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Decomposition of Hydrocarbons to Hydrogen and Carbon

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 Applied Catalysis A: General 359 (2009) 1–24

Contents lists available at ScienceDirect

Applied Catalysis A: General

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

Review

Decomposition of hydrocarbons to hydrogen and carbon

Shakeel Ahmed a, Abdullah Aitani a,*, Faizur Rahman a, Ali Al-Dawood b, Fahad Al-Muhaish b
a
The Research Institute, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
b
Research & Development Center, Saudi Aramco, Dhahran 31311, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Article history: This review assesses technologies and catalysts pertaining to the catalytic decomposition of
Received 7 November 2008 hydrocarbons for the CO2-free generation of hydrogen for fuel cell applications through a single-step
Received in revised form 6 February 2009 cracking (decomposition, decarbonization, dehydrogenation, pyrolysis, splitting, or dissociation) of
Accepted 23 February 2009
hydrocarbons. It discusses and systematically categorizes the options for hydrocarbon decomposition to
Available online 9 March 2009
hydrogen and carbon. This decomposition helps to reduce green house gases by co-producing valuable
carbon products such as carbon black or graphite-like carbon (carbon nanotubes or carbon filaments).
Keywords:
The catalytic approach comprises metal and carbon-based catalysts while plasma-based decomposition
Review
depends on thermal or non-thermal methods. Almost all the proposed processes are applicable to a
Cracking
Hydrocarbons variety of gaseous and liquid hydrocarbon fuels, and some of these processes can potentially produce a
Decomposition stream of high-purity hydrogen. There have been successful attempts to use catalysts to reduce the
Decarbonization maximum temperature of the thermal decomposition of hydrocarbons. Common catalysts used are
Dehydrogenation noble and transition metals such as Ni, Fe, Pd, Co, Mo, etc., supported on high surface area ceramic
Dissociation substrates such as A12O3 and SiO2, etc. Several other publications disclose the use of carbon-based
Engine materials as catalysts for decomposition of hydrocarbons into H2 and carbon. The other non-catalytic
Gasoline decomposition methods include non-thermal low-temperature plasmas such as RF (radio frequency), dc
Hydrogen
(direct current) generators, microwave plasmatrons, and arc plasma jet.
Carbon
ß 2009 Elsevier B.V. All rights reserved.
Catalytic
Methane
Plasma
Pyrolysis
Thermo-catalytic

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Onboard hydrogen generation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Hydrogen generation by catalytic routes (SMR, POX and ATR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Hydrogen generation by plasma route . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Onboard hydrogen supplementation to gasoline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Hydrocarbon decomposition processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1. Catalytic and non-catalytic decomposition processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. Decomposition reaction and energy requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4. Decomposition by metal catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.1. Features of metal-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4.2. Decomposition of gaseous hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.2.1. Monometallic catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
4.2.2. Bimetallic catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.3. Decomposition of liquid hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
5. Decomposition by carbon catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5.1. Features of decomposition by carbon catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5.2. Decomposition over carbonaceous materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

* Corresponding author. Tel.: +966 38603007; fax: +966 3860 4509.

E-mail address: maitani@kfupm.edu.sa (A. Aitani).

0926-860X/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2009.02.038
2 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24

5.3. Decomposition over carbon black and activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

6. Decomposition by plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
6.1. Features of hydrocarbon decomposition by plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
6.2. Decomposition by DC RF plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
6.3. Plasma versus catalytic approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

economy reduces H2 costs and motivates H2 economy progress.

Nomenclature The objective of hydrocarbon decomposition is to eliminate or
drastically reduce the amount of CO2 emitted from primary fuel
resources. A wide variety of decomposition methods and
AC activated carbon
techniques have been reported in the literature for the generation
APGP atmospheric-pressure glow plasma of carbon-free H2 from gaseous or liquid hydrocarbon fuels [1].
CB carbon black There is steadily increasing awareness of the need to reduce CO2
CFC catalytic filamentous carbon emissions to limit global warming. Many scientists now believe
CH4 methane that an increase in the concentration of CO2 and other green house
CNG compressed natural gas gas (GHG) such as methane and nitrous oxide, will increase the
CNF carbon nanofibers mean global temperature of the earth. In general, CO2 comprises
CNM carbon nanomaterials 85–95% of the total GHG emissions. Transportation is certainly the
CNT carbon nanotubes sector that has the largest potential impact for reducing GHG
emissions. Motor vehicles are a major source of CO2. Globally,
CO carbon monoxide
transport related emissions of CO2 are growing rapidly accounting
CO2 carbon dioxide
for 20–25% of the CO2 release in the atmosphere [2].
CVD chemical vapor deposition
Fuel consumption and CO2 emission of a vehicle are two
DC direct current indissociable parameters. According to the U.S. Environmental
EGR exhaust gas recirculation Protection Agency (EPA) estimates [3], the average annual amount
FC fuel cell of CO2 emitted by a passenger car is about 4.6 ton (equivalent to 1.3
FBR fluidized bed reactor ton of elemental carbon) assuming a total annual consumption of
FCV fuel cell vehicle about 2000 l of gasoline. In other words, the combustion of one
GHG green house gas gallon of conventional gasoline produces about 8.9 kg of CO2 and
H2 hydrogen the average car CO2 emission is about 230 g/km. Table 1 presents
H2S hydrogen sulfide the emission rates for hydrocarbons, CO, CO2, oxides of nitrogen
(NOx) and particulate matter. The calculations for ‘annual emission’
HC hydrocarbons
and ‘fuel consumption’ were based on an average annual mileage of
HFPP high-frequency pulsed plasma
20,000 km (12,500 miles) and a fuel economy of 10 km/l or 23.8
ICE internal combustion engine miles per gallon (mpg). These emission factors and fuel consump-
IPFC integrated plasma fuel cell tion rates are for gasoline-fuelled passenger cars and light-duty
LHDC liquid hydrocarbons decomposition trucks only [3].
LHV lower heating value
MW multi-walled 2. Onboard hydrogen generation
NOx nitrogen oxides
NG natural gas The development of an onboard system capable of converting
POX partial oxidation liquid hydrocarbon fuels, such as gasoline, into a stream of H2-rich
gas and carbon would make it possible to power internal
PrOx preferential oxidation
combustion engine (ICE) vehicles using standard fuels with H2.
RF radio frequency
Capturing and storing carbon onboard the vehicle could help
SEM scanning electron microscopy
mitigate climate change [4]. The advantage of onboard fuel
SI spark ignition processing for H2 and carbon production is clear: the utilization of
SMR steam CH4 reforming conventional fuels at improved efficiency and lower pollution
SW single-walled levels. The advantage of using liquid hydrocarbons as a H2 storage
TCD thermo-catalytic decomposition medium is that the current fuel distribution infrastructure can be
TEM transmission electron microscopy used for the transportation, storage, and dispersal of the liquid
UHC unburned hydrocarbons
Table 1
WGS Water gas shift
Total annual emissions of passenger car [3].
XRD X-ray diffraction
ZEV zero emission vehicle Pollutant/fuel Emission and fuel Annual emissions and
consumption rate fuel consumption
(per 100 km driven) (20,000 km)

