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Selection of a diesel fuel surrogate for the prediction of auto-ignition under HCCI engine conditions
J.J. Hernandez
a

a,*

, J. Sanz-Argent a, J. Benajes b, S. Molina

cnico), Universidad de Castilla-La Mancha, Avenida Camilo Jose Cela s/n. 13071, Ciudad Real, Spain E.T.S.I. Industriales (Edicio Polite b rmicos, Universidad Polite cnica de Valencia, Camino de Vera s/n. 46022, Valencia, Spain CMT-Motores Te Received 21 February 2007; received in revised form 9 May 2007; accepted 9 May 2007 Available online 11 June 2007

Abstract Homogeneous charged compression ignition (HCCI) is a promising combustion concept able to provide very low NOx and PM diesel engine emissions while keeping good fuel economy. Since HCCI combustion is a kinetically controlled process, the availability of a kinetic reaction mechanism to simulate the oxidation (low and high temperature regimes) of a diesel fuel is necessary for the optimisation, control and design of HCCI engines. Motivated by the lack of information regarding reliable diesel fuel ignition values under real HCCI diesel engine conditions, a diesel fuel surrogate has been proposed in this work by merging n-heptane and toluene kinetic mechanisms. The surrogate composition has been selected by comparing modelled ignition delay angles with experimental ones obtained from a single cylinder DI diesel engine tests. Modelled ignition angle results are in agreement with the experimental ones, both results following the same trends when changing the engine operating conditions (engine load and speed, start of injection and EGR rate). The eect of EGR, which is one of the most promising techniques to control HCCI combustion, depends on the engine load. High EGR rates decrease the n-heptane/toluene mixture reactivity when increasing the engine load but the opposite eect has been observed for lower EGR rates. A chemical kinetic analysis has shown that the inuence of toluene on the ignition time is signicant only at low initial temperature. More delayed combustion processes have been found when toluene is added, the dehydrogenation of toluene by OH (termination reaction) being the main kinetic path involved during toluene oxidation. 2007 Elsevier Ltd. All rights reserved.
Keywords: Auto-ignition; Diesel HCCI combustion; Fuel surrogate; Chemical kinetic analysis

1. Introduction The increase of the environmental concern and the more stringent regulations about pollutants emissions from internal combustion engines [1,2] make necessary the search of alternatives for current automotive engine combustion processes. One of the technologies which is receiving attention is the homogeneous charge compression ignition (HCCI), based on the combination of traditional spark ignition (SI) and compression ignition (CI) processes, and providing very low NOx and particulate matter (PM) emissions while keeping a good fuel economy [35]. Unlike diesel combusCorresponding author. Tel.: +34 926295300x3880; fax: +34 926295361. E-mail address: JuanJose.Hernandez@uclm.es (J.J. Hernandez). 0016-2361/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2007.05.019
*

tion, where the fuel injection and in-cylinder turbulence phenomena are of great importance, or gasoline engine combustion, where a ame front propagates from the spark towards the cylinder walls, during the HCCI combustion process a fresh oxidant/fuel charge is compressed until it auto-ignites in the combustion chamber due to the high pressure and temperature reached. In SI and CI engines, the physical phenomena, such as the ame development (SI) or the fuel atomization or evaporation (CI), dominate the combustion process, so a proper design and optimization of traditional engines does not require an exhaustive knowledge of the chemical kinetic behaviour of the fuel, but just the fullment of some fuel requirements, such as the octane number (ON) or the cetane number (CN). However, in HCCI engines, auto-ignition and combustion rate are mainly controlled by the fuel chemical kinetics, which

