WO2015000367A1 - 一种环保型近共沸混合制冷剂 - Google Patents

一种环保型近共沸混合制冷剂 Download PDF

Info

Publication number
WO2015000367A1
WO2015000367A1 PCT/CN2014/080384 CN2014080384W WO2015000367A1 WO 2015000367 A1 WO2015000367 A1 WO 2015000367A1 CN 2014080384 W CN2014080384 W CN 2014080384W WO 2015000367 A1 WO2015000367 A1 WO 2015000367A1
Authority
WO
WIPO (PCT)
Prior art keywords
hfc
refrigerant
component
hfe
environment
Prior art date
Application number
PCT/CN2014/080384
Other languages
English (en)
French (fr)
Inventor
郭智恺
谢品赞
方小青
Original Assignee
浙江蓝天环保高科技股份有限公司
中化蓝天集团有限公司
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 浙江蓝天环保高科技股份有限公司, 中化蓝天集团有限公司 filed Critical 浙江蓝天环保高科技股份有限公司
Priority to US14/899,944 priority Critical patent/US20160137896A1/en
Priority to EP14820667.5A priority patent/EP3018184B1/en
Priority to KR1020177021283A priority patent/KR102019575B1/ko
Priority to KR1020157037196A priority patent/KR20160047434A/ko
Publication of WO2015000367A1 publication Critical patent/WO2015000367A1/zh
Priority to US16/216,339 priority patent/US10752819B2/en
Priority to HRP20191457 priority patent/HRP20191457T1/hr
Priority to US16/924,894 priority patent/US11136483B2/en
Priority to US17/466,812 priority patent/US11549042B2/en

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • 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
    • 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
    • C09K2205/32—The mixture being azeotropic

