MXPA97001644A - Improved hydrocarbon lubricants for use with inmiscib refrigerants - Google Patents

Abstract

The present invention relates to fluid refrigeration compositions comprising a hydrocarbon lubricant, an immiscible refrigerant and an additive capable of reducing the interfacial tension between the hydrocarbon lubricant and the refrigerant.

Description

IMPROVED HYDROCARBON LUBRICANTS FOR USE WITH REFRIGERANTS IMMISCIBLE This request is a continuation in part of the application NO. No. 08 / 426,500 filed on April 20, 1995 application Serial No. 08 / 301,694 filed September 7, 1994. This invention relates to fluid refriger- ation compositions comprising a hydrocarbon lubricant, such as mineral oil, a coolant immiscible with the hydrocarbon lubricant, and an additive capable of reducing the internal tension between the hydrocarbon lubricant and the immiscible coolant. More particularly this invention comprises a fluid cooling position comprising a hydrocarbon lubricant, such as mineral oil, a fluorocarbon refrigerant immiscible with the hydrocarbon lubricant and a surfactant capable of reducing the interfacial tension between the hydrocarbon lubricant and the hydrocarbon lubricant. the luorohydroca coolant bureau. For approximately the past 60 years, chlorofluorocarbons (CFCs) have been used commercially as heat exchange fluids in systems designed for refrigeration and air conditioning applications. These types of compounds have also been employed as propellants, foam blowing agents, and cleaning solvents for the electronics and aerospace industries. CFC-12 (dichlorodif luormetan), - CFC-115 (1-chloro-1, 1, 2, 2, 2-pentaf luoretane), and CFC-113 (1,1,2-trichloro-1, 2 , 2-trifluoethane) are examples of these compounds. In the early 1970s, Rowland and Molina hypothesized that the high stability inherent in CFCs provided these molecules with a very long life in a lower atmosphere. Consequently, they traveled slowly into the atmosphere, where the chlorine radicals are separated from the CFC molecules by the ultraviolet radiation effect of the sun. Radicals then attack the ozone found in this atmospheric layer decreasing its concentration. This urged the aerosol industry in the mid-70s to gradually replace the chemicals with environmentally safer alternatives that would fill their product specifications. In the mid-1980s, the detection of a drop in the concentration of ozone over Antarctica, an effect that is currently dispersing to other areas of the globe, has urged many nations to restrict and eventually disappear production and Use of CFCs before the end of the century. Consequently, various compounds have been suggested for use as alternative refrigerants. These compounds belong to the chemical families of hydrochlorofluorocarbon (HCFC) and hydrofluorocarbon (HFC). Examples of HCFCs are R-22 (hydrochlorodifluoromethane), R-123 (1,1-dichloro-2, 2, 2-trifluoroethane), and R-124 (1-chloro-1, 2,2, 2 -tetraf Luoretano). HCFCs have much lower ozone depletion potentials than CFCs because even when chlorine is present in these molecules, they contain hydrogen atoms that cause their decomposition to occur at lower levels of the atmosphere. However, since depletion of the ozone layer is currently continuing and expanding to other areas of the globe, there is a lot of legislative pressure to eventually restrict and discard these chemicals well. Therefore, these are perceived as short-term alternative cooling alternatives. The currently used mixtures of naphthenic mineral oil, alkylbenzenes and naphthenic co / alkylbenzene mineral oil have traditionally filled the lubrication and operation requirements of HCFC-loaded refrigeration systems. Examples of HFCs are R-134a (1, 1, 1, 2-tetraf luoreta not), R-152a (1, 1-difluoroethane, R-32 (difluoromethane), R-143a (1,1 1 - trifluoroethane), R-125 (1, 1, 1, 2, 2-pentaf 1 uroethane) and azeotropic and zotropic mixtures consisting of any of these, others, HFC components. These molecules are not ozone-depleting and, therefore, have now been adopted as alternative long-term refrigerants. While HFC refrigerants may have desirable physical properties that make them suitable for long-term refrigerant alternatives, they lack miscibility with naphthenic mineral oils traditionally used as refrigeration compressor lubricants. The chemical stability and miscibility of mineral oils with CFC and HCFC refrigerants, the chemical compatibility with all system components, the low bonding and pouring points, high dielectric strength, and proper viscosity provide the properties that improve the fuj total processing once loaded into the system. The use of naphthenic refrigeration oils in refrigeration or air conditioning applications where HFCs are used as refrigerants has been considered by some to be inappropriate due to the immiscibility of both fluids. The belief is that the immissibility