CN111073603B - Mixed hydrocarbon refrigerant and its application - Google Patents
Mixed hydrocarbon refrigerant and its application Download PDFInfo
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- CN111073603B CN111073603B CN201911395972.4A CN201911395972A CN111073603B CN 111073603 B CN111073603 B CN 111073603B CN 201911395972 A CN201911395972 A CN 201911395972A CN 111073603 B CN111073603 B CN 111073603B
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/40—Replacement mixtures
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Abstract
The invention discloses a mixed hydrocarbon refrigerant and application thereof, wherein the refrigerant contains propylene, propane and tetrafluoropropene, and the content of the propylene is 81-99 wt%, the content of the propane is 0.5-10 wt%, and the content of the tetrafluoropropene is 0.5-10 wt% based on the total weight of the refrigerant. The refrigerant provided by the invention has the advantages that the mixed hydrocarbon refrigerant obtained by mixing specific raw materials according to a specific ratio has a wide application range on the working pressure, and is suitable for replacing R22 refrigerant and R410a refrigerant; the mixed hydrocarbon refrigerant provided by the invention not only has faster refrigeration speed and more obvious energy-saving effect, but also can suppress combustion and explosion.
Description
Technical Field
The invention relates to the field of refrigerant research and development, in particular to a mixed hydrocarbon refrigerant and application thereof.
Background
The use of chlorofluorocarbon (CFCs) and Hydrofluorocarbon (HCFCs) refrigerants causes damage to the atmospheric ozone layer, and therefore the commonly used refrigerants R12 and R22 have been eliminated from the field of refrigeration and air conditioning.
The refrigerants R134a and R410a have zero destructive effect on the ozone layer, but have high greenhouse effect.
In addition, the refrigerating capacity of R134a is only 60% of that of the R22 unit, the thermal conductivity of R134a is reduced by 10% compared with that of R22, and the water absorption of R134a is 20 times of that of R22, so that the operation and maintenance cost of the equipment is higher; although the efficiency of R410a is better than that of R134a, the defects of too high working pressure, high requirements on optimization and pressure resistance of pipeline parts, need of improving the design of a heat exchanger and a unit, high investment, operation and maintenance cost and the like exist; and because they have certain greenhouse effect, the greenhouse gas effect generated by R410a even partially exceeds that of R22.
CN1693408A discloses a alkane mixture refrigerant, which adopts 55-62% of R290 and 38-45% of R600a, and replaces R134a at the evaporation temperature of-25 ℃ to 5 ℃. The refrigerant is simple and convenient to mix, has low cost, is only 1/20 of R134a, saves more energy than R134a, and reduces the use cost.
CN101270274A discloses an energy-saving environment-friendly wear-resistant canned hydrocarbon refrigerant, which adopts a mixed hydrocarbon refrigerant of 54-65% of R290, 30-40% of R600a and 3-8% of low-temperature refrigeration lubricating oil (the main component is heavy alkylbenzene) with the pour point of-38 ℃ to-25 ℃ to replace the traditional refrigerants of chlorofluorocarbon R12 (Freon) and fluorine-containing refrigerant R134a, effectively solves the problem that the existing hydrocarbon refrigerant causes the compressor to wear and pull the cylinder frequently due to the characteristics of over-drying and good oil solubility, and has the energy-saving rate of 10-20%.
CN101402847A discloses a hydrocarbon refrigerant replacing R22, comprising a mixed hydrocarbon refrigerant of 80-89% of R290 and 11-20% of R600 a. But the refrigerant needs to be used in a dedicated refrigeration tank and corresponding tank filling steps.
CN104059614A discloses a mixed alkane refrigerant, which is characterized by being prepared by mixing the following components in percentage by weight: 81-99% of propylene, 0.5-10% of isobutane and 0.5-20% of propane.
