CN108585129B - Three-dimensional electrode wastewater treatment method and equipment with recovery function - Google Patents
Three-dimensional electrode wastewater treatment method and equipment with recovery function Download PDFInfo
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- CN108585129B CN108585129B CN201810714591.7A CN201810714591A CN108585129B CN 108585129 B CN108585129 B CN 108585129B CN 201810714591 A CN201810714591 A CN 201810714591A CN 108585129 B CN108585129 B CN 108585129B
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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
- C02F1/46109—Electrodes
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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
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4619—Supplying gas to the electrolyte
Abstract
Have recovery functionA three-dimensional electrode wastewater treatment method and equipment comprise particle electrode preparation, a three-dimensional electrode electrolysis device and a magnet recovery device. Preparing large-particle nano-scale Pt-SnO 2 /Fe 3 O 4 Particle electrodes. Pt-SnO 2 /Fe 3 O 4 The particle electrode has the characteristics of large specific surface area, high catalytic performance, good conductivity, convenient recycling of the magnet with strong magnetic performance and the like. By Pt-SnO 2 /Fe 3 O 4 The three-dimensional electrode electrolytic device of the particle electrode has simple process and strong oxidizing capability, and the guide cylinder and the aeration device improve the overall operation efficiency, so that the treated wastewater is discharged after reaching the standard. The magnetic groove position distribution in the magnetic recovery device has obvious effect, convenient recovery and high recovery rate, and the recovery rate of the particle electrode is more than or equal to 99.0 percent.
Description
Technical Field
The invention relates to a three-dimensional electrode wastewater treatment method and equipment with a recovery function, and belongs to the technical field of industrial wastewater advanced treatment.
Background
Along with the growth of industry and the acceleration of urban process, the pollution to water body is more and more serious, especially the chemical wastewater discharged in the production process of chemical industry has complex water quality components and more byproducts, the wastewater treatment does not reach the standard, the reaction raw materials are often solvent substances or compounds with annular structures, and the wastewater treatment difficulty is increased. Incomplete reaction of chemical raw materials or the use of a large amount of solvent in production into a wastewater system results in high pollutant content in wastewater. In addition, many organic pollutants in fine chemical wastewater are toxic and harmful to organisms, such as halogen compounds, nitro compounds, dispersing agents or surfactants with bactericidal effect and the like, which are harmful to human health. Meanwhile, the problems of more substances which are difficult to degrade in the wastewater, low B/C, poor biodegradability, high wastewater chromaticity and the like are also the problems to be solved in the water treatment process.
In the research process of industrial wastewater treatment, the current general attention is paid to the primary treatment by utilizing a sewage treatment field, and the conventional water treatment methods, such as a physical method, a physicochemical method, a biological treatment method and the like, have poor treatment effect on the refractory wastewater. The electrochemical oxidation method is a process of degrading pollutants in wastewater through a series of physicochemical reactions in a specific electrochemical reactor, wherein organic matters are changed into inorganic matters, and toxic and harmful matters are changed into non-toxic and harmless matters. The method is characterized by simple equipment, convenient maintenance, high catalytic efficiency, no secondary pollution, no need of external reagent addition, small influence by temperature and the like, and is known as an environment-friendly technology. The research on the electrocatalytic advanced treatment of wastewater is favorable for advanced treatment of wastewater pollution, and has very strong practical significance. The three-dimensional electrode is developed on the basis of the two-dimensional electrode, and the third electrode, namely the particle electrode, is added on the basis of the two-dimensional electrode, so that the wastewater treatment efficiency is improved. The two-dimensional electrode or the three-dimensional electrode electrocatalytic oxidation method plays an important role in treating wastewater, but has no simulation device of a system and corresponding matched equipment, and the catalytic performance of the anode plate and the particle electrode is unstable, so that the wastewater treatment efficiency is low, and the treatment requirement on organic pollutants cannot be met. And the powdery particle electrode is not easy to recycle after being used, so that the material cost is increased, and the resource is wasted.
