JP2014198310A - Compact electrolytic water generator - Google Patents
Compact electrolytic water generator Download PDFInfo
- Publication number
- JP2014198310A JP2014198310A JP2013075137A JP2013075137A JP2014198310A JP 2014198310 A JP2014198310 A JP 2014198310A JP 2013075137 A JP2013075137 A JP 2013075137A JP 2013075137 A JP2013075137 A JP 2013075137A JP 2014198310 A JP2014198310 A JP 2014198310A
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- Prior art keywords
- water
- ozone
- anode
- cathode
- electrolyzed water
- 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
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 112
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 41
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Images
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- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
本発明は、脱臭、殺菌や洗浄等に用いられる主としてオゾンガス、オゾン水、過酸化水素水の製造に用いる小型電解水生成装置に関する。 The present invention relates to a small electrolyzed water generating apparatus mainly used for producing ozone gas, ozone water, and hydrogen peroxide water, which is used for deodorization, sterilization, cleaning, and the like.
［殺菌消毒液］
従来、広範な環境における殺菌消毒剤として、次亜塩素酸ナトリウム、次亜塩素酸カルシウム、ジクロロイソシアヌル酸ナトリウム等の塩素系殺菌剤が広く用いられている。中でも次亜塩素酸ナトリウム等次亜塩素酸塩は、価格面と効果の点で汎用されているが、医療、食品工業等、種々の分野で要求される微生物の殺菌、滅菌に対して、更にその効力を向上させるための多くの提案が特許文献１〜３に報告されている。
通常、このような組成物は各成分を水中に添加するか、各成分を含有する水溶液を混合することで調製される。
[Disinfectant]
Conventionally, chlorine-based disinfectants such as sodium hypochlorite, calcium hypochlorite, and sodium dichloroisocyanurate have been widely used as disinfectants in a wide range of environments. Among them, hypochlorite such as sodium hypochlorite is widely used in terms of price and effect, but for further sterilization and sterilization of microorganisms required in various fields such as medical and food industries. Many proposals for improving the efficacy are reported in
Usually, such a composition is prepared by adding each component to water or mixing an aqueous solution containing each component.
［電解水の代替利用］
しかしながら、塩素系殺菌剤を多量に使用すると弊害が発生する。例えば大量に食材を取り扱う工場、小売店では１００ｍｇ／Ｌを越える次亜塩素酸ナトリウムによる洗浄を行っており、これが食材の味を損なうのみならず危険性（トリハロメタンの増加）を生じさせるため問題視されている。
これを解決することを主目的として、電気分解により生成される電解水が、農業、食品、医療等の分野において有用であることが鋭意検討され、日本を中心に電解水、或いは、オゾン水への代替利用が進んでいる。クリーンな電気エネルギーを利用して、電極表面で化学反応を制御することにより、水素、酸素、オゾン、過酸化水素などを合成できるが、特に陽極での酸化反応では、水処理に有効な酸化剤（有効塩素、オゾンなど過酸化物）が生成し、一部ＯＨラジカルなどの活性種も発生することが知られている（強酸性電解水の基礎知識、オーム社）。
[Alternative use of electrolyzed water]
However, when a large amount of chlorine-based disinfectant is used, harmful effects occur. For example, factories and retailers that handle large amounts of food are washed with sodium hypochlorite exceeding 100 mg / L, which not only impairs the taste of the food but also creates danger (increased trihalomethane). Has been.
With the main purpose of solving this, electrolyzed water generated by electrolysis has been eagerly studied to be useful in fields such as agriculture, food, and medicine, and it has been converted to electrolyzed water or ozone water mainly in Japan. Alternative use of is progressing. Hydrogen, oxygen, ozone, hydrogen peroxide, etc. can be synthesized by controlling the chemical reaction on the electrode surface using clean electrical energy, but it is an oxidant effective for water treatment, especially in the oxidation reaction at the anode. (Peroxides such as effective chlorine and ozone) are produced, and it is known that some active species such as OH radicals are also generated (basic knowledge of strongly acidic electrolyzed water, Ohm).
電解水の優れた殺菌・消毒作用に着目し、医療現場や家庭での利用、例えば患部、切開部、留置カテーテルの経皮開口部等の殺菌、消毒、あるいはキッチン用品、ベビー用品、家具等の家庭用品、トイレ、浴槽等の住居まわりの殺菌、消毒に使用することが検討されている。このような電解水は、溶解によりイオンが生じる溶質、例えば塩化ナトリウム等を添加し、また必要に応じｐＨ調整のための酸を添加した水（被電解水）を、電気分解することによって得られる。 Paying attention to the excellent sterilization and disinfection action of electrolyzed water, use in medical field and home, such as sterilization, disinfection of affected area, incision, percutaneous opening of indwelling catheter, etc. or kitchen supplies, baby products, furniture, etc. It is considered to be used for sterilization and disinfection of household items, toilets, bathtubs and other residential areas. Such electrolyzed water is obtained by electrolyzing water (electrolyzed water) to which a solute that generates ions upon dissolution, such as sodium chloride, is added, and where necessary an acid for adjusting the pH is added. .
［電解水の種類］
電解水は食品添加物以外にも利用可能である。電解セルでの陽極反応は、水のみの場合、
Electrolyzed water can be used in addition to food additives. The anodic reaction in the electrolysis cell is only water,
塩酸、塩化物イオンを添加した場合には、式（３）及び（４）に従って次亜塩素酸が生成するが、
陰極反応では、水素を過剰に溶解している水素水、アルカリイオン水などの合成可能である。
このように、食品添加物として認可される酸性水のほかに、電解質の選択による複数の過酸化物を含有する電解水が製造できる。
In the cathode reaction, hydrogen water in which hydrogen is excessively dissolved, alkali ion water, or the like can be synthesized.
Thus, in addition to acidic water approved as a food additive, electrolyzed water containing a plurality of peroxides can be produced by selecting an electrolyte.
［電解水の特徴］
食品添加物として認可されている電解水の種類には、
ａ）電解次亜水（２０〜２００ｍｇ／Ｌ、ｐＨ＞７．５、水道水または０．２〜２％の食塩水原料、無隔膜セル）
ｂ）微酸性電解水（１０〜８０ｍｇ／Ｌ、５＜ｐＨ＜６．５、２〜６％の塩酸原料、無隔膜セル）
ｃ）弱酸性電解水（１０〜６０ｍｇ／Ｌ、２．７＜ｐＨ＜５、濃厚食塩水原料、有隔膜３室セル）
ｄ）強酸性電解水（２０〜６０ｍｇ／Ｌ、２．２＜ｐＨ＜２．７、０．２％以下の食塩水原料、有隔膜２室セル）
がある（食安発０４２６第１号）。
[Characteristics of electrolyzed water]
The types of electrolyzed water that are approved as food additives include:
a) Electrolytic hyponitrous acid (20 to 200 mg / L, pH> 7.5, tap water or 0.2 to 2% saline raw material, non-diaphragm cell)
b) Slightly acidic electrolyzed water (10 to 80 mg / L, 5 <pH <6.5, 2 to 6% hydrochloric acid raw material, non-diaphragm cell)
c) Weakly acidic electrolyzed water (10 to 60 mg / L, 2.7 <pH <5, concentrated saline raw material, diaphragm 3-cell cell)
d) Strongly acidic electrolyzed water (20-60 mg / L, 2.2 <pH <2.7, 0.2% or less saline raw material, two-chamber cell)
(Food Safety 0426 No. 1).
これらの中で酸性水のメリットは、
（１）ＴＨＭは酸性では生成しにくいため安全性が優れている。
（２）耐性菌が発生しにくい、オンサイトで管理がしやすい。
（３）アルカリ性電解水との併用処理ができる。
（４）水道水のような感覚で利用でき、手指に匂いが残らない。
（５）直前での使用で十分（殺菌時間が短い）。
などである。
従来の次亜塩素ナトリウム薬液処理では２００ｍｇ／Ｌまで食品添加物として認可されているものの、味覚も悪くなり、残留性があるのに比較して、これらの電解水は装置としての初期投資はかかるが、低濃度で殺菌効果が高く、有益である。
Among these, the merit of acidic water is
(1) THM is excellent in safety because it is difficult to produce when acidic.
(2) Resistant bacteria are unlikely to be generated and easy to manage on site.
(3) Combined treatment with alkaline electrolyzed water is possible.
(4) It can be used like tap water, and there is no smell left on the fingers.
(5) Use immediately before is sufficient (disinfection time is short).
Etc.
Although the conventional sodium hypochlorite chemical treatment is approved as a food additive up to 200 mg / L, the electrolysis water takes an initial investment as a device compared to the poor taste and persistence. However, the low concentration has a high bactericidal effect and is beneficial.
