CN113956850A - Environment-friendly mixed refrigerant, preparation method thereof and refrigeration system - Google Patents
Environment-friendly mixed refrigerant, preparation method thereof and refrigeration system Download PDFInfo
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- CN113956850A CN113956850A CN202111211253.XA CN202111211253A CN113956850A CN 113956850 A CN113956850 A CN 113956850A CN 202111211253 A CN202111211253 A CN 202111211253A CN 113956850 A CN113956850 A CN 113956850A
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 117
- 238000005057 refrigeration Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 185
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 claims abstract description 35
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims abstract description 34
- 239000007791 liquid phase Substances 0.000 claims abstract description 31
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 14
- 239000000306 component Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 29
- 230000007613 environmental effect Effects 0.000 description 5
- 238000004378 air conditioning Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60H—ARRANGEMENTS OF HEATING, COOLING, VENTILATING OR OTHER AIR-TREATING DEVICES SPECIALLY ADAPTED FOR PASSENGER OR GOODS SPACES OF VEHICLES
- B60H1/00—Heating, cooling or ventilating [HVAC] devices
- B60H1/32—Cooling devices
-
- 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
-
- 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
-
- 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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- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application relates to the technical field of refrigerants, in particular to an environment-friendly mixed refrigerant, a preparation method of the environment-friendly mixed refrigerant and a refrigeration system. The environment-friendly mixed refrigerant comprises a first component and a second component, wherein: the first component is monofluoromethane, and the second component is one or two of 2,3,3, 3-tetrafluoropropene and trans-1, 3,3, 3-tetrafluoropropene. The environment-friendly mixed refrigerant comprises 12-48% of a first component and 52-88% of a second component in percentage by mole. The components of the environment-friendly mixed refrigerant are mixed and stirred in a normal-temperature liquid-phase state to obtain the environment-friendly mixed refrigerant. The environment-friendly mixed refrigerant provided by the embodiment of the invention can better replace R134a refrigerant, on one hand, the environment-friendly and safety characteristics of the refrigerant are considered, on the basis that GWP is less than 150, the safety level is not lower than A2L, on the other hand, the high-temperature refrigeration and low-temperature heating performance is ensured, the energy efficiency is basically equivalent to R134a, the volume refrigeration/heating capacity is improved by more than 10%, and the maximum capacity can be improved by 121%.
Description
Technical Field
The application relates to the technical field of refrigerants, in particular to an environment-friendly mixed refrigerant, a preparation method of the environment-friendly mixed refrigerant and a refrigeration system.
Background
In order to cope with climate change, new energy automobiles are being developed vigorously in various countries in the world, but the problems of battery safety, battery service life, battery endurance and the like are faced, and the whole automobile thermal management is a key technology for solving the problems. The heat pump air conditioner is a core component of the whole vehicle heat management, and the performance of the heat pump air conditioner is directly influenced by the refrigerant. Most countries have a vehicle air-conditioning refrigerant of R134a (1,1,1, 2-tetrafluoroethane) with a GWP (global warming potential) as high as 1300, and will be in the face of replacement. At present, the use of GWP (global warming potential) is forbidden by passenger car air conditioners which are already determined by countries of European Union>150, the heat pump air conditioners of the enterprises in countries of the European Union have been switched to R744 (CO) under the regulation2) And R1234yf (2,3,3, 3-tetrafluoropropene) refrigerant. The GWP of CO2 is 1, has good heat transfer characteristic and is widely applied to the field of heat pump water heaters, but because the critical temperature is lower (304.13K), the operation under the refrigeration working condition is transcritical circulation, the irreversible loss of the circulation is large, the refrigeration energy efficiency is generally low, and the CO is put into research and development in the running enterprises of the early nineties2An automobile air conditioner, however, the problem of low refrigeration energy efficiency in a high-temperature environment is still not solved. The GWP of R1234yf is 1, the physical property of the refrigerant is similar to that of R134a of the existing vehicle air-conditioning refrigerant, and the refrigerant can directly replace R134a refrigerant, so the refrigerant is widely applied to passenger vehicle air-conditioning in countries of European Union, but the normal-pressure boiling point of R1234yf is high (243.67K), the heating capacity and energy efficiency are low in low-temperature environment, the heating demand can be met only by a PTC heating mode, and the cruising ability of the battery is greatly reduced.
Disclosure of Invention
In order to solve the technical problem of poor environmental protection performance of the R134a refrigerant in the prior art, the primary object of the present invention is to provide an environmental protection mixed refrigerant which has good environmental performance, has extremely low GWP, can simultaneously take account of thermal performance, and can replace the R134a refrigerant.
