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Refrigerants
Protecting the
Ozone Layer
V o l u m e 1
UNEP
2 0 0 1U P DAT E
This booklet is one of a series of reports prepared by the OzonAction Programme of the United Nations Environment
Programme Division of Technology, Industry and Economics (UNEP DTIE). UNEP DTIE would like to give special thanks to the
following organizations and individuals for their work in contributing to this project:
United Nations Environment Programme (UNEP)
Ms. Jacqueline Aloisi de Larderel, Director, UNEP DTIE
Mr. Rajendra M. Shende, Chief, UNEP DTIE Energy and OzonAction Unit
Ms. Cecilia Mercado, Information Officer, UNEP DTIE OzonAction Programme
Mr. Andrew Robinson, Programme Assistant, UNEP DTIE OzonAction Programme
Editor: Geoffrey Bird
Design and layout: ampersand graphic design, inc.
Printed in Malta by Interprint Limited
This brochure is available on-line at www.uneptie.org/ozonaction/library/
© 2001 UNEP
This publication may be reproduced in whole or in part and in any form for educational and non-profit purposes without special
permission from the copyright holder, provided acknowledgement of the source is made. UNEP would appreciate receiving a
copy of any publication that uses this publication as a source.
No use of this publication may be made for resale or for any other commercial purpose whatsoever without prior permission
in writing from UNEP.
The technical papers in this publication have not been peer-reviewed and are the sole opinion of the authors. The designations
employed and the presentation of the material in this publication therefore do not imply the expression of any opinion
whatsoever on the part of the United Nations Environment Programme concerning the legal status of any country, territory, city
or area or of its authorities, or concerning delimitation of its frontiers or boundaries. Moreover, the views expressed do not
necessarily represent the decision or the stated policy of the United Nations Environment Programme, nor does citing of trade
names or commercial processes constitute endorsement.
ISBN: 92-807-2159-3
Refrigerants
Protecting the
Ozone Layer
V o l u m e 1
UNEP
2 0 0 1U P DAT E
Contents
Foreword 3
Acknowledgements 4
Executive summary 5
Ozone depletion: an overview 6
The Montreal Protocol 8
Chapter summaries 12
Prospects for action:
• Domestic refrigeration 15
• Commercial refrigeration 20
• Cold storage, food processing and industrial refrigeration 23
• Unitary air conditioning and heat pumps 26
• Air conditioning via water chillers 28
• Transport refrigeration 31
• Mobile air conditioning 33
• Heat pumps 35
• Refrigerant conservation 37
Resources: 40
• Secretariats and Implementing Agencies 41
• Contact points 42
• Further reading 44
• Glossary 45
About the UNEP DTIE OzonAction Programme 46
About the UNEP Division of Technology, Industry and Economics 48
Foreword
When the Montreal Protocol on Substances that Deplete the Ozone Layer came into force, in 1989, it
had been ratified by 29 countries and the EEC, and set limits on the production of eight man-made
chemicals identified as ozone depleting substances (ODS). By July 2001 there were more than 170
Parties (i.e. signatories) to the Protocol, both developed and developing countries, and production
and consumption of over 90 substances were controlled.
Linking these two sets of figures, which attest to the success of the Montreal Protocol, is a process of
elimination of ODS in which ratification of the Protocol was only a first step. It was recognized from
the start that the Protocol must be a flexible instrument and that it should be revised and extended to
keep pace with scientific progress. It was also recognized that developing countries would face
special problems with phase out and would need assistance if their development was not to be
hindered. To level the playing field, the developing countries were given extra time to adjust
economically and to equip. A Multilateral Fund (MLF) was also set up early in the process to provide
financial and technical support for their phase out efforts.
Exchanges of information and mutual support among the Parties to the Montreal Protocol – via the
mechanisms of the MLF – have been crucial to the Protocol’s success so far. They will continue to be
so in the future. Even though many industries and manufacturers have successfully replaced ODS
with substances that are less damaging to the ozone layer or with ODS-free technology, lack of up-
to-date, accurate information on issues surrounding ODS substitutes continues to be a major
obstacle for many Parties, especially developing country Parties.
To help stimulate and support the process of ODS phase out, UNEP DTIE’s OzonAction Programme
provides information exchange and training, and acts as a clearinghouse for ozone related
information. One of the most important jobs of the OzonAction programme is to ensure that all those
who need to understand the issues surrounding replacement of ODS can obtain the information and
assistance they require. Hence this series of plain language reports – based on the reports of UNEP’s
Technical Options Committees (TOC) – summarizing the major ODS replacement issues for decision
makers in government and industry. The reports, first published in 1992, have now been updated to
keep abreast of technological progress and to better reflect the present situation in the sectors they
cover: refrigerants; solvents, coatings and adhesives; fire extinguishing substances; foams; aerosols,
sterilants, carbon tetrachloride and miscellaneous uses; and methyl bromide. Updating is based on
the 1998 reports from the TOCs and includes further information from the TOCs until 2000.
Updating of the reports at this point is particularly timely. The ‘grace period’ granted to developing
countries under the Montreal Protocol before their introduction of a freeze on CFCs came to an end in
July 1999. As developing countries now move to meet their Protocol commitments, accurate and up-
to-date information on available and appropriate technologies will be more important than ever if the
final goal of effective global protection of the ozone layer is to be achieved.
The publications in this series summarize the current uses of ODS in each sector, the availability of
substitutes and the technological and economic implications of converting to ODS-free technology.
Readers requiring more detailed information should refer to the original reports of the UNEP Technical
Options Committees (see Further Reading) on which the series is based.
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
3
Acknowledgements
List of the reporting (full) members of the Refrigeration Technical Options Committee. The names of
people proposed by former experts as replacements but who are still subject to final government
approval and recommendation to UNEP are given in italics. This report was written by Dr Lambert
Kuijpers (TEAP Co-Chair and Refrigeration TOC Co-Chair). The people listed below also gave freely
of their time to ensure that this publication, while written in plain language, reflects accurately the
more detailed information in the sources used.
UNEP TOC REFRIGERATION, A/C AND HEAT PUMPS’
REPORTING MEMBERS FOR THE ASSESSMENT 2000-2002
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
4
Co-chairs Affiliation Country Dr. Radhey S. Agarwal IIT Delhi India
Dr. Lambert Kuijpers Cochair UNEP TEAP Netherlands
Mr. Ward Atkinson Sun Test Engineering USA
Mr. James A. Baker Delphi Automotive Systems USA
Mr. Julius Banks US EPA USA
Mr. Marc Barreau ATOFINA France
Dr. Steven Bernhardt DuPont Fluoroproducts USA
Mr. Jos Bouma IEA Heat Pump Centre Netherlands
Dr. Dariusz Butrymowicz Institute of Fluid-Flow Machinery of Polish Academy Polandof Sciences
Mr. James M. Calm Engineering Consultant USA
Dr. Denis Clodic Centre d’Energetique, Ecole des Mines de Paris France
Mr. Daniel Colbourne Calor Gas Limited Great Britain
Mr. Jim Crawford The Trane Company USA
Dr. Sukumar Devotta National Chemical Laboratory India
Mr. László Gaal Hungarian Refrigeration and Air Conditioning Association Hungary
Dr. Kenneth E. Hickman Consultant USA
Mr. Martien Janssen Re/genT Consultancy Netherlands
Mr. Makoto Kaibara Matsushita Electric Industrial Co. Ltd. Japan
Dr. Ftouh Kallel Batam, Societe Hela D’Electromenager Tunisia
Dr. Ing. Michael Kauffeld DTI Energy, Danish Technological Institute Denmark
Mr. Fred J. Keller CARRIER Corporation USA
Prof. Dr. Ing. Jürgen Köhler Institut für Thermodynamik Denmark
Dipl. Ing. Holger König Axima Refrigeration GmbH Denmark
Prof. Dr. Ing. H. Kruse FKW GmbH Denmark
Mr. Edward J. McInerney GE Appliance Park 35-1001 USA
Mr. Mark Menzer ARI USA
Mr. Haruo Onishi Daikin Industries Ltd. Japan
Mr. Hezekiah B. Okeyo Department of Industrial Development, Uchumi House Kenya
Dr. Roberto de Aguiar Peixoto Maua Institute of Technology Brazil
Mrs. Frédérique Sauer Dehon Service S.A. France
Mr. Adam M. Sebbit Makerere University Uganda
Mr. Stephan Sicars Siccon Denmark
Mr. Arnon Simakulthorn Thai Compressor Manuf. Co. Ltd Thailand
Prof. Aryadi Suwono Bandung Institute of Technology Indonesia
Dr. Pham van Tho Ministry of Fisheries Vietnam
Ms. Trude Tokle SINTEF Energy Research Norway
Mr. Vassily N. Tselikov CPPI Russian Federation
Mr. Paulo Vodianitskaia Multibrás SA Eletrodomésticos Brazil
Mr. Kiyoshige Yokoi MATSUSHITA Refr Co Japan
Executive summary
CFC production has been phased out in the non-Article 5 countries and phase out is underway in the
Article 5 countries. To date, the main substitutes for CFCs in both developed and developing
countries have been HCFCs and HFCs. HCFCs are transitional substances and alternatives to them,
mainly blends of HFCs, and also HCs and ammonia, have become commercially available for many
applications. As a result, HFCs currently have a large share of the replacement market. If high
obsolescence costs are to be avoided, a rational approach to phase out of HCFC consumption
should include a minimum period to allow for development and commercialization of alternatives and
for rational phasing in of new equipment. For the short term, the transitional HCFCs are still a valid
option for refrigeration and air conditioning (A/C) equipment.
For the long term, however, only five important global refrigerant options remain for the vapour
compression cycle (as well as various non vapour compression methods):
• hydrofluorocarbons (HFCs, HFC-blends with 400 and 500 number designation);
• ammonia (R-717);
• hydrocarbons and blends (HCs, e.g. HC-290, HC-600, HC-600a etc.);
• carbon dioxide (CO2, R-744);
• water (R-718).
None of these is perfect. All have advantages and disadvantages that should be considered by
governments, equipment manufacturers and equipment users. For instance, HFCs have relatively high
global warming potentials, ammonia is more toxic than the other options, and both ammonia and
hydrocarbons are flammable. Appropriate equipment design, maintenance and use can help to
overcome these concerns, though sometimes at the cost of greater capital investment or lower
energy efficiency. Energy efficiency relates directly to global warming and greenhouse gas emissions.
It therefore remains an important issue for all refrigeration technologies, and should be considered
along with the factors described above. Next to ozone depletion, global warming is the main
environmental issue governing the selection of refrigerant technologies for the near-, mid- and long-
term. Although this issue is not covered by the Montreal Protocol, it nevertheless forms an important
criterion in the ongoing “environmental acceptability” debate. Interest in ammonia and the
hydrocarbons is stimulated, at least in part, by the fact that the HFCs are greenhouse gases which
may be subject to control measures in future. However, safety aspects also imply stringent emission
controls for ammonia and hydrocarbons. Similarly, energy efficiency research is partly encouraged by
the contribution of energy production to carbon dioxide (CO2) emissions.
The five refrigerant options mentioned above are at different stages of development or
commercialization. HFCs are widely applied in many sectors and ammonia and hydrocarbons are
enjoying growth in sectors where they can be accommodated easily. CO2 equipment is being
developed for certain applications and the first systems have reached the commercial market.
Equipment using water has been developed and may see some increase in use in limited
applications. Work by several committees is underway to develop standards to permit the application
of new refrigerants. Companies intend to reach limits that are accepted worldwide in those standards.
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
5
Ozone depletion: an overview
Most of the oxygen in the Earth’s atmosphere is in the form of molecules containing two oxygen
atoms, known by the familiar chemical symbol O2. In certain circumstances, three atoms of oxygen
can bond together to form ozone, a gas with the chemical symbol O3. Ozone occurs naturally in the
Earth’s atmosphere where its concentration varies with altitude. Concentration peaks in the
stratosphere at around 25–30 kilometres from the Earth’s surface and this region of concentration of
the gas is known as the ozone layer.
The ozone layer is important because it absorbs certain wavelengths of ultraviolet (UV) radiation from
the Sun, reducing their intensity at the Earth’s surface. High doses of UV radiation at these
wavelengths can damage eyes and cause skin cancer, reduce the efficiency of the body’s immune
system, reduce plant growth rates, upset the balance of terrestrial and marine ecosystems, and
accelerate degradation of some plastics and other materials.
A number of man-made chemicals are known to be harmful to the ozone layer. They all have two
common properties: they are stable in the lower atmosphere and they contain chlorine or bromine.
Their stability allows them to diffuse gradually up to the stratosphere where they can be broken down
by solar radiation. This releases chlorine and bromine radicals that can set off destructive chain
reactions breaking down other gases, including ozone, and thus reducing the atmospheric
concentration of ozone. This is what is meant by ozone depletion. The chlorine or bromine radical is
left intact after this reaction and may take part in as many as 100,000 similar reactions before
eventually being washed out of the stratosphere into the troposphere.
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
6
Effects of CFCs on stratoshperic ozone
UV radiation CFCl3
CFCl2
chlorineradical
chlorinemonoxide free
chlorineradical
ozone(O3)
series of reactions
oxygenmolecule
(O2)
+
When gases containing
chlorine, such as CFCs,
are broken down in the
atmosphere, each chlorine
atom sets off a reaction that
may destroy hundreds of
thousands of ozone molecules.
