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Water Contamination in Ammonia Refrigeration Plant

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THE DANFOSS JOURNAL 3.

2000
Water contamination in ammonia refrigeration plant
....................................................................................................................................................................................................................................................
By Per Skærbæk Nielsen,
Product Manager
Fig. 2 The bottle test vessels, evaporators, condensers, etc., or
Bottle test – shows the affinity between NH3 and H2O
DANFOSS INDUSTRIAL water condensate might appear because
REFRIGERATION of temperature variations before the system
NH3 NH3
is charged with refrigerant. Such water
Vapour Vapour contamination can and should be avoided
partly by drying out the system thoroughly,
H20+NH3 and partly by ensuring adequate vacuum
in the system before the ammonia is
charged and the plant started.

Every day, Danfoss Industrial Refrigera- H20 When a plant is in operation, water can
tion (DIR) has to use its knowledge and find its way in when service work is being
resources to help customers all over the Always use a check valve when evacuating through water carried out, by accident (e.g. corrosion in
world solve problems with industrial chillers) or when on the low-pressure side
refrigeration plant. It is often the case of the plant moist air is sucked in through
Vapour from the system
that the customer’s problem has nothing glands and gaskets that do not seal prop-
to do with our products or the way in erly. Water ingress in this way is especially
which the plant is designed, but is the common if the normal suction pressure
result of completely different factors. is lower than atmospheric pressure.

To help our customers save energy and The air that enters the plant in this way
minimise their service costs, we at DIR If the connection between cause and and which is blown out again on the high-
collated some of our knowledge and ex- effect in a refrigeration plant where the pressure side (either manually or by an
perience in a technical document which ammonia refrigerant has been contami- automatic air purger) is completely dry
was presented to the 1998 annual confe- nated by water is not known there is a because it has yielded all the moisture it
rence of The International Institute of risk of many resources being devoted to contained to the ammonia and hence water
Ammonia Refrigeration (IIAR). This article “curing” the symptoms rather than solving will be accumulated. This is how water
is an abstract of that document and its the real problem. We call this the “vicious accumulates in the plant.
presentation at the conference1). wet circle”. (See fig. 1.)
The aspect to be aware of here is that al-
The “vicious wet circle” The bottle test though automatic air purgers eliminate the
The actual cause of many problems in To understand how large quantities of problem of air in the system, they do not
industrial ammonia refrigeration plants is water enter an ammonia plant it is first solve the problem of water accumulation.
water contamination of the ammonia itself. necessary to look at the affinity that exists
Often, the only visible signs in the plant between water and ammonia. The easiest The size of the problem can be illustrated
are just the result or a symptom of the way to illustrate this phenomenon is by with the help of simple arithmetic:
problem. using the so-called “bottle test”. If 5 litres of air per minute is sucked into
If an empty bottle is turned upside down, a plant and allowed out again through
filled with ammonia vapour and then taken the automatic air separator, and assum-
down into water until the neck is immersed, ing an air temperature of 20°C [68°F]
Fig. 1 Consequences of water contamination “The water will begin to rise up in the bottle – at and air humidity of 80%, in the course of
vicious circle” first slowly and then more quickly – until 10 years the quantity of water dissolved
Incorrect service and maintenance procedures the bottle is almost full of water. The reason in the system ammonia will amount to
is the affinity between water and ammonia; 363.5 litres.
Water penetrates into the system
it is so great that the ammonia vapour
Chemical reactions dissolves in the water. The pressure in the Where is the water?
Problems with oil and sludge, compressor affected bottle thereby falls and water is sucked Because of the great difference between
up into it. the vapour pressures of ammonia and
The bottle test illustrates perfectly how water, an ammonia refrigeration plant
water can suddenly be sucked into an can be regarded as a large distillery where
ammonia refrigeration plant when the only small amounts of water evaporate
refrigerant is being evacuated, for example together with the ammonia. Water thus
during service work when it is normal accumulates in the low-pressure side, i.e.
practice to blow the refrigerant out through in liquid separators, intermediate coolers,
a water-filled container. That is why the etc. while, practically speaking, no water
use of a check valve in the drain line is appears in the high-pressure side.
always recommended when ammonia is
Treating the symptoms, not the real problem
evacuated through water. The valve elim- The extraction of refrigerant in order to
No investigation of water content inates the risk of water suddenly being measure water content should therefore
Increased service and operating costs sucked into the plant (see fig. 2). only be performed on the low-pressure
side, while as much as possible of the
Capacity and energy consumption affected
How and where does water come in? ammonia charge is on the high-pressure
Problems with valves and regulators Water can enter a refrigerating plant in side of the plant. Such measurements
Corrosion many ways. Before starting up, there may will reveal the largest percentage of water
already be water from pressure testing in content.
44
2.2000
THEDANFOSS
THE

