Heat transfer compositions having improved miscibility with lubricating oil

Abstract

A composition including 2,3,3,3-tetrafluoropropene and a lubricating oil including a polyalkylene glycol and a polyol ester, the polyol ester content in the lubricating oil being less than or equal to 25%. A method of lubricating a vapor compression circuit, the method including using a mixture including a polyalkylene glycol and a polyol ester as lubricating oil in the vapor compression circuit, in combination with a heat transfer fluid comprising 2,3,3,3-tetrafluoropropene, the content of polyol ester in the lubricating oil being less than or equal to 25%. Further, the use of said composition in methods for heating or cooling.

Claims

1. A composition comprising 2,3,3,3-tetrafluoropropene and from 5 to 40 wt. % of a lubricating oil, the lubricating oil comprising a polyalkylene glycol and a polyol ester, the content of polyol ester in the lubricating oil being less than or equal to 25%.

2. The composition as claimed in claim 1 comprising from 10 to 40 wt. % of the lubricating oil, and wherein the lubricating oil comprises from 5 to 25 wt. % of polyol ester and from 75 to 95 wt. % of polyalkylene glycol.

3. The composition as claimed in claim 1, wherein the lubricating oil comprises from 7 to 20 wt. % of polyol ester and from 80 to 93 wt. % of polyalkylene glycol.

4. The composition as claimed in claim 1, wherein the lubricating oil comprises from 10 to 15 wt. % of polyol ester and from 85 to 90 wt. % of polyalkylene glycol.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a curve representing the maximum temperature of miscibility of a mixture of 75% of HFO-1234yf and 25% of lubricating oil composed of polyalkylene glycol and polyol ester (on the ordinate, in C.), as a function of the proportion by weight of polyol ester in the lubricating oil (on the abscissa, in %). The straight line plotted on the diagram represents the result that would be expected if the miscibility of HFO-1234yf with the polyalkylene glycol and the polyol ester showed purely additive behavior.

DESCRIPTION OF EMBODIMENTS

(2) Embodiments of the disclosure are now described in more detail and nonexhaustively in the description given below.

(3) Unless stated otherwise, throughout the application the proportions of compounds indicated are given as percentages by weight.

(4) According to the present application, the global warming potential (GWP) is defined relative to carbon dioxide and relative to a duration of 100 years, according to the method given in The scientific assessment of ozone depletion, 2002, a report of the World Meteorological Association's Global Ozone Research and Monitoring Project.

(5) Heat transfer compound, or heat transfer fluid (or refrigerant) means a compound, or a fluid, that is able to absorb heat on evaporating at low temperature and low pressure and to give up heat on condensing at high temperature and high pressure, in a vapor compression circuit. In general, a heat transfer fluid may comprise one, two, three or more than three heat transfer compounds.

(6) Heat transfer composition means a composition comprising a heat transfer fluid and optionally one or more additives that are not heat transfer compounds for the application envisaged.

(7) Embodiments of the disclosure are based on the use of a heat transfer compound, namely HFO-1234yf, and a lubricating oil, to form a heat transfer composition.

(8) The heat transfer composition may be introduced as it is into a vapor compression circuit. Alternatively, on the one hand the heat transfer fluid (comprising HFO-1234yf), and on the other hand the lubricating oil, may be introduced separately into the circuit, at the same point or different points of the circuit. The individual heat transfer compounds may also be introduced separately, if there are several of them.

(9) The lubricating oil comprises a polyalkylene glycol and a polyol ester.

(10) The polyalkylene glycol in the disclosure may comprise polyalkylene glycols of different formulae, mixed together.

(11) The polyol ester in the disclosure may comprise polyol esters of different formulae, mixed together.

(12) In general, a polyalkylene glycol suitable for use in the context of the disclosure comprises from 5 to 50 oxyalkylene repeat units, each containing from 1 to 5 carbon atoms.

(13) The polyalkylene glycol may be linear or branched. It may be a homopolymer or a copolymer of 2, 3 or more than 3 groups selected from the oxyethylene, oxypropylene, oxybutylene, oxypentylene groups and combinations thereof.

(14) Preferred polyalkylene glycols comprise at least 50% of oxypropylene groups.

(15) Preferred polyalkylene glycols are the homopolymers consisting of oxypropylene groups.

