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Abstract Background Soil-derived exogenous ash (EA) poses a challenge toward lignocellulosic autohydrolysis due to its buffering capacity. Previous works focusing on this phenomenon have failed to also investigate the role that soluble salts, and organic matter plays in this system. Herein, sodium phosphate and sodium humate were employed as model buffering compounds representing soluble salts and organic matter and dosed into a de-ashed wheat straw (DWS) autohydrolysis process to show the potential impacts of WS attached soil conditioners on the WS autohydrolysis efficiency which would further affect the enzymatic digestibility of autohydrolyzed WS. Results Results showed that with the increasing loadings of sodium phosphate and sodium humate resulted in elevated pH values (from 4.0 to 5.1 and from 4.1 to 4.7, respectively). Meanwhile, the reductions of xylan removal yields from ~ 84.3–61.4% to 72.3–53.0% by loading (1–30 g/L) sodium phosphate and sodium humate during WS autohydrolysis lead to a significant decrease of cellulose accessibilities which finally lead to a reduction of the enzymatic digestibility of autohydrolyzed WS from ~ 75.4–77.2% to 47.3–57.7%. Conclusion The existence of different types soil conditioner model compounds results in various component fractions from autohydrolyzed WS in the process of autohydrolysis. A lack of sufficient xylan removal was found to drive the significant decrease in enzymatic accessibility. The results demonstrated the various effects of two typical tested soil conditioners on WS autohydrolysis and enzymatic hydrolysis.

Abstract Background The acid buffering capacity of high free ash in waste wheat straw (WWS) has been revealed to be a significant hindrance on the efficiency of autohydrolysis pretreatment. Previous researches have mainly relied on washing to eliminate the influence of ash, and the underlying mechanism of the ash influencing was not extensively investigated. Presently, studies have found that cations can destroy the acid buffering capacity of ash through cation exchange. Herein, different cations were applied to presoak WWS with the aim to overcome the negative effects of ash on autohydrolysis efficiency, further improving its enzymatic digestibility. Results Results showed that cations can be adsorbed on the surface of the material by electrostatic adsorption to change the acid buffering capacity of WWS. The acid buffering capacity of 120 mM Fe2+ presoaked WWS is reduced from 226.3 mmol/pH-kg of original WWS to 79.3 mmol/pH-kg. This reduced the autohydrolysis pretreatment medium pH from 5.7 to 3.8 and promoted the removal of xylan from 61.7 to 83.7%. In addition, the enzymatic digestibility of WWS was enhanced from 49.7 to 86.3% by presoaking with 120 mM Fe2+ solution. The relationship between enzymatic accessibility and hydrophobicity with enzymatic digestibility of the autohydrolyzed WWS was analyzed. Conclusions The results showed that the acid buffering capacity of the high free ash was detrimental for the autohydrolysis efficiency of WWS. After WWS was presoaked with different cations, the acid buffering capacity of ash was weakened by cation exchange and electrostatic adsorption, which improved the autohydrolysis efficiency. The results expound that the enzymatic digestibility of WWS can be enhanced through presoaking to reduce the ash-influencing effect on autohydrolysis.

Background: Soil-derived exogenous ash (EA) poses a challenge toward lignocellulosic autohydrolysis due to its buffering capacity. Previous works focusing on this phenomenon have failed to also investigate the role that soluble salts, and organic matter plays in this system. Herein, sodium phosphate and sodium humate were employed as model buffering compounds representing soluble salts and organic matter and dosed into a de-ashed wheat straw (DWS) autohydrolysis process to show the potential impacts of WS attached soil conditioners on the WS autohydrolysis efficiency which would further affect the enzymatic digestibility of autohydrolyzed WS. Results: Results showed that with the increasing loadings of sodium phosphate and sodium humate resulted in elevated pH values (from 4.0 to 5.1 and from 4.1 to 4.7, respectively). Meanwhile, the reductions of xylan removal yields from ~ 84.3–61.4% to 72.3–53.0% by loading (1–30 g/L) sodium phosphate and sodium humate during WS autohydrolysis lead to a significant decrease of cellulose accessibilities which finally lead to a reduction of the enzymatic digestibility of autohydrolyzed WS from ~ 75.4–77.2% to 47.3–57.7%. Conclusion: The existence of different types soil conditioner model compounds results in various component fractions from autohydrolyzed WS in the process of autohydrolysis. A lack of sufficient xylan removal was found to drive the significant decrease in enzymatic accessibility. The results demonstrated the various effects of two typical tested soil conditioners on WS autohydrolysis and enzymatic hydrolysis. [ABSTRACT FROM AUTHOR]

