CN110843457A - Automobile air conditioner heat pump system adopting environment-friendly refrigerant - Google Patents

Automobile air conditioner heat pump system adopting environment-friendly refrigerant Download PDF

Info

Publication number
CN110843457A
CN110843457A CN201910984126.XA CN201910984126A CN110843457A CN 110843457 A CN110843457 A CN 110843457A CN 201910984126 A CN201910984126 A CN 201910984126A CN 110843457 A CN110843457 A CN 110843457A
Authority
CN
China
Prior art keywords
component
refrigerant
heat pump
pump system
automobile air
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910984126.XA
Other languages
Chinese (zh)
Other versions
CN110843457B (en
Inventor
黄宇杰
于艳翠
赵桓
雷佩玉
梁尤轩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gree Electric Appliances Inc of Zhuhai
Original Assignee
Gree Electric Appliances Inc of Zhuhai
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gree Electric Appliances Inc of Zhuhai filed Critical Gree Electric Appliances Inc of Zhuhai
Priority to CN201910984126.XA priority Critical patent/CN110843457B/en
Publication of CN110843457A publication Critical patent/CN110843457A/en
Application granted granted Critical
Publication of CN110843457B publication Critical patent/CN110843457B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B60H1/00321—Heat exchangers for air-conditioning devices
    • 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
    • B60H1/00485—Valves for air-conditioning devices, e.g. thermostatic valves
    • 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
    • B60H1/3204—Cooling devices using compression
    • 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
    • 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
    • F25B30/00—Heat pumps
    • F25B30/02—Heat pumps of the compression type
    • 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
    • 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
    • C09K2205/11—Ethers
    • 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
    • C09K2205/11—Ethers
    • C09K2205/112—Halogenated ethers
    • 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
    • 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
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/88—Optimized components or subsystems, e.g. lighting, actively controlled glasses

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

The invention provides an automobile air-conditioning heat pump system adopting an environment-friendly refrigerant, which further comprises a compressor, an indoor side heat exchanger, a throttle valve and an outdoor side heat exchanger which are sequentially connected to form a closed loop, wherein the environment-friendly refrigerant used by the automobile air-conditioning heat pump system comprises four components, wherein the four components comprise 4-8% of a first component, 4-80% of a second component, 4-88% of a third component and 4-88% of a fourth component in percentage by mass. The refrigerant adopted in the invention has GWP of less than or equal to 150, has good environmental protection performance and meets the requirement of environmental protection regulations in various regions of the world. The thermal performance of the heat pump system for the automobile air conditioner is equal to or better than that of a heat pump system of a refrigeration system using R134a, so that the heat pump system for the automobile air conditioner adopting R134a refrigerant is replaced.

