JPS61191502A - Method for purifying hydrofluoric acid - Google Patents
Method for purifying hydrofluoric acidInfo
- Publication number
- JPS61191502A JPS61191502A JP3330085A JP3330085A JPS61191502A JP S61191502 A JPS61191502 A JP S61191502A JP 3330085 A JP3330085 A JP 3330085A JP 3330085 A JP3330085 A JP 3330085A JP S61191502 A JPS61191502 A JP S61191502A
- Authority
- JP
- Japan
- Prior art keywords
- hydrofluoric acid
- arsenic
- acid
- compounds
- ppm
- 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims description 26
- 150000001495 arsenic compounds Chemical class 0.000 claims abstract description 23
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 21
- -1 halogen fluoride Chemical class 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 3
- 229940093920 gynecological arsenic compound Drugs 0.000 abstract description 14
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 229910052740 iodine Inorganic materials 0.000 abstract description 2
- 229910052785 arsenic Inorganic materials 0.000 description 16
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 14
- 150000002367 halogens Chemical class 0.000 description 13
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000012776 electronic material Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- FQFKTKUFHWNTBN-UHFFFAOYSA-N trifluoro-$l^{3}-bromane Chemical compound FBr(F)F FQFKTKUFHWNTBN-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- CEBDXRXVGUQZJK-UHFFFAOYSA-N 2-methyl-1-benzofuran-7-carboxylic acid Chemical compound C1=CC(C(O)=O)=C2OC(C)=CC2=C1 CEBDXRXVGUQZJK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910020323 ClF3 Inorganic materials 0.000 description 1
- 101100441092 Danio rerio crlf3 gene Proteins 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- AFOASOGDNUBPHH-UHFFFAOYSA-M [F-].[I+] Chemical class [F-].[I+] AFOASOGDNUBPHH-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000012442 analytical experiment Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229910052787 antimony Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical class [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はフッ化水素酸中に不純物として存在するヒ素化
合物を除去ｌ〜精製フッ化水素酸を得る全く新規な方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a completely new process for removing arsenic compounds present as impurities in hydrofluoric acid to obtain purified hydrofluoric acid.
本発明の方法によって精製されたフッ化水ｉ酸ｄ電子材
料工業および金属工業で特にシリコンの洗浄剤および蝕
刻剤として広く使用されるものである。The fluorinated hydric acid purified by the method of the present invention is widely used in the electronic material industry and the metal industry, especially as a cleaning agent and etching agent for silicone.
従来のフン化水素酸中に含まれる不純物のうちとりわけ
ヒ素およびヒ素化合物は、高性能の半導体素子の作製に
重大々悪影響を及ぼしていることが明らかになり、この
ような用途に特にヒ素の少いフッ化水素酸の需要が増大
［−でいる。Among the impurities contained in conventional hydrofluoric acid, it has become clear that arsenic and arsenic compounds, in particular, have a serious negative effect on the production of high-performance semiconductor devices. Demand for hydrofluoric acid is increasing.
フッ化水素酸の精製法としてこれまでよく知られている
方法は（ａ）フッ化水素酸を蒸留する方法、（１））特
別に精製された原料を用いてフッ化水素ガスを発生させ
る方法ＩＣ）不純物をアルカリ金属塩まだはアルカリ士
金属塩として除去する方法、（ｄ）アルカリイオン存在
下においてフッ化水素酸に酸化剤を添加して反応させる
方法などによっている、（特公昭３９−５６０６号公報
、特公昭４７−１６４０７号公報参照）。Well-known methods for purifying hydrofluoric acid include (a) distilling hydrofluoric acid, and (1) generating hydrogen fluoride gas using specially purified raw materials. IC) A method in which impurities are removed as an alkali metal salt or an alkali metal salt; (d) A method in which an oxidizing agent is added to hydrofluoric acid and reacted in the presence of alkali ions. (Japanese Patent Publication No. 39-5606 (See Japanese Patent Publication No. 47-16407).