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is extremely sensitive to the charge composition and to the pressure and temperature evolution during the compression stroke, so that HCCI combustion is widely assumed to be kinetically controlled [6]. Thus, a deeper understanding of the chemical reactions governing the typical HCCI twostate ignition (low and high temperature oxidation regimes) is necessary in order to develop and optimize the most adequate engine control strategies (leading to the ignition taking place at the desired crank angle). Since commercial engine fuels, gasoline and mainly diesel fuel, consist of a complex mixture of hundreds of medium-high molecular weight hydrocarbons, it is not feasible to consider the oxidation chemistry of all the compounds for modelling targets. Therefore, kinetic studies of commercial fuels can only be carried out by considering surrogate mixtures of a small number of very well known hydrocarbons that simulate properly some of the physical or chemical properties of the original fuel [7], such as vapourliquid equilibrium, viscosity, ignition delay, heat release rate, pollutant emissions, etc. For HCCI purposes, the surrogate mixture should simulate, as accurately as possible, the ignition characteristics of the fuel (fuel reactivity and ignition time), and it would be also desirable that all the chemical classes of hydrocarbons in the original fuel are represented. Over the last years, several detailed chemical reaction mechanisms have been developed and experimentally validated for many dierent classes of compounds, involving both small fuel molecules [8,9] and larger hydrocarbons [10], such as n-heptane and iso-octane. While some research works have been carried out in order to propose kinetic reaction mechanisms for gasoline and other fuel surrogates [1115], there is very little information about the auto-ignition process of diesel fuel. The selection of a diesel surrogate fuel for estimating the auto-ignition time under real HCCI diesel conditions is the main objective of this work. n-Heptane has a cetane number (CN) equal to that of diesel fuel (CN = 56) and its oxidation chemistry is very well known, so it has been widely used as diesel fuel surrogate [1618]. Cetane number is an indicative of the fuel reactivity, and its determination is carried out by using a cooperative fuel research (CFR) engine and very specic engine conditions (injection timing, compression ratio, etc.). However, CN does not seem to be representative enough of the ignition characteristics of a fuel [1922], probably because its experimental determination does not cover a real and wide range of engine conditions and because the physical delay time (involving the fuel atomization and evaporation processes and the mixture with air) is also aecting the ignition timing. In fact, new and more realistic methodologies to measure CN are being currently studied [23,24], and there is still an important lack of reliable diesel ignition indicators. Therefore, the use of CN does not fully justify the selection of a diesel fuel surrogate and other criteria should be used. Some authors [25,26] suggest the consideration, together with the substitute representing the linear paran content of the diesel fuel

(usually n-heptane), of an aromatic compound due to the very high aromatic content of diesel (around 30% in mass), which causes a signicant decrease in the fuel reactivity. As mentioned above, there are very few experimental data regarding the oxidation of diesel fuel, and most of them have been obtained under very well controlled combustion conditions, such as those taking place in perfectly stirred reactors (PSRs). Heywood [27] showed some correlations for the ignition delay time of diesel fuel from earlier experimental works carried out by other researchers, but those ignition delay times include not only the chemical but also the physical delay. Dagaut [28] analysed the oxidation of highly diluted vaporized diesel fuel/air mixtures (0.5% by volume) in a PSR at dierent equivalence ratios (/, dened as the diesel fuel/air mass ratio with respect to the stoichiometric one), from lean to rich conditions (/ = 0.5, 1 and 1.5), and atmospheric pressure, xing the residence time at 0.1 s. This work has been extended recently to higher pressures (up to 10 atm) and equivalence fuel/air ratios (up to / = 2) by Mati et al. [29]. Edenhofer et al. [30] presented temperatures proles in a ow reactor where a well stirred diesel fuel/air mixture was introduced at atmospheric pressure. In this latter work, the onset of cool ames and negative temperature dependence (NTC) and the transition temperature between the dierent kinetic regimes (no reaction, unstable cool ame, cool ame, slow oxidation and thermal explosion) were obtained. However, the operating conditions (temperature, pressure and charge composition) used in the before mentioned experiments are far from those taking place during HCCI engine combustion. Therefore, there is still a very important lack of experimental data to validate kinetic mechanisms of diesel surrogate fuels. In such frame, this work proposes an improved surrogate diesel fuel composition which simulates the auto-ignition time of diesel fuel better than the commonly used nheptane, by comparing experimental ignition time results obtained in a single-cylinder diesel engine operating under HCCI conditions with those coming from the zero-dimensional single-zone kinetic model implemented in the CHEMKIN 4.0 software [31]. A chemical kinetics analysis of the surrogate fuel auto-ignition has also been carried out to identify the dierences between the n-heptane reaction paths and those derived from the consideration of an aromatic compound. CHEMKIN code assumes that temperature, pressure and species concentration are uniform in the combustion chamber, and ignores the dierent temperature of the boundary zones (close to the cylinder walls, crevices, etc.) caused by the heat transfer throughout the walls. Although single zone models are not accurate enough to simulate engine performance and pollutant emissions, they provide, as suggested in other works [4,32], a simple and useful tool for studying some fundamental aspects related to HCCI combustion, such as the prediction of the fuel auto-ignition time. The results of this work can be used for the optimization and improved design of new diesel engines, which use exible injection strategies to reduce

