DE4226431A1 - Ozone-friendly coolant mixt. - in which standard machine oils are readily soluble, comprises 1,1,1,2-tetra:fluoroethane coolant and hydrocarbon additive - Google Patents

Ozone-friendly coolant mixt. - in which standard machine oils are readily soluble, comprises 1,1,1,2-tetra:fluoroethane coolant and hydrocarbon additive

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Publication number
DE4226431A1
DE4226431A1 DE19924226431 DE4226431A DE4226431A1 DE 4226431 A1 DE4226431 A1 DE 4226431A1 DE 19924226431 DE19924226431 DE 19924226431 DE 4226431 A DE4226431 A DE 4226431A DE 4226431 A1 DE4226431 A1 DE 4226431A1
Authority
DE
Germany
Prior art keywords
coolant
mixt
readily soluble
ozone
fluoroethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
DE19924226431
Other languages
German (de)
Inventor
Lothar Dipl Ing Kinne
Lutz Dipl Ing Richter
Klaus Dr Ing Meutzner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institut fuer Luft und Kaeltetechnik Gemeinnuetzige GmbH
Original Assignee
PRIVATES INST fur LUFT und KA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PRIVATES INST fur LUFT und KA filed Critical PRIVATES INST fur LUFT und KA
Priority to DE19924226431 priority Critical patent/DE4226431A1/en
Publication of DE4226431A1 publication Critical patent/DE4226431A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-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
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials 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
    • C09K5/044—Materials 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
    • C09K5/045—Materials 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/11—Ethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40—Replacement mixtures
    • C09K2205/42—Type R12

Abstract

Coolant mixt. for partially or fully hermetic refrigeration cycles is characterised by the addn. of 10-20 wt.% hydrocarbon (A) to the 1,1,1,2-tetrafluoroethane (R134a) coolant. USE/ADVANTAGE - Useful for CF or HFC based coolant mixts. The mixts. have a cooling performance comparable with CFC's, and standard refrigeration machine oils (e.g. mineral oils or polyalkylbenzene derivs.) are more readily soluble in the mixts. In an example, mixt. comprising R134a and 20 wt.% propane (partial pressures 12.0 and 10.4 respectively) gave an evapn. band of 0.02 (O) deg. C, a volumetric cooling performance of 563 (626) kj/m3 and an isentropic performance value of 1.93 (1.95)s at an evapn. temp. of -30 deg. C and a condensation temp. of 40 deg. C; (figs in brackets are for an R12 (CFC) coolant).

Description

Die Erfindung betrifft ein Kältemittelgemisch, das insbesondere in halb- und vollhermetischen Kältekreisläufen Anwendung findet und das kein die Ozonschicht der Erdatmosphäre schädi­ gendes FCKW-Kältemittel enthält.The invention relates to a refrigerant mixture, in particular in semi and fully hermetic Refrigeration circuits are used and that does not damage the ozone layer of the earth's atmosphere CFC refrigerant.

Als Alternative für das abzulösende Kältemittel R 12 hat sich das HFKW-Kältemittel F 134a favorisiert.HFC refrigerant F 134a has become an alternative for the refrigerant R 12 to be removed favors.

Der Einsatz von R 134a bringt aber bekanntlich folgende Nachteile mit sich: Die Kälteleistung sinkt mit fallender Verdampfungstemperatur proportional stärker als bei R 12, während die Antriebsleistung des Verdichters unverändert bleibt oder sogar leicht steig­ ende Tendenz aufweist. Im Ergebnis dessen verschlechtert sich die Leistungszahl des Kreisprozesses, und der Ener­ gieaufwand steigt.As is well known, the use of R 134a has the following disadvantages: The cooling capacity decreases proportionally more with decreasing evaporation temperature than with R 12, while the drive power of the compressor remains unchanged or even increases slightly end tendency. As a result, the coefficient of performance of the cycle and the energy deteriorate gi effort increases.

Die Mischbarkeit chlorfreier Kältemittel mit herkömmlichen Kältemaschinenölen, wie Miner­ alölen oder Ölen auf Polyalylbenzenbasis, ist nicht ausreichend gewährleistet. Geeignet für R 134a erscheinen synthetische Öle auf Esterbasis, für die mit wesentlich höheren Preisen gerechnet werden muß.The miscibility of chlorine-free refrigerants with conventional refrigeration oils, such as miners oil or oils based on polyalylbenzene is not sufficiently guaranteed. Synthetic oils based on ester appear suitable for R 134a, for those with much higher ones Prices must be expected.

