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. 2022 Dec 29;8(1):1047–1059. doi: 10.1021/acsomega.2c06409

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,*
PMCID: PMC9835634  PMID: 36643450

Abstract

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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.

Introduction

The hike in global energy consumption and continual depletion of fossil fuel sources created an emergent need of alternative energy sources. Presently, the nonrenewable sources of energy such as petroleum, natural gas, and coal account for most of the energy consumption.1 Thus, there is an extensive and continual consumption of fossil fuels, which accounts for escalated energy and fuel crises with a significant increment in greenhouse gas (GHG) emission. The exhausting fossil reserves and more dependency upon conventional sources obligated to develop processes for production of energy and chemicals from non-conventional sources such as solar energy, wind energy, hydroenergy, and bioenergy.2 However, exploration of bio-based feedstocks and sources has been in demand for the last few decades. Bioenergy is a potential renewable alternative which is cheaper and readily available and can be used as a sustainable source for production of green chemicals and fuels.3 Of the possible bioenergy options, lignocellulosic biomass (LBM) produced from agricultural waste, forest residues, municipal solid waste, and so forth can be seen as a potential feedstock for production of a variety of renewable products. The most abundant component of LBM is cellulose, which is a potential source for production of C6 sugars from LBM. Thus, the non-expensive LBM-based sugars can be explored for production of biobased chemicals such as ethanol, 5-hydroxymethylfurfural (5-HMF), butanediol, methyl ethyl ketone (MEK), lactic acid, itaconic acid, and so forth.4

Among the possible biobased chemicals from biomass-based C6 sugars, 5-HMF is endorsed as a next-generation platform chemical molecule for production of green polymers, fuels, pharmaceuticals, and other bulk chemicals.5 5-HMF has huge potential to produce furan-based biofuel molecules such as 2,5-dimethyl furan (DMF), 2,5 furandicarboxaldehyde (DFF), and so forth.6 Oxidation of 5-HMF produces 2,5-furan dicarboxylic acid (FDCA), which can be used in large applications for production of green materials, biopolymers, recyclable bottles, carpets, and so forth.7 FDCA is the building block for production of 100% recyclable biobased plastic: “polyethylene furanate (PEF)”. PEF is a furanic polyester which provides potential replacement to petro-based polyethylene terephthalate (PET).8 Therefore, production of 5-HMF from biobased C6 sugars becomes an emergent need of upcoming green industries for production of ecofriendly fuels, chemicals, and energy products.

5-HMF can be produced from C6 sugars via simple acid catalyzed dehydration reaction.9 However, the selectivity of reaction toward the desire product is a crucial parameter and majorly dependent on selectivity of acid catalysts.10 In general, both heterogeneous and homogeneous acid catalysts can be used for producing 5-HMF. The use of a heterogeneous acid catalyst creates difficulties for the availability of the surface area on the catalyst after the surface is fully saturated with reactant molecules.11 While using a homogeneous acid catalyst, reaction is carried out in the same phase; therefore, the degree of interaction between the catalyst and reactant molecules is very high as compared to different phases.12 Therefore, they are highly selective toward producing desired products and can be preferred over heterogeneous catalysts. Hu et al.19 have listed various homogeneous catalysts for HMF production from biomass.13 Several homogeneous catalysts such as oxalic acid, formic acid, HCl, H2SO4,p-toluenesulfonic acid (PTSA), and ionic liquids (ILs) have been reported with 18–90% yield of 5-HMF. Zhao et al.14 have reported a 5-HMF yield of about 18–23%) using acid catalysts (PTSA, oxalic acid, maleic acid, malonic acid, succinic acid) and water as a reaction medium. HCl was also used as a catalyst with a combination of metal chloride (AlCl3) which yielded (53%) 5-HMF.15 Seri et al.16 reported the use of LaCl3 as a Lewis acid catalyst in various organic solvents such as DMF, butanol, DMSO, DMA, sulfolane, and so forth for production of 5-HMF from d-fructose. Among all the tested solvents, DMSO, DMA, and DMF yielded >90% of 5-HMF. However, there are several challenges in terms of catalyst separation, recycle, selectivity of 5-HMF, high-boiling-point organic solvents, and so forth.

