Renewable and Sustainable Energy Reviews 44 (2015) 221–256

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Production of greenhouse gas free hydrogen by thermocatalytic

decomposition of methane – A review
U.P.M. Ashik a, W.M.A. Wan Daud a,n, Hazzim F. Abbas b
a
Department of Chemical Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
Department of Chemical Engineering, University of Nizwa, Al Dakulaya, Oman

art ic l e i nf o a b s t r a c t

Article history: Thermocatalytic decomposition of methane (TCD) is a fully green single step technology for producing
Received 10 June 2014 hydrogen and nano-carbon. This review studying all development in laboratory-scale research on TCD,
Received in revised form especially the recent advances like co-feeding effect and catalyst regeneration for augmenting the
1 December 2014
productivity of the whole process. Although a great success on the laboratory-scale has been fulfilled,
Accepted 12 December 2014
TCD for greenhouse gas (GHG) free hydrogen production is still in its infancy. The need for
commercialization of TCD is greater than ever in the present situation of huge GHG emission. TCD
Keywords: usually examined over various kind of catalysts, such as monometallic, bimetallic, trimetallic, combina-
Catalytic methane decomposition tion of metal–metal oxide, carbonaceous and/or metal doped carbon catalysts. Deactivation of catalysts
Hydrogen production is the prime drawback found in TCD process. Catalyst regeneration and co-feeding of methane with other
Metal-carbon catalysts
hydrocarbon are the two solutions put forwarded in accordance to overcome deactivation hurdle. Higher
Methane co-feeding
amount of co-feed hydrocarbon in situ produce more amount of highly active carbonaceous deposits
Hydrogen separation membrane
which assist further methane decomposition to produce additional hydrogen to a great extent. The
methane conversion rate increases with increase in the temperature and decreases with the flow rate in
the co-feeding process in a similar manner as observed in normal TCD. The presence of co-components
in the post-reaction stream is a key challenge tackled in the co-feeding and regeneration. Hence, this
review hypothesizing the integration of hydrogen separation membrane in to methane decomposition
reactor for online hydrogen separation.
& 2014 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
2. Thermocatalytic decomposition of methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
2.1. Metal catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
2.1.1. Non-supported catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
2.1.2. Metal supported catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
2.1.3. Metal oxide supported catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
2.1.4. Ceramic and red-mud based catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
2.1.5. Thin layer catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
2.1.6. Influence of parameters on activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
2.1.7. Catalytic deactivation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
2.2. Carbonaceous catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
2.2.1. Carbon catalytic activity boost by metal doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
2.2.2. Influence of parameters on activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
2.2.3. Catalytic deactivation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237

Abbreviations: TCD, thermocatalytic decomposition of methane; SRM, steam reforming of methane; POX, partial oxidation; DRM, dry reforming of methane; GHG, green-
house gas; CNF, carbon nano-fibers; MSI, metal–support interaction; GHSV, gas hourly space velocity; TLC, thin layer catalysts; AC, activated carbon; CB, carbon black; ACPS,
activated carbon from palm shell; CNT, carbon nano tube; NCB, nano-sized carbon black; CNF, carbon nano fiber; MWNT, multiwalled nanotube; CLR, coal liquefaction
residue; HES, high-energy sites; HPC, hierarchical porous carbon; OSG, oxygen surface group; OCM, oxidative coupling of methane; DFT, density functional theory
n
Corresponding author. Tel.: þ 60 105023818; fax: þ60 379675319.
E-mail addresses: [email protected] (U.P.M. Ashik), [email protected] (W.M.A. Wan Daud), [email protected] (H.F. Abbas).

http://dx.doi.org/10.1016/j.rser.2014.12.025
1364-0321/& 2014 Elsevier Ltd. All rights reserved.
222 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

3. Comparison between metal and carbonaceous catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237

4. Co-feeding: a promising method for enhancing catalyst stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
4.1. Alkanes as co-feed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
4.2. Ethylene as co-feed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
4.3. Ethanol as co-feed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
4.4. Propylene as co-feed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
4.5. CO2 as co-feed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
4.6. H2S as co-feed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
5. Catalyst regeneration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
5.1. Gasification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
5.2. Combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
5.3. Partial regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
6. Separation of pure hydrogen: a hypothesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
7. Overall conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252

1. Introduction through water electrolysis [11]. The worldwide contribution of

different sources to overall hydrogen production and its sector
Hydrogen, the simplest, the lightest and the most abundant wise-usage are show in Fig. 1. The major contribution of NG for
element in the known universe appears to be one of the auspicious hydrogen production owe to the availability of huge methane
energy carriers, however, the greenest one if produced from reserves in deep ocean bed as well as in industrialized countries
renewable resources. This alternative green fuel is indispensable like United States [12].
in the contemporary scenario of huge greenhouse gas (GHG) Various hydrogen production method were developed, such as
emission from the combustion of fossil fuel. Since, fossil fuels bio-hydrogen production, reviewed elsewhere [13], steam reform-
dominate energy consumption with a market share of 87%, all ing of methane (SRM), partial oxidation (POX), coal gasification,
the while, renewable energy accounts 2% only [1]. According to the water splitting, biomass gasification and thermochemical pro-
International Energy Agency's World Energy Outlook 2012 [2], the cesses [14,15]. Water splitting process, consuming renewable solar
global energy requirement expected to grow by more than one- and wind energy is very fascinating, but not economical because of
third over the period 2035. The rise in energy consumption causes its poor efficiency and higher processing cost. Water can be
the elevation in the emission of GHGs like COx, CxHy, NOx, SOx, etc. directly converted to H2 and O2 with zero CO2 emission by using
[3]. Consequently, atmospheric CO2 level hits awful record highs photoelectrodes with sunlight illumination in aqueous electro-
[4]. This increasing CO2 emissions will lead to anthropogenic lytes. The integration of solar energy concentration systems with
global warming, climate change and ocean acidification, which systems capable to split water is of immense value and impact on
would have severe consequences for ecosystem and for sustain- the energetics and economics worldwide. For this application, the
ability of human society. Moreover, fossil fuel is about to run out of photoelectrode materials must have an appropriate band gap,
availability soon as its limited reserve in earth. Hence, it is special catalytic properties and needs to be stable in the aqueous
essential to place the worldwide energy system onto a more environment under illumination [16]. Unfortunately, nearly all
sustainable, secure and environmentally benign path. Unfortu- known materials today fail to fulfill these conditions [17]. The
nately, sources like wind, solar, bio and nuclear are not desirable highest reported solar to hydrogen conversion efficiency till 1998
for economic energy production, because of their undeveloped was 12.4% [16] for an illuminated area of 0.2 cm2, referring to the
technology, establishment cost and safety concerns. Hence, hydro- lower heat value of hydrogen. Peharz et al. [18], achieved an
gen being considered as a clean fuel as it produces water only on efficiency of 18% in 2007 for the solar to hydrogen production
its combustion [5,6]. Furthermore, H2–O2 fuel cells are environ- under outdoor conditions. The hydrogen production rate obtained
mentally benign and highly efficient device which converts che- with water splitting process is too low due to quick charge
mical energy of hydrogen directly into electricity. However, it recombination of photo-generated electron/hole pairs, quick back-
overcomes the limitations imposed by the Carnot efficiency. ward reaction and inability to utilize visible light efficiently [19].
Hydrogen produces three times higher quantity of energy Furthermore, the dissociation of water is a reaction not favoured
(39.4 kWh kg  1) during its combustion than that produced by thermodynamically; one has to go up to extremely high tempera-
any other fuel on a mass basis, e.g. liquid hydrocarbons tures ( 42200 1C) for obtaining some significant dissociation
(13.1 kWh kg  1) [7]. Hence, one gallon of gasoline has about the degree [20]. Moreover, direct one-step water splitting requires
same energy as one kilogram of hydrogen gas and it is expected the energy intensive process of high temperature oxygen–hydro-
that the hydrogen can replace all forms of fossil fuels in recent gen separation coupled with expensive membrane technology and
future. Approximately 100 times of the present hydrogen produc- therefore is considered of little chance for technical and econom-
tion (more than 3  1012 kg) would have to be produced per year ical viability in the near future. Additionally, gasification and
to fulfill world's demand for fossil fuel. There is no natural reforming of biomass are extensively explored for producing
resource of hydrogen and therefore it is not a primary fuel. Hence, hydrogen from several biomass resources such as forest residues,
hydrogen must be extracted at low cost from other abundant wood wastes, crop residues, waste water treatment, biogas, etc.
primary energy sources like coal, natural gas, naphtha, heavy oil, [21]. Nevertheless, the major limitations of these technologies are
biomass, wastes, solar, wind, or nuclear power, without harming the necessity of coupling of further stages like gas separation/
the environment [8–10]. Global statistics illustrate that 48% (240 purification treatments and the occurrence of further sophisti-
Billion cubic meters (Bcm)/yr) of hydrogen is produced from cated reactions which reduces hydrogen selectivity [22]. Fig. 2
natural gas (NG), 30% (150 Bcm/yr) from petroleum, and 18% depicting different sources, preparation methods, intensity of GHG
(90 Bcm/yr) from coal, while only 4% (20 Bcm/yr) is obtained emission of each process and utilization of hydrogen.
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 223

Fig. 1. (a) Worldwide hydrogen production by sources and (b) sector-wise usage of hydrogen.

potential further applications such as gas (e.g. hydrogen) storage

[29], polymer additives [30], catalyst support or direct catalyst
[31], is the co-product in TCD process. Despite the fact that
hydrogen produced from methane cracking is a pure form of
hydrogen, methane cracking is not used on an industrial scale for
producing hydrogen since the technology is still in laboratory
level. While, industrially emerged hydrogen production technolo-
gies were reviewed elsewhere [32].
Due to its very strong C–H bond (440 kJ/mol) and high
symmetry of the molecular structure, methane is the one of the
most inactive hydrocarbons, and its decomposition can only take
place efficiently at a temperature higher than 1200 1C in the
absence of a catalyst. Various metal and carbonaceous catalysts
have been introduced in the interest of reducing decomposition
temperature. In pursuance of producing CO2 free hydrogen,
Fig. 2. Schematic representation of the sources, preparation methods and utiliza- methane decomposition mechanism mainly involves five steps
tion of hydrogen.
[33] as follows. (i) The chemisorption of methane on the leading
face of a catalyst particle, (ii) detachment of a chemisorbed
SRM and POX are the current thermochemical processes for methane molecule through progressive breaking of four C–H
hydrogen production from methane, the main constituent of NG bonds as follows:
having highest C:H ratio. SRM has been considered as the one of
ðCH4 Þg -ðCH3 Þa þ ðHÞa ð2Þ
the most common and regularly adopted technique for many
years. In spite of its high process efficiency (50%) and compara- This step is followed by a series of surface stepwise dissociation
tively low cost, SRM causes high emissions of COx (at least 1 mol of reactions leading to elemental carbon and hydrogen [34]:
CO2/mol of converted methane) and requires more process energy
ðCH3  x Þa -ðCH2  x Þa þ ðHÞa ð3Þ
[23]. Moreover, fuel reforming process is multifaceted containing
CO elimination by water gas shift reaction together with selective where 0 ox o2; subscripts (a), (c) and (g) denote adsorbed,
CO oxidation. Hence, the post-reaction mixture contains huge crystalline and gaseous species, respectively. (iii) Aggregation of
quantities of CO even after the purification. Similarly, the POX adsorbed atomic hydrogen into molecules, followed by gas phase
process is also causes GHG emission. Consequently, TCD or so- emission,
called methane cracking attracted as a novel technique for eco-
2ðHÞa -ðH2 Þg ð4Þ
friendly hydrogen production. In this moderately endothermic
process, methane is thermally decomposed to solid carbon and (iv) atomic carbon aggregation into encapsulated carbon, lead-
gaseous hydrogen in a technically simple one step process as ing to progressive catalyst deactivation, or atomic carbon diffusion
shown in Eq. (1). through the bulk catalyst from the leading face to the trailing face,
driven by the existing pronounced concentration gradient, and
CH4 -C þ 2H2 ΔH298 K ¼ 74:52 kJ=mol ð1Þ
(v) carbon nucleation followed by the formation and growth of
carbon nano-fibers (CNFs) in the trailing face of the catalyst
particle.
2. Thermocatalytic decomposition of methane
ðCÞa -1=nðCn Þc ðCarbon crystalline growthÞ ð5Þ
Thermocatalytic decomposition of methane (TCD), the most The kinetic laws (pre-exponential factor, activation energy and
economical hydrogen production method, has been extensively reaction order) of each intermediate elementary reaction step are
studied since 1960s [24–28]. The prime benefit of TCD is the near still unknown [35]. TCD process has less environmental impact
elimination of GHG release [12]. Moreover, technically the hydro- compared to commercial hydrogen production method like
gen produced by TCD can directly use as the fuel for H2–O2 fuel SRM. Even though, TCD process is facing many challenges as
cell as well as in internal combustion engine without further follows: catalytic deactivation, presence of unreacted methane in
purification step, hence produced hydrogen is free from COx [23]. out stream, possibility of further components in case of co-feed
Furthermore, nano-carbon, of possible interest for a variety of assisted methane decomposition and formation of COx during
224 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

regeneration of deactivated catalyst. All these titles are discussed methane conversion or hydrogen production of various metal
in details in this review. This segment of review discusses various catalysts had already been studied.
metal and carbon based catalyst briefly, giving special importance
to the recently developed catalysts.
2.1.1. Non-supported catalysts
It has been reported that the rate of methane decomposition of
2.1. Metal catalysts non-supported metal catalysts are in the order of Ni, Co, Ru,
Rh4Pt, Re, Ir 4Pd, Cu, W, Fe, Mo [67]. Among them, Ni, Co and Fe
Over the past few decades, many efforts have been devoted for catalyst gained major attention because of their advantages like
developing simple and efficient synthesis protocols for the pre- availability, low cost, better activity and stability [47,50]. Ni crystal
paration of suitable catalyst in order to realize the TCD process size has immense influence on the methane decomposition and
with a moderate condition. Various metal catalysts [36–39], carbon formation. Its direct relationship with coking threshold
different supports and numerous carbonaceous catalysts have (thermodynamic equilibrium constant) was revealed in 1975 [68].
been studied extensively [40–42]. In addition to hydrogen, ordered Rapid aggregation and carbon encapsulation deactivate non-
nanocarbons are forming with metal catalyst, while carbonaceous supported Ni-catalyst rapidly, especially at a temperature higher
catalysts produce amorphous carbon having a variety of morphol- than 600 1C [57]. However, theoretical thermodynamic equili-
ogy [43,44]. The general reaction mechanism on different metal brium study were evaluated by using a commercial Outokumpu
catalysts has been supposed to be similar. However, the chemical HSC Chemistry 5.11 chemical equilibrium calculation software
composition and preparation method, the support and promoter illustrated that methane conversion is thermodynamically inade-
influence the activity and stability of catalyst and determine the quate at this temperature [69,70], resulting to a low hydrogen
structure and morphology of the carbon formed. Catalytic activity yield [50]. On the other hand, despite showing hasty deactivation
and stability of various kind of catalysts are compared in Table 1, on continuous cycles directing short life time, Fe catalysts have
which comprises the conserved stability, activity and maximum more stability at higher temperature range of 700–1000 1C [71].

Table 1
Catalytic activity and stability of various catalysts recently studied.

Catalyst W Stability and activity maintained Max. CH4 conversion Max. H2 produced t/T/F Ref.

T t at t, T and F

Ni 0.04 650 130 35 – 0/650/45,000a [45]

Ni 0.04 500 37 9 – 0/500/60b [46]
Fe 2 900 475 98 – 14/800/20b [12]
Ni–Cu 1 900 5 96 – 0.5/900/110c [47]
Fe–Cu 0.75 600 5 51 – 1.6/600/110c [48]
Ni–Cu–Al 0.05 800 2.75 – 75 0.5/700/120,000a [33]
Ni/Ce–MCM-41 0.05 580 423 75 – 18/580/75b [49]
Ni–Cu–Zn/MCM-22 1 800 450 85 – 0/750/10b [24]
Ni/SiO2 0.15 600 410 22 – 0/600/– [50]
Ni/SiO2 0.03 650 4 42 – 0/650/15b [51]
Ni/TiO2 0.3 700 8 – 73 0.1/700/20b [52]
Ni/Al2O3 – 700 3 – 73 0/700/12a [53]
Ni/La2O3 0.53 600 5 75 – 1/600/110c [54]
Fe/Al2O3 – 800 3 – 91 0.4/800/1.5a [53]
Fe/Al2O3 0.02 900 6 68 – 0/900/6000a [55]
Fe/MgO 0.15 800 3 – 55 0/800/12,000a [56]
NiCu/Al2O3 10 750 47 – 80 0/750/12,000a [28]
Ni–Ca/SiO2 0.05 580 3 39 – 0/580/100b [57]
Ni–K/SiO2 0.05 580 3 40 – 0/580/100b [57]
Ni–Ce/SiO2 0.05 580 3 90 – 0/580/100b [57]
Ni–Fe/SiO2 0.03 650 44 46 – 0/650/15b [51]
Ni–Cu/SiO2 1 750 45 88 86 5/750/1800a [58]
Ni–Cu–TiO2 0.3 700 8 – 80 0/700/20b [52]
Ni–Cu/MgO – 700 3 – 79 0.75/700/12a [53]
Ni/MgAl2O4 0.1 700 5 37 – 1/550/80b [59]
Ni–Cu/La2O3 0.53 900 426 97 – 0/900/110c [54]
Ni/Ce–SiO2 0.2 600 2 50 – 0.3/600/100b [60]
Fe–Mo/MgO – 800 3 – 92 0/700/1.5a [53]
FeMo/MgO 0.15 950 3 – 96 0.3/950/1000a [56]
FeMo/Al2O3 0.15 800 3 – 88 0/800/12000a [56]
Co/Ce–TiO2 0.2 500 2 5 – 1.9/500/100b [60]
Co/Al2O3/SiO2 – 700 30 90 – 0/700/1900 h  1 [61]
CoO–MoO/Al2O3 0.4 700 2 78.9 – 0/700/250b [62]
Pt–Ni/MgAl2O4 0.1 700 4 45 – 0/700/80b [63]
MgO/SiO2 – 900 200 – 45 0/750/60–65b [64]
K/MgO/SiO2 – 900 200 – 77 0/800/60–65b [64]
Ni/K/MgO/SiO2 – 900 200 – 61 0/700/60–65b [64]
LaNiO3perovskite 0.05 700 4 81 – 1.2/700/15b [65]
LaNiO3perovskite – 800 5 91 – 0.5/800/20b [66]
NiO/La2O3 – 800 5 93 – 0/800/20b [66]

(W¼ weight (g), T ¼temperature (1C); t¼ time (h); F¼ flow rate (amL/(gcat.h) bmL/min cNmL/min, unless other units are stated); conversion (%); –, not mentioned in the
original paper).
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 225

Moreover, Fe-based catalysts produce thin wall carbon nanotubes effects [75]. Lee et al. [62] conduct TCD over CoO–MoO/Al2O3 and
as byproduct, which are invaluable among nanocarbons [72]. found the initial methane conversions are 50.8, 65.5, 71.6, and
Hence, most of the Fe-based catalyst work have devoted for the 78.9% over the catalyst with 10, 20, 30 and 40 wt% CoO–MoO
production of nanocarbon other than hydrogen production. There- loading, respectively. It shows a gradual increase in initial methane
fore, those works are excluded from this review as it is focusing on conversion with metal loading. In a broad-spectrum, the examined
hydrogen production. While, cobalt catalyst did not get as much operating temperatures for Ni-based catalysts are ranged from 500
attention as Ni and Fe catalysts. Partially filled 3d orbitals of Fe, Co to 900 1C with the highest methane conversion of 85% at 750 1C,
and Ni facilitate the dissociation of the hydrocarbon molecules while that for Fe-based catalysts are 200–1200 1C with 4 90%
through partially accepting electrons. This interaction along with methane conversion at 800 1C [12,53,80]. In 1998, Muradov [88]
“back-donation” from the metal into the unoccupied orbital in the generated CO2 free hydrogen yield very close to the equilibrium
hydrocarbon molecule changes the electronic structure of the value with Fe2O3 catalysts at 850 1C. Fe–Mo/MgO [56] withstands
adsorbed molecule so that the dissociation of the molecule occurs temperature up to 950 1C with methane conversion of higher than
[73]. While, copper, a non-transition metal with its 3d shell 90% for 3 h continuously. Fe/Al2O3 [55] also shows better perfor-
completely filled, was observed to yield very less hydrogen and mance at higher temperature. In spite of having better stability at
amorphous carbon. Likewise, noble metals (Rh, Ru and Pt) do not higher temperature range, the overall performance of the Fe-based
provide heartening results in terms of methane conversion in TCD catalysts is not as good as that of Ni-based catalysts. It paved the
[69]. The main advantage of non-supported catalyst is the mag- way to introduce Fe incorporated Ni-based catalysts. The addition
netic properties associated with those materials which facilitate of Fe in to Ni/SiO2 catalysts boost up its activity by about 3 times
the recovery of the catalyst after the reaction, once the latter is without much deactivation [51]. The addition of Cu and Zn in to
mixed with the produced carbon [69,74]. Ni-based catalysts enhance the catalytic stability up to 800 1C with
72% methane conversion [24]. Ni–Cu–SiO2 (50:10:40) shows
higher activity with a maximum methane conversion of 88%
2.1.2. Metal supported catalysts
corresponding to a hydrogen yield of 86% at a temperature
The metal-supported catalyst belongs to the heterogeneous
750 1C and GHSV 1800 mL/h gcat [58]. 10% Cu loading shows
catalysis. The metal would be polarized by the influence of charge
maximum activity, but further addition of Cu lower the activity
enclosed in the support [75], which make changes in their proper-
and stability, especially at high temperature, as the higher amount
ties. Strong Metal–Support Interaction (MSI) increases the disper-
of Cu make the catalyst particles easily in quasi-liquid state. The
sion of metal by decreasing its mobility. MSI can make changes on
addition of Ce enhances the stability of both Ni and Fe-based
the crystallography and the electronic state of the metal particles
catalyst by more than 10 times of that of Ni/SiO2 catalyst
depending on the intensity of the interaction [76]. The factors
[49,60,89]. It is attributed to the conversion of formed carbon to
influencing the catalytic activity are the electronic state of the
COx because of Ce4 þ /Ce3 þ mechanism [49]. Hence, a small amount
metal particles, crystalline size, dispersion of metal particles,
of COx has been detected throughout the experiments.
textural properties, pore geometry of the support [77], catalyst
composition [28], catalyst preparation method [78], and catalyst
rinsing solvent [46]. Numbers of efforts have been devoted in favor
2.1.4. Ceramic and red-mud based catalyst
of improving catalytic activity and stability by bringing changes in
Ceramic materials have high melting point, high resistant to
the above mentioned factors.
chemical attack, good mechanical strength, low acidity, good
Various types of metal supported catalysts like Ni–Cu [24,79],
interaction with metallic phase [59], and do not form metal
Ni–Zn [80], Fe–Pd, Fe–Mo, Fe–Ni [26] and Ni/Cu/Al [81] had been
carbide [64]. All these properties are desirable for a catalyst
introduced in order to improve the activity. Addition of Cu in to Ni
support. Furthermore, unlike metal catalyst, ceramic catalyst can
and Fe by in situ thermal treatment has immense enhancement on
govern the reaction for producing specific product is it's additional
their catalytic activity and stability. Ni–Cu catalyst shows catalytic
advantage [64]. As expected, Ni/MgAl2O4 illustrate better activity
stability up to 700–750 1C with a 70–85% methane conversion
with 37% methane conversion for 1 h without much deactivation
[47,80]. There is no significant catalytic deactivation occurred for
[59]. The contact time of reactant molecules was extremely
300 min. Cu doped Ni produces octopus and porous CNF with high
important for methane decomposition and MgO have the affinity
surface area. Similarly, Cu addition in to Fe improves with 51%
for sustaining hydrogen which was bonded to methane, in this
methane conversion with better life span than monometallic Fe
way it increased the sustain time of methane on the ceramic
catalyst [48]. This higher stability and activity of supported
surface, which was responsible for decomposition of methane.
catalysts explained in terms of ensemble effect, which decreases
However, addition of Pt to the above mentioned ceramic support
the rate of formation of encapsulating carbon. Furthermore,
did not favor catalytic result [63]. Addition of K in to MgO/SiO2
Density functional theory (DFT) calculations show that Cu–W
ceramic catalyst increases its activity to produce 77% maximum
and Cu–Mo composite particles have binding energies in the same
hydrogen yield and stability up to 900 1C even after 200 h [64].
range as Fe, Co and Ni. The addition of a dopant to Cu in an
Doping of K provides greater active sites and surface area to the
appropriate ratio modifies the binding energy into a certain range
catalyst for better decomposition and higher stability. However, K
suitable for C–H bond cleavage formation [82,83]. Moreover, Fe
addition inhibited coke formation and carbon deposition during
gives better results while coupling with Mg, Co, Pd, Ni, and Mo
the decomposition reaction and hence did not suffer fast deactiva-
than monometallic Fe at 700–800 1C [26,84,85].
tion. Silica reacted with potassium oxide to form stable silicates
which was actually responsible for the stability of ceramic materi-
2.1.3. Metal oxide supported catalysts als for better active life [90,91]. Ceramic catalysts produces multi-
Metal supported on metal oxide catalysts (Co/Mo/Al2O3 [62,86], walled carbon nanotubes which approximately same at optimize
Ni–Cu/SiO2 [58], Ni–Cu/Al2O3 [28], Mo–Fe/Al2O3 [87]) have gained temperatures of Ni catalyst. No impurities were detected in
tremendous attention as they exhibit high catalytic activity and nanotubes produced from cracking of methane from ceramics [64].
stability for TCD process. However, the methodology for selecting Red mud is a waste product of the aluminum industry. It is
the third component is not systematically illustrated until now. It composed of iron oxides/oxyhydroxides/hydroxide, aluminum
is reported that oxide support can alter the surface chemistry of oxide/oxyhydroxide/hydroxide, silica, titania and a range of alkali
metal catalyst particles through epitaxial, spillover, and migration and alkaline earth metal compounds such as sodium oxide and
226 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