これらの方法のうちとくに（（１）の方法が高純度フッ
化水素酸を得るにもつとも適していると言われている。Among these methods, method (1) is said to be particularly suitable for obtaining high purity hydrofluoric acid.
しかしながらこの（ａ）の方法では高価な酸化剤例えば
過マンガン酸力１ノウム、重クロム酸カリウムなどを使
用するを常とし、不純物の含有量が高い場合には非常に
不経済な方法であり、まだ用いる薬剤が精製フッ化水素
酸中に混入して汚染をおこす致命的な欠点があるだめ、
工業的精製法としては不向きである。However, this method (a) usually uses expensive oxidizing agents such as permanganate, potassium dichromate, etc., and is extremely uneconomical when the content of impurities is high. However, there is a fatal drawback that the chemicals still used can mix into purified hydrofluoric acid and cause contamination.
It is not suitable as an industrial refining method.
本発明者らはフッ化水素酸中のヒ素化合物の除去方法に
ついて、多数の研究を行ってきた結果、上記のような公
知の方法とは全く異った新規々ヒ素化合物の除去方法を
究明したのである。The present inventors have conducted numerous studies on methods for removing arsenic compounds from hydrofluoric acid, and as a result, have discovered a novel method for removing arsenic compounds that is completely different from the known methods described above. It is.
すなわち本発明者らは、ヒ素化合物を含有するフッ化水
素酸にフッ化・・ロゲンを添加してヒ素化合物と反応さ
せた後、原料フッ化水素酸を蒸留することにより原料中
に含まれていたヒ素化合物は除去し易い型のヒ素化合物
に変わり、単にフッ化水素酸を蒸留することによってヒ
素分を完全に分離除去できる事実を見出したのである。That is, the present inventors added fluorinated chloride to hydrofluoric acid containing an arsenic compound and reacted with the arsenic compound, and then distilled the raw material hydrofluoric acid to remove the fluoride contained in the raw material. They discovered that the arsenic compounds that had been removed were converted into easily removable arsenic compounds, and that the arsenic content could be completely separated and removed simply by distilling hydrofluoric acid.
フッ化ハロゲンは一般式ＸＦ２ｎ−Ｈで表わされる。Fluorinated halogen is represented by the general formula XF2n-H.
式中Ｘは塩素、臭素、沃素のいずれかを示し、Ｆ ・は
フッ素を示しまだｎは０．１．２または３のいずれかの
値をとるものとする。In the formula, X represents chlorine, bromine, or iodine, F.sub.2 represents fluorine, and n takes a value of 0.1.2 or 3.
具体的な化合物は次のような分子式で表わされるもので
ある。A specific compound is represented by the following molecular formula.
フッ化塩素化合物： ＣＩＦ、 ＣＩＦ、、ＣｌＦ５フ
ッ化臭素化合物： ＢｒＦ、 ＢｒＦ ＢｒＦ５Ｂｒ
Ｆ。Chlorine fluoride compound: CIF, CIF, ClF5 Bromine fluoride compound: BrF, BrF BrF5Br
F.
い
フッ化ヨウ素化合物：工Ｆ、 工Ｆ５、 工Ｆ５、工Ｆ
。Fluoride iodine compounds: Engineering F, Engineering F5, Engineering F5, Engineering F
.
これらの化合物はそれぞれ単独であるいは混合物の形で
実際に使用される。These compounds are used individually or in the form of mixtures.
