Development of a Chemical Reaction Mechanism for Alternative

ARTICLE pubs.acs.org/EF

Development of a Chemical Reaction Mechanism for Alternative Aviation Fuels E. Catalanotti,† K. J. Hughes,*,† M. Pourkashanian,† and C. W. Wilson‡ †

Centre for Computational Fluid Dynamics, School of Process, Environmental and Materials Engineering, University of Leeds, Leeds LS2 9JT, United Kingdom ‡ Department of Mechanical Engineering, The University of Sheffield, Sheffield S1 3JD, United Kingdom

bS Supporting Information ABSTRACT: A theoretical model for the oxidation of blends of kerosene, biofuels, and synthetic fuels is proposed in this work, with the biofuel portion being represented by methyl tridecanoate (MTD), a methyl ester with chemical formula C14H28O2, and the synthetic fraction being represented by heptane. The model is based on previous work performed by the authors on the development of a reaction mechanism including kerosene and methyl butanoate (MB), the Aviation Fuel Reaction Mechanism version 2.0 (AFRM v2.0). AFRM v2.0 has been updated through a multi-parameter optimization, including the addition of the reactions for the breakdown of the C-14 methyl ester and a set of reactions for the oxidation of heptane. The final scheme consists of the surrogate kerosene components n-decane and toluene, a surrogate fatty acid methyl ester (FAME) (methyl tridecanoate), and a surrogate of the synthetic paraffinic portion, heptane. The scheme also includes NOx, SOx, and polycyclic aromatic hydrocarbon (PAH) chemistry. Perfectly stirred reactor simulations were compared to experimental results by Dagaut et al. for the oxidation of biokerosene and pure heptane in a jet-stirred reactor at different fuel/O2 equivalence ratios. Because of the lack of available experimental work on blends, burner-stabilized flame validation has been carried out for pure kerosene only.

’ INTRODUCTION Two main alternatives have been proposed to replace kerosene-based jet fuels currently used in aviation: one is represented by blends of 80% kerosene and 20% biodiesel, and another, already produced in South Africa by SASOL, is a blend of 50% kerosene and 50% synthetic fuel, derived by either coal or biomass through the Fischer
Tropsch (FT) process. From a chemical point of view, biodiesel is composed of a complex mixture of fatty acid methyl esters (FAMEs) derived from vegetable oils, while FT synthetic fuel is essentially a mixture of linear alkanes of different C-chain lengths. The aim of this work was the development of a comprehensive detailed chemical reaction mechanism able to reproduce the oxidation of blends of kerosene and alternative fuels, such as biodiesel and FT synthetic fuel. The first issue to be addressed in this work was the development of a model for the combustion of oxygenated compounds with a similar chemical structure to FAMEs. Several studies have investigated the chemistry of oxidation of oxygenated compounds, such as acetic and propanoic acids,1,2 and a number of detailed chemical reaction mechanisms were developed for methyl esters as biofuel surrogates.3
5 Dagaut et al.6 built a model for the combustion of biokerosene basing it on previous studies,7 which showed that the biofuel portion [typically rapeseed methyl esters (RMEs)] could be well-represented by hexadecane. The model showed overall a good agreement with experiments, although it did not consider the chemistry of the methyl ester group and the influence of the presence of oxygen in the fuel on the overall stoichiometry. A reaction mechanism for the oxidation of biokerosene [Aviation Fuel Reaction Mechanism, version 2.0 (AFRM v2.0)] has been r 2011 American Chemical Society

previously developed by the authors using methyl butanoate (MB) for the biofuel portion.8 Although MB has the essential chemical characteristics of typical FAME biofuels, its relatively high oxygen content leads to a lower energy density than would be the case for real fuels; therefore, there is a need to address this problem by increasing the carbon and hydrogen composition by extending the carbon chain. To address this, in this study, a methyl ester with a carbon chain of 13 carbon atoms has been chosen and a detailed chemical kinetic mechanism was created and tested against experimental data for both a blend (20% biofuel and 80% kerosene) and pure kerosene, under a range of conditions, to validate the mechanism. The reaction mechanism for the oxidation of kerosene and methyl tridecanoate (MTD) was initially developed using the AFRM v2.0 as a base8 and, as a result of sensitivity analysis, has been optimized on the basis of data reported in the National Institute of Standards and Technology (NIST) chemical kinetics database9 and evaluated kinetic data for combustion modeling,10 to improve the fit with the experiments. Afterward, the mechanism has been extended by the introduction of selected reactions for the oxidation of heptane based on the reduced reaction mechanism developed by Seiser et al.11 As mentioned before, synthetic fuels are in fact composed of a mixture of alkanes of different C-chain lengths, the reason for choosing heptane is that, in practice, it is not expected that the high-temperature oxidation chemistry will be particularly sensitive to the chain length, and given the fact that heptane is Received: December 17, 2010 Revised: February 22, 2011 Published: March 15, 2011 1465

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Figure 1. MB and MTD chemical structures.