(16) Suitable polyalkylene glycols are described in document U.S. Pat. No. 4,971,712. Other suitable polyalkylene glycols are the polyalkylene glycols having hydroxyl groups at each end, as described in document U.S. Pat. No. 4,755,316. Other suitable polyalkylene glycols are the polyalkylene glycols having a capped hydroxyl end group. The hydroxyl group may be capped with an alkyl group containing from 1 to 10 carbon atoms (and optionally containing one or more heteroatoms such as nitrogen), or a fluoroalkyl group containing heteroatoms such as nitrogen, or a fluoroalkyl group as described in document U.S. Pat. No. 4,975,212, or other similar groups.

(17) When the two hydroxyl end groups of the polyalkylene glycol are capped, we may use the same end group or a combination of two different groups.

(18) The terminal hydroxyl groups may also be capped by forming an ester with a carboxylic acid, as described in document U.S. Pat. No. 5,008,028. The carboxylic acid may also be fluorinated.

(19) When the two ends of the polyalkylene glycol are capped, one or other may be capped with an ester, or else one end may be capped with an ester and the other end may be free or may be capped with the one of the aforementioned alkyl, heteroalkyl or fluoroalkyl groups.

(20) Polyalkylene glycols usable as lubricating oils and commercially available are for example the oils Goodwrench from General Motors, MOPAR-56 from Daimler-Chrysler, Zerol from Shrieve Chemical Products, Planetelf PAG from Total and Daphne Hermetic PAG from Itemitsu. Other suitable polyalkylene glycols are manufactured by Dow Chemical and Denso.

(21) The viscosity of the polyalkylene glycol may be for example from 1 to 1000 centistokes at 40 C., preferably from 10 to 200 centistokes at 40 C. and more especially preferably from 30 to 80 centistokes at 40 C.

(22) The viscosity is determined according to the ISO viscosity grades, in accordance with ASTM standard D2422.

(23) The oil marketed by Denso under the name ND8, having a viscosity of 46 centistokes, is particularly suitable.

(24) The polyol esters are obtained by reaction of a polyol (an alcohol containing at least 2 hydroxyl groups) with a monofunctional or polyfunctional carboxylic acid or with a mixture of monofunctional carboxylic acids. The water formed during this reaction is removed to prevent a back reaction of hydrolysis.

(25) The polyols preferred for synthesis of the polyol esters are those having a neopentyl skeleton, for example neopentyl glycol, trimethylol propane, pentaerythritol and dipentaerythritol, pentaerythritol being the polyol most often used.

(26) The carboxylic acids that react with the polyols to form the esters may comprise from 2 to 15 carbon atoms, and the carbon backbone may be linear or branched. Among these acids, we may notably mention, nonexhaustively, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, 2,2-dimethylpentanoic acid, 3,5,5-trimethylhexanoic acid, adipic acid, succinic acid, and others, as well as mixtures of two or more of these acids, in all proportions.

(27) Certain alcohol functions are not esterified, but their proportion remains low. Thus, the polyol esters may comprise from 0 to 5 relative mol % of CH.sub.2OH units relative to the CH.sub.2O(CO) units.

(28) The preferred polyol esters are those having a viscosity from 1 centistoke to 1000 centistokes at 40 C., preferably from 10 centistokes to 200 centistokes, and advantageously from 30 centistokes to 80 centistokes.

(29) As suitable polyol esters, we may mention as nonlimiting examples the oils Mobil EAL Arctic 68 and 32 (Mobil), Planetelf ACD 32 (Total) and Bitzer BSE 32 (Bitzer).

(30) The proportion of lubricating oil that has to be used in combination with the heat transfer fluid depends on the type of installation in question. In fact, the total amount of lubricating oil in the installation mainly depends on the nature of the compressor, whereas the total amount of heat transfer fluid in the installation mainly depends on the exchangers and the pipework.

(31) In general, the proportion of lubricating oil in the heat transfer composition, in other words relative to the sum of the lubricating oil and of the heat transfer fluid, is from 1 to 99%, preferably from 5 to 50%, for example from 10 to 40% or from 15 to 35%.

(32) The lubricating oil used in the context of the disclosure comprises a proportion of polyol ester less than or equal to 25%.

(33) According to certain embodiments, the lubricating oil comprises at least 1%, or at least 2%, or at least 3%, or at least 4%, or at least 5%, or at least 6%, or at least 7%, or at least 8%, or at least 9%, or at least 10%, or at least 11%, or at least 12%, or at least 13%, or at least 14%, or at least 15%, or at least 16%, or at least 17%, or at least 18%, or at least 19%, or at least 20%, or at least 21%, or at least 22%, or at least 23%, or at least 24% of polyol ester. The higher the proportion of polyol ester in the lubricating oil, the better the miscibility with the heat transfer fluid based on HFO-1234yf.

