LOW GWP CASCADE REFRIGERATION SYSTEM

Information

  • Patent Application
  • 20180017292
  • Publication Number
    20180017292
  • Date Filed
    March 24, 2017
    7 years ago
  • Date Published
    January 18, 2018
    6 years ago
Abstract
Disclosed are cascade refrigerant systems for providing cooling of air located in an enclosure that is occupied by or which will be exposed to humans or other animals during normal use, wherein systems includes; (1) a first, relatively low temperature heat transfer circuit having a first evaporator located within the enclosure and a first heat transfer fluid in the low temperature heat transfer circuit; (2) a second heat transfer circuit located substantially outside the enclosure comprising a second heat transfer fluid; (3) a heat exchanger which serves as the condenser in the low temperature circuit thermally coupled with the high temperature circuit by virtue of rejecting heat into the second heat transfer fluid; and (4) in the high temperature loop of a heat exchanger which transfers heat from the second heat transfer fluid exiting from a high temperature condenser to the portion of the second heat transfer fluid which is traveling to the suction side of the compressor.
Description
FIELD OF THE INVENTION

The present invention relates to high efficiency, low-global warming potential (“low GWP”) air conditioning and/or refrigeration systems and methods for providing cooling that are safe and effective.


BACKGROUND

In typical air conditioning and refrigerant systems, a compressor is used to compress a heat transfer vapor from a lower to a higher pressure, which in turn adds heat to the vapor. This added heat is typically rejected in a heat exchanger, commonly referred to as a condenser. The heat transfer vapor that enters the condenser is condensed to produce a liquid heat transfer fluid at a relatively high pressure. Typically the condenser uses a fluid available in large quantities in the ambient environment, such as ambient outside air, as the heat sink. Once it has been condensed, the high-pressure heat transfer fluid undergoes a substantially isoenthalpic expansion, such would occur by passing the fluid through an expansion device or valve, where it is expanded to a lower pressure, which in turn results in the fluid undergoing a decrease in temperature. The lower pressure, lower temperature heat transfer fluid from the expansion operation then is typically routed to an evaporator, where it absorbs heat and in so doing evaporates. This evaporation process in turn results in cooling of the fluid or body to that it is intended to cool. In many typical air conditioning and refrigeration applications, the cooled fluid is the air which is contained in the region to be cooled, such as the air in the dwelling being air conditioned or the air inside a walk-in cooler or a supermarket cooler or freezer. After the heat transfer fluid is evaporated at low pressure in the evaporator, it is returned to the compressor where the cycle begins once again.


A complex and interrelated combination of factors and requirements is associated with forming efficient, effective and safe air conditioning systems that are at the same time environmentally friendly, that is, have both low GWP impact and low ozone depletion (“ODP” impact. With respect to efficiency and effectiveness, it is important for the heat transfer fluid to operate in air conditioning and refrigeration systems with high levels of efficiency and high relative capacity. At the same time, since it is possible that the heat transfer fluid may escape over time into the atmosphere, it is important for the fluid to have low values for both GWP and ODP.


Applicants have come to appreciate that while certain fluids are able to achieve high levels of both efficiency and effectiveness, and at the same time low levels of both GWP and ODP, many fluids which satisfy this combination of requirements nevertheless suffer from the disadvantage of having deficiencies in connection with safety. For example, fluids which might otherwise be acceptable may be disfavored because of flammability properties and/or toxicity concerns. Applicants have come to appreciate that the use of fluids having such properties is especially undesirable in typical air conditioning and in many refrigeration systems since such flammable and/or toxic fluids may inadvertently be released into the dwelling, walk-in, cold-box, chiller, freezer or transport refrigeration box which is being cooled, thus exposing or potentially exposing the occupants thereof to dangerous conditions. Applicants have also come to appreciate that this problem is even of a more intense concern for relatively small systems, e.g., systems with a capacity of less than 30 kw since for such systems the cost of effective safety protection systems, such as fire protections systems, are frequently not economically viable.


SUMMARY

According to one aspect of the invention, a cascade refrigerant system is provided for providing cooling of air, directly or indirectly but preferably directly, located in an enclosure that is occupied by or which will be exposed to humans or other animals during normal use. As used herein, the term “enclosure” means a space that is at least partially confined (e.g., the enclosure can be opened on one or more sides, or closed) and includes air that has been cooled.


Preferred embodiments of the present systems include at least a first evaporator which is located within the enclosure and is part of a first, relatively low temperature heat transfer circuit. The low temperature heat transfer circuit preferably comprises a first heat transfer fluid in a vapor compression circulation loop comprising at least: a compressor for raising the pressure of the first heat transfer composition; a heat exchanger for condensing at least a portion of the first heat transfer composition from the compressor at a relatively high pressure; an expansion device for lowering the pressure of the heat transfer composition from the condenser; and an evaporator for absorbing heat from the enclosure to be cooled into the heat transfer composition. Preferably one or more of said compressor, condenser and said expansion valve, and most preferably all of these, are located outside the enclosure and the evaporator is located within the enclosure.


The systems of the present invention also preferably include a second heat transfer circuit located substantially outside the enclosure, which is sometimes referred to herein by way of convenience as the “high temperature” loop. The high temperature loop preferably comprises a second heat transfer fluid in a vapor compression circulation loop comprising at least a compressor, a heat exchanger which serves to condense the heat transfer fluid in the high temperature loop, preferably by heat exchange with ambient air outside of the enclosure, and an expansion device for reducing the pressure of the second heat transfer fluid from the compressor.


An important aspect of preferred embodiments of the present invention is that the heat exchanger which serves as the condenser in the low temperature circuit is thermally coupled with the high temperature circuit by virtue of rejecting heat into the second heat transfer fluid, preferably by causing at least a substantial portion of said second heat transfer fluid to evaporate. In this way, the condenser of the low temperature circuit and the evaporator of the high temperature circuit are thermally coupled in this heat exchanger, which is sometimes referred to for convenience as “a cascade heat exchanger” in the systems and methods of the present invention.


Another important aspect of the present invention in preferred embodiments comprises the presence in the high temperature loop of a heat exchanger which has been found to advantageously and unexpectedly improve system performance by transferring heat from the second heat transfer fluid exiting from the high temperature condenser to the portion of the second heat transfer fluid which is traveling to the suction side of the compressor. This heat exchanger is sometimes referred to herein for convenience as a “suction line heat exchanger.”


Another important aspect of the preferred systems is that the first heat transfer fluid which is circulating in the low temperature loop comprises a refrigerant which has a GWP of not greater than about 500, more preferably not greater than about 400, and even more preferably not greater than about 150 and furthermore that the first heat transfer fluid has a flammability that is substantially less than the flammability of the second heat transfer fluid. Preferably, the second heat transfer fluid which is circulating in the high temperature loop also comprises a refrigerant which has a GWP of not greater than about 500, more preferably not greater than about 400, and even more preferably not greater than about 150, but since in normal operation this heat transfer fluid will never enter the enclosure, applicants have found that is advantageous to use a fluid in this high temperature loop that has one or properties that would be considered disadvantageous if it circulated within the enclosure, for example, flammability, toxicity and the like. In this way, the present systems allow additional possible unexpected advantages over systems that would rely only of the first heat transfer composition or only the second heat transfer composition, as explained in detail below.