Background: During pretreatment, hemicellulose is removed from biomass via proton-catalyzed hydrolysis to produce soluble poly- and mono-saccharides. Many kinetic models have been proposed but the dependence of rate on proton concentration is not well-defined; autohydrolysis and dilute-acid hydrolysis models apply very different treatments despite having similar chemistries. In this work, evolution of proton concentration is examined during both autohydrolysis and dilute-acid hydrolysis of hemicellulose from green bamboo. An approximate mathematical model, or "toy model", to describe proton concentration based upon conservation of mass and charge during deacetylation and ash neutralization coupled with a number of competing equilibria, was derived. The model was qualitatively compared to experiments where pH was measured as a function of time, temperature, and initial acid level. Proton evolution was also examined at room temperature to decouple the effect of ash neutralization from deacetylation. Results: The toy model predicts the existence of a steady-state proton concentration dictated by equilibrium constants, initial acetyl groups, and initial added acid. At room temperature, it was found that pH remains essentially constant both at low initial pH and autohydrolysis conditions. Acid is likely in excess of the neutralization potential of the ash, in the former case, and the kinetics of neutralization become exceedingly small in the latter case due to the low proton concentration. Finally, when the hydrolysis reaction proceeded at elevated temperatures, one case of nonmonotonic behavior in which the pH initially increased, and then decreased at longer times, was found. This is likely due to the difference in rates between neutralization and deacetylation. Conclusions: The model and experimental work demonstrate that the evolution of proton concentration during hydrolysis follows complex behavior that depends upon the acetyl group and ash content of biomass, initial acid levels and temperature. In the limit of excess added acid, pH varies very weakly with time. Below this limit, complex schemes are found primarily related to the selectivity of deacetylation in comparison to neutralization. These findings indicate that a more rigorous approach to models of hemicellulose hydrolysis is needed. Improved models will lead to more efficient acid utilization and facilitate process scale-up. [ABSTRACT FROM AUTHOR]

Background: Autohydrolysis of lignocellulosic biomass in liquid hot water has been widely studied owing to its high efficiency and relatively low cost. In the perspective of industrial applications, continuous or semi-continuous processes are more interesting than batch systems. Moreover, microwave heating of pretreatment systems has been proposed to intensify the kinetics of the process. In this study, the autohydrolysis of Arundo donax was performed in pure liquid hot water using a microwave-heated batch reactor and a semi-continuous flow-through reaction system with fast heating rate at the same operating conditions with the aim of performing a systematic comparison between the two different experimental apparatuses. Results: The effect of process temperature and time, biomass to water mass to volume ratio and water flow rate on the concentration and yield of hydrolysis products was investigated. The flow-through set-up allowed us to reach biomass solubilization up to 44.5 wt% on dry basis, while the batch system stopped at 34.5 wt% suggesting that the mass transfer could be the rate-determining step in the solubilization of the constituting biopolymers. For example, in the flow-through layout, using a flow rate of 3.5 mL/min at 200 °C with 20 min of processing time, quantitative recovery of hemicellulose was obtained with limited formation of degradation products. Interestingly, higher cellulose/ hemicellulose extraction ratios were found using the microwave-assisted batch reactor. FTIR analyses of the solid residues recovered after the pretreatment offered independent information on the fractions of liquefied biopolymers complementary to those derived from HPLC and UV-Vis spectroscopy. Conclusions: Collected experimental results indicated that the flow-through system can be adopted to obtain complete solubilization of the hemicellulose fraction of Arundo donax addressing the product distribution in soluble compounds towards fermentable sugars with limited formation of sugar degradation products and with limited penalty in terms of dilution of the hydrolysate solution. It was also found that microwaves can promote cellulose depolymerization and solubilization, thus allowing a more comprehensive utilization of the biomass and that infrared spectroscopy can be a useful technique to estimate the effect of the pretreatment. [ABSTRACT FROM AUTHOR]

Background: The acid buffering capacity of high free ash in waste wheat straw (WWS) has been revealed to be a significant hindrance on the efficiency of autohydrolysis pretreatment. Previous researches have mainly relied on washing to eliminate the influence of ash, and the underlying mechanism of the ash influencing was not extensively investigated. Presently, studies have found that cations can destroy the acid buffering capacity of ash through cation exchange. Herein, different cations were applied to presoak WWS with the aim to overcome the negative effects of ash on autohydrolysis efficiency, further improving its enzymatic digestibility. Results: Results showed that cations can be adsorbed on the surface of the material by electrostatic adsorption to change the acid buffering capacity of WWS. The acid buffering capacity of 120 mM Fe2+ presoaked WWS is reduced from 226.3 mmol/pH-kg of original WWS to 79.3 mmol/pH-kg. This reduced the autohydrolysis pretreatment medium pH from 5.7 to 3.8 and promoted the removal of xylan from 61.7 to 83.7%. In addition, the enzymatic digestibility of WWS was enhanced from 49.7 to 86.3% by presoaking with 120 mM Fe2+ solution. The relationship between enzymatic accessibility and hydrophobicity with enzymatic digestibility of the autohydrolyzed WWS was analyzed. Conclusions: The results showed that the acid buffering capacity of the high free ash was detrimental for the autohydrolysis efficiency of WWS. After WWS was presoaked with different cations, the acid buffering capacity of ash was weakened by cation exchange and electrostatic adsorption, which improved the autohydrolysis efficiency. The results expound that the enzymatic digestibility of WWS can be enhanced through presoaking to reduce the ash-influencing effect on autohydrolysis. [ABSTRACT FROM AUTHOR]