Low-GWP alternative refrigerant capable of replacing R134a, and preparation method and application of low-GWP alternative refrigerant

Abstract

The invention belongs to the technical field of refrigerants, and particularly relates to a low-GWP alternative refrigerant capable of replacing R134a as well as a preparation method and application of the low-GWP alternative refrigerant. The invention relates to a low-GWP (Geotropic Wavelength Protein) alternative refrigerant capable of replacing R134a, which comprises the following components in parts by weight: 70 to 89 parts of 1, 1, 1, 2-tetrafluoroethane, 10 to 20 parts of 1, 1-difluoroethane and 1 to 10 parts of isobutane. As a low-GWP substitute refrigerant capable of replacing R134a, the low-GWP substitute refrigerant has the advantages of excellent environmental protection property, high refrigeration efficiency and good safety on the whole, and can be used for an air conditioning system.

Description

Technical Field

[0001] This invention belongs to the field of refrigerant technology, specifically relating to a low-GWP alternative refrigerant that can replace R134a, its preparation method, and its application. Background Technology

[0002] R134a refrigerant is a widely used HFC refrigerant in air conditioning and heat pump systems, and its main component is tetrafluoroethane. Although R134a has excellent refrigeration performance, its GWP value is relatively high (approximately 1430). In addition, R32 alone, although having a lower GWP (approximately 675), has mild flammability (A2L safety class) and a higher discharge temperature; R152a alone has higher flammability (A2 safety class) and poor refrigeration efficiency; R1216 (hexafluoropropylene) alone has an extremely low GWP (<1), but its thermophysical properties differ significantly from R134a, resulting in poor system compatibility.

[0003] Existing alternatives such as R290, R1234yf, and R410A, while offering improvements in GWP or safety, suffer from issues such as flammability, increased GWP, or significant decreases in refrigeration performance. Therefore, developing a low-GWP, high-performance, safe alternative refrigerant compatible with R134a systems has become an urgent need in the air conditioning industry. The purpose of this invention is to provide a novel hybrid refrigerant with a significantly lower GWP than R134a, while maintaining similar thermodynamic properties and operating characteristics, specifically optimized for refrigeration systems. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a low-GWP alternative refrigerant to R134a, its preparation method, and its applications. This refrigerant possesses advantages such as excellent environmental friendliness, high refrigeration efficiency, and good safety, and can be used in air conditioning systems.

[0005] The technical solution provided by this invention is as follows:

[0006] A low-GWP alternative refrigerant mixture for replacing R134a comprises the following components in parts by weight: 70-89 parts of 1,1,1,2-tetrafluoroethane (R134a, CH2FCF3), 10-20 parts of 1,1-difluoroethane (R152a, CH3CHF2), and 1-10 parts of isobutane (R600a, C4H2O). 10 ).

[0007] Based on the above technical solution:

[0008] The refrigerant provided by this invention has the advantages of significantly reducing the global warming potential by about 24%-35% compared with the existing HFC-134a refrigerant, and having a volumetric cooling capacity and COP that are comparable to or slightly better than those of the existing HFC-134a refrigerant.

[0009] The refrigerant provided by this invention has the advantage of higher safety (by adding R134a to suppress flammability) compared to using 1,1-difluoroethane alone;

[0010] The refrigerant provided by this invention has the advantages of lower operating pressure, higher refrigeration performance, better system compatibility, and no need for large-scale modification of existing R134a systems compared to using 1,1,1,2-tetrafluoroethane alone.

[0011] The refrigerant provided by this invention has the advantage of higher safety compared to using isobutane alone.

[0012] Preferred low-GWP alternative refrigerants to replace R134a include the following components in parts by weight: 70-80 parts of 1,1,1,2-tetrafluoroethane, 10-15 parts of 1,1-difluoroethane, and 1-4 parts of isobutane.