フッ化ハロゲンによるヒ素化合物、の除去作用はフッ化
ハロゲン中のＦがフッ化水素酸中のヒ素化合物を五フッ
化ヒ素もしくは高沸点難揮発性ヒ素化合物例えばポリフ
ルオロアルゼン酸に変えることによるものと考えられる
が、その反応機構の詳細な学理的説明を現在簡明ならし
めることは容易ではない、
フッ化ハロゲンの強力な酸化作用によって、ヒ素は五フ
ッ化ヒ素にまず酸化される。このものはフッ化水素酸よ
りも沸点の低い化合物であるため、適当な条件下ではフ
ッ化水素以外のハロゲン化水素あるいはハロゲンガスと
共に蒸留によってフッ化水素酸よりも低沸点側に前もっ
て留出されることになり、またさらに舌１目すべきこと
はヒ素化合物が高沸点化合物に移行した場合にはポリフ
ルオロアルゼン酸等として確実に釜残と々って残留し、
蒸留されるフッ化水素酸留分中にはほとんどヒ素が含有
されなくなるという事実である。The removal effect of arsenic compounds by fluorinated halogen is due to F in fluorinated halogen converting the arsenic compound in hydrofluoric acid to arsenic pentafluoride or a high boiling point refractory arsenic compound such as polyfluoroarzenic acid. Although it is conceivable, it is currently difficult to provide a detailed scientific explanation of the reaction mechanism. Arsenic is first oxidized to arsenic pentafluoride by the strong oxidizing action of halogen fluoride. Since this compound has a lower boiling point than hydrofluoric acid, under appropriate conditions it can be distilled together with hydrogen halides other than hydrogen fluoride or halogen gas to a lower boiling point than hydrofluoric acid. Furthermore, it is important to note that when arsenic compounds migrate to high boiling point compounds, they will definitely remain in the pot as polyfluoroarzenic acid, etc.
The fact is that the hydrofluoric acid fraction that is distilled contains almost no arsenic.
分析学的な実験から本発明者はフッ化ハロゲンとヒ素化
合物の反応により、これまで知られていなかった高沸点
化合物（例えばポリフルオロアルゼン酸）が円滑に生成
すること、且つフッ化ハロゲンからくるハロゲン化合物
が効果的にフッ化水素酸と分離［−うることを見いだ１
一本発明を完成１−だのである。From analytical experiments, the present inventor found that a hitherto unknown high-boiling point compound (e.g. polyfluoroarzenic acid) is smoothly produced by the reaction between a fluorinated halogen and an arsenic compound, and that Discovering that halogen compounds can be effectively separated from hydrofluoric acid [-1]
This is the first step in completing the invention.
そしてフッ化ハロゲンによるヒ素化合物の除去作用はフ
ッ化ハロゲンの強力な酸化作用のために最初に本発明者
が予想していたよりも極めて効果的に行なわれるのであ
る。The action of removing arsenic compounds by the fluorinated halogen is much more effective than originally anticipated by the inventors due to the strong oxidizing action of the fluorinated halogen.
従来の方法では用いる処理剤の添加量が原料ＨＦに対し
過マンガン酸カリウムの場合Ｉ Ｑ Ｑ ｐｉｎ〜１０
！ ０００ ｐｐｍ 、過酸化水素の場合、９，０００
ｐｐｍと非常に多く必要である。In the conventional method, when the amount of processing agent added is potassium permanganate to the raw material HF, I Q Q pin ~ 10
! 000 ppm, 9,000 for hydrogen peroxide
A very large amount of ppm is required.
本発明の方法によるフッ化ハロゲンの場合には原料ＨＦ
に対し多くの場合１１００ｐｐ以下、好ましくはＩＱｐ
ｐｍ〜ＩＱＱｐｐｍで充分その効果を発揮する。In the case of fluorinated halogen by the method of the present invention, raw material HF
1100 pp or less, preferably IQp
It fully exhibits its effect at pm to IQQppm.
本発明の方法で加えるべきフッ化ハロゲンの量は、原料
フッ化水素酸中のヒ素濃度が数ｐｐｍ〜数十ｐｐｍの場
合には、はぼｓｏｐｐｍ〜ＩＱＱｐｐｍで充分な効果が
発揮されるが、フッ化水素酸にはヒ素化合物のほか一般
に不純物として、被酸化性のイオウ化合物゛、リン化合
物、アンチモン化合物が存在１〜でおり、これらの不純
物もフッ化ハロゲンを消費するため、これらの存在量を
測定してフッ化ハロゲンの添加量の調整をしなければな
らないのは当−然である。When the arsenic concentration in the raw material hydrofluoric acid is from several ppm to several tens of ppm, the amount of fluorinated halogen to be added in the method of the present invention is approximately so ppm to IQQ ppm, but sufficient effects are exhibited. In addition to arsenic compounds, hydrofluoric acid generally contains oxidizable sulfur compounds, phosphorus compounds, and antimony compounds1 as impurities.Since these impurities also consume fluorinated halogens, their abundance is limited. Naturally, it is necessary to measure the amount of halogen fluoride and adjust the amount of halogen fluoride added.