calcium oxide [92]. Of these, the iron compounds are generally the exploited metal catalysts that the activity increase as increasing
major phase constituents. Balakrishnan et al. [92] considered the temperature up to a particular level then deactivation of
methane itself as a reductant and conduct methane decomposition catalyst starts [24,28,45,49]. NiCuAl catalyst has maintained its
over red-mud without any prior reduction step. Red-mud contain- initial activity at low reaction temperatures, that is, 550, 600 and
ing relatively high content of titanium seems to have reduced 650 1C, with low hydrogen production of 20, 26 and 31 vol%,
activity for methane conversion compared to a sample containing respectively, were measured in the outlet gas [33]. On the other
a comparable proportion of iron. The maximum hydrogen forma- hand, the initial hydrogen concentrations were much higher, 55,
tion rate observed, 3.80  10  5 molH2/g s, was associated with a 67 and 70 vol% at 700, 750 and 800 1C, respectively (Fig. 3a).
sample containing the highest proportion of iron and a lower However, the evolving hydrogen concentrations dropped quickly,
concentration of alkali metal [92]. Elsewhere, alkali metals have indicating rapid catalyst deactivation. This effect was more evident
been reported to be very effective poisons for the methane as reaction temperature increased. This rapid deactivation of
decomposition reaction [93]. The efficacy of the red mud samples catalyst at higher temperature is attributed to the metal particle
is variable, which is related to differences in their composition sintering and the formation of more ordered carbon. In a kinetic
which in turn reflects the purity of the bauxite ores from which point of view, temperature and pressure are the main parameters
they are produced. Advanced studies on red mud catalyst has yet
to be conducted.
Table 2
The activation energy of the TCD process reported in literature over different
2.1.5. Thin layer catalysts catalysts.
Thin layer catalysts (TLCs) are recently attracted the attention
Catalyst Ea (kJ/mol) Ref.
of investigators [61,94]. Frusteri et al. [94] found that the Ni and Co
TLC supported on Al2O3 samples suitable for a cyclic dual-step Ni 65.4 [98]
process, which is comprised of TCD and catalyst regeneration by Ni 59 [104]
oxygen without damaging the catalyst. Furthermore, both Ni and Ni 59 [27]
Co exhibit a strong interaction with Al2O3 support surface and it is Ni (111) 53.9 [107]
Ni–Al 64.6 [100]
noticed that the formation of encapsulating carbon is depressed Ni/SiO2 29.5 [102]
and only filamentous carbon forms. Despite of this advantage, Ni Ni–Co–Cu 67.5 [98]
and Co silica supported catalyst were not found apt for long time Ni/SiO2 90 [106]
catalysis as their deactivation by time. In fact, Co/Al2O3/Silica TLC is Ni/TiO2 60 [101]
Ni/Zeolite Y 61.77 [97]
stable up to 700 1C for 32 h and convert more than 80% methane
Ni–Cu/MgO 50.4 [103]
to hydrogen [61]. Cobalt particles strongly adsorb on Al2O3 support Ni/Al2O3–CaO 88 [105]
giving rise to the formation of CoAl2O4-type structures, which
ensure an elevated metal dispersion inhibiting also the occurrence
of sintering phenomena [95,96]. Irrespective of Co loading, initial
Table 3
hydrogen production increases with reaction temperature, while Summary of the main parameter obtained in the experiments at different
the relation between lifetime and activity of TLC catalyst with  1 1
temperature over NiCuAl catalyst (WHSV:120 lg h ) [33].
other operating parameters or catalyst characteristics have yet to cat
be optimized. It is found that, 20% Co ensures both long lifetime
and high hydrogen productivity. T (1C) rCH4,0 (XCH4)eq (%) XCH4 (%) Cdep rC (gC/gcat h)
(mmol/min gcat) (g/gcat)

2.1.6. Influence of parameters on activity 550 10.02 34 10.20 16.4 6.56

Catalyst stability and activity depends on the experimental 600 12.96 52.1 13.19 21.3 8.51
parameters such as reaction temperature, partial pressure, space 650 16.25 64.2 16.17 26 10.40
700 34.27 79.3 31.20 46.8 20.03
velocity, etc. [97]. In general, the hydrogen content in the initial 750 47.60 85 22.06 39 14.18
output of TCD process with metal catalysts is incredibly high, but 800 45.95 91.5 19.41 15.6 16.22
their activity decreases very fast with time. It is clear from

1 1
Fig. 3. (a) Influence of reaction temperature on the evolution of hydrogen concentration at space velocity 120 lg h , (b) influence of space velocity on the evolution of
cat
hydrogen concentration at temperature700 1C [33].
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 227

influencing hydrogen formation rate over time. Kinetic studies are catalyst at high temperatures, although the activation energy for
chemical stages conducted for developing a suitable model which CH4-bond dissociation decreased from 440 kJ/mol in the gas phase
describes the rate of reaction and defines the chemical process to 65 kJ/mol on a Ni (100) surface. Wang and Lua [98] were carried
[98]. Recent studies [99] have shown that the initial C–H bond out kinetic studies on methane decomposition over Ni catalyst and
breaking of CH4 is the rate determining step over the metal found that the average reaction order and activation energy for the
methane decomposition over the unsupported nickel was 0.63 and
65.4 kJ/mol, close to those previously published values furnished
Table 4
in Table 2. The wide range of reported activation energies may be
Summary of the main parameter obtained in the experiments at different space
velocity over NiCuAl catalyst (T:700 1C) [33]. due to many factors, including the difficulty of collecting true
kinetic data and the highly dynamic characteristics of the process
WHSV r0 (mmol/min.gcat) XCH4 (%) Cdep (g/gcat) rC (gC/gcat.h) [100]. Wang and Lua [98] found that, when PCH4 was increased
 1 1 from 0.2 atm to 1 atm, the hydrogen formation rate significantly
(lg h )
cat
increased but the catalyst activity decreased. The faster deactiva-
24 10.38 54.61 45.8 7.02 tion of the catalyst was subjected to a higher reaction temperature,
60 15.01 31.36 39 15.60 which accelerated methane dissociation and increased the diffu-
120 34.27 31.2 46.8 20.06 sion rate. Generally, increasing reaction temperature increases
240 58.31 20.09 64.6 25.84 methane dissociation due to the endothermic nature of the
480 79.95 11.63 84a 33.60
1200 134.74 8.77 141a 56.40
reaction while at the same time the diffusion rate also increases
accordingly. In the case of 2Ni–1Co–1Cu, a faster carbon diffusion
a
Catalyst deactivated. rate at a higher temperature would probably speed up the

Table 5
Comparative study of influence of experimental parameters.

Catalyst Operating conditions Maximum tmax CH4 H2 t Ref.

T F W CH4 H2 At time ‘t’

At tmax

DCC-N103(P) (CB) 850 15,000a 0.1 2 – 0.1 1 – 2 [146]

870 4 – 0.1 2 – 2
900 5 – 0.25 3 – 2
925 5 – 0.1 5 – 2
950 13 – 0.1 7 – 2
CG Norit (CB) 850 20b – – 72 0.1 – 30 4 [138]
50b – – 62 0.1 – 17 4
100b – – 48 0.1 – 8 4
Fluka 05120 850 20b – – 60 0.1 – 38 4
50b – – 51 0.1 – 28 4
NORIT CG (commercial AC) 950 600a 2 – 94 1.1 – 38 4 [125]
900 – 85 0.6 – 30 4
850 – 68 0.5 – 30 4
Xiaolongtan char 1000 200b 10 96 90 0 19 18 2 [155]
850 69 48 0 20 10 2
700 29 20 0.1 9 8 2
600 10 9 0.1 5 5 2
ACPS 850 1764 h  1 20 49.8 47.9 0 – – – [135]
850 882 h  1 40 34.9 62.5 0 – – –
850 441 h  1 80 21.2 77 0 – – –
850 294 h  1 120 16.7 81.6 0 – – –
850 294 h  1 40 13.2 83.1 0 – – –
850 441 h  1 40 22 78.3 0 – – –
850 882 h  1 40 34.9 62.5 0 – – –
850 1764 h  1 40 41.5 57.9 0 – – –
850 882 h  1 40 34.9 62.5 0 – – –
825 882 h  1 40 37.6 60.9 0 – – –
800 882 h  1 40 48.7 50.9 0 – – –
775 882 h  1 40 59.5 39.1 0 – – –
Ni–AC 550 50b 0.20 4 – 0 0 – 1 [105]
650 6 – 0 1 – 2
750 13 – 0 2.5 – 2
850 27 – 0 2.5 – 1
BP1300 (CB) 850 36 h  1 – – 92 0 – 46 6.5 [139]
72 h  1 – – 70 0 – 26 6.5
144 h  1 – – 41 0 – 15 6.5
BP2000 (CB) 850 36 h  1 – – 59 0 – 28 6.5
72 h  1 – – 35 0 – 20 6.5
144 h  1 – – 18 0 – 11 6.5
BP2000 (CB) 950 144 h  1 – – 78 0 – 62 6.5
900 – – 59 0 – 38 6.5
850 – – 18 0 – 11 6.5

(T, temperature (1C); F, flow rate (amL/(gcat.h) bmL/min, unless other units are stated); W, catalyst mass (g); Conversion (%); tmax, time at which maximum methane
conversion or hydrogen production occur (h); t, time (h); –, not mentioned in the original paper).
 228
Table 6
Comparison of catalytic activity of metal and carbonaceous catalyst; initial activity and final activity of recently studied catalysts are listed.

Catalyst Reactor Reaction parameters Initial CH4 H2 t-time d Ref.

T CH4 flow Total flow CH4 H2 At time t

Metal catalysts
Ni FBR 550 – 45,000a o 20 – 8 – 100 130 [45]
Ni FBR 500 60b 90,000a 9 – 6 – 50 52 [46]
Fe FBR 800 – 20b 33 – 98 – 14 – [12]
Ni–Cu CFR 600 – 110c 80 – 84 – 5 – [47]
Ni–Cu CFR 900 – 110c 97 – 40 – 5 –
Fe–Cu CFR 600 – 110c 22 – 32 – 5 – [48]
Ni–Cu–Al FBR 700 – 120,000a – 75 – 70 2.5 – [33]
Ni/Ce–MCM-41 FBR 580 – 75b 70 – 72 – 23 – [49]

U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256
Ni/SiO2 FBR 600 – – 22 – 7 – 10 11 [50]
Ni/SiO2 FBR 650 15b – 42 – 5 – 4 – [51]
Ni/TiO2 FBR 700 – 20b – 70 – 60 8 – [52]
Ni/Al2O3 RBR 700 – – – 73 – 68 3 – [53]
Ni/La2O3 – 600 – 110c 75 – 73 – 5 – [54]
Fe/Al2O3 RBR 800 – – – 90 – 81 3 – [53]
Fe/Al2O3 FlBR 800 – 3000a 62 – 32 – 6 – [55]
Fe/MgO FBR 800 – 12,000a – 55 – 15 3 – [56]
NiCu/Al2O3 FlBR 700 – 12,000a – 69 – 42 7 – [28]
Ni–Ca/SiO2 FBR 580 – 100b 39 – 12 – 3 – [57]
Ni–K/SiO2 FBR 580 – 100b 40 – 5 – 2.5 3
Ni–Ce/SiO2 FBR 580 – 100b 90 – 69 – 3 –
Ni–Fe/SiO2 FBR 650 15b – 46 – 27 – 4 – [51]
Ni–Cu–TiO2 FBR 700 – 20b 80 – 69 – 8 – [52]
Ni–Cu/MgO RBR 700 – – – 76 – 75 3 – [53]
Ni/MgAl2O4 FBR 550 – 80b 34 – 23 – 3 4 [59]
Ni–Cu/La2O3 CFR 600 – 110c 35 – 60 – 10 – [54]
Ni–Cu/La2O3 CFR 700 – 110c 90 – 11 – 10 –
Ni/Ce–SiO2 FBR 600 – 100b 40 – 27 – 1 1.3 [60]
Fe–Mo/MgO RBR 700 – – – 92 – 58 3 – [53]
FeMo/MgO FBR 800 – 1000a – 95 – 85 3 – [56]
FeMo/MgO FBR 800 – 12,000a – 81 – 19 3 –
FeMo/Al2O3 FBR 800 – 12,000a – 88 – 15 2.5 –
Co/Ce–TiO2 FBR 500 – 100b 0 – 5 – 2 – [60]
Pt–Ni/MgAl2O4 FBR 700 – 80b 45 – 3 – 1.6 4 [63]
Co/Al2O3/Silica MLR 650 – 1900 h  1 80 – 10 – 30 – [61]
MgO/SiO2 FBR 750 60–65b – – 45 – 10 200 – [64]
K/MgO/SiO2 FBR 800 60–65b – – 77 – 60 200 –
Ni/K/MgO/SiO2 FBR 700 60–65b – – 61 – 0 1 1
LaNiO3 perovskite – 700 15b – 5 – 58 – 4 – [65]
LaNiO3 perovskite FBR 800 20b – 75 – 74 – 5 – [66]
NiO/La2O3 FBR 650 20b – 62 – 44 – 5 –
(AC)R/SiO2 FBR 850 10b 15,000a 30 – 9 – 2 – [142]
(AC)R/SBA-15 FBR 850 10b 15,000a 27 – 8 – 2 –
CB FBR 850 10b 15,000a 22 – 12 – 2 –

Metal doped carbonaceous catalysts

AC/Pd-5 FBR 850 54b 16,200a 30 – 28 – 4 – [152]
AC/Pd-10 FBR 850 54b 16,200a 38 – 52 – 4 –
AC/Ni-10 FBR 850 54b 16,200a 25 – 15.1 – 4 – [153]
AC/Ni-20 FBR 850 54b 16,200a 71 – 52 – 4 –
AC/Ni-30 FBR 850 54b 16,200a 74 – 61 – 4 –
AC/Ni-40 FBR 850 54b 16,200a 29 – 75 – 4 –
Ni/SHCC FBR 850 – 50b 30 – 80 – 5.5 – [148]
 Ni/SLCC FBR 850 – 50b 30 – 76 – 5.1 –
Ni/RC FBR 850 – 50b 14 – 59 – 9 –
Al/RC FBR 850 – 50b 29 – 60 – 5 – [154]
Si/RC FBR 850 – 50b 23 – 11 – 5 –
AC from coconut FBR 850 – – – 79 – 13 1.5 3.5
(AC)R/SiO2 FBR 850 10b 15,000a 30 – 9 – 2 – [142]
(AC)R/SBA-15 FBR 850 10b 15,000a 27 – 8 – 2 –

Carbonaceous catalysts
CB FBR 850 10b 15,000a 22 – 12 – 2 – [142]
AC (AX-21) FBR 850 – – – 50 – 21 4 – [88]
CB (Vulcan XC-72) FBR 850 – – – 20 – 5 4 –
Graphite FBR 850 – – – 4 – 2 2 3.2
RC (AC) FBR 850 3000a 15,000a 31 – 22 – 10 – [160]
AC-0 (AC) FBR 850 3000a 15,000a 29 – 3 – 2 –
BP2000 (CB) FBR 850 3000a 15,000a 21 – 3 – 4 –
DCC-N103(p) (CB) FBR 950 25b 15,000a 13 – 7 – 2 – [146]

U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256
DCC-N220(p) (CB) FBR 950 25b 15,000a 7 – 6 – 2 –
DCC-N550(p) (CB) FBR 950 25b 15,000a 8 – 5 – 2 –
Carbopack B (CB) FBR 850 20b 38 h  1 – 12 – 12 4 – [138]
Carbopack C (CB) FBR 850 20b 38 h  1 – 8 – 8 8 –
Fluka 03866 (CB) FBR 850 20b 38 h  1 – 68 – 12 4 –
Fluka 05120 (CB) FBR 850 20b 38 h  1 – 60 – 34 8 –
BP2000 (CB) FBR 850 20b 38 h  1 – 59 – 28 8 –
HS-50 FBR 850 20b 38 h  1 – 29 – 17 8 –
CG Norit FBR 850 20b 38 h  1 – 72 – 8 7.5 –
CG (commercial AC) FBR 850 20b 600a 51 67 18 30 4 – [125]
SUPRA (commercial AC) FBR 850 20b 600a 32 49 12 21 4 –
GAC (commercial AC) FBR 850 20b 600a 25 38 16 27 4 –
SCA750 (coal-derived AC) FBR 850 20 b 600a 19 31 3 5 4 –
SCA600 (coal-derived AC) FBR 850 20b 600a 20 32 2 4 4 –
SC800 (coal-derived AC) FBR 850 20b 600a 26 41 2 4 4 –
Shengli lignite char FBR 850 – 200b 87 90 29 38 2 – [155]
Xiaolongtan lignite char FBR 850 – 200b 81 82 17 20 2 –
Binxian bituminous char FBR 850 – 200b 70 68 10 13 1 2
Jincheng anthracite char FBR 850 – 200b 36 27 3 4 1 2
BP1300 (CB) FBR 850 20b 144 h  1 – 42 – 15 6.5 – [139]
BP2000(CB) FBR 850 20b 144 h  1 – 17 – 12 6.5 –

(FBR, fixed bed reactor; FlBR, fluidized bed reactor; CFR, continuous flow reactor; RBR, rotary bed reactor; MLR, multilayer reactor; T, temperature (1C); F, flow rate (amL/(gcat.h)bmL/min, cNmL/min, unless other units are stated);
Conversion (%); t, time (h); d, complete deactivation (h); –, not mentioned in the original paper).

229
230 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

fragmentation of the catalyst [98] and leads to deactivation. Uddin

et al. [97] reported that Ni/Zeolite Y shows reaction order and
activation energy were 2.65 and 61.77 kJ/mol, respectively for
methane decomposition in a fixed bed reactor. The kinetic experi-
ment indicates that the optimum temperature range should be
maintained to achieve the highest performance from 30% Ni/Y
zeolite in terms of hydrogen formation rate, average hydrogen
formation rate, total hydrogen formation, average carbon forma-
tion, total carbon formation, and carbon formation rate.
Furthermore, the catalyst deactivation significantly increases as
space velocity goes up [33,51,59]. NiCuAl exhibit high stability
 1 1
from 20 to 60 lg h with 75 vol% of hydrogen in the outlet
cat
stream (Fig. 3b) [33]. While, at the higher space velocity over 120–
 1 1 Fig. 4. Mechanism proposed for hydrocarbon decomposition on Ni catalysts [111].
1200 lg h , hydrogen concentration severely decreased to
cat
5 vol% within 60 min due to decrease in contact time between
methane molecules and the catalyst surface (Fig.3b). Increasing metal particles originating carbon filaments. Nevertheless, once
the space velocity has two clear effects: the hydrogen concentra- metal crystallites are detached, carbon filaments grow for
tion in the outlet gases diminishes, and the catalyst deactivation extended periods of time, until the metal crystallites become
substantially increases. Furthermore, Xiong et al. [108] stated that deactivated by encapsulating carbon. The reaction steps involved
the activity of supported catalyst strongly depend on the amount are summarized in Fig. 4 [111].
of loaded metal by studying various amount of Ni supported on Many other mechanisms also have been put forwarded by
SiO2. It is due to increasing availability of active sites for reaction. researchers in last decades to explain carbon filament growth.
Uddin et al. [97] stated that the carbon deposition is directly Basically it is considered as a four step process of carbon formation
related to the metal content of the catalyst. The high distribution [113]. (i) Methane chemisorption on the leading face of a catalyst
of nickel species into the zeolite Y cages and, possibly more particle through progressive breaking of the four C–H bonds, (ii)
significantly, the synergistic influence between the microporous aggregation of chemisorbed atomic hydrogen into molecules and
surfaces of zeolite Y and metallic nickel resulted in the higher further emission into gas phase, (iii) diffusion of atomic carbon
catalytic performance of 30% Ni/Y zeolite [109]. A greater electron through catalyst bulk from the leading face to the trailing face, and
density on the surface of metallic nickel and an increase in the finally (iv) carbon nucleation in the catalyst trailing face to the
retention capacity of hydrogen in the Ni/Y zeolite catalysts were formation of CNFs. According to Baker et al. [113] carbon formation
caused by the synergistic effects, which may include the interac- takes place in three steps. Hydrocarbons got adsorbed and
tions between the higher ionic microporous surface of zeolite Y decomposed on active sites of the catalysts as first stage which
and the nickel particles. is followed by dissolution of some of the carbon species into the
bulk and diffusion through the metal particle from the hotter
leading face (exposed to the gas) to the cooler rear face (facing the
2.1.7. Catalytic deactivation support), where carbon is precipitated from the solution to form
The common challenge of TCD of methane process is the carbon filaments. Finally, decreasing the growth rate as the
catalytic deactivation. In general catalytic reaction, the catalyst catalyst encapsulated by carbon formed. Hence, the deactivation
does not maintain permanent activity and selectivity. Some rates have good correlation with carbon diffusion rate. Catalyst can
catalysts deactivate very rapidly, within seconds, on the other maintain its activity if the carbon diffusion rate is greater than the
hand some other catalysts maintain its activity for long time of the carbon formation rate. Otherwise carbon can encapsulate catalyst
order of months. Poisoning, coking (carbon deposition), mechan- and leads to catalyst deactivation. The studies reveal that the
ical degradation and sintering are the main reasons behind the carbon deposition is inversely proportional to methane partial
deactivation of the catalysts [110]. There are number of studies pressure and directly proportional to the temperature [114].
titled on catalytic deactivation in order to lengthen the catalyst Higher carbon accumulation may leads to the disintegration of
life. Most of the studies focused on parameters affecting deactiva- the catalyst. Moreover, carbon formation may affect activity in the
tion, the period of stable catalytic performance and the complete following ways either individually or in combination [115]. The
deactivation time. Table 6 (Metal catalyst) explicitly shows the loss carbon can: (i) adsorb strongly on the active phase surrounding
of catalytic activity of various metal catalysts with time during TCD and blocking access to the active phase surface; (ii) encapsulate
of methane. Table 6 contains initial methane conversion or the active metal particle; (iii) plug the micro and mesopores,
hydrogen production and those at time t and deactivation time, denying access to the active phase inside the pores; (iv) accumu-
if any, at particular experimental parameters with which the late as strong carbon filaments leading to catalyst pellet disinte-
examination had conducted. These previously conducted experi- gration; and (v) in extreme cases, physically block the reactor.
mental results give a clear indication about the catalytic activity The operating conditions like flow rate (GHSV), reaction tem-
loss with time of each catalyst. perature [116], methane partial pressure, and hydrogen partial
Polyaromatic structure with high carbon-to-hydrogen ratio, pressure [114] also strongly influence the catalytic deactivation.
filamentous, amorphous, and graphitic carbon are the different The impact of reaction temperature and flow rate on methane
carbon forms with various chemical structures produced during cracking rate as well as catalytic deactivation is widely studied and
methane cracking [76]. Most of the researchers agreed that the both of them are considered as having such a high influence. The
carbon formation is the main reason of catalyst deactivation [112]. methane decomposition rate and carbon formed during the
Methane decomposition mechanism involves the dissociative reaction done by Suelves et al. [33] over NiCuAl catalyst in a fixed
adsorption of the methane on the metal surface, the dissolution bed reactor at different temperature is furnished in Tables 3 and 4.
and subsequent diffusion of the adsorbed carbon atoms through The maximum carbon deposit was observed at 700 1C, but at
the metal, and the precipitation of carbon at the backside of the higher temperatures like 750 and 800 1C, catalyst were completely
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 231

