Pretreatment Of Lignocellulosic Biomass Research Articles

Deep eutectic solvents assisted laccase pretreatment for improving enzymatic hydrolysis of corn stover.

The efficient and eco-friendly removal of lignin is a critical challenge for bioethanol production from lignocellulosic biomass. Herein, we report the integration of laccase with deep eutectic solvents (DESs) for the pretreatment of corn stover to enhance the production of reducing sugars. Three betaine-based DESs were prepared and tested for their effects on the activity and stability of a bacterial laccase from Bacillus amyloliquefaciens LC02. The aqueous solution of DESs showed no adverse influence on laccase activity, and the laccase thermostability was improved in the presence of DESs. More than 95% of the laccase activity was retained in the DESs solution during the first hour of incubation at 70°C. A red shift in the fluorescence spectra was observed for the laccase in the presence of DESs, indicating conformational changes. The laccase was able to degrade a dimeric lignin model compound by cleaving its β-O-4 bond. The transformation products were identified using LC-MS. The maximal lignin removal from corn stover was achieved by pretreatment using laccase in combination with the betaine-glycerol DES, which also resulted in a yield of fermentable sugar that was 130% higher than the control. This combination strategy provides guidance on the application of laccase and DESs in the pretreatment of lignocellulosic biomass.

Advances in electromagnetic radiation-assisted pretreatment of lignocellulosic biomass as a green method: a review

Advances in electromagnetic radiation-assisted pretreatment of lignocellulosic biomass as a green method: a review

Optimized thermal pretreatment for lignocellulosic biomass of pigeon pea stalks to augment quality and quantity of biogas production

By applying heat to the feedstock during the thermal treatment of biomass for the production of biogas, the organic material's biodegradability can be greatly increased. Biogas production is a huge research area for alternate energy production technology. Increased biodegradability, improved methane yield, pathogen, and weed seed destruction, and overall process efficiency are all benefits of this type of pretreatment. It is a useful pretreatment technique for maximizing the production of biogas because it can decrease inhibitory compounds, and increase the digestibility of biomass. This work focused on increasing the efficiency of biogas production from lignocellulosic biomass of pigeon pea stalks by a novel thermal pretreatment. The pigeon pea stalk is initially imposed to physical pretreatment (PT) by an automatic hammer mill which is considered as a base for comparing performance. Thermal pretreatment was carried out for one hour, and two hours durations at different temperatures like 100 °C, 125 °C, 150 °C, 175 °C, and 200 °C. Compared to physically pretreated pigeon pea stalks, 200ᴼC thermal pretreated pigeon pea stalks for two hours have produced 88.41 % higher biogas, 16.14 % increase of cellulose, 19.9 % higher volatile solid removal, and 3.94 % lesser lignin. The enhanced chemical characteristics were ensured by analyzing the chemical composition variations through the FTIR, XRD, and SEM images. So, this is recommended for enhanced biogas production.

A deep eutectic solvent with a lignin stabilization and functionalization for lignocellulosic biomass pretreatment

This study synthesized a functional deep eutectic solvent (DES) using betaine and glyoxylic acid (GA) for lignocellulosic biomass pretreatment. The Betaine/GA DES pretreatment resulted a high delignification efficiency of 81.89% and xylan removal of 83.25% while preserving most of cellulose. During pretreatment, lignin was stabilized by GA, preventing its condensation and introducing carboxyl groups onto its molecular backbone. The GA stabilized lignin (GASL), with a high β-O-4 linkage content of 62.92%, was depolymerized for phenolic monomer production with a bio-oil yield of 55.40%. Additionally, the functional lignin was used as a surfactant for GASL-based O/W emulsion (GA-O/W emulsion) preparation. With 0.5% of lignin addition and an optimal O/W ratio of 6:4, the resulting GA-O/W emulsion exhibited a high cream index value of 100% and excellent storage stability without any phase transition or emulsion aggregation. When using the lignin to prepare curcumin-encapsulated microcapsules, a cumulative curcumin remaining of 74.19% under UV radiation and an extraordinary encapsulation efficiency of 62.86% were achieved. Furthermore, this DES pretreatment promoted enzymatic saccharification of the pretreated cellulose substrate, resulting in a glucose yield of 91.49%. After adding 15 wt% of the fibers in soft wood pulp for papermaking, the tear index, ring crush strength index, and tensile index of the produced paper-sheets reached 112.04%, 98.58%, and 83.55% of those of the pure softwood pulp papers, respectively.

