Experimental and Detailed Kinetic Modeling Study of the Oxidation of

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Experimental and Detailed Kinetic Modeling Study of the Oxidation of 1-Propanol in a Pressurized Jet-Stirred Reactor (JSR) and a Combustion Bomb B. Galmiche,† C. Togbe,‡ P. Dagaut,*,‡ F. Halter,† and F. Foucher† † ‡

Institut PRISME, Universite d’Orleans, Polytech Vinci
45072 Orleans cedex, France CNRS—INSIS, 1C, Ave de la Recherche Scientifique
45071 Orleans cedex 2, France

bS Supporting Information ABSTRACT: New experimental results were obtained to better characterize and understand the oxidation and combustion of 1-propanol, which is a renewable alcohol usable as an alternative to petrol-derived gasoline. A pressurized jet-stirred reactor (JSR) was used to measure concentration profiles of stable species (reactants, intermediates, and final products) at 10 atm, over a range of temperatures (T = 770
1190 K) and equivalence ratios (j = 0.35
2). A combustion bomb was used to measure burning velocities of 1-propanol/air mixtures at pressures of P = 1
10 bar and T = 423 K, over a range of equivalence ratios (0.7 e j e 1.4) and at 1 bar for temperatures in the range of 323
473 K. The effects of total pressure and temperature on burning velocity were determined under stoichiometric conditions. The oxidation of 1-propanol under these conditions was modeled using a detailed chemical kinetic scheme taken from the literature and a kinetic scheme of ours was extended to the oxidation of 1-propanol. The computational results agreed reasonably well with the present set of experimental data, but the prediction of some intermediates and the burning velocities of 1-propanol/air mixtures under fuel-rich conditions could only be represented using the mechanism proposed here. Reaction path and sensitivity analyses were used to rationalize the results.

1. INTRODUCTION With the announced decline of petrol reserves and a growing concern about global warming caused by still-increasing emissions of greenhouse gas (GHG), the replacement of fossil fuels has become a hot topic. While much effort has been devoted to the development of electrically powered vehicles, in the near future, the substitution of liquid fuels for air transportation or long-distance ground transportation is improbable. In that context, bioderived liquid fuels, which are renewable, are considered for blending future transportation fuels.1,2 They may be less polluting than fossil fuels and could help decrease the net GHG emissions.3 Currently, ethanol represents more than 90% of the worldwide biofuel production.4 Its oxidation kinetics has been extensively studied.5 However, ethanol’s high miscibility with water causes serious storage problems, which is not so important with larger alcohols. Although butanol, which could be used as a blending constituent6 of gasoline, has received much attention recently,7
16 propanol isomers that also represent interesting alternative bioderived fuels17,18 for spark-ignited engines have received less attention. Norton and Dryer19 studied the oxidation of 1-propanol in a turbulent flow reactor at initial temperatures of T = 1020
1120 K and at atmospheric pressure. Li et al.20 studied the oxidation of 1-propanol in low-pressure (15 and 30 Torr) premixed flames at equivalence ratios of j = 0.75 and 1.8, using a molecular-beam mass spectrometry (MBMS) technique. Kasper et al.21 studied three low-pressure premixed 1-propanol flat flames at different equivalence ratios, using two independent MBMS techniques. Johnson et al.22 measured ignition delays of 1-propanol
oxygen
argon mixtures in a shock tube at 1 atm. They have also proposed a r 2011 American Chemical Society

detailed kinetic mechanism that represents their data. Frassoldati et al.23 presented an experimental study of counter-flow nonpremixed flames and a kinetic modeling study of 1-propanol combustion. They have also modeled previous flow reactor, ignition delay times, and low-pressure premixed flames experiments. More recently, Veloo and Egolfopoulos24 measured the burning velocity and extinction strain rates of 1-propanol/air mixtures at 343 K and compared their data to the model of Johnson et al.22 The modeling significantly overpredicted burning velocities and strain rates above stoichiometric conditions. The goal of this study is to provide new experimental data on the kinetics of 1-propanol oxidation using complementary welldefined laboratory experiments operating under high pressure, which is more representative of engine conditions than previous works. Stable species concentration profiles were obtained for 1-propanol oxidation in a JSR at 10 atm (10.13  105 Pa) over a range of equivalence ratios and temperatures. Burning velocities were measured for 1-propanol/air premixed laminar flames at 423 K over a range of pressures and for several equivalence ratios. This new set of experimental results was used to evaluate the accuracy of a detailed chemical kinetic reaction mechanism proposed previously22 for the oxidation of 1-propanol and to propose an extended oxidation mechanism for alcohols, based on our previous modeling efforts.12,14,25
27 The recent mechanism of Johnson et al. was selected because it is relatively small and was Received: March 7, 2011 Revised: April 15, 2011 Published: April 26, 2011 2013

