Heat transfer fluid replacing R-134a

Abstract

A heat transfer method using ternary composition containing 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane and difluoromethane, as a heat transfer fluid in refrigeration systems, to replace R-134a. 1. A method of modifying a heat transfer system containing R-134a comprising removing R-134a and adding a composition comprising a refrigerant consisting essentially of: 70 to 88 wt % of 2,3,3,3-tetrafluoropropene; 4 to 16 wt % of difluoromethane; 8 to 14 wt % of 1,1-difluoroethane; and optionally, a stabilizer.

Claims

1. A method of modifying a heat transfer system containing R-134a comprising removing R-134a and adding a composition comprising a refrigerant consisting essentially of: 70 to 88 wt % of 2,3,3,3-tetrafluoropropene; 4 to 16 wt % of difluoromethane; 8 to 14 wt % of 1,1-difluoroethane; and optionally, a stabilizer.

2. The method as claimed in claim 1, wherein the refrigerant consists essentially of 2,3,3,3-tetrafluoropropene, difluoromethan, 1,1-difluoroethane, and the stabilizer.

3. The method as claimed in claim 2, wherein the stabilizer is selected from the group consisting of nitromethane, ascorbic acid, terephthalic acid, azoles, phenolic compounds, epoxides, phosphites, phosphates, phosphonates, thiols and lactones.

4. The method as claimed in claim 2, wherein stabilizer represents at most 5% by weight relative to the refrigerant.

5. The method as claimed in claim 1, wherein the heat transfer system is of the compression type.

6. The method as claimed in claim 5, wherein the heat transfer system operates with exchangers in countercurrent mode or in crossed-current mode with countercurrent tendency.

7. The method as claimed in claim 1, wherein the composition further comprises a lubricant.

8. The method as claimed in claim 7, wherein the lubricant is selected from the group consisting of mineral oil, alkylbenzene, polyalkylene glycol and polyvinyl ether.

9. The method as claimed in claim 1, wherein the refrigerant consists essentially of: 84 to 88 wt % of 2,3,3,3-tetrafluoropropene; 4 to 14 wt % of difluoromethane; 11 to 14 wt % of 1,1-difluoroethane; and optionally, a stabilizer.

10. The method as claimed in claim 1, wherein the refrigerant consists of: 84 to 88 wt % of 2,3,3,3-tetrafluoropropene; 4 to 14 wt % of difluoromethane; 11 to 14 wt % of 1,1-difluoroethane; and optionally, a stabilizer.

11. The method as claimed in claim 1, wherein the refrigerant consists of: 70 to 88 wt % of 2,3,3,3-tetrafluoropropene; 4 to 16 wt % of difluoromethane; 8 to 14 wt % of 1,1-difluoroethane; and optionally, a stabilizer.

Description

DETAILED DESCRIPTION

(1) The applicant has now discovered that ternary compositions of 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane and difluoromethane are particularly advantageous as heat transfer fluid.

(2) These compositions have both a zero ODP and a GWP below that of existing heat transfer fluids such as R-410A or R-134a.

(3) Moreover, their performance (COP: coefficient of performance, defined as the useful power delivered by the system to the power supplied to or consumed by the system) is greater than that of existing heat transfer fluids such as R-410A or R-134a.

(4) The compositions used as heat transfer fluid in embodiments of the present invention have a critical temperature above 87 C. (the critical temperature of R410A is 70.5 C.). These compositions can be used in heat pumps for supplying heat at temperatures up to 65 C. but also at higher temperatures up to 87 C. (temperature range where R-410A cannot be used).

(5) The compositions used as heat transfer fluid in embodiments of the present invention have temperatures at the compressor outlet equivalent to the values given by R-410A. The pressures at the condenser are lower than the pressures of R-410A and the compression ratios are also lower. These compositions can use the same compressor technology as used with R-410A.

(6) The compositions used as heat transfer fluid in embodiments of the present invention have temperatures at the compressor outlet less than the values given by R-134a. The pressures at the condenser and evaporater are higher than the pressures of R-134a in order to give a lower compression ratios. These compositions can use the same compressor technology as used with R-134a.

(7) The compositions used as heat transfer fluid in embodiments of the present invention have saturated-vapor densities below the saturated-vapor density of R-410A. The volumetric capacities given by these compositions are equivalent to the volumetric capacity of R-410A (between 91 and 95%). Owing to these properties, these compositions operate with smaller pipeline diameters and therefore less head loss in the vapor pipelines, which increases the performance of the installations.