Production of 5-Hydroxymethylfurfural from Hydrolysate of pretreated lignocellulosic biomass in a biphasic system reactor

Production of 5-Hydroxymethylfurfural from Hydrolysate of pretreated lignocellulosic biomass in a biphasic system reactor

Coupling pretreatment of lignocellulosic biomass for enzymatic hydrolysis with electrochemical reduction of CO2 for production of formic acid

A new coupled electrolysis system has been developed by combining pretreatment of lignocellulosic biomass (corn stover) in alkaline anolyte for increasing cellulose digestibility with electrochemical reduction of CO2 on the cathode to produce formic acid. Electrodeposition of Sn on calcinated copper foam results in preparation of an efficient cathode, ED-Sn@CuOx, achieving 83.2% Faradaic efficiency of formate formation with a current density of 69.2 mA/cm2 in an H-type electrolysis cell. The ferricyanide/ferrocyanide redox couple plays an efficient electron mediator to improve the rate of electron transfer. Oxygen evolution reaction can be significantly suppressed, increasing the production rate of formate. Corn stover can be simultaneously pretreated by delignification in alkaline anolyte. Under the relatively optimal condition, the pretreated substrates obtained 96.6% glucose yield and 83.4% xylose yield. By inputting 1 kWh of electricity, the coupled system can obtain 0.27 kg formate with simultaneously pretreating 31.1 kg corn stover, resulting in the production of 14.2 kg fermentable sugars by subsequent enzymatic hydrolysis. However, alkaline delignification in the anolyte also plays an important role in the increase in the pretreatment efficiency.

Production of Low-Cost Adsorbents within a Circular Economy Approach: Use of Spruce Sawdust Pretreated with Desalination Brine to Adsorb Methylene Blue.

A sustainable low-cost activated carbon substitute was produced based on pretreated lignocellulosic biomass, especially spruce sawdust. A harmful liquid waste, desalination brine, was used for the treatment of a solid wood industry waste, spruce sawdust. This approach is in the circular economy theory and aims at the decarbonization of the economy. Pretreated sawdust was tested as an adsorbent appropriate for the removal of a commonly used pollutant, methylene blue, from industrial wastewater. The adsorption capacity of the pretreated material was found to have increased four times compared to the untreated one in the case that the Freundlich equation was fitted to the isotherms' data, i.e., the one with the best fit to the isotherm's experimental data of the three isotherm models used herein. The treatment experimental conditions with desalination brine that gave maximum adsorption capacity correspond to a 1.97 combined severity factor in logarithmic form value. Moreover, a kinetic experiment was carried out with regard to the methylene blue adsorption process. The desalination brine-pretreated sawdust adsorption capacity increased approximately two times compared to the untreated one, in the case when the second-order kinetic equation was used, which had the best fit of the kinetic data of the three kinetic models used herein. In this case, the pretreatment experimental conditions that gave maximum adsorption capacity correspond to -1.049 combined severity factor in logarithmic form. Industrial scale applications can be based on the kinetic data findings, i.e., spruce sawdust optimal pretreatment conditions at 200 °C, for 25 min, with brine solution containing 98.12 g L-1 NaCl, as they are related to a much shorter adsorption period compared to the isotherm data.

Current status and future prospects of pretreatment for tobacco stalk lignocellulose.

