WO2008065331A2 - Diluants frigorigènes pour le hcfc22 - Google Patents

Diluants frigorigènes pour le hcfc22 Download PDF

Info

Publication number
WO2008065331A2
WO2008065331A2 PCT/GB2007/004145 GB2007004145W WO2008065331A2 WO 2008065331 A2 WO2008065331 A2 WO 2008065331A2 GB 2007004145 W GB2007004145 W GB 2007004145W WO 2008065331 A2 WO2008065331 A2 WO 2008065331A2
Authority
WO
WIPO (PCT)
Prior art keywords
hcfc22
hfc
refrigeration
remaining
leakage
Prior art date
Application number
PCT/GB2007/004145
Other languages
English (en)
Other versions
WO2008065331A3 (fr
Inventor
John Edward Poole
Richard Powell
Original Assignee
Rpl Holdings Limited
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 Rpl Holdings Limited filed Critical Rpl Holdings Limited
Publication of WO2008065331A2 publication Critical patent/WO2008065331A2/fr
Publication of WO2008065331A3 publication Critical patent/WO2008065331A3/fr

Links

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
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated hydrocarbons

Definitions

  • This invention relates to a method for progressively extending HCFC22 remaining in a refrigeration, air conditioning or heat pump device after leakage of part of the original charge, by mixing it with a refrigerant comprising one or more organofluorine compounds and optionally HCFC22 and optionally one or more hydrocarbons.
  • refrigerant compositions used as extenders for HCFC22 which are non flammable under all conditions of fractionation, non ozone depleting, of low toxicity, and are compatible when added to HCFC22.
  • the term "extender” means any fluid comprising a fluorocarbon which is used to dilute HCFC22 already being used in a device so that the resulting mixture allows the device to continue operating satisfactorily.
  • the term “progressively” means that as the extender is used on two or more successive occasions to make up the refrigerant charge to the level required for satisfactory operation, the ratio of remaining HCFC22 relative to the added fluorocarbon extender steadily decreases.
  • HCFC22 has an Ozone Depletion Potential (ODP) and is subject to phase out according to the international agreement the Montreal Protocol.
  • ODP Ozone Depletion Potential
  • Non ozone depleting replacements usually require a complete change of lubricant, replacement of all seals in the device and other changes to the hardware which makes such replacements impractical for use in existing devices.
  • Alternative non ozone depleting replacements for HCFC22 contain hydrofluorocarbons (HFCs) with small amounts of hydrocarbons which facilitate miscibility with traditional lubricants commonly found in refrigeration and air conditioning devices. It has been found that such replacements for HCFC22 used with traditional lubricants in a refrigerator or air conditioning device can result in dimensional changes in the seals so that the refrigerant can escape from the device.
  • HFCs hydrofluorocarbons
  • Refrigerant compositions containing HFCs with or without hydrocarbons can have a deleterious effect on seals in a refrigeration or air conditioning device operating only on HCFC22.
  • This invention relates to mixing non ozone depleting refrigerant fluorocarbon compositions with the HCFC22 remaining in a device without adversely affecting the seals while maintaining non flammability.
  • the fluorocarbon composition is mixed with the remaining HCFC22 within the device. This method is called "topping-up”.
  • the remaining HCFC22 is removed from the device, mixed with the fluorocarbon composition and the resulting mixture returned to the device.
  • the individual components of the fluorocarbon composition are mixed successively with the remaining HCFC22 either inside or outside the device. They can be added in any desired order.
  • the refrigerant compositions which are suitable for extending HCFC22 in accordance with this invention comprise mixtures of fluorocarbons, especially hydrofluorocarbons (HFCs), optionally with small amounts of hydrocarbons and optionally with more HCFC22. While it is well known that HFCs can replace Ozone Depleting Substances (ODS) including HCFC22, HFCs are not suitable replacements for HCFC22 in existing refrigeration devices due to their poor miscibility with traditional lubricants and their attack on seals. Replacing CFCs and HCFCs with HFCs requires a change of lubricant to a synthetic oxygen containing lubricant and replacement of the existing seals. This invention enables devices operating on HCFC22 to be gradually converted to alternative non ozone depleting replacements at low cost without any changes required to the hardware or the hydrocarbon oil lubrication.. The remaining HCFC22 contributes to continuing effective oil return.
  • HFCs hydrofluorocarbons
  • HCFC22 has a swelling affect on some seals (eg neoprene) which is incorporated into the design of a refrigeration or air conditioning device.
  • some seals eg neoprene
  • the seals may become degraded with the result that the refrigerant in the device can leak out resulting in a poor performance and ultimately failure of the entire device.