In order to achieve the above object, according to a first aspect of the present invention, there is provided an environment-friendly mixed refrigerant.
An environmentally friendly mixed refrigerant according to an embodiment of the present application, comprising a first component and a second component, wherein: the first component is monofluoromethane, and the second component is one or two of 2,3,3, 3-tetrafluoropropene and trans-1, 3,3, 3-tetrafluoropropene.
Further, the environment-friendly mixed refrigerant comprises 12-48% of a first component and 52% -88% of a second component in mole percentage.
Further, the environment-friendly mixed refrigerant comprises 16-36% of a first component and 64% -84% of a second component in mole percentage.
Further, the environment-friendly mixed refrigerant comprises 24% of a first component and 76% of a second component in molar percentage.
Further, the environment-friendly mixed refrigerant also comprises a third component, and the third component is difluoromethane.
Further, the environment-friendly mixed refrigerant comprises 4-44% of a first component, 24-80% of a second component and 4-52% of a third component in molar percentage.
Further, the environment-friendly mixed refrigerant comprises 16-32% of a first component, 44-80% of a second component and 4-24% of a third component in molar percentage.
Further, the environment-friendly mixed refrigerant comprises 34% of a first component, 52% of a second component and 24% of a third component in mole percentage.
In order to achieve the above object, according to a second aspect of the present invention, there is provided a method for preparing an environmentally friendly mixed refrigerant, for preparing the environmentally friendly mixed refrigerant provided by the first aspect of the embodiments of the present invention, the method comprising the steps of: and mixing and stirring the components of the environment-friendly mixed refrigerant in a normal-temperature liquid-phase state to obtain the environment-friendly mixed refrigerant.
In order to achieve the above object, according to a third aspect of the present invention, there is also provided a refrigeration system, including a working medium, where the working medium includes the environmentally friendly mixed refrigerant provided by the first aspect of the embodiments of the present invention.
The environment-friendly mixed refrigerant provided by the embodiment of the invention can better replace R134a refrigerant, on one hand, the environment-friendly and safety characteristics of the refrigerant are considered, on the basis that GWP is less than 150, the safety level is not lower than A2L, on the other hand, the high-temperature refrigeration and low-temperature heating performance is ensured, the energy efficiency is basically equivalent to R134a, the volume refrigeration/heating capacity is improved by more than 10%, and the maximum capacity can be improved by 121%.
Detailed Description
In order to make the technical solutions of the present application better understood by those skilled in the art, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is obvious that the described embodiments are only partial embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It is noted that the terms "comprises" and "comprising," and any variations thereof, in the description and claims of this application are intended to cover a non-exclusive inclusion, such that a system, article, or apparatus that comprises a list of elements is not necessarily limited to those elements explicitly listed, but may include other elements not expressly listed or inherent to such article or apparatus. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The preparation method of the environment-friendly mixed refrigerant provided by the embodiment of the invention is that the components of the environment-friendly mixed refrigerant are physically mixed into a multi-component mixture in a normal-temperature liquid-phase state according to the corresponding molar ratio, and the multi-component mixture can be mixed and stirred in the normal-temperature liquid-phase state to prepare the environment-friendly mixed refrigerant. The basic parameters of each component in the environment-friendly mixed refrigerant in the embodiment of the invention are shown in the table 1.
TABLE 1 basic parameters of each component substance in the environmentally friendly mixed refrigerant
In order to make the technical solutions better understood by those skilled in the art, the technical solutions will be clearly and completely described below in conjunction with the embodiments of the present application, and the described embodiments are only a part of the embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. The present application will be described in detail with reference to preferred embodiments. Specific examples and comparative examples are given below, in which the proportions of the components are all in mole percent, the sum of the mole percent of the constituent substances of each environment-friendly mixed refrigerant is 100%, and the constitutions of the specific examples and comparative examples are shown in Table 2.
Example 1
Uniformly and physically mixing monofluoromethane (R41) and 2,3,3, 3-tetrafluoropropene (R1234yf) according to a molar ratio of 12:88 at a normal temperature and a liquid phase to obtain a binary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41) and 2,3,3, 3-tetrafluoropropene (R1234yf) is 100%.
Example 2
Uniformly and physically mixing monofluoromethane (R41) and 2,3,3, 3-tetrafluoropropene (R1234yf) according to a molar ratio of 32:68 at a normal temperature and a liquid phase to obtain a binary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41) and 2,3,3, 3-tetrafluoropropene (R1234yf) is 100%.