J.J. Hernandez et al. / Fuel 87 (2008) 655665 Table 1 Engine specications Engine type Fuel injection system Compression ratio Swirl Bore stroke Injector (number and diameter of holes) Direct injection diesel, 4 stroke single cylinder. Second generation common rail 14:1 0 0.068 m 0.079 m 12 86 lm

657

emissions (mainly NOx and particulate matter) by achieving either pure HCCI conditions or a homogeneous lean premixed combustion caused by very early fuel pilot injections prior to the main typical diesel diusion combustion. 2. Experimental setup The engine used for the experimental work was a fourstroke single cylinder diesel engine, with 0.287 l swept volume and four valves. The main engine specications are shown in Table 1. The engine was installed in a completely instrumented engine bench (Fig. 1) with all the facilities required for the operation and control of the engine. A screw compressor provided the required boost pressure (xed at 1.9 bar), while the exhaust gas recirculation (EGR) and the intake dry air temperatures were controlled by external coolers

in order to maintain the desired inlet conditions in a settling chamber upstream of the intake pipe (intake temperature around 333 K). The intake air ow was measured by using a hot wire ow meter. The exhaust back pressure was reproduced using a valve placed in the exhaust system as if it were the turbine of a real engine, controlling the pressure in the exhaust settling chamber. The in-cylinder instantaneous pressure signal was measured with a piezoelectric pressure transducer, with a timing resolution of 0.2 CAD (crank angle degrees), after ltering and averaging 50 consecutive engine cycles for each engine test. The main experimental result providing the auto-ignition time at any engine condition was the heat release rate (HRR) or the cumulative heat release (HR), calculated through a thermodynamic diagnostic procedure [3335]. The thermodynamic diagnostic model uses in-cylinder pressure data and solves the energy equation balance inside the cylinder, assuming uniform pressure and a mean temperature throughout the chamber at each time step. Single cylinder engine tests were carried out at the operating conditions shown in Table 2, trying to modify every one of the main parameters aecting the oxidation kinetics of any fuel, such as the engine load (quantied by the indicated mean eective pressure (IMEP)), the engine speed and the charge composition (quantied by the EGR percentage). All these parameter combinations provide dierent levels of pressure and temperature in the cylinder. As it can be observed in Table 2, HCCI conditions were

Fig. 1. Scheme of the experimental installation.

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Table 2 Engine operating conditions (SOI is negative if injection starts before TDC) Engine speed (rpm) 1500 EGR rate (%) 40 SOI (with respect to TDC) 80 60 60 80 60 2000 40 80 60 60 80 60 IMEP (bar) 5.2 2.8 6.3 4.1 4.9 2.8 6.2 4.1 5.9 3.1 5.8 4.4 5.6 3.2 7.1 4.6

