TW201130751A - Compound apparatus for processing waste water - Google Patents

Abstract

Integrating the electrocoagulation (EC) and electrolytic ozone (EO3) devices in a single container form a compound apparatus able to purify all kinds of waste water. In the integration, the EO3 electrode is placed between the EC electrodes. Hence, the formed compound technology can be called EC with embedded EO3. By applying two types of electrical powers, the EC anode will release coagulant, and EO3 will electrolyze water to generate ozone (O3). In the same chamber, the coagulant and O3 will generate much reaction so that the compound apparatus for processing waste water can purify all kinds of waste water rapidly. In particular, if Fe is used as the EC anode, O3 will react with ferrous ions (Fe2+) generated by Fe anode to generate even powerful oxidants stronger than O3. These powerful oxidants enable the compound technology to remove the chemical oxygen demand (COD), biochemical oxygen demand (BOD), heavy metal, color, total suspended solid(TSS), total organic carbon (TOC), total organic halide (TOX) and microbes from the waste water at a rate 1, 000 times faster than EC or EO3 alone. Due to fast processing, the compound technology also consumes less energy than EC or EO3.

Description

201130751, VI. Description of the invention: [Technical field to which the invention pertains] The present invention combines two electrochemical methods in the same container to treat various wastewaters. More specifically, the present invention is a wastewater treatment apparatus using electrocoagulation (EC) technology and electrolytic ozone (E〇3) technology to remove chemical oxygen demand (COD) in wastewater with high efficiency. ), Biochemical Oxygen Demand (BOD), Heavy Metals, Color, Φ Total Suspended Solids (TSS), Total Organic Carbon (TOC), Total Organic Teeth (TOX), and Microorganisms. [Prior Art] Water is vital to the survival of all living things on Earth. Due to the population boom and the booming of industry and commerce, the amount of pollutants discharged into various waters has increased, making many people in the world unable to access safe drinking water. Coupled with the excessive use of oil to cause global warming, changing the climate in many parts of the world. • Drought or flooding has made the water shortage problem even worse. If the process of purifying water is too much, it will also increase global warming. Most of the contaminants in water come from natural or man-made organics such as petroleum, dyes, carbohydrates, food oils, fats, detergents, fertilizers, proteins, medicines and pesticides. These contaminants are sources of water, TSS, T0C, color and turbidity. Many water pollution cannot be handled by the city: the current commonly used technology to the thief standard, or the treatment method is too expensive or too large, people can not afford. 201130751 General wastewater is treated in three stages (ie three processes) after coarse filtration and adjustment of the pH of the water. The first stage of treatment is chemical coacervation, which is the addition of a precipitant or coagulant to cause precipitation or flocculation of water and remove some of the source of water from the water. After the solids are removed by filtration or scraping, the wastewater is subjected to a second stage or biological digestion process to digest the remaining carbon, nitrogen, phosphorus and sulfur contaminants by anaerobic and aerobic bacteria. Next, in the third stage treatment, the wastewater is further treated by oxidation, ion exchange, electrodialysis, microfiltration or ultrafiltration, reverse osmosis or electrolysis to obtain the desired purity. Both the chemical coacervation method and the bio-digestion method occupy a large area and generate a large amount of sludge, which increases the cost of the overall wastewater treatment. In addition, the biological digestion method produces odor and takes too long, and the aerobic treatment requires a large amount of electric energy to drive air or oxygen into the water to accelerate the reaction. Even some organic molecules cannot be digested by bacteria, but must be decomposed with antibacterial pollutants by means of an oxidant such as ozone. 0 Electrocoagulation (EC) technology is designed to reduce the amount of sludge produced by coagulation and decontamination, and Increase the filtration rate. Generally, the suspended solids are negatively charged, the Ec technique only produces the cations required for coagulation (positively charged), and the inactive anions are completely absent. Due to the disappearance of anions, the amount of sludge produced by EC technology is at least 3G-gas less than chemical coagulation. At the same time, the sludge produced by Ec technology has lower water content, larger particle size and density, and less disintegration of the young ones, making the processing speed of EC technology faster than chemical coagulation. The most important thing is that the EC technology treatment occupies much less than the chemical coagulation method, and the EC technology can replace the chemical coagulation method as a commercial process for wastewater treatment. Lai EC technology can remove many pollutants, but it does not work well with light oil, 201130751 alcohols, aromatic and ammonium salts, and requires ozone (〇3). Reports on the use of ozone to increase the efficacy of EC technology can be found in U.S. Patents 6,902,678, 6,960,301 and 7,513,999, and s〇ng

Separation and Purification Technology^ Vbl. 55} pp 238-245 (2007). Ozone has also been used to enhance the efficacy of chemical coacervation methods', e.g., U.S. Patent No. 5,56,. However, the ozone used in the above-mentioned agglomeration method is a corona discharge method derived from decomposition of air or pure oxygen. Ozone is produced in a separate generator and then dispersed in an EC or chemical coagulation reactor through a specially designed bubbler. Glow Discharge Ozone Generators are bulky, expensive, complex to operate, and inefficient. In contrast, the electrolytic ozone (E〇3) technology directly generates A from the wastewater to be treated, with small bubbles, high efficiency (3〇% vs. 4/〇), small footprint, and no gas transport and dispersion. Therefore, the technology is superior to the glow discharge method in terms of energy consumption and cost. From functional considerations, EC technology and Eq3 technology (10) destructive processing. The latter is the decomposition of the anode, and the latter is the dissociation of water. However, EC technology and E〇3 technology have the following common points: Both electrodes can be immersed in the wastewater to be treated. 2 The concentration of the treatment agent (metal cations and ozone) can be determined by the area, spacing and supply of the electrodes. Power control, and 3) no secondary pollution. These commonalities make Ec technology and Ε〇3 technology easy to combine as "Ε〇3 inlaid in EC", which is called "composite technology" in the present invention, which halved the total area of EC technology and Ε〇3 technology. The composite technology not only preserves the original strengths of the team's technology and the Ε〇3 technology, but also produces an additive effect. Due to the production of some more powerful treatment agents than metal cations and ozone, compound 201130751 • The efficacy of technical treatment of wastewater is more significant than EC technology or E〇3 technology. β EC technology is a water treatment technology with a history of more than 100 years (first in 1906). EC technology uses electrical energy to coagulate, gelatinize or precipitate solids suspended or dissolved in water. In order to generate an electrochemical reaction, the EC technique requires at least a pair of anodes and cathodes, and the electrodes may be plate-shaped, spherical, massive, granular, rod-shaped, linear, reticulated, columnar or tubular. EC technology also requires a direct current (DC) or alternating current (AC) power supply to provide the power needed for processing. The chemical coacervation process in the first stage treatment of wastewater is carried out by adding a large amount of chemicals to the wastewater to cause some contaminants to be coagulated, gelatinized or precipitated. However, among the chemicals added, only the cations have the ability to decontaminate, and the anions are secondary pollution, increasing sludge production and sludge treatment costs. In contrast, the EC technique uses electrolysis of the anode to produce only the cations required for coagulation, and the anions are completely absent. Therefore, the amount of sludge produced by EC technology is at least 30-40% lower than that of chemical coagulation. At the same time, EC technology also provides direct oxidation of the contaminants on the electrodes, or direct reduction reactions, enabling EC technology to quickly handle multiple water contaminations. Table j lists the EC technology to effectively remove various inorganic, organic and microbial contaminations. Table 1 Detergency removal rate of EC technology (%) Contaminants 96 - 99+ Ab Ag, Am, Ba, cd, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Ra, Si, U, Zn, bacteria 'total coliform, color, petroleum, hydrocarbon, insecticide 201130751 90-95 agent, acid-filled manj^TSS As, CN, ρ·, n, Ph, V 70-80 B, Co, Mo 60 -69 NH/'Hg 20-59 K, Se 0-19 Na, Cl. In order to achieve a 99+% decontamination rate, the anode material of the correct EC electrode must be confirmed before any wastewater is treated. Material validation must be completed prior to application of EC technology. From the chemical affinity 姊 (four), the anode material mosquitoes are in the county. For example, Shao (A1) metal is the best hoof material for the treatment of food and plant waste water, and iron (four) gold is the preferred anode material for dyeing and dyeing wastewater. Even with the treatment of wastewater from the same industry, the EC technology used in the processor and electrode structure design, total electrode area, electrode spacing, power supply and water flow speed parameters are often different. Despite the differences in practical applications, all EC technologies have a common goal of increasing the particle size and density of suspended solids in the water and making the solids dissolved in water a precipitate. After the small contaminant particles are formed into large pieces (such as from 0.2 micron to more than 1 micron), they will be separated from the water in the form of colloid, gelatin, scum or sediment. Compared with sludge produced by chemical coacervation, EC technology sludge has low water content, high density, high mechanical strength (not easy to disperse), and therefore easy to remove. The next section will explain the cohesion mechanism of EC technology. Aluminum (AI) and iron (Fe) are the two metals most commonly used as sacrificial anodes for EC electrodes. When a DC or AC power is applied to the anode and cathode of the EC electrode at 201130751*, the aluminum (A1) and iron (Fe), which are the sacrificial anodes of the EC electrode, will undergo oxidation reactions as listed in Equations 1 and 2: A1 —> Al3+ + 3e" (1)

Fe -> Fe2. + 2e- (2) The metal cations produced by equations (1) and (2) will attract and accumulate with negatively charged suspended or dissolved solids in water. The result of positive and negative neutralization causes the contaminants to lose their stability in the water. At the same time as the oxidation reaction occurs, the surface of the cathode, which is made of Al, Fe, copper (Cu) or nickel (Ni), undergoes a reduction reaction as shown in equation (3): 2H2〇+ 2e- -»H2T + 〇H- (3) Equation (3) will trigger the following two important effects: A. The 氲 离子 ion (〇Η·) will react with 丨3+ and Fe2+ to form water-insoluble bismuth oxide |g[Al(〇H)3] and ferrous hydroxide [pe(〇H)2]. The foregoing niobium oxide then adsorbs solids suspended or dissolved in the water to form a colloid or precipitate. B. The colloid suspended in the water adheres to the tiny hydrogen (H2) bubbles and becomes the scum. As long as the wastewater can be treated to the desired water quality in a cost-effective and efficient process, the EC technology processor can make the necessary combination of parameters depending on the nature of the wastewater. First, the same or different metals may be used for the anode and the cathode. The metals selected include: A, Fe, Cu, Ni, Ti, Ag, Mg, Sn, Zn, copper, bronze, and stainless steel. Second, the electrical connections of the electrodes can be unipolar (positive and negative), bipolar (the same electrode with positive and negative electrical), and single and double mixed polarity. Furthermore, EC technology processing can use AC or DC voltages with voltages ranging from 5¥ to 100V. During processing, Ec 201130751 ; The technical processor can be powered by a combination of constant voltage mode, constant current mode, pulse mode or above. In order to promote the agglomeration of suspended or dissolved solids in water, the EC technology reaction time must be sufficient to produce an appropriate amount of coagulant and allow the suspension to grow into large particles. Finally, the sludge produced by the EC technology must be removed by solid-liquid separation techniques. Suitable separation techniques must provide fast on-line operation with the option of: adsorbent, filter, electromagnet, centrifuge, freezer or hopper. If the EC technology processor can not remove more than 70% of the sludge, excessive sludge will be present in the water, which will seriously hinder the efficiency of EC treatment. The history of Ε〇3 technology for wastewater treatment is still longer than EC technology. 1840). In the E〇3 technique, applying a voltage of 24 V DC or less to the E〇3 electrode will cause the water to decompose to generate ozone. The above-mentioned water decomposition reaction is a well-known electrolysis of water, and as long as a voltage of 1 V can occur, the EO3 technique becomes a low voltage technique. The efficiency of ozone production by E〇3 technology is higher than that of glow discharge and ultraviolet radiation, so the cost of E〇3 technology is lower. The EO3 technology of the present invention also has the following advantages: Lu 1. The bribe is used as the surface of the ozone (4), and is produced by tiny bubbles in the water. Small volume boost & sterilization, disinfection, decolorization and deodorization. _ 〇 3 reflection _ is ozonation. 2. The production of ozone can be controlled by the following parameters: total anode area, electrode spacing, supply power and water flow rate. 3. Because the ozone formation reaction is easy to grasp, &&&&&> 4. Waste water can flow through the E〇3 electrode and be immediately treated on the spot “oozonization” 201130751. 5. The E〇3 technology processor is simple in structure and requires only three components: an e〇3 electrode, a container for the electrode, and a DC power supply (providing the power required to generate ozone). As a result, the EO3 technology processor is small, low cost, and easy to place. Unlike EC technology, which provides a variety of electrochemical reactions, the only technique is the oxidation of water molecules on the anode and the two electrochemical reactions on the cathode. The anode of the E〇3 technology processor does not participate in the electrochemical reaction, it is only used to catalyze the electrolysis of water to produce ozone. In fact, the anode of the e〇3 electrode belongs to a stable anode (DSA), which is used for the anode of an environmentally harsh electrolytic cell, such as the anode used in the alkali gas industry. The standard electrode potential E is set with the standard hydrogen electrode as the reference electrode. To illustrate the electrolysis of water, the anodization and cathode reduction of water molecules can be expressed by equations (4) and (5): % pole oxidation 2H20 -> 〇2 + 4H1" + 4e- E° = 1.23V (4) Cathode reduction 2H2〇+ 2e H2 + 〇Η" E° = 〇.〇V (5) Simultaneously with oxygen (〇2), ozone (A) may also be produced together on the anode, but the latter's standard electrode The potential is higher, as shown in equation (6): Ozone generation reaction 3H20~>〇3 + 61^ + 6^ Eo=1.60V (6) Theoretically, the electrolysis of water molecules on the anode It should be possible to produce both oxygen and ozone. However, the anode material used in the electrolysis of water generally produces only oxygen and has no detectable ozone. The foregoing phenomenon results from the oxygen generating potential of the anode material used, that is, the oxygen overcurrent 201130751 (or overvoltage, potential equal to voltage), and E listed in equation (4). In the same way, if the electrolysis of water produces "available" ozone, the oxygen overpotential of the anode material used must be higher than E of equation (6). The value, so that a large amount of Os has appeared before the generation of 〇2. Materials with oxygen overpotentials above 1.60V' include: Pt, Pd, Au (Au), glassy carbon, graphite, β-state lead dioxide (P-Pb〇2), antimony oxide ( Ir〇2), boron-doped diamond film (BDD) and doped tin dioxide (Sn〇2). Among the materials having a high oxygen overpotential, the doped tin dioxide is the best material used in the present invention as the eq3^positive layer. The present invention is based on the following reasons: ) low cost, 2) high production capacity of 3, 3) easy to apply to water treatment, 4) easy expansion and 5) environmental protection. Pure tin dioxide is an n-type semiconductor with a direct band gap of 3_5 eV. Another feature of the use of tin dioxide as the anode catalyst for E〇3 is that the oxygen overpotential of Sn〇2 is higher than that of platinum (pt) by 6 v, so that the efficiency of generating ozone is high. In order to improve the electrical conductivity, Sn 〇 2 may be doped with a metal atom such as Sb or doped with a non-metal ion such as fluoride (F_). In addition, in order to increase the efficiency of producing 03, Sn 〇 2 may also be doped with another metal atom such as (10). Using a bimetallic doping system of Sb and Ni, a Sb-Ni-doped tin dioxide (Sb, Ni_Sn〇2) film has been deposited on a titanium (9) substrate to become an anode of an E〇3 electrode, and is applied to the United States. Patent, the number is 2, m. The document is listed as a reference for the present invention. However, the present invention further improves the US Patent Application No. 12, the process of iu, and the silver (8) as the third _ Jin Guzi, into the enemy's innovative three metal holdings. Miscellaneous system. As applied for No. 12 dirty, 111, the present invention still uses dip 12 201130751 • Decomposition of hot melt solution to deposit sb side. Doped tin dioxide (Sb, Ir, Ni-Sn〇2) film on Ti substrate. However, the atomic ratio of the main metal (Sn) to the mixed metal plate, Ir and Ni) is Sn:Sb: (4) Bu·丨(4): i. [Invention] The present invention is combined with the EC electrode E〇3 electrode. In the same tubular container, the wastewater treatment process of the innovative composite technology is formed. In the composite technology, the wastewater treatment device towel 'EC electrode is shaped like a long metal rod or a long metal tube, and is arranged in a radial shape in the tube. In the middle, the % electrode is a stacked plate-like metal placed in the middle of the EC electrode. The EC electrode and the % electrode have their own power supply 'because the EC f pole and the % electrode operate at different voltages. According to the wastewater treatment, f The composite treatment technology of the wastewater treatment device can be combined with the diameter of the Degree, at the same time with a suitable number of composite technology waste disposal equipment to form a ___ clean, removable independent wastewater treatment system. Then 'with each treatment capacity of the wastewater treatment system, plus treatment targets (such as water and water f ), you can determine - a complete electrical location > _^UeleetiO_t_nem system, ETS) 'Requires several wastewater treatment systems. In the ETS towel's multiple wastewater treatments can be arranged in a space-saving stacking matrix to reduce the system's occupation The most common electrolysis (or sacrificial) anode of the EC electrode is iron (Fe) or aluminum (A1). The cathode is also iron or aluminum. In other words, the anode and cathode of the Ec electrode can be made of the same metal. Or different metals. Regardless of the metal electrode used, the 'EC electrode can be operated with direct current (DC) or alternating current (AC). When operating with Ac, the Ec electrode is used as a sacrificial type 13 201130751; the anode 'provides the need for agglomeration The cations make the EC electrode consume at the same speed. As for the use of iron or shovel as the sacrificial anode, it will depend on the composition of the wastewater. However, if the treatment is fast, the mining ship is a sacrificial anode. The ferrous ion (Fe2+) produced by it will be oxidized by ozone to produce hydroxyl radical (·〇Η), ferrate ion (Fe〇42) and tetraferric ferrite ion [Fe(IV) 〇]2+]. The decontamination ability of free radicals and iron-containing oxidants is stronger than that of strontium and oxygen, so that the rate of compounding organic pollutants is 1000 times faster than EC technology or E〇3 technology. The addition effect, the wastewater treatment device of the composite technology should produce a concentration of 〇3 of at least 20 times that of Fe2+. Therefore, the EC electrode of the composite wastewater treatment device uses a narrow column or tube, and the E〇3 electrode is The plate shape of the width and length ' makes the concentration ratio of 〇3 to Fe2+ the optimum value. Combined with the EC electrode and the EO3 electrode in the same container, ozone (〇3) can be quickly reached to the Fe2+ production site, and rapidly formed.·〇Η, Fe〇42· and [Fe(IV)0]2+. Once these powerful oxidants are produced, they will immediately destroy nearby organic pollutants and microorganisms. The present invention produces a ruthenium 3 catalyst by using a tin dioxide (Sn〇2) film containing three kinds of doped metals as an anode of the EO3 electrode to electrolyze water. In addition to low cost, metal-doped tin dioxide with DC voltage below 24 V, decomposes any wastewater and directly produces 〇3 ° in water. E〇3 uses porous electrodes and open stack assembly, so anode gas (〇3/ 〇 2) and the cathode gas (3⁄4) can freely diffuse the wastewater treatment device filled with the entire composite technology to react with Fe2+. By controlling the number of anodes, electrode area and spacing, power supply, and water flow rate, the E〇3 electrode produces the required amount of 〇3. 201130751 Similarly to control the power supply, the composite technology wastewater treatment device can operate in three modes, namely: EC mode (E〇3 electrode is not powered); E〇3 mode (EC electrode is not powered); and dual reaction mode (EC electrode) Both the E and E electrodes are powered). Depending on the processing target, a suitable operating mode can be used. To quickly reduce the COD, TOC, TSS and color of wastewater, a dual reaction mode, ie a composite technique, should be used. On the other hand, the E〇3 mode must be used to treat contaminants left over from composite technology to produce more purified water. φ EC treatment involves electrochemical reactions and physical processes (such as coagulation), while e〇3 treatment only decomposes pollutants by oxidation. Since the physical process is faster than the oxidation reaction, the decontamination rate of the EC technology is faster than the E〇3 technique. However, the -E〇3 technology purifies the water treated by the EC technology, making the e〇3 technology a “scavenger” that uses EC technology, such as composite technology. However, because EC technology, EO3 technology and composite technology are all electrolytic methods, they are likely to produce charged by-products. The removal of ionic species in water is not the main function of these technologies. Therefore, the present invention removes ionic species left or produced by EC technology, EO3 technology or composite technology by means of capacitance/deionization (CDI) technology. The above and other objects and advantages of the present disclosure will be described in detail below with reference to the accompanying drawings. [Embodiment] [S] The present invention combines the conventional EC and E〇3 electrochemical methods into an innovative wastewater treatment technology. The present invention will be described in detail below through the first figure and the second figure 15 201130751. The first figure shows a wastewater treatment apparatus 10 of the composite technology of the present invention, which allows wastewater to pass through for treatment. The wastewater treatment device 10 includes a tubular processor (not shown), a flange, an EC electrode, and an E 3 electrode. The tubular processor (not shown) includes at least one water inlet and one water outlet. The EC electrode and the E〇3 electrode are placed in the tubular processor (not shown) which is in the tubular device (not shown). The EC electrode and the E〇3 electrode will be described in detail below. The EC electrode is composed of a first EC electrode 11A and a second EC electrode 13's metal rod in a circular arrangement. The E?3 electrode 160 is a stacked metal piece' placed between the first EC electrode 110 and the second EC electrode 130. The dimensions of the first EC electrode 11 〇, the second EC electrode 13 〇 and the e 〇 3 electrode 16 均 are both limited by the inner diameter and length of the tubular processor (not shown). If the inner diameter of the tubular processor (not shown) is 15 cm and the length is 2 m, the second lu-EC electrode 110 and the second EC electrode no can be 8 mm thick, 9 〇-95 cm long metal rod, and EO3 electrode 160 It can be a rectangular metal piece having a width of 7.5 cm and a length of 80 cm. The EC electrode comprises at least an anode, a cathode and a power supply, and further comprising at least one electrical terminal connected to the anode of the EC electrode and a positive pole of the power supply, and at least an electrical terminal connected to the cathode of the Ec electrode and the power supply The negative pole of the device. As shown in the first figure, the first EC electrode 110 has five electrodes, which respectively correspond to five first group electrical ends 201130751: sub-150, and the second EC electrode 130 also has five electrodes, corresponding to five Two sets of electrical terminals 丨7〇, in order to make full use of the anode, the number of cathodes

Forever one more than the anode, for example, the first EC electrode 11〇 and the second EC electrode 130 of the five electrodes, the cathode each accounted for 3, the anode each accounted for 2 'all 6 cathodes will be with the power supply (Figure The negative electrodes, not shown, are connected, and all four anodes are connected to the positive electrode of the power supply (not shown). The Ε〇3 electrode comprises at least an anode, a cathode and a power supply, and at the same time, the electrical contact connects the anode of the ΕΟ3 electrode with the anode of the power supply, and the at least one electrical contact connects the ε〇 The cathode of the 3 electrode and the cathode of the power supply. Similarly, in order to make full use of the anode, the number of cathodes of the ΕΟ3 electrode is always one more than the anode, as shown in the first figure, the electrode 16〇 contains 5 pieces of metal, the cathode can occupy 3 pieces, and the anode can occupy 1 piece. 'The first electrical connection. The point 120 is connected to the anode of the Ε〇3 electrode 160 and the anode of the power supply wire (not shown), and the second electrical contact 140 is connected to the cathode of the Ε〇3 electrode 160 and the power supply. The negative pole (not shown). The flange 101 has eight holes 102, and the holes 1〇2 are used to fix the flange 101 to a tubular processor (not shown). The flange 1〇1 can also fix the first EC electrode 11〇. a set of electrical terminals 15A, a second set of electrical terminals 170 of the second EC electrode 13A, a first electrical contact 120 of the E〇3 electrode 160, and a second electrical contact 14〇 of the EO3 electrode 16〇, thus An EC electrode 110, a second Ec electrode 13A, and an E〇3 electrode 16〇17 201130751 are fixed in the tubular process _not shown). _ As in the relative position of the example shown in the first circle, the pitch of the -EC electrode 110, the electrode 130, and the e〇3 electrode 16〇 is fixed so that there is no spacer between the open-type electrodes. The distance between the first-EC electrode 11A and the second electrode 130 is 2〇_3〇, and is positioned by a plurality of plastic fixing rings. Each of the fixed® rings 103 is a cross-shaped tooth for placing the stacked % electrode 16 turns. The E 〇 3 electrode ΐό〇 has a pitch of 2 mm and is positioned by a fixing clip (not shown) of the first EC electrode 110 and the second EC electrode 130. All the electrolyzers show that the edge of the electrode produces more than the other surfaces of the electrode, which means that the electrode side has higher electrical hysteresis and the electrochemical reaction is more intense. Such a current distribution phenomenon is called a "marginal effect". Therefore, in order to generate a large amount of bubbles in the anode and the cathode, the E〇3 electrode 16 is a porous structure, and the porous structure can also rapidly separate the anode and cathode products 〇3, 〇2, and H2 from the electrode surface, and then fill the entire surface. In the wastewater treatment device 10, it rapidly reacts with Fe2+ and pollutants. In the above description of the e〇3 technique, it is pointed out that the anode of the EO3 electrode 160 is an electrode on which a three-metal Sb, Ir, Ni-doped tin oxide (Sb, Ir, Ni-SnO 2 ) film is deposited on a Ti substrate. As the cathode of the E〇3 electrode 160, a metal such as stainless steel, aluminum, nickel or titanium may be used. When the first EC electrode 110 and the second EC electrode 13 are made of iron (Fe) as an anode and a voltage of 0.5 V or higher is applied thereto, the anode will dissolve 201130751 to produce ferrous ions (Fe2+). Fe2+ is first oxidized by oxygen in air and water to iron ions (Fe3+). Trivalent iron ions and its nitrogen oxides and oxides (ie, iron hydroxide and iron oxide) are strong coagulants that promote water. Contaminants condense. However, if there is a specific oxygen deficiency in the water, such as hydrogen peroxide (H202), Fe2+ will react with h2〇2 to produce a chlorine radical (•OH), as described in equation (7):

Fe2+ + H2〇2 -> Fe3+ + ·〇η + 〇Η- (7) In fact, the combination of Fe and shame is the well-known Fenton's s〇luti〇n, which is a commonly used oxidant for general water treatment. Fenton's solution has better oxidizing power than hydrogen peroxide, which is due to the generation of nitroxide (•OH). In the Fenton reaction, the typical Fe2+ dosage is the working Fe2+ with 5·25 shame. The oxidation capacity of ozone (a) is far better than that of H202 ' 03. It does not react with Fe2+ to produce the 〇h group required for water treatment. 〇3 also rapidly oxidizes Fe to pe3+, and then 〇3 further oxidizes Fe3+ to become expensive. Iron ions, such as hexavalent iron ion Fe6+ (Fe(VI)), or ferrate (Fe042·). Gao Xiancai Linlin bleach or sodium hypochlorite (NaOCl) is synthesized under strong conditions, as described in U.S. Patent No. 6, pp. 33,343 and 6,974,562, and can be illustrated by equations (8) and (9):

Fe3+ + 30H· — Fe(〇H)3 (g) 2Fe(OH)3 + 30Cr + 40H, 2Fe〇42· + 3C1- + 5H20 (9) In the equation (9) towel 'recording 峨: domain acid county (QC1·) is oxidized to ferrate ((10)2·). Since the oxidizing ability of ozone (〇3) is a thousand times stronger than that of ocr (for example, the sterilization rate of ozone is 3, _ times faster than that of chlorine), the generation of strontium ferrite at a high concentration of 201130751 is easier. The above inference can be corroborated by Shanna et al. in the journal j. Waterand He (4), 卯仏 57 (20_ report), which states: "In a strongly oxidizing environment, high-oxidation iron ions such as +4, +5, and %±±j〇^ ^. Groves ^ J. Inorganic Biochemistry, Vol. 働' PP 434-447 (2006) clearly stated in the report: "Fe2+ can be oxidized to tetravalent by ozone (〇3) Iron ion Fe(IV)", as described in Equation 1〇:

Fe2+ + 〇3 [Fe(IV)〇]2+ + 〇2 ferrate ions ruthenium 42-) and quaternary ferrite ions [fenyl [Fe(IV)0]2+] belong to the iron-containing oxidant family. It has stronger ability to eliminate organic pollutants, heavy metals and microorganisms than ozone (〇3). In this case, the waste water treatment device 1G containing iron oxidant has a large storage tank to reduce the footprint of the system. The wastewater treatment device of the composite technology of the present invention simultaneously generates a large amount of Fe2+ and ozone (〇3), causes the hydroxyl radical (·〇Η) and the iron-containing oxidant to be generated online, and immediately performs on-site sterilization. A voltage of 10 V or more and a current density of 1 〇 mA/cm 2 are applied to the anode of the Ε〇 3 electrode 160 in the wastewater treatment apparatus 10, and an anode catalyst of E 〇 3 electrode 160 per square centimeter (Sb, Ir, Ni_Sn 〇 2) It is possible to produce 24 mg of ozone per hour (24 mg 〇3/cm2*hr) in water. The ozone production capacity is proportional to the current enthalpy, which is related to the applied voltage and the conductivity of the water. 1 waste water treatment device 10 is installed with a 7.5cm X 30cm E〇3 electrode 160 anode, the total anode area is 4500 cm2, and when ιον X 45A (4500 cm2 X 1〇mA/cm2) is applied, the branch is installed. The wastewater treatment plant 10 can produce i〇8 g of ozone per hour 20 201130751 *. The solubility of ozone in water is very low, and the lower the temperature, the higher the solubility. In general, only 0.3% of the ozone produced by the anode of the EO3 electrode 16 is dissolved in water, and the rest is maintained in a gaseous state. Whether it is dissolved in water or gaseous ozone, it has oxidizing power. In combination with the high concentration of ozone and the first EC electrode 11 and the iron anode in the second EC electrode 130, the ruthenium free radical and the iron-containing oxidant can be generated in the wastewater treatment device 10 with water flow, destroying various contaminants in the flowing water on the spot. The superiority of the wastewater treatment plant of the composite technology invented by Ruben can eliminate the chemical oxygen demand (COD), biochemical oxygen demand (BOD), color, heavy metal, total organic carbon (TOC) and total organic south in the water. The compound (TOX), total suspended solids* (TSS) and microbes were demonstrated 1,000 times faster than EC technology or E〇3 technology. In addition to the enhanced ability to decontaminate, the wastewater treatment unit of the composite technology has an additive effect, that is, its processing by-product is completely harmless iron oxide (Fe203), which makes the E03 technology possible to produce cancer-causing bromic acid. Salt (BrO〇 disappears. Although the combination of the Ec electrode with aluminum metal as the anode and the _EO3 electrode does not produce ions higher than Al3+, 〇3 can still improve the decontamination rate of the EC electrode using the aluminum anode. This is because 〇3 can destroy the stability of water-soluble or suspended organic pollutants in water. To control the supply of electricity, the wastewater treatment device 10 can be operated in three modes: 1. EC mode: electricity is supplied only to the first EC electrode 11 〇 and the second EC electrode 130. 2. E〇3 mode: power only supplies EO3 electrode 160 〇 This mode produces very little 21 201130751 amount of sludge. 3. Double reaction mode: simultaneously supplies power to the first Ec electrode u〇, Two EC electrodes 130 and EO3 electrodes 160. This mode is used to rapidly eliminate organic pollutants, heavy metals, and microorganisms. The second figure shows a wastewater treatment system 20 including a wastewater treatment apparatus of the composite technology of the present invention. The water treatment system 20 is composed of a metal frame 260 and six waste water treatment devices. The six wastewater treatment devices 2 can be connected in series or in parallel on the metal frame 260. Each wastewater treatment device can be used. According to the treatment, any length of pipe such as 64 (l5em) can be made into any length such as 80 吋 (2m). In order to let the waste water flow through the waste water treatment device 2, one end of the mother branch wastewater treatment device Connect an upward τ word tube 21〇 as the water inlet and the other end to a downward T-shaped tube 250 as the water effluent. When 6 wastewater treatment units are finely scaly, the wastewater is in the total of the wastewater treatment unit 2GG In the stop (four), it is six times the time required for the waste water to be weighed into the waste water treatment device 200. Two waste water treatment devices must be connected in series, as shown in the 23 〇. The device 200 itself, the upward T-shaped tube 210, the T-shaped tube 230, the downward T-shaped tube 250, and the flange 22 are all returned, and polyvinyl chloride (PVQ 'polyethylene (PE), Polypropylene (PP) or fiber-reinforced _>). According to plastics; 'waste treatment equipment and other components The connection can make the hoof contact welding. Each wastewater treatment equipment i 2 (8) has two sets of composite electrodes (not shown), that is, the two-end device-group composite electrode of the composite technology processor 1 (the towel is not shown) The composite electrode is the collective name of the -EC electrode 11Q, the second EC electrode (10) and the % electrode 22 201130751 4 as described in the first figure. As shown in the second figure, there are three sets of terminals 20 on the flange 22 203 and 205. The terminals 1〇1 and 1〇3 are electrical terminals for connecting the ec electrode to an external DC or AC power source (not shown), and the terminal (10) is for connecting the positive and negative ends of the eo3 electrode with - The wire point of the DC power source (not shown) of the Bud... After the composite electrode (not shown) of the wastewater treatment device is locked in the designed position, the flange 220 can be fixed to the wastewater treatment device 200 by using the fixing member 240. . All _ water treatments must meet three requirements. · Short total processing time, low energy consumption and low sludge production. The third figure is a wastewater treatment process diagram of the county (four), and the wastewater treatment system using the wastewater treatment apparatus including the composite technology of the present invention can meet the above three requirements. As shown in the third figure, 'Step S301, wastewater, that is, industrial, commercial or domestic wastewater, is collected. The wastewater is checked at the step of reading to confirm whether the wastewater needs to be validated. If the wastewater contains excessive amounts of oil such as thick oil, scum, mucous membrane, > t floating particles, or the sinking hall, these floating objects or sinking halls must be completely removed, otherwise the composite electrode may be oily or sticky, and may be damaged. scrapped. The removal of the float or precipitate can be accomplished in step S3 〇 2a by means of a low-priced material such as sea sand, charcoal, hearth, grit or zeolite. The residue after adsorption or filtration treatment produces a solid in step 83〇21) which is to be disposed of properly and cannot be disposed of arbitrarily. If the step S3〇2a uses the hearthstone as the adsorbent, the saturated saturated hearth can be used for 4〇〇_5〇 (Λ: temperature for several hours, so that the hearthstone can be reused or become a paving stone. 23 201130751 . After removing the solid or precipitate, the filtrate proceeds to step S303 to check the color of the water to confirm whether decolorization is required. If the water color is opaque, indicating that the water t contains a high concentration of dye or pigment (mostly organic matter), it must be performed in step S304. Decolorization treatment. Although activated carbon can quickly and efficiently remove many dyes and pigments in step S3〇4, the amount of activated carbon is large, and the regeneration cost is low, so it is not suitable for the treatment of a large amount of wastewater. To reduce the processing cost of step S304 The composite technology of the present invention can be used for decolorization treatment. However, the material used for the EC electrode is the anode, and the correct operation parameters of the wastewater treatment device of the composite technology need to be confirmed by prior test. After decolorization treatment, after treatment, The wastewater that does not need to be decolored is also accepted in step S3〇5 - check 'confirm the chemical oxygen demand (COD), biochemical oxygen demand (BOD) of the water, - there is always Whether the carbon (T0C) and total suspended solids (TSS) values are up to standard. If the result of step S305 is affirmative, the wastewater can be advanced to step S3〇7 to check whether the total dissolved solids (TDS) value of the water reaches the standard. If the result of step S305 is negative, the wastewater must be subjected to step S306, processed by the composite technology wastewater treatment device, filtered at step S306a, step S306b produces a solid, φ filtrate is returned to step S3〇5 for confirmation, and step S306 is repeated. The composite technology cycle processing of step S306a, step S306b and step S305. Since the iron anode is continuously generated as long as the iron anode is continuously supplied to the EC electrode, the sludge is continuously generated in step S306, so step S3〇6a must be followed by filtration. To remove sludge, the sludge produced by the composite technology can be removed by a filter without consumables, such as a quartz sand filter cartridge, a ceramic filter, a pressure filter using a backwashable filter material, or a backwashable fiber ultrafilter. Step S306a The filtrate is subjected to a plurality of composite technology cycles until the COD, BOD, TOC, and TSS values of the water reach the standard. The residue of step S306a (main 24 201130) 751 S306b produces solids, which can be used as a general solid component for iron oxide). In the case of all waste water treatment technologies, the composite technology of the present invention deals with unscappedness, that is, Bhagha The composite technology cannot purify the wastewater to the desired conductivity or TDS value. Therefore, the wastewater treatment can include the removal of TDS, which can be recycled through the capacitive deionization technique (CDI) of step S3〇8 until the TM value of the water Finally, proceed to step S32G to generate a sum (4) water or reclaimed water. The processor for CDI removal of 7x>s is called a flow-through capacitor. The FTC and the capacitor H ride together, both of which are composed of parallel positive and negative electrodes, and the electrodes are energized (mainly DC voltage) to generate an electrostatic field. When the wastewater flows through the electrostatic field of the FTC, the ions in the water will be adsorbed by the opposite electrode (ie, electrostatically attracted). That is, the cation of the water towel will be on the bungee, and the anion will be adsorbed on the positive electrode to achieve deionization or TOS. The effect of the value reduction. In the third figure, the composite technique of the paving forest (4) is a loop processing between the transition S3Q6, the step S306a, the step S306b and the step S3〇5, and the CM operation is another loop between the step 307 and the step 3〇8, However, as long as the processing system as shown in the third figure contains a sufficient amount of the composite technology wastewater treatment device and the FTC, the wastewater can also flow from step S3〇1 to step S32, and once it becomes a legitimate discharge water or reclaimed water. In other words, a wastewater treatment system has passed through the Jingcheng meter, which is equipped with a wastewater treatment device, a filter and an FTC unit, which allows the chicken water to flow through the system-times to become the desired water quality and quantity. . The wastewater flows through the system. 25 201130751; In the process, only the wastewater treatment unit and the TM unit use more electric energy. However, the composite technology and CDI processing of the present invention are both fast and low-energy technologies. Therefore, the power consumption is limited. As for the production of sludge compared to chemical coagulation and raw scale, the invention of the invention is a low sludge technology and the CDI treatment is a sludge-free technology (FTC does not decompose water or 3 dyes, nor Any material f) is released, so the sludge production of the electric treatment system as shown in the third process is less than all commercial wastewater treatment technologies currently on the market. In fact, CDI treatment is non-destructive and can recover high-value disclaimers, such as the surface (Pt) 'Pd' gold (Au) and silver (Ag) in electroplating wastewater. - The waste nuclear field of each factory is set up in the secret labor plant and wastewater, and the treatment technology selected for the wastewater treatment site must be determined only for the nature and quantity of wastewater in a certain period. However, if the production line changes due to the demand for the order, such as 'changing the raw materials, formula, machine parameters or capacity, the discharged wastewater will exceed the established treatment capacity of the wastewater treatment plant, and the operation of the wastewater treatment plant will be shut down. Once the wastewater cannot be disposed of, the line will shut down due to the absence of waste water. This phenomenon often occurs when the selected water treatment technology can only handle a certain amount of water, or can only deal with specific pollutants. The decontamination ability of the composite technology of the invention is faster than the composition technology by the addition of EC technology and E〇3 technology, so that the composite technology can process more kinds of wastewater' and greater capacity. Coping with sudden changes in the quality and quantity of the same type of wastewater 0 The following examples respectively treat petrochemical wastewater with EC technology, EO3 technology and composite 26 201130751 technology of the present invention, showing that treating wastewater with the composite technology of the present invention is far superior to conventional EC Technology or E〇3 technology. A petrochemical wastewater filled with black viscous and foul-smelling floats needs to be disposed of to legally discharged water. As shown in the third figure, the floating matter of the wastewater is first removed by a ratio of 100 g of hearthstone to 300 ml of waste water to become a dark red light-transmitting liquid. Next, 1 liter of dark red waste water was taken and placed in a closed container with a simple EC electrode and an E〇3 electrode, respectively, for 1 hour (first treated with EC and then with E〇3). In addition, 1 liter of dark red waste water was taken, and the same simple EC electrode and E〇3 electrode were placed in the same closed container to become the composite technique of the present invention, and then treated for 1 hour. Table 2 lists the dimensions of the easy-to-EC and EO3 electrodes used between the tests and the respective operating voltages and operating currents for water treatment with EC technology and e〇3 technology. Table 2

Technical Anode Cathode Electrode Spacing Voltage Current Iron Rod Aluminum Rod EC Both are 65 mm 20 V 0.7 A 8mm ' Length 7cm E〇3 4 pieces 5 pieces Each piece area 40 cm2 2 mm 9V 5.6 A With EC technology and E〇 3 When the technology treats petrochemical wastewater separately, the power supplied to the EC electrode and the EO3 electrode is listed in Table 2. When the same Ec electrode and EO3 electrode are used to form the composite technology of the present invention to treat wastewater, the power originally applied to the EC electrode and the E〇3 electrode is still used, but the two types of electricity are supplied in the same manner as 27 201130751; Two power supplies). The wastewater treated by EC technology, E〇3 technology and composite technology (the three technologies are treated for 1 hour) is filtered by 0.5 μιη filter paper, and the c〇D of each filtrate and the transmittance at a wavelength of 800 nm are measured. , E〇3 technology and processing efficiency of composite technology. The results are shown in Table 3. · Table 3 Technical EC E〇3 e-E03/EC COD Reaction before 297,736 After reaction 297,588 297,380 94,084 (PPm) Removal rate (%) 0.05 0.07 68.4 Light transmission at 62.4 nm before 800 reaction (% 63.2 65.7 99.8 After the treatment of the entire petrochemical wastewater, the effluent is not treated for dilution, pH adjustment or other pretreatment, and the wastewater is directly treated by EC technology, EO3 technology and composite technology. The technology used in the test and the electrode area of the E〇3 technology are reported to be small, and the power applied by the Ec technology and the E〇3 technology is also only 14 W and 50·4 w. Therefore, as shown in Table 3, the amount of c〇D removed by EC technology and EO3 technology is negligible, and the treated wastewater remains dark red. However, when the same ruthenium electrode is combined with the E 〇 3 electrode to form a composite technique of the present invention, and the same power is used to treat the same amount of waste water, the removal of c 〇 D is greatly increased, and the wastewater is also clarified and odorless. ' 28 201130751

However, the above description is only for the implementation examples of the present disclosure, and the scope of the present invention cannot be limited thereto. That is, the equivalent changes and modifications made by a patent application scope should remain within the scope of the invention. 29 201130751 [Simple description of the drawings] The first figure shows a wastewater treatment apparatus of the composite technology of the present invention. The second figure shows a waste water treatment system comprising a wastewater treatment apparatus of the composite technology of the present invention. The third figure is a flow chart for the treatment of wastewater using the present invention. [Main component symbol description] 20 wastewater treatment system 102 hole 110 first EC electrode 130 second EC electrode 150 first group electrical terminal 170 second group electrical terminal 201 terminal 205 terminal 220 flange 240 fixing member 260 metal frame ίο wastewater treatment Device 101 flange 103 plastic fixed ring 120 first electrical contact 140 second electrical contact 160 E〇3 electrode 200 composite technology wastewater treatment device 203 terminal 210 upward T-tube 230 T-tube 250 downward T Word tube S301-S320 step

Claims (1)

201130751 «; Seven, the scope of application for patents: L A composite technology wastewater treatment device that passes a wastewater for treatment. The wastewater treatment device of the composite technology comprises: a tubular processor comprising at least one water inlet and one water outlet An electrocoagulation electrode is disposed in the composite technology processor, the electrocoagulation electrode includes at least an anode, a cathode and a power supply, the electrocoagulation electrode further comprising at least one electrical terminal connected to the anode of the electrocoagulation electrode The anode of the power supply is connected to the anode of the power supply, and the at least one electrical terminal is connected to the cathode of the electrocoagulation electrode and the cathode of the power supply; an electrolytic ozone electrode is placed in the composite technology processor, the 'electrolysis The ozone electrode comprises at least an anode, a cathode and a power supply. The electrolytic ozone electrode further comprises at least one electrical contact connecting the anode of the electrolytic ozone electrode to the positive pole of the power supply, and at least one electrical contact. a cathode connecting the electrolysis ozone electrode and a cathode of the power supply; and a %-flange And a plurality of holes for fixing to the tubular processor, the flange also fixing the electrocoagulation electrode and the electrolysis ozone 1: pole in the tubular processor. 2. The wastewater treatment apparatus of the composite technology according to claim i, wherein the anode and the cathode of the electrocoagulation electrode are selected from the group consisting of giant, iron, copper, strontium, silver, town, tin, zinc, yellow. At least one of copper, blue steel and stainless steel. 3. If applying for a supplement _ 1 item of Lai's compound Lin's wastewater treatment device', the anode of the 1 coagulated electrode will dissolve and release metal ions when the water towel applies a DC or a voltage. 31 201130751 A wastewater treatment apparatus of the composite technology described in the third embodiment of the invention, wherein the electrocoagulation electrode uses a DC or AC power supply, and the voltage of the power supply is 5V to ι00ν. The wastewater treatment device of the composite technology according to the second aspect of the patent scope of the invention, wherein the electrode of the electrocoagulation f-pole and the cathode include a plate shape, a spherical shape, a block shape, a granular shape, a rod shape, and a line. Shape, mesh, column or tube. The anode of the electrolytic method ozone electrode of the composite technology described in the patent scope of item i includes three kinds of metal-doped tin oxide thin ruthenium. The wastewater treatment device of the composite technology, wherein the anode of the f-solution ozone electrode and the cathode are respectively a porous metal plate. 8. A wastewater treatment device according to the composite technology described in the application The two kinds of doping metals include recording, silver, and recording. 9. The wastewater of the composite technology described in claim 6 of the patent application is in which the three metal doped tin oxide films are applied in water all the time. ·In the case of electric power, the water is decomposed to generate ozone. 10. The wastewater treatment device of the composite technology according to the first aspect of the invention, wherein the cathode of the electrolysis ozone electrode is made of a metal such as stainless steel, aluminum, nickel or titanium. u. If the number of cathodes of the electrocoagulation electrode is more than one, the number of cathodes of the electrolysis method is higher than that of the anode. —································································································· 13. A wastewater treatment system of the model comprising: a metal frame; a wastewater treatment device of the composite technology of any of the items 1 to 12, placed on the gold (four), each ^ The composite technology wastewater treatment device is connected at the end-to-end word tube, at the other end-to-end Τ word tube, each-composite technology: wastewater treatment device _ downward Τ word tube is connected to another The upward τ-shaped tube of the compound technology and the wastewater treatment device, each _ composite technology water treatment device is used for treating - waste water and producing - sludge; plural (four) enchanting 'scale complex touch the waste money device one pair - Correspondingly, the corresponding compound apology of the recording squad corresponds to the downward T-shaped official position of the county, which is used to pass the sludge; and the first-class over-type capacitor unit, including - anode, cathode, power supply, - Inlet and - water outlets, which are connected to the last-to-one τ-tube of the wastewater treatment plant of the composite technology, _ adsorbing a charged species in the wastewater.如 For example, if you apply for a patent, the U-thousands of the waste money management system, in which the waste water enters the wastewater treatment of the composite technology, the first through the - rough over the 'Linly slammed the Weng waste oblique - floating Object or a sinking temple. 15. The wastewater treatment system of claim 13, wherein the composite technology is used to remove the waste and the treatment, Θ iS] 33 201130751 to remove a dye or a pigment from the wastewater. 34