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Title:
HALOGENATED HYDROCARBON REFRIGERANT COMPOSITIONS CONTAINING HYDROCARBON OIL-RETURN AGENTS
Document Type and Number:
WIPO Patent Application WO/2000/042118
Kind Code:
A1
Abstract:
Refrigerant compositions containing hydrocarbon oil-return agents which solubilize mineral and synthetic oil lubricants with hydrofluorocarbon and hydrofluorocarbon/hydrochlorofluorocarbon-based refrigerants are disclosed. These hydrocarbon oil-return agents, having seven through sixteen carbon atoms, as a small proportion of an overall refrigerant composition, permit efficient return of mineral and synthetic oil lubricants from non-compressor zones back to a compressor zone in a refrigeration system operating with hydrofluorocarbon and hydrofluorocarbon/hydrochlorofluorocarbon-based refrigerants.

Inventors:
Bivens, Donald Bernard (210 West Locus Lane Kennett Square, PA, 19348, US)
Minor, Barbara Haviland (233 Greenhaven Drive Elkton, MD, 21921, US)
Yokozeki, Akimichi (Apartment C 109 Congressional Drive Wilmington, DE, 19807, US)
SPAUSCHUS, Hans, O.
Application Number:
PCT/US1999/015935
Publication Date:
July 20, 2000
Filing Date:
July 14, 1999
Export Citation:
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Assignee:
E.I. DU PONT DE NEMOURS AND COMPANY (1007 Market Street Wilmington, DE, 19898, US)
International Classes:
F25B1/00; C09K5/04; C10M101/02; C10M105/04; C10M105/06; C10M107/02; C10M121/02; C10M127/02; C10M169/04; C10N40/30; (IPC1-7): C09K5/04; C10M127/02; C10N40/30
Attorney, Agent or Firm:
Edwards, Mark A. (E.I. du Pont de Nemours and Company Legal Patent Records Center 1007 Market Street Wilmington, DE, 19898, US)
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Claims:
WHAT IS CLAIMED IS:
1. A refrigerant composition comprising: (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom; (b) an oil selected from the group consisting of mineral oils and synthetic oils; and (c) a hydrocarbon oilreturn agent containing from ten to sixteen carbon atoms.
2. A refrigerant composition, comprising: (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom; and (b) a hydrocarbon oilreturn agent containing from ten to sixteen carbon atoms.
3. A lubricant composition for use with a halogenated hydrocarbon refrigerant in compression refrigeration apparatus, comprising: (a) an oil selected from the group consisting of mineral oils and synthetic oils; and (b) a hydrocarbon oilreturn agent containing from ten to sixteen carbon atoms.
4. The composition of claim 1,2 or 3 wherein said hydrocarbon oil return agent forms a solution of said halogenated hydrocarbon with an oil selected from the group consisting of mineral oils and synthetic oils.
5. The composition of claim 1 wherein said hydrocarbon oilreturn agent comprises less than about 10 weight percent of said refrigerant composition.
6. The composition of claim 1 comprising from about 40 to about 99 weight percent halogenated hydrocarbon, from about 1 to about 60 weight percent oil, and from about 0.01 to about 10 weight percent hydrocarbon oilreturn agent.
7. The composition of claims 1 or 2 wherein said halogenated hydrocarbon contains from one to six carbon atoms and at least one atom of fluorine, has a normal boiling point of from about90°C to about 80°C, and optionally contains chlorine and oxygen atoms.
8. The composition of claim 7, wherein said halogenated hydrocarbon is selected from the group consisting of CC12F2 (CFC12), CHC12F (HCFC21), CHC1F2 (HCFC22), CHF3 (HFC23), CH2ClF(HCFC31), CH2F2 (HFC32), CH3F (HFC41), CF3CF3 (FC116), CHC12CF3 (HCFC123), CHCIFCC1F2 (HCFC123a),CHClFCF3(HCFC124), CHF2CC1F2 (HCFC124a), CHF2CF3(HFC125), CH2C1CF3 (HCFC133a), CHF2CHF2(HFC134), CH2FCF3 (HFC134a), CCIF2CH3 (HCFC142b), CHF2CH2F(HFC143), CF3CH3 (HFC143a), CHC1FCH3 (HCFC151a), CHF2CH3 (HFC152a), CHF2CC12CF3 (HCFC225aa), CHC1FCC1FCF3 (HCFC225ba), CHF2CC1FCClF2 (HCFC225bb), CHC12CF2CF3 (HCFC225ca), CHC1FCF2CCIF2 (HCFC225cb), CHF2CF2CC12F (HCFC225cc), CCIF2CHCICF3 (HCFC225da), CC1F2CHFCC1F2 (HCFC225ea), CF3CHFCC12F (HCFC225eb), CHF2CC1FCF3 (HCFC226ba), CHC1FCF2CF3 (HCFC226ca), CHF2CF2CC1F2 (HCFC226cb), CF3CHC1CF3 (HCFC226da), CC1F2CHFCF3 (HCFC226ea), CHF2CF2CF3 (HFC227ca), CF3CFHCF3 (HFC227ea), CHF2CC1FCHF2 (HCFC235ba), CH2FCCIFCF3 (HCFC235bb), CHC1FCF2CHF2 (HCFC235ca), CH2C1CF2CF3 (HCFC235cb), CH2FCF2CClF2(HCFC235cc), CHF2CHClCF3(HCFC235da), CHC1FCHFCF3 (HCFC235ea), CHF2CHFCC1F2 (HCFC235eb), CC1F2CH2CF3 (HCFC235fa), CHF2CF2CHF2 (HFC236ca), CH2FCF2CF3 (HFC236cb), CHF2CHFCF3 (HFC236ea), CF3CH2CF3 (HFC236fa), CH2FCF2CHF2(HFC 245ca), CH3CF2CF3(HFC245cb), CHF2CHFCHF2 (HFC245ea), CH2FCHFCF3 (HFC245eb), CHF2CH2CF3 (HFC245fa), CH2FCF2CH2F (HFC254ca), CH2CF2CHF2(HFC254cb), CH2FCHFCHF2(HFC254ea), CH3CHFCF3(HFC 254eb), CHF2CH2CHF2(HFC254fa), CH2FCH2CF3(HFC254fb), CH3CF2CH3 (HFC272ca), CH3CHFCH2F (HFC272ea), CH2FCH2CH2F (HFC272fa), CH3CH2CF2H(HFC272fb), CH3CHFCH3 (HFC281ea), CH3CH2CH2F (HFC 281fa), CF3CF2CF2CF2H(HFC329p), CF3CF2CFHCF3 (HFC329me), CF3CF2CF2CFH2(HFC338q), CF3CF2CH2CF3(HFC338mf), CF3CF2CFHCF2H (HFC338pe), CF3CFHCF2CF2H (HFC338pce), CHF2CF2CF2CF2H(HFC 338pcc), CF3CFHCFHCF3 (HFC338mee), CF3CF2CF2CF2CF2H (HFC42llp), CF3CF2CFHCF2CF3 (HFC42llmce), CF3CF2CF2CFHCF3 (HFC42llme), CF3CF2CH2CF2CF3(IFC43lOmcf), CF3CF2CF2CH2CF3 (HFC43lOmf), CF3CF2CF2CF2CFH2 (HFC43lOq), CF3CF2CF2CFHCF2H(HFC4310pe), CF3CF2CFHCF2CF2H (HFC43lOpce), CF3CHFCHFCF2CF3 (HFC43lOmee), CF2HCF2CF2CF2CF2H (HFC43lOpccc), CF3CFHCF2CF2CF2H (HFC43 lOpcce), CF3CFHCF2CFHCF3 (HFC43lOmece), CF3CF2CF2CF2CF2CF2H (HFC5213p), C4F9OCH3, and C4F90C2H5.
