Ternary mixed refrigerant based on layered gradient porous nanomaterial and application of ternary mixed refrigerant

Abstract

The invention belongs to the technical field of substitute commercial R410a refrigerants, and particularly relates to a ternary mixed refrigerant based on a layered gradient porous nanomaterial and application of the ternary mixed refrigerant. The ternary mixed refrigerant based on the layered gradient porous nanomaterial comprises the following components in parts by weight: 35-60 parts of difluoromethane (R-32); 35 to 60 parts of 2, 2, 3, 3, 3-tetrafluoropropene (R-1234yf); 3 to 25 parts of trans-1-chloro-3, 3, 3-trifluoropropene (R-1234zd), 3 to 25 parts of 2, 2, 3, 3-trifluoropropene (R-1234zd); and 1-3 parts of a layered gradient porous nano material. When the refrigerant provided by the invention is applied to the fixed compressor, any original refrigerating system does not need to be replaced, transformation can be carried out without any adjustment, and the refrigerant is compatible with the existing lubricating oil of the fixed compressor. The energy-saving effect is good, and energy is saved by 25%-30% compared with that of an original R410a refrigerant.

Description

Technical Field

[0001] The present invention belongs to the technical field of commercial R410a refrigerant replacement, and particularly relates to a ternary mixed refrigerant based on layered gradient porous nanomaterials and applications thereof. Background Art

[0002] R-410a is currently the mainstream refrigerant in commercial refrigeration equipment, with huge annual usage. Although R-410a does not damage the ozone layer, it has a global warming potential (GWP) of 2100, making it environmentally unsuitable. Its high energy consumption during cooling operation does not meet current requirements for efficient, energy-saving, and green refrigerants, such as those with zero ODP and a very low GWP. Summary of the Invention

[0003] To address the shortcomings of existing technologies, the present invention provides a ternary mixed refrigerant based on layered gradient porous nanomaterials and its application. This refrigerant can be retrofitted to stationary compressors without requiring any replacement or modification of the existing refrigeration system. It is also compatible with existing lubricants used in stationary compressors. It offers significant energy savings, achieving 25%-30% savings over existing R410a refrigerants.

[0004] The technical solutions provided by the present invention are as follows:

[0005] A ternary mixed refrigerant based on layered gradient porous nanomaterials comprises the following components in parts by weight: 35-60 parts of difluoromethane (R-32); 35-60 parts of 2,3,3,3-tetrafluoropropylene (R-1234yf); 3-25 parts of trans-1-chloro-3,3,3-trifluoropropylene (R-1234zd); and 1-3 parts of layered gradient porous nanomaterials.

[0006] The R-32 / R-1234yf / R-1234zd ternary refrigerant based on layered gradient porous nanomaterials provided by the above technical solution has the characteristics of high latent heat and excellent thermal conductivity. The high latent heat of the refrigerant improves system operating efficiency. R-410a, like R-22, has a relatively high GWP, and the two values ​​are comparable. Therefore, the present invention overcomes the high GWP problem of the original R-410a.

[0007] By adding an appropriate concentration of lipophilic porous nanomaterials to a multi-component refrigerant working fluid, a colloidal dispersion with good dispersibility can be formed. Due to the spatial confinement effect of the porous nanomaterial, the movement of molecules within the pore size in the material pores is restricted, but the movement of larger molecules in the solution is not affected by this. The spatial confinement effect has a greater impact on small refrigerant molecules with smaller molecular weight, resulting in a corresponding increase in the boiling point of the smaller molecular weight component, making it closer to the boiling point of the larger molecular weight component, thereby forming an azeotropic solution. Specifically, an appropriate concentration of lipophilic porous nanomaterials is added to a multi-component refrigerant working fluid to obtain an azeotropic colloidal dispersion.

[0008] Specifically, the layered gradient porous nanomaterial is selected from one or more of porous organic skeleton nanomaterials, porous ceramic nanomaterials or porous composite functional group polymer nanomaterials.

[0009] More specifically, the porous organic framework nanomaterial is a metal organic framework nanomaterial or a covalent organic framework nanomaterial.

