CN111018062B - Device for treating wastewater by adopting electrocoagulation coupled electrocatalytic oxidation and treatment method thereof - Google Patents
Device for treating wastewater by adopting electrocoagulation coupled electrocatalytic oxidation and treatment method thereof Download PDFInfo
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- CN111018062B CN111018062B CN201911085977.7A CN201911085977A CN111018062B CN 111018062 B CN111018062 B CN 111018062B CN 201911085977 A CN201911085977 A CN 201911085977A CN 111018062 B CN111018062 B CN 111018062B
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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
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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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
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a device for treating wastewater by adopting electrocoagulation-coupled electrocatalytic oxidation and a treatment method thereof, wherein the device comprises an electrocoagulation reactor formed by combining a cathode and an anode which are oppositely arranged and a plurality of rotatable filler bed devices arranged in the electrocoagulation reactor; the device comprises a packed bed device, a hollow bed layer rotating shaft, a packing bed layer electrode, a filler bed layer electrode and a filler bed layer electrode, wherein the packed bed device comprises a non-conductive packed bed, an aeration device arranged in the packed bed and a connecting pipe arranged at the center of the bottom end of the packed bed, the connecting pipe of the aeration device is connected into the hollow bed layer rotating shaft, and the packed bed layer electrode is filled with charged catalytic particle electrodes; the treatment method comprises the steps of adjusting the conductivity and the pH value of the wastewater to be treated, introducing the wastewater into an electrocoagulation reactor, starting a rotating shaft and an aeration device, performing electrocoagulation-electrocatalytic oxidation reaction, standing and centrifuging to obtain clear liquid. The invention can generate adsorption flocs in situ and superoxide anion free radicals and hydroxyl free radicals with strong oxidizing property in the process of treating the wastewater to treat the organic dye wastewater with long carbon chains.
Description
Technical Field
The invention belongs to the field of sewage treatment, and particularly relates to a device for treating wastewater by adopting electrocoagulation-electrocatalytic oxidation and a treatment method thereof.
Background
The electric flocculation is a novel waste water treatment technology. Under the action of an external electric field, soluble metal anode is electrolyzed to generate metal cations, and water in a cathode area is electrolyzed to generate H 2 And surface hydroxyl groups (. OH), the metal cations are combined with the surface hydroxyl groups in the electrolyte solution to form a series of mononuclear or polynuclear hydroxyl complexes and hydroxides, and hydroxide flocs with larger specific surface area and abundant surface hydroxyl groups are gradually formed. The wholeIn the electric flocculation process, part of small molecule pollutants with simple structures can directly get away electrons near the surface of an electrode so as to be degraded by oxidation reduction, but the degradation effect of the part is weaker in the whole system. In addition, the amount of strong oxidizing radicals such as hydroxyl radicals (. OH) generated in the process of electroflocculation is very limited, i.e., the high-grade oxidizing ability of the organic matters which are complex in structure and difficult to degrade is weak.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a device for treating wastewater by adopting electrocoagulation coupled electrocatalytic oxidation, which can improve the treatment efficiency of long carbon chain organic dye wastewater with complex components;
the second purpose of the invention is to provide a method for treating the wastewater.
The technical scheme is as follows: the invention relates to a device for treating wastewater by adopting electrocoagulation-electrocatalytic oxidation, which comprises an electrocoagulation reactor and a plurality of rotatable filler bed layer devices, wherein the electrocoagulation reactor is formed by combining a cathode and an anode which are arranged oppositely; wherein, the filler bed device comprises a non-conductive filler bed, an aeration device arranged in the filler bed and a connecting pipe arranged at the center of the bottom end of the filler bed, the connecting pipe of the aeration device is connected in by a hollow bed rotating shaft, the filler bed is filled with a charged catalytic particle electrode, and the electrocatalytic particle electrode is Fe @ C and SnO 2 A mixture of/Sb/Bi/Ni @ C.
The invention adds a rotatable filler bed layer device (namely a polarity changing device), periodically changes the polarity of the particle electrode, increases the catalytic area of the particle electrode, can relieve the passivation degree of the electrode surface, slows down the hardening rate of the particle electrode, generates hydroxyl free radical (OH) with stronger oxidation property on the particle electrode surface by water and hydroxyl ions in the electrolytic process, and forms high-activity superoxide anion free radical (O) on the particle electrode surface by ozone 2 - ) Thereby improving the degradation efficiency and reducing the energy consumption; oxygen can generate two-electron reduction reaction at the porous cathode to generate hydrogen peroxide (H) 2 O 2 ) The substance not only can promote superoxide anion free radical (O) 2 - ) With the generation of hydroxyl free radical (. OH), and has certain strong oxidizing property; and the polarity of the particle electrode is periodically changed, so that the short-circuit current in the system can be reduced.
