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5-Hydroxymethylfurfural from fructose : An efficient continuous process in a water-dimethyl carbonate biphasic system with high yield product recovery

Sayed, Mahmoud LU ; Warlin, Niklas LU ; Hulteberg, Christian LU orcid ; Munslow, Ian ; Lundmark, Stefan LU ; Pajalic, Oleg ; Tunå, Per LU ; Zhang, Baozhong LU ; Pyo, Sang Hyun LU and Hatti-Kaul, Rajni LU (2020) In Green Chemistry 22(16). p.5402-5413
Abstract

Bio-based 5-hydroxymethylfurfural (5-HMF) and its derivatives have attracted enormous attention due to their valuable market potential. Production of pure 5-HMF is challenging owing to the high reactivity of its functional groups and formation of by-products. In this study, an efficient continuous process for 5-HMF production in a biphasic system and its recovery at high yield and selectivity was developed. After an initial screening of different solvents, a water/dimethyl carbonate (DMC) system was selected for acid catalyzed fructose dehydration in a continuous mode using 0.23 M HCl as a catalyst. Effects of various reaction parameters on substrate conversion, product yield and selectivity, were determined. The process using 30% (w/v)... (More)

Bio-based 5-hydroxymethylfurfural (5-HMF) and its derivatives have attracted enormous attention due to their valuable market potential. Production of pure 5-HMF is challenging owing to the high reactivity of its functional groups and formation of by-products. In this study, an efficient continuous process for 5-HMF production in a biphasic system and its recovery at high yield and selectivity was developed. After an initial screening of different solvents, a water/dimethyl carbonate (DMC) system was selected for acid catalyzed fructose dehydration in a continuous mode using 0.23 M HCl as a catalyst. Effects of various reaction parameters on substrate conversion, product yield and selectivity, were determined. The process using 30% (w/v) fructose in water with three times the volume of DMC at 1 min residence time in a tube reactor at 200 °C provided 96.5% fructose conversion and 87.2% 5-HMF yield with a selectivity of 85.5% and 95.8% in aqueous and organic phases, respectively. Increasing the fructose concentration in the water phase to 52% gave 96.4% conversion and 74% 5-HMF yield. Using a fructose-glucose mixture as substrate had no effect on fructose conversion but affected slightly the selectivity of 5-HMF in the aqueous phase. Recovery of 5-HMF with ≥93% purity from DMC was achieved by solvent evaporation under vacuum, and improved by prior treatment with activated carbon, especially together with Na2CO3. Evaluation of the purified 5-HMF in a reaction with pentaerythritol showed comparable performance to the commercial 5-HMF in the production of a spirocyclic diol, a monomer for the production of polyesters and polyurethane.

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author
; ; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Green Chemistry
volume
22
issue
16
pages
12 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85090772341
ISSN
1463-9262
DOI
10.1039/d0gc01422b
project
STEPS – Sustainable Plastics and Transition Pathways, Phase 1
Farm2Furan: Surplus agricultural feedstocks to furanics
language
English
LU publication?
yes
id
7aeb5d99-944b-49fe-9205-2c279d338139
date added to LUP
2020-09-23 12:59:29
date last changed
2022-05-12 06:42:50
@article{7aeb5d99-944b-49fe-9205-2c279d338139,
  abstract     = {{<p>Bio-based 5-hydroxymethylfurfural (5-HMF) and its derivatives have attracted enormous attention due to their valuable market potential. Production of pure 5-HMF is challenging owing to the high reactivity of its functional groups and formation of by-products. In this study, an efficient continuous process for 5-HMF production in a biphasic system and its recovery at high yield and selectivity was developed. After an initial screening of different solvents, a water/dimethyl carbonate (DMC) system was selected for acid catalyzed fructose dehydration in a continuous mode using 0.23 M HCl as a catalyst. Effects of various reaction parameters on substrate conversion, product yield and selectivity, were determined. The process using 30% (w/v) fructose in water with three times the volume of DMC at 1 min residence time in a tube reactor at 200 °C provided 96.5% fructose conversion and 87.2% 5-HMF yield with a selectivity of 85.5% and 95.8% in aqueous and organic phases, respectively. Increasing the fructose concentration in the water phase to 52% gave 96.4% conversion and 74% 5-HMF yield. Using a fructose-glucose mixture as substrate had no effect on fructose conversion but affected slightly the selectivity of 5-HMF in the aqueous phase. Recovery of 5-HMF with ≥93% purity from DMC was achieved by solvent evaporation under vacuum, and improved by prior treatment with activated carbon, especially together with Na2CO3. Evaluation of the purified 5-HMF in a reaction with pentaerythritol showed comparable performance to the commercial 5-HMF in the production of a spirocyclic diol, a monomer for the production of polyesters and polyurethane.</p>}},
  author       = {{Sayed, Mahmoud and Warlin, Niklas and Hulteberg, Christian and Munslow, Ian and Lundmark, Stefan and Pajalic, Oleg and Tunå, Per and Zhang, Baozhong and Pyo, Sang Hyun and Hatti-Kaul, Rajni}},
  issn         = {{1463-9262}},
  language     = {{eng}},
  number       = {{16}},
  pages        = {{5402--5413}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Green Chemistry}},
  title        = {{5-Hydroxymethylfurfural from fructose : An efficient continuous process in a water-dimethyl carbonate biphasic system with high yield product recovery}},
  url          = {{http://dx.doi.org/10.1039/d0gc01422b}},
  doi          = {{10.1039/d0gc01422b}},
  volume       = {{22}},
  year         = {{2020}},
}