CN1200067C - 一种节能环保混合制冷剂 - Google Patents

一种节能环保混合制冷剂 Download PDF

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CN1200067C
CN1200067C CNB031485324A CN03148532A CN1200067C CN 1200067 C CN1200067 C CN 1200067C CN B031485324 A CNB031485324 A CN B031485324A CN 03148532 A CN03148532 A CN 03148532A CN 1200067 C CN1200067 C CN 1200067C
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顾雏军
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50Solvents
    • C11D7/5004Organic solvents
    • C11D7/5018Halogenated solvents
    • 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
    • C09K3/00Materials not provided for elsewhere
    • C09K3/30Materials not provided for elsewhere for aerosols
    • 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
    • C09K2205/12Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/24Hydrocarbons
    • C11D7/241Hydrocarbons linear
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/28Organic compounds containing halogen
    • YGENERAL 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
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    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
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  • Organic Chemistry (AREA)
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Abstract

本发明涉及了一种节能、环保型混合制冷剂,由CH2F2(R32)、CHF2CF3(R125)、CH2FCF3(R134a)和/或CHF2CHF2(R134)、CH3CH=CH2(R1270)组成。该混合制冷剂不破坏臭氧层,温室效应系数较低,有极好的环境可接受性及优越的热物理、化学性质,可以作为制冷剂替代R22和R502等广泛应用于空调、热泵和制冷装置,在空调及热泵装置中使用可节能30-45%;在制冷装置中使用,可节能25-45%;同时该混合物也可作为热传递介质、喷雾式推进剂、发泡膨胀剂、电绝缘介质、动力循环工作介质、清洗液、溶剂等。

