CN107140716A - A kind of Electrochemical adsorption combination process handles the equipment and processing method of waste water from dyestuff - Google Patents

Abstract

The application provides an electrochemical-adsorption composite process for treating dye wastewater and a treatment method. The main electrode plate of the reactor is composed of a graphite plate cathode loaded with metal copper and palladium and a titanium anode coated with ruthenium, titanium and tin. Anhydrous NaCl and powdered activated carbon are filled between them. The present invention is a kind of high current conductivity, simple operation, and high-efficiency removal of COD and color in dye wastewater. This process can effectively degrade the chroma in dye wastewater, and It is used in the treatment of medium and low concentration dye wastewater.

Description

An electrochemical-adsorption composite process for treating dye wastewater and its treatment method

technical field

The invention belongs to the technical field of sewage treatment, and in particular relates to equipment and a treatment method for treating dye wastewater by an electrochemical-adsorption composite process.

Background technique

With the rapid development of my country's dye production and printing and dyeing industry, the discharge of dye industry wastewater has also increased sharply. According to the data provided by relevant departments, about 1.8 million cubic meters of dye wastewater is discharged into the environment every year in my country. Dye wastewater has high organic content, large chroma, complex components, and a wide range of pH changes. Due to the variety of dyes produced and the development towards anti-photolysis, anti-oxidation, and anti-biological oxidation, the treatment of dye wastewater has become more difficult. Dye wastewater contains a large amount of organic pollutants, which will consume dissolved oxygen in the water body after being discharged into the water body, destroy the balance of the water body ecosystem, and seriously endanger the survival of fish and other aquatic organisms. In view of the above points, the treatment of dye wastewater has become the focus of research at home and abroad.

Traditional methods for treating dye wastewater include physical, chemical, and biological methods. These methods have certain effects on the treatment of dye wastewater, but also have shortcomings.

In order to find a more effective and economical method to fundamentally solve the problem of environmental pollution caused by dye wastewater, people have tried various treatment methods for dye wastewater by using different methods and technologies. Among them, the electrochemical water treatment technology has attracted many researchers at home and abroad. The electrochemical sewage treatment technology has the advantages of simple equipment, convenient operation, small secondary pollution and wide application range.

For this reason, in consideration of the superiority and development trend of the composite process, the present invention takes the alizarin S simulated dye wastewater as the research object, and adopts a treatment method combining electrochemical technology and adsorption technology to improve the electrochemical-adsorption synergistic effect. The composite process for treating dye wastewater has been deeply studied.

Contents of the invention

Technical problem to be solved: This application mainly proposes an electrochemical-adsorption composite process for treating dye wastewater and a treatment method to solve the problem that carbon nitride is a powder material in the prior art, which needs to be stirred during use, and after use Difficult to recycle and other technical issues.

Technical solution: An electrochemical-adsorption composite process for treating dye wastewater, which consists of a DC stabilized power supply, a graphite plate cathode loaded with metal copper and palladium, a ruthenium tin-coated titanium anode, a magnetic stirrer, a waste water storage tank, and a magnetic stirrer , peristaltic pump, overflow port, water inlet valve, water outlet valve and powdered activated carbon, the graphite plate cathode and ruthenium-tin coated titanium anode loaded with metal copper and palladium are respectively arranged in the electrochemistry-adsorption composite process to treat dye wastewater At both ends of the cell body of the equipment, the cathode of the graphite plate loaded with metal copper and palladium is connected to the negative pole of the DC power supply through a wire, the titanium anode coated with ruthenium tin is connected to the positive pole of the DC power supply through a wire, and the cathode of the graphite plate loaded with metal copper and palladium is connected to the positive pole of the DC power supply through a wire. Powdered activated carbon and anhydrous sodium chloride are filled between the ruthenium-tin coated titanium anodes, and the overflow port is set under the top cover of the cell body, which is movably connected with the cell body, and a set of Holes are opened, a magnetic stirrer is provided at the bottom of the pool body, a magnetic stirrer is provided in the pool body, the water inlet valve and the water outlet valve are respectively set on both sides of the pool body, and the waste water storage tank is connected with the water inlet valve through a peristaltic pump. After the reaction in the pool is complete, it will flow out from the outlet valve. When there is too much waste water in the pool, the excess waste water will overflow from the overflow port.

