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# On the Kinetics of 2,5-DMF Oxidation: Experiments and Modeling

Philippe Dagaut, Guillaume Dayma

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Philippe Dagaut, Guillaume Dayma. On the Kinetics of 2,5-DMF Oxidation: Experiments and Modeling. Twenty-Second International Conference on Flow Dynamics, Nov 2025, Sendai, Japan. 2025. hal-05368768

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22nd International Conference on Flow Dynamics

Nov. 10-13, 2025

Sendai International Center,
Sendai, Miyagi, Japan

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# On the Kinetics of 2,5-DMF Oxidation: Experiments and Modeling

Philippe Dagaut¹, Guillaume Dayma¹

¹CNRS, ICARE

1C Avenue de la recherche scientifique, Orleans, 45071, France

## ABSTRACT

2,5-Dimethylfuran-O₂-N₂ mixtures were oxidized in a fused-silica jet-stirred reactor at 1 bar and over a temperature range of 740–1280 K, with equivalence ratios ranging from 0.5 to 4. Samples of the reacting mixtures were collected in Pyrex bulbs using a sonic probe for gas chromatography analysis and sent to a Fourier-transform infrared spectrometer for online quantification. A large number of oxidation products were observed. We used two previously proposed detailed chemical kinetic reaction mechanisms to simulate the experiments and rationalize the results.

## 1. Introduction

2,5-Dimethylfuran (2,5-DMF) is a cyclic ether that has been proposed as a substitute fuel for internal combustion engines. Similarly to ethanol, 2,5-DMF displays distinctive physicochemical characteristics that render it a promising substitute for gasoline. 2,5-DMF displays a greater affinity for gasoline than ethanol. In comparison to ethanol, 2,5-DMF exhibits a higher boiling point, a higher energy density, and a lower solubility in water. The principal characteristics of 2,5-DMF, ethanol, gasoline and diesel [1, 2] are compared in Table 1. In 2007, Roman-Leshkov et al. [3] first proposed a new method of producing 2,5-DMF from the sugars found in biomass. This catalyzed process transforms fructose into 5-hydroxymethylfurfural (5-HMF), an intermediate product that can be converted into 2,5-DMF. This discovery has generated enormous interest in this potential fuel source over the last few decades. The synthesis of 2,5-DMF has been the subject of numerous studies, as reviewed in references [2] and [4]. Using 2,5-DMF as a fuel in engines requires a good understanding of its pyrolysis and oxidation mechanisms. To this end, many research studies have been conducted using various experimental devices, such as flames, reactors, shock tubes and engines. Grela et al. [5] conducted an experimental study on the thermal decomposition (pyrolysis) of 2,5-dimethylfuran (2,5-DMF). They measured the decomposition products of 2,5-DMF in a low-pressure (1 mTorr) flow reactor at high temperatures (1050–1270 K). This led to the proposal of a model for the pyrolysis of 2,5-DMF. In 1998, Lifshitz et al. [6] studied the pyrolysis of 2,5-DMF in a shock tube at 2-3.7 bar and 1070-1370 K. They obtained the distribution of 2,5-DMF decomposition products. They deduced the rate constants of several reactions and developed a kinetic scheme comprising 50 species and 181 reactions. Since then, numerous theoretical and experimental studies have been conducted to improve our understanding of the pyrolysis of 2,5-DMF [7, 8]. The first studies on characterizing 2,5-DMF flames date back to 2009. Wu et al. [9] published a qualitative study on identifying intermediate species in the combustion of the 2,5-DMF/O₂/Ar mixture at 30 Torr and in fuel-rich conditions (φ = 2). Based on the identified species, the researchers proposed different consumption pathways for furan, 2-methylfuran, and 2,5-DMF. Wu et al. completed their studies by measuring the laminar burning velocities of

2,5-DMF/air mixtures as a function of temperature [10] and pressure [11].

