Mixed refrigerant composition and preparation method and application of mixed refrigerant

Abstract

The invention relates to the technical field of energy conversion media, and particularly discloses a mixed refrigerant composition and a preparation method and application of a mixed refrigerant. The mixed refrigerant composition comprises the following components: a component A: 68-80 wt% of pentafluoroethane; a component B: 18 to 30 weight percent of 1, 1-difluoroethane; a component C: 2 to 10 wt% of hydrocarbon; wherein the hydrocarbon comprises propane and isobutane. The refrigerant prepared from the composition is good in refrigeration effect, can effectively replace an R22 refrigerant, is low in greenhouse effect, has an ODP value of 0, can avoid ozone depletion, is not flammable and explosive, and is high in safety in storage and use processes. The device is particularly suitable for refrigeration devices such as air conditioners.

Description

Technical Field

[0001] The present invention relates to the technical field of energy conversion media, and in particular to a mixed refrigerant composition and a preparation method and application of the mixed refrigerant. Background Art

[0002] Refrigerant, also known as coolant, refrigerant, and refrigerant, is a medium substance used to complete energy conversion in various heat engines. These substances usually increase power through reversible phase changes (such as gas-liquid phase change), such as steam in steam engines, refrigerant in refrigerators, etc. When a general steam engine is working, it releases the thermal energy of steam and converts it into mechanical energy to generate motive power; while the refrigerant in the refrigerator is used to transfer heat from low temperature to high temperature.

[0003] As people's environmental awareness continues to increase, humans have begun to continuously develop and select more environmentally friendly refrigerants. The commonly used refrigerant is R22, which is mainly composed of hydrogen, chlorine, fluorine and carbon elements (expressed as HCFC). It has a destructive effect on the ozone layer and is listed as a Class I controlled substance in the Montreal Protocol. This type of substance has been gradually banned in my country. It is mainly composed of hydrogen, chlorine, fluorine and carbon elements (expressed as HCFC) and is low in toxicity. Summary of the invention

[0004] The invention provides a mixed refrigerant composition. The refrigerant prepared by using the mixed refrigerant has good refrigeration effect, can effectively replace R22 refrigerant, has low greenhouse effect, has an ODP value of 0, can avoid ozone layer damage, and is particularly suitable for application in refrigeration devices such as air conditioners.

[0005] According to a first aspect of the present invention, the present invention provides a mixed refrigerant composition, which comprises the following components based on mass percentage: component A: 70-80wt% of pentafluoroethane; component B: 20-30wt% of 1,1-difluoroethane; component C: 2-10wt% of hydrocarbons; wherein the hydrocarbons include propane and isobutane.

[0006] According to a second aspect of the present invention, the present invention provides a method for preparing a mixed refrigerant, the method comprising: adding the composition of the present invention into a mixing device, mixing under pressure, and obtaining a mixed refrigerant after mixing evenly.

[0007] According to a third aspect of the present invention, the present invention provides a mixed refrigerant prepared from the mixed refrigerant composition provided by the present invention.

[0008] According to a fourth aspect of the present invention, the present invention provides a use of the mixed refrigerant of the present invention in a refrigeration device.

[0009] The present invention uses pentafluoroethane (R125), 1,1-difluoroethane (R152a), isobutane (R600a) and propane (R290) as mixed raw materials, which can effectively replace R22 refrigerant for use, and during use, the GWP value generated is significantly lower than that of R22 refrigerant, the ODP value is zero, and the ozone layer damage can be avoided, thereby reducing the impact on the environment; at the same time, according to the detection of a third-party organization (Zhejiang Provincial Chemical Product Quality Inspection Station), the mixed refrigerant prepared by the present invention corresponds to GBGB 30000-2013 and belongs to Class E refrigerant, which is not flammable and explosive, and has high safety during storage and use. During the replacement process, the compressor, copper pipe, etc. that originally use R22 as the refrigerant can be used without replacement.