Table 1. List of Reactions Whose Rates Were Taken from Different Sources than Those of Similar Reactions in AFRM v2.0 reaction RO þ MTD3J h R• þ MTD3O MTD h MP3J þ C10H21 RO þ MTD4J h R• þ MTD4O MTD h TDAOJ þ CH3 RO þ MTDMJ h R• þ MTDMO MTD h ME2J þ C11H23 MTD3J h MTD2D þ H MTD h CH3OCO þ C12H25 MTD3J h MTD3D þ H MTD h CH3O þ C12H25CO MTD3J h MB3D þ C9H19 MTD2J h C11H23CHCO þ CH3O MTD4J h C11H22 þ ME2J MTD2J h MP2D þ C10H21 MTD2D þ R h MTD3D2J þ RH MTD2J h MTD2D þ H MTD3D þ R• h MTD3D2J þ RH RO þ MTD2J h R• þ MTD2O MTD3D2J h C10H20CHCHCO þ CH3O CnH2nþ1CO h CmH2mþ1CHCO þ H CnH2nþ1CO h CH2CO þ CmH2mþ1 CnH2nþ1O h CmH2mþ1CHO þ H C10H20CHCH2 h C3H4 þ C9H19 C10H20CHCH2 h C3H4(A)þ C9H19 CqH2qþ1 f C2H4 þ ClH2lþ1 CqH2qþ1 f C3H6 þ CpH2pþ1 CqH2qþ1 f C4H8 þ CrH2rþ1 CqH2q f C3H5 þ CpH2pþ1 CqH2q f C3H6 þ CpH2p C11H20 f C3H4(P) þ C8H16 C11H20 f C3H3 þ C8H17

reference and comment 5; RO = HO2, CH3O2, C2H5O2, C3H7O2 5 5; RO = HO2, CH3O2, C2H5O2, C3H7O2 5 5; RO = HO2, CH3O2, C2H5O2, C3H7O2 5 5 5 5 5 5 5 5 5 5; R• = OH, HO2, H, CH3, O 5 5; R• = OH, HO2, H, CH3, O 5; RO = HO2, CH3O2, C2H5O2, C3H7O2 5 5; n = 12, ..., 9; m = n
1 5; n = 12, ..., 9; m = n
1 5; n = 12, ..., 9; m = n
1 5 5 21; q = 12
8; l = q
2; p = q
3; r = q
4 18; q = 12
8; l = q
2; p = q
3; r = q
4 18; q = 12
8; l = q
2; p = q
3; r = q
4 9; q = 12
8; l = q
2; p = q
3; r = q
4 9; q = 12
8; l = q
2; p = q
3; r = q
4 9; for C6H10 9; for C6H10

one of the most intensively studied alkanes in terms of its oxidation chemistry, the choice was made to use it as the FT surrogate.

’ MODELING: DEVELOPMENT OF AFRM V2.1 A detailed chemical reaction mechanism for an asymmetric long-chain molecule, such as MTD, would contain several thousands of reactions for hundreds of species if approximations

Figure 2. (a) Schematic representation of the hydrogen abstraction reactions and following decomposition of MTD. (b) Schematic representation of the decomposition of MTD.

were not considered. Because of the very similar structures of MTD and MB (Figure 1), it is sensible to assume that the degradation process of MTD can be described in a similar way as for MB. On this basis, the AFRM v2.08 describing the oxidation of MB was initially chosen as the starting point in the development of the new mechanism for those reactions involving the carbons up to position 4 (Figure 1). The rates for reactions related to carbons 1
3 were kept from the parent mechanism AFRM v2.0, except for the classes of reactions listed in Table 1, for which either no equivalent was found in the mechanism describing the oxidation of MB or there was no indication of the source. In these cases, rates of analogous reactions were taken from the reaction mechanism developed by Herbinet et al.5 for the oxidation of methyl decanoate, which were in agreement with the values reported in the work by Fischer et al.3 From the same work by Herbinet et al.,5 also the rates of reactions involving carbon number 4 were taken. To reduce the steps for the breakdown of the MTD to a minimum and keep the mechanism relatively simple, the reactions of hydrogen abstraction or C
C bond dissociation involving carbons 5
13 were omitted, assuming that the subsequent chemistry that would arise (alkyl radical decomposition) can be encapsulated in the already existing alkyl radical breakdown reactions within the mechanism. Investigations were undertaken to verify the validity of this simplification by an appropriate increase in the A factor of reactions involving carbon number 5, which demonstrated a negligible effect. For the breakdown of long-chain alkyl radicals (i.e., C12H25 and 1466

