JP2574678B2 - Equipment for producing aqueous solution containing peroxide - Google Patents
Equipment for producing aqueous solution containing peroxideInfo
- Publication number
- JP2574678B2 JP2574678B2 JP62197775A JP19777587A JP2574678B2 JP 2574678 B2 JP2574678 B2 JP 2574678B2 JP 62197775 A JP62197775 A JP 62197775A JP 19777587 A JP19777587 A JP 19777587A JP 2574678 B2 JP2574678 B2 JP 2574678B2
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- Prior art keywords
- exchange membrane
- aqueous solution
- cation exchange
- anode
- hydrogen peroxide
- Prior art date
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、カチオン交換膜が装着された電解槽の陰極
面上で酸素を電気化学的に還元してHO2 -（過酸化水素イ
オン）を生成させることにより、MHO2（ただし、Ｍはア
ルカリ金属または水素である。以下、同じ）で表わされ
る過酸化物を含有する水溶液を電気化学的に製造する装
置に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for electrochemically reducing oxygen on a cathode surface of an electrolytic cell equipped with a cation exchange membrane to form HO 2 − (hydrogen peroxide ion). To electrochemically produce an aqueous solution containing a peroxide represented by MHO 2 (where M is an alkali metal or hydrogen; the same applies hereinafter).
カチオン交換膜が装着された電解槽の陰極面上で酸素
を電気化学的に還元して過酸化水素イオンを生成させる
ことにより、アルカリ金属水素過酸化物と過酸化水素と
の混合物（たとえば、 KHO2＋H2O＝KOH＋H2O2 の平衡反応により、混合物としてしかえられない）を製
造する装置としては、 （１）米国特許第4384931号明細書に 陽極（１）／酸水溶液（２）／カチオン交換膜（３）／
アルカリ水溶液（４）／ガス拡散電極からなる陰極
（５）／酸素（６）の順に構成された電解槽（第３図参
照） が、また過酸化水素の製造装置としては、 （２）Kuehnら,J.Electrochem.Soc.第130巻第117頁（19
83）に 陽極（11）／酸水溶液（12）／カチオン交換膜（13）／
酸水溶液（17）／アニオン交換膜（18）／アルカリ水溶
液（14）／ガス拡散電極からなる陰極（15）／酸素（1
6）の順に構成された電解槽（第４図参照） が知られている。By electrochemically reducing oxygen on the cathode surface of an electrolytic cell equipped with a cation exchange membrane to generate hydrogen peroxide ions, a mixture of alkali metal hydrogen peroxide and hydrogen peroxide (for example, KHO 2 + H 2 O = KOH + H 2 O 2 , which can be obtained only as a mixture by an equilibrium reaction). (1) US Pat. No. 4,384,931 discloses an anode (1) / acid aqueous solution (2) / Cation exchange membrane (3) /
An electrolytic cell (see FIG. 3) composed of an alkaline aqueous solution (4) / a cathode (5) composed of a gas diffusion electrode / oxygen (6), and a hydrogen peroxide producing apparatus include: (2) Kuehn et al. , J. Electrochem. Soc. 130, 117 (19
83) Anode (11) / Aqueous acid solution (12) / Cation exchange membrane (13) /
Acid aqueous solution (17) / anion exchange membrane (18) / alkaline aqueous solution (14) / cathode composed of gas diffusion electrode (15) / oxygen (1
An electrolytic cell (see FIG. 4) configured in the order of 6) is known.
〔発明が解決しようとする問題点〕 これらいずれの装置によっても、過酸化水素換算で数
％の濃度の製品がえられるが、両電極間の電気抵抗が大
きく、そのため、槽電圧が高く、消費電力が大きくな
り、また電流密度も40mA/cm2と小さく、したがって装置
の生産性も低い。[Problems to be Solved by the Invention] With any of these devices, a product having a concentration of several percent in terms of hydrogen peroxide can be obtained, but the electric resistance between the two electrodes is large, so that the cell voltage is high and the consumption is low. The power is large and the current density is as low as 40 mA / cm 2, and therefore the productivity of the device is low.
