JPH10140383A - Electrode feeder, its production and electrolytic cell for producing hydrogen peroxide - Google Patents
Electrode feeder, its production and electrolytic cell for producing hydrogen peroxideInfo
- Publication number
- JPH10140383A JPH10140383A JP8315597A JP31559796A JPH10140383A JP H10140383 A JPH10140383 A JP H10140383A JP 8315597 A JP8315597 A JP 8315597A JP 31559796 A JP31559796 A JP 31559796A JP H10140383 A JPH10140383 A JP H10140383A
- Authority
- JP
- Japan
- Prior art keywords
- cathode
- hydrogen peroxide
- electrode
- electrolytic cell
- feeder
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、製造効率が良くかつ電
極成分の溶出が殆どない電極給電体特に過酸化水素製造
用電極給電体、その製造方法及び電解槽に関し、より詳
細には従来のカーボン単体や金属あるいは合金を使用す
る電極給電体と比較して、生成する過酸化水素の分解に
よる収率低下及び電極材料の溶出をほぼ完全に防止でき
る過酸化水素製造用電極給電体、その製造方法及び電解
槽に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode power supply having good production efficiency and little elution of electrode components, in particular, an electrode power supply for hydrogen peroxide production, a method for producing the same, and an electrolytic cell. Electrode feeder for hydrogen peroxide production, which can almost completely prevent reduction in yield due to decomposition of generated hydrogen peroxide and elution of electrode material compared to electrode feeder using carbon alone, metal or alloy, and its manufacture The present invention relates to a method and an electrolytic cell.
【０００２】[0002]
【従来技術とその問題点】過酸化水素は、食品、医薬
品、パルプ、繊維、半導体工業において欠くことのでき
ない有用な基礎薬品である。従来より過酸化水素は、２
−アルキルアントラキノールを自動酸化させることによ
り工業的に得られ、同時に得られるアントラキノンを水
素還元して元のアントラキノンに戻すことで連続的に大
量合成が行なわれている。その精製のためには精留を繰
り返す等の煩雑な操作が必要であり、しかも過酸化水素
が不安定であり長期間の保存が不可能なため、更に輸送
に伴う安全性及び汚染対策の面から、オンサイト型の過
酸化水素製造装置の需要が高まっている。BACKGROUND OF THE INVENTION Hydrogen peroxide is a useful basic chemical indispensable in the food, pharmaceutical, pulp, textile and semiconductor industries. Conventionally, hydrogen peroxide is 2
-An alkylanthraquinol is industrially obtained by autoxidation, and the resulting anthraquinone is hydrogen-reduced and returned to the original anthraquinone for continuous mass synthesis. For the purification, complicated operations such as repeated rectification are required, and hydrogen peroxide is unstable and cannot be stored for a long period of time. Therefore, demand for an on-site type hydrogen peroxide production apparatus is increasing.
【０００３】従来から酸素ガスの還元反応を用いる過酸
化水素の製造が提案され、米国特許第3,592,749 号には
数種類の過酸化水素の電解製造装置が、又米国特許第4,
384,931 号にはイオン交換膜を用いるアルカリ性過酸化
水素溶液の製造方法がそれぞれ開示されている。又米国
特許第3,969,201 号には三次元構造のカーボン陰極とイ
オン交換膜から成る過酸化水素の製造装置が提案されて
いる。しかしこれらの方法では、過酸化水素の生成に必
須であるアルカリの量は生成過酸化水素にほぼ比例して
増加するため、得られる過酸化水素の濃度に対するアル
カリ濃度が高くなり過ぎ用途が限定されてしまう。又米
国特許第4,406,758 号、米国特許第4,891,107 号及び米
国特許第4,457,953 号では多孔性隔膜と疎水性カーボン
陰極を使用する過酸化水素の製造方法が開示され、重量
比（水酸化ナトリウム／過酸化水素）の小さいアルカリ
性過酸化水素水溶液が得られている。しかしこれらの方
法では陽極室から陰極室への電解質溶液の移行量及び移
行速度の制御が困難であり運転条件の管理が煩雑で特に
生成する過酸化水素の割合が一定しないという欠点があ
る。[0003] Production of hydrogen peroxide using a reduction reaction of oxygen gas has been proposed in the past, and US Patent No. 3,592,749 discloses an electrolytic production apparatus for several types of hydrogen peroxide, and US Patent No. 4,592,749.
No. 384,931 discloses a method for producing an alkaline hydrogen peroxide solution using an ion exchange membrane. U.S. Pat. No. 3,969,201 proposes an apparatus for producing hydrogen peroxide comprising a three-dimensionally structured carbon cathode and an ion exchange membrane. However, in these methods, the amount of alkali essential for the production of hydrogen peroxide increases almost in proportion to the produced hydrogen peroxide, so that the alkali concentration relative to the concentration of hydrogen peroxide obtained becomes too high and the application is limited. Would. U.S. Pat. ) Is obtained. However, these methods have disadvantages in that it is difficult to control the amount and speed of the transfer of the electrolyte solution from the anode chamber to the cathode chamber, the management of operating conditions is complicated, and particularly the ratio of generated hydrogen peroxide is not constant.
