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Proefschrift
door
Sander Gersen
geboren op 2 oktober 1976
te Gouda
Promotor: Prof. dr. H.B. Levinsky
Copromotor: Dr. A.V. Mokhov
ISBN 978-90-367-3254-3
Sander Gersen
The work described in this thesis was performed in the Laboratory for Fuel and
Combustion Science at the University of Groningen, Nijenborgh 4, 9747 AG
Groningen, the Netherlands. This project is supported with a grant of the Dutch
Program EET (Economy, Ecology, Technology) a joint initiative of the Ministries of
Economic Affairs, Education, Culture and Sciences and of Housing, Spatial Planning
and the Environment. The program is run by the EET Program Office, SenterNovem.
S.Gersen,
Introduction 5
2.1 Background 27
2.2 Design and Operations 38
2.2.1 Experimental System 32
2.2.2 Gas filling system and filling procedure 33
2.2.3 Instrumentation and data acquisition 34
2.3.4 Determination autoignition delay time 35
2.3.5. Temperature determination 36
Appendix A.1 40
Appendix A.2 41
Appendix A.3 42
Appendix A.4 43
Appendix A.5 44
3.1 Introduction 49
3.2 Experimental approach 51
3.3 Numerical simulation and analysis of experimental data 52
I
3.3.1 Chemical mechanisms 52
3.3.2 Numerical simulations 53
3.4 Results and discussion 56
3.5 Comparison of experimental results with numerical simulations 63
3.6 Summary and conclusions 68
II
Chapter 6: HCN formation and destruction in atmospheric pressure fuel-rich
premixed methane/air flames
Summary 136
Samenvatting 140
Dankwoord 144
III
IV
Inroduction
Introduction
5
Introduction
6
Chapter 1
CHAPTER 1
7
Chapter 1
[ Fuel ] 1
ϕ= . , (1.1)
[Oxidizer ] f st
where the amounts [fuel] and [oxidizer] can be expressed in molar, volume or mass
units, and fst is the ratio of fuel to oxidizer under stoichiometric conditions using the
same units. Here we will generally use moles or mole fraction as units. A mixture is
said to be stoichiometric (ϕ=1) when fuel and oxidizer are present in the ratios
prescribed by the balanced chemical reaction for combustion:
n n
C x H n + ( x + )O2 → xCO2 + H 2 O , (R1.1)
4 2
If the oxidizer in the unburned mixture is in excess, the mixture is said to be fuel-lean
(ϕ<1), while the mixture is called fuel-rich (ϕ>1) when an excess of fuel in the
unburned mixture is present. The gas mixture can remain unreacted, such as in fuel-air
mixtures at room temperature in the absence of an ignition source, or the fuel and
oxidizer react (combust) to form products. Combustion can take place either in a
flame (a reaction front propagates subsonically through the mixture) or in a non-flame
mode (“homogeneous combustion”, reaction occurs simultaneously everywhere in the
mixture). To understand which mode of combustion takes place under a given set of
conditions (temperature, pressure, equivalence ratio), it is necessary to study the
chemical processes in the system in detail. The overall combustion process can be
described by reaction (R1.1). However, it is unrealistic to think that combustion
proceeds via this single reaction because it would require breaking high-energy bonds,
which at room temperature makes this reaction extremely slow. Instead, combustion
occurs in a sequential process involving many reactive intermediate species.
To illustrate this process, we first consider a H2-O2 gas mixture. The conversion of
hydrogen and oxygen to water starts with the formation of reactive species (radicals)
8
Chapter 1
to initiate a chain of reactions [1]. The reactions in which radicals are formed from
stable species are called chain-initiation reactions, and an example of a chain-
initiation reaction is the (endothermic) dissociation reaction:
The H radicals formed in reaction (R1.2) can react further with oxygen molecules,
forming two new radicals, OH and O,
This reaction (R1.3), in which two radicals are created for each radical consumed is
called a chain-branching reaction and is crucially important in combustion processes.
The formation of the radicals OH and O can lead to further chain branching via
In addition, there are reactions in which the number of radicals does not change, such
as
which are called chain-propagating reactions. The reactions in which radicals react to
stable species without forming another radical are called chain-terminating reactions,
as in
Although not strictly chain terminating, since HO2 is a radical, the reaction
9
Chapter 1
is often considered chain terminating because, compared with the “flame radicals”, H,
O and OH, the HO2 radical is relatively unreactive. At low pressures, reaction (R1.7)
is an important chain-terminating reaction because the mildly reactive HO2 radicals
diffuse to the wall, where they react at the surface. Summing the chain-branching and
chain-propagating reactions (R1.3+R1.4+R1.5+R1.5) results in
from which we can see that starting with one radical, three radicals are formed from
the reactants in this simplified mechanism.
For quantitative description of chemical processes the rate of change of the
species concentrations (formation and consumption) should be determined. For
species A in an arbitrary bimolecular elementary reaction,
kf
aA + bB ⇔ cC + dD, (R1.9)
kr
dA
= − k f [ A] a [ B ]b + k r [C ]c [ D] d , (1.2)
dt
where A,B,C,D denote the different species in the reaction, a,b,c,d are the
stoichiometric coefficients of species A,B,C,D, respectively, and kf and kr represent
the forward and reverse rate coefficient of the reaction. For example, the rate of
change of the oxygen radical in reaction (R1.3) is expressed as,
d [O]
= − k Rf1.3 [ H ][O2 ] + k rR1.3 [OH ][O] . (1.3)
dt
The rate coefficients kf and kr are connected through the equilibrium constant Kw. The
reaction rate constant k of a reaction is generally assumed to have a modified-
Arrhenius temperature dependence,
⎛ E ⎞
k = AT b exp ⎜ − A ⎟ , (1.4)
⎝ RT ⎠
10
Chapter 1
d [ n]
= γ + (α − β )[n] , (1.5)
dt
From equation (1.5) three different scenarios can be derived, which are presented
schematically in figure 1.1 a [2].
Figure 1.1a) Schematic of the growth of the concentration of free radicals [n] in time.
b) Schematic of the growth of free radicals [n] in time for the cases with and without
heat release.
11
Chapter 1
For the condition α>β the concentration [n] increases exponentially in time, and
ignition takes place. When α<β, d[n]/dt becomes zero, and no exponential growth of
free radicals occurs (no ignition). The condition α=β results in a linear growth of the
concentration of free radicals, and defines the ignition limit. Equation (1.5) shows that
the growth of the concentration of free radicals is determined by the competition
between the chain branching (R1.3) and chain terminating reactions (R1.7). A very
important parameter in this competition is the temperature, since the chain branching
reaction (R1.3) has large activation energy Ea [3] while that of the chain terminating
reaction (R1.7) is small [4]. Thus, the value of α (chain branching) is strongly
dependent upon the temperature, and β (chain terminating) is more or less
independent of the temperature. At low temperatures the endothermic chain branching
reaction will not proceed rapidly, so the value of α is much smaller than β (α<β), and
ignition does not occur. Increasing the temperature results in an increase in α, while β
remains unchanged; at sufficiently high temperatures α will be larger than β and
ignition occurs. The temperature during the early period of the ignition process
remains more or less constant because the heat release from the branching and
propagating reactions (R1.8) is small, but as the radical concentration grows,
exothermic reactions such as (R1.6) and (R1.7) will produce substantial quantities of
heat. If the heat produced by the exothermic reactions in system exceeds the rate of
heat loss to the surrounding, the temperature in the system will rise. Since the rate of
reaction, and thus the rate of heat release, grows exponentially with temperature, the
overall reaction will auto-accelerate, that is, the system will “explode”. The time
before explosion takes place is called autoignition delay time (figure 1.1b). In this
example, if no heat accumulates in the system (T=constant), no auto-acceleration of
the reaction rate takes place; in this case we speak of “non-explosive” reactions, both
situations are shown in figure 1.1b.
As described above, the dominance of chain branching reaction (R1.3)
characterizes the high temperature regime, while at low and intermediate temperatures
the in essential chain terminating reaction (R1.7) competes effectively with reaction
(R1.3) [5]. Since the rate of a three-body reaction increases with pressure much faster
than the rate of a two-body reaction, there exists a pressure above which reaction
(R1.7) exceeds the rate of the competing reaction (R1.3). Reaction (R1.7) is only a
chain terminating reaction when the produced HO2 radicals will diffuse to the wall
12
Chapter 1
The H radicals so produced can contribute to chain branching via (R1.3) or will
generate more HO2 via reaction (R1.7) and H2O2 itself can contribute to branching via
[5],
Thus at high pressure and moderate temperatures reaction (R1.7) will dominate over
(R1.3), and the number of active centers will grow (α>β) via the sequence of
reactions (R1.7), (R1.10), and (R1.11).
Instead of heating the “cold” gas mixture by the heat release of exothermic
reactions as in this example of a closed homogeneous system, in flames, the mixture
is heated by conduction from the hot flame gases. Furthermore, radicals needed to
decompose the fuel are also transported from the high temperature region of the
flame. As in the closed system described above, the rate of formation of radicals
controls the overall rate of reaction in flames. For flames, however, the chain
initiation and chain-terminating reactions are less important in the
formation/destruction of radicals (α>>β), and the reactions (R1.3)-(R1.5), responsible
for the growth of the radical pool, dominate the overall reaction rate in H2-O2 flames
[6].
The combustion chemistry of hydrocarbon fuels is much more complicated than
that of hydrogen. As an example, we consider a CH4-O2 mixture. Under flame
conditions (α>>β), the most important chain branching reaction in the oxidation of
methane is also reaction (R1.3) [6]. After radicals are transported into the unburned
gas mixture, methane is attacked by the radicals, as in
13
Chapter 1
As can be seen from figure 1.2, the rate coefficient of reaction (R1.12) [7] is much
larger than that for reaction (R1.3) [3]. Thus reaction (R1.12) competes effectively
with reaction (R1.3) for H atoms and reduces the chain branching rate.
Figure 1.2. Reaction rate expressions for reaction R1.3 [3] and reaction R1.12 [7].
The oxidation of the CH3 formed, and the development of the radical pool, is
complicated and slow. This process dominates most of the ignition delay period and is
14
Chapter 1
Figure 1.3. Computed autoignition delay times for stoichiometric H2/air and CH4/air
mixtures at P=30 bar. Calculations were made using the GRI-Mech 3.0
mechanism [11].
Besides their effects on the combustion properties, such as burning velocity and
ignition, the differences in the combustion chemistry of methane and hydrogen have
significant consequences for pollutant formation. One of the main consequences is
that during the combustion of methane (and other hydrocarbons) carbon containing
pollutant species like soot, HCN and CO are formed, while the only pollutant from
hydrogen combustion is NOx. Moreover, the formation of NO in methane combustion
is different than that from H2 combustion; in methane flames an additional mechanism
exist that produces NO via the hydrocarbon intermediate CH [12]:
15
Chapter 1
CH + N 2 ⇔ products ⇔ NO . (R1.14)
( NCN ?, HCN ?)
d ( ρV ) d K
dt
=
dt
∑ ρVYk =0, (1.6)
k =1
where ρ is the overall mass density, V is the system volume and Yk is the mass fraction
of k-th component in the gas mixture. The mass fractions of individual species change
in time according to
dYk
ρ = ω k Wk , k = 1…….K (1.7)
dt
16
Chapter 1
where ωk and Wk are the molar chemical production rate per unit of volume and
molecular weight of the k-th species, respectively. The density is related to
temperature T, pressure p and composition through the ideal gas equation of state:
p
ρ= W, (1.8)
RT
⎛ K Y ⎞
where W = 1/ ⎜ ∑ k ⎟ is the average molecular weight of the mixture. The system
⎝ k =1 M k ⎠
(1.6) – (1.8) consists of (K+1) linearly independent equations and contains (K+3)
unknown parameters: ρ, p, T, V and Yk. Since the system contains more unknowns
than equations, it can be solved only when two unknown parameters (for example, the
measured temperature and pressure) are used as input. The number of input
parameters can be decreased to one if the energy conservation equation is added to the
system. The energy conservation equation can be derived from the first law of
thermodynamics, which states that heat δQ added to the system is equal to the sum of
the change of its internal energy dU and the work PdV of the system against an
external force:
dU + PdV = δ Q . (1.9)
dU dV dQ •
+P = = Q loss . (1.10)
dt dt dt
K
U= ∑ ρVYk uk , (1.11)
k =1
17
Chapter 1
⎛1⎞
d⎜ ⎟ .
ρ 1 K
+ p ⎝ ⎠ + ∑ uk ωkWk = qloss ,
dT
Cv (1.12)
dt dt ρ
k =1
•
where qloss = Q loss /(ρV) is the heat loss per unit of mass and Cv is the specific heat of
T
C vW dT ⎛ ρ ⎞
∫ R T
= ln⎜⎜ ⎟⎟ .
