WO2022105274A1 - 一种新型环保制冷剂及其制备方法 - Google Patents

一种新型环保制冷剂及其制备方法 Download PDF

Info

Publication number
WO2022105274A1
WO2022105274A1 PCT/CN2021/106751 CN2021106751W WO2022105274A1 WO 2022105274 A1 WO2022105274 A1 WO 2022105274A1 CN 2021106751 W CN2021106751 W CN 2021106751W WO 2022105274 A1 WO2022105274 A1 WO 2022105274A1
Authority
WO
WIPO (PCT)
Prior art keywords
environmentally friendly
parts
refrigerant
friendly refrigerant
chloro
Prior art date
Application number
PCT/CN2021/106751
Other languages
English (en)
French (fr)
Inventor
李林辉
洪江永
杨波
张彦
余慧梅
赵阳
任亚文
Original Assignee
浙江衢化氟化学有限公司
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 浙江衢化氟化学有限公司 filed Critical 浙江衢化氟化学有限公司
Publication of WO2022105274A1 publication Critical patent/WO2022105274A1/zh

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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M131/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen
    • C10M131/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen containing carbon, hydrogen and halogen only
    • C10M131/04—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing halogen containing carbon, hydrogen and halogen only aliphatic
    • 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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2211/02—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only
    • C10M2211/022—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions containing carbon, hydrogen and halogen only aliphatic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the invention belongs to the technical field of refrigeration, and in particular relates to a novel environmentally friendly refrigerant and a preparation method thereof.
  • the EU has put forward strict restrictions on refrigerants with high GWP values, which stipulates that starting from January 1, 2017, new vehicles produced in the EU are prohibited from using refrigerants with a GWP value greater than 150; after January 1, 2015 , household refrigerators and freezers filled with HFC refrigerants and their GWP ⁇ 150 are prohibited from being sold in the EU market.
  • R134a 1,1,1,2-Tetrafluoroethane
  • ODP value is 0, has good safety and refrigeration performance, used to replace traditional R22 refrigerant, mainly used in automobiles Refrigeration fields such as air conditioners, heat pumps, chillers, refrigerators and freezers.
  • the GWP value of R134a refrigerant is as high as 1430, which has a strong greenhouse effect and belongs to one of the greenhouse gases controlled by the "Kyoto Protocol".
  • HFO fluorine-containing olefin
  • R1234yf fluorine-containing olefin
  • ODP value is 0, GWP value is less than 4, it is a new type of environmentally friendly refrigerant, but it is expensive, has poor cooling effect, complicated production process, and has a certain weak flammability, which increases refrigeration equipment. Manufacturer's production cost and safety performance.
  • Patent document CN107400502A discloses a ternary mixed refrigerant of difluoromethane, propylene and trifluoroiodomethane to replace R134a.
  • the optimized mixed refrigerant can save energy by up to about 12% compared to R134a, but trifluoroiodomethane has a certain amount of energy. Toxicity, while the mixed refrigerant still has a certain flammable risk.
  • Patent document CN101851490A discloses a compound containing 2,3,3,3-tetrafluoropropene (R1234yf), E-1,3,3,3-tetrafluoropropene (E-R1234ze) and 1,1-difluoroethane (R152a) mixed refrigerant, the mixed refrigerant GWP ⁇ 100, the COP value (energy efficiency ratio) is close to R134a, but the mixed refrigerant has certain flammability, and the content of fluorine-containing olefins is high, which leads to Replacement costs are higher.
  • Patent document CN110628389A discloses a ternary mixed refrigerant for replacing R134a, the first component is the flame retardant trifluoroiodomethane, the second component is trifluoromethyl methyl ether, and the third component is 2, 3,3,3-tetrafluoropropene (R1234yf), 3,3,3-trifluoropropene (R1243zf), E-1,3,3,3-tetrafluoropropene (E-R1234ze), 1,1-difluoropropene
  • the mixed refrigerant Non-flammable preferably refrigerant GWP less than 100, but all mixed refrigerant COP values are less than R134a.
  • the purpose of the present invention is to provide a novel environmentally friendly refrigerant with low GWP, high safety, good refrigeration effect and good lubricant compatibility and a preparation method thereof, aiming at the deficiencies of the prior art.
  • a novel environmentally friendly refrigerant in parts by weight, is composed of the following substances:
  • the global warming potential value of the novel environmentally friendly refrigerant is less than or equal to 150.
  • the global warming potential value of the new environmentally friendly refrigerant is less than or equal to 120.
  • the global warming potential value of the novel environmentally friendly refrigerant is less than or equal to 50.
  • the global warming potential value of the new environmentally friendly refrigerant is less than or equal to 5.
  • the invention also discloses a preparation method of the novel environment-friendly refrigerant.
