JPH07502774A - Compositions useful as refrigerants - Google Patents
Compositions useful as refrigerantsInfo
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- JPH07502774A JPH07502774A JP5512216A JP51221693A JPH07502774A JP H07502774 A JPH07502774 A JP H07502774A JP 5512216 A JP5512216 A JP 5512216A JP 51221693 A JP51221693 A JP 51221693A JP H07502774 A JPH07502774 A JP H07502774A
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- Prior art keywords
- refrigerant composition
- weight
- refrigerant
- tetrafluoroethane
- ether
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Classifications
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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
- 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
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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
-
- 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
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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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 冷媒として有用な組成物 本発明は一般的には冷却及び加熱用途用の冷媒（ｒｅｆｒｉｇｅｒａｎｔ）組成 物、並びに熱伝達装置におけるかかる組成物の使用に関する。さらに詳しくは、 本発明はジクロロジフルオロメタンし冷媒（Ｒｅｆｒｉｇｅｒａｎｔ） Ｒ−１ ２１を代替することを意図する冷媒組成物に関する。[Detailed description of the invention] Compositions useful as refrigerants The invention generally relates to refrigerant compositions for cooling and heating applications. and the use of such compositions in heat transfer devices. For more details, The present invention uses dichlorodifluoromethane as a refrigerant R-1. The present invention relates to a refrigerant composition intended to replace No. 21.
機械的冷却、冷凍設備（ｓｙｓｔｅｍ）及び関連する熱伝達装置例えば熱ポンプ 並びに空気調和装置は周知である。かかる装置においては、適当な沸点をもつ冷 媒液（ｒｅｆｒｉｇｅｒａｎｔ １ｉｑｕｉｄ）は低圧において周囲の帯域から 熱を奪いながら蒸発する。次いで、生成した蒸気は圧縮され、凝縮器に通され、 該凝縮器において上記蒸気が凝縮し、第二の帯域に対して熱を放出する。生成し た凝縮液は膨張弁を通して蒸発器に戻され、そこで冷却、冷凍サイクルが完結す る。前記蒸気を圧縮し且つ前記冷媒液をポンプで送液するのに必要とされる機械 的エネルギーは、電動機（モーター）又は内燃機関によって提供し得る。Mechanical cooling, refrigeration systems and associated heat transfer devices such as heat pumps Air conditioners are also well known. In such equipment, cooling with an appropriate boiling point is required. The refrigerant liquid is removed from the surrounding zone at low pressure. Evaporates while taking away heat. The produced vapor is then compressed and passed through a condenser, In the condenser the vapor condenses and releases heat to the second zone. generate The condensate is returned to the evaporator through the expansion valve, where the cooling and refrigeration cycle is completed. Ru. the machinery required to compress the vapor and pump the refrigerant liquid; The energy can be provided by an electric motor or an internal combustion engine.
冷媒の好ましい諸特性としては、適当な沸点及び高い気化潜熱を有することに加 えて、低毒性、非引火性、非腐食性、高安定性及び不快臭がないことが挙げられ る。Preferred properties of the refrigerant include having a suitable boiling point and high latent heat of vaporization. In addition, it has low toxicity, non-flammability, non-corrosion, high stability and no unpleasant odor. Ru.
これまでに、熱伝達装置は完全に及び部分的にハロゲン化されたクロロフルオロ カーボン冷媒を使用する傾向にある。諸特性の適当な組み合わせをもちしかも長 年の間、最も広範に使用されている冷媒であるシクロロンフルオロメタン（冷媒 Ｒ−１２）を特に挙げ得る。To date, heat transfer devices have been developed using fully and partially halogenated chlorofluorocarbons. There is a tendency to use carbon refrigerants. It has an appropriate combination of characteristics and is long. For years, the most widely used refrigerant, cyclolonfluoromethane (refrigerant R-12) may be mentioned in particular.
しかしながら、近年、完全に及び部分的にハロゲン化されたクロロフルオロカー ボン類が地球を保護するオゾン層に損傷を与え得るという国際的な関心事が大き くなってきており、またこれらクロロフルオロカーボン類の製造と使用を厳しく 制限し、しかも最終的には段階的に完全に廃止すべきであるという一般的な合意 がある。However, in recent years fully and partially halogenated chlorofluorocarbons There is great international concern that carbon dioxide can damage the earth's protective ozone layer. The production and use of these chlorofluorocarbons is becoming increasingly strict. general agreement that it should be restricted and eventually phased out completely There is.
