Selective saccharification of cellulose
into glucose is a critical
step for utilization of lignocellulosic biomass. Molten salt hydrates
(MSHs) have shown promising performance in selectively converting
cellulose into glucose because of the high solubility of cellulose
in the solvent. However, the separation of formed glucose from the
MSHs is still a grand challenge. To address this issue, we developed
a two-step process, where crystalline cellulose is hydrolyzed into
short-chain glucan oligomers in MSHs followed by separation and subsequent
hydrolysis of the formed oligomers into glucose under mild conditions.
The two-step method provides an easy separation for glucan oligomers
from the MSHs without sacrificing the selectivity to glucose. Application
of the method for crystalline cellulose is, however, limited to a
relatively low concentration, 26.2 mg/mL, because of the formation
of byproducts in the MSH that facilitate oligomers degradation. In
this work, reactive adsorption was employed to in situ remove the
byproducts formed during cellulose hydrolysis in the MSH. It was found
that hyper-cross-linked polymer (HCP) made from the polymerization
of 4-vinylbenzyl chloride and divinylbenzene can selectively adsorb
5-hydroxymethylfurfural (5-HMF) and levulinic acid (LA) while showing
negligible sugar adsorption in both water and the MSH. With the reactive
adsorption approach, byproducts including 5-HMF and LA were removed
from the reaction media under reaction conditions, and their negative
effects on oligomer degradation were inhibited. In the presence of
the HCP, the obtained glucan oligomer concentration was enhanced from
less than 54.2 to 247.1 mg mL–1 when the weight
ratio of cellulose was increased to MSH from 1:60 to 1:4, exhibiting
an oligomer yield of 69.5%. The HCP can be effectively separated from
the reaction media by filtration and regenerated by oxidation with
hydrogen peroxide. Application of reactive adsorption with HCP for
cellulose hydrolysis in the MSH provides a promising method to produce
glucan oligomers and glucose with an improved yield and efficiency.