⎝ ρ0 ⎠
(1.13)
T0
It is common to use the ratio of molar heat capacities at constant pressure and constant
volume, γ, and a specific volume v, instead of Cv and ρ. In this case, equation (1.13)
can be rewritten as
T
1 ⎛V ⎞
∫ (γ − 1) T
dT
= ln⎜ 0 ⎟ . (1.14)
⎝V ⎠
T0
Flat laminar premixed flames are ideally suited for combustion research, since
the one-dimensional character offers great advantages for modeling and unambiguous
model-experiment comparison. Moreover, the structure of these flames is
representative for many practical flames. The structure of laminar premixed flames
18
Chapter 1
can be divided in three zones (figure 1.4), the preheat zone, the flame front (reaction
zone) and the post-flame zone (burned-gas zone). In the preheat zone the unburned
gas mixture is heated by conduction and diffusion of species from the flame front; this
zone can be considered as chemically inert. The flame front, located downstream of
the preheat zone is a thin zone (in the order of 1 mm at atmospheric pressure) in
which the fuel is rapidly oxidized by radicals from the post-flame zone as described
above, leading to a steep gradients in temperature and species concentrations. The
flame front is rich in radicals and intermediate species. Although the temperature and
major species in the post-flame zone are close to their equilibrium value, the
concentrations of minor species can differ substantially from their equilibrium value.
In the post-flame zone, the system goes to equilibrium predominantly via radical-
recombination reactions such as (R1.6).
19
Chapter 1
the burning velocity, vL is equal to the velocity of the unburned gasses, (v=vL) the
flame front is stationary in space, and if vu<vL the flame front will be convected
downstream. The laminar burning velocity and the temperature of the burned gas are
completely determined by the properties of the unburned mixture, such as the
equivalence ratio, temperature and the identity of the fuel [2]. Figure 1.5 shows the
interaction of the idealized 1-D flame with a porous-plug burner. Figure 1.5a
illustrates a flat flame stabilized on a burner where the unburned gas velocity is set
equal to the free-flame laminar burning velocity (vu=vL). In this situation, all heat
generated during combustion is transferred completely into the gas mixture and the
flame is essentially adiabatic (neglecting flame radiation). Lowering the unburned gas
velocity vu causes propagation of the flame front towards the burner surface. Since the
porous plug is too dense to allow propagation of the flame into the burner, the flame is
stopped in its upstream propagation. In this case, the flame transfers heat to the burner
by conduction, lowering the flame temperature and thus lowering the actual burning
velocity of the flame vL'. The flame transfers enough heat to the burner to reach a
stationary situation (vu= vL'), illustrated in figure 1.5b. This type of flame is called a
burner-stabilized flame.
Further decrease in the unburned gas velocity results in increasing heat loss and drop
in temperature; ultimately the temperature drops to such a level that α<β and the
flame extinguishes.
20
Chapter 1
d ( ρv) dM
= = 0, (1.15)
dx dx
where v is the mass averaged flow velocity, x is the distance along the line normal to
the burner surface and M is called the mass flux.
conservation of species
where Yk is the mass fraction and Vk is the diffusion velocity, which accounts for the
effect of molecular transport due to concentration gradients of the kth species [2,16].
Since mass can neither be destroyed nor formed in chemical reactions it follows from
(1.15) and (1.16) that,
K d ( ρY (V + v)) K d ( ρ v)
∑ k k
dx
= ∑ ωkWk =
dx
= 0 k=1…K. (1.17)
k =1 k =1
Addition of the ideal gas equation of state (1.8) to the system of equations (1.15, 1.16)
results in a system containing (K+1) linear independent equations. Assuming that the
diffusion velocity Vk is a known function of temperature and species concentrations,
21
Chapter 1
the system contains (K+2) unknown parameters (T, ρ, v and Yk). Therefore an
additional equation should be introduced to solve the system of equations:
conservation of energy
d ⎛ dT ⎞
⎜ ∑ ρYk (v + Vk ) H k − λ ⎟ = 0, (1.18)
dx ⎜ dx ⎟
⎝ k ⎠
where Hk the specific enthalpy of species k and λ the thermal conductivity coefficient.
With the proper choice of the boundary conditions for one-dimensional flames, it is
possible to solve the governing equations [2,16].
Various software packages have been developed, which are able to calculate the
one-dimensional flame structure in only a few minutes by solving the set of governing
equations. The simulation program used in this study is the PREMIX code [17]. This
code is included in the CHEMKIN II simulation package [13]. This package operates
using a reaction mechanism data file as input, along with thermal and transport
properties of the species involved in the mechanism. The program is able to calculate
temperature- and mole fraction profiles in both burner-stabilized and free flames.
In the last decades chemical kinetic mechanisms have been developed to model
combustion of hydrogen (for example, see [18]) and hydrocarbon mixtures ([11,19],
among many others). These mechanisms, used to describe the transformation of
reactants into products, may contain hundreds of species and thousands of elementary
reactions. Improvement of the mechanisms currently in use is necessary, since none of
them can be regarded as comprehensive [20], i.e. accounting for all combustion
phenomena and the predictive power is only accurate for a small range of parameters.
In order to improve the existing chemical mechanisms, they should be validated
against experimental data, where parameters are varied in a well-defined manner.
Sensitivity and rate-of-production analyses are used to design and optimize models.
Using these methods rate-limiting steps and characteristic reaction paths can be
identified [2].
22
Chapter 1
The experimental data obtained in this study have been modeled using different
mechanisms. One of these mechanisms is GRI-Mech 3.0 [11], which is widely used
and has arguably become the “industry standard” for methane in the research
community. This mechanism is optimized to model natural gas combustion and
contains 325 reactions and 53 species, including reactions that describe NO formation
and reburn chemistry.
23
Chapter 1
Literature
24
Chapter 1
25
Chapter 2
Chapter 2
26
Chapter 2
2.1 Background
Over the years, several facilities have been used to investigate autoignition under
strictly controlled experimental conditions, including flow reactors, shock tubes and
rapid compression machines (RCM). While each of these facilities has its merits, their
utility is restricted to certain ranges of pressure, temperature and ignition time.
Flow reactors: In a flow reactor, fuel is injected into a flowing air stream at high
temperature and/or pressure. The combustible mixture propagates through the reactor
and, depending on the velocity ignites at some distance downstream the fuel injector
location. Because the reaction zone is spread over a large distance, the flow reactor
offers the advantage of relatively simple measurements of the evolution of species
concentrations during the ignition process. The main drawback is that pressures
achievable in flow reactors are relatively low; further, since flow reactors makes use
of electric heaters, the maximum air temperature is limited, on the order of 1000K.
One of the most advanced flow reactors was developed at Princeton University, and
provides pressures up to ∼20 bar and temperatures up to ∼1200K [1,2].
Shock tubes: A shock tube uses the compressive heating of a shock wave to
bring a premixed combustible mixture to high temperature and pressure in a very
short time. A shock tube is ideal for studying ignition phenomena with short
characteristic times (order of tens of microseconds) under the conditions obtained. A
limitation of this technique is that the well-controlled test conditions persist for less
than 5 ms [3].
Rapid Compression Machines (RCM): The operating principle of the RCM is to
compress a homogeneous fuel/oxidizer mixture to moderate temperatures
(Tmax ≈ 1200K) and high pressures (Pmax ≈ 70bar) in a cylinder by the motion of a
piston. The RCM offers the advantage that the temperature and pressure of the
compressed mixture can be sustained for times longer than 10ms [4]. Moreover, it
provides a simple method of simulating the processes that take place in practical
devices such as spark engines and Homogeneous Charge Compression Ignition
(HCCI) engines. The time needed to compress the test gas mixtures limits the
minimum characteristic time of investigation to ∼1ms.
Several rapid compression machines have been developed and used to study
autoignition. The RCM developed at the University of Science and Technology at
27
Chapter 2
Lille is a right angle dual piston design RCM [5]. One of the pistons is air driven and
is connected by way of a cam to the other piston that compresses the mixture. The
cam controls the length of the stroke, the initial and final position of the compressing
piston, and prevents piston rebound after ignition. The maximum compression ratio
achievable with this machine is 10. Maximum pressures and temperatures after
compression are reported around 17 bar and 900K, with total times of compression of
20-60 ms. Minetti et al. used this RCM to study autoignition and two-stage ignition of
several hydrocarbon fuels [6-8]. In addition, this group performed measurements of
the temperature distribution in their RCM [4] and found that the gas temperature is
homogeneous for ∼15ms after compression, which is then distorted due to heat loss to
the wall. Griffiths et al. (University of Leeds) studied autoignition behavior of several
fuels [9-12] using an RCM that consists of a pneumatically driven piston. In support
of their experimental work they examined the development of the temperature field in
the combustion chamber of their machine [13,14] and observed that piston motion
during compression causes a roll-up vortex that moves “cold” gas from the wall into
the core. This resulted in a region with adiabatically heated gas directly after
compression containing a plug of colder gas. The Leeds RCM has a maximum
compression ratio around 15 and is able to compress the mixture in 22 ms. Final
pressures up to 20 bar and temperatures up to 1000K have been reported in this
machine. Park and Keck (MIT) developed an RCM [15,16] that consists of a
hydraulically operated piston-cylinder assembly. They also used a piston head with a
special crevice, designed to capture vortices created during compression [15,16], to
improve the homogeneity of the core gas. Lee and Hochgreb (MIT) optimized this
piston design for the suppression of the vortices [17,18], using results of detailed
modeling. Compression ratios of ∼19, maximum peak temperatures of ∼1200K and
maximum peak pressures of ∼70 bar can be achieved in this RCM. The gas mixture
can be compressed within 10 to 30 ms. Several autoignition experiments have been
performed with this machine [19,20]. Simmie and coworkers (National University of
Ireland, Galway) used an RCM, originally built at Shell laboratories [21] that uses two
horizontally opposed pneumatically driven pistons to rapidly compress the gas
mixture. For this machine, the maximum compression ratio reported is 13, the
compression time is ∼10 ms, the maximum peak compression pressure is 44 bar and
temperatures up to 1060 K have been reported. The machine has been used to study
28
Chapter 2
methane ignition [22], among other fuels. Also, this group confirmed the importance
of the crevice in the piston head [22,23]. Recently, a free-piston RCM had been
developed by Donovan et al. (University of Michigan). Compression ratios between
16 and 37, peak pressures around 20 bar and peak temperatures of 2000K have been
reported [24] using this RCM.
Given the wide range of pressures and temperatures achievable, we chose the
MIT design to study autoignition of CH4/H2/oxidizer mixtures. For this reasons a
replica of the MIT RCM was built in our laboratory and used to study autoignition.
29
Chapter 2
30
Chapter 2
The RCM, shown schematically in figure 2.1, and in detail in Appendix A.1,
includes a nitrogen-filled driving chamber, a speed-control oil chamber, an oil
reservoir chamber, a fast acting valve, a combustion chamber and a piston. The speed-
control oil chamber and the oil reservoir chamber, alternately connected and separated
by the fast acting valve are part of the hydraulic system that controls the movement of
the piston. The detailed sequence of operation for the RCM is given in Appendix A.2.
Briefly, after the RCM is triggered, the piston is in the “down” position and the fast
acing valve is in the “up” position, thus connecting the speed control oil chamber and
the oil reservoir chamber. To prepare for the next run, the piston is moved up until it
hits the stroke stop by pressurizing the oil reservoir chamber with ∼3 bar nitrogen.
The fast acting valve is than moved down by pressurizing the chamber above the fast
acting valve with 7 bar nitrogen, and locked in down position using 70 bar oil
pressure. The speed control and the oil reservoir chamber are now no longer
connected hydraulically. By pressurizing the speed control oil chamber with ∼48 bar
high-pressure oil, the piston is firmly locked in place against the stroke stop. After
loading the combustion chamber with the test gas mixture, the driver chamber is
pressurized with ∼35 bar nitrogen. The force on the piston created by the 35 bar
nitrogen pressure in the driving chamber is lower than the opposing force of oil on the
hydraulic piston, and hence the piston assembly is held in position by the stroke stop.
By opening the solenoid valve, the 70 bar oil pressure on the fast acting valve is
released and the fast acting valve will be pushed up by the 48 bar oil pressure in the
speed control chamber. The forces between the driving chamber and speed control
chamber are no longer balanced, and the pressure in the driving chamber causes the
piston to accelerate downward, compressing the test gas in the combustion chamber.
Subsequently, the piston’s acceleration slows, and the piston moves with constant
velocity until it is smoothly decelerated by a hydraulic damper [16]. In the final stage,
the deceleration force and velocity are reduced to zero, so that the final stop of the
piston at the bottom plate occurs without rebound. The piston is held firmly by the
force of driving nitrogen, which is greater than the force of the compressed gas
mixture in the reaction chamber. This allows combustion to take place at constant
volume. Since the area ratio of the piston on the driving side compared to the side of
combustion chamber is 4:1, the pressure inside the combustion chamber may be a
factor of 4 larger than the maximum pressure in the driving chamber before the piston
31
Chapter 2
will move. In the present construction, gas mixtures can be compressed with total
compression times of 15-30 ms up to pressures around 70bar. The piston speed can be
controlled, by varying the pressure in the driving chamber. The characteristics of the
RCM are presented in Table 2.1.
To cover a wide range of compression ratios, the rapid compression machine
was designed with adjustable piston stroke and clearance height. The piston stroke,
which is determined by the initial position of the piston, can be varied by turning the
stroke adjustment screw, see appendix A.1.. The clearance height can be changed by
replacing the clearance ring in the combustion chamber. To simulate temperatures and
pressures realistic for gas engines, different combinations of compression ratios,
initial pressures of the test gas and heat capacity of the diluent gases are used in this
study.
