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.

Lignin detaching from the oxidative delignified softwood during enzymatic hydrolysis and its effect on carbohydrate saccharification.

Most studies about the influence of lignin on enzymatic digestibility of lignocellulose have focused on the content and properties, but less on the detaching behavior of lignin. The samples were prepared from Pinus massoniana wood chips by kraft cooking followed by delignification using oxygen/alkali (KP-O) and chlorine dioxide (KP-D), respectively. Two oxidative delignified samples with a similar lignin content were subject to enzymatic hydrolysis at both pH of 5.0 and 5.5 to investigate the effects of lignin detached rate (LDR) on substrate enzymatic digestibility (SED). The LDRs and the SEDs from both samples increased with the enzymatic hydrolysis time, and the situations of KP-D were much higher than those of KP-O under the same enzymatic hydrolysis time. The results of enzymatic hydrolysis at an elevated pH of 5.5 and the changes in concentration of free cellulase of the two samples indicated that the lignin detaching increased the free cellulase concentration, and thus promoted the enzymatic digestibility. Moreover, lignin distribution analysis by X-ray photoelectric spectroscopy and confocal laser scanning microscopy indicated surface lignin being preferentially detached. This work provided a reference for rationally designing pretreatment strategies, which can improve the efficiency of enzyme hydrolysis of lignocellulosic biomass.

Modified 1,4-butanediol organosolv pretreatment on hardwoodandsoftwood for efficient coproduction of fermentable sugars and lignin antioxidants.

In this work, 1,4-butanediol (BDO) organosolv pretreatment was modified with different additives for efficient coproduction of fermentable sugars and lignin antioxidants from hardwood poplar and softwood masson pine. It was found additives more greatly improved pretreatment efficacy of softwood than hardwood. 3-hydroxy-2-naphthoic acid (HNA) addition introduced hydrophilic acid groups to lignin structure, while 2-naphthol-7-sulphonate (NS) addition promoted lignin removal, both improving cellulose accessibility for enzymatic hydrolysis. Consequently, BDO pretreatment with 90 mM acid and 2-naphthol-7-sulphonate addition achieved near complete cellulose hydrolysis (97.98%) and maximized sugar yield of 88.23% from masson pine at 2% cellulose and 20 FPU/g enzyme loading. More importantly, the recovered lignin possessed great antioxidant activity (RSI = 2.48), due to increased phenolic OH groups, reduced aliphatic OH groups and molecular weight. Results indicated the modified BDO pretreatment could significantly improve enzymatic saccharification of highly-recalcitrant softwood, while enabling coproduction of high-performance lignin antioxidants for full biomass utilization.

Dissolution of lignocellulose with high lignin content in AlCl3/ZnCl2 aqueous system and properties of the regenerated cellulose film.

Herein, a novel method for dissolving lignocellulose at room temperature is proposed by combining deep eutectic solvents (DES) pretreatment and subsequent dissolution in AlCl3/ZnCl2 aqueous system. Results showed that DES pretreatment could significantly increase the dissolubility of lignin-containing cellulose (CL) samples in AlCl3/ZnCl2 aqueous system. The dissolution ratio of the CL sample with 15.6 % lignin content in AlCl3/ZnCl2·3H2O solvent was as high as 90 %. Besides, the mechanism for the remarkable dissolution of CL samples in low water AlCl3/ZnCl2 aqueous solvent was also proposed. Moreover, the dissolved CL sample was regenerated for the production of lignocellulose films, which have excellent ultraviolet (UV) blocking, hydrophobic, mechanical strength, and natural degradation properties. In particular, the films could be completely naturally degraded after 10 days, which provided a promising way to prepare biodegradable lignocellulose materials, and to encourage the potential utilization of renewable lignocellulose in packaging industry.

Modified acid pretreatment to alter physicochemical properties of biomass for full cellulose/hemicellulose utilization.

Acid pretreatment of biomass decomposed hemicelluloses but could not effectively remove lignin, which hindered biomass saccharification and carbohydrates utilization. In this work, 2-naphthol-7-sulfonate (NS) and sodium bisulfite (SUL) were simultaneously added to acid pretreatment, which was found to synergistically increase hydrolysis yield of cellulose from 47.9 % to 90.6 %. Based on in-depth investigations, strong linear correlations were observed between cellulose accessibility and lignin removal, fiber swelling, CrI/cellulose ratio, cellulose crystallite size, respectively, indicating that some physicochemical characteristics of cellulose played significant roles in improving cellulose hydrolysis yield. After enzymatic hydrolysis, 84 % carbohydrates could be liberated and recovered as fermentable sugars for subsequent utilization. Mass balance illustrated that for 100 kg raw biomass, 15.1 kg xylonic acid and 20.5 kg ethanol could be co-produced, indicating the efficient utilization of biomass carbohydrates.

Improving enzymatic saccharification of hardwood through lignin modification by carbocation scavengers and the underlying mechanisms.

In this work, the beneficial effect of carbocation scavenger additives on hardwood pretreatment was revealed by significantly improved biomass saccharification: cellulose hydrolysis yield was increased by over 15% after steam pretreatment of poplar, while that was enhanced by more than 48% after dilute acid pretreatment. Besides, the relative contributions of lignin towards enzyme binding and physical barrier effect for proposed mechanisms were quantified. Results indicated that the addition of carbocation scavenger, 2-naphthol-7-sulfonate, resulted in acid groups incorporation of 62.36 mmol/kg to lignin, which mitigated enzyme non-productive binding. Moreover, enlarged biomass porosity and reduced surface lignin coverage were detected through BET and XPS analysis, respectively, which mostly related to the diminished physical barrier effect of lignin. As a result, the lignin inhibitions were significantly suppressed through the addition of carbocation scavenger, giving rise to significantly improved enzymatic hydrolysis of hardwood.