本発明か関連する型の熱伝達装置は本質的に密閉系であるが、該装置の運転中又 は保守操作中の漏れにより、大気に対して冷媒の損失（ｌｏｓｓ）を生じ得る。Although heat transfer devices of the present or related type are essentially closed systems, during operation of the device or can result in losses of refrigerant to the atmosphere due to leaks during maintenance operations.
従って、完全に及び部分的にハロゲン化されたクロロフルオロカーボン冷媒を、 オゾンを減少させる（ｏｚｏｎｅｄｅｐｌｅｔｉｏｎ）可能性が実質的により少 ない物質好ましくは皆無である物質で代替えすることが重要である。Therefore, fully and partially halogenated chlorofluorocarbon refrigerants, Substantially less potential for ozone depletion It is important to replace the substances with substances that do not exist, preferably with substances that do not exist at all.
大気中のクロロフルオロカーホン冷媒の有意な（ｓｉｇｎｉｆｉｃａｎｔ）濃度 は、オゾンを減少させる可能性のほかに、地球温暖化（いわゆる温室効果）の− 因となるであろう。従って、別の大気成分例えばヒドロキシルラジカルと反応す ることができる結果として比較的短い大気中寿命をもつ冷媒を使用することが望 ましい。Significant concentrations of chlorofluorocarbon refrigerants in the atmosphere In addition to the possibility of reducing ozone, it also has the potential to reduce global warming (the so-called greenhouse effect). It will be the cause. Therefore, it is possible to react with other atmospheric components such as hydroxyl radicals. It is desirable to use refrigerants that have relatively short atmospheric lifetimes as a result of their ability to Delicious.
本発明によれば、冷媒Ｒ−１２の代替品として使用し得る冷媒組成物が提供され る。本発明の組成物は、冷媒化合物であって本質的にオゾンを減少させる可能性 が皆無でありしかも直接的な地球温暖化の可能性が比較的少ない冷媒化合物を含 有する。According to the present invention, a refrigerant composition that can be used as a substitute for refrigerant R-12 is provided. Ru. The compositions of the present invention are refrigerant compounds that inherently have ozone depletion potential. contain refrigerant compounds that have no direct global warming potential and have a relatively low potential for direct global warming. have
従って、本発明によれば１．１．１．２−テトラフルオロエタン（ＣＦ３Ｃ１１ ２Ｆ）と、トリフルオロメチルメチルエーテル（ＣＦ３０ＣＩ（、）及びフルオ ロメチルトリフルオロメチルエーテル（ＣＦ３０ＣＨ２Ｆ）から選択される弗素 化エーテルの少なくとも１種との混合物を含有してなる冷媒組成物が提供される 。According to the invention, therefore, 1.1.1.2-tetrafluoroethane (CF3C11 2F) and trifluoromethyl methyl ether (CF30CI(,) and fluoromethyl ether Fluorine selected from methyl trifluoromethyl ether (CF30CH2F) Provided is a refrigerant composition comprising a mixture with at least one chemical ether. .
本発明の冷媒組成物は、典型的には１．１．１．２−テトラフルオロエタン５〜 ９５重量％と、前記エーテル９５〜５重量％とを含有する。本発明の冷媒組成物 は、オゾンを減少させる可能性が少ないか好ましくは皆無である別の冷媒化合物 、例えば別のハイドロフルオロアルカン類及び／又は残存（ｒｅｓｉｄｕａｌ） 水素原子含有の別の弗素化エーテルを追加成分として含有し得る。本発明の冷媒 組成物に配合し得る別のハイドロフルオロアルカン類の例としては、ジフルオロ メタン（Ｒ−３２）、１．１．１− ）リフルオＯエタン（Ｒ−１４３ａ）、１ ．１．２．２−テトラフルオロエタン（Ｒ−１３４） 、ペンタフルオロエタン （Ｒ−１２５）及び１．１−ジフルオロエタン（Ｒ−ｘｓ２ａ）が挙げられる。The refrigerant composition of the present invention typically comprises 1.1.1.2-tetrafluoroethane 5- 95% by weight and 95-5% by weight of the ether. Refrigerant composition of the present invention is another refrigerant compound that has less or preferably no potential to deplete ozone. , such as another hydrofluoroalkane and/or residual Further fluorinated ethers containing hydrogen atoms may be included as additional components. Refrigerant of the present invention Examples of other hydrofluoroalkanes that may be included in the composition include difluoro Methane (R-32), 1.1.1-) Refluoro-Oethane (R-143a), 1 ．． 1.2.2-tetrafluoroethane (R-134), pentafluoroethane (R-125) and 1,1-difluoroethane (R-xs2a).