Fig. 3 Water content given at evaporating temperature In the case of small commercial ammonia
DANFOSS

refrigeration plant with refrigerant charges


Intermediate cooler (-50; -31) ºC
of less than about 4 kg, it is cheaper to
JOURNAL

Separator or evaporator (-50; -31) ºC


JOURNAL

....................................................................................................................................................................................................................................................
Separator or evaporator -31 ºC replace the whole charge several times
than it is to install or replace a filter drier.
3.2000

175 refrigeration plants, total Danfoss has also looked at other filters on
Water/weight percentage

Measured values
77: ≥ 1% water the market without finding any of them
37: ≥ 2% water suitable for ammonia refrigeration plant.
25: ≥ 3% water

What happens to pressure and tempera-


ture when water enters the plant?
When water becomes mixed with the
ammonia, the thermodynamic properties
of the mixture are different from those of
pure ammonia because changes occur
in the relationship between the pressure
of the respective saturated vapours and
Lowest evaporating temperature in refrigeration plant
the corresponding temperatures. At the
same pressure, an ammonia-water mix-
ture has a higher evaporating temperature
EP temp. (-50;-31)ºC than pure ammonia. A refrigeration plant
Litres EP temp. (-31;5)ºC in which water has mixed with the ammo-
nia must therefore operate with a lower
pressure in the evaporator to maintain
the same evaporating temperature than a
Drained-off water (1)

plant with pure ammonia. This can have


serious consequences on plant capacity
and operating economy.

A rule of thumb says, “at low evaporating


temperatures the power consumption of
the plant rises about 5% for each degree
Celsius the corresponding pressure drops
on the suction side.” The plant capacity
falls markedly at the same time.
Fig. 4 Quantity of drained-off water per plant (1)
An example:
At an absolute pressure of 3 bar [43.5 psia]
the evaporating temperatures will be as
How much water can actually be found How can the water be removed? follows (see fig. 5):
in a plant? In industrial ammonia refrigeration plant, –9.23°C [15.39°F] with pure ammonia
In Denmark, Norway and Sweden, and water is removed by distillation in a water –6.69°C [19.96°F] with 10% water in the
with the participation of the Danish Tech- rectifier where the ammonia slowly evap- ammonia
nological Institute and other bodies, an orates leaving the water behind in the –3.16°C [26.31°F] with 20% water in the
extensive investigation into water content vessel. When this process has been ammonia.
was conducted in 175 industrial ammonia repeated many times, the residue in the Such a change in the evaporating tempera-
refrigeration plants. Of these, 25 contained container is drained off. This normally ture because of water in the ammonia can
more than 3% water, 37 more than 2% consists of water with a content of about have a significant effect on the capacity
and 77 more than 1%. In a few plants, 30-40% ammonia, depending on the and power consumption in, for example, a
water contents of 26%, 24% and 18.5% pressure and temperature at the time of chiller unit. When working with dry expan-
were found (see fig. 3). emptying2). sion on ammonia systems such changes
in pressures and temperatures will be re-
In 65 of the plants examined a water What about filter driers? gistered as superheat by the thermostatic
rectifier was installed to boil off the water. Danfoss has looked into the possibility of expansion valve – without this being the
The quantity of boiled-off water was then producing filter driers for ammonia refri- case. In the event of too high a “false
measured. In two of these plants, 250 litres geration plant. The conclusion is that superheat” the valve will become unable
of water were separated out and in one even though it should be technically fea- to “control” the evaporator.
plant 199 litres. On a further 10 plants, the sible to produce such a filter, it would be
figures were between 100 and 150 litres very expensive and the amount of sepa- What happens “chemically” in the plant?
(see fig. 4). In none of the plants were rated water very small in relation to the Pure ammonia or, as it might be called,
service personnel aware that there might water quantities that exist in ammonia “dry” ammonia is not particularly chemi-
be problems with water in the ammonia. refrigeration plants (a few hundred grams cally reactive. In fact, if ammonia were free
per filter). of water and remained in this condition,
These measurements must be seen in the copper or copper alloys such as brass
light of the recommended water content in could be used in ammonia systems.
ammonia refrigeration plant, i.e. max. 0.3%.

5
THE DANFOSS JOURNAL 3.2000
Fig. 7
Fig. 5: Thermodynamic properties NH3 + H2O
Advantages of keeping systems dry – “The good circle”
Saturation Saturation temperature, °C if Saturation Saturation temperature, °C if
pressure pressure Correct service and maintenance procedures
....................................................................................................................................................................................................................................................
Bar NH3 70% 80% 90% 100% Bar NH3 70% 80% 90% 100%
N20 30% 10% 10% N20 30% 10% 10% Minimum water penetration
0.05 NA NA NA NA -50 0.254 0.326 0.373 0.408
Minimum number of chemical reactions
0.1 NA NA NA NA -48 0.285 0.366 0.420 0.449
0.2 NA NA NA NA -46 0.321 0.411 0.471 0.515 Fewer problems with oil and sludge. Longer service
intervals
0.3 -47.15 NA NA NA -44 0.360 0.460 0.527 0.576
0.4 -42.10 -46.48 -48.82 NA -42 0.402 0.514 0.588 0.644
0.5 -38.00 -42.51 -44.93 46.52 -40 0.449 0.573 0.655 0.717
1.0 -24.07 -28.96 -31.71 -3359 -38 0.500 0.637 0.797 0.797
2.0 -7.71 -13.62 -16.70 -18.85 -36 0.556 0.708 0.808 0.885
3.0 -2.51 -3.16 -6.69 -9.23 -34 0.617 0.784 0.895 0.980
4.0 -10.32 4.45 -0.79 -1.88 -32 0.679 0.986 0.986 1.08

