WO1997015637A1 - Refrigerant - Google Patents

Refrigerant Download PDF

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Publication number
WO1997015637A1
WO1997015637A1 PCT/CN1996/000093 CN9600093W WO9715637A1 WO 1997015637 A1 WO1997015637 A1 WO 1997015637A1 CN 9600093 W CN9600093 W CN 9600093W WO 9715637 A1 WO9715637 A1 WO 9715637A1
Authority
WO
WIPO (PCT)
Prior art keywords
refrigerant
component
weight
content
trifluoroiodomethane
Prior art date
Application number
PCT/CN1996/000093
Other languages
English (en)
Chinese (zh)
Inventor
Mingshan Zhu
Lizhong Han
Xiaoyu Zhao
Mao Ye
Original Assignee
Tsinghua University
Beijing Inoue Qinghua Freeze Technology Co. Ltd.
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
Priority claimed from CN95117039A external-priority patent/CN1053211C/zh
Priority claimed from CN 96106541 external-priority patent/CN1162616A/zh
Application filed by Tsinghua University, Beijing Inoue Qinghua Freeze Technology Co. Ltd. filed Critical Tsinghua University
Priority to AU72769/96A priority Critical patent/AU7276996A/en
Publication of WO1997015637A1 publication Critical patent/WO1997015637A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-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
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/04Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041Materials 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
    • C09K5/044Materials 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
    • C09K5/045Materials 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/11Ethers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/12Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10Components
    • C09K2205/12Hydrocarbons
    • C09K2205/122Halogenated hydrocarbons

