JP2004512393A - Refrigerant composition for centrifugal compression - Google Patents
Refrigerant composition for centrifugal compression Download PDFInfo
- Publication number
- JP2004512393A JP2004512393A JP2002529229A JP2002529229A JP2004512393A JP 2004512393 A JP2004512393 A JP 2004512393A JP 2002529229 A JP2002529229 A JP 2002529229A JP 2002529229 A JP2002529229 A JP 2002529229A JP 2004512393 A JP2004512393 A JP 2004512393A
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- JP
- Japan
- Prior art keywords
- weight
- composition
- heptafluoropropane
- tetrafluoroethane
- composition according
- 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.)
- Abandoned
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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
- 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
Abstract
テトラフルオロエタンとヘプタフルオロプロパンの濃度の合計が組成物の少なくとも９０重量％であるようにテトラフルオロエタンを少なくとも３５重量％とヘプタフルオロプロパンを少なくとも２０重量％含んで成る液状冷媒組成物を開示する。Disclosed is a liquid refrigerant composition comprising at least 35% by weight of tetrafluoroethane and at least 20% by weight of heptafluoropropane such that the sum of the concentrations of tetrafluoroethane and heptafluoropropane is at least 90% by weight of the composition. .
Description
【０００１】
本発明は冷媒組成物（ｒｅｆｒｉｇｅｒａｎｔ ｃｏｍｐｏｓｉｔｉｏｎｓ）に関する。より詳細には、本発明は、遠心圧縮機が用いられている圧縮冷却装置におけるＲ１２の代わりに使用可能な冷媒組成物に関する。
【０００２】
Ｒ１２（ＣＣｌ２Ｆ２）が長年に亘って冷媒組成物として用いられてきた。しかしながら、ＣＦＣガスの使用に関する懸念を考慮して、その使用量を低くするか或は使用量をゼロにする試みがいろいろなされてきた。言い換えれば、Ｒ１２を環境を害さない配合物に置き換える方法が探求されてきた。
【０００３】
ある程度の効果を伴ってＲ１２の代わりに用いられてきた一つの炭化水素はテトラフルオロエタン（Ｒ１３４）である。その理由はその圧力−温度の関係および冷却効果がＲ１２のそれに類似していることによる。実際、容積移送式圧縮機ではＲ１３４がＲ１２の良好な代替品である。
【０００４】
不幸なことには、遠心圧縮機の使用を伴う装置ではＲ１２の代わりにＲ１３４を用いたのでは満足されない。その理由は、同様な熱力学特性を有する必要があるばかりでなくまた同様な蒸気密度特性も有する必要がある点で冷媒に追加的制約が課せられることにある。おおざっぱに言って、蒸気密度は分子量に関係する。Ｒ１２の分子量は１２１であるが、Ｒ１３４の分子量は僅か１０２である。このような差から遠心圧縮機装置で用いられる圧縮機翼車の寸法を変える必要があるばかりでなくその速度も変える必要がある。明らかに、現存装置を改造することなく使用可能な組成物が求められている。
【０００５】
遠心圧縮機を使用する時に冷媒を用いることに関するさらなる複雑さは、遠心圧縮機に「溢れ（ｆｌｏｏｄｅｄ）」蒸発装置が用いられていることにある、即ち冷却サイクル全体に亘って冷媒液がいくらか残存することにある。その結果として、一般に、この装置に含まれている液状組成物の組成とこの装置の中を循環している蒸気の組成が異なる。
【０００６】
本発明の目的は、圧縮機翼車の寸法も速度も変える必要なく遠心圧縮機が用いられている装置で使用可能な冷媒組成物を提供することにある。明らかに、現存装置を改造することなく使用可能な組成物が求められている。