Another important environmental impact of a gas is its contribution to global warming. Global
Warming Potential (GWP) is an estimate of the warming of the atmosphere resulting from release of a
unit mass of gas in relation to the warming that would be caused by release of the same amount of
carbon dioxide. Some ODS and some of the chemicals being developed to replace them are known
to have significant GWPs. For example, CFCs have high GWPs and the non-ozone-depleting
hydrofluorocarbons (HFCs) developed to replace CFCs also contribute to global warming. GWP is an
increasingly important parameter when considering substances as candidates to replace ODS.
During past decades, sufficient quantities of ODS have been released into the atmosphere to damage
the ozone layer significantly. The largest losses of stratospheric ozone occur regularly over the
Antarctic every spring, resulting in substantial increases in UV levels over Antarctica. A similar though
weaker effect has been observed over the Arctic.
At present, scientists predict that, provided the Montreal Protocol is implemented in full, ozone
depletion will reach its peak during the next few years and will then gradually decline until the ozone
layer returns to normal around 2050.
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
7
CFC numbers provide the information
needed to deduce the chemical structure
of the compound. The digit far right
provides information on the number of
fluorine atoms, the digit second from the
right provides information on hydrogen
atoms, and the digit on the left provides
information on carbon atoms. Vacant
valencies are filled with chlorine atoms.
Adding 90 to the number reveals the
numbers of C, H and F atoms more
directly.
How CFC Nomenclature Works
number of carbon atoms minus one (omitted if 0)
CC
FF
FF
ClCl CFC 114
number of hydrogen atoms, plus one
number of fluorine atoms in one molecule
Note: 1. All spare valencies filled by chlorine atoms2. Different isomers are indicated by a suffic of lower case letters3. Bromine atoms are indicated by a suffic B plus number of atoms4. Hundreds number = 4 or 5 for blends (e.g. R-502)
Ozone-depleting Major uses Ozone-depletion substance (ODS) potential (ODP)Chlorofluorocarbons Refrigerants; propellants for spray cans, inhalers, etc.; 0.6–1
(CFC) solvents, blowing agents for foam manufacture
Halons Used in fire extinguishers 3–10
Carbon tetrachloride Feedstock for CFCs, pharmaceutical and agricultural 1.1
chemicals, solvent
1,1,1-trichlorethane Solvent 0.1
(methyl chloroform)
Hydrobromofluorocarbons Developed as ‘transitional’ replacement for CFCs. 0.01–0.52
(HBFCs)
Hydrochlorofluorocarbons Developed as ‘transitional’ replacement for CFCs. 0.02–7.5
(HCFCs)
Methyl bromide Fumigant, widely used for pest control 0.6
Bromochloromethane (CBM) Solvent 0.12
The Montreal Protocol
The Montreal Protocol, developed under the management of the United Nations Environment
Programme in 1987, came into force on 1 January 1989. The Protocol defines measures that
Parties must introduce to limit production and consumption of substances that deplete the ozone
layer. The Montreal Protocol and the Vienna Convention – the framework agreement from which the
Protocol was born – were the first global agreements to protect the Earth’s atmosphere.
The Protocol originally introduced phase out schedules for five CFCs and three halons. However, it
was designed so that it could be revised on the basis of periodic scientific and technical
assessments. The first revisions were made at a meeting of the Parties in London, in 1990, when
controls were extended to additional CFCs and halons as well as to carbon tetrachloride and methyl
chloroform. At the Copenhagen meeting, in 1992, the Protocol was amended to include methyl
bromide and to control HBFCs and HCFCs. A schedule for phase out of methyl bromide was
adopted at the Vienna meeting in 1995, and this was later revised in 1997, in Montreal. In 1999, the
Parties met in Beijing, where they extended control to bromochloromethane (CBM). By July 2001,
there were 177 Parties to the Montreal Protocol and more than 90 chemicals are now controlled.
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
8
Ozone-depleting substances (ODS) covered by the Montreal Protocol and their ozone-depletion potential (ODP)*
* Where ranges of ODP are given, readers requiring the exact ODP for a given CFC, halon, HBFC or HCFC should referto the Handbook for the International Treaties for the Protection of the Ozone Layer, published by the UNEP OzoneSecretariat, or other accredited sources.
How regulation works
All ODS do not inflict equal amounts of damage on the ozone layer. Substances that contain only
carbon, fluorine, chlorine, and/or bromine – referred to as fully halogenated – have the highest
potential for damage. They include CFCs and halons. Other substances, including the
hydrochlorofluorocarbons (HCFCs), developed as replacements for CFCs, also contain hydrogen. This
reduces their persistence in the atmosphere and makes them less damaging for the ozone layer. For
the purposes of control under the Montreal Protocol, ODS are assigned an ozone-depletion potential
(ODP).
Each controlled chemical is assigned an ODP in relation to CFC-11 which is given an ODP of 1.
These values are used to calculate an indicator of the damage being inflicted on the ozone layer by
each country’s production and consumption of controlled substances. Consumption is defined as
total production plus imports less exports, and therefore excludes recycled substances. The relative
ozone-depleting effect of production of a controlled ODS is calculated by multiplying its annual
production by its ODP, results are given in ODP tonnes, a unit used in this series of publications and
elsewhere. The ODS currently covered by the Montreal Protocol are shown, with their ODPs, in the
table on page 8.
Developing countries and the Montreal Protocol
From the outset, the Parties to the Montreal Protocol recognized that developing countries could face
special difficulties with phase out and that additional time and financial and technical support would
be needed by what came to be known as ‘Article 5’ countries. Article 5 countries are developing
countries that consume less than 0.3 kg per capita per year of controlled substances in a certain
base year. They are so called because their status is defined in Article 5 of the Protocol1.
Financial and technical assistance was provided under the 1990 London Amendment which set up
the Multilateral Fund (MLF). Activities and projects under the MLF are implemented by four
implementing agencies: UNDP, UNEP, UNIDO and the World Bank.
Article 5 countries were also granted a ‘grace period’ of 10 years to prepare for phase out.
1999 marked the end of that period for production and consumption of CFCs. Article 5 countries
have, since 1999, entered the ‘compliance’ period in which they will have to achieve specific
reduction targets.
The requirements of the Montreal Protocol as of December 2000 for both developed and Article 5
countries are shown in the table on page 10.
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
9
1 This is often written Article 5(1), indicating that status is defined in paragraph 1 of Article 5 of the Protocol. ‘Article 5Parties’ is also used.
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
10
Requirements of the Montreal Protocol including amendments and adjustments to the end of 1999**
Controlled Substance Reduction in consumption Reduction in consumption and production for and production for developing developed countries (Article 5) countries
CFC-11, CFC-12, CFC- 113,
CFC-114, CFC-115
Base level: 1986
1989: Freeze
1994: 75 per cent
1996: 100 per cent
Base level: Average of 1995–1997
1999: Freeze
2005: 50 per cent
2007: 85 per cent
2010: 100 per cent
Halon 1211, halon 1301, halon
2402
Base level: 1986
1992: 20 per cent
1994: 100 per cent
Base level: Average of 1995–1997
2002: Freeze
2005: 50 per cent
2010: 100 per cent
Other fully halogenated CFCs Base level: 1989
1993: 20 per cent
1994: 75 per cent
1996: 100 per cent
Base level: Average of 1998–2000
2003: 20 per cent
2007: 85 per cent
2010: 100 per cent
Carbon tetrachloride Base level: 1989
1995: 85 per cent
1996: 100 per cent
Base level: Average of 1998–2000
2005: 85 per cent
2010: 100 per cent
1,1,1-trichloroethane
(methyl chloroform)
Base level: 1989
1993: Freeze
1994: 50 per cent
1996: 100 per cent
Base level: Average of 1998–2000
2003: Freeze
2005: 30 per cent
2010: 70 per cent
2015: 100 per cent
HCFCs Consumption
Base level: 1989 HCFC consumption +
2.8 per cent of 1989 CFC consumption
1996: Freeze
2004: 35 per cent
2010: 65 per cent
2015: 90 per cent
2020: 99.5 per cent
2030: 100 per cent
Production
Base level: 1989 HCFC consumption +
2.8 per cent of 1989 CFC consumption
2004: Freeze
Consumption
Base level: 2015
2016: Freeze
2040: 100 per cent
Production
Base level: 2015
2001: Freeze
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
11
0
50
100
150
200
Beijing Amendment
Montreal Amendment
Copenhagen Amendment
London Amendment
Montreal Protocol
Vienna Convention
Agreement
No. of CountriesRatifying
Progress in the ratification of the Montreal Protocol and its amendments
Requirements of the Montreal Protocol including amendments and adjustments to the end of 1999**
Controlled Substance Reduction in consumption Reduction in consumption and production for and production for developing developed countries (Article 5) countries
** The Protocol allows some exemptions, e.g. for "essential uses." Readers requiring full details of phase out for a given substanceshould refer to the Handbook for the International Treaties for the Protection of the Ozone Layer, published by the UNEP OzoneSecretariat, or other accredited sources.
HBFCs 1996: 100 per cent 1996: 100 per cent
Bromochloromethane 2002: 100 per cent 2002: 100 per cent
Methyl bromide Base level: 1991
1995: Freeze
1999: 25 per cent
2001: 50 per cent
2003: 70 per cent
2005: 100 per cent
Base level: Average of 1995-1998
2002: Freeze
2005: 20 per cent
2003: review of reduction schedule
2015: 100 per cent
Source: Caleb Management Services, UK
Chapter summaries
Domestic refrigeration
In the Article 5 countries, transition from CFCs is occurring faster than required by the Montreal
Protocol. Preferred alternatives have been assessed in terms of safety, and of environmental,
functional and performance requirements. Two alternative refrigerants now remain: HFC-134a and
HC-600a. Both of these can provide safe, reliable and efficient domestic refrigerators and freezers.
Analysis of regional requirements and of differences in products selected by consumers provides
insight into selection. The complexity of field repair is increasing with the introduction of new
refrigerants and this has possible implications for several issues. There is a significant difference in
field repair rates between developed and developing countries, at approximately 2 per cent and 10
per cent respectively. Differences arise because of the use environment, extended life, uncertain
power-supply service, aggressive transport conditions and deficient service training. Globally, CFC-12
continues to dominate aftermarket service demand. Increased energy efficiency for domestic
refrigeration is an area of increasing interest.
Commercial refrigeration
Commercial refrigeration uses a wide range of equipment. The refrigeration capacity of centralized
systems in supermarkets varies typically from 20 kW to 1000 kW while stand-alone equipment
capacities are comparable to those of domestic equipment. Stand-alone equipment has traditionally
used CFC-12. Most new equipment uses HFC-134a and some now uses hydrocarbons. The
expected accelerated phase out of HCFCs in Europe has led to the choice of R-404A and R-507A
for new centralized systems. HFC blends – the economically preferred refrigerants – are the usual
choice, although in some European countries certain industries are supplying units that use either
ammonia or hydrocarbons. Units have been installed to evaluate the advantages and the drawbacks
of indirect systems (using a secondary circuit with heat transfer fluids). New concepts for direct
expansion using water cooling, now in operation, are also being evaluated. Other development efforts
are focussing on improving energy efficiency, minimizing charge size, and minimizing refrigerant
emissions.
Industrial refrigeration
Ammonia and HCFC-22 are currently the most commonly used refrigerants for industrial refrigeration,
including cold storage and food processing. It is expected that ammonia will increase in importance in
the future. In these sectors CFCs have been replaced by new systems using ammonia, HCFC-22 and
HFCs where the currently used HFCs are HFC-134a, R-404A and R-507A. The blend R-410A is
expected to become the leading HFC in the future. Hydrocarbons and CO2 are applicable for specific
applications. Retrofit activities in the industrial sectors are lower than predicted several years ago
although various retrofit options have proven to be viable solutions. In some cases, economic or
technical considerations make retrofit impossible. Cold storage and food processing is a more
important sector than industrial refrigeration in Article 5 countries. Here the refrigerants used are, to a
certain degree, CFCs and substitutes, HCFC-22 and ammonia.
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
12
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
13
Unitary air conditioning and heat pumps
Air cooled air conditioners and heat pumps ranging in size from 2 kW to 420 kW comprise the vast
majority of the air conditioning market. Nearly all of these units use HCFC-22 as working fluid,
representing an inventory of approximately 423,000 tonnes of HCFC-22. Significant progress has
been made in developing alternatives to HCFC-22 for this category of products. Hydrocarbon
refrigerants might also be suitable replacements for HCFC-22 in some categories of products, i.e. air-
to-water heat pumps and possibly very low charge level air-to-air systems. Article 5 Parties will have a
significant need for transfer of reclamation and retrofit technologies. At least one retrofit candidate for
HCFC-22 is commercially available: the HFC-blend R-407C.
Air conditioning via water chillers
Refrigerants including fluorocarbons (CFCs, HCFCs, HFCs), ammonia and hydrocarbons are used in
the continuously growing number of water chillers used for air conditioning around the world. Chillers
using fluorocarbons predominate in the installed base and in new units, as initial costs are relatively
low. Because HCFCs and HFCs are similar to CFCs physically and chemically, they can often replace
CFCs in new and existing chillers with less modification of chillers and equipment rooms than for
other replacement refrigerants. However, ammonia and hydrocarbon chillers are enjoying some
growth, particularly in Northern Europe. It must also be mentioned that, in recent years: phase out of
CFC-11 use in existing chillers has slowed significantly; use of ammonia in new systems has grown
more rapidly; very low emission chillers are now being installed; and hydrocarbon chillers have been
introduced in several regional markets.
Transport refrigeration
Transport refrigeration includes refrigeration in ships, railcars, containers and road transport
equipment. It also includes refrigeration and air conditioning on merchant ships, buses and railcars.
