JPH0725707B2 - Method for purifying 1,1,1,2-tetrafluoroethane - Google Patents
Method for purifying 1,1,1,2-tetrafluoroethaneInfo
- Publication number
- JPH0725707B2 JPH0725707B2 JP1094930A JP9493089A JPH0725707B2 JP H0725707 B2 JPH0725707 B2 JP H0725707B2 JP 1094930 A JP1094930 A JP 1094930A JP 9493089 A JP9493089 A JP 9493089A JP H0725707 B2 JPH0725707 B2 JP H0725707B2
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- Prior art keywords
- chf
- hfc
- reaction
- hydrogen
- catalyst
- Prior art date
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Classifications
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 （１） 産業上の利用分野 本発明は、1,1,1,2−テトラフルオロエタン中の微量不
純物を水素と反応させて、1,1,1,2−テトラフルオロエ
タンを精製することに関する。DETAILED DESCRIPTION OF THE INVENTION (1) Field of Industrial Application The present invention is directed to the reaction of trace impurities in 1,1,1,2-tetrafluoroethane with hydrogen to give 1,1,1,2-tetrafluoroethane. It relates to the purification of fluoroethane.
近年、1,1,1,2−テトラフルオロエタン（以降、HFC−13
4a又はCF3CH2Fと略す。）はカーエアコン、冷蔵庫等の
冷媒として、また電子産業用ガスとして注目されてい
る。In recent years, 1,1,1,2-tetrafluoroethane (hereinafter HFC-13
Abbreviated as 4a or CF 3 CH 2 F. ) Is drawing attention as a refrigerant for car air conditioners, refrigerators, etc., and as a gas for the electronic industry.
（２） 従来の技術 HFC−134aの製造法としては、例えば２−クロロ−1,1,1
−トリフルオロエタンを気相でフッ化水素と反応させる
ことにより製造されるが、触媒、反応条件等によりフル
オロアルケン類として、CClF＝CF2（CFC−1113）,CHCl
＝CClF（HCFC−1121）,CHCl＝CF2（HCFC−1122）,CHF＝
CF2（HFC−1123）,CHF＝CHF（HFC−1132）等が、クロロ
フルオロカーボン類として、CCl2F2（CFC−12）,CH2ClF
（HCFC−31）,CClF2CClF2（CFC−114）,CCl2FCF3（CFC
−114a）,CClF2CF3（CFC−115）,CHCl2CF3（HCFC−12
3）,CHClFCF3（HCFC−124）,CH2ClCF3（HCFC−133a）等
が、ハイドロフルオロカーボン類として、CHF2CF3（HFC
−125）,CHF2CHF2（HFC−134）,CH3CF3（HFC−143a）等
の副生成物が生成する。(2) Conventional technology As a method for producing HFC-134a, for example, 2-chloro-1,1,1
-It is produced by reacting trifluoroethane with hydrogen fluoride in the gas phase. CClF = CF 2 (CFC-1113), CHCl as fluoroalkenes depending on the catalyst, reaction conditions, etc.
= CClF (HCFC-1121), CHCl = CF 2 (HCFC-1122), CHF =
CF 2 (HFC-1123), CHF = CHF (HFC-1132), etc. are used as chlorofluorocarbons such as CCl 2 F 2 (CFC-12), CH 2 ClF
(HCFC-31), CClF 2 CClF 2 (CFC-114), CCl 2 FCF 3 (CFC
-114a), CClF 2 CF 3 (CFC-115), CHCl 2 CF 3 (HCFC-12
3), CHClFCF 3 (HCFC-124), CH 2 ClCF 3 (HCFC-133a), etc. are used as hydrofluorocarbons in CHF 2 CF 3 (HFC
−125), CHF 2 CHF 2 (HFC-134), CH 3 CF 3 (HFC-143a) and other by-products are formed.