deactivated by producing 39 and 15.6 gC/gcat. In the opinion of [123,124]. In TCD, carbon bears more advantages as follows:
Zhang et al. [45], at higher temperature the methane decomposi- (1) produced carbon can catalyze further process, hence external
tion rate is too high and hence nucleation rate of carbon too. catalyst required only for the start-up of the action, avoiding the
Hence, the diffusion of carbon could not catch up with the supply of external and usually expensive catalyst produced by
increased nucleation rate; thereby the surfaces of active Ni particle sophisticated production techniques; and (2) it is not essential to
were covered by the deposited carbon and the catalyst deactivated separate produced carbon from the catalyst.
rapidly. Table 4 shows that 141 g of carbon deposited per gcat in Activated carbon (AC) [125], carbon black (CB) [126], coal chars
 1 1 [121], glassy carbon [127], MWNT [43] acetylene black [127],
60 min at a space velocity of 1200 lg h . It is observed that
cat soot [127], graphite [43], diamond powder [127], CNT [43], full-
catalyst become completely deactivated at 480 and erenes [127] and carbon materials with monolithic honeycomb
 1 1 design [128] are the different carbon materials used as catalyst for
1200 lg h space velocity quickly comparing with those at TCD process. Most of the researches have been done on AC
cat
lower space velocities. Moreover, the rate of carbon nucleation (contrived from lignocellulosic precursors like coconut, almond,
would become quicker at higher space velocities which breaks the peach, plum, olive, palm and cherry) and CB because of their noble
competitive balance exist between the carbon diffusion and activity and better stability [34,127,129]. TCD on carbon catalysts,
nucleation. Hence, more active site would be covered with the such as CB, AC, ordered mesoporous carbon, CNF and graphite,
excess nucleated carbon and the catalyst would deactivate more needs a high activation energy (143–236 kJ/mol) and has to be
rapidly. Thus, lower space velocity produce higher hydrogen and operated at higher temperatures (800–1100 1C) than on metal
carbon than at higher space velocities. These results clearly reveal catalysts [34,35,126,130–133]. Different factors are associated with
the influence of space velocity and reaction temperature on activity of carbonaceous catalyst: pore-size distribution [132,134–
catalytic deactivation. Higher temperature deactivates catalyst 137], surface area [138,139], polar surface groups [44,125,140,141],
rapidly and increase hydrogen content in the post-reaction stream. structural disorders, crystallinity [137,142], flow rate [139], reac-
On the other hand, higher space velocity diminishes hydrogen tion temperature [143], composition of reaction gas, pressure
content in the outlet gas stream and deactivates catalyst quickly. [144], etc. While, the genuine reason behind its activity and
According to Suelves et al., [33] thermal sintering of Ni particles reaction mechanism are not completely elucidated yet. Ordered
does not have any influence on catalytic deactivation. A compar- mesoporous material found exhibiting higher activity because of
ison study on the sizes of used catalysts using powder XRD its reduced diffusion restriction, studies were reviewed elsewhere
patterns exhibit comparable sizes at both temperatures of 550 [145]. In general, high temperature and low methane space
and 800 1C [117]. Hence, catalyst deactivation is not the result of Ni velocity favor hydrogen production (Table 5), in a similar manner
sintering during the decomposition conducted in the fixed bed as metal catalysts done.
reactor indicating the possibility of prevention of Ni sintering by It believes that the methane decomposition mechanism over
produced hydrogen. The formation of more ordered carbon is only carbonaceous catalyst initiates with dissociative adsorption of
responsible for deactivation of catalyst at higher temperature [33]. methane followed by a sequence of stepwise surface dissociation
While, Ishihara et al. [118] says that the large amount of deposited reactions leading to formation of elemental carbon and hydrogen,
carbon is not responsible to catalyst deactivation as their 10% as mentioned for metal catalyst [34]. The comprehensive mechan-
Ni/SiO2 catalyst actively crack methane even after depositing up to ism of methane decomposition is yet to be fully elucidated.
a 200-carbon atom/nickel atom ratio. NiCuAl also show lengthen Initially methane molecules interact with chemically reactive
activity for several more hours even after depositing 46.8 g/gcat at carbon crystallites (or other energetic abnormalities and/or active
150 min. This extended activity may be attributed to the catalytic surface radicals) to break C–H bond in order to form new C–C
activity of formed carbon. Those observation supports the space bonds in a hexagon layer of carbon form. This carbon crystallite
limitation in the reactor while running reaction results in deacti- growth is likely to occur at the periphery of existing crystallites
vation [23,119]. [34]. This is new carbon phase formation is constituted by two
processes named carbon nuclei formation and carbon crystallites
growth. The rate of carbon nuclei formation is proportional to HES
2.2. Carbonaceous catalysts density or substrate surface area. The research results among the
AC and CB reveals that, CB has highest stability because of ease of
The hydrogen content in the initial output of TCD of methane accessibility for methane molecules, but its catalytic activity is
process with metal catalysts is incredibly high, but their activity comparatively low [44,138]. While, AC shows very high initial
decreases very fast with time. It is clear that decrease in activity catalytic activity, its stability is pitiable because of the presence of
results from the blocking of catalyst's active site by the carbonac- micropores as well as the prevention of methane diffusion to AC
eous deposit produced according to Eq. (1). Formation of metal pore by huge carbon deposit formed [5]. The activation energies
carbide is the other main challenge of using metal catalysts. These for the activated carbons are in a range from 160 to 201 kJ/mol and
problems have partly overcome by using carbonaceous catalysts. the reaction orders in a range from 0.5 to 0.6 [146]. While, the
Carbonaceous catalysts are highly stable, relatively cheap and reported activation energies for the carbon blacks varied in a wide
resistant to poisoning by sulfur compounds and other elements, range from 148 to 236 kJ/mol and the reaction orders from 0.5 to
and undergo deactivation to a much lower degree than metallic 1.0. However, these differences among various carbon materials
catalysts [120]. Carbon has been using as a catalyst [121] as well as have not well been elucidated and moreover no definite conclu-
a catalyst support [122]. The main advantages of carbon over metal sion has yet been made on the mechanism. Serrano et al. [131]
catalysts are: (1) low cost; (2) high temperature resistance; suggest CB for short and long term reaction as it provide
(3) tolerance to sulfur and other potentially harmful impurities moderately high rate of hydrogen. On the other hand, AC is fare
in feedstock like amino and tarry compounds; (4) production of for short term reaction. The kinetic and deactivation studies reveal
marketable by-product carbon (which could be substantially that AC undergoes fast deactivation, even having high initial rate.
reduce the net cost of hydrogen production); (5) mitigation of AC produced from coconut shells displayed the highest initial
overall CO2 emissions from the process; (6) higher fuel flexibility; activity producing hydrogen up to 70–75 vol%. Unfortunately, it is
and (7) no metal carbides formation, hence metal carbide forma- followed by dramatic drop in catalytic activity to attain a steady
tion can make the metal catalyst regeneration more complicated state of very low hydrogen output within 3 h [88]. Very recently,
232 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

Fig. 5. (a) Image of the carbon based honeycomb monoliths; (b) drawing with the geometric parameters of the monolithic structure [128].

Fig. 6. SEM images of carbon produced from methane decomposition on different NCB at 850 1C: (a) untreated NCB; (b) Ni/NCB; (c) Co/NCB; (d) Pd–Ni/NCB [151].
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 233

Gatica et al. [128] applied monolithic honeycomb design to carbon Co/NCB, indicating extended growth time and improved stability of
material (Fig. 5) for TCD in a mass spectrometer. Similar to other Pd–Ni/NCB. The authors [151] also speculate that carbon flake
catalysts, monoliths also undergo activity loss of 35–50%, 50–67% might be originated from a new carbon crystallite on unsaturated
and 50–55% at 750, 800 and 900 1C during 1 h reaction duration, carbon atoms. Hence, large size carbon flake cannot be produced,
respectively. Eventually, this deactivation is similar or smaller because initially formed carbon atoms can quickly satisfy the
compared to other carbon catalysts. Mass spectrometer signal valency constraints and energetic stabilization of unsaturated
analysis reveals that TCD is highly selective towards pure hydro- carbon atoms in the defects. Eventually, doping of Pd–Ni and Pd–
gen and elemental carbon with similar amount of methane Co with NCB gives poor results than that doped with Ni or Co alone,
disappearance and hydrogen production. Furthermore, monoliths but still it is higher than that of untreated NCB and it improves the
shows satisfactory mechanical resistance with no characteristic stability of NCB slightly.
changes even after TCD process and possess efficient hydrogen Furthermore, the addition of SiO2 or SBA-15 to AC, which
production starting at relatively low temperature of 600 1C. The increases its pore volume and surface area, gives better overall
influence of crystallinity and defect concentration of monoliths on activity than that of un-doped AC with initial activity of 30% and
its activity and nature of carbon produced from methane are under 27% at 850 1C, respectively [142]. Meanwhile, AC and CB have
investigation. larger surface area and pore volume than that of AC/SiO2, but
Muradov [127] studied around 30 different carbonaceous exhibit lower activity because of their very poor micropore
catalysts including samples of elemental carbon, AC, CB, nanos- contribution to the total porosity. Zhang et al. [148] found that
tructured carbons, glassy carbons, graphite, etc. and concluded Ni doped carbon exhibit more stable and consistent activity than
that the disordered forms of carbon (e.g., AC and CB) are cataly- the metal catalysts, coal and CLR-based carbons at 850 1C. CLR
tically more active than the ordered ones (e.g., graphite and based carbons, reduced Ni/SiO2 and Ni/Al2O3 shows 20%, 50% and
diamond). The order of activity of carbon catalysts for TCD 40% initial methane conversion respectively and the activity
according to its structure obeys the following order: amorphous declined to 10% by the first 3 h of examination at 850 1C. Contrary
4 turbostratic 4 graphite [34]. Dislocations, low-coordination to the above results, Ni doped carbon shown an increase in its
sites, vacancies, atoms with free valences, discontinuities and activity with time from a 30% initial methane conversion to 80% by
other energetic abnormalities on the surface of amorphous car- 6 h run. Among the three Ni-doped carbon, Ni/RC bear lower
bons because of irregular array of carbon bonds have imperative activity because of higher sulfur content of CLR than those in SH-
impacts on the activity of carbon catalysts. Remarkably, the entire Coal and SL-Coal may easily poison the Ni active site. Furthermore,
surfaces of the catalyst do not participate in gas–solid interface Jin et al. [67] examined TCD in a fixed bed reactor over commercial
methane decomposition, but it occurs through a dissociative AC from coconut shell supported Fe–Al2O3 catalysts prepared by
adsorption of methane molecules on surface active sites of the impregnation method. Despite of the metal loading quantity, Fe–
catalyst [130]. This portion is termed as high-energy sites (HES) Al2O3/AC convert slight volume of methane (5.7%) only at 750 1C as
[134], can be different in each AC. Furthermore, the edges or the active site of Fe need high temperature to catalyze the
defects on the surface of carbon materials are generally accepted decomposition of methane. It is noticed that loading of Fe and
as the active sites for decomposition [138,147]. Al2O3 decrease the surface area and pore volume of carbon
catalyst. 40% Fe/Al2O3 loading with ratio of 16/24 to 24/16
produces catalysts with narrow mesopore distribution which
2.2.1. Carbon catalytic activity boost by metal doping displayed relatively high methane conversion. Although, loading
Very recently, few researchers explored the possibility to amplify of Al2O3 in to AC (0Fe–40Al/AC) shown poorer activity and stability
the activity of carbonaceous catalyst by doping with small amount with an initial methane conversion of 28.6% and negligible final
of metals; a comprehensive utilization of advantages of both metal conversion of 2.2% after 100 min. However, as increasing the Fe
and carbon [148–150]. In addition, the high temperature reduci- content, the TCD follows a decrease–increase–decrease trend with
bility of carbon is helpful for in-situ reduction of metal oxides reaction time. Especially, on the 40Fe–0Al/AC catalyst, the conver-
supported on carbon carrier to metal catalyst during pre-treatment sion decreases quickly from 21.3% to 12.7% at first 60 min, and then
[67]. This in-situ metal oxide reduction helps to avoid additional increases gradually to 26.7% in another 140 min, followed by a
hydrogen reduction step, which simplifies the conventional pre- steady decrease to 13.1% at 360 min, which suggests that the
paration processes. According to Muradov et al., [34] small amount three-step variation is mainly related with the catalytic behaviors
of metal impurities in the carbon catalysts, whether it is doped or of Fe catalyst. The authors found that the initial catalytic activity is
genuinely present in carbon, govern its activity for methane mainly from the AC itself as xFe–yAl/AC with different Fe content
decomposition. By the addition of metal, carbon turns to amor- shows almost similar initial methane conversion. The weakening
phous which results in the development of active HESs. Hence, of AC with reaction time decreases the methane conversion. After
activity enhancement of catalyst may be proportional to the a particular period of time, methane conversion starts to increase
concentration of the active sites on its surface. The trials conducted with a transitional period before Fe particles reach its full
on nano-sized carbon black (NCB) and AC discloses that the loading capacities. This phenomena results a decrease–increase–decrease
of metals like Co and Ni efficiently increases the initial activity of trend in this TCD of methane which is also found in TCD of
carbonaceous catalysts [105,151]. Chen et al. [151] explains the methane over Ni-doped carbons [148].
higher methane conversion of Co/NCB and Ni/NCB in two ways. Prasad et al. [152] studied the influence of metal quantity on
(i) Ni and Co metal particles can take an important role in activating activity of AC. They found that the initial methane conversion rate
methane molecules in the induction period of methane decom- for AC/Pd-10 is more than that of AC/Pd-5 (Fig. 7a). Higher activity
position to generate the intermediates on the surface of Ni or Co, of AC/Pd-10 is ascribed to its higher surface area (245.17 m2/g) than
and then the active intermediates immigrate to the surface of NCB that of AC/Pd-5 (44.21 m2/g), even after methane cracking. Corre-
and decompose to carbon and hydrogen; (ii) the activity of Ni and spondingly, all AC/Ni catalysts (Ni-10, Ni-20, Ni-30 and Ni-40) also
Co metals are much higher than that of NCB in methane decom- exhibit improved activity than AC [153] (Fig. 7b). It is clear from
position. Hence, methane can be directly decomposed on the Fig. 7b that Ni-30 provide maximum initial methane conversion of
surface of metal particles. The secn-doped carbon catalyst are 74 mol% [153]. At the same time, Ni-40 gives lower initial methane
shown in Fig. 6. Pd–Ni/NCB produces carbon flakes of comparatively conversion of 29 mol%, but 75 mol% conversion after a reaction
larger size (Fig. 6c) than those produced over NCB, Ni/NCB and span of 4 h. The decrease in the activity for the first 2 h in the case
234 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

Fig. 7. Methane conversion (mol%) over AC supported (a) Pd and (b) Ni catalysts (T: 850 1C, VHSV: 1.62 l/hgcat) [152,153].

of Ni-20 and Ni-30 is attributed to BET surface area and crystal size the behavior of metal catalyst. GHSV is the volume of gas feed per
of Ni. Furthermore, the lower particle size of Ni (14–46 nm) may be hour per volume of catalyst. Table 5 covers maximum and final
the reason of the enhancement in methane conversion rate after CH4 conversion/H2 production over various carbon catalysts, those
2 h. Hence, all the AC supported Ni catalysts (Ni-10, Ni-20, Ni-30 are previously studied. Hence, it simplifies the understanding of
and Ni-40) exhibited sophisticated activity in TCD. However, Ni different parameter effect on conversion rate. Generally it is
crystal size increasing and the new crystallite Ni3C formation during observed that the hydrogen production rate increase as decreasing
the process lead to the deactivation of the catalysts [105]. the GHSV [139] as well as increasing the temperature [143]. Low
Addition of silica or silicate increases the microporosity of CLR GHSV allows methane molecule to interact with catalysts as well
derived carbon by 28%, along with the ratio of mesoporosity (2– as to enhance the decomposition rate. The experiments conducted
50 nm) to microporosity ( o2 nm) being close to 1:1, results in the on CB at the temperature 850 1C gives an initial conversion of 17%,
formation of hierarchical porous carbon (HPC) [154]. Among whereas the conversion at 950 1C was 77% [139]. Such type of
the prepared catalysts, 1SiRC (1 g of SiO2 as additive) have the conversion rates are expected because of the endothermic nature
optimum composition towards methane decomposition with a of methane decomposition reaction. Influence of partial pressures
methane conversion about 5% higher than that of RC. Whereas, of methane, PCH4 on methane decomposition is also studied
HPC with Al2O3 as additive (AlRC) exhibit outstanding methane recently. At higher PCH4 the rate of mass gain also increases. Abbas
conversion from 27% to 61% together with fibrous carbon produc- and Baker [143] carried out an attempt to study the effect of PCH4
tion (36 g/gAlRC) after 10 h of experiment in a fixed bed reactor at on the initial specific rate of carbon formation for first time. They
850 1C with a total flow rate of 50 mL/min. For the best of authors' found that at higher PCH4, the catalyst produces maximum quan-
knowledge, production of fibrous carbon reported for the first time tity of carbonaceous deposit in a shorter period, which was
from TCD using carbon-based catalyst. The enhanced catalytic supported by further study results [144]. It is due to the increase
activity of HPC for TCD is attributed to the synergistic effect in the rate of diffusion of methane into the interior part of the
between the micropores and mesopores in it. Hence, the effective particle. The optimal conditions for the catalyst depend on the
collision of methane molecule on the discontinuous surface of the final use of the hydrogen produced. For instance, high temperature
HPC surface offer stronger scattering in a limited space results in and low methane space velocity favor production of high purity
high methane conversion. Fibrous carbon formation mechanism is hydrogen suitable for fuel cells application. Moreover, low
displayed in Fig. 8. Fibrous carbon nucleation and growth starts methane/nitrogen ratio also preferred.
either inside the pores or at the edges of the catalyst particles The pore size distribution has significant influence on the
(Fig. 8a–d). Further methane decomposition for several hours activity of the carbonaceous catalysts. It is well observed that the
leads to block the pore (Fig. 8d–f) by carbon deposit. IR spectro- microporous ( o2 nm) AC deactivated very quickly because of
scopy and EDX studies reveal that intensity of OSGs on HPC the small diameter of micropore which undergone carbon filling
reduced sharply after 10 h running of experiment. Meanwhile, first [134,136]. Virgin and deactivated AC studies reveal that the
formed fibrous carbon contains typical quantity of OSG with the O/ methane decomposition occurs mainly within the AC micropores
C ratio of about 0.03 which is lower than that of fresh AlRC. Hence, [135]. On the other hand, the mesoporous AC (2–50 nm) having
oxygen atoms transferred from the carbon catalyst to the produced high surface area shows better stability and hydrogen production.
fibrous carbons, which also facilitate further catalytic activity. Moreover, pore size distribution of mesoporous carbon causes
Though, the carbon deposits produced on the other samples (CC, higher amount of carbon accumulation [125]. Serrano et al. [132]
RC and SiRC) are amorphous particles, with a negligible contribu- employed ordered mesoporous carbon as an efficient catalyst for
tion to the catalytic activity for methane decomposition and hydrogen production via TCD process for first time. They found
hindering the activation of methane on the active sites. Evidently, that CMK-3 and CMK-5 have higher and more stable activity than
the formation of active fibrous carbons is the key to the excellent the other commercial carbonaceous catalysts. The schematic
catalytic performance on AlRC. representation of CMK-3, CMK-5 and their evolution of weight
increase during temperature programmed methane decomposi-
tion reaction are shown in Fig. 9.
2.2.2. Influence of parameters on activity The most outstanding output was given by CMK-5, which gave
GHSV and temperature are the main parameters influencing productivity close to 1 mol H2/gcat. It is equivalent to 22.4 L (STP)
hydrogen production rate over carbonaceous catalyst, similar to of H2/gcat which is two times the value corresponds to that of
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 235

Fig. 8. The nucleation and growth process of the fibrous carbon deposits described by SEM images: (a) 15 min, (b) 30 min, (c) 45 min, (d) 60 min, (e) 90 min and (f) 10 h in
the TCD of methane over AlRC sample [154].

CB-bp. CMK-5 material presents a reaction rate twice that of the formed carbons do not accumulate within mesopores but
CMK-3 and several times superior to those of CBs. After a slow- leaves the pores towards the outer part of the CMK particles. At
down in hydrogen production rate at 25 min, CMKs maintain the same time there is no correlation has been found between the
almost constant hydrogen production rate [5]. It explains that threshold temperature and parameters like surface area and
236 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

CMK-3 CMK-5
Carbon rods Carbon nanotubes 1200
7
Temperature
6 1100

Temperature (°C)
5 CMK-5 1000

W/W
4
900
3
CMK-3
CB-bp AC-mes
2 800
3 nm cavities from AC-mic
SBA-15 removal 5.8 nm cavities 1
700
70 80 90 100 110 120 130 140
Time/min
Fig. 9. (a) Schematic representation of CMK-3 and CMK-5 structure; (b) evolution of catalyst weight increase in temperature programmed methane decomposition [136].

