An Introduction to the Kalina Cycle

ASME International

Reprinted From

The American Society of Mechanical Engineers

345 East 47th Street
New York. NY 10017

PWR- Vol. 30, Proceedings of the International

Joint Power Generation Conference
Editors: L Kielasa, and G. E. Weed
Book No. H01077 -1996

An Introduction to the Kalina Cycle

HENRY A. MLCAK, PE

ABSTRACT1

many design options such as reheat, regenerative heating,

supercritical pressure, dual pressure, etc. all of which can be
applied in a number of different combinations in a particular
plant.

This paper is intended as a primer on the Kalina cycle - a

novel, efficient power cycle that uses an ammonia-water
mixture as the working fluid. The reader needs no more than a
basic understanding of conventional water based Rankine
cycle power plants to comprehend the basic thermodynamics,
principles and arrangements of Kalina cycle power plants
presented in this paper.

Each Kalina cycle system in the family of designs has a

specific application and is identified by a unique system
number. For example - Kalina Cycle System 5 (KCS5) is
particularly applicable to direct (fuel) fired plants. Kalina Cycle
System 6 (KCS6) is applicable to gas turbine based combined
cycles and Kalina Cycle System 11 (KCSI 1) is applicable to
low temperature geothermal plants. There are a host of other
systems which are applicable for other fuels or heat sources
such as municipal waste, waste gas stream in processing
plants, solar and even nuclear.

INTRODUCTION
Compared to the conventional century-old Rankine cycle, a
Kalina cycle power plant may offer efficiency gains of up to 50
percent for low heat energy sources such as geothermal brine
at 150C to 210C. Gains of up to 20 percent may be realized
for higher temperature heat sources such as direct fired boilers
and exhaust gases from a gas turbine. i.e. bottoming cycle of a
combined cycle plant.

But first, to really benefit from the discussions on the Kalina

cycle, an understanding of the Rankine steam cycle
fundamentals and basic thermodynamics is necessary.

THE RANKINE CYCLE

It is likely that Kalina cycle plants will even cost less to build
than Rankine cycle plants of equal output. Up to 30 percent
savings for low heat applications and up to 10 percent savings
for direct fired or bottoming cycle plants have been
approximated.

In the Rankine cycle, water is heated in a boiler (or a heat

recovery steam generator) to make high temperature, high
pressure vapour or steam. This steam passes through and
turns a turbine as it rapidly expands and cools to a low
temperature, low pressure exhaust. The turbine drives a
generator thus producing electricity. The steam from the
turbine exhaust is then condensed to water using a cooling
medium such as ambient air, or water from a pond or cooling
tower. The ambient air or pond is referred to as the heat sink.
The condensate is then pumped back to the boiler to repeat
the process. A schematic of this simple Rankine cycle is
shown in Fig. 1.

The Kalina cycle is principally a modified Rankine cycle. The

transformation starts with an important process change to the
Rankine cycle - changing the working fluid in the cycle from a
pure component (typically water) to a mixture of ammonia
and water.
The modifications that complete the transformation of the cycle
from Rankine to Kalina consist of proprietary system designs
that specifically exploit the virtues of the ammonia-water
working fluid. These special designs, either applied individually
or integrated together in a number of different combinations,
comprise a family of unique Kalina cycle systems. This is
somewhat analogous to the Rankine cycle which, in fact, has

Rankine cycle plants are inherently poor performers. For

example, the largest and most modern coal fired Rankine
cycle power plants are generally no more than 35 percent
efficient. That is, of the total energy in the fuel that is burned,
only 35 percent of it is converted to electricity.

This paper has been reprinted in SI units in 2004 with

permission of the author

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Fig. 1 Schematic Rankine Cycle Power Plant

The 65 percent energy loss is due to a host of reasons.
Approximately 15 percent energy loss is due to moisture in the
fuel, heat radiation from the furnace walls, low temperature
flue gas from the furnace and auxiliary (parasitic) power.
(Kalina cycle plants will have losses similar to these therefore
further discussion on these particular losses is not pertinent to
the topic of this paper.)

Fig. 2 Second Law Efficiency Limit

In a power cycle, the highest quality energy form available is

the heat source and the lowest quality energy form available is
the heat sink.
Consider a hypothetical ideal power plant with an infinite heat
source at 1000C. The shaded area in Fig. 2A graphically
represents the absolute total work from this power plant while
operating in a heat sink environment of absolute zero
temperature.

The Rankine cycle losses account for the remaining 50

percent. This loss is basically the energy that is still in the
steam at the turbine exhaust. Although this steam has an
enormous amount of energy, it is at such a low pressure and
temperature that it is useless. This energy must, therefore, be
thrown away to the heat sink just to condense the steam to
water so it can be pumped back to the boiler.

Recall the relationship C + 273 = K for absolute

temperatures. Therefore, absolute zero is 0K or -273C.

A quick review of thermodynamics will show why these cycle

losses are so large.

