Design of a CO2 Absorption System in an

Ammonia Plant

Chemical Engineering 403

November 10, 1997

Jason Underwood, Group Leader

Gwendolyn Dawson
Christin Barney
Abstract

The purpose of this project was to design and model a system to separate carbon
dioxide from the feed stream for an ammonia synthesis plant. The CO 2 is then purified
in order to be sold to pay the operating expenses of separation. This design group
developed an intricate separation process consisting of an absorber and a stripper
which results in only trace amounts of CO2 being left in the feed stream. Furthermore,
most of this separated CO2 is recovered, at 99.6% purity, so that it can be sold. This
separation process is completed with the help of a hot potassium carbonate solvent
that is almost completely regenerated.

Introduction

It is necessary to remove the carbon dioxide from the feed stream because it poisons
the iron catalyst found downstream in the ammonia synthesis process. The poisoning
is caused by oxygen, from traces of carbon dioxide or water, absorbing onto the iron
surface and preventing nitrogen absorption. This deactivation process is only
sometimes reversible by reduction with hydrogen. Permanent deactivation can occur
due to exposure over the course of several weeks to oxygen-containing compounds
such as carbon dioxide. The large expense and difficulty in changing out a catalyst
makes preventing their poisoning important.

This carbon dioxide removal is usually done with an absorber-stripper process. The
unit should be located between the low-temperature water gas shift and the
methanation units, just before the ammonia synthesis beds in a typical ammonia plant.
Aspen was used to model the absorber-stripper system. The general design is such that
a carbon dioxide absorbing solvent flows down the absorber while the feed gas flows
up. Then, the rich solvent is regenerated in the stripper at low pressure before
recycling back to the absorber. Next, water is condensed out of the CO 2 that was
removed in the stripper. Figure 1 in the Appendix shows the flow diagram generated
in Aspen of this process. An important decision in the design process was which
solvent to use. Historically, water was the first solvent used in this process but is no
longer used in new plants due to hydrogen losses along with the carbon dioxide.

Monoethanolamine (MEA) is commonly used in existing plants, but hot potassium

carbonate is being used in most new plants. It has a high CO2 capacity and provides
negligible hydrogen losses. The choice was mainly between MEA and potassium
carbonate. This project group chose potassium carbonate solution as its solvent for
reasons which will be detailed later in this report.

Reactions

Several reactions occur in the absorber that remove the carbon dioxide from our feed
stream. Because many of these reactions are ionic reactions, this system can only be
realistically modeled with the 'elec' option in Aspen. In addition to the reactions
described below, the dissociation of water into hydrogen and hydroxide ions is also
modeled. First of all in our system, our solvent, potassium carbonate, dissociates by
the following reaction:

K2CO3 2K+ + CO32-

This reaction sets up the carbonate system in the solution in the absorber. The
carbonate system consists of the three equilibrium reactions of carbonic acid:

H2CO3 + H20 H3O+ + HCO3-

HCO3- + H2O H3O+ + CO32-
CO2 + 2H2O H3O+ + HCO3-

The last reaction describes exactly how the carbon dioxide in the feed stream gets
absorbed into the solution. This carbon dioxide reacts to form mostly bicarbonate ion
which then exists in an equilibrium relationship with potassium bicarbonate as in the
following reaction:

K+ + HCO3- KHCO3

The bottoms stream coming out of the absorber consists of potassium bicarbonate,
bicarbonate ion, carbonate ion, and carbonic acid along with slight impurities. In this
way, all of the carbon dioxide in the feed stream is absorbed into the bottoms solution
that then continues on to the stripper.
In the stripper, essentially, the reverse reactions occur. Equilibrium shifts to the left
side of the above carbonate system equations. This shift in equilibrium occurs largely
because of the huge difference in pressures between the absorber and the stripper. The
stripper removes the carbon dioxide from the solvent and sends in on to be purified
and sold. The regenerated solvent is then recycled back to the absorber to complete
the cycle again. This solvent can be recycled indefinitely, and new solvent needs to be
added to the system only to make up for small solvent losses in the stripper.

Discussion

When designing a carbon dioxide absorption system for an ammonia synthesis plant,
several important design elements must be considered. First of all, the type of solvent
used in the absorber to remove carbon dioxide is an important decision. A solvent
must be chosen based on economics, purity of products, and industry standards.
Secondly, the purity of the stream that is to be sent on to the rest of the ammonia
synthesis plant must be considered. Small amounts of impurities, especially carbon
dioxide, can adversely affect the rest of the downstream process. Thirdly, the purity of
the carbon dioxide product stream must be considered. Less pure product carbon
dioxide is easier to make but is not worth as much when sold on the open market.

