JP2001199712A - Method of producing hydrofluoric acid - Google Patents
Method of producing hydrofluoric acidInfo
- Publication number
- JP2001199712A JP2001199712A JP2000003914A JP2000003914A JP2001199712A JP 2001199712 A JP2001199712 A JP 2001199712A JP 2000003914 A JP2000003914 A JP 2000003914A JP 2000003914 A JP2000003914 A JP 2000003914A JP 2001199712 A JP2001199712 A JP 2001199712A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- hydrofluoric acid
- reaction
- fluoride
- alkali metal
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、フッ酸の製造方法
に関する。TECHNICAL FIELD The present invention relates to a method for producing hydrofluoric acid.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】従来、フ
ッ酸（ＨＦ）を製造するには、蛍石（ＣａＦ2）と硫酸
を反応させてフッ酸と副生物の硫酸カルシウムを生成し
ている。2. Description of the Related Art Conventionally, to produce hydrofluoric acid (HF), fluorite (CaF 2 ) is reacted with sulfuric acid to produce hydrofluoric acid and calcium sulfate as a by-product. I have.
【０００３】この方法によれば、貴重な資源である蛍石
を際限なく消費することとなり、地球環境における資源
の有効利用の観点から非合理的であることは明らかであ
る。According to this method, fluorite, which is a precious resource, is consumed endlessly, which is obviously unreasonable from the viewpoint of effective use of resources in the global environment.
【０００４】一方、従来より、フロンガス製造プラント
などのフッ素化反応プラントから排出されるフッ酸（Ｈ
Ｆ）は、硫酸に吸収させて混酸とした後に、この混酸を
加熱して回収している。混酸の加熱装置にはモネルやハ
ステロイなどの高級材を使用しているが、混酸中のフッ
酸や水分によって腐食が起こる。混酸の有効利用を図る
ことは、フッ素化反応プラントにおける重要課題であ
る。On the other hand, hydrofluoric acid (H) discharged from a fluorination reaction plant such as a CFC gas production plant has been conventionally used.
F) is obtained by heating the mixed acid after absorbing it with sulfuric acid to form a mixed acid. Although high-grade materials such as Monel and Hastelloy are used for the mixed acid heating device, corrosion occurs due to hydrofluoric acid and moisture in the mixed acid. Effective use of mixed acids is an important issue in fluorination reaction plants.
【０００５】本発明の目的は、蛍石を消費することな
く、フッ酸を効率的に製造する方法を提供することにあ
る。An object of the present invention is to provide a method for efficiently producing hydrofluoric acid without consuming fluorite.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、鋭意研究
を重ねた結果、アルカリ金属のフッ化物を硫酸およびフ
ッ酸を含有する混酸と反応させる方法が、工業的に優れ
ていることを見出し、本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies, the present inventors have found that a method of reacting an alkali metal fluoride with a mixed acid containing sulfuric acid and hydrofluoric acid is industrially excellent. As a result, the present invention has been completed.
【０００７】すなわち、本発明は、下記に示すとおりの
フッ酸の製造方法を提供するものである。 項１． アルカリ金属のフッ化物を、硫酸およびフッ酸
を含有する混酸と反応させるフッ酸の製造方法。 項２． アルカリ金属のフッ化物がフッ化ナトリウムで
ある項１に記載の方法。 項３． １００〜５００℃で反応させる項１または２に
記載の方法。That is, the present invention provides a method for producing hydrofluoric acid as described below. Item 1. A method for producing hydrofluoric acid, comprising reacting an alkali metal fluoride with a mixed acid containing sulfuric acid and hydrofluoric acid. Item 2. Item 2. The method according to Item 1, wherein the alkali metal fluoride is sodium fluoride. Item 3. Item 3. The method according to Item 1 or 2, wherein the reaction is carried out at 100 to 500 ° C.
【０００８】[0008]
【発明の実施の形態】本発明においては、アルカリ金属
のフッ化物（フッ化アルカリ金属）を、硫酸およびフッ
酸を含有する混酸と反応させて、フッ酸を製造する。In the present invention, hydrofluoric acid is produced by reacting an alkali metal fluoride (alkali metal fluoride) with a mixed acid containing sulfuric acid and hydrofluoric acid.