or low dispersibility of the refrigerant and lubricant at unitary operating temperatures can provide an improper oil return to the printer. This causes inappropriate thermal transfer due to the oil coating on the inner surface of the heat exchange coils and, in extreme cases, lack of compressor lubricant. The first causes losses of energy efficiency, and the last results in the unit being burned. Jolly et al., U.S. Patent No. 4,941,986 states that the mixture of refrigerant and lubricant must be miscible / soluble and chemically and thermally stable through a wide temperature range, covering the operating temperature range of refrigerant systems. refrigeration and air conditioning. It is generally desirable that the lubricants be soluble / soluble in the refrigerant at concentrations of about 5 to 15% through a temperature range of -40 ° C to 80 ° C. This temperature scale slows the operating temperature of many cooling system designs and air conditioning in the market today. The inventors then described replacing the hydrocarbon lubricating oil with various synthetic materials which are much more expensive than the hydrocarbon oils. Evidently, it is economically and environmentally desirable to provide fluxes of alternative / acrylic hydrocarbon refrigerants, even when immiscible, for use in these systems. In American Society of Heating, Refrigerating and Air Conditioning Engineers, Sanvordenker (1989) and Reyes-Gavilán (1993) have independently noted that the proper oil return is present in domestic refrigeration systems loaded with HFC-134a and direct hydrocarbon oils. Sanvordenker has further explained that this condition depends on the unit configuration; Higher mount units with a horizontal thruster work well, while units with a vertical evaporator function do not work as well. Reyes-Gavilán has shown that using naphthenic mineral oil of low viscosity (70 SUS at 37.89C) in the same type of units as those tested by Sanvordenker, the dependence of the return of oil on unit configuration is erradicable. The agents responsible for return of oil in domestic refrigeration systems, in addition to low viscosity mineral oils with good flow characteristics in the system and proper lubrication operation in compressors, are high coolant velocities and short return lines between the evaporator and compressor. It is conceivable that such refrigeration or air conditioning systems with either low coolant velocities and / or long return lines between the evaporator and the compressor may experience low oil return, resulting in any of the operating problems. of the aforementioned subject. The prior art teaching of the use of hydrocarbon oils in refrigeration or air conditioning systems employing HFC refrigerants is limited. U.S. Patent No. 5,096,606 to Kao Corporation discloses and re vindicates compositions comprising HFCs and polyol esters which can be blended with other lubricants. U.S. Patent No. 5,114,605 to Mitsui Petrochemical discloses a composition comprising a hydrocarbon hydroflu, polyether carbonate and either a mineral oil or an alpha olefin gum. The summary of Japanese Patent No. 4,018,491 discloses that mixtures of an ester oil and a hydrocarbon oil such as mineral oil are compatible with hydrocarbon refrigerants in which the ratio of ester oil to hydrocarbon oil is at least unit. The summary of Japanese Patent No. 1,115,998 describes mixtures of an alkylbenzene, a mineral oil and a hydrofluorocarbon refrigerant. PCT WO / 12849 by Lubrizol suggests using viscosity adjusters such as naphthenic mineral oils. However, no mention is made of improvement in di spersabi 1 or miscibility / solubility characteristics of the hydrocarbon lubricant in the presence of HFC refrigerants. These references teach those skilled in the art the possibility of using blends comprising hydrocarbon lubricants in HFC refrigeration and air conditioning applications. The industry has observed, however; that many hydrocarbon lubricant CFC systems were retro-fitted to use HFC / polyol ester fluids have shown performance degradations, indicative of low oil return to the compressor, when the residual mineral oil content in the polyol ester exceeds 1% of the total lubricant in the system. For purposes of this invention, the term "immiscible" means that a two phase system is formed between refrigerant and lubricant, at least at any point in the scale of operation. typical of -409C to 809C in cooling or air conditioning systems. The general object of this invention is to provide fluid cooling positions comprising a hydrocarbon lubricant, preferably a mineral oil lubricant, and a coolant immiscible with the hydrocarbon lubricant - which contains at least one carbon atom and one carbon atom. fluorine. A more specific object of this invention is to provide fluid cooling compositions comprising a lubricant of mineral oil and a hydrofluorocarbon