Composition of fluoroolefin and fluoroalkane

Abstract

The present invention discloses a composition of fluoroolefin and fluoroalkane, which comprises 70 to 80 parts by weight of 2,3,3,3-tetrafluoropropene, 10 to 20 parts by weight of trans-1,3,3,3-tetrafluoropropene, 5 to 10 parts by weight of 1,1,1,2-tetrafluoroethane, and 2 to 5 parts by weight of difluoromethane. The composition of the present invention has the advantages of low GWP, being environmentally friendly, having a high refrigeration effect, and being highly compatible with lubricants.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates to fluorinated hydrocarbon compositions, and in particular to compositions of fluoroolefins and fluoroalkanes. [Background technology]

[0002] In recent years, the world has become increasingly concerned about potential harm to the Earth's atmosphere and climate. Chlorine-containing compounds, such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and their analogues, are being gradually phased out for use as refrigerants in air conditioning and refrigeration systems due to the ozone-depleting properties associated with many of these compounds. This has led to a growing need for new fluorocarbon and hydrofluorocarbon compounds and compositions as replacements for refrigeration and heat pump applications. For example, there is a need to improve chlorine-containing refrigeration systems by replacing chlorine-containing refrigerants with chlorine-free refrigerant compounds, such as hydrofluorocarbons (HFCs), that do not deplete the ozone layer.

[0003] The main substitute for the refrigerant CFC-12 currently on the market is 1,1,1,2-tetrafluoroethane (HFC-134a). HFC-134a has excellent thermal performance, an ozone depletion potential (ODP) of 0, and is non-flammable. However, it has a global warming potential (GWP) of 1370, which does not meet the current global demands for energy conservation and emission reduction. Therefore, there is an urgent need to develop a new refrigerant that has the same thermal performance as HFC134a but is more environmentally friendly.

[0004] Third-generation refrigerants, such as HFCs, have zero ODP values ​​and do not deplete the ozone layer, but they have high GWP values ​​and are listed as greenhouse gases in the Kyoto Protocol.The European Parliament has restricted the use of fluorine-containing gases with high GWP values ​​through its F-gas regulations, and in the Kigali Amendment, countries agreed on a schedule for reducing HFCs, reaching an international agreement in the area of ​​climate change countermeasures.

[0005] 2,3,3,3-Tetrafluoropropene (HFO-1234yf) has good thermal performance and excellent environmental parameters as a single working fluid refrigerant, with a global warming potential (GWP) of 4, a lower life cycle climate performance (LCCP) than HFC-134a, and the same atmospheric degradation products as HFC-134a. Under the same automotive air conditioning operating conditions, its refrigeration coefficient is lower than HFC-134a and its refrigeration capacity per unit volume is also lower, but HFO-1234yf has a significantly lower exhaust temperature and a larger saturated liquid specific volume. Using HFO-1234yf instead of HFC-134a allows automakers to continue using their existing mobile air-conditioning (MAC) systems. Therefore, HFO-1234yf is considered a potential next-generation automotive refrigerant alternative and is currently being accepted by automakers in Western Europe. HFO-1234yf has clear environmental advantages in terms of GWP and atmospheric lifetime compared to other refrigerants that replace HFC-134a, but is flammable. high , there is a risk of fire.

[0006] When using a refrigerant composition in a refrigeration system, compatibility between the refrigerant composition and the lubricant must also be considered. For a refrigeration fluid-lubricant combination to operate effectively and at an ideal level in a compression refrigeration, air conditioning, and / or heat pump system, the lubricant must be sufficiently soluble in the refrigeration fluid at various operating temperatures. This solubility reduces the lubricant's viscosity, allowing it to flow more easily throughout the system. Without sufficient solubility, the lubricant tends to accumulate in the evaporator coil and other parts of the refrigeration, air conditioning, or heat pump system, resulting in reduced system efficiency. When using a composition in a refrigeration system, sufficient lubricant must be returned to the system's compressor to lubricate it. The suitability of the lubricant is determined by the properties of the refrigerant / lubricant and the system itself. Lubricants currently used in HFC and HCFC refrigerant refrigeration systems include mineral oil, silicone oil, polyalkylbenzene, polyalkylene glycol, polyalkylene glycol ester, polyol ester, and polyvinyl ether. In HFC refrigeration systems, polyalkylene glycol, polyalkylene glycol ester, polyvinyl ether, and polyol ester are generally preferred as lubricants. Mineral oil or polyalkylbenzenes are commonly used as lubricants in HCFC refrigeration systems.

[0007] Potential replacement refrigerants must share many of the properties of the most widely used fluids, including excellent heat transfer properties, chemical stability, low or no toxicity, non-flammability, and compatibility with lubricants.