With the growing demand for sustainable development, tobacco stalks, as a resource-rich and low-cost renewable resource, hold the potential for producing high-value chemicals and materials within a circular economy. Due to the complex and unique structure of tobacco stalk biomass, traditional methods are ineffective in its utilization, making the pretreatment of tobacco stalk lignocellulose a crucial step in obtaining high-value products. This paper reviews recent advancements in various pretreatment technologies for tobacco stalk lignocellulosic biomass, including hydrothermal, steam explosion, acid, alkaline, organic solvent, ionic liquid, and deep eutectic solvent pretreatment. It emphasizes the impact and efficiency of these pretreatment methods on the conversion of tobacco stalk biomass and discusses the advantages and disadvantages of each technique. Finally, the paper forecasts future research directions in the pretreatment of tobacco stalk lignocellulose, providing new insights and methods for enhancing its efficient utilization.

Effects of Sugar Beet Pulp Pretreatment Methods on Hydrogen Production by Dark Fermentation

Methane and hydrogen generated from waste and biomass are renewable resources, which may successfully replace traditional fossil fuels. This paper investigates the enhancement effect of lignocellulosic biomass pretreatment on dark fermentative hydrogen production from sugar beet pulp (SBP). The results showed that sugar beet pulp after pretreatment contained significant amounts of unfermented sugars (mainly glucose, arabinose, galactose, and raffinose), and, therefore, represented an attractive substrate for methane and hydrogen production. The greatest methane yield (495 dm3 CH4/kg VS) was achieved from sugar beet pulp after alkaline pretreatment. High methane production of up to 445 dm3 CH4/kg VS was also obtained using acidic and enzymatic hydrolysis as a preliminary treatment of the pulp. All the pretreatment methods also resulted in the enhancement of hydrogen yield with the highest value of 229 dm3 H2/kg VS achieved using acid hydrolysis compared with 17 dm3 H2/kg VS for raw material subjected to digestion.

Supercharged cellulases show superior thermal stability and enhanced activity towards pretreated biomass and cellulose

Non-productive binding of cellulolytic enzymes to various plant cell wall components, such as lignin and cellulose, necessitates high enzyme loadings to achieve efficient conversion of pretreated lignocellulosic biomass to fermentable sugars. Protein supercharging was previously employed as one of the strategies to reduce non-productive binding to biomass. However, various questions remain unanswered regarding the hydrolysis kinetics of supercharged enzymes towards pretreated biomass substrates and the role played by enzyme interactions with individual cell wall polymers such as cellulose and xylan. In this study, CBM2a (from Thermobifida fusca) fused with endocellulase Cel5A (from T. fusca) was used as the model wild-type enzyme and CBM2a was supercharged using Rosetta, to obtain eight variants with net charges spanning −14 to +6. These enzymes were recombinantly expressed in E. coli, purified from cell lysates, and their hydrolytic activities were tested against pretreated biomass substrates (AFEX and EA treated corn stover). Although the wild-type enzyme showed greater activity compared to both negatively and positively supercharged enzymes towards pretreated biomass, thermal denaturation assays identified two negatively supercharged constructs that perform better than the wild-type enzyme (∼3 to 4-fold difference in activity) upon thermal deactivation at higher temperatures. To better understand the causal factor of reduced supercharged enzyme activity towards AFEX corn stover, we performed hydrolysis assays on cellulose-I/xylan/pNPC, lignin inhibition assays, and thermal stability assays. Altogether, these assays showed that the negatively supercharged mutants were highly impacted by reduced activity towards xylan whereas the positively supercharged mutants showed dramatically reduced activity towards cellulose and xylan. It was identified that a combination of impaired cellulose binding and lower thermal stability was the cause of reduced hydrolytic activity of positively supercharged enzyme sub-group. Overall, this study demonstrated a systematic approach to investigate the behavior of supercharged enzymes and identified supercharged enzyme constructs that show superior activity at elevated temperatures. Future work will address the impact of parameters such as pH, salt concentration, and assay temperature on the hydrolytic activity and thermal stability of supercharged enzymes.

