EXHIBIT M
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`TO DECLARATION OF RAJIV RATNA SINGH
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`PH1 3132772v1 07/05/12
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`Page 1 of 14
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`Arkema Exhibit 1136
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`Page 1 of 14
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`Arkema Exhibit 1136
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`ENERGIES 99
`[2 Iines i,,egib,e]
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`Technical Day
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`Paris-Nord Vllleplnte
`Thursday, September 23, 1999
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`[2 lines illegible]
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`cost more‘?
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`New Refrigerants:
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`Does cooling
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`SUMMARY OF INTERVENTIONS
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`ADEHE
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` ambit I14.
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`Environment and Energy
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`Management Agency
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`SCHOOL OF MINES LIBRARY
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`[bar code]
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`ADEME Technical Day — Paris, September 2311999
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`“New Refrigerants: Does Cooling Have to Cost.M0re?”
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`A Translation of WORDEXPRESS, Worldwide Language Services, Tel. 00.1 (310) 260-7700
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`For Certification of this Translation please see enclosed Affidavit
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`Page 2 of 14
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`Page 2 of 14
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`LIBRARY OF THE
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`"A"°¢§'FAi..‘§.‘§§LE°E
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`143145
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`CCL5769
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`CHARACTERISTICS AND PERFORMANCES
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`OF NEW REFRIGERANTS
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`Denis CLODIC, Young.Soo.CHANG
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`1. The motive for changing refrigerants
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`Refrigeration and air conditioning have been developing since the 19th century. The firstrefrigerant used
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`in thelast years ofthat century was ammonia. Then propane, CO2, and SO; (sulfur dioxide) Wereused.
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`These different liquids have shown a. certain number of limitations, particularly in. terms of safety in large
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`public. applications; Starting in l%0’,.non-toxic, non-flammable refrigerants, CFCS, have been developed,
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`the first of Which, R-.12‘, was ‘invented by—Midg_ey.
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`The family of chlorinated and fluorinated liquids was developed for fifty years, until 1985, the year when
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`evidence was given of the destruction of stratospheric ozone by chlorinated compounds. of the‘CFC. type.
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`These‘ refrigerants, which then covered 90% of the applications, were R-l 1,. R-12, R-22, and R-502; the
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`remaining 10% corresponded to the use of ammonia, mainly in the agrofood industries.
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`The motive for changing refrigerants was established by the Montreal Protocol, which prohibited, starting
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`at the end of 1994, the production of chlorinated molecules in various applications (insulation-foam
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`expansion agents, solvents for the electronics industries, mechanicals industries, etc., aerosol fire-
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`extinguishing agents, and certainly refrigerants. Replacement molecules have been developed and
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`marketed by chemical-engineering companies since .l990,.mainly R-134a and aset of mixtures of
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`refrigerants, all consisting purely of fluorinated compounds, the HFCs mentionedin the following
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`The Kyoto Protocol on limiting greenhouse-gas‘ emissions, Wh_ich constitutes a new constraint, appeared
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`in 1998. Although this protocol does not imply stopping the production of new HFC molecules, any
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`substances that have a ‘high GVVPI value are no longer considered benign with respect to the environment.
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`Implicitly, molecules that have a long lifetime, in the atmosphere, several decades, or centuries, should
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`have their emissions drastically limited, one of the options being not to use them.
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`The regulations to come associated with the Kyoto protocol thus’ create uncertainties in the mid to long
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`term concerning current refrigerants, iftheir GWP is high. The technical environment of cooling and of
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`‘ GSP: ‘Globa1.Warrning Potential
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`SCHOOL OF MINES LIBRARY
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`ADEME Technical Day — Paris, September 23,1999
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`“New Refrigerants: Does Cooling Have to Cost.More?”
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`A Translation of WORDEXPRESS, Worldwide Language Services, Tel. 00.1 (310) 260-7700
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`For Certification of this Translation please see enclosed Affidavit
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`Page 3 of 14
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`Page 3 of 14
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`2. Refrigeration before 01994
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`Refriegeratin-gand air-conditioning devices have an essential characteristic. theyare omnipresent. They
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`havebecome commonplace materials worldwide, and the number of devices is ,greater than
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`1,200,-000,000, of which household refrigerators constitutemore thanhalf.
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`The various technical constraints of refrigerating systems should be analyzed application byapplication.
