Production and Downstream Integration of 5-(Chloromethyl)furfural from Lignocellulose

Abstract

The importance of reducing the strong dependence of the chemical industry on fossil feedstock is no longer a debate. Above-the-ground carbon is abundant, but scalable technologies to supply alternatives to fossil-fuel-derived chemicals and/or materials at the world scale are still not available. Lignocellulosic biomass is the most available carbon source, and a first requirement for its valorization is the complete saccharification of its sugar-bearing components. HCl-based technologies can achieve this at 20 °C and ambient pressure. These principles were disclosed in the 1920s, but the inability to economically separate sugars from acids impeded its commercialization. Avantium Chemicals B.V. developed a modern version of this “Bergius” highly concentrated acid hydrolysis, in which the saccharides in HCl are transformed into furanics without any prior purification, in particular, to 5-(chloromethyl)furfural (CMF). Saccharide conversion to CMF was developed by Mascal in the early 2000s. CMF is extracted in situ using immiscible organic solvents, allowing for an easy product separation. This study not only targets to investigate the viability and optimization of this integrated process but also aims to predict the outcome of the CMF formation reaction by applying design of experiment techniques from the hydrolyzed saccharides varying a broad range of reaction parameters.

One-Pot Conversion of Starch into 5-Chloromethylfurfural and 5-Hydroxymethylfurfural in a Low-Transition Temperature Mixture

“…For example, an impressive yield of 97.6% 5-CMF was recently reported from a mixture of glucose, mannose, and xylose obtained from the acid hydrolysis of Aspen wood chips. However, to prepare the reaction medium, concentrated HCl (32% w/w) was further saturated with HCl gas at 7 bar to obtain a final HCl concentration of 42%w/w, and the produced 5-CMF was extracted using difluorobenzene . Other reported studies have used other halogenated solvents as the extracting medium; therefore, the use of other solvents according to the green chemistry guidelines and less dangerous catalysts should be further explored in future work.…”

Production and Synthetic Possibilities of 5-Chloromethylfurfural as Alternative Biobased Furan

“…A continuous method of production with a coiled flow inverter reactor was presented in which anisole, a green solvent, was fed continuously to produce CMF at a yield of 79% at a residence time of 256 s [58]. The highest CMF yield (96.70%) was reported by Moron et al under low temperature and ambient pressure conditions from initial hydrolysis of aspen wood chips followed by downstream saccharification [66].…”