Ind. Eng. Chem. Res.

2002, 41, 1425-1435 1425

Plasma Pyrolysis of Methane to Hydrogen and Carbon Black

James R. Fincke,* Raymond P. Anderson, Timothy A. Hyde, and Brent A. Detering
Idaho National Engineering and Environmental Laboratory, P.O. Box 1625, Idaho Falls, Idaho 83415-2211

The plasma-driven gas-phase thermal decomposition of methane yielding hydrogen and solid-
phase carbon has been suggested as an environmentally friendly alternative to conventional
methods of producing hydrogen from natural gas. The advantage of the process is that hydrogen
is obtained directly from methane without producing CO2 as a byproduct. The process was
experimentally examined using a modified version of a dc plasma reactor originally developed
for the conversion of methane to acetylene. Carbon yields of 30%, a factor of 6 increase, with a
corresponding decrease in acetylene yield were obtained by simply increasing the residence or
reaction time. A detailed kinetic model that includes the reaction mechanisms resulting in the
formation of acetylene and heavier hydrocarbons through benzene is described. A model for
solid carbon nucleation and growth is included. The model is compared to experimental results
and is used to examine process optimization.

1. Introduction

The most common conventional method of obtaining

hydrogen from natural gas is by steam reforming
followed by the water gas shift reaction,1,2 resulting in
the overall reaction CH4 + 2H2O f CO2 + 4H2. In this
process, half of the hydrogen produced originates from
the hydrocarbon and the other half comes from water.
Steam reforming is applicable to hydrocarbons other
than methane; however, feedstock heavier than naphtha
cannot be used.1 Hydrogen is also routinely produced
from natural gas by partial oxidation (CH4 + 1/2O2 f
CO + 2H2), with the advantage that heavier hydrocar-
bons such as residual oil can be processed. However,
the overall efficiency of the process (50%) is less than Figure 1. Simplified equilibrium diagram for 1 mol of methane.
that of steam-methane reforming (65-75%), and a
source of pure oxygen is required.1,2 The technologies such as ethylene are also used. The thermal cracking
for hydrogen production from natural gas are mature process can use less costly methane directly.
and widely practiced on a large scale for the production The equilibrium dissociation of methane begins at
of methanol, ammonia, and hydrogen for petrochemical around 500 C and is complete by 1000 C. The equi-
plants.1,2 librium products between about 1000 and 2500 C are
solid carbon and molecular hydrogen (Figure 1). As-
Both the steam reforming and partial oxidation
suming that the product stream is at 1000 C and that
processes have the drawback that large quantities of
the process is 100% thermally efficient, the specific
CO2 are produced. If the goal is to minimize the
energy requirement (SER) corresponding to Figure 1 is
emission of greenhouse gases, the CO2 byproduct must
0.933 (kWh)/(Nm3H2). Thermal inefficiencies increase
be captured and sequestered, increasing the cost of the
this number, as does an increase in the temperature of
hydrogen produced. The direct thermal decomposition,
the product stream and the use of additional gases;
or cracking, of methane to produce hydrogen and solid-
process heat recovery decreases it. Recovery of enough
phase carbon is potentially an environmentally friendly
product stream energy to preheat the incoming feed-
alternative. Because the cracking process is highly
stock to 400 C lowers the SER to 0.83 (kWh)/(Nm3
endothermic, the energy source must also be efficient
H2). If decomposition occurs on a solid (perhaps cata-
with low CO2 emissions or renewable with essentially
lytic) surface, lower value coke is formed rather than
zero net emission to maximize the net greenhouse gas
high-quality, generally higher value, carbon black. To
reduction. It is possible to realize a significant net
produce high-quality carbon black, the decomposition
reduction in CO2 emission using conventional, fossil
and soot formation process preferably occurs in the gas
generated, electrical power.3 The thermal cracking
phase. In practice, the rate of formation of unsaturated
process can, in principle, coproduce two valuable prod-
hydrocarbons, primarily acetylene, ethylene, and ben-
ucts, hydrogen and carbon black, improving process
zene, is much faster than the complete decomposition
economics.3 Commercially, carbon black is often ob-
to hydrogen and the subsequent formation of solid
tained by the partial oxidation or thermal decomposition carbon soot, and thermodynamics alone cannot ad-
of acetylene, although other hydrocarbon feedstocks equately describe soot formation. It is inherently a
kinetically limited process composed of a nucleation step
* Corresponding author. Fax: (208) 526-2031. E-mail: JF1@ followed by mass growth. It is known that the formation
inel.gov. of polycyclic aromatic hydrocarbons (PAHs) is a major
10.1021/ie010722e CCC: $22.00 2002 American Chemical Society
Published on Web 02/16/2002
1426 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002
Figure 2. Simplified equilibrium diagram for 1 mol of methane
where the solid phase of carbon is not included as a species.
nucleation mechanism for soot4 and that the formation
of benzene is a precursor to the formation of higher
aromatics. The PAHs increase in molecular weight by
acetylene addition and become hydrogen-deficient
through hydrogen abstraction by atomic hydrogen,
leading to the formation of primary soot particles.
Primary soot particles continue to grow via the decom-
position of acetylene on their surfaces. If the product
stream is rapidly cooled to temperatures where the
products are stable, before soot has time to nucleate and
grow, the composition is frozen and the equilibrium
condition of Figure 1 is never attained. A second,
modified equilibrium diagram excluding solid carbon as
a product is shown in Figure 2. The result is the
formation of acetylene with a maximum theoretical yield
of 98.5% at a temperature of around 1875 C. This
process has been exploited for the production of acety-
lene from methane (see, for example, refs 5 and 6 and
references therein) with the source of energy being an
electrical arc discharge or plasma. Electrically generated
plasmas are the preferred method of introducing large
amounts of energy into a hydrocarbon gas stream at
high temperature while avoiding coke formation on
surfaces and the limitations inherent in heat exchanger
materials.
Several authors have reported the plasma-driven
thermal decomposition of methane and other light
hydrocarbons. In general, the goal was to produce
carbon black utilizing methane as a source of carbon
directly rather than more expensive acetylene or eth-
ylene with hydrogen as a secondary product. Bolouri and
Amouroux7 describe the production of carbon (acetylene)
black by directly processing methane in an RF thermal
plasma. They demonstrated a methane conversion ef-
ficiency approaching 100% and carbon yields as high
as 45%. Most of the remainder of the carbon appeared
as acetylene. In a series of papers, Fulcheri and co-
workers8-11 describe a novel three-phase alternating
Figure 3. Schematic of torch, injector, and reactor; flow is left to right.
current plasma process for the production of carbon
black from methane. They reported carbon yields of 50%
for methane10 and 60% for ethylene11 feeds. Kaverner
Engineering has also reported the coproduction of
hydrogen and carbon black from methane with high
yield, reported to be in the 90-100% range with a
specific energy requirement of 1.1 (kWh)/(Nm3H2),
although detailed process information in the available
literature are lacking and a complete analysis of the
product stream is apparently unpublished.3,12,13 Other
information suggests that the process operates at a
maximum temperature of 1600 C14 and at a pressure
between 2 and 5 atm.15 It is unclear if the high carbon
yield reported is for single pass operation, if uncon-
verted products or products other than hydrogen and
solid carbon are recirculated and reprocessed, or if
process heat recovery is used.
Our goal is to better understand the details of the
chemistry of the plasma thermal conversion of methane
to hydrogen and solid-phase carbon. Furthermore, we
wish to examine the influence of various parameters
(temperature, pressure, residence time, etc.) on process
performance. The challenge is to maximize the yield of
solid carbon and hydrogen while minimizing energy
consumption and gaseous species other that hydrogen.
Our approach is the development of a reasonably
detailed kinetic model that is validated by comparison
to experimental results. The kinetic model includes the
reaction mechanisms resulting in the formation of
acetylene and heavier hydrocarbons through benzene
and solid carbon nucleation and growth. The model is
benchmarked against experimental results and is used
to examine reaction timescales and optimization of
carbon and hydrogen yields.
2. Experimental Results
The test apparatus used was originally designed to
investigate the plasma thermal conversion of methane
to acetylene.5 The original configuration includes an
efficient four-port injector and a carbon-lined reactor
section that provides residence time for reactions to take
place. The original geometry is given in Figure 3. The
apparatus was later modified to increase residence time
by replacing the 12.7 cm reactor section with a 61 cm
reactor section of the same diameter. The carbon liner
was retained in an attempt to minimize thermal losses
to the water-cooled reactor shell. The measured thermal
efficiency of the plasma torch was between 60% and
80%, depending on the gas mixture and flow rates. The
dc plasma torch that is used will not operate for
extended periods of time on pure hydrogen without
severe anode erosion; hence, all test data is acquired
using at least some Ar plasma gas. The processing of
 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002 1427