(8) These compositions are suitable preferably in compression-type refrigeration systems with exchangers operating in countercurrent mode or in crossed-current mode with countercurrent tendency.

(9) Thus, these compositions can be used as heat transfer fluid in heat pumps, optionally reversible, in air conditioning, and in low-temperature and medium-temperature refrigeration employing compression systems with exchangers in countercurrent mode or in crossed-current mode with countercurrent tendency. Embodiments of the present invention therefore relate to the use of ternary compositions of 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane and difluoromethane as heat transfer fluid in refrigeration systems replacing the mixture R-410A or replacing R-134a.

(10) Preferably, these compositions are used in compression-type refrigeration systems with exchangers operating in countercurrent mode or in crossed-current mode with countercurrent tendency.

(11) Preferably, the compositions used in embodiments of the present invention contain essentially from 5 to 83 wt. % of 2,3,3,3-tetrafluoropropene and from 2 to 50 wt. % of 1,1-difluoroethane and from 15 to 75 wt. % of difluoromethane.

(12) Advantageously, the compositions used contain essentially from 5 to 63 wt. % of 2,3,3,3-tetrafluoropropene and from 2 to 25 wt. % of difluoroethane and from 35 to 70 wt. % of difluoromethane.

(13) The compositions that are particularly preferred contain essentially from 40 to 58 wt. % of 2,3,3,3-tetrafluoropropene, from 40 to 50 wt. % of difluoromethane and from 2 to 10 wt. % of 1,1-difluoroethane.

(14) The compositions used in embodiments of the present invention can be stabilized. The stabilizer preferably represents at most 5 wt. % relative to the total composition.

(15) As 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-methylphenol, epoxides (alkyl optionally fluorinated or perfluorinated or alkenyl or aromatic) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphates, phosphonates, thiols and lactones.

(16) Another object of embodiments of the present invention relates to a method of heat transfer in which the aforementioned ternary compositions of 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane and difluoromethane are used as heat transfer fluid in refrigeration systems replacing the mixture R-410A.

(17) Preferably, the method is employed in compression-type refrigeration systems with exchangers operating in countercurrent mode or in crossed-current mode with countercurrent tendency.

(18) The method according to embodiments of the present invention can be implemented in the presence of lubricants such as mineral oil, alkylbenzene, polyalkylene glycol and polyvinyl ether.

(19) The compositions used in embodiments of the present invention are suitable for replacing R-410A or R-134a in refrigeration, air conditioning and heat pumps with the existing installations.

(20) An embodiment of the present invention further relates to the use of ternary compositions of 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane and difluoromethane as heat transfer fluid in refrigeration systems replacing R-134a.

(21) Preferably, these compositions are used in compression-type refrigeration systems, currently using R-134a, with exchangers operating in countercurrent mode or in crossed-current mode with countercurrent tendency.

(22) Preferably, the compositions used to replace R-134a include, consist essentially of, or consist of from 70 to 88 wt. % of 2,3,3,3-tetrafluoropropene, from 8 to 14 wt. % of 1,1-difluoroethane, and from 4 to 16 wt. % of difluoromethane.

(23) Advantageously, the compositions used include, consist essentially of, or consist of from 84 to 88 (or 85 to 88, or 86 to 88) wt. % of 2,3,3,3-tetrafluoropropene, from 11 to 14 wt. % of 1,1-difluoroethane, and from 4 to 14 (or 4 to 13, or 4 to 12) wt. % of difluoromethane.

(24) The compositions used for replacing R-134a can be stabilized. The stabilizer preferably represents at most 5 wt. % relative to the total composition.

(25) As 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-methylphenol, epoxides (alkyl optionally fluorinated or perfluorinated or alkenyl or aromatic) such as n-butyl glycidyl ether, hexanediol diglycidyl ether, allyl glycidyl ether, butylphenylglycidyl ether, phosphites, phosphates, phosphonates, thiols and lactones.

(26) Another embodiment of the present invention relates to a method of heat transfer in which the aforementioned ternary compositions of 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane and difluoromethane are used as heat transfer fluid in refrigeration systems replacing the R134a.

(27) Preferably, the method is employed in compression-type refrigeration systems with exchangers operating in countercurrent mode or in crossed-current mode with countercurrent tendency.

(28) A method according to an embodiment of the present invention can be implemented in the presence of lubricants such as mineral oil, alkylbenzene, polyalkylene glycol and polyvinyl ether.

(29) The compositions used in embodiments of the present invention are suitable for replacing R-134a in refrigeration, air conditioning and heat pumps with the existing installations.

