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Catalytic Dissociation of Hydrocarbons: a Route to CO2-free Hydrogen

Nazim Muradov, Franklyn Smith and Ali Raissi


Florida Solar Energy Center, University of Central Florida
1679 Clearlake Road, Cocoa, Florida 32922, U.S.A.
Abstract
Catalytic dissociation of methane and other hydrocarbons is an environmentally attractive
approach to CO2-free production of hydrogen. This paper discusses several process
development issues related to carbon-catalyzed methane decomposition: (1) factors
determining catalyst activity, (2) kinetics and mechanism of methane decomposition over
carbon catalysts, (3) heat input options for the methane decomposition process, (4) thermoneutral catalytic decomposition of methane. It was determined that the catalytic activity of
carbon materials for methane decomposition is mostly determined by their structural and
surface properties. Three technological approaches to the endothermic process heat supply
including internal, external and thermo-neutral heat input options are analyzed. Catalytic
decomposition of methane in thermo-neutral (or autothermal) regime was studied both
analytically and experimentally using carbon-based catalysts. Carbon products of methane
decomposition are characterized and potential markets for these products are evaluated.
Keywords: Hydrogen, carbon, methane decomposition, catalyst, reactor.
1. Introduction
Fossil fuels are likely to play a major role in hydrogen production in the near- to mediumterm future due to their availability, relatively low cost, and the existing infrastructure for
delivery and distribution. On the other hand, fossil fuels are the main source of CO2 and
other emissions that may cause considerable damage to the environment of our planet.
Currently, most of the industrial hydrogen production is based on steam methane reforming
(SMR) process. It was estimated that the global warming potential (GWP, which is defined
as a combination of CO2, CH4 and N2O emissions expressed as a CO2 equivalence for a 100
year time frame) of hydrogen production via SMR process is 13.7 kg CO2 (equiv.) per kg of
net hydrogen produced [1]. CO2 accounts for 77.6% of the systems GWP. Almost half of
the overall CO2 emissions from SMR process is released in diluted form (i.e., stack gases)
with CO2 concentrations of about 5 vol.%, which are very difficult and costly to treat. Two
options to mitigate the CO2 emissions problem associated with fossil-based hydrogen
production are being actively discussed in the literature: (i) sequestration of CO2 produced by
a SMR hydrogen plant, and (ii) thermal dissociation of NG (or methane) into hydrogen and
elemental carbon. The key risk factor associated with the CO2 sequestration stems from
uncertain long-term ecological consequences of this approach. Recently, there have been
new developments on so-called environmentally benign CO2 sequestration (EBS). The
objectives of EBS are to provide a permanent containment for disposed CO2 and avoid
negative environmental impact of sequestration. The prospective candidate technologies
include mineral carbonation, use of pulverized limestone, etc. [2].

Corresponding author. E-mail address: muradov@fsec.ucf.edu

Thermocatalytic decomposition (TCD) of methane (or NG) has recently attracted the
attention of researchers for it could potentially lead to the development of CO2-free hydrogen
production process [3,4].
CH4 C + 2H2

Ho= 75.6 kJ/mole

(1)

The amount of CO2 emissions from the process could potentially be as low as 0.05 mole
CO2/mole H2 (if methane is used as a process fuel), compared to 0.43 mole CO2/mole H2 for
SMR [3]. CO2 emissions could potentially be eliminated, if a part of hydrogen product
(theoretically, 16%) is combusted to produce process heat.
Due to very strong C-H bonds in methane molecule (440 kJ/mole) its thermal (non-catalytic)
decomposition occurs at very high temperatures (>1200oC).
Different transition metal
catalysts (e.g., Ni, Fe, Co) have been used to reduce the maximum temperature of methane
thermal decomposition [5,6]. The major problems associated with the use of metal catalysts
relate to their rapid deactivation (due to blocking of surface active sites by carbon deposits)
and difficulties with metal-carbon separation. The use of carbon-based catalysts offers
certain advantages over metal catalysts due to their availability, durability and low cost. In
contrast to metal-based catalysts, carbon catalysts are sulfur and temperature resistant and do
not require the separation of a carbon-product from a carbon-catalyst. The technical
feasibility of using carbon materials as catalysts for methane decomposition reaction is
discussed in several publications (e.g., [7,8]). The data on catalytic activity of a variety of
carbon materials of different origin and structure, including a wide range of activated carbons
(AC) and carbon blacks (CB), toward methane decomposition reaction is reported in [8-10].
In this paper we discuss several process development issues related to carbon-catalyzed
methane decomposition:

factors determining carbon catalyst activity,


kinetics and mechanism of methane decomposition over carbon catalysts
heat input options for the methane decomposition process
thermo-neutral catalytic decomposition of methane

