Chenhuan Lai

Remarkable solvent and extractable lignin effects on enzymatic digestibility of organosolv pretreated hardwood.

Low solvent concentration effect on substrate digestibility of ethanol organosolv pretreated sweetgum was examined. Surprisingly, lower ethanol concentration in organosolv pretreatments resulted in faster initial rates and higher 72h hydrolysis yields in pretreated substrates. A strong correlation (r(2)=0.96) between pretreatment combined severity factor and residual xylan/glucan ratio was observed. The residual xylan/glucan ratio was associated with the initial hydrolysis rate closely. Furthermore, it was found that preserving extractable lignin in the pretreated substrates could improve enzymatic hydrolysis yield by 33%. This has an important implication in reducing the pretreatment and enzyme cost, because the typical solvent washing after pretreatment could be eliminated and preserving extractable lignin could reduce enzyme loading. Finally, we observed that xylan removal by xylanase could improve the initial rate by 53% and increase the 72h hydrolysis yield by 21%. The extractable lignin precipitation on pretreated substrates increased the 72h hydrolysis yield by 10%.

Contrasting effects of hardwood and softwood organosolv lignins on enzymatic hydrolysis of lignocellulose.

Identifying an appropriate parameter to elucidate effects of lignin on enzymatic hydrolysis is essential to understand the interactions between enzymes and lignin. Contrasting effects of hardwood organosolv lignin (EOL-SG) and softwood organosolv lignin (EOL-LP) on enzymatic hydrolysis were observed. The addition of EOL-SG (8 g/L) significantly improved the 72 h hydrolysis yields of organosolv pretreated sweetgum (OPSG) and loblolly pine (OPLP) from 49.3% to 68.6% and from 41.2% to 60.8%, respectively. In contrast, the addition of EOL-LP decreased the 72 h hydrolysis yields of OPSG and OPLP to 42.0% and 38.1%, respectively. A strong correlation between the distribution coefficients of cellulase enzymes on lignins and the changes of hydrolysis yields indicated that the inhibitory or stimulatory effects of organosolv lignins on enzymatic hydrolysis were governed by the distribution coefficients (R). The different R values probably were related to the electrostatic interactions, hydrophobic interactions and hydrogen bondings between enzymes and lignin.

Enhanced enzymatic saccharification of corn stover by in situ modification of lignin with poly (ethylene glycol) ether during low temperature alkali pretreatment

A novel pretreatment process of corn stover was established in this study by in situ modification of lignin with poly (ethylene glycol) diglycidyl ether (PEGDE) during low temperature alkali pretreatment. The addition of PEGDE obviously improved the enzymatic hydrolysis by covalently modifying the residual lignins in substrates. Under the optimized conditions (pretreated with 10% (w/w) NaOH and 10% (w/w) PEGDE at 70°C for 2.5h), the total fermentable sugar yield was increased by 46.4%, from 23.7g to 34.7g per 100g raw materials. Additionally, the remaining activities of exo-glucanase and β-glucosidase in supernatant were increased by 58.6% and 40.6% respectively, demonstrating that the enhancement of enzymatic hydrolysis was mainly due to the alleviation of enzyme non-productive binding. Although the isolated lignin modified with PEGDE enhanced the enzymatic hydrolysis of substrates as well, this in situ lignin modification provided an efficient but simple way to improve enzymatic saccharification.

Disparate roles of solvent extractable lignin and residual bulk lignin in enzymatic hydrolysis of pretreated sweetgum

The roles of solvent extractable lignin and residual bulk lignin in enzymatic hydrolysis of Avicel and lignocellulosic biomass were distinguished in this study. Solvent extractable lignin removal reduced the 72 h hydrolysis yields of dilute acid pretreated sweetgum (DASG) and organosolv pretreated sweetgum (OPSG) from 38.1% to 31.8% and from 69.9 to 49.3%, respectively. On the contrary, residual bulk lignin removal enhanced the 72 h hydrolysis yields of DASG and OPSG to 91.7% and 90.5%, respectively. The isolated lignins were added into enzymatic hydrolysis of Avicel, which revealed the positive effect of extractable lignin and the negative effect of residual bulk lignin on enzymatic hydrolysis. The cellulase distribution during the hydrolysis and cellulase adsorption indicated that the extractable lignin could counter the negative effect of residual bulk lignin by reducing the non-productive binding between cellulase and bulk lignin.

An integrated process to produce bio-ethanol and xylooligosaccharides rich in xylobiose and xylotriose from high ash content waste wheat straw

A bio-refinery process of wheat straw pulping solid residue (waste wheat straw, WWS) was established by combining prewashing and liquid hot water pretreatment (LHWP). The results showed that employing a prewashing step prior to the LHWP remarkably improved enzymatic glucose yields from 39.7% to 76.6%. Moreover, after 96h simultaneous saccharification and fermentation (SSF), identical ethanol yields of 0.41g/g-cellulose were obtained despite varied solid loadings (5-30%). Beyond ethanol, enzymatic post-hydrolysis of the prehydrolyzate effectively increased xylobiose and xylotriose yields from 15mg/g-WWS and 14mg/g-WWS to 53mg/g-WWS and 20mg/g-WWS, respectively. For mass balance, about 10.9tons raw WWS will be consumed to produce 1ton ethanol, in addition to producing 614.8kg xylooligosaccharides (XOS) containing 334.3kg xylobiose and 124.8kg xylotriose. The results demonstrated that the integrated process for the WWS bio-refinery is promising, based on value-adding co-production in addition to robust ethanol yields.

Prewashing enhances the liquid hot water pretreatment efficiency of waste wheat straw with high free ash content.

The effect of prewashing process prior to the liquid hot water (LHW) pretreatment of high free ash content waste wheat straw (WWS) was investigated. It was found that prewashing process decreased the ash content of WWS greatly, from 29.48% to 9.82%. This contributed to the lower pH value of prehydrolyzate and higher xylan removal in the following LHW pretreatment. More importantly, the prewashing process effectively increased the cellulose enzymatic hydrolysis efficiency of pretreated WWS, from 53.04% to 84.15%. The acid buffering capacity (ABC) and cation exchange capacity (CEC) of raw and prewashed WWS were examined. The majority of free ash removal from WWS by prewashing resulted in the decrease of the ABC of the WWS from 211.74 to 61.81mmol/pH-kg, and potentially enhancing the efficiency of the follow-up LHW pretreatment.

Improving enzymatic hydrolysis efficiency of wheat straw through sequential autohydrolysis and alkaline post-extraction

In this work, a two-step pretreatment process of wheat straw was established by combining autohydrolysis pretreatment and alkaline post-extraction. The results showed that employing alkaline post-extraction to autohydrolyzed wheat straw could significantly improve its enzymatic hydrolysis efficiency from 36.0% to 83.7%. Alkaline post-extraction lead to the changes of the structure characteristics of autohydrolyzed wheat straw. Associations between enzymatic hydrolysis efficiency and structure characteristics were also studied. The results showed that the factors of structure characteristics such as delignification, xylan removal yield, crystallinity, accessibility and hydrophobicity are positively related to enzymatic hydrolysis efficiency within a certain range for alkaline post-extracted wheat straw. The results demonstrated that autohydrolysis coupled with alkaline post-extraction is an effective and promising method to gain fermentable sugars from biomass.

Co-production of bio-ethanol, xylonic acid and slow-release nitrogen fertilizer from low-cost straw pulping solid residue

A novel bio-refinery sequence yielding varieties of co-products was developed using straw pulping solid residue. This process utilizes neutral sulfite pretreatment which under optimal conditions (160 °C and 3% (w/v) sulfite charge) provides 64.3% delignification while retaining 90% of cellulose and 67.3% of xylan. The pretreated solids exhibited excellent enzymatic digestibility, with saccharification yields of 86.9% and 81.1% for cellulose and xylan, respectively. After pretreatment, the process of semi-simultaneous saccharification and fermentation (S-SSF) and bio-catalysis was investigated. The results revealed that decreased ethanol yields were achieved when solid loading increased from 5% to 30%. An acceptable ethanol yield of 76.8% was obtained at 20% solid loading. After fermentation, bio-catalysis of xylose remaining in fermentation broth resulted in near 100% xylonic acid (XA) yield at varied solid loadings. To complete the co-product portfolio, oxidation ammoniation of the dissolved lignin successfully transformed it into biodegradable slow-release nitrogen fertilizer with excellent agricultural properties.

Synergistic effects of pH and organosolv lignin addition on the enzymatic hydrolysis of organosolv-pretreated loblolly pine

The effect of ethanol organosolv lignin (EOL) on enzymatic hydrolysis was examined at pH 4.8–6.0. The addition of EOL prepared from sweetgum enhanced the enzymatic hydrolysis of organosolv-pretreated loblolly pine (OPLP) by 38.8% and 88.0% at pH 4.8 and 5.6, respectively. The addition of EOL prepared from loblolly pine inhibited the enzymatic hydrolysis of OPLP at pH 4.8 but improved it by 43.0% at pH 5.6. This suggests that the addition of EOL and increase in pH act synergistically to improve the enzymatic hydrolysis of OPLP. The effect of EOL addition on cellulase adsorption onto residual lignins was examined. The results revealed that increasing the pH intensified the suppression of non-productive binding between enzymes and residual lignins by EOL. The potential stabilization effects of EOL on enzymes can contribute to the improvement of enzymatic hydrolysis with EOL at higher pH.

Relations Between Moso Bamboo Surface Properties Pretreated by Kraft Cooking and Dilute Acid with Enzymatic Digestibility

Lignocellulosics pretreatment is intended to dismantle biomass’ natural recalcitrance. Chemical and morphological changes of lignocellulosic materials would occur through varying pretreatment processes. In order to figure out why the acid-pretreated and Kraft-cooked bamboo residues showed very different enzymatic digestibility, the surface properties of pretreated bamboo residues were characterized in this work. It was found that analyzed surface properties were considered to be associating with each corresponding enzymatic digestibility of the pretreated samples. The zeta potentials of pretreated bamboo residues have a negative correlation with enzymatic efficiency. Kraft-cooked substrates were found to posse a less hydrophobic nature and demonstrated higher enzymatic conversion than substrates that were dilute sulfuric acid pretreated. The surface accessibility analysis (BET and Direct Red staining) revealed that the higher enzymatic efficiency of Kraft-cooked materials was mostly due to the larger cellulosic surface area than that in acid-pretreated materials. The results re-affirm that different pretreatments create a variety of surface characteristics, leading to the idea that pretreatment and enzymatic hydrolysis can be favorably turned to maximize carbohydrate recovery from bamboo residues.