【０００７】
本発明に従い、驚くべきことに、Ｒ１３４とＲ２２７（ヘプタフルオロプロパン）の特定の液状配合物が遠心圧縮冷却装置におけるＲ１２の代替品として良好に挙動することを見いだした。本発明に従い、テトラフルオロエタンとヘプタフルオロプロパンの濃度が組成物の少なくとも９０重量％であるようにテトラフルオロエタンを少なくとも３５重量％とヘプタフルオロプロパンを少なくとも２０重量％含んで成る液状冷媒組成物を提供する。
【０００８】
テトラフルオロエタンは２種類の形態で存在する。即ち対称的な１，１，２，２−テトラフルオロエタンとＲ１３４ａとして知られる１，１，１，２−テトラフルオロエタンの形態である。この後者が本発明で用いるに好適である。
【０００９】
ヘプタフルオロプロパンも同様に２種類の異性体形態で存在する。即ちＲ２２７ｅａとして知られる１，１，１，２，３，３，３−ヘプタフルオロプロパン（これが好適である）およびＲ２２７ｃａとして知られる１，１，１，２，２，３，３−ヘプタフルオロプロパンの形態である。
【００１０】
この上に示したように、気相中の組成と液相中の組成が異なる。Ｒ２２７を２０から５２重量％含有し、従ってＲ１３４ａを８０から４８重量％含有して成る配合物は蒸気相中でＲ１２の挙動に±１０％のばらつきの範囲で類似した様式の挙動を示す組成を与えることを見いだした。
【００１１】
本発明の好適な組成物は本質的にＲ１３４とＲ２２７、特にＲ１３４ａとＲ２２７ｅａから成る（即ちこれは２成分系組成物である）が、３番目の成分を少量含有させることも可能である。任意の追加的成分、即ち３番目または高級（ｈｉｇｈｅｒ）成分を本組成物の１０重量％以下、好適には５重量％以下、より好適には２重量％以下の量で存在させることもできる。追加的成分を２種以上用いる場合には、これらの成分の総量を１０重量％以下にする。このような配合の主な目的は全体としての分子量を高くし、それにより蒸気密度を高くすることにあることから、Ｒ２２７をいくらか置き換えるのではなくＲ１３４ａをいくらか置き換える方がより一般的である。可能な追加的成分にはＣ３１８（オクタフルオロシクロブタン）、Ｒ２１８（オクタフルオロプロパン）およびＲ１２５（ペンタフルオロエタン）が含まれる。Ｒ１３４の濃度を一般に８０から３５重量％、好適には７０から４５重量％、より好適には５０から６０重量％にする。Ｒ２２７の濃度を一般に２０から６５重量％、好適には３０から５５重量％、特に４０から５０重量％にする。特に好適な配合物はＲ１３４ａを５２．５％とＲ２２７ｅａを４７．５％からなる配合物である。この好適な配合は、全体としての分子量がＲ１２のそれ、即ち１２１に相当するような配合を得る必要があると言った仮定が基になっている。これはＲ１３４ａが約６０％でＲ２２７ｅａが約４０％の蒸気組成を用いて達成される。
【００１２】
しかしながら、この上に示したように、分子量のみでは、ある配合物が蒸気相中でどのような挙動を示すかが完全には描写されない。それを行うには、また、蒸気密度および蒸気圧特性も訂正する必要がある。
【００１３】
他の好適な配合物はそれを考慮に入れることを試みた配合物、即ちＲ２２７含有量が４５重量％に等しいか或はそれ以下、特に３０から４０、４２．５もしくは４５重量％、好適には３５から４２．５もしくは４５重量％、または３５から４０重量％で残りがＲ１３４の配合物であることを見いだした。特に好適な配合物はＲ１３４ａを約６３．３重量％とＲ２２７ｅａを約３６．７重量％含んで成る。Ｒ２２７ｅａの方がＲ１３４ａより高価なことからそのような配合物の方がより安価である。
【００１４】
本発明は、また、遠心圧縮機が用いられている冷却装置の近くに目的物を置くことを含んで成る物体冷却方法も提供し、この方法では、本発明の組成物が前記圧縮機に供給する液状冷媒であり、そして遠心圧縮機が組み込まれている冷却装置も提供し、この装置では、本発明の組成物が前記圧縮機における液体である。
【００１５】
以下に示す実施例で本発明のさらなる説明を行う。
【００１６】
【表１】
分かるであろうように、実施例２および４の配合物が特に良好な蒸気圧および蒸気密度値を与え、これらの値はＲ１２の値に匹敵するか、或は特に３０℃から４０℃（この温度は通常の凝縮温度であることから一般に最も重要である）の時にはＲ１２の値よりも良好でさえある。[0001]
The present invention relates to refrigerant compositions. More specifically, the present invention relates to a refrigerant composition that can be used in place of R12 in a compression cooling device in which a centrifugal compressor is used.
