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