Fig. 10. SEM (a–c) and TEM (d–f) micrographs of the samples: fresh NW-RC (a,d), fresh RC (b,e) and deactivated RC (c,f) [137].

crystallinity in this experiment. Botas et al. [136] conducted a times. Hence, the rate of the chemical reaction steps regulate the
comparison experiment with CMK-5 and CB-bp at a temperature process. However, the diffusional restrictions enforced by giant
1000 1C. The results reveal that an abrupt fall occurred in activity carbon deposit decrease the approachability of methane molecules
of the CB-bp within 4 h. In the same reaction circumstances, CMK- to the reactive sites. Nonetheless, catalysts maintain a noteworthy
5 maintains a high activity with an almost linear rate of carbon activity even within the diffusional control regime for an extended
deposition for more than 72 h with a carbon deposition of around reaction span, disclosing that the deposited carbon are capable to
25 g/gcat. The hydrogen production rates so obtained for CB-bp is leave the CMKs mesopores intact. Those carbon deposit grows
1  1 towards the outside of the catalyst pore permits these materials to
0.189 mol H2 g h , whereas for CMK-5 has a value of preserve a high catalytic activity for a prolonged period. Moreover,
cat
surface area close to 2000 m2/g and bimodal mesopore system of
 1 1
0.599 mol H2 g h , approving the fairly greater catalytic CMK-5 strengthen it for higher hydrogen production as well as
cat strongest resistance to deactivation in long term methane decom-
activity of CMK-5. It is confirmed that the activity transition in position process [124]. Wang and Lua [156] conducted TCD of
the CMK catalysts at short reaction time is related to the partial methane over prepared ordered mesoporous carbons and commercial
filling of the catalyst pore volume caused by the carbon deposits. carbon materials like disordered microporous carbon, mesoporous
The size and quantity of the carbon formed are small compared to carbon and carbon nanotubes and concluded that initial activity is
the diameter and volume of the catalyst pores at short reaction correlated to the chemical structure of the catalysts such as defects,
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 237

while the long-term activity is related to the physical characteristics 900 min. It proposes that the non-porous carbon deposit grows on
such as the BET surface area and pore volume. the pore mouth and hence the entire porous fresh sample is
Zhang et al. [137] conducted TCD experiments on methane very gradually transformed into non-porous. Moreover, a linear rela-
recently with mesoporous carbon prepared from direct CLR to tionship is found in between the quantity of carbon deposited and
reveal the influence of washing. They prepared a series of catalysts total pore volume [44]. Thus, the pore volume establishes the
without washing, washing with de-ionized water, and washing to maximum amount of carbon that the catalyst can accommodate
be nearly free mineral with 2 M HF, 2 M HCl, and de-ionized water before deactivation, i.e., the maximum hydrogen production per
by sequence. The catalyst without washing contains high mineral mass of catalyst.
content including active metal Fe (about 5.2%) which shows higher Moliner et al. [125] concluded with the results that the catalyst
initial conversion. However, the washing of catalysts results in the deactivation is not only controlled by the amount of carbon
removal of its mineral and the pore structure significantly deposited and it becomes apparent that the capability of the
upgraded, hence they exhibit greater activity and stability. The catalyst to accommodate carbon depends on the experimental
experiments conducted with AC supported with SiO2 or SBA-15 conditions. Two effects can be recognized: (i) molecular sieve
also confirms above results. It has been found that the washing effect and (ii) activated diffusion effect. Molecular sieve effect has
stage removes 43% of the weight from AC/SiO2 catalyst [142]. It a strong association with pore mouth blocking. The pore mouth
indicates that the pores of the catalyst without washing were filled decreases with carbon deposition progresses and inner pore sur-
with some mineral matters or related soluble salts which can be face becomes inaccessible for methane adsorption. Activated
removed easily by washing is responsible for its poor activity. diffusion effect is defined with molecular diffusion of methane to
Furthermore, the washing process creates mesopores on catalyst the inside of minute sized pores. The rate of diffusion increases
surface by removing the soluble salt. The SEM images in the Fig. 10 with temperature which increases the deposition inside the pores.
clearly show the carbon matrix with mineral matters and the Hence, TCD at high temperatures take place mostly inside the
related salts (Fig. 10a) of the catalyst without washing. There is no pores, where majority of the high energy AC surfaces located.
pore can see before washing (Fig. 10d), hence all pores are The mesoporous carbons were directly prepared from CLR by KOH
occupied with mineral. Number of mesopores can be seen at activation termed as RC shows extremely different behavior from
various places (Fig. 10b and e), which confirms that the porosity of other catalysts with a three-step linear variation in deactivation of
the resultant carbon is due to the removal of mineral matter and catalyst with reaction time [34,127]. Methane conversion of RC
the related salts present in the carbon on washing [137]. touches 25% from 41% within first 2 h, and then it goes up slightly
to 27% in another 3 h and decreasing gradually to 13% at 40 h [137].
This behavior indicates the autocatalytic ability of the system.
2.2.3. Catalytic deactivation Catalytic activity decline sharply as the porosity is blocked by the
Similar to the metal catalyst deactivation, shielding of the carbon produced in the earlier stages. Hence, the pores of the carbon
active sites is the major reason of carbon catalyst deactivation catalyst were completely blocked and the surface was thickly covered.
too. The carbon produced as a by-product of TCD process has a Eventually, the produced carbons create new active sites for TCD by
structural order in between that of amorphous and graphite and growing to the outside of the catalyst pores and undergo further
has lower surface area. As mentioned before, while amorphous carbonization with time under the reaction conditions, results in a
carbon shows better activity, well-structured graphitic carbon bear promoted methane conversion to some more extent. With the
poor activity only [157]. Deactivation of the carbonaceous catalyst sequence going, the carbon catalyst shows a better activity and
is a type of transformation of catalyst surface from an active state improved stability for TCD. Moreover, the catalyst will be getting
in the fresh sample to an inactive state in the used sample. In deactivated when the deactivation rate of the earlier active sites is
another words, disordered carbon to more ordered carbon. The higher than the production rate of new ones.
activation energy of the carbon nuclei formation during methane
thermal decomposition (316.8 kJ/mol) is much higher than the
activation energy of the carbon crystallites growth (227.1 kJ/mol) 3. Comparison between metal and carbonaceous catalysts
[34]. This implies that, in general, the rate of carbon crystallites
growth tends to be higher than the rate of carbon nuclei genera- Comparisons between metal and carbonaceous catalysts are
tion. The rapid crystallite growth may lead to the formation of a complicated because of the differences in its active center con-
pseudo-ordered (turbostratic) carbon (accompanied with the loss centration as well as the nature of these active sites. A comparison
in surface area and the concentration of HES) and, as result, loss in of initial and final activity of metal and carbonaceous catalyst has
catalytic activity. done in Table 6. It is reported that mild reaction condition is used
OSGs have the ability to make changes on the catalyst surface to produce better CNFs, but drastic condition is required to get
as it desorbed as CO and CO2 from the surface and pores in the higher hydrogen output [157]. While using metal catalyst, removal
early phase of the reaction. Hence, the long-term deactivation is of produced CNFs without harming deactivated metal catalyst for
not associated to the OSG concentration. While, characteristic of reactivation and re-usage of metal catalyst is necessary require-
carbon deposit have heavy impact on carbon catalyst deactivation. ment for economic hydrogen production. In fact, regeneration of
XRD, XPS and Raman spectroscopy studies on fresh and deacti- catalyst is not required in TCD using carbonaceous catalyst. In the
vated catalysts do not give any characteristic structural difference best of authors' knowledge, only one article is available on the
in fresh and used catalysts [125]. Hence, loss of effective surface comparative study of metal and carbonaceous catalysts. Guil-
area of catalyst particle because of deposition of inactive carbon Lopez et al. [43] have experimented with a series of metal and
plays a major role in deactivation. The experimental results show carbonaceous catalysts for comparison. The different metal cata-
that, 50–100 mgC/gcat is enough to deactivate coal-derived AC, but lysts are as follows, six Ni-based catalysts: commercial bulk nickel
commercial ACs like SUPRA and CG need 350 mg and 450 mg oxide (NiO-com), NiO supported on SiO2 and on Al2O3 (Ni/SiO2 and
carbons per gram catalyst, respectively. Deposition of 450 mg of Ni/Al2O3, respectively), Ni–Al spinel (Ni-spinel) and two NiMgAl-
carbon reduces the surface area from 1300 to 46 m2/g. Lázaro et al. mixed oxides from hydrotalcite-like materials (Ni-ex LDHs) with
[139] confirm the rapid diminish in surface area upon carbon different metal loading. Furthermore, two commercial bulk iron
formation. They observed a decrease in surface area from 1300 m2/ oxides, hematite (Fe2O3-hem) and magnetite (Fe3O4-mag), were
g to 300 m2/g in 120 min and fell gradually to negligible values by used as metal-catalysts too. Six commercial carbons, belong to four
238 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

rate, but undergo drastic deactivation with time, which is clear

from the experimental data furnished in Table 6. However,
carbonaceous catalyst and metal doped carbon catalysts hold
better stability and lower deactivation rate compared to metal
catalysts. Despite of better stability of carbonaceous catalyst,
unfortunately it gives poorer methane conversion than metal
catalysts. In addition, metal catalysts offers very reactive CNTs
[158], carbon filaments [133] or nanocarbons showing properties
of molecular sieves [159], while, carbonaceous catalysts produce
amorphous carbon having a variety of morphology.

4. Co-feeding: a promising method for enhancing catalyst

stability
Fig. 11. Thermo gravimetric decomposition of methane over metal and carbon
catalyst [43].
The main drawback of TCD process, in both carbonaceous and
metal catalysts, is the catalyst deactivation over time due to
encapsulation of active catalytic sites by deposited carbon. The
diverse classes having different properties and morphologies, were deactivation of the catalyst takes place through three different
used as carbon catalysts for methane decomposition: CB, AC, stages [61]. First of all, the dilution of the active phase of the
carbon nanotubes and graphite. Four groups of catalysts were as catalyst by the development of carbon formation, this is attributed
follows: CBs of having different textural properties (Vulcan XC72, by low deactivation rate. Second stage is the encapsulation of the
CB-v; and black pearls 2000, CB-bp), microporous AC (AC-micro), active phase of the catalyst which is indicated by the rapid
mesoporous AC (AC-meso), multi-wall nanotubes (MWNT), and deactivation. Third zone is the complete deactivation of the
graphite (graph)as a highly crystalline carbon catalyst. Considering catalyst could be imputable to the formation of carbon which
BET area, they have classified these six carbon catalysts in to three grow up on the catalyst particle without detaching it from the
groups as follows: low specific surface area (graph), high specific support. Use of carbonaceous catalysts enhance and economize
surface area (AC-meso, AC-micro and CB-bp, which present high TCD compared to metal catalyst, even though well-structured
microporous areas), and intermediate specific surface area (MWNT carbon formed from methane decomposition did not favor con-
and CB-v). tinuous methane decomposition [34]. Two solutions were put
The intrinsic catalytic activity of both metal and carbonaceous forwarded to overcome deactivation and lower stability of cata-
catalysts are completely different. Moreover, the surface reduced lysts. Firstly, co-feeding of methane with other hydrocarbons
metal, Ni particle size and Ni-environment (mixed oxide matrix, which in situ produce carbonaceous deposit having higher activity
spinel or simple oxide) can be the root of the activity of metal than that produced from methane during TCD process. Second
catalyst. In the case of carbon catalysts, it is connected to the solution is the regeneration of deactivated catalysts, performing by
quantity of structural imperfections present in the graphene exposing to appropriate activating agents like oxygen, carbon
layers. Initial activities and catalyst deactivation of the two dioxide or steam at higher temperature [23,114,119].
catalysts types have been studied with the purpose of comparing Introduction of co-feed in to the reaction system, either
the catalytic performance of metal and carbon catalyst. From the alternatively or together, can enhance further decomposition of
experimental results of Guil-Lopez et al. [43], the initial activity methane by inhibiting catalytic deactivation [88]. The activity of
(Tth) follows the order: Ni-ex LDH-II ENi-ex LDH-I 4NiO-com 4 the deposit originating from different hydrocarbon co-feed
Ni-spinel 4AC-meso 4CB-bp EAC-micro4 CB-v 4 Ni/Al2O3 4 decreases in the following order: Cbenzene 4Cacetylene 4Cethylene
MWNT4Ni/SiO2 4graph4 Fe2O3-hem 4 Fe3O4-mag. Moreover, 4Cpropane 4 Cmethane [161]. In spite of giving favorable output,
pre-reduced Ni-ex LDH-II with hydrogen begins decomposition the higher expenditure of co-feeding of unsaturated or aromatic
of methane at lower temperature than the most active non- hydrocarbon keeps away from implementing industrial applica-
reduced Ni-ex LDH-II, because a high temperature is mandatory tions. This section of our review focuses specifically on co-feeding
to reduce Ni2 þ phase.Though, metal catalysts deactivated very of methane with other hydrocarbons. Very small number of
rapidly. research work have done on co-feeding of methane with other
All examined metal and carbon catalysts were undergone hydrocarbons in order to stabilize the catalytic activity. The mainly
deactivation at different degrees which depends on their nature studied hydrocarbons are acetylene [88], ethane [162], ethylene
and methane decomposition pathways. Among the studied group, [163], ethanol [164,165], propane [88,162] and propylene [161].
CB-v shows better resistance to deactivation and its ability is Furthermore, CO2 [166–168], H2S [162,169] and O2 [163] were also
attributed to the well-defined concentric graphene layers, which studied as co-feed of methane. AC, CB and metal catalysts were
generate large inter-particle spaces [131]. It is clear from the employed in co-feed methane decomposition. Among them, AC is
Fig. 11; carbon catalysts are more resistant against deactivation mainly studied as it holds considerable activity, while CB and
than metal catalysts. The resistance against deactivation is calcu- metal catalysts shows poor enhancement in catalytic stability
lated by measuring hydrogen produced after 30 min at 1100 1C, compared to AC. Even though, CB and metal catalysts show better
which implies that a high hydrogen production after 30 min at performance in co-feed experiment than that in decomposition of
1100 1C is associated to a low deactivation degree, and the order as methane alone. Recently published experimental results and
follows: CB-v 4CB-bp 4MWNT⪢graphEFe2O3-hem 4Ni-ex LDH- major findings on TCD in the presence of co-feed are furnished
II4 AC-meso 4Ni-ex LDH-I⪢ NiO-com 4AC-micro4 Ni-spinel 4 in Table 7.
Ni/Al2O3 E Ni/SiO2⪢Fe3O4-mag [43]. Table 6 comprises initial and
final activity as well as the stability of various metal, metal doped 4.1. Alkanes as co-feed
carbon and carbonaceous catalyst under diverse experimental
parameters and reactors. Those prior study results are also In 1998, TCD of methane performed by Muradov [88] in the
revealing that metal catalyst maintain high activity and conversion presence of propane and acetylene individually. He found that the
Table 7
Recently studied TCD of methane with co-feed: a comparison of results and major observations.

Catalyst Operating conditions Physical properties Feed Initial Conversion at tmax tmax tCH4 tH2 t d Ref.

T F W SA iCH4 iH2 CH4 H2 At t

Activated alumina 850 – – – (70%) CH4 þ (30%) C3H8 – 40 – 44 0.1 – 12 4 – [88]

Quartz wool 850 – – – (93%) CH4 þ (7%) C2H2 – 15 – 18 0.5 – 17 1.3 –
Major findings
 Addition of propane do not favor methane decomposition rate.
 (93%) CH4 þ (7%) C2H2 mixture gives higher hydrogen concentration than the theoretically calculated value.

U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256
 Carbon produced from acetylene shows better catalytic activity which enhances methane decomposition.

Commercial CB - BP2000 900 50 1.2 1400 85%CH4 – 30 – 30 0 – 25 2 – [162]

900 50 1.2 1400 85%CH4 þ5%C3H8 – 37 – 37 0 – 32 2 –
900 50 1.2 1400 85%CH4 þ10%C2H6 – 41 – 41 0 – 35 2 –
900 50 1.2 1400 85%CH4 þ10%C2H6 þ5%C3H8 – 43 – 43 0 – 40 2 –
Major findings
Hydrogen and methane was the only reaction product detected.
Individual ethane and propane co-feeding of methane increasing the output hydrogen concentration and quasi steady state of methane.
Ternary mixture of methane, ethane and propane gives best results with 43% and 40% initial and final hydrogen concentration, respectively.
Addition of H2S at 1 h increase H2 volume from 36% to 45%. HS∙ radical formed from H2S attacks methane molecules and results in the formation of H2 and carbon.

PAC 950 10 0.05 1131 CH4 – 36 – 36 0 – 21 4 – [120]

950 10 0.05 1131 CH4–10% C2H4 – 39 – 39 0 – 38 4 –
950 10 0.05 1131 CH4–20% C2H4 – 44 – 44 0 – 43 4 –
WG-12 950 10 0.05 1087 CH4 – 32 – 32 0 – 11 4 –
950 10 0.05 1087 CH4–10% C2H4 – 36 – 36 0 – 30 4 –
950 10 0.05 1087 CH4–20% C2H4 – 38 – 38 0 – 37 4 –
RX-3 950 10 0.05 1124 CH4 – 33 – 33 0 – 10 4 –
950 10 0.05 1124 CH4–10% C2H4 – 34 – 34 0 – 30 4 –
950 10 0.05 1124 CH4–20% C2H4 – 36 – 37 1 – 37 4 –
Major findings
AC catalyzes ethylene decomposition than methane decomposition results in production of more hydrogen from ethylene than from methane in the beginning of reaction.
Activated carbon obtained from pine wood biomass (PAC) shows better initial as well as final activity among the studied catalysts.
Ethylene originated carbon catalyze methane decomposition, while methane originated carbon hindering further methane decomposition.
Increasing temperature produce more hydrogen as reaction shift towards product side at higher temperature.
Continuous introduction of ethylene is an effective method to maintain catalytic stability as ethylene originated carbon shows more activity than methane originated one.

PAC 850 10 0.05 – CH4 9 – 9 – 0 2 – 4 – [163]

Na þ /CaO þPAC 850 10 0.05 þ 0.80 – CH4 þ10%O2 6.4 – 6.4 – 0 3 – 4 –
þ
Li /MgO þPAC 850 10 0.05 þ 0.80 – CH4 þ10%O2 10.5 – 10.5 – 0 5 – 4 –
Major findings
 Oxidative Coupling of Methane (OCM) performed with Na /CaO or Li /MgO catalyst systems for in situ preparation of ethylene followed by TCD of methane over AC.
þ þ

 Li þ /MgO catalyst and 10% O2 containing reaction mixture produces 3–3.5% ethylene yield which is more than that given by Ni þ /CaO.
 PAC þ Na þ /CaO in combined OCM-TCD of methane process produces lower methane conversion than that produced by TCD of methane by PAC catalyst.
 OCM-TCD combined process leads to the production of CO2, ethylene and water in addition to hydrogen.
 CO2 and water enhance catalytic stability by the gasification of produced carbon.
 With increasing time in OCM-TCD combined process, deposition of ethylene originated carbon increases and hence production of hydrogen compared to TCD process.
 OCM-TCD combined process with Li þ /MgO þ PAC catalysts mixture shows 2.5 times more methane conversion than that with PAC alone in TCD process after 4 h of reaction.
 As OCM-TCD combined process produces sub products other than hydrogen, additional purification steps are necessary to get pure hydrogen.

239
 240
Table 7 (continued )

Catalyst Operating conditions Physical properties Feed Initial Conversion at tmax tmax tCH4 tH2 t d Ref.

T F W SA iCH4 iH2 CH4 H2 At t

PAC 950 10 0.05 1131 CH4 – 36 – 36 0 – 21 4 – [161]

950 10 0.05 1131 90% CH4 þ 10% C3H6 – 33 – 33 0 – 31 4 –
950 10 0.05 1131 80% CH4 þ 20% C3H6 – 34 – 36 4 – 36 4 –
WG-12 950 10 0.05 1087 CH4 – 32 – 32 0 – 11 4 –
CH4 þ 10% C3H6 – – – –

U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256
950 10 0.05 1087 90% 29 29 0 26 4
950 10 0.05 1087 80% CH4 þ 20% C3H6 – 31 – 31.5 4 – 31.5 4 –
Norit RX3 Extra 950 10 0.05 1124 CH4 – 33 – 33 0 – 10 4 –
950 10 0.05 1124 90% CH4 þ 10% C3H6 – 24 – 25 4 – 25 4 –
950 10 0.05 1124 80% CH4 þ 20% C3H6 – 29 – 31.5 4 – 31.5 4 –
Major findings
 Propylene decomposition results in production of hydrogen, methane and ethylene as main products and small amount of side products like ethane, propane, butenes in the temperature range 580–640 1C and ethane,
acetylene, propylene in the range 887–1427 1C.
 Carbon produced from propylene and carbon formed by decomposition of the compounds produced upon propylene decomposition can boost TCD of methane.
 Introduction of propylene enhance hydrogen concentration in effluent gas by 3.2 and 4.6 times at 850 1C.
 Propylene does not increase initial catalytic activity, but stabilizes the overall catalyst performance. Furthermore, at 950 1C initial and final hydrogen concentration in effluent gas is same.
 Compared to other catalysts, PAC shows maximum hydrogen production at all temperature range.
 TCD of methane in the presence of propylene producesmore ordered carbon deposit, and some of them have filamentous structure. Despite high crystallinity, this deposit exhibit greater catalytic activity than that originated
from clean methane on its TCD.

AC 950 10 0.05 1090 CH4 – 13 – 16 4 – 16 4 – [164]

950 10 0.05 1090 CH4 þ10%C2H5OH – 22 – 24.5 1 – 21 4 –
950 10 0.05 1090 CH4 þ20%C2H5OH – 27 – 29 1 – 27 4 –
950 10 0.05 1090 CH4 þ30%C2H5OH – 33 – 37 4 – 37 4 –
950 10 0.05 1090 CH4 þ40%C2H5OH – 34 – 40 4 – 40 4 –
Major findings
Effluent gas after simultaneous decomposition of ethanol and methane mixture contains methane, hydrogen, carbon oxide, carbon dioxide, ethylene, ethane, water, acetaldehyde and un-reacted ethanol.
In the mentioned TCD of methane, catalytic surface area decreases from 1090 m2/g to about 10–71 m2/g and hence the pore volume leads to rapid deactivation.
As the ethanol co-feed methane decomposition is a complex process, the initial methane conversion started to count from 25th minute onwards.
Increasing amount of ethanol increases both hydrogen content in the output gas and the stability of catalyst.
Experimental results always stay above the calculated value in all temperatures proves the catalytic enhancement due to ethanol.
Methane originated carbon shows higher crystal ordering and, hence low catalytic activity.

Ni/Al2O3 600 100 0.05 – CH4 þN2(1:1) 34.1 – 36 – 0.15 12 – 2 2.5 [166]
600 100 0.05 – CH4 þCO2 (1:1) 33.4 – 41 – 0.41 30 – 3 –
650 100 0.05 – CH4 þN2 (1:1) 46.3 – 46.3 – 0 2 – 1.5 2
650 100 0.05 – CH4 þCO2 (1:1) 40 – 44 – 0.28 31 – 3 –
700 100 0.05 – CH4 þN2 (1:1) 54.1 – 54.1 – 0 2 – 0.75 1
700 100 0.05 – CH4 þCO2 (1:1) 71.9 – 71.9 – 0 55 – 3 –
Major findings
CO2 and CH4 mixture avoids catalyst deactivation substantially.
Produces synthesis gas with H2:CO ratio near to 1.
Fishbone CNFs formed at 600 1C and ribbon CNFs at 700 1C.
The quantity of carbon deposition declines with increasing temperature.
Presence of CO2 diminishes the encapsulation of catalyst active site via Bouduard reaction.
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 241

(W, weight of catalyst (g); SA, surface area (m2/g); T, temperature (1C); F, total flowrate (mL/min); iCH4, initial methane conversion (%); iH2, initial hydrogen production (%); tmax, time at which maximum methane conversion or
 Influence of H2S on methane decomposition and CO2 reforming were studied on AC (FY5), alumina supported Ni catalyst (NiA) and the mixture of both (FY5 þ NiA) separately using conventional electric and microwave heating
addition of 30 vol% propane did not give pleasing conversion of
methane over activated alumina. Moreover, the hydrogen produc-

[169]
[167]

tion is decreased from an initial value of 40 to 12 vol% in 4 h.

While, the activity of quartz wool for TCD were maintain almost
consistent for around 1.5 h by the introduction of acetylene to
methane, and it shown better hydrogen content in the final stage
–
–
–

–
–
than the initial conversion. This better final catalytic activity
attributed to the carbon produced from acetylene. Mesoporous
 For the experiment conducted at 950 1C, the highest initial methane conversion and final methane conversion to hydrogen is given by the mixtures containing 50% CO2 and 20% CO2, respectively.

CB (BP2000) of having surface area 1400 m2/g has been employed

4
4
4

2
2

to decompose binary mixture of methane–ethane and methane–

propane as well as ternary mixture of methane–ethane–propane
[162]. The decomposition of methane–propane mixture margin-
–
–
–

–
–

ally surges the concentration of hydrogen at the quasi-steady state,

reaching 32% from 25% in methane only decomposition. The best
result was given by ternary mixture with initial hydrogen produc-
19.5

20
24
14

10

tion of 43 and 40 vol% after 2 h. Ethane and/or propane introduc-

tion to the TCD process using the BP2000 catalyst has a promoting
hydrogen production occur (h); t, time (h); d, deactivation time (h);–, not mentioned in the original paper. Note: all experiments were conducted in fixed bed reactor).

effect, given that concentration of hydrogen in the post-reaction

0.55

stream improved primarily because of the contribution of hydro-

0
0
0

gen present in those hydrocarbons. Moreover, a stable hydrogen

concentration is observed in the effluent stream of TCD in the
presence of ethane and propane indicating that the carbon
–
–
–

–
–

deposited from them does not aggravate deactivation of BP2000

 While H2S enhance catalytic stability of FY5, it strongly deactivates metal NiA catalyst because of its lack of tolerance towards sulfur poisoning.

catalyst.
23.5
24.5
30

34
38

4.2. Ethylene as co-feed

 Methane decomposition reaction conducted at 750, 850 and 950 1C with CH4/CO2 mixture, with varying CO2 content from 5% to 50%.

