JPH04243523A - Removal of chlorotrifluoroethane in dichlorofluoroethane - Google Patents
Removal of chlorotrifluoroethane in dichlorofluoroethaneInfo
- Publication number
- JPH04243523A JPH04243523A JP3022886A JP2288691A JPH04243523A JP H04243523 A JPH04243523 A JP H04243523A JP 3022886 A JP3022886 A JP 3022886A JP 2288691 A JP2288691 A JP 2288691A JP H04243523 A JPH04243523 A JP H04243523A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- trifluoroethane
- activated carbon
- type
- dichloro
- 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.)
- Withdrawn
Links
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 title claims abstract description 5
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 title 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 19
- 239000010457 zeolite Substances 0.000 claims abstract description 19
- FWAQVJAOVDYHAF-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethane Chemical compound FC(F)C(F)Cl FWAQVJAOVDYHAF-UHFFFAOYSA-N 0.000 claims abstract description 18
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical group FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 239000010721 machine oil Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 208000005623 Carcinogenesis Diseases 0.000 abstract 1
- 230000036952 cancer formation Effects 0.000 abstract 1
- 231100000504 carcinogenesis Toxicity 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000003507 refrigerant Substances 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、１，１−ジクロロ−２
，２，２−トリフルオロエタン（Ｒ１２３）中の１−ク
ロロ−２，２，２−トリフルオロエタン（Ｒ１３３ａ）
を除去する方法に関するものである。[Industrial Field of Application] The present invention relates to 1,1-dichloro-2
, 1-chloro-2,2,2-trifluoroethane (R133a) in 2,2-trifluoroethane (R123)
The present invention relates to a method for removing .
【０００２】0002
【従来の技術】Ｒ１２３は、規制対象フロンのトリクロ
ロフルオロメタン（Ｒ１１）にかわるターボ冷凍機の冷
媒として、あるいはポリウレタン発泡剤であるＲ１１に
かわる発泡剤として有望な化合物である。BACKGROUND OF THE INVENTION R123 is a promising compound as a refrigerant for centrifugal refrigerators in place of trichlorofluoromethane (R11), a regulated fluorocarbon, and as a blowing agent in place of R11, a polyurethane blowing agent.
【０００３】しかしながら、Ｒ１２３は冷凍機油や金属
等の共存下で分解し、発癌性の疑いがあるＲ１３３ａを
微量ではあるが発生するという新たな問題が提起されて
いる。[0003] However, a new problem has been raised in that R123 decomposes in the coexistence of refrigerating machine oil, metals, etc., and generates a small amount of R133a, which is suspected of being carcinogenic.
【０００４】0004
【発明が解決しようとする課題】本発明は、前述の問題
を解決すべく、Ｒ１２３中のＲ１３３ａを選択的に除去
するものである。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention selectively removes R133a from R123.
【０００５】[0005]
【課題を解決するための手段】本発明は、前述の課題を
解決すべくなされたものであり、１−クロロ−２，２，
２−トリフルオロエタン（Ｒ１３３ａ）を含む１，１−
ジクロロ−２，２，２−トリフルオロエタン（Ｒ１２３
）を活性炭又はゼオライトと接触させ、Ｒ１２３中のＲ
１３３ａの含有量を１０ｐｐｍ以下とすることを特徴と
するＲ１２３中のＲ１３３ａを除去する方法を提供する
ものである。[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems.
1,1- containing 2-trifluoroethane (R133a)
Dichloro-2,2,2-trifluoroethane (R123
) in contact with activated carbon or zeolite, R in R123
The present invention provides a method for removing R133a from R123, characterized in that the content of 133a is 10 ppm or less.
【０００６】Ｒ１２３は、規制対象フロンのＲ１１にか
わる化合物として有力であり、例えばターボ冷凍機用冷
媒やポリウレタン発泡剤として注目されている。[0006] R123 is a promising compound as a substitute for R11, which is a regulated fluorocarbon, and is attracting attention as a refrigerant for centrifugal refrigerators and a polyurethane blowing agent, for example.
【０００７】ターボ冷凍機は、運転中冷媒系統が真空に
なるため、不良の箇所があると周囲の空気が系統内に漏
入することはさけられない。空気が漏入すると凝縮器な
どに滞留して熱交換を阻害し、サイクルの効率を低下さ
せ故障の原因となる。[0007] Since the refrigerant system of a centrifugal refrigerator is in a vacuum state during operation, it is inevitable that surrounding air will leak into the system if there is a defective part. If air leaks, it will accumulate in the condenser etc., inhibiting heat exchange, reducing cycle efficiency and causing failure.
【０００８】このため、ターボ冷凍機には抽気装置を設
置し、１日の運転中、数分程度空気を含んだ冷媒を排出
する。[0008] For this reason, the centrifugal chiller is equipped with an air extraction device, and the refrigerant containing air is discharged for several minutes during one day's operation.