【０００４】更にJournal of Electrochemical Societ
y, vol.130, 1117〜(1983)には陽、陰イオン交換膜を
用い、中間室に硫酸を供給し、酸性の過酸化水素溶液を
安定的に得る方法が提案されている。更に電気化学57巻
ｐ1073（1989）には、陽極として膜電極接合体を使用す
ることで性能を向上させる手法が報告されている。しか
しこれらの方法では電力原単位が掛かり経済性に問題が
あり、更に硫酸の使用及び混入が不可避であるという欠
点があり、現在に至るまで十分に満足できる過酸化水素
の製造方法は得られていない。特開平６−88273 号公
報、６−336687号公報及び６−200389号公報には、三次
元構造のカーボン陰極とイオン交換膜を含む過酸化水素
製造装置、該装置を使用する過酸化水素の高収率での製
造及び電極材料が開示されている。しかしこの装置はそ
の大型化に問題点があることが判明している。即ちカー
ボン板を陰極給電体として使用すると、カーボンが多孔
性であるため反応原料である酸素や生成するアルカリ性
水溶液が透過して脆弱化しやすくなる。目止めとしてフ
ェノール樹脂含浸剤を含浸させることは可能であるが、
該含浸剤が前記アルカリ性水溶液に対する耐性を有しな
いため、有効な対策とはなりえない。又金属や合金を給
電体として使用すると、多くの場合過酸化水素の接触分
解が起こる。金は前記接触分解を比較的起こしにくい
が、高価であるため実用化が困難である。Further, Journal of Electrochemical Societ
y, vol. 130, 1117- (1983) proposes a method for stably obtaining an acidic hydrogen peroxide solution by using sulfuric acid and anion exchange membranes and supplying sulfuric acid to the intermediate chamber. Further, in Vol. 57 of Electrochemistry, p. 1073 (1989), a method of improving performance by using a membrane electrode assembly as an anode is reported. However, these methods have a drawback in that they consume a large amount of electric power and are economically disadvantageous, and furthermore, the use and mixing of sulfuric acid are unavoidable. To date, a sufficiently satisfactory method for producing hydrogen peroxide has been obtained. Absent. JP-A-6-88273, JP-A-6-336687 and JP-A-6-200389 disclose an apparatus for producing hydrogen peroxide including a carbon cathode having a three-dimensional structure and an ion exchange membrane, and a method for producing hydrogen peroxide using the apparatus. Yield production and electrode materials are disclosed. However, it has been found that this device has a problem in increasing its size. That is, when a carbon plate is used as a cathode power supply, since carbon is porous, oxygen, which is a reaction raw material, and an alkaline aqueous solution to be generated easily permeate and become brittle. It is possible to impregnate with a phenolic resin impregnant as a seal,
Since the impregnating agent has no resistance to the alkaline aqueous solution, it cannot be an effective measure. Also, when a metal or alloy is used as a power supply, catalytic decomposition of hydrogen peroxide often occurs. Gold is relatively unlikely to undergo the catalytic cracking, but is expensive and difficult to put into practical use.
【０００５】[0005]
【発明の目的】本発明は、前述の従来技術の問題点を解
決するために、つまり電極給電体としてカーボン単体や
金属又は合金を使用する従来法で生ずることのある電極
や給電体の脆弱化や生成する過酸化水素の分解をほぼ完
全に防止し、効率良く運転できる電極給電体、その製造
方法及び過酸化水素製造用電解槽を提供することを目的
とする。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, that is, the weakening of the electrodes and the power supply which may occur in the conventional method using carbon alone, a metal or an alloy as the electrode power supply. It is an object of the present invention to provide an electrode feeder which can prevent the decomposition of hydrogen peroxide and the generated hydrogen peroxide almost completely and can operate efficiently, a method for producing the same, and an electrolytic cell for producing hydrogen peroxide.
【０００６】[0006]
【問題点を解決するための手段】本発明に係わる電極給
電体は、金属又は合金から成る電極基体表面の少なくと
も電解液に接触する部分にカーボン成分を含む緻密な皮
膜を形成したことを特徴とする過酸化水素製造用電解槽
の電極給電体。金属又は合金から成る電極基体表面の少
なくとも電解液に接触する部分にカーボン成分を含む皮
膜を形成したことを特徴とする電解用給電体であり、該
給電体は、黒鉛等のカーボン成分をフッ素樹脂と混練し
シート状の皮膜に成形し、板状の電極基体表面の少なく
とも電解液に接触する部分に前記皮膜を密着固定して製
造できる。又該電極給電体は２室法及び３室法電解槽の
陰極給電体として使用し電解槽を構成できる。An electrode power supply according to the present invention is characterized in that a dense film containing a carbon component is formed on at least a portion of a surface of an electrode substrate made of a metal or an alloy which is in contact with an electrolytic solution. Electrode feeder of the electrolytic cell for producing hydrogen peroxide. An electrolysis power supply characterized in that a film containing a carbon component is formed at least on a portion of the electrode substrate surface made of a metal or an alloy that comes into contact with the electrolytic solution. To form a sheet-like film, and the film is closely adhered and fixed to at least a portion of the surface of the plate-like electrode substrate which comes into contact with the electrolytic solution. The electrode feeder can be used as a cathode feeder for two-chamber and three-chamber electrolytic cells to form an electrolytic cell.
【０００７】以下本発明を詳細に説明する。従来の電解
による過酸化水素の製造における陽極反応は陽極室中に
存在する水酸イオンの酸化による酸素ガスの発生反応で
あり、化学式で表すと式のようになる。 ４ＯＨ- → Ｏ2 ＋ ２Ｈ2 ０ ＋ ４ｅ 一方の過酸化水素製造の陰極反応は酸素ガスの還元反応
であり、化学式で表すと式のようになる。 Ｏ2 ＋ Ｈ2 ０ ＋ ２ｅ → ＯＨ- ＋ ＨＯ2 - 従来の電解による過酸化水素の分解は式〜により表
される。 ＯＨ- ＋ ＨＯ2 - → Ｏ2 ＋ Ｈ2 ０ ＋ ２ｅ Ｈ2 ０ ＋ ＨＯ2 - ＋ ２ｅ → ３ＯＨ- ２ＨＯ2 - → ２ＯＨ- ＋ Ｏ2 Hereinafter, the present invention will be described in detail. The anodic reaction in the conventional production of hydrogen peroxide by electrolysis is a reaction of generating oxygen gas by oxidizing hydroxyl ions present in the anode chamber, and can be represented by the following chemical formula. 4OH − → O 2 + 2H 2 0 + 4e On the other hand, the cathode reaction in the production of hydrogen peroxide is a reduction reaction of oxygen gas, which can be represented by a chemical formula. O 2 + H 2 0 + 2e → OH - + HO 2 - decomposition of hydrogen peroxide by conventional electrolysis is represented by Formula ~. OH - + HO 2 - → O 2 + H 2 0 + 2e H 2 0 + HO 2 - + 2e → 3OH - 2HO 2 - → 2OH - + O 2
【０００８】式〜の過酸化水素分解反応は、生成す
る過酸化水素イオンが接触分解の触媒能を有する金属や
合金に接触することにより進行する。本発明では過酸化
水素分解の触媒能を有する陰極が、カーボン成分を含む
緻密な皮膜により被覆されているため、過酸化水素を含
む陰極液が前記皮膜を透過して陰極に接触することがな
く、従って生成する過酸化水素の分解が殆どなく（過酸
化水素生成の電流効率が高く維持される）、そのまま陰
極液取出口から槽外に取り出され、所定の用途に使用で
きる。又逆に陰極保護の観点からは該陰極が電極劣化を
招きやすい過酸化水素と接触しないため、脆弱化して寿
命が短縮化することがなくなり、長期間安定した電解操
作を行なうことが可能になる。このことは電極物質が生
成する過酸化水素水溶液中に溶出しないことを意味し、
得られる過酸化水素は不純物の混入のない高純度生成物
として得られる。[0008] The hydrogen peroxide decomposition reaction represented by the formula (1) proceeds when the generated hydrogen peroxide ion comes into contact with a metal or alloy having catalytic catalytic ability for catalytic decomposition. In the present invention, the cathode having a catalytic ability to decompose hydrogen peroxide is coated with a dense film containing a carbon component, so that the catholyte containing hydrogen peroxide does not come into contact with the cathode through the film. Therefore, the generated hydrogen peroxide is hardly decomposed (the current efficiency of hydrogen peroxide generation is maintained at a high level), and the hydrogen peroxide is taken out of the cell from the catholyte outlet to be used for a predetermined purpose. Conversely, from the viewpoint of protection of the cathode, the cathode does not come into contact with hydrogen peroxide, which is liable to cause electrode deterioration. Therefore, the cathode is not weakened and its life is not shortened, and a stable electrolysis operation can be performed for a long time. . This means that the electrode material does not elute into the generated hydrogen peroxide aqueous solution,
The resulting hydrogen peroxide is obtained as a high-purity product free of impurities.
