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Saccharification of cellulose into glucose is a key step for the utilization of lignocellulose. Molten salt hydrate (MSH) is unique in selective hydrolysis of cellulose into glucose but the separation of formed glucose from MSH is challenging due to the high solubility of glucose in MSH. To address this issue, this work developed a method where a small dosage of MSH was applied to impregnate cellulose and convert it into water-soluble sugar with the degree of polymerization (DP) lower than 6, which can be readily hydrolyzed into glucose under mild conditions without sacrificing selectivity. Under the optimized impregnation condition at 110 °C for 2 h, cellulose was selectively converted into water-soluble sugar with a yield of 87.5%. Then the MSH can be efficiently dissolved and removed by anti-solvent isolation with n-butanol, resulting in a sugar recovery of 84.3%. We showed that the separation efficiency was influenced by anti-solvent polarity and oligosaccharides chain-length. Moreover, the production and separation of water-soluble sugar from corn stover was also investigated. 88.9% yield of water-soluble sugar was obtained from the impregnation of corn stover under the optimized reaction conditions. With the addition of n-butanol as an anti-solvent, the water-soluble sugar can be recovered from MSH with a selectivity of 86.7%. [ABSTRACT FROM AUTHOR]

[Display omitted] • Cellulose can be selectively converted into 5-HMF in monophasic MSH solvent. • 44.5 % yield of 5-HMF together with 75.0 % of carbon balance were obtained. • The total B/L acid sites of AlSiO-20 is the key issue in affecting 5-HMF yield. • AlSiO-20 can be recycled for more than 5 times with stable performance. • 5-HMF can be separated from MSH via HCP adsorption. Production of 5-HMF from cellulose is a promising approach for advanced bio-fuels preparation, but the degradation of active 5-hydroxymethylfurfural (5-HMF) is a critical challenge affecting 5-HMF selectivity. To address this issue, biphasic reaction system consisting of water and organic solvent is generally used to in-situ extract 5-HMF into organic phase to inhibit product degradation. Despite the high 5-HMF selectivity achieved in biphasic system, low product concentration and difficulty in separation restrict its industrial applications. Molten salt hydrate (MSH) is unique in cellulose conversion and 5-HMF preservation. In this work, MSH of LiBr was used as monophasic solvent for cellulose conversion and an acidity tunable solid acid AlSiO-x was used as the catalyst. It was found that a relatively high 5-HMF yield of 44.5% together with carbon balance of 75.0% were obtained at 170 °C for 20 min, which is higher than the results ever reported. Importantly, this work proved that the ratio of total Brønsted to Lewis acid sites on solid acid is the key issue affected 5-HMF yield. After reaction, solid acid can be recycled for more than 5 times without catalytic performance decline, and the dissolved 5-HMF can be sufficiently separated from MSH via hyper cross-linked polymer (HCP) adsorption. [ABSTRACT FROM AUTHOR]

Molten salt hydrates (MSH) are unique in overcoming the characteristic recalcitrance of crystalline cellulose. We show that cellulose can be efficiently hydrolyzed into short-chain oligomers and glucose under mild conditions in concentrated LiBr solution without using any additional acid catalyst. Under optimized reaction conditions, short-chain oligomers with a yield of 90.4% can be obtained. Selective hydrolysis in the MSH is effective even at a high initial cellulose concentration (higher than 10 wt%). The obtained oligomers are solvated and soluble in the MSH. We show that amorphous carbon of a large surface area is effective for adsorption of the short-chain oligomers, cellobiose, and glucose from the MSH. The adsorption capacity and adsorption affinity of the carbon increases by ∼4 and ∼15 times in MSH with increasing the oligomer chain length compared to glucose and is negatively influenced by the ion concentration of the MSH. A stepwise hydrolysis process for converting crystalline cellulose into glucose is developed, whereby cellulose is firstly hydrolyzed into soluble short-chain oligomers in the MSH. The oligomers are then separated from the MSH using amorphous carbon and finally hydrolyzed into glucose under mild reaction conditions. [ABSTRACT FROM AUTHOR]

[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]

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]

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]

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]