(30) When the compositions are used to replace R-134a, at least the following advantages may be obtained: high COP and CAP, as compared to when R-134a was used; Discharge temperature lower than R134a; and Pressure ratio lower than R134a and efficiency higher.
Experimental Section
Tools for Calculation

(31) The RK-Soave equation is used for calculating the densities, enthalpies, entropies and the data on liquid-vapor equilibrium of the mixtures. To use this equation it is necessary to know the properties of the pure substances used in the mixtures in question as well as the coefficients of interaction for each binary mixture.

(32) The data required for each pure substance are:

(33) Boiling point, critical temperature and pressure, curve of pressure as a function of temperature from the boiling point to the critical point, the saturated liquid density and saturated vapor density as a function of temperature.

(34) HFC-32, HFC-152a:

(35) The data for these products are published in ASHRAE Handbook 2005 chapter 20, and are also available using Refrop (software developed by NIST for calculating the properties of refrigerants).

(36) HFO-1234yf:

(37) The data for the temperature-pressure curve of HFO-1234yf are measured by the static method. The critical temperature and pressure are measured with a C80 calorimeter marketed by Setaram. The densities, at saturation as a function of temperature, are measured by the vibrating tube densimeter technology developed by the laboratories of the Ecole de Mines (Mining Engineering College) in Paris.

(38) Coefficient of Interaction of the Binary Mixtures

(39) The RK-Soave equation uses coefficients of binary interaction for representing the behavior of the products in mixtures. The coefficients are calculated as a function of experimental data for liquid-vapor equilibrium.

(40) The technique used for the measurements of liquid-vapor equilibrium 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 field rotating at variable speed is used for accelerating attainment of the equilibria. The samples are analyzed by gas chromatography (HP5890 series II) using a catharometer (TCD).

(41) HFC-32/HFO-1234yf, HFC-152a/HFO-1234yf:

(42) The measurements of liquid-vapor equilibrium on the HFC-32/HFO-1234yf binary mixture are performed for the following isotherms: 10 C., 30 C. and 70 C.

(43) The measurements of liquid-vapor equilibrium on the HFC-152a/HFO-1234yf binary mixture are performed for the following isotherms: 10 C.

(44) HFC-32/HFO-152a:

(45) The data on liquid-vapor equilibrium for the HFC-152a/HFC-32 binary mixture are available using Refprop. Two isotherms (20 C. and 20 C.) and two isobars (1 bar and 25 bar) are used for calculating the coefficients of interaction for this binary.

(46) Compression System

(47) Consider a compression system equipped with an evaporator and countercurrent condenser, a screw compressor and a pressure reducing valve.

(48) The system operates with 15 C. of superheating and 5 C. of supercooling. The minimum temperature difference between the secondary fluid and the refrigerant is considered to be of the order of 5 C.

(49) The isentropic efficiency of the compressors is a function of the compression ratio. This efficiency is calculated from the following equation:

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

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

(52) % CAP is the percentage of the ratio of the volumetric capacity supplied by each product to the capacity of R-410A.

(53) The coefficient of performance (COP) is defined as the ratio of the useful power delivered by the system to the power supplied to or consumed by the system.

(54) The Lorenz coefficient of performance (COP.sub.Lorenz) is a reference coefficient of performance. It is a function of temperature and is used for comparing the COPs of different fluids.

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

(56) (The temperatures T are in K)
T.sub.mean.sup.condenser=0.5(T.sub.inlet.sup.condenser+T.sub.outlet.sup.condenser)(2)
T.sub.mean.sup.evaporator=0.5(T.sub.inlet.sup.evaporator+T.sub.outlet.sup.evaporator)(3)

(57) The COP.sub.Lorenz in the case of air conditioning and refrigeration is:

(58) $\begin{array}{cc}\mathrm{COPlorenz}=\frac{T_{\mathrm{mean}}^{\mathrm{evaporator}}}{T_{\mathrm{mean}}^{\mathrm{condenser}}-T_{\mathrm{mean}}^{\mathrm{evaporator}}}\mathrm{The}{\mathrm{COP}}_{\mathrm{Lorenz}}\mathrm{in}\mathrm{the}\mathrm{case}\mathrm{of}\mathrm{heating}\mathrm{is}:& \left(4\right)\\ \mathrm{COPlorenz}=\frac{T_{\mathrm{mean}}^{\mathrm{condenser}}}{T_{\mathrm{mean}}^{\mathrm{condenser}}-T_{\mathrm{mean}}^{\mathrm{evaporator}}}& \left(5\right)\end{array}$

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

(60) % COP/COP.sub.Lorenz is the ratio of the COP of the system relative to the COP of the corresponding Lorenz cycle.