Furthermore, the radius of the packed bed is 10-20 cm, the height of the packed bed is 20-100 cm, and the distance between the packed bed and the cathodes and the anodes on the two sides is 1-5 cm. Fe @ C and SnO 2 In the mixture of/Sb/Bi/Ni @ C, Fe @ C and SnO 2 The mass ratio of/Sb/Bi/Ni @ C is 1: 0.5-3. When the ionic pollutants in the treated wastewater sample are more, the Fe @ C in the filler proportion is more; when the treated waste water sample contains more organic pollutants and oxide pollutants, the SnO in the filler proportion 2 more/Sb/Bi/Ni @ C.
The method for treating the wastewater by adopting the device comprises the following steps: adjusting the conductivity and pH value of the wastewater to be treated, introducing the wastewater into an electrocoagulation reactor, starting a rotating shaft and an aeration device, treating the wastewater for 15-300 min through an electrocatalytic oxidation reaction of an electrocoagulation-packing bed device, and standing and centrifuging to obtain clear liquid.
The invention carries out electrocatalytic oxidation by coupling the electric flocculation with the polarity-variable particle electrode, wherein the electrocatalytic action of the particle electrode releases more floc auxiliary agent Fe 2+ 、Fe 3+ And OH; when organic macromolecular pollutants with long carbon chains (such as rhodamine b, chrome black T and the like) are treated, partial pollutants can be directly subjected to redox degradation, and hydroxyl free radicals (. OH) and superoxide anion free radicals (. O) are generated 2 - ) And the organic matters are degraded by the substances, and the longer carbon chain of the organic matters is broken, so that the flocs generated in the electric flocculation process are promoted to be efficiently coordinated and adsorbed.
Furthermore, the conductivity of the wastewater regulated by the method is 500-10000 us/cm, and the pH value is 4-9. The electrolytic current density of the electric flocculation is 0.5-25 mA/cm 2 . The rotating speed of the rotating shaft is 1-15 r/min.
Furthermore, the aeration rate of the aeration device adopted by the invention is 0.025-0.25L/min. The aeration treatment of the aeration device is carried out by introducing mixed gas of ozone and oxygen, wherein the concentration of the ozone is 0-500 mg/L. The invention is realized by the change of polarity particle electrode systemAerating mixed gas of ozone and oxygen with the ozone concentration of 0-500 mg/L, and catalyzing the ozone into superoxide anion free radicals (O) with higher activity through the catalytic action of a particle electrode 2 - ) Furthermore, superoxide anion radical can also increase the rate of conversion of hydroxyl radical (. OH).
Has the advantages that: compared with the prior art, the invention has the remarkable advantages that: through the device that carries out the coupling with electric flocculation and electrocatalytic oxygen, and then can produce in situ and adsorb floc and the hydroxyl free radical that has strong oxidizing property and handle long carbon chain's organic dye waste water in the in-process of handling waste water.
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention;
FIG. 2 is a top plan view of the apparatus of the present invention with a single packed bed;
FIG. 3 is a top plan view of the apparatus of the present invention with two packed bed units;
FIG. 4 is a top plan view of an apparatus of the present invention having four packed beds;
FIG. 5 is a schematic view of the apparatus of the present invention;
fig. 6 is a schematic view of the rotating shaft in fig. 2 rotated by 180 °.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and examples.
As shown in figure 1, the device for treating wastewater by adopting the electrocoagulation-coupled electrocatalytic oxidation comprises an electrocoagulation reactor formed by combining a cathode 1 and an anode 2 which are oppositely arranged and a plurality of rotatable filler bed devices arranged in the electrocoagulation reactor, wherein the number of the filler bed devices can be 1, 2 or 4, as shown in figures 2 to 4, the radius of the filler bed is 10-20 cm, the height of the filler bed is 20-100 cm, and the distance between the filler bed and the cathodes and the anodes at two sides is 1-5 cm; when a plurality of packing bed layer devices are arranged, the distance between every two adjacent packing beds is 4-6 cm. The anode plate can be a flat iron electrode, the cathode plate is a flat porous electrode material (such as foamed iron, foamed nickel and carbon felt), the thickness of the electrode plate is 3-5 mm, the length of the electrode plate is 250-900 mm, and the width of the electrode plate is 250-1050 mm.
