SECONDARY

REFRIGERANTS

Indirect Refrigeration
1. Primary Refrigerants

Primary refrigerants are those fluids, which are used directly as working fluids, for
example in vapour compression and vapour absorption refrigeration systems. When
used in compression or absorption systems, these fluids provide refrigeration by
undergoing a phase change process in the evaporator. As the name implies,
secondary refrigerants are those liquids, which are used for transporting thermal
energy from one location to other.

2. Secondary Refrigerants

Secondary refrigerants are also

known under the name brine’s or
antifreezes. Of course, if the
operating temperatures are above
0°C, then pure water can also be
used as secondary refrigerant, for
example in large air conditioning
systems. Antifreeze’s or brines
are used when refrigeration is
required at sub-zero
temperatures.

Unlike primary refrigerants, the secondary refrigerants do not undergo phase change
as they transport energy from one location to other. An important property of a
secondary refrigerant is its freezing point. Generally, the freezing point of a brine will
be lower than the freezing point of its constituents. The temperature at which
freezing of a brine takes place it depends on its concentration. The concentration at
which a lowest temperature can be reached without solidification is called as eutectic
point.

3. Reasons For Using A Secondary Refrigerant

The reason for using a secondary refrigerant can depend upon the product to be
cooled, the type and size of the process, and the system design.

The following points illustrate the general application: -

 To avoid contamination of the product or the working environment by the

primary refrigerant.
 To provide a simple system, using a factory assembled packaged unit for the
primary refrigerant and a made to measure secondary system, thus reducing
design and installation costs.
 To provide better contact between the products than could be possible using
a primary refrigerant, i.e. circulation of air.
 To transfer heat over long distances and avoid the problems of pressure
drops and primary refrigerant leaks.
  By using a secondary refrigerant, the primary refrigerant charge is restricted
to the main unit.
 To use a cheaper refrigerant on the secondary side to reduce the cost of the
installation.
 To provide a reservoir of refrigeration by employing large quantities of
secondary refrigerant, this eliminates primary plant short cycling and provides
a backup in the event of main plant breakdown.

4. Desirable Properties Of A Secondary Refrigerant

High Specific Heat Content - The higher this value is, the lower the quantity of
refrigerant required to be circulated for a given load.

Low Density - A fluid with this characteristic will reduce the power required to
circulate it around a system.

Low Viscosity - A fluid with this property will require less effort to circulate it around
the system and subsequently less power and smaller equipment.

Chemically Stable - The fluid should be able to accept pumping stresses without a
changing to its natural state.

Non Corrosive - The fluid should not attack any of the materials within the system
such as pipework, pumps, fittings, and seals.

Thermal Conductivity - A high coefficient would enhance the rate of heat transfer
and hence the rate of cooling, it is therefore a most desirable property.

Non Toxic - One of the primary reasons for using a secondary refrigerant is to avoid
possible contamination of the cooled product. This characteristic is therefore of the
essence.

Non Flammable - The fluid should not provide a fire or explosion risk at any time
during its circulation.

Low Freezing - Compatible with the designed system the refrigerant should not
solidify within the system operating range.

High Boiling Point - The fluid should not evaporate at low temperatures, especially
at normal atmospheric conditions.
3. Components in Indirect Systems and their Function

An indirect secondary fluid system contains all or several of the following main
components: circulation pumps, heat exchangers (evaporators and in cooling units),
air purging devices, expansion vessels, defrosting equipment.

A number of the following components can also be found in an indirect system: shaft
sealings, filters, valves, gaskets, joints, splices, valve sealings, tubes or pipes for
secondary fluid system, drip plates, measuring devices, manometers, etc.

Placing of the various components is considered as well as what is important to think

of in order for the various components proper functioning in the system. The pump
unit is a central part of a secondary fluid system and will be considered first of the
components. Air purging devices and expansions vessels are also treated more
extensively. Heat exchangers and most other mentioned components are dealt with
to some extent.
4. Placing of components

Expansion vessels should be mounted at the suction side of the pump and liquid
filters on the pressure side of the pump. Pumps should be equipped with closing
valves and fully cover drip plates.

A sufficiently high static pressure should be ensured on the suction side of the pump
in order to prevent gas bubbles to appear in the pump.

Micro bubble air purgers and vacuum degassers are mounted in the return pipe.
High point air purgers are mounted on the high points in the system and are
equipped with closing valve in the system.

