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HISTORY OF REFRIGERATION
The Use of Ice for Refrigeration purposes can be traced back to prehistoric times. Ice
and Snow was often stored in areas that offered basic insulation to maintain low
temperatures.
Cooling drinks came into vogue by 1600 in France. Instead of cooling water at
night, people rotated long-necked bottles in water in which saltpeter had been
dissolved. This solution could be used to produce very low temperatures and to
make ice. By the end of the 17th century, iced liquors and frozen juices were
popular in French society.
Before 1800, food preservation used time-tested methods: salting, spicing, smoking,
pickling and drying. There was little use for refrigeration since the foods it primarily
preserved — fresh meat, fish, milk, fruits, and vegetables — did not play as important a
role in diets as they do today. In fact, diets consisted mainly of bread and salted meats.
19th Century
In the early 19th Century Ice became a form of business were It was sold for currency.
Methods were improved to store ICE and ship it to warmer parts of the world.
By the Late 19th Century refrigeration became commercialised. Ice storage and usage
was still the main form of chilling. This however came with its own problems such as
contamination with unwanted substances. The general hygiene of Ice usage became a
problem.
Post 1900's
At the turn of the 20th century the German engineer Carl Von Linde set up a large-scale
process for the production of liquid air and eventually liquid oxygen for use in safe
household refrigerators.
In the middle of the 20th century refrigerated transport also began to be used on trucks
and trailers which also made large improvements to consumer choice and hygiene.
Safety Issues
Refrigerants like sulfur dioxide and methylchloride if leaked can cause ilness and death.
Ammonia had an equally serious toxic effect if it escaped.
Safe and more affordable refrigeration opened up new gateways in business for new
types of food storage, packaging and presentation.
In metalworking, for instance, mechanically produced cold helped temper cutlery and
tools. Iron production got a boost, as refrigeration removed moisture from the air
delivered to blast furnaces, increasing production. Textile mills used refrigeration in
mercerizing, bleaching, and dyeing. Oil refineries found it essential, as did the
manufacturers of paper, drugs, soap, glue, shoe polish, perfume, celluloid, and
photographic materials.
Fur and woolen goods storage could beat the moths by using refrigerated warehouses.
Refrigeration also helped nurseries and florists, especially to meet seasonal needs
since cut flowers could last longer. Moreover, there was the morbid application of
preserving human bodies. Hospitality businesses including hotels, restaurants,
saloons, and soda fountains, proved to be big markets for ice.
In 1973, Prof. James Lovelock reported finding trace amounts of refrigerant gases in
the atmosphere. In 1974, Sherwood Rowland and Mario Molina predicted that
chlorofluorocarbon (CFC's) refrigerant gases would reach the high stratosphere and
there damage the protective mantle of the oxygen allotrope, ozone. In 1985 the "ozone
hole" over the Antarctic had been discovered and by 1990 Rowland and Molina's
prediction was proved correct.
As a result of the potential ozone layer damage. new technologies in refrigerants have
been developed. The most popular are known as hydrofluorocarbons (HFCs), with
an even lower global warming potential, and no known effects at all on the ozone layer.
Currently CFC's are being phased out and new refrigeration plants and appliances are
being made with safer new generation refrigerants.
REFRIGERATION THEORY
Most people associate refrigeration with cold and cooling, yet the practice of
refrigeration engineering deals almost entirely with the transfer of heat. A good
definition of refrigeration is the removal of heat energy so that a space or material is
colder than its surroundings. Heat is an energy which cannot be created, destroyed or
seen however it can be moved.
This is one of the most fundamental concepts that must be understood. Cold is really
only the absence of heat, just as darkness is the absence of light, and dryness is the
absence of moisture.
"Cold is just the absence of heat"
Below is a basic diagram of how heat is displaced in a household refrigerator. The heat
energy is drawn via the evaporator, it is then displaced at the external part of the fridge
via the condenser into the cooler air.
For these reasons, it is important for engineering and maintenance managers that in-
house service technicians and outside contractors working with refrigerants follow
organizations’ written EPA policy and procedures. Well-defined procedures, appropriate
equipment, and sufficient knowledge of refrigerants will reduce accidents and injuries
on the job, and training can make sure organizations achieve these goals.
T R A I N I N G F O R C O MP L I A N C E
Although mandatory, safety and training are only parts of compliance. The EPA
recommends that every organization designate a facility refrigerant compliance
manager and implement a refrigerant compliance management plan. Producing a
program that outlines organization-specific, written refrigeration regulations is the first
step to effective compliance.
It should describe how EPA regulations fit into an organization’s work processes and
should use flow charts and work statements to illustrate key points. The program also
should define the organization’s specific policies and procedures for refrigerant
handling, from purchase through final disposal.
INTEGRATING SAFETY
Section 608 of the Clean Air Act Amendments of 1990, as well as more recently
proposed EPA amendments, require that technicians follow specific procedures while
maintaining, servicing, repairing or disposing of air-conditioning or refrigeration
equipment.