Example 3
Uniformly and physically mixing monofluoromethane (R41) and 2,3,3, 3-tetrafluoropropene (R1234yf) according to a molar ratio of 48:52 at normal temperature and liquid phase to obtain a binary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41) and 2,3,3, 3-tetrafluoropropene (R1234yf) is 100%.
Example 4
Uniformly and physically mixing monofluoromethane (R41) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) at a molar ratio of 16:84 at normal temperature and liquid phase to obtain a binary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Example 5
Uniformly and physically mixing monofluoromethane (R41) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) at a molar ratio of 36:64 at normal temperature and liquid phase to obtain a binary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Example 6
Uniformly and physically mixing monofluoromethane (R41) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) at a molar ratio of 48:52 at normal temperature and liquid phase to obtain a binary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Example 7
Uniformly and physically mixing monofluoromethane (R41), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 12:48:40 at a normal temperature and liquid phase to obtain a ternary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Example 8
Uniformly and physically mixing monofluoromethane (R41), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 24:28:48 at a normal temperature liquid phase to obtain a ternary environment-friendly mixed refrigerant, wherein the sum of the mole percentages of monofluoromethane (R41), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Example 9
Uniformly and physically mixing monofluoromethane (R41), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 36:36:28 at normal temperature and liquid phase to obtain a ternary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Example 10
Uniformly and physically mixing monofluoromethane (R41), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 48:28:24 at normal temperature and liquid phase to obtain the ternary environment-friendly mixed refrigerant, wherein the sum of the mole percentages of monofluoromethane (R41), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Example 11
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) according to a molar ratio of 4:36:60 at a normal temperature and in a liquid phase to obtain a ternary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) is 100%.
Example 12
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) according to a molar ratio of 24:52:24 at normal temperature and liquid phase to obtain the ternary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) is 100%.
Example 13
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) according to a molar ratio of 32:24:44 at normal temperature and liquid phase to obtain the ternary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) is 100%.
Example 14
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) according to a molar ratio of 44:20:36 at a normal temperature and in a liquid phase to obtain a ternary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) is 100%.
Example 15
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 4:36:60 at normal temperature and in a liquid phase to obtain a ternary environment-friendly mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Example 16
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 16:4:80 at normal temperature and liquid phase to obtain a ternary environment-friendly mixed refrigerant, wherein the sum of the mole percentages of monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Example 17
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 32:16:52 at normal temperature and liquid phase to obtain a ternary environment-friendly mixed refrigerant, wherein the sum of the mole percentages of monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Example 18
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 44:16:40 at a normal temperature and in a liquid phase to obtain a ternary environment-friendly mixed refrigerant, wherein the sum of the mole percentages of monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Comparative example 1
Uniformly and physically mixing monofluoromethane (R41) and 2,3,3, 3-tetrafluoropropene (R1234yf) according to a molar ratio of 52:48 at a normal temperature and a liquid phase to obtain a binary mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41) and 2,3,3, 3-tetrafluoropropene (R1234yf) is 100%.
Comparative example 2
Uniformly and physically mixing monofluoromethane (R41) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 56:44 at normal temperature and liquid phase to obtain a binary mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Comparative example 3
Uniformly and physically mixing monofluoromethane (R41), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 68:4:28 at a normal temperature and in a liquid phase to obtain a ternary mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), 2,3,3, 3-tetrafluoropropene (R1234yf) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Comparative example 4
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) according to a molar ratio of 60:8:32 at a normal temperature and in a liquid phase to obtain a ternary mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) is 100%.
Comparative example 5
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) according to a molar ratio of 40:40:20 at a normal temperature and liquid phase to obtain a ternary mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), difluoromethane (R32) and 2,3,3, 3-tetrafluoropropene (R1234yf) is 100%.
Comparative example 6
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 60:8:32 at a normal temperature and in a liquid phase to obtain a ternary mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
Comparative example 7
Uniformly and physically mixing monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) according to a molar ratio of 40:40:20 at a normal temperature and liquid phase to obtain a ternary mixed refrigerant, wherein the sum of the molar percentages of monofluoromethane (R41), difluoromethane (R32) and trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) is 100%.
