Combustion and Flame 207 (2019) 186–195

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Combustion and Flame

journal homepage: www.elsevier.com/locate/combustflame

The internal combustion engine as a CO2 reformer

Hendrik Gossler a, Simon Drost b, Sylvia Porras b, Robert Schießl b, Ulrich Maas b,
Olaf Deutschmann a,∗
a
Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology, Karlsruhe, Germany
b
Institute for Technical Thermodynamics, Karlsruhe Institute of Technology, Karlsruhe, Germany

a r t i c l e i n f o a b s t r a c t

Article history: This paper investigates the concept of using piston engines as chemical reactors to convert CO2 to more
Received 17 January 2019 useful substances. Conditions are presented under which significant conversions of CO2 and CH4 to syn-
Revised 6 March 2019
thesis gas (CO and H2 ) can be achieved in internal combustion engines (ICE). Numerical optimization of
Accepted 20 May 2019
the process based on detailed chemistry is employed to identify initial values of temperature, pressure
and gas composition which theoretically yield maximal CO2 conversions. The optimization results are
Keywords: used to guide experiments in a rapid compression machine (RCM) setup that is used in place of a real
CO2 reforming ICE. The optimization predicts that the addition of molecular oxygen enables the endothermal dry re-
Internal combustion engine forming reaction (CO2 + CH4  2 H2 + 2 CO) to proceed by delivering the required energy from burning
Rapid compression machine
a part of the fuel. Despite combustion taking place, experiments show that over 50% of the CO2 con-
Numerical optimization
tained in mixtures of Ar, O2 , CH4 , DME (dimethylether) and CO2 can be converted to syngas with H2 O as
Detailed chemical kinetics
a by-product.
© 2019 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

1. Introduction
The environmental effects of CO2 emissions are a major prob-
lem of industrialized societies. Beside its appearance as a waste-
product of hydrocarbon combustion [1], CO2 also occurs as one
of the main byproducts in chemical industry. CO2 reforming, or
dry reforming, has gained increased attention in recent years as it
opens a route to utilize the CO2 as a carbon source for more use-
ful products [2], and therefore represents a possibility to reduce
CO2 emissions. Dry reforming is strongly endothermic, and the net
reaction can be formulated as
CO2 + CH4  2 H2 + 2 CO H  = 247 kJ mol−1 .
Besides offering the benefit of removing undesired CO2 , this re-
action is also attractive for applications that require synthesis gas
with low H2 /CO ratios.
In the chemical industry, reforming processes are generally car-
ried out using catalysts that often contain noble metals such as
rhodium and palladium. However, as in the case of dry reform-
ing, the use of precious metal catalysts is often cost prohibitive at
commercial-scale. Although current research suggests that less ex-
pensive catalysts based on nickel or cobalt could be used in dry
∗
Corresponding author.
E-mail address: deutschmann@kit.edu (O. Deutschmann).
URL: http://www.itcp.kit.edu/deutschmann (O. Deutschmann)
reforming, these systems have other disadvantages [3–5]. For ex-
ample, nickel catalysts are susceptible to coking, while cobalt cat-
alysts are reported to suffer from deactivation by oxidation [6,7].
An exploration of alternative methods for CO2 reforming there-
fore appears worthwhile. The physico-chemical properties of the
overall reaction (Eq. 1) impose important constraints for such a
method:
1. Hypothetically, if all kinetic constraints are removed, the system
will instantaneously approach chemical equilibrium. The chem-
ical composition at this equilibrium, and therefore also the ex-
(1) tent of conversion, depends on the thermodynamic conditions.
For the endothermal reaction (Eq. (1)), chemical equilibrium
moves further to the right (i.e. to the side of CO and H2 )
with increasing temperature (at constant pressure). At constant
temperature, equilibrium is shifted to the right when pressure
is decreased. Therefore, based on equilibrium considerations,
high-temperature and low-pressure conditions favor high CO2
conversions. Starting from unreacted “cold” low-pressure con-
ditions, input of energy is hence required to shift equilibrium
to the desired state.
2. Some of the elementary reaction steps underlying Eq. (1) have
very high activation energies. Due to the Arrhenius-like de-
pendence of elementary reaction rate coefficients, high tem-
peratures are required to allow those reactions to proceed at
sufficient speeds and approach equilibrium.

