TWI657053B - Wastewater treatment method - Google Patents

Abstract

A wastewater treatment method includes an acid-base adjustment step, a mixing step, and a treatment step including a catalyst dissociation program and a coagulation filtration program. In the acid-base adjusting step, the pH value of the wastewater containing the contaminant is adjusted to 6 to 9, and the acid-base-adjusted wastewater is obtained. In the mixing step, the acid-base-adjusted wastewater, a plurality of transition metal oxidizing agents, a plurality of dissociating agents, and a plurality of stabilizers are mixed and reacted to obtain a mixed liquid. In the catalyst dissociation process, the mixed solution is brought into contact with a filter medium containing a catalyst to obtain a filtrate. In the coagulation filtration process, the filtrate is brought into contact with a filter medium containing a composite metal to obtain purified water. The wastewater treatment method has better treatment efficiency by using a plurality of transition metal oxidants, a plurality of dissociation agents, the catalyst-containing filter material, and the composite metal-containing filter material.

Description

Wastewater treatment method

The present invention relates to a water treatment method, and more particularly to a wastewater treatment method.

The Chinese Patent Publication No. 101696066 discloses a method for removing organic pollutants in water by intensive treatment of drinking water, comprising the steps of: adding an oxidizing chemical to the water to be treated, and reacting for 0.5 minutes to 10 minutes, and then using the modified particles. The filter material filter bed is filtered. The amount of the oxidizing chemical agent is from 0.2 mg to 5 mg based on the total amount of the water to be treated. The oxidizing chemical agent is, for example, potassium permanganate, hydrogen peroxide, sodium hypochlorite, iron chloride, iron sulfate, aluminum chloride, aluminum sulfate, magnesium chloride or magnesium sulfate. The modified particulate filter bed comprises a filter bed to filter the particulate filter. The filter bed filter particle filter is formed by modifying a substance such as quartz sand, zeolite or ceramsite with a metal oxide. The metal oxide is, for example, an iron oxide, a manganese oxide, or an aluminum oxide. The water treatment method of the patent can quickly and effectively remove pollutants in water, especially refractory organic pollutants which are difficult to be rapidly oxidized and removed by potassium permanganate, ozone and hydrogen peroxide.

Although the water treatment method of the patent can remove pollutants in water, it uses an oxidizing chemical to treat wastewater, and each oxidizing chemical has specificity for pollutants, so it cannot be effectively treated at the same time. There are many kinds of pollutants in water, it is difficult to rapidly oxidize different pollutants, and various pollutants are effectively and completely removed, so there is a problem that the treatment efficiency is not good.

Accordingly, it is an object of the present invention to provide a wastewater treatment method having high processing efficiency.

Thus, the wastewater treatment method of the present invention comprises: an acid-base adjustment step, a mixing step, and a treatment step.

In the acid-base adjusting step, the pH value of the wastewater containing the contaminant is adjusted to 6 to 9, and the acid-base-adjusted wastewater is obtained.

In the mixing step, the acid-base-adjusted wastewater, the plurality of transition metal oxidizing agents, the plurality of dissociating agents, and the plurality of stabilizers are mixed and reacted to obtain a mixed liquid, wherein the mixed liquid contains the acid-base Adjusted wastewater, such transition metal oxidizing agents, such dissociating agents, the stabilizers, and non-chelating transition metal species and coagulating materials formed by the reaction of the transition metal oxidizing agents with the dissociating agents.

The processing step includes a catalyst dissociation procedure and a coagulation filtering procedure. In the catalyst dissociation process, the mixed solution is contacted with a filter medium containing a catalyst to promote oxidation and dissociation of the contaminant in the acid-base-adjusted wastewater and adsorption and adsorption of the oxidation and dissociation reaction. The substance is formed and the filtrate is obtained. In the coagulation filtration process, the filtrate is brought into contact with a filter medium containing a composite metal to cause the filtrate to undergo a precipitation reaction and adsorb the substance formed by the precipitation reaction to obtain purified water.

The effect of the present invention is that the wastewater treatment method has better treatment efficiency by using a plurality of transition metal oxidants, a plurality of dissociation agents, the catalyst-containing filter material, and the composite metal-containing filter material.

The contents of the present invention will be described in detail below.

<acid-base adjustment step>

In the acid-base adjusting step, the pH value of the wastewater containing the contaminant is adjusted to 6 to 9 by using an acid-base reagent. The acid-base reagent is selected according to the pH value of the wastewater containing the pollutants, and the acid-base reagent for the wastewater treatment can be used.