(61) Results, Cooling Mode or Air Conditioning

(62) In cooling mode, the compression system operates between a refrigerant inlet temperature at the evaporator of 5 C. and a refrigerant inlet temperature at the condenser of 50 C. The system delivers cold at 0 C.

(63) The performance of the compositions according to embodiments of the invention in cooling operating conditions is given in Table 1. The values of the constituents (HFO-1234yf, HFC-32, HFC-152a) for each composition are given as percentage by weight.

(64) TABLE-US-00001 TABLE 1 Temp outlet Temp outlet T outlet evap cond Ratio efficiency % COP/ evap ( C.) comp ( C.) cond ( C.) P (bar) P (bar) (w/w) Shift comp % CAP COPLorenz R410A 5 101 50 6.8 30.6 4.5 0.07 79.6 100 50.4 HFO-1234yf HFC-32 HFC-152a 50 45 5 1 95 45 5.6 23.3 4.2 4.00 80.5 92 55.9 45 50 5 2 99 46 5.7 24.4 4.2 3.48 80.3 95 55.4 45 45 10 1 97 45 5.4 22.8 4.2 4.26 80.4 92 56.5 40 50 10 1 100 46 5.6 23.9 4.3 3.87 80.2 95 56.1

(65) TABLE-US-00002 TABLE 2 Discharge Evaporator diff versus condenser Evap- High Low pres- saturation compressor ref saturation orator P P sure isentropic % CAP % COP % wt vapor discharge product liquid Glide (bar) (bar) ratio efficiency (Cooling) (Cooling) R134A 5.0 81.0 0.0 50.0 0.0 13.2 2.4 5.4 75.9 100 100 R32 R1234yf R152a 4 88 8 3.8 71.6 9.5 46.9 1.3 14.1 3.0 4.7 78.7 112 104 6 86 8 2.8 72.4 8.7 45.9 2.2 14.5 3.2 4.6 79.3 121 108 8 84 8 2.2 73.3 7.7 45.1 2.8 15.0 3.4 4.5 79.6 128 111 10 82 8 1.9 74.4 6.7 44.6 3.1 15.5 3.5 4.4 79.7 134 112 12 80 8 1.3 75.2 5.8 44.2 3.8 16.0 3.7 4.3 80.0 141 114 14 78 8 0.6 76.1 4.9 44.0 4.4 16.4 3.9 4.2 80.3 149 117 16 76 8 0.6 77.2 3.8 43.9 4.4 16.9 4.0 4.2 80.3 153 116 4 84 12 3.8 72.7 8.4 47.1 1.3 14.1 3.0 4.7 78.7 112 104 6 82 12 3.1 73.6 7.5 46.2 1.9 14.5 3.1 4.6 79.1 119 107 8 80 12 2.5 74.5 6.6 45.5 2.5 15.0 3.3 4.5 79.4 126 110 10 78 12 1.9 75.4 5.7 45.0 3.1 15.4 3.5 4.4 79.7 134 112 12 76 12 1.3 76.2 4.8 44.6 3.8 15.8 3.6 4.3 80.0 141 115 14 74 12 1.3 77.4 3.7 44.3 3.8 16.3 3.7 4.3 80.0 145 115 16 72 12 0.6 78.2 2.9 44.2 4.4 16.7 3.9 4.3 80.3 152 117 4 82 14 3.8 73.2 7.8 47.3 1.3 14.0 3.0 4.7 78.7 113 105 6 80 14 3.1 74.1 6.9 46.3 1.9 14.5 3.1 4.6 79.0 119 107 8 78 14 2.5 75.0 6.0 45.6 2.5 14.9 3.3 4.5 79.4 126 110 10 76 14 1.9 75.9 5.2 45.1 3.1 15.4 3.5 4.4 79.7 133 113 12 74 14 1.3 76.7 4.3 44.7 3.8 15.8 3.6 4.4 80.0 141 115 14 72 14 1.3 77.9 3.2 44.5 3.8 16.2 3.7 4.4 80.0 145 115 16 70 14 0.6 78.6 2.4 44.3 4.4 16.6 3.9 4.3 80.3 152 117
Results, Heating Mode

(66) In heating mode, the compression system operates between a refrigerant inlet temperature at the evaporator of 5 C. and a refrigerant inlet temperature at the condenser of 50 C. The system delivers heat at 45 C.

(67) The performance of the compositions according to embodiments of the invention in operating conditions in heating mode is given in Table 2. The values of the constituents (HFO-1234yf, HFC-32, HFC-152a) for each composition are given as percentage by weight.