Most systems that used CFCs have been retrofitted or scrapped, except for refrigerated containers
and trucks where existing CFC-using fleets are large. Severe operating conditions mean that emission
rates can be particularly significant in all segments of transport refrigeration. In ships, nearly all
systems use HCFC-22, but HFCs are the preferred future option. Apart from HFCs, work is ongoing
on alternatives including hydrocarbons, ammonia, air-cycle and CO2 for new systems in transport
refrigeration. About half of the refrigerated containers and road vehicles still use CFC-12 today and
need to be retrofitted (mainly with HCFCs and HFCs).
Mobile air conditioning
By the end of 1994, all automobile manufacturers had converted mobile air conditioning systems to
HFC-134a. Existing vehicles with CFC-12 air conditioning are expected to be phased out due to “old
age” by the year 2008. The major issue remaining is to encourage all countries, particularly the Article
5 Parties, to phase out the use of CFC-12 in motor vehicles as soon as possible and to prevent
unnecessary emissions during servicing. Retrofit technology, recovery and recycling of refrigerant, and
service technician training are therefore of the utmost importance. To minimize global warming
emissions, hydrocarbons and CO2 have been proposed as possible long-term replacements for HFC-
134a. Considerable development work is ongoing, particularly for CO2.
Heat pumps
It is estimated that the total existing heating-only heat pump stock in the residential,
commercial/industrial and district heating sectors is roughly 1.7 million units, with a total heating
capacity of about 13,300 MW. Virtually all heat pumps are in use in the developed countries. HFCs
are the most important alternative refrigerant for heat pumps, both for retrofit and in new installations.
HFC-134a is used in medium/large capacity units as a replacement for CFC-12 where R-404A, R-
407C and R-410A are the most promising HFC blend alternatives to replace HCFC-22. To date, the
number of heat pump retrofits has been lower than expected. In recent years, ammonia has attained
a small but growing market share. Propane, propylene and certain hydrocarbon blends are being
used in a limited number of residential heat pumps, mainly in Europe. Heat-pump water heaters using
CO2 as refrigerant have been introduced to the market and the refrigerant is being evaluated for
several other heat pump applications.
Refrigerant conservation
Refrigerant conservation is critical both to maintaining the stock of existing CFC equipment and to
minimizing any environmental (e.g. global warming) or safety impacts associated with the transition
from ODS. Successful measures in the past have included financial incentives and regulations
making containment compulsory. In Article 5 countries, important first steps include tightening up
systems by finding and repairing leaks, and recovering refrigerant when opening the system for
service. In addition to recovery, consideration of recycling and reclaim procedures is also critical.
To be effective, conservation technologies must be matched by technician training and, in some
cases, adaptation of technology.
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Prospects for action
Domestic refrigeration
All non-Article 5 countries and many Article 5 countries have completed transition from CFC-12 to
ozone-safe refrigerants in new equipment in the domestic refrigeration sector. In those Article 5
countries where national transition schedules are influenced by local regulatory initiatives, by
availability of components and resources, and by the engineering time required to re-design and
certify CFC-free models, transition to CFC-free models is occurring in advance of the Montreal
Protocol requirements.
There are now, essentially, two alternatives being used: HFC-134a and HC-600a. No significant new
candidates are expected to emerge because of high development costs and of the extensive supply
infrastructure required. Niche candidates, such as HFC-152a and related blends (in China), will
continue to be a focus for development efforts, given regional availability. Development efforts on
various drop-in blends are expected to continue, but only for after-market service. Appropriate
candidate alternatives must successfully complete comprehensive life-cycle assessments that include
analyses of production, transport, use, service and disposal requirements. Criteria for use of
candidate alternatives include safety, environmental, functional and performance requirements, as well
as many other regional requirements.
Both HFC-134a and HC-600a have zero ozone-depletion potential. HFC-134a is a greenhouse gas.
HC-600a is a Volatile Organic Compound, which may raise issues of compliance with local
regulations. Effective refrigerant recovery can mitigate both of these concerns. Levels of efficiency
obtained with HFC-134a and HC-600a are more or less identical. The reduced gas density of HC-
600a reduces gas-borne noise transmission compared to HFC-134a. Both HFC-134a and HC-600a
will provide safe, reliable, efficient domestic refrigerators and freezers with properly designed units.
The millions of units containing either HFC-134a or HC-600a being produced annually already attest
to the reliability of these domestic refrigerator-freezers.
Refrigerant flammability introduces additional requirements that must be considered as fundamental
criteria for product design and for the application environment. In response to needs introduced by
significant differences in the flammability of candidate refrigerants, product standards throughout the
world are being modified to include minimum requirements.
No-frost products containing HC-600a are now being offered in Europe. Either remote electrical
components or premium-cost special fans, switches and defrost controls are necessary. Evaporators
outside the storage volume (cold wall type) may be desirable to minimize risks or redesign needs.
HFC-134a requires a synthetic polyol ester oil and a molecular sieve dryer such as XH7 or XH9.
Polyol ester oils are hygroscopic and require enhanced manufacturing process control to ensure low
system moisture level. Conversion to electrical insulation materials typically used for HCFC-22
applications may be necessary. Careful attention to system cleanliness and avoidance of potential
sources of contamination are essential. HC-600a uses the familiar naphthenic mineral oil and a
molecular sieve dryer such as XH6. Competent manufacturing processes are required for reliable
application but HC-600a does not demand cleanliness control beyond historic CFC-12 practices.
HC-600a has a 1.8 per cent lower flammability limit in air, amplifying the need for proper factory
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
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ventilation and appropriate electrical equipment standards. Current manufacturing practice uses
97.5–99.5 per cent pure HC-600a. These high purities ensure both thermodynamic performance and
protection against toxicity of probable impurities.
Field repair
Reliable information regarding domestic refrigeration field repair practices, repair frequency and the
consumption of a given type or quantity of fluid is difficult to obtain. Outside of warranty periods, only
a minor fraction of field repairs are carried out by original equipment manufacturers’ service personnel.
The majority of repairs are performed by a large number of individual and small-company service
shops with no established reporting infrastructures.
The high value of capital goods relative to labour costs in many countries exacerbates the situation by
encouraging component rebuilding in small, decentralized service shops. The variable quality of repair
resulting from this practice increases field repair frequency and thus extends the demand for ozone-
depleting substances and obsolete components. Furthermore, the continued use of components that
have energy efficiencies well below those obtained with current practice maintains pressure on power
generation and distribution systems.
Field repair is a general term that includes service, drop-in, conversion and rebuild options. Field
repair of new production refrigerator-freezers containing either HFC-134a or HC-600a refrigerant
should be restricted to the service technique using the refrigerant specified originally. Specific training
of service engineers and technicians is crucial.
Service field repair uses new or recycled CFC-12 when repairing a unit. The original-equipment
naphthenic mineral oil or alkyl benzene synthetic oil continues to be used. Any failed components are
replaced with parts similar to those used in the original equipment. This is the simplest and most
reliable approach (it will most likely continue as long as CFC-12 is available at a reasonable cost).
Drop-in field repair is a technique which changes the refrigerant without changing the lubricant. There
are numerous candidate drop-in refrigerants, ranging from replacement refrigerants to blends
developed for a certain specified (CFC-12) volumetric capacity. Supply sources range from highly
technical multi-national companies to unknown individual entrepreneurs (see Table 1, page 18).
Potential concerns include:
• possible elevated solvency, which may make polymers used in the compressor incompatible with
a refrigerant;
• when using alternative refrigerants, the performance of any given refrigerator-freezer is almost
always unknown. Required charge quantities and techniques are common uncertainties.
As CFC-12 availability and cost become more of a concern, some progress is being made in the use
of the drop-in technique.
Retrofit field repair techniques range from simple changing of refrigerant, lubricant and dryer (if
required) to extensive changes of compressor, refrigerant, lubricant, and dryer, as well as modification
of the expansion device and purging of the system to remove residual original equipment materials
from the system. The simple retrofit technique has limited acceptance. HFC-134a and HC-600a are
the only practicable refrigerants to consider for extensive retrofit techniques which include compressor
replacement. Technology is readily available to implement this option. Optimum charge level will not
be known for either HFC-134a or HC-600a. This is likely to result in less than optimum performance.
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In non-Article 5 countries the distribution of failures is estimated to be 1 per cent during the first five
years (primarily driven by manufacturing quality defects) with an additional cumulative 1 per cent
during the typically remaining 10 to 15 years of product life. In Article 5 countries, distribution is
estimated to be 3 per cent and 7 per cent respectively.
Refrigerant recovery during field repair and product disposal is frequently cited as an opportunity to
reduce emissions of ozone-depleting substances and to extend their availability for service. Both
objectives are valid and achievable. Service and disposal recovery of refrigerants is being practiced in
many non-Article 5 and Article 5 countries. In spite of economic and technological limitations, many
developing countries are ahead of schedule in their industry conversions. However, servicing remains
a very important issue in these countries, partly due to the extended working life of appliances and
partly to power-supply problems such as power cuts and voltage fluctuations which adversely affect
product reliability.
The energy efficiency of domestic refrigerator-freezers is a subject of increasing interest worldwide, on
the part of both consumers and regulators. Widespread energy conservation efforts have been driven
primarily by the need to avoid investment in energy production and to avoid excessive peak electrical
demands. The rapid growth of energy demand in Article 5 countries will probably lead to broader
refrigerator energy regulations to avoid these excessive peaks, and the need for extra investment.
Retirement and replacement of significantly less efficient, older, installed units and universal application
of already widely practiced commercially available state-of-the-art technology could result in large
reductions in global energy consumption. For example – and this holds true for many countries – a
typical 1997 refrigerator-freezer consumes only 30 per cent of the energy required by a 1972 model.
Improving compressor efficiency involves several aspects such as enhancement of motor efficiency,
use of lower speed motors, lower bearing friction, improved fluid heat transfer, use of lower viscosity
oils, and optimization of gas flow through valves, etc.
Continuous refrigeration capacity adjustment through frequency modulation of fixed displacement
compressors has been demonstrated using inverter controlled drive motors. Energy improvements
are variable and depend on the refrigerator design for a specific application. Results achieved are
variable, with the general estimate for improvement being about 10 per cent. Product noise level
modulation with capacity modulation is another favourable aspect of these inverter controlled
compressors.
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Table 1. Field repair of CFC-12/ mineral oil systems
Field Repair Method Repair Type Advantages Disadvantages
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Use virgin or recycledwith either:compressor and oil, ornew CFC-12 compressorand new mineral oil.
Service Compressor materialcompatibility.
Compressor reliability.
System performance.
System performance.
Minimized service complexity.
Cost and availability of CFC-12CFC-12 good now but futureis uncertain.
Replace CFC-12 refrigerant134a and retain mineral oil and change dryer.
Retrofit Acceptable performance inspecific limited applications.
Insolubility issues: oil with HFC-logging and capillary tube, original restrictions.
Performance.
Material incompatibilities.
Brazing more critical.
Replace CFC-12 refrigerantwith HC-600a / HC-290 blendor C1 (HFC/HC azeotrope),retain original mineral oil andensure flammability safety.
Retrofit Moderate cost.
Cooling capacity sameas CFC-12.
Each appliance manufacturermust endorse service procedure(potential flammability issues).
National regulations may prohibit.
Replace CFC-12 refrigerantwith non CFC “drop-in”alternative:
1. R-401A (HCFC/HFCZeotrope–MP39); alkylbenzene oil with wear additive.
Retrofit Moderate cost.
Avoids dependence on CFC-12 availability.
Inquire to compressormanufacturers regarding materialcompatibility and compressorreliability.
Performance issues for someproduct configurations.
Transitional due to HCFCcontent (excluding R-413A).
Possible flammability concernswith R-406A.
Adds refrigerants to serviceinfrastructure.
2. R-406A (HCFC/HCZeotrope–GHG12); originalmineral oil.
3. R-409A (HCFCZeotrope–FX56); original mineral oil.
4. R-413A (PFC/HFC/HCZeotrope–ISCEON49); original mineral oil.
Drop-In
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Replace CFC-12 refrigerantwith HFC-134a and mineral oilwith polyolester oil.
Change XH6 dryer to XH9.
Do not change compressor.
Retrofit Moderate cost. Reduced cooling capacity.
Service complexity (mineral oil flush).
Material compatibility issues.
Probable capillary tube plugging.
Brazing more critical.
Replace CFC-12 compressorwith HFC-134a compressorand polyol ester oil.
Change XH6 dryer to XH9.
Retrofit pluscompressorchange
Compressor materialcompatibility.
Compressor reliability.
Issues known and understood.
High cost.
Service complexity (mineral oil flush).
Some performance degradation.
Replace CFC-12 compressorwith HC-600a compressorand mineral oil.
Retrofit pluscompressorchange
Compressor reliability and materials compatibility.
High cost.
Each manufacturer must endorse serviceprocedure (potentialflammability issues).
National regulations may prohibit.
Space and compressoravailability uncertain.
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Commercial refrigeration
Commercial refrigeration makes use of three main groups of equipment:
• Stand-alone equipment in which all of the components are integrated. Stand-alone equipment
includes wine coolers, beer machines, ice cream machines, and all kinds of display cases sold as
stand-alone equipment.
• Condensing units separated from the cooling (evaporator) equipment which can be a small cold
room, process equipment or a vending machine. A condensing unit is composed of one (or two)
compressor(s), a condenser and a receiver. It may be in a remote location or a machinery room.
• Central systems where compressors are located in a machinery room. Distinction can be made
between two types: direct systems and indirect systems. Direct systems are widespread and
easy to design. The refrigerant circulates from the machinery room to the sales area, where it
evaporates in display cases. Indirect systems comprise primary heat exchangers where refrigerant
cools a heat transfer fluid. This is pumped towards the display cases where it recovers heat and is
then transported back to the primary heat exchanger.
