LECTURE REPORT

Ammonia Synthesis catalysts

(Today and tomorrow-Advances related to catalysts)

Name: Syed Saqib Ali Zaidi (薩一比)

Student ID: 6216000067
Department: School of Chemical Engineering and Technology

Tianjin University, Peiyang Campus

Jinnan District, P.R. China
Ammonia Synthesis catalysts: Today and tomorrow-Advances related to catalysts

Abstract:

Ammonia synthesis optimization is a topic of high interest in industry as the market continues to
expand and demand increases. This proposed process is designed to produce 1,016 metric tons/day
of ammonia at a feed of 5,500 kmol/hr while maintaining the best compromise between production
and purity. Simulated in ASPEN with an adiabatic Gibbs reactor, optimal production is achieved
at 100 bar reactor pressure and a 7.25% purge stream, resulting in 98.96% product stream purity.
The simulated process is comparable to conventional ammonia synthesis plants. Further economic
optimization is focused on compression costs and reactor efficiency. A new ruthenium-based
catalyst with higher activity at lower total pressures can be employed enabling the process to run
at significantly lower pressures while maintaining high ammonia conversion. Installing this
catalyst into a multi-bed radial plug-flow reactor results in an attractive combination of high
production and reduced costs that can be custom made for expansion, retrofit, or grassroots
projects.

Introduction

Ammonia (NH3) is one of the most familiar compounds of nitrogen and hydrogen as well as one
of the world's most valuable industrial and agricultural chemicals. Ammonia is a compound of
nitrogen and hydrogen (and so is covalently bonded) with the formula NH3. Ammonia, either
directly or indirectly, is also a building block for the synthesis of many pharmaceuticals. Although
in wide use, ammonia is both caustic and hazardous. In 2006, worldwide production was estimated
at 146.5 million tones. Ammonia, as used commercially, is often called anhydrous ammonia. This
term emphasizes the absence of water in the material. Ammonia is used throughout the industrial
world as a valuable fertilizer. Ammonia and its compounds, primarily ammonium nitrate and other
ammonium salts, replenish nitrogen in depleted soils. This greatly increases yields of agricultural
crops, especially those that cannot obtain nitrogen from the atmosphere. Common industrial
ammonia synthesis processes consist of a syngas feed stream flowing into a compressor and then
into a catalytic converter bed. The effluent from the converter bed enters a heat exchanger, is
cooled, and then continues into a separation device. Most of the product ammonia is removed,
while some continues in a recycle loop with a purge to remove inserts. The recycle stream enters
another compressor then rejoins the input stream into the reactor.

Ammonia is formed from nitrogen and hydrogen by the reversible reaction given below, and its
production is favored by high pressures and low temperatures.

The objective of this reactor project is to design an ammonia synthesis plant and find the optimum
operating conditions which will yield 1000 metric tons of ammonia per day.
Literature review:

Ammonia is one of the most highly produced inorganic chemicals. There are numerous large-scale
ammonia production plants worldwide, producing a total of 131 million tonnes of nitrogen
(equivalent to 159 million tonnes of ammonia) in 2010. China produced 32.1% of the worldwide
production, followed by India with 8.9%, Russia with 7.9%, and the United States with 6.3%. 80%
or more of the ammonia produced is used for fertilizing agricultural crops. Ammonia is also used
for the production of plastics, fibers, explosives, nitric acid (via the Ostwald process) and
intermediates for dyes and pharmaceuticals. The Romans named the ammonium chloride deposits
found in ancient Libya as 'sal ammoniac us'. Salts of ammonia have been known from very early
times. Ammonia was important to the Muslim alchemists, in the form of sal-ammoniac (nushadir),
as early as the 8th century. It was introduced initially by the Islamic chemist J?bir ibn Hayy?n.
The European alchemists used ammonia since the 13th century. It was also used by dyers in the
middle Ages in the form of fermented urine to alter the colour of vegetable dyes. In the 15th
century, Basilius Valentinus showed that ammonia could be obtained by the action of alkalis on
sal-ammoniac. Gaseous ammonia was first isolated by Joseph Priestley in 1774 and was termed
by him alkaline air. Eleven years later in 1785, Claude Louis Berthollet ascertained its
composition. The Haber-Bosch process to produce ammonia from the nitrogen in the air was
developed by Fritz Haber and Carl Bosch in 1909 and patented in 1910. It was first used on an
industrial scale by the Germans during World War I. Ammonia was used to produce explosives
to sustain their war effort. Before the start of World War I, most ammonia was obtained by the dry
distillation of nitrogenous vegetable and animal products; by the reduction of nitrous acid and
nitrites with hydrogen; and also by the decomposition of ammonium salts by alkaline hydroxides
or by quicklime, the salt most generally used being the chloride (sal-ammoniac).

