WO2005092786A1 - Method of purifying hydrofluoric acid and purification apparatus - Google Patents
Method of purifying hydrofluoric acid and purification apparatus Download PDFInfo
- Publication number
- WO2005092786A1 WO2005092786A1 PCT/JP2005/005575 JP2005005575W WO2005092786A1 WO 2005092786 A1 WO2005092786 A1 WO 2005092786A1 JP 2005005575 W JP2005005575 W JP 2005005575W WO 2005092786 A1 WO2005092786 A1 WO 2005092786A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrofluoric acid
- gas
- fluorine gas
- fluorine
- arsenic compound
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
- C01B7/196—Separation; Purification by distillation
Definitions
- the present invention relates to a method and an apparatus for dissolving fluorine gas in hydrofluoric acid to remove arsenic compounds contained in hydrofluoric acid.
- hydrofluoric acid used for this purpose is required to be a high-purity product with extremely few impurities, and not only hydrofluoric acid but also chemicals used in semiconductor manufacturing are being highly purified year by year. .
- the required metal impurity concentration in chemicals has reached the order of ppm to ppb, and the order of tens of ppt to several ppt. Requires a level of 5ppt or less, and there is an urgent need to develop a method for removing metal impurities.
- Patent Document 1 there is a method using an oxidizing agent such as potassium permanganate.
- an oxidizing agent such as potassium permanganate.
- manganese and chromium contained in the oxidizing agent are distilled off and the purified hydrofluoric acid is contaminated, a divalent iron salt must be used in combination, and further contamination occurs.
- Patent Document 2 water is added to anhydrous hydrofluoric acid, hydrofluoric acid is introduced into an electrolytic device having a nickel electrode, and electrolysis is performed to reduce the arsenic concentration in hydrofluoric acid. Lowering is exemplified. It is obvious that the electrode force composed of metal dissolves in metal hydrofluoric acid as well as the metal impurity, and cannot be used as a chemical for semiconductor manufacturing. Patent Document 3 discloses a method for removing arsenic impurities in hydrofluoric acid.
- This method involves dissolving fluorine gas in hydrofluoric acid, reacting it with the arsenic compound contained in hydrofluoric acid, and purifying it by distillation. If this method is used, hydrofluoric acid that does not dissolve metal impurities can be used. It is a very good method that can be purified. However, according to Patent Document 3, the concentration of arsenic compounds in purified hydrofluoric acid is about 100ppt. Cannot meet the demands of the semiconductor manufacturing industry.
- Patent Document 1 Japanese Patent Publication No. 47-16407
- Patent Document 2 JP-A-6-263406
- Patent Document 3 JP-A-61-151002
- hydrofluoric acid containing an arsenic compound after adding a fluorine gas or a mixed gas of a fluorine gas and an inert gas to hydrofluoric acid containing an arsenic compound, the mixture is allowed to stay for a certain time, and then hydrofluoric acid is added.
- a method for purifying hydrofluoric acid, which is characterized by distillation, is obtained.
- a fluorine gas or a mixed gas of a fluorine gas and an inert gas is added to hydrofluoric acid containing an arsenic compound. After the addition, the solution is kept for 5 minutes or more, and the hydrofluoric acid is distilled off, thereby obtaining a hydrofluoric acid purification method.
- a method for purifying hydrofluoric acid comprising adding a fluorine gas or a mixed gas of a fluorine gas and an inert gas after reducing the content of an arsenic compound to 100 ppb or less. Is obtained.
- an apparatus for adding a fluorine gas or a mixed gas of a fluorine gas and an inert gas to hydrofluoric acid containing an arsenic compound, an apparatus for adding fluorine, and a distillation apparatus An apparatus for purifying hydrofluoric acid, characterized in that a retaining section for hydrofluoric acid is provided between them, is obtained.
- the purification target of the present invention is hydrofluoric acid, more specifically hydrofluoric acid containing an arsenic compound.
- hydrofluoric acid means hydrofluoric acid containing at least 3% or less of water.
- the arsenic compound contained as an impurity in the hydrofluoric acid of the present invention is not particularly limited to any particular type, and any arsenic compound is effectively removed.
- any arsenic compound is effectively removed.
- AsF and AsF can be mentioned. It also exists in forms other than arsenic itself or fluoride.
- Arsenic compounds can also be effectively removed.