Definitions

  • the present invention relates to a refrigerant and a method of using the same in equipment such as refrigeration, air conditioners, heat pumps, and thermostats.
  • BACKGROUND OF THE INVENTION In the prior art, refrigerators, freezers, automobile air conditioners, air conditioners, thermostats, and thermostats, etc. Most of the refrigerants used in the device have been CFC-12 and HCFC-22 for a long time. Because of its low toxicity, non-flammability, non-corrosion, and compatibility with other materials, it has been widely used in the above-mentioned refrigeration, air conditioning, heat pumps, etc. Systems and some other fields.
  • CFCs fluorocarbons
  • HCFCs hydrofluorocarbons
  • the main refrigerant used as an alternative to CFC-12 is 1,1,2-tetrafluoroethane (HFC-134a), which has the advantage of not damaging the ozone layer, and its thermal performance is similar to that of CFC-12.
  • HFC-134a 1,1,2-tetrafluoroethane
  • HCFC-22 As an alternative to HCFC-22, the following main methods are available: (1) R410A (HFC-32 / HFC-125, United States Signal Corporation), weight percent 50/50) azeotropic mixture, but its condensing pressure has increased by 60%, and the refrigeration capacity per unit volume has increased by 40%.
  • the compressor and refrigeration and air-conditioning system need to be redesigned; (2) R407C (HFC) from DuPont and I.CI -32 / HFC- 134a, weight percentage 23/25/52), its COP may be reduced by about 10%, the system needs to be re-optimized, and the greenhouse effect is also large; (3) HFC- 32 / HFC-134a (weight percentage 30/70) mixture, but flammable; (4) American Great Lakes Chemical Company HFC-227ea / HFC-32 mixture (weight percentage 30/70) (CN1083508A), but its greenhouse effect is large.
  • the present invention aims to overcome the shortcomings of the prior art and develop refrigerants that can replace CFC-12 and HCFC-22.
  • the present invention provides a refrigerant comprising the following components:
  • Component A is one or more compounds having fire extinguishing or nonflammable properties selected from the group consisting of: trifluoroiodomethane (CF 3 I, FC-1311), pentafluoroethane (CHF'CF HFC- 125), 1,1,2-tetrafluoroethane (CH 2 FC, HFC-134a) and monogas difluoromethane (CHCl, HCFC-22) , Its content is 10-95% of the total weight of the refrigerant; preferably 40-95%;
  • component B is one or more flammable compounds selected from the group consisting of: methane (HC50), acetamidine ( HC170), Propane (HC290), Cyclopropane (C270), Butane (HC600), Isobutane (HC600a), Difluoromethane
  • component B is not alone difluoromethane (CH: F 2 , HFC-32).
  • the refrigerant provided by the present invention can be prepared by conventional methods, such as the above components Physical mixing can be performed in the liquid phase according to its corresponding proportion.
  • component A of the refrigerant of the present invention may further contain 1, 1, 1, 2, 3, 3, 3-heptafluoropropane (CFJCHFCF] 'HFC-227ea) and / or 1,1,2,2-tetrafluoroethane ((: 1 ⁇ (1 ⁇ , HCFC-134).
  • Models based on calculators are known for advection Layer of ozone has no effect or little effect, that is, their ozone destruction potential (0DP) is zero or less than 0.03.
  • the present invention also provides a method for generating refrigeration, heating and temperature control using the above mixture. Therefore, one of the present invention
  • One aspect is to provide a novel, environmentally acceptable refrigerant, which can be used in refrigeration, heating and temperature control applications.
  • Another feature of the present invention is that the compound of component A is fire extinguishing or non-flammable In combination with the flammable compound of component B, a non-combustible refrigerant mixture with the required cooling, heating and temperature control performance is produced.
  • another aspect of the present invention is to provide a non-combustible refrigerant
  • the third feature of the present invention is that the above-mentioned refrigerant can provide energy efficiency (COP) equivalent to or better than that of CFC-12 or HCFC-22, and has substantially the same volumetric cooling capacity, and is also used for cooling, heating, etc.
  • COP energy efficiency
  • the component A of the refrigerant having the above-mentioned special advantages of the present invention is trifluoroiodomethane (FC-1311), and the component B is propane (HC290), the contents of which are 80-95 3 ⁇ 4 of the weight of the refrigerant, respectively.
  • component A in the refrigerant having the above-mentioned special advantages of the present invention is trifluoroiodomethane (FC-1311), the group Sub-B is propane (HC290) and 1, 1-difluoroethane (HFC-152a), the contents of which are respectively the weight of the refrigerant 60-90%, 3- 10%, and 5-30%, preferably 60-753 ⁇ 4, 3--53 ⁇ 4, and 20-35%; in yet another embodiment, a group of refrigerants having the above-mentioned special advantages of the present invention Fraction A is trifluoroiodomethane (FC-1 311) and 1, 1, 1, 2, 3, 3, 3-heptafluoropropane (HFC-227ea), component B is propane (HC290), and their contents are refrigerants 55-85%, 5-25% and 5-20% by weight, preferably 65-803 ⁇ 4, 5-25% and 10-18%; in another embodiment, in the refriger
  • the above refrigerant mixture can be easily used in place of refrigerators, freezers and automotive air conditioning systems CFC-12.
  • the component A in the refrigerant having the above-mentioned special advantages of the present invention is pentafluoroethane
  • component B is monofluoroethane (HFC-161), and its content is 10-95%, 5-90%, preferably 40-60%, 60- 40%;
  • component A in the refrigerant having the above-mentioned special advantages of the present invention is trifluoroiodomethane (FC-1311) and 1, 1, 2-tetrafluoroethane (HFC-1 34a ),
  • the component B is trifluoromethane (HFC-32), the content of which is 5-40%, 15-60% and 10-50% of the weight of the refrigerant, preferably 10-353 ⁇ 4, 35-60 % And 15-35X;
  • the component A in the refrigerant having the above-mentioned special advantages of the present invention is triiodoiodomethane (FC-1 311), and the component B is difluoromethane ( HFC-32) and 1, 1-difluoroethane (HFC-152a), the contents of which are 10-80%, 10-50