https://doi.org/10.1016/j.combustflame.2019.05.031
0010-2180/© 2019 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
 H. Gossler, S. Drost and S. Porras et al. / Combustion and Flame 207 (2019) 186–195
Compression engines have the potential to fulfill the above-
mentioned requirements, and also feature some more properties
which make them appropriate candidates as reactors:
• The required input of energy (item (1) above) can be provided
in the form of mechanical compression work. This work can
be supplied within relatively short times (down to the scale
of milliseconds). Within these time scales, heat loss processes
can interfere strongly with chemical kinetics. The ability for fast
repetition also means that high mass-flows of CO2 can be con-
verted.
• The high temperatures required to overcome kinetic barriers
(point (2) above) can be provided in engines via compression.
• In contrast to conventional large-scale chemical reactors, com-
pression engines can be operated in a very flexible manner, tol-
erating quite large variations of inputs (mass flow rates, input
pressure and temperature).
• Engines are also able to react promptly to changes in input con-
ditions, and their operation can be adapted to optimal opera-
tion.
Also, from an economic point of view, engines have the advan-
tage of being cheap as the technology is well developed and ro-
bust.
Note that, the higher the conversion, i.e., the more the reaction
(Eq. (1)) is moved to its right side, the more net input of energy
is required for the process. In energy conversion technology, situa-
tions where a temporal and/or local surplus of an otherwise “unus-
able” form of energy (e.g., heat or work) is available for exactly this
purpose, occur quite frequently. The availability of energy from “re-
newable” energy sources such as solar and wind power are subject
to high fluctuations. This leads to gaps between energy demand
and availability. When there is an abundance of (electric) energy,
the energy should ideally be stored in order to compensate times
where the renewable energy sources are not able to meet the de-
mand of energy.
While the literature contains enormous amounts of studies con-
cerning ICEs operated under conventional (i.e. total-oxidation) con-
ditions, substantially less research has been dedicated to their use
as chemical reactors. Recently, a review article has been published
that gives an overview of the past research on fuel reforming in
conjunction with internal combustion engines [8]. Most of the pre-
vious work on in-cylinder fuel reforming has focused on burning
rich fuel-air mixtures to produce synthesis gas via partial oxida-
tion following the reaction
1 possible, both in theory and in the experiments, with suitably cho-
CH4 + O2  2 H2 + CO H  = −35.7 kJ mol−1 .
2
The in-cylinder production of syngas has been shown to work
in engine experiments by numerous groups, e.g. [9–15]. In these
studies, various ways to achieve stable operating conditions (i.e.
low cycle-to-cycle variations) were investigated. Spark ignition (SI),
compression ignition (CI) and homogeneous charge compression
ignition (HCCI) were successfully applied to convert methane-
based fuels to syngas.
Karim and Wierzba [11] operated an engine on rich mix-
tures of methane and oxygenated air, where the mixture was ig-
nited by injecting diesel fuel (CI mode). Yang et al. [12] were
able to demonstrate syngas production in an HCCI process with
added CO. In a combined modeling and experimental study, Wie-
mann et al. [15] investigated a single-cylinder engine operated
on methane/air using spark ignition and homogeneous charge
compression-ignition. In their experiments, n-heptane was added
to reduce auto-ignition temperatures and to stabilize engine oper-
ation.
In a study by a group of researchers at MIT [13], the use of
an engine as a reformer is motivated by economical factors. They
187
outline a concept in which engines form the key component of
compact gas-to-liquids plants. The concept allows the plant to be
operated at a significantly smaller scale in a profitable way, due
to the lower costs associated with engines compared to conven-
tional chemical reactors. Furthermore, a unique feature of their ex-
perimental work was the ability to preheat the inlet gas to over
480° C.
There are also numerous publications that studied the in-
cylinder production of syngas via partial oxidation numeri-
cally, for example [16–18]. In their modeling study, Hegner and
Atakan [18] focused on thermodynamic aspects of a polygenera-
tion process to produce hydrogen. The authors claim that exergetic
efficiencies of up to 80% are achievable compared to the separated
production of power, heat and hydrogen. Their study was later ex-
tended by accompanying experiments in a rapid compression ma-
chine [14]. Here, dimethyl ether (DME) was used as a fuel addi-
tive to allow methane conversions at moderate, technically acces-
sible compression ratios and inlet temperatures, as was done in
the present work. Apart from syngas, small amounts (2 mol %) of
ethylene were produced in the experiments.
In another modeling study, numerical optimization was applied
to maximize the hydrogen yield at the end of the expansion stroke
of an HCCI engine [17]. In the present study we expand on the ap-
proach in [17]. In contrast to previous studies that investigated the
use of engines as reformers to produce syngas, this work focuses
on converting an undesirable species (CO2 ). The production of syn-
gas, which goes along with the CO2 conversion, is regarded as a
side effect (albeit a positive one) only.
The objective of this paper is to demonstrate the concept of us-
ing a piston engine process to convert CO2 to syngas by dry re-
forming. We employ a coupled simulation/experimental approach
in which simulations, together with numerical optimization, are
used to identify operation conditions that theoretically yield opti-
mal conversions. A rapid compression machine (RCM) is used as an
engine simulator to assess whether the predicted conversion levels
can be realized in a process of semi-technical scale. Rapid com-
pression machines are devices which are frequently employed to
investigate chemical reactions under engine-like conditions [19].
In the remainder of this paper we will first describe the mod-
elling approach, which involves simulation of an engine process
with detailed chemistry. The procedure for using the simulation
to identify optimal engine operation points is then outlined. Next,
the RCM experiment setup is described. The results presented af-
terwards show that CO2 conversion levels of over 50 percent are
(2) sen initial composition of the mixture and initial temperatures and
pressures.
2. Methodology
In an engine, there are many operating parameters that can be
varied independently. Examples include the engine speed (rpm),
the inlet gas temperature (T0 ), the inlet pressure (p0 ) and the over-
all gas composition (mole fractions, x). Finding operating points
that will lead to high CO2 conversions is difficult due to the
vast number of combinations of possible operating parameters
and the typically strongly nonlinear dependence of the chemical
conversion on these parameters. For this reason, conducting em-
pirical experiments on a trial-and-error basis is not a practical
approach.
Instead, the approach taken in this paper is to employ numer-
ical optimization in conjunction with detailed chemical kinetics
simulations to predict promising operating points. The optimal op-
erating points proposed by the model are then verified in a rapid
compression machine setup.
188 H. Gossler, S. Drost and S. Porras et al. / Combustion and Flame 207 (2019) 186–195
The dry reforming reaction (Eq. (1)) has a few characteristics
that are important to the scope of the optimization approach. Pre-
liminary simulation studies showed that temperatures exceeding
10 0 0 K are required for any reactions to proceed at sufficiently high
rates. Thus, we can identify the temperature as a key limiting fac-
tor for CO2 conversion. We can assume that the higher the peak
temperature during an engine revolution is, the higher the CO2
conversion becomes. However, it is difficult to attain these high
temperatures in typical experimental setups due to their limited
preheating capabilities and/or insufficiently high compression ra-
tios. Because the initial gas composition itself can affect the re-
sulting temperature profile in a number of ways, the composition
gains an essential role as an engine tuning parameter. The objec-
tive is therefore to find optimal initial gas compositions that im-
plicitly lead to maximum temperatures, that in turn cause a maxi-
mum amount of CO2 to be converted. However, it is not clear what
the exact gas composition should be because there are opposing
effects and constraints.
Argon can be added to reduce the heat capacity of the gas mix-
ture and hence increase the temperature during the compression
phase. But more argon reduces the amount of the reactants (CO2
and CH4 ) that can be added to the mixture. Another way to reach
higher temperatures is to burn a part of the CH4 by adding O2 .
However, the mixture may fail to ignite if there is not enough O2
present; too much O2 , on the other hand, will lead to the produc-
tion of CO2 . Therefore, under the conditions we study, a trade-off
has to be taken: No oxygen addition offers potentially high CO2
conversion, but the inferred low reactivity of the oxygen-free mix-
ture may prevent the engine from realizing this potentially high
conversion. Higher amounts of oxygen tend to increase the mix-
ture’s reactivity, but also favor formation of CO2 , which is coun-
terproductive in a CO2 reforming process. Furthermore, reactivity
could be increased by adding reaction enhancers to the mixture,
such as DME. Adding these enhancers can increase CO2 conversion;
on the other hand, overly large amounts of enhancer increase the
cost and complexity of the process.
These considerations show that the problem of finding condi-
tions for which high CO2 conversion can be achieved is a non-
trivial task. Therefore, an approach based on mathematical opti-
mization is advantageous.
2.1. Modeling approach
2.1.1. Detailed chemistry simulations
The combustion chamber of the RCM is modeled as a batch
reactor with a user-definable variable volume profile. The model
accounts for the temporal change of volume, temperature and
species concentrations using a detailed gas-phase mechanism. Sur-
face reactions and spatial variations within the chamber are not
considered in this model. Heat loss through the cylinder walls is
accounted for using the global heat transfer model according to
Woschni [20].
The modeling approach gives rise to the following system of
coupled differential equations that must be solved simultane-
ously:
dni
= V · ω˙ i , (3)
dt
   temperatures, i.e.
dT n˙ i H i (T ) − n˙ i RT − pV˙ − q˙
=
i
. (4)
dt cV
The volume V enters the simulation as a temporal constraint; it
is computed from tabulated time/volume pairs that are obtained
from the experimental setup:
V = Vcyl (t ) . (5)
Fig. 1. Schematic drawing of the RCM used in this work. When the bumper is in
place as shown, the piston remains at TDC after compression (“RCM mode”). If the
bumper is removed altogether, the piston immediately retracts after reaching TDC
(“RCEM mode”, with zero hold time, tH = 0).
The equation system is closed by using the ideal gas equation
pV = nRT . (6)
The first differential equation (Eq. (3)) describes the temporal
change of moles of each species, and the second (Eq. (4)) describes
the change in temperature. In these equations, t is the time, n is
the amount of substance, and ω˙ is the effective reaction rate (in
mol/m3 /s) for the i-th species. Furthermore, H denotes the molar
enthalpy, R the universal gas constant, T the temperature, p the
pressure, and cV the mixture’s heat capacity (in J/K) at constant
volume. The temporal rates of change of moles and volume are de-
noted by n˙ and V˙ , respectively. Lastly, q˙ represents the heat flux (in
W) from the combustion chamber through the cylinder walls.
The general formula for calculating the effective reaction rates
when using a detailed reaction scheme is given by
 

