Chemical-Catalytic Approaches to the Production of Furfurals and Levulinates from Biomass

Abstract

The synthesis and chemistry of 5-(hydroxymethyl)furfural (HMF), 5-(chloromethyl)furfural (CMF), and levulinic acid (LA), three carbohydrate-derived platform molecules produced by the chemical-catalytic processing of lignocellulosic biomass, is reviewed. Starting from the historical derivation of these molecules and progressing through modern approaches to their production from biomass feedstocks, this review will then survey their principal derivative chemistries, with particular attention to aspects of commercial relevance, and discuss the relative merits of each molecule in the future of biorefining.

Effective conversion of biomass into bromomethylfurfural, furfural, and depolymerized lignin in lithium bromide molten salt hydrate of a biphasic system

“…30 Recently, halomethylfurfurals such as 5-bromomethylfurfural (BMF) and 5-chloromethylfurfural (CMF) have been investigated as platform chemicals for the production of solvents, polymers, and liquid hydrocarbon fuels. [31][32][33][34][35] Diverse approaches were explored, but these processes had some limitations such as high acid loading or concentration, unsatisfactory product yield, and insufficient utilization of hemicelluloses and lignin. 26,27,29,31,32 For effective conversion of biomass to the furans, selection of a proper reaction medium is crucial.…”

Experimental studies towards optimization of the production of 5-(chloromethyl)furfural (CMF) from glucose in a two-phase reactor

“…To eliminate these issues, this study was conducted under isothermal conditions by adding the substrate to a preheated mixture of the remaining components in an open vessel. Furthermore, most of the prior work for producing halomethylfurfurals has involved the use of concentrated HCl (or HBr) in order to achieve high yields over short time frames [12]. Since the boiling point of 12 M HCl is ca.…”

“…Unlike HMF 1, compound 2 can be accessed in high yield from glucose or even directly from cellulosic biomass and, since it is hydrophobic, it presents no problems in its isolation from acidic aqueous reaction media. The synthesis of CMF has been reviewed in detail [12].…”

5‐(Chloromethyl)furfural is the New HMF: Functionally Equivalent But More Practical in Terms of its Production From Biomass

“…However,i ns pite of all this attention and the promise of av ariety of HMF derivatives with the potential to displace petroleume quivalents in the fuel, polymer,a nd chemical markets, the commercialization of HMF has run into an umber of obstacles. [2,3] First, HMF is ap olar,h ydrophilic molecule that is not easily extracted from the aqueous media in which it is usually generated, whiche ncumbersp roduct isolation.T he use of polar aprotics olvents, aqueous phase modifiers, or ionic liquids have been putf orward as alternatives, but these have drawbacks of their own in terms of cost, stability,t oxicity, recycling, and/or catalystr ecovery.S econd, HMF is sensitive to the acidic conditions under which it is produced, leading to the formationo fh umic matter and resin byproducts, which ultimately limits selectivity.F inally,h igh-yielding production of HMF presently relies on fructosea safeedstock. Although the use of glucose and sucrose in the presenceo fc ertain catalysts has also given good results, none of these sugars will ever be competitive with raw,c ellulosic biomass for commercial productiono f1 or indeed any green chemical.…”

“…[6] Luminaries such as Henry J. H. Fenton, Emil Fischer, and Norman Haworth were all variously involved in the study of the synthesis and chemistry of CMF.A sf or HMF,t he production of CMF from fructose could be made to proceed in high yield by treatment with HCl, but the reactiong ave rather poor results with glucose or starch, and virtually no useful outcomes from cellulose or biomass. [3] In 2008, Mascal and Nikitin reported am ethod for the conversion of either glucose, sucrose, or cellulose into 3 in 71-76 %i solated yields, alongside byproducts HMF,L A, and 2-(2hydroxyacetyl)furan (HAF; 4)i nacombinedy ield of up to 15 % (Scheme1). [7] The total yield of simple organic products was thus ar emarkable 85-90%.T he process involved heatingt he 5-(Chloromethyl)furfural (CMF) is ad isruptive innovation in the biorefinery.C hemically,i ti sa tl east as versatile as the wellknown HMF but, unlike HMF,i ti sa ccessible in high yield directly from cellulosic biomass due to its lipophilicity and stabil-ity under acidic conditions, which facilitate isolation.…”