A bifunctional solid organocatalyst, sulfamic acid, was evaluated to produce furfural from xylose and different biomass in an environmentally friendly system comprising Gamma-Valerolactone (GVL) and water. The highest yield (70.19%) of furfural was achieved in a 90% solution of GVL in water containing 10 mol% of sulfamic acid at 190 °C for 15 min from xylose. The potential mechanism of sulfamic acid efficiently catalyzing xylose isomerization and dehydration is presented for the first time. It is hypothesized that another sulfamic acid form, the zwitterionic unit (H 3 N + SO 3 − ) is crucial in efficiently catalyzing isomerization reaction due to its electron-rich sulfonate being superior in attacking the hydrogen atom on C1 leading to the xylose tautomerization to xylulose, a shorter route to furfural, and finally, the NH 2 SO 3 H with strong acidity also promotes the xylulose dehydration to furfural. The above system was evaluated using various biomass species including corncob, Miscanthus × giganteus , the hull and shell of Camellia oleifera (tea) fruit and Aleurites fordii HemsL. (tung) fruit. Almost all these biomass showed excellent furfural yields (over 70%), with tung shell providing the best yield of 92.19% at 200 °C and reaction time of 30 min.
Bioenergy crops provide enormous renewable biomass resources convertible for biofuel production, but lignocellulose recalcitrance fundamentally determines its enzymatic saccharification at high cost and low efficiency. In this study, total 30 diverse Miscanthus lignocellulose substrates were incubated with T. reesei strain to secret lignocellulose-degradation enzymes, and their major wall polymers features (cellulose crystallinity , hemicellulose arabinose and lignin H-monomer) were meanwhile examined with distinct impacts on the enzyme activities . Using characteristic Miscanthus (Msi62) de-lignin residue as inducing substrate with the reesei strain, this study detected that the Msi62-induced enzymes were of consistently higher enhancements on enzymatic saccharification of various lignocellulose residues examined in 17 grassy and woody bioenergy crops, particularly for the hemicellulose hydrolyses , compared to other two reesei -secreted cellulases and three commercial enzymes. Notably, based on SDS-gel protein separation profiling and LC-MS/MS analysis, the Msi62-induced enzymes consist of distinct cellulases (CBHI, BG, EGII) compositions and high-activity xylanases. Therefore, this study has demonstrated an applicable approach to achieve the optimal cellulases and xylanases cocktails that enable for low-costly and high-efficient enzymatic saccharification of diverse lignocellulose sources, providing a potential strategy for large-scale biofuel production in all major bioenergy crops.
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