CHAPTER 1

INTRODUCTION

1.1 Background of Study

The worldwide of current energy needs is supplied by combustion of non-renewable energy

sources, namely fossil fuels, and is associated with the release of large quantities of greenhouse
gases (GHG), especially carbon dioxide (CO2), and other harmful emissions to the atmosphere
such as methane (CH4), nitrous oxide (N2O) and fluorinated gases ( Lotfi et al., 2011).

The gradual depletion of these fossil fuel reserves, and efforts to battle pollution and
greenhouse gas emissions, have generated considerable interest in using alternative sources of
energy. Hydrogen gas may one day replace fossil fuels for various applications such as in
automobiles and power stations ( Malaika et al., 2010). Furthermore, it can be used as input to
the fuel cell, which operates with a relatively high efficiency compared to combustion process
( Weger et al, 2016).

To provide an alternative to existing fuel appropriate method for large-scale production of H2

was developed (Abbas et al., 2009).Currently, hydrogen is produced primarily via catalytic steam
reforming, partial oxidation, and auto-thermal reforming of natural gas. Although these processes
are mature technologies, CO is formed as a by-product, and in order to eliminate it from the
hydrogen stream, complicated and costly separation processes are required ( Amin et al.,
2012).Alternatively, methane cracking can produce 90% concentrated stream of CO-free
hydrogen, mixed with residual methane.

In addition to producing CO-free hydrogen, methane catalytic cracking produces a

significant amount of carbon filaments, which have wide industrial applications, or which
alternatively could be burned to provide the heat necessary for the cracking process (Ahmed et
al., 2009).

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 In this process, methane (CH4) is decomposed to produce elemental carbon and H2.
Therefore, methane cracking generates zero emissions of CO2 compared to steam reforming
method.
CH4 C(s) + 2H2 Equation 1

Increasing demand for CO-free hydrogen has increased interest in the direct catalytic
cracking of natural gas ( Amin et al., 2012), as described by equation (1).As a result of methane
cracking, only hydrogen is produced as a gaseous product in a mixture with un-reacted methane.
Separation of methane and hydrogen can be achieved easily by absorption or membrane
separation to produce a stream of 99% by volume hydrogen, which is much simpler than the
need for further complicated separation processes that deal with CO 2 or CO in the steam
reforming.

In the methane cracking process, catalyst has been recognized as a key component to help
the production of hydrogen ( Mendoza et al., 2016). Methane cracking is not feasible at moderate
temperatures. To achieve a reasonable yield, a temperature higher than 1200 is required. In
order to reduce the operating temperature, catalyst is needs in the reaction to reduce activation
energy (Amin et al., 2012).

Nickel has been described as the most active catalyst for methane cracking among the
iron group metals. Cobalt could potentially be used as a catalyst for methane cracking, but it is
less active, has toxicity issues, and higher cost compared to nickel. Iron has also been studied as
a catalyst for methane catalytic cracking but it showed lower activity compared to nickel.
A direct comparison shows that the methane cracking catalytic activity for the iron group metals
is: Ni > Co> Fe (Amin et al., 2012).

Metal catalysts are usually deposited on supports such as silica (SiO2) or alumina (Al2O3).
In this research alumina is used to support the metal catalyst deposited. Researchers have found
that Ni or Ni/alumina (NiO-Al2O3) exhibited the highest activities compared to Ni/silica (Abbas
et al;2009 and Zhao et al; 2011).

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 In this research, Lanthanum will be added to the nickel catalyst as a promoter.
Lanthanum addition will improved catalyst activity, increased resistance to carbon deposition
and higher stability in comparison to un-promoted materials (Zhao et al., 2011).

1.2 Motivation

Carbon dioxide (CO2) is one of the examples of greenhouse gases in the Earths atmosphere.
The concentration of CO2 in Earths atmosphere has increased during the past century (Robinson
et al., 2007). Global CO2 emissions would need to be reduced greatly in the near future. Almost
all activities associated with our modern societies are dependent on fossil fuels. At present, over
80% of the primary energy consumption of the world comes from combustion of oil, coal and
natural gas (Ryden, 2008).