Appendix A.3 shows the overall diagram of the RCM experimental system,
containing all main lines, pressure meters, oil drums, valves and the oil reservoir. All
lines are made from stainless steel with an inner diameter of 11 mm. The orifice
diameter of the solenoid valve has the same inner diameter (11 mm) as the lines, to
allow maximum throughput of oil. The high-pressure oil was supplied to the speed
control chamber (∼48 bar) and to the fast acting valve (∼70 bar) from two high-
32
Chapter 2
pressure oil accumulators. These oil accumulators contain oil and a bladder filled with
nitrogen to prevent mixing of nitrogen with oil. After ∼25 runs the accumulators were
refilled by oil from the main oil reservoir. Compressed nitrogen from five fifty-liter,
200 bar nitrogen bottles provided the required pressures in all parts of the system. The
operation pressures used, recommended by Park [16], are given in Appendix A.4
All test gas mixtures were prepared in advance in a 10-liter gas bottle and used
to charge the combustion chamber at the required pressure. The gas filling system is
shown in figure 2.2. Before preparing the gas mixture, the gas bottle and the gas lines
connected to it are evacuated to less than 0.5 mbar using a vacuum pump. After
adding an individual component the bottle is closed. Subsequently, the gas lines are
again evacuated and the next mixture component is added to the bottle. The test
mixtures thus prepared were allowed to mix ∼24 hours to ensure homogeneity. Before
filling the combustion chamber, the poppet valve and the solenoid valve are opened,
and the whole system is evacuated to a pressure below 0.5 mbar. The combustion
chamber was filled with the gas mixture to the desired initial pressure, by opening the
bottle that contains the test gas. The poppet valve is then closed and the mixture is
ready for compression. After each run, the compressed gases in the RCM were vented
to the outside air, and the chamber was evacuated again before preparing the next run.
The solenoid valve in the gas-filling line was included for safety purposes, and
electrically connected such that when the solenoid valve used to trigger the fast-acting
valve is open, the solenoid in the gas-filling line is always closed. This prevents flame
propagation back to the gas-mixture bottle when the poppet valve is not properly
closed.
All test gases used in this study have purity greater than 99.5%. The composition
ratios of the gas mixtures are calculated from the measured partial pressures of the
individual gases.
33
Chapter 2
An MKS baratron diaphragm pressure gauge (type 722A) was used for
measuring all partial pressures of the components in the test mixture, and all other
pressures in the gas filling system. This pressure meter has an operating range from 0-
1300 mbar with an accuracy of 0.5% of reading. The dynamic pressures in the
combustion chamber during compression and throughout the post-compression period
were measured using a Kistler 6025B piezoelectric pressure transducer (range 1-250
bar, linearity ± 0.1%) placed at the bottom of the combustion chamber. The signal
from the transducer was amplified by a 5010B Kistler charge amplifier, recorded
digitally by an oscilloscope with a sample rate of 500 kHz and 16-bit resolution, and
processed by a PC. The initial temperatures of the mixture were measured by a Pt-Rh
thermocouple with an accuracy of ± 0.2K, located at the wall of the combustion
chamber. The data acquisition was triggered simultaneously with the opening of the
solenoid for the fast-acting valve.
34
Chapter 2
A typical measured pressure trace is presented in figure 2.3. The gas mixture is
compressed in ∼20ms, to a peak pressure that indicates the end of the compression
event. The majority of the pressure rise in the compression period takes place in a
very short time (<3 ms). During this rapid compression heat losses and radical built up
are not substantial. After the peak compression pressure is reached, the pressure drops
gradually due to heat transfer to the walls. Subsequently, heat release due to
exothermic reactions causes a slight increase in pressure, followed by a sharp increase
in pressure indicating ignition.
The auto ignition delay time is defined in this study as the time interval between
the peak pressure Pc that marks the end of compression and the time of maximum
pressure rise during ignition.
35
Chapter 2
T2
1
∫ γ − 1 d ln T ,
V
ln( 1 ) = (2.1)
V2
T1
T2
1
∫ γ − 1 d ln T = ln P12 ,
P
(2.2)
T1
36
Chapter 2
Figure 2.4, Temperature dependence of γ for the gas mixtures N2, Ar and
CH4/H2/O2/N2/Ar.
The relations (2.1) and (2.2) show that the pressure and temperature of the gas
only depend on the volumetric ratio and the specific heat capacities and the initial
conditions (Pi, Ti) of the gas mixture. Thus for an ideal RCM, the temperature (Tc)
and pressure (Pc) after compression can easily be calculated from equation (2.1) and
(2.2) by measuring only the initial temperature (Ti) and pressure (Pi), and the
mechanical compression ratio CR, which is defined as the ratio of the initial volume
(Vi) to the final volume (Vc) of the reaction chamber. As an example, the pressures
and temperatures are calculated, based on the mechanical compression ratios that can
be obtained in our RCM, for the three aforementioned gases/mixtures using the
relations (2.1) and (2.2), and presented in figure 2.5a and 2.5b. The calculations show
that the larger γ(T) for Ar, in comparison to N2 and the combustible mixture (figure
2.4), results in a much higher temperature and pressure after compression at identical
compression ratio. In reality, the temperatures and pressures will be lower than those
calculated due to heat losses during compression. As an example, for the compressed
CH4/H2/O2/N2/Ar mixture with CR=22.5 and Pi=0.49 bar, we measured a peak
pressure of ∼32 bar (figure 2.3). However, simple adiabatic calculations show that at
CR=22.5 the calculated temperature is 1050K (figure 2.5a) and Pc/Pi=80 (figure 2.5b),
this results in a calculated compressed pressure of ∼40 bar at Pi=0.49bar.
37
Chapter 2
38
Chapter 2
Several studies [26,17] have indicated that vortices created by the motion of the
piston causes unwanted mixing of cold boundary-layer gas into the compressed core
gas, destroying the adiabatic core. It has been shown, both numerically [19,23,27]
using CFD calculations and experimentally [27] by temperature mapping using the
planar laser-induced fluorescence of acetone, that the incorporation of a specially
designed crevice on the piston head successfully suppresses the vortex formation, and
preserves the well-defined homogeneous core region intact. In this study, the creviced
piston head based upon the best design from the MIT RCM [17,18] was used.
39
Chapter 2
Appendix A.1
Stroke
adjustment
Driving chamber
Speed control
chamber Piston
Fast acting
valve
Combustion
chamber
Poppet valve
Pressure
transducer
Figure A.1. Cross Sectional view of the Rapid Compression machine (RCM).
40
Chapter 2
Appendix A.2
The numbers in the operation sequence table below are referring to the numbered
parts (valves, reducers etc.) in appendix A.3.
Step Operation Manometer Pressure (bar) Result
1 Close valve 1
2 Open valve 2
3 Open Valve 5
4 Reducer R2 M4 2 Venting air out of
chambers and lines
5 Close valve 2
6 Reducer R2 M4 48 Pressurizing oil drum
7 Close valve 4
8 Open valve 7
9 Reducer R5 M10 70 Pressurizing oil drum
10 3-way valve 4A in up Connected to solenoid
position
11 3-way valve 1A in up M2 0 Venting driving
position chamber
12 3-way valve 2A in
down position
13 Reducer R3 M5/M8 1Æ3 Lifting piston
14 3-way valve 3A in
down position
15 Reducer R4 M9/M3 7 Lowering fast acting
valve with N2
16 Open valve 4
17 Open solenoid M7 70 Locking fast acting
valve
18 Open valve 2 M1 48 Locking piston
19 3-way valve 3A in up M3 0 Venting N2 fast acting
position valve
20 3-way valve 2A in up M5 0 Drain oil/N2
position
21 Open poppet valve
22 3-way valve 1A in
down position
23 Reducer R1 M6 30 Pressurizing
24 Close poppet valve
25 Close solenoid S1
(close = no current)
26 Close valve 4
27 3-way valve 4A in
down position
28 Check amplifier Reset
29 Close valve 2
30 Open solenoid S1 Fire the RCM
41
Chapter 2
Appendix A.3
42
Chapter 2
Appendix A.4
43
Chapter 2
As described above, the peak temperatures of the core gas at the end of
compression Tc were calculated from the equation (2.2). Since ignition chemistry is
very sensitive to temperature, it is important to estimate the uncertainty in the
calculated peak temperature caused by the uncertainties in the measured parameters.
Assuming that Ti, Pi, Pc and γ are uncorrelated, then the uncertainty in the calculated
peak temperature (ΔTc) can be determined from the following equation:
2
⎛ ∂T ∂T ∂T ∂T ⎞
ΔTc = ⎜ ΔTi + ΔPi + ΔPc + Δγ ⎟ , (A.2)
⎝ ∂Ti ∂Pi ∂Pc ∂γ ⎠
As mentioned in 2.2.3,
ΔTi=±0.2K
ΔPi/P=0.5%
ΔPc/P=0.1%
and Δγ=0.04, based on the accuracy of the determined Cp values [25]. Figure A.2
shows the calculated uncertainty as function of the peak pressure (Pc), by using
equation A.2.
44
Chapter 2
The figure shows that the uncertainty in the peak temperature is better than ±3.5K in
the range of pressures of interest (10-70 bar).
45
Chapter 2
Literature
46
Chapter 2
47
Chapter 3
Chapter 3
48
Chapter 3
3.1 Introduction
49
Chapter 3
(1− β ) β
τ = τ CH τH , (3.1)
4 2
where τH and τCH are the ignition delay times of hydrogen and methane,
2 4
respectively, and β is the mole fraction of hydrogen in the fuel. Recently, the
autoignition delay times of two stoichiometric CH4/H2/air mixtures at pressures from
16 to 40 atm and temperatures between 1000 and 1300 K have been measured in a
shock tube [13]. Because the well-controlled test conditions in a shock tube persist
only for a few milliseconds, the combination of pressure and temperature in this study
was chosen to give ignition delay times <3 ms. Interestingly, while a relatively large
amount of hydrogen was added to the fuel (35%), only a relatively small reduction in
ignition delay time was observed compared to that observed for pure methane. The
experiments also show that the ignition-enhancing effect of hydrogen decreases with
decreasing mixture temperature, and decreases significantly upon increasing pressure
from 16 to 40 atm. The experimental results were compared with calculations
performed using a mechanism [14] that was a modified version of that taken from [7];
the comparison showed substantial disagreement, prompting the authors [13] to
recommend additional experimental and kinetic studies aimed at the autoignition
behavior of methane/hydrogen mixtures.
In this Chapter, we report the autoignition delay times of stoichiometric
methane/hydrogen mixtures using oxygen/nitrogen/argon oxidizers at high pressures
(10 – 70 bar), and temperatures from 950 to 1060 K. The pressures and temperatures
50
Chapter 3
of the unburned mixtures were chosen to give ignition delay times ranging from 2 to
50 ms. The measurements were performed in an RCM and compared with numerical
simulations using different chemical mechanisms, taking into account heat loss
occurring in the period between compression and ignition.
The fuel and oxygen concentrations in the mixtures A-G are in stoichiometric
proportions and mixture H is a fuel lean mixture (ϕ=0.5). The total concentration of
diluting inert gases are close to that of nitrogen in air, while the N2/Ar ratio is chosen
to provide similar temperatures after compression for all fuels. For comparison with
the results of a previous RCM study [6], the measurements are also performed for
pure hydrogen without nitrogen (flame A in Table 3.1). As mentioned above, the
pressures were varied between 10 and 70 bar, and temperatures in the range 950-
1060 K. In addition, a substantial number of measurements were performed along an
isotherm at a peak temperature after compression of 995 ± 4 K between ~25 and ~65
51
Chapter 3
bar (see below), allowing an examination of the pressure dependence of ignition. For
measurements under identical conditions (composition, initial/final pressure), the
reproducibility of the measured ignition delay times is ∼5% and the uncertainty in
deriving the ignition delay time from the measurements is ∼0.3ms. For the data taken
along the isotherm, the variation in temperature (± 4 K) causes a scatter in the results
of ~10-20%.
52
Chapter 3
53
Chapter 3
reactive mixture during the initial stage of the ignition process, when heat release is
marginal. Just prior to ignition, the specific volume can be substantially different from
that of the inert mixture as result of the pressure and temperature increase in the
adiabatic core due to chemical reactions. The error arising from the neglect of heat
release in the estimate of the specific volume on the calculated ignition delay time is
small if the duration of this phase is also small. We anticipate that this effect will be
larger for complex alkanes showing multistage ignition [21] than for the simple fuels
used here, for which only negligible heat release occurs prior to ignition.
In light of these considerations, in the present work we determine the specific
volume from the measured pressure in the period between compression and ignition,
and extrapolate the time dependence derived in this fashion to the region in which
substantial heat release begins. This method bypasses time consuming measurements
in inert gas mixtures, and, as will be seen below, yields fits to the pressure trace that is
on par with those obtained by the other methods [5,21]. While our approach is also
not free from the potential uncertainties due to heat release during ignition, the good
fit to the pressure trace indicates an accuracy of the same order that obtained by
determining the specific volume in the inert mixture.
The implementation of the method is illustrated in figure 3.1, where the
measured pressure trace in mixture B (Table 3.1) is presented together with the
specific volume derived from the pressure. The pressure in the interval from tmax
(point during compression at which the pressure reaches its maximum, Pmax) to tA (at
which heat release is still negligible) is approximated by an exponential time
dependence with a characteristic time τc:
−(τ −τ max) /τ c
P(t ) = ( Pmax − P0 ) exp + P0 , (3.2)
where P0 is the pressure in the combustion chamber at room temperature. The specific
volume, v(t), is calculated from this relation assuming adiabatic expansion of the
“inert” mixture in the core
1/ γ
⎛ P(t ) ⎞
v(t ) = v max ⎜⎜ ⎟⎟ , (3.3)
⎝ Pmax ⎠
54
Chapter 3
where vmax is the specific volume at tmax, and γ is Cp/Cv; v(t) used as an input in
SENKIN for all times t > tmax. The choice of tA is important for the accuracy of this
method. If tA is chosen too large, heat release due to chemical reactions will be
sufficient to substantially slow the pressure drop by heat loss, and the specific volume
thus derived will be inaccurate. To avoid this error, we determine tA using an iterative
procedure. In first approximation, tA is chosen to lie halfway between tmax and the time
of ignition. If the SENKIN calculations using v(t) yield a temperature T(tA), which is
2 K higher than that for the adiabatic core calculated from the measured pressure
trace, tA is decreased (shifted towards tmax); if T(tA) is within 2 K, tA is increased. The
iterations continue until increasing tA increases the temperature by more than 2 K.