本発明の方法はフッ化水素酸水溶液から無水フッ化水素
酸に至る広範囲のフッ化水素酸に適用出来るのであるが
、フッ化ノ・ロゲンは水分と反応して部分的に消費され
ることばなるので、水分はできるだけ少ない方が好まし
く、また水分量に応じて添加量を多くしなければならな
い。The method of the present invention can be applied to a wide range of hydrofluoric acids ranging from an aqueous solution of hydrofluoric acid to anhydrous hydrofluoric acid, but the fluorinated hydrogen reacts with moisture and is partially consumed. Therefore, it is preferable that the amount of water is as low as possible, and the amount added must be increased depending on the amount of water.
多くの実験結果から本発明の方法は水分３係以下の無水
フッ化水素酸に適用した場合極めて合理的かつ経済的に
達成しうるものであり、すぐれた工業的価値を有するも
のである。Many experimental results show that the method of the present invention can be achieved very rationally and economically when applied to anhydrous hydrofluoric acid having a water content of 3 or less, and has excellent industrial value.
体発明の方法で用いるフッ化ハロゲンの形態はその化合
物の物性に従って気体状、液体状、固体状のいずれの形
態であってもよく、またフッ化水素酸溶液、塩素溶液あ
るいは臭素溶液のような形にして用いてもよい。The form of the fluorinated halogen used in the method of the invention may be gaseous, liquid, or solid depending on the physical properties of the compound, and may be in the form of a hydrofluoric acid solution, a chlorine solution, or a bromine solution. It may also be used in the form.
勿論本発明に用いられるフッ化ハロゲンは単独でも二種
以上の混合物でもよくまたハロゲン（Ｆ２・Ｃｅ２、Ｂ
ｒ２、工２）との混合物の形でもよい。Of course, the fluorinated halogen used in the present invention may be used alone or in a mixture of two or more.
It may also be in the form of a mixture with r2 and engineering 2).
一般的には、フッ化ハロゲンのうち常温付近で 。Generally, among fluorinated halogens, at room temperature.
液体状を示すＣｌＦ３、ＢｒＦ、、Ｂ ｒ Ｆ ｓ、工
Ｆ５が保存、計量、仕込み等に対しとくに取扱いやすい
ものであり、これについで気体状のものが使用し易い。ClF3, BrF, BrFs, and F5, which are in liquid form, are particularly easy to handle for storage, measurement, preparation, etc., and gaseous ones are next easier to use.
本発明の方法においてフッ化ハロゲンとヒ素化合物との
反応は温度、圧力に限定されないが、常温常圧下でも迅
速に進行するので、特別な条件や装置を必要とせず無水
フッ化水素酸ではその沸点以下の温度すなわち１０〜２
０°Ｃで実施されるのが好ましい。In the method of the present invention, the reaction between the halogen fluoride and the arsenic compound is not limited to temperature or pressure, but since it proceeds rapidly even at room temperature and pressure, no special conditions or equipment are required. Temperatures below i.e. 10-2
Preferably it is carried out at 0°C.
本発明のフッ化水素酸の蒸留方法は、回分式蒸留精製法
或いは連続式蒸留精製法等が採用され効率のよい分留塔
が付設されているならばより充分な成果が得られる。The method for distilling hydrofluoric acid of the present invention can achieve more satisfactory results if a batch distillation purification method or a continuous distillation purification method is employed and an efficient fractionation column is attached.
