fluorinated reduction technologies 2014 - nedo reduction technologies 2014-toward the prevention of...

Fluorinated Reduction Technologies 2014-Toward the Prevention of Global Warming-

“We are crews　on Spaceship Earth.”

New Energy and Industrial Technology Development Organization

Mar 2014 (8th Edition)

Background and Purpose of R&D

Background and Purpose of R&D………………………………………………… 1

NEDO's Past Contributions… ……………………………………………………… 3

Ongoing NEDO Projects

Technology Development of High-efficiency Non-fluorinated Air-conditioning Systems……………………………………………………………… 4

Completed NEDO projects

Development of HFC-23 Destruction Technology… ……………………………… 5

Development of Technology for Chemical Recycling of HCFC Refrigerants… … 7

Development of Energy-saving Synthetic Technologies to Fluorocarbon Replacements… ……………………………………………………………………… 9

Development of Chlorine Fluorinated Gas Substitutes… ………………………… 10

R&D of SF6 Substitute Gas Cleaning System for Electronic Device Manufacturing…………………………………………………………………………… 11

Development of Non-SF6 Melting Process and Micro Structural Control for High Performance Magnesium Alloy……………………………………………… 13

Project to Support the Practical Implementation and Application of Emission Control Equipment to Control Three Fluorinated Gas Substitutes… …………… 14

Development of Non-fluorinated Energy-saving Refrigeration and Air-conditioning Systems………………………………………………………………………………… 15

Project to Develop Innovative Non-fluorocarbon Heat Insulation Technology…… 17

Contents

Terminology The ozone layer that exists in the upper stratosphere

about 10 to 50 km above the Earth's surface plays a valu-

able role in protecting usagainst harmful ultraviolet rays.

However, since the late 1970s, chemical substances such

as chlorofluorocarbons (CFCs) and hydrochlorofluorocar-

bons (HCFCs) have been depleting the ozone layer.

Because ozone-depleting substances undergo little

chemical change, they reach the stratosphere nearly in-

tact. Once they reach the stratosphere, chemical sub-

stances are broken down by ultraviolet radiation (photoly-

sis) and release ozone-destroying chlorine atoms. As the

ozone layer is depleted, the amount of harmful ultraviolet

rays reaching the Earth increases. This can result in po-

tentially severe effects on the ecosystem as well as in-

creased cases of skin cancer and cataracts.

Global warming is a phenomenon in which the Earth's

average temperature rises due to an increase in the

amount of greenhouse gases, such as CO2, in the

atmosphere. Three gases (Hydrofluorocarbons (HFCs),

perfluorocarbons (PFCs) and sulfur hexafluoride(SF6))

developed and used as substitutes for CFCs and HCFCs

also cause global warming in the same way as CO2, and

the emission of these gases needs to be reduced.

An index that indicates global warming potential rela-

tive to carbon dioxide, which is defined as the reference

gas and whose value is set to 1.0. GWP100 is a numeric

integration value for the greenhouse effect for 100 years.

Ozone depletion

Global warming

Global warming potential (GWP)

An index that indicates ozone depletion potential rela-

tive to CCl3F (CFC-11), which is defined as the reference

gas and whose value isset to 1.0.

Ozone depletion potential (ODP)

Under the Montreal Protocol, CFCs and HCFCs were

designated as controlled substances. Because these

substances deplete the ozone layer, the use of CFCs

was completely phased-out in 1996, and HCFCs will be

substantially phased-out by 2020.

Controlled substances

Fluorinated gas substitutes

HFCs, PFCs and SF6 are three types of gases have no ozone-depleting chlorines, but have high GWP values.

Background and Purpose of R&D

1

(1) Emergence of Ozone Depletion ProblemChlorofluorocarbons (CFCs) were developed by Dr.

Thomas Midgley in 1928 as a substitute for ammonia, a

refrigerant for electric refrigerators. CFCs were also widely

used as foaming agents, detergents and aerosol propellants

due to their useful properties, and became essential chemi-

cals for maintaining existing advanced industrial technolo-

gies and a comfortable living environment.

Professors Sherwood Rowland and Mario Molina of the

University of California published a study in 1974 describing

how CFC gases were depleting the ozone layer.

As a result of the depletion of the ozone layer, the amount

of ultraviolet rays reaching the Earth has increased. This may

adversely affect our health by causing ailments such as skin cancer and cataracts, and may also damage the genes of plants and

animals and endanger their survival. In 1985, the discovery of an ozone hole over the South Pole (Figure 1) raised the impor-

tance of this issue worldwide.

(2) The Montreal Protocol (Control of Ozone-Depleting Substances)Based on the Vienna Convention for the Protection of the

Ozone Layer (1985), the Montreal Protocol was adopted in

1987 as an international framework to control CFC usage.

Since the adoption of the protocol, the production and

import/export of controlled substances (CFCs and hydrochlo-

rofluorocarbons (HCFCs)) have been regulated in stages in

developed countries.In addition, it was decided in September

2007 at the 19th Conference of the Contracting Parties to the

Vienna Convention to reduce consumption of those gases in

stages. The use of CFCs was completely phased-out in 1996,

and the use of HCFCs will be substantially phased-out by

2020（Figure 2）. For this reason, the development of substitutes has been steadily progressing.

In Japan, the production and import/export of ozone-depleting substances have been regulated since 1989, and measures to

steadily reduce production have been implemented.

(1) Fluorinated gas substitutes behave as greenhouse gasesTo protect the ozone layer, CFC and HCFC substitutes such as Hydrofluorocarbons (HFCs), perfluorocarbons (PFCs) and

sulfur hexafluoride (SF6) (three fluorinated gas substitutes), which do not deplete the ozone layer, have been developed and dis-

seminated as substitutes for the controlled substances. However, it became evident that the three fluorinated gas substitutes were

greenhouse gases that contribute to global warming. In addition, it became apparent that the controlled substances, CFCs and

HCFCs, also behave as greenhouse gases.

(2) Framework Convention on Climate Change and the Kyoto ProtocolBased on the United Nations Framework Convention on Climate Change, concluded in 1992 to stabilize atmosph green-

house gas concentrations, the Kyoto Protocol was adopted as a greenhouse gas emission control measure in 1997.Following

ratification by Russia, the Kyoto Protocol entered into force in 2005. Consequently, Japan was obligated to reduce its green-

house gas emissions to 6% below 1990 levels by the first commitment period (2008–2012).

Greenhouse gases that are subject to reduction under the Kyoto Protocol include the three fluorinated gas substitutes(HFCs,

PFCs and SF6) as well as carbon dioxide (CO2), nitrous oxide (N2O) and methane (CH4). Since the global warming potential

Figure1 Ozone Hole

Prepared by Japan Meteorological Agency based on NASA’s satellite observation data

October 1979 October 2011

GWP of Fluorinated Gas Substitutes is Several Hundred to Several Tens of Thousands of Times that of CO2

Baseline year 1989 Year

Control scheduleBased on consumption (production + import volume - export volume) in 1989:

Note 1: Production must not exceed the average of the standard for production and consumption from 2004.

After January 1, 1996: 100% or lowerAfter January 1, 2004: 65% or lowerAfter January 1, 2010: 25% or lowerAfter January 1, 2015: 10% or lowerAfter January 1, 2020: 0% or lower

Based on production (the average of production and consumption) in 1989:

Note 2: The use of supplement refrigerants for refrigeration and air- conditioning up to 0.5% of the baseline level is allowed until 2029.Note 3: The cap on production is set at the average of [HCFC production in 1989 + 2.8% of CFC production in 1989] and [HCFC consumption in 1989 + 2.8% of CFC production in 1989].

