DE4241598A1 - Chlorine-free refrigerant mixt. - based on tri:fluoro:methane and hepta:fluoro:propane - Google Patents

Chlorine-free refrigerant mixt. - based on tri:fluoro:methane and hepta:fluoro:propane

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Publication number
DE4241598A1
DE4241598A1 DE19924241598 DE4241598A DE4241598A1 DE 4241598 A1 DE4241598 A1 DE 4241598A1 DE 19924241598 DE19924241598 DE 19924241598 DE 4241598 A DE4241598 A DE 4241598A DE 4241598 A1 DE4241598 A1 DE 4241598A1
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DE
Germany
Prior art keywords
fluoro
refrigerant
mixt
propane
chlorine
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Withdrawn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
DE19924241598
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German (de)
Inventor
Lothar Dipl Ing Kinne
Hans Dr Rer Nat Lippold
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
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PRIVATES INST fur LUFT und KA
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Priority to DE19924241598 priority Critical patent/DE4241598A1/en
Publication of DE4241598A1 publication Critical patent/DE4241598A1/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Withdrawn legal-status Critical Current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
    • C09K2205/22—All components of a mixture being fluoro compounds
    • 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

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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)
  • Compression-Type Refrigeration Machines With Reversible Cycles (AREA)

Abstract

A refrigerant mixt., for use in compression refrigerating circuits, consists of 12-25 wt.% trifluoromethane (R23,CHF3), 68-86 wt.% hepta-fluoropropane (R227,C3HF7) and 2-7 wt.%, ancillary component, pref. hydrocarbon, esp. dimethylether (DME C2H6O), propane (R270,C3H8) or propylene (R1270,C3H6). ADVANTAGE - The refrigerant mixt. is chlorine-free, has a wide temp. range of phase transformation and permits low pressure ratios.

Description

Die Erfindung betrifft ein chlorfreies Kältemittelgemisch für den Einsatz in Kompressions­ kältekreisläufen, vorzugsweise mit Rekuperatoren.The invention relates to a chlorine-free refrigerant mixture for use in compression cooling circuits, preferably with recuperators.

Bei der Suche nach Alternativstoffen für die abzulösenden FCKW-Kältemittel sollten nach Möglichkeit solche Kältemittelgemische gefunden werden, die bekannte Nachteile von FCKW- Kältemittel-Anlagen überwinden. Beispielsweise ist der Betrieb hermetischer Kältekreisläufe in der Haushaltkühlung dadurch gekennzeichnet, daß der einstufig betriebene Kältemittelverdichter gegen ein sehr hohes Druckverhältnis arbeiten muß, was sich nachteilig auf Prozeßtemperaturen, Energieverbrauch und Geräusch auswirkt.When looking for alternative substances for the CFC refrigerants to be removed should look for Possibility to find such refrigerant mixtures that have known disadvantages of CFC Overcoming refrigerant systems. For example, the operation of hermetic refrigeration cycles in the Household cooling characterized in that the single-stage refrigerant compressor must work against a very high pressure ratio, which is disadvantageous on process temperatures, Energy consumption and noise impact.

Als Alternative für das abzulösende Kältemittel R 12 hat sich das HFKW-Kältemittel R 134a favorisiert. Aber gerade in Kompressionskältekreisläufen mit großer Differenz zwischen Kondensations- und Verdampfungstemperatur ist R 134a durch noch höhere Druckverhältnisse als das abzulösende R 12 gekennzeichnet.HFC refrigerant R 134a has become an alternative for the refrigerant R 12 to be removed favors. But especially in compression refrigeration circuits with a large difference between The condensation and evaporation temperature is R 134a due to even higher pressure ratios marked as the R 12 to be replaced.

Aufgabe der Erfindung ist es, ein chlorfreies Kältemittelgemisch zu finden, das große Temperaturbänder der Phasenumwandlung und damit kleine Druckverhältnisse ermöglicht.The object of the invention is to find a chlorine-free refrigerant mixture, the large one Temperature bands of the phase transition and thus small pressure ratios.

Erfindungsgemäß wird die Aufgabe durch die Merkmale der Patentansprüche gelöst, indem ein Gemisch aus dem tiefsiedenden Kältemittel R 23, dem hochsiedenden Kältemittel R 227 und einer Nebenkomponente, die gute Öllöseeigenschaften besitzt, verwendet wird.According to the invention the object is achieved by the features of the claims, by a Mixture of the low-boiling refrigerant R 23, the high-boiling refrigerant R 227 and a secondary component that has good oil dissolving properties is used.

