HU218032B - Enhanced hydrocarbon lubricants for use with immiscible refrigerants - Google Patents

Abstract

In particular, the invention relates to a refrigerant composition for use as refrigerants and lubricants in refrigeration equipment and air conditioning systems. The coolant composition of the present invention comprises a hydrocarbon lubricant, an at least one fluorinated hydrocarbon refrigerant, non-miscible with an ash hydrogen lubricant, wherein each halogen atom fluorine and an effective amount of additive reduce the boundary tension between the hydrocarbon lubricant and the liquid refrigerant to the point where the coefficient of dispersion of the liquid refrigerant on steel is slightly positive, allowing the refrigerant to remove the hydrocarbon lubricant from the steel, wherein the additive is present in an amount of 0.001 to 5 parts by weight of 100 parts by weight of hydrocarbon lubricant. ŕ

Description

The present invention relates to coolant compositions comprising a hydrocarbon lubricant such as mineral oil, a hydrocarbon lubricant immiscible refrigerant and an additive which reduces the interfacial tension between the hydrocarbon lubricant and the immiscible refrigerant. More particularly, the present invention relates to coolant compositions comprising a hydrocarbon lubricant such as mineral oil, a fluorinated hydrocarbon refrigerant and a surfactant that reduces the interfacial tension between the hydrocarbon lubricant and the fluorinated hydrocarbon refrigerant.

For approximately 60 years, fully chlorinated fluorinated hydrocarbons (chlorofluorocarbons, or CFCs) have been used as refrigerants in refrigeration and air conditioning applications. Compounds of this type have been found to be useful as propellants, foaming agents and cleaning solvents in the electronics industry as well as in space technology. Examples of such compounds are CFC-12 (dichlorodifluoromethane), CFC-115 (1-chloro-1,1,2,2,2-pentafluoroethane) and CFC-113 (1,1,2-trichloro-1), 2,2-trifluoro-ethane).

In the early 1970s, Rowland and Molina assumed that due to the high stability of CFCs, these molecules would remain in the lower layers of the atmosphere for a very long time. It follows that they slowly infiltrate the stratosphere, where chlorine radicals are released from the CFC molecule by the ultraviolet radiation of the sun. The radicals then attack the ozone in this atmospheric layer and reduce its concentration. This triggered the aerosol industry in the mid-1970s to gradually replace these compounds with other compounds that are environmentally safer that meet the requirements of their own products.

In the mid-1980s, it was shown that concentrations of ozone above Antarctica are decreasing, and today they extend to other parts of the world. This has encouraged many countries to restrict, and where appropriate, ban, the production and use of CFCs by the end of this century. As a result, many compounds have been proposed as alternative refrigerants. These compounds are either hydrogen fluoride-containing hydrofluorocarbons (HCFCs) or hydrogen fluoride-containing hydrofluorocarbons (HFCs). Examples of such HCFCs are R-22 (chloro-difluoromethane), R-123 (1,1-dichloro-2,2,2-trifluoroethane) and R-124 (1-chloro-1,2, 2,2-tetrafluoroethane). HCFCs are much less hazardous to ozone than CFCs because they contain chlorine in their molecules, and as a result they are already degraded in the lower layers of the atmosphere. Nowadays, as a result of the continued destruction of the ozone layer, which extends to other parts of the world, there are many places where there is regulatory pressure that restricts or prohibits the use of these chemicals. Therefore, they can only be considered as alternative refrigerants for a short period of time. Currently used naphthenic mineral oils, alkylbenzenes and naphthenic oil-alkylbenzene mixtures have traditionally met the lubrication and power requirements of HCFC-filled cooling systems.

HFCs and materials containing such compounds, such as R-134a (1,1,1,2-tetrafluoroethane), R-152a (1,1-difluoroethane), R-32 (difluoromethane), R-143a (1,1,1-trifluoroethane), R-125 (1,1,1,2,2-pentafluoroethane) and azeotropic and zeotropic mixtures of any of these or other HFC components. These molecules do not damage ozone and, as such, are long-term accepted substitutes for previous coolants. Although HFCs, as coolants, have favorable physical properties that make them suitable for long-term replacement of current coolants, they are not miscible with naphthenic-based mineral oils traditionally used as refrigerant compressor lubricants. The chemical stability of mineral oils, their miscibility with CFCs and HCFCs, their chemical compatibility with all components of the system, their low flocculation and freezing point, their high dielectric constant and their good viscosity provide the properties that enhance their overall performance once charged. into the system.