Table 1. Experimental Parameters Table 2. Chemical Species Considered

Test I Test II species no. species name CHEMKIN symbol
Test Parameters 1 Ar argon AR
pressure (kPa) 85 77.1 2 H2 diatomic hydrogen H2
Ar (slm) 140 140 3 H atomic hydrogen H
H2 (slm) 100 30 4 C carbon (gas) C
net power (kW) 60 60 5 C(s) carbon (graphite) C(S)
avg plasma temperature (K) 6200 11000 6 C2 diatomic carbon C2
reactor length (cm) 12.7 61 7 CH4 methane CH4
CH4 (slm) 120.8 90 8 CH3 methyl CH3
Measured Energy Loss (W/m2) 9 CH2 methylene CH2
10 CH methylidyne CH
injector ring 5.95 106 not present
11 C 2H ethynyl C2H
reactor 1.73 105 2.56 105
12 C2H2 acetylene C2H2
downstream contraction 6.64 105 4.52 105
13 C2H3 vinyl radical C2H3
downstream piping 2.0 105 5.83 104
14 C2H4 ethylene C2H4
Measured Process Performance 15 C2H5 ethyl radical C2H5
conversion efficiency (%) 99.1 99.4 16 C2H6 ethane C2H6
carbon yield (%) 4.67 30.5 17 C3H2 C3H2 radical C3H2
C2H2 yield (%) 85.5 47.5 18 C3H3 2-propynl H2CCCH
C6H6 yield (%) 8.1 13.9 19 a-C3H4 allene C3H4
C2H4 yield (%) 1.7 6.7 20 p-C3H4 methylacetylene C3H4P
other hydrocarbons yield (%) 1.0 1.4 (propyne)
Inlet Boundary Condition 21 C3H5 prop-1-enyl CH2CHCH2
temperature (K) 3450 3900 22 C4H4 vinyl acetylene CH2CHCCH
velocity (m/s) 531.25 44.63 23 n-C4H5 CH2CHCHCH
[Ar] (mole fraction) 0.3613 0.5070 24 i-C4H5 CH2CHCCH2
[H2] (mole fraction) 0.1888 0.0510 25 1,3-C4H6 trans-1,3-butadiene CH2CHCHCH2
[H] (mole fraction) 0.1382 0.1160 26 C4H8 t-2-butene C4H8
[CH4] (mole fraction) 0.3117 0.3260 27 C6H5 phenyl C6H5
28 C6H6 benzene C6H6
29 Csoot(s) carbon (graphite) C(S)
methane directly in the discharge is precluded by the
severe erosion of the tungsten cathode via the formation data sets utilizes the original (short) reactor section used
of volatile tungsten carbides. The power to the plasma in our previous acetylene work (Test I), and the second
torch was adjusted to give a constant 60 kW deposited utilizes the 61 cm reactor section (Test II). In Test II,
in the plasma gas. Because the torch voltage is deter- the methane injector ring was removed, and the injec-
mined by the argon-to-hydrogen ratio, the desired power tion ports were relocated in the modified anode exit to
was obtained by adjusting the discharge current. decrease wall heat losses. In Table 1, the conversion
The measurements have been previously described in efficiency (CE) is defined as CE ) [1 - QCH4P/QCH4in]
detail,5 so only a brief description will appear here. The 100, where QCH4 is the volumetric flow rate of methane
composition of the product stream is analyzed by a at standard temperature and pressure and the super-
Hewlett-Packard series 6890 model G1540A gas chro- scripts P and in denote the product stream and
matograph. Other instrumentation include gas flow process feedstock inflow, respectively. The carbon basis
rates, cooling water flow rates, and various tempera- yield (y) is defined as y ) (mass carbon contained in a
tures and pressures. All instrumentation except for the particular product)/(mass carbon input in feedstock
gas chromatograph are directly interfaced to a data inflow) 100. Methane conversion is essentially com-
acquisition system for continuous recording of system plete in both tests. The measured carbon yields are 4.7%
parameters during a test run. Once the specified process for the short reactor and 30% for the 61 cm reactor. The
power levels, pressures, and gas flow rates are estab- majority of the remaining carbon appears as acetylene,
lished, a residual gas analyzer continuously samples the benzene, and ethylene.
gas stream to verify that major species concentrations The average plasma temperature is obtained from the
stabilize. This ensures that steady state is achieved, that calculated average enthalpy (power deposited in the
the system temperatures equilibrate, and that thermal plasma/mass flow rate of plasma gas) using the tables
masses such as the graphite reactor liner do not in ref 16. The inlet boundary condition assumes that
influence the results. All cooling water flow rates and the injected methane is instantaneously mixed without
inlet and outlet temperatures are monitored and re- dissociation. The resulting mixture enthalpy is used to
corded, allowing a complete system energy balance to determine the inlet boundary condition temperature.
be calculated, in many cases on individual components The plasma composition is assumed to be in equilibrium
such as the injector ring, reactor, and so forth. The at this temperature. Ionization is neglected; at the
presence of inert Ar has the advantage that it provides average plasma temperature the argon is less than 5%
a built in reference for validating the overall process ionized in Test II, and ionization is negligible in Test I.
mass balance. In general, the measured system mass
balance was within (5%. This accuracy is not sufficient 3. Kinetic Modeling
to resolve small amounts of soot production but does
provide a valuable check on an overall measurement A detailed kinetic model was developed to aid in
system performance. In the test cases described, the understanding the pyrolysis process. The model is a one-
solid carbon soot was physically collected and weighed dimensional representation of the fluid dynamics and
to provide an accurate measure of the amount of solid chemistry of the process implemented in the plug flow
carbon produced. reactor application in CHEMKIN, version 3.6.17 The
We have chosen two data sets, summarized in Table chemical species included and their CHEMKIN ther-
1, to use in benchmarking the model. The first of these modynamic database symbols are given in Table 2. The
1428 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002
inlet boundary conditions were given in Table 1. Down-
stream of the inlet, the temperature and pressure are
allowed to vary, as required by conservation of mass,
momentum, and energy. Wall heat transfer, based on
actual energy loss measurements, is included. The
kinetic model includes the reaction mechanisms result-
ing in the formation of acetylene and heavier hydrocar-
bons through benzene. Also included in the model is a
solid carbon nucleation and growth mechanism, as are
reactions resulting in gas-phase carbon as C and C2. The