After January 1, 1996: 100% or lowerAfter January 1, 2004: 25% or lowerAfter January 1, 2015: 15% or lowerAfter January 1, 2020: 0% or lower

Background and Purpose of R&DProtection of Ozone Layer and Conversion to Fluorinated Gas Substitutes

Figure 1 Ozone Hole

Figure 2 Phase-out Schedule for HCFCs

NEDO’s Past Contributions

2

(GWP) of the three fluorinated gas substitutes is several hundred to several tens of thousands of times that of CO2, utmost

efforts towards regulating their emission are required.

(3) Overview of global warming prevention action plan and Kyoto Protocol Target 　 Achievement Plan for three fluorinated gas substitutes

The numeric emission reduction targets specified in

the Kyoto Protocol Target Achievement Plan, which was

announced in 2005 and revised in March 2008, are

shown in Table 1.

As the emissions of the three fluorinated gas

substitutes significantly declined in 2002, it

became clear that the 2010 target of 73 million

tons of CO2 (+2%) stipulated in the Global

Warming Prevention Action Plan was attainable.

Since this target was attainable, a more

aggressive target of 52 million tons or less of

CO2 (+0.1%) was set. Because of the efforts of

each industry, it became clear that even the more

aggressive target of 31 million tons or less of CO2

(-1.6%) was set when the Kyoto Protocol Target

Achievement Plan was revised in March 2008.

(4) Convenience of fluorinated gas chemicals and efforts to reduce usageBecause of their useful properties,

CFCs, HCFCs and the three fluorinated gas

substitutes are used as refrigerants (forre-

frigerators and air-conditioners), industrial

detergents (for electric parts, precision

parts, optical parts, etc.), foaming agents

(for heat insulation materials), semicon-

ductor and liquid crystal manufacturing

(for etching, CVD chamber cleaning, etc.),

electrical insulating equipment, extinguish-

ing agents, and magnesium manufacturing.

They are utilized in a wide range of appli-

cations that are useful in daily life.

Although we benefit from the afore-

mentioned gases, greater efforts are needed

to address the difficult task of reducing the emission of the three fluorinated gas substitutes as much as possible, while also

maintaining the convenience they provide (Figure 3).One of NEDO’s notable contributions is briefly outlined below:

The New Energy and Industrial Technology Development Organization (NEDO) has consistently addressed environmental

issues since its establishment in 1980. In particular, its Environment Department has been promoting the development of new tech-

nologies to reduce burdens on the global environment.

In particular, the department has worked to contribute to phasing out of ozone-depleting substances in accordance with the

Montreal Protocol and to reduce greenhouse gas emissions to help meet Japan’s Kyoto Protocol obligation. Recently, high priority

technology development has been carried out to satisfy Japan’s Kyoto Protocol greenhouse emission obligation by 2012. (Figure4)

NEDO’s Efforts to Reduce Controlled Substances and Three Fluorinated Gas Substitutes

NEDO's Past Contributions

Base year FY2011 FY2010 target emissions between base year and FY2010 target

Energy origin CO2

Non-energy origin CO2①CH4②N2O③

Fluorinated gas substitutes HFCsPFCsSF6

Subtotal A

Subtotal①+②+③

Subtotal④Total（A+①+②+③+④）

Forest carbon sequestration + CDM, etcGreenhouse gas emissions

Mt ̶ CO2

10591059

151

511261̶

1261

853333

201417

Mt ̶ CO2

11731173

110

251308-971211

682022

2132

Mt ̶ CO2

10891089

132

311252-671186

2.3

-1.5

-1.60.0-5.4-6.0

842325

2254

※Base year: 1990 except for the fluorinated gas substitutes, which is 1995. ※Target values for FY2010 are from the Kyoto Protocol Target Achievement Plan revised in March 2008. ※Emissions in FY2011 are from Japan's Greenhouse Gas Inventory Report issued in April 2013.

Table1 Greenhouse Gas Emissions in 2011

Figure 3 Efforts to Reduce Fluorinated Gas Substitutes

NEDO’s Past Contributions

3

The Project to Support the Practical Implementation and Application of Emission Control Equipment to Control Three

Fluorinated Gas Substitutes implemented by NEDO (see page14) has made a significant contribution to achieving the emission

reduction target (-1.6%) set in the Kyoto Protocol Target Achievement Plan for three fluorinated gas substitutes.

The results of the project research and development themes carried out from

FY2006 to FY2010 were favorable, and a total emission reduction (for the first com-

mitment period of the Kyoto Protocol) of approximately 17.8 million tons CO2

equivalent was achieved. The annual average reduction was 3.6 million CO2 tons

(about 18% of the reduction target for fluorinated gas substitutes (-20 million CO2

tons)(Figure 5)). This value is equivalent to a 4.8% reduction of the reduction target

for Japan’s total greenhouse gas emissions.

The newly developed technologies, which have demonstrated their efficacy

through this project, can further contribute to the prevention of global warming by

efforts to promote and propagate them not only in Japan but also in other countries

through licensing or product export as leading-edge Japanese technologies for the

prevention of global warming.

NEDO will continue to promote extensive technology development as measures

against fluorinated gases.

Japan’s first demonstration refrigeration system using natural refrigerants (CO2) as a substitute for fluorinated gas was developed

through the Development of Non-fluorinated Energy-saving Refrigeration and Air-conditioning Systems project (see page 15). Tests were

conducted by installing the system in freezer and refrigerator showcases. The freezer showcases were subsequently installed inactual

supermarkets in order to ensure reliability through the Project to Support the Practical Implementation and Application of Emission

Control Equipment to Control Three Fluorinated Gas Substitutes. In addition, NEDO provided support for a technical demonstration

aimed at addressing technical issues related to performance improvement and dissemination implemented through the same project and

the system was installed in additional supermarkets and convenience stores. Through NEDO’s support, the pace of technology develop-

ment was accelerated and seamless introduction to the market was achieved.

Emission reduction due to NEDO's project

Emission reduction due to activities other than NEDO's project

3.6 Mt/year18%

16.4 Mt/year　　 82%

Contribution of NEDO’s Non-fluorinated Gas Project ②From R&D to domestic demonstration and dissemination

Figure 5 Contribution of NEDO’s 　　　　Project to Emission Reduction 　　　　Target for Fluorinated Gas 　　　　　　　　　Substitutes (-20 million CO2 tons)

Contribution of NEDO’s Fluorinated Gas Project①NEDO’s project accounts for 18% of Japan’s fluorinated gas substitute emission reduction target

Figure 4 NEDO Technology Development for Measures to Reduce Fluorinated Gas Emissions

～1997（H9） 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012 2013（H25～）

Development of Energy-saving Synthetic Technologies for Fluorocarbon Replacements (2002‒2006)

Development of Chlorine CFC

Substitutes (1996‒1997)

R&D on a Cleaning System for Electronic Device Manufacturing Using Substitute Gases for SF6

and Other Gases (1998‒2002)

Development of Non-SF6 Melting Process andMicro-structural Control for High-performance Magnesium Alloy

(2004‒2006)

Project to Support Practical Implementation and Application of Emission Control Equipment to Control Three Fluorinated

Gas Substitutes (2006‒2010)

Development of Non-fluorinated Energy-saving Refrigeration and Air-conditioning Systems (2005‒2010)

Project to Develop Innovative Non-fluorocarbon Heat Insulation Technology

(2006‒2011)

Technology Development of High-efficiency Non-fluorinated Air-conditioning Systems

(2011‒2015)

Development of HFC-23 Destruction technologies (1998‒2001)

Development of Technology for Chemical

Recycling of HCFC Refrigerants(2000‒2001)

Development of common technology

Development of new CFC substitutes

Technology for non-CFCs

Digestion/destruction technology

Completed NEDO Projects

4

In the freezing and air-conditioning field, required refrigerant properties vary depending on the temperature range of use

and equipment size (refrigerant volume, piping length, etc.). NEDO has been carrying out research and development on refrig-

erant conversion aimed at cooling-only commercial refrigerator-freezers and small-scale room air-conditioners. Meanwhile,

active development has not been undertaken for commercial air-conditioners because the scale is far larger than room air-con-

ditioners (Table 2) and it is difficult to clear existing technology barriers for conversion.

