CA2086841C - Near-azeotropic blends for use as refrigerants - Google Patents

Near-azeotropic blends for use as refrigerants Download PDF

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CA2086841C
CA2086841C CA002086841A CA2086841A CA2086841C CA 2086841 C CA2086841 C CA 2086841C CA 002086841 A CA002086841 A CA 002086841A CA 2086841 A CA2086841 A CA 2086841A CA 2086841 C CA2086841 C CA 2086841C
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weight percent
refrigerant
vapor
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Donald Bernard Bivens
Mark Brandon Shiflett
Akimichi Yokozeki
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • 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
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/122—Halogenated 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
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/124—Fluorinated cyclic 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
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/128—Perfluorinated 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
    • C09K2205/22—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
    • C09K2205/32—The mixture being azeotropic

Abstract

A near azeotropic composition which is a blend of pentafluoroethane and 1,1,1-trifluoroethane with 1,2,2,2-tetrafluoroethane or 1,1,2,2-tetrafluoroethane in the proportions of 35 to 65 weight percent of pentafluoroethane, 30 to 60 weight percent of 1,1,1-trifluoroethane and 3 to 15 weight percent of 1,1,2,2-tetrafluoroethane or 1,2,2,2-tetrafluoroethane.

Description

208b841 s'''-' WO 92/01762 ~ PGT/US91/04100 .. _ TITLE
NEAR-AZEOTROPIC BLEtIDS FOR USE AS REFRIGERANTS

The present invention relates to ternary and higher blends of fluorinated hydrocarbons and more specifically to near-azeotrope constant-boiling blends and expands upon refrigerant compositions for cooling and heating applications, as heretofore described in U.S. Patent No. 4,810,403. Such blends are useful as refrigerants, heat transfer media, gaseous dielectrics, expansion agents, aerosol propellants and power cycle working fluids. Concern over the ozone __ 2o depletion potential of certain halocarbons has resulted in a search for alternative compounds having ' lower ozone depletion potentials. A present day commercial binary azeotrohe refrigerant widely used in supermarket refrigerators consists of 48.8 wt%
_ 25 chlorodifluoromethane (HCFC-22) and 51.2 wt$
chloropentafluoroethane ((:FC-115) and is generally referred to as Refrigerant:-502. Due to the presence of chlorine in CFC-115, C(:1F2CF3, is expected to be subject to reduced usage because of its high ozone 30 depletion potential. Additionally chlorine containing medium to low temperature refrigerants which may be subject to reduced usage could be replaced with all HFC containing blends described within.
In refrigeration applications, refrigerant 3~ is often lost through lead;s during operation, such as 208684a 2 PCT/US91/0410D--~

through shaft seals, hose connections, solder joints, and broken lines. In~addition, refrigerant may be released to the atmosphere during maintenance procedures performed on refrigeration equipment.
Most commercial refrigerants which are now ' used are pure fluids or azeotropes, many of these refrigerants have ozone depletion potentials when released to the atmosphere. Some nonazeotropic blends of refrigerants may also be used but they have the l0 disadvantage of changing composition when a portion of the refrigerant charge is leaked or discharged to the atmosphere. Should these blends contain a flammable component, they could also become flammable due to the change of composition which occurs during the leakage of vapor from refrigeration equipment. Refrigeration equipment operation could also be adversely affected due to this change in composition and vapor pressure which results from fractionation.
What is needed, therefore, are substitute refrigerants which maintain important refrigerant properties of vapor pressure: and nonflammability over a wide range of composition::, while also having reduced ozone depletion potEantial.
SUMMARY OF TF~E INVENTION
According to the present invention, near-azeotrope constant-boi7Ling blends have been discovered comprising effeci:ive amounts of pentafluoroethane (HFC-125) and 1,1,1-trifluoroethane (HFC-143a) with one or more of the compounds set forth in Table I:

~~ 92/01762 Generally Chemical Name Accepted Nomenclature chlorodifluoromethane HCFC-22 1,2,2,2-tetrafluoroethane HFC-134a 1,1,2,2-tetrafluoroethane HFC-134 1-chloro-1,1,2,2-tetra.fluoroethane HFC-124a 1-chloro-1,2,2,2-tetrafluoroethane HFC-124 1,1,1,2,3,3,3-heptafluoropropane HFC-227ea 1,1,1,2,2,3,3-heptafluoropropane HFC-227ca perfluorocyclopropane FC-C216 The near-azeotrope constant-boiling compositions are blends of HFC-125 and HFC-143a with any one of HCFC-22, HFC-134a, HFC-134, HFC-124a, HFC-124, HFC-227ea, HFC-227ca, and FC-C216 or mixtures thereof as set forth below. The compositions are chosen such that the blends have vapor pressures substantially equal to the vapor pressure of Refrigerant-502 and other medium to low temperature refrigerants, over a temperature range as encountered in their use as refrigerants such as -50 to 100 degrees Celcius. The compositions have ozone depletion potentials (ODP) and global warming potentials (GWP) of 0 to 0.02 and 0.5 to 1.0 respectively which are substantially lower than the Refrigerant-502 value of 0.25 ODP and 5.1 GWP.
Additional, near-azeotrope constant-boiling blends have been discovered comprising effective amounts of chlorodifluoromethane (HCFC-22) and/or pentafluoroethane (HFC~-125) with one or more of the compounds set forth in Tables I and II:

...
TABLE: II
(3enerally Chemical Name ~~ccepted Nomenclature propane HC-290 octafluoropropane F=C-218 fluoroethane HFC-161 The near azeotrope constant-boiling compositions are blends of HCFC-22 with propane and HFC-125, HC;FC-22 with HFC-143a and HFC-134a, or HCFC-22 with HFC-143a and FC-218. Also, a near-azeotrope constant-boiling composition is a blend of HFC-125 with HFC-161 and HFC-134a. The compositions are chosen such that the blends have vapor pressures substantially equal to the vapor pressure of Refrigerant-502 and other medium to low temperature refrigerants, over a temperature range as encountered in their use as refrigerants such as a -50 to 100 degree Celsius.
The compositions have ozone depletion potentials (ODP) lower than Refrigerant-502, however, blends formulated with octafluoropropane may have global warming potentials lower, or equal to Refrigerant-502 depending on the composition of octafluoropropane.
The near-azeotropic blends may also be used to produce heat by condensing the composition in the vicinity of the body to be heated and thereafter evaporating the condensate.
The use of near-azeotropic blends minimizes the problem of component fractionation and handling in system operations.
Finally, the near-azeotropic blends can be formulated to offer the same advantage as Refrigerant-502 and other medium to low temperature refrigerants as being nonflammable at room temperature and atmospheric pressure.
c -4a-A further aspect of the invention is as follows:
a near-azeotropic composition consisting essentially of pentafluoroethane (HFC-125), 1,1,1-trifluoroethane (HFC-143a) and at least one fluorocarbon selected from the group consisting of 1,1,1,2-tetrafluoroethane (HFC-134a) and 1,1,2,x'.-tetrafluoroethane (HFC-134), in the proportions of 35-65 weight percent HFC-125, 30-60 weight percent, 1,1,1-trifluoroethane (HFC-143a) and 3 to 15 weight percent of the at least one fluorocarbon selected from HFC-134 and HFC-134a.
It is to be noted that HFC-134a is alternatively referred to herein as 1,1,1,2-tetrafluoroethane and 1,2,2,2-tetrafluoroethane.
E

'~? 92/01762 2 p 8 6 8 41 ,_5-DETAILED DESC~tIPTION OF THE INVENTION
Hy refrigeration is meant the utilization of physical change in a substance to produce a cooling or heating effect. The physical change can be, for example, a change from the solid state to the liquid state or a change from the liquid state to the vapor state or the reverse order.
By refrigerant is meant the substance which undergoes physical change in refrigeration.
By ozone depletion potential is meant the ratio of the calculated ozone depletion in the stratosphere resulting from the emission of a compound compared to the ozone depletion potential resulting from the same rate of eamission of CFC-11 which is set at 1Ø A method of calculating ozone depletion potential is described in "'The Relative Efficiency of a Number of Halocarbons for Destroying Stratospheric Ozone"', by D. J. Wuebbles, Lawrence Livermore Laboratory report UCID-~18924, January, 1981, and "'Chlorocarbon Emission Scenarios: Potential Impact on Stratospheric Ozone"', by D. J. Wuebbles, Journal Geophysics Research, 88, 1433-1443, 1983.
By nonflammable is meant a gas mixture in air which will not burn when subjected to a spark igniter as described in "'Limits of Flammability of Gases and Vapours, Bulletin 503, H.F. Coward et al., Washington, U.S. Bureau of Mines, 1952.
By "'vapor preasures substantially equal to the vapor pressure of F;efrigerant-502 and other medium to low temperature refrigerants"' is meant a vapor pressure which is plus or minus twenty-five percent of the vapor pressure of F;efrigerant-502 and other medium to low temperature refrigerants at the same temperature within the range of -50 to 100 degrees Celsius.

WO 92/01762 , PCT/US91/0410~-By substantially lower ozone depletion potential than the ozone depletion of Refrigerant-502 is meant an ozone depletion potential at least fifty percent less'than the ozone depletion potential of Refrigerant-502, i.e. less than 0.125.
By substantially lower global warming potential than the global warming potential of Refrigerant-502 is meant a global warming potential at least fifty percent less than the global warming potential of Refrigerant-502, i.e., less than 2.55.
As mentioned above, when a refrigerant blend contains a flammable component, the possibility of either the discharged vapor or the remaining refrigerant upon leakage becoming flammable constitutes a highly undesirable safety hazard. The present compositions can be so formulated that the lowest boiling and highest boiling components are nonflammable so that even when the intermediate boiling component is flammable, not only is the original composition nonflammable, but additionally, neither the leaking vapor nor the remaining refrigerant becomes flammable.
The present invention provides near-azeotropic blends which have vapor pressures near that of Refrigerant-502 and other medium to low temperature refrigerants and surprisingly even after an 80 percent evaporation loss by weight. A vapor pressure/temperature relation similar to that of Refrigerant-502 and other medium to low temperature 3o refrigerants is particularly desirable since much existing refrigeration equipment which has b=- n designed to use Refrigerant-502 and other me am to low temperature refrigerants can also use the refrigerants of the present invention with little or no modification.