TABLE 2 composition of ingredients of each example and comparative example
| Refrigerant | Component one | Component two | Component three | Molar weight ratio |
| Example 1 | R41 | R1234yf | - | 0.12/0.88 |
| Example 2 | R41 | R1234yf | - | 0.32/0.68 |
| Example 3 | R41 | R1234yf | - | 0.48/0.52 |
| Example 4 | R41 | R1234ze(E) | - | 0.16/0.84 |
| Example 5 | R41 | R1234ze(E) | - | 0.36/0.64 |
| Example 6 | R41 | R1234ze(E) | - | 0.48/0.52 |
| Example 7 | R41 | R1234yf | R1234ze(E) | 0.12/0.48/0.40 |
| Example 8 | R41 | R1234yf | R1234ze(E) | 0.24/0.28/0.48 |
| Example 9 | R41 | R1234yf | R1234ze(E) | 0.36/0.36/0.28 |
| Example 10 | R41 | R1234yf | R1234ze(E) | 0.48/0.28/0.24 |
| Example 11 | R41 | R32 | R1234yf | 0.04/0.36/0.60 |
| Example 12 | R41 | R32 | R1234yf | 0.24/0.52/0.24 |
| Example 13 | R41 | R32 | R1234yf | 0.32/0.24/0.44 |
| Example 14 | R41 | R32 | R1234yf | 0.44/0.20/0.36 |
| Example 15 | R41 | R32 | R1234ze(E) | 0.04/0.36/0.60 |
| Example 16 | R41 | R32 | R1234ze(E) | 0.16/0.04/0.80 |
| Example 17 | R41 | R32 | R1234ze(E) | 0.32/0.16/0.52 |
| Example 18 | R41 | R32 | R1234ze(E) | 0.44/0.16/0.40 |
| Comparative example 1 | R41 | R1234yf | - | 0.52/0.48 |
| Comparative example 2 | R41 | R1234ze(E) | - | 0.56/0.44 |
| Comparative example 3 | R41 | R1234yf | R1234ze(E) | 0.68/0.04/0.28 |
| Comparative example 4 | R41 | R32 | R1234yf | 0.60/0.08/0.32 |
| Comparative example 5 | R41 | R32 | R1234yf | 0.40/0.40/0.20 |
| Comparative example 6 | R41 | R32 | R1234ze(E) | 0.60/0.08/0.32 |
| Comparative example 7 | R41 | R32 | R1234ze(E) | 0.40/0.40/0.20 |
In order to compare the effects of the examples and the comparative examples, the design conditions selected are specifically: the evaporator evaporation temperature (the arithmetic mean of the evaporator inlet temperature and the dew point temperature under the corresponding pressure) was 283.15K, the condenser condensation temperature (the arithmetic mean of the dew point and bubble point temperature in the condenser) was 313.15K, the vapor phase at the evaporator outlet was in the superheated state, the degree of superheat was 5K, the liquid phase at the condenser outlet was in the supercooled state, the degree of supercooling was 5K, and the adiabatic efficiency of the compressor was 0.75. The refrigerants of examples 1 to 18, comparative examples 1 to 7, and R1234yf described above, and CO were used, respectively2The circulation performance parameters of the refrigerant and the R134a refrigerant in the refrigeration system are tested and calculated, and the critical temperature, the GWP value, the refrigerating/heating capacity Qv per unit volume (compared with the refrigerating/heating capacity Qv per unit volume of the R134a refrigerant) are comparedQuantitative ratio), relative coefficient of performance COP (ratio of coefficient of performance to R134a refrigerant), boiling point, and safety rating, as reported in table 3.
Table 3 examples, comparative examples, R134a, R1234yf and CO2Experimental data of
As can be seen from Table 3, the GWP values of the refrigerants obtained in the embodiments of the invention are all less than 150, and the refrigerants have better environmental protection characteristics; the safety level of the refrigerant obtained by each embodiment of the invention is A2L, and the safety performance is excellent; the relative performance coefficients of the refrigerant obtained by the embodiments of the invention are not lower than 0.9, which are basically equivalent to R134a, the relative volume refrigerating/heating capacity is not lower than 1.1, and the maximum relative volume refrigerating/heating capacity is 2.21 times of R134 a; the refrigerant obtained by the embodiments of the invention has higher refrigerating/heating capacity than R1234yf refrigerant, and has higher CO content2The refrigerant has higher refrigeration energy efficiency than the refrigerant. If a certain component in the refrigerant provided by the embodiment of the invention is not in the molar ratio provided by the application, for example, the molar ratio of R41 in the refrigerant obtained by the comparative examples 1,2, 3, 4 and 6 exceeds 48 percent, the safety grades of the components are all A2, and the refrigerant is applied to a secondary loop system required by a vehicle air conditioner; wherein the coefficient of performance of the refrigerants obtained in comparative example 3, comparative example 4 and comparative example 6 is low, lower than 90% of that of R134 a; comparative example 5 and comparative example 7 obtained a refrigerant in which the molar proportion of R32 component exceeded 36%, and whose GWP values were both higher than 150, wherein the coefficient of performance of the refrigerant obtained in comparative example 7 was lower than 90% of R134 a. The refrigerant provided by the embodiment of the invention has the normal pressure bubble point temperature between 67.3 ℃ below zero and 43 ℃ below zero, the normal pressure dew point temperature between 45.8 ℃ below zero and 22.9 ℃ below zero, the refrigerant in the comparative example has the normal pressure bubble point temperature between 71.9 ℃ below zero and 65.8 ℃ below zero, and the normal pressure dew point temperature between 49.3 ℃ below zero and 35.8 ℃, belongs to a low-temperature refrigerant, has relatively higher working temperature, and belongs to normal-temperature refrigerationThe corresponding working temperature requirement of the agent is not as strict as that of a comparative example, and the agent is more suitable for the working environment of an automobile air conditioner.