Technicians can prevent injuries and costly mistakes by consistently following defined
procedures and using common sense when handling refrigeration equipment. Taking
simple precautions can be a substantial leap toward industry-wide safety. Among the
more obvious practices that should become habit for refrigerant technicians are these.
If cylinders will be exposed to temperatures above 130 degrees, technicians should not
fill them more than 60 percent. Hydrostatic pressure can be deadly in an overfilled
refrigerant container. While over-pressure safety devices provide some level of safety,
they do not eliminate risk. An opened valve can spew refrigerant, or the entire tank
might rupture with extreme violence.
Second, technicians should weigh and inspect cylinders carefully before filling. They
also should:
not use cylinders that are dented, rusted, gouged or damaged in any way
examine the valve assembly for leakage, damage or tampering
handle cylinders carefully
store refrigerant cylinders in a vertical position with their valves at the top
become familiar with all pieces of recovery equipment
apply all methods and instruction prescribed by the system’s manual every time
they use the equipment.
Disposable cylinders, which are constructed of common steel, can oxidize and become
weakened by rust. As a result, their wall and seams no longer can tolerate pressure or
contain gases. Technicians should discard rusted containers because they can never
be used for recovery or refilling. To prevent corrosion, technicians should store
containers in dry locations.
Cylinders with residual refrigerant should not be allowed to sit at a job site because
saturated vapor pressure will form if even the smallest amount of liquid is present.
Before discarding a container, technicians should recover any remaining refrigerant per
EPA recovery efficiencies.
Finally, technicians must fill drums to allow vapor space equal to at least 10 percent of
the drum height between the top of the liquid and the drum top. Refillable cylinders
must be retested and recertified every five years, and the test date must be stamped on
the cylinder shoulder. Retesting by visual inspection alone is not permitted.
T R A N S P O R TI N G A N D T R A N S F E R R I N G
In transporting used refrigerant, technicians need to clearly label its container with a
DOT classification tag. When moving a cylinder, they must ensure that it is firmly
strapped onto an appropriate wheeled device. Never roll a cylinder on its base or lay it
down to roll it. Use a forklift truck to move half-ton containers of refrigerant.
Any time a container or system undergoes the transfer of refrigerant, the technician
must check it for refrigerant type, cleanliness and oils used. Also, the container used for
holding transferred refrigerant must be evacuated, and under no circumstances should
workers mix different refrigerants.
T E C H N I C I A N P R O TE C T I O N
Chlorofluorocarbons and hydrochlorofluorocarbons are heavier than air and will replace
air in a confined space. This situation can lead to possible asphyxiation for anyone
working in the space. Oxygen starvation is the leading cause of death in accidents
involving a refrigerant.
Technicians must take extreme care to avoid direct ingestion of refrigerant vapors. If a
spill occurs, they will need to put on a self-contained breathing apparatus or evacuate
the area until it has been properly ventilated.
Also, careless handling of cylinders can result in sudden releases of refrigerant, which
can cause frostbite, skin damage or blindness. To avoid these circumstances, workers
should wear safety glasses with side shields or a full-face shield, safety shoes, hard
hat, long pants, gloves and a long-sleeved shirt.
Workers can prevent accidents around hoses and extension cords by using proper
barriers and signs. Use top-quality, properly attached hoses and lines, place them
where risk is minimal, and inspect hose seals frequently. Wear butyl-lined gloves and
safety glasses when working with hoses. Technicians also can enhance safety by:
ensuring that all power is disconnected and disabled to any equipment requiring
recovery
locking out disconnects with approved lockout devices
opening valves slowly and knowing in advance if liquid vapor will be released
not plugging pressure-relief devices
never applying direct heat to a closed system that contains refrigerant.
Taking precautions when working with any refrigerant can help avoid dangerous
situations and injuries
An HVACR technician is exposed to many personal safety hazards during the course of
a normal workday. In addition to the obvious hazards such as sharp metal, electrical
wiring and climbing ladders, the technician needs to be aware of the safety hazards that
refrigerants pose.
Regular checks on containers and systems for holding pressure, and preparing safety
equipment and procedures to minimize personal exposure after unexpected releases
should help avoid any injuries when handling refrigerants.
BODY’S DEFENCE -
Most refrigerants have undergone extensive toxicity testing before being released for
general refrigeration or air conditioning use. Testing generally involves a range of
exposure levels and times to determine any possible effects on test animals.
Short term exposures at high concentrations indicate any acute hazards such as
irritation, sensitization of the heart or adrenaline and lethal concentration (LC50 is the
amount which kills half the animals in a short amount of time).
Tests that expose animals for longer periods of time, such as 90 days to two years, are
designed to indicate chronic problems. These can include mutagenicity (changes to
cells), reproductive problems, effects on organs or carcinogenicity (cancer-causing).
