Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2022 Dec 29;8(1):1047-1059.
doi: 10.1021/acsomega.2c06409. eCollection 2023 Jan 10.

PolyE-IL Is an Efficient and Recyclable Homogeneous Catalyst for the Synthesis of 5-Hydroxymethyl Furfural in a Green Solvent

Ayush Vasishta  1 , Hitesh S Pawar  1
Affiliations

PolyE-IL Is an Efficient and Recyclable Homogeneous Catalyst for the Synthesis of 5-Hydroxymethyl Furfural in a Green Solvent

Ayush Vasishta et al. ACS Omega. .

Abstract

5-Hydroxymethyl furfural (5-HMF) is a potential platform molecule with multidimensional applications and can be produced from biomass-based hexose sugars. In the present article, polyethyleneimine (PEI)-functionalized polymeric Bronsted acid ionic liquid (PolyE-IL) catalyst has been explored for fructose dehydration in the presence of isopropyl alcohol (IPA) as a green and low-boiling-point (LBP) organic solvent. The use of homogeneous PolyE-IL catalyst provides several specific advantages in terms of high yield, conversion, selectivity, ease of catalyst separation, recycle and reuse, and so forth. PEI with various Bronsted acid counterions such as H2SO4, H3PO4, TsOH, TfOH, and TFA provides the corresponding variables of PolyE-IL such as [PEI]+[HSO3]-, [PEI]+[H2PO4]-, [PEI]+[CF3CO2]-, [PEI]+[TfO]-, and [PEI]+[TsO]-, which are tested for fructose dehydration in the presence of IPA. Of the tested catalysts, only PolyE-IL with [HSO4]-, [CF3CO2]-, [TfO]-, and [TsO]- counterions showed the formation of 5-HMF. [PEI]+[HSO4]- showed the maximum yield of 5-HMF (61%) and selectivity (70%) with (87%) fructose conversion. Thus, further process optimization study was conducted to obtain the maximum yield, conversion, and selectivity. The intensified process provides a maximum yield of 5-HMF of 75% with 85% fructose conversion and 90% selectivity. The catalyst recyclability study showed the consistency in 5-HMF yield (75%), conversion (85%), and selectivity (90%) for five consecutive recycle runs. However, the study of reaction kinetics showed the first-order kinetics with an activation energy of 12.4 kJ/mole by using [PEI]+[HSO4]- catalyst. Thus, the use of an easily recyclable and robust catalyst provides an efficient route for production of 5-HMF in the presence of a green solvent.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. General Reaction Scheme for Synthesis of 5-HMF by Using PolyE-IL
Figure 1
Figure 1
Catalyst performance evaluation (reaction conditions: 0.016 mol fructose, 30 mL of IPA (solvent), catalyst (0.5 g), 120 °C temperature, 120 min time).
Figure 2
Figure 2
Effect of different counterions on fructose conversion, 5-HMF yield, and selectivity (reaction conditions: 0.016 mol fructose, 0.5 g of PolyE-IL counterions, 30 mL of IPA (solvent), 120 °C temperature, 6 h time). PolyE-IL-1: [PEI]+[HSO4]−, PolyE-IL-2:[PEI]+[H2PO4]−, PolyE-IL-3: [PEI]+[CF3CO2]−, PolyE-IL-4: [PEI]+[TfO]−, and PolyE-IL-5: [PEI]+[TsO]−.
Figure 3
Figure 3
Effect of catalyst concentration on fructose conversion, 5-HMF yield, and selectivity (reaction conditions: 0.016 mol fructose, 30 mL of IPA (solvent), 120 °C temperature, 6 h time.).
Figure 4
Figure 4
Effect of reaction medium on fructose conversion, 5-HMF yield, and selectivity (reaction conditions: 0.016 mol fructose, 0.33 g/cc PolyE-IL-1 catalyst, 30 mL of solvents, 120 °C temperature, 6 h time).
Figure 5
Figure 5
Effect of reaction temperature on fructose conversion and 5-HMF yield and selectivity. (Reaction conditions: 0.016 mol of fructose, 0.33 g/cc PolyE-IL-1 catalyst, 30 mL of IPA (solvent), reaction time 6 h).
Figure 6
Figure 6
Effect of reaction time on fructose conversion, 5-HMF yield, and selectivity. (Reaction conditions: 0.016 mol fructose, 0.33 g/cc PolyE-IL-1 catalyst, 30 mL of IPA (solvent), 120 °C temperature).
Figure 7
Figure 7
Effect of substrate concentration on fructose conversion, 5-HMF yield, and selectivity (reaction conditions: 0.33 g/cc PolyE-IL-1 catalyst, 30 mL IPA (solvent), 120 °C temperature, 6 h time).
Figure 8
Figure 8
Effect of pressure on fructose conversion, 5-HMF yield, and selectivity (reaction conditions: 0.016 mol fructose, 0.33 g/cc PolyE-IL-1 catalyst, 30 mL of IPA (solvent), 120 °C temperature, 6 h time).
Figure 9
Figure 9
Effect of rpm on fructose conversion, 5-HMF yield, and selectivity (reaction conditions: 0.016 mol fructose, 0.33 g/cc PolyE-IL-1catalyst, 30 mL of IPA (solvent), 120 °C temperature, 12 bar pressure, 6 h time).
Figure 10
Figure 10
Effect of substrates on fructose conversion, 5-HMF yield, and selectivity (reaction conditions: 0.16 g/cc substrates, 0.33 g/cc PolyE-IL-1 catalyst, 30 mL of IPA (solvent), 120 °C temperature, 12 bar pressure, 6 h time).
Figure 11
Figure 11
Catalyst recycle study on fructose conversion and 5-HMF yield (reaction conditions: 0.0166 mol fructose, 0.33 g/cc PolyE-IL-1 catalyst, 30 mL of IPA (solvent), 120 °C temperature, 12 bar pressure, 6 h time).
See this image and copyright information in PMC

References

    1. U.S. Energy Information Administration. https://www.eia.gov/ (accessed on Dec 14, 2022).
    1. Capellán-Pérez I.; Mediavilla M.; de Castro C.; Carpintero Ó.; Miguel L. J. Fossil fuel depletion and socio-economic scenarios: An integrated approach. Energy 2014, 77, 641–666. 10.1016/j.energy.2014.09.063. - DOI
    1. Perea-Moreno M. A.; Samerón-Manzano E.; Perea-Moreno A. J. Biomass as renewable energy: Worldwide research trends. Sustainability 2019, 11, 863.10.3390/su11030863. - DOI
    1. Isikgor F. H.; Becer C. R. Lignocellulosic biomass: a sustainable platform for the production of bio-based chemicals and polymers. Polym. Chem. 2015, 6, 4497–4559. 10.1039/c5py00263j. - DOI
    1. van Putten R. J.; van der Waal J. C.; de Jong E. D.; Rasrendra C. B.; Heeres H. J.; de Vries J. G. Hydroxymethylfurfural, a versatile platform chemical made from renewable resources. Chem. Rev. 2013, 113, 1499–1597. 10.1021/cr300182k. - DOI - PubMed