As a preferred technical solution of the present invention: the graphite plate cathode loaded with metal copper and palladium is obtained by the ethylene glycol reduction method, and the graphite plate electrode is taken, and the surface is polished by sandpaper to be smooth and smooth, and then soaked in NaOH solution and hydrochloric acid solution successively, Rinse and dry again to prepare a preparatory graphite plate electrode, place the prepared preparatory graphite plate electrode in ethylene glycol solution, ultrasonicate for 1h; weigh 76mg of PdCl ₂ , 72mg of CuCl ₂ ^. 2H ₂ O and 240mg of citric acid Put sodium in a 250mL round bottom flask, add 50mL ethylene glycol EG, stir at room temperature for 1h, then place the graphite plate electrode soaked in ethylene glycol in it, and adjust the reaction mixture with 5wt% KOH/EG solution pH to 9.5-0-10.5, continue to stir at room temperature for 30min, then place the reaction mixture in an oil bath, react at 160°C for 6h, after the reaction, take out the graphite plate electrode, rinse with deionized water, vacuum After drying, a graphite plate cathode loaded with metal copper and palladium is obtained.

As a preferred technical solution of the present invention: the pool body of the equipment for treating dye wastewater by the electrochemical-adsorption composite process is a cuboid with a size of 15cm×10cm×12cm.

As a preferred technical solution of the present invention: the graphite plate cathode loaded with metal copper palladium and the ruthenium-tin coated titanium anode both have a size of 10cm×8cm×0.5cm, and the distance between the two electrodes is 3.0-5.0cm.

As a preferred technical solution of the present invention: the particle size of the powdered activated carbon is 0.15-2.00mm.

As a preferred technical solution of the present invention: the overflow port is 1-5 cm lower than the top of the pool body.

A treatment method for the equipment of the described electrochemical-adsorption composite process for treating dye wastewater, comprising the steps of:

Step 1: Boil the powdered activated carbon in distilled water for 2-4 hours, then rinse with distilled water for 5-10 minutes, dry at 120°C for 24-48 hours after rinsing, take it out, and put it into a graphite plate cathode loaded with metal copper and palladium and ruthenium Between tin-coated titanium anodes, add 20g/L anhydrous sodium chloride at the same time;

Step 2: Turn on the DC power supply, adjust the voltage range to ≤9V, control the intermittent reaction time to ≤30min, open the water inlet valve, turn on the peristaltic pump, and the dye wastewater enters the reactor from the wastewater storage tank. The dye wastewater uses alizarin from simulated wastewater S dye wastewater, initial concentration 200-1000mg/L, COD=600mg/L, chroma 4-6;

The third step, water outlet detection: after the reaction, close the water inlet valve, open the water outlet valve, and the treated dye wastewater flows out from the water outlet valve. After testing, the COD and chroma in the dye wastewater meet the "Comprehensive Wastewater Discharge Standard" (GB8978-1996) can be discharged after

Step 4: When the concentration of dye wastewater increases, resulting in an increase in the concentration of effluent after treatment, which does not meet the "Comprehensive Discharge Standard for Sewage" (GB8978-1996), close the water inlet valve and peristaltic pump, and readjust the voltage and reaction interval time. Return to the normal processing flow until the effluent reaches the standard.

As a preferred technical solution of the present invention: the adjustment method of the four-step readjustment voltage and reaction intermittent time is to increase the voltage 1V, 3V, 5V, 7V and 9V in turn, and adjust the reaction intermittent time 5min, 10min, 15min, 20min , 25min and 30min.

