CN111253912A - Environment-friendly mixed refrigerant replacing R290 - Google Patents
Environment-friendly mixed refrigerant replacing R290 Download PDFInfo
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 120
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims abstract description 53
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 50
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims abstract description 37
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 32
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001282 iso-butane Substances 0.000 claims abstract description 25
- 229940051271 1,1-difluoroethane Drugs 0.000 claims abstract description 16
- 238000005057 refrigeration Methods 0.000 claims abstract description 15
- 239000001294 propane Substances 0.000 claims abstract description 14
- 238000010792 warming Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 19
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 7
- 229920001289 polyvinyl ether Polymers 0.000 claims description 6
- -1 polyol esters Chemical class 0.000 claims description 4
- 229920013639 polyalphaolefin Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 14
- 238000009472 formulation Methods 0.000 description 6
- 238000004378 air conditioning Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 3
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- 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
- 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
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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
- C09K2205/40—Replacement mixtures
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- Lubricants (AREA)
Abstract
The invention provides an environment-friendly mixed refrigerant replacing R290, which comprises a first component, a second component and a third component, wherein: a first component of 1, 1-difluoroethane (R152a), a second component of 2,3,3, 3-tetrafluoropropene (R1234yf), and a third component of one of propane (R290), isobutane (R600a), and propene (R1270), wherein the environmentally-friendly mixed refrigerant has a Global Warming Potential (GWP) of no greater than 150; and ODP is zero, and the flammability is lower than R290, the safety performance is better than R290, the thermal performance is equivalent to or even better than that of R290 refrigerant, and the refrigerant can completely replace R290 to be used in refrigeration setting, especially on household air conditioners.
Description
Technical Field
The invention relates to the technical field of refrigerants, in particular to an environment-friendly mixed refrigerant for replacing R290.
Background
With the trend of environmental protection becoming more serious, and with respect to the "greenhouse effect" of HFCs, the montreal protocol amendment requires a refrigerant which is not ozone-depleting and has a low GWP value to replace the current high GWP refrigerant, and is effectively applied to air conditioning systems. Because the natural working medium R290 has better environmental protection performance and is often used in a household air conditioning system, but because the natural working medium R290 is an A3 flammable refrigerant, the safety is greatly insufficient, and therefore, a refrigerant with good environmental protection performance, high safety and equal or better thermal performance than R290 is urgently needed to replace.
Disclosure of Invention
In view of the above, the invention provides an environment-friendly mixed refrigerant replacing R290, which has good environment-friendly performance, does not damage the atmospheric ozone layer, namely ODP is zero, and has lower GWP (GWP is lower than 150), the safety performance is better than R290, and the thermal performance is not much different from that of R290 or even better, thereby solving the technical problem of poor safety performance of the R290 refrigerant of the existing household air conditioner.
In order to achieve the purpose, the invention adopts the technical scheme that: an environment-friendly mixed refrigerant replacing R290, comprising a first component, a second component and a third component, wherein: the first component is 1, 1-difluoroethane (R152a), the second component is 2,3,3, 3-tetrafluoropropene (R1234yf), and the third component is one of propane (R290), isobutane (R600a), and propene (R1270), wherein the environmentally-friendly mixed refrigerant has a Global Warming Potential (GWP) of not greater than 150.
Further optionally, the first component is 4-48%, the second component is 28-92%, and the third component is 4-28% by mole percentage. The safety performance of the environment-friendly mixed refrigerant prepared by the formula is superior to that of R290, and the thermal performance of the environment-friendly mixed refrigerant is equivalent to or even superior to that of R290.
Further optionally, the first component is 4-40%, the second component is 56-84%, and the third component is 4-20% by mole percentage. The safety performance of the environment-friendly mixed refrigerant prepared by the formula is superior to that of R290, and the thermal performance of the environment-friendly mixed refrigerant relative to R290 is more than 0.99.
Further optionally, the first component is 28-40%, the second component is 56-68%, and the third component is 4-12% by mole percentage. The safety performance of the environment-friendly mixed refrigerant prepared by the formula is superior to that of R290, and the thermal performance of the environment-friendly mixed refrigerant relative to R290 is more than 0.99.