Das erfindungsgemäße ozonfreundliche zeotrope Kältemittelgemisch garantiert bei kleinem Druckverhältnis große Temperaturbänder der Phasenumwandlung und trägt außerdem zur Senkung des Energieverbrauches der Kälteanlage bei. Es wurde gefunden, daß der geringe Anteil der Nebenkomponente das Öllöslichkeitsverhalten des Kältesystems ohne wesentliche Veränderung der thermodynamischen Eigenschaften so verbessert, daß die Verwendung herkömmlicher Kältemaschinenöle, z. B. kostengünstiger Mineralöle, ermöglicht wird.The ozone-friendly zeotropic refrigerant mixture according to the invention guarantees small Pressure ratio large temperature bands of phase change and also contributes to Reduction of the energy consumption of the refrigeration system. It was found that the low proportion the secondary component the oil solubility behavior of the refrigeration system without essential Change in thermodynamic properties so improved that use conventional refrigerator oils, e.g. B. inexpensive mineral oils.

Die Nebenkomponente ist erforderlich, da sich die eigentlichen wirksamen Kältemittel R 227 und R 23 nur sehr schlecht im Kältemaschinenöl lösen. Bei tiefen Temperaturen sind die reinen Öle so hochviskos, daß es zu Verstopfungsstörungen in der Kapillare des Drosselorgans 4 und zu Störungen bei der Ölrückführung kommt. Die Nebenkomponente löst sich sehr gut im Öl und kann dessen Viskosität durchaus um nahezu einer Zehnerpotenz herabsetzen und damit eine stabile Ölrückführung garantieren.The secondary component is necessary because the actual effective refrigerants R 227 and R 23 dissolve very poorly in the refrigerating machine oil. At low temperatures, the pure oils are so highly viscous that there are blockages in the capillary of the throttling element 4 and there are problems with the oil return. The secondary component dissolves very well in the oil and can reduce its viscosity by almost a power of ten and thus guarantee a stable oil return.

Das stark reduzierte Druckverhältnis wirkt sich positiv auf den Energieverbrauch, Geräusche und Verschleiß aus.The greatly reduced pressure ratio has a positive effect on energy consumption, noise and Wear out.

Im Gefolge der großen Temperaturbänder bei der Phasenumwandlung steht Kälte bzw. Wärme bei unterschiedlichem Temperaturniveau zur Verfügung. Das ist auf der kalten Seite z. B. vorteilhaft für Mehrtemperaturkühlgeräte zu nutzen.In the wake of the large temperature bands in the phase change, there is either cold or warmth available at different temperature levels. That is on the cold side e.g. B. advantageous to use for multi-temperature cooling devices.

Bei Wärmepumpeneinsatz entsteht der Vorteil hoher erreichbarer Wärmeträger-Vorlauftempera­ turen bei beherrschbaren Kondensationsdrücken und niedrigen Druckverhältnissen.When using heat pumps, there is the advantage of high achievable heat transfer flow temperatures structures with manageable condensation pressures and low pressure ratios.

An nachfolgendem Ausführungsbeispiel soll die Erfindung näher erläutert werden:The invention will be explained in more detail using the following exemplary embodiment:

In der Abbildung ist die Prinzipschaltung eines Kältekreislaufes mit dem Kondensator 1, dem Rekuperator 2, dem Verdichter 3, dem Drosselorgan 4 und den Verdampfern 5 dargestellt.The illustration shows the basic circuit of a refrigeration cycle with the condenser 1 , the recuperator 2 , the compressor 3 , the throttle element 4 and the evaporators 5 .

Die Verringerung des Druckverhältnisses in diesem Kreislauf wird durch Verwendung eines zeotropen Kältemittelgemisches mit großem Temperaturband bei Verdampfung und Kondensation erreicht. Dadurch wird es möglich, die Verdampfung bei tiefen Temperaturen (z. B. -45 bis zu -35°C) zu beginnen, ohne daß der Kreisprozeß mit unzulässig niedrigem Saugdruck arbeitet. Diese Temperaturen sind beispielsweise vorteilhaft im Tiefkühlfachverdampfer eines Zwei- oder Mehrtemperaturkühlschrankes nutzbar. Verdampfungstemperaturen im Bereich um -20 °C können im nachgeschalteten Normalkühlfachverdampfer zur Wirkung gebracht werden.The reduction in the pressure ratio in this circuit is achieved by using a Zeotropic refrigerant mixture with a large temperature range for evaporation and condensation reached. This makes it possible to control evaporation at low temperatures (e.g. -45 to -35 ° C) to start without the cycle working with impermissibly low suction pressure. These temperatures are advantageous, for example, in the deep-freeze evaporator of a two-oven  Multi-temperature refrigerator can be used. Evaporation temperatures in the range of around -20 ° C can be brought into effect in the downstream cooling compartment evaporator.