In certain preferred embodiments the second refrigerant comprises, more preferably comprises at least about 50% by weight and even more preferably at least about 75% by weight, of trans-1,3,3,3-trifluoropropene (HFO-1234ze(E) and/or HFO-1234yf, and the second refrigerant has a flammability greater than , and preferably substantially greater than about, the flammability of CO2. In another embodiment the second refrigerant comprises, more preferably comprises at least about 75% by weight and even more preferably at least about 80% by weight, of trans-1,3,3,3-trifluoropropene (HFO-1234ze(E) and/or HFO-1234yf.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a generalized process flow diagram of one preferred embodiment of an air conditioning system according to the present invention.



FIG. 2 is a schematic of a typical walk-in cooler refrigeration configuration.





DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Preferred Heat Transfer Compositions

In each of the preferred embodiments described herein the system includes:


(a) a relatively low temperature vapor compression loop comprising a compressor, an expander and an evaporator in fluid communication in said loop, and a first heat transfer composition in said loop comprising a first refrigerant and preferably lubricant for the compressor, said evaporator being located in an enclosure containing air to be cooled and being capable of absorbing heat from said air at about said relatively low temperature;


(b) a relatively high temperature vapor compression loop comprising a compressor, a condenser, an expander, and a suction line heat exchanger in fluid communication in said loop, and a second heat transfer composition in said loop comprising a second refrigerant and preferably lubricant for the compressor, said condenser being capable of transferring heat to a heat sink located outside said enclosure; and


(c) a cascade heat exchanger for condensing said first refrigerant and evaporating said second refrigerant by heat exchange between said first and second refrigerant,


wherein said suction line heat exchanger is in fluid communication with said cascade heat exchanger for receiving at least a portion of said second heat transfer composition exiting said cascade heat exchanger and increases the temperature thereof by absorbing heat from said first heat transfer composition exiting said condenser and thereby reducing the temperature of said first heat transfer composition prior to said first heat transfer composition entering said first loop expander.


As used herein, the terms “relatively low temperature” and “relatively high temperature,” when used together with respect to the first and second heat transfer loops, and unless otherwise indicated, are used in a relative sense to designate the relative temperature of the indicated heat transfer compositions, where those differences are least about 5° C.


Preferably the first refrigerant has a flammability that is substantially less than the flammability of the second refrigerant. In preferred embodiments, the first refrigerant has a flammability according to ASHRAE Standard 34 (which specifies measurement according to ASTM E681) that is classified as Al and the second refrigerant has a flammability according to ASHRAE Standard 34 that is classified as A2L or a higher flammability than A2L, although A2L classification for the second refrigerant is preferred. It is also preferred that the first and the second refrigerant each have a Global Warming Potential (GWP) that is less than about 150.


In preferred embodiments the first refrigerant circulating in the low temperature loop comprises carbon dioxide, preferably consists essentially of carbon dioxide and more preferably in some embodiments consists of carbon dioxide.


It is preferred that the second refrigerant comprises one or more of trans1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), R-227ea, and R-32 and combinations of two or more of these. In preferred embodiments, the second refrigerant comprises at least about 50%, more preferably at least about 80% by weight of 2, 3,3,3-tetrafluoropropene (HFO-1234yf). In other preferred embodiments, the second refrigerant comprises at least about 50%, more preferably at least about 80% by weight of or at least about 75% by weight, more preferably at least about 80% by weight of trans1,3,3,3-tetrafluoropropene (HFO-1234ze(E)). In highly preferred embodiments, the second refrigerant comprises at least about 95% by weight, and in some embodiments consists essentially of or consists of HFO-1234ze(E), HFO-1234yf or combinations of two or more of these.


In other highly preferred embodiments, the second refrigerant comprises from about 70% by weight to about 90% of HFO-1234yf, preferably about 80% by weight of HFO-1234yf and from about 10% by weight to about 30% by weight of R32, preferably about 20% by weight of R-32.


In other highly preferred embodiments, the second refrigerant comprises from about 70% by weight to about 90% of HFO-1234ze(E), preferably about 80% by weight of HFO-1234ze(E) and from about 10% by weight to about 30% by weight of R32, preferably about 20% by weight of R-32.


In other highly preferred embodiments, the second refrigerant comprises from about 85% to about 90% by weight of by weight of trans1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) and from about 10% by weight to about 15% by weight of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), and even more preferably in some embodiments about 88% of trans1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) and about 12% by weight of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).


Those skilled in the art will appreciate in view of the disclosures contained herein that the preferred embodiments of the present invention provide the advantage of utilizing only the safe (relatively low toxicity and low flammability) low GWP refrigerants within the enclosure to be cooled and a relatively less safe, but preferably low GWP refrigerant in the high temperature loop which is located entirely outside of the enclosure.


As used herein, the terms “safe” and “relatively less safe,” when used together with respect to the first and second heat transfer loops, and unless otherwise indicated, are used in a relative sense to designate the relative safety of the indicated heat transfer compositions. Such configuration, especially when the high temperature system includes the preferred suction line heat exchanger, makes the systems and methods of the invention highly preferred for use in a location proximate to the humans or other animals occupying or using the enclosure, as is commonly encountered in walk-in freezers, supermarket coolers and the like.


Preferred embodiments of the second refrigerant are disclosed in the following table:


















Component>>>







Second







Refrigerant







Designation
R-1234yf,
R-1234ze(E),





▾ ▾
wt %
wt %
R-32
R227ea





















SR1 
5
95
0
0



SR2 
10
90
0
0



SR3 
15
85
0
0



SR4 
20
80
0
0



SR4 
25
75
0
0



SR5 
30
70
0
0



SR6 
35
65
0
0



SR7 
40
95
0
0



SR8 
45
50
0
0



SR9 
50
50
0
0



SR10
55
45
0
0



SR11
60
40
0
0



SR12
65
35
0
0



SR13
70
30
0
0



SR14
75
25
0
0



SR15
80
20
0
0



SR16
85
15
0
0



SR17
90
10
0
0



SR18
95
5
0
0



SR19
70
0
30
0



SR20
75
0
25
0



SR21
80
0
20
0



SR22
85
0
15
0



SR23
90
0
10
0



SR24
0
70
30
0



SR25
0
75
25
0



SR26
0
80
20
0



SR27
0
85
15
0



SR28
0
90
10
0



SR29
0
80
0
20



SR30
0
85
0
15



SR31
0
88
0
12



SR32
0
90
0
10



SR33
0
95
0
5









The first heat transfer composition and the second heat transfer compositions also each generally include a lubricant, generally in amounts of from about 30 to about 50 percent by weight of the heat transfer composition, with the balance comprising refrigerant and other optional components that may be present. Combinations of surfactants and solubilizing agents may also be added to the present compositions to aid oil solubility, as disclosed by U.S. Pat. No. 6,516,837, the disclosure of which is incorporated by reference. Commonly used refrigeration lubricants such as Polyol Esters (POEs) and Poly Alkylene Glycols (PAGs), silicone oil, mineral oil, alkyl benzenes (ABs) and poly(alpha-olefin) (PAO) that are used in refrigeration machinery with hydrofluorocarbon (HFC) refrigerants may be used with the refrigerant compositions of the present invention. The preferred lubricants are POEs.


Preferred combinations of first refrigerant, second refrigerant and lubricant according to one aspect of the invention are provided below.















