Efficient synthesis of 5-(chloromethyl)furfural (CMF) from high fructose corn syrup (HFCS) using continuous flow processing

Kohl, Thomas M.; Bizet, Boris; Kevan, Peter G.; Sellwood, C.; Tsanaktsidis, John; Hornung, Christian H.

doi:10.1039/c7re00039a

Cited by 25 publications

(24 citation statements)

References 24 publications

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“…Due to the strong shear force generated by centrifugal forces in the CCCS, liquid-liquid mixing is enhanced considerably, accelerating reactions with fast kinetics that are limited by mass transfer. [134] Typically, microreactors have been used for single liquid phase and biphasic (gas-liquid or liquid-liquid) catalytic transformation of biomass derivatives to valuable products using homogeneous or heterogeneous catalysts (e. g., the (biphasic) synthesis of furans from sugars, [135][136][137][138][139][140][141][142][143][144] (aerobic) oxidation, [144][145][146][147][148][149] and hydrogenation of biomass derivatives [144,[150][151][152][153] ). [126] Another intensified reactor configuration for multiphase (gasliquid or liquid-liquid) catalytic biomass transformation is the spinning disc reactor, consisting of a rotating disc around which fluids are fed.…”

Section: Process Intensification For Biomass Conversionmentioning

confidence: 99%

“…With this, 60 % HMF yield at 91 % fructose conversion could be obtained from the homogeneous acid (0.25 M HCl) catalyzed dehydration of 30 wt% fructose after 2.5-3 min at 180°C in a biphasic aqueous-organic (2 : 3 volume ratio) batch system. [135][136][137][138][139][140][141][142]216] A glass chip-based microreactor was used for the biphasic synthesis of HMF by dehydration of fructose using a mixture of MIBK and 2-butanol as the organic solvent (70/30 wt%) and HCl as the catalyst in the aqueous phase (Table 4, entry 2). [215] By operating such a biphasic system in a microreactor under slug flow operation (Figures 2D, 3B and 5), the superior mixing for an efficient reaction in the aqueous phase is ensured and the extraction rate of HMF towards the non-reactive organic phase is accelerated by the enhanced mass transfer inside droplets/slugs and across the interface (due to internal circulation and high interfacial area available), thus reducing the occurrence of side reactions and increasing the yield and selectivity towards HMF.…”

Section: Homogeneously Catalyzed Furan Synthesis In a Biphasic Systemmentioning

confidence: 99%

“…The reaction towards CMF proceeded much faster as compared to the synthesis of HMF, probably because a highly acidic (37 % HCl) reaction medium was used (Table 4, entry 7). [142] This was most likely due to the higher partition coefficient of CMF in DCE, which resulted in more extraction of CMF from the aqueous phase and thus less byproduct formation. [142] This was most likely due to the higher partition coefficient of CMF in DCE, which resulted in more extraction of CMF from the aqueous phase and thus less byproduct formation.…”

Section: Homogeneously Catalyzed Furan Synthesis In a Biphasic Systemmentioning

confidence: 99%

“…[141] The dehydration of fructose resulted in higher CMF yields when using DCE (74 %) as the organic solvent compared to toluene (60 %) and MIBK (47 %) after 1 min reaction time at 100°C and 10 bar (Table 4, entry 8). [142] CMF yield of 34 % could be obtained from sucrose and 66.7 % from HFCS after 1.5 min using DCM as the extractive solvent at 100°C. Furthermore, the synthesis of CMF was performed from sucrose and high fructose corn syrup (HFCS) as a commercially available fructose feedstock, produced by the enzymatic depolymerization of corn starch.…”

Section: Homogeneously Catalyzed Furan Synthesis In a Biphasic Systemmentioning

confidence: 99%

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Catalytic Transformation of Biomass Derivatives to Value‐Added Chemicals and Fuels in Continuous Flow Microreactors

2019

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Biomass as a renewable and abundantly available carbon source is a promising alternative to fossil resources for the production of chemicals and fuels. The development of biobased chemistry, along with catalyst design, has received much research attention over recent years. However, dedicated reactor concepts for the conversion of biomass and its derivatives are a relatively new research field. Continuous flow microreactors are a promising tool for process intensification, especially for reactions in multiphase systems. In this work, the potential of microreactors for the catalytic conversion of biomass derivatives to value-added chemicals and fuels is critically reviewed. Emphases are laid on the biphasic synthesis of furans from sugars, oxidation and hydrogenation of biomass derivatives. Microreactor processing has been shown capable of improving the efficiency of many biobased reactions, due to the transport intensification and a fine control over the process. Microreactors are expected to contribute in accelerating the technological development of biomass conversion and have a promising potential for industrial application in this area.