3. Selection of the surrogate fuel composition As mentioned before, one of the objectives of this work is the selection of a surrogate to match the auto-ignition time of diesel fuel under real HCCI engine conditions while keeping the simplicity of the kinetic mechanism. The selected surrogate consists of a n-heptane/toluene mixture, which is representative of the alkane and aromatic content of the diesel fuel (which consists of around 37% paranes, 34% naphtenes, 29% aromatics in mass). n-Heptane oxidation simulates the two-stage combustion (cool ame and main combustion) typical of the long-chain hydrocarbons involved in HCCI combustion, and its oxidation kinetics has been the target of several studies and widely validated under engine conditions. On the other hand, toluene has been chosen to represent the diesel aromatic fraction. Aromatic compounds present in diesel fuel are mostly monoaromatics with a number of carbon atoms between 9 and 14 [28]. Their molecular structure can be supposed to be a benzene ring with one or more alkyl radicals. Benzene seems to be too simple to represent the aromatic content of diesel fuel, since it is not a branched molecule, so toluene, the following compound in complexity, could be a better representative of that aromatic fraction. Toluene oxidation has not received as much attention as branched and linear paranes, but some kinetic mechanisms have been proposed in the last years for both low and high temperature regimes [25,36,37]. Due to the lack of information about the low temperature oxidation chemistry of naphtenes, the other main hydrocarbons class in diesel fuel, and to the small amount of alkenes, and in order to avoid additional complexity in the kinetic modelling, no representative component for these classes has been considered. The optimal n-heptane/toluene mixture composition has been obtained, as detailed below, by comparing the modelled CHEMKIN results with those from the experimental tests. The simplicity of the surrogate mixture will also facilitate further reduction of the proposed mechanism to be

achieved by a very early start of injection (SOI), dened with respect to the top dead centre (TDC), which allows the fuel to completely mix with air before ignition. At each engine condition, IMEP was adjusted around the reference values (4 and 6 bar) in order to avoid the onset of knock and an excessive wall jet (liquid fuel which reaches the cylinder walls and does not participate in the combustion process) mainly at very advanced injection. Injection pressure was kept constant for all the tests at 900 bar. EGR rate has been calculated as shown in Eq. (1), where [CO2]atm is the CO2 content in the atmospheric air, and [CO2]int and [CO2]exh are the CO2 concentration in the intake and the exhaust pipe respectively. EGR CO2 int CO2 atm CO2 exh CO2 atm 1

Single cyclinder engine experiments

Fuel/Air composition (Equivalence ratio, EGR) Engine characteristics (compression ratio, speed,)

Wall transfer correlation

In - cylinder instantaneous pressure signal

CHEMKIN 4.0 ICE Reactor

Thermodynamic diagnostic model

Compression stroke initial cond. (temperature, pressure)

Rate of Heat release

Autoignition time criterion

PARAFFIN-AROMATIC COMPOSITION
Fig. 2. Scheme of the methodology used.

J.J. Hernandez et al. / Fuel 87 (2008) 655665 Table 3 Coecients used in the wall temperature correlation A Cylinder head Cylinder block Piston 2.3 2.7 8.6 B 3 3.5 5.5

659

used in CFD codes, and the future consideration of a NOx and PM formation sub-mechanisms to evaluate pollutants emission. The most adequate single components (n-heptane and toluene) kinetic mechanisms were selected among those widely validated in literature. The surrogate kinetic mechanism was built up on a step-wise fashion, using as starting point the n-heptane detailed mechanism proposed by Curran et al. [38]. Then, the reactions needed to describe the oxidation of toluene, proposed by the Lawrence Livermore National Laboratory [25], were added. Finally, the co-oxidation reactions between n-heptane and toluene were selected from those proposed by Andrae et al. [39], thus improving the prediction capability of the kinetic mechanism. The methodology used for the selection of the optimal n-heptane/toluene composition is shown in Fig. 2. Single cylinder engine tests were carried out at the operating conditions shown in Table 2. The in-cylinder instantaneous pressure signal was used as input data of a thermodynamic