Usually, 3 – 4 iterations were performed when analyzing the experimental results. It
should be pointed out that this iteration procedure is coupled to the specific chemical
mechanism being used in the simulations, which itself is the subject of investigation.
Therefore, a computed ignition delay time that is too short by more than a factor of
two or three can result in a value for tA that is too short for a reliable extrapolation.
Fortunately, the chemical mechanisms used here predict the ignition delay with
sufficient accuracy (within a factor of two) to implement the iteration procedure, and
the temporal profiles of specific volume used in the simulations are independent of the
choice of tA.
55
Chapter 3
Figure 3.1. Pressure (a) and specific volume (b) traces in mixture B (Table 3.1) at initial
temperature of 995 K. Curves 1, 2 and 3 denote the results from the measurements, the
calculations assuming constant specific volume after compression, and the calculations using
the specific volume derived from the measured pressure trace, respectively.
The simulated pressure trace using the mechanism of O’Connaire et al. [17] are
presented in figure 3.1. Here we see that the simulated trace agrees with the
experimental trace as well as that reported by the other methods [5,21]. For
comparison, the pressure trace calculated assuming negligible heat loss (specific
volume is constant after compression) is also shown. As can be seen, neglecting heat
loss in the RCM can lead to the (erroneous) conclusion that this chemical mechanism
underpredicts the ignition delay time. However, the more realistic input of an
increasing specific volume shows opposite result – the mechanism actually
overpredicts the ignition delay time.
To assess the quality of the experimental data, we compare the ignition delay
times obtained here with the results of previous RCM studies of the autoignition of
pure hydrogen [5,6]. The ignition delay times from different data sets are scaled by
56
Chapter 3
the oxygen number density (mol/cm3) at the peak pressure after compression [6], and
are presented in figure 3.2 as a function of the reciprocal peak temperature after
compression. As mentioned above, the measured ignition delay time depends
substantially upon the heat losses in the RCM combustion chamber. Based upon the
simulations, we estimate that heat loss in our RCM results in as much as a 35%
increase in the ignition delay time as compared with an ideal adiabatic RCM. As can
be seen from figure 3.2, all experimental results are within an interval of ±35% of our
measurements. Taking into account the assumption of the validity of the scaling
method, and that heat loss can vary significantly between the physically different
machines, we consider the agreement of the results obtained here and the data in the
literature to be excellent.
Figure 3.2. Scaled ignition delay times in pure hydrogen fuel as a function of
reciprocal temperature after compression. Solid lines denote ±35% interval around
the measurements in present work approximated by the relation (3.4), see text.
As can be seen from figure 3.2, the ignition delay time in the pure hydrogen fuel
is exponential function of the reciprocal temperature. The same dependence is
observed for pure methane. Incorporating the pressure dependence using the power
function for number density, we obtain an Arrhenius-like empirical relation for the
functional dependence of the ignition delay time upon pressure and temperature after
compression (Pc and Tc, respectively) for pure hydrogen and methane fuels:
57
Chapter 3
n
⎛P ⎞ ⎛ E ⎞
τ = A⎜ c ⎟ exp⎜ a ⎟ . (3.4)
⎜T ⎟ ⎜ RT ⎟
⎝ c ⎠ ⎝ c⎠
The magnitudes of A, n, and Ea (units: s, Pa, mole, kJ, K) derived for the
stoichiometric mixtures of hydrogen and methane with oxygen are given Table 3.2.
Table 3.2
Fit coefficients
A Ea n
H2 2.82E-13 336 -1.3
CH4 3.23E-2 192 -2.1
It should be pointed out that the negative value of the power n for both gases means
decreasing ignition delay time with increasing pressure. We remark in passing that the
apparent activation energy for hydrogen is in excellent agreement with that observed
in Ref. [6]; while for methane Ea is significantly lower than that obtained in recent
studies [7,14].
To assess whether the recommended mixing expression (3.1) can also be used
for methane/hydrogen mixtures studied in the RCM, ignition delay times have been
measured at constant peak pressure (Pc = 33.5 ± 1 bar) and peak temperature
(Tc = 995 ± 4 K) as a function of hydrogen mole fractions in the fuel. As can be seen
from the results, presented in figure 3.3, replacing methane by hydrogen decreases the
ignition delay time, as reported in shock tube studies [11-13]. Moreover, within the
limits of the experimental uncertainty, the logarithm of the ignition delay time appears
to be linear function of the hydrogen mole fraction, suggesting the utility of mixing
expression (3.1). Anticipating the discussion below, we note that the computed
ignition delay times, using the mechanism from Ref. [19] and accounting for heat loss
as described in Section 3.3.2, predict this trend within the limits of experimental error.
For further analysis, we rewrite the mixing expression (3.1) by using Equation (3.4)
for the ignition delay time in pure fuel:
58
Chapter 3
nH 2 β + nCH 4 (1 − β )
(1 − β ) ⎛ Pc ⎞ ⎛ EH 2 β + ECH 4 (1 − β ) ⎞
τ = AHβ . ACH ⎜ ⎟ exp ⎜⎜ ⎟⎟ . (3.5)
2 4 ⎜T ⎟ RT
⎝ c⎠ ⎝ ⎠
From this relation, at fixed hydrogen mole fraction we expect a linear dependence of
the logarithm of ignition time divided by number density to the power
n = nΗ2β + nCH4(1-β) upon the reciprocal of the temperature. As can be seen from
figure 3.4, which shows the results for different hydrogen mole fractions, the mixing
relation (3.5) approximates the experimental data very well. For the mixtures with H2
content ≤ 20% the effect of hydrogen addition on the ignition delay time is relatively
small, but becomes substantial when the hydrogen fraction is more than 50%. It is
interesting to note that the slope of the lines in figure 3.4 increases with increasing
hydrogen content in the mixture, reflecting the differences in the “overall” activation
energy Ea between the two pure fuels; for hydrogen Ea is two times larger than for
methane (Table 3.2). Thus, at high temperatures, effect of the added hydrogen on the
ignition delay time is more pronounced than at low temperatures, as also observed in
[13].
Figure 3.3. Measured and calculated ignition delay times versus hydrogen mole
fraction in fuel at Pc = 33.5 ± 1 bar and Tc = 995 ± 3 K). The simulations were
performed accounting for heat loss using the mechanism of Petersen et al. [19]. The
solid line is obtained from the mixing relation Equation 3.5, see text.
59
Chapter 3
Figure 3.4. Measured ignition delay times scaled according to equation 3.4 as a
function of reciprocal temperature (symbols), and the calculated results using the
mixing relation (3.5) (lines).
As can be seen in figure 3.4, all measurements obtained along the isotherm at peak
compression temperature ~995 K and fixed hydrogen mole fraction collapse to a small
cluster, which demonstrates that equation (3.5) correctly predicts the pressure
dependence of the ignition delay time. Presenting the isotherm data in figure 3.5 on a
linear scale, as a function of pressure for different volume fractions of hydrogen, we
observe some scatter around the lines from equation (3.5), which is caused by day-to-
day variations in temperature (± 4 K) in the measurements, as mentioned in section
3.2. As observed above, the ignition delay times decrease with increasing pressure for
all hydrogen fractions measured, extending the observations of the recent shock tube
study [13].
60
Chapter 3
Figure 3.5. Measured (symbols) and calculated (lines) autoignition delay times as a
function of pressure at fixed peak compression temperature Tc=995 ± 4 K and
different hydrogen mole fractions in fuel. The calculated curves were obtained using
mixing relation (3.5),
Figures 3.6 to 3.8 show the experimental and calculated autoignition delay times
using different chemical mechanisms. To avoid clutter in the figures, the simulated
data are presented as polynomial trend lines through the calculated points. The
measured and calculated ignition delay times are presented in two sets. The first set
(figures 3.6a-3.8a) includes logarithms of the ignition delay times scaled by (P/T)n as
a function of the reciprocal temperature to eliminate the density dependence and
highlight the expected Arrhenius behavior with temperature. The second set of figures
presents the ignition delay times measured along the 995 ± 4 K compression isotherm.
61
Chapter 3
Figure 3.6. Measured (diamonds) and calculated (lines) autoignition delay times for
pure hydrogen (mixture B in Table 3.1). (a) Scaled delay times vs. reciprocal
temperature; (b) delay time vs. pressure at fixed temperature Tc = 995 ± 4 K.
The results for pure hydrogen (mixture B, Table 3.1) are presented in Fig 3.6. As
can be seen, the calculations using the mechanism from Petersen et al. show excellent
agreement with the measurements over the entire range of pressure and temperature
studied, while the mechanism of Li et al. and the Leeds and RAMEC mechanism
systematically overpredict the measured ignition delay times. Calculations using the
62
Chapter 3
Leeds mechanism and GRI-Mech 3.0 (not shown in figure 3.6) give identical results
for all experimental conditions, which considering their similarity is perhaps not
surprising. Based on the decidedly better agreement obtained using Petersen et al. we
suggest the use of this mechanism for ignition delay studies of hydrogen combustion
under gas turbine conditions, similar to the recommendation made in a recent study
[22].
Figure 3.7 presents the measured and calculated ignition delay times for pure
methane (mixture G, Table 3.1). As can be seen from figure 3.7a, the calculations
using the Leeds and Petersen et al. mechanisms are in excellent agreement with the
experimental results for all conditions measured. The predictions of the RAMEC
mechanism are in reasonable agreement with the experiments at the low temperatures
but substantially underpredict (up to a factor of two) the ignition delay times at high
temperatures. The results of the calculations with GRI-Mech 3.0 are more than a
factor of two higher than the scaled measured ignition delay times for all data in
figure 3.7a. The unscaled data for ignition delay times along the isotherm at
Tc = 995 K presented in figure 3.7b also show excellent agreement between
measurements and calculations with the Leeds and Petersen et al. mechanisms. At this
temperature the RAMEC mechanism slightly underpredicts the measurements at
pressures below 45 bar, but improves with increasing pressure. GRI-Mech 3.0, while
following the experimental trend well, substantially overpredicts the ignition delay in
this range.
63
Chapter 3
Figure 3.7. Measured (diamonds) and calculated (lines) ignition delay times for pure
methane (mixture G in Table 3.1). (a) Scaled delay times vs. reciprocal temperature;
(b) delay time vs. pressure at fixed temperature Tc = 995 ± 4 K.
As observed above, the mechanism proposed by Petersen et al. predicts the ignition
delay time in both pure hydrogen and methane very well, while the predictions of the
other mechanisms considered are poorer. Furthermore, this mechanism also yields the
best agreement with the experiments performed on the hydrogen/methane mixtures.
Consequently, in the following comparisons we only show these computational
results. As can be seen from figure 3.8, the computed ignition delay times are in
64
Chapter 3
excellent agreement with the experiments in the hydrogen/methane mixtures. Over the
entire range of pressure and temperature studied, the agreement between the
calculations and measurements is better than 25%.
Figure 3.8. Measured (symbols) and calculated (lines) autoignition delay times for
hydrogen/methane fuel (mixtures D, E and F in Table 3.1) as a function of reciprocal
temperature (a) and pressure at fixed temperature Tc = 995 ± 4 K (b). The
calculations were performed using Petersen et al.[19].
65
Chapter 3
Given the agreement with the experimental results presented here, we also
compare the predictions of this mechanism with the experimental data reported in Ref.
[13], where a significant disparity between the experimental and numerical results
was observed. Figure 3.9 reproduces the experimental data for the hydrogen/methane
mixtures from Ref. [13], and the computations using Petersen et al.; as was done in
the original report [13], we have simulated the results at constant density. At 16 bar
(figure 3.9a), the current mechanism gives a better reproduction of the experimental
data at T > 1150K, the computations for 15 and 35% now bracketing the experiments;
in this region, the agreement is substantially better than a factor of 2. However, at
lower temperature the agreement is poorer than in the original model [13]. At 40 bar
(figure 3.9b), we observe a similar trend, albeit with a similar agreement to the
original model at lower temperatures. Particularly vexing is the relatively large effect
for the addition of hydrogen predicted by the computations, but which is apparently
much less manifest in the shock tube results, even at high temperature. We remark
that the good predictive power shown in figure 3.8, particularly in reproducing the
trends with pressure and hydrogen addition as well as the magnitude of the results in
the low temperature region, supports the use of the mechanism under these conditions.
66
Chapter 3
Figure 3.9. Comparison of measured (points) and calculated (lines) ignition delay
times for shock tube measurements taken from Ref. [13]. Calculations performed
using mechanism from Petersen et al. [19]; dashed lines calculations at 15% H2, solid
lines calculations at 35% H2 in mixture. Figure (a) at 16 bar, figure (b) at 40 bar.