9. The composition of claim 7 further comprising less than about 10 weight percent of at least one C3 to C5 hydrocarbon.
10. The composition of claims 1 or 3 wherein said oil is selected from the group consisting of paraffins, naphthenes, aromatics, alkylaryls, synthetic paraffins, and polyalphaolefins.
11. The composition of claims 1,2, or 3 wherein said hydrocarbon oilreturn agent comprises hydrocarbons containing eleven to thirteen carbon atoms.
12. A process for producing refrigeration comprising evaporating a composition of claims 1 or 2 in the vicinity of a body to be cooled.
13. A process for producing heat comprising condensing a composition of claims lor 2 in the vicinity of a body to be heated.
14. A process for returning oil from a noncompressor zone to a compressor zone in a compression refrigeration system comprising: (a) contacting an oil, selected from the group consisting of mineral oils and synthetic oils, in the noncompressor zone with a halogenated hydrocarbon, containing at least one carbon atom and one fluorine atom, in the presence of a hydrocarbon oilreturn agent, containing from six to sixteen carbon atoms, to form a solution comprising oil, halogenated hydrocarbon, and hydrocarbon oilreturn agent; and (b) transferring the solution from the noncompressor zone to the compressor zone of the refrigeration system.
15. The process of claim 14 wherein the hydrocarbon oilreturn agent comprises less than about 10 weight percent of the solution comprising halogenated hydrocarbon, oil, and hydrocarbon oilreturn agent.
16. The process of claim 14 wherein the solution comprising halogenated hydrocarbon, oil, and hydrocarbon oilreturn agent comprises from about 40 to about 99 weight percent halogenated hydrocarbon, from about 1 to about 60 weight percent oil, and from about 0.01 to about 10 weight percent hydrocarbon oilreturn agent.
17. The process of claim 14 wherein said halogenated hydrocarbon contains from one to six carbon atoms and at least one atom of fluorine, has a normal boiling point of from about90°C to about 80°C, and optionally contains chlorine and oxygen atoms.
18. The process of claim 17, wherein said halogenated hydrocarbon is selected from the group consisting of CC12F2 (CFC12), CHCl2F(HCFC21), CHC1F2 (HCFC22), CHF3(HFC23), CH2ClF(HCFC31), CH2F2 (HFC32), CH3F (HFC41), CF3CF3 (FC116), CHC12CF3 (HCFC123), CHClFCClF2 (HCFC123a), CHC1FCF3 (HCFC124), CHF2CCIF2 (HCFC124a), CHF2CF3 (HFC125), CH2CICF3 (HCFC133a), CHF2CHF2(HFC134), CH2FCF3(HFC 134a), CC1F2CH3 (HCFC142b), CHF2CH2F(HFC143), CF3CH3 (HFC143a), CHC1FCH3 (HCFC151a), CHF2CH3 (HFC152a), CHF2CC12CF3 (HCFC225aa), CHC1FCC1FCF3 (HCFC225ba), CHF2CCIFCC1F2 (HCFC225bb), CHC12CF2CF3 (HCFC225ca), CHC1FCF2CQ1F2 (HCFC225cb), CHF2CF2CC12F (HCFC 225cc), CC1F2CHCICF3 (HCFC225da), CCIF2CHFCC1F2 (HCFC225ea), CF3CHFCC12F (HCFC225eb), CHF2CC1FCF3 (HCFC226ba), CHC1FCF2CF3 (HCFC226ca), CHF2CF2CC1F2 (HCFC226cb), CF3CHC1CF3 (HCFC226da), CCIF2CHFCF3 (HCFC226ea), CHF2CF2CF3 (HFC227ca), CF3CFHCF3 (HFC 227ea), CHF2CClFCHF2(HCFC235ba), CH2FCCIFCF3 (HCFC235bb), CHC1FCF2CHF2 (HCFC235ca), CH2CICF2CF3 (HCFC235cb), CH2FCF2CCIF2 (HCFC235cc), CHF2CHC1CF3 (HCFC235da), CHClFCHFCF3 (HCFC235ea), CHF2CHFCC1F2 (HCFC235eb), CC1F2CH2CF3 (HCFC235fa), CHF2CF2CHF2 (HFC236ca), CH2FCF2CF3 (HFC236cb), CHF2CHFCF3 (HFC236ea), CF3CH2CF3(HFC236fa), CH2FCF2CHF2(HFC245ca), CH3CF2CF3 (HFC 245cb), CHF2CHFCHF2 (HFC245ea), CH2FCHFCF3 (HFC245eb), CHF2CH2CF3 (HFC245fa), CH2FCF2CH2F (HFC254ca), CH2CF2CHF2 (HFC 254cb), CH2FCHFCHF2(HFC254ea), CH3CHFCF3 (HFC254eb), CHF2CH2CHF2 (HFC254fa), CH2FCH2CF3 (HFC254fb), CH3CF2CH3(HFC 272ca), CH3CHFCH2F (HFC272ea), CH2FCH2CH2F (HFC272fa), CH3CH2CF2H (HFC272fb), CH3CHFCH3(HFC281ea), CH3CH2CH2F(HFC 281fa), CF3CF2CF2CF2H (HFC329p), CF3CF2CFHCF3 (HFC329me), CF3CF2CF2CFH2 (HFC338q), CF3CF2CH2CF3 (HFC338mf), CF3CF2CFHCF2H (HFC338pe), CF3CFHCF2CF2H(HFC338pce), CHF2CF2CF2CF2H(HFC 338pcc), CF3CFHCFHCF3 (HFC338mee), CF3CF2CF2CF2CF2H(HFC4211p), CF3CF2CFHCF2CF3(HFC4211mce),(HFC4211mce), CF3CF2CF2CFHCF3(HFC4211me), CF3CF2CH2CF2CF3 (HFC43lOmcf), CF3CF2CF2CH2CF3 (HFC43lOmf), CF3CF2CF2CF2CFH2(HFC4310q),(HFC4310q), CF3CF2CF2CFHCF2H(HFC4310pe), CF3CF2CFHCF2CF2H (HFC43lOpce), CF3CHFCHFCF2CF3 (HFC43lOmee), CF2HCF2CF2CF2CF2H (HFC43lOpccc), CF3CFHCF2CF2CF2H (HFC43 lOpcce), CF3CFHCFZCFHCF3 (IC43lOmece), CF3CFzCF2CF2CF2CF2H (HFC5213p), C4F90CH3, and C4F9OC2H5.
19. The process of claim 17 wherein said halogenated hydrocarbon further comprises less than about 10 weight percent of at least one C3 to C5 hydrocarbon.
20. The process of claim 14 wherein the oil is selected from the group consisting of paraffins, naphthenes, aromatics, alkylaryls, synthetic paraffins, and polyalphaolefins.
21. The process of claim 14 wherein said hydrocarbon oilreturn agent comprises hydrocarbons containing eleven to thirteen carbon atoms.
Description:
TITLE HALOGENATED HYDROCARBON REFRIGERANT COMPOSITIONS CONTAINING HYDROCARBON OIL-RETURN AGENTS FIELD OF THE INVENTION The present invention relates to refrigerant compositions containing hydrocarbon oil-return agents which solubilize mineral and synthetic oil lubricants with halogenated hydrocarbon refrigerants, thereby permitting efficient return of lubricants from non-compressor zones back to a compressor zone in a refrigeration system.