The wastewater containing contaminants such as, but not limited to, domestic sewage, industrial wastewater, condensed circulating water that has been used in boilers, and circulating water that has been used for condensation, and the like. Contaminants in the wastewater containing contaminants such as, but not limited to, organic or inorganic substances and the like. The organic substance is, for example, potassium hydrogen phthalate or sodium 3-nitrobenzenesulfonate. The inorganic substance is, for example but not limited to, phosphate, hypophosphite, borate, chloride, fluoride, sulfate, nitrate, heavy metal ions, ammonia nitrogen, chloride, fluoride, sulfate, phosphide, Boride, nitro nitrogen, or metal. The metal is, for example, copper, zinc, nickel, iron, or chromium.

<mixing step>

Such transition metal oxidants are for example, but not limited to, transition metal oxides. The transition metal oxide is, for example but not limited to, manganese oxide, vanadium oxide, titanium oxide, or iron oxide. The manganese oxide is, for example but not limited to, manganese oxide (MnO), dimanganese trioxide (Mn ₂ O ₃ ), manganese dioxide (MnO ₂ ), potassium manganate (K ₂ MnO ₄ ), or potassium permanganate ( KMnO ₄ ) and the like. The vanadium oxides such as but not limited to a vanadium oxide (VO), vanadium trioxide (V ₂ O _3), vanadium dioxide (VO _2), or a vanadium pentoxide (V ₂ O ₅₎ and the like. The titanium oxide is, for example but not limited to, titanium oxide (TiO), titanium oxide (Ti ₂ O ₃ ), or titanium dioxide (TiO ₂ ). The iron oxides such as, but not limited to, ferrites comprising iron (III), iron (IV), iron (V), iron (VI), four valence oxyacid salts, ferrous oxide (FeO), trioxide Tetra-iron (Fe ₃ O ₄ ), or ferric oxide (Fe ₂ O ₃ ), and the like. The ferrite is, for example but not limited to, an iron (III) acid salt, an iron (IV) acid salt, an iron (V) acid salt, or an iron (VI) acid salt or the like. The ferrite is for example but not limited to sodium ferrate. Such dissociating agents are for example, but not limited to, mineral acid salts. The mineral acid salt is, for example but not limited to, a carbonate, an aluminate, a phosphate, a sulfate, or a chlorate. The carbonate is for example but not limited to sodium percarbonate. The sulfate salt is, for example but not limited to, potassium peroxymonosulfate or sodium persulfate. Preferably, the mineral acid salt is a combination of a carbonate and a sulfate. Such stabilizers are, for example but not limited to, inorganic salts that can act as electrolytes. The inorganic salt is, for example but not limited to, a citrate or an alkali metal chloride or the like. Preferably, the inorganic salt is a combination of the bismuth citrate and an alkali metal chloride. The citrate is for example but not limited to sodium citrate. The alkali metal chloride is, for example but not limited to, lithium chloride, sodium chloride, potassium chloride or the like. Based on cost and processing efficiency considerations, preferably, in the mixing step, the total amount of the transition metal oxidants, the total amount of the dissociating agents, and the total weight ratio of the stabilizers are in the range of 1:1. ~5:1~5.

The mixed solution comprises the acid-base-adjusted wastewater, the transition metal oxidizing agents, the dissociating agents, the stabilizers, and the plurality of types of redox reactions formed by the transition metal oxidizing agents and the dissociating agents. A non-chelating transition metal oxide and a coagulating substance for oxidizing a contaminant, wherein the non-chelating transition metal oxide has an oxidation number greater than the transition metal oxidant, and is capable of effectively oxidizing the contaminant. For example, the iron oxide containing ferrous iron, the oxide containing ferric iron or the iron oxide containing divalent and ferric iron in the transition metal oxidizing agent and the oxidizing agent in the dissociating agent are higher than the An inorganic acid salt (such as a sulfate) of an iron oxide is subjected to a redox reaction to form a ferrous iron-containing iron oxide as a non-chelating transition metal oxide, and the iron-containing iron formed is formed The oxide reacts with the inorganic acid having a lower oxidation number than the iron oxide containing the ferrous iron in the dissociating agent to form a ferric oxide-containing iron oxide as a coagulating substance. The transition metal oxidizing agents are used to oxidize contaminants, the dissociating agents are used to dissociate or decompose the contaminants, and the stabilizers are used to stabilize the oxidation potential or pH of the mixture to make the non-chelating The compliant transition metal oxide is stable.

