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Reactor Project: Ammonia Synthesis

Josue Villesca, Vidya Bala, Alejandra Garcia

Table of Contents

Abstract
I. Introduction
II. Description of the Process

A. ASPEN Simulation

B. Haldor-Topsoe Plant

III. Economic Optimization


IV. Catalyst

A. Conventional Magnetite

B. Latest Breakthrough--Ruthenium-Based

V. Kellogg Advanced Ammonia Process

A. General Description

B. Retrofit for Pacific Ammonia Incorporated

C. Grassroots Application

VI. Conclusion
VII. Endnotes
VIII. References
IX. Appendix

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.

I. Introduction

The world's first 1000 metric ton per day single train ammonia synthesis plant was
operated by the Mississippi Chemical Corporation in Yazoo City, Mississippi, USA.

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, 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 inerts. 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.

II. 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.
After obtaining the optimum operating conditions for both the adiabatic and
isothermal reactors, the adiabatic was chosen over isothermal for two reasons:
1. Adiabatic reactors are more common in industry.
2. It does not require temperature regulation.

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(2)
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 the iron-magnetite
catalyst.

III. Economic Optimization

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 designs constructed specifically for its optimal employment.

IV. 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.

V. 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.

VI. 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.

VII. Endnotes

1. Catalytic Ammonia Synthesis: Fundamentals and Practice, edited by J.R.


Jennings
Plenum Press, New York, NY, 1991.

2. Phone conversation with Haldor-Topsoe Ammonia Synthesis Plant in Clear


Lake, Texas.

3. Stephen A. Noe, "Catalytic Reactor Bed," US Patent 5 250 270 (1993) to


Kellogg Company

4. Zbigniew Kowalczyk, Slawomir Jodiz, Jan Sentek, "Studies on Kinetics of


Ammonia Synthesis Over Ruthenium Catalyst Supported on Active Carbon,"
Applied Catalysis A: General. vol 138 (1996) p.83-91
5. Ibid

6. "KAAP: Kellogg Advanced Ammonia Process", The M.W. Kellogg Company

7. Ibid
8. Ibid

9. T.A. Czuppon, S.A. Knez, R.B. Strait, "Commercial Review of KAAP and
KRES" The M.W. Kellogg Technology Co., presented at AIChE Safety Symposium
(Sept. 1996) Boston, MA.

10. J.R. Leblanc, "Ammonia 2000 Kellogg Technology for the Future", Asia
Nitrogen `96, Singapore

VIII. References

Catalytic Ammonia Synthesis: Fundamentals and Practice, edited by J.R. Jennings


Plenum Press, New York, NY, 1991.

"Ammonia", Kirk-Othmer Encyclopedia of Chemical Engineering Technology, 4th


ed., Vol 2, (1991) pp. 638-691.

Anders Nielsen, Jorgen Kjaer. Bennie Hansen. "Rate Equation and Mechanism of
Ammonia Synthesis at Industrial Conditions", Journal of Catalysis, Vol 3, (1964)
pp. 68-79.

D.C. Dyson, J.M. Simon, "A Kinetic Expression with Diffusion Correction for
Ammonia Synthesis on Industrial Catalyst", I & EC Fundamentals, Vol 7, (1968)
pp. 604-610.

"Ammonia", Ullman's Encyclopedia of Industrial Chemistry, Vol A2, (1980) pp.


152-209.

Zbigniew Kowalczyk, Slawomir Jodiz, Jan Sentek, "Studies on Kinetics of


Ammonia Synthesis Over Ruthenium Catalyst Supported on Active Carbon",
Applied Catalysis A: General, Vol 138, (1996) pp. 83-91.

Stephen A. Noe, "Catalytic Reactor Bed", US Patent 5 250 270 (1993) to Kellogg
Company.

"Ammonia", The M.W. Kellogg Technology Company.

J.R. Leblanc, "Ammonia 2000 Kellogg Technology for the Future", Asia Nitrogen
`96, Singapore.

T.A. Czuppon, S.A. Knez, R.B. Strait, "Commercial Review of KAAP and KRES",
The M.W. Kellogg Technology Co., presented at AIChE Safety Symposium (Sept.
1996) Boston, MA.
"KAAP: Kellogg Advanced Ammonia Process", The M.W. Kellogg Company.

IX. Appendix