5. Function of components – important to consider

Pumps - check regularly that the pump with fully covering drip plate and splash
protection functions well. Rinse at once away possible spill.

Air purger devices - check regularly that the device functions well and does not
leak as this is important for satisfying operation. Air cause poorer heat transfer and
lower pump capacity in the system and it increases the risk for corrosion and
leakage. Air purging valves shall, at intervals, be dismantled ad cleansed, preferably
with water. Air purging is most efficient when the system is warm.

Expansion vessel - should be checked to ensure that the pump has sufficiently high
static pressure. Make sure that the device has correctly set pre-pressure in pressure
isolated state. The equipment should of course be free of leakage. The pressure of
the system should be checked regularly.

Valves - check regularly that the valves function and are tight. Rinse away possible
spill instantly.

Filter – place filters at the pressured side of the pump. Choose suitable mask size
and clean the filter regularly.

Measuring device - manometers, etc. – Check that the equipment functions and is
free of leakage.
6. Types of secondary refrigerants

Water

Water as refrigerant has very good thermophysical properties. It freezes at 0°C,

which limits the range of application. When operating close to the freezing point,
antifreeze needs to be used. Water is a very strong solvent, referred to as “the
universal solvent”, dissolving many types of substances, including alcohols, glycols,
glycerol, ammonia, and salts. These inorganic and organic fluids can be used as
antifreezes. Water has the second highest specific heat capacity of any known
chemical compound, after ammonia, as well as a high heat of vaporization. Water
has strong corrosive character due to presence of dissolved oxygen and hydrogen
ions .

Inorganic aqueous solutions

Chlorides

The salts of hydrochloric acid (HCl) and metal ion are called chlorides. Chlorides are
known as highly reactive species. Aqueous solutions based on chloride are strongly
corrosive and require buffering and at least two strong inhibitors, which have bad
impact on the environment. For chloride based solutions, it should be sufficient to
use same construction materials as for seawater. In past, chromates were often
used as corrosion inhibitors but now they are viewed as hazardous. Chemicals used
as antifreezes are mostly found to be sodium chloride or calcium chloride. Both are
similar and effective. Adding salt lowers the freezing point of the water, which allows
the liquid to be stable at lower temperatures and cause ice to melt.

Sodium Chloride

Sodium chloride is also known as common salt, table salt, or halite. Sodium chloride
is well soluble in water, non-flammable and has low toxicity. Sodium chloride can be
used in applications involving contact with food and in open systems. A high heat
transfer coefficient can be obtained with aqueous solutions of sodium chloride due to
its good thermophysical properties. However, it has two main drawbacks: relatively
high freezing point, which limits its use to approximately -21°C (22% NaCl solution)
and high corrosivity, requiring corrosion inhibitors.

Calcium Chloride

Calcium chloride is non-toxic, non-flammable and is highly soluble in water. Calcium

chloride can serve as a source of calcium ions in solution and while precipitating
creates insoluble calcium compounds, which can cause additional scaling problems.
In more severe cases, scale can clog heat exchange surfaces and thereby form a
thermal insulating barrier which inhibits heat transfer efficiency, as well as impeding
fluid flow in the system.
Aqueous solutions of calcium chloride have good thermal properties and low
viscosity at low temperatures but are highly corrosive to ferrous materials when
oxygen is present.
Calcium chloride solution has a lower freezing point and can be used at
temperatures down to -50°C (30% CaCl2 solution). The main disadvantages are high
corrosivity, reduced heat transfer coefficient below -20°C and its incompatibility in
direct contact with food. Calcium chloride is not compatible with elastomers made
from 100% soft rubber. It can be used at much lower temperatures than sodium
chloride. Calcium chloride usually contains sufficient alkali to render the freshly
prepared refrigerant slightly alkaline, but when exposed to air, it gradually absorbs
carbon dioxide and oxygen, which makes the solution slightly acidic.

Magnesium Chloride

Magnesium chloride is highly soluble in water and can cause scaling problems like
calcium chloride. Magnesium chloride is much less toxic to environment and is less
corrosive to steel and other iron alloys than sodium chloride. Magnesium chloride
can
be used down to -34°C as 22% solution.

Lithium Chloride

Lithium chloride is highly soluble in water and a highly polar compound. It is more
soluble in polar organic solvents such as methanol and acetone than sodium
chloride or potassium chloride. Lithium chloride can act as a source of chloride ion
and as soluble ionic chloride. Lithium chloride has highly corrosive character.
Ingestion of this compound can result in poisoning or effect on the central nervous
system due to its lithium content. Aqueous solutions of lithium chloride have very
good thermophysical properties down to very low temperatures (-55°C as 22%
solution of LiCl).