In the prior art, in view of the difference of the working pressures applied to the R22 and the R410a refrigerants, the R22 and the R410a refrigerants are difficult to replace, and the new refrigerants used for replacing the R22 and the R410a refrigerants are often required to be separately developed according to different working pressures, so that the research and development work of the refrigerants is increased. Moreover, for the new refrigerant, the problems not only apply to the working pressure, but also need to be comprehensively considered in terms of the refrigeration capacity, energy conservation and environmental protection, greenhouse effect, thermal conductivity, water absorption, flame suppression and explosion suppression of the refrigerant.
Disclosure of Invention
The invention aims to overcome one of the problems in the prior art and provides a mixed hydrocarbon refrigerant which has the advantages of quicker refrigeration, better energy-saving effect, combustion suppression and explosion suppression and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a mixed hydrocarbon refrigerant, wherein the refrigerant contains propylene, propane, and tetrafluoropropene, and the content of propylene is 81 to 99 wt%, the content of propane is 0.5 to 10 wt%, and the content of tetrafluoropropene is 0.5 to 10 wt%, based on the total weight of the refrigerant.
In a second aspect, the invention provides a use of the mixed hydrocarbon refrigerant as described above in a refrigeration apparatus.
The mixed hydrocarbon refrigerant obtained by mixing specific raw materials according to a specific proportion has a wide application range for working pressure, and is suitable for replacing not only R22 refrigerant but also R410a refrigerant; the mixed hydrocarbon refrigerant provided by the invention has the advantages of higher refrigeration speed, more obvious energy-saving effect, lower greenhouse gas effect and flame and explosion suppression performance.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In addition, it should be noted that: in the present invention, reference to "range value" means any value in a range that can be made by the "range value" and any two point values in these "range values".
The invention provides a mixed hydrocarbon refrigerant, wherein the refrigerant contains propylene, propane and tetrafluoropropene, and the content of the propylene is 81-99 wt%, the content of the propane is 0.5-10 wt%, and the content of the tetrafluoropropene is 0.5-10 wt% based on the total weight of the refrigerant.
According to the present invention, the mixed hydrocarbon refrigerant provided by the present invention can be used in place of R22 refrigerant and R410a refrigerant.
According to the invention, the mixed hydrocarbon refrigerant provided by the invention is added with the tetrafluoropropene with the effect of reducing the flammability of the product, thereby being beneficial to reducing the flammability of the mixed hydrocarbon refrigerant and improving the safety.
According to the invention, the mixed hydrocarbon refrigerant provided by the invention has the obvious effects of accelerating the refrigeration speed, improving the energy-saving efficiency and reducing the greenhouse gas effect by synergistically using the propylene, the propane and the tetrafluoropropene according to the proportion. When the mixed hydrocarbon mixture is directly used in a refrigerating device of R22, the energy-saving efficiency of the mixed hydrocarbon mixture compared with that of R22 reaches 17.86-39.29 percent, preferably 28.57-39.29 percent under the same conditions. When the mixed hydrocarbon mixture is directly used in a refrigerating device of R410a, the energy-saving efficiency of the refrigerant reaches 33.3-40% compared with that of R410a under the same conditions.
According to the present invention, it is preferable that the content of propylene is 91 to 97% by weight, the content of propane is 1 to 6% by weight, and the content of tetrafluoropropene is 1 to 6% by weight, based on the total weight of the refrigerant; more preferably, the content of propylene is 91 to 94% by weight, the content of propane is 1.2 to 3.5% by weight, and the content of tetrafluoropropene is 1.2 to 4% by weight, based on the total weight of the refrigerant; the mixed hydrocarbon refrigerant of the present invention within the above preferred content range can achieve faster refrigeration efficiency and more excellent energy saving efficiency when used.
According to the present invention, in consideration of the heat conductivity and low flammability of the refrigerant in combination, it is preferable that the weight ratio of the total content of propane and methyl mercaptan to tetrafluoropropene is 1: (0.375-3.5), preferably 1: (0.5-3); more preferably 1: (1-2.5).
