CN113528091A - HFC-161-containing environment-friendly refrigeration composition - Google Patents
HFC-161-containing environment-friendly refrigeration composition Download PDFInfo
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- CN113528091A CN113528091A CN202110370046.2A CN202110370046A CN113528091A CN 113528091 A CN113528091 A CN 113528091A CN 202110370046 A CN202110370046 A CN 202110370046A CN 113528091 A CN113528091 A CN 113528091A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M131/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen
- C10M131/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen containing carbon, hydrogen and halogen only
- C10M131/04—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen containing carbon, hydrogen and halogen only aliphatic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The invention discloses an environment-friendly refrigeration composition containing HFC-161, which consists of HFC-161, a second component and a third component, wherein the second component is HFO-1234yf and/or HFO-1234ze (E), the third component is HFC-32 and/or HFO-1123, and the mass percentages of the components are as follows: HFC-161: 40% -90%; a second component: 5% -30%; a third component: 5 to 40 percent. The refrigeration composition has the advantages of excellent refrigeration performance and heating performance, capability of realizing in-situ replacement of the original system and the like.
Description
Technical Field
The invention relates to the field of refrigerants, in particular to an environment-friendly refrigeration composition which can replace HCFC-22 and R407C in situ and is used in a system originally using HCFC-22 and R407C.
Background
In recent years, global warming has been increasing, and after CFC refrigerants (such as CFC-11 and CFC-12) are being phased out, HCFC refrigerants have been replaced according to the Montreal protocol for ozone depletion in 1987. HCFC-22 is a typical representative of HCFC refrigerant, and is widely used for refrigeration equipment such as air conditioners and the like due to the characteristics of incombustibility, no toxicity, excellent thermal performance and the like. However, HCFC-22 has a certain destruction effect on the atmospheric ozone layer, the GWP (global warming potential) of the HCFC-22 is as high as 1790, and the HCFC-22 is eliminated in 2020 and can be postponed for 10 years in developing countries according to the Montreal agreement. HFC refrigerant is the refrigerant which is more mainstream at present, such as R134a, R407C, R410A and the like, the GWP value of R134a is 1430 which is lower than that of HCFC-22, but the refrigerating capacity per unit volume is far lower than that of HCFC-22; the refrigerating capacity per unit volume of R407C is close to that of HCFC-22, but the GWP of the refrigerant still reaches 1700; the refrigerating capacity per unit volume of R410A is much higher than that of HCFC-22, but the GWP value is 2100, the greenhouse effect is stronger, and HFC refrigerant is also characterized as greenhouse gas in the protocol of Kyoto protocol of climate change framework convention of United nations. Therefore, the development of a substitute refrigerant with low GWP value, high unit volume refrigeration capacity and good refrigeration effect is urgently needed.
Chinese patent CN100500792C discloses a refrigerant composition for replacing HCFC-22, which consists of 5-25% of HFC-161, 25-50% of HFC-125 and 40-50% of HFC-32, the pressure of the composition is similar to that of HCFC-22, the refrigerant composition can replace HCFC-22 under the condition of not changing main components of a system, but the GWP value of the composition is still as high as 1200-2000, and the greenhouse effect is obvious.
Chinese patent CN101649190B discloses a refrigerant replacing R22, which consists of 35-50% of propylene, 30-40% of propane, 5-16% of 1,1,1, 2-tetrafluoroethane, 5-10% of 1,1, 1-trifluoroethane and liquid CO2, can be directly filled in R22 equipment, but has a GWP value of 1080-1180 and an obvious greenhouse effect.
Chinese patent CN104263323B discloses a mixed refrigerant for replacing HCFC-22, which consists of 58-95% of R161, 4-14% of difluoromethane and 1-29% of dimethyl ether, the unit refrigerating capacity of the mixed refrigerant is better than that of HCFC-22, the GWP value is 49.3-74.76, and the mixed refrigerant still has a space for improvement.
Chinese patent CN105018036B discloses a heat transfer fluid for replacing R410, which consists of 40-58% of 1234yf, 40-50% of R32 and 2-10% of R152, wherein the refrigerant can replace R410, but does not disclose the refrigeration effect and GWP value thereof.
