CN114907817A

CN114907817A - Environment-friendly mixed refrigeration working medium, refrigerant and refrigeration system

Info

Publication number: CN114907817A
Application number: CN202210737095.XA
Authority: CN
Inventors: 张宗云; 曾婧; 宋美琪; 江世恒
Original assignee: Gree Electric Appliances Inc of Zhuhai
Current assignee: Gree Electric Appliances Inc of Zhuhai
Priority date: 2022-06-27
Filing date: 2022-06-27
Publication date: 2022-08-16
Anticipated expiration: 2042-06-27
Also published as: CN114907817B

Abstract

The invention provides an environment-friendly mixed refrigeration working medium, a refrigerant and a refrigeration system. The environment-friendly mixed refrigerant comprises the following components in percentage by mass: 1-42% of propane; 1-67% of trifluoroiodomethane; 25-70% of cyclopropane. Through the synergistic effect of the components, compared with the R134a refrigerant, the mixed refrigerant has lower GWP which is less than 50, and has obvious environmental protection advantage. The environment-friendly mixed refrigerant has excellent thermal performance, the refrigerating capacity Qv and coefficient of performance COP of unit volume are close to or better than R134a, and the refrigerating cycle performance is better. In addition, the boiling point, the critical temperature, the critical pressure and the operating pressure of the refrigeration working medium are close to those of R134a, and the refrigeration working medium can be directly applied to the field of air conditioning refrigeration on the premise of not changing main devices of the existing system and becomes an environment-friendly refrigeration working medium for replacing R134 a.

Description

Environment-friendly mixed refrigeration working medium, refrigerant and refrigeration system

Technical Field

The invention relates to the technical field of refrigeration, in particular to an environment-friendly mixed refrigeration working medium, a refrigerant and a refrigeration system.

Background

Along with the increasing global warming, the environmental protection problem is more and more emphasized, the CFC containing chlorine and no hydrogen in Freon has the largest destructive power to the environment, the HCFC containing hydrogen and chlorine is the second time, the Freon gas is dissipated into the stratosphere, and the chlorine atoms decomposed from the CFC destroy the ozone layer under the action of ultraviolet rays, so that the ultraviolet rays reaching the earth surface are greatly enhanced, the balance of the biological environment is destroyed, the living environment of human is seriously influenced, and the CFC needs to be eliminated.

At present, R134a used in an air conditioning system has good thermal performance, ODP (ozone potential value) is 0, but because the GWP is 1430, the GWP is in a controlled range based on a California correction scheme, and the gradual elimination is a necessary trend, so that the search for a working medium which meets the requirements of both environmental protection and energy efficiency of the capacity of the air conditioning system is urgent. At present, the substitution research of novel refrigerants with low GWP values is carried out internationally from the perspective of single working media and refrigerant compositions, and the novel natural working media such as HFCs substitutes, Hydrofluoroolefins (HFOs) substitutes and hydrocarbon refrigerants are mainly used, and the appropriate composition is sought to meet the requirements of air-conditioning systems on the refrigerants. Refrigerant compositions disclosed in the prior art often have the disadvantages of high GWP or insufficient cycle performance, and therefore, development of new refrigerants having better refrigeration performance, better compatibility with existing systems, and safer and more environmentally friendly properties is required.

Disclosure of Invention

The invention mainly aims to provide an environment-friendly mixed refrigerant, a refrigerant and a refrigeration system, and aims to solve the problems of high GWP (global warming potential) and insufficient refrigeration cycle performance of the refrigerant in the prior art.

In order to achieve the above object, according to one aspect of the present invention, there is provided an environment-friendly mixed refrigerant comprising, by mass: 1-42% of propane; 1-67% of trifluoroiodomethane; 25-70% of cyclopropane.

Further, the environment-friendly mixed refrigerant comprises the following components in percentage by mass: 1-14% of propane; 31-67% of trifluoroiodomethane; 32-68% of cyclopropane.