【０００９】本発明における電極給電体、特に陰極給電
体は、鉄、アルミニウム、銅及びニッケル等の金属又は
ステンレス等の前記金属を主成分とする合金から成る電
極基体にカーボンを主成分とする皮膜を被覆して構成す
る。この皮膜は前述の通り、前記電極基体が実質的に電
極液に接触することを防止するもので、その厚さはこの
電極液との接触を防止するために十分な厚さであれば良
く、通常は0.1 〜５mmである。前記皮膜の形状は前記給
電体に合わせて適宜決定すれば良く、給電体が板状の場
合にはシート状として該給電体の片面を被覆し、メッシ
ュ状である場合には、メッシュ全体が被覆される形状と
すれば良い。前記カーボン成分は耐食性の面から未処理
の炭素質を使用することはできず、黒鉛、グラッシーカ
ーボン、ホウ素などを100 〜10000 ppm ドープした導電
性のダイアモンド及びフッ素処理カーボン等を使用す
る。このカーボン成分はバインダーとして機能するポリ
テトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂粉
末と混練して例えばシート状に加工し、加圧処理又は接
着剤により前記電極基体上に密着固定して被覆する。前
記フッ素樹脂の添加量は導電性が損なわれない範囲で適
宜選択するものとし、混合比は体積で５：１〜１：１が
望ましい。前記加圧処理の圧力は１〜100kgf/cm2程度と
する。前記接着剤は導電性のものを使用することが好ま
しく、導電性を有しない場合には接着面積が全体の２分
の１以下になるようにする。In the present invention, the electrode feeder, particularly the cathode feeder, is a coating comprising carbon as a main component on an electrode substrate made of a metal such as iron, aluminum, copper and nickel or an alloy containing the above metal as a main component such as stainless steel. To cover. As described above, this film is to prevent the electrode substrate from substantially contacting the electrode solution, and its thickness may be any thickness sufficient to prevent contact with the electrode solution. Usually, it is 0.1 to 5 mm. The shape of the film may be appropriately determined according to the power supply.When the power supply is plate-shaped, it covers a single surface of the power supply as a sheet, and when the power supply is mesh-shaped, it covers the entire mesh. What is necessary is just to be the shape made. As the carbon component, untreated carbonaceous material cannot be used from the viewpoint of corrosion resistance, and conductive diamond doped with 100 to 10,000 ppm of graphite, glassy carbon, boron, or the like, fluorine-treated carbon, or the like is used. This carbon component is kneaded with a fluororesin powder such as polytetrafluoroethylene (PTFE) functioning as a binder, processed into, for example, a sheet shape, and is tightly fixed and coated on the electrode substrate by a pressure treatment or an adhesive. The addition amount of the fluororesin is appropriately selected within a range where the conductivity is not impaired, and the mixing ratio is desirably 5: 1 to 1: 1 by volume. The pressure for the pressure treatment is about 1 to 100 kgf / cm 2 . It is preferable to use an electrically conductive adhesive, and when the adhesive has no electrical conductivity, the adhesive area is set to a half or less of the whole.
【００１０】このような構成から成る本発明の電極給電
体は、２室法及び３室法の過酸化水素製造用電解槽の電
極給電体特に陰極給電体として、つまり給電体としての
機能上、電解槽の陽極又は陰極に電気的に接続された状
態で使用される。両極の給電体を同一の給電体で構成し
ても良く、電極液やガスの供給口や取出口を各給電体に
開口させても良い。陽極及び陰極の形状は特に限定され
ないが、金網状、スポンジ状、フェルト状及び粉末焼結
による多孔性を有する形状等の電極液との接触効率の良
い形状とすることが好ましい。電極の厚みは供給するア
ルカリ水溶液や生成する過酸化水素の含むアルカリ水溶
液の電導度が低いことが多いためなるべく薄くすること
が好ましいが、薄過ぎると電極液の流れやガスの流れが
阻害されることがあり、最適範囲は0.5 〜５mmである。
陽極触媒は、陽極室に酸性水溶液を供給して酸素発生を
行なうときは、白金、イリジウムなどの金属或いはそれ
らの酸化物又はカーボンが好ましく、これらの触媒は前
記形状を有するチタン、ニオブ、タンタル、ステンレ
ス、ジルコニウム、カーボン等の耐食性を有する陽極基
体上に、熱分解法、樹脂による固着法、複合めっき法等
により、10〜500 ｇ／ｍ2 程度になるように担持させ
る。The electrode feeder of the present invention having the above-described structure is used as an electrode feeder, particularly a cathode feeder, of a two-chamber method and a three-chamber method electrolytic cell for producing hydrogen peroxide. Used in a state of being electrically connected to the anode or the cathode of the electrolytic cell. The power feeders for both electrodes may be constituted by the same power feeder, and a supply port or an outlet for the electrode solution or gas may be opened in each power feeder. The shape of the anode and the cathode is not particularly limited, but is preferably a shape having good contact efficiency with the electrode solution, such as a wire mesh, a sponge, a felt, and a shape having porosity by powder sintering. The thickness of the electrode is preferably as small as possible because the conductivity of the supplied alkaline aqueous solution or the generated alkaline aqueous solution containing hydrogen peroxide is often low, but if too thin, the flow of the electrode solution and the flow of gas are hindered. In some cases, the optimum range is 0.5 to 5 mm.