Today, most ammonia is produced on a large scale by the Haber process with capacities of up to
3,300 metric tons per day. In this process, N2 and H2 gases are allowed to react at pressures of 200
bar.

Sustainable ammonia production:

Ammonia production depends on plentiful supplies of energy, predominantly natural gas. Due to
ammonia's critical role in intensive agriculture and other processes, sustainable production is
desirable. This is possible by using renewable energy to generate hydrogen by electrolysis of
water. This would be straightforward in a hydrogen economy by diverting some hydrogen
production from fuel to feedstock use. For example, in 2002, Iceland produced 2,000 tons of
hydrogen gas by electrolysis, using excess electricity production from its hydroelectric plants,
primarily for the production of ammonia for fertilizer.[3] The Vemork hydroelectric plant in
Norway used its surplus electricity output to generate renewable ammonia from 1911 to 1971,[4]
requiring 15 MWh/Ton of nitric acid. The same reaction is carried out by lightning, providing a
natural source for converting atmospheric nitrogen to soluble nitrates.[5] In practice, natural gas
will remain the major source of hydrogen for ammonia production as long as it is cheapest As an
alternative to the relatively inefficient electrolysis, hydrogen can be generated from organic wastes
(such as biomass or food-industry waste), using catalytic (thermal) reforming. This releases
hydrogen from carbonaceous substances at only 10-20% of energy used by electrolysis and may
lead to hydrogen being produced from municipal wastes at below zero cost (allowing for the
tipping fees and efficient catalytic reforming, such as cold-plasma).[citation needed] Catalytic reforming
is possible in small, distributed (even mobile) plants, to take advantage of stranded biomass/bio
wastes or natural gas deposits. Conversion of such wastes into ammonia solves the problem of
hydrogen storage, as hydrogen can be released economically from ammonia on-demand, without
the need for high-pressure or cryogenic storage.

It is also easier to store ammonia on-board of vehicles than to store hydrogen, as ammonia is less
flammable than gasoline or LPG.

Waste water is often high in ammonia. Because discharging ammonia laden water into the
environment, even in wastewater treatment plants, can cause problems, nitrification is often
necessary to remove the ammonia. This may be a potentially sustainable source of ammonia in the
future because of its abundance and the need to remove it from the water anyway. Alternatively,
ammonia from waste water is sent into an ammonia electrolyzer (ammonia electrolysis) operating
with renewable energy sources (Solar PV and Wind turbine) to produce hydrogen and clean treated
water. Ammonia electrolysis may require much less thermodynamic energy than water electrolysis
(only 0.06 V in alkaline media).

What are the Properties of Ammonia?

 Ammonia is a colorless gas with a characteristic pungent odor.

 The chemical symbol is NH3.
 The ammonia molecule has a trigonal pyramidal shape with a bond angle of 107.8
degree.
 Ammonia’s polarity and, especially, its ability to form hydrogen bonds, make ammonia
highly miscible with water.
 It is known to have the highest specific heat capacity (the measurable physical quantity
that characterizes the amount of heat required to change a body's temperature by a given
amount) of any substance.
 It is lighter than air.
 It is easily liquefied due to the strong hydrogen bonding between molecules; the liquid
boils at −33.3 °C, and freezes at −77.7 °C to white crystals.

How does Ammonia occur in nature?

Ammonia is found in trace quantities in the atmosphere, being produced from the decay process
of nitrogenous animal and vegetable matter. Ammonia and ammonium salts are also found in
small quantities in rainwater, whereas ammonium chloride (sal-ammoniac) and ammonium sulfate
are found in volcanic districts. The kidneys secrete NH3 to neutralize excess acid. Ammonium
salts also are found distributed through all fertile soil and in seawater. Substances containing
ammonia, or those that are similar to it, are called “ammoniacal”. Ammonia is found on Pluto,
Jupiter and, in small amounts, on Uranus. How is ammonia used?About 80% of the ammonia
produced by industry is used in agriculture as fertilizer. Ammonia is also used as a refrigerant gas,
for purification of water supplies, and in the manufacture of plastics, explosives, textiles,
pesticides, dyes and other chemicals. It is found in many household and industrial-strength
cleaning solutions. Household ammonia cleaning solutions are manufactured by adding ammonia
gas to water and can be between 5 and 10% ammonia. Ammonia solutions for industrial use may
be concentrations of 25% or higher and are corrosive.