(68) TABLE-US-00003 TABLE 3 Temp outlet Temp outlet T outlet evap cond Ratio efficiency % COP/ evap ( C.) comp ( C.) cond ( C.) P (bar) P (bar) (w/w) Shift comp % CAP COPLorenz R410A 5 101 50 6.8 30.6 4.5 0.07 79.6 100 58.8 HFO-1234yf HFC-32 HFC-152a 45 50 5 2 99 46 5.7 24.4 4.2 3.48 80.3 92 63.1 40 50 10 1 100 46 5.6 23.9 4.3 3.87 80.2 91 63.6

(69) TABLE-US-00004 TABLE 4 Evaporator Discharge condenser Evap- pres- saturation compressor diff versus saturation orator High Low sure isentropic % CAP % COP % wt vapor discharge ref product liquid Glide P (bar) P (bar) ratio efficiency Heating Heating R134A 5.0 81.0 0.0 50.0 0.0 13.2 2.4 5.4 75.9 100 100 R32 R1234yf R152a 4 88 8 3.8 71.6 9.5 46.9 1.3 14.1 3.0 4.7 78.7 110 104 6 86 8 2.8 72.4 8.7 45.9 2.2 14.5 3.2 4.6 79.3 117 107 8 84 8 2.2 73.3 7.7 45.1 2.8 15.0 3.4 4.5 79.6 124 109 10 82 8 1.9 74.4 6.7 44.6 3.1 15.5 3.5 4.4 79.7 129 109 12 80 8 1.3 75.2 5.8 44.2 3.8 16.0 3.7 4.3 80.0 136 111 14 78 8 0.6 76.1 4.9 44.0 4.4 16.4 3.9 4.2 80.3 142 113 16 76 8 0.6 77.2 3.8 43.9 4.4 16.9 4.0 4.2 80.3 147 113 4 84 12 3.8 72.7 8.4 47.1 1.3 14.1 3.0 4.7 78.7 110 104 6 82 12 3.1 73.6 7.5 46.2 1.9 14.5 3.1 4.6 79.1 116 106 8 80 12 2.5 74.5 6.6 45.5 2.5 15.0 3.3 4.5 79.4 123 108 10 78 12 1.9 75.4 5.7 45.0 3.1 15.4 3.5 4.4 79.7 129 110 12 76 12 1.3 76.2 4.8 44.6 3.8 15.8 3.6 4.3 80.0 135 111 14 74 12 1.3 77.4 3.7 44.3 3.8 16.3 3.7 4.3 80.0 139 111 16 72 12 0.6 78.2 2.9 44.2 4.4 16.7 3.9 4.3 80.3 146 113 4 82 14 3.8 73.2 7.8 47.3 1.3 14.0 3.0 4.7 78.7 110 104 6 80 14 3.1 74.1 6.9 46.3 1.9 14.5 3.1 4.6 79.0 116 106 8 78 14 2.5 75.0 6.0 45.6 2.5 14.9 3.3 4.5 79.4 123 108 10 76 14 1.9 75.9 5.2 45.1 3.1 15.4 3.5 4.4 79.7 129 110 12 74 14 1.3 76.7 4.3 44.7 3.8 15.8 3.6 4.4 80.0 135 112 14 72 14 1.3 77.9 3.2 44.5 3.8 16.2 3.7 4.4 80.0 139 111 16 70 14 0.6 78.6 2.4 44.3 4.4 16.6 3.9 4.3 80.3 146 113
Results, Low-Temperature Refrigeration

(70) In low-temperature refrigeration mode, the compression system operates between a refrigerant inlet temperature at the evaporator of 30 C. and a refrigerant inlet temperature at the condenser of 40 C. The system delivers cold at 25 C.

(71) The performance of the compositions according to embodiments of the invention in operating conditions in refrigeration mode is given in Table 3. The values of the constituents (HFO-1234yf, HFC-32, HFC-152a) for each composition are given as percentage by weight.

(72) TABLE-US-00005 TABLE 5 Temp outlet Temp outlet T outlet evap cond Ratio efficiency % COP/ evap ( C.) comp ( C.) cond ( C.) P (bar) P (bar) (w/w) Shift comp % CAP COPLorenz R410A 30 149 40 2.7 24.2 9.0 0.06 52.3 100 33.0 HFO-1234yf HFC-32 HFC-152a 45 50 5 27 137 36 2.3 19.1 8.4 3.35 56.9 93 38.8 40 50 10 26 140 35 2.2 18.6 8.5 3.73 56.4 93 38.9