In recent years, however, due to a global change in attitude toward safety assessment of mildly flammable refrigerants, and

with the debut of new technologies for using CO2 refrigerant in a high-pressure supercritical state, the potential for refrigerant

conversion is rapidly increasing in the commercial air-conditioning field. In addition, a BAU* estimate of three fluorinated gas

substitutes emissions is expected to account for about 30% of emissions in the freezing and air-conditioning field by 2020

(Figure 6). Therefore, urgent measures are called for in this field.

This research and development is being conducted on highly-efficient commercial air-conditioners using low GWP refrigerants having substantially low greenhouse effects compared with current refrigerants. Through technology development of both equipment systems and refrigerants, energy saving and a shift to low GWP refrigerants will be promoted in the commercial air-conditioning field, which will subsequently contribute to the prevention of global warming.

*Business-As-Usual (BAU) estimate: This value indicates an est imate in which ongoing measures are maintained.

Technology Development of High-efficiency Non-fluorinated Air-conditioning Systems

R & D p e r i o d

E n t r u s t m e n t

G r a n t a w a r d s

Joint Research/Re-entrustment

Ongoing NEDO Projects

Tokyo University of Science, SUWA, The University of Tokyo, The University of Kyushu

Asahi Glass Co., Ltd., Mitsubishi Heavy Industries, Ltd., Daikin Industries, Ltd., Mitsubishi Electric Corporation, Sanden Corporation, Panasonic Corporation

National Institute of Advanced Industrial Science and Technology, The University of Tokyo, Saga University, Iwaki Meisei University, Kyushu Sangyo University

FY2011–FY2015

Significant progress has been achieved for emission reduction of fluorinated gases compared with other fields, and further-

emission reduction effects are expected to emerge.Given this success, there are high expectations regarding NEDO’s technolo-

gy development efforts. A major ongoing project of NEDO’s Environment Department is outlined below.

Source: Ministry of Economy, Trade and Industry estimate

A few hundred kg to several tonsA few tens to

several hundred kgA few to

several tens kg

About 1 kg

1,3003,260

R-134aR-404A, etc.

1,7251,526

R-410AR-407C, etc.

1,7251,526

R-410AR-407C, etc.

1,725R-410A

About 8,000

About 1 million

About 9.6 million

About 100 million

freezers

PACs for buildings

Other commercial air-conditioners

Room air-conditioners

Range of refrigerant fillercontent per unitＧＷＰType

Predominantly used HFCsEstimated number ofunits in operationEquipment type

Table 2 Types and Filler Contents of Fluorinated Gas Refrigerant Substitutes 　　　　Used in the Air-conditioning Field

[Source: reference material distributed by the 25th Subcommittee for Global Warming Prevention Measures, Chemistry/Biotechnology Sectional Meeting, Industrial Structure Council]

Estimated BAU emissions from freezers andair conditioners in 2020

Household refrigerators

Commercial freezers and air-conditioners

Million tons-CO2

Commercial air-conditioning field:

PAC (packaged air conditioners) for buildings

Other institutional air-conditioners (PAC for shops, PAC for facilities, GHP (Gas Heat Pump), chilling unit for air conditioning)

Large freezers (centrifugal freezers, screw-type freezers) * May be used for air conditioning (central air conditioning for entire buildings, etc.) for large facilities.

Room air-conditioners

Automotive air-conditioners

Other Commercial air-conditioners(Excluding PAC for buildings)PAC for buildings

Large freezers

Other mid-size refrigerator-freezers(Excluding separate type showcases)

Separate type showcases

Small-size refrigerator-freezers

Figure 6 Estimated BAU Emissions from Freezers and Air-conditioners


5

An effluent/waste gas disposal facility (submerged com-

bustion system) that destroys ozone-depleting substances

such as CFCs and HCFCs as well as HFCs, PFCs and SF6,

substances also known as fluorinated greenhouse gases, was

developed for commercialization under this project (Figure

7). The facility also enabled the reuse of recovered fluorine.

The facility decomposes HFC-23 (trifluoromethane:CHF3)

and prevents, as much as possible, the secondary emergence

of harmful substances such as dioxins. HFC-23 is a major

fluorinated greenhouse gas produced as a byproduct during

the manufacture of HCFC-22 (chlorodifluoromethane:

CHCIF2), which is a refrigerant and is also used as feedstock

for resin. Following pyrolytic decomposition, the system

recovers HFC-23 as harmless calcium fluoride. It is now pos-

sible to dispose of any fluorine-containing effluent or waste

gas.

Through the destruction process, as illustrated in Figure

8, fluorine- and chlorine-containing effluents and waste gas-

es can be completely decomposed of at temperatures of

1,200℃ or higher (Figure 9). The system instantaneously cools high-temperature combustion gas using the submerged combus-

tion method (Figure 10), and the hydrogen fluoride and hydrogen chloride generated are treated, respectively, in water absorp-

tion and alkali washing towers.

Please note that the descriptions for each project below were written at the time of project completion.

Figure 7 Fluorinated Gas Disposal Facilities Using Submerged 　　　　 Combustion Method　　　　(a) Submerged combustion furnace　　　　 (Yodogawa Plant, Daikin Industries, Ltd.)　　　　 (b) Post-treatment facility　　　　 (Kashima Plant, Asahi Glass Co., Ltd.)

(a) (b)

Development of HFC-23 Destruction Technology

R & D p e r i o d



Summary

Japan Environmental Management Association for Industry(Asahi Glass Co., Ltd. and Daikin Industries, Ltd.)Furnace body designer/manufacturer: Nittetsu Chemical Engineering Ltd. (now Tsukishima Kankyo Engineering Ltd.)

FY1998–FY2001

Contribution to Addressing Global Warming

Tsukishima Kankyo Engineering Ltd., Asahi Glass Co., Ltd. and Daikin Industries, Ltd. have promoted the development of

equipment to dispose of fluorine- and chlorine-containing effluents and waste gases discharged from fluorinated gas manufac-

turing processes. They have also developed technology and have launched facilities for the pyrolytic treatment of organochlo-

rine waste to recover hydrochloric acid, building a technological base to address the combustion of halogenated substances. As

a result of the Development of HFC-23 Destruction Technology project, which was entrusted by NEDO and carried out from

1998 to 2001, these companies succeeded in disposing of large quantities of HFC-23 through ongoing operation of the tech-

nology.

The developed technology features high-temperature decomposition and a submerged combustion method to treat HFC-23

and restrict the secondary emergence of substances such as dioxins as much as possible, thereby enabling the disposal of any

fluorine-containing waste, such as HFCs, PFCs, SF6 and NF3, as well as CFCs and HCFCs. In addition, halogen resistantmate-

rials to prevent damage to plant equipment were identified. After the project, the two companies that built the facility success-

fully treated the CO2 equivalent of approximately 6.9 million tons of the three fluorinated gas substitutes in 2007, thereby con-

tributing to the mitigation of global warming.