BACKGROUND Mineral oils and alkylbenzenes have been conventionally used as lubricants in chlorofluorocarbon-based (CFC) refrigeration systems. However, the lack of solubility of these lubricants in the replacement, non-ozone depleting, hydrofluorocarbon (HFC) refrigerants has precluded their use and necessitated development and use of alternative lubricants for HFC refrigeration systems based on polyalkylene glycols (PAGs) and polyol esters (POEs). While the PAGs and POEs are suitable lubricants for HFC-based refrigeration systems, they are extremely hygroscopic and can absorb several thousand ppm (parts per million) of water on exposure to moist air. This absorbed moisture leads to problems in the refrigeration system, such as formation of acids which resultant in corrosion of the refrigeration system and formation of intractable sludges. In contrast, mineral oils and alkylbenzenes are much less hygroscopic and have low solubility, less than 100 ppm, for water. Additionally, PAG and POE lubricants are considerably more expensive than the hydrocarbon lubricants, typically on the order of three to six times more expensive. As a consequence, there is a need and an opportunity to resolve this solubility problem so that the refrigeration industry may utilize mineral oil and alkylbenzene lubricants with HFC-based refrigerants.

Hydrochlorofluorocarbon (HCFC) refrigerants are also replacing CFCs, and in instances as mixtures with HFCs. These HCFC-based refrigerant mixtures are less soluble than CFCs in conventional refrigeration lubricants such as mineral oil. A lubricant change from mineral oil to alkylbenzene is often required when the HCFCs or HCFC/HFC mixtures are used to replace pure CFC- based refrigerants, resulting in more expense to the refrigeration industry.