Central systems are found in all kinds of supermarkets. The picture is different for stand-alone
equipment and condensing units. Stand-alone equipment may be either bought or rented, with end
users paying no special attention to the refrigeration system (technical issues are similar to those
encountered for domestic equipment). Only companies installing and maintaining the equipment have
knowledge of the refrigerant used. Condensing units are usually installed by contractors in a wide
variety of shops and convenience stores.
For stand-alone equipment, the principal refrigerant choice for small refrigerating equipment is similar
to that for domestic refrigeration. For instance, wine coolers, water fountains and vending machines
primarily use HFC-134a. A few companies – mainly located in Europe (UK, Sweden, Denmark,
Germany and Austria) but also in India and Australia – are charging equipment in commercial stand-
alone display cases from about 100 g up to 1.5 kg with hydrocarbons (R-600a, R-290 and various
blends of R-600a/R-290 or R-290/R-170). The limit for an HC charge depends greatly on specific
standards and national regulations. Stand-alone display case prototypes running with CO2 have been
developed in Norway. These units are single-stage systems with water cooled condensers.
For condensing units, use of HCFC-22 in new systems is starting to decrease because of the
availability of zero ODP solutions and of forecast changes to HCFC regulations. For low-temperature
applications, R-404A and R-507A are the major options for new equipment in many countries
(including Article 5 countries). For low-temperature applications, the energy efficiency of this option
is slightly higher than for HCFC-22. However, for medium range temperature applications, energy
efficiency is slightly lower, particularly when the condensing temperature is higher than 50 °C.
This leads to oversizing of condensers. Japanese manufacturers are investigating R-407C for
this application.
Technical options for centralized direct expansion systems are based on the same three groups of
refrigerants as for the equipment described above, i.e. HCFC-22, R-404A (the major option in Europe
in low and medium range temperature refrigeration systems); HFC-134a (for the medium
temperature); and R-407C (although the latter is not considered a major option).
Hydrocarbons are being used for some direct systems, particularly in the UK. Depending on the size
of the system, indirect circuits may be required in order to comply with relevant safety standards.
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Cascade systems using ammonia at the first stage and CO2 at the low-temperature stage have been
developed (see ‘Cold storage’).
One major disadvantage of direct expansion centralized systems is the large refrigerant charge.
Average charges are in the range of 1 to 1.5 kg/kW (cooling capacity) for medium temperature, and 3
to 4 kg/kW (cooling capacity) for low temperature. This results in total refrigerant charges varying from
300 to 1500 kg depending on the store sales area. New solutions have been introduced to minimize
the circuit and refrigerant charge, and also to improve energy efficiency. The principle consists in
installing condensing units composed of compressor racks and water condensers in sound-proofed
boxes in the sales area itself. The principal advantage is an almost 50 per cent reduction in refrigerant
charge, as well as improved energy efficiency.
Since 1995, much effort has been invested in evaluating indirect systems using heat transfer fluids,
with the aim, in particular, of lowering HCFC or HFC refrigerant charge or of permitting their
replacement by ammonia or HCs. However, “conservative” direct expansion systems with CFCs,
HCFCs or HFCs still represent more than 95 per cent of centralized systems.
The primary refrigerants used in indirect systems are:
For systems with heat transfer fluids, two innovative techniques deserve attention: systems that use
CO2 as heat-transfer fluid; and solid/liquid phase-change HTF, called ice slurries. Both types have
been developed. Some pilot plants exist but technical and commercial maturity has not yet been
reached. Many different technical issues have to be addressed in the case of indirect systems.
Moreover, additional initial cost could be increased by as much as 20 per cent compared to a
direct expansion system and the pay-back has to be justified via reduced servicing cost over
sufficiently long periods. Energy consumption is either in the same range as non-optimized direct
expansion systems or there is a 5–15 per cent energy consumption increase compared to well
designed systems.
Retrofit options depend on the life of the equipment, national regulations and refrigerant prices.
Retrofit options for stand-alone equipment are completely different from those for centralized systems.
For stand alone equipment the same options as for hermetic systems such as domestic refrigerators
should be considered.
There are two widely used options for retrofit of CFC-12 equipment. One is to use blends, usually
containing HCFC-22 (for example R-401A or R-409A), with limited retrofit efforts. The other is
conversion from CFC-12 to HFC-134a. This involves several steps, including change of the mineral oil
to synthetic oil, change of the expansion device and replacement of the filter dryer.
• ammonia: it is estimated that about 50 systems using ammonia are installed in supermarkets
in Europe;
• hydrocarbons: one German company offers either propylene or propane as primary
refrigerant in systems installed in supermarkets. About ten systems are operating with
charges of several kilograms of HC (propane and HC blend systems are also installed in the
UK and in Sweden);
• HFCs: there are a number of systems using R-404A as primary refrigerant and heat-transfer
fluids for the secondary loop.
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Lubricant requirements dictate that R-502 retrofits are mainly to HCFC-22 based blends (for example
R-402A/B, R-408A). As HCFC-22 is still available for the maintenance of the refrigeration system, it is
essentially a decision related to national regulations. It is technically feasible to change from HCFC-22
to R-404A or R-407C. Oil has to be changed and the system has to be flushed – issues comparable
to those for retrofit from CFC-12 to HFC-134a.
Annual emissions in the range of 15–30 per cent of the initial charge seem to be usual for centralized
systems. A number of emission sources are linked to poor installation, poor maintenance and piping
failures. Refrigerant emissions should decrease in the near future. For details on leak testing, readers
should refer to the chapter on refrigerant conservation. This also applies to recovery during servicing,
particularly when retrofitting.
There are less R-502 systems in supermarkets in Article 5 countries than in developed countries.
Existing large supermarkets built in the last 20 years use HCFC-22 in their centralized systems.
Small and medium supermarkets use CFC-12 in refrigeration systems with condensing units. Use
of CFC-12 is common in stand-alone equipment. Even though CFCs are still available in Article 5
countries, the shift to the use of HFC or other low- or non-ODP refrigerants has begun, especially
in stand-alone equipment. This is because Article 5 country equipment manufacturers export to
non-Article 5 countries.
Large OEM companies are on the way to conversion of their products to non-CFC technologies,
often supported by the Multilateral Fund. There is a problem in the very large segment of national
small and medium sized enterprises manufacturing all kinds of display cases, cabinets, water coolers,
etc. These companies will need special attention in terms of financial and technical support. Some
companies convert equipment from CFC-12 to HFC-134a, others from CFC-12 to HCs. In India, one
manufacturer charges new ice-cream freezers with HCs.
In contrast to the situation in developed countries, repair of used refrigeration equipment, mainly in
the domestic and commercial segments, is common practice. The cost of new equipment is much
higher than that of repair, mainly because of the low labour cost for this activity. In some large Article
5 countries, annual CFC use in the commercial servicing sector is reported to be as much as 50 per
cent of the total CFC consumption. Repair may provide the opportunity to replace CFC-12
refrigerants with “drop-in” HCFC-22 based blends, with, in some cases, the use of HC-blends, with
the proper precautions.
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Cold storage, food processing and industrial refrigeration
The majority of refrigerating systems for cold storage and food processing are of the direct type, with
the refrigerant distributed to heat exchangers in the space or apparatus to be refrigerated. Such
systems are generally custom made and erected on site. Reciprocating compressors are used most
frequently in the lower capacity range, while screw compressors are common in larger systems, in
particular those with ammonia. According to a survey, three out of four CFC systems are still in
operation. Some 70,000 tonnes of CFCs are estimated to be banked in these systems. Refrigerants
for cold storage and food processing are selected among fluids including ammonia, HCFC-22, HFC-
134a, HFC blends and also hydrocarbons.
Industrial refrigeration uses all types of refrigerants, with HCFCs and ammonia representing the
majority of volume. Historically, CFCs – including R-13B1 for specific low-temperature applications –
have made up some 20 per cent of the total. Hydrocarbons occupy a significant portion of the
market in sectors handling flammable fluids. Industrial refrigeration systems are normally located in
industrial areas with very limited public access, meaning toxic or flammable fluids such as ammonia
and hydrocarbons may be used with minimal additional cost.
Ammonia has excellent heat transfer properties and, due to its low molecular weight and high critical
temperature, also has very favourable cycle performance. As a result, systems with ammonia are
known to be more efficient than similar systems with CFCs or HCFC-22. Given ammonia’s zero
GWP, ammonia systems normally give the lowest total equivalent warming impact when direct
systems are used.
Over a couple of decades, halocarbons have improved their market position in cold storage and food
processing, even in countries with long experience with ammonia. Knowledge about ammonia
refrigeration has decreased and lack of competence with ammonia has been observed to be a
growing problem. Conventional ammonia technology, with large specific refrigerant charges, still
prevails. Modern system designs with refrigerant charges only a small fraction of those of yesterday’s
technology may increase applicability and feasibility of use of ammonia as a refrigerant. The
development in Europe indicates how Article 5 countries should approach ammonia for new systems.
Low charge ammonia technology is regarded as being fully mature. Specific charges below 30 grams
per kW refrigeration output which also achieve maximum efficiency have been reported. The low-
pressure receiver system is an efficient alternative: it has a small charge and may be applied for any
refrigerant. The technology is particularly well suited to systems in the lower to medium capacity
ranges, typical of many Article 5 countries. This may improve the economic feasibility of ammonia in
such countries.
In the United States, ammonia has approximately 90 per cent market share for systems of 100 kW
cooling capacity and above. Ammonia has not been commonly used for cold storage and food
processing in Japan. This may change in the future, although only small market shares are expected.
Ammonia has historically been one of the leading refrigerants for various sectors of industrial
refrigeration (in countries with a tradition of using this refrigerant), in spite of its toxic and flammable
nature. The main reasons for choosing ammonia have been cost and efficiency. Improved secondary
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fluids, in particular evaporating/condensing CO2, will minimize the energy penalty from additional
temperature differences. Practical experience with new ammonia technology, including low-charge
designs, is steadily growing. Ammonia is believed to cover 50–60 per cent of the industrial
refrigeration market in Europe. Use is expanding slowly in the USA.
HFC-134a and HFC blends with insignificant temperature glide, (e.g. R-404A), are considered to be
technically fully mature for application in this sector. R-404A and R-507A are currently the most used
HFCs in the sector, primarily as replacements for R-502. They are preferred to HFC-134a due to
higher volumetric capacity and lower system cost. As for commercial refrigeration, system
performance may be substantially lower at high condensing temperatures. This is important for
transfer of HFC technology to Article 5 countries, a great number of which are in regions with a
tropical climate. HFC technology for cold storage and food processing systems is nevertheless
regarded as mature for transfer to Article 5 countries.
In the future, the high capacity HFC refrigerant blend R-410A is expected to gain market share and
probably become the leading fluorocarbon refrigerant. In summary, it is possible to manage without
HCFCs in new cold storage equipment and industrial refrigeration.
Hydrocarbons are long-term, proven refrigerants with excellent thermodynamic properties. Historically,
their use has been restricted to applications within the oil and gas industry and other industries
handling flammable fluids. A certain increase in hydrocarbon consumption has been recorded,
appearing mainly in this sector where pure substances are preferred in flooded systems. Current use
of hydrocarbons is believed to be below 5 per cent of the total in industrial refrigeration.
CO2 technology for low temperature applications such as food freezing has reached the practical
application stage. Cascade systems with CO2 in the lower stage (ammonia in the upper) have proved
to be economically comparable to conventional two-stage ammonia systems for medium-sized food
processing systems (300–400 kW cooling effect at-40°C). For large systems (2 MW cooling effect), a
15 per cent saving in investment may be obtained with the cascade system. The two types of
systems are more or less equivalent with respect to energy efficiency. The same holds for industrial
refrigeration.
Due to low cost and simple retrofit procedures, 60–70 per cent of retrofits so far have involved
HCFCs, including blends with HCFCs. HFCs have been preferred in some 25 per cent of cases.
Retrofit to ammonia may be technically feasible for some larger cold storage and food processing
systems where steel is used as construction material. Hydrocarbons may be used without significant
chemical implications, but flammability restricts their use to a very limited number of systems, in both
cold storage and industrial refrigerators.
Most retrofits of CFC-12 systems have involved HCFC-22, R-401A or R-409A (HCFC blends).
R-413A, an HFC/PFC-blend with some isobutane added to improve mineral oil solubility, is another
alternative. This allows oil flushing to be omitted (experience shows that oil return efficiency depends
on temperature). Retrofit to HFC-134a has also proved to be technically safe, although a certain loss
in capacity may result, together with a certain reduction in COP.
Similar to CFC-12 systems, HCFC-22 and blends with HCFC-22 have been the preferred retrofit
fluids in the majority of cases where R-502 has been used (R-402A and R-408A are the most
commonly used blends). HFCs such as R-404A and R-507A are suitable R-502 replacements with
only small temperature glides. They could be charged into all types of R-502 systems, although the
capacity may be reduced by some 5 per cent.
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Lower price, better efficiency, and probably greater margins with respect to failure, make HCFCs (and
still CFCs) attractive compared to HFCs in many Article 5 countries. In comparison to ammonia,
differences in initial costs may be even more significant than in the developed countries (systems are
generally smaller).
Table 2 shows estimates for halocarbon consumption (CFCs, HCFCs, and HFCs/FCs) and
corresponding refrigerant “banks” as of 1996, according to a ‘best guess scenario’. These estimates
are ‘qualified guesses’, indicating only very rough orders of magnitude.