6

A total of 21 (14 in Japan and eight overseas, of

which three are related to the Clean Development

Mechanism (CDM)) of these decomposition facilities

have been constructed, establishing a safe and reliable

dedicated combustion furnace to destroyfluorinated

gases. The developed equipment is described as a

submerged combustion facility in Article 14, of the Law

Concerning the Recovery and Destruct ion of

Fluorocarbons, under the category of fluorinated gas

destruction facility. Those facilities’ disposal capacity

per plant is the highest in Japan.

According to the Ministry of Economy, Trade and

Industry (METI), the amount of fluorinated gas

destroyed based on this law reached 4,161 tons in

FY2008.

A fluorinated gas destruction system utilizing the

submerged combustion method has a large disposal

capacity compared with other systems as exclusive

combustion furnaces are employed. This type of sys-

tem constitutes the majority of fluorinated gas

destruction systems constructed in Japan.

In order to protect the Earth’s environment, it is

necessary to use centralized facilities to safely

decompose of large quantities of ozone-depleting

controlled substances and the three fluorinated gas

substitutes that contribute to global warming. The

introduction of the submerged combustion method to

centralized facilities significantly contributes to the

protection of the environment, and such facilities are

expected to be used even more in the future due to

recycling measures such as the Home Appliance

Recycling Law and Automobile Recycling Law.

Figure 9 High-intensity 　　　　　　Combustion　　　　 (Vortex Burner)

Figure 10 Structure of Cooling Canister

Figure 8 Process Flow of Fluorinated Gas Destruction System

Awards ・ President’s Prize, Japan Society of Industrial Machinery Manufacturers

30th Excellent Environmental Equipment Award, 2004CFC Destruction Equipment, Nittetsu Chemical Engineering, Ltd.Sponsor: Japan Society of Industrial Machinery ManufacturersSponsors:Ministry of Economy, Trade and Industry, Small and Medium Enterprise Agency

・ Ozone Layer Protection/Global Warming Protection Award8th Economy Trade and Industry Minister’s Award, 2005Asahi Glass Co., Ltd. and Daikin Industries, Ltd., Tsukishima Nittetsu Chemical Engineering Ltd. (now Tsukishima Kankyo Engineering Ltd.)Sponsor: Nikkan Kogyo Shimbun, Ltd.Sponsors: Ministry of Economy, Trade and Industry and the Ministry of the Environment


7

More than 800 tons of HCFC-22 (R22) used as

refrigerant are recovered annually. Although produc-

tion of this refrigerant is allowed until FY2020 under

Japan’s Ozone Layer Protection Law, 35% reductions

in consumption have been required since 2004. At

the time the project was started, recovered refriger-

ants were being destroyed and detoxified (neutral-

ized) using pyrolytic decomposition and the resulting

chemicals, such as CaF2, were being buried as indus-

trial waste.

However, since CaF2, a feedstock for HCFC-22,

is produced in limited geographic areas and could be

depleted in the future, the recycling of HCFC-22 is an important technological development for the practical application of 3R

technology.

The development project resolved the following issues through the application of manufacturing technologies developed

by Asahi Glass Co., Ltd. for fluorocarbon refrigerants, including HCFC-22 and fluororesin, and home appliance recycling

technology developed by Mitsubishi Electric Corporation (Figure 11).

① Efficient storage of recovered refrigerantsDevelopment of filling equipment that specifically controls azeotropic mixtures and facilitates the recovery and transfer of

sufficient volumes of refrigerants to supply purification facilities

② Using purified recovered refrigerants as feedstock for fluororesinDesign and construction of a facility to purify recovered refrigerants and implementation of a purification testing method

for recovered refrigerants and fluororesin manufacturing tests incorporating an existing manufacturing facility

③ Using fluororesin produced from recovered refrigerants for home appliancesApplication of recycled HCFC-22 to produce fluororesin for use in home appliances, taking advantage of its separability

and antifouling properties.

Based on the above, a system with the features described below was established:

(1) Refrigerant recovery systemAn overview of a system, from recovery to transfer/filling, that was installed at Hyper Cycle Systems’ appliance recycling

plant to recover refrigerants from air-conditioners is shown in Figure 12.

Figure 8 Process Flow of Fluorinated Gas Destruction System

Chemical recycling technology for HCFC-22, a fluorocarbon refrigerant used in residential air-conditioners, was devel-

oped as apractical application for 3R technology, which promotes the resolution of issues related to the implementation of the

Home Appliance Recycling Law as part of an effort to establish a recycling-oriented society.

Under this development project, HCFC-22 recovered from residential air-conditioners was used as feedstock for fluoro-

resin, making it possible to reduce HCFC-22 production and the industrial waste generated when HCFC-22 is recycled. Asahi

Glass Co.,Ltd. undertook the development of fractionating and resinification facilities based on technology that refines recov-

ered HCFC-22 to a purity level of 99.95%. Mitsubishi Electric Corporation was responsible for the development of recovery

technology and construction of the facilities.

R & D p e r i o d


Development of Technology for Chemical Recycling of HCFC Refrigerants

Summary

Technical Contents

Asahi Glass Co., Ltd., Mitsubishi Electric Corporation

FY2000

1 2 3

Figure 11 Scope and Concept of Development

8

In the system, the purity of recovered refrigerants was mea-

sured to confirm that the purity of R22 and R12 was within

standards.R22 significantly impacts purification quality and

the combination of R12 and R22 forms an azeotropic mixture.

Refrigerants that met standards were then transferred into a

large cylinder. This process substantially increased the accept-

able amount of refrigerants recovered at the recycling plant.

(2) Refrigerant purification facilities (Figures 13 and 14)

Based on the current results of refrigerant analysis con-

ducted at fluorocarbon refrigerant recovery stations and taking

into consideration the outlook for such refrigerants, it was

determined that R410A (a mixture of R32 and R125), a new

low-boiling refrigerant for residential air-conditioners, and

R134a, a new high-boiling refrigerant for refrigerators, needed

to be removed. In addition, research on azeotropic mixtures

identified that R115 and R12 also need be removed. In particu-

lar, since R12 has been used as a refrigerant for refrigerators,

it can be recovered from recycled refrigerators and mixed at

fluorocarbon refrigerant recovery stations.

Since high-boiling substances that are highly explosive in

the fluororesin manufacturing process (for example, R1112 and

R1113) can be generated in large quantities in the presence of a

high concentration of R12, it is necessary to maintain an R12

concentration in purified refrigerants lower than the control val-

ue.Purification and fluororesin manufacturing tests were con-

ducted using refrigerants recovered by a recovery system that

was newly installed at Hyper Cycle Systems. After removing

residue (mainly oil) and moisture from recovered refrigerants,

R32 and R125, which have lower boiling points than R22, as

well as R12 and R134a, which have higher boiling points than

R22, are subsequently removed through a distillation process,

thereby resulting in R22 containing 180 ppm of R12. A fluoro-

resin manufacturing test was then conducted at an existing

fluororesin manufacturing facility using the R22 obtained.

(3) Manufacturing of resin and performance evaluation (Figure 15)

A product made with PFA fluororesin (a copolymer resin of

4-fluorinated ethylene and perfluoroalkoxyethylene), using R22

derived through the above process, was compared with current-

ly available products. The comparison showed that the perfor-

mance levels of both products were equal.

1 4 52 3

1

2

3

4

5

Air-conditioner Recovery equipment

Recovery cylinder

Purity measuringequipment for R22

Pressure pump

Acceptance/rejectionCylinder

Figure 12 Basic Concept of Recovered Refrigerant Storage Facility

Figure 13 Coolant Purification Facility


Figure 15 Example of Product Produced Using Recovered Fluororesin

After the project, full-scale recovery, transfer and filling systems for recovered refrigerants were established, and related

purification facilities and application for coating materials are contributing to efforts to counter ozone depletion and global

warming, as well as playing a role in boosting home appliance recycling at the same time.