Further, the environment-friendly mixed refrigerant comprises the following components in percentage by mass: 1-8% of propane; 52-67% of trifluoroiodomethane; 25-40% of cyclopropane; and GWP of the environment-friendly mixed refrigerant is less than or equal to 36.

Further, the environment-friendly mixed refrigerant comprises the following components in percentage by mass: 1-14% of propane; 31-58% of trifluoroiodomethane; 36-55% of cyclopropane; and the relative performance coefficient of the environment-friendly mixed refrigerant is more than or equal to 1.012, and the relative performance coefficient is the ratio of the performance coefficients of the environment-friendly mixed refrigerant and 1,1,1, 2-tetrafluoroethane.

Further, the environment-friendly mixed refrigerant comprises 6% of propane, 39% of trifluoroiodomethane and 55% of cyclopropane in percentage by mass; or the environment-friendly mixed refrigerant comprises 14% of propane, 31% of trifluoroiodomethane and 55% of cyclopropane; or the environment-friendly mixed refrigerant comprises 36% of propane, 13% of trifluoroiodomethane and 51% of cyclopropane.

According to another aspect of the invention, a refrigerant is provided, comprising the environmentally-friendly mixed refrigerant of the invention.

Further, the refrigerant also comprises any one or more of a solubilizer, a lubricant and a dispersant.

Further, the lubricant is selected from any one or more of mineral oil, silicone oil and polyol ester.

According to another aspect of the present invention, there is provided a refrigeration system comprising a compressor, a condenser, an evaporator, a throttling element, the compressor, the condenser, the evaporator, the throttling element being connected by a closed circuit having the refrigerant of the present invention therein.

Further, the refrigeration system is an air conditioning system.

By applying the technical scheme of the invention, through the synergistic effect among the components, compared with the R134a refrigerant, the mixed refrigerant has lower GWP, the GWP is less than 50, and the mixed refrigerant has obvious environmental protection advantage. The environment-friendly mixed refrigerant has excellent thermal performance, the unit volume refrigerating capacity Qv and the coefficient of performance COP are close to or better than R134a, and the refrigerating cycle performance is better. In addition, the boiling point, the critical temperature, the critical pressure and the operating pressure of the refrigeration working medium are close to those of R134a, and the refrigeration working medium can be directly applied to the field of air conditioning refrigeration on the premise of not changing main devices of the existing system and becomes an environment-friendly refrigeration working medium for replacing R134 a.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:

FIG. 1 shows a diagram of a compression refrigeration cycle system of the present invention;

wherein the figures include the following reference numerals:

1. a compressor; 2. a condenser; 3. an evaporator; 4. a throttling element.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.

Interpretation of terms:

r134 a: 1,1,1, 2-tetrafluoroethane.

Refrigerating capacity per unit volume Qv: the amount of refrigeration generated per unit volume of refrigerant flowing in a refrigeration system.

Coefficient of performance COP: the cooling capacity obtained by unit power consumption.

Operating pressure: evaporation pressure and condensation pressure.

Compression ratio: ratio of evaporation pressure to condensation pressure.

Slip temperature: the difference between the bubble point temperature and the dew point temperature corresponding to 0.1 MPa.

As described in the background of the present application, the prior art has problems of high GWP of the refrigerant and insufficient performance of the refrigeration cycle. In order to solve the above problem, in an exemplary embodiment of the present application, there is provided an environment-friendly mixed refrigerant, which includes, by mass: 1-42% of propane; 1-67% of trifluoroiodomethane; 25-70% of cyclopropane.