Definitions

  • the present invention relates to a mixed refrigerant, and more particularly to a refrigerant composition which can directly replace HFC-134a without any change and which does not destroy atmospheric ozone potential and has a very low greenhouse effect.
  • HFC-134a 1, 1, 1, 2-tetrafluoroethane
  • CFC-12 has been widely used for its excellent performance, but because of its greenhouse effect value of up to 1430, it was The Kyoto Protocol is listed as one of the first high-GWP refrigerants to be phased out.
  • HFC-134a used in small-scale refrigeration equipment most of them have been replaced by HC_600a, and the replacement of HFC-134a in industrial refrigeration and automotive air-conditioning has become a hot topic and urgent problem to be solved in various countries around the world.
  • HFC-134a substitution is mainly: carbon dioxide (C0 2 ), 1, 1 - difluoroethane (HFC- 152a), 2, 3, 3, 3-tetrafluoropropene (HF0-1234yf) Etc.
  • C0 2 carbon dioxide
  • HFC- 152a 1, 1 - difluoroethane
  • HF0-1234yf 2, 3, 3, 3-tetrafluoropropene
  • HFC-152a has high energy efficiency and low refrigerant price, it has strong flammability and needs to be increased twice.
  • HFC-1234yf discloses a 2, 3, 3, 3-tetrafluoropropene (HFC-1234yf), 1, 1-difluoroethane (HFC_152a) and a mixture of dimethyl ether (DME);
  • CN102703033A discloses a 2, 3, 3, 3-tetrafluoropropene (HFC-1234yf), 1, 1, 1, 2-tetrafluoroethane a mixture of (HFC_134a) and dimethyl ether (DME); CN102066518A (200980122002.
  • HFC-1234yf discloses a 2, 3, 3, 3-tetrafluoropropene (HFC-1234yf), 1,1,1,2_ a mixture of tetrafluoroethane (HFC-134a) and 1,1-difluoroacetamide (HFC_152a); CN102083935A (200980125796.
  • 0 discloses a 1, 1, 1, 2-tetrafluoroethane (HFC- 13 Mixture of 4a), 2, 3, 3, 3-tetrafluoropropene (HFC-1234yf) CN102083935A (200980125796.
  • HFC-134a 1,1,1,2-tetrafluoroacetamidine
  • HFC-1234yf 2,3,3,3-tetrafluoropropene
  • CN102712837A 201080038152.
  • 0 discloses 1,1,1,2-tetrafluoroethane (HFC-134a), 2,3,3,3-tetrafluoropropene (HFC-1234yf) and difluoromethane (HFC) - 32) Composition of the mixture, etc.
  • the refrigerant composition disclosed in the above patent has a high GWP value, or a high flammability, or a large temperature slip, or a low energy efficiency, or a small volumetric refrigeration capacity, or can not be directly filled for HFC- Disadvantages such as the 134a system, it is necessary to develop a refrigerant that replaces HFC-134a with better refrigeration performance, better compatibility with existing systems, and better environmental performance.
  • the object of the present invention is to provide an environment-friendly near-azeotropic refrigerant mixture, which has better environmental performance and performance than HFC-134a, and can be directly replaced by any component in a system using HFC_134a. Low replacement cost refrigerant.
  • an environmentally friendly near-azeotropic refrigerant mixture basically consisting of 2, 3, 3, 3-tetrafluoropropene (HF0-1234yf), trifluoromethyl ether
  • HFE-143a and a third component, the third component being selected from the group consisting of fluoroethane (HFC-161), 1, 1, 1, 2-tetrafluoroethane (HFC-134a), Difluoromethane (HFC-32), dimethyl ether (CH 3 ()CH 3 HFE- 170), propane (HC_290), cyclopropane (C270), one or two or more combinations, and each group
  • HFC-161 fluoroethane
  • HFC-134a 1, 1, 1, 2-tetrafluoroethane
  • Difluoromethane HFC-32
  • dimethyl ether CH 3 ()CH 3 HFE- 170
  • propane HC_290
  • C270 cyclopropane
  • HFE- 143a 1% - 15%
  • the third component 1%_15%.
  • each substance such as fluoroethane
  • HFC-161 1, 1, 1, 2-tetrafluoroethane (HFC-134a), difluoromethane (HFC_32), dimethyl ether (CH 3 ()CH 3 , HFE_170), propane (HC-290) And cyclopropane (C270), any one, two or more may be selected as the third component, and when two or more substances are selected as the third component, each substance may be in any ratio.
  • the environmentally friendly near-azeotropic refrigerant mixture of the present invention preferably has a mass percentage of each component:
  • Third component 1%_10%.
  • the environmentally friendly near-azeotropic refrigerant mixture according to the present invention, further preferred component percentages of the components are:
  • HFE- 143a 5% - 10%
  • Third component 1%_5%.
  • the environmentally friendly near-azeotropic refrigerant mixture of the present invention preferably has a temperature slip of less than 1 ° C and a GWP value of less than 150.
  • the environmentally friendly near-azeotropic refrigerant mixture provided by the invention is suitable for replacing HFC-134a, and is particularly suitable for replacing HFC-134a in automobile air conditioners.