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`Four of them constitute. the cooling chain: home cooling, commercial cooling, refrigerated transportation,
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`and the -agrofood industries’. The others cover air conditioning including heat pumps, water-cooling
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`groups, onboard conditioning (automobiles, railroads, etc.)», and finally, processes other than agrofood
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`Before 1994, five liquids, the essential the-rmophysical propertiesof which are presented in Table 1,
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`pennitted the operation of all systems.
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`Table l — Thermodynamic properties, GWP, and lifetime of the five refrigerants most used in the year
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`1994. [CAL99]
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`Reference
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`Chemical
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`CCHzF
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`CCIFZCF3
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`Mole mass,
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`137-37
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`‘Normal
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`boiling T,
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`(R-115)
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`Lifetime
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`1980
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`11.22/115
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`17.03
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`-33.3
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`133.0
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`11.42
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`* The lifetime of a mixture.makes.no sense directly, only the lifetime of each cornponent'is taken into account. In the case o.fR-502, R-1.15.,
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`which has a. l-ifetime of 700- years, certainly constitutes the predominant factor.
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`R-ll was -essentially used for the water-cooling groups. This application, very common in the United
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`States, represents ‘several tens of thousands of devices. The energy efficiency of these systems was very
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`high, the machines were reliable,—and the overall cost was relatively low.
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`R-12 wasthe first synthetic refrigerant of the. CFC type. It main uses were home cooling and automobile
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`air conditioning. R-12 could also be found in various other applications, particularly in very hot countries,
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`Where‘ condens ation temperatures are high.
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`2 ODP: Ozone Depleting Potential. The values are relative to those of R-1 1, the ODP ofwhich is equal to Lby definition.
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`ADEME Technical Day — Paris, September 23,1999
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`“New Refrigerants: Does Cooling Have to Cost.More?”
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`A Translation of WORDEXPRESS, Worldwide Language Services, Tel. 00.1 (310) 260-7700
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`For Certification of this Translation please see enclosed Affidavit
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`Page 4 of 14
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`Page 4 of 14
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`R-502 is a molecule that appeared in the 1970s. to permit development of single-step low-temperature
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`systems by replacing R-22, which generated too high a push-back temperature for this type of application.
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`This liquid Was manly used in central cooling systems of supermarkets and hypermarkets, but also in a
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`certain number of industrial applications and in. refrigerated transportation.
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`R‘-22 is a HCFC. It includes a hydrogen atom, which reduces its atmospheric lifetirnevery strongly’ (.12
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`years), and its ODP is at least 50 times weaker than that of R-12. This characteristicshas led to a
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`prolongation of its use untilnow and fora few years to come outside Europe. Since the 1960s, this liquid
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`has become the most sold refrigerant because it is also used in the a-grofood industries, in air-conditioning
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`systems, in numerous industrial applications,_ in refrigerated transportation, etc. It is the liquid Whose
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`replacementposes the biggest problem.
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`Ammonia is a refrigerant whose toxicity and flammability have historically restrictedits use to high-
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`power agrofoodeooling. The regulatory constraints on the use of CFCS and HCFCS‘ have led to an
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`extension of the use of ammonia, both in its preferred f1eld,. but also in various applications, in particular
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`for ‘water-cooling groups and new refrigerators using heat transporters.
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`ADEME Technical Day — Paris, September 2311999
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`“New Refrigerants: Does Cooling Have to Cost.More?”
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`A Translation of WORDEXPRESS, Worldwide Language‘ Services, Tel. 00.1 (310) 260-7700
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`For Certification of this Translation please see enclosed Affidavit
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`Page 5 of 14
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`Page 5 of 14
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`Refrigeration starting in the year 2000
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`Table 2 — The new refrigerants [CAL99]
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`Chemical formula
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`Reference
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`3ure HFC bodies
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`1-13421
`'CH2FCF3
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`CHF2CF3
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`roperties
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`Lifetime
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`Physical
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`{-125
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`1-404A
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`R-1 2.5114341/1343
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`102.03
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`120.02
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`97.6
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`-26.1
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`-46.6
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`101.1
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`86.3
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`4.06
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`374
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`1300'
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`2600
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`14.6
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`101.55
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`4.8-3 Mixtures of HFCS
`72.1
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`um{—407C
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`R-3.2/125f134a
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`{-410A
`R-32/125 (50/50)
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`73.5
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`Mixtures based on R-22
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`R-125/290/22
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`R-125r143a/22
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`87.01
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`-451.5
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`83.3
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`2650
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`{-408A
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`J drocarbons
`-IC-890
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`’ropane
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`VCH3CH2CI-I3
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`CH(C'H2]3CH3
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`42.1
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`-1 1 .6
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`96.7
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`4.25
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`20
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`17-03
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`44-“01
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`* The lifetime of a mixture makes no sense, since each component has its own lifetime.