reverse rates were obtained using equilibrium constants
calculated from thermodynamic data. Argon is included
as a third-body collision partner, and its effect on the
equilibrium state is included. The thermodynamic data
is taken from the CHEMKIN17 database.
A simplified soot nucleation and growth model has
been combined with the gas-phase chemistry model. The
soot nucleation and growth reactions are linked to the
gas-phase chemistry by the simplifying assumptions
that the local concentration of benzene determines the
rate of nucleation and that soot mass growth is con-
trolled by the local acetylene concentration. The model
that we will employ is based on the semiempirical model
of Lindstedt.18,19 The model does not have the generality
of the very detailed PAH formation and growth models
of Frenklach and co-workers;4,20,21 however, with ap-
propriate benchmarking, the simplified model should be
adequate to examine timescales and process sensitivity
over a limited range.
The nucleation step used in the present approach is
written as C6H6 T 6Csoot(s) + 3H2, where Csoot(s) has
the thermodynamic and physical properties of solid
carbon. The reaction rate suggested by Lindstedt19 is
first order in C6H6. Note that incipient soot particulates
do not contain hydrogen in this representation. This is
an oversimplification and one of the limitations inherent
in simplified approaches. The issue is that newly formed
soot particles with significant hydrogen content tend to
display a higher reactivity than older particles (as much
as an order of magnitude). To include this behavior in
the soot surface growth step requires that the rate
constant display a temporal dependence on the age of
the particle during the initial growth stage and the
adoption of additional aging equations. Lindstedts
approach avoids this issue by combining the nucleation
and initial mass growth process by assuming that
incipient soot particles contain a certain number of
carbon atoms, nc min. Hence, the number density of
primary soot particles is given by [Csoot(s)]NA/nc min,
where NA is Avogadros number, 6.02 1023 g mol-1.
Lindstedt further assumed that nc min is equal to a C-60
shell, which is the most abundant of the smaller PAH
ions. This assumption gives an initial particle size of
about 1 nm. The rate constant has the Arrhenius form
and an activation energy of about 174 600 J mol-1 was
found to yield good results.22 Lindstedt determined the
pre-exponential factor by comparison to an ethylene
flame.
The second reaction step, which is primarily respon-
sible for the increase in soot mass, is assumed to be
surface growth due to the adsorption of acetylene on the
surface of soot particles and abstraction of the hydro-
gen.4,20 On the basis of measurements, this process was
found to be approximately first-order in acetylene
concentration, and the activation energy was deter-
mined to have a value of around 100 600 J mol-1 in
diffusion flames and premixed flames.18,22 The depen-
dence of the soot mass growth reaction step on particle
surface area is less clear, and many approaches have
been suggested. These idealized approaches can gener-
ally be categorized as follows. (1) The reactivity is
proportional to the available surface area, and the
effects of surface chemistry are accounted for by the use
of a steady-state approximation for the acetylene addi-
tion/hydrogen abstraction sequence. (2) The reaction
rate is simply proportional to the local surface area and
acetylene concentration. (3) The reaction rate is pro-
portional to the number of particles but independent of
surface area. (4) The reaction rate is proportional to the
number of particles, independent of surface area, and
the number of particles is constant.
Lindstedt examined all four models and obtained the
best agreement in diffusion flames using approach 3s
the mass growth step is independent of surface area but
dependent on the number of particles.18,22 The basis for
approach 3 is the work of Brockhorn et al.,23 who showed
that soot growth was not related only to surface area
and could, in fact, be independent of area.23 In essence,
this assumption accounts for, in an approximate way,
the reduced activity of older soot particles. As particles
age, there is a depletion of active surface acetylene
adsorption sites, resulting in a depressed growth rate
as the surface area continues to increase. To maintain
consistency with the original Lindstedt model and the
ease of incorporation into the kinetics model, this is the
approach that we will use. The form of the mass growth
reaction is given by C2H2 T 2C(s) + H2, where C(s) has
the thermodynamic and physical properties of solid
carbon. In the model, both [Csoot(s)] and [C(s)] are
calculated giving both an estimate of the unagglomer-
ated number of primary soot particles, [Csoot(s)]NA/nc min,
and the total amount of soot produced, [C(s)]. The
nucleation reaction C6H6 T 6Csoot(s) + 3H2 has a rate
given by
rC soot(s) ) kC soot(s)[C6H6] ) AC soot(S)e-174 600/RT[C6H6]
where AC soot(s) and [C6H6] are in mol/cm3 and RT is in
J mol-1. The rate of mass growth of the primary
particles is first order in [C2H2] and is proportional to
the number of primary soot particles. The rate expres-
sion is given by
[ ]
NA
rC(s) ) AC(s)e-100 600/RT [Csoot(s)] [C H ]
nc min 2 2
The pre-exponential factors for both the nucleation and
growth reactions will be further discussed when we
compare calculated to experimental results. The com-
plete set of gas-phase reactions and their forward rates
are summarized in Table 3.
4. Comparison of Kinetic Model to Experiment
The calculated axial position-dependent temperature
and velocity corresponding to Test I is shown in Figure
4. The high axial velocity present in the injector section
drops when the larger diameter reactor section is
entered, then increases again in the downstream con-
traction. The temperature decreases monotonically, with
the initial sharp drop corresponding to the rapid dis-
sociation of CH4 and formation of C2H2. The subsequent
temperature decrease is due to wall heat transfer. The
destruction of methane and formation of C1 and C2
product species is shown in Figures 5 and 6, and the
 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002 1429

