Re-examination of dilute acid hydrolysis of lignocellulose for production of cellulosic ethanol after de-bottlenecking the inhibitor barrier.

Dilute acid hydrolysis of lignocellulose biomass had been used for production of cellulosic ethanol since 1940 s. The major technical barrier is the acid catalyzed dehydration of monosaccharides to furan aldehydes (furfural and 5-hydroxymethylfurfural), resulting in the high loss of fermentable sugars and significant inhibition on the fermentability of ethanologenic strains. This study re-examined the dilute acid hydrolysis of corn stover and cellulosic ethanol fermentation after a novel biodetoxification approach was introduced to de-bottleneck the inhibitor barrier. The cocktail of sulfuric acid, phosphoric acid and oxalic acid hydrolyzed corn stover to the 51.1 g/L of glucose (0.50 g/g cellulose) and 18.1 g/L of xylose (0.22 g/g xylan). The furfural, 5-hydroxymethylfurfural and acetic acid in the corn stover hydrolysate were completely removed by Paecilomyces variotii FN89, leading to the successful ethanol fermentation of 24.2 g/L, corresponding to 72.6 kg per metric ton of dry corn stover. No wastewater streams, solid wastes and toxic compounds were generated in hydrolysis, biodetoxification and fermentation. The techno-economic evaluations suggest that the cost reduction of replacing cellulase enzyme with cheap acid catalysts compensated the partial ethanol loss of sugar conversion to inhibitors (21.5-89.1%). The re-examination of acid hydrolysis process reveals that a substantial breakthrough in highly active and selective acid catalyst is required for acid hydrolysis to compete with enzymic hydrolysis for cellulosic ethanol fermentation.

Transformation of lignocellulose to starch-like carbohydrates by organic acid-catalyzed pretreatment and biological detoxification.

Corn dry milling provides a mature model for lignocellulose biorefinery process. To copy this technical success, a crucial step is to transform lignocellulose into starch-like carbohydrates (SLC), similar to milled corn grain and in a similar fashion to corn dry milling. The transformation process should be zero wastewater generation and sufficient fermentable sugar conservation; the product should be in solid particle form, free of toxic residues, and high enzymatic hydrolysis yield and fermentability. Here we designed and verified a SLC transformation process by (i) biodegradable oxalic acid-catalyzed pretreatment, and (ii) simultaneous biodegradation of inhibitors and oxalic acid catalyst. The oxalic acid catalyst was effective on disrupting the lignocellulose structure and also biodegradable at low pH value. The biodetoxification fungus Paecilomyces variotii FN89 was capable of degrading the furan/phenolic aldehydes and oxalic acid simultaneously and ultimately, while the fermentable sugars were well preserved. The obtained SLC from wheat straw and corn stover were similar to dry milled corn meal in terms of morphological properties, fermentable sugar contents, enzymatic hydrolysis yield, elemental contents, and free of inhibitors and acid catalyst. The bioconversion of starch-like wheat straw and corn stover produced 78.5 and 75.3 g/L of ethanol (9.9% and 9.5%, v/v) with the yield of 0.47 and 0.45 g ethanol/g cellulose/xylose, respectively, compared with 78.7 g/L (10.0%, v/v) from corn meal and the yield of 0.48 g ethanol/g starch. Mass balances suggest that the ethanol yield, wastewater generation, and elemental recycling of the SLC from lignocellulose were essentially the same as those of corn meal.