[0013] Preferred low-GWP alternative refrigerants to replace R134a include the following components in parts by weight: 70-80 parts of 1,1,1,2-tetrafluoroethane, 16-20 parts of 1,1-difluoroethane, and 5-10 parts of isobutane.

[0014] Preferred low-GWP alternative refrigerants to replace R134a include the following components in parts by weight: 81-90 parts of 1,1,1,2-tetrafluoroethane, 10-15 parts of 1,1-difluoroethane, and 1-4 parts of isobutane.

[0015] Preferred low-GWP alternative refrigerants to replace R134a include the following components in parts by weight: 81-90 parts of 1,1,1,2-tetrafluoroethane, 16-20 parts of 1,1-difluoroethane, and 5-10 parts of isobutane.

[0016] More preferably, the low GWP alternative refrigerant that can replace R134a comprises the following components in parts by weight: 71 parts of 1,1,1,2-tetrafluoroethane, 12 parts of 1,1-difluoroethane, and 2 parts of isobutane.

[0017] More preferably, the low GWP alternative refrigerant that can replace R134a comprises the following components in parts by weight: 80 parts of 1,1,1,2-tetrafluoroethane, 15 parts of 1,1-difluoroethane, and 5 parts of isobutane.

[0018] More preferably, the low GWP alternative refrigerant that can replace R134a comprises the following components in parts by weight: 88 parts of 1,1,1,2-tetrafluoroethane, 19 parts of 1,1-difluoroethane, and 8 parts of isobutane.

[0019] Specifically: Low-GWP alternative refrigerants that can replace R134a are any combination of the following parts:

[0020] The parts of 1,1,1,2-tetrafluoroethane are 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, and 89.

[0021] The parts of 1,1-difluoroethane are 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.

[0022] The isobutane fractions are 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0023] The present invention also provides a method for preparing the above-mentioned low-GWP alternative refrigerant that can replace R134a, comprising the following steps: according to the weight ratio, injecting the gaseous or liquid components into a pressure-resistant container at room temperature, mixing them uniformly in the liquid phase using a physical mixing method, and obtaining the near-azeotropic R134a alternative refrigerant after standing.

[0024] The present invention also provides applications of the above-mentioned low-GWP alternative refrigerants that can replace R134a, for replacing R134a refrigerant in air-cooled systems; or for replacing R134a refrigerant in water-cooled systems; or for replacing R134a working fluid in heat pumps.

[0025] The beneficial effects of this invention are as follows:

[0026] 1) The GWP value of the refrigerant of this invention is significantly reduced by about 18% to 36% compared with R410A, which has outstanding environmental advantages and is in line with the future development direction of refrigerants;

[0027] 2) Compared with HFC-134a, the refrigerant of this invention has a higher latent heat of vaporization and equivalent or higher refrigeration performance, resulting in high system energy efficiency;

[0028] 3) The evaporation and condensation pressures of the refrigerant are very close to those of HFC-134a, and the compressor refrigeration oil is interchangeable (POE oil can usually be used), making it easy to directly replace the refrigerant.

[0029] 4) The ODP (Ozone Depletion Potential) is zero, meaning it does not damage the ozone layer;

[0030] 5) By adjusting the formula, GWP, refrigeration performance and safety can be flexibly balanced. Detailed Implementation

[0031] The principles and features of the present invention are described below. The embodiments given are only for explaining the present invention and are not intended to limit the scope of the present invention.

[0032] Unless otherwise specified, the test methods used in the embodiments are conventional methods; unless otherwise specified, the materials and reagents used are commercially available.

[0033] Example 1

[0034] A low-GWP alternative refrigerant to replace R134a comprises the following components in parts by weight: 85 parts of 1,1,1,2-tetrafluoroethane, 13 parts of 1,1-difluoroethane, and 2 parts of isobutane.