According to the present invention, in order to further improve the flame and explosion suppression effect of the refrigerant, it is preferable that the refrigerant further contains tetramethylcyclobutane and liquid carbon dioxide, and the content of tetramethylcyclobutane is 0.01 to 2 wt% and the content of liquid carbon dioxide is 0.01 to 2 wt% based on the total weight of the refrigerant; preferably, the content of tetramethylcyclobutane is 0.1-1.5 wt% and the content of liquid carbon dioxide is 0.1-1.5 wt% based on the total weight of the refrigerant.
In view of the flame and explosion suppression effect of the refrigerant according to the present invention, it is preferable that the total content of tetrafluoropropene, tetramethylcyclobutane and liquid carbon dioxide is 0.5 to 14% by weight, preferably 2.5 to 6.5% by weight, based on the total weight of the refrigerant.
According to the invention, the refrigerant also contains methyl mercaptan, wherein the content of the methyl mercaptan is 0.001-0.15 wt%, preferably 0.05-0.1 wt%, based on the total weight of the refrigerant; in the invention, the methyl mercaptan odor indicator is optionally added, which is beneficial to improving the environmental odor of the mixed hydrocarbon refrigerant in use and ensuring more comfortable feeling for users.
The tetrafluoropropene used therein according to the present invention may be any commercially available product, preferably the tetrafluoropropene is refrigeration grade HFO1234yf in case of use with propene, propane and optionally methyl mercaptan, where HFO1234yf can exhibit even more advantageous low flammability.
In the invention, the tetrafluoropropene HFO1234yf, the outer tube is colorless transparent gas, the standard boiling point is-29.45 ℃, and the density is 1.203g/cm3。
According to the present invention, the propylene may be propylene of various purity levels currently used for refrigerants, and the propane may be propane of various purity levels currently used for refrigerants. Preferably, the propylene is R1270 and the propane is R290, which is common in the refrigerant art.
In the present invention, propylene is R1270, and is a colorless, odorless, slightly sweet gas at room temperature. The boiling point is 47.8 ℃, the critical temperature is 92.42 ℃, the purity is more than or equal to 99.5 percent, and the sulfur content is less than or equal to 1.0.
In the invention, the propane is R290, the colorless transparent liquid is free of peculiar smell, the boiling point is-42.1 ℃, the critical temperature is 96.6 ℃, the purity is more than or equal to 99.5 percent, and the sulfur content is less than or equal to 1.0.
According to the present invention, it may have no particular requirement for the production method as long as the components are mixed and stirred before use.
In a second aspect, the invention provides a use of the mixed hydrocarbon refrigerant as described above in a refrigeration apparatus.
According to the present invention, the mixed hydrocarbon refrigerant can be applied to a refrigeration apparatus as a refrigerant, for example, an air conditioning refrigeration apparatus, specifically, a split air conditioner and a central air conditioner, for example.
According to the invention, the mixed hydrocarbon refrigerant is fed to a compressor of a refrigeration unit for compression.
Since the main inventive point of the present invention is about the improvement of the composition of the refrigerant, other conditions and specific operation steps of the refrigeration method may not be particularly limited, and reference may be made to other conditions and specific operation steps of the R22 refrigerant or the R410a refrigerant in the prior art.
According to the method of the invention, since the refrigerant is mainly propylene and the content of propylene is higher than 80%, specifically, the content of propylene is 81-99 wt%, compared with the existing R22 refrigerant or R410a refrigerant, the filling amount can be greatly reduced, when the refrigerant is used for replacing R22 refrigerant, the total consumption of the refrigerant is 0.3-0.6kg, preferably 0.4-0.5kg, relative to the refrigerating capacity of 3.5kW, and the consumption is obviously lower than that of R22 refrigerant and even can reach less than half of that of R22 refrigerant; when the refrigerant according to the formula is used to replace the R410a refrigerant, the total usage amount of the refrigerant is 0.3-0.6kg, preferably 0.4-0.5kg, relative to the refrigeration capacity of 3.5kW, and the usage amount is significantly lower than that of the R410a refrigerant, and even can reach less than half of that of the R22 refrigerant.