[0002]
R12 (CCl 2 F 2 ) has been used as a refrigerant composition for many years. However, in view of the concerns regarding the use of CFC gas, various attempts have been made to reduce its use or to reduce it to zero. In other words, methods have been sought to replace R12 with environmentally benign formulations.
[0003]
One hydrocarbon that has been used in place of R12 with some effect is tetrafluoroethane (R134). The reason is that its pressure-temperature relationship and its cooling effect is similar to that of R12. In fact, R134 is a good replacement for R12 in positive displacement compressors.
[0004]
Unfortunately, in systems involving the use of a centrifugal compressor, the use of R134 instead of R12 is not satisfactory. The reason for this is that additional restrictions are imposed on the refrigerant in that it must have similar thermodynamic properties as well as similar vapor density properties. Roughly speaking, vapor density is related to molecular weight. The molecular weight of R12 is 121, while the molecular weight of R134 is only 102. Due to such differences, it is necessary to change not only the size of the compressor wheel used in the centrifugal compressor device but also the speed thereof. Clearly, there is a need for a composition that can be used without retrofitting existing equipment.
[0005]
An additional complication with using a refrigerant when using a centrifugal compressor is that a centrifugal compressor uses a "flooded" evaporator, ie, some refrigerant liquid remains throughout the cooling cycle. Is to do. As a result, the composition of the liquid composition contained in the device and the composition of the vapor circulating in the device are generally different.
[0006]
An object of the present invention is to provide a refrigerant composition that can be used in a device in which a centrifugal compressor is used without having to change the size and speed of the compressor wheel. Clearly, there is a need for a composition that can be used without retrofitting existing equipment.
[0007]
In accordance with the present invention, it has surprisingly been found that certain liquid formulations of R134 and R227 (heptafluoropropane) perform well as a replacement for R12 in centrifugal compression chillers. According to the present invention, there is provided a liquid refrigerant composition comprising at least 35% by weight of tetrafluoroethane and at least 20% by weight of heptafluoropropane such that the concentration of tetrafluoroethane and heptafluoropropane is at least 90% by weight of the composition. provide.
[0008]
Tetrafluoroethane exists in two forms. That is, it is a symmetric form of 1,1,2,2-tetrafluoroethane and 1,1,1,2-tetrafluoroethane known as R134a. This latter is preferred for use in the present invention.
[0009]
Heptafluoropropane also exists in two isomeric forms. 1,1,1,2,3,3,3-heptafluoropropane known as R227ea (which is preferred) and 1,1,1,2,2,3,3-heptafluoropropane known as R227ca It is a form of.
[0010]
As shown above, the composition in the gas phase is different from the composition in the liquid phase. Formulations containing from 20 to 52% by weight of R227 and thus from 80 to 48% by weight of R134a have compositions which behave in the vapor phase in a manner similar to the behavior of R12 with a variation of ± 10%. I found something to give.
[0011]
Preferred compositions of the present invention consist essentially of R134 and R227, especially R134a and R227ea (ie, this is a two-component composition), but can also contain a small amount of the third component. An optional additional component, a third or higher component, may be present in an amount up to 10%, preferably up to 5%, more preferably up to 2% by weight of the composition. If more than one additional component is used, the total amount of these components should not exceed 10% by weight. It is more common to replace some R134a rather than some R227, since the primary purpose of such a formulation is to increase the overall molecular weight and thereby the vapor density. Possible additional components include C318 (octafluorocyclobutane), R218 (octafluoropropane) and R125 (pentafluoroethane). The concentration of R134 is generally between 80 and 35% by weight, preferably between 70 and 45% by weight, more preferably between 50 and 60% by weight. The concentration of R227 is generally between 20 and 65% by weight, preferably between 30 and 55% by weight, in particular between 40 and 50% by weight. A particularly preferred formulation is a formulation comprising 52.5% R134a and 47.5% R227ea. This preferred formulation is based on the assumption that it is necessary to obtain a formulation whose overall molecular weight corresponds to that of R12, ie 121. This is achieved with a vapor composition of about 60% R134a and about 40% R227ea.