【０００９】ターボ冷凍機中のＲ１２３は、冷凍機油や
共存する金属の影響で分解し、発癌性の疑いがあるＲ１
３３ａを生成する。従って抽気装置から排出されるＲ１
２３中にはＲ１３３ａが微量含まれており、その除去が
必要である。[0009] R123 in centrifugal refrigerators decomposes under the influence of refrigerating machine oil and coexisting metals, and is suspected of being carcinogenic.
33a. Therefore R1 discharged from the bleed system
23 contains a trace amount of R133a, which needs to be removed.
【００１０】Ｒ１３３ａを含んだＲ１２３を活性炭又は
ゼオライトと接触させることにより、Ｒ１３３ａを吸着
除去することができ、Ｒ１２３中のＲ１３３ａの濃度を
無害なレベルである１０ｐｐｍ以下とすることができる
。活性炭とゼオライトは併用することもできる。[0010] By bringing R123 containing R133a into contact with activated carbon or zeolite, R133a can be adsorbed and removed, and the concentration of R133a in R123 can be reduced to a harmless level of 10 ppm or less. Activated carbon and zeolite can also be used together.
【００１１】活性炭は、ヤシガラ系、木炭系、石炭系、
石油ピッチ系等各種の活性炭を採用可能であり、細孔径
が３〜１０Åであるものが好ましい。活性炭の形状は、
粉末又は造粒品あるいは繊維状品を採用することができ
る。[0011] Activated carbon is coconut shell based, charcoal based, coal based,
Various activated carbons such as petroleum pitch type activated carbon can be used, and those having a pore diameter of 3 to 10 Å are preferable. The shape of activated carbon is
Powder, granulated products, or fibrous products can be used.
【００１２】ゼオライトは、下記一般式で表わされるケ
イ酸塩に属する鉱物の一種で天然又は合成物が知られて
いる。Zeolite is a type of mineral belonging to the silicate group represented by the following general formula, and is known as a natural or synthetic product.
【００１３】
Ｍｘ／ｎ ［（ＡｌＯ２）ｘ ・（ＳｉＯ２）ｙ ］・
ｗＨ２ Ｏここで、ｎは陽イオンＭ（Ｎａ，Ｋ，Ｃａ等
アルカリ金属，アルカリ土類金属の元素）の個数、ｗは
単位格子あたりの水分、ｘおよびｙは単位格子あたりの
四面体の全個数である。Mx/n [(AlO2)x ・(SiO2)y ]・
wH2O where n is the number of cations M (alkali metals and alkaline earth metal elements such as Na, K, Ca, etc.), w is water per unit cell, x and y are the total number of tetrahedra per unit cell. It is the number of pieces.
【００１４】又、合成ゼオライトとしてはＡ型ゼオライ
ト、Ｘ型ゼオライト、Ｙ型ゼオライトなどが知られてお
り、本発明のゼオライトには、天然又は合成ゼオライト
を使うことができる。ゼオライトの細孔径は３〜１０Å
であるものが特に好ましい。Also, known synthetic zeolites include A-type zeolite, X-type zeolite, and Y-type zeolite, and natural or synthetic zeolites can be used as the zeolite of the present invention. The pore diameter of zeolite is 3 to 10 Å
Particularly preferred are those.
【００１５】合成ゼオライトの形状は０．５〜５ｍｍ程
度の粒状又は円筒状のものが好ましく、粉末状のゼオラ
イトをベントナイト等の結合剤で固めたものである。ゼ
オライトは、使用前に２００〜４００℃で１〜３時間加
熱処理して活性化しておくことが好ましい。The shape of the synthetic zeolite is preferably granular or cylindrical with a size of about 0.5 to 5 mm, and is obtained by hardening powdered zeolite with a binder such as bentonite. The zeolite is preferably activated by heat treatment at 200 to 400°C for 1 to 3 hours before use.
【００１６】Ｒ１３３ａを含んだＲ１２３を活性炭又は
ゼオライトに接触させる時間や温度あるいは圧力等、特
に限定されるものではないが、およそ５〜１２０秒の接
触時間、室温〜６０℃の温度、常圧〜２ｋｇ／ｃｍ２
（ゲージ圧）が好ましい。[0016] There are no particular limitations on the time, temperature, or pressure in which R123 containing R133a is brought into contact with activated carbon or zeolite, but the contact time is approximately 5 to 120 seconds, the temperature is room temperature to 60°C, and the pressure is normal pressure to 2kg/cm2
(gauge pressure) is preferred.