The anode catalyst is preferably a metal such as platinum, iridium or their oxides or carbon when supplying an acidic aqueous solution to the anode chamber to generate oxygen, and these catalysts are preferably titanium, niobium, tantalum, and titanium having the above-mentioned shape. It is supported on a corrosion-resistant anode substrate such as stainless steel, zirconium, or carbon by a thermal decomposition method, a resin fixing method, a composite plating method, or the like so as to have a weight of about 10 to 500 g / m 2 .
【００１１】一方陰極には酸素と水を供給して過酸化水
素を生成させるが、反応効率上、中性よりアルカリ性と
することが望ましく、触媒及び陰極材料は過酸化水素分
解の少ない金やカーボンを使用することが望ましく、前
述した陽極基体の場合と同様に、適切な形状の陰極基体
上に、熱分解法等により、10〜500 ｇ／ｍ2 程度になる
ように担持させる。又原料である酸素含有ガス、反応生
成ガス、液の供給及び除去を円滑に行なうために、前記
陰極には疎水性又は親水性の材料を分散担持しても良
い。陽極室と陰極室、又は陽極室、中間室と陰極室を区
画する隔膜としては、多孔性のフッ素樹脂やイオン交換
膜が使用される。イオン交換膜はフッ素樹脂系及び炭化
水素系のいずれでも良いが、耐食性の面からは前者が好
ましい。前者の例としてはスルホン酸基或いはカルボン
酸基を有するナフィオン117 、ナフィオン350 、ナフィ
オン902 及びナフィオン961 （以上デュポン社製）があ
る。イオン交換膜は陽極や陰極で生成した各イオンが対
極で消費されることを防止するとともに、本発明のよう
な電極液の電導度が低い場合でも電解を速やかに進行さ
せる機能を有している。On the other hand, oxygen and water are supplied to the cathode to generate hydrogen peroxide. From the viewpoint of reaction efficiency, it is desirable that the catalyst be more alkaline than neutral. It is desirable to use the same as in the case of the above-mentioned anode substrate, and to carry it to about 10 to 500 g / m 2 on a suitably shaped cathode substrate by a thermal decomposition method or the like. Further, in order to smoothly supply and remove the oxygen-containing gas, the reaction product gas and the liquid as the raw materials, a hydrophobic or hydrophilic material may be dispersed and supported on the cathode. A porous fluororesin or an ion-exchange membrane is used as a diaphragm for partitioning the anode chamber and the cathode chamber, or the anode chamber, and the intermediate chamber and the cathode chamber. The ion exchange membrane may be either a fluororesin type or a hydrocarbon type, but the former is preferred from the viewpoint of corrosion resistance. Examples of the former include Nafion 117, Nafion 350, Nafion 902 and Nafion 961 (both manufactured by DuPont) having a sulfonic acid group or a carboxylic acid group. The ion exchange membrane has a function of preventing each ion generated at the anode and the cathode from being consumed at the counter electrode, and promptly performing electrolysis even when the conductivity of the electrode solution is low as in the present invention. .
【００１２】本発明の電解槽の構造は陽イオン交換膜に
より陽極室と陰極室に（陽極ガス室−中間室−陰極室を
含む）区画されること以外に特に限定されないが、本発
明に係わる電解槽のうち２室型電解槽では、陽イオン交
換膜で陽極室と陰極室に区画するとともに、陽極あるい
は陰極により陽極室あるいは陰極室を陽イオン交換膜側
の溶液室と反対側のガス室に区画しても良い。しかしこ
のような構造にすると電極液の電導度が低いと槽電圧が
増加し構造が複雑になり更に気液分離が必要になる等の
不利な点が多い。従って陽極や陰極はイオン交換膜に密
着又は接合することが望ましい。両者を密着させる場合
は前もってそれらを機械的に結合しておくか、或いは電
解時に圧力を加えれば十分であり、加える圧力は0.1 〜
30kgf/cm2 程度が好ましい。電解槽自体は、耐久性及び
過酸化水素の安定化の観点から、ガラス、樹脂ライニン
グ材料、カーボン、耐食性の優れたチタン、ステンレ
ス、ニッケル、ＰＴＦＥ樹脂等を使用して構成すること
が好ましく、金属等の過酸化水素の分解を招く恐れのあ
る材料の場合はその表面つまり電解槽内壁に前述のカー
ボン成分を含む皮膜又は他の耐食性を有する材料から成
る膜を形成することが好ましい。The structure of the electrolytic cell of the present invention is not particularly limited except that it is divided into an anode chamber and a cathode chamber (including an anode gas chamber, an intermediate chamber, and a cathode chamber) by a cation exchange membrane. In a two-chamber electrolyzer, an anolyte compartment and a catholyte compartment are partitioned by a cation exchange membrane, and the anode or cathode compartment is separated by an anode or a cathode into a gas compartment opposite to the solution compartment on the cation exchange membrane side. May be partitioned. However, with such a structure, if the conductivity of the electrode solution is low, the cell voltage increases, the structure becomes complicated, and there are many disadvantages such as the necessity of gas-liquid separation. Therefore, it is desirable that the anode and the cathode are in close contact with or bonded to the ion exchange membrane. When they are brought into close contact with each other, it is sufficient to mechanically connect them in advance, or to apply pressure during electrolysis.
About 30 kgf / cm 2 is preferable. The electrolytic cell itself is preferably made of glass, resin lining material, carbon, titanium, stainless steel, nickel, PTFE resin, etc. excellent in corrosion resistance from the viewpoint of durability and stabilization of hydrogen peroxide. In the case of a material which may cause decomposition of hydrogen peroxide, it is preferable to form a film containing the above-mentioned carbon component or a film made of another corrosion-resistant material on the surface, that is, the inner wall of the electrolytic cell.
