Article

pubs.acs.org/IECR

Methane Dry Reforming at High Temperature and Elevated Pressure:

Impact of Gas-Phase Reactions
Lea C. S. Kahle, Thomas Roussiere,, Lubow Maier, Karla Herrera Delgado, Guido Wasserscha,
Stephan A. Schunk, and Olaf Deutschmann*,,

Institute for Chemical Technology and Polymer Chemistry, and Institute for Catalysis Research and Technology, Karlsruhe
Institute of Technology (KIT), D-76131 Karlsruhe, Germany

hte Aktiengesellschaft, Kurpfalzring 104, D-69123 Heidelberg, Germany

*
S Supporting Information

ABSTRACT: Catalytic dry reforming over a platinum-based catalyst is described experimentally and numerically in a laboratory
pilot-plant ow reactor. The results reveal that coking in the upper part of the catalyst bed and at the entrance of the reactor
occurs, depending on the composition of the reaction mixture and the respective temperature. To a signicant extent, gas-phase
reactions play a role as being the cause for the observed coking behavior in the reforming of methane in the presence of carbon
dioxide at high temperatures of 11231273 K and at 20 bar. Hydrogen addition can inhibit coke formation better than water
addition. The reactor is modeled by a one-dimensional description of the reacting eld using elementary-step reaction
mechanisms of up to 4238 gas-phase reactions among 1034 species and 58 heterogeneous reactions among 8 gas-phase species
and 14 surface-adsorbed species. The study leads an optimized positioning of the catalyst in a technical reformer tube.

INTRODUCTION
Coke formation on catalysts and walls of the reactor pipes are
serious problems in many industrial reactors used, for instance,
for reforming, methanation, and cracking of hydrocarbons. Coke
can be a source for catalyst deactivation and, in severe cases, leads
to blocking of reactor tubes, as well as physical disintegration of
the catalyst support structure.14
Reforming of methane receives great interest both in research
and technology. In order to produce synthesis gas, a mixture of
CO and H2, conventional steam reforming, partial oxidation, and
autothermal reforming are currently used on an industrial
basis.5,6 Dry reforming, at least at elevated pressure levels beyond
10 bar, has not made it into commercialization. Still, among the
dierent ways of syngas production, methane dry reforming has
the advantage of a high potential carbon dioxide input. Another
interesting feature of dry reforming is that the achievable lower
H2/CO ratios can address downstream processes, which typically
are run in the H2/CO ratio range of 12. Such CO-rich syngas
can be a feedstock for the iron-based FischerTropsch to olens
synthesis, hydroformylation, and carbonylation, similar to acetic
acid synthesis.6 One of the main challenges in dry reforming of
methane, especially at elevated pressure, is the prevention of coke
formation. Coke can of course be formed by a variety of
reactions. Apart from the Boudouard reaction (carbon monoxide
disproportionation), another thermodynamically favored reac-
tion that results in coke buildup is the reaction of methane
decarbonation:
CH4 C + 2H 2 (pyrolysis of methane)
Therefore, dry reforming is carried out in the presence of
catalysts that also can help to inhibit carbon deposition. In
particular, Group VIII metal catalysts are of interest.1,68
Commercially, Ni catalysts are preferred, because of inherently
low cost, but the proneness to coking during dry reforming of
methane is still the major limitation, with regard to their use.7,9,10
Noble metals are known to be less prone to coke under
reforming conditions. Ross et al.11 investigated Pt/ZrO2 and Rh/
ZrO2 as the most active and stable catalysts of the Group VIII
metals. Bitter et al.12 identied Pt/ZrO2 as a catalyst with
satisfactory activity and stability for dry reforming of methane at
high temperatures. Also, Bradford and Vannice13 studied a
variety of supported Pt catalysts and examined their coking
resistance. Solymosi et al.14 were the rst to report the presence
of coke precursors in the gaseous phase; they detected the
formation of ethane and traces of ethylene under dry reforming
conditions over Pt/Al2O3.
At high temperatures and elevated pressure, noncatalytic
reactions in the gas phase play an essential role in the formation
of higher hydrocarbons. Methane can be converted directly to
hydrocarbons by thermally induced coupling reactions at high
temperatures.2,1519 The stepwise dehydrogenation of methane
can be explained by free-radical mechanisms.15 Zantho20 and
Chen21 simulated homogeneous gas-phase reactions between
methane and oxygen and achieved satisfactory agreement with
the experimental data on the products ethane and ethylene above
1000 K. Kaltschmitt et al.22 showed that signicant amounts of
C3C4 olens are formed in the gas phase at the reactor entrance,
resulting from the thermal cracking of isooctane. From these and
other literature results, it can be concluded that hydrocarbon
molecules may undergo either pure or oxygen-supported
pyrolysis with the formation of small hydrocarbon radicals.
The principal reaction pathway of the carbon deposition from
Received: April 2, 2013
Revised: July 16, 2013
Accepted: July 29, 2013
Published: July 29, 2013