refrigerant immiscible with mineral oil. Other objects appear later. We have now found that the objects of this invention can be achieved with fluid cooling compositions comprising a hydrocarbon lubricant, a coolant immiscible with the hydrocarbon lubricant it contains when we have one carbon atom and one fluorine atom., and an effective amount of an additive capable of reducing the interfacial tension between the hydrocarbon lubricant and the immiscible refrigerant. The composition of this invention can be used in refrigeration and air conditioning systems with potential oil return difficulties when charged with hydrocarbon oil alone and HFC refrigerants. The goal is to facilitate the return of oil to the compressor by making the coolant and hydrocarbon lubricant more dispersible to each other, allowing the coolant to flush the lubricant off the internal surfaces of the heat exchangers. The invention provides appropriate lubrication and energy efficiency to the unit, while maintaining adequate chemical and thermal stability within the system. Briefly, the cooling fluid co-locations of this invention comprise a hydrocarbon lubricating oil, a coolant containing at least one carbon and one fluorine atom, and an additive capable of reducing the interfacial tension between the hydrocarbon lubricant and refrigerant Suitable hydrocarbon lubricants useful in this invention include paraffinic mineral oils, naphthenic mineral oils, alkylbenzene oils, polyalphadephines and their oligomers and mixtures thereof. The minor amounts (1 to 20% by weight) of alkylbenzene with larger amounts (99 to 80% by weight) of naphthenic mineral oil are particularly useful for improving the solubility or dispersibility of some additives (i.e., surfactants such as as 2,4,7,9-tetram ti l-5-decin-4,7-diol) in the hydrocarbon oil. Suitable refrigerants useful in this invention include those containing at least one carbon atom and one fluorine atom. Examples of suitable refrigerants i include R-22 (chlorodifluoromethane), R-124 (1-chloro-1,2, 2, 2-tetra-fluoroethane), R-134a (1,1,1,1-tetrafluoroethane) , R-143a (1,1,1 -tri-fluoroethane), R-152a (1,1-difluoroethane), R-32 (difluoromethane), R-125 (1, 1, 1, 2,2-pentafluoroethane) ), and mixtures thereof, such as R-404a (R-125 (44% by weight), R-143a (52% by weight), R-134a (4.0% by weight)). These mixtures may also contain propane as a component of the mixture in those applications where the heat exchange fluid is to be used as an intermediate retort fluid for existing refrigeration and air conditioning equipment. If desired, suitable refrigerants can be used with CFC refrigerants, particularly, when the residual amounts of these refrigerants are present in a system that is being fed back. The additives useful in this invention for reducing the interfacial tension between the lubricant and the refrigerant have the property of facilitating the displacement of the oil from the metal surfaces by the refrigerant. This property can be determined by sealing an immiscible refrigerant at room temperature, such as R134a, with the hydrocarbon lubricant, the hydrocarbon lubricant and the additives in a glass tube containing a steel or iron sliver. A two-phase system forms the lower layer with the lubricating oil that forms the upper layer and the refrigerant. The metal spill is then raised to the level of the oil in the tube using a magnet and the oil is allowed to completely wet the metal surface by moving the metal spill rapidly up and down in the oil. The additive is suitable for use in this invention, if the refrigerant displaces the oil when the sliver is slowly lowered into the liquid refrigerant layer. Suitable additives include surfactants, such as 2, 4, 7, 9-tetramet and 1 -5-decin-4,7-diol sold as Surfynol SE, luorocarbon esters sold as FC-430, phosphorus phosphorocarbons. anionics, phosphates, carboxylates (salts and acids), sulfonates, etc., such as HCFpCF gg CH2-CH2SCH2CH2C02Li sold as Zonyl FSA, 0 0 mixture? ?? F (CF2CF2) 3a8 -CH2CH20-P (0NH4) 2 y (F (CF2CF2) 3a8 -CH2C02) 2-P0NH4 sold as Zonyl FSP, Zonyl FSJ, etc. In some cases, it may be desirable to improve the solubility of surfactants in hydrocarbon lubricants with cosolvents or by using hydrocarbon lubricants made of two or more components. For example, as indicated above, minor amounts of alkylbenzene hydrocarbons improve the solubility or dispersity of some additives in mineral oil. Although applicants do not wish to be limited-by no theory, applicants believe that the interfacial tension at the refrigerant (1 fluid) / 1 GS interface is reduced to the point where the refrigerant dispersion coefficient (S) On steel it is slightly positive or very close to zero which allows the refrigerant to move the oil on slight agitation or due to the difference in specific gravity. The concept of dispersion coefficient is defined by: Y = gamma.

