This document summarizes a numerical study of ignition delay times in a perfectly stirred reactor (PSR) using a gasoline fuel surrogate. The study varied initial temperature, pressure, equivalence ratio, inlet temperature and residence time. It was found that ignition delay times in a PSR can differ significantly from batch reactors and depend strongly on residence time. Ignition was easier at higher temperatures and pressures. Rich mixtures also favored ignition at intermediate residence times when initially filled with air. The results provide insights into low-temperature chemistry and ignition in real combustion devices.
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Bachelor's thesis article
1. 40th
Meeting of the Italian Section of the Combustion Institute
NUMERICAL INVESTIGATION OF IGNITION
DELAY TIMES IN A PSR OF GASOLINE FUEL
F. S. Marra*, L. Acampora**, E. Martelli***
marra@irc.cnr.it
*Istituto di Ricerche sulla Combustione – CNR, Napoli, ITALY
*Università degli Studi del Sannio, Benevento, ITALY
**Università della Campania “Luigi Vanvitelli”, Aversa, ITALY
Abstract
This paper reports on preliminary results of a study conducted by simulating the
ignition of a flammable mixture of gasoline and air, in a perfectly stirred reactor
(PSR). Several ignition conditions have been analyzed by varying the initial
temperature, the pressure and the equivalence ratio and temperature of the feeding
mixture. The fuel has been described with a surrogate composed by a mixture of n-
heptane, toluene and iso-octane. The detailed chemical mechanisms proposed by the
CRECK group of Politecnico di Milano, the POLIMI-TOT-NOX-1407, consisting
of 484 species and 19341 reactions has been adopted to achieve a high fidelity in the
reproduction of the ignition delay time.
The effect of mixture composition, pressure, initial temperature and residence time
is illustrated. It is shown that significant deviations from the ignition delay time
(IDT) measured in batch reactor arise. The dependency shown upon the parameters
space can be of great help in explaining the ignition behavior in real engines, which
is often difficult to interpret.
Introduction
Ignition Delay Time (IDT) is a fundamental property of a flammable mixture that
has a strong influence on the performances of transportation engines [1]. It is
extensively adopted also to test the performances of chemical mechanisms aimed at
miming the behavior of real fuels [2]. Because ignition always starts at temperatures
lower than the final temperature reached after the thermochemical conversion, a
proper representation of the low temperature chemistry is required to achieve correct
predictions; a very difficult task especially starting from ambient conditions [3].
IDT, whose exact definition is not univocal, can be determined by measuring the
spontaneous evolution of the mixture in batch conditions, experimentally realized in
batch reactors or, for higher initial temperatures, in shock tubes. The same conditions
are numerically realized by the constant pressure batch reactor model, fixing the
initial conditions of the mixture. However, in real conditions, almost never this is the
effective evolution experimented by the mixture: in combustors, where a regime of
steady ignited conditions is eventually desired, the ignition is an unsteady process
occurring in a flowing reactor at constant pressure, during the continuos mixing with
a fresh mixture; in spark ignited Internal Combustion Engines, a flame develops at
2. 40th
Meeting of the Italian Section of the Combustion Institute
every cycle within a highly recirculating flow at variable pressure and temperature,
thus continuously varying the conditions of subsequent ignition of the propagating
flame. Therefore, while IDT in batch conditions are of paramount importance to
establish fundamental properties of the mixture chemical behavior, the connection
with ignition conditions in practical devices is weaker.
Ignition conditions closer to those just described for combustors can be reproduced
in an unsteady Perfectly Stirred Reactor (PSR). This reactor, extremely simple yet,
include the effect of a flowing stream and therefore the ignition phenomenon can be
studied in a wider range of conditions that include, further to initial mixture
equivalence ratio, pressure and temperature, also the composition and temperature
of the feeding mixture, and the residence time in the reactor. The interplay of this
parameters leads to much complex interactions driving the chemical evolution of the
reactive mixture that, even if a 0-Dimensional description of the system is adopted,
have resemblance with the inner chemical portion of a flame structure propagating
in a not homogeneous field.
This paper reports on preliminary results of this study. Several ignition conditions of
a gasoline-air mixture in a PSR have been simulated by varying the initial
temperature and the equivalence ratio of the feeding mixture, the feeding
temperature and mixture composition, and the pressure. The effect of mixture
composition, pressure, initial temperature and residence time is illustrated. It is
shown that significant deviations from the IDT measured in batch reactor arise.