In addition, the non-chelating transition metal oxides, in combination with the transition metal oxidants and the dissociating agents, are capable of producing stable, highly active oxidative radicals for contamination in the wastewater containing contaminants. The substance, especially for organic substances that are difficult to degrade, undergoes an advanced oxidation reaction and is converted into a substance that is low in toxicity or non-toxic. Under the progress of such an advanced oxidation reaction, it is not necessary to go through a chemical coagulation process, and the amount of sludge generated by the chemical coagulation process can be reduced.

<Processing steps>

[catalytic dissociation procedure]

The catalyst-containing filter medium is used to promote the oxidation and dissociation reaction and adsorb the substances formed by the oxidation and dissociation reaction (for example, organic ions, no base ions, or metal ions, etc.) to obtain a filtrate. The catalyst-containing filter medium has a specific surface area of at least 300 m ² /g. The catalyst-containing filter material includes a filter substrate and a catalyst disposed on the filter substrate. The filter matrix is, for example but not limited to, a natural adsorbent or a synthetic adsorbent or the like. The filter substrate is, for example but not limited to, activated carbon, lignite, modified lignite, zeolite or metal oxide, and the like. The catalyst is, for example but not limited to, metal platinum, metal palladium, zinc oxide, cobalt oxide, or molybdenum oxide. The oxidation and dissociation reaction can be accelerated by the catalyst in the catalyst-containing filter medium, so that the contaminants in the contaminant-containing wastewater are oxidized or decomposed. Further, the filter substrate in the catalyst-containing filter medium can adsorb the substances formed by the oxidation and dissociation reaction to effectively remove unnecessary substances.

[Coagulation filter program]

The composite metal-containing filter medium is used to promote the precipitation reaction and adsorb the substance formed by the precipitation reaction to obtain purified water. The composite metal-containing filter material has a specific surface area of at least 2,000 m ² /g. The composite metal-containing filter material includes a filter substrate and a composite metal disposed on the filter substrate. The filter matrix is, for example but not limited to, a natural adsorbent or a synthetic adsorbent or the like. The filter substrate is, for example but not limited to, activated carbon, lignite, modified lignite, zeolite, or metal oxide. The composite metal is, for example but not limited to, an alloy comprising at least two of iron, aluminum, titanium, copper, and zinc. The precipitation reaction can be accelerated by the composite metal-containing filter material to chemically precipitate the coagulating substance in the filtrate and the substance formed by the oxidation and dissociation reaction. Further, the water in the filtrate can be subjected to an electrochemical redox reaction with the composite metal-containing filter material to generate a hydroxide, and can be subjected to a precipitation reaction with the substance formed by the oxidation and dissociation reaction in the filtrate. Further, the substance formed by the precipitation reaction can be adsorbed through the filter substrate in the composite metal-containing filter medium.

The wastewater treatment method of the present invention further comprises a filtration step after the acid-base adjustment step and before the mixing step.

<Filter step>

In the filtering step, the wastewater subjected to the acid-base adjusting step is subjected to a filtration treatment to remove suspended matter. In a variation of this embodiment, the filtering process may not be required under the load that does not cause the processing step.

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

Example 1

The wastewater treatment method comprises an acid-base adjustment step, a filtration step, a mixing step, and a treatment step.

The acid-base adjustment step: 850 mg of potassium hydrogen phthalate as a pollutant is placed in a 1 liter volumetric flask and water is added to the 1 liter mark of the volume bottle to form a pollutant concentration of 1,000 ppm. Waste water was used to simulate industrial wastewater containing COD at a concentration of 1,000 ppm. Then, the pH value was adjusted to 6, and an acid-base adjusted wastewater was obtained.

The filtering step: filtering the acid-base adjusted wastewater to remove the suspended matter to obtain filtered wastewater.

The mixing step: mixing the filtered wastewater, the oxidizing agent component, the dissociating agent component and the stabilizer component at 15 ° C to 35 ° C for 10 minutes to obtain a mixed solution, wherein the oxidizing agent component and the dissociating agent The weight ratio of the component to the stabilizer component is 1:1:1. The oxidant component comprises manganese dioxide, ferrite and ferric oxide, and the molar ratio of the manganese dioxide, the sodium ferrate and the ferric oxide is 5:5:1. The dissociator component comprises potassium peroxymonosulfate, the sodium persulfate and sodium percarbonate, and the molar ratio of the potassium peroxymonosulfate, the sodium persulfate and the sodium percarbonate is 1:1:1. . The stabilizer component comprises sodium citrate and potassium chloride, and the molar ratio of the sodium citrate and the potassium chloride is 2:1.