Ethylene originated carbon shows higher activity towards

–
–
–

–
–

methane decomposition, but less active towards ethylene decom-

position [34]. In the initial stage of TCD with ethylene co-feed,
23.5
24.5
30

28
38

major portion of hydrogen originates from ethylene. Hence, high

hydrogen and zero ethylene content detected in the initial effluent
gas [120]. PAC shows a 41% of activity loss in TCD at 950 1C within
4 h, while, ethylene assisted methane decomposition maintain its
initial hydrogen production of 44 vol% until 4 h without any
noticeable activity loss. The similar tendency was shown by other
two catalysts, WG-12 and RX-3, at all three temperatures as shown
CH4 þ20%CO2
CH4 þ50%CO2

in Fig. 12(a–c).
CH4 þ1%H2S

 Methane conversion is higher under microwave heating than that of conventional heating.

As ethylene is expensive, Malaika et al. [163] produced it in-situ

by oxidative coupling of methane (OCM) merged with the TCD
CH4

CH4

process in the same reactor. Na þ /CaO or Li þ /MgO catalysts

prepared by impregnation method were employed for OCM
process and AC catalysts for TCD. In the first stage of OCM-TCD
1131
1131
1131

coupled process, methane with admixture of oxygen was flown

–
–

 Influence of H2S on conversion is similar under both heating sources.

through the OCM oxide catalyst over which ethylene was pro-
duced. Then, the un-reacted methane and the post-reaction gases
were allowed to pass over the bed of the AC catalyst to produce
more active carbonaceous catalyst by decomposition of ethylene in
0.05
0.05
0.05

order to maintain catalytic stability. Unfortunately, OCM-TCD

2
2

process is not a favorable method as this process gives lesser

methane conversion than the PAC catalyst done. It may be because
the combined process produces ethane, CO2 and water together
20
20
10
10
10

while TCD produce only hydrogen as gas. Even though, in the final
stage of the coupled process, methane conversion rate is 2.5 times
more than that given by PAC. It is due to the gasification of the
800
800
950
950
950

active site blocking carbonaceous deposit by the produced CO2 and

H2O.

4.3. Ethanol as co-feed

Concurrent decomposition of methane–ethanol mixture pro-

Major findings

Major findings

duces the similar products as pure ethanol produces on its

decomposition. They are methane, hydrogen, carbon monoxide,
sources.
AC - FY5

carbon dioxide, ethylene, ethane, water and acetaldehyde

[164,165]. The theoretical decomposition value obtained by the
AC

addition of individual cracking of methane and ethanol were

242 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

Fig. 12. Influence of ethylene on catalytic activity of catalyst (a) PAC, (b) WX-12 and (c) RX-3 sample at different methane decomposition reaction temperatures. (M and E
stand for methane and ethylene, respectively) [120].

crystallinity of methane-originated carbonaceous deposit drop

down the activity of spent catalyst on pure methane decomposi-
tion process. XRD studies reveals that the carbonaceous deposit
become more ordered with increasing the decomposition tempera-
ture. Fig. 13 shows the XRD spectra of various carbons in the following
order, (a) initial AC; (b) carbon from methane at 850 1C (M-850);
(c) carbon from ethanol at 850 1C (E-850); (d) carbon from metha-
neþethanol at 850 1C (ME-850) and (e) carbon from metha-
e neþethanol at 950 1C (ME-950). Two broad reflexes of carbon
d obtained in the diffractogram are C(002) at 2θ close to 261 and C
(101) at 2θ close to 441. In general, lower value of the ratio between
c the intensities of these bands (C(101)/C(002)) is the characteristic
b
parameter of higher crystal structure ordering degree [139]. C
(101)/C(002) ratio of fresh AC (Fig. 13a) is comparatively high
a which corresponds to higher structural disorder and results in its
higher initial activity. High crystallinity of methane-originated
10 15 20 25 30 35 40 45 50 55 60
carbonaceous deposit drop down the activity of spent catalyst on
Fig. 13. XRD spectra of selected carbon catalysts: (a) initial AC; (b) M-850; (c) E- pure methane decomposition process. Furthermore, pure ethane
850; (d) ME-850; (e) ME-950 [164]. and methane þethane mixture also produce more ordered carbo-
naceous deposit than that of methane (Fig. 13c and d). The impact
always lower than that of methane–ethanol mixture decomposi- of temperature on crystallinity is shown by XRD results and it
tion. This gap between the experimental and theoretical values reveals that the carbonaceous deposit become more ordered with
was 4–5% at 750 and 850 1C [164]. The prominent influence of increasing the decomposition temperature (Fig. 13d and e).
ethanol was observed at 950 1C with a 29% hydrogen concentra- Despite of having low surface area as well as high structural
tion in effluent gas, whereas the theoretical expectation was 21% ordering, carbonaceous deposit obtained from TCD of mixture of
only. This higher output of hydrogen indicates the catalytic methane and ethanol shows higher activity is explain with SEM
influence of ethanol and carbon produced from it. High image shown in Fig. 14. TCD of methane does not make any
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 243

Fig. 14. SEM image of selected carbon samples: (a) initial AC; (b) M-850; (c) E-850; (d) E-850 (higher magnification); (e) ME-850; (f) ME-950 [164].

substantial variations on the sponge-like structure of porous AC the volume of hydrogen generated. Likewise, addition of 20% gives
(Fig. 14a and b). Eventually, the water and carbon dioxide origi- six-fold and 40% gives ten-fold rise in the volume of hydrogen
nated from ethanol decomposition gasify carbon substances which produced.
causes the degradation of the porous structure of AC. Furthermore, Whereas, TCD of methane over AC at 750 1C with the pulse
a novel separate phase grown by the deposited carbon look like a introduction of ethanol at 60 and 120 min causes a diminution in
“wool” (Fig. 14 c and d). This specially structured carbonaceous its catalytic activity [165]. In the pulse introduction of ethanol,
deposit shows much better catalytic activity than that obtained Rechnia et al. [165] introduced methane into the reactor at the rate
from clean methane. The methane conversion increases as increas- of 10 mL/min and cut off after one hour. Then the reactor was
ing the temperature in the co-feeding process in a similar manner rinsed with Ar (10 mL/min) followed by the introduction of
as we observed in normal TCD [120,161,164]. The hydrogen ethanol in to the gas stream using a syringe pump at the rate of
concentration in effluent gas of 40% ethanol co-feed methane 1.4 mL/h for 15, 30 or 60 min. The reactor was again rinsed with Ar
decomposition at its final stage of reaction at 4 h are 19, 24 and after the mentioned time of ethanol decomposition and the
40 vol% at 750, 850 and 950 1C respectively [164]. Similarly, the methane/ethanol decomposition was repeated till the end of 4 h
higher amount of co-feed hydrocarbon also helps to produce more methane decomposition. TCD of methane over AC at 750 1C, the
volume of hydrogen in the decomposition process. The introduc- pulse introduction of ethanol at 60 and 120 min causes a diminu-
tion of 10% ethanol to methane at 750 1C gives a four-fold rise in tion in its catalytic activity. Furthermore, greater carbon catalyst
244 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

deactivation observed when injecting ethanol for longer time. ethanol and propylene assisted methane decomposition gives 40 and
Hence, ethylene formed by the decomposition of ethanol produces 36 vol% final hydrogen production over PAC catalyst at 950 1C,
very small amount of active carbonaceous deposit on its decom- respectively. While, ethylene assisted methane decomposition gives
position. In addition, it is noted that the decrease in surface area of 43 vol%.
carbon catalyst is higher in ethanol assisted methane decomposi-
tion (from 1090 m2/g to 10 m2/g) than in methane alone decom-
position (1090 m2/g to 71 m2/g). The addition of ethanol for 1 h in
to reaction system at 850 1C gave entirely positive result than at 4.5. CO2 as co-feed
750 1C. More interesting fact is the decrease in surface area of
carbon catalyst was similar as at 750 1C indicates the indepen- Introduction of CO2 to TCD process has been investigated in two
ways. Several authors proposed as the second stage of cyclic TCD
dence of catalytic activity on surface area. Unfortunately, the
results obtained at 950 1C were also not favorable as the graphi- process in order to gasify the deposited carbon by Boudouard
reaction (C þCO2-2CO) [170] (see Regeneration). The second
tization of formed carbon was higher at 950 1C prohibit higher
methane conversion. approach is the introduction of CH4:CO2 mixture (core constitu-
ents of biogas) in to the reaction system known as dry reforming of
methane (DRM) or CO2 reforming [171–173]. Co-feeding of CH4
4.4. Propylene as co-feed and CO2, two undesirable GHGs, produces synthesis gas with a
molar ratio 1:1 (Eq. 6) [174–177]. Furthermore, it produces inter-
Decomposition of propylene is a complex process which results esting nanocarbon like fibrous, ribbon, fish-bone type, etc. Synth-
in the formation of hydrogen, methane and ethylene as main esis gas can be utilized as fuel for solid oxide fuel cells or in
products and ethane, propane, butane, acetylene and propyne in Fischer–Tropsch synthesis for producing eco-friendly liquid fuels
small scale. All these formed product and non-decomposed from renewable source such as biogas, and for many further
propylene can undergo further decomposition leading to the applications. A water gas shift reaction together with CO–H2
generation of catalytically active carbonaceous deposit which separation is obligatory if the objective of the process is to produce
helps to maintain longer catalytic stability in TCD. The total pure hydrogen [166]. From a thermodynamic point of view,
amount of hydrogen produced in the process is resultant of two working at high temperature with low CH4:CO2 (o1) ratio is
components: (a) the amount of hydrogen formed in decomposi- more appropriate for reducing carbon formation. On the contrary,
tion of methane, propylene and other in situ produced hydro- moderate temperatures with CH4:CO2 ratio close to one is much
carbons and (b) the amount of hydrogen used in the reactions of more desirable for industrial works [178].
hydrogenation of the unsaturated hydrocarbons produced. Hence,
1
it is difficult to distinguish hydrogen produced from propylene and CH4 þCO2 -2H2 þ2CO; ΔH 298 ¼ 247 kJ mol ð6Þ
methane. In the best of authors' knowledge, the very first attempt
on TCD with propylene as a co-feed has done by Malaika and Initial conversion of methane obtained in the test executed
Kozłowski [161] in 2010. They have thermocatalytically decom- with CH4:CO2 mixtures at 700 1C over Ni/Al2O3 catalyst was higher
posed methane in the presence of 10% or 20% of propylene at 750, than that obtained in the absence of CO2; 71 and 54% respectively
850 and 950 1C over three different AC catalysts for comparison. [166]. Catalytic deactivation happen rapidly after a short time
Co-feeding of 10% or 20% propylene enhances the content of period of stream in the reaction conducted without CO2. Further-
hydrogen in outlet gases in the final phase of the process by more, Ni/Al2O3 catalyst maintained high catalytic stability in the
3.2 and 4.6 times, respectively. Presence of propylene does not presence of CO2 with a maximum conversion of 41%, 44% and 72%
amplify initial activity of catalyst at 950 1C, but aided to maintain at 600, 650 and 700 1C, respectively. Moreover, the final conver-
the catalytic activity without any loss until the experimented span sions were 30%, 31% and 55% at respective temperatures. Adamska
of 4 h. Pure methane decomposition does not make any significant et al. [167] found that the greatest initial conversion and higher
changes on the crystallinity of PAC, but appears as a uniform stability given by the mixture with 50% and 20% CO2 at 950 1C,
coating over PAC results in catalytic deactivation (Fig. 15a and b). respectively. They concluded that, the overall process is the
On the other hand, TCD of methane in the presence of co-feed resultant of the following processes: augmentation of deposited
propylene gives carbonaceous deposit with filamentous structure carbon over the catalyst, CO2 gasification of the carbonaceous
(Fig. 15c). The extended catalytic activity in this process is deposit and partial gasification of the AC catalyst by CO2. Some of
attributed to this filamentous carbon deposit. Beyond everything, the side reaction between CH4 and CO2 do not produce hydrogen
co-feeding of ethylene shows better activity at all temperatures and which is responsible for the slightly poor conversion of methane to
with all studied AC catalysts than that given by propylene as well as hydrogen obtained for processes with stream containing 5 and
ethanol assisted methane decomposition [120,161,164,165]. When 10 vol% CO2.

Fig. 15. SEM images of (a) fresh PAC sample; (b) after reaction with pure methane and (c) after reaction with 80% methane þ 20% propylene mixture at 850 1C [161].
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 245

4.6. H2S as co-feed in the reaction system can appreciably restrict the deactivation of
the carbon catalyst used.
Fidalgo et al. [169] co-feed methane with small amount (0.5–
1.0 vol%) of H2S as well as CO2 and thermodynamically decompose
over individual catalysts like AC (FY5) and Ni/Al2O3 (NiA) and over 5. Catalyst regeneration
mixture of both (FY5 þ NiA). Both electrical furnace and microwave
have been used as heating source of furnace in order of compar- Practically, catalysts used for chemical process do not possess
ison. The AC (FY5) shows 10 vol% higher initial methane conver- permanent activity. Poisoning, coke formation and sintering make
sion in the presence of 1% H2S than that obtained in the absence of catalysts less active over time at various extents. Co-feed of
H2S indicates the tolerance of carbon catalyst to H2S [169]. Though, methane with other hydrocarbon was unsuccessful to avoid
the conversion decreased from 70% to 8% over metal (Ni/Al2O3) complete deactivation of catalysts. Eventually, carbon deposition
catalyst indicates its lack of tolerance toward sulfur impurities. The cannot be prevented as it is a main and unavoidable by-product
pulse introduction of 1% H2S at 60th minute of the process increase of methane decomposition which encapsulate the active site of
hydrogen concentration in the effluent gas from 36% to 45% [162]. catalyst and results in its deactivation. Hence, regeneration of
The theoretical calculation reveals that the complete decomposi- deactivated catalysts by activating agents at elevated temperature
tion of whole 1% H2S can raise the hydrogen concentration in is the ultimate solution for ensuring continuous production of
effluent gas by 1 vol% only. Hence it is clear that the catalytic hydrogen via cyclic decomposition of methane. Combustion and
influence of H2S by the formation of HS∙ radicals which converts gasification of the carbonaceous deposit are the two methods
methane to hydrogen and carbon. Furthermore, experimental usually adopted for catalysts regeneration. Oxygen is using for
results approve that the generation of energetic micro plasmas combustion [114] and gasification of carbon done by steam [119]
within the catalyst/microwave receptor bed produced while using or carbon dioxide [181] as shown in Eqs. (7)–(9) respectively.
microwave heating source directs the system to have a better C þ O2 -CO2 ; ΔH 1073 ¼  394:7 kJ=mol ð7Þ
methane conversions than those obtained under conventional
heating [179,180]. C þ H2 O-CO þH2 ; ΔH1073 ¼ 135:9 kJ=mol ð8Þ
Fig. 16 shows a comparison chart of initial and final hydrogen
production of various metal and carbonaceous catalysts with and C þ CO2 -2CO; ΔH1073 ¼ 174:5 kJ=mol ð9Þ
without co-feed, irrespective of the experimental condition. The During the activation stage of deactivated catalysts, removal of
data have taken from the previously conducted research works. A surface carbon is occurred and restore the surface area. The ratio of
comparison with the visualized results are almost impossible as mass removed is known as burn-off. This regeneration of surface
their experimental parameters are different. Even though, it is area is supported by the formation of large number of OSGs [182],
clear from the chart that major losses in activity have been which help to preserve further activity. The main disadvantage of
occurring with both metal and carbonaceous catalyst in the regeneration process is the requirement of additional purification
absence of co-feed. However, co-feed helps to preserve the activity process in order to get pure hydrogen. Regeneration process
of catalyst for long time. Concurrently, carbonaceous catalysts in results in the formation of comparable quantity of CO2 and CO as
the presence of hydrocarbons, mentioned above, maintain the that produced in SRM process [123,170], which enforce to imple-
initial activity until the end of process, sometimes more than the ment a purification stage. Whereas, steam gasification improves
initial activity. It is worth to note that it shows higher final the overall hydrogen yield by the contribution from H2O. Even
hydrogen production than initial production at higher tempera- without regeneration process, some catalysts like Ni/ZrO2,
ture. The experimental results confirm the views of Muradov [88] Ni/Al2O3, etc. shows continuous activity without much deactiva-
that either pulse or continuous introduction of other hydrocarbon tion [183]. However, such nonstop decomposition process leads to

Fig. 16. Comparison chart of TCD with metal, carbon catalyst and co-feed. The data have taken from previously published articles. Experimental parameters, reactor and
references corresponds to each catalyst are provided in Table 8.
246 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

Table 8
The experimental parameters, reactor and references of each catalyst mentioned in Fig. 16.

Catalyst Reaction condition (T/F/W/SA/t) Reactor Ref.

1 Ni–Cu–Al 700/120,000a/0.05/80/2.5 FB [33]

2 Ni/TiO2 700/20b/0.3/30/8 FB [52]
3 Ni/Al2O3 700/12a/–/124/3 RB [53]
4 Fe/Al2O3 800/1.5a/–/141/3 RB [53]
5 Fe/MgO 800/12,000a/0.15/14.7/3 FB [56]
6 NiCu/Al2O3 700/12,000a/10/–/7 FlB [28]
7 Ni–Cu/MgO 700/12a/–/14/3 RB [53]
8 Fe–Mo/MgO (1) 800/1.5a/–/17/3 RB [53]
9 Fe–Mo/MgO (2) 800/1000a/0.15/15.3/3 FB [56]
10 Fe–Mo/MgO (3) 800/12,000a/0.15/15.3/3 FB [56]
11 FeMo/Al2O3 800/12,000a/0.15/193.3/1.5 FB [56]
12 MgO/SiO2 750/60–65b/–/–/200 FB [64]
13 K/MgO/SiO2 800/60–65b/–/–/200 FB [64]
14 Ni/K/MgO/SiO2 700/60–65b/–/–/1 FB [64]
15 AC-from cocnut 850/–/–/–/3.5 FB [88]
16 AC (AX-21) 850/–/–/–/4 FB [88]
17 CB (VulcanXC-72) 850/–/–/–/4 FB [88]
18 Graphite 850/–/–/–/2 FB [88]
19 CB (Carbopack B) 850/38b/–/100/4 FB [138]
20 CB (Carbopack C) 850/38b/–/10/8 FB [138]
21 CB (Fluka 03866) 850/38b/–/94/4 FB [138]
22 CB (Fluka 05120) 850/38b/–/930/8 FB [138]
23 CB (BP 2000) 850/38b/–/1337/8 FB [138]
24 CB (HS-50) 850/38b/–/40/8 FB [138]
25 AC (CG Norit) (1) 850/38b/–/1300/7.5 FB [138]
26 AC (CG Norit) (2) 850/600a/2/1100/4 FB [125]
27 AC (Norit supra) 850/600a/2/925/4 FB [125]
28 AC (Norit GAC) 850/600a/2/1300/4 FB [125]
29 AC (SCA750) 850/600a/2/360/4 FB [125]
30 AC (SCA600) 850/600a/2/161/4 FB [125]
31 AC (SC800) 850/600a/2/52/4 FB [125]
32 Shengli char 850/200b/10/–/2 FB [155]
33 Xiaolongtan char 850/200b/10/–/2 FB [155]
34 Binxian char 850/200b/10/–/1 FB [155]
35 Jingcheng char 850/200b/10/–/1 FB [155]
36 CB (BP 1300) 850/144 h  1/–/495/6.5 FB [139]
37 CB (BP 2000) 850/144 h  1/–/1337/6.5 FB [139]
38 Activated alumina 850/–/–/–/4 (C3H8) FB [88]
39 Quartz wool 850/–/–/–/1.3 (C2H2) FB [88]
40 AC (PAC) (1) 950/10b/0.05/1131/4 (CH4 only) FB [120]
41 AC (PAC) (2) 950/10b/0.05/1131/4 (CH4 þ20%C2H4) FB [120]
42 AC (PAC) (3) 950/10b/0.05/1131/4 (80%CH4 þ20%C3H6) FB [161]
43 AC (WG-12) (1) 950/10b/0.05/1087/4 (CH4 only) FB [120]
44 AC (WG-12) (2) 950/10b/0.05/1087/4 (CH4 þ20%C2H4) FB [120]
45 AC (WG-12) (3) 950/10b/0.05/1087/4 (80%CH4 þ20%C3H6) FB [161]
46 AC (RX-3) (1) 950/10b/0.05/1124/4 (CH4 only) FB [120]
47 AC (RX-3) (2) 950/10b/0.05/1124/4 (CH4 þ 20%C2H4) FB [120]
48 AC (Norit RX3) 950/10b/0.05/1124/4 (80%CH4 þ20%C3H6) FB [161]
49 CB (BP-2000) (1) 900/50b/1.2/1400/2 (85%CH4) FB [162]
50 CB (BP-2000) (2) 900/50b/1.2/1400/2 (85%CH4 þ5%C3H8) FB [162]
51 CB (BP-2000) (3) 900/50b/1.2/1400/2 (85%CH4 þ10%C2H6) FB [162]
52 CB (BP-2000) (4) 900/50b/1.2/1400/2 (85%CH4 þ10%C2H6 þ5%C3H8) FB [162]
53 AC (1) 850/10b/0.05/1090/4 (CH4 only) FB [164]
54 AC (2) 850/10b/0.05/1090/4 (CH4 þ40%C2H5OH) FB [164]

(T, temperature (1C); F, flow rate (amL/(gcat.h) bmL/min cNmL/min, unless other units are stated); W, weight of catalyst (g); SA, surface area (m2/g); Conversion (%); t¼ time
(h); FB, Fixed Bed Reactor; FlB, Fluidized Bed Reactor; RB, Rotatory Bed reactor; –, not mentioned in the original paper; and co-feed in bracket, if any).

deposition of large amount of carbon which causes increase in of hydrogen for each mole of methane [23]. Ammendola et al.
pressure drop across the catalyst bed from 0.02 to 0.12 atm as well [194] experimented methane (5%CH4 in N2 flow) decomposition
as physical blockage of the reactor. Therefore, carbon removal is over 25 g of CuAl2O4 catalyst in a fluidized bed reactor. Gasification
necessary to avoid such hurdles. Latest catalyst regeneration of produced carbon performed with 5.5 vol% CO2 in N2 stream and
experiments and major findings are furnished in Table 9. 3 vol% steam in N2 stream. They observed that the CO2 regenera-
tion rate decreases after 15 min and only 45% of deposited carbon
5.1. Gasification were gasified after 80 min. Steam also gasified almost similar
amount of carbon as CO2 done. Moreover, the quantity of carbon
Both metal and carbonaceous catalyst can be regenerated by removed during both gasification processes is lower than that
gasification, but the activity of regenerated catalyst varies. The deposited in each previous decomposition step. Even the long
main advantage of gasification process is the inhibition of catalyst term gasification processes were unable to eliminate all carbon
re-oxidation and thermal shocks and supplementary hydrogen deposited on Cu-based catalyst for maintaining a continuous
production from steam. Additional 1.4 moles of hydrogen were production of hydrogen by methane decomposition-catalyst
produced during steam gasification results in an overall 3.4 moles regeneration cycle. Whereas, re-dispersion of Ni-particles in
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 247

Table 9
Recently studied experiments on regeneration of deactivated catalyst: a comparison of results and major observations.