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Section: Process Intensification For Biomass Conversionmentioning

confidence: 99%

Section: Homogeneously Catalyzed Furan Synthesis In a Biphasic Systemmentioning

confidence: 99%

Section: Homogeneously Catalyzed Furan Synthesis In a Biphasic Systemmentioning

confidence: 99%

Section: Homogeneously Catalyzed Furan Synthesis In a Biphasic Systemmentioning

confidence: 99%

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Catalytic Transformation of Biomass Derivatives to Value‐Added Chemicals and Fuels in Continuous Flow Microreactors

2019

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“…The use of biphasic reaction condition with the addition of an in situ extracting immiscible organic solvent during the reaction exhibited superior results in terms of decreased amounts of humins. Recent discoveries 6,7 showed that using a chlorine source (HCl) favored the formation of 5-chloromethylfurfural (CMF) as opposed to HMF. Let alone leaving a very reactive methyl chlorine moiety in place of the hydroxyl group, this Ox.…”

Section: Figure 3 Possible Derivatives From the Furfural Platformmentioning

confidence: 99%

Bio-Sourced Polymers: Recent Advances

Cramail

Bizet

Lamarzelle

et al. 2020

Series on Chemistry, Energy and the Environment

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Synthetic polymers are of major interest in the chemical industry, with a world production superior to 350Mt in 2016. They find applications in all the branches of industry, from packaging films to the stateof-the-art materials for sports and leisure activities, construction and aerospace industry or medical applications. Half of the amount of molecules produced by the petrochemical industry thus finds itself incorporated in the elaboration of polymer materials. With a production of 160Mt / year, ethylene can be considered as the major example of petroleum-based monomers. Green Chemistry introduced in 1998 by Anastase et al. (refer to Chapter 1 of this book), aims at providing solutions to reduce environmental impacts of our society. More precisely, this pursue of a more sustainable chemistry consists in using a source of renewable carbon to both reduce the dependence on fossil resources and thus stabilize greenhouse gas emissions (in particular CO 2 ) at the end of life. The use of renewable resources is of major interest in the elaboration of bio-sourced polymers. By using them, it is possible to mimick the fossil-based polymers -drop-in structures such as biopolyethylene-or to design new chemical structures, such as poly(lactic acid), PLA. Nowadays, the vegetal-based chemistry (renewable resources) mobilizes less than 0.5 % of arable land in the world. Some reminders of the definitions of the terms biomass, biopolymer, biodegradable polymer, bio-sourced polymer, bioplastic, biorefinery may be necessary: Biomass: material of biological origin (elaborated by alive bodies) with the exception of the materials of geological or fossil formation.Biopolymer: polymer developed by alive bodies, extracted from the biomass. Examples: polysaccharides, proteins, bacterial polymers.Biodegradable polymer: polymer the main degradation mechanism of which can be biotic, by enzymatic way. Under the action of micro-organisms and in the presence of oxygen (aerobic conditions), the organic compound decomposes totally within few months into carbon dioxide, water and mineral salts, with the appearance of a new biomass; in the absence of oxygen (anaerobic conditions), the organic compound decomposes totally within few months into carbon dioxide, methane, mineral salts and creation of a new biomass.Bio-sourced (or bio-based) polymer: synthetic polymer partially (generally > 20 %) or totally obtained from by-products stemming from the biomass. The bio-sourced character of a polymer can be determined in particular from its content in C14, according to the standard ASTM D6866. For the materials of totally fossil origin, the content in C14 is null.Bioplastic: term of popularization which indicates a 'biobased plastic' (restricted definition) and/or biodegradable (wider definition).Biorefinery: by analogy with a classic refinery, which works from fossil resources, a bio-refinery handles biomasses to produce, according to the cases, energy, fuels, materials, chemical and polymer products and/or animal and human feed. Today, two biopolymers ac...

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Cellulose fast pyrolysis for platform chemicals: assessment of potential targets and suitable reactor technology

Parihar

Bhattacharya

2019

Biofuels Bioprod Bioref

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The cellulosic component of lignocellulosic biomass can be converted to commercially valuable platform chemicals through pyrolysis provided it is effectively controlled and optimized. This review first discusses the underpinning kinetics and mechanism of cellulose pyrolysis to identify target platform chemicals. Platform chemicals like 5‐hydroxymethyl furfural, 5‐chloromethyl furfural, and levoglucosenone, which are potentially amenable to the pyrolytic conversion of cellulose, are then elucidated. There are laboratory and large‐scale reactor technologies available for converting biomass to bio‐oil but they have not been comprehensively investigated for producing platform chemicals through pyrolysis. This review critically evaluates different reactor types available for developing the catalytic pyrolysis process for converting cellulosic component of biomass to platform chemicals. The fluidized bed reactor stands out as the most suitable reactor technology for the catalytic pyrolysis of cellulose to platform chemicals owing to attributes like short residence time, high heating rate, uniform mixing, efficient heat transfer, and scalability of operations. This article provides perspective on the implementation of this technology for the pyrolysis of the cellulosic component of biomass to platform chemicals. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd

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Efficient synthesis of 5-(chloromethyl)furfural (CMF) from high fructose corn syrup (HFCS) using continuous flow processing

Abstract: Demonstrated synthesis of 5-(chloromethyl)furfural (CMF) from both solid sugars and high fructose corn syrup (HFCS) using continuous flow processing.

Cited by 25 publications

References 24 publications

Catalytic Transformation of Biomass Derivatives to Value‐Added Chemicals and Fuels in Continuous Flow Microreactors

Catalytic Transformation of Biomass Derivatives to Value‐Added Chemicals and Fuels in Continuous Flow Microreactors

Bio-Sourced Polymers: Recent Advances

Cellulose fast pyrolysis for platform chemicals: assessment of potential targets and suitable reactor technology

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