According to the present invention, since the refrigerant of the present invention contains at least 80% by weight of propylene, which makes the refrigerant have good compatibility with lubricating oils known to those skilled in the art, the refrigerant of the present invention can use various lubricating oils known to those skilled in the art as refrigerating machine oil, and preferably heavy alkylbenzene having good low temperature performance and low price is used as refrigerating machine oil used for the refrigerant.
The following will further illustrate the beneficial effects of the mixed hydrocarbon refrigerant and the refrigeration method using the same according to the present invention with reference to specific examples.
The raw materials and manufacturers used in the following examples and comparative examples were as follows:
propylene, propane, tetrafluoropropene HFO1234yf, tetramethylcyclobutane, liquid carbon dioxide, R22 refrigerant, R410a refrigerant, and heavy alkylbenzene lubricants are all commercially available.
The test items and test methods referred to in the following examples and comparative examples are as follows:
environmental protection performance: the refrigerants prepared in the examples and the comparative examples were subjected to environmental safety tests (test standards are 2002- "disinfection technical specifications") entrusted to the safety of products related to environment and health of the centers for disease prevention and control in China, and the test items were acute oral toxicity tests.
Ozone depletion potential: ODP values were used for evaluation, according to GB/T7778-2001 test.
Greenhouse gas effect: the global warming potential (GWP value) was used for evaluation and tested in accordance with GB/T7778-2001.
Flammability and flame and explosion suppression: the testing of the flash point (GB/T261), the explosion limit (GB/T12474) and the self-ignition point (GB/T5332) was carried out on the refrigerants prepared in each example and comparative example by the institute for fire research of the Ministry of public Security.
Example 1
This example illustrates the mixed hydrocarbon refrigerant of the present invention.
Mixed hydrocarbon refrigerant: mixing 94 parts by weight of propylene (R1270), 1.2 parts by weight of propane (R290), 3.1 parts by weight of tetrafluoropropene (HFO1234yf), 0.1 part by weight of methyl mercaptan, 0.8 part by weight of tetramethylcyclobutane and 0.8 part by weight of liquid carbon dioxide, and stirring at 20 ℃ for 10min to obtain a mixed hydrocarbon refrigerant a 1;
through detection, the mixed hydrocarbon refrigerant A is environment-friendly, has no toxicity, has an ODP value of 0 and a GWP value of 20, and shows that the mixed hydrocarbon refrigerant A basically does not cause greenhouse gas effect; meanwhile, the mixed hydrocarbon refrigerant A has a flash point of less than or equal to 0 ℃ (cup closed) at the ambient temperature of 20-28 ℃ and the atmospheric pressure of 101150-101430 Pa), has an explosion limit of 7.5 percent and an auto-ignition point of 458 ℃, and has low flammability and good flame and explosion suppression effects; can be superior to the existing R22 refrigerant and R410a refrigerant.
Example 2
This example illustrates the mixed hydrocarbon refrigerant of the present invention.
Mixed hydrocarbon refrigerant: mixing 91 parts by weight of propylene (R1270), 3.4 parts by weight of propane (R290), 3.5 parts by weight of tetrafluoropropene (HFO1234yf), 0.1 part by weight of methyl mercaptan, 1 part by weight of tetramethylcyclobutane and 1 part by weight of liquid carbon dioxide, and stirring at 21 ℃ for 12min to obtain a mixed hydrocarbon refrigerant A2;
through detection, the mixed hydrocarbon refrigerant A2 is environment-friendly and has no toxicity, and the ODP value is 0, the GWP value is 19.5, so that the greenhouse gas effect is basically not caused; meanwhile, the mixed hydrocarbon refrigerant A2 has a flash point of less than or equal to 0 ℃ (closed cup)) at the ambient temperature of 20-28 ℃ and the atmospheric pressure of 101150 and 101430Pa, has an explosion limit of 8 percent and an auto-ignition point of 460 ℃, and has low flammability and good flame and explosion suppression effects; can be superior to the existing R22 refrigerant and R410a refrigerant.
Example 3
This example illustrates the mixed hydrocarbon refrigerant of the present invention.