The packed bed device comprises a non-conductive packed bed 3, an aeration device 4 arranged at the lower end of the packed bed and a hollow rotating shaft 5 arranged at the central position of the upper end of the packed bed, a connecting pipe of the aeration device 4 is connected into the hollow bed rotating shaft 5, the packed bed 3 is filled with a charged catalytic particle electrode, and the electrode of the charged catalytic particle is Fe @ C and SnO 2 the/Sb/Bi/Ni @ C mixture is commercially available.
The working principle is as follows: when the whole system works, the particle electrodes on the electro-catalytic particle electrode packing layer generate induced electromotive force in an external electric field, namely each particle electrode is equivalent to a micro-electrolysis cell, as shown in figures 5 and 6. Along with the rotation of the packing layer of the electrocatalytic particle electrode, the polarity of the particle electrode filled on the electrocatalytic particle electrode is changed, the passivation degree of the surface of the electrode is relieved, the hardening rate of the particle electrode is slowed down, the area of catalytic reaction is increased, and ozone not only forms high-activity superoxide anion free radicals (O) on the surface of the particle electrode in the electrolytic process 2 - ) And the generation of hydroxyl free radicals (OH) is promoted, so that the degradation efficiency is improved, and the energy consumption is reduced.
In the electric flocculation process, metal cation Fe is electrolyzed out by an anode 2+ Or Fe 3+ Cathodic electrolysis of H 2 And surface hydroxyl (. OH), metal cation Fe 2+ Or Fe 3+ With OH in the waste water to finally form Fe (OH) 2 、Fe(OH) 3 alpha-FeOOH, beta-FeOOH, gamma-FeOOH and other flocs; the particle electrode on the rotatable electrocatalytic particle electrode packing layer is subjected to electrolysis reaction, and not only can metal cation Fe be separated out by electrolysis 2+ And Fe 3+ And the flocculating auxiliary agent can also generate a large amount of substances with high oxidizing property such as hydroxyl free radicals and superoxide anion free radicals, and further degrade and adsorb organic pollutants.
The invention relates to a wastewater treatment method by electrocatalytic oxidation of an electrocoagulation-coupled variable polarity particle electrode, which comprises the following steps:
(1) pretreating the wastewater to be treated with Na 2 SO 4 As an electrolyte for waste water and conditioningThe conductivity is 500-10000 us/cm, and then the pH value of the waste water sample is adjusted to 4-9;
(2) determining the proportion of particle electrode filler, the rotating speed of a rotating particle electrode bed layer, the aeration rate, the ozone concentration of aeration treatment and the magnitude of electrolysis current density according to the type of pollutants in the wastewater;
(3) determining the number of the rotatable filler bed layer devices, determining the distance between a positive electrode plate and a negative electrode plate in the electrocoagulation reactor, performing electrocoagulation-electrocatalytic oxidation reaction treatment, performing synergistic aeration treatment in the treatment process, standing for 15-30 min after the reaction is finished, and performing centrifugation treatment for 5-10 min;
(4) after the treatment steps, the wastewater is subjected to removal rate and COD test.
Example 1
In this example, wastewater containing bisphenol A (BPA) was treated to a total concentration of 50 ppm; the specific treatment steps are as follows:
(1) with Na 2 SO 4 The electrolyte is used, the conductivity of the waste water is adjusted to 10000us/cm, and the pH value of a waste liquid sample is adjusted to 5;
(2) taking an iron electrode as an anode and a porous foam iron electrode as a cathode, wherein the distance between the two electrodes is 22cm, and the size of each electrode plate is 250mm multiplied by 3 mm; a cylindrical filler bed layer device is additionally arranged between the two electrodes, the radius of the cylindrical filler bed layer device is 10cm, and the height of the cylindrical filler bed layer device is 20 cm; electrocatalytic particle electrode packed on a packed bed Fe @ C: SnO 2 The ratio of/Sb/Bi/Ni @ C is 1:1, and the distance between the filler bed layer device and the electrodes on the two sides is 1 cm;
(3) setting the rotation speed of a rotating shaft of the filler bed layer device to be 5r/min, the ozone concentration to be 300mg/L, the aeration speed to be 0.15L/min and the current density of the electrolytic reaction to be 5mA/cm 2 Performing an electrocoagulation-electrocatalytic oxidation reaction for 100 min;
(4) and (3) standing the treated wastewater for 30min after the reaction is finished, and centrifuging for 5 min.
The treated wastewater was subjected to performance testing, and the test results are shown in table 1 below.
