JP2011058748A - Refrigerating circuit and method of improving the same - Google Patents
Refrigerating circuit and method of improving the same Download PDFInfo
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本発明は、冷媒の全部又は１部としてＨＦＯ１２３４ｙｆに代表される不飽和フッ化炭化水素冷媒を含む冷媒が使用される冷凍回路及びその改良法に関する。 The present invention relates to a refrigeration circuit in which a refrigerant containing an unsaturated fluorinated hydrocarbon refrigerant typified by HFO1234yf is used as all or part of the refrigerant, and an improved method thereof.
車両用空調装置などに用いられる冷凍回路には現状では代表的な冷媒としてフルオロカーボンの一種であるＨＦＣ１３４ａが使用されるとともに、代表的な冷凍機油としてポリアルキレングリコール（ＰＡＧ）が使用されている。 Currently, HFC134a, which is a kind of fluorocarbon, is used as a typical refrigerant in a refrigeration circuit used for a vehicle air conditioner and the like, and polyalkylene glycol (PAG) is used as a typical refrigeration oil.
現在、世界規模で地球温暖化を防止する取り組みが盛んに進んでいる。特にＥＵ諸国においてはフロンガス規制において、自動車用の代表的な冷媒ＨＦＣ１３４ａの高い地球温暖化係数（ＧＷＰ１４３０）に対する規制を進め、２０１２年以降の新型車へのこの冷の使用の禁止を、また２０１７年以降には全ての車両へのこの冷媒の使用禁止を決定した。これを受け、世界各地域に同様の規制が波及している。この動向に対して冷媒メーカー、冷凍機油メーカー及び空調機器メーカーは、安全でありながら地球温暖化係数（ＧＷＰ）などのさらなる低減と改善を目指して、新冷媒及び新冷媒用冷凍機油の研究・開発が行われている。このような改善を目指した新冷媒として現在、低ＧＷＰ化を求めて分子内部に不飽和結合を導入し、蒸発温度が−５０℃から−１０℃の範囲にある不飽和フッ化炭化水素冷媒が次世代の冷媒として開発されている。特に、ＨＦＯ１２３４ｙｆやＨＦＯ１２３４ｚｅなどの不飽和フッ化炭化水素冷媒が世界的に採用される見込みが有力である。これらの物質を車両用空調装置などの冷凍回路へ適用できるよう改良を目指した試験研究が盛んになってきた。 Currently, efforts are being made to prevent global warming on a global scale. In EU countries in particular, in the regulation of chlorofluorocarbons, regulations on the high global warming potential (GWP1430) of a typical refrigerant HFC134a for automobiles will be promoted, and the use of this cold in new models after 2012 will be prohibited. Later, we decided to ban the use of this refrigerant in all vehicles. In response, similar regulations are spreading throughout the world. In response to this trend, refrigerant manufacturers, refrigeration oil manufacturers, and air conditioning equipment manufacturers are researching and developing new refrigerants and refrigeration oils for new refrigerants with the aim of further reducing and improving the Global Warming Potential (GWP) while being safe. Has been done. As a new refrigerant aiming at such improvement, an unsaturated fluorinated hydrocarbon refrigerant having an evaporating temperature in the range of −50 ° C. to −10 ° C. by introducing an unsaturated bond inside the molecule in search of low GWP is now available. Developed as the next generation refrigerant. In particular, it is probable that unsaturated fluorinated hydrocarbon refrigerants such as HFO1234yf and HFO1234ze will be adopted worldwide. Test research aimed at improving these materials so that they can be applied to refrigeration circuits such as air conditioners for vehicles has become popular.
ところが、不飽和フッ化炭化水素冷媒は低ＧＷＰ値を特長のひとつとする反面、分子内に不飽和結合を有するためＨＦＣ１３４ａをはじめとする従来の飽和フッ化炭化水素系冷媒と比較して反応性が高く熱・化学的安定性に乏しい。そこで、本発明者らは、不飽和フッ化炭化水素冷媒の代表例であるＨＦＯ１２３４ｙｆについて、この冷媒を実際の冷凍回路に使用した場合の熱・化学的安定性を確認する実験を行ったところ、圧縮機としてベーンロータリー圧縮機を使用し、冷媒としてＨＦＯ１２３４ｙｆを使用し、且つ冷凍機油として代表的なポリアルキレングリコールを使用した実験系の冷凍回路では、特に高速高負荷条件下において、圧縮機内にワックス状の固形物が生成するのに対し、この実験系の冷凍回路においてベーンロータリー圧縮機をレシプロ圧縮機に置換えた実験系の冷凍回路では、高速高負荷条件下においても、ワックス状の固形物は生成しないという事実を確認した。このワックス状の固形物は、冷凍回路の詰まりや冷凍性能の低下を惹き起こすため、冷凍回路の著しい性能低下や故障などの致命的な欠陥になり得る。ワックス状の固形物の生成はＨＦＯ１２３４ｙｆに限られず分子内に同様の不飽和結合を有する他の不飽和フッ化炭化水素冷媒においても生成するものと考えられる。従って、冷凍回路において不飽和フッ化炭化水素冷媒を使用する場合、特に高速高負荷条件下においてもかかるワックス状の固形物が圧縮機内や冷凍回路内に生成するのを防止する必要がある。 However, while unsaturated fluorinated hydrocarbon refrigerants have a low GWP value, they have reactivity in comparison with conventional saturated fluorinated hydrocarbon refrigerants such as HFC134a because they have unsaturated bonds in the molecule. High and poor thermal and chemical stability. Therefore, the present inventors conducted an experiment to confirm the thermal and chemical stability when HFO1234yf, which is a representative example of an unsaturated fluorinated hydrocarbon refrigerant, is used in an actual refrigeration circuit. In an experimental refrigeration circuit using a vane rotary compressor as a compressor, HFO1234yf as a refrigerant, and a typical polyalkylene glycol as a refrigeration oil, a wax is contained in the compressor particularly under high-speed and high-load conditions. In the experimental refrigeration circuit in which the vane rotary compressor is replaced with a reciprocating compressor in this experimental refrigeration circuit, the wax-like solid is Confirmed the fact that it does not generate. Since the wax-like solid causes clogging of the refrigeration circuit and deterioration of the refrigeration performance, it can be a fatal defect such as a significant performance reduction or failure of the refrigeration circuit. The formation of a wax-like solid is not limited to HFO1234yf, but may be generated in other unsaturated fluorinated hydrocarbon refrigerants having similar unsaturated bonds in the molecule. Therefore, when an unsaturated fluorinated hydrocarbon refrigerant is used in the refrigeration circuit, it is necessary to prevent such wax-like solids from being generated in the compressor or the refrigeration circuit even under high speed and high load conditions.