Table 3. Reaction Mechanism and Forward Rate Coefficientsa

C1 and C2 Mechanism
Kf ) R1TR2 exp(-E/RT) Kf ) R1TR2 exp(-E/RT)
no. reaction R1 R2 E ref no. reaction R1 R2 E ref
1 H + H + M T H2 + M 1.80 1018 -1.0 0 24 19 C2H + C2H3 T C2H2 + C2H2 9.64 1011 0.0 0 28
2 CH4 + H T CH3 + H2 1.30 104 3.0 33.6 25 20 C2H + C2H5 T C2H2 + C2H4 1.81 1012 0.0 0 28
3 CH4 + CH T C2H4 + H 3.00 1013 0.0 -1.7 25 21 C2H2 + H T C2H + H2 6.02 1013 0.0 116.4 26
4 CH4 + CH2 T CH3 + CH3 1.30 1013 0.0 39.9 25 22 C2H3 T C2H2 + H 4.73 1040 -8.8 194.5 25
5 CH3 + H T CH4 1.93 1036 -7.0 38.00 25 23 C2H3 + H T C2H2 + H2 1.2 1013 0.0 0 25
6 CH3 + CH3 T C2H6 1.69 1053 -12 81.24 25 24 C2H3 + CH3 T C2H2 + CH4 3.92 1011 0.0 0 28
7 CH3 + CH3 T C2H5 + H 3.01 1013 0.0 56.54 26 25 C2H3 + C2H3 T C2H2 + C2H4 9.64 1011 0.0 0 28
8 CH3 + CH3 T C2H4 + H2 1.00 1016 0.0 134 25 26 C2H4 + CH3 T C2H3 + CH4 4.16 1012 0.0 45.56 26
9 CH3 + M T CH2 + H + M 1.00 1016 0.0 379 25 27 C2H4 + H T C2H3 + H2 1.70 1015 0.0 62.9 25
10 CH3 + M T CH + H2 + M 6.90 1014 0.0 345 27 28 C2H4 + M T C2H2 + H2 + M 2.5 1017 0.0 320 25
11 CH2 + H T CH + H2 6.00 1012 0.0 -7.5 25 29 C2H4 + M T C2H3 + H + M 1.7 1018 0.0 404 25
12 CH2 + CH2 T C2H2 + H2 1.20 1013 0.0 3.4 25 30 C2H5 T C2H4 + H 1.02 1043 -9.1 224.15 25
13 CH2 + CH2 T C2H2 + H + H 1.10 1014 0.0 3.4 25 31 C2H5 + C2H2 T C2H6 + C2H 2.7 1011 0.0 98.11 28
14 CH2 + CH3 T C2H4 + H 4.20 1013 0.0 0 25 32 C2H5 +CH3 T C2H4 + CH4 1.15 1012 0.0 0 26
15 CH2 +C2H T C2H2 + CH 1.81 1013 0.0 0 28 33 C2H5 + C2H5 T C2H4 + C2H6 1.39 1012 0.0 0 29
16 CH2 +C2H3 T C2H2 + CH3 1.81 1013 0.0 0 28 34 C2H6 + H T C2H5 + H2 1.44 109 1.5 31.1 26
17 C2H + H T C2H2 1.81 1014 0.0 0 28 35 C2H6 + CH2 T C2H5 + CH3 2.2 1013 0.0 36.3 30
18 C2H + CH4 T C2H2 + CH3 1.81 1012 0.0 2.08 28 36 C2H6 + CH3 T C2H5 + CH4 1.50 10-7 6.0 25.4 26
Benzene Mechanism
Kf ) R1TR2 exp(-E/RT) Kf ) R1TR2 exp(-E/RT)
no. reaction R1 R2 E ref no. reaction R1 R2 E ref
C3H2 Forming Reactions
37 C2H2 + CH T C3H2 + H 3.00 1013 0.0 0 4
C3H3 Forming Reactions
38 C2H2 + CH2 T C3H3 + H 1.20 1013 0.0 26.48 4 42 p-C3H4 + H T C3H3 + H2 1.15 108 1.9 31.52 4
39 CH3 + C2H T C3H3 + H 2.41 1013 0.0 0 4 43 p-C3H4 + C2H T C2H2 + C3H3 1.00 1013 0.0 0 4
40 a-C3H4 + H T C3H3 + H2 1.15 108 1.9 31.52 4 44 i-C4H5 + H T C3H3 + CH3 2.00 1013 0.0 8.37 4
41 a-C3H4 + C2H T C2H2 + C3H3 1.00 1013 0.0 0 4
C3H4 Forming Reactions
45 C3H3 + H + M T a-C3H4 + M 3.00 1013 0.0 0 4 47 C3H3 + H + M T p-C3H4 + M 3.00 1013 0.0 0 4
46 C2H2 + CH3 T a-C3H4 + H 5.72 1020 -2.36 131.86 4 48 C2H2 + CH3 T p-C3H4 + H 2.72 1018 -1.97 84.56 4
C3H5 Forming Reactions
49 C2H2 + CH3 T C3H5 6.03 1011 0.0 32.23 28
C4H4 Forming Reactions
50 C2H3 + C2H2 T C4H4 + H 2.00 1012 0.0 20.92 31 54 C3H3 + CH2 T C4H4 + H 2.00 1013 0.0 0 9
51 C2H2 + C2H2 T C4H4 2.45 1014 0.0 194.14 32 55 C3H2 + CH3 T C4H4 + H 5.00 1012 0.0 0 4
52 C2H4 + C2H T C4H4 + H 1.20 1013 0.0 0 4 56 i-C4H5 + H T C4H4 + H2 3.00 1013 0.0 0 4
53 n-C4H5 + H T C4H4 + H2 1.50 1013 0.0 0 4
C4H5 Forming Reactions
57 C4H4 + H T n-C4H5 1.30 1051 -11.92 69.5 4 63 1,3-C4H6 T i-C4H5 + H 5.70 1036 -6.27 470.5 4
58 C2H3 + C2H2 T n-C4H5 2.51 105 1.9 8.8 4 64 C4H4 + H T i-C4H5 4.90 1051 -11.92 74.1 4
59 C2H3 + C2H3 T n-C4H5 + H 2.40 1020 -2.04 64.46 9 65 C2H2 + C2H3 T i-C4H5 1.60 1046 -10.98 77.86 4
60 1,3-C4H6 + H T n-C4H5 + H2 1.33 106 2.53 51.2 4 66 C2H3 + C2H3 T i-C4H5 + H 1.20 1022 -2.44 57.35 4
61 1,3-C4H6 T n-C4H5 + H 5.30 1044 -8.62 517.4 4 67 n-C4H5 + H T i-C4H5 + H 3.10 1026 -3.35 72.83 4
62 1,3-C4H6 + H T i-C4H5 + H2 6.65 105 2.53 38.7 4 68 n-C4H5 T i-C4H5 1.50 1067 -16.89 247.4 4
1,3-C4H6 Forming Reactions
69 C2H4 + C2H3 T 1,3-C4H6 + H 2.80 1021 -2.44 61.62 4 70 C2H3 + C2H3 T 1,3-C4H6 1.50 1042 -8.84 52.3 4
2-C4H8 Forming Reactions