ASHRAE Standard 341 provides a safety classification for refrigerants based on
information related to personal exposure. ASHRAE Standard 152 uses this safety rating
and additional toxicity information to set requirements for machinery rooms and sets
limits on the amount of refrigerant allowed in systems outside machinery rooms. Many
blends containing these individual components are also classified.
Exposure levels are values given to refrigerants to indicate how much of the chemical a
person can regularly be exposed to without adverse effects. All toxicity test results are
considered when setting this level. The American Conference of Government and
Industrial Hygienists (ACGIH) sets the TLV-TWA values for chemicals. TLV-TWA
stands for Threshold Limit Value-Time Weighted Average, which is the amount of
chemical a person can be exposed to for 8 hours a day, 40 hours a week, without
adverse effects.
The maximum value for any chemical is 1,000 ppm, though many refrigerants have
shown no effects in toxicity testing at values much higher than that. Other organizations
and chemical producers have similar exposure level indexes based on the same
criteria. These are the Workplace Environmental Exposure Limit (WEEL) set by the
American Industrial Hygiene Association (AIHA); Permissible Exposure Limit (PEL) set
by OSHA; and Acceptable Exposure Limit (AEL) used by DuPont.
There are also the Short Term Exposure Limit (STEL), which is based on a 15-minute
exposure time in any given day as well as the value Immediately Dangerous to Life or
Health (IDLH). These are used to give guidance for machinery room requirements,
ventilation and alarms in an emergency or escape situation, or in circumstances where
short releases of refrigerant are expected, which could include refrigerant transfers or
servicing large equipment.
Toxicity data is usually summarized in great detail on Material Safety Data Sheets
(MSDS). What all of this data means to the technician, however, is that commercial
refrigerants are safe enough to use provided you don't breathe too much of them.
Industry practices for handling refrigerant are intended to minimize personal exposure
as well as reduce releases into the atmosphere.
Flammability Combustion/Decomposition
Flammable refrigerants present an immediate danger when released into the air. The
refrigerant can combine with air at atmospheric pressure and ignite, causing a flame
and possibly an explosion to occur. Because of the obvious hazards, the use of
flammable refrigerants is restricted to controlled environments that have monitors,
proper ventilation, explosion-proof equipment and generally few people near the
equipment (refineries, storage warehouses, breweries, etc.).
Some refrigerants can burn with oxygen, but only at higher pressures or temperatures
and never in air at atmospheric conditions. These are called "combustible" refrigerants.
Underwriter's Laboratories (UL) lists these refrigerants as "Practically Nonflammable."
R-22 and R-134a fall into this category. R-22 was found to cause a combustion hazard
during a pressurized leak test with air. For this reason, most refrigerants should be used
only with pressurized nitrogen for leak testing. As long as refrigerant is not mixed with
large amounts of air, there should be little hazard from these refrigerants during normal
handling and use.
Decomposition can occur with any refrigerant when it gets hot enough (generally above
7000° F). Refrigerant can decompose in systems or containers exposed to fire or other
extreme heat, electrical shorts (burnouts), or in refrigerant lines being soldered or
brazed without being cleared first. Obviously, refrigerant containers or charged systems
should never intentionally be exposed to a flame or torch.
When a refrigerant is decomposed or burned, the primary products formed are acids:
Hydrochloric acid (HCI), if the refrigerant contains chlorine, and hydrofluoric acid (HF), if
it contains fluorine. These products are certainly formed when hydrogen is present,
such as from the breakdown of oil, water or if the refrigerant has hydrogen attached
(like R-22 or R-134a). If oxygen also is present (from air or water), then it's possible to
form carbon monoxide, carbon dioxide and various unsaturated carbonyl compounds --
the most notorious of which is phosgene.
Being extremely toxic in small amounts, phosgene formation was a real concern when
traditional refrigerants (R11, R- 12, R- 113, R- 114) decomposed. Phosgene contains
two chlorine atoms and an oxygen atom. It will only form when oxygen is present and
only the refrigerants with chlorine attached will produce phosgene (not HFCs). R22 has
only one chlorine atom per molecule, so it is extremely difficult, chemically speaking, to
get another one attached to form phosgene. Decomposition of R-22 or HFCs may form
other carbonyl fluorides, however they are not as toxic as phosgene.
The standard practice for handling decomposed refrigerant is to collect the gas, treat
the refrigerant and/or the system for acid contamination, and appropriately dispose of
the burnt gas. Please note that any cylinder or system component exposed to high heat
or fire should be retested or discarded. Cylinders used to recover burnt gas should be
checked and cleaned before being put back into service, especially the valve and/or
pressure relief device.
Physical hazards
The fact that it's a liquified gas under pressure is one of the more obvious hazards of
refrigerant. Sudden, unexpected release of pressurized refrigerant can result in
personal injury.
Frostbite.
Liquid refrigerant suddenly released from high pressure to atmospheric pressure will
flash and boil to vapor. Naturally, the temperature of the refrigerant will drop quickly to
the boiling point and the refrigerant will quickly absorb heat from whatever it is touching.
If the refrigerant is touching skin it can cause frostbite.