従って、本発明が解決しようとする課題は、圧縮機としてベーンロータリー圧縮機を使用し、冷媒として不飽和フッ化炭化水素冷媒を使用し、且つ冷凍機油としてポリアルキレングリコールなどのエーテル系潤滑油を使用する冷凍回路において、冷凍回路の詰まりや冷凍性能の低下の原因となるワックス状の固形物が冷凍回路内に生成するのを防止することにある。 Accordingly, the problem to be solved by the present invention is that a vane rotary compressor is used as a compressor, an unsaturated fluorinated hydrocarbon refrigerant is used as a refrigerant, and an ether-based lubricating oil such as polyalkylene glycol is used as a refrigerator oil. In the refrigeration circuit to be used, it is intended to prevent the formation of wax-like solid matter in the refrigeration circuit that causes clogging of the refrigeration circuit or a decrease in the refrigeration performance.
本発明者らはワックス状の固形物の化学分析を行い、この固形物は融点が約５０℃〜６３℃の低分子量の重合パラフィンであることを確認した。本発明者らはこの分析結果に基づきワックス状の固形物の生成メカニズムを次のように推定している。すなわち、例えばベーンロータリ圧縮機では、シリンダ室内をロータが回転運動するとき、ロータとシリンダ室内壁との接触部及びロータとシリンダ内を低圧室と高圧室とに仕切るベーンとの接触部で、両者が相互に強く押圧された状態で摺動するため、使用する冷凍機油には高度の潤滑性能が要求されるところ、ポリアルキレングリコールなどのエーテル系潤滑油の潤滑性能はベーンロータリ圧縮機にとって必ずしも充分ではない。このため、高速高負荷条件下において、ロータの回転運動に伴い圧縮機構部の摺動表面に局部的に金属活性表面が露出し易くなる。一方、不飽和フッ化炭化水素冷媒は反応性が高く熱・化学的安定性に乏しい。その結果、露出した金属活性表面が反応触媒として作用して、ベーンロータリ圧縮機の圧縮機構部内において高温高圧の冷媒ガス雰囲気下で不飽和フッ化炭化水素冷媒とエーテル系潤滑油のポリオキシアルキレン構造との反応を誘起し、その結果不飽和フッ化炭化水素冷媒の分解と分解物たる重合性オレフィンの生成が起こり、更にこの重合性オレフィンが金属活性表面の重合触媒作用を受けて重合して重合パラフィンを生成するものと推定される。従って、ワックス状の固形物の生成を防止するためには、エーテル系潤滑油の潤滑性能の不足をポリオキシアルキレン構造を有しない他の潤滑油性成分の併用により補うことが有効な手段となり得る。また、不飽和フッ化炭化水素冷媒の分解により生成するフッ化水素を補足する酸補足剤を使用することも有効な手段となり得る。本発明者らはこの観点から各種化合物について検討し、長鎖脂肪族エポキシアルカンがワックス状の固形物の生成防止に非常に効果的である事実を見出した。本発明はかかる技術的知見と着想に基づいて完成されたものである。 The present inventors conducted a chemical analysis of a waxy solid, and confirmed that this solid was a low molecular weight polymerized paraffin having a melting point of about 50 ° C to 63 ° C. Based on this analysis result, the present inventors presume the formation mechanism of a waxy solid as follows. That is, for example, in a vane rotary compressor, when the rotor rotates in the cylinder chamber, both the contact portion between the rotor and the cylinder chamber wall and the contact portion between the rotor and the vane dividing the inside of the cylinder into a low pressure chamber and a high pressure chamber. Since the refrigeration machine oil used is required to have a high level of lubrication performance, the lubrication performance of ether-based lubricants such as polyalkylene glycol is not always sufficient for vane rotary compressors. is not. For this reason, the metal active surface is likely to be locally exposed on the sliding surface of the compression mechanism portion with the rotational movement of the rotor under high speed and high load conditions. On the other hand, unsaturated fluorinated hydrocarbon refrigerants are highly reactive and poor in thermal and chemical stability. As a result, the exposed metal active surface acts as a reaction catalyst, and the polyoxyalkylene structure of the unsaturated fluorinated hydrocarbon refrigerant and the ether-based lubricating oil in the compression mechanism portion of the vane rotary compressor in a high-temperature and high-pressure refrigerant gas atmosphere. As a result, the unsaturated fluorinated hydrocarbon refrigerant is decomposed and a polymerizable olefin is generated as a decomposition product, and this polymerizable olefin is polymerized by polymerization reaction on the metal active surface. Presumed to produce paraffin. Therefore, in order to prevent the formation of a wax-like solid, it can be an effective means to supplement the lack of lubricating performance of the ether-based lubricating oil with the combined use of other lubricating oil components having no polyoxyalkylene structure. . It can also be an effective means to use an acid scavenger that supplements the hydrogen fluoride produced by the decomposition of the unsaturated fluorinated hydrocarbon refrigerant. The present inventors have studied various compounds from this viewpoint, and have found that long-chain aliphatic epoxy alkanes are very effective in preventing the formation of waxy solids. The present invention has been completed based on such technical knowledge and ideas.