Mixed hydrocarbon refrigerant: mixing 97 parts by weight of propylene (R1270), 1.35 parts by weight of propane (R290), 1.4 parts by weight of tetrafluoropropene (HFO1234yf), 0.05 parts by weight of methyl mercaptan, 0.1 parts by weight of tetramethylcyclobutane and 0.1 parts by weight of liquid carbon dioxide, and stirring at 23 ℃ for 25min to obtain a mixed hydrocarbon refrigerant A3;
through detection, the mixed hydrocarbon refrigerant A3 is environment-friendly and has no toxicity, and the ODP value is 0, the GWP value is 19, so that the greenhouse gas effect is basically not caused; meanwhile, the mixed hydrocarbon refrigerant A3 has a flash point of less than or equal to 0 ℃ (cup closed) at the ambient temperature of 20-28 ℃ and the atmospheric pressure of 101150 and 101430 Pa), has an explosion limit of 2.1 percent and an auto-ignition point of 450 ℃, and has lower flammability and better flame and explosion suppression effects; can be superior to the existing R22 refrigerant and R410a refrigerant.
Example 4
This example illustrates the mixed hydrocarbon refrigerant of the present invention.
Mixed hydrocarbon refrigerant: mixing 94 parts by weight of propylene (R1270), 2.8 parts by weight of propane (R290), 1.5 parts by weight of tetrafluoropropene (HFO1234yf), 0.1 part by weight of methyl mercaptan, 0.8 part by weight of tetramethylcyclobutane and 0.8 part by weight of liquid carbon dioxide, and stirring at 25 ℃ for 20min to obtain a mixed hydrocarbon refrigerant A4;
through detection, the mixed hydrocarbon refrigerant A4 is environment-friendly and has no toxicity, and the ODP value is 0, the GWP value is 18, so that the greenhouse gas effect is basically not caused; meanwhile, the mixed hydrocarbon refrigerant A4 has a flash point of less than or equal to 0 ℃ (closed cup)) at the ambient temperature of 20-28 ℃ and the atmospheric pressure of 101150 and 101430Pa, has an explosion limit of 5 percent and an auto-ignition point of 451 ℃, and has lower flammability and better flame and explosion suppression effects; can be superior to the existing R22 refrigerant and R410a refrigerant.
Example 5
This example illustrates the mixed hydrocarbon refrigerant of the present invention.
Mixed hydrocarbon refrigerant: mixing 94 parts by weight of propylene (R1270), 3.1 parts by weight of propane (R290), 1.2 parts by weight of tetrafluoropropene (HFO1234yf), 0.1 part by weight of methyl mercaptan, 0.8 part by weight of tetramethylcyclobutane and 0.8 part by weight of liquid carbon dioxide, and stirring at 26 ℃ for 20min to obtain a mixed hydrocarbon refrigerant A5;
through detection, the mixed hydrocarbon refrigerant A5 is environment-friendly and has no toxicity, and the ODP value is 0, the GWP value is 19.2, so that the greenhouse gas effect is basically not caused; meanwhile, the mixed hydrocarbon refrigerant A5 has a flash point of less than or equal to 0 ℃ (closed cup)) at the ambient temperature of 20-28 ℃ and the atmospheric pressure of 101150 and 101430Pa, has an explosion limit of 6 percent and an auto-ignition point of 455 ℃, so that the mixed hydrocarbon refrigerant has low flammability and good flame suppression and explosion suppression effects; can be superior to the existing R22 refrigerant and R410a refrigerant.
Example 6
This example illustrates the mixed hydrocarbon refrigerant of the present invention.
Mixed hydrocarbon refrigerant: mixing 91 parts by weight of propylene (R1270), 2.4 parts by weight of propane (R290), 3.5 parts by weight of tetrafluoropropene (HFO1234yf), 0.1 part by weight of methyl mercaptan, 1.5 parts by weight of tetramethylcyclobutane and 1.5 parts by weight of liquid carbon dioxide, and stirring at 22 ℃ for 21min to obtain a mixed hydrocarbon refrigerant a 6;
through detection, the mixed hydrocarbon refrigerant A6 is environment-friendly and has no toxicity, and the ODP value is 0, the GWP value is 19.3, so that the greenhouse gas effect is basically not caused; meanwhile, the mixed hydrocarbon refrigerant A6 has a flash point of less than or equal to 0 ℃ (closed cup)) at the ambient temperature of 20-28 ℃ and the atmospheric pressure of 101150 and 101430Pa, has an explosion limit of 9 percent and an auto-ignition point of 470 ℃, and has low flammability and good flame and explosion suppression effects; can be superior to the existing R22 refrigerant and R410a refrigerant.
