Use of R-1233 in liquid chillers

Abstract

This invention relates to the use of chloro-trifluoropropenes as refrigerants in negative-pressure liquid chillers and methods of replacing an existing refrigerant in a chiller with chloro-trifluoropropenes. The chloro-trifluoropropenes, particularly 1-chloro-3,3,3-trifluoropropene, have high efficiency and unexpectedly high capacity in liquid chiller applications and are useful as more environmentally sustainable refrigerants for such applications, including the replacement of R-123 and R-11.

Claims

1. A chiller system comprising a compressor, at least one liquid cooler, at least one condenser, a purge unit, and a refrigerant; wherein said compressor is a centrifugal compressor and said refrigerant comprises 1-chloro-3,3,3-trifluoropropene, and where in the 1-chloro-3,3,3-trifluoropropene comprises greater than 70 wt % the trans-isomer.

2. The chiller system of claim 1 wherein said compressor is a centrifugal compressor.

3. The chiller system of claim 1 wherein said compressor is a multistage compressor.

4. The chiller system of claim 1 wherein said multistage compressor is a centrifugal compressor with 2 or 3 stages.

5. The chiller system of claim 1 wherein said compressor is an oil-free compressor.

6. The chiller system of claim 1 wherein said liquid cooler is a flooded evaporated.

7. The chiller system of claim 1 wherein said compressor contains a lubricant.

8. The chiller system of claim 1 wherein said at least one condenser comprises at least one water-cooled condenser.

9. The chiller system of claim 1 wherein said at least one condenser comprises at least one air-cooled condenser.

10. The chiller system of claim 1 wherein one of said at least one condensers of the chiller system is operated at temperatures ranging from about 26.7 C. (80 F.) to 60 C. (140 F.).

11. The chiller system of claim 1 wherein said chiller system is a heat recovery chiller system.

12. The heat recovery chiller system of claim 11 wherein heat is recovered from water leaving said at least one water-cooled condenser.

13. The heat recovery chiller system of claim 11 wherein heat is recovered from said refrigerant.

14. The chiller system of claim 1 wherein said lubricant is selected from the group consisting of mineral oils, polyol ester oils, polyalklylene glycol oils, polyvinyl ether oils, poly(alphaolefin) oils, alkyl benzene oils and mixtures thereof.

15. The chiller system of claim 1 wherein said lubricant is selected from the group consisting of mineral oils, polyol ester oils, polyvinyl ether oils, alkyl benzene oils and mixtures thereof.

16. The chiller system of claim 1 wherein said 1-chloro-3,3,3-trifluoropropene is greater than 90 wt % trans-isomer.

17. The chiller system of claim 1 wherein said 1-chloro-3,3,3-trifluoropropene is greater than 97 wt % trans-isomer.

18. The chiller system of claim 1 wherein said 1-chloro-3,3,3-trifluoropropene is greater than 99 wt % trans-isomer.

19. The chiller system of claim 1 wherein said 1-chloro-3,3,3-trifluoropropene is essentially the trans-isomer.

20. The chiller system of claim 1 wherein said refrigerant further comprises a hydrofluoroolefin, hydrofluorocarbon, a hydrochlorofluorocarbon, a chlorofluorocarbon, a hydrochloroolefin, a fluoroketone, a hydrofluoroether, a hydrocarbon, ammonia, and mixtures thereof.

21. The chiller system of claim 1 wherein said purge unit comprises a refrigeration system, a pump-out system and system controls.

22. The chiller system of claim 21 where said refrigeration system comprises a compressor, a condenser, an expansion device, an evaporator, and a purge refrigerant.

23. The chiller system of claim 22 where said purge refrigerant comprises one or more of hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, hydrocarbons, hydrofluoroethers, fluoroketones, chlorofluorocarbons, trans-1,2-dichloroethylene, carbon dioxide, dimethyl ether, ammonia, and mixtures thereof.

24. The chiller system of claim 23 where said purge refrigerant comprises HFC-134a, HFC-32, HFC-125, HFC-143a, HFO-1234yf, E-HFO-1234ze, HCFC-22, carbon dioxide, propane, propylene, butane, or mixtures thereof.

25. The chiller system of claim 23 where said purge refrigerant is selected from the group consisting of HFC-134a, HFC-32, HFO-1234yf, E-HFO-1234ze, R-404A, R-507A, R-407A, R-407C, R-407F, R-40711, R-410A, R-513A, R-444A, R-444B, R-445A, R-446A, R-447A, R-447B, R-448A, R-449A, R-449B, R-449C, R-450A, R-451A, R-451B, R-452A, R-452B, R-452C, R-454A, R-454B, R-454C, R-455A, R-456A, R-457A, R-513A, R-513B, R-515A, carbon dioxide, and hydrocarbons; where hydrocarbons.

