carbons, the desilication steps are carried out after carbonization and activation to produce two different types of desilicated RHAC (CD-RHAC and AD-RHAC). Results show that the specific surface area of CD-RHAC and AD-RHAC are 3404.5 and 3451.3 m2 g−1, which are both higher than that of untreated RHAC (2075.1 m2 g−1). Furthermore, Co/Si-x samples exhibit significantly different properties due to the various Co/Si ratios. In a three-electrode system, the capacitance of CD-RHAC and Co/Si-3 can achieve the capacitances of 264.5 and 400.3 F g−1 at the current density of 0.5 A g−1. The CD-RHAC//Co/Si-3 asymmetric solid-state supercapacitor shows an excellent capacitance retention of about 100 % after 6000 cycles and a high energy density of 19.0 Wh kg−1 at a power density of 176.8 W kg−1. Overall, the work offers a feasible pathway to fully utilize the organic and inorganic fractions of lignocellulosic biomass in the field of energy storage.