Figure 14 Process Flow of Recovered CFC Purification Facility


9

The aim of this project was to develop energy-efficient, industrially effective synthesis technology, and thereby contribute

to decreasing the burden on the environment by reducing energy consumption. The project explored and reviewed industrial

processes to synthesize fluorinated gas substitutes. Fluorinated gas substitutes are widely used in the industrial sector and

cause less damage to the ozone layer, do not exacerbate the greenhouse effect, and have less impact on the environment over-

all. Applications include refrigerants (for refrigerators, vehicle air-conditioners, etc.), industrial detergents (for electronic parts,

high-precision processing parts, optical parts,

etc.), foaming agents (for in-situ foaming),

semiconductor and liquid crystal manufacturing

(LCDs for etching, CVDchamber cleaning,

etc.), electrical insulating equipment, extin-

guishing agents, and magnesium manufactur-

ing (Table 3). The following shows an example

of energy-saving synthetic technologies for flu-

orocarbon replacements.

CF3I synthesizing techniqueTosoh-F-Tech Inc. successfully developed a synthesizing process to produce iodotrifluoromethane (CF3I, also known as tri-

fluoromethyl iodide and trifluoroiodomethane) on a commercial scale by directly reacting trifluoromethane (CHF3) and iodine

in the presence of a catalyst. Iodotrifluoromethane is a gas which has a very low GWP equivalent to that of CO2 and is expect-

ed to serve a number of purposes, including use as a PFC substitute gas for manufacturing semiconductors and liquid crystals.

The process developed for producing iodotrifluoromethane is expected to reduce CO2 emissions by approximately 40% com-

pared to conventional production processes.

Application of CF3I as an etching gas for manufacturing semiconductors*Iodotrifluoromethane, which has a GWP that is 1/1000 that of conventional chlorofluorocarbon alternatives, has been used

as a plasma dry etching gas for manufacturing semiconductors. In the process of manufacturing semiconductors compatible

with 32-45nm-generation process technology, it was discovered that the use of CF3I resulted in a reduction of line edge roughness

and an improvement in wiring reliability compared to products manufactured with conventional alternatives.

It was also demonstrated that the use of CF3I combined with exposure to short wavelength extreme ultraviolet (EUV) light

in the etching process is effective for manufacturing semiconductors compatible with next-generation 22 nm chip technology

(Figure 16).

This project aimed to accelerate the practical application of CF3I to next-generation semiconductor processing technology.

*Although this research was concluded in FY2006, it has been continued by Semiconductor Leading Edge Technologies,

Inc. in its Etching Performance Evaluation Using New CFC Substitutes project.

Application of CF3I and HFO-1234ze(E) as cover gases for magnesium die castingMagnesium is an element that is widely used due to its much lighter weight and higher specific strength relative to iron, as

well as the ease with which it can be recycled. The use of cover gas in die casting, the main method used to manufacture mag-

nesium products, prevents the surface of molten magnesium in a melting furnace from being exposed to air, thereby suppress-

ing high-temperature oxidation (combustion). SF6 has traditionally been used as the primary cover gas, but due to its extreme-

R & D p e r i o d


Development of Energy-saving Synthetic Technologies for Fluorocarbon Replacements

Summary

Technical Contents

Asahi Glass Co., Ltd., Daikin Industries, Ltd., Central Glass Co., Ltd., ZEON Corporation, Tosoh F-Tech, Inc., Japan Aluminium Association, Nagaoka University of Technology, Chiba Institute of Technology, Tosei Co., Ltd., Ahresty Co.,Ltd.

National Institute of Advanced Industrial Science and Technology, Ulvac, Inc., Tohoku University

FY2000–FY2006

Re-ent rustment

Table 3 Industrial Applications for New Fluorinated Substitutes Industrial Application New Fluorinated Substitutes Refrigerant HFE-143m Industrial detergent HFE-347pc-f Foaming agent (for in-situ foaming) HFE-254pc Semiconductor/LCD manufacturing CxFy, CF3I, COF2

Electrical equipment insulation CF3I Extinguishing agent CF3I Cover gas for magnesium die-casting CF3I, HFO-1234ze(E)

Table 3 Industrial Applications for New Fluorinated Substitutes

10

Summary and Technical Contents

Development of Chlorine Fluorinated Gas SubstitutesJapan Environmental Management Association for Industry, ZEON Corporation, National Institute ofMate-rials andChemical Research (now the National Institute of Advanced Industrial Science and Technology)


FY1996–FY1997R & D p e r i o d

ly high GWP value of 23,900, the development of substitute gases with lower GWP values is required. In this project, two SF6

substitutegases, 1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) and iodotriflu-

oromethane (CF3I), were developed. Both have GWP values that are 1/1000

that of SF6 and they are as nonflammable and effective as SF6 in suppressing

high-temperature combustion of magnesium.

A number of magnesium manufacturers in Japan are already using HFO-

1234ze(E), which has contributed to a significant reduction in greenhouse

gas emissions.

These gases are expected to serve as SF6 substitutes for the manufacture

of magnesium alloy die cast products and to significantly reduce greenhouse

gas emissions.

Crosssection

Plane

Through hole process Wiring process

Awards2009: 12th Ozone Layer Protection and Global Warming Prevention Award for Excellent Performance

The Montreal Protocol requires that the production of ozone-depleting substances such as chlorofluorocarbons (CFCs) be

phased-out in order to protect the ozone layer. In accordance with the ratification of the Kyoto Protocol, Japan is also obligated

toreduce its greenhouse gas emissions to counter global warming, reinforcing the need to shift to fluorinated gas substitute

compounds.

This project established industrial synthesis technology for CFC and HCFC substitutes with lower ozone depletion poten-

tial and lower GWP. Specifically, it has become possible to easily form two environmentally benign five-membered ring fluo-

rine compounds, octafluorocyclopentene (Figure 17) and heptafluorocyclopentene (Figure 18), in large quantities through

improved yields using a synthesis method with hydrogen fluoride.

It also has been discovered that these compounds can be applied as gases for manufac-

turing semiconductors and LCDs as well as industrial detergents as a substitute for

organochlorine compounds that have been conventionally used but which have an adverse

impact on the environment. Such industrial applications were developed by studying vari-

ous types of data on compound properties, including global environmental impact, physi-

cochemical constants, stability, impact on materials and the results of safety tests conduct-

ed in accordance with the Act on the Evaluation of Chemical Substances and Regulation

of Their Manufacture, Etc.

Fig. 20 Heptafluoro-cyclopentene

Application: Dry etching gas

Application: Industrial detergent

Fig. 19 Octafluoro-cyclopentene

Figure 17 Octafluorocyclopentene

Figure 18 Heptafluorocyclopentene


Awards

ZEON Corporation is mass producing the two chemical compounds developed in this project. A survey that it conducted

showed that octafluorocyclopentene accounts for more than half of the global market for dry etching gases (contact hole

size:100-200 nm), and that the market for heptafluorocyclopentene as an HCFC substitute detergent has expanded. Synthesis

methods and applications for these two new CFC and HCFC substitutes were developed in Japan ahead of other countries and

have attracted attention overseas.