本発明者らは本発明の方法に関し、多数の実験を行い本
発明の優秀性を確認しだのであるが、それらの実験例の
ことごとくについて示すことは繁雑にすぎるので多数の
実験例の中から数例を抽出して以下に実施例として示す
ことにする。The present inventors conducted numerous experiments regarding the method of the present invention and confirmed the superiority of the present invention, but since it would be too complicated to describe all of the experimental examples, only a few of the numerous experimental examples will be presented. A few examples will be extracted and shown below as examples.
従って本発明の方法は、単に以下に示す実施例のみに限
定して解釈されるべきでなく、本発明の趣旨と精神を逸
脱せざる限りにおいて、任意にその実施態様を変更［〜
で、実施し得ることは当然である。Therefore, the method of the present invention should not be construed as being limited to the examples shown below, and the embodiments may be arbitrarily changed without departing from the spirit and spirit of the present invention.
Of course, it can be implemented.
実施例１
還流冷却器および蒸留管を備えたポリ（トリフルオロク
ロルエチレン）製容器（容ｉ １ ／ｌ ） ＩＩＣ、
フッ化水素酸（ＨＦ ９９．９％ Ａｓ １０ ｐｐｍ
） ８００ ｇを入れ、三フッ化塩素（ＣＩＦ３’）
を原料のＨＦ’に対しＣｄ Ｆ３中のＦがａｏｐｐｍに
なるように添加して５〜６時間煮沸して反応させたのち
、容器をさらに加熱してフッ化水素酸を分留し精製フッ
化水素酸を得た、
この精製フン化水素酸のヒ素含有量を測定１〜だところ
０．００１ｐｐｍ以下であり、電子材料用のフッ化水素
酸として有用々ものであった。Example 1 Container made of poly(trifluorochloroethylene) equipped with a reflux condenser and a distillation tube (capacity i 1 /l) IIC,
Hydrofluoric acid (HF 99.9% As 10 ppm
) Add 800 g of chlorine trifluoride (CIF3')
is added to the raw material HF' so that the F in CdF3 becomes aoppm, and the mixture is boiled for 5 to 6 hours to react.The container is further heated to fractionally distill the hydrofluoric acid to produce purified fluoride. The arsenic content of the purified hydrofluoric acid obtained was measured to be 0.001 ppm or less, and was useful as hydrofluoric acid for electronic materials.
実施例２
実施例１と同じ装置を用い、容器にフッ化水素酸（ＨＦ
９９．９％ Ａｓ ｌｐｐｍ） ８００９を入れ、三
フッ化臭素（ＢｒＦ）を原料のＨＦに対しＢ ｒ Ｆ
ｓ中のＦがＩＱＱｐｐｌＨになるように添加してやや加
圧して３０°Ｃで２時間反応させたのち、フッ化水素酸
を蒸留し精製フッ化水素酸を得た。この精製フッ化水素
酸のヒ素含有量を測定１−たところ０・ＱＱ１ｐｐｍ以
下であシミ子材料用のフッ化水素酸として有用なもので
あった。Example 2 Using the same equipment as in Example 1, hydrofluoric acid (HF) was added to the container.
Add 99.9% As lppm) 8009 and add bromine trifluoride (BrF) to the raw material HF.
After adding F in s to IQQpplH and reacting at 30°C for 2 hours under slightly increased pressure, hydrofluoric acid was distilled to obtain purified hydrofluoric acid. The arsenic content of this purified hydrofluoric acid was measured and found to be less than 0.QQ1 ppm, which was found to be useful as hydrofluoric acid for Shimiko material.
実施例３
実施例１と同じ装置を用い、容器にフッ化水素酸（ＨＦ
９９．８％ Ａｓ ８ ｐｐＩｎ） ８００９を入れ
、五フッ化ヨウ素（工Ｆ５）を原料のＨＦに対し工Ｆ５
中のＦが７５ｐｐｍになるように添加して１５°Ｃで１
夜放置して反応させたのち、フッ化水素酸を蒸留し精製
フッ化水素酸を得た。この精製フッ化水素酸のヒ素含有
量を測定したところ、０．００１ｐｐｍ以下であり電子
材料用のフッ化水素酸として有用なものであった。Example 3 Using the same equipment as in Example 1, a container was filled with hydrofluoric acid (HF).