Aufgabe der Erfindung ist die Schaffung eines Kältemittelgemisches, das auf der Grundlage eines FKW- oder HFKW-Kältemittels, vorzugsweise des Kältemittels R 134a, vor allem im Bereich tieferer Verdampfungstemperaturen Kälteleistungen und Leistungszahlen erwarten läßt, die mindestens in der Größe derjenigen von R 12 liegen.The object of the invention is to provide a refrigerant mixture based on a HFC or HFC refrigerant, preferably the refrigerant R 134a, especially in Range of lower evaporation temperatures, cooling capacities and performance figures can be expected, which are at least as large as those of R 12.

Die Aufgabe der Erfindung wird durch die Merkmale der Patentansprüche gelöst.The object of the invention is solved by the features of the claims.

Die Vorteile des Einsatzes der erfindungsgemäßen Kältemittelgemische liegen in der Sicherung bzw. Verbesserung von Kälteleistung und Leistungszahl gegenüber R 12. Dadurch entfällt auch die Notwendigkeit der Neuanpassung von Motor und Verdichter, was besonders für bestehende Anlagen bedeutungsvoll ist.The advantages of using the refrigerant mixtures according to the invention lie in the security or improvement of cooling capacity and coefficient of performance compared to R 12. This also eliminates the need to readjust the engine and compressor what is particularly important for existing systems.

Ein weiterer Vorteil entsteht vor allem auch für die Kältemittelumrüstung vorhandener Kälte­ anlagen. Da die Nebenkomponenten der vorgeschlagenen Gemische auch einen Beitrag zur Verbesse­ rung der Öllöslichkeitsbedingungen für chlorfreie Kältemittel in bisherigen R-12-Ölen leisten, kann auf die aufwendige Umrüstung der Anlagen auf die neuen Öle verzichtet werden. Another advantage arises above all for the refrigerant retrofitting of existing cold Investments. Because the minor components of the proposed mixtures also contribute to improvement oil solubility conditions for chlorine-free refrigerants in previous R-12 oils, the time-consuming retrofitting of the systems to the new oils can be dispensed with.  

Es können auch die praktischen Fragen unberücksichtigt bleiben, die sich aus dem höheren Feuchtigkeitsgehalt von Esterölen ergeben.The practical questions arising from the higher can also be disregarded Moisture content of ester oils.

Die Wahl der Gemischpartner und ihrer Konzentration erfolgte ferner unter dem Aspekt der Minimierung der Temperaturbänder während der Phasenumwandlung, so daß sich die Gemi­ sche im praktischen Betrieb nahezu wie reine Kältemittel verhalten.The choice of the mixture partners and their concentration was also made under the aspect of Minimization of the temperature bands during the phase change, so that the Gemi behave almost like pure refrigerants in practical operation.

Im nachfolgenden Ausführungsbeispiel werden die thermischen und kalorischen Größen für 20 Masse-% der Nebenkomponente im Gemisch mit R 134a für -30°C Verdampfungstemperatur und 40°C Kondensationstemperatur dargestellt und mit R-12- und R-134a-Werten verglichen.In the following exemplary embodiment, the thermal and caloric variables for 20 Mass% of the secondary component in a mixture with R 134a for -30 ° C evaporation temperature and 40 ° C condensation temperature and compared with R-12 and R-134a values.

Es ist bekannt, daß sich nicht alle resultierenden praktischen Eigenschaften und Wirkungen des Systems Kältemittelgemisch/Kältemaschinenöl theoretisch vorhersagen lassen. It is known that not all of the resulting practical properties and effects of the Systems refrigerant mixture / refrigeration machine oil theoretically predict.  

Im Kalorimeterversuch konnte deshalb für das Gemisch R 134a/Dimethylether im erfindungs­ gemäßen Konzentrationsbereich für die Bedingungen -30°C Verdampfungstemperatur/40°C Kondensationstemperatur - eine Verbesserung der Leistungszahl gegenüber R-12-Betrieb bis zu 12% ermittelt werden.In the calorimeter experiment it was therefore possible for the mixture R 134a / dimethyl ether in the invention appropriate concentration range for the conditions -30 ° C evaporation temperature / 40 ° C Condensation temperature - an improvement in the coefficient of performance compared to R-12 operation be determined to 12%.

Der Kreisprozeß wurde zunächst mit R 134a und R 12-Öl betrieben. Durch Zugabe der Nebenkomponente Dimethylether zu R 134a konnten die zuvor beobachteten Entmischungser­ scheinungen sofort und vollständig behoben werden.The cycle was initially operated with R 134a and R 12 oil. By adding the Secondary component dimethyl ether to R 134a could the previously observed demixers appearances are resolved immediately and completely.

