CN116083054B

CN116083054B - Environment-friendly mixed refrigeration working medium, refrigerant and refrigeration system

Info

Publication number: CN116083054B
Application number: CN202211665994.XA
Authority: CN
Inventors: 张宗云; 宋美琪; 曾婧; 江世恒
Original assignee: Gree Electric Appliances Inc of Zhuhai
Current assignee: Gree Electric Appliances Inc of Zhuhai
Priority date: 2022-12-23
Filing date: 2022-12-23
Publication date: 2024-05-28
Anticipated expiration: 2042-12-23
Also published as: CN116083054A

Abstract

The invention provides an environment-friendly mixed refrigerant, a refrigerant and a refrigerating system. The environment-friendly mixed refrigeration working medium comprises the following components in percentage by mass: 38-98% of propane; 1 to 28 percent of trifluoromethyl methyl ether; propylene 1-40%. The mixed environment-friendly refrigerant has the advantages of ODP value of 0, low GWP value, good cycle performance and working pressure similar to R134a, and can well solve the problem of higher GWP value of the existing R134a refrigerant; the heat performance is excellent, the coefficient of performance COP is equivalent to R134a, the refrigerating capacity per unit volume is superior to that of R134a, and the heat pump water heater can be directly used as a long-term substitute working medium of R134a to be applied to an air conditioner refrigerating system on the premise of not changing main devices.

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

With the increasing global warming, environmental protection is becoming more and more important, the chlorine-containing and hydrogen-free fluorocarbon CFCs in freons have the greatest environmental destruction, and the hydrogen-containing and chlorine-containing fluorocarbon HCFCs are inferior to each other, so that these freon gases are dissipated into the stratosphere, and due to the effect of ultraviolet rays, chlorine atoms decomposed from chlorofluorocarbons destroy the ozone layer, which results in the great enhancement of ultraviolet rays reaching the earth surface, damages the balance of biological environment, seriously affects the living environment of human beings, and needs to be eliminated.

R134a used in the current air conditioning system has good thermal performance, ODP (ozone potential value) is 0, but because GWP is 1430 and the GWP is in the controlled range of the basic plus modification, phase-out is already a necessary trend, so that it is urgent to find working media which meet the requirements of environmental protection and the energy efficiency of the air conditioning system. At present, from the point of view of single working medium and refrigerant composition, substitution research of novel low GWP value refrigerants is often carried out internationally, mainly including novel HFCs substitutes, hydrofluoroolefin (HFOs) substitutes and hydrocarbon refrigerant natural working media, and proper compositions are sought to meet the requirements of an air conditioning system on the refrigerants.

However, the existing disclosed refrigerant compositions have the disadvantages of higher GWP, insufficient cycle performance, etc., and therefore, development of new refrigerants having better refrigeration performance, better compatibility with existing systems, and safer and more environmentally friendly performance is required.

Disclosure of Invention

The invention mainly aims to provide an environment-friendly mixed refrigerant, a refrigerant and a refrigerating system, so as to solve the problem that the refrigerant in the prior art cannot achieve both environment-friendly performance and thermodynamic performance.

In order to achieve the above object, according to one aspect of the present invention, there is provided an environment-friendly mixed refrigerant comprising, in mass percent: 38-98% of propane; 1 to 28 percent of trifluoromethyl methyl ether; propylene 1-40%.

Further, the environment-friendly mixed refrigerant comprises the following components in percentage by mass: 45-98% of propane; 1 to 18 percent of trifluoromethyl methyl ether; propylene 1-40%.

Further, the environment-friendly mixed refrigerant comprises the following components in percentage by mass: 45-58% of propane; 8-18% of trifluoromethyl methyl ether; 24-40% of propylene.

Further, the environment-friendly mixed refrigerant comprises 45% of propane, 25% of trifluoromethyl methyl ether and 30% of propylene in percentage by mass.

Further, the environment-friendly mixed refrigerant comprises, by mass, 49% of propane, 11% of trifluoromethyl methyl ether and 40% of propylene.

Further, the environment-friendly mixed refrigerant comprises, by mass, 52% of propane, 8% of trifluoromethyl methyl ether and 40% of propylene.

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

Further, the refrigerant also comprises any one or more of a lubricant, a solubilizer and a dispersing agent; the lubricant is selected from 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 and a throttling element connected by a closed circuit having a refrigerant therein, the refrigerant being a refrigerant as described above in the present invention.

Further, the refrigeration system is an air conditioning system.