Ammonia

Ammonia is a colourless fluid with a characteristic pungent smell. As a gas it is

lighter than air and more flammable. It is easily liquefied due to the strong hydrogen
bonding between molecules. Ammonia is well soluble in water. Comparison of the
physical properties of ammonia with water shows that ammonia has lower melting
point, boiling point, density, viscosity due to the weaker hydrogen bonding in
molecule. Ammonia is highly toxic to organisms. The aqueous solution of ammonia
has basic character.

Ammonia causes strong irritation to eyes, skin, and respiratory tract. Ammonia is
highly corrosive and not compatible with elastomers made from 100% soft rubber,
isoprene, natural rubber, polyurethane, silicon rubbers and copper.

Ammonia continues to be used as a refrigerant in large industrial processes such as

bulk ice-making and industrial food processing. Since the implication of haloalkanes
as being major contributors to ozone depletion, ammonia is again being attractive as
a refrigerant . Aqueous solutions of ammonia have very good thermophysical
properties down to -55°C (25% NH3 solution).
Potassium Carbonate

Potassium carbonate is a white salt soluble in water, which forms a strongly alkaline
solution. As well as potassium formate, potassium carbonate has a high pH, about
11.5 - 12.5 and is irritating to skin, mucous membrane of eyes and upper respiratory
tract. Aqueous solutions of potassium carbonate have good thermal properties and
rather low viscosity at low temperatures. At high pH of 12 this salt becomes very
corrosive to zinc, soft solder, and aluminium. Potassium carbonate can be used
down to -38°C (40% K2CO3 solution).

Organic Aqueous Solutions

Glycols

Ethylene and propylene glycol water based solutions are popular secondary
refrigerants due to their low corrosivity character and low fire hazards. There is a
problem with ethylene glycol solutions due to their potential toxicity both to the
environment, animals, and food products. Also, the decrease in thermal conductivity
of water solutions as the glycol concentration increases is problematic.

Glycols seem to be less corrosive to carbon steel than alcohols and chloride salts. In
case of glycol solutions, the corrosion potential is comparatively the same as for the
water with which the glycol has been mixed. This means that almost the same
construction material can be used for glycol-based solutions as for freshwater
systems (this comprises also alcohol-based solutions).

After longer time use, glycols start to be slightly acid because of oxidation or
decomposition, which implies an increase of the corrosion potential.

Glycol solutions need to be properly inhibited. Without inhibitors, glycols can be

oxidized into acidic products. The rate of oxidation is influenced by temperature,
degree of aeration, and other factors to which glycol solution is exposed. Thus, the
oxidizing agents and chromates should be avoided while working with glycol
solution.

Ethylene Glycol

Ethylene glycol is colourless, practically odourless, and miscible with water. When
properly inhibited, it has relatively low corrosivity - an advantage when compared to
salt-based refrigerants. Ethylene glycol solution can be used as secondary
refrigerants at rather low temperatures down to -51°C as 40% solution.

Ethylene glycol is toxic, so it is not suitable for open systems, food, and
pharmaceutical applications.

Ethylene glycol is slightly flammable and harmful to environment. Short-term

exposure can result in irritation of eyes, skin and respiratory system; long-term
exposure can have effects on the central nervous system and eyes.
Propylene Glycol

Propylene glycol has similar properties as ethylene glycol. Propylene glycol is slightly
water polluting and practically non-toxic to humans.

The industrial norm recommends replacing ethylene glycol by propylene glycol.

Propylene glycol has low fire hazard when exposed to heat or flame.

Propylene glycol can have quite low pH that might affect the corrosion potential.

Propylene glycol in its inhibited form has the same low corrosivity as ethylene glycol.
Additionally, propylene glycol can be used in food applications. Due to its high
viscosity at low temperatures, propylene glycol is used down to -50°C as 60%
solution.

Glycerol

Glycerol is a colourless, doorless and viscous liquid. Glycerol has three hydrophilic
hydroxyl groups that are responsible for its solubility in water and its hygroscopic
nature. Glycerol has very high viscosity at low temperatures. Glycerol is
environmentally friendly and non-toxic. Glycerol can be used down to -35°C (60%
glycerol solution). Glycerol can be mixed with ethyl alcohol without any other additive
and create a new product .