Mathematical Model
The governing ordinary differential equations of the adiabatic, constant pressure PSR
fed by a mixture of 𝑁𝑆 species with mass fraction 𝑌𝑖, molecular weight 𝑊𝑖 and
temperature 𝑇, can be given as [4]:
𝑑𝑌𝑖
𝑑𝑡
=
𝑌𝑖,𝑓 − 𝑌𝑖
𝜏
+
𝑊𝑖𝑟𝑖
𝜌𝑉
, 𝑖 = 1, … , 𝑁𝑆 (1)
𝑑𝑇
𝑑𝑡
= ∑
𝑌𝑖,𝑓(ℎ𝑖,𝑓 − ℎ𝑖)
𝜏 𝑐𝑃
𝑁𝑆
𝑖=1
− ∑
𝑊𝑖𝑟𝑖ℎ𝑖
𝜌𝑉𝑐𝑃
𝑁𝑆
𝑖=1
(2)
where ℎ𝑖 are the enthalpies of species 𝑖, 𝑟𝑖 the their reaction rate. The subscript 𝑓
indicates the feeding (inlet) conditions and 𝜏 = 𝜌𝑉/𝑚
̇ 𝑓 is the nominal residence time
and related to the reactor volume (𝑉) and the mass flow rate (𝑚
̇ 𝑓). 𝑐𝑃 is the constant
pressure specific heat coefficient of the mixture.
Mixtures formed by air and gasoline are considered. Air is supposed to have 76.7 %
mass of nitrogen and 23.3 % mass oxygen. The fuel has been described with a
surrogate composed by a mixture of n-heptane, toluene and iso-octane
(0.630 𝑖C8H18 + 0.200 C7H8 + 0.170 𝑛C7H16) [5]. The detailed chemical
mechanisms proposed by the CRECK group of Politecnico di Milano [], the
POLIMI-TOT-NOX-1407, composed by 484 species and 19341 reactions has been
3. 40th
Meeting of the Italian Section of the Combustion Institute
adopted to achieve a high fidelity in the reproduction of the ignition delay time.
The IDTs in the PSR (PSR-IDT) at different working conditions have been obtained
by computing the time instant of the maximum in the signal of temperature rise
velocity. However, every simulation has been successively verified to filter out cases
with failed ignitions.
Results
PSR-IDTs have been evaluated at different residence times assuming that only air is
initially present in the reactor while the reactor is fed with the flammable mixture.
With respect to an auto-ignition process in a batch reactor, the ignition in this
configuration differs substantially. The most influencing factors are expected to be
the time required to supply the inflammable mixture and the heat loss determined by
the outflow of the expanding mixture.
Typical ignition curves versus time are represented in Fig. 1 for 𝑃 = 48 atm, 𝑇𝑖 =
1200 K, 𝑇0 = 1000 K, 𝜑 = 1, and different values of 𝜏. To make comparable the
different cases, the time has been non-dimensionalized with the respective residence
time. It is recognized that the ignition process is quite different changing the
residence time. Two different stages are recognized, a fast (that occurs in a time
shorter than the residence time) and a delayed stage.
Figure 1. Time evolution of the temperature (left) and OH mass fraction (right)
versus non-dimensional time.
A complete picture of the conditions for which the ignition of the mixtures is possible
is given in Fig. 2. Several trends can be recognized, mostly confirming expectation.
As expected, an increase of the temperatures, both 𝑇0 and 𝑇𝑖𝑛, favors ignition.
Residence time and inlet temperature play a major role: ignition becomes very
difficult, and allowed only at the highest inlet temperatures, when a very short
residence time is considered. Higher pressure always enlarges the region of ignition.
The mixture composition has a very little effect at the lowest residence times, while
4. 40th
Meeting of the Italian Section of the Combustion Institute
its effect is significant especially at intermediate residence times.
Figure 2. Ignition maps in the temperatures plane (1000/𝑇𝑖𝑛, 1000/𝑇0) at pressures
of 12 and 48 atm. From top to bottom is increasing residence time. From left to
right is increasing equivalence ratio.
5. 40th
Meeting of the Italian Section of the Combustion Institute
In these cases, the ignition is favored by rich mixtures. This is easily explained in
coupling with the initial, pure air, content of the reactor: a flammable mixture more
rapidly forms in the reactor during the first instants, and the heat released helps the
stabilization of ignited regime conditions.
Figure 3. IDT for a stoichiometric mixture from experiments in batch reactors
(black circles, adapted from [], high pressure conditions) and IDT from present
computations in PSR, 𝑃 = 48 atm (colors are for different residence times, empty
symbols for constant 𝑇𝑖𝑛 , filled symbols for constant 𝑇0).