[0010] More specifically, the porous ceramic nanomaterial is selected from silicon carbide porous nanomaterial or titanium nitride and silicon nitride composite porous nanomaterial.

[0011] Porous ceramic nanomaterials can be selected from existing technologies, for example, silicon carbide (SiC) porous nanomaterials can be purchased from the porous ceramic special nano silicon carbide brand products of Changzhou Angxing New Carbon Materials Co., Ltd., or the silicon carbide (SiC) porous nanomaterials in the patent "A method for preparing silicon carbide nanoporous materials" with application number CN201510512302.1 can be used; titanium nitride-silicon nitride (TiN / Si3N4) porous nanomaterials can be purchased from the titanium nitride-silicon nitride nanocomposite material brand products of Qiyue Biotechnology Co., Ltd.

[0012] Preferably, the following components are included in parts by weight: 50-55 parts of difluoromethane; 35-40 parts of 2,3,3,3-tetrafluoropropylene; 8-12 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

[0013] Preferably, the following components are included in parts by weight: 40-45 parts of difluoromethane; 35-40 parts of 2,3,3,3-tetrafluoropropylene; 18-22 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

[0014] Preferably, the following components are included in parts by weight: 55-60 parts of difluoromethane; 50-55 parts of 2,3,3,3-tetrafluoropropylene; 20-25 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

[0015] Preferably, the following components are included in parts by weight: 35-40 parts of difluoromethane; 55-60 parts of 2,3,3,3-tetrafluoropropylene; 3-7 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

[0016] Preferably, the following components are included in parts by weight: 55-60 parts of difluoromethane; 55-60 parts of 2,3,3,3-tetrafluoropropylene; 10-15 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

[0017] Preferably, the following components are included in parts by weight: 40-45 parts of difluoromethane; 35-40 parts of 2,3,3,3-tetrafluoropropylene; 3-5 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

[0018] Preferably, the following components are included in parts by weight: 48-53 parts of difluoromethane; 38-43 parts of 2,3,3,3-tetrafluoropropylene; 8-13 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

[0019] Preferably, the following components are included in parts by weight: 45-50 parts of difluoromethane; 40-45 parts of 2,3,3,3-tetrafluoropropylene; 5-8 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

[0020] The preparation method of a ternary mixed refrigerant based on layered gradient porous nanomaterials comprises the following steps:

[0021] S1. distilling and purifying three raw materials: difluoromethane, 2,3,3,3-tetrafluoropropene and trans-1-chloro-3,3,3-trifluoropropene;

[0022] S2. The purity of the three raw materials is tested using Agilent chromatography to ensure that their purity reaches refrigerant grade 99.96%;

[0023] S3. Connect the fully automatic mixing tank;

[0024] S4. Evacuate the fully automatic mixing tank to achieve negative pressure;

[0025] S5. The four raw materials are added to the automatic mixing tank in proportion by weight;

[0026] S6 start the automatic mixing device for stirring for 3-6 hours, preferably 3-5 hours;

[0027] S7. The finished product after stirring - azeotropic refrigerant was tested to detect the accuracy of the weight ratio of each component;

[0028] S8. After the product is stirred in the mixing device, it is stable for 3-6 hours, preferably 3-5 hours, and then sampled and tested again;

[0029] S9. Connect the fully automatic packaging machine at the lower end of the mixing device to package the finished product.

[0030] It can also be prepared by referring to existing common methods.

[0031] The present invention also provides an application of a ternary mixed refrigerant based on the layered gradient porous nanomaterial, which is used to replace R-410a refrigerant, such as commercial R-410a refrigerant.

[0032] Replacing R-410a with the ternary mixed refrigerant based on the layered gradient porous nanomaterial provided by the present invention can solve the following problems of R-410a:

[0033] 1. The refrigerant of the present invention has the characteristic of high auto-ignition point, which prevents flammable and explosive accidents;

[0034] 2. The refrigerant of the present invention is used in the original R-410a air conditioner, and the installation and after-sales service are convenient, safe and efficient;

[0035] 3. Compared with the original R-410a, the refrigerant of the present invention can save 25%-30% of energy;

[0036] 4. The operating pressure of the refrigerant of the present invention is only 70% of the original R-410a, which can extend the service life of the air-conditioning compressor;

[0037] 5. The unit cooling capacity of the refrigerant of the present invention is greater than that of the original R-410a, and the charging amount is only 75% of the original R-410a, which is more economical.

[0038] Specifically, it can be used as a refrigerant for a flooded cooler, a dry evaporative cooler, a direct expansion cooler, a refrigeration medium for a stationary air-conditioning system, or a heating medium for a heat pump.

[0039] The refrigerant provided by the present invention was used to directly replace R-410a in tests on original equipment. Due to its large latent heat of evaporation and faster cooling rate per unit time, its refrigeration efficiency is high. Three years of uninterrupted experimental data have proved that it has a good energy-saving effect. When used in fixed commercial air-conditioning equipment using R-410a as the refrigerant, energy savings of 25%-30% can be achieved.

[0040] The refrigerant provided by the present invention has improved flame retardancy and a lower global warming potential (GWP). During the experimental period, 25 ignition tests were conducted, demonstrating the refrigerant's strong flame retardancy. The refrigerant provided by the present invention is non-flammable and non-toxic. It does not damage the ozone layer and has an extremely low greenhouse effect.

[0041] The refrigerant provided by the present invention has a higher cooling capacity than R-410a, which can enable the compressor to be unloaded in advance. Due to the mixing of layered gradient porous nanomaterials, it has better flow properties and low delivery pressure, which reduces the working pressure of the compressor. Unloading in advance and reducing the working pressure can effectively extend the service life of the compressor.

[0042] The chemical properties of the various components of the refrigerant provided by the present invention are relatively stable. DETAILED DESCRIPTION

[0043] The principles and features of the present invention are described below. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0044] Unless otherwise specified, the test methods used in the examples are conventional methods; the materials and reagents used are commercially available reagents and materials unless otherwise specified.

[0045] The porous nanomaterials were purchased from the titanium nitride-silicon nitride nanocomposite material brand product of Qiyue Biotechnology Co., Ltd.

[0046] Example 1

[0047] A refrigerant replacing R-410a is prepared by fully mixing the following raw materials in parts by weight: 48 parts of difluoromethane; 43 parts of 2,3,3,3-tetrafluoropropylene; 7 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1 part of a layered gradient porous nanomaterial.

[0048] The preparation method is as follows:

[0049] S1. Difluoromethane, 2,3,3,3-tetrafluoropropene, and trans-1-chloro-3,3,3-trifluoropropene are distilled and purified on the production line. The distillation tower must be high enough to produce 99.99% refrigerant raw materials.

[0050] S2. The purity of the three raw materials is tested using Agilent chromatography to ensure that their purity reaches refrigerant grade 99.96%;

[0051] S3. Connect the new fully automatic mixing tank;

[0052] S4. Evacuate the new fully automatic mixing tank to achieve negative pressure;

[0053] S5. Add the four qualified raw materials to the new fully automatic mixing tank according to the weight ratio;

[0054] S6. Start the new fully automatic mixing device and stir for three hours;

[0055] S7. After stirring for three hours, the finished product - the mixed refrigerant - is tested to check the accuracy of the weight ratio of its components.

[0056] S8. After the product is stirred in the mixing device for three hours and then stabilized for three hours, sample and test again;

[0057] S9. Connect the lower end of the mixing device to mix the layered gradient porous nanomaterials and perform subpackaging on the fully automatic subpackaging machine to obtain the finished product.

[0058] Example 2

[0059] A refrigerant for replacing R-410a is prepared by fully mixing the following raw materials in parts by weight: 53 parts of difluoromethane; 38 parts of 2,3,3,3-tetrafluoropropene; 10 parts of trans-1-chloro-3,3,3-trifluoropropene; and 1 part of a layered gradient porous nanomaterial.

[0060] The preparation method is basically the same as that of Example 1.

[0061] Example 3

[0062] A refrigerant replacing R-410a is prepared by fully mixing the following raw materials in parts by weight: 43 parts of difluoromethane; 38 parts of 2,3,3,3-tetrafluoropropylene; 20 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 2 parts of layered gradient porous nanomaterial.