Alcohols

Alcohol is any organic compound in which a hydroxyl group (-OH) is bound to a

carbon atom of an alkyl or substituted alkyl group. The hydroxyl group generally
makes the alcohol molecule polar. Because of hydrogen bonding, alcohols tend to
have higher boiling points than comparable hydrocarbons and ethers. Alcohols, like
water, can show either acidic or basic properties. They are generally slightly weaker
acids than water.

Methyl Alcohol

Methanol is an antifreeze solution used in industrial refrigeration systems and ground

source heat pumps. Similar to glycols, this solution can be inhibited to stop
corrosion. It can be used at temperatures as low as -40°C owing to its relatively good
heat transfer in this temperature range. The main disadvantage is its toxicological
effects. It is considered more harmful than ethylene glycol and consequently is used
only for process applications located outdoors. Additionally, methanol is flammable
and creates a potential fire hazard where it is stored, handled, or used. Methyl
alcohol is not compatible with elastomers, soft rubber, and polyurethane.
Ethyl Alcohol

Ethanol is a flammable, colourless, non-toxic chemical organic compound. Vapours

may form explosive mixtures with air. Most vapours are heavier than air. Ethanol has
very low surface tension, which may result in leakage in sealing devices and cause
foaming. As a flammable liquid, it requires certain handling and storage precautions.
Ethanol due to its hydroxyl group is behaving like weak acid. Ethanol has high
viscosity at low temperatures and is used down to -45°C at concentration 60%.

Betaine

Betaine (trimethyl glycine) is a by-product of the sugar industry obtained from sugar
beet. Betaine is completely non-toxic and environmentally friendly secondary
refrigerant. This solution was found to have good freezing protection and good heat
transfer properties. Betaine is claimed to have natural protection behaviour against
corrosion. The heat capacity of betaine is slightly lower than glycol solutions. The
viscosity of betaine is very similar to ethylene glycol. Tests showed that betaine even
without any inhibitor is less corrosive than water. However, betaine needs some
additives used for corrosion protection, pH stability, anti-foaming, colouring, and
flavouring.

Potassium Organic Salts

Potassium organic salts are known as environmentally friendly secondary

refrigerants that lately have been popular on market. They are alkaline solutions of
high pH value. They are harmful to galvanized surfaces and zinc materials.

Potassium Acetate

Potassium acetate has low hazard potential. Inhalation may cause mild irritation.
Aqueous solutions of potassium acetate have in comparison with potassium formate
and potassium carbonate, lower pH, about 7.5 - 8.5. Potassium acetate can be used
as antifreezes instead of chloride salts. It offers the advantage of being less
corrosive, however it is more expensive. Potassium acetate is not compatible with
elastomers made from 100 % polyurethane. Potassium acetate has quite good
thermal properties also at low temperatures. Potassium acetate as a 44% solution
can be used down to -53°C.
Corrosion Factors

A variety of natural and system operation factors can have significant effects on the
corrosion rate of materials used in indirect systems. The variables include type of
secondary refrigerant and its corrosion behaviour, fluid velocity, pH, concentration of
solution, temperature, dissolved oxygen, scaling properties and the type of materials
used.

Corrosion Behaviour of Secondary Refrigerants

Chlorides are well known as highly reactive species. Aqueous solutions based on
chlorides are strongly corrosive and require buffering and at least two strong
inhibitors, which have negative impact on the environment. The flow rate of
secondary refrigerants containing chlorides through carbon steel pipe system is
restricted to avoid removing the ferric chloride coating on the pipe surface which
protects against erosion corrosion. Zinc can be used, but for low temperature
application special steels are required to avoid embitterment. Titanium is unsuitable
for chloride containing secondary refrigerants and should be avoided.

Ammonia, as well as chlorides, is highly corrosive and not compatible with

elastomers made from 100% soft rubber, isoprene, natural rubber, polyurethane,
silicon rubbers and copper. Construction materials for ammonia fluids are dependent
on the operating temperature. Impurities in liquid ammonia solution such as air can
cause stress corrosion cracking (SCC) of mild steel. Ammonia is also highly
corrosive towards copper and zinc elements.

Potassium salts are alkaline solutions of high pH value. They are harmful to
galvanized surfaces and zinc elements, but they are defined as having moderate
corrosion character. Potassium acetate is not compatible with elastomers made from
100% polyurethane. The compatible elastomers with potassium formate are e.g.,
nitrile rubber, chlorobutadiene rubber, polyvinylchloride, polyamide, polyethylene.
Potassium carbonate at high pH becomes very corrosive to zinc, soft solder and
aluminium.

Ethylene and propylene glycol are popular secondary refrigerants due to their low
corrosivity and low fire hazard. Glycols seem to give less corrosion on carbon steel
than alcohols and chloride salts. In case of glycol solutions, the corrosion potential is
comparatively the same as for the water. This means that almost the same
construction material can be used for glycol-based solutions as for freshwater
systems.

Methyl and ethyl alcohol, like water, can show either acidic or basic properties and
they are generally defined as low corrosive refrigerants.

Betaine has natural protection properties against corrosion and is less corrosive than
water .
7. Freezing Point

The freezing point temperature, or freezing point, is the temperature at which ice
crystals starts to appear in the solution.

The eutectic temperature is the highest temperature at which full solidification can be
achieved as illustrated in the drawing below.

When salts such as calcium or sodium chloride are

dissolved in water, the solution has a lower freezing
point than pure water.

As more salt is dissolved in the water, the freezing

point lowers in temperature until the eutectic point is
reached.

If additional salts are added, the concentration is

increased above this point, it will have the reverse
affect and the freezing temperature will rise.

The eutectic concentration of brine is that concentration where no further

lowering of the freezing temperature can be achieved by the addition of more
salts.

The freezing point should be below the lowest expected temperature and sufficiently
below the normal operating temperature of the secondary fluid so that it can be
pumped without difficulty through the system. However, the freezing point, or
concentration, should not be too high to take advantages of the good thermo-
physical properties of water. A temperature difference of 10K between the freezing
point and the normal operating temperature is usually recommended.
7. Good preparation & maintenance are essential when using secondary
refrigerants
 
 
These fluids can be one of the least expensive components of a system if they are
sourced and used correctly. There is also plenty of advice available in the market,
and product data sheets and safety data sheets should also be consulted before
use.

Preparation

Always check that the system is correctly sized and material compatibility exists with
the fluid to be used for all the components, such as pumps, pipework, material and
joint seals. It is important to make sure a system is clean, free of dirt, grime, rust and
other particles, and has no stagnant water in it. Test for leaks before filling, charge
slowly to avoid air pockets and purge any entrapped air.

Dilution

Secondary refrigerants come as concentrated or ready to use products. The correct

dilution for freezing protection is essential and the density and viscosity of that
concentration should be considered. When these fluids get close to their freezing
point, their viscosity increases, making them harder to pump. Concentrated product
should be diluted with demineralised or de-ionised water to protect the longevity of
the system. This is because it will be free of Chlorides, Sulphates or Calcium which
can cause problems such as sludge or scale to form. It is often simpler to use a
ready to use product which has already been diluted to the required concentration.

Corrosion Protection

Good quality secondary refrigerants will contain corrosion inhibitors which is a key
feature for the longevity of any fluid. Some products now also use organic inhibitors,
and they are longer lasting and give better thermal transfer properties as they only
form a protective film if there is a sign of corrosion. Traditional mineral based
inhibitors will otherwise form a protective layer on the wall of the system.

Maintenance

Regularly check the PH levels to ensure there are no signs of corrosion and also
check the concentration of the liquid to ensure there are no risks of freezing. Drain or
top up the system with a good quality glycol and ensure the correct concentration
levels are met. Topping up a system with water can dilute the protection levels and
potentially cause costly damage to a system so don’t be tempted to cut corners.
Glycol Maintenance

The glycol solution must be checked at least once a year in accordance with the
manufacturer's recommendations. A base line analysis should be performed within
two to four weeks of initial mixing. This measurement will be used to verify that the fill
was completed properly and will serve as a reference point for comparison with
future test results. As a bare minimum, the solution should be analysed for glycol
concentration, solution pH and general fluid quality.

Glycol Concentration Testing

Propylene Glycol and Ethylene Glycol are often mixed at many different dilution

ratios. The solution concentration is directly related to its freeze point. Failure to
properly monitor your freeze point will initially lead to product slushing and ultimately
bulk freezing.

When freezing occurs, it often leads to damaged pipes and loss of product. In some
cases, ethylene glycol is dangerous if consumed by animals or
humans. Concentration can be easily and accurately checked using a handheld
refractometer. Most quality instruments will test glycol concentrations from 0 to 55%
directly, are portable, and require no complicated adjustments for temperature.

Handheld Refractometer Digital Refractometer