[0010] The various raw materials R125, R152a, R600a and R290 used in the environmentally friendly mixed refrigerant provided by the present invention are easy to obtain in the market. Compared with the quota system sales of R22, there will be a total reduction in a certain period, so the price of R22 refrigerant used in the terminal is relatively high. Therefore, the raw material cost used in the present invention is low, and it only needs to use professional equipment to directly mix according to the ratio under a suitable pressure, and it can be used after reaching the corresponding ratio and mixing evenly. The market prospect is broad and the market can be continuously supplied. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 It is a comparison diagram of the bubble point pressure curve and dew point vapor pressure curve of the mixed refrigerant 11 and the saturated vapor pressure curve of R22, which shows that the bubble point and dew point vapor pressure of the mixed refrigerant of the present invention are slightly different from the saturated vapor pressure of R22, and can be used as a substitute for R22 (at the same temperature, the closer the bubble point pressure and dew point pressure are to R22, the better the direct substitution performance). DETAILED DESCRIPTION

[0012] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0013] The invention provides a mixed refrigerant composition, which comprises the following components: component A: 70-80 wt% of pentafluoroethane; component B: 20-30 wt% of 1,1-difluoroethane; component C: 2-10 wt% of hydrocarbons; wherein the hydrocarbons include propane and isobutane.

[0014] The refrigerant prepared by using the composition of the present invention has good refrigeration effect, can effectively replace R22 refrigerant, has low greenhouse effect, has an ODP value of 0, can avoid ozone layer damage, and is particularly suitable for use in refrigeration devices such as air conditioners.

[0015] According to a preferred embodiment of the present invention, the composition comprises the following components: component A: 72-76 wt% of pentafluoroethane; component B: 22-26 wt% of 1,1-difluoroethane; component C: 1.5-3.5 wt% of isobutane, 1-3 wt% of propane.

[0016] According to a preferred embodiment of the present invention, in the composition, the content of pentafluoroethane is 71.5-72.5wt%, for example, 71.6wt%, 71.7wt%, 71.8wt%, 71.9wt%, 72wt%, 72.1wt%, 72.2wt%, 72.3wt%, 72.4wt% and the like.

[0017] According to a preferred embodiment of the present invention, in the composition, the content of 1,1-difluoroethane is 23.5-25.5wt%, for example, 23.8wt%, 24wt%, 24.2wt%, 24.4wt%, 24.6wt%, 24.8wt%, 25wt%, 25.2wt%, 25.4wt% and the like.

[0018] According to a preferred embodiment of the present invention, in the composition, the content of isobutane is 1.8-2.5wt%, for example, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt% and the like.

[0019] According to a preferred embodiment of the present invention, in the composition, the content of propane is 1-1.5wt%, for example, 1.1wt%, 1.15wt%, 1.2wt%, 1.25wt%, 1.3wt%, 1.35wt%, 1.4wt% and the like.

[0020] The invention provides a method for preparing a mixed refrigerant, which comprises: adding the composition of the invention into a mixing device, mixing under pressure, and obtaining the mixed refrigerant after mixing evenly.

[0021] In the present invention, there is no special requirement for the mixing temperature in the preparation method. The following is an exemplary description, but the scope of the present invention is not limited thereto. According to a preferred embodiment of the present invention, the mixing temperature is not higher than 50°C, preferably 20-30°C.

[0022] In the present invention, there is no special requirement for the mixing pressure in the preparation method. The following is an exemplary description, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the mixing pressure is not higher than 1.94 MPa, preferably 1.53-1.77 MPa.

[0023] In the present invention, there is no special requirement for the mixing time in the preparation method. The following is an exemplary description, but the scope of the present invention is not limited thereto. According to a preferred embodiment of the present invention, the mixing time is 1-5 hours.

[0024] The mixed refrigerant prepared by the present invention has an ODP value of 0, a GWP value of no more than 610, good refrigeration effect, can effectively replace R22 refrigerant, has a low greenhouse effect, can avoid ozone layer damage, is non-flammable and non-explosive, has high safety during storage and use, and is particularly suitable for use in refrigeration devices such as air conditioners. During the replacement process, the compressor, copper pipe, etc. that originally use R22 as the refrigerant can be used without replacement.

[0025] The present invention will be described in detail below through examples.

[0026] In the following embodiments,

[0027] ODP is the ozone depletion potential parameter. The smaller the ODP value, the less damage to the ozone layer.

[0028] GWP is the global warming potential parameter. The smaller the GWP value, the less greenhouse gas emissions and the more environmentally friendly it is. It is measured by the method of greenhouse gas (GHG) emissions = activity data (AD) × emission factor (EF);

[0029] The EER value is the energy efficiency ratio. The higher the EER value, the higher the refrigeration conversion rate, the better the refrigeration effect, and the lower the energy consumption. The specific calculation method is well known to those skilled in the art and will not be described here.