  • the refrigerant compositions which are the subject of this convention when added to HCFC22 with the resultant mixture containing as low as 10% of HCFC22 have no deleterious effect on the seals in the device while not affecting the operation of the device.
  • Various terms have been used in patent literature to describe refrigerant mixtures and are used in this specification. The following definitions are taken from ASHRAE Standard 34:
  • Azeotrope an azeotropic blend is one containing two or more refrigerants whose equilibrium vapour and liquid phase compositions are the same at a given pressure. Azeotropic blends exhibit some segregation of components at other conditions. The extent of the segregation depends on the particular azeotrope and the application.
  • Azeotropic temperature the temperature at which the liquid and vapour phases of a blend have the same mole fractionation of each component at equilibrium for a specified pressure.
  • Near azeotrope a zeotropic blend with a temperature glide sufficiently small that it may be disregarded without consequential error in analysis for a specific application.
  • Zeotrope blends comprising multiple components of different volatilities that, when used in refrigeration cycles, change volumetric composition and saturation temperatures as they evaporate (boil) or condense at constant pressure.
  • Temperature glide the absolute value of the difference between the starting and ending temperatures of a phase-change process by a refrigerant within a component of a refrigerating device, exclusive of any subcooling or superheating. This term usually describes condensation or evaporation of a zeotrope .
  • refrigerant compositions which are suitable for extending HCFC22 in accordance with this invention may not aversely affect the performance of the device, and may not result in the formation harmful azeotropic mixtures which have vapour pressures higher than equipment designed for HCFC22 can withstand.
  • a method for progressively extending HCFC22 remaining in a refrigeration, air conditioning or heat pump device after leakage of part of the original charge of HCFC22 comprises the steps of mixing the HCFC22 with one or more hydrofluorocarbons, fluoropropenes or fluorocarbon iodide selected from the following list: HFC32, HFC125, HFC143a, HFC134a, HFC152a, HFC 134, HFC227ea, 1,1,1,2-tetrafluoropropene, c-1,1,1,3- tetrafluoropropene, t- 1, 1 , 1 ,3-tetrafluoropropene, 1 , 1, 1,2,3-pentafluoropropene, 1,1,1,3,3-pentafluoropropene and trifluoro-iodomethane.
  • hydrofluorocarbons, fluoropropenes or fluorocarbon iodide selected from the following list: HFC32,
  • Suitable hydrocarbons having a boiling point in the range -50 0 C to +50 0 C include 2-methylpropane, propane, 2,2-dimethylpropane, n- butane, 2-methylbutane, propene, n-butene and mixtures thereof.
  • Especially preferred extenders are commercially available blends comprising
  • HFCs that have been assigned ASHRAE numbers so their hazard ratings are already known by the industry.
  • Such blends include, but are not limited to, R404A, R407A, R407B, R407C, R407E, R415A, R417A, R418A, R419A, R420A, R421A, R421B, R422A, R422B, R422C, R422D, R424A, R425A, R426A, R427A, R428A and R507A.
  • compositions of the fluorocarbon and fluorocarbon/hydrocarbon blends which are suitable for extending HCFC22 meet one or more of the following criteria:
  • the low or high temperatures achieved should be similar to those achieved by the device when operating with its design charge of HCFC22 alone,
  • the discharge pressure from the compressor is not more than 30% greater when operating with its design charge of HCFC22 alone
  • the pressure at the compressor suction port is at least 85% of the suction pressure when operating with its design charge of HCFC22 alone
  • the refrigeration or heating capacity is not less than 83% of that achieved when operating with its design charge of HCFC22 alone,
  • the cooling or heating Coefficient of Performance is at least 82% of that of HCFC22 when operating with its design charge of HCFC22 alone, the mixed HCFC22/fluorocarbon-containing refrigerant in the device is nonflammable according to the criteria set out in ASHRAE Standard 34.
  • compositions of fluorocarbon and fluorocarbon/hydrocarbon blends which are suitable for extending HCFC22 in accordance with this invention are used to progressively replace HCFC22 in a device containing a centrifugal compressor, then the molecular weight of the blend is also an important parameter in selecting the extender.
  • the latter should have a molecular weight in the range 75 to 95, more preferably 80 to 90 and most preferably 83 to 88.
  • blends with molecular weights within one unit of that of HCFC22 which is 86.47.
  • At least a small proportion of HCFC22 is retained as part of the refrigerant in a device even after multiple additions of the fluorocarbon comprising extender. This is especially preferable for two reasons. Firstly, HCFC22 together with the lubricating oil helps to swell the polymer seals in semi-hermetic and open devices thus minimising the loss of refrigerant. In some instances completely replacing
  • HCFC22 by an HFC or by an HFC plus hydrocarbon containing refrigerant can result in degradation of the polymer seals resulting in refrigerant leaks.