A Mini Review on the Influence of Different Intermediate Mass Transfer Effects on the Chemical Pretreatment of Lignocellulosic Biomass

ABSTRACTChemical pretreatment of lignocellulosic biomass (LCB) in the presence of an alkaline catalyst is one of the major pretreatment processes that recover cellulose, hemicellulose, and lignin at effective process conditions and also for the production of bioethanol. Replacement of conventional catalysts with waste‐derived catalysts in the pretreatment process will be helpful for the development of low‐cost biorefinery. The continuous impact of different mass transfer properties during the chemical pretreatment of LCB will affect the final yield of products at a high reaction time and has been reviewed in the current study. Intraparticle diffusion of an alkaline catalyst into LCB is going to determine the diffusion of the selected catalyst within the porous biomass structure, which helps in the enhancement of the final yield of the product recovery at low‐process conditions. The diffusion of the synthesized catalyst within the selected biomass during the chemical pretreatment process is a rate‐limiting step that influences the final recovery yield of desired products. Enhancement of the biomass pretreatment reaction through the assessment of the diffusivity using the modified Nernst–Einstein relation is also discussed. Determination of different unique mass transfer properties rate of diffusion, diffusivity flux, and mass transfer coefficient are also to be analyzed to advance the reaction rate of the pretreatment process.

Scaling-up fungal pretreatment of lignocellulose biomass: Impact on nutritional value, ruminal degradability, methane production, and performance of lactating dairy cows

Scaling-up fungal pretreatment of lignocellulose biomass (LCB) for ruminant nutrition has become a major research challenge in recent years. This study systematically investigated the effectiveness of fungal (Pleurotus ostreatus) pretreatment (for 30 days under solid state fermentation (SSF)) of large quantities (8400 kg) of lime-pasteurized wheat straw, in terms of improvement in nutritional value, in vitro ruminal fermentation characteristics and methane (CH4) production potential. We further investigated the effects of stepwise replacement of untreated wheat straw (UTWS) with the lime pasteurized P. ostreatus treated wheat straw (PTWS) on dry matter intake (DMI), apparent total tract digestibility, production performance, CH4 emission and feed efficiency of lactating dairy cows. The results revealed that PTWS had lower lignin (P< 0.001), hemicellulose (P< 0.001) and cellulose (P< 0.05) contents and higher crude protein (CP; P< 0.001) content and cellulose to lignin ratio (P< 0.01), as compared to UTWS. The PTWS had higher in vitro DM digestibility (IVDMD; P< 0.001), total gas production (IVGP; P< 0.01), total volatile fatty acids (VFAs, P< 0.01) and propionate (P< 0.05) concentration, and lower (P< 0.05) pH and CH4 gas production during 72 h in vitro fermentation. Notably, the fungus degraded 33.3 % lignin at the expense of 6.56 % cellulose, and markedly increased CP content (46.3 %), IVDMD (20.2 %), IVGP (16.8 %) and VFAs (10.0 %) production, and decreased CH4 production (10.3 %). The aflatoxin B1 concentration of PTWS was <5.0 µg/kg, and mycelium concentration was 181.9 mg/kg DM, reflecting safe and effective tretment of the straw. Replacement of 32 % UTWS in total mixed ration with the PTWS, increased DMI (0.84 kg/day; P = 0.01), apparent total tract DM digestibility (5.5 g/100 g; P< 0.05) and milk yield (1.17 liter/day; P= 0.032), and decreased CH4 emission (1.45 g/kg DMI; P< 0.05). In conclusion, hydrated lime can replace traditional high-tech pasteurization methods for the fungal pretreatment of LCB, and present prospects for scaling up the process for ruminant nutrition.