【００１７】[0017]
【実施例】合成ゼオライト又は活性炭を充填した内径２
５ｍｍ、長さ１８０ｍｍのステンレス製容器を、ターボ
冷凍機の抽気回収装置の排出口へ設置し、常圧、約２５
℃でＲ１３３ａを含むＲ１２３を通した。この容器への
入口及び出口におけるＲ１２３中のＲ１３３ａの濃度を
ガスクロマトグラフ法により測定した。結果を表１に示
す。[Example] Inner diameter 2 filled with synthetic zeolite or activated carbon
A stainless steel container with a diameter of 5 mm and a length of 180 mm was installed at the outlet of the bleed air recovery device of the turbo chiller, and the container was heated to normal pressure, approximately 25 mm.
R123 containing R133a was passed through at °C. The concentration of R133a in R123 at the inlet and outlet of this container was measured by gas chromatography. The results are shown in Table 1.
【００１８】[0018]
【表１】[Table 1]
【００１９】ＭＳ−１３Ｘ；直径４．３ｍｍ，長さ８．
５ｍｍの円筒状Ｘ型ゼオライト（ユニオン昭和社製）Ｍ
Ｓ−５Ａ；直径１．４ｍｍ，長さ４．０ｍｍの円筒状Ａ
型ゼオライト（ユニオン昭和社製）
ＭＳ−４Ａ；直径４．５ｍｍ球状Ａ型ゼオライト（ユニ
オン昭和社製）
ＭＳ−３Ａ；直径３．２ｍｍ，長さ６．５ｍｍの円筒状
Ａ型ゼオライト（ユニオン昭和社製）
４ＧＧ；クラレ社製４〜６メッシュの活性炭MS-13X; diameter 4.3 mm, length 8.
5mm cylindrical X-type zeolite (manufactured by Union Showa Co., Ltd.) M
S-5A: Cylindrical A with a diameter of 1.4 mm and a length of 4.0 mm
type zeolite (manufactured by Union Showa Co., Ltd.) MS-4A: spherical type A zeolite with a diameter of 4.5 mm (manufactured by Union Showa Co., Ltd.) MS-3A; cylindrical type A zeolite with a diameter of 3.2 mm and a length of 6.5 mm (manufactured by Union Showa Co., Ltd.) 4GG; 4-6 mesh activated carbon manufactured by Kuraray Co., Ltd.)
【００２０
】0020
]
【発明の効果】本発明に従えば、ターボ冷凍機用冷媒や
ポリウレタン発泡剤として有望なＲ１２３中に含まれる
Ｒ１３３ａを効率的に無害なレベルまで除去することが
できる。According to the present invention, R133a contained in R123, which is promising as a refrigerant for centrifugal chillers and a polyurethane blowing agent, can be efficiently removed to a harmless level.
Claims (3)
タン（Ｒ１３３ａ）を含む１，１−ジクロロ−２，２，
２−トリフルオロエタン（Ｒ１２３）を活性炭又はゼオ
ライトと接触させ、Ｒ１２３中のＲ１３３ａの含有量を
１０ｐｐｍ以下とすることを特徴とするＲ１２３中のＲ
１３３ａを除去する方法。Claim 1: 1,1-dichloro-2,2, containing 1-chloro-2,2,2-trifluoroethane (R133a)
R in R123, which is characterized by contacting 2-trifluoroethane (R123) with activated carbon or zeolite, and controlling the content of R133a in R123 to 10 ppm or less.
How to remove 133a.
タンを含む１，１−ジクロロ−２，２，２−トリフルオ
ロエタンがターボ冷凍機の抽気装置から排出されるもの
である請求項１の方法。Claim 2: A claim in which 1,1-dichloro-2,2,2-trifluoroethane containing 1-chloro-2,2,2-trifluoroethane is discharged from an air extraction device of a turbo chiller. Method of item 1.
Åである請求項１の方法。Claim 3: The activated carbon or zeolite has a pore diameter of 3 to 10.
2. The method of claim 1, wherein .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3022886A JPH04243523A (en) | 1991-01-23 | 1991-01-23 | Removal of chlorotrifluoroethane in dichlorofluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3022886A JPH04243523A (en) | 1991-01-23 | 1991-01-23 | Removal of chlorotrifluoroethane in dichlorofluoroethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04243523A true JPH04243523A (en) | 1992-08-31 |
Family
ID=12095161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3022886A Withdrawn JPH04243523A (en) | 1991-01-23 | 1991-01-23 | Removal of chlorotrifluoroethane in dichlorofluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04243523A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994022793A1 (en) * | 1993-04-06 | 1994-10-13 | E.I. Du Pont De Nemours And Company | Separation of chloropentafluoroethane from pentafluoroethane |
-
1991
- 1991-01-23 JP JP3022886A patent/JPH04243523A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994022793A1 (en) * | 1993-04-06 | 1994-10-13 | E.I. Du Pont De Nemours And Company | Separation of chloropentafluoroethane from pentafluoroethane |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980514 |