NR
 
NS
νs j
ω˙ i = f (c, T ) = kj νij − νi j
 cs , (7)
j s
which is a function of both species concentrations c and tempera-
ture. Here, ν  denotes the stoichiometric coefficients of the prod-
ucts, while ν  denotes those of the reactants. The total number of
reactions and species are given by NR and NS , respectively. The rate
coefficient k is described either by an extended Arrhenius law, or,
in case the reaction is pressure-dependent, by the “F-Center” for-
mulation by Troe et al. [21]. The unit of k depends on the reaction
order.
The heat flux q˙ through the chamber walls is described by the
basic relationship for convective heat transfer
q˙ (t ) = h(t ) · Apiston + Ahead + Aliner (t ) T (t ) , (8)
where h is the heat transfer coefficient that is obtained by the
Woschni relation (in W/m2 /K, see below). Furthermore, A is the
area of the particular engine part as denoted by the index. The
area of the liner is the cylindrical part of the combustion cham-
ber, and is therefore dependent on time (cf. Fig. 1). The tempera-
ture difference in the above equation applies to the gas and wall
T (t ) = Tgas (t ) − Twall . (9)
The temperature Twall was taken to be equal to the inlet tempera-
ture of the gas (462 K) for all simulations; in practice, typical wall
temperature variations in engine-like devices [22] are small rela-
tive to the gas temperature Tgas , so that they do not impede the
realism of the model.
 H. Gossler, S. Drost and S. Porras et al. / Combustion and Flame 207 (2019) 186–195 189