The use of naphthenic-based oils in refrigeration or air-conditioning systems using HFCs as refrigerants is not considered suitable by many because the two liquids are immiscible. It is believed that if the refrigerant and the lubricant are immiscible or slightly dispersible at the operating temperature of the unit, the oil return to the compressor may be inadequate. This can weaken the heat transfer due to the fact that the inner wall of the heat exchanger tubes is covered with oil and, in extreme cases, can cause a lack of lubricant in the compressor. The former leads to reduced energy efficiency and the latter to burn-out of the unit.

According to U.S. Patent No. 4,941,986 to Dolly et al., Refrigerant and lubricant mixture components must be miscible / soluble and thermally stable over a wide range of temperatures, including operating temperatures of refrigeration and air conditioning equipment. It is generally desirable for the lubricant to be miscible / soluble in the refrigerant at concentrations ranging from about 5% to about 15% and at temperatures between -40 ° C and 80 ° C. This temperature range is the typical operating temperature for commercially available refrigeration and air conditioning systems.

The authors of the cited patent then disclose the replacement of hydrocarbon lubricating oils with various synthetic materials which are substantially more expensive than hydrocarbon oils. Obviously, it is economically and environmentally desirable to provide a refrigerant containing hydrocarbon oil and alternative coolant for use in such systems, even if the components thereof are incompatible.

HU 218 032 Β

At the American Society of Heating, Refrigeration and Air Conditioning Engineers, two authors, Sanvordenker in 1989 and Reyes-Gavilan in 1993, independently showed that there was adequate oil return in HFCs that They are filled with -134a and straight chain hydrocarbon oil. Sanvordenker further explained that this situation depends on the design of the equipment; the equipment consisting of superimposed units with horizontal evaporator works well, while the equipment consisting of adjacent units with vertical evaporator works well, but it does not function properly. Reyes-Gavilan, however, pointed out that when low viscosity naphthenic mineral oil (having a viscosity of 13.3 x ^{10 6} m ² / s at 37.8 ° C, or 70 SUS according to ASTM D 2422) is used in the same type of equipment as Sanvordenker tested, it completely eliminates the dependence of oil return on the design of the equipment. In household refrigeration equipment, oil reflux, in addition to mineral oils of low viscosity and good flow characteristics and good lubricity, depends on high refrigerant speed and short return line from the evaporator to the compressor. Refrigerants or air conditioners that have a low refrigerant flow rate and / or a long return line from the evaporator to the compressor may have a lower oil return, which may result in the aforementioned operating problems.

BACKGROUND OF THE INVENTION The use of hydrocarbon oils in HFC-based refrigeration and air conditioning systems is scarce. U.S. Patent 5,096,606 (Kao Corporation) and related claims disclose compositions containing HFCs and polyolesters that can be mixed with other lubricants.

The composition disclosed in Mitsui Petrochemical, U.S. Patent No. 5,114,605, contains a hydrogen-containing fluorinated hydrocarbon, a polyether carbonate and either a mineral oil or an alpha-olefin oligomer.

Japanese Patent 4,018,491 discloses that mixtures containing ester oils and hydrocarbon oils, such as petroleum oils, may be compatible with hydrogen-containing fluorinated hydrocarbon coolants if they contain at least an equal ratio of ester oil to hydrocarbon oil.

Japanese Patent Specification No. 1,115,998 discloses mixtures containing alkylbenzene, mineral oil, and hydrogen-containing fluorinated hydrocarbon coolants.

In PCT WO / 12849 (Lubrizol), viscosity regulators such as naphthenic mineral oils are suggested. However, there is no discussion in this document of how to improve the dispersibility or miscibility / solubility of a hydrocarbon lubricant in the presence of HFC coolant.

The possibility of using mixtures of hydrocarbon lubricants readable from these references in HFC refrigerant and air conditioning systems. However, in the industry, it has been found that many hydrocarbon lubricated CFC systems that have been converted to HFC / polyol ester refrigerant have a poorer performance, indicating poor oil return to the compressor. This was the case when the amount of mineral oil remaining in the polyol ester exceeded 1% of the total amount of lubricant in the system.