SECOND HEAT TRANSFER
FIRST HEAT TRANSFER



COMPOSITION
COMPOSITION

















Regrig.,

Lub,

Regrig.,

Lub,


EMBODIMENT
Refrig.
wt %
Lub
wt %
Refrig.
wt %
Lub
wt %


















1
1234yf
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


2
1234yf
80-89
PAG
11-20
CO2
80-90
POE
11-20


4
1234yf
90-99
POE
 1-10
CO2
90-99
POE
 1-10


5
1234yf
80-89
POE
11-20
CO2
80-90
POE
11-20


6
1234ze(E)
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


7
1234ze(E)
80-89
PAG
11-20
CO2
80-90
POE
11-20


8
1234ze(E)
90-99
POE
 1-10
CO2
90-99
POE
 1-10


9
1234ze(E)
80-89
POE
11-20
CO2
80-90
POE
11-20


10
SR1
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


11
SR1
80-89
PAG
11-20
CO2
80-90
POE
11-20


12
SR1
90-99
POE
 1-10
CO2
90-99
POE
 1-10


13
SR1
80-89
POE
11-20
CO2
80-90
POE
11-20


14
SR2
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


15
SR2
80-89
PAG
11-20
CO2
80-90
POE
11-20


16
SR2
90-99
POE
 1-10
CO2
90-99
POE
 1-10


17
SR2
80-89
POE
11-20
CO2
80-90
POE
11-20


18
SR3
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


19
SR3
80-89
PAG
11-20
CO2
80-90
POE
11-20


20
SR3
90-99
POE
 1-10
CO2
90-99
POE
 1-10


21
SR3
80-89
POE
11-20
CO2
80-90
POE
11-20


22
SR4
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


23
SR4
80-89
PAG
11-20
CO2
80-90
POE
11-20


24
SR4
90-99
POE
 1-10
CO2
90-99
POE
 1-10


25
SR4
80-89
POE
11-20
CO2
80-90
POE
11-20


26
SR5
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


27
SR5
80-89
PAG
11-20
CO2
80-90
POE
11-20


28
SR5
90-99
POE
 1-10
CO2
90-99
POE
 1-10


29
SR5
80-89
POE
11-20
CO2
80-90
POE
11-20


30
SR6
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


31
SR6
80-89
PAG
11-20
CO2
80-90
POE
11-20


32
SR6
90-99
POE
 1-10
CO2
90-99
POE
 1-10


33
SR6
80-89
POE
11-20
CO2
80-90
POE
11-20


34
SR7
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


35
SR7
80-89
PAG
11-20
CO2
80-90
POE
11-20


36
SR7
90-99
POE
 1-10
CO2
90-99
POE
 1-10


37
SR7
80-89
POE
11-20
CO2
80-90
POE
11-20


38
SR8
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


39
SR8
80-89
PAG
11-20
CO2
80-90
POE
11-20


40
SR8
90-99
POE
 1-10
CO2
90-99
POE
 1-10


41
SR8
80-89
POE
11-20
CO2
80-90
POE
11-20


41
SR9
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


42
SR9
80-89
PAG
11-20
CO2
80-90
POE
11-20


43
SR9
90-99
POE
 1-10
CO2
90-99
POE
 1-10


44
SR10
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


45
SR10
80-89
PAG
11-20
CO2
80-90
POE
11-20


46
SR10
90-99
POE
 1-10
CO2
90-99
POE
 1-10


47
SR10
80-89
POE
11-20
CO2
80-90
POE
11-20


48
SR11
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


49
SR11
80-89
PAG
11-20
CO2
80-90
POE
11-20


50
SR11
90-99
POE
 1-10
CO2
90-99
POE
 1-10


51
SR11
80-89
POE
11-20
CO2
80-90
POE
11-20


52
SR12
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


53
SR12
80-89
PAG
11-20
CO2
80-90
POE
11-20


54
SR12
90-99
POE
 1-10
CO2
90-99
POE
 1-10


55
SR12
80-89
POE
11-20
CO2
80-90
POE
11-20


56
SR13
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


57
SR13
80-89
PAG
11-20
CO2
80-90
POE
11-20


58
SR13
90-99
POE
 1-10
CO2
90-99
POE
 1-10


59
SR13
80-89
POE
11-20
CO2
80-90
POE
11-20


60
SR14
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


61
SR14
80-89
PAG
11-20
CO2
80-90
POE
11-20


62
SR14
90-99
POE
 1-10
CO2
90-99
POE
 1-10


63
SR14
80-89
POE
11-20
CO2
80-90
POE
11-20


64
SR15
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


65
SR15
80-89
PAG
11-20
CO2
80-90
POE
11-20


66
SR15
90-99
POE
 1-10
CO2
90-99
POE
 1-10


67
SR15
80-89
POE
11-20
CO2
80-90
POE
11-20


68
SR16
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


69
SR16
80-89
PAG
11-20
CO2
80-90
POE
11-20


70
SR16
90-99
POE
 1-10
CO2
90-99
POE
 1-10


71
SR16
80-89
POE
11-20
CO2
80-90
POE
11-20


72
SR17
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


73
SR17
80-89
PAG
11-20
CO2
80-90
POE
11-20


74
SR17
90-99
POE
 1-10
CO2
90-99
POE
 1-10


75
SR17
80-89
POE
11-20
CO2
80-90
POE
11-20


76
SR18
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


77
SR18
80-89
PAG
11-20
CO2
80-90
POE
11-20


78
SR18
90-99
POE
 1-10
CO2
90-99
POE
 1-10


79
SR18
80-89
POE
11-20
CO2
80-90
POE
11-20


80
SR19
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


81
SR19
80-89
PAG
11-20
CO2
80-90
POE
11-20


82
SR19
90-99
POE
 1-10
CO2
90-99
POE
 1-10


83
SR19
80-89
POE
11-20
CO2
80-90
POE
11-20


84
SR20
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


85
SR20
80-89
PAG
11-20
CO2
80-90
POE
11-20


86
SR20
90-99
POE
 1-10
CO2
90-99
POE
 1-10


87
SR20
80-89
POE
11-20
CO2
80-90
POE
11-20


88
SR21
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


89
SR21
80-89
PAG
11-20
CO2
80-90
POE
11-20


90
SR21
90-99
POE
 1-10
CO2
90-99
POE
 1-10


91
SR21
80-89
POE
11-20
CO2
80-90
POE
11-20


92
SR22
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


93
SR22
80-89
PAG
11-20
CO2
80-90
POE
11-20


94
SR22
90-99
POE
 1-10
CO2
90-99
POE
 1-10


95
SR22
80-89
POE
11-20
CO2
80-90
POE
11-20


96
SR23
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


97
SR23
80-89
PAG
11-20
CO2
80-90
POE
11-20


98
SR23
90-99
POE
 1-10
CO2
90-99
POE
 1-10


99
SR23
80-89
POE
11-20
CO2
80-90
POE
11-20


100
SR24
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


101
SR24
80-89
PAG
11-20
CO2
80-90
POE
11-20


102
SR24
90-99
POE
 1-10
CO2
90-99
POE
 1-10


103
SR24
80-89
POE
11-20
CO2
80-90
POE
11-20


104
SR25
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


105
SR25
80-89
PAG
11-20
CO2
80-90
POE
11-20


106
SR25
90-99
POE
 1-10
CO2
90-99
POE
 1-10


107
SR25
80-89
POE
11-20
CO2
80-90
POE
11-20


108
SR26
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


109
SR26
80-89
PAG
11-20
CO2
80-90
POE
11-20


110
SR26
90-99
POE
 1-10
CO2
90-99
POE
 1-10


111
SR26
80-89
POE
11-20
CO2
80-90
POE
11-20


112
SR27
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


113
SR27
80-89
PAG
11-20
CO2
80-90
POE
11-20


114
SR27
90-99
POE
 1-10
CO2
90-99
POE
 1-10


115
SR27
80-89
POE
11-20
CO2
80-90
POE
11-20


116
SR28
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


117
SR28
80-89
PAG
11-20
CO2
80-90
POE
11-20


118
SR28
90-99
POE
 1-10
CO2
90-99
POE
 1-10


119
SR28
80-89
POE
11-20
CO2
80-90
POE
11-20


120
SR29
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


121
SR29
80-89
PAG
11-20
CO2
80-90
POE
11-20


122
SR29
90-99
POE
 1-10
CO2
90-99
POE
 1-10


123
SR29
80-89
POE
11-20
CO2
80-90
POE
11-20


124
SR30
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


125
SR30
80-89
PAG
11-20
CO2
80-90
POE
11-20


126
SR30
90-99
POE
 1-10
CO2
90-99
POE
 1-10


127
SR30
80-89
POE
11-20
CO2
80-90
POE
11-20


128
SR31
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


129
SR31
80-89
PAG
11-20
CO2
80-90
POE
11-20


130
SR31
90-99
POE
 1-10
CO2
90-99
POE
 1-10


131
SR31
80-89
POE
11-20
CO2
80-90
POE
11-20


132
SR32
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


133
SR32
80-89
PAG
11-20
CO2
80-90
POE
11-20


134
SR32
90-99
POE
 1-10
CO2
90-99
POE
 1-10


135
SR32
80-89
POE
11-20
CO2
80-90
POE
11-20


136
SR33
90-99
PAG
 1-10
CO2
90-99
POE
 1-10


137
SR33
80-89
PAG
11-20
CO2
80-90
POE
11-20


138
SR33
90-99
POE
 1-10
CO2
90-99
POE
 1-10


139
SR33
80-89
POE
11-20
CO2
80-90
POE
11-20









System Operating Conditions