Catalyst composition Catalyst preparation Reactor Regenerating conditions Regenerating gas Ref.
T/F/W/SA

Ni(30%)/Al2O3 Co-precipitation TGA 550 and 600/675b/0.1/– 3% O2/97%N2 [114]

Major findings
 Regeneration with O2 eliminate all carbon deposited on the catalysts as well as converts metallic Ni to nickel oxide.
 Initial activity of catalyst for hydrogen production is recovered by each regeneration step, unfortunately the regenerated catalyst deactivate more rapidly than that of
fresh catalyst in continuous cyclic process.
 Regeneration causes segregation of Ni particle on Al2O3 support which accelerates lowering of reduction temperature to 250 1C from 550 1C of fresh catalyst.
 An increase in the size of Ni crystallites occurred during regeneration step induces reduction in the carbon formation rate. Hence, the combined reduction–regeneration
process causes severe loss of catalytic activity.

Ni/SiO2, Ni/TiO2, Ni/Al2O3 and Pd–Ni/ Impregnation FBR 480/75a/–/– O2/Ar [170]
SiO2
Major findings
 CO formation was negligible under the experimental condition.
 More than 98% of deposited carbon converted in to CO2 over each cycle.
 Activity of Ni/SiO2 decline over each cycle because of sintering of Ni metal particle with repeated cycle.
 Activity of Ni/TiO2 improved after first regeneration and shows constant value after second cycle.
 Activity of Ni/Al2O3 improved remarkably from the first to third cycle, afterwards activity came down.
 Initial activity of Pd–Ni/SiO2 was completely recovered by regeneration, but methane conversion with time-on-stream slightly decreased over successive cycles.

Ni/αAl2O3 and Ni/γAl2O3 Wet impregnation TGA 500 and 550/–/0.01/– O2 (Air) [184]
Major findings
 Ni/αAl2O3 (non-porous) completely lost its activity by 6 cycles, but Ni/γAl2O3 (porous) remain even after 24 cycles.
 In Ni/αAl2O3, NiAl2O4 formed after each regeneration steps which reduces total surface area and hence activity. Ni sintering also facilitate deactivation.
 In Ni/γAl2O3, Ni crystalline phase has been transformed to amorphous on repeated cycle and this amorphous phase is active towards methane decomposition even after
24 cycles.
 Both catalysts produced Cβ and Cγ type carbons as the leading deposit.

Ni/SiO2, Ni/αAl2O3,Ni/γAl2O3 Impregnation FlBR 550/–/–/– O2 (Air) [185]

Major findings
 Complete carbon removal were achieved on all three catalyst.
 Ni/SiO2 shows higher methane conversion in second cycle than in first one.
 Ni/SiO2 has better stability as no crystal structural change occurred on regeneration.
 Activity of both Ni/αAl2O3, Ni/γAl2O3 deteriorated very quickly on regeneration at elevated temperature because of high sintering and attrition.

58.0% Ni–15.0% Mg (NMA-I) Co-precipitation Quartz 700 (for CO2) and 600 (for O2) /100a/ 10%CO2 or 10%O2/Ar [186]
reactor 0.06/64
18.0% Ni–46.0% Mg (NMA-II) Co-precipitation Quartz 700 (for CO2) and 600 (for O2) /100a/ 10%CO2 or 10%O2/Ar
reactor 0.06 /73
Major findings
 The most stable catalyst was NMA-II with low Ni-loading, but NMA-I with high Ni-loading show higher activity.
 Hydrogen produced per Ni-content for both catalysts were almost same (8.5 a.u. for NMA-I and 9 a.u. for NMA-II). NMA-I and NMA-II convert 48% and 39% CH4
respectively.
 Higher activity shown by both regenerated catalyst than that of fresh one.
 In terms of the amount of hydrogen produced, regeneration with CO2 proved to be better than that with O2. Moreover, CO2 does not re-oxidize nickel during
regeneration.
 Regeneration with O2 decreases Ni reduction temperature but CO2 not.
 Size of Ni particles after CO2 or O2 regeneration were almost same.

Co–CeO2/MgO/Al2O3 and Ni–CeO2/ Impregnation and FBR 500/–/0.10–0.15/– O2 or CO2 [187]

MgO/Al2O3 calcination
Major findings
 Co-based catalyst deactivate much faster than the Ni-based catalyst.
 Cumulative hydrogen yield (H2/Co or Ni mole ratio) was 7.1 and 9.5 on Co and Ni respectively.
 In the first regeneration cycle, oxidation occurred at a higher rate on Ni catalyst (2.5 min) compared to Co catalyst (4.2 min).
 In spite of oxidizing more than 90% of deposited carbon by both catalysts, Co-catalyst undergone subsequent deactivation over cycle and Ni-catalyst maintain activity
until 6 experimented cycles.
 Regeneration by CO2 limits the formation of NiO and hence CO in subsequent methane decomposition.
 Carbon removal percentage is similar for both CO2 and O2, but carbon removal rate is 20 times slower with CO2 compared to O2.

CuAl2O4 Wet impregnation FlBR 800/–/25/– 5 vol% and a 21 vol% O2 in CO2 and [188]
air (O2)
Major findings
 Oxy-combustion treatment removes all carbon deposited on each decomposition (about 600 mg).
 Additional amount of O2 after removal of carbon re-oxidize the catalyst.
 Bed temperature increase by 45 1C and 20 1C has been occurred during catalyst regeneration with 21 vol% and 5 vol% O2 in CO2, respectively.
 In both oxygen concentration, the hydrogen production rate comes down during each consecutive decomposition cycle and this lessening is severe with 21 vol% O2 in
CO2.
 H2 production decreases during air regeneration in alumina reactor over cycles with largest deactivation degree.
 3%, 20% and 30% catalytic activity loss has been found after a 30 min regeneration by 5% O2–CO2 stream, 21% O2–CO2 stream and air, meanwhile the bed temperature rise
was 20, 45 and 65 1C, respectively.
248 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

Table 9 (continued )

Catalyst composition Catalyst preparation Reactor Regenerating conditions Regenerating gas Ref.
T/F/W/SA

CuAl2O4 Wet impregnation FlBR 800/–/25/156 2.5 vol% O2/N2 [189]

Major findings
 Total amount of carbon deposited (23–25 mgC/gcat) converted to COx and surface of catalyst become clean.
 2.5 vol% O2/N2completely restores the activity of catalyst over repeated decomposition–regeneration cycle.
 Regeneration time higher than 2 min is essential to achieve a steady hydrogen production. Additionally, it should be less than 1 min for suppressing CO2 production.

5-wt% Ni/γ-Al2O3 Wet impregnation TGA 500/–/0.1–1/– 21 vol% and vol% O2 (air) [190]
Major findings
 Regeneration with high concentration of oxygen would produce high temperature which results in loss of catalytic activity over cycle.
 Catalyst disintegrated to fine powder on regeneration cycle.
 Regenerated catalyst produces thinner carbon filaments than those given by fresh catalyst.
 There is no loss of nickel found in regeneration cycle.
 Partial carbon gasification of carbon with 5.25% O2 give higher H2 production over each cycle.
 Most of active metal agglomerated got encapsulated over regeneration but not deactivate permanently.
 Partial regeneration has been found as a hopeful approach to overcome the drawbacks of catalyst deactivation-complete regeneration cycle in TCD.

Bituminous coal char – FBR 950/–/13&11/– 0.46% O2 in N2 [191]

Major findings
 63% hydrogen production has reduced to 12% by 180 min of methane decomposition.
 All oxygen has been utilized for carbon oxidation process.
 Activity partially recovered on regeneration.
 Activity increased with the regeneration time – initial hydrogen yield are 19%, 24% and 30% after regeneration of 10, 20 and 30 min, respectively.

5,10 and 15-wt% Ni/γ-Al2O3 Wetness impregnation TGA 500 and 600/–/0.02/– O2 (Air) [192]
Major findings
 Oxidation remove central core carbons first as it bear less structural order than outer skin.
 Partial oxidation eases the diffusion of methane towards the catalyst for decomposition in upcoming cycle.
 Higher temperature gives higher yield, but deactivate faster.

ACPS – TGA 900, 950 and 1000/50/0.01/1027 CO2 [110]

Major findings
 Initial specific rate of carbon formation (r0) and the final mass gain of the catalyst diminished after each CO2 regeneration.
 Lower activity loss shown at severe regeneration temperature.
 TCD of methane conducted at 950 1C together with gasification of deactivated ACPS at 1000 1C has given the enhanced stability and superior efficiency.

PAC – FBR 950/10/0.05/– CO2 [167]

Major findings
 Short term CO2 regeneration removes carbon with incompact structure which lowers catalytic activity.
 Drop in catalytic activity is small for longer CO2 pulses.
 A general loss in activity occurred irrespective of CO2 pulse duration.
 Effectiveness of catalyst regeneration by CO2 increases with increasing the temperature and duration of CO2 pulse.
 Methane decomposition at 750 1C and regeneration at 950 1C did not give good result, but methane decomposition at 850 1C and regeneration at 950 1C gave much
better result.

AC - CG Norit – FlBR 700, 800, 900, 925 and 950/–/4/1300 CO2 [181]
Major findings
 At severe regeneration steps, e.g.: 925 1C, higher burn-off degree and specific surface area were obtained because of the new surface area produced by further activation
of the virgin CG-Norit sample.
 Good correlation exists in between concentration of oxygenated groups and initial methane conversion on each regeneration cycle.
 Regeneration also removes initial AC - CG Norit as the produced carbon has graphitic structure with more resistant for gasification.
 A gradual lowering is detected in the burn-off degree, surface area and OSGs over decomposition/regeneration cycle.

ACPS – TGA 850, 900, 950 and 1000/50/0.01/1027 CO2 [193]

Major findings
 Temperature has a strong influence on gasification of virgin and deactivated ACPSs
 There is no significant loss in initial gasification activity observed in the gasification cycle conducted at 900 and 950 1C, but it is decreasing after third gasification cycle of
the experiment conducted at 1000 1C.

16.4 wt% Ni/SiO2 Wet-impregnation FBR 550/–/0.2/250 O2 (Air) and H2O (steam) [23]
Major findings
 Both steam and O2 completely restore the activity of catalyst.
 Oxidation process was faster than steam gasification.
 Steam gasification produces additional hydrogen on the expense of external thermal energy.
 Carbon deposited with two layers and the inner layer is more resistant to steam gasification which remains even after gasification.
 Steam gasification starts at nickel–carbon interface and is catalyzed by nickel.

Ni/Metal oxides and Ni/Zeolites Physical mixing and FBR 500/–/0.4/– Steam (H2O) [183]
impregnation
Major findings
 Maintained without dropping pressure across the catalyst bed in both parallel reactors by gasifying almost 95% of deposited carbon.
 The amount of H2 produced per mole of the methane converted was 3.9 7 0.05.
 Ni/ZrO2 and Ni/Ce(72)NaY are promising catalysts for the cyclic stepwise steam reforming of methane to hydrogen and CO2 at a low temperature (500 1C).
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 249

Table 9 (continued )

Catalyst composition Catalyst preparation Reactor Regenerating conditions Regenerating gas Ref.
T/F/W/SA

15 wt% Ni/SiO2 Impregnation FBR 650/–/0.2/– Steam (H2O) [119]

Major findings
 No significant loss in initial methane conversion (24–34%) and catalytic activity during continuous decomposition/regeneration cycle.
 SEM and XRD results indicate most of the carbon has been removed from catalyst surface.
 The average crystallite size of the Ni-particles remains unaltered throughout the repeated cycles.
 Traces of NiO appear on longer exposure of steam, but it reduced back to nickel on cracking step.

CuAl2O4 Wet impregnation FlBR 800/8.7 cm/s/25/156 Air, 5.5%CO2 and 3% steam in N2 [194]
stream
Major findings
Air regenerate complete activity of catalyst within 15 min by converting carbon to CO and CO2.
CO2 remove 45% of carbon only even after regeneration process of 80 min.
Fast regeneration occurred in the first 30 min and rate came down with steam. Remove 45% of carbon with a span of 70 min.
50% carbon removal degree for air, steam and CO2 are 6.5, 100 and 140 min respectively.

(FBR, fixed bed reactor; FlBR, fluidized bed reactor; TGA, thermogravimetric analyzer; T, temperature (1C); F, flowrate (amL/min, b
NmL/min, unless other units are stated);
W, weight of catalyst (g); SA, surface area (m2/g); –, not mentioned in the original paper).

NMA-I and NMA-II catalysts occurred during cyclic regeneration

process and the size of the CO2 regenerated catalyst decreases and
shows better performance than that of fresh catalyst [186]. Two of
the authors (Abbas and Daud) [110] used thermobalance to
regenerate deactivated ACPS by CO2. The initial activity and
ultimate mass gain of regenerated catalyst decrease after each
regeneration steps. They observed a less decline in mass gain with
catalyst regenerated at 950 1C compared to those regenerated at
850 1C. As gasification progresses, a decrease of surface area occurs
because of growth, overlap and coalescence of pores, which leads
to the transformation of large micropores into mesopores; as a
result, the gasification rate is decreased. The CO2 gasification
conducted on different types of chars at temperature 1000–
1300 1C shows a maximum value of carbon gasification rate
followed by a weakening [195]. The shorter pulse introduction of
CO2 destroys incompact structured carbon only and makes the
system more compact and results in the loss of activity [167].
Eventually, long term CO2 pulse can collapse the structure of
deposited carbon causes less activity loss. Hence, moderate tem-
perature (750 1C) is favorable for methane decomposition as it
produce lower amount of carbon and higher temperature (950–
1000 1C) for regeneration as it can gasify more carbon for smooth Fig. 17. Hydrogen production after regeneration cycles: (a) 900 1C-4 h and
cyclic process [110,167]. Additionally, severe regeneration condi- (b) 925 1C-2 h [181].
tion increase surface area and OSGs on the deactivated carbon.
Pinilla et al. [181] regenerated 50% and 80% surface area of the gasification. They have concluded that among the studied metal
deactivated AC-CG Norit at 900 and 925 1C respectively. The catalysts, Ni/ZrO2 and Ni/Ce(72)NaY are promising catalysts for the
observed activities of regenerated AC catalysts over the cycle are cyclic methane decomposition–regeneration process. Aiello et al.
shown in Fig. 17. At 900 1C, 1st, 2nd and 3rd cycles shows initial [119] successfully regenerated 15 wt% Ni/SiO2 with steam at 650 1C
activity of 75%, 60% and 30% respectively. While, at 925 1C 2nd and for up to 10 consecutive cycles without any noteworthy activity
3rd cycle shows similar results. There is correlation observed loss and crystal structural changes. Regeneration removed almost
between BET area and converted carbon, and initial conversion all deposited carbon from Ni/SiO2 except small packets of graphitic
rate and OSGs. Hence, the lower the surface area and higher carbon which resist steam regeneration. The carbon formed on
oxygen groups after regeneration, the lower carbon accumulation catalyst as a two layers. The upper layer of 25–30% of total carbon
and higher initial conversion rate in the subsequent stages. All deposited is more resistance towards steam gasification. Steam
experimental results proved that the regeneration of catalyst by regeneration takes place in the nickel–carbon interface with the
CO2 is more effective at high temperature and long process catalytic influence of nickel which enhances initial hydrogen
duration. production during steam regeneration [23]. It provides easier
Choudhary et al. [183] described continuous production of access of steam to the interior to evaporate inner less graphitic
hydrogen by methane cracking followed by catalyst regeneration carbon wall which helps continuous production of hydrogen.
with steam at 500 1C in two parallel fixed bed reactors. A series of
Ni-containing metal oxide (Ni/M¼ 1.0) catalysts and nickel (10 wt 5.2. Combustion
%) impregnated zeolite catalysts were used for examination. Ni/
ZrO2 catalyst produce 0.82 g carbon per gram catalyst by 6 h (36 The combustion of carbon with oxygen is capable to eliminate
cycle) process and 95% of catalyst were removed by steam all the carbon formed on the catalyst with a better performance
250 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

than CO2. The advantage of combustion is the in situ formation of deposited in the prior decomposition step, therefore, no accumu-
heat which eases further methane decomposition and it is much lation of carbon is observed. The further amount of oxygen re-
faster than gasification process. Lower methane concentrations is oxidizes the catalyst which is already reduced by methane during
preferred for decomposition-carbon combustion cycle, since it the previous decomposition step. Ammendola et al. [189] simulate
produce less carbon which can prevent thermal sintering of the a cyclic process by switching two feeds CH4 (5 vol%) in N2 for
catalyst because of the high heat release on carbon oxidation. about 25 min and air regeneration for 4 min, 2 min, 1 min and
Moreover, lower O2 concentration is suitable for combustion 30 s. They concluded that the regeneration time of more than
process as combustion with higher O2 concentration would result 2 min is necessary for a stable hydrogen production and it should
rise in temperature which may leads to the loss of catalytic be less than 1 min for suppressing CO2 production. Amin et al. [184]
activity. In addition, catalyst with low metal wt.% is favorable for conducted methane decomposition and catalyst regeneration in a
combustion regeneration [48]. Hence, low MSI in the low metal thermal gravimetric analyzer with air using 10 mg of non-porous
loaded catalyst promote carbon formation at the back-side of catalyst (Ni/αAl2O3) or porous (Ni/γAl2O3). Regeneration at 550 1C
metal particle causing detachment of metal from carrier texture. was faster than that at 500 1C reveals the temperature dependency of
This carbon can be easily gasify with oxygen without effecting the regeneration. Furthermore, non-porous catalyst regenerated in a
catalyst. faster rate than the porous catalyst at both 500 and 550 1C because
Saraswat and Pant [58] regenerate Ni–Cu/SiO2 catalyst with a carbon deposited only over the external surface of non-porous
flow of O2 with N2 in a volumetric ratio of 1:3 at 550 1C. First and catalyst which is more accessible for gasification.
second regeneration cycles had shown a similar trend with small
loss in activity from 88% to 80%. In addition, third regeneration 5.3. Partial regeneration
cycles brought the activity to 67% from 79%. It is worthwhile to
note that, H2 and CH4 are the only constituents perceived in the Partial regeneration is a better solution to overcome the
post-reaction stream within the TCD limit of their examination. Li disadvantages relating to catalyst sintering and deactivation dur-
and Smith [187] experimented decomposition of 5% CH4 in helium ing regeneration process. The main filament of formed carbon is
at 500 1C over 0.10–0.15 g of Co–CeO2/MgO/Al2O3 and Ni–CeO2/ difficult to oxidize. Therefore, in partial regeneration process, the
MgO/Al2O3 and O2 regeneration in tapered element oscillating encapsulated carbon is oxidized by leaving the carbon filament to
microbalance configured as a fixed bed microreactor. Co catalyst grow [192]. This filament can hold the metal particle at the tip of
did not show any significant activity in the initial stage of second the filaments through which carbon diffuses to the support for
cycle and no measurable change occurred during the followed precipitation. Hence, partial regeneration maintains the activity of
induction period of 30 min. Moreover, induction period of catalyst over several numbers of cycles leaving main skeletal body
Co-catalyst increased as the number of decomposition–oxidation of the filament intact. Rahman et al. [190] conducted the regen-
cycles increased. Hence, Co-catalyst deactivate as number of cycle eration process with 5.25% O2 until the catalyst mass dropped to
increased as regeneration steps fails to remove carbon completely. near 30% of maximum mass reached in the first cycle. They
Moreover, methane reduces NiO faster than Co3O4 because of the observed 28% and 23% higher mass gain during the second and
lack of induction period for Ni-catalyst. O2 regeneration step third reaction cycle compared to the corresponding previous step.
remove more than 90% of deposited carbon in a very high rate Furthermore, the mass gain observed in the sixth reaction cycle
on both catalyst. After carbon removal by oxidation, Ni particles was around 3.3% higher than the original mass gain in the first
maintained its size equivalent to that of the reduced catalyst as reaction cycle. Instead of complete gasification, partial gasification
shown in TEM micrographs in Fig. 18. Hence, Ni catalyst show of the deposited carbon is a strategy that can maintain significant
better performance in cyclic reaction compared to Co catalyst. activity of the catalyst. Very limited research articles are available
Furthermore, higher methane decomposition activity and on partial regeneration, further studies have to be conducted on
improved stability is indicated by a higher initial methane con- this opportunity.
version rate and hydrogen production from facile reduction of the
NiO by methane facilitates improved performance of Ni catalyst
over Co catalyst in cyclic reaction. Ammendola et al. [194] proved 6. Separation of pure hydrogen: a hypothesis
that oxygen completely regenerate CuAl2O4 catalyst by removing
690 mg of carbon within 15 min with increasing bed temperature The catalyst must be recovered and reused to improve the
by 10 1C. Each combustion step completely removes carbon economy of the process, if the main aim of TCD is hydrogen

Fig. 18. TEM micrographs of Ni–CeO2/MgO/Al2O3 catalyst. (a) after reduction; (b) after CH4 decomposition and (c) after carbon oxidation with O2/He [187].
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 251

production. Unfortunately, catalyst regeneration and methane co- effectiveness even at low gas volumes are the main advantages of
feeding generate components other than hydrogen like methane, membrane separation techniques [196]. Moreover, the membrane
carbon monoxide, carbon dioxide, ethylene, ethane, water, acet- separation processes consume less energy with the ability of
aldehyde, propane, butane, acetylene, propyne and off course the continuous operation. Furthermore, the solid physical nature of
un-reacted co-feed in the post-reaction mixture [34,161,164,165]. membrane act as a barrier which permeate selected materials only
It demands an additional purification step to obtain pure hydrogen across it. In the view of TCD process, the main advantage of
appropriate for PEMFCs and other industrial applications. In fact, a membrane separation is that it can be incorporated with methane
purification step is required even in decomposition of pure decomposition reactor as it successfully implemented in SRM and
methane as it's out stream contains mixture of hydrogen and POX processes [199,200]. The membranes can continuously remove
un-reacted methane. Pressure swing adsorption (PSA), cryogenic hydrogen from the reaction site and shift the equilibrium of methane
distillation, and membrane separation are the three techniques conversion reactions towards the product side according to Le-
using for hydrogen separation purpose [196,197]. PSA method Chatelier's principle. Hence, the membrane integrated methane
works on the basis of adsorption capability of adsorbent to adsorb decomposition reactor can be used to produce high purity hydrogen
more impurities at higher gas partial pressure than at lower gas with improved overall system efficiency (Fig. 19). The major concern
partial pressure [198]. This method extensively used in chemical in integrating membrane with methane decomposition reactor is the
and petrochemical industries for purification. Cryogenic distillation temperature limitations due to the thermal stability of membrane.
process generally used for moderate purification of hydrogen (up to Hence, it is worthwhile to note that there are numerous TCD
95%) at relatively low temperature. Cryogenic process purify hydrogen experiments displays striking results at temperature below 800 1C
utilizing the difference in boiling temperatures of the feed compo- with and without co-feed (Fig. 16 and Table 6). Moreover, inorganic
nents. Hence, hydrogen is highly volatile than hydrocarbons. membranes can bear better stability even at high-temperature [201].
Apart from PSA and cryogenic distillation, recently developed Recently, numerous research efforts have been emphasized on
membrane separation techniques have been mostly utilizing as a integration of inorganic membranes with methane decomposition
promising method to separate high-purity hydrogen. Ease of reactor with a view to break the chemical equilibrium exist in
operation, low investment cost, low energy consumption, and cost methane decomposition reaction towards the product side for

Fig. 19. Schematic representation of overall process of methane conversion to pure hydrogen.