2013 American Chemical Society 11920 dx.doi.org/10.1021/ie401048w | Ind. Eng. Chem. Res. 2013, 52, 1192011930
Industrial & Engineering Chemistry Research
methane was proposed by Becker and Huttinger23,24 and is
shown in Figure 1.
Figure 1. Model of pyrocarbon deposition from methane.49
Under fuel-rich conditions, the small radicals react, thus
leading to the formation of light hydrocarbons, particularly
acetylene (C2H2). Subsequently, large hydrocarbon molecules
containing a suciently large number of carbon atoms, e.g.,
aromatics (such as benzene (C6H6)) and polycyclic aromatic
hydrocarbons (PAHs) (such as naphthalene, anthracene, and
pyrene) are formed in a homogeneous phase.25,26 Carbon can be
deposited by means of surface reactions of these coke precursors
on a carbon surface by condensation of small hydrocarbons to
larger entities and assemblies (macro molecules) in the gas
phase.27 Various sets of elementary reactions are available in the
literature, which are suitable for modeling studies for
homogeneous gas-phase reactions for oxidation and pyrolysis
of hydrocarbons, which originate mainly from datasets available
from combustion kinetics. 2835 Optimization of reactor
conditions and design can be facilitated by the use of
computational models that incorporate elementary reaction
mechanisms.36
In this study, the catalytic dry reforming over a Pt-based
catalyst was studied experimentally in a test unit consisting of a 6-
fold reactor with dimensions similar to industrially used reformer
tubes. The coke formation at the entrance of the catalytic bed was
observed during the experiments at dierent carbon-to-steam
(C/S) ratios and temperatures. Figure 2 shows the comparison
Figure 2. Pictures taken of the removal of spent catalyst from the
reactor.
of the fresh and aged Pt-catalyst. After several hours of
experimental use, the coke deposition changes the appearance
of the light-gray powder to black. Particularly, the upper region of
the catalyst bed is covered by carbon deposits. This observation
was our motivation to examine the gas-phase reactions in
methane reforming to gain an understanding of coke formation
on catalysts and reactor tube walls initiated by homogeneous
reactions. In this study, rst, a catalytic reference case with a Pt-
supported catalyst is studied experimentally and numerically.
Then, focus is placed upon upstream gas-phase reactions, to
investigate coke deposition in the ow reactor. The experimental
and numerical setups are treated as a laboratory pilot plant for
catalytic dry reforming processes to study the potential
11921
Article
heterogeneous and homogeneous reactions, which will also be
relevant in reformer units of industrial scale. Homogenous
conversion of the feed gas and the formation of coke precursors
are investigated for dierent C/S ratios. In order to gain deeper
understanding, experiments are performed at a pressure of 20 bar
and within a temperature range of 11231273 K. Using
elementary-step gas-phase reaction mechanisms, species proles
and the product compositions are numerically predicted at
dierent temperatures and compared to the experimental data.
EXPERIMENTAL SETUP AND REACTOR DESIGN
In the laboratory pilot plant, the inside vertical ow reactor
consists of a ceramic tube, 12 mm in inner diameter and 1400
mm in length. Operating temperatures up to 1273 K and
pressures up to 40 bar can be applied. The reactor is surrounded
by a furnace 800 mm long to reach isothermal behavior in the
midsection of the reactor over a length of 300 mm, where the
catalyst is placed. The experimentally obtained temperature
proles along the reactor at three dierent operating temper-
atures of the quasi-isothermal zone are shown in Figure 3.
Figure 3. Experimentally obtained temperature proles along the
reactor at three temperatures of the quasi-isothermal zone: 1123 K, 1223
K, and 1273 K. These proles are used for the simulations.
The ceramic tube is studied without (noncatalytic case) and
with a Pt-supported catalyst (catalytic case). For the catalytic
tests, a 40-mL catalytic bed of Pt-containing pellets is placed in a
primary ceramic tube and maintained in the isothermal zone of
the furnace. Downstream of the catalyst zone, the catalyst bed is
supported on a ceramic frit. The porosity of the bed is = 0.35
and the catalytic area-to-volume ratio is 2800 m1. The catalytic
active surface was determined by CO-TPDs. The ratio between
the catalytically active and the geometrical surface area is
calculated to be 20, corresponding to a platinum dispersion of
8%; this value serves as a model parameter.
Upstream of the catalyst, a bed of corundum pellets is arranged
in order to reduce the residence time in the hot temperature
zone. The dierent experimental setups are shown in Figure 4.
The product stream is analyzed by gas chromatography (GC)
and Fourier transform infrared (FTIR) spectroscopy. The FTIR
analysis was used to quantify the amount of water in the gas
phase. The accuracy of the analyzed components (CH4, CO2,
CO, H2O, and H2) is 25 ppm on an absolute basis. Traces of
ethane, ethylene, propane, propylene, butane, and butylene can
be quantied on the ame ionization detector (FID) in the GC
system.
KINETIC TESTS
Catalytic Case. CH4 and CO2 conversions were measured
under reforming conditions for a molar CH4/CO2 ratio of unity
under dry conditions (absence of water in feed gas) and including
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Article