Der Abschluß der Verdampfung erfolgt dann bei Temperaturen um -10 bis 5°C im Rekupe­ rator 2 durch Wärmeaufnahme vom abschließend kondensierenden Kältemittelgemisch.The conclusion of the evaporation then takes place at temperatures around -10 to 5 ° C in the recuperator 2 by absorbing heat from the finally condensing mixture of refrigerants.

Analog gestalten sich die Temperaturverläufe auf der warmen Seite des Kältekreislaufes. Die Wahl eines solchen Kältemittelgemisches gestattet Kondensationsanfangstemperaturen von 60°C ohne Überschreitung zulässiger Kondensationsdrücke. Das Ende der Kondensation wird dann im Rekuperator 2 bei Temperaturen um 25 bis 15°C erreicht.The temperature profiles on the warm side of the refrigeration cycle are analogous. The choice of such a refrigerant mixture allows initial condensation temperatures of 60 ° C without exceeding permissible condensation pressures. The end of the condensation is then reached in the recuperator 2 at temperatures around 25 to 15 ° C.

Die damit einhergehende Senkung des Kondensationsdruckes hat ein niedriges Druckverhältnis zur Folge, was der Aufgabenstellung entspricht.The associated lowering of the condensation pressure has a low pressure ratio result, which corresponds to the task.

Berücksichtigt werden muß, daß die Verringerung der wirksamen Enthalpiedifferenz im Verdampfer 5 gegenüber vollständiger Phasenumwandlung mit einem höheren Förderstrom des Verdichters 3 auszugleichen ist. Es wird daher eine konstruktive Optimierung des Kältekreislaufes mit dem Ziel notwendig, daß der Energiegewinn durch Reduzierung der vom Druckverhältnis abhängigen Verluste größer ausfällt als der Energiemehrbedarf infolge Vergrößerung des Verdich­ terhubvolumens.It must be taken into account that the reduction in the effective enthalpy difference in the evaporator 5 compared to complete phase transformation must be compensated for with a higher flow rate of the compressor 3 . It is therefore a constructive optimization of the refrigeration cycle necessary with the aim that the energy gain by reducing the pressure-dependent losses turns out larger than the additional energy requirements due to the increase in compression terhubvolumens.

Claims (4)

1. Kältemittelgemisch für den Einsatz in Kompressions-Kältekreisläufen, dadurch gekennzeich­ net, daß es zu 12-25 Masse-% aus dem tiefsiedenden Kältemittel Trifluormethan (R 23, CHF3), zu 68-86 Masse-% aus dem höhersiedenden Kältemittel Hepafluorpropan (R 227, C3HF7) und aus 2-7 Masse-% einer Nebenkomponente, vorzugsweise einer Kohlenwasserstoffverbindung, besteht.1.Refrigerant mixture for use in compression refrigeration circuits, characterized in that it is 12-25% by mass from the low-boiling refrigerant trifluoromethane (R 23, CHF 3 ), 68-86% by mass from the higher-boiling refrigerant hepafluoropropane ( R 227, C 3 HF 7 ) and 2-7 mass% of a secondary component, preferably a hydrocarbon compound. 2. Kältemittelgemisch nach Anspruch 1, dadurch gekennzeichnet, daß als Nebenkomponente Dimethylether (DME, C2H6O) eingesetzt wird.2. Refrigerant mixture according to claim 1, characterized in that dimethyl ether (DME, C 2 H 6 O) is used as the secondary component. 3. Kältemittelgemisch nach Anspruch 1, dadurch gekennzeichnet, daß als Nebenkomponente Propan (R 270, C3H8) eingesetzt wird.3. A refrigerant mixture according to claim 1, characterized in that propane (R 270, C 3 H 8 ) is used as the secondary component. 4. Kältemittelgemisch nach Anspruch 1, dadurch gekennzeichnet, daß als Nebenkomponente Propylen (R 1270, C3H6) eingesetzt wird.4. A refrigerant mixture according to claim 1, characterized in that propylene (R 1270, C 3 H 6 ) is used as the secondary component.
DE19924241598 1992-12-10 1992-12-10 Chlorine-free refrigerant mixt. - based on tri:fluoro:methane and hepta:fluoro:propane Withdrawn DE4241598A1 (en)

