A nano quaternary mixed refrigerant and its application

Abstract

The present invention belongs to the field of refrigerant technology, and specifically relates to a nano quaternary mixed refrigerant and its application. The nano quaternary mixed refrigerant is composed of the following components in parts by weight: tetrafluoropropylene R-1234ZE: 35-60 parts; propane R-290: 25-55 parts; trifluoroiodomethane R-13I1: 10-30 parts; porous nano metal material 2-5 parts. The nano quaternary mixed refrigerant provided by the present invention has the characteristics of green environmental protection, high efficiency and energy saving, and can be used to replace R-22 and R-407C refrigerants in fixed compressors for household, industrial and commercial purposes.

Description

Technical Field

[0001] The invention belongs to the technical field of refrigerants, and in particular relates to a nano quaternary mixed refrigerant and application thereof. Background Art

[0002] R-22 and R-407C are currently the mainstream refrigerants for household, industrial and commercial refrigeration equipment, and are used in huge quantities every year. R-22 damages the ozone layer, and its global warming potential reaches / (GWP) 1700. It is not environmentally friendly, and its energy consumption is relatively high during refrigeration operation, which cannot meet the current national requirements for high-efficiency, energy-saving and green refrigerants. In order to protect the ozone layer and reduce the greenhouse effect, not only is the ODP of the refrigerant required to be zero, but the GWP must also meet domestic and international standards. Therefore, it is necessary to develop green, energy-saving and environmentally friendly refrigerants. Summary of the invention

[0003] In order to solve the deficiencies of the prior art, the present invention provides a nano quaternary mixed refrigerant and its application. The nano quaternary mixed refrigerant provided by the present invention has the characteristics of green environmental protection, high efficiency and energy saving, and can be used to replace R-22 and R-407C refrigerants in fixed compressors for household, industrial and commercial use, solving the problems of high pollution and high energy consumption of R-22 and R-407C refrigerants in current household, industrial and commercial refrigeration equipment.

[0004] The technical solution provided by the present invention is as follows:

[0005] A nanometer quaternary mixed refrigerant is composed of the following components in parts by weight: 35-60 parts of tetrafluoropropylene R-1234ZE; 25-55 parts of propane R-290; 10-30 parts of trifluoroiodomethane R-13I1; and 2-5 parts of porous nanometer metal material.

[0006] In the above technical solution:

[0007] R-290 not only has zero ODP, but also zero GWP;

[0008] R-1234ZE not only has zero ODP, but also a GWP of only 0.19;

[0009] R-13I1 not only has zero ODP and a GWP of only 1, but also has a large cooling capacity and functions as a flame retardant and increases the auto-ignition point;

[0010] The addition of porous nano-metal materials not only improves the hardness of the compressor tank, but also promotes azeotropy and enhances lubrication and leak-blocking functions;

[0011] The combination of the above four raw materials has the characteristics of large latent heat, good thermal conductivity, and improved system operation efficiency. Although R-290 is flammable, R13I1 is added for flame retardancy to overcome the shortcomings of the raw materials.

[0012] Preferably, it is composed of the following components in parts by weight: tetrafluoropropylene R-1234ZE: 45-55 parts; propane R-290: 25-35 parts; trifluoroiodomethane R-13I1: 15-25 parts; porous nano-metal material: 2-5 parts.

[0013] Preferably, it is composed of the following components in parts by weight: tetrafluoropropylene R-1234ZE: 40-50 parts; propane R-290: 30-40 parts; trifluoroiodomethane R-13I1: 10-20 parts; porous nano-metal material: 2-5 parts.

[0014] Preferably, it is composed of the following components in parts by weight: tetrafluoropropylene R-1234ZE: 43-53 parts; propane R-290: 33-43 parts; trifluoroiodomethane R-13I1: 13-23 parts; porous nano-metal material: 2-5 parts.