Chinese patent CN110373158A discloses a thermal cycle working medium, which can be: HFO-1123, HFO-1234yf and/or 1234ze (E), an efficiency factor with respect to R410A and a freezing capacity are good, a GWP value < 10; the working medium may be: 30-90% of HFO-1123, 5-55% of HFO-1234yf and 10% of R134 a/5% of R125/(10-30%) of R32, wherein the efficiency coefficient and the refrigerating capacity are good relative to R410A, and the GWP value is 68-204. None of the above compositions disclose the possibility of in situ substitution of R410A and the specific refrigeration capacity of the composition.
Disclosure of Invention
In order to solve the technical problems, the invention provides an environment-friendly refrigeration composition with good refrigeration performance, low GWP value and low flammability, and the in-situ substitution of HCFC-22 and R407C is realized by adjusting the proportion of each component.
The purpose of the invention is realized by the following technical scheme:
an environment-friendly refrigeration composition containing HFC-161, the refrigeration composition comprises HFC-161, a second component and a third component, the second component is HFO-1234yf and/or HFO-1234ze (E), the third component is HFC-32 and/or HFO-1123, and the mass percentages of the components are as follows: HFC-161: 40% -90%; a second component: 5% -30%; a third component: 5 to 40 percent. Preferably, the refrigeration composition has an HFC-161: 70% -90%; a second component: 5% -20%; a third component: 5 to 20 percent.
The refrigeration composition has a GWP value of < 300, more preferably the refrigeration composition has a GWP value of < 150. The refrigeration composition can be used as a heat transfer medium, particularly, the refrigeration composition in the proportioning range is used for replacing HCFC-22 and R407C as the heat transfer medium in refrigeration systems such as automobile air conditioners, household air conditioners, commercial air conditioners, refrigeration cases, freezers or refrigeration houses, can be dissolved with lubricating oil in the original refrigeration systems, and through further proportioning design, parameters such as evaporation pressure, condensation pressure and the like of the refrigeration composition are equivalent to HCFC-22 and R407C, so that in-situ replacement of the refrigeration composition is realized.
In one technical scheme, the refrigeration composition is directly filled into a refrigeration system which originally uses HCFC-22 and R407C. During the operation of the refrigeration system, the refrigeration composition and the lubricant are inevitably contacted and dissolved to form a liquid mixture, so that the phenomenon that the two are not dissolved and accumulated in a coil, a pipeline or a heat transfer component (such as an evaporator) of the refrigeration system to reduce the working efficiency of the system is avoided.
Preferably, therefore, the present invention provides a liquid mixture comprising the environmentally friendly refrigeration composition as defined in any one of the above and a lubricating oil present in the liquid mixture in an amount of at most 50% by weight, and the refrigeration composition and the lubricating oil in the liquid mixture are compatible and non-demixing in the entire temperature range of-50 ℃ to 100 ℃. More preferably, the lubricating oil is present in the liquid mixture in an amount of up to 10 wt.%, and the refrigeration composition and lubricating oil in the liquid mixture are miscible over the entire temperature range of-40 ℃ to 80 ℃; most preferably, the lubricating oil is present in the liquid mixture in an amount of 2 to 3 wt%.
The lubricating oil is selected from at least one of polyol ester (POE), polyalkylene glycol (PAG), PAG oil, silicone oil, mineral oil, Alkylbenzene (AB), polyvinyl ether (PVE) and poly (alpha-olefin) (PAO). Further preferably, the lubricating oil is POE.
In a more preferred embodiment, when the refrigeration composition is used in a refrigeration system originally using HCFC-22, R407C, the lubricating oil may be further adjusted to improve heat transfer performance. More preferably, on the basis of optimizing the lubricating oil, matching parameters such as parts (an evaporator, a condenser, a throttling device and the like) and a filling amount and the like in the original system are optimally designed and adjusted so as to improve the heat transfer efficiency. Most preferably, on the basis of the above, the performance of the compressor is further adjusted and optimized to improve the COP.
Compared with the prior art, the invention has the beneficial effects that:
1. the refrigeration composition has zero ODP, low GWP value and weak flammability, has environmental performance superior to that of substituted HCFC-22 and R407C, meets the requirements of low GWP and weak flammability, and is suitable for commercial application.
2. The refrigerating composition has better refrigerating effect and heating performance than or equal to HCFC-22 or R407C under the same working condition, and can be used in systems such as automobile air conditioners, household air conditioners, commercial air conditioners, refrigerating boxes, freezing boxes or refrigeratory and the like.
3. The refrigeration composition has good chemical stability and does not generate self-decomposition reaction at the high temperature of 175 ℃.