Frostbite damages skin by freezing water inside the skin cells, which can expand and
burst the cell walls. To treat frostbite cover the exposed area with warm (not hot) water
or a wet compress. The skin must recover slowly or more damage can occur. Do not
rub the affected area to try to warm it as it may inflict more damage. Protective clothing,
gloves and eye protection are effective at preventing frostbite by keeping liquid
refrigerant away from the skin.
Cylinders or systems without pressure relief devices could break if the refrigerant
pressure inside were to exceed the strength of the cylinder or system component. This
type of failure can be quite hazardous if the refrigerant is at a high pressure or solid
material is blown loose. Containment failures are caused by one of two things: The
refrigerant pressure has increased above the pressure rating of the cylinder or system,
or something has happened to the cylinder or system so that it will no longer hold
normal refrigerant pressure.
Refrigerant tubing, hoses, system components and some refrigerant cylinders surely
would fail at some elevated pressure without certain safety provisions. Various pressure
relief devices are used to lower the pressure back to safe limits by releasing some or all
of the refrigerant.
Valves on many refrigerant cylinders are fitted with spring-loaded pressure relief valves.
These are typically set to release pressure somewhere above typical refrigerant
pressures at normal use or transportation temperatures, but below the maximum
service pressure of the cylinder. When the pressure is reduced to a safe level the valve
should close itself.
Other cylinders or storage vessels are fitted with burst discs as the pressure relief
device. These are pieces of metal designed to break at some preset pressure, again
lower than the maximum service pressure of the container. In the case of a burst disc,
the entire contents of the container will be released. This is also the case with a fusible
plug, which is designed to melt at a certain temperature. It's used to relieve the
pressure in a tank or system in a fire situation before the pressure gets high enough to
burst the tank, tubing or system component.
The best way to avoid pressure-related hazards is to always use cylinders and system
components that have the correct pressure rating for the refrigerant you're using. Table
1 lists the typical cylinder service pressures that manufacturers and distributors use for
various refrigerants. Pressure ratings for system components must be chosen based on
the application and expected service pressures for the intended application. Pressure
ratings are also based on the refrigerant chosen. Always check for signs of damage or
excessive wear before filling recovery cylinders, picking up new refrigerant cylinders or
attaching new parts to a system.
Safety information
1. Any crew member, who discovers that there is a Freon leak must Move to an area of fresh air and warn
other crew members; Inform the chief engineer immediately; Open up windows and doors and ventilate
the space using fans or blowers, if practicable; If he feels any unusual health effects, seek medical advice.
2. All crew members should be aware of the hazards which may be associated with handling of refrigerants
on board.
3. Freon vapour is heavier than air and may accumulate in low-lying areas, at deck level, displacing oxygen
and posing an asphyxiation hazard.
4. Odour is not an adequate indicator of the presence of Freon and does not provide reliable warning of
hazardous concentrations.
5. Freons are generally non-flammable and non-combustible, however, when involved in a fire or in contact
with heated surfaces (>480°C), Freons decompose producing hydrogen chloride, hydrogen fluoride,
phosgene, and chlorine. All of these decomposition products are acutely toxic and are very hazardous even
in low concentrations.
6. Freons are incompatible with perchloric acid, chromium trioxide, nitric acid, chemically active metals
(such as aluminium and zinc), alkali metals (such as sodium and potassium); and alkaline earth metals
(such as beryllium, magnesium, and calcium).
7. Freons generally have a low order of toxicity. However, exposure to relatively high concentrations (>100
ppm) may produce adverse effects on health. Possible exposure routes include inhalation, ingestion,
skin and eye contact.
8. Freon vapour may cause irritation of the eyes, nose, throat, and mucous membrane at low
concentrations. At high concentrations, Freon vapour may cause pulmonary oedema and neurological
problems such as central nervous system depression, dizziness, headache, drowsiness, tremors,
seizures, confusion, lack of coordination, loss of consciousness, and paralysis. 9. Inhalation of high
concentrations may also result in temporary alteration of the heart’s electrical activity. The sensitivity of the
heart to the arrhythmogenic action of epinephrine will increase, causing irregular pulse, palpitations, or
inadequate circulation. Deliberate inhalation (‘sniffing’) may cause death without warning.
10. At extremely high concentrations; several thousand parts per million (ppm), Freon vapour has the
potential to reduce the amount of oxygen available for breathing, especially in confined spaces, which can
lead to asphyxiation.
11. Skin contact with liquid Freon can cause frostbite. Repeated skin contact with Freon gas may also
cause drying with rashes. 12. Chronic exposure to Freon may produce weakness, pain, and
paresthesias (a sensation of numbness, tingling or burning) in the legs. Chronic fluorocarbon exposure has
been linked with motor, memory and learning deficits. Long-term inhalation of high concentrations may also
lead to abnormal liver function with hepatic lesions.