  • component B is cyclopropane (C270) and monofluoroethane (HFC-161), the content of which is 10-70%, 5- 20% and 20- 50%, preferably 40-60%, 10-20-203 ⁇ 4 and 25-453 ⁇ 44; in another embodiment, component A in the refrigerant having the above-mentioned special advantages of the present invention is trifluoromethane (FC-131 1) And pentafluoroethane (HFC-125), the component B is monogas acetamidine (HFC-161), the content of which is 5-50%, 20-60% and 20-60% of the weight of the refrigerant, It is preferably 5-15%, 30-50% and 40-55%.
  • the above refrigerant mixture can be easily used to replace HCFC-22 in air conditioning systems. It should be understood that the refrigerant mixture of the present invention may also contain other non-interfering components, such as lubricating oil, etc., in order to generate new Mixed refrigerant. Any such mixture is included within the scope of the present invention.
  • the refrigerant mixture of the present invention is useful in refrigeration and / or heating applications. In one embodiment of the present invention, that is, the embodiment of vapor compression refrigeration or heating, the refrigerant mixture of the present invention can be used, if necessary, can be used in the case of a suitable lubricant. In another of the present invention In one embodiment, that is, the refrigerant mixture of the present invention can be used in the embodiment of the thermostat.
  • the non-invention can be more fully explained through the following examples, and the following examples should be understood to be included in the present invention, but only Exemplary, not for the leisure of the present invention. The best embodiment of the present invention Example 1-4 Example 1
  • Embodiment 1 FC-1 31 1 and 20% HC290, which are 80% by weight, were physically mixed in a liquid phase to obtain a refrigerant 1.
  • Example 2
  • Example 3 was mixed 70% of HC290 (-131 1, 103 ⁇ 4 of HC290 and 20% of HFC-152a in a liquid phase to obtain a refrigerant 2.
  • Example 3 was mixed 70% of HC290 (-131 1, 103 ⁇ 4 of HC290 and 20% of HFC-152a in a liquid phase to obtain a refrigerant 2.
  • FC-1 311, 40% HFC_152a, and HFC-227ea of 103 ⁇ 4 were mixed in a liquid phase to obtain a refrigerant 4 by weight.
  • the thermal performance of the refrigerant prepared in the above example was calculated and listed in Table 1.
  • thermal performance The thermal performance (COP and cooling capacity) of the refrigerant mixture of the present invention is better than CFC-12, see Table 4.
  • the volumetric refrigeration capacity is approximately equal to CFC-12. This shows that the refrigerant of the present invention can directly use the original CFC-12 compressor without modification, while the volumetric refrigeration capacity of isobutane is very small, and the original compressor must be modified. Table 4
  • the refrigerant mixture provided by the present invention not only has good thermal performance, but also does not damage the odor layer, does not produce a greenhouse effect, has no haze reaction, and is non-toxic, and meets environmental protection requirements.
  • the slip temperature of the refrigerant 2 of the present invention is less than 1 ° C, so the refrigerant is a non-flammable sub-boiling mixture, which can be applied to the original refrigerating oil and directly filled.
  • the compressor and the main components in the system do not need No modification is required for the production line. Its performance is better than other existing alternatives, and it can be used as a long-term refrigerant to replace CFC-12.
  • Example 4 mixed with 45% by weight of HFC-125, 5 % of E170 and 50% of HFC-161 in the liquid phase to obtain refrigerant 9, which is used in an air-conditioning heat pump system instead of HCFC-22.
  • Example 10
  • the present invention has the following advantages and beneficial effects (taking the refrigerant 5 prepared in Example 5 of the present invention as an example): a.
  • Environmental performance The ozone destruction potential (0DP) of the refrigerant is zero, and The greenhouse effect coefficient (GWP) number is 1600. It can be seen that the refrigerant of the present invention fully meets the requirements for protecting the ozone layer, and the greenhouse effect is equivalent to HCFC-22.
  • Table 6 shows the comparison with HCFC-22 and other alternatives. Table 6
  • GWP 1700 1900 1600 1 100 about 1600 b.
  • Thermal parameters Under the design conditions of the air-conditioning heat pump system, the refrigerant pressure of the refrigerant 5 prepared in Example 5 and the pressure value of the refrigerant in the condenser, the pressure ratio of the compressor, and the exhaust gas temperature are compared with HCFC-22. Very similar, and the exhaust temperature is the lowest, the temperature slip is smaller than that of R407C and HFC-32 / HFC-134a. The comparison results are shown in Table 7.
  • thermo performance of the refrigerant 5 prepared in Example 5 is basically equivalent to that of HCFC-22, and among various alternatives, the refrigerant 5 of the present invention has the highest COP and the largest cooling capacity, which means charging and filling The minimum amount, see Table 8. This shows that refrigerant 5 can be charged directly. Table 8
  • Table 11 shows that the refrigerants 11 and 12 of the present invention are not only similar to the thermal performance of HCFC-22, but also better than the other three alternatives.
  • Example 1 3-16 Example 1 3
  • HCFC-22 with a weight percentage of 523 ⁇ 4 and 48% HFC-152a are mixed in a liquid phase to obtain a refrigerant 1 3, which is used in a refrigerator, a freezer and other systems as a transitional replacement for CFC-12.
  • HCFC-22 with 203 ⁇ 4, HFC-227ea with 203 ⁇ 4 and HFC-152a with 603 ⁇ 4 are mixed in liquid phase to obtain refrigerant 14 for use in refrigerators, freezers and other systems as a transitional replacement for CFC-12.
  • the thermal performance test of the refrigerator shows that the thermal performance such as the cooling speed, start-up performance, and temperature of the freezer and storage compartments of the refrigerant of the present invention completely complies with the Chinese national standard GB8059.
  • the filling volume of the agent was reduced by about 10%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)