2. Factors Determining Carbon Catalyst Activity


2.1. Factors Determining Carbon Catalyst Activity
Many of chemical properties of carbon materials, including their catalytic activity has been
shown to be related to the presence of impurities and various surface groups [11]. The
amount and type of impurities present depend on the carbon origin and the method of
preparation. Earlier we reported that transition metals (Fe, Ni, V, etc.) present in CB and AC
have a minor effect on the catalytic activity for methane decomposition [12]. The effect of
surface oxygenated groups is more complex and is not completely understood. According to
[9], oxygenated surface groups play a major role in reactivity of AC for methane
decomposition reaction. In our previous work we reported that although carbon-oxygen
surface groups may play a role in methane dissociation, particularly, at the initial stage of the
process, the catalytic activity of carbons, in general, could not be solely attributed to the
presence of such surface functional groups [12].
It is well known that the majority of catalytic reactions in a gas-solid interface involve
surface defects, dislocations, vacancies, low-coordination sites, etc. Therefore, the possibility
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of this type of catalytic action in the carbon-catalyzed methane decomposition reaction needs
to be closely examined. Various modifications of carbon could be distinguished in terms of
crystallinity or the degree of order, i.e. from highly ordered carbons, such as graphite and
diamond, to less ordered (turbostratic and pyrolytic carbons) and, finally, to disordered (or
amorphous, microcrystalline) carbons, such as carbon black, charcoal, activated carbon. On
the surface of amorphous carbons, the regular array of carbon bonds is disrupted, forming
free valences, discontinuities (i.e., the edges and corners of crystallites) and other energetic
abnormalities that could be generalized as high-energy sites (HES). Evidently, the surface
concentration of HES increases with the decrease in carbon crystallite size, and, vice versa,
decreases as carbon becomes more ordered (e.g., during graphitization). Amorphous carbons
(e.g., AC, CB) are particularly active in methane decomposition reaction, compared to wellordered carbons such as graphite, diamond, and carbon nanotubes. This may point to the
direct correlation between the surface concentration of HES and catalytic activity in methane
decomposition reaction. The driving force for the catalytic action of carbon is that carbon
atoms in HES tend to react with approaching methane molecules in order to satisfy their
valency requirements and energetically stabilize.
It would be worthwhile to give some more consideration to how carbon structure affects its
catalytic activity. The carbon-carbon distance within the hexagon layers in amorphous
carbons is the same as in graphite (1.420 ), however, interlayer spacing is considerably
larger (about 3.6 vs 3.354 in graphite) [13]. XRD studies conducted in this work
demonstrated that in the original carbon black sample (BP2000) the plates are not stacked in
a columnar arrangement, but, instead, are randomly oriented with respect to each other.
However, after exposure to hydrocarbons the ordering in the columnar (or stacking)
direction has evolved. The distance between layers (d-spacing) was found to be d =3.4948
, which lies between the d-spacing for amorphous carbon and pure graphite. Thus, carbons
produced by decomposition of methane and propane feature more ordered structure compared
to amorphous carbons, but they are less structurally ordered than graphite (which is
characteristic of turbostratic carbon). This clearly correlates with the order of catalytic
activity of carbons toward methane decomposition (amorphous>turbostratic> graphite).
Thus, the difference in catalytic activity between different carbons can be explained by the
difference in their crystallinity and surface morphology.
2.2. Kinetics of Methane Decomposition over Carbon Catalyst
The apparent reaction order of carbon-catalyzed methane decomposition reaction was
determined to be 0.5 for both AC- and CB-based catalysts [10,14]. Thus, the rate equation
for carbon-catalyzed decomposition of methane can be written as follows:

rCH = kPCH
4

0.5

(2)

