JPH03176434A - Removing of hydrogen fluoride - Google Patents
Removing of hydrogen fluorideInfo
- Publication number
- JPH03176434A JPH03176434A JP31458589A JP31458589A JPH03176434A JP H03176434 A JPH03176434 A JP H03176434A JP 31458589 A JP31458589 A JP 31458589A JP 31458589 A JP31458589 A JP 31458589A JP H03176434 A JPH03176434 A JP H03176434A
- Authority
- JP
- Japan
- Prior art keywords
- component
- difluoroethane
- chloro
- mixture
- hydrogen fluoride
- 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.)
- Granted
Links
- 229910000040 hydrogen fluoride Inorganic materials 0.000 title claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims description 12
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 12
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 claims 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 abstract description 13
- 229940126062 Compound A Drugs 0.000 abstract 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract 2
- 239000012808 vapor phase Substances 0.000 abstract 2
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 12
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、フッ化水素（以下、ＨＦと呼ぶ）と１−りａ
ロー１．１−ジフルオロエタン（以下、Ｒ−１４２ｂと
呼ぶ）の混合物から、ＨＦを除去し、Ｒ−１４２ｂを濃
縮する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides hydrogen fluoride (hereinafter referred to as HF) and
The present invention relates to a method for removing HF and concentrating R-142b from a mixture of rho-1,1-difluoroethane (hereinafter referred to as R-142b).
Ｒ−１４２ｂは、通常、１，１．１−トリフルオロエタ
ンや、ｌ、１−ジクロロエチレンなどの塩化炭化水素と
ＨＰを反応させることにより製造される。しかし、Ｒ−
１４２ｂは、ＨＦと共沸混合物を形成し、Ｒ−１４２ｂ
を分離濃縮することば極めて困難である。R-142b is usually produced by reacting HP with a chlorinated hydrocarbon such as 1,1,1-trifluoroethane or 1,1-dichloroethylene. However, R-
142b forms an azeotrope with HF, R-142b
It is extremely difficult to separate and concentrate.
これまで実施されている方法としては、これらの混合物
を水性相により洗浄する方法（英国特許第１，３２３，
２３４号参照）の他、液相分離が用いられている。例え
ば、特公平１−１４２１０号公報にはＨＦ、！：Ｒ−１
４２ｂの混合物に１，１−ジクロロ−１−フルオロエタ
ンを添加し、これを分液することによりＲ−１４２ｂと
１．１−ジクロロｌ−フルオロエタンからなる有機物相
中のＴ（Ｆ’含量を低減させる方法が開示されている。The methods practiced so far include washing these mixtures with an aqueous phase (UK Patent No. 1,323,
234), liquid phase separation is also used. For example, in Japanese Patent Publication No. 1-14210, HF,! :R-1
By adding 1,1-dichloro-1-fluoroethane to the mixture of R-142b and separating the liquid, the T(F' content) in the organic phase consisting of R-142b and 1,1-dichloro-1-fluoroethane was determined. A method for reducing this is disclosed.
しかし、この方法では分液装置のほかにＲ−１４２ｂと
ｌ。However, this method uses R-142b and l in addition to the liquid separation device.
ｌ−ジクロロ−１−フルオロエタン（以下、Ｒ−１４１
ｂと呼ぶ）を分離するための設備を必要とするなど必ず
しも有効な方法とは言えない。l-dichloro-1-fluoroethane (hereinafter referred to as R-141
This method cannot necessarily be said to be effective, as it requires equipment for separating (referred to as b).
本発明者らは、ＨＦとＲ−１４２ｂを主体とする混合物
からＨＦを除去する方法について研究を重ねた結果、こ
の混合物中にＲ−１４２ｂより沸点の低い第３成分を存
在させ、これを気液平衡状態においた場合、その気相部
のＨＰ／Ｒ−１４２ｂの比率は液相中のそれに比べて低
い値であること、例えば６ｋｇ／ｃｍ”の圧力を示すＨ
Ｆ／Ｒ−１４２ｂのモル比が４０／６０の混合物に全圧
が１１１＜ｇ／Ｃｘ”になるまで第３成分を加えた場合
、気相部における前記モル比が８５／１５と低くなるこ
とを見い出し本発明を完成した。As a result of repeated research into a method for removing HF from a mixture mainly consisting of HF and R-142b, the present inventors discovered that a third component with a lower boiling point than R-142b was present in the mixture, and this was removed by gas. When placed in a liquid equilibrium state, the ratio of HP/R-142b in the gas phase is a lower value than that in the liquid phase, for example, H indicating a pressure of 6 kg/cm''.
When the third component is added to a mixture with a F/R-142b molar ratio of 40/60 until the total pressure becomes 111<g/Cx'', the molar ratio in the gas phase becomes as low as 85/15. They discovered this and completed the present invention.
本発明は、ＨＦとＲ−１４２ｂを含む混合物中にＲ−１
４２ｂより低い沸点を持つ第３成分を存在させ、これを
気液平衡状態におき、その気相部をそのままあるいは液
化させて回収することを特徴とする。また、上記混合物
を同様の第３成分の存在下で蒸留することを特徴とする
。さらに本発明のもう一つの特徴は上記混合物を同様の
第３成分の存在下で蒸留したのち、この第３成分を除去
して得られる主としてＨＦとＲ−１４２ｂからなる混合
物を蒸留することによりＨＦをＲ−１４２ｂとの共沸混
合物として除くことである。The present invention provides R-1 in a mixture containing HF and R-142b.
The method is characterized in that a third component having a boiling point lower than that of 42b is present, the third component is brought into a vapor-liquid equilibrium state, and the gas phase is recovered as is or after being liquefied. The method is also characterized in that the above mixture is distilled in the presence of a similar third component. Furthermore, another feature of the present invention is that after distilling the above mixture in the presence of a similar third component, the mixture obtained by removing this third component is distilled to obtain HF and R-142b. is removed as an azeotrope with R-142b.
前述のごと＜ＨＰとＲ−１４２ｂの混合系には共沸が存
在し、通常の蒸留ではＨＦ／Ｒ−１４２ｂノモル比で４
０／６０以上ｉ、：Ｒ−１４２ｂをａ縮することはでき
ない。言い替えると、この組成比の液相は平衡状態にあ
る気相の組成比と同一となる。ここに気体の第３成分を
存在させると気相中には当然この第３成分が増加するが
、ＨＦとＲ−１４２ｂとの比率に着目した場合、液相中
よりも気相中のＲ−１４２ｂの割合が増加する。これに
伴って共沸点はよりＲ−１４２ｂに富む方向に移動する
ことが明らかになった。As mentioned above, there is an azeotrope in the mixed system of HP and R-142b, and in normal distillation, the no molar ratio of HF/R-142b is 4.
i, :R-142b cannot be a-condensed by 0/60 or more. In other words, the liquid phase having this composition ratio is the same as the composition ratio of the gas phase in an equilibrium state. If a gaseous third component is present here, this third component will naturally increase in the gas phase, but when focusing on the ratio of HF and R-142b, R- in the gas phase is higher than in the liquid phase. 142b increases. It has become clear that, along with this, the azeotropic point moves in a direction richer in R-142b.
本発明に用いる第３成分は、系の圧力を高める働きをす
る。したがって、Ｒ−１４２ｂより低い沸点を持つもの
でなければならない。塩化水素、１．１．１−）リフル
オロエタン（以下、Ｒ−１４３８と呼ぶ）、窒素および
アルゴン等の不活性ガスが好適に用いられる。特に好ま
しいものは塩化水素であり、後述のごとく、塩素化炭化
水素とＨＦを反応させてＲ−１４２ｂを製造する際に副
生ずる塩化水素を用いることが最も有効である。The third component used in the present invention serves to increase the pressure of the system. Therefore, it must have a lower boiling point than R-142b. Inert gases such as hydrogen chloride, 1.1.1-)rifluoroethane (hereinafter referred to as R-1438), nitrogen and argon are preferably used. Particularly preferred is hydrogen chloride, and as will be described later, it is most effective to use hydrogen chloride, which is produced as a by-product when producing R-142b by reacting a chlorinated hydrocarbon with HF.
気液平衡状態にある系の内部圧力は、第３成分が存在す
るため同じ温度でも高くなるが、系内圧力を高くするこ
とのみが目的ではない。温度を上げることにより圧力を
上げても共沸組成に顕著な変化はない。Although the internal pressure of a system in a gas-liquid equilibrium state is high even at the same temperature due to the presence of the third component, the purpose is not only to increase the system internal pressure. There is no significant change in the azeotropic composition when increasing the pressure by increasing the temperature.
第３成分の圧力は、０．２〜２０ ｋｇ／ａｍ’が好ま
しい。０ 、２ｋｇ／ａｍ”以下では効果が小さく、２
０ｋｇ／ｃｍ”以上では気相部のＲ−１４２ｂ分圧が低
くなるため好ましくない。特に好ましい圧力は０゜２か
ら１０ ｋｇ７ｃｍ”の範囲である。The pressure of the third component is preferably 0.2 to 20 kg/am'. 0. Below 2kg/am", the effect is small;
If the pressure exceeds 0 kg/cm", the partial pressure of R-142b in the gas phase becomes low, which is undesirable. Particularly preferred pressure is in the range of 0°2 to 10 kg/cm".
本発明を実施するためには、蒸留装置を用いることが好
ましい。この蒸留装置は、蒸留に必要な機能を備えてい
ればどのようなものでも使用可能である。単蒸留の装置
でも段塔を備えた精留装置でもよい。後者の場合が特に
好ましい結果となる。In order to carry out the present invention, it is preferable to use a distillation apparatus. Any distillation device can be used as long as it has the functions necessary for distillation. It may be a simple distillation device or a rectification device equipped with a plate column. The latter case gives particularly favorable results.
またバッチ蒸留、連続蒸留のいずれでも実施可能である
。Further, either batch distillation or continuous distillation can be carried out.
第３成分は、スチルあるいは段塔の中央から供給し、凝
縮器のトップから抜き出される。圧力が維持されるよう
に供給と抜き出しの量を調節する。The third component is fed from the center of the still or tray column and withdrawn from the top of the condenser. Adjust the amount of supply and withdrawal to maintain pressure.
本発明は１，１．１−トリフルオロエタンまたは１．１
−ジクロロエチレンを、無触媒または触媒の存在下、Ｈ
Ｆでフッ素化して得られるＲ−１４２ｂとＨＦを含む混
合物からＨＦを除去するのに有効に使用できる。通常、
これらの反応では気相から生成物を抜き出す。得られる
混合物中にはＲ−１４２ｂＳＨＦ’および塩化水素の他
にＲ−１４１ｂ、Ｒ−１４３ａおよびその他少量の有機
物が含まれている。これらの成分は任意の割合で含まれ
ていてよい。この混合物は、既に第３成分（）（ＣＣお
よびＲ−１４３ａ）を含んでいるので、特に他の第３成
分を供給しないでもそのまま蒸留装置に導き、圧力を維
持しながら抜き出していればよい。The present invention relates to 1,1,1-trifluoroethane or 1.1
-dichloroethylene without or in the presence of a catalyst, H
It can be effectively used to remove HF from a mixture containing R-142b and HF obtained by fluorination with F. usually,
These reactions extract products from the gas phase. The resulting mixture contains R-141b, R-143a and small amounts of other organic substances in addition to R-142bSHF' and hydrogen chloride. These components may be included in any proportion. Since this mixture already contains the third component () (CC and R-143a), it is sufficient to introduce it as it is to the distillation apparatus and extract it while maintaining the pressure without particularly supplying the other third component.
必要があればさらに添加してもよい。蒸留装置のトップ
のＨＦ／１４２ｂモル比は上記混合物のそれより低くな
る。Further addition may be made if necessary. The HF/142b molar ratio at the top of the distillation apparatus will be lower than that of the above mixture.
上記方法によりＨＦを除去して濃縮されたＲ−１４２ｂ
と第３成分と少量のＨＦの混合物からは、そのまま水洗
する、あるいは冷却後分液によりＨＦ層とＲ−１４２ｂ
層に分離するなど公知の方法でさらにＨＦが除かれる。R-142b concentrated by removing HF by the above method
From the mixture of the third component and a small amount of HF, the HF layer and R-142b can be separated by washing with water as is or by separating the liquids after cooling.
Further HF is removed by known methods such as separation into layers.
しかし、本発明によればこの混合物からさらに有効にＨ
Ｆを除去することが可能である。すなわち、この混合物
から蒸留により第３成分を除去し、得られるＲ−１４２
ｂとＨＦの混合物を再度蒸留する。第３成分かないので
、ＨＦとＲ−１４２ｂの共沸はモル比でＨＦ：Ｒ−１４
２ｂ＝４０：６０に戻り、低沸点成分としてこの共沸混
合物か除去される。その結果、ＨＦを含まないＲ−１４
２ｂを得ることができる。この共沸混合物は再度、第３
成分の存在下で前述の処理が繰り返される。このように
して、すべてのＨＦを有効に利用しなからＲ−１４２ｂ
を単独で得ることができる。However, according to the present invention, H
It is possible to remove F. That is, the third component is removed from this mixture by distillation, and the resulting R-142
The mixture of b and HF is again distilled. Since there is no third component, the azeotrope of HF and R-142b is the molar ratio of HF:R-14
2b=40:60, and this azeotrope is removed as a low-boiling component. As a result, R-14 containing no HF
2b can be obtained. This azeotrope is again
The foregoing process is repeated in the presence of the ingredients. In this way, all HF can be used effectively and R-142b
can be obtained alone.
以下、実施例により更に詳細に説明する。Hereinafter, it will be explained in more detail with reference to Examples.
実施例１
真空にした５ＵＳ３１６製高圧容器に、ＨＦとｒ（−１
４２ｂをモル比４０／６０になるように充填し、温度を
３７．５℃に保ち、系内圧力を６に９／ｃｘ’にした。Example 1 HF and r(-1
42b was charged at a molar ratio of 40/60, the temperature was maintained at 37.5°C, and the system internal pressure was set at 6:9/cx'.
ここに第３成分であるＨＣＱを１１゜０ｋｙ／ｃｍ”に
なるまで加圧した。１時間、同じ温度に維持し、平衡に
達するのを待ち、この状態における気相部のＨＣとＲ−
１４２ｂのモル比を測定した。その結果、Ｒ−１４２ｂ
／ＨＦのモル比は８５／１５であった。HCQ, the third component, was pressurized to 11°0 ky/cm". The temperature was maintained at the same temperature for 1 hour, and equilibrium was reached. HCQ and R-
The molar ratio of 142b was measured. As a result, R-142b
/HF molar ratio was 85/15.
実施例２
塩化水素の代わりにＮ、を用いたことを除いて、実施例
１と同様に実験および測定を行なった。気相部のＲ−１
４２ｂ／ＨＦのモル比は８５／１５であった。Example 2 Experiments and measurements were conducted in the same manner as in Example 1, except that N was used instead of hydrogen chloride. R-1 in the gas phase
The molar ratio of 42b/HF was 85/15.
実施例３〜５
ＨＣ（ｌの圧力を変えたことを除いて、実施例１と同様
に、実験および測定を行なった。条件および結果を実施
例１および２とともに表１に示す。Examples 3 to 5 Experiments and measurements were conducted in the same manner as in Example 1, except that the pressure of HC (l) was changed. The conditions and results are shown in Table 1 together with Examples 1 and 2.
比較例１および２
ＨＣＣを添加しなかったことおよび、実験条件を変えた
ことを除いて、実施例１と同様に、実験および測定を行
なった。条件および結果を表１に示す。Comparative Examples 1 and 2 Experiments and measurements were conducted in the same manner as in Example 1, except that HCC was not added and the experimental conditions were changed. The conditions and results are shown in Table 1.
第１表
実施例 全圧
番号 ｋｇ／ａｘ”
ＩＣ（２圧
ｋｇ／ａｍ”
温度
℃
気相部モル比
Ｒ−１４２ｂ ＨＰ
実施例１ １１．０ ５．０ ３７．５ ８５
１５実施例２ １１．０ ５．０（Ｎ、） ３
７．５ ８５ １５実施例３ ６．５ ０，５
３７．５ ７３ ２７実施例４ ７．０ １
．０ ３７゜５ ８０ ２０実施例５ ９．０
３．０ ３７．５ ８２ １ｇ比較例１
４．０ ０，０ ２４．５ ６０ ４０比
較例２ ７．０ ０．０ ４７．５ ６２
３８ただし、液相組成モル比はＲ−１４２ｂ／ＨＦ＝６
０／４０である。Table 1 Examples Total pressure number kg/ax" IC (2 pressure kg/am" Temperature °C Gas phase molar ratio R-142b HP Example 1 11.0 5.0 37.5 85
15 Example 2 11.0 5.0 (N,) 3
7.5 85 15 Example 3 6.5 0,5
37.5 73 27 Example 4 7.0 1
．． 0 37°5 80 20 Example 5 9.0
3.0 37.5 82 1g Comparative Example 1
4.0 0.0 24.5 60 40 Comparative Example 2 7.0 0.0 47.5 62
38 However, the liquid phase composition molar ratio is R-142b/HF=6
It is 0/40.
比較例１および２かられかるように、系内圧力４ｋｇ／
ｃｔｘ”で、気相部のＨＦ’／Ｒ−１４２ｂはモル比４
０／６０の組成を示す。この組成は、系内圧カフｋｇ／
ｃｘ”に上げても大きな変化は見られない。As seen from Comparative Examples 1 and 2, the system pressure was 4 kg/
ctx", the molar ratio of HF'/R-142b in the gas phase is 4.
Shows the composition of 0/60. This composition is system pressure cuff kg/
Even if you raise it to "cx", there is no big change.
一方、第３成分であるＨＣＱまたは窒素を存在させるこ
とにより、気相部のＨＦ／Ｒ−１４２ｂは顕著に低下し
ている。On the other hand, the presence of HCQ or nitrogen, which is the third component, significantly reduces HF/R-142b in the gas phase.
実施例６
ＳＵＳ３１６製３５０ｘＱのスチル部のある蒸留塔（２
０段）にＲ−１４２ｂ２５０ｇ（２，５モル）およびＨ
Ｆ３４ｙ（１，７モル）を仕込み、スチルを４０℃に加
熱するとともに、塔の下段に塩化水素ガスを重量換算で
毎分１ｇ供給した。塩化水素ガスの供給にしたがって、
系内圧力は徐々に上昇した。Example 6 Distillation column (2
0 stage), 250 g (2.5 mol) of R-142b and H
F34y (1.7 mol) was charged, the still was heated to 40°C, and hydrogen chloride gas was supplied to the lower stage of the column at 1 g per minute in terms of weight. According to the supply of hydrogen chloride gas,
The pressure in the system gradually increased.
圧力を９から１１ｋｇ／ｃｚ”に維持するように塔頂コ
ンデンサのガス放出パルプを調節した。ガスの放出を開
始してから１時間後にこのガスをサンプリングし、分析
した。その結果、塩化水素６２モル％、Ｒ−１４２ｂ３
２モル％、ＨＦ６モル％であった。この時の塔頂ガス温
度は３３℃であった。The gas release pulp in the overhead condenser was adjusted to maintain the pressure between 9 and 11 kg/cz. One hour after gas release began, the gas was sampled and analyzed. As a result, hydrogen chloride 62 Mol%, R-142b3
2 mol%, HF 6 mol%. The top gas temperature at this time was 33°C.
Ｒ−１４２ｂ：Ｉ−ＩＰのモル比は８４：１６となる。The molar ratio of R-142b:I-IP is 84:16.
比較例３
塩化水素ガスを供給しなかったことおよび系内圧力を維
持するためにガス放出パルプを閉じたままにしたことを
除いて実施例６と同様にして蒸留操作および分析を行な
った。この時、塔頂圧力は６ｋｇ／ｃｍ”で温度は４０
℃を示した。塔頂ガスのモル比はＲ−１４２ｂ：ＨＦ＝
５９：４１であり、仕込み組成と全く同一であった。Comparative Example 3 Distillation operation and analysis were carried out in the same manner as in Example 6, except that hydrogen chloride gas was not supplied and the gas release pulp was kept closed to maintain system pressure. At this time, the tower top pressure was 6 kg/cm" and the temperature was 40
℃ was shown. The molar ratio of the top gas is R-142b:HF=
The ratio was 59:41, which was exactly the same as the starting composition.
実施例７
ＳＵ８３１６製３Ｑの容器に１．１．１−トリクロロエ
タン２６７ｇ（２モル）およびＨＦ’２０００ｇ（１０
０モル）を仕込み、８０℃で２時間加熱した。Example 7 267 g (2 mol) of 1.1.1-trichloroethane and 2000 g of HF' (10
0 mol) and heated at 80°C for 2 hours.
反応の進行に従って、主反応生成物であるＲ−１４２ｂ
と塩化水素が発生するため、系内圧力が８から１０ｋｇ
／ａｘ”に維持されるように、容器上部に連結した充填
塔と５℃の冷水により冷却したコンデンサーを通して発
生ガスを放出した。このガスは全量を回収した。この中
にはＲ−１４２ｂが１．８１９（１，８モル）、ＨＦが
６９（０，３モル）含まれていた。Ｒ−１４２ｂ：ＨＦ
のモル比は８６：１４となり、Ｒ−１４２ｂとＨＰの２
成分系の共沸点より大きくずれた比率になることが分か
る。As the reaction progresses, the main reaction product R-142b
and hydrogen chloride are generated, so the system pressure increases from 8 to 10 kg.
The generated gas was discharged through a packed tower connected to the top of the vessel and a condenser cooled with cold water at 5°C so as to maintain the temperature at .819 (1.8 mol), HF was contained 69 (0.3 mol).R-142b: HF
The molar ratio of R-142b and HP is 86:14.
It can be seen that the ratio deviates significantly from the azeotropic point of the component system.
さらに、回収ガスを液化して蒸留塔に仕込み、スチル温
度を徐々に上げていくとコンデンサから、最初に塩化水
素が、次にＲ−１４３ａが留出した。Furthermore, the recovered gas was liquefied and charged into a distillation column, and when the still temperature was gradually raised, first hydrogen chloride and then R-143a were distilled out from the condenser.
その次にＲ−１４２ｂ：ＨＦが６０：４０（モル比）の
留出が見られ、これが終了した後の蒸留塔スチル中の液
体はＨＦを約１００ｐ州含むＲ−１４２ｂであった。Next, distillation of R-142b:HF at a molar ratio of 60:40 was observed, and after this was completed, the liquid in the still of the distillation column was R-142b containing about 100 parts of HF.
Claims (3)
フルオロエタンを含む混合物中に１−クロロ−１，１−
ジフルオロエタンより低い沸点を持つ第３成分を存在さ
せ、これを気液平衡状態におき、その気相部をそのまま
あるいは液化させて回収することを特徴とするフッ化水
素と１−クロロ−１，１−ジフルオロエタンを含む混合
物からフッ化水素を除去する方法。(1) In a mixture containing at least hydrogen fluoride and 1-chloro-1,1-difluoroethane, 1-chloro-1,1-
Hydrogen fluoride and 1-chloro-1,1 characterized in that a third component having a boiling point lower than difluoroethane is present, the third component is brought into a gas-liquid equilibrium state, and the gas phase is recovered as it is or after being liquefied. - A method for removing hydrogen fluoride from a mixture containing difluoroethane.
フルオロエタンを含む混合物を１−クロロ−１，１−ジ
フルオロエタンより低い沸点を持つ第３成分の存在下で
蒸留することを特徴とするフッ化水素と１−クロロ−１
，１−ジフルオロエタンを含む混合物からフッ化水素を
除去する方法。(2) Fluorine fluoride, characterized in that a mixture containing at least hydrogen fluoride and 1-chloro-1,1-difluoroethane is distilled in the presence of a third component having a boiling point lower than that of 1-chloro-1,1-difluoroethane. hydrogen chloride and 1-chloro-1
, a method for removing hydrogen fluoride from a mixture containing 1-difluoroethane.
フルオロエタンを含む混合物を１−クロロ−１，１−ジ
フルオロエタンより低い沸点を持つ第３成分の存在下で
蒸留したのち、該第３成分を除去して得られる主として
フッ化水素と１−クロロ−１，１−ジフルオロエタンか
らなる混合物を蒸留することによりフッ化水素をフッ化
水素／１−クロロ−１，１−ジフルオロエタンの共沸混
合物として除くことを特徴とするフッ化水素の除去方法
。(3) After distilling a mixture containing at least hydrogen fluoride and 1-chloro-1,1-difluoroethane in the presence of a third component having a boiling point lower than that of 1-chloro-1,1-difluoroethane, the third component By distilling the mixture obtained by removing hydrogen fluoride and 1-chloro-1,1-difluoroethane, hydrogen fluoride is converted into an azeotrope of hydrogen fluoride/1-chloro-1,1-difluoroethane. A method for removing hydrogen fluoride, characterized by removing hydrogen fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1314585A JP2778162B2 (en) | 1989-12-04 | 1989-12-04 | How to remove hydrogen fluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1314585A JP2778162B2 (en) | 1989-12-04 | 1989-12-04 | How to remove hydrogen fluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03176434A true JPH03176434A (en) | 1991-07-31 |
| JP2778162B2 JP2778162B2 (en) | 1998-07-23 |
Family
ID=18055066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1314585A Expired - Fee Related JP2778162B2 (en) | 1989-12-04 | 1989-12-04 | How to remove hydrogen fluoride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2778162B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996011176A1 (en) * | 1994-10-07 | 1996-04-18 | Daikin Industries, Ltd. | Method of separating pentafluoroethane and process for producing pentafluoroethane by utilizing said method |
-
1989
- 1989-12-04 JP JP1314585A patent/JP2778162B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996011176A1 (en) * | 1994-10-07 | 1996-04-18 | Daikin Industries, Ltd. | Method of separating pentafluoroethane and process for producing pentafluoroethane by utilizing said method |
| US5849160A (en) * | 1994-10-07 | 1998-12-15 | Daikin Industries, Ltd. | Process of separating pentafluoroethane and process of producing pentafluoroethane using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2778162B2 (en) | 1998-07-23 |
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