The mixed environment-friendly refrigerant has the advantages of ODP value of 0, low GWP value, good cycle performance and working pressure similar to R134a, and can well solve the problem of higher GWP value of the existing R134a refrigerant. The heat performance is excellent, the coefficient of performance COP is equivalent to R134a, the refrigerating capacity per unit volume is superior to that of R134a, and the heat pump water heater can be directly used as a long-term substitute working medium of R134a to be applied to an air conditioner refrigerating system on the premise of not changing main devices. Compared with the prior art, the invention has the advantages that:

1. environmental friendliness: compared with R134a refrigerant, the mixed environment-friendly refrigerant has a lower GWP value and obvious environment-friendly advantage.

2. The method is directly used: the mixed environment-friendly refrigerant disclosed by the invention has good thermal performance, and when the mixed environment-friendly refrigerant is applied to air conditioner refrigeration equipment, the refrigeration cycle performance is superior to that of R134a, the working pressure is similar to that of R134a, and the novel refrigerant can be directly filled on the premise of not changing main devices of a system.

3. The molecular mass is small: the molecular mass of the mixed environment-friendly refrigeration working medium is small relative to R134a, so that the mixed environment-friendly refrigeration working medium has good fluidity, and is beneficial to prolonging the service life of a compressor.

4. The sliding temperature is small: the sliding temperature of the mixed environment-friendly refrigeration working medium is lower than 1 ℃, belongs to near-azeotropic mixtures, and eliminates adverse effects caused by temperature sliding.

5. The compression ratio is low: the pressure ratio of the mixed environment-friendly refrigeration working medium is lower than R134a, so that the power consumption of the compressor can be reduced, and the mixed environment-friendly refrigeration working medium is beneficial to long-term operation of the compressor.

Drawings

The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:

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

Wherein the above 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, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.

It should be noted that the terms "comprising" and "having," and any variations thereof, in the description and claims of the present application are intended to cover a non-exclusive inclusion, such that a system, article, or apparatus that comprises a list of elements is not necessarily limited to those elements expressly listed but may include other elements not expressly listed or inherent to such article or apparatus. The specific meaning of the above terms in the present application can be understood by those skilled in the art according to the specific circumstances.

As described in the background art of the invention, the prior art has the problem that the refrigerant cannot achieve both the environmental protection performance and the thermal performance. In order to solve the above problems, in an exemplary embodiment of the present invention, an environment-friendly mixed refrigerant is provided, which comprises, in mass percent: 38-98% of propane; 1 to 28 percent of trifluoromethyl methyl ether; propylene 1-40%.

The invention combines the above-mentioned several refrigerating working media specifically, selects proper components, and makes the environment-friendly mixed refrigerating working medium have low GWP value, zero ODP environmental protection characteristic, excellent thermodynamic performance, coefficient of performance COP equivalent to R134a and unit volume refrigerating capacity superior to R134a through the relationship of complementary advantages and balance of environmental protection performance and thermodynamic performance. The operating pressure is similar to R134a, and can be directly used without changing the main components of the system. The refrigerant can be used for replacing R134a in the field of refrigeration and air conditioning.

The composition contains a plurality of refrigeration working mediums, the mixed working mediums have lower GWP values by playing the synergistic effect among the refrigeration working mediums, the volume refrigeration capacity superior to that of R134a can be obtained by adopting the mixed refrigeration working mediums for refrigeration, and meanwhile, the problem that the existing refrigerant (R134 a) has higher GWP values is solved, so that the composition is an environment-friendly mixed refrigeration working medium. In conclusion, the mixed refrigerant has the advantages of low GWP value and better refrigerating capacity per unit volume.

Typically, but not limited to, in the environment-friendly mixed refrigerant, the mass percentage of propane is 38％、39％、40％、41％、42％、43％、44％、45％、46％、47％、48％、49％、50％、51％、52％、53％、54％、55％、56％、57％、58％、59％、60％、61％、62％、63％、64％、65％、66％、67％、68％、69％、70％、71％、72％、73％、74％、75％、76％、77％、78％、79％、80％、81％、82％、83％、84％、85％、86％、87％、88％、89％、90％、91％、92％、93％、94％、95％、96％、97％、98％ or a range value consisting of any two values of the mass percentage; the mass percent of the trifluoromethyl methyl ether is 1％、2％、3％、4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％、21％、22％、23％、24％、25％、26％、27％、28％ or a range value consisting of any two values of the mass percent; the mass percentage of propylene is 1％、2％、3％、4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％、20％、21％、22％、23％、24％、25％、26％、27％、28％、29％、30％、31％、32％、33％、34％、35％、36％、37％、38％、39％、40％ or the range value formed by any two values of the propylene, and the sum of the mass percentages of the components of the environment-friendly mixed refrigerant accords with 100 percent.