Description

Automobile air conditioner heat pump system adopting environment-friendly refrigerant
Technical Field
The invention relates to a refrigeration technology, in particular to an automobile air conditioning heat pump system adopting an environment-friendly refrigerant.
Background
Because the 1,1,1, 2-tetrafluoroethane (R134a) has the characteristics of no toxicity, incombustibility, no corrosion, good material compatibility and the like, the composite material is widely applied to the fields of automobile air conditioners and other refrigeration systems. But because of its too high potential for greenhouse effect (GWP value) (up to 1300), according to the requirements of the fluorine-containing greenhouse gas (F-gas) control legislation that has been passed in the european union: since 1/2011, the eu will prohibit newly produced automotive air conditioners from using refrigerants having GWP values greater than 150; in six years from 1 month and 1 day in 2011 to 1 month and 1 day in 2017, the refrigerant with the GWP value larger than 150 is proportionally and gradually eliminated by using the automobile air conditioner; from 1/2017, all automotive air conditioners will be prohibited from using refrigerants with GWP values greater than 150.
Therefore, it is a trend and necessity that the automobile air conditioner uses the refrigerant with low GWP value, R134a used in the automobile air conditioner will be eliminated, and no perfect solution for replacing R134a (GWP: 1430) is found at present, and due to the characteristics of R134a, the heating capacity per unit volume of the automobile air conditioner heat pump system using R134a is low, so that the compressor volume is large (the displacement is large), and finally the system COP is low. The refrigerant has the characteristic of balancing the physical properties of the refrigerant, so the research on the refrigerant becomes a hot spot of research of scholars and enterprises at home and abroad, and although part of refrigerants in the prior art meet lower GWP values, the thermal performance can not meet the requirements usually, and better refrigerating and heating effects can not be realized. The need for a refrigerant that simultaneously meets lower GWP and has good thermal performance is imminent.
Disclosure of Invention
In view of the above, the invention provides an automobile air-conditioning heat pump system using an environment-friendly refrigerant, which has good environment-friendly performance and a GWP of less than 150, meets the requirements of environmental regulations in various regions of the world, and has performance equivalent to or better than that of an R134a heat pump system, thereby replacing the automobile air-conditioning heat pump system using R134 a.
In order to achieve the purpose, the invention adopts the technical scheme that: an automobile air-conditioning heat pump system adopting an environment-friendly refrigerant, wherein the automobile air-conditioning heat pump system further comprises a compressor, an indoor side heat exchanger, a throttle valve and an outdoor side heat exchanger which are sequentially connected to form a closed loop, and the environment-friendly refrigerant used by the automobile air-conditioning heat pump system comprises four components which are 4-8% of a first component, 4-80% of a second component, 4-88% of a third component and 4-88% of a fourth component in percentage by mass; wherein the first component is one of pentafluoroethane (R125), 1,1,1, 2-tetrafluoroethane (R134a) and 1,1,1,2,3,3, 3-heptafluoropropane (R227 ea); the second component is trifluoroiodomethane (R13I 1); the third component is one of trifluoromethyl methyl ether (RE143a), isobutane (R600a), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), 3,3, 3-trifluoropropene (R1243zf), 2,3,3, 3-tetrafluoropropene (R1234 yf); the fourth component is dimethylether (RE 170); the GWP of the environment-friendly refrigerant is less than or equal to 150, and the ODP is 0.
Further optionally, the four components comprise, by mass, 4% to 8% of the first component, 4% to 40% of the second component, 32% to 68% of the third component and 4% to 36% of the fourth component, the GWP of the environment-friendly refrigerant is less than or equal to 150, the ODP is 0, and the refrigerant has better heating capacity per unit volume and COP compared with R134 a.
Further optionally, the four components are 8% of the first component, 20% of the second component, 68% of the third component and 4% of the fourth component by mass. The refrigerant has a better heat generation per unit volume and COP than R134 a.
Further optionally, the first component is 1,1,1, 2-tetrafluoroethane (R134 a). The environment-friendly refrigerant with the first component of 1,1,1, 2-tetrafluoroethane (R134a) has better performance than the refrigerant with the first component of other substances provided in the invention in terms of slip temperature, capacity and energy efficiency relative to R134 a.
Further optionally, the third component is 1, 1-difluoroethane (R152 a). The environment-friendly refrigerant of the third component 1, 1-difluoroethane (R152a) has better performance than the refrigerant of the other substances provided by the invention in terms of capacity and energy efficiency relative to R134 a.
Further alternatively, the first component is 4% by mass of 1,1,1, 2-tetrafluoroethane (R134a), the second component is 4% by mass of trifluoroiodomethane (R13I1), the third component is 56% by mass of 1, 1-difluoroethane (R152a), and the fourth component is 36% by mass of dimethylether (RE 170). The refrigerant has a GWP of less than 150, a glide temperature of 0.07 ℃, a relative COP of 1.006 compared to R134a, and is a more preferred refrigerant.