It is generally contemplated that operating conditions used in the present systems and methods can be varied widely in view of the disclosure contained herein depending upon the specific applications. However, many preferred applications will advantageously use operating parameters within the ranges indicated in the table below, with all amounts understood to be modified by “about”:
















BROAD
INTERMEDIATE
NARROW


















Evaporating
  −45 to −25
  −40 to −30
−35


temperature of





the low stage





evaporator, ° C.





Condensing
−10 to 10
−5 to 5
0


temperature of





the low-stage, ° C.





Evaporating temperature
−15 to 5 
−10 to 0 
−5


of the high-stage, ° C.





Condensing
35 to 55
40 to 50
45C


Temperature of





the high-stage, ° C.





Evaporator
 0 to 15
 0 to 10
5


Superheat (each stage),





° C.





Temperature rise
 5 to 25
10 to 20
15


in the suction line of





the low-stage, ° C.





Temperature rise
 0 to 15
 0 to 10
5


in the suction





line of the high-





stage, ° C.





Subcooling at both
 0 to 10
 0 to 5
0


expansion





devices of high





and low stages, ° C.





Compressor discharge
from about 120
from about 125
not greater


temperature (low and
to about130
to about 130
than 125


high stage), ° C.









When operating within the process conditions according to the present invention, the use of the suction line heat exchanger as described herein preferably produces at least a 2% COP improvement, more preferably at least about 3% COP improvement, and even more preferably a 4% COP improvement compared to the same system but without a suction-line heat exchanger according to the present invention.


In the following descriptions, components or elements of the system which are or can be generally the same or similar in different embodiments are designated with the same number or symbol.


One preferred refrigeration system is illustrated in FIG. 1. The refrigeration system is designated generally as 10. The boundaries designates generally as 100 represent schematically the enclosure. The low temperature loop comprises compressor 11, condensing side 12A of the cascade exchange 12, expansion valve 14 and evaporator 15. As illustrated, evaporator 15 is located within enclosure 100, together with any of the associated conduits and other connecting and related equipment to transport the first heat transfer composition to and from the enclosure boundary. Although the evaporator 14 is preferably located inside the enclosure, and is disclosed in the illustrated figure as being located inside of the enclosure 100, it will be appreciated that in certain embodiments it may be desirable and/or necessary to provide the expander 14 outside of the enclosure. The high temperature loop comprises compressor 21, evaporating side 12B of the cascade exchange 12, expansion valve 24 and condenser 25, all located outside of enclosure 100, together with any of the associated conduits and other connecting and related equipment. The high temperature circuit also includes suction line heat exchanger 50 which enables the exchange of heat between the second heat transfer composition stream 30 exiting condenser 25 and the second heat transfer composition stream 31 exiting the evaporating side 12B of the cascade heat exchanger 12.


Although it is contemplated that the relative size of the first and second refrigeration loops according to the present invention maybe vary widely within the scope hereof, applicants have found that highly advantageous results can be achieved in certain embodiments by judicious selection of the relative sizes of the refrigeration loops. More specifically, it is contemplated and understood that under normal operating conditions the heat transfer composition contained in the first refrigeration loop and in the second refrigeration loop will never mix or intermingle. However, applicants have come to appreciate that the possibility of such intermixing of first and second refrigerants might occur for example, in the case of leakage in the cascade heat exchanger. This mixed refrigerant stream may then, in the event of a leak within the enclosure being cold, become exposed to humans or other animals located in or near the enclosure. Accordingly, in order to ensure continued safe operation even in the case of such leakage, applicants have come to appreciate that careful and judicious selection of the relative refrigeration loop sizes can result in a safe system even in the event of such a leakage.


While applicants contemplate that the systems and compositions of the present invention will be useful in many refrigeration applications, preferred applications include refrigeration systems and methods used in applications such as treating the air, including cooling and/or heating, in enclosures such as residential dwellings, office space, warehouses and the like, and in connection with enclosures used to keep items cool by cooling the air in the enclosure, such as walk-in boxes, cold-boxes, transport refrigeration boxes and the like. As used herein, the term “transport refrigeration box” is used to designate cold/insulated boxes which are located on or comprise a portion or substantially all of a truck trailer. Furthermore, in preferred applications the capacity of the system according to the present invention is less than about 30 kW. In preferred applications the capacity of the system according to the present invention is less than about 15 kW, and in yet further applications the capacity of the system according to the present invention is less than about 10 kW.


Examples of several preferred systems, methods and compositions are described below:


A. First Refrigerant is CO2 and Second Refrigerant is R-1234ze(E)


By way of example, applicants have considered a cascade refrigeration system according to the present invention in which the first refrigerant consists of CO2 in the second refrigerant consists of R01234ze(E). In order to arrive at a refrigeration system according to the present invention which is safe, even in the event of intermixing between the first and second refrigerants, applicants have determined the flammability of various mixtures (including vapor and liquid) of these components as follows:
















Composition
Ratio












Number
R1234ze
CO2
CO2 to R1234ze
Flammability














1
99%
 1%
0.01
Vapor and liquid






flammable


2
90%
10%
0.11
Liquid flammable


3
70%
30%
0.43
Liquid flammable


4
50%
50%
1.00
Liquid flammable


5
46%
54%
1.17
Non-Flammable


6
40%
60%
1.50
Non-Flammable


7
30%
70%
2.33
Non-Flammable


8
 5%
95%
19.00
Non-Flammable









Based upon the above considerations and analysis, and preferred aspects of the present invention in which the first refrigerant consists essentially of CO2 and a second refrigerant consists essentially of R-1234ze(E), it is preferred that the weight ratio of the loading of the first refrigerant (e.g. CO2) in the low temperature loop to the second refrigerant (e.g. R-1234ze(E)) is not less than about 1.2. In such embodiments, the system of the present invention will remain safe, i.e., contain only nonflammable refrigerant, even in the event of complete intermixing between the first and the second refrigerant compositions.