本発明の冷媒組成物に含有させ得る別の弗素化エーテル類の例は、残存水素原子 を有する弗素化ジメチルエーテルである。Another example of fluorinated ethers that can be contained in the refrigerant composition of the present invention is residual hydrogen atoms. It is a fluorinated dimethyl ether with
本発明の冷媒組成物は別の冷媒化合物を含有し得るが、本発明の好ましい冷媒組 成物は本質的に１．１．１．２−テトラフルオロエタンと、トリフルオロメチル メチルエーテル及びフルオロメチルトリフルオロメチルエーテルから選択される 弗素化エーテルの少なくとも１種とからなる。Although the refrigerant compositions of the present invention may contain other refrigerant compounds, preferred refrigerant compositions of the present invention The composition consists essentially of 1.1.1.2-tetrafluoroethane and trifluoromethyl. selected from methyl ether and fluoromethyl trifluoromethyl ether and at least one fluorinated ether.
本発明の冷媒組成物は共沸性（ａｚｅｏｔｒｏｐｉｃ）であり得るが、該組成物 は好ましくは共沸性又は共沸点混合物様のものである。Although the refrigerant compositions of the present invention can be azeotropic, the compositions is preferably azeotropic or azeotrope-like.
本発明の１つの態様においては、本発明の冷媒組成物は１．１．１．２−テトラ フルオロエタンとフルオロメチルトリフルオロメチルエーテルの混合物からなり 得る。この種の特定の組成物は、本質的に前記の成分からなるものである。かか る組成物は典型的には、１．１．１．２−テトラフルオロエタン２５〜７５重量 ％と、フルオロメチルトリフルオロメチルエーテル７５〜２５重量％とからなる 。必須成分として１．１．１゜２−テトラフルオロエタンとフルオロメチルトリ フルオロメチルエーテルとを含有してなる冷媒組成物は、多くの用途において冷 媒Ｒ−１２を適切に代替し得る。しかしながら、かかる組成物は特に熱ポンプ及 び自動車用空気調和装置においてＲ−１２の代替品として有用である。In one embodiment of the invention, the refrigerant composition of the invention comprises 1.1.1.2-tetra Consists of a mixture of fluoroethane and fluoromethyl trifluoromethyl ether obtain. Particular compositions of this type consist essentially of the components mentioned above. Kaka The composition typically contains 25-75% by weight of 1.1.1.2-tetrafluoroethane. % and 75-25% by weight of fluoromethyl trifluoromethyl ether. . 1.1.1゜2-tetrafluoroethane and fluoromethyl trifluoride as essential components. Refrigerant compositions containing fluoromethyl ether are used in many applications. Medium R-12 may be suitably substituted. However, such compositions are particularly useful for heat pumps and It is useful as a substitute for R-12 in air conditioners and automobile air conditioners.
熱ポンプ及び自動車用空気調和装置は、高い吐出し温度、典型的には約８０℃で 運転される。該温度は凝縮器においてかなり高い圧力をもたらす傾向にある。か かる装置における作動流体として１．１．１．２−テトラフルオロエタンとフル オロメチルトリフルオロメチルエーテルとの配合物を使用することにより、前記 の高い吐出し温度において、冷媒Ｒ−１２又は１．１．１．２−テトラフルオロ エタン（冷媒Ｒ−１２の一般的に容認された代替品）か使用される場合に可能で ある凝縮器圧力よりも低い凝縮器圧力を得ることが可能である。本発明者らの研 究により、１，１．１．２−テトラフルオロエタン７５重量％と、フルオロメチ ルトリフルオロメチルエーテル２５重量％とからなる冷媒組成物を使用すると８ ０℃の吐出し温度において約１７．７バールの凝縮器圧力が達成し得ることが示 される。Heat pumps and automotive air conditioners operate at high discharge temperatures, typically around 80°C. be driven. Such temperatures tend to result in fairly high pressures in the condenser. mosquito 1.1.1.2-tetrafluoroethane and fluorine as working fluids in such devices. By using a formulation with oromethyl trifluoromethyl ether, the At high discharge temperatures of refrigerant R-12 or 1.1.1.2-tetrafluoro Possible if ethane (a generally accepted alternative to refrigerant R-12) is used. It is possible to obtain a condenser pressure lower than a certain condenser pressure. The inventors' research Studies have shown that 75% by weight of 1,1.1.2-tetrafluoroethane and fluoromethyl When using a refrigerant composition consisting of 25% by weight of trifluoromethyl ether, 8 It has been shown that a condenser pressure of approximately 17.7 bar can be achieved at a discharge temperature of 0°C. be done.