- the amount of the arsenic compound present as an impurity is 100 ppb or less, preferably 50 ppb or less, and more preferably 100 ppb or less.
- the content of arsenic compound Hydrofluoric acid greater than this may be removed by a known method in advance, and then the purification of the present invention may be used.
- the arsenic concentration is reduced to 5 ppt or less by applying the method of the present invention after the arsenic compound is once reduced to 100 ppb or less. When lOOppb or more is contained, the residence time of the method of the invention may be long.
- fluorine gas is added to hydrofluoric acid containing the above impurities.
- the fluorine gas used may be a single gas or a mixed gas with another inert gas.
- the inert gas include helium, argon, and nitrogen.
- the added fluorine gas is at least 50 ppm, preferably at least 60 ppm, more preferably at least 70 ppm, based on hydrofluoric acid.
- the effect saturates even at 80 ppm or more, so the upper limit is preferably set to 80 ppm from an economic viewpoint!
- the concentration of the impurities be 5% or less because the removal efficiency is increased. It is more preferable to be 1% or less!
- the residence time is at least 5 minutes, preferably at least 5 minutes and 30 seconds, more preferably at least 6 minutes.
- the above operation is preferably carried out at a temperature lower than the boiling point of hydrofluoric acid, that is, at 0 to 20 ° C.
- the present invention it is possible to reduce the arsenic content to 5 ppt or less, and it becomes possible to produce ultrapure chemicals.
- the refining device of the present invention includes a device for adding a fluorine gas, that is, a portion for blowing a fluorine gas through a pipe or a vessel equipped with a gas blowing nozzle and then retaining the fluorine gas for a certain period of time before moving to a distillation step.
- the stagnation section may be a container, or may be a simple pipe.
- a baffle plate or the like may be provided inside the container so that the reaction between the fluorine gas and the arsenic compound proceeds. Iron, stainless steel, fluorinated resin, etc. can be used for the contact portion with hydrofluoric acid.
- distillation method a batch distillation purification method, a continuous distillation purification method, or other distillation methods can be appropriately used.
- the raw hydrofluoric acid (99.9%, arsenic 15ppb) was continuously supplied to a rectification unit having a tetrafluoroethylene cooler and a tetrafluoroethylene packed tower at lOOKgZ.
- a rectification unit having a tetrafluoroethylene cooler and a tetrafluoroethylene packed tower at lOOKgZ.
- the water was continuously added so that the fluorine gas concentration became 50 ppm.
- a stagnant section was provided so that hydrofluoric acid to which the fluorine gas was added reached the rectifier after 5 minutes, and rectification was performed.
- the arsenic content of the purified hydrofluoric acid obtained by continuous operation for 10 hours was measured by this method and found to be 5 ppt.
- the present invention after adding fluorine gas to hydrofluoric acid containing an arsenic compound and allowing it to stay for a certain period of time, by performing rectification, it is possible to obtain ultrapure hydrofluoric acid of 5 ppt or less. it can.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of purifying hydrofluoric acid by which hydrofluoric acid having a purity as extremely high as 5 ppt or below can be obtained. The method is characterized by adding fluorine gas or a gaseous mixture of fluorine gas and an inert gas to hydrofluoric acid containing an arsenic compound, causing the resultant mixture to reside for a certain period, and then distilling the hydrofluoric acid.
Description
明 細 書 Specification
フッ化水素酸の精製法及び精製装置 Hydrofluoric acid purification method and purification device
技術分野 Technical field
[0001] 本発明はフッ化水素酸にフッ素ガスを溶解させ、フッ化水素酸に含有するヒ素化合 物を除去する方法、装置に関する。 The present invention relates to a method and an apparatus for dissolving fluorine gas in hydrofluoric acid to remove arsenic compounds contained in hydrofluoric acid.
背景技術 Background art
[0002] フッ化水素酸の代表的な用途には、半導体製造工程でのシリコン酸ィ匕膜のエッチ ング、洗浄等が挙げられる。この用途に使用されるフッ化水素酸には極めて不純物 の少ない高純度品が要求されており、フッ化水素酸に限らず半導体製造に使用され る薬品は年々高純度化が進められて 、る。半導体の高集積ィ匕にともな 、要求される 薬品中の金属不純物濃度は ppmオーダーから ppbオーダー、数十 pptから数 pptレ ベルにまで達しており、特に最先端半導体製造に使用される薬品では 5ppt以下の レベルが要求されており、金属不純物除去方法の開発が急務となっている。 [0002] Typical uses of hydrofluoric acid include etching, cleaning, and the like of a silicon oxide film in a semiconductor manufacturing process. Hydrofluoric acid used for this purpose is required to be a high-purity product with extremely few impurities, and not only hydrofluoric acid but also chemicals used in semiconductor manufacturing are being highly purified year by year. . With the high integration of semiconductors, the required metal impurity concentration in chemicals has reached the order of ppm to ppb, and the order of tens of ppt to several ppt. Requires a level of 5ppt or less, and there is an urgent need to develop a method for removing metal impurities.