[0063] The preparation method is basically the same as that of Example 1.

[0064] Example 4

[0065] A refrigerant replacing R-410a is prepared by fully mixing the following raw materials in parts by weight: 58 parts of difluoromethane; 53 parts of 2,3,3,3-tetrafluoropropene; 23 parts of trans-1-chloro-3,3,3-trifluoropropene; and 1 part of a layered gradient porous nanomaterial.

[0066] The preparation method is basically the same as that of Example 1.

[0067] Example 5

[0068] A refrigerant replacing R-410a is prepared by fully mixing the following raw materials in parts by weight: 38 parts of difluoromethane; 58 parts of 2,3,3,3-tetrafluoropropene; 5 parts of trans-1-chloro-3,3,3-trifluoropropene; and 2 parts of layered gradient porous nanomaterial.

[0069] The preparation method is basically the same as that of Example 1.

[0070] Example 6

[0071] A refrigerant replacing R-410a is prepared by fully mixing the following raw materials in parts by weight: 58 parts of difluoromethane; 58 parts of 2,3,3,3-tetrafluoropropylene; 13 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1 part of a layered gradient porous nanomaterial.

[0072] The preparation method is basically the same as that of Example 1.

[0073] Example 7

[0074] A refrigerant replacing R-410a is prepared by fully mixing the following raw materials in parts by weight: 43 parts of difluoromethane; 38 parts of 2,3,3,3-tetrafluoropropylene; 4 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 3 parts of layered gradient porous nanomaterials.

[0075] The preparation method is basically the same as that of Example 1.

[0076] Example 8

[0077] A refrigerant replacing R-410a is prepared by fully mixing the following raw materials in parts by weight: 51 parts of difluoromethane; 41 parts of 2,3,3,3-tetrafluoropropylene; 11 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 2 parts of layered gradient porous nanomaterial.

[0078] The preparation method is basically the same as that of Example 1.

[0079] Comparative Example 1

[0080] Refer to Example 1, except that the layered gradient porous nanomaterial is not added in the preparation method.

[0081] The refrigerants prepared in the above embodiments are used as test objects and tested according to relevant standards of the prior art to obtain the physical property parameters of each refrigerant.

[0082] Taking the data measured in Example 1 as an example, its physical properties are as follows:

[0083] Boiling point ≈ -51.5℃, safety A2L, slip temperature ≈ 0.5℃, latent heat at 5℃ ≈ 248kJ / kg, latent heat at 40℃ ≈ 190.7kJ / kg, condensing pressure at 40℃ ≈ 2.093MPa, GWP ≈ 341. Compared with R410a, the 40℃ / 5℃ pressure ratio is reduced from 2.58 to 2.56.

[0084] From the above physical parameters, it can be seen that the refrigerant provided by the present invention has the characteristics of replacing R-410a, and its biggest advantage is that its GWP value is much smaller than R-410a, followed by energy saving in operation.

[0085] It can be seen from the physical property parameters of Comparative Example 1 that the slip temperature can be significantly reduced by more than 0.5° C. by adding the layered gradient porous nanomaterial.

[0086] Effect Examples

[0087] In order to further illustrate the energy-saving advantages of the refrigerant provided by the present invention, the present invention installed two split-type heat pump units, namely Unit 1 and Unit 2, in an application laboratory to conduct actual energy-saving experiments.

[0088] The application laboratory is equipped with two split heat pump units, Unit 1 and Unit 2. Unit 1 operates with the original R-410a refrigerant, while Unit 2 operates with the refrigerant of the present invention. A 550-day energy-saving test was conducted, and the overall energy-saving rate reached over 28%. The application laboratory hardware equipment is identical (same manufacturer, same model, same type, same power, same operating conditions).