Where S is the coefficient of dispersion of the fluid (1) against the fluid (2) on the surface of a third phase, (3) a solid. The terms "Y" are the respective interfacial tensions. Spontaneous dispersion will occur if S 0. Other influences such as differences in specific gravity or energy to the mechanical cut are also applied, but S will denote the contribution of itiiterfacial tensions as it is influenced by additives or surfactants. 1 = refrigerant 2 = 1GS 3 = Steel surface in the case where no additive is present 23 12 13 and Y12 is a significant positive number as is evident from the prominent meniscus between the two phases. Also, since the oil preferentially moistens and continues to wet the steel even with some degree of agitation: This leads to the conclusion that Y12 + Y, 3 Y23 After the addition of certain surfactants, a deferent behavior results which is described by: 23 12 13 by observation: Y12 -? 0 (flat meniscus) Y9 2? 3 (coolant displaces oil on the steel surface) This leads to the conclusion that the dispersion coefficient for coolant on steel approaches 0 or becomes slightly positive, in the presence of certain additives which reduce Y12 + Y13 faster than Y23- The additive or surfactant can be used in the range of 0.001 to 5 parts by weight per 100 parts by weight of lubricating oil. The concentrates can be prepared containing up to 100 parts by weight of surfactant per 100 parts by weight of lubricating oil for the purpose of adding the same cooling systems containing lubricating oils of hydrocarbon that do not contain surfactant or quantities unsuitable for the purpose wanted. The weight ratio of lubricating oil to immiscible coolant can vary from 0.10 to 15 parts by weight per 100 parts by weight of refrigerant as is conventional in this branch. As noted above, the industry has observed that many retrocar- ried hydrocarbon / CFC lubricant systems for using HFC / polyol ester fluids have shown performance impairments, indicative of low return of oil to the compressor, when the content of residual mineral oil in the polyol ester exceeds 1% of the total lubricant in the system. Surprisingly, we have found that the addition of relatively small amounts of polyol ester lubricants to the compositions of this invention improves the solubility or dispersibility of some additives (i.e., surfactants such as 1, 3, 7.9- tetramethi-5-decin-4,7-diol) in the hydrocarbon oil. In such a case, the weight ratio of polyol ester to hydrocarbon lubricant can vary from about 1:99 to 1: 3, preferably 1:19 to 1: 4. Consequently, we believe it is advantageous to retro-fit CFC hydrocarbon lubricant systems to use HFCs by adding concentrated compositions containing polyol ester and surfactant such as 2,4,7,9-tetramethyl-5-decin-4,7-diol or ester. fluorinated directly to the compressor system with no additional hydrocarbon lubricant as long as the surfactant in the compressor system constitutes 0.001 parts by weight per 100 parts by weight of the 1 fluid in the compressor. The polymer ester / surfactant concentrate may comprise about 0.1 to 100 parts by weight of surfactant age per 100 parts of the polyol ester. Suitable polyol esters comprise polyhydric alcohol esters of monocarboxylic aliphatic acids which have 4 to 25 carbon atoms alone or together with di or tri carboxylic acids. Suitable polyhydric alcohols can contain from 2 to 6 hydroxy groups, such as neopentyl alcohol, 1,1,1-trimethoxyethane, 1, 1, 1 -trimetiol propane, pentaerythritol etc. Suitable aliphatic carboxylic acids include branched and unbranched acids such as butyric acid, isobutyric acid, 2-ethylhexanoic acid, n-octanoic acid, vale rich acid, isopentanoic acid, hexanoic acid, heptanoic acid, nonanoic acid, stearic acid, etc. Dicarboxylic acids, such as maleic acid, succinic acid, adipic acid, etc. and tricarboxylic acids such as trimellitic acid can be used in small amounts to adjust the viscosity of the polyol ester. Table I presents appropriate stability and wear improver additives that can be used with hydrocarbon lubricants that employ surfactants in cooling and air conditioning applications with lubricant immiscible coolants.

