Non-combustible mixed refrigerant having low greenhouse effect and application thereof

Abstract

A non-combustible mixed refrigerant having a low greenhouse effect and an application thereof, the mixed refrigerant comprises the following components in mass fractions: 4-31.5% of R125, 50-80% of R1234ze (E) and 12-22% of R1234yf. Under the cooperation of each component dosage range, the mixed refrigerant becomes non-combustible, the ODP is 0, and the GWP is not greater than 1000. The present invention may be used in a refrigeration system, does not destruct ozone, reduces the greenhouse effect, and has a low slip temperature, relating to ternary azeotropic or near-azeotropic refrigerants, and being beneficial for the stable operation of a refrigeration system. The mixed refrigerant may also be used as a foaming agent or an aerosol propellant, and has the advantages of being non-combustible, having a low ozone destruction index, and being environmentally friendly, safe and reliable.

Claims

1. A mixed refrigerant comprising, by mass fraction, 4-31.5% of R125, 50-80% of R1234ze(E) and 12-22% of R1234yf, and the mixed refrigerant further contains CF.sub.3I.

2. The mixed refrigerant according to claim 1, wherein the mixed refrigerant is non-flammable and azeotropic or near-azeotropic.

3. The mixed refrigerant according to claim 1, wherein the mixed refrigerant has an ODP of 0 and a GWP 1000.

4. The mixed refrigerant according to claim 1, wherein the mixed refrigerant has an ODP of 0 and a GWP 400.

5. The mixed refrigerant according to claim 4, wherein the mixed refrigerant has an ODP of 0 and a GWP 150.

6. The mixed refrigerant according to claim 1, wherein the mixed refrigerant further contains R32.

7. The mixed refrigerant according to claim 6, wherein the mixed refrigerant further includes a stabilizer.

8. The mixed refrigerant according to claim 7, wherein the stabilizer includes one selected from the group consisting of alkyl aryl ether, thioalcohol, lactones, thioether, nitromethane, alkylsilane, benzophenone derivatives, diethylene terephthalic acid and diphenyl terephthalic acid, or a mixture of at least two selected therefrom.

9. The mixed refrigerant according to claim 1, wherein the mixed refrigerant further includes a stabilizer.

10. The mixed refrigerant according to claim 9, wherein the stabilizer includes one selected from the group consisting of alkyl aryl ether, thioalcohol, lactones, thioether, nitromethane, alkylsilane, benzophenone derivatives, diethylene terephthalic acid and diphenyl terephthalic acid, or a mixture of at least two selected therefrom.

11. The mixed refrigerant according to claim 1, wherein the mixed refrigerant further includes a stabilizer.

12. The mixed refrigerant according to claim 11, wherein the stabilizer includes one selected from the group consisting of alkyl aryl ether, thioalcohol, lactones, thioether, nitromethane, alkylsilane, benzophenone derivatives, diethylene terephthalic acid and diphenyl terephthalic acid, or a mixture of at least two selected therefrom.

13. A refrigeration system comprising the mixed refrigerant according to claim 1, 6, 9, 7, 11, 10, 8 or 12.

14. The refrigeration system according to claim 13, wherein the refrigeration system further comprises lubricating oil.

15. The refrigeration system according to claim 14, wherein the lubricating oil comprises any one selected from the group consisting of natural mineral oil, polyalkylene glycol, polyol ester, alkyl benzene, poly-alfa olefin and polyvinyl ether, or a combination of at least two selected therefrom.

Description

DETAILED DESCRIPTION

(1) The technical solutions of present disclosure will be further illustrated by way of the following embodiments. It should be understood by those skilled in the art that these embodiments are only intended to aid the understanding of the present disclosure and should not to be considered as limitation thereto.

Example 1

(2) In this example, a mixed refrigerant comprised, by mass fraction, 4% of R125, 76% of R1234ze(E) and 20% of R1234yf was provided.

Example 2

(3) In this example, a mixed refrigerant comprised, by mass fraction, 4% of R125, 74% of R1234ze(E) and 22% of R1234yf was provided.

Example 3

(4) In this example, a mixed refrigerant comprised, by mass fraction, 10% of R125, 72% of R1234ze(E) and 18% of R1234yf was provided.

Example 4

(5) In this example, a mixed refrigerant comprised, by mass fraction, 15% of R125, 68% of R1234ze(E) and 17% of R1234yf was provided.

Example 5

(6) In this example, a mixed refrigerant comprised, by mass fraction, 31.1% of R125, 55.2% of R1234ze(E) and 13.7% of R1234yf was provided.

Example 6

(7) In this example, a mixed refrigerant comprised, by mass fraction, 31.5% of R125, 50% of R1234ze(E), and 18.5% of R1234yf was provided.

Example 7

(8) In this example, a mixed refrigerant comprised, by mass fraction, 4% of R125, 80% of R1234ze(E) and 16% of R1234yf was provided.

(9) Under the air conditioning test conditions of ARI Standard 520: evaporation temperature 7.2° C., condensation temperature 54.4° C., superheat temperature 11.1° C., undercooling temperature 8.3° C. and compressor isentropic efficiency 0.8, the environmental parameters, physical properties and thermal properties of R134a and the mixed refrigerants in Examples 1-7 were measured and results are listed in Table 1.