  • the automotive air conditioning system can directly charge the mixed refrigerant to replace the HFC-134a without changing any of the equipment components.
  • the environmentally friendly near-azeotropic refrigerant mixture of the present invention has the following advantages over the prior art disclosed:
  • the environmental performance is better than HFC-134a, the ozone depletion potential 0DP value is zero, and the global warming potential GWP value is significantly lower than HFC-134a;
  • Evaporation pressure, condensing pressure and pressure ratio are equivalent to HFC-134a, the unit volume cooling capacity is higher than HFC_134a, the temperature slip is small, the COP value is greater than HFC-134a, the exhaust temperature is lower, and the performance is excellent;
  • the refrigerant of the present invention can be directly used in the system using HFC-134a without changing any components of the equipment, and is compatible with the piping components of the refrigeration system originally using HFC-134a, and can reduce the amount of filling , to improve energy efficiency, has the advantages of saving resources and saving energy.
  • the trifluoromethane (Ch' 3 ()CH 3 , HFE- 143a) of the above composition has a molecular formula of CF 3 ()CH 3 , a molecular weight of 100. 04, a standard boiling point of -24. 0 ° C , a critical
  • the temperature was 104. 8 ° C
  • the critical pressure was 3.59 MPa
  • the GWP value was 750.
  • the fluoroethane (HFC-161) of the above composition has a molecular formula of CH 3 CH 2 F, a molecular weight of 48. 06, a standard boiling point of -37. 1 ° C, a critical temperature of 102. 2 ° C, a critical pressure.
  • the value is 4. 7Mpa, and the GWP value is 12.
  • the second component of the above-mentioned composition is a difluoromethane (HFC-32) having a molecular formula of CH 2 F 2 , a molecular weight of 52. 02, a standard boiling point of -51. 7 V, a critical temperature of 78. 2 ° C, a critical pressure of 5 78MPa, GWP value is 675. 1 , 1, 1, 2-tetrafluoroethane (HFC- 134a) having a molecular formula of CH 2 FCF 3 , a molecular weight of 102. 03, a standard boiling point of -26. 1 ° C, a critical temperature of 101. The critical pressure is 4. 06MPa, and the GWP value is 1430.
  • HFC-32 difluoromethane
  • HFC- 134a 1, 1, 2-tetrafluoroethane having a molecular formula of CH 2 FCF 3 , a molecular weight of 102. 03, a standard boiling point of -
  • the dimethyl ether (HFE-170) of the above composition has a molecular formula of CH 3 OCH 3 , a molecular weight of 46. 07, a normal boiling point of -24. 8 ° C, a critical temperature of 127.2 ° C, a critical pressure of 5. 34MPa, GWP value is about 1.
  • the above-mentioned component is a propane (HC-290) having a molecular formula of CH 3 CH 2 CH 3 , a molecular weight of 44. 10, a standard boiling point of -42. 1 ° C, a critical temperature of 96. 7 ° C, a critical pressure of 4. 25MPa, GWP value is about 20.
  • HC-290 propane having a molecular formula of CH 3 CH 2 CH 3 , a molecular weight of 44. 10, a standard boiling point of -42. 1 ° C, a critical temperature of 96. 7 ° C, a critical pressure of 4. 25MPa, GWP value is about 20.
  • the Vapor (C-270) having a molecular weight of CH 2 CH 2 CH 2 , a molecular weight of 42. 08, a standard boiling point of -31. 5 V, a critical temperature of 125. 2V, a critical pressure of 5. 58MPa, GWP value is about 20.
  • Example 1 HF0-1234yf, HFE-143a and C270 were physically mixed in a liquid phase at a mass percentage of 70:15:15.
  • Example 2 HF0-1234yf, HFE-143a and E170 were physically mixed in a liquid phase at a mass percentage of 75:15:10.
  • Example 3 HF0-1234yf, HFE-143a and R134a were physically mixed in a liquid phase at a mass percentage of 80:10:5.
  • Example 4 HF0-1234yf, HFE_143a and R290 were physically mixed in a liquid phase at a mass percentage of 90:5:5.
  • Example 5 HF0-1234yf, HFE-143a and R161 were physically mixed in a liquid phase at a mass percentage of 94:1:5.
  • Example 6 HF0-1234yf, HFE-143a and R32 were physically mixed in a liquid phase at a mass percentage of 98:1:1.
  • Table 1 compares the environmental performance of the above examples with HFC-134a. 0 (100 ⁇ ) ⁇ The 0DP value with CFC-11 as the reference value 1. 0, GWP value with C0 2 as the reference value 1. 0 (100 years). Table 1 Comparison of environmental performance Working medium 0DP GWP
  • HFC-134a 0 1430 As can be seen from Table 1, the above-mentioned examples have zero ozone layer potential (0DP) values, and the global warming potential (GWP) values are 15 to 150, both smaller than HFC-134a and comply with the EU MAC.
  • the directive has a GWP value of not more than 150 for automotive air-conditioning refrigerants, which has much less impact on the environment than HFC-134a, and has excellent environmental performance. It is a long-term replacement for HFC_134a.

