JP2006336035A - Electrolysis tank and method for producing nitrogen trifluoride by using the same - Google Patents
Electrolysis tank and method for producing nitrogen trifluoride by using the same Download PDFInfo
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- JP2006336035A JP2006336035A JP2005158783A JP2005158783A JP2006336035A JP 2006336035 A JP2006336035 A JP 2006336035A JP 2005158783 A JP2005158783 A JP 2005158783A JP 2005158783 A JP2005158783 A JP 2005158783A JP 2006336035 A JP2006336035 A JP 2006336035A
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 26
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 55
- 239000011347 resin Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 238000005192 partition Methods 0.000 claims description 21
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 abstract description 7
- 125000006850 spacer group Chemical group 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000003014 reinforcing effect Effects 0.000 description 9
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 235000003270 potassium fluoride Nutrition 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
本発明は、電極の隔板に工夫がなされた電解槽およびそれを用いた三フッ化窒素の製造方法に関する。 The present invention relates to an electrolytic cell in which an electrode separator is devised and a method for producing nitrogen trifluoride using the electrolytic cell.
酸性フッ化アンモニウムまたはフッ化アンモニウムとフッ化水素を原料とするか、さら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て溶融塩電解法により三フッ化窒素ガスの製造あるいは、酸性フッ化カリウムあるいはフッ化カリウムとフッ化水素を原料として同様にフッ素ガスを製造する場合には、陽極から発生する三フッ化窒素あるいはフッ素ガスと陰極から発生する水素ガスが混合すると爆発性の混合ガスとなるため隔板が設けられた電解槽を用いて反応が行われる。隔板としては金属も使用可能であるが溶解すると言う問題があるので樹脂性、特にフッ素樹脂で覆った金属（特許文献１）、あるいはフッ素樹脂そのものを利用する（特許文献２）ことが一般的である。
樹脂製、特にフッ素樹脂の隔板は溶融塩に溶解しないので好適であるが、電極の改良、運転条件の最適化などで長時間の運転が可能になると、高温での運転では隔板の自由端（隔板の電解槽などに固定していない側の端）側が変形し、隔板として効果を発揮できないと言う問題が生じた。 Resin, especially fluororesin diaphragms are suitable because they do not dissolve in the molten salt. However, if long-term operation is possible by improving the electrodes and optimizing operating conditions, the diaphragms can be freely operated at high temperatures. The end (end of the side plate not fixed to the electrolytic cell or the like) side was deformed, resulting in a problem that the effect as a partition plate could not be exhibited.
本発明の目的は、長時間の溶融塩電解反応を行うに好適な電解槽およびそれを用いた三フッ化窒素ガスの製造方法を提供することにある。 An object of the present invention is to provide an electrolytic cell suitable for performing a molten salt electrolysis reaction for a long time and a method for producing nitrogen trifluoride gas using the electrolytic cell.
本発明者は、上記課題を解決する為に、鋭意検討したところ、隔壁の一部を補強するだけで変形を押さえることが可能であることを見出し本発明を完成した。 The present inventor has intensively studied to solve the above problems, and found that the deformation can be suppressed only by reinforcing a part of the partition wall, and the present invention has been completed.
即ち、本発明は、陽極から発生するガスと陰極から発生するガスとを隔離するための、少なくとも一部が補強されている樹脂製隔板を備えた三フッ化窒素ガス製造用電解槽である。 That is, the present invention is an electrolytic cell for producing nitrogen trifluoride gas, which is provided with a resin diaphragm at least partially reinforced to separate a gas generated from an anode from a gas generated from a cathode. .
本発明はまた、上記電解槽を用い、無水フッ化水素とアンモニアを原料とし、電解温度が８０℃以上１５０℃以下の条件で電解することを特徴とする三フッ化窒素ガスの製造方法である。 The present invention is also a method for producing nitrogen trifluoride gas, characterized in that electrolysis is performed using anhydrous hydrogen fluoride and ammonia as raw materials and an electrolysis temperature of 80 ° C. or higher and 150 ° C. or lower using the electrolytic cell. .