Enhancing biogas production through photocatalytic pretreatment of rice straw co-digested with cow dung and food waste using a novel g-C3N4/SiO2/bentonite catalyst

This study investigates the application of a novel composite photocatalyst, g-C3N4/SiO2/ Bentonite, for rice straw pretreatment, aiming to enhance biogas production in anaerobic digestion. The photocatalytic pretreatment disrupts rice straw's lignin and hemicellulose structures, reducing silica content for improved microbial degradation. Five 2 L anaerobic digesters were employed with rice straw as the substrate and co-digestion materials, including cow dung and food waste. Rice straw treated with the g-C3N4/7.5% SiO2/5% Bentonite catalyst exhibited a remarkable 37% increase in methane yield compared to untreated rice straw. This photocatalytic process led to a 31% increase in cellulose content and a 30% reduction in lignin after 6 hours of pretreatment. Simultaneously, silica content in the rice straw decreased to 6.4% after 6 hours, resulting in a 48% increase in the carbon proportion. These findings underscore the potential of integrated photocatalysts for significantly enhancing biogas production efficiency through the pretreatment of lignocellulosic biomass.

Tuning Structural Characteristics of Corn Stover Through Ammonium and Sodium Sulfite (ASS) Pretreatment for Enhanced Enzymatic Hydrolysis.

The ammonia fiber expansion (AFEX) pretreatment of lignocellulosic biomass offers a significant advantage in terms of obtaining high glucan conversion, with the added benefit of ammonia being fully recyclable. However, despite the high efficiency of AFEX in pretreating lignocellulose, relatively high enzyme loading is still required for effective cellulose conversions. In this study, we have updated the AFEX pretreatment method; ammonia and sodium sulfite (ASS) can be used to produce a more digestible substrate. The results demonstrate that ASS-pretreated corn stover (CS) yields a higher fermentable sugar yield compared with AFEX pretreatment, even at lower enzyme loadings. Specifically, at an enzyme loading of 12 mg protein/g glucan, ASS-CS achieved 88.8% glucose and 80.6% xylose yield. Characterization analysis reveals that lignin underwent sulfonation during ASS pretreatment. This modification results in a more negative zeta potential for ASS-CS, indicating a reduction in nonproductive adsorption between lignin and cellulase through increased electrostatic repulsion.

Deletion of yghZ in Escherichia coli promotes growth in presence of furfural with xylose as carbon source.

Thermo-acidic pretreatment of lignocellulosic biomass is required to make it amenable to microbial metabolism and results in generation of furfural due to breakdown of pentose sugars. Furfural is toxic to microbial metabolism and results in reduced microbial productivity and increased production costs. This study asks if deletion of yghZ gene which encodes a NADPH-dependent aldehyde reductase enzyme results in improved furfural tolerance in Escherichia coli host. The ∆yghZ strain-SSK201-was tested for tolerance to furfural in presence of 5% xylose as a carbon source in AM1 minimal medium. At 96h and in presence of 1.0g/L furfural, the culture harboring strain SSK201 displayed 4.5-fold higher biomass, 2-fold lower furfural concentration and 15.75-fold higher specific growth rate (µ) as compared to the parent strain SSK42. The furfural tolerance advantage of SSK201 was retained when the carbon source was switched to glucose in AM1 medium and was lost in rich LB medium. The findings have potential to be scaled up to a hydrolysate culture medium, which contains furan inhibitors and lack nutritionally rich components, under bioreactor cultivation and observe growth advantage of the ∆yghZ host. It harbors potential to generate robust industrial strains which can convert lignocellulosic carbon into metabolites of interest in a cost-efficient manner.

