Acid‐Assisted Ball Milling of Cellulose as an Efficient Pretreatment Process for the Production of Butyl Glycosides

Abstract

Ball milling of cellulose in the presence of a catalytic amount of H2SO4 was found to be a promising pre-treatment process to produce butyl glycosides in high yields. Conversely to the case of water, n-butanol has only a slight effect on the recrystallization of ball-milled cellulose. As a result, thorough depolymerization of cellulose prior the glycosylation step is no longer required, which is a pivotal aspect with respect to energy consumption. This process was successfully transposed to wheat straw from which butyl glycosides and xylosides were produced in good yields. Butyl glycosides and xylosides are important chemicals as they can be used as hydrotropes but also as intermediates in the production of valuable amphiphilic alkyl glycosides.

Transglycosylation: A Key Reaction to Access Alkylpolyglycosides from Lignocellulosic Biomass

“…ChemSusChem 2018ChemSusChem , 11,1395ChemSusChem -1409 www.chemsuschem.org 2018 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim which can be further processedt od ownstream chemicals such as glucose, 5-hydroxymethylfurfural,o rh exitols. [23] Cellulose was first impregnated with 10 wt %o f H 2 SO 4 and was then ball-milled for 1h.N ext, the recovered acidulated glucans were suspended in 30 equivalents of n-butanol and heateda tr eflux for 3h(Scheme 5). [23] Cellulose was first impregnated with 10 wt %o f H 2 SO 4 and was then ball-milled for 1h.N ext, the recovered acidulated glucans were suspended in 30 equivalents of n-butanol and heateda tr eflux for 3h(Scheme 5).…”

“…[22] Inspired by this work, JØrôme and co-workers recently reported the direct transglycosylation of cellulosew ith n-butanol in at wo-step process. [23] Hence,e xtensive depolymerization of cellulose during the mechanocatalytic step is not mandatory before the glycosylation reaction. Undert hese conditions, n-butyl-a/b-d-glucosides were produced in 62 % yield.…”

Alcoholysis: A Promising Technology for Conversion of Lignocellulose and Platform Chemicals

“…Boissou et al. (Scheme ) reported that the mechanocatalytic treatment of acid‐impregnated cellulose was more advantageous for glycosylation (alcoholysis) than hydrolysis . After H 2 SO 4 ‐assisted ball milling, the yield of glucose in cellulose hydrolysis was only 11 %, whereas that of butyl glycosides reached 56 % in butanol at 117 °C for 5 h. Kinetic data suggested that the glycosylation rate of acid‐assisted ball‐milled cellulose was seven times faster than that of hydrolysis.…”

“…Boissou et al (Scheme 2) reported that the mechanocatalytic treatment of acid-impregnated cellulose was more advantageous for glycosylation( alcoholysis) than hydrolysis. [18] After H 2 SO 4 -assisted ball milling,t he yield of glucosei nc ellulose hydrolysis was only 11 %, whereas that of butyl glycosides reached5 6% in butanol at 117 8Cf or 5h.K inetic data suggested that the glycosylationr ate of acid-assisted ball-milled cellulose was seven times faster than that of hydrolysis.T he water mediuml eads to the recrystallization of ball-milled cellulose to ah igher degree of structural order,w hereas it is obviously inhibited in n-butanol. More critically,t his acid-assisted ball-mill-ing method can be adopted to convert raw wheat straw, at ype of lignocellulose feed.…”

Mechanochemical Decomposition of Crystalline Cellulose in the Presence of Protonated Layered Niobium Molybdate Solid Acid Catalyst

“…As the necessity of environmentally benign processes has grown, attention has focusedo ne asily separables olid catalysts for converting cellulose, [6,8,12,13] such as ion-exchange resins, [14] sulfonated carbon materials, [15,16] sulfonatedc arbon-silica nanocomposites, [17] weakly acidic amorphous carbons, [18,19] az eolite-templated carbon, [20] graphene oxide, [21] metal oxides, [22] and supported metal catalysts. [15,17,[24][25][26][27] Although amorphous cellulose can be more easily decomposed into oligosaccharides compared to crystalline cellulose, [28,29] the poor affinity between cellulose and mostc atalysts needs to be overcome. [15,17,[24][25][26][27] Although amorphous cellulose can be more easily decomposed into oligosaccharides compared to crystalline cellulose, [28,29] the poor affinity between cellulose and mostc atalysts needs to be overcome.…”