Figure 3 reports the PSR-IDT computed at 𝑃 = 48 atm for a stoichiometric mixture
using different residence time, and different initial and feeding temperatures. For
comparison, classically defined IDT in a batch reactor at the same stoichiometric and
pressure conditions are also reported. Several interesting observations can be made.
The PSR-IDT initially filled with air mainly depends on the residence time and is
very roughly proportional to this parameter: about an order of magnitude can be
expected by changing the temperatures but it is difficult to observe the ignition of
the mixture in a time much shorter than 1/10𝑡 even at the highest temperatures.
Following these indications, ignition delay times in real devices could greatly differ
from the ideal IDT. The effect of changing 𝑇𝑖𝑛 at constant 𝑇0 (empty symbols in Fig.
3) is very weak. Instead, significant variations are found by changing the initial
temperature in the reactor. This can be interpreted by observing that, due to the
immediate mixing of the feeding mixture with the mixture in the reactor at the
beginning of the phenomenon, the temperature of the latter mixture predominates in
the first ignition stage. Instead, successful ignition is mostly dependent on the
feeding temperature, because of the role of the feeding mixture energy content in
sustaining the reaction progress.
6. 40th
Meeting of the Italian Section of the Combustion Institute
Conclusions
The paper illustrates the first preliminary results obtained from the study of the
ignition process of a gasoline in a constant pressure PSR. Several important
indications are deduced from this kind of analysis, that can extend the importance of
the study of IDT in batch reactors. For instance, it has been shown that the PSR-IDT
is roughly proportional to the residence time, thus implicating that low temperature
chemistry can be sustained in a time interval much longer than that observed in batch
reactors. Furthermore, the chemical evolution in this kind of reactor involves a much
larger spectrum of mixtures composition, due to the continuos feeding of the
reactants. It makes possible the observation, in a zero-dimensional reactor, of a large
variety of reaction conditions, including those involving the combination of
molecules formed during initial dissociations with molecules formed during the last
stages of products formation.
Acknowledgements
The authors are very grateful to Luca Gravante, Antonio Di Felice and Giacomo De
Vico for their contribution to the setup of the numerical procedures and the collection
and processing of the large amount of data produced.
References
[1] Lefebvre, A.W., Gas Turbine Combustion, CRC Press, 2010.
[2] Lu, T., Law, C.K., “Toward accommodating realistic fuel chemistry in large-
scale computations”, Prog. En. Comb. Sci. 35: 192–215 (2009).
[3] Battin-Leclerc, F., “Detailed chemical kinetic models for the low-temperature
combustion of hydrocarbons with application to gasoline and diesel fuel
surrogates”, Prog. En. Comb. Sci. 34:440–498 (2008).
[4] Wada, T., Jarmolowitz, F., Abel, D., Peters, N., “An Instability of Diluted
Lean Methane/Air Combustion: Modeling and Control”, Comb. Sci. Tech.
183:1–19 (2010).
[5] Gauthier, B.M., Davidson, D.F., Hanson, R.K., “Shock tube determination of
ignition delay times in full-blend and surrogate fuel mixtures”, Comb. Flame
139:300–311 (2004).
[6] Faravelli, T., Frassoldati, A., and Ranzi, E., “Kinetic modeling of the
interactions between NO and hydrocarbons in the oxidation of hydrocarbons
at low temperatures”, Comb. Flame 132:188–207 (2003).
[7] Frassoldati, A., Faravelli, T., and Ranzi, E., “Kinetic modeling of the
interactions between NO and hydrocarbons at high temperature”, Comb.
Flame, 135:97–112 (2003).
7. 40th
Meeting of the Italian Section of the Combustion Institute
NUMERICAL INVESTIGATION OF IGNITION
DELAY TIMES IN A PSR OF GASOLINE FUEL
F. S. Marra*, L. Acampora**, E. Martelli***
marra@irc.cnr.it
*Istituto di Ricerche sulla Combustione – CNR, Napoli, ITALY
*Università degli Studi del Sannio, Benevento, ITALY
**Università della Campania “Luigi Vanvitelli”, Aversa, ITALY
Errata corrige
Because of a last minute mistake, the images reported for Fig. 1 in the submitted
paper were taken from a wrong directory, where not converged solutions where
saved. The system of ODE integrated is very stiff and a careful check of each solution
was needed to purge not converged results, a not trivial task because of the large
number of solution processed. The correct Fig. 1is here below reported.
Figure 1. Time evolution of the temperature (left) and CO mass fraction (right)
versus non-dimensional time.