978-1-4244-2800-7/09/$25.00 ©2009 IEEE ICIEA 2009

Environmental Protection and Refrigerants Substitution Strategy

Yin LIU 1. School of Environmental & Municipal Engineering

Xi’an University of Architecture and Technology Xi’an, China

2. School of Energy & Environment Zhongyuan University of Technology

Zhengzhou, China hvacr@126.com

Guanghui ZHOU

School of Energy & Environment Zhongyuan University of Technology

Zhengzhou, China gh@zzti.edu.cn

Angui LI

School of Environmental & Municipal Engineering Xi’an University of Architecture and Technology

Xi’an, China visitli@yahoo.com.cn

Abstract—In current, the refrigerants of the refrigeration and air-conditioning are more about CFC and HCFC, these substances are damaging to the ozone layer and greenhouse. 1987 launched the "Montreal Protocol" is to protect the Earth's ozone layer international document, and in 1997 launched the "Kyoto Protocol" is to slow global warming international document. The two documents gave the specific need of the CFC and HCFC Refrigerants cut out a time limit, and often based on scientific observations out to adjust the pace and the whole is speeding up. In this paper, China for example, the refrigerant application and development, environmental impacts and substitution technologies of the developing countries explored. It considered that developing countries should actively engage in green refrigerants research. At the same time, they should not to limit or speed up to cut out the HCFC substances. Contrary, they should take full advantage of the 30 years of material HCFC the "grace period" for developing countries by the international community and make HCFC substances full play active role out of the CFC substances.

Index Terms—Refrigerants, HCFC, CFC, HFC, Substitution, Strategy

I. INTRODUCTION Global warming has become a common concern of all

countries in the world, limiting greenhouse gas emissions and prevent the destruction of ozone depleting substances has been used to reach a consensus [1]. Currently, the most refrigerant of the refrigeration and air-conditioning system is CFC and HCFC; it can damage to the ozone layer and cause greenhouse effect. In 1976, UNEP (United Nations Environment Programmer) council discusses the ozone layer damage, UNEP and WMO (World Meteorological Organization) established the Ozone Layer Coordination Committee (CCOL), regular assessment of the damage the ozone layer. 1977 holds a meeting of ozone layer experts, 1981 started out internal discussion between the Government for international

agreements on the destruction of ozone depleting substances, and in March 1985 formulated the "Vienna Convention on the Protection of the Ozone Layer", and it encourages the Government to cooperation on study in a planned way, observing the ozone layer, supervision the production of CFCs and exchange of information. States Parties to the Convention promises to take the general measures for protect human health and the environment on the ozone layer change by humanity activities. "Vienna Convention" is a framework agreement; it does not contain legally binding controls and objectives. In September 16, 1987, 46 countries in Montreal, Canada signed the "Agreement on Substances that Deplete the Ozone Layer to the Montreal Protocol," it is the international documents of protect the Earth's ozone layer, started to take concrete actions to protect the ozone layer. 1997 launched the "United Nations Framework Convention on Climate Change Kyoto Protocol, the Kyoto Protocol", it is the international document to slow global warming. The two documents gave the specific prescribes on the use of refrigeration and air-conditioning installation of a large number of refrigerants and eliminated the requirement for a specific, and it often adjusted based on scientific observations. Generally speaking, he paces of the whole process is accelerating. In July 14, 1989, China formally joined the "Vienna Convention", in June 1991, in the "Vienna Convention" and the second meeting of the Parties to the "Montreal Protocol" Parties to the third meeting, China formally announced to add "the Montreal Protocol "London Amendment. April 2003, the Chinese Government signed the "Montreal Protocol" Copenhagen amendment. At the same time, the "China phasing out ozone-depleting substances national programmer" was compiled in 1992 and in 1997 the programmer has been revised to identify suitable for China's national conditions substitutes and alternative technologies, and further clear-out strategy and the overall industry out plan, proposed workable policy measures and the supervision and management system. As a yield big country of air conditioning

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producing, refrigerant of HCFC alternative will have a significant impact on China refrigeration and air-conditioning industry.

II. REFRIGERANTS DEVELOPMENT From a historical perspective, the development of

refrigerant has experienced three stages [2] [3]:

The first phase, from 1830 to 1930, the refrigerants were mainly NH3, HC, CO2, air and other natural refrigerants, some toxic, some flammable. Even though used for a 100-year-long, when the CFC and HCFC refrigerants were found, the refrigerants acted decisively to achieve a significant first transition.

The second phase, from 1930 to 1990, mainly uses chlorine Synthesis refrigerant, which CFC (R11, R12, R114) and HCFC (R22, R142b). As human discovered and understand the damage to the ozone layer, people discovered, the chlorine atom or bromine atoms of these compounds react with ozone in the atmosphere above the stratospheric, consumption of ozone and damage to the ozone layer. Since 1987 the international community signed the "Montreal Protocol" to gradually reduce and stop production serious damage to the ozone layer, CFC and halon, the ozone layer damage has been eased, but to restore to a few decades ago level, is likely to have dozens years. After 60 years later, these refrigerants found to damage the ozone layer. For the needs of environmental protection, the refrigerant was forced to realize the second transition.