[0003] このような現状に対し、フッ化水素酸の中のヒ素化合物を除去する方法もいくつか 開発されて 、る。特許文献 1によれば過マンガン酸カリウム等の酸化剤を用いる方法 がある。しカゝしながら、酸化剤に含まれるマンガン、クロム分の留出がおこり精製フッ 化水素酸が汚染するので、 2価の鉄塩を併用しなければならず、さらなる汚染が発生 する。 [0003] Under such circumstances, several methods for removing arsenic compounds in hydrofluoric acid have been developed. According to Patent Document 1, there is a method using an oxidizing agent such as potassium permanganate. However, since manganese and chromium contained in the oxidizing agent are distilled off and the purified hydrofluoric acid is contaminated, a divalent iron salt must be used in combination, and further contamination occurs.
[0004] 特許文献 2によれば無水フッ化水素酸に水分を添加し、ニッケル電極を有する電 解装置にフッ化水素酸を導入し、電気分解することによりフッ化水素酸中のヒ素濃度 を下げることが例示されて 、る。し力しながら金属で構成される電極力もメタル不純物 力 Sフッ化水素酸に溶解することは明白であり、半導体製造用の薬品として使用できな い。特許文献 3にはフッ化水素酸中のヒ素不純物の除去方法が例示されている。フッ 素ガスをフッ化水素酸に溶解させ、フッ化水素酸に含有するヒ素化合物と反応させた 後、蒸留精製する方法であり、この方法を用いればメタル不純物の溶解もなぐフッ 化水素酸を精製することが可能であり大変優れた方法である。し力しながら、特許文 献 3によれば精製したフッ化水素酸中のヒ素化合物濃度は lOOppt程度であり、現在
の半導体製造業界力 の要求には応えることができない。 [0004] According to Patent Document 2, water is added to anhydrous hydrofluoric acid, hydrofluoric acid is introduced into an electrolytic device having a nickel electrode, and electrolysis is performed to reduce the arsenic concentration in hydrofluoric acid. Lowering is exemplified. It is obvious that the electrode force composed of metal dissolves in metal hydrofluoric acid as well as the metal impurity, and cannot be used as a chemical for semiconductor manufacturing. Patent Document 3 discloses a method for removing arsenic impurities in hydrofluoric acid. This method involves dissolving fluorine gas in hydrofluoric acid, reacting it with the arsenic compound contained in hydrofluoric acid, and purifying it by distillation.If this method is used, hydrofluoric acid that does not dissolve metal impurities can be used. It is a very good method that can be purified. However, according to Patent Document 3, the concentration of arsenic compounds in purified hydrofluoric acid is about 100ppt. Cannot meet the demands of the semiconductor manufacturing industry.
特許文献 1：特公昭 47— 16407号公報 Patent Document 1: Japanese Patent Publication No. 47-16407
特許文献 2：特開平 6— 263406号公報 Patent Document 2: JP-A-6-263406
特許文献 3：特開昭 61-151002号公報 Patent Document 3: JP-A-61-151002
発明の開示 Disclosure of the invention
発明が解決しょうとする課題 Problems to be solved by the invention
[0005] 上記問題点を解決するため、本発明者らは、鋭意検討した結果、ヒ素化合物を含 有するフッ化水素酸にフッ素ガスを溶解させた後、フッ素とヒ素化合物が十分に反応 するための時間滞留させ、次に蒸留することにより超高純度なフッ化水素酸を得られ ることを見出し、本発明に至ったのである。 [0005] In order to solve the above problems, the present inventors have conducted intensive studies. As a result, after dissolving fluorine gas in hydrofluoric acid containing an arsenic compound, fluorine and the arsenic compound sufficiently react. It was found that ultra-high-purity hydrofluoric acid could be obtained by keeping the solution for a period of time and then distilling it, and reached the present invention.