ILs are found to be interesting in the field of catalysis and organic synthesis due to their characteristic physicochemical properties such as high solubility, low viscosity, high polarity, negligible vapor pressure, high solvation, hydrogen bonding, and so forth.17 Thus, ILs are also extensively studied for production of 5-HMF due to selectivity and specific catalytic activity.18 Hu et al. reported use of various IL-based catalysts for production of 5-HMF.19 Moreau and Lansalot-Matras20 have reported the use of 1-butyl 3-methylimidazolium tetrafluoroborate [BMIm]BF4 and 1-butyl 3-methyl imidazolium hexafluorophosphate [BMIM]PF6 using DMSO as a reaction solvent to obtain up to 50% yield of 5-HMF in 3 h. HMF yields up to 88.7% have been reported using 1-methyl-3-(butyl-4-chlorosulfonyl)-imidazolium chlorosulfate ([MBCIm]SO3Cl) at 80 °C for 4 h.21 Zhang et al.22 have reported 92% yield of HMF with 99% fructose conversion using [BMIm]Cl with GeCl4. It is noted that mostly DMF and DMSO are used as reaction solvents, which are high-boiling-point organic solvents and not recommended from a green chemistry perspective.23 The separation of DMF and DMSO is also difficult, which adds to operating expenses. However, the higher yields of 5-HMF and fructose conversion were achieved, but low recyclability, a large amount of requirement, toxicity, and cost create hurdles in using them in large-scale operations and therefore limit the use of ILs.24 Therefore, it is desirable to replace these non-green solvents with low-boiling-point green solvents, which can be easily recovered after the reaction. Separation, recycle, and reuse are the significant parameters for use of IL at a large scale.25 Moreover, the process for the synthesis of IL utilizes expensive chemicals, which increases the cost of ILs. Thus, ILs become unaffordable materials for large-scale processes, even though they have higher selectivity and characteristic properties. Therefore, the focus was shifted toward polymeric ILs, which can be easily separated and recycled due to their characteristic high molecular weight. Qiu et al.26 have reported the use of a polymeric ionic liquid (PIL-Sn) catalyst using DMSO as a reaction medium at 130 °C for 1 h to obtain the yield of 51.1% 5-HMF from glucose. Chen and Liu27 have reported the use of P[BVIM]Cl with CrCl2-supported polymeric IL catalyst to yield 68.5% 5-HMF at 120 °C for 3 h in the presence of DMF. Similarly, P[BVIM]Cl with Et2AlCl-supported PIL catalyst was also reported by Chen and Liu, yielding 49% 5-HMF at 120 °C for 3 h in the presence of DMF.27

In our previous study, we have identified polyethyleneimine (PEI) as an architecture backbone for the synthesis of Bronsted acid IL having tunable acidity, higher thermal stability, easy separation, recyclability, and reuseability.28 In the present study, we have explored PolyE-IL as a recyclable Bronsted acid catalyst for conversion of fructose into 5-HMF in a green and low-boiling-point solvent. A set of PolyE-IL catalysts with tunable acidity and characteristic properties were tested for fructose dehydration. Furthermore, the process intensification study was conducted for the influence of operating parameters such as the effect of counterion, catalyst concentration, reaction time, temperature, substrate, concentration, and so forth to obtain optimum operating conditions. The reaction kinetics study was conducted in order to check the order and activation energy by using PolyE-IL catalyst. Thus, the use of IPA as a low-boiling-point green solvent and PolyE-IL as an easily recyclable catalyst provides ease of catalyst and reaction solvent handling protocol for the synthesis of 5-HMF (Scheme 1).

Scheme 1. General Reaction Scheme for Synthesis of 5-HMF by Using PolyE-IL.

Scheme 1

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Experimental Section

Materials and Methods

The substrates fructose, glucose, sucrose, galactose, and PEI with 98% purity were purchased from Sigma-Aldrich. The organic solvents IPA and ethyl acetate were commercial grade organic solvents (purity >99%) and used without further purification. The 5-HMF, fructose, glucose, sucrose, and galactose standards were purchased from Sigma-Aldrich. All the solvents and chemicals used for high-pressure liquid chromatography (HPLC) analysis are analytical grade chemicals and solvents.

HPLC Analysis

HPLC analysis was carried out on an Agilent system with an RI detector and a Bio-Rad Aminex HPX 87-H, 300 mm × 7.8 mm ion-exchange column. The analysis was performed using the mobile phase of 5 mM H2SO4 in deionized water at 50 °C and 0.6 mL/min. The liquid samples were centrifuged and diluted with deionized water and filtered before injecting into the instrument.

Fourier Transform Infrared Spectrometry Analysis

FTIR (Fourier transform infrared spectrometry) was used to identify and qualify the functional groups. In the present study, a Prestige 21 Shimadzu (Kyoto, Japan) FTIR instrument equipped with a DTGS detector and coupled with a Golden Gate Single Reflection Diamond ATR System (GS10500 Series) was used to study the interactions between the different components. The 500–4000 cm–1 regions, with a spectral resolution of 4 cm–1, were measured for all of the presented FTIR spectra, while the number of co-added scans varied from 45 scans of the materials by FTIR transmittance. The FTIR spectra were processed by Prestige software (IR solution, software version 1.50, Shimadzu, Kyoto, Japan). The ATR accessory contained a diamond crystal, shaped like an inverted prism, where the area of the measuring surface of the crystal was 2 × 2 mm2.

