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Development of ammonia synthesis

Article · September 2011

DOI: 10.1109/NatPC.2011.6136449

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 Development of Ammonia Synthesis
Poppy Puspitasari
Electrical and Electronic Engineering Department
University Technology PETRONAS
Bandar Seri Iskandar, 31750 Tronoh Perak Malaysia
e-mail : povopivi@gmail.com
Abstract— Ammonia production is a high energy and
capital-intensive industry as it obliges high temperature
(400-500oC) and also high pressure (150-300 bar) for its
daily processes. Two moles of ammonia are obtained by
reacting one mole of nitrogen and three moles of hydrogen
gases in the existence of conventional catalyst which are
magnetite (Fe3O4). The process to produce ammonia is
known as Haber-Bosch process which was developed and
patented by Fritz Haber and Carl Bosch in 1916. Since
then more work on ammonia production was carried out
with the goal to achieve higher ammonia yield.
Keywords- Ammonia Synthesis, Reactor, Yield
I. INTRODUCTION
Ammonia has been ranked number two on the list of
chemicals requiring the most energy to be produced.
Identifying better way to synthesize ammonia could have a
major impact on the production of ammonia.
Using Haber process, only 15% of nitrogen and hydrogen
were converted to ammonia. By repetitive recycling of the
unreacted nitrogen and hydrogen, the overall conversion is
about 98% [1].
2H2 (g) + N2 (g)  2NH3 (g) (1)
Based on Le Chatelier Principle, reactions conducted at higher
pressure will favor the forward reaction producing more
ammonia.
Catalysts are materials that can be reacted to enhance the rate
of ammonia production. The presence of catalyst precursors is
very essential for ammonia production. Good catalyst support
can increase the rate of ammonia because of active chemical
reaction. Brookhaven et.al. [2] revealed the metal ruthenium
could be more efficient in ammonia synthesis. It was reported
that ruthenium catalyst displayed five times higher activity
under same temperature and at half of the pressure [3]. A new
approach by using nanomaterials as catalyst can achieve very
high rate of ammonia production [4]. Reducing catalyst size to
nanometers will greatly increase the surface area which in turn
increases the level of catalytic activity.
Noorhana Yahya
Fundamental Applied Sciences Deparment
University Technology PETRONAS
Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia
e-mail: noorhana_yahya@petronas.com.my
Magnetic induction is a new discovery in ammonia
production. By applying magnetic field to the catalyst, it will
reduce the cost of production. Instead of high pressure and
temperature, the electromagnetic field can result high yield of
ammonia at room temperature and ambient pressure [4].
Ferromagnetism is a phenomenon in which the electrical
uncharged material strongly attracts to each other. This
ferromagnetic material aligns the electrons parallel to each
other against the force of thermal agitation [5]. Because of
good alignment, the catalytic actvity can easily improve the
reaction rate for ammonia production.
Currently, magnetite (Fe3O4) is used as the catalyst in
ammonia synthesis. It is incorporated with aluminum,
potassium, calcium and irreducible oxides [5]. Due to the easy
cation substitution for Al3+ and Fe3+, the uniform distribution
of aluminum in solid can be obtained [6]. A new finding
suggested that wustite as a new catalyst in ammonia synthesis
[7] has an increase of 30% compared to those obtained from
magnetite. Wustite is favourable compared to magnetite due to
its ability to be reduced while maintaining its mechanical
strength and thermoresistency. Also ruthenium based catalyst
has potential due to its long term stability and activity also low
pressure and temperature condition for ammonia productions
[8]. Ruthenium with potassium metal is suggested as a very
effective catalyst which performed greatly under atmospheric
pressure [9]. High ammonia yield approximately 40-50% was
produced using Ru/C catalyst. The temperature and pressure
conditions are 370-400°C and 50-100 atm respectively [10].
The major disadvantage of this catalyst is its extremely high
cost [11-12].
Arrhenius kinetic energy was first proposed by a Dutch
chemist J.H. Van’t Hoff in 1884 and was justified by Swedish
chemist Svante Arrhenius in 1889, five years later [13]. It is
remarkably accurate for the dependency of temperature with
the constant reaction rate. It can be seen as the best empirical
relationship in modeling temperature variance coefficient. It
was mentioned that an increase of 10 degree Celsius doubles
the reaction rate which is supported by Arrhenius. The amount
of energy required to ensure reaction happens is known as
activation energy. Upon collision, this energy can be used to
bend and break bonds leading to chemical reactions.
978-1-4577-1884-7/11/$26.00 ©2011 IEEE
Activation energy can be regarded as the height of the
potential barrier or energy barrier separating between the
potential energy of reactants and the product of reactions.