26. The chiller system of claim 25 wherein said hydrocarbon is selected form the group consisting of propane, butane, isobutane, propylene and mixtures thereof.

27. A method detecting leaks in the chiller system of claim 1 that comprises monitoring the frequency of pump-out cycles of said purge unit.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic of a typical chiller system.

(2) FIG. 2 is a chart of COP for R-123, R-1233zd, and R-1234yf at an evaporator temperature of 10 C.

(3) FIG. 3 is a chart of CAP for R-123, R-1233zd, and R-1234yf at an evaporator temperature of 10 C.

(4) FIG. 4 is a chart of COP for R-123, R-1233zd, and R-1234yf at an evaporator temperature of 0 C.

(5) FIG. 5 is a chart of CAP for R-123, R-1233zd, and R-1234yf at an evaporator temperature of 0 C.

(6) FIG. 6 is a chart of COP for R-123, R-1233zd, and R-1234yf at an evaporator temperature of 5 C.

(7) FIG. 7 is a chart of CAP for R-123, R4233zd, and R-1234yf at an evaporator temperature of 5 C.

(8) FIG. 8 is a chart of COP for R-123, R-1233zd, and R-1234yf at an evaporator temperature of 10 C.

(9) FIG. 9 is a chart of CAP for R-123, R-1233zd, and R-1234yf at an evaporator temperature of 10 C.

DETAILED DESCRIPTION OF THE INVENTION

(10) The chloro-trifluoropropene refrigerant composition of the present invention can be added to a new chiller system or be employed in a method of topping-off or retrofitting an existing chiller system. The chloro-trifluoropropene refrigerant composition of the present invention is particularly useful in chillers, preferably those operated at negative pressure, using centrifugal compressors and flooded evaporators. The retrofit method, comprises the steps of removing the existing refrigerant from the chiller system while optionally retaining a substantial portion of the lubricant in said system; and introducing to said system a composition comprising a chloro-trifluoropropene refrigerant of the present invention which is miscible with the lubricant present in the system without the need for addition surfactants and/or solubilizing agents. In topping-off an existing chiller system, the chloro-trifluoropropene refrigerant of the present invention is added to top-off a refrigerant charge or as a partial replacement either to replace refrigerant lost or after removing part of the existing refrigerant and then adding the chloro-trifluoropropene refrigerant of the present invention. The preferred chloro-trifluoropropene refrigerant of the present invention is preferably 1-chloro-3,3,3-trifluoropropene and/or 2-chloro-3,3,3-trifluoropropene, and more preferably trans-1-chloro-3,3,3-trifluoropropene.

(11) As used herein, the term substantial portion refers generally to a quantity of lubricant which is at least about 50% (all percentages herein are by weight unless indicated otherwise) of the quantity of lubricant contained in the refrigeration system prior to removal of the prior refrigerant. Preferably, the substantial portion of lubricant in the system according to the present invention is a quantity of at least about 60% of the lubricant contained originally in the refrigeration system, and more preferably a quantity of at least about 70%.

(12) Any of a wide range of known methods can be used to remove prior refrigerants from a chiller system while removing less than a major portion of the lubricant contained in the system. According to preferred embodiments, the lubricant is a hydrocarbon-based lubricant and the removal step results in at least about 90%, and even more preferably at least about 95%, of said lubricant remaining in the system. The removal step may readily be performed by pumping the original refrigerants in the gaseous state out of a refrigeration system containing liquid state lubricants, because refrigerants are quite volatile relative to traditional hydrocarbon-based lubricants. The boiling point of refrigerants are generally under 30 C. whereas the boiling point of mineral oils are generally over 200 C. Such removal can be achieved in any of a number of ways known in the art, including, the use of a refrigerant recovery system. Alternatively, a cooled, evacuated refrigerant container can be attached to the low pressure side of a refrigeration system such that the gaseous prior refrigerant is drawn into the evacuated container and removed. Moreover, a compressor may be attached to a refrigeration system to pump the prior refrigerant from the system to an evacuated container. In light of the above disclosure, those of ordinary skill in the art will be readily able to remove the prior refrigerants from chiller systems and to provide a refrigeration system comprising a chamber having therein a hydrocarbon-based lubricant and a chloro-trifluoropropene refrigerant according to the present invention.

(13) A method of the present invention comprises introducing to a chiller system, a composition comprising at least one chloro-trifluoropropene refrigerant of the present invention miscible with the lubricant present in the system, if a lubricant is used. The lubricants in the chiller system can be hydrocarbon lubricating oils, oxygenated lubrication oils or mixtures thereof.