第１表に、１． ］、、 １．２−テトラフルオロエタン（表中のＲ−１３４ａ ）と、フルオロメチルトリフルオロメチルエーテル（表中のＥ−１３４ａ）とか らなる本発明の多数の冷媒組成物の性能を示す。評価した冷媒組成物の各成分の 重量％を表の第２行目に示す。すなわち、１．１．１．２−テトラフルオロエタ ン７５重量％とフルオロメチルトリフルオロメチルエーテル２５重量％とからな る冷媒組成物、 １．１． ］、、 ］２テトラフルオロエタン２５重量量とフ ルオロメチルトリフルオロメチルエーテル５０重量％とからなる冷媒組成物；及 び１．１．１．２−テトラフルオロエタン２５重量％とフルオロメチルトリフル オロメチルエーテル７５重量％とからなる冷媒組成物のそれぞれを評価した。評 価のために選択した運転条件は、家庭用冷却、冷蔵装置において存在する運転条 件を代表する。具体的には、これらの条件は下記のとおりであった。Table 1 shows 1. ],, 1,2-tetrafluoroethane (R-134a in the table ) and fluoromethyl trifluoromethyl ether (E-134a in the table) 1 shows the performance of a number of refrigerant compositions of the present invention comprising: of each component of the refrigerant composition evaluated. The weight percentages are shown in the second line of the table. That is, 1.1.1.2-tetrafluoroethane and 25% by weight of fluoromethyl trifluoromethyl ether. Refrigerant composition, 1.1. ],,]2 Tetrafluoroethane 25 weight amount and fluoroethane A refrigerant composition comprising 50% by weight of fluoromethyl trifluoromethyl ether; and and 1.1.1.2-tetrafluoroethane 25% by weight and fluoromethyl trifluor Each refrigerant composition consisting of 75% by weight of olomethyl ether was evaluated. Review The operating conditions selected for the represent the case. Specifically, these conditions were as follows.
蒸発器温度ニー２５℃ 冷却器温度：４０°Ｃ 過熱・ ４５℃ 過冷却＝１０℃ 冷却能カニ ＩＫＷ 等エントロピー圧縮効率・ ７５％ 表に示す冷媒組成物の性能パラメーター、すなわち凝縮器圧力、蒸発器圧力、吐 出し温度、戻りガス温度、容積流（ｖｏｌｕｍｅｔｒｉｃ ｆｌｏｗ）、装置効 率（性能係数；該係数は圧縮器に供給された機械的エネルギーに対する達成され た冷却能力の比を表わす）、冷却、冷凍能力（圧縮器の単位行程容積当たりの冷 却能力）及び蒸発器のグライド（ｇＨｄｅ）（冷媒組成物か蒸発器中で沸騰する 温度範囲）は、全て当該技術において認識されているパラメーターである。Evaporator temperature knee 25℃ Cooler temperature: 40°C Overheating/45℃ Supercooling = 10℃ Cooling Crab IKW Isentropic compression efficiency: 75% The performance parameters of the refrigerant composition given in the table, namely condenser pressure, evaporator pressure, discharge Output temperature, return gas temperature, volumetric flow, equipment efficiency coefficient of performance; the coefficient is the amount of mechanical energy achieved relative to the mechanical energy supplied to the compressor. cooling capacity (refrigerating capacity per unit stroke volume of the compressor) cooling capacity) and evaporator glide (gHde) (refrigerant composition boils in the evaporator) temperature range) are all art-recognized parameters.
また、比較として、同一運転条件下における冷媒Ｒ−１２と１．１．１．２−テ トラフルオロエタン（これは冷媒Ｒ−１２の一般的に容認された代替品である） の性能も第１表に示す。Also, for comparison, refrigerant R-12 and 1.1.1.2-te under the same operating conditions. trifluoroethane (which is a generally accepted replacement for refrigerant R-12) The performance of is also shown in Table 1.
第１−表から、１．１．１．２−テトラフルオロエタンとフルオロメチルトリフ ルオロメチルエーテルとを含有してなる本発明の冷媒組成物か、冷媒Ｒ−１２の 冷却、冷凍装置内性能とあまりかけ離れていな０性能を示し得ることか明白であ る。さらにまた、評価した混合冷媒組成物全部について、蒸発器のグライドはわ ずか０．２℃であり、かかる組成物が共沸混合物様であることを示した。From Table 1, 1.1.1.2-tetrafluoroethane and fluoromethyltrif The refrigerant composition of the present invention containing fluoromethyl ether or refrigerant R-12. It is clear that it is possible to exhibit zero performance that is not very different from the performance inside the cooling and refrigeration equipment. Ru. Furthermore, for all mixed refrigerant compositions evaluated, the evaporator glide was 0.2° C., indicating that the composition was azeotrope-like.