  • the degradation may take the form of excessive swelling and mechanical weakening of the seal or shrinking due to extraction of a seal component or previously dissolved HCFC22 and oil. Retaining some HCFC22 in a device helps to prevent this from happening.
  • the reliability of a compressor in a refrigeration, air conditioning or heat pump device is enhanced by the presence of "extreme pressure” (EP) additives in the lubricant such as a small quantity of an organophosphorus or organochlorine.
  • EP extreme pressure
  • CFCs and HCFCs contribute to the lubrication of compressors by acting as extreme pressure additives since they produce small quantities of metal chlorides on metal bearing surfaces under typical operating conditions. Since the level of additives required is low, even the oil used with the previous R22 or R502 charge can contain sufficient chlorine-containing compounds to give adequate protection. However, should the oil be changed, the chlorine-containing compounds will be flushed from the device thus losing their extreme pressure lubrication protection. The retention of some HCFC22 in a device is, therefore, advantageous.
  • HFC and HFC/hydrocarbon blends which are suitable for extending HCFC22 in accordance with this invention preferably comprise at least 5% of HCFC22, more preferably more than 10%.
  • Compositions of the HFC and HFC/hydrocarbon blends which are suitable for extending HCFC22 in accordance with this invention can contain optionally 5% to 95% by weight of HCFC22 with the rest of the blend comprising HFC components and optionally hydrocarbons.
  • a method of extending HFC22 in a refrigeration or air conditioning device which contains HCFC22 as a refrigerant comprising the steps of adding a refrigerant composition comprising a combination selected from one of the following mixtures:
  • a hydrocarbon additive selected from the group consisting of 2-methylpropane, propane, 2,2-dimethylpropane, n-butane, 2-methylbutane, propene, n-butene, isobutane and mixtures thereof, and optionally HCFC22.
  • a first preferred extender is selected from the following mixtures:
  • a second preferred extender is selected from the following mixtures:
  • a particularly preferred extender consists essentially of:
  • An especially preferred extender consists essentially of: R125 63%
  • a most preferred extender consists essentially of: R125 77.5%
  • Another preferred extender consists essentially of: R125 25%
  • Yet another preferred extender consists essentially of: R125 25% R32 21%
  • a preferred extender consists essentially of: R125 25%
  • Another preferred extender consists essentially of: R125 25%
  • a most preferred extender consists essentially of: R125 44%
  • a particularly preferred extender consists essentially of: R125 50%
  • An especially preferred extender consists essentially of: R125 25%
  • a preferred composition which may be used as an extender consists essentially of:
  • composition which may be used as an extender consists essentially of:
  • composition which may be used as anextender consists essentially of:
  • R125 was evaluated using NISTs Cycle D program to progressively extend R22 in a refrigerator operating under the following conditions.
  • a plot of refrigeration capacity against extender fraction relative to R22 in Chart 1 shows that the capacities of all the mixtures are better than that of pure R22.
  • a plot of refrigeration capacity against extender fraction relative to R22 in Chart 2 shows that the capacity is at least as good as or better than that of pure R22 until nearly 80% of the R22 has been replaced.
  • RS-52 (R428A) was evaluated using NIST' s Cycle D program to progressively extend R22 in a refrigerator operating under the following conditions.
  • System cooling capacity (kW) 100.00
  • Compressor isentropic efficiency 0 .750
  • Compressor volumetric efficiency 0.82
  • Pressure drop (in sat. temp.) ( 0 C): in the suction line 1.5 in the discharge line 1.5
  • Evaporator temperature ( 0 C) -35.0
  • R422A was evaluated using NIST' s Cycle D program to progressively extend R22 in a refrigerator operating under the following conditions.
  • a plot of refrigeration capacity against extender fraction relative to R22 in Chart 4 shows that the capacity is at least as good as or better than that of pure R22 until at least 80% of the R22 has been replaced.
  • R422A as an extender for R22
  • RS-44 (R424A) was evaluated using NIST' s Cycle D program to progressively extend R22 in a refrigerator operating under the following conditions.
  • RS-44 (R424A) was evaluated using NIST's Cycle D program to progressively extend R22 in an air conditioning unit operating under the following conditions.
  • a plot of refrigeration pressure against extender fraction relative to R22 in Chart 7 shows that the pressures of all the mixtures are below that of pure R22.
  • RS-44 is therefore a good extender for R22 where the discharge pressure must not exceed that of R22 because of pressure limitations set by the equipment design.
  • R407C was evaluated using NIST' s Cycle D program to progressively extend R22 in a chiller driven by a centrifugal compressor operating under the following conditions.

Landscapes

  • 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)
  • Polyurethanes Or Polyureas (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un procédé destiné à diluer progressivement le HCFC22 restant dans un appareil de réfrigération, un appareil de climatisation ou une pompe à chaleur après la fuite d'une partie de la charge de départ, par mélange de ce composé avec un frigorigène comprenant un ou plusieurs composés organofluorés et, éventuellement, du HCFC22 et un ou plusieurs hydrocarbures.
PCT/GB2007/004145 2006-11-27 2007-10-30 Diluants frigorigènes pour le hcfc22 WO2008065331A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0623551.9 2006-11-27
GB0623551A GB0623551D0 (en) 2006-11-27 2006-11-27 Refringement extenders for HCFL 22

Publications (2)

Publication Number Publication Date
WO2008065331A2 true WO2008065331A2 (fr) 2008-06-05
WO2008065331A3 WO2008065331A3 (fr) 2008-08-07

Family

ID=37636516

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2007/004145 WO2008065331A2 (fr) 2006-11-27 2007-10-30 Diluants frigorigènes pour le hcfc22

Country Status (2)

Country Link
GB (1) GB0623551D0 (fr)
WO (1) WO2008065331A2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2253685A1 (fr) * 2009-06-12 2010-11-24 Solvay Fluor GmbH Composition réfrigérante
US20110191268A1 (en) * 2007-10-12 2011-08-04 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US20160222268A1 (en) * 2014-09-25 2016-08-04 Daikin Industries, Ltd. Composition comprising hfc and hfo
US10266736B2 (en) 2010-06-25 2019-04-23 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
CN113789156A (zh) * 2021-09-26 2021-12-14 浙江巨化联州制冷科技有限公司 一种传热组合物及其应用与传热系统

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201002625D0 (en) 2010-02-16 2010-03-31 Ineos Fluor Holdings Ltd Heat transfer compositions
GB201002622D0 (en) 2010-02-16 2010-03-31 Ineos Fluor Holdings Ltd Heat transfer compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6526764B1 (en) * 2000-09-27 2003-03-04 Honeywell International Inc. Hydrofluorocarbon refrigerant compositions soluble in lubricating oil
US6606868B1 (en) * 1999-10-04 2003-08-19 Refrigerant Products, Ltd. R 22 replacement refrigerant
US20060191665A1 (en) * 2004-12-28 2006-08-31 Ponder Kenneth M Refrigerant for low temperature applications

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6606868B1 (en) * 1999-10-04 2003-08-19 Refrigerant Products, Ltd. R 22 replacement refrigerant
US6526764B1 (en) * 2000-09-27 2003-03-04 Honeywell International Inc. Hydrofluorocarbon refrigerant compositions soluble in lubricating oil
US20060191665A1 (en) * 2004-12-28 2006-08-31 Ponder Kenneth M Refrigerant for low temperature applications

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110191268A1 (en) * 2007-10-12 2011-08-04 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US8333901B2 (en) * 2007-10-12 2012-12-18 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
JP2010285620A (ja) * 2009-06-12 2010-12-24 Solvay Fluor Gmbh 冷媒組成物
AU2010202346B2 (en) * 2009-06-12 2012-06-07 Solvay Fluor Gmbh Refrigerant composition
US8444873B2 (en) 2009-06-12 2013-05-21 Solvay Fluor Gmbh Refrigerant composition
EP2253685A1 (fr) * 2009-06-12 2010-11-24 Solvay Fluor GmbH Composition réfrigérante
US10266736B2 (en) 2010-06-25 2019-04-23 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US11760911B2 (en) 2010-06-25 2023-09-19 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US10844260B2 (en) 2010-06-25 2020-11-24 Mexichem Amanco Holding S.A. De C.V. Heat transfer compositions
US9644125B2 (en) * 2014-09-25 2017-05-09 Daikin Industries, Ltd. Composition comprising HFC and HFO
US9663694B2 (en) 2014-09-25 2017-05-30 Daikin Industries, Ltd. Composition comprising HFC and HFO
US9663695B2 (en) 2014-09-25 2017-05-30 Daikin Industries, Ltd. Composition comprising HFC and HFO
US9745497B2 (en) 2014-09-25 2017-08-29 Daikin Industries, Ltd. Composition comprising HFC and HFO
US9663696B2 (en) 2014-09-25 2017-05-30 Daikin Industries, Ltd. Composition comprising HFC and HFO
US9574123B2 (en) 2014-09-25 2017-02-21 Daikin Industries, Ltd. Composition comprising HFC and HFO
US20160222268A1 (en) * 2014-09-25 2016-08-04 Daikin Industries, Ltd. Composition comprising hfc and hfo
CN113789156A (zh) * 2021-09-26 2021-12-14 浙江巨化联州制冷科技有限公司 一种传热组合物及其应用与传热系统
CN113789156B (zh) * 2021-09-26 2023-07-25 浙江巨化联州制冷科技有限公司 一种传热组合物及其应用与传热系统

Also Published As

Publication number Publication date
WO2008065331A3 (fr) 2008-08-07
GB0623551D0 (en) 2007-01-03

Similar Documents

Publication Publication Date Title
JP5830029B2 (ja) 低温冷却用の非オゾン破壊性かつ低地球温暖化係数の冷媒
EP1765953B1 (fr) Composition refrigerante
US9062237B2 (en) Refrigerant composition
JP6062061B2 (ja) 低ｇｗｐの熱伝達組成物
WO2008065331A2 (fr) Diluants frigorigènes pour le hcfc22
AU769199B2 (en) R 22 replacement refrigerant
CN111500262A (zh) 制冷剂
JPH0585970A (ja) 冷 媒
WO2007099350A1 (fr) Composition réfrigérante
EP2125986A1 (fr) Composition réfrigérante
CA2706035C (fr) Compostion frigorigene
WO2008059199A1 (fr) Compositions réfrigérantes n'épuisant pas l'ozone pour remplacer le hcfc22
EP3969535A1 (fr) Composition réfrigérante

Legal Events

Date Code Title Description
NENP Non-entry into the national phase in:

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07824389

Country of ref document: EP

Kind code of ref document: A2

122 Ep: pct application non-entry in european phase

Ref document number: 07824389

Country of ref document: EP

Kind code of ref document: A2