Hybrid refrigerant compositions and methods of making and using same

Abstract

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

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of energy conversion medium, in particular to a mixed refrigerant composition and a preparation method of the mixed refrigerant and application thereof. BACKGROUND

[0002] Refrigerant, also known as coolant, refrigerant, snow, is a medium substance in various heat engines to complete energy conversion. These substances usually increase power through reversible phase change (such as gas-liquid phase change), such as steam in steam engine, snow in refrigeration machine, etc. Generally, the steam engine releases the heat energy of steam to convert into mechanical energy to generate motive power when working; and the snow of the refrigeration machine is used to transfer heat at low temperature to high temperature.

[0003] With the continuous enhancement of people's environmental protection concept, people begin to develop and select more environmentally friendly refrigerants. The commonly used refrigerant is R22, which is mainly composed of hydrogen, chlorine, fluorine and carbon elements (represented as HCFC), has a destructive effect on the ozone layer, and is listed as a controlled substance in the Montreal Protocol. This kind of substance has been gradually prohibited for use in China, and is mainly composed of hydrogen, chlorine, fluorine and carbon elements (represented as HCFC), and is low in toxicity. SUMMARY

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

[0005] According to the first aspect of the present application, the present application 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 hydrocarbon; wherein the hydrocarbon includes propane, isobutane.

[0006] According to the second aspect of the present application, the present application provides a preparation method of the mixed refrigerant, which comprises: adding the composition of the present application into a mixing device, pressurizing and mixing, and obtaining the mixed refrigerant after uniform mixing.

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

[0008] According to the fourth aspect of the present application, the present application provides application of the mixed refrigerant in refrigeration devices.

[0009] The present application uses pentafluoroethane (R125), 1,1-difluoroethane (R152a), isobutane (R600a) and propane (R290) as mixed refrigerant raw materials, which can effectively replace R22 refrigerant for use, and the GWP value generated during use is significantly reduced compared with R22 refrigerant, the ODP value is zero, and the destruction of the ozone layer can be avoided, thereby reducing the impact on the environment; at the same time, according to the detection of a third party institution (Zhejiang Province Chemical Product Quality Inspection Station), the mixed refrigerant prepared by the present application belongs to the pentane refrigerant according to GB GB 30000-2013, is not flammable and explosive, and has high safety in storage and use. During the replacement process, the compressor, copper pipe and the like originally using R22 as the refrigerant medium do not need to be replaced and can be used.

[0010] The various raw materials R125, R152a, R600a and R290 used in the environmentally friendly mixed refrigerant provided by the present application are convenient to obtain on the market, and compared with R22, the sales are subject to quota system, and there will be total reduction within 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 application is low, and only professional equipment is needed to directly mix according to the proportion under suitable pressure, and the mixed refrigerant can be used after reaching the corresponding proportion and being uniformly mixed, so the market prospect is broad, and the market can be continuously supplied. BRIEF DESCRIPTION OF DRAWINGS

[0011] Figure 1 is a comparison diagram of the bubble point pressure curve and the dew point vapor pressure curve of the mixed refrigerant 11 and the R22 saturated vapor pressure curve, which illustrates that the bubble point and the dew point vapor pressure of the mixed refrigerant of the present application are small in difference from the R22 saturated vapor pressure, and can be used as a replacement working medium of R22 (the closer the bubble point pressure and the dew point pressure to R22 under the same temperature, the better the direct replacement performance). DETAILED DESCRIPTION

[0012] The endpoints of the ranges and any values disclosed in this document are not limited to the precise values stated. The endpoints of the ranges and values are to be rounded to the nearest significant figure. For values which are not atomic weights, values can be rounded off to the nearest 0.1, 0.01 or 0.001. For numerical ranges which include either endpoint, both include the endpoint. For numerical ranges which exclude either endpoint, each endpoint is independently excluded. The ranges and values are to be understood to encompass minor variations from the numerical values given. For values which are atomic weights, the number of significant figures will be the same as the number of significant figures in the atomic weight itself. The ranges and values are to be understood to encompass i) the whole number average of the endpoint values, ii) the range of values between the endpoints, iii) the individual values within the range, and iv) any new ranges or values which can be derived from i), ii) or iii) by combining the endpoints and individual values.