［オゾン水の特徴］
前記の電解水のような機能水の中にオゾン水がある。オゾンは強力な酸化剤であり、殺菌性に優れ、また、使用後は安全な酸素にもどる、塩分を含まないため腐食を生じにくいなどの特長を有する。オゾン水は既に食品添加物リストに登載され、米国ＦＤＡ（食品医薬品局）で食品貯蔵、製造工程での殺菌剤として認可（２００１年）が得られている。既に食品工場内の殺菌、食品そのものの殺菌に多くの実績がある。最近では、皮膚科、眼科、歯科などの医療現場、獣医科分野においても、これまでの殺菌水と同等以上の効果を発揮しつつ、生体への負荷を軽減できることが注目されている。
オゾン水のメリットとして、
（１）オゾン（ＯＨラジカル）殺菌効果は細胞壁の酸化破壊であり無差別性のため耐性菌が存在しないといえる。
（２）残留性がない。
などがあり、必要に応じて他の残留性を有する酸化剤（過酸化水素、次亜塩素酸塩、過硫酸塩、過炭酸塩など）と併用すれば、より有効な殺菌処理が可能となる。
[Features of ozone water]
Among functional waters such as the electrolyzed water is ozone water. Ozone is a strong oxidizer, has excellent bactericidal properties, returns to safe oxygen after use, and does not contain salt, so it does not easily corrode. Ozone water has already been listed on the food additive list and has been approved by the US FDA (Food and Drug Administration) as a disinfectant in food storage and manufacturing processes (2001). There are already many achievements in sterilization in food factories and foods themselves. Recently, in medical fields such as dermatology, ophthalmology, dentistry, and veterinary medicine, attention has been paid to the ability to reduce the burden on the living body while exhibiting the same or better effect than conventional sterilized water.
As an advantage of ozone water,
(1) The ozone (OH radical) bactericidal effect is oxidative destruction of the cell wall, and it can be said that there are no resistant bacteria due to indiscriminateness.
(2) There is no persistence.
If used in combination with other oxidizing agents (hydrogen peroxide, hypochlorite, persulfate, percarbonate, etc.) as needed, more effective sterilization can be achieved. .
［オゾン水の従来製法］
オゾン水は従来から放電型のオゾンガス発生器を用いて製造することが一般的であり、数ｍｇ／Ｌのオゾン水を容易に製造でき、浄水処理、食品洗浄分野で利用されている。しかしながら、瞬時応答性に優れたハンディかつ高濃度なオゾン水装置の発生器としては以下の理由により不適当であった。
（１）オゾンをいったんガスとして発生させ、その後、水に溶解させる２つの工程を必要とすること。
（２）後述する電解法に比較して生成オゾン濃度が低いため高圧下で水中に注入し、溶解させ、製造する必要がある。
（３）発生電源が高電圧・高周波のため、小型化しにくい。
（４）放電によるオゾン水生成装置では、オゾンガス発生能力が安定するまで時間（数分間の待機時間）を要し、瞬時に一定濃度のオゾン水を調製することが困難である。
[Conventional manufacturing method of ozone water]
Conventionally, ozone water is generally produced using a discharge-type ozone gas generator, and several mg / L of ozone water can be easily produced and used in the field of water purification and food washing. However, it is unsuitable as a generator of a handy and high-concentration ozone water apparatus with excellent instantaneous response for the following reasons.
(1) Two steps of generating ozone once as a gas and then dissolving it in water are required.
(2) Since the generated ozone concentration is lower than that of the electrolysis method described later, it is necessary to inject it into water under high pressure, dissolve it, and manufacture it.
(3) Since the generated power supply is high voltage and high frequency, it is difficult to reduce the size.
(4) In the ozone water generating device by discharge, it takes time (a waiting time of several minutes) until the ozone gas generating ability is stabilized, and it is difficult to instantaneously prepare ozone water having a constant concentration.
［電解オゾン製造法］
電解法は、放電法に比較して電力原単位は劣るが、高濃度のオゾンガス及び水が容易に得られる特徴により、電子部品洗浄などの特殊分野で汎用されている。原理的に直流低圧電源を用いるため、瞬時応答性、安全性に優れており、小型のオゾンガス、オゾン水発生器としての利用が期待されている。また、用途に応じて電池駆動、発電機駆動、交流直流変換駆動が選択できる。
[Electrolytic ozone production method]
The electrolysis method is inferior in terms of electric power unit as compared with the discharge method, but is widely used in special fields such as electronic component cleaning due to the feature of easily obtaining high-concentration ozone gas and water. Since a DC low-voltage power supply is used in principle, it has excellent instantaneous response and safety, and is expected to be used as a small ozone gas and ozone water generator. Also, battery drive, generator drive, and AC / DC conversion drive can be selected according to the application.
オゾンガスを効率よく発生させるには、適切な触媒と電解質を選択することが不可欠である。電極材料として、白金などの貴金属、α−二酸化鉛、β−二酸化鉛、フルオロカーボンを含浸させたグラッシーカーボン、ダイヤモンドが知られている。電解質としては、硫酸、リン酸、フッ素基含有などの水溶液が利用されてきたが、これらの電解質は取り扱いが不便であり広く使用されてはいない。固体高分子電解質を隔膜として用い、純水を原料とする水電解セルは、その点で管理がしやすく、汎用されている。従来からの触媒である二酸化鉛では、１２重量％以上の高濃度なオゾンガスが得られる（非特許文献１参照）。 In order to efficiently generate ozone gas, it is essential to select an appropriate catalyst and electrolyte. Known electrode materials include noble metals such as platinum, α-lead dioxide, β-lead dioxide, glassy carbon impregnated with fluorocarbon, and diamond. As electrolytes, aqueous solutions containing sulfuric acid, phosphoric acid, fluorine groups and the like have been used, but these electrolytes are inconvenient to handle and are not widely used. A water electrolysis cell using a solid polymer electrolyte as a diaphragm and using pure water as a raw material is easy to manage in that respect and is widely used. With lead dioxide, which is a conventional catalyst, ozone gas having a high concentration of 12% by weight or more can be obtained (see Non-Patent Document 1).
直接合成方式と呼ばれるシステムでは、特許文献７に記載されているように、電極近傍の溶液に十分な流速を与えることで、ガス化する前にオゾン水として取り出すようにしている。また、純水以外の原料水を電解系に供給する場合は、貴金属電極触媒自体の活性が水質の影響を受けるため、寿命や効率などの電解性能が変動することは注意を要する。特許文献８では、導電性ダイヤモンドが機能水（オゾン含む）用電極として有用であることが開示されている。 In a system called a direct synthesis method, as described in Patent Document 7, a sufficient flow rate is given to a solution in the vicinity of an electrode so as to be taken out as ozone water before gasification. In addition, when raw material water other than pure water is supplied to the electrolytic system, the activity of the noble metal electrode catalyst itself is affected by the water quality, so care must be taken that the electrolytic performance such as life and efficiency fluctuates. Patent Document 8 discloses that conductive diamond is useful as an electrode for functional water (including ozone).
［小型装置の開発］
医療現場や家庭でより簡易に殺菌、消毒等を行うために、携帯可能な小型の電解水噴出器が提案されている（特許文献４〜６）。小型であれば、室内、水回り、食器、衣類等の家庭用あるいは業務用の消臭、殺菌、漂白、又は人体、例えば手指等の殺菌、消毒等に広く使用することができる。
[Development of small equipment]
In order to perform sterilization, disinfection, and the like more easily at medical sites and homes, portable small electrolyzed water ejectors have been proposed (
このため、前記課題の多くを解決でき、安価かつ高性能を得ることができ、携帯可能な、あるいは小さいスペースに設置可能な小型の電解セルの開発が望まれている。
小型のオゾンガス発生器など、空気清浄化を目的として、幾つかの発明がなされている。
１）特許文献９には、内部にオゾンガス生成装置を有する受話器を開示している。
２）特許文献１０には、電話機のケーシング内に、オゾン発生装置と吸着剤を配し、循環ファンによってオゾンをハンドセットに送り、臭気を吸着剤に導く構造とする。
３）特許文献１１には、電解型オゾン発生装置及びそれを用いた携帯型電子機器が開示されている。
４）特許文献１２には、マイナスイオン発生部付き通信端末装置が開示されている。外部装置との通信機能と利用者が通話するための送受話器等を備えた通信端末装置で、通信端末装置の表面にマイナスイオン発生部を設けた通信端末装置の一実施例であるＰＨＳ端末において、公衆通信網との通信機能としてのインタフェースであるアンテナと、利用者が通話するための送受話器部の送話部と受話部とを備えたＰＨＳ端末の操作部背面側と、送受話器部との表面にマイナスイオン発生部とを設けたものである。
５）特許文献１３には、携帯電話機にマイナスイオンを発生するイオン発生部１を備えたものが提案されている。
６）特許文献１４には、水にオゾンを発生させる装置で、印刷回路基板上にオゾン発生用電極回路が形成されていて、陰極表面を粗くすることで水素ガスの気泡を大きく成長させ、結果として、オゾン水濃度が増加できることが開示されている。
For this reason, it is desired to develop a small electrolysis cell that can solve many of the above problems, can be obtained at low cost and with high performance, and can be carried or installed in a small space.