For purposes of the present invention, the term "immiscible" or "immiscible" means that the coolant and the lubricant form a two-phase system, at least when the temperature is typical for the operation of the refrigeration and air conditioning systems within the range of -40 ° C to 80 ° C. falls into the interval.

It is an object of the present invention to provide a coolant composition comprising a hydrocarbon lubricant, preferably a mineral oil lubricant, and a refrigerant immiscible with the mineral oil lubricant, the latter having at least one carbon atom and at least one fluorine atom. It is a further object of the present invention to provide a coolant composition comprising a mineral oil lubricant and a hydrogen immiscible hydrofluorocarbon refrigerant. Other objects of the invention will be apparent from the following.

It has been found that the object of the present invention can be achieved by a coolant composition comprising a hydrocarbon lubricant which is immiscible with a hydrocarbon lubricant and has at least one carbon atom and at least one fluorine atom in its molecule and an effective amount of additive that reduces interfacial tension. hydrocarbon lubricant and immiscible refrigerant.

The composition of the present invention can be used in refrigeration and air conditioning systems where oil reflux may be difficult when filled with straight chain hydrocarbon oils and HFCs as refrigerants. Our aim is to facilitate the return of oil to the compressor by making the refrigerant and the hydrocarbon lubricant more dispersible with one another, thereby allowing the refrigerant to wash the lubricant from the inside of the heat exchangers. The invention provides the equipment with adequate lubrication and energy efficiency, while maintaining adequate chemical and thermal stability in the system.

In summary, the coolant composition of the present invention comprises a hydrocarbon lubricating oil, a refrigerant containing at least one carbon atom and at least one fluorine atom, and an additive that can reduce the interfacial tension between the hydrocarbon lubricant and the refrigerant.

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Suitable lubricants for use in the present invention include paraffin-based mineral oils, naphthenic-based mineral oils, alkylbenzene oils, poly-alphaolefins and their oligomers, and mixtures thereof. With small amounts (1-20 wt.%) Of alkylbenzene with higher amounts (99-80 wt.%) Of naphthenic mineral oil, certain additives (namely surfactants such as 2,4,7,9-tetramethyl-5-decin-4,7) are particularly preferred. -diol) to improve its solubility or dispersibility in hydrocarbon oil.

Suitable refrigerants for the purposes of the present invention are compounds having at least one carbon atom and at least one fluorine atom in their molecule. Suitable refrigerants include R-22 (chlorodifluoromethane), R-124 (1-chloro-1,2,2,2-tetrafluoroethane), R-134a (1,1,1, 2-tetrafluoroethane), R-143a (1,1,1-trifluoroethane), R-152a (1,1-difluoroethane), R-32 (difluoromethane), R-125 (1, 1,1,2,2-pentafluoroethane) and mixtures thereof, such as R-404a (44% R-125, 52% R-143a and 4.0% R-134a). These mixtures may even contain propane as their component when the heat exchange fluid is temporarily used to restart existing refrigeration or air conditioning equipment. If desired, the appropriate refrigerant compounds may be used in combination with the CFC compound refrigerant, especially if the restart medium contains a residual refrigerant.

Additives useful in reducing the interfacial tension between the lubricant and the refrigerant according to the invention have the property of facilitating the removal of oil from the metal surfaces by the refrigerant. This property can be determined by filling a glass tube in which a steel or iron shard is placed with a refrigerant compound immiscible with a hydrocarbon lubricant, such as R-134a, a hydrocarbon lubricant and an additive to be tested, at room temperature and soldering the glass tube. . A two-phase system is formed in which the lubricating oil forms the upper layer and the refrigerant forms the lower layer. The metal shear is then raised with a magnet in the tube above the level of the oil, and by rapidly moving it up and down in the oil, it is possible for the oil to completely wet the surface of the metal. An additive is considered to be suitable for the invention if the refrigerant removes the oil when the fragment is slowly lowered into the liquid refrigerant layer.