Hydrocarbons (HC) 85.0 g 17 kg

1. Introduction Carbon monoxide (CO) 775 g 155 kg
Oxides of nitrogen (NOx) 59.4 g 12 kg
This review studied various hydrocarbon decomposition Particulate matter (PM10) 1.6 g 0.3 kg
Carbon dioxide (CO2) 23.1 kg 4620 kg
methods reported in the literature for reducing automotive CO2
Gasoline consumption 9.9 l 1980 l
emissions as part of carbon management. The ‘value-added’ carbon
 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
hydrocarbon. Moreover, the development of fuel-efficient engines
that produce fewer pollutants has been a major objective for many
years. The response of engine manufacturers, oil refiners, academic
researchers and catalyst industries to this public policy pressure
has been remarkable [5]. A steady increase in fuel economy and a
decrease in unwanted emissions have been achieved. However, it
is now believed that a new approach to reduce CO2 emissions is
required.
2.1. Hydrogen generation by catalytic routes (SMR, POX and ATR)
Turning gasoline into H2-rich gas for automobiles has been the
object of much R&D. Jamal and Wyszynski [6] reviewed the use of
H2 and H2-enriched gasoline as a fuel for SI-engines and the
techniques used to generate H2 from liquid fuels such as gasoline
and methanol, onboard the vehicle. Processes such as thermal
decomposition, SMR, POX, and exhaust gas reforming were
discussed. The authors discussed onboard generation of H2 for
use as an alternative or supplemental fuel for spark ignition
engines. A considerable amount of both theoretical and experi-
mental work has been done in this field. Predictive and
experimental results of the various investigators were reviewed
and summarized. The authors claimed that the difficulty of
gasifying or handling the solid carbon makes hydrocarbon
decomposition not suitable for onboard H2 generation.
There are various strategies to provide H2 to the engine. If H2 is
stored onboard in a tank, the mixture will consist of pure H2 and
gasoline. If H2 is obtained by processing a certain fraction of
gasoline in an onboard POX reformer, two different reformer gases
can be obtained. The first has a typical composition (by volume):
21% H2, 24% CO and 55% N2 (ignoring trace components). Since
such reaction is exothermic, the lower heating value (LHV) of the
reformer gas is roughly 15% lower than that of the incoming
gasoline [7]. The second gas is obtained water-gas shift reaction
and has a typical composition of 45% H2, 20% CO2 and 35% N2.
Allgeier et al. [8] presented a brief comparison of the various
types of onboard reformers (Table 2). A storage for reformate gas is
needed to cover the time during the reformer is being warmed up
to its operation temperature and as a buffer during high dynamic
transients. A wide variety of processes are available for onboard H2
generation from gaseous or liquid fuels [9]. The three main
onboard processes differ according to the nature of the primary
fuel used (ammonia, methanol, ethanol, gaseous or liquid
hydrocarbons) and to the chemical reactions involved (decom-
position, steam reforming or POX). Onboard generation of H2 is
certainly feasible from a technical standpoint but it is far from
evident that it could simply replace pure H2, stored in compressed
tanks or liquefied. Trimm et al. [5] reviewed the onboard
conversion of methanol, methane, propane, and octane to H2. A
Table 2
Properties of different onboard reformer types [8].
Process Advantages
Catalytic partial oxidation C-POX  Quick start-up (<10 s)
 No H2O necessary
 Compact
 Good dynamics
Steam reforming SR  High H2 portion (40%)
 High-pressure operation possible
 High efficiency (90–93%)
Auto-thermal reforming ATR  H2 portion (30%)
 Quick start-up
 Efficiency (85–90%)
 Good dynamics
3
combination of oxidation and steam reforming (indirect POX) or
direct POX is the most promising processes for H2 fuel cell. Indirect
POX involves combustion of part of the fuel to produce sufficient
heat to drive the endothermic steam reforming reaction. Direct
POX is favored only at high temperatures and short residence times
but is highly selective. However, indirect partial oxidation is shown
to be the preferred process for all fuels.
Other researchers investigated the utilization of auto-thermal
reforming (ATR) of gasoline for onboard generation of H2 [10,11].
ATR has been widely accepted as the most promising route to meet
efficiency, weight and volume, durability, and cost goals for
onboard fuel processors for automotive fuel cell systems.
Reforming catalysts are being developed to meet the unique
operating requirements for reforming complex fuel mixtures, such
as gasoline. Huffman and co-workers [12] and Goodman and co-
workers [13] used dehydrogenation of liquid hydrocarbons (such
as cycloalkanes) to produce CO-free H2. The advantage of using
liquid hydrocarbons as a H2 storage medium is that the current
distribution infrastructure can be used for the transportation,
storage, and dispersal of the liquid hydrocarbon. Supported-
bimetallic catalysts based on Fe, Ni and Pt are among the most used
catalysts.
2.2. Hydrogen generation by plasma route
Several different plasma reactors have been developed by
different research groups for onboard H2 generation from gasoline
using POX and ATR. Only a few plasma reactors have however been
developed for SMR of hydrocarbons. Several researchers [14–18]
have developed a non-thermal plasma reactor based on gliding arc
technology for gasoline reforming. These technologies are claimed
to be the most relevant techniques for onboard H2 generation
suitable for a large range of fuel flow rate. The initial version of a 2-l
plasmatron device required as much as 2 kW of electrical energy to
operate. The unit was developed to use an average of less than
100 W. Early systems took many seconds to produce H2 from cold
exhaust, an important disadvantage in real-world use, as emissions
are highest at this time. The latest versions were running in less
than a second. Moreover, the first prototypes produced H2 at just
one flow rate, however, recent prototypes managed transient or
varying flow demands equally well [14].
2.3. Onboard hydrogen supplementation to gasoline
The concept of H2 supplementation to gasoline in SI-engines
relies on the improvement of the thermal efficiency of engines
using conventional hydrocarbon fuels by supplementing them
with relatively small quantities of H2. The addition of H2 to the
cylinder charge can extend the lean limit equivalence ratio while
Disadvantages
 Low efficiency (83–86%)
 Low H2 portion (20%)
 Low-pressure operation only
 High temperature (1000 8C)
 Start-up, poor dynamics
 Size
 H2O required
 Temperature 600–700 8C
 Size
 Temperature 800–900 8C
 Pressures > 1000 kPa difficult
4 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
maintaining a sufficiently high flame speed. This will eliminate the
need to treat NOx emissions altogether. In this way the main fuel is
used more efficiently and only a small quantity of H2 is needed.
Jamal and Wyszynski [6] concluded that the operation of the
engine with 5–10 wt.% of H2 fuel makes it possible to operate the
engine in the very lean regime, which would not have been
possible without the presence of H2. A small amount of H2 added to
the air intake of a gasoline engine would enhance the flame
velocity and thus permit the engine to operate with leaner air to
gasoline mixture than otherwise possible. Although combustion
engines are expected to remain the dominant form of propulsion
for the next 20–30 years, there will be a wider range of vehicle
technologies and fuel types to address the economic, social and
environmental challenges of increased mobility.
The introduction of H2 as a supplemental automotive fuel
could be hindered by serious logistic problems. Worldwide, no
distribution system exists for H2, and its storage as a high-
pressure gas or cryogenic liquid requires vehicle capabilities
which do not exist commercially. These potential difficulties,
however, can be avoided by generating H2 in an onboard gas
generator using gasoline or other liquid hydrcarbons as feedstock.
Conte and Boulouchos [7] suggested that combustion of mixtures
of H2 and gasoline appears to be a good opportunity to join the
major advantages given by both fuels, avoiding many problems,
especially if small amounts of H2 are produced onboard directly
from gasoline. Use of H2 and gasoline blends seems to be
especially suitable for part load operation and reduction of
emissions during cold start. Some researchers have suggested that
a move toward a mix of transportation fuels and H2 may offer a
potential solution for reducing CO2 emissions. Because of the
lower carbon content of the fuel mix (gasoline and H2), it will be
possible to achieve carbon emission reduction. The technology of
using H2 as a combustion enhancement in ICE has been researched
and proven for many years. The benefits are factual and well
documented.
Cohn [17] summarized the benefits of H2 addition as follows:
i. H2 addition provides a large increase in fuel octane number.
ii. High octane fuel allows higher performance engines (turbo-
charging, high compression ratio).
iii. Engines can be smaller and more efficient.
iv. H2 addition also facilitates ultra-lean burn.
v. Engine efficiency can be increased by up to 30%.
Beister and Smaling [18] reported on the progress made with
the Hydrogen-Enhanced Combustion Engine (HECE) concept, as
applied to an SUV-class 3.2-l V6 test engine. The promise of HECE is
that the addition of a small amount of H2 to the cylinder charge can
allow homogeneous charge ultra-lean burn combustion engines to
operate much leaner than otherwise possible. Enhancing gasoline
combustion with a small H2 gas stream pointed toward a potential
estimated improvement in gasoline fuel economy of 20–30%,
depending upon the baseline engine.
In another application, Cohn [17] installed and tested the
plasmatron fuel converter on a commercial diesel car engine
thereby reducing NOx emissions by 80%. The goal of diesel
reformation by the plasmatron was the conversion of the heavy
diesel compounds into H2, CO, and light hydrocarbons for use in
after-treatment applications. The onboard H2 gas was used as a
low-cost, highly efficient, clean-burning, fast-starting regenerator
of particulate matter and NOx filters, which are used in diesel
exhaust gas after-treatment. For NOx catalyst regeneration
applications, the plasmatron may be turned on for a few seconds
every half minute or so. For diesel particulate filter applications,
the plasmatron could well be operated for a few minutes every few
hours resulting in much smaller duty cycles [15].
The addition of H2-rich gas to gasoline in an ICE seems to be
particularly suitable for achieving a near-zero emission Otto
engine, which would be able to easily meet the most stringent
regulations [7]. A bottled blend of CO, H2, and N2 (24%, 21%, 55% by
volume) was chosen to simulate the most likely output of a POX
reformer suitable for ICE applications. Experiments were carried
out on a Lombardini 4-stroke, 2-cylinder, 0.5-l engine, model LGW
523 OHC. The engine was equipped with a water-cooled EGR line
and water trap. Investigation on flame propagation was carried out
using ion-detection probes on the cylinder head surface and an
optical spark plug for light emission detection in the ignition
phase.
The results of measurements included fuel consumption,
engine efficiency, exhaust emissions, analysis of the heat release
rates and combustion duration, for both pure gasoline and blends
with H2-reformer gas. Simulations were performed to better
understand the engine behavior and NOx formation. The results
showed a significant decrease of unburned hydrocarbons (UHC)
and NOx emissions to near-zero. Light increase in CO emissions was
detected and CO2 emissions could be reduced by 3.5% in the FTP
cycle. Moreover, a significant increase of engine efficiency was
measured, which seems to be enough to compensate and
overcome the losses due to POX of gasoline in the onboard
reformer [7].
A conceptual design for the reduction of CO2 emissions from
transportation vehicles was proposed for producing hydrogen and
carbon using known hydrocarbon decomposition technology
onboard a vehicle. The produced hydrogen is then used in ICE
thus reducing CO2 emissions [4]. One of the advantages of the
proposed conceptual onboard fuel decomposition system is that
the vehicle will still be fuelled by liquid hydrocarbons (gasoline or
diesel), thus avoiding many of the direct infrastructure problems
associated with H2. Part of the gasoline (25 vol.%) is decomposed
onboard, and converted into H2 and carbon. H2 is then burned in
the engine and carbon is stored onboard for further sale, depending
on its quality. The decomposition of gasoline does not introduce
any energy losses since exhaust energy is used for the process.
However, the onboard fuel decomposer and carbon storage may
introduce some weight penalty.
Allgeier et al. [8] reported on the advanced emission and fuel
economy concept by using combined injection of gasoline and H2
in SI-engines. The authors tested concept for an SI-engine
consisting of combined injection of gasoline and H2. An H2-
enriched gas mixture was injected additionally to gasoline into the
engine manifold. The gas composition represents the output of an
onboard gasoline reformer. The simulations and measurements
showed substantial improvements in the combustion process
resulting in reduced cold start and warm up emissions and
optimized part load operation. The replacement of gasoline by H2-
rich gas during engine start led to zero hydrocarbons in the exhaust
gas. The mixed fuel operation enabled high EGR rates up to 50% or
extended lean burn limits resulting in reduced pumping losses and
increased effective engine efficiency.
3. Hydrocarbon decomposition processes
3.1. Catalytic and non-catalytic decomposition processes
The literature on the decomposition of hydrocarbons is based
on either catalytic (metal or metal-based) or non-catalytic
(thermal or plasma). The thermal decomposition of CH4 has been
used for decades for the production of carbon black (CB) with
hydrogen being a fuel for the process. Table 3 presents a summary
of literature highlighting the types of catalysts used, temperature,
and carbon products for the decomposition of hydrocarbons.
Almost all reviewed papers addressed the decomposition of
 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
Table 3
Catalytic and non-catalytic decomposition of hydrocarbons [19,20].
Parameter Temperature range (8C)
500–700 650–950
Catalysts used Ni-based Fe-based
Carbon product Filament Filament
natural gas (methane) into H2 and carbon black. Very few papers
discussed the decomposition of liquid hydrocarbons for onboard
applications.
There have been attempts to use catalysts to reduce the
maximum temperature of the thermal decomposition of hydro-
carbons. Common catalysts used are mainly transition and noble
metals such as Ni, Fe, Pd, Co, etc., supported on high surface area
ceramic substrates such as A12O3 and SiO2, etc. Among all the
catalysts investigated, nickel appears to provide the highest
activity and is most commonly used for this purpose. Other
papers disclose the use of carbon-based materials for decomposi-
tion of hydrocarbons into H2 and carbon. Among the advantages of
this process are fuel flexibility, relative simplicity and compact-
ness, clean carbon by-product, and reduction in CO2 and CO
emissions. Carbon deposition on the catalyst surface is the greatest
barrier to the transfer of the catalytic technology from the
laboratory to the industrial scale [21]. Most of the investigations
were aimed at methane decomposition for CO2-free H2 production
for stationary applications. However, there are few studies
targeting mobile applications for enhancing ICE efficiency or
possible fuel cell applications as well.
In order to capitalize on the performance of a highly active
catalyst, an efficient reactor must be designed. In the literature,
there are many suggestions and there are also a few patents. Some
of these have obviously not been tried out extensively and are not
so well suited for onboard H2 generation. In general, several types
of reactors, including tubular, fixed-bed, fluid wall, spouted and
fluidized bed reactors (FBR), are evaluated, and the latter is
considered the most promising for a large-scale operation. In FBR,
the bed of fine catalyst particles behaves as a well-mixed body of
liquid giving rise to high particle-to-gas heat and mass transfer.
However, for onboard applications, the use of FBR requires further
investigations. Several issues including heat input, catalyst with-
drawal, and regeneration need to be addressed [22]. The bulk of the
economics literature concerning decomposition of hydrocarbons
H2 reports economics of H2 production for large-scale purposes,
however, a few references are available related to onboard
applications. However, H2 production cost is a function of the
quality of carbon produced and its selling price.
3.2. Decomposition reaction and energy requirements
Various publications reported the different methods of produ-
cing H2 and carbon from hydrocarbons [23–30]. In the thermal-
based processes, hydrocarbon stream was pyrolyzed at high
temperature (over 1400 8C) by partial combustion of the hydro-
carbons and water quenching to prevent the reverse reaction. The
efficiency and the yield were extremely low. Another challenge in
hydrocarbon decomposition was difficulty in handling the carbon
build up on a continuous basis. Since no water or air is present, no
carbon oxides (e.g., CO or CO2) are formed, eliminating the need for
secondary reactors for water gas shift (WGS), preferential
oxidation (PrOx), or CO2 removal stages. Consequently, this
process offers significant emissions reduction.
The decomposition process is applicable to a variety of gaseous
and liquid hydrocarbon fuels, and it can potentially produce a
stream of H2 with the purity up to 95 vol.% (the balance-methane).
5
850–950 650–1050 1200–1300
Carbon-based Ni, Co, Fe, Pd, Pt, Cr, Ru, Mo Thermal/plasma
Turbostratic filament Graphitic turbostratic Amorphous
From the point of view of carbon sequestration, it is easier to
separate, handle, transport, and store solid carbon than gaseous
CO2. The thermal cracking accomplishes the removal and
separation of carbon in a single-step. The major drawback of the
thermal decomposition method is the energy loss associated with
the sequestration of carbon. Thus, cracking may be the preferred
option for natural gas and other hydrocarbons with high H2/C ratio.
The thermal decomposition of hydrocarbons can be represented by
the simplified net reaction:
Cn Hm ! nCs þ 12mH2 DH ¼ hydrocarbon dependent
Other compounds may also be formed, depending on the
reaction kinetics and on the presence of impurities in the raw
materials. The above reaction yields a carbon-rich condensed
phase and a H2-rich gas-phase. For instance, the decomposition of
CH4 is relatively a moderate endothermic reaction (the major
problem is the strong C–H bond):
CH4 ! Cs þ 2H2 DH ¼ þ 75:6 kJ=mol
The thermal energy requirement per mole of H2 produced is
only 37.8 kJ/mol H2 compared to 63 kJ/mol H2 for SMR. Less than
10% of the methane heating value is needed to drive the
endothermic process. The amount of CO2 emissions from the
process could potentially be as low as 0.05 mol CO2/mol H2 (if CH4
is used as a process fuel), compared to 0.43 mol CO2/mol H2 for
SMR. CO2 emissions could potentially be eliminated, if part of the
H2 product (theoretically, 16%) is combusted to produce process
heat. Muradov et al. [30] investigated several technological
approaches to the decomposition process heat supply including
internal, external and auto-thermal (or thermo-neutral) options
(Fig. 1). The auto-thermal option offered certain advantages over
other approaches due to its simplicity and versatility. Fig. 2
illustrates two possible technological concepts of CH4 decomposi-
tion process employing FBR with an internal and external heat
supply, respectively [20]. According to concept (A) in Fig. 2, the
heat input is provided by the heaters (e.g., heat pipes, catalytic
burners, heat exchangers, etc.) located within the FBR reaction
zone (in some cases, the primary heat source could be located
outside the reactor) [20].
Muradov et al. [22] discussed the option for supplying heat by
feeding a relatively small amount of O2 to generate enough heat to
carry out endothermic CH4 decomposition reaction. Although,
similarly to POX, the process would use about 2–3 times less O2
since the reaction does not proceed to syngas as a final product.
Concept (B) in Fig. 2 depicts the schematics of the decomposition
process with external heat supply, similar to the fluid catalytic
cracking or fluid coking processes. The process employs two fluid-
solid vessels: a reactor and a heater with catalyst particles
circulating between vessels in a fluidized state [22].
Bautista et al. [31] used theoretical analysis to predict the
temperature of CH4 decomposition in a planar stagnation-point
flow over a catalytic carbon surface. H2 is produced by means of a
heterogeneous reaction mechanism, which is modelled with five
heterogeneous reactions, including adsorption and desorption
reactions. The mass species, momentum, and energy conservation
equations for the gas-phase were solved, taking into account the
temperature of decomposition. Therefore, the critical temperature
6 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24

Fig. 1. Heat input options: internal (A), external (B) and thermo-neutral (C). Three process heat input options for decomposition of CH4. NG, natural gas; HRG, hydrogen-rich
gas; SG, stack gases; HC, heat carrier. (1) Methane decomposition reactor, (2) reactor heater, (3) catalyst particles heater [30].

conditions for the catalytic thermal decomposition were found by
using a high activation energy analysis for the desorption kinetics
of the adsorbed hydrogen component. Specifically, the numerical
estimations showed that, for increasing values of the velocity
gradient associated with the stagnation flow, the temperature of
decomposition increased, depending on the surface coverages of
the product species.
4. Decomposition by metal catalysts
4.1. Features of metal-based catalysts
Various monometallic and bimetallic catalysts were investi-
gated for the decomposition of gaseous and liquid hydrocarbons to
H2 and carbon materials [19,20]. The majority of the studies were
conducted using conventional fixed-bed reactors with few using
fluidized bed or membrane reactors. A variety of reaction methods
and techniques have been disclosed in the patented literature [32–
38]. In particular, Ni-based catalysts have attracted the attention of
majority of researchers due to their high catalytic activity and the
capability of producing high-value carbon products such as CNF or
CNT at moderate temperatures (500–700 8C). Other metal catalysts
such as Fe, Cu, Co were also investigated. Fe-based catalysts
operate at a somewhat higher temperature range. Noble metals (Pt,
Rh, Pd) have been used as promoters to improve the thermal
stability of transition metal catalysts and their capability to
accumulate carbon. The high-cost of non-conventional metals
prevents using them as catalysts for commercial utilization.
Bimetallic catalysts based on Fe, Ni, Pd, Cu, and other metals
were studied and some of these catalysts produced higher yields of
H2 compared to monometallic catalysts. Various support materials
including silica, alumina, magnesia, titania, zirconia, ceria, zeolites

