Composition based on 1,3,3,3-tetrafluoropropene

Abstract

A composition including a lubricant based on polyol esters (POEs) or PVE and a refrigerant F including from 1 to 99% by weight of trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze) and from 1 to 99% by weight of 1,1,1,2-tetrafluoroethane. Also, the use of the composition including a lubricant and refrigerant in refrigeration, air conditioning and heat pumps.

Claims

1. A composition comprising at least one lubricant comprising at least one polyol ester or at least one polyvinyl ether and a refrigerant comprising from 5 to 10% by weight of trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), from 5 to 50% by weight of 1,1,1,2-tetrafluoroethane, and at least one selected from the group of hydrofluorocarbons and hydrofluoroolefins, wherein the at least one selected from the group of hydrofluorocarbons and hydrofluoroolefins includes 2,3,3,3-tetrafluoropropene.

2. The composition according to claim 1, wherein the refrigerant further comprises a hydrofluorocarbon.

3. The composition according to claim 1, wherein the refrigerant comprises: from 5 to 10% by weight of trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), from 5 to 40% by weight of 1,1,1,2-tetrafluoroethane, and at least one selected from the group of hydrofluorocarbons and hydrofluoroolefins, wherein the at least one selected from the group of hydrofluorocarbons and hydrofluoroolefins includes 2,3,3,3-tetrafluoropropene.

4. The composition according to claim 1, wherein the refrigerant comprises: from 5 to 10% by weight of trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), from 10 to 30% by weight of 1,1,1,2-tetrafluoroethane, and at least one selected from the group of hydrofluorocarbons and hydrofluoroolefins, wherein the at least one selected from the group of hydrofluorocarbons and hydrofluoroolefins includes 2,3,3,3-tetrafluoropropene.

5. The composition according to claim 1, wherein the refrigerant comprises: from 5 to 10% by weight of trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze), from 20 to 30% by weight of 1,1,1,2-tetrafluoroethane, and at least one selected from the group of hydrofluorocarbons and hydrofluoroolefins, wherein the at least one selected from the group of hydrofluorocarbons and hydrofluoroolefins includes 2,3,3,3-tetrafluoropropene.

6. The composition according to claim 1, wherein the at least one lubricant comprises at least one polyol ester, wherein the at least one polyol ester is obtained from a polyol having a neopentyl backbone.

7. The composition according to claim 6, wherein the polyol having a neopentyl backbone is selected from the group consisting of neopentyl glycol, trimethylolpropane, and dipentaerythritol.

8. The composition according to claim 1, wherein the at least one lubricant comprises at least one polyol ester, wherein the at least one polyol ester is obtained from a linear or branched carboxylic acid containing from 2 to 15 carbon atoms.

9. The composition according to claim 1, wherein the at least one lubricant comprises at least one polyol ester, wherein the at least one polyol ester is between 10 and 50% by weight of the composition.

10. The composition according to claim 1, wherein the polyvinyl ether represents between 10 and 50% by weight of the composition.

11. The composition according to claim 1, wherein the at least one lubricant comprises at least one polyvinyl ether, wherein the polyvinyl ether is a copolymer of the following two units: ##STR00002##

12. The composition according to claim 11, wherein the polyvinyl ether has from 50 to 95% by weight of Unit 1.

13. The composition according to claim 1, wherein out of the total wt % of trans-HFO-1234ze and 1,1,1,2-tetrafluoroethane, trans-HFO-1234ze contributes an amount of 20-30% by weight and 1,1,1,2-tetrafluoroethane contributes an amount of 70-80% by weight.

Description

DETAILED DESCRIPTION

(1) A subject of the present application is therefore a composition comprising at least one lubricant based on polyol esters (POEs) or on polyvinyl ether (PVE) and a refrigerant F comprising from 1 to 99% by weight of trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze) and from 1 to 99% by weight of 1,1,1,2-tetrafluoroethane.

(2) Preferably, the composition according to the present invention comprises at least one lubricant based on polyol esters (POEs) or on polyvinyl ether (PVE) and a refrigerant F comprising from 5 to 95% by weight of trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze) and from 5 to 95% by weight of 1,1,1,2-tetrafluoroethane.