(14) An embodiment of the present invention is a chiller system comprising (1) a compressor, (2) at least one liquid cooler, (3) at least one condenser, and (4) a chloro-trifluoropropene refrigerant of the present invention. The chiller system may also comprise a purge unit. The compressor of said chiller system is preferably a centrifugal compressor. In an embodiment of the present invention, the compressor in the chiller system has from 1 to 12 stages, preferably 2 or 3 stages, even more preferably 2 stages. In an embodiment of the present invention, the compressor in the chiller system uses a lubricating oil. In another embodiment of the present invention, the compressor is an oil-free compressor, preferably an oil-free compressor using magnetic bearings or using hybrid bearings.

(15) A purge unit of the chiller system of the present invention can be used to remove non-condensable gases, including air, and moisture that enter the chiller system. In a preferred embodiment of the present invention the purge system comprises a refrigeration system, a venting or pump-out system, system controls, and preferably also comprises a filter drier. In another preferred embodiment of the present invention the refrigeration system of the purge system comprises a compressor, a condenser (such as a condensing coil), an expansion device (such as an expansion valve), an evaporator (such as an evaporator coil), and a purge refrigerant. The evaporator of the refrigeration system of the purge unit is preferably located inside of a purge tank. Preferably the purge system operates with the evaporator at lower temperature and pressure than condenser of the chiller. In a preferred embodiment of the present invention the purge unit is connected to the condenser of the chiller, more preferably just above the level of liquid refrigerant in the condenser of the chiller, where refrigerant vapor and non-condensables may be drawn from the chiller to the purge unit.

(16) In one embodiment of the present invention is a method of operation for the purge system of the chiller system of the present invention. The purge system may be operated such that refrigerant and non-condensables are drawn from the chiller into a purge tank where refrigerant from the chiller system may be condensed in the purge tank due to the lower temperature and/or pressure of the purge tank than the condenser of the chiller. The condensed, liquid refrigerant is sent back to the condenser of the chiller system via a return line. Air and other non-condensables will accumulate in the purge tank; this insulates the evaporator of the purge unit to heat transfer and decreases the temperature of the purge refrigerant leaving the evaporator of the purge system. The temperature leaving the evaporator of the purge unit is called the purge suction temperature. In an embodiment of the present invention the purge suction temperature is used to control the operation of the purge unit; when the purge suction temperature drops below a set-point the purge unit controller initiates a pump-out process. In a preferred embodiment of the present invention, this pump-out process includes switching of one or more valves to isolate the purge tank, opening a pump-out line to a pump-out compressor, turn on the pump-out compressor, pump the contents of the purge tank to a filtration unit. Refrigerant from the chiller system removed during a pump-out process may be collected in the filtration unit for return to the condenser of the chiller system. The air and other non-condensables may be vented from the exit of the filtration unit or optionally connected to a chiller vent line.

(17) In an embodiment of the present invention the purge unit has a filter drier in the refrigerant return line between the purge tank of purge unit and the condenser of the chiller system.