B. First Refrigerant is CO2 and Second Refrigerant is SR26


By way of further example, applicants have considered a cascade refrigeration system according to the present invention in which the first refrigerant consists of CO2 and the second refrigerant consists of a SR26 (80:20 weight ratio combination of R-1234ze(E);R-32). In order to arrive at a refrigeration system according to the present invention which is safe, even in the event of intermixing between the first and second refrigerants, applicants have determined the flammability of various mixtures (including vapor and liquid) of these components as follows:
















Composition
Ratio













R1234ze + R32

CO2 to



Number
(0.8/0.2)
CO2
R1234ze + R32
Flammability














1
100% 
 0%
0
Vapor and






liquid






flammable


2
99%
 1%
0.01
Vapor and






liquid






flammable


3
90%
10%
0.11
Liquid






flammable


5
70%
30%
0.43
Liquid






flammable


6
50%
50%
1.00
Liquid






flammable


7
49%
51%
1.04
Non-Flammable


8
40%
60%
1.50
Non-Flammable


9
30%
70%
2.33
Non-Flammable


10
 5%
95%
19.00
Non-Flammable









Based upon the above considerations and analysis, and preferred aspects of the present invention in which the first refrigerant consists essentially of CO2 and a second refrigerant consists essentially of SR26, it is preferred that the weight ratio of the loading of the first refrigerant (e.g. CO2) in the low temperature loop to the second refrigerant (e.g. SR26) is not less than about 1.0. In such embodiments, the system of the present invention will remain safe, i.e., contain only nonflammable refrigerant, even in the event of complete intermixing between the first and the second refrigerant compositions.


C. First Refrigerant is CO2 and Second Refrigerant is R-32


By way of additional example, applicants have considered a cascade refrigeration system according to the present invention in which the first refrigerant consists of CO2 and the second refrigerant consists of a R-32. In order to arrive at a refrigeration system according to the present invention which is safe, even in the event of intermixing between the first and second refrigerants, applicants have determined the flammability of various mixtures (including vapor and liquid) of these components as follows:


















Composition
Ratio














Number
R32
CO2
CO2 to R32
Flammability
















1
100% 
 0%
0
Vapor and liquid







flammable



2
99%
 1%
0.01
Vapor and liquid







flammable



3
90%
10%
0.11
Vapor and liquid







flammable



4
80%
20%
0.25
Liquid flammable



5
70%
30%
0.43
Liquid flammable



6
60%
40%
0.67
Liquid flammable



7
53%
47%
0.89
Non-Flammable



8
50%
50%
1.00
Non-Flammable



9
40%
60%
1.50
Non-Flammable



10
10%
90%
9.00
Non-Flammable



11
 5%
95%
19.00
Non-Flammable









Based upon the above considerations and analysis, and preferred aspects of the present invention in which the first refrigerant consists essentially of CO2 and a second refrigerant consists essentially of SR26, it is preferred that the weight ratio of the loading of the first refrigerant (e.g. CO2) in the low temperature loop to the second refrigerant (e.g. SR26) is not less than about 0.9. In such embodiments, the system of the present invention will remain safe, i.e., contain only nonflammable refrigerant, even in the event of complete intermixing between the first and the second refrigerant compositions.


D. First Refrigerant is CO2 and Second Refrigerant is Ethane


By way of additional example, applicants have considered a cascade refrigeration system according to the present invention in which the first refrigerant consists of CO2 and the second refrigerant consists of ethane. In order to arrive at a refrigeration system according to the present invention which is safe, even in the event of intermixing between the first and second refrigerants, applicants have determined the flammability of various mixtures (including vapor and liquid) of these components as follows:
















Composition
Ratio












Number
Ethane
CO2
CO2 to Ethane
Flammability














1
100%
 0%
0
Vapor and liquid






flammable


2
 90%
10%
0.11
Vapor and liquid






flammable


3
 80%
20%
0.25
Vapor and liquid






flammable


4
 70%
30%
0.43
Liquid flammable


5
 60%
40%
0.67
Liquid flammable


6
 50%
50%
1.00
Liquid flammable


7
 40%
60%
1.50
Liquid flammable


8
 37%
63%
1.70
Non-Flammable


9
 30%
70%
2.33
Non-Flammable


10
 20%
80%
4.00
Non-Flammable


11
 10%
90%
9.00
Non-Flammable


12
 5%
95%
19.00
Non-Flammable









Based upon the above considerations and analysis, and preferred aspects of the present invention in which the first refrigerant consists essentially of CO2 and a second refrigerant consists essentially of ethane, it is preferred that the weight ratio of the loading of the first refrigerant (e.g. CO2) in the low temperature loop to the second refrigerant (e.g. SR26) is not less than about 1.7. In such embodiments, the system of the present invention will remain safe, i.e., contain only nonflammable refrigerant, even in the event of complete intermixing between the first and the second refrigerant compositions.


E. First Refrigerant is CO2 and Second Refrigerant is Propane


By way of additional example, applicants have considered a cascade refrigeration system according to the present invention in which the first refrigerant consists of CO2 and the second refrigerant consists of propone. In order to arrive at a refrigeration system according to the present invention which is safe, even in the event of intermixing between the first and second refrigerants, applicants have determined the flammability of various mixtures (including vapor and liquid) of these components as follows:
















Composition
Ratio












Number
Propane
CO2
CO2 to Propane
Flammability














1
100%
 0%
0
Vapor and liquid






flammable


2
 90%
10%
0.11
Liquid flammable


3
 80%
20%
0.25
Liquid flammable


4
 70%
30%
0.43
Liquid flammable


5
 60%
40%
0.67
Liquid flammable


6
 50%
50%
1.00
Liquid flammable


7
 40%
60%
1.50
Liquid flammable


8
 30%
70%
1.70
Liquid flammable


9
 20%
80%
1.50
Liquid flammable


10
 10%
90%
9.00
Non-Flammable


11
 5%
95%
19.00
Non-Flammable









Based upon the above considerations and analysis, and preferred aspects of the present invention in which the first refrigerant consists essentially of CO2 and a second refrigerant consists essentially of propane, it is preferred that the weight ratio of the loading of the first refrigerant (e.g. CO2) in the low temperature loop to the second refrigerant (e.g. propane) is greater than 4. In such embodiments, the system of the present invention will remain safe, i.e., contain only nonflammable refrigerant, even in the event of complete intermixing between the first and the second refrigerant compositions.


EXAMPLES
Comparative Example C1

Comparative Example Cl as described below is based on a typical walk-in cooler refrigeration system as illustrated in FIG. 2.


In FIG. 2, the boundaries of the cooler are represented schematically by the box 100. Enclosed within the cooler box is the evaporator 15 and expander 14. Compressor 11 and condenser 20 are located outside the cooler box 100. The refrigerant circulating within this refrigeration loop is refrigerant R-404A (52 wt. % R-143a, 44 wt. % R-125 and 4 wt. % R-134a).


The following operating parameters are used:

    • Evaporating temperature of evaporator 15=−35° C.
    • Condensing temperature of condenser 200=45° C.
    • Isentropic efficiency of expander 14=63%
    • Evaporator Superheat=5° C.
    • Temperature rise in the compressor suction line=20° C.
    • Expansion device subcooling=0° C.


      The operation of this typical system produces a compressor discharge temperature of 108.3° C.