すなわち、本発明の冷凍回路は、冷媒を圧縮するベーンロータリー圧縮機を備える冷凍回路において、前記冷媒がその一部又は全部として不飽和フッ化炭化水素冷媒を含有し、冷凍機油がポリオキシアルキレン構造を有するエーテル系潤滑油からなり、前記エーテル系潤滑油が長鎖脂肪族エポキシアルカンを含有することを特徴としている。この発明によれば、前記エポキシアルカンが、圧縮機の運転に伴い引き起される不飽和フッ化炭化水素冷媒の分解と重合性分解物の重合に起因する重合パラフィンの生成とを防止する重合パラフィン防止剤として機能する。 That is, the refrigeration circuit of the present invention is a refrigeration circuit including a vane rotary compressor for compressing a refrigerant, wherein the refrigerant contains an unsaturated fluorinated hydrocarbon refrigerant as part or all of the refrigerant, and the refrigeration oil has a polyoxyalkylene structure. It is characterized by comprising an ether type lubricating oil having a long chain aliphatic epoxy alkane. According to the present invention, the epoxy alkane prevents the polymerization of the unsaturated fluorinated hydrocarbon refrigerant caused by the operation of the compressor and the generation of the polymerized paraffin resulting from the polymerization of the polymerizable decomposition product. Functions as an inhibitor.
また、本発明の冷凍回路の改良法は、冷媒を圧縮するベーンロータリー圧縮機を備える冷凍回路の改良法において、前記冷媒がその一部又は全部として不飽和フッ化炭化水素冷媒を含有し、冷凍機油がポリオキシアルキレン構造を有するエーテル系潤滑油からなり、前記エーテル系潤滑油が長鎖エポキシアルカンを含有することにより、前記圧縮機の運転に伴い惹起される前記不飽和フッ化炭化水素冷媒の分解と重合性分解物の重合に起因する重合パラフィンの生成とを防止することを特徴としている。 The refrigeration circuit improvement method of the present invention is the refrigeration circuit improvement method including a vane rotary compressor that compresses the refrigerant, wherein the refrigerant contains an unsaturated fluorinated hydrocarbon refrigerant as part or all of the refrigeration circuit. The machine oil is composed of an ether-based lubricating oil having a polyoxyalkylene structure, and the ether-based lubricating oil contains a long-chain epoxy alkane, whereby the unsaturated fluorinated hydrocarbon refrigerant caused by the operation of the compressor. It is characterized by preventing the formation of polymerized paraffin resulting from the decomposition and polymerization of a polymerizable decomposition product.
上記構成において熱・化学的安定性が特に低い分子末端にＣＨ２＝ＣＨ−又はＣＨ２＝ＣＦ−の基を有する不飽和フッ化炭化水素冷媒が用いられる場合にも、重合パラフィンの生成を効果的に防止できる。また、上記構成において不飽和フッ化炭化水素冷媒として代表的なＨＦＯ１２３４ｙｆ及びＨＦＯ１２３４ｚｅが用いられる場合にも、重合パラフィンの生成を効果的に防止できる。上記構成において、長鎖エポキシアルカンとしては、炭素原子数８〜２５のエポキシアルカンが好ましい。 Even when an unsaturated fluorinated hydrocarbon refrigerant having a CH2 = CH- or CH2 = CF- group at the molecular end having a particularly low thermal / chemical stability in the above configuration is used, it is possible to effectively produce polymerized paraffin. Can be prevented. Moreover, also when typical HFO1234yf and HFO1234ze are used as an unsaturated fluorinated hydrocarbon refrigerant in the above configuration, the formation of polymerized paraffin can be effectively prevented. In the above configuration, the long-chain epoxy alkane is preferably an epoxy alkane having 8 to 25 carbon atoms.
本発明の冷凍回路及びその改良法は、家電、住宅空調、流通分野などに利用されるあらゆる冷凍回路に適用可能であり、特に車両空調装置用冷凍回路として好適である。車両空調装置用冷凍回路において本発明を適用することにより、ＨＦＯ１２３４ｙｆなどの不飽和フッ化炭化水素冷媒を使用して環境負荷を低減し且つ従来と同様の動作安定性を達成した冷凍回路を実現することが可能となる。 The refrigeration circuit and its improvement method of the present invention can be applied to any refrigeration circuit used in home appliances, residential air conditioning, distribution fields, etc., and is particularly suitable as a refrigeration circuit for a vehicle air conditioner. By applying the present invention to a refrigeration circuit for a vehicle air conditioner, an refrigeration circuit is realized that uses an unsaturated fluorohydrocarbon refrigerant such as HFO1234yf to reduce the environmental load and achieve the same operational stability as before. It becomes possible.