【０００９】本発明における反応系内においては、次の
反応が行われている。The following reaction is carried out in the reaction system of the present invention.
【００１０】 ２ＭＦ＋Ｈ2ＳＯ4＋ＨＦ→３ＨＦ＋Ｍ2ＳＯ4 （式中、Ｍはアルカリ金属を示す。） アルカリ金属のフッ化物としては、フッ化ナトリウム
（ＮａＦ）、フッ化リチウム（ＬｉＦ）、フッ化カリウ
ム（ＫＦ）、フッ化ルビジウム（ＲｂＦ）、フッ化セシ
ウム（ＣｓＦ）などが挙げられる。中でも、フッ化ナト
リウムが好ましい。2MF + H 2 SO 4 + HF → 3HF + M 2 SO 4 (wherein, M represents an alkali metal.) As the alkali metal fluoride, sodium fluoride (NaF), lithium fluoride (LiF), potassium fluoride (KF), rubidium fluoride (RbF), cesium fluoride (CsF) and the like. Among them, sodium fluoride is preferable.
【００１１】フッ化ナトリウム（ＮａＦ）はどのように
して得られたものであってもよい。フッ化ナトリウムの
製造方法としては、例えば、(1)フッ酸（ＨＦ）と水酸
化ナトリウム（ＮａＯＨ）の反応、(2)ヘキサフルオロ
ケイ酸（Ｈ2ＳｉＦ6）と水酸化ナトリウムの反応、(3)
ヘキサフルオロケイ酸ナトリウム（Ｎａ2ＳｉＦ6）と水
酸化ナトリウムの反応、(4)リン鉱石と水酸化ナトリウ
ムの反応などが挙げられる。ヘキサフルオロケイ酸は、
蛍石からフッ酸を製造する際に産業廃棄物として副生す
るため、上記(2)のようにヘキサフルオロケイ酸を用い
て得られたフッ化ナトリウムをフッ酸製造に用いると、
資源の有効利用が図れる。[0011] Sodium fluoride (NaF) may be obtained in any manner. Examples of the method for producing sodium fluoride include (1) a reaction between hydrofluoric acid (HF) and sodium hydroxide (NaOH), (2) a reaction between hexafluorosilicic acid (H 2 SiF 6 ) and sodium hydroxide, and 3)
Examples include a reaction between sodium hexafluorosilicate (Na 2 SiF 6 ) and sodium hydroxide, and (4) a reaction between phosphate rock and sodium hydroxide. Hexafluorosilicic acid is
When hydrofluoric acid is produced from fluorite, it is by-produced as industrial waste, so when using sodium fluoride obtained using hexafluorosilicic acid as in (2) above for hydrofluoric acid production,
Effective use of resources can be achieved.
【００１２】硫酸およびフッ酸を含有する混酸も、どの
ようにして得られたものであってもよい。例えば、フロ
ンガス製造プラントなどのフッ素化反応プラントから排
出されるフッ酸（ＨＦ）を硫酸に吸収させて得た混酸を
用いることもできる。この場合には、フッ素化反応プラ
ントにおいて混酸を加熱してフッ酸を回収する工程が省
けるので、混酸の加熱装置の省略やユーティリティーの
削減などが可能となる。しかも、副生混酸をフッ酸の製
造に用いるため、資源の有効利用が図れる。The mixed acid containing sulfuric acid and hydrofluoric acid may be obtained in any manner. For example, a mixed acid obtained by absorbing hydrofluoric acid (HF) discharged from a fluorination reaction plant such as a fluorocarbon gas production plant with sulfuric acid can be used. In this case, the step of heating the mixed acid to recover the hydrofluoric acid in the fluorination reaction plant can be omitted, so that the heating device for the mixed acid and the number of utilities can be reduced. Moreover, since the by-product mixed acid is used for the production of hydrofluoric acid, resources can be effectively used.