Fig. 2. Schematic diagram of H2 and carbon production via catalytic decomposition of natural gas with an internal (A) and external (B) heat supply [22].
 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
and carbon materials were investigated to understand their role in
determining the nature of surface carbon and CO content in H2
product stream. Product carbons in metal-based hydrocarbon
decomposition catalysts were of high-value carbon materials,
including CNT or CNF. Other forms of carbon include graphitic,
turbostratic and carbidic carbon are usually accompanied by rapid
catalyst deactivation due to blocking of its active sites by carbon
deposits.
4.2. Decomposition of gaseous hydrocarbons
Most of the studies on the decomposition of gaseous hydro-
carbons were conducted using Ni-based catalysts. Other metals
investigated included Fe, Cu, Co, Pd and others. Various options
including different metals, supports, reaction conditions, and
reactor configuration were investigated to extend the catalysts life
and activity. Almost all the catalysts showed drop in their catalytic
activity with time-on-stream due to deposition of carbon. In some
process studies the catalyst regenerated by passing hot steam over
the catalyst bed to oxidize the carbon to carbon dioxide and form
more H2.
4.2.1. Monometallic catalysts
Ni catalysts: Most of the Ni-based catalyst studies were
basically on the decomposition of CH4 with some attention given
to the kinetics and the interaction of CH4 with Ni surfaces. Pohlenz
[32] operated a pilot plant with the capacity of 118 l/min for the
continuous production of H2 via catalytic decomposition of CH4 in
a fluidized bed of Ni-catalyst particles at 815–1100 8C. The
deactivated catalyst was continuously removed from the reactor
to the regeneration section where carbon was burned off, and the
Fig. 3. TEM images of CNF formed by CH4 decomposition over Ni catalyst at various time-on-stream: (A) 30 min, (B) 60 min, (C) 90 min, and (D) CNF [41].
7
regenerated catalyst was recycled to the reactor. Nakamura [33]
disclosed a reaction apparatus for the decomposition of ethylene to
produce high-purity H2 and carbon black (CB) over nickel particles.
At 400 8C, the yield of CB was about 88 wt.%.
The decomposition activity and longevity of the Ni-based
catalysts were mainly influenced by the amount of Ni and type of
support material. Many investigators correlated the decomposi-
tion activity results with NiO crystallite size, Ni metal surface area
and acidity of the catalysts [39–41]. The catalytic activity of the
pure Ni catalysts for CH4 decomposition was strongly related to the
crystalline size of the reduced Ni. The Ni catalyst with crystalline
size of about 10.8 nm had the highest carbon and H2 yields, and the
nickel crystalline of about 20 nm gave relatively lower carbon
yields. Further increasing the nickel crystalline size to about 24 nm
led to extremely low catalytic activity, and an increase up to 26 nm
resulted in total deactivation toward CH4 decomposition. Li et al.
[41] reported a novel Ni catalyst for CH4 decomposition to H2 and
CNF. The carbon yields of 354–398 gC/gNi were obtained before the
catalyst completely deactivated in about 75 h on stream with a
maximum CH4 conversion of about 10%. Fig. 3 shows high-
resolution TEM images of deposited carbon that was growing with
a filamentous structure. The Ni particles (darker spot) were all
located at the tip of CNFs.
Italiano et al. [42] investigated a new structured multilayer
reactor made of Ni-based thin layer catalysts for CH4 decomposition
500–600 8C. The influence of Ni loading (5–50 wt.%), Ni particle size,
reaction temperature, and GHSV on the reaction pattern was
evaluated. A volcano shape relationship between H2 space time yield
and Ni loading with a maximum range of 20–25 wt.% was found. H2
productivity and catalyst lifetime were controlled by the nature of
the coke formed on Ni active species. Temperature and GHSV
8 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
Fig. 4. CH4 conversion versus TOS over un-supported reduced NiO catalysts at
500 8C [43].
significantly affected both the kinetics and the mechanism
filamentous carbon (FC) formation. At temperatures less than
600 8C and low GHSV, the prevailing formation of FC prolonged
catalyst lifetime, while at 600 8C and high GHSV encapsulating
carbon was formed, causing a sudden decline in catalytic activity.
Cai et al. [43] used NiO nanoparticles as catalyst precursor for
CH4 decomposition at 300–500 8C. The advantage of using un-
supported reduced NiO catalyst was that the decomposition
reaction can be operated relatively at a lower reactor temperature.
The results showed uniform CH4 to H2 conversion rates of nearly
50% over periods of 2–3 h before carbon removal was required. The
un-supported NiO precursor particles better accommodated
carbon deposits made of small filaments or fibers. The NiO
generated from NiCl2 with an average particle size of 7.5 nm
showed the best performance for CH4 decomposition at 500 8C as
shown in Fig. 4. This high stability implied that the carbon
deposition capacity (often expressed by C/Ni ratio) is very high. The
9 nm size NiO particles prepared from nickel nitrate provided an
intermediate activity and stability performance among the three
experimental catalysts, and the 10 run size NiO particles prepared
Fig. 5. Schematics of FBR reactor for catalytic decomposition of CH4 to H2 and CNFs [50].
from the nickel acetate exhibited the lowest catalytic activity as
well as the lowest stability over time.
Very high concentration (up to 90 wt.%) of Ni catalysts was used
in the direct cracking of CH4 to produce H2 and filamentous carbon
[35]. However, CH4 conversion was quite low; 8% at 500 8C, 15% at
550 8C, and complete deactivation at 600 8C. High Ni content
catalysts (>50 wt.%) prepared from hydrotalcite clay-like structure
by co-precipitating mixed aqueous solution of Ni nitrate with
Na2CO3 were also used for the decomposition of CH4 [44]. It was
found that the maximum CH4 conversion occurred at 650 8C
irrespective of Ni loading, though the maximum value of
conversion increased with the increase in Ni content. A stable
production of H2 with more than 80 vol.% purity for over 10 h, and
at the same time 180 g of nanocarbon production on 1 g of catalyst
with a tubular morphology, were achieved. It was also reported
that the morphology of nanocarbon product was influenced by H2
in the feed itself.
Several studies addressed the interaction of Ni with Al2O3
support compared to other supports [45–49]. Murata et al. [47]
found that Ni-based catalysts supported on Al2O3 catalysts were
more active and stable for CH4 decomposition than Ni/SiO2 under
similar operating conditions. The catalyst activities at 550 8C
decreased in the following order: Ni/Ca/Al2O3 > Ni/Al2O3 > Co/
Al2O3 > Fe/Al2O3 > Fe/SiO2. The carbons formed after 14 h reaction
at 550 8C were of bent filamentous shape and of graphite-like
structure, and metallic Ni particles were located on the tip of the
filament, the diameters of which were between 55 and 77 nm. In a
similar study, Rahman et al. [49] studied CH4 decomposition over
5-wt.% Ni/g-Al2O3 in a thermobalance. Results showed that the
faster rates for carbon deposition obtained at high temperatures
(600–650 8C) were accompanied by faster deactivation. A similar
trend was observed for lower initial masses of catalyst (0.1–0.2 g).
Finally, a method of partial gasification was proposed as a
promising route for catalyst regeneration.
Parmon [50] reported the development of a Ni-based catalyst
with CH4 conversion at 60–77% and H2 yield of 80 vol.% at 700–
800 8C in a pilot with a revolving reactor system as shown in Figs. 5
and 6. The rotation of the fluidized bed reactor (FBR) was necessary
because of major magnification of volume of the catalyst at
formation CNFs. The reactor included a system for an input of raw
material and outlet of reactionary gases, electromotor with a
reducer, system of rotary seals ensuring leak-proof at gyration,
heating system and alone reactor.
 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
Fig. 6. Schematic of pilot reactor for catalytic decomposition of CH4 to H2 and CNFs
[50].
Mimura et al. [51] developed a high throughput screening (HTS)
method for identifying supported nickel catalysts for the decom-
position of CH4. Porous materials such as H-beta (SiO2/
Al2O3 = 150), H-beta (25), and H-ZSM-5 (90) were highly effective
supports for CH4 decomposition. The total time to find three active
catalysts among 18 catalysts could be reduced to about one-third
of that required with the conventional method. A Ni content of 5–
10 mmol g-support1 was adequate. The HTS results were con-
sistent with the results obtained using a conventional reactor.
Amiridis and co-workers [52–55] studied decomposition of
gaseous hydrocarbons such as CH4 and ethane over Ni/SiO2
catalysts in the temperature range 450–650 8C. The initial high
activity of the catalyst yielded 35% CH4 conversion at 550 8C. The
authors postulated that deactivation was due to spatial limitations
imposed on long cylindrical hollow filaments with a Ni particle at
the tip of each individual filament. In addition to H2 and
filamentous carbon, CH4 was formed during the decomposition
of ethane. Measurements conducted at different temperatures and
space velocities suggested that H2 was the primary product, while
CH4 was formed in a secondary step, presumably the hydrogena-
tion of surface carbon or CHy fragments. Almost complete initial
conversion of ethane was observed at a space velocity of
18,000 ml/g h at temperatures above 500 8C. Although the initial
yield of hydrogen increases with temperature, the rate of catalyst
deactivation also increases at higher temperatures. As a result, the
overall amounts of H2 produced and ethane converted over the
lifetime of the catalyst reach maxima at 500 8C.
Inoue and co-workers [56] studied the influence of catalyst
support, reaction gas and mechanism of CH4 decomposition over
Ni catalysts using thermogravimetric apparatus. The Ni/Zr catalyst
resulted in a high yield of multi-walled CNT along with H2. The
initial rate of CH4 decomposition increased with increasing
reaction temperature at 400–680 8C, but decreased with reaction
temperature above 700 8C. The CNT formed at higher temperatures
had more graphite-like structure than those obtained at lower
temperatures. Feed gas containing CH4 and H2 caused slow
deactivation of the catalyst, thereby carbon yield increased with
increasing partial pressure of H2 in the feed gas. It was concluded
that the most important factor governing the carbon yield is the
morphology of the catalyst support, which contributes to the
internal pressure of CNT thus determining their chemical
potentials.
In another study, Asai et al. [57] investigated the mechanism of
CH4 decomposition at high temperatures to elucidate the desirable
9
negative activation energy for the decomposition. For Ni/Al2O3, the
initial rate of carbon formation increased with reaction tempera-
ture up to 680 8C. However, the initial rate decreased at higher
reaction temperatures, implying that the reaction had apparent
negative activation energy, although thermodynamic considera-
tions suggest that higher temperatures should favor the decom-
position of CH4. The reaction order with respect to CH4 was ca. 1.4,
irrespective of the reaction temperature, whereas the reaction
order with respect to hydrogen changed from 0.5 to 0 by
increasing the reaction temperature from less than 700 8C to more
than 720 8C.
Goodman and co-workers [58,59] studied the decomposition of
CH4 over Ni supported on SiO2, H-ZSM-5, or HY. Maximum CH4
conversion (45%) was obtained at 550 8C along with a drop in the
release of CO concentrations (2500 ppm dropping to 750 ppm) and
CO2 (<500 ppm) in the product stream. The study highlighted the
dependence of the type of carbon formed and the amount of CO
evolved on the nature of the support. No filamentous carbon was
observed on Ni/H-ZSM-5 at elevated CH4 decomposition tempera-
tures, whereas Ni/HY and Ni/SiO2 showed filamentous carbon
formation over the entire temperature range studied (450–600 8C).
While two forms of carbon (carbidic and graphitic) were observed
on the Ni/SiO2 after CH4 decomposition at 450 8C, only graphitic
carbon was observed at 550 8C. The rate of CO formation was
observed to be highest on Ni/H-ZSM-5 and lowest on Ni/SiO2
(50 ppm). The low levels of CO coupled with the stability of the
catalysts for CH4 decomposition make this an interesting
conceptual process for H2 production. Regeneration studies have
shown that there is no loss of activity for CH4 decomposition at
450 8C on Ni/H-ZSM-5 over many reaction cycles.
Takenaka et al. [60–63] investigated CH4 decomposition at
550 8C and subsequent gasification of the CNF with CO2 into CO at
650 8C were performed over supported Ni catalysts (Ni/SiO2, Ni/
TiO2, Ni/Al2O3) and Ni supported fused silica. The catalytic activity
of Ni/F–SiO2 for the decomposition of CH4 decreased slightly after
the third cycle but the conversion of the carbons to CO was always
greater than 95%. All Ni catalysts deactivated with TOS due to
deposition of a large amount of CNF. Subsequent contact of CO2
with CNF on the deactivated catalysts resulted in the formation of
CO with a conversion of the carbons higher than 95%. Catalytic
activity of Ni/SiO2 for CH4 decomposition was high at early cycles,
however, the activity decreased gradually with the repeated cycles.
On the other hand, Ni/TiO2 and Ni/Al2O3 showed high activity for
CH4 decomposition and the activity was kept high during the
repeated cycles. As indicated earlier, the changes in catalytic
activities could be explained by changes in particle sizes of Ni
metal, i.e., Ni metal particles in Ni/SiO2 aggregated into ones larger
than 150 nm with the repeated cycles, while the particle sizes of Ni
metal in Ni/TiO2 and Ni/Al2O3 remained at an effective range for
CH4 decomposition (60–100 nm).
The decomposition of CH4 over 13 wt.% Ni/TiO2 showed first
order reaction with activation energy of 60 kJ/mol which was the
lowest activation energy reported in the literature for this reaction
[64]. It was also found that the adsorption of CH4 on the surface
was the rate-controlling step. The developed model indicated the
