CN112011311B - Non-azeotropic environment-friendly refrigerant, preparation method thereof and dehumidification system - Google Patents

Non-azeotropic environment-friendly refrigerant, preparation method thereof and dehumidification system Download PDF

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CN112011311B
CN112011311B CN202010812842.2A CN202010812842A CN112011311B CN 112011311 B CN112011311 B CN 112011311B CN 202010812842 A CN202010812842 A CN 202010812842A CN 112011311 B CN112011311 B CN 112011311B
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azeotropic
environment
friendly refrigerant
refrigerant
friendly
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CN112011311A (en
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黄泽清
黄明月
梁祥飞
郑波
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Gree Electric Appliances Inc of Zhuhai
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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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F3/00—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems
    • F24F3/12—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling
    • F24F3/14—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling by humidification; by dehumidification
    • 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
    • C09K2205/12—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
    • 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
    • C09K2205/34—The mixture being non-azeotropic

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  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
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  • Organic Chemistry (AREA)
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Abstract

The application relates to the technical field of refrigerants, in particular to a non-azeotropic environment-friendly refrigerant, a preparation method of the non-azeotropic environment-friendly refrigerant and a dehumidification system. The non-azeotropic environment-friendly refrigerant comprises monofluoromethane and trifluoroiodomethane, and the GWP value of the non-azeotropic environment-friendly refrigerant is not higher than 65. And mixing and stirring the components of the non-azeotropic environment-friendly refrigerant in a room-temperature liquid-phase state to obtain the non-azeotropic environment-friendly refrigerant. The non-azeotropic environment-friendly refrigerant provided by the invention has proper sliding temperature, can be well matched with a novel dehumidification system, has obviously improved cycle refrigeration coefficient and unit power consumption dehumidification capacity compared with the existing mixed refrigerant, has good environment-friendly safety performance, lower global warming potential and low flammability, and is suitable for an air-conditioning dehumidification system or other systems needing large sliding temperature refrigerants.

