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WO1993007231A1 - Nouvelles compositions de pentafluoroethane et de monochlorodifluoromethane - Google Patents

Nouvelles compositions de pentafluoroethane et de monochlorodifluoromethane Download PDF

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Publication number
WO1993007231A1
WO1993007231A1 PCT/US1992/008065 US9208065W WO9307231A1 WO 1993007231 A1 WO1993007231 A1 WO 1993007231A1 US 9208065 W US9208065 W US 9208065W WO 9307231 A1 WO9307231 A1 WO 9307231A1
Authority
WO
WIPO (PCT)
Prior art keywords
compositions
refrigerant
weight percent
refrigeration
temperature
Prior art date
Application number
PCT/US1992/008065
Other languages
English (en)
Inventor
Earl August Eugene Lund
Ian Robert Shankland
Rajiv Ratna Singh
Original Assignee
Allied-Signal Inc.
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 Allied-Signal Inc. filed Critical Allied-Signal Inc.
Priority to EP92920818A priority Critical patent/EP0606342A1/fr
Priority to JP5506942A priority patent/JPH06511489A/ja
Priority to BR9206584A priority patent/BR9206584A/pt
Publication of WO1993007231A1 publication Critical patent/WO1993007231A1/fr

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

Definitions

  • This invention relates to novel compositions of pentafluoroethane and chlorodifluoromethane. These mixtures have unusual efficiency and capacity as fluids for heating and cooling.
  • Fluorocarbon based fluids have found widespread use in industry for refrigeration, air conditioning and heat pump applications.
  • Vapor compression cycles are one form of refrigeration.
  • the vapor compression cycle involves changing the refrigerant from the liquid to the vapor phase through heat absorption at a low pressure, and then from the vapor to the liquid phase through heat removal at an elevated pressure.
  • the refrigerant is vaporized in the evaporator which is in contact with the body to be cooled.
  • the pressure in the evaporator is such that the boiling point of the refrigerant is below the temperature of the body to be cooled.
  • the formed vapor is then removed by means of a compressor in order to maintain the low pressure in the evaporator.
  • the temperature and pressure of the vapor are then raised through the additional of mechanical energy by the compressor.
  • the high pressure vapor then passes to the condenser whereupon heat exchange takes place with a cooler medium and the sensible and latent heats are removed with subsequent condensation.
  • the hot liquid refrigerant then passes to the expansion valve and is ready to cycle again.
  • While the primary purpose of refrigeration is to remove energy at low temperature, the primary purpose of a heat pump is to add energy at higher temperature.
  • Heat pumps are considered reverse cycle systems because, for heating, the operation of the condenser is interchanged with that of the refrigeration evaporator.
  • chlorofluorocarbons have gained widespread use in refrigeration applications including air conditioning and heat pump applications owing to their unique combination of chemical and physical properties.
  • refrigerants utilized in vapor compression systems are either single component fluids or azeotropic mixtures.
  • the alternative or substitute materials must also possess those properties unique to the CFC's including chemical stability, low toxicity, non-flammability, and efficiency in use.
  • the latter characteristic is important, for example, in air conditioning and refrigeration where a loss in refrigerant thermodynamic performance or energy efficiency may have secondary environmental impacts through increased fossil fuel usage arising from an increased demand for electrical energy.
  • refrigerants utilized in vapor compression systems are either single component fluids or azeotropic mixtures.
  • the latter are binary mixtures, but for all refrigeration purposes behave as single component fluids.
  • Nonazeotropic mixtures have been disclosed as refrigerants for example in U.S. Patent 4,303,536 but have not found widespread use in commercial applications.
  • condensation and evaporation temperatures of single component fluids are defined clearly. If we ignore the small pressure drops in the refrigerant lines, the condensation or evaporation occurs at a single temperature corresponding to the condenser or evaporation pressure. For mixtures ' being employed as refrigerants, there is no single phase change temperature but a range of temperatures. This range is governed by the vapor-liquid equilibrium behavior of the mixture. This property of mixtures is responsible for the fact that when nonazeotropic mixtures are used in the refrigeration cycle, the temperature in the condenser or the evaporator has no longer a single uniform value, even if the pressure drop effect is ignored. Instead, the temperature varies across the equipment, regardless of the pressure drop. In the art this variation in the temperature across an equipment is known as temperature glide.