How can people be exposed to ammonia?

Most people are exposed to ammonia from inhalation of the gas or vapors. Since ammonia exists
naturally and is also present in cleaning products, exposure may occur from these sources. The
widespread use of ammonia on farms and in industrial and commercial locations also means that
exposure can occur from an accidental release or from a deliberate terrorist attack.

Anhydrous ammonia gas is lighter than air and will rise, so that generally it dissipates and does
not settle in low-lying areas. However, in the presence of moisture (such as high relative humidity),
the liquefied anhydrous ammonia gas forms vapors that are heavier than air. These vapors may
spread along the ground or into low-lying areas with poor airflow where people may become
exposed.

What is ammonia’s mechanism of action?

Ammonia interacts immediately upon contact with available moisture in the skin, eyes, oral cavity,
respiratory tract, and particularly mucous surfaces to form the very caustic ammonium hydroxide.
Ammonium hydroxide causes the necrosis of tissues through disruption of cell membrane lipids
(saponification) leading to cellular destruction. As cell proteins break down, water is extracted,
resulting in an inflammatory response that causes further damage.

What are the immediate health effects of ammonia exposure?

Inhalation: Ammonia is irritating and corrosive. Exposure to high concentrations of ammonia in

air causes immediate burning of the nose, throat and respiratory tract. This can cause bronchiolar
and alveolar edema, and airway destruction resulting in respiratory distress or failure. Inhalation
of lower concentrations can cause coughing, and nose and throat irritation. Ammonia's odor
provides adequate early warning of its presence, but ammonia also causes olfactory fatigue or
adaptation, reducing awareness of one's prolonged exposure at low concentrations.

Children exposed to the same concentrations of ammonia vapor as adults may receive a larger dose
because they have greater lung surface area-to-body weight ratios and increased minute volumes-
to-weight ratios. In addition, they may be exposed to higher concentrations than adults in the same
location because of their shorter height and the higher concentrations of ammonia vapor initially
found near the ground.

Skin or eye contact: Exposure to low concentrations of ammonia in air or solution may produce
rapid skin or eye irritation. Higher concentrations of ammonia may cause severe injury and burns.
Contact with concentrated ammonia solutions such as industrial cleaners may cause corrosive
injury including skin burns, permanent eye damage or blindness. The full extent of eye injury may
not be apparent for up to a week after the exposure. Contact with liquefied ammonia can also cause
frostbite injury.

Ingestion: Exposure to high concentrations of ammonia from swallowing ammonia solution

results in corrosive damage to the mouth, throat and stomach. Ingestion of ammonia does not
normally result in systemic poisoning.

How is ammonia exposure treated?

There is no antidote for ammonia poisoning, but ammonia's effects can be treated, and most
people recover. Immediate decontamination of skin and eyes with copious amounts of water is
very important. Treatment consists of supportive measures and can include administration of
humidified oxygen, bronchodilators and airway management. Ingested ammonia is diluted with
milk or water.

Will laboratory tests assist in making treatment decisions if someone has been
exposed to ammonia?

Laboratory testing for ammonia exposure will not be useful in making emergency treatment
decisions. Medical tests that can detect ammonia in blood or urine are available. However, because
ammonia is normally found in the body, these test results cannot serve as biomarkers of exposure.
After exposure to low levels, ammonia is either rapidly cleared from the body or metabolized to
compounds found endogenously at appreciable levels. Clinical indices of body ammonia or
nitrogen levels after exposure to exogenous ammonia have shown no or minimal change from prior
levels. Exposure to high concentrations is immediately and overtly toxic, generally providing an
adequate basis for diagnosis.

How is Ammonia Synthesized?