Further optionally, the compressor is a scroll compressor. The scroll compressor has high volumetric efficiency and small vibration and noise, and is favorable for improving the energy efficiency of the system.
Further optionally, the deviation of the discharge temperature of the compressor of the heat pump system of the automobile air conditioner is less than 3.5 ℃.
Further optionally, the vehicle air conditioner heat pump system includes a lubricant therein. The lubricant has good compatibility with the refrigerant, ensures the normal operation of the heat pump system of the automobile air conditioner, and has positive influence on the service life of the system.
Further optionally, the compressor comprises a lubricant selected from at least one of mineral oil, 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.
Further optionally, a stabilizer is contained in the heat pump system for automobile air conditioner. The stabilizer can increase the stability of the environment-friendly refrigerant used by the heat pump system of the automobile air conditioner and improve the heat exchange efficiency of the environment-friendly refrigerant.
Further optionally, the stabilizer is selected from: one of a diene-based compound, a phosphate, a phenol compound, and an epoxide, and mixtures thereof.
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 refrigerant.
The invention has the beneficial effects that:
(1) the GWP value of the refrigerant used in the system is lower than 150, and the refrigerant meets the requirements of environmental regulations in various regions around the world.
(2) The invention relates to a nonflammable trifluoroiodomethane (R13I1) substance added into a refrigerant used in an automobile air-conditioning heat pump system by adopting an environment-friendly refrigerant, which can weaken the flammability of other components by increasing the mass ratio of the nonflammable substance, thereby obtaining the refrigerant with good safety performance, wherein the GWP of the refrigerant is less than or equal to 150.
(3) Compared with the R134a working medium, the refrigerant has obvious environmental protection advantages, and simultaneously has good thermal performance, and the capacity and the energy efficiency of the automobile air-conditioning heat pump system using the refrigerant are equivalent to those of the automobile air-conditioning heat pump system using the R134a working medium, so that the refrigerant can replace the R134a working medium.
(4) The refrigerant sliding temperature of the invention is less than 1 ℃, is a near azeotropic refrigerant, and eliminates the adverse effect caused by the temperature sliding. The heat pump system of the automobile air conditioner adopting the refrigerant does not need to set a coping scheme to prevent the heat exchange efficiency reduction caused by temperature slippage in the compressor.
Drawings
The above and other objects, features and advantages of the present disclosure will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings. The drawings described below are merely some embodiments of the present disclosure, and other drawings may be derived from those drawings by those of ordinary skill in the art without inventive effort.
FIG. 1 is a diagram of an automotive air conditioning heat pump system in accordance with an embodiment of the present invention;
in the figure:
1-a compressor; 2-indoor heat exchanger; 3-a throttle valve; 4-outdoor heat exchanger;
detailed description of the preferred embodiments
According to the requirements of the automobile air-conditioning system on the refrigerant, the refrigerant is required to have low GWP, zero ODP and high safety, in order to meet the performance, the refrigerant has the advantages of good environmental protection and good thermal performance, and the substances of the third component with the standard boiling point which is not much different from that of R134a, namely trifluoromethyl methyl ether (RE143a), isobutane (R600a), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), 3,3, 3-trifluoropropene (R1243zf), 2,3,3, 3-tetrafluoropropene (R1234yf) and the substances of the fourth component, namely dimethyl ether (RE170), are added into the formula, but the substances provided by the third component and the fourth component have flammability and the safety performance of the prepared refrigerant is poor, so the substances of the first component, namely pentafluoroethane (R125) and 1,1 are added into the formula, 1, 2-tetrafluoroethane (R134a) and 1,1,1,2,3,3, 3-heptafluoropropane (R227ea) and a substance of a second component, namely trifluoroiodomethane (R13I1) play the role of a flame retardant, so that the refrigerant provided by the invention not only has the GWP of less than 150, but also has the thermal performance and the sliding temperature of less than 1 ℃ and good safety performance.
The embodiment provides an automobile air-conditioning heat pump system using an environment-friendly refrigerant, and the automobile air-conditioning heat pump system further comprises a compressor 1, an indoor side heat exchanger 2, a throttle valve 3 and an outdoor side heat exchanger 4 which are sequentially connected to form a closed loop, preferably, the outdoor side heat exchanger 4 in the automobile air-conditioning heat pump system is used as an evaporator, and the indoor side heat exchanger 2 is used as a condenser, preferably, the compressor 1 is a scroll compressor, preferably, the compressor discharge temperature deviation of the automobile air-conditioning heat pump system is less than 3.5 ℃, preferably, the automobile air-conditioning heat pump system comprises a lubricant, further preferably, the lubricant is at least one substance selected from mineral oil, 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 substances.