volumetric flow rate, catalyst weight, and temperature to be
decisive parameters in scale-up considerations and in the
extrapolation of laboratory-scale experimental results. Choudhary
et al. [65,66] screened different supports for Ni catalysts including
ZrO2, MgO, ThO2, CeO2, UO3, B2O3 or MoO3 and zeolites such as
HZSM-5, H, HM, NaY, Ce(72)NaY, or Si-MCM-41. H2 was produced
at stoichiometric amounts continuously at a constant H2 produc-
tion rate at low temperature (500 8C) in two parallel catalytic
reactors operated in cyclic manner. The process involved two
simultaneous reactions: first, catalytic decomposition of CH4 to H2
and carbon (deposited on the catalyst), and second, gasification of
10 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
the carbon deposited on the catalyst by steam to H2 and CO2. The
process showed best performance at an optimum value of the feed
switchover time. The Ni/ZrO2 and Ni/Ce(72)NaY showed promising
results for this cyclic process.
Ni catalysts supported by carbon materials was studied by
various researchers [67–74] for the decomposition of CH4 and
ethylene. Graphite, activated carbon (AC), CNT and CNF were used
as the carbon supports. Otsuka et al. [68] used Ni catalysts
supported on carbon materials to avoid a costly elimination
treatment of the catalyst from the formed CNF. The Ni/carbon
catalysts prepared by the impregnation of various carbon materials
with Ni(NO3)2 dissolved in acetone, followed by reduction in
hydrogen at 300 8C, showed better catalytic performance in the
decomposition of CH4 than those prepared by the impregnation
with aqueous Ni(NO3)2. The Ni (40 wt.%)/CNF showed the highest
catalytic performance giving a C/Ni value (moles of deposited
carbon per mole of Ni on the catalyst) of 1920 until complete
deactivation of the catalyst. An estimate of the average size of Ni
crystallites from XRD measurement suggested that the carbons
deposited from CH4 on various Ni/CNF would modify the size of Ni
crystallites during the reaction. It is suggested that 20 nm Ni
crystallites are most active for the growth of CNF.
Reshetenko and co-workers [70,71] studied CH4 decomposition
over Ni/catalytic filamentous carbon (CFC) at low temperatures.
The CFC supports were produced by CH4 decomposition over co-
precipitated Ni–Al2O3 (CFC (Ni)), Ni–Cu–Al2O3 (CFC (Ni–Cu)), Co–
Al2O3 (CFC (Co)), Fe–Al2O3 (CFC (Fe)), Fe–Co–Al2O3 (CFC (Fe–Co))
and Fe–Ni–Al2O3 (CFC (Fe–Ni)) catalysts with high metal loadings.
The highest yield of secondary carbon was found to reach 268.5 g/
gNi on Ni/CFC (Fe–Ni) catalyst at 525 8C. The authors suggested
that highly porous carbon supports were more suitable for
development of Ni/CFC catalyst for CH4 decomposition. Fig. 7
presents the curves of CH4 conversion versus TOS for various
supported Ni/CFC catalysts. The high activity of Ni/CFC catalysts
was accounted for the size of Ni particles (50 nm in size) that was
almost optimal for the filament growth. The following factors
might be responsible for the secondary growth of carbon on Ni/FC
systems:
i. Choice of the catalyst precursor (NiCl2).
ii. Textural properties of the support (the presence of pores larger
than 100 nm in size, and high porosity of the support).
iii. Surface structure of the filament with exposed graphite basal
planes provides weak metal–support interaction that makes
the system labile.
Fig. 7. Global kinetics of CH4 conversion over Ni/CFC catalysts (525 8C, CH4
pressure = 1 atm, space velocity = 45 l/g cat h) [70].
Ethylene decomposition over Ni supported on novel CNT and
CNF under consecutive reaction/regeneration cycles [72]. These
studies highlighted the effects of support chemical composition,
catalyst synthesis method and Ni metal loading on the catalytic
activity and stability of nickel. A novel 0.5 wt.% Ni/CNT catalyst
which showed the highest value of a constant H2 product yield
(17.5 mol H2/mol Ni), following consecutive reaction (complete
deactivation) regeneration (20% O2/He, 400 8C) cycles, ever
reported in the open literature has been developed.
Bai et al. [74] investigated Ni/activated carbon (AC) for CH4
decomposition which showed higher activity than AC itself and can
be operated at high temperatures to achieve much higher CH4
decomposition rate. The decomposition experiments revealed that
deactivated Ni/AC catalysts had a larger Ni crystal size than the
fresh ones, which led to the deactivation of the catalysts. A new
crystallite Ni3C in the catalyst was formed during CH4 decom-
position, which might be another disadvantageous factor for
catalyst deactivation. FC formation was observed and interlaced
with the deactivated catalyst surface. The formation of zigzag FC
with Ni metal on the tip shows that the mechanism of FC formation
and growth over AC may be the same as that of over Ni catalysts
supported on other supports. Temperature had great effect not
only on CH4 decomposition but also on the formation and the
characterization of FC. At 750 8C, acceptable CH4 decomposition
performance and better FC formation were obtained.
Deposited carbon appeared either as long filaments a few
nanometres in diameter emerging from Ni particles or as uniform
coatings [75]. Structural characterization shows that both carbon
forms have similar graphitic structures. The characterization study
shows that catalyst become deactivated when deposited carbon
prevents CH4 diffusion toward Ni surface. Diffusion is prevented in
much higher extent by coating carbon than by filaments. Operating
conditions promoting high decomposition rates enhance coating
versus filaments formation and shorten the catalyst life.
Other monometallic catalysts: compared to Ni-based catalysts,
other monometallic catalysts (Co, Fe, Cu) yield low carbon
formation in CH4 decomposition. Avdeeva et al. [76] investigated
carbon deposition on Co catalysts for CH4 decomposition at 475–
600 8C. Catalyst preparation method, type of support and
temperature regimes were found to strongly influence the
decomposition reaction with best performance are found with
the co-precipitated 60–75 wt.% Co–alumina catalysts at 500 8C. In
contrast to Ni-based catalysts, the carbon filaments with hollow-
like core morphology were produced on the Co catalysts.
Takenaka et al. [77] investigated the effect of supports on CF
formation for Co-based catalysts. The Al2O3 and MgO supports
were found to be superior to the SiO2 and TiO2 supports for CF
formation. CH4 conversion versus TOS for various supports is
plotted in Fig. 8. The 10–30 nm range for Co particles was preferred
for CF formation. It was found that the temperature had a
significant influence in determining the nature of the CF. MW-CF
were formed in the temperature range of 600–700 8C, whereas
helically coiled and bamboo-like CF were preferentially formed at
800 8C. It was also found that Co metal particles in the supported
Co catalysts were always present at the tip of CNF and CNT at
600 8C, while they were located in the hollow of CNT in addition to
the tip of them during the reaction at temperatures above 700 8C.
Smith and co-workers [78–81] investigated the kinetics, effect
of metal–support interaction and filamentous carbon (FC) forma-
tion thresholds on Co/SiO2 catalysts. The effect of Co dispersion,
reaction temperature and the presence of CO or H2 on the kinetics
of CH4 decomposition over 5–30 wt.% Co/SiO2 catalysts. Metal–
support interaction was studied by adding BaO, La2O3 or ZrO2 to
SiO2. Competition between FC formation and encapsulating carbon
formation controlled the catalyst deactivation rate. The initial CH4
decomposition activity increased and the catalyst deactivation rate
 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
Fig. 8. Change of CH4 conversion as a function of TOS at 500 8C over Co catalysts
supported on different supports [77].
decreased as Co dispersion decreased in the range 13–5%. Indirect
evidence for CHx migration from the metal to the support was
reported. The migration is much less important than FC formation
in removing carbon from the metal surface and thereby main-
taining catalyst activity during CH4 decomposition. The presence
of H2 or CO reduced the net rate of carbon deposition and increased
the net rate of carbon removal by diffusion through the Co,
respectively.
Ermakova and co-workers [82,83] investigated CH4 decom-
position on un-supported Fe powder as well as supported Fe
catalysts. With the exception of SiO2 support, the other supports
(Fe/Al2O3, Fe/TiO2) gave similar CF yields as un-supported Fe
powder (17 g CF/g cat). The study on Fe/SiO2 catalyst showed that
the silicates depended on their concentration in the catalyst could
provide a promoting effect or an inhibiting effect on CF formation.
The Fe/SiO2 catalyst with optimal silicate content showed a yield of
45 g CF/g Fe. Although the yield of CF on Fe-based catalysts was
small, Fe-based catalysts produced predominantly thin walled CF
(considered to be more valuable than other CF).
Takenaka et al. [84] investigated the structural changes of Fe
species and the nature of the CF formed during CH4 decomposition
reaction on Fe/Al2O3 and Fe/SiO2 catalysts. The study showed that
small sized Fe particles were transformed into Fe3C while the
larger particles were converted into carbon atom saturated a-Fe
species. The supports had a significant effect on the nature of the CF
formed during the reaction; multi-walled CF and chain like carbon
fibers were formed on Fe/Al2O3, while CF composed of spherical
carbon units were formed along with chain like carbon fibers on Fe/
SiO2 catalysts. Konieczny et al. [85] studied the effect of Fe-based
catalyst preparation methodology on the activity for CH4 decom-
position. The catalyst was synthesized from magnetite by
reduction in the presence of a reducing gas (CH4 or H2) using a
fixed-bed flow reactor at atmospheric pressures and from 800 to
900 8C. Reduction under CH4 was found to synthesize a catalyst
with the desired properties and smallest preparation time (2 h).
The main advantages of these catalysts included their ability to
completely decompose CH4 (as compared to a maximum of 81% by
other catalysts) and to maintain high reactivity for a long period of
time (more than 75 h).
Ammendola et al. [86–88] studied CH4 decomposition and
catalyst regeneration strategies of Cu/g-Al2O3 having different
copper content in fixed-bed and fluidized bed within the
11
temperature range 800–1000 8C. The nature of the active phase
and the best catalyst composition was determined by comparison
with reference compounds containing copper oxide and copper
aluminate, respectively. The results showed that, although a
mechanical regeneration of surface catalyst by attrition was not
possible, there were are some promising features to carry out the
decomposition process in a fluidized bed reactor for a continuous
hydrogen production. The advantages of this catalytic system
were: relatively high catalytic activity over that reported for
carbon- and nickel-based catalysts; and relatively high mechanical
resistance to attrition. This catalyst could be used in fluidized bed
reactor (FBR) applications, considering that, in addition to a low
attrition rate, it was also characterized by carbon deposition
without formation of CNF with the metal particles on their tips. In
this framework, the formation of CNF should be avoided due to
attrition phenomena occurring in FBR which could remove the
active metal particles from the support. Three different strategies
of catalyst regeneration, carbon combustion in air, CO2 gasification
and steam gasification were also analyzed.
Wang et al. [89] demonstrated that molten magnesium was an
efficient catalyst for the homogeneous decomposition of hydro-
carbons such as CH4, ethane, and polyolefins (plastic and rubber),
for the generation of H2 and micrometer size carbon particles. The
catalyst lost activity because of the evaporation of metal Mg. The
activity was restored by heating the upper cold section of the
reactor to slide Mg back to the reactor bed. Mg2C3 was identified as
reaction intermediate in the reaction. In the decomposition of
polyolefins, CH4 was the only gaseous by-product and can be
recycled back to the reactor for H2 and carbon generation.
4.2.2. Bimetallic catalysts
Studies on hydrocarbon decomposition over bimetallic cata-
lysts such as a combination of Cu, Fe, Ni, Pd, and other metals
showed that these catalysts were more active and produced higher
yields of H2 compared to monometallic catalysts.
4.2.2.1. Cu-based bimetallic catalysts. Carbon filaments and nano-
metric carbon particles formed from CH4 decomposition on nano-
sized Ni–Cu/Al2O3 catalyst at 720–830 8C were investigated with a
transmission electron microscope. Bamboo-shaped carbon fila-
ments were found formed at moderate temperatures. Their
morphology depended on the amount of copper doped into the
catalyst, the composition of the feed gas and the reaction
temperature. Cu doping enhanced the catalyst stability when
employed in a suitable amount. However, it made the catalyst
particles to become quasi-liquid state at 700–740 8C in CH4
decomposition. Consequently, the catalyst particles were easily cut
into small particles and encapsulated by the growing carbon
layers. The tendency became pronounced with the increase of Cu
content. This effect might play an important role for the
deactivation at high temperature [90,91].
Li and co-workers [92,93] examined the decomposition of CH4
using a co-precipitated Ni–Cu/Al2O3 catalyst in a two-stage FBR at
two different reaction temperature schemes, i.e., constant
temperature and pre-induction operation. This allowed the
fluidized catalysts to decompose CH4 with high activity in the
high-temperature condition; then the carbon produced will diffuse
effectively to form CNTs in both low and high-temperature regions.
The two-stage nano-agglomerate FBR is shown in Fig. 9. Unlike the
fixed-bed reactor/single-stage FBR studies, wherein a rapid
catalyst deactivation was observed at 850 8C, the catalyst showed
significantly lower deactivation rate in the two-stage FBR. The
authors believed that the two-stage temperature operation
decreased the disparity in carbon production and diffusion rates.
At constant temperatures, the catalyst showed quasi-stable
activity below 640 8C for a notable time period, while its
12 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24

