CN110591649B - Near-azeotropic mixed working medium, heat exchange system and HVACR system - Google Patents
Near-azeotropic mixed working medium, heat exchange system and HVACR system Download PDFInfo
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- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical group FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims abstract description 60
- YFMFNYKEUDLDTL-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)C(F)(F)F YFMFNYKEUDLDTL-UHFFFAOYSA-N 0.000 claims abstract description 59
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims abstract description 59
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical group F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims abstract description 34
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 78
- 239000012530 fluid Substances 0.000 claims description 46
- 239000003507 refrigerant Substances 0.000 claims description 46
- 238000005057 refrigeration Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 12
- 239000007791 liquid phase Substances 0.000 description 43
- 230000000052 comparative effect Effects 0.000 description 18
- 238000009835 boiling Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 2
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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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
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with refrigerants
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B41/00—Fluid-circulation arrangements
- F25B41/40—Fluid line arrangements
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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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Abstract
The invention provides a near-azeotropic mixed working medium, which comprises four components, wherein the first component is 1,1,1, 2-tetrafluoroethane (R134a) accounting for 1-43% of the mass; the second component is 1 to 97 percent of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass; the third component is trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) accounting for 1-97% by mass; the fourth component is 1 to 17 mass percent of 1,1,1,2,3,3, 3-heptafluoropropane (R227 ea). The near-azeotropic mixed working medium not only has the environmental protection characteristics of low GWP and zero ODP, but also has excellent thermal performance and small temperature slippage, and can be used as a mixed working medium which replaces R134a and is harmless to the ozone layer.
Description
Technical Field
The invention relates to a refrigerant technology, in particular to a near-azeotropic mixed working medium, a heat exchange system and an HVACR system.
Background
The refrigerant is a carrier for realizing energy conversion and utilization of the refrigeration system, and the quality of the thermodynamic performance of the refrigerant plays a crucial role in the energy utilization efficiency of the system. In recent years, two major environmental problems, ozone depletion and greenhouse effect, have attracted global attention.
The novel environment-friendly energy-saving working medium is required to have more excellent environmental performance. Firstly, the Ozone Depletion Potential (ODP) is 0 and the greenhouse effect potential (GWP) is small; secondly, the safety performance is good, namely the flammability is low or the incombustibility is low; thirdly, the toxicity is low, and the national relevant regulations are met; fourthly, the thermodynamic property is excellent, and the circulation efficiency is higher. Generally, the existing pure refrigerant is difficult to meet all requirements of replacing the refrigerant, and the mixed refrigerant may concentrate the advantages of all components to form a novel refrigerant meeting various requirements of environmental protection, safety, performance and the like. Meanwhile, the mixed refrigerant has low use cost, and is beneficial to relieving the pressure of China on the elimination of CFCs and HCFCs refrigerants and industrial upgrading.
However, the main components of the existing mixed refrigerant are HFCs, ODP values are 0, but the mixed refrigerant has a high GWP value, and cannot be used as a long-term substitute refrigerant. The Chinese invention patent with publication number CN101671544A proposes that a mixed refrigerant with the components of R22, R142b and R21 is used to replace R12. All the components of the mixed refrigerant contain chlorine atoms, and the ODP value of the mixed refrigerant is not zero, so the mixed refrigerant cannot be called as an environment-friendly refrigerant. The Chinese invention patent with the publication number of CN1740262A provides a mixed refrigerant with the components of R290, R600a and THT (tetrahydrothiophene), and the mass ratio of the mixed refrigerant used for replacing R12 is as follows: 61%, 38.5% and 0.5%. Wherein, the components R290 and R600a are all inflammable and explosive substances and occupy 99.5 percent of mass proportion, thereby limiting the filling amount of the mixed refrigerant. The Chinese invention patent with publication number CN101307223A proposes a mixed refrigerant with components of R134, R152a and R600a, and the optimized mass ratio of the mixed refrigerant is 1-25%, 40-81% and 18-35%. The refrigerant has smaller condensation and evaporation slip temperatures and thermodynamic performance slightly lower than that of R12, but the refrigerant has poorer environmental protection performance due to the fact that the refrigerant contains R134a and R152a with larger mass ratio and the GWP of the two refrigerants is higher. The chinese invention patent with publication number CN101003723A discloses a mixed refrigerant with components R152a, R227ea and R125, all of which have higher GWP values, and thus do not have better environmental protection performance.