(34) According to certain embodiments, the lubricating oil comprises at most 1%, or at most 2%, or at most 3%, or at most 4%, or at most 5%, or at most 6%, or at most 7%, or at most 8%, or at most 9%, or at most 10%, or at most 11%, or at most 12%, or at most 13%, or at most 14%, or at most 15%, or at most 16%, or at most 17%, or at most 18%, or at most 19%, or at most 20%, or at most 21%, or at most 22%, or at most 23%, or at most 24% of polyol ester. The lower the proportion of polyol ester in the lubricating oil, the better the stability of the lubricating oil.

(35) According to a particular embodiment, the lubricating oil used consists of the mixture of polyalkylene glycol and polyol ester described above, with the exception of any other lubricating compound.

(36) According to an alternative embodiment, another lubricating compound is used in combination with the polyalkylene glycol, in the lubricating oil. It may notably be selected from oils of mineral origin, silicone oils, paraffins of natural origin, naphthenes, synthetic paraffins, alkylbenzenes, poly-alpha-olefins, polyvinyl ethers. The polyvinyl ethers are preferred. When another lubricating compound is used in combination with the polyalkylene glycol, it is desirable for the miscibility of HFO-1234yf with this lubricating compound to be greater than the miscibility of HFO-1234yf with the polyalkylene glycol. This is the case notably for at least some of the compounds of the polyvinyl ether type.

(37) The heat transfer compound mainly used in the context of the disclosure is HFO-1234yf.

(38) However, the heat transfer compositions according to the disclosure may optionally comprise one or more additional heat transfer compounds, besides HFO-1234yf. These additional heat transfer compounds may notably be selected from hydrocarbons, hydrofluorocarbons, ethers, hydrofluoroethers and fluoroolefins.

(39) According to particular embodiments, the heat transfer fluids according to the disclosure may be binary compositions (consisting of two heat transfer compounds) or ternary compositions (consisting of three heat transfer compounds) or quaternary compositions (consisting of four heat transfer compounds), in combination with the lubricating oil to form the heat transfer compositions according to the disclosure.

(40) It is preferred, however, for the heat transfer fluid present in the heat transfer composition according to the disclosure to consist essentially of, or even consist of, HFO-1234yf. Alternatively, the proportion of HFO-1234yf in the heat transfer fluid (i.e. relative to the sum of the heat transfer compounds) is preferably greater than or equal to 30%, or 40%, or 50%, or 60%, or 70%, or 80%, or 90%, or 95%.

(41) The other additives that may be used in the context of the disclosure may notably be selected from stabilizers, surfactants, tracing agents, fluorescent agents, odoriferous agents and solubilizers.

(42) The stabilizer or stabilizers, when they are present, preferably represent at most 5 wt % in the heat transfer composition. Among the stabilizers, we may notably mention nitromethane, ascorbic acid, terephthalic acid, azoles such as tolutriazole or benzotriazole, phenolic compounds such as tocopherol, hydroquinone, t-butyl hydroquinone, 2,6-di-tert-butyl-4-methyl phenol, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, epoxides (alkyl optionally fluorinated or perfluorinated or alkenyl or aromatic) such as n-butylglycidyl ether, hexanedioldiglycidyl ether, allylglycidyl ether, butylphenylglycidyl ether, phosphites, phosphates such as tricresyl phosphates, thiols and lactones.

(43) As tracing agents (that are detectable), we may mention deuterated or non-deuterated hydrofluorocarbons, deuterated hydrocarbons, perfluorocarbides, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide and combinations thereof. The tracing agent is different from the heat transfer compound or compounds making up the heat transfer fluid.

(44) As solubilizers, we may mention hydrocarbons, dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles, chlorocarbides, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes. The solubilizer is different from the heat transfer compound or compounds making up the heat transfer fluid.

(45) As fluorescent agents, we may mention naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins and derivatives and combinations thereof.

(46) As odoriferous agents, we may mention alkyl acrylates, allyl acrylates, acrylic acids, acrylic esters, alkyl ethers, alkyl esters, alkynes, aldehydes, thiols, thioethers, disulfides, allylisothiocyanates, alkanoic acids, amines, norbornenes, derivatives of norbornenes, cyclohexene, heterocyclic aromatic compounds, ascaridole, o-methoxy(methyl)phenol and combinations thereof.