Table 2. Forecast of demand of halocarbon refrigerants
Consumption, tonnes/year Refrigerant inventory, tonnes
CFCs HCFCs HFCs CFCs HCFCs HFCs
Industrialized 7700 17600 3400 77000 109000 6800
countries (2600) (5900) (1100) (26000) (36000) (2200)
Article 5 countries1900 (500) 1900 (500) - 7500 (2500) 7500 (2500) -
Total 12700 25900 4500 113000 155000 9000
* cold storage
** industrial refrigeration
Future demands have been forecast on the basis of current consumption and the existing banks, and
‘most likely’ future development (see Table 3). The future development in Article 5 countries has been
estimated using a separate model.
Table 3. Forecast of future demand for halocarbons
Refrigerant 1998 2000 2005
Developed Countries CFCs 6150 (2050) 4400 (1470) 2090 (700)
HCFCs 16790 (5600) 16160 (5390) 12470 (4160)
HFCs 5040 (1680) 7320 (2440) 9130 (3040)
Total 27980 (9330) 27880 (9300) 23690 (7900)
Article 5 Countries CFCs 1890 (520) 1910 (540) 1590 (430)
HCFCs 1950 (550) 2060 (590) 2650 (780)
HFCs 10 (0) 30 (10) 110 (40)
Total 3580 (1070) 4000 (1140) 4350 (1250)
*to be supplied from recovered (servicing, retrofits) and stockpiled reserves. By 2000 and 2005,
available amounts of recycled CFCs will (by definition) be sufficient to cover remaining service
demands. To achieve this, the activity with respect to CFC system retrofit has to increase very
considerably.
**The first figure indicates the demand for cold storage, the second one for industrial refrigeration.
**
*
***
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Unitary air conditioning and heat pumps (air-cooled systems)
Air-cooled air conditioners and heat pumps with capacities from 2.0 kW to 420 kW comprise the vast
majority of the air conditioning market. All are electrically driven, vapour-compression systems. They
use hermetic rotary, reciprocating or scroll compressors for units with capacities up to about 100 kW
and semi-hermetic reciprocating or screw compressors for units with capacities up to 420 kW. Nearly
all of these units use HCFC-22 as the working fluid. Refrigerant charge quantities are proportional to
capacity. Assuming an average charge of approximately 0.3 kg per kW of capacity, the estimated
1700 million kW of installed capacity represent around 423,000 tonnes of HCFC-22 (see Table 4).
Air-cooled air conditioners and heat pumps generally fall into four distinct categories, based primarily
on capacity: room air conditioners; duct-free packaged and split systems; ducted systems; and single
packaged units.
Room air conditioners range in cooling capacity from less than 2.0 kW to 10.5 kW (with an average of
2.7 kW). Worldwide, approximately 12.7 million room and packaged terminal air conditioners were
sold in 1996, each containing an average of 0.64 kg of HCFC-22.
In many parts of the world, the greatest demand is for the duct-free split system. Duct-free split
systems include a compressor and heat exchanger unit installed outside the space to be cooled or
heated. The outdoor unit is connected via refrigerant piping to one or more fan coils inside the
conditioned space. Approximately 89 million duct-free units are installed worldwide. Duct-free split
systems, ranging in cooling capacity from 2.0 kW to 20 kW (average 3.8 kW), have average HCFC-22
charge levels of 0.32 to 0.34 kg per kW of cooling capacity.
Ducted residential air conditioners and heat pumps systems dominate the North American market
where central, forced-air heating systems require the installation of a duct system supplying air to
each room of a residence or small areas within commercial or institutional buildings. About 55 million
ducted split systems are currently in service worldwide, the majority in North America. Cooling
capacities range from 5 kW to 17.5 kW (average 10.9 kW) and each has an average HCFC-22
charge of 0.26 kg per kW of capacity.
Approximately 16 million commercial unitary air conditioners and heat pumps are installed worldwide.
They range in cooling capacity from about 20 kW to as much as 420 kW (average 23.0 kW).
Commercial unitary equipment carries an average HCFC-22 charge of about 0.31 kg per kW of
capacity.
Table 4. Estimated 1996 unit population and HCFC-22 inventories
Product Category Unit Population HCFC-22 Inventory (tonnes)
Room and packaged A/C 79 million 51000
and heat pumps
Duct-free packaged and split systems 89 million 112000
Ducted split systems 55 million 155000
Commercial unitary systems 16 million 105000
Total 239 million 423000
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Current trends indicate that two HFC blends, R-410A and R-407C, are the leading candidates to
replace HCFC-22 in these categories of products, with R-410A being the predominant replacement in
new products. R-407C may be one of the most likely interim to long-term replacements for HCFC-22
in large capacity (greater than 50 kW) unitary products.
In addition, commercialization of HC-290 (propane) is possible for certain applications. Several
research projects are currently being conducted on trans-critical CO2 refrigeration cycles. The trans-
critical CO2 cycle is also being investigated for residential air conditioning and heat pump
applications. Commercial viability needs to be studied further.
A significant concern is the use of hydrocarbon refrigerants as retrofit replacements for HCFC-22 in
systems not redesigned to mitigate safety risks. HC-290 has similar performance (capacity and
efficiency) to HCFC-22 but the flammable nature of this refrigerant, combined with the high charge
levels of this category of products, raises significant safety concerns for this practice. Simply replacing
HCFC-22 with hydrocarbon refrigerants can be very dangerous in many types of unitary products if
extensive system modifications are not made. Hydrocarbon refrigerants may offer acceptable retrofit
solutions in very low charge level systems.
A system life/unit population model was used to predict HCFC-22 usage for the 1996–2015 period.
Three HCFC-22 replacement scenarios were used to predict total annual HCFC-22 requirements, the
amount of HCFC-22 obtained through reclamation, and the net requirement for new HCFC-22. The
total demand for HCFC-22 in 2015 is calculated to be between 46,000 and 100,000 tonnes. The
results also show the benefits of aggressive recycling programmes in both developed and developing
countries. In 2015, 20 to 50 per cent of refrigerant demand (depending on the phase out scenario)
could be met with recycled refrigerant.
The refrigerant usage model was also used to predict the developing countries’ usage for each year
of the analysis. This was done by estimating the percentage of total world production sold in
developing countries for each year of the analysis. Whereas the HCFC-22 amount for the year 2000
is estimated to be about 18,000 tonnes, the amount of HCFC-22 estimated to be needed in 2015 will
be between 29,000 and 75,000 tonnes. The broad range is the result of different assumptions for the
use of non-ODP alternatives.
compressorexpansion
valve condenser coilscooling coils
air conditioned space
refrigerant circuit
cool air inlets
extraction grills
air intake
filtersfan
Basic principle of a ducted, unitary air conditioning system
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
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Air conditioning via water chillers
Water chillers cool or heat water which is then pumped through a heat exchanger in an air handler or
fan-coil unit which cools and dehumidifies or heats air. Water chillers using the vapour-compression
cycle are manufactured with capacities from about 7.0 kW to over 35,000 kW. Centrifugal
compressors are used for capacities from 350 kW to over 35,000 kW. HCFC-22 has been used in
small chillers and in large centrifugal ones. CFC-11 and CFC-12 have essentially been replaced in
new equipment production, by HCFC-123 and HFC-134a respectively (see Table 5). HFCs, HFC
blends (including R-410A and R-407C), ammonia and hydrocarbons are beginning to replace some
HCFC-22 based units, especially in the European Union (see Table 6).
Table 5. Air conditioning chillers in service (1997)
Chiller Type and Approx. No. of Refrigerant in Use 1997 Shipments
Refrigerant Units in Service (kt) of New Units
Centrifugal and
Screw Chillers:
CFC-11 88000 33.0 0
CFC-12 15300 6.6 0
HCFC-22 35000 14.0 1500
R-500 5400 0.9 0
HCFC-123 28300 9.8 5600
HFC-134a 15500 2.4 3960
Ammonia 2100 0.24 285
Hydrocarbons Insufficient data available
*Includes CFC-12 in R-500 chillers**Excludes any chillers produced in the Article 5 countries
Table 6. EU chiller production in 1997
Refrigerant Number of Units Per cent of Units
HCFC-22 35687 87.16%
R-407C 2806 6.85%
HFC-134a 2037 4.97%
R-717 285 0.70%
Other 1300 32%
Total 40945 100.00%
Non-HCFC-22 5258 12.84%
The ‘alternative technologies’ most feasible for the current phase out timetable are those which are
already in production. Of these, the three which are deemed to be most suitable for water chilling are
the vapour-compression cycle using ammonia as a working fluid, the absorption cycle, and zeotropic
refrigerant mixtures.
HCFC-22 has been viewed for several years as a part of the solution to the problems posed by
phase out of CFC-12 and other CFCs. In terms of efficiency and cost, HCFC-22 is the best HCFC
**
**
*
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choice presently available for positive displacement chillers, complemented by HFC-134a. The
replacement refrigerants for HCFC-22 that appear most promising in terms of their ability to satisfy
performance and safety criteria are blends of HFCs such as R-407C. The blends which seem best for
use with flooded evaporators, common in chillers larger than 700 kW, are those which, like R-410A,
are azeotropes or near azeotropes. Blends such as R-410A have COPs similar to HCFC-22 in a direct
expansion system, at significantly higher pressure levels requiring substantial product redesign and
retooling.
HFC-134a is being used in positive displacement water chillers as a replacement for CFC-12. The
volumetric flow characteristics of HFC-134a are similar to those for CFC-12. Compressor and
equipment sizes are similar. Chiller costs are not therefore significantly affected by the change from
CFC-12 to HFC-134a, except for the increase in refrigerant and lubricant costs. The excellent heat
transfer characteristics of HFC-134a offset the slightly lower cycle efficiency.
HCFC-123 is used in centrifugal chillers with capacities from 350 kW to 10,000 kW. HCFC-123
combines a relatively low environmental impact with the ability to replace CFC-11 quickly in existing
chillers of recent manufacture. The refrigerant’s low environmental impact is attributable to four factors:
low ODP, low GWP, low emissions of current-design HCFC-123 chillers, and the highest known
theoretical efficiency of all HCFCs and HFCs. HCFC-123 is a key replacement for CFC-11, due to its
relative chemical and physical similarity to CFC-11 allowing it to replace CFC-11 in new and existing
chillers without extensive modifications. This makes HCFC-123 critical to the transition from CFCs in
the chiller sector.
The number of compressor stages required to use ammonia in centrifugal chillers limits the practical
application to machines with positive displacement compressors. With some development and
adaptation, it is certain that ammonia systems could be applied more widely for water chilling,
including a wider range of air conditioning applications. Recommended practice limits the use of
ammonia in public buildings to systems that utilize a secondary heat transfer fluid (intrinsic in chillers),
confining the ammonia to the machine room where alarm devices can ensure safety.
Although hydrocarbon refrigerants have a long history of use in industrial chillers in petrochemical
plants, they have not been used in large amounts in comfort air conditioning chiller applications, owing
to reservations about system safety. Typical HCs promoted as HCFC-22 replacements include HC-
290, HC-1270 and blends. They exhibit favourable materials compatibility, oil solubility and a
thermodynamic efficiency comparable to that of HCFC-22.
CO2 is being investigated by several researchers for a wide range of potential applications using the
trans-critical cycle. The cycle exhibits a significant temperature glide on the high temperature side,
which might be attractive for water-cooled chillers or for water heating. There is no known application
to water cooling chillers to date.
Water is a thermodynamically attractive refrigerant that is non-toxic, non-flammable and has no
adverse impact on the environment. However, it is a very low pressure refrigerant. Traditionally water
has been used in specialty applications with steam aspirators, rarely with vapour compressors except
in the case of mechanical vapour re-compression systems. Recent applications use water as a
refrigerant to produce ice slurries by direct evaporation from a pool of water. Cost increases of up to
50 per cent over conventional systems are likely.
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Absorption chillers are inherently larger and considerably more expensive than vapour-compression
chillers. Absorption systems have therefore had only limited market success in the Western market. In
Japan, where electricity prices are much higher, absorption chillers dominate the market.
The retrofit options that exist for each chiller are dependent upon the specific refrigerant for which the
chiller was originally designed. HCFC-123 became available in 1989 to retrofit existing CFC-11
chillers. Its solvent properties are different from those of CFC-11. System capacity may be reduced by
0–20 per cent, depending on heat exchanger effectiveness and matching of the compressor to the
load. HFC-134a also became available in 1989, to retrofit existing CFC-12 chillers.
There are currently no satisfactory replacement refrigerants for use in existing equipment designed for
HCFC-123. HFC-245fa is being investigated as a potential alternative. It has similar vapour pressure
and appears to have good stability and low toxicity. It may also be less aggressive to motor insulation
and may thus have advantages as a retrofit refrigerant for CFC-11 chillers.
However, much of the existing stock of installed equipment still requires CFCs for servicing. It is too
early to know whether recycling efforts will provide a sufficient supply of CFCs to meet servicing
needs until the remaining machines are replaced or retrofitted. It has been estimated that over 70 per
cent of the CFC chillers in service in the United States in 1990 were still in service in the last quarter
of 1998. The other 30 per cent have either been replaced or converted to HCFCs or HFCs. Based on
informal data, progress does not appear to have been faster in other countries. This rate of
conversion is significantly slower than predicted.
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Transport refrigeration
Transport refrigeration includes transport of refrigerated products in reefer ships, intermodal
refrigerated containers, refrigerated railcars and by road transport including trailers, diesel trucks and
small trucks. It also includes the use of refrigeration and air conditioning on merchant ships above
300 gross tonnes and air conditioning in buses and railcars. The transport volume of reefer ships has
decreased in recent years compared to intermodal refrigerated containers, for which the share of the
total volume was estimated at 55 per cent by the millennium.
Since the working environment in all subsections of transport refrigeration is severe, emissions are, on
average, higher than those in other areas.