The invention discloses a preparation method of an environment-friendly mixed refrigerant adopted in an automobile air-conditioning heat pump system, which comprises the following steps: one of the first component, the second component, the third component and the fourth component contained in the refrigerant is selected, and the refrigerant is prepared by physically mixing the first component 4-8 wt%, the second component 4-80 wt%, the third component 4-88 wt% and the fourth component 4-88 wt% in a normal-temperature normal-pressure liquid-phase state according to the mass ratio of different substances and uniformly mixing the components. Wherein: the first component provides materials such as pentafluoroethane (R125), 1,1,1, 2-tetrafluoroethane (R134a) and 1,1,1,2,3,3, 3-heptafluoropropane (R227 ea); the second component provides a material that is trifluoroiodomethane (R13I 1); the third component provides materials of trifluoromethyl methyl ether (RE143a), isobutane (R600a), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), 3,3, 3-trifluoropropene (R1243zf), 2,3,3, 3-tetrafluoropropene (R1234 yf); the fourth component provides dimethyl ether (RE 170). The basic parameters of each component substance are shown in the table 1:
TABLE 1 basic parameters of the component materials in the refrigerant
Figure BDA0002236160410000071
Specific examples are given below in which the proportions of the components are mass percentages and the sum of the mass percentages of the component substances of each refrigerant is 100%. In each of the examples and comparative examples, the components were physically mixed in a liquid phase at a constant mass ratio at room temperature and normal pressure, and uniformly mixed to obtain a refrigerant.
Example 1, pentafluoroethane (R125), trifluoroiodomethane (R13I1), 1-difluoroethane (R152a), and dimethylether (RE170) were physically mixed at a mass ratio of 4:56:16:24 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Example 2a refrigerant was obtained by physically mixing four components of pentafluoroethane (R125), trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and dimethylether (RE170) at a mass ratio of 4:60:8:28 in a liquid phase at normal temperature and pressure, and uniformly mixing.
Example 3a refrigerant was obtained by physically mixing four components of pentafluoroethane (R125), trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and dimethylether (RE170) at a mass ratio of 4:4:4:88 in a liquid phase at normal temperature and pressure, and uniformly mixing.
Example 4, pentafluoroethane (R125), trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), and dimethylether (RE170) were physically mixed at a mass ratio of 4:4:4:88 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Example 5, pentafluoroethane (R125), trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), and dimethylether (RE170) were physically mixed at a mass ratio of 4:16:64:16 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Example 6, pentafluoroethane (R125), trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf) and dimethylether (RE170) were physically mixed at a mass ratio of 4:4:4:88 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Example 7, pentafluoroethane (R125), trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf) and dimethylether (RE170) were physically mixed at a mass ratio of 4:4:84:8 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Example 8, 1,1, 2-tetrafluoroethane (R134a), trifluoroiodomethane (R13I1), trifluoromethyl methyl ether (RE143a), and dimethylether (RE170) were physically mixed at room temperature and normal pressure in a mass ratio of 4:4:4:88, and uniformly mixed to obtain a refrigerant.
Example 9 a refrigerant was prepared by physically mixing 1,1,1, 2-tetrafluoroethane (R134a), trifluoroiodomethane (R13I1), trifluoromethyl methyl ether (RE143a), and dimethylether (RE170) at room temperature under normal pressure in a liquid phase at a mass ratio of 8:64:8: 20.
Example 10, 1,1, 2-tetrafluoroethane (R134a), trifluoroiodomethane (R13I1), 1, 1-difluoroethane (R152a), and dimethylether (RE170) were physically mixed at room temperature and normal pressure in a liquid phase at a mass ratio of 4:4:56:36, and uniformly mixed to obtain a refrigerant.
Example 11, 1,1,1, 2-tetrafluoroethane (R134a), trifluoroiodomethane (R13I1), 1, 1-difluoroethane (R152a), and dimethylether (RE170) were physically mixed at a mass ratio of 4:4:4:88 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Example 12 a refrigerant was obtained by physically mixing 1,1,1, 2-tetrafluoroethane (R134a), trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and dimethylether (RE170) at a mass ratio of 8:60:12:20 in a liquid phase at normal temperature and pressure, and uniformly mixing the components.
Example 13 a refrigerant was prepared by physically mixing 1,1,1, 2-tetrafluoroethane (R134a), iodotrifluoromethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), and dimethylether (RE170) at room temperature under normal pressure in a liquid phase at a mass ratio of 8:48:36: 8.
Example 14, 1,1, 2-tetrafluoroethane (R134a), trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf), and dimethylether (RE170) were physically mixed at a mass ratio of 4:4:4:88 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Example 15, 1,1, 2-tetrafluoroethane (R134a), trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf) and dimethylether (RE170) were physically mixed at a mass ratio of 8:20:68:4 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Example 16, 1,1,1, 2-tetrafluoroethane (R134a), trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf) and dimethylether (RE170) were physically mixed at a mass ratio of 4:4:4:88 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Example 17, 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), 1, 1-difluoroethane (R152a) and dimethylether (RE170) were physically mixed at a mass ratio of 4:56:8:32 in a liquid phase at normal temperature and pressure, and uniformly mixed to obtain a refrigerant.
Example 18, 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), 1, 1-difluoroethane (R152a) and dimethylether (RE170) were physically mixed at a mass ratio of 4:64:8:24 under normal temperature and pressure in a liquid phase, and a refrigerant was obtained by uniformly mixing the components.
Example 19, four components of 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), isobutane (R600a) and dimethylether (RE170) were physically mixed at a mass ratio of 4:4:4:88 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Example 20, four components of 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), isobutane (R600a) and dimethylether (RE170) were physically mixed at a mass ratio of 4:48:4:44 in a normal temperature and pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Example 21 a refrigerant was obtained by physically mixing 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and dimethylether (RE170) at a mass ratio of 4:52:40:4 under normal temperature and pressure in a liquid phase, and uniformly mixing the components.
Example 22 a refrigerant was obtained by physically mixing 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and dimethylether (RE170) at a mass ratio of 4:68:4:24 under normal temperature and pressure in a liquid phase, and uniformly mixing the components.
Example 23 a refrigerant was obtained by physically mixing four components of 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf) and dimethylether (RE170) at a mass ratio of 4:32:60:4 under normal temperature and pressure in a liquid phase, and uniformly mixing.
Example 24, 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf) and dimethylether (RE170) were physically mixed at a mass ratio of 4:4:20:72 under normal temperature and pressure, and uniformly mixed to obtain a refrigerant.
Example 25 a refrigerant was obtained by physically mixing four components of 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf) and dimethylether (RE170) at room temperature and normal pressure in a liquid phase at a mass ratio of 4:68:4: 24.
Example 26 a refrigerant was obtained by physically mixing four components, 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf) and dimethylether (RE170), at a mass ratio of 4:4:88:4 under normal temperature and pressure in a liquid phase, and uniformly mixing the components.
Example 27 a refrigerant was obtained by physically mixing four components, 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf) and dimethylether (RE170), at a mass ratio of 4:80:4:12 under normal temperature and pressure in a liquid phase, and uniformly mixing the components.
Example 28 a refrigerant was obtained by physically mixing four components of 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf) and dimethylether (RE170) at a mass ratio of 4:40:36:20 under normal temperature and pressure in a liquid phase and uniformly mixing.
Example 29 a refrigerant was obtained by physically mixing four components, 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf) and dimethylether (RE170), at a mass ratio of 8:52:32:8 under normal temperature and pressure in a liquid phase, and uniformly mixing the components.
Comparative example 1,1,1, 1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), 3,3, 3-trifluoropropene (R1243zf) and dimethylether (RE170), and the four components were physically mixed at a mass ratio of 10:40:10:40 in a liquid phase at normal temperature and pressure, and were uniformly mixed to obtain a refrigerant.
Comparative example 2, 1,1,1,2,3,3, 3-heptafluoropropane (R227ea), trifluoroiodomethane (R13I1), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)) and dimethylether (RE170), and the four components were physically mixed at a mass ratio of 6:0:50:44 under normal temperature and pressure in a liquid phase, and were uniformly mixed to obtain a refrigerant.
Comparative example 3, 1,1,1, 2-tetrafluoroethane (R134a), trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf) and dimethylether (RE170), and the four components were physically mixed in a mass ratio of 6:82:4:8 at normal temperature and pressure in a liquid phase, and were uniformly mixed to obtain a refrigerant.
Comparative example 4, pentafluoroethane (R125), trifluoroiodomethane (R13I1), 2,3,3, 3-tetrafluoropropene (R1234yf) and dimethylether (RE170) were physically mixed at a mass ratio of 8:42:50:0 in a normal-temperature normal-pressure liquid phase, and uniformly mixed to obtain a refrigerant.
Table 2 compares the refrigerants of the above examples and comparative examples with basic parameters such as molecular weight, normal boiling point and environmental properties of R134 a.
TABLE 2 basic thermophysical parameters of the refrigerants
Figure BDA0002236160410000131