  • the components are physically mixed in a liquid phase state according to their weight percentages to obtain the novel environment-friendly refrigerant.
  • the R152a refrigerant described in the present invention has excellent environmental protection performance, its flammability hinders its application in refrigeration systems. Although its flammability is reduced by mixing it with non-flammable HFCs refrigerants, such mixed refrigerants The GWP value is higher than 150, which cannot meet the environmental protection requirements.
  • the cis-1-chloro-2,3,3,3-tetrafluoropropene (Z-R1244yd) described in the present invention has an ODP value of 0, GWP ⁇ 1, and is non-toxic and non-flammable, but its unit volume And the cooling capacity per unit mass is too small, it is difficult to replace high GWP refrigerants such as R134a.
  • trifluoroiodomethane has certain toxicity
  • HFC with flame retardancy has a higher GWP value, which has certain deficiencies.
  • Adding Z-R1224yd and E-R1233zd as flame retardants to flammable refrigerants can not only reduce their flammability, but also ensure GWP value ⁇ 150.
  • the novel environmentally friendly refrigerant of the present invention simultaneously contains cis-1-chloro-2,3,3,3-tetrafluoropropene (Z-R1224yd) and trans-1-chloro-3,3,3-trifluoropropene (E -R1233zd) is a new environmentally friendly refrigerant with an ODP value of 0 and a GWP value of ⁇ 150.
  • the novel environmentally friendly refrigerant of the present invention combines the advantages of each component by optimizing the formula, and through the synergistic effect of each component, the unfavorable factors are reduced to the greatest extent, and the present invention has a good effect, not only reducing the flammability of R152a, but also improving the The refrigerating performance of Z-R1224yd and E-R1233zd, the refrigerating effect and capability of the new environmentally friendly refrigerant of the present invention are equivalent to R134a, and can directly replace R134a.
  • the novel environmentally friendly refrigerant of the present invention has good compatibility with lubricants.
  • the lubricants include natural mineral oil, alcohol lubricants, ester lubricants, benzene derivative lubricants, and polyolefin lubricants. Oil or polyolefin lubricating oil.
  • the raw materials in the present invention are all commercially available.
  • the present invention has the following advantages:
  • the ODP value of the new refrigerant of the present invention is 0, the GWP value is less than 150, and the environmental performance is better than that of the R134a refrigerant.
  • R152a in the novel refrigerant of the present invention is high, and the cost is far lower than that of the fourth-generation refrigerant represented by R1234yf, which reduces the cost of replacing R134a.
  • the novel refrigerant of the present invention has good flame retardancy due to the existence of Z-R1224yd and E-R1233zd, which improves its safety performance.
  • the refrigerating capacity per unit volume of the novel refrigerant of the present invention is basically equal to that of R134a, and the COP value and refrigerating capacity per unit mass are higher than those of R134a, which can greatly reduce the amount of refrigerant in the refrigeration system and save energy.
  • the mixed refrigerant of the present invention is relatively close to the working conditions of the R134a refrigerant, and can directly replace the R134a.
  • the novel refrigerant of the present invention has good compatibility with lubricating oil, and has good cycle performance and higher stability.
  • the lubricants tested were mineral oil, silicone oil, polyalkylbenzene (PAB), polyalkylene glycol (PAG), polyol ester (POE) and polyvinyl ether (PVE). During the test, two kinds of lubricants were selected and mixed with each 50% by weight, and then mixed with the test substance.
  • test substance/lubricant composition is as follows:
  • the refrigerant composition of the present invention has higher stability when in contact with the lubricant in the compressor refrigeration system.
  • the ODP value of the refrigerant prepared in the embodiment of the present invention is 0, and the GWP value is less than 150, which is far less than the GWP value of R134a.
  • the mixed refrigerant changes from weakly flammable (A2L) to non-flammable (A1). This shows that the addition of HCFO refrigerant greatly improves the combustion characteristics of R152a refrigerant and improves its safety performance.
  • the COP value of each example is higher than that of R134a.
  • the suction pressure and condensing pressure of Examples 1-5 are basically equivalent to R134a, and R134a can be directly replaced.
  • the refrigerating capacity per unit volume of Example 1-5 is slightly lower than that of R134a, and its suction pressure can be appropriately increased to further narrow the gap, and its refrigerating capacity per unit mass is nearly twice that of R134a, which can greatly reduce the charging of the new type of mixed refrigerant. quantity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Lubricants (AREA)