本発明によれば、圧縮機としてベーンロータリー圧縮機を使用し、冷媒として不飽和フッ化炭化水素冷媒を使用し、且つ冷凍機油としてポリオキシアルキレン構造を有するエーテル系潤滑油を使用する冷凍回路において、エーテル系潤滑油の潤滑性能の不足を長鎖エポキシアルカンの併用により補うとともに、不飽和フッ化炭化水素冷媒の分解により生成し冷媒の更なる分解を助長するフッ化水素を長鎖エポキシアルカンのエポキシ基で補足することにより、圧縮機構部の摺動に伴う金属活性表面の露出を防止して、これにより圧縮機構部内において高温高圧の冷媒ガス雰囲気下で不飽和フッ化炭化水素冷媒とエーテル系潤滑油のポリオキシアルキレン構造とが露出した金属活性表面の触媒作用を受けて反応することを防止でき、その結果冷凍回路の詰まりや冷凍性能の低下の原因となる重合パラフィンの生成を防止することができる。 According to the present invention, in a refrigeration circuit using a vane rotary compressor as a compressor, an unsaturated fluorinated hydrocarbon refrigerant as a refrigerant, and an ether-based lubricating oil having a polyoxyalkylene structure as a refrigeration oil In addition to supplementing the lack of lubrication performance of ether-based lubricants with the combined use of long-chain epoxy alkanes, hydrogen fluoride, which is generated by the decomposition of unsaturated fluorinated hydrocarbon refrigerants and promotes further decomposition of the refrigerant, is By supplementing with an epoxy group, exposure of the metal active surface due to sliding of the compression mechanism portion is prevented, and thereby the unsaturated fluorinated hydrocarbon refrigerant and the ether system in a high-temperature and high-pressure refrigerant gas atmosphere in the compression mechanism portion. It is possible to prevent the polyoxyalkylene structure of the lubricating oil from reacting with the catalytic action of the exposed metal active surface. It is possible to prevent the formation of polymerization paraffin cause a reduction in the circuit of clogging or freezing performance.
図１は車両用空調装置などに用いられる冷凍回路の基本的な構成を示している。図１において、冷凍回路１は、冷媒を圧縮する圧縮機２と、圧縮した冷媒を凝縮する凝縮器３と、凝縮した冷媒を減圧・膨張させる減圧・膨張手段としての膨張弁４と、減圧・膨張した冷媒を蒸発させる蒸発器５とを備えており、この冷凍回路１中を冷媒がその状態を変化させながら循環される。
FIG. 1 shows a basic configuration of a refrigeration circuit used in a vehicle air conditioner or the like. In FIG. 1, a
本発明で使用するベーンロータリー圧縮機には特に制限はない。圧縮機の構成材料として鉄系材料のほか、アルミニウム、マグネシウム又はその合金などの軽金属系材料が使用可能である。圧縮機構部において可動側のロータは慣性力を低減させるために鉄系材料よりも比重が小さなアルミニウム、マグネシウム又はその合金などの軽金属系材料が使用される場合が多い。これらの鉄系材料や軽金属系材料はいずれも純粋の金属素材の状態では高い反応性に富んでいるが、通常はその表面は酸化被膜で覆われて金属素材の活性が抑えられた状態にある。しかし、冷凍機油の潤滑性能が不充分であると、酸化被膜がロータの回転運動に伴う摩擦などにより失われて金属活性表面が露出する。金属活性表面が露出すると、その金属素材の高い反応性のために、この金属活性表面は極めて高い触媒作用を呈する。従って、高温高圧状態の冷媒雰囲気下でエーテル系潤滑油と不飽和フッ化炭化水素冷媒とがこの金属活性表面に接触すると、この金属活性表面の触媒作用を受けてエーテル系潤滑油のポリオキシアルキレン構造と不飽和フッ化炭化水素冷媒が反応する。この反応により不飽和フッ化炭化水素冷媒の分解と分解物たる重合性オレフィンの生成が起こり、更にこの重合性オレフィンが金属活性表面の重合触媒作用を受けて高温高圧の冷媒ガス雰囲気下で重合して重合パラフィンを生成することになる。しかしながら、本発明によれば、エーテル系潤滑油は長鎖エポキシアルカンを含有し、この長鎖エポキシアルカンは高温高圧の冷媒ガス雰囲気下でも不飽和フッ化炭化水素冷媒と反応することはないので、エーテル系潤滑油の潤滑性能の不足を補って金属活性表面の露出を防止する一方、不飽和フッ化炭化水素冷媒の分解により生成し冷媒の更なる分解を助長するフッ化水素と反応してこれを消失させ、これにより不飽和フッ化炭化水素冷媒の分解と分解物たる重合性オレフィンの生成を防止するとともに、重合性オレフィンの重合による重合パラフィンの生成を防止する。 