Several inventions have been made for the purpose of air purification, such as a small ozone gas generator.
1) Patent Document 9 discloses a receiver having an ozone gas generator inside.
2)
3) Patent Document 11 discloses an electrolytic ozone generator and a portable electronic device using the same.
4) Patent Document 12 discloses a communication terminal device with a negative ion generator. In a communication terminal device having a communication function with an external device and a handset for a user to talk, a PHS terminal which is an embodiment of a communication terminal device provided with a negative ion generator on the surface of the communication terminal device A back side of an operation unit of a PHS terminal including an antenna as an interface as a communication function with a public communication network, a transmitter and receiver of a transmitter / receiver unit for a user to talk, a transmitter / receiver unit, The negative ion generating part is provided on the surface of the substrate.
5) Patent Document 13 proposes a mobile phone provided with an
6) Patent Document 14 discloses an apparatus for generating ozone in water, in which an electrode circuit for generating ozone is formed on a printed circuit board, and by making the cathode surface rough, bubbles of hydrogen gas grow greatly. It is disclosed that the ozone water concentration can be increased.
これまでの小型のオゾン電解セルでは、以下の課題があった。
（１）純水や井戸水、水道水を原料とする場合、溶液抵抗が大きいため、電解効率が悪い。
（２）伝導性を付与するために通常電解質を加えるが、用途によっては電解質を添加できない場合があった。
（３）イオン交換膜などを用いるとイオン伝導性が向上し、反応効率の増加が期待できるが、電極との接合が困難であった。
（４）該膜は通常非多孔性であり、通常は電解液の供給と生成物の除去のために、多孔性の電極が利用し、その形状が複雑であった。
（５）イオン交換能を有する粒子を電極間に充填してもよいが、組み立て上及び構造上、多くの制約があった。
然るに、前述のとおり、これまで小型の電解セルは提案されてきたが、具体的なセル仕様については開示がなかった。通常は、伝導性の乏しい電解液を電解することは困難であり、導電性を付与するイオン交換膜樹脂成分や支持電解質を添加するしかなかった。イオン交換膜成分がある場合、水道水原料で電解すると、陰極および膜内に硬度成分が付着し、電解が継続できなかった。酸による洗浄は手間であった。
Conventional small ozone electrolysis cells have the following problems.
(1) When pure water, well water, or tap water is used as a raw material, the electrolytic resistance is poor because the solution resistance is large.
(2) Although an electrolyte is usually added to impart conductivity, the electrolyte may not be added depending on the application.
(3) When an ion exchange membrane or the like is used, ion conductivity is improved and an increase in reaction efficiency can be expected, but it is difficult to join the electrode.
(4) The membrane is usually non-porous, and a porous electrode is usually used for supplying an electrolytic solution and removing a product, and its shape is complicated.
(5) Particles having ion exchange capacity may be filled between the electrodes, but there are many restrictions on assembly and structure.
However, as described above, a small electrolysis cell has been proposed so far, but no specific cell specification has been disclosed. Usually, it is difficult to electrolyze an electrolyte solution having poor conductivity, and an ion exchange membrane resin component and a supporting electrolyte that impart conductivity are only added. When there was an ion exchange membrane component, electrolysis with a tap water raw material caused a hardness component to adhere to the cathode and the membrane, and electrolysis could not be continued. Cleaning with acid was laborious.
本発明は、これらの問題を解決し、水道水や純水のような高抵抗率かつ不純物の多い原料水においても、安定的に、低電力でオゾン水、オゾンガスを発生できる小型電解水生成装置を提供することにある。 The present invention solves these problems, and a small electrolyzed water generating apparatus that can stably generate ozone water and ozone gas with low power even in raw water with high resistivity and many impurities such as tap water and pure water. Is to provide.
本発明における第１の解決課題は、上記目的を達成するため、オゾン発生用陽極と陰極とを微小間隔を設けて対設し、前記オゾン発生用陽極と前記陰極間に原料水を供給して原料水を電解し、前記オゾン発生用陽極よりオゾンを含有する電解生成物を生成する小型電解水生成装置において、前記陽極と前記陰極との間隔を１０μｍ〜１００μｍとしたことを特徴とする小型電解水生成装置を提供することにある。 In order to achieve the above object, the first problem to be solved in the present invention is that an ozone generating anode and a cathode are provided with a small gap therebetween, and raw water is supplied between the ozone generating anode and the cathode. In a small electrolyzed water generating apparatus that electrolyzes raw water and generates an electrolyzed product containing ozone from the ozone generating anode, the space between the anode and the cathode is 10 μm to 100 μm. It is to provide a water generator.
本発明における第２の解決課題は、上記目的を達成するため、前記陽極と前記陰極との間隔を１０μｍ〜５０μｍとしたことを特徴とする小型電解水生成装置を提供することにある。 The second problem to be solved in the present invention is to provide a small electrolyzed water generating apparatus characterized in that the distance between the anode and the cathode is 10 μm to 50 μm in order to achieve the above object.
本発明における第３の解決課題は、上記目的を達成するため、前記微小間隔に中性隔膜を設けたことを特徴とする小型電解水生成装置を提供することにある。 A third problem to be solved in the present invention is to provide a small electrolyzed water generating apparatus characterized in that a neutral diaphragm is provided at the minute interval in order to achieve the above object.
本発明における第４の解決課題は、上記目的を達成するため、前記電解生成物が、オゾンと過酸化水素を含有する電解生成物であることを特徴とする小型電解水生成装置を提供することにある。 A fourth problem to be solved in the present invention is to provide a small electrolyzed water generating apparatus characterized in that the electrolysis product is an electrolysis product containing ozone and hydrogen peroxide in order to achieve the above object. It is in.
本発明における第５の解決課題は、上記目的を達成するため、前記オゾン発生用陽極の少なくとも表面が導電性ダイヤモンド又は白金のいずれか一つの陽極触媒を有することを特徴とする小型電解水生成装置を提供することにある。 A fifth problem to be solved in the present invention is to achieve the above object, wherein at least the surface of the ozone generating anode has an anode catalyst of any one of conductive diamond and platinum, and a small electrolyzed water generating device Is to provide.
本発明における第６の解決課題は、上記目的を達成するため、前記オゾン発生用陽極及び陰極の電極投影面当たりの電流密度が０．０５Ａ／ｃｍ2〜から１Ａ／ｃｍ2であることを特徴とする小型電解水生成装置を提供することにある。 A sixth problem to be solved in the present invention is that, in order to achieve the above object, the current density per electrode projection surface of the ozone generating anode and cathode is from 0.05 A / cm 2 to 1 A / cm 2. The present invention is to provide a small electrolyzed water generating apparatus.
本発明における第７の解決課題は、上記目的を達成するため、前記電解におけるセル電圧が３０Ｖ以下であることを特徴とする小型電解水生成装置を提供することにある。 A seventh problem to be solved in the present invention is to provide a small electrolyzed water generating device characterized in that a cell voltage in the electrolysis is 30 V or less in order to achieve the above object.
本発明における第８の解決課題は、上記目的を達成するため、前記原料水が１ＫΩｃｍ〜１８ＭΩｃｍの抵抗率を有することを特徴とする小型電解水生成装置を提供することにある。 An eighth problem to be solved by the present invention is to provide a small electrolyzed water generating apparatus characterized in that the raw water has a resistivity of 1 KΩcm to 18 MΩcm in order to achieve the above object.
本発明は、イオン交換膜を使用することなく、スペーサーにより又は中性隔膜により、陽極と陰極の間隔が１０μｍ〜１００μｍの微小間隔、好ましくは、１０μｍ〜５０μｍの微小間隔を形成し、少なくともオゾンを電解合成するための小型電解水生成装置であり、オゾン以外の電解生成物として、過酸化水素を電解合成することができ、好ましくは、陽極触媒が導電性ダイヤモンド、白金のいずれかを用い、電極の投影面当たりの電流密度が０．０５Ａ／ｃｍ2〜から１Ａ／ｃｍ2とし、原料水が１ＫΩｃｍ〜１８ＭΩｃｍの抵抗率の抵抗率を有していて、セル電圧が３０Ｖ以下とすることにより、水道水のような高抵抗率かつ不純物の多い原料水においても、安定的に、低電力でオゾン水、オゾンガスを発生できる小型電解水生成装置を得ることができる。
即ち、本発明によれば、水道水や純水を原料とし、特に電解質を添加せず、安全にオゾン、オゾンガス、オゾン水を電解合成でき、また過酸化水素も合成できる小型簡便な装置となり、しかも、イオン交換膜がないため、スケールによる膜の閉塞、洗浄の手間がなく、汎用性が高い装置を得ることができる。
According to the present invention, a space between the anode and the cathode is formed by a spacer or by a neutral diaphragm without using an ion exchange membrane, and a minute interval of 10 μm to 100 μm, preferably a minute interval of 10 μm to 50 μm, and at least ozone is formed. It is a small electrolyzed water generating device for electrosynthesis, and can electrolyze hydrogen peroxide as an electrolysis product other than ozone. Preferably, the anode catalyst uses either conductive diamond or platinum, and an electrode When the current density per projection plane is from 0.05 A / cm 2 to 1 A / cm 2 , the raw material water has a resistivity of 1 KΩcm to 18 MΩcm, and the cell voltage is 30 V or less, A small electrolyzed water generator capable of generating ozone water and ozone gas stably and at low power even in raw water with high resistivity and high impurities such as tap water It is possible.