[0030] The boiling point was measured by the Antoine equation calculation method;

[0031] The bubble point, dew point vapor pressure and R22 saturated vapor pressure are calculated using the mathematical expressions of the bubble point equation and the dew point equation (Note: the bubble point equation is a mathematical expression that characterizes the relationship between the composition of a liquid mixture and the operating temperature and pressure; the dew point equation is a mathematical expression that represents the relationship between the composition of a gas mixture and the operating temperature and pressure).

[0032] Pentafluoroethane (R125) is a commercial product of Zhejiang Quhua Fluorine Chemical Co., Ltd.

[0033] 1,1-Difluoroethane (R152a) is a commercial product of Zhejiang Yonghe Refrigeration Co., Ltd.;

[0034] Isobutane (R600a) is a commercial product of Puyang Fengda Fine Chemical Co., Ltd.;

[0035] Propane (R290) is a commercial product of Puyang Fengda Fine Chemical Co., Ltd.

[0036] Example 1

[0037] In terms of mass percentage, 70% R125, 25% R152a, 4% R600a and 1% R290 were added to a mixing device in proportion in liquid state, and mixed at 25°C and 1.62 MPa for 4 hours to obtain a mixed refrigerant 1. The performance parameters were tested, and the results are shown in Table 2.

[0038] Example 2

[0039] In terms of mass percentage, 70.5% of R125, 24.5% of R152a, 3% of R600a and 2% of R290 were added to a mixing device in a liquid state according to a certain proportion, and mixed for 4 hours at 25°C and 1.62MPa to obtain a mixed refrigerant 2. The performance parameters of the mixed refrigerant were tested, and the results are shown in Table 2.

[0040] Example 3

[0041] In terms of mass percentage, 71.3% of R125, 23.7% of R152a, 2% of R600a and 3% of R290 were added to a mixing device in a proportion in liquid state, and mixed at 25°C and 1.62MPa for 4 hours to obtain a mixed refrigerant 3. The performance parameters were tested, and the results are shown in Table 2.

[0042] Example 4

[0043] In terms of mass percentage, 72.7% of R125, 23.3% of R152a, 1% of R600a and 3% of R290 were added to a mixing device in a liquid state according to a certain proportion, and mixed for 4 hours at 27°C and 1.68 MPa to obtain a mixed refrigerant 4. The performance parameters of the mixed refrigerant were tested, and the results are shown in Table 2.

[0044] Example 5

[0045] In terms of mass percentage, 73% of R125, 22% of R152a, 4% of R600a and 1% of R290 were added to a mixing device in a proportion in liquid state, and mixed for 4 hours at 27°C and 1.68 MPa to obtain a mixed refrigerant 5. The performance parameters were tested, and the results are shown in Table 2.

[0046] Example 6

[0047] In terms of mass percentage, 71.5% of R125, 22.5% of R152a, 1% of R600a and 5% of R290 were added to a mixing device in a proportion in liquid state, and mixed for 3.5 hours at 29° C. and 1.7 MPa to obtain a mixed refrigerant 6. The performance parameters of the mixed refrigerant were tested, and the results are shown in Table 2.

[0048] Example 7

[0049] In terms of mass percentage, 73% of R125, 24% of R152a, 2% of R600a and 1% of R290 were added to a mixing device in a liquid state according to a certain proportion, and mixed for 3.5 hours at 30°C and 1.71 MPa to obtain a mixed refrigerant 7. The performance parameters of the mixed refrigerant were tested, and the results are shown in Table 2.

[0050] Example 8

[0051] In terms of mass percentage, 76% of R125, 21.5% of R152a, 1.5% of R600a and 1% of R290 were added to a mixing device in a liquid state according to a certain proportion, and mixed for 3.5 hours at 29° C. and 1.7 MPa to obtain a mixed refrigerant 8. The performance parameters of the mixed refrigerant were tested, and the results are shown in Table 2.

[0052] Example 9

[0053] In terms of mass percentage, 78% R125, 20% R152a, 1% R600a and 1% R290 were added to a mixing device in a proportion in liquid state, and mixed at 30° C. and 1.7 MPa for 3.5 hours to obtain a mixed refrigerant 9. The performance parameters of the mixed refrigerant were tested, and the results are shown in Table 2.

[0054] Example 10

[0055] In terms of mass percentage, 70% of R125, 20% of R152a, 5% of R600a and 5% of R290 were added to a mixing device in a liquid state according to a certain proportion, and mixed for 4 hours at 27° C. and 1.65 MPa to obtain a mixed refrigerant 10. The performance parameters of the mixed refrigerant 10 were tested, and the results are shown in Table 2.

[0056] Embodiment 11

[0057] In terms of mass percentage, 72.1% of R125, 23.8% of R152a, 2.9% of R600a and 1.2% of R290 were added to a mixing device in a liquid state according to a certain proportion, and mixed for 4 hours at 27° C. and 1.68 MPa to obtain a mixed refrigerant 11. The performance parameters of the mixed refrigerant 11 were tested, and the results are shown in Table 2.

[0058]

Performance test

[0059] 1. The saturated liquid properties of the mixed refrigerant 11 were tested and compared with R22. The results are shown in Table 1, which shows that the liquid properties of the mixed refrigerant of the present invention are similar to those of R22 and can be used as a substitute for R22.

[0060] 2. The various properties of the mixed refrigerants obtained in Examples 1 to 11 were tested in a saturated liquid state and compared with R22 refrigerant. The results are shown in Table 2.

[0061] 3. Carry out comparative test of refrigeration conditions on mixed refrigerant 11, obtain its bubble point vapor pressure curve and dew point vapor pressure curve, and compare them with the saturated vapor pressure curve of R22, such as Figure 1 As shown, the curve marked with × is the saturated vapor pressure curve of R22, the curve above the saturated vapor pressure curve of R22 is the bubble point vapor pressure curve of the mixed refrigerant 11, and the curve below is the dew point vapor pressure curve of the mixed refrigerant 11, indicating that the bubble point and dew point vapor pressures of the mixed refrigerant of the present invention are slightly different from the saturated vapor pressure of R22, and can be used as an alternative working fluid to R22.

[0062] Table 1 Comparison of properties of mixed refrigerant 11 and R22 saturated liquid

[0063]

[0064]

[0065] Table 2 Comparison of performance parameters with R22

[0066] serial number Boiling point℃ ODP GWP EER Example 1 -40.5 0 578 +7.9％ Example 2 -40.1 0 601 +7.5％ Example 3 -40.0 0 536 +8.0％ Example 4 -40.0 0 490 +8.0％ Example 5 -39.8 0 499 +7.8％ Example 6 -39.5 0 507 +7.8％ Example 7 -39.4 0 492 +7.4％ Example 8 -39.7 0 483 +8.0％ Example 9 -38.9 0 455 +7.7％ Example 10 -38.5 0 462 +8.2％ Embodiment 11 -40.6 0 428 +9.3％ R22 -40.8 0.05 1700 +4％

[0067] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A mixed refrigerant composition, characterized in that: The composition comprises the following components: Component A: 68-80 wt% of pentafluoroethane; Component B: 18-30 wt% of 1,1-difluoroethane; Component C: 2-10wt% hydrocarbon; Wherein, the hydrocarbons include propane and isobutane.

2. The composition according to claim 1, wherein The composition comprises the following components: Component A: 72-76 wt% of pentafluoroethane; Component B: 22-26 wt% of 1,1-difluoroethane; Component C: 1.5-3.5 wt% of isobutane; Component D: 1-3 wt% propane.

3. The composition according to claim 1 or 2, wherein The content of pentafluoroethane is 71.5-72.5 wt%.

4. The composition according to any one of claims 1 or 2, wherein The content of 1,1-difluoroethane is 23.5-25.5wt%.

5. The composition according to any one of claims 1 or 2, wherein The content of isobutane is 1.8-2.5 wt%.

6. The composition according to any one of claims 1 or 2, wherein The content of propane is 1-1.5 wt%.

7. A method for preparing a mixed refrigerant, characterized in that: The method comprises: adding the composition described in any one of claims 1 to 6 into a mixing device, mixing under pressure, and obtaining a mixed refrigerant after mixing evenly.

8. The method according to claim 7, wherein: Mixing conditions include: The temperature is not higher than 50°C, preferably 20-30°C; and / or The pressure is not higher than 1.94 MPa, preferably 1.53-1.77 MPa; and / or The time is 1-5h.

9. The mixed refrigerant prepared according to claim 7 or 8, wherein the mixed refrigerant preferably has an ODP value of 0 and a GWP value not higher than 610, preferably 420-610.

10. Use of the refrigerant according to claim 9 in a refrigeration device.

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