[0015] Preferably, it is composed of the following components in parts by weight: tetrafluoropropylene R-1234ZE: 43-53 parts; propane R-290: 28-38 parts; trifluoroiodomethane R-13I1: 18-28 parts; porous nano-metal material: 2-5 parts.

[0016] Preferably, it is composed of the following components in parts by weight: tetrafluoropropylene R-1234ZE: 35-45 parts; propane R-290: 33-43 parts; trifluoroiodomethane R-13I1: 15-30 parts; porous nano-metal material: 2-5 parts.

[0017] Preferably, it is composed of the following components in parts by weight: tetrafluoropropylene R-1234ZE: 45-60 parts; propane R-290: 30-45 parts; trifluoroiodomethane R-13I1: 10-15 parts; porous nano-metal material: 2-5 parts.

[0018] Preferably, it is composed of the following components in parts by weight: tetrafluoropropylene R-1234ZE: 42-58 parts; propane R-290: 40-55 parts; trifluoroiodomethane R-13I1: 10-15 parts; porous nano-metal material: 2-5 parts.

[0019] Preferably, it is composed of the following components in parts by weight: tetrafluoropropylene R-1234ZE: 40-50 parts; propane R-290: 40-50 parts; trifluoroiodomethane R-13I1: 10-20 parts; porous nano-metal material: 2-5 parts.

[0020] Specifically, the porous nanometal material is selected from the existing MOF-205 material and nickel-based Ni-MOF material. For example, MOF-205 porous nanomaterial can be purchased from Qiyue Biotechnology Co., Ltd.; nickel-based Ni-MOF porous nanomaterial can be purchased from the porous nickel-based Ni-MOF material brand product of Xi'an Ruixi Biotechnology Co., Ltd.

[0021] The present invention also provides the application of the nano quaternary mixed refrigerant for replacing R-22 or R-407C in a full-liquid, dry evaporative cooler, a direct expansion cooler, a fixed air-conditioning system or a mobile air-conditioning system.

[0022] Specific: Refrigeration systems for flooded, dry evaporative coolers, direct expansion coolers, fixed air conditioning systems or mobile air conditioning systems.

[0023] The nanometer quaternary mixed refrigerant provided by the present invention can be applied to fixed compressors with an input power of 1KW-500KW, without replacing any original refrigeration system or making any adjustments; the energy-saving effect is good, saving 20-30% energy compared with the original R-22 and R-407C refrigerants.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1) The refrigerant provided by the present invention can be directly injected into the refrigeration equipment originally using R-22 and R-407C or added at any time, without replacing any parts of the refrigeration equipment, thus realizing the "drop in" (direct injection) and "add in" (add at any time) in the field of fluorine product R-22 and R-407C replacement. The raw materials tetrafluoropropylene, fluoroethane, trifluoroiodomethane, and porous nano-metal materials in the energy-saving and environmentally friendly refrigerant provided by the present invention have low water solubility, will not chemically react with the lubricating oil in the original equipment using R-22 and R-407C, and are compatible with the lubricating oil in the original equipment. Therefore, it does not require any replacement of the original refrigeration equipment and is a refrigerant that can be put into use without adjustment, thus avoiding the huge waste of equipment caused by the replacement of refrigerants and the unnecessary economic losses to users.

[0026] 2) The refrigerant for household, industrial and commercial air conditioning systems provided by the present invention directly replaces R-22 and R-407C and is tested on the original equipment. Because of its large latent heat of evaporation and faster cooling speed per unit time, its refrigeration efficiency is high. The experimental data of three years in the laboratory prove that it has good energy-saving effect. It can save 20-30% of energy when applied to fixed industrial and commercial air conditioning equipment with R-22 and R-407C as refrigerants. Trifluoroiodomethane has better flame retardancy and lower GWP value, as proved by the results of 30 ignition tests in the laboratory in three years. At the same time, the ignition point, flash point and toxicity tests were conducted by the Institute of Chemistry. The auto-ignition point reached 675 degrees, proving that trifluoroiodomethane has strong flame retardancy. Therefore, the refrigerant provided by the present invention is non-flammable, non-toxic, and has a flash point of 100 degrees closed cup. While not destroying the ozone layer, it also has extremely low greenhouse effect.

