CN110835190A - Wastewater treatment system and method for degrading Cu-EDTA by electric flocculation coupling ultraviolet light - Google Patents
Wastewater treatment system and method for degrading Cu-EDTA by electric flocculation coupling ultraviolet light Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers
Abstract
The invention provides a wastewater treatment system and method for degrading Cu-EDTA by electrocoagulation-coupled ultraviolet light. The wastewater treatment method of the invention comprises the following steps: an electrolysis step, a standing precipitation step, an ultraviolet photolysis step and a pH adjustment step. According to the characteristics of the Cu-EDTA complex wastewater, the electrocoagulation technology is combined with the ultraviolet degradation technology, namely, ferrous iron is quickly added by utilizing iron anode electrolysis to form an anoxic environment, then a large amount of structural ferrous iron is generated to replace Cu-EDTA with Fe (III) -EDTA, Cu is removed by adsorption and precipitation, and Fe (III) -EDTA is removed by utilizing the ultraviolet degradation technology. The method has the characteristics of convenience, quickness and no introduction of impurity anions by electrolyzing in-situ fed iron, is coupled with an ultraviolet light degradation technology, has the Cu-EDTA removal efficiency of more than 99 percent, and is a green, economic, safe and practical heavy metal complexing wastewater treatment technology.
Description
Technical Field
The invention relates to a wastewater treatment system and method for degrading Cu-EDTA by electrocoagulation-coupled ultraviolet light, belonging to the technical field of environmental protection and sewage treatment.
Background
In the production of circuit boards, various electroplating additives are usually used, and the additives are complex in components and contain chelating agents capable of forming stable chelates with heavy metals, wherein EDTA is the most typical, metal copper is complexed with EDTA to form a Cu-EDTA complex in a chemical copper deposition process, the stability of the complex is extremely strong, the complex is not easy to degrade, and if the complex is not effectively treated, the complex can cause serious influence on the living environment of human beings and even harm the health of human beings.
In the conventional sewage treatment method, free metal ions can be easily removed by the conventional processes such as alkaline precipitation or ion exchange, but if the free metal ions are complexed with EDTA, the stability is high, and the free metal ions are difficult to remove by the conventional sewage treatment method. At present, the treatment method of the wastewater containing Cu-EDTA mainly comprises an adsorption method, a Fenton oxidation method, a photocatalysis method, a replacement method, an oxidation precipitation method and the like. However, the above-mentioned methods are limited in large part by relatively high cost, poor selectivity, low efficiency, and high sensitivity to solution chemistry. The displacement-precipitation method based on the ferric salt is widely concerned because of relatively low cost and high Cu removal efficiency, but the ferric salt displacement method is complicated to operate, is easy to introduce new impurity metal ions, has high requirements on the pH value of Cu-EDTA wastewater, has a good removal effect only on acidic wastewater with the pH value less than 3, and has a poor removal effect on wastewater with the pH value more than or equal to 3. In the electric flocculation method in the prior art, iron ions can be added in situ by using the iron plate anode, and the method has the characteristics of being more convenient and quicker compared with the addition of iron salts, and not introducing impurity anions, but has the defect of lower degradation efficiency on EDTA.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides the system and the method for treating the wastewater by degrading the Cu-EDTA through the electrocoagulation-coupling ultraviolet light, so that both Cu ions and the EDTA in the wastewater can be removed at higher efficiency, the production cost is lower, the device is simple and easy to maintain, resources are saved, the environment is protected, and secondary pollution is avoided.