本発明の好ましい態様においては、冷媒組成物は１．１．１．２−テトラフルオ ロエタンと、トリフルオロメチルメチルエーテルとの混合物を、必要ならばフル オロメチルトリフルオロメチルエーテル及び／又は残存水素原子を有する別の弗 素化エーテルの少なくとも１種及び／又は別のハイドロフルオロアルカンの少な くとも１種と一緒（こ含有してなる。特に好ましい冷媒組成物は、１．１．１． ２−テトラフルオロエタンとトリフルオロメチルメチルエーテルとから本質的（ こなる混合物である。In a preferred embodiment of the invention, the refrigerant composition comprises 1.1.1.2-tetrafluorofluoride. If necessary, add a mixture of loethane and trifluoromethyl methyl ether to Oromethyl trifluoromethyl ether and/or another fluoromethyl ether with residual hydrogen atoms at least one hydrogenated ether and/or at least one other hydrofluoroalkane Particularly preferred refrigerant compositions include at least one species of refrigerant. Essentially from 2-tetrafluoroethane and trifluoromethyl methyl ether ( This is a mixture.
１、１．１．２−テトラフルオロエタンとトリフルオロメチルメチルエーテルと の混合物を含有してなる冷媒組成物が、冷却、冷凍サイクルにおいて冷媒Ｒ−１ ２と同様の性能を示すことが認められた。結果として、冷却、冷凍装置及び関連 する熱伝達装置において作動流体として現在広く使用される冷媒Ｒ−１２に代え てかかる組成物を使用し得る。1,1.1.2-tetrafluoroethane and trifluoromethyl methyl ether A refrigerant composition containing a mixture of refrigerant R-1 in a cooling or refrigeration cycle It was observed that the performance was similar to that of No. 2. As a result, cooling, refrigeration equipment and related Replaces refrigerant R-12, which is currently widely used as a working fluid in heat transfer devices. Such compositions may be used.
さらにまた、１．１．１．２−テトラフルオロエタンとトリフルオロメチルメチ ルエーテルとを含有してなる組成物は、トリフルオロメチルメチルエーテルの特 に短い大気寿命（約３．６年）により恩恵を受ける、すなわち直接的な地球温暖 化の可能性か低いことを示し得る。Furthermore, 1.1.1.2-tetrafluoroethane and trifluoromethylmethylene The composition containing trifluoromethylmethyl ether is benefits from a short atmospheric lifetime (approximately 3.6 years), i.e. direct global warming. This may indicate that the possibility of change is low.
１、、１．１．２−テトラブルオロエタンとトリフルオロメチルメチルエーテル とに基づいた好ましい冷媒組成物は、１．１．１．２−テトラフルオロエタン５ 〜７５重量％とトリフルオロメチルメチルエーテル９５〜２５重量％とからなる 。この種の特に好ましい冷媒組成物は、１．１．１．２−テトラフルオロエタン ５〜６０重量％とトリフルオロメチルメチルエーテル９５〜４０重量％とからな り、１．１．１．２−テトラフルオロエタン２５〜５０重量％とトリフルオロメ チルメチルエーテル７５〜５０重量％とからなる組成物が特に好ましい。従って 、好ましい組成物は、直接的な地球温暖化の可能性がより一層少ない組成物を与 えるトリフルオロメチルメチルエーテルが実質的な（ｓｕｂｓｔａｎｔｉａ＋） 量で存在することに特徴がある。しかしながら、かかる組成物もまた驚くべきこ とにレフリジラントＲ−１２と同等の、冷却、冷凍設備における性能を示す。1,,1.1.2-Tetrafluoroethane and trifluoromethyl methyl ether A preferred refrigerant composition based on 1.1.1.2-tetrafluoroethane 5 ~75% by weight and 95-25% by weight of trifluoromethyl methyl ether . A particularly preferred refrigerant composition of this type is 1.1.1.2-tetrafluoroethane 5 to 60% by weight and 95 to 40% by weight of trifluoromethyl methyl ether. 1.1.1.2-tetrafluoroethane 25-50% by weight and trifluoromethane Particularly preferred are compositions comprising 75 to 50% by weight of methyl ether. Therefore , preferred compositions provide compositions with even less direct global warming potential. trifluoromethyl methyl ether is substantial (substantia+) It is characterized by its existence in quantity. However, such compositions also have surprisingly It shows the same performance in cooling and refrigeration equipment as Refrigilant R-12.