(18) In an embodiment of the present invention the purge refrigerant of the purge system comprises one or more refrigerants selected from the group hydrofluorocarbons, hydrochlorofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, hydrocarbons, hydrofluoroethers, fluoroketones, chlorofluorocarbons, trans-1,2-dichloroethylene, carbon dioxide, dimethyl ether, ammonia, and mixtures thereof. Exemplary hydrofluorocarbons include difluoromethane (HFC-32); 1-fluoroethane (HFC-161); 1,1-difluoroethane (HFC-152a); 1,2-difluoroethane (HFC-152); 1,1,1-trifluoroethane (HFC-143a); 1,12-trifluoroethane (HFC-143); 1,1,1,2-tetrafluoroethane (HFC-134a); 1,1,2,2-tetrafluoroethane (HFC-134); 1,1,1,2,2-pentafluoroethane (HFC-125); 1,1,1,3,3-pentafluoropropane (HFC-245fa); 1,1,2,2,3-pentafluoropropane (HFC-245ca); 1,1,1,2,3-pentafluoropropane (HFC-245eb); 1,1,1,3,3,3-hexafluoropropane (HFC-236fa); 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea); 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,3,4,4,5,5,5-decafluoropropane (HFC-4310), and mixtures thereof. Exemplary hydrochlorofluorocarbons include difluorochloromethane (R-22). Exemplary chlorofluorocarbons include trichlorofluoromethane (R-11), dichlorodifluoromethane (R-12), 1,1,2-trifluoro-1,2,2-trifluoroethane (R-113), 1,2-dichloro-1,1,2,2-tetrafluoroethane (R-114), chloro-pentafluoroethane (R-115) and mixtures thereof. Exemplary hydrocarbons include propane, butane, isobutane, n-pentane, iso-pentane, neo-pentane, cyclopentane, and mixtures thereof. Exemplary hydrofluoroolefins include 3,3,3-trifluorpropene (HFO-1234zf), 2,3,3,3-tetrafluoropropene (HFO-1234yf), E-1,2,3,3,-pentafluoropropene (E-HFO-1225ye), Z-1,2,3,3,3-pentafluoropropene (Z-HFO-1225ye), E-1,1,1,3,3,3-hexafluorobut-2-ene (E-HFO-1336mzz), Z-1,1,1,3,3,3-hexafluorobut-2-ene (Z-HFO-1336mzz), 1,1,1,4,4,5,5,5-octafluoropent-2-ene (HFO-1438mzz) and mixtures thereof. Exemplary hydrochlorofluoroolefins include E-1-chloro-3,3,3-trifluoropropene (E-HCFO-1233zd), Z-1-chloro-3,3,3-trifluoropropene (Z-HCFO-1233zd), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf). Exemplary hydrofluoroethers include 1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane, 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxy-butane and mixtures thereof. Preferably the refrigerant of the purge system comprises a hydrofluorocarbon, hydrchlorofluorocarbon, hydrofluoroolefin, hydrocarbon, carbon dioxide, or mixtures thereof, more preferably the refrigerant of the purge system comprises HFC-134a, HFC-32, HFC-125, HFC-143a, HFO-1234yf E-HFO-1234ze, HCFC-22, carbon dioxide, propane, propylene, butane, or mixtures thereof. In another embodiment of the present invention the refrigerant of the purge system is selected from the group of refrigerants with ASHRAE designations consisting of HFC-134a, HFC-32, R-404A, R-507A, R-407A, R-407C, R-407F, R-407H, R-410A, R-513A, R-444A, R-444B, R-445A, R-446A, R-447A, R-44713, R-448A, R-449A, R-449B, R-449C, R-450A, R-451A, R-451B, R-452A, R-452B, R-452C, R-454A, R-454B, R-454C, R-455A, R-456A, R-457A, R-513A, R-513B, R-515A. In another embodiment of the present invention the refrigerant of the purge system is a selected from the group consisting of R-404A, R-507A, R-407A, R-407F, R-407H, R-448A, R-449A, R-449B, R-452A, R-452C, R-454A, R-457A.

(19) Another embodiment of the present invention is a method a leak detection for the chiller system of the present that comprises monitoring the frequency of pump-out cycles of the purge unit.

(20) In another embodiment of the present invention, the compressor in the chiller system is an oil-free compressor where the chloro-trifluoropropene refrigerant of the present invention acts a lubricating agent. In an embodiment of the present invention, the liquid cooler in the chiller system is a flooded evaporator. In an embodiment of the present invention, the condenser in the chiller system is a water-cooled condenser. In another embodiment of the present invention, the condenser of the chiller system is an air-cooled condenser.

(21) In another embodiment of the present invention, the chiller system is a heat recovery Chiller system comprising (1) a compressor, (2) at least one liquid cooler, (3) one or more condensers, and (4) a chloro-trifluoropropene refrigerant of the present invention. In another embodiment of the present invention, the liquid cooler of the chiller system is preferably a flooded evaporator, with one portion operated at a pressure below atmospheric pressure. In another embodiment of the present invention, the chiller system is a heat recovery chiller system containing one or multiple water-cooled condensers, and heat is recovered from the water leaving one of the condensers. In another embodiment of the present invention, the chiller system is a heat recovery chiller system and the condenser of the heat recovery chiller system is a water-cooled condenser or air-cooled condenser and heat is recovered from the refrigerant. In another embodiment, the chiller system is a heat recovery chiller system where the compressor is a centrifugal compressor.

(22) Another embodiment of the present invention is a process for producing heating in a heat recovery chiller system or heat-pump chiller. In an embodiment of the present invention, the liquid cooler of the chiller system in the method is preferably a flooded evaporator with one portion operated at a pressure below atmospheric pressure. In an embodiment of the present invention, at least one of the condensers of the chiller system in the method is preferably operated at temperatures ranging from about 26.7 C. (80 F.) to 60 C. (140 F.), preferably from about 29.4 C. (85 F.) to 55 C. (131 F.).

(23) Another embodiment of the present invention is a method of producing cooling using the chiller system of the present invention. In an embodiment of the present invention, the method of producing cooling uses a liquid cooler of the chiller system which is preferably a flooded evaporator with one portion operated at a pressure below atmospheric pressure. In an embodiment of the present invention, the method of producing cooling uses a condenser of the chiller system that is preferably operated at temperatures ranging from about 26.7 C. (80 F.) to 60 C. (140 F.), preferably from about 29.4 C. (85 F.) to 55 C. (131 F.).