(10) TABLE-US-00001 TABLE 1 Example Example Example Example Example Example Example 1 2 3 4 5 6 7 R134a ODP 0 0 0 0 0 0 0 0 GWP 127 127 317 476 986 999 127 1300 Molecular 114.27 114.27 114.61 114.9 115.84 115.86 114.27 102.03 weight (g/mol) Evaporating 301.33 302.24 333.59 360.66 447.42 456.28 299.88 376.84 pressure (kPa) Condensing 1113.4 1112.88 1161.66 1204.81 1367.53 1379.60 1115.79 1475.82 pressure (kPa) Exhaust 64.9 64.89 63.4 62.3 60.3 54.95 65.44 74.8 temperature (° C.) Temperature 1.46 1.49 3.24 4.49 7.12 7.31 1.41 — glide (° C.) COP* 1.06 1.06 1.11 1.14 1.22 1.23 1.05 1 Cooling 0.89 0.89 0.88 0.87 0.84 0.83 0.90 1 capacity* Volume 0.8 0.8 0.88 0.94 1.16 1.17 0.80 1 cooling capacity*
Remarks: * in Table 1 indicates a relative value compared to the corresponding value of R134a, wherein COP is Coefficient of Performance.

(11) It can be seen from Table 1 that the mixed refrigerants as prepared in Examples 1-7 had an ODP of 0 and a GWP of less than or equal to 1000 and they belonged to azeotropic or near-azeotropic refrigerants, which were beneficial to the stable operation of the system. The evaporating pressure and condensing pressure of the mixed refrigerants were equivalent to those of R134a, and they can be directly used to replace R134a in systems without great modification. Compared with R134a, the cooling capacity and volume cooling capacity of the mixed refrigerants were both lower than those of R134a by about 10%; COP was 5-23% higher than that of R134a, and the exhaust temperature was also lower, which was beneficial to decreasing the exhaust temperature of the compressor.

(12) The explosion limits of the mixed refrigerants in Examples 1-7, R600a (R600a was used to verify the accuracy of equipment used in the flammability test), R1234ze(E) and R1234yf were measured according to the ASHRAE 34 standard. The experiments were performed in a 12L round bottom flask. The ignition source was the induction spark between two electrodes with an alternating current of 30 mA, 15KV and a spark duration of 0.4 s. The electrodes were L-shape, made of tungsten and had a diameter of 1 mm. The two electrodes were 6.4 mm apart.

(13) The electrodes were mounted at a height of ⅓ from the bottom of the bottle. The angle of flame propagation was determined by observation and was used to determine the flammability. If the angle between the center of the electrodes and the flame frontier on the flask wall was less than 90 degree, the refrigerant was non-flammable; if the angle was greater than 90, it was flammable. The test results are shown in Table 2, wherein LFL represents the lower flammable limit, UFL represents the upper flammable limit.

(14) TABLE-US-00002 TABLE 2 Refrigerant LFL (v %) UFL (v %) Notes R600a 1.8 8.5 R1234ze(E) 7 9.5 R1234yf 6.2 12.3 Example 1 NA NA None-flammable Example 2 NA NA None-flammable Example 3 NA NA None-flammable Example 4 NA NA None-flammable Example 5 NA NA None-flammable Example 6 NA NA None-flammable Example 7 NA NA None-flammable

(15) Table 2 shows that the mixed refrigerants of the this disclosure were non-flammable.

(16) The mixed refrigerants of Examples 1-7 were charged into a pressure resistant container with an observation window. The temperature in the container was kept at 25° C. and the mixed refrigerant was in a vapor-liquid equilibrium state. The initial vapor pressure in the container was measured, and then the refrigerant in the container was discharged slowly in order to keep the temperature constant until 50% weight percent of the mixed refrigerant was discharged. At this time, a part of liquid was still present in the container. The vapor pressure was measured again.

(17) Changes in pressure values before relief ant that after relief are shown in Table 3.

(18) TABLE-US-00003 TABLE 3 Pressure before Pressure after 50% relief relief Change in Refrigerant (kPa) (kPa) pressure(%) Example 1 583.3 560.64 3.9 Example 2 588.36 565.67 3.9 Example 3 619.1 580.27 6.3 Example 4 652.35 600.27 8 Example 5 768.17 680.22 11.4 Example 6 786.61 700.98 10.9 Example 8 572.79 550.54 3.9

(19) Table 3 shows that pressure changes before and after relief were less than 12% and that the mixed refrigerants were azeotropic or near-azeotropic.

(20) The embodiments above are used to illustrate the mixed refrigerants of the present disclosure and use thereof; however, the present disclosure is not limited to the above embodiments, and it does not mean that the present disclosure must rely on the above embodiments to be implemented. It should be understood by those skilled in the art that any improvements of the present disclosure, the equivalent replacement of the raw materials of the present disclosure, the addition of auxiliary components and the selection of specific means etc. will all fall within the scope of protection and disclosure of present disclosure.