The refrigerant mixture proposed in the existing documents often has the defects of higher GWP value, flammability, smaller volume refrigerating capacity, larger temperature slippage and the like, so the development of refrigerator refrigerants with higher refrigerating performance, better compatibility with the existing systems and better environmental protection performance is particularly urgent.
Disclosure of Invention
In view of the above, the invention provides a near-azeotropic mixed working medium, which has a GWP of 600 or less and an ODP of 0, has obvious environmental protection advantages, and has good thermal performance, and can not only solve the problem that the GWP of the existing refrigerant for replacing R134a is relatively high, but also prevent the problem that the heat exchange efficiency is reduced due to the sliding temperature of the refrigerant in the process of using the refrigerant by a refrigeration device because the sliding temperature is 0.52 ℃ or less.
In order to achieve the purpose, the invention adopts the technical scheme that: a near-azeotropic mixed working medium comprises four components, wherein the first component is 1,1,1, 2-tetrafluoroethane (R134a) accounting for 1-43% of the mass; the second component is 1-97% of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass; the third component is trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) accounting for 1-97% by mass; the fourth component is 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) accounting for 1-17% by mass.
Further optionally, the near-azeotropic mixture working medium comprises four components, wherein the first component is 30-43% by mass of 1,1,1, 2-tetrafluoroethane (R134 a); the second component is 36-68% of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass; the third component is trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) accounting for 1-22% by mass; the fourth component is 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) accounting for 1-6% of the mass. The mass ratio of the four components of the near-azeotropic mixed working medium is respectively in the range, so that the near-azeotropic mixed working medium has better refrigeration performance and small temperature slippage.
Further optionally, the near-azeotropic mixture comprises four components, wherein the first component is 39% by mass of 1,1,1, 2-tetrafluoroethane (R134 a); the second component is 55 percent of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass; the third component is trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) accounting for 4 mass percent; the fourth component is 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) accounting for 2% of mass, and the quaternary near-boiling mixed working medium is an optimal formula in consideration of comprehensive properties such as flammability, GWP, refrigerating capacity and energy efficiency.
Further optionally, the near-azeotropic mixture working medium comprises four components, wherein the first component is 1-15% by mass of 1,1,1, 2-tetrafluoroethane (R134 a); the second component is 1-86% of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass; the third component is trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) accounting for 1-86% by mass; the fourth component is 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) accounting for 12-17% by mass. The mass ratio of the four components of the near-azeotropic mixed working medium is in the range, and the near-azeotropic mixed working medium has low flammability and low GWP.
Further optionally, the near-azeotropic mixture is composed of four components, wherein the first component is 14% by mass of 1,1,1, 2-tetrafluoroethane (R134 a); the second component is 73% of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass; the third component is trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) accounting for 1 percent of the mass; the fourth component is 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) accounting for 12% by mass. The quaternary near-boiling mixed working medium is an optimal formula in consideration of comprehensive properties such as combustibility, refrigeration capacity and energy efficiency.
Further optionally, the near-azeotropic mixture working medium comprises three components, wherein the first component is 1-43% by mass of 1,1,1, 2-tetrafluoroethane (R134 a); the second component is 56-98% of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass; the third component is 1 to 13 mass percent of 1,1,1,2,3,3, 3-heptafluoropropane (R227 ea).
Further optionally, the near-azeotropic mixture working medium comprises three components, wherein the first component is 30-43% of 1,1,1, 2-tetrafluoroethane (R134a) by mass; the second component is 56-69% of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass; the third component is 1 to 6 mass percent of 1,1,1,2,3,3, 3-heptafluoropropane (R227 ea). The mass ratio of the four components of the near-azeotropic mixed working medium is respectively in the range, so that the near-azeotropic mixed working medium has better refrigerating capacity and energy efficiency performance and small temperature slippage.