MODELING APPROACH
The blank as well as the lled reactor tube is modeled using a
one-dimensional (1-D) description of the reactive ow. Either a
plug ow or a 1-D packed-bed model is applied. For the
simulations, tools of the DETCHEM software package37
DETCHEMPLUG and DETCHEMPACKEDBEDare used. Ele-
mentary-step reaction mechanisms were coupled with the ow-
eld models, as described below.
The model assumes that (a) there is no variation in the
transverse direction, and (b) axial diusion of any quantity is
negligible, compared to the corresponding convective term.
Then, both plug ow and packed bed are dened by the following
equations:
Continuity equation:
Ng
d(u)
= av siMi
dz i=1 (1)

Species conservation:

Figure 4. Schematic diagrams of the noncatalytic blank reactor (left) d(Yi )

u i v si Mi = Mi(av si + i )
+ Ya
and the reactor lled with a bed of Pt-based catalyst (right) (z is the axial dz (2)
position along the reactor). All schematic diagrams are used for a plug-
ow simulation (values given in meters (m)). Conservation of energy:
Ng Ng + Ns
d(cpT )
10% H2O (Table 1) under isothermal conditions. An inlet total
uAc + i hiMi + sihiMiav
dz
volume ow of 1.86 104 m3/s is used, including 5% argon as
i=1 i=1

an internal standard, with a pressure of 20 bar. 4

Noncatalytic Case. Experiments without catalyst material
are conducted using dierent inlet gas mixtures that consist of
methane and carbon dioxide with variations of the partial
pressure of hydrogen and water. Three furnace temperatures
(1123, 1173, and 1223 K) are applied (see Table 1).
For each measurement, the same order of partial pressure
settings is carried out regarding the compositional variation of
the gas mixture entering the reactor. First, the composition of
CH4/CO2 = 1.0, including 40% of water, is applied. When steady
state is reached, the amount of steam is decreased in steps of 10%
down to dry conditions. The same procedure of partial pressure
adjustments is repeated for hydrogen as the co-feed, instead of
water. The measurements are performed in a blank reactor with
20 mL of corundum and with a corundum-lled upper section of
the reactor. An inlet total volume ow of 1.86 104 m3/s is used
inn reference to standard conditions (298.15 K, 1013.25 mbar).
All measurements in this study are carried out at a pressure of 20
bar.
= U (Tw Tz)
dh (3)
Equation of state:
pM = RT (4)
In the above equations, is the density, u the velocity, av the
catalytic area-to-volume ratio, the porosity, Ac the area of cross
section of the channel, Ng the number of gas-phase species, Ns the
number of surface species, si the molar rate of production of
species i by surface reaction, i the molar rate of production of
species i by the gas-phase reaction, Mi the molecular mass of
species i, Yi the mass fraction of species i, cp the specic heat
capacity of species i, hi the specic enthalpy of species i, U the
overall heat-transfer coecient, Tw the wall temperature, Tz the
gas temperature, p the pressure, and M the average molecular
weight.
In case of the plug-ow model, the porosity is = 1. The area-
to-volume ratio (av) denes the circumference to cross section of

Table 1. Inlet Compositions Given in Mole Fractionsa

X (CH4) X (CO2) X (H2O) X (H2) temperature [K] pressure [bar] volume ow [L/h] catalytic
1 0.475 0.475 1123 20 67 +
2 0.425 0.425 0.1 1123, 1173, 1223 20 67 +
3 0.425 0.425 0.1 1123, 1173, 1223 20 67
4 0.375 0.375 0.2 1123, 1173, 1223 20 67
5 0.325 0.325 0.3 1123, 1173, 1223 20 67
6 0.275 0.275 0.4 1123, 1173, 1223 20 67
7 0.425 0.425 0.1 1123, 1173, 1223 20 67
8 0.375 0.375 0.2 1123, 1173, 1223 20 67
9 0.325 0.325 0.3 1123, 1173, 1223 20 67
10 0.275 0.275 0.4 1123, 1173, 1223 20 67

a
5% argon is used as dilution gas.