TABLE 1 parameters of example 1 and performance index of treated wastewater
| Performance of | Organic contaminant removal rate/%) | COD removal Rate/%) |
| Parameter(s) | 95.21 | 88.99 |
Comparative example 1
The comparative example is basically the same as the example 1, except that the electrocatalysis process is not coupled, namely a rotatable filler bed device is not additionally arranged between the cathode and the anode, and the specific treatment steps are as follows:
(1) with Na 2 SO 4 The electrolyte is used, the conductivity of the waste water is adjusted to 10000us/cm, and the pH value of a waste liquid sample is adjusted to 5;
(2) taking an iron electrode as an anode and a porous foam iron electrode as a cathode, wherein the size of an electrode plate is 250mm multiplied by 3mm, and the distance between the two electrodes is 5 cm;
(3) setting the ozone concentration at 300mg/L, the aeration rate at 0.15L/min, and the electrolytic current density at 2mA/cm 2 Carrying out electrolytic reaction for 30 min;
(4) and (3) standing the treated wastewater for 30min after the reaction is finished, and centrifuging for 5 min.
The wastewater treated by the comparative example was subjected to performance testing, and the testing results are shown in table 2 below.
TABLE 2 parameters of comparative example 1 and performance index of treated wastewater
| Performance of | Organic contaminant removal rate/%) | COD removal Rate/%) |
| Parameter(s) | 70.61 | 50.32 |
It can be known from the comprehensive table 1 and table 2 that when treating bisphenol A-containing wastewater, the removal rate of organic pollution and the COD degradation rate in the wastewater sample can be improved by additionally arranging a rotary particle electrode bed layer device coupled with an electrocatalytic oxidation technology in the process of electrocoagulation electrolysis. In example 1, a large number of hydroxyl radicals, superoxide anion radicals and other substances with strong oxidizing property are generated to break the molecular structure of a long carbon chain, and in addition, the particle electrode can not only electrocatalyze active groups, but also electrolyze more flocculation aids.
Example 2
In this example, Methyl Blue (MB) -containing wastewater was treated to a total concentration of 100 ppm; the specific treatment steps are as follows:
(1) with Na 2 SO 4 The electrolyte is used, the conductivity of the waste water is adjusted to be 6000us/cm, and the pH value of the waste liquid sample is adjusted to be 4;
(2) taking an iron electrode as an anode and a porous foam iron electrode as a cathode, wherein the distance between the two electrodes is 45cm, and the size of each electrode plate is 850mm multiplied by 1050mm multiplied by 5 mm; two cylindrical packing bed layers are additionally arranged between the two electrodes, the radius of the packing bed is 20cm, and the height of the packing bed is 100 cm; electrocatalytic particle electrode filler Fe @ C SnO filled on filler bed 2 The ratio of/Sb/Bi/Ni @ C is 1:2, the distance between the filler bed layer devices and the electrodes on the two sides is 5cm, and the distance between the two filler bed layer devices is 4cm；
(3) Setting the rotation speed of the filler bed layer device to be 10r/min, the ozone concentration to be 400mg/L, the aeration speed to be 0.25L/min and the current density of the electrolytic reaction to be 10mA/cm 2 Performing an electric flocculation-electrocatalytic oxidation reaction for 200 min;
(4) and (3) standing the treated wastewater for 20min after the reaction is finished, and centrifuging for 10 min.
The treated wastewater was subjected to performance testing, and the test results are shown in table 3 below.
TABLE 3 parameters of example 2 and performance index of treated wastewater
| Performance of | Decolorization rate/%) | COD removal Rate/%) |
| Parameter(s) | 92.86 | 89.32 |
Comparative example 2
This comparative example is essentially the same as example 2, except that the rotatable packing bed apparatus has a rotational speed of 0 and the specific treatment steps are as follows:
(1) with Na 2 SO 4 The electrolyte is used, the conductivity of the waste water is adjusted to be 6000us/cm, and the pH value of the waste liquid sample is adjusted to be 4;
(2) taking an iron electrode as an anode and a porous foam iron electrode as a cathode, wherein the size of an electrode plate is 850mm multiplied by 1050mm multiplied by 5mm, and the distance between the two electrodes is 45 cm; two cylindrical packing bed layer devices are additionally arranged between the two electrodes, the radius of the packing bed is 20cm, and the height of the packing bed is 100 cm; electrocatalytic particles packed on packed bedElectrode filler Fe @ C SnO 2 The ratio of/Sb/Bi/Ni @ C is 1:2, the distance between the filler bed layer devices and the electrodes on the two sides is 5cm, and the distance between the two filler bed layer devices is 4 cm;
(3) setting the ozone concentration to 400mg/L, the aeration rate to 0.25L/min and the current density of the electrolytic reaction to 10mA/cm 2 Performing an electric flocculation-electrocatalytic oxidation reaction for 200 min;
(4) and (3) standing the treated wastewater for 20min after the reaction is finished, and centrifuging for 10 min.
The wastewater treated by the comparative example was subjected to performance testing, and the testing results are shown in table 4 below.
TABLE 4 parameters of comparative example 2 and performance index of treated wastewater
| Performance of | Decolorization ratio/% | COD removal Rate/%) |
| Parameter(s) | 79.16 | 78.32 |
It can be seen from the combination of tables 3 and 4 that, when the methyl blue-containing wastewater is treated, under the same other conditions, the removal rate is significantly improved when the rotational speed of the rotatable packing bed is 10r/min compared with that when the rotational speed is 0. The polarity of the particle electrode is reversed along with the rotation of the filler bed layer device, so that the passivation degree and the hardening degree of the particle working electrode of the whole system are relieved, the current efficiency is improved, and the removal rate is improved.
Example 3
In the embodiment, Methyl Orange (MO) wastewater is treated, and the total concentration of the wastewater is 600 ppm; the specific treatment steps are as follows:
(1) with Na 2 SO 4 The electrolyte is used, the conductivity of the waste water is adjusted to 10000us/cm, and the pH value of the waste liquid sample is adjusted to 9;
(2) taking an iron electrode as an anode and a porous foam iron electrode as a cathode, wherein the distance between the two electrodes is 100cm, and the size of each electrode plate is 900mm multiplied by 800mm multiplied by 4 mm; four cylindrical packing bed layers are additionally arranged between the two electrodes, the radius of the packing bed is 20cm, and the height of the packing bed is 75 cm; electrocatalytic particle electrode filler Fe @ C SnO filled on filler bed 2 The ratio of/Sb/Bi/Ni @ C is 1: 3; the distance between the filler bed layer devices and the electrodes on the two sides is 4cm, and the distance between the filler bed layer devices is 6 cm;
(3) setting the rotation speed of the filler bed layer device to be 15r/min, the ozone concentration to be 500mg/L, the aeration speed to be 0.25L/min and the current density of the electrolytic reaction to be 25mA/cm 2 Performing electric flocculation-electrocatalytic oxidation reaction for 15 min;
(4) and (3) standing the treated wastewater for 15min after the reaction is finished, and centrifuging for 5 min.
The treated wastewater was subjected to performance testing, and the test results are shown in table 5 below.
TABLE 5 parameters of example 3 and performance index of treated wastewater
| Performance of | Decolorization ratio/% | COD removal Rate/% |
| Parameter(s) | 93.21 | 82.99 |
Example 4
This example is substantially the same as example 3 except that the aeration rate of the ozone-oxygen mixed gas is different. The specific treatment steps are as follows:
(1) with Na 2 SO 4 The electrolyte is used, the conductivity of the waste water is adjusted to 10000us/cm, and the pH value of the waste liquid sample is adjusted to 9;
(2) taking an iron electrode as an anode and a porous foam iron electrode as a cathode, wherein the distance between the two electrodes is 100cm, and the size of each electrode plate is 900mm multiplied by 800mm multiplied by 4 mm; four cylindrical packing bed layers are additionally arranged between the two electrodes, the radius of the packing bed is 20cm, and the height of the packing bed is 75 cm; electrocatalytic particle electrode filler Fe @ C SnO filled on filler bed 2 The ratio of/Sb/Bi/Ni @ C is 1: 3; the distance between the filler bed layer devices and the electrodes on the two sides is 4cm, and the distance between the filler bed layer devices is 6 cm;
(3) setting the rotation speed of the filler bed device to be 15 r/min; the concentration of ozone is 500 mg/L; the aeration rate is 0.025L/min, and the current density of the electrolytic reaction is 25mA/cm 2 Performing electric flocculation-electrocatalytic oxidation reaction for 15 min;
(4) and (3) standing the treated wastewater for 15min after the reaction is finished, and centrifuging for 5 min.
The wastewater treated in this example was subjected to performance tests, and the test results are shown in table 6 below.
TABLE 6 parameters of example 4 and performance index of treated wastewater
As can be seen from a combination of tables 5 and 6, the difference in aeration rate under otherwise identical conditions means that the amount of ozone in the system is different, and the yield of superoxide radicals formed by electrolysis is different, i.e., the amount of highly oxidative active radicals in the entire system is different. The results of the two experiments will differ under the same conditions.
Example 5
In the embodiment, the rhodamine B (RhB) wastewater is treated, and the total concentration of the wastewater is 50 ppm; the specific treatment steps are as follows:
(1) with Na 2 SO 4 The electrolyte is used, the conductivity of the waste water is adjusted to 4000us/cm, and the pH value of a waste liquid sample is adjusted to 6;
(2) taking an iron electrode as an anode and a carbon felt electrode as a cathode, wherein the distance between the two electrodes is 73cm, and the size of each electrode plate is 700mm multiplied by 600mm multiplied by 4 mm; four cylindrical packing bed layers are additionally arranged between the two electrodes, the radius of the packing bed is 15cm, and the height of the packing bed is 55 cm; electrocatalytic particle electrode filler Fe @ C SnO filled on filler bed 2 The ratio of/Sb/Bi/Ni @ C is 1: 3; the distance between the filler bed layer devices and the electrodes on the two sides is 4cm, and the distance between the filler bed layer devices is 5 cm;
(3) setting the rotation speed of a filler bed layer device to be 15r/min, the ozone concentration to be 450mg/L, the aeration speed to be 0.15L/min and the current density of electrolytic reaction to be 20mA/cm 2 Performing an electrocoagulation-electrocatalytic oxidation reaction for 300 min;
(4) and (4) standing the treated wastewater for 25min after the reaction is finished, and centrifuging for 8 min.
The treated wastewater was subjected to performance testing, and the test results are shown in table 7 below.
TABLE 7 parameters of example 5 and indexes of treated wastewater
| Performance of | Decolorization ratio/% | COD removal Rate/%) |
| Parameter(s) | 96.65 | 90.56 |
Example 6
The procedure of this example is essentially the same as example 5, except that the rotatable packing bed apparatus has a packing ratio of Fe @ C: SnO 2 The ratio of/Sb/Bi/Ni @ Ti @ C is 1:1, and the specific treatment steps are as follows:
(1) with Na 2 SO 4 The electrolyte is used, the conductivity of the waste water is adjusted to 2000us/cm, and the pH value of a waste liquid sample is adjusted to 6;
(2) taking an iron electrode as an anode and a carbon felt electrode as a cathode, wherein the distance between the two electrodes is 73cm, and the sizes of the electrode plates are 700mm multiplied by 600mm multiplied by 4 mm; four cylindrical packing bed devices are additionally arranged between the two electrodes, the radius of each cylindrical packing bed device is 15cm, and the height of each cylindrical packing bed device is 55 cm; electrocatalytic particle electrode packing packed on a packed bed Fe @ C: SnO 2 The ratio of/Sb/Bi/Ni @ C is 1: 1; the distance between the filler bed layer devices and the electrodes on the two sides is 4cm, and the distance between the filler bed layer devices is 5 cm;
(3) setting the rotation speed of a filler bed layer device to be 15r/min, the ozone concentration to be 450mg/L, the aeration speed to be 0.15L/min and the current density of electrolytic reaction to be 20mA/cm 2 Performing an electrocoagulation-electrocatalytic oxidation reaction for 300 min;
(4) and (4) standing the treated wastewater for 25min after the reaction is finished, and centrifuging for 8 min.
The treated wastewater was subjected to performance testing, and the test results are shown in table 8 below.
TABLE 8 parameters and performance index of treated wastewater of example 6
| Performance of | Decolorization ratio/% | COD removal Rate/%) |
| Parameter(s) | 90.98 | 85.82 |
From a combination of tables 7 and 8, it can be seen that SnO 2 When the ratio of the filler/Sb/Bi/Ni @ Ti @ C is increased, hydroxyl radical OH and superoxide anion radical (. O) can be generated 2 - ) The oxidant degrades complex organic matters and breaks long and complex carbon chains, which is very beneficial to the coordination and adsorption of flocs generated by electric flocculation and pollutants with short carbon chains and simple structures, thereby improving the decolorization rate and the removal rate of the wastewater.
Example 7
In the embodiment, the chrome black T (EBT) wastewater is treated, and the total concentration of the wastewater is 100 ppm; the specific treatment steps are as follows:
(1) with Na 2 SO 4 The electrolyte is used, the conductivity of the waste water is adjusted to 2000us/cm, and the pH value of the waste liquid sample is adjusted to 5;
(2) taking an iron electrode as an anode and a porous foamed nickel electrode as a cathode, wherein the distance between the two electrodes is 28cm, and the size of each electrode plate is 500mm multiplied by 350mm multiplied by 4 mm; two cylindrical packing bed layer devices are additionally arranged between the two electrodes, the radius of the cylindrical packing bed layer devices is 10cm, and the height of the cylindrical packing bed layer devices is 30 cm; electrocatalytic particle electrode filler Fe @ C SnO filled on filler bed 2 The ratio of/Sb/Bi/Ni @ C is 1: 3; the distance between the filler bed layer devices and the electrodes on the two sides is 4cm, and the distance between the filler bed layer devices is 4 cm;
(3) setting the rotation speed of the filler bed layer device to be 15r/min, the ozone concentration to be 350mg/L, the aeration speed to be 0.15L/min and the current density of the electrolytic reaction to be 0.5mA/cm 2 Performing an electrocoagulation-electrocatalytic oxidation reaction for 300 min;
(4) and (4) standing the treated wastewater for 25min after the reaction is finished, and centrifuging for 8 min.