Example 7
This example illustrates the mixed hydrocarbon refrigerant of the present invention.
Mixed hydrocarbon refrigerant: stirring 94 parts by weight of propylene (R1270), 2.4 parts by weight of propane (R290), 3.5 parts by weight of tetrafluoropropene (HFO1234yf) and 0.1 part by weight of methyl mercaptan at 24 ℃ for 26min to obtain a mixed hydrocarbon refrigerant A7;
through detection, the mixed hydrocarbon refrigerant A7 is environment-friendly and has no toxicity, and the ODP value is 0, the GWP value is 19.8, so that the greenhouse gas effect is basically not caused; meanwhile, the mixed hydrocarbon refrigerant A7 has a flash point of less than or equal to 0 ℃ (closed cup)) at the ambient temperature of 20-28 ℃ and the atmospheric pressure of 101150 and 101430Pa, the explosion limit is 6.5 percent, the spontaneous combustion point is 455 ℃, so that the mixed hydrocarbon refrigerant is low in flammability and has good flame suppression and explosion suppression effects; can be superior to the existing R22 refrigerant and R410a refrigerant.
Example 8
This example illustrates the mixed hydrocarbon refrigerant of the present invention.
Mixed hydrocarbon refrigerant: mixing 94 parts by weight of propylene (R1270), 2 parts by weight of propane (R290) and 4 parts by weight of tetrafluoropropene (HFO1234yf), and stirring at 23 ℃ for 24min to obtain a mixed hydrocarbon refrigerant A8;
through detection, the mixed hydrocarbon refrigerant A8 is environment-friendly and has no toxicity, and the ODP value is 0, the GWP value is 19.9, so that the greenhouse gas effect is basically not caused; meanwhile, the mixed hydrocarbon refrigerant A8 has a flash point of less than or equal to 0 ℃ (closed cup)) at the ambient temperature of 20-28 ℃ and the atmospheric pressure of 101150 and 101430Pa, has an explosion limit of 7 percent and an auto-ignition point of 456 ℃, and has low flammability and good flame suppression and explosion suppression effects; can be superior to the existing R22 refrigerant and R410a refrigerant.
Example 9
This example illustrates the mixed hydrocarbon refrigerant of the present invention.
Mixed hydrocarbon refrigerant: mixing 94 parts by weight of propylene (R1270), 1.3 parts by weight of propane (R290), 3.1 parts by weight of tetrafluoropropene (HFO1234yf), 0.8 part by weight of tetramethylcyclobutane and 0.8 part by weight of liquid carbon dioxide, and stirring at 26 ℃ for 25min to obtain a mixed hydrocarbon refrigerant A9;
through detection, the mixed hydrocarbon refrigerant A9 is environment-friendly and has no toxicity, and the ODP value is 0, the GWP value is 19.7, so that the greenhouse gas effect is basically not caused; meanwhile, the mixed hydrocarbon refrigerant A9 has a flash point of less than or equal to 0 ℃ (closed cup)) at the ambient temperature of 20-28 ℃ and the atmospheric pressure of 101150-101430Pa, the explosion limit is 7.8%, the spontaneous combustion point is 455 ℃, so that the mixed hydrocarbon refrigerant is low in flammability and has good flame suppression and explosion suppression effects; can be superior to the existing R22 refrigerant and R410a refrigerant.
Example 10
This example illustrates the mixed hydrocarbon refrigerant of the present invention.