(24) In an embodiment of the present invention, the chloro-trifluoropropene refrigerant is 1-chloro-3,3,3-fluoropropene, which may comprise a mixture of the trans- and cis-isomers of 1-chloro-3,3,3-fluoropropene, preferably predominantly the trans-isomer, more preferably greater than 70 wt % of the trans-isomer, more preferably greater than 90 wt % of the trans-isomer, more preferably greater than 97 wt % of the trans-isomer, and even more preferably greater than 99 wt % of the trans-isomer. In another embodiment of the present invention, the chloro-trifluoropropene refrigerant is essentially trans-1-chloro-3,3,3-trifluoropropene.

(25) Another embodiment of the present invention is a process for producing cooling in a chiller system comprising compressing a refrigerant in a compressor, and evaporating the refrigerant in the vicinity of a body to be cooled, wherein said refrigerant comprises chloro-trifluoropropene.

(26) In an embodiment of the present invention, the refrigerant of the present invention has an acoustic velocity close to that of R-123 or R-11, preferably where the acoustic velocity of the refrigerant of the present invention is within 10% of the acoustic velocity of R-123 or R-11 at conditions at the inlet of the compressor of the chiller system. In another embodiment of the present invention, the acoustic velocity of the refrigerant of the present invention is less than bout 150 m/s at 40 C. and 1 bar, preferably less than about 145 m/s at 40 C. and 1 bar. In another embodiment of the present invention, the acoustic velocity of the refrigerant of the present invention is from about 130 to about 150 m/s at conditions of the compressor of the chiller system.

(27) In addition to the chloro-trifluoropropene refrigerant of the present invention, the composition introduced into the system can include an additional refrigerant selected from hydrofluorcarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochloroolefins, hydrofluoroethers, fluoroketones, hydrocarbons, ammonia, or mixtures thereof, preferably where the additional refrigerant is non-flammable and/or the resulting refrigerant composition is non-flammable.

(28) The hydrofluorocarbon can be selected from difluromethane (HFC-32), 1-fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), 1,2-difluoroethane (HFC-152), 1,1,1-trifluoroethane (HFC-143a), 1,1,2-trifluoroethane (HFC-143), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), 1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,2,2,3-pentafluoropropane (HFC-245ca), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,3,3-pentafluorbutane (HFC-365mfc), 1,1,1,2,3,4,4,5,5,5-decafluoropropane (HFC-4310) and mixtures thereof.

(29) The hydrochlorofluorocarbon can be selected from 1,1-dichloro-2,2,2-trifluoroethane (R-123), 1-chloro-1,2,2,2-tetrafluoroethane (R-124), 1,1-dichloro-1-fluoroethane (R-141b). 1-chloro-1,1-difluoroethane (R-142b) and mixtures thereof, preferably R-123.

(30) The chlorofluorcarbons can be trichlorofluoromethane (R-11), dichlorodifluoromethane (R-12), 1,1,2-trichloro-1,2,2-trifluoroethane (R-113), 1,2-dichloro-1,1,2,2-tetrafluoroethane (R-114), chloropentafluoroethane (R-115), or mixtures thereof, preferably R-11.

(31) Exemplary hydrofluoroethers include 1,1,1,2,2,3,3-heptafluoro-3-methoxy-propane, 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxy-butane, or mixtures thereof. An exemplary fluoroketone is 1,1,1,2,2,4,5,5,5-nonafluoro-4(trifluoromethyl)-3-pentanone.

(32) The hydrofluoroolefins can be a C3 to C5 hydrofluoroolefin containing at least one fluorine atom, at least one hydrogen atom and at least one alkene linkage. Exemplary hydrofluoroolefins include 3,3,3-trifluoropropene (HFO-1234zf), E-1,3,3,3-tetrafluoropropene, (E-HFO-1234ze), Z-1,3,3,3-tetrafluoropropene (Z-HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf), E-1,2,3,3,-pentafluoropropene (E-HFO-1255ye), Z-1,2,3,3,3-pentafluoropropene (Z-HFO-125ye), E-1,1,1,3,3,3-hexafluorobut-2-ene (E-HFO-1336mzz), Z-1,1,1,3,3,3-hexafluorobut-2-ene (Z-HFO-1336mzz), 1,1,1,4,4,5,5,5-octafluoropent-2-ene (HFO-1438mzz) or mixtures thereof.

(33) An exemplary hydrochloroolefin is trans-1,2-dichloroethylene.

(34) The hydrocarbons can C3 to C7 alkanes, preferably butanes, pentanes, or mixtures thereof, more preferably n-pentane, isopentane, cyclopentane, or mixtures thereof.

(35) Current chiller lubricants include, but are not limited to, mineral oils, polyol ester oils, polyalkylene glycol oils, polyvinyl ether oils, poly(alphaolefin) oils, alkyl benzene oils and mixtures thereof. Preferred chiller lubricants are mineral oils, polyol ester oils, and polyvinyl ether oils. The chloro-trifluopropenes of the present invention were found to be miscible with mineral oils as well as other chiller lubricants.