Abstract

本发明公开了一种新型环保制冷剂，按重量份数，其组成为：1,1-二氟乙烷1～98份，顺式1-氯-2,3,3,3-四氟丙烯1～98份，反式-1-氯-3,3,3-三氟丙烯1～98份。本发明还公开了该新型环保制冷剂的制备方法。本发明的新型环保制冷剂具有GWP低、安全性高、制冷效果和润滑剂相容性好的优点。

Description

一种新型环保制冷剂及其制备方法 技术领域
本发明属于制冷技术领域，具体涉及一种新型环保制冷剂及其制备方法。
背景技术
随着臭氧层消耗和温室效应环境问题越来越突出，国际社会制定了淘汰氟氯烃(CFC)、含氢氯氟烃(HCFC)的《蒙特利尔议定书》和限制温室气体的《京都议定书》。2016年10月，《蒙特利尔议定书》第28次缔约方会议达成了限控温室气体的氢氟烃(HFC)的基加利修正案，确定了削减具有较高GWP值的氢氟烃(HFC)的时间，将HFC的淘汰也提上了日程。欧盟境内对高GWP值的制冷剂提出了较为严格的限制，其中规定2017年1月1日起，在欧盟境内生产的新车，禁止使用GWP值大于150的制冷剂；2015年1月1日以后，充罐HFC制冷剂且其GWP≥150的家用冰箱和冷冻箱禁止在欧盟市场销售。
1,1,1,2-四氟乙烷(R134a)具有无毒、不然、无腐蚀、ODP值为0，具有良好的安全和制冷性能，用于替代传统的R22制冷剂，主要应用于汽车空调、热泵、冷水机组、冰箱冷柜等制冷领域。但是R134a制冷剂GWP值高达1430，温室效应较强，属于《京都议定书》控制的温室气体之一。为了避免氢氟烃给环境带来的温室效应，美国Honeywell和Dupont公司联合开发了一种含氟烯烃(HFO)—2,3,3,3-四氟丙烯(R1234yf)，用于替代R134a等高GWP值制冷剂。R1234yf制冷剂无毒，ODP值为0，GWP值＜4，是一种新型环保制冷剂，但是其价格昂贵，制冷效果不佳，生产工艺复杂，而且具有一定的弱可燃性，增加了制冷设备厂商的生产成本和使用安全性能。
专利文献CN107400502A公开了一种二氟甲烷、丙烯、三氟碘甲烷三元混合制冷剂用于替代R134a，优化后的混合制冷剂相对R134a最高可节能12％左右，但是三氟碘甲烷具有一定的毒性，同时混合制冷剂仍存在一定的可燃风险。
专利文献CN101851490A公开了一种含有2,3,3,3-四氟丙烯(R1234yf)、E-1,3,3,3-四氟丙烯(E-R1234ze)和1,1-二氟乙烷(R152a)的混合制冷剂，该混合制冷剂GWP<100，COP值(能效比)与R134a接近，但是该混合制冷剂具有一定的可燃性，而且其中含 氟烯烃含量较高，这就导致了替代成本较高。
专利文献CN110628389A公开了一种三元混合制冷剂用于替代R134a，第一组分为阻燃剂三氟碘甲烷，第二组分为三氟甲基甲基醚，第三组分为2,3,3,3-四氟丙烯(R1234yf)、3,3,3-三氟丙烯(R1243zf)、E-1,3,3,3-四氟丙烯(E-R1234ze)、1,1-二氟乙烷(R152a)、1,1,1,2-四氟乙烷(R134a)、1,1,1,2,3,3,3-七氟丙烷(R227ea)中的一种，该混合制冷剂不可燃，优选制冷剂GWP小于100，但是所有混合制冷剂COP值均小于R134a。
发明内容
本发明的目的是针对现有技术的不足，提供一种GWP低、安全性高、制冷效果好、润滑剂相容性好的一种新型环保制冷剂及其制备方法。
为了实现上述目的，本发明采用的技术方案为：一种新型环保制冷剂，按重量份数，由以下物质组成：
1,1-二氟乙烷                 1～98份
顺式1-氯-2,3,3,3-四氟丙烯    1～98份