Mixed hydrocarbon refrigerant: mixing 85 parts by weight of propylene (R1270), 8.9 parts by weight of propane (R290), 4.4 parts by weight of tetrafluoropropene (HFO1234yf), 0.1 part by weight of methyl mercaptan, 0.8 part by weight of tetramethylcyclobutane and 0.8 part by weight of liquid carbon dioxide, and stirring at 28 ℃ for 20min to obtain a mixed hydrocarbon refrigerant A10;
through detection, the mixed hydrocarbon refrigerant A8 is environment-friendly and has no toxicity, and the ODP value is 0, the GWP value is 19.1, so that the greenhouse gas effect is basically not caused; meanwhile, the mixed hydrocarbon refrigerant A8 has a flash point of less than or equal to 0 ℃ (closed cup)) at the ambient temperature of 20-28 ℃ and the atmospheric pressure of 101150 and 101430Pa, the explosion limit is 8.8 percent, the spontaneous combustion point is 469 ℃, and the mixed hydrocarbon refrigerant has low flammability and good flame and explosion suppression effects; can be superior to the existing R22 refrigerant and R410a refrigerant.
Comparative example 1
A mixed hydrocarbon refrigerant was prepared in the same manner as in example 1, except that:
mixed hydrocarbon refrigerant: 80 parts by weight of propylene (R1270), 13.9 parts by weight of propane (R290), 4.4 parts by weight of tetrafluoropropene (HFO1234yf), 0.1 part by weight of methyl mercaptan, 0.8 part by weight of tetramethylcyclobutane and 0.8 part by weight of liquid carbon dioxide were mixed to obtain a mixed hydrocarbon refrigerant DA 1.
Comparative example 2
A mixed hydrocarbon refrigerant was prepared in the same manner as in example 1, except that:
mixed hydrocarbon refrigerant: 94 parts by weight of propylene (R1270), 3 parts by weight of propane (R290) and 3 parts by weight of isobutane were mixed to obtain a mixed hydrocarbon refrigerant DA 2.
Comparative example 3
A mixed hydrocarbon refrigerant was prepared in the same manner as in example 1, except that:
mixed hydrocarbon refrigerant: 94 parts by weight of propane (R290), 3 parts by weight of propylene (R1270) and 3 parts by weight of isobutane were mixed to obtain a mixed hydrocarbon refrigerant DA 3.
Application example 1
A refrigerating device: 1.5 p of a split air conditioner suitable for R22 refrigerant;
the refrigeration method comprises the following steps: the indoor unit of the refrigerating device is arranged at the length, width and height of 4.5 multiplied by 3.3 multiplied by 2.8m3The refrigerants a1-a10 and DA1-DA3 and the refrigerant R22 prepared in examples 1 to 10 and comparative examples 1 to 3 were fed to the compressor of the refrigerating apparatus, respectively (adjusted space temperature was 35 ℃), wherein the amounts of the refrigerants a1-a10 and DA1-DA3 and the refrigerant R22 were used, as shown in table 1.
And (3) testing:
(1) cooling speed: the time taken to decrease the space temperature from 35 ℃ to 25 ℃ was measured and the results are shown in table 1;
(2) energy saving rate: the power consumption (degree) for reducing the space temperature from 35 ℃ to 25 ℃ and maintaining the temperature at 25 ℃ within 60min was measured, and the corresponding energy saving rate was measured, the results are shown in table 1;
the energy saving rate is (R22 power consumption-corresponding refrigerant power consumption)/R22 power consumption multiplied by 100%
(3) Refrigerating capacity: the amount of refrigerant consumed was measured with respect to the cooling capacity of 3.5kW, and the results are shown in Table 1
Table 1.
Application example 2
A refrigerating device: 1.5 pieces of split air conditioner suitable for R410a refrigerant;
the refrigeration method comprises the following steps: the indoor unit of the refrigerating device is arranged at the length, width and height of 4.5 multiplied by 3.3 multiplied by 2.8m3Refrigerants a1-a10 and DA1-DA3 and refrigerant R410a prepared in examples 1 to 10 and comparative examples 1 to 3 were fed to a compressor of a refrigerating apparatus together with lubricant heavy alkylbenzene, respectively (adjusted space temperature was 35 ℃), wherein the amounts of refrigerants a1-a10 and DA1-DA3 and refrigerant R410a were used as shown in table 2.