The apparent activation energies for carbon-catalyzed methane decomposition varied in a


wide range not only within different types of carbon (e.g., AC vs CB), but also within the
family of carbons. For example, amongst the AC-based catalysts tested, the apparent
activation energies (Ea) varied in a range of 160-201 kJ/mole (at 600-900oC). These data are
in fairly good agreement with the reported activation energies for a number of coal-derived
AC (186-198 kJ/mol [10]). For CB-based catalysts, the measured Ea were somewhat higher
(205-236 kJ/mole, at the same conditions). It is interesting to note that the values of
activation energies for carbon-catalyzed methane decomposition lie between the Ea for non-

catalytic and metal-catalyzed reactions. For the reference, the activation energies for noncatalytic methane decomposition were reported in the range of 370-433 kJ/mol (e.g., [15]),
whereas, Ea for metal-catalyzed reactions were reported 60 kJ/mol (e.g., [16]).
No definite conclusion has yet been made on the mechanism for carbon-catalyzed methane
decomposition. Most likely, the reaction starts with dissociative adsorption of methane
molecule on the HES on the carbon surface, as described by the following schematics and the
equation 3:

(CH4)g (CH3)a + (H)a

(3)

This is followed by a series of surface stepwise dissociation reactions leading to elemental


carbon and hydrogen:
(CH3)a (CH2)a + (H)a

(4)

(CH2)a (CH)a + (H)a

(5)

(CH)a (C)a + (H)a

(6)

n(C)a 1/n(Cn)c

(7)

2(H)a (H2)g

(8)

where: subscripts (a), (c) and (g) denote adsorbed, crystalline and gaseous species,
respectively. Equation 7 relates to carbon crystallite growth.
3. Heat input options for methane catalytic decomposition
Methane decomposition is a moderately endothermic reaction: the thermal energy
requirement per mole of hydrogen produced is only 37.8 kJ/mole H2 compared to 63 kJ/mole
H2 for SMR. Less than 10% of the methane heating value is needed to drive the endothermic
process. Figure 1 (A, B and C) illustrates three possible technological concepts of heat
supply to the endothermic TCD process. According to the option (A) the heat source is
located inside the reaction zone. It could be a heat pipe, a heat exchanger or a tubular
catalytic burner that uses NG or a portion of hydrogen product as a fuel. As an example, the
use of sodium-based heat pipes as a mode of efficient heat transfer in methane steam
reformers has been demonstrated in [17]. This approach lends itself to coupling with hightemperature gas-cooled nuclear reactors (HTGR) or solar thermal source (e.g., solar

concentrators), and potentially it could provide a process for zero-emission hydrogen


production.
(A)
HC

(B)

H2

H2

(C)
SG

H2,
(CO2)

CH
NG

NG

NG
O2

Cc
1

carbon

carbon

air

carbon

Figure 1. Three process heat input options for thermocatalytic decomposition of methane.
NG- natural gas, HC- heat carrier, SG- stack gases, Cc- cold carbon particles, CH- hot
carbon particles. 1- methane decomposition reactor, 2- reactor heater, 3- catalyst particles
heater, 4- thermo-neutral reactor.