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a plug-ow reactor. For circular channels this parameter is 2/r, CO + H 2O CO2 + H 2 R H 0 = 41.2 kJ/mol
where r is the radius of the channel. (11)
The main focus of the modeling is on the chemical source
0
terms i and si. In both cases, homogeneous and heterogeneous CH4 C + 2H 2 R H = 74.9 kJ/mol (12)
reactions, DETCHEM can handle elementary-step reaction
mechanisms. 2CO CO2 + C R H 0 = 172.4 kJ/mol (13)
The gas-phase reaction source term i is written as follows:
The reactions can be described by a recently developed
KG Ng

detailed surface reaction mechanism consisting of 58 reactions
i = ikkfk c j jk among 8 gas-phase and 12 surface-adsorbed species used. The
k=1 j=1 (5) mechanism suggests that methane adsorbs dissociatively on the
platinum surface. The rst step involves CH4 decomposition in
where KG is the sum of gas-phase reactions, Ng is the number of
which the cleavage of CH bonds at the catalytic surface leads up
gas-phase species, ik is the stoichiometric coecient, and cj are
to adsorbed carbon and hydrogen. Further interaction of
the species concentrations.
adsorbed carbon species CHx (x = 0, 1, 2, 3) with adsorbed
The surface species equation si can be written in an analogous
atomic oxygen, formed from CO2 or H2O decomposition,
way as a sum of KR reactions among Ng gas-phase and Ns surface
produces CO. Adsorbed CO2 can also react catalytically by the
species:
reverse water-gas shift reaction to CO and H2O via an adsorbed
KR Ng + Ns COOH intermediate. The formed H2O can, in turn, react with

si = ikkfk c j jk methane and hydrocarbon radicals.
k=1 j=1 (6) The dry reforming process on the Pt catalyst surface is
described as follows:
kfk is the rate coecient, for which a modied Arrhenius
expression is applied for surface reactions: CH4 + (5 x)Pt(s) CHx(s) + CH4 + (4 x)H(s)
Eak Ns (14)
ik i
exp
k
k fk = Ak T exp
RT i=1 RT (7) CO2 (s) + H(s) COOH(s) + Pt(s)
Here, the parameter ik is used to dene coverage-dependent CO(s) + OH(s) (15)
activation energies. For adsorption reactions, the rate coecient
is described through sticking coecients: CO2 (s) + C(s) 2CO(s) (16)

Si0 RT C(s) + O(s) CO(s) + Pt(s) (17)

k fk =
2Mi (8) C(s) + OH(s) CO(s) + H(s) (18)
is the surface site density that describes the maximum surface
concentration of adsorbed species, the number of adsorbing CH4 + (4 x)OH(s) + Pt(s)
sites, and S0i the sticking coecient. The platinum surface site CHx(s) + CH4 + (4 x)H2O(s)
density, using a value of = 2.72 105 mol/m2, is dened from (19)
the number of surface Pt atoms in one monolayer (1 ML = 1.67
1015 atoms/cm2) estimated for Pt(111) surface with a CH4 + (4 x)O(s) + Pt(s)
rectangular unit cell. CHx(s) + CH4 + (4 x)OH(s) (20)
The system of equations is solved using the dierential
algebraic equation solver LIMEX.37 OH(s) + H(s) H 2O(s) + Pt(s) (21)
When provided with a set of input conditions, the program
solves the 1D equations and outputs the velocity, temperature, [Note: In these equations, Pt(s) is a free platinum side; (s)
and mole fraction of each species along the centerline of the denotes adsorbed species.]
reactor. Inlet and boundary conditions of the simulation are Coke formation is caused by methane decomposition and the
taken from the experiment. Boudouard reaction (CO disproportionation). Carbon may be

gasied by steam or oxygen, as well as by an excess of hydrogen.

REACTION MECHANISM Noncatalytic Case. In order to avoid incorrect conclusions
Catalytic Case. Especially for a description of the inuence of due to uncertainties of one individual reaction mechanism, three
water on dry reforming, a surface reaction mechanism was models are used to model the homogeneous chemical conversion
developed for combined dry/steam reforming over platinum. in the gas phase. Aromatic hydrocarbons (AHs) and polycyclic
The detailed reaction mechanism makes it possible to describe aromatic hydrocarbons (PAHs) are included to accentuate
the main global processes in the system CH4/CO2/H2O as dry eective coke precursors. No adjustments were made to the
and steam reforming reactions, water-gas shift reaction, carbon kinetic parameters of any elementary chemical reaction.
formation reactions, methane cracking, and gasication of carbon Gas-Phase Reaction Mechanism 1 (M1). The mechanism
by steam or oxygen. is based on the well-known detailed scheme developed for
isooctane combustion at Lawrence Livermore National Labo-
CH4 + CO2 2CO + 2H 2 R H 0 = 247 kJ/mol ratory (LLNL),38,39 which consists of 4238 reactions among
(9) 1034 species, most of which are reversible. This mechanism was
0
later coupled with a detailed toluene scheme by Dagaut et al.,40
CH4 + H 2O CO + 3H 2 R H = 206 kJ/mol which is discussed by Andrae et al.41 The toluene mechanism was
(10) validated by experiments on toluene oxidation in an atmospheric
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jet-stirred reactor, by the simulation of benzene oxidation from