~O 92/01762 2 0 8 6 8 4 1 pCT/L1S91/04100 The preferred halocarbon components in the blends are listed in the Table III:
Boiling Refrigerant Chemical Formula Pt j'C) DP GWP

R-502 CHC1F2 CC1F2CF3 -50.0 .25 5.1 HFC-125 CHF2CF3 48.5 .0 .65 HFC-143a CF3CH3 -47.6 .0 .76 HCFC-22 CHC1F2 -40.8 .05 .37 HFC-134a CF3CH2F -26.5 .0 .29 HFC-134 CHF2CHF2 -19.7 .0 .30 HFC-124a CHF2CC1F2 -10.2 .02 .10 HFC-124 CHC1FCF3 -12.0 .02 .10 HFC-227ea CF3CHFCF3 -18.0 .0 HFC-227ca CF3CF2CHF2 -17.0 .0 HFC-161 CH3CFH2 -37.1 .0 FC-C216 CF2CF2CF2 (cyclic) -31.5 .0 FC-218 CF3CF2CF3 -36.5 .0 HC-290 CH3CH2CH3 -42.1 .0 The blends of the instant invention comprise HCFC-22 and/or HFC-125 with one or more of the others from Table III.
The near-azeotropic blends of the instant invention can be prepared by any convenient method including mixing or combining the desired component amounts. A preferred .method is to weigh the desired component amounts and 'thereafter combine them in an appropriate container.
The near-aze~otropic blends of the present invention have the following compositions:
- 35 to 65, preferalbly 50 to 60, and most preferably 55.0 weight percent HFC-125: 30 to 60, preferably 35 to ~45, and most preferably 40.0 WO 92/01762 ~ ~ ~ ~ ~ '~ -8- PCT/US91/04100-weight percent HFC-143a; and 3 to 15, preferably 3 to 10, and most preferably 5.0 weight percent HFC-134a.

- 35 to 65, preferably 50 to 60, and most preferably 55.0 weight percent HFC-125: 30 to 60, preferably 35 to 45, and most preferably 40.0 weight percent HFC-143a; and 3 to 15, preferably 3 to 10, and most preferably 5.0 weight percent HFC-134.

35 to 65, preferably 50 to 60, and most -preferably 55.0 weight percent HFC-125: 30 to 60, preferably 35 to 45, and most preferably 40.0 weight percent HFC-143a; and 3 to 15, preferably 3 to 10, and most preferably 5.0 weight percent HFC-124a.

- 35 to 65, preferably 50 to 60, and most preferably 55.0 weight percent HFC-125; 30 to 60, preferably 35 to 45, and most preferably 40.0 weight percent HFC-143a; and 3 to 15, preferably 3 to l0, and most preferably 5.0 weight percent HFC-124.

- 35 to 65, preferably 50 to 60, and most preferably 55.0 weight percent HFC-125; 30 to 60, preferably 35 to 45, and most preferably 40.0 weight percent HFC-143a; and 3 to 15, preferably 3 to 10, and most preferably 5.0 weight percent HFC-227ea.

- 35 to 65, preferably 50 to 60, and most preferably 55.0 weight percent HFC-125: 30 to 60, 3o preferably 35 to 45, and most preferably 40.0 weight percent HFC-143a; and 3 to 15, preferably 3 to l0, and most preferably 5.0 weight percent HFC-227ca.

- 35 to 65, preferably 50 to 60, and most preferably 55.0 weight percent HFC-125; 30 to 60, -~ 92/01762 ~ 6 ~ ~ ~ pCT/US91/04100 -g-preferably 35 to 45, and most preferably 40.0 weight percent HF'C-143a: and 3 to 15, preferably 3 to 10, and most: preferably 5.0 weight percent FC-CZ16.
~ 5 to 30, preferably 15 to 25, and most preferably 20.0 weight percent HFC-125; 30 to 60, preferably 30 to 40, and most preferably 35.0 weight percent HFC-143a; and 30 to 55, preferably 40 to 50, and most preferably 9.5.0 weight percent HCFC-22.
- 30 to 55, preferably 40 to 50, and most preferably 45.0 weight percent HCFC-22: 30 to 60, preferably 45 to 55, and most preferably 50.0 weight percent HF'C-143a; and 3 to 15, preferably 3 to 10, and most: preferably 5.0 weight percent HFC-134a.
- 1 to 98.9, preferably 30 to 85, and most preferably 45 to 65 weight percent HCFC-22; 0.1 to 15, preferably 1 to 10, and most preferably 2 to 5 weight percent propane; and 1 to 98.9, preferably 14 to 69, and most preferably 33 to 53 weight percent HF'C-125.
- 60 to 90, preferably 75 to 85, and most preferably 80.0 weight percent HFC-125: 5 to 20, preferably 10 to 15, and most preferably 15.0 weight percent HF'C-161; and 3 to 15, preferably 3 to 10, and most preferably 5.0 weight percent HFC-134a.
- 30 to 50, preferably 35 to 45, and most preferably 37.0 weight percent HCFC-22; 20 to 60, 3o preferably 25 to 40, and most preferably 28.0 weight percent HF'C-143a; and 10 to 45, preferably to 40, and most preferably 35.0 weight percent FC-218.
There are other ternary and higher blends having these desirable: characteristics that could be fonaulated by those skilled in the art from the WO 92/01762 2 ~ ~ ~ 8 41 p~/US91/0410(i-halocarbons defined and exemplified herein. For example, other blends that may be formulated for the purposes of this invention are:
TABLE IV
Lictuid Weight Percentage Most Blend Components Acceptable Preferred Preferred HFC-125/HFC-143a/ 35-65/30-60/ 45-55/35-45/ 50/40/5/5 HFC-134/HFC-134a 3-15/3-15 3-10/3-10 HFC-125/HFC-143a/ 35-65/30-60/ 35-50/30-40/ 40/35/5/20 HFC-134a/HCFC-22 3-15/30-55 3-10/15-25 HFC-125/HFC-143a/ 35-65/30-60 45-55/30-40/ 50/35/10/5 HFC-134a/HFC-124a 3-20/3-15 5-15/3-10 In addition, more than one halocarbon can be selected from each of the temperature ranges. The objective of this description is not to identify every possible blend composition, but to illustrate our discovery of the unexpected properties that the ternary (or higher) blends can take on, depending on the components, and the chosen compositions.
The refrigerant of the instant invention can be prepared by a simple mixing process as is well known to those skilled in the art.
Specific examples of the present invention will now be set forth. Unless otherwise stated, all percentages are by weight. It is to be understood that these examples are merely illustrative and are in no way to be interpreted as limiting the scope of this invention.