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Table 1. JSR Experimental Conditions (Residence Time, τ = 0.7 s; Pressure, P = 1 atm) Initial Mole Fraction equivalence ratio, j

1-propanol

O2

N2

0.35

0.001500

0.019286

0.979214

0.5

0.001500

0.013500

0.985000

1 2

0.001500 0.001500

0.006750 0.003375

0.991750 0.995125

already tested against burning velocities in the very recent work of Veloo and Egolfopoulos.24

2. EXPERIMENTAL SECTION 2.1. Jet-Stirred Reactor (JSR). We described previously28,29 the JSR experimental setup used in the present work. It consisted of a 4-cm outside diameter (OD) spherical fused-silica reactor equipped with four nozzles, each with an inner diameter (ID) of 1 mm. High-purity reactants were used in these experiments: oxygen (99.995% pure) and 1-propanol (>99.5% pure) (from Aldrich, CAS No. 71-23-8) were used. The reactants were diluted with nitrogen ( ethylene > propene

4. RESULTS AND DISCUSSION 4.1. Jet-Stirred Reactor (JSR). The experiments were performed at a constant pressure of 10 atm and a constant mean residence time of 0.7 s. The equivalence ratio was varied from fuel-lean to fuel-rich conditions (0.35, 0.5, 1, and 2). The fuel initial concentration was 1500 ppm. The temperature ranged from 770 K to 1190 K. A good repeatability of the measurements was observed, and a reasonably good carbon balance (better than 100 ( 15%) was determined. The concentration profiles of the reactants (1-propanol and O2) and products (H2, H2O, CO, CO2, CH2O, CH4, C2H4, C2H6, C2H2, C3H6, CH3CHO,

Many oxygenates for which kinetics of oxidation are not always well-known35
38 can be released via the oxidation of alcohols. Generally, aldehydes are important products of alcohol oxidation.12,14,16,27,39,40 Here, formaldehyde and propanal were the main aldehydes produced during the oxidation of 1-propanol. Acetaldehyde and 2-propenal were formed at much lower concentration. These aldehydes are among the potential pollutants emitted from incomplete fuel combustion. Therefore, we have compared their maximum intermediate concentrations measured at 10 atm, 0.7 s, and j = 1 during the JSR oxidation of a series of alcohols. In these experiments, the initial carbon content was 4500 ppm for 1- and 2-propanol, 4000 ppm for 1-butanol 2015

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Figure 2. Experimental (large symbols) and computed (lines and small symbols) concentration profiles obtained from the oxidation of 1-propanol in a JSR at j = 0.5, P = 10 atm, and τ = 0.7 s.

Figure 3. Experimental (large symbols) and computed (lines and small symbols) concentration profiles obtained from the oxidation of 1-propanol in a JSR at φ = 1, P = 10 atm, and τ = 0.7 s.

and ethanol, 5000 ppm for 1-pentanol, and 6000 ppm for 1-hexanol. In order to compare the data, the results were scaled to 4000 ppm of carbon. According to these scaled data, the oxidation of 1-alcohols generates similar intermediate concentrations of formaldehyde (average value of 133 ppm), 45% higher than from 2-alcools (i.e., 130 ppm for ethanol, 116 ppm for

1-propanol, 148 ppm for 1-butanol, 135 ppm for 1-pentanol, and 136 ppm for 1-hexanol; 93 ppm for 2-propanol and 91 ppm for 2-butanol; uncertainties of 10%). The data showed that the oxidation of ethanol yielded much larger quantities of acetaldehyde than the other alcohols (i.e., 254 ppm for ethanol, 48 ppm for 1-propanol, 59 ppm for 1-butanol, 54 ppm for 1-pentanol, and 2016

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Figure 4. Experimental (large symbols) and computed (lines and small symbols) concentration profiles obtained from the oxidation of 1-propanol in a JSR at j = 2, P = 10 atm, and τ = 0.7 s.

Figure 6. Sensitivity spectrum for the JSR oxidation of 1-propanol at 900 K, τ = 0.7 s, and j = 1. Only the most-sensitive reactions are shown. Note: A, B, and CC3H6OH respectively represent 1-C3H6OH, 2-C3H6OH, and 3-C3H6OH.

Figure 5. Experimental concentration profiles (large symbols) and computed concentration profiles (small symbols, continuous lines (this model), and dashed lines (literature model)) obtained from the oxidation of 1-propanol in a JSR at j = 1, P = 10 atm, and τ = 0.7 s.