Description

Non-azeotropic environment-friendly refrigerant, preparation method thereof and dehumidification system
Technical Field
The application relates to the technical field of refrigerants, in particular to a non-azeotropic environment-friendly refrigerant, a preparation method of the non-azeotropic environment-friendly refrigerant and a dehumidification system.
Background
Generally speaking, the heat exchange temperature difference in the air dehumidification process is large, and the dehumidification energy consumption of the conventional air conditioning dehumidification system is high and the efficiency is low. The invention patent with publication number CN108375135A discloses a novel high-efficiency dehumidification system, which can effectively reduce the heat exchange temperature difference by using the temperature slippage characteristic of the non-azeotropic refrigerant, thereby reducing the irreversible loss in the heat transfer process, and simultaneously increasing the suction pressure of the compressor to reduce the power consumption. The applicant researches and finds that the high efficiency performance of a dehumidification system cannot be fully exerted by the existing non-azeotropic refrigerant, and the main reason is that the novel dehumidification system requires that the working medium has a slip temperature matched with the temperature difference of an air inlet and an air outlet during evaporation, and the slip temperature during condensation is not too high. The non-azeotropic refrigerant which is commonly used at present cannot be matched with the refrigerant well. On the other hand, with the global increasing emphasis on environmental issues, there are also more stringent requirements on the environmental protection and safety of new refrigerants in society.
Disclosure of Invention
In order to solve the technical problems that a non-azeotropic refrigerant in the prior art cannot be effectively matched with a novel dehumidification system and has poor environmental benefit, the invention mainly aims to provide the non-azeotropic environment-friendly refrigerant, improve the environmental performance under the condition of realizing better matching with the novel dehumidification system, and provide a preparation method of the non-azeotropic environment-friendly refrigerant and a dehumidification system applying the non-azeotropic environment-friendly refrigerant.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a non-azeotropic environment-friendly refrigerant.
The non-azeotropic environment-friendly refrigerant comprises monofluoromethane and trifluoroiodomethane, and the GWP value of the non-azeotropic environment-friendly refrigerant is not higher than 65.
Further, the non-azeotropic environment-friendly refrigerant comprises 12-52% of monofluoromethane and 48-88% of trifluoroiodomethane by mass percentage.
Further, the non-azeotropic environment-friendly refrigerant comprises 20-52% of monofluoromethane and 48-80% of trifluoroiodomethane by mass percentage.
Further, the non-azeotropic environment-friendly refrigerant comprises 36-52% of monofluoromethane and 48-64% of trifluoroiodomethane by mass percentage.
Further, the non-azeotropic environment-friendly refrigerant comprises 47.7 percent of monofluoromethane and 52.3 percent of trifluoroiodomethane by mass percentage.
In order to achieve the above object, according to a second aspect of the present invention, there is also provided a method for preparing a non-azeotropic environment-friendly refrigerant, for preparing the non-azeotropic environment-friendly 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 non-azeotropic environment-friendly refrigerant in a room-temperature liquid-phase state to obtain the non-azeotropic environment-friendly refrigerant.
In order to achieve the above object, according to a third aspect of the present invention, there is also provided a dehumidification system, including a working medium, where the working medium includes the non-azeotropic environment-friendly refrigerant according to the first aspect of the embodiments of the present invention.
The non-azeotropic environment-friendly refrigerant provided by the invention has proper sliding temperature, can be well matched with a novel dehumidification system, has obviously improved cycle refrigeration coefficient and unit power consumption dehumidification capacity compared with the existing mixed refrigerant, has good environment-friendly safety performance, has GWP lower than 65 and low flammability, and is suitable for an air-conditioning dehumidification system or other systems needing large sliding temperature refrigerants.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, serve to provide a further understanding of the application and to enable other features, objects, and advantages of the application to be more apparent. The drawings and their description illustrate the embodiments of the invention and do not limit it. In the drawings:
fig. 1 is a structural diagram of a dehumidification system according to an embodiment of the present invention;
fig. 2 is a trend chart of a non-azeotropic environment-friendly refrigerant and R407C in a dehumidification system under different working conditions for per unit power consumption according to an embodiment of the present invention;
fig. 3 is a trend chart of the non-azeotropic environment-friendly refrigerant and the energy efficiency of R407C in the dehumidification system under different working conditions, according to the embodiment of the invention.
In the figure:
1. a compressor; 2. a first throttle valve; 3. a flash tank; 4. a second throttle valve; 5. a throttle valve; 6. a first condenser; 7. a second condenser; 8. a first evaporator; 9. a second evaporator.
Detailed Description
In order to make the technical solutions 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 with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only partial 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.
It is noted that the terms "comprises" and "comprising," and any variations thereof, in the description and claims of this application and the above-described drawings are intended to cover non-exclusive inclusions, such that a system, product 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 product 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.
It should be noted that GWP shown in tables 1-2 of this document is referred to as "IPCC, 2013: clinical Change 2013: The Physical Science base. restriction of Working Group I to The Fifth Assessment Report of The Interactive Panel Change [ Stocker, T.F., D.Qin, G.K.Plattner, M.Tignor, S.K.Allen, J.Boschung, A.Naues, Y.Xia, V.Bex and P.M.Midgley (eds.) ]. Cambridge version, Cambridge, Kiteddom and New York, NY, USA,1535 pp."; other parameters are given by REFPROP 8.0.
The preparation method of the non-azeotropic environment-friendly refrigerant provided by the embodiment of the invention is that the components of the non-azeotropic environment-friendly refrigerant, namely monofluoromethane (R41) and trifluoroiodomethane (R13I1), are physically mixed into a binary mixture according to the corresponding mass ratio under the normal temperature and normal pressure liquid phase state, and the binary mixture can be mixed and stirred under the normal temperature and normal pressure liquid phase state to prepare the non-azeotropic environment-friendly refrigerant. Among them, monofluoromethane (R41) belongs to HFCs refrigerant, has excellent thermophysical properties and transmission characteristics, has ODP of 0 and low GWP, but monofluoromethane (R41) belongs to 3 flammable refrigerants, and the flammability limits the application range thereof. Trifluoroiodomethane (R13I1) is used for matching with monofluoromethane (R41) to obtain proper sliding temperature and other thermodynamic properties, and trifluoroiodomethane (R13I1) is an excellent flame retardant which can weaken the flammability of the refrigerant and meet the requirement of safety.
The basic parameters of each component in the non-azeotropic environment-friendly refrigerant in the embodiment of the invention are shown in the table 1.
TABLE 1 basic parameters of the components of non-azeotropic refrigerant
Figure BDA0002631617780000051