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`132-3
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`4 Home c00liJ1g_[UNE98], [UNE97]
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`Replacement of R-12 by R-13 4a started in 1992 for refrigeration. The different therrnodynamic properties‘
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`between R-12 and R- 13 4a, although minimal, have necessitated new developments, in particular,
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`improvement in he1_metic_compressors for freezers.
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`l\/Iarketing of R-134a has "led to a very large number ofstudies: on working out new lubricants. In fact,
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`since R-13 4a is not miscible with mineral oils or alkylhenzene, new lubricants have been developed,
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`essentially the polyesters (POE). R&D continues,-and polyvinyl esters (PVE) now appear on the market.
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`ADEME Technical Day — Paris, September 23,1999
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`“New Refrigerants: Does Cooling Have to Cost.More?”
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`A Translation of WORDEXPRESS, Worldwide Language Services, Tel. 00.1 (310) 260-7700
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`For Certification of this Translation please see enclosed Affidavit
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`Page 6 of 14
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`Page 6 of 14
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`Independent of these technical, developments, and after an active political campaign conducted in
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`particular by GreenPeace in Germany, some hydrocarbons, including R—600a (isobutene) have been
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`proposed as refrigerants to replace R-12. In fact, numerous‘ inflammable liquids (propane, isobutene,
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`butane, and mixtures thereof).have thermodynamic properties that are interesting for use as refrigerants.
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`Their flammability was the.-main reason for their use being stopped in the 1930s.
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`Based on this-political pressure and the impact of environmental campaigns-in Germany, in Sweden, in
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`Great Britain, and more generally in the countries of Northern Europe, companies such as Bosche,
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`Siemens, Electrolux, and Liebherr, have marketed models of refrigerators and freezers that «operate on R-
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`600a. At this time, 30% ofthe European refrigerator market uses flammable refrigerants. "Possible
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`developments in the European regulations associated with the Kyoto Protocol may be an increase in the
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`use of R-600a in home cooling.
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`O Commercial cooling
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`Commercial cooling covers a greatvariety of devices.
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`Devices of the “groupe loge” [meaning unknown] type (small vending machines, ice-cream machines,
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`beer coolers, drink distributors) constitute devices whose components. are close to those used in home
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`cooling. The refrigerant used is mainly R-13-4a, -and in certain countries, in particular Great Britain,
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`devices operating with flammable liquids appear.
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`For installations of low and medium power, cooling between 1 and 10 kW, cooling is produced by
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`condensation units. These are smallplatforms including one or more compressors associated with an air
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`condenser that produces cooling for one or more refrigerating devices (small cold chambers, vending
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`machines). These refrigerating units, typical of cooling in neighborhood stores andspecializedfood
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`businesses (butcher shops, delicatessens, bakeries, pastry shops), use either R-13 4a or R-404A today.
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`In supermarkets and hypermarkets, R-502 was replaced first by ‘transitional mixtures based on R-22, such
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`as R-402A or R-408A, and it‘ new installations, it has been replaced by R-404A. R-22is still present in
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`installations‘ with positive cooling, and it will bereplaced, ofiten for reasons of uniformity of the liquids.
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`used, by R-404A. In certain cases, R-134acan also be used.
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`0 Refrigerated transportation’
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`The liquids mainly used are R-12, R-22, and R-502. At this time, R-404A is present in most of the
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`systems, with the exceptionof refrigerated containers, which operate essentially with R-134a. Systems
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`operating with R-410A have also been proposed.
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`ADEME Technical Day — Paris, September 23,1999
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`“New Refrigerants: Does Cooling Have to Cost.More?”
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`A Translation of WORDEXPRESS, Worldwide Language Services, Tel. 00.1 (310) 260-7700
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`For Certification of this Translation please see enclosed Affidavit
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`Page 7 of 14
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`Page 7 of 14
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`The Merchant‘ Marine, which obviously has specialconstraints for maintenance in various ports
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`worldwide, has chosen R-410A.