Fig. 9. Two-stage nano-agglomerate FBR for CH4 decomposition [92].

performance decayed fast above this temperature and a quick The results showed that coiled nanofibers and the CNF ropes were
deactivation was observed at 740 8C. However, for reaction at grown on Ni–Cu catalysts.
740 8C, the durability was improved if the catalyst was induced for
10 min at 550 8C in the reaction atmosphere. 4.2.2.2. Fe-bimetallic catalysts. Shah et al. [98–102] studied the
Wang et al. [94] found that a Ni–Cu–MgO catalytic system catalytic dehydrogenation of CH4 using nanoscale, binary, Fe–M
maintained its activity for the decomposition of CH4 at high levels (M = Pd, Mo, or Ni) catalysts supported on alumina. At the reaction
for substantially long periods of time at 665–725 8C. TEM temperatures of approximately 700–800 8C and space velocity of
examinations revealed that the solid carbon consisted exclusively 600 ml/g h, the product stream was composed of over 80 vol.% of
of CNF possessing a ‘‘platelet’’ structure, in which the graphite H2, with the balance being unconverted CH4. Fig. 10 shows that the
layers are aligned in a direction perpendicular to the axis of the product carbon was in the form of potentially useful MW-CNT.
fiber. In sharp contrast, the Ni–MgO catalyst exhibited negligible Shen et al. [103] compared the catalytic performance of Fe–Ni
activity at temperatures above 650 8C. Li et al. [95] carried CH4 catalysts supported on Mg(Al)O that were prepared by nanopar-
decomposition over Ni–Cu/Nb2O5 in a fixed-bed reactor at ticle (np) synthesis impregnation and incipient wetness (IW)
atmospheric pressure. The addition of Nb2O5 increased the yield methods for the non-oxidative dehydrogenation of CH4 to H2 and
of H2 and carbon capacity of high loading bimetallic Ni–Cu CNT. Compared with the Fe–Ni/Mg(Al)O catalyst prepared by
catalysts, and prolonged the lifetime of these catalysts in CH4 incipient wetness, the nanoparticle catalyst was more easily
decomposition at high temperature. The maximal yield of H2 was
7274 mol H2/mol Ni for 65Ni–25Cu–5Nb2O5 catalyst at 600 8C,
which is one of the highest values of the catalysts for CH4
decomposition reported so far. TPR results showed that the
reduction temperature of Ni–Cu alloy is lower than that of single
Ni- or Cu-supported samples and the well-crystallized Ni–Cu
species was formed in bimetallic catalysts.
A series of Cu–Ni–Al catalysts at a (Ni + Cu)/Al mole ratio of 3
and Cu/Ni mole ratio in the range of 0.03–0.4 was prepared by co-
precipitation from corresponding metal nitrate solutions at
alkaline pH [96]. CH4 conversion tests at 670 8C showed a
significantly enhanced catalytic reactivity of 2 mol% Cu-doped
catalysts as compared to a pristine Ni catalyst. A higher copper
doping led to a less significant improvement in catalytic reactivity.
Solovyev et al. [97] reported that Ni–Cu/SiO2 catalyst exhibited the
best activity and selectivity at 600 8C. Total H2 yield of 60.8 mol H2/
g cat (during 24 h time-on-stream) and the total H2:CH4 ratio of 8.4
were obtained during propane decomposition under these optimal
conditions. The possible reaction scheme of propane decomposi-
tion over Ni-based catalysts and the reasons of increasing the
selectivity of H2 were discussed. At temperatures above 600 8C CNF Fig. 10. SEM image MW-CNT grown by CH4 decomposition over prereduced Mo–Fe/
with thin coating of pyrocarbon on their surface were obtained. Al2O3 catalyst [98].
 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
Fig. 11. TOS and CH4 conversion over Fe–Ni np/Mg(Al)O (0.2 g loading) and Fe–Ni IW/Mg(Al)O (1.0 g loading) catalysts at 600 and 650 8C. The dashed line shows the
equilibrium conversion at that temperature.
reduced at a lower temperature (600 8C in H2) and exhibited
enhanced CH4 dehydrogenation and longer life-times at both 600
and 650 8C as shown in Fig. 11. Each reduced Fe–Ni nanoparticle
functioned as an active site for the growth of CNT. The CNT were in
the form of multi-walled nanotubes (MWNT) of relatively uniform
diameter. An invar-like Fe–Ni–C alloy phase was believed to be the
active phase for CH4 dehydrogenation. The deactivation of the
nanoparticle catalyst was principally due to encapsulation of
catalyst particles by the CNT.
4.2.2.3. Ni-bimetallic catalysts. Wang and Baker [104] disclosed a
method for decomposing CH4 over two hybrid catalysts repre-
sented by the formula: NixMgyO at 500–525 8C and NixMgyCuzO at
750–760 8C. The catalysts, which contain a higher level of active
Ni-sites (higher than 25%) were capable of a extending lifetime as
well as substantially higher H2 and carbon yields even at higher
reaction temperatures when compared to conventional mono-
metallic catalysts. In a series of experiments the influence of
adding a small amount of a third component to the Ni–MgO
catalyst formulation on the decomposition of CH4 was explored.
Catalysts were prepared by introducing 8.7 wt.% of Cu, Co or Fe,
respectively into the 78% Ni–MgO system and then reacted in
60 ml/min CH4 at 550 8C. In most cases, the reactions were
conducted for as long as the catalytic activity was maintained at
greater than 4%. The results showed that that under the reaction
conditions employed none of the additives appeared to enhance
the catalytic activity of the 78% Ni–MgO system. On the other hand,
the addition of Cu was unexpectedly found to exert a significant
impact on the lifetime of the catalyst system.
Otsuka and co-workers [105–108] investigated the modifica-
tion of Ni catalysts with Pd to enhance the catalytic activity and life
for CH4 decomposition. In particular, the supported Ni catalysts
modified with Pd showed high turnover number of hydrogen
formation at temperatures higher than 700 8C with a high one-pass
methane conversion (>70%). CH4 decomposition on Ni/SiO2 or Pd/
SiO2 formed CNF with Ni or Pd metal particles at the tips of them.
Ni metal in Ni/SiO2 was transformed into Ni carbides at the
deactivation stage of the catalyst for methane decomposition. Pd
metal particles in Pd/SiO2 were fragmented into smaller ones
13
during methane decomposition. On the other hand, Pd–Ni/SiO2
produced CNF of different shapes than those on Ni/SiO2 and Pd/
SiO2, i.e., branched CNF. The local structure and average crystallite
size of Pd–Ni alloys in Pd–Ni/SiO2 did not change appreciably
during methane decomposition, but the shape of alloy particles
changed gradually. The number of facets on Pd–Ni alloy particles
that precipitated carbon atoms increased during methane decom-
position. This explains the increase in the catalytic life as well as
the formation of branched CNF.
The addition of Cu or Pd into Ni/SiO2 catalyst elongated its
catalytic life for the propane decomposition [109]. Especially, Ni–
Pd/SiO2 catalyst showed higher activity and longer life for the
decomposition of propane at 550 and 600 8C, compared to Ni/SiO2
and Ni–Cu/SiO2 catalysts. Ni–Pd/SiO2 catalyst was deactivated
gradually with time-on-stream during the decomposition of
propane due to the deposition of large amounts of carbon.
However, the activity of the catalyst for the propane decomposi-
tion was recovered completely by the gasification of deposited
carbon with CO2 into CO.
Cunha et al. [110] assessed Ni and Co Raney-type catalysts for
CH4 decomposition by comparing the measured conversions with
the equilibrium values. The activity, selectivity and stability were
dependent on the alloy composition and preparation method
(conventional or quenched alloy types), as well as the operating
conditions. Textural properties, chemical compositions and
catalyst performances were determined, and the carbon deposits
were characterized by different techniques. The catalysts obtained
from Raney-type alloys prepared by quenching showed better
performance for CH4 decomposition than conventional systems,
with conversions approaching equilibrium. The stability of the
catalysts could be extended by increasing the contact time and by
H2 pre-treatment of the catalysts. The carbon deposits consist
mostly of CNF and CNT.
The decomposition of CH4 over Mn–Ni//TiO2 catalysts was
investigated at 725 8C and GHSV of 2700 h1 [111]. The effects of
catalyst synthesis and pre-treatment of 15 mol% MnOx/20 mol%
NiO/TiO2 catalysts were identified. The 15 mol% MnOx/20 mol%
NiO/TiO2 catalyst that was prepared using the impregnation
method without any pre-treatment showed high activity for the
14 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
Fig. 12. Kinetic curves of CH4 conversion over Pd/Al2O3 and Pd–M/Al2O3 (M = Ni, Co,
Rh, Fe, Cu and Ag) at 700 8C [113].
CH4 decomposition reaction along with the formation of CNT. The
regenerated samples showed no significant decrease in CH4
conversion after up to six cycles of decomposition and regenera-
tion. The XRD patterns of the regenerated samples indicated that
no apparent structural change occurred.
Fig. 13. SEM images of Pd–M/Al2O3 (M = Ni, Co Rh and Fe) catalysts after deactivation for CH4 decomposition at 700 8C [113].
Ni-loaded catalysts supported on oxidized diamond showed the
highest catalytic activity for the decomposition of CH4 [112].
Oxidized diamond was useful as a novel unique catalytic support
material. When oxidized diamond was used as a catalyst support
material, Ni-loaded oxidized diamond catalyst showed the highest
H2 yield. Whisker-type carbon nanomaterials were produced on
Ni–Pd-loaded/oxidized diamond catalysts for CH4 decomposition.
4.2.2.4. Pd-bimetallic catalysts. Ogihara et al. [113] concluded that
highly concentrated H2 (>94 vol.%) and CNF can be deposited by
CH4 decomposition in a temperature range of 700–850 8C. Pd-
based alloys containing Ni, Co, Rh, or Fe showed high activity and
long life for CH4 decomposition at 700 8C. Fig. 12 shows the kinetic
curves of CH4 conversion over bimetallic supported catalysts at
700 8C in a flow rate of 80 ml mon1 with 0.03 g of catalyst. Fig. 13
shows SEM images of Pd–M/Al2O3 catalysts (M = Ni, Co, Rh, and Fe)
after deactivation for CH4 decomposition at 700 8C.
4.3. Decomposition of liquid hydrocarbons
From a thermodynamic point of view, the decomposition of
liquid hydrocarbons is more favorable than the decomposition of
CH4, since almost 1.5–2 times less energy is required to produce a
unit volume of H2. Supported-bimetallic catalysts based on Fe, Ni
and Pt were among the most used catalysts. The decomposition of
cycloalkanes was examined over Ni/fumed silica (Ni/F–SiO2) at a
temperature of 500 8C [114]. The main products were H2 and CNF
with a low concentration by-product CH4. The number of carbons
deposited per one Ni atom after complete deactivation of the
 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24 15

Fig. 14. C/Ni and selectivity of H2 formation for the decompositions of different C6-
alkanes over Ni/F–SiO2 at 500 8C. (&) C/Ni; ( ) selectivity of H2 formation [114].

catalyst was in the range of 750–1000 depending on the starting Fig. 15. Change in the formation rates of (a) H2 and (b) CH4 as a function of time-on-
alkanes. The selectivity of H2 formation increased as the number of stream during the decomposition of the model kerosene over Ni-based catalysts
carbon in the molecular structure of alkanes increased. The authors [115].
concluded that gasoline range alkanes (various C6-alkanes and
C8H18) were superior to the light alkanes (<C4) for selective
decomposition into H2 and carbon. The C/Ni values and the
selectivities of H2 formation till the complete deactivation
(occurred within 150 min) of the catalyst for the formation of
H2 for C6-alkanes are indicated in Fig. 14.
Takenaka et al. [115] investigated the decomposition of
kerosene over Ni-based catalysts using various types of support
materials including vapor-grown carbon fiber (VGCF), Al2O3, SiO2
(Cab-O-Sil), and TiO2. Ni/TiO2 catalyst showed the highest activity
and longest life for the decomposition of a mixture of tert-
butylcyclohexane, n-dodecane, and diethylbenzene (denoted as
kerosene). Supported Ni catalysts were deactivated rapidly during
the decomposition of diethylbenzene, whereas H2 was formed
efficiently through the decomposition of tert-butylcyclohexane
and n-dodecane. The catalytic performance of supported Ni
catalysts for the decomposition of diethylbenzene was improved
by the addition of Zn species. Significant activity lost occurred
during 20–30 min and complete activity loss was observed within
60–75 min [115]. Fig. 15 shows the change in the formation rates
of H2 and CH4 as a function of TOS in the decomposition of the
model kerosene over different Ni-based catalysts at 500 8C using
0.09 g catalyst, partial pressure of model kerosene = 4 kPa, and
total flow rate = 60 ml/min. By increasing the reaction temperature Fig. 16. Yields of H2 and CH4 in the decomposition of the model kerosene 600 8C
[115].
from 500 to 600 8C the H2 yield increased but there was no effect on
the catalyst life. The H2 yields at 600 8C were higher in the order of
Ni/TiO2 > Pd–Ni/SiO2 > Fe/Al2O3 > Ni–Cu/SiO2, whereas the order increased from 550 to 600 8C, the formation rate of H2 became
at 500 8C was Ni/TiO2 > Ni–Cu/SiO2 > Ni–Pd/SiO2 > Ni/VGCF significantly higher. In addition, the deactivation of the catalyst at
(Fig. 16). 600 8C with TOS was more gradual.
Ni–Pd/SiO2 showed high catalytic activity for the decomposi- Huffman and co-workers [12,102] investigated the dehydro-
tion of commercial kerosene [109]. Especially, Ni–Pd/SiO2 catalyst genation of liquid hydrocarbons (such as cycloalkanes) over
showed higher activity and longer life for the decomposition of nanoscale binary Fe–M (M = Pd, Mo, or Ni) catalysts supported
propane at 550 and 600 8C, compared to Ni/SiO2 and Ni–Cu/SiO2 on alumina. Catalytic decomposition of cyclohexane using the
catalysts. Fig. 17 shows the changes of the formation rates of H2 (4.5 wt.% Fe–0.5 wt.% Pd)/Al2O3 catalyst produced primarily H2,
and CH4 as a function of time-on-stream in the decomposition of benzene, and un-reacted cyclohexane below 450 8C, but only H2,
commercial kerosene. In both the reactions of kerosene, hydrogen CH4, and CNT above 500 8C. Fig. 18 shows TOS behavior of the (Fe–
and methane were formed and their formation rates decreased Pd)/Al2O3 catalyst for cyclohexane decomposition at 625 8C.
gradually with time-on-stream. As the reaction temperature Significant deactivation of the catalyst began after about 1.5 h
16 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
Fig. 17. Changes of the formation rates of H2 (a) and CH4 (b) as a function of TOS in
the decomposition of commercial kerosene over Ni–Pd/SiO2 catalyst at 550 8C (*)
and 600 8C (*) [109].
Fig. 18. Products distribution of cyclohexane decomposition over (Fe–Pd)/Al2O3 at
625 8C [102].
TOS, where CH4 is dimerized and polymerized to yield C2+
products. CNTs exhibited two distinct forms depending on the
reaction temperature. Above 600 8C, they were predominantly in
the form of MW-CNTs with parallel walls in the form of concentric
graphene sheets. At or below 500 8C, CNF with capped and
truncated stacked-cone structure were produced. At 625 8C, the
decomposition of cyclohexane produced a mixture of the two types
of carbon nanostructures.
The dehydrogenation of a Jet A hydrocarbon mixture was
investigated by Goodman and co-workers [116] for the production
of hydrogen for fuel cell applications. Because of their relative
importance with respect to the spectrum of hydrocarbons in the
mixture, cyclohexane and decalin were investigated indepen-
dently. A hybrid catalyst, Pt/g-Al2O3–ZrO2/SO42 was designed to
enhance the H2 production yields. Sulfated zirconia is a well-
known superacid catalyst and can be incorporated into a Pt/g-
alumina catalyst to increase its acidity. Pt–Sn/g-alumina-ZrO2/
SO42 hybrid catalysts were prepared by calcining a physical
Fig. 19. Experimental apparatus of spouted reactor used for propene decomposition
[117].
mixture of Pt–Sn/g-Al2O3 to ZrO2/SO42consisting of a mass ratio
of 6–4 at 550 8C for 12 h. For identical operating conditions the H2
production yield over this hybrid catalyst is 5% higher than
achieved with Pt/g-alumina.
Uemura et al. [117] proposed two-stage successive decom-
position spouted-bed reactors from recycled plastics. They
investigated the effect of the type of spouting medium on the
decomposition behavior of propene in a reaction apparatus as
shown in Fig. 19. In the first reactor, plastic chips were fed into the
reactor and instantaneously decomposed into lower hydrocarbons
(mainly propene). In the second reactor, the hydrocarbons were
further decomposed into carbon and H2 using four types of
spouting medium (Ni-plated a-alumina, Pd-plated a-alumina, Ni-
impregnated g-alumina, and a-alumina). The Ni-impregnated g-
alumina gave the best conversion and H2 yield. The results were
attributed to the well-known tendency for Ni-impregnated g-
alumina to have a higher metal dispersion than Ni-plated a-
alumina. It was likely that many Ni particles were still accessible
for propene because of the filamentous carbon mechanism for
nickel, in which nickel particles are attached at the outer end of the
filament formed. On the other hand, for other spouting media, this
advantage could not be expected.
5. Decomposition by carbon catalysts
5.1. Features of decomposition by carbon catalysts
The use of carbon as catalysts and supports to decompose
hydrocarbons offer certain advantages over metal-based catalysts
due to their availability, durability, low-cost, sulfur resistance, and
much higher temperatures withstand. Muradov [23–25] pioneered
the decomposition of hydrocarbons over carbonaceous materials.
The concept is based on the catalytic decomposition of CH4 over
active carbon particles for production of H2-rich gas and carbon
deposition on the surface of original carbon particles. The most
important features of carbon-based decomposition route are as
follows:
i. It can be catalyzed by carbon produced in the process, so that an
external catalyst would not be required (except for the start-up
operation).
 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
ii. The separation of carbon product from the carbon catalyst is not
necessary.
iii. Valuable carbon by-product is yielded.
A variety of carbon materials of different origins and structures,
including a wide range of activated carbon (AC), carbon black (CB),
microcrystalline graphites and nanostructured carbons have been
reported in the literature. The experimental data evidenced a
general trend of increasing catalytic activity in the decomposition
of hydrocarbons with the increase in carbon surface area, which
points to a heterogeneous catalytic nature of the reaction. Most of
the reported literature used CH4 as feed, however, some
publications discussed some aspects related to the decomposition
of liquid hydrocarbons such as hexane, octane, gasoline, kerosene
and diesel. Addition of special dopants (e.g., ZnO, CaO, Zn, Fe, etc.)
to the carbon material prevents production of H2S when sulfurous
feeds are used [25].
5.2. Decomposition over carbonaceous materials
Cha et al. [118] disclosed a method for decomposing
hydrocarbon gases using carbon (char) and applying radio
frequency (RF) as heating source. Carbon is an excellent RF
energy absorber and also a good reducing agent. When char is
placed in RF electric field, its temperature rapidly increases, and a
tremendous temperature gradient will be established between
the bulk gas-phase and char particles. Since feed gas was produced
from mild coal gasification therefore CO was also present in
substantial amount in the final H2-rich gas mixture. The CO and
hydrocarbon species could also be converted to H2 using RF
energy. Fig. 20 depicts the schematic of the apparatus that was
proposed by for the electromagnetic-catalyzed production of H2
and AC. CH4 began to dissociate at above 150 W of RF power. A 96%
conversion was achieved at 550 W. The outlet gas temperature
was less than 80 8C.
Murata et al. [119] disclosed a process for H2 production from
the decomposition of CH4 and other hydrocarbons by contacting
them with fine particles of a carbonaceous material obtained by
arc discharge between carbon electrodes and having a large
external surface area. Carbonaceous materials also included: soot
obtained from the thermal decomposition of different organic
Fig. 20. Schematic diagram of apparatus for producing H2 using electromagnetic-catalyzed reaction [118].
17
compounds or the combustion of fuels, CNTs, activated charcoal,
fullerenes C60–C70, and, finely divided diamond. CH4 feed was
diluted with an inert gas (preferable CH4 concentration in the
range 0.8–5 vol.%). An increase in CH4 concentration in feedstock
from 1.8 to 8 vol.% resulted in a drastic drop in CH4 conversion
from 64.6 to 9.7% (at 950 8C). It was stated that during
hydrocarbon decomposition (the experiments usually ran for
30 min) the carbon samples gradually lost their catalytic activity.
It was suggested that oxidizing gases like H2O or CO2 be added to
the pyrolyzing zone to improve the catalyst life. However, this
would inevitably contaminate H2 with carbon oxides and require
an additional purification step. The authors also suggested that
the spent catalyst be combusted, that would be very wasteful,
especially, considering the high-cost of the carbon materials used
in the process.
Arild [120] proposed a compact decomposition system for
use onboard vehicles using carbon as a catalyst for pre-
processing of gaseous hydrocarbons for H2 production for
polymer electrolyte fuel cell (PEFC). Fig. 21 shows the schematic
drawing of the system. Chu [121] disclosed used a system and
method that used nanostructured carbon as catalyst to produce
H2 and further nanostructured carbon as products using a
spouted-bed reactor. Several heat input options were proposed
including electrical resistive heating, radio frequency (RF)
heating, microwave, thermal plasma, solar energy and even
nuclear energy. The decomposition of CH4 and propane was
conducted using carbon catalyst at 1350 8C for up to 4 h. The
process was precisely controlled in such a way that the carbon
particles generated in reaction had a unique nanostructure so
their surfaces can act as catalytic sites for the decomposition of
hydrocarbons.
Huang et al. [122] studied the catalytic role of carbons in the
decomposition of CH4. Using first principles calculations at the
density functional theory level, the authors demonstrated that the
defective carbons can be used as catalysts for CH4 decomposition,
without the need for other catalysts and the catalytic sites can be
regenerated by the deposition of carbon decomposed from CH4, to
make the hydrogen production a continuous process. Additionally,
since no other gases are produced in the process, the cost of CO2
sequestration and hydrogen purification from CO contamination
will be dramatically reduced.
18 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
Fig. 21. Schematics of compact pyrolytic system adapted to use in vehicles for producing H2 as fuel [120].
5.3. Decomposition over carbon black and activated carbon
Muradov et al. [123–128] screened over 30 different samples of
elemental carbon, including a variety of ACs, CBs, nanostructured
carbons (including, carbon nanotubes and fullerenes C60/70),
graphites, glassy carbon and synthetic diamond powders for the
catalytic activity in CH4 decomposition. It was found that the
catalytic activity of carbons is mostly determined by their origin,
structure and surface area. A series of experiments on the catalytic
decomposition of a wide range of liquid hydrocarbons (pentane,
hexane, octane, gasoline, and diesel fuel) was conducted using
different carbon-based catalysts [23].
The decomposition of CH4 over samples of AC and CB catalysts is
shown in Figs. 22 and 23. AC catalysts featured relatively high
catalytic activity in CH4 decomposition reaction at the temperatures
of 850–900 8C. At this temperature range and the residence time of
few seconds, the initial concentration of H2 in the effluent gas after
the catalytic (fixed or fluidized bed) reactor using AC particles was
50–60 vol.% (the balance-unconverted CH4) [124]. The catalytic
activity, however, dropped synchronously with the loss in the
carbon surface area due to deposition of catalytically inactive carbon
Fig. 22. CH4 decomposition over samples of activated carbons [124].
species produced from CH4. The subsequent treatment of the
deactivated carbon sample with steam and/or CO2 at 900–1000 8C
drastically increases its surface area and completely restores its
original catalytic activity toward CH4 decomposition.
Different thermo-catalytic reactors for the decomposition of
CH4, propane and gasoline using carbon catalysts were investi-
gated [123]. The results are summarized in Table 4. The data on the
hydrocarbon conversion and the effluent gas composition were
related to the average quasi-steady state values. The effluent of
propane and higher hydrocarbons decomposition contained,
besides H2, CH4, a mixture of C2, C3, and C4-alkanes and olefins
which were easily identified. However, the analyses of liquid
products were much more complex.
High surface area AC and CB catalysts were used in the
decomposition of selected hydrocarbons (propane, CH4, gasoline
vapor) [25]. The hydrocarbon feedstock entered the lower section
of the catalytic reactor, thermally decomposed within the catalyst
layer, and the products of its decomposition (H2 mixed with small
amounts of CH4) exited via a ceramic filter located at the top
section of the reactor. The reactor temperature and the hydro-
carbon residence time within the catalytic zone were maintained
Fig. 23. CH4 decomposition over various samples of carbon black [124].
 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24 19