There is no restriction | limiting in particular in the vane rotary compressor used by this invention. In addition to iron-based materials, light metal materials such as aluminum, magnesium, or alloys thereof can be used as the constituent material of the compressor. In order to reduce the inertial force, in the compression mechanism section, a light metal material such as aluminum, magnesium, or an alloy thereof having a specific gravity smaller than that of the iron material is often used. Although these iron-based materials and light metal-based materials are both highly reactive in the state of pure metal materials, their surfaces are usually covered with an oxide film and the activity of the metal materials is suppressed. . However, if the lubricating performance of the refrigerating machine oil is insufficient, the oxide film is lost due to friction associated with the rotational movement of the rotor and the metal active surface is exposed. When the metal active surface is exposed, the metal active surface exhibits a very high catalytic action due to the high reactivity of the metal material. Therefore, when an ether type lubricating oil and an unsaturated fluorinated hydrocarbon refrigerant come into contact with the metal active surface in a high-temperature and high-pressure refrigerant atmosphere, the metal active surface is catalyzed and the polyoxyalkylene of the ether type lubricating oil. The structure reacts with the unsaturated fluorinated hydrocarbon refrigerant. This reaction causes the decomposition of the unsaturated fluorinated hydrocarbon refrigerant and the production of a polymerizable olefin as a decomposition product, and this polymerizable olefin undergoes polymerization catalysis on the metal active surface and polymerizes in a high-temperature and high-pressure refrigerant gas atmosphere. As a result, polymerized paraffin is produced. However, according to the present invention, the ether-based lubricating oil contains a long-chain epoxy alkane, and this long-chain epoxy alkane does not react with the unsaturated fluorinated hydrocarbon refrigerant even in a high-temperature and high-pressure refrigerant gas atmosphere. This compensates for the lack of lubrication performance of ether-based lubricants and prevents exposure of the active metal surface, while reacting with hydrogen fluoride, which is generated by the decomposition of unsaturated fluorinated hydrocarbon refrigerant and promotes further decomposition of the refrigerant. As a result, the decomposition of the unsaturated fluorinated hydrocarbon refrigerant and the production of the polymerizable olefin as a decomposition product are prevented, and the production of polymerized paraffin due to the polymerization of the polymerizable olefin is prevented.
本発明で使用される不飽和フッ化炭化水素冷媒としては、例えば１，２，３，３−テトラフルオロ−１−プロペン（ＨＦＣ−１２３４ｙｅ）；１，３，３，３−テトラフルオロ−１−プロペン（ＨＦＣ−１２３４ｚｅ）；２，３，３，３−テトラフルオロ−１−プロペン（ＨＦＣ−１２３４ｙｆ）；１，１，２，３−テトラフルオロ−１−プロペン（ＨＦＣ−１２３４ｙｃ）；１，１，３，３−テトラフルオロ−１−プロペン（ＨＦＣ−１２３４ｚｃ）；２，３，３−トリフルオロ−１−プロペン（ＨＦＣ−１２４３ｙｆ）；３，３，３−トリフルオロ−１−プロペン（ＨＦＣ−１２４３ｚｆ）；１，１，２−トリフルオロ−１−プロペン（ＨＦＣ−１２４３ｙｃ）；１，１，３−トリフルオロ−１−プロペン（ＨＦＣ−１２４３ｚｃ）；１，２，３−トリフルオロ−１−プロペン（ＨＦＣ−１２４３ｙｅ）；１，３，３−トリフルオロ−１−プロペン（ＨＦＣ−１２４３ｚｅ）；３，３，３−トリフルオロプロペン（ＨＦＣ−１２４３ｚｆ）などのハイドロフルオロプロペン：２，３，３，４，４，４−ヘキサフルオロ−１−ブテン（ＣＦ３ＣＦ２ＣＦ＝ＣＨ２）；３，３，３−トリフルオロ−２−（トリフルオロメチル）−１−プロペン（ＣＨ２＝Ｃ（ＣＦ３）２）；１，１，１，３，４−ペンタフルオロ−２−ブテン（ＣＦ３ＣＨ＝ＣＦＣＨ２Ｆ）；３，３，４，４，４−ペンタフルオロ−１−ブテン（ＣＦ３ＣＦ２ＣＨ＝ＣＨ２）；２，３，３，４，４−ペンタフルオロ−１−ブテン（ＣＨ２＝ＣＦＣＦ２ＣＨＦ２）；３，３，４，４−テトラフルオロ−１−ブテン（ＣＨ２＝ＣＨＣＦ２ＣＨＦ２）；３，３−ジフルオロ−２−（ジフルオロメチル）−１−プロペン（ＣＨ２＝Ｃ（ＣＨＦ２）２）；３，３，４，４，４−ペンタフルオロ−２−（トリフルオロメチル）−１−ブテン（ＣＨ２＝Ｃ（ＣＦ３）ＣＦ２ＣＦ３）；３，４，４，４−テトラフルオロ−３−（トリフルオロメチル）−１−ブテン（（ＣＦ３）２ＣＦＣＨ＝ＣＨ２）；２，４，４，４−テトラフルオロ−３−（トリフルオロメチル）−１−ブテン（ＣＨ２＝ＣＦＣＨ（ＣＦ３）２）；４，４，４−トリフルオロ−３−（トリフルオロメチル）−１−ブテン（ＣＨ２＝Ｃ（ＣＦ３）ＣＨ２ＣＦ３）などのハイドロフルオロブテン：３，３，４，４，５，５，５−ヘプタフルオロ−１−ペンテン（ＣＦ３ＣＦ２ＣＦ２ＣＨ＝ＣＨ２）；２，３，３，４，４，５，５−ヘプタフルオロ−１−ペンテン（ＣＨ２＝ＣＦＣＦ２ＣＦ２ＣＨＦ２）；３，３，４，５，５，５−ヘキサフルオロ−１−ペンテン（ＣＨ２＝ＣＨＣＦ２ＣＨＦＣＦ３）；４，５，５，５−テトラフルオロ−４−（トリフルオロメチル）−１−ペンテン（ＣＨ２＝ＣＨＣＨ２ＣＦ（ＣＦ３）２）などのハイドロフルオロペンテン： ３，３，４，４，５，５，６，６，６−ノナフルオロ−１−ヘキセン（ＣＦ３ＣＦ２ＣＦ２ＣＦ２ＣＨ＝ＣＨ２）；４，４，５，５，６，６，６−ヘプタフルオロ−１−ヘキセン（ＣＨ２＝ＣＨＣＨ２ＣＦ２ＣＦ２ＣＦ５）などのハイドロフルオロヘキセンが挙げられる。不飽和フッ化炭化水素冷媒の中でも特に分子末端にＣＨ２＝ＣＨ−又はＣＨ２＝ＣＦ−の基を有するものはポリオキシアルキレン構造を有するエーテル系潤滑油とベーンロータリー圧縮機内で反応して重合パラフィンを生成させる程度が分子末端にこれらの基を有しないものよりも顕著である。従って、これらの基を有する不飽和フッ化炭化水素冷媒を使用する冷凍回路に対し本発明の適用は特に有効である。 Examples of the unsaturated fluorinated hydrocarbon refrigerant used in the present invention include 1,2,3,3-tetrafluoro-1-propene (HFC-1234ye); 1,3,3,3-tetrafluoro-1- Propene (HFC-1234ze); 2,3,3,3-tetrafluoro-1-propene (HFC-1234yf); 1,1,2,3-tetrafluoro-1-propene (HFC-1234yc); 1,1 , 3,3-tetrafluoro-1-propene (HFC-1234zc); 2,3,3-trifluoro-1-propene (HFC-1243yf); 3,3,3-trifluoro-1-propene (HFC- 1243zf); 1,1,2-trifluoro-1-propene (HFC-1243yc); 1,1,3-trifluoro-1-propene (HFC-1243zc); 1 2,3-trifluoro-1-propene (HFC-1243ye); 1,3,3-trifluoro-1-propene (HFC-1243ze); 3,3,3-trifluoropropene (HFC-1243zf), etc. Hydrofluoropropene: 2,3,3,4,4,4-hexafluoro-1-butene (CF3CF2CF = CH2); 3,3,3-trifluoro-2- (trifluoromethyl) -1-propene (CH2) = C (CF3) 2); 1,1,1,3,4-pentafluoro-2-butene (CF3CH = CFCH2F); 3,3,4,4,4-pentafluoro-1-butene (CF3CF2CH = CH2) 2,3,3,4,4-pentafluoro-1-butene (CH2 = CFCF2CHF2); 3,3,4,4-tetrafluoro-1-butene (CH = CHCF2CHF2); 3,3-difluoro-2- (difluoromethyl) -1-propene (CH2 = C (CHF2) 2); 3,3,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene (CH2 = C (CF3) CF2CF3); 3,4,4,4-tetrafluoro-3- (trifluoromethyl) -1-butene ((CF3) 2CFCH = CH2); 2,4,4 , 4-tetrafluoro-3- (trifluoromethyl) -1-butene (CH2 = CFCH (CF3) 2); 4,4,4-trifluoro-3- (trifluoromethyl) -1-butene (CH2 = Hydrofluorobutenes such as C (CF3) CH2CF3): 3,3,4,4,5,5,5-heptafluoro-1-pentene (CF3CF2CF2CH = CH2); 4,4,5,5-heptafluoro-1-pentene (CH2 = CFCF2CF2CHF2); 3,3,4,5,5,5-hexafluoro-1-pentene (CH2 = CHCF2CHFCF3); Hydrofluoropentenes such as 5-tetrafluoro-4- (trifluoromethyl) -1-pentene (CH2 = CHCH2CF (CF3) 2): 3,3,4,4,5,5,6,6,6-nonafluoro Examples include hydrofluorohexene such as -1-hexene (CF3CF2CF2CF2CH═CH2); 4,4,5,5,6,6,6-heptafluoro-1-hexene (CH2═CHCH2CF2CF2CF5). Among the unsaturated fluorinated hydrocarbon refrigerants, those having a CH2 = CH- or CH2 = CF- group at the molecular end react with an ether-based lubricating oil having a polyoxyalkylene structure in a vane rotary compressor to produce polymerized paraffin. The degree of generation is more prominent than those not having these groups at the molecular ends. Therefore, the application of the present invention is particularly effective for a refrigeration circuit using an unsaturated fluorinated hydrocarbon refrigerant having these groups.