Autohydrolysis of sugarcane bagasse with water reuse: Impacts on residues’ composition and enzymatic hydrolysis

This work presents a new sequential approach to the sugarcane bagasse autohydrolysis process in a way that the liquor from the previous reaction was reused in the next one, and the makeup water for the next batch was used to wash the solid fraction before being added to the liquor in the next batch. This approach was suggested first as a way of reducing the water usage in the process, and second as a way of concentrating the liquor in any interesting component, working with the possibility of losing efficiency towards the glucose production through a cellulose loss to the liquor or enzymatic efficiency loss from a higher inhibitor concentration. Two sets of five sequential batches were performed: one washing the solids with the makeup water prior to the enzymatic step (Set 2), and the other one without the washing step (Set 1), looking forward to the effects of the water reuse over the glucose production and the liquor composition. Autohydrolysis pretreatment removed most of the hemicellulose (∼94 %), with liquor recycling improving its removal until the third batch and stabilizing after that. Although the washing step showed little impact on the composition of the solids, it was determinant to the success of the enzymatic hydrolysis, since it was possible to maintain the cellulose to glucose yield around 53% throughout the batches. There was a 64 % reduction in the water used in the sequential reactions without interfering in the glucose production, which indicates that the proposed strategy could be successfully used to reduce costs and environmental impacts associated with the pretreatment of lignocellulosic biomass.

Combined leaching and steam explosion pretreatment of lignocellulosic biomass for high quality feedstock for thermochemical applications

A novel pretreatment approach was developed in the present study to simultaneously reduce the content of inorganic troubling elements (TEs) and improve biomass energy density, i.e., combined leaching and steam explosion (SE) pretreatment with mechanical pressing. Three different high-ash-containing biomass feedstocks were studied – wheat straw (WS), spruce bark (SB), and empty fruit bunches of oil palm (EFB). Before studying the combined pretreatment, the impact of individual pretreatment was determined in-depth on biomass composition and ash-transformation behaviour. In leaching pretreatment, the effect of leaching with steam explosion condensate (SEC), dilute acetic acid and water was studied comprehensively. The solid (raw and treated) and liquid samples (leachate, SEC, hydrolysate) were characterized for a detailed comparative analysis. The ash-fusion and −transformation behaviour of raw and pretreated biomass was studied in-depth using advanced multicomponent thermodynamic equilibrium modelling (TEM) and push-rod dilatometry. After combined pretreatment, a considerably high reduction in TEs content was noted: 82–98 % K, 93–99 % Na, 80–99 % Cl, 34–90 % S, 3–77 % Mg, ash 43–63 %, 26–67 % P, and 19–63 % Ca. Simultaneously, heating values of all three feedstocks increased by 1.3–2.3 MJ/kg, reaching up to 20–22 MJ/kg. TEM results reveal that much lesser amounts of molten slag and volatile inorganic compounds were formed in pretreated samples compared to raw and SE biomass, such as K2Si5MgO12, KCl, KPMgO4, K2Si2O5, CaSiO3, and MgSiO3 in WS; Na2CO3, K2CO3, K2CaC2O6, KPMgO4, and CaCO3 in SB. Due to higher energy density and lower propensity towards ash-related issues, combined pretreated WS and SB have a high potential to be used in large-scale thermochemical applications.

Multi enzyme production from mixed untreated agricultural residues applied in enzymatic saccharification of lignocellulosic biomass for biofuel

Lignocellulose recalcitrance essentially dictates high cost and low efficiency of its enzymatic saccharification. The complex lignocellulosic structure is a major obstacle to enzymatic saccharification and green ionic liquid pretreatment methods face difficulty of water washing prior enzymatic hydrolysis. Ionic liquid tolerant lignocellulolytic enzymes overcome the inhibition of enzymes during enzymatic saccharification and eliminated water washing step after pretreatment of lignocellulosic biomass. The cell wall composition cellulose, hemicellulose, and lignin, three main wall polymers of various agricultural residues and food waste lignocellulose substrates also affected the enzyme activities secreted by the B. subtilis strain. This study explores the potential of the halophilic, alkalophilic, and ionic liquid (IL)-tolerant strain Bacillus subtilis BC-001 for the simultaneous production of hydrolytic enzymes essential for lignocellulosic bio-refinery processes. BC-001 produced cellulase, amylase, xylanase, pectinase and protease are 70.41, 87.14, 65.50, 122.55 and 66.48 U/mL, respectively under optimized fermentation conditions. Cellulase produced by BC-001 retained more than 80% activity after 72 hours in 20% w/w of different ILs tested and enzymes retained more than 68% activities after 12 h in 50% w/w ILs. Employing such IL-stable cellulase, enzymatic saccharification is conducted without water washing on rice straw (RS) that has been pretreated with various ILs, including 1-ethyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, and choline chloride. This research is novel as the study marks the first instance of multi-hydrolytic enzyme production from a novel alkalophilic, halophilic, thermophilic, and IL-tolerant bacterial strain using a mixture of untreated agricultural residues.