Claims (4)

1. Kältemittelgemisch für den Einsatz in halb- und vollhermetischen Kältekreisläufen, da­ durch gekennzeichnet, daß dem Kältemittel 1,1,1,2-Tetrafluorethan (R 134a) 10 bis 20 Masse-% einer Kohlenwas­ serstoffverbindung als Nebenkomponente zugesetzt sind.1. refrigerant mixture for use in semi and hermetic refrigeration circuits, characterized in that the refrigerant 1,1,1,2-tetrafluoroethane (R 134a) 10 to 20 mass% of a hydrocarbon compound are added as a secondary component. 2. Kältemittelgemisch nach Anspruch 1, dadurch gekennzeichnet, daß als Nebenkomponente Dimethylether (C2H6O) zugesetzt wird.2. Refrigerant mixture according to claim 1, characterized in that dimethyl ether (C 2 H 6 O) is added as a secondary component. 3. Kältemittelgemisch nach Anspruch 1, dadurch gekennzeichnet, daß als Nebenkomponente Propan (C3H8) zugesetzt wird.3. Refrigerant mixture according to claim 1, characterized in that propane (C 3 H 8 ) is added as a secondary component. 4. Kältemittelgemisch nach Anspruch 1, dadurch gekennzeichnet, daß als Nebenkomponente Propylen (C4H6) zugesetzt wird.4. Refrigerant mixture according to claim 1, characterized in that propylene (C 4 H 6 ) is added as a secondary component.
DE19924226431 1992-08-10 1992-08-10 Ozone-friendly coolant mixt. - in which standard machine oils are readily soluble, comprises 1,1,1,2-tetra:fluoroethane coolant and hydrocarbon additive Withdrawn DE4226431A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19924226431 DE4226431A1 (en) 1992-08-10 1992-08-10 Ozone-friendly coolant mixt. - in which standard machine oils are readily soluble, comprises 1,1,1,2-tetra:fluoroethane coolant and hydrocarbon additive

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19924226431 DE4226431A1 (en) 1992-08-10 1992-08-10 Ozone-friendly coolant mixt. - in which standard machine oils are readily soluble, comprises 1,1,1,2-tetra:fluoroethane coolant and hydrocarbon additive

Publications (1)

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DE4226431A1 true DE4226431A1 (en) 1994-02-17

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2753452A1 (en) * 1996-09-17 1998-03-20 Malek Alfi THERMODYNAMIC FLUID COMPOSED OF PROPANE AND R 134A FOR REFRIGERATION AND AIR CONDITIONING
US6207071B1 (en) * 1994-07-19 2001-03-27 Nippon Mitsubishi Oil Corporation Fluid composition comprising HFC refrigerant and alkylbenzene-based refrigerator oil
WO2002026913A2 (en) * 2000-09-27 2002-04-04 Honeywell International Inc. Fluorocarbon refrigerant compositions
US6516837B2 (en) 2000-09-27 2003-02-11 Honeywell International Inc. Method of introducing refrigerants into refrigeration systems
US6783691B1 (en) 1999-03-22 2004-08-31 E.I. Du Pont De Nemours And Company Compositions of difluoromethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane and hydrocarbons
US8444873B2 (en) 2009-06-12 2013-05-21 Solvay Fluor Gmbh Refrigerant composition

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6207071B1 (en) * 1994-07-19 2001-03-27 Nippon Mitsubishi Oil Corporation Fluid composition comprising HFC refrigerant and alkylbenzene-based refrigerator oil
FR2753452A1 (en) * 1996-09-17 1998-03-20 Malek Alfi THERMODYNAMIC FLUID COMPOSED OF PROPANE AND R 134A FOR REFRIGERATION AND AIR CONDITIONING
WO1998012277A1 (en) * 1996-09-17 1998-03-26 Centre Technique Des Industries Mecaniques Propane based refrigerant mixture
US6783691B1 (en) 1999-03-22 2004-08-31 E.I. Du Pont De Nemours And Company Compositions of difluoromethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane and hydrocarbons
WO2002026913A2 (en) * 2000-09-27 2002-04-04 Honeywell International Inc. Fluorocarbon refrigerant compositions
WO2002026913A3 (en) * 2000-09-27 2002-05-30 Honeywell Int Inc Fluorocarbon refrigerant compositions
US6516837B2 (en) 2000-09-27 2003-02-11 Honeywell International Inc. Method of introducing refrigerants into refrigeration systems
US6640841B2 (en) 2000-09-27 2003-11-04 Honeywell International Inc. Method of introducing refrigerants into refrigeration systems
US8444873B2 (en) 2009-06-12 2013-05-21 Solvay Fluor Gmbh Refrigerant composition

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Owner name: INSTITUT FUER LUFT- UND KAELTETECHNIK GEMEINNUETZI

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