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`6 Agrofood processes and other processes [DUC98], [GUI98]
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`The two liquids mainlyused are ammonia and ‘R422. In countries such as France, these two liquids are
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`distributed inalmost numbers with equipment using R-502. Taking the very long lifetime of these
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`installations and the prohibition on using. R-.22 into. account, the situation will not start to improve until.
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`the year 2000. A double developmentcan be envisioned: on the one hand, increasingvthe use of ammonia
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`when the additional cos_ts.are considered to be acceptable, and on the other hand, changing to R-404A for
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`installations that usually operate with R-22.
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`Depending on environmental. sensitivity, the optimal choice may be different in different countries.
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`6 Water-cooling groups
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`Water-cooling groups are most often manufactured and loaded for factories, since the equipment is
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`connected to water circuits. The sizes of these materials can be verydifferent, and the compressor
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`technologies can also be different. 30 % of these devices are used in industrial processes, 70 %in air
`conditions.
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`For low-power systems, up to 100 _kW, the wat_er‘-cooling groups operate with alternating piston
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`compressors and increasingly with Scroll compressors. Until now, these systems have been operating
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`essentially with R-22. In this series of applications, R-22 can be replaced by a large number of liquids:
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`ammonia, R-407C, R-410A, or R-404A.
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`Groups with power between 100 kW.and l Mwsinvolve mainly screw compressors that operate
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`essentially with R-22. The same choice apply as previously.
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`For water-cooling groups of highpower operating with centrifuges compressors, developmentsin Europe
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`are essentially with 'R- 13 4a. This solution will probably be retained in the future.
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`0 Air collditioning [BIV94]
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`In air conditioning,_the sizes of the devices vary greatly, going from split systems with. a refrigerating.
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`power of "2 kW to.roof—top units having a power of .100 to 400ikW. The liquid used at present is R-22.
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`ADEME Technical Day — Paris, September 23,, 1999
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`“New Refrigerants: Does Cooling Have to Cost.More?”
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`A Translation of WORDEXPRESS, Worldwide Language Services, Tel. 00.1 (310) 260-7700
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`For Certification of this Translation please see enclosed Affidavit
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`Page 8 of 14
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`Page 8 of 14
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`For small devices, in particular split systems up to a power of‘ 10 kW, R-40 1A has theadvantage, for
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`equal sizes, ofincreasingthe refrigerating power. R-407C (a mixture with temperature sliding) has a.
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`capability for direct conversion of existing installations, on condition’ that the oil be changed. The
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`reference lubricant for R-407C is usually a polyester oi1.(POE), while the oil usually used. with R-22 is
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`alkyl benzene.
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`R-13 4a can be used in high-power ‘installations, but increasing the size of the compressor constitutes a
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`major inconvenience. The best cost/effectiveness compromises are currently being evaluated .-at both the
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`European level and the World level.
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`¢ Onboard conditioning
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`For ‘this~application, passing from R-12 to R-l34a is taking place at almost the same time as for home cooling.
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`Taking the international nature of automobile manufacturing into account, most companies consider that a uniform
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`choice at the world level is preferable. Considering the relatively high GWP of R—l34a,.several European
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`automobile builders —. essentially Mercedes and BMW — have developed prototypes operating with CO1. An annual
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`evaluation is made under the auspices of the SAE (Society of Automotive Engineers) to analyze the advantages and
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`inconveniences of the three technical options ‘available, R—l34a, propane, and CO2. Agreement exists on the fact that
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`propane can be used only in indirect systems, fof obvious safety reasons. The evaluation of these systems also
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`concerns both energy efficiency and the impact of refrigerant emissions. Other aspects, such as maintenance
`facilities, are also taken. into account.
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`4 Analysis of the—pe.1'fo1'mances offliquids replacing R422. Onboard conditioning [DOM93],
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`[FISQ3], [DUCE-38:]
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`The energy efficiency of refrigerating systems depends essentially on the overall design of the system. Design
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`involves numerous choices concerning the size, structure, exchange technologies, type of compressor, and regulation
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`strategy. Among these choices, the refrigerant constitutes an essential element of the development of the system, but
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`overall energy efficiency cannot be associated directly with the nature of the refrigerant:
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`However, the thermodynamic properties of liquids can be compared for refrigeration energy cycles defined for the
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`temperature levels of condensation and evaporation and by using different compressor yields (isentropic and
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`volum etric). These comparisons give indications, but they do not thereby give the final result on the real energy
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`efficiency of the system. In contrast, certain thermodynamic properties imply certain advantages or inconveniences
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`for particular conditions of use. This-is particularly the case for liquids who se critical temperatures are clearly lower
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`than those of-the liquids they replace, which implies low direct performances that should be compensated for in the
`overall design ofnew refrigerating systems.
