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Table of Contents
Abstract
I. Introduction
II. Description of the Process
A. ASPEN Simulation
B. Haldor-Topsoe Plant
A. Conventional Magnetite
B. Latest Breakthrough--Ruthenium-Based
A. General Description
C. Grassroots Application
VI. Conclusion
VII. Endnotes
VIII. References
IX. Appendix
Abstract
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.
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.
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.
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.
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.
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
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
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
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.
Stephen A. Noe, "Catalytic Reactor Bed", US Patent 5 250 270 (1993) to Kellogg
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