FR2753452A1 - THERMODYNAMIC FLUID COMPOSED OF PROPANE AND R 134A FOR REFRIGERATION AND AIR CONDITIONING - Google Patents

THERMODYNAMIC FLUID COMPOSED OF PROPANE AND R 134A FOR REFRIGERATION AND AIR CONDITIONING Download PDF

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Publication number
FR2753452A1
FR2753452A1 FR9611410A FR9611410A FR2753452A1 FR 2753452 A1 FR2753452 A1 FR 2753452A1 FR 9611410 A FR9611410 A FR 9611410A FR 9611410 A FR9611410 A FR 9611410A FR 2753452 A1 FR2753452 A1 FR 2753452A1
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Prior art keywords
propane
refrigeration
air conditioning
fluids
tetrafluoroethane
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FR9611410A
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French (fr)
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FR2753452B1 (en
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Priority to FR9611410A priority Critical patent/FR2753452B1/en
Priority to PCT/FR1997/001595 priority patent/WO1998012277A1/en
Priority to AU42129/97A priority patent/AU4212997A/en
Priority to EP97940210A priority patent/EP0946668A1/en
Publication of FR2753452A1 publication Critical patent/FR2753452A1/en
Application granted granted Critical
Publication of FR2753452B1 publication Critical patent/FR2753452B1/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/12Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40Replacement mixtures
    • C09K2205/43Type R22

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

This propane based refrigerant mixture designed for replacing difluorohydrochloromethane (R22) is an azeotropic or quasi-azeotropic two-component mix of propane and a second constituent selected among 1,1,1,2-tetrafluoroethane (R134a) or R22. It contains wt.35 % to 58 % of propane and 65 % to 42 % of R134a, or it contains about 35 wt.% of propane and 65 % of R22.

Description

La présente invention concerne un fluide composé d'un mélange de deux fluides, à savoir, du propane et du 1,1,1 ,2-tétrafluoroéthane (HFR134a). Ce fluide est destiné au domaine de la réfrigération, du conditionnement de l'air et des pompes à chaleur, en tant que fluide thermodynamique. The present invention relates to a fluid composed of a mixture of two fluids, namely, propane and 1,1,1,2-tetrafluoroethane (HFR134a). This fluid is intended for the field of refrigeration, air conditioning and heat pumps, as a thermodynamic fluid.

A la suite du protocole de Montréal, et de la réglementation des substances qui en découle, certains fluides de la classe des hydrochlorofluoro- carbones (HCFC) seront interdits. Or, leur remplacement n'est pas correctement assuré par les fluides actuellement proposés. Following the Montreal Protocol and the regulation of substances deriving therefrom, certain fluids of the hydrochlorofluorocarbon (HCFC) class will be prohibited. However, their replacement is not properly ensured by the fluids currently offered.

Ces fluides posent des problèmes de performance, de fiabilité, pour les fluides artificiels, et des problèmes de risque pour l'utilisateur pour les fluides dits naturels. These fluids pose problems of performance, reliability, for artificial fluids, and risk problems for the user for so-called natural fluids.

Le mélange des deux fluides, proposé ici, donne, dans une plage de composition relativement large, propane/1,1,1,2-tétrafluoroéthane (HFR134a), entre 35 %/65 %, et 58 %/42 %, des propriétés thermodynamiques et thermophysiques se rapprochant fortement des propriétés des fluides à remplacer. Ils sont comparables notamment aux propriétés du chlorodifluorométhane (HCFC-22), utilisé à la fois en réfrigération, pompes à chaleur, et conditionnement de l'air. The mixture of the two fluids, proposed here, gives, in a relatively wide composition range, propane / 1,1,1,2-tetrafluoroethane (HFR134a), between 35% / 65%, and 58% / 42%, thermodynamics and thermophysics closely approximating the properties of the fluids to be replaced. They are comparable in particular to the properties of chlorodifluoromethane (HCFC-22), used both in refrigeration, heat pumps, and air conditioning.

Les mélanges proposés ici, objets du brevet, présentent des qualités de quasi-azéotropie, à savoir, un faible glissement de température, à l'évaporation et en condensation. Elles leur confere un comportement proche d'un fluide simple. The mixtures proposed here, which are the subject of the patent, exhibit qualities of quasi-azeotropy, namely, a low temperature slip, on evaporation and in condensation. They give them behavior close to a simple fluid.

Un minimum de glissement de température pour la plage se situant entre moins 40"C et la température critique existe pour la composition 45 %/55 %, propane/t, t, 1 ,2-tétrafluoroéthane (HFR 134a). A minimum temperature drift for the range between minus 40 "C and the critical temperature exists for the composition 45% / 55%, propane / t, t, 1, 2-tetrafluoroethane (HFR 134a).

