Clean Synthesis of 5-Hydroxymethylfurfural and Levulinic Acid by Aqueous Phase Conversion of Levoglucosenone over Solid Acid Catalysts

Abstract

Levoglucosenone (LGO) is an emerging biorenewable platform for the fine and commodity chemical industries. Herein, we report an aqueous phase conversion of LGO to 5-hydroxylmethylfurfural (HMF) and levulinic acid (LA) over solid acid catalyst. Several types of solid acid catalysts such as zeolites, strongly acidic ion-exchange resin, and sulfonated activated carbon were investigated for this reaction. Among the tested catalysts, ZSM-5 and Amberlyst 70 showed the best performances for selectively producing the target products, resulting in the highest total yield of HMF and LA at 72.2% on a molar basis. Factors decreasing the reaction selectivity were identified through the comparison of catalysts and kinetic analysis to the pore morphology, presence of Lewis acid sites, and formation of degradation products directly from LGO or its hydrated product. ZSM-5 and Amberlyst 70, after a single-batch experiment, contained deposits from the degradation products but could be reused with little loss in activity, although calcination was required for ZSM-5. The catalytic system, employing LGO as feedstock and recyclable solid acid catalysts, uses only water as reaction media and thus has the potential to be a clean route for producing the key building blocks HMF and LA.

Rapid, High‐Yield Fructose Dehydration to 5‐Hydroxymethylfurfural in Mixtures of Water and the Noncoordinating Ionic Liquid [bmim][OTf]

“…Of the 94 productso btained from these sugars, 25 were selected as involving feasible technologiest hat are suitablef or large-scale prototype testing in ap ilot plant. [11][12][13] Other research has focused on optimizingh eterogeneous catalysts for dehydration reactions involving both metal catalysts [14][15][16][17][18][19][20] and supported ionic liquids. [3] The main route to form HMF is by the dehydration of sugars, [4] and important resultsh ave been achieved for HMF production using ionic liquids.…”

“…[10] Deep eutectic solvents andw ater have also been investigated for the dehydration of fructose into HMF but improvedy ields are still needed. [11][12][13] Other research has focused on optimizingh eterogeneous catalysts for dehydration reactions involving both metal catalysts [14][15][16][17][18][19][20] and supported ionic liquids. [21,22] In particular, ionic liquidsw ith halide counteranions have provenv ery efficient for the production of HMF from fructose, glucose,a nd cellulose with both Brønsted and Lewis acid catalysts.…”

Sulfated Zirconia with Different Crystal Phases for the Production of Ethyl Levulinate and 5‐Hydroxymethylfurfural

“…Over the past decade, a number of acid catalysts have been developed to efficiently catalyze the various acid‐catalyzed reactions . Homogeneous acid catalysts (HCl, H 2 SO 4 , etc.)…”

“…[19][20][21] Over the past decade, a number of acid catalysts have been developed to efficiently catalyze the various acid-catalyzed reactions. [22][23][24][25][26][27][28][29] Homogeneous acid catalysts (HCl, H 2 SO 4 , etc.) exhibit good catalytic performance due to their homogeneous distribution in protic solvent.…”

Fast Synthesis of Hydroxymethylfurfural from Levoglucosenone by Mixing with Sulphuric Acid and Heating in a Microtube Reactor

“…The target product from LGO in current market is limited mainly to dihydrolevoglucosenone, which is used as solvent (Sherwood et al, 2014), but extensive studies have revealed the potential to be a type of platform chemical similarly to HMF (Krishna et al, 2018). Recent studies (Krishna et al, 2016;He et al, 2017;Huang et al, 2019b) have identified LGO as an alternative feedstock for HMF.…”