[0035] The preparation method of refrigerant is as follows:

[0036] According to the above proportions, accurately measure and inject the high-purity raw materials sequentially into a clean, dry pressure-resistant steel cylinder at room temperature (20-25℃) and in a liquid state. After evacuating the cylinder to remove air, purge it with a small amount of inert gas (such as nitrogen) and evacuate again. Finally, fill the cylinder with the mixed working fluid and place it on a rolling mixer to mix for at least 2 hours to ensure uniform mixing of all components. After standing for 24 hours, it is ready for use.

[0037] Example 2

[0038] A low-GWP alternative refrigerant to replace R134a comprises the following components in parts by weight: 76 parts of fluoroethane, 19 parts of 1,1-difluoroethane, and 5 parts of isobutane.

[0039] The refrigerant is prepared as follows: same as in Example 1.

[0040] Example 3

[0041] A low-GWP alternative refrigerant to replace R134a comprises the following components in parts by weight: 70 parts of 1,1,1,2-tetrafluoroethane, 20 parts of 1,1-difluoroethane, and 10 parts of isobutane.

[0042] The refrigerant is prepared as follows: same as in Example 1.

[0043] Example 4

[0044] A low-GWP alternative refrigerant to replace R134a comprises the following components in parts by weight: 89 parts of fluoroethane, 10 parts of 1,1-difluoroethane, and 1 part of isobutane.

[0045] The refrigerant is prepared as follows: same as in Example 1.

[0046] Example 5

[0047] A low-GWP alternative refrigerant to replace R134a comprises the following components in parts by weight: 74 parts of 1,1,1,2-tetrafluoroethane, 18 parts of 1,1-difluoroethane, and 8 parts of isobutane.

[0048] The refrigerant is prepared as follows: same as in Example 1.

[0049] Example 6

[0050] A low-GWP alternative refrigerant to replace R134a comprises the following components in parts by weight: 80 parts of 1,1,1,2-tetrafluoroethane, 15 parts of 1,1-difluoroethane, and 5 parts of isobutane.

[0051] The refrigerant is prepared as follows: same as in Example 1.

[0052] Example 7

[0053] A low-GWP alternative refrigerant to replace R134a comprises the following components in parts by weight: 83 parts of 1,1,1,2-tetrafluoroethane, 14 parts of 1,1-difluoroethane, and 3 parts of isobutane.

[0054] The refrigerant is prepared as follows: same as in Example 1.

[0055] The infusion volumes for the seven embodiments described above are shown in Table 1:

[0056] Table 1. Comparison of R134a infusion volume in Examples 1-7:

[0057]

[0058] The selected design condition is: medium temperature condition. The unit type is suitable for temperate air conditioning of T1 climate type (GB / T7725-2004), and the following values ​​are taken: evaporation temperature = 7.2℃, subcooling = 5℃, condensation temperature = 54.4℃, superheat = 7℃. The compressor isentropic efficiency is 0.8 in the calculation.

[0059] According to the requirements of the national standard GB / T 7725-2022 "Room Air Conditioners", the following data were experimentally measured on the Gree split wall-mounted room air conditioner: KFR-32GW / (32583)FNAa-A3, and the performance parameters were compared: coefficient of performance (COP), relative coefficient of performance (COP), volumetric cooling capacity (Qv), relative unit volumetric cooling capacity (Qv), condensing pressure, GWP, latent heat of vaporization, temperature glide, and lower flammability limit, as shown in Table 2.

[0060] Table 2. Comparison of performance parameters of 7 embodiments of the present invention with R134a

[0061]

[0062] As can be seen from the data in the table above, compared with R134a, the present invention has the following advantages in performance:

[0063] 1) Significantly improved environmental friendliness: The GWP values ​​of all embodiments were lower than those of R134a, with a significant reduction. Among them, the GWP of Embodiment 3 was the lowest, which was 28.1% lower than that of R134a.

[0064] 2) Excellent cooling performance: The cooling capacity per unit volume of all embodiments (except embodiment 4) is higher than that of R134a, while the COP is similar to that of R134a, indicating that they have comparable or better energy efficiency.