That is, according to the present invention, tap water or pure water is used as a raw material, and in particular, an electrolyte is not added, and ozone, ozone gas, ozone water can be safely electrolytically synthesized, and hydrogen peroxide can also be synthesized. In addition, since there is no ion exchange membrane, there is no trouble of clogging the membrane with a scale and the trouble of washing, and a highly versatile device can be obtained.
本発明者は、小型電解水生成装置１例として、３０μｍの電極間距離のダイヤモンド電極からなるセルを用い、電極間に純水を供給して電解試験を実施したところ、オゾンガスの発生を確認したことにある。
純水の抵抗率を１ＭΩｃｍとすると、１０Ｖ程度の低い電圧において、陽陰電極反応における活性化過電圧の合計を５Ｖとして、０．０５Ａ／ｃｍ2以上のオゾンが発生可能となる比較的大きな電流が流れるのは１μｍ以下の距離であり、並行平板系のような電解セルにおいてこのような狭い極間に電極を向かい合わせる構造は、原料水あるいは生成したガスの物質移動が困難であり実用性に乏しい。従って、低電圧で電解質成分を含まない系での電解、特にオゾン発生は非常に困難と思われており、３０Ｖ程度の低電圧で、３０μｍの電極間距離では、上記の電流が流れることを予想できなかった。
As an example of a small electrolyzed water generating apparatus, the present inventor used a cell made of a diamond electrode with a distance of 30 μm between electrodes, and conducted an electrolysis test by supplying pure water between the electrodes, and confirmed generation of ozone gas. There is.
When the resistivity of pure water is 1 MΩcm, a relatively large current that can generate ozone of 0.05 A / cm 2 or more is obtained at a low voltage of about 10 V, where the total activation overvoltage in the positive and negative electrode reaction is 5 V. The flowing distance is 1 μm or less, and the structure in which the electrodes face each other between such narrow electrodes in an electrolysis cell such as a parallel plate system is difficult to transfer the raw material water or the generated gas, and is not practical. . Therefore, electrolysis in a system that does not contain an electrolyte component at a low voltage, especially the generation of ozone, is considered to be very difficult, and it is expected that the above current will flow at a low voltage of about 30 V and a distance between electrodes of 30 μm. could not.
従来は、このような電解条件と電解セル構造を達成することは通常困難であると考えられてきた。また、１０μｍ以下の距離に設置すると、発生気泡の滞留による液の流れが阻害され、細かな金属粒子などが原料水に存在するとショートし、流量を得るために吐出力の大きなポンプが必要となる。
通常は、数１００μｍ以上の極間を保つ必要が生じる。しかし、このときのセル電圧は、純水であれば、０．１Ａ／ｃｍ2を流すために１，０００Ｖもの電圧を与える必要が生じる。これは人体に危険であるし、オゾンの発生に要する電力原単位の大幅な増加を招き、また、電解セルに使用する各種金属材料の腐食を加速する。使用材料の耐電圧特性、発熱によるオゾン電流効率の低下を起こさない条件が満たされない。
Conventionally, it has been considered that it is usually difficult to achieve such electrolytic conditions and electrolytic cell structures. If installed at a distance of 10 μm or less, the flow of the liquid due to the retention of the generated bubbles is hindered, and if fine metal particles or the like are present in the raw water, a short circuit occurs and a pump with a large discharge force is required to obtain a flow rate. .
Usually, it is necessary to maintain a gap of several hundred μm or more. However, if the cell voltage at this time is pure water, it is necessary to apply a voltage of 1,000 V in order to pass 0.1 A / cm 2 . This is dangerous for the human body, causes a significant increase in the power consumption required for generating ozone, and accelerates the corrosion of various metal materials used in the electrolysis cell. The withstand voltage characteristics of the materials used and conditions that do not cause a decrease in ozone current efficiency due to heat generation are not satisfied.
本発明者は、上記の知見に基づき、純水のような導電性の低い溶液を供給して、オゾンを電解して合成するための小型電解水生成装置について検討した結果、ある適切な電極間間隔を有するセル構造と電解条件下を与えれば３０Ｖ以下の安全な電圧において、高濃度のオゾン水、あるいはオゾンガスを発生できる電解セル構造体を見出すことに成功した。 Based on the above findings, the present inventor has studied a small electrolyzed water generator for synthesizing and synthesizing ozone by supplying a low-conductivity solution such as pure water. The inventors have succeeded in finding an electrolytic cell structure capable of generating high-concentration ozone water or ozone gas at a safe voltage of 30 V or less by giving a cell structure having an interval and electrolytic conditions.
以下、図面とともに本発明を詳細に説明する。
超純水における電解原理：
超純水は、水のイオン積が、ｐＫｗ＝１４（２５℃）であり、［Ｈ+］と［ＯＨ-］がそれぞれ１０-7Ｍ存在するが、電気抵抗率は１８．２ＭΩｃｍである。尚、水道水には、様々なイオンが溶けているため、電気抵抗率はおよそ１０ｋΩｃｍで、電流が流れやすい。それに比べ超純水の電気抵抗率は、水道水の１０００倍以上で、電気分解し、電流を流すことは容易ではないと考えられる。
超純水に単位面積当たりの電極で１ｍＡの電流を流す場合を考える。図１のように水が１ｃｍ四方の立方体の場合、
Electrolysis principle in ultrapure water:
Ultrapure water has an ionic product of pKw = 14 (25 ° C.) and 10 −7 M of [H + ] and [OH − ], but has an electrical resistivity of 18.2 MΩcm. In addition, since various ions are dissolved in tap water, the electrical resistivity is about 10 kΩcm, and current easily flows. On the other hand, the electrical resistivity of ultrapure water is 1000 times or more of tap water, and it is considered that it is not easy to electrolyze and to pass current.
Consider a case in which a current of 1 mA is passed to ultrapure water with electrodes per unit area. When water is a 1 cm square cube as shown in Fig. 1,
均一な電解質水溶液に浸した電極に、１Ｖの電圧をかけたとする。横軸が空間座標、縦軸が電位のモデル図（以後同様）で考えると、図３に示すように、電圧をかけた瞬間、一方の極から他方の極まで１Ｖの電位差が直線的にかかる。 It is assumed that a voltage of 1 V is applied to an electrode immersed in a uniform electrolyte aqueous solution. Considering a model with a horizontal coordinate on the horizontal axis and a potential on the vertical axis (hereinafter the same), as shown in FIG. 3, a voltage difference of 1 V is linearly applied from one pole to the other as soon as a voltage is applied. .
電極に電場を与えると、電位の符号と反対符号のイオンが溶液から電極に引き寄せられ、同じ符号のイオンは電極から引き離される。すると両電極付近の電解液には、電極とは異なる符号のイオンが過剰に分布することになり、
次に、本発明に至る実験的検証の結果を示す。
実験的検証１：
図５に示すように、１ｃｍ×１ｃｍの白金板２枚と、厚さの分かっているスペーサーを用いて、実験を行った。本実験で用いた極間距離は、厚さ１０μｍ、２０μｍ、５５μｍのテフロンシートであり、超純水に浸けながら、直流電源を用いて電流電圧測定を行った。
Next, the results of experimental verification leading to the present invention will be shown.
Experimental verification 1:
As shown in FIG. 5, an experiment was performed using two 1 cm × 1 cm platinum plates and a spacer with a known thickness. The distance between the electrodes used in this experiment was a Teflon sheet having a thickness of 10 μm, 20 μm, and 55 μm, and the current and voltage were measured using a DC power supply while being immersed in ultrapure water.
各電極間距離で電流電圧測定を行った結果として図６に示すグラフを得た。線ａ、ｂ、ｃは、それぞれ、極間距離は、厚さ１０μｍ、２０μｍ、５５μｍの場合を示したものであり、参考として、電気抵抗率１８ＭΩｃｍで厚さ１０μｍ、断面積１ｃｍ2の仮想の抵抗器（電気抵抗１８ｋΩ）を示すグラフを線ｄとして示した。 The graph shown in FIG. 6 was obtained as a result of measuring the current voltage at the distance between the electrodes. Lines a, b, and c show the case where the distance between the poles is 10 μm, 20 μm, and 55 μm, respectively. As a reference, the virtual resistivity is 18 MΩcm, the thickness is 10 μm, and the cross-sectional area is 1 cm 2 . A graph showing a resistor (electrical resistance 18 kΩ) is shown as a line d.
前述のように、電圧が低い時はほとんど電流が流れない。ところが、電圧が２Ｖ付近に達すると超純水に急激に電流が流れ出した。この現象はＬ＝１０μｍ、２０μｍのときには顕著に見られたが、Ｌ＝５５μｍのときにはあまり見られなかった。これは２Ｖの電圧は溶液抵抗による電圧損失と界面の過電圧（水乖離反応電圧を含むと２Ｖ）、理論分解電圧の和であるが、電極間距離が大きいと抵抗損失が０．８Ｖを越え、電解が進行できる１．２３Ｖより大きな値にならないためである。抵抗損失が０．８Ｖ以下になるような距離で、初めて電解電流が継続して流れ出すためである。
実験的検証２：
図７に示す通り、１ｃｍ×４ｃｍの白金板２枚と、厚さ２５μｍのテフロンシート、水を送り出すための４溶媒低圧グラディエントポンプを用いた。一枚の白金板には、水を出し入れするための穴を開け、その穴に合わせてテフロンシートに水の通り道となる切れ込みを入れた。６０ｍＬ／ｈ以下の流速で実験を行った。
図８にその結果を示した。約１．２Ｖ、１．７Ｖ付近で電流値の急激な上昇が見られた。また、流速が大きいときは電流値が小さく、流速が小さいときは電流値が大きくなるという結果になった。
約１．２Ｖ、１．７Ｖ付近で電流値が急激に上昇したことについて、これらの電圧付近で電極付近に大量のイオンが発生し、超純水のイオン濃度が高まったことは明らかである。
Experimental verification 2:
As shown in FIG. 7, two 1 cm × 4 cm platinum plates, a 25 μm thick Teflon sheet, and a four-solvent low pressure gradient pump for feeding water were used. A hole for taking in and out water was made in one platinum plate, and a notch to be a water passage was made in the Teflon sheet in accordance with the hole. The experiment was conducted at a flow rate of 60 mL / h or less.
The results are shown in FIG. A sudden increase in current value was observed around 1.2V and 1.7V. In addition, the current value was small when the flow rate was large, and the current value was large when the flow rate was small.
It is clear that a large amount of ions are generated in the vicinity of the electrodes near these voltages and the ion concentration of ultrapure water is increased with respect to the sudden increase in the current value in the vicinity of about 1.2 V and 1.7 V.
本発明において、オゾンが発生するような大きい電流密度が安定して流れた理由は、次のようなプロセスが想定される。
電位差の和が水の分解電圧の値である１．２３Ｖを越えると、陽極では水の酸化が進行し、酸素とプロトンが生成、陰極では水の還元が進行して、水素ガスと水酸イオンが生成する。１．５１Ｖを越えれば、理論的にはオゾン、１．７Ｖ以上では過酸化水素も生成する。
When the sum of the potential differences exceeds the water decomposition voltage value of 1.23 V, the oxidation of water proceeds at the anode, oxygen and protons are generated, and the reduction of water proceeds at the cathode, resulting in hydrogen gas and hydroxide ions. Produces. If it exceeds 1.51V, theoretically, ozone is also generated at ozone above 1.7V.
電流が流れ続けることで、各式の反応により生成するイオンの濃度が増加しつつ、溶液内を拡散、電気泳動し始める。陽極近傍にはプロトンが増加、陰極近傍には水酸イオンが増加し、やがて輸率の違いを反映した溶液中央部分で、プロトンと水酸イオンが会合する。実際には、プロトンが陰極に向かい、水酸イオンが陽極に向かい、それぞれの移動度に従い移動するため、プロトン移動度が大きい分、溶液の陰極寄りにて会合、水を合成していることが推定される。図９にはその様子を図で説明している。
各濃度は設定された電流に相当するイオンの移動と会合速度が等しくなるまで増加した後、定常の濃度状態となる。
As the current continues to flow, the concentration of ions generated by the reaction of each formula increases, and diffusion and electrophoresis begin in the solution. Protons increase in the vicinity of the anode, and hydroxide ions increase in the vicinity of the cathode. Eventually, protons and hydroxide ions associate at the center of the solution reflecting the difference in transport number. Actually, protons move toward the cathode and hydroxide ions move toward the anode, and move according to their respective mobility. Presumed. FIG. 9 illustrates this state.
Each concentration increases until the ion migration and the association rate corresponding to the set current become equal, and then reaches a steady concentration state.
イオンの生成機構としては、中性攪乱現象による水分解という反応があり、上記電解反応に並列的に進行する可能性がある。 As an ion generation mechanism, there is a reaction of water splitting due to a neutral disturbance phenomenon, which may proceed in parallel with the electrolytic reaction.
また、電解セルを通過した水の伝導度は、ほぼ原料の値と等しくなる。これはプロトンと水酸イオンが会合した後に、伝導度が低下することを示唆している。 Further, the conductivity of water that has passed through the electrolytic cell is substantially equal to the value of the raw material. This suggests that the conductivity decreases after protons and hydroxide ions associate.
次に、流速に応じて電流値が変化したことについて説明する。電流が一定に流れていることは、イオンが電流に応じて生成していることを意味する。流速が小さいときは電極間のイオン濃度が高くなり電流が流れやすかった一方、流速が大きいときは、電極間のイオン濃度が低くなり、電流が流れにくかった。この傾向は原料の抵抗率が１ｋΩｃｍから１００ｋΩｃｍのときに顕著となった。これは原料水の抵抗率（導電率）に比較して、電解で生じるイオンによる導電率の増加分が同程度であることを示唆している。 Next, the fact that the current value has changed according to the flow rate will be described. A constant current means that ions are generated according to the current. When the flow rate was small, the ion concentration between the electrodes was high and current flowed easily, whereas when the flow rate was high, the ion concentration between the electrodes was low and current flow was difficult. This tendency became remarkable when the resistivity of the raw material was 1 kΩcm to 100 kΩcm. This suggests that the increase in conductivity due to ions generated by electrolysis is comparable to the resistivity (conductivity) of the raw material water.
実験的検証３：
円柱状の白金棒の円盤面を並行に配置し、５μｍの精度で２電極間距離を制御し、電流−電圧曲線を測定した。直径３ｍｍ、長さ４０ｍｍの円柱状の白金棒を２本用い、対向させる円盤面を＃８０００のラッピングフィルムシートで研き鏡面化した。電解には空気飽和した蒸留水を用いた。０．１ｍＭ−ＫＣｌ水溶液（Ａ）と、純水（Ｂ）を５００μｍ以下の電極間距離で電解したときの電流−電圧曲線は、図１０（Ａ）、（Ｂ）に示す通り、０．１ｍＭのイオンが存在するとき（Ａ）としないとき（Ｂ）で、流れる電流は若干異なるものの１Ｖ以上で、数１０μＡ（０．１ｍＡ／ｃｍ2）の電流が観察され、これらの電気抵抗率はそれほど異ならないことを示唆する。図１０（Ｂ）の１．２〜１．５Ｖの電流値の立ち上がりから電流−電圧曲線の傾きを求め、電気抵抗率を計算した。電極間距離５００〜５０μｍでは、水の電気抵抗率はほとんど一定で、１１０μｍのとき２２７ｋΩ・ｃｍの最小値を示した。
Experimental verification 3:
The disk surfaces of cylindrical platinum rods were arranged in parallel, the distance between the two electrodes was controlled with an accuracy of 5 μm, and the current-voltage curve was measured. Two cylindrical platinum rods having a diameter of 3 mm and a length of 40 mm were used, and the opposing disk surfaces were sharpened with a # 8000 wrapping film sheet to make a mirror surface. Distilled water saturated with air was used for electrolysis. As shown in FIGS. 10 (A) and 10 (B), the current-voltage curve when 0.1 mM-KCl aqueous solution (A) and pure water (B) are electrolyzed at a distance of 500 μm or less is 0.1 mM. (A) and when (B) are present, the flowing current is slightly different, but a current of several tens of μA (0.1 mA / cm 2 ) is observed at 1 V or more, and their electrical resistivity is not much. Suggest not to be different. The slope of the current-voltage curve was obtained from the rise of the current value of 1.2 to 1.5 V in FIG. 10B, and the electrical resistivity was calculated. When the distance between the electrodes was 500 to 50 μm, the electrical resistivity of water was almost constant, and when it was 110 μm, the minimum value of 227 kΩ · cm was shown.
図１０（Ａ）、（Ｂ）において、電極間距離：（ａ）１００，（ｂ）２００，（ｃ）３００，（ｄ）４００，（ｅ）５００μｍ、掃引速度０．０１Ｖ／ｓを示したものである。
図１１は、０〜８Ｖの純水電解における電流−電圧曲線を示したものであり、電極間距離は、（ａ）１３，（ｂ）２５，（ｃ）５０，（ｄ）１００，（ｅ）２００，（ｆ）３００μｍである。図１１より、１０Ｖ以下の電圧、１０μｍ以上の電極距離で得られる最大電流密度は、約７０ｍＡ／ｃｍ2であった。電極間隔が狭いことで、気泡生成がイオンの移動を妨げることも原因と推定され、好適な距離があることを示唆している。
10A and 10B, the distance between the electrodes: (a) 100, (b) 200, (c) 300, (d) 400, (e) 500 μm, and sweep rate of 0.01 V / s are shown. Is.
FIG. 11 shows a current-voltage curve in pure water electrolysis of 0 to 8 V, and the interelectrode distances are (a) 13, (b) 25, (c) 50, (d) 100, (e ) 200, (f) 300 μm. From FIG. 11, the maximum current density obtained at a voltage of 10 V or less and an electrode distance of 10 μm or more was about 70 mA / cm 2 . It is presumed that the gap between the electrodes is so small that bubble generation hinders the movement of ions, suggesting that there is a suitable distance.
次に、本発明に使用するセル構造、電解条件、原料水、陽極材料、陰極材料、隔膜について詳述する Next, the cell structure, electrolysis conditions, raw water, anode material, cathode material, and diaphragm used in the present invention will be described in detail.
［セル構造］
図７は、本発明の小型電解水生成装置の１例を示したものであり、平行平板構造を有しており、セル内における液流れは層流となる。また、図１２、１３に示すような円筒型構造又は図１４及び１５に示すような円板型構造としてもよい。また、少なくとも片方の電極が開口部を有する構造であってもよい。液供給および排出口はセル構造に従って任意に設計される。図１２の小型電解水生成装置では、水流は円筒の間隙を流れる。図１３のセルでは、上部からの水流の一部がセル内部にて電極面に垂直方向に変わる。
図１４の小型電解水生成装置では、陽極に構成された供給口から上部に向かって水流が生じる。図１５の小型電解水生成装置では、上部からの水流の一部を小型電解水生成装置内部にて電極面に垂直方向に変わる。
図１３〜１５の小型電解水生成装置では、電極が板状でないため、電極間の距離が離れている場所では電解は進行しない。
本発明の小型電解水生成装置の最大の特徴点は、オゾン発生用陽極と陰極とを微小間隔を設けて対設し、前記オゾン発生用陽極と前記陰極間に原料水を供給して原料水を電解し、前記オゾン発生用陽極よりオゾンを含有する電解生成物を生成する小型電解水生成装置において、前記陽極と前記陰極との間隔を１０μｍ〜１００μｍとしたことにある。この電極間距離は、抵抗損失を低下させるためになるべく小さくすべきであるが、水を供給する際の圧力損失を小さくするため、１０μｍ〜１００μｍにするのが好ましい。更に、１０μｍ〜５０μｍにすることが更に好ましい。
[Cell structure]
FIG. 7 shows an example of the small electrolyzed water generating apparatus of the present invention, which has a parallel plate structure, and the liquid flow in the cell is a laminar flow. Further, a cylindrical structure as shown in FIGS. 12 and 13 or a disk-type structure as shown in FIGS. Further, at least one of the electrodes may have a structure having an opening. The liquid supply and discharge ports are arbitrarily designed according to the cell structure. In the small electrolyzed water generating apparatus of FIG. 12, the water flow flows through the gap between the cylinders. In the cell of FIG. 13, a part of the water flow from the upper part changes in the direction perpendicular to the electrode surface inside the cell.
In the small electrolyzed water generating device of FIG. 14, a water flow is generated from the supply port configured in the anode toward the top. In the small electrolyzed water generating device of FIG. 15, a part of the water flow from above is changed in the direction perpendicular to the electrode surface inside the small electrolyzed water generating device.
In the small electrolyzed water generating apparatus of FIGS. 13-15, since an electrode is not plate-shaped, electrolysis does not advance in the place where the distance between electrodes is separated.
The greatest feature of the small electrolyzed water generating device of the present invention is that the ozone generating anode and the cathode are provided with a small gap therebetween, and the raw water is supplied between the ozone generating anode and the cathode. In the small electrolyzed water generating apparatus that generates an electrolyzed product containing ozone from the ozone generating anode, the distance between the anode and the cathode is set to 10 μm to 100 μm. The distance between the electrodes should be as small as possible in order to reduce the resistance loss, but is preferably 10 μm to 100 μm in order to reduce the pressure loss when water is supplied. Furthermore, it is more preferable to set it as 10 micrometers-50 micrometers.
［電解条件］
電解条件としては、合成するオゾン安定性から温度は４０℃以下が好ましく、必要であれば外部から冷却し、水温度を下げておくことが好ましい。電流密度としては大きいほどオゾン電流効率が高くなるが、水温の上昇は避ける必要があるため、０．０５〜１Ａ／ｃｍ2が好ましい。
この電流密度の範囲は、オゾンが電解により発生するのに適する電流密度域を示したものであり、０．０５〜１Ａ／ｃｍ2にすることが更に好ましい。
圧力損失は電解により気泡が発生すると増加するため、これを考慮して高い吐出圧力（１ＭＰａ〜１０ＭＰａ）をもつポンプなどの外部供給手段装置を付加する必要がある。一方で流量が大きい場合、ガスの蓄積、平均気泡率は低減するが、小型装置としての実用性、経済性を踏まえると、高圧かつ流量が大きいポンプは使用に適さない。本発明における気泡発生量は供給水量と同等レベルとなる。
前記電解におけるセル電圧は、電極などの金属部材が腐食劣化しますので、３０〜５０Ｖ以下にすることが好ましい。更に、３０Ｖ以下にすることが好ましい。また、人体に近く接触するような使用方法を想定した場合、このような低電圧に維持することは安全上重要です。
[Electrolysis conditions]
As electrolysis conditions, the temperature is preferably 40 ° C. or less in view of the stability of ozone to be synthesized. If necessary, it is preferable to cool from the outside and lower the water temperature. The larger the current density, the higher the ozone current efficiency. However, since it is necessary to avoid an increase in water temperature, 0.05 to 1 A / cm 2 is preferable.
This current density range represents a current density range suitable for ozone to be generated by electrolysis, and is more preferably 0.05 to 1 A / cm 2 .
Since pressure loss increases when bubbles are generated by electrolysis, it is necessary to add an external supply means device such as a pump having a high discharge pressure (1 MPa to 10 MPa) in consideration of this. On the other hand, when the flow rate is large, the gas accumulation and the average bubble rate are reduced. However, considering the practicality and economy as a small device, a high pressure and high flow rate pump is not suitable for use. The amount of bubbles generated in the present invention is the same level as the amount of supplied water.
The cell voltage in the electrolysis is preferably set to 30 to 50 V or less because metal members such as electrodes corrode and deteriorate. Furthermore, it is preferable to set it to 30 V or less. In addition, it is important for safety to maintain such a low voltage when it is assumed to be used in close contact with the human body.
［原料水］
原料水としては純水が好ましい。原料水の低効率は、１ｋΩｃｍ以上が好ましく、特に１ＭΩｃｍ以上がより好ましい。本発明における原料水の低効率の最大値は、１８ＭΩｃｍであり、この値は、超純水で得られる究極の水抵抗率で、水の固有の解離定数に相当する値です。
純水以外に過酸、必要に応じて過酸化物を生成するために電解質溶液を用いることができる。このような塩としては、例えば、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム、塩化アンモニウム、硫酸ナトリウム、炭酸ナトリウム、塩酸、硫酸、水酸化ナトリウム、アンモニア等から選ばれる一種又は二種以上をあげることができる。しかしながら本発明では主にオゾンを得ることが目的であるため、それらの濃度は１ｍＭ以下に限定的されるべきである。
[Raw material water]
The raw water is preferably pure water. The low efficiency of the raw material water is preferably 1 kΩcm or more, more preferably 1 MΩcm or more. The maximum value of the low efficiency of the raw material water in the present invention is 18 MΩcm, and this value is the ultimate water resistivity obtained with ultrapure water and corresponds to the intrinsic dissociation constant of water.
In addition to pure water, an electrolyte solution can be used to generate a peracid and, if necessary, a peroxide. Examples of such salts include one or more selected from sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium chloride, sodium sulfate, sodium carbonate, hydrochloric acid, sulfuric acid, sodium hydroxide, ammonia and the like. be able to. However, since the purpose of the present invention is mainly to obtain ozone, their concentration should be limited to 1 mM or less.
溶液のｐＨはアルカリや酸の添加により制御でき、殺菌効果を向上できるが、本発明のセルにおいては限定的な添加量において有効である。有機酸を使用することが溶液のｐＨ制御の容易性の点から好ましい。ここで、水溶性の有機酸としては、コハク酸、乳酸、酢酸、クエン酸、酒石酸等をあげることができる。アルカリ性に調製するためには、炭酸ナトリウム、炭酸水素ナトリウム、炭酸アンモニウム塩などが好ましい。これらの弱酸や弱塩基は抵抗率が一般に小さい。 The pH of the solution can be controlled by adding an alkali or an acid, and the bactericidal effect can be improved. However, in the cell of the present invention, it is effective at a limited addition amount. It is preferable to use an organic acid from the viewpoint of easy pH control of the solution. Here, examples of the water-soluble organic acid include succinic acid, lactic acid, acetic acid, citric acid, and tartaric acid. In order to prepare it alkaline, sodium carbonate, sodium bicarbonate, ammonium carbonate and the like are preferable. These weak acids and weak bases generally have a low resistivity.
原料水には、さらに殺菌力を向上させるため、界面活性剤を添加してもよい。溶液に界面活性剤を添加すると、電極表面の濡れ性が向上し、気泡の離脱が促進される。また、目的であるカビや菌の細胞膜との親和性も向上するので、殺菌効果が向上する。
界面活性剤としては、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩等の陰イオン界面活性剤、塩化ベンザルコニウム等の陽イオン界面活性剤、アミンオキサイド（例えばアルキルジメチルアミンオキサイド）等の両性界面活性剤、ポリグリセリン脂肪酸エステル、アルキルグリコシド等の非イオン界面活性剤等を使用することができる。界面活性剤の溶液における濃度は、０．０１〜１０重量％とすることが好ましい。
A surfactant may be added to the raw material water in order to further improve the sterilizing power. When a surfactant is added to the solution, the wettability of the electrode surface is improved and the release of bubbles is promoted. Moreover, since the affinity with the cell membrane of the target mold or fungus is improved, the bactericidal effect is improved.
Surfactants include anionic surfactants such as alkylbenzene sulfonates and polyoxyethylene alkyl ether sulfates, cationic surfactants such as benzalkonium chloride, and amphoteric compounds such as amine oxides (eg alkyldimethylamine oxide). Nonionic surfactants such as surfactants, polyglycerin fatty acid esters, and alkyl glycosides can be used. The concentration of the surfactant in the solution is preferably 0.01 to 10% by weight.
溶液、この他、殺菌力や清涼感を向上させる等のためにアルコールを添加してもよく、また、必要に応じて香料、色素、界面活性剤以外の殺菌剤、増粘剤、酵素、漂白剤、キレート剤、塩素化合物以外の電解質、防錆剤、ビルダーおよびエタノールやパラペンなどの防腐剤等を添加してもよい。特に、保存安定性の面からは被電解水が防腐剤を含有することが好ましい。
また、炭酸、酢酸、エタノールなどを溶解させておくと、オゾンの利用効率、安定性が向上することが知られている。これはそれらのオゾン溶解度が水の溶解度より大きくオゾンガスを有効にオゾン水として利用できること、または、オゾン分解を加速するＯＨラジカルをトラップする作用があり、オゾン水を安定化するためである。従って、これらの物質を原料水に適量溶解させておくことは好ましい。
Alcohol may be added to improve the bactericidal power and refreshing sensation of the solution, etc. In addition, if necessary, bactericides other than fragrances, pigments, surfactants, thickeners, enzymes, bleaching Agents, chelating agents, electrolytes other than chlorine compounds, rust inhibitors, builders and preservatives such as ethanol and parapenes may be added. In particular, from the viewpoint of storage stability, the electrolyzed water preferably contains a preservative.
Further, it is known that the use efficiency and stability of ozone are improved by dissolving carbonic acid, acetic acid, ethanol and the like. This is because their ozone solubility is greater than that of water and ozone gas can be used effectively as ozone water, or has the effect of trapping OH radicals that accelerate ozone decomposition, and stabilizes ozone water. Therefore, it is preferable to dissolve these substances in appropriate amounts in the raw water.
水道水、井戸水、海水などの金属イオンを多く含む処理対象では、陰極表面に水酸化物或いは、炭酸化物が沈殿し反応が阻害される恐れがある。また陽極表面にはシリカなどの酸化物が析出する。これを防ぐために、逆電流を適当な時間（１分から１時間）ごとに与えることにより、陰極では酸性化し、陽極ではアルカリ化するため、発生ガス及び供給水の流動により加速され、析出物の脱離反応が容易に進行する。 In a processing target containing a large amount of metal ions such as tap water, well water, seawater, etc., there is a possibility that hydroxide or carbonate precipitates on the cathode surface and the reaction is hindered. In addition, an oxide such as silica is deposited on the surface of the anode. In order to prevent this, a reverse current is applied every appropriate time (1 minute to 1 hour), so that it is acidified at the cathode and alkalized at the anode. The separation reaction proceeds easily.
［陽極］
オゾンを電解合成する電極としては、白金やダイヤモンド電極が知られている。ダイヤモンドは熱伝導性、光学的透過性、高温かつ酸化に対しての耐久性に優れており、特にドーピングにより電気伝導性の制御も可能であることから、半導体デバイス、エネルギー変換素子として有望とされている。ダイヤモンド電極は水の電解酸化では酸素以外にオゾン、過酸化水素の生成が報告されている。ダイヤモンド触媒は陽極の一部に存在すればよく、前記基材の一部が露出していても支障ない。
基材としてはＳｉ（単結晶，多結晶）のみならず，Ｎｂ、Ｔａ、Ｚｒ、Ｔｉや、Ｍｏ、Ｗ、黒鉛、各種カーバイド上にも合成可能である。
代表的なダイヤモンドの製法である熱フィラメントＣＶＤ法について以下に説明する。炭素源となるメタンＣＨ4など炭化水素ガス、或いはアルコールなどの有機物を用い、ＣＶＤチャンバー内に水素ガスと共に送り込み、還元雰囲気に保ちながら、フィラメントを熱し、炭素ラジカルが生成する温度１８００−２４００℃にする。このときダイヤモンドが析出する温度（７５０〜９５０℃）領域に電極基材を設置する。水素に対する炭化水素ガス濃度は０．１〜１０ｖｏｌ％、圧力は２０ｈＰａ〜１０１３ｈＰａ（１気圧）である。
ダイヤモンドが良好な導電性を得るために、原子価の異なる元素を微量添加することは不可欠である。ホウ素ＢやリンＰの好ましい含有率は１０〜１００００ｐｐｍであり、更に好ましくは１００〜３０００ｐｐｍである。原料化合物にはトリメチルボロン（ＣＨ3）3Ｂを用いるが、毒性の少ない酸化ホウ素Ｂ2Ｏ3、５酸化２燐Ｐ2Ｏ5などの利用も好ましい。
[anode]
Platinum and diamond electrodes are known as electrodes for electrolytically synthesizing ozone. Diamond is promising as a semiconductor device and an energy conversion element because it has excellent thermal conductivity, optical transparency, high temperature and durability against oxidation, and electrical conductivity can be controlled by doping in particular. ing. Diamond electrodes have been reported to generate ozone and hydrogen peroxide in addition to oxygen in the electrolytic oxidation of water. The diamond catalyst may be present in a part of the anode, and there is no problem even if a part of the base material is exposed.
The base material can be synthesized not only on Si (single crystal, polycrystal) but also on Nb, Ta, Zr, Ti, Mo, W, graphite, and various carbides.
A hot filament CVD method, which is a typical diamond manufacturing method, will be described below. Using a hydrocarbon gas such as methane CH 4 as a carbon source, or an organic substance such as alcohol, it is sent together with hydrogen gas into the CVD chamber, and while maintaining a reducing atmosphere, the filament is heated to a temperature 1800-2400 ° C. at which carbon radicals are generated. To do. At this time, an electrode base material is installed in a temperature (750 to 950 ° C.) region where diamond is deposited. The hydrocarbon gas concentration with respect to hydrogen is 0.1 to 10 vol%, and the pressure is 20 hPa to 1013 hPa (1 atm).
In order for diamond to obtain good conductivity, it is indispensable to add a trace amount of elements having different valences. The preferable content rate of boron B or phosphorus P is 10-10000 ppm, More preferably, it is 100-3000 ppm. Trimethylboron (CH 3 ) 3 B is used as the raw material compound, but it is also preferable to use boron oxide B 2 O 3 , pentoxide 5 phosphorus P 2 O 5, etc., which are less toxic.
［陰極］
陰極反応は主に水素発生であり、水素に対して脆化しない電極触媒が好ましく、白金族金属、ニッケル、ステンレス、チタン、ジルコニウム、金、銀、カーボンなどが好ましい。陰極基材としてはステンレス、ジルコニウム、カーボン、ニッケル、チタン、ダイヤモンドなどの金属に限定される。本発明の装置では、オゾンや過酸化物の溶解した水と接触する配置となるため、酸化耐性に優れたものが好ましい。
[cathode]
The cathode reaction is mainly hydrogen generation, and an electrode catalyst that does not embrittle with hydrogen is preferable, and platinum group metals, nickel, stainless steel, titanium, zirconium, gold, silver, carbon, and the like are preferable. The cathode substrate is limited to metals such as stainless steel, zirconium, carbon, nickel, titanium and diamond. In the apparatus of the present invention, since it is arranged to come into contact with water in which ozone or peroxide is dissolved, an apparatus excellent in oxidation resistance is preferable.
［隔膜］
電極反応で生成した活性な物質を安定に保つために中性隔膜を利用することは好ましい。膜はフッ素樹脂系、炭化水素樹脂系のいずれでも良いが、オゾンや過酸化物耐食性の面で前者が好ましい。該隔膜は、陽極、陰極で生成した物質が反対の電極で消費されるのを防止する。多孔性材料を電極間に充填してもよく、ウェブ状に繊維化した該材料も利用可能である。材料の空隙率としては液の均一な分散と抵抗率の考慮から２０〜９０％が好ましい。孔或いは材料粒子のサイズとしては５μｍ〜１０μｍが好ましい。
尚、スペーサーを用いて、電極間の間隔を維持できれば、隔膜は、必ずしも設ける必要は、ない。一方、隔膜の代わりに、イオン交換膜を設けると、ｐＨの分布が生じるため、スケールの析出は中性膜に比較して増加し、スケールによる膜の閉塞が生じるおそれがあり、好ましくない。一方、隔膜を使用した場合、生成物質の分離、対極での消耗を抑制する役割が期待される。
[diaphragm]
In order to keep the active substance produced by the electrode reaction stable, it is preferable to use a neutral diaphragm. The film may be either a fluororesin or a hydrocarbon resin, but the former is preferable in terms of ozone and peroxide corrosion resistance. The diaphragm prevents the material produced at the anode and cathode from being consumed at the opposite electrode. A porous material may be filled between the electrodes, and the material fiberized into a web shape can also be used. The porosity of the material is preferably 20 to 90% in consideration of uniform dispersion of the liquid and resistivity. The size of the pores or material particles is preferably 5 μm to 10 μm.
In addition, if the space | interval between electrodes can be maintained using a spacer, it is not necessary to necessarily provide a diaphragm. On the other hand, when an ion exchange membrane is provided instead of the diaphragm, the pH distribution is generated, so that the deposition of scale increases as compared with the neutral membrane, and the membrane may be blocked by the scale, which is not preferable. On the other hand, when a diaphragm is used, it is expected to play a role of suppressing the separation of product substances and the consumption at the counter electrode.
次に本発明の実施例、参考例及び比較例を示す。 Next, Examples, Reference Examples and Comparative Examples of the present invention will be shown.
＜実施例１〜９＞
電極として導電性ダイヤモンド触媒（ホウ素ドープ濃度１５００ｐｐｍ）を形成したＳｉ基板製の平板（電極有効幅１ｃｍ、有効長さ３ｃｍ、板厚さ０．２ｃｍ）を陽極として用い、陰極として、同等の面積を有する白金板（板厚さ０．５ｍｍ）を、図７のように極間が１０μｍになるように配置した。純水の流量を電磁定量ポンプにより３０〜１２０ｍＬ／Ｈとし、電流密度を０．０６Ａ／ｃｍ2から０．２Ａ／ｃｍ2まで流した。オゾン水濃度は２５０ｎｍのオゾン吸収光量から紫外分光光度計を用いて定量するか、あるいは１％ＫＩの中性溶液（リン酸緩衝液）にオゾンを含むガスの一定量を注入して振り混ぜ、２ＫＩ＋Ｏ3＋Ｈ2Ｏ→Ｉ2＋２ＫＯＨ＋Ｏ2により遊離したヨウ素の呈色を波長３５２ｎｍ付近での吸光度を測定し、算定した（吸収光度法オゾン定量、実験化学講座９分析化学［Ｉ］のｐ．２９参照）。また、過酸化水素濃度は、試料に硫酸チタンを添加し、チタン錯体を形成させ、その４１０ｎｍの吸収ピークから算出、定量した。
上記電解条件の組み合わせにおいて、得られたセル電圧、オゾン水濃度の結果を表１に示した。いずれの実施例においてもオゾンの生成が確認され、セル電圧は３０Ｖ以下であった。また、実施例１、４、５、７では２ｍｇ／Ｌ以上の過酸化水素が生成した。
<Examples 1-9>
A flat plate made of a Si substrate (electrode
Table 1 shows the results of cell voltage and ozone water concentration obtained in the combination of the above electrolysis conditions. In any of the examples, generation of ozone was confirmed, and the cell voltage was 30 V or less. In Examples 1, 4, 5, and 7, 2 mg / L or more of hydrogen peroxide was generated.
＜実施例１０〜２４、２６、参考例２５、２７＞
実施例１〜９と同様の電解セルを用いて、極間は１０μｍ、３０μｍ、５０μｍに設定し、水道水の流量を３０〜２４０ｍＬ／ｈとし、電流密度を０．１Ａ／ｃｍ2から０．３Ａ／ｃｍ2まで流した。同様の測定方法を用いてオゾン水濃度を計測したところ、多くの組み合わせにおいて１ｍｇ／Ｌ以上であることがわかった。表１中、１ｍｇ／Ｌ以下と記載されている欄においても、オゾンの存在は確認できた。過酸化水素は、いずれの場合においても１〜数ｍｇ／Ｌの濃度を確認した。参考例２５、２７においても電解に支障はないが、セル電圧が３０Ｖを越えており、参考例とした。
<Examples 10 to 24 and 26, Reference Examples 25 and 27>
Using the same electrolytic cell as in Examples 1 to 9, the gap between the electrodes was set to 10 μm, 30 μm, and 50 μm, the flow rate of tap water was set to 30 to 240 mL / h, and the current density was changed from 0.1 A / cm 2 to 0.2 μm. The flow rate was 3 A / cm 2 . When the ozone water concentration was measured using the same measurement method, it was found that the concentration was 1 mg / L or more in many combinations. In Table 1, the presence of ozone was also confirmed in the column described as 1 mg / L or less. In each case, hydrogen peroxide was confirmed to have a concentration of 1 to several mg / L. In Reference Examples 25 and 27, there was no problem in electrolysis, but the cell voltage exceeded 30 V, and it was taken as a reference example.
＜実施例２８＞
同様の試験を白金陽極で実施したところ、電圧は１６Ｖとなり、オゾン水濃度は１ｍｇ／Ｌであった。
<Example 28>
When the same test was conducted with a platinum anode, the voltage was 16 V and the ozone water concentration was 1 mg / L.
＜比較例２９＞
電極間距離を５μｍとし実施例１と同様に実施したところ、所定の水量を流せず、結果として電圧上昇となった。
<Comparative Example 29>
When the distance between the electrodes was set to 5 μm and the same operation as in Example 1 was performed, a predetermined amount of water could not be flowed, resulting in a voltage increase.
＜実施例３０＞
電極間距離を１００μｍとし実施例４と同様に実施したところ、電圧が３０Ｖ以上となり、電流密度は０．０１Ａ／ｃｍ2で、オゾンの発生はわずかであった。
<Example 30>
When the distance between the electrodes was set to 100 μm and the same operation as in Example 4 was performed, the voltage was 30 V or more, the current density was 0.01 A / cm 2 , and the generation of ozone was slight.
本発明は、水道水や純水を原料とし、特に電解質を添加せず、安全にオゾン、オゾンガス、オゾン水を電解合成でき、また過酸化水素も合成できるとともに、セル形状は平板を平行に向い合せた構造であり、あるいは円筒を２重構造とした、小型簡便な装置となり、しかも、イオン交換膜がないため、スケールによる膜の閉塞、洗浄の手間がなく、汎用性が高い装置を得ることができ、小型装置を必要とする広い用途に使用することができる。 In the present invention, tap water or pure water is used as a raw material, and it is possible to safely synthesize ozone, ozone gas, and ozone water without adding any electrolyte, and also to synthesize hydrogen peroxide, and the cell shape faces the flat plate in parallel. A compact and simple device with a combined structure or a double cylinder structure, and since there is no ion exchange membrane, there is no need for clogging and cleaning of the membrane due to the scale, and a highly versatile device is obtained. And can be used in a wide range of applications that require a small device.
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| CN112281184A (en) * | 2020-09-17 | 2021-01-29 | 浙江清越科技有限公司 | Device and method for electrochemically generating hydrogen peroxide |
| CN114703488A (en) * | 2022-05-13 | 2022-07-05 | 天津市大陆制氢设备有限公司 | Water electrolysis method adopting hydrogen evolution and oxygen evolution promoter |
| US11939687B2 (en) | 2019-02-22 | 2024-03-26 | Kogakuin University | Water electrolysis apparatus, and sterilization/cleaning method and method for decomposing/removing harmful substance, each using water electrolysis apparatus |
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| CN112281184A (en) * | 2020-09-17 | 2021-01-29 | 浙江清越科技有限公司 | Device and method for electrochemically generating hydrogen peroxide |
| CN114703488A (en) * | 2022-05-13 | 2022-07-05 | 天津市大陆制氢设备有限公司 | Water electrolysis method adopting hydrogen evolution and oxygen evolution promoter |
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