【００１３】原料である酸素含有ガスは、二酸化炭素を
前もって除去した空気、市販の酸素ボンベ内の酸素ガス
を使用しても良いが、別に設置した電解槽を使用して電
気分解により製造した酸素ガスとすることもでき、更に
ＰＳＡ（Pressure Swing Adsorption)装置により空気を
濃縮した酸素富化空気を使用しても良い。酸素の供給量
は理論量の1.5 〜30倍程度が良く、供給前に水と接触さ
せて湿潤化することは、濃度の均一化と膜の保護上、望
ましいことである。陰極室で生成するアルカリの濃度は
前段の過酸化水素の生成に適するように設定することが
でき、アルカリ例えば水酸化ナトリウム濃度が２〜15％
のとき、生成するアルカリ性過酸化水素水溶液の過酸化
水素濃度が１〜５重量％となる。回収量は用途にも依存
するが、過酸化水素が１〜５重量％、水酸化ナトリウム
が１〜10％である。電解条件としては、温度を30〜60
℃、電流密度を１〜50A/dm2 とすることが好ましい。As the oxygen-containing gas as a raw material, air from which carbon dioxide has been removed in advance or oxygen gas in a commercially available oxygen cylinder may be used, but oxygen gas produced by electrolysis using a separately installed electrolytic cell may be used. Gas may be used, and oxygen-enriched air obtained by concentrating the air with a PSA (Pressure Swing Adsorption) device may be used. The supply amount of oxygen is preferably about 1.5 to 30 times the stoichiometric amount, and it is desirable to wet it by contacting it with water before supply in order to make the concentration uniform and protect the membrane. The concentration of the alkali generated in the cathode chamber can be set so as to be suitable for the generation of hydrogen peroxide in the preceding stage.
At this time, the concentration of hydrogen peroxide in the generated aqueous alkaline hydrogen peroxide solution is 1 to 5% by weight. The amount of recovery depends on the application, but 1-5% by weight of hydrogen peroxide and 1-10% by weight of sodium hydroxide. As the electrolysis conditions, the temperature is 30-60
C., and the current density is preferably 1 to 50 A / dm 2 .
【００１４】図１は本発明に係わる電解用給電体を有す
る過酸化水素製造用電解槽の一例を示す概略縦断面図で
ある。２室型電解槽１は、パーフロオロカーボンスルホ
ン酸型等の陽イオン交換膜２により陽極室３と陰極室４
とに区画され、該陽極室３内には繊維状、スポンジ状又
はフェルト状の金属から成る陽極５が上下に電解液供給
及び取出用の空間が形成されるように収容されている。
該陽極５には、上部近傍に陽極液供給口６を又下部近傍
に陽極液取出口７を有する陽極給電体８が電気的に接続
され、該陽極給電体８を通して陽極５に給電される。FIG. 1 is a schematic longitudinal sectional view showing an example of an electrolytic cell for producing hydrogen peroxide having a power supply for electrolysis according to the present invention. The two-chamber electrolytic cell 1 is composed of an anode chamber 3 and a cathode chamber 4 by a cation exchange membrane 2 such as a perfluorocarbon sulfonic acid type.
An anode 5 made of a fibrous, sponge-like or felt-like metal is accommodated in the anode chamber 3 so as to form upper and lower spaces for supplying and removing an electrolytic solution.
An anode feeder 8 having an anolyte supply port 6 near the upper part and an anolyte outlet 7 near the lower part is electrically connected to the anode 5, and the anode 5 is supplied with power through the anode feeder 8.
【００１５】一方前記陰極室４には、黒鉛等のカーボン
系材料から成る繊維状、スポンジ状又はフェルト状の陰
極９が上下に電解液供給及び取出用の空間が形成される
ように収容されている。該陰極９には、上部近傍に陰極
液供給口10を又下部近傍に陰極液取出口11を有し更に前
記陰極９に接触する面に、例えば黒鉛等のカーボン系材
料とバインダーであるＰＴＦＥ粉末の混合物を形成して
成る緻密な皮膜12を被覆した陰極給電体13が電気的に接
続され、該陰極給電体13を通して陰極９に給電される。
陽極室３及び陰極室の周囲はそれぞれ陽極ガスケット14
及び陰極ガスケット15によりシールされ、又前記陽極給
電体８及び陰極給電体13の外側には、それぞれ陽極室枠
16及び陰極室枠17が位置し、両室枠を内側に向かって押
圧することにより前記イオン交換膜２、両極５及び９、
両電極給電体８及び13が一体化されている。On the other hand, in the cathode chamber 4, a fibrous, sponge-like or felt-like cathode 9 made of a carbon-based material such as graphite is accommodated so as to form upper and lower spaces for electrolyte supply and extraction. I have. The cathode 9 has a catholyte supply port 10 near the upper part and a catholyte outlet 11 near the lower part, and further has a carbon-based material such as graphite and PTFE powder as a binder on the surface in contact with the cathode 9. The cathode feeder 13 covered with the dense film 12 formed by the mixture of the above is electrically connected, and power is supplied to the cathode 9 through the cathode feeder 13.
An anode gasket 14 is provided around the anode chamber 3 and the cathode chamber.
And a cathode gasket 15, and an anode chamber frame is provided outside the anode power supply 8 and the cathode power supply 13, respectively.
16 and the cathode chamber frame 17 are located, and by pressing both chamber frames inward, the ion-exchange membrane 2, the electrodes 5 and 9,
Both electrode feeders 8 and 13 are integrated.
【００１６】このような構成から成る電解槽１の陰極室
４に陰極液供給口10から酸素含有ガスを含む純水の陰極
液を、陽極室３に陽極液供給口６から水酸化ナトリウム
水溶液等をそれぞれ供給しながら両極間に通電すると、
酸素を溶解した陰極液が陰極９に接触し式に従って酸
素が還元されて過酸化水素イオンが生成する。陰極９に
給電する陰極給電体13の陰極側表面にカーボンとＰＴＦ
Ｅから成る緻密な皮膜が成形されているため、前記過酸
化水素イオンは前記皮膜12を透過せず陰極９表面に達す
ることがない。従って過酸化水素が分解したり、陰極９
が劣化したり陰極物質が陰極液中に溶出することもな
い。従って陰極液取出口11から取り出される過酸化水素
水溶液中には電解により生成するものとほぼ同量の過酸
化水素が分解することなく含有され、又電極物質の混入
による純度低下もない。更に前記陰極９が陰極液と直接
接触することがなく、長期間に亘って安定した運転が可
能になる。A catholyte containing pure gas containing oxygen-containing gas is supplied from the catholyte supply port 10 to the catholyte chamber 4 of the electrolytic cell 1 having the above-described configuration, and an aqueous solution of sodium hydroxide or the like is supplied from the anolyte supply port 6 to the anode chamber 3. When supplying electricity between both poles while supplying
The catholyte in which oxygen is dissolved contacts the cathode 9 and oxygen is reduced according to the formula to generate hydrogen peroxide ions. Carbon and PTF are provided on the cathode side surface of the cathode power supply 13 for supplying power to the cathode 9.