トリフルオロメチルメチルエーテルは僅かに可燃性であり、本発明者らの研究に よればこのエーテルを４０重量％を越える量で含有し且つ１．１．１．２−テト ラフルオロエタンを４０重量％未満で含有してなる混合冷媒組成物もまた可燃性 であることが示唆される。熱伝達装置が本質的に密閉系であること及びある種の 装置、例えば家庭用冷却、冷蔵装置は該冷媒をほんの少量含んでいるだけである ことを記憶にととめると、かかる冷媒組成物の潜在的な可燃性は実際問題として 問題ではあり得ないと思われる。さらにまた、地球温暖化の可能性を逆に低減さ せた（ｏｐｐｏｓｉｔｅ ｒｅｄｕｃｅｄ）大量のトリフルオロメチルメチルエ ーテルを含有してなる冷媒組成物を使用することの利点は、可燃性に対して（ｏ ｐｐｏｓｉｔｅ）起こり得る不都合よりもまさる。しかしながら、もし可燃性が 関心事である場合には、その場合には１．１．１゜２−テトラフルオロエタン７ ０〜９５重量％と、トリフルオロメチルメチルエーテル３０〜５重量％とを含有 する組成物か好ましく、非引火性の点からみて、１，１．１．２−テトラフルオ ロエタン７０〜８５重量％と、トリフルオロメチルメチルエーテル３０〜１５重 量％とを含有する組成物が特に好ましい。 ′ 第２表に、１．１．１．２−テトラフルオロエタン（表中のＲ−１３４ａ）と、 トリフルオロメチルメチルエーテル（表中のＥ−１４３ａ）とを含有してなる本 発明の多数の冷媒組成物の性能を示す。評価した冷媒組成物の各成分の重量％を 表の第２行目に示す。すなわち、１．１．１．２−テトラフルオロエタン７５重 量％とトリフルオロメチルメチルエーテル２５重量％とからなる冷媒組成物、１ ，１，１．２−テトラフルオロエタン５０重量％とトリフルオロメチルメチルエ ーテル５０重量％とからなる冷媒組成物：及びＩ、 １．、１．２−テトラフル オロエタン２５重量％とトリフルオロメチルメチルエーテル７５重量％とからな る冷媒組成物のそれぞれを評価した。評価のために選択した運転条件は、家庭用 冷却、冷蔵装置に存在する運転条件を代表している。具体的には、これらの条件 は下記の通りであった。Trifluoromethyl methyl ether is slightly flammable and According to this, the ether contains more than 40% by weight and Mixed refrigerant compositions containing less than 40% by weight of lafluoroethane are also flammable. It is suggested that The heat transfer device is essentially a closed system and certain Equipment, such as domestic cooling and refrigeration equipment, contains only small amounts of the refrigerant. Keeping in mind that the potential flammability of such refrigerant compositions is It doesn't seem like it could be a problem. Furthermore, the possibility of global warming can be conversely reduced. Opposite reduced large amount of trifluoromethyl methyl ether The advantage of using refrigerant compositions containing pposite) outweighs any possible inconvenience. However, if flammable If so, then 1.1.1°2-tetrafluoroethane7 Contains 0 to 95% by weight and 30 to 5% by weight of trifluoromethyl methyl ether. From the viewpoint of non-flammability, 1,1.1.2-tetrafluorocarbon is preferred. 70-85% by weight of loethane and 30-15% by weight of trifluoromethyl methyl ether Particularly preferred are compositions containing %. ′ Table 2 shows 1.1.1.2-tetrafluoroethane (R-134a in the table), A book containing trifluoromethyl methyl ether (E-143a in the table) 1 illustrates the performance of a number of refrigerant compositions of the invention. The weight percent of each component of the evaluated refrigerant composition Shown in the second row of the table. That is, 1.1.1.2-tetrafluoroethane 75 Refrigerant composition consisting of % by weight and 25% by weight of trifluoromethyl methyl ether, 1 , 50% by weight of 1,1,2-tetrafluoroethane and trifluoromethylmethyl ethane. A refrigerant composition consisting of 50% by weight of ether: and I, 1. , 1.2-tetraflu 25% by weight of oroethane and 75% by weight of trifluoromethyl methyl ether. Each of the refrigerant compositions was evaluated. The operating conditions selected for the evaluation were those for domestic It represents the operating conditions that exist in cooling and refrigeration equipment. Specifically, these conditions was as follows.