Therefore, the environment-friendly mixed refrigerant provided by the invention not only has the environment-friendly characteristic of low GWP, but also has excellent safety performance, the energy efficiency is basically equivalent to that of R134a, the volume refrigeration/heating is greatly improved, and the environment-friendly mixed refrigerant can be better applied to automobile air conditioners.
The current new energy automobile alternative refrigerant needs to have the following characteristics: good environmental protection property, GWP<150; for direct cooling systems, the safety rating of the refrigerant is not lower than A2L, and the safety rating is classified according to ASHRAE 34-2019 and is classified into a (low toxicity), B (high toxicity), 1 (no flame spread), 2L (micro-ignition), 2 (combustible) and 3 (combustible); can stably operate in a wide temperature range of-35 to 50 ℃, has good thermodynamic property, and has better high-temperature refrigeration energy efficiency than CO2And the low-temperature heating capacity is better than that of R134a or R1234 yf. The refrigerant provided by the patent is a mixed refrigerant suitable for new energy vehicles, which is formed by mixing a plurality of components in R41 (monofluoromethane), R32 (difluoromethane), R1234yf (2,3,3, 3-tetrafluoropropene), and R1234ze (E) (trans-1, 3,3, 3-tetrafluoropropene), and can meet the requirement of the new energy vehicles for replacing the refrigerant.
The embodiment of the invention also correspondingly protects a refrigeration system using the environment-friendly mixed refrigerant provided by the embodiment of the invention as a working medium, the refrigeration system can be applied to electric appliances including but not limited to air conditioners, refrigerators, dehumidifiers and the like, and other components and working principles of the refrigeration system are applicable to the prior art and are not described herein again.
Some embodiments in this specification are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. An environmentally friendly mixed refrigerant comprising a first component and a second component, wherein: the first component is monofluoromethane, and the second component is one or two of 2,3,3, 3-tetrafluoropropene and trans-1, 3,3, 3-tetrafluoropropene.
2. The environmentally friendly mixed refrigerant of claim 1, comprising 12-48% of the first component and 52% -88% of the second component, in mole percent.
3. The environmentally friendly mixed refrigerant of claim 1, comprising 16-36% of the first component and 64% -84% of the second component, in mole percent.
4. The environmentally friendly mixed refrigerant of claim 1, comprising 24% of the first component and 76% of the second component, in mole percent.
5. The environmentally friendly mixed refrigerant of claim 1, further comprising a third component, the third component being difluoromethane.
6. The environmentally friendly mixed refrigerant of claim 5, comprising, in mole percent, 4-44% of the first component, 24-80% of the second component, and 4-52% of the third component.
7. The environmentally friendly mixed refrigerant of claim 5, comprising 16-32% of the first component, 44-80% of the second component, and 4-24% of the third component, in mole percent.
8. The environmentally friendly mixed refrigerant of claim 5, comprising, in mole percent, 34% of the first component, 52% of the second component, and 24% of the third component.
9. A method for preparing an environmentally friendly mixed refrigerant according to any one of claims 1 to 8, comprising the steps of: and mixing and stirring the components of the environment-friendly mixed refrigerant in a normal-temperature liquid-phase state to obtain the environment-friendly mixed refrigerant.
10. A refrigeration system, characterized in that the refrigeration system comprises a working medium, wherein,
the working fluid comprises the environment-friendly mixed refrigerant as set forth in any one of claims 1 to 8.
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