Quantitative correlation analysis between particle liquefaction and saccharification through dynamic changes of slurry rheological behavior and particle characteristics during high-solid enzymatic hydrolysis of sugarcane bagasse.

This study identified the intrinsic relationships among slurry rheology, particle characteristics, and lignocellulosic liquefaction/saccharification based on correlation analysis and principal component analysis during the hydrolysis of sugarcane bagasse pretreated by deep eutectic solvents (DES) and mechanical milling (MM). The DES-MM pretreated lignocellulosic slurry (20% solids) exhibited high apparent viscosity of 1.4 × 104 Pa·s and shear stress of 929.0 Pa under steady state. Glucose production had a negative linear correlation with slurry viscosity (R2, 0.69-0.97), whereas its correlation with yield stress (R2, 0.85-0.98) depended on the particle liquefaction rate. The availability of free water provided a major contribution to improving slurry rheology. However, the size reduction of submillimeter particles and the changes in particle hydrophilicity during liquefaction were not significantly correlated with rheological changes. Various interrelated particle characteristics and rheological changes were integrated into two simple principal variables to predict glucose production with a high R2 of 0.96.

Dual assistance of surfactants in glycerol organosolv pretreatment and enzymatic hydrolysis of lignocellulosic biomass for bioethanol production.

This study investigated an innovative strategy of incorporating surfactants into alkaline-catalyzed glycerol pretreatment and enzymatic hydrolysis to improve lignocellulosic biomass (LCB) conversion efficiency. Results revealed that adding 40 mg/g PEG 4000 to the pretreatment at 195 °C obtained the highest glucose yield (84.6%). This yield was comparable to that achieved without surfactants at a higher temperature (240 °C), indicating a reduction of 18.8% in the required heat input. Subsequently, Triton X-100 addition during enzymatic hydrolysis of PEG 4000-assisted pretreated substrate increased glucose yields to 92.1% at 6 FPU/g enzyme loading. High-solid fed-batch semi-simultaneous saccharification and co-fermentation using this dual surfactant strategy gave 56.4 g/L ethanol and a positive net energy gain of 1.4 MJ/kg. Significantly, dual assistance with surfactants rendered 56.3% enzyme cost savings compared to controls without surfactants. Therefore, the proposed surfactant dual-assisted promising approach opens the gateway to economically viable enzyme-mediated LCB biorefinery.

Surfactants facilitated glycerol organosolv pretreatment of lignocellulosic biomass by structural modification for co-production of fermentable sugars and highly reactive lignin.

This study reported that surfactants could facilitate the organosolv pretreatment of lignocellulosic biomass (LCB) to produce fermentable sugars and highly active lignin. Under the optimized conditions, the surfactant-assisted glycerol organosolv (saGO) pretreatment achieved 80.7% delignification with a retention of 93.4% cellulose and 83.0% hemicellulose. The saGO pretreated substrate exhibited an excellent enzymatic hydrolyzability, achieving 93% of glucose yield from the enzymatic hydrolysis at 48 h. Structural analysis showed that the saGO lignin contained rich ß-O-4 bondings with less repolymerization and lower phenolic hydroxyl groups, thus forming highly reactive lignin fragments. The analysis evidenced that the surfactant graft the lignin by structural modification, which was responsible for the excellent substrate hydrolyzability. The co-production of fermentable sugars and organosolv lignin almost recovered a gross energy (87.2%) from LCB. Overall, the saGO pretreatment holds a lot of promise for launching a novel pathway towards lignocellulosic fractionation and lignin valorization.

Advances in organosolv modified components occurring during the organosolv pretreatment of lignocellulosic biomass.

The valorization of organosolv pretreatment (OP) is a required approach to the industrialization of the current enzyme-mediated lignocellulosic biorefinery. Recent literature has demonstrated that the solvolysis happening in the OP can modify the soluble components into value-added active compounds, namely organosolv modified lignin (OML) and organosolv modified sugars (OMSs), in addition to protecting them against excessive degradation. Among them, the OML is coincidental with the "lignin-first" strategy that should render a highly reactive lignin enriched with ß-O-4 linkages and less condensed structure by organosolv grafting, which is desirable for the transformation into phenolic compounds. The OMSs are valuable glycosidic compounds mainly synthesized by trans-glycosylation, which can find potential applications in cosmetics, foods, and healthcare. Therefore, a state-of-the-art OP holds a big promise of lowering the process cost by the valorization of these active compounds. Recent advances in organosolv modified components are reviewed, and perspectives are made for addressing future challenges.