First aid
1. Eyes - If eye tissue is frozen, obtain medical attention immediately. If eye tissue is not frozen,
immediately flush eyes with large amounts of water for at least 15 minutes, occasionally lifting the lower
and upper eyelids. If irritation, pain, swelling, tearing, or sensitisation to light persists, obtain medical
attention as soon as possible.
2. Skin - If frostbite has occurred, do not rub the affected area. Flush with water or remove frozen clothing
from frostbitten area and seek medical attention immediately. Otherwise, immediately remove
contaminated clothing and wash contaminated area with soap and water for at least 15 minutes. Seek
medical attention, especially if redness, itching, or burning is evident.
3. Ingestion - If Freons are ingested, do not induce vomiting, as the hazard of aspirating the material into
the lungs is greater than allowing it to progress through the intestinal tract. Drink one to two glasses of
warm water and obtain medical attention if necessary.
4. Inhalation - Move the exposed individual to fresh air immediately. If the person is not breathing, give
artificial respiration. If the person has difficulty breathing, give oxygen. Seek medical attention.
Safe handling
Best practices for the safe handling of refrigerants include:
1. Store refrigerants in a clean, dry area out of direct sunlight, where temperature that does not exceed
50°C;
2. Never pressurise refrigerant systems or vessels with air for leak testing or any other purpose;
3. Never tamper with cylinder valves or pressure relief devices;
4. Never reuse or recharge disposable cylinders;
5. Wear protective clothing such as gloves and eye protection when handling any refrigerant;
6. Avoid contact with liquid refrigerant because frostbite may occur;
7. Avoid exposure to vapours through spills or leaks;
8. Evacuate the area if a large spill occurs. Return only after the area has been properly ventilated;
9. Verify proper cylinder hookup to the system;
10. Check to be sure the cylinder label matches the colour code;
11. Open cylinder valves slowly;
12. Avoid rough handling of refrigerant cylinders;
13. Do not perform any repair on pressurised equipment. Verify that the system has been completely
evacuated with a vacuum pump before opening any lines;
14. Before welding or brazing, evacuate the equipment and then break the vacuum with air or nitrogen;
15. Always ventilate the work area before using open flames
The following precautions are recommended for the safe handling of used
refrigerant:
Use personal protective equipment, such as side shield glasses, gloves, safety shoes
and hard hat, when filling and handling cylinders.
Avoid skin contact with liquid refrigerant since it may cause frostbite.
Be aware that inhalation of high concentrations of refrigerant vapor is harmful and may
cause heart irregularities, unconsciousness or death. Since vapor is heavier than air.
avoid low areas without suitable ventilation.
Do not apply open flame or heat cylinder above 125° F (52° C).
Do not artificially cool cylinder.
Use only cylinders designed and marked for refrigerant recovery service. DO NOT
REUSE cylinders intended for virgin refrigerant service. Make certain the cylinder is
charged only with the refrigerant for which it is designated and labeled. DO NOT mix
different refrigerants in the same cylinder.
PRE-FILL PROCEDURES
Prior to filling a recovery cylinder, identify the refrigerant to be recovered and make
certain the cylinder is marked and labeled for that refrigerant. Read all labels.
Make certain the cylinder retest date has not expired. Do not fill if the present date is
more than 5 years past the most recent marked test date.
Inspect cylinder for signs of damage, such as dents, gouges, corrosion. Do not fill
damaged cylinders.
Inspect valve for damage and ease of operation.
Determine maximum allowable gross (filled) weight—this should be prominently marked
on the side of the cylinder.
FILLING PROCEDURE
Be sure you have an accurate scale suitable for weighing the cylinder and contents, a
proper gauge set manifold and proper hoses and connectors.
Be sure cylinder is free standing on the scale with no restriction of free movement
caused by hoses, connections, etc.
Monitor pressure during filling carefully. DO NOT exceed maximum service pressure
which is stamped on shoulder or collar of the cylinder.
Monitor gross weight during filling to assure that overfilling does not occur.
Shut off valve if maximum gross weight or service pressure is reached. DO NOT
OVERFILL.
After recovery, close cylinder valve securely.
Check weigh cylinder.
PRE-SHIPMENT PROCEDURES
On one of the Belgian ships, the second engineer came to the engine control room and found it
extremely warm. He went to check on the A/C compressors. Noting a loss of Freon in the
system, he decided to check for leaks. Based on his previous experience, he checked the
switchboard room first, as similar leaks had occurred there before. On entering the switchboard
room he ‘smelled’ Freon gas and instantly started to feel dizzy. Fortunately,
he managed to turn round and made it out of the room safely. Having left the switchboard room,
the engineer had to sit down in order to recover from the dizziness. After this near-miss, the
room was entered with breathing apparatus, the source of the Freon leak was found, the system
was isolated, the leak repaired and the room thoroughly ventilated. On another vessel, a low
level alarm of Freon in the refrigerator compressor was observed in the engine control room.
The chief engineer decided to recharge the system, using a flexible hose linking a full Freon
cylinder and the recharging valve located on the compressor. After recharging, he closed
the supply valve on the cylinder, then closed the valve on the compressor and released the
pressure from the hose. After disconnecting the hose, the chief engineer observed that
the recharging valve on the compressor was leaking. He decided temporarily to fit a threaded
plug over the leaking valve to control the gas before a repair attempt could be made. He
momentarily removed the leather glove he was wearing and while threading the plug, a jet of
liquid Freon splashed on his left hand, causing severe frost burns. Fortunately the ship was
in port, so he was taken for medical treatment ashore.
Root cause/contributory factors
1. Lack of procedures;
2. Inadequate situational awareness;
3. Poor risk assessment;
4. Failure to use personal protective equipment (PPE) properly;
5. Failure of the recharging valve spindle; or
6. Recharging valve not closed properly (due to hard turning of the spindle),
which allowed Freon to escape.
Corrective actions
SMS procedures reviewed as health and safety hazards
of refrigerant gases were not adequately addressed in the
manuals.
In 1973, Prof. James Lovelock reported finding trace amounts of refrigerant gases in
the atmosphere. In 1974, Sherwood Rowland and Mario Molina predicted that
chlorofluorocarbon (CFC's) refrigerant gases would reach the high stratosphere and
there damage the protective mantle of the oxygen allotrope, ozone. In 1985 the "ozone
hole" over the Antarctic had been discovered and by 1990 Rowland and Molina's
prediction was proved correct.
As a result of the potential ozone layer damage. new technologies in refrigerants have
been developed. The most popular are known as hydrofluorocarbons (HFCs), with
an even lower global warming potential, and no known effects at all on the ozone layer.
The future of refrigeration at the beginning of the 21st Century is now very driven by
conservation and has many different demands placed on it.
So a clean and green method of refrigeration is the future and we will look into the
different ideas and progress thus far.
M A G E N TI C R E F R I G E R A TI O N
Karl Sandeman, a physicist at Cambridge University, UK, has helped resolve the
practical issues, the cooling power of the 21st century fridge will come from a 19th
century discovery - and it promises to cut energy consumption by 40% and save the
ozone layer.
The key is a material that cools when it is put in a magnetic field. The idea - which is
ambitious, but feasible - is to replace the present system used by refrigerators the world
over. Your kitchen fridge has a compressor, which turns a gas into a liquid, releasing
heat (which you'll feel at the back of the fridge). The liquid is then pumped round the
inside walls of the fridge, where it draws heat from the contents; that turns it into a gas,
which is pumped on to the compressor.
But what if you could replace the fluid with a magnet? "The amazing thing about
magnetism is that it's actually a quantum mechanical phenomenon," says Sandeman.
"It's all down to something mysterious called spin. The electrons act almost like a
miniature bar magnet."
Temperature change
As a quantum mechanical property of the electron, spin is usually taken to mean its
rotational momentum (like the Earth rotating around its axis). That momentum -
described as "up" or "down" - creates a tiny magnetic field. When all the electrons in a
material spin in the same way, their fields combine to create what we perceive as
magnetism. However, an iron magnet heated to 700C will "disorder" and lose its
powers, known as a magnetic phase transition.
In 1881, the German physicist Emil Warburg put a block of iron into a strong magnetic
field and found it increased very slightly in temperature. Scientists now know the
electrons pivot in the field to align at a lower energy state, releasing surplus energy.
The metal warms up in what's known as the magnetocaloric effect, which is greatest
near the magnetic phase transition temperature.
"If you can suddenly alter the degree of ordering of all these little spins, then you get a
large response," says Sandeman. For iron at room temperature, the response is just
0.1C. Some materials cool in a magnetic field, a property that's used in low temperature
research. Finding the right room temperature material is the key to a magnetic fridge,
where the cooling power is derived from a positive magnetocaloric effect coupled to
heat exchange.
One material works nicely: the element gadolinium (Gd). It's a silvery-white metal that's
strongly attracted by a magnet, has a magnetic disordering temperature of 20C, and a
giant magnetocaloric effect of several degrees. A waste product from permanent
magnet manufacture, gadolinium costs around £100 per kg; a magnetic fridge would
use 0.15kg. Sandeman's current research, however, is looking at other possibilities.
"The quest is to get away from these expensive rare earth materials and look for
magnetic materials which have a phase transition at room temperature," says
Sandeman, whose research job at Cambridge University is funded by the Royal
Society. He also works with Professor Derek Fray, a leading expert in materials
chemistry. "What I'm actually working with is an alloy of two magnetic materials, cobalt
and manganese," says Sandeman.
When these elements are mixed with non-magnetic "spacers" like silicon, the cost falls
to £5 per kg. Strangely, his latest experimental alloy has a negative magnetocaloric
effect - it cools in a magnetic field. This could also be harnessed for fridges through a
heat exchange process.
A Cambridge University spin-out company, Camfridge Ltd, has built two prototype
magnetic fridges that use gadolinium. While the latest one is little more than fridge
innards, the team - which includes Sandeman as chief scientific officer, Fray and
experienced business people - is striving to develop the revolutionary effect for
commercial exploitation in fridges and, perhaps, air conditioning.
"It's a sea change in thinking," says Sandeman. "It never ceases to amaze me how you
can take a block of this stuff and stick it into a [magnetic] field. The prototype is
operational and has achieved a large temperature span."
A magnetic fridge works like this. Powdered gadolinium (with coarse grains for good
heat transfer qualities) is put into a magnetic field. It heats up as the randomly ordered
magnetic moments - the electrons with spin - are aligned, or "ordered", by the field. The
newly-acquired heat - a boost of between 2-5C, depending on the gadolinium's original
temperature - is removed by a circulating fluid, like a conventional fridge.
The magnetic field is removed and the gadolinium cools below its starting temperature
as the electrons resume their previously disordered state. Heat from the system to be
cooled - your fridge interior - can then be transferred to the now cooler metal. Then all
you do is endlessly repeat. But unlike conventional fridges, which need very toxic
chemicals, the only liquid needed for heat transfer is water, alcohol or, more likely,
antifreeze.
A more advanced prototype next year will optimally bring together three elements -
temperature span, cooling power and efficiency - along with a faster motor. This will
allow less gadolinium to be used with a smaller magnet, saving materials costs.
Camfridge's managing director, Neil Wilson, says: "In terms of technical specification,
that prototype will get us to a domestic fridge. Commercial manufacturers have hit the
wall; there is not much more they can do. We're wanting to cut the energy use by half."
Professor Stephen Blundell, of Oxford University, also understands the issues well, as
he's written a textbook on magnetism and researches magnetic properties in materials.
Magnetocaloric effects are becoming more practical, he thinks, thanks to improved
magnet technology and new materials. A magnetic fridge would be compact, less noisy
and won't need harmful gases.
"I think this technology has real potential, but it is still at the early stages. The claims of
40% efficiency savings seem a little speculative, though not completely unreasonable,"
says Blundell.
Some 15% of UK energy is used in refrigeration and cooling for air conditioning, and
much more in warmer countries. Garry Staunton, head of low carbon research at the
Carbon Trust, which is financially supporting the magnetic fridge's development along
with Cambridge University and other investors, says that 22m tonnes of UK carbon
dioxide emissions annually are due to refrigeration and air conditioning. Efficiency
improvements to domestic fridges since 1990 have seen a 27% reduction in their
energy use.
Increasing energy efficiency with new technology is the key to stabilising and reducing
carbon emissions. Consumers seem willing to support and demand new energy-
efficient appliances in their homes, while everyone has felt the sharply rising cost of
electricity. As the fridge magnet moves inside the fridge, it may become the exciting
new green technology of the 21st century.
C A R B O N D I O X I D E R E F R I G E R A TI O N
Purdue engineers will present several papers detailing new findings about carbon
dioxide as a refrigerant, including:
Creation of the first computer model that accurately simulates the performance of
carbon-dioxide-based air conditioners. The model could be used by engineers to design
air conditioners that use carbon dioxide as a refrigerant. A paper about the model will
be presented on July 26 during a special session sponsored by the U.S. Army in which
researchers from several universities will present new findings.
Carbon dioxide is promising for systems that must be small and light-weight, such as
automotive or portable air conditioners. Various factors, including the high operating
pressure required for carbon-dioxide systems, enable the refrigerant to flow through
small-diameter tubing, which allows engineers to design more compact air conditioners.
More stringent environmental regulations now require that refrigerants removed during
the maintenance and repair of air conditioners be captured with special equipment,
instead of being released into the atmosphere as they have been in the past. The new
"recovery" equipment is expensive and will require more training to operate, important
considerations for the U.S. Army and Air Force, which together use about 40,000
portable field air conditioners. The units, which could be likened to large residential
window-unit air conditioners, are hauled into the field for a variety of purposes, such as
cooling troops and electronic equipment.
"For every unit they buy, they will need to buy a recovery unit," Groll says. "That's a
significant cost because the recovery unit is almost as expensive as the original unit.
Another problem is training. It can be done, but it's much more difficult than using
carbon dioxide, where you could just open a valve and release it to the atmosphere."
The recovery requirement would not apply to refrigerants made from natural gases,
such as carbon dioxide, because they are environmentally benign, says Groll, who
estimates that carbon dioxide systems probably will take another five to 10 years to
perfect.
Carbon dioxide was the refrigerant of choice a century ago, but it was later replaced by
synthetic chemicals.
"It was actually very heavily used as a refrigerant in human-occupied spaces, such as
theaters and restaurants, and it did a great job," says Groll, who is chair of the Gustav
Lorentzen Conference.
But one drawback to carbon dioxide systems is that they must be operated at high
pressures, up to five times as high as commonly seen in current technology. The need
to operate at high pressure posed certain engineering challenges and required the use
of heavy steel tubing.