Fig. 20. Schematic of the fuel cell set-up that used methane catalytic decomposition product as the fuel integrated with a Pd membrane for in-situ separation of hydrogen.
A: catalytic decomposition reactor, B: Pd membrane separator, C: PEMFC; 1: electrical furnace, 2: Ni/Al2O3 catalyst, 3: quartz tube, 4: gas valve, 5: Pd membrane, 6: back
pressure valve, 7: water bottle, 8: Nafion membrane, 9: catalyst layer, 10: gas diffusion layers, 11: graphite stage [202].
252 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

getting an improved methane conversion rate at lower tempera- than CO2 in the regeneration process. O2 completely regenerate
tures. Many researchers effectively employed Pd, Pd-alloy CuAl2O4 catalyst by removing 690 mg of deposited carbon within
[203,204], Pd–Cu [205], Ni [206], V [207], Pd–Ag film [208] 15 min. Despite regeneration restore initial activity of catalyst, the
membranes in SRM and POX processes. Studies conducted in regenerated catalyst undergo fast deactivation in the following
membrane reactor reveal that Pd–Ag membrane is effective in decomposition cycle. Eventually, a purification process is obliga-
increasing the methane decomposition activity at temperatures tory because of the accompanied un-reacted methane in the out
lower than 500 1C [199]. Sun et al. [202] conducted TCD of stream and hence the other co-components including COx in case
methane in a quartz tube reactor integrated with Pd membrane of co-feeding and regeneration. This review concludes by hypothe-
for hydrogen purification. Methane catalytic decomposition reac- sizing the possibility of on line purification of hydrogen by the
tor integrated with on-line Pd membrane for hydrogen separation integration of a membrane separation technique with the methane
used by them contains three parts, the catalytic decomposition decomposition reactor. Also, authors are indicating the promi-
reactor (Part A), the Pd membrane separator (Part B) and the nence of more research effort should be devoted in order to avoid
PEMFC (Part C) as shown in Fig. 20. The reactor had three parts; GHG emission by purifying and potentially applying produced
catalytic decomposition reactor, Pd membrane separator and nano carbon in nano technology fields; hence regeneration stage
PEMFC. Methane decomposition had performed over 70 wt% Ni/ can be skipped. Henceforth, advanced studies must unambigu-
Al2O3 at 700 1C and gained 83% hydrogen production in the post- ously conducted on designing membrane integrated methane
reaction stream. When the reactor integrated to Pd-membrane, decomposition reactor, which should preserve all genuine char-
they found a sharp increase in hydrogen content to  98%. This acteristics of catalyst for decomposition–regeneration cycle for
high content of hydrogen can be attributed to reaction equilibrium simple, reliable and continuous hydrogen preparation and separa-
shift towards product side according to Le-Chatelier's principle. tion process, as schematized in Fig. 19. Once as mentioned TCD
The experimental results proves that Pd-based membranes are process achieves GHG free hydrogen production, it would be a
highly efficient for hydrogen separation process because of its very milestone in fuel technology for a green impending aeon. Hope-
high hydrogen permeability. Much works are already in progress fully, we will see numerous exciting advancements in methane
for studying the opportunities of filling the membrane module decomposition and hydrogen purification processes in the not too
with catalyst which is expected to enhance water gas shift reaction distant future.
by converting CO to CO2 for additional hydrogen production
together with its purification.
Acknowledgment

7. Overall conclusion The authors gratefully acknowledge financial support from the
Postgraduate Research Fund (UM.C/HIR/MOHE/ENG/11), University of
TCD has been considering as the most reliable and beneficial Malaya, Malaysia.
method for the production of pure hydrogen for fuel cell and
further applications. This review is intended to provide a critical
and wide-ranging assessment of the miscellaneous catalysts, co- References
feeding and regeneration of deactivated catalyst in TCD. Metal,
carbonaceous and metal doped carbonaceous catalysts are com- [1] Statistical review of world energy. BP; 2012.
prehensively and thoroughly studied and found that carbonaceous [2] World energy outlook. IEA; 2012.
[3] Olivier Jos GJ, Janssens-Maenhout G, Peters Jeroen AHW. Trends in global
catalyst and metal doped carbon catalysts hold better stability and CO2 emissions. PBL 2012, report by PBL Netherlands Environmental Assess-
lower deactivation rate compared to metal catalysts, but hold ment Agency, ISBN: 978-92-79-25381-2.
poorer methane conversion compared to metal catalysts. Gener- [4] Fourth assessment report: climate change. IPCC; 2007.
[5] Serrano DP, Botas JA, Fierro JLG, Guil-López R, Pizarro P, Gómez G. Hydrogen
ally, Ni-based metal catalysts and Ni-doped carbon catalysts bear production by methane decomposition: origin of the catalytic activity of
improved activity than others. Most of the researchers accom- carbon materials. Fuel 2010;89:1241–8.
plished that high temperature and low flow rate is adequate for [6] Stephens-Romero S, Carreras-Sospedra M, Brouwer J, Dabdub D, Samuelsen
S. Determining air quality and greenhouse gas impacts of hydrogen infra-
getting high purity hydrogen. It is believed that, initial catalytic
structure and fuel cell vehicles. Env Sci Technol 2009;43:9022–9.
activity resembles to the chemical structure of the catalyst and [7] Züttel A. Hydrogen storage methods. Naturwissenschaften 2004;91:157–72.
long term activity corresponds to the physical characteristics of [8] Nasir Uddin M, Daud WMAW, Abbas HF. Potential hydrogen and non-
catalyst. The foremost challenges face during TCD process are the condensable gases production from biomass pyrolysis: insights into the
process variables. Renew Sustain Energy Rev 2013;27:204–24.
separation of pure hydrogen and deactivation of the catalyst [9] Navarro RM, Sanchez-Sanchez MC, Alvarez-Galvan MC, Fd Valle, Fierro JLG.
because of the reasons like sintering and obstruction of the active Hydrogen production from renewable sources: biomass and photocatalytic
site by carbon; the un-avoidable by-product in methane cracking. opportunities. Energy Environ Sci 2009;2:35–54.
[10] Ueno Y, Fukui H, Goto M. Operation of a two-stage fermentation process
There are abundant studies done on deactivation and described producing hydrogen and methane from organic waste. Environ Sci Technol
many deactivation mechanisms, but the final assumption varied 2007;41:1413–9.
with various researchers and failed to accomplish the genuine [11] Balat M, Balat M. Political, economic and environmental impacts of biomass-
based hydrogen. Int J Hydrog Energy 2009;34:3589–603.
reason of deactivation other than carbon encapsulation. Regenera- [12] Konieczny A, Mondal K, Wiltowski T, Dydo P. Catalyst development for
tion of the deactivated catalysts and co-feeding of methane with thermocatalytic decomposition of methane to hydrogen. Int J Hydrog Energy
other hydrocarbons which in situ produce more active carbon are 2008;33:264–72.
[13] Brentner LB, Peccia J, Zimmerman JB. Challenges in developing biohydrogen
the two technical approaches put forwarded in order to overcome as a sustainable energy source: implications for a research agenda. Environ
the deactivation hurdle. It is found that the addition of 40% ethanol Sci Technol 2010;44:2243–54.
to methane enhances hydrogen production by ten times than that [14] Abbas HF, Daud WMAW. Influence of reactor material and activated carbon
on the thermocatalytic decomposition of methane for hydrogen production.
in the absence of ethanol. Furthermore, regeneration of the
Appl Catal A: Gen 2010;388:232–9.
deactivated catalyst with steam, CO2 or O2 found precisely effec- [15] Wang S. Application of solid ash based catalysts in heterogeneous catalysis.
tive and favors cyclic decomposition–regeneration process. Steam Environ Sci Technol 2008;42:7055–63.
gasification improves hydrogen content in the post reaction [16] Khaselev O, Turner JA. A monolithic photovoltaic-photoelectrochemical
device for hydrogen production via water splitting. Science 1998;280:425–7.
stream by its own hydrogen contribution of 1.4 moles per [17] Nowotny J, Sorrell CC, Sheppard LR, Bak T. Solar-hydrogen: environmentally
methane. However, O2 has shown twenty times better efficiency safe fuel for the future. Int J Hydrog Energy 2005;30:521–44.
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 253

[18] Peharz G, Dimroth F, Wittstadt U. Solar hydrogen production by water hydrogen and nanocarbon via methane decomposition. Int J Hydrog Energy
splitting with a conversion efficiency of 18%. Int J Hydrog Energy 2007;32: 2010;35:3509–21.
3248–52. [50] Venugopal A, Naveen Kumar S, Ashok J, Hari Prasad D, Durga Kumari V,
[19] Ni M, Leung MKH, Leung DYC, Sumathy K. A review and recent developments Prasad KBS, et al. Hydrogen production by catalytic decomposition of
in photocatalytic water-splitting using for hydrogen production. Renew methane over Ni/SiO2. Int J Hydrog Energy 2007;32:1782–8.
Sustain Energy Rev 2007;11:401–25. [51] Wang W, Wang H, Yang Y, S. Jiang. Ni–SiO2 and Ni–Fe–SiO2 catalysts for
[20] Kodama T. High-temperature solar chemistry for converting solar heat to methane decomposition to prepare hydrogen and carbon filaments. Int J
chemical fuels. Prog Energy Combust Sci 2003;29:567–97. Hydrog Energy 2012;37:9058–66.
[21] Westermann P, Jørgensen B, Lange L, Ahring BK, Christensen CH. Maximizing [52] Lázaro MJ, Echegoyen Y, Alegre C, Suelves I, Moliner R, Palacios JM. TiO2 as
renewable hydrogen production from biomass in a bio/catalytic refinery. Int J textural promoter on high loaded Ni catalysts for methane decomposition.
Hydrog Energy 2007;32:4135–41. Int J Hydrog Energy 2008;33:3320–9.
[22] Jana P, de la Peña O’Shea VA, Coronado JM, Serrano DP. Mild temperature [53] Pinilla JL, Utrilla R, Lázaro MJ, Moliner R, Suelves I, García AB. Ni- and Fe-
hydrogen production by methane decomposition over cobalt catalysts based catalysts for hydrogen and carbon nanofilament production by
prepared with different precipitating agents. Int J Hydrog Energy 2012;37: catalytic decomposition of methane in a rotary bed reactor. Fuel Process
7034–41. Technol 2011;92:1480–8.
[23] Zhang T, Amiridis MD. Hydrogen production via the direct cracking of [54] Figueiredo JL, Órfão JJM, Cunha AF. Hydrogen production via methane
methane over silica-supported nickel catalysts. Appl Catal A: Gen 1998;167: decomposition on Raney-type catalysts. Int J Hydrog Energy 2010;35:
161–172. 9795–9800.
[24] Saraswat SK, Pant KK. Ni–Cu–Zn/MCM-22 catalysts for simultaneous produc- [55] Torres D, de Llobet S, Pinilla JL, Lázaro MJ, Suelves I, Moliner R. Hydrogen
tion of hydrogen and multiwall carbon nanotubes via thermo-catalytic production by catalytic decomposition of methane using a Fe-based catalyst
decomposition of methane. Int J Hydrog Energy 2011;36:13352–60. in a fluidized bed reactor. J Nat Gas Chem 2012;21:367–73.
[25] Jang HT, Cha WS. Hydrogen production by the thermocatalytic decomposi- [56] Pinilla JL, Utrilla R, Karn RK, Suelves I, Lázaro MJ, Moliner R, et al. High
tion of methane in a fluidized bed reactor. Korean J Chem Eng 2007;24: temperature iron-based catalysts for hydrogen and nanostructured carbon
374–7. production by methane decomposition. Int J Hydrog Energy 2011;36:7832–43.
[26] Shah N, Panjala D, Huffman GP. Hydrogen production by catalytic decom- [57] Zapata B, Valenzuela MA, Palacios J, Torres-Garcia E. Effect of Ca, Ce or K
position of methane. Energy Fuels 2001;15:1528–34. oxide addition on the activity of Ni/SiO2 catalysts for the methane decom-
[27] Li Y, Chen J, Qin Y, Chang L. Simultaneous production of hydrogen and position reaction. Int J Hydrog Energy 2010;35:12091–7.
nanocarbon from decomposition of methane on a nickel-based catalyst. [58] Saraswat SK, Pant KK. Synthesis of hydrogen and carbon nanotubes over
Energy Fuels 2000;14:1188–94. copper promoted Ni/SiO2 catalyst by thermocatalytic decomposition of
[28] Pinilla JL, Suelves I, Lázaro MJ, Moliner R, Palacios JM. Parametric study of the methane. J Nat Gas Sci Eng 2013;13:52–9.
decomposition of methane using a NiCu/Al2O3 catalyst in a fluidized bed [59] Nuernberg GDB, Foletto EL, Campos CEM, Fajardo HV, Carreño NLV, Probst
reactor. Int J Hydrog Energy 2010;35:9801–9. LFD. Direct decomposition of methane over Ni catalyst supported in
[29] Tibbetts GG, Meisner GP, Olk CH. Hydrogen storage capacity of carbon magnesium aluminate. J Power Sources 2012;208:409–14.
nanotubes, filaments, and vapor-grown fibers. Carbon 2001;39:2291–301. [60] Tapia-Parada K, Valverde-Aguilar G, Mantilla A, Valenzuela MA, Hernández E.
[30] McAllister P, Wolf EE. Ni-catalyzed carbon infiltration of carbon-fiber Synthesis and characterization of Ni/Ce–SiO2 and Co/Ce–TiO2 catalysts for
substrates. Carbon 1992;30:189–200. methane decomposition. Fuel 2013;110:70–5.
[31] Toebes ML, Bitter JH, van Dillen AJ, de Jong KP. Impact of the structure and [61] Italiano G, Delia A, Espro C, Bonura G, Frusteri F. Methane decomposition
reactivity of nickel particles on the catalytic growth of carbon nanofibers. over Co thin layer supported catalysts to produce hydrogen for fuel cell. Int J
Catal Today 2002;76:33–42. Hydrog Energy 2010;35:11568–75.
[32] Chaubey R, Sahu S, James OO, Maity S. A review on development of industrial [62] Lee K-Y, Yeoh W-M, Chai S-P, Ichikawa S, Mohamed AR. Catalytic decom-
processes and emerging techniques for production of hydrogen from renew- position of methane to carbon nanotubes and hydrogen: the effect of metal
able and sustainable sources. Renew Sustain Energy Rev 2013;23:443–62. loading on the activity of CoO-MoO/Al2O3 catalyst. Fuller Nanotub Carbon
[33] Suelves I, Pinilla JL, Lázaro MJ, Moliner R, Palacios JM. Effects of reaction Nanostruct 2012;21:158–70.
conditions on hydrogen production and carbon nanofiber properties gener- [63] Nuernberg GDB, Fajardo HV, Foletto EL, Hickel-Probst SM, Carreño NLV,
ated by methane decomposition in a fixed bed reactor using a NiCuAl Probst LFD, et al. Methane conversion to hydrogen and nanotubes on Pt/Ni
catalyst. J Power Sources 2009;192:35–42. catalysts supported over spinel MgAl2O4. Catal Today 2011;176:465–9.
[34] Muradov N, Smith F, T-Raissi A. Catalytic activity of carbons for methane [64] Hussain T, Iqbal M. Pyrolysis of methane by catalytic properties exhibited by
decomposition reaction. Catal Today 2005;102–103:225–33. ceramics. J Anal Appl Pyrolysis 2011;90:106–11.
[35] Dufour A, Celzard A, Ouartassi B, Broust F, Fierro V, Zoulalian A. Effect of [65] Sierra Gallego G, Barrault J, Batiot-Dupeyrat C, Mondragón F. Production of
micropores diffusion on kinetics of CH4 decomposition over a wood-derived hydrogen and MWCNTs by methane decomposition over catalysts originated
carbon catalyst. Appl Catal A: Gen 2009;360:120–5. from LaNiO3 perovskite. Catal Today 2010;149:365–71.
[36] Trimm DL. The formation and removal of coke from nickel catalyst. Catal Rev [66] Maneerung T, Hidajat K, Kawi S. LaNiO3 perovskite catalyst precursor for
1977;16:155–89. rapid decomposition of methane: influence of temperature and presence of
[37] Bartholomew CH. Carbon deposition in steam reforming and methanation. H2 in feed stream. Catal Today 2011;171:24–35.
Catal Rev 1982;24:67–112. [67] Jin L, Si H, Zhang J, Lin P, Hu Z, Qiu B, et al. Preparation of activated carbon
[38] Rostrup-Nielsen JR. Coking on nickel catalysts for steam reforming of supported Fe–Al2O3 catalyst and its application for hydrogen production by
hydrocarbons. J Catal 1974;33:184–201. catalytic methane decomposition. Int J Hydrog Energy 2013;38:1–8.
[39] Takenaka S, Ishida M, Serizawa M, Tanabe E, Otsuka K. Formation of carbon [68] R-NJ R. Steam reforming catalysts: an investigation of catalysts for tubular
nanofibers and carbon nanotubes through methane decomposition over steam reforming of hydrocarbons. Copenhagen: Teknisk Forlag A/S; 1975.
supported cobalt catalysts. J Phys Chem B 2004;108:11464–72. [69] Jana P, de la Peña O’Shea VA, Coronado JM, Serrano DP. Cobalt based
[40] Ashok J, Naveen Kumar S, Subrahmanyam M, Venugopal A. Production of catalysts prepared by Pechini method for CO2-free hydrogen production by
COX free hydrogen by catalytic decomposition of methane over Ni/HY methane decomposition. Int J Hydrog Energy 2010;35:10285–94.
catalysts. Catal Lett 2007;118:139–45. [70] Roine A. HSC Chemistry 5.11. Outokumpu Research Oy, Pori, Finland; 2002.
[41] Ashok J, Kumar SN, Subrahmanyam M, Venugopal A. Pure H2 production by [71] Takenaka S, Serizawa M, Otsuka K. Formation of filamentous carbons over
decomposition of methane over Ni supported on hydroxyapatite catalysts. supported Fe catalysts through methane decomposition. J Catal 2004;222:
Catal Lett 2008;121:283–90. 520–31.
[42] Takenaka S, Ogihara H, Yamanaka I, Otsuka K. Decomposition of methane [72] Ermakova MA, Ermakov DY. Ni/SiO2 and Fe/SiO2 catalysts for production of
over supported-Ni catalysts: effects of the supports on the catalytic lifetime. hydrogen and filamentous carbon via methane decomposition. Catal Today
Appl Catal A: Gen 2001;217:101–10. 2002;77:225–35.
[43] Guil-Lopez R, Botas JA, Fierro JLG, Serrano DP. Comparison of metal and [73] Dupuis A-C. The catalyst in the CCVD of carbon nanotubes—a review. Prog
carbon catalysts for hydrogen production by methane decomposition. Appl Mater Sci 2005;50:929–61.
Catal A: Gen 2011;396:40–51. [74] Otsuka K, Ogihara H, Takenaka S. Decomposition of methane over Ni
[44] Suelves I, Pinilla JL, Lázaro MJ, Moliner R. Carbonaceous materials as catalysts catalysts supported on carbon fibers formed from different hydrocarbons.
for decomposition of methane. Chem Eng J 2008;140:432–8. Carbon 2003;41:223–33.
[45] Zhang W, Ge Q, Xu H. Influences of reaction conditions on methane [75] Chambers A, Nemes T, Rodriguez NM, Baker RTK. Catalytic behavior of
decomposition over non-supported Ni catalyst. J Nat Gas Chem 2011;20: graphite nanofiber supported nickel particles. 1. Comparison with other
339–44. support media. J Phys Chem B 1998;102:2251–8.
[46] Zhang W, Ge Q, Xu H. Influences of precipitate rinsing solvents on ni catalyst [76] Li Y, Li D, Wang G. Methane decomposition to COx-free hydrogen and nano-
for methane decomposition to COx-free hydrogen†. J Phys Chem A carbon material on group 8–10 base metal catalysts: a review. Catal Today
2009;114:3818–23. 2011;162:1–48.
[47] Cunha AF, Órfão JJM, Figueiredo JL. Methane decomposition on Ni–Cu alloyed [77] Salmones J, Wang JA, Valenzuela MA, Sánchez E, Garcia A. Pore geometry
Raney-type catalysts. Int J Hydrog Energy 2009;34:4763–72. influence on the deactivation behavior of Ni-based catalysts for simultaneous
[48] Cunha AF, Órfão JJM, Figueiredo JL. Methane decomposition on Fe–Cu Raney- production of hydrogen and nanocarbon. Catal Today 2009;148:134–9.
type catalysts. Fuel Process Technol. 2009;90:1234–40. [78] Chen D, Christensen KO, Ochoa-Fernández E, Yu Z, Tøtdal B, Latorre N, et al.
[49] Guevara JC, Wang JA, Chen LF, Valenzuela MA, Salas P, García-Ruiz A, et al. Synthesis of carbon nanofibers: effects of Ni crystal size during methane
Ni/Ce-MCM-41 mesostructured catalysts for simultaneous production of decomposition. J Catal 2005;229:82–96.
254 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