目的物であるHFC−134a中に含まれる前記のような不純
物の量は少量でも更に減少させることが望ましく、特に
フルオロアルケン類およびクロロフルオロカーボン類は
含有されないことが望ましく、従来、これは慣用法、例
えば分別蒸溜により達成されられていた。しかしなが
ら、従来の方法では目的物であるHFC−134aと沸点が近
似している不純物、また共沸組成を有する不純物の分別
蒸溜は極めて困難であり、特にフルオロアルケン類およ
びクロロフルオロカーボン類が分離除去できず0.3wt％
以下の濃度で含有されていた。It is desirable to further reduce the amount of the above-mentioned impurities contained in the target product HFC-134a even in a small amount, and it is particularly desirable that fluoroalkenes and chlorofluorocarbons are not contained. For example, it was achieved by fractional distillation. However, according to the conventional method, it is extremely difficult to fractionally distill an impurity having a boiling point similar to that of the target product, HFC-134a, and an impurity having an azeotropic composition, and in particular, fluoroalkenes and chlorofluorocarbons can be separated and removed. Without 0.3 wt%
It was contained in the following concentrations.
このため、例えば1,1−ジフルオロ−２−クロロエチレ
ンを不純物として含むHFC−134aの精製法として金属過
マンガン酸塩または過マンガン酸塩の水溶液と接触させ
る方法（特開昭53−105404）が知られているが操作が煩
雑であり実用的でない。Therefore, for example, as a purification method of HFC-134a containing 1,1-difluoro-2-chloroethylene as an impurity, a method of contacting with metal permanganate or an aqueous solution of permanganate (JP-A-53-105404) is known. It is known, but the operation is complicated and not practical.
一方、水添脱ハロゲン反応および水素化反応について
は、例えば1,1,2−トリクロロ−1,2,2−トリフルオロエ
タンの水添脱ハロゲン反応によるトリフルオロエチレン
の製造方法（特開昭62−61936）、クロロトリフルオロ
エチレンの水添脱ハロゲン反応によるトリフルオロエチ
レンの製造方法（US−3564064）、またCF2XCFYZ式で表
される４〜５個の弗素原子を有するハロエタンの水添脱
ハロゲン反応によるテトラフルオロエタンの製造方法
（GB−1578933）等が知られているが、HFC−134a中に含
有される前記のような低濃度の不純物、特にフルオロア
ルケン類およびクロロフルオロカーボン類を同時に除去
する高純度のHFC−134a精製法はなく、工業的に有利な
精製方法の開発が望まれている。On the other hand, with respect to the hydrodehalogenation reaction and hydrogenation reaction, for example, a method for producing trifluoroethylene by hydrodehalogenation reaction of 1,1,2-trichloro-1,2,2-trifluoroethane (JP-A-62-62 -61936), a method for producing trifluoroethylene by hydrodehalogenation reaction of chlorotrifluoroethylene (US-3564064), and hydrodesorption of haloethane having 4 to 5 fluorine atoms represented by the CF 2 XCFYZ formula. A method for producing tetrafluoroethane by a halogen reaction (GB-1578933) and the like are known, but such low-concentration impurities contained in HFC-134a, particularly fluoroalkenes and chlorofluorocarbons, are simultaneously removed. There is no such high-purity HFC-134a purification method as described above, and development of an industrially advantageous purification method is desired.
（３） 発明が解決しようとする課題 本発明者等は従来の欠点を克服すべく検討した結果、HF
C−134a中の微量不純物、特にフルオロアルケン類およ
びクロロフルオロカーボン類を水素と反応させることに
より、HFC−134aは反応することなく、フルオロアルケ
ン類およびクロロフルオロカーボン類を同時に除去し、
クロロ化合物を含有しない高純度なHFC−134aを収率よ
く精製する方法を見出し本発明を完成した。(3) Problems to be Solved by the Invention As a result of investigations made by the present inventors to overcome the conventional drawbacks, HF
By reacting trace impurities in C-134a, especially fluoroalkenes and chlorofluorocarbons with hydrogen, HFC-134a removes fluoroalkenes and chlorofluorocarbons simultaneously without reaction,
The present invention has been completed by finding a method for purifying high-purity HFC-134a containing no chloro compound in a high yield.
（４） 課題を解決するための手段 HFC−134aの製造方法としては、例えば２−クロロ−1,
1,1−トリフルオロエタンを気相でフッ化水素と反応さ
せることにより製造されるが、触媒、反応条件等により
前記のような種々の副生成物が生成する。これらの副生
成物は従来、慣用法、例えば分別蒸溜により分離除去さ
れていたが目的物であるHFC−134aと沸点が近似してい
る不純物、また共沸組成を有する不純物の分別蒸溜によ
る分離除去は極めて困難であり、特にフルオロアルケン
類およびクロロフルオロカーボン類が分離除去できず0.
3wt％以下の濃度で含有されていた。本発明は、HFC−13
4a中のこれらの微量不純物、特にフルオロアルケン類お
よびクロロフルオロカーボン類を水素と反応させ水添反
応と水添脱ハロゲン反応によりHFC−134aは反応するこ
となく、フルオロアルケン類およびクロロフルオロカー
ボン類を同時に除去するHFC−134aの精製法に関するも
のである。(4) Means for Solving the Problems As a method for producing HFC-134a, for example, 2-chloro-1,
It is produced by reacting 1,1-trifluoroethane with hydrogen fluoride in the gas phase, but various by-products as described above are produced depending on the catalyst, reaction conditions and the like. These by-products were conventionally separated and removed by a conventional method, for example, fractional distillation, but impurities having a boiling point similar to that of the target product, HFC-134a, and impurities having an azeotropic composition were separated and removed by fractional distillation. Is extremely difficult, especially because fluoroalkenes and chlorofluorocarbons cannot be separated and removed.
It was contained at a concentration of 3 wt% or less. The present invention, HFC-13
These trace impurities in 4a, especially fluoroalkenes and chlorofluorocarbons, are reacted with hydrogen to remove HFC-134a at the same time without reacting HFC-134a by hydrogenation reaction and hydrodehalogenation reaction. The present invention relates to a method for purifying HFC-134a.
本発明は、触媒として第VIII族白金族金属の存在下で行
なうことを必須の要件とする。第VIII族白金族金属触媒
としては、白金、パラジウム、ロジウム、イリジウム、
ルテニウムおよびオスミウムを使用することができ、原
料としてはこれらの金属、金属酸化物または塩である。The present invention essentially requires that it be carried out in the presence of a Group VIII platinum group metal as a catalyst. Group VIII platinum group metal catalysts include platinum, palladium, rhodium, iridium,
Ruthenium and osmium can be used and the raw materials are these metals, metal oxides or salts.
本発明に使用できる担体とては、アルミナ、活性炭、シ
リカまたはチタンを用いることができ、金属の担持率は
0.05％以上であるならば目的とする反応が収率よく進行
する。As the carrier that can be used in the present invention, alumina, activated carbon, silica or titanium can be used, and the metal loading rate is
If it is 0.05% or more, the desired reaction proceeds in good yield.
本触媒の調製方法としては、例えば前記した金属塩を水
性溶媒、例えば水、メタノールまたはアセトン等に溶解
し、前記した担体を浸漬、吸着させ、次いで溶媒留去処
理を行い、更に水素で加熱還元処理することにより調製
することができる。また、市販品も用いることができ
る。The catalyst can be prepared by, for example, dissolving the above metal salt in an aqueous solvent such as water, methanol or acetone, soaking and adsorbing the above carrier, then distilling off the solvent, and further heating and reducing with hydrogen. It can be prepared by treating. Moreover, a commercial item can also be used.
以上のごとくして得られた触媒は、以下に述べる条件下
に使用するものである。The catalyst obtained as described above is used under the conditions described below.
本発明は、前記記載の方法で調製された触媒の存在下で
HFC−134a中の不純物、特にフルオロアルケン類および
クロロフルオロカーボン類を低温で水素と反応させるこ
とにより、HFC−134aを収率よく高純度に精製すること
ができる。The present invention is conducted in the presence of a catalyst prepared by the method described above.
By reacting impurities in HFC-134a, particularly fluoroalkenes and chlorofluorocarbons, with hydrogen at a low temperature, HFC-134a can be purified in high yield with high purity.
原料の導入にあたっては、HFC−134a中の不純物、特に
フルオロアルケン類およびクロロフルオロカーボン類と
水素とのモル比は1:1から1:4までの間で変動させ得る
が、通常、化学量論量の水素を使用するのが好ましい。When introducing the raw material, the molar ratio of hydrogen to impurities in HFC-134a, particularly fluoroalkenes and chlorofluorocarbons, can be varied from 1: 1 to 1: 4, but usually the stoichiometric amount is used. It is preferred to use hydrogen.
また、水素は窒素、ヘリウム、アルゴン等の不活性気体
を希釈剤として使用することもできる。In addition, hydrogen can be used as an inert gas such as nitrogen, helium or argon.
触媒に対する原料の空間速度（SV0）は、50から10000hr
-1の範囲を選択することができる。The space velocity (SV 0 ) of the raw material with respect to the catalyst is 50 to 10,000 hours
A range of -1 can be selected.
反応温度は使用する触媒の活性、またHFC−134a中の不
純物、特にフルオロアルケン類およびクロロフルオロカ
ーボン類の濃度、また空間速度（SV0）に依存して適宜
決められるが通常は室温から250℃の範囲で円滑に反応
が進行する。The reaction temperature is appropriately determined depending on the activity of the catalyst used, the concentrations of impurities in HFC-134a, particularly the fluoroalkenes and chlorofluorocarbons, and the space velocity (SV 0 ). The reaction proceeds smoothly within the range.
次に本発明を実施例により更に詳細に説明する。Next, the present invention will be described in more detail with reference to Examples.
（６） 実施例 原料例 １ まず２−クロロ−1,1,1−トリフルオロエタンを原料と
して用いて気相でフッ化水素と反応させることにより製
造された反応粗精製物を従来の慣用法、分別蒸溜により
精製をしたところ、次のような組成物が回収された。(6) Example Raw Material Example 1 First, a reaction crude product produced by reacting 2-chloro-1,1,1-trifluoroethane as a raw material with hydrogen fluoride in a gas phase is used in a conventional method. After purification by fractional distillation, the following composition was recovered.
このような従来の分別蒸溜ではHFC−134a中に微量不純
物として、フルオロアルケン類およびクロロフルオロカ
ーボン類が含有される。 In such conventional fractional distillation, HFC-134a contains fluoroalkenes and chlorofluorocarbons as trace impurities.
実施例 １ 塩化第二白金酸を水に溶解し、これに1.6mm球状アルミ
ナ担体を浸漬、吸着させ、次いで100℃の温度で溶媒留
去処理を行い、300℃にて空気焼成後、450℃にて水素還
元した。白金の担持率としては１％である。このように
して得られた１％白金／アルミナ触媒を電気炉により包
囲された長さ50cm、内径2.5cmのSUS製反応管内に40ml充
填した。反応条件として、反応温度100℃、原料として
原料例１を使用しガス量として30NL/h、水素は５％水素
／ヘリウム希釈品を使用しガス量として3NL/hでそれぞ
れ供給し、排出ガスをアルカリ水溶液で洗浄により副生
HClを除去し、モレキュラシーブスで乾燥後、液体窒素
を用いて回収し気液クロマトグラフィーにて分析を行っ
たところ次のような組成であった。Example 1 Dichloroplatinic acid was dissolved in water, 1.6 mm spherical alumina carrier was immersed and adsorbed in this solution, and then the solvent was distilled off at a temperature of 100 ° C., after air calcination at 300 ° C., 450 ° C. Was reduced with hydrogen. The platinum loading rate is 1%. 40 ml of the 1% platinum / alumina catalyst thus obtained was filled in a SUS reaction tube surrounded by an electric furnace and having a length of 50 cm and an inner diameter of 2.5 cm. As reaction conditions, the reaction temperature is 100 ° C., the raw material example 1 is used as the raw material, the gas amount is 30 NL / h, the hydrogen is diluted with 5% hydrogen / helium, and the gas amount is 3 NL / h, and the exhaust gas is supplied. By-product by washing with alkaline aqueous solution
After removing HCl and drying with molecular sieves, it was recovered by using liquid nitrogen and analyzed by gas-liquid chromatography to find the following composition.
CF3CH2F 99.9092 CH3CF3 0.0158 CHF2CF3 0.0109 CHF2CH2F 0.0116 CHF2CHF2 0.0245 CHF2CH3 0.0280 単位:wt％ HFC−134a中の微量不純物、フルオロアルケン類および
クロロフルオロカーボン類は水素と反応させることによ
り同時に除去された。CF 3 CH 2 F 99.9092 CH 3 CF 3 0.0158 CHF 2 CF 3 0.0109 CHF 2 CH 2 F 0.0116 CHF 2 CHF 2 0.0245 CHF 2 CH 3 0.0280 Unit: wt% Trace impurities in HFC-134a, fluoroalkenes and chlorofluorocarbons The classes were simultaneously removed by reacting with hydrogen.
更にこの除去された回収品を従来の慣用法、分別蒸溜に
より精製し分析したところ次のような組成であった。Further, the recovered product thus removed was purified and analyzed by a conventional conventional method of fractional distillation, and the composition was as follows.
CF3CH2F 99.9245 CH3CF3 0.0142 CHF2CF3 0.0101 CHF2CH2F 0.0012 CHF2CHF2 0.0231 CHF2CH3 0.0269 単位:wt％ 実施例 ２ 触媒として実施例１記載の同様の方法で調製した１％パ
ラジウム／アルミナからなる1.6mm球状触媒40mlを充填
した以外は実施例１と同様の条件で反応、回収し、気液
クロマトグラフィーにて分析を行ったところ次のような
組成であった。CF 3 CH 2 F 99.9245 CH 3 CF 3 0.0142 CHF 2 CF 3 0.0101 CHF 2 CH 2 F 0.0012 CHF 2 CHF 2 0.0231 CHF 2 CH 3 0.0269 Unit: wt% Example 2 As a catalyst, in the same manner as in Example 1 The reaction and recovery were carried out under the same conditions as in Example 1 except that 40 ml of the prepared 1.6 mm spherical catalyst made of 1% palladium / alumina was charged, and the composition was analyzed by gas-liquid chromatography. It was
CF3CH2F 99.9136 CH3CF3 0.0165 CHF2CF3 0.0098 CHF2CH2F 0.0092 CHF2CHF2 0.0238 CHF2CH3 0.0271 単位:wt％ 更にこの除去された回収品を従来の慣用法、分別蒸溜に
より精製し分析したところ次のような組成であった。CF 3 CH 2 F 99.9136 CH 3 CF 3 0.0165 CHF 2 CF 3 0.0098 CHF 2 CH 2 F 0.0092 CHF 2 CHF 2 0.0238 CHF 2 CH 3 0.0271 Unit: wt% Furthermore, the recovered product removed by the conventional method The composition was as follows when purified by distillation and analyzed.
CF3CH2F 99.9136 CH3CF3 0.0165 CHF2CF3 0.0098 CHF2CH2F 0.0092 CHF2CHF2 0.0238 CHF2CH3 0.0271 単位:wt％ 比 較 例 硝酸ニッケルを水に溶解しこれに実施例１と同様の1.6m
m球状アルミナ担体を浸漬、吸着させ、次いで100℃の温
度で溶媒留去処理を行い、350℃にて空気焼成後、450℃
にて水素還元した。ニッケル担持率としては10％であ
る。ニッケルは水素化触媒として工業的に広範な用途を
持っている。このようにして調製した10％ニッケル／ア
ルミナ触媒40mlを充填した以外は実施例１と同様の反応
条件で反応し回収物を分析したところ、全く反応は進行
せず入口組成と同様であった。更に、反応温度を200℃
と上昇させたが変わらなかった。CF 3 CH 2 F 99.9136 CH 3 CF 3 0.0165 CHF 2 CF 3 0.0098 CHF 2 CH 2 F 0.0092 CHF 2 CHF 2 0.0238 CHF 2 CH 3 0.0271 Unit: wt% Comparative example Nickel nitrate dissolved in water Example 1.6m same as 1
m Spherical alumina carrier is soaked and adsorbed, then the solvent is distilled off at a temperature of 100 ° C, air-baked at 350 ° C, and then 450 ° C.
Was reduced with hydrogen. The nickel loading rate is 10%. Nickel has a wide range of industrial uses as a hydrogenation catalyst. The reaction was conducted under the same reaction conditions as in Example 1 except that 40 ml of the 10% nickel / alumina catalyst thus prepared was charged, and the recovered substance was analyzed. The reaction did not proceed at all, and the composition was the same as that at the inlet. Furthermore, the reaction temperature is 200 ° C.
I raised it, but it did not change.
実施例 ３ 触媒として実施例１記載と同様の方法で調製した0.3％
白金／アルミナからなる1.6mm球状触媒40mlを充填した
以外は実施例１と同様の条件下で反応、回収し気液クロ
マトグラフィーにて分析を行ったところ次のような組成
であった。Example 3 0.3% prepared as a catalyst in the same manner as in Example 1
The reaction and recovery were carried out under the same conditions as in Example 1 except that 40 ml of a 1.6 mm spherical catalyst composed of platinum / alumina was charged, and the composition was as follows when analyzed by gas-liquid chromatography.
CF3CH2F 99.9264 CH3CF3 0.0152 CHF2CF3 0.0092 CHF2CH2F 0.0009 CHF2CHF2 0.0231 CHF2CH3 0.0252 単位:wt％ 実施例 ４ 実施例１と同様の触媒及び量を使用し反応条件として、
反応温度200℃、原料として原料例１を使用しガス量と
して600NL/h、水素は５％水素／ヘリウム希釈品をガス
量として8NL/hでそれぞれ供給した。排出ガスをアルカ
リ水溶液で洗浄、モレキュラシーブスで乾燥後、液体窒
素を用いて回収後、気液クロマトグラフィーにて分析し
たところ次のような組成であった。CF 3 CH 2 F 99.9264 CH 3 CF 3 0.0152 CHF 2 CF 3 0.0092 CHF 2 CH 2 F 0.0009 CHF 2 CHF 2 0.0231 CHF 2 CH 3 0.0252 Unit: wt% Example 4 Use the same catalyst and amount as Example 1. As reaction conditions,
The reaction temperature was 200 ° C., the raw material example 1 was used as the raw material, the gas amount was 600 NL / h, and the hydrogen gas was 5% hydrogen / helium diluted product, and the gas amount was 8 NL / h. The exhaust gas was washed with an alkaline aqueous solution, dried with molecular sieves, recovered with liquid nitrogen, and analyzed by gas-liquid chromatography to have the following composition.
CF3CH2F 99.9087 CH3CF3 0.0165 CHF2CF3 0.0110 CHF2CH2F 0.0112 CHF2CHF2 0.0248 CHF2CH3 0.0278 単位:wt％ 原料例 ２ ２−クロロ−1,1,1−トリフルオロエタンを原料として
用いて気相でフッ化水素と反応させ、分別蒸溜により精
製したところ、次のような組成であった。CF 3 CH 2 F 99.9087 CH 3 CF 3 0.0165 CHF 2 CF 3 0.0110 CHF 2 CH 2 F 0.0112 CHF 2 CHF 2 0.0248 CHF 2 CH 3 0.0278 Unit: wt% Raw material example 2 2-Chloro-1,1,1-tri When fluoroethane was used as a raw material and reacted with hydrogen fluoride in the gas phase and purified by fractional distillation, the composition was as follows.