【００１３】混酸中における硫酸とフッ酸の混合割合
は、特に限定されないが、重量比で、Ｈ2ＳＯ4：ＨＦ＝
９５〜８０：５〜２０であるのが好ましい。この混酸は
数％の水分を含んでいてもよいが、反応効率の点から
は、できるだけ水分が少ないのが好ましい。Although the mixing ratio of sulfuric acid and hydrofluoric acid in the mixed acid is not particularly limited, the weight ratio of H 2 SO 4 : HF =
95-80: 5-20 is preferred. This mixed acid may contain a few percent of water, but from the viewpoint of reaction efficiency, it is preferable that the mixed acid contains as little water as possible.
【００１４】本発明におけるアルカリ金属のフッ化物と
混酸との反応比は、混酸中の硫酸含有量により変化す
る。アルカリ金属のフッ化物と混酸中の硫酸が、ＭＦ：
Ｈ2ＳＯ4＝２：０．８〜１．２（モル比）となるように
して反応させるのが好ましい。In the present invention, the reaction ratio between the alkali metal fluoride and the mixed acid changes depending on the sulfuric acid content in the mixed acid. The sulfuric acid in the mixed acid with the alkali metal fluoride is MF:
H 2 SO 4 = 2: 0.8~1.2 react as a (molar ratio) is preferable.
【００１５】反応温度は、１００〜５００℃が好まし
く、２５０〜３００℃がより好ましい。[0015] The reaction temperature is preferably from 100 to 500 ° C, more preferably from 250 to 300 ° C.
【００１６】反応圧力は、特に限定されず、大気圧、減
圧、加圧のいずれでもよい。The reaction pressure is not particularly limited, and may be atmospheric pressure, reduced pressure, or increased pressure.
【００１７】滞留時間は、１〜４時間が好ましく、２〜
３時間がより好ましい。The residence time is preferably 1 to 4 hours,
3 hours is more preferred.
【００１８】反応容器は、特に限定されない。また、バ
ッチ式、連続式のいずれで反応させてもよい。The reaction vessel is not particularly limited. Moreover, you may make it react by either a batch type or a continuous type.
【００１９】反応により生成したＨＦガスは、凝縮、精
留などの通常の手段を用いて単離することができる。The HF gas produced by the reaction can be isolated by using ordinary means such as condensation and rectification.
【００２０】[0020]
【発明の効果】本発明によれば、蛍石を消費することな
く、フッ酸を効率的に製造することができるので、資源
の有効利用が図れる。According to the present invention, hydrofluoric acid can be efficiently produced without consuming fluorite, so that resources can be effectively used.
【００２１】[0021]
【実施例】以下、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの実施例によってなんら限定
されるものではない。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.
【００２２】実施例１ 攪拌装置とＴＩＣ（温度指示・コントロール装置）を備
えた２Ｌ反応器に、ＮａＦ粉体（３００ｇ、７．１４ｍ
ｏｌ）を入れ、攪拌しながら定量ポンプにより９８％Ｈ
2ＳＯ4（３６０ｇ、３．６０ｍｏｌ）とＨＦ（３０ｇ、
１．５０ｍｏｌ）との混酸を添加した。添加終了後に、
２８０℃まで昇温して３時間反応させた。生成したＨＦ
を水に吸収させ、中和滴定によりＨＦ生成量を測定し
た。ＨＦへの変化率は９９モル％であった。Example 1 A 2 L reactor equipped with a stirrer and a TIC (temperature indicating / controlling device) was charged with NaF powder (300 g, 7.14 m).
ol) and 98% H by means of a metering pump while stirring.
2 SO 4 (360 g, 3.60 mol) and HF (30 g,
(1.50 mol). After the addition,
The temperature was raised to 280 ° C. and reacted for 3 hours. Generated HF
Was absorbed in water, and the amount of HF produced was measured by neutralization titration. The rate of change to HF was 99 mol%.
【００２３】実施例２ 反応温度を２００℃とする以外は実施例１と同様にして
反応を行った。ＨＦへの変化率は５６モル％であった。Example 2 A reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 200 ° C. The conversion to HF was 56 mol%.
【００２４】実施例３ 反応温度を１５０℃とする以外は実施例１と同様にして
反応を行った。ＨＦへの変化率は３０モル％であった。Example 3 A reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 150 ° C. The rate of change to HF was 30 mol%.