Due to this problem, methane cracking of hydrocarbons has gained more interest as a CO-
free hydrogen production method. Hydrogen produced by methane cracking is free of CO and
CO2, making methane cracking a suitable method to produce H2 for proton exchange membrane
(PEM) fuel cells which require pure H2 ( Weger et al., 2016). Methane, which has the highest
percentage of hydrogen or carbon among hydrocarbons, is gaining even more interest due to
recent commercial applications of carbon filaments, which is the only by-product of the cracking
process (Amin et al., 2012).

Not only carbon filaments can be used in commercial applications, their production also
helps to minimize the emissions of greenhouse gases as the product carbon is not released, but
instead used. The elemental carbon produced may possess an economic value because it is
essential in the production of carbon filaments, which can be used in a variety of manufacturing
applications (Abanades et al., 2012).

1.3 Problem statement

In the methane cracking, one of the main challenges accompanying with metal catalysts is
the deactivation of catalyst.

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 The reason for the gradual deactivation of catalysts is due to the deposition of encapsulates
carbon on the catalyst surface, which results in blocking of active sites and a reduction in catalyst
surface area (Amin et al., 2012).

The carbon formed in this reaction is one of the products, which means its production cannot
be stopped. The reaction system and catalyst should be improved to retain good activity and
stability despite the formation of extensive amounts of carbon (Ibrahim et al., 2015).

1.4 Objectives

The following are the objective of this research:

1) To investigate the effects of lanthanum as promoter on nickel based catalyst for

hydrogen production via methane cracking.

2) To evaluate the morphology of NiO-Al2O3 catalyst before and after the methane cracking
process towards carbon deposition problem.

1.5 Scopes of Study

The following are the scope of this research:

1) Preparing the NiO-Al2O3 catalyst using wet impregnation method at different proportion of
lanthanum (La) in nickel catalyst (2%, 4% and 6%).

2) Conducting methane cracking study in fixed bed reactor by investigating 3 parameter:

(i) Reaction temperature (500, 550, 600 )
(ii) Methane concentration in the mixture of CH4/N2 (50/50, 65/35 and 80/20)
(iii) Methane flow rate (80, 100, 120 mL/min)

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 3) Characterization of catalyst using Scanning Electron Microscopy (SEM) and Thermal
Gravimetric Analyzer (TGA).

CHAPTER 2
LITERATURE REVIEW

2.1 Hydrogen Production

Hydrogen is the most abundant element in the universe. Hydrogen is also a promising
source of "clean" fuel on Earth. Hydrogen is typically produced by heating natural gas with
steam to form a mixture of hydrogen and carbon monoxide called syngas, which is then
separated to produce hydrogen (Samanta and Verma, 2015).

2.1.1 Steam Reforming

Hydrogen can be produced via catalytic steam reforming, partial oxidation, and auto-
thermal reforming of natural gas. Steam reforming is widely used for producing hydrogen.
However, CO is formed as a by-product, and in order to eliminate it from the hydrogen stream,
complicated and costly separation processes are required ( Amin et al., 2012).

Steam reforming involves a multiple stage process. The first stage is the highly
endothermic catalytic reforming of methane conducted at high temperature (800 900), while
the second stage is the catalytic water gas shift (WGS) reaction, the third stage is the separation
of the H2CO2 mixture using pressure-swing adsorption (PSA) (Amin et al, 2012).

2.1.2 Methane Cracking

Methane catalytic cracking is a process by which carbon monoxide-free hydrogen can be

produced. Despite the fact that hydrogen produced from methane cracking is pure form of
hydrogen, methane cracking is not used on an industrial scale for producing hydrogen since it is
not economically competitive with other hydrogen production processes. However, pure
hydrogen demand is increasing annually either in amount or in number of applications that
require carbon monoxide-free hydrogen (Lofti et al.,2011).