(47) The method of heat transfer according to the disclosure is based on the use of an installation comprising a vapor compression circuit that contains a heat transfer composition (i.e. a heat transfer fluid and at least one lubricating oil). The method of heat transfer may be a method for heating or cooling a fluid or a body.

(48) The vapor compression circuit comprises at least one evaporator, a compressor, a condenser and a pressure reducing valve, as well as lines for transporting fluid between these elements. The evaporator and the condenser comprise a heat exchanger allowing heat exchange between the heat transfer fluid and another fluid or body.

(49) As compressor, we may notably use a single-stage or multistage centrifugal compressor or a mini-centrifugal compressor. Rotary compressors, of the piston or screw type, may also be used. The compressor may be driven by an electric motor or by a gas turbine (for example supplied with the exhaust gases of a vehicle, for mobile applications) or by gearing.

(50) The installation may comprise a turbine for generating electricity (Rankine cycle).

(51) The installation may also optionally comprise at least one circuit of heat-transfer fluid used for transferring heat (with or without change of state) between the heat transfer fluid circuit and the fluid or body to be heated or cooled.

(52) The installation may also optionally comprise two vapor compression circuits (or more), containing identical or different heat transfer fluids. For example, the vapor compression circuits may be coupled together.

(53) The vapor compression circuit functions according to a conventional vapor compression cycle. The cycle comprises change of state of the heat transfer fluid from a liquid phase (or liquid/vapor two-phase system) to a vapor phase at a relatively low pressure, then compression of the fluid in the vapor phase to a relatively high pressure, change of state (condensation) of the heat transfer fluid from the vapor phase to the liquid phase at a relatively high pressure, and reduction of the pressure to begin the cycle again.

(54) In the case of a cooling process, heat obtained from the fluid or the body that is being cooled (directly or indirectly, via a heat-transfer fluid) is absorbed by the heat transfer fluid, during evaporation of the latter, at a relatively low temperature compared to the environment. The cooling processes comprise air conditioning processes (with mobile installations, for example in vehicles, or stationary installations), refrigeration and freezing or cryogenics.

(55) In the case of a heating process, heat is given up (directly or indirectly, via a heat-transfer fluid) from the heat transfer fluid, during condensation of the latter, to the fluid or the body that is being heated, at a relatively high temperature compared to the environment. The installation for applying heat transfer is in this case called a heat pump.

(56) It is possible to use any type of heat exchanger for employing the heat transfer fluids according to the disclosure, and notably co-current heat exchangers or, preferably, countercurrent heat exchangers. It is also possible to use microchannel exchangers.

(57) Embodiments of the disclosure are particularly suitable for the application of air conditioning processes in mobile or stationary installations, and more particularly automotive air conditioning.

(58) Preferably, and notably in the context of automotive air conditioning processes, the inlet temperature of the heat transfer fluid at the evaporator is from 10 C. to 20 C., notably from 0 C. to 10 C., more especially preferably about 5 C.

(59) Preferably, and notably in the context of automotive air conditioning processes, the temperature of the start of condensation of the heat transfer fluid at the condenser is from 25 C. to 60 C., notably from 30 C. to 50 C., more especially preferably from 35 C. to 45 C., and for example about 40 C.

(60) It should be noted that addition of a polyol ester to a heat transfer composition comprising (or consisting of) HFO-1234yf as heat transfer fluid, as well as a lubricating oil comprising (or consisting of) polyalkylene glycol, improves the miscibility of the heat transfer fluid with the lubricating oil, i.e. increases the temperature threshold of appearance of the immiscibility zone (defined as the temperature starting from which the compounds in liquid phase form an emulsion). This makes it possible to increase the possibilities for using the heat transfer fluid, for example making it possible to use it at a higher condensation temperature.