The third phase, from 1990 to date, HFC refrigerant entering the main period. Third-generation refrigerants solve the destruction of the ozone layer, at the time known as "the environmental quality", the "green refrigerants" or "fluorine-free refrigerants", has been described as a long-term substitute. However, with the increase in production of these refrigerants, a strong greenhouse effect was brought. In addition to CO2, fluorinated gases are also major greenhouse gases, in particular to the fluoride or fluoride-based carbon compounds, known as the "F-Gases", fluorine gases include HFCs, PFCs, SF6 and etc., which widely used in industrial production and daily life, such as refrigerators, air conditioners, insulation materials and medical aerosols. These gases are fluorinated, and the day-to-day use of their unique environment and security interests (not to damage the ozone layer, low toxicity and non-flammable). Even so, they may be in the atmosphere in the hundreds or thousands of years and gradually accumulating to cause a strong greenhouse effect. It is the restricted substances part of the Kyoto Protocol.

III. APPLICATION OF REFRIGERANTS

A. Refrigerant production Application Status in China China has become a huge output of the refrigeration and

air-conditioning countries. In refrigeration and air-conditioning products, from small room air conditioner to more than 1,000 kW cooling capacity of the screw chiller, the HCFC-22 has been wildly, only a few products used HFCs refrigerants. HCFC-22 is in a dominant position in Chinese refrigeration and air-conditioning products, roughly in the ratio of about 85%. In current, China has 19 HCFC-22 production enterprises, and total capacity for nearly 500,000 tons, the annual output about 350,000 tons, 20-30% for the raw materials for the fluorine, 70-80% for ODS use [4]. In ODS use, about 40% for exports and 50% for the refrigeration and air-conditioning consumption, and 10% for other industries, such as foam. Clearly, not only for Chinese refrigeration and air-conditioning industry, but also for the fluorine chemical industry of Chinese consumption, the substitution of HCFC-22 occupies an extremely important position [5].

B. The comparison of developing and developed countries Figure 1 and Figure 2 is the UNEP [6] statistics developed

and developing countries HCFC production and consumption trends in the changes during the period 1989-2004, (not include data before 1989, because before 1989, the date of developing countries is less, and the gap greater). Figure 1 and Figure 2 show that the developed countries HCFC emissions to the atmosphere in the historical responsibility of the total amount are several times higher than that of developing countries. If calculated on a per-capita, the volume of the difference may be several times. From the output and the total consumption in 2004, while the total production of the developed countries is only slightly less than the developing countries, the total consumption of developing countries is 53% of the developing countries, but from their per capita output and consumption of view, they are many times more than developing countries. Moreover, the contrast to the currently developed and the developing countries the penetration of refrigeration and air-conditioning, even the rapid development country China compares with the United States and Japan. Both the refrigeration and air-conditioning products per capita volume and per capita consumption of refrigerant, United States and Japan are several times than China. Table 1 gives the per capita output and per capita consumption of HCFC of China, United States and Japan, in comparison to the data, the United States, Japan is 3.5 to 5.6 times of China. According to survey in 2004, 90% of the domestic air-conditioning still using R22 in the United States [7].

TABLE I. THE COMPARED THE PER CAPITA OUTPUT AND PER CAPITA CONSUMPTION OF HCFC OF CHINA, UNITED STATES AND JAPAN (UNEP 2007)

Population Billion HCFC

t(ODP) Maximum

Year Baseline t(ODP)

Per capita g/P

Relative value %

CHINA 12.39 Output 18 101.2 2005年 14.6 100 Consumption 11 928.0 2005年 9.6 100

USA 2.63 Output 15 297.6 1998年 15 389.6 58.1 389 Consumption 14 139.9 1998年 15 248.4 53.7 559

JAPAN 1.26 Output 6 296.2 1995年 5 645.4 50.0 342 Consumption 5 748.7 1995年 5 554.9 45.6 475

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02040

6080

100

120

140

Developing country Developed country

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P)3

1989

1990

1991

1992

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1996

1997

1998

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2000

2001

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2004

05

101520253035

Figure 1. The change trend of HCFC production of developing and

developed countries (UNEP 2007)

Developing country Developed country

The

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0 t)(

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510

1520

25

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1989

1990

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1996

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1998

1999

2000

2001

2002

2003

2004

0

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40

60

80

100

120

Figure 2. The change trend of HCFC consumption of developing and

developed countries (UNEP 2007)

