JPH0757915B2 - Improved electrolyzer - Google Patents
Improved electrolyzerInfo
- Publication number
- JPH0757915B2 JPH0757915B2 JP61276795A JP27679586A JPH0757915B2 JP H0757915 B2 JPH0757915 B2 JP H0757915B2 JP 61276795 A JP61276795 A JP 61276795A JP 27679586 A JP27679586 A JP 27679586A JP H0757915 B2 JPH0757915 B2 JP H0757915B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- partition plate
- anode
- generated
- electrolysis
- 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.)
- Expired - Lifetime
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、溶融塩電解法による三弗化窒素ガス（NF3）
の製造の際に使用される電解槽の改良に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to nitrogen trifluoride gas (NF 3 ) produced by a molten salt electrolysis method.
The present invention relates to improvement of an electrolytic cell used in the manufacture of a metal.
（従来の技術） 酸性フッ化アンモニウムまたはフッ化アンモニウムと弗
化水素を原料とするNH4F・HF系や、これに更に酸性フッ
化カリウムまたはフッ化カリウムを原料として加えたKF
・NH4F・HF系溶融塩電解法によるNF3ガスの製造の製造
を行なう場合、電解槽には陽極から発生するガスと陰極
から発生するガスを隔離するための隔板が設けられてい
る。(Prior art) NH 4 F / HF system using ammonium acid fluoride or ammonium fluoride and hydrogen fluoride as raw materials, and KF obtained by adding potassium acid fluoride or potassium fluoride as the raw material
・ When manufacturing NF 3 gas by the NH 4 F ・ HF molten salt electrolysis method, the electrolytic cell is provided with a partition plate for separating the gas generated from the anode and the gas generated from the cathode. .
上記電解槽においては、陽極からはNF3ガスが、陰極か
らは水素ガス（H2）が発生する。この二種類のガス、即
ち、NF3ガスとH2ガスは、混合すると爆発の危険性が極
めて大きいので、発生した二種類のガスの電解槽内での
混合を防ぐ目的で、陽極と陰極を隔離するための隔板が
設けられている。さらに、この隔板には電解浴に腐蝕さ
れにくい鉄、銅、ニッケルなどの金属板が通常使用され
ている。In the above electrolytic cell, NF 3 gas is generated from the anode and hydrogen gas (H 2 ) is generated from the cathode. These two types of gas, that is, NF 3 gas and H 2 gas, have an extremely high risk of explosion when mixed, so the anode and the cathode are set to prevent mixing of the generated two types of gas in the electrolytic cell. A partition plate is provided for isolation. Further, a metal plate made of iron, copper, nickel or the like which is not easily corroded by the electrolytic bath is usually used for this partition plate.
しかし、この様に電解槽には隔板を設けているにもかか
わらず、この電解槽を用いてNF3ガスの製造を行なう
と、陽極から発生するNF3ガス中に少なからずH2ガスが
混在してきて、爆発限界内のガスが生成する場合があ
る。これは、溶融塩電解時に隔板の複極化現象が起こ
り、複極化した隔板の陽極と相対する面からH2ガスが発
生し、このH2ガスがNF3ガスと混合し、爆発限界内の混
合ガスを生成するからである。However, despite the fact that the electrolytic cell is provided with a partition plate as described above, when NF 3 gas is produced using this electrolytic cell, H 2 gas is generated to a large extent in the NF 3 gas generated from the anode. When mixed, a gas within the explosion limit may be generated. This is because the bipolarization phenomenon of the diaphragm occurs during molten salt electrolysis, H 2 gas is generated from the surface of the bipolarized diaphragm facing the anode, and this H 2 gas mixes with NF 3 gas and explodes. This is because the mixed gas within the limit is generated.
そこで、このような爆発限界内の混合ガスの生成を防止
するため、従来は陽極発生ガス中にN2等の不活性ガスを
混入させ、陽極発生ガス中に混入するH2ガスの濃度を低
下させることで爆発の危険を回避する方法が取られて来
た。Therefore, in order to prevent the generation of such mixed gas within the explosion limit, conventionally, by mixing an inert gas such as N 2 into the anode-generated gas, the concentration of H 2 gas mixed in the anode-generated gas is reduced. By doing so, a method has been taken to avoid the danger of explosion.
