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[Display omitted] • LiBr hydrate/acetone system is efficient for converting crystalline cellulose (MCC) to 5-hydroxymethylfurfural (5-HMF). • 75.1% yield of 5-HMF together with 13.7% yield of glucose were obtained from MCC conversion with the addition of AlCl 3. • DFT calculations indicated glucose isomerization rather than crystalline cellulose hydrolysis is the rate-determining step in cellulose conversion into 5-HMF. • Produced 5-HMF can be efficiently recovered by hyper-cross-linked polymer adsorption. • reaction system can be recycled 5 times without reducing 5-HMF selectivity. 5-hydroxymethylfurfural (5-HMF) is a crucial biomss-derived fuel precursor with versatile conversion pathways to advanced fuels. However, direct production of 5-HMF from crystalline cellulose is critical challenging due to the inefficient deconstruction of recalcitrant cellulose structure. Molten salt hydrates (MSHs) are unique in cellulose deconstruction and dissolution. In this work, a biphasic system of LiBr hydrate/acetone was established. It was found that 93.4% yield of 5-HMF can be efficiently converted from fructose without any catalysts. With the addition of AlCl 3 to adjust Lewis acidity, an enhanced 5-HMF yield of 75.1% together with 13.7% of glucose were directly produced from cellulose, showing a promising carbon balance of 88.8%. A proposed mechanism for cellulose conversion was studied by density functional theory (DFT) calculations, demonstrating that the isomerization of glucose to fructose rather than crystalline cellulose hydrolysis was the rate-determining step. After reaction, the formed 5-HMF can be efficiently recycled from solvent via hyper-cross-linked polymer adsorption and the reaction system can be recycled for more than 5 times without reducing 5-HMF selectivity. [ABSTRACT FROM AUTHOR]

Molten salt hydrates (MSHs) are remarkable in breaking through the recalcitrant structure of microcrystalline cellulose and raw biomass. After being pretreated in 60 wt% LiBr at 130 °C for 2 h, cellulose crystallinity as well as degree of polymerization (DP) decreased. It was found that 91.3% yield of pretreated cellulose was removed from MSHs by filteration followed by being hydrolyzed into glucose with a high yield of 75.3% by dilute acid under mild reaction conditions. The pretreatment process also works on raw corn stover hydrolysis. After being pretreated at 100 °C for 5 h, 88.4% yield of cellulose in biomass was recovered and can be hydrolyzed into 54.9% yield of glucose with dilute acid. It was found that the cellulose in corn stover can be easier degraded compared with microcrystalline cellulose during MSHs pretreatment, which dues to the formation of acetic acid from hemicellulose hydrolysis. The proposed pretreatment technique presents a promising potential for glucose production from biomass in a commercial way. Unlabelled Image • MSHs pretreatment effectively decreased cellulose crystallinity and DP. • After being pretreated at 130°C for 2 h, 91.3% of cellulose was removed from MSHs via filtration. • Enhanced glucose yield of 75.3% was obtained from pretreated cellulose hydrolysis at mild condition. • 88.4% cellulose recovery and 54.9% glucose yield were obtained from MSHs pretreatment and hydrolysis, respectively. [ABSTRACT FROM AUTHOR]

Molten salt hydrate (MSH) is unique in cellulose dissolution and in one-pot conversion of crystalline cellulose into 5-hydroxymethylfurfural (5-HMF). However, low yield of 5-HMF was obtained using raw biomass substrate in MSHs. Herein, we investigated conversion of raw biomass towards HMF using MSHs. We showed that the release of acetic acid from hemicellulose degradation in MSH is a key to influence the yield of 5-HMF. Thus, an autohydrolysis pretreatment method was proposed to remove hemicellulose before conversion of cellulose into 5-HMF. After being pretreated at 180 °C for 40 min, hemicellulose was removed from biomass with 91.8% yield of cellulose remained in solid part. By eliminating the negative effect of acetic acid, 5-HMF yield was significantly improved from 40.9% to 64.6%, together with 9.3% yield of glucose for cellulose conversion in MSH/acetone at 180 °C for 20 min. [ABSTRACT FROM AUTHOR]

Selective hydrolysis of crystalline cellulose to cello-oligosaccharides in molten salt hydrates (MSHs) is a promising method for valorization of lignocellulose. However, the by-products derived from cellulose hydrolysis can facilitate cello-oligosaccharide degradation and decrease its selectivity. To address this issue, lignin-based hyper cross-linked polymers (LHCPs) were prepared to in situ adsorb by-products during hydrolysis and thus prevent cello-oligosaccharides from degradation. The synthesized LHCP‐33%, with a high lignin content of 33%, showed a remarkable surface area of 708.7 m2 g−1 and good hydrophilicity, exhibiting a promising adsorption capacity of 340 mg g−1 towards 5-hydroxymethylfurfural (5-HMF), which is supposed to be the major cellulose-derived by-product. We showed that 5-HMF adsorption was driven by the formation of CH-π bonds between 5-HMF and aromatic rings on LHCP. When LHCP‐33% was employed in cellulose hydrolysis, the yield of cello-oligosaccharide can be efficiently enhanced from 39.5% to 78.2%. This work offered a new application of lignin in enhanced cello-oligosaccharide production from cellulose. [Display omitted] • 78.2 % yield of cello-oligosaccharide can be selectively produced from crystalline cellulose saccharification via in situ adsorption of by-products on lignin-based hyper cross-linked polymer (LHCP). • The synthesized LHCP shows a high surface area and good hydrophilcity which is beneficial for by-products adsorption. • The adsorption of hydrolysis-derived 5-hydroxymethylfurfural (5-HMF) on LHCP is driven by the formation of CH-π bonds rather than hydrogen bonds. • This approach provides a new alternative in utilization of lignin for high-valued cello-oligosaccharide production from cellulose. [ABSTRACT FROM AUTHOR]