In the concept (B) the process heat is introduced to the reactor by externally heated catalyst
particles similar to fluid catalytic cracking or fluid coking processes widely used in refineries.
The process employs two fluid-solid vessels: a reactor and a heater with catalyst particles
circulating between the vessels in a fluidized state. Catalyst particles are heated by hot
combustion gases (burning part of NG or off-gas from H2 separation unit) and carry
necessary heat to the reactor to accomplish NG decomposition. This technological approach
has been described in our previous publication [18].
According to the concept (C) a relatively small amount of oxygen is fed to the reactor along
with the methane feedstock to generate necessary heat to carry out the endothermic methane
decomposition reaction. One can notice that the concept looks similar to the well-known
partial oxidation (POx) process. There is, however, a fundamental disparity between two
processes. In particular, POx process proceeds to complete conversion of methane into
synthesis gas and, therefore, it requires relatively large amount of oxygen (O2:CH4 =0.5
mole/mole). In contrast, the objective of oxygen-assisted methane decomposition is to
maximize the yields of both hydrogen and carbon products by introducing oxygen in the
quantity just enough to sustain the endothermic methane decomposition reaction. Thus, the
process involves the combination of an endothermic (methane decomposition) and
exothermic (methane combustion) processes in one apparatus (i.e., the process operates in a
thermo-neutral, or autothermal regime). Hereafter we refer to the process as autothermal
pyrolysis (ATP) process. It is evident that the ATP process would use much less oxygen and,
consequently, produce less CO2 emissions than POx or SMR due to relatively low
endothermicity of methane decomposition (it is almost three times less endothermic than
SMR, per mole of H2) and the fact that it does not proceed to synthesis-gas as a final product.
Advantageously, in the ATP process, most of the feedstock carbon ends up in the form of
elemental carbon rather than CO2.

4. Thermo-neutral Catalytic Decomposition of Methane


4.1. Thermodynamic analysis of autothermal pyrolysis of methane
AspenPlusTM chemical process simulator (CPS) was used to conduct thermodynamic analysis
of CH4-O2 system. The reactions involved were modeled using a Gibbs reactor to minimize
the free energy in order to calculate thermodynamic parameters of the process at the given
operating conditions. Input parameters are: inlet pressure and temperature, reactor
temperature and pressure, and (or feed CH4-O2 composition). Peng-Robinson property
package was used for the reaction equilibrium calculations. Methane conversion, products
yields, pyrolysis gas composition, process enthalpy, entropy and Gibbs energy flows as a
function of temperature, pressure and have been determined. The temperature range of
T=300-1200oC, pressures of P=0.1-2.5 MPa and O2/CH4 ratio of = 0-1.5 (mole/mole) were
chosen for the thermodynamic analysis of the process.
Figure 2 illustrates the temperature dependence of hydrogen and carbon yields with as a
variable at P=200 kPa.

110
O2/CH 4=0.0-0.5

P = 200 kPa

100

0.6

90

0.7
0.8

H2 yield (%)

80
70

0.9

60

1.0

50

1.2

40
30

1.5

20
10
0
250

350

450

550

650

750

850

950

1050

1150

1250

Temperature ( C)

100.0
O2/CH 4=0.0

P = 200 kPa

90.0

0.1

Carbon yield (%)

80.0
70.0

0.2

60.0
50.0

0.3

40.0
30.0
20.0
10.0
1.2

0.0
250

350

450

0.4

0.8
0.9
1.0
550

0.7
650

0.6

0.5

750

850

950

1050

1150

1250

Temperature ( C)

Figure 2. Temperature dependence of hydrogen (A) and carbon (B) yields with O2/CH4 ratio
as a variable (P=200 kPa).