La température critique de ces mélanges est de tordre de 82/85"C, et la pression critique correspondante est de l'ordre de 40/41 bars, selon les proportions des deux composants. The critical temperature of these mixtures is twist of 82/85 "C, and the corresponding critical pressure is of the order of 40/41 bars, depending on the proportions of the two components.

Outre les propriétés thermodynamiques et thermophysiques de ces mélanges, ils présentent une forte amélioration en matière de risque, en comparaison avec les fluides inflammables purs. In addition to the thermodynamic and thermophysical properties of these mixtures, they present a strong improvement in terms of risk, in comparison with pure flammable fluids.

Cette réduction de l'inflammabilité est liée à la fois à la réduction des quantités de fluide inflammable nécessaires, entre 35 % et 58 % par rapport aux fluides purs, mais aussi, la présence en phase gazeuse d'un fluide ininflammable, plus lourd que l'air, contribue à réduire l'inflammabilité. This reduction in flammability is linked both to the reduction in the quantities of flammable fluid required, between 35% and 58% compared to pure fluids, but also, the presence in the gas phase of a non-flammable fluid, heavier than air, helps reduce flammability.

L'inflammabilité de la composition est réduite du fait de la liaison azéotropique dans la plaque de mélange mentionnée, et notamment autour de 45 %/55 % propane/l,l,l,2-tétrafluoroéthane (HFR134a). Elle est inférieure à 45 % propane. The flammability of the composition is reduced due to the azeotropic bond in the mentioned mixing plate, and in particular around 45% / 55% propane / l, l, l, 2, tetrafluoroethane (HFR134a). It is less than 45% propane.

L'application des mélanges, objets du brevet, ne nécessite pas de modification majeure des installations appliquant les fluides appelés à disparaître, (échangeurs, compresseurs, régulation) ni la nature des huiles de lubrification. The application of the mixtures, which are the subject of the patent, does not require any major modification to the installations applying the fluids that are about to disappear (exchangers, compressors, regulation) or the nature of the lubricating oils.

Les deux fluides sont classés comme étant non-toxiques. Le 1,1,1,2 tétrafluoroéthane (HFR134a) est classé non-inflammable. Both fluids are classified as non-toxic. 1,1,1,2 tetrafluoroethane (HFR134a) is classified as non-flammable.

Un avantage certain de ces mélanges réside dans la disponibilité en quantités industrielles des deux composants, avec un très faible coût du propane. Ils offrent ainsi à l'industriel une solution avec de bonnes performances, une bonne fiabilité de produit, et une réduction très importante du risque lié à l'inflammabilité. A certain advantage of these mixtures lies in the availability in industrial quantities of the two components, with very low cost of propane. They thus offer the manufacturer a solution with good performance, good product reliability, and a very significant reduction in the risk linked to flammability.

Le propane est un gaz à effet de serre négligeable, et le mélange du propane avec le 1,1,1 ,2-tétrafluoroéthane (HFR134a) réduit l'effet de serre direct de ce dernier dans la proportion du mélange. On recherchera, pour chaque application, la composition la plus appropriée, ayant, à la fois les performances recherchées, et la plus faible quantité de propane, avec un glissement de température le plus faible possible. A titre d'exemple, dans le cas des rafraichis- seurs d'air, fonctionnant à des températures de l'ordre de 10 C à 15"C, le mélange 35 %/65 % représente une solution avantageuse, puisque le glissement de température est d'environ 0,2"C à 50"C de température de condensation, et de l'ordre de 1"C, à environ 10 C de température d'évaporation. Pour des applications telles que les refroidisseurs de lait, fonctionnant autour de 0 C, le mélange 40 %/60 % propane/l,l,l,2-tétrafluoroéthane (HFR134a) est applicable. Dans le cas de la réfrigération nécessitant des températures d'évaporation de l'ordre de moins 30"C, et en dessous, le mélange 45 %/55 %, propane/l,l,l,2-tétrafluoro- éthane (HFR134a) est plus adapté. La composition mentionnée dans la ligne précédente est utilisable pour toutes les applications citées ci-dessus, étant la plus proche de l'azéotropie. Pour réduire la pression de service, ou l'inflammabilité, un troisième fluide, de type hydrofluorocarbone (HFC), par exemple, peut être ajouté en faibles quantités, dans certains cas. La préparation de mélange à une proportion donnée peut se faire de diverses façons, en phase liquide, ou en phase vapeur, avec pesée, mesure de débits des composants, ou mesure de propriétés thermiques ou thermodynamiques.  Propane is a negligible greenhouse gas, and mixing propane with 1,1,1,2-tetrafluoroethane (HFR134a) reduces the direct greenhouse effect of the latter in the proportion of the mixture. For each application, the most appropriate composition will be sought, having both the desired performance and the lowest amount of propane, with the lowest possible temperature shift. By way of example, in the case of air coolers, operating at temperatures of the order of 10 ° C. to 15 ° C., the mixture 35% / 65% represents an advantageous solution, since the temperature sliding is about 0.2 "C at 50" C of condensation temperature, and about 1 "C, at about 10 C of evaporation temperature. For applications such as milk coolers, operating around 0 C, the mixture 40% / 60% propane / l, l, l, 2-tetrafluoroethane (HFR134a) is applicable. In the case of refrigeration requiring evaporation temperatures of the order of minus 30 "C, and below, the mixture 45% / 55%, propane / l, l, l, 2-tetrafluoroethane (HFR134a) is more suitable. The composition mentioned in the previous line can be used for all the applications mentioned above, being the closest to azeotropy. To reduce the working pressure, or the flammability, a third fluid, of hydrofluorocarbon type (HFC), for example, can be added in small quantities in some cases. Mixing preparation at a given proportion can be done in various ways, in the liquid phase, or in the vapor phase, with weighing, measurement of component flow rates. , or measurement of thermal or thermodynamic properties.