Table 4
Themocatalytic decomposition of hydrocarbons on different types of carbon catalysts [123].

Hydrocarbon Catalyst Reactor T (8C) Conv. % H2 CH4 C2H6 C2H4 (C2H2) C3+

CH4 CB, BP2000 PBR 950 30.9 47.2 52.7 0 0.1 0

CH4 Acetylene black PBR 850 23.3 37.8 61.9 0.1 0.2 0
CH4 CB, XC-72 PBR 850 28.0 43.7 56.2 0 0.1 0
CH4 CB, BP2000 FBR 850 9.1 16.7 83.1 0 0.2 0
CH4 – TR 1200 53.8 63.8 27.4 0.1 1.2 (7.5) 0
CH4:H2 1:4 – FVR 1200 89.3 10.7 0 0 0
CH4:C3H8 (3:1) CB, BP2000 FBR 850 38.2 50.1 2.1 9.0 0.6 0
CH4:C2H4 3:1 CB, BP2000 FBR 850 36.2 53.9 2.0 7.9 0
Propane AC, KE PBR 800 100.0 88.3 11.7 0 0 0
Propane Acetylene black PBR 850 100.0 62.1 37.9 0 0 0
Propane CB, BP2000 FBR 850 98.0 27.0 39.5 1.5 29.4 2.6
Gasoline AC, KE PBR 800 100.0 49.4 37.6 2.1 9.8 1.1
Gasoline CB, BP2000 FBR 850 100.0 52.0 33.2 2.1 11.1 1.6
CH4:gasoline CB, BP2000 FBR 850 – 40.0 55.5 0.3 3.0 1.2

PBR: packed bed reactor; TR: tubular reactor; FBR: fluidized bed reactor; FVR: free volume reactor; AC: activated carbon; CB: carbon black; BP: black pearls.

in the range of 850–950 8C, and 20–50 s, respectively (depending
on the hydrocarbon). CH4 and propane were directly introduced
into the reactor, whereas, gasoline was evaporated and pre-heated
to 250 8C before entering the reactor.
Initially, the catalyst filled approximately one-third of the
reactor volume, leaving the rest of the space for the carbon to be
produced during the reaction. As the reaction proceeded, the
produced carbon gradually filled almost whole volume of the
reactor. At this point the feed was stopped, the reactor was cooled
down and the carbon was dislodged from the reactor. Fig. 24
presents the results of propane and gasoline decomposition over
selected carbon catalysts [25]. The results showed that H2 with
80 vol.% could be produced over AC at 880–920 8C. The use of CB,
however, produced pyrolysis gas with somewhat lower H2
concentration (in average, 70 vol.%). The XRD results showed that
turbostratic structure of carbon was produced as main carbon
product. Fig. 25 presents a conceptual block-diagram of a power
generation system comprising a reformer combined with fuel cell
intended for mobile or portable applications.
Several options were suggested to provide heat input to the
reactor such as:
i. Catalytic combustion of a fraction of the hydrocarbon fuel.
ii. Catalytic combustion of the anode exhaust gas (H2–CH4
mixture).
iii. The resistive heating of the reactor (equipped with a
membrane) using a fraction of the electrical output of the FC
(in case of propane, approximately 20% of the output).
The latter case presents a zero emission option. The specific
energy of a propane-reformer was in excess of 1 kWth h/kg
(including fuel storage). 4.5 kg of carbon was produced per kg of
H2 using propane as fuel. The results proved that it was technically
feasible to develop a hydrocarbon fuel reformer for onboard/
portable fuel cell applications without (or drastically reduced) CO2
emissions. In another disclosure, Muradov [125] combined of the
reactor with a gas separation unit to allow production of high-
purity H2 (at least, 99.0 vol.%). The technical feasibility of the
approach was demonstrated and the major aspects of the
invention were verified through laboratory-scale tests [126]. The
process was operated at a low temperature (T < 800 8C) and a low
rate of decomposition was reported. It relied on high surface area
carbon particles such as CB, AC or even ceramic powders. However,
several researchers reported that no clear relationship exists
between surface area of CB and ACs and the catalytic activity for
CH4 decomposition.
Lee and co-workers [129–134] conducted extensive studies on
the decomposition of CH4 over AC and CB catalysts in FBR. The
kinetic study revealed that the AC catalysts deactivated rapidly and
showed similar deactivation pattern. Smaller particles exhibited
higher activity than larger particles, indicating that the intra-
particle mass transport effect exists. Since the smaller particles
deactivated somewhat more slowly, the pore mouth blocking
seemed to occur especially in large particles [129]. Fig. 26 shows
the schematic diagram of FBR used in the study [131]. AC catalysts
showed good catalytic activity at the beginning of the reaction and
deactivated rapidly due to carbon deposition on the active sites.
The carbon deposition resulted in the deactivation of the catalyst
and it was either in the form of carbon filaments or carbon

