TW201113224A - Power type waste water treatment system - Google Patents
Power type waste water treatment system Download PDFInfo
- Publication number
- TW201113224A TW201113224A TW98134606A TW98134606A TW201113224A TW 201113224 A TW201113224 A TW 201113224A TW 98134606 A TW98134606 A TW 98134606A TW 98134606 A TW98134606 A TW 98134606A TW 201113224 A TW201113224 A TW 201113224A
- Authority
- TW
- Taiwan
- Prior art keywords
- electric energy
- wastewater treatment
- energy type
- type wastewater
- treatment system
- Prior art date
Links
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Description
201113224 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種以使用電解方式來進行廢水或是污水 之處理裝置；特別是有關於提供一種電能式之廢水或是污水之 處理裝置，其係組合電凝聚（EC)裝置以及臭氧產生裝置，並 於電凝聚（EC)裝置以及臭氧產生裝置施加一電源後，藉由對 廢水連續流過電極之處理方式’以廢水為產生處理劑之媒介或 原料，來將廢水中的污染物當場(in-situ)去除，以達到廢水或是 污水之排放標準。 【先前技術】 飲用水的消毒殺菌對人體健康可謂至為重要之一環。不論 水的來源為何’其中必然含有某些形式的微生物，包括細菌、 病毒或單細胞生物等。在此等微生物中’致病有機體引起的腹 瀉、傷寒、肝炎和霍亂等病症’可能導致飲用者的死亡。因此 基於安全考量’飲用前必須將水中的各種病原體消滅。此外， 來自工廠和農地的毒性有機化合物、醆、鹼、肥料以及殺蟲劑 等，亦可能流入供應民生用水的蓄水場。由於這些化合物極可 能致癌，因此也須於使用這些被污染的水之前，宜先行對此污 染水中的化合物解毒或消毒° 對污染水的消毒方法主要有四種’亦即加氯消毒、氯胺消 毒、臭氧消毒以及紫外線消毒；顯然地，在上述這些方法中， 使用氯（Cl2)氣、次氣酸鈉（Na〇Cl)溶液或次氯酸鈣[Ca(OCl)2] 粉末等的加氣消毒法使用最為廣泛。然而’除了添加化學藥劑 之外，亦可能如美國專利第3,622,479、4,512,865以及7,011，750 號等案所述，利用電氣化學產生次氯酸根離子以達成加氯消毒。 201113224 雖然加氯消毒的可行性已經確認，但其處理過程中所產生 的臭氣、異味，以及其反應緩慢、酸鹼值範圍狹窄和消毒殘劑 餘物可能成為致癌物質⑽闕為人料n肖毒法係利用 f成於氨（nh3)與次氯酸鹽（ocr)之間的消毒劑，然而不論 氣酸鹽或氯胺皆無法對有害化學藥劑產生解毒作用，因此氣胺 消毒法之效果仍有不足。 臭氧消毒與紫外_毒則為兩種錢留疑慮之消毒技術。 事實上’紫外線消毒法係如美國專利第4,230,571與4,968,483 號案所揭示’以紫外雜射氧氣而產生消毒用的臭氧。此外， 紫外線輻射亦透過形成氫氧自由基（·〇Η)而提升臭氧的殺菌 效果’這是因為氫氧自由基為較臭氧更強之氧化劑，如美國專 利第7,063,794號案所述。然而，紫外線並無法消滅梨形鞭毛蟲 或隱抱子蟲（OyptospoHdium)包囊，且亦不適合處理因其中 含有大量懸浮固體、關、有色或芳香族化合物而導致光線減 .弱的水。然而，對於含有毒化學藥劑的工業用水之消毒而言， 氣外線雖然作用緩慢但通常頗具成效。因此，若以紫外線做為 臭氧於消毒解毒的方式，則可獲致最佳效果。 若要快速的產生臭氧時’其製造通常施以極高的電壓，例 如3000V之高電壓，然後藉由電暈放電以分解氧分子而形成氧 的三原子同素異形物。因此，用電即佔總臭氧生產操作成本之 26-43%，且放電過程中’易於產生例如氮氧化物（Ν〇χ)等污 染空氣之物質。另外，如何將氣體均勻分佈於水中’則成為另 -方面的問題。因此’由效率角度觀之’使用低電壓之水電解 來f生的臭氧方式，亦即習知的電解臭氧，相較於氣體加工或 電暈放電更具效率。現已有愈來愈多文獻報告提供將電解臭氧 用於水的消毒和解毒之技術，如美國專利帛5，術，55〇 ; 201113224 5,686,051 ; 5,744,028 ; 6,328,862 ; 6,733,638 ; 6,902,670 與 6,984,295號等案所揭露者，此處僅略舉數例。 此外’就水的消毒解毒而言，臭氧為安全、乾淨、便利以 及強效之氧化劑。臭氧的應用範圍廣及個人口腔衛生、居家清 潔與洗滌’乃至於工業加工和廢水處理。目前全世界已至少有 十七國將臭氧療法採用為合法的醫學療法。雖然臭氧療法尚未 通過美國食品藥物管理局（FDA)核可，但已至少有十二州通 過立法，允許臭氧療法成為一種可供選擇的治療方式。臭氧的 醫療用途可見於美國專利第4,968,483號案之血液氧化療法 (haematological)，美國專利第5,834,030號案之外傷治療以及 美國專利第6,902,670號案中，用於清洗血液透析機導管以取代 可能產生化學殘留的醋酸或甲醛。於工業應用上，如美國專利 第6,851,873及6,983,756號案所述，將臭乳用於制除光阻薄膜， 以及如美國專利第7,029,589號案所述’分解揮發性有機化學 物。臭氧於上述之所有應用中提供破壞性的氧化作用，而其許 多新型態之應用，如消除固體、液體和氣體污染物，亦正逐漸 被開發。 無疑地’臭氧為一種可多方面應用的消毒劑。然而，臭氧 產生過程中伴隨的煙霧卻影響了人們對臭氧的評價，甚至恭遍 將臭氧誤解為危險或致命化學物，而#友善的媒介。這是2為 臭氧之氣體壽命有限（約3〇分鐘），故臭氧並不適於儲存1送， 故必須於使用前或使用當場再即時生產。如上文中所述，雖然 低電壓電解法為最佳的臭氧產生方式（例如：前述之至2的 號等專利）’但卻同樣存在三個問題。問題之一是以電解水來形 成臭氧，其所需之陽極材料為鉑（pt)戒β-二氧化岛（pb〇 )。 然而，钻的價格極高，且於室溫下無法有效產生臭氧另外 201113224 一氧化紐雖然可於室溫下有效產生臭氧9但鉛為一環境有害 θ’而遭許多國家禁止用於水質處理。接著，前案電解臭氧方 法的問題之二在於臭氧生產需要離子交換膜（membrane)。此 離子交換膜除了成本高昂外，由於離子交換膜易受污染物污 染’因此不能直接放置於廢水中，故其使用的範圍亦有嚴格限 制。很明顯地，使用離子交換膜產生電解臭氧僅能如同電暈放 電—樣’須先於他處形成臭氧，而後再將氣體輸送至水中以為 /肖母之用。因此’亦產生電解臭氧的第三種問題，亦即無法達 見努即時消毒的效果。是以’吾人亟需尋求一種效率高且經 濟的電解水生成臭氧方式，以達成便利有效使用臭氧的目標。 【發明内容】 馨於上述之發明背景中，為了符合產業上某 來，本發明# 一 Λ 皿、而 可以在 一主要的目在提供一種電能式廢水的處理系統， 卜不需添加任何化學成份狀況下，藉由對廢水的電 生臭乳，以達到要消毒的目的。 產 本發明之另一主尊沾 么姑, 要的目的在於提供一種電能式廢水的處理 ::會:=:::解_取代任何添加化學成份的方: 本發明之之再—主& ,的目的在於提供一種電能式廢水的虛 理系統純用廢水連續流的處 為產生處關之媒介或 因此心廢水 去除，故本發明之H切^將廢水巾的污染物當場(in-situ) 何化學成份狀況下，㈣7處理U 6GG可以在不需添加往 生產用水。 藉由對廢水的電解使得廢水處理或再生成 本發明之再一主要 系統，以電解之方式來處^於提供—種電能式廢水的處理 廢水，可以提高廢水的回收率，、 Μ 201113224 增加水的再利用，進一步達到省水之功能。 本發明之還有一主要的目的在於提供一種電能式廢水的處 理系統’其可依據所要處理之廢水成份做不同的電能式電解装 置之組合，使得廢水的處理系統可以符合客製化之需求。 本發明之再一主要目的在於提供一種電能式廢水的處理系 統係以摻雜二氧化錫（M-Sn02)膜為電極，以進行各種廣水 之電解與消秦，若配合適當裝置，可以使得經過處理後的廢水 達到生物飲 用標準。 矣本發明之再一主要目的在於提供一種電能式廢水的處理系 、=* ’係以摻雜二氧化錫（M-Sn02)膜為電極作為產生臭氧反應， 工，摻雜二氡化錫（M_Sn〇2)厚膜之電極具有產生大量臭氧之 1 力能’故可降低電能之消耗。 依據上述之目的，本發明首先提供一種電能式之廢水處理 ^辑^係由一電凝聚裝置（EC)與一臭氧產生裝置串接所組成， 置 h電此式之廢水處理系統之特徵在於：廢水經過電凝聚裝 後（ec)並與電凝聚裝置（EC)中的陽極電極與陰極電極反應 再經由臭氧產生裝置中的堆疊電極處理。 本發明接著提供一種電能式之廢水處理模組，包括一電凝201113224 VI. Description of the Invention: [Technical Field] The present invention relates to a treatment device for performing waste water or sewage by using an electrolytic method; in particular, for providing an electric energy type wastewater or sewage treatment device, The invention relates to a combined electrocoagulation (EC) device and an ozone generating device, and after a power source is applied to the electrocoagulation (EC) device and the ozone generating device, the wastewater is used as a treatment agent by treating the wastewater continuously through the electrode. Medium or raw material to remove in-situ contaminants from wastewater to meet wastewater or wastewater discharge standards. [Prior Art] Disinfection of drinking water is one of the most important aspects of human health. Regardless of the source of the water, it must contain certain forms of microorganisms, including bacteria, viruses or single-celled organisms. In such microorganisms, diseases such as diarrhea, typhoid, hepatitis and cholera caused by pathogenic organisms may cause death to the drinker. Therefore, based on safety considerations, various pathogens in the water must be eliminated before drinking. In addition, toxic organic compounds, alfalfa, alkalis, fertilizers, and pesticides from factories and agricultural land may also flow into water storage sites that provide water for people's livelihood. Since these compounds are highly likely to cause cancer, it is also necessary to detoxify or disinfect the compounds in the contaminated water before using these contaminated water. There are four main methods for disinfecting contaminated water, namely chlorination and chloramine. Disinfection, ozone disinfection, and ultraviolet disinfection; obviously, in the above methods, chlorine (Cl2) gas, sodium hypochlorite (Na〇Cl) solution or calcium hypochlorite [Ca(OCl)2] powder is added. Gas disinfection is the most widely used. However, in addition to the addition of chemicals, hypochlorite ions may be generated by electrochemistry to achieve chlorination as described in U.S. Patent Nos. 3,622,479, 4,512,865 and 7,011,750. 201113224 Although the feasibility of chlorination has been confirmed, the odor and odor generated during the treatment, as well as its slow reaction, narrow pH range and residue of disinfectant residue may become carcinogens (10) The toxic method uses a disinfectant that is formed between ammonia (nh3) and hypochlorite (ocr). However, neither the gas sulphate nor the chloramine can detoxify the harmful chemical agents. The effect is still insufficient. Ozone disinfection and UV-toxicity are disinfection techniques for both types of money. In fact, the ultraviolet disinfection method, as disclosed in U.S. Patent Nos. 4,230,571 and 4,968,483, produces ozone for disinfection by ultraviolet miscible oxygen. In addition, ultraviolet radiation also enhances the bactericidal effect of ozone by forming a hydroxyl radical (·〇Η). This is because the hydroxyl radical is a stronger oxidant than ozone, as described in U.S. Patent No. 7,063,794. However, ultraviolet light does not destroy the P. cerevisiae or OyptospoHdium encapsulation and is not suitable for treating water that is weakened by a large amount of suspended solids, colored, or aromatic compounds. However, for the disinfection of industrial water containing toxic chemicals, the gas line is slow but usually effective. Therefore, if ultraviolet light is used as a means of disinfecting and detoxifying ozone, the best results can be obtained. In order to rapidly generate ozone, it is usually manufactured by applying a very high voltage, for example, a high voltage of 3000 V, and then decomposing oxygen molecules by corona discharge to form a three-atomic allotrope of oxygen. Therefore, the electricity consumption accounts for 26-43% of the operating cost of the total ozone production, and during the discharge process, substances which pollute the air such as nitrogen oxides (Ν〇χ) are easily generated. In addition, how to distribute the gas evenly in the water becomes another problem. Therefore, the ozone method of using low-voltage water electrolysis from the viewpoint of efficiency, that is, conventional electrolytic ozone, is more efficient than gas processing or corona discharge. More and more literature reports have been published on the use of electrolytic ozone for the disinfection and detoxification of water, such as US Patent 帛 5, surgery, 55 〇; 201113224 5, 686, 051; 5, 744, 028; 6, 328, 862; 6, 733, 638; 6, 902, 670 and 6, 984, 295, etc. The exposer, just to name a few. In addition, in terms of disinfection and detoxification of water, ozone is a safe, clean, convenient and potent oxidant. Ozone is used in a wide range of applications, including oral hygiene, home cleaning and washing, and even industrial processing and wastewater treatment. At least 17 countries around the world have adopted ozone therapy as a legitimate medical therapy. Although ozone therapy has not yet been approved by the US Food and Drug Administration (FDA), at least 12 states have passed legislation that allows ozone therapy to be an alternative treatment. The medical use of ozone can be found in the blood oxidative therapy (haematological) of the U.S. Patent No. 4,968,483, the esthetic treatment of the U.S. Patent No. 5,834,030, and the U.S. Patent No. 6,902,670, which is used to clean the hemodialysis catheter to replace the possible chemistry. Residual acetic acid or formaldehyde. Styrofoam is used to make photoresist films as described in U.S. Patent Nos. 6,851,873 and 6,983,756, the disclosure of which is incorporated herein by reference. Ozone provides destructive oxidation in all of the above applications, and many of its new applications, such as the elimination of solid, liquid and gaseous contaminants, are being developed. Undoubtedly, ozone is a disinfectant that can be applied in many ways. However, the accompanying smog in the ozone production process has affected people's evaluation of ozone, and even misunderstood ozone as a dangerous or deadly chemical, and #friendly media. This is a gas with a limited life of 2 (about 3 minutes), so ozone is not suitable for storage, so it must be produced immediately before use or on the spot. As described above, although the low-voltage electrolysis method is the optimum ozone generation method (e.g., the aforementioned Patent No. 2), there are three problems. One of the problems is to form ozone by electrolyzing water, and the anode material required is platinum (pt) or β-oxide island (pb〇). However, the price of the drill is extremely high and ozone cannot be effectively produced at room temperature. 201113224 Although it can effectively produce ozone at room temperature, lead is an environmentally harmful θ' and is prohibited from being used for water treatment in many countries. Next, the second problem of the prior method of electrolyzing ozone is that ozone production requires an ion exchange membrane. In addition to the high cost, the ion exchange membrane is strictly limited in its use because the ion exchange membrane is susceptible to contamination by contamination and therefore cannot be directly placed in the wastewater. Obviously, the use of an ion exchange membrane to produce electrolytic ozone can only be as corona discharge-like, and ozone must be formed before it, and then the gas is transported to the water for use. Therefore, the third problem of electrolytic ozone is also produced, that is, the effect of instant disinfection cannot be achieved. Therefore, it is urgent for us to seek an efficient and economical method of generating ozone by electrolyzed water to achieve the goal of facilitating the effective use of ozone. SUMMARY OF THE INVENTION In the above-mentioned background of the invention, in order to comply with the industry, the present invention can provide a treatment system for an electric energy type wastewater in a main purpose, without adding any chemical components. Under the condition, the electric odor milk of the waste water is used for the purpose of disinfection. Another main purpose of the present invention is to provide a treatment for electric energy type wastewater::::::: Solution_Replace any party that adds chemical components: Re-invention of the present invention-main & The purpose of the invention is to provide a waste water system of electric energy type waste water. The continuous flow of pure waste water is used as a medium to generate the waste or thus the waste water is removed. Therefore, the H cut of the present invention will bring the pollutants of the waste water on the spot (in-situ Under the condition of chemical composition, (4) 7 treatment of U 6GG can be done without adding water to production. By the electrolysis of wastewater, the wastewater treatment or regeneration is still another major system of the invention, and the treatment wastewater of the electric energy type wastewater can be provided by electrolysis to improve the recovery rate of the wastewater, Μ 201113224 Reuse to further achieve the function of water saving. Still another object of the present invention is to provide a treatment system for an electric energy type wastewater which can be combined with different electric energy type electrolyzers depending on the composition of the wastewater to be treated, so that the treatment system of the wastewater can meet the needs of customization. Another main object of the present invention is to provide an electric energy type wastewater treatment system which uses a doped tin oxide (M-SnO 2 ) film as an electrode to perform electrolysis and quenching of various kinds of water, and if equipped with appropriate devices, The treated wastewater reaches the bio-drinking standard. A further main object of the present invention is to provide a treatment system for electric energy type wastewater, which is based on a doped tin dioxide (M-SnO 2 ) film as an electrode for generating an ozone reaction, and is doped with tin antimonide ( M_Sn〇2) The thick film electrode has a strong energy to generate a large amount of ozone, thus reducing the consumption of electrical energy. According to the above object, the present invention firstly provides an electric energy type wastewater treatment system which is composed of an electrocoagulation device (EC) and an ozone generating device connected in series. The waste water treatment system of the electric type is characterized in that: The wastewater is electrocoagulated (ec) and reacted with the anode and cathode electrodes in the electrocoagulation unit (EC) and then through the stacked electrodes in the ozone generator. The present invention further provides an electric energy type wastewater treatment module including a coagulation
St要〆 :CEC)與一臭氧產生裝置串接所組成之電能式之廢水處 模級 電源供應器以及一泵浦，其中該電能式之廢水處理 之特徵在於：廢水經過電凝聚裝置（EC)並與電凝聚裝置 C)中的陽極電極與陰極電極反應後，再經由臭氧產生裝置 中的堆疊電極處理。 能式 月還提供—種電能式之廢水處理系統，係由複數個電 包括一廢水處理模組所組成，而每一該電能式之廢水處理模組 聚裝置（EC)與一臭氧產生裝置串接所組成之電能 201113224 式之廢水處理系統、—電β 之廢水處理系統之特徵在:供應器以及一泵浦，其中該電能式 並與每一電凝聚裝置廢尺、、’至過母一電凝聚裝置（EC) 再經由每一臭氧產生裝番 的以極電極與陰極電極反應後， 、 ^巾的堆疊電極處理。 【實施方式】 本發明在此所探討的方 及臭氧之電能式電解裝置^為—種電壓電解水產生電凝聚以 列的描述巾提㈣盡料 了賴魏_本發明，將在下 於臭氧產生裝置之技藝者所地，本發明的施行並未限定 斤热翫的特殊細節。另一方面，眾·所 周知的低電壓電解水產生臭 A ^ 、氧之過程並未描述於細節中，以避 免也成本發明不必要之限制。本發明的較佳實施例會詳細描述 如I ’㈣除了這些詳細描述之外，本發㈣可以廣泛地施行 在其他的實施财，且本發明的範解受限定，其以之後的專 利耗圍為準。 -氧化錫（Sn02)為—種無毒性半導體，其目前已被廣泛 用於感應器、電池、電變色窗戶、太陽能電池以及液晶顯示器 (L )的生產如R. K〇tz之「使用超高伏陽極進行電氣化 子廢水處理’第-輯·二氧化錫陽極之物理及電氣化學特性」 以及應用電氣化學期刊第21卷第，第14 2()頁（顧年） 所指出，純二氧化錫為-n型半導體，具有—約為3 5eV的直 接能隙。另外’三氧化錫尚具有其他特性：⑴高化學和電氣化 學穩定性；⑺高電子傳導性以及(3)高析氧過電位（high〇xygen evolution overpotendai)。其中對於電解臭氧尤有助益的性能是 二氧化錫的氧過電位較Ιό高為G.6V。由成本角度觀之，二氧化 錫亦較#更具優勢。雖則美國專利第5,364,5Q9、4,839,〇〇7和 3,627,669號等案中對於以二氧化錫進行廢水處理已有敘及，但 201113224 其於材料改良與反應器或電解器應之效率仍有待改進。二氧化 錫可摻雜一或多種金屬，例如銻（Sb)、鎳（Ni)、鐵（Fe)、 訂（Ru)、#⑻、把（Pd)、錢（Rh)㈣（c。），或者其亦 可與一非金屬摻雜，如氟（F)。此外，為提昇臭氧產生效率，St. 〆: CEC) is an electric energy type mold-level power supply and a pump composed of an ozone generating device connected in series, wherein the electric energy type wastewater treatment is characterized in that the wastewater passes through an electrocoagulation device (EC). And after reacting with the anode electrode and the cathode electrode in the electrocoagulation device C), it is further processed through the stacked electrode in the ozone generating device. Energy-type monthly also provides an electric energy type wastewater treatment system, which is composed of a plurality of electric power including a wastewater treatment module, and each of the electric energy type wastewater treatment module assembly device (EC) and an ozone generating device string The electric energy treatment system of the 2011201124 type of waste water treatment system, the electric waste water treatment system is characterized by: a supply device and a pump, wherein the electric energy type is combined with each electric coagulation device, and the The electrocoagulation device (EC) is further processed by the stacked electrode of each of the ozone generating devices after the electrode and the cathode electrode are reacted. [Embodiment] The invention and the ozone electric energy type electrolyzing device discussed herein are a type of voltage electrolyzed water to produce electrocoagulation, and the description of the towel is provided. (4) As far as the Lai Wei is concerned, the invention will be produced under ozone. The particulars of the present invention are not limited by the practice of the present invention. On the other hand, the well-known process of producing odor A ^ and oxygen by low-voltage electrolyzed water is not described in detail to avoid unnecessary limitations of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S) In addition to these detailed descriptions, the present invention can be widely implemented in other implementations, and the scope of the present invention is limited by the following patents. quasi. - Tin oxide (Sn02) is a non-toxic semiconductor that has been widely used in the production of inductors, batteries, electrochromic windows, solar cells, and liquid crystal displays (L) such as R. K〇tz. The voltaic anode is used for the treatment of electrified wastewater. The physico-chemical and electro-chemical properties of the tin-tin oxide anode, and the Journal of Applied Electrochemistry, Vol. 21, No. 14 2 () (Gu yin), pure tin dioxide is An n-type semiconductor having a direct energy gap of about 35 eV. In addition, 'tin trioxide has other properties: (1) high chemical and electrical chemical stability; (7) high electron conductivity and (3) high oxygen evolution overpotendai. Among them, the performance that is particularly helpful for electrolytic ozone is that the oxygen overpotential of tin dioxide is higher than G.6V. From a cost perspective, tin dioxide is also more advantageous than #. Although the use of tin dioxide for wastewater treatment has been described in U.S. Patent Nos. 5,364,5Q9, 4,839, 〇〇7 and 3,627,669, etc., but the efficiency of the material improvement and reactor or electrolyzer is still to be improved. . Tin dioxide may be doped with one or more metals, such as antimony (Sb), nickel (Ni), iron (Fe), platinum (Ru), #(8), p (Pd), money (Rh) (four) (c.), Or it may be doped with a non-metal such as fluorine (F). In addition, in order to improve the efficiency of ozone production,
Wang Y-H與其研究團隊將二氧化锡㈣種金屬摻雜，其技術可Wang Y-H and his research team doped tin dioxide (four) metals, the technology can be
見於電氣化學協會期刊第152卷第u輯，第197至第2〇〇頁 (2005年）令「摻銻及鎳氧化錫電極上的臭氧電解生成」一文。 本發明參考上述文獻發展出特有製造方法。此外，現有技術已 將一氧化錫（Sn02 )鍵在金屬上（例如：鐵，以形成馬口鐵）， 可作為食品級的容器，因此，以二氧化錫（Sn〇2)所製造成的 電極，可以安全地於水中電解出臭氧，再經由適當之處理（例 如經過RO逆滲透處理）後，以提供生物飲用水的。 一般而言，製造銻鎳摻雜二氧化錫電極需先準備一些包含 特定比例的錫、錄和鎳前驅物的酒精溶液，例如鎳：録：錫=1 : 1〇 · 600，並將此酒精溶液塗佈於鈦（Ti)基板上。接著，將塗 =在鈦基板上的酒精溶液經.3⑻。c的高熱分解以轉化為 一種娣鎳摻雜二氧化錫層；再接著將上述之塗佈及高熱分解的 :驟重複數次，例如:在—較佳的過程要經過1〇次以上的高熱 最後再將帶有多重塗佈層的鈦基板以500-600°C燒結 二里/至2小時。會經過如此複雜的過程，實乃因為塗佈與高 摻刀解，％進行的次數和熱處理條件均密切影響製造出的銻鎳 述雜化錫電極的臭氧形成能力和可靠性 ，同時，本發明上 佳，^路之加熱製程所獲得之多重塗佈層所製成的電極品質極 可使_摻雜二氧化錫電極於室溫下可產生超過罵臭氧 生電流效率。其—. 極的P 另一方面，本發明並驗證銻鎳摻雜二氧化錫電 下待性’有益於電解臭氧作為較難處理的工業廢水處理 201113224 的有效使用： 1. 本發明之銻鎳摻雜二氧化錫電極之製造方法可用於製 &大尺寸（即使向達15英吋直徑）及各種形狀的銻鎳摻雜二氧 化錫電極。 2. 本發明所製造之銻鎳摻雜二氧化錫電極，可直接以廢水 為媒介進行電解而直接於廢水中產生臭氧，故不須使用如氣化 鈉或硫酸等特定電解質。 3. 當本發明製造之銻鎳掺雜二氧化錫電極在處理低氣化 物含量的廢水時，可使用不鏽鋼做為陰極，例如選用316、314 或304等級之不銹鋼作為陰極；而對於高氯化物含量的水，例 如海水，可使用鈦做為陰極。 4. 本發明所製造之銻鎳摻雜二氧化錫電極不需要使用離 子交換膜分離陽極和陰極。 本發明所製造之録銻摻雜二氧化錫電極，其形成於録錄 摻雜二氧化錫電極上的臭氧和氧氣氣泡非常細緻。同時過氧化 氫（HA2)會配合臭氧而產生，這是因微小臭氧氣泡和陰極的 氫氣反應而形成，其產生方式與雨雪尹過氧化氫自然生成之作 用類似。 6. ¥水流以高速（每分鐘1〇公升或以上）流經本發明所 製造之銻鎳摻雜二氧化錫電極時，不會對於臭氧生成效能造成 明顯負面影響。 依據上述之結果，本發明可以利用銻鎳摻雜二氧化錫電極 作靈活配置設計，以製造出各種具成本效益之臭氧產生器。 首先’如第1圖所示’係一種流通式臭氧產生器1〇。如第 1圖所示，臭氧產生器10係由複數個陽極電極140及複數個陰 極電極160交互配置於一外殼120中，以形成一種電極交互堆 201113224See the Journal of the Electrochemical Association, Vol. 152, Vol. u, pp. 197–2 (2005), “Opdomation of Ozone Electrolysis on Antimony Doped and Nickel Tin Oxide Electrodes”. The present invention develops a unique manufacturing method with reference to the above documents. In addition, in the prior art, tin oxide (SnO 2 ) is bonded to a metal (for example, iron to form a tinplate), and can be used as a food-grade container. Therefore, an electrode made of tin dioxide (Sn〇2) is used. It is safe to electrolyze ozone in water and then provide biological drinking water after appropriate treatment (for example, after reverse osmosis treatment by RO). In general, the preparation of yttrium-nickel-doped tin dioxide electrodes requires the preparation of some alcohol solutions containing a specific proportion of tin, nickel and nickel precursors, such as nickel: recorded: tin = 1: 1 〇 600, and this alcohol The solution was coated on a titanium (Ti) substrate. Next, apply the = alcohol solution on the titanium substrate through .3 (8). The high thermal decomposition of c is converted into a ruthenium nickel doped tin dioxide layer; then the coating and high thermal decomposition described above are repeated several times, for example: in the preferred process, more than 1 heat is required Finally, the titanium substrate with multiple coating layers is sintered at 500-600 ° C for two minutes / to 2 hours. After such a complicated process, it is because the coating and the high-doping solution, the number of times of the heat treatment and the heat treatment conditions closely affect the ozone forming ability and reliability of the manufactured bismuth-nickel hybrid tin electrode, and at the same time, the present invention The superior electrode quality obtained by the multiple coating layers obtained by the heating process can make the _doped tin oxide electrode produce more than the ozone current generation efficiency at room temperature. On the other hand, the present invention and the verification of ruthenium-doped tin dioxide electrocautery are beneficial to the effective use of electrolytic ozone as a more difficult industrial wastewater treatment 201113224: 1. The nickel-nickel of the present invention The method of manufacturing a doped tin oxide electrode can be used to fabricate <large size (even up to 15 inches in diameter) and various shapes of bismuth-nickel doped tin dioxide electrodes. 2. The ruthenium-nickel-doped tin dioxide electrode produced by the present invention can directly generate electricity by directly electrolyzing waste water into waste water, so that it is not necessary to use a specific electrolyte such as gasified sodium or sulfuric acid. 3. When the nickel-doped tin-doped tin electrode produced by the present invention is used to treat low-gas content wastewater, stainless steel can be used as the cathode, for example, 316, 314 or 304 grade stainless steel is used as the cathode; and for the high chloride For the content of water, such as seawater, titanium can be used as the cathode. 4. The ruthenium nickel doped tin dioxide electrode produced by the present invention does not require the use of an ion exchange membrane to separate the anode and cathode. The ruthenium-doped tin dioxide electrode produced by the present invention has very fine ozone and oxygen bubbles formed on the recorded doped tin dioxide electrode. At the same time, hydrogen peroxide (HA2) is produced in combination with ozone, which is formed by the reaction of tiny ozone bubbles with the hydrogen of the cathode, and is produced in a manner similar to the natural generation of rain and snow. 6. The water flow at a high speed (1 liter or more per minute) flows through the yttrium-nickel-doped tin dioxide electrode produced by the present invention, and does not have a significant negative effect on the ozone generation efficiency. Based on the above results, the present invention can be flexibly configured using a ruthenium-nickel doped tin oxide electrode to produce various cost effective ozone generators. First, as shown in Fig. 1, a flow type ozone generator 1 is used. As shown in FIG. 1, the ozone generator 10 is alternately disposed in a casing 120 by a plurality of anode electrodes 140 and a plurality of cathode electrodes 160 to form an electrode interaction stack.
疊之結構，其中以綈鎳摻雜二氣化錫電極來形成陽極堆疊⑽， 而以不鐵鋼、欽、錄金屬片形成陰極堆疊16〇。每一陽極14〇 面對一平行陰極⑽，反之亦然。此外，亦可使用—非導電材 料作為電極間的隔板（第1圖中未示)，以防止電極發生電氣短 路。：非導電材料可以是聚丙烯、聚乙稀、尼奥普林、尼龍或 聚四氟乙稀。在-較佳之實施例中，此非導電材料之隔板所形 成之框架’可使電極間之間隙保持在。.5至5匪的距離。很明 顯地’在第1圖中的水流係以如路徑流貫臭氧產生器故會 ^/成抓通式之臭氧產生n 1()。此外，帛i圖中的電源供應器模 組180可以進一步配置一種超級電容器（SuperCapacit〇r)或是 一個升壓電路（boost circuit)，用來提供一個15V至2〇v之電 壓至％極堆疊140與陰極堆疊160的接點上，而水流通過臭氧 產生器10之後可經完全消毒或殺菌。而藉由增加電極面積或是 增加陽極-陰極對的數量，均可提昇反應器處理性能或臭氧產 量。而在一較佳之實施方式中，可於電源供應器模組18〇中再 加入一個脈波寬度調整裝置（PWM) 181，以便使用者能依據 所要調整電源供應器模組180之輸出電壓，進而控制臭氧產生 益10的反應速率。 接著，請參考第2A圖，圖中顯示一個以本發明之製造方法 所製造之録鎳摻雜二氧化錫之鈦（Ti)電極板1〇〇Α，鈦電極板 100A上配置有複數個成幾何形狀排列的孔洞n〇A，例如：以 同心方式排列（包括：圓形電極板時之同心圓排列；矩形電極 板時之同心環排列）’使得廢水可以經過鈦電極板l〇〇A上的孔 洞110A。在本發明之實施例中，無論此鈦基板之尺寸為何，鈦 電極板100A上配置的孔洞之總面積應佔鈦電極板1〇〇A總幾何 面積之5%至20%範圍内。然而，在一般處理狀況下，本發明 11 201113224 對於孔洞110A之總面積應佔鈦電極板100A總幾何面積之比例 並不加以限制，其可依實施要處理的廢水特性來決定》在此要 強調，本發明之孔洞可採用任何形式，並以任何方式排列，而 第2A圖所示則為本發明之一較佳實施例。同時，每一鈦電極板 100A上的孔洞110A之直徑、孔洞之數量以及圓環之數量與間 距’均依廢水所需達到的淨度目標值而定。在實際形成各項應 用所需之孔洞前’可先利用數學模式來決定電極上之開口所應 排成之圖案。 上述之鈦電極板100A係用來做為本發明之臭氧產生裝置 的陽極電極。當本發明之臭氧產生裝置在處理低氯化物含量的 廢水時，可使用不鑛鋼做為陰極，其中不鏞鋼之材料包括316、 14或304等級之不錄鋼。請參考第2B圖，為陰極之不繡鋼基 板100B上也配置有複數個孔洞hob，複數個孔洞hob之環形 排列方式與陽極之鈦電極板100A上的孔洞11〇A相似，兩者間 的差異僅在孔洞的配置位置不相同，即當兩者成上下堆疊結構 ，，鈦電極板100A與陰極電極板100B之間的孔洞u〇a/11〇b 弋不會形成上下重疊的，其示意圖如第2(：圖所示。第2C圖係 =紙電極板ΙΟΟΑ與不鏽鋼電極板丨咖堆疊後之俯視示意圖， 二示出相鄰電極上交錯排列之孔洞環。由於每一孔洞係錯開 預定距離’ gj此，欲接受處理之廢水必須以近似$形婉誕穿 過交錯排列之孔洞方可流出。 在母片如第2A圖與第2B圖所示之鈦電極板與不鐘 第電極板100B所示之周緣均設有—〇形環13()，如第2〇圖與A stacked structure in which an anode stack (10) is formed by doping a tin-depleted tin electrode with neodymium nickel, and a cathode stack 16 is formed by a non-ferrous steel, a metal sheet, and a metal sheet. Each anode 14 面对 faces a parallel cathode (10) and vice versa. Alternatively, a non-conductive material may be used as a separator between the electrodes (not shown in Fig. 1) to prevent electrical shorting of the electrodes. : The non-conductive material may be polypropylene, polyethylene, neoprene, nylon or polytetrafluoroethylene. In the preferred embodiment, the frame formed by the spacer of the non-conductive material maintains the gap between the electrodes. .5 to 5 inches distance. It is obvious that the water flow in Fig. 1 produces n 1 () by ozone flowing through the ozone generator as a path. In addition, the power supply module 180 in the diagram can be further configured with a supercapacitor or a boost circuit for providing a voltage of 15V to 2〇v to the % pole stack. 140 is connected to the cathode stack 160, and the water stream is passed through the ozone generator 10 for complete sterilization or sterilization. By increasing the electrode area or increasing the number of anode-cathode pairs, reactor performance or ozone production can be increased. In a preferred embodiment, a pulse width adjusting device (PWM) 181 can be added to the power supply module 18 , so that the user can adjust the output voltage of the power supply module 180 according to the desired voltage. Controlling the rate at which ozone produces a benefit of 10. Next, please refer to FIG. 2A, which shows a nickel-doped tin-doped titanium (Ti) electrode plate 1 manufactured by the manufacturing method of the present invention. The titanium electrode plate 100A is provided with a plurality of layers. The geometrically arranged holes n〇A, for example, are arranged in a concentric manner (including concentric circles when circular electrode plates are arranged; concentric rings are arranged when rectangular electrode plates are used) so that waste water can pass through the titanium electrode plates 10A Hole 110A. In the embodiment of the present invention, regardless of the size of the titanium substrate, the total area of the holes disposed on the titanium electrode plate 100A should be in the range of 5% to 20% of the total geometric area of the titanium electrode plate 1A. However, under normal processing conditions, the present invention 11 201113224 does not limit the ratio of the total area of the holes 110A to the total geometric area of the titanium electrode plate 100A, which may be determined according to the characteristics of the wastewater to be treated. The holes of the present invention may be in any form and arranged in any manner, and Figure 2A shows a preferred embodiment of the invention. At the same time, the diameter of the hole 110A, the number of holes, and the number and spacing of the rings on each of the titanium electrode plates 100A depend on the target value of the purity required for the wastewater. Before the actual formation of the holes required for each application, a mathematical model can be used to determine the pattern in which the openings on the electrodes should be arranged. The above titanium electrode plate 100A is used as an anode electrode of the ozone generating apparatus of the present invention. When the ozone generating apparatus of the present invention is used to treat low chloride content wastewater, non-mineral steel may be used as the cathode, and the material of the non-barium steel includes the 316, 14 or 304 grade unrecorded steel. Referring to FIG. 2B, a plurality of holes hob are also disposed on the cathode blank substrate 100B. The annular arrangement of the plurality of holes hob is similar to the hole 11〇A on the anode electrode plate 100A of the anode. The difference is only in the arrangement position of the holes, that is, when the two are stacked on top of each other, the holes u〇a/11〇b 之间 between the titanium electrode plate 100A and the cathode electrode plate 100B do not overlap one another, As shown in the second figure (2: Fig. 2C is a schematic plan view of the paper electrode plate and the stainless steel electrode plate stacked, and the second is a staggered hole ring on the adjacent electrode. For the distance of 'gj, the wastewater to be treated must flow through the staggered holes in a similar shape. The titanium plate and the second electrode plate shown in Figures 2A and 2B. The circumference shown in 100B is provided with a 〇-shaped ring 13(), as shown in Figure 2
堆晶E圖所不’其作用係在鈦電極板1〇〇A與陰極電極板100B 時，用以達到密封陽極電極板與陰極電極板之邊緣。〇形 3〇之材質可選自諸如三元乙丙橡膠（EpDM)之橡膠、聚石夕 12 201113224 氧、胺基曱酸酯或聚丙稀（PP)，厚度則為0.6至1公厘，且環 之外徑大於陽極之鈦電極板100A與陰極電極板100B之直經， 内徑則小於鈦電極板100A與陰極電極板ιοοΒ之直徑，而内、 外徑之差即為該0形環130之寬度。 請參考第3圖，將複數個如第2A圖與第2B圖所示之欽電 極板100A與陰極電極板100B垂直堆疊成一個電極板堆疊結構 200，若將此電極板堆疊結構200置入於一電解槽中，再將正電 極150 ( + )與負電極150 (-)之連接端曝露於電解槽外部時， 即可形成一獨立之臭氧產生裝置（未顯示於圖中）。如圖3所 示，臭氧產生裝置是將複數個第2A圖與第2B圖所示之鈦電極 板100A與陰極電極板100B間隔地垂直堆疊而成，例如：將鈦 電極板100A作為奇數電極，而陰極電極板1〇〇B作為偶數電 極；然後’將正電極之鈦電極板1〇〇A與負電極之陰極電極板 麵間隔地堆疊即可形成-獨立之臭氧產生裝置。然後，將每 -片鈦電極板謹與一正電極連接；另外，再將每一片 極板謂B與-負電極連接。至於，臭氧產生裝置要由多少欽電 極板H)()A來組成’則可以視所要產生之臭氧需求量而定。 臭氧產生裝置為例，其係由21片電極板所組 二片（頂端電極)與第21片（底端電極)以及盆 =的母一奇數鈦電極板剛Α定為正電極，而每一配置於每一奇 數鈦電極板_A之間的偶數陰極 當臭氧產生裝置上的正電極與 疋為負電極。故 备雷炻、鱼Μ B ”負電極與-直流電源之正電極與 2電極連射，即可在廢水巾經由電解 強調，上述於録鎳摻雜二氧化鎮昊氧在此要 錦摻雜二氧化錫之鈦（Ti)電極板麵形成^方1== 洞為本發明之較佳實_，_，當闕摻雜二氧㈣之鈦㈤ 201113224 電極板100A或是銻鎳摻雜二氧化錫之鈦（Ti)電極板1〇〇B上 沒有孔洞時，其所形成之堆疊電極2〇〇也可以達到直接在廢水 中產生臭氧之功能。 當臭氧產生裝置之曝露於電解槽外部之正電極與負電極與 一個低DC電源（例如24V或以下之電供應器_p〇wer supply) 的兩電極連接後，陽極（鈦電極板100A )便能使水分解，在水 中直接產生臭氧（與氧氣）；陰極（不繡鋼電極板；不繡鋼之 材質包括：SS304，SS304L，SS316，SS316L，SS410，SS410L， SS43〇等）則產生氫氣，如下列反應方程式（1)與（2): 陽極反應： 8 H20 -> 〇2 + 2 〇3 + 16 H+ + 16 e' (1) 陰極反應： 2 H20 + 2 e -> H2 + 2 OH* (2) 此外’電解槽中的陽極電極與陰極電極間無隔離，陽極電 極產生的臭氧會與陰極電極產生的氫氣進行下列的反應方程式 為： 2 〇3 + H2 —> H2〇2 + 2 〇2 (3) 反應方程式（3)所產生之雙氧水（h2〇2)也是一種強氧 匕齊I具有殺菌與刀解有機污染物的功能。更重要的是，臭氧 還會與雙氧水反應產生氩氣自由基（•OH Hydroxyi Radical)。 •OH基的氧化能力比ο;更強，分解有機污染物的速率比〇3迅 速萬倍以上。而在本發明之臭氧產生裝置中，產生氫氣自由基 (·〇Η)說明如下。 臭氧的自分解可以通過與水中〇H-離子反應生成Η〇2·離 子’其反應方程式為： 〇3 + 〇Η_-> Η〇2_ + 〇2 (4) 201113224 再由於臭氧產生裝置中已含有過氧化氫（h2o2)，如反應方 程式（3)，則H2〇2又會將水分解以產生h〇2-，其反應方程式 為： Η2〇2 + Η20 Η02· + Η30+ (5) 反應方程式（4)及（5)所生成的ΗΟ_2是自由基·ΟΗ產 生的誘發劑，其反應方程式為：. 〇3 +Η〇2* ·〇Η+ 〇2* +〇2 (6) 當自由基·〇Η —旦產生後’就發生如下鏈反應： 〇3 + ·ΟΗ-> Η〇2 +〇2 ：(V) 〇3 + 〇3 — 〇3 +〇2 (8) 03'+ Η20 ·0Η + 0H +02 (9) 除了上述反應外，還存在·〇Η OH與Η2〇2反應比上述反應慢得多 自由基與Η2〇2反應，但 ，故可以被忽略。 若水中存在有機污染物ρ，則反應方程式為： Ρ+·ΟΗ —產物或中間物 （1〇) 此外’有機物Ρ與臭氧的直接氧化反應方程式為： Ρ+ 〇3 —產物或中間物 （11) 15 201113224 最後，反應方程式（Η)會再進一步氧化成二氧化碳（<C〇2) 及水（H20)，其氧化反應方程式為： P + 〇3-> 產物或中間物->C02+H20 (12) 若所要處理的廢水令含有醇類時，則其與本發明之臭氧產 生裝置的反應概述如下。一般的醇類以ROH根表示，故R〇H 根會先被氧化為醛類（RCHO)，接著，醛類（RCHO)再被氧 化為酮類（RCOR)，然後酮類（RC0R)再被氧化為有機酸 (RCOOH)，此有機酸（RCOOH)即為一種氧化過程的中間 物（P) ’最終此中間物（P)再被氧化為二氧化碳（c〇2)及 水（Ηβ)，總結之氧化反應方程式為： ROH RCHO -> RCOR -> RCOOH ^ P C02 + H20 (13) 經由上述之說明，本發明之臭氧產生裝置可以將廢水中的 有機物分解成二氧化碳（C〇2)及水（H2〇)。同樣地，本發明 之臭氧產生裝置可以氧化分解的有機物還包括含紛廢水；此含 酴廢水中主要3有盼基化合物，如苯盼、甲酴、二甲盼和石肖基 甲酚等，而此酚廢水其主要來自焦化廠、煤氣廠、石油化工廠、 絕緣材料廠等工業部門以i石油裂解制乙烯、合成苯酚、聚醯 胺纖維、合成染料、有機農藥和酚醛樹脂生產過程所產生之廢 水。在此要強調，上述以含醇類廢水以及含酚類廢水來說明本 發明之臭氧產生裝置可以將廢水中的有機物分解成二氧化碳 (C〇2)及水（H2〇 )’然而’廢水中的有機物還包括其他類型 者’例如：對不飽和脂肪烴和芳香烴類化合物等也是有效的。 綜合上述’本發明之臭氧產生裝置可以藉由直接氧化（在 陽極上）、間接氧化（與〇3/Η2〇2/·〇Η反應）、直接還原（在 陰極上）與間接還原（與Η2反應）等過程來達到殺菌/除臭/ 褪色/漂白等作用。 201113224 第4圖即為本發明之臭氧產生裝置300中的堆疊電極結構 200之一實施例的示意圖。堆疊電極結構200以上蓋310及下 蓋330配合螺桿、螺絲與螺帽（未顯示於圖中）固定後，水由臭氧 產生裝置之進水口（ 320)進入，流經堆疊電極結構200後，由 出水口（ 320 )流出經過處理的水。再次說明，堆疊電極結構 200之電極配置方式，可以如第1圖所示之流通式配置方式來 形成一個流通式臭氧產生器10。此外，堆疊電極結構200之電 極是以正電極與負電極交又堆疊而成，並以單極性組態與DC 電源供應器連線，如第3圖所示。 在本發明第4圖之臭氧產生裝置300中，無論其堆疊電極 結構200之配置方式，其均具有產生1 Kg 03/hour的能力，並 且可以依據所要處理的廢水狀態，來設計出所需要產生的臭氧 量300來客製化地（或稱case-by-case)製造出每一個廢水處理 案所需之臭氧產生裝置300。 隨著產業的發展，特別是化學工業、染整工業造紙工業食 品加工業以及半導體相關製造工業（包括1C製造之異丙醇廢 水、化學研磨廢水、液晶面板之彩色濾光片之製造廢水）等， 在產品的製造過程中使用大量的有機溶劑或是化學合成之有機 溶劑，這些有機溶劑或是化學合成之有機溶劑所產生之製造廢 水通常具有毒性並且很難被自然分解，故形成了高濃度的化學 需氧量（Chemical Oxygen Demand ; COD)，造成 了環境污染。 而一般工業廢水或是生活污水中，以COD與濁度為兩項最 難去除的污染物。事實上，濁度常為懸浮性COD所構成，去除 濁度後，COD即跟著降低。同樣地，濁度來自懸浮固體（SS)， 濁度去除後，SS也跟著降低。如前所述，本發明之臭氧產生裝 置在臭氧的氧化分解有機污染物的過程中，包含許多階段的化 17 201113224 學反應（如反應方程式1〜13)，每一階段的速率較慢，故要處 理高COD濃度（例如數萬或數十萬ppm)的事業廢水時，就需 要花費較大的電能以及較多的時間。然而，在習知技術中，電 凝聚裝置（Electro-coagulation; EC)可以降低廢水中的COD 濃度，例如：美國專利第3969345號、第4123340、第4159235號、 第5271814號、第5587057號、第5611907號、第5611907號等，均已 揭露使用電凝聚裝置（Electro-coagulation; EC)來移除廢水中 的雜質。 接著’請參考第5圖，係本發明之使用柱狀電極所形成電 凝聚裝置（EC)之示意圖。如第5圖所示，本發明之電凝聚裝 置400係由一個電解槽410以及配置於電解槽410中的至少一 對陽極電極柱430與陰極電極柱450以及一沉澱物排出孔470。 當以本發明之電凝聚裝置（EC) 400來處理廢水時，就是 將廢水輸入至電解槽410中，使得至每一根陽極電極柱430與 每一根陰極電極柱450浸入廢水中，如第5圖所示；接著，將 陽極電極柱430及陰極電極柱450與一個直流電源（DC power supply )連接，藉由直流電源所提供之電流作用，使得陽極電極 柱430釋放出離子’因此使得廢水中的離子成分被吸引到電極 柱430及陰極電極柱450的表面上，以形成氧化與還原反應。 例如’使用鐵作陽極電極(也稱為犧牲陽極）以及使用鋁作為陰極 電極時，當陽極電極柱430和陰極電極柱45〇通上直流電流後， 陽極電極溶解出亞鐵離子Fe+2和Fe+、然後在水中與陰極電極 電解出的氫氧根離子（〇H-)生成Fe(〇H)2和Fe(〇H)3，其反 應方程式如下： 陽極反應The layer E is not used for the titanium electrode plate 1A and the cathode electrode plate 100B to seal the edges of the anode electrode plate and the cathode electrode plate. The material of the 〇3〇 may be selected from rubber such as ethylene propylene diene monomer (EpDM), poly sylvestre 12 201113224 oxygen, amino phthalate or polypropylene (PP), and the thickness is 0.6 to 1 mm, and The outer diameter of the ring is larger than the diameter of the titanium electrode plate 100A and the cathode electrode plate 100B of the anode, and the inner diameter is smaller than the diameter of the titanium electrode plate 100A and the cathode electrode plate ιοο, and the difference between the inner and outer diameter is the 0-ring 130 The width. Referring to FIG. 3, a plurality of zirconia plates 100A and cathode electrode plates 100B as shown in FIGS. 2A and 2B are vertically stacked into an electrode plate stack structure 200. If the electrode plate stack structure 200 is placed in In an electrolytic cell, when the connection end between the positive electrode 150 (+) and the negative electrode 150 (-) is exposed to the outside of the electrolytic cell, a separate ozone generating device (not shown) can be formed. As shown in FIG. 3, the ozone generating device is formed by vertically stacking a plurality of titanium electrode plates 100A and cathode electrode plates 100A shown in FIG. 2A and FIG. 2B, for example, using titanium electrode plate 100A as an odd electrode. The cathode electrode plate 1〇〇B is used as an even electrode; then the titanium electrode plate 1A of the positive electrode and the cathode electrode plate of the negative electrode are stacked at intervals to form an independent ozone generating device. Then, each of the titanium electrode plates is connected to a positive electrode; in addition, each of the plates is connected to a negative electrode. As for the amount of the ozone generating device H)()A, the ozone generating device can be determined depending on the amount of ozone demand to be generated. An example of an ozone generating device is a two-piece (top electrode) and a twenty-first electrode (bottom electrode) and a mother-odd odd-numbered titanium electrode plate of 21 electrode plates, which are each set as a positive electrode, and each of them is a positive electrode. The even cathodes disposed between each of the odd-numbered titanium electrode plates _A are the negative electrodes on the ozone generating device. Therefore, the thunder and the fish Μ B ” negative electrode and the positive electrode of the DC power supply and the 2 electrode are sprayed together, which can be emphasized in the wastewater towel by electrolysis, and the above-mentioned nickel-doped oxidized oxidized yttrium is doped here. Titanium oxide (Ti) electrode plate surface formation ^ 1 = = hole is the preferred embodiment of the invention _, _, when yttrium doped with oxygen (four) of titanium (5) 201113224 electrode plate 100A or yttrium nickel doped dioxide When there is no hole in the tin-titanium (Ti) electrode plate 1〇〇B, the stacked electrode 2〇〇 formed can also directly generate ozone in the wastewater. When the ozone generating device is exposed to the outside of the electrolytic cell After the electrode and the negative electrode are connected to the two electrodes of a low DC power source (for example, an electric supply of 24V or less), the anode (titanium electrode plate 100A) can decompose water and directly generate ozone in the water (with Oxygen); cathode (non-steel plate; non-steel material including: SS304, SS304L, SS316, SS316L, SS410, SS410L, SS43〇, etc.) produces hydrogen, such as the following reaction equations (1) and (2): Anode reaction: 8 H20 -> 〇2 + 2 〇3 + 16 H+ + 16 e' (1) Cathodic reaction: 2 H20 + 2 e -> H2 + 2 OH* (2) In addition, there is no isolation between the anode electrode and the cathode electrode in the electrolytic cell, and the ozone generated by the anode electrode reacts with the hydrogen generated by the cathode electrode in the following reaction. The equation is: 2 〇3 + H2 —> H2〇2 + 2 〇2 (3) The hydrogen peroxide (h2〇2) produced by the reaction equation (3) is also a kind of strong oxygen oxime. I have bactericidal and knife-dissolved organic pollutants. More importantly, ozone reacts with hydrogen peroxide to produce argon free radicals (•OH Hydroxyi Radical). • The oxidizing power of OH groups is stronger than that of OH; the rate of decomposition of organic pollutants is 10,000 times faster than that of 〇3. Further, in the ozone generating apparatus of the present invention, the generation of hydrogen radicals (·〇Η) is explained below. The self-decomposition of ozone can be carried out by reacting with H-ion ions in water to form Η〇2· ions', and the reaction equation is: 3 + 〇Η_-> Η〇2_ + 〇2 (4) 201113224 Since the ozone generating device already contains hydrogen peroxide (h2o2), as in the reaction equation (3), H2〇2 will decompose the water to produce H〇2-, the reaction equation is: Η2〇2 + Η20 Η02· + Η30+ (5) The ΗΟ_2 generated by the reaction equations (4) and (5) is an inducer of free radical ΟΗ, and its reaction equation is: 〇3 +Η〇2* ·〇Η+ 〇2* +〇 2 (6) When the free radicals are generated, the following chain reaction occurs: 〇3 + ·ΟΗ-> Η〇2 +〇2 :(V) 〇3 + 〇3 — 〇3 +〇2 (8) 03'+ Η20 ·0Η + 0H +02 (9) In addition to the above reaction, the presence of 〇Η OH and Η2〇2 is much slower than the above reaction. The radical reacts with Η2〇2, but it can be ignored. If organic pollutant ρ is present in the water, the reaction equation is: Ρ+·ΟΗ—product or intermediate (1〇) In addition, the direct oxidation reaction equation for 'organic matter Ρ and ozone is: Ρ+ 〇3—product or intermediate (11 15 201113224 Finally, the reaction equation (Η) is further oxidized to carbon dioxide (<C〇2) and water (H20), and the oxidation reaction equation is: P + 〇3-> product or intermediate->C02 +H20 (12) If the wastewater to be treated is such that it contains an alcohol, its reaction with the ozone generating apparatus of the present invention is summarized as follows. The general alcohol is represented by the ROH root, so the R〇H root will be first oxidized to the aldehyde (RCHO), then the aldehyde (RCHO) will be oxidized to the ketone (RCOR), and then the ketone (RC0R) will be Oxidation to organic acid (RCOOH), this organic acid (RCOOH) is an intermediate of the oxidation process (P) 'The final intermediate (P) is then oxidized to carbon dioxide (c〇2) and water (Ηβ), summary The oxidation reaction equation is: ROH RCHO -> RCOR -> RCOOH ^ P C02 + H20 (13) According to the above description, the ozone generating device of the present invention can decompose organic matter in wastewater into carbon dioxide (C〇2) and Water (H2〇). Similarly, the oxidatively decomposable organic matter of the ozone generating device of the present invention further includes waste water; the main strontium-containing waste water contains a compound of a promiscuous group such as benzophenone, formazan, dimethyl sulphate, and succinyl cresol. Phenol wastewater mainly comes from industrial processes such as coking plants, gas plants, petrochemical plants, and insulating materials plants. Wastewater from the production of petroleum, synthetic phenol, polyamide fibers, synthetic dyes, organic pesticides and phenolic resins. . It should be emphasized here that the above-mentioned ozone generating device of the present invention containing alcohol-containing wastewater and phenol-containing wastewater can decompose organic matter in wastewater into carbon dioxide (C〇2) and water (H2〇). Organics also include other types of 'for example: also for unsaturated aliphatic hydrocarbons and aromatic hydrocarbons and the like. The above-mentioned 'Ozone generating device of the present invention can be directly oxidized (on the anode), indirectly oxidized (reacted with 〇3/Η2〇2/·〇Η), directly reduced (on the cathode) and indirectly reduced (with Η2) Reactions and other processes to achieve sterilization / deodorization / fading / bleaching. 201113224 Figure 4 is a schematic illustration of one embodiment of a stacked electrode structure 200 in an ozone generating device 300 of the present invention. After the stacked electrode structure 200 above the cover 310 and the lower cover 330 are fixed with the screw, the screw and the nut (not shown), the water enters through the water inlet (320) of the ozone generating device, and flows through the stacked electrode structure 200. The water outlet (320) flows out of the treated water. Again, the electrode arrangement of the stacked electrode structure 200 can be such that a flow-through ozone generator 10 can be formed in a flow-through configuration as shown in FIG. In addition, the electrodes of the stacked electrode structure 200 are stacked with the positive and negative electrodes and connected to the DC power supply in a unipolar configuration, as shown in Figure 3. In the ozone generating apparatus 300 of Fig. 4 of the present invention, regardless of the arrangement of the stacked electrode structures 200, it has the ability to generate 1 Kg 03/hour, and can design the required generation depending on the state of the wastewater to be treated. Ozone amount 300 is used to create an ozone generating device 300 required for each wastewater treatment case in a case-by-case manner. With the development of the industry, especially in the chemical industry, the dyeing and finishing industry, the paper industry, the food processing industry, and the semiconductor-related manufacturing industry (including the 1C manufacturing of isopropanol wastewater, chemical grinding wastewater, liquid crystal panel color filter manufacturing wastewater), etc. In the manufacturing process of the product, a large amount of organic solvent or a chemically synthesized organic solvent is used. The manufacturing wastewater produced by these organic solvents or chemically synthesized organic solvents is generally toxic and difficult to be naturally decomposed, thus forming a high concentration. Chemical Oxygen Demand (COD), causing environmental pollution. In general industrial wastewater or domestic sewage, COD and turbidity are the two most difficult to remove pollutants. In fact, turbidity is often composed of suspended COD, and after removal of turbidity, COD is reduced. Similarly, the turbidity comes from suspended solids (SS), and after the turbidity is removed, the SS is also reduced. As described above, the ozone generating apparatus of the present invention contains many stages of the process of oxidative decomposition of organic pollutants by ozone (e.g., reaction equations 1 to 13), and the rate of each stage is slow, so To handle high-COD concentrations (for example, tens of thousands or hundreds of thousands of ppm) of commercial wastewater, it takes a lot of electricity and more time. However, in the prior art, electrocoagulation (EC) can reduce the concentration of COD in wastewater, for example, U.S. Patent Nos. 3,969,345, 4,123,340, 4,159,235, 5,718,814, 5,587,057, No. 5611907, No. 5,561,907, etc., have disclosed the use of electrocoagulation (EC) to remove impurities in wastewater. Next, please refer to Fig. 5, which is a schematic view of an electrocoagulation apparatus (EC) formed by using a columnar electrode of the present invention. As shown in Fig. 5, the electrocoagulation device 400 of the present invention comprises an electrolytic cell 410 and at least a pair of anode electrode columns 430 and cathode electrode columns 450 disposed in the electrolytic cell 410 and a sediment discharge port 470. When the wastewater is treated by the electrocoagulation device (EC) 400 of the present invention, the wastewater is input into the electrolytic cell 410 such that each of the anode electrode columns 430 and each of the cathode electrode columns 450 are immersed in the wastewater, such as 5; then, the anode electrode column 430 and the cathode electrode column 450 are connected to a DC power supply, and the anode electrode column 430 releases ions by the action of the current supplied by the DC power source. The ionic components in the ionic components are attracted to the surfaces of the electrode column 430 and the cathode electrode column 450 to form an oxidation and reduction reaction. For example, when 'iron is used as the anode electrode (also called sacrificial anode) and aluminum is used as the cathode electrode, when the anode electrode column 430 and the cathode electrode column 45 are connected with a direct current, the anode electrode dissolves the ferrous ion Fe+2 and Fe+, then hydrogen ions (〇H-) electrolyzed in the water and the cathode electrode form Fe(〇H)2 and Fe(〇H)3, and the reaction equation is as follows:
Fe->Fe+2+2e~ (14) 201113224Fe->Fe+2+2e~ (14) 201113224
Fe+2—Fe+3+e_ (15) 陰極反應 2H20+ 2e'-^20H"+ H2 (16) 則在本發明之電凝聚裝置（EC)中的總反應方程式為Fe+2—Fe+3+e_ (15) Cathodic reaction 2H20+ 2e'-^20H"+ H2 (16) The total reaction equation in the electrocoagulation device (EC) of the present invention is
Fe+2+ 2(OH 卜 Fe(OH)2 (17) 及Fe+2+ 2(OH 卜Fe(OH)2 (17) and
Fe+3+3(OH)--^Fe(OH)3 (18)Fe+3+3(OH)--^Fe(OH)3 (18)
由上之反應方程式可知，當電凝聚裝置（EC) 400之陽極 電極430與陰極電極450連接適當之直流電源或交流電源時， 陽極電極430 (最常用的材料為鐵或銘）將被電解產生鐵離子 (Fe2+)或鋁離子（Al3+)及其他產物：例如：電子、氫離子與 氧氣等。同時’陰極電極450產生：氫氣與氫氧根離子（OH·)。 金屬陽離子（例如：鐵離子）可直接與懸浮性COD或水溶性 COD結合，凝聚成大粒徑的顆粒而沉澱至電解槽41〇之底部並 可藉由排出孔470排出，故可使廢水中的COD濃度迅速下降。 另一方面’金屬陽離子（例如：鐵離子）也可與氫氧根離子（〇Η·) 形成有絮凝作用的聚合物，再進一步的去除廢水中的COD。此 外’浮於水中的凝聚物還能被陽極電極430與陰極電極450所 產生的氣泡吸附’成為可以刮除或溢流的浮渣（froth )。因此， 電凝聚裝置（EC) 400的處理包含表1所列之多元反應： 表1: EC處理所提供之反應 # 反應 反應内容 1 直接氧化 污染物在陽極上氧化分解成為:離子/co2/h2o 2 間接氧化 污染物被氧氣氧化分解成為:離子/co2/h2o 3 直接還原 污染物在陰極上還原成為:沉積物或揮發有機物 19 201113224 4 間接還原 … ，-~___ 」亏/染辦皮氫氣還原成為:沉積物或捏發性右機物 5 凝聚 ^ 7λ I-1* r% 物聚结為大顆粒 6 浮除 污染物被氫氣或氧氣氣泡吸附成盎这、、杰 7 中和/沉澱 jimm r/oH-1 由於表1之多元反應的結果顯示，使用電凝聚裝置（ec) 4〇〇能提供快速的除污效果，例如：當廢水流過電凝聚裝置（ec) 後，其廢水中的COD便會減少約80%。此外，在本實施例中， 作為陽極的鐵材料可以是生鐵、黑鐵、鑄鐵 '光圓鐵、skd6〇 與SS430等。 請繼續參考第6圖，係本發明之電凝聚裝置（EC)示意圖。 如第6圖所示，本發明之電凝聚裝置（EC) 4〇〇是以一個内部 直徑2〇Cm的電解槽410來將陽極電極43〇與陰極電極45〇分成 兩圈安置於頂蓋420上，並且配合螺桿、螺絲與螺帽（未顯示於 圖中）等固定。電解槽410進一步配置有一進水口 44〇以及一出 水口 460，以提供廢水進出電凝聚裝置（EC) 400的通道；而 電凝聚裝置處理過程所產生之污泥，則可由沉殿物排出孔47〇 排出。此外，要強調的是，在本發明對電凝聚裝置（EC) 4〇〇 中的電極數目、面積、間距、正負電極的排列、單極性 (monopolar)或雙極性（bipolar)組態、DC或AC供電、以及 電壓/電流的設定等，並未加以限制，其僅為本發明之一實施 例，而實際之電凝聚裝置（EC)結構是可以視廢水水質測試與 處理目標而設計，以使電凝聚裝置（EC) 400處理後的廢水達 到下列指標： 1. 水流速率 200-300 Liter/minute。 2. 水流過一個電凝聚裝置（EC)後，其COD/SS/濁度去除 20 201113224 80%。 3·水流過一個電凝聚裝置（£C)後，可去除1 Kg之COD 並且只消耗lkWh或以下之電能。 依據上述’本發明以電凝聚裝置（EC) 4〇〇來對廢水進行處 理時，其具有下列的效益： 1·不使用化學品，只需供應電能即可對廢水進行處理，故 乾淨無污染》 • 2.污泥量比「化學混凝法」少3〇%以上（因為電凝聚裝 置不需添加陰離子）。 3. 電凝聚裝置所產生之污泥的含水量少（4〇%以上）， 可作為無毒的固體廢棄物處理（此標準已獲得USEpA認可）。 4. 電凝聚裝置所產生之污泥的聚結強度高，不易分散，因 此容易過濾（成為泥餅）去除。 5. 電凝聚裝置所能去除之污染物的種類多，去除率常可達 90%以上。 . 6.電凝聚裝置能使高濃度的廢水快速減少污染物（如 COD)。 7.電凝聚裝置的工作溫度範圍廣（冷熱不影響處理）。 8·電凝聚裝置處理器不含機械零件（僅陽極是唯一需要更 換的耗材）。 9·金屬陽離子凝聚劑容易控制於「適時適量」產生。 10·電凝聚裝置佔地小（例如：以每日38〇〇m3或38〇〇cmd 處理畺的電凝聚裝置系統來估計，其佔地約為14.1坪）。 然而’本發明之電凝聚裝置（EC) 400非萬能，以目前技 術而言’其在廢水的處理限制包括： 21 201113224 ι·電凝聚裝置無法去除一價金屬離子9如驗金屬離子 (Na+、Κ+) 〇 2·電凝聚裝置處理後的水之導電度（或TDS)高於處理前。 3·電凝聚裝置對一些溶解性較強的COD之去除率低。 4·電凝聚裝置處理無法將廢水減至極低的濃度。 因此’電凝聚裝置需要其他電處理技術的輔助，來回收事 業與生活廢水。例如：在本發明對電凝聚裝置（Ec ) 400之後 再與一個臭氧產生裝置300串接在一起，即可形成一個電能式 廢水處理裝置，可以用來處理高濃度COD之廢水。而選擇將臭 氧產生裴置300與電凝聚裝置（EC) 4〇〇組合成廢水處理裝置 之目的’是因為臭氧產生裝置300能提供電凝聚裝置（EC) 400 所無法達到之處理效果，包括： 臭氧產生裝置300能將廢水中的COD減至近乎0 ppm。 2·臭氧產生裝置300不產生污泥（因為，污染物被氧化及 還原為C〇2與η2〇)。 3·臭氧產生裝置300中的臭氧(〇3)反應後成為氧氣，且不 會遺留金屬陽離子。 凊參考第7圖，係表示本發明之一種電能式廢水處理裝置 之功能方塊示意圖。如第7圖所示’本發明之電能式廢水處理 裝置600包括一個電凝聚裝置（ec) 400以及一個臭氧產生裝 置300’其中臭氧產生裝置如第4圖所示，而電凝聚裝置（EC) 400如第6圖所示。故當廢水經由電凝聚裝置（EC ) 400之進 水口 440進入至電解槽410中，廢水在電解槽410中與陽極電 極430及陰極電極450進行反應後，在適當之直流電源之供應 下’依據反應方程式（14 )〜（18 )之結果，可以將廢水中的 COD減少約80% ;接著’處理過的廢水會由出水口 460送皇臭 201113224 氧產生裝置3〇〇之進水口 320 ,然後廢水再流經堆疊電極結構 200後’依據反應方程式（丨）〜（12)之氧化結果，可將廢水 中剩餘的有機物分解成二氧化破及水，然後，由出水口 320流 出經過處理並符合標準的水。很明顯地，為了能增加本發明之 電能式廢水處理裝置6〇〇之反應效率，以節省電能，在本發明 之一較佳實施例中，係在電凝聚裝置（EC) 400之進水口 440 之前先配置一過濾裝置620，其目的在預先過濾廢水中大於1〇 微米以上的物質；接著，還可以在電凝聚裝置（EC) 400之出 φ 水口 460與臭氧產生裝 置300之進水口 320之間也配置一個過 遽裝置64〇，其主要目的在過濾於電凝聚裝置（EC) 400中產 生的聚合物（例如：過濾大於0.5微米之聚合物）；最後，本 發明還可以在臭氧產生裝置300之出水口 34〇處也配置一個過 滤裝置660，其主要目的在過濾臭氧產生裝置630中微小的雜 質（例如：過濾大於〇.2微米之雜質），以確保處理後的品質可 以作為生產用水。很明顯地，本發明之之電能式廢水處理裝置 600在整個處理過程中，係採用廢水連續流過電極之處理方式， I 因此疋以廢水為產生處理劑之媒介或原料，來將廢水中的污染 物當場(in-situ)去除，故本發明之電能式廢水處理裝置600可以 在不需添加任何化學成份狀況下，藉由對廢水的電解使得廢水 處理或再生成生產用水，故不會產生二次公害。 當本發明之電能式廢水處理裝置600與/電源供應器（未 顯示於圖中）以及一泵浦配（未顯示於圖中）置於一活動架上 時，即可形成一獨立且可移動之電能式廢水處理模組，其中電 能式廢水處理裝置係由至少一個電凝聚裝置（EC) 400與至少 一個臭氧產生裝置300串接所組成，然後使用至少一個泵浦， 用以將廢水抽入至電凝聚裝置（EC) 400的電解槽中；當每一 23 201113224 個電凝聚裝置（EC)與每—個臭氧產生裝置與電源供應器連接 後，廢水便能夠與配置在電凝聚裝置（Ec)働之電解槽中的 陽極電極及陰極電極钟氧_原反應，使得廢水巾的c〇d很 快的降低’然後，再將廢水送到臭氧產生裝置卜使得廢 水與堆疊電極200進行反應後，即可使廢水中的c〇d降低至接 近〇。同樣地’為使本發明之電能式廢水處理模組能具有更好 的政果田電月廢水處理模組使用多個電凝聚裝置（ec) 4〇〇 時，其彼此間是使用並聯方式連接，另外，當電能式廢水處理 模組使用多個臭氧產生裝置扇肖，其彼此間也是使用並聯方 式連接。 此外，於本發明之電能式廢水處理模組中加入一些過濾裝 置時，除可以加快廢水之處理速度外，還可以降低電能的消耗。 故在本發明之電能式廢水處理模組申，可以在電凝聚裝置（EC) 400之進水口之前先配置一過濾裝置，其目的在預先過濾廢水 中大於10微米以上的物質；接著，還可以在電凝聚裝置（Ec) 4〇〇之出水口與臭氧產生裝置3〇〇之進水口之間也配置一個過 ;慮裝置’其主要目的在過濾於電凝聚裝置（EC) 400中產生的 聚合物（例如：過濾大於0.5微米之聚合物）；最後，本發明 還可以在臭氧產生裝置300之出水口處也配置一個過濾裝置， 其主要目的在過濾臭氧產生裝置中微小的雜質（例如：過濾大 於0.2微米之雜質），以確處理後的水可以作為生產用水。 很明顯地，若需要提高單位時間的廢水處理量，f以將使 用複數個電能式廢水處理模組來，形成一個電能式廢水處理系 統來進行廢水的處理。此種以附加（Add-on)方式來形成模組 化的系統具有下列的優勢： 1.依廢水之污染物種類與再生目標，設計最經濟實用之組 24 201113224 合系統。 2. 組合系統以並聯的數條獨立作業線運轉’不會因某一個 電處理unit出狀況而停機。 3. 組合系統易於擴大產能.、安裝、搬遷與維修。 4. 電處理units可重疊安置，進一步縮小系統的佔地。 組合系統或其次系統之使用地點（Point of use)無限制。 經由適當數量的組合，本發明之電能式廢水處理系統能將高 COD且具有濁度之廢水處理至如下之標準： _ 1. COD 自 1，500 ppm 減至 40 ppm 或以下。 2. SS減至20 ppm以下。 3. 色度 < 500 ADMI 值。 4. 1500 CMD處理量，產生約1噸污泥。 5. 回收自生產線流出的90%廢水’再用於生產。 故本發明之電能式廢水處理系統可在完全不用任何化學品 下’將廢水從污黑混〉蜀的狀態被轉化為清澈之生產用水’同時 可以提高廢水的回收率至90 %，故可以直接再用於生產，進一 步達到節省用水之功能。 • 當經過本發明之電能式廢水處理裝置600、電能式廢水處理 模組或是電能式廢水處理系統處理後的水（包括符合放流標準 的水以及可以作為生產用的水），若當處理後的廢水經過一個檢 測裝置檢測並符合放流標準的水後’再將其經一個RO逆滲透 裝置過滤時，即可達到人類飲用標準。 嗜參考第8圖，係本發明之電能式之廢水處理系統之再一 較佳之實施例，此電能式之廢水處理系統700可以將廢水處理 至達到人類飲用標準。如第8圖所示，當廢水經過本發明之電 能式廢水處理裝置6〇〇、電能式廢水處理模組或是電能式廢水 25 201113224 處理系統處理後*並經過一檢測裝置650檢測合格後$即可以 作為生產用水；若再將檢測合格之水經一個RO逆滲透裝置720 過濾後，即可達到人類飲用標準。而在一較佳之實施例中，可 將經RO逆滲透裝置720過濾後的水再經過一次的臭氧產生裝 置300的處理（即消毒）後，即可達到人類直接飲用標準。 雖然本發明之電能式廢水處理系統中的電凝聚裝置以及 臭氧產生裝置的特定結構與其實施例，已於前述說明中揭露， 然而，其所揭露之内容僅為本發明之電能式廢水處理系統之實 施方式之一，故其所揭露之内容並非用來限制本發明之其他實 施方式。故本發明除了上述詳細的描述外，還可以廣泛地在其 他的實施例中施行，例如：在電凝聚裝置以及臭氧產生裝置結 構中的電極配置方式、電凝聚裝置以及臭氧產生裝置結構的固 定方式，以及電凝聚裝置以及臭氧產生裝置的特定組合結構 登。因此，精於此技藝者能在不脫離本案前述所揭露之精神與 範疇下做各種不同形式的改變，均應包含在下述申請專利範圍 内。 【圖式簡單說明】 第1圖係本發明之流通式臭氧產生器之示意圖。 第2A圖〜第2E圖係本發明之臭氧產生裝置之電極示意圖。 第3圖係將本發明之臭氧產生裝置中的堆疊電極之示意圖。 第4圖係本發明之臭氧產生裝置中的堆疊電極之另一實施 例示意圖。 第5圖係本發明之電凝聚裝置之電解槽中的反應示意圖。 第6圖係本發明之電凝聚裝置的示意圖。 第7圖係本發明之電能式之廢水處理系統的功能方塊示意 201113224 第8圖係本發明之電能式之廢水處理系統的另一實施例之 功能方塊示意圖。 【主要元件符號說明】 10 100A、100B 110A、110B 120 130 140/160 150 180 181 200 300 310 320 330 340 400 410 420 430 ' 450 440 460 470 600 流通式臭氧產生器 電極板 電極板上的孔洞 外殼 0形環 陽/陰極電極板 正負電極連接端 電源供應器模組 脈波寬度調整裝置（PWM) 電極板堆疊結構 臭氧產生裝置 上蓋 進水口 下蓋 出水口 電凝聚裝置 電解槽 頂蓋 電極 進水口 出水口 沉澱物排出孔 電能式之廢水處理系統 27 201113224 620 ' 640 ' 660 過濾裝置 650 檢測裝置 720 RO逆滲透裝置It can be seen from the above reaction equation that when the anode electrode 430 of the electrocoagulation device (EC) 400 is connected to the cathode electrode 450 with a suitable DC power source or an AC power source, the anode electrode 430 (the most commonly used material is iron or inscription) will be electrolyzed. Iron ions (Fe2+) or aluminum ions (Al3+) and other products: for example: electrons, hydrogen ions and oxygen. At the same time, the cathode electrode 450 produces: hydrogen and hydroxide ions (OH·). The metal cation (for example, iron ion) can be directly combined with the suspended COD or the water-soluble COD, aggregated into particles of a large particle size, and precipitated to the bottom of the electrolytic cell 41, and can be discharged through the discharge hole 470, so that the wastewater can be discharged. The COD concentration drops rapidly. On the other hand, a metal cation (for example, iron ion) can form a flocculating polymer with a hydroxide ion (〇Η·), and further remove COD from the wastewater. Further, the agglomerates floating in water can also be adsorbed by the bubbles generated by the anode electrode 430 and the cathode electrode 450 into froth which can be scraped or overflowed. Therefore, the treatment of electrocoagulation apparatus (EC) 400 includes the multi-element reactions listed in Table 1: Table 1: Reactions provided by EC treatment # Reaction reaction content 1 Direct oxidation of pollutants on the anode is oxidatively decomposed into: ion / co2 / h2o 2 Indirect oxidation of pollutants is oxidized and decomposed by oxygen to: ion/co2/h2o 3 Direct reduction of contaminants on the cathode to reduce: deposits or volatile organic compounds 19 201113224 4 Indirect reduction... ,-~___ ” Loss/dyeing hydrogen reduction Become: sediment or pinch right object 5 Condensation ^ 7λ I-1* r% Condensation into large particles 6 Floating contaminants are adsorbed by hydrogen or oxygen bubbles into an ang, this, Jie 7 neutralization / precipitation jimm r/oH-1 As a result of the multivariate reaction of Table 1, the use of an electrocoagulation unit (ec) 4〇〇 provides a fast decontamination effect, for example, when wastewater flows through the electrocoagulation unit (ec), its wastewater The COD will be reduced by about 80%. Further, in the present embodiment, the iron material as the anode may be pig iron, black iron, cast iron 'light round iron, skd6 〇 and SS430, and the like. Please refer to Fig. 6 for a schematic view of the electrocoagulation device (EC) of the present invention. As shown in Fig. 6, the electrocoagulation device (EC) 4 of the present invention is an electrolytic cell 410 having an inner diameter of 2 〇 Cm for dividing the anode electrode 43 〇 and the cathode electrode 45 两 into two turns to be placed on the top cover 420. Upper, and fixed with screws, screws and nuts (not shown in the figure). The electrolysis tank 410 is further provided with a water inlet 44 〇 and a water outlet 460 to provide a passage for the wastewater to enter and exit the electrocoagulation device (EC) 400; and the sludge generated by the electrocoagulation device treatment process may be discharged from the sinking body 47. 〇 discharge. In addition, it is emphasized that the number, area, spacing, arrangement of positive and negative electrodes, monopolar or bipolar configuration, DC or in the electrocoagulation device (EC) 4〇〇 of the present invention are The AC power supply, the voltage/current setting, and the like are not limited, and are only one embodiment of the present invention, and the actual electrocoagulation device (EC) structure can be designed according to the wastewater water quality test and processing target, so that The wastewater treated by electrocoagulation unit (EC) 400 meets the following criteria: 1. Water flow rate 200-300 Liter/minute. 2. After the water flows through an electrocoagulation unit (EC), its COD/SS/turbidity removal is 20 201113224 80%. 3. Water flowing through an electrocoagulation unit (£C) removes 1 Kg of COD and consumes only lkWh or less. According to the above invention, when the wastewater is treated by an electrocoagulation device (EC) 4, the following benefits are obtained: 1. Without using chemicals, the wastewater can be treated only by supplying electric energy, so it is clean and pollution-free. 》 2. The amount of sludge is less than 3〇% less than the “chemical coagulation method” (because the electrocoagulation unit does not need to add an anion). 3. The sludge produced by the electrocoagulation unit has a small water content (more than 4%) and can be treated as non-toxic solid waste (this standard has been approved by USEPA). 4. The sludge produced by the electrocoagulation device has high coalescence strength and is not easily dispersed, so it is easy to be filtered (to become a mud cake). 5. There are many types of pollutants that can be removed by electrocoagulation devices, and the removal rate is often over 90%. 6. Electrocoagulation devices enable high concentrations of wastewater to rapidly reduce pollutants (such as COD). 7. The electrocoagulation device has a wide operating temperature range (cold heat does not affect the treatment). 8. The electrocoagulation unit processor does not contain mechanical parts (only the anode is the only consumable that needs to be replaced). 9. The metal cation aggregating agent is easily controlled in a "timely and appropriate amount". 10. The electrocoagulation device occupies a small area (for example, it is estimated to be about 14.1 pings by an electrocoagulation system that treats helium at 38 〇〇m3 or 38 〇〇cmd per day). However, the electrocoagulation device (EC) 400 of the present invention is not versatile, and in the current technology, its treatment limitations in wastewater include: 21 201113224 ι· electrocoagulation device cannot remove monovalent metal ions such as metal ions (Na+, Κ+) 〇2·The electrical conductivity (or TDS) of the treated water after electrocoagulation is higher than before treatment. 3. The electrocoagulation device has a low removal rate of some highly soluble COD. 4. The electrocoagulation unit treatment cannot reduce the wastewater to an extremely low concentration. Therefore, electrocoagulation devices require the assistance of other electrical treatment technologies to recover industrial and domestic wastewater. For example, after the electrocoagulation device (Ec) 400 of the present invention is connected in series with an ozone generating device 300, an electric energy type wastewater treatment device can be formed, which can be used to treat wastewater having a high concentration of COD. The purpose of combining the ozone generating device 300 with the electrocoagulation device (EC) 4〇〇 into a wastewater treatment device is selected because the ozone generating device 300 can provide a treatment effect that the electrocoagulation device (EC) 400 cannot achieve, including: The ozone generating device 300 is capable of reducing the COD in the wastewater to nearly 0 ppm. 2. The ozone generating device 300 does not produce sludge (because the contaminants are oxidized and reduced to C〇2 and η2〇). 3. Ozone (?3) in the ozone generating apparatus 300 reacts to become oxygen, and metal cations are not left behind. Referring to Fig. 7, there is shown a functional block diagram of an electric energy type waste water treatment apparatus of the present invention. As shown in Fig. 7, the electric energy type waste water treatment apparatus 600 of the present invention includes an electrocoagulation apparatus (ec) 400 and an ozone generating apparatus 300', wherein the ozone generating apparatus is as shown in Fig. 4, and the electrocoagulation apparatus (EC) is shown. 400 is shown in Figure 6. Therefore, when the wastewater enters the electrolytic cell 410 through the water inlet 440 of the electrocoagulation device (EC) 400, the wastewater reacts with the anode electrode 430 and the cathode electrode 450 in the electrolytic cell 410, and is then supplied under the supply of a suitable DC power source. As a result of the reaction equations (14) to (18), the COD in the wastewater can be reduced by about 80%; then the treated wastewater is sent to the water inlet 320 by the water outlet 460, and then the water inlet 320 is used. After the wastewater flows through the stacked electrode structure 200, the remaining organic matter in the wastewater can be decomposed into dioxide dioxide and water according to the oxidation results of the reaction equations (丨)~(12), and then discharged from the water outlet 320 to be treated and conformed to Standard water. It is apparent that in order to increase the reaction efficiency of the electric energy type wastewater treatment apparatus 6 of the present invention to save electrical energy, in a preferred embodiment of the present invention, the water inlet 440 of the electrocoagulation apparatus (EC) 400 is provided. A filter device 620 is previously provided for the purpose of pre-filtering substances greater than 1 〇 micron in the wastewater; and then, at the water outlet 460 of the electrocoagulation device (EC) 400 and the water inlet 320 of the ozone generating device 300. An enthalpy device 64 〇 is also interposed, the main purpose of which is to filter the polymer produced in the electrocoagulation device (EC) 400 (for example, to filter a polymer larger than 0.5 μm); finally, the present invention can also be used in an ozone generating device. A filter device 660 is also disposed at the water outlet 34 of the 300, the main purpose of which is to filter minute impurities in the ozone generating device 630 (for example, filtering impurities larger than 2.2 μm) to ensure that the treated quality can be used as production water. . Obviously, the electric energy type wastewater treatment device 600 of the present invention adopts a treatment method in which waste water continuously flows through the electrode during the whole process, so that the waste water is used as a medium or a raw material for generating a treatment agent. The pollutants are removed in-situ, so the electric energy type waste water treatment device 600 of the present invention can treat the wastewater or regenerate the production water by electrolysis of the wastewater without adding any chemical components, so that it does not occur. Second public hazard. When the electric energy type wastewater treatment device 600 of the present invention and the / power supply (not shown) and a pump (not shown) are placed on a movable frame, an independent and movable can be formed. The electric energy type wastewater treatment module, wherein the electric energy type wastewater treatment device is composed of at least one electrocoagulation device (EC) 400 and at least one ozone generating device 300 connected in series, and then at least one pump is used to draw the wastewater into the water. Into the electrolysis cell of the electrocoagulation device (EC) 400; when each 23 201113224 electrocoagulation device (EC) is connected to each of the ozone generating devices and the power supply, the wastewater can be disposed in the electrocoagulation device (Ec The anode electrode and the cathode electrode in the electrolytic cell of the crucible are reacted with oxygen to make the c〇d of the wastewater towel quickly decrease. Then, the wastewater is sent to the ozone generating device to make the wastewater react with the stacked electrode 200. , so that the c〇d in the wastewater can be reduced to near 〇. Similarly, in order to enable the electric energy type wastewater treatment module of the present invention to have a better guoguotian electric moon wastewater treatment module using a plurality of electrocoagulation devices (ec) 4, they are connected in parallel with each other. In addition, when the electric energy type wastewater treatment module uses a plurality of ozone generating device fans, they are also connected to each other in parallel. In addition, when some filtering devices are added to the electric energy type wastewater treatment module of the present invention, in addition to speeding up the treatment speed of the wastewater, the power consumption can be reduced. Therefore, in the electric energy type wastewater treatment module of the present invention, a filtering device may be disposed before the water inlet of the electrocoagulation device (EC) 400 for the purpose of pre-filtering substances larger than 10 microns in the wastewater; An argon is also disposed between the water outlet of the electrocoagulation device (Ec) 4 and the water inlet of the ozone generating device 3; the main purpose of the device is to filter the polymerization generated in the electrocoagulation device (EC) 400. Finally, the present invention may also be provided with a filtering device at the outlet of the ozone generating device 300, the main purpose of which is to filter minute impurities in the ozone generating device (for example: filtration). More than 0.2 micron impurities), so that the treated water can be used as process water. Obviously, if it is necessary to increase the amount of wastewater treatment per unit time, f will use a plurality of electric energy type wastewater treatment modules to form an electric energy type wastewater treatment system for wastewater treatment. Such an additive-to-module system has the following advantages: 1. Designing the most economical and practical group according to the type of pollutants and the recycling target of wastewater 24 201113224 Combined system. 2. The combined system operates in parallel independent lines. It does not stop due to the condition of one of the electrical processing units. 3. The combined system is easy to expand production capacity, installation, relocation and maintenance. 4. The electrical processing units can be placed in an overlapping manner to further reduce the footprint of the system. There is no limit to the point of use of the combined system or its secondary system. Through an appropriate number of combinations, the electric energy wastewater treatment system of the present invention can treat high COD and turbid wastewater to the following standards: _ 1. COD is reduced from 1,500 ppm to 40 ppm or less. 2. SS is reduced to less than 20 ppm. 3. Chroma < 500 ADMI value. 4. 1500 CMD throughput, producing about 1 ton of sludge. 5. Recycle 90% of the wastewater from the production line' for reuse in production. Therefore, the electric energy type wastewater treatment system of the invention can convert the waste water into a clear production water by completely removing the waste water from the state of being contaminated with black chemicals, and can improve the recovery rate of the wastewater to 90%, so it can be directly It is used in production to further achieve the function of saving water. • Water treated by the electric energy type wastewater treatment device 600, the electric energy type wastewater treatment module or the electric energy type wastewater treatment system of the present invention (including water that meets the discharge standard and water that can be used as production), if treated The human waste standard can be reached when the wastewater is tested by a detection device and meets the discharge standard water's and then filtered through an RO reverse osmosis unit. Referring to Fig. 8, which is a further preferred embodiment of the electric energy type wastewater treatment system of the present invention, the electric energy type wastewater treatment system 700 can treat wastewater to human drinking standards. As shown in Fig. 8, when the wastewater is treated by the electric energy type wastewater treatment device 6〇〇, the electric energy type wastewater treatment module or the electric energy type wastewater 25 201113224 processing system of the present invention* and passed the test by a detecting device 650, That is, it can be used as production water; if the qualified water is filtered through a RO reverse osmosis device 720, the human drinking standard can be achieved. In a preferred embodiment, the water filtered by the RO reverse osmosis unit 720 can be subjected to the treatment (i.e., disinfection) of the ozone generating unit 300 once to achieve the human direct drinking standard. Although the specific structure of the electrocoagulation device and the ozone generating device in the electric energy type wastewater treatment system of the present invention and its embodiment have been disclosed in the foregoing description, the disclosed content is only the electric energy type wastewater treatment system of the present invention. The disclosure is not intended to limit other embodiments of the invention. Therefore, in addition to the above detailed description, the present invention can be widely practiced in other embodiments, for example, an electrode arrangement in an electrocoagulation device and an ozone generating device structure, an electrocoagulation device, and a fixing manner of an ozone generating device structure. And a specific combination structure of the electrocoagulation device and the ozone generating device. Therefore, those skilled in the art can make various changes in the form without departing from the spirit and scope of the invention as described in the foregoing. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a flow-through ozone generator of the present invention. 2A to 2E are schematic views of electrodes of the ozone generating apparatus of the present invention. Fig. 3 is a schematic view showing a stacked electrode in the ozone generating apparatus of the present invention. Fig. 4 is a view showing another embodiment of a stacked electrode in the ozone generating apparatus of the present invention. Fig. 5 is a schematic view showing the reaction in the electrolytic cell of the electrocoagulation device of the present invention. Figure 6 is a schematic view of the electrocoagulation device of the present invention. Fig. 7 is a functional block diagram of an electric energy type wastewater treatment system of the present invention. 201113224 Fig. 8 is a functional block diagram showing another embodiment of the electric energy type wastewater treatment system of the present invention. [Main component symbol description] 10 100A, 100B 110A, 110B 120 130 140/160 150 180 181 200 300 310 320 330 340 400 410 420 430 '450 440 460 470 600 Flow-through ozone generator electrode plate electrode plate hole housing 0-shaped ring anode/cathode electrode plate positive and negative electrode connection end power supply module pulse width adjusting device (PWM) electrode plate stack structure ozone generating device upper cover water inlet lower cover water outlet electrocoagulation device electrolytic cell top cover electrode inlet Spout sediment discharge hole electric energy type wastewater treatment system 27 201113224 620 ' 640 ' 660 filter device 650 detection device 720 RO reverse osmosis device
2828
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW98134606A TW201113224A (en) | 2009-10-13 | 2009-10-13 | Power type waste water treatment system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW98134606A TW201113224A (en) | 2009-10-13 | 2009-10-13 | Power type waste water treatment system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201113224A true TW201113224A (en) | 2011-04-16 |
Family
ID=44909554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW98134606A TW201113224A (en) | 2009-10-13 | 2009-10-13 | Power type waste water treatment system |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TW201113224A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI658867B (en) * | 2016-08-24 | 2019-05-11 | 林信湧 | Gas generator |
| TWI658866B (en) * | 2016-08-24 | 2019-05-11 | 林信湧 | Gas generator |
-
2009
- 2009-10-13 TW TW98134606A patent/TW201113224A/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI658867B (en) * | 2016-08-24 | 2019-05-11 | 林信湧 | Gas generator |
| TWI658866B (en) * | 2016-08-24 | 2019-05-11 | 林信湧 | Gas generator |
| US10350378B2 (en) | 2016-08-24 | 2019-07-16 | Hsin-Yung Lin | Gas generator |
| US10385463B2 (en) | 2016-08-24 | 2019-08-20 | Hsin-Yung Lin | Gas generator |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU767548B2 (en) | Electrolytic apparatus, methods for purification of aqueous solutions and synthesis of chemicals | |
| KR100379123B1 (en) | Electrolytic apparatus and methods for purification of aqueous solutions | |
| He et al. | Evaluation of sono-electrocoagulation for the removal of Reactive Blue 19 passive film removed by ultrasound | |
| JP4392354B2 (en) | High electrolysis cell | |
| AU2007257247B2 (en) | Electrolytic activation of water | |
| US20130264197A1 (en) | Nanocatalytic electrolysis and flocculation apparatus | |
| US20120031852A1 (en) | Graphene based electrodes for electrochemical reactions, and electrooxidation process for the removal of contaminants from liquids using said electrodes | |
| CN104671364A (en) | Electrochemical wastewater treatment method for removing salts and refractory organic matters synchronously | |
| GB2515324A (en) | Electrolytic advance oxidation processes to treat wastewater, brackish and saline water without hydrogen evolution | |
| JP2009190016A (en) | Method for preventing and removing biofilm in electrolytic capacitor for water purification | |
| CN108358363A (en) | A kind of deep treatment method of organic sewage with high salt | |
| CN105384222A (en) | Waste water electric flocculation treatment device | |
| CN107298490B (en) | Electrochemical reactor, method for removing chloride ions in wastewater through electric flocculation, precipitated product and application | |
| TW201130751A (en) | Compound apparatus for processing waste water | |
| WO2014165998A1 (en) | Treatment of a waste stream through production and utilization of oxyhydrogen gas | |
| TW201113224A (en) | Power type waste water treatment system | |
| Govindaraj et al. | Electrochemical treatment of endocrine-disrupting chemical from aqueous solution | |
| CN205258091U (en) | Electric flocculation equipment of waste water | |
| TW200932956A (en) | Configurable ozone generators | |
| WO2011054155A1 (en) | Electric energy type wastewater treatment system | |
| KR200307692Y1 (en) | Functional drinking water supply apparatus for Indoor electrolytic treatment of microorganism contaminated | |
| CN213569931U (en) | Sterilizing and water purifying integrated machine | |
| Chang et al. | Study on the efficacy of sterilization in tap water by electrocatalytic technique | |
| CN101896432A (en) | The method of preconditioning drinking water | |
| KR100454165B1 (en) | Indoor electrolytic apparatus for treatment of microorganism- contaminated and functional drinking water |