0.46 atm to 10 atm, the ignition of benzeneoxygenargon
mixtures, and the combustion of benzene in ames. The merged
mechanism consisted of 8927 reactions among 1082 species.
Gas-Phase Reaction Mechanism 2 (M2). This second
mechanism from the Golovitchev group42 consists of 690
reactions among 130 species. Species from C1 through C8 are
considered, and the mechanism is applicable for a wide range of
conditions (6401760 K; 155 bar).43,44
Gas-Phase Reaction Mechanism 3 (M3). The third
mechanism was applied as well. It is derived from various
literature sources based on the work by the Dean group,45,46 and
eventually led to 3611 reactions among 420 species, including the
reaction pathway for aromatic and some polyaromatic hydro-
carbons, such as naphthalene, anthracene, and pyrene.22
For the simulation of noncatalytic reforming of methane,
mechanism M2 is mainly used, because of its short processing
time.
More-detailed descriptions of, e.g., the formation of
polyaromatic precursors or C3/C4 olens can be achieved
through the use of mechanisms M1 and M3.

RESULTS AND DISCUSSION

Catalytic Case. Methane and CO2 conversion under dry
conditions and including 10% H2O is modeled at dierent
temperatures and compared to the experimental data. Gas-phase
simulations, calculated with reaction mechanism M1, are
included upstream of the catalytic zone. As shown in Figures
5a and 5b, the conversions are close to the thermodynamic
equilibrium. The methane conversion is lower than the CO2
conversion, although they are fed into the system with a molar
ratio of 1:1. This dierence indicates the occurrence of the
reserve water-gas shift (rWGS) reaction,
CO2 + H 2 CO + H 2O
The H2/CO molar ratios that are less than unity are also
explained by the rWGS (see Figure 5c).
Figure 6 shows the numerical product proles along the
catalytic bed at 1123 K and under dry conditions. Catalytic
conversion takes place and not only the major products H2 and
CO but also H2O are formed. The rapid formation of H2O and
CO and the slower formation of H2 can be related to the rWGS
reaction again. Rostrup-Nielson et al. have also shown that the
WGS reaction is extremely rapid under typical methane
reforming conditions.47
The computed surface coverage along the reactor length of the
catalyst shows a surface carbon concentration at the catalytic
entrance zone that decreases with reactor length (see Figure 6,
right). The experiments conrm this behavior. Under dry
reforming conditions, coke is observed upstream of the catalytic
zone and at the entrance of the catalyst bed, even at 1123 K
(Figure 2). There is less coke formation within the catalyst
section and downstream of the catalyst section, because of the
lower concentration of methane in the gas phase, which is mostly
converted on the catalyst surface. Since gas-phase reactions can
take place in front of the catalytic zone, coke can be formed by
homogeneous pyrolysis as well. It is supposed that coke is not
only formed catalytically on the surface but also from the gas
phase. It should be noted that coke formation and buildup is a
transient process in real catalytic systems, including many
carbonaceous atomic layers. The growth of a coke layer is not
implemented in the present surface reaction model, i.e., the
simulations can only compute a maximum of one monolayer of
11924
Figure 5. Catalytic conversion of (a) CH4, (b) CO2, and (c) the H2/CO
molar ratio, all as a function of temperature for CH4/CO2 = 1/1 under
dry conditions; 20 bar; 5% Ar as dilution. Symbols = experiment at 1123
K, lines = simulation, dashed lines = equilibrium composition at given
temperature.
carbon on the surface. Therefore, the model has shown where
coking take place in the reactor instead of the amount of coke
deposition. Subsequently, the catalytic eect of carbon to further
coke deposition is not considered in the model and the time of
the reactor breakdown due to blockages cannot be predicted.
To avoid coke deposition in the experimental reactor setup,
10% steam was included to shift the equilibrium and allow for less
coke formation. The experiments were carried out at temper-
atures higher than those under totally dry reforming
conditions. Figure 7 shows the calculated and measured CH4
and CO2 conversions, as well as the resulting H2/CO ratios. The
same trends in conversion and H2/CO ratio, as discussed with
regard to Figure 5, are observed.
Methane and CO2 are not fully converted at the temperatures
studied. Consequently, gas-phase reactions may also occur
downstream of the catalyst bed. The remaining methane may be
converted by cracking and coupling reactions that produce
carbon precursors downstream of the catalytic zone. However,
little coke deposition was observed. The model does not predict
coke formation downstream the catalyst bed in the gas phase,
which can be understood being due to high hydrogen and water
concentrations and a lower methane concentration in the
downstream gas ow.
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Industrial & Engineering Chemistry Research
Figure 6. Computed product distribution in the catalyst bed and numerically predicted surface coverage of adsorbed species as a function of axial