67
Chapter 3
Figure 3.10. Measured (symbols) and calculated (lines) ignition delay times for 50%
H2 in the fuel at ϕ = 1.0 and ϕ = 0.5 (Mixtures C and H, respectively, in Table 3.1) as
a function of pressure at fixed temperature Tc = 995 ± 4 K. The calculations were
performed using Petersen et al. [19].
68
Chapter 3
[19] is observed for all fuel mixtures studied. Over the entire operational range of
temperatures and pressures used in the present study, the differences between the
measured and calculated values of the ignition delay time are less than 10% for pure
fuels and better than 25% for the hydrogen/methane mixtures.
69
Chapter 3
Literature
70
Chapter 3
71
Chapter 4
Chapter 4
72
Chapter 4
73
Chapter 4
absorption lines are impossible to resolve due to the large number of strong and
overlapping water lines.
Figure 4.1. Calculated absorption spectra for a gas mixture of 0.3% C2H2 and 18%
H2O in N2 at 1800K (a) and 300K (b). Line positions, strengths and broadening
coefficients are taken from [8-10] and [11], respectively.
74
Chapter 4
75
Chapter 4
4.2 Burner
The burner was affixed to a positioner that moves the burner with a precision of
0.1 mm, to allow measurement of axial profiles of species concentration and
temperature.
76
Chapter 4
Figure 4.3. Experimental set-up used for transport, mixing, and analysis of the fuel-
air mixture.
Figure 4.3 shows the flow scheme for the burner feed gases and the system for
analyzing the composition of the unburned fuel-air mixture. The flow rates of all
gases were measured by calibrated mass-flow meters (Bronkhorst, EL-FLOW),
digitized by an analog-digital converter and processed by a PC. The flow ranges of the
meters were selected to provide an accuracy of better than 5%. All fuels used in this
study were supplied in cylinders with purity better than 99.99% and dry, filtered air
was supplied by an oil-free compressor. The gases were mixed in a tube 50 cm long,
and a small part was diverted to a Maihak Unior 610 gas analyzer for measuring the
methane and oxygen mole fractions in the fuel-air mixture, while the rest is supplied
to the burner system. The by-pass burner makes it possible to vary the flow rate
through the burner during the experiment without changing the choked flows of the
individual gases.
The equivalence ratio ϕ of the fuel-oxidizer mixtures was calculated according
the following expression (described in detail in chapter 1),
77
Chapter 4
[CH 4 ] 1 [H ] 1
ϕ= . + 2 . . (4.1)
[O2 ] f st ,CH 4 [O2 ] f st , H 2
Whereas it is possible to determine the equivalence ratio through measuring the flow
rates, to increase accuracy we determined ϕ based on measuring CH4 and O2 mole
fractions in the unburned mixture using the Maihak analyzer. In CH4/air flames,
measuring only the CH4 mole fraction in the cold mixture is sufficient to calculate the
complete mixture composition, since the oxygen/nitrogen ratio in the mixture known.
This procedure provided accuracy better than 2% for all equivalence ratios used. To
determine the composition of the cold unburned mixtures of the CH4/H2/air flames,
the CH4 and O2 mole fractions are both measured using the Maihak gas analyzer, the
N2 mole fraction is calculated from the measured O2 mole fraction and the known
ratio [O2]/[N2] in air, and the H2 mole fraction is calculated from the balance,
⎛ [N ] ⎞
[ H 2 ] = 1 − [CH 4 ] meas − [O2 ]meas. − [O2 ]meas. * ⎜⎜ 2 ⎟⎟ . (4.2)
⎝ [O2 ] ⎠ air
Based on this method, the accuracy of the equivalence ratios determined was better
than 5% in all CH4/H2/air flames measured. Detailed information on the uncertainty
analyses can be found in [13]. The mass flux is calculated from the measured mass
flow, assuming the surface area of the burner is equal to that of the flame. The
accuracy of the mass flux through the burner surface was estimated approximately
10%, determined by the uncertainties in the measured mass flow rate and the
uncertainty in the flame area.
78
Chapter 4
Figure 4.4 shows a schematic of the probe sampling system. All flames were
sampled by a quartz microprobe having a similar design to that described in [14], with
an orifice diameter of about 100 μm. For the acetylene measurements, with exception
of the probe tip, the quartz probe was cooled over a distance of 35 cm by water at
12οC. After passing an ice-cooled water trap, the sampled gas flowed through a 1 m-
length stainless-steel tube sealed on both ends by quartz windows to form a
measurement cell. The pressure in the tube was monitored by an electronic pressure
transducer and kept constant at 100 mbar by a vacuum pump installed in the exit of
the sampling system; this provided rapid removal and quenching of the gas sample.
Because HCN is soluble in water, measurement of this component was performed
using an uncooled probe and water at room temperature in the cooling trap. In this
case no condensation of water from the combustion gases in the cooling trap was
observed during sampling.
79
Chapter 4
To estimate the degree of conversion of C2H2 and HCN to other products during
sampling, the probe is modeled as a closed system containing a homogeneous gas
mixture, described in detail in chapter 1. The model uses a prescribed cooling rate,
based on characteristic time scales in the experimental set-up to calculate the mixture
composition history profile. The probe modeling was divided in two parts: rapid
adiabatic expansion in the probe tip (τ1) followed by cooling of the sample at constant
pressure (τ2). During expansion in the probe tip the gas sample undergoes a rapid
decrease in pressure and temperature, described by,
−t / τ
P = ( Pmax . − P0. ) exp 1 . (4.3)
The temperature drop associated with the pressure drop is calculated in the program
using equation (2.2), by assuming isentropic flow conditions. The characteristic
cooling time in the probe tip used was τ1 =10-4 s, which is one order longer than
estimated by assuming critical flow in the probe orifice. The initial composition and
temperature were varied in the model using the results of one-dimensional flame
calculations, described in detail in chapter 1. The temperature (T0) of the gas flow in
the probe immediately after expansion is taken from the temperature calculations in
the probe tip at a probe backpressure (P0) of 0.1 bar and put in the model. Further
downstream of the probe tip the gas is cooled at constant pressure (P0=0.1 bar) to
room temperature (Tmin) by heat transfer to the coolant, according to,
In the model we used τ2=0.5s; this value is one order higher than that based on heat
transfer estimations. GRI-Mech 3.0 [15] is used as chemical mechanism in the
calculations.
80
Chapter 4
81
Chapter 4
4.6.1 Theory
⎛ I (v ) ⎞
ln⎜⎜ 0 ⎟⎟ = α (v)l , (4.5)
⎝ I (v ) ⎠
where S(T) is the line intensity or integrated absorption coefficient per unit pressure
(expressed in cm-2atm-1), f(v) the spectral line function (normalized such that
∞
∫ f (v)dv = 1),
−∞
P the pressure and xm the species mole fraction. The line function f(v)
depends on temperature and the collisional environment of the molecule. The shape of
f(v) depends upon the type of broadening. Doppler broadening is due to thermal
motion of molecules and collisional broadening is a result of perturbations in the
energy levels of absorbing molecules caused by collision with the other molecules.
Since the parameters of the line function f(v) are often unknown, it is better to
integrate the left and right parts of equation (4.5) over the entire line profile and
substitute (4.6) into (4.5) in order to determine the species mole fraction:
∞
I 0 (v )
∫ ln I (v )
dv
x m = −∞ . (4.7)
S (T ) Pl
82
Chapter 4
The measured intensities always contain a certain amount of noise, which limits
the smallest detectable absorption. The dominating source of noise is often 1/f noise
[23], which is larger at low frequencies and will decrease at higher frequencies.
Wavelength-modulation absorption spectroscopy (WMAS) is an effective technique
to reduce the noise, and thereby increase the detectability. The principle of WMAS is
smooth modulation of the wavelength at a certain frequency followed by detection of
the modulated laser radiation at the original modulation frequency or at one of its
harmonics. One of the advantages of modulation spectroscopy is that only the noise
centered on the detection frequency will influence the measurements. The detection is
83
Chapter 4
shifted to higher frequencies where the 1/f noise is smaller. The basic approach is to
modulate the wavelength of the laser radiation around its center (here using the
frequency of the radiation, vc, in the derivation) at frequency fm with a modulation
amplitude va. The instantaneous frequency v(t) of the laser radiation can than be
represented as,
After absorption in the medium, the intensity of the modulated, transmitted laser
beam I(v(t)) and the reference laser beam I0(v(t)) are related by the Lambert-Beer law,
already introduced in (4.5). WMAS is usually used for samples that have low
absorptions. This allows expanding the exponent in equation. (4.5) in a Taylor series.
By neglecting the higher order terms in the Taylor series one obtains:
∞
I (vc + v a sin 2πf m t ) = ∑ H n (vc , va ) sin 2πnf mt . (4.10)
n =0
The nth harmonic component of the intensity of the transmitted laser beam Hn(vc,va),
for n≥1 is expressed as
t
1
H n (vc , va ) =
2π ∫ I (vc + va sin 2π fmt ) sin 2π fmntdt . (4.11)
−t
To simplify the analyses we assume that the laser intensity is independent of the
frequency. In this case Hn can be written as,
84
Chapter 4
Any of the harmonics (n=1,2…) can be used; however optimum signals are
generated using second-harmonic detection [21]. The increased sensitivity of the
second-harmonic detection technique arises in part from the elimination of featureless
background signals. For detecting weak absorptions it is important to maximize the
harmonic signals by optimizing the modulation amplitudes. The simulated second
harmonic signals shown in figure 4.7 are calculated for different modulation
85
Chapter 4
va
indices m = , using an exact solution to the integral in equation (4.11) for a
Δv1 / 2
Lorentzian line shape [24]. Here, Δν1/2 is the half width at half maximum (HWHM) of
the absorption line.
As can be seen from figure 4.7, the 2f-line shapes becomes broader with
increasing modulation index and reaches the maximum peak height at a modulation
index m∼2. The maximum peak height occurs at m∼2 for all line shapes [24,25]. In
environments where the absorption is very low, the modulation index is often set to a
value close to m∼2; for cases in which it is necessary to reduce interferences from
nearby transitions, the modulation index is decreased to minimize the broadening of
the 2f-line shape.
86
Chapter 4
Figure 4.8 shows the basic schematic of the experimental setup for Tunable
Diode Laser Absorption Spectroscopy (TDLAS) used for direct absorption
measurements of acetylene. The radiation from a New Focus 6326 tunable diode
laser, with a linewidth less than 300 kHz, was directed through the absorption cell.
Before entering the cell, a part of the laser radiation was split off to produce the
reference signal. The powers of the reference and sample beams were measured by
New Focus 2033 large area photodiodes with internal amplifiers. The photodiode
signals were digitized and processed by a PC. The laser wavelength was swept over
the span of 30 GHz with a scan rate 150 MHz/s by applying a voltage to the
piezoceramic plate, which moves the tuning end-mirror inside the laser. The
measurements were performed in the region around 1530 nm, where the P (9)
absorption line of the ν1 + ν3 band of C2H2 is located [8]. This line was selected
because of its relatively high oscillator strength [9] and lack of interference from
transitions of other flame molecules.
87
Chapter 4
When comparing the measurements performed in the calibration gases with those of
the combustion products, no differences were found in absorption line shapes. This
implies that the spectral line function in equation (4.6) is independent of the gas
composition in the current experiments. This result is perhaps to be expected, since
88
Chapter 4
the broadening efficiencies of C2H2 and N2 for the acetylene lines are comparable
[10], while the concentrations of the other gases with unknown broadening efficiency
are low.
Taking into account that the spectral line function is the same in the calibration
gas and in combustion products one derives from equation. (4.7),
v2
⎛ I (v ) ⎞ ⎛ I (v ) ⎞
∫ ln⎜⎜⎝ I0(v) ⎟⎟⎠dv ∑ ln⎜⎜⎝ I0(vii) ⎟⎟⎠
v1
x M = xcal. = xcal. i , (4.13)
v2 ⎛ I 0cal (vi ) ⎞
∫ln⎜
⎛ I 0call. (v) ⎞
⎜ I
⎟dv
⎟
∑ln⎜⎜
⎝
⎟
I cal (vi ) ⎟⎠
v ⎝ cal ⎠ i
1
where the subscripts cal and i refer to the calibration gas and i-th measured point,
respectively. In the current experimental setup, for acetylene mole fractions above
1000 ppm, the accuracy of the measured C2H2 concentrations is ~5%, and is
determined mainly by the uncertainty in the calibration gas concentration. At low
acetylene mole fractions, the uncertainties in the measured integral absorption
coefficient become dominant, which results in deteriorating accuracy, up to 15% at
100 ppm C2H2. While equation (4.7) only requires one calibration point to determine
the measured acetylene concentration, to verify the possible influence of non-linearity
in the detection system, the integral absorption coefficient was measured in
calibration gases with different C2H2 concentrations. As can be seen from figure 4.10,
showing the results of these measurements, the detection system possesses excellent
linearity: deviation of the fitted and experimental values is less than 5%.
89
Chapter 4
Figure 4.10. Integrated absorption coefficient of the C2H2 P(9) line of the ν1+ν3 band
as a function of acetylene mole fraction diluted in N2. Solid line is a linear fit.