Disclosure of Invention
The invention discloses a three-dimensional electrode wastewater treatment method and equipment with a particle electrode recycling function, aiming at solving the problems of high cost, difficult degradation of organic matters, complex process, large occupied area of a treatment device, secondary pollution, additional addition of an oxide medicament, unstable catalytic performance of a common three-dimensional electrode material, low wastewater treatment efficiency, difficult recovery and the like existing in the existing industrial wastewater treatment technology.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a particle electrode suitable for industrial wastewater treatment is characterized in that the overall structure of the particle electrode is Pt-SnO 2 /Fe 3 O 4 The carrier is Fe 3 O 4 In Fe 3 O 4 The carrier is provided with active ingredient SnO 2 And Pt, wherein the mole fraction content of each component is Fe:35-93%, sn:6.2-58%, pt:0.8-7%; the preparation process adopts a three-step method: fe (Fe) 3 O 4 Is prepared from SnO 2 /Fe 3 O 4 Preparation of (C) Pt-SnO 2 /Fe 3 O 4 Is prepared by the following steps.
The specific preparation process of the particle electrode comprises the following steps:
Fe 3 O 4 is prepared from the following steps: preparing 50% hydrazine hydrate, 0.5mol/L ferrous sulfate solution, 5mol/L sodium hydroxide solution and ethylene glycol into a mixed solution according to a volume ratio of 2:2:1:20, then placing the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a volume of 80-500 ml, placing the hydrothermal reaction kettle into a muffle furnace for treatment at 200 ℃ for 24 hours, cooling, washing the hydrothermal reaction kettle with distilled water until the pH value is 7, and finally drying the hydrothermal reaction kettle in a vacuum drying oven at 40 ℃ for 6 hours to obtain large-particle magnetic Fe 3 O 4 Hexahedral nanoparticles as carriers.
SnO 2 /Fe 3 O 4 Is prepared from the following steps: dissolving tin chloride in glycol and deionized water in a volume ratio of 1:1 to prepare a solution A; preparing 2.5 mol/L sodium hydroxide solution as solution B, slowly adding the solution B into the solution A until white suspension appears, and then adding Fe prepared by the method 3 O 4 The carrier is stirred uniformly and then dispersed by ultrasonic, then the carrier is moved into a reaction kettle to be heated for 12 hours at 180 ℃, cooled and washed, finally dried for 4 hours in a vacuum drying oven at 60 ℃ to obtain the nano-scale metal composite oxidationSnO as a material 2 /Fe 3 O 4 The mole fraction content of each component of the particles is Fe:37.5-93.75%, sn:6.25-62.5%. .
Pt-SnO 2 /Fe 3 O 4 Is prepared from the following steps: preparing chloroplatinic acid and SnO with ice water (less than 5 ℃) 2 /Fe 3 O 4 The mixed solution with the molar ratio of 1:8 is dispersed for 30-50min by ultrasonic; preparing 0.1mol/L sodium borohydride solution by using ice water, and then adjusting the pH value of the sodium borohydride solution to be 12 by using 0.5mol/L NaOH solution, so as to prepare the sodium borohydride solution for use at present; slowly adding chloroplatinic acid and SnO into sodium borohydride solution under stirring 2 /Fe 3 O 4 Mixing the solution to obtain a mixture, placing the mixture in an ice bath for 3 hours, centrifuging the precipitate, washing the precipitate with ultrapure water and ethanol, drying the precipitate in a vacuum drying oven at 80 ℃ for 6 hours, and loading a high-activity noble metal catalyst Pt to SnO, wherein the molar ratio of sodium borohydride to chloroplatinic acid is 1:2 2 /Fe 3 O 4 On the surface, pt-SnO is prepared 2 /Fe 3 O 4 Particle electrodes.
The Pt-SnO 2 /Fe 3 O 4 The particle electrode is hexahedral nano particles with magnetism, and the particle size is between 500 and 800 nm; snO (SnO) 2 And Pt as active components, are uniformly and firmly inlaid in Fe by means of Van der Waals force and mechanical force 3 O 4 On carrier particles; by adjusting the addition amount of each reactant, pt-SnO with different loading amounts can be prepared 2 /Fe 3 O 4 Particle electrodes.
A three-dimensional electrode wastewater treatment method with a recovery function by adopting the particle electrode is characterized in that firstly, the three-dimensional electrode is adopted to electrolyze industrial wastewater, then, a magnet is utilized to adsorb the particle electrode in the electrolyzed industrial wastewater, and the particle electrode is recovered and recycled.
