JPH04264039A - Removal of 1,1-dichloroethylene in 1,1-dichloro-1-fluoroethane - Google Patents
Removal of 1,1-dichloroethylene in 1,1-dichloro-1-fluoroethaneInfo
- Publication number
- JPH04264039A JPH04264039A JP3026079A JP2607991A JPH04264039A JP H04264039 A JPH04264039 A JP H04264039A JP 3026079 A JP3026079 A JP 3026079A JP 2607991 A JP2607991 A JP 2607991A JP H04264039 A JPH04264039 A JP H04264039A
- Authority
- JP
- Japan
- Prior art keywords
- dichloroethylene
- dichloro
- fluoroethane
- catalyst
- impurity
- 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.)
- Pending
Links
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 title claims abstract description 29
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 4
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004821 distillation Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005108 dry cleaning Methods 0.000 abstract description 2
- 239000003925 fat Substances 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000003599 detergent Substances 0.000 abstract 1
- 230000004907 flux Effects 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 18
- 238000005660 chlorination reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000011437 continuous method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 alkaline Substances 0.000 description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PJWGBIYISLWPAW-UHFFFAOYSA-N [Cl].C(=C)(Cl)Cl Chemical compound [Cl].C(=C)(Cl)Cl PJWGBIYISLWPAW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、ウレタンフォ−ムの発
泡剤、油脂、フラックス除去用洗浄剤、ドライクリ−ニ
ング用溶剤として有用である１，１−ジクロロ−１−フ
ルオロエタンの製造に際して蒸留により除くことが困難
な１，１−ジクロロエチレンを除去する方法に関するも
のである。[Industrial Application Field] The present invention is a method for distilling 1,1-dichloro-1-fluoroethane in the production of 1,1-dichloro-1-fluoroethane, which is useful as a blowing agent for urethane foam, a cleaning agent for removing fats and oils, and a solvent for dry cleaning. The present invention relates to a method for removing 1,1-dichloroethylene, which is difficult to remove.
【０００２】0002
【従来技術およびその問題点】１，１−ジクロロ−１−
フルオロエタンを製造する方法には１）１，１−ジクロ
ロエチレンにフッ化水素を五塩化アンチモン、四塩化錫
等の金属塩化物を触媒として用いたり、または無触媒の
もとに付加させる方法、２）１，１，１−トリクロロエ
タンを五塩化アンチモン、四塩化錫等の金属塩化物を触
媒として用いたり、または無触媒の条件でフッ化水素に
よって塩素−フッ素の原子交換を行なう方法がある。前
者の方法には例えば米国特許２，４９５，４０７があり
、１，１，１−トリクロロエタンを無触媒でフッ化水素
と反応させる方法は文献（Ｊ．Ｈ．Ｂｒｏｗｎ，Ｗ．Ｂ
．Ｗａｌｌｅｙ：Ｊ．Ｓｏｃ．Ｃｈｅｍ．Ｉｎｄ．，Ｖ
ｏｌ．６７，３３２）や特公昭５０−５６８１に見られ
る。ところで、１，１−ジクロロエチレンを原料とする
場合には未反応原料が残ることにより１，１−ジクロロ
エチレンが１，１−ジクロロ−１−フルオロエタン中に
混入し、また、１，１，１−トリクロロエタンを原料と
する場合でも１，１，１−トリクロロエタンの脱塩化水
素等による１，１−ジクロロエチレンの副生により１，
１−ジクロロエチレンが１，１−ジクロロ−１−フルオ
ロエタン中に混入するのを避けられないが、１，１−ジ
クロロエチレンの沸点は３１．７℃と１，１−ジクロロ
−１−フルオロエタンの沸点の３２℃と極めて近く、通
常の精製法である蒸留法は適用できなかった。[Prior art and its problems] 1,1-dichloro-1-
Methods for producing fluoroethane include 1) a method of adding hydrogen fluoride to 1,1-dichloroethylene using a metal chloride such as antimony pentachloride or tin tetrachloride as a catalyst or without a catalyst; 2) ) There is a method in which atomic exchange of chlorine and fluorine is carried out using 1,1,1-trichloroethane using a metal chloride such as antimony pentachloride or tin tetrachloride as a catalyst, or with hydrogen fluoride in the absence of a catalyst. The former method includes, for example, U.S. Pat.