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 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 non-azeotropic environment-friendly refrigerant is 100%.
Example 1
The non-azeotropic environment-friendly refrigerant is obtained by physically and uniformly mixing monofluoromethane (R41) and trifluoroiodomethane (R13I1) at the normal temperature and the normal pressure according to the mass ratio of 12: 88.
Example 2
The non-azeotropic environment-friendly refrigerant is obtained by physically and uniformly mixing monofluoromethane (R41) and trifluoroiodomethane (R13I1) at the normal temperature and the normal pressure according to the mass ratio of 16: 84.
Example 3
The non-azeotropic environment-friendly refrigerant is obtained by physically and uniformly mixing monofluoromethane (R41) and trifluoroiodomethane (R13I1) at the normal temperature and the normal pressure according to the mass ratio of 20: 80.
Example 4
The non-azeotropic environment-friendly refrigerant is obtained by physically and uniformly mixing monofluoromethane (R41) and trifluoroiodomethane (R13I1) at a mass ratio of 24:76 at normal temperature and normal pressure in a liquid phase.
Example 5
The non-azeotropic environment-friendly refrigerant is obtained by physically and uniformly mixing monofluoromethane (R41) and trifluoroiodomethane (R13I1) according to the mass ratio of 28:72 at normal temperature and normal pressure.
Example 6
The non-azeotropic environment-friendly refrigerant is obtained by physically and uniformly mixing monofluoromethane (R41) and trifluoroiodomethane (R13I1) at the normal temperature and the normal pressure according to the mass ratio of 32: 68.
Example 7
The non-azeotropic environment-friendly refrigerant is obtained by physically and uniformly mixing monofluoromethane (R41) and trifluoroiodomethane (R13I1) at the normal temperature and the normal pressure according to the mass ratio of 36: 64.
Example 8
The non-azeotropic environment-friendly refrigerant is obtained by physically and uniformly mixing monofluoromethane (R41) and trifluoroiodomethane (R13I1) at the normal temperature and the normal pressure according to the mass ratio of 40: 60.
Example 9
The non-azeotropic environment-friendly refrigerant is obtained by physically and uniformly mixing monofluoromethane (R41) and trifluoroiodomethane (R13I1) according to the mass ratio of 44:56 at normal temperature and normal pressure.
Example 10
The non-azeotropic environment-friendly refrigerant is obtained by physically and uniformly mixing monofluoromethane (R41) and trifluoroiodomethane (R13I1) at the mass ratio of 47.7:52.3 under the normal temperature and pressure liquid phase.
Example 11
The non-azeotropic environment-friendly refrigerant is obtained by physically and uniformly mixing monofluoromethane (R41) and trifluoroiodomethane (R13I1) at the normal temperature and the normal pressure according to the mass ratio of 52: 48.
The above examples were compared with the basic parameters of R407C, such as molecular weight, normal boiling point, environmental properties, slip temperature, etc., and are reported in table 2.
TABLE 2 basic parameters of non-azeotropic refrigerants
Figure BDA0002631617780000071
(Note: in each example, the condensation slip temperature is the difference between the dew point temperature at a temperature of 40 ℃ and the bubble point temperature at the bubble point pressure, and the evaporation slip temperature is the difference between the dew point temperature at a temperature of 10 ℃ and the bubble point temperature at the bubble point pressure.)
As can be seen from Table 2, the environmental performance of the non-azeotropic environment-friendly refrigerant provided by the invention is far better than that of R407C, and the GWP of the non-azeotropic environment-friendly refrigerant is not higher than 65, wherein the GWP of the non-azeotropic environment-friendly refrigerant prepared in examples 1-4 is lower than 30; the non-azeotropic environment-friendly refrigerant has a slip temperature higher than R407C, wherein the condensation slip temperature is higher than 4.90 ℃, and the evaporation slip temperature is higher than 5.87 ℃.
Referring to fig. 1, an alternative dehumidification system to which embodiments of the present invention provide a non-azeotropic eco-friendly refrigerant may be applied is shown, and as shown in fig. 1, the dehumidification system includes a compressor 1, a first throttle valve 2, a flash tank 3, a second throttle valve 4, a throttle valve 5, a first condenser 6, a second condenser 7, a first evaporator 8, and a second evaporator 9. The specific working process is as follows: the high temperature refrigerant discharged from the compressor 1 is condensed into a two-phase state by the first condenser 6 and then introduced into the flash tank 3 through the first throttle valve 2. The refrigerant from the flash evaporator 3 is divided into two parts, wherein the gas phase refrigerant rich in low boiling point components enters a second condenser 7 to be condensed into liquid, and then enters a first evaporator 8 through a second throttling valve 4 to exchange heat; the liquid phase refrigerant rich in the high boiling point component is throttled by the throttle valve 5 and then mixed with the refrigerant rich in the low boiling point component after heat exchange by the first evaporator 8, and then enters the second evaporator 9 for heat exchange. The refrigerant discharged from the second evaporator 9 is sucked into the compressor, compressed, and discharged, thereby completing the cycle. From the viewpoint of humid air, the humid air is first cooled to a temperature close to the dew point temperature by the second evaporator 9, and then enters the first evaporator 8 to be dehumidified. The low-temperature and low-moisture content wet air from the first evaporator 8 is heated to a proper temperature by the second condenser 7 and the first condenser 6 in sequence and then sent to the user end.
The non-azeotropic environment-friendly refrigerant provided by the embodiment 10 of the invention and R407C were simulated by using the dehumidification system shown in FIG. 1, and the evaporation temperature, the condensation temperature, the relative specific power consumption dehumidification amount and the relative EER of the dehumidification system were compared under different moisture absorption conditions, and the results are shown in Table 3, FIG. 2 and FIG. 3.
Table 3 comparison of the properties of example 10 with R407C
Figure BDA0002631617780000081
As can be seen from table 3, fig. 2 and fig. 3, under different dehumidification conditions, the number of operation and relative thermodynamic performance (i.e., relative efficiency EER and relative unit power consumption dehumidification amount) of the non-azeotropic environment-friendly refrigerant in embodiment 10 of the present invention in the thermodynamic parameters (i.e., evaporation temperature and condensation temperature) of the dehumidification system shown in fig. 1 are better than those of the refrigerant R407C, and not only the unit power consumption dehumidification amount is large, but also the energy efficiency is significantly improved compared with R407C, where the performance index of the dehumidification system in the dehumidification mode is the unit power consumption dehumidification amount, and the performance index of the refrigeration mode is the refrigeration coefficient EER. In addition, by comparing the performance parameters of the non-azeotropic environment-friendly refrigerant provided by the embodiments 1 to 9 and 11 of the present invention and the performance parameter of the refrigerant R407C by using the dehumidification system shown in fig. 1, the operation number and the relative thermal performance of the thermal parameters of the non-azeotropic environment-friendly refrigerant provided by the embodiments 1 to 9 and 11 of the present invention are superior to those of the refrigerant R407C. It should be noted that the non-azeotropic environment-friendly refrigerant provided by the embodiment of the present invention is not limited to be applied to the dehumidification system shown in fig. 1, and the dehumidification system shown in fig. 1 is only schematically illustrated.
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 (6)