71 2-C4H8 T CH3 + C3H5 1.00 1013 0.0 334.72 42 72 2-C4H8 T 1,3-C4H6 + H2 1.00 1013 0.0 271.96 43
C6H6 Destruction Reactions
73 C6H5 + H + M T C6H6 9.30 1014 0.0 53.35 4
C6H6 Forming Reactions
74 C2H2 + C4H4 T C6H6 4.47 1011 0.0 125.90 33 76 C2H3 + n-C4H5 T C6H6 + H2 1.84 10-13 7.07 -15.11 35
75 n-C4H5 + C2H2 T C6H6 + H 1.60 1016 -1.33 22.6 4 77 C3H3 + C3H3 T C6H6 3.00 1011 0.0 0 36
Gas-Phase Carbon Reactions
78 CH2 + CH2 T CH3 + CH 2.40 1014 0.0 41.57 37 83 C2 + M T C + C + M 3.72 1014 0.0 580.53 40
79 CH2 + M T CH + H 4.00 1015 0.0 347.54 38 84 C2H + C2H T C2H2 + C2 1.81 1012 0.0 0 28
80 C + H2 T CH + H 4.00 1014 0.0 97.28 39 85 C2H2 + M T C2 + H2 + M 4.57 107 0.0 17.20 41
81 CH + M T C + H + M 1.90 1014 0.0 280.19 38 86 C2H + M T C2 + H + M 3.61 1015 0.0 598.17 40
82 CH2 + M T C + H2 + M 1.30 1014 0.0 246.93 38 87 C2H + H T C2 + H2 3.61 1013 0.0 118.25 40
a Units are cm, mol, s, and E in kJ mol-1.
C3-C6 species along with solid carbon soot appear in s (0.25 cm). The spatial (time) dependency of the
Figures 7 and 8. The concentration of diatomic gaseous dissociation of methane and C2H2 formation is not
carbon, C2, is <1 10-10 and does not appear in Figure resolved in Figures 5-8. A plot of the C1 and C2 product
6. At the initial temperature of 3450 K, the methane species, represented on a greatly expanded spatial scale,
dissociation process has a timescale of approximately 4 appears in Figure 9. Early in the process, the major
1430 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002
Figure 4. Calculated axial temperature and velocity profiles
corresponding to Test I conditions.
Figure 5. Calculated hydrogen and C1 hydrocarbon species
behavior corresponding to Test I conditions.
Figure 6. Calculated C2 hydrocarbon species behavior corre-
sponding to Test I conditions.
dissociation products are the methyl (CH3) and atomic
hydrogen radicals. The major species formed are the
ethynyl radical (C2H), the vinyl radical (C2H3), acetylene
(C2H2), and ethylene (C2H4). Ethane (C2H6) and the
ethyl radical (C2H5) are produced in relatively smaller
quantities along with the methylene radical (CH2). At
approximately 0.01 cm, the concentration of methyl
radicals is near its maximum as is the concentration of
ethylene. Ethylene dissociates into acetylene and hy-
drogen and reacts with the methyl and atomic hydrogen
radicals to form the C2H3 radical that also dissociates
into acetylene or can further react with methyl and
hydrogen radicals to also form acetylene. Clearly, the
methyl radical plays a major role in the formation of
acetylene. The steady-state acetylene concentration is
attained at around 0.05 cm. The chemistry is extremely
rapid at these temperatures and is much faster than
the physical injection and mixing process. The results
of an acetylene formation sensitivity analysis (not
Figure 7. Calculated C3-C4 hydrocarbon species behavior cor-
responding to Test I conditions.
Figure 8. Calculated solid carbon soot formation profile corre-
sponding to Test I conditions.
Figure 9. Calculated behavior of C1-C2 hydrocarbon species
corresponding to Test I conditions plotted on an expanded abscissa.
shown) indicate that the dissociation process is the rate-
controlling step at these temperatures. In reality, the
rate of dissociation of CH4 and the formation of C2H2
at these temperatures will be limited not by the rate of
reaction but by the fluid mechanics and heat transfer
associated with the physical injection and mixing pro-
cess.
The spatially dependent formation of the C3-C4
hydrocarbons is shown in Figure 7, and a composite
graph of the major C1 and C2 species along with C6 and
solid carbon appear in Figure 8. The mass growth of
 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002 1431