Integrated process for the coproduction of fermentable sugars and lignin adsorbents from hardwood.

This work proposed an integrated process based on alkali-sulfite (AlkSul) pretreatment to coproduce fermentable sugars and lignin adsorbents from hardwood. Different from conventional liquid hot water (LHW) pretreatment, this pretreatment improved cellulose accessibility through selective lignin removal and modification, resulting in significantly enhanced biomass saccharification. Over 75% of the original cellulose and hemicellulose was released and could be recovered as fermentable sugars after pretreatment and subsequent enzymatic hydrolysis. Meanwhile, lignin residues from pretreatment hydrolysate and enzymatic hydrolysate showed lead ions adsorption capacities of 156.25 and 68.49 mg/g, respectively, indicating both streams of lignin residues were favorable adsorbents for heavy metal ions. The improved adsorption capacity of lignin residues was primarily due to the lignin modification as sulfur-containing functional groups incorporation during the integrated pretreatment. Results demonstrated the integrated alkali-sulfite pretreatment improved biomass saccharification, while coproducing lignin adsorbents for wastewater treatment, which can promote the sustainability of lignocellulosic biorefinery.

Two-stage alkali-oxygen pretreatment capable of improving biomass saccharification for bioethanol production and enabling lignin valorization via adsorbents for heavy metal ions under the biorefinery concept.

Converting lignin into value-added products in current lignocellulosic biorefineries has been challenging, which in turn restricts the commercialization of many lignocellulosic biorefineries. In this work, a two-stage alkali-oxygen assisted liquid hot water pretreatment (AlkOx) was proposed as the first step of biorefinery. This alkali-oxygen pretreatment facilitated biomass fractionation by solubilizing majority of lignin in water-soluble fraction, while remaining most of cellulose and hemicellulose in water-insoluble fraction. As a result, biomass saccharification was significantly improved by selective removal and oxidative modification of lignin through alkali-oxygen pretreatment. Moreover, lignin residues from both pretreatment hydrolysate and enzymatic hydrolysate were shown to be favorable adsorbents for Pb(II) ions, with adsorption capacity of 263.16 and 90.91 mg/g, respectively. Results demonstrated that this integrated process could not only improve biomass saccharification but also enable lignin valorization, which encouraged the holistic utilization of lignin residues as part of an integrated biorefinery.

Hydrocarbon rich bio-oil production, thermal behavior analysis and kinetic study of microwave-assisted co-pyrolysis of microwave-torrefied lignin with low density polyethylene.

This study aims to enhance the quality of biofuel through microwave torrefaction pretreatment for lignin. Low density polyethylene (LDPE) was added as a hydrogen source during microwave co-pyrolysis along with the microwave-torrefied lignin (MTL). The thermal degradation behavior and kinetic study of MTL co-pyrolysis with LDPE by microwave-assisted heating was investigated as well. The results indicated that the hydrocarbon content in the bio-oil obtained from microwave co-pyrolysis of MTL and LDPE increased significantly (about 80%). It was also noticed that the aromatic hydrocarbon content increased from 1.94% to 22.83% with the addition of LDPE. Thermal behavior analysis and reaction kinetic study showed that the addition of LDPE into MTL had the effect of promoting thermal degradation and improving reaction rate during microwave-assisted pyrolysis.

The influence of lignin on steam pretreatment and mechanical pulping of poplar to achieve high sugar recovery and ease of enzymatic hydrolysis.

With the goal of enhancing overall carbohydrate recovery and reducing enzyme loading refiner mechanical pulping and steam pretreatment (210°C, 5 min) were used to pretreat poplar wood chips. Neutral sulphonation post-treatment indicated that, although the lignin present in the steam pretreated substrate was less reactive, the cellulose-rich, water insoluble component was more accessible to cellulases and Simons stain. This was likely due to lignin relocation as the relative surface lignin measured by X-ray photoelectron spectroscopy increased from 0.4 to 0.8. The integration of sulphite directly into steam pretreatment resulted in the solubilisation of 60% of the lignin while more than 80% of the carbohydrate present in the original substrate was recovered in the water insoluble fraction after Na2CO3 addition. More than 80% of the sugars present in the original cellulose and xylan could be recovered after 48 h using an enzyme loading of 20 mg protein/g cellulose at a 10% substrate concentration.

Lactic Acid Production from Pretreated Hydrolysates of Corn Stover by a Newly Developed Bacillus coagulans Strain.

An inhibitor-tolerance strain, Bacillus coagulans GKN316, was developed through atmospheric and room temperature plasma (ARTP) mutation and evolution experiment in condensed dilute-acid hydrolysate (CDH) of corn stover. The fermentabilities of other hydrolysates with B. coagulans GKN316 and the parental strain B. coagulans NL01 were assessed. When using condensed acid-catalyzed steam-exploded hydrolysate (CASEH), condensed acid-catalyzed liquid hot water hydrolysate (CALH) and condensed acid-catalyzed sulfite hydrolysate (CASH) as substrates, the concentration of lactic acid reached 45.39, 16.83, and 18.71 g/L by B. coagulans GKN316, respectively. But for B. coagulans NL01, only CASEH could be directly fermented to produce 15.47 g/L lactic acid. The individual inhibitory effect of furfural, 5-hydroxymethylfurfural (HMF), vanillin, syringaldehyde and p-hydroxybenzaldehyde (pHBal) on xylose utilization by B. coagulans GKN316 was also studied. The strain B. coagulans GKN316 could effectively convert these toxic inhibitors to the less toxic corresponding alcohols in situ. These results suggested that B. coagulans GKN316 was well suited to production of lactic acid from undetoxified lignocellulosic hydrolysates.