Suitable additives include, but are not limited to, surfactants such as 2,4,7,9-tetramethyl-5-decin-4,7diol, marketed under the tradename Surfynol SE, fluorinated hydrocarbon esters under the tradename FC-430, phosphates, carboxylates (salts and acids), sulfonates and other similar compounds such as F (CF, CF ₂ ) _{3 8} -CH ₂ CH ₂ SCH ₂ CH ₂ CO ₂ Li, marketed as Zonyl FSA, and F (CF ₂ CF ₂ ) _{3 S} -CH ₂ CH ₂ O-PO (ONH ₄ ) ₂ and the compounds of the formula [F (CF ₂ CF ₂ ) _{3 - 8} -CH ₂ CH ₂ O] ₂ PO (ONH ₄ ), which are Zonyl FSP and Zonyl FSJ as well as other similar compounds.

Optionally, it may be advantageous to increase the solubility of the surfactant in the hydrocarbon lubricant by co-solvents or by using hydrocarbon lubricants consisting of two or more components. For example, as noted above, a small amount of alkylbenzene hydrocarbon improves the solubility of some additives in mineral oil.

Without being bound by any theory, it is assumed that the interfacial tension at the refrigerant (liquid) / lubricant (1 GS) interface is reduced to the point where the liquid dispersion coefficient of the refrigerant on the steel is slightly positive or very close to zero. allows the refrigerant to remove the oil by gentle movement or by the weight difference of the species.

The scattering coefficient is defined as: Y = gamma.

s = Y ₂₃ -Y, 2 -Y ₁₃ where S is the dispersion coefficient of liquid (1) against liquid (2) on the surface of a third phase solid (3). Each interface voltage is denoted by the Y symbol. Spontaneous dispersal occurs when S> 0. Other effects, such as specific gravity differences or mechanical shear energy, also apply, but S indicates the contribution of interfacial stresses as influenced by additives or surfactants.

= refrigerant 2 = lubricant (1 GS)

3 = the steel surface

In the absence of additive 0> Y ₂₃ —Y [ ₂ —Y | ₃ and Y _{2 are} a non-zero positive number, as shown by the prominent meniscus between the two phases. Because oil preferentially moisturizes steel and continues to do so, even after some movement ^ 13 ^{> Λ |} ^ 23From this, it follows that Y12 + Y, 3> Y ₂ 3 ·

Adding certain surfactants to the system changes its behavior, which can be described as follows:

0 <Y ₂ 3 ~ Y i ₂ -Yi ₃ observed:

Y | _{2 to} 0 (flat meniscus)

Y ₂₃ > Y _{) 3} (the refrigerant removes oil from the steel surface).

This leads to the conclusion that the scattering coefficient of the refrigerant on the steel is close to zero or takes a small positive value in the presence of certain additives which reduce the value of Y _{) 2} + Y ₍₃ ) faster than the value of Y ₂₃ .

The additive or surfactant may be used in an amount of 0.001 to 5 parts by weight per 100 parts by weight of lubricating oil. Concentrates may be prepared containing up to 100 parts by weight of surfactant per 100 parts by weight of lubricating oil for the purpose of adding it to cooling systems containing hydrocarbon lubricating oils,

EN 218 032 Β and in which the surfactant is either not present at all or is not present in the desired amount.

The weight ratio of lubricating oil to immiscible refrigerant may range from 0.10 parts to 15 parts by weight per 100 parts by weight of refrigerant, as is customary in the art.

As mentioned above, industrial experience has shown a reduction in power to the oil return to the compressor when hydrocarbon lubricant / CFC systems are restarted using HFC / polyol ester fluids and the amount of mineral oil remaining in the polyol ester exceeds 1%. Surprisingly, it has been found that the addition of a relatively small amount of a polyolester lubricant to the composition of the present invention results in a higher solubility of certain additives (namely surfactants such as 2,4,7,9-tetramethyl-5-decin-4,7-diol). or dispersed in mineral oil. In this case, the weight ratio of polyol esters to hydrocarbon lubricant may range from about 1:99 to 1: 3, preferably from about 1:19 to 1: 4.

Accordingly, it is preferred to restart the CFC system with a hydrocarbon lubricant using HFC such that a polyol ester and a surfactant such as 2,4,7,9-tetramethyl-5-decin-4,7-diol or a fluorinated ester are directly added to the compressor system. a concentrate composition is added with or without the addition of additional hydrocarbon lubricant, provided that the amount of surfactant in the compressor system is at least 0.001 parts by weight per 100 parts by weight of the liquid lubricants in the compressor system.