Haber-Bosch process: The Haber process, also called the Haber–Bosch process, is the nitrogen
fixation reaction of nitrogen gas and hydrogen gas, over an enriched iron or ruthenium catalyst,
which is used to industrially produce ammonia. The Haber process is important because previous
to its discovery, ammonia had been difficult to produce on an industrial scale, and fertilizer
generated from ammonia today is responsible for sustaining one-third of the Earth's population.
Synthesis of ammonia was done by using an iron catalyst promoted with K2O, CaO and Al2O3:

N2 (g) + 3 H2 (g) --> 2 NH3 (g)

This is done at between 300 and 550 degree C, passing the gases over four beds of catalyst, with
cooling between each pass to maintain a reasonable equilibrium constant, a quantitative index of
the relative amounts of products and reactants present at equilibrium. . On each pass only about
15% conversions occurs, but any unreacted gases are recycled, so that eventually an overall
conversion of 98% can be achieved. The steam reforming, shift conversion, carbon dioxide
removal, and methanation steps each operate at absolute pressures of about 2.5–3.5 MPa (25–35
bar), and the ammonia synthesis loop operates at absolute pressures ranging from 6–18 MPa (60–
180 bar), depending upon which proprietary design is used. The bar is a unit of pressure equal to
100 kilo pascals. Mpa refers unit of pressure known as Pascal. Prioir to World War I, most
ammonia was obtained by the dry distillation of nitrogenous vegetable and animal waste products,
including camel dung, where it was distilled by the reduction of nitrous acid and nitrites with
hydrogen; in addition, it was produced by the distillation of coal, and also by the decomposition
of ammonium salts (NH4Cl) by alkaline hydroxides such as quicklime (CaO), the salt most
generally used being the chloride (sal-ammoniac) thus:

2 NH4Cl + 2 CaO --> CaCl2 + Ca (OH) 2 + 2 NH3

Catalytic hydrogenation: These days, the typical modern ammonia-producing plant first converts
natural gas (i.e., methane) or liquefied petroleum gas (such gases are propane and butane) or
petroleum naphtha into gaseous hydrogen. The process used in producing the hydrogen begins
with removal of sulfur compounds from the natural gas (because sulfur deactivates the catalysts
used in subsequent steps). Catalytic hydrogenation, the addition of hydrogen converts organo-
sulfur (RSH) compounds into gaseous hydrogen sulfide:

H2 + RSH --> RH + H2S (g)

 The hydrogen sulfide is then removed by passing the gas through beds of zinc oxide where
it is adsorbed and converted to solid zinc sulfide:

H2S + ZnO --> ZnS + H2O

 Catalytic steam reforming (method of producing hydrogen) of methane (CH4) is then used
to form hydrogen plus carbon monoxide:

CH4 + H2O --> CO + 3 H2

  In the next step, the water gas shift reaction is used to convert the carbon monoxide into
carbon dioxide and more hydrogen:

CO + H2O --> CO2 + H2

 The carbon dioxide is then removed either by absorption processes. Adsorption is the
adhesion of atoms, ions, biomolecules or molecules of gas, liquid, or dissolved solids to a
surface.
 The final step in producing the hydrogen is to use catalytic meth nation to remove any
small residual amounts of carbon monoxide or carbon dioxide from the hydrogen:

CO + 3 H2 --> CH4 + H2O

CO2 + 4 H2 --> CH4 + 2 H2O

 To produce the desired end-product ammonia, the hydrogen is then reacted with nitrogen
(derived from process air) using a magnetite catalyst under high pressure to form anhydrous
liquid ammonia by Haber’s process:

3 H2 + N2 --> 2 NH3

What are the uses of Ammonia?

 As a Fertilizer: Roughly, 83% of ammonia is used as fertilizers either as its salts or as

solutions.
 As a cleaner: Household ammonia is a solution of NH3 in water (i.e., ammonium
hydroxide) used as a general purpose cleaner for many surfaces.
 As a refrigerant: Due to its good vaporization properties, ammonia is an attractive
refrigerant.
 As a fuel: Liquid ammonia was used as the fuel of the rocket airplane. Although not as
powerful as other fuels, it left no soot in the reusable rocket engine and its density
approximately matches the density of the oxidizer, liquid oxygen, which simplified the
aircraft's design.
 Ammonia contributes significantly to the nutritional needs of terrestrial organisms by
serving as a precursor to food and fertilizers.