In order to achieve the purpose, the invention adopts the technical scheme that:
the utility model provides an electric flocculation coupling ultraviolet degradation Cu-EDTA's effluent disposal system, includes electrolysis unit, its characterized in that: a standing precipitation unit, an ultraviolet photolysis unit and a pH adjusting unit are sequentially connected behind the electrolysis unit;
the electrolysis unit comprises a first water container, the first water container is provided with a first water inlet and a first-stage water outlet, the first-stage water outlet is arranged at the top end of the side wall of the container, positive and negative electrodes are arranged in the first water container, the positive and negative electrodes are iron plates, the distance between the electrodes is 0.5 cm-2 cm, and the positive and negative electrodes are respectively connected with the positive and negative electrodes of a direct-current power supply arranged outside the first container;
the standing and precipitating unit comprises a second water container, a second water inlet and a second-stage water outlet are formed in the second water container, and the second water inlet is connected with the first-stage water outlet;
the ultraviolet photolysis unit comprises a third water container, a third water inlet and a third-stage water outlet are formed in the third water container, one or more ultraviolet lamps are mounted in the third water container, and the ultraviolet lamps are uniformly and vertically placed around the container wall;
the pH adjusting unit comprises a fourth water container, a fourth water inlet and a fourth-stage water outlet are formed in the fourth water container, the fourth-stage water outlet is a purified water outlet, and the fourth water inlet is connected with the third-stage water outlet of the ultraviolet photolysis unit water container.
The technical scheme of the invention is further improved by the following steps:
stirring devices can be respectively arranged in the first water container, the third water container and the fourth water container.
And a turbidity testing device is arranged at a secondary water outlet of the standing precipitation unit.
The fourth water container of the pH adjusting unit is made of alkali-resistant materials, an alkali liquor adding device is arranged outside the fourth water container, and the alkali liquor adding device comprises an alkali liquor storage tank and a metering pump.
The standing precipitation unit can be combined with the front electrolysis unit or the rear ultraviolet photolysis unit into a unit, and the water container, the water inlet and the water outlet of the water container are shared.
In the electrolysis unit, when the pH of the wastewater is lower<3, the current required for treating each liter of wastewater is not less than 0.2A; when the pH value of the wastewater is more than or equal to 3, the current for treating each liter of wastewater is not less than 0.4A; the ultraviolet light intensity range of the ultraviolet photolysis unit is 5mW/cm2～50mW/cm2。
A wastewater treatment method of a wastewater treatment system for degrading Cu-EDTA by electrocoagulation coupled ultraviolet light comprises the following steps:
s1, electrolysis step: introducing the Cu-EDTA wastewater into an electrolysis unit, rapidly adding a large amount of ferrous iron into the wastewater through an electrolytic iron anode to oxidize the ferrous iron in the wastewater into ferric iron, replacing copper ions in the Cu-EDTA, and converting the Cu-EDTA in the original wastewater into Fe (III) -EDTA; in the electrolysis unit, when the pH value of the wastewater is less than 3, the current required for treating each liter of wastewater is not less than 0.2A; when the pH value of the wastewater is more than or equal to 3, the current for treating each liter of wastewater is not less than 0.4A;
s2, standing and precipitating: standing the wastewater electrolyzed in the step S1 for 10-20 minutes to precipitate floccules generated by electrolysis, and discharging the supernatant after standing through a water outlet;
s3, ultraviolet photolysis: introducing the wastewater discharged in the step S2 into an ultraviolet photolysis unit, so that Fe (III) -EDTA generates a catalytic reaction under the irradiation of ultraviolet light, the EDTA is degraded and removed, and iron ions are dissociated in water; the ultraviolet light intensity range of the ultraviolet photolysis unit is 5mW/cm2～50mW/cm2；
S4, pH adjusting step: and (4) introducing the wastewater discharged in the step (S3) into a pH adjusting unit, adjusting the pH value of the wastewater to make the wastewater be alkaline with the pH value being more than or equal to 9, removing free iron ions and copper ions in the wastewater to finish the wastewater purification process, and discharging the purified water from a purified water outlet.
The technical proposal of the invention is further improved by the following steps:
in step S4, the pH value of the wastewater is adjusted to be NaOH solution or other alkali liquor added into the wastewater.