Claims (2)

REVENDICATIONS 1. Mélange quasiazéotropique contenant en masse 35 % à 58 % de propane et 65 % à 42 % de 1,1,1 ,2-tétrafluoroéthane (HFR134a).1. Quasiazeotropic mixture containing by mass 35% to 58% of propane and 65% to 42% of 1,1,1,2-tetrafluoroethane (HFR134a). 2. Utilisation d'un mélange selon la revendication 1 comme fluide frigorigène pour la réfrigération, ou le conditionnement d'air. 2. Use of a mixture according to claim 1 as a refrigerant for refrigeration or air conditioning.
FR9611410A 1996-09-17 1996-09-17 THERMODYNAMIC FLUID COMPOSED OF PROPANE AND R 134A FOR REFRIGERATION AND AIR CONDITIONING Expired - Fee Related FR2753452B1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
FR9611410A FR2753452B1 (en) 1996-09-17 1996-09-17 THERMODYNAMIC FLUID COMPOSED OF PROPANE AND R 134A FOR REFRIGERATION AND AIR CONDITIONING
PCT/FR1997/001595 WO1998012277A1 (en) 1996-09-17 1997-09-10 Propane based refrigerant mixture
AU42129/97A AU4212997A (en) 1996-09-17 1997-09-10 Propane based refrigerant mixture
EP97940210A EP0946668A1 (en) 1996-09-17 1997-09-10 Propane based refrigerant mixture

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR9611410A FR2753452B1 (en) 1996-09-17 1996-09-17 THERMODYNAMIC FLUID COMPOSED OF PROPANE AND R 134A FOR REFRIGERATION AND AIR CONDITIONING

Publications (2)

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FR2753452A1 true FR2753452A1 (en) 1998-03-20
FR2753452B1 FR2753452B1 (en) 1998-12-04

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EP (1) EP0946668A1 (en)
AU (1) AU4212997A (en)
FR (1) FR2753452B1 (en)
WO (1) WO1998012277A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05117645A (en) * 1991-10-28 1993-05-14 Matsushita Electric Ind Co Ltd Working fluid
EP0565265A1 (en) * 1992-04-04 1993-10-13 Star Refrigeration Ltd. Refrigerant composition
DE4226431A1 (en) * 1992-08-10 1994-02-17 Privates Inst Fuer Luft Und Ka Ozone-friendly coolant mixt. - in which standard machine oils are readily soluble, comprises 1,1,1,2-tetra:fluoroethane coolant and hydrocarbon additive
WO1995008602A1 (en) * 1993-09-22 1995-03-30 Star Refrigeration Limited Replacement refrigerant composition

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5842224B2 (en) * 1978-12-28 1983-09-17 ダイキン工業株式会社 mixed refrigerant
GB2228739B (en) * 1989-03-03 1992-07-22 Star Refrigeration Refrigerant
JP3428032B2 (en) * 1990-11-21 2003-07-22 イネオス フラウアー ホールデイングス リミテッド Coolant composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05117645A (en) * 1991-10-28 1993-05-14 Matsushita Electric Ind Co Ltd Working fluid
EP0565265A1 (en) * 1992-04-04 1993-10-13 Star Refrigeration Ltd. Refrigerant composition
DE4226431A1 (en) * 1992-08-10 1994-02-17 Privates Inst Fuer Luft Und Ka Ozone-friendly coolant mixt. - in which standard machine oils are readily soluble, comprises 1,1,1,2-tetra:fluoroethane coolant and hydrocarbon additive
WO1995008602A1 (en) * 1993-09-22 1995-03-30 Star Refrigeration Limited Replacement refrigerant composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9324, Derwent World Patents Index; AN 93-191774, XP002029910 *

Also Published As

Publication number Publication date
AU4212997A (en) 1998-04-14
FR2753452B1 (en) 1998-12-04
EP0946668A1 (en) 1999-10-06
WO1998012277A1 (en) 1998-03-26

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