蒸発器温度ニー２５℃ 冷却器温度：４０℃ 過熱・ ４５℃ 過冷却 １０℃ 冷却能カニ ＩＫ！ 等エントロピー圧縮効率 ７５％ 表に示す冷媒組成物の性能パラメーター、すなわち凝縮器圧力、蒸発器圧力、吐 出し温度、戻りガス温度、容積流、装置効率（性能係数、該係数は圧縮器に供給 された機械的エネルギーに対する達成された冷却能）Ｊの比を表わす）、冷却、 冷凍能力（圧縮器の単位行程容積当たりの冷却能力）及び蒸発器のグライド（ｇ ｌｉｄｅ）（冷媒組成物が蒸発器中で沸騰する温度範囲）は、全て当該技術にお いて認識されているパラメーターである。Evaporator temperature knee 25℃ Cooler temperature: 40℃ Overheating/45℃ Supercooling 10℃ Cooling ability crab IK! Isentropic compression efficiency 75% The performance parameters of the refrigerant composition given in the table, namely condenser pressure, evaporator pressure, discharge output temperature, return gas temperature, volumetric flow, equipment efficiency (performance coefficient, this coefficient is supplied to the compressor represents the ratio of the achieved cooling power to the mechanical energy applied), cooling, Refrigeration capacity (cooling capacity per unit stroke volume of the compressor) and evaporator glide (g (temperature range at which the refrigerant composition boils in the evaporator) is entirely within the skill of the art. It is a recognized parameter.
また、比較として、同一運転条件下における冷媒Ｒ−１２と１．１．１．２−テ トラフルオロエタン（これは冷媒Ｒ−１２の一般的に容認された代替品である） の性能も第２表に示す。Also, for comparison, refrigerant R-12 and 1.1.1.2-te under the same operating conditions. trifluoroethane (which is a generally accepted replacement for refrigerant R-12) The performance of is also shown in Table 2.
第２表から、１，１，１．２−テトラフルオロエタンとトリフルオロメチルメチ ルエーテルとを含有してなる本発明の冷媒組成物が、冷媒Ｒ−１２の性能と同等 の冷却、冷凍装置内性能を示し得ることが明白である。さらにまた、評価した混 合冷媒組成物全部について、蒸発器のグライドは本質的に皆無であり、かかる組 成物が共沸混合物様であることを示した。From Table 2, 1,1,1,2-tetrafluoroethane and trifluoromethylmethylene The refrigerant composition of the present invention containing refrigerant R-12 has the same performance as refrigerant R-12. It is clear that the cooling performance within the refrigeration equipment can be shown. Furthermore, the evaluated confusion For all combined refrigerant compositions, there is essentially no evaporator glide; The product was shown to be azeotrope-like.
本発明の冷媒組成物は簡単な混合法により調製し得る。The refrigerant composition of the present invention can be prepared by a simple mixing method.
本発明の冷媒組成物は、あらゆる型の圧縮サイクル式熱伝達装置において有用で ある。従って、本発明の冷媒組成物は、該冷媒組成物を凝縮させ、その後に冷却 されるべき物体との熱交換関係において該冷媒組成物を蒸発させることを伴う方 法によって冷却を提供するのに使用し得る。また、本発明の冷媒組成物は、該冷 媒組成物を加熱されるべき物体との熱交換関係において凝縮させ、その後に該冷 媒組成物を蒸発させることを伴う方法によって加熱を提供するのに使用し得る。The refrigerant compositions of the present invention are useful in all types of compression cycle heat transfer devices. be. Therefore, the refrigerant composition of the present invention allows the refrigerant composition to be condensed and then cooled. methods that involve evaporating said refrigerant composition in a heat exchange relationship with an object to be may be used to provide cooling by any method. Further, the refrigerant composition of the present invention The medium composition is condensed in heat exchange relationship with the object to be heated, and then the cooling is performed. It can be used to provide heating by methods that involve evaporating the medium composition.
本発明の組成物は、短い大気寿命と、オゾンを減少させることが本質的に皆無で あることとを兼備した能力と効率との間に良好な歩み寄り（ｃｏｍｐｒｏｍｉｓ ｅ）を提供する。前記組成物は、冷媒Ｒ−１２によって現在満たされている用途 、例えば家庭用冷凍、冷蔵、自動車用空気調和及び冷凍食品輸送に特に適してい る。The compositions of the present invention have short atmospheric lifetimes and essentially no ozone depletion. A good compromise between the ability to do something and efficiency. e). The composition is suitable for applications currently filled by refrigerant R-12. , especially suitable for household refrigeration, refrigeration, automobile air conditioning and frozen food transportation, for example. Ru.