  • Another object of the invention is to provide such compositions for use in the aforementioned applications which are environmentally acceptable.
  • Still another object of the invention is to provide such compositions which exhibit a small temperature glide.
  • Yet another object of the invention is to provide such compositions which may be used as a replacement for Refrigerant 502.
  • Refrigerant 502 is a blend of 48.8 weight percent HCFC-22 and 51.2 weight percent CFC-115 (monochlorodifluoromethane) .
  • compositions comprising from about 25 to about 75 weight percent pentafluoroethane (HFC- 125) and from about 75 to about 25 weight percent ono- chlorodifluoromethane (HCFC-22) which are useful in cooling and heating applications.
  • HFC- 125 pentafluoroethane
  • HCFC-22 ono- chlorodifluoromethane
  • compositions of the invention comprise from about 30 to about 70 weight percent HFC-125 and from about 70 to about 30 weight percent HCFC-22.
  • compositions of the invention comprise from about 40 to about 60 weight percent HFC-125 and from about 60 to about 40 weight percent HCFC-22.
  • compositions of the invention comprise about 50 weight percent of HFC-125 and about 50 weight percent of HCFC-22.
  • the compositions of the invention may be used in a method for producing refrigeration which involves condensing a fluid comprising the compositions and thereafter evaporating the refrigerant in the vicinity of a body to be cooled.
  • this process is conventional.
  • compositions of the invention may be used in a method for producing heating which involves condensing a fluid comprising the compositions in the vicinity of a body to be heated and thereafter evaporating the refrigerant.
  • this process is conventional.
  • the HFC-125 and HCFC-22 components of the novel compositions of the invention are known materials, preferably they should be used in sufficiently high purity so as to avoid the introduction of adverse influences upon the properties of the system.
  • the novel compositions of the invention exhibit, at certain operating conditions, a higher refrigeration capacity than that of either of its HFC-125 or HCFC-22 components. This result is particularly surprising in view of the fact that these mixtures exhibit negative deviations from Raoult's Law which suggest lower vapor pressures and correspondingly of the invention also exhibit an unexpectedly low temperature glide.
  • compositions may include one or more additional components, such as auxiliary refrigerants or heating media, lubricants or other additives.
  • additional components may or may not form azeotropic compositions with the HFC-125 and HCFC-22 components.
  • propane which may be added to enhance solubility of lubricants (particularly mineral oils) in the HFC-125/HCFC-22 compositions of this invention. If propane is used as an additive, it should be present in an amount effective to improve the solubility of the lubricant in the claimed composition. Generally, about 1.1 to about 7.6 and, preferably about 2.2 to about 6.6 weight percent of the propane based on the weight of the HFC- 125 and HCFC-22 is effective for this purpose (or from about l to about 7 and, preferably about 2 to about 6 weight percent based on the entire composition) .
  • the propane which is present forms an azeotrope with the HFC-125 component of the compositions of the invention.
  • VLE vapor-liquid equilibrium
  • the VLE of the system was measured by charging a stainless steel cell of approximately 150 cubic centimeter volume with a known amount of HFC-125.
  • the vessel was equipped with a magnetically driven stirrer and a 0-3000 kPa pressure transducer accurate to + 0.2%.
  • the VLE cell was frozen to reduce the vapor pressure of the first component and then a known amount of HCFC-22 was added.
  • the vessel was submerged in a constant temperature bath controlled to within + 0.03K.
  • the vapor pressure measurement was recorded once thermal equilibrium was attained.
  • the vapor phase and the liquid phase samples were taken and analyzed on a gas chromatograph after shutting down the stirrer. This procedure was repeated at different HFC-125 and HCFC-22 compositions. Table I summarizes the results of these experiments.