(3) The composition which is particularly preferred comprises at least one lubricant based on polyol esters (POEs) or on polyvinyl ether (PVE) and a refrigerant F comprising from 30 to 91% by weight of trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234ze) and from 9 to 70% by weight of 1,1,1,2-tetrafluoroethane.

(4) The refrigerant F may also comprise other hydrofluorocarbons.

(5) The fluid F has the advantage of being more effective than trans-HFO-1234ze and, in addition, the stability of the refrigerant in the presence of POE or PVE is greater compared with that of trans-HFO-1234ze in the presence of PAG.

(6) Polyol esters are obtained by reaction of a polyol (an alcohol containing at least 2 hydroxyl groups —OH) with a monofunctional or plurifunctional carboxylic acid or with a mixture of monofunctional carboxylic acids. The water formed during this reaction is eliminated in order to prevent the reverse reaction (i.e. hydrolysis).

(7) According to the present invention, the preferred polyols are those which have a neopentyl backbone, such as neopentyl glycol, trimethylolpropane, pentaerythritol and dipentaerythritol; pentaerythritol is the preferred polyol.

(8) The carboxylic acids may contain from 2 to 15 carbon atoms, it being possible for the carbon backbone to be linear or branched. Mention may in particular be made of 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 and succinic acid, and mixtures thereof.

(9) Some alcohol functions are not esterified, however their proportion remains low. Thus, the POEs can comprise between 0 and 5 relative mol % of CH.sub.2—OH units relative to the —CH.sub.2—O—(C═O)— units.

(10) The preferred POE lubricants are those which have a viscosity of from 1 to 1000 centiStokes (cSt) at 40° C., preferably from 10 to 200 cSt, and advantageously from 30 to 80 cSt.

(11) The polyvinyl ether (PVE) oils are preferably copolymers of the following 2 units:

(12) ##STR00001##

(13) The properties of the oil (viscosity, solubility of the refrigerant and miscibility with the refrigerant in particular) can be adjusted by varying the m/n ratio and the sum m+n. The preferred PVE oils are those which have 50 to 95% by weight of units 1.

(14) According to one preferred embodiment of the invention, the lubricant represents between 10 and 50%, inclusive, by weight of the composition.

(15) The refrigerant F may also comprise additives such as odorous compounds.

(16) A subject of the present invention is also the use of the abovementioned composition in refrigeration, in particular domestic or commercial refrigeration, cold rooms, the food industry, the processing industry, refrigerated transport (trucks, boats); air conditioning, in particular domestic, commercial or industrial air conditioning, where the appliances used are chillers or direct expansion appliances; and heat pumps, in particular medium- and high-temperature heat pumps.

(17) By virtue of their low glide temperature, the compositions according to the present invention can be used both in equipment with dry-expansion evaporators and in equipment with evaporators operating in a flooded system.

EXPERIMENTAL SECTION

(18) The thermal stability trials are carried out according to standard ASHRAE 97-2007: “sealed glass tube method to test the chemical stability of materials for use within refrigerant systems”.

(19) The test conditions are as follows:

(20) weight of refrigerant: 2.2 g

(21) weight of lubricant: 5 g

(22) temperature: 200° C.

(23) duration: 14 days

(24) The lubricant is introduced into a 42.2 ml glass tube. The tube is then evacuated under vacuum and then the refrigerant F is added thereto. The tube is then welded in order to close it and placed in an oven at 200° C. for 14 days.

(25) At the end of the test, various analyses are carried out: the gas phase is recovered in order to be analysed by gas chromatography: the main impurities were identified by GC/MS (gas chromatography coupled with mass spectrometry). The impurities coming from the refrigerant F and those coming from the lubricant can thus be combined; the lubricant is analysed: colour (by spectrocolorimetry, Labomat DR Lange LIC220 Model MLG131), water content (by Karl Fischer coulometry, Mettler DL37) and acid number (by quantitative determination with 0.01N methanolic potassium hydroxide). 3 commercial lubricants were tested: the PAG ND8 oil, the POE Ze-GLES RB68 oil and the PVE FVC 68D oil.