The optimization of sodium hydroxide (NaOH) pre-treatment for reducing sugar production from rice husk using response surface methodology (RSM)

Lignocellulosic biomass is an abundant renewable resource which amounts to 1.3 billion tonnes per year and can be used in a variety of sustainable applications. It is primarily made up of tightly bound cellulose, hemicellulose, and lignin. However, hemicellulose dissolution and delignification pose significant challenges to the utilisation of reducing sugar. To solve this issue, alkaline pretreatment was utilised. The aim of lignocellulosic biomass pretreatment is to break down the complex structure of the biomass and provide better access to the components that can be converted into useful reducing sugar. Response Surface Methodology (RSM) was used to identify the optimal values for the factors influencing the pretreatment. The optimisation parameters were sodium hydroxide concentration (1 – 4 % w/v), pretreatment time (15 – 60 minutes), and solid loading (6 – 16% w/v). Rice husk, which was used as biomass, was hydrolysed enzymatically to produce reduced sugar. The optimum conditions for producing the highest reducing sugar of 15.18 mg/mL from rice husk were 1.67% w/v sodium hydroxide pretreatment, 59.44 minutes of pretreatment time, and 7.67% w/v solid loading. As a result, less alkaline reagents can be used with a longer pretreatment time, thus lowering the cost of pretreatment. Therefore, this shows that RSM was one of the best methods to replace the conventional technique for optimising the parameters of rice husk alkaline pretreatment for reducing sugar production.

Comprehensive understanding of co-producing fermentable sugar, furfural, and xylo-oligosaccharides through the pretreatment with CTAB-based deep eutectic solvent containing Brønsted and Lewis acid

The deep eutectic solvents (DESs) with additional functionalities synthesized using the cationic surfactant cetyltrimethylammonium bromide (CTAB) have gained attention due to their remarkable enzymatic enhancement capability. By combining CTAB, lactic acid, and FeCl3, a DES containing both Brønsted and Lewis acids was synthesized and the pretreatment parameters were optimized using response surface methodology. The results demonstrated the selective and efficient delignification (83.2 %) and xylan removal (76.3 %) from canola straw by CTAB:LA:Fe3+, resulting in an increased saccharification efficiency of 81.8 %. Besides, abundant furfural (3.36 g/L) and xylo-oligosaccharides (3.41 g/L) were co-produced during pretreatment, providing comprehensive insights into the efficient co-production of fermentable sugars, furfural, and xylo-oligosaccharides. A thorough analysis of mass balance and energy flow was conducted to evaluate the entire process. Then, molecular dynamics (MD) simulations and quantum chemical calculations were performed on lignocellulosic biomass models and elucidate the interactions between the biomass and CTAB:LA:Fe3+ at the molecular level through the independent gradient model (IGM), thus explaining the high removal efficiency of hemicellulose and lignin. Furthermore, the physicochemical properties of the DESs were investigated, and molecular-level insights into the mechanism of CTAB:LA:Fe3+ pretreatment of lignocellulosic biomass were proposed in conjunction with biomass characterization such as FT-IR and CLSM, as well as MD simulations.