課題を解決するための手段 Means for solving the problem
[0006] 本発明によれば、ヒ素化合物を含有するフッ化水素酸にフッ素ガス又はフッ素ガス と不活性なガスとの混合ガスを添加した後、一定時間滞留させた後、フッ化水素酸を 蒸留する事を特徴とするフッ化水素酸の精製法が得られる。 According to the present invention, after adding a fluorine gas or a mixed gas of a fluorine gas and an inert gas to hydrofluoric acid containing an arsenic compound, the mixture is allowed to stay for a certain time, and then hydrofluoric acid is added. A method for purifying hydrofluoric acid, which is characterized by distillation, is obtained.
[0007] また、本発明によれば、前記フッ化水素酸の精製法にぉ 、て、ヒ素化合物を含有す るフッ化水素酸にフッ素ガス又はフッ素ガスと不活性なガスとの混合ガスを添加した 後、 5分以上滞留させた後、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 の精製法が得られる。 [0007] Further, according to the present invention, in the hydrofluoric acid purification method, a fluorine gas or a mixed gas of a fluorine gas and an inert gas is added to hydrofluoric acid containing an arsenic compound. After the addition, the solution is kept for 5 minutes or more, and the hydrofluoric acid is distilled off, thereby obtaining a hydrofluoric acid purification method.
[0008] また、本発明によれば、前記 、ずれかのフッ化水素酸の精製法にお!、て、ヒ素化合 物を含有するフッ化水素酸に、フッ素ガスを 50ppm以上添加することを特徴とするフ ッ化水素酸の精製法が得られる。 [0008] Further, according to the present invention, in the above-mentioned method for purifying hydrofluoric acid, it is preferable that 50 ppm or more of fluorine gas is added to hydrofluoric acid containing an arsenic compound. A characteristic hydrofluoric acid purification method is obtained.
[0009] 本発明によれば、ヒ素化合物の含有量を lOOppb以下とした後にフッ素ガス又はフ ッ素ガスと不活性ガスとの混合ガスを添加することを特徴とするフッ化水素酸の精製 法が得られる。 [0009] According to the present invention, a method for purifying hydrofluoric acid, comprising adding a fluorine gas or a mixed gas of a fluorine gas and an inert gas after reducing the content of an arsenic compound to 100 ppb or less. Is obtained.
[0010] また、本発明によれば、ヒ素化合物を含有するフッ化水素酸にフッ素ガス又はフッ 素ガスと不活性なガスとの混合ガスを添加する装置と、フッ素を添加する装置と蒸留 装置の間にフッ化水素酸の滞留部を設けたことを特徴とするフッ化水素酸の精製装 置が得られる。
発明の効果 [0010] Further, according to the present invention, an apparatus for adding a fluorine gas or a mixed gas of a fluorine gas and an inert gas to hydrofluoric acid containing an arsenic compound, an apparatus for adding fluorine, and a distillation apparatus An apparatus for purifying hydrofluoric acid, characterized in that a retaining section for hydrofluoric acid is provided between them, is obtained. The invention's effect
[0011] 本発明によればヒ素化合物を含有するフッ化水素酸にフッ素ガスを添加して、一定 時間滞留させた後、精留を行うことにより 5ppt以下という超高純度なフッ化水素酸を 得ることができる。 According to the present invention, after adding fluorine gas to hydrofluoric acid containing an arsenic compound and allowing it to stay for a certain period of time, rectification is performed to produce ultrapure hydrofluoric acid of 5 ppt or less. Obtainable.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
[0012] まず、本発明について、更に詳細に説明する。 First, the present invention will be described in more detail.
本発明の精製対象は、フッ化水素酸であり、更に詳しくはヒ素化合物を含有するフ ッ化水素酸である。ここでフッ化水素酸とは少なくとも全体の 3%以下の水分を含有 するフッ化水素酸を意味する。 The purification target of the present invention is hydrofluoric acid, more specifically hydrofluoric acid containing an arsenic compound. Here, hydrofluoric acid means hydrofluoric acid containing at least 3% or less of water.