[0065] 3) Good thermodynamic properties: The condensation pressure is slightly lower than that of R134a, ensuring good compatibility with existing R134a systems and allowing for direct injection as a replacement.

[0066] Based on the above-mentioned performance advantages, this invention has the following advantages when replacing R134a:

[0067] 1) High feasibility of substitution: Since the working pressure and thermal properties are very close to those of R134a, it can be directly replaced by filling in the existing R134a system without replacing major components (such as compressors and heat exchangers) and lubricating oil, resulting in low modification costs.

[0068] 2) Improve system energy efficiency: The comparable cooling capacity per unit volume and slightly higher COP value are expected to enable the system to maintain or slightly improve its cooling capacity and operating efficiency after replacement.

[0069] 3) Meets environmental regulations: The significantly reduced GWP value enables systems using this refrigerant to meet current and future environmental regulations, extending the market life cycle of the equipment.

[0070] Stable and reliable operation: The near-azeotropic properties reduce performance fluctuations and operational risks caused by component separation in different parts of the system.

[0071] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A low-GWP alternative refrigerant that can replace R134a, characterized in that, It includes the following components in parts by weight: 70-89 parts of 1,1,1,2-tetrafluoroethane, 10-20 parts of 1,1-difluoroethane, and 1-10 parts of isobutane.

2. The low-GWP alternative refrigerant to R134a according to claim 1, characterized in that, It includes the following components in parts by weight: 70-80 parts of 1,1,1,2-tetrafluoroethane, 10-15 parts of 1,1-difluoroethane, and 1-4 parts of isobutane.

3. The low-GWP alternative refrigerant to R134a according to claim 1, characterized in that, It includes the following components in parts by weight: 70-80 parts of 1,1,1,2-tetrafluoroethane, 16-20 parts of 1,1-difluoroethane, and 5-10 parts of isobutane.

4. The low-GWP alternative refrigerant to R134a according to claim 1, characterized in that, It includes the following components in parts by weight: 81-90 parts of 1,1,1,2-tetrafluoroethane, 10-15 parts of 1,1-difluoroethane, and 1-4 parts of isobutane.

5. The low-GWP alternative refrigerant to R134a according to claim 1, characterized in that, It includes the following components in parts by weight: 81-90 parts of 1,1,1,2-tetrafluoroethane, 16-20 parts of 1,1-difluoroethane, and 5-10 parts of isobutane.

6. The low-GWP alternative refrigerant to R134a according to claim 1, characterized in that, It comprises the following components in parts by weight: 71 parts of 1,1,1,2-tetrafluoroethane, 12 parts of 1,1-difluoroethane, and 2 parts of isobutane.

7. The low-GWP alternative refrigerant to R134a according to claim 1, characterized in that, It includes the following components in parts by weight: 80 parts of 1,1,1,2-tetrafluoroethane, 15 parts of 1,1-difluoroethane, and 5 parts of isobutane.

8. The low-GWP alternative refrigerant to R134a according to claim 1, characterized in that, It includes the following components in parts by weight: 88 parts of 1,1,1,2-tetrafluoroethane, 19 parts of 1,1-difluoroethane, and 8 parts of isobutane.

9. A method for preparing a low-GWP alternative refrigerant that can replace R134a according to any one of claims 1 to 8, characterized in that, Includes the following steps: According to the stated weight ratio, the gaseous or liquid components are injected into a pressure-resistant container at room temperature, and then mixed evenly in the liquid state using a physical mixing method. After standing, the product is obtained.

10. An application of a low-GWP alternative refrigerant that can replace R134a according to any one of claims 1 to 8, characterized in that: Used to replace R134a refrigerant in air-cooled systems; Alternatively, it can be used to replace R134a refrigerant in water-cooling systems; Alternatively, it can be used to replace the R134a working fluid in heat pumps.

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