The polyol ester / surfactant concentrate may contain from about 0.1 to about 100 parts by weight of surfactant per 100 parts by weight of polyol ester.

Suitable polyol esters for the purposes of the present invention are esters of C4-C25 aliphatic monocarboxylic acids, alone or in combination with di- and tricarboxylic acids, and multifunctional alcohols. The ester-forming multifunctional alcohols may have from 2 to 6 carbon atoms, such as neopentyl alcohol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, pentaerythritol and the like. Suitable aliphatic carboxylic acids include straight and branched chain carboxylic acids such as butyric acid, isobutyric acid, 2-ethylhexanoic acid, n-octanoic acid, valeric acid, isopentanoic acid, hexanoic acid, heptanoic acid, nonanoic acid, steric acid and the like. carboxylic acids. Dicarboxylic acids such as maleic acid, succinic acid, adipic acid and tricarboxylic acids such as trimellitic acid can be used in small amounts to adjust the viscosity of the polyol ester.

Table 1 shows stabilizer and anti-wear additives which are suitable for use with hydrocarbon lubricants as surfactants in lubricant immiscible refrigerant and air conditioning equipment.

Table 1

Trade name Chemical and functional properties of the additive Crowd% BHT phenolic antioxidant 0.5 Irganox L-57 amine antioxidant 0.5 Reomet 39 triazole derivative, copper corrosion inhibitor 0.5 ERL4221 epoxide 0.5 Syn-O-Ad 8478 triaryl phosphate ester, anti-wear agent 5.0 RC8210 additive sulfur containing high pressure additive 2.5

Example 1

A 9 mL glass tube was charged with 0.050 mL of 37.8 ° C 13.3x10 ⁶ m ² / s (70 SUS) of a naphthenic mineral oil (Suniso 1GS) containing 0.5 wt% of the surfactant to be tested and a 6 mm steel and 0.70 ml of 1,1,1,2-tetrafluoroethane (R-134a) and the glass tube is soldered. A two-phase system is formed in which the naphthenic mineral oil forms the upper phase and the fluorinated hydrocarbon the lower phase. The metal fragment is completely moistened with oil by rapidly moving it up and down in the oil phase using a magnet. The metal fragment is then lowered slowly into the tetrafluoroethane phase. The results obtained are summarized in Table 2.

Table 2

Surfactant The behavior of the mixture Diisoamyl (PIB) - succinate The oil adheres to the splinters. The oil adheres to the glass. EXP 5159-197 (Fluorinated ester, Organics) Dispersibility is improved, but the oil adheres to the splinters and the glass. Tetrakis (2- ethylhexanol) pentaerythritol The oil adheres to the splinters and the glass. Surfynol SE The oil separates from the splinters and the glass. The two phases are highly dispersible in each other. Surfynol TG The oil adheres to the splinters and the glass. EX 1038 (Carboxylic acid dimer ester) The oil adheres to the splinters and the glass. FC-430 The oil is removed by R-134a from the fragment and the glass. The two phases are highly dispersible in each other. FC-431 The oil adheres to the splinters and the glass. FC-740 The oil adheres to the splinters and the glass. High foaming.

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As is clear from the above data, Surfynol SE, which contains 2,4,7,9-tetramethyl-5-decin-4,7-diol, and FC-430, which contains a fluorinated ester, are suitable for use in the present invention.

Example 2

A 9 mL glass tube was charged with 0.050 mL of 37.8 ° C Napoleic mineral oil (Suniso 1 GS) having a viscosity (70 SUS) of 13.3 x 10 ~ ⁶ m ² / s (70 SUS) containing 0.05% by weight of surfactant to be tested (Surfynol SE). or FC-430), place a 6 mm steel shard in a glass tube and add 0.70 mL of 1,1,1,2-tetrafluoroethane (R-134a) and solder the glass tube. A two-phase system is formed in which the upper phase is naphthenic mineral oil and the lower phase is fluorinated hydrocarbon. The metal fragment is completely moistened with oil by rapidly moving it up and down with the aid of a magnet in the oil phase. The fragment is then slowly lowered into the tetrafluoroethane phase. For both test substances, R-134a removes oil from the metal shard and glass. The lubricant and refrigerant layer are highly dispersible with each other, allowing R-134a to remove oil from the metal shard and glass.

