CN115785908A - Refrigerant for high-temperature air source heat pump - Google Patents

Refrigerant for high-temperature air source heat pump Download PDF

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Publication number
CN115785908A
CN115785908A CN202211345830.9A CN202211345830A CN115785908A CN 115785908 A CN115785908 A CN 115785908A CN 202211345830 A CN202211345830 A CN 202211345830A CN 115785908 A CN115785908 A CN 115785908A
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refrigerant
heat pump
air source
source heat
tetrafluoroethane
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孙金金
程双
武加耀
温靖
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Ma'anshan Noca Technology Co ltd
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Ma'anshan Noca Technology Co ltd
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Abstract

The invention discloses a refrigerant for a high-temperature air source heat pump, which belongs to the field of air compressor refrigerants and comprises tetrafluoroethane, difluoromethane, pentafluoroethane and propane, wherein the mass ratio of each refrigerant is as follows: 72-85% of tetrafluoroethane, 6-8% of difluoromethane, 6-8% of pentafluoroethane and 2% of propane. Adding a lubricant into the air source heat pump, wherein the lubricant comprises one or more of mineral oil, silicone oil, naphthylamine antioxidant and succinic acid antirust agent. The invention solves the problems of low working energy efficiency and easy carbonization in the compressor caused by high boiling point of the refrigerant tetrafluoroethane at low temperature of the high-temperature air source heat pump.