本発明の電解槽は溶融塩を電気分解するに好適であり、特に三フッ化窒素ガスの製造に好適であり工業的に極めて価値がある。 The electrolytic cell of the present invention is suitable for electrolyzing a molten salt, particularly suitable for producing nitrogen trifluoride gas, and is extremely valuable industrially.
以下、本発明について説明する。 The present invention will be described below.
図１は、本発明の実施に好適な、三フッ化窒素ガス製造用電解槽の一例を示す縦断面であり、図２は、図１におけるＡ−Ａ’矢視図を示す。 FIG. 1 is a longitudinal sectional view showing an example of an electrolytic cell for producing nitrogen trifluoride gas suitable for the implementation of the present invention, and FIG. 2 shows a view taken along the line A-A ′ in FIG. 1.
この例では、陽極電極２を取り囲むように樹脂製隔板５が設置され、樹脂製隔板５は、陽極電極２とともに着脱可能に保持される。陰極電極１及び陽極電極２には、それぞれ陰極接続棒及び陽極接続棒が取り付けられており、電解槽蓋板にそれぞれ固定用袋ナット１３及び１４にて固定されている。また、この電解槽蓋板は、電解槽本体に蓋板用ボルトナット１０にて着脱自在に固定されている。電解槽本体と電解槽蓋板との間には、気密性を高めるためにパッキン等が挟まれていても良く、このパッキンも耐食性の高いフッ素樹脂などで構成されていることが好ましい。８はスチーム・工水入口、９はスチーム・工水出口を示し、主に洗浄時にスチームまたは工水を導入、排出することで電解槽を加熱、あるいは冷却することができる。電解時には、樹脂製隔板５で隔離された陽極気相部及び陰極気相部に希釈ガスとして窒素ガス（Ｎ2）が導入される。生成した陽極発生ガスである三フッ化窒素ガスと陰極発生ガスである水素ガスはそれぞれ希釈され、電解槽蓋板に設けた陰極ガス発生出口管１１から陰極ガスが陰極ガス出口ライン３へ、陽極ガス発生出口管１２から陽極ガスが陽極ガス出口ライン４へそれぞれ導出される。 In this example, a resin diaphragm 5 is installed so as to surround the anode electrode 2, and the resin diaphragm 5 is detachably held together with the anode electrode 2. A cathode connecting rod and an anode connecting rod are attached to the cathode electrode 1 and the anode electrode 2, respectively, and fixed to the electrolytic cell lid plate by fixing cap nuts 13 and 14, respectively. The electrolytic cell lid plate is detachably fixed to the electrolytic cell body by a lid plate bolt and nut 10. A packing or the like may be sandwiched between the electrolytic cell main body and the electrolytic cell lid plate in order to improve airtightness, and this packing is also preferably made of a highly corrosion-resistant fluororesin or the like. Reference numeral 8 denotes a steam / work water inlet, and 9 denotes a steam / work water outlet. The electrolyzer can be heated or cooled mainly by introducing and discharging steam or work water during cleaning. At the time of electrolysis, nitrogen gas (N 2 ) is introduced as a dilution gas into the anode vapor phase portion and the cathode vapor phase portion separated by the resin diaphragm 5. The generated nitrogen trifluoride gas as the anode generating gas and the hydrogen gas as the cathode generating gas are respectively diluted, and the cathode gas is supplied from the cathode gas generation outlet pipe 11 provided on the electrolytic cell lid plate to the cathode gas outlet line 3. Anode gas is led out from the gas generation outlet pipe 12 to the anode gas outlet line 4 respectively.
