Cellulose nanofibril-polymer hybrids for protecting drilling fluid at high salinity and high temperature.

A copolymer (PADH) was first synthesized from 2-acrylamido-2-methylpropane sulfonic acid (AMPS), N,N-dimethylacrylamide (DMA), and 2-Hydroxyethyl acrylate (HEA) by UV-induced polymerization. Subsequently, cellulose nanofibrils (CNFs) were introduced into the copolymer through ironic cross-linking between ferric ions and carboxylate groups as well as sulfonic acid groups to produce a hybrid product (PADHC-Fe3+-3). The salt tolerance and thermal stability of the copolymers and the hybrid product were investigated. The results showed that the optimum HEA dosage was 5% (in relation to the total mass of AMPS and DMA). In addition, the fluid loss test showed that the hybrid product PADHC-Fe3+-3 had excellent salt tolerance (maximum tolerance: 26.5 wt% NaCl and 32 wt% combined salts) and thermal stability (maximum tolerance: 200 °C). The SEM images indicated that the filter cakes became denser after the addition of PADHC-Fe3+-3. The results demonstrated that the cross-linked hybrid product was very promising for industrial application in drilling engineering.

Ethanol production from bamboo using mild alkaline pre-extraction followed by alkaline hydrogen peroxide pretreatment.

A sequential two-stage pretreatment process comprising alkaline pre-extraction and alkaline hydrogen peroxide pretreatment (AHP) was investigated to convert bamboo carbohydrates into bioethanol. The results showed that mild alkaline pre-extraction using 8% (w/w) sodium hydroxide (NaOH) at 100°C for 180min followed by AHP pretreatment with 4% (w/w) hydrogen peroxide (H2O2) was sufficient to generate a substrate that could be efficiently digested with low enzyme loadings. Moreover, alkali pre-extraction enabled the use of lower H2O2 charges in AHP treatment. Two-stage pretreatment followed by enzymatic hydrolysis with only 9FPU/g cellulose led to the recovery of 87% of the original sugars in the raw feedstock. The use of the pentose-hexose fermenting Saccharomyces cerevisiae SR8u strain enabled the utilization of 95.7% sugars in the hydrolysate to reach 4.6%w/v ethanol titer. The overall process also enabled the recovery of 62.9% lignin and 93.8% silica at high levels of purity.

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.

Increasing efficiency of enzymatic hemicellulose removal from bamboo for production of high-grade dissolving pulp.

To improve the efficiency of enzymatic hemicellulose removal from bamboo pre-hydrolysis kraft pulp, mechanical refining was conducted prior to enzyme treatment. Refining significantly improved the subsequent hemicellulose removal efficiency by xylanase treatment. Results showed that when PFI refining was followed by 3h xylanase treatment, the xylan content of the bamboo pre-hydrolysis kraft pulp (after first stage oxygen delignification) could be decreased to 2.72% (w/w). After bleaching of enzyme treated pulp, the alpha-cellulose content was 93.4% (w/w) while the xylan content was only 2.38%. The effect of refining on fibre properties was investigated in terms of freeness, water retention value, fibre length and fibrillation characteristics. The brightness, reactivity and viscosity were also determined to characterize the quality of final pulp. Results demonstrated the feasibility of combining refining and xylanase treatment to produce high quality bamboo dissolving pulp.

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.

High gravity and high cell density mitigate some of the fermentation inhibitory effects of softwood hydrolysates.

After steam pretreatment of lignocellulosic substrates the fermentation of the biomass derived sugars to ethanol is typically problematic because of both the generally low sugar concentrations that can be supplied and the presence of naturally occurring and process derived inhibitors. As the majority of the inhibitory materials are usually associated with the hemicellulose rich, water soluble component, this fraction was supplemented with glucose to simulate high solids, un-detoxified substrate to see if a high gravity/high cell consistency approach might better cope with inhibition. Several yeast strains were assessed, with the Tembec T1, T2 and Lallemand LYCC 6469 strains showing the greatest ethanol productivity and yield. The addition of supplemental glucose enabled the faster and quantitatively higher removal of hydroxymethylfurfural (HMF). High cell density could provide effective fermentation at high sugar concentrations while enhancing inhibitor reduction. A 77% ethanol yield could be achieved using strain LYCC 6469 after 48 h at high cell density. It was apparent that a high cell density approach improved ethanol production by all of the evaluated yeast strains.