実施例 ５ 実施例１と同様の触媒及び量を使用し反応条件として、
反応温度200℃、原料として原料例２を使用しガス量と
して30NL/h、水素は５％水素／ヘリウム希釈品をガス量
として3NL/hでそれぞれ供給した。排出ガスをアルカリ
水溶液で洗浄、モレキュラシーブスで乾燥後、液体窒素
を用いて回収後、気液クロマトグラフィーにて分析した
ところ次のような組成であった。 Example 5 Using the same catalyst and amount as in Example 1, as reaction conditions,
The reaction temperature was 200 ° C., the raw material example 2 was used as the raw material, the gas amount was 30 NL / h, and the hydrogen gas was 5% hydrogen / helium diluted product and the gas amount was 3 NL / h, respectively. The exhaust gas was washed with an alkaline aqueous solution, dried with molecular sieves, recovered with liquid nitrogen, and analyzed by gas-liquid chromatography to have the following composition.
CF3CH2F 99.8776 CHF2CF3 0.0201 CHF2CHF2 0.0751 CH3CF3 0.0278 単位:wt％ 更にこの除去された回収品を分別蒸溜により精製し分析
したところ次のような組成であった。CF 3 CH 2 F 99.8776 CHF 2 CF 3 0.0201 CHF 2 CHF 2 0.0751 CH 3 CF 3 0.0278 Unit: wt% Furthermore, the recovered product thus removed was purified by fractional distillation and analyzed to have the following composition.
CF3CH2F 99.9081 CHF2CF3 0.0116 CHF2CHF2 0.0711 CH3CF3 0.0092 単位:wt％ （７） 効果 本発明によれば従来、非常に困難であったHFC−134a中
の微量不純物、特にフルオロアルケン類およびクロロフ
ルオロカーボン類が同時除去でき、クロロ化合物を含有
しない高純度のHFC−134aを収率よく精製できる。CF 3 CH 2 F 99.9081 CHF 2 CF 3 0.0116 CHF 2 CHF 2 0.0711 CH 3 CF 3 0.0092 Unit: wt% (7) Effect According to the present invention, trace impurities in HFC-134a, which has been very difficult in the past according to the present invention, In particular, fluoroalkenes and chlorofluorocarbons can be simultaneously removed, and high-purity HFC-134a containing no chloro compound can be purified in good yield.
Claims (1)
れる不純物のクロロフルオロカーボン類を、第VIII族白
金族金属触媒の存在下で水素と反応させた後、蒸溜で分
離除去することを特徴とする1,1,1,2−テトラフルオロ
エタンの精製法。1. Impurity chlorofluorocarbons contained in 1,1,1,2-tetrafluoroethane are reacted with hydrogen in the presence of a Group VIII platinum group metal catalyst, and then separated and removed by distillation. A method for purifying 1,1,1,2-tetrafluoroethane, which is characterized in that
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1094930A JPH0725707B2 (en) | 1989-04-14 | 1989-04-14 | Method for purifying 1,1,1,2-tetrafluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1094930A JPH0725707B2 (en) | 1989-04-14 | 1989-04-14 | Method for purifying 1,1,1,2-tetrafluoroethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02273634A JPH02273634A (en) | 1990-11-08 |
| JPH0725707B2 true JPH0725707B2 (en) | 1995-03-22 |
Family
ID=14123688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1094930A Expired - Lifetime JPH0725707B2 (en) | 1989-04-14 | 1989-04-14 | Method for purifying 1,1,1,2-tetrafluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725707B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0607911D0 (en) * | 2006-04-21 | 2006-05-31 | Ineos Fluor Holdings Ltd | Process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001287A (en) * | 1989-02-02 | 1991-03-19 | E. I. Du Pont De Nemours And Company | Purification of saturated halocarbons |
-
1989
- 1989-04-14 JP JP1094930A patent/JPH0725707B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02273634A (en) | 1990-11-08 |
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