本発明の特徴は、樹脂製隔板５の一部を補強したことにあり、図１に示す例では、樹脂製隔板５の自由端に被覆樹脂６で被覆された補強板７で補強された態様を示している。 A feature of the present invention resides in that a part of the resin partition plate 5 is reinforced, and in the example shown in FIG. 1, the free end of the resin partition plate 5 is reinforced by a reinforcing plate 7 covered with a coating resin 6. The embodiment is shown.
以下、さらに各部を詳細に説明する。 Hereinafter, each part will be further described in detail.
（樹脂製隔板）
本発明の隔板に用いる樹脂は、電解液に対して耐性があり、電解時の温度条件下に十分な耐熱性を有する樹脂であれば特に限定されないが、とりわけフッ素樹脂であることが好ましい。フッ素樹脂としては、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。
(Resin separator)
The resin used for the diaphragm of the present invention is not particularly limited as long as it is resistant to the electrolytic solution and has sufficient heat resistance under the temperature conditions during electrolysis, but is preferably a fluororesin. Examples of the fluororesin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene. -Commonly known ones such as a perfluoroalkyl vinyl ether copolymer and a chlorotrifluoroethylene-ethylene copolymer can be suitably used.
隔板の製造方法は特に限定されるものではないが、通常、樹脂板を所望の形状に切断、折り曲げ、溶接等により加工すればよい。 Although the manufacturing method of a partition plate is not specifically limited, Usually, what is necessary is just to process a resin plate by cutting, bending, welding, etc. into a desired shape.
本発明は、樹脂製の隔板が補強されていることに特徴がありその他の条件については公知の装置、工夫を採用することができ、好ましい範囲も適宜定めれば良い。 The present invention is characterized in that a resin partition plate is reinforced, and other devices can be employed for other conditions, and a preferable range may be determined as appropriate.
隔板の厚みは、薄い方が重量及びコスト面で有利であるが、薄くなるほど変形しやすくなる傾向がある。通常、１ｍｍ〜１０ｍｍ、好ましくは２ｍｍ〜５ｍｍとするのが望ましい。 The thinner the separator, the more advantageous in terms of weight and cost. However, the thinner the separator, the easier it is to deform. Usually, 1 mm to 10 mm, preferably 2 mm to 5 mm is desirable.
隔板は、電解を阻害することなく陽極発生ガスと陰極発生ガスとが混合しないように隔離できれば、どの位置に取り付けても良い。隔板はイオン種の移動を阻害するのでその下端は電極下端よりも上に位置することが好ましい。隔板と電極との好ましい位置関係については既に公知であり、特開平３−１４０４８８、特開平３−１７０６８７、特開平４−６３２９１などに示された関係を維持するのが好ましい。 The partition plate may be attached at any position as long as it can be isolated so as not to mix the anode-generating gas and the cathode-generating gas without inhibiting electrolysis. Since the diaphragm inhibits the movement of ionic species, the lower end thereof is preferably positioned above the lower end of the electrode. The preferable positional relationship between the diaphragm and the electrode is already known, and it is preferable to maintain the relationship described in JP-A-3-140488, JP-A-3-170687, JP-A-4-63291, and the like.
（補強）
補強は、隔板の変形が起こる個所に対して、その変形を抑制するのに効果的な位置を少なくとも１個所補強するが、高温で長時間運転を行った場合、隔板の自由端の変形が大きく、この変形を押さえ込めるように補強するのが好ましい。より好ましくは、樹脂製隔板の自由端または自由端の上方を、厚さ１ｍｍ以上１０ｍｍ以下の板で補強する。当該補強板としては、隔板と同様の樹脂板あるいは、金属板にフッ素樹脂などの樹脂を被覆したものなどが好ましい。また、隔板の自由端を折り曲げて２重にすることも可能である。また、棒状のものを用いて補強することもできる。その材質は、前述の補強板と同様なものが好ましい。
(Reinforcement)
Reinforcement reinforces at least one location that is effective for suppressing deformation of the partition where deformation occurs. However, when the operation is performed for a long time at a high temperature, deformation of the free end of the separation plate It is preferable to reinforce so that this deformation can be suppressed. More preferably, the free end of the resin partition plate or above the free end is reinforced with a plate having a thickness of 1 mm or more and 10 mm or less. The reinforcing plate is preferably a resin plate similar to the partition plate or a metal plate coated with a resin such as a fluororesin. It is also possible to fold the free end of the partition plate into two. Moreover, it can also reinforce using a rod-shaped thing. The material is preferably the same as that of the aforementioned reinforcing plate.