The experimental sep-up used for the WMAS experiments with second harmonic
detection is almost identical to that presented schematically in figure 4.8. The only
difference is that we do not use the reference beam. The laser frequency v is
modulated around the center frequency vc by applying a sinusoidal voltage from an
external generator to the piezoceramic plate which moves the tuning end mirror inside
the laser. The modulation depth va, and frequency fm, in equation (4.8) are chosen to
be ∼0.67 GHz and 0.5 kHz, respectively, to provide maximal sensitivity for the
present experimental setup [21]. The power of the transmitted laser beam is digitized
90
Chapter 4
1 N
2 fm
I 2 f (vc ) =
N
∑ I (v ) ⋅ sin(2π
i =1
i c
fs
i) . (4.14)
The summation (4.14) is performed with the number of samples N ~ 10000, which
corresponds 0.2 s total sampling time. Further increasing the number of samples does
not result in substantial improvement in the signal-to-noise ratio. The HCN
measurements were performed in the region around 1545 nm where the P(13)
absorption line of the ν2 band of HCN is located [17]. This line was selected because
of its relatively high oscillator strength and lack of interference from other flame
molecules. To cover the entire absorption line, the center frequency vc is tuned in
steps of 0.12 GHz over span of ∼10 GHz by changing the mean voltage applied to the
piezotransducer. The improvement in signal-to-noise ratio obtained using WMAS as
compared to direct absorption is illustrated in figure 4.11. The measured direct
absorption profile measured in a gas mixture containing 90 ppm HCN in N2 is shown
in figure. 4.11a. Figure 4.11b shows a typical HCN second harmonic spectrum in the
same gas mixture. As can be seen, the signal-to-noise ratio is improved by more than
one order by using WMAS with second harmonic detection.
91
Chapter 4
Figure. 4.11a.) Direct absorption scan of 90 ppm HCN in nitrogen in the vicinity of
the P(13) line of ν2 Σ-Σ band, b.) Second harmonic signal in the same mixture for the
same absorption transition.
92
Chapter 4
Substituting (4.15) into the Lambert-Beer law for optically thin absorption layers (4.9)
and taking the Fourier transform, while taking into account that according (4.8) v is a
function of time, we receive the following expression for the Fourier transform of the
transmitted signal at frequency f,
I% ( f ) = I 0 ( f ) − I 0α BG ( f )l − I 0 g ( f ) S (T ) PxM l , (4.16)
where the tilde above the variable denotes its Fourier transform. As we can see from
this expression, the measured signal consists in general of three terms. The first two
terms in (4.16) are due to the frequency dependence of the laser power and
background absorption coefficient. In the case of sinusoidal modulation and second
harmonic detection (f = 2fm), these terms will vanish only when laser power and
background absorption coefficient are constant or one of them is linearly dependent
upon the laser frequency v. The term I 0 (2 f m ) − I 0α BG (2 f m )l can be determined by
measuring the second harmonic signal in media without HCN molecules. The
measurements, performed at a height of 10 mm above the burner surface in a
methane-air flame with equivalence ratio ϕ = 1.3 and mass flux ρν=0.015g/cm2s
where HCN concentration is expected to be very low, showed that in the spectral
region used in the present work the background I 0α BG (2 f m ) does not exceed the
signal from HCN at mole fraction of 5 ppm. Because the concentrations of main flame
components that contribute to the background absorption coefficient (H2O, CO and
CO2) vary only slightly with equivalence ratio, the value of I 0 (2 f m ) − I 0α BG (2 f m )l
was used for deriving HCN concentrations in all CH4/air flames studied here. To
determine the background for the CH4/H2/air flames, a similar reference flame (ϕ=1.3
93
Chapter 4
and ρν=0.015g/cm2.s) was used with the same percentage of hydrogen added as for
the flames under investigation.
A typical second harmonic spectrum of HCN, measured in a flame at ϕ=1.4, at 2
mm above the burner surface, is presented in figure 4.12a. The second harmonic
spectrum of HCN ( I 0 g (2 f m ) S (T ) Pxml ), shown in figure 4.12c, was obtained by
subtracting the measured second harmonic signal of the reference flame
( I 0 (2 f m ) − I 0α BG (2 f m )l ), given in figure 4.12b, from that shown in figure 4.12a. In
figure 4.12c, we can see the characteristic shape expected for the second derivative of
the bell-shaped spectral line profile.
Using the second harmonic signal to derive quantitative information on species
concentrations is rather difficult. Direct fitting according to the expression (4.16)
requires knowledge of functional dependence of both absorption spectral line and
laser intensity upon frequency. Moreover, direct integration of the second harmonic
signal would yield a value close to zero. To overcome these difficulties, the extracted
second harmonic signal is integrated over a sufficiently large region [v1, v2] in the
vicinity of the HCN spectral line. From the expression (4.16) it follows that
v2
xm = C ∫ I0 (2 fm ) − I% (2 fm ) − I0α BG (2 fm )l dv , (4.17)
v1
1
C= . (4.18)
v2
S (T ) Pl ∫ I0 g (2 fm) dv
v1
94
Chapter 4
Figure 4.12a) 2f-signal measured in a flame with ϕ=1.4 and ρν=0.01g/cm2.s at 2mm
from the burner surface, b) 2f signal measured in the reference flame (ϕ=1.3,
ρν=0.15g/cm2.s at 10mm from the burner surface), c) Extracted second harmonic
spectrum of HCN.
95
Chapter 4
Figure 4.13. Integrated absolute value of the second harmonic signal in the vicinity of
the P(13) line of ν2 Σ-Σ band as a function of HCN concentrations in N2.
96
Chapter 4
Literature
97
Chapter 4
18. R. G. Pilston, J. U. White: A long path gas absorption cell, J. Opt. Soc. Am.
44, 572–573 (1954).
19. J. U. White: Long optical paths of large aperture, J. Opt. Soc. Am. 32, 285–
288 (1942).
20. A. O’Keefe, D. A. G. Deacon: Cavity ring-down optical spectrometer for
absorption measurements using pulsed laser sources, Rev. Sci. Instrum. 59,
2544 (1988).
21. J.A. Silver, Applied Optics, 31 (6) (1992) 707-717.
22. P. Kluczynski, J. Gustafsson, A. M. Lindberg, O. Axner, Spectrochimica
Acte Part B, 56 (2001) 1277-1354.
23. C. Th. J. Alkemade, T. J. Hollander, W. Snelleman, P. J. Th. Zeegers,
International Series in Natural Philosophy 3 (1982) 272 .
24. R. Arndt, Appl. Opt. 36 (8) (1965) 2522-2524.
25. J. Reid, D. Labie, Appl. Phys. B 26 (1981) 203-210.
98
Chapter 5
Chapter 5
99
Chapter 5
5.1 Introduction
As discussed in previous chapters, one of the major advances of the last decades
in the combustion science is the prediction of flame structure by numerical
simulations using detailed transport and chemical mechanisms. Because of the
complexity of these mechanisms and uncertainties in the rates of the key chemical
reactions, the predictive power of the numerical simulations can be tested only by
comparing calculated and measured flame properties under well-defined experimental
conditions. The comparison of the spatial profiles of intermediate species is
particularly important for testing the adequacy of chemical mechanisms. One of the
key intermediates in many high temperature processes is acetylene (C2H2), which
plays important role in the formation of polycyclic aromatic hydrocarbons and soot in
hydrocarbon combustion [1-3] and in the chemical vapor deposition of diamond [4].
Acetylene has been extensively investigated in both atmospheric- and low-pressure
flat premixed flames [5-11]. At atmospheric pressure, large discrepancies have been
observed [8,11] between measured results and those calculated based on the C2H2
submechanism derived from Miller and Mellius [12]. However, the acetylene
measurements in these studies were performed using extractive probe sampling,
which as discussed in Chapter 4 has a serious drawback, i.e., the distortion of the
composition and temperature profiles in the flame. Estimating the magnitude of this
distortion, for example, from chemical reactions on the probe surface or acceleration
of the combustion products into the probe orifice are rather difficult [13]. Moreover,
these estimates (as was done in Chapter 4) require detailed knowledge of the kinetics
of the chemical reactions involving the measured species that itself is the subject of
investigation. These complications necessitate the verification of the results obtained
by the extractive probe by an independent technique. Recently, we have reported the
measurement of native C2H2 in a fuel-rich methane/air flame at equivalence ratio
ϕ = 1.55, using spontaneous Raman scattering [14]. This method thus provides us
with the means to verify the results of extractive probe sampling for acetylene
measurement, and to deliver reliable experimental results regarding C2H2 formation
and destruction in atmospheric-pressure methane/air flames.
Towards this end, we have measured the profiles of C2H2 mole fraction in flat
atmospheric-pressure rich-premixed methane/air flames using both spontaneous
Raman scattering and microprobe gas sampling followed by tunable diode laser
100
Chapter 5
5.2 Experimental
101
Chapter 5
The temperature measurements showed that all the flames studied had a domain with
constant temperature extending at least 20 mm radially from the centerline, and from
3 mm to 15 mm in the axial direction. As typical examples of the temperature
measurements, the radial profile at height 10 mm above the burner surface and
centerline axial profile in flame A are presented in Figs. 5.1 and 5.2, respectively. The
radial profile shows a core region of ~ 20 mm length of constant temperature
surrounded by a layer where the temperature is higher due to penetrating surrounding
air through the nitrogen shroud. The axial centerline temperature profile is in excellent
agreement with the flame calculations, indicating the robustness of the GRI-Mech 3.0
[16] mechanism in predicting the burning velocities of CH4/air flames and marginal
radiative heat losses in these flames. The excellent agreement between measured and
calculated axial temperature profiles was observed in all flames studied.
102
Chapter 5
Figure 5.2. Axial centreline temperature profile measured in flame A. Solid line and
diamonds denote flame calculations and measurements, respectively.
103
Chapter 5
was observed in temperature and hydroxyl profiles in other flames [17,18], and is the
result of the acceleration of the combustion products into the probe orifice [13].
Shifting the probe profile results in agreement with the Raman profiles to better than
20% (also observed in Ref. [14] at ϕ = 1.58), which substantiates the extractive probe
technique for the measurements of acetylene presented below.
Figure 5.3. Axial centerline profiles of acetylene mole fraction in methane/air flame,
ϕ = 1.50 and ρv = 0.008 g/(cm2·s). Symbols denote Raman (triangles) and probe
(squares with solid line) measurements; the dashed line denotes the shifted probe
measurements.
At mole fractions below 500 ppm the acetylene Raman spectrum was barely
distinguishable in the noise, while the signal-to-noise ratio of the TDLAS spectrum
remained higher than 10 for mole fractions down to 100 ppm. This difference in the
limit of detectability precludes comparison of probe and Raman data in the flames
with low C2H2 mole fraction in the post-flame zone. However, due to the modest
changes in flame structure upon changing the equivalence ratio from ϕ = 1.5 to
ϕ = 1.4, we do not expect the accuracy of the probe measurements observed at
ϕ = 1.58 and ϕ = 1.5 to deteriorate substantially. The results of the extractive probe
measurements of acetylene at equivalence ratios ϕ = 1.5, 1.45 and 1.4 at different
mass fluxes are presented in figure 5.4-5.6. Consistent with the results in figure 5.3
and those presented in Ref. [14], all experimental acetylene profiles are shifted
104
Chapter 5
1.3 mm towards the burner surface. As can be seen from the figures, at a fixed
equivalence ratio the maximum C2H2 mole fraction depends only slightly on the mass
flux, while C2H2 oxidation in the post-flame zone increases substantially in the flames
at higher the mass flux, caused by the higher gas temperatures (given in Table 5.1). At
the same time, decreasing the equivalence ratio from ϕ = 1.5 to 1.4 decreases the
peak C2H2 mole fraction by nearly a factor of two.
Figure 5.4. Axial profiles of acetylene mole fraction in methane/air flames, ϕ = 1.5.
Symbols denote probe measurements in flames A (squares), B (diamonds) and C
(triangles). The dashed lines denote flame calculations with GRI-Mech 3.0, and the
solid lines are the results of calculations with the increased rate coefficient for
C2H2 + OH Æ CH2CO + H discussed in the text.
105
Chapter 5
Figure 5.5. Axial profiles of acetylene mole fraction in methane/air flames, ϕ = 1.45.
Symbols denote probe measurements in flames D (squares), E (diamonds) and F
(triangles). Solid lines denote flame calculations with the increased rate coefficient
for C2H2 + OH Æ CH2CO + H discussed in the text.
Figure 5.6. Axial profiles of acetylene mole fraction in methane/air flames, ϕ = 1.40.
Symbols denote probe measurements in flames G (squares), H (diamonds) and I
(triangles). Solid lines denote flame calculations with the increased rate coefficient
for C2H2 + OH Æ CH2CO + H discussed in the text.