Figure 10. Calculated axial temperature and velocity profiles

corresponding to Test II conditions.

Figure 12. Calculated behavior of major species contributing to

the gas-phase formation of benzene (Test II conditions).

Table 4. Comparison of Calculated and Measured

Results
Test I Test II
mole fraction mole fraction
species measured calculated measured calculated
Ar 0.293 0.287 0.363 0.371
H2 0.564 0.581 0.547 0.471
C2H2 0.1135 0.109 0.076 0.0752
C4H8 trace trace
C3H4 1.8 10-6 trace
C2H4 0.002 14 0.002 90 0.002 67 0.002 94
Figure 11. Calculated solid carbon soot formation profile corre- C2H6 trace trace
sponding to Test II conditions. C6H6 0.0034 0.000 196 0.005 94 0.000 268
CH4 0.002 35 0.0012 0.001 33 0.001 05
solid carbon effectively terminates once the temperature C(s) 0.0180 0.0181 0.0672 0.0769
drops below 1500 K. The production of incipient soot
particles or nuclei terminates at a temperature of with the formation of benzene C6H6 and does not include
approximately 2000 K. The transient behavior in species the progression to heavier hydrocarbons. The mecha-
concentration at relatively long time periods, well nism is complicated and includes both C2 + C4 channels
downstream of the injection location, is controlled by and C3H3 + C3H3 channels. The C3H3 + C3H3 reaction
the decrease in temperature due to wall heat transfer route, which is assumed to proceed in the forward
and is also affected by the formation of solid carbon. In direction only, is likely to be a process that involves
this region, populations of ethylene, ethane, vinyl several elementary reactions represented by a single
acetylene, and benzene increase at the expense of the global reaction.4 This is because the resulting nonaro-
H, CH3, C2H, C3H2, C3H3, and C6H5 species. In particu- matic C6H6 adduct must undergo extensive internal
lar, concentrations of ethylene increase significantly, arrangements before becoming a hot, stable benzene
and some back reaction to CH4 is predicted. Selected molecule. This reaction is assumed to proceed in the
results of a similar calculation for the 61 cm reactor, forward direction only because the resulting excited
Test II, appear in Figures 10-12. The temperature and benzene molecule can subsequently stabilize or will
velocity history is shown in Figure 10, and the major dissociate to phenyl (C6H5) and H.4 The dissociation of
C1, C2, and C6 species, including solid carbon, appear benzene to phenyl is the major destruction mechanism
in Figure 11. Consistent with the results in Figure 8, included in the current model.
solid carbon growth effectively terminates once the Of the reactions that can result in C3H3 formation,
temperature drops below 1500 K. A more detailed view sensitivity analysis indicates that the reaction CH3 +
of the species important to the formation of benzene C2H T C3H3 + H is the rate-controlling step over a wide
appears in Figure 12. The calculation is terminated range of temperatures. Thus, the rate at which C3H3 is
when the temperature drops below 500 K and the formed is ultimately dependent on the concentrations
species concentrations have stabilized. A summary of of CH3 and C2H. In the C2 + C4 channel, the C4 species
calculated results as compared to experimental observa- considered are C4H4 and n-C4H5. The formation of both
tions appear in Table 4. n-C4H5 and i-C4H5 have also been included for com-
Because of its fundamental importance in combustion pleteness. These processes consist primarily of reactions
and soot formation processes, the mechanisms leading between C4H4, C2H2, C2H3, and 1,3-C4H6. It has been
to benzene formation have been heavily studied.4 And, argued in ref 44 that the concentration of n-C4H5 could
while many uncertainties concerning the detailed reac- not be in concentrations large enough to form benzene
tion pathways exist, the proposed mechanisms seem to because the radicals rapidly transfer to the isomer
reproduce the major details of the C3-C6 chemistry for i-C4H5 via n-C4H5 + H T i-C4H5 + H. The isomer
a variety of combustion cases.4 The model that we have transfer reaction has been included. In general, the
implemented is similar to, though slightly simpler than, predicted concentrations of n-C4H5 and i-C4H5 are
the very detailed work of ref 4. The model terminates relatively small, and its inclusion has very little influ-
1432 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002
Figure 13. Acetylene consumption as a function of pressure (Test
II conditions).
ence on calculated benzene concentrations. The benzene
concentration steadily increases as the temperature of
the reactants decreases, primarily as a result of the
C3H3 + C3H3 f C6H6 reaction (Figure 12). Sensitivity
analysis indicates that the C3H3 + C3H3 channel is the
dominant reaction pathway in this model under our
conditions.
Examination of the results tabulated in Table 4
indicate that the yields of acetylene, ethylene, and the
conversion of methane are reasonably well represented.
These are the major species that are experimentally
observed, although at larger methane feed rates, pro-
padiene and t-2-butene are also present in measurable
quantities.5 In both Tests I and II results, the model
significantly underpredicts the experimentally mea-
sured amount of benzene by a factor of approximately
20. An equilibrium calculation corresponding to the Test
II gas mixture (4.6/1/3 Ar/H2/CH4) indicates that the
maximum equilibrium concentration of benzene is ap-
proximately 3 mol % at 1350-1450 K, significantly
greater than the measured value of around 0.6%. The
benzene feature is relatively narrow (see Figure 2 for a
representative example) with a width of only 400-600
K depending on the actual mixture. For the benzene
concentrations to approach equilibrium via gas-phase
reactions, there must be significant residence time in
the 1350-1450 K temperature range. In addition, the
gas-phase reactions must be sufficiently fast to approach
equilibrium, and the reactants, primarily C3H3 that is
produced by reactions between CH3 and C2H, must be
present in adequate quantities. In the 1350-1450 K
range (spatially, 50-60 cm; Figure 12), the predicted
population of CH3 and C2H are not sufficient to result
in the formation of an equilibrium concentration of C6H6
(Figure 13). Ultimately, the kinetic bottleneck in the
gas-phase chemistry is the rapid formation and rela-
tively stability of the acetylene molecule at high tem-
peratures. Thus, the concentration of C6H6 that can be
achieved via gas-phase reactions is kinetically limited.
The measured concentration of C6H6, while less than
the maximum possible equilibrium value, is however
Table 5. Forward Rate Coefficients for Soot Nucleation and Growth, Comparison of Lindstedts18 Recommended Rates,
and the Rates Used in This Worka
reaction
1 C6H6 T 6Csoot(s) + 3H2
2 C2H2 + Csoot(s) T Csoot(s) + 2C(s) + H2
1* C6H6 T 6Csoot(s) + 3H2
2* C2H2 + Csoot(s) T Csoot(s) + 2C(s) + H2
a Units are cm, mol, s, and E in kJ mol-1.
significantly larger than can be accounted for by the gas-
phase reaction model alone. It is well-known that
acetylene can be catalytically converted directly to
benzene (and other products in generally smaller quan-
tities) by reaction over various catalytic surfaces. These
reactions readily proceed at temperatures of 300-750
C.45-48 We surmise that the experimentally observed
benzene concentrations are a result of the catalytic
conversion of acetylene on surfaces within the apparatus
and that, in fact, the gas-phase kinetic model is a
reasonable representation of the gas-phase chemistry
contribution to the observed benzene concentration.
Because of the large surface area represented by the
downstream piping, relatively large amounts of benzene
may be formed in regions where soot mass growth has
already terminated because of gas cooling by wall heat
transfer. That is, the gas temperature has dropped
below approximately 1500 K. The majority of the solid
carbon is collected downstream of the hot sections in a
filter bank that precedes the exhaust handling equip-
ment, suggesting that surface decomposition does not
play a dominant role. In proceeding with our examina-
tion of soot nucleation and growth, we will assume that
the predicted gas-phase concentrations of benzene are,
in fact, representative of the environment in which the
majority of solid carbon forms.
Table 5 contains a comparison between the soot
nucleation and growth rates recommended by Lind-
stedt18 (reactions 1 and 2) and the values used in this
work (reactions 1* and 2*). We have retained the
originally recommended values for the nucleation reac-
tion along with the assumption that nc min ) 60. Best
agreement, as defined by matching both the acetylene
concentration and mass of solid carbon produced, was
obtained by increasing Lindstedts original pre-expo-
nential value for reaction 2 by a factor of 5. The results
of both Tests I and II are reasonably well represented
by this choice of rate coefficients (Table 4). Clearly, the
kinetic model could be further refined with the avail-
ability of additional detailed data. However, the results
obtained with the minor adjustment of a single param-
eter are encouraging.
5. Process Optimization
The benchmarked kinetic model can now be used to
examine the details of the conversion process and, in
particular, ways of increasing yield. One should keep
in mind that the conditions examined should not vary
too much from that of the benchmarking tests. The two
most obvious methods of increasing yield are increasing
the process pressure, which increases the local molar
concentration of reactants, and increasing the nucle-
ation rate. An increase in the nucleation rate can be
accomplished by artificially introducing nucleation sites
by seeding, or perhaps simply through the use of
consumable graphite electrodes. By using graphite
Kf ) R1TR2 exp (-E/RT)
R1 R2 E ref
0.75 105 0.0 174.6 18
1.00 1013 0.0 100.6 18
0.75 105 0.0 174.6 this work
5.00 1013 0.0 100.6 this work