Beneficial effects: Compared with the prior art, the equipment and treatment method of an electrochemical-adsorption composite process for treating dye wastewater described in this application have the following technical effects:

1. To improve the traditional three-dimensional electrode, by introducing a new electrode pair, a graphite plate loaded with metal copper palladium and a ruthenium-tin-titanium anode, powdered activated carbon and anhydrous NaCl are added between the electrodes as electrolytes to form a current efficiency High, strong oxidation capacity, low energy consumption, good COD removal and decolorization effects, easy operation, wide application range of dye wastewater treatment devices and processes, and has positive significance for the treatment of dye wastewater;

2. A new electrode pair is adopted, with copper palladium supported on graphite plate as cathode and titanium anode coated with ruthenium tin. Then it forms a three-dimensional electrode reactor with powdered activated carbon in the reactor, which greatly increases the specific surface area of the electrode and enhances the electrolysis effect;

3. The electrochemical-adsorption composite process is adopted, and the treatment process is mainly based on electrochemistry and supplemented by adsorption method. The two are skillfully combined to realize time saving and energy saving, and greatly improve the effect of treating dye wastewater;

4. Powdered activated carbon is used as a filler, which can be used as both an electrolyte and an adsorbent. The top cover of the reactor can be uncovered, and holes are opened on the top cover, which is convenient for the assembly of the reactor and the replacement of the filler, and facilitates the discharge of gas during the reaction process;

5. Using a series of electrochemical reactions that occur in the electrolyte sodium chloride, intermediates such as HClO, OCl-, HClO3 with strong oxidative properties can be generated to oxidize and degrade organic matter, so that the chroma removal effect of dye wastewater is very good ;

6. Connect the power supply at both ends of the reactor, and the activated carbon becomes charged particles in the electric field, which can act as a carrier for electrochemical redox. The organic refractory molecules complete the process of gaining and losing charges on this carrier, and break and decompose into small molecules. It can be directly oxidized and decomposed into H ₂ O and CO ₂ . The powdered activated carbon acts as the third electrode in the electrochemical-adsorption composite process, thereby greatly increasing the specific surface area of the electrode and enhancing the electrolysis effect;

7. After treatment of different concentrations of raw wastewater (200mg/L, 600mg/L, 1000mg/L), the removal rate of COD and chroma in the wastewater reached 85%~90%, indicating that the process is effective for dye wastewater The processing effect is very efficient.

Description of drawings:

Fig. 1 is a structural schematic diagram of a reactor for treating dye wastewater by the electrochemical-adsorption composite process of the present application.

Explanation of reference signs: 1. DC stabilized voltage power supply, 2. Graphite plate cathode loaded with metal copper and palladium, 3. Ruthenium-tin-coated titanium anode, 4. Magnetic stirrer, 5. Wastewater storage tank, 6. Magnetic stirrer, 7. Peristaltic pump, 8. Overflow port, 9-1 water outlet valve, 9-2 water inlet valve, 10. Powdered activated carbon.

detailed description

The specific embodiment of the present invention will be described in further detail below in conjunction with the accompanying drawings: the ruthenium-tin-coated titanium anode in the embodiment was purchased from Shaanxi Baoji CNMC Special Metals Co., Ltd.