,.
..~(O 92/01762 t PCT/US91/04100 Impact of Vapor Leakage on Vapor Pressure at 24'C.
TABLE
V

V~ or Press ures Refrigerant/ 0% Eva porated80% Evaporated Composition _p,sia psia (KPaI Chan (KPa) a R-502 171.1 (1180) 171.1 (1180)0.0 HFC-125/HFC-143x/ 176.2 (1215) 165.2 (1139)6.2 HFC-134x(55/40/5) HFC-125/HFC-143x/ 176.3 (1216) 164.3 (1133)6.8 HFC-134(55/40/5) HFC-125/HFC-143x/ 179.0 (1234) 173.4 (1196)3.1 HFC-124x(55/40/5) HFC-125/HFC-143x/ 178.2 (1229) 169.1 (1166)5.1 HFC-124(55/40/5) HFC-125/HFC-143x/ 179.1 (1235) 171.5 (1182)4.2 HFC-227ea(55/40/5) HFC-125/HFC-143x/ 179.5 (1238) 174.8 (1205)2.6 FC-C216(55/40/5) HFC-125/HFC-143x/ 170.3 (1174) 160.1 (1104)6.0 HCFC-22(20/35/45) HCFC-22/HFC-143x/ 160.8 (1109) 156.8 (1081)4.0 HFC-134a(45/50/5) HCFC-22/Propane/ 206.3 (1422) 187.4 (1292)9.2 .

HFC-125(45/10/45) HFC-125/HFC-161/ 194.1 (1338) 181.7 (1253)12.4 HFC-134x(80/15/5) HCFC-22/HFC-143x/ 174.7 (1205) 160.0 (1103)8.4 FC-218(37/28/35) * 87% evaporated Example 1 demonstrates that all of the near-azeotropic blends of the present invention exhibit very low vapor pressure changes after 80 or PCT/US91 /04100-..

more percent by weight of the charge was leaked away.
This vapor pressure versus leak performance behavior closely approximates that of a Refrigerant-502 alone.
The vapor pressure performance indicates that the near-azeotropic blends would maintain their vapor pressure characteristics, even if 80 weight percent of the refrigerant were to be lost.
HFC-227ca is very similar to HFC-227ea and can be substituted therefore in similar proportions.

"''~ 92/01762 PCT/US91/04100 EXAMPLE

TABLE VI

efriaerant Perf ormance compr..aor Hxit ~J R.fri'vrant Capacity COP Praasur.l.mp D?

Composition Btulmin osia (KPa) ~~ ~QCZ
(kW) R-302 80.1(1107)1.19 282(1911) 239(113).0 (.0) BFC-123 82.2(1462)1.69 327(2233) 223(106).0 (.0) HFC-125/8PC-113x/ 82.7(133)1.82307(2111) 227(108).8 (.) 1 8FC-131a (33/10/3) ~

!~C-12518lC-113x/ 82.6(1431)1.83307(2117) 229(109)1.1 (.6) mro-131 (ssllols) ~C-123/BTC-113x1 80.3(1111)1.8230i(2096y 229(109)2.0(1.0) 8FC-121 (s5J1015) 1 ~C-125/8lrC-113x1 11.1(1130)1.81307(2117) 226(108)1.1 (.7) ~C-227sa (33/1013) iBrC-12311~C-113x/ 85.6(1501)1.93291(Z008) 233(121).7 (.1) BC1C-22 (20/33113) dCtC-221~C-113x1 81.1(1123)1.96277(1910) 256(123).6 (.3) ~C-131a (13150/5) BCTC-22/Propaa.l 80.1(1107)1.88290(1999) 253(123)1.6 (.9) ~C-125 (13/10/15) ~C-1251~C-1611 71.3(1309)1.81291(2027) 239(115)1.5 (.e) 8!'C-131a (80/15/3) 2 9C!'C-22/~C-113x/ 79.1(1395)1.90212(1911) 232(111).1 (.l) FC-218 (33/10/23) Conditions test were run under:

Condenser Temp 11 5'F (46'C) Evaporator Temp -3 0'F (-34'C) 30 Suction superheated o Temp 9 5'F (35'C) t Heat Exchanger used n refrigeration cycle i Compressor Efficien cy assumed 1.0 * based on a compres sor displacementof 3.5 ft3/min (0.099 m3/min) 35 ** represents condens ing temperature differential across condenser 208b841 Example 2 data suggest that the near-azeotropic blends compare quite favorably with the commercial Refrigerant-502 refrigeration performance. Also, pentafluoroethane (HFC-125), the refrigerant recognized by the refrigeration industry as a plausible substitute for Refrigerant-502 has a 10-15 percent decrease in energy efficiency. Energy efficiency is measured by coefficient of performance (COP). Therefore, the present blends of l0 chlorodifluoromethane (HCFC-22) and/or pentafluoroethane (HFC-125) with one or more additional components exhibit a substantial improvement in energy efficiency. All the blends have better energy efficiencies than pentafluoroethane (HFC-125) alone and some better than Refrigerant-502.
HCFC-124a is very similar to HCFC-124 and can be substituted therefore in similar proportions, HFC-227ca is very similar to HFC-227ea and can be substituted therefore in similar proportions, and FC-C216 can be substituted as a third component giving similar refrigeration performance.

A blend was prepared consisting of liquid concentrations of 57.9% pentafluoroethane (HFC-125) and 42.1% 1,1,1-trifluoroethane (HFC-143a). The vapor pressure of the blend was 185.5 psia (1279 KPa) at 24 deg Celcius. After 84.6% of the initial blend charge was lost via a vapor leak, the liquid composition had changed to 53.2% HFC-125 and 46.8% HFC-143a. The vapor composition of HFC-143a was 39.1% initially and increased to 44.3%. The vapor pressure decreased to 172.5 psia (1189 KPa). The conclusion of this test was the HFC-143a composition would continue to increase during the remainder of the leak and this blend will become flammable; therefore, a third %~O 92/01762 O 8 6 8 't ~ PCT/US91/04100 component is necessary when blending HFC-125 and HFC-143a to prevent the blend from becoming flammable.

A blend was prepared consisting of liquid concentrations of 55.8% pentafluoroethane (HFC-125), 38.4% 1,1,1-trifluoroethane (HFC-143a), and 5.8%
1,2,2,2-tetrafluoroethane (HFC-134a). The ozone depletion potential of the blend is 0 and the global l0 warming potential was .calculated to be 0.68. Compared with Refrigerant-502 the blend has no ozone depletion potential and a 87% reduction in global warming potential. The vapor pressure was within 5% of the vapor pressure of Refrigerant-502 over the temperature range of -50 - 100 deg Celcius. At 24 deg Celcius, the blend had a vapor pressure of 176.2 psia (1215 KPa) compared with a vapor pressure of 171.1 psia (1180 KPa) for Refrigerant-502.
To illustrate the surprisingly small changes in vapor pressure with compositional changes that occur during vapor leaks, vapor was allowed to leak from a suitable container holding the liquid blend and equilibrium vapor. After 96% of the initial blend charge had been lost via the vapor leak, the liquid compositions had changE;d to 45.9% HFC-125, 37.3%
HFC-143a, and 16.8% HFC:-134a. The vapor pressure after an 80% leak had decreased to 165.2 (1139 KPa) at 24 deg Celcius, being within 3.5% of the Refrigerant-502 vapor pressure.
3o To illustrate: the nonflammability of the blend, liquid and vapor samples were analyzed at the beginning and end of the leak test as well as vapor samples taken at blend charge weight losses of 5 to 95% in increments of 5%. The highest HFC-143a concentration was 39.2% in the vapor at 69.6% weight loss. At this point, the total vapor content was 53.8% HFC-125, 39.2% HFC-143a, and 7.0% HFC-134a. The lower flammability limit at this point of HFC-125 and HFC-143a is above 39.2% at room temperature, therefore, with only 39.2% HFC-143a the blend is nonflammable at room temperature and atmospheric pressure.

Another blend was prepared consisting of liquid compositions of 53.7% pentafluoroethane (HFC-125), 41.0% 1,1,1-trifluoroethane (HFC-143a), and 5.3% 1,1,2,2-tetrafluoroethane (HFC-134). The ozone depletion potential of the blend is 0 and the global warming potential was calculated to be 0.68. Compared with Refrigerant-502 the blend has no ozone depletion potential and a 87% reduction in global warming potential. The vapor pressure of the blend was 176.3 psia (1216 KPa) at 24 deg Celcius compared with 17 1.1 psia (1180 KPa) for Refrigerant-502. After 97.7% of the initial blend charge was lost via a vapor leak, the liquid compositions had changed to 43.3% HFC-125, 39.0% NFC-143a, and 17.7% HFC-134. The vapor pressure after 80% leak had decreased to 164.3 psia (1133 KPa) at 24 deg Celcius, being within 6.4% of the Refrigerant-502 vapor pressure. The highest HFC-143a concentration was 42.7% in the vapor at 85% weight loss. At this point, the total vapor content was 51.0% HFC-125, 42.7% HFC-143a, and 6.3% HFC-134.
Again, experimentally, th::~ maximum nonflammable concentration of HFC-143a .gin HFC-125 at any air concentration is above 42.7% at room temperature;
therefore, with only 42.7% HFC-143a, the blend is nonflammable at room temperature and atmospheric pressure.

~0 92/01762 2 O g 6 g 4 1 _.17-Another blend was prepared consisting of liquid compositions of 20.7% pentafluoroethane (HFC-125), 35.7% 1,1,7.-trifluoroethane (HFC-143a), and 43.6% chlorodifluoromesthane (HCFC-22). The ozone depletion potential waa calculated to be 0.02 and the global warming potential 0.56. A 92% and 89%
reduction in ozone depletion and global warming potentials, respectively. The vapor pressure of the l0 blend was 170.3 psia ('1174 KPa) at 24 deg Celcius compared with 171.1 ps~ia (1180 KPa) for Refrigerant-502. After 87 % of the initial blend charge was lost via a vapor leak, the liquid composition had changed to 8.6% HFC-125, 30.3%
HFC-143a, and 61.1% HC'FC-22. The vapor pressure had decreased to 160.1 psi.a (1104 KPa) at 24 deg Celcius being within 6.5% of the Refrigerant-502 vapor pressure. The highest. HFC-143a concentration was 36.9% in the vapor at 46.4% weight loss, again being a nonflammable blend at room temperature and atmospheric pressure.

A blend was prepared consisting of liquid concentrations of 37.2% chlorodifluoromethane (HCFC-22), 28.1% 1,1,1-trifluoroethane (HFC-143a), and 34.7% octafluoropropane (FC-218). The ozone depletion of the blend is 0.02 and the global warming potential is dependent on the concentration of FC-218. Compared with Refrigerant-502 the blend has lower ozone depletion potential and may be formulated to have lower or equal global warming potential to Refrigerant-502. At 24 deg Celcius, the blend had a vapor pressure of 174.7 Asia (1205 KPa) compared with the vapor pressure of 171.1 psia (1180 KPa) for Refrigerant-502.

WO 92/01762 ~ PCT/US91/04100-To illustrate the surprisingly small changes in vapor pressure with compositional changes that occur during vapor leaks, vapor was allowed to leak from a suitable container holding the liquid blend and equilibrium vapor. After 95.6% of the initial blend charge had been lost via the vapor leak, the liquid compositions had changed to 50.3% HCFC-22, 30.3%
HFC-143a, and 19.4% FC-218. The vapor pressure after an 80% leak had decreased to 168.4 psia (1161 KPa) at 24 deg Celcius, being within 2% of the Refrigerant-502 vapor pressure. Due to the increase in HFC-143a liquid composition the vapor was allowed to continue leaking. Initial liquid compositions were again measured at 50.7% HCFC-22, 30.9% HFC-143a, and 18.4%
FC-218. After 94.5% of the blend charge at the above liquid compositions had been lost after further evaporation via a vapor leak, the liquid compositions had changed to 74.0% HCFC-22, 25.4% HFC-143a, and 0.6%
FC-218. Again, the vapor pressure after an 80% leak had decreased to 160.0 psia (110 3 KPa) at 24 deg Celsius, being within 6.5% of the Refrigerant-502 vapor pressure,.
To illustrate the nonflammability of the blend, liquid and vapor samples were analyzed at the beginning and end of both leak tests as well as vapor samples taken at blend charge weight losses of 5 to 95% in increments of 5%. The highest HFC-143a concentration was 33.4% in the vapor at 78.8% weight loss during the continued leak test. At this point, the total vapor content was 56.4% HCFC-22, 33.4%
HFC-143a, and 10.2% FC-218. Experimentally, the maximum nonflammable concentration of HFC-143a in HFC-125 at any air concentration is above 33.4%
HFC-143a at room temperature, therefore, with only 33.4% HFC-143a, the blend is nonflammable at room temperature and atmospheric pressure.

~~O 92/01762 ~ ~ ~ $ 4 1 -1.9-A commercial icemaker was used to evaluate the performance of the near-azeotrope blends with Refrigerant-502. liigh and low side pressure were measured as well as inlet and exit temperature around the condenser, evaporator, and compressor. The energy consumption was measured and the quality and quantity of ice produced. For similar operating conditions the blends o~f HCFC-22/HFC-143a/HFC-125, HFC-125/HFC-143a/HFC-134a, and HFC-125/Propane/HCFC-22 performed essentially the same as Refrigrant-502.
EXAMgLE 9 -~ COMPARATIVE EXAMPLE
A study shows. that a mixture of HCFC-22, propane, and HFC-125 at: the following composition is constant boiling. Allowing 50 weight percent of the mixture to leak out as vapor at room temperature the vapor pressure changes less than 10 percent. (IQ) is initial liquid composition, (FQ) is final liquid 2o composition, (1-5) is vapor compositions, (VP) is vapor pressure, (DP) is. change in vapor pressure from original mixture, and (leakage) represents the weight % leakage.
TABLE VII

SAMPL E LEAKAGE COMPOSIT ION (Weigfit %) VP DP

HCFC-22;~ HFC-125 propane sia IQ 0 90.C1 8.0 2.0 164.3 ---1 10 84.Ei 11.8 3.5 163.3 0.6 2 20 85.i' 11.1 3.2 162.3 1.2 3 30 86.ft 10.4 2.8 161.3 1.8 4 40 88.7. 9.5 2.4 160.1 2.6 5 50 89.4 8.6 2.0 159.0 3.2 FQ 50 93.i~ 5.3 1.0 159.0 3.2 ~ ~ ~
~ ~ ~
~

TABLE
VIII

SAMPLE LEAKAGE COMPOSI TION (Weight %1 VP DP

HCFC-22 HFC-,~5 o ane sia IQ 0 70.0 28.0 2.0 178.8 ---1 10 60.7 35.9 3.4 177.5 0.7 2 20 62.1 34.8 3.0 176.2 1.5 3 30 63.7 33.6 2.8 174.8 2.2 4 40 65.5 32.1 2.4 173.1 3.2 5 50 67.6 30.3 2.1 171.4 4.1 FQ 50 77.2 21.8 1.1 171.4 4.1 TABLE
IX

SAMPLE LEAKAGE COMPOSI TTON (Weight %~ VP DP

HCFC-22 HFC-125 Propane sia IQ 0 50.0 48.0 2.0 191.3 ---1 10 41.9 54.8 3.3 190.2 0.6 2 20 42.9 54.1 3.0 189.0 1.2 3 30 44.0 53.2 2.7 187.8 1.8 4 40 45.4 52.2 2.4 186.3 2.6 5 50 47.1 50.9 2.1 184.6 3.5 FQ 50 56.6 42.3 1.1 184.6 3.5 TA BLE X
SAMPLE E G COMPOSIT ION (Weight %~ VP DP

HCFC-22 HFC-125 Propane s'a IQ 0 30.0 68.0 2.0 201.8 ---1 10 25.5 71.1 3.4 200.9 0.4 2 20 26.0 ~ 70.9 3.1 199.9 0.9 3 30 26.6 70.6 2.8 198.9 1.4 4 40 27.4 70.2 2.4 197.7 2.0 5 50 28.2 69.7 2.1 196.5 2.6 FQ 50 33.6 65.3 1.1 196.5 2.6 -~'~Q 92/01762 0 TABLE XI

" SAMPLE LEAKAGE CO ~OSI TION (Weight %) VP DP

HCFC-~ HFC-125 propane sia IQ 0 10.0 88.0 2.0 209.8 ---1 10 9.1 87.2 3.7 208.8 0.5 2 20 9.3 . 87.5 3.3 207.7 1.0 3 30 9.4 87.7 2.9 206.7 1.5 4 40 9.6 88.0 2.4 205.4 2.1 5 50 9.8 88.2 2.0 204.2 2.7 FQ 50 10.6 88.4 0.9 204.2 2.7 TA BLE XII
SAMPLE LEAKAGE COMF~OSI TION lWeiqht %) VP DP

HCFC-;~ HFC-125 gropane s'a IQ 0 80.0 5.0 15.0 180.2 ---1 10 74.0 7.7 18.3 179.7 0.3 2 20 74.8 7.2 18.0 179.1 0.6 3 30 75.8 6.6 17.6 178.5 0.9 4 40 76.9 6.0 17.2 177.7 1.4 5 50 78.1 5.3 16.6 176.8 1.9 FQ 50 84.5 3.2 12.3 176.8 1.9 TAB LE XIII
S~ AMPLELEAKAGE COMF~OSI TION (Weight %) VP DP

HCFC-~ AFC-125 ropane sia IQ 0 60.0 25.0 15.0 196.9 ---1 10 50.1 33.1 16.7 195.9 0.5 2 20 51.5 31.9 16.6 194.9 1.0 3 30 53.0 30.5 16.5 193.8 1.6 4 40 54.8 28.9 16.3 192.4 2.3 5 50 56.9 27.0 16.1 190.8 3.1 FQ 50 67.7 18.8 13.4 190.8 3.1 WO 92/01762 2 0. ~' ~ y 4 PCT/US91 /0410~'-TABLE XIV

SAM1~ LEAKAGE COMPOS TTION i lW

e q t %y VP Dp HCFC-22 FC- 5 Propane sia IQ 0 90.0 45.0 15.0 211.7 ---1 10 31.6 52.4 16.0 211.0 0.3 2 20 32.5 51.5 16.0 210.2 0.7 3 30 33.6 50.5 15.9 209.2 1.2 4 40 35.0 49.2 15.8 208.1 1.7 5 50 36.6 47.8 15.6 206.7 2.4 FQ 50 47.0 39.0 14.1 206.7 2.4 TABLE XV

SAMPLE LEAKAGE COMPOSI TION (Weight %) VP DP

HCFC-22 FC- 5 Propane s'a IQ 0 20.0 65.0 15.0 224.9 ---1 10 15.6 68.4 16.0 224.6 0.1 2 20 16.1 68.0 15.9 224.2 0.3 3 30 16.6 67.6 15.8 223.7 0.5 4 40 17.2 67.1 15.7 223.1 0.8 5 50 18.0 66.5 15.5 222.4 1.1 FQ 50 23.6 62.2 14.1 222.4 1.1 TA BLE XVI
SAMPLE LEAIU1GE COMPOSIT ION (Weight %) VP DP

C C- C- 5 o a sia IQ 0 10 97.0 2.0 212.1 ---1 10 1.0 95.2 3.8 210.9 0.6 2 20 1.0 95.6 3.4 209.6 1.2 3 30 10 96.1 2.9 208.3 1.8 4 40 1.0 96.5 2.5 206.9 2.5 5 50 10 97.0 2.0 205.4 3.2 FQ 50 1.0 98.1 0.9 205.4 3.2 2Ov8~6841 -"~~ 92/01762 PCT/US91104100 'TABLE
XVII

SAMPLE EAKAGE COMPOSI TION (Weight %) VP DP
~

, HCFC-~ I1FC-125 Propane sia a IQ 0 97.0 1.0 2.0 158.7 ---1 10 94.8 1.6 3.6 158.0 0.4 2 20 95.3 1.4 3.3 157.4 0.8 3 30 95.8 1.3 2.9 156.7 1.3 4 40 96.4 1.2 2.4 155.9 1.8 5 50 96.9 1.1 2.0 155.2 2.2 FQ 50 98.4 0.6 1.0 155.2 2.2 TAB LE XVIII

SAMPLE LEAKAGE COMPOSI mr_pN ght %l VP DP
(Wei NCFC-~ NFC-125 Propane sia IQ 0 98.9 1.0 0.1 152.5 ---1 10 98.2 1.6 0.2 152.4 0.1 2 20 98.4 1.5 0.1 152.3 0.1 3 30 98.5 1.3 0.1 152.2 0.2 4 40 98.7 1.2 0.1 152.1 0.3 5 50 98.9 1.0 0.1 152.0 0.3 FQ 50 99.3 0.6 0.1 152.0 0.3 ~A HLE XIX
Sue, ~ COMF~OSI TION (Weigfit VP DP
Mgr %) pLE

~~ AFC-125 Propane sia j%1 IQ 0 49.95 49.95 0.1 184.5 ---1 10 42.7 57.1 0.2 184.0 0.3 2 20 43.5 56.3 0.2 183.4 0.6 3 30 44.5 55.3 0.2 182.7 1.0 4 40 45.7 54.1 0.2 181.9 1.4 5 50 47.2 52.7 0.1 181.0 1.9 FQ 50 56..0 43.9 0.1 181.0 1.9 X4'86841 TABLE
XX

SAMPLE LEAKAGE COMPOSI TION (Wei ght %) Vp pp HCFC-22 HFC-125 Propane sia IQ 0 1.0 98.9 0.1 199.9 -__ 1 10 1.0 98.8 0.2 199.8 0.1 2 20 1.0 98.8 0.2 199.7 0.1 3 30 1.0 98.9 0.1 199.6 0.2 4 40 1.0 98.9 0.1 199.5 Ø2 5 50 1.0 98.9 0.1 199.4 0.3 FQ 50 1.0 98.9 0.1 199.4 0.3 Additional fluorocarbons, ethers, and hydrocarbons can be added to HCFC-22 and HFC-125 comprising effective amounts of ethane, butane, isobutane, dimethyl ether (DME), propylene, and difluoromethane (HFC-32) to make mixtures which are constant-boiling and could be useful as replacements for Refrigerant-502 and other medium-to-low-tempera-ture refrigerants. This Example is not intended to identify all compositions of these constant-boiling mixtures, but rather to show that these mixtures are constant boiling.
A study shows that mixtures of HCFC-22 and HFC-125 with the following additional compounds in oaring amounts in Table XXI form constant-boiling mixtures.

~O 92/01762 2 0 8 6 8 41 - PCT/US91/04100 Impact of Vapor LeaiCage Pressure on Vapor at 25'C

TABLE XXI

Vapor P ressures Refrigerant/ 0% E~raporated Evaporated 50%

Composition psia psia %Chanqe Ethane (49/49/2) 206.7 187.7 9.2 Butane (49/49/2) 181.8 177.1 2.6 Isobutane (49/49/2) 183.4 179.5 2.1 DME (49/49/2) 178.2 170.0 4.6 Propylene (49/49/2) 186.1 182.1 2.1 HFC-32 (40/40/20) 216.6 210.0 3.0 Additional components i:rom Table I, II, or III could be added to form quate:-nary and greater mixtures. For example, a mixture of HCFC-22/HFC-125/HFC-32/HFC-134a and/or HFC-134 could bE: formed.

Claims (8)

CLAIMS:
1. A near-azeotropic composition consisting essentially of pentafluoroethane (HFC-125), 1,1,1-trifluoroethane (HFC-143a) and at least one fluorocarbon selected from the group consisting of 1,1,1,2-tetrafluoroethane (HFC-134a) and 1,1,2,2-tetrafluoroethane (HFC-134), in the proportions of 35-65 weight percent HFC-125, 30-60 weight percent, 1,1,1-trifluoroethane (HFC-143a) and 3 to 15 weight percent of at least one fluorocarbon selected from the group consisting of HFC-134 and HFC-134a.
2. A composition according to Claim 1 which is a ternary blend of HFC-125, HFC-143a and either HFC-134 or HI=C-134a.
3. A composition according to Claim 1 or Claim 2 which comprises 50 to 60 weight percent of HFC-125, 35 to 45 weight percent of HFC-143a and 3 to weight percent of HFC-134a.
4. A composition according to Claim 3 which comprises about 55 weight percent of HFC-125, about 40 weight percent of HFC-143a and about 5 weight percent of HFC-134a.
5. A composition according to Claim 1 or 2 which comprises 50 to 60 weight percent of HFC-125, 35 to 45 weight percent of HFC-143a and 3 to 10 weight percent of HFC-134.
6. A composition according to Claim 5 which comprises about 55 weight percent HFC-125, about 40 weight percent of HFC-143a and about 5 weight percent of HFC-134.
7. A process for producing refrigeration which comprises evaporating a composition of any one of Claims 1-6 in the vicinity of a body to be cooled.
8. Use of a composition as claimed in any one of Claims 1 to 6 as a replacement for refrigerant 502 wherein R502 consists of about 48.8 weight percent chlorodifluoromethane (HFC-22) and about 51.2 weight percent chloropentafluoroethane (CFC-115).
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