補強板の隔板への取付は、例えば、樹脂あるいは樹脂被覆を施した金属板を使用する場合は、樹脂溶接にて取り付けることができる。 The reinforcing plate can be attached to the partition plate by, for example, resin welding when using a resin or a metal plate coated with resin.
ここで、補強板は、陽極側に取り付けるのが好ましく陽極と隔板の最も近い部分（補強部）の距離については３０ｍｍ以下であっても良い。 Here, the reinforcing plate is preferably attached to the anode side, and the distance between the anode and the closest part (reinforcing portion) between the anode plate and the reinforcing plate may be 30 mm or less.
以下の要件については発明の構成から明らかなように何ら制限はないが既に好ましい態様については公知でありそのような技術を利用することができる。 The following requirements are not limited at all as is apparent from the constitution of the invention, but preferred embodiments are already known and such techniques can be used.
（電極）
陽極、陰極ともに高純度のニッケル電極を用いるのが特に望ましい。
(electrode)
It is particularly desirable to use high purity nickel electrodes for both the anode and the cathode.
（電解槽筐体）
電解槽筐体（電解槽本体及び蓋板）は、フッ素樹脂の被膜をライニングまたはコーティングして形成しておくことは特に好ましい。
(Electrolytic cell housing)
It is particularly preferable that the electrolytic cell casing (electrolytic cell main body and lid plate) be formed by lining or coating a fluororesin film.
（電解液）
電解液は、アンモニア（ＮＨ3）およびフッ化水素（ＨＦ）を利用するのが一般的であり、フッ化水素として無水フッ化水素を用いる等、好ましい態様についても公知でありそのような技術を利用することが可能である。
(Electrolyte)
The electrolytic solution generally uses ammonia (NH 3 ) and hydrogen fluoride (HF), and preferred embodiments such as the use of anhydrous hydrogen fluoride as hydrogen fluoride are well known, and such a technique is used. It is possible to use.
（電解方法）
好ましい態様については公知でありそのような技術を利用することができる。本発明は、電解温度を８０℃以上１５０℃以下の条件で電解する場合に特に有効である。
(Electrolysis method)
Preferred embodiments are known and such techniques can be utilized. The present invention is particularly effective when electrolysis is performed at a temperature of 80 ° C. or higher and 150 ° C. or lower.
（実施例１）
一辺が１７０ｍｍで、厚みが５．５ｍｍのニッケル製金属板を陽極、陰極とし、また、陽極を厚み３ｍｍ、奥行き２５０ｍｍ、幅８０ｍｍ、深さ２３０ｍｍのフッ素樹脂製隔板で覆うことにより、図１に示すような電解槽を作製した。更には該隔板の下端の周囲に、厚さ２ｍｍのフッ素樹脂で被覆した厚さ２ｍｍ、長さ２４５ｍｍ、幅２０ｍｍのニッケル板、及び厚さ２ｍｍ、長さ８０ｍｍ、幅２０ｍｍのニッケル板を溶接することにより隔板の補強を行った。陽極と隔板の補強部の距離は、２６．７ｍｍであった。
Example 1
A nickel metal plate having a side of 170 mm and a thickness of 5.5 mm is used as an anode and a cathode, and the anode is covered with a fluororesin separator having a thickness of 3 mm, a depth of 250 mm, a width of 80 mm, and a depth of 230 mm. An electrolytic cell as shown in FIG. Furthermore, a nickel plate with a thickness of 2 mm, a length of 245 mm, a width of 20 mm, and a nickel plate with a thickness of 2 mm, a length of 80 mm, and a width of 20 mm is welded around the lower end of the partition plate with a 2 mm-thick fluororesin. By doing so, the partition plate was reinforced. The distance between the anode and the reinforcing part of the partition plate was 26.7 mm.