Advances and perspectives on mass transfer and enzymatic hydrolysis in the enzyme-mediated lignocellulosic biorefinery: A review.

Enzymatic hydrolysis is a critical process for the cellulase-mediated lignocellulosic biorefinery to produce sugar syrups that can be converted into a whole range of biofuels and biochemicals. Such a process operating at high-solid loadings (i.e., scarcely any free water or roughly ≥ 15% solids, w/w) is considered more economically feasible, as it can generate a high sugar concentration at low operation and capital costs. However, this approach remains restricted and incurs "high-solid effects", ultimately causing the lower hydrolysis yields with increasing solid loadings. The lack of available water leads to a highly viscous system with impaired mixing that exhibits strong transfer resistance and reaction limitation imposed on enzyme action. Evidently, high-solid enzymatic hydrolysis involves multi-scale mass transfer and multi-phase enzyme reaction, and thus requires a synergistic perspective of transfer and biotransformation to assess the interactions among water, biomass components, and cellulase enzymes. Porous particle characteristics of biomass and its interface properties determine the water form and distribution state surrounding the particles, which are summarized in this review aiming to identify the water-driven multi-scale/multi-phase bioprocesses. Further aided by the cognition of rheological behavior of biomass slurry, solute transfer theories, and enzyme kinetics, the coupling effects of flow-transfer-reaction are revealed under high-solid conditions. Based on the above basic features, this review lucidly explains the causes of high-solid hydrolysis hindrances, highlights the mismatched issues between transfer and reaction, and more importantly, presents the advanced strategies for transfer and reaction enhancements from the viewpoint of process optimization, reactor design, as well as enzyme/auxiliary additive customization.

Efficient co-production of xylooligosaccharides and glucose from lignocelluloses by acid/pentanol pretreatment: Synergetic role of lignin removal and inhibitors.

A novel technology for co-production of xylooligosaccharides (XOS) and glucose from Monterey pine sawdust and wheat straw was introduced using dilute acid (DA)/pentanol pretreatment. Effects of pretreatment severity (PS), lignin removal, and inhibitors with byproduct concentrations on XOS production were investigated. Optimal identified conditions (PS: 3.71; 170 °C, 45 min) resulted in maximum XOS of 48.65 % (pine sawdust) and 46.85 % (wheat straw), due to appropriate lignin removal (pine sawdust, 88.5 %; wheat straw, 89.7 %) and formation of small amounts of inhibitors and byproducts. Enzymatic hydrolysis of optimal pretreated solid residues yielded 88.65 % and 93.34 % glucose in pine sawdust and wheat straw, respectively. Biomass characterization revealed that DA/pentanol pretreatment enhanced porosity and pore size along with removal of amorphous fractions in both samples, thereby increasing cellulose accessibility and glucose yield. This study demonstrated lignin removal and low formation of inhibitors and byproducts, effectively enhancing XOS and glucose production from lignocellulosic biomass.

Positive role of non-catalytic proteins on mitigating inhibitory effects of lignin and enhancing cellulase activity in enzymatic hydrolysis: Application, mechanism, and prospective.

Fermentable sugar production from lignocellulosic biomass has received considerable attention and has been dramatic progress recently. However, due to low enzymatic hydrolysis (EH) yields and rates, a high dosage of the costly enzyme is required, which is a bottleneck for commercial applications. Over the last decades, various strategies have been developed to reduce cellulase enzyme costs. The progress of the non-catalytic additive proteins in mitigating inhibition in EH is discussed in detail in this review. The low efficiency of EH is mostly due to soluble lignin compounds, insoluble lignin, and harsh thermal and mechanical conditions of the EH process. Adding non-catalytic proteins into the EH is considered a simple and efficient approach to boost hydrolysis yield. This review discussed the multiple mechanical steps involved in the EH process. The effect of physicochemical properties of modified lignin on EH and its interaction with cellulase and cellulose are identified and discussed, which include hydrogen bonding, hydrophobic, electrostatic, and cation-π interactions, as well as physical barriers. Moreover, the effects of different conditions of EH that lead to cellulase deactivation by thermal and mechanical mechanisms are also explained. Finally, recent advances in the development, potential mechanisms, and economic feasibility of non-catalytic proteins on EH are evaluated and perspectives are presented.

A tailored bifunctional carbon catalyst for efficient glycosidic bond fracture and selective hemicellulose fractionation.