TABLE I Example of Appropriate Additives (Stabilization and Anti-Wear) Brand Chemical and Functional Characterization by Weight of BHT Additive Phenolic Antioxidant 0.5 Irganox L-57 Amine Antioxidant 0.5 Reomet 39 Copper Corrosion Inhibitor derj_ 0.5 triazole ford ERL 4221 Epoxide 0.5 Syn-0-Ad 8478 Tri-ester anti-wear agent 5.0 aryl phosphate Durad Anti-wear agent phosphate ester 5.0 Aditive RC8210 Sulfurized Expression Agent 2.5 Example I A 9 mL glass tube was charged with 0.050 L of naphthenic mineral 70 SUS (Suniso 1GS) containing 0.5% by weight of candidate surfactant, a steel sliver of 6 m and 0.70 ml of 1, 1, 1, 2-tetraf luoretane (R-134a) and sealed. A two-phase system with naphthenic mineral oil consisting of the top layer and the hydrofluorocarbide was placed in the bottom layer. The metal chip was completely wetted with oil moving the chip rapidly up and down in the oil phase using a magnet. The splinter was then lowered slowly into the tetrafluorean layer. The results are shown below in Table II.

TABLE II Surfactant Mixing Agent Diisoamyl Succinate (PIB) The oil adheres to the splinter. The oil is wounded to the glass EXP 5159-197 (fluorinated ester made Improvement in dispersabi 1 ida by Organics) but the oil adheres to asti lia and Tetraquis glass (2-eti lhexanol) The oil adheres to a Pentaerythritol tilla and glass Surfynol SE Oil removed from splinter and glass with refrigerant. Two highly dispersible coatings Surfynol tG The oil adheres to both the squeegee and glass.

TABLE II (continued) Surfactant Mixing Behavior EX 1038 (carbolic acid dimer ester) Oil adheres to box 1 and glass FC-430 Separated oil and glass for R ~ 134a Two highly dispersible layers FC-431 Oil adheres Tillage and glass FC-740 Oil adheres to glass and slabs Excessive foam.

The above data clearly show that Surfynol SE comprising 2, 4, 7, 9-tetramethi-5-decin-4,7-diol and FC-430 qu comprising a fluorinated ester are suitable for use in this invention.

Example II A 9 ml glass tube was charged with 0.050 ml of naphthenic mineral oil 70 SUS (Suniso 1GS) containing 0.05% by weight of candidate surfactant (Surfynol SE or FC-430), a 6 mm steel sliver and 0.70 ml of 1, 1, 1, 2-tetraf luoreta not (R-134a) and sealed. A two-phase system was formed with the naphthenic mineral oil constituting the upper layer and the luocarbon hydrofoil the lower layer. The metal splinter was completely wetted with oil by moving the splinter rapidly up and down the oil phase using a magnet. The astile was then lowered slowly towards the tetra-fluoroethane layer. For both candidates, the oil is separated from the asylate and glass by R-134a. Both layers of lubricant and coolant are very dispersible to each other, causing the oil to separate from the surface of the astilal and glass mediant R-134a.