The purity of the two product streams will be discussed here while the solvent choice
will be considered in the next section. The first product stream consists of mainly
hydrogen and nitrogen which will be combined in a later part of the process to make
ammonia. This stream may also contain water, and this will not adversely affect the
downstream process. Most importantly, this stream must not contain appreciable
amounts of carbon dioxide because this compound is a catalyst poison in the ammonia
synthesis process. Ideally, this stream will also contain very little carbon monoxide as
well. In this particular project, however, the feed stream into the absorber contains a
significant amount of carbon monoxide that will not be removed in the absorber. In a
normal situation, this carbon monoxide would already be converted to carbon dioxide
before the stream goes into the carbon dioxide absorber.

The second product stream is the pure carbon dioxide stream that comes out of the
stripper. Because high purity carbon dioxide yields a high market price, we chose to
produce a product gas that is 99.5% carbon dioxide. The impurity in the stream is
mostly water. This high purity allows us to sell our product carbon dioxide to
industries that demand only the purest carbon dioxide, and because of this, we can get
as much as $50/ton for our product carbon dioxide.

Choice of Solvent
The solvent to be used in the absorber is a very important design consideration.
Traditionally, monoethanolamine or diethanolamine was chosen to adsorb the carbon
dioxide from the feed. Now, however, most new plants are designed to use potassium
carbonate for many crucial and convincing reasons.

First of all, potassium carbonate is a more efficient absorber of carbon dioxide than
either monoethanolamine or diethanolamine. This means that for a given amount of
solvent, potassium carbonate can absorb more carbon dioxide than the other two
common solvents, Why is this important? If less solvent is needed, then piping
systems and absorber volume can be smaller. In addition, the cost of the solvent is less
because less is needed and potassium carbonate is cheaper than the traditional
solvents.

Secondly, the use of potassium carbonate over the other two solvents eliminates the
need for a heat exchanger between the absorber and the stripper. In a potassium
carbonate system the stripper runs cooler than the absorber. This is not true for the
traditional solvents. Traditional solvents require the heating of the bottoms stream
from the absorber before it reaches the stripper, but a potassium carbonate system
requires no such heating. The elimination of this heat exchanger increases profitability
of the plant because heat exchangers are both costly to purchase and maintain.

Thirdly, potassium carbonate increases the safety of the carbon dioxide removal
system. Traditional solvent absorb not only carbon dioxide but small amounts of
hydrogen as well. This hydrogen then continues through the stripper and the out the
top stream with the carbon dioxide. Beside decreasing the purity of the product carbon
dioxide stream, this hydrogen poses a safety threat, Flashing off hydrogen can cause
fires or explosions if proper precautions are not taken. Using potassium carbonate
reduces the risk of such accidents.

Finally, the most convincing argument for the use of potassium carbonate as a solvent
is that this is the present industry standard. There are many plants that use
monoethanolamine and diethanolamine, but these plants were built a long time ago
and don't yet have potassium carbonate capabilities. Most new plants use potassium
carbonate, and even some existing plants are deciding to convert over to potassium
carbonate as their solvent of choice. This evidence shows that potassium carbonate is
significantly better than the traditional solvents.

Discussion of Optimal Design

In order to remove CO2 from the feed stream, two main vessels are needed: an
absorber and a stripper. Inside the absorber, chemical reactions will occur in which
the CO2 is chemically absorbed onto the solvent and this compound, along with water,
will flow out the bottom of the absorber. That stream will then go through a flash
chamber to lower the temperature and pressure of the liquid (and to separate out some
CO2) before proceeding onto the stripper where the CO2 will separate out from the
solvent. Both the absorber and stripper were modeled in Aspen using the Radfrac
modules.

Absorber Design

The absorber was modeled using three theoretical stages and no condenser or reboiler.
The K2CO3 and water stream, the solvent, flowed in from above the top stage while
the feed stream from the low-temperature water-gas shift flowed into the column at
the bottom. Both the feed stream and the hot potassium carbonate solution entered the
absorber at 250 degrees Celsius and 50 bar. The solvent entered as a liquid while the
feed stream came in as a gas. The following is a table showing data from the two
streams entering the absorber and the streams coming out of it.

Feed Stream Solvent Bottoms Feed to Ammonia

Temperature (C) 250 250 268 241
Pressure (bar) 50 50 38 40
Vapor Fraction 1.00 0 0 1.00
Mole Flow (lbmol/hr) 19462 2653 9378 14650
Mass Flow (lb/hr) 303920 182133 310749 175304
Mole Flow (lbmol/hr)
Water 6246 1551 5143 2353
H2 7441 - .534 7440
N2 2978 - .101 2978
CO 1795 - .582 1794
CO2 919 - 625 trace
AR 37 - .03 37
KHCO3 - - - trace
CH4 46 - .112 46
K2CO3 - 1102 - -
+
K - - 2205 -
H3O+ - - trace -
-
HCO3 - - 596 -
OH- - - 7 -
2-
CO3 - - 801. -
As the table shows, the absorber does a very good job of removing CO2 from the feed
stream coming out of the low-temperature water-gas shift. Only a trace amount of
CO2 is remaining in the stream that will be sent on to the ammonia synthesis portion
of the plant. The CO2 is all in the bottom stream-mostly in the form of dissolved CO2,
but some of it is also in the ionized state. The absorber operates across a temperature
range from 268 degrees Celsius to 241 degrees Celsius. There is a pressure drop of 2
bar down the column (from 40 bar at the top to 38 bar at the bottom).

The absorber was sized and an economic analysis completed using the Aspen cost
package. It was determined that the optimal size of the column is 36 feet in length and
12 feet in diameter. There will be 11 actual trays, and the cost of the column will be
almost $500,000. The absorber, like all parts of the plant, must be made of reinforced
stainless steel with thick walls due to the high pressures in the system. Also, a small
amount of an anti-corrosive agent must be added to the solvent stream to prevent
corrosion in the system. A commonly used agent is vanadium pentoxide. A catalyst
can also be added to the system if more CO2 needs to be removed from the system. In
this case, a catalyst is not needed. However, one might be necessary depending on
how much CO2 is fed into the absorber.

The purified feed stream is sent from the top of the absorber to the ammonia synthesis
reactors. Essentially, we have completed the goal of our project: to remove as much
CO2 as possible from the feed stream in order to prevent catalysis poisoning
downstream. However, for economic reasons it is beneficial to regenerate the solvent
and sell the carbon dioxide. The remaining two flash units and the stripper are
designed to purify CO2 and regenerate solvent.

First Flash Unit

After leaving the bottom of the absorber, the solvent and CO2 travel to a flash unit
which will create a vapor stream consisting of water and some of the CO2 in the
system. The flash also serves to lower the temperature and pressure of the solvent
stream in order to allow it to enter the stripper at optimal conditions for separation of
CO2 from the solvent. The following table shows the data from the stream entering the
flash and the two outlet streams.

Stream From Absorber CO2 and Water Stream to Stripper

Temperature (C) 268 121 121
Pressure (bar) 38 5 5
Vapor Fraction 0 1.00 0
Mole Flow (lbmol/hr) 9378 353 8718
Mass Flow (lb/hr) 310749 13999 37565
Mole Flow (lbmol/hr)
Water 5143 57 4785
H2 .534 .533 .001
N2 .101 .101 -
CO .582 .572 .01
CO2 625 294 23
AR .03 .03 .001
KHCO3 - - -
CH4 .112 .096 .016
K2CO3 - - -
K+ 2205 - 2205
+
H3O trace - trace
HCO3- 596 - 1205
-
OH 7 - .085
CO32- 801 - 500

The absorber was sized and an economic analysis completed using the Aspen cost
package. It was determined that the optimal flash unit is 6.67 feet in diameter and will
cost approximately $40,200.

Stripper Design

After running through the flash, the stream with primarily water and ions is sent to the
top of the stripper. In the stripper, the reverse of the reactions in the absorber occur.
Here, the CO2 is released from the solution as a vapor and, along with steam, travels
out the top of the stripper. The remaining solution, which is almost entirely potassium
and carbonate ions, comes out the bottom of the stripper and is sent back to the
absorber to be re-used. The solution will react in the stripper with steam coming in
from the bottom. The stripper contains 10 theoretical plates and there is almost no
pressure drop across the column (2 bar at top to 1.8 bar at bottom). The temperature
ranges from 141 degrees Celsius at the top of the column to 147 degrees Celsius at the
bottom. The stripper utilizes a condenser. The ratio of the liquid flowing in the top of
the column to the distillate is approximately 2.65:1. The following table show the
streams coming in and out of the stripper:

Feed to Stripper Water CO2 stream Regenerated Solvent

Temperature (C) 121 120 141 147
Pressure (bar) 5 10 2 1.8
Vapor Fraction 0 1.00 1.00 0
Mole Flow(lbmol/hr) 8718 1653 3283 7635
Mass Flow (lb/hr) 297298 29788 73978 253107
Mole Flow(lbmol/hr)
Water 4785 1653 2712 4264
H2 .001 - .001 trace
N2 - - - trace
CO .01 - .01 trace
CO2 23 - 571 .185
AR .001 - .001 trace
KHCO3 - - - -
CH4 .016 - .016 trace
K2CO3 - - -
+
K 2205 - - 2205
H3O+ trace - - trace
-
HCO3 1205 - - 118
-
OH .085 - - 10
CO32- 500 - - 1038

Using the Aspen cost program, the stripper was found to be 7.5 feet in diameter and
28 feet long. It will cost $160,400 including the condenser.

Second Flash Unit

The regenerated solvent is now ready to be sent back to the absorber. Before the
CO2 can be sold, though, it must be separated from the water. This is done in a final
flash tank. The CO2 and steam streams from both the first flash tank and the stripper
are combined and fed into a final flash tank in which the pressure is 5 bar and the
temperature is lowered to 10 degrees C. In this manner, the CO2 is removed as a vapor
and the water is liquefied so that it can be used elsewhere in the plant. The following
table shows the streams into and out of our final flash unit:

From first Flash From Stripper Pure CO2 Pure Water

Temperature (C) 121 141 10 10
Pressure (bar) 5 2 5 5
Vapor Fraction 1.00 1.00 1.00 0
Mole Flow (lbmol/hr) 353 3283 855.672 2780
Mass Flow (lb/hr) 13999 73978 37565 50413
Mole Flow (lbmol/hr)
Water 57 2712 2.226 2766.786
H2 .533 .001 .533 <.001
N2 .101 - .101 <.001
CO .572 .01 .557 .025
CO2 294 571 852.137 12.858
AR .03 .001 .028 .003
KHCO3 - - - -
CH4 .096 .016 .089 .025
K2CO3 - - - -
+
K - - - -
H3O+ - - - .014
-
HCO3 - - - .014
OH- - - - trace
2-
CO3 - - - trace

This flash chamber will cost $43,400 according to Aspen.

Analysis of Design

This design clearly meets the stated goals of the project. The ammonia stream is
purged of CO2, ensuring that no catalyst will be poisoned downstream. Also, 93% of
the CO2 entering the system is recovered at a purity of 99.6%. This CO2 amounts to
164,663 tons produced per year. At the current selling price of $45-50 a ton, the
CO2 recovery system generates $8,233,147 in revenue for the plant. Also, virtually all
of the K2CO3 is regenerated. A comparison of the regenerated solvent to the original
solvent feed indicates there is more water and CO32- in the system and less HCO3-.
The water can be removed through a simple separation process. The equilibrium
between HCO3- and CO32- can probably be shifted more in favor of HCO3- if
necessary.

There is a definite economic benefit for using K2CO3 over MEA as was stated earlier.
Most separation systems which use MEA as the solvent use a heat exchanger between
the absorber and stripper for the solvent. When using potassium carbonate as the
solvent, this heat exchanger is not necessary because the stripper can be run at a lower
temperature than the absorber. This means savings on equipment. The price of the
K2CO3 necessary to start up the unit is also less expensive than MEA. In bulk and
from the same vendor, K2CO3 was $0.5885/lb while MEA was $0.69/lb. Potassium
carbonate was also found for $0.4285/lb from another vendor; this price is used to
calculate feed costs. The following table summarizes our capital costs. We believe
much of the operating costs will be offset by the revenue generated through
CO2 purification.

Capital Cost Analysis

Absorber 500,000
First Flash 40,200
Stripper 160,400
Second Flash 43,400
Solvent 78,073
Total Capital Costs $822,073
Safety Considerations

The safety of an operation is always an important design concern. Thicker-walled

vessels and piping will be needed to contain the high pressures in the absorber, but
this is true throughout an ammonia production facility. Care must be taken in handling
the hot solvent solution. It is a skin and eye irritant and would cause thermal burns on
contact. From the material safety data sheets available, K2CO3 appears to be less of a
health hazard than MEA. MEA is also more reactive with a variety of materials. When
the facility design is closer to completion, the standard process hazard safety analysis
will be done.

Conclusion

This project design clearly meets the most important goal-to remove as much CO2 as
possible from the ammonia feed stream in order to prevent catalyst poisoning. The
project also separates out this CO2 to an extremely high purity, allowing the plant to
make as much money as possible off of the system. We believe that those qualities, in
addition to the use of potassium carbonate solvent make this plant design an excellent
choice for a CO2 absorption system.

Appendix

1. Aspen Flowchart for our System

References

Strelzoff, Samuel, ìSection 3: Carbon Dioxide Absorption,î Technology and

Manufacture of Ammonia, Robert E. Krieger Publishing Company, Inc.: 1988, pp.
193-248.
Twigg, Martyn V., Catalyst Handbook: second edition, Manson Publishing Ltd: 1996,
pp. 80, 340-343, 404-409.

Encyclopedia of Industrial Chemistry. Vol A.5, pp. 172-175