[0027] 3) The refrigerant for household, industrial and commercial air conditioning systems provided by the present invention has a unit refrigeration capacity of 126% of that of R-22 and R-407C, so its filling amount is 75% of that of R-22 and R-407C.

[0028] 4) The cooling capacity of the refrigerant provided by the present invention is 4-8% higher than that of R-22 and R-407C, which can make the compressor unloaded in advance. At the same time, the refrigerant provided by the present invention is a mixed refrigerant whose average molecular weight is smaller than that of R-22 and R-407C products, has good flowability, 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.

[0029] 5) The product of the present invention has an ozone layer ODP of zero and a GOP greenhouse index of 8, which is one hundred and twenty times that of the traditional refrigerant R22. For example, a large chiller of 1000KW / H refrigeration equipment runs 5000 hours per year. By comparing greenhouse gases with new and old refrigerants and calculating carbon emissions, 600 tons of carbon emissions can be reduced per year.

[0030] 6) The present invention replaces the refrigerants of traditional refrigeration equipment for household, industrial and commercial air conditioners, and reduces the energy consumption of the equipment by more than 20%. For example, a large chiller of 1000KW / H refrigeration equipment runs 5000 hours per year and consumes 5 million kWh of electricity per year. If the energy saving is calculated by 20%, 1 million kWh of electricity can be saved.

[0031] 7) Household, industrial and commercial air conditioning equipment with a capacity of 1000KW / H and running for 5000 hours per year can reduce carbon emissions by 985 tons per year.

[0032] 8) Household, industrial and commercial air-conditioning equipment 1000KW / H, running 5000 hours per year, comparing greenhouse gas emissions and energy saving of 20% between new and old refrigerants, saving 1 million kWh of electricity, reducing carbon emissions by 985 tons per year, and reducing emissions by 1585 tons per year in total.

[0033] 9) The product of the present invention contains porous nano-metal materials. After the compressor of the refrigeration equipment is operated, the compressor tank absorbs the nano-particles, which increases the wear resistance of the compressor tank by 30% and extends the service life of the compressor by more than 30%. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a preparation flow chart of the refrigerant provided by the present invention. DETAILED DESCRIPTION

[0035] 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.

[0036] 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.

[0037] Example 1

[0038] An energy-saving and environmentally friendly refrigerant for household, industrial and commercial refrigeration equipment, which is prepared by fully mixing the following raw materials in parts by weight: tetrafluoropropylene R-1234ZE: 50 parts; propane R-290: 30 parts; trifluoroiodomethane R-13I1: 15 parts; porous nano-metal material 5 parts. The preparation method is as follows:

[0039] S1. The purity of the four raw materials is tested by Agilent Colorimeter to ensure that their purity reaches the refrigerant grade of 99.96%;

[0040] S2. Connect the new fully automatic mixing tank;

[0041] S3. Evacuate the new fully automatic mixing tank to achieve negative pressure;

[0042] S4. Add the qualified raw materials into the new automatic mixing tank according to the weight ratio;

[0043] S5. Start the new fully automatic mixing device to stir for three hours;

[0044] S6. The finished product after three hours of stirring - the mixed refrigerant was tested to detect the accuracy of the weight ratio of each component;

[0045] S7. After the product is stirred in the mixing device for three hours, it is stabilized for three hours and then sampled and tested again;

[0046] S8. Connect the fully automatic packaging machine at the lower end of the mixing device to package the finished product.

[0047] The process can be referred to Figure 1 .