Fig. 25. Schematic diagram of pyrolytic fuel reformer coupled with PEM fuel cell (1)
Fig. 24. Production of H2-rich gas via catalytic decomposition of propane and catalytic decomposition reactor, (2) fuel tank, (3) fuel cell stack, (4) sulfur trap, (5)
gasoline vapor using carbon catalysts [25]. methanator [25].
20 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
Fig. 26. Schematic diagram of fluidized bed reactor used for the decomposition of
AC catalysts [131].
agglomerates. Fig. 27 shows CH4 conversion as a function of time
with different types of AC at the temperature of 850 8C and gas
velocity of 1 Umf (minimum fluidized velocity).
Using different types of CBs the decomposition of CH4 was
investigated under atmospheric pressure at 750–1050 8C [132]. CB
catalysts exhibited stable catalytic activity despite carbon deposi-
tion. However, no trend could be deduced between the activity and
the surface area of fresh samples. The reaction order was near unity
and the activation energies over carbon blacks were significantly
lower than those over activated carbons. The decomposition of CH4
was investigated over AC and CB catalysts at 800–925 8C in a FBR
equipped with continuous withdrawal of the carbon products from
the reactor [134]. Distinctive difference was observed in the
Fig. 27. CH4 conversion as a function of time with different types ACs at 850 8C and
gas velocity of 1 Umf (0.9 l/g cat) [131].
catalytic activities of two carbon catalysts. The AC catalyst
exhibited higher initial activity which decreased significantly with
time. However, the CB catalyst exhibited somewhat lower initial
activity compared to the AC catalyst, but its activity quickly
reached a quasi-steady state and was sustained over time. The
effect of various operating parameters such as the reaction
temperature and the gas velocity on the reaction rate was
investigated.
Bai et al. [135] carried out CH4 decomposition over AC catalysts
in a fixed-bed, quartz-tube flow reactor. The kinetics of CH4
decomposition and surface properties changes before and after
reaction were investigated. As a non-carbon-based material, active
alumina was also used to compare and understand the catalytic
decomposition mechanism of CH4 over different materials. A
reaction order of 0.5 was obtained for CH4 decomposition over AC
catalysts and activation energies in the range from 117 to 185 kJ/
mol. AC catalysts showed higher activity on CH4 decomposition
than active alumina and the catalytic behavior was different too.
The difference is attributed to two steps of CH4 decomposition over
catalyst: carbon nuclei formation and carbon crystallites growth
with activation energies of 317 and 227 kJ/mol, respectively. The
pore size change in the course of CH4 decomposition over ACs
indicates that the catalytic reaction occurs mainly in the
micropores. Activated alumina has different pore properties and
carbon deposition in mesopores of the alumina is responsible for
the catalytic activity.
Krzyzynski and Kozlowski [136] tested the decomposition of
CH4 using ACs obtained from the same precursor (brown coal) by
its activation with KOH. The microporous carbon samples had
different surface areas but were of similar structure because of
the common origin. The results did show any correlation
between the surface area of the catalysts and their initial
catalytic activity indicating that the number of catalytically
active sites does not depend directly on the surface area of the
catalysts. However, it was found that at higher surface area the
resistance of the catalysts to deactivation increases. The process
of pore blocking (mainly micropores) by the carbonaceous
deposit formed during CH4 decomposition was responsible for
catalyst deactivation.
The use of CBs was investigated by Dunker et al. [137] for the
decomposition of CH4 in a quartz FBR (97 cm  4.2 cm). Experi-
ments were run for 400–2000 min using three types of CB, at
temperatures of 810–980 8C, and space velocities of 95–210 h1.
Under optimum conditions, the decomposition produced 40% H2 in
the reactor effluent, solid carbon that remained on the carbon bed,
and little else. However, at the higher temperatures (>965 8C), gas-
phase decomposition occurred with formation of polycyclic
aromatic hydrocarbons and suspended carbon particles. Typically,
H2 production decreased during the first 50 min then remained
approximately constant for an extended period and finally fell to a
low rate by 1600–2000 min.
Ashok et al. [40] studied several AC catalysts for CH4
decomposition activity at higher temperature. All the ACs showed
high initial activity followed by a smooth decrease until the steady
state. Besides their dissimilar surface areas, the initial activities of
all ACs were in narrow range and this was because a part of the
surface of ACs. Typical CH4 decomposition activities over AC
catalysts at 800 8C are presented in Fig. 28. The deactivation
behavior of catalysts was apparently due to the carbon deposition
in the pores of ACs produced by CH4 decomposition. Surface
studies revealed the increase in catalytic activity of catalysts in CH4
decomposition reaction with the increase in carbon surface area,
which points to heterogeneous catalytic nature of the reaction. The
catalytic activity, however, dropped synchronously with the loss in
the carbon surface area due to deposition of catalytically inactive
carbon species produced from CH4.
 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
Fig. 28. CH4 decomposition activities over activated carbons [40].
Suelves and co-workers [138–142] conducted several studies
on the use of carbonaceous materials for CH4 decomposition. The
initial reaction rate of decomposition was related to the surface
chemistry of the catalyst, in particular to the concentration of
oxygenated groups. Mesoporous carbons with high surface area
provided more stable and sustainable H2 production. Different
types of CBs with high external surface area, easily accessible to
CH4 molecules had been explored as an alternative to ACs. CBs with
high surface area provide relatively high CH4 decomposition rate.
While for the AC there was a rapid deactivation, for the CB samples,
the process went on until most of the surface was covered by
carbon crystallites produced from CH4. A kinetic study using CB
(BP2000) and AC (CG Norit) showed that the reaction order of the
two catalysts was 0.5. The activation energies over these catalysts
were 141 and 238 kJ/mol, respectively. CH4 decomposition
reaction over carbon catalysts seems to be controlled by two
simultaneous processes: first, decrease in CH4 decomposition rate
due to the blocking of catalytic active sites by the carbon species
deposited, and secondly, an increase in CH4 decomposition rate
due to the formation of catalytically active carbon species
produced from CH4.
6. Decomposition by plasma
6.1. Features of hydrocarbon decomposition by plasma
Among the different plasma characteristics, one can distinguish
two main categories: thermal plasma and non-thermal plasma
[26–28]. Table 5 presents the features of thermal and non-thermal
plasmas. For thermal plasma applications, electrical power
injected in the discharge is relatively high (e.g., higher than
1 kW) and the neutral species and the electrons interact for times
longer than microseconds, so that they have approximately the
same temperature (around 5000–10,000 K). The temperature in
the reactor, and the energy consumption, are thus both very high,
and the cooling of the electrodes is generally necessary to reduce
Table 5
Features of thermal and non-thermal plasmas [143].
Thermal plasma Non-thermal plasma
 Very high plasma power and density  Low gas temperature and very
high electron temperature
 High gas temperature  Low power density
 No selective chemical process can  Chemical selectivity may
be achieved be achieved
21
their thermal evaporation and ion-impact erosion. The use of this
technology is therefore not relevant for fuel cell applications,
which require an efficient production of H2 in terms of energy
consumption [16].
Plasmas, both thermal and non-thermal, have been extensively
studied for the decomposition and conversion of hydrocarbons.
Different kinds of plasmas and operational conditions produce
different product distributions. Plasma has been found to be
suitable for the decomposition of hydrocarbons, and for chemical
synthesis selection. Various researchers have investigated the use
of glow discharge, dielectric barrier discharge (DBD), corona, arc
plasma-jet, radio frequency (RF) plasma, and thermal plasma. In
some cases, the use of plasma has resulted in the carbon being
produced and isolated in solid form, thus avoiding the cost of
sequestering CO2.
Thermal plasma processes, with dc and/or RF excitation in
plasma-torches, have turned out to be very effective and clean,
without emission of green house gases and other pollutants, as
compared to conventional processes. Reaction enthalpies in the
process are supplied from external electrical power through arc
and/or inductively coupled discharges, and the high reaction
temperatures of 2000–10,000 K are easily achievable. This is not
obtainable by catalytic chemical reactions. The dc thermal plasma
process was developed and commercialized by Kvaerner Engineer-
ing to co-produce CB and H2.
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 decom-
position of CH4 and other light hydrocarbons. In general, their goal
was to produce CB utilizing CH4 as a source of carbon directly,
rather than more expensive acetylene or ethylene, with H2 as a
secondary product. However, the energy cost of these thermal
plasma processes poses critical issues for widespread use of this
technology.
6.2. Decomposition by DC RF plasma
Kim and Takahashi [144] demonstrated the use of dc-RF hybrid
thermal plasmas for the production of H2 and CB from CH4.
Appropriate operational conditions and reactor geometries were
first predicted from theoretical considerations and numerical
simulations. Plasma temperatures and equilibrium compositions
of the CH4/Ar mixture were obtained using thermodynamic data
and by the Gibbs free energy minimization method, respectively.
The temperature and velocity distributions inside the reactor were
also computed to get reactor design data, and to examine the heat
balance over the reaction chamber. One-dimensional gas-phase
kinetic simulations on the CH4 decomposition process were
performed, to estimate major species and their mole fraction, by
considering the detailed reaction mechanism. For the synthesis
experiments on continuous production of H2 and CB, a stainless
steel reactor and a dc-RF hybrid torch were fabricated. All
experiments were conducted at an atmospheric pressure environ-
ment with the reactor pre-heated for 20 min by applying a 3-MHz
RF plate power of 30 kW and a dc power of 7.6 kW. Once the steady
conditions were established, CH4 gas was injected radially into the
hybrid plasma jet. The plasma-torch used in the experiments is
shown in Fig. 29.
For the synthesis experiments for the continuous production of
H2 and CB, a stainless steel reaction chamber (0.4 m in outer
diameter, 1.5 m in length) was used. A dc-RF hybrid torch (a dc
torch with an 8-mm anode nozzle, coupled with an RF torch having
a 50-mm-diameter confinement tube) was fabricated on the basis
of theoretical considerations. The injected CH4 was converted
22 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
Fig. 29. Cross-sectional view of a dc-RF hybrid thermal plasma-torch used for CH4
decomposition into H2 and CB [144].
mostly into H2 with a small volume fraction of C2H2, and the fine
carbon particles of 50–200 nm were identified from their TEM
images. The produced CB exhibited a great degree of crystal-
lization, and seems to have a great potential for conductive
applications like electrical cells. High-resolution TEM images also
show a specific structure of the produced CB, which has not been
observed in conventional furnace blacks. The CB produced in their
work possesses large specific surface areas and high adsorption
capacities as well, and they assert that their dc-RF hybrid plasma
system is very effective for the production of CB, with improved
properties for their applications.
Tsai and Chen [145] discussed a single-stage, non-catalytic, dry
CH4 plasmalysis process for producing mainly H2 and carbon
powders using an atmospheric-pressure microwave plasma
reactor is demonstrated. A high selectivity of H2 and carbon
powders, and a low required energy consumption of H2 could be
obtained simultaneously at a low-applied power and a high inlet
concentration of CH4 ([CH4]in), reaching 86.0% (selectivity of H2),
50.7% (selectivity of carbon), and 6.7 eV/molecule–H2, respec-
tively, at 0.8 kW when CH4 gas was fed from the downstream of the
cavity resonator. In addition, large amounts of nanocarbon
powders, which consisted of carbon atoms and had a graphite-
rhombohedral structure with a particle size of about 50 nm, were
produced. These particles had potential for using as a support for
platinum catalysts in fuel cells.
6.3. Plasma versus catalytic approach
Non-thermal plasma can accelerate chemical reactions at low
temperature as well, through the generation of active species by fast
electrons. If active species, generated by non-thermal plasma, are
capable of promoting many cycles of chemical transformation, then
a high specific productivity of plasma can be combined with the low
energy consumption of traditional catalysts. Thus it is that this so-
called plasma/catalysis approach has generated strong interest in
recent decades. Some hydrocarbon conversion processes, in
particular CH4 decomposition into H2 and CB, are endothermic
reactions, and to cover process enthalpy and to shift chemical
equilibrium to H2 and carbon, reactions must be at high temperature
in any case. Nevertheless, the temperature level required to shift
chemical equilibrium is relatively low (600–1000 K), and one can
use, for the process, relatively low-potential heat, while plasma will
be applied only as a catalytic agent for active species generation.
Comparing the plasma approach with conventional catalytic
technology, Deminsky et al. [146] concluded that the catalytic
methods, essentially in the case of small- and moderate-scale
portable applications, has certain problems because of relatively
low specific productivity, high metal capacity, and equipment size.
Thermal plasma replaces catalysis, and accelerates chemical
reactions, mainly because of its high-temperature features. The
advantages of the thermal plasma chemical methods lie in the
extremely high specific productivity of the apparatus, the low
investment, and the operation costs. However, relatively high
electric energy consumption applies certain restrictions on the
possible applications of the thermal plasma approach.
7. Conclusions
A wide variety of methods and techniques have been reported
in the literature for the endothermic decomposition of hydro-
carbons to H2 and different types of carbon. These approaches can
be categorized into thermal, catalytic (metal and carbon-based)
and plasma methods. Almost all the proposed processes are
applicable to a variety of gaseous and liquid hydrocarbon fuels, and
some of the processes can potentially produce a stream of high-
purity H2. While the decomposition reaction has been extensively
investigated, unfortunately less attention has been devoted to
energy balance and economical issues of the process. Very few
publications addressed the heat supply options for the decom-
position reaction. Nowadays, the decomposition of hydrocarbons
is drawing attention for the production of not only pure H2, but also
high-value carbon nanomaterials such as CNFs and CNTs.
Many different metal and carbon catalysts have been investi-
gated for the hydrocarbon decomposition reaction. However, the
choice of a suitable catalyst depends on many factors, such as
reactor design, economy and estimated reactor temperature. There
have been serious attempts to use catalysts to reduce the
maximum temperature of the thermal decomposition of hydro-
carbons. Common catalysts used are noble and transition metals,
such as Ni, Fe, Cu, Co, Mo, Pd, Rh, Pt, Nb, etc., supported on high
surface area ceramic substrates, such as A12O3 and SiO2, etc. Nickel
catalysts have been extensively studied due to their relatively
higher activities compared to other transition metals as well the
high-purity of carbon nanoproduct. Carbon deposition on the
catalyst surface is the greatest barrier to the transfer of the
catalytic technology from the laboratory to commercialization.
The plasma approach is relatively an attractive alternative for
the production of H2 and carbon since it replaces catalysts and
accelerates chemical reactions. Researchers have investigated
various kinds of non-thermal low-temperature plasmas such as
dielectric barrier discharge, arc plasma-jet, radio frequency
plasma, direct current generators, and microwave plasmatrons.
The progress in these types of plasmas depends obviously on the
development of a suitable and energy efficient onboard device that
can generate such plasma.
Acknowledgements
The authors wish to thank the support of Saudi Aramco,
Dhahran and the Research Institute at King Fahd University of
Petroleum & Minerals, Dhahran, in publishing this review.
References
[1] N. Muradov, T. Veziroglu, Intl. J. Hydrogen Energy 33 (2008) 6804–6839.
[2] P. Leduc, B. Dubar, A. Ranini, G. Monnier, Oil Gas Sci. Technol.-IFP 58 (2003) 115–
127.
[3] EPA, Average Annual Emissions and Fuel Consumption for Gasoline Fueled
Passenger Cars and Light Trucks, EPA Emission Facts No. 420-F-022, EPA Office
of Transportation and Air Quality, August 2005.
[4] A. Al-Dawood, F. Al-Muhaish, WO Patent 2006/094137, 8 September 2006.
[5] D. Trimm, Z. Onsan, Catal. Rev. 43 (2001) 31–82.
[6] Y. Jamal, M. Wyszynski, Intl. J. Hydrogen Energy 19 (1994) 557–572.
 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24 23