．． Walley: J. Soc. Chem. Ind. ,V
ol. 67,332) and Special Publication No. 50-5681. By the way, when 1,1-dichloroethylene is used as a raw material, unreacted raw materials remain and 1,1-dichloroethylene is mixed into 1,1-dichloro-1-fluoroethane. Even when trichloroethane is used as a raw material, 1,1-dichloroethylene is by-produced by dehydrochlorination of 1,1,1-trichloroethane,
Although it is unavoidable that 1-dichloroethylene is mixed into 1,1-dichloro-1-fluoroethane, the boiling point of 1,1-dichloroethylene is 31.7°C, which is the boiling point of 1,1-dichloro-1-fluoroethane. The temperature was extremely close to 32°C, and the usual purification method, distillation, could not be applied.
【０００３】一般に望ましい精製法としては、固体によ
る吸着法があるが、モレキュラーシーブ５Ａ，４Ａ，３
Ａ，１３Ｘ，酸性アルミナ、中性アルミナ、塩基性アル
ミナ、シリカゲル、珪藻土などでは１，１−ジクロロエ
チレンの選択的吸着は起こらない。活性炭の一部の品種
は、１，１−ジクロロエチレンの選択的吸着性を示すが
、回分処理、充填塔による流通処理のいずれの場合も極
めて処理容量が小さく実用には供しえない。[0003] A generally desirable purification method is a solid adsorption method, but molecular sieves 5A, 4A, 3
A, 13X, acidic alumina, neutral alumina, basic alumina, silica gel, diatomaceous earth, etc. do not selectively adsorb 1,1-dichloroethylene. Some types of activated carbon exhibit selective adsorption properties for 1,1-dichloroethylene, but their processing capacity is extremely small in both batch processing and distribution processing using packed towers, making them unsuitable for practical use.
【０００４】0004
【問題点を解決するための手段】本発明者らは、鋭意検
討を行なった結果、少なくとも１，１−ジクロロエチレ
ンと１，１−ジクロロ−１−フルオロエタンを含む混合
物に塩素を添加し、１，１−ジクロロエチレンを塩素化
することにより１，１−ジクロロエチレンを１，１，１
，２−テトラクロロエタンとして除去し、容易に１，１
−ジクロロエチレンを実質上含まない１，１−ジクロロ
−１−フルオロエタンが得られることを見出し、本発明
に到達した。[Means for Solving the Problems] As a result of intensive studies, the present inventors added chlorine to a mixture containing at least 1,1-dichloroethylene and 1,1-dichloro-1-fluoroethane. , 1-dichloroethylene is chlorinated to convert 1,1-dichloroethylene into 1,1,1
, 2-tetrachloroethane and easily removed as 1,1
- It has been discovered that 1,1-dichloro-1-fluoroethane substantially free of dichloroethylene can be obtained, and the present invention has been achieved.
【０００５】すなわち本発明は、少なくとも１，１−ジ
クロロエチレンと１，１−ジクロロ−１−フルオロエタ
ンを含む混合物に塩素を添加し、１，１−ジクロロエチ
レンを塩素化することを特徴とする１，１−ジクロロ−
１−フルオロエタン中の１，１−ジクロロエチレンの除
去方法である。That is, the present invention is characterized in that 1,1-dichloroethylene is chlorinated by adding chlorine to a mixture containing at least 1,1-dichloroethylene and 1,1-dichloro-1-fluoroethane. 1-dichloro-
This is a method for removing 1,1-dichloroethylene in 1-fluoroethane.
【０００６】本発明は、１，１，１−トリクロロエタン
とフッ化水素を無触媒あるいは触媒の存在下で回分式ま
たは連続的に反応させたり、１，１−ジクロロエチレン
を原料にして同様の条件で反応させて得られた少なくと
も１，１−ジクロロエチレンと１，１−ジクロロ−１−
フルオロエタンを含む混合物に塩素を添加し、１，１−
ジクロロエチレンを塩素化することにより１，１−ジク
ロロエチレンを１，１，１，２−テトラクロロエタンと
して除去し、１，１−ジクロロエチレンを実質的に含ま
ない１，１−ジクロロ−１−フルオロエタンを得ること
からなる１，１−ジクロロ−１−フルオロエタン中の１
，１−ジクロロエチレンの除去方法である。The present invention involves reacting 1,1,1-trichloroethane and hydrogen fluoride batchwise or continuously in the absence of a catalyst or in the presence of a catalyst, or reacting 1,1-dichloroethylene as a raw material under similar conditions. At least 1,1-dichloroethylene obtained by the reaction and 1,1-dichloro-1-
Adding chlorine to a mixture containing fluoroethane produces 1,1-
1,1-dichloroethylene is removed as 1,1,1,2-tetrachloroethane by chlorinating dichloroethylene to obtain 1,1-dichloro-1-fluoroethane substantially free of 1,1-dichloroethylene. 1 in 1,1-dichloro-1-fluoroethane consisting of
, 1-dichloroethylene.
【０００７】本発明における塩素化は通常の方法によれ
ばよく、四塩化錫、鉄、塩化鉄等の触媒の存在下で、ま
たは無触媒のもとに行なうことができる。しかし、無触
媒時や四塩化錫のような弱い塩素化触媒を用いた場合に
は加熱しなければ塩素化が進まないため、常温常圧でも
塩素化を進められる鉄や塩化鉄を触媒として用いるのが
より好ましく、１，１−ジクロロ−１−フルオロエタン
をほとんど分解することなく塩素化を進めることができ
る。Chlorination in the present invention may be carried out by a conventional method, and can be carried out in the presence of a catalyst such as tin tetrachloride, iron, iron chloride, or the like, or in the absence of a catalyst. However, if no catalyst is used or a weak chlorination catalyst such as tin tetrachloride is used, chlorination will not proceed unless heated, so iron or iron chloride, which can proceed with chlorination even at room temperature and pressure, is used as a catalyst. It is more preferable that 1,1-dichloro-1-fluoroethane be chlorinated without being substantially decomposed.
【０００８】本発明の塩素化反応は、回分式、連続式の
いずれの方法でも行なうことができる。回分式方法は、
被処理物中に塩素を吹込んで溶解させ、この溶液に触媒
を投入し、攪拌して反応させた後、不純物除去品を回収
するという操作を繰り返す方法である。連続式方法は、
塩素と被処理物を触媒を充填した反応管中に連続的に流
通させ、不純物除去品を連続的に回収する方法である。The chlorination reaction of the present invention can be carried out either batchwise or continuously. The batch method is
This is a method that repeats the following operations: blowing chlorine into the material to be treated to dissolve it, adding a catalyst to the solution, stirring to cause a reaction, and recovering the product from which impurities have been removed. The continuous method is
This is a method in which chlorine and the material to be treated are continuously passed through a reaction tube filled with a catalyst, and the product from which impurities have been removed is continuously recovered.
【０００９】また、触媒の形状は、回分式方法において
は粉末、粒状等のものが用いられ、連続式方法において
は粉末、粒状または通常の充填物、すなわちラシヒリン
グ、マクマホン等やスチールウール等を用いることがで
きる。[0009] Regarding the shape of the catalyst, powder, granules, etc. are used in the batch method, and powder, granules, or ordinary fillers, such as Raschig rings, McMahons, steel wool, etc., are used in the continuous method. be able to.
【００１０】本発明における塩素化は被処理物中に少量
の水分が混入していても可能であるが、水分の混入は装
置の腐食などの原因となるため予め硫酸あるいはシリカ
ゲル、モレキュラーシーブ等の乾燥剤で脱水しておくこ
とが望ましい。Chlorination in the present invention can be carried out even if a small amount of water is mixed in the material to be treated, but since the mixing of water can cause corrosion of the equipment, chlorination with sulfuric acid, silica gel, molecular sieve, etc. It is preferable to dehydrate with a desiccant.
【００１１】また、塩素化は被処理物中に反応原料や反
応生成物に由来するＨＣｌ、ＨＦが混入していても可能
であるが、ＨＣｌ、ＨＦの混入は塩素化の反応速度を低
下させるため予め除去しておくことが望ましい。[0011]Also, chlorination is possible even if HCl and HF derived from reaction raw materials and reaction products are mixed into the material to be treated, but the mixing of HCl and HF reduces the reaction rate of chlorination. Therefore, it is desirable to remove them in advance.
【００１２】上記の回分式、連続式のいずれの方法にお
いても溶解させる塩素の量は被処理物中の１，１−ジク
ロロエチレンに対してモル比で１以上であればよいが、
副反応の抑制や後処理にかかる負荷の軽減などの点から
１〜５であるのがより好ましい。[0012] In either of the above batch-type or continuous-type methods, the amount of chlorine to be dissolved may be at least 1 in molar ratio to 1,1-dichloroethylene in the material to be treated.
From the viewpoint of suppressing side reactions and reducing the load on post-treatment, it is more preferable that the number is 1 to 5.
【００１３】回分式方法の場合、触媒濃度は０．０１〜
３０重量％の範囲で設定できる。また、反応は数分でほ
ぼ完結するので反応時間は１０分以上とすればよいが、
副反応の抑制や処理能率の向上などの点から１０分〜１
時間とするのがより好ましい。[0013] In the case of the batch method, the catalyst concentration is from 0.01 to
It can be set within a range of 30% by weight. Also, since the reaction is almost completed in a few minutes, the reaction time should be at least 10 minutes.
10 minutes to 1 minute to suppress side reactions and improve processing efficiency
It is more preferable to set it as time.
【００１４】連続式方法の場合、被処理物の流通速度は
触媒と被処理物の接触時間が３０分〜３時間となるよう
に設定するのが好ましい。本発明における処理温度は、
０〜１００℃の範囲で設定できる。In the case of a continuous method, the flow rate of the material to be treated is preferably set so that the contact time between the catalyst and the material to be treated is 30 minutes to 3 hours. The processing temperature in the present invention is
It can be set in the range of 0 to 100°C.
【００１５】本発明における処理圧力は、特に限定され
ないが、装置の安全性などの点から０〜２ｋｇ／ｃｍ２
Ｇがより好ましい。本発明の方法により塩素化すること
によって１，１−ジクロロエチレンは１，１，１，２−
テトラクロロエタンとなるが、この１，１，１，２−テ
トラクロロエタンの沸点は１３０℃であり１，１−ジク
ロロ−１−フルオロエタンの沸点の３２℃と充分な差が
あるため、通常の精製法である蒸留法を適用することに
より容易に１，１−ジクロロ−１−フルオロエタンを分
離精製することが可能となる。[0015] The processing pressure in the present invention is not particularly limited, but is 0 to 2 kg/cm2 from the viewpoint of equipment safety.
G is more preferred. By chlorinating according to the method of the present invention, 1,1-dichloroethylene can be converted into 1,1,1,2-
The boiling point of 1,1,1,2-tetrachloroethane is 130°C, which is sufficiently different from the boiling point of 1,1-dichloro-1-fluoroethane (32°C), so it cannot be purified normally. By applying the distillation method, it becomes possible to easily separate and purify 1,1-dichloro-1-fluoroethane.
【００１６】[0016]
【実施例】以下、実施例により本発明を具体的に説明す
る。
実施例１〜５
１，１，１−トリクロロエタンをフッ素化して合成した
１，１−ジクロロエチレン、１，１−ジクロロ−１−フ
ルオロエタン、１−クロロ−１，１−ジフルオロエタン
、１，１，１−トリクロロエタンを含む粗１，１−ジク
ロロ−１−フルオロエタンに所定量の塩素を吹込み溶解
させた。所定量の触媒を前記の溶液に投入し、マグネテ
ィックスターラーで所定時間攪拌した。反応後、触媒と
サンプルを分離し、サンプルを水洗、アルカリ洗、水洗
した後、ガスクロマトグラフで分析した。塩素化処理の
前後における１，１−ジクロロエチレン濃度を表１に示
す。またこの時、１，１，１，２−テトラクロロエタン
の生成は観測されたがそれ以外の新たな副生成物は見ら
れなかった。[Examples] The present invention will be specifically explained below with reference to Examples. Examples 1 to 5 1,1-dichloroethylene, 1,1-dichloro-1-fluoroethane, 1-chloro-1,1-difluoroethane, 1,1,1 synthesized by fluorinating 1,1,1-trichloroethane - A predetermined amount of chlorine was blown into crude 1,1-dichloro-1-fluoroethane containing trichloroethane to dissolve it. A predetermined amount of catalyst was added to the above solution and stirred with a magnetic stirrer for a predetermined time. After the reaction, the catalyst and sample were separated, and the sample was washed with water, alkaline, and water, and then analyzed using a gas chromatograph. Table 1 shows the 1,1-dichloroethylene concentrations before and after the chlorination treatment. At this time, the production of 1,1,1,2-tetrachloroethane was observed, but no other new by-products were observed.