Since a heat sink temperature of absolute zero is only possible

in deep outer space, all of the work indicated in Fig. 2A cannot
be realized here on earth. The shaded area in Fig. 2B
indicates the portion of the absolute work that must be forfeited
because our heat sink temperature is much higher than
absolute zero. Another way to look at Fig. 2B is that amount of
absolute total work that our heat sink, acting as a heat source
itself, could do in an absolute zero environment. For our
example, a heat sink temperature of 10C, (283 degrees
above absolute zero) is used.

FIRST LAW, SECOND LAW & EXERGY

The first law of thermodynamics, often referred to as the law
of conservation of energy, deals with nothing more than the
accounting of energy. That is, all energy, in whatever form,
must be accounted for. For example, in a heat exchanger heat
energy loss by one stream is equal to the heat gained by the
other. In a power cycle, the heat input to the system is equal to
the sum of work and any waste heat produced or discharged
during the process.

The difference is shown by the shaded area in Fig. 2C. This

shaded area shows the energy available to do work. For an
ideal engine, it represents the maximum potential work from a
given heat source in a specific heat sink environment.

The above stated 35 percent cycle efficiency is a first law

efficiency because it is no more than a simple measure of the
work component performed by the input heat energy. (Power
plant heat rates are just another way to slate the first law
efficiency.)

Notice how the heat sink temperature limits an engine from

achieving 100 percent conversion of the heat energy to work
energy. The ratio (T2 T1) / (T2- T0) is the second law
efficiency limit. Using absolute temperatures and T0 = 0, the
second law efficiency limit (or our example is:

While the first law tells us how much, it doesnt tell us why.
Why are the losses what they are? The answer to this question
is crucial for ones understanding of a more efficient cycle.

(1273 283) / 1273

or, 77.8%.

This leads us to the second law of thermodynamics. This law

basically says that work will, or can be done by an energy
medium as it goes from a high temperature to a low
temperature inside a heat engine such as a turbine.

Potential work and exergy are other terms for this second
law efficiency limit.
Now suppose the heat source temperature is changed from
1000 to 250C. The exergy for this heat source is an amazing
low:
(523 283)/ 523
or, 45.9%.

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You can visualize this by pencilling in the changes in Figures

2A and 2C. This tells us that, even for a perfect engine, most
of the energy in this low temperature heat source would be
forfeited to the heat sink. (This should help to explain why it is
more difficult to exploit low temperature heat sources for
generating electricity where heat sources temperatures are
150C or lower.)
Lets suppose again that on a hot summer day the heat sink
temperature raises from 10C to 50C. The exergy decreases
from 77.8 percent to 74.6 percent for the 1000C heat source
and decreases from 45.9 percent to 38.2 percent for the 250C
heat source.
As you can see, either lowering the heat source temperature
or raising the heat sink temperature, lowers the exergy.
Conversely, either raising the heat source temperature or
lowering the heat sink temperature, raises the exergy.
If one could, somehow, directly use the heat source and heat
sink in an ideal heat engine, the above stated second law
efficiency limits would also be the first law efficiencies for our
hypothetical plants. And, of course, these efficiencies would be
the highest possible.

Fig. 3

But unfortunately this is not the case. Heat engines like todays
turbines need a medium to go between the heat source and
heat sink. This medium is a working fluid.

Second Law Efficiency

For our example, lets assume that, economically, the working

fluid can be condensed at a temperature no lower than 30C,
or 20C above the heat sink temperature of 10C.

A turbine in a closed loop power cycle has direct contact with

only the working fluid. This means that the turbine work is
determined, not by the actual heat source and heat sink
temperatures, but by the temperatures of the working fluid.

The work that this working fluid is capable of producing in an

ideal turbine is shown by the area between the hot working
fluid temperature and the cold working fluid temperature. See
Figure 3B. Notice that this area, and therefore the work is now
less that the potential maximum work shown in Fig. 3A and
previously shown in Fig. 2C. Destruction of exergy has taken
place because of the working fluid.

Go back to our 1000C infinite heat source and 10C heat sink
example that has a second law limit efficiency of 77.8 percent.
Lets introduce a working fluid and some real life design
limitations into our hypothetical plant. To do work, our working
fluid needs to be heated by the heat source. But 1000C is
way too hot to handle with current pipe materials. The current
metallurgy technology limit in power plants is around 600C.
For the sake of this exercise, lets assume that the working
fluid boils at a constant temperature of 600C as it absorbs
energy from the 1000C heat source.

The ratio of the work produced to the total heat source

energy is:
(873 303) / 1273
or, 44.8 %.
Now dont confuse this with a new second law efficiency limit.
i.e. exergy. This 44.8 percent is actually the first law
efficiency of our ideal turbine doing work with a working fluid.
This tells us that our hypothetical power cycle is producing
much less work than the potential work which was previously
calculated to be 77.9 percent. This exercise shows the
importance of keeping the working fluid temperature as high as
possible as it absorbs heat and as low as possible as it rejects
heat.