【００２５】実施例４ 反応温度を１００℃とする以外は実施例１と同様にして
反応を行った。ＨＦへの変化率は３モル％であった。Example 4 A reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 100 ° C. The rate of change to HF was 3 mol%.
Claims (3)
フッ酸を含有する混酸と反応させるフッ酸の製造方法。1. A method for producing hydrofluoric acid, comprising reacting an alkali metal fluoride with a mixed acid containing sulfuric acid and hydrofluoric acid.
ウムである請求項１に記載の方法。2. The method according to claim 1, wherein the alkali metal fluoride is sodium fluoride.
または２に記載の方法。3. The reaction at 100 to 500 ° C.
Or the method of 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000003914A JP4508333B2 (en) | 2000-01-12 | 2000-01-12 | Method for producing hydrofluoric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000003914A JP4508333B2 (en) | 2000-01-12 | 2000-01-12 | Method for producing hydrofluoric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001199712A true JP2001199712A (en) | 2001-07-24 |
| JP4508333B2 JP4508333B2 (en) | 2010-07-21 |
Family
ID=18532775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000003914A Expired - Fee Related JP4508333B2 (en) | 2000-01-12 | 2000-01-12 | Method for producing hydrofluoric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4508333B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002029706A (en) * | 2000-07-10 | 2002-01-29 | Daikin Ind Ltd | Device and method for manufacturing hydrogen fluoride |
| WO2011129563A2 (en) * | 2010-04-12 | 2011-10-20 | Kcc Corporation | Method of preparing anhydrous hydrogen fluoride by using sodium aluminum tetrafluoride and reaction device for the same |
| KR20210003246A (en) * | 2018-05-08 | 2021-01-11 | 오브쉐스트보 에스 오그라니첸노이 오트베트스트벤노스티유 “노비에 키미체스키에 프로덕티” | Method of treating hexafluorine silicic acid to produce hydrogen fluoride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4997799A (en) * | 1973-01-25 | 1974-09-17 | ||
| JPS49101292A (en) * | 1973-02-01 | 1974-09-25 | ||
| JPS5235196A (en) * | 1975-07-31 | 1977-03-17 | Daikin Ind Ltd | Method for recovery of hydrogen fluoride |
-
2000
- 2000-01-12 JP JP2000003914A patent/JP4508333B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4997799A (en) * | 1973-01-25 | 1974-09-17 | ||
| JPS49101292A (en) * | 1973-02-01 | 1974-09-25 | ||
| JPS5235196A (en) * | 1975-07-31 | 1977-03-17 | Daikin Ind Ltd | Method for recovery of hydrogen fluoride |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002029706A (en) * | 2000-07-10 | 2002-01-29 | Daikin Ind Ltd | Device and method for manufacturing hydrogen fluoride |
| JP4599673B2 (en) * | 2000-07-10 | 2010-12-15 | ダイキン工業株式会社 | Hydrogen fluoride production apparatus and production method |
| WO2011129563A2 (en) * | 2010-04-12 | 2011-10-20 | Kcc Corporation | Method of preparing anhydrous hydrogen fluoride by using sodium aluminum tetrafluoride and reaction device for the same |
| WO2011129563A3 (en) * | 2010-04-12 | 2012-03-08 | Kcc Corporation | Method of preparing anhydrous hydrogen fluoride by using sodium aluminum tetrafluoride and reaction device for the same |
| KR101169066B1 (en) * | 2010-04-12 | 2012-07-26 | 주식회사 케이씨씨 | Method of reusing sodium aluminum tetrafluoride obtained as a byproduct from monosilane production |
| KR20210003246A (en) * | 2018-05-08 | 2021-01-11 | 오브쉐스트보 에스 오그라니첸노이 오트베트스트벤노스티유 “노비에 키미체스키에 프로덕티” | Method of treating hexafluorine silicic acid to produce hydrogen fluoride |
| KR102491311B1 (en) | 2018-05-08 | 2023-01-27 | 오브쉐스트보 에스 오그라니첸노이 오트베트스트벤노스티 유 “노비에 키미체스키에 프로덕티” | Method for producing hydrogen fluoride by treating hexafluorine silicic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4508333B2 (en) | 2010-07-21 |
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