Description

Refrigerant for high-temperature air source heat pump
Technical Field
The invention belongs to the field of air source heat pump compressors, and particularly relates to a refrigerant for a high-temperature air source heat pump.
Background
The temperature of hot water generated by conventional heating of the air source heat pump is within 60 ℃, the air source heat pump can generate hot water with the temperature of more than 85 ℃ along with the improvement of the air source heat pump technology, higher temperature not only has requirements on parts such as a compressor, an expansion valve and the like, but also is very important for selecting a refrigerant with proper high temperature, the high-pressure protection is caused by the pressure of the refrigerant possibly too high to influence the working efficiency of equipment, and the carbonization of the lubricating oil of the refrigerant and the like are caused due to too high temperature.
The patent refers to CN105754682a for the refrigerant oil of compressor and the refrigerant mixture of compressor, which describes the addition of refrigerant oil to the compressor, but in the air source heat pump with lower temperature, the refrigerant is required to have lower boiling point, and the critical temperature and critical pressure are required to be appropriate, otherwise, the internal pressure is too high, which easily causes the carbonization problem.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the problem of carbonization caused by deposition frequently due to higher boiling point of the existing refrigerant is solved.
In order to solve the technical problems, the inventor obtains the technical scheme of the invention through practice and summary, and the invention discloses a refrigerant for a high-temperature air source heat pump, wherein the refrigerant comprises tetrafluoroethane, difluoromethane, pentafluoroethane and propane, and the mass ratio of the refrigerants is as follows:
72-85% of tetrafluoroethane, 6-8% of difluoromethane, 6-8% of pentafluoroethane and 2% of propane.
Tetrafluoroethane, chemical name 1,1,1,2-tetrafluoroethane, formula CH2FCF3. The single tetrafluoroethane refrigerant is also called R-134a refrigerant, namely R134a, HFC134a and HFC-134a, because R-134a belongs to HFC substances, the refrigerant does not destroy the ozone layer at all, is an environment-friendly refrigerant which is approved and recommended to be used by most countries in the world at present, is also a mainstream environment-friendly refrigerant at present, and is widely used for being added in the initial installation and maintenance process of new refrigeration air-conditioning equipment.
The common performance of the R-134a refrigerant is that the boiling point is minus 26.1 ℃ under the standard atmospheric pressure, the critical temperature is 101.1 ℃, and the critical pressure is 4.067MPa. The performance is better, and the refrigerant is suitable for being used as the main component of the refrigerant in the high-temperature air source heat pump.
Propane refrigerant alone, also called R-290 refrigerant, is called R290 refrigerant, R290 and R290 belong to hydrocarbon refrigerant, and the ozone layer is not damaged at all, the greenhouse effect is very small, the refrigerant belongs to the most environment-friendly refrigerant at present, and from the viewpoint of environment protection, almost all countries around the world have no limit on the initial installation of the R290 refrigerant on new refrigeration equipment and the use of the R290 refrigerant in the after-sale maintenance process. The R-290 refrigerant has the common performances of boiling point of-42.2 ℃ under the standard atmospheric pressure, critical temperature of 96.67 ℃ and critical pressure of 4.24MPa. In common, the standard boiling point of difluoromethane is-51.6 ℃, the critical temperature under the standard atmospheric pressure is 72,5 ℃, and the critical pressure is 5.8MPa; pentafluoroethane is generally found to have a normal boiling point of-48.4 ℃ and a critical temperature at standard atmospheric pressure of 72.5 ℃ which is comparable to difluoromethane.
And adding a lubricant into the air source heat pump, wherein the lubricant comprises one or more of mineral oil, silicone oil, naphthylamine antioxidant and succinic acid antirust agent.
The mineral is ester oil, and the ester oil can be divided into diester, polyol ester and aromatic ester according to the number and position of ester groups of reaction products. The diester has good viscosity index and low-temperature fluidity, but the thermal oxidation stability is poor; the polyol ester has excellent thermal oxidation stability and hydrolytic stability, low evaporation loss and better lubricating property; the aromatic ester has low production cost, low evaporation loss, high solubility and thermal oxidation stability due to the benzene ring structure, and low viscosity index.
In a further technical scheme, the standard boiling point is between-46.5 and-38.6 ℃, the critical temperature is between 95.9 and 99.6 ℃, and the critical pressure is between 4.32 and 4.08MPa.
In a further technical scheme, the silicone oil is methyl silicone oil.
In still further embodiments, the naphthylamine antioxidant comprises one or both of alpha-naphthylamine and N-phenylaniline.
The oxidation stability is one of the most important properties of the compressor oil, is the most key index for representing the service life of the compressor oil, and is generally improved by adding an antioxidant. The amine antioxidant has good high-temperature oxidation resistance, has good effects of prolonging induction period and inhibiting oil product later oxidation, is particularly stable at 200 ℃ for diphenylamine and alpha-naphthylamine, has synergistic effect when being compounded with the phenol antioxidant and amines, and has more remarkable effect in the aspect of oxidation resistance.
In a still further aspect, the base succinic acid rust inhibitor includes dodecenylsuccinic acid.
The rust prevention and corrosion prevention is one of the most basic performances of lubricating oil, particularly for lubricating oil in a compressor, an oil product is usually in direct contact with compressed gas and is easily influenced by pollutants such as moisture in the gas, and the water has low solubility under high pressure and is more easily separated out to be mixed with the oil product, so that the equipment is accelerated to be rusted. Rust inhibitors are generally polar substances, the polar groups of which are present when they come into contact with metals. Can adsorb to the metal surface and form the protection film, prevent corrosive medium and metal contact, play rust-resistant effect, and ester oil can form the competitive adsorption relation at the metal surface and rust inhibitor because polarity is strong, influences rust inhibitor result of use.
In a further aspect, the mineral oil is a naphthenic mineral oil for HCFC refrigerants.
In a further technical scheme, the antioxidant accounts for 0.5-1.0% of the mass of the lubricant, and the mass ratio of the antioxidant to the antirust agent is 1:1.35.
compared with the prior art, the invention can obtain the following technical effects:
a refrigerant for a high-temperature air source heat pump can be used for solving the problem of difficult carbonization due to high boiling point, high critical temperature and low critical pressure when producing high-temperature water; the critical temperature and critical pressure in tetrafluoromethane are excellent in a compressor, but the normal boiling point is high in a low-temperature environment, so that expansion is easy to occur in the operation of the compressor, otherwise, the internal pressure is easily too high, so that the carbonization problem is easy to occur. The invention adopts the filling of difluoromethane, pentafluoroethane and propane into tetrafluoroethane to reduce the comprehensive performance, and combines lubricating oil to realize the reduction of boiling point without great change of critical temperature and critical pressure. The refrigerant for the high-temperature air source heat pump has the advantages of low cost, easiness in preparation and good environmental friendliness.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The application of the principles of the present invention will now be described in further detail with reference to specific embodiments.
The refrigerant comprises tetrafluoroethane, difluoromethane, pentafluoroethane and propane, and the lubricant comprises one or more of mineral oil, silicone oil, naphthylamine antioxidant and succinic acid antirust agent.
The silicone oil is methyl silicone oil. The naphthylamine antioxidant comprises one or two of alpha-naphthylamine or N-phenylaniline. The base succinic acid rust inhibitor comprises dodecenylsuccinic acid. The mineral oil is naphthenic mineral oil used in HCFC refrigerant. The antioxidant accounts for 0.5-1.0 percent of the mass of the lubricant, and the mass ratio of the antioxidant to the antirust is 1:1.35.
specifically, in the following examples, the lubricant is polyol ester mineral oil, the silicone oil is methyl silicone oil, the naphthylamine antioxidant is alpha-naphthylamine, and the base succinic acid rust inhibitor is dodecenylsuccinic acid.
The following table is table 1, table 1 being part of the physical properties of tetrafluoroethane, difluoromethane, pentafluoroethane and propane.
Component (A) Molecular weight Normal boiling point deg.C Critical temperatureDEG C Critical pressure MPa
Tetrafluoroethane 102.03 -26.1 101.1 4.067
Difluoromethane 52.023 -51.6 72.5 5.808
Pentafluoroethane 120.02 -48.45 72.5 4.95
Propane (E) 44.096 -42.2 96.67 4.24
Example 1
A refrigerant for a high-temperature air source heat pump is additionally arranged in a unified test environment, and comprises tetrafluoroethane, difluoromethane, pentafluoroethane and propane, wherein the mass ratios of the refrigerants are as follows:
the mass percent of tetrafluoroethane is 72%, the mass percent of difluoromethane is 6%, the mass percent of pentafluoroethane is 6%, and the mass percent of propane is 2%. Are often all gaseous fills.
Example 2
A refrigerant for a high-temperature air source heat pump is additionally arranged in a unified test environment, and comprises tetrafluoroethane, difluoromethane, pentafluoroethane and propane, wherein the mass ratios of the refrigerants are as follows:
74% by mass of tetrafluoroethane, 6% by mass of difluoromethane, 6% by mass of pentafluoroethane and 2% by mass of propane. Are often all gaseous fills.
Example 3
A refrigerant for a high-temperature air source heat pump is additionally arranged in a unified test environment, and comprises tetrafluoroethane, difluoromethane, pentafluoroethane and propane, wherein the mass ratios of the refrigerants are as follows:
76% by mass of tetrafluoroethane, 6% by mass of difluoromethane, 6% by mass of pentafluoroethane and 2% by mass of propane. Are often all gaseous fills.
Example 4
A refrigerant for a high-temperature air source heat pump is additionally arranged in a unified test environment, and comprises tetrafluoroethane, difluoromethane, pentafluoroethane and propane, wherein the mass ratios of the refrigerants are as follows:
the mass percent of tetrafluoroethane is 78%, the mass percent of difluoromethane is 6%, the mass percent of pentafluoroethane is 6%, and the mass percent of propane is 2%. Are often all gaseous fills.
Example 5
A refrigerant for a high-temperature air source heat pump is additionally arranged in a unified test environment, and comprises tetrafluoroethane, difluoromethane, pentafluoroethane and propane, wherein the mass ratios of the refrigerants are as follows:
the mass percent of tetrafluoroethane is 80%, the mass percent of difluoromethane is 6%, the mass percent of pentafluoroethane is 6%, and the mass percent of propane is 2%. Are often all gaseous fills.
Example 6
A refrigerant for a high-temperature air source heat pump is additionally arranged in a unified test environment, and comprises tetrafluoroethane, difluoromethane, pentafluoroethane and propane, wherein the mass ratios of the refrigerants are as follows:
the mass percent of tetrafluoroethane is 82%, the mass percent of difluoromethane is 6%, the mass percent of pentafluoroethane is 6%, and the mass percent of propane is 2%. Are often all gaseous fills.
Example 7
A refrigerant for a high-temperature air source heat pump is additionally arranged in a unified test environment, and comprises tetrafluoroethane, difluoromethane, pentafluoroethane and propane, wherein the mass ratios of the refrigerants are as follows:
the mass percent of tetrafluoroethane is 84%, the mass percent of difluoromethane is 7%, the mass percent of pentafluoroethane is 6%, and the mass percent of propane is 6%. Are often all gaseous fills.
Table 2 below shows the measured normal boiling point, critical temperature and critical pressure of the refrigerants measured in the above examples 1 to 7.
Figure BDA0003917187720000061
In summary, difluoromethane, pentafluoroethane and propane were filled into tetrafluoroethane, maintaining the mixing ratio: (72-85%): (6-8%): (6-8%): 2 percent, the boiling point of the bottom of the product can be better ensured to be basically maintained between minus 46.5 ℃ and minus 38.6 ℃ under the condition of mixing the lubricant, and the better critical temperature and critical pressure can be ensured at the temperature, so that the carbonization problem can be better overcome.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (7)