Abstract

La présente invention concerne un réfrigérant constitué d'un composant A et d'un composant B. Le composant A, qui est ininflammable ou incombustible, représente 10 % à 95 % en poids. Ce composant A est constitué d'un ou de plusieurs composés appartenant au groupe des iodotrifluorométhane, pentafluoroéthane, 1,1,1,2-tétrafluoroéthane et chlorodifluorométhane. Le composant B, qui est inflammable, représente 5 % à 90 % en poids. Ce composant B est constitué d'un ou de plusieurs composés appartenant au groupe des méthane, éthane, propane, cyclopropane, butane, isobutane, difluorométhane, 1,1-difluoroéthane, 1,1,1-trifluorotéhane, éther diméthylique, fluoroéthane, propylène et éther éthylique. Si le composant A n'est que 1,1,1,2-tétrafluoroéthane, le composant B n'est pas le difluorométhane seul. Si le composant A n'est que pentafluoroéthane, le composant B n'est pas le difluorométhane seul. Si le composant A est un mélange de pentafluoroéthane et de 1,1,1,2-tétrafluoroéthane, le composant B n'est pas le difluorométhane seul. Le composant A peut contenir facultativement du 1,1,1,2,3,3,3-heptafluoropropane et/ou du 1,1,2,2-tétrafluoroéthane. Ce réfrigérant présente plus d'avantages que les produits de remplacement des CFC-12 et HCFC-22 pour ce qui est de l'effet sur l'environnement, ainsi que pour ce qui est des paramètres et des propriétés thermodynamiques, etc. L'invention concerne également des procédé d'utilisation du réfrigérant pour des applications en matière de réfrigération, de chauffage et de régulation thermique.
PCT/CN1996/000093 1995-10-20 1996-10-18 Refrigerant WO1997015637A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU72769/96A AU7276996A (en) 1995-10-20 1996-10-18 Refrigerant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN95117039A CN1053211C (zh) 1995-10-20 1995-10-20 长期性替代氟利昂-12的制冷剂
CN95117039.2 1995-10-20
CN 96106541 CN1162616A (zh) 1996-06-19 1996-06-19 一种新的绿色制冷剂
CN96106541.9 1996-06-19

Publications (1)

Publication Number Publication Date
WO1997015637A1 true WO1997015637A1 (fr) 1997-05-01

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PCT/CN1996/000093 WO1997015637A1 (fr) 1995-10-20 1996-10-18 Refrigerant

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AU (1) AU7276996A (fr)
WO (1) WO1997015637A1 (fr)

Cited By (39)