Landscapes

  • 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

本发明公开了一种环保型近共沸混合制冷剂，基本由HFO-1234yf、HFE-143a 和第三组分组成，且各组分的质量百分比为：HFO-1234yf：70％-98％；HFE-143a： 1％-15％；第三组分：1％-15％。本发明所述制冷剂环境友好、热力性能优秀、可直接在原使用HFC-134a的系统不更改任何零部件实现灌注式替代，可作为 HFC-134a的长期替代物。

Description

一种环保型近共沸混合制冷剂 技术领域
本发明涉及一种混合制冷剂， 尤其涉及一种可不作任何改变而直接替代 HFC-134a的、不 破坏大气臭氧潜能且温室效应极低的制冷剂组合物。 背景技术
1， 1， 1， 2-四氟乙烷（HFC-134a)作为 CFC-12的替代物， 以其优异的使用性能得到了广泛 的应用， 但由于其具有高达 1430的温室效应值， 被"京都议定书"列为首批淘汰的高 GWP值 制冷剂之一。 对于应用于小型制冷设备中的 HFC-134a， 大部分已经采用 HC_600a予以替代， 而对于应用于工商制冷与汽车空调中的 HFC-134a 的替代已经成为世界各国研究的热点和急 需解决的问题。
目前国际社会对 HFC-134a 替代的研究方向主要为： 二氧化碳 （C02 )、 1， 1_二氟乙烷 (HFC- 152a)、 2， 3， 3， 3-四氟丙烯 (HF0-1234yf ) 等， 但这些方案均各有优缺点。 使用 C02环 保性能好、 不可燃， 但系统压力高、 能效低， 系统需重新设计、 替代成本高； 使用 HFC-152a 虽然能效高、 制冷剂价格低， 但其可燃性强、 需增加二次回路等造成替代成本高； 使用 HF0-1234yf虽然可燃性低、 系统改造小， 但能效低、 制冷量小。 因此世界各国均在持续开展 HFC-134a替代物的研究， 其中混合制冷剂是一个主要的研究方向。
在现有技术中，专利文件 CN1285699C 200410084844. 5 )公开了一种以氟乙烷 （HFC_161 )、 1, 1- 二氟乙烷 （HFC-152a ) 和 1， 1， 1， 2- 四氟乙烷 （HFC_134a ) 组成的三元组合物； CN101671542A ( 200910018489. 4) 公开了一种以 2， 3， 3， 3-四氟丙烯 (HFO- 1234yf )、 1， 1-二 氟乙烷（HFC-152a)和异丁烷组成的混合物； CN101864277A ( 201010196224. 6 )公开了一种 以 2， 3， 3， 3- 四氟丙烯 （HFC-1234yf)、 1， 1- 二氟乙烷 （HFC_152a) 和二甲醚 (DME) 组成 的混合物； CN102703033A ( 201210165277. 0 ) 公开了一种以 2， 3， 3， 3- 四氟丙烯 (HFC-1234yf)、l， 1， 1， 2-四氟乙烷 （HFC_134a)和二甲醚（DME)组成的混合物； CN102066518A ( 200980122002. 5 ) 公开了一种以 2， 3， 3， 3- 四氟丙烯 ( HFC- 1234yf )、 1，1，1，2_四氟乙烷 (HFC- 134a)和 1， 1_二氟乙焼（HFC_152a)组成的混合物； CN102083935A ( 200980125796. 0 ) 公开了一种 1， 1， 1， 2-四氟乙烷 (HFC- 134a)、 2， 3， 3， 3-四氟丙烯 (HFC-1234yf ) 组成的混合 物； CN102083935A ( 200980125796. 0 ) 公 开 了 一 种 1， 1， 1， 2- 四氟乙焼 (HFC- 134a)、 2， 3， 3， 3-四氟丙烯 (HFC-1234yf )组成的混合物； CN102712837A ( 201080038152. 0 )公开了 一种 1， 1， 1， 2-四氟乙烷（HFC-134a)、 2， 3， 3， 3-四氟丙烯 (HFC-1234yf )和二氟甲烷 (HFC- 32 ) 组成的混合物等。
上述专利中公开的制冷剂组合物存在或 GWP 值偏高、 或可燃性较强、 或温度滑移较大、 或能效较低、 或容积制冷量较小、 或不可直接充灌应用于 HFC-134a系统等缺点， 因此需要 开发具有制冷性能更优秀、与现有系统兼容性更好以及环保性能更佳的替代 HFC-134a的制冷 剂。
发明内容
本发明的目的在于提供一种环保型近共沸混合制冷剂， 该种制冷剂的环境性能和使用性 能均优于 HFC-134a， 可在使用 HFC_134a的系统中不改变任何部件直接替代使用的、 低替代 成本的制冷剂。
为达到发明目的本发明采用的技术方案是： 一种环保型近共沸混合制冷剂， 基本由 2， 3， 3， 3-四氟丙烯 （HF0-1234yf )、 三氟甲醚
( '興、 HFE- 143a) 和第三组分组成， 所述第三组分选自氟乙烷 (HFC- 161 )、 1， 1， 1， 2-四 氟乙烷 (HFC- 134a)、 二氟甲烷 (HFC- 32)、 二甲醚 ( CH3()CH3 HFE- 170)、 丙烷 （HC_290)、 环 丙烷 （C270 ) 中的一种、 两种或三种以上组合， 且各组分的质量百分比为：
HF0-1234yf: 70%-98%；
HFE- 143a: 1%- 15%;
第三组分： 1%_15%。
当第三组分中的各物质用于配制本发明所述近共沸混合制冷剂时， 各物质如氟乙烷
(HFC- 161 )、 1， 1， 1， 2-四氟乙烷（HFC-134a)、二氟甲烷（HFC_32)、二甲醚（CH3()CH3, HFE_170)、 丙烷 （HC-290 ) 和环丙烷 （C270 ) 中， 可以选择任意一种、 两种或三种以上作为第三组分， 当选择两种以上物质作为第三组分时， 各物质间可以是任何比例。
本发明所述的环保型近共沸混合制冷剂， 其优选的各组分质量百分比为：
HF0-1234yf: 75%- 94%;
HFE- 143a: 5%- 15%;
第三组分： 1%_10%。 本发明所述的环保型近共沸混合制冷剂， 其进一步优选的各组分质量百分比为：
HF0-1234yf: 85%- 94%;
HFE- 143a: 5%- 10%;
第三组分： 1%_5%。
本发明所述的环保型近共沸混合制冷剂， 优选温度滑移小于 1 °C， GWP值小于 150。
本发明提供的环保型近共沸混合制冷剂适合用于替代 HFC-134a， 尤其适合在汽车空调中 用于替代 HFC-134a。 当在在汽车空调中用于替代 HFC_134a时， 所述汽车空调系统可以不改 变任何设备部件， 直接充注所述混合制冷剂以替代 HFC-134a。 本发明的环保型近共沸混合制 冷剂与现有公开的技术相比， 具有以下优点：
