The role of the molecular formula of ZnCl2·nH2O on its catalyst activity: a systematic study of zinc chloride hydrates in the catalytic valorisation of cellulosic biomass

Bodachivskyi, Iurii; Kuzhiumparambil, Unnikrishnan; Williams, D. Bradley G.

doi:10.1039/c9cy00846b

Cited by 43 publications

(26 citation statements)

References 48 publications

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“…Conversions of softwood-derived cellulose in ZnCl 2 ·4.25H 2 O, co-solvent system comprising [C 4 mim]Cl and ChCl/oxalic acid, or in ethanol (water content < 0.2%) were performed according to the respective references.…”

Section: Methodsmentioning

confidence: 99%

Catalytic Valorization of Native Biomass in a Deep Eutectic Solvent: A Systematic Approach toward High-Yielding Reactions of Polysaccharides

Bodachivskyi

Kuzhiumparambil

Williams

2019

ACS Sustainable Chem. Eng.

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This work investigates catalytic reactions of raw, bulk, native biomass (poly)carbohydrates in the choline chloride/oxalic acid deep eutectic solvent. In particular, we systematically explore the reactivity of native glucans, fructans, and xylans in model transformations of refined substrates and unrefined cellulosic materials in the catalyst–solvent. We show that α-linked glucose polymers, fructans, and xylans are all amenable to hydrolytic processing, and only the linear polysaccharide cellulose remains rather intractable under our conditions. Improved fundamental understanding of the chemistry permits tuning the reaction parameters toward high yielding conversion of undervalued terrestrial and marine biomass into significantly value-added glucose (yield up to 68 wt %), fructose (yield up to 60 wt %), xylose (yield up to 73 wt %), 5-(hydroxymethyl)furfural (yield up to 14 mol %), or furfural (yield up to 72 mol %). Under these optimized conditions, cellulose remains as an unreacted portion, which could be recovered and very effectively beneficiated, delivering additional useful chemicals in high yields from the biomass and optimizing toward total use of the biomass. We realize efficient conversions of polysaccharides of the biomass into high yields of useful small molecules.

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Section: Methodsmentioning

confidence: 99%

Catalytic Valorization of Native Biomass in a Deep Eutectic Solvent: A Systematic Approach toward High-Yielding Reactions of Polysaccharides

Bodachivskyi

Kuzhiumparambil

Williams

2019

ACS Sustainable Chem. Eng.

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“…The cellulose chain gains flexibility, and therefore, water molecules penetrate the network, producing the dissolution of cellulose. 37 Several studies have investigated the dissolution and hydrolysis of cellulose dissolved in inorganic salt hydrates; 7,38,39 however, the separation of obtained sugars from inorganic salt hydrates is very difficult due to the high solubility of sugars in the dissolution media, and despite some promising studies, such separation remains a challenge. 38 The aim of this work is to study the dissolution of cellulose in different inorganic salt hydrates and its subsequent precipitation by the addition of excess water.…”

Section: Introductionmentioning

confidence: 99%

High enhancement of the hydrolysis rate of cellulose after pretreatment with inorganic salt hydrates

et al. 2020

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“…It has been reported that the coordinated water number influences the acidity and thus the catalytic activity [13b] . LiCl with 2–5 coordinated waters was separately examined for esterification of LA with BuOH.…”

Section: Resultsmentioning

confidence: 99%

Spontaneous Biphasic System with Lithium Chloride Hydrate for Efficient Esterification of Levulinic Acid

Wang

Cui

et al. 2022

ChemistrySelect

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An efficient approach for synthesis of levulinate from biomass‐derived levulinic acid (LA) and n‐butyl alcohol (BuOH) in molten salt hydrates (MSH) with microwave irridiation was reported. A series of molten salt hydrates were evaluated in terms of their catalytic activity and pH value without any additional catalyst. Introduction of AlCl3 greatly increased the yield of butyl levulinate(BL). As high as 95.5 % BL yield was obtained in LiCl ⋅ 3H2O+AlCl3 system. Reaction mechanism study shows that LiCl ⋅ 3H2O can promote the esterification of LA with BuOH by enhancing the protonation of LA. LiCl is able to expel the formed BL into organic‐phase, and then boost up esterification efficiency. Both separation of BL and strong hygroscopicity of LiCl ⋅ 3H2O promoted the esterification reaction equilibrium. High‐efficient esterification of LA with BuOH realized separation of LA from MSH. Activation energies of BL formation are 70.9 kJ/mol in LiCl ⋅ 3H2O and 31.8 kJ/mol in AlCl3+LiCl ⋅ 3H2O.

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The role of the molecular formula of ZnCl₂·nH₂O on its catalyst activity: a systematic study of zinc chloride hydrates in the catalytic valorisation of cellulosic biomass

Abstract: We show the efficient and direct transformation of a range of low value cellulosic substrates such as lignocellulose and algal biomass, into higher value chemicals, including low molecular weight reducing saccharides and furanoid products.

Cited by 43 publications

References 48 publications

Catalytic Valorization of Native Biomass in a Deep Eutectic Solvent: A Systematic Approach toward High-Yielding Reactions of Polysaccharides

Catalytic Valorization of Native Biomass in a Deep Eutectic Solvent: A Systematic Approach toward High-Yielding Reactions of Polysaccharides

High enhancement of the hydrolysis rate of cellulose after pretreatment with inorganic salt hydrates

Spontaneous Biphasic System with Lithium Chloride Hydrate for Efficient Esterification of Levulinic Acid

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