As can be seen from Table 2, the environmental performance of the heat pump system for the automobile air conditioner provided by the invention is far better than that of R134a, the thermal performance (the relative unit volume heating capacity and the relative efficiency COP are basically above 0.9) is equivalent to that of R134a, the GWP is less than 150, the glide temperature of the refrigerant is low, the refrigerant belongs to a near-azeotropic mixture, the adverse effect caused by the temperature glide is eliminated, and the problem of refilling after the refrigerant leaks is not considered.
The refrigerants corresponding to the above-mentioned embodiments and comparative examples were used in the heat pump system for an automobile air conditioner proposed in the present invention instead of the R134a refrigerant. As shown in fig. 1, a refrigerant is compressed into a high-temperature and high-pressure gas in a compressor 1, condensed into a medium-temperature and medium-pressure liquid by an indoor heat exchanger 2, throttled into a medium-temperature and low-pressure gas-liquid two-phase by a throttle valve 3, evaporated into a low-temperature and low-pressure gas by an outdoor heat exchanger 4, and finally circulated in the compressor 1.
Table 3 compares the heating cycle performance of the vehicle air conditioning system, i.e., the evaporation temperature of 0 ℃, the condensation temperature of 36 ℃, the superheat degree of 5 ℃, and the supercooling degree of 7 ℃ calculated according to the isentropic efficiency of 0.7, with the thermodynamic parameters (i.e., the compression ratio and the exhaust temperature) and the relative thermodynamic performance (i.e., the relative refrigerating capacity per unit volume and the relative COP) of R134a, calculated by simulation calculation using the refrigerants of the above-mentioned example and comparative example under the same conditions.
Table 3 performance comparison of refrigerant with R134a
Figure BDA0002236160410000141
Figure BDA0002236160410000151
(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 thermal performance, i.e., the volume heating capacity and the efficiency COP value of the refrigerant provided by the present invention are equivalent to those of R134a, and the refrigerant can be an environment-friendly refrigerant replacing R134 a. Because the automobile air conditioning system is easy to leak, the temperature slip of the mixed working medium is as small as possible, and the influence of the leakage on the mixture ratio of the mixed refrigerant is reduced, the slip temperature of the refrigerant provided by the invention is less than or equal to 0.5 ℃, and the problem of refilling after leakage is not required to be considered. Preferably, the refrigerant prepared by using the first component 1,1,1, 2-tetrafluoroethane (R134a) has smaller slip temperature and higher capacity and energy efficiency compared with the refrigerants of other examples, wherein the capacity and the energy efficiency are higher compared with those of R134 a. Preferably, the refrigerant prepared by using the third component 1, 1-difluoroethane (R152a) has higher capacity and energy efficiency relative to R134a compared with the refrigerants of other embodiments. Preferably, the four-component composition formula comprises 8% of the first component, 20% of the second component, 68% of the third component and 4% of the fourth component, and the prepared refrigerant has better heat production per unit volume and COP (coefficient of performance) compared with R134 a. Further preferably, the refrigerant prepared from 4% of 1,1,1, 2-tetrafluoroethane (R134a), 4% of trifluoroiodomethane (R13I1), 56% of 1, 1-difluoroethane (R152a), and 36% of dimethylether (RE170) in example 10 has a GWP of less than 150, a glide temperature of 0.07 ℃, and a relative COP of 1.006 as compared with R134a, and is more preferred.
In summary, when the content of the components of the formula is changed or the refrigerant prepared by the components is changed, the components cannot well play a synergistic effect, the sliding temperature and/or the flammability of the refrigerant can be increased, and the heat exchange effect and the environmental protection performance of a unit are influenced when the refrigerant is used. Comparative examples 1 to 4, the obtained refrigerant not only has large temperature slippage, but also has part of refrigerant with GWP higher than 150, which does not meet the requirement of the heat pump system of the automobile air conditioner. Therefore, the refrigerant provided by the invention not only has the environmental protection characteristics of GWP and zero ODP which are not more than 150, but also has the thermal performance equivalent to R134a and small temperature slip through the synergistic effect of all the components.
In conclusion, the GWP of the refrigerant adopted by the heat pump system for the automobile air conditioner is less than or equal to 150, the refrigerant has good environmental protection performance, and meets the requirement of environmental protection regulations in various regions of the world. The thermal performance of the heat pump system for the automobile air conditioner is equivalent to or better than that of a heat pump system of a refrigeration system using R134a, so that the heat pump system for the automobile air conditioner is used for replacing the heat pump system for the automobile air conditioner using R134a refrigerant, the temperature slippage is small, the refrigerant is near azeotropic refrigerant, the volumetric refrigerating capacity and the energy efficiency of the refrigerant are equivalent to those of the heat pump system for the automobile air conditioner using R134a refrigerant, and the problem of refilling after the refrigerant leaks is not considered.
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 (9)