During the 1930s, carbon dioxide was replaced by synthetic refrigerants, called
chlorofluorocarbons, or CFCs, which worked well in low-pressure systems. But
scientists later discovered that those refrigerants were damaging the Earth's
stratospheric ozone layer, which filters dangerous ultraviolet radiation. CFCs have since
been replaced by hydrofluorocarbons, which are not hazardous to the ozone layer but
still cause global warming.
However, recent advances in manufacturing and other technologies are making carbon
dioxide practical again. Extremely thin yet strong aluminum tubing can now be
manufactured, replacing the heavy steel tubing.
Carbon dioxide offers no advantages for large air conditioners, which do not have
space restrictions and can use wide-diameter tubes capable of carrying enough of the
conventional refrigerants to provide proper cooling capacity. But another natural
refrigerant, ammonia, is being considered for commercial refrigeration applications,
such as grocery store display cases, Groll says.
Engineering those systems is complicated by the fact that ammonia is toxic, requiring a
more elaborate design in which the ammonia refrigerant is isolated from human-
occupied spaces. The first ammonia systems are currently being tested in Europe, and
results will be presented during the Gustav Lorentzen Conference, Groll says.
Groll's work is funded by the U.S. Army, Air Force and the American Society of Heating,
Refrigerating and Air-Conditioning Engineers, as well as the Air Conditioning and
Refrigeration Technology Institute
S O L A R P OW E R
A network of steel pipes and tanks tucked behind a small building at the University of
Florida could lead to a new method of creating two seemingly unrelated products --
electricity and refrigeration -- by tapping into the power of the sun.
The pipes and tanks are the guts of a just-launched experiment to test what Yogi
Goswami, a UF professor of mechanical engineering, describes as a novel solar- or
geothermal-powered thermodynamic cycle.
The system, first des"We’ve seen that it works in theory, and we’ve set up this
experimental system to prove that it works in practice," said Goswami, a specialist in
solar energy who also is director of UF’s Solar Energy & Energy Conversion
Laboratory.
Described in the Journal of Solar Energy Engineering last year, will attempt to verify
what Goswami describes as a new combination of two classic thermodynamic cycles:
the Rankine, or steam cycle, and the absorption-refrigeration cycle.
Both cycles are standard fare in engineering textbooks. The Rankine cycle, typically
found in large power plants, uses heat to boil water and create pressurized steam,
spinning a turbine and producing electricity. The absorption-refrigeration cycle, seen in
large commercial refrigeration units, chills air through boiling and condensing ammonia.
In Goswami’s experimental set-up, hot water is used to heat pressurized ammonia past
its boiling point, generating ammonia steam. This is possible because ammonia
maintained at the pressure required to spin the turbine boils at a far lower temperature,
around 212 degrees Farenheit, than water in the same circumstances, which requires
temperatures of at 400 to 500 degrees. In theory, the hot water would come from deep
underground or solar collectors, although for the purposes of the experiment a
household hot-water heater is used.
The next step is for the pressurized ammonia vapor to spin a turbine and produce
electricity (a process simulated in the experiment through using a heat exchanger and
expansion valve). The unique part is what happens next. As the ammonia spins the
turbine, it actually falls below room temperature, reaching lows of 32 degrees or lower --
cold enough to make ice. The result can be used for refrigeration or air conditioning.
"The unique thing we’re doing is that we can remove so much of the energy from the
ammonia in the turbine that it actually becomes very cold," Goswami said. "We can
then use that cold gas to our advantage for air conditioning or to create ice."
The system is not the first to attempt to use solar or geothermal power to drive a
turbine, Goswami said. The Solar Energy Generating System, a mammoth facility in the
Mojave desert in Southern California, has used specially designed hot water collectors
to produce as much as 354 megawatts of power -- enough for 70,000 homes. But the
collectors are extremely expensive, making the power more costly than electricity
produced with fossil fuel technology.
"The problem has been that the capital cost is about $3,500 per kilowatt of capacity," he
said. "To make it competitive, we really need to bring that cost to less than $2,000."
Goswami said his system is more economical because it can use off-the-shelf
collectors. Although it could be used on a large scale, the system would be ideal for
homes that could easily take advantage of both the electricity and the refrigeration, he
said.
"What we’re looking at is we can have a power plant to give you as low as five
kilowatts, so a power plant is good enough for a household," he said.
Another application for the technology is to milk additional energy from the hot waste
water produced by conventional power plants. Even the most efficient power plants
today capture only 30 to 40 percent of the energy in the fuel, releasing the bulk of the
remainder in the form of heat -- much of it as hot water with sometimes damaging
environmental consequences. Goswami said his system, installed on the outlet pipes
for the hot water, could leach 20 to 30 percent more energy from the system while also
cooling down the water. As a result, the plant could generate extra electricity while
gaining cooling capability for on-site refrigeration or air conditioning needs, he said.
The research is funded with a $175,000 grant from the U.S. Department of Energy,
which is interested in developing the geothermal application of the technology.
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