62 ppm for 1-hexanol; 93 ppm for 2-propanol and 91 ppm for 2-butanol; uncertainties of 10%). An example of the modeling results obtained using the mechanism of Johnson et al. is presented in Figure 5. That figure

shows that the formation of several intermediates is not well predicted: the model overpredicts the formation of formaldehyde and 2-propenal, and it underpredicts the formation of propanal, acetaldehyde, ethylene, and propene. In fact, formation routes were missing in that scheme for propanal, one of the main intermediates, resulting in some of the observed discrepancies between computations and data. Therefore, we extended the mechanism used previously for the oxidation of 1-alcohols,12,14,25
27 under conditions similar to that of the present work. In that proposed model, the fuel initially reacts by oxidation with molecular oxygen and by thermal decomposition. The kinetics of the bimolecular initiation by oxygen were taken from the kinetic scheme of Johnson et al.22 The kinetics of the molecular elimination yielding propene and water and the decomposition yielding OH and n-C3H7 were also taken from that previous study.22 For the other decomposition reactions and the metathesis reactions of the fuel with small radicals (O, H, OH, HO2, CH3, HCO, 2017

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1-C3H6OH reacts via thermal decomposition and oxidation with molecular oxygen: 848: 1-C3 H6 OH f CH3 HCO þ CH3

RðC3 H6 OHÞ¼
0:245

1-C3 H6 OH þ O2 a C2 H5 CHO

1077:

þ HO2

RðC3 H6 OHÞ ¼
0:687

2-C3H6OH also reacts via thermal decomposition and oxidation with O2: 2-C3 H6 OH a C3 H6 þ OH

1075:

RðC3 H6 OHÞ ¼
0:96

2-C3 H6 OH þ O2 f CH3 HCO þ CH2 O

1080:

þ OH

RðC3 H6 OHÞ ¼
0:04

3-C3H6OH mainly decomposes and also oxidizes:

Figure 7. Main reaction paths for the oxidation of 1-propanol in a JSR at 10 atm, 900 K, τ = 0.7 s, and j = 1. The thickness of the arrows indicates the importance of the route.

844:

3-C3 H6 OH f CH2 OH þ C2 H4

1079:

3-C3 H6 OH þ O2 f C3 H5 OH þ HO2

RðC3 H6 OHÞ ¼
0:95

RðC3 H6 OHÞ ¼
0:04

C3H7O decomposes by beta-scission via: CH2OH, CH3O, and C2H5), the rate constants were assumed based on the corresponding reactions for other alcohols.27 The proposed kinetic model represents reasonably well the present JSR data (see Figures 1
4). According to first-order sensitivity analyses (Figure 6), the rate of oxidation of the fuel is highly sensitive to the kinetics of metathesis reactions with OH, yielding (i) 2-C3H6OH, which, in turn, produces propene, (ii) 1-C3H6OH, which, in turn, produces propanal; and (iii) 3-C3H6OH that subsequently decomposes to C2H4 and CH2OH. The reaction sequence H þ O2 f HO2 f H2 O2 f 2OH

At that temperature, ethylene has accumulated; it is produced by the decomposition of 3-C3H6OH and the oxidation of ethyl radicals:

also favors the fuel consumption by providing OH radicals that, in turn, react with the fuel. Two reactions consuming OH are mainly influential for reducing the fuel’s oxidation rate:

Methane that accumulates until ca. 1050 K is mainly formed via reactions of CH3:

1073:

C3 H7 O a C2 H5 þ CH2 O

RðC3 H7 OÞ ¼
0:74

1074:

C3 H7 O a C2 H5 CHO þ H

RðC3 H7 OÞ ¼
0:26

RðC2 H4 Þ ¼ 0:34

3-C3 H6 OH f CH2 OH þ C2 H4

CH3 þ HO2 a CH4 þ O2 CH2 O þ CH3 a HCO þ CH4

117: HO2 þ OH f H2 O þ O2

Normalized rates of formation and consumption for every species (noted as R in the following equations) were computed to delineate the main reaction paths (see Figure 7). The computations indicated that under stoichiometric conditions, at 900 K, which corresponds to the temperature at which 41% of oxygen had reacted, 1-propanol reacts essentially via metathesis with OH (the reaction numbers refer to their order of appearance in the proposed kinetic scheme):

1097
1099:

1075: 1072: 1077:

RðC3 H7 OHÞ ¼
0:05

n-C3 H7 OH þ OH a H2 O

2-C3 H6 OH a C3 H6 þ OH

RðC3 H6 Þ ¼ 0:289 RðC3 H6 Þ ¼ 0:66

RðC3 H7 OHÞ ¼
0:29

1-C3 H6 OH a H þ C2 H5 CHO

1-C3 H6 OH þ O2 a C2 H5 CHOþ HO2

RðpropanalÞ ¼ 0:69 RðpropanalÞ ¼ 0:08

Acetylene is a minor product of 1-propanol oxidation. It is produced via: 149: C2 H3 þ O2 a C2 H2 þ HO2

RðC3 H7 OHÞ ¼
0:15

n-C3 H7 OH þ OH a H2 O þ 2-C3 H6 OH

n-C3 H7 OH þ CH3 a CH4 þ C3 H7 O isomers

i-C3 H7 þ O2 a C3 H6 þ HO2

289:


826: 1092:

RðCH4 Þ ¼ 0:22

Propene also accumulates until ca. 820 K, at which it is mainly formed via the decomposition of 2-C3H6OH:

RðC3 H7 OHÞ ¼
0:39

þ 3-C3 H6 OH

RðCH4 Þ ¼ 0:26

Propanal is essentially produced through the two reactions:

n-C3 H7 OH þ OH a H2 O þ C 3 H7 O

RðC2 H4 Þ ¼ 0:22

RðCH4 Þ ¼ 0:35

n-C3 H7 OH þ OH a H2 O þ 1-C3 H6 OH

1091:

820: C2 H5 þ O2 a C2 H4 þ HO2

42:

and

1090:

RðC2 H4 Þ ¼ 0:3

844:

CH2 O þ OH f HCO þ H2 O

1089:

136: C2 H4 þ HO2 a C2 H4 O2 H

p-C3 H4 þ H a C2 H2 þ CH3

RðC2 H2 Þ ¼ 0:31 RðC2 H2 Þ ¼ 0:55

4.2. Laminar Burning Velocities. We determined the laminar burning velocities of 1-propanol/air mixtures under premixed 2018

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Figure 9. Laminar burning velocities of 1-propanol/air mixtures (a) at 1 bar and T = 423 K (this work) and 343 K (ref 24) and (b) at 3 bar and 423 K. The data (symbols) are compared to the computations (lines).

Figure 8. (a) Illustration of the spherical flame front propagation for a stoichiometric 1-propanol/air mixture at 0.1 MPa and 423 K; the interval time between two successive pictures is 1.2 ms. (b) Markstein length measurements.

conditions at 1
10 bar. The data were measured at 1 bar over the range of equivalence ratios of 0.75
1.45 and a more limited range at higher pressures. The error in the burning velocities measurements was ca. (2 cm/s. Figure 8a shows the recorded spherical flame front propagation for a stoichiometric 1-propanol/air mixture at 0.1 MPa and 423 K. The burned gas Markstein length, a characteristic value of the flame sensibility to stretch, is plotted in Figure 8b. A decrease of the Markstein length is observed when equivalence ratio is increased. The obtained values remain positive over a wide range of equivalence ratios, indicating that, as observed experimentally, flame fronts are generally not affected by thermodiffusive instabilities. The present

Figure 10. Effect of (a) temperature at 1 bar and (b) pressure at T = 423 K on laminar burning velocities of 1-propanol/air mixtures. The data (symbols) are compared to the model predictions (lines).

data were used to further assess the accuracy of the proposed kinetic scheme whereas, as already reported,22 that proposed earlier by Johnson et al.22 overestimated the burning velocities of stoichiometric to fuel-rich flames (see Figures 9 and 10). Figure 9 compares the computed and experimental laminar burning velocities as a function of equivalence ratio. The experimental data indicates that the burning velocity increases between j = 0.75 and j ≈ 1.05, and then decreases at higher equivalence ratios, with a maximum burning velocity measured of 60.5 cm/s 2019

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Table 2. Effect of Total Pressure on the Burning Velocity of Stoichiometric Alcohol/Air Laminar Premixed Flames fuel

a

exponent of pressure

initial temperature (K)

pressure (MPa)

reference

average for C1
C6 alcoholsa


0.23

298
700

0.1
4

for details, see ref 39

1-propanol


0.23

423

0.1
1

this work

averageb


0.23

this work

Includes methanol, ethanol, 2-propanol, 1-butanol, and 1-hexanol. b Including the present measurements for 1-propanol.

311 (C3H6 þ H a AC3H5 þ H2) that consume H-atoms tend to reduce the computed burning velocity. This is also the case for reaction 301 (C3H6 þ OH a aC3H5 þ H2O) that produces lessreactive radicals (aC3H5, i.e., allyl) and reaction 633 (C3H7OH þ OH a H2O þ 2-C3H6OH) that will also contribute to allyl formation via the reaction sequence 2-C3H6OH f C3H6 f aC3H5.

