JPH0742454B2 - Working medium mixture - Google Patents
Working medium mixtureInfo
- Publication number
- JPH0742454B2 JPH0742454B2 JP62142335A JP14233587A JPH0742454B2 JP H0742454 B2 JPH0742454 B2 JP H0742454B2 JP 62142335 A JP62142335 A JP 62142335A JP 14233587 A JP14233587 A JP 14233587A JP H0742454 B2 JPH0742454 B2 JP H0742454B2
- Authority
- JP
- Japan
- Prior art keywords
- working medium
- mixture
- medium mixture
- temperature
- present
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
Classifications
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
- Y02B30/52—Heat recovery pumps, i.e. heat pump based systems or units able to transfer the thermal energy from one area of the premises or part of the facilities to a different one, improving the overall efficiency
-
- 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
Landscapes
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、冷凍機、ヒートポンプ等に使用し得る新規な
作動媒体混合物に関する。TECHNICAL FIELD The present invention relates to a novel working medium mixture that can be used in refrigerators, heat pumps and the like.
［従来技術］ 空調，冷凍および冷蔵機器（冷凍サイクル・ヒートポン
プサイクル）、廃熱回収発電（ランキンサイクル）、熱
交換機器（ヒートパイプ）等が実用化しない試験開発さ
れている。[Prior Art] Air conditioning, refrigeration and refrigeration equipment (refrigeration cycle / heat pump cycle), waste heat recovery power generation (Rankine cycle), heat exchange equipment (heat pipe), etc. have been tested and developed for practical use.
これらの機器に用いる作動媒体には、水をはじめプロパ
ンやブタン等の炭化水素類，トリクロロモノフルオロメ
タン（Ｒ−11）や、1,2−ジクロロテトラフルオロエタ
ン（Ｒ−114）等のフロン類、又はアンモニア等が知ら
れている。The working medium used in these devices includes water, hydrocarbons such as propane and butane, and fluorocarbons such as trichloromonofluoromethane (R-11) and 1,2-dichlorotetrafluoroethane (R-114). , Or ammonia is known.
［発明の目的］ フロン類は毒性が少なく、非可燃性で化学的にも安定で
あり、沸点の異なる各種フロンが容易に入手できること
から、作動媒体としての評価研究が活発に行なわれてい
る。本発明者等は、熱回収効率（特に、冷凍庫，冷蔵
庫，冷暖房機器，給湯機器あるいは廃熱回収を目的とし
たヒートポンプなど）の高いフロン類の探索を進めた結
果、テトラフルオロエタンと標準沸点として−50〜−35
℃を有するハロゲン化炭化水素、特に水素原子を少なく
とも１つ含むハロゲン化炭化水素よりなる作動媒体混合
物は、混合前の単独成分に比べ、成績係数や冷凍能力等
が改善し得ることを見出すことができた。本発明は、こ
のような作動媒体混合物を新規に提案するものである。[Object of the Invention] CFCs are less toxic, non-flammable, chemically stable, and various CFCs having different boiling points are easily available. Therefore, evaluation studies as working media have been actively conducted. The present inventors have advanced the search for CFCs having high heat recovery efficiency (in particular, a freezer, a refrigerator, an air conditioner, a water heater, a heat pump for recovering waste heat, etc.), and as a result, tetrafluoroethane and −50 to −35
It has been found that a working medium mixture composed of a halogenated hydrocarbon having a temperature of 0 ° C., particularly a halogenated hydrocarbon containing at least one hydrogen atom, can improve the coefficient of performance, the refrigerating capacity, etc., as compared with a single component before mixing. did it. The present invention newly proposes such a working medium mixture.