There should be a correct number of molecules with energy
equal or greater than the activation energy. Le Chatelier
Principle shows that rates of reaction decreases with
increasing temperature. This can be related with barrier less
reactions, in which the reaction proceeding relies on the
capture of molecules in a potential well. Increasing
temperature leads to a reduction of collision is expressed as a
reaction cross section that decreases with increasing
temperature. Also, the kinetic energy can be related to
chemical thermodynamics study of the interrelation of heat
and with chemical reactions. The thermodynamics potential
are the quantitative measures of energy stored as they evolve
from an initial state to the final state. The fundamental laws of
the four equations or ‘fundamental Gibbs free energy, are
typically used in order to predict the energy exchanges.
Arrhenius equation demonstrated that,
−𝐸𝑎
𝑘 = 𝐴𝑒 ( 𝑅𝑇 ) (2)
where,
Ea= the activation energy,
R = 8.314 x 10-3 kJ mole-1 K-1
T = temperature (K),
A = proportionality constant
Taking the natural logarithm of Arrhenius equation gives,
𝐸𝑎 1 was also studied [22]. It was found that specific surface area
ln(𝑘) = − ( ) 𝑥 ( ) + ln(𝐴) (3)
𝑅 𝑇
Y= mx + b (4)
1 Ruthenium promoted by potassium metal has been projected
Plot ln(k) vs and the data will give straight line and by
𝑇
determining the slope, the value of activation energy can be
calculated.
II. AMMONIA SYNTHESIS
In early 1970, British Petroleum Company, cooperated with
M.W. Kellog Company was created new type of catalyst,
which is Ruthenium with carbon support (Ru/C). The yield of
ammonia was successfully increased to around 40-50% by
using this Ru/C catalyst, [14]. The temperature and pressure
required also reduced to 370-400oC and 50-100 atm [14].
Nevertheless, this temperature and pressure are still
considered high and the price of Ru is very expensive
compared to iron. It has been reported that carbon have a
tendencies to react with H2 to produce methane, CH4 during
the catalytic activity [15]. In the meantime in 1996, a group of
researchers reported and patented a new high-activity
ammonia synthesis catalyst based on wustite which was
increased the reaction rate by 30% compared to the traditional
catalyst. However, this catalyst is less active than those based
on magnetite and much less resistant to thermal deactivation
[16]. It is believed that nanotechnology can give an enormous
impact in terms of profits to the industry and environment.
Efficiency of the catalytic reaction could be increased by
applying nanocatalyst and the operation condition
(temperature and pressure) required for the reaction will be
lower. The less rigorous reaction condition, high cost savings
can be created in terms of materials used, electricity, labor
used etc. The industry will also experience the condition of
environmental friendly because nanocatalyst can result in
100% catalyst selectivity for a desired product [17].
Traditionally and conventionally magnetite (Fe 3O4) was used
as catalyst for ammonia synthesis. Typical promoter for
magnetite are aluminium, potassium and calcium [18].
Therefore, magnetite is known as a precursor due to the easy
cation substitution of Al3+ for Fe3+, thus homogeneous
distribution of aluminium in solid can be gained [19].
Nowadays, wustite was proposed as a new precursor for
ammonia synthesis catalyst [20]. 30% yield of ammonia was
obtained by using wustite as catalyst, compared to magnetite.
It was also reported that wustite appears to be encouraging to
magnetite due to its ability to be reduced while
thermoresistancy and mechanical strength are fully maintained
[20].
Several research groups in the past decades have been studied
that ruthenium-based catalyst was a promising candidate to
replace magnetite for ammonia synthesis. The ruthenium-
based catalyst is well known to its long term stability and
activity. It is also capable to produce high ammonia yield in
low pressure and low temperature conditions [21]. Ru/MgO
catalyst synthesized by sol-gel method for ammonia synthesis
and metal dispersion were increased when increasing Ru
carbonyl complex concentration. The highest ammonia
formation rate was studied on magnesia supported ruthenium
Ru/MgO (Ru: 7.1 wt. %) with high surface (290 m2/g) [49].
as a very active catalyst for non conventional ammonia
synthesis which may be carried out under atmospheric
pressure [23]. Ruthenium supported on -Al2O3 which was
varied with KOH was tested as ammonia synthesis catalyst
under atmospheric pressure. It was found that the highest
hourly yield of ammonia was achieved with 8% Ru/Al2O3-
KOH at 623K and atmospheric pressure [24]. By using Ru/C
catalyst, high ammonia yield approximately 40-50% was
successfully produced at 370-400oC and 50-100 atm
respectively. The disadvantage was high cost of ruthenium
[25]. Regarding the price of ruthenium, it was reported that
carbon have a tendencies to react with H2 to produce methane,
(CH4) during the catalytic activity [26]. It is well known that
iron and ruthenium are good catalysts for ammonia synthesis
at different temperatures. Mutual influence in various scopes
on these two active catalysts was reported. It was studied that
although ruthenium is very active at optimum temperature
(573-623K), the existence of iron had resulted in very low
activity, signifying negative synergism of iron and ruthenium
[27]. Ammonia synthesis by using Ru/C catalysts with specific
carbon supports namely activated carbon fiber (ACF),
activated carbon (AC), and carbon molecular sieve (CMS) was
observed. The ammonia synthesis was obtained in 350-450oC
and 3.0 MPa in a microreactor. The result was found that Ru –
Ba/ACF gave the highest turnover-frequency (TOF) value
(0.089 s-1) due to high purity and electronic conductivity of
ACF [28]. Structure sensitivity of ruthenium catalysts
supported on the graphitised carbon was also studied.