Example 3

We re-commissioned a solenoid-controlled, pumpable, mid-temperature, multi-zone freezer rack in a supermarket in New England, with a freezer rack with two five-door (3 m ³ each) freezer compartments at a height of about 1.8 to 2.1 m from fodem level (Copelametic Model No. R-76 WMT3T) and evaporators at the bottom of each freezer compartment. The refrigerant gas and oil were passed through a suction and return line of approximately 6.1 m long with a 2.22 cm diameter vertical and horizontal sections before entering the compressor via a 3.5 cm pipe. The system was filled with R-402A composition (13.6 kg fill) containing 38% by weight R-125 (pentafluoroethane), 60% by weight R-22 (chlorodifluoromethane) and 2% by weight. It contained R-290 (propane) and an alkylbenzene lubricating oil having a viscosity of 42.8 x ΙΟ ^-6 m ² / s (200 SUS) at 37.8 ° C, containing anti-wear and anti-foaming agents. When the unit operating temperature dropped below -20.55 ° C, the lubricant level in the compressor was reduced and the oil pressure switch turned the unit off. The system was then operated at -17.8 ° C to ensure proper oil pressure and lubrication.

The oil was drained from the system with little alkylbenzene remaining; filled with oil at a viscosity (150 SUS) of 37.8 ° C, 32 x 10 ⁶ m ² / s (150 SUS), containing predominantly naphthenic mineral oil, 10% w / w alkylbenzene and 0.05% w / w Surfynol SE; | Air was vented for 1 hour and then operated for 1 hour to purge residual alkylbenzene oil from the system. Meanwhile, the oil pressure switch did not turn off and the chambers reached -27.2 ° C and -23.3 ° C, respectively. After 1 hour, the oil was drained again and replaced with fresh 150 SUS oil containing 10% by weight of alkylbenzene and 0.05% by weight of Surfynol SE in the presence of a predominantly naphthenic mineral oil. Both freezing chambers were operated for two months at temperatures between -23.3 ° C and -26.1 ° C without any difficulty in the oil reflux.

Example 4

The compositions listed in Table 3 below, when tested with R-134a and 2,4,7,9-tetramethyl-5-decin-4,7-diol surfactants, gave promising results. In the table Hl at 40 ° C is 12x10 ⁶ m ² / s naphthenic mineral oil, H-2 at 40 ° C is 38 x 10 ~ ⁶ m ² / s viscosity naphthenic white mineral oil, H-3 at 40 ° C 29-30 x 10 Naphthenic mineral oil having a viscosity of ~ ⁶ m ² / s, H-4 at 40 ° C 18x10 ^-6 m ² / s viscosity naphthenic mineral oil, H-5 at 40 ° C 29-30 χ 10 ~ ⁶ m ² / s viscous alkyl benzene, a polyol ester of P1 trimethylolpropane with 70% valeric acid and 30% isovaleric acid, P-2 a polyol ester of pentaerythritol and 2-ethylhexanoic acid, and P-3 a polyol ester of pentaerythritol with valeric acid, isovaleric acid and adipic acid .

Table 3

Quantity of lubricant (weight) Quantity of surfactant (parts by weight) 99.95 H-1 0.05 91.90 H and 8.0 P 0.10 87.80 H and 12.0 P 0.20 99.95 H-2 0.05 84.90 H-2 and 15.0 P-2 0.10 84.80 H-2 and 15.0 P-2 0.20 89.95 H-3 and 10.0 H-5 0.05 89.90 H-3 and 10.0 P-3 0.10 84.80 H-3 and 15.0 P-3 0.20 94.45 H-4 and 5.0 H-5 0.05 94.40 H-4 and 5.0 P-3 0.10 92.80 H-4 and 7.0 P-3 0.20

Example 5

This example illustrates the use of anionic fluorinated hydrocarbon surfactants in the composition of the invention. Example 2 is repeated with the exception that the lubricant used is naphthenic oil ISO 10 and the anionic and nonionic fluorinated hydrocarbon surfactants listed in Table 4 are tested. The Zonyl FSN and Zonyl FSO F _{(CF2 CF2) 3} _ ₈ CH ₂ CH ₂ O (CH ₂ CH ₂ O) H, compounds of formula _X, different numbers of ethylene oxide units. In the table, AN refers to anionic, NON to nonionic.