And (3) testing:
(1) cooling speed: the time taken to decrease the space temperature from 35 ℃ to 25 ℃ was measured and the results are shown in table 2;
(2) energy saving rate: the power consumption (degree) for reducing the space temperature from 35 ℃ to 25 ℃ and maintaining the temperature at 25 ℃ within 60min was measured, and the corresponding energy saving rate was measured, the results are shown in table 2;
energy saving rate (R410a power consumption-corresponding refrigerant power consumption)/R410 a power consumption x 100%
(3) Refrigerating capacity: the consumption of refrigerant was measured with respect to the cooling capacity of 3.5kW, and the results are shown in table 2.
TABLE 2
As can be seen from tables 1 and 2: when the mixed hydrocarbon refrigerant provided by the invention is adopted and propylene, propane and tetrafluoropropene are synergistically used according to the proportion, the energy-saving efficiency of the mixed hydrocarbon refrigerant reaches 17.86-39.29 percent, and preferably 28.57-39.29 percent compared with that of R22 refrigerant under the same conditions when the mixed hydrocarbon mixture is directly used in a refrigerating device of R22. When the mixed hydrocarbon mixture is directly used in a refrigerating device of R410a, the energy-saving efficiency of the refrigerant reaches 33.3-40% compared with that of R410a under the same conditions.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The application of the mixed hydrocarbon refrigerant in a refrigerating device to replace R22 refrigerant or R410a refrigerant is characterized in that the mixed hydrocarbon refrigerant contains propylene, propane and tetrafluoropropene, and the content of the propylene is 81-97 wt%, the content of the propane is 0.5-10 wt% and the content of the tetrafluoropropene is 0.5-10 wt% based on the total weight of the mixed hydrocarbon refrigerant;
when the mixed hydrocarbon refrigerant is used for replacing R22 refrigerant, the using amount of the refrigerant is 0.3-0.6kg relative to the refrigerating capacity of 3.5 kW;
wherein, when the mixed hydrocarbon refrigerant is used for replacing the R410a refrigerant, the usage amount of the refrigerant is 0.3-0.6kg relative to the refrigeration capacity of 3.5 kW.
2. The use according to claim 1, wherein the content of propylene is 91-97 wt%, the content of propane is 1-6 wt%, and the content of tetrafluoropropene is 1-6 wt%, based on the total weight of the mixed hydrocarbon refrigerant.
3. The use according to claim 1, wherein the mixed hydrocarbon refrigerant further comprises methyl mercaptan, wherein the amount of methyl mercaptan is from 0.001 to 0.15% by weight, based on the total weight of the refrigerant.
4. The use according to claim 3, wherein the content of methyl mercaptan is from 0.05 to 0.1% by weight, based on the total weight of the mixed hydrocarbon refrigerant.
5. Use according to claim 4, wherein the weight ratio of the total content of propane and methyl mercaptan to tetrafluoropropene is 1: (0.375-3.5).
6. Use according to claim 5, wherein the weight ratio of the total content of propane and methyl mercaptan to tetrafluoropropene is 1: (0.5-3).
7. The use according to claim 1, wherein the mixed hydrocarbon refrigerant further comprises tetramethylcyclobutane and liquid carbon dioxide, and the content of tetramethylcyclobutane is 0.01-2 wt% and the content of liquid carbon dioxide is 0.01-2 wt% based on the total weight of the mixed hydrocarbon refrigerant.
8. The use according to claim 7, wherein the total content of tetrafluoropropene, tetramethylcyclobutane and liquid carbon dioxide is 2.5-6.5 wt% based on the total weight of the mixed hydrocarbon refrigerant.
9. Use according to any one of claims 1 to 8, wherein the tetrafluoropropene is HFO1234 yf.
10. The use according to claim 1, wherein the refrigeration device is an air conditioner, which uses heavy alkylbenzene as a refrigerator oil.
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