Example III A supermarket freezer lattice at average solenoid temperature below multi-zone pump in New England, equipped with two five-door freezer lattice cabinets (each of 2,990.19 1), one compressor (Ethic cup Model No. R-76 WMT3T) placed at approximately 1.83 to 2.13 from the ground, and evaporators on the floor of each tank were retro-fitted. The refrigerant gas and oil travel through approximately 6.10 meters of vertical diameter 22.26 mm and horizontal suction return lines before reaching the compressor through a tube of 34.94 mm. The system was loaded with R-402A (load of 13.61 kilograms), which comprised 38% by weight of R125 (pentaf luoretane), 60% by weight of R22 (hydrochloride lumetanole) and 2% by weight of R290 (propane). ) and a lubricating oil of alkyl benzene 200 SUS containing anti-wear and foaming agents. Since the unit operated less than -20.5Q the lubricant level in the compressor dropped and the oil pressure switch disconnected the unit. The system was then operated at approximately -17,789C to maintain the proper oil and lubrication pressure. The oil was drained from the system leaving some residual alkyl benzene; it was charged with 150 SUS oil comprising primarily naphthenic mineral oil, 10% by weight of alkylbenzene and 0.05% by weight of Surfynol SE; it was evacuated for 1/2 hour and left running for 1 hour to wash the residual alkylbenzene oil from the system. During this time, the oil pressure switch was not disconnected and temperatures of -17 C and -239 C were reached for the respective lattices. After one hour, the oil was again drained from the system and replaced in fresh 150 SUS oil comprising mainly naphthenic mineral oil, 10% by weight alkylbenzene and 0.05% by weight of Surfy nol SE. Both freezers have been operated for two months at -23QC to -269C with no oil return difficulties.

Example IV The compositions listed below in Table III were tested with R-134a and 2,4,7,9-tetramethyl-5-decin-4,7-diol surfactant with hopeful results. In the Table, H-1 means a naphthenic mineral oil 12cSt at 40QC, H2 means a white naphthenic mineral oil 38cSt at 409C, H-3 means a naphthenic mineral oil of 29 to 30cSt at 40QC, H-4 means a naphthenic mineral oil 18cSt at 40eC, H-5 means alkybenzene 29 at 30 cSt at 409C, Pl means a polyester of trimetiolpropane, 70% of valeric acid and 30% of isovaleric acid, P2 means a polyester of pentaerythritol and acid 2- ethenohexaenoic acid and P3 means a polyester of pentaerythritol, valeric acid, isovaleric acid and adipic aciic acid, Ionic candidates listed below in Table IV. Zonyl FSN and Zonyl FSO are F (CF2CF2) 3_8 -CH2CH20 (CH2CH20)? H which have different levels of oxyethylene units. In Table AN it means anionic and NON means nonionic.

TABLE IV Surfactant Type% in Weight Activity Zonyl FSP AN 0.05 Partial removal of the oil from the shaft the AN Complete removal of the oil from the shaft Zonyl FSA AN 0.05 None 0.50 Partial removal of oil from the splinter.

Zonyl FSJ AN 0.05 Complete removal of the oil from the chip 0.50 Complete removal of the oil from the chip Zonyl FSN NON 0.05 None 0.50 None Zonyl FSO NON 0.05 None 0.50 None The above data clearly shows that surfactant surfactants of anionic luorohydrocarbons are suitable for use in this invention.

Comparison Example in an effort to displace the lubricant from the shaft without any additive from the lubricating compositions of this invention comprising mixtures of either 90% by weight of mineral oil and 10% by weight of polyester or 70% by weight of Mineral oil and 30% by weight polyester were tested in the manner described in Example II using naphthenic mineral oil ISO 10 and either polyester P-1, which means a polyolyester of trimethylolpropane and 30% of valeric acid and P- 2, which means a poiolyester of 2-ethylhexanoic acid, 79% of neopentyl glycol and 21% of pentae ritritol. The results are shown in Table V.