As an optimization scheme of the wastewater treatment method, the method further comprises the following steps:
s4.1, detecting the pollutant concentration of the purified water discharged in the step S4, and adjusting the water flow speed of the introduced wastewater: when the concentration of the pollutants in the purified water outlet is lower than the set standard, the flow rate of the introduced wastewater is increased, otherwise, the flow rate of the introduced wastewater is reduced, so that the pollutants have enough residence time in the electrolysis unit.
S2.1, adjusting the standing time of the standing precipitation unit: and detecting the turbidity of the wastewater at the water outlet of the standing and precipitating unit, increasing or decreasing the standing time according to the turbidity, if the turbidity of the wastewater at the water outlet is lower than a set standard, decreasing the standing time of the standing and precipitating unit, and if the turbidity of the wastewater at the water outlet is higher than the set standard, increasing the standing time of the standing and precipitating unit.
According to the technical scheme provided by the invention, the wastewater treatment system comprises four units, firstly, the electrolysis unit replaces copper in Cu-EDTA through the iron plate anode, and the smaller the distance between the electrodes of the electrolysis unit is, the smaller the resistance formed between the electrodes is, so that the more favorable the reduction of power consumption is; then settling the electrolyzed wastewater by a standing settling unit, and discharging supernatant through a secondary water outlet in the middle of a second container of the standing settling unit after settling; the supernatant enters an ultraviolet photolysis unit, and is irradiated by an ultraviolet lamp in a third water container to perform catalytic degradation on the inflowing wastewater, so that EDTA is partially or completely degraded and removed. And finally, the pH value of the wastewater is adjusted by a pH adjusting unit so as to remove free iron ions and copper ions, and an alkali liquor adding device is arranged outside a fourth container of the unit, so that the addition of the alkali liquor is more convenient and quicker. A stirring device is arranged in the first water container, so that the wastewater and the suspended matters can be uniformly mixed, and the reaction is accelerated; a stirring device is arranged in the third water container, so that the wastewater can be more uniform through ultraviolet light catalysis; a stirring device is arranged in the fourth water container to ensure thatThe alkali liquor is mixed more evenly. The device of the wastewater treatment system has simple structure and convenient maintenance, and has good removal effect on acidic and alkaline Cu-EDTA wastewater. According to the wastewater treatment method, in the electrolysis step, a large amount of ferrous iron is rapidly added into the wastewater through an electrolytic iron anode to form an anoxic environment, a large amount of structural ferrous iron is generated, copper ions are displaced and adsorbed for precipitation, the discharged wastewater is subjected to standing and precipitation, the supernatant is discharged into an ultraviolet photolysis unit for photocatalysis, and EDTA is partially or completely degraded and removed; finally, free iron ions and a small amount of possibly unremoved copper ions in the water are removed through a pH adjusting step, and the wastewater purification process is completed. The whole wastewater treatment method has simple steps, comprehensively applies electrolysis and photolysis, has good degradation effect, greatly improves the removal efficiency of Cu-EDTA, does not need to add ferric ions into the wastewater by adopting the method, saves the cost, improves the working efficiency and has simple operation steps. When the method adopted by the invention is used for replacing copper ions, the power supply of the electrode is only needed to be switched on, and O does not need to be introduced into water2Or N2And the like, compared with the traditional structural ferrous iron synthesized by electrocoagulation or direct addition of medicaments, the method has the characteristics of energy conservation and high treatment efficiency, has wide pH application range, and does not introduce impurity ions. During electrolysis, free copper ions in water are partially separated out on the iron plate electrode in the form of copper simple substances, so that the purer copper simple substances are conveniently recycled, and the copper ions in water are removed, so that the method is resource-saving and environment-friendly.
Drawings
FIG. 1 is a schematic view showing the structure of a wastewater treatment system according to example 1 of the present invention.
FIG. 2 is a graph showing the time-dependent change in the residual ratio of total EDTA and the residual ratio of Cu-EDTA in a water sample during the whole process of example 1.
FIG. 3 is a schematic view of the structure and wastewater flow of embodiment 2 of the wastewater treatment system of the present invention.
In the figure: 1. an electrolysis unit; 2. an ultraviolet photolysis unit; a pH adjusting unit; 4. a first water container; 5. a cathode; 6. an anode; 7. a direct current power supply; 8. a first stirring device; 9. a third water container; 10. an ultraviolet lamp; 11. a third stirring device; 12. a fourth water container; 13. a fourth stirring device; 14. a standing and precipitating unit; 15. a water pump; 16. a first valve; 17. a second water container; 18. a second valve; 19. a third valve; 20. a fourth valve; 21. a sodium hydroxide holding tank; 22. metering pump valve.
Detailed Description
The invention is further illustrated by the following examples:
as shown in fig. 1, example 1 can be used in a laboratory simulation system including an electrolysis unit 1, an ultraviolet photolysis unit 2, and a PH adjustment unit 3, which are sequentially disposed, and wastewater sequentially passes through the electrolysis unit 1, the ultraviolet photolysis unit 2, and the PH adjustment unit 3.
The electrolysis unit 1 of this embodiment combines the unit of settling that stews, includes first water container 4, and first water container 4 is diameter 85mm, and high 130 mm's cylinder reactor, and the open-top of first water container 4 is first water inlet. The first water container 4 is provided with a cathode and an anode, the cathode 5 and the anode 6 both select pure iron sheet electrodes, the size of the two electrodes is 80mm multiplied by 15mm, the thickness is 1mm, and the distance between the two electrodes is 2.0 cm. A direct current power supply 7 and a first stirring device 8 are arranged outside the first water container 4, the direct current power supply 7 is a stable direct current power supply and is responsible for supplying current to the two electrodes, and the first stirring device 8 enables the wastewater in the first water container 1 to be electrolyzed more uniformly. The direct current power supply 7 is provided with a ammeter and an output end, the anode of the output end is connected with the anode 6, and the cathode of the output end is connected with the cathode 5.
The UV photolysis unit 2 comprises a third water container 9 and a UV lamp 10, wherein the third water container 9 is a cylindrical reactor with a diameter of 85mm and a height of 130mm, and the UV lamp 10 has a UV intensity of about 20mW/cm2And a third stirring device 11 is arranged outside the third water container 9, the third stirring device 11 enables the liquid in the reactor to be more uniformly irradiated by the ultraviolet lamp, and the ultraviolet lamp 10 is used for degrading Fe (III) -EDTA displaced from the electrolysis unit 1.
The pH adjusting unit 3 comprises a fourth water container 12, the fourth water container 12 is a cylindrical reactor with the diameter of 85mm and the height of 130mm, a fourth stirring device 13 is arranged outside the fourth water container 3, and the fourth stirring device 13 can enable the added alkali liquor to be mixed more uniformly when the pH value of the wastewater is adjusted.
The wastewater treatment method adopting the wastewater treatment system comprises the following specific implementation steps:
s1, electrolysis step: 500mL of a solution containing 0.3mM Cu-EDTA and 50mM Na was added to the first water container 4 in the electrolytic unit 12SO4The first stirring device 8 is turned on, the current is output by the direct current power supply 7 at 200mA, and electrolysis is carried out for 30min, so that the Cu-EDTA contained in the water is converted into Fe (III) -EDTA.
S2, standing and precipitating: after the reaction of the electrolysis unit 1 is finished, the first stirring device is closed, and the solution is allowed to stand in the first water container 4 for 15min until the clear liquid is not turbid.
S3, ultraviolet photolysis: and (3) introducing the supernatant part of the solution after standing into a third water container 9 of the ultraviolet photolysis unit 2, opening a third stirrer device 11 and an ultraviolet lamp 10, and stopping the reaction after the reaction is carried out for 30min, wherein Fe (III) -EDTA carries out a photocatalytic reaction under the irradiation of ultraviolet light in the process, so that the EDTA is partially or completely degraded into carbon dioxide, and iron ions are dissociated in water.
S4, pH adjusting step: the solution after the reaction in the ultraviolet photolysis unit 2 is entirely poured into the pH adjustment unit 3, the fourth stirring device 13 is opened, and a 1mM NaOH solution is slowly dropped thereinto to have a pH of 9, so that the metal ions free in the solution can be precipitated and removed to obtain a completely treated aqueous solution.
This example is mainly carried out by detecting the concentration changes of Cu-EDTA and total EDTA in the aqueous solution at different time points in the reaction and comparing with the initial concentrations of Cu-EDTA and total EDTA in the wastewater, i.e. C/C0Referring to fig. 2, it can be seen from fig. 2 that the concentration of Cu-EDTA and total EDTA in the final effluent is less than 1% at a current of 200mA, that is, the removal rate of Cu-EDTA and total EDTA can reach over 99% and remain stable.
As shown in fig. 3, example 2 can be used for practical production, and includes an electrolysis unit 1, a standing precipitation unit 14, an ultraviolet photolysis unit 2, and a pH adjustment unit 3, which are sequentially disposed, and wastewater sequentially passes through the electrolysis unit 1, the standing precipitation unit 14, the ultraviolet photolysis unit 2, and the pH adjustment unit 3.
The electrolysis unit 1 comprises a first water container 4, a first water inlet is formed in the bottom of the first water container 4, a first-stage water outlet is formed in the top end of the side wall of the first water container, and a first-stage water outlet is formed in the top end of the side wall of the first water container, so that displacement is precipitated, and precipitates of wastewater flowing into the next unit are reduced; the first water container 4 is internally provided with a cathode and an anode, the distance between the electrodes is 0.5 cm-2 cm, the cathode and the anode are made of common iron materials, a water pump 15 and a direct current power supply (not shown in the figure) are arranged outside the first water container, the water pump 15 is adopted to introduce the wastewater into the first water container 4, the external direct current power supply provides current for the cathode and the anode, the current passing through the cathode and the anode is controlled, and when the pH value of the wastewater is less than 3, the current required for treating each liter of wastewater is not less than 0.2A; when the pH value of the wastewater is more than or equal to 3, the current for treating each liter of wastewater is not less than 0.4A; one or more groups of the cathode and the anode can be selected according to actual production needs.
The standing and precipitating unit 14 comprises a second water container 17, a second water inlet of the second water container 17 is positioned at the top of the side wall and is connected with a first-stage water outlet through a first pipeline, a first valve 16 is arranged in the first pipeline, a second-stage water outlet is arranged in the middle of the side wall of the second water container 17, and a turbidity testing device (not shown in the figure) is arranged at the second-stage water outlet.
The ultraviolet photolysis unit 2 comprises a third water container 9, a water inlet of the third water container 9 is positioned at the top of the side wall of the third water container and is connected with a secondary water outlet through a second pipeline, a second valve 18 is arranged in the second pipeline, a tertiary water outlet of the third water container 9 is positioned at the bottom of the side wall of the third water container, a third stirring device 11 and 2 ultraviolet lamps 10 are installed in the third water container 9, and the wastewater is irradiated by the ultraviolet lamps more uniformly through the third stirring device 11; the number of the ultraviolet lamps 10 is not fixed and can be determined according to the size of the container, and the ultraviolet lamps 10 are uniformly and vertically placed around the side wall of the third water container 9.
The pH adjusting unit 3 comprises a fourth water container 12, a fourth stirring device 13 is arranged inside the fourth water container 12, a fourth water inlet of the fourth water container 12 is located at the top of the side wall of the fourth water container and is connected with a third-level water outlet through a third pipeline, a third valve 19 is arranged in the third pipeline, a fourth-level water outlet of purified water of the fourth water container 12 is located at the bottom of the side wall of the fourth water container, a fourth-level water outlet is connected with a fourth pipeline, and a fourth valve 10 is arranged in the fourth pipeline. A set of alkali liquor feeding device is arranged outside the fourth water container 12. The alkali liquor adding device comprises an alkali liquor storage tank 21 and a metering pump, a metering pump valve 22 is arranged on the metering pump, and the alkali liquor enters the fourth water container 12 through the metering pump valve 22. The fourth water container 12 is made of an alkali-resistant material.
In the embodiment, a stirring device can be additionally arranged in the first water container to uniformly mix the wastewater and the suspended matters, so that the reaction is accelerated.
The wastewater treatment method adopting the wastewater treatment system comprises the following specific implementation steps:
the device used in the embodiment is the device in the second embodiment of the wastewater treatment system for degrading Cu-EDTA by electroflocculation coupling ultraviolet light, and the specific steps are as follows:
s1, electrolysis step: the Cu-EDTA wastewater is introduced into a first water container 4 of an electrolysis unit 1 through a water pump 15, a direct current power supply 7 is switched on, an anode iron plate in the first container 4 is rapidly electrolyzed, namely a large amount of ferrous iron is added into the wastewater, the ferrous iron is oxidized to generate more stable ferric iron, dissolved oxygen is exhausted in the oxidation process of the ferrous iron to form an anoxic environment with DO <0.2mg/L, and the structural ferrous iron is accumulated. The stability constant of Fe (III) -EDTA under acidic condition is much higher than that of Cu-EDTA. For acidic waste waters with a pH <3, Cu-EDTA is mainly replaced by ferric iron to Fe (III) -EDTA. In the wastewater with the pH value of more than or equal to 3, the structural state ferrous iron can replace and reduce the complex state Cu. The replaced Fe (III) -EDTA is easier to remove than Cu-EDTA, and simultaneously, most of copper is eliminated in the iron precipitate, part of copper is separated out on the cathode iron sheet, and the copper simple substance on the iron sheet is convenient to recycle.
S2, standing and precipitating: opening a first valve 16 of the first pipeline, allowing the electrolyzed wastewater to enter a second container 17 of the standing sediment 14 through a second water inlet, standing for 20 minutes to allow floccules generated by electrolysis to sediment, and discharging the supernatant after standing through a secondary water outlet at the middle upper part; the detection device detects the turbidity of the wastewater at the secondary water outlet of the standing precipitation unit, and the standing time is increased or reduced according to the turbidity. When the turbidity measured in the second-stage water outlet is higher, the standing time of the standing precipitation unit is increased, otherwise, the standing time is reduced, so that the wastewater at the second-stage water outlet can be uniformly irradiated by the ultraviolet lamp in the ultraviolet photolysis unit to react completely and reduce the power consumption.
S3, ultraviolet photolysis: the second valve 18 of the second pipeline is opened, the wastewater enters the third container 9 of the ultraviolet photolysis unit 2 through the third water inlet, the switches of the two ultraviolet lamps 10 and the third stirring device 11 are opened, so that Fe (III) -EDTA generates catalytic reaction under the irradiation of the two ultraviolet lamps 10, the EDTA is partially or completely degraded into carbon dioxide, and is removed, iron ions are dissociated in the water, the stirring device 11 can ensure that the wastewater is irradiated by the ultraviolet light more uniformly, the catalytic degradation is more complete, the effect is better, and the ultraviolet light intensity range is 5mW/cm2～50mW/cm2。
S4, pH adjusting step: opening a valve 19 of a third pipeline, enabling the wastewater to enter a fourth container 12 of the pH adjusting unit 3 through a fourth water inlet, pressing a metering pump valve 22 of an alkali liquor adding device to enable NaOH solution in an alkali liquor storage tank 21 to slowly enter the fourth container 12, starting a fourth stirring device 13, adjusting the pH value of the wastewater to enable the wastewater to become alkaline solution with the pH value being more than or equal to 9, enabling free iron ions and copper ions in the solution to be precipitated and removed to obtain completely-treated aqueous solution, completing the wastewater purification process, opening a fourth valve 20 of a fourth pipeline, and discharging purified water from a fourth-stage water outlet.
Monitoring the concentration of Cu-EDTA and total EDTA in the treated water solution, optimizing energy consumption according to the treatment effect of Cu-EDTA complexing wastewater, and adjusting the water flow speed of introduced wastewater: when the concentration of the pollutants in the purified water outlet is lower than a set standard, the flow rate of the introduced wastewater is increased, otherwise, the flow rate of the introduced wastewater is reduced, so that the pollutants have enough residence time in the electrolysis unit, the water quality at the purified water outlet is ensured to reach the standard, and the energy consumption is reduced; .
According to the characteristics of the Cu-EDTA complex wastewater, the electrocoagulation technology is combined with the ultraviolet degradation technology, namely, ferrous iron is quickly added by utilizing iron anode electrolysis to form an anoxic environment, then a large amount of structural ferrous iron is generated to replace Cu-EDTA with Fe (III) -EDTA, Cu is removed by adsorption and precipitation, and Fe (III) -EDTA is removed by utilizing the ultraviolet degradation technology. According to the invention, iron is added in situ through electrolysis, compared with the characteristic that iron salt is directly added, the method is convenient and quick, and impurity anions are not introduced, and the system has better removal efficiency on Cu and EDTA by coupling the ultraviolet light degradation technology. The invention is a green, economical, safe and practical heavy metal complexing wastewater treatment technology.
The wastewater treatment system for degrading Cu-EDTA by the electrocoagulation coupled ultraviolet light has a simple equipment structure, and has a good removal effect on Cu-EDTA wastewater with different pH values by utilizing the double combination of electrolysis and photolysis. The method has simple steps and high efficiency, and the combined action of the ferric iron and the structural state ferrous iron ensures that the method has wider pH adaptation range. Through detection, the removal rate of Cu-EDTA in the wastewater can reach more than 99%, and the wastewater has high removal rate and stable effect.
Claims (10)
1. The utility model provides an electric flocculation coupling ultraviolet degradation Cu-EDTA's effluent disposal system, includes electrolysis unit, its characterized in that: a standing precipitation unit, an ultraviolet photolysis unit and a pH adjusting unit are sequentially connected behind the electrolysis unit;
the electrolysis unit comprises a first water container, the first water container is provided with a first water inlet and a first-stage water outlet, the first-stage water outlet is arranged at the top end of the side wall of the container, positive and negative electrodes are arranged in the first water container, the positive and negative electrodes are iron plates, the distance between the electrodes is 0.5 cm-2 cm, and the positive and negative electrodes are respectively connected with the positive and negative electrodes of a direct-current power supply arranged outside the first container;
the standing and precipitating unit comprises a second water container, a second water inlet and a second-stage water outlet are formed in the second water container, and the second water inlet is connected with the first-stage water outlet;
the ultraviolet photolysis unit comprises a third water container, a third water inlet and a third-stage water outlet are formed in the third water container, more than one ultraviolet lamp is installed in the third water container, and the ultraviolet lamps are uniformly and vertically placed around the container wall;
the pH adjusting unit comprises a fourth water container, a fourth water inlet and a fourth-stage water outlet are formed in the fourth water container, the fourth-stage water outlet is a purified water outlet, and the fourth water inlet is connected with the third-stage water outlet of the ultraviolet photolysis unit water container.
2. The wastewater treatment system for degrading Cu-EDTA by electrocoagulation-coupled ultraviolet light according to claim 1, wherein: stirring devices can be respectively arranged in the first water container, the third water container and the fourth water container.
3. The wastewater treatment system for degrading Cu-EDTA by electrocoagulation-coupled ultraviolet light according to claim 1, wherein: and a turbidity testing device is arranged at a secondary water outlet of the standing precipitation unit.
4. The wastewater treatment system for degrading Cu-EDTA by electrocoagulation-coupled ultraviolet light according to claim 1, wherein: the fourth water container of the pH adjusting unit is made of alkali-resistant materials, an alkali liquor adding device is arranged outside the fourth water container, and the alkali liquor adding device comprises an alkali liquor storage tank and a metering pump.
5. The wastewater treatment system for degrading Cu-EDTA by electrocoagulation-coupled ultraviolet light according to claim 1, wherein: the standing precipitation unit can be combined with the front electrolysis unit or the rear ultraviolet photolysis unit into a unit, and the water container, the water inlet and the water outlet of the water container are shared.
6. The wastewater treatment system for degrading Cu-EDTA by electrocoagulation-coupled ultraviolet light according to claim 1, wherein: in the electrolysis unit, when the pH of the wastewater is lower<3, the current required for treating each liter of wastewater is not less than 0.2A; when the pH value of the wastewater is more than or equal to 3, the current for treating each liter of wastewater is not less than 0.4A; the ultraviolet light intensity range of the ultraviolet photolysis unit is 5mW/cm2～50mW/cm2。
7. The wastewater treatment method of the wastewater treatment system for degrading Cu-EDTA by using the electric flocculation coupling ultraviolet light as claimed in claim 1, which comprises an electrolysis step, and is characterized by comprising the following specific steps:
s1, electrolysis step: introducing the Cu-EDTA wastewater into an electrolysis unit, rapidly adding a large amount of ferrous iron into the wastewater through an electrolytic iron anode to oxidize the ferrous iron in the wastewater into ferric iron, replacing copper ions in the Cu-EDTA, and converting the Cu-EDTA in the original wastewater into Fe (III) -EDTA; in the electrolysis unit, when the pH value of the wastewater is less than 3, the current required for treating each liter of wastewater is not less than 0.2A; when the pH value of the wastewater is more than or equal to 3, the current for treating each liter of wastewater is not less than 0.4A;
s2, standing and precipitating: standing the wastewater electrolyzed in the step S1 for 10-20 minutes to precipitate floccules generated by electrolysis, and discharging the supernatant after standing through a water outlet;
s3, ultraviolet photolysis: introducing the wastewater discharged in the step S2 into an ultraviolet photolysis unit, so that Fe (III) -EDTA generates a catalytic reaction under the irradiation of ultraviolet light, the EDTA is degraded and removed, and iron ions are dissociated in water; the ultraviolet light intensity range of the ultraviolet photolysis unit is 5mW/cm2～50mW/cm2；
S4, pH adjusting step: and (4) introducing the wastewater discharged in the step (S3) into a pH adjusting unit, adjusting the pH value of the wastewater to make the wastewater be alkaline with the pH value being more than or equal to 9, removing free iron ions and copper ions in the wastewater to finish the wastewater purification process, and discharging the purified water from a purified water outlet.
8. The method for treating the wastewater generated by degrading the Cu-EDTA by the electrocoagulation-coupled ultraviolet light as recited in claim 7, wherein: in step S4, the pH value of the wastewater is adjusted to be NaOH solution or other alkali liquor added into the wastewater.
9. The method for treating wastewater by degrading Cu-EDTA through electrocoagulation-coupled ultraviolet light as claimed in claim 7, further comprising the following steps:
s4.1, detecting the pollutant concentration of the purified water discharged in the step S4, and adjusting the water flow speed of the introduced wastewater: when the concentration of the pollutants in the purified water outlet is lower than the set standard, the flow rate of the introduced wastewater is increased, otherwise, the flow rate of the introduced wastewater is reduced, so that the pollutants have enough residence time in the electrolysis unit.
10. The method for treating wastewater by degrading Cu-EDTA through electrocoagulation-coupled ultraviolet light as claimed in claim 7, further comprising the following steps:
s2.1, adjusting the standing time of the standing precipitation unit: and detecting the turbidity of the wastewater at the water outlet of the standing and precipitating unit, increasing or decreasing the standing time according to the turbidity, if the turbidity of the wastewater at the water outlet is lower than a set standard, decreasing the standing time of the standing and precipitating unit, and if the turbidity of the wastewater at the water outlet is higher than the set standard, increasing the standing time of the standing and precipitating unit.
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