Nonflammable mixed refrigerants (MR) for use with very low temperature throttle-cycle refrigeration systems

• US RE40,627 E1
• Filed: 01/07/2005
• Issued: 01/27/2009
• Est. Priority Date: 06/28/2000
• Status: Expired due to Term

• Current Assignee: Edwards Vacuum, LLC (Atlas Copco AB)
• Original Assignee: Brooks Automation Incorporated (Azenta, Inc.)
• Inventors: Podtchereniaev, Oleg, Mogarichni, Vladimir, Yudin, Boris, Flynn, Kevin P.
• Primary Examiner(s): Doerrler; William C
• Application Number:
  US11/032,701
• Time in Patent Office: 1,481 Days
• Field of Search: 62/114,335,277 252/67,69
• US Class Current: 62/114
• CPC Class Codes: C09K 2205/112 Halogenated ethers
• CPC Class Codes: C09K 2205/128 Perfluorinated hydrocarbons C09K2205/124, C09K2205/126 take precedence
• CPC Class Codes: C09K 2205/13 Inert gases
• CPC Class Codes: C09K 5/045 containing only fluorine as halogen
• CPC Class Codes: F25B 2400/16 Receivers
• CPC Class Codes: F25B 2400/18 Refrigerant conversion
• CPC Class Codes: F25B 39/02 Evaporators
• CPC Class Codes: F25B 41/043 in the circuit between evaporator and compressor
• CPC Class Codes: F25B 9/006 the refrigerant containing more than one component F25B9/004 takes precedence
• CPC Class Codes: F25D 31/002 Liquid coolers, e.g. beverage cooler receptacle coolers F25D31/006
• CPC Class Codes: F28D 7/024 the conduits of only one medium being helically coiled tubes, the coils having a cylindrical configuration

Abstract

Refrigerants containing HCFC'"'"'s are replaced with new blends by using R-236fa and R-125, or R-125 with R-245fa, or R-236ea, or R-134a with R-236fa in place of HCFC'"'"'s. No hardware or oil composition changes are required to maintain temperatures, pressures and capacity substantially unchanged in a refrigeration system.

Claims

1. Refrigerant blends not containing HCFC for use in a very low temperature refrigeration system, said refrigerant blends in mol percent comprising:

Overall rangeComponent(mole %)Argon 

4-36R-1410-55R-2310-50R-125 

5-20R-236fa 

7-40

!

2. Refrigerant blends as in claim 1 and further comprising at least one additional component in each said blend, the components maintaining the same proportions relative to each other after addition of said additional component.

3. Refrigerant blends as in claim 1, wherein said refrigeration system is a compressor cycle in one of an autorefrigerating cascade having a liquid/vapor phase separator, throttle device refrigeration system, and a Klimenko type system.

4. Refrigerant blends as in claim 1 wherein said refrigerating system alternatively permits flow of cold refrigerant or flow of hot refrigerant to an evaporator.

5. Refrigerant blends not containing HCF'"'"'s HCFC as in claim 1, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, in said earlier blends HCF'"'"'s HCFC being greater than 0 mol percent.

6. Refrigerant blends as in claim 1, wherein said refrigeration system includes an object being cooled by the refrigerant, said object being at least one of

(a) a metal element in a vacuum chamber freezing out and trapping undesired gasses such as water vapor,

(b) a heat exchanger removing heat from a secondary fluid stream including at least one of a liquid, gas, condensing gas, and condensing gas mixture,

(c) a metal element having internal refrigerant flow passages and cooling at least one of a silicon wafer, piece of glass, plastic piece and an aluminum disc with or without a magnetic coating on it, and

(d) a biological freezer to at least one of freeze and store biological tissues.

7. Refrigerant blends as in claim 1, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

97. Refrigerant blends not containing HCFC as in claim 1, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, said earlier blends comprising at least one flammable component.

98. Refrigerant blends according to claim 97, wherein said earlier blends comprised a hydrocarbon.

109. Refrigerant blends according to claim 1, and further comprising lubricating oil in a range of less than approximately 1% by weight.

110. Refrigerant blends according to claim 109, wherein said oil comprises a POE type lubricating oil.

111. Refrigerant blends according to claim 109, wherein said oil comprises a PAG type lubricating oil.

135. Refrigerant blends according to claim 1, wherein the mol percents are the mol percents in circulation through the compressor of the refrigeration system.