IV. HCFC IS IDEAL TRANSITIONAL SUBSTITUTION Figure 3 comparisons the ODP and GWP of the main pure

compounds CFC, HCFC and HFC. Visible from the map, CFC refrigerant is not only having the highest value ODP, but also has the relatively high value of GWP, whether from the destruction of the ozone layer and global climate change, CFC substances need to be controlled and prohibition of the Use. The ODP value of is HFC refrigerant zero, but it has higher value of GWP. HFC has no damage to the ozone layer, but for global climate change, it is still considerable influence. Thus, the "Kyoto Protocol", HFC and CFC, HCFC type substances "greenhouse gas" emissions to increase its control. HCFC refrigerants such as damage to the ozone layer and global climate change, the impact of relatively small. World Meteorological Organization and the investigation report pointed out that the chlorine atoms in the atmosphere peaked in the period, HCFC generated by chlorine atoms accounts for only 1% [3].

In 1994, Scientific Assessment Report of Ozone Depletion of UNEP found that all controlled substances, HCFC on the stratospheric load of minimizing the impact of Cl. Even cease all HCFC emissions of substances after 2004, for the impact to stratospheric Cl load reduce, its contribution is only about 5% in the next 50 years.

Figure 4 shows the impact on of global climate change of CFC, HCFC and HFC-134a. It clearly shows the HCFC on the impact of global climate change is far smaller than the CFC.

Evidently, HCFC has slower ODP value (0.012 ~ 0.086), shorter atmospheric lifetime survival (1.4 years to 18.5 years)

and the lower value of GWP (120 ~ 2300). The ODP value of HCFC is more than 98% of small than CFC, and its atmospheric survival if short about 80% than CFC. HCFC’s destruction of the ozone layer is very small and in the controlled substances the combined effects on the environment of HCFC are the smallest too. Generally believe of the international community, HCFC is a kind of very necessary transition of the refrigerant during the elimination of CFC for developing countries, it has to guarantee the timely out CFC [8].

Figure 3. The change trend of HCFC consumption of developing and

developed countries (UNEP 2007)

Figure 4. CFC, HCFC and HFC-134a on the impact of global climate change

Zhu [3] comparison the substitute products R107C, R410 and HFC-134a of HCFC-22 in detailed, although alternative products are zero ODP, can completely eliminate the threat of damage to the ozone layer, but its GWP also higher. They are "greenhouse gases" on global warming too and have the same direct impact of R22 [9]. From limiting greenhouse gas emissions and the technical problems of view, the R107C, R410 and HFC-134a are not satisfactory. For the implementation of the "Kyoto Protocol", HFC was eliminated sooner or later.

V. REFRIGERANTS SUBSTITUTION STRATEGY IN CHINA China is a refrigerant production and consumption power

country, refrigeration and air-conditioning industry rapid development in recent years. The refrigerants substitution of China was concerned by the international environmental organizations and international interest groups. The refrigerants substitution of China should consider environmental issues, historical responsibility, the reality of the development of the national interests, the development of enterprises, industries situation and the interests of consumers:

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(1) China has signed the amendment resolution of "Montreal Protocol", responsibility and the obligation to complete the R12, R11, and other alternative work of CFC, which have been smoothly implemented;

(2) As a developing country, should not accelerate the process of restrictions on the use or eliminated of HCFC. Contrary, China should take full advantage of the developing countries about nearly 30 years "grace period" of HCFC by the international community, and give full active play of HCFC in the process of the CFC substances. Furthermore, the HFC has higher greenhouse, and the refrigeration and air-conditioning systems, and its main components and equipment must be changed when use HFC. It has grave differences on making HFC as a long-term substitute of international community. In this 30 "grace period" it is still possible to develop new long-term substitutes; the pattern of long-term substitutes may change completely [3].

(3) Use the characteristic that the refrigerant of the refrigeration and air-conditioning industry was used in the confined system in used, improve the system of closed, lower leakage rate, raise the system energy efficiency, reduce filled volume. Establish maintenance and recovery system [5].

(4) Actively carry out the research and application of natural refrigerants (ammonia, hydrocarbons and CO2) and other recent natural refrigerants (R152a and R1230) [2].

(5) Compressor is the key of refrigeration system; China should actively develop the compressor of long-term use and high energy efficiency ratio [10].

(6) Research the new type of nano-materials green refrigerant [11].

VI. CONCLUSION China is already the greenhouse gas emissions power

country in the world, refrigeration and air-conditioning industry has become an important pillar industry, "fluoride bans" on will have a significant impact on Chinese refrigeration and air-conditioning industry. First of all, as "Vienna Convention", "Montreal Protocol" and the "Kyoto Protocol" parties, China must fulfil commitments; secondly, as a developing country,

China should make full use of the international community to developing countries of the "grace period"; at the same time, China should also actively participate in a new refrigeration and cooling equipment research and development, and constantly promote international refrigeration industry sustained and rapid development.

ACKNOWLEDGMENT Financial supports from Science and Technology Office,

Henan, China. Project Number 072102240013

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