1998: 1998 Environmental Protection Agency (EPA) Stratospheric Ozone Protection Award2000: 8thChemical and Biotechnology Tsukuba Prize, Tsukuba Foundation for Chemical and Biotechnology

Figure 16 Configuration of Next-generation Semiconductors Produced with CF3I Gas


11

The following studies and research and development were carried out with the goal of developing gas for chemical vapor

decomposition (CVD) cleaning with a lower environmental burden, including a lower GWP:

1) Study on the basic performance of reaction gas for cleaning

2) R&D on new substitute gases for CVD

3) R&D on CVD equipment using new substitute gases

4) Comprehensive evaluation study

Corrosion and the durability of CVD

chambers and materials for exhaust equip-

ment when SF6 substitute gases are used

were evaluated, and research was conducted

on how to improve CVD cleaning efficien-

cy and reduce greenhouse gas emissions.

Research was also conducted on new sub-

stitute cleaning gases in an effort to reduce

greenhouse gas emissions. In addition, a

prototype plasma CVD apparatus was

developed for the semiconductor manufac-

turing process (Figure 19).

Figure 19 Schematic Diagram of Experiment Facility

R & D p e r i o d


R&D of SF6 Substitute Gas Cleaning System for Electronic Device Manufacturing

Summary

Research Institute of Innovative Technology for the Earth (RITE), Fuji Research Institute Corporation, Asahi Glass Co.,Ltd., Kanto Denka Kogyo Co., Ltd., Showa Denko K.K., Daikin Industries, Ltd., Anelva Corporation, Hitachi Kokusai Electric Inc., Japan Vacuum Technology Co., Ltd., Tokyo Electron Limited, Fujitsu Limited, Hitachi, Ltd., Matsushita Electric Industrial Co., Ltd., Toshiba Corporation, Mitsubishi Electric Corporation, Oki Electric Industry Co., Ltd., Sony Corporation, NEC Corporation, Sanyo Electric Co., Ltd., Sharp Corporation, Semiconductor Leading Edge Technologies, Inc. (SELETE), Japan Electronics and Information Technology Industries Association (JEITA)

National Institute of Advanced Industrial Science and Technology, Ibaraki University, Anelva Corporation,Central Glass Co., Ltd.

FY1998–FY2002

Cleaning gas

Cathode(upper electrode)

Anode(lower electrode)

Manufactured by ULVAC

Inlet of gas for ICP

Remote ICP source

Inlet of gas for CCPRF

OESFTIR

QMS

DPMBP

● CCP: Capacitively coupled plasma● ICP: Inductively coupled plasma● OES: Optical emission spectroscopy● FTIR: Fourier transform infrared spectroscopy● QMS: Quadruple mass spectroscopy● MBP: Mechanical booster pump, DP: Dry pump

Plasma Plasma

Diluted N2

Abatementsystem

Since gases with high GWP values are currently being used for semiconductor manufacturing, the resulting emissions need

to be reduced as soon as possible to protect the global environment. A BAU estimate of greenhouse gas emissions from semi-

conductor manufacturing, lower actual emissions because of this project, and a 2010 target are shown in Figure 20. It is esti-

mated that emissions would have increased 10% a year and would have amounted to about four times their current level if no

measures had been taken. As shown in Figure 20, emissions in 2001 were approximately five million tons, about the same as

the level in the base year of 1995.

Although it is estimated that the use of fluorinated substitute gases and greenhouse gas emissions will increase in the

future, Japan’s voluntary target is to reduce its emissions by 10% or more by 2010 through such measures as increasing instal-

lations of abatement equipment, utilizing substitute gases, optimizing processes and adopting new processes. (Figure 20)

New substitute gases that can be used in the processes for manufacturing electronic devices such as semiconductor ICs

Technical Contents

2000: 32nd JCIA Award for Technological Excellence from the Japan Chemical Industry Association2003: 2ndGreen and Sustainable Chemistry Award, Minister of the Environment

Green & Sustainable Chemistry Network, Japan (GSCN)2008: 11th Ozone Layer Protection and Global Warming Prevention Award for Excellent Performance


12

andLCDs have been developed in order to

reduce the use of fluorinated substitute gases

and the emission of greenhouse gases with high

GWP values, such as SF6.More specifically, the

gases are designed to be used in the plasma

CVD cleaning process for insulation film.

Various gases were evaluated as substitute

cleaning gases for CVD equipment. It became

clear that COF2 (carbonyl fluoride) can reduce

greenhouse gas emissions by 99% or more

(Table 4) while retaining a cleaning speed (etch-

ing rate) equivalent to that of C2F6 (Figure 21).

This is because the GWP100 of COF2 is low

( ≒ 1) and its by-products contain only trace

amounts of high GWP gases.Moreover, COF2

has an advantage in that it does not require spe-

cial abatement equipment due to its high reac-

tivity with water.

A reduction of greenhouse gas emissions

and the total cost of CVD cleaning systems is

possible by using gases, with comprehensive

safety measures, that are reactive and that have

superior cleaning ability, such as COF2, rather

than gases that are stable in the atmosphere,

such as conventional PFC or SF6. In addition,

an ongoing evaluation of the cleaning properties

of COF2 showed no increased particles and sta-

ble deposition. This suggests potential for appli-

cation to the mass production of semiconduc-

tors.

With regard to F2, it was discovered through

an evaluation of its basic properties that it has

superior cleaning properties and results in

almost no greenhouse gas emissions and is

therefore more environmentally friendly.

However, there remain some issues regarding

how to supply and handle F2, making it difficult

to apply F2 to large-scale facilities.

Figure 21 Relationship between Etching Rate and Gas Concentration

Estimated emissions Actual emissions

25.0

20.0

15.0

10.0

5.0

0.0

Tota

l em

issi

ons

(mill

ion

GW

P-t

on)

95 96 97 98 99 00 01 02Year

03 04 05 06 07 08 09 10

Estimated emissions (business-as-usual)

Actual emissions

Target value

Figure 20 Estimated Emissions, Actual Emissions and Targeted Value for 2010

Table 4 Comparison of GHG Emissions Relative to C2F6

Daikin Industries, Ltd. first produced COF2 on a commercial basis as a CVD cleaning gas in 2003. Kochi Casio Co., Ltd.,

an affiliate of Casio Computer Co., Ltd. and a producer of TFT-LCDs, adopted COF2 as a cleaning gas for its manufacturing-

processes in 2005. Kochi Casio received a special award at the 9thOzone Layer Protection and Global Warming Prevention

Grand Prix in 2006 for its introduction of COF2. In the future, use of COF2 is expected to expand to the semiconductor and

LCD industries.


*Roughly calculated values when manufacturing gases (gas leakage) and/or in cleaning processes (plasma energy, energy during abatement, gas leakage after abatement)

Technologies Emissions

Existingtechnologies

Innovative technology

C2F6

C2F6+abatement

NF3+abatement

COF2+abatement

100%

23%

0.80%

0.30%


13

Melting and refining process technology for magnesium and technology to solidify magnesium alloys without the use of

SF6 gas as well as molding process technology that improves the mechanical properties of magnesium alloy (Figure 22) were

developed in this project.

Through the process of developing melting and refining process

technology for magnesium, the optimum amount of calcium to be

added to molten magnesium was identified, eliminating the need to

use SF6 gas. In addition, industrial melting process technology for

magnesium alloys containing calcium, impurity/inclusion removal

and analysis technologies, and crystal grain refinement technology for

manufacturing billet were established. The conditions necessary for

producing actual components were also clarified.

The development of molding process technology established pro-

duction methods for specific components and products by developing

high-toughness expansion process technology, including extruding,

cupping and rolling of magnesium alloys containing calcium, high

creep resistance injection-molding process technology using particle

composites of magnesium and reinforced materials, and high rigidity

combined processing technology.

This project contributed to the practical use of magnesium alloy as

a structural material for motorcycles and expanded structural materials

for railcars and health-care products, as well as the production of

welding rods and screws that connect structural components (Figure

23). Application of the developed materials to the production of

motorcycles, railcars and automobiles will result in lighter weight

transport vehicles, lower energy consumption and, therefore, reduced

CO2 emissions.