（発明が解決しようとする問題点） しかし、この方法は隔板の複極化を防止するという方法
ではないので、NF3ガス中にH2ガスが混入したままであ
り、根本的な問題解決にはならず、電解条件によっては
依然爆発の危険性は残っている。隔板の一部または全部
に絶縁材を使用することは、隔板が関与する電子移動を
阻害する有効な手段である。ところで、食塩電解に代表
される水溶液系電解が工業的に一般的である。該水溶液
系電解では電解液あるいは生成ガスに対して、耐久性を
有する絶縁材はいくつか知られるところである。ところ
が、本発明が対象とする電解は、溶融塩の腐食性、生成
ガスであるNF3ガスの反応性が強いこと、更に操作温度
が高いなど一般的な電解とは性格が大きく異なり、更
に、本発明が対象とする、前記した電解条件における各
種絶縁材の耐久性に関する情報は皆無と言ってよく、通
常一般の技術を適用することは困難である。(Problems to be solved by the invention) However, since this method is not a method of preventing bipolarization of the partition plate, H 2 gas remains mixed in the NF 3 gas, and the fundamental problem is solved. However, there is still a risk of explosion depending on the electrolysis conditions. The use of an insulating material for part or all of the diaphragm is an effective means of inhibiting the electron transfer involving the diaphragm. By the way, aqueous solution electrolysis typified by salt electrolysis is industrially general. In the aqueous solution electrolysis, some insulating materials having durability against the electrolytic solution or the generated gas are known. However, the electrolysis targeted by the present invention, the corrosiveness of the molten salt, the reactivity of the NF 3 gas that is the generated gas is strong, the character of the electrolysis is greatly different from the general electrolysis such as a high operating temperature, It can be said that there is no information on the durability of various insulating materials under the above-mentioned electrolysis conditions, which is the subject of the present invention, and it is usually difficult to apply general techniques.
更に、隔板は、前記の通りその材質が鉄、銅、ニッケル
などの金属板であるので、電解浴に腐蝕されにくいとは
いえ、若干の腐蝕は免れ難いという問題もある。Further, since the partition plate is a metal plate made of iron, copper, nickel or the like as described above, it is difficult to be corroded by the electrolytic bath, but there is a problem that some corrosion is inevitable.
（問題点を解決するための手段） 上記、隔板の複極化を防止する方法として、隔板の電気
電導性を無くする方法は考えられるが、極めて強い腐食
性雰囲気、かつ高温である本法の電解条件下での隔板材
料の電気的特性及び電気化学的特性に関する報告は全く
なく、該方法での複極化防止を工業的に実施することは
容易ではないと考えられていた。(Means for Solving the Problems) As a method for preventing the bipolarization of the partition plate, a method of eliminating the electrical conductivity of the partition plate is considered, but it is an extremely strong corrosive atmosphere and a high temperature. There is no report on the electrical and electrochemical properties of the diaphragm material under the electrolytic conditions of the method, and it was considered that it is not easy to industrially carry out the prevention of bipolarization by the method.
本発明者等は、根本的な解決手段である隔板の複極化防
止について種々検討を重ねた結果、隔板の材質をフッ素
系樹脂とすれば隔板の複極化を防止することが可能で、
しかも隔板も腐蝕されないことを見出し、本発明を完成
させるに至ったものである。The present inventors have made various studies on prevention of bipolarization of a partition plate, which is a fundamental solution, and as a result, if the material of the partition plate is a fluororesin, it is possible to prevent bipolarization of the partition plate. Possible,
Moreover, they have found that the partition plate is not corroded, and have completed the present invention.
すなわち、本発明は、溶融塩電解法による三弗化窒素ガ
スの製造に際し、陽極から発生する該三弗化窒素ガスと
陰極から発生する水素ガスを隔離するための隔板がフッ
素系樹脂からなることを特徴とする改良された電解槽で
ある。That is, in the present invention, in the production of nitrogen trifluoride gas by the molten salt electrolysis method, the partition plate for separating the nitrogen trifluoride gas generated from the anode and the hydrogen gas generated from the cathode is made of a fluororesin. It is an improved electrolytic cell characterized by the above.
本発明を図面に基いて更に詳細に説明する。The present invention will be described in more detail with reference to the drawings.
陽極から発生するガスと陰極から発生するガスを隔離す
るための隔板の形状には色々なものがある。例えば、隔
板が平板状である場合、隔板が陽極または陰極を取り巻
く形状である場合などがあり、特殊な例としては、蓋板
の中央部が下方にＵ字形に折曲っていてこの折曲り部が
隔板の役割を果す形状のものもある。There are various shapes of the partition plate for separating the gas generated from the anode and the gas generated from the cathode. For example, the partition plate may have a flat plate shape, or the partition plate may have a shape surrounding an anode or a cathode. As a special example, the central portion of the lid plate is bent downward in a U shape, and In some cases, the bent portion plays the role of a partition plate.
第１図は隔板が平板状である場合の、第３図は隔板が陽
極を取り巻く形状である場合の、第５図は隔板が陰極を
取り巻く形状である場合の、第７図は隔板が陽極を取り
巻く形状でありかつ電解槽本体が陰極である場合の、第
９図は蓋板の中央部がＵ字形に折曲っていて該折曲り部
が隔板の役割を果たす形状の場合の、夫々の電解槽の縦
断面図であり、第２図は第１図の、第４図は第３図の、
第６図は第５図の、第８図は第７図の、第10図は第９図
の、夫々のＡ−Ａ′矢視図を示す。FIG. 1 shows the case where the partition plate is flat, FIG. 3 shows the case where the partition plate surrounds the anode, and FIG. 5 shows when the partition plate surrounds the cathode. When the partition plate has a shape surrounding the anode and the electrolytic cell body is the cathode, FIG. 9 shows a shape in which the central portion of the lid plate is bent in a U shape and the bent portion functions as the partition plate. FIG. 2 is a longitudinal sectional view of each electrolytic cell in the case of FIG. 2, FIG. 2 of FIG. 1, FIG. 4 of FIG.
6 shows a view of FIG. 5, FIG. 8 shows a view of FIG. 7, and FIG. 10 shows a view of FIG.
この種の電解槽の中には、第１図〜第10図に示す様に、
電解槽の底板部には底板の上にフッ素系樹脂板２が設け
てあって、底板の腐蝕を防止する様になっているものも
ある。また、陽極５または陰極６に接続されている接続
棒7a,7bと蓋板３とは絶縁材8a,8bで絶縁されていて、更
に接続棒7a,7bは、例えば、接続棒固定用袋ナット9a,9b
で蓋板３に間接的に固定されている。In this type of electrolytic cell, as shown in FIGS. 1 to 10,
In some cases, the bottom plate portion of the electrolytic cell is provided with a fluorine-based resin plate 2 on the bottom plate to prevent corrosion of the bottom plate. The connecting rods 7a, 7b connected to the anode 5 or the cathode 6 and the cover plate 3 are insulated from each other by insulating materials 8a, 8b, and the connecting rods 7a, 7b are, for example, cap nuts for fixing the connecting rods. 9a, 9b
Is indirectly fixed to the lid plate 3.
本発明の隔板に用いるフッ素系樹脂は、例えば、ポリテ
トラフルオロエチレン、ポリクロロトリフルオロエチレ
ン、ポリビニリデンフルオライド、ポリビニルフルオラ
イド、テトラフルオロエチレン−ヘキサフルオロプロピ
レン共重合体、テトラフルオロエチレン−エチレン共重
合体、テトラフルオロエチレン−パーフルオロアルキル
ビニルエーテル共重合体、クロロトリフルオロエチレン
−エチレン共重合体等通常公知のものが何れも好適に使
用可能である。The fluororesin used for the partition plate of the present invention is, for example, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene. Any of the commonly known compounds such as copolymers, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, chlorotrifluoroethylene-ethylene copolymers can be preferably used.
以下、実施例により本発明を更に具体的に説明する。Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１ ポリテトラフルオロエチレン製の隔板を用い、KF・NH4F
・4HFなる組成の溶融塩を原料として、100℃での電解を
240時間行った。電解中の複極化現象も起こらず、ま
た、電解終了後、隔板に変化は認められなかった。Example 1 Using a partition plate made of polytetrafluoroethylene, KF · NH 4 F
・ Electrolysis at 100 ℃ using molten salt of 4HF as raw material
I went for 240 hours. No bipolarization phenomenon occurred during electrolysis, and no change was observed in the diaphragm after the electrolysis was completed.
実施例２ テトラフルオロエチレン−パーフルオロアルキルビニル
エーテル共重合体製の隔板を用い、NH4F・2HFなる組成
の溶融塩を原料として、120℃での電解を240時間行っ
た。電解中に複極化現象も起こらず、また、電解終了
後、隔板に変化は認められなかった。Example 2 Using a partition plate made of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, electrolysis was carried out at 120 ° C. for 240 hours using a molten salt having a composition of NH 4 F · 2HF as a raw material. No bipolar phenomenon occurred during electrolysis, and no change was observed in the diaphragm after the electrolysis was completed.
比較例１ フッ素ゴム（商品名バイトン）製の隔板を用いた他は、
実施例２と同様に行った。およそ120時間経過した後よ
り、陽極ガス中に水素ガスが若干混入する現象が見られ
た。電解終了後の隔板には劣化が認められ、該混入は劣
化部分よりガスが滲出したものと認められた。Comparative Example 1 Other than using a partition plate made of fluororubber (trade name Viton),
The same procedure as in Example 2 was performed. After a lapse of about 120 hours, a phenomenon in which hydrogen gas was slightly mixed in the anode gas was observed. Deterioration was observed in the partition plate after completion of electrolysis, and it was confirmed that gas was exuded from the deteriorated portion due to the mixing.
（作用及び発明の効果） 以上、詳細に説明したように、本発明の電解槽は、隔板
がフッ素系樹脂であるので、従来問題であった隔板の複
極化を完全に防止することが出来、これによって溶融塩
電解の際の陽極から発生するNF3ガスやF2ガス中にH2ガ
スの混入を完全に防止することが可能となった。勿論こ
れによって爆発の問題も完全に解消できるので、溶融塩
電解によるNF3ガスやF2ガスの工業的製造が可能とな
り、その経済的効果は極めて大である。また隔板がフッ
素系樹脂であるので隔板の腐蝕も完全に防止出来る点も
大いに評価される。(Operation and Effect of the Invention) As described in detail above, in the electrolytic cell of the present invention, since the partition plate is a fluororesin, it is necessary to completely prevent the bipolarization of the partition plate, which has been a conventional problem. This made it possible to completely prevent H 2 gas from being mixed into NF 3 gas and F 2 gas generated from the anode during molten salt electrolysis. Of course, this also completely eliminates the problem of explosion, which makes it possible to industrially produce NF 3 gas and F 2 gas by molten salt electrolysis, and its economic effect is extremely large. In addition, since the partition plate is made of a fluororesin, it is also highly evaluated that it can completely prevent corrosion of the partition plate.
第１図は隔板が平板上である場合の、第３図は隔板が陽
極を取り巻く形状である場合の、第５図は隔板が陰極を
取り巻く形状である場合の、第７図は隔板が陽極を取り
巻く形状でありかつ電解槽本体が陰極である場合の、第
９図は蓋板の中央部が下方にＵ字形に折曲っていて該折
曲り部が隔板の役割を果たす形状の場合の、夫々の電解
槽の縦断面図であり、第２図は第１図の、第４図は第３
図の、第６図は第５図の、第８図は第７図の、第10図は
第９図の夫々のＡ−Ａ′矢視図を示す。 図において、 １……電解槽本体、２……フッ素系樹脂板、 ３……蓋板、４……電解浴、 ５……陽極、６……陰極、 7a,7b……接続棒、8a,8b……絶縁材、 9a,9b……接続棒固定用袋ナット、 10……隔板、11……隔板固定用蓋板、 12……陽極発生ガス出口管、 13……陰極発生ガス出口管、 14……パッキング、 15……蓋板用ボルトナット、 16……隔板固定用ボルト、 を示す。FIG. 1 shows the case where the partition plate is flat, FIG. 3 shows the case where the partition plate surrounds the anode, and FIG. 5 shows the case where the partition plate surrounds the cathode. In the case where the partition plate has a shape surrounding the anode and the electrolytic cell body is the cathode, FIG. 9 shows that the central portion of the lid plate is bent downward in a U shape, and the bent portion functions as the partition plate. FIG. 2 is a vertical sectional view of each electrolytic cell in the case of a shape, FIG. 2 is FIG. 1, FIG.
FIG. 6, FIG. 6 shows a view of FIG. 5, FIG. 8 shows a view of FIG. 7 and FIG. In the figure, 1 ... Electrolyte body, 2 ... Fluorine resin plate, 3 ... Lid plate, 4 ... Electrolyte bath, 5 ... Anode, 6 ... Cathode, 7a, 7b ... Connecting rod, 8a, 8b ... Insulation material, 9a, 9b ... Cap nut for fixing connecting rod, 10 ... Separator plate, 11 ... Separator plate fixing lid plate, 12 ... Anode-generated gas outlet pipe, 13 ... Cathode-generated gas outlet Tube, 14 ... Packing, 15 ... Lid plate bolt and nut, 16 ... Separator plate fixing bolt.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭58−100688（ＪＰ，Ａ) 特開 昭60−155502（ＪＰ，Ａ) 特公 昭47−16418（ＪＰ，Ｂ１) 特公 昭54−36152（ＪＰ，Ｂ２) 電気化学協会編「電気化学便覧」第２版 （昭49−10−20）丸善Ｐ．558−563，731 −732 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-58-100688 (JP, A) JP-A-60-155502 (JP, A) JP-B 47-16418 (JP, B1) JP-B 54- 36152 (JP, B2) Electrochemical Society ed., "Electrochemical Handbook" Second Edition (Sho 49-10-20) Maruzen P. 558-563, 731-732
Claims (1)
に際し、陽極から発生する該三弗化窒素ガスと陰極から
発生する水素ガスを隔離するための隔板がフッ素系樹脂
からなることを特徴とする改良された電解槽。1. When producing nitrogen trifluoride gas by a molten salt electrolysis method, a partition plate for separating the nitrogen trifluoride gas generated from the anode and the hydrogen gas generated from the cathode is made of a fluororesin. An improved electrolyzer characterized by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61276795A JPH0757915B2 (en) | 1986-11-21 | 1986-11-21 | Improved electrolyzer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61276795A JPH0757915B2 (en) | 1986-11-21 | 1986-11-21 | Improved electrolyzer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63130790A JPS63130790A (en) | 1988-06-02 |
| JPH0757915B2 true JPH0757915B2 (en) | 1995-06-21 |
Family
ID=17574482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61276795A Expired - Lifetime JPH0757915B2 (en) | 1986-11-21 | 1986-11-21 | Improved electrolyzer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0757915B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0243400A (en) * | 1988-08-03 | 1990-02-13 | Mitsui Toatsu Chem Inc | Electrolytic cell |
| KR100286717B1 (en) * | 1998-06-30 | 2001-06-01 | 박호군 | Improved Method of Making Fluorine |
| KR102615096B1 (en) * | 2017-10-31 | 2023-12-15 | 칸토 덴카 코교 가부시키가이샤 | Electrolyzer for producing nitrogen trifluoride gas and its partition wall |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5436152A (en) * | 1977-08-26 | 1979-03-16 | Nec Corp | Clock synchronization circuit between central processors |
| JPS5937351B2 (en) * | 1981-12-11 | 1984-09-08 | 旭硝子株式会社 | Electrolytic cell for fluorine generation |
| US4511440A (en) * | 1983-12-22 | 1985-04-16 | Allied Corporation | Process for the electrolytic production of fluorine and novel cell therefor |
-
1986
- 1986-11-21 JP JP61276795A patent/JPH0757915B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 電気化学協会編「電気化学便覧」第２版（昭４９−１０−２０）丸善Ｐ．５５８−５６３，７３１−７３２ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63130790A (en) | 1988-06-02 |
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