Procedure for the Synthesis of PolyE-IL-1 Catalyst

The synthesis of PolyE-ILs was conducted according to previously reported process.28 Approximately 1 g of PEI in 2 g of deionized water was dissolved in a 100 mL RBF (round-bottom flask) with a condenser, thermometer, addition funnel, vent, nitrogen blanketing arrangement, magnetic stirrer, and heating arrangement. The solution was mixed properly for 15 min at room temperature (35 °C). The calculated amount of H2SO4 (9.16 mmol) was added dropwise into RBF under vigorous stirring at 35–40 °C. Then H2SO4 was added dropwise with vigorous stirring to form 1:1 mol ratio mixture with PEI. After completion of addition, a light-yellow viscous liquid was observed and the resulting mixture was heated at 60 °C for 1 h to obtain the [PEI]+ [HSO4]− (PolyE-IL-1) catalyst.

General Reaction Procedure for Production of 5-HMF

The 5-HMF synthesis reactions were conducted in 100 mL batch pressure autoclave reactor assembly having PID control, agitation, a digital temperature and pressure sensor, a sampling valve, a release valve, and so forth. About 3 g (0.0166 mol) of fructose with 30 mL of IPA solvent was added in a 100 mL batch reactor vessel. The pre-calculated amount of PolyE-IL-1 catalyst (PEI IL with sulfuric acid as a counterion: [PEI]+ [HSO4]−) was added to the reactor, and the reactor vessel was closed properly with clamps. Then the reactor vessel was flushed with nitrogen 2–3 times, and about 10 bar of nitrogen pressure was purged inside the reactor. Then all the required reaction parameters were set on a PID control panel to obtain desired operating conditions. The reaction temperature was 120 °C, and the speed of agitation was set at 360 rpm. The samples were withdrawn after every 1 h by using a sampling valve and subjected to HPLC analysis. The reaction mixture was subjected to vacuum distillation in order to recover IPA. Crude 5-HMF was extracted using ethyl acetate and [PEI]+ [HSO4]− [PolyE-IL-1] catalyst was recovered and reused for another reaction. The fructose percent conversion (%X), HMF percent yield (%Y), and selectivity (%S) were calculated using the following equations:

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where CFruct,initial and CFruct,final are the initial and final fructose concentrations, respectively, and CHMF is the HMF concentration.

Results and Discussion

In order to overcome the barrier of catalyst separation, a polymeric Bronsted acid (PolyE-IL-1) catalyst has been studied in the present study. Thus, in-detail experimentation for catalyst screening, counterion selection, and process parameter optimization has been conducted.

Catalyst Performance Evaluation

It was noted that in the prior art H2SO4, PTSA was widely reported as an excellent homogeneous catalyst for 5-HMF synthesis to obtain the desired yield and selectivity.29,30 Thus, in order to evaluate the performance of PolyE-IL-1catalyst, homogeneous Bronsted acid catalysts of H2SO4 (sulfuric acid), PTSA, H3PO4 (phosphoric acid), TfOH (triflic acid), and TFA (trifluoracetic acid) were selected for catalyst performance evaluation. The performance of tested catalysts in terms of percentage yield and fructose conversion is shown in (Figure 1). In the previous study by our research group, IPA was found as an excellent green and low-boiling solvent for the synthesis of 5-HMF.31 Thus, in the present study of catalyst screen, IPA was selected as a reaction medium.

Figure 1.

Figure 1

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Catalyst performance evaluation (reaction conditions: 0.016 mol fructose, 30 mL of IPA (solvent), catalyst (0.5 g), 120 °C temperature, 120 min time).

The fructose dehydration reaction can be accelerated by any acid catalyst at the desire temperature.32 In the present study, >50% fructose conversion was noted with all the selected catalysts, but the formation of 5-HMF was observed only for PolyE-IL, H2SO4, PTSA, and TFA, while H3PO4 and TfOH did not show the formation of 5-HMF, even though the fructose conversion was 52 and 44%, respectively. It is noted that the pKa value of H2SO4 (−3), PTSA (−2.8), and TFA (0.5) is very small; thus, it could favor dehydration reaction. However, the pKa value of H3PO4 is 2.16; thus, it could not produce accessible H+ ions for fructose dehydration, but it was also noted that the pKa value of TfOH is −15, even though it is not showing the formation of 5-HMF. Thus, it can be speculated that the pKa value of the homogeneous catalyst is not a constraint to dehydrate the fructose. Other parameters such as accessibility of H+ ions, hydrophilicity, hydrophobicity, and surface interaction of fructose with the catalyst are also important for efficient dehydration.

The use of PolyE-IL-1, H2SO4, PTSA, and TFA catalyst showed >35% 5-HMF yield in the presence of IPA as a green and low-boiling-point solvent (LBP). The comparable yield of 5-HMF >50% was observed in the case of PolyE-IL-1 (60%), H2SO4 (52%), and PTSA (64%) with fructose conversions of 80, 75, and 88%, respectively. It was reported that the recycle and reuse of PTSA is a complex, multistep, and expensive unit operation.33 The good yield of 5-HMF was obtained with >80% fructose conversion in the presence of PolyE-IL-1catalyst. Thus, it can be speculated that the PolyE-IL-1catalyst can be a good choice of fructose dehydration in the presence of green and LBP solvent IPA. Moreover, the characteristic properties of PolyE-IL-1catalyst such as (a) ease of separation due to a high molecular weight, (b) a simple one-pot synthesis process, (c) tuneable acidity, and so forth can also be taken into consideration for improving process throughputs. The tuneable acidity in terms of variable counterions can provide a wide platform for improving conversion, yield, and selectivity. Thus, further study was conducted for the selection of counterion for PolyE-IL-1catalyst.

Counterion Screening for PolyE-IL Catalyst

The characteristic property of PolyE-IL catalyst to tune acidity provides a series of PolyE-IL catalysts with variable acidity.28 The acidity of PolyE-IL catalyst can be tuned by changing the counterion. The catalyst screening study depicted that the use of H2SO4, PTSA, and TFA showed the formation of 5-HMF, while H3PO4 and TfOH did not show the formation of 5-HMF. It was observed that only the acidity of the catalyst is not the contributing parameter for the homogeneous catalyst; other physicochemical properties of the synthesized catalyst can also contribute for the selective formation of 5-HMF. Thus, in order to study the effect of counterions, Bronsted acids H3PO4, H2SO4, PTSA (TsOH), TfOH, and TFA (CF3CO2H) were selected to obtain the corresponding counterions [H2PO4]−, [HSO4]−, [TsO]−, [TfO]−, and [CF3CO2]−, respectively. The influence of counterions on fructose conversion, 5-HMF yield, and selectivity is shown in Figure 2.

Figure 2.

Figure 2

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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]−.

It was observed that of the tested counterion [HSO4]−, TFA [CF3CO2]−, [TfO]−, and [TsO]− showed the formation of 5-HMF with at least 36% fructose conversion, while [H2PO4]− did not show the formation of 5-HMF. The remarkable effect of counterion was observed in the case of TfOH; the use of TfOH as such did not show any formation of 5-HMF, but the use of [TfO]− as a counterion with [PEI]+ showed the formation of 5-HMF (>2%) with 36% fructose conversion. This will provide strong evidence for the contribution of physicochemical properties of the catalyst for the efficient fructose dehydration in the presence of IPA. Thus, it can be speculated that the use of polymeric IL is beneficial for selective fructose dehydration instead of using Bronsted acid as such. The formation of an ionic complex between the base and counterion favors for fructose dehydration reaction. The maximum yield of 5-HMF (61%) with 87% conversion and 70% selectivity was observed for [HSO4]− counterion. However, [CF3CO2]−and [TsO]− showed 43 and 36% yield of 5-HMF with 74 and 72% conversion, respectively. This can be observed due to controlled release of H+ ions and favorable physicochemical properties of PolyE-IL catalyst in the presence of [HSO4]− counterion. Thus, PolyE-IL catalyst with [HSO4]− counterion was selected for further process optimization study in order to improve the yield, conversion, and selectivity.

Process Optimization Study

Process parameters such as temperature, pressure, catalyst concentration, substrate concentration, time, rpm, and substrate kinds are necessary in order to obtain the maximum yield, conversion, and selectivity of the desired product, which contributed for improving the process economics.

Effect of Catalyst Concentration

The catalyst concentration plays a crucial role in selectivity and process economics.34 In the case of homogeneous catalysis, availability of accessible active sites is dependent on the catalyst concentration, while the amount of catalyst directly contributes to operating as well as capital cost of the overall process. Tschirner et al.35 have reported the influence of catalyst concentration in a biphasic solvent where HMF yield increases with the increase in concentration up to a certain limit and then decreased steadily. Therefore, the formation of unwanted impurities and side products in the fructose dehydration reaction can be controlled by means of catalyst loading. In the present study to test the effect of PolyE-IL-1 on percentage yield, conversion, and selectivity, the PolyE-IL-1 concentration was varied from 0.06 to 0.46 g/cc. The influence of catalyst concentration on percentage yield, conversion, and selectivity is shown in (Figure 3).

Figure 3.

Figure 3

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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.).

The blank reaction was conducted in the absence of PolyE-IL-1, and it was observed that there is no formation of 5-HMF in the reaction mixture. The remarkable formation of 5-HMF was observed when PolyE-IL-1 catalyst was added in the reaction. It was noted that the fructose conversion increases with the increase in the catalyst concentration from 0.06 to 0.46 g/cc. However, the percentage yield and selectivity increase gradually up to 0.33 g/cc of catalyst loading and then decreased slowly on further increase in PolyE-IL-1 concentration. The formation of unwanted side products such as humins and condensation and polymerization products could be the cause for lower 5-HMF yield and selectivity with increased catalyst concentration.31 The practical observation after completion of reaction depicting the sedimentation of black residue is shown (Figure S8). The FTIR spectra of black residue confirms the formation of humin and condensation and polymerization products. It was noted that there is no formation of levulinic acid and formic acid at higher catalyst concentrations, which is confirmed by HPLC (Figure S5). The maximum yield of 5-HMF (74%) and selectivity (90%) with conversion (81%) was observed at 0.33 g/cc PolyE-IL-1 loading; thus, it was selected for further process intensification study.

Effect of Reaction Medium

The use of a green, recyclable, and easily separable reaction medium is one of the major process parameters for efficient synthesis of 5-HMF.36 Thus, several organic solvents such as alcohols, IPA (isopropyl alcohol), TBA (tertiary butyl alcohol), and NBA (normal butyl alcohol); nitrile, ACN (acetonitrile); ketone, MIBK (methyl isobutyl ketone) and MEK (methyl ethyl ketone); DMF (dimethylformamide); and DMSO (dimethyl sulfoxide) were widely tested for dehydration of fructose to 5-HMF.33,37,38 However, nowadays, researchers have focused on LBP solvents for 5-HMF synthesis, such as IPA, TBA, NBA, and IAA. It was noted that the reaction medium also plays a crucial role in the fructose dehydration; thus, the selection of the desire catalyst role of the organic solvent is also important.

In order to test the effect of solvent and to obtain a suitable solvent for high yield and conversion of 5-HMF in the presence of PolyE-IL-1 catalyst, various organic solvents were tested for fructose dehydration. The green and LBP solvents such as IPA, TBA, NBA, and IAA were selected as reaction media, and their performance was compared with that of DMF and DMSO. The influence of reaction medium on percentage yield, conversion, and selectivity is shown in Figure 4. The remarkable formation of 5-HMF was observed in all the tested organic solvents. Of the selected low-boiling alcoholic solvents, the yield of 5-HMF decreases with increasing C-chain length of alcohols. The visual observation of the reaction mixture clearly depicted the difference in color of the reaction mixture from faint-yellow to yellow to dark-yellow in the case of TBA, NBA, and IAA, respectively. The higher percentage conversion (>75%) and the lower percentage yield (<55%) in the case of TBA, NBA, and IAA could be due to the formation of other side products. The in-process HPLC analysis of the reaction mixture does not depict the extra peaks in the chromatogram; thus, it can be speculated that the unknown formed side products were not detectable through HPLC. Thus, these unknown side products could be humins and other condensation products, which were confirmed by FTIR analysis of the residue in the crude mixture (Figure S9), while DMF and DMSO also show a high yield of 5-HMF (80%) with 83% and 82% fructose conversion, respectively. However, of the selected LBP alcoholic solvents, the use of IPA showed 73% yield of 5-HMF with 80% fructose conversion. Thus, IPA was selected as a green and LBP organic solvent for fructose dehydration in the presence of PolyE-IL catalyst.

Figure 4.

Figure 4

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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).

Effect of Reaction Temperature

The controlled reaction temperature is an important process parameter for selective fructose dehydration which resulted in the formation of insoluble humins, soluble polymers, condensation and decomposition products, and other unwanted products.39 The 5-HMF selectivity was remarkably affected due to the reaction temperature.40 Thus, in the present study, the PolyE-IL-catalyzed fructose dehydration was performed at variable temperatures of 110–160 °C in order to check the influence of temperature on 5-HMF selectivity. The influence of reaction temperature on 5-HMF yield and fructose conversion is shown (Figure 5).

Figure 5.

Figure 5

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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).

It was observed that the fructose conversion increases with growth of reaction temperature from 110 to 160 °C, while the 5-HMF yield and selectivity increase with temperature up to 120 °C and then decrease remarkably. The maximum fructose conversion (83%) and 5-HMF yield (75%) and selectivity (90%) were observed at 120 °C. It was noted that the yield and selectivity decreased up to 25 and 10% at elevated reaction temperatures of 140 and 160 °C, respectively. The remarkable drop in 5-HMF yield and conversion at elevated reaction temperature could be observed due the formation of side products such as insoluble humins, soluble polymers, condensation and decomposition products, and other unwanted products. The dark-brown color of the reaction mixture confirms the formation of humins and side products (Figure S10). However, in the present study, it was confirmed that there is no formation of levulinic acid (LA) and formic acid (FA) (Figure S5). Thus, it can be speculated that there is no rehydration of 5-HMF to the formation of LA and FA.

Effect of Reaction Time

Wang et al.41 have reported the remarkable effect of reaction time on fructose conversion and 5-HMF selectivity. It was noted that the fructose conversion increases initially with reaction time and then decreases at a prolongated reaction time. Thus, the PolyE-IL-1-catalyzed fructose dehydration was studied by changing the reaction time from 0 to 10 h for the effect of reaction time on fructose dehydration. The influence of reaction time on fructose conversion, 5-HMF yield, and selectivity is shown (Figure 6).

Figure 6.

Figure 6

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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).

It was observed that the PolyE-IL-1-catalyszed fructose dehydration is remarkably affected by variation in reaction time. The initial reading at 0 h was noted after achieving the reaction temperature of 120 °C, and 27% fructose conversion with 1.2% 5-HMF yield was observed. It depicts the remarkable catalytic activity of PolyE-IL-1 catalyst. On increasing the reaction time up to 6 h, 5-HMF yield increased significantly and then declined gradually. The maximum 5-HMF yield (76%) was observed at 8 h. It was observed that the fructose conversion was increased up to 92% for 10 h of reaction time, but the yield and selectivity dropped to 68 and 74%, respectively.

Effect of Substrate Concentration

Li et al.42 have reported the effect of initial substrate concentrations (0.25–0.75) g. It was observed that 5-HMF yield increases initially but decreases with an increase in fructose concentration. In our present study, the substrate (fructose) concentration was varied from 0.1 to 0.36 g/cc as shown in Figure 7.

Figure 7.

Figure 7

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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).

It was observed that 0.16 g/cc of substrate concentration was selected at an optimized catalyst concentration, reaction temperature, and time. There was no significant effect of fructose concentration over a conversion that is greater than 80%, while the yield and selectivity decreased significantly beyond 0.16 g/cc concentration. The conversion is increased up to 95%, whereas the yield and selectivity decreased to 65 and 45% at 0.23 and 0.36 g/cc, respectively.

Effect of Inert Gas Pressure

In general, the rate of reaction increases by increasing reaction pressure, which helps to shift the reaction equilibrium toward right.43 However, reaction pressure is also an important parameter to accelerate the reaction. In the present study to test the effect of reaction pressure, fructose dehydration was conducted at optimized reaction parameters and reaction pressure was varied by pressurizing a batch reactor with inert gas N2. The influence of inert gas pressure on percentage yield, conversion, and selectivity of reaction is shown in Figure 8.

Figure 8.

Figure 8

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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).

In the present study, IPA was selected as a green and LBP reaction medium; it was noted that the fructose dehydration was favored >110 °C. Thus, in order to maintain the liquidity of the reaction mixture, inert gas pressure plays a crucial role. Thus, fructose dehydration was conducted with variable pressure of inert gas. The blank reaction was conducted in the absence of inert gas pressure, which depicted a significantly low yield of 5-HMF (31%). However, the yield, conversion, and selectivity increase remarkably on increasing inert gas pressure. The yield and selectivity of 5-HMF increased 2-fold when the reaction pressure increased from 6 to 12 bar. However, on further increase in reaction pressure, there is no further remarkable increase in the yield and selectivity. The maximum 5-HMF yield (75%) and conversion (85%) were obtained at 12 bar reaction pressure; thus, it is selected for further study.

Effect of rpm

The agitation plays a significant role in increasing the yield of 5-HMF. When the reaction mixture is mixed with the impeller inside the reactor, the mass-transfer rate between the reactant and catalyst molecules throws a significant impact on 5-HMF production. Xiao and Huang44 have reported the effect of agitation to study the mass-transfer limitation in a batch reactor and observed the increment in 5-HMF yield with rpm up to a certain point and remained constant on further increment. Thus, a specific speed of agitation is necessary for effective mass transfer for catalytic reaction. To test the influence of speed of agitation for PolyE-IL-1-catalyzed fructose dehydration, reactions were conducted at variable rpm. The influence of rpm on percentage yield, conversion, and selectivity is shown in Figure 9.

Figure 9.

Figure 9

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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).

It was observed that the fructose conversion (∼85%) does not get affected significantly by varying the rpm, but the 5-HMF yield and selectivity influenced remarkably. The 5-HMF yield increases notably from 35 to 75% with an rpm of 120–360 and then decreases gradually. Similarly, the selectivity increases notably from 38 to 90% with an rpm of 120–360 and then decreases gradually. The maximum yield of 5-HMF (75%) and selectivity (90%) with 85% fructose conversion was observed at 360 rpm; thus, it is selected for further study.

Effect of Substrate Types

It was reported that the hexose sugars are preferable for dehydration to 5-HMF.45 Of the possible hexose sugars, fructose is the most favorable substrate due to its chemistry at C2 carbon.45 In order to test the efficiency of PolyE-IL-1 catalyst for dehydration of other hexose sugars, various substrates such as glucose, sucrose, and galactose are also tested under the optimized conditions. The influence of substrate on percentage conversion, yield, and selectivity is shown in Figure 10.

Figure 10.

Figure 10

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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).

It was noted that all the tested substrates show remarkable formation of 5-HMF in the presence of PolyE-IL-1 catalyst and IPA as a reaction medium. The maximum yield (75%) and selectivity (90%) of 5-HMF with 85% conversion were observed for fructose. However, the in the case of glucose, sucrose, and galactose, the percentage conversion is almost 80%, but the yield and selectivity of 5-HMF are decreased significantly as compared to fructose. Sucrose yielded 60% 5-HMF with 70% 5-HMF selectivity, while glucose yielded 54% HMF with 75% selectivity. The lowest yield (38%) of 5-HMF was observed for galactose with 65% selectivity. The drop-in yield for glucose, sucrose, and galactose could be observed due to the unfavorable chemistry at C2 carbon of C6 sugars.46 The dehydration of glucose to 5-HMF proceeded with isomerization and formation of fructofuranose intermediates.47 Thus, the formation of fructose and fructofuranose intermediate is an important step for the formation of 5-HMF. However, the highest yield was observed for fructose in the presence of PolyE-IL-1 catalyst.