position along the catalytic bed of the reactor for dry reforming conditions at 1123 K and 20 bar; CH4/CO2/Ar = 0.475/0.475/0.05.
Figure 7. Catalytic conversion of CH4 and CO2 and H2/CO product
ratio as a function of temperature for CH4/CO2 = 1/1 including 10%
H2O; symbols = experiment, lines = simulation.
Noncatalytic Case. At high temperatures and high pressure,
chemical reactions do not exclusively occur on the catalyst
surface but also in the gaseous ow. Therefore, homogeneous
conversion was computed for a blank reactor as a rst step
toward a better understanding of the role of gas-phase reactions.
The experimentally obtained temperature proles as shown in
Figure 3 are used for the simulations (see Figure 8). As expected,
Figure 8. Computed mole fractions as a function of axial position along
the reactor; blank reactor tube due to homogeneous conversions in the
gas phase only, 10% H2, CH4/CO2 = 1; 20 bar, mechanism M2; the
cross-hatched region shows the position of the demonstrated catalyst
bed.
the conversion of the reactants increases with rising temper-
atures. Signicant gas-phase reactions begin to occur in the
section upstream of the catalytic bed. In experiments, severe coke
formation has been observed in front of the catalyst.
In Figure 9, the conversions of CH4 and CO2 are shown at the
outlet of the empty reactor tube. The agreement between
computed and measured conversion for all temperatures implies
that only gas-phase reactions are responsible for the conversion
11925
Article
and that mechanism M2, in principle, is able to treat the problem.
Figure 10 shows the species mole fractions along the reactor
length. Unsaturated light hydrocarbons are formed using all three
reaction mechanisms (M1M3), even though there are
signicant quantitative dierences. The formation of products
in the gas phase signicantly starts at a reactor length of 0.3 m,
where the wall temperature is higher than 1150 K. This behavior
indicates that the formation of coke precursors is mainly
leveraged by the temperature. Downstream, at z = 1 m, the wall
temperature decreases and the mole fractions of the byproducts
remain constant or even decrease, except for ethane (C2H6). It is
assumed that C2H6 increases due to ongoing coupling processes.
The decrease of C2H4 and C2H2 at higher temperatures can be
explained by formation of aromatics from acetylene and ethylene,
which is shown in Figure 11. Signicant amounts of C3C4
olens (1,2-propadiene, propene, propyne, n-butene (1-butene,
2-butene), isobutene, and 1,3-butadiene) are formed as a result of
methane pyrolysis and coupling of hydrocarbons. Ongoing
coupling processes further downstream form benzene, for
instance, by dimerization of acetylene and vinylacetylene.18
Furthermore, a combination of acetylene and AHs may lead to
the formation of PAHs, such as naphthalene, anthracene, and
pyrene, all of which are potential precursors for carbon formation
and deposition.
Norinaga et al.48 showed the chemical kinetics of pyrolysis of
ethylene and under conditions relevant for the chemical vapor
deposition of pyrolytic carbon at 1173 K. Their kinetic model
predicted the proles of the major pyrolysis products well.
Higher temperatures favor H-abstraction, thus enhancing the
formation of the highly unsaturated hydrocarbons acetylene,
diacetylene, and benzene. The behavior observed in our
reforming reactor is in agreement with those pyrolysis studies.
Figure 12 reveals the production of byproducts as a function of
temperature in simulation and experiment. The higher the
temperature, the higher is the mole fraction of byproducts. The
simulation with mechanism M2 predicts more C2H6 and less
C2H4 than the other two mechanisms. These characteristics of
the mechanisms are likely to be related to the occurrence of less
hydrocarbon species and missing coupling reactions in the
simpler mechanism. At 1173 K, mechanisms M1 and M3 predict
the experiment well, in contrast to the prediction at 1223 K,
where all mechanisms predict too little ethane.
VARYING THE CH4/CO2 RATIO
Certainly, the formation of coke precursors and the occurrence of
carbon deposition are dependent not only on the reactor
temperature but also on the gas inlet composition, e.g., the CH4/
CO2 inlet ratio (see Figure 13). Increasing CH4 inlet
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Figure 9. Computational conversion of CH4 and CO2 at the end of the reactor tube; blank reactor tube, 10% H2, CH4/CO2 = 1; 20 bar, mechanism M2.
Figure 10. Species mole fraction in the quasi-isothermal temperature
zone (1223 K) of the reactor; blank reactor tube, 10% H2, CH4/CO2 =
1; 20 bar (case 3 in Table 1).
Figure 11. Numerically predicted proles of coke precursors as a
function of axial position along the reactor; blank reactor tube, CH4/
CO2/H2 = 0.425/0.425/0.1, quasi-isothermal zone 1223 K, 20 bar,
mechanism M1.
Figure 12. Byproduct formation as a function of temperature for CH4/
CO2/H2/Ar = 0.325/0.325/0.3/0.05; blank reactor tube; symbols =
experiment, lines = simulation (dotted line = mechanism M1, dashed
line = mechanism M2, solid line = mechanism M3).