(36) In addition to the chloro-trifluoropropene refrigerant miscible with the lubricant of the present invention, the composition introduced into the system can include other additives or materials of the type used in refrigerant compositions to enhance their performance in refrigeration systems. For example, the composition can include extreme pressure and antiwear additives, oxidation stability improvers, corrosion inhibitors, viscosity index improvers, pour and floc point depressants, antifoaming agents, viscosity adjusters, UV dyes, tracers, and the like.

(37) The following non-limiting examples are hereby provided as reference:

EXAMPLES

Liquid Chiller Performance Data

(38) The performance of the refrigerants R-123 (1,1-dichloro-2,2,2-trifluoroethane), R-1233zd (1-chloro-3,3,3-trifluoropropene, predominantly trans-isomer), and R-1234yf (2,3,3,3-tetrafluoropropene) in a liquid chiller application were evaluated in the following examples. In each example, data is provided at a given evaporator temperature and at multiple condenser temperatures, ranging from 30 C. to 55 C. The isentropic efficiency in each case was 0.7. Data for R-123 and R-1234yf are provided as comparative examples.

(39) In the following examples, the following nomenclature is used: Condenser discharge temperature: T cond Condenser pressure: P cond Evaporator pressure: P evap Pressure difference between condenser and evaporator: P diff Pressure ratio of the condenser to the evaporator: P ratio Coefficient of Performance (energy efficiency): COP Capacity: CAP

Example 1

(40) In this example, the following conditions were used:

(41) Evaporator temperature=10 C. Compressor inlet temperature=5 C. isentropic efficiency=0.7. The results are tabulated in Table 1.

(42) FIGS. 2 and 3 show the COP and CAP of R-1233zd and R-1234yf relative to R-123.

(43) TABLE-US-00001 TABLE 1 T evap 10 C. Internal heat exchanger inlet compressor 5 C. isentropic efficiency 0.7 Tcond evap P cond P P diff P ratio CAP ( C.) (kPa) (kPa) (kPa) (p/p) (KJ/m.sup.3) COP R-1234yf 30.0 219 772 554 3.53 1456 3.6 35.0 219 882 663 4.03 1372 3.1 40.0 219 1003 785 4.58 1287 2.7 45.0 219 1137 918 5.19 1200 2.3 50.0 219 1283 1064 5.86 1111 2.0 55.0 219 1443 1224 6.59 1019 1.7 R-1233zd 30.0 28 155 127 5.51 280 3.9 35.0 28 184 156 6.54 269 3.4 40.0 28 217 189 7.71 257 2.9 45.0 28 254 226 9.04 245 2.6 50.0 28 296 268 10.52 233 2.3 55.0 28 343 314 12.18 222 2.1 R-123 30.0 20 110 90 5.44 206 4.0 35.0 20 131 111 6.47 199 3.5 40.0 20 155 135 7.66 192 3.1 45.0 20 182 162 9.00 184 2.7 50.0 20 213 192 10.52 177 2.4 55.0 20 247 227 12.23 169 2.2

Example 2

(44) In this example, the following conditions were used:

(45) Evaporator temperature=0 C. Compressor inlet temperature=5 C. Isentropic efficiency=0.7. The results are tabulated in Table 2.

(46) FIGS. 4 and 5 show the COP and CAP of R-1233zd and R-1234yf relative to R-123.

(47) TABLE-US-00002 TABLE 2 T evap 0 C. Internal heat exchanger inlet compressor 5 C. isentropic efficiency 0.7 Tcond evap P cond P P diff P ratio CAP ( C.) (kPa) (kPa) (kPa) (p/p) (KJ/m.sup.3) COP R-1234yf 30.0 312 772 461 2.48 2152 5.3 35.0 312 882 570 2.83 2035 4.4 40.0 312 1003 691 3.22 1915 3.7 45.0 312 1137 825 3.64 1793 3.1 50.0 312 1283 971 4.11 1668 2.7 55.0 312 1443 1131 4.62 1540 2.3 R-1233zd 30.0 46 155 109 3.37 463 5.6 35.0 46 184 138 4.00 444 4.7 40.0 46 217 171 4.72 426 4.0 45.0 46 254 208 5.53 407 3.5 50.0 46 296 250 6.43 389 3.0 55.0 46 343 297 7.45 370 2.7 R-123 30.0 33 110 77 3.36 337 5.7 35.0 33 131 98 4.00 325 4.8 40.0 33 155 122 4.74 314 4.1 45.0 33 182 149 5.57 302 3.6 50.0 33 213 180 6.51 290 3.1 55.0 33 247 215 7.56 279 2.8

Example 3

(48) In this example, the following conditions were used:

(49) Evaporator temperature=5 C. Compressor inlet temperature=10 C. Isentropic efficiency=0.7. The results are tabulated in Table 3.