Table 1 2.1.3. Chemical kinetic model

Nomenclature.
Development of chemical kinetic models has been a main sub-
Notation Unit ject of research in the last decades, mainly because of their major
α Heat transfer scaling factor – role in the simulation of internal combustion systems as well as in
ν Stochiometric coefficient – the description of species time-profiles in fuel combustion and ox-
φ Fuel equivalence ratio – idation [23]. Several reaction mechanisms have been developed in
ω˙ Effective reaction rate mol/m3 /s the past in order to describe hydrocarbon fuel combustion [24–32].
A Area m2
Using this well-validated and valuable information, Por-
B Bore m
c Species concentration mol/m3 ras et. al. [33] compiled a reaction mechanism based on the exist-
cV Mixture heat capacity at J/mol/K ing methane combustion and pyrolysis model of Hidaka et al. [30],
constant volume the C1 -C4 hydrocarbon oxidation mechanism of Heghes [31] devel-
C1 Constant (2.892) –
oped for the description of conventional combustion and the DME
C2 Constant (3.24×10−3 ) –
h Heat transfer coefficient W/m2 /K mechanism of Zhao et al. [32]. The resulting assembled mechanism
Hi Molar enthalpy of species i J/mol was adapted specifically for the description of polygeneration pro-
k Rate coefficient mol, m, s cesses of CH4 /DME mixtures at large equivalence ratios φ up to
n Amount of substance mol 20. It consists of 578 elementary steps and 90 species and was
NR Total number of reactions –
validated against RCM and shock tube ignition delay times mea-
NS Total number of species –
p Pressure Pa surements as well as against RCEM and flow reactor species pro-
rc Compression ratio – files experimental data between a temperature range of 600 K to
q˙ Heat flux W 1500 K and pressures of 10 bar to 30 bar [33,34].
R Universal gas constant J/mol/K
Detailed chemistry simulations presented in this work were
t Time s
T Temperature K
performed using this kinetic model. The mechanism will be pub-
U Internal energy J lished in a separate article, however, an electronic version of it is
Ui Molar internal energy of species i J/mol attached to this work as supplemental material.
V Volume m3
Vd Displacement volume m3
w Instantaneous gas velocity m/s
2.2. Optimization procedure
x Mole fraction –
X Conversion m/s The purpose of the optimization is to predict engine operating
conditions (the optimization variables) under which as much CO2
as possible (the objective function) is converted. There are many
The formula by Woschni provides a spatially-averaged instanta- operating parameters that can be varied, for example the engine
neous heat transfer coefficient and is given by speed (N, commonly in rpm, represented in the RCM by the com-
pression duration), the compression ratio (rc ), the inlet gas temper-
h(t ) = α · B−0.2 p(t )0.8 T (t )−0.53 w(t )0.8 . (10) ature (T0 ), the inlet pressure (p0 ) or the overall initial gas compo-
sition (mole fractions, x0 ). However, the problem can be simplified
Here, B is the bore (equal to the diameter of the cylindrical com- given the preliminary considerations outlined in the beginning of
bustion chamber), p is the instantaneous pressure (in bar) and T Section 2. The number of optimization variables can be reduced
the instantaneous temperature. A scaling factor (α ) exists to match because one of the key limiting factors is the maximum attainable
a particular experimental setup (see Section 2.1.2). The instanta- temperature. Hence, in the optimization, the initial gas tempera-
neous gas velocity w is given by ture is not included as an optimization variable and is set to al-
ways be T0 = 462 K. This value corresponds to the maximum tem-
Vd Tref
w(t ) = C1 c̄piston + C2 [ p(t ) − pmot (t )] , (11) perature admissible in our RCM setup. For better transferability of
prefVref
the results to the technical system, the initial pressure was taken
where C1 and C2 are constants (see Table 1), c̄piston is the mean to be 1.013 bar for all simulations and experiments. Furthermore,
piston speed, and Vd is the displaced volume. The variables Tref , the compression ratio is set to rc = 10, as this is representative for
pref and Vref denote “reference values” of temperature, pressure and a typical spark-ignition engine.
volume, for which the corresponding initial values are used. The In a real engine, the engine speed represents a suitable tun-
last term in the above equation in square brackets is a measure for ing parameter, as it influences ignition timing and residence time.
the combustion taking place and is equal to the difference between However, in an RCM, the engine speed (corresponding to compres-
the instantaneous pressures when the engine is fired and when it sion rate) is constrained to a small range, which considerably limits
is motored. In our simulations, the motoring pressure is obtained the usefulness of this parameter as an optimization variable. In all
by simulating the cycle while neglecting chemical reactions. For optimization simulations, we therefore use the same volume pro-
more details, the reader is referred to the original publication by file. The only remaining optimization variables are hence the mole
Woschni [20]. fractions x0 of the initial gas composition. In this study, the gas is
composed of the five species Ar, CH4 , DME, O2 and CO2 . The opti-
mization is carried out by keeping the initial CO2 amount constant
2.1.2. Scaling the heat transfer coefficient at a certain value and allowing the optimizer to vary the remain-
The scaling factor (α ) in the Woschni heat transfer correlation ing four species. This procedure is repeated for initial CO2 values
(Eq. 10) was varied in order to best match a pressure curve from from 10% to 50%.
the experimental setup prior to the optimization. The pressure pro- The objective function to be maximized is the CO2 conversion
file from the experiment was recorded using a gas feed of pure that we define as
nitrogen to rule out any misleading effects due to chemical reac- nCO2 (t0 ) − nCO2 (t ) nCO2 (t )
tion. Other experimental parameters were set to match those of XCO2 (t ) = =1− , (12)
nCO2 (t0 ) nCO2 (t0 )
the later optimization simulations: T0 = 462 K, p0 = 1.0 bar, rc =
10. The fit to the pressure profile resulted in a value of α = 99.6, where nCO2 is the time-dependent number of moles of CO2 . In the
which was then used in all subsequent simulations. optimization, the value is calculated for tf = 300 ms, which is the
190 H. Gossler, S. Drost and S. Porras et al. / Combustion and Flame 207 (2019) 186–195
compression time plus a certain hold time. We formulate the opti-
mization problem as
nCO2 (tf )
max XCO2 = 1 − , (13)
x0 nCO2 (t0 )
subject to the linear constraints
 Initial temperature T0
x0,i = 1 , (14)
i
9x0,DME − 1x0,CH4 = 0 , (15)
x0,i ≥ 0 , (16)
x0,Ar ≥ 0.02 . (17)
The linear constraints formulated above are to ensure that the
sum of all mole fractions equals unity (Eq. (14)), that the fuel
is composed of 90% CH4 and 10% DME by volume (Eq. 15), and
that each component can only take on positive values (Eq. (16)).
Furthermore, Eq. (17) constrains the amount of argon to above
2%. This last constraint is in place to reflect requirements of the
accompanying experiments, where a certain amount of helium
is required as a reference for the gas analysis instrument (see
Section 3 for more details). For simplicity, the optimization does
not additionally take helium into account. Instead, a part of the ar-
gon is substituted by helium in the experiments.
The optimization problem is solved using the derivative-based
SQP algorithm from the MATLAB Optimization Toolbox (see Chap-
ter 18 in [35] for a description of the algorithm). The actual simula-
tion code is part of the DETCHEM package [36] and is written in C,
C++ and Fortran. The code computes the objective function value
along with the derivatives with respect to the optimization vari-
ables. MATLAB calls the simulation code via a dynamic library that
passes the objective function value and the derivatives back. The
derivatives are calculated by algorithmic differentiation using the
Adept [37] software in conjunction with the CVODES solver that
is part of the sundials package [38]. The CVODES solver is used to
compute sensitivities in forward-mode.
2.3. Equilibrium chemistry simulations
In addition to the detailed simulations, states along a RCM
trajectory corresponding to chemical equilibrium were simulated.
This was done to bring the results of the detailed chemistry sim-
ulations in context with a (hypothetical) process where there are
no kinetic obstacles to the reactions. This theoretical limit aids in
the interpretation of the modeling and experimental results from
detailed chemistry, as will be described below.
For this, the temporal histories of internal energy U(t) and vol-
ume V(t) of the RCM simulation were used as an input; internal
energy U(t) was computed as the mole-weighted sum of the molar
internal energies of all species in the mixture:

NS
U (t ) = U i (T (t ) ) · ni (t ) , (18)
i=1
with the temperature-dependent molar internal energy of the
i−th species U i and its molar amount ni . Instantaneous values
T(t) and ni (t) were taken from the corresponding detailed chem-
istry simulation trajectory. The equilibrium states have the same
(time-dependent) internal energy and volume as the correspond-
ing states from detailed simulations.
Table 2
Parameters of the RCM setup.
Bore B 82 mm
Stroke L 74 mm
Compression ratio rc 8 to 12
Displaced volume Vd 0.4 L
Clearance volume Vc 6.6 cm3
300 K to 462 K
Initial pressure p0 0.5 to 1.5 bar
The equilibria represent the states that would result in the RCM
if the system would instantaneously react to the maximum possi-
ble extent, always adapting to transient thermodynamical condi-
tions (U(t) and V(t)), which constantly change during the process
due to compression and heat losses.
The equilibrium for given values of Ufix and Vfix is given by the
state of maximum entropy at those conditions. While a direct so-
lution of U, V equilibrium via entropy maximization is possible, it
is sometimes plagued by numerical problems, especially for rich
mixtures. On the other hand, for the related problem of finding the
equilibrium for given values of T, p (by minimizing Gibbs enthalpy),
a highly robust and efficient algorithm is known [39]. Therefore,
we used this as a numerical tool to obtain U, V-equilibria by an
iterative procedure. The first step involves expressing the equilib-
rium moles (ni ) for isothermal-isobaric conditions as a function of
T and p:
ni = n˜ i,eq (T , p) (i = 1, . . . , NS ) (19)
To obtain the equilibrium for given U and V rather than for given T
and p, the nonlinear system of two simultaneous equations in the
two unknowns T, p