[0089] Two modular units in the application laboratory (with the refrigerants prepared in Examples 1 to 8 and Comparative Example 1) were operated for 550 working days, and the energy saving rate was calculated by collecting daily data on a computer. At present, the compressors of Units 1 and 2 are operating normally, and the specific energy saving effects are as follows:

[0090] Example Group 1 2 3 4 5 6 7 8 Energy saving rate (%) 30.4 30.1 28.3 29.6 27.9 31.1 27.5 29.9

[0091] The energy saving rate is calculated as follows: (original R-410a energy consumption - embodiment energy consumption) / original R-410a energy consumption.

[0092] According to the energy saving data, we can see that:

[0093] 1) Compared with R-410a refrigerant, the refrigerant provided by the present invention can significantly improve energy saving rate by more than 27%;

[0094] 2) The present invention can significantly increase the energy saving rate by 5-8% by adding layered gradient porous nanomaterials.

[0095] 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 in the scope of protection of the present invention.

Claims

1. A ternary mixed refrigerant based on layered gradient porous nanomaterials, characterized in that: The invention comprises the following components in parts by weight: 35-60 parts of difluoromethane; 35-60 parts of 2,3,3,3-tetrafluoropropylene; 3-25 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

2. The ternary mixed refrigerant based on layered gradient porous nanomaterials according to claim 1, characterized in that: The layered gradient porous nanomaterial is selected from one or more of porous organic skeleton nanomaterials, porous ceramic nanomaterials or porous composite functional group polymer nanomaterials.

3. The ternary mixed refrigerant based on layered gradient porous nanomaterials according to claim 2, characterized in that: The porous organic framework nanomaterial is a metal organic framework nanomaterial or a covalent organic framework nanomaterial.

4. The ternary mixed refrigerant based on layered gradient porous nanomaterials according to claim 2, characterized in that: The porous ceramic nanomaterial is selected from silicon carbide porous nanomaterial or titanium nitride and silicon nitride composite porous nanomaterial.

5. The ternary mixed refrigerant based on layered gradient porous nanomaterials according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 50-55 parts of difluoromethane; 35-40 parts of 2,3,3,3-tetrafluoropropylene; 8-12 parts of trans-1-chloro-3,3,3-trifluoropropylene; 1-3 parts of layered gradient porous nanomaterial; Alternatively, the composition comprises the following components in parts by weight: 40-45 parts of difluoromethane; 35-40 parts of 2,3,3,3-tetrafluoropropylene; 18-22 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

6. The ternary mixed refrigerant based on layered gradient porous nanomaterials according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 55-60 parts of difluoromethane; 50-55 parts of 2,3,3,3-tetrafluoropropylene; 20-25 parts of trans-1-chloro-3,3,3-trifluoropropylene; 1-3 parts of layered gradient porous nanomaterial; Alternatively, the composition comprises the following components in parts by weight: 35-40 parts of difluoromethane; 55-60 parts of 2,3,3,3-tetrafluoropropylene; 3-7 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

7. The ternary mixed refrigerant based on layered gradient porous nanomaterials according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 55-60 parts of difluoromethane; 55-60 parts of 2,3,3,3-tetrafluoropropylene; 10-15 parts of trans-1-chloro-3,3,3-trifluoropropylene; 1-3 parts of layered gradient porous nanomaterial; Alternatively, the composition comprises the following components in parts by weight: 40-45 parts of difluoromethane; 35-40 parts of 2,3,3,3-tetrafluoropropylene; 3-5 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

8. The ternary mixed refrigerant based on layered gradient porous nanomaterials according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 48-53 parts of difluoromethane; 38-43 parts of 2,3,3,3-tetrafluoropropylene; 8-13 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterials. Alternatively, the composition comprises the following components in parts by weight: 45-50 parts of difluoromethane; 40-45 parts of 2,3,3,3-tetrafluoropropylene; 5-8 parts of trans-1-chloro-3,3,3-trifluoropropylene; and 1-3 parts of layered gradient porous nanomaterial.

9. Use of a ternary mixed refrigerant based on layered gradient porous nanomaterials according to any one of claims 1 to 8, characterized in that: Used to replace R-410a refrigerant.

10. The use according to claim 9, characterized in that: It can be used as a refrigerant for flooded coolers, dry evaporative coolers, direct expansion coolers, cooling media for stationary air conditioning systems, or heating media for heat pumps.