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The unique molecular structure of cellulose makes it challenging to dissolve at room temperature (R.T.), and the dissolution mechanism remains unclear. In this study, we employed ZnCl 2 aqueous solution for cellulose dissolution at R.T., proposing a novel four-stage dissolution mechanism. The efficient dissolution of cellulose in ZnCl 2 aqueous solution at R.T. involves four indispensable stages: rapid migration of hydrated Zn 2+ ions towards cellulose, sufficient penetration between cellulose sheets, strong interaction with cellulose hydroxyl groups, and effective dispersion of separated cellulose chains. The proposed four-stage dissolution mechanism was validated through theoretical calculations and experimental evidence. The hydrated Zn 2+ ions in ZnCl 2  + 3.5H 2 O solvent exhibited ideal migration, penetration, interaction, and dispersion abilities, resulting in efficient cellulose dissolution at R.T. Moreover, only slight degradation of cellulose occurred in ZnCl 2  + 3.5H 2 O at R.T. Consequently, the regenerated cellulose materials obtained from ZnCl 2  + 3.5H 2 O (R.T.) exhibited better mechanical properties. Notably, the solvent recovery rate reached about 95 % based on previous usage during five cycles. The solvent is outstanding for its green, low-cost, efficiency, simplicity, R.T. conditions and recyclability. This work contributes to a better understanding of the cellulose dissolution mechanisms within inorganic salt solvents at R.T., thereby guiding future development efforts towards greener and more efficient cellulosic solvents., Competing Interests: Declaration of competing interest The authors declare no competing interests., (Copyright © 2024 Elsevier B.V. All rights reserved.)

An efficient pretreatment with various concentrations of FeCl 3 (0.005-0.2 mol/L) was developed to extract hemicellulose in sugarcane bagasse and enhance the enzymatic hydrolysis of cellulose in pretreated solids. It was found that 0.025 mol/L FeCl 3 pretreated substrate yielded a high glucose yield of 80.1% during enzymatic hydrolysis. Then the characterization of raw material and pretreated solids was carried out to better understand how hemicellulose removal affected subsequent enzymatic hydrolysis. In addition, Tween 80 and Bovine Serum Albumin (BSA) were added to promote enzymatic hydrolysis of pretreated substrate. Together with that obtained from pretreatment, the highest glucose yield reached 97.7% with addition of Tween 80, meanwhile, a reduction of 50% loading of enzyme yielded the same level of glucose. However, the increased yields with additives decreased gradually as the hydrolysis time was extended. Furthermore, the enhancement mechanisms of Tween 80 and BSA were determined., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Enhancement of eucalyptus enzymatic saccharification by synergy of ZnCl 2 hydrate pretreatment and bovine serum albumin (BSA) was investigated in this study. The result showed that the ZnCl 2 hydrate pretreatment could not only selectively extract up to ∼100% of the hemicellulose from eucalyptus, but also convert portion of high crystalline cellulose I into low crystalline cellulose II, which both beneficial for enhancing subsequent pretreated solids enzymatic saccharification. The addition of BSA into enzymatic hydrolysis step could significantly promote the glucose release from pretreated solids, especially, under the low enzyme loading. Furthermore, the material balance indicated that the highest glucose yield of this study was 35.5g/100g raw material, which representing 90.3% of glucose in raw eucalyptus, combined with the xylose yield, 13.9g/100g eucalyptus, it can be concluded that ZnCl 2 hydrate pretreatment offered the potential to co-produce xylose and glucose from eucalyptus., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Experiments for cellulose depolymerization by synergy of zinc chloride hydrate (ZnCl 2 ·RH 2 O) and sulfated titania catalyst (SO 4 2- /TiO 2 ) were investigated in this study. The results showed the introduction of sulfate into the TiO 2 significantly enhanced the catalyst acid amount, especially for Brønsted acid site, which is beneficial for subsequent cellulose depolymerization. ZnCl 2 ·RH 2 O hydrate, only a narrow composition range of water, specifically 3.0≤R≤4.0, can dissolve cellulose, which finally resulted the cellulose with low crystallinity and weak intrachain and interchain hydrogen bond network. Coupling of ZnCl 2 ·RH 2 O hydrate and SO 4 2- /TiO 2 catalyst as a mixed reaction system promoted cellulose depolymerization, and the products can be adjusted by the control of reaction conditions, the low temperature (80-100°C) seemed beneficial for glucose formation (maximal yield 50.5%), and the high temperature (120-140°C) favored to produce levulinic acid (maximal yield 43.1%). Besides, the addition of organic co-solvent making HMF as the main product (maximal yield 38.3%)., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The effect of ultrasonic pretreatment coupled with HCl-FeCl3 catalyst was evaluated to hydrolyze cellulose amorphous regions. The ultrasonic pretreatment leads to cavitation that affects the morphology and microstructure of fibers, enhancing the accessibility of chemical reagent to the loosened amorphous regions of cellulose. In this work, Fourier transform infrared spectroscopy (FTIR) was used to identify characteristic absorption bands of the constituents and the crystallinity was evaluated by the X-ray diffraction (XRD) technique. The results indicated that appropriate ultrasonic pretreatment assisted with FeCl3 can enhance the acid hydrolysis of amorphous regions of cellulose, thus improving the crystallinity of the remaining hydrocellulose. It was observed that sonication samples that were pretreated for 300 W and 20 min followed by acid hydrolysis had maximum of 78.9% crystallinity. The crystallinity was 9.2% higher than samples that were not subjected to ultrasound. In addition, the average fines length decreased from 49 μm to 37 μm., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Pretreatment combining FeCl3 and Tween80 was performed for cellulose-to-ethanol conversion of eucalyptus alkaline peroxide mechanical pulping waste fibers (EAWFs). The FeCl3 pretreatment alone showed a good effect on the enzymatic hydrolysis of EAWFs, but inhibited enzyme activity to some extent. A surfactant, Tween80, added during FeCl3 pretreatment was shown to significantly enhance enzyme reaction by eluting enzymatic inhibitors such as iron(III) that are present at the surface of the pretreated biomass. Treatment temperature, liquid-solid ratio, treatment time, FeCl3 concentration, and Tween80 dosage for pretreatment were optimized as follows: 180 °C, 8:1, 30 min, 0.15 mol/L, and 1% (w/v). Pretreated EAWFs under such optimal conditions provided enzymatic glucose (based on 100 g of oven-dried feedstock) and substrate enzymatic digestibility of EAWFs of 34.8 g and 91.3% after 72 h of enzymatic hydrolysis, respectively, with an initial cellulase loading of 20 FPU/g substrate.