[0008] Based on the above ideas, researchers have developed several compositions based on HFO-1234yf, adding other ingredients to enhance the refrigeration effect, improve compatibility with lubricants, and combine the advantages of each ingredient to minimize their disadvantages.

[0009] For example, Chinese Patent Publication No. CN101851490A discloses a refrigerant composition to replace HFC-134a, which consists of 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)), and 1,1-difluoroethane (HFC152a).

[0010] For example, Chinese Patent Publication No. CN101864277A discloses a mixture consisting of 2,3,3,3-tetrafluoropropene, 1,1-difluoroethane and dimethyl ether (DME).

[0011] For example, Chinese Patent Publication No. CN102066518A discloses a mixture of 2,3,3,3-tetrafluoropropene, 1,1,1,2-tetrafluoroethane and 1,1-difluoroethane.

[0012] For example, Chinese Patent Publication No. CN102083935A discloses a mixture of 1,1,1,2-tetrafluoroethane and 2,3,3,3-tetrafluoropropene.

[0013] For example, Chinese Patent Publication No. CN104403637A discloses a tetrafluoropropene composition with good compatibility with lubricants and a method for preparing the same, which comprises 0.4 to 15 parts by weight of fluorine-modified Ni-containing hydrotalcite, 0.002 to 0.25 parts by weight of a silane coupling agent, 49.5 to 985 parts by weight of a lubricant, 4,000 to 90,000 parts by weight of 2,3,3,3-tetrafluoropropene, 0 to 60,000 parts by weight of fluoroethane, 0 to 15,000 parts by weight of 1,1-difluoroethane, 0 to 5,000 parts by weight of isobutane, and 0.8 to 1 part by weight of bis(trifluoromethylsulfonyl)imidized 3-methyl-1-propylpyridine.

[0014] The refrigerant compositions disclosed in the above patents have drawbacks such as high GWP, inability to be directly charged into refrigeration systems, high flammability, and inability to use mineral oils. Therefore, there is a need to develop new refrigerants that have better refrigeration performance, better compatibility with existing systems, and better environmental protection. Summary of the Invention [Problem to be solved by the invention]

[0015] The technical problem that the present invention aims to solve is to provide a fluoroolefin and fluoroalkane composition that is environmentally friendly, has a high refrigeration effect, is compatible with lubricants, and has a low GWP. [Means for solving the problem]

[0016] To solve the above technical problems, the present invention is realized by the following technical solution: A composition of fluoroolefin and fluoroalkane, the composition of which is 70 to 80 parts by weight of 2,3,3,3-tetrafluoropropene, 10 to 20 parts by weight of trans-1,3,3,3-tetrafluoropropene, 5 to 10 parts by weight of 1,1,1,2-tetrafluoroethane, and 2 to 5 parts by weight of difluoromethane.

[0017] In a preferred embodiment of the present invention, the fluoroolefin and fluoroalkane composition of the present invention further contains a lubricant, and the lubricant is one or two selected from mineral oil, silicone oil, polyol ester, polyalkylene glycol, and polyalkylbenzene.

[0018] In a preferred embodiment of the present invention, the fluoroolefin and fluoroalkane composition of the present invention has a global warming potential (GWP) of 150 or less.

[0019] The present invention further discloses a method for preparing the composition of fluoroolefin and fluoroalkane, namely, physically mixing the components in their weight percentages in liquid phase to obtain the composition.

[0020] The most common liquefied gas propellants are hydrocarbons such as butane, isobutane, and propane. Dimethyl ether and HFC-152a, either alone or mixed with hydrocarbon propellants, are also used. However, all of these liquefied gas propellants are highly flammable, and when incorporated into aerosol formulations, they typically produce flammable aerosol products. The present invention provides compositions preferably containing HFO-1234yf for use in medicinal aerosols, including spray cleaners and certain industrial aerosol products, due to the non-flammability of the aerosol products.

[0021] The concept of the present invention is to enhance the refrigeration effect by adding other components to HFO-1234yf, improve compatibility with lubricants, and reduce GWP and flammability. The fluoroolefin and fluoroalkane composition of the present invention can be used as a refrigerant and aerosol propellant in place of HFC-134a.

[0022] The HFO-1234yf described in this invention has good thermal performance and excellent environmental parameters as a single working fluid refrigerant, with a global warming potential (GWP) of 4, a lower life cycle climate performance (LCCP) than HFC-134a, and the same atmospheric decomposition products as HFC-134a. Under the same operating conditions of an automobile air conditioner, HFO-1234yf has a lower refrigeration coefficient and lower refrigeration capacity per unit volume than HFC-134a, but it also has a very low exhaust temperature and a large saturated liquid specific volume.