Further optionally, the third component is isobutane (R600 a). The safety performance of the environment-friendly mixed refrigerant prepared by the formula is superior to that of R290, and the thermal performance of the environment-friendly mixed refrigerant relative to R290 is more than 0.99.
Further optionally, the sum of the mole percentages of the first component, the second component, and the third component, in mole percent, is 100%, wherein: the first component is 4-48%, the second component is 28-92%, and the third component is 4-28%.
Further optionally, the flammability of the environmentally friendly mixed refrigerant is A2 or A2L.
The invention also provides a composition, which comprises 1-5% of lubricant and 95-99% of the environment-friendly mixed refrigerant replacing R290 in mole percentage.
Further optionally, wherein the lubricant is selected from at least one of silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (α -olefins), or a combination of at least two thereof.
The invention also provides a refrigeration system using the environmentally friendly mixed refrigerant or the composition.
The invention also provides refrigeration equipment, and the refrigeration equipment adopts the refrigeration system.
Further optionally, the refrigeration equipment is any one of a central air conditioner, a heat pump air conditioner and a household air conditioner.
Compared with R290 refrigerant, the environment-friendly mixed refrigerant has obvious environment-friendly advantages, the heat transfer composition has good thermal performance, the GWP of the heat transfer composition is lower than 150, and the ODP is 0; after the refrigerant is applied to a refrigerating system, the relative unit volume refrigerating capacity and the relative efficiency COP of the refrigerant are equivalent to or even better than those of the refrigerating system using the R290 refrigerant, and meanwhile, the safety performance of the refrigerant is superior to that of the R290 refrigerant, so that the refrigerant can be used in the refrigerating system instead of the R290 refrigerant.
The components of the present invention are commercially available or can be prepared by methods known in the art. The content ratio of each component in the invention is obtained by screening a large amount, which is a condition for ensuring the excellent performance of the environment-friendly mixed refrigerant.
Detailed Description
The preparation method of the environment-friendly mixed refrigerant used by the refrigeration system comprises the steps of physically mixing various components such as 1, 1-difluoroethane (R152a), 3,3, 3-tetrafluoropropene (R1234yf), propane (R290), isobutane (R600a) and propene (R1270) in a normal-temperature normal-pressure liquid phase state according to different molar ratios according to the technical scheme, and uniformly mixing to form the environment-friendly mixed refrigerant. The basic parameters of the component materials are shown in Table 1.
TABLE 1 basic parameters of each component substance in the environment-friendly mixed refrigerant
Specific examples and comparative examples are given below, in which the proportions of the components are molar ratios and the sum of the molar ratios of the component substances of each of the environment-friendly mixed refrigerants is 100%. In each embodiment, the components are physically mixed in liquid phase according to a fixed molar ratio under the normal temperature and pressure liquid phase state, and the environment-friendly mixed refrigerant is obtained after uniform mixing.
In example 1, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propane (R290), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 24:72:4, and were uniformly mixed to obtain an environmentally friendly mixed refrigerant.
In example 2, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propane (R290), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 28:68:4, and were uniformly mixed to obtain an environmentally friendly mixed refrigerant.
Example 3, three components of 1, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propane (R290) were physically mixed at room temperature and normal pressure in a liquid phase at a molar ratio of 32:64:4, and uniformly mixed to obtain an environmentally friendly mixed refrigerant.
In example 4, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propane (R290), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 36:60:4, and were uniformly mixed to obtain an environmentally friendly mixed refrigerant.
In example 5, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propane (R290), were physically mixed at room temperature and normal pressure in a liquid phase at a molar ratio of 48:48:4, and were uniformly mixed to obtain an environmentally friendly mixed refrigerant.
In example 6, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a), were physically mixed at room temperature and normal pressure in a liquid phase at a molar ratio of 20:72:8, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 7, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a), were physically mixed at room temperature and normal pressure in a liquid phase at a molar ratio of 24:68:8, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 8, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a), were physically mixed at room temperature and normal pressure in a liquid phase at a molar ratio of 28:68:4, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 9, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 32:64:4, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 10, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a), were physically mixed at room temperature and normal pressure in a liquid phase at a molar ratio of 36:60:4, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 11, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 40:56:4, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 12, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 44:28:28, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 13, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propene (R1270), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 4:92:4, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 14, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propene (R1270), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 8:88:4, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 15, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propene (R1270), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 12:84:4, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 16, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propene (R1270), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 16:80:4, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 17, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propene (R1270), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 20:76:4, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 18, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propene (R1270), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 24:72:4, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 19, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propene (R1270), were physically mixed at room temperature and normal pressure in a liquid phase at a molar ratio of 48:48:4, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 20, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 4:84:12, and were uniformly mixed to obtain an environmentally friendly mixed refrigerant.
In example 21, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 8:72:20, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 22, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a), were physically mixed at room temperature and pressure in a liquid phase at a molar ratio of 8:80:12, and mixed uniformly to obtain an environmentally friendly mixed refrigerant.
In example 23, three components, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a), were physically mixed at room temperature and normal pressure in a liquid phase at a molar ratio of 12:68:20, and were uniformly mixed to obtain an environmentally friendly mixed refrigerant.
Comparative example 1, three components of 1, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propane (R290) were physically mixed at room temperature and normal pressure in a liquid phase at a molar ratio of 32:4:64, and mixed uniformly to obtain a mixed refrigerant.
Comparative example 2, three components of 1, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a) were physically mixed at room temperature and normal pressure in a liquid phase at a molar ratio of 20:12:68, and mixed uniformly to obtain a mixed refrigerant.
Comparative example 3: physically mixing three components of 1, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and isobutane (R600a) at the normal temperature and pressure according to the molar ratio of 2:70:28, and uniformly mixing to obtain the mixed refrigerant.
Comparative example 4: the three components of 1, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propane (R290) are physically mixed according to a molar ratio of 50:28:22 under normal temperature and pressure liquid phase, and the mixture is uniformly mixed to obtain the mixed refrigerant.
Comparative example 5: the three components of 1, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propane (R290) are physically mixed according to the molar ratio of 48:24:28 under normal temperature and pressure liquid phase, and the mixture is uniformly mixed to obtain the mixed refrigerant.
Comparative example 6: the three components of 1, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propene (R1270) are physically mixed according to the molar ratio of 4:94:2 under normal temperature and pressure liquid phase, and the mixture is uniformly mixed to obtain the mixed refrigerant.
Comparative example 7: the three components of 1, 1-difluoroethane (R152a), 2,3,3, 3-tetrafluoropropene (R1234yf) and propene (R1270) are physically mixed according to the molar ratio of 42:28:30 under normal temperature and pressure liquid phase, and the mixture is uniformly mixed to obtain the mixed refrigerant.
Table 2 compares the above examples and comparative examples with basic parameters of molecular weight, critical temperature and environmental properties of R290, in which flammability was calculated according to the theoretical model in the paper published in 2019 by NIST, wherein flammability was decreased in the order of A3, A2 and A2L.
TABLE 2 basic parameters of mixed refrigerants
The present embodiment also provides a composition comprising a lubricant and 1 to 5 mole percent of an eco-friendly mixed refrigerant replacing R290 in any one of the above embodiments, and 95 to 99 mole percent of an eco-friendly mixed refrigerant replacing R290, preferably wherein the lubricant is at least one selected from the group consisting of silicone oil, Polyalkylbenzene (PAB), polyol ester (POE), polyalkylene glycol (PAG), polyalkylene glycol ester (PAG ester), polyvinyl ether (PVE), poly (α -olefin), or a combination of at least two thereof.
The embodiment also provides a refrigeration device, wherein any one of the refrigeration device central air conditioner, the heat pump air conditioner and the household air conditioner is adopted, and the adopted refrigeration system uses any one of the environment-friendly mixed refrigerants or compositions in the embodiments. Further preferably, the refrigeration system uses the environmentally friendly mixed refrigerant of any one of the embodiments.
The ternary refrigerant provided by the embodiment and the comparative example is applied to a household air conditioning system, exchanges heat in an air conditioning unit, is compressed and throttled, and replaces R290 refrigerant.
Table 3 compares thermodynamic parameters (i.e., compression ratio and exhaust temperature) and relative thermodynamic properties (i.e., relative refrigerating capacity per unit volume and relative efficiency COP) of the above-described examples and R290 in terms of isentropic compression under refrigeration conditions (evaporator outlet temperature of 283.15K, condenser outlet temperature of 313.15K, vapor phase at the evaporator outlet of superheated state, superheat degree of 5K, liquid phase at the condenser outlet of subcooled state, subcooling degree of 5K, adiabatic efficiency of compressor of 0.75) with the mixed refrigerant of the comparative example.
Table 3 performance comparison of mixed refrigerant with R290
The analysis in table 2 and table 3 shows that compared with the mixed refrigerant in the comparative example, the environment-friendly mixed refrigerant in the present example maintains the flammability, GWP, relative volumetric refrigerating capacity, and other properties of the prepared environment-friendly mixed refrigerant in a good state through the synergistic effect between the components.
It was found that, when the molar percentages of the second component and the third component in the formulation were out of the range of the values provided by the present invention, i.e., the second component was less than the minimum value of 28% provided by the present invention, and the third component was out of the range of 28% provided by the present invention, it was possible to prepare a mixed refrigerant having strong ignitability of a3 refrigerant and hardly any improvement in thermal properties with respect to R290 refrigerant, particularly comparative example 2 having a relative volumetric refrigerating capacity of only 50% of that of R290 refrigerant, and thus, it was not possible to use it as a preferred substitute refrigerant for R290 refrigerant.
It can be seen from comparative examples 3-7 that when the molar percentage of any one of the first, second and third components in the formulation is outside the range provided by the present invention, i.e., above or below the range provided by the present invention, the prepared mixed refrigerant has further reduced flammability relative to R290, but has a greater reduction in energy efficiency relative to R290, reaching only 87% of R290 at most, and has poor thermal performance. Therefore, it cannot be used as a preferable alternative refrigerant for the R290 refrigerant.
Therefore, the mixed environment-friendly refrigerant provided by the invention has the GWP of less than 150 through the synergistic effect among the first component, the second component and the third component, is good in environment-friendliness, and has safety performance superior to R290 because the flammability of all the refrigerants is A2L or A2.
As can be seen from tables 2 and 3, the volume cooling capacity of the environment-friendly mixed refrigerant provided by the present embodiment is only about 77% of that of R290, but the COP value is equivalent to, even better than, R290, and the refrigerant can be an environment-friendly refrigerant replacing R290. From the analysis of examples 6-11 and examples 20-23, the third component is preferably isobutane (R600a), and the flammability of the environmentally friendly mixed refrigerant with the component is lower than that of R290, and the relative COP is better than that of the third component which is one of propane (R290) and propylene (R1270); it has further been analyzed that, in the formulation of isobutane (R600a) as the third component, preferably, in terms of mole percentage, the mixed environment-friendly refrigerant prepared from the formulation of 4% to 40% of 1, 1-difluoroethane (R152a), 56% to 84% of 2,3,3, 3-tetrafluoropropene (R1234yf) and 4% to 20% of isobutane (R600a) has a relative COP of greater than 0.9; further, the analysis shows that the relative COP of the environment-friendly mixed refrigerant prepared by the formula with the molar percentages of 28-40% of 1, 1-difluoroethane (R152a), 56-68% of 2,3,3, 3-tetrafluoropropene (R1234yf) and 4-12% of isobutane (R600a) is greater than 0.99 due to R290. Further preferred, in mole percent, is 1, 1-difluoroethane (R152 a): 2,3,3, 3-tetrafluoropropene (R1234 yf): the formulation with 40:56:4 isobutane (R600a) produced the environmentally friendly mixed refrigerant with a relative COP of up to 1.003, which is the most preferred formulation.