本発明者らは、上記従来の装置における陽極に接する
酸水溶液の室を除いて、陽極の片面にカチオン交換膜を
接合させ、該カチオン交換膜とは反対側に陽極と接する
水を配置させた、すなわち、陽極付近を、水／陽極／カ
チオン交換膜（ただし、該カチオン交換膜は該陽極の片
面に接合されている）の順の構成のものとすることによ
り、従来法における上記酸水溶液自体およびそこに発生
する酸素の気泡による電気抵抗がなくなり、陽極から発
生する酸素は電気抵抗にまったく影響のない背面の水側
に抜けて、電気抵抗が大幅に低下することとなることを
見い出し、本発明に到達した。The present inventors joined a cation exchange membrane to one side of the anode except for the chamber of the acid aqueous solution in contact with the anode in the above conventional apparatus, and arranged water in contact with the anode on the side opposite to the cation exchange membrane. That is, by forming the vicinity of the anode in the order of water / anode / cation exchange membrane (the cation exchange membrane is bonded to one side of the anode), the acid aqueous solution itself in the conventional method is used. And found that the electrical resistance due to the oxygen bubbles generated there disappeared, and the oxygen generated from the anode escaped to the water side on the back, which had no effect on the electrical resistance, and the electrical resistance was greatly reduced. The invention has been reached.
すなわち、本発明の要旨は、カチオン交換膜が装着さ
れた電解槽の陰極面上で酸素を電気化学的に還元して過
酸化水素イオンを生成させることにより、MHO2で表わさ
れる過酸化物を含有する水溶液を電気化学的に製造する
装置において、 イ）上記カチオン交換膜が陽極の、陰極側の面に接合さ
れており、かつ ロ）該カチオン交換膜の反対側に、該陽極に接して水が
存在している 構造を備えている、過酸化物を含有する水溶液を電気化
学的に製造する装置、にある。That is, the gist of the present invention is to form a peroxide represented by MHO 2 by electrochemically reducing oxygen on a cathode surface of an electrolytic cell equipped with a cation exchange membrane to generate hydrogen peroxide ions. An apparatus for electrochemically producing an aqueous solution containing: a) the cation exchange membrane is bonded to the cathode side of the anode; and b) the cation exchange membrane is in contact with the anode on the opposite side of the cation exchange membrane. An apparatus for electrochemically producing an aqueous solution containing a peroxide, the apparatus comprising a structure in which water is present.
該カチオン交換膜は、耐久性のあるフッ素樹脂系のも
のであって、水素イオンの伝導性のよいスルホン酸基を
もつものが望ましい。このようなものとして、たとえ
ば、ナフィオン（デュポン社製）がある。The cation exchange membrane is preferably of a durable fluororesin type and has a sulfonic acid group having good conductivity of hydrogen ions. For example, there is Nafion (manufactured by DuPont).
カチオン交換膜と陽極とを接合する方法として、触媒
粒子とポリ四フッ化エチレンとを混合し、シート状に成
形して電極シートをえ、カチオン交換膜に該電極シート
をホットプレスする方法もあるが、電気抵抗および接合
強度の点で電極金属を化学メッキする方法のほうが好ま
しい。このカチオン交換膜は強酸性膜となるので、この
接合金属種は、耐酸性材料に限られるが、活性の点で白
金族金属またはそれらの酸化物が望ましく、その中でも
陽極過電圧の低いイリジウムあるいはイリジウム，ルテ
ニウムなどの合金や酸化物がよい。As a method of joining the cation exchange membrane and the anode, there is also a method of mixing catalyst particles and polytetrafluoroethylene, forming a sheet, obtaining an electrode sheet, and hot-pressing the electrode sheet on the cation exchange membrane. However, a method of chemically plating an electrode metal is preferable in terms of electric resistance and bonding strength. Since this cation exchange membrane becomes a strongly acidic membrane, this bonding metal species is limited to an acid-resistant material, but platinum group metals or their oxides are desirable in terms of activity, and among them, iridium or iridium having a low anode overvoltage is preferable. Alloys and oxides such as ruthenium are preferred.