[0013] 本発明のフッ化水素酸に不純物として含有されているヒ素化合物は、特にその種 類に限定されるものではなぐいずれも有効に除去される。例えば、フッ化物の形とし て、 AsF、 AsF、があげられる。また、ヒ素自体あるいはフッ化物以外の形で存在す[0013] The arsenic compound contained as an impurity in the hydrofluoric acid of the present invention is not particularly limited to any particular type, and any arsenic compound is effectively removed. For example, as a form of fluoride, AsF and AsF can be mentioned. It also exists in forms other than arsenic itself or fluoride.
3 5 3 5
るヒ素化合物も有効に除去することができる。 Arsenic compounds can also be effectively removed.
[0014] 不純物として存在するヒ素化合物の量は、 lOOppb以下、好ましくは 50ppb以下、よ り好ましくは lOppb以下である。ヒ素化合物の含有量力これより多いフッ化水素酸は 予め公知の方法で除去し、その後本発明の精製を用いればよい。 lOOppb以下とな るまでヒ素化合物を一旦減少させた後本発明方法を適用することによりヒ素濃度が 5 ppt以下となる。 lOOppb以上含有している場合には、発明方法の滞留時間を長時 間とればよい。 [0014] The amount of the arsenic compound present as an impurity is 100 ppb or less, preferably 50 ppb or less, and more preferably 100 ppb or less. The content of arsenic compound Hydrofluoric acid greater than this may be removed by a known method in advance, and then the purification of the present invention may be used. The arsenic concentration is reduced to 5 ppt or less by applying the method of the present invention after the arsenic compound is once reduced to 100 ppb or less. When lOOppb or more is contained, the residence time of the method of the invention may be long.
[0015] なお、ここにおける公知の方法としては、例えば、特開平 61— 151002公報記載の 方法が好ましい。 [0015] As a known method here, for example, a method described in JP-A-61-151002 is preferable.
本発明の実施に際しては、上記不純物を含むフッ化水素酸にフッ素ガスを添加す る。使用するフッ素ガスは単独、或いは他の不活性なガスとの混合ガスでもよい。不 活性なガスとしては、ヘリウム、アルゴン、窒素等が挙げられる。添加するフッ素ガス はフッ化水素酸に対して 50ppm以上、好ましくは 60ppm以上、より好ましくは 70pp m以上である。ただ、 80ppm以上としても効果は飽和するため経済上の観点から上 限は 80ppmとすることが好まし!/、。 In carrying out the present invention, fluorine gas is added to hydrofluoric acid containing the above impurities. The fluorine gas used may be a single gas or a mixed gas with another inert gas. Examples of the inert gas include helium, argon, and nitrogen. The added fluorine gas is at least 50 ppm, preferably at least 60 ppm, more preferably at least 70 ppm, based on hydrofluoric acid. However, the effect saturates even at 80 ppm or more, so the upper limit is preferably set to 80 ppm from an economic viewpoint!
[0016] なお、添加するフッ素ガス又はフッ素ガスと不活性なガスとの混合ガス中における
不純物の濃度は、 5%以下とすることが、除去効率が上がるため好ましい。 1%以下と することがより好まし!/、。 [0016] In the fluorine gas to be added or in a mixed gas of the fluorine gas and the inert gas, It is preferable that the concentration of the impurities be 5% or less because the removal efficiency is increased. It is more preferable to be 1% or less!
[0017] フッ素ガスを添加した後、蒸留操作を行うまでに、添加したフッ素ガスとヒ素化合物 が十分に反応せしめる時間滞留させなくてはならない。滞留時間は、 5分以上、好ま しくは 5分 30秒以上、より好ましくは 6分以上である。上記操作はフッ化水素酸の沸点 以下の温度すなわち 0— 20°Cで実施することが好ましい。 [0017] After the fluorine gas is added, it must be retained for a period of time sufficient for the added fluorine gas to react with the arsenic compound before the distillation operation is performed. The residence time is at least 5 minutes, preferably at least 5 minutes and 30 seconds, more preferably at least 6 minutes. The above operation is preferably carried out at a temperature lower than the boiling point of hydrofluoric acid, that is, at 0 to 20 ° C.
本発明を用いれば、ヒ素含有量を 5ppt以下にも低減することが可能であり、超高純 度薬品の製造が可能になる。 According to the present invention, it is possible to reduce the arsenic content to 5 ppt or less, and it becomes possible to produce ultrapure chemicals.