8. Refrigerant blends not containing HCFC'"'"'s , for use in a very low temperature refrigeration system where the evaporator temperature is as low as 105 K, said refrigerant blends comprising:

Ingredient NameRange (% by mol)1At least one of neon (Ne) or 

0.0-10.0helium (He)2At least one of argon (Ar) or10.0-45.0nitrogen (N2)3R-14 (CF4)20.0-50.04R-23 (CHF3)10.0-30.05R-125 (C2HF5) 

8.0-15.06R-134a0.0-5.07Other high boiling components;

0.0-3.0at least one of R-236fa, E-347,R-245fa, R-4112

!

wherein the mol percents are the mol percents in circulation through the evaporator of the refrigeration system;

and wherein the refrigerant blends operate to avoid freezeout in operation of the refrigeration system.

9. Refrigerant blends as in claim 8 and further comprising at least one additional component in each said blend, the components maintaining the same proportions relative to each other after addition of said additional component.

10. Refrigerant blends as in claim 8, wherein said refrigeration system is a compressor cycle in one of an autorefrigerating cascade having a liquid/vapor phase separator, throttle device refrigeration system, and a Klimenko type system.

11. Refrigerant blends as in claim 8 wherein said refrigerating system alternatively permits flow of cold refrigerant or flow of hot refrigerant to an evaporator.

12. Refrigerant blends not containing HCF'"'"'s HCFC as in claim 8, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, in said earlier blends HCF'"'"'s HCFC being greater than 0 mol percent.

13. Refrigerant blends as in claim 8, wherein said refrigeration system includes an object being cooled by the refrigerant, said object being at least one of

(a) a metal element in a vacuum chamber freezing out and trapping undesired gasses such as water vapor,

(b) a heat exchanger removing heat from a secondary fluid stream including at least one of a liquid, gas, condensing gas, and condensing gas mixture,

(c) a metal element having internal refrigerant flow passages and cooling at least one of a silicon wafer, piece of glass, plastic piece and an aluminum disc with or without a magnetic coating on it, and

(d) a biological freezer to at least one of freeze and store biological tissues.

14. Refrigerant blends as in claim 8, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

99. Refrigerant blends not containing HCFC as in claim 8, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, said earlier blends comprising at least one flammable component.

100. Refrigerant blends according to claim 99, wherein said earlier blends comprised a hydrocarbon.

112. Refrigerant blends according to claim 8, and further comprising lubricating oil in a range of less than approximately 1% by weight.

113. Refrigerant blends according to claim 112, wherein said oil comprises a POE type lubricating oil.

114. Refrigerant blends according to claim 112, wherein said oil comprises a PAG type lubricating oil.

15. Refrigerant blends not containing HCFC'"'"'s , for use in a very low temperature refrigeration system with low temperature (evaporator) as low as 118 K, said refrigerant blends comprising:

Ingredient NameRange (% by mole)1At least one of argon (Ar) or10.0-40.0nitrogen (N2)2R-1420.0-50.03R-23 

0.0-35.04R-125 

0.0-10.05R-134a0.0-6.06At least one of E-347, R-4112R-236fa, or R-245fa.

!

wherein the mol percents are the mol percents in circulation through the evaporator of the refrigeration system;

provided that at least one of E-347, R-4112, R-236fa, or R-245fa is present in the blend;

and wherein the refrigerant blends operate to avoid freezeout in operation of the refrigeration system.

16. Refrigerant blends as in claim 15 and further comprising at least one additional component in each said blend, the components maintaining the same proportions relative to each other after addition of said additional component.

17. Refrigerant blends as in claim 15, wherein said refrigeration system is a compressor cycle in one of an autorefrigerating cascade having a liquid/vapor phase separator, throttle device refrigeration system, and a Klimenko type system.

18. Refrigerant blends as in claim 15 wherein said refrigerating system alternatively permits flow of cold refrigerant or flow of hot refrigerant to an evaporator.

19. Refrigerant blends not containing HCF'"'"'s HCFC as in claim 3 15, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, in said earlier blends HCF'"'"'s HCFC being greater than 0 mol percent.