Figure 14. Solid carbon soot formation as a function of pressure
(Test II conditions).
Figure 15. Acetylene consumption as a function of increased
nucleation sites (Test II conditions).
Figure 16. Solid carbon soot formation as a function of increased
nucleation sites (Test II conditions).
electrodes, the erosion process will naturally introduce
significant quantities of solid carbon nucleation sites,
although their reactivity may differ from that of a PAH
nucleation and growth site.
Figures 13 and 14 contain axial plots of acetylene and
solid carbon mole fractions for the conditions and
geometry of Test II for the conditions of the actual test,
0.763 atm, and for a 25% and 50% increase in operating
pressure. The wall heat transfer rates are assumed to
remain unchanged. Even modest increases in operating
pressure substantially enhance the rate of depletion of
acetylene and rate of formation of solid carbon. A 50%
increase in operating pressure to 1.145 atm is predicted
to result in an almost complete conversion to hydrogen
and solid carbon, assuming that the wall heat transfer
rates do not change. Figures 15 and 16 contain axial
plots of acetylene and solid carbon mole fractions for
an increase in nucleation sites by factors of 2, 3, 4, and
Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002 1433
Figure 17. Methane destruction as a function of power input
(adiabatic reactor).
Figure 18. Temperature profile as a function of power input
(adiabatic reactor).
Figure 19. Acetylene consumption as a function of power input
(adiabatic reactor).
6. All other conditions remain the same. Assuming the
same reactivity, at least a factor of 6 increase in nuclei
density is required to achieve complete conversion. In
all the calculated results presented thus far, the conver-
sion of acetylene to hydrogen and solid carbon is
effectively terminated or quenched by wall heat trans-
fer. Better management of wall heat transfer can
increase hydrogen and carbon yield while lowering the
required plasma power input dramatically.
Finally, in Figures 17-20, we show calculated results
for a constant area (50.0 mm diameter, 175 cm long)
adiabatic wall reactor operating at plasma power inputs
between 12.6 and 16.7 kW. The plasma gas is hydrogen
(50 slm), corresponding to the industrially preferred
plasma gas composition, and it is assumed that 100 slm
CH4 is injected post discharge. The methane is assumed
to instantaneously mix with the H2 stream, and the
mixture comes to temperature equilibrium without
1434 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002
Figure 20. Solid carbon soot formation as a function of power
input (adiabatic reactor).
methane dissociation in the same manner that the
boundary conditions were chosen for Tests I and II
calculations.
The destruction of methane appears in Figure 17.
Approximately 15.9 kW of plasma power is required for
complete methane conversion. The corresponding tem-
perature profiles appear in Figure 18. The initial
temperature drop corresponds to the endothermic for-
mation of acetylene followed by the release of energy in
the acetylene decomposition process. For complete
methane conversion, the exit temperature is approxi-
mately 1800 K. The corresponding acetylene and solid
carbon mole fractions appear in Figures 19 and 20.
Complete conversion of the acetylene to carbon is
achieved at a power input of 15.1 kW; however, the
overall process conversion is less than complete because
of the unconverted fraction of methane remaining
(Figure 17).
The specific energy requirement corresponding to the
15.9 kW case is 1.325 (kWhr)/(Nm3H2). Approximately
1.7 kW is required to heat the hydrogen torch gas,
resulting in a specific energy requirement of approxi-
mately 1.2 (kWhr)/(Nm3H2) for methane conversion
alone. Contrast this number to the theoretical SER
(product stream at 1000 C) of 0.933 (kWhr)/(Nm3H2).
The kinetics of the decomposition of methane, the
necessary intermediate step of acetylene formation and
the subsequent decomposition to carbon and hydrogen
in a reasonable time period, and reactor length require
higher product temperature, necessitating higher inlet
temperature or power input. This results in a SER
approximately 30% higher than indicated by equilibri-
um thermodynamics. The use of a separate plasma gas
increases the SER another 10% or so. Efficient waste
heat recovery and thermal management is necessary to
approach the thermodynamic minimum SER of 0.933
(kWhr)/(Nm3H2).
6. Summary and Discussion
The plasma-driven gas-phase thermal decomposition
or cracking of methane (natural gas) to yield hydrogen
and solid-phase carbon has been examined. This process
has been suggested as an environmentally friendly
alternative to conventional hydrogen production meth-
ods that result in the release of large quantities of CO2
to the environment. The process was experimentally
addressed using a modified version of a dc plasma
reactor developed for the plasma thermal conversion of
methane to acetylene. The initial attempt at optimizing
carbon yield by increasing residence time resulted in a
6-fold increase to a yield of 30%. Process details and
optimization were subsequently examined by using a
detailed kinetic model.
The kinetic model developed reproduces the major
features of the product stream and provides useful
information on the relative timescales of methane
dissociation, acetylene formation, and the ultimate
decomposition to hydrogen and solid carbon. The model
significantly underpredicts the measured concentrations
of benzene. The major source of this discrepancy is
thought to be enhancement by surface reactions. Ther-
mal conversion to acetylene is a necessary and unavoid-
able step that precedes gas-phase decomposition. The
thermal conversion of methane to acetylene is kineti-
cally fast as compared to residence time in the reactor
and, in a real apparatus, will be physically limited by
the timescales associated with the fluid mechanics and
heat transfer of the injection and mixing process. The
decomposition of acetylene to solid carbon soot is inher-
ently a kinetically limited process, composed of a
nucleation step followed by mass growth. The formation
of heavier hydrocarbons, primarily benzene, is the
limiting step in the nucleation process. The rate of soot
growth by acetylene decomposition of the surface of an
incipient soot particle is controlled by the acetylene
concentration and temperature. Soot mass growth ef-
fectively terminates when gas temperatures drop below
1500 K. The rate of soot growth can be enhanced by
increasing the process pressure, artificially increasing
the number of nucleation sites, and by improved ther-
mal management through minimization of wall heat
losses. For efficient gas-phase conversion of methane to
hydrogen and solid carbon to take place, the specific
energy input to the system must exceed the theoretical
thermodynamic minimum SER by approximately 30%.
This is due to the kinetics and thermodynamics of
methane dissociation and necessary production of acety-
lene that precedes the decomposition to hydrogen and
solid carbon. For SER to approach the theoretical
minimum product stream, excess or waste energy must
be recovered.
Acknowledgment
This work was performed under the auspices of the
U.S. Department of Energy under DOE Field Office,
Idaho, Contract No. DE-AC07-99ID13727 and was sup-
ported in part by the U.S. DOE National Hydrogen
Program, the U.S. DOE Office of Science, Engineering
Research Program, and by internal Laboratory Directed
Research and Development Funds. Indirect support
through the use of existing apparatus was supplied by
U.S. DOE National Energy Technology Laboratory
under the Gas to Liquids Product Line.
Literature Cited
(1) Padro, C. E. G.; Putsche, V. Survey of the Economics of
Hydrogen Technologies; NREL/TP-570-27079; National Renewable
Energy Laboratory: Golden, CO, 1999.
(2) Basye, L.; Swaminathan, S. Hydrogen Production CostssA
Survey; DOE/GO/10170-T18; Scentech, Inc.: Bethesda, MD, 1997.
(3) Gaudernack, B.; Lynum, S. Hydrogen from Natural Gas
Without Release of CO2 to the Atmosphere. Int. J. Hydrogen
Energy 1998, 23, 1087.
(4) Wang, H.; Frenklach, M. A Detailed Kinetic Modeling Study
of Aromatics Formation in Laminar Premixed Acetylene and
Ethylene flames. Combust. Flame 1997, 110, 173.