1. The non-azeotropic environment-friendly refrigerant is characterized by consisting of 12-52% of monofluoromethane and 48-88% of trifluoroiodomethane by mass percent, and the GWP value of the non-azeotropic environment-friendly refrigerant is not higher than 65.
2. A non-azeotropic environment-friendly refrigerant according to claim 1, which comprises 20 to 52 mass% of monofluoromethane and 48 to 80 mass% of trifluoroiodomethane.
3. A non-azeotropic environment-friendly refrigerant according to claim 1, which comprises 36 to 52 mass% of monofluoromethane and 48 to 64 mass% of trifluoroiodomethane.
4. A non-azeotropic environmental friendly refrigerant according to claim 1, which comprises 47.7% by mass of monofluoromethane and 52.3% by mass of trifluoroiodomethane.
5. A method for preparing a non-azeotropic environment-friendly refrigerant according to any one of claims 1 to 4, comprising the steps of: and mixing and stirring the components of the non-azeotropic environment-friendly refrigerant in a room-temperature liquid-phase state to obtain the non-azeotropic environment-friendly refrigerant.
6. A dehumidification system comprising a working fluid, wherein the working fluid comprises the non-azeotropic environmental protection refrigerant of any one of claims 1 to 4.
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CN102239228A (en) * 2008-12-02 2011-11-09 墨西哥化学阿玛科股份有限公司 Heat transfer compositions
CN102660229A (en) * 2012-04-26 2012-09-12 中科赛凌（北京）科技有限公司 Incombustible mixed refrigerant suitable for copious cooling temperature of 90-140DEG C below zero
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WO2018022888A1 (en) * 2016-07-29 2018-02-01 Honeywell International Inc. Heat transfer compositions, methods and systems
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CN110257014A (en) * 2019-07-19 2019-09-20 珠海格力电器股份有限公司 Mixed refrigeration working medium
CN110373157A (en) * 2019-07-22 2019-10-25 珠海格力电器股份有限公司 Refrigerant composition and method for preparing same
CN110822755A (en) * 2019-11-27 2020-02-21 江苏天舒电器有限公司 Heat pump system using non-azeotropic refrigerant mixture