1. The utility model provides an adopt vehicle air conditioner heat pump system of environmental protection refrigerant, vehicle air conditioner heat pump system still includes compressor (1), indoor side heat exchanger (2), choke valve (3) and outdoor side heat exchanger (4) and connects gradually and form closed circuit, its characterized in that: the environment-friendly refrigerant used by the heat pump system of the automobile air conditioner comprises four components, wherein the four components comprise 4-8% of a first component, 4-80% of a second component, 4-88% of a third component and 4-88% of a fourth component in percentage by mass; wherein,
the first component is one of pentafluoroethane (R125), 1,1,1, 2-tetrafluoroethane (R134a) and 1,1,1,2,3,3, 3-heptafluoropropane (R227 ea); the second component is trifluoroiodomethane (R13I 1); the third component is one of trifluoromethyl methyl ether (RE143a), isobutane (R600a), 1-difluoroethane (R152a), trans-1, 3,3, 3-tetrafluoropropene (R1234ze (E)), 3,3, 3-trifluoropropene (R1243zf), 2,3,3, 3-tetrafluoropropene (R1234 yf); the fourth component is dimethylether (RE 170); the GWP of the environment-friendly refrigerant is less than or equal to 150, and the ODP is 0.
2. An automotive air conditioning heat pump system using an environmentally friendly refrigerant as set forth in claim 1, wherein: the four components comprise, by mass, 4% -8% of a first component, 4% -40% of a second component, 32% -68% of a third component and 4% -36% of a fourth component, the GWP of the environment-friendly refrigerant is less than or equal to 150, and the ODP is 0.
3. An automotive air conditioning heat pump system using an environmentally friendly refrigerant as set forth in claim 1 or 2, wherein: the first component is 1,1,1, 2-tetrafluoroethane (R134 a).
4. A heat pump system for an air conditioner of an automobile using an eco-friendly refrigerant as set forth in claim 3, wherein: the third component is 1, 1-difluoroethane (R152 a).
5. An automotive air conditioning heat pump system using an environmentally friendly refrigerant as set forth in claim 1, wherein: the compressor (1) is a scroll compressor.
6. An automobile air conditioning heat pump system using an environmentally friendly refrigerant as set forth in any one of claims 1 to 5, wherein: the compressor discharge temperature deviation of the automobile air conditioning heat pump system is less than 3.5 ℃.
7. The air conditioning system of claim 6, wherein the compressor comprises a lubricant selected from at least one of mineral oil, silicone oil, Polyalkylbenzene (PAB), polyol ester (POE), polyalkylene glycol (PAG), polyalkylene glycol ester (PAG ester), polyvinyl ether (PVE), poly (α -olefin), and combinations thereof.
8. An automotive air conditioning heat pump system using an environmentally friendly refrigerant as set forth in claim 7, wherein: the heat pump system for the automobile air conditioner comprises a stabilizer.
9. An automotive air conditioning heat pump system using an environmentally friendly refrigerant as set forth in claim 8, wherein: the stabilizer is selected from: one of a diene-based compound, a phosphate, a phenol compound, and an epoxide, and mixtures thereof.
CN201910984126.XA 2019-10-16 2019-10-16 Automobile air conditioner heat pump system adopting environment-friendly refrigerant Active CN110843457B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910984126.XA CN110843457B (en) 2019-10-16 2019-10-16 Automobile air conditioner heat pump system adopting environment-friendly refrigerant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910984126.XA CN110843457B (en) 2019-10-16 2019-10-16 Automobile air conditioner heat pump system adopting environment-friendly refrigerant