Figure 21 Relationship between Etching Rate and Gas Concentration

Figure 22 Production of Materials with Non-SF Melting Process

Figure 23 Applications for Materials Developed in this Project

One aim of this project was to develop magnesium processing technology without the use of SF6 gas, a gas that has an

extremely high GWP value of 23,900, by adding calcium to molten magnesium in order to make the alloy, and products con-

taining the alloy, nonflammable. Another aim was to produce magnesium parts that are lighter than conventional aluminum

alloys but which have comparable or superior mechanical properties. In order to accomplish these objectives, melting and

refining process technology as well as solidification technology that gives a very fine grain microstructure were developed.

R & D p e r i o d


Development of Non-SF6 Melting Process andMicrostructural Control for High- performance Magnesium Alloy

Summary

Technical Contents

Sankyo Tateyama Aluminium, Inc., Sumitomo Electric Industries, Ltd., The Japan Steel Works, Ltd., Daido Steel Co.,Ltd.

FY2004–FY2006

Fig. 24 Production of Materials with Non-SF Melting Process

Material for chipping

Chipping

Combined machining

3-D deformed material

Material for rolling

Remelting

Rolling Thin sheet

Cupped material (rod)CuppingExtruded material

for cupping

Extruded materialExtrusionMelting/Continuous cast

Billet

Extruded material

Cupped material (rod)

Rolled thin sheet

Combined deformed material

Fig. 25 Applications for Materials Developed in this Project

Materials for machining

Welding rod

Motorcycle handlebars

Screws

Robotic arm

Flat-screen television

Motorcycle framesForged pistons

Wheel

Artificial leg

Healethcare productsCar carriersBullet train

2009: Toyama Alloy, an affiliate company of Sankyo Tateyama Aluminum, Inc., won the 12th Ozone Layer Protection and Global 　　　Warming Prevention Award for Excellent Performance (sponsored by Nikkan Kogyo Shimbun Ltd. and supported by the　　　Ministry of Economy, Trade and Industry and the Ministry of the Environment).

Awards

14

Ozone-depleting substances such as controlled substances (CFCs and HCFCs) are required to be phased out in order to

protect the ozone layer under the terms of the Montreal Protocol. For this reason, three fluorinated gas substitutes (HFCs,

PFCs and SF6) that do not deplete the ozone layer were developed as alternatives to controlled substances. They have been

used as refrigerants (for freezers/refrigerators, air-conditioning equipment and vehicle air-conditioners), foaming agents, deter-

gents, insulation, etc., due to their useful properties. The use and emissions of these substitute gases are expected to increase as

ozone-depleting substances are phased out. However, since these three substitute gases can stably exist in the atmosphere for a

long period of time and because they have an extremely high GWP value, emissions resulting from their use must be reduced

in accordance with the terms of the Kyoto Protocol.

In this project, advanced and broadly applicable

equipment and technology development proposals

related to emission reduction in all fields and indus-

try sectors that use the three fluorinated gas substi-

tutes were solicited. Outstanding proposals were

then subsidized as leading model projects (applied

research at an advanced stage) in order to promote

practical application (see Figure 24).

Until FY2007, this project was known as the

Project to Support the Practical Implementation and

Application of Emission Control Equipment and

Facilities to Control Three Fluorinated Gas Substitutes.

The following shows some of the results of the

project (Figures 25 to 27).

2008: NKK Co., Ltd. was awarded the Economy, Trade and Industry Minister’s Award at the 11th Ozone Layer Protection and Global 　　　Warming Prevention Award for Excellent Performance ceremony.2011: COOP Sapporo was awarded the Economy, Trade and Industry Minister’s Award at the 14th Ozone Layer Protection and Global 　　　Warming Prevention Award ceremony for the introduction of non-fluorinated showcases.2012: Lawson, Inc.was awarded the Economy, Trade and Industry Minister’s Award at the 14th Ozone Layer Protection and Global 　　 Warming Prevention Award ceremony for its installation of refrigeration systems at convenience stores.

*Sponsored by the Nikkan Kogyo Shimbun Ltd. and supported by the Ministry of Economy, Trade and Industry and the Ministry of the Environment.

Awards

Project to Support the Practical Implementation and Application of Emission Control Equipment to Control Three Fluorinated Gas Substitutes

FY2006-2010R & D P e r i o d

Figure 24 Project Overview

H F C P F C S F 6

Research of application technology and practical application technology development of equipment and relevant technology to collect/remove the three fluorinated gas substitutes

Research of application technology and practical application technology development of equipment and relevant technology free of the three fluorinated gas substitutes

Research of application technology and practical application technology development of equipment and relevant technology to produce alternatives to the three fluorinated gas substitutes

Prom

otio

n of

em

issi

on c

ontro

l mea

sure

s fo

r thr

ee

fluor

inat

ed g

as s

ubst

itues

Cleaning of electronic materials

Semiconductors and liquid crystal manufacturing

Magnesium casting manufacturing

Production and maintenance of equipment in which dielectric gas is used.

Production and maintenance of industrial freezers/refrigerators, air conditioners, vending machines, vehicle air conditioners, residential air conditioners and refrigerators

Aerosol products, MDI, etc., manufacturing

Insulation and foaming agent manufacturing

Production of HFC・PFC・SF6

Target technologies and industries:All technologies and industries in which the three fluorinated gas substitutes are utilized

Examples of subsidy applications:

Figure 25 Project result 1:Fluorocarbon- free air duster production 　　　　　　facility (NKK Co., Ltd.)

Figure 26 Project result 2: COF2 production and storage (Kanto Denka Kogyo)

Figure 27 Project result 3: Small, high-performance CFC- recovery unit　　　　　 (Asada Co., Ltd.)


15

The production and use of refrigerants such as CFCs and HCFCs are to be phased out in accordance with the Montreal

Protocol’s control measures to protect the ozone layer. Because of this, refrigerants that use fluorinated gas substitutes were

developed. The air-conditioning and refrigeration industry promptly responded, and their most common models now employ-

fluorinated gas substitutes. Some of these substitute compounds, however, have extremely high GWP values and the emission

of these gases must be reduced in accordance with the Kyoto Protocol.

Although some air-conditioners that use fluorocarbon-free refrigerants that have low GWP have been commercialized,

they are not widely used yet due to low energy efficiency and because of safety concerns, including worries about the potential

for refrigerant leakage. Moreover, it is a technical challenge to utilize fluorocarbon-free refrigerants in air-conditioners and

research is still, therefore, ongoing. In order to

realize commercialization, it will be necessary

not only to develop elemental equipment but also

a safe, highly energy-efficient system.

NEDO carried out a project to promote the

improvement and development of safe and com-

fortable refrigeration and air-conditioning sys-

tems using fluorocarbon-free substances that do

not damage the ozone layer, have a low impact

on the environment and a low GWP, while aim-

ing at further reducing the overall environmental

impact from the viewpoint of energy saving (see

Figure 28).