( 1 ) 环境性能优于 HFC-134a， 消耗臭氧层潜能 0DP值为零， 全球变暖潜能 GWP值均较 HFC-134a有大幅度降低；
( 2 ) 使用安全， 可燃性弱；
( 3 )蒸发压力、冷凝压力和压比等均与 HFC-134a相当， 单位容积制冷量高于 HFC_134a， 温度滑移小， COP值大于 HFC-134a， 排气温度较低， 使用性能优秀；
( 4) 在不改变设备任何部件的前提下， 本发明制冷剂可直接用于原使用 HFC-134a的系 统中， 与原使用 HFC-134a的制冷系统管路部件兼容， 并可减少充灌量， 提高能效比， 具有节 省资源、 节约能源的优点。 具体实施方式
本发明提供的制冷剂， 其制备方法是将 2， 3， 3， 3-四氟丙烯 （HF0-1234yf )、 三氟甲醚 ( CF,0C¾ , HFE- 143a)和选自氟乙烷 (HFC- 161 )、 1， 1， 1， 2-四氟乙烷（HFC_134a)、 二氟甲烷 (HFC- 32)、 二甲醚 ( ϋΠ,θαΐ,, HFE-170 ), 丙烷 ( HC- 290)、 环丙烷 ( C270 ) 中的一种、 两种或 三种以上组合按照其相应的配比在液相状态下进行物理混合。
上述组分中的 2， 3， 3， 3-四氟丙烯（HF0-1234yf)，其分子式为 CH2CFCF3，分子量为 114. 04， 标准沸点为 -29. 35 °C， 临界温度为 94. 7°C， 临界压力为 3. 38MPa， GWP值为 4。
上述组分中的三氟甲醚 ( Ch'3()CH3、 HFE- 143a), 其分子式为 CF3()CH3， 分子量为 100. 04， 标准沸点为 -24. 0°C , 临界温度为 104. 8°C， 临界压力为 3. 59MPa， GWP值为 750。
上述组分中的氟乙烷（HFC-161 ),其分子式为 CH3CH2F，分子量为 48. 06，标准沸点为 -37. 1 °C， 临界温度为 102. 2°C， 临界压力为 4. 7Mpa， GWP值为 12。
上述组分中的二氟甲烷（HFC-32 ),其分子式为 CH2F2， 分子量为 52. 02，标准沸点为 -51. 7 V， 临界温度为 78. 2°C， 临界压力为 5. 78MPa， GWP值为 675。 上述组分中的 1， 1， 1， 2- 四氟乙烷 (HFC- 134a)， 其分子式为 CH2FCF3， 分子量为 102. 03， 标准沸点为 -26. 1 °C， 临界温度为 101. 1 °C， 临界压力为 4. 06MPa， GWP值为 1430。
上述组分中的二甲醚（HFE-170 ),其分子式为 CH3OCH3，分子量为 46. 07，标准沸点为 -24. 8 °C， 临界温度为 127. 2°C， 临界压力为 5. 34MPa， GWP值约为 1。
上述组分中的丙烷（HC-290 ), 其分子式为 CH3CH2CH3， 分子量为 44. 10， 标准沸点为 -42. 1 °C， 临界温度为 96. 7°C， 临界压力为 4. 25MPa， GWP值约为 20。
上述组分中的环丙烷（C-270 ),其分子式为 CH2CH2CH2，分子量为 42. 08，标准沸点为 -31. 5 V， 临界温度为 125. 2V , 临界压力为 5. 58MPa， GWP值约为 20。
下面的实施例为用来说明本发明的几个具体实施方式， 但并不将本发明局限于这些具体 实施方式。 本领域技术人员应该认识到， 本发明涵盖了权利要求书范围内所可能包括的所有 备选方案、 改进方案和等效方案。 实施例 1 : 将 HF0-1234yf、 HFE-143a和 C270在液相下按 70: 15： 15的质量百分比进行物理 混合。
实施例 2: 将 HF0-1234yf、 HFE-143a和 E170在液相下按 75: 15： 10的质量百分比进行物理 混合.
实施例 3: 将 HF0-1234yf、 HFE-143a和 R134a在液相下按 80: 10： 5的质量百分比进行物理 混合。
实施例 4: 将 HF0-1234yf、 HFE_143a和 R290在液相下按 90: 5： 5的质量百分比进行物理 混合。
实施例 5: 将 HF0-1234yf、 HFE-143a和 R161在液相下按 94: 1： 5的质量百分比进行物理混 合。 实施例 6： 将 HF0- 1234yf、 HFE- 143a和 R32在液相下按 98： 1： 1的质量百分比进行物 理混合。
现将上述实施例的性能与 HFC-134a进行比较， 说明本发明的特点和效果。
1、 环境性能
表 1比较了上述实施例与 HFC-134a的环境性能。 其中 0DP值以 CFC-11作为基准值 1. 0， GWP值以 C02作为基准值 1. 0 ( 100年）。 表 1 环境性能比较 工质 0DP GWP
实施例 1 0 120
实施例 2 0 115
实施例 3 0 150
实施例 4 0 40
实施例 5 0 15
实施例 6 0 20
HFC- 134a 0 1430 从表 1中可以看出，上述实施例的臭氧层消耗潜能（0DP)值均为零，全球变暖潜能（GWP) 值为 15〜150， 均小于 HFC-134a且符合欧盟 MAC指令对汽车空调制冷剂 GWP值不大于 150的 要求， 对环境的影响远小于 HFC-134a， 环境性能十分优异， 是 HFC_134a的长期替代物。
2、 温度滑移 表 2 温度滑移表
Figure imgf000006_0001
从表中可见， 除实施例 6以外各实施例的温度滑移均小于 1 °C， 表明为近共沸混合物， 有 利于系统的稳定运行。
3、 热工参数及热力性能
在汽车空调工况下 （即蒸发温度 = -1. 0°C， 冷凝温度 = 62. 0°C， 吸气温度 = 9°C， 过冷温 度= 57°C )， 上述实施例与 HFC-134a的热工参数（BP: 蒸发压力 P。、冷凝压力 Pk、压比 Pk/ P。、 排气温度 t2 ) 及相对热力性能 （即： 相对 C0P、 相对单位质量制热量 q。、 相对单位容积制热 量 、 相对单位容积耗功量 ) 的比较见表 3。
上述相对热力性能是指各实施例热力性能与 HFC-134a热力性能的比值， 相对密度是指 25 °C时的相对液体密度。 表 3 热工参数及热力性能的比较
Figure imgf000007_0001
从表 3可见， 在汽车空调工况下， 上述各实施例的冷凝压力均与 HFC-134a相当， 压比和 排气温度均低于 HFC-134a， 可直接充灌于原使用 HFC_134a的系统中； 上述各实施例的的密 度均低于 HFC-134a， 可以减少系统工质的充灌量； 各实施例的容积制冷量和 COP 值均高于 HFC-134a, 具有节能效果。