Consequently, there is a need and opportunity to resolve this low solubility

problem so that the refrigeration industry may utilize HCFC and HCFC/HFC- based refrigerants with mineral oil lubricants.

For the foregoing reasons there is a need in the refrigeration industry for providing oil-return agents that create a solution of lubricant oil (dispersed phase) in a HFC-and/or HCFC-based refrigerant (continuous phase), which permits improved lubricant oil transport through a refrigeration system and lubricant oil return back to the refrigeration system compressor from other refrigeration system zones.

SUMMARY The present invention is directed to a refrigerant composition that satisfies the aforesaid need. The refrigerant composition comprises: (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom; (b) an oil selected from the group consisting of mineral oils and synthetic oils; and (c) a hydrocarbon oil-return agent containing from ten to sixteen carbon atoms.

The present invention also relates to a refrigerant composition, comprising: (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom; and (b) a hydrocarbon oil-return agent containing from ten to sixteen carbon atoms.

The present invention further relates to a lubricant composition for use with a halogenated hydrocarbon refrigerant in compression refrigeration apparatus, comprising: (a) an oil selected from the group consisting of mineral oils and synthetic oils; and (b) a hydrocarbon oil-return agent containing from ten to sixteen carbon atoms.

Additionally, the present invention pertains to a process for returning oil from a non-compressor zone to a compressor zone in a compression refrigeration system comprising: (a) contacting an oil, selected from the group consisting of mineral oils and synthetic oils, in the non-compressor zone with a halogenated hydrocarbon, containing at least one carbon atom and one fluorine atom, in the presence of a hydrocarbon oil-return agent, containing from six to sixteen carbon atoms, to form a solution comprising oil, halogenated hydrocarbon, and hydrocarbon oil-return agent; and (b) transferring the solution from the non- compressor zone to the compressor zone of the refrigeration system.

DETAILED DESCRIPTION The present invention relates to refrigerant compositions comprising: (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom; (b) an oil selected from the group consisting of mineral oils and synthetic oils; and (c) a hydrocarbon oil-return agent containing from ten to sixteen carbon atoms, wherein said hydrocarbon oil-return agent forms a solution of said halogenated hydrocarbon and said oil.

The present invention further relates to compositions comprising: (a) a halogenated hydrocarbon containing at least one carbon atom and one fluorine atom; and (b) a hydrocarbon oil-return agent containing from ten to sixteen carbon atoms, wherein said hydrocarbon oil-return agent forms a solution of said halogenated hydrocarbon with an oil selected from the group consisting of mineral oils and synthetic oils.

The present invention further relates to lubricant compositions for use with halogenated hydrocarbon refrigerants in compression refrigeration apparatus, comprising: (a) an oil selected from the group consisting of mineral oils and synthetic oils; and (b) a hydrocarbon oil-return agent containing from ten to sixteen carbon atoms, wherein said oil-return agent forms a solution of said oil with halogenated hydrocarbon refrigerant.

The present invention further relates to a process for returning oil from a non-compressor zone to a compressor zone in a compression refrigeration system comprising: (a) contacting an oil, selected from the group consisting of mineral oils and synthetic oils, in the non-compressor zone with a halogenated hydrocarbon, containing at least one carbon atom and one fluorine atom, in the presence of a hydrocarbon oil-return agent, containing from six to sixteen carbon atoms, to form a solution comprising oil, halogenated hydrocarbon, and hydrocarbon oil-return agent; and (b) transferring the solution from the non- compressor zone to the compressor zone of the refrigeration system.

Halogenated hydrocarbons of the present invention contain at least one carbon atom and one fluorine atom. Of particular utility are halogenated hydrocarbons having 1-6 carbon atoms containing at least one fluorine atom, optionally containing chlorine and oxygen atoms, and having a normal boiling point of from-90°C to 80°C. By normal boiling point is meant the temperature at which a liquid composition's vapor pressure is equal to one atmosphere. These halogenated hydrocarbons may be represented by the general formula CwF2w+2-x-yHxClyOz, wherein w is 1-6, x is 1-9, y is 0-3, and z is 0-2. Preferred of the halogenated hydrocarbons are those in which w is 1-6, x is 1-5, y is 0-1, and z

is 0-1. Such halogenated hydrocarbons are commercial products available from a number of sources such as E.I. du Pont de Nemours & Co., Fluoroproducts, Wilmington, DE, 19898, USA, or are available from custom synthesis companies such as PCR Inc., P. O. Box 1466, Gainesville, Florida, 32602, USA, and additionally by synthetic processes disclosed in art such as The Journal of Fluorine Chemistry, or Chemistry of Organic Fluorine Compounds, edited by Milos Hudlicky, published by The MacMillan Company, New York, N. Y., 1962.