4. Under the working condition of a standard air conditioner, the evaporation pressure, the condensation pressure and the like of the refrigerating composition replacing HFC-22/R407C are all equivalent to HCFC-22/R407C, the unit volume refrigerating capacity/unit volume heating capacity is higher than or equivalent to HCFC-22/R407C, the COP value is basically higher than HCFC-22/R407C, and the comprehensive performance is close to that of HCFC-22/R407C.
5. The refrigerating composition has good intermiscibility with POE lubricating oil, can be directly used in a refrigerating system originally using HCFC-22 or R407C on the premise of not changing main parts of equipment, is compatible with a pipeline part of the refrigerating system originally using HCFC-22 or R407C, can reduce the filling amount, improves the refrigerating effect and has the advantage of energy conservation.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
The invention provides a refrigeration composition, which is prepared by physically mixing fluoroethane (HFC-161, R161), 2,3,3, 3-tetrafluoropropene (HFO-1234yf), Trans-1,3,3, 3-tetrafluoropropene (HFO-1234ze (E)), difluoromethane (HFC-32, R32) and trifluoroethylene (HFO-1123) in a liquid phase according to the corresponding proportion of each component.
Example 1: HFC-161, HFO-1234ze (E) and HFO-1123 are physically mixed in the liquid phase at a mass ratio of 80:10: 10.
Example 2: HFC-161, HFO-1234yf and HFO-1123 are physically mixed in the liquid phase at a mass ratio of 80:10: 10.
Example 3: HFC-161, HFO-1234ze (E) and HFC-32 are physically mixed in the liquid phase in a mass ratio of 80:10: 10.
Example 4: HFC-161, HFO-1234yf and HFC-32 are physically mixed in the liquid phase at a mass ratio of 60:20: 20.
Example 5: HFC-161, HFO-1234yf and HFC-32 are physically mixed in the liquid phase at a mass ratio of 40:20: 40.
Comparative example 1: HFC-161, HFO-1234ze (E) and HFO-1234yf are physically mixed in the liquid phase at a mass ratio of 10:20: 70.
Comparative example 2: HFC-161, HFO-1234ze (E) and HFC-32 are physically mixed in the liquid phase at a mass ratio of 20:75: 5.
Environmental Performance vs. flammability
The environmental performance and the fire rating of the above examples, comparative examples and HFC-22, R407C are given in table 1 below. Wherein the ODP value takes CFC-11 as a reference value of 1.0, and the GWP value takes CO2As a reference value of 1.0(100 years).
TABLE 1 environmental Properties and flammability
| Working medium | ODP | GWP | Grade of combustion |
| Example 1 | 0 | 3.6 | 2 |
| Example 2 | 0 | 3.6 | 2 |
| Example 3 | 0 | 71 | 2 |
| Example 4 | 0 | 138 | 2 |
| Example 5 | 0 | 205 | 2 |
| Comparative example 1 | 0 | 6 | 2L |
| Comparative example 2 | 0 | 35 | 2L |
| HCFC-22 | 0.05 | 1790 | 1 |
| R407C | 0 | 1700 | 1 |
As can be seen from Table 1, the GWP of each example is lower than that of HCFC-22 and R407C, and the environmental performance is excellent; the burning grade of each embodiment is similar to that of each proportion, and the safety is equivalent.
Thermal parameter and thermal performance comparison of HFC-22 and R407C substituted refrigeration composition under standard air conditioner working condition
The thermal parameters and the thermodynamic properties of the refrigeration compositions of examples 1 to 5, the compositions of comparative example 1 and comparative example 2, HCFC-22 and R407C were compared under standard air conditioning conditions (the invention used: evaporation temperature 7.2 ℃; condensation temperature 54.4 ℃; suction temperature 18.3 ℃; supercooling temperature 46.1 ℃ and mechanical efficiency 1.0), and the comparison results are shown in Table 2 below:
TABLE 2 comparison of thermal parameters and thermal Properties of HCFC-22, R407C alternative compositions
As can be seen from Table 2, the refrigeration compositions of examples 1 to 5 have densities less than that of HCFC-22, R407C, comparative examples 1 and 2, and refrigeration capacities per unit mass greater than that of HCFC-22, R407C, comparative examples 1 and 2, indicating that the refrigeration compositions of examples 1 to 5 can reduce the refrigerant charge of the system.