反式-1-氯-3,3,3-三氟丙烯     1～98份
优选的，按重量份数，由以下物质组成：
1,1-二氟乙烷                 35～98份
顺式1-氯-2,3,3,3-四氟丙烯    1～32份
反式-1-氯-3,3,3-三氟丙烯     1～33份
更优选的，按重量份数，由以下物质组成：
1,1-二氟乙烷                 85～92份
顺式1-氯-2,3,3,3-四氟丙烯    1～14份
反式-1-氯-3,3,3-三氟丙烯     1～14份
最优选的，按重量份数，由以下物质组成：
1,1-二氟乙烷                 88～92份
顺式1-氯-2,3,3,3-四氟丙烯    4～7份
反式-1-氯-3,3,3-三氟丙烯     3～7份
优选的，所述的新型环保制冷剂全球变暖潜能值小于等于150。
进一步优选的，所述的新型环保制冷剂全球变暖潜能值小于等于120。
更优选的，所述的新型环保制冷剂全球变暖潜能值小于等于50。
最优选的，所述的新型环保制冷剂全球变暖潜能值小于等于5。
本发明还公开了该新型环保制冷剂的制备方法，将所述组分按其重量百分比在液相状态下进行物理混合，得到所述的新型环保制冷剂。
本发明所述的R152a制冷剂虽然环保性能优越，但是可燃性阻碍了其在制冷系统的应用，虽然通过将其与不可燃的HFCs制冷剂混合降低了它们的可燃性，但是这类混合制冷剂GWP值高于150，不能满足环保要求。
本发明所述的顺式-1-氯-2,3,3,3-四氟丙烯(Z-R1244yd)ODP值为0，GWP<1，具有无毒、不可燃特性，但是其单位容积量和单位质量制冷量偏小，难以替代R134a等高GWP值制冷剂。
本发明所述的反式-1-氯-3,3,3-三氟丙烯(E-R1233zd)是一种新型发泡剂和制冷剂，ODP值为0，GWP＝1，具有无毒、不可燃特性，但作为制冷剂制冷效果稍差。
在常用的阻燃剂中，三氟碘甲烷具有一定的毒性，具有阻燃性的HFC的GWP值较高，均有一定的不足。将Z-R1224yd和E-R1233zd作为阻燃剂添加到可燃制冷剂中，不仅可以降低其可燃性，还能保证GWP值<150。
本发明的新型环保制冷剂同时含有顺式1-氯-2,3,3,3-四氟丙烯(Z-R1224yd)和反式-1-氯-3,3,3-三氟丙烯(E-R1233zd)的新型环保制冷剂，其ODP值为0，GWP值<150。本发明的新型环保制冷剂通过优化配方，结合了各组分的优势，通过各组分协同作用，最大程度减少了不利因素，具有很好的效果，不仅降低了R152a的可燃性，还提高了Z-R1224yd和E-R1233zd的制冷性能，本发明的新型环保制冷剂制冷效果和能力与R134a相当，可直接替换R134a。
本发明的新型环保制冷剂与润滑剂相容性较好，可选地，所述润滑剂包括天然矿物油、醇类润滑油、酯类润滑油、苯的衍生物润滑油、聚烯烃类润滑油或聚烯醚类润滑油。
本发明中的原料均可市售取得。
与现有技术相比，本发明具有以下优点：
1、本发明的新型制冷剂ODP值为0，GWP值<150，环境性能优于R134a制冷剂。
2、本发明的新型制冷剂中廉价的R152a含量高，成本远低于以R1234yf为代表的 第四代制冷剂，降低了替代R134a的成本。
3、本发明的新型制冷剂由于Z-R1224yd和E-R1233zd的存在具有良好阻燃性，提高了其安全性能。
4、本发明的新型制冷剂其单位容积制冷量与R134a基本相当，COP值和单位质量制冷量高于R134a，可以大大降低制冷系统中制冷剂的充罐量并节约能耗。
