The difference in the enzymatic hydrolysis yield of acid-catalyzed steam-exploded corn stover (ASC) before and after washing with water reached approximately 15 % under the same conditions. The reasons for the difference in the yield between ASC and washed ASC (wASC) were determined through the analysis of the composition of ASC prehydrolyzate and sugar concentration of enzymatic hydrolyzate. Salts produced by neutralization (CaSO4, Na2SO4, K2SO4, and (NH4)2SO4), sugars (polysaccharides, oligosaccharides, and monosaccharides), sugar-degradation products (weak acids and furans), and lignin-degradation products (ethyl acetate extracts and nine main lignin-degradation products) were back-added to wASC. Results showed that these products, except furans, exerted negative effect on enzymatic hydrolysis. According to the characteristics of acid-catalyzed steam explosion pretreatment, the five sugar-degradation products’ mixture and salts [Na2SO4, (NH4)2SO4] showed minimal negative inhibition effect on enzymatic hydrolysis. By contrast, furans demonstrated a promotion effect. Moreover, soluble sugars, such as 13 g/L xylose (decreased by 6.38 %), 5 g/L cellobiose (5.36 %), 10 g/L glucose (3.67 %), as well as lignin-degradation products, and ethyl acetate extracts (4.87 %), exhibited evident inhibition effect on enzymatic hydrolysis. Therefore, removal of soluble sugars and lignin-degradation products could effectively promote the enzymatic hydrolysis performance.

High-efficiency xylose utilization is one of the restrictive factors of bioethanol industrialization. However, xylonic acid (XA) as a new bio-based platform chemical can be produced by oxidation of xylose with microbial. So, an applicable technology of XA bioconversion was integrated into the process of bioethanol production. After corn stover was pretreated with acid-catalyzed steam-explosion, solid and liquid fractions were obtained. The liquid fraction, also named as acid-catalyzed steam-exploded corn stover (ASC) prehydrolyzate (mainly containing xylose), was catalyzed with Gluconobacter oxydans NL71 to prepare XA. After 72 h of bioconversion of concentrated ASC prehydrolyzate (containing 55.0 g/L of xylose), the XA concentration reached a peak value of 54.97 g/L, the sugar utilization ratio and XA yield were 94.08 and 95.45 %, respectively. The solid fraction was hydrolyzed to produce glucose with cellulase and then fermented with Saccharomyces cerevisiae NL22 to produce ethanol. After 18 h of fermentation of concentrated enzymatic hydrolyzate (containing 86.22 g/L of glucose), the ethanol concentration reached its highest value of 41.48 g/L, the sugar utilization ratio and ethanol yield were 98.72 and 95.25 %, respectively. The mass balance showed that 1 t ethanol and 1.3 t XA were produced from 7.8 t oven dry corn stover.

•NaOH was very suitable to back extraction regeneration of the extractant.•NaOH could remove 100% acetic acid from the extractant.•The regenerated extractant reused ten cycles had no problem.Trialkylamine was an effective extractant for the removal of inhibitors from corn stover prehydrolyzate. Ethanol fermentability of the extracted prehydrolyzate was improved significantly. An approach for regeneration and valuable solutes (mainly acetic acid) recovery from such extractant was to back-extract the extractant containing inhibitors with sodium hydroxide. The influences of NaOH concentration, aqueous–organic phase ratio (A/O) on the extractant regeneration were investigated. The results indicated that 17.5 g/l NaOH could remove 100% acetic acid at A/O of 1:1. 175 g/l NaOH at A/O of 1:10 could also reach the same effect. Likewise, the results of 175 g/l NaOH at A/O of 1:1 repeatedly back-extracted the extractant for ten cycles were the same as before. The performance of regenerated extractant on extraction the corn stover prehydrolyzate showed almost no change after reused ten cycles. So NaOH was very suitable to regenerate the extractant containing inhibitors in bioethanol industry.

The prehydrolyzate obtained from acid-catalyzed steam-exploded corn stover (ASC) mainly contains xylose and a number of inhibitory compounds that inhibit ethanol fermentation by Pichia stipitis. In this study, the effects of the ASC prehydrolyzate, specifically those of the carbohydrate-degradation products, lignin-degradation products (which were extracted from ASC prehydrolyzate using ethyl acetate), and six major phenolic compounds (added to pure-sugar media individually or in combination), on ethanol fermentation were investigated. Results indicate that the effects of the carbohydrate-degradation products were negligible (10 h delayed) compared with those of pure-sugar fermentation, whereas the effects of the lignin-degradation products were significant (52 h delayed). Meanwhile, the inhibitory effects of the major phenolic compounds were not caused by certain types of inhibitors, but were due to the synergistic effects of various inhibitors.

•An integrated process was to produce ethanol, vanillin, and xylooligosaccharides.•NaOH pretreatment was to obtain the solid residue and the liquid fraction.•The residue after enzymatic hydrolysis was further fermented to produce ethanol.•The liquid was firstly hydrolyzed with xylanase to produce xylooligosaccharides.•The liquid after xylanase hydrolysis was further oxidized to produce vanillin.This study aims to present an integrated process that can be used to produce ethanol, vanillin, and xylooligosaccharides from Camellia oleifera shell. After the shell was pretreated with NaOH, two fractions were obtained: solid and liquid fractions. The solid fraction was hydrolyzed with cellulase and then fermented with Pichia stipitis to produce ethanol. The liquid fraction was subjected to oxidation to prepare vanillin or hydrolysis with xylanase to prepare xylooligosaccharides. The optimal pretreatment conditions of an orthogonal test were as follows: 12% NaOH concentration; 120 °C; 150 min; and liquid–solid ratio of 10.0. After pretreatment, the solid fraction containing cellulose and a small part of xylan at 10% substance concentration via enzymatic hydrolysis and glucose–xylose cofermentation could obtain 17.35 g/L of ethanol, 80.90% of the theoretical yield. The liquid fraction was initially hydrolyzed with xylanase to produce 1758.63 mg/L of xylooligosaccharides (DP2–6) and then oxidized to produce 322.07 mg/L of vanillin.