The equipment for implementing the three-dimensional electrode wastewater treatment method with the recovery function is characterized by comprising a three-dimensional electrode electrolysis device and a magnet recovery device, wherein the output end of the three-dimensional electrode electrolysis device is connected with the input end of the magnet recovery device.
The three-dimensional electrode electrolysis device consists of an electrolysis bath and an electrolysis bath cover plate arranged at the top of the electrolysis bath, wherein the electrolysis bath comprises a bath body, and a water sample inlet and a water injection pump are arranged at the upper part of the bath body; the lower part of the tank body is provided with a sampling valve, an electrolytic tank water outlet and an aeration device; an anode titanium rod, an anode plate, a cathode titanium rod and a cathode plate are arranged in the tank body, the upper end of the anode titanium rod and the upper end of the cathode titanium rod penetrate through the electrolytic tank cover plate and are respectively connected with the anode and the cathode of an electrolytic power supply, the lower part of the anode titanium rod is connected with the anode plate, and the lower part of the cathode titanium rod is connected with the cathode plate; a guide cylinder is arranged between the anode plate and the cathode plate, and water flow channels are reserved at the upper end and the lower end of the guide cylinder; an exhaust valve and a dosing port are arranged on the cover plate of the electrolytic tank.
The magnet recovery device comprises a recovery tank and a recovery cover plate arranged at the top end of the recovery tank, wherein the bottom of one side of the recovery tank is provided with a recovery tank inlet and is connected with a water outlet of the electrolytic tank through a transition pipe and a transition valve, and the upper part of the other side of the recovery tank is provided with a water sample outlet; the recovery cover plate is provided with a plurality of downwardly extending magnet grooves, and magnets are placed in the magnet grooves.
The recovery tank is made of transparent glass, and the recovery cover plate is made of PC polycarbonate; the recovery groove is cuboid, the number of the magnet grooves arranged on the recovery cover plate is three, two magnet grooves are symmetrically arranged near the inlet of the recovery groove, and the positions of the two magnets N, S are opposite, so that most of particle electrodes can be adsorbed; a magnet groove is arranged on the water sample outlet accessory to adsorb the residual particle electrode, so that a small amount of particle electrode is prevented from losing.
The invention has the advantages that: by adopting the novel advanced wastewater treatment method, the time for treating industrial wastewater is shortened, the degradation efficiency is improved, and the nano-scale large-particle Pt-SnO with high magnetism and high catalytic oxidation performance is prepared 2 /Fe 3 O 4 Particle electrodes. The three-dimensional electrode electrocatalytic oxidation method for treating wastewater has the advantages of thorough oxidation treatment, no secondary pollution, simple equipment operation, high running efficiency, simple and convenient particle electrode recovery, high recovery rate, and low cost due to the cyclic utilization of the particle electrode, and the wastewater deeply treated by the industrial wastewater treatment system meets the discharge of industrial wastewaterRequirements.
The invention can carry out advanced treatment on the wastewater and has a recovery function. By Pt-SnO 2 /Fe 3 O 4 The three-dimensional electrode electrolysis device of the particle electrode has simple process, no oxide medicament is required to be added, the oxidation is thorough, no secondary pollution is caused, the treated wastewater can reach the discharge standard, the operation efficiency is high, and the degradation efficiency is improved; the particle electrode recovery device has the characteristics of simplicity, convenience, high recovery rate and the like. Therefore, the method has excellent application prospect in the advanced treatment of industrial wastewater and the treatment of organic wastewater difficult to biodegrade.