In this study, cornstalk was pretreated by an acid-chlorite delignification procedure to enhance the conversion of cornstalk to bio-oil in hot-compressed water liquefaction. The effects of the pretreatment conditions on the compositional and structural changes of the cornstalk and bio-oil yield were investigated. It was found that acid-chlorite pretreatment changed the main components and physical structures of cornstalk and effectively enhanced the bio-oil yield. Shorter residence time favored production of the total bio-oil products, whereas longer time led to cracking of the products. A high water loading was found to be favorable for high yields of total bio-oil and water-soluble oil. GC-MS analysis showed that the water-soluble oil and heavy oil were the complicated products of C(5-10) and C(8-11) organic compounds.

Two types of pure cellulose, Avicel PH-101 and Whatman filter paper, were treated with an acid-chlorite delignification procedure in the presence of varying amounts of incorporated lignin, and the molecular weight distributions and degrees of polymerization (DP) of derivatized cellulose were determined by gel permeation chromatography (GPC). Avicel samples with 0% added lignin showed a DP reduction of nearly 5% during acid-chlorite delignification, compared to a 1% drop in DP with 30% added lignin. Lignin-free filter paper samples showed a DP reduction of nearly 35% after hollocellulose delignification. This drop in DP was reduced to less than 12% for samples which contained 30% lignin. Thus, the presence of lignin in biomass samples minimized the DP reduction of cellulose due to acid catalyzed cleavage during acid-chlorite delignification., (Copyright 2010 Elsevier Ltd. All rights reserved.)

The catalytic performance of various metal chlorides in the conversion of cellulose to levulinic acid in liquid water at high temperatures was investigated. The effects of reaction parameters on the yield of levulinic acid were also explored. The results showed that alkali and alkaline earth metal chlorides were not effective in conversion of cellulose, while transition metal chlorides, especially CrCl(3), FeCl(3) and CuCl(2) and a group IIIA metal chloride (AlCl(3)), exhibited high catalytic activity. The catalytic performance was correlated with the acidity of the reaction system due to the addition of the metal chlorides, but more dependent on the type of metal chloride. Among those metal chlorides, chromium chloride was found to be exceptionally effective for the conversion of cellulose to levulinic acid, affording an optimum yield of 67 mol % after a reaction time of 180 min, at 200 degrees C, with a catalyst dosage of 0.02 M and substrate concentration of 50 wt %. Chromium metal, most of which was present in its oxide form in the solid sample and only a small part in solution as Cr3+ ion, can be easily separated from the resulting product mixture and recycled. Finally, a plausible reaction scheme for the chromium chloride catalyzed conversion of cellulose in water was proposed.