The Figure 2 indicates that the hydrogen yield is not appreciably affected by the change in
O2/CH4 ratio within the range of 0< <0.5. However, at >0.5 hydrogen yield drops
markedly, which is accompanied with the increase in water production yield. In contrast,
carbon yield is quite sensitive to even slight increase in value in a whole range of O2/CH4
ratios. At >0.6 carbon is not present among the reaction products at temperatures above
800oC.
The total enthalpy flow within the reactor as a function of temperature and was determined.
The total enthalpy flow rate was calculated as a sum of outlet enthalpies of all products minus
sum of inlet enthalpies of CH4-O2 mixtures. A negative enthalpy flow indicates that at the
given conditions (, T and P) the reactive system produces heat, which would require the
removal of the excess heat from the reactor. In contrary, positive enthalpy flow indicates that
at given conditions a certain amount of thermal energy has to be supplied to the reactor in
order to accomplish methane decomposition. It was found that for the practical range of
temperatures (600-900oC) and pressures of P=0.1-2.5 MPa the enthalpy flow is close to zero
(which corresponds to autothermal or thermo-neutral regime) at O2/CH4 ratio of 0.2.
4.2. Engineering Aspects of Hydrogen Production via ATP of NG
Figure 3 depicts a simplified block-diagram of the ATP process with NG as a feedstock. The
presence of oxygen in the feedstock results in the production of CO byproduct that would
require the addition of water-gas shift (WGS) reactors to the technological chain of the
process. However, due to relatively low concentration of CO in the gaseous product (17
vol.%) the WGS unit in ATP process would be much smaller than that in conventional SMR
or POx processes. In the final stage of the process, high-purity hydrogen (>99.99 vol.%)
could be recovered from H2-CO2 gaseous mixture using off-the-shelf gas separation units
(e.g., a pressure-swing adsorption, or a H2-permeable membrane, or a cryogenic separation).
Unconverted methane is separated from the gaseous mixture and recycled to the reactor.
Due to relatively low endothermicity of the methane decomposition reaction and the
elimination (or reduction in size) of energy-intensive steam production and gas conditioning
stages, the CO2 emission from the ATP process could potentially be much less than that from
conventional processes. It is estimated that CO2 emissions from ATP process could be as low
as 0.17 m3/m3 H2, which is almost three times less (per m3 H2) than that from the SMR
process (or about five times less than from steam-oxygen gasification of coal).
Advantageously, CO2 byproduct is produced in a concentrated form (close to 100 v.%),
which simplifies its capture and sequestration. Due to the fact that ATP process produces
relatively small amounts of CO2 (compared to conventional processes) it would be preferable
to sequester CO2 by one of the EBS methods (see section 1).
On the down side, ATP process utilizes oxygen production unit, which may add to the cost of
hydrogen production. The usage of air instead of oxygen may result in a larger and more
expensive gas separation unit. Therefore, alternative means of introducing oxygen into the
fluidized bed reactor have to be considered. One promising approach relates to the use of
ceramic oxygen-permeable membranes. It is well known that dense ceramic membranes
made of the mixture of ionic and electron conductors are permeable to oxygen at elevated
temperatures. For example, perovskite-type oxides (e.g., La-Sr-Fe-Co, Sr-Fe-Co and Ba-SrCo-Fe based mixed oxide systems) are good oxygen-permeable ceramics. Oxygen
permeation rates (or oxygen flux density) could reach 10 mL/min.cm2 and higher. Extensive
research has been carried out on the application of ceramic O2-permeable membranes to POx
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and other processes requiring pure oxygen. For example, a membrane reactor containing O2permeable ceramic membrane made of Ba0.5Sr0.5Co0.8Fe0.2O3- was applied to partial
oxidation of methane at 900oC [19].

CH4 recycle

H2 (99.99 v.%)

2
H2O
CO2 (100 v.%)
1
catalyst
O2

O2

to EBS of CO2

NG
6
carbon product

Figure 3. Schematic diagram of hydrogen and carbon production via catalytic autothermal
pyrolysis of natural gas. 1- fluidized bed reactor, 2- cyclone, 3- heat exchanger, 4- water gas
shift reactor, 5- gas separation unit, 6- carbon particle grinder, 7- catalyst regeneration unit.

Figure 4 depicts a conceptual drawing of the ATP fluidized bed reactor equipped with a
tubular oxygen-permeable dense ceramic membrane (for simplicity, only two tubular
membrane units are shown on the drawing). A detail of the ceramic membrane wall
explaining the mechanism of oxygen permeation through the membrane is shown on the left
side of the Figure 4. The gradient of oxygen pressure (or its chemical potential, ) is the
driving force for oxygen transport across the ceramic membrane. Advantageously, the O2permeable ceramic membranes efficiently operate at the same temperature range as ATP
process (i.e., 800-900oC).
Stoichiometrically, ATP process requires 2.5 times less oxygen
per mole of methane than POx (O2/CH4 ratios for these processes are 0.2 and 0.5,
respectively). Consequently, oxygen flux requirements for a membrane in the case of ATP
process would be much less demanding compared to POx process (which may potentially
have important practical implications). The advantages of using O2-permeable membrane are
two fold: (i) it would potentially reduce the hydrogen production cost (by eliminating an air
separation plant), and (ii) CO2 byproduct could be produced in a concentrated form (100
vol.%), which would simplify its potential sequestration (preferably, via EBS option).
We conducted a series of proof-of-the-concept experiments on oxygen-assisted catalytic
decomposition of methane using AC (lignite) as a catalyst. We observed that at O2:CH4=0.2
(molar) ratio and the temperature range of 850-1000oC the yields of two major reaction