(61) More generally, embodiments of the disclosure make it possible to undertake replacement of any heat transfer fluid in all heat transfer applications, and for example in automotive air conditioning. For example, the heat transfer fluids and heat transfer compositions according to the disclosure may serve for replacing: 1,1,1,2-tetrafluoroethane (R134a); 1,1-difluoroethane (R152a); 1,1,1,3,3-pentafluoropropane (R245fa); mixtures of pentafluoroethane (R125), of 1,1,1,2-tetrafluoroethane (R134a) and of isobutane (R600a), namely the R422s; chlorodifluoromethane (R22); the mixture of 51.2% of chloropentafluoroethane (R115) and of 48.8% of chlorodifluoromethane (R22), namely R502; any hydrocarbon; the mixture of 20% of difluoromethane (R32), 40% of pentafluoroethane (R125) and 40% of 1,1,1,2-tetrafluoroethane (R134a), namely R407A; the mixture of 23% of difluoromethane (R32), 25% of pentafluoroethane (R125) and 52% of 1,1,1,2-tetrafluoroethane (R134a), namely R407C; the mixture of 30% of difluoromethane (R32), 30% of pentafluoroethane (R125) and 40% of 1,1,1,2-tetrafluoroethane (R134a), namely R407F; R1234ze (1,3,3,3-tetrafluoropropene).

EXAMPLES

(62) The following examples illustrate but do not limit the disclosure.

Example 1Miscibility of HFO-1234yf with Lubricating Oil

(63) The miscibility of HFO-1234yf with a lubricating oil based on polyalkylene glycol and/or polyol ester is investigated in this example.

(64) The polyalkylene glycol is the oil PAG ND8 supplied by Nippon Denso.

(65) The polyol ester is the oil POE Ze-GLES RB68 supplied by Nippon Oil.

(66) The procedure is as follows: put the lubricating oil in a 16.4-ml glass tube (sealable tube) weighing the amount put in exactly; add the desired amount of refrigerant (heat transfer compound); seal the tube by welding it; completely immerse the tube in a thermostatically controlled bath filled with water at room temperature. The tank used is made of Plexiglas, which makes it possible to visualize the fluid/oil mixture. The tubes are arranged vertically in tube holders; close the tank at the top with metal plates for protection in case of breakage of a tube; heat the water gradually and observe the temperature starting from which the mixture becomes two-phase. The maximum temperature, so as not to reach excessively high pressures, is 80 C. The temperature is first increased in steps of 5 C. with a plateau of 10 minutes each time, and when the temperature at which the mixture becomes immiscible is reached, the temperature is altered with changes of 1 C.

(67) Production of an emulsion indicates immiscibility of the mixture.

(68) FIG. 1 illustrates the surprising improvement in miscibility of the polyalkylene glycol with HFO-1234yf that is obtained by adding polyol ester, the actual maximum temperature of miscibility (curve) being above the theoretical maximum temperature of miscibility (straight line) extrapolated as a function of the maximum temperature of miscibility of the pure polyalkylene glycol and of the pure polyol ester. This FIGURE was obtained with HFO-1234yf/lubricating oil mixtures containing 25% of lubricating oil. The immiscibility zone corresponds to the domain located above the curve, and the zone of miscibility corresponds to the domain situated beneath the curve.

(69) Adding from 15 to 25% of polyol ester for example makes it possible to extend the zone of miscibility by about 7 to 8 degrees relative to the expected value.

Example 2Thermal Stability of the Lubricating Oil

(70) The thermal stability of the lubricating oils used in example 1 is investigated in this example.

(71) The tests are carried out according to standard ASHRAE 97-2007.

(72) The test conditions are as follows: mass of lubricant: 5 g; temperature: 200 C.; duration: 14 days.

(73) The tests were carried out by adding 5000 ppm of water to the lubricating oil, which is considered to be a relatively high water content.

(74) The lubricating oil is put in a 16.4-mL glass tube. The tube is then drawn out under vacuum and then welded to seal it, and placed in a stove at 200 C. for 14 days.

(75) At the end of the test, the oils are analyzed: with respect to their color, by spectrocolorimetry (for a slight coloration the results are given in Hazen, up to 700 and for a strong coloration the results are given in Gardner, from 3 to 15); with respect to water content (measurement by Karl Fischer coulometry); with respect to the acid number (Total Acid Number or TAN, titration with methanolic KOH at 0.01 N).

(76) The results are summarized in the following table:

(77) TABLE-US-00001 100% 15% POE 35% POE 55% POE 80% POE 100% Oil PAG 85% PAG 65% PAG 45% PAG 20% PAG POE Color 5.2 4.2 325 320 330 110 Gardner Gardner Hazen Hazen Hazen Hazen Water 5300 4900 4300 4900 4500 5000 content (ppm) Acid 4.7 8.8 16.2 14.8 13.1 12.3 number (mg KOH/g)

(78) It can be seen that in order to maintain satisfactory thermal stability, the content of polyol ester in the oil must be kept less than or equal to about 25%, notably less than or equal to about 20%, and ideally less than or equal to 15%.