Examples of the halogenated hydrocarbons are: CC12F2 (CFC-12), CHC12F (HCFC-21), CHC1F2 (HCFC-22), CHF3 (HFC-23), CH2CIF (HCFC-31), CH2F2 (HFC-32), CH3F (HFC-41), CF3CF3 (FC-116), CHC12CF3 (HCFC-123), CHCIFCC1F2 (HCFC-123a), CHClFCF3 (HCFC-124), CHF2CCIFz (HCFC-124a), CHF2CF3 (HFC-125), CH2C1CF3 (HCFC-133a), CHF2CHF2 (HFC-134), CH2FCF3 (HFC-134a), CCIF2CH3 (HCFC-142b), CHF2CH2F (HFC-143), CF3CH3 (HFC-143a), CHC1FCH3 (HCFC-151a), CHF2CH3 (HFC-152a), CHF2CC12CF3 (HCFC-225aa), CHC1FCC1FCF3 (HCFC-225ba), CHF2CC1FCC1F2 (HCFC-225bb), CHC12CF2CF3 (HCFC-225ca), CHCIFCF2CCIF2 (HCFC-225cb), CHF2CF2CC12F (HCFC-225cc), CCIF2CHCICF3 (HCFC-225da), CCIF2CHFCC1F2 (HCFC-225ea), CF3CHFCC12F (HCFC-225eb), CHF2CClFCF3 (HCFC-226ba), CHC1FCF2CF3 (HCFC-226ca), CHF2CF2CCIF2 (HCFC-226cb), CF3CHC1CF3 (HCFC-226da), CC1F2CHFCF3 (HCFC-226ea), CHF2CF2CF3 (HFC-227ca), CF3CFHCF3 (HFC-227ea), CHF2CCIFCHF2 (HCFC-235ba), CH2FCC1FCF3 (HCFC-235bb), CHC1FCF2CHF2 (HCFC-235ca), CH2C1CF2CF3 <BR> <BR> (HCFC-235cb), CH2FCF2CC1F2 (HCFC-235cc), CHF2CHC1CF3 (HCFC-235da), CHC1FCHFCF3 (HCFC-235ea), CHF2CHFCC1F2 (HCFC-235eb), CC1F2CH2CF3 (HCFC-235fa), CHF2CF2CHF2 (HFC-236ca), CH2FCF2CF3 (HFC-236cb), CHF2CHFCF3(HFC-236ea), CF3CH2CF3(HFC-236fa), CH2FCF2CHF2(HFC- 245ca), CH3CF2CF3(HFC-245cb), CHF2CHFCHF2 (HFC-245ea), CH2FCHFCF3 (HFC-245eb), CHF2CH2CF3 (HFC-245fa), CH2FCF2CH2F (HFC-254ca), CH2CF2CHF2 (HFC-254cb), CH2FCHFCHF2(HFC-254ea), CH3CHFCF3 (HFC- 254eb), CHF2CH2CHF2 (HFC-254fa), CH2FCH2CF3 (HFC-254fb), CH3CF2CH3 (HFC-272ca), CH3CHFCH2F (HFC-272ea), CH2FCH2CH2F (HFC-272fa), CH3CH2CF2H (HFC-272fb) CH3CHFCH3 (HFC-281ea), CH3CH2CH2F (HFC- 281fa), CF3CF2CF2CF2H (HFC-329p), CF3CF2CFHCF3 (HFC-329me), CF3CF2CF2CFH2 (HFC-338q), CF3CF2CH2CF3 (HFC-338mf), CF3CF2CFHCF2H (HFC-338pe), CF3CFHCF2CF2H (HFC-338pce), CHF2CF2CF2CF2H (HFC- 338pcc), CF3CFHCFHCF3 (HFC-338mee), CF3CF2CF2CF2CF2H (HFC-42-llp), CF3CF2CFHCF2CF3 (HFC-42-1 lmce), CF3CF2CF2CFHCF3 (HFC-42-llme), CF3CF2CH2CF2CF3 (HFC-43-lOmcf), CF3CF2CF2CH2CF3 (HFC-43-lOmf),

CF3CF2CF2CF2CFH2 (HFC-43-lOq), CF3CF2CF2CFHCF2H (HFC-43-lOpe),<BR> <BR> <BR> <BR> <BR> CF3CF2CFHCF2CF2H(IHFC-43-lOpce), CF3CHFCHFCF2CF3 (HFC-43-lOmee), CF2HCF2CF2CF2CF2H (HFC-43-lOpccc), CF3CFHCF2CF2CF2H (HFC-43- lOpcce), CF3CFHCF2CFHCF3 (HFC-43-lOmece), CF3CF2CF2CF2CF2CF2H (HFC-52-13p), C4F90CH3, and C4F90C2H5. Preferred of the halogenated hydrocarbons are: CHC1F2 (HCFC-22), CHF3 (HFC-23), CH2F2 (HFC-32), CHC1FCF3 (HCFC-124), CHF2CF3 (HFC-125), CHF2CHF2 (HFC-134), CH2FCF3 (HFC-134a), CF3CH3 (HFC-143a), CHF2CH3 (HFC-152a), CHF2CF2CF3 (HFC- 227ca), CF3CFHCF3 (HFC-227ea), CF3CH2CF3 (HFC-236fa), CHF2CH2CF3 (HFC-245fa), CHF2CF2CF2CF2H (HFC-338pcc), CF3CHFCHFCF2CF3 (HFC-43- lOmee), and azeotropic and azeotrope-like halogenated hydrocarbon compositions such as: HCFC-22/HFC-152a/HCFC-124 (R-401A, R-401B, R-401C), HFC- 1251HFC-143alHFC-134a (R-404A), HFC-32/HFC-125/HFC-134a (R-407A, R- 407B, R-407C), HCFC-22/HFC-143a/HFC-125 (R-408A), HCFC-22/HCFC- 124/HCFC-142b (R-409A), HFC-32/HFC-125 (R-410A), and HFC-125/HFC- 143a (R-507).

The halogenated hydrocarbons of the present invention may further comprise up to 10 weight percent of at least one C3 to Cs hydrocarbon, e. g., propane, propylene, cyclopropane, n-butane, i-butane, and n-pentane. Examples of halogenated hydrocarbons containing such C3 to Cs hydrocarbons are azeotrope-like compositions of HCFC-22/HFC-125/propane (R-402A, R-402B) and HCFC-22/octafluoropropane/propane (R-403A, R-403B).