[0018] 本発明の精製装置は、フッ素ガスを添加する装置すなわち、ガス吹き込みノズルを 備えた配管や容器でフッ素ガスを吹き込み、ついで蒸留工程に移行する前に一定 時間滞留させる部分を備えている。滞留部は容器でもよいが単なる配管でもよい。滞 留部が容器の場合はフッ素ガスとヒ素化合物との反応が進むように容器内部に邪魔 板などを設けることもできる。フッ化水素酸の接触部分は鉄、ステンレス、フッ素榭脂 などが使用できる。 [0018] The refining device of the present invention includes a device for adding a fluorine gas, that is, a portion for blowing a fluorine gas through a pipe or a vessel equipped with a gas blowing nozzle and then retaining the fluorine gas for a certain period of time before moving to a distillation step. . The stagnation section may be a container, or may be a simple pipe. When the retaining section is a container, a baffle plate or the like may be provided inside the container so that the reaction between the fluorine gas and the arsenic compound proceeds. Iron, stainless steel, fluorinated resin, etc. can be used for the contact portion with hydrofluoric acid.
なお、蒸留方法は、回分式蒸留精製法あるいは連続式蒸留精製法その他の蒸留 方法を適宜利用できる。 As the distillation method, a batch distillation purification method, a continuous distillation purification method, or other distillation methods can be appropriately used.
[0019] 以下、本発明の実施例について、詳細に説明するが、本発明はこれに限定される わけではない。 Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto.
実施例 1 Example 1
[0020] 原料フッ化水素酸（99. 9%、ヒ素 15ppb)をテトラフルォロエチレン製冷却器とテト ラフルォロエチレン製の充填塔を有する精留装置に lOOKgZ時で連続的に供給し た。フッ化水素酸供給装置直後に備え付けてあるフッ素ガス供給口からフッ素ガス濃 度が 50ppmになるように連続的に添カ卩した。フッ素ガス供給口力もフッ素ガスを添カロ されたフッ化水素酸が 5分後に精留装置に到達するように滞留部を設け、精留を行 つた。この方法で 10時間連続運転して得られた精製フッ化水素酸のヒ素含有量を測 定したところ 5pptであつた。 [0020] The raw hydrofluoric acid (99.9%, arsenic 15ppb) was continuously supplied to a rectification unit having a tetrafluoroethylene cooler and a tetrafluoroethylene packed tower at lOOKgZ. Was. From the fluorine gas supply port provided immediately after the hydrofluoric acid supply device, the water was continuously added so that the fluorine gas concentration became 50 ppm. For the fluorine gas supply port, a stagnant section was provided so that hydrofluoric acid to which the fluorine gas was added reached the rectifier after 5 minutes, and rectification was performed. The arsenic content of the purified hydrofluoric acid obtained by continuous operation for 10 hours was measured by this method and found to be 5 ppt.
実施例 2 Example 2
[0021] 実施例 1と同じ装置を用いて、滞留部の容積を変えて、フッ素ガスを 50ppm添加し
たフッ化水素酸が精留装置に到達する時間を変えて、 10時間連続運転して得られ た精製フッ化水素酸のヒ素含有量を測定した。測定結果を表 1に示す。 [0021] Using the same apparatus as in Example 1, changing the volume of the stagnation section, adding 50 ppm of fluorine gas. The arsenic content of the purified hydrofluoric acid obtained by continuously operating the hydrofluoric acid for 10 hours was measured while changing the time required for the hydrofluoric acid to reach the rectification device. Table 1 shows the measurement results.
[表 1] [table 1]
実施例 3 Example 3
[0023] 実施例 1と同じ装置を用いて、フッ素ガスの添加濃度を変えて、フッ化水素酸が精 留装置に到達する時間を 5分とし、 10時間連続運転して得られた精製フッ化水素酸 のヒ素含有量を測定した。測定結果を表 2に示す。 [0023] Using the same apparatus as in Example 1, the concentration of fluorine gas was changed, the time required for hydrofluoric acid to reach the rectification apparatus was set to 5 minutes, and the purified hydrofluoric acid obtained by continuous operation for 10 hours was obtained. The arsenic content of the hydrofluoric acid was measured. Table 2 shows the measurement results.