The invention further optimizes the content of each component by comprehensively considering each numerical value of each proportion of the components, such as GWP value, qv value, COP value, evaporation pressure, condensation pressure and the like, and in an optimized implementation mode, the environment-friendly mixed refrigeration working medium comprises the following components in percentage by mass: 45-98% of propane; 1 to 18 percent of trifluoromethyl methyl ether; propylene 1-40%. The environment-friendly mixed refrigerant in the range has lower GWP value, higher Qv value and COP value, and the evaporating and condensing pressures are more similar to those of R134 a.

The invention further combines the above refrigerants specifically, selects proper component content to realize further advantage complementation, and in a preferred embodiment, the environment-friendly mixed refrigeration working medium comprises the following components in percentage by mass: 45-58% of propane; 8-18% of trifluoromethyl methyl ether; 24-40% of propylene.

Specifically, in a preferred embodiment, the environment-friendly mixed refrigerant comprises 45% of propane, 25% of trifluoromethyl methyl ether and 30% of propylene in percentage by mass. Or in a preferred embodiment, the environment-friendly mixed refrigerant comprises 49% of propane, 11% of trifluoromethyl methyl ether and 40% of propylene in percentage by mass. Or in a preferred embodiment, the environment-friendly mixed refrigerant comprises 52% of propane, 8% of trifluoromethyl methyl ether and 40% of propylene in percentage by mass. The mixed refrigeration working medium with the combination can further give consideration to environmental protection performance and thermal performance, and has better comprehensive performance.

In another exemplary embodiment of the present invention, a refrigerant is provided, including a refrigerant, where the refrigerant is an environment-friendly mixed refrigerant of the present invention, and has a lower GWP value and good thermodynamic cycle performance.

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

In yet another exemplary embodiment of the present invention, there is also provided a refrigeration system, as shown in fig. 1, which includes a compressor, a condenser, an evaporator, and a throttling element, wherein the compressor, the condenser, the evaporator, and the throttling element are connected by a closed circuit, and a refrigerant is provided in the closed circuit, and the refrigerant is the refrigerant of the present invention. The low-pressure mixed refrigerant (refrigerant) exchanges heat between the evaporator 3 and indoor air to release cold energy, then the low-pressure gaseous refrigerant enters the compressor 1 to be compressed into a high-temperature high-pressure gaseous state, exchanges heat with outdoor air through the condenser 2 to release heat, condenses into a high-pressure liquid refrigerant, and throttles into a gas-liquid two-phase low-pressure refrigerant through the throttling element 4. The refrigerant composition in the invention exchanges heat, is compressed and throttled in the single-stage compression air conditioner to replace R134a refrigerant.

In a preferred embodiment, the refrigeration system is an air conditioning system, and the refrigerant of the present application can be used for the air conditioning system to directly replace the existing environment-friendly refrigerant of R134 a.

The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.

The basic parameters of each component substance of the environment-friendly mixed refrigerant are shown in table 1.

TABLE 1

A plurality of specific examples are given below, wherein the proportions of the components are mass percentages, and the sum of the mass percentages of the components of each environment-friendly mixed refrigerant is 100%. In each example and comparative example, the components are physically mixed in liquid phase according to a fixed mass ratio at a temperature of 23-27 ℃ and a pressure of 0.1MPa, and the mixture is uniformly mixed to obtain the composition.

Example 1:

R290, RE143a and R1270 were mixed in the liquid phase at 38:27:35 mass percent.

Example 2:

R290, RE143a and R1270 were mixed in the liquid phase at 42:28:30 mass percent.

Example 3:

R290, RE143a and R1270 were mixed in the liquid phase at 45:25:30 mass percent.

Example 4:

r290, RE143a and R1270 were mixed in the liquid phase at 49:11:40 mass percent.

Example 5:

R290, RE143a and R1270 were mixed in the liquid phase at 52:8:40 mass percent.

Example 6:

R290, RE143a and R1270 were mixed in the liquid phase at 58:18:24 mass percent.

Example 7

R290, RE143a and R1270 were mixed in the liquid phase at 98:1:1 mass percent.