Hybrid Examples H1A-H1D

A hybrid system based on the typical refrigeration system as illustrated in Example 1 is formed but a suction line heat exchanger is inserted so as to absorb heat into the R-404A exiting the evaporator and thereby increasing the temperature of R-404A entering the compressor by absorbing heat from R-404A exiting the condenser prior to that stream entering expander. Operation using a suction line heat exchanger with Effectiveness values varying from 35% to 85% are evaluated. The results are reported in the following Table H1, together with the result of comparative Example C1 for comparison:














TABLE H1






C1
H1A
H1B
H1C
H1D




















Effectiveness,
 0 (no heat
35
55
75
85


%*
exchanger)






Compressor
108.3
133.1
150.0
166.5
174.7


Discharge







Temperature,







° C.





*Effectiveness % of the suction line heat exchanger as used herein refers to the percentage of ideal operation with no heat loss






As can be seen from the results reported above, modifying a typical system to include a suction line heat exchanger is not viable since in every case there is a substantial, and unwanted and undesirable, increase in the compressor discharge temperature as a result of operating such a hybrid system.


Examples 1A-1E, 2A-2E, 3A-3E, 4A-4E and 5A-5E

A cascade refrigeration system having a suction line heat exchanger as illustrated in FIG. 1 is operated using each of the following refrigerants in the low temperature loop (the second refrigerant): HFO-1234ze(E); HFO-1234yf; SR21(80 wt % HFO-1234yf and 20 wt % R-32); SR26 (80 wt % HFO-1234ze(E) and 20 wt % R-32); and SR31(88 wt % HFO-1234ze(E) and 12 wt % R-32). The refrigerant in the high temperature loop is CO2. Using these refrigerants, the cascade system of the present invention is operated according to the following parameters:

    • Evaporating temperature of the low stage (evaporator 15)=−35° C.
    • Condensing temperature of the low-stage=(cascade condenser 12A)=0° C.
    • Evaporating temperature of the high-stage (evaporator 25)=−5° C.
    • Condensing Temperature of the high-stage (cascade condenser 12B)=45° C.
    • Isentropic efficiency of the low-stage expander (expander 14)=65%
    • Isentropic efficiency of the high-stage expander (expander 24)=63%
    • Evaporator Superheat (both evaporators)=5° C.
    • Temperature rise in the suction line of the low-stage=15° C.
    • Temperature rise in the suction line of the high-stage=5° C.
    • Subcooling at both expansion devices of high and low stages=0° C.
    • Suction-line Liquid-line heat exchanger Effectiveness=vary from 0% to 85%.


      Table 1/5-DT below shows the results in terms of discharge temperature for each example, with result from Comparative Example 1 being shown for comparison:









TABLE 1/5







DT













C1 and







1A-5A
1B-5B
1C-5C
1D-5D
1E-5E















Effective-
 0 (no heat
35
55
75
85


ness, %*
exchanger)











Refrigerant
Compressor Discharge Temperature, ° C.















R-404A
108.3
133.1
150.0
166.5
174.7


HFO-
 70
87
97
106
111


1234ze(E)







(Examples







1A-1E)







HFO-1234yf
 65
81
91
100
105


(Examples







2A-2E)







SR21
 68
85
95
104
109


(Examples







3A-3E)







SR26
 88
102
110
117
121


(Examples







4A-4E)







SR31
 81
96
104
112
116


(Examples







5A-5E)









As revealed by the table above, all Examples of the present invention satisfy the preferred compressor discharge temperatures of the present invention, and in all cases the discharge temperature is substantially superior to the performance of the typical system and even the hybrid system.


Table 1/5-COP below shows the results in terms of COP for each example, with result from Comparative Example 1 being shown for comparison:









TABLE 1/5







COP













C1 and







1A-5A
1B-5B
1C-5C
1D-5D
1E-5E





Effective-
0 (no heat
35
55
75
85


ness, %*
exchanger)











Refrigerant
COP (COP/% COP compared to Comparative Example 1)















R-404A
0.89/100






HFO-
1.12/125
1.14/128
1.16/130
1.17/131
1.18/132


1234ze(E)







(Examples







1A-1E)







HFO-1234yf
1.07/121
1.11/125
1.13/127
1.15/129
1.16/130


(Examples







2A-2E)







SR21
1.11/125
1.39/128
1.15/130
1.17/131
1.18/132


(Examples







3A-3E)







SR26
1.11/125
1.13/127
1.14/128
1.15/129
1.16/130


(Examples







4A-4E)







SR31
1.08/121
 1.1/123
1.11/125
1.12/126
1.13/127


(Examples







5A-5E)









As revealed by the table above, all Examples of the present invention result in improved COP of at least 121% compared to the system of Comparative Example 1. In addition all systems of the present invention which include a suction-line heat exchanger show at least an additional 2% improvement versus the system of the present invention without heat exchanger, and a systems with 55% or higher heat exchanger effectiveness for the suction line heat exchanger show at least an additional 3% improvement versus the system without heat exchanger.


Examples 6A-6E, 7A-7E, 8A-8E, 9A-9E

A cascade refrigeration system having no suction line heat exchanger and a suction line heat exchanger as illustrated in FIG. 1 is operated using each of the following refrigerants in the low temperature loop (the second refrigerant) and CO2 in the high temperature loop (showing the GWP of each refrigerant):















Component>>>





Second





Refrigerant





Designation
R-1234ze(E),




▾ ▾
wt %
R-32, wt %
GWP


















EX6
0
100
677


EX7
10
90
609


EX8
20
80
542


EX9
30
70
474









Using the same operating conditions identified in Examples 1-5, the system of FIG. 1 is operated with each of the refrigerants EX6-EX9, and Table 6/9-DT below shows the results in terms of discharge temperature for each example, with result from Comparative Example 1 being shown for comparison:









TABLE 6/9







DT













C1 and







6A-9A
6B-9B
6C-9C
6D-9D
6E-9E















Effective-
 0 (no heat
35
55
75
85


ness, %*
exchanger)











Refrigerant
Compressor Discharge Temperature, ° C.















R-404A
108
133
150
167.5
175


Examples
125
145
157
168
174


6A-6E)







Examples
121
140
151
162
167


7A-7E)







Examples
117
136
146
156
161


7A-7E







Examples
113
130
140
150
154


7A-7E









As revealed by the table above, using the refrigerants EX6-EX9 produce acceptable discharge temperatures (within the scope of preferred discharge temperature range) for cascade systems without a suction line heat exchanger (effectiveness=0). However, none of the refrigerants produce acceptable discharge temperatures (within the scope of preferred discharge temperature range) for cascade systems for any of the values of effectiveness from 35% to 85%.


Examples 10A -10E, 11A -11E, 12A-12E, 13A-13E, 14A-14E, 15A-15E

A cascade refrigeration system having no suction line heat exchanger and a suction line heat exchanger as illustrated in FIG. 1 is operated using each of the following refrigerants in the low temperature loop (the second refrigerant) and CO2 in the high temperature loop:















Component>>>





Second





Refrigerant





Designation
R-1234ze(E),




▾ ▾
wt %
R-32, wt %
GWP


















EX10
40
60
407


EX11
50
50
339


EX12
60
40
271


EX13
70
30
204


EX14
80
20
136


EX15
90
10
69









Using the same operating conditions identified in Examples 1-5, the system of FIG. 1 is operated with each of the refrigerants EX10-EX15, and Table 10/15-DT below shows the results in terms of discharge temperature for each example, with result from Comparative Example 1 being shown for comparison:









TABLE 10/15







DT













C1 and







10A-15
10B-15B
10C-15C
10D-15D
10E-15E















Effective-
 0 (no heat
35
55
75
85


ness, %*
exchanger)











Refrigerant
Compressor Discharge Temperature, ° C.