[0048] Example 2

[0049] A refrigerant replacing R-22 and R-407C is prepared by fully mixing the following raw materials in parts by weight: tetrafluoropropylene R-1234ZE: 45 parts; propane R-290: 35 parts; trifluoroiodomethane R-13I1: 15 parts; porous nano-metal material 5 parts. The preparation method is basically the same as that of Example 1.

[0050] Example 3

[0051] A refrigerant replacing R-22 and R-407C is prepared by fully mixing the following raw materials in parts by weight: tetrafluoropropylene R-1234ZE: 45 parts; propane R-290: 30 parts; trifluoroiodomethane R-13I1: 20 parts; porous nano-metal material 5 parts. The preparation method is basically the same as that of Example 1.

[0052] Example 4

[0053] A refrigerant that replaces R-22 and R-407C is prepared by fully mixing the following raw materials in parts by weight: tetrafluoropropylene R-1234ZE: 45 parts; propane R-290: 25 parts; trifluoroiodomethane R-13I1: 25 parts; and 5 parts of porous nanometal material. The preparation method is basically the same as that of Example 1.

[0054] Example 5

[0055] A refrigerant that replaces R-22 and R-407C is prepared by fully mixing the following raw materials in parts by weight: tetrafluoropropylene R-1234ZE: 40 parts; propane R-290: 35 parts; trifluoroiodomethane R-13I1: 20 parts; and porous nanometal material 35 parts. The preparation method is basically the same as that of Example 1.

[0056] Example 6

[0057] A refrigerant that replaces R-22 and R-407C is prepared by fully mixing the following raw materials in parts by weight: tetrafluoropropylene R-1234ZE: 35 parts; propane R-290: 35 parts; trifluoroiodomethane R-13I1: 25 parts; and porous nanometal material 5 parts. The preparation method is basically the same as that of Example 1.

[0058] Example 7

[0059] A refrigerant that replaces R-22 and R-407C is prepared by fully mixing the following raw materials in parts by weight: tetrafluoropropylene R-1234ZE: 35 parts; propane R-290: 35 parts; trifluoroiodomethane R-13I1: 27 parts; and 3 parts of porous nanometal material. The preparation method is basically the same as that of Example 1.

[0060] Example 8

[0061] A refrigerant that replaces R-22 and R-407C is prepared by fully mixing the following raw materials in parts by weight: tetrafluoropropylene R-1234ZE: 35 parts; propane R-290: 34 parts; trifluoroiodomethane R-13I1: 27 parts; and 2 parts of porous nanometal material. The preparation method is basically the same as that of Example 1.

[0062] Performance Test:

[0063] Comparative Example 1 is R-22, and Comparative Example 2 is R-407C.

[0064] The performance test results are shown in the following table:

[0065]

[0066]

[0067] Effect example

[0068] In order to further illustrate the energy-saving advantages of the refrigerant provided by the present invention, two modular units were installed in Application Laboratory No. 1 of the company's Engineering Research Center, which are divided into Unit 1 and Unit 2; two compressors of central air conditioners were installed in Application Laboratory No. 2, which are divided into Compressor No. 1 and Compressor No. 2; actual energy-saving experiments were carried out, and the specific test contents were taken as examples for explanation.

[0069] Two modular units were installed in the No. 1 application laboratory, namely Unit 1 and Unit 2. One was R-22 and the other adopted the product of the present invention. Energy-saving tests were conducted for 750 working days, and the comprehensive energy-saving rate reached 26.37%.

[0070] Application Laboratory No. 2 is equipped with two central air-conditioning compressors, namely compressor No. 1 and compressor No. 2. One compressor is R-407C and the other compressor adopts the product of the present invention. After 750 working days of energy-saving tests, the comprehensive energy-saving rate also reached more than 27.45%.

[0071] The two application laboratories have the same hardware equipment (same manufacturer, same model, same type, same power, same working conditions).