【００１７】[0017]
【表１】[Table 1]
【００１８】実施例６
０．６３５８％の１，１−ジクロロエチレンを含む１，
１−ジクロロ−１−フルオロエタンに塩素／１，１−ジ
クロロエチレンが１．４になるように塩素ガスを溶解さ
せた。これを５０ｇの鉄粉を充填した内径２ｃｍ、長さ
４０ｃｍのガラス製反応管に線速２０ｃｍ／ｈで流通さ
せた。反応管出口のサンプルを水洗、アルカリ洗、水洗
した後、ガスクロマトグラフで分析したところ、１，１
−ジクロロエチレンの濃度は０．００１７％であった。Example 6 1, containing 0.6358% 1,1-dichloroethylene
Chlorine gas was dissolved in 1-dichloro-1-fluoroethane so that the ratio of chlorine/1,1-dichloroethylene was 1.4. This was passed through a glass reaction tube with an inner diameter of 2 cm and a length of 40 cm filled with 50 g of iron powder at a linear velocity of 20 cm/h. After washing the sample at the outlet of the reaction tube with water, alkaline washing, and water, it was analyzed using a gas chromatograph.
- The concentration of dichloroethylene was 0.0017%.
【００１９】[0019]
【発明の効果】本発明方法によれば１，１−ジクロロ−
１−フルオロエタンの製造に際して蒸留により除くこと
が困難な１，１−ジクロロエチレンを常温常圧下でも短
時間で容易に除去することができるという効果を奏する
。[Effect of the invention] According to the method of the present invention, 1,1-dichloro-
This has the effect that 1,1-dichloroethylene, which is difficult to remove by distillation during the production of 1-fluoroethane, can be easily removed in a short time even at room temperature and pressure.
Claims (1)
，１−ジクロロ−１−フルオロエタンを含む混合物に塩
素を添加し、１，１−ジクロロエチレンを塩素化するこ
とを特徴とする１，１−ジクロロ−１−フルオロエタン
中の１，１−ジクロロエチレンの除去方法。Claim 1: At least 1,1-dichloroethylene and 1
, 1-dichloro-1-fluoroethane, by adding chlorine to the mixture containing 1,1-dichloro-1-fluoroethane to chlorinate the 1,1-dichloroethylene. Removal method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3026079A JPH04264039A (en) | 1991-02-20 | 1991-02-20 | Removal of 1,1-dichloroethylene in 1,1-dichloro-1-fluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3026079A JPH04264039A (en) | 1991-02-20 | 1991-02-20 | Removal of 1,1-dichloroethylene in 1,1-dichloro-1-fluoroethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04264039A true JPH04264039A (en) | 1992-09-18 |
Family
ID=12183631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3026079A Pending JPH04264039A (en) | 1991-02-20 | 1991-02-20 | Removal of 1,1-dichloroethylene in 1,1-dichloro-1-fluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04264039A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5318673A (en) * | 1992-04-17 | 1994-06-07 | Solvay (Societe Anonyme) | Process for the purification of 1,1-dichloro-1-fluoroethane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0324024A (en) * | 1989-06-07 | 1991-02-01 | Atochem North America Inc | Removal of unsaturated carbon compound from 1,1-dichloro-1- fluoroethane |
| JPH03118339A (en) * | 1989-09-12 | 1991-05-20 | Soc Atochem | Method for purification of 1, 1-dichloro-1- fluoroethane |
-
1991
- 1991-02-20 JP JP3026079A patent/JPH04264039A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0324024A (en) * | 1989-06-07 | 1991-02-01 | Atochem North America Inc | Removal of unsaturated carbon compound from 1,1-dichloro-1- fluoroethane |
| JPH03118339A (en) * | 1989-09-12 | 1991-05-20 | Soc Atochem | Method for purification of 1, 1-dichloro-1- fluoroethane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5318673A (en) * | 1992-04-17 | 1994-06-07 | Solvay (Societe Anonyme) | Process for the purification of 1,1-dichloro-1-fluoroethane |
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