5、在制冷剂替代过程中，蒸发/冷凝压力接近会大大减少替代的设备成本，本发明的混合制冷剂与R134a制冷剂工作条件比较接近，可直接替换R134a。
6、本发明的新型制冷剂与润滑油相容性好，具有良好的循环性能和更高的稳定性。
具体实施方式
以下结合具体实施例对本发明进行进一步的说明，但本发明并不局限于所述的实施例。
实施例1-5
将1,1-二氟乙烷(R152a)，顺式1-氯-2,3,3,3-四氟丙烯(Z-R1224yd)，反式-1-氯-3,3,3-三氟丙烯(E-R1233zd)在液相状态下进行物理混合，得到制冷剂组合物。具体组成见表1。
表1实施例1-5所得制冷剂组合物的组成
实施例 R152a(kg) Z-R1224yd(kg) E-R1233zd(kg)
实施例1 92 4 4
实施例2 90 7 3
实施例3 88 5 7
实施例4 85 14 1
实施例5 85 1 14
性能测试：
(1)通过基团贡献法计算各实施例的绝对燃烧速度，并根据GB/T7778-2017确定各混合制冷剂的安全分类。结果见表2。
表2实施例1-5所得制冷剂组合物的环境性能和安全性能
编号 ODP GWP 安全分类 摩尔质量
        (g/mol)
R134a 0 1430 A1 102.03
实施例1 0 114 A2L 68.94
实施例2 0 112 A2L 69.62
实施例3 0 109 A1 70.53
实施例4 0 106 A1 72.00
实施例5 0 106 A1 71.38
(2)根据GB/T 10079-2018规定的制冷工况下(吸气饱和温度7℃，排气饱和温度54.5℃，吸气温度18.5℃，过冷度8.5℃)，将上述各实施例与R134a的环境参数、物性参数、热工性能参数进行了对比，结果见表3。
表3实施例1-5所得制冷剂组合物的制冷性能
Figure PCTCN2021106751-appb-000001
(3)可混溶性测试
所测试的润滑剂为矿物油、硅油、多烷基苯(PAB)、聚亚烷基二醇(PAG)、多元醇酯(POE)和聚乙烯基醚(PVE)。测试时，选用两种润滑剂按各50％重量百分比混合后，再与测试物质混合。
采用小型压缩机，加入测试物质/润滑剂组合物，在40℃下，测试测试物质/润滑剂组合物与制冷系统中所使用的金属接触时，与润滑剂的相容性。判定测试物质/润滑剂在整个温度范围内以所有测试比例都可混溶。测试物质/润滑剂组合物如下：
(a)Z-R1224yd和矿物油/硅油
(b)E-R1233zd和PAG/硅油
(c)实施例1的制冷剂组合物和PAB/硅油
(d)实施例2的制冷剂组合物和PAG/POE
(e)实施例3的制冷剂组合物和矿物油/硅油
(f)实施例4的制冷剂组合物和硅油/PAB
(g)实施例5的制冷剂组合物和PVE/硅油
在试验过程中发现，本发明的制冷剂组合物与压缩机制冷系统中的润滑剂接触时，具有更高的稳定性。
由表2、表3可知，本发明实施例所制备的制冷剂ODP值为0，GWP值小于150，远远小于R134a的GWP值。当Z-R1224yd和E-R1233zd总含量高于12％时，混合制冷剂由弱可燃(A2L)变为不可燃(A1)。这说明HCFO制冷剂的添加极大地改善了R152a制冷剂的燃烧特性，提高了其安全性能。
各实施例的COP值均高于R134a。实施例1-5的吸气压力和冷凝压力与R134a基本相当，可直接替换R134a。实施例1-5单位容积制冷量比R134a略低，可以适当增加其吸气压力进一步缩小其差距，且其单位质量制冷量是R134a的将近2倍，可以大大降低新型保混合制冷剂的充注量。综合上述结果，当R152a含量不低于85％时，其整体环境、制冷性能优于R134a，可直接替代R134a制冷系统。