20. Refrigerant blends as in claim 15, wherein said refrigeration system includes an object being cooled by the refrigerant, said object being at least one of

(a) a metal element in a vacuum chamber freezing out and trapping undesired gasses such as water vapor,

(b) a heat exchanger removing heat from a secondary fluid stream including at least one of a liquid, gas, condensing gas, and condensing gas mixture,

(c) a metal element having internal refrigerant flow passages and cooling at least one of a silicon wafer, piece of glass, plastic piece and an aluminum disc with or without a magnetic coating on it, and

(d) a biological freezer to at least one of freeze and store biological tissues.

21. Refrigerant blends as in claim 15, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

101. Refrigerant blends not containing HCFC as in claim 15, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, said earlier blends comprising at least one flammable component.

102. Refrigerant blends according to claim 101, wherein said earlier blends comprised a hydrocarbon.

115. Refrigerant blends according to claim 15, and further comprising lubricating oil in a range of less than approximately 1% by weight.

116. Refrigerant blends according to claim 115, wherein said oil comprises a POE type lubricating oil.

117. Refrigerant blends according to claim 115, wherein said oil comprises a PAG type lubricating oil.

22. Refrigerant blends not containing HCFC'"'"'s , for use in a very low temperature refrigeration system with low temperature (evaporator) as low as 130 K, said refrigerant blends comprising:

Ingredient NameRange (% by mole)1At least one of argon (Ar) or 

2.0-40.0%nitrogen (N2)2R-1410.0-50.0%3R-2310.0-40.0%4R-125 

0.0-40.0%5R-134a 

0.0-15.0%6At least one of R-245fa, R- 

 

 

 

0.0-30.00% 10.0%236fa, E-347, or R-4112.

!

wherein the mol percents are the mol percents in circulation through the evaporator of the refrigeration system;

provided that at least one of R-245fa, R-236fa, E-347, or R-4112 is present in the blend;

and wherein the refrigerant blends operate to avoid freezeout in operation of the refrigeration system.

23. Refrigerant blends as in claim 22 and further comprising at least one additional component in each said blend, the components maintaining the same proportions relative to each other after addition of said additional component.

24. Refrigerant blends as in claim 22, wherein said refrigeration system is a compressor cycle in one of an autorefrigerating cascade having a liquid/vapor phase separator, throttle device refrigeration system, and a Klimenko type system.

25. Refrigerant blends as in claim 22 wherein said refrigerating system alternatively permits flow of cold refrigerant or flow of hot refrigerant to an evaporator.

26. Refrigerant blends not containing HCF'"'"'s HCFC as in claim 22, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, in said earlier blends HCF'"'"'s HCFC being greater than 0 mol percent.

27. Refrigerant blends as in claim 22, wherein said refrigeration system includes an object being cooled by the refrigerant, said object being at least one of

(a) a metal element in a vacuum chamber freezing out and trapping undesired gasses such as water vapor,

(b) a heat exchanger removing heat from a secondary fluid stream including at least one of a liquid, gas, condensing gas, and condensing gas mixture,

(c) a metal element having internal refrigerant flow passages and cooling at least one of a silicon wager, piece of glass, plastic piece and an aluminum disc with or without a magnetic coating on it, and

(d) a biological freezer to at least one of freeze and store biological tissues.

28. Refrigerant blends as in claim 4 22, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

103. Refrigerant blends not containing HCFC as in claim 22, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, said earlier blends comprising at least one flammable component.

104. Refrigerant blends according to claim 103, wherein said earlier blends comprised a hydrocarbon.

118. Refrigerant blends according to claim 22, and further comprising lubricating oil in a range of less than approximately 1% by weight.

119. Refrigerant blends according to claim 118, wherein said oil comprises a POE type lubricating oil.

120. Refrigerant blends according to claim 118, wherein said oil comprises a PAG type lubricating oil.

29. Refrigerant blends not containing HCFC'"'"'s , for use in a very low temperature refrigeration system with low temperature (evaporator) as low as 140 K, said refrigerant blends comprising:

Ingredient NameRange (% by mol)1At least one of argon (Ar) or 

2.0-40.0%nitrogen (N2)2R-1410.0-50.0%3R-2310.0-40.0%4R-125 

0.0-30.0%5R-134a 

0.0-15.0%56At least one of R-236fa, R- 

 

 

 

0.0-10.0% 15.0% 245fa, E-347, or R-4112.

!

wherein the mol percents are the mol percents in circulation through the evaporator of the refrigeration system;

provided that at least one of R-236fa, R-245fa, E-347, or R-4112 is present in the blend;

and wherein the refrigerant blends operate to avoid freezeout in operation of the refrigeration system.

30. Refrigerant blends as in claim 29 and further comprising at least one additional component in each said blend, the components maintaining the same proportions relative to each other after addition of said additional component.

31. Refrigerant blends as in claim 29, wherein said refrigeration system is a compressor cycle in one of an autorefrigerating cascade having a liquid/vapor phase separator, throttle device refrigeration system, and a Klimenko type system.

32. Refrigerant blends as in claim 29 wherein said refrigerating system alternatively permits flow of cold refrigerant or flow of hot refrigerant to an evaporator.

33. Refrigerant blends not containing HCF'"'"'s HCFC as in claim 29, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, in said earlier blends HCF'"'"'s HCFC being greater than 0 mol percent.

34. Refrigerant blends as in claim 29, wherein said refrigeration system includes an object being cooled by the refrigerant, said object being at least one of

(a) a metal element in a vacuum chamber freezing out and trapping undesired gasses such as water vapor,

(b) a heat exchanger removing heat from a secondary fluid stream including at least one of a liquid, gas, condensing gas, and condensing gas mixture,

(c) a metal element having internal refrigerant flow passages and cooling at least one of a silicon wafer, piece of glass, plastic piece and an aluminum disc with or without a magnetic coating on it, and

a biological freezer to at least one of freeze and store biological tissues.

35. Refrigerant blends as in claim 29, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

105. Refrigerant blends not containing HCFC as in claim 29, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, said earlier blends comprising at least one flammable component.

106. Refrigerant blends according to claim 105, wherein said earlier blends comprised a hydrocarbon.

121. Refrigerant blends according to claim 29, and further comprising lubricating oil in a range of less than approximately 1% by weight.

122. Refrigerant blends according to claim 121, wherein said oil comprises a POE type lubricating oil.

123. Refrigerant blends according to claim 121, wherein said oil comprises a PAG type lubricating oil.

36. Refrigerant blends not containing HCFC'"'"'s , for use in a very low temperature refrigeration system with low temperature (evaporator) as low as 155 K, said refrigerant blends comprising:

Ingredient NameRange (% by mole)1At least one of argon (Ar) or 0.0-40.0%nitrogen (N2)2R-145.0-50.0%3R-235.0-40.0%4R-1250.0-40.0%5R-134a0.0-30.0%6At least one of R-236fa, or0.0-30.0%R-245fa7At least one of E-347 or R-41120.0-20.0%

!

wherein the mol percents are the mol percents in circulation through the evaporator of the refrigeration system;

provided that at least one of R-236fa, R-245fa, E-347, or R-4112 is present in the blend;

and wherein the refrigerant blends operate to avoid freezeout in operation of the refrigeration system.

37. Refrigerant blends as in claim 36 and further comprising at least one additional component in each said blend, the components maintaining the same proportions relative to each other after addition of said additional component.

38. Refrigerant blends as in claim 36, wherein said refrigeration system is a compressor cycle in one of an autorefrigerating cascade having a liquid/vapor phase separator, throttle device refrigeration system, and a Klimenko type system.

39. Refrigerant blends as in claim 36 wherein said refrigerating system alternatively permits flow of cold refrigerant or flow of hot refrigerant to an evaporator.

40. Refrigerant blends not containing HCF'"'"'s HCFC as in claim 36, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, in said earlier blends HCF'"'"'s HCFC being greater than 0 mol percent.

41. Refrigerant blends as in claim 36, wherein said refrigeration system includes an object being cooled by the refrigerant, said object being at least one of

(d) a metal element in a vacuum chamber freezing out and trapping undesired gasses such as water vapor,

(e) a heat exchanger removing heat from a secondary fluid stream including at least one of a liquid, gas, condensing gas, and condensing gas mixture,

(f) a metal element having internal refrigerant flow passages and cooling at least one of a silicon wafer, piece of glass, plastic piece and an aluminum disc with or without a magnetic coating on it, and

a biological freezer to at least one of freeze and store biological tissues.

42. Refrigerant blends as in claim 36, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

107. Refrigerant blends not containing HCFC as in claim 36, said blends operating as a replacement in a refrigeration system to provide substantially the same thermodynamic performance in said system as provided by earlier blends of components, said earlier blends comprising at least one flammable component.

108. Refrigerant blends according to claim 107, wherein said earlier blends comprised a hydrocarbon.

124. Refrigerant blends according to claim 36, and further comprising lubricating oil in a range of less than approximately 1% by weight.

125. Refrigerant blends according to claim 124, wherein said oil comprises a POE type lubricating oil.

126. Refrigerant blends according to claim 124, wherein said oil comprises a PAG type lubricating oil.

43. Refrigerant blends not containing HCFC for use in a very low temperature refrigeration system, said refrigerant blends selected from the group comprising Blend A, Blend B, Blend C, and Blend D where the components of each blend in mol percent are as follows:

Molar Fraction (percent)ComponentBlend ABlend BBlend CBlend DArgon132418 

8R-1434263524R-2328222132R-12511111211R-236fa141714 

25.

!

44. A refrigerant blend free of HCFC containing a mixed refrigerant comprising a fluorocarbon, at least one gas selected from the group consisting of Ar and N₂, and at least one of R-236fa, R-245fa, HFE, and R-4112, the at least one R-236fa, R-245fa, HFE, and R-4112 in a total amount not greater than 3.0 mol %;

wherein the mol percents are the mol percents in circulation through the evaporator of the refrigeration system; and

wherein the refrigerant blends operate to avoid freezeout in operation of the refrigeration system.

45. The refrigerant blend of claim 44, wherein the refrigerant blend is configured for use in a very low temperature refrigeration system.

46. The refrigerant blend of claim 44, wherein HFE comprises E-347.

47. The refrigerant blend of claim 44, wherein the fluorocarbon comprises R-14.

48. The refrigerant blend of claim 44, further comprising a lubricant oil.

49. The refrigerant blend of claim 48, comprising approximately 1 wt % to 10 wt % of the lubricant oil.

50. The refrigerant blend of claim 48, wherein the lubricant oil comprises POE-type lubricant oil.

51. The refrigerant blend of claim 48, wherein the lubricant oil comprises PAG-type lubricant oil.

91. The refrigerant blend of claim 44, wherein the mixed refrigerant further comprises at least one of Ne or He.

127. The refrigerant blend of claim 48, comprising less than approximately 1 wt % of the lubricant oil.

128. The refrigerant blend of claim 127, wherein said oil comprises a POE type lubricating oil.

129. The refrigerant blend of claim 127, wherein said oil comprises a PAG type lubricating oil.

52. A refrigerant blend free of HCFC containing a mixed refrigerant comprising:

at least one of Ar or N₂;

R-14;

R-125;

R-23; and

at least one of R-236fa, R-245fa, E-347, or R-4112.

53. The refrigerant blend of claim 52, wherein the refrigerant blend is configured for use in a very low temperature refrigeration system.

54. The refrigerant blend of claim 52, wherein the mixed refrigerant comprises not greater than 55.0 mol % of the R-14.

55. The refrigerant blend of claim 52, wherein the mixed refrigerant comprises not greater than 40.0 mol % of the R-23.

56. The refrigerant blend of claim 52, wherein the mixed refrigerant comprises not greater than 40.0 mol % of the R-125.

57. The refrigerant blend of claim 52, wherein the mixed refrigerant comprises not greater than 40.0 mol % of the at least one of R-236fa, R-245fa, E-347, or R-4112.

58. The refrigerant blend of claim 52, wherein the mixed refrigerant comprises not greater than 30.0 mol % of the at least one of R-236fa, R-245fa, E-347, or R-4112.

59. The refrigerant blend of claim 52, wherein the mixed refrigerant comprises not greater than 10.0 mol % of the at least one of R-236fa, R-245fa, E-347, or R-4112.

60. The refrigerant blend of claim 52, wherein the mixed refrigerant comprises not greater than 6.0 mol % of the at least one of R-236fa, R-245fa, E-347, or R-4112.

61. The refrigerant blend of claim 52, wherein the mixed refrigerant comprises not greater than 3.0 mol % of the at least one of R-236fa, R-245fa, E-347, or R-4112.

62. The refrigerant blend of claim 52, wherein the mixed refrigerant further comprises R-134a.

63. The refrigerant blend of claim 62, wherein the mixed refrigerant comprises not greater than 15.0 mol % of the R-134a.

92. The refrigerant blend of claim 52, wherein the mixed refrigerant further comprises at least one of Ne or He.

136. The refrigerant blend of claim 52, wherein the mixed refrigerant comprises not greater than 50.0 mol % of the R-23.

64. The refrigerant blend free of HCFC containing a mixed refrigerant comprising a fluorocarbon, E-347, and at least one gas selected from the group consisting of Ar or N₂.

65. The refrigerant blend of claim 64, wherein the refrigerant blend is configured for use in a very low temperature refrigeration system.

93. The refrigerant blend of claim 64, wherein the mixed refrigerant further comprises at least one of Ne or He.

66. A method of refrigerating, the method comprising:

using an HCFC-free refrigerant blend in a refrigeration system, the HCFC-free refrigerant blend containing a mixed refrigerant comprising;

at least one of Ar or N₂;

R-14;

R-125;

R-23; and

at least one of R-236fa, R-245fa, E-347, or R-4112; and

cooling an evaporator of the refrigeration system.

67. The method of claim 66, wherein the refrigeration system is designed for use of HCFC-containing refrigerant blends, wherein the HCFC-free refrigerant blend is a replacement refrigerant.

68. The method of claim 66, wherein cooling comprises cooling the evaporator to a temperature as low as 155K.

69. The method of claim 66, wherein cooling comprises cooling the evaporator to a temperature as low as 140K.

70. The method of claim 66, wherein cooling comprises cooling the evaporator to a temperature as low as 130K.

71. The method of claim 66, wherein cooling comprises cooling the evaporator to a temperature as low as 118K.

72. The method of claim 66, wherein the HCFC-free refrigerant blend further comprises lubricant oil.

73. The method of claim 72, wherein the HCFC-free refrigerant blend comprises approximately 1 wt % to 10 wt % of the lubricant oil.

74. The method of claim 72, wherein the lubricant oil comprises POE-type lubricant oil.

75. The method of claim 72, wherein the lubricant oil comprises PAG-type lubricant oil.

94. The refrigerant blend of claim 66, wherein the mixed refrigerant further comprises at least one of Ne or He.

130. The method of claim 72, wherein the HCFC-free refrigerant blend comprises less than approximately 1 wt % of the lubricant oil.

131. The method of claim 130, wherein said oil comprises a POE type lubricating oil.

132. The method of claim 130, wherein said oil comprises a PAG type lubricating oil.

76. A refrigerant blend free of HCFC comprising (i) a mixed refrigerant comprising at least one of R-236fa and R-245fa, and (ii) lubricant oil, wherein the refrigerant blend has a freezing temperature not greater than 150.0K.

77. The refrigerant blend of claim 76, wherein the lubricant oil comprises POE-type lubricant oil.

78. The refrigerant blend of claim 76, wherein the refrigerant blend comprises approximately 1 wt % to 10 wt % of the lubricant oil.

79. The refrigerant blend of claim 76, wherein the freezing temperature is not greater than 140K.

80. The refrigerant blend of claim 76, further comprising at least one gas selected from Ar and N₂.

81. The refrigerant blend of claim 76, further comprising R-14.

82. The refrigerant blend of claim 76, further comprising R-23.

83. The refrigerant blend of claim 76, further comprising R-125.

84. The refrigerant blend of claim 76, further comprising R-218.

95. The refrigerant blend of claim 80, further comprising at least one gas selected from the group consisting of Ne and He.

133. The refrigerant blend of claim 76, wherein the refrigerant blend comprises less than approximately 1 wt % of the lubricant oil.

134. The refrigerant blend of claim 76, wherein the lubricant oil comprises PAG-type lubricant oil.

85. A refrigerant blend free of HCFC containing a mixed refrigerant comprising:

at least one of Ar or N₂;

R-14;

R-23; and

R-125.

86. The refrigerant blend of claim 85, wherein the refrigerant blend is configured for use in a very low temperature refrigeration system.

87. The refrigerant blend of claim 85, further comprising R-134a.

96. The refrigerant blend of claim 85, wherein the mixed refrigerant further comprises at least one of Ne or He.

88. A refrigerant blend free of HCFC containing a mixed refrigerant comprising:

R-14;

R-125;

R-23; and

at least one of R-236fa, R-245fa, E-347, or R-4112.

89. The refrigerant blend of claim 88, wherein the refrigerant blend is configured for use in a very low temperature refrigeration system.

90. The refrigerant blend of claim 88, further comprising R-134a.

137. Refrigerant blends not containing HCFC for use in a very low temperature refrigeration system, said refrigerant blends in mol percent comprising:

Overall rangeComponent(mole %)Argon 

4-36R-1410-55Total of R-170 and any R-23 in blend10-50R-125 

5-20R-236fa 

7-40

!

provided that at least some R-170 is present in the blend.

138. Refrigerant blends as in claim 137, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

139. Refrigerant blends according to claim 137, and further comprising lubricating oil in a range of less than approximately 1% by weight.

140. Refrigerant blends according to claim 139, wherein said oil comprises a POE type lubricating oil.

141. Refrigerant blends according to claim 139, wherein said oil comprises a PAG type lubricating oil.

142. Refrigerant blends not containing HCFC, for use in a very low temperature refrigeration system where the evaporator temperature is as low as 105 K, said refrigerant blends comprising:

Range (%Ingredient Nameby mol)1At least one of neon (Ne) or 

0.00-10.0helium (He)2At least one of argon (Ar) or10.0-45.0nitrogen3R-14 (CF4)20.0-50.04Total of R-170 (Ethane) and any R-23 (CHF3) in blend10.0-30.05R-125 (C2HF5) 

8.0-15.06R-134a0.0-5.07Other high boiling components;

0.0-3.0at least one of R-236fa,E-347, R-245fa, R-4112

!

provided that at least some R-170 is present in the blend.

143. Refrigerant blends as in claim 142, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

144. Refrigerant blends according to claim 142, and further comprising lubricating oil in a range of less than approximately 1% by weight.

145. Refrigerant blends according to claim 144, wherein said oil comprises a POE type lubricating oil.

146. Refrigerant blends according to claim 144, wherein said oil comprises a PAG type lubricating oil.

147. Refrigerant blends not containing HCFC, for use in a very low temperature refrigeration system with low temperature (evaporator) as low as 118 K, said refrigerant blends comprising:

Ingredient NameRange (% by mole)1At least one of argon (Ar) or10.0-40.0nitrogen (N2)2R-1420.0-50.03Total of R-170 and any R-23 in blend10.0-40.04R-1250.0-35.05R-134a 

0.0-10.06At least one of E-347, R-4112,0.0-6.0R-236fa or R-245fa

!

wherein the mol percents are the mol percents in circulation through the evaporator of the refrigeration system;

provided that at least some R-170 is present in the blend;

provided that at least one of E-347, R-4112, R-236fa or R-245fa is present in the blend;

and wherein the refrigerant blends operate to avoid freezeout in operation of the refrigeration system.

148. Refrigerant blends as in claim 147, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

149. Refrigerant blends according to claim 147, and further comprising lubricating oil in a range of less than approximately 1% by weight.

150. Refrigerant blends according to claim 149, wherein said oil comprises a POE type lubricating oil.

151. Refrigerant blends according to claim 149, wherein said oil comprises a PAG type lubricating oil.

152. Refrigerant blends not containing HCFC, for use in a very low temperature refrigeration system with low temperature (evaporator) as low as 130 K, said refrigerant blends comprising:

Ingredient NameRange (% by mole)1At least one of argon (Ar) or 

2.0-40.0%nitrogen (N2)2R-1410.0-50.0%3Total of R-170 and any R-23 in blend10.0-40.0%4R-125 

0.0-40.0%5R-134a 

0.0-15.0%6At least one of R-245fa, R- 

0.0-10.0%236fa, E-347, or R-4112

!

wherein the mol percents are the mol percents in circulation through the evaporator of the refrigeration system;

provided that at least some R-170 is present in the blend;

provided that at least one of R-245fa, R-236fa, E-347, or R-4112 is present in the blend;

and wherein the refrigerant blends operate to avoid freezeout in operation of the refrigeration system.

153. Refrigerant blends as in claim 152, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

154. Refrigerant blends according to claim 152, and further comprising lubricating oil in a range of less than approximately 1% by weight.

155. Refrigerant blends according to claim 154, wherein said oil comprises a POE type lubricating oil.

156. Refrigerant blends according to claim 154, wherein said oil comprises a PAG type lubricating oil.

157. Refrigerant blends not containing HCFC, for use in a very low temperature refrigeration system with low temperature (evaporator) as low as 140 K, said refrigerant blends comprising:

Ingredient NameRange (% by mole)1At least one of argon (Ar) or 

2.0-40.0%nitrogen (N2)2R-1410.0-50.0%3Total of R-170 and any R-23 in blend10.0-40.0%4R-125 

0.0-30.0%5R-134a 

0.0-15.0%6At least one of R-236fa, R- 

0.0-10.0%245fa, E-347, or R-4112

!

wherein the mol percents are the mol percents in circulation through the evaporator of the refrigeration system;

provided that at least some R-170 is present in the blend;

provided that at least one of R-236fa, R-245fa, E-347, or R-4112 is present in the blend;

and wherein the refrigerant blends operate to avoid freezeout in operation of the refrigeration system.

158. Refrigerant blends as in claim 157, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

159. Refrigerant blends according to claim 157, and further comprising lubricating oil in a range of less than approximately 1% by weight.

160. Refrigerant blends according to claim 159, wherein said oil comprises a POE type lubricating oil.

161. Refrigerant blends according to claim 159, wherein said oil comprises a PAG type lubricating oil.

162. Refrigerant blends not containing HCFC, for use in a very low temperature refrigeration system with low temperature (evaporator) as low as 155 K, said refrigerant blends comprising:

Ingredient NameRange (% by mole)1At least one of argon (Ar) or0.0-40.0%nitrogen (N2)2R-145.0-50.0%3Total of R-170 and any R-23 in blend5.0-40.0%4R-1250.0-40.0%5R-134a0.0-30.0%6At least one of R-236fa, or0.0-30.0%R-245fa7At least one of E-347 or R-41120.0-20.0%

!

wherein the mol percents are the mol percents in circulation through the evaporator of the refrigeration system;

provided that at least some R-170 is present in the blend;

provided that at least one of R-236fa, R-245fa, E-347, or R-4112 is present in the blend;

and wherein the refrigerant blends operate to avoid freezeout in operation of the refrigeration system.

163. Refrigerant blends as in claim 162, and further comprising lubricating oil in a range of approximately 1% to 10% by weight, said oil being one of POE type and PAG type.

164. Refrigerant blends according to claim 162, and further comprising lubricating oil in a range of less than approximately 1% by weight.

165. Refrigerant blends according to claim 164, wherein said oil comprises a POE type lubricating oil.

166. Refrigerant blends according to claim 164, wherein said oil comprises a PAG type lubricating oil.

167. A refrigerant blend free of HCFC containing a mixed refrigerant comprising:

at least one of Ar or N₂;

R-14;

R-125;

R-170; and

at least one of R-236fa, R-245fa, E-347, or R-4112.

168. The refrigerant blend of claim 167, wherein the mixed refrigerant comprises not greater than 40.0 mol % of a total of R-170 and any R-23 present in the blend.

169. The refrigerant blend of claim 167, wherein the mixed refrigerant comprises not greater than 50.0 mol % of a total of R-170 and any R-23 present in the blend.

170. A method of refrigerating, the method comprising:

using an HCFC-free refrigerant blend in a refrigeration system, the HCFC-free refrigeration blend containing a mixed refrigerant comprising;

at least one of Ar or N₂;

R-14;

R-125;

R-170; and

at least one of R-236fa, R-245fa, E-347, or R-4112; and

cooling an evaporator of the refrigeration system.

171. The method of claim 170, wherein the HCFC-free refrigerant blend further comprises lubricant oil.

172. The method of claim 171, wherein the HCFC-free refrigerant blend comprises approximately 1 wt % to 10 wt % of the lubricant oil.

173. The method of claim 171, wherein the lubricant oil comprises POE-type lubricant oil.

174. The method of claim 171, wherein the lubricant oil comprises PAG-type lubricant oil.

175. A refrigerant blend free of HCFC comprising (i) a mixed refrigerant comprising R-170 and at least one of R-236fa and R-245fa, and (ii) lubricant oil, wherein the refrigerant blend has a freezing temperature not greater than 150.0K.

176. A refrigerant blend according to claim 175, further comprising R-23.

177. A refrigerant blend free of HCFC containing a mixed refrigerant comprising:

at least one of Ar or N₂;

R-14;

R-170; and

R-125.

178. A refrigerant blend free of HCFC containing a mixed refrigerant comprising:

R-14;

R-125;

R-170; and

at least one of R-236fa, R-245fa, E-347, or R-4112.