［発明の構成］ 本発明における、テトラフルオロエタンには、1,1,2,2
−テトラフルオロエタン（Ｒ−134）と1,1,1,2−テトラ
フルオロエタン（Ｒ−134a）の２種類の異性体が知られ
ているが、互いに物性が類似しているため、これらを単
独で用いてもよく、また、これらの混合物を用いても良
い。[Structure of the Invention] In the present invention, tetrafluoroethane includes 1,1,2,2
-Two types of isomers, tetrafluoroethane (R-134) and 1,1,1,2-tetrafluoroethane (R-134a), are known, but they are similar in physical properties to each other. They may be used alone or as a mixture thereof.
標準沸点として−50〜−35℃を有するハロゲン化炭化水
素としては、以下の化合物が好ましい。なお、標準沸点
として−50℃以下を有するハロゲン化炭化水素は、テト
ラフルオロエタンとの標準沸点の差が極めて大きく、圧
力一定の状態での露点温度および沸点温度の差が極めて
大きくなり、熱源流体および負荷流体の熱交換器での温
度勾配を考慮しても実用的でない。さらに、標準沸点と
して−50℃以下を有するハロゲン化炭化水素を混合使用
する場合は、高圧が極めて高くなってしまう欠点があ
る。反対に、標準沸点として−35℃以上を有するハロゲ
ン化炭化水素を混合した場合は、共沸混合物を形成する
特殊な場合を除き、一般に、圧縮機単位容積当りの冷凍
能力が低下するとともに、低圧が極めて低くなってしま
い実用的でない。また、ハロゲン化炭化水素のなかで、
水素原子を１つ以上含む化合物は、水素原子を全く含ま
ない化合物に比し、蒸発潜熱が大きくなる傾向があり、
冷凍能力、加熱能力および成績係数の向上にとって好ま
いいことを見出した。なお、ハロゲン化炭化水素として
は、単独またはこれら混合物を用いても良い。さらに、
ハロゲン化炭化水素の中で、異性体が存在する場合は、
単独、または混合使用しても良い。The following compounds are preferable as the halogenated hydrocarbon having a normal boiling point of −50 to −35 ° C. Halogenated hydrocarbons having a standard boiling point of -50 ° C or less have a very large difference in standard boiling point from tetrafluoroethane, and a very large difference in dew point temperature and boiling point temperature under a constant pressure condition. It is not practical even considering the temperature gradient in the heat exchanger of the load fluid. Further, when a halogenated hydrocarbon having a normal boiling point of -50 ° C or lower is mixed and used, there is a drawback that the high pressure becomes extremely high. On the other hand, when a halogenated hydrocarbon having a normal boiling point of −35 ° C. or higher is mixed, the refrigerating capacity per unit volume of the compressor is generally reduced, and the low pressure is reduced except for a special case of forming an azeotropic mixture. Is too low to be practical. Also, among halogenated hydrocarbons,
Compounds containing one or more hydrogen atoms tend to have higher latent heat of vaporization than compounds containing no hydrogen atoms,
We have found that it is good for improving freezing capacity, heating capacity and coefficient of performance. The halogenated hydrocarbon may be used alone or as a mixture thereof. further,
Among the halogenated hydrocarbons, if isomers exist,
You may use individually or in mixture.
メタン誘導体としては、CHClF2（R22）を挙げることが
できる。Examples of the methane derivative include CHClF 2 (R22).
エタン誘導体としては、CClF2−CF3（R115）、CHF2−CF
3（R125）、CF3−CH3（R143a）、CH2F−CH3（R161）を
挙げることができる。As ethane derivatives, CClF 2 -CF 3 (R115), CHF 2 -CF
3 (R125), CF 3 -CH 3 (R143a), mention may be made of CH 2 F-CH 3 (R161 ).
共沸混合媒体としては、R502（R22/R115混合物）を挙げ
ることができる。As the azeotropic mixture medium, R502 (R22 / R115 mixture) can be mentioned.