(50) FIGS. 6 and 7 show the COP and CAP of R-1233zd and R-1234yf relative to R-123.

(51) TABLE-US-00003 TABLE 3 T evap 5 C. Internal heat exchanger inlet compressor 10 C. isentropic efficiency 0.7 Tcond evap P cond P P diff T-out CAP ( C.) (kPa) (kPa) (kPa) comp KJ/m.sup.3) COP R-1234yf 30.0 368 772 404 39 2610 6.7 35.0 368 882 514 45 2472 5.4 40.0 368 1003 635 51 2332 4.4 45.0 368 1136 768 56 2188 3.7 R-1233zd 30.0 58 154 96 44 585 7.0 35.0 58 183 125 50 562 5.7 40.0 58 216 158 55 539 4.8 45.0 58 254 196 61 516 4.1 R-123 30.0 41 110 69 44 423 7.2 35.0 41 131 90 50 409 5.8 40.0 41 155 114 56 395 4.9 45.0 41 182 141 61 381 4.2

Example 4

(52) In this example, the following conditions were used:

(53) Evaporator temperature=10 C. Compressor inlet temperature=15 C. Isentropic efficiency=0.7. The results are tabulated in Table 4.

(54) FIGS. 8 and 9 show the COP and CAP of R4233zd and R1234yf relative to R-123.

(55) TABLE-US-00004 TABLE 4 T evap 10 C. Internal heat exchanger inlet compressor 15 C. isentropic efficiency 0.7 Tcond evap P cond P P diff P ratio CAP ( C.) (kPa) (kPa) (kPa) (p/p) (KJ/m.sup.3) COP R-1234yf 30.0 432 772 340 1.79 3097 8.7 35.0 432 882 450 2.04 2936 6.7 40.0 432 1003 571 2.32 2773 5.4 45.0 432 1137 705 2.63 2606 4.4 50.0 432 1283 851 2.97 2435 3.7 55.0 432 1443 1011 3.34 2258 3.1 R-1233zd 30.0 72 155 83 2.16 731 9.1 35.0 72 184 112 2.57 703 7.1 40.0 72 217 145 3.03 674 5.8 45.0 72 254 182 3.55 646 4.8 50.0 72 296 224 4.13 618 4.1 55.0 72 343 271 4.78 591 3.6 R-123 30.0 51 110 59 2.17 528 9.3 35.0 51 131 80 2.58 510 7.3 40.0 51 155 104 3.05 493 5.9 45.0 51 182 131 3.59 475 5.0 50.0 51 213 162 4.19 458 4.3 55.0 51 247 196 4.88 440 3.7

(56) Representative data from Tables 1 through 4 is charted in FIGS. 2 through 9.

(57) In all of these examples, the efficiency of R-1233zd was very close to that of R-123, being within a few percent of the efficiency of R-123. In contrast, the efficiency of R-1234yf was significantly lower than that of R-1233zd and R423, being from 6.4% lower to over 20% lower than that of R-123. It was also unexpectedly discovered that the capacity of R-1233zd was from 30% to 40% greater than that of R-123.

(58) It is also shown that for R-1233zd and for R-123 the system is operated as a negative-pressure system, where the pressure in the evaporator is below ambient. For R-1234yf the entire system is operated at positive-pressure.

(59) R-1233zd was found to provide a close match to operating pressures, pressure ratio, and pressure difference of R423 and can be used as a more environmentally acceptable replacement.

Example 5

Liquid Chiller Performance Data for Trans-1233zd and Cis-1233zd

(60) The performance of cis and trans 1233zd in a single-stage liquid chiller was evaluated in the following examples. In each example, data is provided at a given evaporator temperature and at multiple condenser discharge temperatures, ranging from 30 C. to 45 C. In each case, there is 5 C. of evaporator superheat and 5 C. of condenser subcooling. The isentropic compressor efficiency in each case was 0.7.

(61) In the following examples, the following nomenclature is used: Evaporator temperature: Tevap Condenser discharge temperature: Tcond Condenser pressure: cond P Evaporator pressure: evap P Coefficient of Performance (energy efficiency): COP Capacity: CAP

(62) The trans-1233zd (1-chloro-3,3,3-trifluoropropene, >99% trans-isomer) and cis-1233zd (cis-1-chloro-3,3,3-trifluoropropene, >99% cis-isomer) are evaluated for use in a single-stage chiller as explained above. The results are shown in Tables 5 to 8.

(63) TABLE-US-00005 TABLE 5 Evaporator Temperature = 10 C. Tcond evap P cond P CAP ( C.) (kPa) (kPa) (KJ/m.sup.3) COP trans-1233zd 30.0 31 154 308 4.12 35.0 31 182 297 3.58 40.0 31 214 286 3.14 45.0 31 250 274 2.78 cis-1233zd 30.0 12 75 134 4.08 35.0 12 91 128 3.53 40.0 12 109 123 3.09 45.0 12 130 117 2.73

(64) TABLE-US-00006 TABLE 6 Evaporator Temperature = 0 C. Tcond evap P cond P CAP ( C.) (kPa) (kPa) (KJ/m.sup.3) COP trans-1233zd 30.0 49 154 492 5.92 35.0 49 182 475 4.97 40.0 49 214 457 4.25 45.0 49 250 440 3.69 cis-1233zd 30.0 20 75 230 5.90 35.0 20 91 221 4.94 40.0 20 109 212 4.21 45.0 20 130 203 3.64

(65) TABLE-US-00007 TABLE 7 Evaporator Temperature = 5 C. Tcond evap P cond P CAP ( C.) (kPa) (kPa) (KJ/m.sup.3) COP trans-1233zd 30.0 60 154 613 7.37 35.0 60 182 592 6.02 40.0 60 214 571 5.05 45.0 60 250 549 4.32 cis-1233zd 30.0 26 75 296 7.36 35.0 26 91 285 6.00 40.0 26 109 274 5.02 45.0 26 130 262 4.28

(66) TABLE-US-00008 TABLE 8 Evaporator Temperature = 10 C. Tcond evap P cond P CAP ( C.) (kPa) (kPa) (KJ/m.sup.3) COP trans-1233zd 30.0 74 154 757 9.54 35.0 74 182 732 7.49 40.0 74 214 706 6.11 45.0 74 250 680 5.12 cis-1233zd 30.0 32 75 378 9.55 35.0 32 91 364 7.48 40.0 32 109 350 6.09 45.0 32 130 336 5.09

(67) The COP of trans-1233zd is about the same or greater than cis-1233zd while the capacity of trans-1233zd is about twice that or more than cis-1233zd.

Example 6

Mixtures of Trans-1233zd and Cis-1233zd

(68) To examine the potential effect of a mixture of both trans- and cis-isomers on the performance or operation of a centrifugal chiller, a vapor-liquid equilibrium test on a mixture of trans-1233zd and cis-1.233zd was conducted to evaluate the potential for fractionation.

(69) To a clean, glass 35 mL sampling vial was added 4.0 gram of cis-1233zd and 16.1 gram of trans-1233zd, providing an overall ratio of cis-1233zd-to-trans-1233zd of 19.9/80.1 wt/wt. The mixture was left to equilibrate to room temperature. The vapor portion and the liquid portion were analyzed by Gas Chromatography (GC). The ratio of cis-to-trans isomers in the vapor portion was found to be 12.2/87.8 wt/wt; the ratio of cis-1233zd-to-trans-1233zd in the liquid portion was significantly different, and found to be 21.3/78.6 wt/wt. This exemplifies that mixtures of trans-1233zd and cis-1.233zd may fractionate as is a zeotropic mixture.

Example 7

Acoustic Velocity

(70) The acoustic velocity for R-11, R-123, R-134a, R-1233zd and R-1234yf were determined at 40 C. and 1 bar. The acoustic velocity of R-1233zd is close to that of R-11 and closer to that of R-123 than either R-134a or R-1234yf.

(71) TABLE-US-00009 TABLE 9 Acoustic Velocity of Refrigerants Conditions: 40 C. and 1 bar. Acoustic Velocity Refrigerant (m/s) R123 131.9 R-11 142.0 R-1233zd 143.7 R-1234yf 155.6 R-134a 165.7

Example 8

Dimensionless Specific Seed

(72) The performance of R-123, R-1233zd, and R-1234yf in a liquid chiller was determined as in example 2, with a compressor inlet temperature at 5 C. and a condenser temperature at 40 C. The results are shown in Table 10, which also gives the ratio of the dimensionless specific speed, , of the refrigerant to that of R-123 (.sub.123), assuming the chillers are operated to deliver the same capacity of cooling. R-1233zd was found to be a good replacement for R-123 as compared to R-1234yf.

(73) TABLE-US-00010 TABLE 10 Dimensionless Specific Speed of Refrigerants at Equivalent Cooling Capacity Evaporator Temp: 5 C. Condenser Temp: 40 C. P Temp Refrigerant Compressor (bar) ( C.) /.sub.123 R123 inlet 0.33 5 1 outlet 1.55 58 R-1233zd inlet 0.46 5 0.76 outlet 2.17 58 R-1234yf inlet 3.12 5 0.44 outlet 10.03 52

(74) These results show that R-1233, particularly R-1233zd is useful as a refrigerant for liquid chillers, particularly negative-pressure chillers, and especially in large systems due to the efficiency benefits of R-1233zd over R-1234yf or similar refrigerants.