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Figure 3. Major species profiles for the oxidation of biokerosene (80% kerosene and 20% MTD) in a jet-stirred reactor (j, 0.5; P, 10 atm; and τ, 0.5 s). Filled squares, experiments; black lines, simulations performed with the initial MTD mechanism; red lines, optimized version AFRM v2.1; and blue lines, AFRM v2.2.

Figure 4. Minor species profiles for the oxidation of biokerosene (80% kerosene and 20% MTD) in a jet-stirred reactor (j, 0.5; P, 10 atm; and τ, 0.5 s). Filled squares, experiments; black lines, simulations performed with the initial MTD mechanism; red lines, optimized version AFRM v2.1; and blue lines, AFRM v2.2.

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Figure 5. Major species profiles for the oxidation of biokerosene (80% kerosene and 20% MTD) in a jet-stirred reactor (j, 1.0; P, 10 atm; and τ, 0.5 s). Filled squares, experiments; black lines, simulations performed with the initial MTD mechanism; red lines, optimized version AFRM v2.1; and blue line, AFRM v2.2.

Figure 6. Minor species profiles for the oxidation of biokerosene (80% kerosene and 20% MTD) in a jet-stirred reactor (j, 1.0; P, 10 atm; and τ, 0.5 s). Filled squares, experiments; black lines, simulations performed with the initial MTD mechanism; red lines, optimized version AFRM v2.1; and blue lines, AFRM v2.2. 1468

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Table 2. List of Modified Reaction Rates for the Development of the AFRM v2.1a original Arrhenius parameters A

reaction

A

Ea

n
18

Ea

97. OH þ CO = H þ CO2

7.9  10

1.2

3.2  10

1.6


173

118. HO2 þ CO = OH þ CO2

2.5  10
10

0

11877

4.9  10
11

0

11877

36. H þ O2 = O þ OH

1.4  10
10

0

7253

8.0  10
11

0


1726

1.0  10
16

1.5


252

7.9  10
11

0


16

82. OH þ H2 = H þ H2O

3.6  10

1.5

85. OH þ HO2 = O2 þ H2O

4.8  10
11

0


12

35

7253
1726
308

333. H þ O2 (þM) = HO2 (þM)

2.5  10

0.6

0

1.5  10
13

0.6

0

99. OH þ CH2O = HCO þ H2O

5.7  10
15

1.2


225

1.3  10
15

1.4


349

166. HCO þ O2 = HO2 þ CO 116. HO2 þ CH3 = O2 þ CH4

1.3  10
11 1.7  10
12

0 0

201 0

1.3  10
10 5.7  10
14

0 0.8

201
800

165. HCO þ M = H þ CO þ M

3.1  10
7


1.0

8555

9.9  10
7

676. C3H5 = C2H2 þ CH3

2.4  10


9.9

41304

2.4  1048

48

1600. C6H5O þ O = HCO þ 2C2H2 þ CO a

n
17

modified Arrhenius parameters

3

Units: K for Ea and cm molecules


1
1

s

or s


1

5.0  10
11

0

0

5.0  10
11


1.2
10 0.1

8955 41304 1500

for A.

Figure 7. Sensitivity analysis results for selected species in a lean biokerosene flame (j, 0.5; P, 10 atm; τ, 0.5 s; and T, 850 K).

C11H23), the rates already contained in AFRM v2.08 for the decomposition of C10H21 were used, while for reactions of decomposition of high-molecular-weight primary alkenes (i.e., C12H24 and C11H22), data reported in the NIST database for C6H12 were used. The thermodynamic data of the new species introduced in the mechanism were taken from the work by Herbinet et al.5 for the hydrocarbon species: C9H19, C9H18, C8H17, C8H16, C6H12, and C5H10. For those species whose thermodynamic data were not available, the Thermo Estimation

for Radicals and Molecules (THERM) program12 based on Benson’s group additivity method13 was used to estimate the properties and produce an appropriate set of NASA polynomial coefficients. The NOx chemistry section was taken from the Gas Research Institutes Mechanism, version 2.11.14 The mechanism was then extended by the addition of sulfur and polycyclic aromatic hydrocarbon (PAH) chemistry. The SOx chemistry section describes the chemistry of simple sulfur species based on the work by Hughes et al.,15,16 which itself extended the sulfur 1469