This study proposed a mild chlorination-sulfonation approach to synthesize magnetic carbon acid bearing with catalytic SO3H and adsorption Cl bifunctional sites on polydopamine coating. The catalysts exerted good textural structure and surface chemical properties (i.e., porosity, high specific surface area of >70 m2/g, high catalytic activity with 0.86-1.1 mmol/g of SO3H sites and 0.8%-1.9% of Cl sites, and abundant hydrophilic functional groups), rendering a maximum cellobiose adsorption efficiency of ∼40% within 6 h. Moreover, the catalysts had strong fracture characteristics on different α-/ß-glycosidic bonds with 85.4%-93.9% of disaccharide conversion, while selectively fractionating hemicellulose from wheat straw with 64.3% of xylose yield and 93.4% of cellulose retention. Due to the stable interaction between parent polydopamine support with Fe core and functional groups, the catalysts efficiently recovered by simple magnetic separation had good reusability with minimal losses in catalytic activity.

Towards biomass production and wastewater treatment by enhancing the microalgae-based nutrients recovery from liquid digestate in an innovative photobioreactor integrated with dialysis bag.

Microalgae-based nutrients recovery from liquid anaerobic digestate of swine manure has been a hotspot in recent decades. Nevertheless, in consideration of the high NH4+-N content and poor light penetrability exhibited by the original liquid digestate, uneconomical pretreatment on liquid digestate including centrifugation and dilution are indispensable before microalgae cells inoculation. Herein, aiming at eliminating the energy-intensive and freshwater-consuming pretreatment on liquid digestate and enhancing microalgae growth, the dialysis bag which permits nutrients transferring across its wall surface whereas retains almost all matters characterized by impeding light transmission within the raw liquid digestate was integrated into a column photobioreactor (DB-PBR). Consequently, light availability of microalgae cells in DB-PBR was elevated remarkably and thus contributed to a 357.58% improvement on microalgae biomass concentration in DB-PBR than the conventional PBR under 80 µmol m-2 s-1. Likewise, superior nutrients removal efficiencies from liquid digestate were obtained in DB-PBR (NH4+-N: 74.84%, TP: 63.75%) over the conventional PBR (NH4+-N: 30.27%, TP: 16.86%). Furthermore, higher microalgae biomass concentration (1.87 g L-1) and nutrients removal efficiencies (NH4+-N: 95.12%, TP: 76.87%) were achieved in the DB-PBR by increasing the light intensity to 140 µmol m-2 s-1. More importantly, the DB-PBR may provide a simple and greener solution to purify other kinds of wastewater.

Glycerol organosolv pretreatment can unlock lignocellulosic biomass for production of fermentable sugars: Present situation and challenges.

The complex structure of lignocellulosic biomass forms the recalcitrance to prevent the embedded holo-cellulosic sugars from undergoing the biodegradation. Therefore, a pretreatment is often required for an efficient enzymatic lignocellulosic hydrolysis. Recently, glycerol organosolv (GO) pretreatment is revealed potent in selective deconstruction of various lignocellulosic biomass and effective improvement of enzymatic hydrolysis. Evidently, the GO pretreatment is capable to modify the structure of dissolved components by glycerolysis, i.e., by trans-glycosylation onto glyceryl glycosides and by hydroxylation grafting onto glyceryl lignin. Such modifications tend to protect these main components against excessive degradation, which can be mainly responsible for the obviously less fermentation inhibitors arising in the GO pretreatment. This pretreatment can provide opportunities for valorization of emerging lignocellulosic biorefinery with production of value-added biochemicals. Recent advances in GO pretreatment of lignocellulosic biomass followed by enzymatic hydrolysis are reviewed, and perspectives are made for addressing remaining challenges.

Carbon cloth facilitates semi-continuous anaerobic digestion of organic wastewater rich in volatile fatty acids from dark fermentation.

The anaerobic digestion of wastewater rich in volatile fatty acids (VFAs) provides a sustainable approach for methane production whilst reducing environmental pollution. However, the anaerobic digestion of VFAs may not be stable during long-term operation under a short hydraulic retention time. In this study, conductive carbon cloth was supplemented to investigate the impacts on the anaerobic digestion of VFAs in wastewater sourced from dark fermentation. The results demonstrated that the failure of anaerobic digestion could be avoided when carbon cloth was supplemented. In the stable stage, the methane production rate with carbon cloth supplementation was improved by 200-260%, and the chemical oxygen demand (COD) removal efficiency was significantly enhanced compared with that in the control without carbon cloth. The relative abundance of potential exoelectrogens on the carbon cloth was increased by up to 8-fold compared with that in the suspension. Electrotrophic methanogens on the carbon cloth were enriched by 4.2-17.2% compared with those in the suspension. The genera Ercella and Petrimonas along with the methanogenic archaea Methanosaeta and Methanosarcina on the carbon cloth may facilitate direct interspecies electron transfer, thereby enhancing methane production.