106
Chapter 5
5.4 Conclusions
107
Chapter 5
Literature
108
Chapter 6
Chapter 6
109
Chapter 6
6.1 Introduction
To date, the vast majority of the methods developed to lower NOx emissions are
based on decreasing the flame temperature: either through flue-gas recirculation or
fuel-lean combustion. Application of these methods to obtain the lowest NOx possible
ultimately leads to deteriorating flame stability. Decreasing the temperature of fuel-
rich flames, which can be more stable than fuel-lean flames, is often not considered to
be promising as an NOx control strategy because the key initiation reaction of the
Fenimore mechanism [1]
CH + N 2 = HCN + N (R6.1)
has a relatively low activation energy [2], and as such should be less sensitive to
flame temperature than the Zeldovich mechanism. However, experiments performed
in premixed fuel-rich natural-gas/air flames [3], showed that the measured NO mole
fractions decrease with increasing upstream heat loss, suggesting that varying the
flame temperature by altering the degree of burner stabilization can influence the NO
production in rich flames. Recent experiments at low pressure [4] have supported
these observations, and analyzed the effects of burner stabilization on Fenimore NO
formation. On the other hand, it is also possible that part of the observed decrease in
NO with flame temperature can be caused by the retardation of the conversion of the
HCN formed in reaction (R6.1), or other fixed-nitrogen species (so-called Total Fixed
Nitrogen or TFN) to NO, as suggested in [5, 6]. In this case, the “residual” TFN either
will be converted to NO in the second stage of combustion or emitted into the
environment with flue gases. To resolve this uncertainty, and to determine the
ultimate low NOx potential of fuel-rich combustion, it is essential to measure HCN in
these flames. The experimental investigations of HCN formation and destruction
performed thus far have seeded flames with bound-nitrogen additives, where the
reaction between CH and N2 is of minor importance. HCN measurements in
methane/air flames are scarce and often contradictory. For example, one study [6]
reported “as ϕ increases the maximum concentration of HCN increases initially, but
falls again in very fuel-rich flames”, while another study [7] observed a strong
increase in HCN with equivalence ratio. Moreover, Ref. [7] states that the HCN
concentration is not very dependent upon the temperature, while the reported HCN
110
Chapter 6
concentrations at T = 2560 K are almost one order of magnitude higher than those at
the same equivalence ratio (ϕ = 1.20) in Ref. [6] in the methane/air flame. Further, we
are not aware of HCN measurements in which the flame temperature was varied at
fixed equivalence ratio.
Although there are numerous experimental observations in fuel-rich flames (for
example, Ref. [8] and references therein) showing correlations between the measured
NO and CH mole fractions, as well as direct high-temperature measurements of the
rate constant of reaction (R6.1) [9,10] that reasonably agree with the results of flame
modeling, controversy about this reaction is not resolved [11]. Reaction (R6.1) as
written is “spin-forbidden”, and to reconcile theory and experiment a near unit
probability of crossing between doublet and quartet potential surfaces had to be
assumed [12]. Recently, ab initio RRKM calculations have been performed for the
reaction CH + N2 Æ products [13,14], which showed that the reaction between CH
and N2 takes place mainly through the “spin-allowed” channel:
CH + N 2 = NCN + H , (R6.2)
while reaction (R6.1) is not important. These calculations have been supported by
NCN detection in a low-pressure CH4/air flame [15], although the measurements were
not quantitative. It should be pointed out that theoretical results giving (R6.2) does not
contradict the experimental observations: the rate constant of the reaction (R6.1) was
determined without measurement of the products, while rapid conversion of any NCN
produced in (R6.2) to NO will preserve the correlation between the CH mole fraction
and NO formation. The experimental determination of the concentration profiles of
HCN in flames in which we expect significant Fenimore NO formation will help
resolve the uncertainty as to both the primary products of CH + N2 and the role of
HCN as a stable intermediate in NO formation.
Towards this end we measure the axial profiles of the mole fraction of HCN in
burner-stabilized rich-premixed methane/air flames at equivalence ratios ϕ = 1.3-1.5
at different flame temperatures, similar to the method followed in Chapter 5. In these
flames the HCN mole fractions are of order of a few tens of ppm. Whereas the
sensitivity of the absorption method allows measuring such low concentrations, the
strong background from the hot bands in the water absorption spectrum has frustrated
111
Chapter 6
direct in-situ HCN measurements in flames thus far. To circumvent this problem, we
follow the approach described in Chapter 4, and use microprobe sampling and
wavelength modulation absorption spectroscopy with second harmonic detection,
supplemented with CARS temperature measurements. As was done in Chapter 5 for
acetylene, the experimental observations are compared with one-dimensional flame
calculations.
6.2 Experimental
112
Chapter 6
Table 6.1
Flame ϕ ρv, g/cm2·s T, K
A 1.3 0.007 1775
B 1.3 0.011 1855
C 1.3 0.015 1942
D 1.4 0.008 1842
E 1.4 0.01 1910
F 1.4 0.014 1950
G 1.5 0.005 1763
H 1.5 0.008 1852
The temperature measurements showed that all the flames studied had a domain
with constant temperature extending at least 20 mm radially from the centerline, from
3 mm to 15 mm in the axial direction. Moreover, the measured temperatures in this
domain were in excellent agreement with the flame calculations using GRI-Mech 3.0
[17], indicating marginal radiative heat losses in these flames.
The axial HCN profiles measured in flames with equivalence ratios ϕ = 1.3, 1.4
and 1.5 are presented in figures 6.1, 6.2 and 6.3, respectively. The experimental
profiles of HCN mole fraction were shifted downstream, as in done chapter 5, where
the shift of ~1.3 mm was observed between acetylene concentrations profiles
measured by the Raman and probe techniques. Since the equivalence ratios and mass
fluxes are close to those in chapter 5, we apply the same shift (1.3 mm) to the
measured HCN profiles.
113
Chapter 6
Figure 6.1 Axial profiles of HCN mole fractions in methane air flames, ϕ = 1.3.
Symbols denote probe measurements in flames A (squares), B (diamonds) and C
(triangles). Lines denote flame calculations in flames A (solid), B (dashed) and C
(dotted).
Figure 6.2. Axial profiles of HCN mole fractions in methane air flames, ϕ = 1.4.
Symbols denote probe measurements in flames D (squares), E (diamonds) and F
(triangles). Lines denote flame calculations in flames D (solid), E (dashed) and F
(dotted).
114
Chapter 6
Figure 6.3. Axial profiles of HCN mole fractions in methane air flames, ϕ = 1.5.
Symbols denote probe measurements in flames G (squares) and H (diamonds). Lines
denote flame calculations in flames G (solid) and H (dashed).
As can be seen from figure 6.1-6.3, the measured HCN concentrations peak in
the region of the flame front, and decrease (albeit gradually) in the post-flame zone.
The maximum measured HCN mole fractions are only slightly dependent upon
equivalence ratio and mass flux, and do not exceed 15 ppm in all the flames studied
here. In flames with ϕ = 1.3 and 1.4, increasing the mass flux at fixed equivalence
ratio results in shifting the maxima towards the burner surface and accelerating the
HCN burnout. Both effects are expected based upon the reduced degree of
stabilization and the concomitant increase in flame temperature. At ϕ = 1.5 the
maximum is shifted so far downstream that the HCN burnout region is beyond the
measurement domain. The observation of 5-10 ppm of “residual” HCN downstream
of the flame front that is only slowly oxidized supports the conclusion drawn in earlier
studies of NO formation in the burnout region of rich methane flames [5]. It is
interesting to point out the strong temperature dependence of the HCN burnout. For
example, the change in residence time between flames D and F by nearly a factor of
two should lead to an increase in the HCN mole fraction at the same axial position.
However, we observe a decrease in HCN mole fraction by nearly a factor of two, most
likely caused by the relatively modest (~100 K) increase in the flame temperature.
Also interesting is the strong shift downstream of the maximum in the HCN profiles
115
Chapter 6
and the reduced oxidation rate in the post flame zone with increasing equivalence
ratio at fixed flame temperature, illustrated by comparing the flames B, D and H,
which have almost the same temperature (~1850 K) but increasing the equivalence
ratios from ϕ = 1.3 to 1.5.
Large discrepancies are observed between the measured results and those
calculated using the GRI-Mech 3.0 chemical mechanism. As can be seen from figures
6.1– 6.3, the calculations significantly overpredict the measured HCN mole fractions
for all mass fluxes at equivalence ratios ϕ = 1.3 and 1.4. At ϕ = 1.5, the calculated
HCN profiles are in surprisingly good agreement with the measurements for
ρv = 0.008 g/(cm2s), while the experimental results are underpredicted for ρv = 0.005
g/(cm2s). At the same time, GRI-Mech 3.0 predicts the qualitative trends in the
burnout region reasonably well. This suggests that adjustment of the rates of the
reactions that form and consume HCN in the flame front in GRI-Mech 3.0 would
improve the predictions substantially.
According to the GRI-Mech 3.0 scenario, HCN is formed mainly in reaction
(R6.1) between CH and N2. A substantial part of the nitrogen atoms produced in this
reaction will also be converted to HCN. First they react with CH3 to form H2CN
CH 3 + N = H 2 CN + H (R6.3)
and then H2CN dissociates into HCN and H; here too, the HCN produced will be
oxidized to NO. Oxidation of HCN in the flame front occurs mainly by
To lower the predicted peak HCN mole fraction, either the rate of formation must be
decreased or the rate of consumption increased.
To improve the agreement for the results shown above, the rate of the reaction
(R6.1) must be decreased by a factor 2.5. This reaction, being the first step of the
Fenimore mechanism, ultimately determines amount of NO that will be produced in
fuel-rich hydrocarbon flames [1,2]; changing its rate will result in large disagreement
with numerous experimental and modeling studies of the NO formation, for which
there is currently good agreement [4] en references therein). Alternatively, decreasing
the calculated HCN mole fraction in the flame front by varying the rate constant of the
116
Chapter 6
reaction (R6.4) requires increasing its rate by more than 10 times. The rate constant of
this reaction was determined both experimentally and by transition state calculations
[18-20]. Very good agreement (~30%) was observed between calculations and
measurements in the temperature region from 450 K up to 2400 K. Moreover, the rate
constant of this reaction was used as an optimization variable for the GRI-Mech 3.0
mechanism, where it was already increased by a factor 1.45. Further increase will
bring the rate constant of reaction (R6.4) far beyond the specified margins of
uncertainty.
A possible explanation for the discrepancy between measured and calculated
HCN concentrations can be found in considering the products of the reaction between
CH and N2 asserted in ref. [14]. The NCN formed in this reaction can be converted
directly to NO in the following reactions:
NCN + O = CN + NO (R6.5)
and
Reactions (R6.5)-(R6.8) are supposed to be fast [15,21], with the result that the rate of
the reaction between CH and N2 controls NO formation. At the same time, reactions
(R6.5) and (R6.6) produce NO directly while bypassing HCN formation.
Unfortunately, information on NCN kinetics is very scarce. The reactions (R6.5)-
(R6.8) were included in the modeling study of the NO reburning in a flow reactor
[21], where their rates were estimated. It should be pointed out that the reaction (R6.6)
between NCN and O2 can be important in the fuel-rich highly stabilized flames, where
oxygen is removed relatively slowly, yielding the broad flame front in which the O2
concentrations are one to two orders larger than those of O, H and OH .
117
Chapter 6
118
Chapter 6
Figure 6.4. Axial profiles of HCN mole fractions in methane air flame F. Triangles
denote measured HCN concentrations. Lines denote flame calculations using GRI-
Mech 3.0 mechanism with NCN removal reactions [21] (solid – unchanged rate
constants, dashed – the rate constants are 1.0·1013cm3/(mol·s) for all NCN removing
reactions) and dotted - GRI-Mech 3.0 without NCN removal reactions).
It should be pointed out that variation of the rate constants should be performed
very cautiously, remaining inside any expected uncertainty limits. A recent theoretical
study [23] and experiments at room temperature [24] both yielded rates of the reaction
(R6.6) between NCN and O2 that are orders of magnitude lower than that from Ref.
[21]. This large disparity dissuades us from trying optimizing the rate constants of the
reactions (R6.5)-(R6.8) based on the results presented here. In addition, it was
possible to optimize the rates to fit one experiment adequately; however, good
prediction for one experiment resulted in a poorer prediction for other experiments.
Further experimental and theoretical studies of NCN kinetics are needed for a better
understanding of NO and HCN formation in hydrocarbon flames.
119
Chapter 6
6.4 Conclusions
120
Chapter 6
Literature
121
Chapter 6
122
Chapter 7
Chapter 7
123
Chapter 7
7.1 Introduction
Stringent emission regulations for greenhouse gases and the drive to conserve
the finite supplies of fossil fuels have resulted in increased interest in the possible
addition of sustainable hydrogen to natural gas. In spite of any potential advantage to
hydrogen addition in this regard, a negative effect on other aspects of combustion
performance, such as increased pollutant emissions (NOx, soot), must be weighed in
the overall considerations. Recently, several studies on the effect of hydrogen addition
to hydrocarbons have been conducted regarding extinction limits [1], burning
velocities [2-4] and engine performance [5]. However, very few flame structure
studies have been performed on hydrogen-hydrocarbon mixtures, and all of these
pertained to non-premixed flames. For example, the effect of hydrogen was studied in
a hydrogen-natural-gas composite fuel in turbulent jet flames [6], and showed that
increasing the hydrogen concentration resulted in an increase in soot, CO and NOx
formation. Another study [7] added natural gas and propane to coflow hydrogen
diffusion flames; a decrease in soot formation and an increase in NOx with increasing
hydrogen content were found. In the same type of flames, intermediate radicals were
measured [8,9] and a decrease in CH radical concentration was observed with
increasing hydrogen content. In these studies, the increase in NOx emission was
ascribed to the increasing flame temperature with hydrogen content, which promotes
thermal NOx production. However, the measured decrease in CH concentration with
hydrogen content suggests that hydrogen addition to hydrocarbon flames reduces the
NOx emissions contributed from the Fenimore mechanism. The analysis of the
chemistry in the coflow diffusion flame studies described above suffers from the
complication of multidimensional transport and the fact that the difference in diffusive
behavior between the relative heavy hydrocarbon fuels and hydrogen is very large.
For this reason, measurements of key intermediates species in pollutant formation
using premixed one-dimensional flames can yield a more unambiguous contribution
to understanding the consequences of hydrogen addition for the chemistry of pollutant
formation. To date, no quantitative studies have been reported on the effect of
hydrogen addition on pollutant formation in one-dimensional flames.