[0023] The trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)) described in the present invention has excellent environmental parameters, a GWP of 6, a Life Cycle Climate Performance (LCCP) lower than that of HFC-134a, atmospheric decomposition products equivalent to those of HFC-134a, and system performance superior to that of HFC-134a. Therefore, it is considered to be the most promising substitute for HFC-134a in industries such as refrigerants and aerosol propellants.

[0024] The fluoroolefin and fluoroalkane composition of the present invention contains 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, 1,1,1,2-tetrafluoroethane, and difluoromethane as blending components, and combines the advantages of each component while minimizing their disadvantages. The composition of the present invention has the advantages of low GWP, environmental friendliness, high cooling effect, and good compatibility with lubricants.

[0025] All of the raw materials of the present invention are commercially available. [Effects of the Invention]

[0026] Compared with the prior art, the present invention has the following advantages: 1. The fluoroolefin and fluoroalkane composition of the present invention has an ODP of 0 and a GWP of less than 150, and has excellent environmental performance. 2. The fluoroolefin and fluoroalkane composition of the present invention has a low discharge temperature, which can extend the life of the compressor and improve the reliability of the refrigeration equipment. 3. The fluoroolefin and fluoroalkane composition of the present invention has good compatibility with lubricants and high stability. 4. The fluoroolefin and fluoroalkane composition of the present invention can directly replace HFC-134a, eliminating the need to replace the compressor. 5. The fluoroolefin and fluoroalkane compositions of the present invention have good flame retardancy. DETAILED DESCRIPTION OF THE INVENTION

[0027] The present invention will now be further described with reference to specific examples, but the present invention is not limited to the above examples.

[0028] Example 1 4 2,3,3,3-tetrafluoropropene, trans-1,3,3,3-tetrafluoropropene, 1,1,1,2-tetrafluoroethane, and difluoromethane were physically mixed in the liquid phase at these weight percentages to obtain a composition, the composition of which is shown in Table 1. [Table 1]

[0029] Performance measurement: (1) Relative COP, relative capacity, and discharge temperature measurements The inlet temperature of the compressor was set to 50°C, and the COP value, relative capacity and discharge temperature of the test substance were measured within the temperature range of the condenser and evaporator. The results are shown in Table 2. [Table 2] As can be seen from Table 2, the compositions of the present invention have higher energy efficiency than HFC-134a, and compressors using the compositions of the present invention produce lower discharge temperatures than HFC-134a.

[0030] (2) Miscibility measurement The lubricants tested were mineral oil (C3), silicone oil, alkylbenzene (Zerol 150), polyalkylene glycol (PAG), and polyol ester. Two types of lubricants were mixed at 50% by weight, and then mixed with the test material. Using a small compressor, the test substance / lubricant composition was added and tested at 40°C to determine the compatibility of the test substance / lubricant composition with the lubricant when in contact with metals used in refrigeration systems. It was determined that the test substance / lubricant was miscible at all test ratios over the temperature range. The test substance / lubricant composition was as follows: (a) HFO-1234ze and mineral oil / silicone oil (b) HFO-1234yf and polyalkylene glycol / silicone oil (c) 1# Composition and alkylbenzene / silicone oil (d) 2# Composition and Polyalkylene Glycol / Polyol Ester (e) 3# Composition and Polyalkylene Glycol / Alkyl Benzene (f) 4# Composition and Silicone Oil / Alkylbenzene When tested, the compositions of the present invention have been found to have greater stability when in contact with lubricants in compressor refrigeration systems.

[0031] (3) Flammability measurement Flammability test: Flammability test was performed according to the US standard ASTM-E681-01, where LFL is the lower limit of flammability, and the higher the LFL value, the lower the flammability. The results are shown in Table 3. [Table 3]

Claims

1. The composition is 70 to 80% by weight of 2,3,3,3-tetrafluoropropene, 10 to 20% by weight of trans-1,3,3,3-tetrafluoropropene, 5 to 8% by weight of 1,1,1,2-tetrafluoroethane, and 2 to 5% by weight of difluoromethane; The LFL value is 6.28 or more and 6.74 or less. have higher energy efficiency than HFC-134a, and compressors using the composition produce lower discharge temperatures than HFC-134a; further comprising a lubricant; the lubricant is a mixture of two components selected from mineral oil, silicone oil, polyol ester, polyalkylene glycol, and polyalkylbenzene, each mixed in a ratio of 50% by weight; A composition of a fluoroolefin and a fluoroalkane, characterized by:

2. 2. The composition of claim 1, wherein the composition has a global warming potential of 150 or less.

3. 2. The method for preparing a composition of a fluoroolefin and a fluoroalkane according to claim 1, wherein the components of the composition are physically mixed in a liquid phase in these weight percentages to obtain the composition.

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