Figure 11. Sensitivity spectrum for the burning velocity of 1-propanol in air at 1 atm and j = 1 for reactions 6 (H þ O2 a OH þ O), 7 (H þ O2 þ M a HO2 þ M), 23 (CO þ OH a CO2 þ H), 26 (HCO þ M a H þ CO þ M), 50 (CH3 þ CH3 a C2H5 þ H), 301 (C3H6 þ OH a aC3H5 þ H2O), 311 (C3H6 þ H a aC3H5 þ H2), 571 (C2H4 þ H (þ M) a C2H5 (þ M)), 630 (C3H7OH þ OH a H2O þ 1-C3H6OH), 633 (C3H7OH þ OH a H2O þ 2-C3H6OH).

at 1 bar and 423 K, and 51 cm/s at 1 bar and 343 K.24 At 3 bar, the maximum burning velocity was 47.4 cm/s. The variation of laminar burning velocity, relative to the equivalence ratio j, is well-predicted by the model. The maximum computed burning velocity at 1 bar is 44.8 cm/s at j = 1.1 and T = 343 K, and 62.8 cm/s at j = 1.1 and T = 423 K. At 3 bar and 423 K, the maximum computed burning velocity is 49.9 cm/s at j = 1.1. Therefore, the model underestimates the maximum burning velocities as well as those of fuel-lean mixtures at 343 K, whereas, at 423 K, it represents the present data well. The effect of temperature and total pressure on the burning velocity of nearly stoichiometric flames (j = 1.05) was also studied (see Figure 10). The results show that increasing the initial temperature increases the burning velocity: the burning velocity is increased by a factor of 2 by changing the initial temperature from 50 °C (323 K) to 200 °C (473 K). The proposed model predicts the effect of temperature on burning velocity well. The present experimental and computed results also show that the burning velocity decreases by a factor of ∼2 by increasing the total pressure from 1 bar to 10 bar at 423 K. These results are consistent with earlier observations made with other C1
C6 alcohols in the literature.39 The present data indicated that the burning velocity varies as a function of P
0.23, which is fully consistent with an average value of P
0.23 derived from the literature data for C1
C6 alcohols (see Table 2). The proposed model predicts the experimentally observed pressure dependency well (see Figure 10). Sensitivity analyses were performed to determine the reaction mostly influencing the computed burning velocity (Figure 11). The positive effect of increasing the rates of reactions 6 (H þ O2 a OH þ O), 23 (CO þ OH a CO2 þ H), 26 (HCO þ M a H þ CO þ M), 571 (C2H4 þ H (þ M) a C2H5 (þ M)), and 630 (C3H7OH þ OH a H2O þ 1-C3H6OH) that produce H-atoms or consume the fuel was computed. Conversely, reactions 7 (H þ O2 þ M a HO2 þ M),
50 (C2H5 þ H a CH3 þ CH3), and

5. CONCLUSION New experimental results were obtained for the oxidation of 1-propanol under elevated pressure using a jet-stirred reactor (JSR) and a combustion bomb. Concentration profiles of reactants, stable intermediates, and reaction products were measured in a JSR at 10 atm over a range of equivalence ratios (j = 0.35
4) and temperatures (T = 770
1190 K). Laminar burning velocities were measured for premixed 1-propanol/air laminar flames at 1
10 bar. According to the experiments, the burning velocity of stoichiometric 1-propanol/air mixtures varied as P
0.23. That result is consistent with the literature data available for C1
C6 alcohols. The oxidation of 1-propanol in the abovementioned experimental configurations was modeled using a detailed chemical kinetic reaction mechanism taken from the literature. That kinetic mechanism yielded modeling results in reasonably good agreement with our experimental data obtained in a JSR and a combustion bomb, although some intermediates were not well-predicted. A reaction mechanism was proposed, based on a previous oxidation scheme for alcohols. That new scheme allowed better modeling of the presently obtained dataset. Reaction path analyses and sensitivity analyses were performed to interpret the results. ’ ASSOCIATED CONTENT

bS

Supporting Information. The JSR data, kinetic mechanism, associated thermochemistry, and transport data used here in CHEMKIN format. (TXT) This material is available free of charge via the Internet at http://pubs.acs.org.

’ AUTHOR INFORMATION Corresponding Author

*Tel.: þ33(0) 238 255466. Fax: þ33(0) 238 696004. E-mail: [email protected].

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dx.doi.org/10.1021/ef2003552 |Energy Fuels 2011, 25, 2013–2021