Example 1

As shown in Figure 1, an electrochemical-adsorption composite process is used to treat dye wastewater. It consists of a DC stabilized power supply 1, a graphite plate cathode 2 loaded with metal copper and palladium, a ruthenium-tin-coated titanium anode 3, a magnetic stirrer 4, Wastewater storage tank 5, magnetic stirrer 6, peristaltic pump 7, overflow port 8, water outlet valve 9-1, water inlet valve 9-2 and powdered activated carbon 10 are composed, and the graphite plate cathode 2 of described loading metal copper palladium is made of Manufactured by ethylene glycol reduction method, take the graphite plate electrode, sand the surface smooth and flat, put it into NaOH solution and hydrochloric acid solution for soaking in turn, then rinse and dry to prepare the prepared graphite plate electrode, place the prepared prepared graphite plate electrode on In ethylene glycol solution, sonicate for 1 h; weigh 76 mg of PdCl ₂ , 72 mg of CuCl ₂ ^. 2H ₂ O and 240 mg of sodium citrate in a 250 mL round bottom flask, add 50 mL of ethylene glycol EG, and stir at room temperature for 1 h , then place the above-mentioned graphite plate electrode soaked in ethylene glycol in it, adjust the pH of the reaction mixture to 9.5-0-10.5 with 5wt% KOH/EG solution, continue to stir at room temperature for 30min, and then put the reaction mixture Put it in an oil bath and react at 160°C for 6 hours. After the reaction, take out the graphite plate electrode, rinse it with deionized water, and dry it in vacuum to obtain a graphite plate cathode loaded with metal copper and palladium. Electrochemical-adsorption composite process is used to treat dye wastewater The pool body of the equipment is a cuboid with a size of 15cm×10cm×12cm. The graphite plate cathode 2 and the ruthenium-tin-coated titanium anode 3 loaded with metal copper and palladium are respectively arranged in the equipment of the electrochemical-adsorption composite process for treating dye wastewater. At both ends of the cell body, the graphite plate cathode 2 loaded with metal copper palladium and the ruthenium tin-coated titanium anode 3 both have a size of 10 cm × 8 cm × 0.5 cm, and the distance between the two electrodes is 3.0 cm. The graphite plate cathode 2 loaded with metal copper palladium Connect to the negative pole of the DC stabilized voltage power supply 1 through a wire, connect the ruthenium-tin-coated titanium anode 3 to the positive pole of the DC stabilized voltage power supply 1 through a wire, and fill the powder between the graphite plate cathode 2 loaded with metal copper and palladium and the ruthenium-tin-coated titanium anode 3 activated carbon 10 and anhydrous sodium chloride, the powdered activated carbon particles 10 have a particle size of 0.15 mm, and the overflow port 8 is located under the top cover of the pool body. The overflow port 8 is 1 cm lower than the top of the pool body, the top cover of the pool body is flexibly connected with the pool body, a set of openings are arranged on the top cover, a magnetic stirrer 4 is provided at the bottom of the pool body, and a magnetic stirrer 6 is provided in the pool body , the outlet valve and the inlet valve 9-2 are arranged on both sides of the pool body respectively, and the waste water storage tank 5 is connected to the inlet valve 9-2 through the peristaltic pump 7. -1 flows out, when there is too much waste water in the pool, the too much waste water overflows from the overflow port 8.

The processing methods specifically include the following:

Step 1: Boil powdered activated carbon 10 in distilled water for 2 hours, then rinse with distilled water for 5 minutes to remove water-soluble and volatile substances, dry it at 120°C for 24 hours after rinsing, take it out, and put it into the loaded metal copper palladium Between the graphite plate cathode 2 and the ruthenium-tin-coated titanium anode 3, the distance between the two electrode plates is 3.0 cm, and 20 g/L NaCl is added between the electrode plates.

Step 2: Turn on the DC power supply 1, adjust the voltage to 5V, control the intermittent reaction time for 5 minutes, open the water inlet valve 9-2, and turn on the peristaltic pump 7. The dye wastewater enters the reactor from the wastewater storage tank 5, and the dye wastewater is simulated wastewater. Alizarin S dye wastewater, initial concentration 200mg/L, COD=600mg/L, chroma 4.

The third step, water outlet detection: after the reaction, close the water inlet valve 9-2, open the water outlet valve 9-1, the treated dye wastewater flows out from the water outlet valve 9-1, and detect the COD and chroma in the dye wastewater after treatment, After 15 minutes of reaction, the COD and chroma removal rates of the treated raw wastewater reached 98% and 90%, respectively, forming a clear contrast with the raw wastewater.

Step 4: When the concentration of dye wastewater increases, causing the treated effluent to fail to meet the "Integrated Wastewater Discharge Standard" (GB8978-1996), close the water inlet valve 9-2 and peristaltic pump 7, and adjust the voltage and reaction interval time , until the water reaches the standard and the normal processing flow is restored, the adjustment method of re-adjusting the voltage and the intermittent reaction time is to increase the voltage 1V, 3V, 5V, 7V and 9V in turn, and adjust the intermittent reaction time to 5min, 10min, 15min, 20min, 25min and 30min .