Further optionally, the near-azeotropic mixture is composed of three components, wherein the first component is 37% by mass of 1,1,1, 2-tetrafluoroethane (R134 a); the second component is 61% by mass of 2,3,3, 3-tetrafluoropropene (R1234 yf); the third component is 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) accounting for 2% of mass, and the ternary near-working boiling mixed working medium is an optimal formula in consideration of comprehensive properties such as flammability, refrigerating capacity and energy efficiency.
Further optionally, the near-azeotropic mixture working medium comprises three components, wherein the first component is 1-17% by mass of 1,1,1, 2-tetrafluoroethane (R134 a); the second component is 72-88% of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass; the third component is 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) accounting for 11-13% by mass. The mass ratio of the four components of the near-azeotropic mixed working medium is respectively in the above range, and the near-azeotropic mixed working medium has low flammability and low GWP.
Further optionally, the near-azeotropic mixture is composed of three components, wherein the first component is 15% by mass of 1,1,1, 2-tetrafluoroethane (R134 a); the second component is 74 percent of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass; the third component is 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) accounting for 11 percent of the mass. The ternary near-working boiling mixed working medium is an optimal formula in consideration of comprehensive properties such as combustibility, refrigeration capacity and energy efficiency.
Further optionally, the near-azeotropic mixture of working fluids, which has a Global Warming Potential (GWP) of no greater than 600.
Further optionally, the near-azeotropic mixture has an Ozone Depletion Potential (ODP) equal to zero.
Further optionally, the glide temperature of the near-azeotropic mixed working medium is more than 0 ℃ and less than or equal to 0.5 ℃, so that the problem of heat exchange efficiency reduction caused by temperature glide is avoided.
The invention also provides a composition comprising a lubricant and the near-azeotropic mixture according to any of the above.
Further alternatively, wherein the lubricant is selected from ester oils, which have a good compatibility with the composition of the present invention, ensuring the proper operation of the refrigeration system in which it is used, while having a positive effect on the lifetime of the refrigeration system.
The present invention also provides a method of replacing an existing heat exchange fluid contained in a heat exchange system, comprising: removing at least a portion of said existing heat exchange fluid from said system, said existing heat exchange fluid being R134a, and replacing said existing heat exchange fluid by introducing a near-azeotropic working fluid according to any of the preceding claims, ensuring that said near-azeotropic working fluid or composition comprising three components has a refrigeration capacity of from 90% to 110% of the refrigeration capacity of R134a refrigerant, and ensuring that said near-azeotropic working fluid or composition comprising four components has a refrigeration capacity of from 70% to 110% of the refrigeration capacity of R134a refrigerant.
The invention also provides a heat exchange system, which adopts any near azeotropic mixed working medium or any composition as a heat exchange medium.
Further optionally, the heat exchange system is an HVACR system.
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 number of components, and is a condition for ensuring the excellent performance of the mixed quality which is harmless to the ozone layer.
The invention has the beneficial effects that:
(1) the 1,1,1, 2-tetrafluoroethane and the 1,1,1,2,3,3, 3-heptafluoropropane introduced by the invention are non-combustible components, and the flammability of other components, namely 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) can be weakened through the content change of the non-combustible components, so that a mixed working medium which is harmless to an ozone layer and has good safety performance is obtained, wherein GWP is less than or equal to 600, and ODP is 0.
(2) Compared with R134a refrigerant, the mixed working medium harmless to the ozone layer has the same relative volume refrigerating capacity and relative COP, and can be used as the mixed working medium harmless to the ozone layer to replace R134a refrigerant.
(3) In addition to the volumetric refrigerating capacity and energy efficiency, the selection of the components of the mixed working medium harmless to the ozone layer also considers temperature slippage, the combination with larger boiling point difference among the group members is possible to form a non-azeotropic mixture with larger phase change temperature difference (slippage temperature), and the slippage temperature of the mixed working medium is less than 0.5 ℃.
Detailed Description
The invention relates to a method for preparing a near-azeotropic mixed working medium, which is to physically mix 1,1,1, 2-tetrafluoroethane (R134a) and 2,3,3, 3-tetrafluoropropene (R1234yf) with trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) or with a plurality of components such as 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) and the like in a liquid phase state at the temperature of 23-27 ℃ and the pressure of 0.1MPa according to corresponding mass ratio. Wherein 1,1,1, 2-tetrafluoroethane and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) are non-combustible components, and the combustibility of the rest components can be weakened by adding the non-combustible components, so that the safety requirement is met. The basic parameters of the component materials are shown in Table 1.
TABLE 1 basic parameters of the component substances in the working mixture
A plurality of specific examples and comparative examples are given below, wherein the proportions of the components are mass percentages, and the sum of the mass percentages of the component substances of each near-azeotropic mixed working medium is 100%.
Example 1, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 1:1:97:1, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 2, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 1:97:1:1, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 3, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 15:68:11:6, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 4, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 21:55:22:2, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 5, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 25:64:6:5, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 6, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 30:57:9:4, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 7, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 35:43:20:2, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 8, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 43:36:20:1, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 9 a near azeotropic mixture was obtained by liquid phase physical mixing of four components, 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 6:86:3: 5.
Example 10, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 4:3:86:7, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 11, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 20:75:1:4, and mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 12, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 39:55:4:2, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 13, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 14:73:1:12, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 14, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 4:86:1:9, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 15, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 2:4:77:17, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 16, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 29:64:2:5, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 17, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 14:73:1:12, and the mixture was mixed uniformly to obtain a near-azeotropic mixed working fluid.
Example 18, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 43:56:1, and mixed uniformly to obtain a near-azeotropic working fluid mixture.
Example 19, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 15:74:11, and mixed uniformly to obtain a near-azeotropic working fluid mixture.
Example 20A near azeotropic mixture was prepared by liquid phase physical mixing of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) at 23 deg.C-27 deg.C and 0.1MPa in a mass ratio of 20:74: 6.
Example 21 a near azeotropic mixture was prepared by liquid phase physical mixing of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 25:69: 6.
Example 22, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 30:65:5, and mixed uniformly to obtain a near-azeotropic working fluid mixture.
Example 23a near azeotropic mixture was prepared by liquid phase physical mixing of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 17:72: 11.
Example 24, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 10:78:12, and mixed uniformly to obtain a near-azeotropic working fluid mixture.
Example 25A near azeotropic mixture was prepared by liquid phase physical mixing of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) at 23 deg.C-27 deg.C and 0.1MPa in a mass ratio of 2:85: 13.
Example 26, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 1:98:1, and mixed uniformly to obtain a near-azeotropic working fluid mixture.
Example 27 a near azeotropic mixture was prepared by liquid phase physical mixing of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 1:88: 11.
Example 28, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 37:61:2, and mixed uniformly to obtain a near-azeotropic working fluid mixture.
Example 29, three components, 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 14:74:12, and mixed uniformly to obtain a near-azeotropic working fluid mixture.
Example 30, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 6:85:9, and mixed uniformly to obtain a near-azeotropic working fluid mixture.
Comparative example 1, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 45:4:36:15, and mixed uniformly to obtain a working fluid mixture.
Comparative example 2, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 0:7:76:17, and mixed uniformly to obtain a working fluid mixture.
Comparative example 3, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 7:0:76:17, and mixed uniformly to obtain a working fluid mixture.
Comparative example 4, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 2:81:0:17, and mixed uniformly to obtain a working fluid mixture.
Comparative example 5, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 19:5:76:0, and mixed uniformly to obtain a working fluid mixture.
Comparative example 6, four components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 1:5:75:19, and mixed uniformly to obtain a working fluid mixture.
Comparative example 7, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) are subjected to liquid phase physical mixing at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa according to a mass ratio of 0:89:11, and the mixture is uniformly mixed to obtain a mixed working medium.
Comparative example 8, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) are subjected to liquid phase physical mixing according to the mass ratio of 34:53:13 at the temperature of 23-27 ℃ and the pressure of 0.1MPa, and the mixed working medium is obtained after uniform mixing.