R-404A
108
133
150
167.5
175


Examples
109
125
134
143
148


10A-10E







Examples
104
120
128
137
141


11-11E







Examples
100
114
122
130
134


12A-12E







Examples
 94
108
116
124
128


13A-13E







Examples
 88
102
110
117
121


14A-14E







Examples
 81
95
103
111
115


15A-15E









As revealed by the table above, using the refrigerants EX10-EX15 results in a second refrigerant with a GWP value below 500, but not each refrigerant produces an acceptable discharge temperature (i.e., within the scope of preferred discharge temperature range). For cascade systems without a suction line heat exchanger (effectiveness=0), the discharge temperature is acceptable. However, for systems with a suction line heat exchanger, each of EX10 -EX13 refrigerants produce unacceptable discharge temperatures for the desired effectiveness values of 85% or above. Only EX 14 and EX 15 provide acceptable discharge temperatures for suction line heat exchangers having any of the tested effectiveness values. These finding are summarized below:

    • At 35% effectiveness, greater than 30% of R1234ze(E) is required
    • At 55% effectiveness: greater than 50% of R1234ze(E) is required
    • At 75% effectiveness: greater than 60% of R1234ze(E) is required
    • At 85% effectiveness: greater than 70% of R1234ze(E) is required
    • Compositions containing at least about 78% of R-1234ze(E) are acceptable for all effectiveness values of the suction line heat exchanger and produce a GWP value of about 150 or less.


Table 11/15-COP below shows the results in terms of COP for each example, with result from Comparative Example 1 being shown for comparison:









TABLE 10/15







COP













C1 and







10A-15A
10B-15B
10C-15C
10D-15D
10E-15E





Effective-
0 (no heat
35
55
75
85


ness, %*
exchanger)











Refrigerant
COP (COP/% COP compared to Comparative Example 1)















R-404A
0.89/100






Examples
 1.1/123
1.11/124
1.1/124
1.1/124
1.1/124


10A-10E







Examples
 1.1/124
 1.1/124
1.1/125
1.1/125
1.1/125


11-11E







Examples
 1.1/124
 1.1/125
1.1/125
1.1/126
1.1/126


12A-12E







Examples
 1.1/125
 1.1/127
1.1/128
1.2/129
1.2/130


13A-13E







Examples
 1.1/125
 1.1/127
1.1/129
1.2/130
1.2/131


14A-14E







Examples
 1.1/125
 1.1/128
1.2/130
1.2/131
1.2/132


15A-15E









As revealed by the table above, all Examples of the present invention result a COP of at least 121% compared to the system of Comparative Example 1. In addition the use of the refrigerant of Example 15 in all tested systems of the present invention which include a suction-line heat exchanger show at least an additional 2% improvement versus the system of the present invention without the suction-line heat exchanger, The use of the refrigerant of Example 14 in tested systems of the present invention which include a suction-line heat exchanger with and effectiveness of at least 55% show at least an additional 2% improvement versus the system of the present invention without the suction-line heat exchanger and (as shown in Table 11/15-DT) have an acceptable discharge temperature. The use of the refrigerant of Example 13 in tested systems of the present invention which include a suction-line heat exchanger with and effectiveness of at least 55% but less than about 85% show at least an additional 2% improvement versus the system of the present invention without the suction-line heat exchanger and (as shown in Table 11/15-DT) have an acceptable discharge temperature.


In contrast, while the use of the refrigerant of Example 12 in tested systems of the present invention which include a suction-line heat exchanger with an effectiveness of at least 75% show at least an additional 2% improvement versus the system of the present invention without the suction-line heat exchanger, as shown in Table 11/15-DT, this refrigerant does not provide an acceptable discharge temperature for this conditions.


Examples 16A-16E, 17A-17E, 18A-18E, 19A-19E

A cascade refrigeration system having no suction line heat exchanger and a suction line heat exchanger as illustrated in FIG. 1 is operated using each of the following refrigerants in the high temperature loop (the second refrigerant) and CO2 in the low temperature loop (showing the GWP of each refrigerant):















Component>>>





Second





Refrigerant





Designation
R-1234yf,




▾ ▾
wt %
R-32, wt %
GWP


















EX16
0
100
677


EX17
10
90
609


EX18
20
80
542


EX19
30
70
474









Using the same operating conditions identified in Examples 1-5, the system of FIG. 1 is operated with each of the refrigerants EX16-EX19, and Table 16/19-DT below shows the results in terms of discharge temperature for each example, with result from Comparative Example 1 being shown for comparison:









TABLE 16/19







DT













C1 and







16A-19A
16B-19B
16C-19C
16D-19D
16E-19E





Effective-
 0 (no heat
35
55
75
85


ness, %*
exchanger)











Refrigerant
Compressor Discharge Temperature, ° C.















R-404A
108
133
150
167.5
175


Examples
125
145
157
168
174


16A-16E)







Examples
119
138
149
160
166


17A-17E)







Examples
113
132
142
153
158


18A-18E







Examples
107
125
136
146
151


19A-19E









As revealed by the table above, using the refrigerants EX16-EX19 produce acceptable discharge temperatures (within the scope of preferred discharge temperature range) for cascade systems without a suction line heat exchanger (effectiveness=0). However, none of the refrigerants produce acceptable discharge temperatures (within the scope of preferred discharge temperature range) for cascade systems for any of the values of effectiveness from 35% to 85%.


Examples 20A-20E, 21A-21E, 22A-22E, 23A-23E, 24A-24E, 25A-25E

A cascade refrigeration system having no suction line heat exchanger and a suction line heat exchanger as illustrated in FIG. 1 is operated using each of the following refrigerants in the low temperature loop (the second refrigerant) and CO2 in the high temperature loop:















Component>>>





Second





Refrigerant





Designation
R-1234ze(E),




▾ ▾
wt %
R-32, wt %
GWP


















EX20
40
60
407


EX21
50
50
339


EX22
60
40
271


EX23
70
30
204


EX24
80
20
136


EX25
90
10
69









Using the same operating conditions identified in Examples 1-5, the system of FIG. 1 is operated with each of the refrigerants EX20-EX25, and Tables 20/25-DT below shows the results in terms of discharge temperature for each example, with result from Comparative


Example 1 being shown for comparison:









TABLE 20/25







DT













C1 and







20A-25
20B-25B
20C-25C
20D-25D
20E-25E















Effective-
 0 (no heat
35
55
75
85


ness, %*
exchanger)











Refrigerant
Compressor Discharge Temperature, ° C.















R-404A
108
133
150
167.5
175


Examples
102
125
134
143
148


20A-20E







Examples
 97
113
123
132
137


21-21E







Examples
 92
107
116
125
130


22A-22E







Examples
 86
102
110
119
123


23A-23E







Examples
 81
96
109
112
116


24A-24E







Examples
 74
89
97
105
110


25A-25E









As revealed by the table above, using the refrigerants EX21-EX25 results in a second refrigerant with a GWP value below 500, but not each refrigerant produces an acceptable discharge temperature (i.e., within the scope of preferred discharge temperature range). For cascade systems without a suction line heat exchanger (effectiveness=0), the discharge temperature is acceptable. However, for systems with a suction line heat exchanger, each of refrigerants EX20-EX22 produces unacceptable discharge temperatures for the desired effectiveness values of 85% or above. Only EX 23, EX24 and EX 25 provide acceptable discharge temperatures for suction line heat exchangers for all tested effectiveness values. These findings are summarized below:

    • At 35% effectiveness, greater than 30% of R1234yf is required
    • At 55% effectiveness: greater than 40% of R1234yf is required
    • At 75% and 85% effectiveness: greater than 60% of R1234yf is required