以下、本発明の作動媒体を用いた冷凍サイクルシステム
のフローシートを示す第１図に従って本発明を詳細に説
明する。第１図の１は圧縮機、２は凝縮器、3,3′は負
荷流体用配管、４は減圧装置、５は蒸発器、6,6′は熱
源流体用配管を示す。Hereinafter, the present invention will be described in detail with reference to FIG. 1 showing a flow sheet of a refrigeration cycle system using the working medium of the present invention. In FIG. 1, 1 is a compressor, 2 is a condenser, 3 and 3'are load fluid pipes, 4 is a pressure reducing device, 5 is an evaporator, and 6 and 6'are heat source fluid pipes.
第１図に示す冷凍サイクルシステムにおいて作動媒体は
圧縮機１で圧縮された後、凝集器２に導かれ、該凝縮器
２中で管３より導入される負荷流体により冷却されて凝
縮する。一方、負荷流体は凝縮器２中で逆に加熱され管
３′を経て負荷加熱に供される。つぎに凝縮した作動媒
体は減圧装置４により減圧された後、蒸発器に導かれ、
該蒸発器５中で管６より導入され管６′から排出される
熱源流体により加熱された後、再び圧縮機１に吸引され
上記のサイクルを繰り返す。一方、熱源流体は蒸発器５
中で逆に冷却され、管６′を経て冷却に供される。In the refrigeration cycle system shown in FIG. 1, the working medium is compressed by the compressor 1, then guided to the aggregator 2, and cooled and condensed by the load fluid introduced from the pipe 3 in the condenser 2. On the other hand, the load fluid is inversely heated in the condenser 2 and supplied to the load heating through the pipe 3 '. Next, the condensed working medium is decompressed by the decompression device 4 and then guided to the evaporator,
After being heated in the evaporator 5 by the heat source fluid introduced from the pipe 6 and discharged from the pipe 6 ', it is sucked into the compressor 1 again and the above cycle is repeated. On the other hand, the heat source fluid is the evaporator 5
Inside it is cooled in reverse and subjected to cooling via pipe 6 '.
第２図及び第３図は第１図に示す冷凍サイクルシステム
における作動媒体のサイクルを圧力−エンタルピー線図
上に記入したものである。作動媒体の飽和蒸気を断熱圧
縮した場合、湿り状態になるものを第２図に、乾き状態
になるものを第３図に示す。2 and 3 are diagrams in which the cycle of the working medium in the refrigeration cycle system shown in FIG. 1 is entered on the pressure-enthalpy diagram. When saturated vapor of the working medium is adiabatically compressed, a wet state is shown in FIG. 2 and a dry state is shown in FIG.
第１図の圧縮機による作動媒体の変化は第２図及び第３
図の符号８から９あるいは13から14の変化に、凝縮器に
作動媒体の変化は９→10→11→あるいは14→15→16→17
の変化に、減圧装置による作動媒体の変化は11から12あ
るいは17から18の変化に、蒸発器による作動媒体の変化
は12から８あるいは18から13の変化にそれぞれ対応す
る。The change of the working medium by the compressor of FIG. 1 is shown in FIGS.
The change from 8 to 9 or 13 to 14 in the figure, the change of working medium in the condenser is 9 → 10 → 11 → or 14 → 15 → 16 → 17
Change of the working medium by the decompressor corresponds to the change of 11 to 12 or 17 to 18, and the change of the working medium by the evaporator corresponds to the change of 12 to 8 or 18 to 13, respectively.
本発明の作動媒体を用いた第１図の冷凍サイクルシステ
ムの運転条件として蒸発器における作動媒体の蒸発終り
温度（符号７あるいは13の温度。以下、蒸発温度とい
う）と凝縮器における作動媒体の凝縮始めの温度（符号
９あるいは15の温度。以下、凝縮温度という）を設定し
た。第１表から第３表に本発明の作動媒体を用いた上記
の冷凍サイクルシステムにおける成績係数、圧縮機単位
排除体積当りの冷凍能力を記す。As the operating conditions of the refrigeration cycle system of FIG. 1 using the working medium of the present invention, the end temperature of evaporation of the working medium in the evaporator (the temperature of reference numeral 7 or 13; hereinafter referred to as the evaporation temperature) and the condensation of the working medium in the condenser The initial temperature (the temperature of code 9 or 15; hereinafter referred to as the condensation temperature) was set. Tables 1 to 3 show the coefficient of performance and the refrigerating capacity per unit excluded volume of the compressor in the refrigeration cycle system using the working medium of the present invention.