Add 99.8% As 8 ppIn) 8009 and add iodine pentafluoride (F5) to the raw material HF.
Add so that the F inside is 75 ppm and heat at 15°C.
After leaving to react overnight, the hydrofluoric acid was distilled to obtain purified hydrofluoric acid. When the arsenic content of this purified hydrofluoric acid was measured, it was found to be 0.001 ppm or less, which was found to be useful as hydrofluoric acid for electronic materials.
実施例４
ｒｂ −ｂｋ ＩｑＩ ｈ Ｉ−ｒ：’Ｉ ＋
−＊七５巨表 口ｉ １− ＃ 、！ｕ Ｉｚｒ −
１、、、／し、し１式島匍（ＨＦ ９９．９％ Ａｓ
１ｏｐｐｍ） ｓｏａｇを入れ、塩素ガスとフッ素ガス
とを当モル反応させて得だガス状の一塩化フッ素（ｃｒ
ｔ）を原料のＨＦ’に対しＣｇＦ中のＦが８０ｐｐｍに
なるように吹き込んで１夜放置して反応させたのち、フ
ッ化水素酸を蒸留し精製フッ化水素酸を得だ。Example 4 rb -bk IqI h I-r:'I +
-*75 giant table mouth i 1- #,! u Izr -
1,,,/shi,shi type 1 Shimakou (HF 99.9% As
Fluorine monochloride (Cr
t) was blown into the raw material HF' so that the F content in CgF was 80 ppm, and the mixture was left to react overnight, and then the hydrofluoric acid was distilled to obtain purified hydrofluoric acid.
この精製フッ化水素酸のヒ素含有量を測定したところ０
．００１ ｐｌ）１１１以下であり、電子材料用のフッ
化水素酸として有用なものであった。When the arsenic content of this purified hydrofluoric acid was measured, it was 0.
．． 001 pl) 111 or less, and was useful as hydrofluoric acid for electronic materials.
実施例５
実施例１と同じ装置を用い、容器にフッ化水素酸（Ｌ・
ｙ ９９．８％ Ａ８９ ｐｐｍ） ａｏｏｐを入れ、
液体状の三フッ化臭素を冷却して得た固体状の三フッ化
臭素（Ｂ ｒ Ｆ ｓ ）を原料のＨＦに対しＢ ｒ
Ｆ ３中のＦが７０〜ｓｏｐｐｍになるように添加して
３時間煮沸して反応させたのち、フッ化水素酸を蒸留し
精製フッ化水素酸を得た。この精製フッ化水素酸のヒ素
含有量を測定したところ、０．００１ ｐｐｍ以下であ
り、電子材料用のフッ化水素酸として有用なものであつ
た、−
趣施例６
実施例１と同じ装置を用い、容器にフッ化水素酸（ＨＦ
’ ９７．５１ Ａ８７ｐｐｍ、 Ｈ２Ｏ２，４５％）
８００ｇを入れ、三フッ化塩素（ＣＡ’Ｆ３）を原料の
ＨＦに対しＣＩ Ｆ３中のＦが１ｏ口〜１５Ｑｐｐｍに
なるように添加して、１夜放置して反応させたのち、フ
ッ化水素酸を蒸留し精製フッ化水素酸を得だ。この精製
フッ化水素酸のヒ素含有量を測定したところ、０．００
１ｐｐｍ以下であり、電子材料用のフッ化水素酸として
有用なものであった。Example 5 Using the same equipment as in Example 1, hydrofluoric acid (L.
y 99.8% A89 ppm) Add aoop,
Solid bromine trifluoride (B r F s ) obtained by cooling liquid bromine trifluoride is mixed with HF as a raw material.
After adding so that F in F3 was 70 to soppm and reacting by boiling for 3 hours, hydrofluoric acid was distilled to obtain purified hydrofluoric acid. When the arsenic content of this purified hydrofluoric acid was measured, it was 0.001 ppm or less, and it was found to be useful as hydrofluoric acid for electronic materials. - Example 6 Same device as Example 1 using hydrofluoric acid (HF) in a container.