Oils of the present invention are oils conventionally employed as lubricants in refrigeration apparatus with CFC-based refrigerants. Such oils and their properties are discussed in the 1990 ASHRAE Handbook, Refrigeration Systems and Applications, chapter 8, titled"Lubricants in Refrigeration Systems", pages 8.1-8.21. Oils of the present invention comprise the family of compounds commonly known in this field as mineral oils. Mineral oils comprise paraffins (straight-chain and branched-carbon-chain, saturated hydrocarbons), naphthenes (cycloparaffins), aromatics (unsaturated, cyclic hydrocarbons containing one or more rings characterized by alternating double bonds), and nonhydrocarbons (molecules containing atoms such as sulfur, nitrogen, or oxygen in addition to carbon and hydrogen). Oils of the present invention further comprise the family of compounds commonly known in this field as synthetic oils. Synthetic oils comprise alkylaryls (such as linear and branched-alkyl-chain alkylbenzenes), synthetic paraffins, and polyalphaolefins. Examples of commercially available lubricant oils of the present invention are Suniso 3GS, Sontex 372LT, and

Calumet@ RO-30 (all previous three being naphthenes), Zerol 150 (an alkylbenzene), and"BVM 100 N" (a paraffin).

The hydrocarbon oil-return agents of the present invention are employed in an effective amount in the present inventive compositions such that a solution of halogenated hydrocarbon and lubricating oil is formed. By"solution" is meant that halogenated hydrocarbon and oil become more miscible in the presence of hydrocarbon oil-return agents such that oil is returned as a homogenous solution with halogenated hydrocarbon from non-compressor zones to a compressor zone in a refrigeration system in a quantity, which maintains acceptable compressor lubrication and thus overall refrigeration system operation.

In the present inventive compositions comprising halogenated hydrocarbon containing at least one carbon atom and one fluorine atom, oil selected from the group consisting of mineral oils and synthetic oils, and hydrocarbon oil-return agent, it is preferred that less than about 10 weight percent of the total composition is hydrocarbon oil-return agent. In a more preferred sense, less than about 5 weight percent of the total composition (comprising halogenated hydrocarbon, oil, and hydrocarbon oil-return agent) is hydrocarbon oil-return agent. Hydrocarbon oil-return agent concentrations greater than about 10 weight percent of the total composition are typically not needed to obtain adequate oil return and have been observed to negatively influence the viscosity of the lubricating oil leading to inadequate lubrication and stress on, or mechanical failure of, the refrigeration apparatus. Higher oil-return agent concentrations than about 10 weight percent of the total composition have also been observed to negatively influence the capacity and performance of a refrigerant composition.

An effective amount of hydrocarbon oil-return agent in the present inventive compositions leads to halogenated hydrocarbon and oil becoming miscibilized to the extent that adequate return of oil in a compression refrigeration system from non-compressor (e. g., evaporator) to compressor zones is obtained.

Hydrocarbon oil-return agent of the present inventive compositions comprises aliphatic, straight, branched, or cyclic chain hydrocarbons having at least seven carbon atoms and sixteen or less carbon atoms. For example, heptanes, octanes, nonanes, decanes, undecanes, kerosene, and mixtures thereof, and in particular refined kerosene with a sulfur content less than 0.2 weight%.

Preferred of the hydrocarbon oil-return agents are those which are classified as combustible (as opposed to flammable) by ASTM D-93. So-classified combustible hydrocarbons are preferred as oil-return agents as their use in any quantity will not result in flammability being rendered to a refrigeration composition. A preferred hydrocarbon oil-return agent has from seven to sixteen

carbon atoms A more preferred hydrocarbon oil-return agent has from eleven to thirteen carbon atoms. A most preferred commercially available compound useful as hydrocarbon oil-return agent is Isopart) H. Isopar H is a high purity Cll to C12 iso-parafinic with low aromatics sold by Exxon Chemical, USA.

Compounds are typically considered flammable if the flash point is less than 37°C. Though flash points in the table below may be measured by slightly different methods, there is a trend of increasing flash point with carbon chain length. Chain lengths below ten carbon atoms may begin to become flammable. A nonflammable hydrocarbon oil-return-agent or carrier reduces flammability in refrigeration and air conditioning systems versus use of compounds such as propane, butane, isobutane and pentane, disclosed in the art as useful in promoting oil return. Also a larger amount of non-flammable hydrocarbon oil-return-agent than flammable hydrocarbon may be used without effecting system flammability. Hydrocarbon Formula Flash Pt (°C) Boiling Pt (°C) Flammability Propane CH3CH2CH3-104-42 Flammable Isobutane (CH3) 3CH-84-12 Flammable Butane CH3 (CH2) 2CH3-60-1 Flammable Pentane CH3 (CH2) 3CH3-40 36-38 Flammable Hexane CH3 (CH2) 4CH3-22 to-26 65-69 Flammable Heptane CH3 (CH2) 5CH3-8 92-100 Flammable OctaneCH3 (CH2) 6CH316125-127Flammable Nonane CH3 (CH2) 7CH3 31 151 Flammable Decane CH3 (CH2) 8CH3 46 174 Combustible Kerosene HC mixture 43-82 151-301 Combustible Isopar Cn-Cu57182Combustible Isoparaffin Undecane CH3 (CH2) 9CH3 60 196 Combustible Dodecane CH3 (CH2) 10CH3 71 215-217 Combustible Tridecane CH3 (CH2) 11CH3 79 234 Combustible Tetradecane CH3 (CH2) l2CH3 100 252 Combustible Pentadecane CH3 (CH2) l3CH3 132 270 Combustible Hexadecane CH3 (CH2) 14CH3 135 287 Combustible Mineral oil Paraffin Oil 199 260-360 Combustible The present refrigerant compositions comprising halogenated hydrocarbon, oil, and hydrocarbon oil-return agent generally comprise 40-99

weight% halogenated hydrocarbon, 1-60 weight% oil, and 0.01-10 weight% hydrocarbon oil-return agent, based on the total composition weight. More preferably, such compositions comprise 50-90 weight% halogenated hydrocarbon, 10-50 weight% oil, and 0.01-5 weight% hydrocarbon oil-return-agent.