Pt-SnO prepared by the invention 2 /Fe 3 O 4 The particle electrode has the characteristics of large specific surface area, high catalytic performance, good conductivity, strong magnetism and the like. Fe (Fe) 3 O 4 The carrier not only serves as a carrier to provide an adhesion area of the active material, but also serves as an active material, and similar to the Fenton reaction, the OH is rapidly generated to be extremely strong in oxidizing property and participates in the electrocatalytic reaction. SnO (SnO) 2 Is a semiconductor composite metal oxide, has high oxygen evolution potential and good conductivity, and is SnO 2 The semiconductor solid solution has certain crystal defects, and more empty points and active points are formed on the surface of the carrier, so that more oxidative crystal oxygen is generated. The addition of noble metal Pt not only can directly catalyze oxide and accelerate O 2 And H 2 Generation of H 2 O 2 But also promote the generation of reducing hydrogen to reduce trivalent ferrotitanium ions in the carrier into Fe 2+ Accelerating Fenton reaction to generate more OH. Pt-SnO 2 /Fe 3 O 4 The particle electrode can generate a large amount of OH to catalyze, oxidize and degrade wastewater, and the characteristic of high magnetism is convenient to recycle after being recovered by a magnet.
The three-dimensional electrode electrolytic device consists of an electrolytic tank and an electrolytic tank cover plate, wherein the electrolytic tank is made of transparent glass material, and the cover plate is made of PC polycarbonate material; the recovery tank in the magnet recovery device adopts transparent glass material, and the apron adopts the PC polycarbonate material, adopts transparent glass material, PC polycarbonate material, guarantees intensity, high temperature resistant corrosion-resistant, and chemical stability is good, and the device is lighter, and transparent glass material, PC polycarbonate material also more conveniently observe the inside behavior of reactor simultaneously.
The upper opening of the guide cylinder is favorable for circulation to two sides, the lower cylindrical cylinder is stable and firm, the four aeration holes of the aeration device are all positioned at the lower side of the inner diameter of the guide cylinder, and gas can be completely introduced into the guide cylinder for central-circumferential circulation flow guiding, so that the particle electrode and the wastewater are fully mixed.
The magnet recovery cover plate consists of three cylindrical magnet grooves, two long magnet grooves are arranged at the inlet of the near transition pipe and are symmetrically arranged, the two magnets N, S are oppositely arranged, so that the adsorption of large-department particle electrodes is facilitated, a short magnet groove is arranged at the outlet of the near water sample, the residual particle electrodes are adsorbed, and the loss of a small amount of particle electrodes is avoided. The particle electrodes are adsorbed on the magnet groove, finally, the magnet recovery cover plate is taken out, and after the magnet is taken out, the particle electrodes automatically fall off and are collected, and more than 99% of the particle electrodes can be recovered.
The invention is based on the preparation of Pt-SnO with high magnetism and high catalytic performance 2 /Fe 3 O 4 The particle electrode assembles a three-dimensional electrode system. In the process of electrocatalytic oxidation of wastewater by using a three-dimensional electrode, a large amount of high-oxidability OH is generated by direct oxidation and indirect oxidation of an anode and high-catalytic oxidation of a particle electrode to oxidize refractory organic matters in the wastewater, so that the wastewater is discharged up to the standard, the oxidizing capacity is extremely high, the wastewater treatment time is short, and the efficiency is high. And (5) recycling the particle electrode after the wastewater is subjected to electrolysis treatment by using a magnet. The electrolysis device has simple operation, high running efficiency, simple and convenient recovery device and high recovery rate.
The COD after treatment is less than or equal to 35mg/L and BOD by the treatment method 5 15mg/L or less, 30mg/L or less TSS, 15mg/L or less total nitrogen, 1mg/L or less total phosphorus and 40 or less chroma, meets the national first-level sewage discharge standard, achieves the recovery rate of the particle electrode of 99% or more, is recycled, and reduces the cost.
Drawings
FIG. 1 is a schematic view of the general construction and workflow of a three-dimensional electrode wastewater treatment facility of the present invention; FIG. 2 is a top view of the electrolytic cell aeration device of the present invention;
fig. 3 is a plan view of the magnet recycling apparatus of the present invention.
Reference numerals illustrate: (1) an electrolysis power source; (2) a power switch: (3) a voltage adjustment knob; (4) a current adjustment knob; (5) a positive electrode; (6) a negative electrode; (7) an electrolytic cell; (8) water sample inlet; (9) a water injection pump; (10) a sampling valve; (11) a transition valve; (12) cathode titanium rod; (13) anode titanium rod; (14) a cathode plate; (15) anode plates; (16) a particle electrode; (17) an aeration device; (18) an air inlet; (19) an aeration hole; (20) an electrolytic cell cover plate; (21) titanium rod insertion holes; (22) an exhaust valve; (23) a dosing port; (24) a guide cylinder; (25) a recovery tank; (26) a transition tube; (27) a water sample outlet; (28) a magnet recovery cover plate; (29) a magnet slot; (30) a magnet.