Claims

权利要求书
1. 一种环保型近共沸混合制冷剂， 基本由 HF0-1234yf、 HFE_143a和第三组分组成， 所述第 三组分选自 HFC-161、 HFC- 134a HFC_32、 HFE_170、 HC_290、 C270中的一种、 两种或三种以 上组合， 且各组分的质量百分比为：
HF0-1234yf: 70%-98%；
HFE- 143a: 1%- 15%;
第三组分： 1%_15%。
2. 按照权利要求 1所述的环保型近共沸混合制冷剂， 其特征在于所述制冷剂各组分的质量 百分比为：
HF0-1234yf: 75%- 94%;
HFE- 143a: 5%- 15%;
第三组分： 1%_10%。
3. 按照权利要求 1所述的环保型近共沸混合制冷剂， 其特征在于所述制冷剂各组分的质量 百分比为：
HF0-1234yf: 85%- 94%;
HFE- 143a: 5%- 10%;
第三组分： 1%_5%。
4. 按照权利要求 1至 3之一所述的环保型近共沸混合制冷剂， 其特征在于所述制冷剂的温 度滑移小于 rc。
5. 按照权利要求 1至 3之一所述的环保型近共沸混合制冷剂，其特征在于所述制冷剂的 GWP 值小于 150。
6. 按照权利要求 1至 3之一所述的环保型近共沸混合制冷剂， 其特征在于所述制冷剂用于 替代 HFC- 134a。
7. 按照权利要求 5所述的环保型近共沸混合制冷剂， 其特征在于所述制冷剂在汽车空调中 用于替代 HFC-134a。
8. 按照权利要求 6所述的环保型近共沸混合制冷剂， 其特征在于所述制冷剂汽车空调系统 不改变任何设备部件， 直接充注所述混合制冷剂以替代 HFC-134a。
PCT/CN2014/080384 2013-07-05 2014-06-20 一种环保型近共沸混合制冷剂 WO2015000367A1 (zh)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US14/899,944 US20160137896A1 (en) 2013-07-05 2014-06-20 Environmentally friendly near-azeotropic mixed refrigerant
EP14820667.5A EP3018184B1 (en) 2013-07-05 2014-06-20 Environment-friendly near-azeotropic mixed refrigerant
KR1020177021283A KR102019575B1 (ko) 2013-07-05 2014-06-20 친환경형 근사-공비 혼합 냉매
KR1020157037196A KR20160047434A (ko) 2013-07-05 2014-06-20 친환경형 근사-공비 혼합 냉매
US16/216,339 US10752819B2 (en) 2013-07-05 2018-12-11 Environmentally friendly near-azeotropic mixed refrigerant
HRP20191457 HRP20191457T1 (hr) 2013-07-05 2019-08-12 Ekološki prihvatljivo kvazi-azeotropno sredstvo za hlađenje
US16/924,894 US11136483B2 (en) 2013-07-05 2020-07-09 Environmentally friendly near-azeotropic mixed refrigerant
US17/466,812 US11549042B2 (en) 2013-07-05 2021-09-03 Environmentally friendly near-azeotropic mixed refrigerant

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310282218.6 2013-07-05
CN201310282218.6A CN104277765B (zh) 2013-07-05 2013-07-05 一种环保型近共沸混合制冷剂

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US14/899,944 A-371-Of-International US20160137896A1 (en) 2013-07-05 2014-06-20 Environmentally friendly near-azeotropic mixed refrigerant
US16/216,339 Division US10752819B2 (en) 2013-07-05 2018-12-11 Environmentally friendly near-azeotropic mixed refrigerant

Publications (1)

Publication Number Publication Date
WO2015000367A1 true WO2015000367A1 (zh) 2015-01-08

Family

ID=52143089

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/080384 WO2015000367A1 (zh) 2013-07-05 2014-06-20 一种环保型近共沸混合制冷剂

Country Status (6)

Country Link
US (4) US20160137896A1 (zh)
EP (1) EP3018184B1 (zh)
KR (2) KR20160047434A (zh)
CN (1) CN104277765B (zh)
HR (1) HRP20191457T1 (zh)
WO (1) WO2015000367A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107513373A (zh) * 2017-02-22 2017-12-26 唐建 一种应用于空调/热泵系统中的环保制冷剂

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113604200A (zh) * 2017-01-13 2021-11-05 霍尼韦尔国际公司 制冷剂、热传递组合物、方法和系统
WO2020072564A1 (en) * 2018-10-04 2020-04-09 The Chemours Company Fc, Llc Azeotropic compositions of hfo-1234yf and hydrocarbons
CN110655909B (zh) * 2019-09-12 2020-11-27 珠海格力电器股份有限公司 一种适用于汽车空调的环保混合冷媒
CN110591650B (zh) * 2019-09-12 2020-09-25 珠海格力电器股份有限公司 一种适用于离心式制冷机组的热传递组合物
US20230348770A9 (en) * 2019-12-18 2023-11-02 The Chemours Company Fc, Llc Compositions of hfo-1234yf and r-161 and systems for using the compositions
CN113046029B (zh) * 2021-02-09 2022-06-28 浙江衢化氟化学有限公司 一种含有氟代烯烃的组合物及其制备方法
CN113563847B (zh) * 2021-07-27 2022-04-15 珠海格力电器股份有限公司 四元环保混合制冷剂、其制备方法及制冷系统
CN114181664B (zh) * 2021-12-09 2022-09-23 珠海格力电器股份有限公司 一种环保混合制冷工质、制冷剂及制冷系统
CN114992919B (zh) * 2022-06-27 2023-06-06 珠海格力电器股份有限公司 制冷工质、制冷剂及制冷系统

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1285699C (zh) 2004-09-29 2006-11-22 浙江蓝天环保高科技股份有限公司 一种替代cfc－12的环保型制冷剂
CN101297016A (zh) * 2005-03-04 2008-10-29 纳幕尔杜邦公司 包含氟代烯烃的组合物
CN101671542A (zh) 2009-09-29 2010-03-17 山东东岳化工有限公司 一种制冷剂组合物
CN101747867A (zh) * 2009-10-13 2010-06-23 天津大学 含有HFO-1234yf(CF3CF=CH2)的有机朗肯循环混合工质
CN101864277A (zh) 2010-06-03 2010-10-20 集美大学 低gwp值的制冷剂组合物
CN102066518A (zh) 2008-06-11 2011-05-18 阿克马法国公司 基于氢氟烯烃的组合物
CN102083935A (zh) 2008-07-01 2011-06-01 大金工业株式会社 包含1,1,1,2-四氟乙烷(HFC134a)和2,3,3,3-四氟丙烯(HFO1234yf)的制冷剂组合物
CN102216411A (zh) * 2008-11-19 2011-10-12 纳幕尔杜邦公司 包含2，3，3，3-四氟丙烯和烃的组合物及其用途
CN102215917A (zh) * 2008-11-19 2011-10-12 纳幕尔杜邦公司 四氟丙烯组合物及其使用
CN102703033A (zh) 2012-05-24 2012-10-03 浙江大学 一种环保制冷剂及其制备方法
CN102712837A (zh) 2009-08-28 2012-10-03 墨西哥化学阿玛科股份有限公司 传热组合物

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050211949A1 (en) * 2003-11-13 2005-09-29 Bivens Donald B Detectable refrigerant compositions and uses thereof
US20060243944A1 (en) * 2005-03-04 2006-11-02 Minor Barbara H Compositions comprising a fluoroolefin
EP2044167A1 (en) * 2006-07-12 2009-04-08 Solvay Fluor GmbH Method for heating and cooling using fluoroether compounds, compositions suitable therefore and their use
WO2008033570A2 (en) * 2006-09-15 2008-03-20 E. I. Du Pont De Nemours And Company Method of detecting leaks of fluoroolefin compositions and sensors used therefor
JP5848903B2 (ja) * 2011-07-01 2016-01-27 出光興産株式会社 圧縮型冷凍機用潤滑油組成物
WO2014179583A2 (en) * 2013-05-01 2014-11-06 United Technologies Corporation Falling film evaporator for power generation systems