[0072] The two module units in the No. 1 application laboratory (using the refrigerants prepared in Examples 1 to 8) were operated for 750 working days, and the energy saving rate was calculated by collecting daily data with a computer. At present, the compressors of Units 1 and 2 are working normally. The specific energy saving rate calculation method is as follows.

[0073]

[0074] The two compressor units of the central air conditioner of the No. 2 application laboratory (with the refrigerant prepared in Examples 1 to 8) were operated for 750 working days, and the energy saving rate was calculated by collecting daily data by computer. At present, the No. 1 compressor unit and the No. 2 compressor unit are operating normally. The specific energy saving rate calculation method is as follows.

[0075]

[0076] 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 principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A nano quaternary mixed refrigerant, characterized in that: The invention is composed of the following components in parts by weight: 35-60 parts of tetrafluoropropylene R-1234ZE; 25-55 parts of propane R-290; 10-30 parts of trifluoroiodomethane R-13I1; and 2-5 parts of porous nano-metal material.

2. The nano quaternary mixed refrigerant according to claim 1, characterized in that: The invention is composed of the following components in parts by weight: 45-55 parts of tetrafluoropropylene R-1234ZE; 25-35 parts of propane R-290; 15-25 parts of trifluoroiodomethane R-13I1; and 2-5 parts of porous nano-metal material.

3. The nano quaternary mixed refrigerant according to claim 1, characterized in that: The invention is composed of the following components in parts by weight: 40-50 parts of tetrafluoropropylene R-1234ZE; 30-40 parts of propane R-290; 10-20 parts of trifluoroiodomethane R-13I1; and 2-5 parts of porous nano-metal material.

4. The nano quaternary mixed refrigerant according to claim 1, characterized in that: The invention is composed of the following components in parts by weight: 43-53 parts of tetrafluoropropylene R-1234ZE; 33-43 parts of propane R-290; 13-23 parts of trifluoroiodomethane R-13I1; and 2-5 parts of porous nano-metal material.

5. The nano quaternary mixed refrigerant according to claim 1, characterized in that: The invention is composed of the following components in parts by weight: 43-53 parts of tetrafluoropropylene R-1234ZE; 28-38 parts of propane R-290; 18-28 parts of trifluoroiodomethane R-13I1; and 2-5 parts of porous nano-metal material.

6. The nano quaternary mixed refrigerant according to claim 1, characterized in that: The invention is composed of the following components in parts by weight: 35-45 parts of tetrafluoropropylene R-1234ZE; 33-43 parts of propane R-290; 15-30 parts of trifluoroiodomethane R-13I1; and 2-5 parts of porous nano-metal material.

7. The nano quaternary mixed refrigerant according to claim 1, characterized in that: It is composed of the following components in parts by weight: Tetrafluoropropylene R-1234ZE: 45-60 parts; propane R-290: 30-45 parts; trifluoroiodomethane R-13I1: 10-15 parts; porous nanometal material 2-5 parts; Alternatively, tetrafluoropropylene R-1234ZE: 42-58 parts; propane R-290: 40-55 parts; trifluoroiodomethane R-13I1: 10-15 parts; porous nanometal material 2-5 parts; Alternatively, tetrafluoropropylene R-1234ZE: 40-50 parts; propane R-290: 40-50 parts; trifluoroiodomethane R-13I1: 10-20 parts; porous nano-metal material: 2-5 parts.

8. The nano quaternary mixed refrigerant according to claim 1, characterized in that: The porous nano-metal material is selected from MOF-205 material or nickel-based Ni-MOF material.

9. An application of the nano quaternary mixed refrigerant according to any one of claims 1 to 8, characterized in that: For use as a replacement for R-22 or R-407C in flooded, dry evaporative coolers, direct expansion coolers, stationary air conditioning systems, or mobile air conditioning systems.

10. The use according to claim 9, characterized in that: Refrigeration systems for flooded, dry evaporative coolers, direct expansion coolers, stationary air conditioning systems or mobile air conditioning systems.

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