Detailed Description
As shown in fig. 1, in the three-dimensional electrode wastewater treatment method with recovery function of the present invention, first, industrial wastewater is electrolyzed by a three-dimensional electrode electrolyzer (left part of dotted line in fig. 1), the electrolyzed industrial wastewater is input to a magnet recovery device (right part of dotted line in fig. 1), and particle electrodes in the electrolyzed industrial wastewater are adsorbed and recovered by a magnet therein.
The equipment for implementing the three-dimensional electrode wastewater treatment method with the recovery function is shown in figures 1-3, and consists of a three-dimensional electrode electrolysis device and a magnet recovery device. The three-dimensional electrode electrolysis device consists of an electrolysis tank 7 and an electrolysis tank cover plate 20, wherein the electrolysis tank 7 comprises a water sample inlet 8, a water injection pump 9, a transition valve 11, a sampling valve 10, an anode titanium rod 13, an anode plate 15, a cathode titanium rod 12, a cathode plate 14 and an aeration device 17, and the electrolysis tank cover plate 20 consists of two symmetrical titanium rod holes 21, two symmetrical exhaust valves 22, a dosing port 23 and a guide cylinder 24 of wastewater. The anode plate 15 and the cathode plate 14 are respectively connected with the anode titanium rod 13 and the cathode titanium rod 12 and are fixed on the electrolytic tank cover plate 20, the electrolytic tank cover plate 20 is installed and fixed on the electrolytic tank 7, the exhaust valve 22 is opened, the transition valve 11 and the sampling valve 10 are closed, the water injection pump 9 is opened, waste water enters the electrolytic tank 7 to the reflux position at the upper part of the guide cylinder 24 through the water sample inlet 8, the water injection pump 9 is closed, the particle electrode 16 is added from the dosing port 23, then the particle electrode 16 is uniformly distributed in the electrolytic tank 7 through the aeration of the aeration device 17, the electrolytic power supply 1 is opened, and the waste water is subjected to electrolytic treatment. The aeration device 17 is provided with four aeration holes 19 which are uniformly distributed at the center of the tank bottom. The guide cylinder 24 below the electrolytic cell cover plate 20 fully mixes the particle electrode 16 and the wastewater in an aeration state and forms a center-circumference circulation guide in the electrolytic cell 7. The sampling valve 10 is opened at regular intervals to sample the water quality of the test wastewater. When the wastewater quality reaches the discharge standard, the transition valve 11 is opened, the water injection pump 9 is opened to feed flushing water, and the wastewater in the electrolytic tank 7 and the particle electrode 16 are slowly flushed into the magnet recovery device.
The magnet recovery device comprises a transition pipe 26, a water sample outlet 27, a recovery groove 25 and a magnet recovery cover plate 28, wherein the magnet recovery cover plate 28 comprises three cylindrical magnet grooves 29, two long magnet grooves 29 are arranged at the near inlet, the short magnet grooves 29 are symmetrically arranged at the near outlet, the particle electrode 16 and wastewater are flushed into the recovery groove 25 together through the transition pipe 26, the particle electrode 16 is adsorbed on the magnet grooves 29 under the adsorption of the three magnets 30, the magnet recovery cover plate 28 is taken out after the particle electrode 16 is fully recovered, the particle electrode 16 automatically falls and is collected after the magnet 30 is taken out, more than 99% of the particle electrode 16 can be recovered, the particle electrode 16 can be continuously used after being dried, and water is discharged from the water sample outlet 27.
The parameters of the water quality after the equipment treatment are as follows: COD is less than or equal to 35mg/L and BOD 5 15mg/L or less, 30mg/L or less of TSS, 15mg/L or less of total nitrogen, 1mg/L or less of total phosphorus and 40 or less of chromaticity, meets the national first-level sewage discharge standard, and the recovery rate of the particle electrode is equal to or more than 99%.