The processing step includes a catalyst dissociation procedure and a coagulation filtering procedure. In the catalyst dissociation procedure, the mixed solution was contacted with a filter medium containing a catalyst at a temperature of 15 ° C to 35 ° C for 3 minutes to obtain a filtrate. The catalyst-containing filter medium includes alumina as a filter matrix and molybdenum oxide as a catalyst. In the coagulation filtration process, the filtrate was contacted with a filter medium containing a composite metal at a temperature of 15 ° C to 35 ° C for 3 minutes to obtain purified water. The composite metal-containing filter material includes modified lignite as a filter matrix, and iron and titanium oxynitride as a composite metal.

Examples 2 to 19 and Comparative Examples 1 to 5

Examples 2 to 19 and Comparative Examples 1 to 5 were carried out in the same manner as in Example 1, except for the type and concentration of the contaminant, the ratio of each component in the mixing step, or the acid in the acid-base adjusting step. Base values, see Tables 1 to 4.

Comparative Example 6

Comparative Example 6 was carried out in the same manner as in Example 5, except that in Comparative Example 6, the processing steps of Example 5 were not carried out, and Table 4 was referred to.

Comparative Example 7

Comparative Example 7 was carried out in the same manner as in Example 5, except that in Comparative Example 7, the coagulation treatment procedure in the processing procedure of Example 5 was not performed, and Table 4 was referred to.

Comparative Example 8

The wastewater treatment method comprises an acid-base adjustment step, a filtration step, a mixing step, and a treatment step.

The acid-base adjustment step: mixing water with potassium hydrogen phthalate as a pollutant to simulate industrial wastewater containing COD at a concentration of 1,000 ppm, and then adjusting the pH to 3.5 to obtain acid-base adjustment Waste water.

The filtering step: filtering the acid-base adjusted wastewater to remove the suspended matter to obtain filtered wastewater.

The mixing step: mixing the filtered wastewater, 250 mg of hydrogen peroxide and 500 mg of ferrous sulfate (FeSO ₄ ) at a temperature of 25 ° C for 30 minutes, and adjusting the pH when the yellow-red turbidity is exhibited To 7 to 8, then, add 100 mg of polyaluminium chloride (PAC as a coagulant) and 2 mg of polyacrylamide (PAM as a flocculant), followed by static Set and remove the supernatant after standing.

The processing step includes a first filter and a second filter. In the first filtration procedure, the supernatant was contacted with a filter medium containing a catalyst at a temperature of 15 ° C to 35 ° C for 3 minutes to obtain a filtrate. The catalyst-containing filter medium includes alumina as a filter matrix and molybdenum oxide as a catalyst. In the second filtration step, the filtrate is contacted with a filter medium containing a composite metal at a temperature of 15 ° C to 35 ° C for 3 minutes to obtain purified water. The composite metal-containing filter material includes modified lignite as a filter matrix, iron as a composite metal, and titanium oxynitride.

Comparative Example 9

Comparative Example 9 was carried out in the same manner as in Comparative Example 8, except for the main processing steps. In Comparative Example 9, the processing procedure of Comparative Example 8 was not performed, and Table 4 is referred to.

The test methods for the pollutants of the examples and the comparative examples are based on the detection method in the Environmental Inspection Institute of the Environmental Protection Agency of the Republic of China. The detection method is as follows: the method for detecting the chemical oxygen demand in water of the number W515.54A - potassium dichromate reflux method, the method for detecting ammonia nitrogen in water numbered W448.51B - the indophenol colorimetric method, the water numbered W427.53B Phosphorus detection method - spectrophotometer / vitamin C method, number W306.55A water silver, cadmium, chromium, copper, iron, manganese, nickel, lead and zinc detection method - flame atomic absorption spectrometry, number W404. 53A method for detecting boron in water - curcumin colorimetric method, method for detecting chloride salt in water with the number W407.51C - silver nitrate titration method, method for detecting fluoride salt in water numbered W413.52A - fluorine selective electrode method, number W430 .51C Water Sulfate Detection Method - Turbidity Method, and Water Nitrate Nitrogen Test Method No. W419.51A - Spectrophotometer Method. Among them, the detection method of the sodium phosphite is the water phosphorus detection method numbered W427.53B.