Since the dense film made of E is formed, the hydrogen peroxide ions do not permeate the film 12 and do not reach the surface of the cathode 9. Therefore, hydrogen peroxide is decomposed and the cathode 9
Is not degraded or the cathode material is eluted into the catholyte. Therefore, the aqueous solution of hydrogen peroxide taken out from the catholyte outlet 11 contains almost the same amount of hydrogen peroxide as that generated by electrolysis without decomposition, and there is no decrease in purity due to mixing of electrode materials. Further, the cathode 9 does not come into direct contact with the catholyte, and stable operation can be performed for a long period of time.
【００１７】[0017]
【実施例】次に本発明の電極給電体を使用する過酸化水
素製造に関する実施例を記載するが、該実施例は本発明
を限定するものではない。EXAMPLES Next, examples relating to the production of hydrogen peroxide using the electrode power feeder of the present invention will be described, but the examples do not limit the present invention.
【００１８】[0018]
【実施例１】ステンレス繊維を編んで調製した陽極、黒
鉛製フェルトから成る陰極（電極面積はそれぞれ0.5 dm
2)を陽イオン交換膜ナフィオン350 （デュポン社製）の
両面に密着させた。黒鉛粉末（ＴＧＰ−７、東海カーボ
ン株式会社製）とフッ素樹脂粉末（30Ｊ、三井フロロケ
ミカル株式会社製）を混合し焼成して調製した厚さ１mm
の緻密なシートをステンレス板の表面に張り付けて陰極
給電体とし、該陰極給電体を前記陰極に接続した。Example 1 An anode prepared by knitting stainless steel fiber and a cathode made of graphite felt (electrode area is 0.5 dm each)
2 ) was adhered to both surfaces of a cation exchange membrane Nafion 350 (manufactured by DuPont). A graphite powder (TGP-7, manufactured by Tokai Carbon Co., Ltd.) and a fluororesin powder (30J, manufactured by Mitsui Fluorochemicals, Inc.) are mixed and fired to prepare a 1 mm thick.
Was attached to the surface of a stainless steel plate to form a cathode power supply, and the cathode power supply was connected to the cathode.
【００１９】陰極室に、市販の酸素ガスボンベから酸素
ガスを毎分400 mlで、かつ純水を毎分2.5 mlでそれぞれ
供給し、陽極室には濃度40ｇ／ｌの十分な量の水酸化ナ
トリウムを供給した。温度を30℃とし両極間に2.5 Ａの
電流を流したところ、槽電圧は1.8 Ｖであり、陰極液取
出口から15ｇ／ｌの過酸化水素を含む濃度40ｇ／ｌであ
る水酸化ナトリウム水溶液が得られた。重量比（水酸化
アルカリ／過酸化水素）は2.6 、過酸化水素生成の電流
効率は95％であった。又48時間経過後の陰極液取出口で
得られた生成物中にはニッケルの溶解成分は検出されな
かった。400 ml / min of oxygen gas and 2.5 ml / min of pure water are supplied to the cathode chamber from a commercially available oxygen gas cylinder, and a sufficient amount of sodium hydroxide having a concentration of 40 g / l is supplied to the anode chamber. Was supplied. When the temperature was set to 30 ° C. and a current of 2.5 A was passed between the two electrodes, the cell voltage was 1.8 V, and an aqueous solution of sodium hydroxide having a concentration of 40 g / l containing 15 g / l hydrogen peroxide was obtained from the catholyte outlet. Obtained. The weight ratio (alkali hydroxide / hydrogen peroxide) was 2.6, and the current efficiency of hydrogen peroxide generation was 95%. After 48 hours, no nickel dissolved component was detected in the product obtained at the catholyte outlet.
【００２０】[0020]
【比較例１】皮膜をステンレス板表面に張り付けなかっ
たこと以外は実施例１と同一条件で作製した電解槽を使
用し実施例１と同一条件で運転を行なったところ、槽電
圧は1.7 Ｖであり、陰極液取出口から12ｇ／ｌの過酸化
水素を含む濃度45ｇ／ｌである水酸化ナトリウム水溶液
が得られた。重量比は3.8 、過酸化水素生成の電流効率
は80％であった。得られた過酸化水素水溶液中には若干
量のステンレス溶解成分が検出された。Comparative Example 1 An electrolytic cell prepared under the same conditions as in Example 1 was operated under the same conditions as in Example 1 except that the film was not stuck to the surface of the stainless steel plate, and the cell voltage was 1.7 V. In this case, an aqueous solution of sodium hydroxide having a concentration of 45 g / l containing 12 g / l of hydrogen peroxide was obtained from the catholyte outlet. The weight ratio was 3.8, and the current efficiency of hydrogen peroxide generation was 80%. Some amount of dissolved stainless steel was detected in the obtained aqueous hydrogen peroxide solution.
【００２１】[0021]
【発明の効果】本発明に係わる電極給電体は、金属又は
合金から成る電極基体表面の少なくとも電解液に接触す
る部分にカーボン成分を含む緻密な皮膜を形成したこと
を特徴とする過酸化水素製造用電解槽の電極給電体であ
る。従来のカーボン単体や金属あるいは合金を使用する
電極給電体では、カーボン単体の場合は多孔性のカーボ
ン単体内に生成する過酸化水素水溶液等の電極液が浸透
して電極が脆弱化して寿命の短縮化が生じ、又電極物質
が溶出して過酸化水素水溶液が汚染されるという欠点が
ある。更にステンレス等の金属電極では過酸化水素の分
解が生じて電流効率が低下し、又金電極は過酸化水素の
分解は殆ど生じないのに対し、高価すぎるという欠点を
有している。これに対し、本発明に係わる電極給電体の
ように、カーボン成分を含む緻密な皮膜を、電極液との
接触面に形成した電極給電体では、前記皮膜が電極液を
透過させないため、生成過酸化水素の分解による電流効
率の低下、電極の劣化及びそれに伴う過酸化水素水溶液
の汚染がなく、目的通り過酸化水素生成の電流効率を高
く維持したまま、電極の寿命短縮及び過酸化水素水溶液
の汚染を効果的に防止できる。更に本発明の電極給電体
を使用すると、電解槽の大型化に容易に対応でき、大量
の過酸化水素製造に適した電解槽を構成できる。The electrode power supply according to the present invention is characterized in that a dense film containing a carbon component is formed on at least a portion of the surface of an electrode substrate made of a metal or an alloy which comes into contact with an electrolytic solution. It is an electrode feeder of the electrolytic cell for use. With conventional electrode feeders that use carbon alone or metals or alloys, in the case of carbon alone, the electrode solution such as an aqueous solution of hydrogen peroxide generated in the porous carbon alone penetrates, weakening the electrode and shortening its life There is a drawback in that the electrode material is eluted and the aqueous hydrogen peroxide solution is contaminated. Further, a metal electrode such as stainless steel is decomposed with hydrogen peroxide to lower the current efficiency, and a gold electrode is hardly decomposed with hydrogen peroxide, but has the disadvantage of being too expensive. On the other hand, in the electrode power supply body in which a dense film containing a carbon component is formed on the contact surface with the electrode solution as in the electrode power supply body according to the present invention, the film does not allow the electrode solution to permeate, and thus the generation of the electrode solution is insufficient. There is no decrease in current efficiency due to decomposition of hydrogen oxide, deterioration of the electrode and the accompanying contamination of the aqueous hydrogen peroxide solution. Pollution can be effectively prevented. Further, by using the electrode power supply of the present invention, it is possible to easily cope with an increase in the size of the electrolytic cell, and to configure an electrolytic cell suitable for producing a large amount of hydrogen peroxide.
【００２２】又本発明に係わる電極給電体の製造方法
は、黒鉛、グラッシーカーボン、ダイアモンド及びフッ
素処理カーボンから選択されたカーボン成分をフッ素樹
脂と混練しシート状の皮膜に成形した後、金属又は合金
から成る板状の電極基体表面の少なくとも電解液に接触
する部分に前記皮膜を密着固定することを特徴とする過
酸化水素製造用電解槽の電極給電体の製造方法である。
この製造方法により製造される電極給電体も同様の効果
を生じさせる。The method of manufacturing an electrode power supply according to the present invention is characterized in that a carbon component selected from graphite, glassy carbon, diamond and fluorinated carbon is kneaded with a fluororesin, formed into a sheet-like film, and then formed into a metal or alloy. A method for producing an electrode feeder for an electrolytic cell for producing hydrogen peroxide, characterized in that the film is closely adhered and fixed to at least a portion of the surface of a plate-shaped electrode substrate which comes into contact with an electrolytic solution.
The electrode feeder manufactured by this manufacturing method also produces the same effect.
【００２３】前述の電極給電体は、２室法及び３室法の
過酸化水素製造用電解槽に組み込んで使用でき、本発明
の効果を確実に発揮させるためには、電解槽をガラス、
樹脂ライニング材料等の耐食性がありかつ過酸化水素分
解を生じさせない材料で構成することが望ましい。電解
槽が耐食性はあるが過酸化水素分解を生じさせる金属や
合金が構成されている場合には、陰極室内壁を、カーボ
ン成分を含む皮膜等の耐食性がありかつ過酸化水素分解
を生じさせない材料でが被覆することが望ましい。The above-mentioned electrode feeder can be used by being incorporated in an electrolytic cell for producing hydrogen peroxide in a two-chamber method or a three-chamber method. In order to reliably exert the effects of the present invention, the electrolytic cell is made of glass,
It is desirable to use a material such as a resin lining material which has corrosion resistance and does not cause decomposition of hydrogen peroxide. If the electrolytic cell is made of a metal or alloy that is corrosion-resistant but decomposes hydrogen peroxide, the inner wall of the cathode should be made of a corrosion-resistant material that does not cause decomposition of hydrogen peroxide, such as a coating containing a carbon component. It is desirable to coat with.
【図１】本発明に係わる電解槽の一例を示す概略縦断面
図。FIG. 1 is a schematic longitudinal sectional view showing an example of an electrolytic cell according to the present invention.
１・・・２室型電解槽 ２・・・ 陽イオン交換膜 ３
・・・陽極室 ４・・・陰極室 ５・・・陽極 ６・・
・陽極液供給口 ７・・・陽極液取出口 ８・・・陽極
給電体 ９・・・陰極 10・・・陰極液供給口 11・・
・陰極液取出口12・・・皮膜 13・・・陰極給電体 14
・・・陽極ガスケット 15・・・陰極ガスケット 16・
・・陽極室枠 17・・・陰極室枠DESCRIPTION OF SYMBOLS 1 ... Two-chamber electrolytic cell 2 ... Cation exchange membrane 3
... Anode room 4 ... Cathode room 5 ... Anode 6 ...
・ Anolyte supply port 7 ・ ・ ・ Anolyte outlet 8 ・ ・ ・ Anode power supply 9 ・ ・ ・ Cathode 10 ・ ・ ・ Cathode supply port 11 ・ ・
・ Cathode liquid outlet 12 ・ ・ ・ Coating 13 ・ ・ ・ Cathode feeder 14
・ ・ ・ Anode gasket 15 ・ ・ ・ Cathode gasket 16 ・
..Anode compartment frame 17 ・ ・ ・ Cathode compartment frame
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成８年１１月１４日[Submission date] November 14, 1996
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１９[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１９】陰極室に、市販の酸素ガスボンベから酸素
ガスを毎分400 mlで、かつ純水を毎分2.5 mlでそれぞれ
供給し、陽極室には濃度40ｇ／ｌの十分な量の水酸化ナ
トリウムを供給した。温度を30℃とし両極間に2.5 Ａの
電流を流したところ、槽電圧は1.8 Ｖであり、陰極液取
出口から15ｇ／ｌの過酸化水素を含む濃度40ｇ／ｌであ
る水酸化ナトリウム水溶液が得られた。重量比（水酸化
アルカリ／過酸化水素）は2.6 、過酸化水素生成の電流
効率は95％であった。又48時間経過後の陰極液取出口で
得られた生成物中にはステンレスの溶解成分は検出され
なかった。400 ml / min of oxygen gas and 2.5 ml / min of pure water are supplied to the cathode chamber from a commercially available oxygen gas cylinder, and a sufficient amount of sodium hydroxide having a concentration of 40 g / l is supplied to the anode chamber. Was supplied. When the temperature was set to 30 ° C. and a current of 2.5 A was passed between the two electrodes, the cell voltage was 1.8 V, and an aqueous solution of sodium hydroxide having a concentration of 40 g / l containing 15 g / l hydrogen peroxide was obtained from the catholyte outlet. Obtained. The weight ratio (alkali hydroxide / hydrogen peroxide) was 2.6, and the current efficiency of hydrogen peroxide generation was 95%. No dissolved components of stainless steel were detected in the product obtained at the catholyte outlet after 48 hours.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山根 源三 神奈川県藤沢市石川1145番地Ｂ−203号 (72)発明者 錦 善則 神奈川県藤沢市藤沢１丁目１番の23 (72)発明者 島宗 孝之 東京都町田市本町田3006番地30 (72)発明者 矢口 時也 東京都江戸川区東篠崎２−３−２ 王子製 紙株式会社江戸川研究センター製紙技術研 究所内 (72)発明者 山田 信夫 東京都江戸川区東篠崎２−３−２ 王子製 紙株式会社江戸川研究センター製紙技術研 究所内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Genzo Yamane 1145, Ishikawa, Fujisawa-shi, Kanagawa B-203 No. 72 (72) Inventor Yoshinori Nishiki 1-2-1 Fujisawa, Fujisawa-shi, Kanagawa 23-72 (72) Inventor Shimamune Takayuki 3006-30 Honmachida, Machida-shi, Tokyo (72) Inventor Tokiya Yaguchi 2-3-2 Higashishinozaki, Edogawa-ku, Tokyo Oji Paper Co., Ltd. Edogawa Research Center Papermaking Research Laboratory (72) Inventor Nobuo Yamada Tokyo 2-3-2 Higashishinozaki, Edogawa-ku, Tokyo Oji Paper Co., Ltd. Edogawa Research Center Papermaking Technology Laboratory
Claims (4)
なくとも電解液に接触する部分にカーボン成分を含む緻
密な皮膜を形成したことを特徴とする過酸化水素製造用
電解槽の電極給電体。1. An electrode feeder for an electrolytic cell for producing hydrogen peroxide, wherein a dense film containing a carbon component is formed on at least a portion of the surface of an electrode substrate made of a metal or an alloy which comes into contact with an electrolytic solution.
イアモンド及びフッ素処理カーボンから選択されたカー
ボン成分をフッ素樹脂と混練しシート状の皮膜に成形し
た後、金属又は合金から成る板状の電極基体表面の少な
くとも電解液に接触する部分に前記皮膜を被覆すること
を特徴とする過酸化水素製造用電解槽の電極給電体の製
造方法。2. A plate-like electrode substrate surface made of a metal or an alloy after kneading a carbon component selected from graphite, glassy carbon, conductive diamond and fluorine-treated carbon with a fluororesin to form a sheet-like film. A method for producing an electrode feeder for an electrolytic cell for producing hydrogen peroxide, comprising coating at least a portion of the electrode feeder with an electrolytic solution with the film.
極室と陰極を収容した陰極室に区画された電解槽の陰極
室に酸素含有ガス及び水を供給して電解し、過酸化水素
を含む水溶液を得る過酸化水素製造用電解槽において、
前記陰極に給電するための陰極給電体として、金属又は
合金から成る電極基体表面の少なくとも電解液に接触す
る部分にカーボン成分を含む皮膜を形成した陰極給電体
を使用することを特徴とする電解槽。3. An oxygen-containing gas and water are supplied to a cathode chamber of an electrolytic cell partitioned by a cation exchange membrane into an anode chamber accommodating an anode and a cathode chamber accommodating a cathode, and the cell contains hydrogen peroxide. In an electrolytic cell for producing hydrogen peroxide to obtain an aqueous solution,
An electrolytic cell characterized in that a cathode power feeder having a film containing a carbon component formed on at least a portion of the surface of an electrode substrate made of a metal or an alloy which is in contact with an electrolytic solution is used as a cathode power feeder for feeding power to the cathode. .
が被覆されている請求項３に記載の電解槽。4. The electrolytic cell according to claim 3, wherein the inner wall of the cathode chamber is coated with a film containing a carbon component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31559796A JP3596997B2 (en) | 1996-11-12 | 1996-11-12 | Electrode feeder, method for producing the same, and electrolytic cell for producing hydrogen peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31559796A JP3596997B2 (en) | 1996-11-12 | 1996-11-12 | Electrode feeder, method for producing the same, and electrolytic cell for producing hydrogen peroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10140383A true JPH10140383A (en) | 1998-05-26 |
| JP3596997B2 JP3596997B2 (en) | 2004-12-02 |
Family
ID=18067273
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31559796A Expired - Fee Related JP3596997B2 (en) | 1996-11-12 | 1996-11-12 | Electrode feeder, method for producing the same, and electrolytic cell for producing hydrogen peroxide |
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| Country | Link |
|---|---|
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|---|---|---|---|---|
| WO2003097535A1 (en) * | 2002-05-17 | 2003-11-27 | Nippon Oil Corporation | Aqueous solution for diluting water-soluble metal working fluid, apparatus for production thereof, fluid coolant, and apparatus for production of fluid coolant |
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1996
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003097535A1 (en) * | 2002-05-17 | 2003-11-27 | Nippon Oil Corporation | Aqueous solution for diluting water-soluble metal working fluid, apparatus for production thereof, fluid coolant, and apparatus for production of fluid coolant |
| JP2009248059A (en) * | 2008-04-10 | 2009-10-29 | Niigata Univ | Simultaneously manufacturing apparatus for ozone water and hydrogen peroxide water |
| JP2010007133A (en) * | 2008-06-27 | 2010-01-14 | Daiso Co Ltd | Method and device for producing metal indium |
| JP2010007151A (en) * | 2008-06-30 | 2010-01-14 | Chlorine Eng Corp Ltd | Sulfuric acid electrolytic cell and sulfuric acid recycle type cleaning system |
| CN103695958A (en) * | 2013-12-13 | 2014-04-02 | 南开大学 | Configuration of air diffusion cathode for efficiently producing hydrogen peroxide and preparation method thereof |
| WO2019093033A1 (en) * | 2017-11-10 | 2019-05-16 | 株式会社東芝 | Hydrogen peroxide water manufacturing device |
| WO2019093036A1 (en) * | 2017-11-10 | 2019-05-16 | 株式会社東芝 | Water treatment system |
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| JP2019089004A (en) * | 2017-11-10 | 2019-06-13 | 株式会社東芝 | Hydrogen peroxide solution production apparatus |
| JP2021142522A (en) * | 2017-11-10 | 2021-09-24 | 株式会社東芝 | Hydrogen peroxide solution production apparatus |
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|---|---|
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