diagnostic model in order to obtain the experimental rate of heat release, while the same engine conditions were simulated to obtain the modelled HRR by using the internal combustion engine (ICE) sub-routine from CHEMKIN 4.0. As mentioned before, experimental HCCI conditions were achieved with a very early fuel injection. Consequently, the diesel fuel/air mixture was supposed to be homogeneous from the end of the injection process, since the physical ignition delay can be considered negligible compared to the chemical one. The initial charge composition for the simulations was calculated from the engine equivalence ratio and the EGR rate, the former being estimated from the exhaust gas composition. An empirical lm coecient correlation for modelling heat transfer to the walls was used in order to consider the non-adiabatic behaviour of diesel engines. Among these correlations, Woschni equation is probably the most widely used for internal combustion engines calculations [40]. However, some authors [41,42] have shown that Woschni correlation overestimates the heat losses because it calculates a higher gas velocity (caused by the pressure dierences between the burnt products and the reactants zone) than that derived from HCCI conditions (where pressure dierences inside the combustion chamber are negligible). The latter eect is even more signicant when using a single-zone model, as in this work, in which the combustion is supposed to involve almost instantaneously all the reactants mass. Thus, a modication of the Woschni correlation

a
Normalized HRR

1.0 0.8 0.6 0.4 0.2 0.0 -30 -20 -10 0

Experimental 100% Hep-0% Tol 50% Hep-50% Tol

b
Normalized HRR

1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -30 -20 -10 0 CAD

Experimental 100% Hep-0% Tol 50% Hep-50% Tol

10

20

30

10

20

30

CAD

c
Normalized HRR

1.0 0.8 0.6 0.4 0.2 0.0 -30 -20 -10 0

Experimental 100% Hep-0% Tol 50% Hep-50% Tol

d
Normalized HRR

1.0 0.8 0.6 0.4 0.2 0.0

Experimental 100% Hep-0% Tol 50% Hep-50% Tol

10

20

30

-30

-20

-10

10

20

30

CAD

CAD

Fig. 3. Experimental and modelled HRR evolution for dierent engine conditions: (a) n = 1500 rpm, EGR = 40%, IMEP = 6.3 bar, SOI = 60; (b) n = 1500 rpm, EGR = 60%, IMEP = 2.8 bar, SOI = 80; (c) n = 2000 rpm, EGR = 40%, IMEP = 5.9 bar, SOI = 80; (d) n = 2000 rpm, EGR = 60%, IMEP = 4.6 bar, SOI = 60.

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recently obtained by Chang et al. [42] has been used. The thermodynamic diagnostic model has provided the optimal tting coecients values used in the correlation for the engine tested (CW1 = 5.0, CW2 = 0.2, C2 = 3.24 103). This adjustment has been made following the polytropic

coecient methodology explained in [43], which is based on the properties of the G points described in [44]. Average engine wall temperatures (C) for the piston, the cylinder head and the cylinder block have been calculated from Eq. (2) [43], where sm (m/s) is the mean piston speed, Tref

a
Cumulative HR

1.0 0.8 0.6 0.4 0.2 0.0

Experimental 100% Hep-0% Tol 50% Hep-50% Tol

b
Cumulative HR

1.0 0.8 0.6 0.4 0.2 0.0

Experimental 100% Hep-0% Tol 50% Hep-50% Tol

-30

-20

-10

10

20

30

-30

-20

-10

10

20

30

CAD

CAD

c
Cumulative HR

1.0 0.8 0.6 0.4 0.2 0.0

Experimental 100% Hep-0% Tol 50% Hep-50% Tol

d
Cumulative HR

1.0 0.8 0.6 0.4 0.2 0.0

Experimental 100% Hep-0% Tol 50% Hep-50% Tol

-30

-20

-10

10

20

30

-30

-20

-10

10

20

30

CAD

CAD

Fig. 4. Experimental and modelled cumulative HR for dierent engine conditions: (a) n = 1500 rpm, EGR = 40%, IMEP = 6.3 bar, SOI = 60; (b) n = 1500 rpm, EGR = 60%, IMEP = 2.8 bar, SOI = 80; (c) n = 2000 rpm, EGR = 40%, IMEP = 5.9 bar, SOI = 80; (d) n = 2000 rpm, EGR = 60%, IMEP = 4.6 bar, SOI = 60.