Table 1      Example 1 2 3 4 5 6 Contaminant Potassium hydrogen phthalate COD concentration (ppm) 1,000 Acid-base adjustment step pH 6 9 6 6 6 6 Mixing step Transition metal oxidant species Manganese dioxide: Sodium ferrate: Trioxide Iron = 5:5:1 (mole ratio) Total amount (mg) 1 Dissociation agent type potassium peroxymonosulfate: sodium persulfate: sodium percarbonate = 1:1:1 (mole ratio) total amount (mg 1 1 1 3 5 10 Stabilizer type sodium citrate: potassium chloride = 2:1 (mole ratio) total amount (mg) 1 1 1 3 5 10 The oxidizing agent component, the dissociating agent component and the stability The weight ratio of the components is 1:1:1 1:1:1 1:3:3 1:5:5 1:10:10 Treatment step Catalyst dissociation procedure Catalyst filter media Molybdenum oxide filter matrix alumina Coagulation filtration program containing composite metal filter material composite metal iron and titanium oxide filter matrix modified brown coal evaluation project COD concentration in purified water (ppm) 25 43 156 73 25 21 COD removal rate (%) 97.5 95.7 84.4 92.7 97.5 97.9

Table 2      Example 7 8 9 10 11 Contaminant Metal Copper Metal Zinc Metal Nickel Metal Ferric Metal Chromium Contaminant Concentration (ppm) 500 Acid-base Adjustment Step pH 6 6 6 6 6 Mixing Step Transition Metal Oxidant Type Manganese Dioxide: Sodium Ferrate: Ferric oxide = 5:5:1 (mole ratio) Total amount (mg) 1 Dissociation agent type potassium peroxymonosulfate: sodium persulfate: sodium percarbonate = 1:1:1 (mole ratio) Dosage (mg) 5 Stabilizer type Sodium citrate: Potassium chloride = 2:1 (mole ratio) Total amount (mg) 5 Weight ratio of the oxidizing agent component, the dissociating agent component and the stabilizer component :5:5 Process Step Catalyst Dissociation Procedure Containing Catalyst Filter Media Catalyst Molybdenum Oxide Filter Matrix Alumina Coagulating Filtration Program Containing Composite Metal Filter Media Composite Metal Iron and Titanium Dioxide Filter Matrix Modified Brown Coal Evaluation Project Purification Water Contaminant concentration (×10-2ppm) 19.3 17.1 8.9 1.2 108 Contaminant removal rate (%) 99.961 99.966 99.982 99.998 99.784

table 3      Example 12 13 14 15 16 17 18 19 Source of pollution ammonium chloride potassium hydrogen phosphate boric acid sodium fluoride sodium sulfate sodium hypophosphite sodium nitrate pollutant ammonia nitrogen phosphorus boron chloride ion fluoride ion sulfate phosphorus nitrate concentration Ppm) 1,000 Acid-base adjustment step pH 6 Mixing step Transition metal oxidant type Manganese dioxide: Sodium ferrate: Ferric oxide = 5:5:1 (Mo Erbi) Total amount (mg) 1 Dissociation type peroxyus acid Potassium hydrogenate: sodium persulfate: sodium percarbonate = 1:1:1 (mole ratio) total amount (mg) 5 stabilizer type sodium citrate: potassium chloride = 2:1 (mole ratio) total amount ( Mg) 5 The oxidizer component, the dissociator component and the stabilizer component weight ratio 1:5:5 Treatment step Catalytic dissociation procedure Catalyst-containing filter catalyst Molybdenum oxide filter matrix Alumina coagulating filter program Concentration of pollutants in purified water (ppm) with composite metal-containing filter material composite metal iron and titanium oxide filter matrix modified lignite evaluation project 8.4 29.2 7.21 106.35 19.8 324.6 181 53.5 Contaminant removal rate (%) 99.2 97.1 99.3 89.7 97.9 67.5 81.9 94.7