As many European countries are to ban HCFC-22 in new installations, ships due for delivery in the
next few years will most probably be fitted with long-term HCFC-22 alternatives. To reduce the initial
charge and improve the possibility for reduced leakage, most will be delivered with indirect systems
and a secondary refrigerant in the future. Alternative HFC blend candidates today are R-404A and R-
507 but it is estimated that, as of 2000, R-410A will dominate the marine market as replacement for
HCFC-22 in new systems. Due to the increased refrigeration capacity of the product, systems can be
made more compact with reduced initial refrigerant charge on each ship.
There are approximately 410,000 intermodal container units in operation today. Unfortunately half of
them use CFC-12 as a refrigerant. Each unit contains around 5 kg of refrigerant. Average lifetime of a
container is estimated to be 15 years and 50 per cent of the units in operation today with CFC-12 are
expected to still be operating in 2003 and beyond. Units made in recent years use HFC-134a, R-
404A and HCFC-22.
However, there is a potential for use of non-fluorocarbon refrigerants such as CO2 with a trans-critical
vapour compression cycle with internal heat exchange. Containers are currently being tested and a
high tonnage could switch to this refrigerant in the next 5–10 years if technological aspects meet user
requirements.
Non-fluorocarbon refrigerants such as hydrocarbons and ammonia will not be allowed as refrigerants
in containers as their flammabilities contravene International Maritime Organization (IMO) legislation.
There are approximately 80,000 refrigerated railcars in use worldwide today, of which 60 per cent are
in the former Soviet Union. The majority of these units use CFC-12 as refrigerant. With two
refrigeration units per railcar each containing approximately 15 kg of refrigerant, the total pool is 2,400
tonnes. Out of this, 1,500 tonnes are CFC-12; the rest is mainly HFCs. In North America, it is
estimated that 500 railcars using R-404A are in service.
The total world fleet of refrigerated vehicles is estimated at around 1,000,000. Of these about 30 per
cent are trailer units, 40 per cent are independent truck units and the remainder are smaller units with
the refrigeration unit driven by the truck engine. HFC-134a, R-404A, and HCFC-22 are currently used
in production. This leads to a bank of 1,000 tonnes of HCFC-22 and nearly 3,000 tonnes of HFCs.
Because of the onerous operating conditions, annual service requirements account for 20–25 per
cent of the pool.
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In a recent development in Germany and other European countries an HC (propane) was tested and
approved. It is now on offer as an off-the-shelf product. The flammability risk of this substance means
that safety precautions should be taken, including a refrigerant leak detector in the trailer and
adequate training for drivers.
There are more than 30,000 ships of all types (tankers, general cargo, cruise ship and ferries) in
excess of 300 gross tonnes. Ninety-five per cent of the fleet uses HCFC-22 as a refrigerant, the rest
still mainly using CFCs. The total HCFC bank may be around 30,000 tonnes, including fishing fleets
and navies. Emission rates for naval vessels are high, due to their special operating conditions.
However, it is estimated that better maintenance and improved quality have reduced amounts leaked
by 20 per cent. Although HCFC-22 is still used for new equipment, use of HFC-134a, R-404A and R-
507 is increasing. In the cruise ship sector, where huge HVAC systems are used, most systems are
delivered with HFC-134a. However, the latest product manufactured in Europe has chiller equipment
using R-410A.
There are an estimated 320,000 buses and coaches with air conditioning worldwide, the majority of
which are now using HCFC-22 (152,000) and HFC-134a (68,000). It is estimated that the largest
growth will be in Europe in the next five years, since air conditioning in buses is not yet fully
developed. HFC-134a will be the preferred refrigerant. Leakage rates are relatively high, estimated to
be 50 per cent of the initial charge annually, due to the fact that most systems use long lengths of
polymer tubing.
In Germany all new high-speed trains will use air cycle systems for their air conditioning. R-407C has
been selected for new trains in France and Spain.
It is possible to retrofit from CFC-12 to HCFC-22. It is also possible to convert to R-401A/B or R-
409A. These have similar pressure and capacity to CFC-12 but are interim solutions that contain
HCFCs. HFC-134a demands a level of system cleanliness that might be difficult to obtain in old
systems operating with CFC-12. It is therefore not recommended, especially as capacity and
performance at low temperature do not compare with those of CFC-12. Interim solutions are
therefore used, particularly when the equipment has few years of operational service left. Long-term
solutions to retrofit from CFC-12 are available today and these offer the best environmental solution.
In transport, in sub-sectors such as containers, buses and trucks, where use may well be for more
than five years, retrofitting to R-404A or R-413A will probably take place. One of the world’s major
LPG/LPN gas carriers has decided to retrofit its HCFC-22 systems to HC-290 and HC-1270.
However, in this situation there is a crew working with hydrocarbons taking daily care of safety
aspects and all the equipment required is intrinsically safe. From a thermodynamic point of view,
the ships converted so far have shown advantages over HCFC-22.
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Mobile air conditioning
All new vehicles produced since 1995 have been equipped with HFC-134a air conditioning (A/C)
systems (with the exception of very limited production of CFC-12 systems in China, India and Korea).
HFC-134a is therefore clearly the globally accepted mobile air conditioning refrigerant.
There is a significant service concern associated with new vehicles equipped with HFC-134a A/C
systems entering the world market. Given the availability of low cost CFC-12, and the lack of
adequate service infrastructure in Article 5 countries, there is a tendency to convert these
new vehicles systems from HFC-134a to CFC-12. New vehicles are expected to continue to be
equipped with HFC-134a A/C systems until an alternative that offers an economically viable
environmental advantage with respect to global climate change can be identified, developed, and
commercialized.
Mobile A/C systems relate to global warming in two ways: directly as a result of emission of refrigerant
to the atmosphere, (e.g. from system leakage and servicing); and indirectly from the release of CO2from burning fuel to power the A/C system and to carry its weight. To date, two future systems are
under study as potential replacements for HFC-134a: trans-critical CO2 and hydrocarbons.
The CO2 system and its applicability to mobile air conditioning have been studied as part of a
European Union project known as the RACE Project. The results of this were released recently in the
form of technical papers. The consensus emerging from the RACE Project is that – although many
questions remain concerning safety, quality, efficiency, maintenance and commercialization – the
trans-critical CO2 system appears to be a promising technology for mobile air conditioning. Significant
system development remains necessary prior to commercialization. CO2 systems were projected to
cost 20 per cent more and weigh 2.5 kg more than HFC-134a systems.
The use of flammable hydrocarbon refrigerants in future vehicles has been proposed for reasons
similar to those for CO2, i.e. they are non-ozone depleting and have very low global warming
potentials. While they are excellent refrigerants, flammability makes them a significant potential safety
hazard for use in mobile A/C. A recent paper by a major A/C system supplier suggests that
hydrocarbons should be considered if safety concerns are adequately addressed through cooperation
between vehicle and A/C system manufacturers. Concerns about flammability can be significantly
reduced, if not completely eliminated, through the use of a secondary circuit with the flammable
refrigerant contained in the engine compartment. Such indirect systems may require 5–10 per cent
additional energy to operate.
The existing CFC-12 fleet is expected to be phased out by the year 2008. Efforts to accelerate
complete phase out would, of course, be environmentally beneficial. Refrigerant recycling has been
proven to be of value, both economically and environmentally. Experience with multiple refrigerants
(CFC-12, HFC-134a, and several retrofit refrigerant blends) has shown that, with refrigerant recycling
and reuse, it is very important to prevent refrigerant cross-contamination in mobile A/C systems.
Mixing of refrigerants can lead to high compressor discharge pressures, loss of cooling, deterioration
of A/C system materials and possible system failure.
Retrofitting of the CFC-12 based fleet has occurred, but not nearly to the extent predicted. This is
probably due to stockpiling prior to the ban on CFC production, to CFC-12 recycling, and to
smuggling of CFC-12 into developed countries, especially those where the cost price of CFC-12 is
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high. HFC-134a is the only retrofit refrigerant recommended and supported by vehicle manufacturers.
With adequate supply of CFC-12, the service industry has only recently started to retrofit the CFC-12
fleet. A typical time to consider retrofitting is when a major component fails and the system requires
servicing. Replacement components should have comparable performance levels if the cooling
performance after retrofit is to be comparable to the original system.
Hydrocarbons have been used in some countries (e.g. Australia) as a retrofit refrigerant for CFC-12
systems. Use of a flammable refrigerant in CFC-12 mobile A/C systems not specifically designed to
handle such refrigerants safely is a dangerous practice, due to the risk of passenger injury from fire
and/or explosion. The use of flammable refrigerants in HFC-134a mobile A/C systems has been
banned in some states in Australia and in the United States. Supporters of flammable refrigerants
have acknowledged safety concerns and have recommended A/C system modifications prior to their
use. These considerations should be taken into account in any effort to design new systems using
flammable refrigerants.
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Heat pumps (heating only and heat recovery)
The vast majority of heat pumps currently in operation are electrically driven, closed-cycle
compression type systems. Systems driven by gas engines or absorption cycle heat pumps, directly
fired or employing waste heat, have found niche markets. Refrigerants currently used in heat pumps
are CFCs, HCFCs, HFCs, ammonia and hydrocarbons (HCs).
Heating-only heat pumps are used for space and water heating in residential, commercial/institutional
and industrial buildings, and in district heating and cooling plants. In industry, heat pumps are used
for heating of process streams, heat recovery and hot water/steam production. They are often an
integral part of industrial processes used for drying, evaporative concentration and distillation, etc. It
is estimated that the total heating-only heat pump stock in residential and commercial sectors
(including district heating) is roughly 1.7 million units, with a total heating capacity of about 13,300
MW. The corresponding figures for industrial heat pumps are 8,500 units and a total heating capacity
of 3,000 MW.
In developed countries, HCFC-22 is still used as one of the main refrigerants in heat pumps. In
developing countries (e.g. China) CFC-12 still accounts for a large portion of the refrigerants, together
with HCFC-22. Developed country manufacturers have introduced HFC alternatives to replace their
HCFC heat pump models. HFC-134a and R-404A have been on the market for more than five years.
The first models using R-407C entered the market in 1996/97, units using R-410A in 1998/99. Non-
ODP and low-GWP refrigerants are environmentally safe alternatives to CFCs and HCFCs in heat
pump systems. The most promising potential refrigerants in this group are ammonia, hydrocarbons
(e.g. propane, propylene, and blends of hydrocarbons), carbon dioxide and water.
The thermodynamic and physical properties of HFC-134a are similar to those of CFC-12 and R-500
and it is regarded as the main successor to CFC-12 in medium-temperature heat pump systems.
HFC-134a is used in many new heat pump installations. HFC-152a was considered a promising
alternative refrigerant to CFCs because of its favourable thermodynamic and physical properties and
low GWP factor. There are many examples of successful small heat pumps using HFC-152a, e.g. in
the United States, Scandinavia and China. However, its flammability makes adequate safety measures
necessary to ensure safe operation and maintenance.
R-404A, R-407C and R-410A are the preferred HFC-blends for replacement of HCFC-22 in heat
pump applications. The systems have to be optimized in order to bring performance in line with
HCFC systems (large-surface heat exchangers, control systems, improved compressor design, etc.).
Ammonia has excellent thermodynamic properties and ammonia based heat pumps typically achieve
3–5 per cent better energy efficiency than systems using CFC-12, HCFC-22 or HFC-134a. The
volumetric refrigeration capacity is approximately the same as for HCFC-22. Ammonia gives high
compressor discharge temperatures and, at high temperature lifts, two-stage compression is
necessary to avoid operational problems. Initial costs will therefore increase. However, energy
efficiency will also increase by 30–35 per cent.
As for all sectors, the most important hydrocarbons for medium-temperature heat pump applications
are propane (HC-290), propylene (HC-1270) and blends of propane/iso-butane and ethane/propane.
Several North European manufacturers of heat pumps are using HC-290 or HC-1270 as refrigerants
in small residential and commercial water-to-water and air-to-water heat pumps. A number of
prototype heat pumps with HC-290 and other hydrocarbons have been installed. The units are limited
in size and are also designed for low refrigerant charge.
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Heat pumps with CO2 as the refrigerant are now being commercialized for tap water heating. A CO2heat pump may produce hot water with temperatures up to 95 °C, much higher than traditional heat
pump water heaters, without operational problems. CO2 requires components with higher pressure
ratings and smaller flow channels than are commonly used today. Such components have been
developed for a large range of capacities. Investigations are ongoing into use of CO2 as refrigerant for
several applications such as heating in residential buildings and heat pump dryers.
Heat pump refrigerants can be re-used or recovered or heat pumps can be retrofitted with alternative
refrigerants. In general, the number of heat pumps retrofitted so far has been lower than expected. It
was not technically feasible or economically justifiable to retrofit or dismantle all heating-only heat
pumps using CFCs by 1995/96. Reuse and recovery of refrigerants still play an important role.
As in most sub-sectors, retrofitting from CFC-12 to HFC-134a is quite common and the precautions
that need to be taken are well known. Common ternary blends for retrofitting of heat pumps
manufactured to use CFC-12 and R-500 are R-401A, R-401B and R-409A. There have been
discussions about using hydrocarbons as retrofits for CFC-12. Retrofitting from CFC-12 to
hydrocarbons is more likely to use an HC-290/600a blend than HC-290, since the blend better
matches the characteristics of CFC-12. Flammability means that use of hydrocarbons for retrofit
applications may be limited by local ordinances and safety codes. To date, retrofits from CFC-12 to
hydrocarbons in heat pumps are not common.
HFC blends for retrofitting heat pumps using R-502 have been commercially available since 1993/94.