(26) TABLE-US-00001 PAG ND8 POE Ze-GLES RB68 PVE FVC 68D Trans-HFO- Trans-HFO- Trans-HFO- Refrigerant HFC-134a 1234ze HFC-134a 1234ze 1234ze By-products in the gas phase: from the 100 ppm 4000 ppm + 100 ppm 500 ppm + 3% + 1800 ppm refrigerant 6000 ppm 1500 ppm (HFO-1234yf) (HFO-1234yf) (HFO-1234yf) from the 1.5% 2% 500 ppm 800 ppm 2% lubricant Analysis of the lubricant: colour 400 Hazen 17 Gardner 300 Hazen 300 Hazen 6 Gardner water content 1200 ppm 1100 ppm 160 ppm 500 ppm 500 ppm acid number 1.5 mg KOH/g 10 mg KOH/g 0.3 mg KOH/g 0.6 mg KOH/g 1.1 mg KOH/g It is noted that trans-HFO-1234ze in the presence of POE or PVE improves the stability of the lubricant. In addition, in the presence of POE, the stability of the refrigerant is also improved.

(27) Applications

(28) Thermodynamic performance of the systems using the mixtures in question

(29) Calculation Tools

(30) The RK-Soave equation is used for the calculation of the densities, enthalpies, entropies and the liquid-vapour equilibrium data of the mixtures. The use of this equation requires knowledge of the properties of the pure substances used in the mixtures in question and also the coefficients of interaction for each binary combination.

(31) The data necessary for each pure substance are:

(32) boiling point, critical pressure and temperature, curve of pressure as a function of temperature starting from the boiling point to the critical point, saturated liquid and saturated vapour densities as a function of temperature.

(33) The data on HFCs are published in the ASHRAE Handbook 2005 chapter 20 and are also available under Refrop (software developed by NIST for calculating the properties of refrigerants).

(34) The HFO temperature-pressure curve data are measured by the static method. The critical pressure and temperature are measured using a C80 calorimeter sold by Setaram. The densities, at saturation as a function of temperature, are measured by means of the vibrating tube densimeter technology developed by the laboratories of the dcole des Mines de Paris [French Engineering School].

(35) Coefficient of Binary Interaction:

(36) The RK-Soave equation uses coefficients of binary interaction to represent the behaviour of products in mixtures. The coefficients are calculated according to experimental liquid-vapour equilibrium data.

(37) The technique used for the liquid-vapour equilibrium measurements is the static analytical cell method. The equilibrium cell comprises a sapphire tube and is equipped with two Rolsitm electromagnetic samplers. It is immersed in a cryothermostat bath (Huber HS40). Magnetic stirring driven by a magnetic field rotating at a variable speed is used to accelerate the reaching of the equilibria. The sample analysis is carried out by gas chromatography (HP5890 series II) using a katharometer (TCD).

(38) HFC-134a/Trans-HFO-1234ze

(39) The liquid-vapour equilibrium measurements on the HFC-134a/trans-HFO-1234ze binary combination are carried out for the following isotherm: 20° C.

(40) Compression System

(41) Consider a compression system equipped with an evaporator, a condenser, a liquid-vapour exchanger (internal exchanger), a screw compressor and a pressure regulator.

(42) The system operates with 15° C. of overheat and an internal exchanger between the outlets of the condenser and of the evaporator.

(43) The isentropic efficiency of the compressors depends on the compression ratio. This efficiency is calculated according to the following equation:

(44) $\begin{array}{cc}{\eta }_{\mathrm{isen}}=a-{b\left(\tau -c\right)}^2-\frac{d}{\tau -e}& \left(1\right)\end{array}$

(45) For a screw compressor, the constants a, b, c, d and e of the isentropic efficiency equation (1) are calculated according to the standard data published in the “Handbook of air conditioning and refrigeration, page 11.52”.

(46) The coefficient of performance (COP) is defined as being the useful power supplied by the system over the power provided or consumed by the system.

(47) The Lorenz coefficient of performance (COPLorenz) is a reference coefficient of performance. It depends on temperatures and is used to compare the COPs of the various refrigerants.

(48) The Lorenz coefficient of performance is defined as follows:

(49) (the temperatures T are in K)
T.sub.average.sup.condenser=T.sub.inlet.sup.condenser−T.sub.outlet.sup.condenser  (2)
T.sub.average.sup.evaporator=T.sub.outlet.sup.evaporator−T.sub.inlet.sup.evaporator  (3)

(50) The Lorenz COP in the case of conditioned air and refrigeration:

(51) $\begin{array}{cc}\mathrm{COPlorenz}=\frac{T_{\mathrm{average}}^{\mathrm{evaporator}}}{T_{\mathrm{average}}^{\mathrm{condensor}}-T_{\mathrm{average}}^{\mathrm{evaporator}}}& \left(4\right)\end{array}$

(52) The Lorenz COP in the case of heating:

(53) $\begin{array}{cc}\mathrm{COPlorenz}=\frac{T_{\mathrm{average}}^{\mathrm{condensor}}}{T_{\mathrm{average}}^{\mathrm{condensor}}-T_{\mathrm{average}}^{\mathrm{evaporator}}}& \left(5\right)\end{array}$

(54) For each composition, the coefficient of performance of the Lorenz cycle is calculated as a function of the corresponding temperatures.

(55) The % COP/COPLorenz is the ratio of the COP of the system relative to the COP of the corresponding Lorenz cycle.

(56) Results in Cooling Mode

(57) In cooling mode, the compression system operates between an evaporation temperature of −5° C. and a condensation temperature of 50° C.

(58) The values of the constituents (HFC-134a, trans-HFO-1234ze) for each composition are given as percentage by weight.

(59) TABLE-US-00002 Temp Temp T evap comp T pressure inlet outlet condensation regulator Evap P Cond P Ratio Comp % % COP/ Cooling mode (° C.) (° C.) (° C.) inlet (bar) (bar) (w/w) Glide efficiency CAP COPLorenz HFO-1234ze −5 73 50 42 1.8 10.0 5.6 0.00 74.8 100 54 HFO-1234ze HFC-134a  5 95 −5 81 50 42 2.4 13.1 5.4 0.03 75.9 136 56 10 90 −5 81 50 42 2.4 13.0 5.4 0.07 75.8 135 55 20 80 −5 80 50 42 2.3 12.8 5.5 0.16 75.6 131 55 30 70 −5 79 50 42 2.3 12.6 5.5 0.26 75.3 128 55 40 60 −5 79 50 42 2.2 12.3 5.6 0.34 75.1 124 54 50 50 −5 78 50 42 2.1 12.0 5.6 0.40 74.9 120 54 60 40 −5 78 50 42 2.1 11.7 5.7 0.44 74.7 116 54 70 30 −5 77 50 42 2.0 11.3 5.7 0.43 74.6 112 54 80 20 −5 76 50 42 1.9 10.9 5.7 0.37 74.5 108 54 90 10 −5 75 50 42 1.8 10.5 5.7 0.24 74.6 104 54 95  5 −5 74 50 42 1.8 10.3 5.7 0.14 74.6 102 54

(60) Results in Heating Mode

(61) In heating mode, the compression system operates between an evaporation temperature of −5° C. and a condensation temperature of 50° C.

(62) The values of the constituents (HFC-134a, trans-HFO-1234ze) for each composition are given as percentage by weight.

(63) TABLE-US-00003 Temp Temp T evap comp T pressure inlet outlet condensation regulator Evap P Cond P Ratio Comp % % COP/ Heating mode (° C.) (° C.) (° C.) inlet (bar) (bar) (w/w) Glide efficiency CAP COPLorenz HFO-1234ze −5 73 50 42 1.8 10.0 5.6 0.00 74.8 100 62 HFO-1234ze HFC-134a  5 95 −5 81 50 42 2.4 13.1 5.4 0.03 75.9 136 63 10 90 −5 81 50 42 2.4 13.0 5.4 0.07 75.8 135 63 20 80 −5 80 50 42 2.3 12.8 5.5 0.16 75.6 131 63 30 70 −5 79 50 42 2.3 12.6 5.5 0.26 75.3 128 63 40 60 −5 79 50 42 2.2 12.3 5.6 0.34 75.1 124 62 50 50 −5 78 50 42 2.1 12.0 5.6 0.40 74.9 120 62 60 40 −5 78 50 42 2.1 11.7 5.7 0.44 74.7 116 62 70 30 −5 77 50 42 2.0 11.3 5.7 0.43 74.6 112 62 80 20 −5 76 50 42 1.9 10.9 5.7 0.37 74.5 108 62 90 10 −5 75 50 42 1.8 10.5 5.7 0.24 74.6 104 62 95  5 −5 74 50 42 1.8 10.3 5.7 0.14 74.6 102 62