Example 2

As shown in Figure 1, an electrochemical-adsorption composite process is used to treat dye wastewater. It consists of a DC stabilized power supply 1, a graphite plate cathode 2 loaded with metal copper and palladium, a ruthenium-tin-coated titanium anode 3, a magnetic stirrer 4, Wastewater storage tank 5, magnetic stirrer 6, peristaltic pump 7, overflow port 8, water outlet valve 9-1, water inlet valve 9-2 and powdered activated carbon 10, the electrochemical-adsorption composite process is used to treat dye wastewater The pool body of the equipment is a cuboid with a size of 15cm*10cm*12cm. The graphite plate cathode 2 loaded with metal copper palladium and the ruthenium-tin-coated titanium anode 3 are respectively arranged in the pool of the equipment for treating dye wastewater by electrochemical-adsorption composite process At both ends of the body, the graphite plate cathode 2 loaded with metal copper and palladium is obtained by the ethylene glycol reduction method. The graphite plate electrode is taken, and the surface is smoothed and smoothed with sandpaper, soaked in NaOH solution and hydrochloric acid solution in turn, rinsed and dried. Prepare the prepared graphite plate electrode, place the prepared prepared graphite plate electrode in the ethylene glycol solution, and ultrasonicate for 1 h; weigh 76 mg of PdCl ₂ , 72 mg of CuCl ₂ ^. 2H ₂ O and 240 mg of sodium citrate in a 250 mL round bottom Add 50mL of ethylene glycol EG to the flask, stir at room temperature for 1h, then place the graphite plate electrode soaked in ethylene glycol in it, adjust the pH of the reaction mixture to 9.5- 0-10.5, continue to stir at room temperature for 30 minutes, then put the reaction mixture in an oil bath, and react for 6 hours at 160 ° C. After the reaction, take out the graphite plate electrode, wash it with deionized water, and dry it in vacuum to obtain the loaded metal The graphite plate cathode of copper palladium, the graphite plate cathode 2 loaded with metal copper palladium and the ruthenium tin-coated titanium anode 3 are all 10cm*8cm*0.5cm in size, the distance between the two electrodes is 4.0cm, and the graphite plate loaded with metal copper palladium The cathode 2 is connected to the negative pole of the DC stabilized power supply 1 through a wire, the ruthenium-tin coated titanium anode 3 is connected to the positive pole of the DC stabilized power supply 1 through a wire, and between the cathode 2 of the graphite plate loaded with metal copper and palladium and the ruthenium-tin coated titanium anode 3 Fill powdered activated carbon 10 and anhydrous sodium chloride, the particle size of powdered activated carbon 10 is 0.170 mm, and the overflow port 8 is arranged under the top cover of the pool body. The overflow port 8 is 3cm lower than the top of the pool body, the top cover of the pool body is movably connected with the pool body, a group of openings are provided on the top cover, a magnetic stirrer 4 is provided at the bottom of the pool body, and a magnetic stirrer 6 is provided in the pool body , the water outlet valve 9-1 and the water inlet valve 9-2 are respectively arranged on both sides of the pool body, and the waste water storage tank 5 is connected to the water inlet valve 9-2 through the peristaltic pump 7. After the waste water reacts completely in the pool body, the The outlet valve (9-1) flows out, and when there is too much waste water in the pool, the excess waste water overflows from the overflow port (8).

The processing methods specifically include the following:

Step 1: Boil the powdered activated carbon 10 in distilled water for 3 hours, then rinse it with distilled water for 8 minutes to remove the water-soluble and volatile substances in it, dry it at 120°C for 36 hours after rinsing, take it out, and put it into the loaded metal copper palladium Between the graphite plate cathode 2 and the ruthenium-tin-coated titanium anode 3, the distance between the two electrode plates is 3.0 cm, and 20 g/L NaCl is added between the electrode plates.

Step 2: Turn on the DC power supply 1, adjust the voltage to 5V, control the reaction interval time for 15 minutes, open the water inlet valve 9-2, and turn on the peristaltic pump 7, and the dye wastewater enters the reactor from the wastewater storage tank 5. The dye wastewater is simulated wastewater Alizarin S dye wastewater, initial concentration 600mg/L, COD=600mg/L, chromaticity 5.

The third step: water outlet detection: after the reaction, close the water inlet valve 9-2, open the water outlet valve 9-1, and the treated dye waste water will flow out from the water outlet valve 9-1. After 25 minutes of reaction, the removal rate of COD and chroma in the treated wastewater has reached 90%.

Step 4: When the concentration of the dye wastewater increases, resulting in an increase in the concentration of the effluent after treatment, which does not meet the "Comprehensive Discharge Standard for Sewage" (GB8978-1996), close the water inlet valve 9-2 and the peristaltic pump 7, and re-adjust the voltage and Reaction interval time, until the effluent reaches the standard and the normal processing flow is resumed. The method of readjusting the voltage and the intermittent reaction time is to increase the voltage by 1V, 3V, 5V, 7V and 9V in turn, and adjust the intermittent reaction time to 5min, 10min, 15min, 20min, 25min and 30min.

Example 3

As shown in Figure 1, a device for treating dye wastewater by electrochemical-adsorption composite process consists of a DC stabilized power supply 1, a graphite plate cathode 2 loaded with metal copper, a ruthenium-tin-coated titanium anode 3, a magnetic stirrer 4, and wastewater Composed of storage tank 5, magnetic stirrer 6, peristaltic pump 7, overflow port 8, water outlet valve 9-1, water inlet valve 9-2 and powdered activated carbon 10, the equipment for treating dye wastewater by the electrochemical-adsorption composite process The pool body is a cuboid with a size of 15cm*10cm*12cm. The graphite plate cathode 2 and ruthenium-tin-coated titanium anode 3 loaded with metal copper and palladium are respectively arranged in the pool body of the equipment for treating dye wastewater by electrochemical-adsorption composite process At both ends, the graphite plate cathode 2 loaded with metal copper and palladium is obtained by the ethylene glycol reduction method. The graphite plate electrode is taken, and the surface is polished with sandpaper to be smooth and flat, and then soaked in NaOH solution and hydrochloric acid solution in turn, and then rinsed and dried. To obtain the prepared graphite plate electrode, place the prepared prepared graphite plate electrode in the ethylene glycol solution, ultrasonicate for 1 h; weigh 76 mg of PdCl ₂ , 72 mg of CuCl ₂ ^. 2H ₂ O and 240 mg of sodium citrate in a 250 mL round bottom flask and add 50mL ethylene glycol EG, stir at room temperature for 1h, then place the graphite plate electrode soaked in ethylene glycol in it, adjust the pH of the reaction mixture to 9.5-0 with 5wt% KOH/EG solution -10.5, continue to stir at room temperature for 30 minutes, then place the reaction mixture in an oil bath, and react for 6 hours at 160 ° C. After the reaction, take out the graphite plate electrode, wash it with deionized water, and obtain the supported metal copper after vacuum drying The graphite plate cathode of palladium, the graphite plate cathode 2 loaded with metal copper palladium and the ruthenium-tin coated titanium anode 3 are all 10cm*8cm*0.5cm in size, the distance between the two electrodes is 5.0cm, and the graphite plate cathode loaded with metal copper palladium 2 is connected to the negative pole of the DC stabilized power supply 1 through a wire, and the ruthenium-tin-coated titanium anode 3 is connected to the positive pole of the DC stabilized power supply 1 through a wire, and the graphite plate cathode 2 loaded with metal copper and palladium is filled with the ruthenium-tin-coated titanium anode 3 Powdered activated carbon 10 and anhydrous sodium chloride, powdered activated carbon particle 10 particle diameter is 2.00mm, overflow port 8 is arranged under the tank body top cover. The overflow port 8 is 5cm lower than the top of the pool body, the top cover of the pool body is movably connected with the pool body, a group of openings are provided on the top cover, a magnetic stirrer 4 is provided at the bottom of the pool body, and a magnetic stirrer 6 is provided in the pool body , the water outlet valve 9-1 and the water inlet valve 9-2 are respectively arranged on both sides of the pool body, and the waste water storage tank 5 is connected to the water inlet valve 9-2 through the peristaltic pump 7. After the waste water reacts completely in the pool body, the Outlet valve 9-1 flows out, and when the waste water in the pond body is too much, too much waste water overflows from overflow port 8.

The processing methods specifically include the following:

Step 1: Boil the powdered activated carbon 10 in distilled water for 4 hours, then rinse it with distilled water for 10 minutes to remove the water-soluble and volatile substances in it, dry it at 120°C for 48 hours after rinsing, take it out, and put it into the loaded metal copper palladium Between the graphite plate cathode 2 and the ruthenium-tin-coated titanium anode 3, the distance between the two electrode plates is 3.0 cm, and 20 g/L NaCl is added between the electrode plates.

Step 2: Turn on the DC power supply 1, adjust the voltage to 9V, control the intermittent reaction time for 30 minutes, open the water inlet valve 9-2, and turn on the peristaltic pump 7. The dye wastewater enters the reactor from the wastewater storage tank 5. The dye wastewater is simulated wastewater. Alizarin S dye wastewater, initial concentration 1000mg/L, COD=600mg/L chromaticity 6.

The third step, water outlet detection: after the reaction, close the water inlet valve 9-2, open the water outlet valve 9-1, the treated dye wastewater flows out from the outlet valve 9-1, and detect the COD and chroma in the dye wastewater after treatment; After 50 minutes of reaction, the removal rate of COD and chroma in the waste water after reaction reaches 85%, and it can be discharged after reaching the "Integrated Wastewater Discharge Standard" (GB8978-1996).

Step 4: When the concentration of dye wastewater increases, causing the treated effluent to fail to meet the "Integrated Wastewater Discharge Standard" (GB8978-1996), close the water inlet valve 9-2 and peristaltic pump 7, and adjust the voltage and reaction interval time , until the water reaches the standard and the normal processing flow is restored, the adjustment method of re-adjusting the voltage and the intermittent reaction time is to increase the voltage 1V, 3V, 5V, 7V and 9V in turn, and adjust the intermittent reaction time to 5min, 10min, 15min, 20min, 25min and 30min .

High current efficiency, strong oxidation ability, low energy consumption, good COD removal and decolorization effects, convenient operation, and wide application range.

The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above embodiments, and can also be made without departing from the gist of the present invention within the scope of knowledge possessed by those of ordinary skill in the art. Variations.

Claims (8)

1. the equipment that a kind of electrochemistry-absorption combination process handles waste water from dyestuff, it is characterised in that：By D.C. regulated power supply（1）、 The graphite sheet cathode of carried metal copper palladium（2）, ruthenium tin coating Ni―Ti anode（3）, magnetic stirring apparatus（4）, wastewater storage tank（5）, magnetic force Stirrer（6）, peristaltic pump（7）, overfall（8）, outlet valve（9-1）, water intaking valve（9-2）And powdered active carbon（10）Composition, The graphite sheet cathode of the carried metal copper palladium（2）With ruthenium tin coating Ni―Ti anode（3）It is respectively provided at electrochemistry-absorption combination process Handle the pond body two ends of the equipment of waste water from dyestuff, the graphite sheet cathode of carried metal copper palladium（2）Pass through wire and DC voltage-stabilizing electricity Source（1）Negative pole is connected, ruthenium tin coating Ni―Ti anode（3）Pass through wire and D.C. regulated power supply（1）Positive pole is connected, carried metal copper palladium Graphite sheet cathode（2）With ruthenium tin coating Ni―Ti anode（3）Between powder filler shaped activated carbon（10）And anhydrous sodium chloride, overfall （8）It is located at below pond body top cover, the pond body top cover is flexibly connected with pond body, pond body top cover is provided with one group of perforate, pond body bottom Portion is provided with magnetic stirring apparatus（4）, pond body is interior to be provided with magnetic stir bar（6）, described outlet valve（9-1）And water intaking valve（9-2）Point Pond body both sides, wastewater storage tank are not located at（5）Pass through peristaltic pump（7）With water intaking valve（9-2）It is connected, when waste water has reacted in pond body Quan Hou, by outlet valve（9-1）Outflow, when waste water is excessive in pond body, excessive waste water is from overfall（8）Overflow.

2. the equipment that electrochemistry according to claim 1-absorption combination process handles waste water from dyestuff, it is characterised in that：Institute State the graphite sheet cathode of carried metal copper palladium（2）It is made by reduction of ethylene glycol method, takes graphite plate electrode, sand paper polishing surface is smooth It is smooth, it is sequentially placed into NaOH solution and hydrochloric acid solution and soaks, then rinse and dry, preparation graphite plate electrode is made, will be made Preparation graphite plate electrode as in ethylene glycol solution, ultrasonic 1h；Weigh 76mg PdCl₂, 72mg CuCl₂ ^.2H₂O and 240mg sodium citrate adds 50mL ethylene glycol EG in 250mL round-bottomed flasks, and 1h is stirred at room temperature, then will be above-mentioned The graphite plate electrode being soaked in ethylene glycol is placed therein, with 5wt% KOH/EG solution adjust reaction mixture pH to 9.5-0-10.5, continues that 30min is stirred at room temperature, then reaction mixture is placed in oil bath pan, 6h is reacted at 160 DEG C, After reaction terminates, graphite plate electrode is taken out, with deionized water rinsing, the graphite cake that carried metal copper palladium is obtained after vacuum drying is cloudy Pole.

3. the equipment that electrochemistry according to claim 1-absorption combination process handles waste water from dyestuff, it is characterised in that：Institute The pond body for stating the equipment of electrochemistry-absorption combination process processing waste water from dyestuff is cuboid, and size is 15cm × 10cm × 12cm.

4. the equipment that electrochemistry according to claim 1-absorption combination process handles waste water from dyestuff, it is characterised in that：Institute State the graphite sheet cathode of carried metal copper palladium（2）With ruthenium tin coating Ni―Ti anode（3）Size is 10cm × 8cm × 0.5cm, two electricity Anode-cathode distance 3.0cm-5.0cm.

5. the equipment that electrochemistry according to claim 1-absorption combination process handles waste water from dyestuff, it is characterised in that：Institute State powdered active carbon particle（10）Particle diameter is 0.15mm-2.00mm.

6. the equipment that electrochemistry according to claim 1-absorption combination process handles waste water from dyestuff, it is characterised in that：Institute State overfall（8）Less than pond body top 1cm-5cm.

7. a kind of processing side of the equipment of any described electrochemistry of claim 1-6-absorption combination process processing waste water from dyestuff Method, it is characterised in that：Comprise the following steps：

The first step：By powdered active carbon（10）It is placed in distilled water and boils 2-4h, then use distilled water flushing 5-10min, rushes 24-48h is dried at 120 DEG C to take out, be put into the graphite sheet cathode of carried metal copper palladium after the completion of washing（2）With ruthenium tin coating titanium sun Pole（3）Between, while adding 20g/L anhydrous sodium chlorides；

Second step：Dc source (1) is opened, voltage range≤9V, control reaction intermittent time≤30min is adjusted, opens water inlet Valve（9-2）, open peristaltic pump（7）, waste water from dyestuff is from wastewater storage tank（5）Into in reactor, waste water from dyestuff uses simulated wastewater Alizarin red S waste water from dyestuff, initial concentration 200-1000mg/L, COD=600mg/L, colourity 4-6；

3rd step, water outlet detection：Water intaking valve is closed after reaction（9-2）, open outlet valve（9-1）, waste water from dyestuff after processing by Outlet valve（9-1）COD and colourity reach in waste water from dyestuff after outflow, detection process《Integrated wastewater discharge standard》（GB8978- 1996）After can discharge；

4th step：When the rise of waste water from dyestuff concentration, cause aqueous concentration after processing to raise, do not reach《Integrated wastewater discharge standard》 （GB8978-1996）, close water intaking valve（9-2）And peristaltic pump（7）, voltage and reaction intermittent time are readjusted, until water outlet Recover normal process flow after up to standard.

8. the processing method of the equipment of electrochemistry according to claim 7-absorption combination process processing waste water from dyestuff, it is special Levy and be：4th step readjust voltage and reaction the intermittent time adjusting method for heighten successively voltage 1V, 3V, 5V, 7V and 9V, regulation reaction intermittent time 5min, 10min, 15min, 20min, 25min and 30min.