Insight into the evolution of the proton concentration during autohydrolysis and dilute-acid hydrolysis of hemicellulose

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 non-monotonic 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.Applied Science, Faculty ofForestry, Faculty ofNon UBCChemical and Biological Engineering, Department ofWood Science, Department ofReviewedFacult

A biorefinery scheme to fractionate bamboo into high-grade dissolving pulp and ethanol

Background: Bamboo is a highly abundant source of biomass which is underutilized despite having a chemical composition and fiber structure similar as wood. The main challenge for the industrial processing of bamboo is the high level of silica, which forms water-insoluble precipitates negetively affecting the process systems. A cost-competitive and eco-friendly scheme for the production of high-purity dissolving grade pulp from bamboo not only requires a process for silica removal, but also needs to fully utilize all of the materials dissolved in the process which includes lignin, and cellulosic and hemicellulosic sugars as well as the silica. Many investigations have been carried out to resolve the silica issue, but none of them has led to a commercial process. In this work, alkaline pretreatment of bamboo was conducted to extract silica prior to pulping process. The silica-free substrate was used to produce high-grade dissolving pulp. The dissolved silica, lignin, hemicellulosic sugars, and degraded cellulose in the spent liquors obtained from alkaline pretreatment and pulping process were recovered for providing high-value bio-based chemicals and fuel. Results An integrated process which combines dissolving pulp production with the recovery of excellent sustainable biofuel and biochemical feedstocks is presented in this work. Pretreatment at 95 °C with 12% NaOH charge for 150 min extracted all the silica and about 30% of the hemicellulose from bamboo. After kraft pulping, xylanase treatment and cold caustic extraction, pulp with hemicellulose content of about 3.5% was obtained. This pulp, after bleaching, provided a cellulose acetate grade dissolving pulp with α-cellulose content higher than 97% and hemicellulose content less than 2%. The amount of silica and lignin that could be recovered from the process corresponded to 95 and 77.86% of the two components in the original chips, respectively. Enzymatic hydrolysis and fermentation of the concentrated and detoxified sugar mixture liquor showed that an ethanol recovery of 0.46 g/g sugar was achieved with 93.2% of hydrolyzed sugars being consumed. A mass balance of the overall process showed that 76.59 g of solids was recovered from 100 g (o.d.) of green bamboo. Conclusions The present work proposes an integrated biorefinery process that contains alkaline pre-extraction, kraft pulping, enzyme treatment and cold caustic extraction for the production of high-grade dissolving pulp and recovery of silica, lignin, and hemicellulose from bamboo. This process could alleviate the silica-associated challenges and provide feedstocks for bio-based products, thereby allowing the improvement and expansion of bamboo utilization in industrial processes.Applied Science, Faculty ofNon UBCChemical and Biological Engineering, Department ofReviewedFacult