1. The refrigerant for the high-temperature air source heat pump is characterized by comprising tetrafluoroethane, difluoromethane, pentafluoroethane and propane, wherein the mass ratio of the tetrafluoroethane to the difluoromethane is as follows:
72-85% of tetrafluoroethane, 6-8% of difluoromethane, 6-8% of pentafluoroethane and 2% of propane;
and adding a lubricant into the air source heat pump, wherein the lubricant comprises one or more of mineral oil, silicone oil, naphthylamine antioxidant and succinic acid antirust agent.
2. The refrigerant for the high-temperature air source heat pump as recited in claim 1, wherein the normal boiling point is-46.5 to-38.6 ℃, the critical temperature is 95.9 to 99.6 ℃, and the critical pressure is 4.32 to 4.08MPa.
3. The refrigerant for a high-temperature air source heat pump as claimed in claim 1, wherein: the silicone oil is methyl silicone oil.
4. The refrigerant for a high-temperature air source heat pump as claimed in claim 1, wherein: the naphthylamine antioxidant comprises one or two of alpha-naphthylamine or N-phenylaniline.
5. The refrigerant for a high-temperature air source heat pump as claimed in claim 1, wherein: the base succinic acid rust inhibitor comprises dodecenylsuccinic acid.
6. The refrigerant for a high-temperature air source heat pump as claimed in claim 1, wherein: the mineral oil is naphthenic mineral oil used in HCFC refrigerant.
7. The refrigerant for a high-temperature air source heat pump as claimed in claim 1, wherein: the antioxidant accounts for 0.5-1.0 percent of the mass of the lubricant, and the mass ratio of the antioxidant to the antirust is 1:1.35.
CN202211345830.9A 2022-10-31 2022-10-31 Refrigerant for high-temperature air source heat pump Pending CN115785908A (en)

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