The retrofitting procedure for HFC-blends is similar to that for HFC-134a, with a change of lubricant
from mineral oil to a polyolester lubricant. The most frequently used retrofit blend in heat pumps is R-
404A. A number of HCFC blends have been developed as short term alternatives to retrofit R-502
units. Common near-azeotropic retrofit blends are R-402A, R-402B, and R-408A. The retrofit
procedure is simple and inexpensive.
R-290, propylene (R-1270) and HC blends are possible retrofit candidates for HCFC-22. The
volumetric refrigeration capacity of propane is almost the same as with HCFC-22, and no compressor
modifications are needed. However, the above comments regarding flammability apply.
Estimated CFC and HCFC demand for heating-only heat pumps in 1998 was 480 tonnes for CFC
and 710 tonnes for HCFC. Assessments indicate that the total annual refrigerant demand for heat
pumps will be about 2,000 tonnes in 2005, of which 70–80 per cent will be HFCs and the rest
HCFCs, ammonia and hydrocarbons. Availability of high-quality recovered refrigerants for service
purposes is an important factor.
compressor
expansionvalve
condensing coils
coolwater
warm water
pump
riverheat
source
evaporatorrefr
iger
ant
circ
uit
swimming pool
Basic principle of a heat pump system
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
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Refrigerant conservation
Refrigerant conservation is now a major consideration in refrigerating system design, installation, and
service. Environmental impacts from refrigerant release include not only ozone depletion but also
global warming. Safety issues come into play for refrigerants such as hydrocarbons or ammonia.
Conservation also addresses the servicing needs of existing equipment. Since CFC and HCFC
production is reduced and will be halted in future, refrigerant supplies will dwindle and recovered
quantities will be necessary for both non-Article 5 and Article 5 countries. While progress has been
made in limiting refrigerant emissions over the last three years, refrigerant conservation is an issue that
continues to require full attention. Conservation can be obtained for all kinds of refrigeration and air-
conditioning equipment in all phases of equipment life cycle, through design and construction of leak-
tight and easily serviced systems, leak detection and repair, recovery during service, and recovery at
disposal.
Recovery/recycling/reclaim requirements have been implemented for some years in certain countries
and have shown positive results. However, many countries have yet to implement such requirements.
Few countries have developed comprehensive containment policies including both recovery and leak
tightness. Initiatives generally come from the field, where refrigerant is beginning to be regarded as too
expensive to be wasted.
In addition to phasing out ODS production under the Montreal Protocol, governments can help to
reduce ozone depletion by strongly encouraging containment. One basic approach is simply to make
refrigerant recovery compulsory. In addition to direct regulation, both non-Article 5 and Article 5
governments can encourage containment in a number of ways including research and development,
information dissemination, and financial incentives.
Every attempt should be made to design sealed systems that will not leak during service life, and to
minimize service requirements that require opening of the system. The potential for leakage is first
addressed by system design. The lower the charge of refrigerant in a system, the lower the emission
in case of system rupture.
Proper installation of refrigerating systems contributes to proper operation and containment during the
useful life of the equipment. Refrigerating systems must be tested regularly to ensure that they are well
sealed, properly charged, and operating correctly. Refrigerant should not be released during
maintenance and scrapping of the system.
Service must be improved in order to reduce emissions. However, such improvement depends in part
on the price end-users are willing to pay, as emission reduction has always, so far, proved more
expensive than topping up cooling systems with refrigerant. It is necessary to make end-users
understand that the money they pay for refrigerant must be saved and spent on improved
maintenance. Such steps have already been taken in some cases. For example, in the United States
a tax on refrigerant makes containment more cost-effective. Of course, full technician training is
essential for proper handling and containment of refrigerants.
There are three general types of leak detection: global and local methods, and automated
performance monitoring. Global methods indicate that a leak exists somewhere, but they do not
locate leaks. They are useful at the end of construction and whenever the system is opened for repair
or retrofit. Local methods pinpoint the location of the leak and are the usual methods used during
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
38
servicing. Automated performance-monitoring systems indicate that a leak exists by alerting operators
to changes in equipment performance.
Refrigerant recovery equipment has been developed and is available with a wide range of features
and prices. Some special explosion-proof equipment also exists for recovery of flammables.
Refrigerant conservation requires definition of the efficiency or completeness of recovery.
The need for refrigeration containment has led to the development of a specific terminology; the
following definitions apply:
Recovery of the liquid is the quickest method, and should be the priority when recovering quantities
above 50 kg, as time-loss is a decisive argument against carrying out recovery. Vapour recovery is
necessary, since the only way of checking that all liquid has been evaporated is to lower the pressure
in the system below the saturation vapour pressure of the refrigerant. Recovery by compressor is the
most common solution. Most compression recovery units are suitable for recovering vapour even for
low pressure values down to 10 kPa.
Recycling is one of three available options for dealing with recovered refrigerants. The other two are
direct reuse and reclaiming. Unlike direct reuse, recycling equipment is used to remove oil, acid,
particulates, chloride, moisture, and non-condensable (air) contaminants from used refrigerants.
Recycling performance can be measured by applying standard test methods to contaminated
refrigerants. Some restrictions have been placed on the use of recycled refrigerant because it is not
necessarily analysed before each use. This has even led to legal restrictions on recycled refrigerant.
For example, in France recycled refrigerant can only be used in the system from which it came.
A range of recycling equipment is available at a wide range of prices. At present, the automotive air-
conditioning industry is the only sector where recycling is preferred. Acceptance in other sectors will
depend on national regulations, recommendations from cooling system manufacturers, existence of
other solutions such as a reclaim station, variety and type of systems, and the preference of the
service contractor.
Reclaimed refrigerant means refrigerant that has been processed and verified by analysis to meet new
product specifications, such as those given in ARI 700-93. This has the advantage of avoiding
possible system breakdowns which would lead to further refrigerant emission. As reclaimed
refrigerant meets new product specifications, it often has the support of equipment manufacturers.
Recover: means removing refrigerant in any condition from a system and storing it in an external
container.
Recycle: means reducing contaminants in used refrigerants by separating oil, removing non-
condensables, and using devices such as filter-dryers to reduce moisture, acidity, and
particulate matter.
Reclaim: means processing used refrigerant to new product specifications. Chemical analysis of
the refrigerant is required to determine that appropriate specifications are met. The identification
of contaminants and required chemical analysis has to refer to national or international
standards for new product.
Dispose: means destroying used refrigerant in an environmentally responsible manner.
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
39
More and more technologies are being developed for destruction and several have become
economically attractive. Two technologies, liquid injection and rotary furnace incinerators, are widely
used. They have been specially tested for the destruction of CFCs and have the required destruction
efficiency of 99.99 per cent.
Although the wide range of specific conditions in Article 5 countries makes generalization difficult, a
few characteristics emerge across the refrigeration infrastructures of those countries that distinguish
them from the refrigeration infrastructures of developed countries. These characteristics favour the
adoption of strategies for containing and conserving refrigerant in Article 5 countries that are slightly
different from those applied in developed countries. Characteristics include:
• The relatively low price of CFC refrigerants. Because CFCs are not scheduled to be phased out at
short notice in most Article 5 countries, they remain relatively inexpensive in the majority of them.
This decreases economic incentives to conserve CFC refrigerants.
• The relatively low cost of labour compared to equipment. Low labour rates may favour
conservation approaches that are more labour-intensive than those historically pursued in
developed countries. Technician training is the only solution here.
• Absence of refrigerant reclamation infrastructures. A well-developed infrastructure for reclaiming
refrigerant requires large numbers of reusable refrigerant containers, refrigerant purification centres,
a system for tracking returned refrigerant and a means of disposing of irretrievably contaminated
refrigerant. The amount of refrigerant to be recovered in countries using small quantities of
refrigerant is not likely to justify operation of a centralized “Reclaim Centre” for one country only.
obsolete
recycledrefrigerant
to recovery depot
analysis
use in refrigeration equipment
treatment
disposal ofnon–recyclable fluid
recovery
Steps in the recovery and recycling of refrigerants
• Uneven maintenance. In many Article 5 countries, routine maintenance of air-conditioning and
refrigeration equipment has been rare in the past. To successfully implement conservation
approaches, which rely heavily on regular maintenance, countries would have to change attitudes.
• Unreliable power and parts supplies. In many Article 5 countries, frequent voltage fluctuations
increase the incidence of compressor burnouts aggravating refrigerant contamination problems
and discouraging refrigerant recycling. These fluctuations may also damage electrical recovery
equipment.
There is no shortage of leak detection devices, conservation methods, or recovery/recycling
equipment available from developed countries. However, provision of such equipment will not, of itself,
guarantee refrigerant conservation in Article 5 countries. Experience has shown that in order to be
effective, containment programmes must match equipment with training and with continuing
incentives to use the equipment. Incentives may be: financial (e.g. deposit-refund systems similar to
those used in Australia and France); professional (building on technicians’ pride in completing training
and in using the most advanced equipment and techniques); or environmental (showing technicians
that they have the power to help heal the ozone layer). Refrigerant Management Plans (RMPs) which
focus on low-volume consuming Article 5 countries include these different aspects. The RMP is a key
component for reduction in consumption of all ODS, because a significant portion of all ODS used is
consumed in refrigeration and air-conditioning. To meet the target of CFC phase out, emphasis should
be placed initially, but not only, on replacing CFCs in new and existing equipment as well as on
refrigerant conservation through recovery/ recycling/reclaim and leak reduction.
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
40
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
41
Resources
Secretariats and Implementing Agencies
Multilateral Fund Secretariat
Dr. Omar El Arini
Chief Officer
Secretariat of the Multilateral Fund for
the Montreal Protocol
27th Floor, Montreal Trust Building
1800 McGill College Avenue
Montreal, Quebec H3A 6J6
Canada
Tel: 1 514 282 1122
Fax: 1 514 282 0068
E-mail: secretariat@unmfs.org
Web site: www.unmfs.org
UNEP Ozone Secretariat
Mr. Michael Graber
Acting Executive Secretary
UNEP Ozone Secretariat
PO Box 30552
Gigiri, Nairobi
Kenya
Tel: 2542 623-855
Fax: 2542 623-913
Email: Michael.grabber@unep.org
Web site: www.unep.org/ozone
UNEP
Mr. Rajendra M. Shende, Chief
Energy and OzonAction Unit
United Nations Environment Programme
Division of Technology, Industry and Economics
(UNEP DTIE)
39-43 quai Andre Citroen
75739 Paris Cedex 15
France
Tel: 33 1 44 3714 50
Fax: 33 1 44 3714 74
Email: ozonaction@unep.fr
Web site: www.uneptie.org/ozonaction
UNDP
Dr. Suely Carvalho, Deputy Chief
Montreal Protocol Unit, EAP/SEED
United Nations Development Programme
(UNDP)
304 East 45th Street
Room FF-9116,New York, NY 10017
United States of America
Tel: 1 212 906 6687
Fax: 1 212 906 6947
Email: suely.carvalho@undp.org
Web site: www.undp.org/seed/eap/montreal
UNIDO
Mrs. H. Seniz Yalcindag, Chief
Industrial Sectors and Environment Division
United Nations Industrial Development
Organization (UNIDO)
Vienna International Centre
P.O. Box 300
A-1400 Vienna
Austria
Tel: (43) 1 26026 3782
Fax: (43) 1 26026 6804
E-mail: yalcindag@unido.org
Web site: www.unido.org
World Bank
Mr. Steve Gorman, Unit Chief
Montreal Protocol Operations Unit
World Bank, 1818 H Street NW
Washington DC 20433
United States of America
Tel: 1 202 473 5865
Fax: 1 202 522 3258
Email: sgorman@worldbank.org
Web site: www.esd.worldbank.org/mp/home.cfm
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
42
Airconditioning and Refrigeration Institute
1501 Wilson Boulevard, 6th Floor
Arlington, VA 22209-2403
United States
Tel: 1 703 524 8800
Fax: 1 703 528 3816
Online: www.ari.org
Alternative Fluorocarbon Environmental
Acceptability Study
The West Tower Suite 400
1333 H Street NW
Washington DC 20005
United States
Tel: 1 202 898 0906
Fax: 1 202 789 1206
American Society of Heating, Refrigerating and
Airconditioning Engineers
1791 Tullie Circle, NE
Atlanta, GA 30329
United States
Tel: 1 404 636 8400
Fax: 1 404 321 5478
Online: www.ashrae.org
Chinese Association of Refrigeration
Building 11, South No. 1 Lane
2nd Section of Sanlihe
100045 Beijing
Tel: 86 10 685 30717
Fax: 86 10 685 36262
E-mail: dscao@263.net.cn
European Council of Chemical Manufacturers
Federations (CEFIC)
(Mr. B. Jenssen, Secretary)
Avenue E. Van Nieuwenhuyse, 4
1160 Brussels
Belgium
Tel: 32 2 676 7240
Fax: 32 2 676 7301
E-mail: bje@cefic.be
Eurovent / European Committee of Manufacturers
of Refrigeration Equipment (CECOMAF)
Reyerslaan 80
1030 Brussels
Belgium
Tel: 32 2 706 7985
Fax: 32 2 706 7966
E-mail: info@eurovent-cecomaf.org
French Institute of Refrigeration (AFF)
c/o Union Syndicale des Constr. de Materiel
39–41 Rue Louis Blanc
92400 Courbevoie
Cedex 72, 92038 Paris
France
Tel: 331 4717 6292
Fax: 331 4717 6427
German Refrigeration Society (DKV)
Pfaffenwaldring 10
70569 Stuttgart
Germany
Tel: 49 711 685 3200
Fax: 49 711 685 3242
E-mail: dkv@itw.uni-stuttgart.de
Institute of Refrigeration
c/o Miriam Rodway, Ass. Secretary
Kelvin House
76 Mill Lane
Carshalton
Surrey SM5 2JR
United Kingdom
Tel: 44 20 8647 7033
Fax: 44 20 8773 0165
E-mail: ior@ior.org.uk
International Institute of Ammonia Refrigeration
1200, 19th Street, NW, Suite 300
Washington, DC 20036-2412
United States
Tel: 1 202 857 1110
Fax: 1 202 233 4579
E-mail: Kent_Anderson@iiar.org
Contact Points
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
43
International Institute of Refrigeration
177 Boulevard Malesherbes
75017 Paris
France
Tel: 331 4227 3235
Fax: 331 4763 1798
E-mail: iifiir@iifiir.org
Japanese Association of Refrigeration
San-El Building
4th Floor, No 8
San-El-Cho, Shinjuku-ku
Tokyo
Japan
Tel: 81 3 3359 5231
Fax: 81 3 3359 5233
Motor Vehicle Manufacturers Association
Environmental Activities Staff
GM Technical Center
30400 Mound Road
Warren, MI 48090-9015
United States
Tel: 1 313 872 4311
Fax: 1 313 872 5400
UNEP Refrigeration Technical Options Committee
c/o co-chair Dr. L. Kuijpers
TEMA - TDO
Technical University Pav A58
PO Box 513
5600 MB Eindhoven
The Netherlands
Tel: 31 49 247 63 71
Fax: 31 40 246 66 27
E-mail: lambermp@wxs.nl
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
44
Further reading
AFEAS 1997, Energy and Global Warming Impacts of HFC Refrigerants and Emerging Technologies,
J.R. Sand, S.K. Fischer and V.D. Baxter, AFEAS, Washington, D.C., U.S.A.