Comparative example 1:

R290, RE143a and R1270 were mixed in the liquid phase at 22:46:32 mass percent for physical mixing

Comparative example 2:

r290, RE143a and R1270 were mixed in the liquid phase at 36:39:25 mass percent of the components are physically mixed

Comparative example 3:

R290, RE143a and R1270 were mixed in the liquid phase at 54:40:6 mass percent for physical mixing

Comparative example 4:

r290, RE143a and R1270 were mixed in the liquid phase at 63:32:5 mass percent for physical mixing

The performance parameters of the environment-friendly mixed refrigerant of examples 1 to 7, comparative examples 1 to 4 and R134a are shown in Table 2.

TABLE 2

The slip temperature is the difference between the bubble point temperature and the dew point temperature corresponding to 0.1 MPa.

As can be seen from Table 2, the environment-friendly mixed refrigerant composition provided by the invention has a lower GWP value, has a GWP of <150, has a GWP of <100 in a preferred range, and has the advantage of more obvious environment protection compared with R134 a. Meanwhile, the molecular weight is smaller than that of R134a, so that the material has better fluidity and contributes to prolonging the service life of the compressor. The sliding temperature of the mixed refrigerant is smaller, and the sliding temperature of the listed embodiments is lower than 1 ℃, belongs to near-azeotropic mixtures, and eliminates adverse effects caused by temperature sliding.

The comparative results of the thermodynamic parameters (i.e., compression ratio and discharge temperature) and the relative thermodynamic properties (i.e., relative refrigerating capacity Qv and coefficient of performance COP) of the above examples 1 to 7, comparative examples 1 to 4 and R134a under the refrigerating conditions (i.e., evaporation temperature of 10 ℃, condensation temperature of 45 ℃, degree of superheat of 3 ℃, degree of supercooling of 7 ℃, and adiabatic efficiency of compressor of 0.7) are shown in table 3.

TABLE 3 Table 3

As can be seen from Table 3, the evaporating and condensing pressures of the various embodiments of the present invention are similar to R134a. Compression ratios lower than R134a may reduce compressor power consumption and may be beneficial for long term operation of the compressor. The coefficient of performance COP of the whole system is equivalent to R134a, and the refrigerating capacity per unit volume is better than that of R134a. Furthermore, it can be seen from the comparative examples that when the ratio of each component is out of the range of the present invention, the GWP values of comparative example 1 and comparative example 2 are high, the coefficient of performance COP is relatively low, the GWP values of comparative example 3 and comparative example 4 are high, the refrigerating capacity Qv per unit volume is relatively low, and the overall properties are inferior to those of the compositions of examples.

In summary, the environment-friendly mixed refrigerant provided by the invention has the environment-friendly characteristics of low GWP value and zero ODP under the design working condition and within the optimal proportion range calculated by theory, and has excellent thermal performance, the coefficient of performance COP is equivalent to R134a, and the refrigerating capacity per unit volume is better than that of R134a. The operating pressure is similar to R134a, and can be directly used without changing the main components of the system. The refrigerant can be used for replacing R134a in the field of refrigeration and air conditioning.

The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. 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:

38-98% of propane;

1 to 28 percent of trifluoromethyl methyl ether;

Propylene 1-40%.

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

45-98% of propane;

1 to 18 percent of trifluoromethyl methyl ether;

Propylene 1-40%.

3. The environment-friendly mixed refrigerant according to claim 1 or 2, characterized in that the environment-friendly mixed refrigerant comprises, in mass percent:

45-58% of propane;

8-18% of trifluoromethyl methyl ether;

24-40% of propylene.

4. The environment-friendly mixed refrigerant as claimed in claim 1, wherein the environment-friendly mixed refrigerant comprises 45% of propane, 25% of trifluoromethyl methyl ether and 30% of propylene in mass percent.

5. The environment-friendly mixed refrigerant as claimed in claim 1, wherein the environment-friendly mixed refrigerant comprises, in mass percent, 49% of propane, 11% of trifluoromethyl methyl ether and 40% of propylene.

6. The environment-friendly mixed refrigerant as claimed in claim 1, wherein the environment-friendly mixed refrigerant comprises, in mass percent, 52% of propane, 8% of trifluoromethyl methyl ether and 40% of propylene.

7. A refrigerant comprising a refrigerant medium, wherein the refrigerant medium is an environmentally friendly mixed refrigerant medium as defined in any one of claims 1 to 6.

8. The refrigerant of claim 7, further comprising any one or more of a lubricant, a solubilizing agent, a dispersant; 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 and a throttling element connected by a closed circuit having a refrigerant therein, wherein the refrigerant is the refrigerant of claim 7 or 8.

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