[79] Hornés A, Bera P, Fernández-García M, Guerrero-Ruiz A, Martínez-Arias A. consideration for the catalyst deactivation. Appl Catal A: Gen 2004;272:
Catalytic and redox properties of bimetallic Cu–Ni systems combined with 219–27.
CeO2 or Gd-doped CeO2 for methane oxidation and decomposition. Appl [108] Xiong J, Dong X, Dong Y, Hao X, Hampshire S. Dual-production of nickel foam
Catal B: Environ 2012;111–112:96–105. supported carbon nanotubes and hydrogen by methane catalytic decom-
[80] Lua AC, Wang HY. Decomposition of methane over unsupported porous position. Int J Hydrog Energy 2012;37:12307–16.
nickel and alloy catalyst. Appl Catal B: Environ 2013;132–133:469–78. [109] de Lucas A, Garrido A, Sánchez P, Romero A, Valverde JL. Growth of carbon
[81] Suelves I, Lázaro MJ, Moliner R, Echegoyen Y, Palacios JM. Characterization of nanofibers from Ni/Y zeolite based catalysts: effects of Ni introduction
NiAl and NiCuAl catalysts prepared by different methods for hydrogen method, reaction temperature, and reaction gas composition. Ind Eng Chem
production by thermo catalytic decomposition of methane. Catal Today Res 2005;44:8225–36.
2006;116:271–80. [110] Abbas HF, Daud WMAW. Thermocatalytic decomposition of methane for
[82] Li Z, Larsson JA, Larsson P, Ahuja R, Tobin JM, O’Byrne J, et al. Copper/ hydrogen production using activated carbon catalyst: regeneration and
molybdenum nanocomposite particles as catalysts for the growth of characterization studies. Int J Hydrog Energy 2009;34:8034–45.
bamboo-structured carbon nanotubes. J Phys Chem C 2008;112:12201–6. [111] Figueiredo JL. Carbon formation and gasification on nickel. In: Figueiredo J,
[83] O’Byrne JP, Li Z, Tobin JM, Larsson JA, Larsson P, Ahuja R, et al. Growth of editor. Progress in catalyst deactivation. Netherlands: Springer; 1982. p. 45–63.
carbon nanotubes from heterometallic palladium and copper catalysts. J Phys [112] Zhang Y, Smith K. Carbon formation thresholds and catalyst deactivation
Chem C 2010;114:8115–9. during CH4 decomposition on supported Co and Ni catalysts. Catal Lett
[84] Shah N, Pattanaik S, Huggins FE, Panjala D, Huffman GP. XAFS and 2004;95:7–12.
Mössbauer spectroscopy characterization of supported binary catalysts for [113] Baker RTK, Barber MA, Harris PS, Feates FS, Waite RJ. Nucleation and growth
nonoxidative dehydrogenation of methane. Fuel Process Technol 2003;83: of carbon deposits from the nickel catalyzed decomposition of acetylene.
163–73. J Catal 1972;26:51–62.
[85] Punnoose A, Shah N, Huffman GP, Seehra MS. X-ray diffraction and electron [114] Villacampa JI, Royo C, Romeo E, Montoya JA, Del Angel P, Monzón A. Catalytic
magnetic resonance studies of M/Fe/Al2O3 (M ¼Ni, Mo and Pd) catalysts for decomposition of methane over Ni-Al2O3 coprecipitated catalysts: reaction
CH4 to H2 conversion. Fuel Process Technol 2003;83:263–73. and regeneration studies. Appl Catal A: Gen 2003;252:363–83.
[86] Qian W, Liu T, Wei F, Wang Z, Li Y. Enhanced production of carbon [115] Amin AM, Croiset E, Epling W. Review of methane catalytic cracking for
nanotubes: combination of catalyst reduction and methane decomposition. hydrogen production. Int J Hydrog Energy 2011;36:2904–35.
Appl Catal A: Gen 2004;258:121–4. [116] Ermakova MA, Ermakov DY, Kuvshinov GG. Effective catalysts for direct
[87] Shah N, Wang Y, Panjala D, Huffman GP. Production of hydrogen and carbon cracking of methane to produce hydrogen and filamentous carbon: Part I.
nanostructures by non-oxidative catalytic dehydrogenation of ethane and Nickel catalysts. Appl Catal A: Gen 2000;201:61–70.
propane. Energy Fuels 2004;18:727–35. [117] Pinilla JL, Suelves I, Lázaro MJ, Moliner R, Palacios JM. Activity of NiCuAl
[88] Muradov NZ. CO2-free production of hydrogen by catalytic pyrolysis of catalyst in methane decomposition studied using a thermobalance and the
hydrocarbon fuel. Energy Fuels 1998;12:41–8. structural changes in the Ni and the deposited carbon. Int J Hydrog Energy
[89] Tang L, Yamaguchi D, Burke N, Trimm D, Chiang K. Methane decomposition 2008;33:2515–24.
over ceria modified iron catalysts. Catal Commun 2010;11:1215–9. [118] Ishihara T, Miyashita Y, Iseda H, Takita Y. Decomposition of Methane over Ni/
[90] Hussain ST, Nadeem MA, Mazhar M. Effect of potassium addition on the SiO2 catalysts with membrane reactor for the production of hydrogen. Chem
product selectivity of Ru:Mn/alumina supported catalyst system for Fischer– Lett 1995;24:93–4.
Tropsch reaction. Catal Commun, 9; 2008. p. 2048–52. [119] Aiello R, Fiscus JE, Loye H-Cz, Amiridis MD. Hydrogen production via the
[91] Hussain ST, Gul S, Mazhar M, Anjum DH, Larachi F. Effect of surface structure direct cracking of methane over Ni/SiO2: catalyst deactivation and regenera-
on the catalytic behavior of Ni:Cu/Al and Ni:Cu:K/Al catalysts for methane tion. Appl Catal A: Gen 2000;192:227–34.
decomposition. J Nat Gas Chem 2008;17:374–82. [120] Malaika A, Kozłowski M. Influence of ethylene on carbon-catalysed decom-
[92] Balakrishnan M, Batra VS, Hargreaves JSJ, Monaghan A, Pulford ID, Rico JL, position of methane. Int J Hydrog Energy 2009;34:2600–5.
et al. Hydrogen production from methane in the presence of red mud [121] Dufour A, Celzard A, Fierro V, Martin E, Broust F, Zoulalian A. Catalytic
-making mud magnetic. Green Chem 2009;11:42–7. decomposition of methane over a wood char concurrently activated by a
[93] Ermakova MA, Ermakov DY, Chuvilin AL, Kuvshinov GG. Decomposition of pyrolysis gas. Appl Catal A: Gen 2008;346:164–73.
methane over iron catalysts at the range of moderate temperatures: the [122] Jüntgen H. Activated carbon as catalyst support: a review of new research
influence of structure of the catalytic systems and the reaction conditions on results. Fuel 1986;65:1436–46.
the yield of carbon and morphology of carbon filaments. J Catal 2001;201: [123] Muradov N, Chen Z, Smith F. Fossil hydrogen with reduced CO2 emission:
183–97. modeling thermocatalytic decomposition of methane in a fluidized bed of
[94] Frusteri F, Italiano G, Espro C, Arena F. CH4 decomposition on Ni and Co thin carbon particles. Int J Hydrog Energy 2005;30:1149–58.
layer catalysts to produce H2 for fuel cell. Catal Today 2011;171:60–6. [124] Serrano DP, Botas JÁ, Pizarro P, Gómez G. Kinetic and autocatalytic effects
[95] Chai S-P, Zein SHS, Mohamed AR. The effect of reduction temperature on Co- during the hydrogen production by methane decomposition over carbonac-
Mo/Al2O3 catalysts for carbon nanotubes formation. Appl Catal A: Gen eous catalysts. Int J Hydrog Energy 2013;38:5671–83.
2007;326:173–9. [125] Moliner R, Suelves I, Lázaro MJ, Moreno O. Thermocatalytic decomposition of
[96] Chai S-P, Zein SHS, Mohamed AR. Preparation of carbon nanotubes over methane over activated carbons: influence of textural properties and surface
cobalt-containing catalysts via catalytic decomposition of methane. Chem chemistry. Int J Hydrog Energy 2005;30:293–300.
Phys Lett 2006;426:345–50. [126] Lee EK, Lee SY, Han GY, Lee BK, Lee T-J, Jun JH, et al. Catalytic decomposition
[97] Nasir Uddin M, Wan Daud WMA, Abbas HF. Kinetics and deactivation of methane over carbon blacks for CO2-free hydrogen production. Carbon
mechanisms of the thermal decomposition of methane in hydrogen and 2004;42:2641–8.
carbon nanofiber Co-production over Ni-supported Y zeolite-based catalysts. [127] Muradov N. Catalysis of methane decomposition over elemental carbon.
Energy Convers Manag 2014;87:796–809. Catal Commun 2001;2:89–94.
[98] Wang HY, Lua AC. Deactivation and kinetic studies of unsupported Ni and [128] Gatica JM, Gómez DM, Harti S, Vidal H. Monolithic honeycomb design
Ni–Co–Cu alloy catalysts used for hydrogen production by methane decom- applied to carbon materials for catalytic methane decomposition. Appl Catal
position. Chem Eng J 2014;243:79–91. A: Gen 2013;458:21–7.
[99] Abbott HL, Harrison I. Methane dissociative chemisorption on Ru(0001) and [129] Lázaro MJ, Pinilla JL, Utrilla R, Suelves I, Moliner R, Moreno F, et al. H2  CH4
comparison to metal nanocatalysts. J Catal 2008;254:27–38. mixtures produced by carbon-catalyzed methane decomposition as a fuel for
[100] Kvande I, Chen D, Yu Z, Rønning M, Holmen A. Optimization and scale-up of internal combustion engines†. Energy Fuels 2010;24:3340–5.
CNF production based on intrinsic kinetic data obtained from TEOM. J Catal [130] Kim MH, Lee EK, Jun JH, Kong SJ, Han GY, Lee BK, et al. Hydrogen production
2008;256:204–14. by catalytic decomposition of methane over activated carbons: kinetic study.
[101] Sharif Zein SH, Mohamed AR, Talpa Sai PS. Kinetic studies on catalytic Int J Hydrog Energy 2004;29:187–93.
decomposition of methane to hydrogen and carbon over Ni/TiO2 catalyst. Ind [131] Serrano DP, Botas JA, Guil-Lopez R. H2 production from methane pyrolysis
Eng Chem Res 2004;43:4864–70. over commercial carbon catalysts: kinetic and deactivation study. Int J
[102] Fukada S, Nakamura N, Monden J, Nishikawa M. Experimental study of Hydrog Energy 2009;34:4488–94.
cracking methane by Ni/SiO2 catalyst. J Nucl Mater 2004;329–333(Part B): [132] Serrano DP, Botas JA, Pizarro P, Guil-Lopez R, Gomez G. Ordered mesoporous
1365–9. carbons as highly active catalysts for hydrogen production by CH4 decom-
[103] Borghei M, Karimzadeh R, Rashidi A, Izadi N. Kinetics of methane decom- position. Chem Commun 2008;0:6585–7.
position to COx-free hydrogen and carbon nanofiber over Ni–Cu/MgO [133] Lee KK, Han GY, Yoon KJ, Lee BK. Thermocatalytic hydrogen production from
catalyst. Int J Hydrog Energy 2010;35:9479–88. the methane in a fluidized bed with activated carbon catalyst. Catal Today
[104] Snoeck JW, Froment GF, Fowles M. Kinetic study of the carbon filament 2004;93–95:81–6.
formation by methane cracking on a nickel catalyst. J Catal 1997;169:250–62. [134] Krzyżyński S, Kozłowski M. Activated carbons as catalysts for hydrogen
[105] Bai Z, Chen H, Li B, Li W. Methane decomposition over Ni loaded activated production via methane decomposition. Int J Hydrog Energy 2008;33:6172–7.
carbon for hydrogen production and the formation of filamentous carbon. Int [135] Abbas HF, Daud WMAW. Hydrogen production by thermocatalytic decom-
J Hydrog Energy 2007;32:32–7. position of methane using a fixed bed activated carbon in a pilot scale unit:
[106] Chesnokov VV, Chichkan AS. Production of hydrogen by methane catalytic apparent kinetic, deactivation and diffusional limitation studies. Int J Hydrog
decomposition over Ni–Cu–Fe/Al2O3 catalyst. Int J Hydrog Energy 2009;34: Energy 2010;35:12268–76.
2979–85. [136] Botas JA, Serrano DP, Guil-López R, Pizarro P, Gómez G. Methane catalytic
[107] Zavarukhin SG, Kuvshinov GG. The kinetic model of formation of nanofibrous decomposition over ordered mesoporous carbons: a promising route for
carbon from CH4–H2 mixture over a high-loaded nickel catalyst with hydrogen production. Int J Hydrog Energy 2010;35:9788–94.
 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256 255

[137] Zhang J, Jin L, Liu S, Xun Y, Hu H. Mesoporous carbon prepared from direct [166] Pinilla JL, de Llobet S, Suelves I, Utrilla R, Lázaro MJ, Moliner R. Catalytic
coal liquefaction residue for methane decomposition. Carbon 2012;50: decomposition of methane and methane/CO2 mixtures to produce synthesis
952–9. gas and nanostructured carbonaceous material. Fuel 2011;90:2245–53.
[138] Suelves I, Lázaro MJ, Moliner R, Pinilla JL, Cubero H. Hydrogen production by [167] Adamska A, Malaika A, Kozłowski M. Carbon-catalyzed decomposition of
methane decarbonization: carbonaceous catalysts. Int J Hydrog Energy methane in the presence of carbon dioxide†. Energy Fuels 2010;24:3307–12.
2007;32:3320–6. [168] Asai K, Takane K, Nagayasu Y, Iwamoto S, Yagasaki E, Inoue M. Decomposi-
[139] Lázaro MJ, Pinilla JL, Suelves I, Moliner R. Study of the deactivation mechan- tion of methane in the presence of carbon dioxide over Ni catalysts. Chem
ism of carbon blacks used in methane decomposition. Int J Hydrog Energy Eng Sci 2008;63:5083–8.
2008;33:4104–11. [169] Fidalgo B, Muradov N, Menéndez JA. Effect of H2S on carbon-catalyzed
[140] Zhuang QL, Kyotani T, Tomita A. DRIFT and TK/TPD analyses of surface oxygen methane decomposition and CO2 reforming reactions. Int J Hydrog Energy
complexes formed during carbon gasification. Energy Fuels 1994;8:714–8. 2012;37:14187–94.
[141] Bai Z, Li W, Bai J, Li B, Chen H. The effects of textural properties and surface [170] Otsuka K, Takenaka S, Ohtsuki H. Production of pure hydrogen by cyclic
chemistry of activated carbon on its catalytic performance in methane decomposition of methane and oxidative elimination of carbon nanofibers on
decomposition for hydrogen production. Energy Sources Part A: Recovery, supported-Ni-based catalysts. Appl Catal A: Gen 2004;273:113–24.
Util Environ Eff 2012;34:1145–53. [171] Bachiller-Baeza B, Mateos-Pedrero C, Soria MA, Guerrero-Ruiz A, Rodemerck
[142] Zhang J, Jin L, He X, Liu S, Hu H. Catalytic methane decomposition over activated U, Rodríguez-Ramos I. Transient studies of low-temperature dry reforming of
carbons prepared from direct coal liquefaction residue by KOH activation with methane over Ni-CaO/ZrO2-La2O3. Appl Catal B: Environ 2013;129:450–9.
addition of SiO2 or SBA-15. Int J Hydrog Energy 2011;36:8978–84. [172] Pino L, Vita A, Cipitì F, Laganà M, Recupero V. Hydrogen production by
[143] Abbas HF, Baker IF. Thermocatalytic decomposition of methane using methane tri-reforming process over Ni–ceria catalysts: effect of La-doping.
activated carbon: studying the influence of process parameters using Appl Catal B: Environ 2011;104:64–73.
factorial design. Int J Hydrog Energy 2011;36:8985–93. [173] Yan Z-F, Ding R-G, Song L-H, Qian L. Mechanistic study of carbon dioxide
[144] Abbas HF, Daud WMAW. Deactivation of palm shell-based activated carbon reforming with methane over supported nickel catalysts. Energy Fuels
catalyst used for hydrogen production by thermocatalytic decomposition of 1998;12:1114–20.
methane. Int J Hydrog Energy 2009;34:6231–41. [174] Zhu X, Huo P, Zhang Y-p, Cheng D-g, Liu C-j. Structure and reactivity of
[145] Serrano DP, Coronado JM, de la Pena O'Shea VA, Pizarro P, Botas JA. Advances plasma treated Ni/Al2O3 catalyst for CO2 reforming of methane. Appl Catal B:
in the design of ordered mesoporous materials for low-carbon catalytic Environ 2008;81:132–40.
hydrogen production. J Mater Chem A 2013;1:12016–27. [175] González AR, Asencios YJO, Assaf EM, Assaf JM. Dry reforming of methane on
[146] Ryu BH, Lee SY, Lee DH, Han GY, Lee T-J, Yoon KJ. Catalytic characteristics of Ni–Mg–Al nano-spheroid oxide catalysts prepared by the sol–gel method
various rubber-reinforcing carbon blacks in decomposition of methane for from hydrotalcite-like precursors. Appl Surf Sci 2013;280:876–87.
hydrogen production. Catal Today 2007;123:303–9. [176] Chen W, Zhao G, Xue Q, Chen L, Lu Y. High carbon-resistance Ni/CeAlO3-Al2O3
[147] Lee SY, Kwak JH, Han GY, Lee TJ, Yoon KJ. Characterization of active sites for catalyst for CH4/CO2 reforming. Appl Catal B: Environ 2013;136–137:
methane decomposition on carbon black through acetylene chemisorption. 260–8.
Carbon 2008;46:342–8. [177] Amin MH, Mantri K, Newnham J, Tardio J, Bhargava SK. Highly stable
[148] Zhang J, Jin L, Li Y, Hu H. Ni doped carbons for hydrogen production by ytterbium promoted Ni/γ-Al2O3 catalysts for carbon dioxide reforming of
catalytic methane decomposition. Int J Hydrog Energy 2013;38:3937–47. methane. Appl Catal B: Environ 2012;119–120:217–26.
[149] Morales-Torres S, Silva AMT, Maldonado-Hódar FJ, Machado BF, Pérez- [178] Edwards JH, Maitra AM. The chemistry of methane reforming with carbon
Cadenas AF, Faria JL, et al. Pt-catalysts supported on activated carbons for dioxide and its current and potential applications. Fuel Process Technol
catalytic wet air oxidation of aniline: activity and stability. Appl Catal B: 1995;42:269–89.
Environ 2011;105:86–94. [179] Domínguez A, Fidalgo B, Fernández Y, Pis JJ, Menéndez JA. Microwave-
[150] Li H, Yu D, Hu Y, Sun P, Xia J, Huang H. Effect of preparation method on the assisted catalytic decomposition of methane over activated carbon for free
structure and catalytic property of activated carbon supported nickel oxide hydrogen production. Int J Hydrog Energy 2007;32:4792–9.
catalysts. Carbon 2010;48:4547–55. [180] Fidalgo B, Domínguez A, Pis JJ, Menéndez JA. Microwave-assisted dry
[151] Chen J, He M, Wang G, Li Y, Zhu ZJ. Production of hydrogen from methane reforming of methane. Int J Hydrog Energy 2008;33:4337–44.
decomposition using nanosized carbon black as catalyst in a fluidized-bed [181] Pinilla JL, Suelves I, Utrilla R, Gálvez ME, Lázaro MJ, Moliner R. Hydrogen
reactor. Int J Hydrog Energy 2009;34:9730–6. production by thermo-catalytic decomposition of methane: regeneration of
[152] Prasad JS, Dhand V, Himabindu V, Anjaneyulu Y, Jain PK, Padya B. Production active carbons using CO2. J Power Sources 2007;169:103–9.
of hydrogen and carbon nanofibers through the decomposition of methane [182] Lázaro MJ, Gálvez ME, Artal S, Palacios JM, Moliner R. Preparation of
over activated carbon supported Pd catalysts. Int J Hydrog Energy 2010;35: steam-activated carbons as catalyst supports. J Anal Appl Pyrolysis 2007;78:
10977–83. 301–15.
[153] Sarada Prasad J, Dhand V, Himabindu V, Anjaneyulu Y. Production of [183] Choudhary VR, Banerjee S, Rajput AM. Continuous production of H2 at low
hydrogen and carbon nanofibers through the decomposition of methane temperature from methane decomposition over Ni-containing catalyst fol-
over activated carbon supported Ni catalysts. Int J Hydrog Energy 2011;36: lowed by gasification by steam of the carbon on the catalyst in two parallel
11702–11. reactors operated in cyclic manner. J Catal 2001;198:136–41.
[154] Zhang J, Jin L, Li Y, Si H, Qiu B, Hu H. Hierarchical porous carbon catalyst for [184] Amin AM, Croiset E, Constantinou C, Epling W. Methane cracking using Ni
simultaneous preparation of hydrogen and fibrous carbon by catalytic supported on porous and non-porous alumina catalysts. Int J Hydrog Energy
methane decomposition. Int J Hydrog Energy 2013;38:8732–40. 2012;37:9038–48.
[155] Wei L, Tan Y-s, Han Y-z, Zhao J-t, Wu J, Zhang D. Hydrogen production by [185] Amin AM, Croiset E, Malaibari Z, Epling W. Hydrogen production by methane
methane cracking over different coal chars. Fuel 2011;90:3473–9. cracking using Ni-supported catalysts in a fluidized bed. Int J Hydrog Energy
[156] Wang HY, Lua AC. Hydrogen production by thermocatalytic methane 2012;37:10690–701.
decomposition. Heat Transf Eng 2012;34:896–903. [186] Guil-López R, La Parola V, Peña MA, Fierro JLG. Hydrogen production via CH4
[157] Abbas HF, Wan Daud WMA. Hydrogen production by methane decomposi- pyrolysis: regeneration of ex hydrotalcite oxide catalysts. Catal Today
tion: a review. Int J Hydrog Energy 2010;35:1160–90. 2006;116:289–97.
[158] Muradov N, Smith F, Huang C, T-Raissi A. Autothermal catalytic pyrolysis of [187] Li J, Smith KJ. Methane decomposition and catalyst regeneration in a cyclic
methane as a new route to hydrogen production with reduced CO2 emis- mode over supported Co and Ni catalysts. Appl Catal A: Gen 2008;349:116–24.
sions. Catal Today 2006;116:281–8. [188] Ammendola P, Chirone R, Ruoppolo G, Russo G. Regeneration of spent catalysts in
[159] de la Casa-Lillo MA, Moore BC, Cazorla-Amorós D, Linares-Solano A. Mole- oxy-combustion atmosphere. Exp Therm Fluid Sci 2010;34:262–8.
cular sieve properties obtained by cracking of methane on activated carbon [189] Ammendola P, Chirone R, Ruoppolo G, Russo G. Regeneration of deactivated
fibers. Carbon 2002;40:2489–94. catalysts for TCD process by carbon oxidation in a fluidized bed reactor. Third
[160] Zhang J, Jin L, Hu H, Xun Y. Effect of composition in coal liquefaction residue European Combustion Meeting ECM, 2007; 2007.
on catalytic activity of the resultant carbon for methane decomposition. Fuel [190] Rahman M, Croiset E, Hudgins R. Catalytic decomposition of methane for
2012;96:462–8. hydrogen production. Top Catal 2006;37:137–45.
[161] Malaika A, Kozłowski M. Hydrogen production by propylene-assisted decom- [191] Sun Z-q, Wu J-h, Haghighi M, Bromly J, Ng E, Wee HL, et al. Methane cracking
position of methane over activated carbon catalysts. Int J Hydrog Energy over a bituminous coal char. Energy Fuels 2007;21:1601–5.
2010;35:10302–10. [192] Koc R, Alper E, Croiset E, Elkamel A. Partial regeneration of Ni-based catalysts
[162] Pinilla JL, Suelves I, Lázaro MJ, Moliner R. Influence on hydrogen production for hydrogen production via methane cracking. Turk J Chem 2008;32:
of the minor components of natural gas during its decomposition using 157–68.
carbonaceous catalysts. J Power Sources 2009;192:100–6. [193] Abbas HF, Daud WMAW. An experimental investigation into the CO2
[163] Malaika A, Krzyżyńska B, Kozłowski M. Catalytic decomposition of methane gasification of deactivated activated-carbon catalyst used for methane
in the presence of in situ obtained ethylene as a method of hydrogen decomposition to produce hydrogen. Int J Hydrog Energy 2010;35:141–50.
production. Int J Hydrog Energy 2010;35:7470–5. [194] Ammendola P, Chirone R, Ruoppolo G, Russo G. Regeneration strategies of
[164] Rechnia P, Malaika A, Krzyżyńska B, Kozłowski M. Decomposition of methane deactivated catalysts for thermo-catalytic decomposition process in a flui-
in the presence of ethanol over activated carbon catalyst. Int J Hydrog Energy dized bed reactor. Combust Sci Technol 2008;180:869–82.
2012;37:14178–86. [195] Liu T-f, Fang Y-t, Wang Y. An experimental investigation into the gasification
[165] Rechnia P, Malaika A, Najder-Kozdrowska L, Kozłowski M. The effect of reactivity of chars prepared at high temperatures. Fuel 2008;87:460–6.
ethanol on carbon-catalysed decomposition of methane. Int J Hydrog Energy [196] Adhikari S, Fernando S. Hydrogen membrane separation techniques. Ind Eng
2012;37:7512–20. Chem Res 2006;45:875–81.
256 U.P.M. Ashik et al. / Renewable and Sustainable Energy Reviews 44 (2015) 221–256

[197] Yu J, Tan M, Liu PKT, Sahimi M, Tsotsis TT. Hydrogen production from [203] Uemiya S, Matsuda T, Kikuchi E. Hydrogen permeable palladium–silver alloy
biomass-derived syngas using a membrane reactor based process. Ind Eng membrane supported on porous ceramics. J Membr Sci 1991;56:315–25.
Chem Res 2013;53:819–27. [204] Shigarov AB, Kirillov VA. Modeling of membrane reactor for steam methane
[198] Sircar S, Golden TC. Purification of hydrogen by pressure swing adsorption. reforming: from granular to structured catalysts. Theor Found Chem Eng
Sep Sci Technol 2000;35:667–87. 2012;46:97–107.
[199] Ishihara T, Kawahara A, Fukunaga A, Nishiguchi H, Shinkai H, Miyaki M, et al. [205] Acha E, Requies J, Barrio VL, Cambra JF, Güemez MB, Arias PL, et al. PdCu
CH4 decomposition with a Pd  Ag hydrogen-permeating membrane reactor membrane integration and lifetime in the production of hydrogen from
for hydrogen production at decreased temperature. Ind Eng Chem Res methane. Int J Hydrog Energy 2013;38:7659–66.
2002;41:3365–9. [206] Ryi S-K, Park J-S, Kim D-K, Kim T-H, Kim S-H. Methane steam reforming
[200] Zhang Y, Li Q, Shen P, Liu Y, Yang Z, Ding W, et al. Hydrogen amplification of with a novel catalytic nickel membrane for effective hydrogen production.
coke oven gas by reforming of methane in a ceramic membrane reactor. Int J J Membr Sci 2009;339:189–94.
Hydrog Energy 2008;33:3311–9. [207] Matsuka M, Higashi M, Ishihara T. Hydrogen production from methane using
[201] Tsuru T, Yamaguchi K, Yoshioka T, Asaeda M. Methane steam reforming by vanadium-based catalytic membrane reactors. Int J Hydrog Energy
microporous catalytic membrane reactors. AIChE J 2004;50:2794–805. 2013;38:6673–80.
[202] Sun L, Liu Y, Wang W, Ran R, Huang Y, Shao Z. Methane catalytic decom- [208] Borgognoni F, Tosti S, Vadrucci M, Santucci A. Pure hydrogen production in a
position integrated with on-line Pd membrane hydrogen separation for fuel Pd–Ag multi-membranes module by methane steam reforming. Int J Hydrog
cell application. Int J Hydrog Energy 2010;35:2958–63. Energy 2011;36:7550–8.