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Table 4

surfactant agent type Weight ⁰ / » Effect observed Zonyl FSP AN 0.05 The oil was partially detached from the metal shard 0.50 The oil is completely detached from the metal shard Zonyl FSA AN 0.05 No effect 0.50 The oil was partially detached from the metal shard Zonyl FSJ AN 0.05 The oil is completely detached from the metal shard 0.50 The oil is completely detached from the metal shard Zonyl FSN NON 0.05 No effect 0.50 No effect Zonyl FSO NON 0.05 No effect 0.50 No effect

The above data clearly show that the anionic fluorinated hydrocarbons can be suitably used in the composition of the invention.

Comparative example

Attempts have been made to remove the lubricant from the metal shred with non-additive compositions of the present invention containing either 90% by weight mineral oil and 10% by weight polyol ester or 70% by weight mineral oil and 30% polyol ester. Example 2 was carried out using naphthenic mineral oil ISO 10 and polyol ester P-1, which is an ester of trimethylolpropane with 70% by weight of valeric acid and 30% by weight of isovaleric acid, or P-2 polyol ester which is 2 ester of ethanehexanoic acid with 79% by weight of neopentyl glycol and 21% by weight of pentaerythritol. The results are summarized in Table 5.

Table 5

Type of polyol cstcr The amount (crowd%) Results E.g 10% The oil adheres to the metal shard and the glass 30% The oil adheres to the metal shard and the glass P-2 10% The oil adheres to the metal shard and the glass 30% The oil adheres to the metal shard and the glass

PATENT CLAIMS

Claims (14)

PATIENT INDIVIDUAL POINTS A coolant composition comprising a hydrocarbon lubricant, a hydrocarbon lubricant which is at least one carbon atoms, which is not miscible with a hydrocarbon lubricant, wherein each halogen atom is a fluorine atom and an effective amount of an additive to interfacial tension between the hydrocarbon lubricant and the liquid refrigerant. reducing to a point where the coefficient of dispersion of the liquid refrigerant on the steel is slightly positive, allowing the refrigerant to remove the hydrocarbon lubricant from the steel, wherein the additive is present at a concentration of 0.001 to 5 parts by weight per 100 parts of hydrocarbon lubricant. 2. A composition according to claim 1, wherein the hydrocarbon lubricant comprises paraffin-based mineral oil. 3. The composition of claim 1, wherein the hydrocarbon lubricant comprises naphthenic oil. 4. A composition according to claim 1, wherein the hydrocarbon lubricant is an alkylbenzene oil. 5. The composition of claim 1, wherein the hydrocarbon lubricant comprises a polyalphaolefin and oligomers thereof. 6. The composition of claim 1, wherein the hydrocarbon lubricant is naphthenic-based mineral oil and alkylbenzene oil, wherein the naphthenic-based mineral oil is present in higher amounts than the alkylbenzene oil. 7. The composition of claim 6 wherein the hydrocarbon lubricant is a paraffin-based mineral oil. 8. A composition according to claim 6, wherein the fluorinated hydrocarbon comprises 1,1,1,2-tetrafluoroethane. 9. A composition according to claim 6, wherein the fluorinated hydrocarbon comprises pentafluoroethane. 10. The composition of claim 6, further comprising difluoromochlorochloromethane. 11. A composition according to claim 1, wherein the additive is 2,4,7,9-tetramethyl-5-decin-4,7-diol. 12. The composition of claim 1, wherein the refrigerant component is incompatible with the total temperature range of -40 ° C to 80 ° C. 13. A coolant composition comprising, as a hydrocarbon lubricant, a paraffin-based mineral oil, a naphthenic-based mineral oil, an alkylbenzene oil, at least one of its alpha-olefin and its oligomers, and a hydrocarbon lubricant immiscible with at least one carbon and at least one fluorine. and an effective amount of an additive that reduces the interfacial tension between the hydrocarbon lubricant and the liquid refrigerant so that the refrigerant can remove the lubricant from the internal surfaces of the heat exchangers and lines. 14. A method for restarting compressor systems, comprising adding a polyol ester lubricant and 2,4,7,9-tetramethyl-5-decin-4,7-diol to the compressor system simultaneously.