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1285699C (zh) 2004-09-29 2006-11-22 浙江蓝天环保高科技股份有限公司 一种替代cfc－12的环保型制冷剂
CN101297016A (zh) * 2005-03-04 2008-10-29 纳幕尔杜邦公司 包含氟代烯烃的组合物
CN102066518A (zh) 2008-06-11 2011-05-18 阿克马法国公司 基于氢氟烯烃的组合物
CN102083935A (zh) 2008-07-01 2011-06-01 大金工业株式会社 包含1,1,1,2-四氟乙烷(HFC134a)和2,3,3,3-四氟丙烯(HFO1234yf)的制冷剂组合物
CN102216411A (zh) * 2008-11-19 2011-10-12 纳幕尔杜邦公司 包含2，3，3，3-四氟丙烯和烃的组合物及其用途
CN102215917A (zh) * 2008-11-19 2011-10-12 纳幕尔杜邦公司 四氟丙烯组合物及其使用
CN102712837A (zh) 2009-08-28 2012-10-03 墨西哥化学阿玛科股份有限公司 传热组合物
CN101671542A (zh) 2009-09-29 2010-03-17 山东东岳化工有限公司 一种制冷剂组合物
CN101747867A (zh) * 2009-10-13 2010-06-23 天津大学 含有HFO-1234yf(CF3CF=CH2)的有机朗肯循环混合工质
CN101864277A (zh) 2010-06-03 2010-10-20 集美大学 低gwp值的制冷剂组合物
CN102703033A (zh) 2012-05-24 2012-10-03 浙江大学 一种环保制冷剂及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HE MAOGANG ET AL.: "Thermodynamic analysis of the fluoroether alternative refrigerants", JOURNAL OF ENGINEERING THERMOPHYSICS, vol. 31, no. 2, 31 March 2011 (2011-03-31), pages 145 - 147, XP055252418 *
See also references of EP3018184A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107513373A (zh) * 2017-02-22 2017-12-26 唐建 一种应用于空调/热泵系统中的环保制冷剂

Also Published As

Publication number Publication date
US20190112513A1 (en) 2019-04-18
EP3018184B1 (en) 2019-07-10
US20200339854A1 (en) 2020-10-29
US20210395591A1 (en) 2021-12-23
CN104277765A (zh) 2015-01-14
US11136483B2 (en) 2021-10-05
KR20160047434A (ko) 2016-05-02
CN104277765B (zh) 2017-12-08
HRP20191457T1 (hr) 2019-11-29
US11549042B2 (en) 2023-01-10
US10752819B2 (en) 2020-08-25
KR102019575B1 (ko) 2019-09-06
US20160137896A1 (en) 2016-05-19
EP3018184A1 (en) 2016-05-11
KR20170091183A (ko) 2017-08-08
EP3018184A4 (en) 2016-07-20

Similar Documents

Publication Publication Date Title
US11549042B2 (en) Environmentally friendly near-azeotropic mixed refrigerant
AU2013244830B2 (en) Compositions based on 2,3,3,4,4,4-hexafluorobut-1-ene
EP3012307B1 (en) Mixed refrigerant
CN107987797A (zh) 一种替代hcfc-22的环保混合制冷剂
WO1997015637A1 (fr) Refrigerant
EP2970734A1 (en) Compositions and method for refrigeration
CN109852348A (zh) 环保混合工质
WO2011038570A1 (zh) 一种制冷剂组合物
WO2011035546A1 (zh) 一种环保制冷剂
CN102229793A (zh) 一种低gwp值的制冷剂
CN112940683A (zh) 一种环保型制冷组合物
CN102241962A (zh) 一种低gwp值的组合物
CN102676119B (zh) 一种低gwp制冷剂及其制备方法
CN102229794A (zh) 一种低gwp值的制冷剂组合物
CN106543965B (zh) 一种三元混合制冷剂
CN106543963B (zh) 一种环保型制冷组合物
CN105820799A (zh) 一种含HFO-1234ze(E)的环保型制冷组合物
CN110655909B (zh) 一种适用于汽车空调的环保混合冷媒
WO2022105274A1 (zh) 一种新型环保制冷剂及其制备方法
CN108841360B (zh) 一种含全氟甲基乙烯基醚的组合物制冷剂
CN101182408A (zh) 一种三元混合制冷剂组合物
KR101572757B1 (ko) R32와 RC270과 R1234yf를 사용하는 3원 혼합냉매
CN114989784A (zh) 制冷剂及其制备方法
WO2009155822A1 (zh) 一种热泵系统用的混合工质
Ramu et al. Theoretical Assessment of R32/R125/R600a as a Potential Replacement for R-22

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14820667

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2014820667

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 14899944

Country of ref document: US

ENP Entry into the national phase

Ref document number: 20157037196

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE