8.

Switching to Alternative Refrigerant

1
8.1 Control of CFSs

In June 1974, Professor F. S. Rowland and Dr. M. J. Molina have published a paper
pointing out a possibility that CFCs may have a deleterious effect on the ozone layer
and impact on the human being and ecological system. This paper evoked a great
debate in the U.S. and concern over increasing global depletion led to a ban on CFCs
usage.

(1) Phenomenon of Ozone Layer Depletion

Ultraviolet rays of certain wavelength were found to be harmful to the biology, such as
inducing skin cancer and affecting genes. Ozone layer effectively blocks this
ultraviolet rays from reaching the earth and protects various forms of life on Earth.
In 1985, Dr. Farman in England has discovered that the ozone layer was thinned from
its normal concentrations in the ozone layer above Antarctica in spring and recovered to
the normal level in summer. On the image transmitted from the satellite has
confirmed this thinning in the ozone layer above Antarctica. Because it appeared
like a “hole” developed in the ozone layer, this phenomenon was called “ozone hole”.
It has been long suggested that Freon and other CFSs destroy the ozone layer and
create a threat to animal life on the Earth because of ultraviolet rays. Many
researches and studies have been undertaken to determine the relationship between
the ozone layer depletion and CFCs.
(2) Mechanism of Ozone Layer Depletion
Ultraviolet rays dissociate molecular oxygen into oxygen atoms. These oxygen atoms
then combine with nondissociated molecular oxygen to yield ozone. Ozone is formed
near the equator where there is a lot of solar radiation. Once it has been formed, it
spreads toward the poles together with slow atmospheric flow and forms the ozone
layer.
CFCs are very stable substances, which are not dissolved on the earth and in the
troposphere. They reach the stratosphere and become permeated. The theory of
CFCs destroying the ozone layer is as follows; CFCs containing chlorine go through
photodecomposition by ultraviolet rays and release chlorine. Then a chemical reaction
occurs using this chlorine as catalyst and destroys the ozone layer. Once chlorine has
reached the stratosphere, it keeps destroying ozone for a long period of time (See Fig.
8.1.).
(3) Major Development of CFCs Control
In 1985, “Vienna Convention for the Protection of the Ozone Layer” was adopted. The
amended protocol provided that the consumption of ozone depleting substance should be
controlled below 25% based on the consumption level of CFSs in 1986 starting from
January 1994 and should be banned totally from 1996.

2
 Sun

Sun
Ultraviolet rays Ultraviolet rays

Ultraviolet rays

Stratosphere

Dissolve CFCs
troposphere
Generate ozone
Destroy ozone
Diffuse CFCs
Altitude (km)

[Figure 8.1] Mechanism of formation and depletion of ozone

[Table 8.1] History of CFCs Control

1974 Professor Rowland and Dr. Molina at Univ. California, US,

indicated the ozone layer depletion by CFCs.
1977 United Nations Environment Programme (UNEP)
determined to discuss the CFCs control issue.
1978 The production of aerosol-spray using CFCs as propellants
was banned in the United States.
1979 The use of CFCs in aerosol-spray was banned in Canada
and Northern Europe.
EC directed to freeze the production capability of CFC-11 and 12 and reduction
1980
efforts of CFCs for aerosol-sprays. Japan followed this movement.

1985 UNEP adopted the Vienna Convention for the Protection

of the Ozone Layer.and Northern Europe.
Montreal Protocol on Substances that Deplete the Ozone
1987
Layer was adopted and took effect in January 1989.
Japan promulgated the Law Concerning the Protection of the Ozone
1988
Layer Through the Control of Specified Substances and Others.
Ministry of the Environment and Ministry of International Trade and Industry promulgated
1989
the guidelines for control of discharged and rationalization of use of specified CFCs.

1990 Japan promulgated the amendment and notification of the Government Ordinance
Concerning the Recovery, Purification and Reproduction of CFC Refrigerant..
Fourth Session of the Conference of the Parties to the Montreal
1992 Protocol was held. Cease of production of the specified CFCs was
agreed to move up to the end of 1995 and the control and cease of
production of HCFC in 2020 in principle.

3
Expanding Knowledge

Specified CFCs under Control

Montreal Protocol specified the following five CFCs as substances to be controlled to
protect the ozone layer (Table 8.2). These are called “specified CFCs”.

[Table 8.2] The kind of specified CFCs

Name Chemical ODP* Application

formula
Methane CFC-11 CCl3F 1.0 Refrigerant, aerosol-spray,
foaming-agent, detergent
CFC-12 CCl2F2 1.0 Refrigerant, aerosol-spray,
foaming-agent
Ethane CFC-113 C2Cl3F3 0.8 Detergent

CFC-114 C2Cl2F4 1.0 Aerosol-spray, foaming-agent

CFC-115 C2ClF5 0.6 Dry etching agent

*Ozone Depletion Potential:

Estimated value (relative value) of the ozone destructive power asked for CFC-11 as 1.0

Although HCFC-22 used in residential air-conditioning contains Cl- base, since it also
contains a H- base, it is easily discomposed in the atmosphere and does not reach the
ozone layer easily. The ODP is 0.05. Although HCFC is not specified as specified CFC,
since the impact is not zero, it was agreed that the production is ceased in 2020.

8.2 Alternative CFCs and Adaptation of Automotive Air-Conditioning

(1) Selection of Alternative CFCs

Alternative CFCs for automotive air-conditioning should satisfy the following
characteristics:
① Exerts no depletion effect to ozone layer
② Possesses safety (no toxicity, nonflammable)

4
③ Secures system performance
④ Easy to be produced at a low cost
Table 8.3 indicates the candidates of alternative CFCs having been examined. Among
them, a new substance HFC-134a was selected. As to the safety, the Program for
Alternative Fluorocarbon Toxicity Testing (PAFT), consists of global manufacturers of
CFCs, has conducted a toxicity test and confirmed that it imposes no threat to the
human being.

(2) Characteristic Change due to Alternative CFCs and Adaptation to the Change
Table 8.4 indicates the difference in thermodynamic characteristic between
conventional CFC-12 and alternative HFC-134a. Figure 8.2 indicates the difference of
saturation line between the two.

[Table 8.3] The characteristic of various refrigerants Toxicity

Nonflammable
Refrigerant Performance

Total
Existing Single
refrigerant
Mixture

New Single
refrigerant

Mixture

Comparison with CFC-12

[Table 8.4] The difference in thermodynamic characteristic between two refrigerants

Chemical formula

Molecular weight

Gas specific
volume
Boiling point (C.)

Critical Temp. (C.)

Critical Pressure (kPa.)

Latent heat of
evaporation
Thermal conductivity
[ ]

5
 Pressure

Temp.
[Figure 8.2] Saturation pressure line of refrigeration
Refrigerant capacity : same condition
Condensation Temp.: 60 oC
4.8oC drop in
Evaporation Temp..: 0 oC
outlet temp.
0.15Mpa increase
in high temp.

Pressure Specific volume

20％ drop in
flow volume
7%rise
7% risein
inpower
power

Enthalpy
[Table 8.3] The characteristic difference on the refrigeration cycle on the Mollier diagram

Figure 8.3 indicates the characteristic difference on the refrigeration cycle resulting
from the characteristic difference on the Mollier diagram. Since HFC-134a has high
latent heat of evaporation, it requires less flow volume of refrigerant. However, since
the gas specific volume is large, it requires almost the same volume for compressor.
With HFC-134a, the pressure on the high-pressure side becomes a little higher than
that of CFC-12. The consumption power of compressor is also larger by approx. 7%.
To secure the equivalent performance after switching to the new refrigerant, the heat
release of condenser is increased in many cases.
Due to differences of pressure characteristics, the setting value of expansion valves and
pressure switch should also be changed.

6
 Compared to CFC-12, HFC-134a has the following characteristics:
(1) Low compatibility with conventional compressor oil (mineral oil)
(2) High water solubility (tends to contain water easily)
(3) High expansibility and permeability to sealing and hose materials.
Therefore changes should be made accordingly after switching to HFC-134a. Figure 8.4
indicates the problems in the refrigeration cycle for HFC-134a and changes required as
countermeasure.

Problems of HFC-134a Changes

Difference of Insoluble in compressor oil for 1. Compressor oil

Physical Properties CFC-12 (does not lubricate) - New compressor oil should be used.

Soluble in seal material for 2. Seal material

CFC-12 (causes gas leak) - New seal material should be used.
- Hose material should be changed.

Contains water easily 3. Desiccant

(internal corrosion occurs easily) ・Desiccant should be changed.

Difference of Pressure and load are high at a high 4. System Matching

Characteristics temperature. (does not cool properly) - Performance should be improved.
Magnet clutch and condenser
- Specification (Setting value) should be changed.
Pressure switch, Expansion valve, STV

Service-Related No compatibility of refrigerant, 5. Prevention of wrong connection, charging, and usage

oil, and O-ring - Piping joint should be changed.
- Charging valve should be changed.
- Service tool should be changed.
- Tools and parts for HFC-134a should be identified.

[Figure 8.4] Problems of HFC-134a and changes required as countermeasure

Expanding Understanding

Name of CFCs

How to Read the Name of CFCs Ex.

7
 Number of Number of Number of Symmetry
carbon atoms hydrogen fluorine Indication
-1 atoms +1 atoms

In the order of high symmetry

(Symmetry) (Asymmetry)
No suffix, a, b, c …

8.3 Adaptation of Already-Sold Vehicles

(1) Retrofit Adaptation

In the market, there are still many automotive air-conditioning using old refrigerant
CFC-12. When it is not possible to supply CFC-12 at a time of repair, some of the parts
must be exchanged so that the alternative refrigerant HFC-134a can be used (called
“retrofit”). From around 1994, automotive air-conditioning manufacturers have
started to perform retrofit to already-sold vehicles.
Specific procedure of retrofit differs according to the production year of the vehicle.
Some automotive air-conditioning manufacturers had started to produce CFC-12
automotive air-conditioning system that installs parts compatible with both HFC-12
and HFC-134a refrigerant from around 1993 as a preparation to retrofit so that the
exchange procedure is minimum.
When CFC-12 and HFC-134a are mixed, efficiency of refrigeration cycle lowers.
Moreover, when chlorine in CFC-12 reacts with PAG oil, oxidation and deterioration of
PAG oil occurs and sludge is produced. Therefore, charging adaptor only for retrofit
was provided to prevent charging inadequate refrigerant.
Table 8.5 summarizes the minimum retrofit items.

8
 [Table 8.5] Retrofit items
Item Description
Application of caution label Notice
Provision of adaptor for charging valve Quick joint method (conventionally screw method)
Charging of HFC-134a refrigerant Charge 7% less than the specified amount
Charging of oil Charge 20% more than the specified amount
Exchange the receiver Exchange the desiccant

[Table 8.6] Refrigerant Recovery Method

Method Cooling Method Compression Method

Principle Refrigerant in the recovery container is cooled The refrigerant in the refrigeration cycles is

and liquefied. When the refrigerant in the compressed and drawn out directly with a

recovery container is liquefied and the compressor. After compression, it is liquefied

pressure decreases, the refrigerant to be with condenser and recovered.

recovered moves to the recovery container.

Radiated heat Liquefied

Drawn out/compressed (Condensed)
CFCs moved
Cooled
Gasified Liquefied
(Evaporated) (Condensed) Gasified Compressor
Liquid
(Evaporated)
Recovered matter Liquid CFCs Recovery container
Recovery container
(Recovered matter)

Characte ①Because the recovered gas does not go ① Since the recovered gas goes through the

ristic through the compressor, different
refrigerating machine oils do not mix.
②Because of low pressure, it is easy to handle.
③Suitable for small amount recovery.
compressor, different refrigerating machine oil
mix.
② The device should be able to withstand a high
pressure.
③ Suitable for middle and large amount of

recovery.

Example Refrigerant reclaimer (ESR-10ACR, Denso) CFC recovery unit (HR5000-2, Hitachi Auto

of Systems)

Products

9
With some vehicles, hoses and shaft seal of the compressor must also be replaced
besides the basic procedure.

(2) Refrigerant Recovering Device

Since Japan has no laws and regulations on the recovery of CFCs refrigerant as in the
U.S. and Europe, recovery and recycling of refrigerant as social system is still not well
developed as in the U.S. and Europe. However, recovery and recycling of refrigerant
during service are relatively well performed.
CFCs recovery device for automotive air-conditioning generally recovers CFCs in a form
of gas from the cycle. The methods are classified into two types depending on whether
the recovered gas refrigerant is liquefied by cooling or by compression (See Table. 8.6).
After tramp materials, such as oil, impurities, water and air, are removed, CFCs are
charged directly into repaired car on the site so that CFCs are not released into the
atmosphere. Some companies recover CFCs from all over the country and refine them
to provide as like-new CFCs.

10
 8.4 Actions Against Global Warming

(1) Global Warming and CFCs

The Earth receives radiant energy from the sun and releases the heat as infrared rays.
However, the atmospheric layer on the surface of the Earth, which includes water and
CO2, preserves infrared rays radiated from the Earth in the atmosphere and feeds it
back to the surface of the Earth. Due to this phenomenon, the surface of the Earth is
maintained in a comfortable environment with average temperature of 15℃(Fig. 8.5).
This phenomenon is called “greenhouse effect”. Calculation estimates that, if there
were no greenhouse effect, the Earth’s surface would have been -23℃ covered with ice
all over. Here, water and CO2 are called “greenhouse effect gas”.
“Global warming” refers to the climate change resulting from the temperature increase
due to overdose of greenhouse effect by the concentration increase of greenhouse gas in
the air with expansion of human activities. According to the data presented by Dr.
Keeling, the concentration of CO2 in the air has increased by over 10% in the last 30
years (Fig. 8.6). It has been suggested that the global warming in recent years has
been so drastic that has never been observed in the last ten thousand years.
While CO2 and water do not, CFCs absorb infrared rays with wavelength of 8000nm to
12000nm at a rate of 1000 times higher than that of CO2. Therefore, CFCs are also
considered to be one of the major greenhouse effect gases.
To cope with the global warming, Intergovernmental Panel for Climate Change (IPCC)
consisting of scientists from all over the world was organized by the United Nations in
November 1988 to conduct studies and researches at an international level. Based on
this activity, Framework Convention on Climate Change was adopted, providing that
the total emission of greenhouse effect gases such as CO2 should be stabilized, at the
United Nations Conference on Environment and Development (in Rio de Janeiro,
Brazil) in June 1992. 154 countries signed this convention.

Sun
Greenhouse effect gas
Observation point:
Hawaii, Mauna, Loa
H2o, CO2, CFCs
Sunlight
Infrared rays

Earth
Average temp. of 15℃ Year

[Figure 8.5] The mechanism of greenhouse effect [Figure 8.6] Change of concentration of CO2 in the air

11
In December 1997, the Third Session of the Conference of the Parties to the United
Nations Framework Convention on Climate Change (COP3) was held in Kyoto, Japan,
and the protocol was prepared. It was decided to direct emission reduction efforts to
six types of gases: carbon dioxide (CO2), methane (CH4), nitrous oxide (N2O),
hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), and sulphur hexafluoride (SF6),
by the United States, EU and Japan.

(2) Current and Future Movements

In Japan, 18% of total CO2 emission results from automobiles (Fig. 8.7). To cope with
the global warming, automobile industry makes commitment such as new combustion
technologies for ultra-low fuel consumption and lightweight vehicles mainly made of
aluminum. Since refrigeration industry also uses CFCs with large greenhouse effect,
some endeavors are being made to cope with the global warming.

No identify Waste Energy conversion section Public welfare section

Power Power supply loss An electric entrepreneur For home use
Self- In-house generator For business use
consu
mption
Heat supply entrepreneur Transportation section
Town gas manufacturer Car, railroad
Direct
Coke manufacturer Domestic ship
Conversion Oil refining Domestic aviation
Transport Petrochemistry
Self-consumption and loss
Direct Others
Total emission
Industrial section
Power Industry Agriculture-and-forestry fisheries
Public
welfare Mining, the construction industry
Manufacturing industry
Food, fiber
Direct Power
Paper and valve
Lime Chemical industry,
stone Steel, nonferrous metal
Metal machine, others
[Figure 8.7] CO2 emission in Japan (in 1991/Carbon conversion)
(Daily automobile newspaper’s automobile handbook in 1994)

Total Equivalent Warming Impact (TEWI) is a measure that indicates the impact of
refrigeration system on the global warming quantitatively. International Institute of
Refrigeration (IIR) recommended that when selecting refrigeration system, TEWI
should be used as a guideline (April 1993). TEWI is a measure that indicates the
impact of a refrigeration system in its entire life cycle in a corresponding amount of CO2.
It is the total of direct effect from refrigerant release into the atmosphere and the
indirect effect from energy consumption resulting from operating the system and
transportation.

12
TEWI=GWP x Amount of Released Refrigerant + Amount of Released CO2 by Operating
the Automotive Air-Conditioning (Increased amount of fuel consumption)

GWP: Global Warming Potential

It is also called “warming coefficient of refrigerant” and indicated by the equivalent

CO2 amount.
Because CFCs gases are hardly decomposed in the atmosphere, it indicates the
impact in 100 years.

Table 8.7 summarizes the TEWI evaluation of major refrigeration system. HFC-134a,
an alternative refrigerant to CFC-12, indicates 1300 in GWP, marking a large decrease
from 7300 of CFC-12. TEWI of HFC-134a also decreased to about one fifth of CFC-12.
However, even when 1 kg of HFC-134a is released into the atmosphere, it corresponds
to a release of 1300 kg CO2 in 100 years. Therefore recovery of HFC-134a is already
mandatory at a time of service like specified CFCs in the U.S. and Europe.

[Figure 8.7] TEWI evaluation of major refrigeration A/C system

Cycle Refrigerant

A/C drive Influence by refrigerant 13,600

13,600

Compressor Vapor Improved

driven compression HFC-134a (Includes refrigerant recovery)

Propane

Stirling Helium

Heat
driven Adsorption H2O

H2O
Absorption
Ammonia

1999

13
In Japan, the automobile industry has started to recover HFC-134a voluntarily. In the
future, automotive air-conditioning system with a smaller impact on the global
warming, that is, with smaller TEWI value should be suggested.

14