Through the synergistic effect of the components with different energy efficiency and GWP values of the refrigeration working medium, compared with the conventional R134a refrigeration working medium, the mixed working medium has lower GWP, the GWP is less than 300, and the mixed working medium has obvious environmental protection advantage. The environment-friendly mixed refrigerant has excellent thermal performance, the unit volume refrigerating capacity Qv and the coefficient of performance COP are close to or better than R134a, and the refrigerating cycle performance is better. In addition, the boiling point, the critical temperature, the critical pressure and the operating pressure of the refrigeration working medium are close to those of R134a, and the refrigeration working medium can be directly applied to the field of air conditioning refrigeration on the premise of not changing main devices of the existing system and becomes an environment-friendly refrigeration working medium for replacing R134 a. In addition, the molecular mass of the mixed refrigerant is less than R134a, the fluidity is good, and the service life of the compressor is prolonged; the slip temperature is low, so that adverse effects caused by temperature slip can be eliminated; a compression ratio lower than R134a reduces compressor power consumption and benefits long-term compressor operation.

In a preferred embodiment, the environment-friendly mixed refrigerant comprises the following components in percentage by mass: 1-14% of propane; 31-67% of trifluoroiodomethane; 32-68% of cyclopropane. When the mass percentages of the three components in the refrigerant composition are within the ranges, the refrigerant composition has lower GWP, the GWP of the refrigerant composition is less than 50, and the refrigerant composition has the advantages of low carbon and environmental protection and also has better thermodynamic cycle performance.

Preferably, the environment-friendly mixed refrigerant comprises the following components in percentage by mass: 1-8% of propane; 52-67% of trifluoroiodomethane; 25-40% of cyclopropane; the GWP of the trifluoroiodomethane is smaller, and the GWP of the environment-friendly mixed refrigerant with the composition is less than or equal to 36. When the three components of the refrigerant composition are respectively in the above ranges in mass percent, the GWP is less than 50, and the refrigerant composition also has higher coefficient of performance COP and excellent cycle performance.

Preferably, the environment-friendly mixed refrigerant comprises the following components in percentage by mass: 1-14% of propane; 31-58% of trifluoroiodomethane; 36-55% of cyclopropane; the cyclopropane has smaller molecular weight, the relative performance coefficient of the environment-friendly mixed refrigerant with the composition is more than or equal to 1.012, and the relative performance coefficient is the ratio of the performance coefficients of the environment-friendly mixed refrigerant and 1,1,1, 2-tetrafluoroethane.

In some embodiments, the environment-friendly mixed refrigerant comprises 6% of propane, 39% of trifluoroiodomethane and 55% of cyclopropane in percentage by mass; or the environment-friendly mixed refrigerant comprises 14% of propane, 31% of trifluoroiodomethane and 55% of cyclopropane; or the environment-friendly mixed refrigerant comprises 36% of propane, 13% of trifluoroiodomethane and 51% of cyclopropane, and the comprehensive performance is better.

In yet another exemplary embodiment of the present application, there is also provided a refrigerant, including the eco-friendly mixed refrigerant of the present application, having a low GWP value and good refrigeration cycle performance.

In order to improve the fluidity and system applicability of the refrigerant, in a preferred embodiment, the refrigerant further comprises any one or more of a lubricant, a solubilizer and a dispersant. There is no particular limitation on the kind of lubricant, and lubricants commonly used in the art are all suitable for use in the present application. In a preferred embodiment, the lubricant is selected from any one or more of mineral oil, silicone oil, polyol ester.

In yet another exemplary embodiment of the present application, there is also provided a refrigeration system, as shown in fig. 1, comprising a compressor 1, a condenser 2, an evaporator 3, a throttling element 4, wherein the compressor 1, the condenser 2, the evaporator 3, the throttling element 4 are connected by a closed circuit, having a refrigerant of the present application therein. The low-pressure mixed refrigerant (refrigerant) exchanges heat with indoor air in the evaporator 3 to release cold, then the low-pressure gaseous refrigerant enters the compressor 1 to be compressed to high-temperature high-pressure gaseous state, exchanges heat with outdoor air through the condenser 2 to release heat, is condensed to high-pressure liquid refrigerant, and is throttled by the throttling element 4 to be gas-liquid two-phase low-pressure refrigerant.