Claims (9)

  1. 一种新型环保制冷剂，其特征在于，按重量份数，由以下物质组成：
    1,1-二氟乙烷                 1～98份
    顺式1-氯-2,3,3,3-四氟丙烯    1～98份
    反式-1-氯-3,3,3-三氟丙烯     1～98份。
  2. 根据权利要求1所述的新型环保制冷剂，其特征在于，按重量份数，由以下物质组成：
    1,1-二氟乙烷                 35～98份
    顺式1-氯-2,3,3,3-四氟丙烯    1～32份
    反式-1-氯-3,3,3-三氟丙烯     1～33份。
  3. 根据权利要求1所述的新型环保制冷剂，其特征在于，按重量份数，由以下物质组成：
    1,1-二氟乙烷                 85～92份
    顺式1-氯-2,3,3,3-四氟丙烯    1～14份
    反式-1-氯-3,3,3-三氟丙烯     1～14份。
  4. 根据权利要求1所述的新型环保制冷剂，其特征在于，按重量份数，由以下物质组成：
    1,1-二氟乙烷                 88～92份
    顺式1-氯-2,3,3,3-四氟丙烯    4～7份
    反式-1-氯-3,3,3-三氟丙烯     3～7份。
  5. 根据权利要求1所述的新型环保制冷剂，其特征在于，所述的新型环保制冷剂全球变暖潜能值小于等于150。
  6. 根据权利要求1所述的新型环保制冷剂，其特征在于，所述的新型环保制冷剂全球变暖潜能值小于等于120。
  7. 根据权利要求1所述的新型环保制冷剂，其特征在于，所述的新型环保制冷剂全球变暖潜能值小于等于50。
  8. 根据权利要求1所述的新型环保制冷剂，其特征在于，所述的新型环保制冷剂全球变暖潜能值小于等于5。
  9. 权利要求1所述的新型环保制冷剂的制备方法，其特征在于，将所述组分按其重量百分比在液相状态下进行物理混合，得到所述的新型环保制冷剂。
PCT/CN2021/106751 2020-11-23 2021-07-16 一种新型环保制冷剂及其制备方法 WO2022105274A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011319675.4A CN112552875B (zh) 2020-11-23 2020-11-23 一种新型环保制冷剂及其制备方法
CN202011319675.4 2020-11-23