'97.51 A87ppm, H2O2, 45%)
Add 800 g of chlorine trifluoride (CA'F3) to the raw material HF so that the F in CI F3 becomes 10 to 15 Qppm, leave it to react overnight, and then add hydrogen fluoride. Distill the acid to obtain purified hydrofluoric acid. When the arsenic content of this purified hydrofluoric acid was measured, it was found to be 0.00.
It was 1 ppm or less, and was useful as hydrofluoric acid for electronic materials.
（施例７
凝縮還流装置および蒸留管を備えたポリ（トリフルオロ
クロルエチレン）製容器（容量１ｅ）に、液体状の三フ
ッ化臭素（Ｂ ｒ Ｆ ３）が原料のＨＥ’に対しＢ
ｒ Ｆ ３中のＦとして７５〜１１００ｐｐになるよう
に加えられたフッ化水素酸（ＨＦ ９９．８係Ａ日８ｐ
ｐｍ）を、連続的に２００ｇΔ時の供給速度で仕込んで
加熱し精留する。(Example 7) In a poly(trifluorochloroethylene) container (capacity 1e) equipped with a condensation reflux device and a distillation tube, liquid bromine trifluoride (B r F 3) was added to
r Hydrofluoric acid added to 75-1100pp as F in F3 (HF 99.8% A day 8p
pm) is continuously charged at a feed rate of 200 gΔh, heated and rectified.
この方法で８時間連続運転して得た精製フン化水素酸の
ヒ素含有量を測定したところｏ、ｎｏ１ｐｐｍ以下であ
り、電子材料用のフッ化水素酸として有用なものであっ
た。When the arsenic content of purified hydrofluoric acid obtained by continuous operation for 8 hours in this method was measured, it was found to be less than 1 ppm, and was found to be useful as hydrofluoric acid for electronic materials.
Claims (1)
塩素、臭素、沃素のいずれかを示し、Ｆはフッ素を示し
、ｎは０、１、２または３のいずれかの値を示す）で表
わされる化合物群から選ばれた少くとも一つのフッ化ハ
ロゲンを、ヒ素化合物を含有するフッ化水素酸に添加し
てヒ素化合物と反応させた後フッ化水素酸を蒸留するこ
とを特徴とするフッ化水素酸の精製法。(1) Represented by the general formula Hydrofluoric acid, characterized in that at least one halogen fluoride selected from a group of compounds is added to hydrofluoric acid containing an arsenic compound, reacted with the arsenic compound, and then the hydrofluoric acid is distilled. Acid purification method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3330085A JPS61191502A (en) | 1985-02-20 | 1985-02-20 | Method for purifying hydrofluoric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3330085A JPS61191502A (en) | 1985-02-20 | 1985-02-20 | Method for purifying hydrofluoric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61191502A true JPS61191502A (en) | 1986-08-26 |
| JPH0261404B2 JPH0261404B2 (en) | 1990-12-20 |
Family
ID=12382697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3330085A Granted JPS61191502A (en) | 1985-02-20 | 1985-02-20 | Method for purifying hydrofluoric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61191502A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4892625A (en) * | 1987-01-27 | 1990-01-09 | Tama Chemicals Co., Ltd. | Method for producing high purity chemicals |
| WO2005092786A1 (en) * | 2004-03-29 | 2005-10-06 | Stella Chemifa Corporation | Method of purifying hydrofluoric acid and purification apparatus |
-
1985
- 1985-02-20 JP JP3330085A patent/JPS61191502A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4892625A (en) * | 1987-01-27 | 1990-01-09 | Tama Chemicals Co., Ltd. | Method for producing high purity chemicals |
| WO2005092786A1 (en) * | 2004-03-29 | 2005-10-06 | Stella Chemifa Corporation | Method of purifying hydrofluoric acid and purification apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0261404B2 (en) | 1990-12-20 |
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