The system pressure and pressure ratio of the refrigeration compositions of examples 1-5 are equivalent to those of HCFC-22 and R407C, indicating that the refrigeration compositions can be directly used in a system using HCFC-22 or R407C.
The refrigerating capacity per unit volume of the refrigerating composition in the embodiment 1-5 is equivalent to that of HCFC-22 and R407C, and is much higher than that of the refrigerating composition in the comparative example 1 and the refrigerating composition in the comparative example 2. The refrigeration compositions of examples 1 to 4, except the refrigeration composition of example 5, all had energy efficiency ratios greater than HCFC-22 and R407C, indicating that they had comparable or superior use effects to HCFC-22 and R407C.
Third, HFC-22, R407C substitute the refrigeration composition to compare the thermal parameter and thermal performance under the heating condition
Under the condition of the heating technology (the invention adopts that the evaporation temperature is minus 16.1 ℃, the condensation temperature is 31.4 ℃, the suction temperature is minus 5.0 ℃, the supercooling temperature is 20.0 ℃, and the mechanical efficiency is 1.0), the thermal parameters and the thermodynamic properties of the refrigeration compositions of the examples 1 to 5, the compositions of the comparative examples 1 and 2, HCFC-22 and R407C are compared, and the comparison result is shown in the following table 3:
TABLE 3 comparison of thermal parameters and thermal Properties of HCFC-22, R407C alternative compositions
As can be seen from Table 3, the heating capacity per unit mass of examples 1 to 5 is greater than that of HCFC-22 and R407C, and comparative examples 1 and 2, indicating that the refrigeration compositions of examples 1 to 5 can reduce the refrigerant charge of the system. The system pressure and pressure ratio of the refrigeration compositions of examples 1-5 are equivalent to those of HCFC-22 and R407C, indicating that the refrigeration compositions can be directly used in a system using HCFC-22 or R407C. The refrigerating compositions of examples 1-5 have a heating capacity per unit volume equivalent to that of HCFC-22 and R407C, much higher than that of comparative examples 1 and 2. The refrigeration compositions of examples 1 to 4, except the refrigeration composition of example 5, all had energy efficiency ratios greater than HCFC-22 and R407C, indicating that they had comparable or superior use effects to HCFC-22 and R407C.
Claims (7)
1. An environment-friendly refrigeration composition containing HFC-161, which is characterized in that: the refrigeration composition comprises HFC-161, a second component and a third component, wherein the second component is HFO-1234yf and/or HFO-1234ze (E), the third component is HFC-32 and/or HFO-1123, and the mass percentages of the components are as follows:
HFC-161：40％～90％；
a second component: 5% -30%;
a third component: 5 to 40 percent.
2. An environmentally friendly refrigeration composition comprising HFC-161 as recited in claim 1 wherein: the refrigeration composition comprises the following components in percentage by mass:
HFC-161：70％～90％；
a second component: 5% -20%;
a third component: 5 to 20 percent.
3. An environmentally friendly refrigeration composition comprising HFC-161 as recited in claim 1 or 2 wherein: the refrigeration composition is used as a heat transfer medium.
4. An environmentally friendly refrigeration composition comprising HFC-161 as recited in claim 1 wherein: the refrigerant composition has a GWP of less than 300 and is useful as a heat transfer medium in place of HCFC-22, R407C.
5. Use of an environmentally friendly refrigeration composition comprising HFC-161 as claimed in any one of claims 1 to 4, wherein: the refrigeration composition is used in an automotive air conditioner, a household air conditioner, a commercial air conditioner, a refrigerator, a freezer or a freezer.
6. A liquid mixture characterized by: the liquid mixture comprising the environmentally friendly refrigeration composition of any one of claims 1 to 4 and a lubricating oil present in the liquid mixture in an amount of up to 50% by weight, and the refrigeration composition and lubricating oil in the liquid mixture being compatible over the entire temperature range of-50 ℃ to 100 ℃.
7. The liquid mixture according to claim 6, wherein: the lubricating oil is selected from at least one of polyol ester (POE), polyalkylene glycol (PAG), PAG oil, silicone oil, mineral oil, Alkylbenzene (AB), polyvinyl ether (PVE) and poly (alpha-olefin) (PAO).
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| CN113528090B (en) | 2023-09-26 |
| CN113528090A (en) | 2021-10-22 |
| CN113528091B (en) | 2023-03-24 |
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