In a preferred embodiment, the refrigeration system is an air conditioning system, and the refrigerant used in the air conditioning system can directly replace the existing environment-friendly refrigerant R134 a.

The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.

The invention combines the following refrigeration working fluid composition comprising propane (R290), trifluoroiodomethane (R13I1) and cyclopropane (RC 270). Wherein the proportions of the components are mass percent, and the sum of the mass percent of the components of each refrigeration working medium composition is 100 percent. When the combination mode is determined, the components of the refrigeration working medium are subjected to liquid phase physical mixing at the temperature of 23-27 ℃ and the pressure of 0.1MPa according to the corresponding mass ratio. The basic parameters of the component materials are shown in Table 1.

TABLE 1

Example 1

R290, R13I1 and RC270 are physically mixed in the liquid phase at a mass ratio of 1:58: 41.

Example 2

R290, R13I1 and RC270 were physically mixed in the liquid phase at 6:39:55 mass%.

Example 3

R290, R13I1 and RC270 are physically mixed in the liquid phase at a mass ratio of 6:58: 36.

Example 4

R290, R13I1 and RC270 were physically mixed in the liquid phase at a mass ratio of 8:52: 40.

Example 5

R290, R13I1 and RC270 are physically mixed in the liquid phase at a mass ratio of 14:31: 55.

Example 6

R290, R13I1 and RC270 are physically mixed in the liquid phase at a mass ratio of 8:67: 25.

Example 7

R290, R13I1 and RC270 are physically mixed in the liquid phase at a mass ratio of 22:31: 47.

Example 8

R290, R13I1 and RC270 are physically mixed in the liquid phase at a mass ratio of 24:6: 70.

Example 9

R290, R13I1 and RC270 were physically mixed in the liquid phase at 36:13:51 mass%.

Example 10

R290, R13I1 and RC270 were physically mixed in the liquid phase at 42:2:56 mass%.

Comparative example 1

R290, R13I1 and RC270 were physically mixed in the liquid phase at 56:30:14 mass%.

Comparative example 2

R290, R13I1 and RC270 are physically mixed in the liquid phase at a mass ratio of 62:23: 15.

Comparative example 3

The refrigerant is a single R134 a.

Comparative example 4

R290 and R13I1 were physically mixed in the liquid phase at 50:50 mass%.

Comparative example 5

R290 and RC270 were physically mixed in the liquid phase at a mass ratio of 50: 50.

Comparative example 6

R13I1 and RC270 were physically mixed in the liquid phase at 50:50 mass%.

The performance parameters of the mixed refrigerant of examples 1 to 10 and comparative examples 1 to 6 are shown in table 2.

TABLE 2

As can be seen from table 2, the refrigerant provided in the embodiment of the present application has a lower GWP, which is <50, and within the preferred range GWP <36, and has a more obvious environmental protection advantage compared with R134 a. Meanwhile, the molecular weight of the refrigerant is smaller than that of R134a, so that the refrigerant has better fluidity and is beneficial to prolonging the service life of the compressor. The boiling point, critical temperature and critical pressure are similar to those of R134a, and the product can be used as a long-term substitute of R134 a. In addition, the mixed refrigerant of the embodiment of the application has a small slip temperature, the slip temperatures of the listed embodiments are all lower than 3 ℃, the mixed refrigerant belongs to a near-azeotropic mixture, and adverse effects caused by temperature slip are eliminated.

Compared with comparative examples 4 to 6, the embodiment of the invention enables the mixed working medium to have lower GWP through the synergistic effect of the components with different energy efficiency and GWP values of the refrigeration working medium with specific components.

The results of comparison of the thermodynamic parameters (i.e., compression ratio and discharge temperature) and the relative thermodynamic properties (i.e., relative refrigerating capacity per unit volume and relative efficiency COP) of examples 1 to 10 and comparative examples 1 to 6 above under the refrigeration conditions (i.e., 10 ℃ evaporation temperature, 45 ℃ condensation temperature, 3 ℃ superheat degree, 7 ℃ supercooling degree, and 0.7 compressor adiabatic efficiency) are shown in table 3.