Table 4      Comparative Example 1 2 3 4 5 6 7 8 9 Contaminant Potassium hydrogen phthalate COD concentration (ppm) 1000 Acid-base adjustment step pH 11 4 6 6 6 6 6 3.5 3.5 Mixing step Transition metal oxidant type Manganese dioxide: High-speed rail Sodium: Ferric oxide = 5:5:1 (mole ratio) H2O2 H2O2 Total amount (mg) 1 1 1 1 1 1 1 250 250 Dissociation type is the same as Table 1 - Same as Table 1 - Same as Table 1 -- -- Total dosage (mg) 1 1 0 5 0 5 5 -- -- The type of stabilizer is the same as Table 1 -- -- Same as Table 1 -- -- Total dosage (mg) 1 1 0 0 5 5 5 - - the weight ratio of the oxidizing agent component, the dissociating agent component and the stabilizer component is 1:1:1 1:1:1 - 1:5:0 1:0:5 1:5:5 1 :5:5 -- -- Treatment step: Catalyst-containing filter material Molybdenum oxide -- Molybdenum oxide -- Molybdenum oxide -- Filter base alumina -- Alumina -- Alumina -- Composite material containing composite metal Iron and Titanium Dioxide - Iron and Titanium Dioxide - Iron and Titanium Dioxide - Filtered Matrix Modified Brown Coal - Modified Brown Coal --- Lignite Quality - Evaluation items purified water COD concentration (ppm) 640 390 729 54 352 371 126 213 427 COD removal efficiency (%) 36.0 61.0 27.1 94.6 64.8 62.8 87.4 78.7 57.3

In summary, by using a plurality of oxidizing agents, a plurality of dissociating agents, the catalyst-containing filter material, and the composite metal-containing filter material, the wastewater treatment method of the present invention has better treatment efficiency, so that the object of the present invention can be achieved. .

However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the simple equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still Within the scope of the invention patent.

Claims (9)

A wastewater treatment method comprising: an acid-base adjustment step of adjusting a pH value of a wastewater containing pollutants to 6 to 9 to obtain an acid-base adjusted wastewater; and a mixing step of the acid-base adjusted wastewater a plurality of transition metal oxidizing agents, a plurality of dissociating agents, and a plurality of stabilizers are mixed and reacted to obtain a mixed liquid, wherein the mixed liquid comprises the acid-base adjusted wastewater, a transition metal oxidizing agent, a dissociating agent, and a stabilizer. And a non-chelating transition metal substance and a coagulating substance formed by reacting the transition metal oxidizing agent with the dissociating agent; and a treating step comprising a catalyst dissociation process, contacting the mixed solution with the filter medium containing the catalyst, The filtrate is obtained by causing the acid-base-adjusted waste water to undergo oxidation and dissociation reaction with the mixed solution and adsorbing the substance formed by the oxidation and dissociation reaction; a coagulation filtration program, the filtrate is The filter medium containing the composite metal is contacted to cause the filtrate to undergo a precipitation reaction and adsorb the substance formed by the precipitation reaction to obtain purified water. . The wastewater treatment method according to claim 1, wherein the total amount of the transition metal oxidizing agents, the total amount of the dissociating agents, and the total weight ratio of the stabilizers are in the range of 1:1 to 5:1. 5. The wastewater treatment method according to claim 1, wherein in the catalyst dissociation process, the catalyst-containing filter medium comprises a filter substrate and a catalyst disposed on the filter substrate. The wastewater treatment method according to claim 3, wherein the filter substrate is selected from the group consisting of activated carbon, lignite, modified lignite, zeolite, or metal oxide, and the catalyst is selected from the group consisting of metal platinum, metal palladium, and zinc oxide. a substance, a cobalt oxide, or a molybdenum oxide. The wastewater treatment method according to claim 1, wherein in the coagulation filtration process, the composite metal-containing filter material comprises a filter substrate and a composite metal disposed on the filter substrate. The wastewater treatment method according to claim 5, wherein the filtration substrate is selected from the group consisting of activated carbon, lignite, modified lignite, zeolite, or metal oxide, and the composite metal is selected from the group consisting of iron, aluminum, titanium, and copper. And an alloy of at least two of zinc. The wastewater treatment method according to claim 1, further comprising a filtration step after the acid-base adjustment step and before the mixing step. The wastewater treatment method according to claim 1, wherein in the mixing step, the transition metal oxidant is a transition metal oxide, and the transition metal oxide is selected from the group consisting of manganese oxide, vanadium oxide, and titanium oxide. , or iron oxides. The wastewater treatment method according to claim 8, wherein the manganese oxide is selected from the group consisting of manganese monoxide, manganese trioxide, manganese dioxide, potassium manganate, or potassium permanganate; the vanadium oxide is selected from the group consisting of Vanadium oxide, vanadium trioxide, vanadium dioxide, or vanadium pentoxide; the titanium oxide is selected from the group consisting of titanium oxide, titanium oxide, or titanium dioxide; the iron oxide is selected from the group consisting of ferrite, oxidation Ferrous, ferric oxide, or ferric oxide.