The further present compositions comprising: halogenated hydrocarbon, and hydrocarbon oil-return agent; and oil and hydrocarbon oil-return agent comprise weight ratios of components identical with those found in the present compositions comprising halogenated hydrocarbon, oil, and hydrocarbon oil-return agent. That is to say, in the present compositions, the weight ratio of halogenated hydrocarbon to oil is from about 0.6 (40/60) to about 99 (99/1), and the weight ratio of oil to hydrocarbon oil-return agent is from about 0.1 (1/10) to about 6000 (60/. 01).

The present invention further comprises processes for producing refrigeration comprising evaporating the present refrigeration compositions in the vicinity of a body to be cooled and processes for producing heat comprising condensing the present refrigeration compositions in the vicinity of a body to be heated.

The present invention further relates to processes for solubilizing a halogenated hydrocarbon in an oil comprising contacting the halogenated hydrocarbon with the oil in the presence of an effective amount of hydrocarbon oil-return agent which forms a solution of the halogenated hydrocarbon and the oil, wherein the halogenated hydrocarbon contains at least one carbon atom and one fluorine atom, and the oil is selected from the group consisting of mineral oils and synthetic oils.

The present invention further relates to processes for returning oil from a non-compressor zone to a compressor zone in a refrigeration system comprising: (a) contacting the oil in the non-compressor zone with at least one halogenated hydrocarbon in the presence of an effective amount of a hydrocarbon oil-return agent and (b) transferring the oil from the non-compressor zone to the compressor zone of the refrigeration system, wherein the halogenated hydrocarbon contains at least one carbon atom and one fluorine atom, and the oil is selected from the group consisting of mineral oils and synthetic oils.

The present invention further relates to processes for transferring an oil from a low pressure zone to a compressor zone in a refrigeration system, comprising:

(a) contacting the oil in the low pressure zone of the refrigeration system with at least one halogenated hydrocarbon in the presence of an effective amount of a hydrocarbon oil-return agent and (b) transferring the oil from the low pressure zone to the compressor zone of the refrigeration system, wherein the halogenated hydrocarbon contains at least one carbon atom and one fluorine atom, and the oil is selected from the group consisting of mineral oils and synthetic oils.

EXAMPLES In the following examples, percentages (%) shown without a label refer to the weight percent of a given material in the total composition being discussed. The error in the oil return measurements reported is 0.5 wt%.

EXAMPLE 1 Oil return was tested in an oil-return apparatus as follows. Liquid refrigerant was fed from a pressurized cylinder through copper tubing to a heater where it was vaporized. The refrigerant vapor then passed through a pressure regulator and metering valve to control flow at a constant rate of 1,000-1,100 cc per minute and 1 atm pressure. The refrigerant vapor was fed to another copper tube 180 cm in length and 0.635 cm outer diameter formed into a U-shape placed in a constant temperature bath. The U-shaped tube (U-tube) began with a straight vertical section 37 cm long then bent to a horizontal section 27 cm long at the bottom of the bath. The tube then rose vertically in a zig-zag pattern with four 23 cm lengths, followed by another vertical straight section 23 cm long. The U-tube was filled with 10 grams of oil, optionally containing hydrocarbon oil-return agent, which was added to the U-tube through the 37 cm vertical tube. Vapor refrigerant passed slowly through the oil in the U-tube. Refrigerant and oil exiting the U-tube was collected in a receiver and refrigerant allowed to evaporate. Oil was then weighed to determine how much was carried out of the U-tube by the refrigerant.

Refrigerant R404A (44 wt% HFC-125,52 wt% HFC-143a, and 4 wt% HFC-134a) was placed in the refrigerant cylinder. HAB 22 oil (HAB 22 is a branched alkylbenzene oil sold by Nippon Oil) or HAB plus hydrocarbon oil- return-agent IsoparX H was placed in the copper U-tube, wherein total oil and oil- return agent equaled 10 grams. The constant temperature bath was held at a temperature of-20°C. Refrigerant vapor was fed through the U-tube at a flow rate of 1,100 cubic centimeters per minute and weight of oil in the receiver measured at 6,10,20 and 30 minute time intervals. POE 22 polyol ester oil was compared as a baseline to HAB 22. Data are shown in Table 1 below.

TABLE 1

Wt% of Oil Returned Oil Composition in U-tube 6 Min 10 Min 20 Min POE 1.0 10.6 18.9 HAB 22 0 6.1 16.2 3% Isopar@HinHAB2209.6 19.2

Results show oil return is equivalent to POE when IsoparE) H is added to hard alkylbenzene oil (HAB 22).

EXAMPLE 2 The apparatus and procedure of Example 1 was used to test refrigerant R401A (53 wt% HCFC-22,13 wt% HFC-152a and 34 wt% HFC-124). Suniso3GS mineral oil with and without Isopar0 H was compared to a baseline of Zerol 150 alkyl benzene. Results are shown in Table 2.

TABLE 2 Weight % of Oil Returned Oil Composition in U-6 10 20 tube: Min Min Min 3GS 0 1.2 19.7 1 Zerol 150 0 9.6 31.2 3% Isopar (E) H in 3GS 0.4 14.0 30.6

Results show addition of Isopar0 H to 3GS mineral oil provides equivalent oil return to Zerol 150 alkyl benzene.

EXAMPLE 3 The apparatus and procedure of Example 1, with exceptions discussed below, was used to test refrigerant R407C (23 wt% HFC-32,25 wt% HFC-125and 52 wt% HFC-134a). Suniso0 3GS mineral oil, with and without hydrocarbon oil

return agent Isopart) H, was compared to POE. The constant temperature bath was held at-20°C. Results are shown in Table 3.

TABLE 3 Weight % Oil Returned _ Oil Composition in U-tube6 min 10 min 20 min POE 3.1 14.1 26.5 3GS 0 0 0 3% Isopar (D H in 3GS O O 0.3 6% Isopar (B) H in 3GS 0 0 6.7 15% Isopar0 H in 3GS 10.0 18.7 27.3 Results show addition of Isopar0 H to 3GS oil improves oil return and oil return performance of 15% Isopart) H in 3GS is equivalent to POE.

EXAMPLE 4 The apparatus and procedure of Example 1, with exceptions discussed below, was used to test refrigerant R404A (44 wt% HFC-125,52 wt% HFC-143a, and 4 wt% HFC-134a). SunisoX 3GS mineral oil, with and without hydrocarbon oil return agent Isopar# H, was compared to POE. The constant temperature bath was held at-20°C. Results are shown in Table 4.

TABLE 4 Weight % Oil Returned Oil Composition in U-tube 6 min 10 min 20 min POE 0 6. 2 18.9 12%IsoparX H in 3GS 4. 2 13. 3 23.3 15%IsoDar (E) H in 3GS 9. 6 16. 3 25.0 18% Isopar (E) H in 3GS 17. 1 24. 3 33. 8 Results show addition of Isopar0 H to 3GS oil improves oil return and oil return performance of 12,15 and 18% Isopar# H in 3GS are improved versus POE lubricant.

EXAMPLE S The kinematic viscosity in centistokes of Isopar0 H and pentane in 3GS mineral oil were compared to POE 22 oil at-15°C as shown in Table 5 below. The test method used was ASTM method D446.

TABLE 5 Kinematic Viscosity, Cst At-15°C POE 589.5 3GS 2936.7 3GS+6% Isopar (E) H1277.3 3GS + 12% IsoparX H 611.4 3GS + 3% Pentane 971.6 The data show 12% Isopar H in 3GS mineral oil approaches the viscosity of POE at-15°C. Addition of 3% pentane to 3GS provides less viscosity reduction.

Flammability is also increased when using pentane, while Isopar0 H is not flammable.

EXAMPLE 6 Tests were conducted to determine if R404A (44 wt% HFC-125,52 wt% HFC-143a, and 4 wt% HFC-134a) could be used in a Hussmann supermarket frozen food display case (Model HICA-0146-PLK), using conventional lubricant oil Suniso 3GS. The display case was outfitted with a Copeland semi-hermetic reciprocating compressor (Model KAL-016L) equipped with a sight glass in the oil sump. The frozen food case was installed in the indoor room of an environmental chamber and the condensing unit installed in the outdoor room.

The two units were connected by 5/8 inch outer diameter copper tubing in the suction line and by 1/2 inch outer diameter copper tubing in the liquid line. A 300 cc sample cylinder was installed between two valves in the liquid line. To determine oil circulation, the valves were closed to trap a refrigerant/oil sample during system operation. The sample cylinder was removed and weighed, refrigerant slowly evaporated, then cylinder reweighed to determine amount of refrigerant. Weight of oil remaining was used to calculate % oil in refrigerant or % oil circulation. Refrigerant R502 (48.8 wt% wt% CFC-115 (chloropentafluoroethane)) with 3GS oil was used as a baseline for comparison.

Capacity is intended to mean the change in enthalpy of the refrigerant in the evaporator per pound of refrigerant circulated, i. e. the heat removed by the refrigerant in the evaporator per time. Coefficient of performance (COP) is intended to mean the ratio of the capacity to compressor work. It is a measure of refrigerant energy efficiency. Results are shown in Table 6.

TABLE 6 Refrigerant/Oil Oil Circulation Capacity Combination t (Kbt COP R502/3GS 0.16 3.26 1.67 R404A/3 GS * 0.12 3.31 1. 70 R404A/6 % Isopar H in 0.15 3.26 1.65 3GS**

* Oil level in sight glass dropped below view ** 0. 3% IsoparX H based on refrigerant and oil The data show addition of 6 wt% Isopar H provides similar COP, capacity, and oil circulation to the baseline R502/3GS system. Without Isopar H, the oil level drops in the sight glass indicating insufficient oil return.

EXAMPLE 7 The Hussmann supermarket frozen food display case of Example 6 was used to study the concentration profile of Isopar H during system operation. 3GS mineral oil containing 15% Isopar (B) H was charged to the oil sump and the system was charged with R407C. After 48 hours of operation, the oil located in the oil sump and the oil in the liquid line after the condenser were analyzed for % Isopar H concentration and a mass balance was calculated as shown in Table 7 below.

TABLE 7 Location Time (hrs) wt% Isopar H Oil sump 0 15.0 Oil sump 48 2.3 Liquid line 48 3.2 Evaporator 48 9.5 The data show IsoparX H is volatile enough to be carried out of the oil sump and deposited in the evaporator. The presence of Isopar0 H in the evaporator reduces oil viscosity allowing the oil in the evaporator to return to the compressor.

The reduction of Isopar0 H concentration in the oil sump from 15% to 2.3% keeps oil viscosity sufficiently high in the sump to minimize impact on compressor lubrication.