The environment-friendly mixed refrigerant replacing R290 provided by the embodiment has the environment-friendly characteristics of lower GWP than 150 and zero ODP, has the flammability lower than R290, has better safety performance than R290, has equivalent or even better thermal performance than that of the R290 refrigerant, and can completely replace R290 to be used in refrigeration settings, especially household air conditioners.
In summary, the present invention provides an environment-friendly mixed refrigerant replacing R290, which comprises a first component, a second component and a third component, wherein: a first component of 1, 1-difluoroethane (R152a), a second component of 2,3,3, 3-tetrafluoropropene (R1234yf), and a third component of one of propane (R290), isobutane (R600a), and propene (R1270), wherein the environmentally-friendly mixed refrigerant has a Global Warming Potential (GWP) of no greater than 150; and ODP is zero, and the flammability is lower than R290, the safety performance is better than R290, the thermal performance is equivalent to or even better than that of R290 refrigerant, and the refrigerant can completely replace R290 to be used in refrigeration setting, especially on household air conditioners.
Exemplary embodiments of the present disclosure are specifically illustrated and described above. It is to be understood that the present disclosure is not limited to the precise arrangements, instrumentalities, or instrumentalities described herein; on the contrary, the disclosure is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (12)
1. An environment-friendly mixed refrigerant replacing R290, which is characterized by comprising a first component, a second component and a third component, wherein: the first component is 1, 1-difluoroethane (R152a), the second component is 2,3,3, 3-tetrafluoropropene (R1234yf), and the third component is one of propane (R290), isobutane (R600a), and propene (R1270), wherein the environmentally-friendly mixed refrigerant has a Global Warming Potential (GWP) of not greater than 150.
2. The environmentally friendly mixed refrigerant as recited in claim 1 in place of R290, wherein the first component is 4% to 48%, the second component is 28% to 92%, and the third component is 4% to 28% by mole.
3. The environmentally friendly mixed refrigerant as recited in claim 2 in place of R290, wherein the first component is 4% to 40%, the second component is 56% to 84%, and the third component is 4% to 20% by mole.
4. The environmentally friendly mixed refrigerant as recited in claim 2 in place of R290, wherein the first component is 28% to 40%, the second component is 56% to 68%, and the third component is 4% to 12% by mole.
5. The environmentally friendly mixed refrigerant replacing R290 as set forth in claim 2, wherein said third component is isobutane (R600 a).
6. The environmentally friendly mixed refrigerant as recited in claim 1 in place of R290, wherein the sum of the mole percentages of the first component, the second component and the third component is 100%, wherein: the first component is 4-48%, the second component is 28-92%, and the third component is 4-28%.
7. The environment-friendly mixed refrigerant replacing R290 as claimed in any one of claims 1 to 6, wherein the flammability of the environment-friendly mixed refrigerant is A2 or A2L.
8. A composition comprising a lubricant and the environmentally friendly mixed refrigerant of any one of claims 1 to 7 replacing R290, wherein the lubricant is 1 to 5 mole percent, and the environmentally friendly mixed refrigerant of any one of claims 95 to 99 mole percent.
9. The composition of claim 8, wherein the lubricant is at least one member selected from the group consisting of silicone oils, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (α -olefins), and combinations of at least two members.
10. A refrigeration system using the environmentally friendly mixed refrigerant of any one of claims 1 to 7 or the composition of any one of claims 8 to 9.
11. A refrigerating apparatus characterized by employing the refrigerating system of claim 10.
12. The refrigerating apparatus as recited in claim 11, wherein said refrigerating apparatus is any one of a central air conditioner, a heat pump air conditioner and a household air conditioner.
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CN113980649A (en) * | 2021-11-09 | 2022-01-28 | 珠海格力电器股份有限公司 | Mixed refrigerant and air conditioning system |
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CN115627155A (en) * | 2022-09-08 | 2023-01-20 | 珠海格力电器股份有限公司 | Quaternary environment-friendly mixed refrigerant, and preparation method and application thereof |
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