Publications (2)

Publication Number Publication Date
CN110843457A true CN110843457A (en) 2020-02-28
CN110843457B CN110843457B (en) 2021-01-15

Family

ID=69596772

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910984126.XA Active CN110843457B (en) 2019-10-16 2019-10-16 Automobile air conditioner heat pump system adopting environment-friendly refrigerant

Country Status (1)

Country Link
CN (1) CN110843457B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111995987A (en) * 2020-07-31 2020-11-27 珠海格力电器股份有限公司 Mixed refrigerant and air conditioning system
CN112552876A (en) * 2020-12-10 2021-03-26 珠海格力电器股份有限公司 Mixed refrigerant and air conditioning system
CN114181664A (en) * 2021-12-09 2022-03-15 珠海格力电器股份有限公司 Environment-friendly mixed refrigeration working medium, refrigerant and refrigeration system
CN114716975A (en) * 2022-04-08 2022-07-08 大连理工大学 Heat transfer working medium suitable for reverse Carnot circulation system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101020812A (en) * 2007-03-14 2007-08-22 山东东岳化工有限公司 Environment protection refrigerant composition
CN101824305A (en) * 2010-04-06 2010-09-08 中国科学院理化技术研究所 Mixed refrigerant containing trifluoroiodomethane
US20110253927A1 (en) * 2010-04-15 2011-10-20 E. I. Du Pont De Nemours And Company Compositions comprising e-1,2-difluoroethylene and uses thereof
CN107250315A (en) * 2015-02-09 2017-10-13 旭硝子株式会社 Idle call working media used for electric vehicle and idle call working media composition used for electric vehicle
CN109988546A (en) * 2017-12-29 2019-07-09 特灵国际有限公司 Lower GWP refrigerant composition
CN110317576A (en) * 2019-07-22 2019-10-11 珠海格力电器股份有限公司 Mixed refrigerant and refrigerating device comprising same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101020812A (en) * 2007-03-14 2007-08-22 山东东岳化工有限公司 Environment protection refrigerant composition
CN101824305A (en) * 2010-04-06 2010-09-08 中国科学院理化技术研究所 Mixed refrigerant containing trifluoroiodomethane
US20110253927A1 (en) * 2010-04-15 2011-10-20 E. I. Du Pont De Nemours And Company Compositions comprising e-1,2-difluoroethylene and uses thereof
CN107250315A (en) * 2015-02-09 2017-10-13 旭硝子株式会社 Idle call working media used for electric vehicle and idle call working media composition used for electric vehicle
CN109988546A (en) * 2017-12-29 2019-07-09 特灵国际有限公司 Lower GWP refrigerant composition
CN110317576A (en) * 2019-07-22 2019-10-11 珠海格力电器股份有限公司 Mixed refrigerant and refrigerating device comprising same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111995987A (en) * 2020-07-31 2020-11-27 珠海格力电器股份有限公司 Mixed refrigerant and air conditioning system
CN112552876A (en) * 2020-12-10 2021-03-26 珠海格力电器股份有限公司 Mixed refrigerant and air conditioning system
CN112552876B (en) * 2020-12-10 2021-11-16 珠海格力电器股份有限公司 Mixed refrigerant and air conditioning system
CN114181664A (en) * 2021-12-09 2022-03-15 珠海格力电器股份有限公司 Environment-friendly mixed refrigeration working medium, refrigerant and refrigeration system
CN114181664B (en) * 2021-12-09 2022-09-23 珠海格力电器股份有限公司 Environment-friendly mixed refrigeration working medium, refrigerant and refrigeration system
CN114716975A (en) * 2022-04-08 2022-07-08 大连理工大学 Heat transfer working medium suitable for reverse Carnot circulation system

Also Published As

Publication number Publication date
CN110843457B (en) 2021-01-15

Similar Documents

Publication Publication Date Title
CN110843457B (en) Automobile air conditioner heat pump system adopting environment-friendly refrigerant
CN110591651B (en) Refrigerant composition for household air conditioner
CN110878195B (en) Coolant containing trifluoroiodomethane, mixture containing coolant and heat exchange system
WO1994000529A1 (en) Refrigerant blends containing 1,1,1,2,3,3,3-heptafluoropropane
CN110628389B (en) Low-combustible or non-combustible mixed refrigerant containing CF3I
CN112391145B (en) Environment-friendly hydrocarbon mixed refrigerant replacing R134a and application thereof
CN110684509B (en) Environment-friendly mixed refrigerant and heat exchange system
CN112745803B (en) Mixed refrigerant and air conditioning system
CN110878196A (en) Quaternary mixed environment-friendly refrigerant and composition
CN110845997B (en) Heat transfer medium and composition suitable for cooler
CN112080254B (en) Ternary environment-friendly refrigerant and preparation method thereof
CN112300761B (en) Refrigerant, preparation method thereof and air conditioning system
CN112680193B (en) Mixed refrigerant, heat exchange system and household appliance
CN110628388B (en) Mixed working medium suitable for scroll compressor and automobile air conditioning system
CN112552875B (en) Novel environment-friendly refrigerant and preparation method thereof
CN110628387B (en) Low-flammability heat transfer composition and heat exchange system
KR20140091139A (en) Vapor compression refrigeration/airconditioning equipment with suction line heat exchanger for improving energy efficiency using R1234ze
CN110645743A (en) Centrifugal water chilling unit adopting environment-friendly refrigerant
CN111944490B (en) Mixed refrigerant, refrigerating system and air conditioner
CN115627155B (en) Quaternary environment-friendly mixed refrigerant, and preparation method and application thereof
CN114752356B (en) Refrigerant and application thereof
CN113025279B (en) Composition containing fluoroolefin and preparation method thereof
CN110819304B (en) Low-flammability heat exchange medium and heat exchange system
CN114940888B (en) Refrigerant and preparation method thereof
CN113046029B (en) Composition containing fluoroolefin and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant