TW401373B - Electrolytic ozone generating apparatus - Google Patents
Electrolytic ozone generating apparatus Download PDFInfo
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- TW401373B TW401373B TW086117241A TW86117241A TW401373B TW 401373 B TW401373 B TW 401373B TW 086117241 A TW086117241 A TW 086117241A TW 86117241 A TW86117241 A TW 86117241A TW 401373 B TW401373 B TW 401373B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
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Abstract
Description
401373 五、發明說明（23 ) 補充 f修正概ί之401373 V. Description of the invention (23) Supplement f
圖4爲單向平衡閥13的結構示意圖 主要元件對照表 1 加水口蓋 2 加水口 3 氫氣出口 4 陰極水箱 5 反應介質 6 陰極循環水管 7 陽極循環水管 8 臭氧發生器 9 陽極循環水管 10-11 冷卻風機 1 2 循環水管 13 單向平衡閥 14 陰極循環水管 15 螺母 16 備用放水口. 17 隔離管 18 陽極水箱 18a 集氣面 18b 導氣管 19 水位檢測密封管 2 0 永磁體 -------------------—訂I:--------線"、 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用尹國國家標準（CNS)A4規格（210 X 297公釐） -26- 401373 五、發明説明（彳) 發明領域 本發明相關於一種電解式臭氧產生裝置’它係一種電 化學技術及臭氧應用技術領域。 發明背景 採用臭氧法消毒滅菌的優點越來越受到人們的重視。 目前較多採用高頻高壓的電暈放電法產生臭氧’而硏究與 發展電化學方法產生高濃度臭氧已引起廣泛的關注。電化 學方法生產臭氧的基本原理是眾所周知的：臭氧產生以去 離子水爲原料，在外加直流電源時，陰，陽電極的電化學 反應式爲： 陰極析氫反應式：2H' + 2e_— Hd (1) 陰極氧去極化反應式：1/2 02+21^ + 2 6- — Η 2 0 ( 2 ) 陽極主反應式：H2〇—l/3 〇3个+ 2 e- + 2 Η ' ( 3 ) 經濟部中央梯準局員工消費合作社印聚 陽極副反應式：Η 2 Ο — 1 / 2 0 2个+ 2 e · + 2 Η ' ( 4 ) 陽極反應產生的質子在直流電場作用下以水溶劑化質 子形式通過陽離子交換膜向陰極遷移。 根據以上電化學反應原理可知，構成一最基本的電解 式臭氧產生裝置的核心部份是一電解槽。該電解槽必須具 -4 - (請先閱讀背面之注意事項來、填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 461375 五、發明說明（24 2 1 浮子 2 2 2 4 2 5 2 6 2 7 2 8 2 9 3 0 3 1 3 2 3 3 3 4 3 7 3 8 3 9 4 0 4 1 4 2 4 3 4 4 舌簧管 微孔阻礙板 出氣口 螺母 墊圈 導流夾板 防腐片 密封墊 陰極至框架 導流板 陰極多孔集流片 陰極催化劑膜片 陽離子交換膜片 陽極催化劑膜片 陽極多孔集流片 陽極室框架 陽極散熱片 絕緣墊圈 螺栓 引流螺釘 墊圈 陰極水箱接口 陽極水箱接口Figure 4 shows the structure of the one-way balance valve 13. The main components are compared with the table 1 water inlet cover 2 water inlet 3 hydrogen outlet 4 cathode water tank 5 reaction medium 6 cathode circulating water pipe 7 anode circulating water pipe 8 ozone generator 9 anode circulating water pipe 10-11 cooling Fan 1 2 Circulating water pipe 13 One-way balancing valve 14 Cathode circulating water pipe 15 Nut 16 Spare water outlet. 17 Isolating pipe 18 Anode water tank 18a Air collecting surface 18b Air duct 19 Water level detecting sealing tube 2 0 Permanent magnet ------- ------------— Order I: -------- line ", (Please read the precautions on the back before filling this page) This paper size applies Yin National Standard ( CNS) A4 specification (210 X 297 mm) -26- 401373 V. Description of the invention (i) Field of the invention The present invention relates to an electrolytic ozone generating device, which is a field of electrochemical technology and ozone application technology. BACKGROUND OF THE INVENTION The advantages of sterilization by ozone method are receiving increasing attention. Currently, high frequency and high voltage corona discharge methods are used to generate ozone ', and research and development of electrochemical methods to generate high concentrations of ozone have attracted widespread attention. The basic principle of electrochemical production of ozone is well known: ozone is produced using deionized water as the raw material. When a DC power supply is applied, the electrochemical reaction formula of the cathode and anode is: Cathodic hydrogen evolution reaction formula: 2H '+ 2e_— Hd ( 1) Cathodic oxygen depolarization reaction formula: 1/2 02 + 21 ^ + 2 6- — Η 2 0 (2) Anode main reaction formula: H2〇—l / 3 〇3 pieces + 2 e- + 2 Η ' (3) The secondary reaction formula of the printed poly anode of the consumer cooperative of the Central Government Bureau of the Ministry of Economic Affairs: Η 2 〇 — 1/2 0 2 + 2 e · + 2 Migration to the cathode through a cation exchange membrane as a water-solvated proton. According to the above electrochemical reaction principle, it can be known that the core part constituting a most basic electrolytic ozone generating device is an electrolytic cell. The electrolytic cell must have -4-(Please read the precautions on the back to complete this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 461375 V. Description of the invention (24 2 1 Float 2 2 2 4 2 5 2 6 2 7 2 8 2 9 3 0 3 1 3 2 3 3 3 4 3 7 3 8 3 9 4 0 4 1 4 2 4 3 4 4 air reed tube micro-hole blocking plate air outlet nut washer Spoiler anticorrosive sheet gasket cathode to frame deflector cathode porous current collector cathode catalyst diaphragm cation exchange membrane anode catalyst diaphragm anode porous current collector anode chamber frame anode heat sink insulation washer bolt drain screw washer cathode water tank interface Anode water tank interface
(請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用令國國家標準（CNS)A4規格（210 X 297公釐） -27- 經濟部中央標準局員工消費合作社印製 401373 at ___ _____B7 五、發明説明（2 ) 有陽極，陰極，電解質和原料水。 中國大陸專利申請CN 8 6 1 0 8 7 9 2A描述了一 種固體聚合物電解質結構，該結構包含一塊膜片，許多導 電顆粒及一塊導電透水性基體構件，其中導電顆粒和導電 透水性基體（作爲集電板）以物理或電學方式互相接觸並 嵌入膜片中’或與膜片結合在一起。其中膜片一般優選擇 採用碳氟化合物材料。爲使導電透水性基體嵌入到碳氟化 合物膜中，最好使碳氟化合物處於熱塑狀態。導電性透水 基體包括碳布，碳紙，金屬網，金屬氈以及多孔金屬片等 ，以碳布爲佳。使用各種技術可以把電催化活性顆粒加到 膜片表面中，包括加壓，與溶劑混合以及與膜片或其它聚 合物的粉末摻合。其中一種具體作法是：先製備一種如用 熱塑狀態下的聚四氟乙烯或膜片之類的粘合劑將電催化活 性顆粒結合在一起所組成的薄膜，黏合材料/催化劑的組 合物以處於多孔薄膜狀態爲準。然後，該薄膜可以層壓於 集電極和膜片之間。 薄膜可以用一種處於熱塑狀態的離子交換膜片混合料 來製備，該離子交換膜中含有1 0% (重量）粒度爲3 0 微米，其上有5 %鉑的碳顆粒。該混合料可以在3 1 0 °C 的溫度和1噸/英寸2 ( 1 5 5大氣壓）的壓力下熱壓 1 · 25分鐘，製備一種厚度小於〇 . 5毫米的薄膜 。該薄膜可以常規的熱壓技術層壓於碳布集電板和膜片之 間。爾後，可以將碳布嵌入膜片中’其方法爲：在1 2 0 。(：的溫度和大氣壓力下將膜片/碳布二者一起預熱3 0秒(Please read the precautions on the back before filling this page) This paper size is applicable to the national standard (CNS) A4 (210 X 297 mm) of the paper size. 5. Description of the invention (2) There are anode, cathode, electrolyte and raw water. The Chinese mainland patent application CN 8 6 1 0 8 7 9 2A describes a solid polymer electrolyte structure including a membrane, a plurality of conductive particles, and a conductive water-permeable substrate member, wherein the conductive particles and the conductive water-permeable substrate (as (Collector plates) are in physical or electrical contact with each other and embedded in the diaphragm 'or combined with the diaphragm. Among these diaphragms, fluorocarbon materials are generally preferred. In order for the conductive and water-permeable substrate to be embedded in the fluorocarbon film, it is preferable that the fluorocarbon is in a thermoplastic state. The conductive water-permeable substrate includes carbon cloth, carbon paper, metal mesh, metal felt, and porous metal sheet. Carbon cloth is preferred. Electrocatalytically active particles can be added to the surface of the membrane using a variety of techniques, including pressurization, mixing with solvents, and blending with powder of the membrane or other polymer. One of the specific methods is to first prepare a thin film composed of electro-catalytically active particles by using a binder such as polytetrafluoroethylene or a membrane in a thermoplastic state, and bonding the material / catalyst composition to It is in the state of porous film. The film can then be laminated between the collector and the diaphragm. The film can be prepared from a thermoplastic ion exchange membrane mix containing 10% (by weight) carbon particles with a particle size of 30 microns and 5% platinum on it. The mixture can be hot-pressed at a temperature of 3 10 ° C and a pressure of 1 ton / inch 2 (155 atmospheres) for 1.25 minutes to prepare a film having a thickness of less than 0.5 mm. The film can be laminated between a carbon cloth collector plate and a diaphragm by a conventional hot pressing technique. Thereafter, the carbon cloth can be embedded in the film sheet 'by the method: 1 2 0. (: Preheat both diaphragm / carbon cloth for 30 seconds under the temperature and atmospheric pressure
In- I t^i— n I ^ * ^ - 4 (請先閲讀背面之注意事項f寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4规格（2丨0X297公釐） -5- A7 A7In- I t ^ i— n I ^ * ^-4 (Please read the notes on the back f to write this page) This paper size is applicable to China National Standard (CNS) A4 (2 丨 0X297mm) -5- A7 A7
--------------------訂----一-----線· - -* (諳先閲讀背面之注意事項再填寫本頁> _B7 五、發明說明（25 ) 45 環狀密封唇 4 6 陽極水箱接口 4 7 陽極水箱接口 4 8 限壓閥口 4 8a 限壓塞 4 9 單向平衡閥下閥體 5 0 膜片 51 單向平衡閥上閥體 52 陽極水箱接口 52a 阻礙孔 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -28 - 五、發明説明 A7 B7 左右，接著在同樣的溫度和1 - 2噸/英寸 5 5 經濟部中央標準局員工消費合作杜印製 3 1 0大氣壓）的壓力下加熱2 2 5秒，再在2 - 3噸/ 英寸2 ( 3 1 0 — 4 6 5大氣壓）的壓力下加熱約6 0秒。 J P，平4 一 8 8 1 8 2提出採用美國杜邦公司製造 的全氟磺酸陽離子交換膜（1 1 7型），在其表面塗敷商 品離子粉（離子交換樹脂粉末）的懸浮（懸濁）液，施加 5kg/cm2的壓力，在180 - 200°C的溫度下加熱 3 0分鐘而形成多孔質離子交換樹脂層，這種離子交換樹 脂層表層厚度爲1 0 0微米。在形成的離子交換樹脂層上 緊密配置以氧化鉛形成一個多孔層面作爲陽極電極。在離 子交換膜的與這個多孔層面相對的面上採用化學鍍的方法 形成釘金屬膜作爲陰極。 製備氧化鉛陽極的具體做法是，首先將含7 5%鈦， 2 5 %鉑的塗敷液塗敷在以燒結钽粉做成的板狀基體上， 通過熱分解形成基體中的由鉑/鉬構成的中間層。以 8 0 0克/升的硝酸錯水溶液作電解液，添加少量的硝酸 後’加熱到7 0 °C，將前述的基體及鈦板浸入此電解質中 ’預先用1 OA/dm2的電流密度進行予電解，然後再用 4 A / d m 2電流密度在前述的基體表面上電沉積^^ 一二氧 化鉛層’作爲陽極。該二氧化鉛層表層厚度爲1 〇 〇 ，以1.Okg/cm2的壓力將這個電沉積二氧化鉛層陽 極緊壓在離子交換膜的離子交換樹脂層一側，形成電極結 構體 1?’平2-43389 和]?，平2-4339〇 表紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） n In Hi -- - -I— - -- I - I · -Η5"-1 In K - I . I —II 丁 Λ·"』 、" (請先閱讀背面之注意事項«%寫本頁) -6- 經濟部中央標隼局員工消費合作社印製 A7 B7 五、發明説明Q ) 提出了離子交換樹脂膜和二氧化鉛電極連接體的製造方法 。該方法在陽離子或者陰離子交換樹脂膜的一側配置含錯 離子水溶液，在另一側配置次亞氯酸水溶液（或者溴的水 溶液），使在上述離子交換樹脂膜的一側表面析出二氧化 鉛鍍層作爲電解水製造臭氧的陽極催化劑。 U S 4 9 2 7 8 0 0介紹了一種含有二氧化鉛電解沉 積層的電極催化劑及這種電極催化劑的製備方法，催化劑 沉積層中分散有含/5 -二氧化鉛粉末的顆粒。這些顆粒中 含有/3 -二氧化鉛粉末和可選擇加入的電解共催化劑，電 解共催化劑是PTEE(聚四氟乙烯），瓊脂，全氟離子 交換樹脂等中的一種。這種電極催化劑在電解水製備臭氧 和電解水溶液製備過氧化物方面很有用處。 上述專利申請的共同特點是：電解質均採用固體聚合 物電解質（SPE)，通常爲全氟磺酸陽離子交換膜，該 陽離子交換膜在電解槽中既作電解質，又兼作陰極室和陽 離子之間的隔離膜。 陰極材料（催化劑）通常採用的是鉑族金屬，金，銀 ，鎳，釕或它們的混合物。 陽極材料（催化劑）通常採用鉛系金屬，金或其混合 物以及玻璃碳，二氧化錯。 如上所述的採用固體聚合物電解質的電解式臭氧產生 器的製備方法涉及到以下三種技術： 一是通過熱壓技藝製備電極複合膜，這一技藝程序複 雜，條件苛刻，需要很高的壓力和溫度，使製造成本增加 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 2们公釐） (請先閱讀背面之注意事項#、填寫本I) 订-------------------- Order ---- a ----- line ·--* (谙 Please read the notes on the back before filling this page > _B7 V. Description of the invention (25) 45 Ring-shaped sealing lip 4 6 Anode water tank connection 4 7 Anode water tank connection 4 8 Pressure limiting valve port 4 8a Pressure limiting plug 4 9 Lower check valve body 5 0 Diaphragm 51 Unidirectional Body valve on balance valve 52 Anode water tank connection 52a Obstructed hole The paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) -28-V. Description of the invention A7 B7, then at the same temperature and 1- 2 ton / inch 5 5 Consumers ’cooperation with the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China Du printed 3 10 atmospheres of pressure) for 2 2 5 seconds, and then at 2-3 tons / inches 2 (3 1 0 to 4 6 5 atmospheres) Heat under pressure for about 60 seconds. JP, Hei 4-8 8 1 8 2 proposed the use of a perfluorosulfonic acid cation exchange membrane (type 1 17) manufactured by DuPont of the United States, and the suspension (suspension) of commercial ion powder (ion exchange resin powder) was coated on the surface. ) Liquid, apply a pressure of 5kg / cm2, and heat at 180-200 ° C for 30 minutes to form a porous ion exchange resin layer. The surface thickness of this ion exchange resin layer is 100 microns. On the formed ion exchange resin layer, a porous layer was closely arranged with lead oxide to serve as an anode electrode. A nail metal film was formed on the surface of the ion exchange membrane opposite to this porous layer by using electroless plating as a cathode. The specific method for preparing a lead oxide anode is to first apply a coating solution containing 75% titanium and 25% platinum on a plate-shaped substrate made of sintered tantalum powder, and form a platinum / An intermediate layer made of molybdenum. An 800 g / l aqueous solution of nitric acid was used as the electrolyte. After adding a small amount of nitric acid, 'heated to 70 ° C, immersed the aforementioned substrate and titanium plate in this electrolyte' with a current density of 1 OA / dm2 in advance. Pre-electrolysis was performed, and then a lead dioxide layer was electrodeposited on the surface of the aforementioned substrate with a current density of 4 A / dm 2 as the anode. The thickness of the surface layer of the lead dioxide layer is 100, and the electrodeposited lead dioxide layer anode is pressed against the ion exchange resin layer side of the ion exchange membrane at a pressure of 1.0 kg / cm2 to form an electrode structure 1? ' Ping 2-43389 and] ?, Ping 2-4339〇 The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) n In Hi---I----I-I · -Η5 "- 1 In K-I. I —II DING Λ """, " (Please read the notes on the back «% write this page first) -6- Printed by the Consumer Standards Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 5. Description of the invention Q) A method for manufacturing an ion exchange resin film and a lead dioxide electrode connecting body is proposed. In this method, an aqueous solution containing a wrong ion is disposed on one side of a cation or anion exchange resin film, and an aqueous solution of hypochlorous acid (or an aqueous solution of bromine) is disposed on the other side, so that lead dioxide is precipitated on one surface of the ion exchange resin film. The coating serves as an anode catalyst for the production of ozone by electrolyzing water. U S 4 9 2 7 8 0 0 introduces an electrode catalyst containing a lead dioxide electrolytic deposition layer and a method for preparing the electrode catalyst. Particles containing / 5-lead dioxide powder are dispersed in a catalyst deposition layer. These particles contain / 3-lead dioxide powder and an optional electrolytic co-catalyst. The electrolytic co-catalyst is one of PTEE (polytetrafluoroethylene), agar, and perfluoro ion exchange resin. This electrode catalyst is useful in the production of ozone by electrolyzing water and the production of peroxides by electrolytic water solutions. The common feature of the above patent applications is that the electrolyte is a solid polymer electrolyte (SPE), usually a perfluorosulfonic acid cation exchange membrane. The cation exchange membrane in the electrolytic cell serves as both the electrolyte and the cathode compartment and the cation. Isolation film. Cathode materials (catalysts) are usually platinum group metals, gold, silver, nickel, ruthenium or mixtures thereof. Anode materials (catalysts) are usually lead-based metals, gold or mixtures thereof, and glassy carbon, dioxide. The above-mentioned method for preparing an electrolytic ozone generator using a solid polymer electrolyte involves the following three technologies: First, the electrode composite membrane is prepared by a hot pressing technique. This technique procedure is complicated, the conditions are severe, and high pressure and pressure are required. The temperature increases the manufacturing cost. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 2 mm) (Please read the precautions on the back #, fill out this I). Order
五、發明説明（5 ) 。並且經這種工藝成型的膜如不能及時組裝成產生器整體 ，則由於室溫和存放空間的濕度變化，膜的含水量也產生 相應的變化，這樣會出現電極/膜組合體的變形。 二是通過滲透式化學鍍（即無電解電鍍），這種方式 在離子交換膜的一側或兩側沉積一層有電催化劑，該法使 用的金屬離子，氧化物或還原劑的濃度在化學鍍過程中會 產生變化，難以保護每次製備的膜/電極組合體的均勻， 必須嚴格保證各種成份的濃度，溫度，ρ Η値的恒定，否 則難以保證製備催化劑的質量。 第三，陽極催化劑製備（如採用二氧化鉛時）以多孔 鈦爲基體，在此基體上再陽極電極沉積一層；0 -二氧化鉛 層，此電鍍液中需要保證一定的鉛離子和其他添加劑的濃 度（包括上述彌散電鍍法中的/5 -二氧化鉛顆粒， PTFE，瓊脂，全氟離子交換樹脂等各種成分），此技 藝中ρ Η値產生改變時鍍層中二氧化鉛的晶型也隨之產生 變化。 經濟部中央標準局員工消費合作社印製 Γ·#— (請先閲讀背面之注意事項祝资寫本頁) 因此，現在技術中涉及到採用固體聚合物電解質的電 解式臭氧產生裝置中催化劑/離子交換膜電極的製備方法 ’存在著缺點與不足，即：製備技藝過程複雜，生產成本 高’不易工業化規模生產。 另外，在電解式臭氧產生裝置中所產生的電化學反應 〔參見反應式（3 )和（4 )〕產生臭氧和氧氣時必須要 消耗原料水；電化學反應〔參見反應式（1)和（2)〕 中要消耗質子，該質子是由陽極反應產生的，並經陽離子 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -8 - Α7 Β7 五、發明説明ς ) 交換膜遷移至陰極/陽離子交換膜界面。而質子遷移時總 是以水溶劑化的形式進行，因而隨著電化學反應的進行， 丨場極室內原料水量不斷減少而陰極室內原料水量逐漸增多 ’同時伴隨著電極的電化學反應，其反應界面產生熱量， 如不採用散熱措施則會降低臭氧的產生效率。 發明目的 本發明的目的在於克服上述現有技術中電極製備技藝 複雜’生產成本高的缺點，提供一種電解式臭氧產生裝置 ’該裝置具有由分立的膜片組成的固體聚合物電解質膜複 合電極構件，電極製造技藝簡單，生產成本低，易於工業 化規模生產，同時’本發明的電解式臭氧產生裝置的陰陽 極室內原料水自動平衡’可輸出壓力高於大氣壓的臭氧， 臭氧產生效率高。 本發明的另一目的是提供一種製備上述電解式臭氧產 生裝置中的電解式臭氧產生路的方法。 經濟部中央標準局員工消費合作社印製 ---------Γ·笨--- (請先閲讀背面之注意事項-fir壤寫本頁) 發明槪要 本發明的電解式臭氧產生裝置包括電解式臭氧產生， 通過陽極循環水管與臭氧發生器的陽極室相連的陽極水箱 ’通過陰極循環水管與臭氧產生器的陰極室相連的陰極水 箱。 按照本發明的電解式臭氧產生裝置，其中的電解式臭 氧產生器包括獨立的陽離子交換膜片，分別緊靠於陽離子 本紙張尺度通用中國國家標準（CNS ) Α4規格（210X297公釐） -9- 401373 A7 ________B7_ 五、發明説明（7 ) 交換膜片兩側的獨立的陽極催化劑膜片和獨立的陰極催化 劑膜片，在陽極催化劑膜片的另一側的陽極多孔集流片， 在陰極催化劑膜片的另一側的陰極多孔集流片。 所述的陽離子交換膜片是現有技術中常用的全氟磺酸 陽離子交換樹脂，所述的陽極催化劑膜片是含有聚四氟乙 烯和二氧化鉛的厚度爲0 . 2 — 0 . 3 m m的膜，所述的 陰極催化劑膜片是含有聚四氟乙烯和鈿碳粉的厚度爲〇 . 1 - 0 . 2 m m的膜’所述的陽極多孔集流片是表面塗有 一層含鈉’鍚和銻的導電氧化物的燒結式多孔鈦片，所述 的陰極多孔集流片是燒結式多孔鈦片。 在本發明的電解式臭氧產生裝置中，陰極水箱的位置 高於陽極水箱，在陰極水箱與陽極水箱之間連接著單向平 衡閥（或通斷型電磁閥），實現原料水自動平衡及使本裝 置可輸出帶壓力的臭氧。陽極水箱和陰極水箱內的原料水 既是產生臭氧的原料，又是陰，陽兩極的循環冷卻劑。 本發明電解式臭氧產生裝置中的臭氧產生器的製備方 法包括： 經濟部中央標準局員工消費合作社印製 a·將含有5—15%(重量）鉑的鉑碳粉和聚四氟 乙烯乳液（懸浮液）與適量的二次蒸餾水在8 Ot：左右的 水浴中攪拌成糊狀’然後在3 0 - 4 0°C溫度下反複碾壓 成0·1—0.2mm厚的膜片，其中聚四氟乙烯重量占 鉑碳粉重量的5 - 1 5 %，將所碾壓的膜片在5 0 - 6 0 °C下烘乾並剪切成所需尺寸，製得陰極催化劑膜片（3 3 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -10- A7 B7 五、發明説明（8 ) b _將二氧化鉛粉和聚四氟乙烯乳液與適量的二次蒸 餾水在8 0°C左右的水浴中攪拌成糊狀，然後在3 0〜 4 0°C溫度下反複碾壓成〇 · 2-0 · 3mm厚的膜片， 其中聚四氟乙烯重量占二氧化鉛重量的1 - 5%，將所碾 壓的膜片在5 0 — 6 Ot下烘乾並剪切成所需尺寸，製得 陽極催化劑膜片（35); c .將燒結式多孔鈦片經過脫脂和用5 0 — 2 0% ( 重量）的鹽酸刻蝕予處理，用二次蒸餾水漂洗至無氯離子 後曬乾，然後在其表面塗敷含有鉛，鍚，銻的有機溶液， 在5 0 〇 - 5 3 0 °C電爐中氧化，使其表面形成一薄層含 鉑，鍚，銻的導電氧化物，製得陽極多孔集流片（3 6 ) d ·將燒結式多孔鈦片經過脫脂和用5 - 2 0 % (重 量）的鹽酸刻蝕予處理，用二次蒸餾水漂洗至無氯離子後 曬乾，製得陰極多孔集流片（3 2 )。 本發明的臭氧產生器是由上述獨立元件配合以其它本 領域眾所周知的必備元件組裝而成的。 經濟部中央標準局員工消費合作社印製 ^1. m j - I- .^ϋ i - -I n . j n -I • 5 、-e - I - (請先閱讀背面之注意事項！^寫本頁) 發明的詳細說明 以下參照附圖對本發明的電解式臭氧產生裝置作進一 步詳細說明： 本發明的電解式臭氧產生裝置包括電解式臭氧產生器 8，通過循環水管7與臭氧產生器8的陽極室相連的陽極 水箱18，通過循環水管6與臭氧產生器8的陰極室相連 本紙張只j!適用中國國家標準（CNS ) A4規格（210X297公釐） " ~" -11 - 402373 A7 _____B7_ 五、發明説明（9 ) 的陰極水箱4，單向平衡閥13，冷卻風機10，1 1 ， 水位檢測器1 9，2 0，2 1，2 2和隔離管1 7。 其中電解式臭氧產生器8包括陽離子交換膜片34， 陽極催化劑膜片3 5，陽極多孔集流片3 6，陽極室框架 3 7，陽極散熱片3 8，陰極催化劑膜片3 3，陰極多孔 集流片32，陰極室框架30，導流板31 ，防腐片 28 ’導流夾板27 ’密封墊29及螺栓40，螺母25 ’墊圈2 6 ’ 4 2，絕緣墊圈3 9，引流螺釘4 1。 本發明的電解式臭氧產生裝置中陽極水箱1 8上端有 集氣面1 8 a ，使陽極氣體迅速無滯留排出。集氣面上有 細長導氣管1 8 b，導氣管頂部有臭氧和氧氣出口 2 4， 出氣口 2 4內有微孔阻尼板2 3，陽極水箱內設有隔離管 經濟部中央標準局貝工消費合作社印製 (請先閲讀背面之注意事項*45寫本頁) 1 7，由石英管或鈦管構成。陽極反應產生的陽極氣體（ 臭氧’氧）及循環水由此管導入陽極水箱，此隔離管1 7 的設置減少了臭氧與陽極水箱內原料水的接觸溶解。臭氧 及氧氣經集氣面1 8 a迅速進入導氣管1 8 b，並在導氣 管上端實現了氣/水分離。分離後的臭氧及氧氣透過微孔 阻尼板2 3，由臭氧，氧氣出口 2 4導出。 陰極水箱4的位置高於陽極水箱1 8，其頂部有加水 口 2 ’加水口蓋1，氫氣出口 3。陰極水箱4內裝有水位 檢測器1 9 ’ 2 0，2 1 ，2 2 ’該水位檢測器由舌簧管 2 2，浮子2 1 ，永磁體2 0 ’水位檢測密封管1 9構成 。陰極水箱內水位過高或過低時，輸出信號，使產生器停 止工作。 本紙張尺度適用中國國家標準（C1SS ) A4规格（210X297公釐） -12- 經濟部中央標準局員工消費合作社印製 A7 __B7 五、發明説明（1〇 ) 陰極循環水管6將陰極水箱4和陰極室框架3 0連結 成水循環回路’通過水循環將陰極反應時產生的熱量及時 帶出。 陽極循環水管7將陽極水箱1 8和陽極室框架3 7連 結成水循環回路’通過水循環將陽極反應時產生的熱及時 帶出。 根據電解式臭氧產生器電化學反應原理，陽極反應式 3和4中臭氧和氧的產生需消耗原料水，該反應產生的質 子以水溶劑化的形式通過陽離子交換膜向陰極遷移，當電 解反應繼續進行時’陽極水箱內原料水不斷被消耗，而陰 極水箱內原料水不斷增加。陰極水箱內增加的原料水不能 逆向通過陽離子交換膜返回陽極水箱，最終造成陽極水箱 的原料水完全耗盡的結果。 爲了解決上述問題’本發明在陰極水箱與陽極水箱之 間設置一單向平衡閥。 參見圖1 ’圖4，單向平衡閥13係由上閥體51 ， 膜片5 0 ’下閥體4 9所組成。其中上閥體5 1設有陰極 水箱接口 4 3 ，陽極水箱接口 5 2，接口 5 2中有阻尼孔 5 2 a ，環狀密封唇4 5 ;單向平衡下閥體4 9設有陽極 水箱接口 47 ，限壓閥口 48，限壓塞48a。 單向平衡閥上閥體51的陰極水箱接口43與陰極水 箱4相連接，陽極水箱接口 5 2與陽極水箱1 8相連接， 其下閥體4 9的陽極水箱接口 4 7與陽極水箱1 8相連接 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） ^1- - - I ' I --- 1 - - ^^1 I*^v m 1 - 1^1 - ί I τ» .- ,--, (請先閲讀背面之注意事項再4'寫本頁) -13- 經濟部中央標準局員工消費合作社印製 401373 A7 __ B7 五、發明説明（n ) 在臭氧產生器開始工作時，陽極水箱1 8內的臭氧和 氧氣由於微孔阻尼板2 3的阻尼，逐漸形成壓力P，該壓 力P通過單向平衡閥上閥體5 1的陽極水箱接口 5 2和下 閥體4 9的陽極水箱接口 4 7傳遞到膜片5 0兩側，此時 ’上閥體5 1內由於還有陰極水箱接口 4 3，所以形成原 料水從陽極水箱1 8到陰極水箱4的流動。水流流經陽極 水箱接口 5 2的阻尼孔5 2 a而產生一壓力降ΔΡ。ΔΡ 的產生使膜片5 0兩側形成壓力差，膜片5 0在此壓力差 作用下偏向上閥體5 1方向，直至壓到環狀密封唇4 5上 ’此時切斷了陰極水箱4與陽極水箱1 8的水流通道。膜 片5 0由於陽極水箱1 8內的壓力P的保持而保持該狀態 。此時本發明的臭氧產生器裝置可以以壓力P輸出臭氧和 氧氣。 當本臭氧產生效率停止工作後，壓力P逐漸消失，若 陰極水箱4的水位高於陽極水箱1 8的水位，膜片5 0受 水位壓差作用偏向下閥體4 9方向，陰極水箱4與陽級水 箱1 8通過單向平衡閥又連通，陰，陽極兩水箱內水位會 逐漸恢復平衡。 單向平衡閥的限壓塞4 8a，在陽極水箱18內壓力 過高時，將被壓開，起到限壓保護作用。 本發明的電解式臭氧產生裝置除了在陰極水箱4與陽 極水箱1 8之間設置一單向平衡閥外，還可設置一通斷型 電磁閥’可同樣實現水平衡的目的，通斷型電磁閥在本裝 置起動時關斷陰陽極水箱的通道；在本裝置停止工作時， 本紙張尺度適财關家辟（CNS ) A4· ( 2丨GX297公釐) '~~' ' -14- I- I I - I I—- - -I I I- 1— 1 ---H I 丁 - - - (請先閲讀背面之注意事項寫本頁) 經濟部中央標準局員工消费合作社印製 A7 _____B7_ 五、發明説明（12 ) 通斷型電磁閥接通陰，陽極水箱的通道。 冷卻風機1 0，1 1安裝在電解式臭氧產生器8的下 部，其冷卻風向上吹過散熱片3 8，陽極水箱1 8及陰極 水箱4而起到輔助散熱作用。 本發明中的臭氧產生器是採用下面的經不同技藝分另1J 製備的獨立膜片冷壓製成的。 本發明所採用的陽離子交換膜3 4是美國杜邦公司生 產的全氟磺酸陽離子交換膜（型號1 1 7 )。其處理技術 是：用1 0%的過氧化氫在8 0 - 9 0°C浸煮一小時以除 去膜中有機物雜質。經大量6 0 °C左右的二次蒸餾水漂洗 後再放入8 0 - 9 0 °C 2 m ο 1 / 1的硫酸中浸煮半小 時以除去少量金屬離子，最後用大量6 0°C左右的二次蒸 餾水漂洗至中性，保存於二次蒸餾水中待裝配時用。 陰極催化劑膜片3 3的製備技藝是：將含有5 - 1 5 % (重量）鉛的鈾碳粉（2 0 0孔過篩）與聚四氟乙烯乳 液（懸浮液）和適量二次蒸餾水在8 0 °C左右水浴中攪拌 成糊狀，然後在30 — 40 °C溫度下反複碾壓成0 . 1_ 0.2mm厚的膜片。其中聚四氟乙烯重量占鈾碳粉重量 的5 — 1 5%。將所碾壓的膜片經50 - 60 °C烘乾’並 剪切成所需的尺寸，待裝配時用。由此技藝製成的陰極催 化劑膜片具有多孔導電性質，在該催化劑膜片/陽離子交 換膜接觸界面產生的氫氣和伴隨質子遷移的水能順利通過 陰極催化劑膜片微孔進入陰極室。 陽極催化劑膜片3 5的製備技藝是：將二氧化鉛粉（ 本紙張尺度適用中國國家榇準（CNS ) Α4規格（210Χ297公釐） (请先閲讀背面之注意事項寫本頁) 4Γ -15- 4Q13T9 A7 B7 五、發明説明（13 ) 1 8 0孔過篩）與聚四氟乙烯乳液（懸浮液）以及適量二 次蒸餾水在8 Ot左右攪拌成糊狀。然後在3 0 - 4 0°C 溫度下碾壓成0.2_0.3mm的膜片。其中聚四氟乙 烯占二氧化鉛粉重量的1 — 5%。將該膜片經5 0 — 6 0 乞烘乾後剪切成所需的尺寸保存，待裝配時用。由此技藝 製成的陽極催化膜片具有多孔導電性，在陽極催化劑膜片 /陽離子交換膜接觸界面產生的臭氧和氧能順利通過陽極 催化劑膜片微孔進入陽極室；同時原料水能通過該膜片微 孔逆向遷移進入陽極催化劑膜片/陽離子交換膜反應界面 ，參與陽極反應。一部分原料水伴隨質子通過陽離子交換 膜遷移至陰極室。 經濟部中央標準局員工消費合作社印製 陽極多孔集流片3 6的製備技藝是：將燒結式的多孔 鈦片（最大孔徑爲26//m，透氣率爲1 19M3/m2· h k P a )經過脫脂和用5 — 2 0% (重量）的鹽酸刻蝕 予處理後，用二次蒸餾水漂洗至無氯離子後曬乾。然後在 其表面塗敷含有鉑，鍚，銻的有機溶液，在5 0 0 -5 3 0 °C的電爐中氧化，使其表面形成一薄層含鋁，錫， 銻的導電氧化物，防止多孔集流片在通過陽極電流時產生 鈍化。經上述技藝製成的多孔集流片具有導電和氣液導通 功能（即氣體產物可通過該集流片離開電極反應界面；而 原料水可通過該集流片進入電極反應界面）。其中所述的 含有鉑，錫，銻的有機溶液的重量百分組成爲： 濃鹽酸 S — I - 2 % 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16- 經濟'邱中央標準局員工消費合作社印製 A7 B7 五、發明説明（14 ) :S „ c 1 4 · 5 Η 2 0 5 - 1 0 %·· S ». c 1 3 0.5 -1 · 5%； C4H9〇H 60-90%。 陰極多孔集流片3 2的製備技藝是：將燒結式多孔鈦 片（最大孔徑爲2 6 ，透氣率爲1 1 9M3/m2 . hkPa)經脫脂後用5 — 20% (重量）的鹽酸刻蝕， 用二次蒸餾水漂洗至無氯離子，曬乾，保存，待裝配時用 。該多孔集流片具有導電和氣液導通功能。 導流板3 1爲金屬鈦板，經加工形成有縱橫溝槽的零 件’如圖3所示。該導流板分別裝配在陰，陽極框架內構 成陰，陽極兩室。其有縱橫溝槽的面分別面對陰，陽極多 孔集流片。導流板3 1之縱橫溝槽內可容納原料水，在溝 槽內原料水和氣體產物對流，擴散。導流板具有導電冷卻 功能。 陽極室框架3 7採用聚四氟乙烯材料，加工成獨立元 件，如圖3所示。該框架設有上，下氣水嘴，並分別與陽 極水箱1 8相連接，構成陽極室內原料水循環回路。借助 陽極反應產生的氣體（臭氧，氧）上升力和以陽極室內原 料水溫高於陽極水箱水溫的溫差爲動力，形成水的自動循 環而起到冷卻作用。 陰極室框架3 0選擇有機玻璃或A B S塑料加工成型 ，如圖3所示。該框架設有上，下氣水嘴，並分別與陰極 水箱4相連接，構成陰極室內原料水循環回路.借助陰極 反應產生的氣體（氫）上升力和以陰極室內原料水溫高於 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閲讀背面之注意事項身填寫本頁) 、'1T' -17- Α7 Β7 五、發明説明U ) 陰極水箱水溫的溫差爲動力，形成水的自動循環而起到冷 卻作用。 密封墊2 9選擇矽橡膠材料製成，它確保陰，陽兩室 內產生的氣體和原料水的密封。 防腐片2 8選擇金屬鈦材料，防止導流夾板腐蝕。導 流夾板2 7採用硬質合金鋁板製成，並作爲產生器陰，陽 電極與外接直流電源相連接。 本發明的臭氧產生器係由上述各元件採用冷壓裝配方 法製成，其裝配順序是： IW極散熱片3 8，導流夾板2 7，防腐片2 8，密封 墊29，導流板3 1 ，陽極室框架37，密封墊29，陽 極多孔集流片36，陽極催化劑膜片35，陽離子交換膜 3 4 ’陰極催化劑膜片3 3 ’陰極多孔集流片3 2，密封 墊2 9 ’導流板3 1 ’陰極室框架3 〇，密封墊2 9，防 腐片28，導流夾板27，然後用螺栓，螺母，墊圈，絕 緣墊圈緊固。 經濟部中央標準局員工消費合作社印装 (請先閲讀背面之注意事項寫本頁) 本發明的電解式臭氧產生裝置的製備技藝簡單，組裝 方便’與現有技術的臭氧產生裝置相比，本發明裝置的成 本可降低3 0 - 5 0%。並且本發明的電解式臭氧產生裝 置的陰陽極水箱內原料水可自動平衡，最高可輸出高於大 氣壓0.IMPa的臭氧。裝置可長期穩定進行，臭氧產 生效率高’下表是本發明的裝置與現有技術的一些電解式 臭氧產生裝置的臭氧產生效率的比較： 本紙張尺度適财關家鱗（CNS ) A4^ ( 2iqx297公楚） -18- 401373 at ___B7 五、發明説明（16 ) 槽電壓 電流密度 臭氧產生效率 參考文獻 (V) (A/cm2) (%) 本發明 3.5 1.5 18-20 現有技術1 3.6 1.0 16 US4927800 現有技術2 4.0 8 JP43390/90 現有技術3 3.3 1.0 13 JP20488/91 現有技術4 4.0 7 JP43389/90 現有技術5 1.0 13-16 US5203972 實施例： 實施例1 : 電解式臭氧產生器（ 8 )的製備 (請先閲讀背面之注意事項寫本頁) 經濟部中央標準局員工消費合作社印裝 a .陽離子交換膜（34)的製備：將117型全氟 磺酸陽離子交換膜（杜邦公司產品）用10%的過氧化氫 在9 0°C浸煮一小時以除去膜中有機物雜質，經大量6 0 °C的二次蒸餾水漂洗後再放入80 °C 2mo 1/1的硫 酸中浸煮半小時以除去少量的金屬離子，最後用大量6 0 °C的二次蒸餾水漂洗至中性，保存於二次蒸餾水中待裝配 時用。 b ·陰極催化劑膜片（3 3 )的製備：將含有6 % ( 重量）鉑的鉑碳粉（2 0 0孔過篩）與聚四氟乙烯乳劑（ 懸浮液）和適量二次蒸餾水在8 0 °C左右水浴中攪拌成糊 狀，然後在3 5 °C溫度下反複碾壓成0 . 1mm厚的膜片 。其中聚四氟乙烯重量占鈾碳粉重量的1 0%。所碾壓的 膜片於6 0°C供乾，並剪切成所需的尺寸，待裝配時用。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -19- 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（17 ) C ·陽極催化劑膜片（3 5 )的製備：將/3 —二氧化 鉛粉（1 8 0孔過篩）與聚四氟乙烯乳劑（懸浮液）以及 適量二次蒸餾水在8 0°C左右攪拌成糊狀。然後在4 0°C 溫度下碾壓成0.2mm的膜片。其中聚四氟乙烯占二氧 化鉛粉重量的2 %。該膜片經5 5 °C烘乾後剪切成所需的 尺寸保存，待裝配時用。 d .陽極多孔集流片（3 6 )的製備：將燒結式的多 孔鈦片（最大孔徑爲2 6 "m，透氣率爲1 1 9M3/m2 • h k P a )經過脫脂和用1 〇 %鹽酸刻蝕予處理後，用 二次蒸餾水漂洗至無氯離子後曬乾。然後在其表面塗敷含 有鉑，錫，銻的有機溶液，在5 2 0 °C的電爐中氧化，使 其表面形成一薄層含鈾，錫，銻的導電氧化物。其中所述 的含有鈾，錫，銻的有機溶液的重量百分組成爲： 濃鹽酸 1 % ； S „ C 1 4 · 5 H a 0 8 % ： S .> C 1 3 1.0%; C 4 H 9 Ο H 8 5%。 e.陰極多孔集流片（32)的製備：將燒結式多孔 鈦片（最大孔徑爲2 6 ，透氣率爲1 1 9M3/m2 · h k P a )經脫脂後用1 0%鹽酸刻蝕，用二次蒸餾水漂 洗至無氯離子，曬乾，保存，待裝配時用。 將上述製備的五個元件剪切成8 c m2大小的方塊，配 合其它元件，按照陽極散熱片（3 8 ) ’導流來板（2 7 本紙張尺度適用中國國家梂準（CNS ) A4規格（210 X 297公釐） (請先閲讀背面之注意事項®寫本頁) "° -20- 40f37氟 五、發明説明（18 ) )’防腐片（28) ’密封墊（29)，導流板（31) ’陽極室框架（37) ’密封墊（29)，陽極多孔集流 (請先閲讀背面之注意事項翁寫本頁} 片（36) ’陽極催化劑膜片（3 5)，陽離子交換膜（ 34) ’陰極催化劑膜片（3 3)，陰極多孔集流片（ 32) ’密封墊（29)，導流板（3 1)，陰極室框架 (30)，密封墊（29)，防腐片（28)，導流夾板 (2 7 )的順序排列，其中的導流板（3 1 )採用丄〇 mm厚的金屬鈦板加工製成，其—面均勻分布7個寬 2 . 5mm，深度爲6 mm的溝槽：陰極室框架 以有機玻璃材料注塑成型，框架內有3 1 X 3 1 X 9 m m 3 的空間’其上下氣水連接嘴內徑爲4 m m ;陽極室框架（ 經濟部中央標準局員工消費合作社印製 3 7 )以聚四氟乙儲加工製成’其形狀大小和內容積與陰 極室框架（3 0 )完全一致；防腐片（2 8 )均採用工業 純鈦’厚度爲〇 · 8mm，面積爲40x40mm2;導流 夾板（2 7 )爲硬質合金鋁材，厚度爲8mm，面積爲 60x60mm2;然後用螺栓（40)，螺母（25)， 墊圈（26，42)和絕緣墊圈（39)緊固，即得到本 發明的電解式臭氧產生器（8)。 實施例2 :電解式臭氧產生器（8 )的製備 a .陽離子交換膜（34)的製備：將117型全氟 磺酸陽離子交換膜（杜邦公司產品）用1〇%的過氧化氫 在8 0 °C浸煮一小時以除去膜中有機物雜質，經大量6 〇 °C的二次蒸餾水漂洗後再放入8 0 °C 2 m ο 1 / 1的硫 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -21 - 觎m a? ’ B7 1、發明説明（19 ) 酸中浸煮半小時以除去少量的金屬離子，最後用大量6 ◦ °C的二次蒸餾水漂洗至中性，保存於二次蒸餾水中待裝配 時用。 b .陰極催化劑膜片（33)的製備：將含有12% (重量）鉑的鉑碳粉（2 0 0孔過篩）與聚四氟乙烯乳劑 (懸浮液）和適量二次蒸餾水在8 0 °C左右水浴中攪拌成 糊狀，然後在4 0 °C溫度下反複碾壓成0 . 2mm厚的膜 片。其中聚四氟乙烯重量占鈾碳粉重量的1 5%。所碾壓 的膜片於6 烘乾，並剪切成所需的尺寸，待裝配時用 0 C .陽極催化劑膜片（35)的製備：將二氧化鉛粉 (1 8 0孔過篩）與聚四氟乙烯乳劑（懸浮液）以及適量 二次蒸餾水在8 0°C左右攪拌成糊狀。然後在3 5 °C溫度 下碾壓成0 · 2 mm的膜片。其中聚四氟乙烯占二氧化鉛 粉重量的1 %。該膜片經6 烘乾後剪切成所需的尺寸 保存，待裝配時用。 d .陽極多孔集流片（3 6 )的製備：將燒結式的多 孔鈦片（最大孔徑爲2 6 //m，透氣率爲1 1 9M3/m2 • h k P a )經過脫脂和用1 0 %鹽酸刻蝕予處理後，用 二次蒸餾水漂洗至無氯離子後曬乾。然後在其表面塗敷含 有鉑，錫，銻的有機溶液，在5 0 0 °C的電爐中氧化，使 其表面形成一薄層含鈾’錫’銻的導電氧化物。其中所述 的含有鈾，錫，鍊的有機溶液的重量百分組成爲： (請先閱讀背面之注意事項身填寫本頁) 訂 經濟部中央標準局員工消#合作社印^ 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） -22- 0 % 2 % 20 0 % 2 % 20 五、 發明説明（ 濃鹽酸 9% ; H2ptc 16.6Η2〇 s n c 1 ^ . 5 Η 2 Ο 1 0 % ; S b C 1 3 c > H 9 Ο H 7 8%。 e .陰極多孔集流片（3 2 )的製備：將燒結式多孔 欽片（最大孔徑爲2 6#m，透氣率爲1 1 9M3/m2 . h k P a )經脫脂後用丨〇 %鹽酸刻蝕，用二次蒸餾水漂 洗至無氯離子，B麗乾，保存，待裝配時用。 按照與實施例1相同的方法，將上述製得的元件與其 它元件裝配成本發明的電解式臭氧產生器（8 )。 實施例3 :電解式臭氧產生器（8 )的製備 a .陽離子交換膜（34)的製備：將1 磺酸陽離子交換膜（杜邦公司產品）用1 〇% 在8 5 °C浸煮一小時以除去膜中有機物雜質， °C的二次蒸餾水漂洗後再放入8 0 °C 2 m 〇 酸中浸煮半小時以除去少量的金屬離子，最後 °C的二次蒸餾水漂洗至中性，保存於二次蒸餾 時用。 b .陰極催化劑膜片（3 3 )的製備：將 (重量）鈾的鉛碳粉（2 0 0孔過篩）與聚四 (懸浮液）和適量二次蒸餾水在8 0°C左右水 糊狀，然後在3 0 °C溫度下反複碾壓成0 . 1 片。其中聚四氟乙烯重量占鈾碳粉重量的5% 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項寫本頁) 、3 經濟部中央標準局員工消費合作社印製 1 7型全氟 的過氧化氫 經大量6 0 1 / 1的硫 用大量6 0 水中待裝配 含有1 0 % 氟乙烯乳劑 浴中攪拌成 m m厚的膜 。所碾壓的 -23- 經濟部中央標準扃員工消費合作社印掣 軸75 - 五、發明説明（21 ) 膜片於6 0°C烘乾，並剪切成所需的尺寸，待裝配時用。 c ·陽極催化劑膜片（3 5 )的製備：將Θ —二氧化 錯粉（1 8 0孔過篩）與聚四氟乙烯乳劑（懸浮液）以及 適量二次蒸餾水在8 0°C左右攪拌成糊狀。然後在3 溫度下碾壓成〇·3mm的膜片。其中聚四氟乙烯占二氧 化給粉重量的1 · 5 %。該膜片經6 0 X：烘乾後剪切成所 需的尺寸保存，待裝配時用。 d ·陽極多孔集流片（3 6 )的製備：將燒結式的多 孔鈦片（最大孔徑爲2 6 # m，透氣率爲1 1 9 Μ 3 /m 2 • h k P a )經過脫脂和用1 〇 %鹽酸刻蝕予處理後，用 二次蒸餾水漂洗至無氯離子後曬乾。然後在其表面塗敷含 有鈾’錫，銻的有機溶液，在5 2 0 °C的電爐中氧化，使 其表面形成一薄層含舶，錫，銻的導電氧化物。其中所述 的含有鉑，錫，銻的有機溶液的重量百分組成爲： 濃鹽酸 1.5%； S n C 1 1 · 5 Η 2 0 5 % ； S ,> C 1 3 0.5%： C 4 H 9 0 H 90%。 e ·陰極多孔集流片（3 2 )的製備：將燒結式多孔 鈦片（最大孔徑爲2 6 ，透氣率爲1 1 9M3/m2 · h k P a )經脫脂後用1 0 %鹽酸刻蝕，用二次蒸餾水漂 洗至無氯離子，曬乾，保存，待裝配時用。 按照與實施例1相同的方法，將上述製得的元件與其 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1^ m -- - - --1 1^1 n I m i In ^^1 - .¾. , i (請先閲讀背面之注意事項一^寫本頁) -24 - A7 ________B7 五、發明説明（22 ) 它元件裝配成本發明的電解式臭氧產生器（8 )。 實施例4:本發明的電解式臭氧產生裝置的組裝和應用 採用實施例1製得的電解式臭氧產生器（8 )和下述 元件： 1 5 00毫升的陰極水箱（4) ，1 2 00毫升的陽 極水箱（1 8 ) ’單向平衡閥（1 3 )，冷卻風機（1 0 ’11) ’陽極循環水管（7)，陰極循環水管（6)， 水位檢測器（1 9，2 0，2 1，2 2 )和隔離管（1 7 )按照本領域習知的方法安裝形成本發明的電解式臭氧產 生裝置。 本實施例的電解式臭氧產生裝置在以1 . 5A/cm2 的電流密度進行時，產生器槽電壓爲3 . 5±0 . IV， 在環境溫度爲2 5 °C左右時，連續進行2 4小時，陰，陽 極水箱中的原料水溫可維持在3 0°C左右，臭氧產生效率 爲 1 8 %。 從陽極水箱可以輸出高於大氣壓〇.〇8MPa壓力 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項寫本頁) 的臭氧。 附圖簡要說明： 圖1爲本發明的電解式臭氧產生裝置的結構示意圖。 圖2爲圖1中固體聚合物電解質膜複合電極電解式臭 氧產生裝置（8 )的裝配示意圖。 圖3爲圖2的展開圖。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -25- 401373 五、發明說明（23 ) 補充 f修正概ί之5. Description of the invention (5). And if the membrane formed by this process cannot be assembled into the whole generator in time, the moisture content of the membrane will change accordingly due to changes in humidity at room temperature and storage space, which will cause deformation of the electrode / membrane assembly. The second is through penetration chemical plating (ie, electroless plating). In this way, an electrocatalyst is deposited on one or both sides of the ion exchange membrane. The concentration of metal ions, oxides or reducing agents used in this method is electroless plating. Changes occur during the process, and it is difficult to protect the uniformity of the membrane / electrode assembly prepared each time. The concentration, temperature, and ρ 各种 of the various components must be strictly maintained, otherwise it is difficult to ensure the quality of the prepared catalyst. Third, the preparation of anode catalyst (such as when using lead dioxide) uses porous titanium as the substrate, and then deposits a layer of anode electrode on this substrate; 0-lead dioxide layer, this plating solution needs to ensure certain lead ions and other additives Concentration (including various components such as / 5-lead dioxide particles, PTFE, agar, perfluoro ion exchange resin, etc. in the above-mentioned dispersion plating method). In this technique, the crystal form of lead dioxide in the coating is also changed when ρ Η 値 is changed. Changes follow. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Γ · # — (Please read the notes on the back to write this page) Therefore, the current technology involves catalysts / ions in electrolytic ozone generators using solid polymer electrolytes. There are disadvantages and deficiencies in the preparation method of the exchange membrane electrode, that is, the preparation process is complicated and the production cost is high. It is not easy to produce on an industrial scale. In addition, the electrochemical reaction (see reaction formulas (3) and (4)) generated in the electrolytic ozone generating device must consume raw water when generating ozone and oxygen; the electrochemical reaction [see reaction formulas (1) and ( 2)] protons are consumed. The protons are produced by the anode reaction and are cationized. The size of this paper applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm). -8-Α7 Β7 V. Description of the invention) Exchange membrane Migrate to the cathode / cation exchange membrane interface. Proton migration always occurs in the form of water solvation, so as the electrochemical reaction progresses, the amount of raw material water in the field of the electrode decreases and the amount of raw material water in the cathode room gradually increases. The interface generates heat. Without heat dissipation measures, the efficiency of ozone generation will be reduced. OBJECTS OF THE INVENTION The purpose of the present invention is to overcome the disadvantages of the complicated electrode preparation technology in the prior art described above, and to provide an electrolytic ozone generator. The device has a solid polymer electrolyte membrane composite electrode member composed of discrete membranes. The electrode manufacturing technique is simple, the production cost is low, and it is easy to produce on an industrial scale. At the same time, the "automatic balance of raw material water in the anode and anode chambers of the electrolytic ozone generator of the present invention" can output ozone with a pressure higher than atmospheric pressure, and has high ozone production efficiency. Another object of the present invention is to provide a method for preparing an electrolytic ozone generating circuit in the above-mentioned electrolytic ozone generating device. Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs -------- Γ · Ben --- (Please read the precautions on the back-write this page on fir soil) Invention 槪 The electrolytic ozone generation of the present invention is required The device includes an electrolytic ozone generator, an anode water tank connected to the anode chamber of the ozone generator through an anode circulating water pipe, and a cathode water tank connected to the cathode chamber of the ozone generator through a cathode circulating water pipe. According to the electrolytic ozone generating device of the present invention, the electrolytic ozone generator includes independent cation exchange membranes, which are respectively close to the cation. The paper is a common Chinese national standard (CNS) A4 specification (210X297 mm) -9- 401373 A7 ________B7_ 5. Description of the invention (7) Independent anode catalyst membrane and independent cathode catalyst membrane on both sides of the exchange membrane, anode porous current collector on the other side of the anode catalyst membrane, and cathode catalyst membrane A cathode porous current collector sheet on the other side of the sheet. The cation exchange membrane is a perfluorosulfonic acid cation exchange resin commonly used in the prior art, and the anode catalyst membrane contains 0.2 to 0.3 mm of polytetrafluoroethylene and lead dioxide. Membrane, said cathode catalyst membrane is a membrane containing polytetrafluoroethylene and rhenium carbon powder with a thickness of 0.1-0.2 mm, said anode porous current collector sheet is coated with a layer containing sodium ' A sintered porous titanium sheet with conductive oxide of antimony, and the cathode porous current collector sheet is a sintered porous titanium sheet. In the electrolytic ozone generating device of the present invention, the position of the cathode water tank is higher than that of the anode water tank, and a one-way balancing valve (or an on-off type solenoid valve) is connected between the cathode water tank and the anode water tank to realize automatic balance of raw water and make This device can output ozone with pressure. The raw water in the anode water tank and the cathode water tank is not only the raw material for generating ozone, but also the circulating coolant of the anode and cathode. The preparation method of the ozone generator in the electrolytic ozone generating device of the present invention includes: printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs a. Platinum carbon powder and polytetrafluoroethylene emulsion containing 5-15% by weight of platinum ( Suspension) and an appropriate amount of twice-distilled water in 8 Ot: left and right water bath to stir into a paste ', and then repeatedly rolled at a temperature of 30-40 ° C into a 0.1-0.2mm thick film, where poly The weight of tetrafluoroethylene accounts for 5-15% of the weight of platinum carbon powder. The rolled membrane is dried at 50-60 ° C and cut to the required size to obtain a cathode catalyst membrane (3 3 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -10- A7 B7 V. Description of the invention (8) b _Put lead dioxide powder and polytetrafluoroethylene emulsion with an appropriate amount of secondary distilled water Stir in a water bath at about 80 ° C to form a paste, and then repeatedly roll it at a temperature of 30 to 40 ° C to a thickness of 0.2-0.3 mm, in which the weight of polytetrafluoroethylene accounts for lead dioxide. 1 to 5% by weight, the rolled membrane is dried at 50 to 6 Ot and cut to a desired size to obtain an anode catalyst Sheet (35); c. The sintered porous titanium sheet is degreased and pre-treated with 50 to 20% by weight of hydrochloric acid, rinsed with secondary distilled water to be free of chloride ions, dried, and then on the surface An organic solution containing lead, thorium and antimony was applied and oxidized in an electric furnace at 500-530 ° C to form a thin layer of a conductive oxide containing platinum, thorium and antimony on the surface to obtain a porous anode current collector. Sheet (3 6) d. The sintered porous titanium sheet is degreased and pre-treated with 5-20% by weight of hydrochloric acid, rinsed with secondary distilled water to be free of chloride ions, and dried to obtain a cathode porous aggregate. Streaming film (3 2). The ozone generator of the present invention is assembled by combining the above independent components with other necessary components well known in the art. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ 1. Mj-I-. ^ ϋ i--I n. jn -I • 5, -e-I-(Please read the notes on the back! ^ Write this page) Detailed description of the invention The following is an explanation of the electrolytic ozone generator of the present invention with reference to the drawings. Further detailed description: The electrolytic ozone generating device of the present invention includes an electrolytic odor The generator 8, the anode water tank 18 connected to the anode chamber of the ozone generator 8 through the circulating water pipe 7, and the anode water tank 18 connected to the cathode generator of the ozone generator 8 through the circulating water pipe 6. This paper only applies to Chinese National Standard (CNS) A4 specifications ( 210X297 mm) " ~ " -11-402373 A7 _____B7_ V. Cathode water tank 4 of the invention description (9), one-way balance valve 13, cooling fan 10, 1 1, water level detector 1 9, 2 0, 2 1, 2 2 and isolation tube 1 7. The electrolytic ozone generator 8 includes a cation exchange membrane 34, an anode catalyst membrane 35, an anode porous current collector sheet 36, an anode chamber frame 37, an anode heat sink 3 8, a cathode catalyst membrane 3 3, and a cathode porous Current collecting piece 32, cathode chamber frame 30, deflector 31, anti-corrosion sheet 28 'deflector 27' seal 29 and bolt 40, nut 25 'washer 2 6' 4 2, insulating washer 3 9, drainage screw 4 1 . In the electrolytic ozone generating device of the present invention, the anode water tank 18 has a gas collecting surface 18 a at the upper end, so that the anode gas can be discharged quickly without retention. There is an elongated air guide tube 1 8 b on the gas collecting surface, ozone and oxygen outlets 2 4 on the top of the air guide tube, and a microporous damping plate 2 3 in the air outlet 2 4. The anode water tank is provided with an isolation tube. Printed by a consumer cooperative (please read the note on the back * 45 to write this page) 1 7. It is composed of quartz tube or titanium tube. The anode gas (ozone 'oxygen) and the circulating water produced by the anode reaction are introduced into the anode water tank through this tube. The isolation tube 17 is arranged to reduce the contact and dissolution of ozone and the raw material water in the anode water tank. Ozone and oxygen quickly enter the air duct 18 b through the gas collecting surface 18 a, and the gas / water separation is realized at the upper end of the air duct. The separated ozone and oxygen pass through the microporous damping plate 2 3 and are led out by the ozone and oxygen outlets 2 4. The position of the cathode water tank 4 is higher than that of the anode water tank 18, and the top is provided with a water inlet 2 ', a water inlet cover 1 and a hydrogen outlet 3. The cathode water tank 4 is provided with a water level detector 19 '2 0, 2 1, 2 2'. The water level detector is composed of a reed tube 22, a float 21, and a permanent magnet 20 0 'water level detection sealed tube 19. When the water level in the cathode water tank is too high or too low, a signal is output to stop the generator. This paper size is applicable to China National Standard (C1SS) A4 (210X297 mm) -12- Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 __B7 V. Description of the invention (10) Cathode circulating water pipe 6 The cathode water tank 4 and the cathode The chamber frame 30 is connected to form a water circulation circuit, and the heat generated during the cathode reaction is taken out in time by the water circulation. The anode circulating water pipe 7 connects the anode water tank 18 and the anode chamber frame 37 to form a water circulating circuit ', and the heat generated during the anode reaction is taken out in time by water circulation. According to the electrochemical reaction principle of the electrolytic ozone generator, the production of ozone and oxygen in the anode reaction formulas 3 and 4 requires the consumption of raw water. The protons produced by this reaction migrate to the cathode through the cation exchange membrane in a water-solvated form. When continuing, the raw water in the anode water tank is continuously consumed, while the raw water in the cathode water tank is continuously increasing. The raw material water in the cathode water tank cannot be returned to the anode water tank through the cation exchange membrane in the reverse direction, and the raw water in the anode water tank is completely depleted. In order to solve the above problem, the present invention provides a one-way balancing valve between the cathode water tank and the anode water tank. Referring to Fig. 1 'to Fig. 4, the one-way balancing valve 13 is composed of an upper valve body 51 and a diaphragm 50' and a lower valve body 49. The upper valve body 51 is provided with a cathode water tank interface 4 3, the anode water tank interface 5 2, the interface 5 2 has a damping hole 5 2 a, and a ring-shaped sealing lip 4 5; the unidirectional balanced lower valve body 4 9 is provided with an anode water tank. Connection 47, pressure limiting valve port 48, pressure limiting plug 48a. The cathode water tank interface 43 of the valve body 51 on the one-way balancing valve is connected to the cathode water tank 4, the anode water tank interface 5 2 is connected to the anode water tank 18, and the lower valve body 4 9 of the anode water tank interface 4 7 and the anode water tank 1 8 The size of this paper is applicable to China National Standard (CNS) A4 (210X297 mm) ^ 1---I 'I --- 1--^^ 1 I * ^ vm 1-1 ^ 1-ί I τ » .-,-, (Please read the precautions on the back before writing this page 4) -13- Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 401373 A7 __ B7 V. Description of the invention (n) Start at the ozone generator During operation, the ozone and oxygen in the anode water tank 18 due to the damping of the micro-orifice damping plate 23 gradually develop a pressure P, which passes through the anode water tank interface 5 2 and the lower valve body of the upper body 51 of the one-way balance valve. 4 9 The anode water tank interface 4 7 is transmitted to both sides of the diaphragm 50. At this time, because there is also the cathode water tank interface 4 3 in the upper valve body 51, the raw material water flows from the anode water tank 18 to the cathode water tank 4. . Water flows through the damping hole 5 2 a of the anode water tank interface 5 2 to generate a pressure drop ΔP. The generation of ΔP causes a pressure difference between the two sides of the diaphragm 50. Under this pressure difference, the diaphragm 50 is biased upwardly toward the valve body 51 until it presses on the annular sealing lip 4 5. At this time, the cathode water tank is cut off. 4 and 8 water flow channels with anode water tank. The diaphragm 50 is maintained in this state by the pressure P in the anode water tank 18 being maintained. At this time, the ozone generator device of the present invention can output ozone and oxygen at a pressure P. When the ozone generation efficiency stops working, the pressure P gradually disappears. If the water level of the cathode water tank 4 is higher than the water level of the anode water tank 18, the diaphragm 50 will be biased downward to the valve body 49 by the water level pressure difference, and the cathode water tank 4 and The positive water tanks 18 and 18 are connected again through a one-way balancing valve. The water levels in the negative and positive water tanks will gradually return to equilibrium. The pressure limiting plug 4 8a of the one-way balance valve will be opened when the pressure in the anode water tank 18 is too high, and it will perform pressure limiting protection. In addition to the one-way balancing valve provided between the cathode water tank 4 and the anode water tank 18, the electrolytic ozone generating device of the present invention can also be provided with an on-off solenoid valve, which can also achieve the purpose of water balance. On-off solenoid valve When the device is started, the channel of the cathode and anode water tank is turned off; when the device is stopped, the paper size is suitable for financial and family protection (CNS) A4 · (2 丨 GX297 mm) '~~' '-14- I- II-II—---II I- 1— 1 --- HI Ding---(Please read the notes on the back to write this page first) A7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _____B7_ V. Description of the invention ( 12) The on-off solenoid valve connects the channels of the cathode and anode water tanks. The cooling fans 10, 11 are installed at the lower part of the electrolytic ozone generator 8, and the cooling air blows upward through the fins 38, the anode water tank 18, and the cathode water tank 4 to assist the heat dissipation. The ozone generator in the present invention is made by cold-pressing the following independent diaphragms prepared through different techniques and 1J. The cation exchange membrane 34 used in the present invention is a perfluorosulfonic acid cation exchange membrane (model 1 1 7) produced by DuPont of the United States. The treatment technology is: 10% hydrogen peroxide is immersed at 80-90 ° C for one hour to remove organic impurities in the membrane. After rinsing with a large amount of secondary distilled water at about 60 ° C, immerse it in sulfuric acid of 2 m ο 1/1 for half an hour to remove a small amount of metal ions, and finally use a large amount of about 60 ° C Rinse the secondary distilled water to neutrality, and store in the secondary distilled water for assembly. The preparation technology of the cathode catalyst membrane 33 is: uranium carbon powder (200 holes sieved) containing 5-15% by weight of lead, and a polytetrafluoroethylene emulsion (suspension) and an appropriate amount of secondary distilled water. Stir in a water bath at about 80 ° C to form a paste, and then repeatedly roll at a temperature of 30 to 40 ° C to a thickness of 0.1 mm to 0.2 mm. The weight of polytetrafluoroethylene is 5 to 15% of the weight of uranium toner. The rolled membrane is dried at 50-60 ° C and cut to the required size for use during assembly. The cathode catalyst membrane produced by this technique has porous conductive properties. Hydrogen generated at the catalyst membrane / cation exchange membrane contact interface and water accompanied by proton migration can smoothly pass through the micropores of the cathode catalyst membrane and enter the cathode chamber. The preparation technique of the anode catalyst membrane 3 5 is: the lead dioxide powder (this paper size applies to China National Standard (CNS) A4 specifications (210 × 297 mm) (please read the precautions on the back to write this page) 4Γ -15 -4Q13T9 A7 B7 V. Description of the invention (13) 1 80 holes sieved) and polytetrafluoroethylene emulsion (suspension) and an appropriate amount of secondary distilled water are stirred into a paste at about 8 Ot. Then rolled at a temperature of 30-40 ° C into a 0.2_0.3mm film. Among them, polytetrafluoroethylene accounts for 1-5% of the weight of lead dioxide powder. After drying the membrane, it will be cut to the required size and stored for use during assembly. The anode catalytic membrane produced by this technology has porous conductivity, and ozone and oxygen generated at the anode catalyst membrane / cation exchange membrane contact interface can smoothly enter the anode chamber through the micropores of the anode catalyst membrane; meanwhile, raw water can pass through the anode chamber. The micropores of the membrane reversely migrate into the anode catalyst membrane / cation exchange membrane reaction interface and participate in the anode reaction. A part of the raw material water moves to the cathode compartment along with the protons through the cation exchange membrane. The preparation technique of printed anode porous current collector sheet 36 by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs is: sintered porous titanium sheet (with a maximum pore size of 26 // m and an air permeability of 1 19M3 / m2 · hk P a) After degreasing and pre-treatment with 5-20% by weight of hydrochloric acid, it is rinsed with double distilled water until it is free of chloride ions and then dried. Then the surface is coated with an organic solution containing platinum, rhenium and antimony, and oxidized in an electric furnace at 500-530 ° C to form a thin layer of conductive oxide containing aluminum, tin and antimony on the surface to prevent The porous current collector is passivated when passing through the anode current. The porous current collector made by the above technique has the functions of electrical conduction and gas-liquid conduction (that is, gas products can leave the electrode reaction interface through the current collector; and raw water can enter the electrode reaction interface through the current collector). The weight percentage of the organic solution containing platinum, tin, and antimony described herein is: concentrated hydrochloric acid S — I-2% This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -16- Economic 'Qiu Printed by A7 B7, Consumer Cooperatives of the Central Bureau of Standards 5. Description of Invention (14): S „c 1 4 · 5 Η 2 0 5-1 0% ·· S». C 1 3 0.5 -1 · 5%; C4H9〇 H 60-90%. The preparation technique of cathode porous current collector 32 is: sintered porous titanium plate (maximum pore size is 26, air permeability is 1 1 9M3 / m2.hkPa), after degreasing, use 5-20% (Weight) hydrochloric acid etching, rinse with distilled water until no chloride ions, dry, save, and use when assembled. The porous current collector has electrical conductivity and gas-liquid conduction function. The deflector 31 is a metal titanium plate, The parts formed with longitudinal and horizontal grooves after processing are shown in Fig. 3. The deflectors are respectively assembled in the cathode, and the anode frame constitutes the cathode and the anode. The faces with the longitudinal and horizontal grooves face the cathode respectively, and the anode is porous. Flow piece. The vertical and horizontal grooves of the deflector 31 can contain raw water, and the raw water and gas products convect in the groove. The deflector has a conductive cooling function. The anode chamber frame 37 is made of Teflon material and processed into independent components, as shown in Figure 3. The frame is provided with upper and lower gas nozzles, and is connected with the anode water tank 1 respectively. The 8 phases are connected to form the raw material water circulation circuit in the anode room. With the rise of the gas (ozone, oxygen) generated by the anode reaction and the temperature difference between the raw material water temperature in the anode room and the temperature of the anode water tank as the power, the automatic water circulation is formed. Cooling effect. The cathode chamber frame 30 is made of organic glass or ABS plastic, as shown in Figure 3. The frame is provided with upper and lower gas nozzles, and is connected to the cathode water tank 4, respectively, to form a raw material water circulation circuit in the cathode chamber. The gas (hydrogen) rising force generated by the cathode reaction and the temperature of the raw material water in the cathode chamber are higher than the paper standard. The Chinese National Standard (CNS) A4 specification (210 × 297 mm) is applied. (Please read the precautions on the back and fill in this page first.) , '1T' -17- Α7 Β7 V. Description of the invention U) The temperature difference of the water temperature of the cathode water tank is used as the power to form an automatic circulation of water and play a cooling role. It is made of silicon rubber material, which ensures the sealing of the gas and raw water produced in the yin and yang rooms. Anti-corrosion sheet 2 8 Choose the metal titanium material to prevent the deflector splint from corrosion. The deflector splint 2 7 is made of hard alloy aluminum plate. The ozone and anode electrodes of the generator are connected with an external DC power source. The ozone generator of the present invention is made of the above components by cold pressing assembly method, and the assembly sequence is: IW pole heat sink 3 8, deflector 2 7, anticorrosive sheet 2 8, gasket 29, deflector 3 1, anode chamber frame 37, gasket 29, anode porous current collector sheet 36, anode catalyst membrane 35, cation exchange membrane 3 4 'cathode catalyst membrane 3 3 'cathode porous current collecting sheet 3 2, gasket 2 9' deflector 3 1 'cathode chamber frame 3 〇, gasket 2 9, anticorrosive sheet 28, deflector splint 27, and then use bolts, nuts, washers, insulation The washer is tightened. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back to write this page) The electrolytic ozone generator of the present invention has simple preparation technology and easy assembly. Compared with the prior art ozone generator, The cost of the device can be reduced by 30-50%. In addition, the raw material water in the cathode and anode water tanks of the electrolytic ozone generating device of the present invention can be automatically balanced, and can output ozone higher than atmospheric pressure of 0.1 MPa. The device can perform stably for a long time, and the ozone production efficiency is high. The following table is a comparison of the ozone production efficiency of the device of the present invention and some electrolytic ozone generation devices of the prior art: This paper is suitable for financial institutions (CNS) A4 ^ (2iqx297 (Gongchu) -18- 401373 at ___B7 V. Description of the invention (16) Reference voltage (V) (A / cm2) (%) Reference voltage of the tank voltage and current density ozone generation The present invention 3.5 1.5 18-20 Prior art 1 3.6 1.0 16 US4927800 Existing technology 2 4.0 8 JP43390 / 90 Existing technology 3 3.3 1.0 13 JP20488 / 91 Existing technology 4 4.0 7 JP43389 / 90 Existing technology 5 1.0 13-16 US5203972 Example: Example 1: Preparation of an electrolytic ozone generator (8) (Please read the notes on the back first to write this page) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs a. Preparation of cation exchange membrane (34): 117 type perfluorosulfonic acid cation exchange membrane (product of DuPont) % Hydrogen peroxide is immersed at 90 ° C for one hour to remove organic impurities in the membrane, rinsed with a large amount of secondary distilled water at 60 ° C and then immersed in 80 ° C 2mo 1/1 sulfuric acid for half an hour Remove a small amount of metal ions, and finally rinsed to neutral with a large number of secondary 6 0 ° C distilled water, distilled water, when the secondary assembly to be stored. b. Preparation of cathode catalyst diaphragm (3 3): platinum carbon powder (200 holes sieved) containing 6% (weight) platinum with polytetrafluoroethylene emulsion (suspension) and appropriate amount of secondary distilled water at 8 The film was stirred in a water bath at about 0 ° C to form a paste, and then repeatedly rolled at a temperature of 3 5 ° C to a thickness of 0.1 mm. Among them, the weight of polytetrafluoroethylene accounts for 10% of the weight of uranium carbon powder. The rolled diaphragm is dried at 60 ° C and cut to the required size for use during assembly. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -19- Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (17) C. Anode catalyst membrane (3 5) Preparation: Mix / 3-lead dioxide powder (180 holes sieved) with polytetrafluoroethylene emulsion (suspension) and an appropriate amount of secondary distilled water at about 80 ° C to form a paste. It was then rolled into a 0.2mm film at 40 ° C. Among them, polytetrafluoroethylene accounts for 2% of the weight of lead dioxide powder. The membrane is dried at 5 5 ° C and cut to the required size for storage before use in assembly. d. Preparation of anode porous current collector sheet (3 6): sintered porous titanium sheet (maximum pore size is 2 6 " m, air permeability is 1 1 9M3 / m2 • hk P a), degreased and treated with 1 〇 After etching with% hydrochloric acid, rinse with secondary distilled water until there is no chloride ion, and then dry. Then the surface is coated with an organic solution containing platinum, tin, and antimony, and oxidized in an electric furnace at 520 ° C to form a thin layer of conductive oxide containing uranium, tin, and antimony on the surface. The weight percentage of the organic solution containing uranium, tin, and antimony described therein is: concentrated hydrochloric acid 1%; S „C 1 4 · 5 H a 0 8%: S. ≫ C 1 3 1.0%; C 4 H 9 〇 H 8 5%. E. Preparation of cathode porous current collector sheet (32): sintered porous titanium sheet (with a maximum pore size of 26 and an air permeability of 1 1 9M3 / m2 · hk P a) is used after degreasing Etching with 10% hydrochloric acid, rinsing with distilled water until there are no chloride ions, drying it, storing it, and using it after assembly. Cut the five components prepared above into 8 c m2 squares, cooperate with other components, and follow the anode Heat sink (3 8) 'Flow guide plate (2 7 This paper size applies to China National Standard (CNS) A4 size (210 X 297 mm) (Please read the precautions on the back side first write this page) " ° -20- 40f37 fluorine V. Description of the invention (18)) 'Anticorrosive sheet (28)' Seal (29), deflector (31) 'Anode chamber frame (37)' Seal (29), anode porous current collector (Please read the precautions on the back first and write this page) Sheet (36) 'Anode catalyst membrane (3 5), Cation exchange membrane (34)' Cathode catalyst membrane (3 3), negative Porous current collector sheet (32) 'Seal (29), deflector (31), cathode chamber frame (30), seal (29), anticorrosive sheet (28), deflector (2 7) Arrangement, where the deflector (31) is made of 丄 0mm thick metal titanium plate, which has 7 grooves with a width of 2.5mm and a depth of 6mm evenly distributed on the surface: the cathode chamber frame is made of plexiglass Material injection molding, there is a space of 3 1 X 3 1 X 9 mm 3 in the frame 'the inner diameter of the upper and lower air and water connection nozzles is 4 mm; the anode chamber frame (printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, printed by 3 7) Tetrafluoroethylene storage processing is made into 'the shape, size and inner volume are completely consistent with the cathode chamber frame (30); the anticorrosive sheet (2 8) is made of industrial pure titanium', the thickness is 0.8mm, the area is 40x40mm2; the guide splint (2 7) is a hard alloy aluminum material with a thickness of 8mm and an area of 60x60mm2; and then fastened with bolts (40), nuts (25), washers (26, 42) and insulating washers (39) to obtain the invention Electrolytic ozone generator (8). Example 2: Preparation of electrolytic ozone generator (8) a. Production of cation exchange membrane (34) Preparation: The 117 type perfluorosulfonic acid cation exchange membrane (product of DuPont) was soaked with 10% hydrogen peroxide at 80 ° C for one hour to remove organic impurities in the membrane, and after a large amount of 60 ° C for two times After rinsing with distilled water, put it at 80 ° C 2 m ο 1/1 of the sulphur paper standard applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm) -21-觎 ma? 'B7 1. Description of the invention (19) Soak in acid for half an hour to remove a small amount of metal ions. Finally, rinse with a large amount of secondary distilled water at 6 ◦ ° C to neutrality, and store in secondary distilled water for assembly. b. Preparation of cathode catalyst membrane (33): platinum carbon powder (200 holes sieved) containing 12% (weight) platinum and polytetrafluoroethylene emulsion (suspension) and appropriate amount of secondary distilled water at 80 In a water bath at about ° C, stir into a paste, and then repeatedly roll at a temperature of 40 ° C to form a 0.2 mm thick film. The weight of polytetrafluoroethylene accounts for 15% of the weight of uranium toner. The rolled membrane is dried at 6 and cut to the required size, and 0 C is used for assembly. Preparation of anode catalyst membrane (35): sieving lead dioxide powder (180 holes) Stir with polytetrafluoroethylene emulsion (suspension) and an appropriate amount of secondary distilled water at about 80 ° C to form a paste. It is then rolled at a temperature of 35 ° C into a membrane of 0 · 2 mm. Among them, polytetrafluoroethylene accounts for 1% of the weight of lead dioxide powder. After drying, the membrane is cut to the required size and stored for use during assembly. d. Preparation of anode porous current collector sheet (3 6): sintered porous titanium sheet (maximum pore size is 2 6 // m, air permeability is 1 1 9M3 / m2 • hk P a) after degreasing and using 1 0 After etching with% hydrochloric acid, rinse with secondary distilled water until there is no chloride ion, and then dry. Then the surface is coated with an organic solution containing platinum, tin, and antimony, and oxidized in an electric furnace at 500 ° C to form a thin layer of conductive oxide containing uranium 'tin' antimony on its surface. The weight of the organic solution containing uranium, tin, and chains is divided into: (Please read the precautions on the back and fill in this page first) Order the staff of the Central Standards Bureau of the Ministry of Economic Affairs Standard (CNS) A4 specification (210X297 mm) -22- 0% 2% 20 0% 2% 20 V. Description of the invention (concentrated hydrochloric acid 9%; H2ptc 16.6Η2〇snc 1 ^. 5 Η 2 〇 10 0%; S b C 1 3 c > H 9 Ο H 7 8%. E. Preparation of cathode porous current collecting sheet (3 2): sintered porous sheet (maximum pore size is 2 6 # m, air permeability is 1 1 9M3 / m2.hk P a) After degreasing, it is etched with 0% hydrochloric acid, rinsed with distilled water until no chloride ions, dried, stored, and used until assembly. According to the same method as in Example 1, the The assembly of the above-mentioned components and other components into the electrolytic ozone generator (8) of the invention. Example 3: Preparation of an electrolytic ozone generator (8) a. Preparation of a cation exchange membrane (34): 1 sulfonic acid Cation exchange membrane (product of DuPont) was immersed in 10% at 85 ° C for one hour to remove organic impurities in the membrane, ° After rinsing with C in distilled water, immerse it in 80 ° C 2 m 〇 acid for half an hour to remove a small amount of metal ions. Finally, rinse in distilled water at ° C to neutrality, and store it in secondary distillation. b. Preparation of cathode catalyst membrane (33): paste (weight) uranium lead carbon powder (200 holes sieved) with polytetra (suspension) and appropriate amount of secondary distilled water at 80 ° C And then repeatedly rolled into 0.1 pieces at a temperature of 30 ° C. Among them, the weight of polytetrafluoroethylene accounts for 5% of the weight of uranium toner. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). (Please read the notes on the back first to write this page). 3 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 1 Type 7 perfluorinated hydrogen peroxide. A large amount of 6 0 1/1 of sulfur is used in a large amount of 60. 10% vinyl fluoride emulsion was stirred into a mm-thick film. The rolled -23- Central Standard of the Ministry of Economy 扃 Staff Consumer Cooperative Cooperative Printing Shaft 75-V. Description of the invention (21) The film was baked at 60 ° C Dry and cut to the required size for use during assembly. C · Preparation of anode catalyst membrane (3 5): Θ — Stirred dioxide powder (sieved with 180 holes), polytetrafluoroethylene emulsion (suspension) and an appropriate amount of secondary distilled water are stirred into a paste at about 80 ° C. Then rolled at 3 ° C to 0 · 3mm film. Polytetrafluoroethylene accounts for 1.5% of the weight of the powder. This film is dried after being cut to the required size and stored for use in assembly. d. Preparation of anode porous current collector sheet (3 6): sintered porous titanium sheet (maximum pore size is 2 6 # m, air permeability is 1 1 9 M 3 / m 2 • hk P a) after degreasing and using After 10% hydrochloric acid is etched and pre-treated, it is rinsed with secondary distilled water to be free of chloride ions and then dried. Then, the surface is coated with an organic solution containing uranium'tin and antimony, and oxidized in an electric furnace at 520 ° C, so that a thin layer of conductive oxide containing ferrite, tin, and antimony is formed on the surface. The weight percent of the organic solution containing platinum, tin, and antimony described therein is: concentrated hydrochloric acid 1.5%; S n C 1 1 · 5 Η 2 0 5%; S, > C 1 3 0.5%: C 4 H 9 0 H 90%. e · Preparation of cathode porous current collector sheet (3 2): sintered porous titanium sheet (maximum pore size is 2 6 and air permeability is 1 1 9M3 / m2 · hk P a) is etched with 10% hydrochloric acid after degreasing , Rinse with double distilled water until there is no chloride ion, dry it, store it, and use it for assembly. According to the same method as in Example 1, the above-prepared element and its paper size were applied to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1 ^ m-----1 1 ^ 1 n I mi In ^^ 1-.¾., I (please read the precautions on the back first ^ write this page) -24-A7 ________B7 V. Description of the invention (22) Its component assembly cost is the electrolytic ozone generator (8) of the invention. Embodiment 4: The assembly and application of the electrolytic ozone generating device of the present invention uses the electrolytic ozone generator (8) prepared in Example 1 and the following components: a cathode water tank (4) of 1500 ml, 1200 Milliliter anode water tank (1 8) 'one-way balance valve (1 3), cooling fan (1 0 '11)' anode circulating water pipe (7), cathode circulating water pipe (6), water level detector (1 9, 2 0 2 1, 2 2) and the isolation tube (1 7) are installed according to methods known in the art to form the electrolytic ozone generating device of the present invention. When the electrolytic ozone generating device of this embodiment is performed at a current density of 1.5 A / cm2, the generator tank voltage is 3.5 ± 0. IV, and the ambient temperature is about 2 5 ° C, which is continuously performed for 2 4 The temperature of the raw material water in the anode and anode water tanks can be maintained at about 30 ° C, and the ozone generation efficiency is 18%. The anode water tank can output a pressure higher than the atmospheric pressure of 0.08MPa. The ozone printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back first to write this page). Brief description of the drawings: FIG. 1 is a schematic structural diagram of an electrolytic ozone generating device according to the present invention. Fig. 2 is an assembly schematic diagram of the electrolytic ozone generating device (8) of the solid polymer electrolyte membrane composite electrode in Fig. 1. FIG. 3 is a developed view of FIG. 2. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -25- 401373 V. Description of the invention (23) Supplement f
圖4爲單向平衡閥13的結構示意圖 主要元件對照表 1 加水口蓋 2 加水口 3 氫氣出口 4 陰極水箱 5 反應介質 6 陰極循環水管 7 陽極循環水管 8 臭氧發生器 9 陽極循環水管 10-11 冷卻風機 1 2 循環水管 13 單向平衡閥 14 陰極循環水管 15 螺母 16 備用放水口. 17 隔離管 18 陽極水箱 18a 集氣面 18b 導氣管 19 水位檢測密封管 2 0 永磁體 -------------------—訂I:--------線"、 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用尹國國家標準（CNS)A4規格（210 X 297公釐） -26- 461375 五、發明說明（24 2 1 浮子 2 2 2 4 2 5 2 6 2 7 2 8 2 9 3 0 3 1 3 2 3 3 3 4 3 7 3 8 3 9 4 0 4 1 4 2 4 3 4 4 舌簧管 微孔阻礙板 出氣口 螺母 墊圈 導流夾板 防腐片 密封墊 陰極至框架 導流板 陰極多孔集流片 陰極催化劑膜片 陽離子交換膜片 陽極催化劑膜片 陽極多孔集流片 陽極室框架 陽極散熱片 絕緣墊圈 螺栓 引流螺釘 墊圈 陰極水箱接口 陽極水箱接口Figure 4 shows the structure of the one-way balance valve 13. The main components are compared with the table 1 water inlet cover 2 water inlet 3 hydrogen outlet 4 cathode water tank 5 reaction medium 6 cathode circulating water pipe 7 anode circulating water pipe 8 ozone generator 9 anode circulating water pipe 10-11 cooling Fan 1 2 Circulating water pipe 13 One-way balancing valve 14 Cathode circulating water pipe 15 Nut 16 Spare water outlet. 17 Isolating pipe 18 Anode water tank 18a Air collecting surface 18b Air duct 19 Water level detecting sealing tube 2 0 Permanent magnet ------- ------------— Order I: -------- line ", (Please read the precautions on the back before filling this page) This paper size applies Yin National Standard ( CNS) A4 specification (210 X 297 mm) -26- 461375 V. Description of the invention (24 2 1 Float 2 2 2 4 2 5 2 6 2 7 2 8 2 9 3 0 3 1 3 2 3 3 3 4 3 7 3 8 3 9 4 0 4 1 4 2 4 3 4 4 Reed tube micro hole obstruction plate air outlet nut washer baffle plate anticorrosive sheet gasket cathode to frame deflector cathode porous current collector cathode cathode membrane cation exchange membrane Sheet anode catalyst diaphragm anode porous current collecting sheet anode chamber frame anode heat sink insulating washer bolt drainage Screw washer Cathode water tank connection Anode water tank connection
(請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用令國國家標準（CNS)A4規格（210 X 297公釐） -27- A7 A7(Please read the precautions on the back before filling out this page) The paper size applies the national standard (CNS) A4 (210 X 297 mm) -27- A7 A7
--------------------訂----一-----線· - -* (諳先閲讀背面之注意事項再填寫本頁> _B7 五、發明說明（25 ) 45 環狀密封唇 4 6 陽極水箱接口 4 7 陽極水箱接口 4 8 限壓閥口 4 8a 限壓塞 4 9 單向平衡閥下閥體 5 0 膜片 51 單向平衡閥上閥體 52 陽極水箱接口 52a 阻礙孔 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -28 --------------------- Order ---- a ----- line ·--* (谙 Please read the notes on the back before filling this page > _B7 V. Description of the invention (25) 45 Ring-shaped sealing lip 4 6 Anode water tank connection 4 7 Anode water tank connection 4 8 Pressure limiting valve port 4 8a Pressure limiting plug 4 9 Lower check valve body 5 0 Diaphragm 51 Unidirectional Body valve on balance valve 52 Anode water tank connection 52a Obstructed hole The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -28-
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97209412 | 1997-03-07 | ||
| CN97122126A CN1128759C (en) | 1997-03-07 | 1997-11-19 | Electrolytic ozone generator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW401373B true TW401373B (en) | 2000-08-11 |
Family
ID=25744409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW086117241A TW401373B (en) | 1997-03-07 | 1997-11-17 | Electrolytic ozone generating apparatus |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP3025473B2 (en) |
| CN (1) | CN1128759C (en) |
| AU (1) | AU6288498A (en) |
| TW (1) | TW401373B (en) |
| WO (1) | WO1998040535A1 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001181876A (en) | 1999-12-22 | 2001-07-03 | Teeiku Wan Sogo Jimusho:Kk | Ozone generating electrolytic cell and its manufacturing method |
| TW200528390A (en) * | 2004-02-25 | 2005-09-01 | Toshiba Mitsubishi Elec Inc | Apparatus and method of producing ozone gas |
| CN1900367A (en) * | 2005-07-20 | 2007-01-24 | 徐名勇 | Anode structure of electrolytic ozone generator |
| CN2854261Y (en) * | 2005-07-20 | 2007-01-03 | 徐名勇 | Thin-film check valve used in ozone/ozone water loop |
| HUP0501204A2 (en) * | 2005-12-23 | 2007-07-30 | Thales Rt | Ozone generating electrolytic cell |
| CN101250710B (en) * | 2008-03-28 | 2010-06-09 | 陕西科技大学 | Electrolytic ozone generator and preparation technique for cathode catalysis layer thereof |
| CN101289749B (en) * | 2008-06-04 | 2010-10-06 | 徐伟钧 | Spring bearer plate structure for fastening anodic of electrolytic ozone generator |
| CN101698942B (en) * | 2009-02-11 | 2011-08-10 | 徐名勇 | Ozone generator for use in membrane electrode electrolysis |
| CN201746592U (en) * | 2010-06-22 | 2011-02-16 | 刘迅 | Water electrolysis device |
| CN102181879A (en) * | 2011-04-12 | 2011-09-14 | 周美荣 | Electrolytic ozone generating device capable of recycling cathode water |
| CN103498954B (en) * | 2013-10-11 | 2015-07-08 | 苏州竞立制氢设备有限公司 | Double-system balance valve |
| CN104032326B (en) * | 2014-03-03 | 2017-02-01 | 上海维埃姆环保科技有限公司 | Titanium steel guide plate and generator adopting the guide plate |
| CN103981532A (en) * | 2014-05-30 | 2014-08-13 | 李欣 | Novel membrane electrode electrolysis ozone generator |
| CN107469121A (en) * | 2017-09-29 | 2017-12-15 | 深圳欧威奇科技有限公司 | A kind of air purifying and sterilizing machine |
| CN107441543A (en) * | 2017-09-29 | 2017-12-08 | 深圳欧威奇科技有限公司 | Air purifying and sterilizing machine |
| CN108301013B (en) * | 2018-02-14 | 2020-05-12 | 中氧科技（广州）有限公司 | Preparation method of modified lead dioxide anode for ozone |
| CN108977828B (en) * | 2018-10-19 | 2023-11-03 | 胡松 | Membrane electrode electrolytic ozone generator and preparation process thereof |
| CN109338399A (en) * | 2018-11-19 | 2019-02-15 | 武汉威蒙环保科技有限公司 | A kind of built-in gas water cyclic electrolysis formula ozone generating-device |
| CN112744903A (en) * | 2019-10-30 | 2021-05-04 | 无锡维邦工业设备成套技术有限公司 | Electrolyzed water ozone-making type purified water sterilization system |
| CN114293211B (en) * | 2021-12-30 | 2023-09-05 | 深圳康诚博信科技有限公司 | Ozone generator with rapid disassembly and assembly structure and preparation method of cathode prefabricated film of ozone generator |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4316782A (en) * | 1980-05-29 | 1982-02-23 | Regents Of The University Of California | Electrolytic process for the production of ozone |
| JP2840753B2 (en) * | 1989-03-31 | 1998-12-24 | 株式会社ササクラ | Ozone electrolytic production method |
| JPH0320488A (en) * | 1989-06-19 | 1991-01-29 | Permelec Electrode Ltd | Method for generating ozone by water electrolysis |
| US5460705A (en) * | 1993-07-13 | 1995-10-24 | Lynntech, Inc. | Method and apparatus for electrochemical production of ozone |
| CN2229460Y (en) * | 1993-11-24 | 1996-06-19 | 武汉大学 | Solid polymer electrolyte film electrode electrolytic ozonator |
| JPH07157301A (en) * | 1993-12-08 | 1995-06-20 | Hitachi Maxell Ltd | Ozone generator |
-
1997
- 1997-11-17 TW TW086117241A patent/TW401373B/en not_active IP Right Cessation
- 1997-11-19 CN CN97122126A patent/CN1128759C/en not_active Expired - Fee Related
-
1998
- 1998-03-04 AU AU62884/98A patent/AU6288498A/en not_active Abandoned
- 1998-03-04 WO PCT/CN1998/000030 patent/WO1998040535A1/en active Application Filing
- 1998-03-09 JP JP10057071A patent/JP3025473B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AU6288498A (en) | 1998-09-29 |
| CN1128759C (en) | 2003-11-26 |
| WO1998040535A1 (en) | 1998-09-17 |
| JPH111789A (en) | 1999-01-06 |
| JP3025473B2 (en) | 2000-03-27 |
| WO1998040535A8 (en) | 1999-06-10 |
| CN1195643A (en) | 1998-10-14 |
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