NS
U i (T ) · n˜ i,eq (T , p) − Ufix = 0 , (20)
i=1
p
NS − Vfix = 0 (21)
i
n˜ i,eq (T , p) · RT
was solved numerically using a Newton method [40]. The solution
values T, p are the desired equilibrium values Teq , peq , respectively,
for the given Ufix and Vfix . The species moles ni,eq at this equilib-
rium are ni,eq = n˜ i,eq (Teq , peq ), thus fully determining the equilib-
rium at Ufix , Vfix .
3. Experimental methods
A rapid compression machine (RCM) was used to perform the
experiments in place of a real engine to reduce apparatus complex-
ity and to allow more well-defined initial and boundary conditions.
The RCM setup has been described in detail by Werler et al. [41],
therefore only a brief overview of the machine is given, with a de-
scription of some modifications.
The main components of the RCM are shown in Fig. 1; Table 2
gives a technical overview of geometrical and operating parame-
ters. The central part of the setup is a piston-cylinder device that
is used to compress a test gas within the combustion chamber.
The combustion chamber is surrounded by an oil bath to adjust
the initial temperature. The piston head is equipped with a quartz
pressure transducer (Kistler 6061 B) for measuring the time re-
solved in-cylinder pressure. The position of the piston is measured
by a potentiometric position sensor (Burster type 7812) which is
screwed to the piston rod. Post-processing the piston position data
yields the volume profile of the combustion chamber over time.
A mixing vessel is used for preparation of the test gas in order
to achieve homogeneous conditions. The gases are added sequen-
tially and an absolute pressure transducer (Baratron type 121A)
 H. Gossler, S. Drost and S. Porras et al. / Combustion and Flame 207 (2019) 186–195
0.45
0.4
0.35
0.3
Volume / L
0.25
0.2 RCM
0.15
RCEM
0.1
RCEM
0.05 RCM
0 0
0 50 100 150
Time / ms
Fig. 2. Exemplary volume and pressure profiles of the experimental setup using an
ignitable CH4 /O2 /Ar mixture, highlighting the differences between RCM and RCEM
modes of operation. At t = 50 ms top-dead center is reached, which corresponds to
an engine running at a speed of 600 rpm.
measures the accumulated partial pressures. The volume of the
mixing vessel and its total interior pressure are both one order of
magnitude larger than in the combustion chamber, resulting in the
gas mass inside the vessel being two orders of magnitude larger.
This allows performing multiple RCM shots with the same initial
mixture.
The machine is equipped with a creviced piston that swallows
the roll-up vortex, helping to grant homogeneous thermal condi-
tions in the compressed gas [42–44]. Furthermore, the combustion
chamber is surrounded by a thermostatically controlled oil bath to
keep the temperature at the desired level.
A knee lever system pushes the piston towards the right into
the cylinder, thus compressing the gas in the combustion cham-
ber. Maximum compression is reached when the knee lever is fully
stretched and aligned with the piston rod and the piston itself (top
dead center, TDC). A bumper prevents the knee lever from moving
past the stretched position further downwards in order to keep the
piston from retracting back. In this way, isochoric conditions are
met after the compression phase. We refer to this mode of opera-
tion as “RCM mode”.
Alternatively, the bumper can be removed from the setup after
some adjustable hold time (tH = 0, . . . , ∞), and the knee lever can
then move downwards past the stretched position immediately af-
ter the compression phase, which in effect retracts the piston after
the hold time. We refer to this operation mode as “RCEM mode”,
short for rapid compression expansion machine mode. This mode,
with compression and subsequent expansion, is similar to a recip-
rocating internal combustion engine; various realizations of such
rapid compression-expansion machines have been presented, and
have been used as a simplified, well-controlled replacement of pis-
ton engines [45].
Figure 2 shows typical volume and pressure profiles of the
setup using an ignitable CH4 /O2 /Ar mixture, highlighting the dif-
ferences between RCM and RCEM operation modes. The solid lines
denote the volume (left axis) and the dashed lines denote the pres-
sure (right axis). The blue lines are the profiles recorded in RCM
mode (i.e. with the bumper in place), while the red lines were
recorded in RCEM mode. The traces start at t = 0, where the cylin-
der is filled with the unreacted mixture. In the compression phase
(until t = 50 ms), the volume and pressure curves of both modes
coincide. As the volume decreases from its initial value of 0.45 L to
0.05 L, the pressure rises from 1.0 bar to about 20 bar as per near-
adiabatic compression. In these examples, ignition occurs in both
operation modes near TDC (at 50 ms), detectable by a sharp pres-
sure rise up to 40 bar. Here, the ignition directly follows compres-
191
45 40
CO2 conversion / %
40 35
35
30
30
Pressure / bar
25
25
20 RCM
20
RCEM
15 15
0.6 0.8 1 1.2 1.4 1.6
10 Initial pressure / bar
5 Fig. 3. Comparison of CO2 conversions for RCM and RCEM operation modes at
T0 = 462 K. With increasing initial pressures, ignition occurs and the CO2 conversion
200 tends towards the same value (32%) for both modes of operation. Mole fractions of
the gas before compression: 8% CO2 , 14.8% CH4 , 1.6% DME, 15.1% O2 , 55.5% Ar, 5%
He.
sion. Therefore, no pressure decrease after TDC (which would be
common in a typical RCM experiment when ignition delay times
are measured) is visible.
After compression (from t = 50 ms), the difference between
RCM and RCEM modes becomes evident. In RCM mode, isochoric
conditions prevail, with the volume remaining at the constant min-
imum value of 0.05 L. The pressure decay in this region is solely
due to heat loss through the cylinder walls. In RCEM mode, the
expansion phase immediately follows the compression phase (hold
time tH = 0), like in a piston engine. The volume increases again af-
ter reaching its minimum value at TDC, resulting in a much faster
pressure decay than in the RCM case. However, the piston only par-
tially retracts due to geometrical constraints of the setup. Conse-
quently, the volume does not reach its initial value of 0.45 L. Fur-
thermore, it can be seen that the piston slightly oscillates during
the expansion phase.
After an experiment, the piston is retracted and it is waited un-
til the temperature has fallen to near its pre-compression value.
Then, samples from the in-cylinder gas mixture are extracted and
analyzed in a gas chromatographic (GC) analyzer (Agilent 490 Mi-
cro GC). Using helium as an inert reference and argon as a carrier
gas, this GC allows to measure multiple species, including CO2 and
lower hydrocarbons.
Experiments were carried out using the gas mixtures of CH4 ,
CO2 , O2 , DME and Ar predicted by the optimization. For simplic-
ity, helium was not included in the optimization. Therefore, 2 to
5% of the argon was substituted by helium in the experiments to
be able to quantify the mixture’s exact composition from the chro-
matograms. The CO2 conversion was then calculated according to
Eq. (12).
4. Results
4.1. RCM and RCEM operation modes
If operated with short hold times, RCEM mode more closely
resembles conditions in a real engine than RCM mode. However,
running experiments in RCEM mode over prolonged time periods
causes excessive wear to the setup. Therefore, RCM mode is pre-
ferred in order to avoid damage to the setup. This leads to the
question whether results obtained in RCM mode can be meaning-
fully extrapolated to real engine conditions.
Figure 3 shows a comparison between both operation modes. In
these measurements, the gas mixture (specified in the figure cap-
tion) was compressed at constant initial temperature (T0 = 462 K)
at varying initial pressures. Afterwards, the gas was analyzed and
the CO2 conversions were obtained. The measurements were car-
ried out in RCM mode (red crosses) and in RCEM mode (blue
circles).
192 H. Gossler, S. Drost and S. Porras et al. / Combustion and Flame 207 (2019) 186–195
10 15 20 25 30 35
55
50
CO2 conversion / %
45
40
35
30
25
40
Optimal inlet mole fractions / %
35
30
25
20
15
10
5 2.1
0 2
10 15 20 25 30 35
CO2 inlet mole fractions / %
Fig. 4. Top graph: predicted (line) and experimental (dots) CO2 conversions as func-
tion of CO2 inlet mole fractions at T0 = 462 K and p0 = 1.0 bar. Each dot corresponds
to the mean value of three samples analyzed in the gas chromatograph. Experimen-
tal and simulation results obtained in RCM mode. Bottom graph: gas composition
required to achieve the CO2 conversion shown on the top. The fuel is composed of
90% CH4 and 10% DME.
In Fig. 3, the initial pressure serves as a parameter to control
ignition. At low inlet pressures, the mixture fails to ignite and
hence none of the CO2 is converted. When the initial pressure is
increased, ignition occurs and the CO2 conversion approaches a
constant value, in this case of around 32%. This is true for both
operation modes. Both modes show a minimum initial pressure
that is required for ignition. From the data in Fig. 3, one can rec-
ognize that for RCEM mode, a pressure of 1.2 bar is required for
stable ignition, while for RCM mode, it is 0.7 bar (although this
might not be easily discernible in the figure). The reason for this is
that ignition delay is longer at lower pressures. If the ignition de-
lay is shorter than the RCEM’s expansion time (for pressures above
1.2 bar in Fig. 3), there is no difference in CO2 conversion between
RCM mode and RCEM mode. At lower pressures, the expansion in
RCEM mode does not allow ignition to happen. Therefore, the CO2
conversions differ between the two modes at low pressures.
Hence, RCEM mode and RCM mode deliver similar results, pro-
vided that ignition occurs. If ignition does occur, then the CO2 con-
versions will be the same for both RCM and RCEM modes of oper-
ation. We therefore conclude that data obtained in RCM mode can
be used to infer information on the feasibility of the process under
engine conditions. A real engine may even be advantageous over
the RCM, as there are more options to trigger ignition in an ICE,
for example by a spark.
4.2. CO2 conversion
Figure 4 shows the optimal gas composition (bottom graph)
along with the related CO2 conversions (top graph), both as func-
tions of CO2 mole fractions at the inlet. The bottom graph should
be interpreted as follows. If the engine is to be operated with 20%
(per volume) of CO2 in the inlet, then the optimal composition of
the remaining 80% is: 3.6% argon (red line, left axis), 33.0% oxy-
gen (blue line, left axis), and 43.5% fuel (9:1 mixture of CH4 and
DME, black line, left axis). This mixture corresponds to a φ -value
(gray line, right axis) of 2.77. The resulting maximum attainable
40 45 50 CO2 conversion of 51.0% is shown in the top graph (blue line). Only
Experiment CH4 , DME and O2 enter the formula to calculate φ ; The oxygen
Simulation contained in the CO2 is not included in the calculation.
The dots are the experimental values as determined by gas-
chromatographic analysis of gas samples from the RCM combus-
tion chamber. Using the gas composition predicted by the numer-
ical optimization, the CO2 conversions in the experiment closely
follow the values of the simulations.
2.9 Note that the optimization was carried out with a constraint
Fuel
O2 2.8
in place that restricts the argon mole fractions to values greater
Ar than or equal to 2%, as the GC unit requires a certain amount of
2.7 reference gas to be present. With increasing CO2 mole fractions,
2.6 it can be seen that the mole fraction of argon tends towards this
minimum value. While it is conceivable that the inert gas is not
2.5
Optimal
required here to attain similarly high CO2 conversions, we would
2.4 not have been able to quantify the results.
2.3
4.3. Evolution of states during the RCM process
2.2
Figures 5 and 6 both show the simulated temporal evolution of
selected species (top) and temperature (bottom). The conditions in
40 45 50 the simulation are the optimal values for CO2 initial mole fraction
of 20%, as shown in Fig. 4. Figure 5 shows the data on a conven-
tional time axis; this gives a realistic impression of the dynamics
of the process. Figure 6 shows the same data, but with a differently
scaled time axis, helping to better discern the different phases of
the RCM process.
For the detailed kinetics curves (solid lines, labeled with “kin.”),
starting at t = 0 with unreacted mixture at the initial temperature
of 462 K and pressure of 1.0 bar, compression leads to a temper-
ature rise that is visible at approx. t = 50 ms. This triggers auto-
ignition near 75 ms which then evolves into combustion, visible
by the very steep rise in temperature and almost instantaneous
species conversion. At this point in time, CH4 and CO2 get con-
sumed very quickly, while CO rises from 0 to about 35% mole frac-
tion. The temperature reaches a maximum at about t = 80.6 ms,
and then decreases rapidly due to heat losses (“cool-down” phase).
It asymptotically approaches the pre-compression temperature of
462 K. The species, in contrast, do not notably change in this cool-
down phase. Instead, their mole fraction values remain close to
the values at t = 80 ms. After t = 300 ms temperature has nearly
reached its initial value of 462 K.
The curves for equilibrium show a different behavior (dashed
lines, labeled with “equil”.). At t = 0, the temperature at the U, V-
equilibrium is already high (close to 20 0 0 K). The species mole
fractions differ from the detailed chemistry solution as well. There
is practically no methane at equilibrium, while more CO2 and CO
is present than in the kinetics simulations. During compression,
the equilibrium temperature changes only slightly. Its maximum
value of about 2100 K is reached near t = 70 ms, which is more
than 300 K below the maximum temperature in the kinetics simu-
lations.
Between t = 80 ms and 82 ms, the chemical reactions proceed
quickly due to the high temperatures, allowing the system to reach
equilibrium for all state variables (species, temperature). Conse-
quently, the curves for detailed chemistry and equilibrium coin-
cide in this region (near t = 82 ms). This can be seen well in the
center section of the time axis in Fig. 6. Afterwards, when the
temperature has dropped to about 1500 K, some reactions are no
longer fast enough and the species states become “frozen”. From
this point on, the system can no longer adapt its chemical state to
the changing conditions during the cool-down phase. This is visi-
ble in Fig. 6 where the detailed states then deviate from the equi-
librium curve at t = 88 ms. The deviation between detailed solu-
tion and equilibrium is considerable for all species. Notably, dur-
ing cool-down, equilibrium methane rises from its previous value
 H. Gossler, S. Drost and S. Porras et al. / Combustion and Flame 207 (2019) 186–195 193