Conversely, aqueous or “wet” ammonia is Wear in orifice elements such as floats and The real problem is solved and not just the symptoms
very chemically reactive and very aggres- expansion valves becomes greater when Investigation of water content. Use of water rectifier
sive towards copper, copper alloys, zinc, the ammonia contains water. The water units
etc. “Wet” ammonia is highly corrosive creates corrosion in the orifice, i.e. it adds Reduced service and operating costs
and can lead to galvanic corrosion of the corrosion to the erosion and cavitation
Capacity and energy consumption not affected
valves, which in turn might result in regula- already taking place. Furthermore, water
tion problems. This corrosive environment in the ammonia might intensify the cavi- Fewer problems with valves and regulators
together with vibration and/or pulsation can tation affecting the orifice (even though Minimum risk of corrosion
also give rise to the phenomenon known this has not been scientifically proved).
as “fretting corrosion” where surface metal Wear from erosion is also intensified by
fatigue, wear and corrosion becomes in- the larger amounts of rust and sludge
tensified by the presence of the other two. particles that circulate in the system. It is thus a very good idea to make the
Under these conditions, mechanical reg- inspection of system water content a part
ulators and valves can either seize up Conclusion of normal service and maintenance proce-
completely or malfunction because of in- It can be concluded that ammonia refri- dures. Finally, the installation of a water
creased friction (see fig. 6). geration plants often contain more than rectifier can be an attractive investment
the maximum recommended 0.3% water. in terms of operating economy.
What about the oil? This can be because automatic air purgers
Ammonia containing water and oxygen “hide” leakage and allied problems which The “good dry circle”
also reacts with the oil in the compressor allow water to accumulate in the system. Now let us look at the “good dry circle”
and creates reaction products. Some of Another cause is that personnel who ser- where the real problem is cured rather
these are organic acids that react with vice such plants are not always very well than just the symptoms (see fig. 7).
the ammonia and form complex nitrogen acquainted with water-related problems.
compounds (e.g. sludge, salt and soap The initial step is to follow the correct
products) all of which are highly injurious procedure in starting up and servicing
to the plant. the plant. The better these instructions
Fig. 6 are observed the fewer the problems with
Characteristic of the nitrogen compounds Water-related problems on valves and mechanical oil and sludge become, and the smaller
regulators
is that: becomes the risk of corrosion. Problems
– they are partially soluble in ammonia Rust and sludge with mechanical valves and regulators
“Fretting” corrosion
(the ammonia becomes coloured), Valves, filters can become blocked or seize up will thus be fewer.
– they do not dissolve in oil, Vibration/pulsation
– they are able to pass through the oil Fatigue in asperities Making sure that the plant runs with
separator together with the ammonia, Asperities break off minimum water content means lower
Loose particles on surface + corrosion
– they create sludge in the compressor Particles grow in size service and operating costs, without
and throughout the whole system Increased friction negatively affecting capacity and power
Increased wear
(valves, regulators, evaporators), Valves and regulators seize up consumption.
– they act as catalysts which accelerate
the on-going process by creating more For further information, please contact
Many small movements Per Skærbæk Nielsen, tel.: +45 8738
damaging nitrogen compounds.
9641, fax: +45 8628 0801, or e-mail:
Orifice wear in an ammonia plant? psn.dkacd@danfoss.com
It is well known that the orifices can be
subjected to wear because of the erosion 1) A copy of the DIR (Danfoss Industrial Refrigeration)
and cavitation that occur in the orifice technical document “Effects of Water Contamination
in Ammonia Refrigeration Systems” can be obtained
where expansion takes place. Erosion is from the author of this article.
caused by the flowing medium, which at 2Fe + 02 → Fe0, black 2) For a more detailed description of how water content
certain points can reach a velocity almost 3Fe0 + 1/2 02 → Fe304, blue/black is measured and how water is boiled off in ammonia
2Fe0 + 1/2 02 → 3Fe2 03 , red/brown → wear systems refer to the IIAR (The International Institute
the same as that of sound. Cavitation Fe203 + H20 → 2Fe00H, red/brown → rust of Refrigeration) technical bulletin no. 108.
arises because small bubbles in the
ammonia implode (collapse).

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