上記化合物は単独又は２種以上の混合物として使用される。また、上記化合物とともには飽和ハロゲン化炭化水素冷媒又は炭化水素冷媒を併用することも可能である。代表的な飽和フッ化炭化水素冷媒としては、例えば１，１，１，２−テトラフルオロエタン（Ｒ１３４ａ）、１，１−ジフルオロエタン（Ｒ１５２ａ）、ジフルオロメタン（Ｒ３２）、ペンタフルオロエタン（Ｒ１２５）、１，１，１−トリフルオロエタン（Ｒ１４３ａ）、１，１，１，２，３，３，３−ヘプタフルオロプロパン（Ｒ２２７ｅａ）、１，１，１，３，３−ペンタフルオロブタン（Ｒ３６５ｍｆｃ）、２，２，−ジクロロ−１，１，１−トリフルオロエタン（Ｒ１２３）、１，１，１，３，３−ペンタフルオロプロパン（Ｒ２４５ｆａ）、１，２−ジクロロ−１，１，２，２−テトラフルオロエタン（Ｒ１２４）、１，１，１，３，３，３−ヘキサフルオロプロパン（Ｒ２３６ｆａ）が挙げられる。代表的な炭化水素冷媒としては、例えばプロパン、プロピレン、シクロプロパン、ｎ−ブタン、イソブタン、ｎ−ペンタン、２−メチルブタン（イソペンタン）、シクロブタン、シクロペンタン、２，２−ジメチルプロパン、２，２−ジメチルブタン、２，３−ジメチルブタン、２，３−ジメチルペンタン、２−メチルヘキサン、３−メチルヘキサン、２−メチルペンタン、３−エチルペンタン、３−メチルペンタン、シクロヘキサン、ｎ−ヘプタン、メチルシクロペンタン、およびｎ−ヘキサンが挙げられる。 The said compound is used individually or in mixture of 2 or more types. In addition, a saturated halogenated hydrocarbon refrigerant or a hydrocarbon refrigerant can be used in combination with the above compound. Typical saturated fluorinated hydrocarbon refrigerants include, for example, 1,1,1,2-tetrafluoroethane (R134a), 1,1-difluoroethane (R152a), difluoromethane (R32), pentafluoroethane (R125), 1,1,1-trifluoroethane (R143a), 1,1,1,2,3,3,3-heptafluoropropane (R227ea), 1,1,1,3,3-pentafluorobutane (R365mfc) 2,2, -dichloro-1,1,1-trifluoroethane (R123), 1,1,1,3,3-pentafluoropropane (R245fa), 1,2-dichloro-1,1,2, Examples include 2-tetrafluoroethane (R124) and 1,1,1,3,3,3-hexafluoropropane (R236fa). Typical hydrocarbon refrigerants include, for example, propane, propylene, cyclopropane, n-butane, isobutane, n-pentane, 2-methylbutane (isopentane), cyclobutane, cyclopentane, 2,2-dimethylpropane, 2,2- Dimethylbutane, 2,3-dimethylbutane, 2,3-dimethylpentane, 2-methylhexane, 3-methylhexane, 2-methylpentane, 3-ethylpentane, 3-methylpentane, cyclohexane, n-heptane, methylcyclo Examples include pentane and n-hexane.
本発明で使用される長鎖エポキシアルカンとしては、例えば１，２−エポキシノナン、１，２−エポキシデカン、１，２−エポキシウンデカン、１，２−エポキシドデカン、１，２−エポキシテトラデカン、１，２−エポキシペンタデカン、１，２−エポキシヘキサデカン、１，２−エポキシヘプタデカン、１，２−エポキシオクタデカン、１，２−エポキシノナデカンなどの炭素原子数８〜２５のエポキシアルカンが好ましい。長鎖エポキシアルカンのエーテル系潤滑剤に対する添加量は０．５〜１５重量が好ましく、封入冷媒量に対する添加量は０．１〜３重量％が好ましい。 Examples of the long-chain epoxy alkane used in the present invention include 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, Epoxyalkanes having 8 to 25 carbon atoms such as 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane and 1,2-epoxynonadecane are preferred. The addition amount of the long-chain epoxy alkane to the ether lubricant is preferably 0.5 to 15% by weight, and the addition amount to the amount of the encapsulated refrigerant is preferably 0.1 to 3% by weight.
本発明による重合パラフィンの生成防止効果は以下の実施例及び比較例により確認することができる。実施例及び比較例において図１に示される冷凍回路が用いられる。冷凍回路のベーンロータリー圧縮機はアルミニウム合金製のシリンダ、アルミニウム合金製のローター及びアルミニウム合金製のベーンを備えている。冷凍回路内にＨＦＯ１２３４ｙｆ冷媒を所定量充填し、ベーンロータリー圧縮機内に表１に記載の処方の混合物を所定量充填する。実施例及び比較例のエーテル系潤滑油には極圧剤としてリン酸トリクレシルを潤滑油に対し１．０％添加する。ベーンロータリー圧縮機の回転数を６０００ｒｐｍに設定し、この回転速度で４００時間に亘って冷凍回路を連続運転する。運転終了後に圧縮機内及び冷凍回路の配管内を点検してワックス状の固形物（重合パラフィン）の生成の有無を確認する。この確認実験により表１に記載の結果が得られる。表１の効果の欄における判定基準は次の通りである。
○：目視で確認できる固形物は存在しない。
×：目視で確認できる固形物が存在する。
The effect of preventing the formation of polymerized paraffin according to the present invention can be confirmed by the following examples and comparative examples. In the examples and comparative examples, the refrigeration circuit shown in FIG. 1 is used. The vane rotary compressor of the refrigeration circuit includes an aluminum alloy cylinder, an aluminum alloy rotor, and an aluminum alloy vane. A predetermined amount of HFO1234yf refrigerant is filled in the refrigeration circuit, and a predetermined amount of the mixture of the formulations shown in Table 1 is filled in the vane rotary compressor. To the ether-based lubricating oils of Examples and Comparative Examples, 1.0% of tricresyl phosphate as an extreme pressure agent is added to the lubricating oil. The rotational speed of the vane rotary compressor is set to 6000 rpm, and the refrigeration circuit is continuously operated at this rotational speed for 400 hours. After the operation is completed, the inside of the compressor and the piping of the refrigeration circuit are inspected to confirm whether waxy solids (polymerized paraffin) are generated. The results shown in Table 1 are obtained by this confirmation experiment. The judgment criteria in the column of effects in Table 1 are as follows.