DESCRIPTION OF THE PROCESS

With respect to the reactor, three questions needed to be addressed in modeling a typical ammonia
synthesis plant:

1. What kind of reactor: plug flow or Gibbs?

2. Under what operating conditions: adiabatic or isothermal?
3. At what specified temperatures and pressures?
The first question, for all practical purposes, was not a choice to make; the simulation was run with a
Gibbs reactor because of insufficient kinetic data available to execute a plug flow reactor simulation.
This was due to proprietary rights on the catalysts and their resulting kinetic data. The remaining two
questions were answered together. In choosing between an adiabatic or isothermal reactor, pressure was
varied in the adiabatic reactor while holding the temperature of the feed constant, and temperature was
varied in the isothermal reactor while holding its pressure constant. The adiabatic Gibbs reactor gave
the best results near 100 bar as seen on the graph entitled "Adiabatic Gibbs Reactor." This is close to the
point of intersection of the product flow line and the purity line, analogous to the point of equilibrium
between supply and demand in economics. Pressure of 100 bar represented the best trade-off between
the amount of NH3 produced in the product stream and the purity of the product stream. This pressure
was chosen as the constant operating pressure of the isothermal Gibbs reactor. The isothermal Gibbs
reactor gave the best results near 275 oC as seen on the graph entitled "Isothermal Gibbs Reactor." This
temperature has the same implications as the pressure of 100 bar did for the adiabatic Gibbs reactor.
The final ammonia plant simulated in ASPEN was based on an adiabatic Gibbs reactor operated
at a pressure of 100 bar and modeled with the Peng-Robinson thermodynamic package. Peng-
Robinson is well suited for use with gas and hydrocarbon processing and refining. The input feed
stream for the process was 5500 kmol/hr at 40 oC at the following mole percentages: 74.2% H2,
24.7% N2, 0.8% CH4, and 0.3% Ar.(1) The product (bottoms) stream from the flash tank produced
ammonia at a rate of 1016 metric tons per day (2486 kmol/hr) at a purity of 98.96%. The recycle
purge was operated at 7.25% of the flash tops stream or 1.49% of the input feed stream. The
remaining pieces of the process flow diagram included two multistage compressors, a heat
exchanger, and a flash vessel. The first compressor was modeled as an ideal three stage compressor
and increased the pressure of the input feed stream to 100 bar before entering the reactor. The heat
exchanger following the reactor used ammonia (assumed to be produced by the plant) as the
refrigerant to cool down the process stream from 375 oC to -30 oC before entering the flash vessel.
The flash vessel was also operated at -30 oC and had a pressure drop of 5 bar. The second
compressor was an ideal two stage compressor and increased the pressure of the recycle stream to
100 bar before merging with the feed stream and entering the reactor.

The Haldor-Topsoe Ammonia Synthesis Process:

Due to the lack of kinetic data, attempts were made to obtain physical plant data regarding
production rates, reactor layouts and sizes, and other operating conditions. Plants contacted
included Pacific Ammonia Incorporated in Kitimat, British Columbia, Canada; Dupont in
Beaumont, Texas; and Haldor-Topsoe in Clear Lake, Texas. The Haldor-Topsoe plant most closely
approximated the simulated ammonia plant. Thus, this plant and its associated data were chosen
as the real world model of the simulation.
The Haldor-Topsoe plant produces over 1500 metric tons per day of NH3 using a two bed
converter with internal heat exchangers. This converter is based on the iron-magnetite catalyst, the
most commonly used today. Their recycle purge operates at 7.26% of the separation stream or
1.86% of the input feed stream. These numbers strongly agree with the purges of 7.25% and 1.49%
in the simulated plant. Comparisons of the entrance stream into and exit stream from the reactors
can be made in the following table.

As evidenced, the simulation yielded similar purge percentages and comparable stream
compositions. Slightly higher impurity levels of the Haldor-Topsoe feed, resulting in catalyst
inhibition, may account for some of the differences. The reactor sizes given were 30 m3 and 75
m3 for the first and second beds, respectively. Of this volume, approximately 2/3 is taken up by
theiron-magnetitecatalyst.