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`ADEME Technical Day — Paris, September 23,1999
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`“New Refrigerants: Does Cooling Have to Cost.More?”
`
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`
`
`A Translation of WORDEXPRESS, Worldwide Language Services, Tel. 00.1 (310) 260-7700
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`For Certification of this Translation please see enclosed Affidavit
`
`
`
`Page 9 of 14
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`Page 9 of 14
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`The results'of1;he cal'c'ulatio_ns'preserniin Table 3 ooirespond to an air-condifioning insw_1lation for the followirig
`c0ttditi°n5= ._
`with superheatingiof 10K,
`1' evaporation;
`+ 2
`1‘ condensation: +50 withfsubcooling of 10 K.
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`'I'he.de-\'elopn1cnts»o’f“the.isentrop,it_: and volumetric yields dependoiti the compressor size-, J, accordirig to the
`formulas prcscntte,cl_.bel'(3W:i
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`Volumetric yield:
`1}, = 1 — 0.021
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`Isemropic yielcfi
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`11,, =- 0.95‘ — 0;-00'4(1 -5)‘ — O.’5f(:- -70:31)
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`The I‘efi'i‘g§rati.ng‘p0W¢r chosen- for K-22 typically corresponds to an-esidentiial air-conditioning system for an
`individual house with a large area.
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`Table ‘3 — Cl1ar'a‘cteristics'?of R422 for the specifi‘ecIapp‘lication“
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`The yield cha1'act«_eristics are takenfrom manufactuter’sdata. This application peirnits verification thatthe
`coefficierit of perfonnancje of the system isj1e1ative1y« high; The «following evaluation is made by
`volumetric compressor flow me account.
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`same
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`Propane and 8,_l_ll‘nI0lfI:iE
`717) _imp1_y'tha‘L these materials can‘ be exploited identically
`The re‘sults“g_iven for‘ propane (R-220) and ammonia
`in comparison to systems operating with.I-[FCs, which is -not the ‘cased for an air‘/"air installationsystem. The results
`presented» here are Ttherefore only purely theoretic'al,.sinceiIheyr correspond Imhe case where these liquids coiildbe
`used directly in'refrigemtii-ig/‘air 'exbhm1ger's. "Safety consiriairits may prohibit such<us‘ie‘. It wouldthen be lnecessary to
`me, ‘for -example, an indirect system to"produce refrigeratimi alone or even to rejectithe heat of condensation In this
`case, the additioml temperature gaps associated withrthc heat-‘transport 'circuit‘iznply~coeffi'ciei1t ofperformances
`tlimareeclearly be-lowthose menfioned in these cycle calculations
`
`Tcdmiéfil Di? * .P.fl.|‘iS."_$_°lJ'l‘fl1|i?¢¥ 331.-.1999:
`“New Refrigeiams: Do_es_Coolin,g'Have_to Cost More?’
`
`A Triunsldtion of WORDEXPRESS, Woddwide Language-5erv‘I'ces,M rest. 00! (310) 260-2700
`For Certification of this Translation please see enclosed
`
`Page 10 of 14
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`Page 10 of 14
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`Table 4 ~ Comparison of performances of’R—‘22 and replacementliquids
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`nZ
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`—-d
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`R 410A
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`R-4070 n
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`.6 R-134 and ‘nlixtures of HFCS
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`The similarity of columns 1 and 4 shows, for R-407C inparticular, that even if the yield of the compressor may be
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`more favorable with a liquid (R—407C here), this does not indicate that the coefficient of performance of the system
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`would be higher. In fact, for an air exchanger, the temperature sliding implies an energy‘ penalty that indicates a
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`coefficient of performance for R—407C predicted to be 5 % below that of the same .instal‘lation operating with R22.
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`On the other hand, Table 4 indicates that certain liquids, such as R-404A and especially R-410A, permit a higher or
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`clearly higher refrigeratingpower tobe arranged, but this assumes a. complete modification of the installation to
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`adapt thecolnpressor and the diam eters. of the pipesto the new liquid.
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`It turns out, however, that neither R-404A nor, especially, R.-410A. isa direct replacement liquid. It is the same for
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`R—.l38a, whoseeoefficient of performance for the cycle ‘being studied may be slightly higher, but which also
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`assumes that the compressor and the exchangers are redesigned to take advantage of this liquid.