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Application Number Priority Date Filing Date Title
DE19924241598 DE4241598A1 (en) 1992-12-10 1992-12-10 Chlorine-free refrigerant mixt. - based on tri:fluoro:methane and hepta:fluoro:propane

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DE19924241598 DE4241598A1 (en) 1992-12-10 1992-12-10 Chlorine-free refrigerant mixt. - based on tri:fluoro:methane and hepta:fluoro:propane

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DE4241598A1 true DE4241598A1 (en) 1994-06-16

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010010768A1 (en) 2009-03-10 2010-09-16 Institut für Luft- und Kältetechnik gGmbH Working mixture for equipments to produce cold or transfer heat, where the equipments are built from a refrigerant circuit with a compressor, a condenser, a throttle unit and an evaporator, comprises a mixture of carbon dioxide and propene

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE359049C (en) * 1918-05-27 1922-09-18 Halleck Wager Seaman Refrigerant for compression refrigeration machines
DE383182C (en) * 1918-05-27 1923-10-11 Halleck Wager Seaman Refrigerant for compression refrigeration machines
DE697055C (en) * 1937-09-06 1940-10-04 Escher Wyss Werke Lindau G M B Procedure for securing the operation of compression refrigeration machines
DE1769371A1 (en) * 1967-05-15 1971-08-12 Allied Chem Cooling media
SU637419A1 (en) * 1977-07-21 1978-12-15 Одесский Технологический Институт Холодильной Промышленности Refrigerant
SU1086003A1 (en) * 1982-11-03 1984-04-15 Одесский Технологический Институт Холодильной Промышленности Refrigerant for low-temperature compression refrigeration machine
EP0451692A2 (en) * 1990-04-04 1991-10-16 Daikin Industries, Limited Refrigerant
EP0492777A2 (en) * 1990-12-05 1992-07-01 Star Refrigeration Ltd. Multi-component refrigerant
WO1992011338A1 (en) * 1990-12-17 1992-07-09 E.I. Du Pont De Nemours And Company Constant boiling compositions of fluorinated hydrocarbons
WO1992016597A1 (en) * 1991-03-18 1992-10-01 Allied-Signal Inc. Non-azeotropic refrigerant compositions comprising difluoromethane; 1,1,1-trifluoroethane; or propane
EP0509673A1 (en) * 1991-04-18 1992-10-21 Imperial Chemical Industries Plc Refrigerant compositions

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE359049C (en) * 1918-05-27 1922-09-18 Halleck Wager Seaman Refrigerant for compression refrigeration machines
DE383182C (en) * 1918-05-27 1923-10-11 Halleck Wager Seaman Refrigerant for compression refrigeration machines
DE697055C (en) * 1937-09-06 1940-10-04 Escher Wyss Werke Lindau G M B Procedure for securing the operation of compression refrigeration machines
DE1769371A1 (en) * 1967-05-15 1971-08-12 Allied Chem Cooling media
SU637419A1 (en) * 1977-07-21 1978-12-15 Одесский Технологический Институт Холодильной Промышленности Refrigerant
SU1086003A1 (en) * 1982-11-03 1984-04-15 Одесский Технологический Институт Холодильной Промышленности Refrigerant for low-temperature compression refrigeration machine
EP0451692A2 (en) * 1990-04-04 1991-10-16 Daikin Industries, Limited Refrigerant
EP0492777A2 (en) * 1990-12-05 1992-07-01 Star Refrigeration Ltd. Multi-component refrigerant
WO1992011338A1 (en) * 1990-12-17 1992-07-09 E.I. Du Pont De Nemours And Company Constant boiling compositions of fluorinated hydrocarbons
WO1992016597A1 (en) * 1991-03-18 1992-10-01 Allied-Signal Inc. Non-azeotropic refrigerant compositions comprising difluoromethane; 1,1,1-trifluoroethane; or propane
EP0509673A1 (en) * 1991-04-18 1992-10-21 Imperial Chemical Industries Plc Refrigerant compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Derwent-Abstract: wpat database: JP 04332786 A *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010010768A1 (en) 2009-03-10 2010-09-16 Institut für Luft- und Kältetechnik gGmbH Working mixture for equipments to produce cold or transfer heat, where the equipments are built from a refrigerant circuit with a compressor, a condenser, a throttle unit and an evaporator, comprises a mixture of carbon dioxide and propene

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