  • the theoretical performance of a refrigerant at specific operating conditions can be estimated from the thermodynamic properties of the refrigerant using standard refrigeration cycle analysis techniques, see for example, "Fluorocarbons Refrigerants Handbook", ch. 3, Prentice-Hall. (1988), by R.C. Downing.
  • the coefficient of performance, COP is a universally accepted measure, especially useful in representing the relative thermodynamic efficiency of a refrigerant in a specific heating or cooling cycle involving evaporation or condensation of the refrigerant. In refrigeration engineering this term expresses the ratio of the useful refrigeration to the energy applied by the compressor in compressing the vapor.
  • the capacity of a refrigerant represents the volumetric efficiency of the refrigerant.
  • this value expresses the capability of a compressor to pump quantities of heat for a given volumetric flow rate of refrigerant.
  • a refrigerant with a higher capacity will deliver more cooling or heating power.
  • a similar calculation can also be performed for nonazeotropic refrigerant blends.
  • the temperature glide of the mixture compositions claimed is small enough to be negligible and does not pose a problem for conventional refrigeration units. This was an unexpected discovery since it is known that for ideal mixtures the temperature glide is approximately one-third of the boiling point difference. (Ref: P.S. Burr and G. G. Haselden, "Proceedings of the Institute of Refrigeration, pp. 18-26, Vol. 71, 1974-5) . Based on this rule, the temperature glide for the mixture compositions claimed would be expected to be about 4°F. Surprisingly, the actual temperature glide for the claimed mixtures is about 1°F which is much smaller than what would have been expected.
  • Table II depicts the relationships of COP, capacity, compressor discharge pressure and the compressor discharge temperature, respectively, as a function of the mixture composition at an average condensing temperature of 100"F.
  • Table III depicts the relationship of the same quantities as a function of compositions at an average condensing temperature of 140°F.
  • Tables II and III in the composition ranges studied, the blends provide a modest improvement in COP compared to that attainable with Refrigerant 502.
  • the blends also produce discharge temperatures and pressures similar to that produced by Refrigerant 502 used in the art. It is noted from these Tables that HCFC-22 alone gives a higher discharge temperature in a compressor. A high discharge temperature usually results in a loss of compressor reliability. We have already noted the loss in capacity with HFC-125 at high condensing temperatures.
  • the compositions of the invention give low discharge temperatures similar to those obtained with Refrigerant 502 without the loss in capacity associated with HFC-125 alone. This shows that one could replace the ozone layer destroying Refrigerant 502 with the claimed compositions of HFC-125 and HCFC- 22 in existing refrigeration machines without substantial modifications.
  • Tables II and III document the unexpected advantages that result from combining HCFC-22 with HFC- 125 in certain proportions.
  • the condensing temperatures in air cooled low temperature refrigeration systems located in hot climates are in the order of 140 ⁇ F.
  • the refrigeration capacity of the nonazeotropic mixtures containing 30 to 70 percent by weight HFC-125 is higher than that of HCFC-22 or HFC-125 alone, as the data in Table III indicate.
  • this result is surprising in view of the fact that these mixtures exhibit negative deviations from Raoult's Law which suggest lower vapor pressures and correspondingly lower refrigeration capacities.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne certaines compositions de pentafluoroéthane et de chlorodifluorométhane présentant une efficacité et une capacité inhabituelles à chauffer et refroidir, telles que des fluides de chauffage et de refroidissement. Ces compositions peuvent comporter des additifs tels que des lubrifiants, certains de ces additifs tels que le propane améliorant la solubilité des lubrifiants.
PCT/US1992/008065 1991-10-03 1992-09-23 Nouvelles compositions de pentafluoroethane et de monochlorodifluoromethane WO1993007231A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP92920818A EP0606342A1 (fr) 1991-10-03 1992-09-23 Nouvelles compositions de pentafluoroethane et de monochlorodifluoromethane
JP5506942A JPH06511489A (ja) 1991-10-03 1992-09-23 ペンタフルオロエタンおよびモノクロロジフルオロメタンを含む新規な組成物
BR9206584A BR9206584A (pt) 1991-10-03 1992-09-23 Novas composições compreendendo penta fluor-etano e mono-cloro-di-fluor-metano e processos para produzir refrigeração e aquecimento