本発明によってアルカリ金属水素過酸化物と過酸化水
素との混合物を製造する場合は、第１図に示すように、
水（27）／陽極（21）／カチオン交換膜（23）（ただ
し、該カチオン交換膜は該陽極の片面に接合されてい
る）／アルカリ水溶液（24）／ガス拡散電極からなる陰
極（25）／酸素（26）の順に構成された電解槽を使用す
ればよい。該アルカリ水溶液としては、たとえば、水酸
化ナトリウム，水酸化カリウム等の水溶液をあげること
ができる。その濃度は、0.1〜10Mの広範な範囲で使用す
ることができるが、液抵抗の小さい１〜10Mの範囲がよ
い。酸素は、純粋なものである必要はなく、たとえば、
空気等でもよい。When producing a mixture of an alkali metal hydrogen peroxide and hydrogen peroxide according to the present invention, as shown in FIG.
Water (27) / Anode (21) / Cation exchange membrane (23) (However, the cation exchange membrane is bonded to one side of the anode) / Aqueous alkaline solution (24) / Cathode consisting of gas diffusion electrode (25) / Oxygen (26) may be used. Examples of the alkaline aqueous solution include aqueous solutions of sodium hydroxide, potassium hydroxide and the like. The concentration can be used in a wide range of 0.1 to 10M, but a range of 1 to 10M having a small liquid resistance is preferable. Oxygen need not be pure, for example,
It may be air or the like.
また、過酸化水素を製造する場合は、第２図に示すよ
うに、水（47）／陽極（31）／カチオン交換膜（33）
（ただし、該カチオン交換膜は該陽極の片面に接合され
ている）／酸水溶液（37）／アニオン交換膜（38）／ア
ルカリ水溶液（34）／ガス拡散電極からなる陰極（35）
／酸素（36）の順に構成された電解槽を使用すればよ
い。In the case of producing hydrogen peroxide, as shown in FIG. 2, water (47) / anode (31) / cation exchange membrane (33)
(However, the cation exchange membrane is bonded to one side of the anode) / acid aqueous solution (37) / anion exchange membrane (38) / alkaline aqueous solution (34) / cathode (35) composed of gas diffusion electrode
/ Oxygen (36) may be used.
該アルカリ水溶液および酸素は、前記と同じものでよ
い。酸水溶液は、通常の鉱酸、たとえば硫酸，硝酸，塩
酸等でよい。この濃度も、0.1〜10Mの後半な範囲で使用
することができるが、液抵抗の点で１〜10Mの範囲がよ
い。もっとも、たとえば、過酸化水素を含む希硫酸の製
造を目的とする場合など、さらに低濃度にすることもで
きる。The alkaline aqueous solution and oxygen may be the same as described above. The aqueous acid solution may be a conventional mineral acid such as sulfuric acid, nitric acid, hydrochloric acid, or the like. This concentration can be used in the latter half range of 0.1 to 10 M, but is preferably in the range of 1 to 10 M in terms of liquid resistance. However, for example, for the purpose of producing dilute sulfuric acid containing hydrogen peroxide, the concentration can be further reduced.
電解室の温度は、過酸化水素イオンの自己分解を抑え
るために50℃以下が好ましい。The temperature of the electrolysis chamber is preferably 50 ° C. or lower in order to suppress the self-decomposition of hydrogen peroxide ions.
該アニオン交換膜は、アルカリおよび過酸化水素に対
して耐久性を備えていなければならない。本発明者ら
は、特開昭59−12250および特開昭60−1234の両公報に
開示された一般式 （式中、ＸはＦまたはCF3;lは０〜５の整数;mは０また
は1;nは１〜５の整数;pおよびｑはいずれも正の整数で
あって、その比p/qは２〜16;R1,R2およびR3はいずれも
低級アルキル基（ただし、R1とR2とはそれらが一体とな
ってテトラメチレン鎖またはペンタメチレン鎖を形成し
ていてもよい）;R4はＨまたは低級アルキル基（ただ
し、R3と一体となってエチレン鎖またはトリメチレン鎖
を形成していてもよい）;Z-はハロゲンイオン;aは２〜1
0の整数である） で表わされる共重合体からなるアニオン交換膜が上記の
耐久性を充分に備えており、かつ従来提案されていたも
のよりも電流密度がはるかに高く、本発明に好適に使用
することができることを見出した。従来は、このような
耐久性を備えたものが知られておらず、したがって、酸
素の電気化学的還元による過酸化水素の製造法として実
用性ある方法はなかったのである。The anion exchange membrane must have durability against alkali and hydrogen peroxide. The present inventors have disclosed a general formula disclosed in both JP-A-59-12250 and JP-A-60-1234. (Wherein X is F or CF 3 ; l is an integer of 0 to 5; m is 0 or 1; n is an integer of 1 to 5; p and q are both positive integers, and their ratio p / q is 2 to 16; R 1 , R 2 and R 3 are each a lower alkyl group (provided that R 1 and R 2 may be combined to form a tetramethylene chain or a pentamethylene chain R 4 is H or a lower alkyl group (however, may form an ethylene chain or trimethylene chain together with R 3 ); Z − is a halogen ion;
An anion exchange membrane comprising a copolymer represented by the formula (1) is sufficiently provided with the above-mentioned durability, and has a much higher current density than conventionally proposed ones. Found that it can be used. Heretofore, there has been no known method having such durability, and there has been no practical method for producing hydrogen peroxide by electrochemical reduction of oxygen.