[0024] [表 2]
フッ素ガス添加濃度 (ppm) ヒ素濃度（ppt)[Table 2] Fluorine gas addition concentration (ppm) Arsenic concentration (ppt)
30 20 30 20
40 10 40 10
50 5 50 5
60 3 60 3
70 2 70 2
80 1以下 80 1 or less
90 1以下 90 1 or less
産業上の利用可能性 Industrial applicability
本発明によればヒ素化合物を含有するフッ化水素酸にフッ素ガスを添加して、一定 時間滞留させた後、精留を行うことにより 5ppt以下という超高純度なフッ化水素酸を 得ることができる。
According to the present invention, after adding fluorine gas to hydrofluoric acid containing an arsenic compound and allowing it to stay for a certain period of time, by performing rectification, it is possible to obtain ultrapure hydrofluoric acid of 5 ppt or less. it can.
Claims
[1] ヒ素化合物を含有するフッ化水素酸にフッ素ガス又はフッ素ガスと不活性なガスとの 混合ガスを添加した後、一定時間滞留させた後、フッ化水素酸を蒸留する事を特徴 とするフッ化水素酸の精製法。 [1] After adding a fluorine gas or a mixed gas of a fluorine gas and an inert gas to hydrofluoric acid containing an arsenic compound, the mixture is retained for a certain period of time, and then hydrofluoric acid is distilled. Hydrofluoric acid purification method.
[2] ヒ素化合物を含有するフッ化水素酸にフッ素ガス又はフッ素ガスと不活性なガスとの 混合ガスを添加した後、 5分以上滞留させた後、フッ化水素酸を蒸留することを特徴 とする請求項 1に記載のフッ化水素酸の精製法。 [2] After adding fluorine gas or a mixed gas of fluorine gas and inert gas to hydrofluoric acid containing an arsenic compound, it is retained for at least 5 minutes and then hydrofluoric acid is distilled. The method for purifying hydrofluoric acid according to claim 1, wherein
[3] ヒ素化合物を含有するフッ化水素酸に、フッ素ガスを 50ppm以上添加することを特 徴とする請求項 1又は 2に記載のフッ化水素酸の精製法。 [3] The method for purifying hydrofluoric acid according to claim 1 or 2, wherein 50 ppm or more of fluorine gas is added to hydrofluoric acid containing an arsenic compound.
[4] ヒ素化合物の含有量を lOOppb以下とした後にフッ素ガス又はフッ素ガスと不活性ガ スとの混合ガスを添加することを特徴とする請求項 1乃至 3のいずれ力 1項記載のフッ 化水素酸の精製法。 [4] The fluorine according to any one of [1] to [3], wherein a fluorine gas or a mixed gas of a fluorine gas and an inert gas is added after the content of the arsenic compound is reduced to 100 ppb or less. Hydrogen acid purification method.
[5] ヒ素化合物を含有するフッ化水素酸にフッ素ガス又はフッ素ガスと不活性ガスとの混 合ガスを添加する装置と、フッ素を添加する装置と蒸留装置の間にフッ化水素酸の 滞留部を設けたことを特徴とするフッ化水素酸の精製装置。
[5] Apparatus for adding fluorine gas or a mixed gas of fluorine gas and inert gas to hydrofluoric acid containing an arsenic compound, and retention of hydrofluoric acid between the apparatus for adding fluorine and the distillation apparatus An apparatus for purifying hydrofluoric acid, comprising a unit.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004096278A JP2005281048A (en) | 2004-03-29 | 2004-03-29 | Method and apparatus for refining hydrofluoric acid |
| JP2004-096278 | 2004-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005092786A1 true WO2005092786A1 (en) | 2005-10-06 |
Family
ID=35056104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2005/005575 WO2005092786A1 (en) | 2004-03-29 | 2005-03-25 | Method of purifying hydrofluoric acid and purification apparatus |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2005281048A (en) |
| TW (1) | TW200536780A (en) |
| WO (1) | WO2005092786A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114180526A (en) * | 2021-12-16 | 2022-03-15 | 浙江博瑞电子科技有限公司 | Method for preparing electronic-grade hydrogen fluoride and electronic-grade hydrofluoric acid by removing arsenic in hydrogen fluoride through ultrasonic coupling micro-current |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5188064B2 (en) * | 2006-12-15 | 2013-04-24 | ステラケミファ株式会社 | Method for recovering hydrofluoric acid and hydrochloric acid |
| MX357878B (en) | 2014-12-18 | 2018-07-27 | Mexichem Fluor Sa De Capital Variable | Process for purification of hydrofluoric acid including obtaining arsenious acid by-product. |
| KR102256840B1 (en) * | 2020-12-23 | 2021-05-27 | (주)후성 | Elimination and treatment method of Arsenic compound in hydrogen fluoride for manufacturing of ultra-high-purity hydrogen fluoride |
| KR102310763B1 (en) * | 2021-06-03 | 2021-10-08 | 램테크놀러지 주식회사 | Purification method and apparatus for ultra-high purity hydrogen fluoride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61151002A (en) * | 1984-12-25 | 1986-07-09 | Hashimoto Kasei Kogyo Kk | Method of purifying hydrofluoric acid |
| JPS61191502A (en) * | 1985-02-20 | 1986-08-26 | Hashimoto Kasei Kogyo Kk | Method for purifying hydrofluoric acid |
| JPH11507001A (en) * | 1995-06-05 | 1999-06-22 | スターテック・ベンチャーズ・インコーポレーテッド | On-site production of ultrapure hydrofluoric acid for semiconductor processing |
-
2004
- 2004-03-29 JP JP2004096278A patent/JP2005281048A/en not_active Withdrawn
-
2005
- 2005-03-25 WO PCT/JP2005/005575 patent/WO2005092786A1/en active Application Filing
- 2005-03-28 TW TW94109546A patent/TW200536780A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61151002A (en) * | 1984-12-25 | 1986-07-09 | Hashimoto Kasei Kogyo Kk | Method of purifying hydrofluoric acid |
| JPS61191502A (en) * | 1985-02-20 | 1986-08-26 | Hashimoto Kasei Kogyo Kk | Method for purifying hydrofluoric acid |
| JPH11507001A (en) * | 1995-06-05 | 1999-06-22 | スターテック・ベンチャーズ・インコーポレーテッド | On-site production of ultrapure hydrofluoric acid for semiconductor processing |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114180526A (en) * | 2021-12-16 | 2022-03-15 | 浙江博瑞电子科技有限公司 | Method for preparing electronic-grade hydrogen fluoride and electronic-grade hydrofluoric acid by removing arsenic in hydrogen fluoride through ultrasonic coupling micro-current |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005281048A (en) | 2005-10-13 |
| TW200536780A (en) | 2005-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8821821B2 (en) | Method for the purification of fluorine | |
| US4032621A (en) | Preparation of hydrogen fluoride with low levels of arsenic, iron and sulfite | |
| EP0345354B1 (en) | Process for purifying nitrogen-fluoride | |
| TWI555702B (en) | Method and apparatus for recycling waste sulfuric acid | |
| TW201442944A (en) | Method for manufacturing high purity sulfuric acid | |
| WO2005092786A1 (en) | Method of purifying hydrofluoric acid and purification apparatus | |
| WO2007050505A1 (en) | Andhydrous hydrogen fluoride composition and method of producing the same | |
| JPS61151002A (en) | Method of purifying hydrofluoric acid | |
| EP0617696B1 (en) | Process for purifying hydrogen fluoride | |
| TW460626B (en) | A process for producing high-purity nitrogen trifluoride gas | |
| EP0517723B1 (en) | Process for purifying hydrogen fluoride | |
| US5100639A (en) | Process for purifying hydrogen fluoride | |
| US7569122B2 (en) | Method for purifying nitrogen trifluoride | |
| CN111886674B (en) | Gas for substrate processing, storage container, and substrate processing method | |
| US5411726A (en) | Process for purifying hydrogen fluoride | |
| JP4535269B2 (en) | Hydrogen production apparatus and hydrogen production method | |
| KR100432593B1 (en) | A process for purifying nitrogen trifluoride gas | |
| JP3043741B1 (en) | Method for producing high-purity phosphoric acid | |
| JP2007176770A (en) | Method of producing high purity fluorine gas and apparatus for producing high purity fluorine gas | |
| KR20130009201A (en) | Method for manufacturing of ultra-high-purity hydrofluoric acid | |
| US7229601B2 (en) | Ammonia reclamation system | |
| CN114852978A (en) | Preparation system and method for directly producing electronic-grade nitric acid from ammonia gas | |
| JPS61191502A (en) | Method for purifying hydrofluoric acid | |
| CN118308739A (en) | Production device and process of ultra-high purity hydrofluoric acid | |
| WO1997018158A1 (en) | Manufacture of very low arsenic hydrogen fluoride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| DPEN | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101) | ||
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| WWW | Wipo information: withdrawn in national office |
Country of ref document: DE |
|
| 122 | Ep: pct application non-entry in european phase |