* Cited by examiner, † Cited by third party
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WO1999041325A1 (fr) * 1998-02-13 1999-08-19 Suk Jae Oho Composition refrigerante
WO1999048993A1 (fr) * 1998-03-26 1999-09-30 Ikon Corporation Compositions a base de melanges de trifluoro-iodomethane, tetrafluoroethane et difluoroethane
WO2000039242A1 (fr) * 1998-12-29 2000-07-06 Star Refrigeration Limited Composition pouvant se vaporiser
WO2000056834A1 (fr) * 1999-03-22 2000-09-28 E.I. Du Pont De Nemours And Company Compositions de difluoromethane, pentafluoroethane, 1,1,1,2-tetrafluoroethane et d'hydrocarbures
US6261472B1 (en) * 1996-11-04 2001-07-17 E. I. Du Pont De Nemours And Company Azeotrope-like compositions containing fluoroethane
WO2002026913A2 (fr) * 2000-09-27 2002-04-04 Honeywell International Inc. Compositions refrigerantes d'hydrocarbure chlorofluore
US6524495B1 (en) * 1999-11-10 2003-02-25 Korea Institute Of Science And Technology Refrigerant mixture comprising difluromethane, pentafluroethane and 1,1,1-trifluoroethane
US6604368B1 (en) 1999-10-04 2003-08-12 Refrigerant Products, Ltd. R 12 replacement refrigerant
US6606868B1 (en) 1999-10-04 2003-08-19 Refrigerant Products, Ltd. R 22 replacement refrigerant
US6629419B1 (en) 1999-10-04 2003-10-07 Refringerant Products Ltd. CFC 12 replacement refrigerant
KR100414762B1 (ko) * 2000-12-01 2004-01-13 에이씨엠텍(주) 냉매 r-500 대체용 혼합 냉매 조성물
US6841087B2 (en) * 2002-04-19 2005-01-11 Korea Institute Of Science And Technology Refrigerant composition comprising difluoromethane, 1,1,1-trifluoroethane and 1,1,1,2-tetrafluoroethane
US6991743B2 (en) 2002-03-19 2006-01-31 Rpl Holdings Limited Refrigerant for centrifugal compressors
KR100582453B1 (ko) * 2004-01-29 2006-05-23 주식회사이맥솔루션 Hc/hfc계 혼합냉매 조성물
WO2006069362A3 (fr) * 2004-12-21 2007-03-01 Honeywell Int Inc Compositions d'iodocarbone stabilisees
US7465698B2 (en) 2004-04-16 2008-12-16 Honeywell International Inc. Azeotrope-like compositions of difluoromethane and trifluoroiodomethane
US7479477B2 (en) 2004-04-16 2009-01-20 Honeywell International Inc. Azeotrope-like compositions of difluoromethane and trifluoroiodomethane
EP2017320A1 (fr) * 2004-04-16 2009-01-21 Honeywell International Inc. Compositions de trifluoroiodométhane de type azéotrope
US7605117B2 (en) 2004-04-16 2009-10-20 Honeywell International Inc. Methods of replacing refrigerant
US7622435B2 (en) 2004-04-16 2009-11-24 Honeywell International Inc. Methods of replacing refrigerant
DE202010014196U1 (de) * 2010-10-13 2011-03-17 Lauda Dr.R.Wobser Gmbh&Co.Kg Kältemittel auf der Basis mindestens eines nicht halogenierten brennbaren Kohlenwasserstoffs
US7972528B2 (en) 2006-03-03 2011-07-05 Rpl Holdings Limited Refrigerant composition
CN101649189B (zh) * 2009-09-04 2012-05-23 西安交通大学 一种含三氟碘甲烷的环保混合制冷剂
CN102965081A (zh) * 2012-11-28 2013-03-13 湖北绿冷高科节能技术有限公司 一种制冷剂及其制备方法
US8444873B2 (en) 2009-06-12 2013-05-21 Solvay Fluor Gmbh Refrigerant composition
US8551354B2 (en) 2006-03-03 2013-10-08 Rpl Holdings Limited Refrigerant composition
CN104212414A (zh) * 2013-06-03 2014-12-17 中化蓝天集团有限公司 一种混合制冷剂
US8999191B2 (en) 2013-03-15 2015-04-07 National Refrigerants, Inc. R22 replacement refrigerant
US9023231B2 (en) 2009-12-21 2015-05-05 Rpl Holdings Limited Non ozone depleting and low global warming potential refrigerants for low temperature refrigeration
US9175201B2 (en) 2004-12-21 2015-11-03 Honeywell International Inc. Stabilized iodocarbon compositions
US9920230B2 (en) 2004-12-21 2018-03-20 Honeywell International Inc. Use of low GWP refrigerants comprising CF3I with stable lubricants
US10208235B2 (en) 2007-11-16 2019-02-19 Honeywell International Inc. Heat transfer compositions, methods and systems
US10253233B2 (en) 2015-03-27 2019-04-09 Rpl Holdings Limited Non-ozone depleting and low global warming refrigerant blends
US20190136108A1 (en) * 2004-12-21 2019-05-09 Honeywell International Inc. Stabilized iodocarbon compositions
WO2021119375A1 (fr) * 2019-12-12 2021-06-17 The Chemours Company Fc, Llc Compositions réfrigérantes comprenant r-32, r-134a, et cf3i
US20210253925A1 (en) * 2007-11-16 2021-08-19 Honeywell International Inc. Hydrofluorocarbon/trifluoroiodomethane/hydrocarbons refrigerant compositions
CN113980649A (zh) * 2021-11-09 2022-01-28 珠海格力电器股份有限公司 一种混合制冷剂和空调系统
US11459497B2 (en) 2017-11-27 2022-10-04 Rpl Holdings Limited Low GWP refrigerant blends
US11827834B2 (en) 2020-10-22 2023-11-28 Rpl Holdings Limited Thermal pump refrigerants

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