Table 20/25-COP below shows the results in terms of COP for each example, with result from Comparative Example 1 being shown for comparison:









TABLE 20/25







COP













C1 and







20A-25A
20B-25B
20C-25C
20D-25D
20E-25E





Effective-
0 (no heat
35
55
75
85


ness, %*
exchanger)











Refrigerant
COP (COP/% COP compared to Comparative Example 1)















R-404A
0.89/100






Examples
 1.1/122
1.11/122
1.1/122
1.1/122
1.1/122


20A-20E







Examples
 1.1/121
 1.1/122
1.1/123
1.1/123
1.1/123


21-21E







Examples
 1.1/121
 1.1/122
1.1/123
1.1/124
1.1/124


22A-22E







Examples
 1.1/121
 1.1/123
1.1/124
1.2/125
1.2/125


23A-23E







Examples
 1.1/121
 1.1/123
1.1/124
1.1/126
1.1/127


24A-24E







Examples
 1.1/121
 1.1/124
1.1/126
1.1/128
1.2/129


25A-25E









As revealed by the table above, all Examples of the present invention result a COP of at least 121% compared to the system of Comparative Example 1. In addition the use of the refrigerant of Examples 24 and 25 in all tested systems of the present invention which include a suction-line heat exchanger show at least an additional 2% improvement versus the system of the present invention without the suction-line heat exchanger, and the refrigerant of Examples 22 and 23 shows at least an additional 2% improvement versus the system of the present invention without the suction-line heat exchanger for heat exchangers with effectiveness of 55% or greater. The use of the refrigerant of Examples 22 in tested systems of the present invention which include a suction-line heat exchanger with an effectiveness of at least 75% show at least an additional 2% improvement versus the system of the present invention without the suction-line heat exchanger.


Importantly, the use of the refrigerant of Examples 24 and 25 in all tested systems of the present invention which include a suction-line heat exchanger not only show at least an additional 2% improvement versus the system of the present invention without the suction-line heat exchanger, such refrigerants (as shown in Table 21/25-DT) have an acceptable discharge temperature for all levels of suction line heat exchanger effectiveness tested. The use of the refrigerant of Examples 22 and 23 in tested systems of the present invention which include a suction-line heat exchanger with an effectiveness of 55% show not only at least an additional 2% improvement versus the system of the present invention without the suction-line heat exchanger but (as shown in Table 21/25-DT) also have an acceptable discharge temperature.


In contrast, while the use of the refrigerant of Example 20 does not demonstrate at least a 2% improvement for any values of heat exchanger effectiveness, and while Examples 21 and 22 show at least a 2% improvement for heat exchanger effectiveness values of 75% and 85%, these values of heat exchanger effectively do not does not provide an acceptable discharge, as shown in Table 20/25-DT, this refrigerant does not for this conditions.

Claims
  • 1. A heat transfer system for cooling the contents of an enclosure comprising: (a) a relatively low temperature vapor compression loop comprising a compressor, an expander and an evaporator in fluid communication in said loop, and a first heat transfer composition in said loop comprising a first refrigerant and lubricant for the compressor, said evaporator being located in said enclosure and being capable of absorbing heat from fluid in said enclosure at about said relatively low temperature;(b) a relatively high temperature vapor compression loop comprising a compressor, a condenser, an expander, and a suction line heat exchanger in fluid communication in said loop, and a second heat transfer composition in said loop comprising a second refrigerant and preferably lubricant for the compressor, said condenser being capable of transferring heat to a heat sink located outside said enclosure; and(c) a cascade heat exchanger for condensing said first refrigerant and evaporating said second refrigerant by heat exchange between said first and second refrigerant,
  • 2. The system of claim 1 wherein the first refrigerant has a flammability that is substantially less than the flammability of the second refrigerant.
  • 3. The system of claim 1 wherein the first refrigerant has a flammability classified as Al under ASHRAE 34 (as measured by ASTM E681) and the second refrigerant has a flammability that is classified as A2L under ASHRAE 34 (as measured by ASTM E681) or a higher flammability than A2L.
  • 4. The system of claim 1 wherein the first and the second refrigerant each have a Global Warming Potential (GWP) that is less than about 150.
  • 5. The system of claim 1 wherein each of said compressors and said expanders and said condenser are not located in the enclosure.
  • 6. The system of claim 5 wherein the suction line heat exchanger is not located in the enclosure.
  • 7. The system of claim 1 wherein said second refrigerant comprises one or more of trans1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), R-227ea, R-32 and combinations of two or more of these.
  • 8. The system of claim 1 wherein said second refrigerant comprises at least about 80% by weight of 2, 3,3,3-tetrafluoropropene (HFO-1234yf).
  • 9. The system of claim 1 wherein said second refrigerant consists essentially of HFO-1234ze(E), HFO-1234yf or combinations of these.
  • 10. The system of claim 1 wherein said second refrigerant comprises from about 70% by weight to about 90% by weight of HFO-1234yf and from about 10% by weight to about 30% by weight of R32.
  • 11. The system of claim 10 wherein said second refrigerant comprises from about 80% by weight of HFO-1234yf and about 20% by weight of R32.
  • 12. The system of claim 1 wherein said second refrigerant comprises from about 70% by weight to about 90% by weight of HFO-1234yze(E) and from about 10% by weight to about 30% by weight of R32.
  • 13. The system of claim 1 wherein said second refrigerant comprises about 80% by weight of HFO-1234ze(E) and about 20% by weight of R32.
  • 14. The system of claim 1 wherein said second refrigerant comprises from about 85% to about 90% by weight of trans1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) and from about 10% by weight to about 15% by weight of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).
  • 15. The system of claim 1 wherein said second refrigerant comprises from about 88% by weight of trans1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) and from about 10% by weight to about 12% by weight of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea).
  • 16. The system of claim 1 wherein the evaporating temperature of said first refrigerant in said relatively low temperature vapor compression loop is from about −45° C. to about −25° C.
  • 17. The system of claim 16 wherein the evaporating temperature of said second refrigerant in said relatively high temperature vapor compression loop is from about −15° C. to about 5° C.
  • 18. The system of claim 17 wherein the condensing temperature of said first refrigerant in said relatively low temperature vapor compression loop is from about −5° C. to about −5° C.
  • 19. The system of claim 18 wherein the condensing temperature of said second refrigerant in said relatively high temperature vapor compression loop is from about 40° C. to about 50° C.
  • 20. The system of claim 19 wherein said first refrigerant comprises carbon dioxide and said second refrigerant comprises one or more of trans1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf), R-227ea, R-32 and combinations of two or more of these.
CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority to Provisional Application 62/313,177, filed Mar. 25, 2016, which is incorporated herein by reference in its entirety. The present application is also a continuation-in-part of U.S. application Ser. No. 15/400,891, filed Jan. 6, 2017, now pending, which in turn claims the priority benefit of Provisional application 62/275,382, filed Jan. 6, 2016, each of which is incorporated herein by reference in its entirety. The present application is also a continuation-in-part of U.S. application Ser. No. 15/434,400, filed Feb. 16, 2017, now pending, which in turn claims the priority benefit of 62/295,731, filed Feb. 16, 2016, the entire contents of each of which is hereby incorporated by reference.

Provisional Applications (3)
Number Date Country
62313177 Mar 2016 US
62275382 Jan 2016 US
62295731 Feb 2016 US
Continuation in Parts (2)
Number Date Country
Parent 15400891 Jan 2017 US
Child 15468292 US
Parent 15434400 Feb 2017 US
Child 15400891 US