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008076272A2 (en) * 2006-12-15 2008-06-26 E. I. Du Pont De Nemours And Company Compositions comprising 1,2,3,3,3-pentafluoropropene with z- and e-isomer ratio optimized for refrigeration performance
CN102239228A (en) * 2008-12-02 2011-11-09 墨西哥化学阿玛科股份有限公司 Heat transfer compositions
CN102660229A (en) * 2012-04-26 2012-09-12 中科赛凌（北京）科技有限公司 Incombustible mixed refrigerant suitable for copious cooling temperature of 90-140DEG C below zero
CN107614652A (en) * 2015-06-01 2018-01-19 旭硝子株式会社 Working medium for heat cycle, heat circulating system composition and heat circulating system
WO2018022888A1 (en) * 2016-07-29 2018-02-01 Honeywell International Inc. Heat transfer compositions, methods and systems
CN110028937A (en) * 2019-04-26 2019-07-19 中国科学院理化技术研究所 A kind of non-combustible cool storage medium of mixing
CN110257014A (en) * 2019-07-19 2019-09-20 珠海格力电器股份有限公司 Mixed refrigeration working medium
CN110373157A (en) * 2019-07-22 2019-10-25 珠海格力电器股份有限公司 Refrigerant composition and method for preparing same
CN110822755A (en) * 2019-11-27 2020-02-21 江苏天舒电器有限公司 Heat pump system using non-azeotropic refrigerant mixture

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