WO2011054155A1

WO2011054155A1 - Electric energy type wastewater treatment system

Info

Publication number: WO2011054155A1
Application number: PCT/CN2009/074857
Authority: WO
Inventors: 薛立人; 李皞白
Original assignee: 冠亚智财股份有限公司
Priority date: 2009-11-06
Filing date: 2009-11-06
Publication date: 2011-05-12
Also published as: CN102712508A

Abstract

An electric energy type wastewater treatment module comprises an electric energy type wastewater treatment system, a power supply and a pump. The electric energy type wastewater treatment system comprises an electriccoagulation (EC) set and an ozone generator in series. In the electric energy type wastewater treatment module, wastewater is firstly treated with the anode and cathode in the electriccoagulation (EC) set, and then treated with the stack electrode in the ozone generator.

Description

电能式废水处理*** 技术领域本发明涉及一种以使用电解方式来进行废水或是污水处理装置；特别是有关于提供一种电能式废水或是污水处理装置，其组合了电凝聚（EC )装置以及臭氧产生装置，并于电凝聚（ EC )装置以及臭氧产生装置施加一电源后，通过使废水连续流过电极的处理方式，以废水为产生处理剂的媒介或原料，来将废水中的污染物当场 (in-situ)去除，以达到废水或污水的排放标准。背景技术饮用水的消毒杀菌对人体健康可谓至为重要之一环。不论水的来源为何，其中必然含有某些形式的微生物，包括细菌、病毒或单细胞生物等。在这些微生物中，致病有机体引起的腹泻、伤寒、肝炎和霍乱等病症，可能导致饮用者的死亡。因此基于安全考虑，饮用前必须将水中的各种病原体消灭。此外，来自工厂和农地的毒性有机化合物、酸、碱、肥料以及杀虫剂等，亦可能流入供应民生用水的蓄水场。由于这些化合物极可能致癌，因此也须于使用这些被污染的水之前，宜先行对此污染水中的化合物解毒或消毒。对污染水的消毒方法主要有四种，即加氯消毒、氯胺消毒、臭氧消毒以及紫外线消毒；显然地，在上述这些方法中，使用氯（C12 ) 气、次氯酸钠 ( NaOCl )溶液或次氯酸钙 [Ca(OCl)2]粉末等的加氯消毒法使用最为广泛。然而，除了添加化学药剂之外，亦可能如美国专利第 3,622,479、 4,512,865 以及 7,011,750 号等申请中所述，利用电化学产生次氯酸根离子以达成加氯消毒。虽然加氯消毒的可行性已经确认，但其处理过程中所产生的臭气、异味，以及其反应緩慢、酸碱值范围狭窄和消毒剂残余物可能成为致癌物质的缺点则为人诟病。氯胺消毒法是利用形成于氨（NH3 ) 与次氯酸盐（OC1- )之间的消毒剂，然而不论氯酸盐或氯胺皆无法对有害化学药剂产生解毒作用，因此氯胺消毒法之效果仍有不足。臭氧消毒与紫外线消毒则为两种无残留疑虑的消毒技术。事实上，紫外线消毒法系如美国专利第 4,230,571 与 4,968,483 号所揭示，以紫外线辐射氧气而产生消毒用的臭氧。此外，紫外线辐射也通过形成氢氧自由基（·ΟΗ ) 而提升臭氧的杀菌效果，这是因为氢氧自由基为较臭氧更强的氧化剂，如美国专利第 7,063,794 号所述。然而，紫外线并无法消灭梨形鞭毛虫或隐孢子虫（Cryptosporidium ) 包嚢，且亦不适合处理因其中含有大量悬浮固体、混浊、有色或芳香族化合物而导致光线减弱的水。然而，对于含有毒化学药剂的工业用水的消毒而言，紫外线虽然作用緩慢但通常颇具成效。若要快速产生臭氧，其制造通常施以极高的电压，例如 3000V 的高电压，然后通过电暈放电以分解氧分子而形成氧的三原子同素异形物。因此，用电即占总臭氧生产操作成本的 26-43%, 且放电过程中，易于产生例如氮氧化物（NOx ) 等污染空气之物质。另外，如何将气体均匀分布于水中，则成为另一方面的问题。因此，从效率角度来看，使用低电压的水电解来产生臭氧的方式，亦即习知的电解臭氧，相较于气体加工或电暈放电更具效率。现已有愈来愈多文献报告提供将电解臭氧用于水的消毒和解毒的技术，如美国专利第 5,407,550; 5,686,051 ; 5,744,028; 6,328,862; 6,733,638; 6,902,670 与 6,984,295号等所披露的，此处仅略举数例。此外，就水的消毒解毒而言，臭氧为安全、千净、便利以及强效的氧化剂。臭氧的应用范围广及个人口腔卫生、居家清洁与洗涤，乃至于工业加工和废水处理。目前全世界已至少有十七国将臭氧疗法釆用为合法的医学疗法。虽然臭氧疗法尚未通过美国食品药物管理局（FDA ) 审批，但已至少有十二州通过立法，允许臭氧疗法成为一种可供选择的治疗方式。臭氧的医疗用途可见于美国专利第 4,968,483 号的血液氧化疗法（ haematological ) , 美国专利第 5,834,030号的外伤治疗以及美国专利第 6,902,670号中，用于清洗血液透析机导管以取代可能产生化学残留的醋酸或甲醛。在工业应用上，如美国专利第 6,851,873及 6,983,756号所述，将臭氧用于剥除光阻薄膜，以及如美国专利第 7,029,589 号所述，分解挥发性有机化学物。臭氧在上述所有应用中提供破坏性的氧化作用，而其许多新的应用，如消除固体、液体和气体污染物，亦正逐渐被开发。臭氧无疑是一种可多方面应用的消毒剂。然而，臭氧产生过程中伴随的烟雾却影响了人们对臭氧的评价，甚至普遍将臭氧误解为危险或致命化学物，而非友善的媒介。这是因为臭氧的气体寿命有限（约 30 分钟），故臭氧并不适于储存运送，故必须于使用前或使用当场实时生产。如上文中所述，虽然低电压电解法为最佳的臭氧产生方式（例如：前述之 '550至' 295号等专利；)，但却同样存在三个问题。问题之一是以电解水来形成臭氧，其所需之阳极材料为铂（Pt ) 或 β-二氧化铅 ( β— PbO2 ) 。然而，铂的价格极高，且于室温下无法有效产生臭氧。另外，二氧化铅虽然可于室温下有效产生臭氧，但铅为一环境有害物，而遭许多国家禁止用于水质处理。接着，前述专利的电解臭氧方法的问题之二在于臭氧生产需要离子交换膜（membrane ) 。此离子交换膜除了成本高昂外，由于离子交换膜易受污染物污染，因此不能直接放置于废水中，故其使用的范围亦有严格限制。很明显地，使用离子交换膜产生电解臭氧仅能如同电暈放电一样，须先于他处形成臭氧，而后再将气体输送至水中以为消毒之用。因此，亦产生电解臭氧的第三种问题，亦即无法达成现场实时消毒的效果。因此，现有技术亟需寻求一种效率高且经济的电解水生成臭氧方式，以达成便利有效使用臭氧的目标。发明内容本发明的目的之一是提供一种电能式废水的处理***，可以在不需添加任何化学成份状况下，通过对废水的电解来产生臭氧，以达到消毒的目的。本发明另一目的在于提供一种电能式废水的处理***，以电凝聚的电解方来取代任何添加化学成份的方式，故不会产生二次公害。本发明另一目的在于提供一种电能式废水的处理***，其釆用废水连续流过电极的处理方式，因此是以废水为产生处理剂的媒介或原料，来将废水中的污染物当场 (in-situ)去除，故本发明的电能式废水处理装置可以在不需添加任何化学成份状况下，通过对废水的电解使得废水得到处理或再生成生产用水。本发明的再一目的在于提供一种电能式的废水处理***，其以电解方式来处理废水，可以提高废水的回收率，以增加水的再利用，进一步达到省水功能。本发明的另一目的在于提供一种电能式废水处理*** ,其可依据所要处理废水的成份做不同的电能式电解装置的组合，使得废水的处理***可以依据客户所要处理的废水进行不同的设计（即符合客制化之需求）。本发明的再一目的在于提供一种电能式废水的处理***，其以掺杂二氧化锡（M-SnO2 ) 的膜为电极，以进行各种废水的电解与消毒，若配合适当装置，可以使得经过处理后的废水达到生物饮用标准。本发明的又一目的在于提供一种电能式的废水处理***，其以掺杂二氧化锡 ( M-SnO2 ) 的膜为电极用于产生臭氧的反应，由于掺杂二氧化锡 ( M-SnO2 ) 厚膜的电极具有产生大量臭氧的功能，故可降低电能消耗。依据上述目的，本发明首先提供一种电能式废水处理***，其由一电凝聚装置（EC )与一臭氧产生装置串接所组成，其中该电能式废水处理***的特征在于：废水经过电凝聚装置（EC ) 并与电凝聚装置（EC ) 中的阳极电极与阴极电极反应后，再经由臭氧产生装置中的堆栈电极处理。本发明接着提供一种电能式废水处理模块，包括一电凝聚装置（EC ) 与一臭氧产生装置串接所组成的电能式废水处理***、电源供应器以及泵，其中该电能式废水处理模块的特征在于：废水经过电凝聚装置（EC )并与电凝聚装置（EC ) 中的阳极电极与阴极电极反应后，再经由臭氧产生装置中的堆栈电极处理。本发明还提供一种电能式废水处理***其由多个电能式废水处理模块所组成，而每一电能式废水处理模块包括电凝聚装置（EC )与臭氧产生装置串接所组成的电能式废水处理***、电源供应器以及泵，其中该电能式废水处理***的特征在于：废水经过每一电凝聚装置（EC )并与每一电凝聚装置 ( EC )中的阳极电极与阴极电极反应后，再经由每一臭氧产生装置中的堆栈电极处理。附图说明图 1是本发明的流通式臭氧产生器的示意图。图 2A〜2E是本发明臭氧产生装置的电极示意图。图 3是本发明臭氧产生装置中堆栈电极的示意图。图 4是本发明臭氧产生装置中的堆栈电极另一实施例的示意图。图 5是本发明电凝聚装置电解槽中的反应示意图。图 6是本发明电凝聚装置的示意图。图 7是本发明电能式废水处理***的功能方块示意图。图 8是本发明电能式废水处理***另一实施例的功能方块示意图。主要组件符号说明 BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for performing wastewater or sewage treatment using an electrolytic method; in particular, to provide an electric energy type wastewater or a sewage treatment apparatus, which is combined with an electrocoagulation (EC) apparatus And an ozone generating device, and after applying a power source to the electrocoagulation (EC) device and the ozone generating device, the waste water is used as a medium or a raw material for generating a treating agent by treating the waste water continuously flowing through the electrode, thereby causing pollution in the wastewater. The in-situ is removed to meet wastewater or wastewater discharge standards. BACKGROUND OF THE INVENTION Sterilization of drinking water is an important part of human health. Regardless of the source of the water, it must contain certain forms of microorganisms, including bacteria, viruses or single-celled organisms. Among these 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, acids, 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, chloramine disinfection, ozone disinfection and UV disinfection; obviously, in these methods, chlorine (C12) gas, sodium hypochlorite (NaOCl) solution or hypochlorous is used. The chlorination method of calcium acid [Ca(OCl)2] powder or the like is most widely used. However, in addition to the addition of chemical agents, it is also possible to electrochemically produce hypochlorite ions for chlorination as described in U.S. Patent Nos. 3,622,479, 4, 512, 865, and 7, 011, 750. Although the feasibility of chlorination has been confirmed, the odors and odors generated during the treatment, as well as the slow reaction, narrow pH range and the possibility that the residue of the disinfectant may become a carcinogen are rickets. The chloramine disinfection method utilizes a disinfectant formed between ammonia (NH3) and hypochlorite (OC1-). However, whether chlorate or chloramine cannot detoxify harmful chemicals, chloramine disinfection method The effect is still insufficient. Ozone disinfection and UV disinfection are two disinfection techniques without residue. In fact, the ultraviolet disinfection method is disclosed in U.S. Patent Nos. 4,230,571 and 4,968,483, to ultraviolet radiation. Oxygen produces ozone for disinfection. In addition, ultraviolet radiation also enhances the bactericidal effect of ozone by forming a hydroxyl radical (·ΟΗ) 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 eliminate the inclusion of P. cerevisiae or Cryptosporidium, and it is not suitable for treating water that is weakened by a large amount of suspended solids, turbid, colored or aromatic compounds. However, for the disinfection of industrial water containing toxic chemicals, ultraviolet light is slow but usually effective. To produce ozone quickly, it is usually manufactured by applying a very high voltage, such as a high voltage of 3000V, and then corona discharge to decompose oxygen molecules to form a three-atomic allotrope of oxygen. Therefore, the electricity consumption accounts for 26-43% of the total ozone production operation cost, and during the discharge process, substances such as nitrogen oxides (NOx) which are polluted by air are apt to be generated. In addition, how to uniformly distribute the gas in the water becomes a problem on the other hand. Therefore, from the viewpoint of efficiency, the use of low-voltage water electrolysis to generate ozone, that is, conventional electrolytic ozone, is more efficient than gas processing or corona discharge. There are now more and more literature reports providing techniques for the use of electrolytic ozone for the disinfection and detoxification of water, as disclosed in U.S. Patent Nos. 5,407,550, 5,686,051, 5,744,028, 6,328,862, 6, 733, 638, 6, 902, 670 and 6, 984, 295, et al. To name a few. In addition, ozone is a safe, clean, convenient and potent oxidant for the disinfection and detoxification of water. 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 used 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 allowing ozone therapy to be an alternative treatment. The medical use of ozone can be found in the blood oxidative therapy (haematological) of U.S. Patent No. 4,968,483, the trauma treatment of U.S. Patent No. 5,834,030, and the U.S. Patent No. 6,902,670, which is used to clean the hemodialysis machine catheter to replace the acetic acid which may cause chemical residues. Or formaldehyde. In an industrial application, as described in U.S. Patent Nos. 6,851,873 and 6,983,756, ozone is used to strip the photoresist film, and as described in U.S. Patent No. 7,029,589, the volatile organic chemical is decomposed. Ozone provides destructive oxidation in all of the above applications, and many new applications, such as the elimination of solid, liquid and gaseous contaminants, are being developed. Ozone is undoubtedly 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, rather than a friendly medium. This is because ozone has a limited gas life (about 30 minutes), so ozone is not suitable for storage and transportation, so it must be produced in real time before use or on the spot. As described above, although the low voltage electrolysis method is the best ozone generation method (for example, the aforementioned '550 to '295 patents, etc.), But there are also three problems. One of the problems is to electrolyze water to form ozone. The anode material required is platinum (Pt) or beta-lead dioxide (β-PbO2). However, platinum is extremely expensive and does not produce ozone efficiently at room temperature. In addition, although lead dioxide can effectively produce ozone at room temperature, lead is an environmental hazard and is prohibited from being used for water treatment in many countries. Next, the second problem of the electrolytic ozone method of the aforementioned patent is that ozone production requires an ion exchange membrane. In addition to the high cost of this ion exchange membrane, since the ion exchange membrane is easily contaminated by pollutants, it cannot be directly placed in the wastewater, so the scope of its use is also strictly limited. Obviously, the use of ion exchange membranes to produce electrolytic ozone can only be as corona discharge, ozone must be formed before it, and then the gas is transported to the water for disinfection. Therefore, the third problem of electrolytic ozone is also generated, that is, the effect of on-site real-time disinfection cannot be achieved. Therefore, the prior art urgently needs to find an efficient and economical method for generating ozone by electrolyzed water to achieve the goal of facilitating efficient use of ozone. SUMMARY OF THE INVENTION One object of the present invention is to provide a treatment system for an electric energy type waste water, which can generate ozone by electrolysis of waste water without adding any chemical components to achieve the purpose of disinfection. Another object of the present invention is to provide a treatment system for an electric energy type wastewater, in which the electrocoagulation electrolysis is substituted for any way of adding chemical components, so that secondary pollution is not caused. Another object of the present invention is to provide a treatment system for an electric energy type waste water, in which a waste water continuously flows through an electrode, so that waste water is used as a medium or a raw material for producing a treatment agent to cause pollutants in the waste water to be present ( In-situ), the electric energy type wastewater treatment device of the present invention can treat wastewater or regenerate production water by electrolysis of wastewater without adding any chemical components. Still another object of the present invention is to provide an electric energy type wastewater treatment system which treats wastewater by electrolysis, which can improve the recovery rate of wastewater, increase water reuse, and further achieve water saving function. Another object of the present invention is to provide an electric energy type wastewater treatment system which can make a combination of different electric energy type electrolyzing devices according to the components of the wastewater to be treated, so that the wastewater treatment system can be designed differently according to the wastewater to be treated by the customer. (ie meet the needs of customization). A further object of the present invention is to provide a treatment system for an electric energy type wastewater, which uses a film doped with tin dioxide (M-SnO2) as an electrode to perform electrolysis and disinfection of various waste waters, and if equipped with appropriate devices, The treated wastewater is brought to the biological drinking standard. It is still another object of the present invention to provide an electric energy type wastewater treatment system using a film doped with tin dioxide (M-SnO2) as an electrode for generating ozone reaction due to doping of tin dioxide (M-SnO2) The thick film electrode has the function of generating a large amount of ozone, so that the power consumption can be reduced. 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, wherein the electric energy type wastewater treatment system is characterized in that: the wastewater is electrocoagulated The device (EC) is reacted with the anode electrode and the cathode electrode in the electrocoagulation device (EC), and then processed through the stack electrode in the ozone generating device. The invention further provides an electric energy type wastewater treatment module, comprising an electric energy type wastewater treatment system, a power supply device and a pump, which are composed of an electrocoagulation device (EC) and an ozone generating device connected in series, wherein the electric energy type wastewater treatment module The waste water is passed through an electrocoagulation device (EC) and reacted with an anode electrode and a cathode electrode in the electrocoagulation device (EC), and then processed through a stack electrode in the ozone generator. The invention also provides an electric energy type wastewater treatment system, which is composed of a plurality of electric energy type wastewater treatment modules, and each electric energy type wastewater treatment module comprises an electric energy type wastewater composed of an electrocoagulation device (EC) and an ozone generating device connected in series. a treatment system, a power supply, and a pump, wherein the electric energy type wastewater treatment system is characterized in that: after each wastewater is passed through each electrocoagulation device (EC) and reacted with an anode electrode and a cathode electrode in each electrocoagulation device (EC), It is then processed via a stack electrode in each ozone generating device. BRIEF DESCRIPTION OF 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. Figure 3 is a schematic illustration of a stack electrode in the ozone generating apparatus of the present invention. Figure 4 is a schematic illustration of another embodiment of a stack 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 apparatus of the present invention. Figure 6 is a schematic illustration of an electrocoagulation device of the present invention. Figure 7 is a functional block diagram of the electric energy type wastewater treatment system of the present invention. Figure 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 流通式臭氧产生器 100A、 100B 电极板 110A、 110B 电极板上的孑 L洞 120 夕卜壳 10 Flow-through ozone generator 100A, 100B electrode plate 110A, 110B 孑 L hole on the electrode plate 120