EconomicOptimization

There are a number of means to further optimize these processes. These are not simulated in
ASPEN due to the difficulty in obtaining detailed quantitative data but are presented here as
options that would result in a more efficient and economically advantageous process. The primary
areas of focus in economic optimization are compression costs and reactor efficiency. High
operating pressures applied in industrial practice (>100 bar) are usually necessary for a favorable
equilibrium position and high rate of reaction, as well as ammonia recovery at higher temperatures
to reduce refrigeration costs. However the compression power necessary to achieve such pressures
is one of the most significant expenses in a plant. A means to reduce this cost is to install centrifugal
compressors driven by steam turbines, equipment used in modern plants today that take advantage
of steam produced elsewhere in the process.(3)

While this is of some advantage, it is not the most significant improvement that can be made. If
reactor efficiency can be increased such that lower synthesis pressures can be employed without
compromising ammonia conversion, then the costs related to compression and efficiency can be
truly reduced and the process economically optimized. This can be achieved through the use of a
high activity ruthenium-based synthesis catalyst relatively new to the market. The catalyst is to be
used in conjunction with modern reactor designsconstructedspecificallyforitsoptimalemployment.

Catalyst

The industrial process of ammonia synthesis has been generally based on the reaction of hydrogen
and nitrogen at high pressure over a catalytic surface. Traditionally the catalyst of choice is an
iron-based catalyst with magnetite as its major component. An attractive alternative to this
catalytic system is proposed here as a means of increasing ammonia conversion at lower pressures,
and thus reducing energy consumption in compressors at a lower capital cost.

The proposed system utilizes a promoted ruthenium catalyst deposited on thermally modified
active carbon, forming porous cylindrical pellets about 0.8 mm in diameter and 3-5 mm long,
which has been available to industry relatively recently.(4) This catalyst is up to twenty times more
active than fused iron catalyst at relatively high conversion degrees. More importantly, although
temperature variations have similar effects on the two catalysts, the effects of ammonia
concentration are significantly different. Iron-based catalyst activity depends strongly on PNH3
(partial pressure of ammonia). As PNH3 increases from 1 mol% to 10 mol% the rate of the process
decreases 10 to 25-fold. In contrast, the activity of ruthenium-based catalysts is only slightly
affected by changes in PNH3, as well as changes in total pressure. Promoted ruthenium catalyst
deposited on active graphite therefore has been found to have excellent low pressure and low
temperature performance.(5) This is of great importance to industrial practice, taking into account
contemporary tendencies to lower the applied pressure and thus reduce energy consumption.

Further benefits of using the ruthenium-based catalyst are found in capital cost savings. As lower
pressures are used in the process, there is greater flexibility in process compressor driver selection.
Thinner-walled and lighter vessels, piping, and fittings can be employed safely, all of which are
equipment more commonly fabricated world-wide and therefore cheaper. This new catalyst opens
a world of possibilities for industrial ammonia synthesis optimization, maintaining high ammonia
conversion and safety standards at significantly reduced costs and increased profit.

Kellogg Advanced Ammonia Process

In 1979, British Petroleum approached M.W. Kellogg to participate in the development of a new
ruthenium-based catalyst. It was known at that time that replacing the conventional iron-based
catalyst, which was used for over 80 years, with this new catalyst would increase productivity.
Several pilot plant tests were performed using ruthenium supported on a proprietary carbon
structure with various co-promoters. (6) It was evident that significant economic benefits would
be attained with this new catalyst, and so it was chosen to be an integral part of what is now known
as the Kellogg Advanced Ammonia Process (KAAP).

KAAP can be implemented in one of three ways: as an expansion to an already existing plant, as
a retrofit design to an already existing plant, or as a grassroots design when building a brand new
plant. In 1988, KAAP had its first commercial exposure after Ocelot Ammonia Company in
Kitimat, British Colombia (now known as Pacific Ammonia Incorporated or PAI), contracted
M.W. Kellogg to evaluate its existing ammonia plant for potential capacity increases and to
provide a suitable retrofit design. This company's ammonia plant was ideal for KAAP's first
demonstration since its synthesis loop had separate feed streams for hydrogen and nitrogen and
allowed the KAAP reactor to be run under a variety of stream ratios (7).