○: There is no solid matter that can be visually confirmed.
X: A solid substance that can be visually confirmed exists.
上表において、ＰＰＧはポリプロピレングリコールを主構造として分子末端をエーテル変性処理したポリアルキレングリコールを表し、％は封入冷媒量に対する重量％を表す。
In the above table, PPG represents polyalkylene glycol in which polypropylene glycol is the main structure and the molecular ends are ether-modified, and% represents weight% with respect to the amount of encapsulated refrigerant.
表１に示すように、実施例１〜８のようにエーテル系潤滑油（ＰＡＧ）に重合パラフィン防止剤として長鎖エポキシアルカンを添加する場合には、回転数６０００ｒｐｍ、連続運転時間４００時間の高温高負荷条件下においても、重合パラフィンは発生しないのに対し、比較例にように長鎖エポキシアルカンを添加しない場合には、同条件下において、重合パラフィンが発生する。 As shown in Table 1, when adding a long-chain epoxy alkane as a polymerized paraffin inhibitor to an ether-based lubricating oil (PAG) as in Examples 1 to 8, the rotation speed was 6000 rpm and the continuous operation time was 400 hours. Even under high load conditions, polymerized paraffin is not generated, whereas when no long-chain epoxy alkane is added as in the comparative example, polymerized paraffin is generated under the same conditions.
本発明は家電、住宅空調、流通分野などに利用されるあらゆる冷凍回路に適用可能であり、特に車両空調装置用冷凍回路において、ＨＦＯ１２３４ｙｆなどの不飽和フッ化炭化水素冷媒を使用して環境負荷を低減し且つ従来と同様の動作安定性を達成した冷凍回路を実現することが可能である。 The present invention can be applied to any refrigeration circuit used in home appliances, residential air conditioning, distribution fields, etc., and particularly in a refrigeration circuit for a vehicle air conditioner, using an unsaturated fluorinated hydrocarbon refrigerant such as HFO1234yf to reduce environmental impact. It is possible to realize a refrigeration circuit that reduces and achieves the same operational stability as conventional ones.
１ 冷凍回路
２ 圧縮機
３ 凝縮器
４ 減圧・膨張手段としての膨張弁
５ 蒸発器
DESCRIPTION OF
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| JP2011058748A true JP2011058748A (en) | 2011-03-24 |
| JP5719105B2 JP5719105B2 (en) | 2015-05-13 |
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| JP2009210263A Active JP5719105B2 (en) | 2009-09-11 | 2009-09-11 | Refrigeration circuit |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112012001273T5 (en) | 2011-03-17 | 2013-12-19 | Akebono Brake Industry Co., Ltd. | Electric brake with parking mechanism |
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| WO1997024415A1 (en) * | 1995-12-28 | 1997-07-10 | Daikin Industries, Ltd. | Refrigerating machine oil and refrigerator using same |
| WO2008061079A2 (en) * | 2006-11-14 | 2008-05-22 | Honeywell International Inc. | Fluorocarbon stabilizers |
| WO2008108365A1 (en) * | 2007-03-08 | 2008-09-12 | Idemitsu Kosan Co., Ltd. | Lubricant for compression type refrigerating machine and refrigeration system using the same |
| WO2009057475A1 (en) * | 2007-10-29 | 2009-05-07 | Nippon Oil Corporation | Refrigerator oil and working fluid composition for refrigerating machine |
| WO2009066727A1 (en) * | 2007-11-22 | 2009-05-28 | Idemitsu Kosan Co., Ltd. | Lubricant composition for refrigerating machine and compressor using the same |
| WO2009066722A1 (en) * | 2007-11-22 | 2009-05-28 | Idemitsu Kosan Co., Ltd. | Lubricating oil composition for refrigerating machine |
| JP2009191210A (en) * | 2008-02-15 | 2009-08-27 | Idemitsu Kosan Co Ltd | Lubricating oil composition for refrigerator |
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2009
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997024415A1 (en) * | 1995-12-28 | 1997-07-10 | Daikin Industries, Ltd. | Refrigerating machine oil and refrigerator using same |
| WO2008061079A2 (en) * | 2006-11-14 | 2008-05-22 | Honeywell International Inc. | Fluorocarbon stabilizers |
| WO2008108365A1 (en) * | 2007-03-08 | 2008-09-12 | Idemitsu Kosan Co., Ltd. | Lubricant for compression type refrigerating machine and refrigeration system using the same |
| WO2009057475A1 (en) * | 2007-10-29 | 2009-05-07 | Nippon Oil Corporation | Refrigerator oil and working fluid composition for refrigerating machine |
| WO2009066727A1 (en) * | 2007-11-22 | 2009-05-28 | Idemitsu Kosan Co., Ltd. | Lubricant composition for refrigerating machine and compressor using the same |
| WO2009066722A1 (en) * | 2007-11-22 | 2009-05-28 | Idemitsu Kosan Co., Ltd. | Lubricating oil composition for refrigerating machine |
| JP2009191210A (en) * | 2008-02-15 | 2009-08-27 | Idemitsu Kosan Co Ltd | Lubricating oil composition for refrigerator |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112012001273T5 (en) | 2011-03-17 | 2013-12-19 | Akebono Brake Industry Co., Ltd. | Electric brake with parking mechanism |
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