[7] E. Conte, K. Boulouchos, SAE 2004-01-0972. [72] P. Savva, G. Olympiou, C. Costa, A. Ryzhkov, Esftathiou, Catal. Today 102–103
[8] T. Allgeier, M. Klenk, T. Landenfeld, E. Conte, K. Boulouchos, SAE 2004-0101270. (2005) 78–82.
[9] M.M. Prignet, Revue Institut Francais du Petrole 52 (1997) 349–360. [73] K. Takehira, T. Ohi, T. Shishido, T. Kawabata, K. Takaki, Appl. Catal. A: Gen. 283
[10] Y. Shi, J. Van Pelt, R. Khan, M. Ruffo, J. Zhao, B. Bowers, J. Cross, ECS Trans. 5 (2007) (2005) 137–143.
645–654. [74] Z. Bai, H. Chen, B. Li, W. Li, Intl. J. Hydrogen Energy 32 (2007) 32–37.
[11] X. Karatzas, B. Lindstrom, M. Nilsson, L. Pettersson, Chem. Eng. J. 142 (2008) 309– [75] I. Suelves, M. Lazaro, R. Moliner, B. Corbella, J. Palacios, Intl. J. Hydrogen Energy
317. 30 (2005) 1555–1567.
[12] Y. Wang, Y.N. Shah, G. Huffman, Energy Fuels 18 (2004) 1429–1433. [76] L. Avdeeva, D. Kochubey, S. Shaikhutdinov, Appl. Catal. Gen. 177 (1999) 43–51.
[13] B. Wang, G.F. Froment, D.W. Goodman, J. Catal. 253 (2008) 239–243. [77] S. Takenaka, M. Ishida, M. Serizawa, E. Tanabe, K. Otsuka, J. Phys. Chem. B 108
[14] L. Bromberg, D. Cohn, A. Rabinovich, N. Alexeev, A. Samokhin, R. Ramprasad, S. (2004) 11464–11472.
Tamhankar, Intl. J. Hydrogen Energy 25 (2000) 1157–1161. [78] Y. Zhang, K.J. Smith, Catal. Today 77 (2002) 257–268.
[15] L. Bromberg, L.K. Hadidi, D. Cohn, Presented at MIT Plasma Science Fusion Center [79] X. Li, Y. Zhang, K.J. Smith, Appl. Catal. A: Gen. 264 (2004), 81–.
PSFC/JA-05-10, August 2005. [80] Y. Zhang, K.J. Smith, Catal. Lett. 95 (2004) 7–12.
[16] T. Paulmier, L. Fulcheri, Chem. Eng. J. 106 (2005) 59–71. [81] Y. Zhang, K.J. Smith, J. Catal. 231 (2005) 354–364.
[17] D. Cohn, Presented at the Coalition for Plasma Science, May 2004. [82] M. Ermakova, D. Ermakov, A. Chuvilin, G. Kuvshinov, J. Catal. 201 (2001) 183–
[18] U. Beister, R. Smaling, MTZ 66 (2005) 17–19. 197.
[19] N. Muradov, T. Veziroglu, Intl. J. Hydrogen Energy 30 (2005) 225–237. [83] M. Ermakova, D. Ermakov, Catal. Today 77 (2002) 225–233.
[20] T.V. Choudhary, D.W. Goodman, Catal. RSC 19 (2006) 164–183. [84] S. Takenaka, M. Serizawa, K. Otsuka, J. Catal. 222 (2004) 520–531.
[21] J. Holladay, J. Hu, D.L. King, Y. Wang, Catal. Today 139 (2009) 244–260. [85] A. Konieczny, K. Mondal, T. Wiltowski, P. Dydo, Intl. J. Hydrogen Energy 33
[22] N. Muradov, F. Smith, A. T-Raissi, in: Proceedings of 15th Saudi-Japan Catalyst (2008) 264–272.
Symposium, KFUPM, Dhahran, November 2005. [86] P. Ammendola, R. Chirone, L. Lisi, G. Ruoppolo, G. Russo, J. Mol. Catal. A: Chem.
[23] N. Muradov, Energy Fuels 12 (1998) 41–48. 266 (2008) 31–39.
[24] N. Muradov, Intl. J. Hydrogen Energy 26 (2001) 1165–1173. [87] P. Ammendola, R. Chirone, G. Ruoppolo, G. Russo, Combust. Sci. Tech. 180 (2008)
[25] N. Muradov, J. Power Sources 118 (2003) 320–322. 869–882.
[26] P. Gaudernack, S. Lynum, Intl. J. Hydrogen Energy 21 (1998) 1087–1093. [88] P. Ammendola, R. Chirone, G. Ruoppolo, G. Russo, R. Solimene, Intl. J. Hydrogen
[27] M. Steinberg, Intl. J. Hydrogen Energy 24 (1999) 771–777. Energy 33 (2008) 2679–2694.
[28] L. Fulcheri, Carbon 40 (2002) 169–176. [89] K. Wang, W.S. Li, X.P. Zhou, J. Mol. Catal. A: Chem. 283 (2008) 153–157.
[29] J. Halloran, Intl. J. Hydrogen Energy 33 (2008) 2218–2224. [90] J. Chen, Y. Li, Y. Ma, Y. Qin, L. Chang, Carbon 39 (2001) 1467–1473.
[30] N. Muradov, F. Smith, C. Huang, A. T-Raissi, Catal. Today 116 (2006) 281– [91] J. Chen, Y. Li, Z. Li, X. Zhang, Appl. Catal. A: Gen. 269 (2004) 179–186.
288. [92] W. Qian, T. Liu, F. Wei, Z. Wang, G. Luo, Y. Li, Appl. Catal. A: Gen. 260 (2004) 223–
[31] O. Bautista, F. Mendez, C. Trevino, Intl. J. Hydrogen Energy 33 (2008) 7419–7426. 228.
[32] J. Pohlenz, U.S. Patent 3,284,161 (1966). [93] D. Li, J. Chen, Y. Li, Intl. J. Hydrogen Energy 34 (2009) 299–307.
[33] N. Nakamura, US Patent 5,914,093, Jun 22, 1999. [94] H. Wang, R. Baker, J. Phys. Chem. B 108 (2004) 20273–20277.
[34] S. Cantacuzene, US Patent 6,315,977, November 13, 2001. [95] J. Li, G. Lu, K. Li Wang, J. Mol. Catal. A: Chem. 221 (2004) 105–112.
[35] P. Colombani, E. Cremonesi, EP Patent 1227062, July 31, 2002. [96] A. Naghash, Z. Xu, T. Etsell, Chem. Mater. 17 (2005) 815–821.
[36] D. Sioui, D.G. Towler, A. Oroskar, L. Zhou, S. Dunne, S. Kulprathipanja, L. Galperin, [97] E. Solovyev, D. Kuvshinov, D. Ermakov, G. Kuvshinov, Intl. J. Hydrogen Energy 34
F. Modica, T. Voskoboinikov, US Patent 6,506,510, January 14, 2003. (2009) 1–14.
[37] X. Chu, WO Patent 05/108287, November 17, 2005. [98] N. Shah, D. Panjala, G. Huffman, Energy Fuels 15 (2001) 1528–1532.
[38] N. Breuer, O. Marquardt, US Patent 6,939,634, September 6, 2003. [99] G. Huffman, N. Shah, Y. Wang, F. Huggins, Prepr. Pap. -Am. Chem. Soc., Di Fuel
[39] D. Gozzi, A. Latini, WO Patent 06/040788, April 20, 2006. Chem. 49 (2004) 731–732.
[40] J. Ashok, M. Subrahmanyam, A. Venugopal, Catal. Surveys Asia 12 (2008) 229– [100] N. Shah, Y. Wang, D. Panjala, G. Huffman, Energy Fuels 18 (2004) 727–733.
237. [101] N. Shah, D. Panjala, G. Huffman, US Patent No. 6,875,417, April 5, 2003.
[41] Y. Li, B. Zhang, X. Xie, J. Liu, Y. Xu, W. Shen, J. Catal. 238 (2006) 412–422. [102] Y. Wang, N. Shah, G. Huffman, Catal. Today 99 (2005) 359–362.
[42] G. Italiano, C. Espro, F. Arena, F. Frusteri, A. Parmaliana, Stud. Surf. Sci. Catal. 162 [103] W. Shen, F. Huggins, N. Shah, G. Jacob, Y. Wang, X. Shi, G. Huffman, Appl. Catal.
(2006) 633–640. 351 (2008) 102–110.
[43] M. Cai, Y. Li, W. Shen, J. Rogers, WO Patent No. 2007/100333, September 7, 2007. [104] H. Wang, H.R. Baker, US Patent No. 6,995,115, February 7, 2006.
[44] Y. Li, J. Chen, Y. Qin, L. Chang, Energy Fuels 14 (2000) 1188–1192. [105] K. Otsuka, S. Takenaka, Intl. J. Hydrogen Energy 26 (2001) 191–192.
[45] L. Piao, Y. Li, J. Chen, L. Chang, J. Lin, Catal. Today 74 (2002) 145–153. [106] K. Otsuka, H. Ohtsuki, S. Takenaka, Appl. Catal. A: Gen. 273 (2004) 113–122.
[46] J. Villacampa, C. Royo, E. Romeo, J. Montoya, P. Angel, A. Monzon, Appl. Catal. A: [107] K. Otsuka, S. Takenaka, Catal. Surveys Asia 8 (2004) 77–90;
Gen. 252 (2003) 363–383. S. Takenaka, Y. Shigeta, E. Tanabe, K. Otsuka, J. Catal. 220 (2003) 468–477.
[47] K. Murata, K.M. Inaba, M. Miki, T. Yamaguchi, React. Kin. Catal. Lett. 85 (2005) [108] S. Takenaka, Y. Shigeta, E. Tanabe, K. Otsuka, J. Phys. Chem. B 108 (2004) 7656–
21–28. 7662.
[48] M. Hazra, A. Elkamel, E. Croiset, in: Proceedings Intl. Hydrogen Energy Congress [109] S. Takenaka, K. Kawashima, H. Matsune, M. Kishida, Appl. Catal. A: Gen. 321
IHEC 2005, Istanbul, July 2003. (2007) 165–174.
[49] M. Rahman, E. Croiset, R. Hudgins, Top. Catal. 37 (2006) 137–145. [110] A. Cunha, J. Orfao, J. Figueiredo, Appl. Catal. A: Gen. 348 (2008) 103–112.
[50] V. Parmon, Presented at the ICS Meeting on Technologies for Hydrogen Produc- [111] S. Zein, A. Mohamed, Energy Fuels 18 (2004) 1336–1343.
tion and Fuel Cells, Trieste, Italy, March 2005. [112] K. Nakagawa, M. Yamagishi, H. Nishimoto, N. Ikenaga, T. Suzuki, T. Kobayashi, M.
[51] N. Mimura, M. Inaba, K. Murata, J. Japan Petroleum Institute 46 (2003) 133–137. Gamo, T. Ando, Chem. Mater. 15 (2003) 4571–4573.
[52] T. Zhang, M. Amiridis, Appl. Catal. A: Gen. 167 (1998) 161–172. [113] H. Ogihara, H.S. Takenaka, I. Yamanaka, E. Tanabe, A. Genseki, K. Otsuka, J. Catal.
[53] M. Amiridis, C. Bernales, WO Patent 99/43609, September 2, 1999. 238 (2006) 353–360.
[54] R. Aiello, J. Fiscus, H. Loye, M. Amiridis, Appl. Catal. A: Gen. 192 (2000) 227– [114] K. Otsuka, Y. Shigeta, S. Takenaka, Intl. J. Hydrogen Energy 27 (2002) 11–18.
232. [115] S. Takenaka, Y. Kobayashi, K. Otsuka, Energy Fuels 18 (2004) 1775–1783.
[55] S. Chin, Y. Chin, M. Amiridis, Appl. Catal. A: Gen. 300 (2006) 8–13. [116] B. Wang, G. Froment, D.W. Goodman, J. Catal. 253 (2008) 239–243.
[56] Y. Nagayasu, A. Nakayama, S. Kurasawa, S. Iwamoto, E. Yagasaki, M. Inoue, J. [117] Y. Uemura, Y.K. Baba, H. Ohe, Y. Ohzuno, Y. Hatate, J. Mater. Cycles Waste
Japan Petroleum Institute 48 (2005) 301–307. Manage. 5 (2003) 94–97.
[57] K. Asai, Y. Nagayasu, K. Takane, S. Iwamoto, E. Yagasaki, K. Ishii, M. Inoue, J. Japan [118] C. Cha, H. Bauer, R. Grimes, US Patent 5,164,054, November 17, 1992.
Petroleum Institute 51 (2008) 42–49. [119] K. Murata, H. Ushijima, K. Fujita, US Patent 5,650,132, July 22, 1997.
[58] T. Choudhary, C. Sivadinarayana, A. Klinghoffer, D. Goodman, Stud. Surf. Sci. [120] V. Arild, WO Patent 00/21878, April 20, 2000.
Catal. 136 (2001) 197–205. [121] X. Chu, US Patent Appl. 20,040,253,168, December 16, 2004.
[59] T. Choudhary, T.C. Sivadinarayana, C. Chusuei, A. Klinghoffer, D. Goodman, J. [122] L. Huang, E. Santiso, M. Nardelli, K. Gubbins, J. Chem. Phys. 128 (2008) 214702.
Catal. 199 (2001) 9–18. [123] N. Muradov, Progress Report DOE Contract DE-FC36-99GO10456, 2000.
[60] S. Takenaka, H. Ogihara, I. Yamanaka, K. Otsuka, Appl. Catal. A: Gen. 217 (2001) [124] N. Muradov, Catal. Commun. 2 (2001) 89–92.
101–110. [125] N. Muradov, US Patent 6,653,005, November 25, 2003.
[61] S. Takenaka, H. Ogihara, K. Otsuka, J. Catal. 208 (2002) 54–63. [126] N. Muradov, US Patent 6,670,058, December 30, 2003.
[62] S. Takenaka, S. Kobayashi, H. Ogihara, K. Otsuka, J. Catal. 217 (2003) 79–87. [127] N. Muradov, F. Smith, A. Raissi, Catal. Today 102–103 (2005) 225–323.
[63] S. Takenaka, Y. Tomikubo, E. Kato, K. Otsuka, Fuel 83 (2004) 47–57. [128] N. Muradov, Z. Chen, F. Smith, Intl. J. Hydrogen Energy 30 (2005) 1149–1158.
[64] S. Zein, A. Mohamed, P. Sai, Ind. Eng. Chem. Res. 43 (2004) 4864–4870. [129] M. Kim, E. Lee, J. Jun, G. Han, S. Kong, B. Lee, T. Lee, K. Yoon, Korean J. Chem. Eng.
[65] V. Choudhary, S. Banerjee, A. Rajput, J. Catal. 198 (2001) 136–141. 20 (2003) 835–839.
[66] V. Choudhary, A. Rajput, US Patent Appl. 20,040,118,047, June 24, 2004. [130] M. Kim, E. Lee, J. Jun, S. Kong, G. Han, B. Lee, T. Lee, K. Yoon, Intl. J. Hydrogen
[67] P. Chen, WO Patent 02/04345, January 17, 2002. Energy 29 (2004) 187–193.
[68] K. Otsuka, H. Ogihara, S. Takenaka, Carbon 41 (2003) 223–233. [131] K. Lee, G. Han, K. Yoon, B. Lee, Catal. Today 93–95 (2004) 81–86.
[69] K. Otsuka, Y. Abe, N. Kanai, Y. Kobayashi, S. Takenaka, E. Tanabe, Carbon 42 [132] E. Lee, S. Lee, G. Han, B. Lee, T. Lee, J. Jun, K. Yoon, Carbon 42 (2004) 2641–2648.
(2004) 727–736. [133] K. Lee, G. Han, K. Yoon, B. Lee, Presented at the Intl. Hydrogen Energy Congress,
[70] T. Reshetenko, L. Avdeeva, Z. Ismagilov, A. Chuvilin, Carbon 42 (2004) 143–148. IHEC 2005, Istanbul, July 2005.
[71] T. Reshetenko, L. Avdeeva, Z. Ismagilov, A. Chuvilin, V. Fenelonov, Catal. Today [134] J. Jung, W. Nam, K. Yoon, G. Han, Korean J. Chem. Eng. 24 (2007) 674–678.
102–103 (2005) 115–120. [135] Z. Bai, H. Chen, B. Li, W. Li, J. Anal. Appl. Pyrol. 73 (2005) 335–341.
24 S. Ahmed et al. / Applied Catalysis A: General 359 (2009) 1–24
[136] S. Krzyzynski, M. Kozlowski, Intl. J. Hydrogen Energy 33 (2008) 6172–6177.
[137] A. Dunker, S. Kumar, P. Mulawa, Intl J. Hydrogen Energy 31 (2006) 473–482.
[138] R. Moliner, I. Suelves, M. Lazaro, O. Moreno, Intl. J. Hydrogen Energy 30 (2005)
293–300.
[139] I. Suelves, J. Pinilla, M. Lazaro, R. Moliner, Intl. J. Hydrogen Energy 32 (2007)
3320–3326.
[140] M. Lazaro, J. Pinilla, I. Suelves, R. Moliner, Intl. J. Hydrogen Energy 33 (2008)
4104–4111.
[141] J. Pinilla, I. Suelves, M. Lazaro, R. Moliner, Chem. Eng. J. 138 (2008) 301–306.
View publication stats
[142] I. Suelves, M. Lazaro, R. Moliner, J. Pinilla, H. Cubero, Chem. Eng. J. 140 (2008)
432–438.
[143] A. Fridman, A. Gutsol, Y. Cho, C. Kalra, Presented at the Workshop on Carbon-Free
Production of Hydrogen from Fossil Fuels, Global Climate and Energy Project
(GCEP), Stanford, April, 2004.
[144] K. Kim, S. Takahashi, IEEE Trans. Plasma Sci. 33 (2005) 813–823.
[145] C. Tsai, K. Chen, Intl. J. Hydrogen Energy 34 (2009) 833–838.
[146] M. Deminsky, V. Jivotov, B. Potapkin, V. Rusanov, Pure Appl. Chem. 74 (2002)
413–418.