concentration leads to more aromatics, such as C6H6. The
concentration of ethylene and acetylene is found to decrease
slightly with increasing CH4:CO2 ratio. Cracking of methane and
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Figure 13. Numerical coke precursor distribution for varying CH4/CO2
ratios at 1173 K at the end of the empty reactor tube (mechanism M2).
ongoing coupling reactions of hydrocarbons may be the sensitive
reactions leading to coke deposition. This indicates an inuence
of the partial pressure of methane on the formation of coke
precursors.
INFLUENCE OF H2 ADDITION
The addition of hydrogen inhibits the pyrolysis of methane and
hydrocarbons in general, at least to a certain extent, therby
limiting the deposition rates of carbon from hydrocarbons.49,50
The strength of the inhibiting eect for coke precursor
formation depends largely on the carbon/hydrogen ratio and the
molecular structure of the hydrocarbons. Carbon deposition
from highly unsaturated, linear hydrocarbons, such as acetylene,
is less inhibited than that from less-unsaturated hydrocarbons,
such as ethane.50 The formation and growth of hydrocarbons23
and, especially, the formation of carbon from aromatic
hydrocarbons are strongly inhibited by the addition of
hydrogen.50,51 The simulations of the homogeneous conversion
of dry reforming of CH4 show the same trends in Figure 14.
The higher the additional hydrogen partial pressure in the gas
phase, the less coke precursors are formed. These experimental
observations can be predicted by simulation with all three models
(Figure 15).
INFLUENCE OF H2O ADDITION
Water is also known to be an inhibitor of carbon deposition from
hydrocarbons. However, experiments under dry reforming
conditions with water at 1223 K could not be carried out, because
of massive coking in the reactor system. Even at 1123 K, coke
formation in the reactor tube was experimentally observed. The
illustrated simulation data in Figure 16 show the inuence of
H2O on the formation of C6H6. At 1223 K, the concentration of
benzene is predicted to be 3000 ppm for 40% water and 7000
ppm for 10% water addition. Even at 1173 K, a concentration of
dx.doi.org/10.1021/ie401048w | Ind. Eng. Chem. Res. 2013, 52, 1192011930
Industrial & Engineering Chemistry Research
Figure 14. Numerical ethane (left) and benzene (right) concentrations for varying H2 inlet concentrations at dierent temperatures at the end of the
empty reactor tube, mechanism M2.
Figure 15. Product distribution as a function of temperature for CH4/
CO2 = 1/1 at dierent hydrogen concentrations of the empty ow
reactor; symbols = experiment, lines = simulation.
Figure 16. Numerical C6H6 mole fraction as a function of temperature
for CH4/CO2 = 1/1 at dierent H2O concentrations of the empty ow
reactor; mechanism M2.
5002000 ppm benzene is observed. These high amounts of
benzene will surely lead to coke deposition.
Comparing the inuence of hydrogen addition versus H2O
addition, a much higher conversion of methane is observed for
water addition (see Figure 17). This behavior is explained by the
fact that hydrogen inhibits the rate of methane cracking stronger
than water. The reaction ow analysis in Figure 18 shows two
parallel pathways to form methyl:
CH4 H CH3 (pathway (1))
CH4 + OH CH3 + H 2O
(pathway (2))
The addition of 10% water does not aect pathway (1) but
pathway (2) decreases by 26%. Because of the addition of 10%
hydrogen, pathway (1) shifts the equilibrium and passes in the
direction of the methane formation. Methyl is formed totally via
pathway (2). The next step to form carbon precursors is a
coupling reaction of two methyl radicals to form ethane (C2H6),
which further reacts to form ethylene (C2H5) via H-separation.
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Figure 17. Numerical reactant conversion, as a function of axial position
along the reactor; blank ceramic tube, CH4/CO2 = 1, 10% H2 (10%
H2O), 1223 K, mechanism M2.
Figure 18. Alternated reaction pathway analysis (mechanism M2) of the
conversion of methane at 1173 K; 20 bar; CH4/CO2 = 1 for totally dry
reforming conditions (DR) and with 10% water and 10% hydrogen
addition, respectively. The pathways lead to coke precursor formation
from methane.
This step decreases by 11% because of water addition and by 74%
because of hydrogen addition.
To summarize, both additives, water and hydrogen, decrease
the conversion of methane, with regard to totally dry conditions.
Nevertheless, hydrogen has a stronger eect than water.
The conversions of CH4 and CO2 with additional 10% water at
the end of the empty reactor tube in the experiment and the
simulation are given in Table 2. The addition of water slightly
decreases the formation of coke precursors, with regard to totally
dry conditions. The simulations are in agreement with the
experimentally observed methane and CO2 conversions.
Figure 19 shows the mole fraction of the products along the
reactor length, simulated with mechanism M2. In the case of
steam addition, signicant amounts of C2H4 are formed around z
= 0.5 m. The isothermal zone starts at this position. Usually, the
initial part of the catalyst bed would be placed here in a laboratory
dx.doi.org/10.1021/ie401048w | Ind. Eng. Chem. Res. 2013, 52, 1192011930
Industrial & Engineering Chemistry Research
Table 2. Comparison of Experimental and Simulated
Conversions of Methane and Carbon Dioxide Including 10%
H2O at Two Dierent Temperatures
1123 K 1173 K
experiment simulation experiment simulation
CH4 amount [%] 0.5 1.4 10 12
CO2 amount [%] 0 0.1 4.3 5 as in the hydrogen case. This infers that water does not inhibit
Figure 19. Numerical product proles as a function of axial position
along the reactor; blank reactor tube, 10% H2 (H2O), CH4/CO2 = 1; 20
bar, mechanism M2.
and industrial reactor. In that case, a high amount of C2-species
would already enter the bed and support the formation of
carbonaceous layers and coke on the catalytic surface.
OPTIMIZATION OF THE REACTOR SETUP
The results discussed above are used for the optimization of the
design of the reactor, such as position and length of catalytic bed
and the operating conditions, such as the feed composition. One
of the key design variables is the residence time of the gases in the
noncatalytic section of the reactor, i.e., the entrance zone, and the
temperature prole in that zone. Since the diameter and the
length of the reactor were xed because of design reasons, the
residence time can be varied by choosing the porosity and the
amount of insert material inside the reactor.
Furthermore, fewer precursors will form at low temperatures
and with an additional catalyst, especially in the nonisothermal
front-zone of the reactor. Large homogeneous sections and long
residence times at high temperatures lead to gas-phase reactions
and precursor formation. Hence, a compromise must be made
between saving catalyst material and increase of coke precursors
and carbon formation due to gas-phase reactions.
CONCLUSION
Catalytic dry reforming of methane at high temperatures of
11231223 K and a pressure of 20 bar was studied in order to
derive a model for coke formation. Homogeneous reactions play
a major role, being the cause of precursor-induced coke
deposition in the catalyst bed and in the preheating zone
upstream of the catalyst bed. Conversion of CH4 and CO2 also
occurs in the gaseous phas,e which could be conrmed by pure
gas-phase experiments and numerical investigations. From a
mechanistic viewpoint, a signicant extent of hydrocarbons is
initially formed by methane dehydrogenation and further
coupling reactions of hydrocarbon radicals, which could be
numerically simulated using detailed gas-phase kinetic models. It
is shown numerically and experimentally that CO2 and CH4
conversion increase with rising temperature; therefore, the mole
fraction of the hydrocarbons rises signicantly above 1223 K. In
contrast, hydrogen inhibits the formation of coke precursors.
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This study also reveals that the strength of the inhibition depends
on the carbon/hydrogen ratio and the molecular structure of the
hydrocarbons.
Experiments including dierent amounts of water show coking
on the reactor tube wall. Homogeneous numerical product
distributions under dry reforming conditions including water
predict a faster increase of the precursors at the isothermal zone
coke precursor formation in the gas phase strongly and, as a
consequence, coke deposition. The inhibition eect of H2O
could be clearly shown in the presence of a catalyst.
The impact of gas-phase reactions on the overall performance
in catalytic reforming of hydrocarbons can support the design
and optimization of technical reformers. Long residence times in
the noncatalytic reactor part lead to a signicant formation of
coke precursors and, therefore, to coke deposition in the reactor.
The study gives background data that allow optimum positioning
of the catalyst bed in a laboratory or industrially used reactor and
give indications why certain regimes of temperature, pressure,
and reactive gas composition pose high challenges for catalyst
performance for dry reforming on a technical scale. Therefore,
this study can aid in reactor design and the choice of reaction
conditions in order to limit coke deposition.
*
ASSOCIATED CONTENT
S Supporting Information
The surface reaction mechanism that was used for the catalytic
simulations but not shown. This information is available free of
charge via the Internet at http://pubs.acs.org/.
AUTHOR INFORMATION
Corresponding Author
*Fax: 0049 721 608 44805. E-mail: deutschmann@kit.edu.
Author Contributions
The manuscript was written through contributions of all authors.
All authors have given approval to the nal version of the
manuscript.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
The authors are grateful for the nancial support of the German
Federal Ministry of Economics and Technology (No. FKZ
0327856A) and our project partners BASF, Linde AG, hte AG,
Technische Universitat Munchen, and Universitat Leipzig for
fruitful discussions on the dry reforming of methane. L.K. deeply
values Dr. Steen Tischers input on simulations pertaining to
DETCHEM.
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