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`Column 2 indicatesthat, compared to R.-22, the flow ‘ratios of all the liquids are extremely different, except. for R-
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`407C, which has properly. been conceived as the replacement liquid.
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`These Various datajperrnit development axesto be defined for new installations. and Verification that the
`thermodynamic properties themselves cannot be concluded.
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`S. Prospects
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`Although the regulations associated with the Montreal protocol translate into a rapid schedule for stopping the
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`production of CF_Cs¥and HCFCs, it seems less probable that H'FCs—can disappear rapidly on the word scale.
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`ADEME Technical Day — Paris, September 23,1999
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`“New Refrigerants: Does Cooling Have to Cost.More?”
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`A Translation of WORDEXPRESS, Worldwide Language Services, Tel. 00.1 (310) 260-7700
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`For Certification of this Translation please see enclosed Affidavit
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`Page 11 of 14
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`liuids
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`- mm 1.
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`Page 11 of 14
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`This is due both to the safety constraints associated with the use of hydrocarbons or ammonia and to the fact that no
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`Simple chemical molecule that has allthe. desirable characteristics is currently available.
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`4 Expanding the use of toxic and flammable liquids [UNE97]
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`Flammable liquids can be used rationally in two series ofapplications:
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`in industrial applications, where the use of such liquids is acceptable from the safety viewpoint anddoes not imply a
`significant additional cost. This is essentially the case in hydrocarbon refineries, but also in certain.chemica1—
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`engineering installations,
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`in uses where refrigerants are use with very small loads. Depending on the ‘country, this concept of very small load
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`will surely vary greatly. ln these cases, the additional cost of safe use of flammable refrigerants should be limited,
`since open competition exists ‘with HFCS.
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`Outside these two cases, an option proposed systematically for dangerous liquids is that of indirect systems, where
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`the coolness is transferred to the space to be cooled by a transport circuit. This design permits the refrigeration
`system to be confined. to a machine room. The social acceptability of such distributed machine rooms inall types of
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`buildings varies from onecountry to. another, and has yet to be verified extensively. Ammonia, a toxic liquid, is
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`accepted in industrial systems, because the personnel areequipped and trained to avoid the effects of panic. On the
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`other hand, in commercial uses, it does not seem plausible to consider evacuation of customers as normal behavior.
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`6 Development of new molecules and new mixtures [CAL97]
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`No ideal refrigerant exists, since there is a deep contradictionbetween the use of molecules witha very short
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`lifetime inthe atmosphere and the fact that the molecules should not be toxic or flammable. ln fact, the more
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`hydrogen a molecule contains, the easier it is for it todecompose rapidly in the atmosphere (this is due particularly
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`to the affinity of the hydroxyl radical —OH and hydrogen), and the larger the number of hydrogen atoms is, the. more
`flammable it is.
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`There is a new demand in chemical engineering for the developmentof mixtures or pure bodies that are neither toxic
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`norflammable and whose GWP is‘ low. R-32 is already the object of intensive research, since, it is the only HFC
`whose GWP is less than 1000. It is moderately flammable, and several Japanese companies are studying its use, both
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`as pure bodies and in mixtures.
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`Families of compounds such as fluoroetliers have been studied [B lV98], butfew candidates seem to emerge.
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`ADEME Technical Day — Paris, September 23,1999
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`“New Refrigerants: Does Cooling Have to Cost More?”
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`A Translation of WORDEXPRESS, Worldwide Language Services, Tel. 00.1 (310) 260-7700
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`For Certification of this Translation please see enclosed Affidavit
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`Page 12 of 14
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`Page 12 of 14
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`t Drastic. reduction in the alnolutt and confulement Of the refrigerants
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`The. most spectacular and most imniediate msults m ay be accompanied by a. drastic rcductism in HFC loads and in
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`obtaining as xtery high {eve} of crontineznent, in order m hmit their aaicfiitiunai ixnpasat on the
`eifcct.
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`L’>epam§':ng on the appiications, it. is possibk to iimit their effect the bad by oven" $13 $22. 1\3ex*.= paths are opening for
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`(ht: dav eleptment of mndensatinn sqystems that permit both a reducmm in. the I~efrig._>,_erant bad and an i311;>rt>&'~e1n-ant. in
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`tn:erg§.~' e