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Figure 8. Sensitivity analysis results for selected species in a lean biokerosene flame (j, 0.5; P, 10 atm; τ, 0.5 s; and T, 1200 K).

reaction mechanism developed by Alzueta et al.17 The section describing PAH chemistry up to the size of four fused benzene rings as a precursor to soot particle formation was based on the so-called Hydrogen Abstraction Acetylene Addition (HACA) mechanism proposed by Appel et al.18 Some examples of reactions enclosed in the mechanism are shown in panels a and b of Figure 2. MTD undergoes a reaction through hydrogen abstraction and C
C dissociation and subsequently breaks down into smaller fragments already present in the MB scheme and long-chain hydrocarbons in the form of alkanes or alkenes. The final mechanism consisted of 321 species, 101 irreversible and 1538 reversible reactions, and included kerosene, MTD, NOx, SOx, and PAH oxidation chemistry.

’ KINETIC MODELING TOOLS The perfectly stirred rector simulations were performed using the PSR19 component of CHEMKIN, a FORTRAN computer program,20 that predicts the steady-state temperature and composition of the species in a perfectly stirred reactor. The stirred reactor consists of a small, thermally insulated chamber that has inlet and outlet ducts. The assumption adopted in these calculations is that the mixing process is infinitely fast and, thus, that the rate of conversion from reactants to products is controlled by chemical reaction rates and not mixing processes. Therefore, complicating factors that would be caused by spatial temperature and concentration gradients are avoided. Sensitivity Analysis. While the PSR19 module of CHEMKIN has its own built-in sensitivity analysis routine, the decision was made to use the SPRINT FORTRAN code,21 in this instance, to investigate the effect

of rate coefficient perturbations on the temperature and species outputs. The program was setup to perform identical simulations to PSR19 and manipulated to aid in the sensitivity analysis by the use of automated scripts. The customized version of the code performed an initial simulation with all rate coefficient parameters at their original values. Then, the code loops over the number of reactions, in turn increasing the rate coefficient of that particular reaction by an arbitrarily chosen percentage, 25% in this case, and performs a new simulation. Therefore, at the end of the procedure, an output file of temperature and species mole fractions is generated that allows for the effect of the change in each rate coefficient to be easily assessed for any species of interest.

’ RESULTS AND DISCUSSION: MECHANISM OPTIMIZATION AND VALIDATION The performance of the mechanism has been tested using experimental data by Dagaut et al.6 for the oxidation of a blend of 80% kerosene and 20% RMEs in a jet-stirred reactor for a lean (j = 0.5) and stoichiometric (j = 1.0) mixture at a pressure of 10 atm and residence time of 0.5 s, and results for selected major and minor species are denoted by the black lines in Figures 3
6. In both lean and stoichiometric cases, the results indicated the same type of discrepancies between simulations and experiments. For the major species, the main problems occurred in the CO
CO2 conversion, with there being a large underprediction of CO at high temperatures and, especially in the stoichiometric case, an overprediction of CO2 at low temperatures. In the case of the minor species, there was a tendency to underpredict hydrogen and methane profiles over most of the temperature range and 1470

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Figure 9. Comparison of experimental and simulated mole fractions for a rich (φ = 1.7) atmospheric premixed kerosene flame. Filled squares, experiments from Doute et al.;22 black lines, initial MTD mechanism; red lines, modified version AFRM v2.1; and dashed lines, AFRM v1.1.23

the temperature dependence of the C2 species, ethene, and ethyne was unsatisfactory. To improve the performance of the mechanism, sensitivity analysis was performed using a customized version of the SPRINT code,21 which allowed for the identification of the most influential reactions responsible for the concentration profiles of each particular species at defined temperatures. The results of the sensitivity analysis are shown in Figure 7 for 850 K and Figure 8 for 1200 K. As expected, the main reaction controlling the conversion of CO to CO2 at either low or high temperature was the oxidation of CO with OH, which produces CO2 and H. Second in importance at low temperatures was the reaction of CO with HO2, while at high temperatures, the branching reaction between H and O2, leading to O and OH radicals, was also prominent, as was the case for the CH4 concentration profile at high temperatures. The importance of these three reactions is related to the fact that they govern the OH levels in the mixture; therefore, modifications applied on these rates had a massive impact on the performance of the mechanism. It was observed that a reduction of the rate of these reactions would allow for better prediction of CO2, CO, and CH4. In terms of the minor species, particularly interesting is the modeling of C2H2 because of its role as a precursor in the PAH formation. In addition to those reactions already mentioned in the context of the major species, its prediction was sensitive to the reactions 333, 85, 166, and 676. The other minor species discussed, H2 and CH4, were also sensitive to reactions 82 and 116. With suitable modifications to these rate coefficients, keeping in mind the necessity to retain values consistent with the ranges reported in the NIST database9 and evaluated kinetic data for combustion modeling,10 an attempt was made to improve