TABLE 3

As can be seen from table 3, the evaporating pressure and the condensing pressure of the refrigerant in the embodiments of the present application are similar to those of R134a, and can be directly used instead of R134a, and the compression ratio is lower than R134a, so that the power consumption of the compressor can be reduced, and the compressor is beneficial to long-term operation. And the coefficient of performance COP of each embodiment is equivalent to or better than R134a compared with the refrigerating capacity per unit volume of R134a, and the cycle performance is excellent. It can be seen from comparative examples 1 and 2 that the coefficient of performance COP is relatively low when the components of the refrigerant are outside the range of proportions for the present application.

Compared with comparative examples 4 to 6, the embodiment of the invention enables the mixed working medium to have better refrigeration cycle performance through the synergistic effect of the components with different energy efficiency and GWP values of the refrigeration working medium with specific components.

In summary, the refrigerant of the present application not only has the environmental protection characteristics of low GWP value and zero ODP under the condition of designing the system working condition and in the optimal proportion range of theoretical calculation, but also has excellent thermal performance, the unit volume refrigerating capacity Qv and the coefficient of performance COP are close to or superior to R134a, the operating pressure is close to R134a, and the refrigerant can be directly applied to the air-conditioning refrigeration field to become the environmental protection refrigerant replacing R134 a.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The environment-friendly mixed refrigerant is characterized by comprising the following components in percentage by mass:

1-42% of propane;

1-67% of trifluoroiodomethane;

25-70% of cyclopropane.

2. The environment-friendly mixed refrigerant according to claim 1, wherein the environment-friendly mixed refrigerant comprises, in mass percent:

1-14% of propane;

31-67% of trifluoroiodomethane;

32-68% of cyclopropane.

3. The environment-friendly mixed refrigerant according to claim 1, wherein the environment-friendly mixed refrigerant comprises, in mass percent:

1-8% of propane;

52-67% of trifluoroiodomethane;

25-40% of cyclopropane;

and GWP of the environment-friendly mixed refrigerant is less than or equal to 36.

4. The environment-friendly mixed refrigerant according to claim 1, wherein the environment-friendly mixed refrigerant comprises, in mass percent:

1-14% of propane;

31-58% of trifluoroiodomethane;

36-55% of cyclopropane;

and the relative performance coefficient of the environment-friendly mixed refrigerant is more than or equal to 1.012, and the relative performance coefficient is the ratio of the performance coefficients of the environment-friendly mixed refrigerant and 1,1,1, 2-tetrafluoroethane.

5. The eco-friendly mixed refrigerant according to any one of claims 1 to 4, wherein the eco-friendly mixed refrigerant comprises, in mass%, 6% of the propane, 39% of the trifluoroiodomethane and 55% of the cyclopropane; or

The environment-friendly mixed refrigerant comprises 14% of propane, 31% of trifluoroiodomethane and 55% of cyclopropane; or

The environment-friendly mixed refrigerant comprises 36% of propane, 13% of trifluoroiodomethane and 51% of cyclopropane.

6. A refrigerant comprising a refrigerant, characterized in that the refrigerant is the environment-friendly mixed refrigerant of any one of claims 1 to 5.

7. The refrigerant according to claim 6, further comprising any one or more of a solubilizer, a lubricant, and a dispersant.

8. The refrigerant according to claim 7, wherein the lubricant is selected from any one or more of mineral oil, silicone oil, and polyol ester.

9. A refrigeration system comprising a compressor, a condenser, an evaporator, a throttling element, said compressor, condenser, evaporator, throttling element being connected by a closed circuit, said closed circuit having a refrigerant therein, characterized in that said refrigerant is a refrigerant according to any one of claims 6 to 8.

10. The refrigeration system of claim 9, wherein the refrigeration system is an air conditioning system.