Effects of foam nickel supplementation on anaerobic digestion: Direct interspecies electron transfer.

Stimulating direct interspecies electron transfer with conductive materials is a promising strategy to overcome the limitation of electron transfer efficiency in syntrophic methanogenesis of industrial wastewater. This paper assessed the impact of conductive foam nickel (FN) supplementation on syntrophic methanogenesis and found that addition of 2.45 g/L FN in anaerobic digestion increased the maximum methane production rate by 27.4 % (on day 3) while decreasing the peak production time by 33 % as compared to the control with no FN. Cumulative methane production from day 2 to 6 was 14.5 % higher with addition of 2.45 g/L FN than in the control. Levels of FN in excess of 2.45 g/L did not show benefits. Cyclic voltammetry results indicated that the biofilm formed on the FN could generate electrons. The dominant bacterial genera in suspended sludge were Dechlorobacter and Rikenellaceae DMER64, whereas that in the FN biofilm was Clostridium sensu stricto 11. The dominant archaea Methanosaeta in the FN biofilm was enriched by 14.1 % as compared to the control.

Hydrogen fermentation of organic wastewater with high ammonium concentration via electrodialysis system.

An advanced electrodialysis fermentation system was set up to remove ammonium during hydrogen fermentation. When the voltage was increased from 0 to 6 V, the average ammonium removal rate was improved from 8.7 to 31.1 mg/L/h at an initial ammonium concentration of 3000 mg/L. A model based on the Nernst-Plank equation and porous media properties of ion exchange membranes was successfully implemented to predict the ammonium removal performance. When such a system was fed with synthetic wastewater at an ammonium concentration of 3000 mg/L for hydrogen fermentation, a significant increase in specific hydrogen yield was observed in the experiment group at 4 V. Specific hydrogen yield was 225.0 mL/g glucose, this value is 47.9% higher than the control. Moreover, ammonium concentration in experiment group was reduced to 701.6 mg/L at 72 h when voltage was set at 4 V, which is 63.7% lower than that in 0 V experiment group.

Enhancing fermentative hydrogen production with the removal of volatile fatty acids by electrodialysis.

A three-chamber electrodialysis bioreactor comprising fermentation, cathode and anode chambers was proposed to remove in situ volatile fatty acids during hydrogen fermentation. The electrodialysis voltage of 4 V resulted in a volumetric hydrogen productivity of 1878.0 mL/L from the fermentation chamber, which is 55.4% higher than that (1208.5 mL/L) of the control group without voltage applied. Gas production was not observed in the cathode and anode chambers throughout fermentation. By applying different voltages (0-6 V), the hydrogen content accumulated to 54.6%-84.7%, and it exhibited increases of 7.1%-66.4% compared with that of the control. Meanwhile, the maximum concentrations of acetate and butyrate in the fermentation chamber decreased to 10.3 and 13.1 mmol/L at a voltage of 4 V, respectively, which are 68.0% and 62.4% lower than that for the control.

An annular photobioreactor with ion-exchange-membrane for non-touch microalgae cultivation with wastewater.

To eliminate the negative impacts of pollutants in wastewater (such as suspended solids, excess N, P, heavy metals) on microalgae growth, an annular ion-exchange-membrane photobioreactor (IEM-PBR) was proposed in this study. The IEM-PBR could avoid direct mixing of algae cells with wastewater by separating them into two chambers. In the IEM-PBR, the nutrients (mainly N and P) in wastewater continuously permeated into microalgae cultures through the ion-exchange-membrane for microalgae growth, while the pollutants hardly permeated into microalgae cultures. Three types of representative wastewater were investigated to evaluate the performance of the IEM-PBR. When cultivated with wastewater containing excess nutrients, high turbidity and excess heavy metals, microalgae biomass concentrations were significantly improved from 2.34, 2.15 and 0gL(-1) in the traditional PBR to 4.24, 3.13 and 2.04gL(-1) in the IEM-PBR. Correspondingly, the removal efficiencies of N and P in wastewater were also greatly improved by using the IEM-PBR.