表から理解されるように混合することにより、混合前の
単独成分に比べ成績係数や冷凍能力が改善されている。
成績係数が大きいと消費電力が少なくて済むため好まし
く、冷凍能力が大きいと冷凍装置が小さくて済むため好
ましい。成績係数を重視した好ましい混合組成（モル
比）は、例えばR22/R134aでは1/99〜99〜１、R125/R134
aでは1/99〜40/60、R502〜R134aでは1/99〜50/50であ
る。また、成績係数を維持しながら冷凍能力を重視した
好ましい混合組成（モル比）は、例えばR125/R134aでは
1/99〜99/1、R502/R134aでは1/99〜99/1である。As can be seen from the table, by mixing, the coefficient of performance and the refrigerating capacity are improved as compared with the single component before mixing.
A large coefficient of performance is preferable because it consumes less power, and a large refrigerating capacity is preferable because a refrigerating apparatus is small. The preferred mixed composition (molar ratio) with an emphasis on the coefficient of performance is, for example, R22 / R134a, which is 1/99 to 99-1 and R125 / R134.
It is 1/99 to 40/60 for a and 1/99 to 50/50 for R502 to R134a. In addition, the preferred mixture composition (molar ratio) that emphasizes refrigerating capacity while maintaining the coefficient of performance is, for example, in R125 / R134a.
1/99 to 99/1, and 1/99 to 99/1 for R502 / R134a.
本発明の作動媒体混合物は低温〜中温、高温分野の空
調、冷凍および冷蔵を目的とした冷凍サイクルに応用す
る場合に特に有効であるが、ランキンサイクル用あるい
は、その他各種の熱回収技術用の作動媒体として使用す
ることもできる。本発明の作動媒体混合物は熱安定性が
優れており、通常の使用条件においては安定剤を必要と
しないが、苛酷な使用条件のため熱安定性の向上が必要
な場合には、ジメチルホスファイト、ジイソプロピルホ
スファイト、ジフェニルホスファイト等のホスファイト
系化合物、又はチオホスファイト系化合物、あるいはト
リフェノキシホスフインサルファイド、トリメチルホス
フインサルファイド等のホスフインサルファイド系化合
物、その他の安定剤を作動媒体100重量部に対し、１重
量部前後の少量添加すればよい。The working medium mixture of the present invention is particularly effective when applied to a refrigeration cycle for the purpose of air conditioning, refrigeration and refrigeration in low-to-medium temperature and high-temperature fields, but it operates for Rankine cycle or other various heat recovery techniques. It can also be used as a medium. The working medium mixture of the present invention has excellent thermal stability and does not require a stabilizer under normal use conditions, but when it is necessary to improve heat stability due to severe use conditions, dimethyl phosphite is used. Phosphite-based compounds such as diisopropyl phosphite and diphenyl phosphite, or thiophosphite-based compounds, or phosphine sulfide-based compounds such as triphenoxyphosphine sulfide and trimethylphosphine sulfide, and other stabilizers as a working medium 100% by weight A small amount of about 1 part by weight may be added to each part.
［発明の効果］ 本発明の作動媒体混合物は、冷凍サイクル効率すなわち
冷凍、加熱効率に優れ、混合前の単独成分に比し、大幅
な改善が認められる。 [Effects of the Invention] The working medium mixture of the present invention is excellent in refrigeration cycle efficiency, that is, refrigeration and heating efficiency, and is significantly improved as compared with the single component before mixing.