The treated wastewater was subjected to performance testing, and the test results are shown in table 9 below.
TABLE 9 parameters and treated wastewater Performance indicators for example 7
| Performance of | Decolorization ratio/% | COD removal Rate/% |
| Parameter(s) | 95.87 | 88.56 |
Example 8
The procedure of this example was substantially the same as in example 7 except that the rotatable packed bed unit was rotated at a rate of 1 r/mim; the specific treatment steps are as follows:
(1) with Na 2 SO 4 The electrolyte is used, the conductivity of the waste water is adjusted to 2000us/cm, and the pH value of the waste liquid sample is adjusted to 5;
(2) taking an iron electrode as an anode and a porous foamed nickel electrode as a cathode, wherein the distance between the two electrodes is 28cm, and the size of each electrode plate is 500mm multiplied by 350mm multiplied by 4 mm; two cylindrical packing bed layer devices are additionally arranged between the two electrodes, the radius of the cylindrical packing bed layer devices is 10cm, and the height of the cylindrical packing bed layer devices is 30 cm; electrocatalytic particle electrode filler Fe @ C SnO filled on filler bed 2 The ratio of/Sb/Bi/Ni @ C is 1: 3; the distance between the filler bed layer devices and the electrodes on the two sides is 4cm, and the distance between the filler bed layer devices is 4 cm;
(3) setting the rotation speed of the filler bed layer device to be 1r/min, the ozone concentration to be 350mg/L, the aeration speed to be 0.15L/min and the current density of the electrolytic reaction0.5mA/cm 2 Performing an electrocoagulation-electrocatalytic oxidation reaction for 300 min;
(4) and (4) standing the treated wastewater for 25min after the reaction is finished, and centrifuging for 8 min.
The treated wastewater was subjected to performance tests, and the test results are shown in table 10 below.
TABLE 10 parameters of example 8 and indexes of treated wastewater
| Performance of | Decolorization ratio/% | COD removal Rate/%) |
| Parameter(s) | 88.91 | 80.56 |
It can be seen from a combination of tables 9 and 10 that the rotational speed of the rotatable packing bed is too slow to facilitate contaminant removal. The rotation speed is too slow, namely the stirring effect of the whole system is weakened, the pollutants can not be fully contacted with the surface of the particle electrode, and the electron transfer is weakened; the dissolved amount of ozone in the system can be increased by a certain rotating speed, so that the particle electrodes are more fully contacted with ozone and oxygen, and more OH and O are generated 2 - And the like.
Example 9
In this embodiment, the treatment of phosphite (phosphite) containing wastewater with an initial concentration of 0.5mol/L includes the following steps:
(1) adjusting the conductivity of the wastewater to 500us/cm, and adjusting the pH value of the wastewater sample to 7;
(2) using an iron electrode asThe anode and the porous foam iron electrode are used as the cathode, the distance between the two electrodes is 26cm, and the size of the electrode plate is 250mm multiplied by 3 mm; a cylindrical filler bed layer device is additionally arranged between the two electrodes, the radius of the cylindrical filler bed layer device is 10cm, and the height of the cylindrical filler bed layer device is 20 cm; electrocatalytic particle electrode filler Fe @ C SnO filled on filler bed 2 The ratio of/Sb/Bi/Ni @ C is 1: 1; the distance between the bed layer and the polar plate is 3 cm;
(3) setting the rotation speed of the filler bed layer device to be 5r/min, the ozone concentration to be 400mg/L, the aeration speed to be 0.1L/min and the current density of the electrolytic reaction to be 5mA/cm 2 Performing an electric flocculation-electrocatalytic oxidation reaction for 100 min;
(4) and (3) standing the treated wastewater for 30min after the reaction is finished, and centrifuging for 5 min.
The treated wastewater was subjected to performance testing, and the test results are shown in table 11 below.
TABLE 11 parameters and performance indices of treated wastewater of example 9
| Performance of | TP removal Rate/%) |
| Parameter(s) | 90.23 |
Example 10
The procedure of this example was substantially the same as in example 9 except that the ozone concentration of the aerated mixed gas was 0; the specific treatment steps are as follows:
(1) adjusting the conductivity of the wastewater to 500us/cm, and adjusting the pH value of the wastewater sample to 7;
(2) taking an iron electrode as an anode and a porous foam iron electrode as a cathode, wherein the distance between the two electrodes is 26cm, and the size of an electrode plate is 250mm multiplied by 3 mm; a cylindrical filler is additionally arranged between the two electrodesThe radius of the bed layer device is 10cm, and the height of the bed layer device is 20 cm; electrocatalytic particle electrode filler Fe @ C SnO filled on filler bed 2 The ratio of/Sb/Bi/Ni @ C is 1: 1; the distance between the bed layer and the polar plate is 3 cm;
(3) setting the rotation speed of the filler bed layer device to be 5r/min, the ozone concentration to be 0, the aeration speed to be 0.1L/min and the current density of the electrolytic reaction to be 5mA/cm 2 Performing an electric flocculation-electrocatalytic oxidation reaction for 100 min;
(4) and (3) standing the treated wastewater for 30min after the reaction is finished, and centrifuging for 5 min.
The treated wastewater was subjected to performance tests, and the test results are shown in table 12 below.
TABLE 12 parameters of example 10 and performance index of treated wastewater
| Performance of | TP removal Rate/%) |
| Parameter(s) | 66.13 |
From a review of tables 11 and 12, it can be seen that when treating ionic contaminants such as phosphite, more free radicals are required to oxidize the ionic contaminants into floc-adsorbed phosphates, i.e., ozone is required to generate superoxide anion radicals (. O) 2 - ) And assists in accelerating the production of hydroxyl radicals (. OH), the key to the overall phosphorus removal in the treatment of phosphite is the amount of phosphite oxidized.
In addition to the above examples, the SnO of the present invention 2 SnO in/Sb/Bi/Ni @ C particulate electrode Filler 2 The mass ratio of Sb to Bi to Ni is 12:1:1.5:1: 0.5. Aeration devices are known in the art.
Claims (8)
1. The utility model provides an adopt device of electric flocculation coupling electrocatalytic oxidation treatment waste water which characterized in that: the device comprises an electric flocculation reactor formed by combining a cathode and an anode which are oppositely arranged, and a plurality of rotatable filler bed layer devices which are arranged in the electric flocculation reactor and are used for periodically changing the polarity of particle electrodes; wherein, the packed bed device comprises a non-conductive packed bed, an aeration device arranged at the lower end of the packed bed and a rotating shaft arranged at the central position of the packed bed, the packed bed is filled with a charge catalytic particle electrode which is Fe @ C and SnO 2 Mixture of/Sb/Bi/Ni @ C, Fe @ C and SnO 2 The mass ratio of/Sb/Bi/Ni @ C is 1: 0.5-3.
2. The apparatus for treating wastewater by coupling electric flocculation and electrocatalytic oxidation as set forth in claim 1, wherein: the radius of the packed bed is 10-20 cm, the height of the packed bed is 20-100 cm, and the distance between the packed bed and the cathodes and the anodes on the two sides is 1-5 cm.
3. A method of treating wastewater using the apparatus of claim 1, comprising the steps of: adjusting the conductivity and pH value of the wastewater to be treated, introducing the wastewater into an electrocoagulation reactor, starting a rotating shaft and an aeration device, treating the wastewater for 15-300 min through an electrocatalytic oxidation reaction of an electrocoagulation-packing bed device, and standing and centrifuging to obtain clear liquid.
4. A method for treating wastewater according to claim 3, wherein: the electrolytic current density of the electric flocculation is 0.5-25 mA/cm 2 。
5. A method for treating wastewater according to claim 3, wherein: the rotating speed of the rotating shaft is 1-15 r/min.
6. A method for treating wastewater according to claim 3, wherein: the aeration rate of the aeration device is 0.025-0.25L/min.
7. The method of treating wastewater according to claim 6, wherein: the aeration treatment of the aeration device is carried out by introducing mixed gas of ozone and oxygen, and the concentration of the ozone is 0-500 mg/L.
8. A method for treating wastewater according to claim 3, wherein: the adjusted conductivity is 500-10000 us/cm, and the pH value is 4-9.
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| CN104709978A (en) * | 2015-02-12 | 2015-06-17 | 北京工商大学 | Rotary cage net type electric flocculation reactor |
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| CN104709978A (en) * | 2015-02-12 | 2015-06-17 | 北京工商大学 | Rotary cage net type electric flocculation reactor |
| CN104787941A (en) * | 2015-04-07 | 2015-07-22 | 凯天环保科技股份有限公司 | Advanced oxidative coupling device and process for treating organic wastewater difficult to degrade |
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