Ammonia synthesis studies have found that the reaction rates
(400oC, 63 bar, 8.5% NH3 or 400oC, 90 bar, 11.5% NH3)
showed in terms of TOF had increased versus particle size in
spite of of the type of promoter [28]. Nowadays, Yahya et al
was proposed a new type of nanocatalyst, namely
Mn0.8Zn0.2Fe2O4 [29]. The catalyst was synthesis using sol-gel
method and was reacted under electromagnetic (EM)
induction. It was obtain high yield ammonia due to the
synergism of Mn, and Fe metal (which was reduced in
hydrogen gas) and the EM induction.
There are two other factors besides catalysts that could assist
in the ammonia yield which are promoter and support. It is
well known that metal crystallites particularly in nano scale
range have high surface area and surface energy. Therefore,
the agglomeration is favored to overcome these side effects
which finally lead to the formation of bigger crystallite size.
The catalytic activity would take place occasionally due to less
surface area available for the reactants to be adsorbed a
process. In order to make sure that the catalyst works
efficiently, small amount of chemical additive or promoter is
often added. There are two categories of promoter which are
textural or carrier and electronic.
One of the best solutions to avoid agglomeration problem is
by adding metal crystallites on the carrier or supporter. Carrier
which acquire great features such as outstanding thermal
stability and high surface area is highly needed. Alumina,γ-
Al2O3 is well known as typical carrier for ammonia synthesis
catalyst. It has high surface area (100-300 m2/g) and also able
to endure at higher temperature environment. Furthermore,
higher degree of dispersion of metal crystallites on carrier is
also needed which could stimulate the catalytic activity. This
can be achieved through the synthesis approach [30].
Electronic promoter is another crucial component for catalyst
and usually doped in relatively small amount. Nevertheless,
disproportionate doping may reduce the catalytic activity as it
can largely cover the surface of metal crystallites. Example of
promoter for ammonia synthesis catalyst is potash or
potassium hydroxide (KOH). Potassium, K+ performs as
electron donor which donates it electrons directly into d-
orbital of iron. The continuous donation will generates a high
electron density region of iron. regrettably, this occurrence
will lead to the destabilization of iron. Therefore, the surplus
electrons will be transferred to the π antibonding orbitals (π*)
in nitrogen molecules. The occupation of antibonding orbital
makes the N≡N elongate and weaker. As a consequence, the
N≡N bond cleavage is increased [31, 32].
III. MICROREACTOR
Microreactor channels has become important since they offer
several advantages over conventional analytical techniques
including small volume requirements, portability, fast
sampling times, ability to multiplex and compatible with other
technique [33]. Mostly microreactor has multiple parallel
channels with diameter between 10 to several hundred
micrometers where the chemical reaction occur [34].
Microreactor as miniaturized chemical reactors has been used
in many application such as hydrogen reforming process [35],
biochemical analysis [36], catalyst and material screening
[34]. There has been reported the microreactor system of gas-
solid-liquid channels, with the solid-catalyst in most cases
[33]. The most difficult part for that system is about the
pressure drops, the achievement of large catalyst surface areas,
and the maximization of heat transfer in exothermic systems.
Some researcher has been reported for green chemistry by
using microreactors. The review of this research was explores
that miniaturization reactor may revolutionise chemical
synthesis, highlighting in particular the environmental benefits
of this new technology which include in situ reagent
generation, solvent free mixing, and integrated separation
techniques [37]. The applications of microstructured reactors
for heterogeneous catalysed gas phase reactions has been
investigated. Many examples of partial oxidations were
described including the process of ethylene oxide synthesis
[38]. There has been reported that by using microdevice,
carbon monoxide concentration was able to reduce in a
hydrogen-rich methanol reformate gas from 0.5% to 10%
ppm. This device integrates two heat exchanger and a reactor-
heat exchanger in a single device with a volume and mass of
only 60cm3 and 150g and reaches a heat recovery of 90% [39].
IV. CONCLUSION
There are many ways to achieve the high yield of ammonia.
Choosing the best condition for the optimum yield is the
important thing. High temperature and high pressure condition
are not suitable for green environment. The new method to
synthesis ammonia is by using the magnetic field in the
ambient condition. The reactor can be develop more smaller
and efficient by using microreactor operated in ambient
condition.
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