Description

一种节能环保混合制冷剂
技术领域
本发明主要涉及供热、制冷、热工动力等工程技术领域,特别是涉及一种适合于空调、热泵及制冷装置的节能环保型多元混合制冷剂。
背景技术
众所周知,空调、冷冻机、冰箱等传统制冷、热泵装置中,通常采用从烷烃系列衍生物中得到的卤代烃作为制冷剂,现有技术中,一氯二氟甲烷(CHClF2,R22,沸点-40.8℃)和R502(由R22和R115组成的共沸混合物)已广泛用作如空调,冷冻机、冰箱之类制冷装置中的制冷剂;同时卤代烃还大量应用于消防、清洗、生产泡沫聚合物等领域。
但是,近年来由于含氯氟烃而引起同温层中臭氧层破坏日益严重并成为全球性的环境问题,《保护臭氧层维也纳公约》和《关于消耗臭氧层物质的蒙特利尔议定书》等国际公约及《中国逐步淘汰消耗臭氧层物质国家方案》已对这种严重威胁臭氧层的含氯氟烃的使用和生产量进行限制,并制定了进行淘汰的严格时间表,将在今后完全禁止使用和生产,转而采用不含氯的碳氢化合物、氟代烃类等。所以世界各国广大科技工作者,特别是从事制冷工程技术开发研究的工程技术人员投入大量人力和物力,寻找其性能较好且对大气臭氧层无破坏作用的新型制冷剂,并要求能适用于制冷设备及零部件。经多年的开发研究,虽已找到一些制冷剂物质,例如不含氯的氟代烃包括二氟甲烷(CH2F2,R32,沸点-52℃),五氟乙烷(CF3CHF2,R125,沸点-48℃),1,1,1,2-四氟乙烷(CF3CH2F,R134a,沸点-27℃),1,1,2,2-四氟乙烷(CHF2CHF2,R134,沸点-23℃),丙烯(CH3CH=CH2,沸点-25℃)等,然而在不含氯的氟化烃中,包括R32、R125、R134a、R1270等在内的单组分制冷剂有着其自身不可克服的缺点,如碳氢化合物、R32、143a具可燃性;R32、R125的沸点比R22低,从而使热泵装置中的冷凝压力变得很高;R134a沸点比R22高并使热泵装置的冷凝压力降低,制冷能力低,因此难以单一地作为R22的替代物。
而多元混合制冷剂最近在全世界都引起广泛的研究兴趣,它通过对几种优选的单组分制冷剂以合理的配比进行混合,可具有优良的热工性能和化学性能,克服或减弱其中某一单组分制冷剂所具有的缺点,多元混合制冷剂已被很多研究单位认为是代替制冷剂R22、R502等的极具发展潜力的新型制冷剂。如美国专利4,978,467申请的二元混合制冷剂R32/R125可能是具有实用价值的混合制冷剂,但是现有混合制冷剂仅适合一定应用范围,局限性较大,因为制冷剂都有它自身固定特点及适用范围,对不同蒸发温度区、冷凝温度区域没有一种混合制冷剂都同时可以适用,而且现有文献中所介绍的制冷剂在制冷、热泵和空调设备中,节能效果有限,一般为5-10%;另外,使用现有制冷剂往往要求对原制冷剂、热泵及空调设备作较多的改造,方能适用,这将给实际应用和推广带来诸多困难。
发明内容
发明人经过长期从事开发研究、生产实践开发了一系列作为环保节能型多元混合制冷剂可替代R22和R502的混合物,取得一定效果;同时,在研究开发过程中,发明人发现在特定组成成份及组成比例的多元混合制冷剂具有显著节能效果,比传统的制冷剂和现有的混合制冷剂高出10%,甚至高达15%,使在热泵和空调装置中可节能30-45%,在制冷装置中可节能25-45%,而且对制冷设备等无需较大改型,仅需变动少量部件即可。
本发明的目的在于克服现有技术不足,提供一种沸点等热工参数适宜、无毒、节能效果显著,对大气的臭氧层无破坏、温室效应系数低的多元混合物,该混合物可作为环保节能型多元混合制冷剂应用,同时也可作为热传递介质、喷雾式推进剂、发泡膨胀剂、电绝缘介质、动力循环工作介质、清洗液、溶剂等。
本发明提供的一种多元混合制冷剂,其中CH2F2(R32)为5-60%(质量百分比),CHF2CF3(R125)为3-70%(质量百分比),CH2FCF3(R134a)和/或CHF2CHF2(R134)为1-70%(质量百分比),CH3CH=CH2(R1270)为1-10%(质量百分比)。
本发明提供的一种多元混合制冷剂,其中CH2F2(R32)为20-40%(质量百分比),CHF2CF3(R125)为35-55%(质量百分比),CH2FCF3(R134a)和/或CHF2CHF2(R134)为5-30%(质量百分比),CH3CH=CH2(R1270)为1-3%(质量百分比)组成。
所述CH2FCF3(R134a)和CHF2CHF2(R134)可以单独使用或任意比例混合使用。
由于CH3CH=CH2(R1270)与润滑油良好的相溶性,该混合制冷与润滑油的相溶性有了明显的改善,同时通过优选的组分比例,使该混合制冷剂在实际应用的制冷、空调、热泵装置中可均匀稳定的存在和循环。
如前文所述,R32、R125、R134、R134a、R1270的臭氧消耗潜能值ODP都为0,不会破坏大气臭氧层。
本发明提供的混合制冷剂用于热泵及空调装置能提高装置性能系数30-45%,节能30-45%;用于制冷装置中能提高装置的性能系数25-45%,节能25-45%。
空调及制冷装置性能系数的定义为空调及制冷装置单位功率消耗所产生的制冷量。热泵装置性能系数的定义为该装置单位功率消耗所产生的供热量。杂质定义为在这种混合物中,除R32、R125、R134、R134a、R1270之外,混合物里所混入的任何别种物质。
根据多种目的和要求,只要对本发明所公开混合物的基本性质无明显不利影响,可以将抗蚀剂、稳定剂、指示剂、荧光检漏剂等其它物质添加到本发明所公开的混合物中,改变该混合物某些特性。
因此,本发明提供的混合制冷剂是一种优异的环保节能型制冷剂。由此可见,本发明提供的节能环保型混合制冷剂对大气臭氧层没有破坏作用,节能效果显著,温室效应系数较低;同时它有着优越的热物理、化学性质和润滑性能;在贮存容器或空调应用装置中可均匀稳定存在,可广泛使用于制冷、热泵及空调装置中,而且在实际应用于制冷、热泵及空调装置时需改动的设备部件较少。
本发明提供的混合制冷剂可通过本领域技术人员根据各组分在某一环境温度下的不同饱和压力,按照从低到高的顺序,利用密闭系统和计量设备直接灌装即可。
具体实施方案
本发明用下列实施例来进一步说明本发明,这将有助于本发明及其优点的理解,但本发明保护范围并不限于实施例,本发明的保护范围由权利要求书来限定。
实施例1
将按质量百分比40%的CH2F2(R32),50%的CHF2CF3(R125),8%的CH2FCF3(R134a)和/或CHF2CHF2(R134),2%的CH3CH=CH2(R1270)组成多元混合制冷剂,该混合制冷剂的0DP值为0,对臭氧层无破坏作用,温室效应系数较低;用于热泵及空调装置能提高装置的性能系数39%,节能42%,用于制冷装置能提高装置的性能系数37%,节能40%。
实施例2
将按质量百分比30%的CH2F2(R32),40%的CHF2CF3(R125),28%的CH2FCF3(R134a)和/或CHF2CHF2(R134),2%的CH3CH=CH2(R1270)组成多元混合制冷剂,该混合制冷剂的ODP值为0,对臭氧层无破坏作用,温室效应系数较低;用于热泵及空调装置能提高装置的性能系数37%,节能40%,用于制冷装置能提高装置的性能系数37%,节能39%。