130 O形环 140/160 卩曰 /阴极电极板 130 O-ring 140/160 卩曰 / cathode electrode plate

150 正负电极连接端 180 电源供应器模块 150 positive and negative electrode connection 180 power supply module

181 脉波宽度调整装置（PWM ) 200 电极板堆栈结构 181 Pulse Width Modulator (PWM) 200 Electrode Plate Stack Structure

300 臭氧产生装置 310 上盖 300 Ozone generating device 310 Cover

320 进水口 330 下盖 320 water inlet 330 lower cover

340 出水口 400 电凝聚装置 340 water outlet 400 electrocoagulation device

410 电解曹 420 顶盖 430、 450 电极 440 进水口 410 Electrolytic Cao 420 Top Cover 430, 450 Electrode 440 Inlet

460 出水口 470 沉淀物 4 出孑 L 460 water outlet 470 sediment 4 out 孑 L

600 电能式废水处理*** 620、 640、 660 过滤装置 600 electric energy wastewater treatment system 620, 640, 660 filter unit

650 检测装置 720 RO逆渗透装置具体实施方式本发明在此披露一种电压电解水产生电凝聚以及臭氧的电能式电解装置。为了能彻底地了解本发明，将在下列的描述中提出详尽的说明。显然地，本发明的实施并未限定于臭氧产生装置发明普通技术人员所熟习的特殊细节。另一方面，众所周知的低电压电解水产生臭氧的过程并未描述于细节中，以避免造成本发明的不必要限制。本发明的较佳实施例会详细描述如下，然而除了这些详细描述外，本发明还可以广泛地以其它实施方式来实施中，本发明的保护范围以权利要求书的限定为准。二氧化锡（SnO₂ ) 为一种无毒性半导体，其目前已被广泛用于感应器、电池、电变色窗户、太阳能电池以及液晶显示器（LCD ) 的生产。如 R. K0tz 「使用超高伏阳极进行电气化学废水处理，一辑：二氧化锡阳极的物理及电气化学特性」以及应用电气化学期刊第 21卷第 1辑， 14-20页（ 1971年）所指出，纯二氧化锡为一 n型半导体，具有一约为 3.5 eV的直接能隙。另外，二氧化锡尚具有其它特性：（1)高化学和电化学稳定性；（2)高电子传导性以及 (3)高析氧过电位 ( high oxygen evolution overpotential ) 。其中对于电解臭氧尤有帮助的性能是二氧化锡的氧过电位较铂高为 0.6V。从成本角度来看，二氧化锡亦较铂更具优势。虽然美国专利第 5,364,509、 4,839,007和 3,627,669 号等对于以二氧化锡进行废水处理已有叙及，但其在材料改良与反应器或电解器的效率方面仍有待改进。二氧化锡可掺杂一或多种金属，例如锑（Sb ) 、镍（ Ni ) 、铁（ Fe ) 、 4了（ Ru ) 、铂（ Pt ) 、钯（ Pd ) 、铑（ Rh )和钴（ Co ) , 或者其亦可与一非金属掺杂，如氟（F )。此外，为提升臭氧产生效率， Wang Y-H与其研究团队将二氧化锡与两种金属掺杂，其技术可见于电气化学协会期刊第 152卷第 11辑，第 197至 200页（ 2005年）， "掺锑及镍氧化锡电极上的臭氧电解生成，，一文。本发明参考上述文献发展出特有制造方法。此外，现有技术已将二氧化锡 ( SnO₂ )镀在金属上（例如：铁，以形成马口铁），可作为食品级的容器，因此，以二氧化锡（SnO₂ ) 所制造成的电极，可以安全地于水中电解出臭氧，再经由适当处理（例如经过 RO ( reverse osmosis ) 逆渗透处理）后，以提供生物饮用水。一般而言，制造锑镍掺杂二氧化锡电极需先准备一些包含特定比例的锡、娣和镍前驱物的酒 ^青溶液，例如镍： 4弟：锡 =1 ： 10 ： 600 , 并将此酒賴- 溶液涂布于钛（Ti )基板上。接着，将涂布在钛基板上的酒精溶液经 100-300 °C的高热分解，以转化为一种锑镍掺杂二氧化锡层；再接着将上述涂布及高热分解的步 4聚重复数次；例如：在一较佳的过程要经过 10 次以上的高热分解。最后，再将带有多重涂布层的钛基板以 500-600 °C烧结 30分钟至 2小时。需要经过如此复杂的过程，是因为涂布与高温分解循环进行的次数和热处理条件均密切影响制造出的锑镍掺杂二氧化锡电极的臭氧形成能力和可靠性，同时，本发明上述所公开的加热过程所获得的多重涂布层所制成的电极质量极佳，可使锑镍掺杂二氧化锡电极于室温下可产生超过 30%臭氧产生电流效率。另一方面，本发明还-险证锑镍掺杂二氧化锡电极的以下特性，有益于电解臭氧作为较难处理的工业废水处理的有效使用： 650 DETECTION DEVICE 720 RO Reverse Osmosis Apparatus DETAILED DESCRIPTION OF THE INVENTION The present invention herein discloses an electric energy type electrolysis apparatus that produces electrocoagulation and ozone by voltage electrolysis of water. In order to fully understand the present invention, a detailed description will be given in the following description. Obviously, the practice of the invention is not limited to the specific details familiar to those skilled in the art of ozone generating devices. On the other hand, the well-known process of generating ozone by low-voltage electrolyzed water is not described in detail to avoid unnecessarily limiting the invention. The preferred embodiments of the present invention are described in detail below, but the invention may be embodied in other embodiments, and the scope of the invention is defined by the scope of the claims. Tin dioxide (SnO ₂ ) is a non-toxic semiconductor that is currently used in the production of inductors, batteries, electrochromic windows, solar cells, and liquid crystal displays (LCDs). Such as R. K0tz "Ultra-high-volt anodes for electro-chemical wastewater treatment, Series: Physical and Electrochemical Characteristics of Tin Oxide Anodes" and Applied Electrochemistry, Vol. 21, No. 1, pp. 14-20 (1971), pure Tin dioxide is an n-type semiconductor having a direct energy gap of about 3.5 eV. In addition, tin dioxide has other properties: (1) high chemical and electrochemical stability; (2) high electron conductivity and (3) high oxygen evolution overpotential. Among them, the performance that is particularly helpful for electrolytic ozone is that the oxygen overpotential of tin dioxide is 0.6V higher than that of platinum. From a cost perspective, tin dioxide is also more advantageous than platinum. Although the use of tin dioxide for wastewater treatment has been described in U.S. Patent Nos. 5,364,509, 4,839,007 and 3,627,669, etc., there is still room for improvement in material improvement and efficiency of the reactor or electrolyzer. Tin dioxide can be doped with one or more metals such as bismuth (Sb), nickel (Ni), iron (Fe), ruthenium (Ru), platinum (Pt), palladium (Pd), ruthenium (Rh) and cobalt. (Co), or it may also be doped with a non-metal such as fluorine (F). In addition, in order to improve the efficiency of ozone production, Wang YH and his research team doped tin dioxide with two metals. The technique can be found in the Journal of the Electrochemical Association, Vol. 152, No. 11, pp. 197-200 (2005), the antimony-doped tin oxide and nickel oxide electrode in electrolytic ozone generation according to the present invention ,, a text document to develop specific reference to the above production method in addition, the prior art has tin dioxide (SnO ₂₎ coating on a metal (e.g.: iron, In order to form a tinplate, it can be used as a food-grade container. Therefore, an electrode made of tin dioxide (SnO ₂ ) can safely electrolyze ozone in water and then be treated appropriately (for example, by RO (reverse osmosis) After infiltration treatment, to provide biological drinking water. In general, the preparation of yttrium-nickel-doped tin dioxide electrode requires preparation of some liquor containing a specific proportion of tin, antimony and nickel precursors, such as nickel: 4 brother : tin = 1: 10: 600, and the solution is coated on a titanium (Ti) substrate. Next, the alcohol solution coated on the titanium substrate is decomposed by high heat at 100-300 °C. In order to convert into a ruthenium nickel doped tin dioxide layer; then the above coating and high thermal decomposition step 4 is repeated several times; for example: in a preferred process, more than 10 times of high thermal decomposition. Finally, The titanium substrate with multiple coating layers is then sintered at 500-600 ° C for 30 minutes to 2 hours. This complicated process is required because the number of coatings and pyrolysis cycles and heat treatment conditions are closely related to the production. The ozone forming ability and reliability of the yttrium-nickel-doped tin dioxide electrode, and the electrode made by the multiple coating layers obtained by the above-mentioned heating process of the present invention are excellent in quality, and can be doped with lanthanum nickel. The tin oxide electrode can generate more than 30% ozone generating current efficiency at room temperature. On the other hand, the invention also has the following characteristics of the nickel-doped tin-doped electrode, which is beneficial to the electrolytic ozone treatment as a more difficult industrial wastewater treatment. Effective use:

1. 本发明的锑镍掺杂二氧化锡电极的制造方法可用于制造大尺寸（即使高达 15英寸直径）及各种形状的锑镍掺杂二氧化锡电极。 2. 本发明所制造的锑镍掺杂二氧化锡电极，可直接以废水为媒介进行电解而直接于废水中产生臭氧，故不须使用如氯化钠或硫酸等特定电解质。 1. The method for producing a bismuth-nickel-doped tin oxide electrode of the present invention can be used to produce a nickel-doped tin-doped electrode of a large size (even up to 15 inches in diameter) and various shapes. 2. The ruthenium-nickel-doped tin dioxide electrode produced by the invention can directly generate electricity by directly electrolyzing waste water as a medium to generate ozone, so that it is not necessary to use a specific electrolyte such as sodium chloride or sulfuric acid.

3. 当本发明制造的锑镍掺杂二氧化锡电极在处理低氯化物含量的废水时，可使用不锈钢故为阴极，例如选用 316、 314或 304等级的不锈钢作为阴极；而对于高氯化物含量的水，例如海水，可使用钛做为阴极。 3. When the yttrium-nickel-doped tin dioxide electrode produced by the present invention is used to treat low-chloride-containing wastewater, stainless steel may 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 water content, such as seawater, titanium can be used as the cathode.

4. 本发明所制造的锑镍掺杂二氧化锡电极不需要使用离子交换膜分离阳极和阴极。 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.

5. 本发明所制造的锑镍掺杂二氧化锡电极，其形成于锑镍掺杂二氧化锡电极上的臭氧和氧气气泡非常细致。同时过氧化氢（H₂O₂ )会配合臭氧而产生，这是因微小臭氧气泡和阴极的氢气反应而形成，其产生方式与雨雪中过氧化氢自然生成的作用类似。 5. The ruthenium nickel doped tin dioxide electrode produced by the present invention has very fine ozone and oxygen bubbles formed on the yttrium nickel doped tin dioxide electrode. At the same time, hydrogen peroxide (H ₂ O ₂ ) 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 formation of hydrogen peroxide in rain and snow.

6. 当水流以高速 (每分钟 10公升或以上）流经本发明所制造锑镍掺杂二氧化锡电极时，不会对于臭氧生成效能造成明显负面影响。依据上述结果，本发明可以利用锑镍掺杂二氧化锡电极作灵活配置设计，以制造出各种具成本效益的臭氧产生器。首先，图 1所示是一种流通式臭氧产生器 10。如图 1所示，臭氧产生器 10由多个阳极电极 140及多个阴极电极 160交互配置于一外壳 120中，以形成一种电极交互堆栈结构，其中以锑镍掺杂二氧化锡电极来形成阳极堆栈 140, 而以不锈钢、 4太、镍金属片形成阴极堆栈 160。每一阳极 140面对一平行阴极 160, 反之亦然。此外，亦可使用一非导电材料作为电极间的隔板（图 1中未示），以防止电极发生短路。此非导电材料可以是聚丙烯、聚乙烯、尼奥普林（氯丁橡胶）、尼龙或聚四氟乙烯。在一较佳实施例中，此非导电材料隔板所形成的框架，可使电极间的间隙保持在 0.5-5mm的距离。艮明显地，在图 1中的水流是以蜿蜒路径流贯臭氧产生器 10, 故会形成流通式臭氧产生器 10。此外，图 1中的电源供应器模块 180可以进一步配置一种超级电容器（Super Capacitor ) 或是一个升压电路 ( boost circuit ) , 用来提供一个 15V至 20V的电压至阳极堆栈 140与阴极堆栈 160的接点上，而水流通过臭氧产生器 10 后可经完全消毒或杀菌。而通过增加电极面积或是增加阳极-阴极对的数量，均可提升反应器处理性能或臭氧产量。而在一较佳实施方式中，可于电源供应器模块 180中再加入一个脉波宽度调整装置（PWM ) 181 , 以便使用者能依据所要调整电源供应器模块 180 的输出电压，进而控制臭氧产生器 10的反应速率。接着，请参考图 2A, 图中显示一个以本发明制造方法所制造的锑镍掺杂二氧化锡的钛（ Ti ) 电极板 100A, 钛电极板 100A上配置有多个成几何形状排列的孔洞 110A, 例如：以同心方式排列（包括：圓形电极板时的同心圓排列；矩形电极板时的同心环排列），使得废水可以经过钛电极板 100A上的孔洞 110A。在本发明的实施例中，无论此钛基板的尺寸为何，钛电极板 100 A上配置的孔洞总面积应占钛电极板 100 A总几何面积的 5 %至 20 %范围内。然而，在一般处理状况下，本发明对于孔洞 110A总面积应占太电极板 100 A 总几何面积的比例并不加以限制，其可依实施要处理的废水特性来决定。在此要强调，本发明的孔洞可釆用任何形式，并以任何方式排列，而图 2A 所示则为本发明的一较佳实施例。同时，每一太电极板 100A 上的孔洞 110A直径、孔洞数量以及圓环数量与间距，均依废水所需达到的净度目标值而定。在实际形成各应用所需的孔洞前，可先利用数学模式来决定电极上开口所应 4 成的图。上述钛电极板 100 A是用来做为本发明臭氧产生装置的阳极电极。当本发明的臭氧产生装置在处理低氯化物含量的废水时，可使用不锈钢做为阴极，其中不锈钢材料包括 316、 314或 304等级的不锈钢。请参考图 2B, 阴极不绣钢基板 100B上也配置有多个孔洞 110B, 多个孔洞 110B的环形排列方式与阳极钛电极板 100A上的孔洞 110A相似，两者间的差异仅在孔洞的配置位置不相同，即当两者成上、下堆栈结构时，太电极板 100A与阴极电极板 100B 之间的孔洞 110A/110B是不会形成上下重迭的，其示意图如图 2C所示。图 2C是将太电极板 100A与不锈钢电极板 100B堆栈后的俯视示意图，其显示出相邻电极上交错排列孔洞环。由于每一孔洞错开一预定距离，因此，欲接受处理的废水，必须以近似 S形蜿蜒穿过交错排列孔洞方可流出。在每片如图 2A与图 2B所示的太电极板 100A与不锈钢电极板 100B所示周缘均设有一 O形环 130, 如图 2D与图 2E所示，其作用是在钛电极板 100 A与阴极电极板 100B堆栈时，用以达到密封阳极电极板与阴极电极板边缘。 O形环 130的材质可选自诸如三元乙丙橡胶（EPDM )的橡胶、聚硅氧、胺基甲酸酯或聚丙烯（PP ) , 厚度则为 0.6至 1毫米，且环的外径大于阳极太电极板 100A与阴极电极板 100B的直径，内径则小于太电极板 100A与阴极电极板 100B的直径，而内、外径之差即为该 O形环 130的宽度。请参考图 3 ,将多个如图 2A与图 2B所示的钛电极板 100A与阴极电极板 100B 垂直堆栈成一个电极板堆栈结构 200, 若将此电极板堆栈结构 200 置入于一电解槽中，再将正电极 150 ( + )与负电极 150 ( - )的连接端曝露于电解槽外部时，即可形成一独立臭氧产生装置（未显示于图中）。如图 3所示，臭氧产生装置是将多个 2A图与 2B图所示钛电极板 100A与阴极电极板 100B间隔地垂直堆栈而成，例如：将太电极板 100A作为奇数电极，而阴极电极板 100B作为偶数电极；然后，将正电极的太电极板 100 A与负电极的阴极电极板 100B 间隔地堆栈即可形成一独立的臭氧产生装置。然后，将每一片太电极板 100A与一正电极连接；另夕卜，再^]夺每一片阴极电极板 100B与一负电极连接。至于臭氧产生装置要由多少钛电极板 100A来组成，则可以视所要产生臭氧需求量而定。以本发明的一标准的臭氧产生装置为例，其由 21 片电极板所组成，其中的第 1 片（顶端电极）与第 21 片（底端电极）以及其间的每一奇数钛电极板 100A定为正电极，而每一配置于每一奇数钛电极板 100A之间的偶数阴极电极板 100B定为负电极。因此当臭氧产生装置上的正电极与负电极与一直流电源的正电极与负电极连接后，即可在废水中经由电解方式产生臭氧。在此要强调，上述在锑镍掺杂二氧化锡是钛 ( Ti ) 电极板 100A或是锑镍掺杂二氧化锡的太 ( Ti )电极板 100B形成同心方式排列的孔洞为本发明的较佳实施例，然而，当锑镍掺杂二氧化锡钛 ( Ti )电极板 100A 或是锑镍掺杂二氧化锡的钛（Ti ) 电极板 100B 上没有孔洞时，其所形成的堆栈电极 200也可以达到直接在废水中产生臭氧的功能。当臭氧产生装置的曝露于电解槽外部的正电极和负电极与一个 4氐 DC 电源（例如 24V或以下的电供应器 -power supply )的两电极连接后，阳极（太电极板 100A )便能使水分解，在水中直接产生臭氧（与氧气）；阴极（不绣 4冈电极板；不缘4冈材质包括： SS304, SS304L, SS316, SS316L, SS410, SS410L, SS430等）则产生氢气，如下列反应方程式（1) 与（²)：阳极反应： 6. When the water stream flows through the nickel-doped tin-doped tin electrode produced by the present invention at a high speed (10 liters per minute or more), it does not have a significant negative effect on the ozone generation efficiency. Based on the above results, the present invention can utilize a niobium-nickel doped tin dioxide electrode for flexible configuration design to manufacture various cost-effective ozone generators. First, FIG. 1 shows a flow-through ozone generator 10. 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 structure in which a nickel-doped tin oxide electrode is used. The anode stack 140 is formed, and the cathode stack 160 is formed of stainless steel, 4 tera, and nickel metal sheets. Each anode 140 faces a parallel cathode 160 and vice versa. In addition, a non-conductive material may be used as a separator between the electrodes (not shown in Fig. 1) to prevent short-circuiting of the electrodes. This non-conductive material may be polypropylene, polyethylene, neoprene (neoprene), nylon or polytetrafluoroethylene. In a preferred embodiment, the frame formed by the non-conductive material spacer maintains the gap between the electrodes at a distance of 0.5-5 mm. Specifically, the water flow in Fig. 1 flows through the ozone generator 10 in a meandering path, so that the flow-through ozone generator 10 is formed. In addition, the power supply module 180 of FIG. 1 can be further configured with a supercapacitor or a boost circuit for providing a voltage of 15V to 20V to the anode stack 140 and the cathode stack 160. The water is passed through the ozone generator 10 and can be completely sterilized or sterilized. 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 adjustment device (PWM) can be added to the power supply module 180. 181, so that the user can control the reaction rate of the ozone generator 10 according to the output voltage of the power supply module 180 to be adjusted. Next, referring to FIG. 2A, there is shown a nickel-tin-doped tin-doped titanium (Ti) electrode plate 100A manufactured by the manufacturing method of the present invention. The titanium electrode plate 100A is provided with a plurality of geometrically arranged holes. 110A, for example: arranged in a concentric manner (including concentric arrangement of circular electrode plates; concentric ring arrangement of rectangular electrode plates) so that waste water can pass through the holes 110A in the titanium electrode plate 100A. 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 100 A should be in the range of 5% to 20% of the total geometric area of the titanium electrode plate 100 A. However, under normal processing conditions, the present invention does not limit the ratio of the total area of the holes 110A to the total geometric area of the electrode plates 100 A, which may be determined depending on the characteristics of the wastewater to be treated. It is emphasized herein that the holes of the present invention can be used in any form and arranged in any manner, and Figure 2A shows a preferred embodiment of the present invention. At the same time, the diameter of the hole 110A on each of the electrode plates 100A, the number of holes, and the number and spacing of the rings are determined according to the target value of the cleanliness required for the wastewater. Before actually forming the holes required for each application, the mathematical mode can be used to determine the 40% of the opening on the electrode. The above titanium electrode plate 100 A 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, stainless steel can be used as the cathode, wherein the stainless steel material includes stainless steel of grade 316, 314 or 304. Referring to FIG. 2B, the cathode stainless steel substrate 100B is also provided with a plurality of holes 110B. The annular arrangement of the plurality of holes 110B is similar to the hole 110A on the anode titanium electrode plate 100A. The difference between the two is only in the hole arrangement. The positions are different, that is, when the two are in the upper and lower stack structures, the holes 110A/110B between the electrode plate 100A and the cathode electrode plate 100B are not overlapped vertically, and the schematic view is as shown in FIG. 2C. 2C is a top plan view showing the stack of the electrode plate 100A and the stainless steel electrode plate 100B, which shows the staggered hole rings on the adjacent electrodes. Since each hole is staggered by a predetermined distance, the wastewater to be treated must flow out through the staggered holes in an approximately S-shaped shape. An O-ring 130 is disposed on each of the peripheral edges of the electrode plate 100A and the stainless steel electrode plate 100B as shown in FIGS. 2A and 2B, as shown in FIG. 2D and FIG. 2E, and functions as a titanium electrode plate 100 A. When stacked with the cathode electrode plate 100B, it is used to seal the edges of the anode electrode plate and the cathode electrode plate. The material of the O-ring 130 may be selected from rubber such as ethylene propylene diene monomer (EPDM), polysiloxane, urethane or polypropylene (PP), and has a thickness of 0.6 to 1 mm, and the outer diameter of the ring. The diameter of the anode electrode plate 100A and the cathode electrode plate 100B is larger than the diameter of the electrode plate 100A and the cathode electrode plate 100B, and the difference between the inner and outer diameters is the width of the O-ring 130. Referring to FIG. 3, a plurality of titanium electrode 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 an electrolytic cell Then, when the connection end of the positive electrode 150 (+) and the negative electrode 150 (-) is exposed outside the electrolytic cell, an independent 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 2A and 2B titanium electrode plates 100A and a cathode electrode plate 100B, for example, using the electrode plate 100A as an odd electrode and a cathode electrode. The plate 100B is used as an even electrode; then, the positive electrode plate 100A of the positive electrode and the cathode electrode plate 100B of the negative electrode are stacked at intervals to form a separate ozone generating device. Then, each piece of the electrode plate 100A is connected to a positive electrode; in addition, each piece of the cathode electrode plate 100B is connected to a negative electrode. As for how many titanium electrode plates 100A the ozone generating device is composed of, it is possible to determine the amount of ozone required. Taking a standard ozone generating device of the present invention as an example, it is composed of 21 electrode plates, wherein the first piece (top electrode) and the 21st piece (bottom electrode) and each odd titanium electrode plate 100A therebetween The positive electrode is designated as a positive electrode, and each of the even cathode electrode plates 100B disposed between each of the odd-numbered titanium electrode plates 100A is defined as a negative electrode. Therefore, when the positive electrode and the negative electrode on the ozone generating device are connected to the positive electrode and the negative electrode of the DC power source, ozone can be generated by electrolysis in the wastewater. It should be emphasized here that the above-mentioned holes in which the yttrium-nickel-doped tin dioxide is a titanium (Ti) electrode plate 100A or a yttrium-nickel-doped tin dioxide (T) electrode plate 100B are concentrically arranged are the present invention. A preferred embodiment, however, when the yttrium-nickel-doped tin-titanium (Ti) electrode plate 100A or the yttrium-nickel-doped tin-doped titanium (Ti) electrode plate 100B has no holes, the stacked electrode 200 is formed. It is also possible to achieve the function of generating ozone directly in the wastewater. When the positive electrode and the negative electrode of the ozone generating device exposed to the outside of the electrolytic cell are connected to two electrodes of a 4 氐 DC power source (for example, a power supply of 24 V or less), the anode (the electrode plate 100A) can be Decompose water, produce ozone directly (with oxygen) in water; cathode (not embroidered 4 electrode plates; not only 4 materials including: SS304, SS304L, SS316, SS316L, SS410, SS410L, SS430, etc.) generate hydrogen, such as The following reaction equations (1) and ( ² ): Anodic reaction:

8 H₂O→ O₂ + 2 O₃ + 16 H+ + 16 e" (1) 阴极反应： 8 H ₂ O→ O ₂ + 2 O ₃ + 16 H+ + 16 e" (1) Cathodic reaction:

2 H₂O + 2 e→H₂ + 2 OH (2) 此夕卜，电解槽中的阳极电极与阴极电极间无隔离，阳极电极产生的臭氧会与阴极电极产生的氢气进行下列的反应： 2 H ₂ O + 2 e→H ₂ + 2 OH (2) Further, there is no isolation between the anode electrode and the cathode electrode in the electrolytic cell, and ozone generated by the anode electrode The following reactions are carried out with hydrogen produced by the cathode electrode:

2 O₃ + H₂→ H₂O₂ + 2 O₂ (3) 反应方程式（3 ) 所产生的双氧水（H₂O₂ ) 也是一种强氧化剂，具有杀菌与分解有机污染物的功能。更重要的是，臭氧还会与双氧水反应产生氢气自由基（ ·ΟΗ-Ηγ ·οχγ1 Radical ) 。 ·ΟΗ基的氧化能力比 Ο₃更强，分解有机污染物的速率比 Ο₃迅速万倍以上。而在本发明的臭氧产生装置中，可以产生氢气自由基（·ΟΗ ) , 具体说明如下。臭氧的自分解可以通过与水中 ΟΗ—离子反应生成 ΗΟ^2- 离子，其反应方程式为： 2 O ₃ + H ₂ → H ₂ O ₂ + 2 O ₂ (3) Hydrogen peroxide (H ₂ O ₂ ) produced by the reaction equation (3) is also a strong oxidant, which has the function of sterilizing and decomposing organic pollutants. More importantly, ozone also reacts with hydrogen peroxide to produce hydrogen radicals (·ΟΗ-Ηγ ·οχγ1 Radical ). · The oxidizing ability of sulfhydryl groups is stronger than that of Ο ₃ , and the rate of decomposition of organic pollutants is more than 10,000 times faster than Ο ₃ . On the other hand, in the ozone generating apparatus of the present invention, hydrogen radicals (·ΟΗ) can be generated, which are specifically described below. The self-decomposition of ozone can form ruthenium ^2- ion by reacting with cesium ^- ion ions in water. The reaction equation is:

Ο₃ + ΟΗ→ΗΟ₂ + Ο₂ (4) 再由于臭氧产生装置中已含有过氧化氢（Η₂Ο₂ ) , 如反应方程式（3 ) , 则 Η₂Ο₂又会将水分解以产生 ΗΟ₂-, 其反应方程式为： Ο ₃ + ΟΗ→ΗΟ ₂ + Ο ₂ (4) Since the ozone generating device already contains hydrogen peroxide (Η ₂ Ο ₂ ), such as the reaction equation (3), Η ₂ Ο ₂ will decompose the water to produce ΗΟ ₂ -, the reaction equation is:

Η₂Ο₂ + Η₂Ο→ΗΟ₂ + Η₃Ο⁺ (5) 反应方程式（4 ) 及（5 ) 所生成的 ΗΟ₂ 是自由基 ·ΟΗ产生的诱发剂，其反应方程式为： _{_{_{Η 2 Ο 2 + Η 2 Ο}}} → ΗΟ 2 + Η 3 Ο + (5) Scheme (4) and (5) generated ΗΟ ₂ · ΟΗ radical inducing agent is produced, the reaction equation is:

Ο₃ +ΗΟ₂ → ·ΟΗ+ Ο₂ +Ο₂ (6) 当自由基 ·ΟΗ—旦产生后，就发生如下链反应： Ο ₃ +ΗΟ ₂ → ·ΟΗ+ Ο ₂ +Ο ₂ (6) When the free radicals are generated, the following chain reaction occurs:

Ο₃ + ·ΟΗ→ ΗΟ₂ +0₂ (7) Ο ₃ + ·ΟΗ→ ΗΟ ₂ +0 ₂ (7)

Ο₃ + Ο₃ →Ο₃ +Ο₂ (8) Ο ₃ + Ο ₃ →Ο ₃ +Ο ₂ (8)

Ο₃ + Η₂Ο→ ·ΟΗ + OH +Ο₂ (9) 除了上述反应外，还存在 ·ΟΗ 自由基与 Η₂Ο₂反应，但 ·ΟΗ与 Η₂Ο₂ 反应比上述反应慢得多，故可以被忽略。若水中存在有机污染物 Ρ, 则反应方程式为： Ο ₃ + Η ₂ Ο → · ΟΗ + OH + Ο ₂ (9) In addition to the above reaction, there is also a reaction between 自由基 and Η ₂ Ο ₂ , but the reaction between ΟΗ and Η ₂ Ο ₂ is much slower than the above reaction. , so it can be ignored. If organic pollutants are present in the water, the reaction equation is:

Ρ+ ·ΟΗ→产物或中间物 (10) 此外，有机物 Ρ与臭氧的直接氧化反应方程式为： P+ O₃→产物或中间物 (11) 最后，反应方程式（ 11 )会再进一步氧化成二氧化碳（CO₂ )及水（H₂O ) , 其氧化反应方程式为： Ρ+ ·ΟΗ→product or intermediate (10) In addition, the direct oxidation reaction equation for organic matter and ozone is: P+ O ₃ → product or intermediate (11) Finally, the reaction equation (11) is further oxidized to carbon dioxide (CO ₂ ) and water (H ₂ O ). The oxidation reaction equation is:

P + O₃→ 产物或中间物→CO₂+ H₂O (12) 若所要处理的废水中含有醇类时，则其在本发明的臭氧产生装置中的反应概述如下。一般的醇类以 ROH表示，故 ROH会先被氧化为醛类（ RCHO ) , 接着，醛类（RCHO )再被氧化为酮类（RCOR ) , 然后酮类（RCOR )再被氧化为有机酸（RCOOH ) , 此有机酸（RCOOH ) 即为一种氧化过程的中间物（P ) , 最终此中间物（P ) 再被氧化为二氧化碳 ( CO₂ ) 及水（Η₂Ο ) , 其氧化反应路线为： P + O ₃ → product or intermediate → CO ₂ + H ₂ O (12) If the wastewater to be treated contains alcohol, the reaction thereof in the ozone generating apparatus of the present invention is summarized as follows. The general alcohol is represented by ROH, so ROH is first oxidized to aldehyde (RCHO). Then, the aldehyde (RCHO) is oxidized to ketone (RCOR), and then the ketone (RCOR) is oxidized to organic acid. (RCOOH), the organic acid (RCOOH) is an intermediate (P) of the oxidation process, and finally the intermediate (P) is oxidized to carbon dioxide (CO ₂ ) and water (Η ₂ Ο ), and its oxidation reaction The route is:

ROH→ RCHO→ RCOR→ RCOOH→P→ C0₂ + H₂O (13) 经由上述的说明，本发明的臭氧产生装置可以将废水中的有机物分解成二氧化碳 ( CO₂ ) 及水（H₂O ) 。同样地，本发明臭氧产生装置可以氧化分解的有机物还包括含酚废水；此含酚废水中主要含有酚基化合物，如苯酚、甲酚、二甲酚和肖基甲酚等，而此酚废水其主要来自焦化厂、煤气厂、石油化工厂、绝缘材料厂等工业部门以及石油裂解制乙烯、合成苯酚、聚酰胺纤维、合成染料、有机农药和酚醛树脂生产过程所产生的废水。在此要强调，上述以含醇类废水以及含酚类废水来说明本发明的臭氧产生装置可以将废水中的有机物分解成二氧化碳 ( CO₂ ) 及水（ H₂O ) , 然而，废水中的有机物还包括其它类型者，例如：对不饱和脂肪烃和芳香烃类化合物等也是有效的。综合上述，本发明的臭氧产生装置可以通过直接氧化（在阳极上）、间接氧化（与 Ο₃/ Η₂Ο₂/·ΟΗ反应）、直接还原（在阴极上）与间接还原（与 ¾ 反应）等过程来达到杀菌 /除臭 /褪色 /漂白等作用。图 4即为本发明的臭氧产生装置 300中的堆栈电极结构 200的一实施例的示意图。堆栈电极结构 200以上盖 310及下盖 330、配合螺杆、螺丝与螺帽 (未显示于图中）固定后，水由臭氧产生装置进水口（320 )进入，流经堆栈电极结构 200 后，由出水口（320 ) 流出经过处理的水。再次说明，堆栈电极结构 200的电极配置方式，可以如图 1所示的流通式配置方式来形成一个流通式臭氧产生器 10。此外，堆栈电极结构 200的电极是以正电极与负电极交叉堆栈而成，并以单极性组态与 DC电源供应器联机，如图 3所示。在本发明图 4的臭氧产生装置 300中，无论其堆栈电极结构 200的配置方式如何，其均具有产生 1 kg O₃/hour的能力，并且可以依据所要处理的废水状态，来设计出所需要产生的臭氧量 300来个性化地 (或称 case-by-case ) 制造出每一个废水处理场所所需的臭氧产生装置 300。随着产业的发展，特别是化学工业、染整工业、造纸工业、食品加工业以及半导体相关制造工业（包括 IC 制造的异丙醇废水、化学研磨废水、液晶面板的彩色滤光片的制造废水）等，在产品的制造过程中使用大量的有机溶剂或是化学合成有机溶剂，这些有机溶剂或是化学合成有机溶剂所产生的制造废水通常具有毒性并且很难被自然分解，故形成了高浓度的化学需氧量 (Chemical Oxygen Demand; COD), 造成了环境污染。而一般工业废水或是生活污水中，以 COD与浊度为两最难去除的污染物。事实上，浊度常为悬浮性 COD所构成，去除浊度后， COD即跟着降低。同样地，浊度来自悬浮固体（SS ) , 浊度去除后， SS也跟着降低。如前所述，本发明臭氧产生装置在臭氧的氧化分解有机污染物的过程中，包含许多阶段的化学反应（如反应方程式 1〜13 ) , 每一阶段的速率较慢，故要处理高 COD 浓度（例如数万或数十万 ppm ) 的废水时，就需要花费较大的电能以及较多的时间。然而，在现有技术中，电凝聚装置（Electro-coagulation; EC )可以降氐度水中 ό COD浓度， Ϊ列 ^口：美国专矛】 3969345号、 4123340、 4159235 号、 5271814号、 5587057号、 5611907号、 5611907号等，均已公开使用电凝聚装置（Electro-coagulation; EC ) 来移除废水中的杂质。接着，请参考图 5 , 是本发明的使用柱状电极所形成电凝聚装置（EC ) 的示意图。如图 5所示，本发明的电凝聚装置 400由一个电解槽 410以及配置于电解槽 410中的至少一对阳极电极柱 430与阴极电极柱 450以及一沉淀出孑 470。当以本发明的电凝聚装置（ EC ) 400来处理废水时，就是将废水输入至电解槽 410中，使得每一才艮阳极电极柱 430与每一才艮阴极电极柱 450浸入废水中，如图 5所示；接着，将阳极电极柱 430及阴极电极柱 450与一个直流电源连接，藉由直流电源所提供的电流作用，使得阳极电极柱 430释放出离子，因此使得废水中的离子成分被吸引到电极柱 430及阴极电极柱 450的表面上，以形成氧化与还原反应。例如，使用铁作阳极电极 (也称为牺牲阳极) 以及使用铝作为阴极电极时，当阳极电极柱 430和阴极电极柱 450通上直流电流后，阳极电极溶解出亚铁离子 Fe⁺² 和 Fe⁺³，然后在水中与阴极电极电解出的氢氧才艮离子（OH— ) 生成 Fe(OH)₂和 Fe(OH)₃, 其反应方程式如下：阳极反应 ROH→RCHO→ RCOR→ RCOOH→P→C0 ₂ + H ₂ O (13) According to the above description, the ozone generating device of the present invention can decompose organic matter in wastewater into carbon dioxide (CO ₂ ) and water (H ₂ O). . Similarly, the oxidatively decomposed organic matter of the ozone generating device of the present invention further includes phenol-containing wastewater; the phenol-containing wastewater mainly contains a phenol-based compound such as phenol, cresol, xylenol and succinyl cresol, and the phenol wastewater It is mainly from industrial sectors such as coking plants, gas plants, petrochemical plants, and insulating materials plants, as well as wastewater from the production of petroleum cracking ethylene, synthetic phenol, polyamide fiber, synthetic dyes, organic pesticides and phenolic resins. It should be emphasized here that the ozone generating device of the present invention described above with alcohol-containing wastewater and phenol-containing wastewater can decompose organic matter in wastewater into carbon dioxide (CO ₂ ) and water (H ₂ O), however, in wastewater. Organic substances also include other types, such as: It is also effective for unsaturated aliphatic hydrocarbons and aromatic hydrocarbon compounds. In summary, the ozone generating apparatus of the present invention can be directly oxidized (on the anode), indirectly oxidized (reacted with Ο ₃ / Η ₂ Ο ₂ /·ΟΗ), directly reduced (on the cathode) and indirectly reduced (reacted with 3⁄4) ) and other processes to achieve sterilization / deodorization / fading / bleaching. 4 is a schematic diagram of an embodiment of a stacked electrode structure 200 in an ozone generating apparatus 300 of the present invention. After the stacked electrode structure 200 is fixed above the cover 310 and the lower cover 330, and the matching 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 form a flow-through ozone generator 10 in a flow-through configuration as shown in FIG. In addition, the electrodes of the stacked electrode structure 200 are formed by stacking a positive electrode and a negative electrode, and are connected to the DC power supply in a unipolar configuration, as shown in FIG. In the ozone generating apparatus 300 of FIG. 4 of the present invention, regardless of the configuration of the stacked electrode structure 200, it has the ability to generate 1 kg O ₃ /hour, and can design the required generation according to the state of the wastewater to be treated. The ozone amount 300 is used to personally (or case-by-case) the ozone generating device 300 required for each wastewater treatment site. With the development of the industry, especially in the chemical industry, dyeing and finishing industry, paper industry, food processing industry and semiconductor-related manufacturing industries (including IC manufacturing of isopropanol wastewater, chemical grinding wastewater, liquid crystal panel color filter manufacturing wastewater ), etc., use a large amount of organic solvents or chemically synthesized organic solvents in the manufacturing process of the products. The manufacturing wastewater generated by these organic solvents or chemically synthesized organic solvents is usually 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 the 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 chemical reactions (e.g., reaction equations 1 to 13) in the process of oxidative decomposition of organic pollutants by ozone, and the rate of each stage is slow, so that high COD is handled. At a concentration (for example, tens of thousands or hundreds of thousands of ppm) of wastewater, it takes a lot of electric energy and more time. However, in the prior art, Electro-coagulation (EC) can lower the concentration of όCOD in the water, and the 口 ^ : : : : : 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 No. 5611907, No. 5611907, etc., have disclosed the use of electro-coagulation (EC) to remove impurities in wastewater. Next, please refer to FIG. 5, which is a schematic view of an electrocoagulation device (EC) formed 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 precipitation enthalpy 470. When the wastewater is treated by the electrocoagulation device (EC) 400 of the present invention, the wastewater is introduced 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 As shown in FIG. 5, the anode electrode column 430 and the cathode electrode column 450 are connected to a DC power source, and the anode electrode column 430 releases ions by the current supplied by the DC power source, thereby causing the ion component in the wastewater to be It is 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 referred to as sacrificial anode) and aluminum is used as the cathode electrode, when the anode electrode column 430 and the cathode electrode column 450 are subjected to a direct current, the anode electrode dissolves ferrous ions Fe ^{+ 2} and Fe. ⁺³ , then electricity in the water and cathode electrode The dissolved hydrogen and oxygen ions (OH— ) form Fe(OH) ₂ and Fe(OH) ₃ , and the reaction equation is as follows:

Fe→Fe⁺²+2e (14) Fe ² →Fe⁺³+e (15) 阴极反应 Fe→Fe ⁺² +2e (14) Fe ² →Fe ⁺³ +e (15) Cathodic reaction

2H₂O⁺ 2e →2OH + H₂ (16) 则在本发明的电凝聚装置（EC ) 中的总反应方程式为 Fe ² + 2(OH) → Fe(OH)₂ (17) 及 2H ₂ O ⁺ 2e → 2OH + H ₂ (16) The total reaction equation in the electrocoagulation device (EC) of the present invention is Fe ² + 2(OH) → Fe(OH) ₂ (17) and

Fe ³ + 3(OH) →Fe(OH)₃ (18) 由上面的反应方程式可知，当电凝聚装置（EC ) 400 的阳极电极 430 与阴极电极 450连接适当直流电源或交流电源时，阳极电极 430 (最常用的材料为铁或铝）将被电解产生铁离子（Fe²⁺ ) 或铝离子（Al³⁺ ) 及其它产物：例如：电子、氢离子与氧气等。同时，阴极电极 450产生：氢气与氢氧根离子 (OH―)。金属阳离子（例如：铁离子）可直接与悬浮性 COD或水溶性 COD 结合，凝聚成大粒径的颗粒而沉淀至电解槽 410底部并可藉由排出孔 470排出，故可使废水中的 COD 浓度迅速下降。另一方面，金属阳离子（例如：铁离子）也可与氢氧根离子（OH— ) 形成有絮凝作用的聚合物，再进一步的去除废水中的 COD。此外，浮于水中的凝聚物还能被阳极电极 430与阴极电极 450所产生的气泡吸附，成为可以刮除或溢流的浮渣（froth ) 。因此，电凝聚装置（ EC ) 400的处理包含表 1所列的多元反应：表 1: EC处理所提供的反应 Fe ³ + 3(OH) →Fe(OH) ₃ (18) From the above reaction equation, 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 aluminum) will be electrolytically produced to produce iron ions (Fe ²⁺ ) or aluminum ions (Al ³⁺ ) and other products: eg 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 410 and can be discharged through the discharge hole 470, so that the COD in the wastewater can be made. The concentration drops rapidly. On the other hand, metal cations (for example, iron ions) can also form a flocculated polymer with hydroxide ions (OH-), and further remove COD from the wastewater. Further, the agglomerates floating in the water can be adsorbed by the bubbles generated by the anode electrode 430 and the cathode electrode 450, and become froth which can be scraped or overflowed. Therefore, the treatment of electrocoagulation unit (EC) 400 contains the multivariate reactions listed in Table 1: Table 1: Reactions provided by EC treatment

5 凝聚污染物与金属离子 /金属氢氧化物聚结为大颗粒

5 Condensed pollutants and metal ions/metal hydroxides coalesce into large particles

6 浮除污染物被氢气或氧气气泡吸附成为浮渣 6 Floatation Contaminants are adsorbed by hydrogen or oxygen bubbles into scum

7 中和 /沉淀污染物与 H+/OH―中和或产生沉淀由于表显示 1的多元反应的结果，使用电凝聚装置（ EC ) 400能提供快速的除污效果，例如：当废水流过电凝聚装置（ EC ) 后，废水中的 COD便会减少约 80%。此外，在本实施例中，作为阳极的铁材料可以是生铁、黑铁、铸铁、光圓铁、 SKD60与 SS430等。请继续参考图 6, 其是本发明的电凝聚装置（EC )示意图。如图 6所示，本发明的电凝聚装置（EC ) 400是以一个内部直径 20cm的电解槽 410来将阳极电极 430与阴极电极 450分成两圏安置于顶盖 420上，并且配合螺杆、螺丝与螺帽（未显示于图中）等固定。电解槽 410 进一步配置有一进水口 440 以及一出水口 460 , 以提供废水进出电凝聚装置（ EC ) 400的通道；而电凝聚装置处理过程所产生的污泥，则可由沉淀物排出孔 470排出。此外，要强调的是，在本发明对电凝聚装置（EC ) 400中的电极数目、面积、间距、正负电极的列、单极性（monopolar ) 或双极性 ( bipolar ) 组态、 DC 或 AC 供电、以及电压 /电流的设定等，并未加以限制，其仅为本发明的一实施例，而实际电凝聚装置（ EC ) 的结构是可以视废水水质测试与处理目标而设计，以使电凝聚装置（EC ) 400处理后的废水达到下列指标： 7 Neutralization/precipitating contaminants and H+/OH-neutralization or precipitation As a result of the multivariate reaction shown in Table 1, the use of electrocoagulation unit (EC) 400 provides rapid decontamination, eg when wastewater flows through electricity After coagulation (EC), the COD in the wastewater is reduced by about 80%. Further, in the present embodiment, the iron material as the anode may be pig iron, black iron, cast iron, round iron, SKD60 and SS430, or the like. Please refer to FIG. 6, which is a schematic diagram of the electrocoagulation device (EC) of the present invention. As shown in FIG. 6, the electrocoagulation device (EC) 400 of the present invention divides the anode electrode 430 and the cathode electrode 450 into two layers on the top cover 420 by an electrolytic cell 410 having an inner diameter of 20 cm, and is fitted with a screw and a screw. It is fixed with a nut (not shown in the figure). The electrolytic cell 410 is further provided with a water inlet 440 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 electrocondensation device treatment process can be discharged from the sediment discharge hole 470. Furthermore, it is emphasized that the number, area, spacing, columns of positive and negative electrodes, monopolar or bipolar configuration, DC in the electrocoagulation device (EC) 400 of the present invention. 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. The wastewater treated by the electrocoagulation device (EC) 400 is subjected to the following indicators:

1. 水流速率 200-300 L/min。 1. Water flow rate 200-300 L/min.

2. 水流过一个电凝聚装置（EC ) 后，其 COD/SS/浊度去除 80%。 2. After the water flows through an electrocoagulation unit (EC), its COD/SS/turbidity is removed by 80%.

3. 水流过一个电凝聚装置（ EC )后，可去除 1 kg COD并且只消耗 lkWh 或以下的电能。依据上述，本发明以电凝聚装置（EC ) 400来对废水进行处理时，其具有下列的效益： 3. After passing through an electrocoagulation unit (EC), water can remove 1 kg of COD and consume only lkWh or less. According to the above, the present invention has the following benefits when the wastewater is treated by an electrocoagulation device (EC) 400:

1. 不使用化学品，只需供应电能即可对废水进行处理，故千净无污染。 1. Without the use of chemicals, the wastewater can be treated only by supplying electricity, so it is clean and free of pollution.

2. 污泥量比化学混凝法少 30% 以上（因为电凝聚装置不需添加阴离子）。 2. The amount of sludge is 30% less than the chemical coagulation method (because the electrocoagulation device does not need to add anion).

3. 电凝聚装置产生的污泥的含水量少（40% 以上），可作为无毒的固体废弃物处理（此标准已获得 US EPA认可）。 4. 电凝聚装置产生的污泥的聚结强度高，不易分散，因此容易过滤（成为泥饼）去除。 3. The sludge produced by the electrocoagulation unit has less water content (more than 40%) and can be treated as non-toxic solid waste (this standard has been approved by US EPA). 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) to be removed.

5. 电凝聚装置能去除的污染物的种类多，去除率常可达 90% 以上。 5. The electrocoagulation device can remove a large number of pollutants, and the removal rate is often more than 90%.

6. 电凝聚装置能使高浓度的废水快速减少污染物（如 COD ) 。 6. Electrocoagulation devices enable high concentrations of wastewater to rapidly reduce pollutants (such as COD).

7. 电凝聚装置的工作温度范围广（冷热不影响处理）。 7. The electrocoagulation device has a wide operating temperature range (cold heat does not affect the treatment).

8. 电凝聚装置处理器不含机械零件（仅阳极是唯一需要更换的耗材）。 8. The electrocoagulation unit processor does not contain mechanical parts (only the anode is the only consumable that needs to be replaced).

9. 金属阳离子凝聚剂容易控制其产生量。 9. The metal cation aggregating agent is easy to control the amount of its production.

10. 电凝聚装置占地小 (例如：以每日 3800 m³或 3800 CMD处理量的电凝聚装置***来估计，其占地约为 45〜50平方米）。然而，本发明的电凝聚装置（EC ) 400非万能，以目前技术而言，其在废水的处理限制包括： 10. The electrocoagulation device occupies a small area (for example, it is estimated to be about 45 to 50 square meters with an electrocoagulation system that processes 3800 m ³ or 3800 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:

1. 电凝聚装置无法去除一价金属离子，如碱金属离子（Na⁺、 K⁺ ) 。 1. Electrocoagulation devices cannot remove monovalent metal ions such as alkali metal ions (Na ⁺ , K ⁺ ).

2. 电凝聚装置处理后的水的导电度（或 TDS ) 高于处理前。 2. The conductivity (or TDS) of the treated water after electrocoagulation is higher than before treatment.

3. 电凝聚装置对一些溶解性较强的 COD去除率低。 3. The electrocoagulation device has a low removal rate of some CODs with high solubility.

4. 电凝聚装置处理无法将废水减至极氐的浓度。因此，电凝聚装置需要其它电处理技术的辅助，来回收工业与生活废水。例如：在本发明中，将电凝聚装置（EC ) 400与一个臭氧产生装置 300串接在一起，即可形成一个电能式废水处理装置，可以用来处理高浓度 COD 的废水。而选择将臭氧产生装置 300与电凝聚装置（ EC ) 400组合成废水处理装置目的，是因为臭氧产生装置 300能提供电凝聚装置（EC ) 400所无法达到的处理效果，包括： 4. The electrocoagulation unit is unable to treat the wastewater to a very high concentration. Therefore, electrocoagulation devices require the assistance of other electrical processing technologies to recover industrial and domestic wastewater. For example, in the present invention, an electrocoagulation device (EC) 400 and an ozone generating device 300 are connected in series to form an electric energy type wastewater treatment device which can be used for treating high concentration COD wastewater. The purpose of combining the ozone generating device 300 with the electrocoagulation device (EC) 400 into a wastewater treatment device is that the ozone generating device 300 can provide a treatment effect that the electrocoagulation device (EC) 400 cannot achieve, including:

1. 臭氧产生装置 300能将废水中的 COD减至近乎 0 ppm。 1. Ozone generating unit 300 reduces COD in wastewater to nearly 0 ppm.

2. 臭氧产生装置 300不产生污泥（因为，污染物被氧化及还原为 CO₂ 与 H₂O ) 。 2. The ozone generating device 300 does not produce sludge (because the pollutants are oxidized and reduced to CO ₂ and H ₂ O).

3. 臭氧产生装置 300中的臭氧 (O₃)反应后成为氧气，且不会遗留金属阳离子。请参考图 7, 其表示本发明的一种电能式废水处理装置的功能方块示意图。如 7图所示，本发明的电能式废水处理装置 600包括一个电凝聚装置（ EC ) 400 以及一个臭氧产生装置 300, 其中臭氧产生装置如图 4所示，而电凝聚装置（EC ) 400如图 6所示。故当废水经由电凝聚装置（EC ) 400的进水口 440进入至电解槽 410中，废水在电解槽 410中与阳极电极 430及阴极电极 450进行反应后，在适当直流电源的供应下，依据反应方程式（ 14 ) 〜 ( 18 ) 的结果，可以将废水中的 COD减少约 80%; 接着，处理过的废水会由出水口 460送至臭氧产生装置 300的进水口 320, 然后废水再流经堆栈电极结构 200后，依据反应方程式（ 1 ) 〜（ 12 ) 的氧化结果，可将废水中剩余的有机物分解成二氧化碳及水，然后，由出水口 320流出经过处理并符合标准的水。艮明显地，为了能增加本发明的电能式废水处理装置 600的反应效率，以节省电能，在本发明的一较佳实施例中，在电凝聚装置（EC ) 400的进水口 440 之前先配置一过滤装置 620, 其目的是预先过滤废水中大于 10 ^啟米以上的物质；接着，还可以在电凝聚装置（EC ) 400的出水口 460与臭氧产生装置 300 的进水口 320之间也配置一个过滤装置 640, 其主要目的在过滤在电凝聚装置（ EC ) 400中产生的聚合物（例如：过滤大于 0.5微米的聚合物）；最后，本发明还可以在臭氧产生装置 300的出水口 340处也配置一个过滤装置 660, 其主要目的是过滤臭氧产生装置 630中微小的杂质（例如：过滤大于 0.2微米的杂质），以确保处理后的质量可以作为生产用水。艮明显地，本发明的电能式废水处理装置 600在整个处理过程中，釆用废水连续流过电极的处理方式，因此是以废水为产生处理剂的媒介或原料，来将废水中的污染物当场 (in-situ)去除，故本发明的电能式废水处理装置 600可以在不需添加任何化学成份状况下，通过对废水的电解完成废水处理或再生成生产用水，故不会产生二次公害。当本发明的电能式废水处理装置 600与一电源供应器（未显示于图中）以及一泵配（未显示于图中）置于一活动架上时，即可形成一独立且可移动的电能式废水处理模块；其中电能式废水处理装置是由至少一个电凝聚装置 ( EC ) 400与至少一个臭氧产生装置 300串接所组成，然后使用至少一个泵浦，用以将废水抽入至电凝聚装置（ EC ) 400的电解槽中；当每一个电凝聚装置（EC )与每一个臭氧产生装置与电源供应器连接后，废水便能够与配置在电凝聚装置（EC ) 400的电解槽中的阳极电极及阴极电极进行氧化还原反应，使得废水中的 COD 4艮快降氏，然后，再将废水送到臭氧产生装置 300 中，使得废水与堆栈电极 200进行反应后，即可使废水中的 COD降低至接近 0。同样地，为使本发明的电能式废水处理模块能具有更好的效果，当电能式废水处理模块使用多个电凝聚装置（EC ) 400时，其彼此间是使用并联方式连接，另外，当电能式废水处理模块使用多个臭氧产生装置 300时，其彼此间也是使用并联方式连接。此外，在本发明的电能式废水处理模块中加入一些过滤装置时，除可以加快废水处理速度外，还可以降低电能的消耗。故在本发明的电能式废水处理模块中，可以在电凝聚装置（ EC ) 400的进水口之前先配置一过滤装置，其目的是预先过滤废水中大于 10 ^啟米以上的物质；接着，还可以在电凝聚装置（EC ) 400的出水口与臭氧产生装置 300的进水口之间也配置一个过滤装置，其主要目的在过滤于电凝聚装置（EC ) 400中产生的聚合物（例如：过滤大于 0.5 ^啟米的聚合物）；最后，本发明还可以在臭氧产生装置 300的出水口处也配置一个过滤装置，其主要目的在过滤臭氧产生装置中微小的杂质（例如：过滤大于 0.2 ^啟米杂质），以确处理后的水可以作为生产用水。很明显地，若需要提高单位时间的废水处理量，可以使用多个电能式废水处理模块来形成一个电能式废水处理***。此种以附加（Add-on ) 方式来形成模块化的***具有下列的优势： 3. Ozone (O ₃ ) in the ozone generating device 300 reacts to become oxygen, and does not leave metal cations Ion. Please refer to FIG. 7, which is a functional block diagram of an electric energy type wastewater treatment apparatus of the present invention. As shown in Fig. 7, the electric energy type waste water treatment apparatus 600 of the present invention comprises 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) 400 is as Figure 6 shows. 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 then, under the supply of a suitable DC power source, according to the reaction. As a result of the equations (14) to (18), the COD in the wastewater can be reduced by about 80%; then, the treated wastewater is sent from the water outlet 460 to the water inlet 320 of the ozone generating device 300, and then the wastewater flows through the stack. After the electrode structure 200, according to the oxidation results of the reaction equations (1) to (12), the remaining organic matter in the wastewater can be decomposed into carbon dioxide and water, and then the treated and standard-compliant water is discharged from the water outlet 320. Specifically, in order to increase the reaction efficiency of the electric energy type waste water treatment apparatus 600 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 disposed before a filtering device 620, the purpose of which is to pre-filter substances above 10 μm in the wastewater; and then also between the water outlet 460 of the electrocoagulation device (EC) 400 and the water inlet 320 of the ozone generating device 300. A filtration device 640 whose primary purpose is to filter the polymer produced in the electrocoagulation device (EC) 400 (e.g., to filter polymers greater than 0.5 microns); finally, the present invention may also be at the water outlet 340 of the ozone generating device 300. A filtering device 660 is also provided, the primary purpose of which is to filter minute impurities (e.g., to filter impurities greater than 0.2 microns) in the ozone generating device 630 to ensure that the treated mass can be used as process water.艮 obviously, the electric energy type waste water treatment device 600 of the present invention processes the continuous flow of waste water 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 in-situ removal process allows the electric energy type wastewater treatment device 600 of the present invention to complete the wastewater treatment or regenerate the production water by electrolysis of the wastewater without adding any chemical components, so that no secondary pollution occurs. . When the electric energy type waste water treatment device 600 of the present invention is placed on a movable frame with a power supply (not shown) and a pump (not shown), an independent and movable structure can be formed. An 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 pump the wastewater into the electricity In the electrolytic cell of the coagulation device (EC) 400; after each electrocoagulation device (EC) is connected to each of the ozone generating devices and the power supply, the wastewater can be disposed in the electrolytic cell disposed in the electrocoagulation device (EC) 400 The anode electrode and the cathode electrode perform a redox reaction, so that the COD in the wastewater is rapidly decreased, and then the wastewater is sent to the ozone generating device 300. In the process, after the wastewater is reacted with the stack electrode 200, the COD in the wastewater can be reduced to near zero. Similarly, in order to make the electric energy type wastewater treatment module of the present invention have a better effect, when the electric energy type wastewater treatment module uses a plurality of electrocoagulation devices (EC) 400, they are connected to each other in parallel, and in addition, when When the electric energy type wastewater treatment module uses a plurality of ozone generating devices 300, 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 wastewater treatment speed, 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, the purpose of which is to pre-filter the material in the wastewater more than 10 ^ Kaimi; A filter device may also be disposed between the water outlet of the electrocoagulation device (EC) 400 and the water inlet of the ozone generating device 300 for the purpose of filtering the polymer produced in the electrocoagulation device (EC) 400 (for example: filtration) Finally, the present invention can also be provided with a filtering device at the water 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 greater than 0.2 ^) Kaimi impurities), so that the treated water can be used as production water. Obviously, if it is necessary to increase the amount of wastewater treatment per unit time, a plurality of electric energy type wastewater treatment modules can be used to form an electric energy type wastewater treatment system. Such a system that is modular in an add-on manner has the following advantages:

1. 依废水污染物种类与再生目标，设计最经济实用的组合***。 1. Design the most economical and practical combination system according to the type of wastewater pollutants and the target of regeneration.

2. 组合***以并联的数条独立作业线运转，不会因某一个电处理单元出故障而停机。 2. The combined system operates in parallel independent lines and does not stop due to the failure of one of the electrical processing units.

3. 组合***易于扩大产能、安装、搬迁与维修。 3. The combined system is easy to expand capacity, installation, relocation and maintenance.

4. 电处理单元可重迭安置，进一步缩小***的占地。组合***或其次***的使用地点（ point of use ) 无限制。经由适当数量的组合，本发明的电能式废水处理***能将高 COD且具有浊度的废水处理至如下标准： 4. The electrical processing unit 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. The electric energy waste water treatment system of the present invention can treat high COD and turbid wastewater to the following standards via an appropriate number of combinations:

1. COD 自 1,500 ppm 减至 40 ppm或以下。 1. COD has been reduced from 1,500 ppm to 40 ppm or less.

2. SS减至 20 ppm以下。 3. 色度 < 500 ADMI值。 2. SS is reduced to less than 20 ppm. 3. Chroma < 500 ADMI value.

4. 1500 CMD处理量，产生约 1 屯污泥。 4. 1500 CMD throughput, producing about 1 屯 sludge.

5. 回收自生产线流出的 90 % 废水，再用于生产。故本发明的电能式废水处理***可在完全不用任何化学品下 ,将废水从污黑混浊的状态被转化为清澈的生产用水，同时可以提高废水的回收率至 90 %, 故可以直接再用于生产，进一步达到节省用水的功能。当经过本发明的电能式废水处理装置 600、电能式废水处理模块或是电能式废水处理***处理后的水（包括符合放流标准的水以及可以作为生产用的水），若当处理后的废水经过一个检测装置检测并符合放流标准的水后，再将其经一个 RO逆渗透装置过滤时，即可达到人类饮用标准。请参考图 8, 是本发明的电能式废水处理***的再一较佳实施例，此电能式废水处理*** 700可以将废水处理至达到人类饮用标准。如图 8所示，当废水经过本发明电能式废水处理装置 600、电能式废水处理模块或是电能式废水处理***处理后，并经过一检测装置 650检测合格后，即可以作为生产用水；若再将检测合格的水经一个 RO逆渗透装置 720过滤后，即可达到人类饮用标准。而在一较佳实施例中，可将经 RO逆渗透装置 720过滤后的水再经过一次的臭氧产生装置 300的处理（即消毒）后，即可达到人类直接饮用标准。虽然本发明的电能式废水处理***中的电凝聚装置以及臭氧产生装置的特定结构与其实施例，已于前述说明中披露，然而，其所披露的内容仅为本发明电能式废水处理***的实施方式之一，故其所披露的内容并非用来限制本发明的其它实施方式。故本发明除了上述详细的描述外，还可以广泛地在其它的实施例中施行，例如：在电凝聚装置以及臭氧产生装置结构中的电极配置方式、电凝聚装置以及臭氧产生装置结构的固定方式，以及电凝聚装置以及臭氧产生装置的特定组合结构等。因此，本领域技术人员能在不脱离本申请的精神与范畴下丈各种不同形式的改变，这些均应包含在权利要求所限定的范围内。 5. Recycle 90% of the wastewater from the production line for reuse. Therefore, the electric energy type wastewater treatment system of the invention can convert the waste water into a clear production water from the state of black turbidity without any chemicals, and can improve the recovery rate of the wastewater to 90%, so it can be directly reused. In production, it further achieves the function of saving water. When the 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 the treated wastewater After being tested by a detection device and meeting the discharge standard water, it is then filtered through an RO reverse osmosis unit to achieve human drinking standards. Referring to Figure 8, there is still another preferred embodiment of the electric energy type wastewater treatment system of the present invention which 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 600, the electric energy type wastewater treatment module or the electric energy type wastewater treatment system of the present invention, and passed the test by a detecting device 650, it can be used as production water; The qualified water is filtered through an RO reverse osmosis device 720 to achieve human drinking standards. 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 implementation of the electric energy type wastewater treatment system of the present invention. The disclosure is not intended to limit other embodiments of the invention. Therefore, the present invention can be widely practiced in other embodiments in addition to the above detailed description, 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, various modifications of the various forms can be made by those skilled in the art without departing from the spirit and scope of the invention.

Claims

权利要求书 Claim

1. 一种电能式废水处理***，其由一电凝聚装置（EC ) 与一臭氧产生装置串接所组成，其特征在于： An electric energy type wastewater treatment system comprising an electrocoagulation device (EC) and an ozone generating device in series, characterized in that:

废水经过该电凝聚装置（EC ) 并与该电凝聚装置（EC ) 中的阳极电极与阴极电极反应后，再经由该臭氧产生装置中的堆栈电极处理。 The wastewater passes through the electrocoagulation device (EC) and reacts with the anode electrode and the cathode electrode in the electrocoagulation device (EC), and then is treated by the stack electrode in the ozone generating device.

2. 如权利要求 1所述的电能式废水处理***，其中该电凝聚装置中的阳极电极与阴极电极均为柱^ I 电极。 2. The electric energy type wastewater treatment system according to claim 1, wherein the anode electrode and the cathode electrode in the electrocoagulation device are both column electrodes.

3. 如权利要求 2所述的电能式废水处理***，其中该阳极电极材质是自下列中选出：生铁、黑铁、铸铁、光圓铁、 SKD60与 SS430。 3. The electric energy waste water treatment system according to claim 2, wherein the anode electrode material is selected from the group consisting of: pig iron, black iron, cast iron, round iron, SKD60 and SS430.

4. 如权利要求 1所述的电能式废水处理***，其中该臭氧产生装置中的堆栈电极是由多个阳极电极与多个阴极电极交互间断地堆栈形成。 4. The electric energy type waste water treatment system according to claim 1, wherein the stack electrode in the ozone generating device is formed by intermittently stacking a plurality of anode electrodes and a plurality of cathode electrodes.

5. 如权利要求 4所述的电能式废水处理***，其中该堆栈电极中的阳极电极的基板的材质为钛。 The electric energy type waste water treatment system according to claim 4, wherein the substrate of the anode electrode in the stacked electrode is made of titanium.

6. 如权利要求 5所述的电能式废水处理***，其中该堆栈电极中的阳极电极的基板的表面材料为具有至少一种金属掺杂的二氧化锡。 6. The electric energy type waste water treatment system according to claim 5, wherein a surface material of the substrate of the anode electrode in the stacked electrode is tin oxide having at least one metal doping.

7. 如权利要求 6所述的电能式废水处理***，其中该具有至少一种金属掺杂二氧化锡中的该金属是自下列中选出：镍、锑、铁、钌、铂、钯、铑和钴。 7. The electric energy waste water treatment system according to claim 6, wherein the metal having at least one metal-doped tin dioxide is selected from the group consisting of nickel, ruthenium, iron, ruthenium, platinum, palladium,铑 and cobalt.

8. 如权利要求 4所述的电能式废水处理***，其中该阴极电极的材质是自下列中选出：铂、不锈钢及镍。 8. The electric energy waste water treatment system according to claim 4, wherein the material of the cathode electrode is selected from the group consisting of platinum, stainless steel, and nickel.

9. 如权利要求 8所述的电能式废水处理***，其中该不锈钢材质是自下列中选出： SS304, SS304L, SS316, SS316L, SS410, SS410L, SS430。 9. The electric energy waste water treatment system of claim 8, wherein the stainless steel material is selected from the group consisting of: SS304, SS304L, SS316, SS316L, SS410, SS410L, SS430.

10. 如权利要求 4所述的电能式废水处理***，其中该阳极电极上包含多个穿孔。 10. The electric energy waste water treatment system according to claim 4, wherein the anode electrode comprises a plurality of perforations.

11. 如权利要求 4所述的电能式废水处理***，其中该阴极电极上包含多个穿孔。 11. The electric energy type wastewater treatment system according to claim 4, wherein the cathode electrode comprises a plurality of perforations.

12. 如权利要求 1所述的电能式废水处理***，其中该电凝聚装置与该臭氧产生装置之间进一步配置一过滤装置。 12. The electric energy type waste water treatment system according to claim 1, wherein a filter device is further disposed between the electrocoagulation device and the ozone generating device.

13. 如权利要求 1所述的电能式废水处理***，其进一步包括 RO逆渗透装置，该 RO逆渗透装置与该臭氧产生装置连接。 13. The electric energy waste water treatment system of claim 1 further comprising an RO reverse osmosis device coupled to the ozone generating device.

14. 如权利要求 13所述的电能式废水处理***，其进一步包括另一臭氧产生装置，该臭氧产生装置与该 RO逆渗透装置连接。 14. The electric energy waste water treatment system of claim 13 further comprising another ozone generating device coupled to the RO reverse osmosis device.

15. —种电能式废水处理模块，包括电凝聚装置（EC ) 与臭氧产生装置串接所组成的电能式废水处理***、电源供应器以及泵，其特征在于： 15. An electric energy type wastewater treatment module, comprising an electric energy type wastewater treatment system, a power supply device and a pump comprising an electrocoagulation device (EC) and an ozone generating device connected in series, wherein:

16. 如权利要求 15所述的电能式废水处理模块，其中该电凝聚装置中的阳极电极与阴极电极均为柱^ I 电极。 16. The electric energy type wastewater treatment module according to claim 15, wherein the anode electrode and the cathode electrode in the electrocoagulation device are both column electrodes.

17. 如权利要求 16所述的电能式废水处理模块，其中该阳极电极的材质自下列中选出：生铁、黑铁、铸铁、光圓铁、 SKD60与 SS430。 17. The electric energy waste water treatment module according to claim 16, wherein the material of the anode electrode is selected from the group consisting of: pig iron, black iron, cast iron, round iron, SKD60 and SS430.

18. 如权利要求 15所述的电能式废水处理模块，其中该臭氧产生装置中的堆栈电极是由多个阳极电极与多个阴极电极交互间断地堆栈形成。 18. The electric energy type wastewater treatment module according to claim 15, wherein the stack electrode in the ozone generating device is formed by intermittently stacking a plurality of anode electrodes and a plurality of cathode electrodes.

19. 如权利要求 18所述的电能式废水处理模块，其中该堆栈电极中的阳极电极基板的材质为钛。 19. The electric energy waste water treatment module according to claim 18, wherein the anode electrode substrate in the stacked electrode is made of titanium.

20. 如权利要求 18所述的电能式废水处理模块，其中该堆栈电极中的阳极电极的基板的表面材料为具有至少一种金属掺杂的二氧化锡。 20. The electric energy waste water treatment module of claim 18, wherein the surface material of the substrate of the anode electrode in the stacked electrode is tin dioxide having at least one metal doping.

21. 如权利要求 20的所述电能式废水处理模块，其中该具有至少一种金属掺杂二氧化锡中的该金属自下列中选出：镍、锑、铁、 4了、铂、钯、铑和钴。 21. The electric energy type wastewater treatment module of claim 20, wherein the metal having at least one metal-doped tin dioxide is selected from the group consisting of: nickel, ruthenium, iron, tetra, platinum, palladium,铑 and cobalt.

22. 如权利要求 18所述的电能式废水处理模块，其中该阴极电极的材质是自下列中选出：铂、不锈钢及镍。 22. The electric energy waste water treatment module of claim 18, wherein the material of the cathode electrode is selected from the group consisting of platinum, stainless steel, and nickel.

23. 如权利要求 22所述的电能式废水处理模块，其中该不锈钢材质是自下列族群中选出： SS304, SS304L, SS316, SS316L, SS410, SS410L, SS430。 23. The electric energy wastewater treatment module of claim 22, wherein the stainless steel material is selected from the group consisting of: SS304, SS304L, SS316, SS316L, SS410, SS410L, SS430.

24. 如权利要求 18所述的电能式废水处理模块，其中该阳极电极上包含多个穿孔。 24. The electric energy wastewater treatment module of claim 18, wherein the anode electrode comprises a plurality of perforations.

25. 如权利要求 18所述的电能式废水处理模块，其中该阴极电极上包含多个穿孔。 25. The electric energy wastewater treatment module of claim 18, wherein the cathode electrode comprises a plurality of perforations.

26. 如权利要求 15所述的电能式废水处理模块，其中该电凝聚装置与该臭氧产生装置之间进一步配置一过滤装置。 26. The electric energy type wastewater treatment module of claim 15, wherein a filter device is further disposed between the electrocoagulation device and the ozone generating device.

27. 如权利要求 15所述的电能式废水处理模块，其进一步包括 RO逆渗透装置，该 RO逆渗透装置与该臭氧产生装置连接。 27. The electrically powered wastewater treatment module of claim 15 further comprising an RO reverse osmosis device coupled to the ozone generating device.

28. 如权利要求 27所述电能式废水处理模块，其进一步包括另一臭氧产生装置，该臭氧产生装置与该 RO逆渗透装置连接。 28. The electric energy waste water treatment module of claim 27, further comprising another ozone generating device coupled to the RO reverse osmosis device.

29. 一种电能式废水处理***，系由多个电能式废水处理模块所组成，而每一该电能式废水处理模块包括电凝聚装置（EC )与臭氧产生装置串接所组成的电能式废水处理***、电源供应器以及泵，其特征在于： 29. An electric energy type wastewater treatment system, which is composed of a plurality of electric energy type wastewater treatment modules, and each of the electric energy type wastewater treatment modules comprises an electric energy type wastewater formed by a series connection of an electrocoagulation device (EC) and an ozone generating device. A processing system, a power supply, and a pump, characterized by:

废水经过每一该电凝聚装置（EC ) 并与每一该电凝聚装置（EC ) 中的阳极电极与阴极电极反应后，再经由每一该臭氧产生装置中的堆栈电极处理。 The wastewater is passed through each of the electrocoagulation devices (EC) and reacted with the anode and cathode electrodes in each of the electrocoagulation devices (EC), and then through the stacked electrodes in each of the ozone generating devices.

30. 如权利要求 29所述的电能式废水处理***，其中该电凝聚装置中的阳极电极与阴极电极均为柱^ I 电极。 30. The electric energy type wastewater treatment system according to claim 29, wherein the anode electrode and the cathode electrode in the electrocoagulation device are both column electrodes.

31. 如权利要求 30所述的电能式废水处理***，其中该阳极电极材质自下列中选出：生铁、黑铁、铸铁、光圓铁、 SKD60与 SS430。 31. The electric energy waste water treatment system of claim 30, wherein the anode electrode material is selected from the group consisting of: pig iron, black iron, cast iron, round iron, SKD 60 and SS430.

32. 如权利要求 29所述的电能式废水处理***，其中该臭氧产生装置中的堆栈电极是由多个阳极电极与多个阴极电极交互间断地堆栈形成。 32. The electric energy waste water treatment system according to claim 29, wherein the stack electrode in the ozone generating device is formed by intermittently stacking a plurality of anode electrodes and a plurality of cathode electrodes.

33. 如权利要求 32所述的电能式废水处理***，其中该堆栈电极中的阳极电极的基板的材质为钛。 33. The electric energy waste water treatment system according to claim 32, wherein the substrate of the anode electrode in the stacked electrode is made of titanium.

34. 如权利要求 33所述的电能式废水处理***，其中该堆栈电极中的阳极电极的基板的表面材料为具有至少一种金属掺杂的二氧化锡。 34. The electric energy waste water treatment system according to claim 33, wherein a surface material of the substrate of the anode electrode in the stacked electrode is tin dioxide having at least one metal doping.

35. 如权利要求 34所述的电能式废水处理***，其中该具有至少一种金属掺杂二氧化锡中的该金属自下列中选出：镍、锑、铁、 4了、铂、钯、铑和钴。 35. The electric energy wastewater treatment system of claim 34, wherein the metal having at least one metal-doped tin dioxide is selected from the group consisting of: nickel, ruthenium, iron, tetra, platinum, palladium,铑 and cobalt.

36. 如权利要求 32所述的电能式废水处理***，其中该阴极电极材质系自下列族群中选出：铂、不锈钢及镍。 36. The electric energy wastewater treatment system of claim 32, wherein the cathode electrode material is selected from the group consisting of platinum, stainless steel, and nickel.

37. 如权利要求 36所述的电能式废水处理***，其中该不锈钢材质是自下列中选出： SS304, SS304L, SS316, SS316L, SS410, SS410L, SS430。 37. The electric energy wastewater treatment system of claim 36, wherein the stainless steel material is selected from the group consisting of: SS304, SS304L, SS316, SS316L, SS410, SS410L, SS430.

38. 如权利要求 32所述的电能式废水处理***，其中该阳极电极上包含多个穿孔。 38. The electric energy wastewater treatment system of claim 32, wherein the anode electrode comprises a plurality of perforations.

39. 如权利要求 32所述的电能式废水处理***，其中该阴极电极上包含多个穿孔。 39. The electric energy wastewater treatment system of claim 32, wherein the cathode electrode comprises a plurality of perforations.

40. 如权利要求 29所述的电能式废水处理***，其中该电凝聚装置与该臭氧产生装置之间进一步配置过滤装置。 The electric energy type waste water treatment system according to claim 29, wherein a filter device is further disposed between the electrocoagulation device and the ozone generating device.

41. 如权利要求 29所述的电能式废水处理***，其进一步包括 RO逆渗透装置，该 RO逆渗透装置与该臭氧产生装置连接。 41. The electric energy waste water treatment system of claim 29, further comprising an RO reverse osmosis unit coupled to the ozone production unit.

42. 如权利要求 41所述的电能式废水处理***，其进一步包括另一臭氧产生装置，该臭氧产生装置与该 RO逆渗透装置连接。 42. The electric energy waste water treatment system of claim 41, further comprising another ozone generating device coupled to the RO reverse osmosis device.

43. —种电能式废水处理***，包括： 43. An electric energy wastewater treatment system, comprising:

泵，将废水吸出； Pump, pumping out wastewater;

第一过滤装置，用以过滤经过该泵加压吸出的废水； a first filtering device for filtering waste water sucked out by the pump;

电凝聚装置（EC ) , 由一电解槽以及配置于该电解槽中的至少一对阳极电极与阴极电极组成，其中该电解槽的进水端与该过滤装置连接；第二过滤装置，其一端与该电凝聚装置的该电解槽的一出水端连接； An electrocoagulation device (EC) consisting of an electrolysis cell and at least one pair of anode electrodes and cathode electrodes disposed in the electrolysis cell, wherein the inlet end of the electrolysis cell is connected to the filtering device; the second filtering device has one end Connected to a water outlet end of the electrolysis cell of the electrocoagulation device;

一臭氧产生装置，由一电解槽以及配置于该电解槽中的由阳极电极与阴极电极交叉堆栈形成的堆栈电极所组成，其中该电解槽进水端与该第二过滤装置的另一端连接；第三过滤装置，其一端与该臭氧产生装置的该电解槽的一出水端连接；以及 An ozone generating device, comprising an electrolytic cell and a stacked electrode disposed in the electrolytic cell, wherein the inlet end of the electrolytic cell is connected to the other end of the second filtering device; a third filtering device, one end of which is connected to a water outlet end of the electrolytic cell of the ozone generating device;

电源供应模块，其与该电凝聚装置（EC )及该臭氧产生装置连接，以提供该电凝聚装置（ EC ) 及该臭氧产生装置所需的电源。 A power supply module is coupled to the electrocoagulation device (EC) and the ozone generating device to provide the electrocoagulation device (EC) and a power source required for the ozone generating device.

44. 如权利要求 43所述的电能式废水处理***，其中该电凝聚装置中的阳极电极与阴极电极均为柱^ I 电极。 44. The electric energy waste water treatment system according to claim 43, wherein the anode electrode and the cathode electrode in the electrocoagulation device are both column electrodes.

45. 如权利要求 44所述的电能式废水处理***，其中该阳极电极的材质自下列中选出：生铁、黑铁、铸铁、光圓铁、 SKD60与 SS430。 45. The electric energy waste water treatment system according to claim 44, wherein the material of the anode electrode is selected from the group consisting of: pig iron, black iron, cast iron, round iron, SKD60 and SS430.

46. 如权利要求 44所述的电能式废水处理***，其中该臭氧产生装置中的堆栈电极是由多个阳极电极与多个阴极电极交互间断地堆栈形成。 46. The electric energy waste water treatment system according to claim 44, wherein the stack electrode in the ozone generating device is formed by intermittently stacking a plurality of anode electrodes and a plurality of cathode electrodes.

47. 如权利要求 46所述的电能式废水处理***，其中该堆栈电极中的阳极电极的基板的材质为钛。 47. The electric energy waste water treatment system according to claim 46, wherein the substrate of the anode electrode in the stacked electrode is made of titanium.

48. 如权利要求 47所述的电能式废水处理***，其中该堆栈电极中阳极电极的基板的表面材料为具有至少一种金属掺杂的二氧化锡。 48. The electric energy waste water treatment system of claim 47, wherein the surface material of the substrate of the anode electrode in the stacked electrode is tin dioxide having at least one metal doping.

49. 如权利要求 48所述的电能式废水处理***，其中该具有至少一种金属掺杂二氧化锡中的该金属是自下列中选出：镍、锑、铁、钌、铂、钯、铑和钴。 49. The electric energy wastewater treatment system of claim 48, wherein the metal having at least one metal-doped tin dioxide is selected from the group consisting of: nickel, ruthenium, iron, ruthenium, platinum, palladium,铑 and cobalt.

50. 如权利要求 46所述的电能式废水处理***，其中该阴极电极的材质是自下列中选出：铂、不锈钢及镍。 50. The electric energy waste water treatment system of claim 46, wherein the cathode electrode is selected from the group consisting of platinum, stainless steel, and nickel.

51. 如权利要求 50所述的电能式废水处理***，其中该不锈钢材质是自下列中选出： SS304 , SS304L, SS316 , SS316L, SS410 , SS410L, SS430。51. The electric energy waste water treatment system of claim 50, wherein the stainless steel material is selected from the group consisting of: SS304, SS304L, SS316, SS316L, SS410, SS410L, SS430.

52. 如权利要求 43所述的电能式废水处理*** ,其进一步包括一 RO逆渗透装置，该 RO逆渗透装置与该第三过滤装置连接。 52. The electric energy wastewater treatment system of claim 43 further comprising an RO reverse osmosis unit coupled to the third filter unit.

53. 如权利要求 51所述的电能式废水处理***，其进一步包括另一臭氧产生装置，该臭氧产生装置与该 RO逆渗透装置连接。 53. The electric energy waste water treatment system of claim 51, further comprising another ozone generating device coupled to the RO reverse osmosis device.

54. 如权利要求 43所述的电能式废水处理***，其进一步包括一检测装置，该检测装置系与该第三过滤装置连接。 54. The electric energy wastewater treatment system of claim 43 further comprising a detection device coupled to the third filtration device.