Recycle Study of the Catalyst

In order to develop an energy-efficient, economic, and environment-friendly process, recycle and reuse of the catalyst is an important step to improve the operating expenses.48 The PolyE-IL-1 catalyst is a high-molecular-weight Bronsted IL having higher solubility in water but having negligible solubility in several water immiscible solvents.28 Thus, this characteristic property is beneficial for separation of the catalyst from the reaction mixture by means of simple liquid–liquid extraction and evaporation. After completion of reaction, IPA was evaporated through vacuum distillation, the bottom was mixed with water to extract the catalyst, and ethyl acetate was used to extract 5-HMF. The higher partition of 5-HMF in EA allows easy separation of 5-HMF from the evaporated reaction mixture. The simple evaporation of the aqueous layer provides PolyE-IL-1 catalyst. In order to test the recycle performance of the PolyE-IL-1 catalyst, fructose dehydration was conducted with the recycled catalyst. The influence of the recycled catalyst on percentage yield, conversion, and selectivity is shown in Figure 11.

Figure 11.

Figure 11

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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).

The PolyE-IL-1 catalyst was tested for five consecutive recycle runs and used as such for fructose dehydration after each cycle. It was observed that the PolyE-IL-1 catalyst after recycle and reuse showed the consistency in yield (75%), conversion (85%), and selectivity (∼90%). The structural changes in the recycled catalyst were confirmed by using FTIR, and the resulting FTIR spectrum was compared with FTIR of the fresh catalyst. The comparison of FTIR spectrum of the fresh catalyst and the catalyst recycled after the fifth recycle run did not show any significant deviation in the characteristic peaks of PolyE-IL-1 catalyst. Thus, it can be speculated that the PolyE-IL-1 catalyst has excellent stability during the recycle, which helps to improve the process economics.

Performance Equation for the Batch Reactor

In the present study, fructose dehydration in the presence of PolyE-IL-1 catalyst was conducted in a batch pressure autoclave reactor with a four pitch bled impeller. The batch reactions where conducted in discrete time intervals. Ideally, it is assumed that all the molecules in the batch reactors have same residence time.49 In order to obtain the exact time required to convert fructose molecule into 5-HMF, it is important to validate the experimental data through the performance equation for the batch reactor. Thus, the present experimental data for fructose conversion and rate of reaction were used to study the performance equation for the batch reactor as below.

It is assumed that the concentration distribution of the reactant is uniform throughout the reactor since the rate of mixing at each point is the same.

The mole balance equation for conversion of fructose to 5-HMF is

graphic file with name ao2c06409_m004.jpg
graphic file with name ao2c06409_m005.jpg 4
graphic file with name ao2c06409_m006.jpg 5
graphic file with name ao2c06409_m007.jpg 6

where N = the no. of initial moles of fructose, V = volume of reaction mixture within reactor, and dN = the change in number of moles.

Therefore

graphic file with name ao2c06409_m008.jpg 7
graphic file with name ao2c06409_m009.jpg 8

Therefore, reaction time

graphic file with name ao2c06409_m010.jpg 9

Integrating the above equation, we get

graphic file with name ao2c06409_m011.jpg 10
graphic file with name ao2c06409_m012.jpg 11

Since the reaction is in the liquid phase, for a constant volume system, V = V0.

Therefore, the design equation is

graphic file with name ao2c06409_m013.jpg 12

where t is the reaction or residence time (h), CFruct,initial is the initial concentration of fructose (g/mL), X is the conversion of fructose, and (−r) is the reaction rate of fructose. The performance curve (X vs 1/(–r)) and residence time calculations are shown in the Supporting Information.

Rate Kinetic Study for Fructose Dehydration by Using PolyE-IL-1 Catalyst

Kinetics of a chemical reaction is one of the important parameters for determining a reaction rate model which is helpful for the interpretation of the change in concentration of a reactant or product with respect to time.50 It gives inference to reject or support a reaction mechanism that varies with the experimental result. The study of reaction kinetics of catalytic reaction is helpful for designing the reactor for the required reaction.

In order to study the reaction kinetics, in-process samples were collected at different time intervals and the respective concentration of fructose and 5-HMF was estimated by using HPLC. It was observed that the concentration of both fructose and 5-HMF varies with respect to time at different temperatures, while at a higher temperature, the concentration of 5-HMF decreases with increase in time (Figure S11). This could be observed due to further deterioration of 5-HMF or the formation of humins, polymers, and condensation products.

From Figure S12, the plot between −ln(1 – X) and time (t), it was evident that the order of reaction was 1 with slope k (Table S1), with zero intercept for different temperatures, and therefore, the best fit plot for the fructose dehydration reaction is the first-order rate equation. Therefore, it was inferred that the rate doubles if the concentration is doubled and the rate becomes halved when the concentration is halved. The integrated rate equation for first order in terms of conversion was derived and expressed (eqs 4–9) (Supporting Information).

Further, activation energy was determined by using Arrhenius equation51

graphic file with name ao2c06409_m014.jpg 13

Now, taking log both the sides, we get

graphic file with name ao2c06409_m015.jpg 14

where k is the rate constant, R is the universal gas constant (8.314 J/mol/K), A is the pre-exponential factor, and Ea is the activation energy (kJ/mol).

It was observed that the rate constant (k) increases exponentially with decreasing activation energies and increasing temperature or the rate constant decreases exponentially with increasing activation energies and decreasing temperature (Table S1). Figure S13 shows the Arrhenius plot (ln k vs 1/T) for determining activation energy.

Zhao et al.52 reported the activation energy of 33.75 kJ/mole for fructose dehydration to 5-HMF in DMSO medium for the PTSA-catalyzed system and 96.51 kJ/mole for the oxalic acid-catalyzed system at 100–140 °C. Li et al.53 reported the activation energy of about 112 kJ/mole for the formic acid-catalyzed system and 125 kJ/mole for the acetic acid-catalyzed system at 180–220 °C. Also, 123 kJ/mole of activation energy was reported by Fachri et al.54 in the H2SO4-catalyzed system at 140–180 °C. Asghari and Yoshida55 studied the kinetics of fructose dehydration and reported 160.6 kJ/mole of activation energy using HCl catalyst at 210–270 °C. Table 1 summarizes the comparison of activation energy required for the PolyE-IL-1-catalyzed system and activation energies required for various catalytic systems. The activation energy of 12.4 kJ/mol is observed for the present PolyE-IL-1-catalyzed system, which is quite less as compared to the reported systems. Therefore, due to the low activation energy, the present system is less energy-intensive and highly productive.

Table 1. Comparison of Activation Energies for Different Systems.

sr. no catalyst reaction conditions (solvent, temp, pressure) activation energy (kJ/mol) reference
1 oxalic acid DMSO at 110–140 °C 96.51 Zhao et al. (2011)
2 PTSA DMSO at 110–140 °C 33.75 Zhao et al. (2011)
3 formic acid water at 180–220 °C and 100 bars 112 Li et al. (2009)
4 acetic acid water at 180–220 °C and 100 bars 125 Li et al. (2009)
5 H2SO4 water at 140–180 °C 123 Fachri et al. (2015)
6 HCl (pH-1.8) water at 210–270 °C and 40 bars 160.6 Asghari et al. (2007)
7 Bronsted acid (pH-1.8) water at 210–270 °C 159.1 Nikbin et al. (2012)
8 HCl–KCl water at 74–147 °C 115 Swift et al. (2014)
9 activated carbon water at 160–220 °C and 50 bars 135 Sairanen et al. (2014)
10 H2SO4 water–acetone at 180–300 °C and 200 bars 99 Bicker et al. (2003)
11 PolyE-IL(PEI-H2SO4) IPA at 120 °C and 12 bars 12.4 present work
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Conclusions

In the present article, Bronsted acid polymeric IL catalyst PolyE-IL-1 was explored as a selective and efficient catalyst for fructose dehydration in the presence of a green and low-boiling-point organic solvent. The maximum yield of 5-HMF (75%) and selectivity (90%) with (85%) fructose conversion were achieved under optimized reaction conditions. It was observed that the operating parameters such as counterion, catalyst concentration, reaction time, temperature, substrate concentration, and so forth greatly affected the conversion, yield, and selectivity. The combination of a recyclable catalyst and green LBP solvent provides several advantages to the reported system, such as

  • a

    Ease of recyclability of PolyE-IL-1 catalyst helps to improve the process economics and advantageous from a green chemistry point of view.

  • b

    Selective dehydration of fructose into 5-HMF without the formation of levulinic and formic acid.

  • c

    Use of the green low-boiling solvent IPA adds benefits to ease of solvent recovery and improving the process cost.

The kinetic study showed the first-order reaction with the activation energy of 12.4 kJ/mole. Requirement of low activation energy adds benefits to reaction selectivity, productivity, process economics, and so forth. Therefore, the present catalytic system provides a platform for development of a green, efficient, environmentally and economically scalable and feasible process.

Acknowledgments

The authors are grateful for the financial support from the Department of Biotechnology (DBT), Ministry of Science and Technology, India.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.2c06409.

  • Process HPLC analysis chromatograms; HPLC analysis of STD; calculations of kinetic study; performance curve; plots for order kinetics; and pictorial images of the reaction mixture, the reactor, and so forth (PDF)

The authors declare no competing financial interest.

Supplementary Material

ao2c06409_si_001.pdf (464KB, pdf)

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Supplementary Materials

ao2c06409_si_001.pdf (464KB, pdf)

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