第１表 會 ＢＰ＝泡立ち点 會會 ｐｐ＝ 露点 第２表 ★ ＢＰ＝泡立ち点 會☆ Ｄｐ＝ 露点 国際調査報告 １ｍ−一、、、、、、ＰＣＴ／ＧＢ ９２１０２３８２フロントページの続き （７２）発明者 モリソン、ジェームス、デーピッドイギリス国、チェシャー・ シイダブリュ９・８キユイー、ノースウィッチ、モールトン、ニットリーズ・レ ーン、１２Table 1 Meeting BP = bubble point Meeting pp= Dew point Table 2 ★ BP = bubble point Meeting☆ Dp= Dew point international search report 1m-1,,,,,,PCT/GB 92102382Continuation of front page (72) Inventor: Morrison, James, David Cheshire, United Kingdom Cdbrew 9.8 Kiyui, Northwich, Moulton, Knitley's Les 12
Claims (14)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB929200521A GB9200521D0 (en) | 1992-01-10 | 1992-01-10 | Compositions useful as refrigerants |
| GB9200521.4 | 1992-01-10 | ||
| PCT/GB1992/002382 WO1993014173A1 (en) | 1992-01-10 | 1992-12-23 | Compositions useful as refrigerants |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07502774A true JPH07502774A (en) | 1995-03-23 |
Family
ID=10708415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5512216A Pending JPH07502774A (en) | 1992-01-10 | 1992-12-23 | Compositions useful as refrigerants |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0620837A1 (en) |
| JP (1) | JPH07502774A (en) |
| KR (1) | KR940703902A (en) |
| AU (1) | AU666694B2 (en) |
| BR (1) | BR9207035A (en) |
| CA (1) | CA2126185A1 (en) |
| GB (1) | GB9200521D0 (en) |
| WO (1) | WO1993014173A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07504889A (en) * | 1991-12-03 | 1995-06-01 | ユナイテッド ステーツ インバイオロンメンタル プロテクション エイジェンシー | Refrigerant composition and method of use thereof |
| BR9207027A (en) * | 1992-01-10 | 1995-12-05 | Ici Plc | Refrigerant composition heat transfer device and processes to provide cooling and heating |
| US5605882A (en) * | 1992-05-28 | 1997-02-25 | E. I. Du Pont De Nemours And Company | Azeotrope(like) compositions of pentafluorodimethyl ether and difluoromethane |
| EP0680503A1 (en) * | 1993-01-20 | 1995-11-08 | Imperial Chemical Industries Plc | Refrigerant compositions |
| EP0856038B2 (en) * | 1995-10-20 | 2009-10-28 | Minnesota Mining And Manufacturing Company | Hydrofluoroethers as low temperature refrigerants |
| US5819549A (en) * | 1996-10-16 | 1998-10-13 | Minnesota Mining And Manufacturing Company | Secondary loop refrigeration system |
| USRE37054E1 (en) | 1996-10-16 | 2001-02-20 | Minnesota Mining And Manufacturing Company | Secondary loop refrigeration system |
| CN110591650B (en) * | 2019-09-12 | 2020-09-25 | 珠海格力电器股份有限公司 | Heat transfer composition suitable for centrifugal refrigerating unit |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4961321A (en) * | 1989-02-28 | 1990-10-09 | W. R. Grace & Co.-Conn. | Bis (difluoromethyl) ether refrigerant |
| EP0882761B1 (en) * | 1990-03-12 | 2004-10-20 | E.I. Du Pont De Nemours And Company | Azeotropic composition of 1,1,1,2-tetrafluoroethane and dimethyl ether |
| BR9207027A (en) * | 1992-01-10 | 1995-12-05 | Ici Plc | Refrigerant composition heat transfer device and processes to provide cooling and heating |
| US5605882A (en) * | 1992-05-28 | 1997-02-25 | E. I. Du Pont De Nemours And Company | Azeotrope(like) compositions of pentafluorodimethyl ether and difluoromethane |
-
1992
- 1992-01-10 GB GB929200521A patent/GB9200521D0/en active Pending
- 1992-12-23 EP EP93900352A patent/EP0620837A1/en not_active Withdrawn
- 1992-12-23 BR BR9207035A patent/BR9207035A/en not_active Application Discontinuation
- 1992-12-23 WO PCT/GB1992/002382 patent/WO1993014173A1/en not_active Application Discontinuation
- 1992-12-23 KR KR1019940702373A patent/KR940703902A/en not_active Application Discontinuation
- 1992-12-23 AU AU31687/93A patent/AU666694B2/en not_active Ceased
- 1992-12-23 JP JP5512216A patent/JPH07502774A/en active Pending
- 1992-12-23 CA CA002126185A patent/CA2126185A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0620837A1 (en) | 1994-10-26 |
| CA2126185A1 (en) | 1993-07-22 |
| BR9207035A (en) | 1995-12-06 |
| WO1993014173A1 (en) | 1993-07-22 |
| AU3168793A (en) | 1993-08-03 |
| GB9200521D0 (en) | 1992-02-26 |
| KR940703902A (en) | 1994-12-12 |
| AU666694B2 (en) | 1996-02-22 |
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