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

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

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

[0016] According to a preferred embodiment of the present application, the content of pentafluoroethane in the composition 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 application, the content of 1,1-difluoroethane in the composition 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 application, the content of isobutane in the composition 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 application, the content of propane in the composition 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 present application provides a preparation method of a mixed refrigerant, which comprises: adding the composition of the present application into a mixing device, pressurizing and mixing, and obtaining a mixed refrigerant after uniform mixing.

[0021] In the present application, the temperature of mixing in the preparation method is not particularly required, and the following exemplary description is provided, but the scope of the present application is not limited thereto, according to a preferred embodiment of the present application, the temperature of mixing is not higher than 50℃, and is preferably 20-30℃.

[0022] In the present application, the pressure for mixing in the preparation method is not particularly required, and the following exemplary description is provided, but the scope of the present application is not limited thereto. According to a preferred embodiment of the present application, the pressure for mixing is not higher than 1.94 MPa, and preferably is 1.53-1.77 MPa.

[0023] In the present application, the time for mixing in the preparation method is not particularly required, and the following exemplary description is provided, but the scope of the present application is not limited thereto. According to a preferred embodiment of the present application, the time for mixing is 1-5 h.

[0024] The mixed refrigerant prepared in the present application has an ODP value of 0 and a GWP value of not higher than 610, has good refrigeration effect, can effectively replace R22 refrigerant, has low greenhouse effect, can avoid destruction of ozone layer, is not flammable and explosive, has high safety in storage and use, and is particularly suitable for application in refrigeration devices such as air conditioners. In the replacement process, the compressor and copper pipe originally using R22 as refrigerant medium can be used without replacement.

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

[0026] In the following examples,

[0027] ODP is the ozone depletion potential parameter, and the smaller the ODP value, the smaller the destruction of the ozone layer;

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

[0029] The EER value is the energy efficiency ratio, and 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 is measured by the antoine equation calculation method;

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

[0032] Pentafluoroethane (R125) is a commercially available product of Zhejiang Quhua Fluorochemical Co., Ltd.;

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

[0034] Isobutane (R600a) is commercially available from Puyang Fengda Fine Chemical Co., Ltd.

[0035] Propane (R290) is commercially available from Puyang Fengda Fine Chemical Co., Ltd.

[0036] Example 1

[0037] 70% of R125, 25% of R152a, 4% of R600a and 1% of R290 were added into a mixing device in proportion in liquid state, and after mixing at 25°C, 1.62 MPa for 4 h, mixed refrigerant 1 was obtained. Its performance parameters were tested, and the results are shown in Table 2.

[0038] Example 2

[0039] 70.5% of R125, 24.5% of R152a, 3% of R600a and 2% of R290 were added into a mixing device in proportion in liquid state, and after mixing at 25°C, 1.62 MPa for 4 h, mixed refrigerant 2 was obtained. Its performance parameters were tested, and the results are shown in Table 2.

[0040] Example 3

[0041] 71.3% of R125, 23.7% of R152a, 2% of R600a and 3% of R290 were added into a mixing device in proportion in liquid state, and after mixing at 25°C, 1.62 MPa for 4 h, mixed refrigerant 3 was obtained. Its performance parameters were tested, and the results are shown in Table 2.

[0042] Example 4

[0043] 72.7% of R125, 23.3% of R152a and 1% of R600a and 3% of R290 were added into a mixing device in proportion in liquid state, and after mixing at 27°C, 1.68 MPa for 4 h, mixed refrigerant 4 was obtained. Its performance parameters were tested, and the results are shown in Table 2.

[0044] Example 5

[0045] 73% of R125, 22% of R152a, 4% of R600a and 1% of R290 were added into a mixing device in proportion in liquid state, and after mixing at 27°C, 1.68 MPa for 4 h, mixed refrigerant 5 was obtained. Its performance parameters were tested, and the results are shown in Table 2.

[0046] Example 6

[0047] By mass percentage, 71.5% R125, 22.5% R152a, 1% R600a, and 5% R290 were added to a mixing device in liquid form in a specific ratio. After mixing at 29°C and 1.7 MPa for 3.5 hours, mixed refrigerant 6 was obtained. Its performance parameters were tested, and the results are shown in Table 2.