One of the key intermediate species in the formation of soot in rich hydrocarbon
flames is acetylene [10] and understanding the fate of this species is essential to
understand soot inception. Also, acetylene is a precursor of the CH radical [11], which
124
Chapter 7
125
Chapter 7
7.2 Experimental
126
Chapter 7
performed by using the measured mass flux through the burner surface as an input
parameter.
Figure 7.1. Calculated flame temperature as function of the mass flux for a pure
methane (solid line) and a methane/hydrogen, 50/50 mixture (dashed line), both
having an equivalence ratio of ϕ=1.5.
127
Chapter 7
128
Chapter 7
Figure 7.2. Axial profiles of HCN mole fraction in CH4/air flames and CH4/H2/air
flames, ϕ = 1.4. Symbols denote probe measurements in flames E (squares), F
(diamonds), G (circles) and H (triangles). The lines denote flame calculations using
GRI-Mech 3.0 in flames E (dashed), F (dotted) G (bold solid) and H (thin solid).
Figure 7.3. Axial profiles of HCN mole fraction in CH4/air flames and CH4/H2/air
flames, ϕ = 1.5. Symbols denote probe measurements in flames I (diamonds), J
(squares) and K (triangles). The solid lines denote flame calculations using GRI-
Mech 3.0 in flames I (dashed), J (solid) and K (dotted).
129
Chapter 7
130
Chapter 7
The effect of replacing 23% methane by hydrogen, at constant mass flux, on the
C2H2 profiles is illustrated in figure 7.4. The results show for equivalence ratios 1.3
and 1.5 (Flames A-D in Table 1) that H2 addition only slightly decreases the measured
peak C2H2 mole fraction. This small reduction of C2H2 is essentially the same as the
∼15% decrease “naively” expected from dilution when 23% methane is replaced by
hydrogen, here too making the simple assumption that C2H2 formation is directly
proportional to the concentration of hydrocarbons in the fuel. No substantial
difference in the measured C2H2 concentration is observed in the post flame zone for
the flames with (B, D) and without hydrogen addition (A, C).
In addition, the predicted C2H2 profiles obtained using GRI-Mech 3.0 are compared
with the measurements. As can be seen from figure 7.4, the calculated C2H2 profile
(dashed line) shows substantially higher peak concentrations and slower decay in the
post flame zone for flame D. Although not presented, the computed C2H2 profiles for
the other flames shown in figure 7.4 show similar discrepancies, as expected from the
results presented in Chapter 5 and in Ref. [19]. Replacing the rate coefficient of the
reaction C2H2 + OH → CH2CO +H used in the GRI 3.0 mechanism by the expression
4.87 x 1013exp(-12000cal/RT) cm3mol-1s-1 recommended in chapter 5 yields very
good agreement between measurements and calculations for all flames studied, as can
be seen in the figure.
131
Chapter 7
Figure 7.4. Axial profiles of HCN mole fraction in CH4/air flames and CH4/H2/air
flames, ϕ = 1.5 and 1.3. Symbols denote probe measurements in flames A (circles), B
(squares), C (diamonds) and D (triangles). The dashed line denotes flame the
calculation with GRI-3.0, and other lines, flame A (bold solid lines), flame B (thin
solid line), flame C (bold doted line) and flame D (thin dotted line) are the result of
calculations with the increased rate coefficient for C2H2+OH→CH2CO+H.
7.4 Conclusion
132
Chapter 7
zone as compared to the measurements for all flames at ϕ=1.4. Increasing the
hydrogen content in the fuel for the flames at ϕ=1.5 results in roughly the same
systematic decrease in the calculated HCN concentration as measured. However, this
observed reduction is probably caused by the reduction in temperature caused by
increased stabilization, which is not supported by the measurements presented in this
thesis, and not due to a “hydrogen effect”.
The C2H2 measurements show that the addition of 23% hydrogen results in only
a marginal reduction of the C2H2 concentration for the flames measured at ϕ=1.3 and
1.5, suggesting that hydrogen addition does not have any significant effect on the
flame processes responsible for C2H2 formation/consumption in CH4/air flames.
Comparison between calculated and measured profiles shows significant
overprediction of the maximum C2H2 concentration and a much slower predicted
decay of C2H2 in the post flame zone. As expected from Chapter 5, replacing the rate
coefficient of the reaction C2H2 + OH → CH2CO +H used in the GRI-Mech 3.0
mechanism by 4.87 x 1013exp(-12000cal/RT) cm3mol-1s-1 resulted in good agreement
between measured and calculated C2H2 profiles for all flames studied.
133
Chapter 7
7.5 Literature
134
Chapter 7
18. L.V. Moskaleva, M.C. Lin, Proc. Combust. Inst. 28 (2000) 2393-2401.
19. E. W. Kaiser, T. J. Wallington, M. D. Hurley, J. Platz, H.J. Curran, W. J.
Pitz, C. K. Westbrook, J. Phys. Chem. A., 104 (2000) 8194-8206.
135
Summary
136
Summary
(960-1100 K). Under stoichiometric conditions the experimental results show that
replacing methane by hydrogen results in a reduction in the measured ignition delay
time. At moderately low concentrations of hydrogen (≤ 20%) only a weak effect on
the measured ignition time is observed, while at 50% hydrogen content in the fuel a
substantial reduction in ignition delay time is seen under all measured conditions.
Moreover, the measurements show that the effects of hydrogen in promoting ignition
increases with temperature and decreases with pressure. Experimental results for 50%
hydrogen in the fuel at equivalence ratio ϕ = 0.5 are essentially identical to those at
ϕ = 1.0. These results suggest that the adverse affects of hydrogen addition to natural
gas on engine knock may be limited for hydrogen fractions of only a few tens of
percent. Comparison between measured and calculated ignition delay times shows
very good agreement for all fuel mixtures using the proposed mechanism of Petersen
et al. (E. L. Petersen, D. M. Kalitan, S. Simmons, G. Bourgue, H. J. Curran and J. M.
Simmie, Proc. Combust. Inst .31 (2007) 447-454.)
Chapter 4 describes the experimental protocols for concentration measurements
of HCN and C2H2 in one-dimensional flames using extractive probe sampling
followed by analysis using tunable diode laser absorption spectroscopy (TDLAS) at
∼1.5 μm. The calibration procedure for acetylene is performed by measuring the
absorption coefficient in a gas sample containing a known concentration of acetylene
under the same experimental conditions as those existing for the flame samples. At
mole fractions above 1000 ppm, the accuracy of the measured C2H2 is ∼5%;
decreasing C2H2 mole fraction results in deteriorating accuracy, to 15% at 100 ppm.
The same calibration procedure is performed for the HCN measurements. However, to
increase the sensitivity wavelength modulation absorption spectroscopy (WMAS)
with second harmonic detection is used. The accuracy of the measured HCN mole
fraction in the sampled flame gases is better than 30% at concentrations above 3 ppm.
Before examining the effects of hydrogen addition on the formation and consumption
of these species, their profiles are first measured and analyzed in flames using pure
methane as fuel.
Chapter 5 presents measurements of C2H2 concentration profiles in one-
dimensional atmospheric-pressure rich premixed methane/air flames using
spontaneous Raman scattering and an extractive probe sampling technique (Chapter
4). Excepting a shift of approximately 1.3 mm, resulting from the acceleration of the
137
Summary
combustion products in the probe orifice, the axial Raman and probe profiles are in
very good agreement. The measurements show that changing the equivalence ratio
from ϕ = 1.4 to 1.5 results in an increase of the peak C2H2 mole fraction by nearly a
factor two. At fixed equivalence ratio, the maximum C2H2 mole fraction depends only
slightly on the flame temperature, while the C2H2 oxidation in the post flame zone
increases substantially in the flames with increasing flame temperature. Comparison
of measured C2H2 profiles with those calculated, using the GRI-Mech 3.0 chemical
mechanism, shows a much faster post-flame decay in the experimental results.
Increasing the pre-exponential factor in the rate coefficient of reaction
C2H2 + OH → CH2CO + H to 1.7 x 1012 cm3mol-1s-1 in the range 1760 – 1850 K
yields excellent agreement between computed and experimental results.
In Chapter 6 the formation and consumption of HCN in fuel-rich atmospheric
pressure methane/air flames is discussed. Towards this end, axial HCN and
temperature profiles have been measured at equivalence ratios ϕ = 1.3, 1.4 and 1.5.
For the richest flame studied (ϕ = 1.5) very slow oxidation of HCN in the post flame
zone is observed, demonstrating “residual” HCN in the post flame gases of fuel-rich
methane/air flames. The HCN measurements show that increasing the flame
temperature at fixed equivalence ratio does not result in significant changes in the
HCN peak mole fraction, while the HCN oxidation in the post-flame gases increases
substantially. Decreasing the equivalence ratio leads to faster HCN oxidation in the
post flame zone. Large discrepancies are observed between measured and calculated
HCN profiles using GRI-Mech 3.0. Attempts to bring the calculations using GRI-
Mech 3.0 into agreement with the experimental observations by changing the rates of
key formation and consumption reactions within the uncertainties in the literature
were unsuccessful. Consideration of NCN as a primary product of the reaction
between CH and N2, based on recent theoretical studies, allows improvement in the
agreement between measured and calculated HCN concentrations. However, the lack
of information on the rate constants of the NCN reactions at high temperatures
precludes unambiguous conclusions regarding this mechanism.
Chapter 7 is an extension of Chapters 5 and 6 and examines the effect of
hydrogen addition on the formation and consumption of HCN and C2H2 in fuel-rich
stabilized methane/air flames. The HCN measurements at ϕ = 1.4 and 1.5 show that
increasing the hydrogen fraction in the mixture at constant flame temperature results
138
Summary
139
Samenvatting
De steeds strengere eisen ten aanzien van CO2 emissies en de verwachting dat nog
binnen deze eeuw de reserves van fossiele brandstof uitgeput zullen zijn, heeft geleid
tot toenemende belangstelling in het gebruik van aardgas/waterstof mengsels als
alternatieve brandstof in verbrandingsapparatuur. Deze apparatuur is gewoonlijk
afgesteld voor de locale brandstof, en het zal duidelijk zijn dat veranderingen in
brandstofsamenstelling niet tot verslechterd gedrag mag leiden. Doordat de
verbrandingseigenschappen van waterstof sterk verschillen ten opzichte van aardgas
(Hoofdstuk 1), is de vraag in hoeverre het gedrag van verbrandingsapparatuur zoals
gasmotoren, branders en turbines (negatief) beïnvloed zal worden door het aardgas
met waterstof te verrijken. De aanwezigheid van waterstof kan bijvoorbeeld de
vorming van milieuschadelijke emissies bevorderen bij verbrandingsapparatuur en
leiden tot klopverschijnselen (ongecontroleerde ontsteking) in gasmotoren. Om deze
praktische consequenties adequaat te doorgronden is het essentieel de veranderingen
in de onderliggende fysische en chemische processen die verantwoordelijk zijn voor
het verbrandingsgedrag te onderzoeken, wanneer waterstof wordt toegevoegd. De
zelfontstekingseigenschappen vermeld in dit proefschrift geven nieuwe inzichten in
het ontstekingsgedrag van methaan, waterstof en methaan/waterstof
brandstofmengsels, onder condities relevant voor klopverschijnselen in gasmotoren.
Daarnaast geven de ruimtelijke verdelingen van de molfracties van C2H2 en HCN,
belangrijke tussencomponenten in de vorming van respectievelijk roet en NOx,
gemeten in één-dimensionale CH4/lucht en CH4/H2/lucht vlammen bij atmosferische
druk inzicht in veranderingen in de vorming van milieuschadelijke stoffen als gevolg
van waterstof toevoeging. De metingen die in dit proefschrift worden gepresenteerd
worden ook gebruikt om de nauwkeurigheid te testen van verschillende chemische
mechanismen die gebruikt zouden kunnen worden voor het voorspellen van het
verbrandingsgedrag van waterstof/aardgas mengsels.
Op basis van een ontwerp van MIT is in ons lab een Rapid Compression
Machine (RCM) gebouwd, waarmee onder gecontroleerde omstandigheden die
relevant zijn voor gasmotoren zelfontsteking kan worden onderzocht (Hoofdstuk 2).
Resultaten tonen aan dat de RCM een brandbaar mengsel tot drukken tot ~70 bar en
temperaturen tot ∼1100 K comprimeert, waarbij het merendeel van deze
drukverhoging plaatsvindt in een zeer korte tijd (<3 ms). De temperatuur van het
gecomprimeerde mengsel is berekend aan de hand van de gemeten druk, door gebruik
te maken van de isentropische relaties van een ideaal gas. Binnen het bereik van de
140
Samenvatting
141
Samenvatting
142
Samenvatting
143
Dankwoord
144
Dankwoord
Naast werk was er tijd voor ontspanning, daarvoor wil ik mijn vrienden erg
bedanken. Natuurlijk wil ik mijn familie bedanken en in het bijzonder mijn ouders;
Wim en Anneke voor hun steun en vertrouwen in mij.
Verder wil ik Daniëla speciaal bedanken voor het ontwerpen van de prachtige
omslag van mijn proefschrift.
En natuurlijk wil ik Sandra bedanken voor al haar liefde en energie die ze me heeft
gegeven om door te gaan met mijn promotieonderzoek, met name tijdens de
momenten waarin het onderzoek niet verliep zoals ik dat wilde.
145