the predictions of all of the major and minor species observed. A list of the reactions adjusted along with the original and modified values of the rate parameters are reported in Table 2. The optimized version of the mechanism was designated AFRM v2.1, and the performance was tested against the same experimental data for biokerosene6 as before. The results are also shown in Figures 3
6 by the red lines. Significant improvements were achieved in the overall performance, especially for major species, such as CO, CO2, and CH4, but also for minor species. Additional data from a different experimental system were modeled to check that these changes did not have any unforeseen negative effects. In this respect, species profile measurements from Doute et al.22 for a rich (φ = 1.7) atmospheric premixed kerosene flame were investigated, and the results of the simulations are shown in Figure 9, which also shows a comparison to a version previously developed for the oxidation of pure kerosene, AFRM v1.1,23 and used as a base in the construction of AFRM v2.0.8

’ DEVELOPMENT OF AFRM V2.2 As discussed in the Introduction, to provide the capability of simulating blends of synthetic FT fuels with kerosene, a set of reactions describing the oxidation chemistry of heptane was incorporated into AFRM v2.1 to produce AFRM v2.2. The reactions chosen were taken from a reduced mechanism developed by Seiser et al.;11 the degree of complexity of the AFRM v2.1 would not justify the choice of using the detailed mechanism developed by the same authors,24 also considering that the detailed version will behave very similarly to the reduced one. For cases where duplicate reactions belonging to the two 1471

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Figure 10. Species profiles for the oxidation of heptane in a jet-stirred reactor (j, 1.0; P, 10 atm; and τ, 1.0 s). Filled squares, experiments; black lines, simulations performed with the detailed heptane mechanism;24 blue lines, reduced heptane mechanism;11 and red lines, AFRM v2.2.

different mechanisms were expressed with different Arrhenius parameters, a choice was taken to eliminate the corresponding reactions from the heptane mechanism and to keep the rate parameters from AFRM v2.1. A total of 83 species and 368 reversible reactions were added to the scheme, leading to the final mechanism consisting of 404 species and 2007 reactions, including 102 reactions for the oxidation of 14 nitrogen species14 and 111 reactions for the oxidation of 22 sulfur species.15
17 Figure 10 shows a comparison between the reduced heptane mechanism,11 the detailed heptane mechanism,24 AFRM v2.2, and experimental measurements on the oxidation of pure heptane in a jet-stirred reactor.25 The figure shows in general the correct behavior of the AFRM v2.2. The Dagaut et al. experimental data for biokerosene discussed in the previous section have also been simulated using AFRM v2.2, and the results are reported in Figures 3
6 as the set of blue lines. These show that the addition of a set of reactions

from the heptane mechanism has not substantially affected the performance of the mechanism and that it is still able to predict kerosene
biodiesel blends, indicating that this additional set is not significant for the modeling of kerosene
biodiesel blends.

’ CONCLUSIONS Reaction mechanisms describing the combustion of a kerosene surrogate fuel and a biofuel represented by MB have been extended to include a higher molecular-weight FAME with a more realistic energy density representative of real biofuels, MTD. The performance of this mechanism in predicting various experimental data has been tested, and sensitivity analysis was used to identify the most influential reactions within the scheme. Tuning the rate parameters of several of these reactions within realistic bounds consistent with data reported in the NIST 1472

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Energy & Fuels chemical kinetic database9 and evaluated rate data10 has enabled the performance against experimental data to be significantly improved. A further modification has been applied to the mechanism to construct a comprehensive detailed chemical reaction mechanism able to reproduce the oxidation of blends of kerosene and alternative fuels, such as biodiesel and FT synthetic fuel. This consists of the addition of a set of reactions describing the oxidation of heptane to produce the final mechanism, AFRM v2.2, which has been again compared to experimental data for validation.

’ ASSOCIATED CONTENT

bS

Supporting Information. Aviation Fuel Reaction Mechanism (AFRM). This material is available free of charge via the Internet at http://pubs.acs.org.

’ AUTHOR INFORMATION Corresponding Author

*Telephone: þ44-0113-343-2481. E-mail: [email protected]. uk.

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