Comparative example 9, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) are subjected to liquid phase physical mixing at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa according to a mass ratio of 11:89:0, and the mixture is uniformly mixed to obtain a mixed working medium.
Comparative example 10, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) were physically mixed in a liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 25:60:15, and mixed uniformly to obtain a working fluid mixture.
Comparative example 11, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) were physically mixed in liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 45:50:5, and mixed uniformly to obtain a working fluid mixture.
Comparative example 12, three components of 1,1,1, 2-tetrafluoroethane (R134a), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) were physically mixed in liquid phase at a temperature of 23 ℃ to 27 ℃ and a pressure of 0.1MPa in a mass ratio of 89:0:11, and mixed uniformly to obtain a working fluid mixture.
Table 2 compares the above examples and comparative examples with basic parameters of molecular weight, normal boiling point and environmental properties of R134 a.
TABLE 2 basic parameters of the mixed working substances
As can be seen from Table 2, the GWP of the quaternary and ternary mixed working medium provided by the invention is less than or equal to 600, the ODP is 0, and the working medium has obvious environmental protection advantage and the GWP is far lower than that of R134 a. In addition, the molecular weight of the mixed working medium is slightly larger than that of R134a, and the critical point of the mixed working medium is lower than that of R134 a.
Meanwhile, by combining the data of the embodiment and the comparative example, it can be seen that when the contents of the components in the formula or the composition of the prepared mixed working medium are changed, the components cannot play a good synergistic effect, the GWP and/or the slip temperature and/or the flammability of the mixed working medium can be increased, and the heat exchange effect and the environmental performance of a unit when the mixed working medium is used are influenced, for example, the mass percentage ratio of the component R134a is increased in the comparative example 1, and the GWP of the obtained quaternary mixed working medium is 1087.9 which is obviously higher than the highest value of the GWP of the mixed working medium of the invention. Other comparative examples show that the GWP of the obtained quaternary mixed working medium is obviously reduced by increasing the mass percentage ratio of the component II, the component III and the component IV, but the standard boiling point of the quaternary mixed working medium is increased, so that the refrigeration efficiency is influenced. While reducing the number of components in the formulation also increases GWP and/or glide temperature and/or flammability, e.g., removing component R134a or component R227ea from the formulation increases flammability; the GWP is too high by removing the component R1234yf from the formulation.
Table 3 compares the thermodynamic parameters (i.e. compression ratio and exhaust temperature) and relative thermodynamic performance (i.e. relative refrigerating capacity per unit volume and relative efficiency COP) of the mixed working medium in the above embodiment under the refrigeration condition of an HVACR system (i.e. evaporation temperature of 6 ℃, condensation temperature of 36 ℃, superheat degree of 5 ℃, and supercooling degree of 5 ℃).
TABLE 3 comparison of Performance of working mixtures with R134a
(slip temperature is the difference between dew point temperature and bubble point temperature under working pressure, maximum value is taken)
As can be seen from Table 3, the volumetric refrigeration capacity of part of the refrigerant formulation is greater than that of R134a, and the temperature glide is less than or equal to 0.1 ℃, which belongs to azeotropic refrigerants. The volume refrigerating capacity of other refrigerant formulas is less than R134a volume refrigerating capacity, the relative volume refrigerating capacity of most formulas is not less than 0.9, the relative volume refrigerating capacity of a small amount of formulas is about 0.7, the temperature slippage is less than 0.52 ℃, and the refrigerant belongs to a near azeotropic refrigerant. The energy efficiency COPs of all formulations were less than the energy efficiency COPs of R134a, but greater than 0.9. Wherein the refrigerating capacity of the ternary mixed working medium is 90-110% of that of the R134a refrigerant, and the refrigerating capacity of the quaternary mixed working medium is 70-110% of that of the R134a refrigerant.
Comparative example analysis shows that when the content of the components in the formula is changed or the prepared mixed working medium is formed, the components cannot well play a synergistic effect, the sliding temperature and/or the inflammability of the mixed working medium are/is increased, and the heat exchange effect and the environmental protection performance of a unit are influenced when the mixed working medium is used. Meanwhile, the sliding temperature and/or the flammability can be increased by reducing the types of components in the formula, and GWP, relative volume refrigerating capacity, energy efficiency and temperature sliding indexes are all equivalent to those of the embodiment, but the invisible problem, namely the flammability exists. The mixed refrigerant of the patent has certain mixture ratio which is not combustible, and a small amount of mixture ratio has weak combustibility.