TABLE V Polyester% by weight of Polyester Results P-1 10% The oil adheres to asti 1 and glass. 30% Oil adheres to asti 1 la and glass P-2 10% Oil adheres to asti 1 la and glass 30% Oil adheres to asti 1 la and glass

Claims (24)

CLAIMS:

1. - A fluid cooling composition comprising a hydrocarbon lubricant, a coolant immiscible with the hydrocarbon lubricant containing at least one carbon atom and a fluorine atom, and an additive capable of reducing the interfacial tension at the interface between the hydrocarbon lubricant and the liquid refrigerant to the point where the coefficient (s) of dispersion of liquid refrigerant on steel is H positively or very close to zero, allowing the refuent to displace hydrocarbon lubricant from the steel where the additive it is present in a concentration of 0.001 to 5 parts by weight per 100 parts by weight of hydrocarbon lubricant.

2. The composition of claim 1, wherein the hydrocarbon lubricant comprises a paraffinic mineral oil.

3. - The composition of claim 1, wherein the hydrocarbon lubricant comprises a naphthenic oil.

4. The composition of claim 1, wherein the hydrocarbon lubricant comprises an alkylbenzene oil.

5. The composition of claim 1, wherein the hydrocarbon lubricant comprises a polyalphaolefin and its oligomers.

6. The composition of claim 1, wherein the hydrocarbon lugricant comprises a larger amount of naphthenic mineral oil and a minor amount of an alkylbenzene oil.

7. The composition of claim 6, wherein the hydrocarbon lugricant is a paraffinic mineral oil.

8. The composition of claim 1, wherein the refrigerant comprises a hydrofluorocarbon.

9. The composition of claim 8, wherein both the halogen groups of the hydrofluorocarbon are fluorine.

10. The composition of claim 9, wherein the hydrofluorocarbon comprises 1,1,1,2-tetrafluoroethane.

11. The composition of claim 9, wherein the hydrofluorocarbon comprises pentaf luoroethane.

12. The composition of claim 9, wherein the composition also comprises diformonocloromethane.

13. The composition of claim 1, wherein the additive comprises a surfactant.

14. The composition of claim 13, wherein the surfactant comprises 2,4,7,9-tetramethyl-5-decin-4,7-thiol.

15. The composition of claim 14, wherein the composition contains a polyol ester lubricant in a weight ratio of polyol ester to hydrocarbon lubricant of approximately 1:99 to 1: 3.

16. The composition of claim 13, wherein the surfactant comprises a fluoryester.

17. The composition of claim 13, wherein the surfactant comprises an anionic f luorohydrocarbon.

18. The composition of claim 1, wherein the refrigerant is immiscible through the full temperature scale of -40QC to 80SC with the lubricant.

19. A fluid refrigeration composition comprising a hydrocarbon lubricant comprising at least one member selected from the group consisting of paraffinic mineral oil, naphthenic mineral oil, alkyl alcohol oil, a polyalphaolefin and its oligomers , a refrigerant in i cible with the hydrocarbon lubricant containing at least one carbon atom and one fluorine atom, and an effective amount of an additive capable of reducing the interfacial tension between the hydrocarbon lubricant and the liquid refrigerant in a manner that the refrigerant can displace the lubricant from the internal surfaces of the heat exchangers and lines.

20. A composition comprising a lubricant of polyol ester and 2, 4, 7, 9-tetramethyl-5-decin-, 7-diol.

21. The composition of claim 19, wherein the 2,4,7,9-tetramethyl-5-decin-4,7-diol is present in a concentration of about 0.1 to 100 parts by weight per 100 parts in weight of polyol ester.

22. A composition comprising a lubricant of polyol ester and fluorinated ester.

23. A composition comprising a polyol ether lubricant and an anionic fluorohydrocarbon.

24. - The method of retro-fitting a compressor system comprising the step of adding a concentrate comprising a polyol ester lubricant and 2,4,7,7-tetramethyl-5-decin-4,7-diol to the system compressor.