JPH061730A - Purification of 1,1,1,2-tetrafluoroethane - Google Patents
Purification of 1,1,1,2-tetrafluoroethaneInfo
- Publication number
- JPH061730A JPH061730A JP15924792A JP15924792A JPH061730A JP H061730 A JPH061730 A JP H061730A JP 15924792 A JP15924792 A JP 15924792A JP 15924792 A JP15924792 A JP 15924792A JP H061730 A JPH061730 A JP H061730A
- Authority
- JP
- Japan
- Prior art keywords
- hcfc
- tetrafluoroethane
- hfc
- trifluorochloroethane
- reaction mixture
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は冷凍機の冷媒として用い
られているフロン１２の代替冷媒として有望な１,１,
１,２−テトラフルオロエタンの精製法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a promising alternative refrigerant for CFC 12 used as a refrigerant for refrigerators.
The present invention relates to a method for purifying 1,2-tetrafluoroethane.
【０００２】[0002]
【従来の技術】１,１,１,２−テトラフルオロエタン(以
下ＨＦＣ−１３４ａ)は１,１,１−トリフルオロクロロ
エタンまたはトリクロロエチレンをクロムを主成分とす
る触媒の存在下、主として気相でフッ素化することによ
って得られるが、副生物として１,１−ジフルオロクロ
ロエチレン(以下ＨＣＦＣ−１１２２)が混入する。この
ＨＣＦＣ−１１２２をＨＦＣ−１３４ａから除くため
に、たとえば特開昭５３−１０５４０４にはＨＦＣ−１
３４ａとＨＣＦＣ−１１２２をフッ化水素と共に１００
〜２７５℃の温度で酸化クロムまたは塩基性フッ化クロ
ムに接触させる方法及び金属過マンガン酸塩と緊密に接
触させる方法が、特開平２−２６８１２４には活性炭に
よる吸着除去方法が記載されている。2. Description of the Related Art 1,1,1,2-Tetrafluoroethane (hereinafter HFC-134a) is mainly in a gas phase in the presence of a catalyst containing 1,1,1-trifluorochloroethane or trichloroethylene as a main component of chromium. Although obtained by fluorinating, 1,1-difluorochloroethylene (hereinafter referred to as HCFC-1122) is mixed as a by-product. In order to remove this HCFC-1122 from HFC-134a, HFC-1 is disclosed in, for example, JP-A-53-105404.
34a and HCFC-1122 together with hydrogen fluoride to 100
A method of contacting with chromium oxide or basic chromium fluoride at a temperature of ˜275 ° C. and a method of intimately contacting with metal permanganate are described in JP-A-2-268124, and a method of adsorption removal with activated carbon is described.
【０００３】[0003]
【発明が解決しようとする課題】これらの方法の内、フ
ッ化水素とともに１００〜２７５℃の温度で酸化クロム
または塩基性フッ化クロムに接触させる前者の方法では
反応のために特殊な材質の反応器を追加する必要があ
り、吸着剤を用いる後者の方法では再生のための設備を
要し、またＨＣＦＣ−１１２２を完全に除去できないな
どといずれも満足できるものではなかった。本発明の目
的はこれらの欠点を解決し、ＨＦＣ−１３４ａ中に含ま
れるＨＣＦＣ−１１２２を効率的に除去する精製方法を
提供することにある。Among these methods, the former method of contacting chromium oxide or basic chromium fluoride with hydrogen fluoride at a temperature of 100 to 275 ° C. involves reaction of a special material for the reaction. However, the latter method using an adsorbent requires equipment for regeneration, and HCFC-1122 cannot be completely removed. An object of the present invention is to solve these drawbacks and to provide a purification method for efficiently removing HCFC-1122 contained in HFC-134a.
【０００４】[0004]
【課題を解決するための手段】本発明はＨＦＣ−１３４
ａ中に不純物として混入するＨＣＦＣ−１１２２をハロ
スルフォン酸と反応させることにより除去することを特
徴とする。本発明に用いるハロスルフォン酸のハロゲン
はフッ素または塩素の内から選ばれる。すなわちＨＳＯ
3ＦまたはＨＳＯ3Ｃlなる化学式で示されるフルオロス
ルフォン酸またはクロロスルフォン酸が好適に用いられ
る。特に好ましいのはフルオロスルフォン酸である。用
いられるハロスルフォン酸は硫酸または無水硫酸で希釈
されていてもよく、その濃度は特に限定しないが５０w
t.％以上が好ましく、−２０〜４０℃の温度及び１〜１
０kg／cm2abs.の圧力において有効にＨＣＦＣ−１１２
２を含んだＨＦＣ−１３４ａを処理することができる。The present invention provides HFC-134.
It is characterized in that HCFC-1122 mixed as an impurity in a is removed by reacting it with halosulfonic acid. The halogen of the halosulfonic acid used in the present invention is selected from fluorine and chlorine. Ie HSO
Fluorosulfonic acid or chlorosulfonic acid represented by the chemical formula 3 F or HSO 3 Cl is preferably used. Particularly preferred is fluorosulfonic acid. The halosulfonic acid used may be diluted with sulfuric acid or sulfuric anhydride, and the concentration thereof is not particularly limited, but is 50w.
t.% or more is preferable, a temperature of -20 to 40 ° C and 1-1
Effectively at a pressure of 0 kg / cm 2 abs. HCFC-112
HFC-134a containing 2 can be processed.
【０００５】処理されるＨＣＦＣ−１１２２の濃度はＨ
ＦＣ−１３４ａに対して２mol％以下であることが好ま
しく、これ以上ではＨＣＦＣ−１１２２の除去効率が低
下するため有効とはいえない。また反応混合物は、１,
１,１−トリフルオロクロロエタンまたはトリクロロエ
チレンをクロムを主成分とする触媒の存在下、主として
気相でフッ素化反応させて副生する塩化水素および未反
応のフッ化水素を含んでいても良く、約１００〜３６０
０hr-1で処理することができる。The concentration of HCFC-1122 processed is H
It is preferably 2 mol% or less with respect to FC-134a, and if it is more than this, it is not effective because the removal efficiency of HCFC-1122 decreases. Also, the reaction mixture is 1,
In the presence of a catalyst containing 1,1-trifluorochloroethane or trichloroethylene as a main component of chromium, hydrogen chloride which is by-produced mainly by a fluorination reaction in a gas phase and unreacted hydrogen fluoride may be contained. 100-360
It can be processed at 0 hr -1 .
【０００６】このＨＣＦＣ−１１２２の処理装置は、洗
浄塔方式やバブリング方式または撹はん方式など処理に
必要な機能を備えていればどのようなものでも良い。ま
たバッチ処理または連続処理のいずれでも実施可能であ
る。本発明は、１,１,１−トリフルオロクロロエタンま
たはトリクロロエチレンをクロムを主成分とする触媒の
存在下、主として気相でフッ素化して得られるＨＦＣ−
１３４ａと副生するＨＣＦＣ−１１２２を含む反応混合
物からＨＣＦＣ−１１２２を除去するのに最も有効であ
る。本発明の最も好ましい実施態様を以下に示す。The HCFC-1122 processing apparatus may be of any type as long as it has a function required for processing, such as a washing tower system, a bubbling system, or a stirring system. Further, either batch processing or continuous processing can be carried out. The present invention is an HFC-based product obtained by fluorinating 1,1,1-trifluorochloroethane or trichloroethylene mainly in the gas phase in the presence of a catalyst containing chromium as a main component.
It is most effective in removing HCFC-1122 from a reaction mixture containing 134a and by-produced HCFC-1122. The most preferred embodiment of the present invention is shown below.
【０００７】本発明に用いられる処理装置の一例をフロ
ーシートにて図−１に示す。通常前記の反応では生成物
を気相で抜き出す。得られる反応混合物中にはＨＦＣ−
１３４ａ、１,１,１−トリフルオロクロロエタン、フッ
化水素および塩化水素の他に少量のＨＣＦＣ−１１２２
等の有機物が含まれている。この反応混合物から好まし
くはフッ化水素および塩化水素を除去したＨＦＣ−１３
４ａ、１,１,１−トリフルオロクロロエタンおよび少量
のＨＣＦＣ−１１２２等の有機物を含む混合物ガス１が
第１処理装置２に導かれる。An example of the processing apparatus used in the present invention is shown in a flow sheet in FIG. Usually, in the above reaction, the product is withdrawn in the gas phase. HFC-in the reaction mixture obtained
134a, 1,1,1-trifluorochloroethane, hydrogen fluoride and hydrogen chloride in addition to a small amount of HCFC-1122
Contains organic substances such as. HFC-13, preferably free of hydrogen fluoride and hydrogen chloride from the reaction mixture
A mixture gas 1 containing 4a, 1,1,1-trifluorochloroethane and a small amount of an organic substance such as HCFC-1122 is introduced to the first treatment device 2.
【０００８】この第１処理装置２において、混合物ガス
１中に含まれているＨＣＦＣ−１１２２はフルオロスル
フォン酸と向流接触し処理される。上部よりＨＣＦＣ−
１１２２を含まないＨＦＣ−１３４ａおよび１,１,１−
トリフルオロクロロエタンが処理ガス５として得られ
る。下部にはフルオロスルフォン酸と少量の１,１,１−
トリフルオロクロロエタンが残り、第２処理装置３に導
かれる。第２処理装置３において上部より１,１,１−ト
リフルオロクロロエタンが留出ガス６として抜き出され
反応系に循環することができる。下部のフルオロスルフ
ォン酸は冷却槽４に導かれ前述の処理が繰り返される。
ＨＣＦＣ−１１２２はスルフォン化され固形物として処
理槽に蓄積するが、蒸留することにより除くことができ
る。このようにしてすべてのガスをロスすること無く不
純物であるＨＣＦＣ−１１２２を除去することができ
る。In this first treatment apparatus 2, HCFC-1122 contained in the mixture gas 1 is treated in countercurrent contact with fluorosulfonic acid. HCFC- from above
HFC-134a and 1,1,1-without 1122
Trifluorochloroethane is obtained as process gas 5. Fluorosulfonic acid and a small amount of 1,1,1-
Trifluorochloroethane remains and is led to the second processing device 3. In the second treatment device 3, 1,1,1-trifluorochloroethane can be extracted from the upper part as a distillate gas 6 and circulated in the reaction system. The lower fluorosulphonic acid is guided to the cooling tank 4 and the above-mentioned treatment is repeated.
HCFC-1122 is sulfonated and accumulates in the treatment tank as a solid, but can be removed by distillation. In this way, HCFC-1122 as an impurity can be removed without loss of all gases.
【０００９】[0009]
【実施例】以下、実施例によりさらに本発明を詳細に説
明する。 実施例１ 真空にしたフッ素樹脂製容器にフルオロスルフォン酸と
ＨＣＦＣ−１１２２を０.１４mol％含んだＨＦＣ−１３
４ａをそれぞれ１０g充填し２５℃で撹はん後、気相部
のＨＦＣ−１３４ａ中のＨＣＦＣ−１１２２を測定し
た。その結果ＨＣＦＣ−１１２２は検出されなかった。EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 HFC-13 containing 0.14 mol% of fluorosulfonic acid and HCFC-1122 in a vacuum-made fluororesin container.
4 g of each of 4a was filled and stirred at 25 ° C., and then HCFC-1122 in HFC-134a in the gas phase was measured. As a result, HCFC-1122 was not detected.
【００１０】実施例２ 内径９.５mmのガラス管にフルオロスルフォン酸１０gを
いれ２５℃に保ち、ＨＣＦＣ−１１２２を０.１４mol％
含んだＨＦＣ−１３４ａを３０ml／minで吹き込み、出
口のＨＦＣ−１３４ａ中のＨＣＦＣ−１１２２を測定し
た。その結果ＨＣＦＣ−１１２２は検出されなかった。Example 2 10 g of fluorosulfonic acid was placed in a glass tube having an inner diameter of 9.5 mm and kept at 25 ° C., and 0.14 mol% of HCFC-1122 was added.
The contained HFC-134a was blown at 30 ml / min, and HCFC-1122 in the outlet HFC-134a was measured. As a result, HCFC-1122 was not detected.
【００１１】実施例３ フルオロスルフォン酸をクロロスルフォン酸に変えたこ
とを除いて実施例２と同様に実験および測定を行った。
その結果ＨＣＦＣ−１１２２は検出されなかった。Example 3 Experiments and measurements were carried out in the same manner as in Example 2 except that the fluorosulfonic acid was changed to chlorosulfonic acid.
As a result, HCFC-1122 was not detected.
【００１２】実施例４ フッ素樹脂製容器にフルオロスルフォン酸１００gをい
れ、フッ化水素が６６.３mol％、塩化水素が８.７mol
％、ＨＦＣ−１３４ａが２.９mol％、１,１,１−トリフ
ルオロクロロエタンが２２.０８mol％、ＨＣＦＣ−１１
２２が０.０２mol％からなるガスを３０ml／minで吹き
込み、出口のＨＦＣ−１３４ａ中のＨＣＦＣ−１１２２
を測定した。その結果ＨＣＦＣ−１１２２は検出されな
かった。実施例１〜４でわかるようにハロスルフォン酸
で処理することによりＨＦＣ−１３４ａ中の不純物であ
るＨＣＦＣ−１１２２を除去することができる。Example 4 100 g of fluorosulfonic acid was placed in a fluororesin container, and hydrogen fluoride was 66.3 mol% and hydrogen chloride was 8.7 mol.
%, HFC-134a is 2.9 mol%, 1,1,1-trifluorochloroethane is 22.08 mol%, HCFC-11
HCFC-1122 in HFC-134a at the outlet was blown with gas consisting of 0.02 mol% of 22 at 30 ml / min.
Was measured. As a result, HCFC-1122 was not detected. As can be seen from Examples 1 to 4, HCFC-1122 which is an impurity in HFC-134a can be removed by treating with halosulfonic acid.
【図１】 本発明に用いられるＨＣＦＣ−１１２２の処
理装置の一例のフローシートを示す。FIG. 1 shows a flow sheet of an example of a processing apparatus for HCFC-1122 used in the present invention.
１…混合物ガス、 ２…第１処理装置、 ３…第２処理装置、 ４…冷却槽、 ５…処理ガス、 ６…留出ガス。 1 ... Mixture gas, 2 ... 1st processing apparatus, 3 ... 2nd processing apparatus, 4 ... Cooling tank, 5 ... Processing gas, 6 ... Distillation gas.
Claims (4)
び／又はトリクロロエチレンをフッ素化触媒の存在下、
気相でフッ素化して得られる１,１,１,２−テトラフル
オロエタンを含む反応混合物中に不純物として存在する
１,１−ジフルオロクロロエチレンをハロスルフォン酸
と反応させることにより除去する事を特徴とする１,１,
１,２−テトラフルオロエタンの精製法。1. 1,1,1-Trifluorochloroethane and / or trichloroethylene in the presence of a fluorination catalyst,
Characterized by removing 1,1-difluorochloroethylene existing as an impurity in a reaction mixture containing 1,1,1,2-tetrafluoroethane obtained by fluorination in a gas phase by reacting with halosulfonic acid Let 1, 1,
Purification method of 1,2-tetrafluoroethane.
ロエチレンの濃度が１,１,１,２−テトラフルオロエタ
ンに対して２mol％以下である特許請求の範囲第１項記
載の精製法。2. The purification method according to claim 1, wherein the concentration of 1,1-difluorochloroethylene in the reaction mixture is 2 mol% or less with respect to 1,1,1,2-tetrafluoroethane.
化水素が含まれている特許請求の範囲第１項記載の精製
法。3. The purification method according to claim 1, wherein the reaction mixture contains hydrogen fluoride and / or hydrogen chloride.
り、圧力が１〜１０kg／cm2abs.の範囲にある特許請求
の範囲第１項記載の精製法。4. The purification method according to claim 1, wherein the contact temperature is in the range of −20 to 40 ° C. and the pressure is in the range of 1 to 10 kg / cm 2 abs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15924792A JPH061730A (en) | 1992-06-18 | 1992-06-18 | Purification of 1,1,1,2-tetrafluoroethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15924792A JPH061730A (en) | 1992-06-18 | 1992-06-18 | Purification of 1,1,1,2-tetrafluoroethane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH061730A true JPH061730A (en) | 1994-01-11 |
Family
ID=15689574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15924792A Pending JPH061730A (en) | 1992-06-18 | 1992-06-18 | Purification of 1,1,1,2-tetrafluoroethane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH061730A (en) |
-
1992
- 1992-06-18 JP JP15924792A patent/JPH061730A/en active Pending
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