[0048] Example 7

[0049] By mass percentage, 73% R125, 24% R152a, 2% R600a, and 1% R290 were added to a mixing device in liquid form in a specific ratio. After mixing at 30°C and 1.71 MPa for 3.5 hours, mixed refrigerant 7 was obtained. Its performance parameters were tested, and the results are shown in Table 2.

[0050] Example 8

[0051] By mass percentage, 76% R125, 21.5% R152a, 1.5% R600a, and 1% R290 were added to a mixing device in liquid form in a specific ratio. After mixing at 29°C and 1.7 MPa for 3.5 hours, mixed refrigerant 8 was obtained. Its performance parameters were tested, and the results are shown in Table 2.

[0052] Example 9

[0053] By mass percentage, 78% R125, 20% R152a, 1% R600a, and 1% R290 were added to a mixing device in liquid form in a specific ratio. After mixing at 30°C and 1.7 MPa for 3.5 hours, mixed refrigerant 9 was obtained. Its performance parameters were tested, and the results are shown in Table 2.

[0054] Example 10

[0055] By mass percentage, 70% R125, 20% R152a, 5% R600a, and 5% R290 were added to a mixing device in liquid form in the specified proportions. After mixing at 27°C and 1.65 MPa for 4 hours, mixed refrigerant 10 was obtained. Its performance parameters were tested, and the results are shown in Table 2.

[0056] Example 11

[0057] By 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 liquid form in a specific ratio. After mixing at 27°C and 1.68 MPa for 4 hours, mixed refrigerant 11 was obtained. Its performance parameters were tested, and the results are shown in Table 2.

[0058] [Performance Testing]

[0059] 1. The saturated liquid property test of the mixed refrigerant 11 is carried out and compared with R22, and the results are shown in Table 1, which shows that the liquid property of the mixed refrigerant of the application is similar to that of R22, and can be used as a substitute for R22.

[0060] 2. The properties of the mixed refrigerants obtained in Examples 1-11 are detected under saturated liquid state and compared with R22 refrigerant, and the results are shown in Table 2.

[0061] 3. The refrigeration working condition comparative test of the mixed refrigerant 11 is carried out, and the bubble point vapor pressure curve and the dew point vapor pressure curve are obtained, which are compared with the saturated vapor pressure curve of R22, as shown in Table 3. Figure 1 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 the saturated vapor pressure curve of R22 is the dew point vapor pressure curve of the mixed refrigerant 11, which shows that the bubble point and dew point vapor pressure of the mixed refrigerant of the application are similar to the saturated vapor pressure of R22, and can be used as a substitute for R22.

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

[0063]

[0064] Table 2 Comparison table of performance parameters with R22

[0065]

[0066] The preferred embodiments of the application are described in detail above, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the application and fall within the protection scope of the application.

Claims

1. A mixed refrigerant composition characterized in that, The composition comprises the following components: Component A: 68-80wt% of pentafluoroethane; Component B: 18-30wt% of 1,1-difluoroethane; Component C: 1.5-3.5wt% of isobutane; Component D: 1-3wt% of propane; the sum of the mass percentages of each component is 100wt%.

2. The composition of claim 1, wherein, The composition comprises the following components: Component A: 72-76wt% of pentafluoroethane; Component B: 22-26wt% of 1,1-difluoroethane; Component C: 1.5-3.5wt% of isobutane; Component D: 1-3wt% of propane; the sum of the mass percentages of each component is 100wt%.

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

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

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

7. A method of producing a mixed refrigerant, characterized by, The method comprises: adding the composition of any one of claims 1-6 into a mixing device, pressurized mixing, and obtaining a mixed refrigerant after uniform mixing.

8. The method of claim 7, wherein, The mixing conditions comprise: a temperature not higher than 50℃; and / or a pressure not higher than 1.94MPa; and / or a time of 1-5h.

9. The method of claim 8, wherein, The mixing conditions comprise: a temperature of 20-30℃; and / or a pressure of 1.53-1.77MPa.

10. The mixed refrigerant prepared according to claim 7 or 8.

11. The mixed refrigerant of claim 10, wherein, The mixed refrigerant has an ODP value of 0 and a GWP value not higher than 610.

12. The mixed refrigerant of claim 11, wherein, The mixed refrigerant has a GWP value of 420-610.

13. Use of the refrigerant of claim 10 or 11 in a refrigeration device.

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