【図面の簡単な説明】 第１図は本発明の１実施例を説明するための冷凍サイク
ルのフローシート、第２図および第３図は本発明の作動
媒体混合物を用いたサイクルを圧力−エンタルピー線図
に記入した図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart of a refrigeration cycle for explaining one embodiment of the present invention, and FIGS. 2 and 3 show a pressure-enthalpy cycle of a working medium mixture of the present invention. It is the figure which entered in the diagram.
Claims (2)
50〜−35℃であるハロゲン化炭化水素を必須成分とする
ことを特徴とする作動媒体混合物。1. Tetrafluoroethane and normal boiling point of −
A working medium mixture comprising a halogenated hydrocarbon of 50 to -35 ° C as an essential component.
を１つ含む化合物である特許請求の範囲第１項記載の作
動媒体混合物。2. The working medium mixture according to claim 1, wherein the halogenated hydrocarbon is a compound containing at least one hydrogen atom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62142335A JPH0742454B2 (en) | 1987-06-09 | 1987-06-09 | Working medium mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62142335A JPH0742454B2 (en) | 1987-06-09 | 1987-06-09 | Working medium mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63308085A JPS63308085A (en) | 1988-12-15 |
| JPH0742454B2 true JPH0742454B2 (en) | 1995-05-10 |
Family
ID=15312964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62142335A Expired - Lifetime JPH0742454B2 (en) | 1987-06-09 | 1987-06-09 | Working medium mixture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0742454B2 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0730311B2 (en) * | 1987-09-21 | 1995-04-05 | ダイキン工業株式会社 | Coolant |
| JPH075880B2 (en) * | 1987-09-21 | 1995-01-25 | ダイキン工業株式会社 | Coolant |
| JP2596776B2 (en) * | 1988-02-04 | 1997-04-02 | 株式会社荏原製作所 | heat pump |
| AU7470991A (en) * | 1990-03-23 | 1991-10-21 | California Institute Of Technology | Near azeotropic mixture substitute for dichlorodifluoromethane |
| JP2792191B2 (en) * | 1990-04-04 | 1998-08-27 | ダイキン工業株式会社 | Coolant |
| DE69118208T2 (en) * | 1990-07-26 | 1996-09-05 | E.I. Du Pont De Nemours And Co., Wilmington, Del. | Quasi-azeotropic mixtures for use as refrigerants |
| BE1005222A3 (en) * | 1991-01-18 | 1993-06-01 | Solvay | Compositions comprising 1,1,1,2-tetrafluoroethane and uses thereof. |
| US5725791A (en) * | 1991-03-28 | 1998-03-10 | E. I. Du Pont De Nemours And Company | Azeotropic and azeotrope-like compositions of 1,1,2,2-tetrafluoroethane |
| US5182040A (en) * | 1991-03-28 | 1993-01-26 | E. I. Du Pont De Nemours And Company | Azeotropic and azeotrope-like compositions of 1,1,2,2-tetrafluoroethane |
| US5622645A (en) * | 1992-01-24 | 1997-04-22 | Gu; Chujun | Nonazeotropic working fluid media for use in thermodynamic cycle applications |
| US5458798A (en) * | 1993-02-05 | 1995-10-17 | E. I. Du Pont De Nemours And Company | Azeotropic and azeotrope-like compositions of a hydrofluorocarbon and a hydrocarbon |
| JP2867932B2 (en) * | 1995-12-14 | 1999-03-10 | ダイキン工業株式会社 | Coolant |
| WO1997031080A1 (en) * | 1996-02-21 | 1997-08-28 | E.I. Du Pont De Nemours And Company | Refrigerant composition comprising 1,1,2,2-tetrafluoroethane |
| US8444873B2 (en) | 2009-06-12 | 2013-05-21 | Solvay Fluor Gmbh | Refrigerant composition |
-
1987
- 1987-06-09 JP JP62142335A patent/JPH0742454B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63308085A (en) | 1988-12-15 |
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