以上の説明から明らかなように、本発明によれば、 （１）槽電圧を大幅に低下させ、かつ電流密度を高くす
ることができる。As apparent from the above description, according to the present invention, (1) the cell voltage can be significantly reduced and the current density can be increased.
（２）陽極で発生する酸素をそのまま陰極側へ供給する
酸素として使用することができる。(2) Oxygen generated at the anode can be used as it is as oxygen supplied to the cathode side.
（従来の装置では、該酸素が酸水溶液中をバブリング
し、酸ミストを同伴してくるので、拡散電極およびアル
カリ水溶液の寿命の低下を防ぐために、酸ミストの除去
設備および耐酸性の配管が必要となる。） （３）槽電圧が低くかつ電流効率が高いので、装置をコ
ンパクトにすることができ、したがって、オンサイトに
設置することができる。(In the conventional apparatus, since the oxygen bubbling in the acid aqueous solution and entraining the acid mist, in order to prevent the life of the diffusion electrode and the alkaline aqueous solution from being shortened, an acid mist removing facility and an acid-resistant pipe are required. (3) Since the cell voltage is low and the current efficiency is high, the apparatus can be made compact, and thus can be installed on-site.
実施例１ 表面粗化処理をしたナフィオン117カチオン交換膜の
片面に、テトラアンミン白金（II）塩水溶液（Ptとして
100mg、全量150ml）を接触させて白金錯イオンを吸着さ
せたのち、水洗し、水素化ホウ素ナトリウム水溶液（濃
度0.05wt％、全量150ml）を上記片面に接触させて1.0mg
/cm2の白金析出層を膜の片面にえた。ついで、 ヘキサクロロイリジウム（IV）酸カリウムIrとして100m
g ヒドロキシルアミン塩酸塩5wt％水溶液 10ml 水和ヒドラジン20wt％ 5ml 水 残り を混合してえたpH8.0、全量300mlのイリジウムのメッキ
浴によって、上記白金析出層上に1mg/cm2のイリジウム
層を析出させて、陽極付カチオン交換膜（片面接合体）
をえた。Example 1 One surface of a surface-roughened Nafion 117 cation exchange membrane was coated with a tetraammineplatinum (II) salt aqueous solution (as Pt).
100 mg, a total amount of 150 ml) was allowed to adsorb the platinum complex ion, and then washed with water.
A platinum deposition layer of / cm 2 was provided on one side of the film. Then, 100m as potassium hexachloroiridate (IV) Ir
g hydroxylamine hydrochloride 5 wt% aqueous solution 10ml hydrazine hydrate 20 wt% 5 ml water remaining and the E by mixing pH 8.0, by the plating bath of iridium total amount 300 ml, precipitation of an iridium layer 1 mg / cm 2 on the platinum deposited layer Let cation exchange membrane with anode (single-sided bonded body)
I got
この陽極付カチオン交換膜と 構造 交換容量 0.91meq/g・乾燥樹脂 電気抵抗 5.9Ω・cm2 厚さ 440μｍ のアニオン交換膜（38）と0.2〜１μｍの黒鉛粒子85wt
％からなるガス拡散電極（35）とを第２図に示すように
設置して、電極面積50cm2,陰極室間隔（ガス拡散電極
（35）とアニオン交換膜（38）との間）6mm,中間室間隔
（陽極付カチオン交換膜（33）とアニオン交換膜（38）
との間）4mmの電解層を製作し、陰極室に2M KOH水溶液
（34）を循環し、中間室に1M H2SO4水溶液（37）を供
給して電解した。This cation exchange membrane with anode and its structure Exchange capacity 0.91meq / g ・ Dry resin Electric resistance 5.9Ω ・ cm 2 Thickness 440μm anion exchange membrane (38) and 0.2-1μm graphite particles 85wt
% Gas diffusion electrode (35) is installed as shown in FIG. 2, the electrode area is 50 cm 2 , the space between the cathode chambers (between the gas diffusion electrode (35) and the anion exchange membrane (38)) is 6 mm, Inter-chamber spacing (cation exchange membrane with anode (33) and anion exchange membrane (38)
Fabricated an electrolytic layer between) 4 mm and circulates 2M KOH solution (34) to the cathode chamber, and electrolysis was performed by supplying 1M H 2 SO 4 aqueous solution (37) to the intermediate chamber.
電流５〜7.5Aで第５図に示すように電流効率80〜100
％をえた。At a current of 5 to 7.5 A, the current efficiency is 80 to 100 as shown in FIG.
% Gained.
槽電圧は、電解開始後、過酸化水素イオン濃度の増加
とともに上昇し、そののち一定値となる。この定常状態
における槽電圧は、電流密度を高くするほど高くなる。
本実施例におけるこの槽電圧と電流密度との関係は、第
６図に示すとおりであった。After the start of electrolysis, the cell voltage increases with an increase in the concentration of hydrogen peroxide ions, and then becomes a constant value. The cell voltage in this steady state increases as the current density increases.
The relationship between the cell voltage and the current density in this example was as shown in FIG.
2M KOH水溶液（34）を100ml/minの容量で循環し、1M
H2SO4水溶液（37）を1ml/minの流量で供給し、３カ月
連続運転を行なった。中間室からオーバーフローする液
の過酸化水素濃度は、7.5wt％程度まで達し、その後一
定となった。該製品液流量は、約2ml/minであった（中
間室へは、上記H2SO4水溶液だけでなく、水素イオン，
水酸イオンおよび過酸化水素イオンのほかこれらイオン
とともに電気化学的移動水がカチオン交換膜（33）およ
びアニオン交換膜（38）を通って入ってくる）。槽電圧
は、4.5V付近を推移した（供給するH2SO4水溶液の濃度
を2Mにして同様に運転したが、その場合は、3.8V付近を
推移した。）。この３カ月の連続運転の間、上記アニオ
ン交換膜（38）はまったく劣化せず、かつカチオン交換
膜（33）−陽極（31）接合体の剥離等の変化も観察され
なかった。Circulate a 2M KOH aqueous solution (34) at a volume of 100 ml / min,
The H 2 SO 4 aqueous solution (37) was supplied at a flow rate of 1 ml / min, and the continuous operation was performed for three months. The concentration of hydrogen peroxide in the liquid overflowing from the intermediate chamber reached about 7.5 wt%, and then became constant. The product liquid flow rate was about 2 ml / min (to the intermediate chamber, not only the H 2 SO 4 aqueous solution but also hydrogen ions,
Hydroxide ions and hydrogen peroxide ions as well as electrochemically transferred water along with these ions enter through the cation exchange membrane (33) and the anion exchange membrane (38)). The cell voltage fluctuated around 4.5 V (the same operation was performed with the concentration of the supplied H 2 SO 4 aqueous solution being 2 M, but in this case, it fluctuated around 3.8 V). During the three months of continuous operation, the anion exchange membrane (38) did not deteriorate at all, and no change such as peeling of the cation exchange membrane (33) -anode (31) assembly was observed.
比較例１ 第４図に示すようにカチオン交換膜（13）を、陽極
（11）と接合せずに使用し、陽極（11）を別途設け、そ
れら（11）（13）の間の陽極室間隔を2mmとし、そこの
陽極液を1M H2SO4水溶液（12）とする以外は、上記の
実施例１と同じ条件にして電解した。5Aおよび7.5Aにお
ける槽電圧は、実施例１の場合にくらべ、それぞれ0.8V
および1.5Vも高く、実施例１におけるカチオン交換膜−
陽極接合の効果が顕著であった。Comparative Example 1 As shown in FIG. 4, a cation exchange membrane (13) was used without being joined to an anode (11), an anode (11) was separately provided, and an anode chamber between the (11) and (13) was used. Electrolysis was carried out under the same conditions as in Example 1 except that the interval was 2 mm and the anolyte therein was a 1M H 2 SO 4 aqueous solution (12). The cell voltage at 5 A and 7.5 A was 0.8 V, respectively, as compared with the case of Example 1.
Cation exchange membrane in Example 1
The effect of anodic bonding was remarkable.
本比較例における定常状態の槽電圧と電流密度との関
係は、第６図に示すとおりであった。The relationship between the cell voltage and the current density in the steady state in this comparative example was as shown in FIG.
実施例２ 実施例１における電解槽の中間室およびアニオン交換
膜を除いた、第１図に示す構造の電解槽を用い、陰極室
（陽極（21）付カチオン交換膜（23）とガス拡散電極
（25）との間）にKOHでなく2M NaOH水溶液を循環する
ことを除いては、実施例１と同じ条件で電解を行なっ
た。第６図に示すように、電流5Aで電流効率は70〜80％
であった。また、アルカリ金属水素過酸化物と過酸化水
素との合計の過酸化水素換算濃度は、約5wt％まで達
し、電槽電圧は、3.5V付近で推移した。３カ月連続運転
を行なったが、カチオン交換膜と陽極との間の剥離等の
変化は観測されなかった。Example 2 An electrolytic cell having the structure shown in FIG. 1 except for the intermediate chamber of the electrolytic cell and the anion exchange membrane in Example 1 was used, and a cathode chamber (a cation exchange membrane (23) with an anode (21) and a gas diffusion electrode) were used. Electrolysis was performed under the same conditions as in Example 1 except that a 2M aqueous solution of NaOH instead of KOH was circulated in (between (25)). As shown in Fig. 6, the current efficiency is 70-80% at the current of 5A.
Met. In addition, the total hydrogen peroxide concentration of the alkali metal hydrogen peroxide and hydrogen peroxide reached about 5 wt%, and the cell voltage changed around 3.5 V. After three months of continuous operation, no change such as peeling between the cation exchange membrane and the anode was observed.
本実施例における定常状態の槽電圧と電流密度との関
係は、第６図に示すとおりであった。The relationship between the cell voltage and the current density in the steady state in this example was as shown in FIG.
比較例２ 第３図に示すようにカチオン交換膜（３）を、陽極
（１）と接合せずに使用し、陽極（１）を別途設け、そ
れら（１）（３）の間の陽極室間隔を2mmとし、そこの
陽極液を1M H2SO4水溶液（２）とする以外は、上記の
実施例２と同じ条件にして電解した。5Aおよび7.5Aにお
ける槽電圧は、比較例１の場合と同じく、実施例２の場
合にくらべ、それぞ0.8Vおよび1.5Vも高かった。Comparative Example 2 As shown in FIG. 3, the cation exchange membrane (3) was used without being joined to the anode (1), the anode (1) was separately provided, and the anode chamber between the (1) and (3) was used. Electrolysis was performed under the same conditions as in Example 2 except that the interval was 2 mm and the anolyte was an aqueous solution of 1M H 2 SO 4 (2). The cell voltage at 5 A and 7.5 A was 0.8 V and 1.5 V higher than that of Example 2 as in Comparative Example 1.
本比較例における定常状態の槽電圧と電流密度との関
係は、第６図に示すとおりであった。The relationship between the cell voltage and the current density in the steady state in this comparative example was as shown in FIG.
第１〜４図はいずれもカチオン交換膜が装着された電解
槽の陰極面上で酸素を電気化学的に還元して過酸化水素
イオンを生成させることにより、過酸化物を含有する水
溶液を電気化学的に製造する装置の例における各室，電
極およびイオン交換膜の配列を示すものであり、そのう
ち第１図は本発明の実施例２によるアルカリ金属水素過
酸化物、第２図は本発明の実施例１による過酸化水素、
第３図は比較例２のアルカリ金属水素過酸化物および第
４図は比較例１の過酸化水素をそれぞれ製造する装置に
係わる。第５図は、本発明の実施例１における過酸化水
素の生成量と電気量の関係を示すグラフである。第６図
は実施例１および２ならびに比較例１および２における
定常状態の槽電圧と電流密度との関係を比較して示すグ
ラフである。 図面中 1,11,21,31……陽極 2,12,17,37……酸水溶液 3,13,23,33……カチオン交換膜 4,14,24,34……アルカリ水溶液 5,15,25,35……ガス拡散電極からなる陰極 6,16,26,36……酸素 27,47……水 18,38……アニオン交換膜FIGS. 1 to 4 show that an aqueous solution containing a peroxide is produced by electrochemically reducing oxygen to produce hydrogen peroxide ions on the cathode surface of an electrolytic cell equipped with a cation exchange membrane. FIG. 1 shows an arrangement of chambers, electrodes and ion exchange membranes in an example of an apparatus for chemical production, wherein FIG. 1 shows an alkali metal hydrogen peroxide according to Example 2 of the present invention, and FIG. Hydrogen peroxide according to Example 1 of
FIG. 3 relates to an apparatus for producing alkali metal hydrogen peroxide of Comparative Example 2 and FIG. 4 relates to an apparatus for producing hydrogen peroxide of Comparative Example 1, respectively. FIG. 5 is a graph showing the relationship between the amount of generated hydrogen peroxide and the amount of electricity in Example 1 of the present invention. FIG. 6 is a graph comparing the relationship between the cell voltage and the current density in the steady state in Examples 1 and 2 and Comparative Examples 1 and 2. In the drawing, 1,11,21,31 …… Anode 2,12,17,37 …… Aqueous acid solution 3,13,23,33 …… Cation exchange membrane 4,14,24,34 …… Alkaline solution 5,15, 25,35… Cathode composed of gas diffusion electrodes 6,16,26,36 …… Oxygen 27,47… Water 18,38 …… Anion exchange membrane
フロントページの続き (72)発明者 川見 洋二 大阪府河内長野市片添町92 (72)発明者 庫内 康博 神奈川県厚木市岡田1775番地 (72)発明者 福田 健市 山口県新南陽市長田町13番13号 (72)発明者 清田 徹 神奈川県厚木市岡田1775番地 (56)参考文献 特開 昭58−213885（ＪＰ，Ａ) 特開 昭56−69384（ＪＰ，Ａ) 特公 昭53−4073（ＪＰ，Ｂ２)Continued on front page (72) Inventor Yoji Kawami 92, Katazoecho, Kawachinagano-shi, Osaka (72) Inventor Yasuhiro Kouuchi 1775-1 Okada, Atsugi-shi, Kanagawa-ken (72) Inventor Ken-shi Fukuda 13 Nagatacho, Shinnanyo-shi, Yamaguchi Prefecture No. 13 (72) Inventor Toru Kiyota 1775 Okada, Atsugi-shi, Kanagawa Prefecture (56) References JP-A-58-213885 (JP, A) JP-A-56-69384 (JP, A) JP-A-53-4073 (JP, B2)
Claims (4)
面上で酸素を電気化学的に還元してHO2 -を生成させるこ
とにより、MHO2（ただし、Ｍはアルカリ金属または水素
である）で表わされる過酸化物を含有する水溶液を電気
化学的に製造する装置において、 イ）上記カチオン交換膜が陽極の、陰極側の面に接合さ
れており、かつ ロ）該カチオン交換膜の反対側に、該陽極に接して水が
存在している 構造を備えていることを特徴とする過酸化物を含有する
水溶液の製造装置。1. A oxygen on the cathode surface of the cation exchange membrane is mounted electrolytic cell and electrochemically reduced HO 2 - by forming a, MHO 2 (however, M is an alkali metal or hydrogen A) wherein the cation exchange membrane is bonded to the surface of the anode on the cathode side, and b) the opposite of the cation exchange membrane. An apparatus for producing an aqueous solution containing peroxide, comprising a structure in which water is present in contact with the anode on the side.
チオン交換膜は該陽極の片面に接合されている）／アル
カリ水溶液／ガス拡散電極からなる陰極／酸素の順に構
成されてなる特許請求の範囲（１）項記載のアルカリ金
属水素過酸化物と過酸化水素との混合物を含有する水溶
液の製造装置。2. A method comprising the steps of water / anode / cation exchange membrane (the cation exchange membrane is bonded to one side of the anode) / aqueous alkaline solution / cathode comprising gas diffusion electrode / oxygen. An apparatus for producing an aqueous solution containing a mixture of an alkali metal hydrogen peroxide and hydrogen peroxide according to item (1).
チオン交換膜は該陽極の片面に接合されている）／酸水
溶液／アニオン交換膜／アルカリ水溶液／ガス拡散電極
からなる陰極／酸素の順に構成されてなる特許請求の範
囲（１）項記載の過酸化水素を含有する水溶液の製造装
置。3. A cathode comprising water / anode / cation exchange membrane (the cation exchange membrane is joined to one side of the anode) / acid aqueous solution / anion exchange membrane / alkali aqueous solution / gas diffusion electrode / oxygen The apparatus for producing an aqueous solution containing hydrogen peroxide according to claim 1, which is constituted in order.
は０または1;nは１〜５の整数;pおよびｑはいずれも正
の整数であって、その比p/qは２〜16;R1,R2,R3はいずれ
も低級アルキル基（ただし、R1とR2が一体となってテト
ラメチレン鎖またはペンタメチレン鎖を形成してもよ
い）;R4はＨまたは低級アルキル基（ただしR3と一体と
なってエチレン鎖またはトリメチレン鎖を形成していて
もよい）;Z-はハロゲンイオン;aは２〜10の整数であ
る。） で表わされる共重合体からなるものである特許請求の範
囲（３）項記載の過酸化水素を含有する水溶液の製造装
置。4. An anion exchange membrane of the general formula (Wherein X is F or CF 3 ; l is 0 or an integer of 1 to 5; m
N is an integer of 1 to 5; p and q are both positive integers, and the ratio p / q is 2 to 16; R 1 , R 2 , and R 3 are all lower alkyl groups (However, R 1 and R 2 may be combined to form a tetramethylene chain or a pentamethylene chain); R 4 is H or a lower alkyl group (however, an ethylene chain or a trimethylene chain is combined with R 3) Z - is a halogen ion; a is an integer of 2 to 10. The apparatus for producing an aqueous solution containing hydrogen peroxide according to claim 3, wherein the apparatus comprises a copolymer represented by the following formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62197775A JP2574678B2 (en) | 1987-08-07 | 1987-08-07 | Equipment for producing aqueous solution containing peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62197775A JP2574678B2 (en) | 1987-08-07 | 1987-08-07 | Equipment for producing aqueous solution containing peroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6442590A JPS6442590A (en) | 1989-02-14 |
| JP2574678B2 true JP2574678B2 (en) | 1997-01-22 |
Family
ID=16380142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62197775A Expired - Lifetime JP2574678B2 (en) | 1987-08-07 | 1987-08-07 | Equipment for producing aqueous solution containing peroxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2574678B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2699793B2 (en) * | 1993-01-05 | 1998-01-19 | 王子製紙株式会社 | Method for producing hydrogen peroxide |
| US7699198B2 (en) * | 2005-05-02 | 2010-04-20 | Belkin International, Inc. | Attachment mechanism for use with a portable electronic device, and method of manufacturing same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS534073A (en) * | 1976-07-01 | 1978-01-14 | Nippon Nodaron Kk | Method of producing hollow vinyl ball exposing character* picture pattern or the like |
| JPS5669384A (en) * | 1979-11-09 | 1981-06-10 | Asahi Glass Co Ltd | Preparation of caustic alkali |
| DE3370657D1 (en) * | 1982-05-28 | 1987-05-07 | Bbc Brown Boveri & Cie | Process for the electrolytic production of hydrogen peroxide, and use thereof |
-
1987
- 1987-08-07 JP JP62197775A patent/JP2574678B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6442590A (en) | 1989-02-14 |
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