Normalized HRR

0.8 0.6 0.4 0.2 0

-40 -30 -20 -10 0 10 20 30

10% HRR main combustion

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 -40

Cumulative HR

SOC
Cool Flames -30 -20 -10 0 10 20 30

CAD
Fig. 5. Denition of the start of combustion (SOC).

J.J. Hernandez et al. / Fuel 87 (2008) 655665

661

SOC (exp)-SOC (mod) (CAD)

(K) the coolant temperature, qint (kg/m3) the intake air density and A and B are empirical constants, shown in Table 3. T wall T ref A qint sm
0:8

6 5 4 3 2 1 0 -1 -2 -3 0 1 2 3 4 5 6 7 8

n=1500, EGR= 40 n=2000, EGR= 40 n=1500, EGR= 60 n=2000, EGR= 60

B IMEP

SOC (CAD)

Figs. 3 and 4 show, as an example, the experimental and the modelled HRR and the cumulative HR evolutions for four selected engine conditions and two surrogate compositions. Both experimental and modelled HRR are characterized by two peaks, corresponding to the onset of cool ame (low temperature chemistry) and to the complete combustion (high temperature oxidation), respectively. The modelled HRR evolution shows a very sharp shape (as also observed in the cumulative HR curve) and narrow peaks as a consequence of the single-zone character of the CHEMKIN sub-routine. In this paper, the start of combustion (SOC) (auto-ignition angle) was dened, similarly as in other works [45,46] and shown in Fig. 5, as the crank angle corresponding to 10% of the cumulative heat released during the high temperature combustion process. The optimum n-heptane/toluene composition has been be selected as that minimizing the statistical mean square error (MSE) dened as, s PN 2 i1 SOCi exp SOCi mod MSE 3 N where N is the number of engine tests, SOCi(exp) and SOC,i(mod) are the experimental and modelled auto-ignition angles respectively, dened with respect to TDC (being negative if ignition occurs before TDC). As shown in Fig. 6, the composition of the surrogate fuel which provides a lowest MSE value is 50% n-heptane/50% toluene in mass. Fig. 7 shows the dierences between experimental and modelled ignition angle results (where positive values represent experimental ignition angles delayed with respect to the modelled one), while Fig. 8 shows, as an example, the eect of the engine operating conditions at 2000 rpm. As it can be observed in Fig. 7, modelled results are reasonably similar to the experimental ones, although larger difn-heptane content (% in mass)
4.0 3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 100 90 80 70 60 50 40

IMEP (bar)
Fig. 7. Dierences between experimental and modelled SOC values for all the engine operating conditions (lled symbols: SOI = 80 CAD, empty symbols: SOI = 60 CAD).

4 2 0 -2 -4 -6 -8 -10 -12 -14 -16

2 3 4 5 6 7 8

SOI=-60 EGR=40 SOI=-80 EGR=40 SOI=-60 EGR=60 SOI=-80 EGR=60

IMEP (bar)

Fig. 8. Experimental (solid lines) and modelled (dashed lines) SOC values at 2000 rpm.

10

20

30

40

50

60

Toluene content (% in mass)

Fig. 6. MSE values for dierent surrogate compositions.

ferences have been obtained at low engine speed and high engine load, both conditions associated with higher ratios of heat transfer to the engine walls. These latter dierences are probably caused by the lm coecient correlation used for the calculation, which underestimates the modelled heat transfer. As shown in Fig. 8, the eect of EGR depends on the engine load. At large EGR rates, higher IMEP values lead to a more delayed start of combustion, while the opposite trend has been obtained at low EGR rates. This trend could be due to the dierent values of the engine equivalence ratio. At high EGR rates and IMEP values, this ratio is close to stoichiometric due to the low oxygen content in the oxidant, generating a lower amount of reactive radicals (such as OH and H). These radicals preferably react with the fuel to produce less reactive intermediates, thus delaying the auto-ignition process. The advance of the SOI also delays the SOC. This can be explained by the lower adiabatic coecient of the fuel/air mixture with respect to pure air, which causes lower cylinder pressure and temperature during the compression stroke.

MSE (CAD)

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4. Chemical kinetics analysis This paragraph analyses the main dierences between the reaction kinetics of pure n-heptane and that derived from the addition of toluene, the latter causing higher fuel ignition delay times. In order to clearly identify the eect of toluene at the temperature range typical of diesel HCCI combustion, constant volume simulations have been carried out by using the CHEMKIN code (closed homogeneous batch reactor sub-routine). Fig. 9 shows temperature evolutions for several n-heptane/toluene mixtures (in mass) at two dierent initial temperature values, 800 K (a) and 1200 K (b). The rst one causes the fuel to rstly oxidize following the low temperature chemistry, while for the second one (1200 K) only the high temperature paths take place. It can be observed that the inuence of the toluene content on the nal temperature reached for both low and high initial temperature values is not signicant. However, its inuence on the ignition delay time is higher for low initial temperature, being unnoticeable for 1200 K. The larger delay found at 800 K when toluene is added is due to the lower heat release during the low temperature oxidation, since toluene does not show any cool ame behaviour [47]. In addition, at low temperature of 800 K toluene is expected to rapidly convert into stable intermediates, mainly benzaldehyde and phenol (as shown in Fig. 10),
Concentration (moles/cm3 )

1.0x10 8.0x10 6.0x10 4.0x10

-6

-7

-7

Moles of toluene removed Moles of benzaldehyde Moles of phenol Moles of 2-buten-1,4-dial Moles of benzene Total intermediates moles

-7

2.0x10

-7

0.0
0.000 0.002 0.004 0.006 0.008 0.010

time (s)

Fig. 10. Intermediates evolution for a 50% n-heptane/50% toluene mixture (T = 800 K, p = 10 bar, equivalence fuel/air ratio = 0.6).

by reacting with the very reactive radicals generated during the n-heptane low temperature reactions, thus decreasing the reactivity of the mixture. A sensitivity analysis has been performed in order to identify the main reaction paths involved during the n-heptane/toluene mixture oxidation under HCCI conditions. The inuence of a model parameter on the selected output is evaluated through the sensitivity coecient (Eq. (4)), which are dened as: s ou oa 4

a
Temperature (K)

2500 2000 1500 1000 500 0 0 0.002 0.004 0.006 0.008

where u and a represent the output and the parameter investigated respectively. In this case, the sensitivity of the pre-exponential factor (A) of each reaction rate constant on the mixture temperature (T) has been calculated in its normalized form (Eq. (5)), in order to allow for comparison between values.
100% Hep-0% Tol 80% Hep-20% Tol 60% Hep-40% Tol 50% Hep-50% Tol 0.01

A oT o lnT T oA o lnA

time (s)

b
Temperature (K)

3000 2500 2000 1500 1000 500 0 0 0.0002 0.0004 0.0006

Since the inuence of toluene is greater at the low temperature regime, the normalized sensitivity coecients have been evaluated for initial temperature values lower than 1000 K. Two dierent equivalence ratios were analysed in order to study the eect of mixture composition. As shown in Fig. 11, the most sensible reactions for toluene submechanism are the dehydrogenation of toluene by OH and O2 (reactions R1 and R2, respectively). R1 : R2 : C6 H5 CH3 OH ! C6 H5 CH2 H2 O C6 H5 CH3 O2 ! C6 H5 CH2 HO2

100% Hep-0% Tol 80% Hep-20% Tol 60% Hep-40% Tol 50% Hep-50% Tol

time (s)
Fig. 9. Temperature proles for dierent constant volume simulations (a) T = 800 K, p = 10 bar, equivalence fuel/air ratio = 0.6; (b) T = 1200 K, p = 10 bar, equivalence fuel/air ratio = 0.6.

Both reactions are in competition, since R1 corresponds to a termination reaction due to the lower reactivity of the benzyl radical compared to the hydroxyl radical, and R2 corresponds to a branching reaction (which favours the oxidation process). Termination reactions decrease the reactivity of the mixture by eliminating reactive radicals, thus causing lower heat release during the low temperature regime, while the reaction of toluene with molecular

J.J. Hernandez et al. / Fuel 87 (2008) 655665

663

C7H15O2-2=C7H14OOH2-4 C7H15O2-3=C7H14OOH3-5 C7H14OOH1-3O2=n-C7KET13+OH n-C7H16+OH=C7H15-3+H2O C6H5CH3+OH=C6H5CH2+H2O C6H5CH3+O2=C6H5CH2j+HO2 C7H15O2-4=C7H14OOH4-1 Equivalence ratio 0.4 Equivalence ratio 0.8

-0.25

-0.15

-0.05

0.05

0.15

0.25

s
Fig. 11. Maximum normalized sensitivity coecients of temperature to reaction rates (T = 800 K, p = 10 bar).

0 -2000
40 ROP (moles/m3s)

-4000 -6000 -8000 -10000

20

0 -25 -24 -23 -22 CAD -21 -20

Total c6h5ch3+oh=c6h5ch2j+h2o c6h5ch3+o2=c6h2ch2j+ho2

-12000 -25

-24

-23

-22

-21

-20

CAD

Fig. 12. Rate of production analysis for toluene at low temperature.

oxygen have the opposite eect. Temperature is very sensible to reaction R2 especially for rich mixtures, since the availability of oxygen controls the R2 reaction rate (oxygen reacts preferably with the n-heptane secondary CH bonds rather than the toluene primary CH bonds). The inuence of toluene on the overall reactivity of the mixture depends on the importance of each path (R1 and R2) during the fuel oxidation. This has been evaluated performing a rate of production (ROP) analysis to determine the contribution of reactions R1 and R2 to the net production or destruction rates of toluene. As can be seen in Fig. 12, the most important route consuming toluene is reaction R1, being the toluene decomposition through reaction R2 negligible. Therefore, the higher toluene content in the mixture, the higher removal of reactive radicals and the lower mixture reactivity at low temperature. 5. Conclusions An improved surrogate diesel fuel composition has been proposed to simulate the auto-ignition time of diesel fuel in HCCI combustion. The surrogate fuel consists of a 50% n-heptane/50% toluene mixture (in mass). This composition has been selected by comparing modelled delay time

values with those coming from HCCI single cylinder engine tests. The engine operating conditions were modied in order to consider all the important parameters controlling the two-stage oxidation kinetics typical of diesel HCCI combustion, such as the engine load, the engine speed, the start of injection (SOI) and the charge composition (quantied by the EGR). In order to provide simplicity to the kinetic reaction mechanism and to facilitate its further reduction to be used in CFD codes, no representative component for alkenes (whose amount in diesel fuel is not signicant) and naphtenes (whose low temperature oxidation process is still uncertain) has been considered. Modelled delay time results are in agreement with the experimental ones, following both results very similar trends when changing the engine operating conditions. The use of EGR, which is one of the most promising techniques to control diesel HCCI combustion, appears to have a very important eect on the delay time. At high engine loads, higher EGR rates cause a more delayed combustion process due to the excess of fuel, which acts as a reactive radical sink, while the opposite occurs at low EGR rates. A chemical kinetics analysis has been carried out to identify the main reaction paths derived from the addition of toluene to the commonly used n-heptane. This analysis shows that toluene has no inuence on the delay time for high initial temperature values (one step combustion) but decreases the mixture reactivity when using low initial temperature (two stage oxidation). The latter is due both to the absence of cool ames for toluene and to the lack of reactive radicals (OH, H, O) because they are preferably consumed by toluene to produce stable compounds (benzaldehyde and phenol). The two most signicant paths controlling the low temperature oxidation when toluene is used are the dehydrogenation of toluene by OH (termination reaction) and O2 (branching reaction). Although the latter should increase the reactivity of the n-heptane/toluene mixture, mainly for high fuel/air equivalences ratios, a rate of production analysis has shown that this reaction is negligible as compared with that of dehydrogenation by OH, which leads to higher auto-ignition delay times.

ROP (moles/m3s)

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