The KAAP system was successfully started up in November of 1992. It consisted of a KAAP
reactor which was installed downstream from the magnetite converter already in existence. This
KAAP reactor was a two-bed radial flow converter with a unique proprietary sealing system which
avoided hot spots within the catalyst bed. The KAAP catalyst was loaded in its oxidized state, just
as most catalysts are, although it is only active in the reduced state. Therefore, fresh synthesis gas,
which heated the catalyst bed to ~300o, was used to for the reduction process. The synthesis loop
operated at the original design pressure of 2000 psia. Partially preheated feed exits a 2-bed Kellogg
converter loaded with magnetite catalyst and enters a steam superheater and generator, which
generates a pressure of 3000 psia. This feed stream, containing 15% ammonia, then passes into the
KAAP converter through a side inlet to the first bed. When the gas leaves the second bed, ammonia
concentration is increased to about 19%. A continuous purge is required in this retrofit because the
expanded plant contains more inerts than in the original synloop. After the entire KAAP retrofit
was completed, PAI had an energy savings of 0.6 mmBTU/mt.(8) This more efficient and highly
flexible system has been very easy to operate and has paved the way for grassroots facilities.

Grassroots designs are different from retrofit and expansion designs in that they use 3 and 4 bed
intercooled reactors. The first bed uses conventional iron catalyst while the remaining beds utilize
the highly active KAAP catalyst. The reason for this is so that the iron catalyst can take advantage
of high ammonia reaction rates at low ammonia concentrations. As the reaction progresses,
however, the ammonia concentrations increase, and the iron catalyst loses its effectiveness.(9) The
KAAP catalyst is then used to produce high exit ammonia concentrations at low pressures, since
it can be used at high ammonia concentrations.

The grassroots ammonia plants typically utilize KAAP in conjunction with KRES, the Kellogg
Reforming Exchange System. Together, these processes have a multitude of benefits, several of
which stem from the sole implementation of KAAP. The lower pressure synthesis loop, which
leads to significant capital savings, results from the use of a single case gas compressor with
thinner walled and lighter vessels, fittings, and pipings. This synthesis loop is also advantageous
in that it uses energy more efficiently by recovering heat at a much higher temperature, yielding a
40% decrease in energy conversion relative to conventional designs.(10) Since the synthesis loop
is less complex than in other plants, operator attention is expected to be less as well. In addition,
all of these benefits bring with them an expectation of greater reliability.

Economic and environmental aspects:

When it was first invented, the Haber process needed to compete against another industrial process,
the Cyanamide process. However, the Cyanamide process consumed large amounts of electrical
power and was more labor-intensive than the Haber process.

The Haber process now produces 450 million tonnes of nitrogen fertilizer per year, mostly in the
form of anhydrous ammonia, ammonium nitrate, and urea. Three to five percent of the world's
natural gas production is consumed in the Haber process (around 1–2% of the world's annual
energy supply). In combination with pesticides, these fertilizers have quadrupled the productivity
of agricultural land.

With average crop yields remaining at the 1900 level the crop harvest in the year 2000 would have
required nearly four times more land and the cultivated area would have claimed nearly half of all
ice-free continents, rather than under 15% of the total land area that is required today.
Due to its dramatic impact on the human ability to grow food, the Haber process served as the
"detonator of the population explosion", enabling the global population to increase from 1.6 billion
in 1900 to today's 7 billion. Nearly 80% of the nitrogen found in human tissues originated from
the Haber-Bosch process. Since nitrogen use efficiency is typically less than 50%, farm runoff
from heavy use of fixed industrial nitrogen disrupts biological habitats.

CONCLUSION

The proposed ammonia synthesis design produces 1,016 metric tons/day of ammonia at a feed of
5,500 kmol/hr. Although the lack of kinetic data deterred the completion of the plug flow
simulation, a Gibbs reactor successfully emulated the desired results. The Haldor-Topsoe plant in
Clear Lake, Texas, was chosen as the model for the conventional ammonia plant due to its
comparable operation to the proposed simulation and its use of iron-based catalyst. This process
could be further optimized by lowering compression costs and utilizing a more efficient reactor.
Replacing the conventional catalyst with the new ruthenium-based catalyst in a multi-bed reactor
can achieve these goals. The industrial process may be safely and productively operated at lower
temperatures, thus reducing costs and increasing profit.

M.W. Kellogg takes full advantage of this superior catalyst in its breakthrough technology known
as the Kellogg Advanced Ammonia Process, or KAAP. KAAP, implemented as either a retrofit,
expansion, or grassroots design, has proven to have significant benefits, such as reduced capital
costs and energy savings. Kellogg's new ammonia synthesis configuration leads to a economically
advantageous and flexible ammonia plant.
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