Publications (1)

Publication Number Publication Date
WO2022105274A1 true WO2022105274A1 (zh) 2022-05-27

Family

ID=75044769

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/106751 WO2022105274A1 (zh) 2020-11-23 2021-07-16 一种新型环保制冷剂及其制备方法

Country Status (2)

Country Link
CN (1) CN112552875B (zh)
WO (1) WO2022105274A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112552875B (zh) * 2020-11-23 2022-03-08 浙江衢化氟化学有限公司 一种新型环保制冷剂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103534328A (zh) * 2011-05-19 2014-01-22 旭硝子株式会社 工作介质及热循环系统
CN108779048A (zh) * 2016-02-25 2018-11-09 Ａｇｃ株式会社 1-氯-2,3,3,3-四氟丙烯的制造方法
CN111183200A (zh) * 2017-08-18 2020-05-19 科慕埃弗西有限公司 Z-1-氯-2，3，3，3-四氟丙-1-烯的组合物和用途
CN112552875A (zh) * 2020-11-23 2021-03-26 浙江衢化氟化学有限公司 一种新型环保制冷剂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103534328A (zh) * 2011-05-19 2014-01-22 旭硝子株式会社 工作介质及热循环系统
CN108779048A (zh) * 2016-02-25 2018-11-09 Ａｇｃ株式会社 1-氯-2,3,3,3-四氟丙烯的制造方法
CN111183200A (zh) * 2017-08-18 2020-05-19 科慕埃弗西有限公司 Z-1-氯-2，3，3，3-四氟丙-1-烯的组合物和用途
CN112552875A (zh) * 2020-11-23 2021-03-26 浙江衢化氟化学有限公司 一种新型环保制冷剂及其制备方法

Also Published As

Publication number Publication date
CN112552875B (zh) 2022-03-08
CN112552875A (zh) 2021-03-26

Similar Documents

Publication Publication Date Title
CA2798620C (en) Compositions and methods for refrigeration
AU2019427789B2 (en) Composition containing refrigerant, and refrigeration method using said composition, operating method for refrigeration device, and refrigeration device
CN110699043B (zh) 一种环保混合制冷工质
JP2019214720A (ja) 冷媒を含有する組成物、熱移動媒体及び熱サイクルシステム
WO1994000529A1 (en) Refrigerant blends containing 1,1,1,2,3,3,3-heptafluoropropane
CN110878195B (zh) 一种含三氟碘甲烷的冷媒和含有其的混合物和换热系统
CN110878196B (zh) 一种四元混合环保制冷剂及组合物
CN110843457B (zh) 一种采用环保制冷剂的汽车空调热泵系统
JP2016539209A (ja) 冷媒
EP3825381B1 (en) Use of a refrigerant-containing composition
WO2022105274A1 (zh) 一种新型环保制冷剂及其制备方法
CN102241962A (zh) 一种低gwp值的组合物
WO2021062963A1 (zh) 一种氟代烯烃和氟代烷烃的组合物
JP6211068B2 (ja) 冷媒ガス組成物
CN106543963B (zh) 一种环保型制冷组合物
CN110655909B (zh) 一种适用于汽车空调的环保混合冷媒
WO2022017109A1 (zh) 一种含有氟代烃的组合物及其制备方法
EP3722390B1 (en) Composition containing refrigerant including r32, r125, r143a, and r134a and refrigeration method using said composition, method for operating refrigerator, and refrigerator
CN113025279B (zh) 一种含有氟代烯烃的组合物及其制备方法
WO2019228094A1 (zh) 一种中高温热泵混合工质
CN113046029B (zh) 一种含有氟代烯烃的组合物及其制备方法
CN113528090B (zh) 一种可替代r410a的环保型制冷组合物
CN118126680A (zh) 一种传热组合物及其制备方法
WO2009155822A1 (zh) 一种热泵系统用的混合工质

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: 21893426

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21893426

Country of ref document: EP

Kind code of ref document: A1