After producing work in the turbine, our working fluid will have
to give up its remaining heat to the heat sink via a heat
exchanger.
An important aspect of heat exchanger design must be
explained at this point. A basic parameter in sizing heat
exchangers is called pinch point. This is simply the minimum
temperature difference or temperature driving force between
fluids. If there is a large temperature difference between fluids,
the hotter fluid can easily transfer energy to the cooler fluid
with very little surface in a heat exchanger. However, if the
temperature difference is small, the surface (and cost) of the
heat exchanger increases exponentially. A point is reached
where it becomes cost prohibitive to further reduce the
temperature difference between the two fluids.

The percent of the potential work converted to actual work (in

our example 44.8 / 77.8, or 57.6 percent) is a measure of the
second law efficiency. To clarify further, 57.6 percent of the
potential work in the heat source is actually converted to work.
This second law efficiency makes for a good comparison of
power cycles because it eliminates measuring something we
have little control over - the heat sink.

ANALYZING THE LOSSES

Now we can begin to analyse why cycle losses are what they
are. In the previous exercise, two types of losses prevented all
of the exergy from being converted into work. These are
technological and thermo-economic losses. Refer again to Fig.
3 as these are briefly explained below.
Technological Losses
Our working fluid was limited to only 600C because we really
do not have piping material that can practically handled higher
temperatures. Losses in exergy that occur because of limits

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like this are called technological losses. Losses due to our

imperfect turbines, pumps and compressors are other
examples of technological losses.

Now, note that even with these losses, the area of Fig. 4B, and
thus the actual work could be larger if the working fluid
paralleled the heat source and cooling water curves. However,
since the working fluid water boils and condenses at a
constant temperature while the heat source and cooling water
have variable temperatures this is not possible. These
differences account for the structural losses in a power cycle.
As previously stated, reducing these structural losses is the
goal of Kalina cycle designs.

Advances in technology are still being made but at a much

slower pace than they were decades ago because of
diminishing returns (more research effort for incrementally
fewer gains in efficiency). The Kalina cycle does not solve or
reduce these technological losses; however it is important to
note that any technological advances made to benefit the
Rankine cycle will also benefit the Kalina cycle.

This finally brings us to the lifeblood of the Kalina cycle - an

ammonia-water mixture working fluid.

Thermo-economic Losses
The cold working fluid was set 20 degrees C above the heat
sink temperature because of economics. For our example, we
assumed that reducing this 20 degrees difference any further
would have increased the incremental capital cost of our heat
exchanger above the value of an incremental increase in
power output. Losses in exergy that occur because of limits
like this in boilers, condensers, cooling towers, etc. are called
thermo-economic losses. Thermo-economic decisions will still
have to make in Kalina cycle plants in the same basic manner
that they are currently made in Rankine cycle plants.

AMMONIA-WATER MIXTURE
Ammonia-water mixtures have many basic features unlike that
of either pure water or pure ammonia. A mixture of the two
fluids behaves like a totally new fluid altogether. There are four
primary differences.
First, an ammonia-water mixture has a varying boiling and
condensing temperature. Conversely, both pure water and
pure ammonia have constant boiling and condensing
temperatures.

Structural Losses
The groundwork has now been laid to address the real focus
of the Kalina cycle - increasing cycle efficiency by reducing
structural losses.

Second, the thermo-physical properties of an ammonia-water

mixture can be altered by changing the ammonia
concentration. The thermo-physical properties of water and
ammonia are fixed.

In the real world, heat sources are not infinite. Power plant
heat sources such as hot gases and geothermal brine are
sensible and limited. That is, the temperature of the heat
source cools as it gives up its energy to the working fluid. On
the other hand, working fluids in a Rankine cycle absorb much
of this heat at a constant temperature due to the constant
boiling nature of a pure component like water.

Third, ammonia-water has thermo-physical properties that

causes mixed fluid temperatures to increase or decrease
without a change in the heat content. The temperature of water
or ammonia do not change without a change in energy.
The final difference is not really a change in a basic feature,
but rather an important change in a fluid property. This is the
freeze temperature. Water freezes at a relatively high
temperature of 0C, while pure ammonia freezes at -78C.
Solutions of ammonia-water have very low freezing
temperatures.

On the turbine exhaust side, we have a heat sink environment

that is essentially at a constant temperature. However, a finite
cooling medium of water or air is used. This finite medium
increases in temperature as it absorbs heat from the steam
working fluid exiting from the turbine. Conversely, the steam
being condensed does so at a constant temperature.

Phase Diagram

Figure 4 shows a more accurate graphical depiction of the

Rankine cycle process. The area in Fig. 4A represents the
potential work of a given heat source and heat sink, while Fig.
4B represents the actual work of a Rankine cycle. The
Rankine cycle actual work is superimposed over the potential
work. First note the metal limit and pinch point that reduce the
actual work. These are the technological and thermo-economic
losses previously discusses.

The essence of the Kalina cycle takes advantage of the first

feature change - the ability of an ammonia-water mixture, at
any given pressure. to boil or condense at a variable
temperature.

Fig. 5 Ammonia-Water Phase Diagram

Fig. 4 Structural Losses

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This is in distinct contrast to the constant boiling/condensing

temperature of a pure fluid like water.

Varying Boiling Temperature

As previously stated, the heat input to a power plants working
fluid is from sensible/limited heat sources. Therefore the
temperature of the heat source drops as it gives up its energy
to the working fluid.

Ammonia has a low boiling and condensing temperature

compared to water. Therefore, ammonia in a mixture with
water is the more volatile component of the two. This means
that when an ammonia-water liquid is heated, mostly ammonia
will boil off first, i.e. distillation will start to occur. Conversely,
when an ammonia-water vapour is cooled, mostly water will
condense first.

Because of the variable boiling temperature, the temperature

rise of an ammonia-water mixture, in a counter-flow heat
exchanger, more closely follows the straight line temperature
drop of a sensible heat source.

This unique feature is illustrated in a phase diagram shown in

Fig. 5. This diagram plots temperature vs. ammonia-water
concentration for ammonia-water mixtures at 550 kPa. (Each
phase diagram plot is for a specific pressure).

This is illustrated in Fig. 6, which shows the temperature profile

of a liquid ammonia-water working fluid being heated by a
stream of exhaust gas. The working fluid, at 3450 kPa - 70
percent ammonia-water liquid, has an initial temperature of
38C and is heated to a 260C superheated vapour. The
stream of exhaust gas has an initial temperature of 288C.

Point I at 156C is the saturation point of pure water. This is

the temperature where water boils or steam condenses at a
pressure of 550 kPa. Similarly, point 2, at 6.9C is the
saturation point of pure ammonia at 550 kPa.

As the ammonia-water solution at 38C is heated, it reaches

saturated liquid point first at 93C and then saturated vapour
point at 184C. The vapour is then superheated another 76C
to reach its final temperature of 260C. The exhaust gas in this
example is cooled from 288C to approximately 93C as it
gives up its energy to the ammonia-water.

Now notice the two curves in between. The bottom curve is the
saturated liquid, or boil point for the different concentrations of
ammonia-water. This is where initial vaporization occurs when
the mixture is heated or where complete condensation occurs
when cooled. The top curve indicates the saturated vapour, or
dew point where complete vaporisation or initial condensation
occurs.

Now using the same available heat source and the same
temperature pinch point, the heat absorption characteristic of
3450 kPa pure water will be examined next.

When an ammonia-water mixture is vaporized or condensed, a

phase diagram conveys a lot about the process. For example,
consider a sub-cooled 70 percent liquid ammonia (in water)
mixture, a common mix in the Kalina cycle. When heat is
applied, the mixture starts to vaporize at 21C, shown as point
3 in the diagram. As heat continues to be applied, the
temperature rises and more of the mixture (remember mostly
ammonia at first) vaporizes.

As shown in Fig. 7, the water is heated from its initial

temperature of 38C to its saturation temperature of 242C. As
heat continues to be absorbed, the saturated water boils and
goes from saturated liquid to saturated vapour without a
change in temperature. The saturated vapour or steam is then
superheated to its final temperature of 260C.

After the solution starts to boil, but before it is fully vaporized,

the solution actually has two separate components - vapour
and liquid. For example, at 66C, the 70 percent average
solution is shown at point 4. The vapour component of this
solution is shown at point 5. As indicated, this vapour contains
a rich solution of 97 percent ammonia (and 3 percent water).
The liquid component at point 6 contains a lean 36 percent
ammonia in water solution.
Using the lever-arm principle, the fraction of the total mass that
is 97 percent ammonia rich vapour is given by the relation:
(pt4- pt6) / (pt5-pt6)
(70- 36) / (97 - 36)
or, 55.7%.
The fraction of the total mass that is 36 percent ammonia liquid
is given by the relation:
(pt5 - pt4) / (pt5 - pt6)
(97 - 70) / (97 - 36)
or 44.3%.
Further heating continues to raise the temperature of the
solution. And in so doing, vaporization of the liquid fraction
continues until all of the mixture reaches a saturated vapour
state at 116C, point 7. Additional heating results in
superheating the ammonia-water vapour.
This process is completely reversed when ammonia-water
vapour condenses as heat is removed.

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Fig. 6 Heat Exchange Process - Heat Source to 3450 kPa

Ammonia-Water Solution

Fig. 7 Heat Exchange Process - Heat Source to 3450 kPa

Water

Fig. 8 Heat Exchange Process - Heat Source to 690 kPa

Water

Fig. 9 Heat Source Process - Heat Source to 55 kPa Water

It is clearly shown in Fig. 7 that the high constant boiling

temperature of water limited the amount of energy that could
be extracted from the heat source.

Water would have to be lowered to a vacuum of 55 kPa before

it could extract the same amount of energy as the 3450 kPa
ammonia-water working fluid. See Figure 9. Note how the
average temperature of this working fluid is lowered even
further by the low constant boiling temperature of the 55 kPa
water.

Also note the final temperature of the exhaust gas almost

260C. The water cannot utilize the rest of the energy in the
flue gas from 260C on down.

So, although a high average working fluid temperature is

desired to increase efficiency in the Rankine cycle, a lower
pressure/lower saturation temperature may be necessary to
simply increase the amount of heat extracted from a
sensible/limited energy source. Now you should be able to see
the kind of compromises that are made in Rankine cycle
plants.

As you can see, the 3450 kPa water absorbed only 15 percent
of the total energy absorbed by the ammonia-water. Now it
doesnt even matter how efficient the rest of the plant can
convert this fluid to work because 85 percent of the available
energy is not being used.
So lets try to absorb more of the heat source energy by
lowering the boiling temperature. Another plot, Fig. 8 shows
the same comparison for water at 690 kPa. As can be seen,
lowering the pressure (and therefore the saturation
temperature) increases the amount of heat that can be
extracted. In this case, water at 690 kPa extracts 62 percent
of the amount extracted by the 3450 kPa ammonia-water
working fluid.

Such compromises are reduced in the Kalina cycle. As

illustrated in these comparisons, one can get both relatively
high average temperature and high energy transfer with
ammonia-water as the working fluid.
An interesting side note - designers of larger bottoming
(Rankine) cycles in gas turbine based combined cycle plants
often increase cycle efficiency by using two or even three
different pressure levels to stair step through the heat
absorption process. The highest pressure water extracts
energy from the highest temperature exhaust gas, while the
lower pressure water extracts energy from the lower
temperature gas.

But wait. While more of the heat source energy was indeed
extracted, lowering the boiling temperature of the working fluid
lowered the average temperature of the hot working fluid. And
from our previous discussions, we know that lowering the
average hot working fluid temperature lowers the second law
efficiency.

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This increases both the average temperature of the working

fluid in the HRSG and the total amount of energy extracted
from the gas while still making available a high pressure steam
for the turbine. The lower pressure steam is admitted to the
turbine at different inter-stage points. An ammonia-water
mixture working fluid that parallels the heat source
temperature profile eliminates the complexity of these multipressure systems.

This brings us to the next advantage of the Kalina cycle variable condensing temperature makes possible a high
degree of energy recuperation.
Refer back to the phase diagram in Fig. 5 for a 70/30 mixture
at 550 kPa. Point 7 depicts the 116C saturated ammoniawater vapour at the turbine exhaust while point 3 depicts the
21C saturated ammonia-water liquid at the condenser outlet.
Note that the working fluid must drop 95 degrees C in the total
condensation process from turbine outlet to condenser outlet.

Fig. 11 Heat
Condensation

2070 kPa

Exchange

Process

Recuperation-

550 kPa

Figure 10 shows a schematic of a fundamental Kalina cycle

design that capitalizes on this temperature difference. The
condensed 21 C ammonia-water at the condenser outlet is
pumped so a recuperative heat exchanger to absorb heat from
the 116C turbine exhaust flow while, at the same time helping
to condense the exhaust flow.

Fig. 10 Schematic Recuperation Condensation

Varying Condensing Temperature
Both steam in a Rankine cycle and ammonia-water vapour in
a Kalina cycle will exhaust from a condensing turbine at or
near their respective vapour saturation points. However, given
equal condenser cooling water temperatures, the ammoniawater will have a significantly higher pressure and temperature
than the steam.

A temperature profile curve of this process is shown in Fig.11.

In this example, half of the energy in the turbine exhaust fluid
normally loss so the heat sink is recuperated.
This figure shows how the variable condensing working fluid of
a Kalina cycle makes it possible for a low pressure, high
temperature stream to transfer heat so a high pressure, low
temperature stream.

The higher pressure is a result of ammonia being more volatile

than water. The higher temperature is a result of the variable
condensing temperature feature of an ammonia-water mixture.

Now, lets focus on the final condensation process.

For example, given a condenser supplied with 16C cooling

water, steam in a Rankine cycle should exhaust from a turbine
at approximately its saturated vapour conditions of 4 kPa and
29C. This steam will condense to its saturated liquid
conditions at essentially the same pressure and temperature.
With the same cooling water, ammonia-water vapour will exit a
turbine at its saturated vapour conditions of 550 kPa and
116C. This vapour, however, will not fully condense until
cooled to its 550 kPa saturated liquid temperature of 21C.

Refer again to Fig. 4 and note how the condensed water

temperature depends on the exit cooling water temperature,
not the inlet cooling water temperature. Again, this is due to
the constant condensing temperature of steam Therefore,
work is loss in a Rankine cycle due so the structural
difference between the working fluid and the cooling water.
Figure 11 shows the heat exchange process for an equivalent
condenser in a Kalina cycle. Note how the final ammoniawater working fluid temperature depends on the inlet cooling
water temperature - not the higher exit temperature, thus
keeping the average heat rejection temperature of the working
fluid low.

If you apply the concepts presented in the first part of this

paper, you should realize that this high 116C turbine exhaust
temperature in the Kalina cycle would tend to increase the
average heat rejection temperature and, as a result, decrease,
not increase the cycle efficiency. This would be exactly right if
the exhaust fluid went directly to the condenser - but it doesnt.
The high temperature of the ammonia-water makes its energy
available to do further work while in the Rankine cycle the
low temperature of the steam makes its energy unavailable
for further work.

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Fig. 13 Phase Diagram Absorption-Condensation

Fig. 12 Schematic Absorption-Condensation

There is also a secondary benefit of this Kalina cycle design.
Since the temperature rise of the cooling water for the
ammonia- water can be higher than that for condensing steam,
the cooling water flow rate for the ammonia-water can be less
than that required for the steam. This means smaller cooling
towers, pumps and piping, along with lower auxiliary power
requirement for pumping and cooling Lower fans.
This can result in significant capital cost savings for the cooling
system and further increases in the net power plant output for
the Kalina cycle.
Specific Composition Change
Fig. 14 Energy-Mass Balance Heat of Mixing

The Kalina cycle has a design option that can effectively

reduce the pressure and temperature of the vapour at the
turbine exhaust.

This bit of design genius not only reduces the turbine exhaust
pressure, but reduces the exhaust temperature as well. As Fig.
13 shows, the temperature of the ammonia-water vapour at
the turbine exhaust is reduced from 116C, point 3, to 88C
(point 4).

Taking a page out of an ammonia absorption refrigeration

design book, the Kalina cycle has the ability to readily change
the thermo-physical properties of the working fluid in different
parts of the cycle by changing the ratio of the ammonia-water
mixture.

Overall Composition Change

A simplified arrangement for this part of the Kalina cycle is

depicted in Fig. 12. In this example, a 70 percent ammonia
working fluid exits the turbine. This fluid first passes through a
recuperator as explained in the previous section. After the
recuperator, a very lean mixture of 34 percent ammonia from a
distillation system is sprayed in the stream. This spray
changes the concentration of the turbine exhaust stream from
70 to 45 percent ammonia. The stream is then condensed to a
final temperature of 21C.

Another feature of the Kalina cycle is that the composition of

the ammonia-water mixture, and therefore the thermo-physical
properties of the working fluid can be readjusted throughout
the entire system if operating parameters change.
For any given Kalina cycle arrangement there is an optimum
ammonia-water mix for a given cooling (heat sink) temperature
and a given heat source temperature. If one or both of these
temperatures change, the mix in the cycle can be easily
adjusted to again optimize the cycle efficiency for the new
conditions.

This absorption-condensation process can be graphically

explained by Fig. 13. This figure shows two ammonia-water
phase diagrams - one for 550 kPa and one for 205 kPa. As
shown, if the fluid was condensed at 70 percent concentration
and 21C, it would have a condensing pressure of 550 kPa
(point 1). By changing the concentration to 45 percent, the
condenser can - at the same heat sink temperature - condense
the turbine exhaust at 205 kPa (point 2).

For most plants, the cooling temperature changes significantly

with the season of the year and within a particular season, the
temperature will change moderately every hour. While it may
not be practical to change the mixture every hour, the mixture
can certainly be changed on a seasonal basis. The mix can be
changed to optimize plant efficiency for an expected average
cooling temperature during a certain period of time.
Most fuel fired plants will not see a change in the heat source
temperature, however plants utilizing other heat sources may.
A plant that utilizes waste heat from a process plant may see a
temperature change due to a process output change. A
geothermal plant may see its heat source temperature
degrade with time as the resource area is developed and more

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of the geothermal steam or brine is used. Again, as these

conditions change over time, the ammonia water mix can be
adjusted to give optimum performance.

Just a small amount of ammonia in water greatly reduces the

freezing temperature. For example, even a lean 25/75
ammonia-water solution has a very low freezing temperature
of -51C.

The ability to change the mixture, and thus the thermodynamic

properties of the working fluid offers an extra degree of control
simply not possible in conventional Rankine power cycles.
Heat Release of Solution
Another unique feature of ammonia-water properties occurs in
mixing. Two separate streams of ammonia-water can be mixed
together to form a single stream that has a temperature that is
actually higher or lower than either one of the two individual
streams.

Fig. 16 A Schematic
Arrangement; -15C db

Winter

Condenser

Series

As a result, condensation temperatures of ammonia-water

fluids can go down to arctic temperatures.
Air cooled condensers do in fact have to be used to exploit this
advantage. Kalina cycle plants utilizing water cooled
condensers would, of course, be subjected to the same 0C
temperature limitation because of freezing of the cooling water.
Fig. 15 Phase Diagram Heat of Mixing

Air cooled condensers do give a lacklustre performance in

warm climates. It is a fact that air cooled condensers do not
benefit from the evaporative cooling that cooling towers
provide. Thus plants with air cooled condensers will have
lower efficiencies at summer temperatures. But as with every
project, specific site conditions, water availability, seasonal
peaking load, etc. must be considered to determine if a
particular design is justified.

Figure 14 shows an energy-mass balance for a simple mix. As

shown, the two incoming streams are at 15.6C. The outgoing
stream is at 37.8C.
This phenomenon is caused by a reaction referred to as heat
of mixing. As the name implies, heat release is a result of
mixing and occurs when a lean solution and a rich solution are
mixed together.

Kalina cycle plant designers must therefore weigh the winter

time advantage against the summer time disadvantage, or
they might consider another design option that w not even be
considered for Rankine cycle plants. This is the installation of a
water cooled condenser an air cooled condenser arranged in
series. This arrangement is possible in a Kalina cycle plant
again because of the variable condensing temperature.

The phase diagram in Fig. 15 should help to explain this

phenomenon. This diagram plots enthalpy vs. ammonia-water
concentration for mixtures at 689 kPa. Notice how the mixing
line in this example crosses isothermal lines.
The advantage of this feature is in heat transfer. For example,
if an external heat source or an internal heat recuperation
process stream was at 38C, no heat transfer to the combined
stream in Fig. 14 could be possible because there would be no
temperature difference between the two streams. However,
this same source of heat could transfer heat into each stream
individually because the temperature of each is 22 degrees C
cooler.

Figure 1 6A depicts this arrangement for winter operation. The

turbine exhaust flow, after first going through a recuperator,
would next go through a water cooled first stage condenser.
Here, the exhaust flow would continue its condensation
process started in the recuperator. The lowest temperature of
the ammonia-water out of this condenser would be 13C or so.
(This is limited by the cooling water approaching freezing
conditions in the cooling tower.)

Operation Below Freezing Temperatures

We have established that lower heat sink temperatures
increase the exergy, i.e. potential work of a heat source.
However, water based Rankine cycle plants cannot take
advantage of this additional potential when the heat sink
temperature drops below 5C or so. This is, of course,
because plant operators will start to control the water
temperature to prevent freeze damage. So even though
nature, by lowering temperatures below freezing, gives an
opportunity to increase cycle efficiency, Rankine cycle plants
simply cannot take advantage of it.

The fluid would next flow to the air cooled final stage
condenser where final condensation would occur. A final
temperature of around -3.9C could be obtained with a dry
bulb temperature of -15C. This is about 16.7C lower than
had only a water cooled condenser been installed.

Kalina cycle plants, however, can take advantage of this

opportunity. Ammonia has a very low freezing temperature.

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All this points to the fact that the innovation and technology of
the Kalina cycle is in the process itself, not in the equipment or
materials. There are no major equipment developmental
hurdles.
Even for binary geothermal plants, where most plants use a
hydrocarbon base working fluid, ammonia-water has other
major advantages over its competition. First, ammonia-water
has higher heat transfer rates than hydrocarbons. Size of heat
exchangers, therefore, will be smaller and less costly. Second,
hydrocarbon fluids have higher molecular weights than
ammonia-water. As a result, ammonia-water can produce
equal power outputs at significantly lower flow rates. And
finally, the hazards of working with ammonia-water are
significantly less than with hydrocarbons.
So what about the hazards of working around ammonia?
Ammonia is actually a very common, widely used, and
regularly handled chemical. There has been decades of
working with ammonia in hundreds of synthesis plants,
thousands of ammonia absorption refrigeration systems as
well as countless fertilizer feed stock distribution centres. Even
in conventional power plants, ammonia has been used for
decades to control the pH of the working fluid. Ammonia is
also being used more frequently for NOx emission control
systems and inlet air chillers on gas turbines.

Fig. 16 B Schematic - Summer Condenser Series

Arrangement; 38C db, 18C wb
For a 70 percent ammonia-water mixture, the exhaust
pressure is effectively lowered from 411 kPa, the saturation
pressure of 13C to 228 kPa, the saturation pressure of -3.9C.

Large quantities of anhydrous ammonia are handled on a

regular basis in farming communities. Farmers and ranchers
have many uses for anhydrous ammonia which result in
direct releases to the environment. As a nitrogenous fertilizer,
pure ammonia is injected 10 to 15 cm below the surface of the
soil at a rate of 100 to 450 litres per acre. This gaseous
ammonia is adsorbed on the surface of clay and humus
particles. Anhydrous ammonia is also used to prepare protein
feeds for cattle and sheep, as a herbicide to kill pesky weeds
and as a defoliant to hasten the shedding of cotton leaves to
facilitate mechanical harvest.

Figure 16B depicts the arrangement for summer operation.

Through proper valving, the role of the condensers would be
reversed. The first stage condenser would be air cooled and
the final stage condenser would be water cooled.
A site with a 38C dry bulb temperature and 18C wet bulb
temperature would produce cooling water at around 23C.
Ammonia-water coming out of the air cooled first stage
condenser would be approximately 49C. The final condensing
temperature coming out of the water cooled final stage
condenser would be around 28C - about 21 degrees C lower
than had only an air cooled condenser been - utilized. Here,
the exhaust pressure is lowered from 1262 kPa, the saturation
pressure of 49C, to 703 kPa, the saturation pressure of 28C.

This extensive industrial and agricultural experience has

resulted in a maturity of the safety standards applicable for
working with anhydrous ammonia. These standards have a
proven track record in ensuring safe and environmentally
responsible ammonia handling facilities.

MISCELLANEOUS

Due to the distinctive, pungent suffocating odour and irritation

properties, even at low concentrations, ammonia is self
alarming and actually serves as its own warning agent. No
person will voluntarily remain in an area that has injurious
concentrations of ammonia.
The strong odor ensures
operators maintain a tight plant.

Conventional axial flow steam turbines can be used in Kalina

cycle plants. This is possible because the molecular weight of
ammonia and water are similar - 17 for ammonia and 18 for
water.
Turbines for Kalina cycle plants will also be smaller and
therefore less expense than turbines in Rankine cycle plants.
This is because Kalina cycle plants can utilize back pressure
turbines as condensing turbines.

Anhydrous ammonia is flammable but difficult to ignite. It can

only ignite in a very narrow concentration range - 16 to 25
percent by volume in air with an open flame. Ammonia will not
support combustion after the ignition source is withdrawn.
Ammonia is gaseous at atmospheric pressure. It is lighter than
air and. therefore, easy to vent off.

Turbines in Rankine cycle plants exhaust to a condenser

under vacuum, whereas Kalina cycle plants exhaust to a
condenser under pressure. This creates a big difference in
specific volumes and therefore a big difference in the size of
the flow area in the exhausting turbine.

Ammonia is an ecologically safe industrial chemical when

handled properly. It readily combines with water and carbon
dioxide to form relatively harmless compounds. It is even
reported to benefit the environment by neutralizing acidic
pollutants in the air.

For example, the specific volume of a 70 percent ammoniawater mixture exhausting from a turbine at its dew point of 550
kPa and 116C is 0.326 cubic meter per kilogram. The specific
volume of steam at the same condensing temperature of 21C
but at its saturation pressure of 23 kPa is an amazing 54.2
cubic meters per kilogram.

Ammonia is rendered harmless when diluted sufficiently with

water. These lean ammonia-water solutions have numerous
industrial and household uses, especially as cleansers.
Blowdown solutions too lean to be reused in a Kalina cycle
plant can be sold back to the supplier of ammonia for these
other markets.

There are no special materials required for ammonia-water

mixtures. Carbon steel is quite acceptable for low temperature
applications. Alloys already familiar to the power industry are
acceptable for high temperature service. The only material that
is not acceptable is copper or copper bearing alloys.

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is an abundant supply of low temperature geothermal energy

sources and waste heat process streams that are not
economically feasible to develop using current technologies.

CONCLUSION
Most efficiency improvement programs for Rankine power
cycles generally target only one or two specific designs at a
time. Cycle designs like higher pressures and temperatures, or
more reheats hope to gain only a fraction of a percentage point
in efficiency. These efficiency gains generally come at a very
high cost. Consequently, gains are often not economically
justified.

The claims of the Kalina cycle technology have been

supported by a 3 Megawatt pilot plant in Canoga Park,
California. This plant utilizes 543C waste heat from a gas fired
furnace as its heat source. Several Kalina cycle projects are
currently in the design stage. Heat sources for these projects
include geothermal, gas turbine exhaust gas (combined cycle),
coal fired and municipal waste.

The Kalina cycle, on the other hand, presents a host of new

ideas to the power industry at one time. Each idea alone has a
potential of several percentage points gain in efficiency. And
because of this higher efficiency, the physical size of certain
plant equipment will be smaller. Smaller boilers, smaller
pollution control systems, smaller fuel handling systems,
smaller ash handling systems, and smaller cooling systems will
be required for a given power output. This, coupled with the
fact that the turbines will also be smaller and standard
materials can be employed throughout the plant, means that
these efficiency gains may actually come at a lower cost than
current Rankine cycle plants.

ACKNOWLEDGMENT
The author wishes to acknowledge the substantial assistance
of Dr. A. I. Kalina. H. M Leibowitz and Y. Lerner of Exergy. Inc.
during the preparation of this article.

BIBLIOGRAPHY
Kalina. A. 1.. Combined Cycle System With Novel Bottoming
Cycle. ASME Paper 84-GT-173

The Kalina cycle does not require technological breakthroughs

in equipment design. There is only a lack of experience with an
ammonia-water working fluid in the power industry. As such,
knockout risks associated with the Kalina cycle are minimized.

Leibowitz. H. M. et al, Start-up and Operating Experience of

the Kalina Cycle Demonstration Plant. Technical Paper TP 9227 presented at ASME Cogen Turbo Congress. Houston.
Texas, September 1992.

It is important to realize that the Kalina cycle can take

advantage of other technological advances in metallurgy,
turbines and combustion/emissions control processes that are
sure to be made in the future. Since these types of
enhancements do not directly affect the power cycle process,
Kalina cycle plants can incorporate these advances when they
become available.

Marston. C. H.. Parametric Analysis of the Kalina Cycle.

Journal of Engineering for Gas Turbines and Power. Vol. 112.
pp 107-116.
American National Standard for Equipment, Design, and
Installation of Ammonia Mechanical Refrigerating Systems.
ANSI/lIAR 2-1992.

It is also important to point out that the Kalina cycles

combined higher efficiency and lower cost advantages should
make possible the exploitation of new energy resources. There

Safety Code for Mechanical Refrigeration. ASHRAE 15-1992.

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