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US77068891A 1991-10-03 1991-10-03
US770,688 1991-10-03

Publications (1)

Publication Number Publication Date
WO1993007231A1 true WO1993007231A1 (fr) 1993-04-15

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PCT/US1992/008065 WO1993007231A1 (fr) 1991-10-03 1992-09-23 Nouvelles compositions de pentafluoroethane et de monochlorodifluoromethane

Country Status (8)

Country Link
EP (1) EP0606342A1 (fr)
JP (1) JPH06511489A (fr)
CN (1) CN1070936A (fr)
AU (1) AU2672292A (fr)
BR (1) BR9206584A (fr)
CA (1) CA2120237A1 (fr)
MX (1) MX9205556A (fr)
WO (1) WO1993007231A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5616276A (en) * 1990-07-26 1997-04-01 E. I. Du Pont De Nemours And Company Azeotrope-like refrigerants with chlorodifluoromethane, pentafluoroethane, and C2 -C4 hydrocarbon
US5723057A (en) * 1995-02-17 1998-03-03 Elf Atochem S.A. Pseudo-azeotropic mixture of chlorodifluoromethane, 1,1,1-trifluoroethane and pentafluoroethane, and its application as a refrigerant in low-temperature refrigeration
US6106740A (en) * 1995-08-18 2000-08-22 Imperial Chemical Industries Plc Non-azeotropic refrigerant composition of CO2, R-125, R-143a and R-22
US6299792B1 (en) 1998-01-16 2001-10-09 E. I. Du Pont De Nemours And Company Halogenated hydrocarbon refrigerant compositions containing polymeric oil-return agents

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104482598A (zh) * 2014-12-22 2015-04-01 常熟市兴华机电设备安装工程有限责任公司 一种高功效节能型空调

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0331760A1 (fr) * 1987-09-21 1989-09-13 Daikin Industries, Limited Refrigerant
US4978467A (en) * 1989-09-26 1990-12-18 Allied-Signal Inc. Azeotrope-like compositions of pentafluoroethane and difluoromethane
GB2247462A (en) * 1990-08-29 1992-03-04 Star Refrigeration Two component refrigerant
WO1992011338A1 (fr) * 1990-12-17 1992-07-09 E.I. Du Pont De Nemours And Company Compositions d'hydrocarbures fluores a point d'ebullition constant
EP0419042B1 (fr) * 1989-09-12 1994-10-19 Star Refrigeration Ltd. Réfrigérant à trois composants
EP0492777B1 (fr) * 1990-12-05 1995-05-10 Star Refrigeration Ltd. Refrigérant multicomposant

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0331760A1 (fr) * 1987-09-21 1989-09-13 Daikin Industries, Limited Refrigerant
EP0419042B1 (fr) * 1989-09-12 1994-10-19 Star Refrigeration Ltd. Réfrigérant à trois composants
US4978467A (en) * 1989-09-26 1990-12-18 Allied-Signal Inc. Azeotrope-like compositions of pentafluoroethane and difluoromethane
GB2247462A (en) * 1990-08-29 1992-03-04 Star Refrigeration Two component refrigerant
EP0492777B1 (fr) * 1990-12-05 1995-05-10 Star Refrigeration Ltd. Refrigérant multicomposant
WO1992011338A1 (fr) * 1990-12-17 1992-07-09 E.I. Du Pont De Nemours And Company Compositions d'hydrocarbures fluores a point d'ebullition constant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN 20 September 1988 & JP,A,63 105 088 ( SANYO ELECTRIC ) 10 May 1988 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5616276A (en) * 1990-07-26 1997-04-01 E. I. Du Pont De Nemours And Company Azeotrope-like refrigerants with chlorodifluoromethane, pentafluoroethane, and C2 -C4 hydrocarbon
US5723057A (en) * 1995-02-17 1998-03-03 Elf Atochem S.A. Pseudo-azeotropic mixture of chlorodifluoromethane, 1,1,1-trifluoroethane and pentafluoroethane, and its application as a refrigerant in low-temperature refrigeration
US6106740A (en) * 1995-08-18 2000-08-22 Imperial Chemical Industries Plc Non-azeotropic refrigerant composition of CO2, R-125, R-143a and R-22
US6299792B1 (en) 1998-01-16 2001-10-09 E. I. Du Pont De Nemours And Company Halogenated hydrocarbon refrigerant compositions containing polymeric oil-return agents

Also Published As

Publication number Publication date
AU2672292A (en) 1993-05-03
CN1070936A (zh) 1993-04-14
BR9206584A (pt) 1995-11-21
EP0606342A1 (fr) 1994-07-20
MX9205556A (es) 1993-04-01
JPH06511489A (ja) 1994-12-22
CA2120237A1 (fr) 1993-04-15

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