0 50 100 150 200 250 300 librium. In contrast, the detailed kinetics simulations predict that
45
during cool-down CO2 stays near its low value of the “hot” phase,
40 CH (kin.)
4
where both equilibrium and detailed simulations coincide and pre-
CO (equil.) H (kin.) CO (kin.) dict xCO2 ≈ 5%.
35 2
The observed high CO2 conversion levels exceeding 50% in both
H (equil.)
Mole fractions / %

30 2
the detailed chemistry simulations and the experiment therefore
25 CO (equil.)
reflect the tendency to preserve the chemical composition of equi-
H O (kin.)
libria (that are reached in the “hot” phase of the process) through-
20 CO2 (kin.) 2
H O (equil.)
2
out the expansion. The lower temperatures that result during
CO (equil.)
15 2 expansion quench CO2 producing reactions, so that the low CO2
levels from earlier “hot” equilibria are preserved.
10
Interestingly, heat loss alone leads to a sufficiently fast tem-
CO2 (kin.)
5 CO2 (equil.)
perature decay, allowing this effect to be observed in the RCM,
CH (equil.)
4
even in absence of the expansion stroke. The expansion stroke lets
the mixture attain low temperatures much faster than heat loss
through the cylinder walls alone and therefore may present an op-
Temperature / K

2000 T (equil.)
tion to further improve CO2 conversions. However, when the RCM
1500 is operated in this way (RCEM mode), ignition timing becomes a
key issue (see also Fig. 3).
T (equil.)
1000 Figure 6 shows that CO2 conversion occurs on a timescale of
T (kin.) a few milliseconds. Within this timescale, a mixture with initially
T (kin.)
500 uniform temperature distribution will develop a non-uniform dis-
0 50 100 150 200 250 300 tribution due to heat transfer from the gas to the cylinder walls.
Time / ms Despite the fact that the simulation model does not take into ac-
Fig. 5. Temporal evolution of selected species (top) and temperature (bottom) dur- count effects of thermal stratification, the experiment and simula-
ing a RCM process, showing detailed kinetics (solid lines, “kin.”) and equilibrium tion show a good agreement in achieved CO2 conversion.
(dashed lines, “equil.”) simulations. Initial conditions correspond to the optimal val- At a first glance, this agreement would be surprising. There is
ues for CO2 initial mole fraction of 20%: T0 = 462 K, p0 = 1.0 bar, 20% CO2 , 39.15% a plausible explanation, however: We propose that for the studied
CH4 , 4.35% DME, 33.0% O2 , 3.6% Ar.
conditions, the detailed dynamics of combustion and heat release
during the in-cylinder process are not crucial for the final amount
0 20 40 60 80 80.5 81 81.5 82 100 150 200 of CO2 conversion. The important requirements for the conversion
45
are that
40 CH 4 (kin.)
CO (equil.) • the gas reaches a sufficiently high maximum temperature to be
35 H
2 able to overcome kinetic barriers and approach chemical equi-
Mole fractions / %