In conclusion, the near-azeotropic mixed working medium has the environment-friendly characteristics of low GWP and zero ODP, has excellent thermal performance, and can be used as an environment-friendly refrigerant for replacing R134a, wherein the volume refrigerating capacity and the energy efficiency COP of the mixed working medium harmless to an ozone layer used by a refrigerating device are equivalent to those of the mixed working medium using R134a, and the temperature slippage is small under the same refrigerating working condition. Meanwhile, the near-azeotropic mixed working medium provided by the invention can be selectively added with additives such as lubricant, stabilizer, super-strong agent and the like according to the requirements of a refrigerating system to enhance the performance of the mixed working medium harmless to the ozone layer and the stability of the refrigerating system.
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 (8)
1. A near azeotropic mixed working medium is characterized in that the near azeotropic mixed working medium comprises four components, wherein,
the first component is 1,1,1, 2-tetrafluoroethane (R134a) accounting for 30-43% of the mass;
the second component is 36-68% of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass;
the third component is trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) accounting for 1-22% by mass;
the fourth component is 1 to 6 mass percent of 1,1,1,2,3,3, 3-heptafluoropropane (R227 ea); wherein the mass ratio is based on the total mass of all the components of the near-azeotropic mixed working medium.
2. A near-azeotropic mixed working medium is characterized in that the near-azeotropic mixed working medium comprises three components, wherein,
the first component is 1 to 43 mass percent of 1,1,1, 2-tetrafluoroethane (R134 a);
the second component is 56-98% of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass;
the third component is 1 to 13 mass percent of 1,1,1,2,3,3, 3-heptafluoropropane (R227 ea); wherein the mass ratio is based on the total mass of all the components of the near-azeotropic mixed working medium.
3. A near-azeotropic mixture according to claim 2, wherein said near-azeotropic mixture comprises three components, wherein,
the first component is 1,1,1, 2-tetrafluoroethane (R134a) accounting for 30-43% of the mass;
the second component is 56-69% of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass;
the third component is 1 to 6 mass percent of 1,1,1,2,3,3, 3-heptafluoropropane (R227 ea); wherein the mass ratio is based on the total mass of all the components of the near-azeotropic mixed working medium.
4. A near-azeotropic mixture according to claim 2, wherein said near-azeotropic mixture comprises three components, wherein,
the first component is 1 to 17 mass percent of 1,1,1, 2-tetrafluoroethane (R134 a);
the second component is 72-88% of 2,3,3, 3-tetrafluoropropene (R1234yf) by mass;
the third component is 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) accounting for 11-13% of the mass; wherein the mass ratio is based on the total mass of all the components of the near-azeotropic mixed working medium.
5. A near-azeotropic mixture as claimed in any one of claims 1 to 4, wherein: the near-azeotropic mixture of working fluids, which has a Global Warming Potential (GWP) of not more than 600, and an Ozone Depletion Potential (ODP) equal to zero.
6. A method of replacing an existing heat exchange fluid contained in a heat exchange system, comprising: removing at least a portion of said existing heat exchange fluid from said system, said existing heat exchange fluid being R134a, and replacing said existing heat exchange fluid by introducing a near-azeotropic working mixture according to any of claims 1-5, to provide a refrigeration capacity of 70% to 110% of that of R134a refrigerant.
7. A heat exchange system using the near azeotropic mixture according to any one of claims 1 to 5.
8. The heat exchange system of claim 7, wherein: the heat exchange system is an HVACR system.
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| CN105567172A (en) * | 2004-04-29 | 2016-05-11 | 霍尼韦尔国际公司 | Azeotrope-like compositions of tetrafluoropropene & hydrofluorocarbons |
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| CN105378022A (en) * | 2013-03-15 | 2016-03-02 | 霍尼韦尔国际公司 | Compositions and method for refrigeration |
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