Claims (5)

1、一种节能环保型制冷剂,由CH2F2为5-60%(质量百分比),CHF2CF3为3-70%(质量百分比),CH2FCF3和/或CHF2CHF2为1-70%(质量百分比),CH3CH=CH2为1-10%(质量百分比)组成。
2、根据权利要求1的节能环保型制冷剂,由CH2F2为20-40%(质量百分比),CHF2CF3为35-55%(质量百分比),CH2FCF3和/或CHF2CHF2为5-30%(质量百分比),CH3CH=CH2为1-3%(质量百分比)组成。
3、根据权利要求1的节能环保型制冷剂,由CH2F2为30%(质量百分比),CHF2CF3为40%(质量百分比),CH2FCF3和/或CHF2CHF2为28%(质量百分比),CH3CH=CH2为2%(质量百分比)组成。
4、根据权利要求1或2或3的制冷剂,用于热传递介质、喷雾式推进剂、发泡膨胀剂、电绝缘介质、动力循环工作介质、清洗液、溶剂的用途。
5、根据权利要求1或2或3的制冷剂,可以将抗蚀剂、稳定剂、指示剂、荧光检漏剂添加其中,改变该混合物的某些特性。
CNB031485324A 2003-07-02 2003-07-02 一种节能环保混合制冷剂 Expired - Fee Related CN1200067C (zh)

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GB0622562D0 (en) * 2006-11-11 2006-12-20 Rpl Holdings Ltd Non ozone depleting refrigerant composition for replacing hcfc 22
FR2903700B1 (fr) * 2007-09-27 2012-03-16 Arkema France Compositions a base d'hydrocarbures.
JP6841066B2 (ja) * 2017-02-03 2021-03-10 ダイキン工業株式会社 フッ素化炭化水素の混合物を冷媒として使用する方法、及び当該混合物を冷媒として使用した冷凍装置
CN114276784B (zh) * 2021-12-22 2024-06-25 江苏华复保利环保科技有限公司 一种车用三元混合制冷剂及其制备方法和制冷设备

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CN107987795A (zh) * 2017-11-15 2018-05-04 绵阳双甘科技有限公司 一种节能环保混合制冷剂

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