(5) Fincke, J. R.; Anderson, R. P.; Hyde, T.; Detering, B. A.;
Wright, R.; Bewley, R. L.; Haggard, D. C.; Swank, W. D.; Plasma
Thermal Conversion of Methane to Acetylene. Plasma Chem.
Plasma Process. 2002, 22, 105.
(6) Holmen, A.; Olsvik, O.; Rokstad, O. A. Pryolysis of Natural
Gas: Chemistry and Process Concepts. Fuel Process. Technol.
1995, 42, 249.
(7) Bolouri, K.; Amouroux, J. Reactor Design and Energy
Concepts for a Plasma Process of Acetylene Black Production.
Plasma Chem. Plasma Process. 1986, 6, 335.
(8) Fulcheri, L.; Schwob, Y.; Variot, B.; Flamant, G.; Badie, J.;
Vallbona, G.; Fischer, F.; Kassabji, F.; Saint Just, J. A 3-Phase A.
C. Plasma Process for Carbon Black Production from Methane.
Therm. Plasma Processes, VDI-Ber. 1995, 1166, 525.
(9) Fulcheri, L.; Schwob, Y. From Methane to Hydrogen, Carbon
Black and Water. Int. J. Hydrogen Energy 1995, 20, 197.
(10) Fulcheri, L.; Flamant, G.; Variot, B.; Ravary, B.; Badie, J.
M. Characterization of a 3-Phase AC Plasma Reactor for Carbon
Black Synthesis from Natural Gas. Proceedings of the 12th
International Symposium on Plasma Chemistry; Heberlein, J. V.,
et al., Eds.; University of Minnesota: Minneapolis, MN, 1995; p
1159.
(11) Fabry, F.; Flamant, G.; Fulcheri, L. Carbon Black Process-
ing by Thermal Plasma, Analysis of the Particle Formation
Mechanism. Chem. Engr. Sci. 2001, 56, 2123.
(12) Lynum, S.; Haugsten, K.; Hox, K.; Hugdahl, J. Plasma
Torch Device for Chemical Processes. U.S. Patent 5,846,674, 1996.
(13) Lynum, S.; Haugsten, K.; Hox, K.; Hugdahl, J.; Myklebust,
N. Method for Combustion of Hydrocarbons. U.S. Patent 5,725,616,
1998.
(14) Lynum, S.; Hox, K.; Hugdahl, J. Production of Carbon
Black. U.S. Patent 5,527,518, 1996.
(15) Wurster R.; Zittel, W. Hydrogen Energy. Workshop on
Energy Technologies to Reduce CO2 Emissions in Europe: Pros-
pects, Competition, Synergy. Energieonderzoek Centrum Neder-
land ECN, Petten, 1994.
(16) Boulos, M.; Fauchais, P.; E. Pfender, Thermal Plasmass
Fundamentals and Applications; Plenum Press: New York, 1994;
Vol. 1.
(17) The CHEMKIN Collection, version 3.6; Reaction Design:
San Diego, CA, 2000.
(18) Lindstedt, P. R. Simplified Soot Nucleation and Surface
Growth Steps for Non-Premixed Flames. Soot Formation in
Combustion; Bockhorn, H., Ed.; Springer-Verlag: New York, 1994;
p 417.
(19) Lindstedt, R. P. A Simplified Mechanism for Soot Forma-
tion in Non-Premixed Flames. Aerothermodynamics in Combus-
tors; Lee, R., Whitelaw, J., Wung, T., Eds; Springer-Verlag:
New York, 1992; p 145.
(20) Kennedy, I. M. Models of Soot Formation and Oxidation.
Prog. Energy Combust. Sci. 1997, 23, 95.
(21) Appels, J.; Bockhorn, H.; Frenklach, M. Kinetic Modeling
of Soot Formation with Detailed Chemistry and Physics: Laminar
Premixed Flames of C2 Hydrocarbons. Combust. Flame 2000, 121,
122.
(22) Leung, K. M.; Lindstedt, P. P.; Jones, W. P. A Simplified
Mechanism for Soot Formation in Nonpremixed Flames. Combust.
Flame 1991, 87, 289.
(23) Wieschnowsky, U.; Bockhorn, H.; Etrring, F. Some New
Observations Concerning the Mass Growth of Soot in Premixed
Hydrocarbon-Oxygen Flames. 22nd International Symposium on
Combustion; The Combustion Institute: Pittsburgh, PA, 1988; p
343.
(24) Cohen, N.; Westberg, K. R. Chemical Kinetic Data Sheets
for High-Temperature Chemical Reactions. J. Phys. Chem. Ref.
Data 1983, 12, 531.
(25) Wrantz, J.; Maas, U.; Dibble, R. W. Combustion; Springer:
New York, 1996; p 67.
(26) Baulch, D. L.; Cobos, C. J.; Cox, R. A.; Esser, C.; Frank,
P.; Just, P. T.; Kerr, J. A.; Pilling, M. J.; Troe, J.; Walker, R. W.;
Warnatz, J. Evaluated Kinetic Data for Combustion Modeling. J.
Phys. Chem. Ref. Data 1992, 21, 411.
(27) Warnatz, J. Rate Coefficients in the C/H/O System.
Combustion Chemistry; Gardiner, W. C., Jr., Ed.; Springer-
Verlag: New York, 1984; p 197.
Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002 1435
(28) Tsang W.; Hampson, R. F. Chemical Kinetic Data Base
for Combustion Chemistry. Part I. Methane and Related Com-
pounds. J. Phys. Chem. Ref. Data 1986, 15, 1087.
(29) Adachi, H.; Basco, N.; James, D. G. L. A Quantitative
Study of Alkyl Radical Reactions by Kinetic Spectroscopy III.
Absorption Spectrum and Rate Constants of Mutual Interaction
for the Ethyl Radical. Int. J. Chem. Kinet. 1979, 11, 995.
(30) Bohland, T.; Dobe, S.; Temps, F.; Wagner, H. G. Kinetics
of the Reactions Between CH2 (X3B1)-Radicals and Saturated
Hydrocarbons in the Temperature Range 296 K-707 K. Ber.
Bunsen-Ges. Phys. Chem. 1985, 89, 1110.
(31) Fahr A.; Stein, S. E. Reactions of Vinyl and Phenyl
Radicals with Ethyne, Ethene, and Benzene. International Sym-
posium on Combustion 1989, 22, 1023.
(32) Ogura, H. Pyrolysis of Acetylene Behind Shock Waves.
Bull. Chem. Soc. Jpn. 1977, 50, 1044.
(33) Chanmugathas C.; Heicklen, J. Pyrolysis of Acetylene-
Vinylacetylene Mixtures Between 400 and 500 C. Int. J. Chem.
Kinet. 1986, 18, 701.
(34) Weissman M A.; Benson, S. W. Rate Parameters for the
Reactions of C2H3 and C4H5 with H2 and C2H2. J. Phys. Chem.
1988, 92, 4080.
(35) Westmoreland, P. R.; Dean, A. M.; Howard, J. B.; Longwell,
J. P. Forming Benzene in Flames by Chemically Activated
Isomerization. J. Phys. Chem. 1989, 93, 8171.
(36) Wu, C. H.; Kern, R. D. Shock-Tube Study of Allene
Pyrolysis. J. Phys. Chem. 1987, 91, 6291.
(37) Frank P.; Just, T. High-Temperature Reactions of Triplet
Methylene and Ketene with Radicals. J. Phys. Chem. 1986, 90,
2226.
(38) Dean J.; Hanson, R. K. CH and C-Atom Time Histories
in Dilute Hydrocarbon Pyrolysis: Measurements and Kinetics
Calculations. Int. J. Chem. Kinet. 1992, 24, 517.
(39) Dean, J.; Davidson, D. F.; Hanson, R. K. A Shock Tube
Study of Reactions of C atoms with H2 and O2 Using Excimer
Photolysis of C3O2 and C Atom Atomic Resonance Absorption
Spectroscopy. J. Phys. Chem. 1991, 95, 183.
(40) Beck W. H.; Mackie, J. C. Formation and Dissociation of
C2 from High-Temperature Pyrolysis of Acetylene. J. Chem. Soc.,
Faraday Trans. 1975, 71, 1363.
(41) Schulz, G.; Klotz, H.-D.; Spangenberg, H.-J., Reaktions-
modell zur Bruttokinetik der Pyrolyse von Methan im Stoss-
wellenrohr bei Temperaturen von 1800 K bis 2500 K, Z. Chem.
1985, 25, 88.
(42) Jeffers P.; Bauer, S. H. The Homogeneous Pyrolysis of
2-Butenes. Int. J. Chem. Kinet. 1974, 6, 763.
(43) Alfassi, Z. B.; Golden, D. M.; Benson, S. W. The Very Low-
Pressure Dehydrogenation of cis-2-Butene. The Activation Energy
of 1,4-H2 Elimination. Int. J. Chem. Kinet. 1973, 5, 991.
(44) Miller, J. A.; Melius, C. F. Kinetic and Thermodynamic
Issues in the Formation of Aromatic Compounds in Flames of
Aliphatic Fuels. Combust. Flame 1992, 91, 21.
(45) Fields, E. K.; Winzenburg, M. L.; A. DeMarco, D. Process
for Preparation of Fuel Additives from Acetylene. U.S. Patent
Number 4,585,897, 1986.
(46) Wizenburg M. L.; DeMarco, D. A. Process for Converting
a Wet Acetylene Containing Stream to Aromatics Using a Zinc-
Promoted Crystalline, Borosilicate Molecular Sieve Catalyst Com-
position. U.S. Patent Number 4,982,032, 1991.
(47) Timmons, R. B.; He, Y.; Jang, W.-L. Zeolite Catalyzed
Conversion of Acetylene. U.S. Patent Number 5,118,893, 1992.
(48) Meriandeau, P.; Tiep, L. V.; Ha, V. T. T.; Naccache, C.;
Szabo, G. Aromatization of Methane over Mo/H-ZSM-5 Catalyst:
on the Possible Reaction Intermediates. J. Mol. Catal. A: Chem.
1999, 144, 469.
Received for review August 31, 2001
Revised manuscript received December 11, 2001
Accepted December 12, 2001
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