該電解槽中に、予め調製したモル比（ＨＦ／ＮＨ４Ｆ）が２．０のＮＨ４Ｆ−ＨＦ系溶融塩２０ｋｇを投入し、電解温度１１５℃、電解電流２０Ａで電解を行い、三フッ化窒素ガスを製造した。電解中、槽電圧は７．０Ｖ〜７．２Ｖで安定していた。電解中のガスクロマトグラフィー分析では、陽極ガス中に水素ガスの混入や、陰極ガス中の三フッ化窒素ガスの混入は認められず、また、運転４００時間後の該隔板の形状は、変形等はなく運転後と同様であり、再び三フッ化窒素ガス製造用電解槽に利用することが可能であった。 In the electrolytic cell, 20 kg of NH 4 F-HF molten salt having a molar ratio (HF / NH 4 F) prepared in advance of 2.0 is charged, and electrolysis is performed at an electrolysis temperature of 115 ° C. and an electrolysis current of 20 A. Nitrogen fluoride gas was produced. During electrolysis, the cell voltage was stable at 7.0 V to 7.2 V. In gas chromatographic analysis during electrolysis, no mixing of hydrogen gas into the anode gas or nitrogen trifluoride gas into the cathode gas was observed, and the shape of the diaphragm after 400 hours of operation was deformed. It was the same as that after the operation, and it could be used again for the electrolytic cell for producing nitrogen trifluoride gas.
（実施例２）
フッ素樹脂による被覆を行ったニッケル板の代わりに、厚さ３ｍｍのフッ素樹脂板を該隔板の下端周囲に溶接した以外は実施例１と同様の条件で電解槽を作製し、電解を行った。電解中、槽電圧は７．１〜７．３Ｖで安定しており、ガスクロマトグラフィー分析では陽極ガス中の水素ガスの混入や陰極ガス中の三フッ化窒素ガスの混入は認めらなかった。また、運転４００時間後の該隔板の形状は、変形等はなく、運転後と同様であり、再利用が可能であった。
(Example 2)
An electrolytic cell was prepared and electrolyzed under the same conditions as in Example 1 except that a 3 mm thick fluororesin plate was welded around the lower end of the partition plate instead of the nickel plate coated with the fluororesin. . During the electrolysis, the cell voltage was stable at 7.1 to 7.3 V, and in the gas chromatography analysis, no mixing of hydrogen gas in the anode gas or nitrogen trifluoride gas in the cathode gas was observed. Further, the shape of the partition plate after 400 hours of operation was not deformed and was the same as that after the operation, and could be reused.
（比較例１）
該隔板に補強が何も施されていないものを用いた以外は、実施例１と同様の条件で電解槽を作製し、電解を行った。およそ２０時間経過した後より、陽極ガス中に水素ガスが、また陰極ガス中に三フッ化窒素ガスが混入する現象が認められ、３０時間を経過した時点で陰極ガス中の三フッ化窒素ガス濃度が１ｖｏｌ．％を超えたため、電解を停止した。電解終了後の該隔板下端は波打つように変形しており、且つ下端の幅が短くなっていた。該隔板を使用すると、陽極ガス中に水素ガスが、また陰極ガス中に三フッ化窒素ガスが混入し、爆発性の混合気が形成されることが懸念されるため、もはや再利用することは不可能であった。
(Comparative Example 1)
An electrolytic cell was produced and electrolyzed under the same conditions as in Example 1 except that the diaphragm was not reinforced. After about 20 hours, a phenomenon in which hydrogen gas is mixed into the anode gas and nitrogen trifluoride gas is mixed into the cathode gas, and when 30 hours have passed, the nitrogen trifluoride gas in the cathode gas is observed. Concentration is 1 vol. % Was exceeded, so the electrolysis was stopped. The lower end of the partition plate after electrolysis was deformed to wave, and the width of the lower end was shortened. When using the diaphragm, hydrogen gas is mixed into the anode gas and nitrogen trifluoride gas is mixed into the cathode gas, and there is a concern that an explosive mixture is formed. Was impossible.