<table><caption>Table 1 Main physicochemical characteristics of ethanol, 2,5-dimethylfuran, gasoline and Diesel.</caption><thead><tr><th rowspan="2">Properties</th><th colspan="4">Fuel</th></tr><tr><th>Ethanol</th><th>2,5-DMF</th><th>gasoline</th><th>Diesel</th></tr></thead><tbody><tr><td>Chemical formula</td><td>C<sub>2</sub>H<sub>6</sub>O</td><td>C<sub>6</sub>H<sub>8</sub>O</td><td>C<sub>4</sub>-C<sub>14</sub></td><td>C<sub>8</sub>-C<sub>25</sub></td></tr><tr><td>Molecular weight (g/mol)</td><td>46.07</td><td>96.13</td><td>102</td><td>≈ 200</td></tr><tr><td>Density (Kg/L)</td><td>0.79</td><td>0.89</td><td>0.74</td><td>≈ 0.84</td></tr><tr><td>Boiling point (°C)</td><td>77.3</td><td>93</td><td>27-225</td><td>180-317</td></tr><tr><td>Lower calorific value (MJ/kg)</td><td>26.8</td><td>33.7</td><td>42.7</td><td>43</td></tr><tr><td>Energy density (MJ/L)</td><td>33.9</td><td>37.8</td><td>57.7</td><td>51.2</td></tr><tr><td>Auto-ignition temperature (°C)</td><td>434</td><td>286</td><td>420</td><td>246</td></tr><tr><td>Research octane number</td><td>120</td><td>119</td><td>95</td><td>—</td></tr><tr><td>Cetane number</td><td>5-8</td><td>9</td><td>10-15</td><td>40-55</td></tr></tbody></table>

In 2010, Tian et al. [12] used a constant-volume spherical combustion chamber to measure the laminar flame speeds of 2,5-dimethylfuran (2,5-DMF), ethanol, and gasoline at atmospheric pressure and several initial temperatures (50, 75, and 100 °C) and equivalence ratios (φ) ranging from 0.6 to 2. The first detailed kinetic model of the oxidation and pyrolysis of 2,5-DMF was proposed in 2013 by Sirjean et al. [13]. They obtained the first measurements of the auto-ignition times of 2,5-DMF/O₂/Ar mixtures using a shock tube at 1 and 4 bar, 1300–1831 K, and φ = 0.5, 1, and 1.5. Validation of the model was conducted using experimental results and
pyrolysis data [6].

Somers et al. published a detailed study on the pyrolysis and oxidation of 2,5-DMF [14]. They provided a large set of data obtained using different experimental devices and techniques: (a) they measured species concentrations during the pyrolysis of 2,5-DMF in a shock tube, (b) they obtained auto-ignition delay times in a shock tube at atmospheric to high-pressure (20 and 80 bar), (c) they determined the species concentration profiles in a jet-stirred reactor, and (d) they determined laminar flame speeds at atmospheric pressure. In addition, they developed a kinetic reaction mechanism for the oxidation of 2,5-DMF. In 2014, three in-depth studies on the oxidation of furan and its derivatives (2-methyl furan and 2,5-dimethyl furan) were published. They reported the evolution of the concentration of species in premixed flame of furan [15], 2-methyl furan [16], and 2,5-DMF [17] under similar conditions (20 and 40 mbar at φ = 1 and 1.7). The concentration profiles of the species (reactants, products, stable intermediate species and radicals) were obtained as a function of the distance from the burner. A kinetic model was developed.

An experimental study associated with kinetic modeling of the pyrolysis of 2,5-DMF was also published by Cheng et al. [18]. They proposed a detailed kinetic model (1173 reactions and 285 species) inspired by different mechanisms from the literature. They also provided, for the pyrolysis of 2,5-DMF, new experimental data obtained using a flow reactor at different temperatures (780-1470 K) and pressures (30, 50 and 760 Torr).

Alexandrino et al. [19] published in 2015 their experimental and modeling work on the pyrolysis and oxidation of 25-DMF. They discussed the influence of temperature (500-1400 K), pressure (1-40 bar), 25-DMF concentration (100-4500 ppm), and φ on the conversion of 2,5-DMF using different flow reactors. They used their experimental data to validate their kinetic model (1314 reactions and 255 species) inspired by the mechanism proposed by Sirjean et al. [13].

Tran et al. [20, 21] have also worked on the construction of furans oxidation model (furan, 2-MF and 2,5-DMF). They introduced reactions with C₈ aromatic hydrocarbons and a sub-mechanism for the formation of polycyclic aromatic hydrocarbons (PAHs) up to C₁₆ was included. They also determined the temperature and concentration profiles of the species in laminar flames of 2-MF and 2,5-DMF, in fuel-rich conditions (φ = 1.7) and at low pressure (40 kPa). These experimental results were used to validate their model.

Eldeeb [22] studied the oxidation of 2,5-DMF and isooctane (model compound for gasoline) in shock tube. Autoignition delay measurements were performed at 5-12 atm, in the temperature range 1009-1392 K, and at φ=0.5-2. They also developed a kinetic model of oxidation for the iso-octane/2,5-DMF mixture. The kinetic mechanism of 2,5-DMF oxidation derives from that of Somers et al. [14]. Their shock tube data were used for model validation. Several studies were also performed in engines and pollutant emissions during the combustion of

2,5-DMF and blends with gasoline were determined [23-30].

To complement our previous research [14], we conducted experiments on the oxidation kinetics of 2,5-DMF in a well-stirred reactor and simulated the results using models proposed by Somers et al. [14] and Tran et al. [20].

## 2. Method

The experiments were conducted in a 42-mL fused silica jet-stirred reactor (JSR) [31]. We used an HPLC pump with an online degasser to inject the fuel, which was 99% pure. The fuel was delivered to a vaporizer assembly with an N₂ flow. Before entering the JSR, the fuel and oxygen flows were separated to prevent fuel oxidation. The nitrogen and oxygen flow rates were controlled by mass flowmeters. We checked the JSR for thermal homogeneity using a silica-protected thermocouple. We studied the oxidation of 2,5-dimethylfuran (2,5-DMF) with initial mole fractions of X(2,5-DMF, in) ranging from 0.1 to 0.15%, with residence times of 0.07 and 0.1 seconds. Operating conditions were 1 bar, 740-1280 K, and fuel-lean to fuel-rich (φ = 0.5-4).

Samples of the reacting mixtures were collected in Pyrex bulbs using a sonic probe for gas chromatography (GC) analyses. GC-TCD, GC-FID, and GC-MS were used. Online FTIR quantification was also performed to measure H₂O, CH₂O, CO, and CO₂.

Kinetic modeling was performed using the PSR code from the Chemkin II computer code library [32]. We used the kinetic reaction mechanism proposed by Somers et al.

<figure><img src="image_4.png" /><figcaption>Fig. 1 Mole fraction of 2,5-DMF in a JSR (φ=0.5, 1.0, and 2.0; X(2,5-DMF,in) = 0.1%, RT = 0.07s). Data (symbols) are compared to simulations using Somers' model.</figcaption></figure>

for the oxidation of 2,5-DMF under various conditions, including earlier JSR oxidation data at 10 bar. We also tested the mechanism proposed by Tran et al. [20].

## 3. Results and Discussion

Many oxidation products were detected during the oxidation of the fuel. They ranged from H₂ to indene. Figure 1 shows an example of the present results.

From that figure, one can see that the model is in agreement with the data and that the fuel conversion is
not very sensitive to the initial oxygen content. Both
models represent well the fuel conversion and formation
of final products and main intermediates. However, they
fail to represent other products such as propadiene,
propyne and but-1-yne.

4. Concluding Remarks

In this study, we identified a substantial number of
oxidation products of 2,5-DMF at atmospheric pressure
across a range of fuel-to-air ratios, encompassing fuel-
lean to fuel-rich conditions. These findings augment
those previously obtained at 10 bar [14]. Two established
models from the literature were employed to simulate the
experiments, exhibiting a satisfactory degree of
alignment with the data. Model improvements are needed
to represent a range of intermediate stable products.

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Acknowledgements

This work received financial support from the LabEx CAPRYSSES (ANR-11-LABX-006-01) and from the European Research Council under the European Community's Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement no. 291049 2G-CSafe.