ASHRAE Standard 34-1989R, Number designation and safety classification of refrigerants – First
public review draft, American Society of Heating, Refrigerating and Air-Conditioning Engineers,
Atlanta, USA, 1991.
Baker, J.A., Mobile Air Conditioning and the Global Climate - A Summary of the Phoenix Alternate
Refrigerant Forum - July 15-18,1998, Proceedings The Earth Technologies Forum, October 26-28,
1998, Washington DC.
Bivens, Donald B., Minor, Barbara H., Fluorethers and Other Next-Generation Fluids, Proceedings of
the Refrigerants for the 21st Century Conference, Gaithersburg, Maryland, October 1997.
Bullock, C. E., Theoretical Performance of Carbon Dioxide in Subcritical and Transcritical Cycles,
Proceedings of the Refrigerants for the 21st Century Conference, Gaithersburg, Maryland,
October 1997.
Calm, J.M. and Didion, D.A., Tradeoffs in Refrigerant Selections: Past, Present and Future,
Proceedings of the Refrigerants for the 21st Century Conference, NIST, Gaithersburg, MD USA,
October 1997 (see also International Journal of Refrigeration, 21(4), 308-321, June 1998).
Clodic, D. and Sauer, F. for the French Association of Refrigeration (A.F.F.), Paris, The Refrigerant
Recovery Book, 1994 ASHRAE Edition.(Vademecum de la Récupération des CFC, 1993 PYC
Edition).
Clodic, D. Zero Leaks. ASHRAE Edition. 1998. (Zéro Fuites, 1997 PYC Edition).
Clodic, D., and Cai, W., Tests and Simulations of Various Hydrocarbons in Room Air Conditioners and
Refrigerators, Proceedings of the IIR Natural Refrigerants Conference, Aarhus, Denmark, 1996.
Gentner, H. (BMW), Passenger Car Air Conditioning Using Carbon Dioxide as Refrigerant,
Proceedings IIR Natural Working Fluids ‘98 Conference, June 2-5, 1998, Oslo, Norway.
Kuijpers, L., Lessons Learned-From Montreal to Kyoto? The Imperative of Full Implementation,
Proceedings 1998 Earth Technologies Forum Conference, Washington D.C., 26-28 October 1998.
Kuijpers, L., The Impact of the Montreal and the Kyoto Protocol on New Developments in
Refrigeration and A/C, Proceedings IIR B2 Meeting, Delhi, India, 18-20 March 1998.
McLinden M. O., Optimum refrigerants for non-ideal cycles: An analysis employing corresponding
states, Proceedings IIR Purdue Refrigeration Conference and ASHRAE Purdue CFC Conference, W.
Lafayette, lndiana, July 17-20, 1990. pp 69-79.
Midgley, T., “From the periodic table to production”, Ind. and Engr. Chemistry 29 241-244, 1937.
Nekså, P, et al., CO2 Heat Pump Prototype Systems-Experimental Results, EA/IIR Workshop on CO2
Technology in Refrigeration, Air Conditioning & Heat Pump Systems. Trondheim, Norway, May 1997.
Tiedemann, T., Burke, M., Kruse, H., Recent Developments to Extend the Use of Ammonia.
Proceedings of the 1996 International Refrigeration Conference at Purdue, University of Purdue,
Indiana, USA, July 23-26, 1996.
United Nations Environmental Programme, 1998 Assessment Report of the Refrigeration, Air
Conditioning and Heat Pumps Technical Options Committee, UNEP, 1998, ISBN 92-807-1731-6.
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
45
Wertenbach, J. and Caesar, R. (Daimler-Benz), An Environmental Evaluation of an Automobile Air
Conditioning System with CO2 Versus HFC-134a as Refrigerant, Proceedings IIR Natural Working
Fluids ‘98 Conference, June 2-5, 1998, Oslo, Norway.
WMO, Global Ozone Research and Monitoring Project – Report No.44, Scientific Assessment of
Ozone Depletion: 1998, WMO, February 1999, ISBN 92-807-1722-7
Wuebbles, D.J. and Calm, J.M., An Environment Rational for Retention of Endangered Chemical
Species, Science, 278, 1090-1091, November 1997.
“Designation and Safety Classification of Refrigerants,” ANSI/ASHRAE Standard 34-1997, American
Society of Heating, Refrigerating, and Air-Conditioning Engineers (ASHRAE), Atlanta, GA, 1997
J. M. Calm, “Refrigerant Database,” Air-Conditioning and Refrigeration Technology Institute (ARTI),
Arlington, VA, August 1998
Intergovernmental Panel on Climate Change (IPCC) of the World Meteorological Organization (WMO)
and the United Nations Environment Programme (UNEP), “Climate Change 1995 – Contribution of
Working Group I to the Second Assessment Report of the Intergovernmental Panel on Climate
Change,” edited by J. T. Houghton, L. G. Meira Filho, B. A. Callander, N. Harris, A. Kattenberg, and K.
Maskell, Cambridge University Press, Cambridge, UK, 1996
“Scientific Assessment of Ozone Depletion: 1994,” chaired by D. L. Albritton, R. T. Watson, and P. J.
Aucamp, report 37, World Meteorological Organization (WMO), Global Ozone Research and
Monitoring Project, Geneva, Switzerland; United Nations Environment Program (UNEP), Nairobi,
Kenya; National Oceanic and Atmospheric Administration (NOAA), Washington, DC, USA; National
Aeronautics and Space Administration (NASA), Washington, DC, USA; February 1995
Glossary
AFEAS Alternative Fluorocarbon Environmental Acceptability Study
CEIT Country with Economy in Transition
CFC chlorofluorocarbons
COP Coefficient of Performance
DTIE Division of Technology, Industry and Economics (UNEP DTIE)
GWP Global Warming Potential
HC hydrocarbon
HCFC hydrochlorofluorocarbons
HFC hydrofluorocarbons
HTF Heat Transfer Fluid, or “secondary refrigerant”
MLF Multilateral Fund for the Implementation of the Montreal Protocol
ODP Ozone Depleting Potential
ODS Ozone Depleting Substance
OEM Original Equipment Manufacture
PAC Packaged Air Conditioner
RAC Room Air Conditioner
TEAP Technology and Economic Assessment Panel
TEWI Total Equivalent Warming Impact
TOC Technical Options Committee
UNEP United Nations Environment Programme
VOC Volatile Organic Compound
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
46
About the UNEP DTIE OzonAction Programme
Nations around the world are taking concrete actions to reduce and eliminate production and
consumption of CFCs, halons, carbon tetrachloride, methyl chloroform, methyl bromide and HCFCs.
When released into the atmosphere these substances damage the stratospheric ozone layer – a
shield that protects life on Earth from the dangerous effects of solar ultraviolet radiation. Nearly every
country in the world has committed itself under the Montreal Protocol to phase out the use and
production of ODS. Recognizing that developing countries require special technical and financial
assistance in order to meet their commitments under the Montreal Protocol, the Parties established
the Multilateral Fund and requested UNEP, along with UNDP, UNIDO and the World Bank, to provide
the necessary support. In addition, UNEP supports ozone protection activities in Countries with
Economies in Transition (CEITs) as an implementing agency of the Global Environment Facility (GEF).
Since 1991, the UNEP DTIE OzonAction Programme has strengthened the capacity of governments
(particularly National Ozone Units or “NOUs”) and industry in developing countries to make informed
decisions about technology choices and to develop the policies required to implement the Montreal
Protocol. By delivering the following services to developing countries, tailored to their individual needs,
the OzonAction Programme has helped promote cost-effective phase out activities at the national and
regional levels:
Information Exchange
Provides information tools and services to encourage and enable decision makers to make informed
decisions on policies and investments required to phase out ODS. Since 1991, the Programme has
developed and disseminated to NOUs over 100 individual publications, videos, and databases that
include public awareness materials, a quarterly newsletter, a web site, sector-specific technical
publications for identifying and selecting alternative technologies and guidelines to help governments
establish policies and regulations.
Training
Builds the capacity of policy makers, customs officials and local industry to implement national ODS
phase out activities. The Programme promotes the involvement of local experts from industry and
academia in training workshops and brings together local stakeholders with experts from the global
ozone protection community. UNEP conducts training at the regional level and also supports national
training activities (including providing training manuals and other materials).
Networking
Provides a regular forum for officers in NOUs to meet to exchange experiences, develop skills, and
share knowledge and ideas with counterparts from both developing and developed countries.
Networking helps ensure that NOUs have the information, skills and contacts required for managing
national ODS phase out activities successfully. UNEP currently operates 8 regional/sub-regional
Networks involving 109 developing and 8 developed countries, which have resulted in member
countries taking early steps to implement the Montreal Protocol.
Refrigerant Management Plans (RMPs)
Provide countries with an integrated, cost-effective strategy for ODS phase out in the refrigeration and
air conditioning sectors. RMPs have to assist developing countries (especially those that consume low
volumes of ODS) to overcome the numerous obstacles to phase out ODS in the critical refrigeration
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
47
sector. UNEP DTIE is currently providing specific expertise, information and guidance to support the
development of RMPs in 60 countries.
Country Programmes and Institutional Strengthening
Support the development and implementation of national ODS phase out strategies especially for low-
volume ODS-consuming countries. The Programme is currently assisting 90 countries to develop their
Country Programmes and 76 countries to implement their Institutional-Strengthening projects.
For more information about these services please contact:
Mr. Rajendra Shende, Chief, Energy and OzonAction Unit
UNEP Division of Technology, Industry and Economics
OzonAction Programme
39-43, quai André Citroën
75739 Paris Cedex 15 France
E-mail: ozonaction@unep.fr
Tel: +33 1 44 37 14 50
Fax: +33 1 44 37 14 74
www.uneptie.org/ozonaction.html
UNEP�
PROTECTING THE OZONE LAYER • TECHNICAL BROCHURE UPDATES • REFRIGERANTS
48
About the UNEP Division of Technology, Industry and Economics
The mission of the UNEP Division of Technology, Industry and Economics is to help decision-makers
in government, local authorities, and industry develop and adopt policies and practices that:
• are cleaner and safer;
• make efficient use of natural resources;
• ensure adequate management of chemicals;
• incorporate environmental costs;
• reduce pollution and risks for humans and the environment.
The UNEP Division of Technology, Industry and Economics (UNEP DTIE), with its head office in Paris,
is composed of one centre and four units:
• The International Environmental Technology Centre (Osaka), which promotes the adoption and use
of environmentally sound technologies with a focus on the environmental management of cities
and freshwater basins, in developing countries and countries in transition.
• Production and Consumption (Paris), which fosters the development of cleaner and safer
production and consumption patterns that lead to increased efficiency in the use of natural
resources and reductions in pollution.
• Chemicals (Geneva), which promotes sustainable development by catalysing global actions and
building national capacities for the sound management of chemicals and the improvement of
chemical safety world-wide, with a priority on Persistent Organic Pollutants (POPs) and Prior
Informed Consent (PIC, jointly with FAO).
• Energy and OzonAction (Paris), which supports the phase out of ozone depleting substances in
developing countries and countries with economies in transition, and promotes good management
practices and use of energy, with a focus on atmospheric impacts. The UNEP/RISØ Collaborating
Centre on Energy and Environment supports the work of the Unit.
• Economics and Trade (Geneva), which promotes the use and application of assessment and
incentive tools for environmental policy and helps improve the understanding of linkages between
trade and environment and the role of financial institutions in promoting sustainable development.
UNEP DTIE activities focus on raising awareness, improving the transfer of information, building
capacity, fostering technology cooperation, partnerships and transfer, improving understanding of
environmental impacts of trade issues, promoting integration of environmental considerations into
economic policies, and catalysing global chemical safety.
www.unep.orgUnited Nations Environment Programme
P.O. Box 30552 Nairobi, KenyaTel: (254 2) 621234Fax: (254 2) 623927
E-mail: cpiinfo@unep.orgweb: www.unep.org
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