１ 陰極電極
２ 陽極電極
３ 陰極ガス出口ライン
４ 陽極ガス出口ライン
５ 樹脂製隔板
６ 樹脂製隔板の補強板の被覆樹脂
７ 樹脂製隔板の補強板
８ スチーム・工水入口
９ スチーム・工水出口
１０ 蓋板用ボルトナット
１１ 陰極ガス発生出口管
１２ 陽極ガス発生出口管
１３ 陽極接続棒固定用袋ナット
１４ 陰極接続棒固定用袋ナット
DESCRIPTION OF SYMBOLS 1 Cathode electrode 2 Anode electrode 3 Cathode gas exit line 4 Anode gas exit line 5 Resin partition plate 6 Coating resin of resin diaphragm reinforcement plate Resin reinforcement plate 8 Steam / work water inlet 9 Steam / engineering Water outlet 10 Bolt nut 11 for lid plate Cathode gas generation outlet tube 12 Anode gas generation outlet tube 13 Cap nut 14 for fixing anode connecting rod Cap nut for fixing cathode connection rod
Claims (3)
A method for producing nitrogen trifluoride gas, characterized in that electrolysis is performed using anhydrous hydrogen fluoride and ammonia as raw materials under the conditions of an electrolysis temperature of 80 ° C or higher and 150 ° C or lower using the electrolytic cell according to claim 1 or 2.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017057950A1 (en) * | 2015-10-02 | 2017-04-06 | 후성정공 주식회사 | Collector of electrolyzer for manufacturing nitrogen trifluoride and method for manufacturing same |
| WO2019049834A1 (en) * | 2017-09-06 | 2019-03-14 | 関東電化工業株式会社 | Electrode and production method therefor, and production method for regenerated electrode |
| WO2019087885A1 (en) | 2017-10-31 | 2019-05-09 | 関東電化工業株式会社 | Electrolytic bath for producing nitrogen trifluoride gas, and partition therefor |
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| JPS55141596A (en) * | 1979-04-24 | 1980-11-05 | Kawasaki Steel Corp | Improvement of soldering property of cold rolled stainless steel strip treated by bright annealing |
| JP2000104187A (en) * | 1998-09-29 | 2000-04-11 | Mitsui Chemicals Inc | Electrolytic cell (1) |
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| KR101771862B1 (en) * | 2015-10-02 | 2017-08-28 | 후성정공 주식회사 | Collector of electrolyzer for manufacturing nitrogen trifluoride and manufacturing method the same |
| WO2017057950A1 (en) * | 2015-10-02 | 2017-04-06 | 후성정공 주식회사 | Collector of electrolyzer for manufacturing nitrogen trifluoride and method for manufacturing same |
| JPWO2019049834A1 (en) * | 2017-09-06 | 2020-08-20 | 関東電化工業株式会社 | Electrode, method for manufacturing the same, and method for manufacturing regenerated electrode |
| WO2019049834A1 (en) * | 2017-09-06 | 2019-03-14 | 関東電化工業株式会社 | Electrode and production method therefor, and production method for regenerated electrode |
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| WO2019087885A1 (en) | 2017-10-31 | 2019-05-09 | 関東電化工業株式会社 | Electrolytic bath for producing nitrogen trifluoride gas, and partition therefor |
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