products: hydrogen and carbon steadily increased, while the COx yields remained almost
independent of temperature. The yields of water and C2 hydrocarbons dropped at the same
range of temperatures. The molar fraction of hydrogen in the products mix (including carbon
and water) reached 60 mol.% at 1000oC, which is in fairly good agreement with the
thermodynamic equilibrium data (within less than 10% margin of error). Among gaseous and
non-condensable products of the reaction the hydrogen yield reached 80 vol.%.
H2-rich gas
air

air

lean air

lean air

O2-permeable
ceramic
membrane
1/2O2
O2 (II)

O 1/2O2

e
2e 2e-

O2 (I)

CH4

air
O2-

O2-

catalyst
particles

NG
Figure 4. Schematics of ATP fluidized bed reactor equipped with a tubular oxygenpermeable ceramic membrane. The section on the left shows the detail of the ceramic
membrane wall (explaining the mechanism of O2 permeation across the membrane).

5. Evaluation of markets for carbon products from methane decomposition


X-ray diffraction (XRD) analysis of carbons produced by methane decomposition over
carbon-based catalysts revealed that the baseline crystallographic structure of carbons is
consistent with the turbostratic structure. It was found, however, that at certain operational
conditions catalytic methane (or propane) decomposition produced filamentous carbons (with
and without metal catalysts). Figure 5 depicts SEM and TEM images of carbon filaments
produced by non-catalytic (B) and iron-catalyzed (A) decomposition of methane.

Figure 5. TEM (A) and SEM (B) images of filamentous carbons obtained by iron-catalyzed
and non-catalytic decomposition of methane, respectively.

It is technically feasible to utilize the carbon products of methane decomposition for


manufacturing structural carbon materials (similar to commercial carbon composites and
manufactured graphites). Manufactured graphites and other commercial carbon composite
materials are made by mixing petroleum coke particles with a binder-pitch. During thermal
treatment, the pitch binder is pyrolyzed to form a coke that bridges the carbon particles and
serves as a permanent binding material. The resulting composite is much stronger than
conventional structural materials, e.g., concrete, firebricks, etc. We contemplate that similar
products could be produced from the carbon products of methane decomposition by binding
them with a low-cost and abundant byproduct of oil refining: petroleum pitch. As discussed
earlier, the carbon particles produced by catalytic decomposition of methane over carbon
catalysts exhibited turbostratic structure, and in many respects are similar to petroleum coke
particles. The carbon composites comprising NG-derived carbon filaments and carbon
particles may be formed into a carbon brick (using pitch as a binder) that has mechanical
strength similar to commercial carbon-carbon composites. Building and construction
industries could potentially provide practically unlimited markets for carbon products of
hydrocarbon decomposition.
6. Conclusion
In the near- to medium-term future, hydrogen production most likely will continue to rely
upon fossil fuels, primarily, natural gas. However, present-day hydrogen production
technologies produce enormous amounts of CO2 emissions. Thermocatalytic decomposition
of methane is an environmentally attractive option for producing both hydrogen and carbon
without (or with drastically reduced) CO2 emissions. The value-added carbon byproducts
could be marketed, thus reducing the net cost of hydrogen production. Methane
decomposition is a moderately endothermic reaction. Several technological approaches to
the process heat supply including internal, external and thermo-neutral heat input options are

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discussed in this paper. The use of ceramic oxygen-permeable membranes could


significantly simplify the process and reduce the cost of hydrogen production. Thermoneutral decomposition of methane was verified both analytically (AspenPlusTM) and
experimentally using carbon-based catalysts. Carbon products of methane (hydrocarbon)
decomposition processes could potentially be used for the production of advanced carboncomposite materials to be utilized in building and construction areas.
Acknowledgements
This work was supported by NASA Glenn Research Center. The authors thank Dr. C. Huang
for the assistance with conducting AspenPlusTM simulations.
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