R & D p e r i o d


Development of Non-fluorinated Energy-savingRefrigeration and Air-conditioning Systems

Summary

Shin Nippon Technologies Co., Ltd., Daikin Air-conditioning and Environmental Lab. Ltd. (now Daikin Industries, Ltd.) ,Chubu Electric Power Co., Inc., Mitsubishi Heavy Industries, Ltd., Earthship Co., Ltd., Honda R&D Co., Ltd., The Japan Refrigeration and Air Conditioning Industry Association, National Institute of Advanced Industrial Science and Technology, The University of Tokyo, Kyushu University

Daikin Industries, Ltd., Sinko Industries, Ltd., Mitsubishi Electric Corporation, Panasonic Corporation, SandenCorporation, MAC Co., Ltd., Mitsubishi Heavy Industries Air-Conditioning & Thermal Systems Corporation, IKE RefTecCo., Ltd., Sanrei Corporation, Maekawa Mfg. Co., Ltd., General HeatPump Industry Co., Ltd., SANYO Electric Co.,Ltd.,(now Panasonic Corporation) Mitsubishi Heavy Industries, Ltd.

FY2005–FY2010


Figure 28 Outline of Technology Development

Sanden Corporation, a participant in this project, successfully developed a refrigeration and air-conditioning system for

convenience stores. This system employs ammonia (NH3), which does not deplete the ozone layer and has no global warming

effect, as a refrigerant. The greatest challenge in using ammonia is its odor and toxicity. Sanden enhanced the safety of the sys-

tem by minimizing the use of ammonia, completely sealing the ammonia in an outdoor unit, and eliminating the use of ammo-

nia inside convenience stores.

Based on a final verification using a laboratory with a built-in full-scale small store, the new system will improve the ener-

gy efficiency of convenience stores by approximately 21%. Verification tests were also conducted at a number of convenience

stores in Japan. The new system is expected to be introduced to approximately 42,000 stores nationwide, which will reduce

CO2 emissions by as much as 640,000 tons per year, thereby contributing to the mitigation of global warming. In addition, the

world's first non-fluorinated refrigeration and air-conditioning system for convenience stores was put on the market in

FY2009.

Technical Contents

16

Awards2009: Sanden Corporation was awarded the Economy, Trade and Industry Minister’s Award at the 12th Ozone Layer Protection and Global Warming Prevention Award ceremony* for its development and practical application of energy-efficient refrigeration and air-conditioning systems equipped with non-fluorinated refrigerants for use at small stores. 2010: SANYO Corporation was awarded the Economy, Trade and Industry Minister’s Award at the 12th Ozone Layer Protection and Global Warming Prevention Award ceremony* for refrigeration and air-conditioning systems equipped with non-fluorinated refrigerants for use at small stores.

*Sponsored by the Nikkan Kogyo Shimbun Ltd. and supported by the Ministry of Economy, Trade and Industry and the Ministry of the Environment.

Figure 29 Development of Refrigeration Systems for Supermarkets Equipped with CO2 Refrigerants

Figure 30 Forecast of CO2 Emissions Reduction Effect Resulting from CO2 Refrigeration Systems

Refrigerating unit

Freezer showcases

CO2 refrigerants

Overview of the system

One of stores where the systems have been introduced on a trial basis Maxvalu Express Rokugodote Ekimae

Two-stage rotary CO2 compressor

Second compression

First compressionIntermediate cooling

heat exchanger

Motor

70

35

27

R404A refrigerationsystems

Non-fluorinatedrefrigeration systems

24

0

60

50

40

30

20

10

0

Direct effectIndirect effect

CO

2 em

issi

ons

(t)CO2 reduction effect

Maximum of about 60%

SANYO Electric Co., Ltd., another participant in this project, developed Japan’s first refrigeration system using natural

refrigerants (CO2) for use in refrigerated showcases in supermarkets (Figure 29). Though it is neither toxic nor flammable,

CO2 as a refrigerant has some drawbacks. It is less efficient and requires a higher working pressure compared to HFCs. In par-

ticular, in summer, when ambient temperatures exceed 30℃, it is not possible to attain a highly-efficient refrigeration cycle

with CO2 refrigerant. To overcome this, SANYO developed a circuit cycle that employs CO2 refrigerant to achieve a high-

efficiency refrigeration cycle. SANYO succeeded in developing the system without having to make special modifications by

employing, in the newly developed cycle, a two-stage rotary CO2 compressor. In addition, because CO2 refrigerant has a

high heat transfer capacity, it is possible to use smaller diameter pipes when building systems. As a result, the weight of copper

piping used in the system can be reduced by up to 37%, thereby saving resources.

Demonstration experiments of the system, which can reduce power consumption by approximately 10% compared to con-

ventional systems, were confirmed at supermarkets. In addition, considering the direct impact on power consumption reduc-

tion and the indirect impact on refrigerant leakage, the system can reduce CO2 emissions by a maximum of approximately

60% (Figure 30). SANYO Electric introduced the system to the market in FY2010.

Project to Develop Innovative Non-Fluorocarbon Heat Insulation Technology

R & D p e r i o d



Kyoto University, National Institute of Advanced Industrial Science and Technology, Nisshinbo Chemical Inc., C. I. Kasei Co., Ltd., Tokyo University of Science, Asahi Fiber Glass Co., Ltd., Toray Industries, Inc., Kaneka Corporation, Tokyo Institute of Technology, Japan Testing Center for Construction Materials, Achilles Corporation

Asahi Glass Co., Ltd., BASF INOAC Polyurethanes Ltd., Achilles Corporation

Yamagata University, Hokkaido Northern Regional Building Research Institute

FY2007–FY2011



17

Figure 31 Overview of Technology Development

Rigid urethane foam is widely utilized in building structures. However, because insulation and foaming agents made from fluorinated gas substitutes have a high global GWP, there is a need to develop insulation and foaming agents from chemicals

with lower GWP values.

In response, non-fluorocarbon insulation and foaming agents utilizing gases with lower GWP values, such as CO2 or

cyclopentane, are being developed.

However, several issues need to be addressed regarding new non-fluorinated foaming agents, such as insulating efficiency,

combustibility during manufacturing, and workability, before they can commercialized.

NEDO undertook this project to develop innovative technology for non-fluorocarbon insulation materials used as building

insulation materials. The features of non-fluorocarbon insulation materials are an insulation efficiency equal or superior to

conventional rigid urethane foam materials and a high insulation efficiency for a long period of time.

The following four major technologies were developed in the project:（Figure31 and Figure32）・Technology to control high porosity foam structure by mixing micrometer-sized pores and nanometer-sized pores in order to improve insulation efficiency of CO2 foam insulation materials

・Technology to control the diffusion process of foaming agents contained in pores in order to maintain long-term insulation efficiency

・Synthesis technology to produce HFO foaming agents with a low GWP as a substitute for conventionally used foaming agents with a high GWP

・Technology to produce heat insulation materials by hybridizing aerogels which have an extremely high insulation efficiency with polymer

Based on the above-mentioned technology development, there are future prospects for commercialization of non-fluorocar-

bon heat insulation having the same insulation efficiency as fluorinated foaming agents.

With the aim of evaluating the developed heat insulation materials, two other technologies were developed: technology to

measure insulation efficiency and thermal conductivity in order to evaluate developed heat insulation materials and technolo-

gy to evaluate the practicality of developed heat insulation materials.（Figure32-(4)）

It is expected that the development of new non-fluorocarbon insulation materials having a high insulating efficiency will

reduce CO2 emissions. In addition, since the development of this technology is expected to benefit not only the construction

industry but also other industries that use insulation materials, such as for refrigeration and transportation, the ripple effect is

expected to significantly boost climate change prevention efforts.

Summary

Technical Contents


Figure 32 Development Results

High porosity form structure by mixing micrometer-sized pores and nanometer-sized pores

Multi-layer foam structure to control diffusion process of forming agent in order to maintain insulation efficiency

Aerogel/polymer composite heat insulation material

Device designed for measurement of thermal conductivity of insulation material by using alternating thermal wave attenuation

(1) (2)

(3) (4)

Fluorinated Reduction Technologies 2014-Toward the Prevention of Global Warming-

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