[0012]
However, as shown above, molecular weight alone does not completely describe how certain formulations behave in the vapor phase. To do so, the vapor density and vapor pressure characteristics also need to be corrected.
[0013]
Other suitable formulations are those which have attempted to take this into account, i.e. the R227 content is equal to or less than 45% by weight, in particular from 30 to 40, 42.5 or 45% by weight, preferably Found 35 to 42.5 or 45% by weight, or 35 to 40% by weight, with the remainder being a formulation of R134. A particularly preferred formulation comprises about 63.3% by weight R134a and about 36.7% by weight R227ea. Such formulations are less expensive because R227ea is more expensive than R134a.
[0014]
The invention also provides a method of cooling an object, comprising placing an object near a cooling device in which a centrifugal compressor is used, wherein the composition of the invention is supplied to said compressor. Also provided is a refrigeration system which is a liquid refrigerant which incorporates a centrifugal compressor, wherein the composition of the invention is the liquid in said compressor.
[0015]
The following examples further illustrate the present invention.
[0016]
[Table 1]
As can be seen, the formulations of Examples 2 and 4 give particularly good vapor pressure and vapor density values, which are comparable to the values of R12, or in particular from 30 ° C to 40 ° C (this Temperature is generally the most important since it is the normal condensation temperature) even better than the value of R12.
Claims (13)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/GB2000/003596 WO2002024829A1 (en) | 2000-09-19 | 2000-09-19 | Centrifugal compression refrigerant compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004512393A true JP2004512393A (en) | 2004-04-22 |
Family
ID=9885742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002529229A Abandoned JP2004512393A (en) | 2000-09-19 | 2000-09-19 | Refrigerant composition for centrifugal compression |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1325097A1 (en) |
| JP (1) | JP2004512393A (en) |
| AU (2) | AU7302100A (en) |
| BR (1) | BR0017337B1 (en) |
| CA (1) | CA2424842A1 (en) |
| CZ (1) | CZ2003734A3 (en) |
| WO (1) | WO2002024829A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK0998539T3 (en) | 1997-07-15 | 2002-10-28 | Rhodia Ltd | refrigerant compositions |
| US7258813B2 (en) | 1999-07-12 | 2007-08-21 | E.I. Du Pont De Nemours And Company | Refrigerant composition |
| GB0223724D0 (en) | 2002-10-11 | 2002-11-20 | Rhodia Organique Fine Ltd | Refrigerant compositions |
| EP1572829B1 (en) | 2002-11-29 | 2011-11-09 | E.I. Du Pont De Nemours And Company | Chiller refrigerants |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| AU4649593A (en) * | 1992-06-25 | 1994-01-24 | Great Lakes Chemical Corporation | Refrigerant blends containing 1,1,1,2,3,3,3-heptafluoropropane |
| WO1999025786A1 (en) * | 1997-11-18 | 1999-05-27 | Alliedsignal Inc. | Hydrofluorocarbon refrigerants |
-
2000
- 2000-09-19 JP JP2002529229A patent/JP2004512393A/en not_active Abandoned
- 2000-09-19 WO PCT/GB2000/003596 patent/WO2002024829A1/en active Application Filing
- 2000-09-19 AU AU7302100A patent/AU7302100A/en active Pending
- 2000-09-19 BR BRPI0017337-1A patent/BR0017337B1/en not_active IP Right Cessation
- 2000-09-19 EP EP00960853A patent/EP1325097A1/en not_active Withdrawn
- 2000-09-19 CZ CZ2003734A patent/CZ2003734A3/en unknown
- 2000-09-19 CA CA002424842A patent/CA2424842A1/en not_active Abandoned
- 2000-09-19 AU AU2000273021A patent/AU2000273021B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| CZ2003734A3 (en) | 2003-09-17 |
| AU2000273021B2 (en) | 2006-09-14 |
| CA2424842A1 (en) | 2002-03-28 |
| BR0017337A (en) | 2003-07-29 |
| EP1325097A1 (en) | 2003-07-09 |
| BR0017337B1 (en) | 2010-11-03 |
| AU7302100A (en) | 2002-04-02 |
| WO2002024829A1 (en) | 2002-03-28 |
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