5
 During the methane cracking process, un-reacted CH4 is separated from H2, and is re-
circulated to the reactor. While the gas feedstock for methane cracking is mainly composed of
CH4, other hydrocarbons present are cracked in the same way as CH4 by thermal splitting of the
C-H bonds (Weger et al., 2016).

2.2 Catalyst Materials

The catalyst function is to reduce the activation energy required for methane
decomposition, leading to lower operating temperatures. Non-catalytic methane cracking is very
slow for practical application at temperatures below 1000, while catalytic cracking of methane
can be conducted at temperatures as low as 500 (Ermakova et al., 2000).

2.2.1 Based Catalyst

Transition metals such as Iron (Fe), Nickel (Ni) and Cobalt (Co) are often used for
methane cracking because of their tendency for carbide formation (Fakeeha et al., 2016).Nickel
has been described as the most active catalyst for methane cracking among the iron group metals.

Cobalt could potentially be used as a catalyst for methane cracking, but it is less active,
has toxicity issues, and higher cost compared to nickel. Iron has also been studied as a catalyst
for methane catalytic cracking but it showed lower activity compared to nickel.

Figure 2.1: Catalyst structure of nickel (ii) oxide (NiO)

(Source:https://www.webelements.com/compounds/nickel/nickel_oxide.html)

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 The figure 2.1 shows Nickel (II) oxide is the chemical compound with the formula NiO.
Nickel (II) oxide has the rock salt crystal structure, which is slightly distorted from a cubic
symmetry below 250 C, above that temperature it is perfectly in cubic shape (Amin et al., 2012).

2.2.2 Supporter

Supported catalysts are often applied because they combine a relatively high dispersion
amount of active surface with a high degree of thermo stability of the catalytic component
( Perego and Villa , 1997).

The selection of a support is based on its having certain desirable characteristics.

Principally their characteristic is based on Table 2.1.

Table 2.1: Characteristics of selection a support ( Perego and Villa , 1997)

No. Characteristics
1. Inertness.
2. Desirable mechanical properties, including attrition resistance, hardness
and compressive strength.

3. Stability under reaction and regeneration conditions.

4. Surface area. High surface area is usually, but not always, desirable.

5. Porosity, including average pore size and pore size distribution. High
area implies fine pores, but relatively small pores (for example < 5 nm)
could become plugged during impregnation, especially if high loading is
sought.

6. Low cost.

Of a wide variety of possible materials, only two of them possess a good combination of
the characteristics mentioned, they are alumina and silica. Both of them are the most
common used in industry( Tang et al. , 2010).Considering methane cracking catalyst will be
exposed under high temperatures; silica containing supports which would exhibit unstable
performance cannot be used. Thus leaves alumina as the most logical choice of a support.
Figure 2.2 shows the alumina structural that used as the supporter in this study.

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 Figure 2.2: Aluminium Oxide (Al2O3) Crystal Structure (Source:
https://www.slideshare.net)

Aluminium oxide or alumina is a chemical compound of aluminium and oxygen with

the chemical formula Al2O3. This alumina can stabilize the catalytic particles such as oxide,
metal or sulphide. The catalytic particles are help hold the active sites. Researchers have found
that Ni or Ni/alumina (NiO-Al2O3) exhibited the highest activities compared to Ni/silica (Abbas
et al;2009 and Zhao et al; 2011).Methane cracking on Ni/Al2O3 catalysts is the well-established
commercial process for the production of hydrogen (Zhao et al., 2011).

2.2.3 Promoter

Promoter is a substance added to a solid catalyst to improve its performance in

a chemical reaction. By itself the promoter has little or no catalytic effect. Some promoters
interact with active components of catalysts and thereby alter their chemical effect on the
catalyzed substance. The interaction may cause changes in the electronic or crystal structures of
the active solid component (Edwards et al., 2014).

In this study, lanthanum will be used as a promoter. Figure 2.3 shows crystal structure of
lanthanum.

Figure 2.3: Crystal structure of lanthanum

(source:https://www.webelements.com/lanthanum/crystal_structure.html)

8
 According to Zhao et al. (2011), lanthanum can be a promotion of the activity of each
active site or simply to an improvement in the dispersion of the catalyst. Adding amount of
lanthanum to nickel catalysts can decrease the average NiO crystallite diameter which leads to
higher activity and stability. However, excessive addition would cause deactivation quickly sites
(Samia et al., 2015).

The addition of lanthanum ions appears to affect the activities in two opposing ways: at
low concentrations, the lanthanum promotes the activity, while at higher concentrations, it
poisons it. Moreover, according to France et al., (2014), adding lanthanum can prevent sintering
by the formation of a lanthanum aluminate layer on the surface.

2.3 Catalyst Preparation

2.3.1 Impregnation Method

Impregnated catalysts are usually obtained from preformed supports by impregnation

with the active phase (Malaika et al, 2010). The mixing operation often consists of impregnating
a powder with a solution of the active substance precursors. Quite a number of hydrogenation
catalysts are prepared in this way.

After the catalyst is prepared using impregnation, the catalyst needs to be activated prior
to reaction. The pre-treatment includes calcination and reduction. The calcination step helps in
removing any residual precursor species and to change the precursor material to metal oxide
(Al-Fatesh and Fakeeha, 2012). The reduction step is required after calcination to transform
metal oxide to the active metal phase.

2.3.2 Co-Precipitation

Some preparation of Catalysts Ni-Al2O3 was prepared using co-precipitation method.

The Ni-Al2O3 catalysts were prepared as follows: an aqueous solution containing requisite
amounts of Ni (NO3)23H2O and Al (NO3)39H2O were simultaneously precipitated using an
aqueous solution containing potassium hydroxide; during the process, pH was maintained around

9
9.5 - 10. The co-precipitated mass was thoroughly washed, filtered and dried at 110C for 12 h in
air followed by calcination in furnace (Chattopadhyay et al., 2011).

2.4 Deactivation of catalyst

Coking or the formation of carbon is one of the main reasons of catalyst deactivation
(Palero et al., 2012). Methane decomposes at the gas or metal interface, producing carbon which
dissolves and diffuses through and around the catalyst particle to the metal or support interface,
detaching the catalyst particle from the support, forming a filament with the catalyst particle on
the filament's tip (Samanta and Verma, 2015).

Carbon diffusion through the metal particle has been proposed as the rate controlling step,
and deactivation is a result of space limitation in the reactor is a result of a solubility limitation of
carbon in nickel when the dissolved carbon reaches its saturation concentration, which leads to
encapsulating carbon formation ( Palero et al., 2012).

2.5 Carbon Formation

There are three types of coke that form during methane cracking on supported metal
catalysts, namely polymeric, filamentous, and graphitic carbon. Polymeric coke is produced
during thermal decomposition of hydrocarbons, while the filamentous and graphitic carbons are
formed during catalytic cracking of hydrocarbons; the classification here is related to the reaction
conditions (Fakeeha et al., 2016).

Coke can also be characterized based on its reactivity with hydrogen, water, and oxygen.
The formation of coke on nickel is a multistage process. The process starts with methane
adsorption followed by several dehydrogenation reactions and ends with coke formation, as
shown in Figure 2.4.

After methane is adsorbed on the fresh nickel catalyst and the hydrogen is released, the
remaining deposited carbon dissolves in nickel forming a layer of uniform concentration solution

10
of carbon in nickel at the gas side; the carbon concentration is equivalent to the gas-phase
solubility of carbon in nickel (Amin et al.;2012 and Bartholomew et al.; 2015).

Then carbon diffuses through the nickel particle to the support side until the carbon
solution of nickel is supersaturated with respect to the filamentous carbon; at that time,
nucleation of filamentous carbon begins with carbon filament growth, encapsulating carbon
forms, which slows the cracking rate and ultimately deactivates the catalyst (Amin et al., 2012).

Figure 2.4: Schematic of the classical mechanism of carbon filament formation

(Amin et al., 2012)

Due to the presence of excess carbon on the gas side of the nickel surface, some carbon
deposits on the nickel surface form encapsulating carbon, which is responsible for catalyst
deactivation. As the encapsulating carbon deposits on nickel, a gradual decrease in available
nickel surface area for methane cracking occurs.

In addition, this gradual decrease in active surface area results in less heat input to the
metal particle, which decreases the rate of carbon diffusion through the nickel particles by
reducing the carbon solubility. This, in turn, slows down the removal of carbon at the gas side
which further increases the rate of encapsulating carbon deposition .Because of these cause and
effect phenomena, the active nickel particles ultimately become completely encapsulated by
carbon and filament growth ceases(Amin et al., 2012).

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2.6 Parameter effect Methane Cracking

2.6.1 Temperature

Reaction temperature has a great influence of catalyst activity, catalyst lifetime and
morphology of carbon nanotubes produced. Temperature elevation results in a disproportionately
rapid catalyst deactivation. At high temperature, it is believed that catalyst will appear where the
catalyst particles are easily cut into small particles and the small particles are found easily
encapsulated by the carbon layer formed during methane decomposition, contributing to faster
catalyst deactivation. On the other hand, at low temperature, the catalyst remains in solid state
rather than in liquid state (Awadallah et al., 2015) and it sustains the activity of catalysis process.

Lower temperature is inappropriate for methane decomposition process because of a

noticeably longer reaction time due to the decrease in the methane conversion. Basically,
decision on the desired reaction temperature is determined based on the optimized profitability
between the cost of recycling un-reacted methane resulting from lower methane conversion at
lower temperature and the cost of the catalyst replacement, due to faster catalyst deactivation, at
high temperature operation conditions ( Chai et al., 2004).

2.6.2 Methane Concentration

As demonstrated in Figure 2.5 under the heading of Methane Concentration, with an

increase in methane concentration in the feed was an increase in the rate of methane
decomposition. As more methane is fed, more hydrogen is produced. An increase in methane
feed concentration results to more available methane that can come in contact with the catalyst
which results to an increase in hydrogen in the effluent (Palero et al., 2012).

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 Figure 2.5: Optimal solution plot for methane decomposition rate (Palero et al., 2012)

2.6.3 Methane Flow Rate

According Amin et al., (2012) the purpose of the study at different flow rates was to
determine whether the flow rate has any effect on the cracking reaction and to determine which
flow rate was adequate to study methane cracking .

Figure 2.6: Effect of gas flow rate and temperature on carbon capacity (Amin et al., 2012)

The effect of flow rate and temperature on carbon capacity for the porous catalyst is seen
in Figure 2.6. In this study, the carbon capacity is defined as the maximum normalized amount of
carbon deposited after complete catalyst deactivation (Amin et al., 2012). At 500 and 550,
increasing the flowrate from 120 to 240 ml/min has little effect on carbon capacity. However, at
higher temperatures (600 and 650) similar changes in flow rates lead to a decrease in carbon
capacity.

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2.7 Fixed Bed Reactor

Reactors can be classified based on different criterion such as size, reactor material,
methods of charging and discharging or type of fluid flow. For fluid solid heterogeneous
system reaction rate is based on mass of solid catalyst rather than on reactor volume. In
laboratory scale, the reactions are carried out in micro reactors with diameters ranging from 1 5
mm for testing up to 0.1 1gm of catalysts. In industry, diameter and height of reactors can vary
from 1 to 10 m and 2 to30 m respectively. The reactor materials also vary depending on usage.
Laboratory reactors are usually made of glass, quartz or stainless steel with few mm wall
thicknesses. The large industrial reactors depending on usage are usually made of mild steel or
stainless steel or other alloys. The wall thickness can range from of 6-15 mm depending on
process pressure (Eigenberger, 1992).

Depending on the operation, reactor can be batch, mixed flow or packed bed type. The
choice of reactor depends on the type of reaction. For examples, many hydrogenation reactions
are carried out in CSTR while many of the solid catalysts are tested in fixed bed reactor. Reactor
selection also depends on the type of catalyst and its activity, selectivity and deactivation
behavior.

Advantages of fixed bed reactor include ideal plug flow behavior, lower maintenance
cost and reduced loss due to attrition and wear. These reactors are mainly used for measuring
reaction kinetics and catalyst activity at different conditions of temperature and pressure.

CHAPTER 3

METHODOLOGY

3.1 Overall workflow

In this research, nickel catalyst will be prepared using impregnation method. The catalyst
will be prepared to produce H2 via methane cracking process. Figure 3.1 shows the overall
workflow of process.

14
 Catalyst preparation will be done by impregnation method

Next, the catalyst will be used in methane cracking process.

The catalyst will be characterized using SEM while the amount

of the carbon deposited will be calculated using TGA.

Figure 3.1: The overall workflow of the process

3.2 Material

3.2.1 Chemical

Lanthanum (III) nitrates hexahydrate, nickel (III) nitrate hexahydrate, aluminium oxide, methane
gas, hydrogen gas, nitrogen gas.

3.2.2 Equipment/Apparatus/Tools

Cotton wool, gas bag, hot plate, beaker 250mL, crucible, Magnetic stirrer, Furnace, Fixed bed
reactor and gas chromatograph.

3.3 Procedure/Method

3.3.1 Catalyst Preparation

(a)Wet Impregnation

The alumina (Al2O3) will be dried overnight in the oven at 150 C. A solution of nickel
nitrate hexahydrate (Ni (NO3)26H2O) will be prepared in de-ionized water. Then the alumina
and lanthanum (III) nitrate hexahydrate (La(NO3)3 6H2O) will be added together into the

15
solution. The lanthanum promoted NiO - Al2O3 catalyst will be weighted with weight ratio,
Ni/La/Al: (10/2/88, 10/4/86, and 10/6/84). Lastly, the slurry will be stirred in a beaker over a hot
plate at 80 C for 3 hours.

(b)Drying

The prepared slurry catalyst then will be dried in the oven overnight at 105 C.

(c)Calcination

The catalyst will be calcined in air at 600 C in the furnace for 3 hours.

3.3.2Methane Cracking

150 gram of catalysts will be weighted and placed on the cotton wool. The catalyst is first
reduced in a stream of 10% H2 and 90% N2 at 750 C for 1 hour. After that, the catalyst will be
purged with N2 for 0.5 hours and heated to the different reaction temperature (500C, 550C and
600C). Methane cracking will be carried out by contacting methane with the catalyst.

The methane (CH4) concentration in CH4-N2 mixture will be varied to 50/50, 65/35 and
80/20 .The flow rate of inlet gas will be adjusted to 80, 100 and 120 mL/min. The decomposition
experiment will be run for 4 hours before any significant carbon accumulation started to block
the fixed bed reactor, resulting in a constraint of gas flow. The composition is analyzed by using
gas chromatograph. The methane conversion will be calculated from the outlet methane
concentration.

3.4 Characterization of Catalyst

In this research, Scanning Electron Microscopy (SEM) and Thermal Gravimetric

Analyzer (TGA) will be used in the experiment. SEM will be used to study the catalyst
morphology while TGA will be used to calculate the amount of carbon deposited due to methane
cracking.

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3.5 Experiment Set-up

Figure 3.2 shows the set-up of the apparatus for catalysis activity.

Nitrogen

Hydrogen

Methane

Thermocouple

Catalyst Bed

Cotton Wool

Furnace
Reactor

Gas Gas
Collector Chromatograph
Output

Figure 3.2: Catalysis activity test station

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 Research Planning Gantt chart
SEM1

Task/ W W W W W W W W W W W W W W
week 1 2 3 4 5 6 7 8 9 1 1 1 1 1
0 1 2 3 4
Research proposal drafting
Research proposal submission
Chemical requisition form
submission
Research proposal presentation
Minor report submission
Chapter 1-4 drafting
Partial thesis submission
SEM 2
Apparatus preparation
Conducting experiment
Sample and data collection
Data analysis
Thesis writing
Thesis submission

Completed task
In completed task

Milestones

0% 30% 50% 100%

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