30 librium
CO (equil.) • the cool-down phase is fast enough to let the chemical state
25
freeze at a point of some high-temperature equilibrium
20 CO (kin.)
2
H O
2
These requirements can be achieved in different regions of the
15 CO2 (equil.) in-cylinder mixture (e.g., central or closer to walls), even if they
10
are affected by heat transfer to a different extent, and with differ-
CO2 (kin.) ent timing during the cycle. For instance, even near-wall regions,
5 CO (equil.)
2
CH (equil.)
which during an engine cycle first would remain relatively cold
4
by heat transfer, can later attain the high temperatures required
for efficient CO2 conversion by thermal contact to burned regions.
Temperature / K

2000 T (equil.)
They can auto-ignite by mixing with hot burned gas, and then fur-
ther increase their temperature by chemical reaction.
1500
5. Conclusions
1000

T (kin.)
500
0 20 40 60 80 80.5
Time / ms
Fig. 6. Temporal evolution of selected species (top) and temperature (bottom) dur-
ing a RCM process, showing detailed kinetics (solid lines, “kin.”) and equilibrium
(dashed lines, “equil.”) simulations. Same data as in Fig. 5, but with differently
scaled time axis, helping to better discern the different phases of the RCM process.
Center section: “hot” phase. Right section: “cool-down” phase.
of zero up to xCO2 ,eq = 7%. This is in accordance with the princi-
ple of Le Chatelier and Braun for the endothermal CO2 reforming
reaction CO2 + CH4  2 CO + 2 H2 . Also, the equilibrium mole
fraction of CO2 rises during the cool-down phase to approx. 16%,
which is close to its pre-compression value. Hence, no notable
CO2 conversion would result if the system always followed equi-
Our work shows that CO2 conversion by dry reforming yielding
CO and H2 can be carried out in piston engines. As a by-product,
81 81.5 82 100 150 200 water is produced. From this viewpoint, the engine can be seen
as a multi-purpose chemical converter, which is both capable of
producing power (in conventional combustion mode), but also able
to deliver useful products (syngas) from CO2 .
A combination of numerical simulation and optimization was
used to identify operating conditions that yield high conversions,
exceeding 50%; experiments in a rapid compression machine show
that these predictions are realistic, both with respect to the opti-
mal conditions and with respect to the achieved conversions. The
optimization approach was not only helpful to reduce the number
of experiments, but also to determine whether CO2 conversion in
an engine is possible in the first place.
One result of the optimization is that addition of oxygen to the
initial mixture of CH4 and CO2 helps improve the conversion by
194 H. Gossler, S. Drost and S. Porras et al. / Combustion and Flame 207 (2019) 186–195
providing the high temperatures (via exothermal chemical reac-
tions during oxidation of CH4 ) that overcome kinetic barriers of
the underlying elementary reactions, and that also shift the equi-
librium of the overall chemical reaction to the desired right side.
Despite the combustion of CH4 that then takes place, there is still
a net conversion of CO2 .
In fact, for the typical engine conditions studied here, ignition
is crucial for any significant CO2 conversions to occur. The methane
oxidation was a required aid that delivered the required tempera-
tures which were not attainable by compression alone in the par-
ticular RCM setup used here. How these temperatures are attained
does not play a role. If alternative methods for providing the high
temperatures (e.g., higher compression rations, higher initial tem-
peratures, etc.) would exist, then these would allow dry reforming
to proceed without the oxidation. In our study, we relied on auto-
ignition to achieve conversion. In a real engine, there are more
options to trigger ignition, for example, spark ignition. Although
RCEM mode more closely resembles real engine conditions with
its compression and expansion strokes, we found experimentally
that considering the simpler RCM mode (compression stroke only)
is sufficient to predict the CO2 conversion under engine conditions.
The dynamics of the conversion process can be regarded as a
two-step sequence: After compression and combustion, high tem-
peratures exceeding 2400 K result. This allows reactions to quickly
proceed to chemical equilibrium, which at these high temperatures
is on the CO/H2 side of the overall reaction equation. In the fol-
lowing cool down/expansion phase, internal energy and pressure
decrease rapidly. The chemistry in the combustion chamber first
follows the equilibrium for these transient thermodynamical con-
ditions, with a tendency to proceed back to the CH4 /CO2 side.
However, these reverse reactions are quenched at lower tempera-
tures (approx. 1500 K at the studied conditions), largely preserving
the favorable equilibrium from the previous “hot” phase. This is a
key phenomenon for the success of the conversion process.
The experimental setup used in this work had a compression
ratio of approximately 10, and the maximum initial temperature
was 462 K. These two points are the limiting factors to the maxi-
mum attainable temperature in the combustion chamber by work
alone. Future work will focus on whether CO2 can be converted
without combustion. Furthermore, the H2 /CO ratio of the syngas
mixture that exits the engine is quite low. For downstream conver-
sion processes the mixture would need to be enriched with H2 .
The conversion levels we found are encouraging for use of dry
reformation in technical applications. A real engine offers addi-
tional parameters to fine-tune the process, so that the achievable
conversions can likely be increased even more.
Acknowledgments
This research was supported by the Deutsche Forschungs-
gemeinschaft within the framework of the DFG research unit
FOR 1993 “Multi-functional conversion of chemical species and
energy” (projects SCHI647/3-2 and DE659/10-2). Hendrik Gossler
gratefully acknowledges financial support by the Karlsruhe House
of Young Scientists (KHYS) at KIT for a research visit at the Col-
orado School of Mines, USA. A cost-free license of DETCHEM TM
and financial support by Steinbeis GmbH & Co. KG für Technolo-
gietransfer (STZ 240 Reaktive Strömung) are gratefully acknowl-
edged.
Supplementary material
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.combustflame.2019.05.
031.
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