The electrolytic power supply 1 is a constant-current and voltage-stabilized power supply, can regulate current constant-current output, and consists of a power switch 2, a voltage regulating knob 3, a current regulating knob 4, a positive electrode 5 and a negative electrode 6, wherein the positive electrode 5 is connected with an anode titanium rod 13 of the electrolytic tank 7, and the negative electrode 6 is connected with a cathode titanium rod 12 of the electrolytic tank 7.
The particle electrode 16 is Pt-SnO 2 /Fe 3 O 4 The particle electrode is added in an amount of 0.25g/L to 2g/L. Pt-SnO 2 /Fe 3 O 4 The particle electrode is hexahedral nanoparticle with magnetism, and the particleThe diameter is between 500 and 800 nm. SnO (SnO) 2 And Pt as active components, are uniformly and firmly inlaid in Fe by means of Van der Waals force and mechanical force 3 O 4 On the particles. The molar contents of the components are respectively as follows: 35% -93%, sn:6.2% -58%, pt:0.8% -7%.
The anode plate 15 is Ti/SnO 2 -Sb 2 O 5 -Pt-coated titanium plate anode with current density of 20mA/cm 2 -50mA/cm 2 The oxide anode comprises a titanium matrix and an active coating on the surface of the titanium matrix, wherein the active coating consists of SnO 2 、Sb 2 O 5 And Pt, the mole fractions of the components are Sn:85.5% -89.55%, sb:9.5% -9.95%, pt: 0.5-5%, and the coating load is more than or equal to 5g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The preparation process of the anode plate comprises the following steps:
a. pretreatment of a titanium plate substrate: grinding the surface of the titanium plate to form uneven pitted surface, removing oil and dirt, cleaning, and then placing 10% -30% of H 2 C 2 O 4 Treating in solution for 0.5-1.5h under slightly boiling condition in a kitchen, cleaning with distilled water, and storing in distilled water.
b. Titanium plate surface coating: dissolving tin chloride, antimony chloride and chloroplatinic acid with a certain mass fraction into 2.5-5ml hydrochloric acid with a mass fraction of 37%, adding n-butanol to prepare a solution, uniformly smearing the solution on a treated titanium plate back and forth, then placing the titanium plate in an 80 ℃ oven for drying for 5min, repeatedly smearing and drying for 15-20 times, finally placing the titanium plate in a muffle furnace for roasting for 3-5h at 550 ℃ and repeatedly roasting for 5-10 times, and finally preparing Ti/SnO 2 -Sb 2 O 5 -Pt electrode.
The cathode 14 is made of titanium plate.
The magnet 30 is a neodymium iron boron magnet, the cost performance is high, the magnetism is strong, two long magnets are arranged at the inlet of a near transition pipe in the system and are symmetrically arranged, the positions of the two magnets N, S are oppositely arranged, a short magnet is arranged at the outlet of a near water sample, and the recovery rate of the particle electrode 16 is more than or equal to 99%.
The water sample inlet 8 is connected with a pretreatment system for removing suspended matters or directly extracts substandard wastewater when the wastewater is introduced; when the particle electrode 16 is recovered and the treated water reaching the standard is discharged, the water sample inlet 8 is switched to directly extract the washing water meeting the requirements.
According to the technical method listed in the summary of the invention, the industrial wastewater was subjected to a further treatment according to the parameters in the following 2 examples, respectively. Relevant parameters in the industrial wastewater before and after treatment are analyzed according to a national standard test method, and the recovery rate of the particle electrode is tested, and the result is shown in table 1.
Application example 1: injecting Pt-SnO into printing and dyeing industrial wastewater from water sample inlet 2 /Fe 3 O 4 The addition amount of the particle electrode is 1g/L, aeration is carried out, and the effective area of the anode plate is 8cm 2 The current density was 30mA/cm 2 And discharging after electrolysis for 20 min.
Application example 2: injecting synthetic ammonia industrial wastewater, pt-SnO from water sample inlet 2 /Fe 3 O 4 The addition amount of the particle electrode is 1.2g/L, aeration is carried out, and the effective area of the anode plate is 8cm 2 The current density was 45mA/cm 2 And discharging after 25min of electrolysis time.
TABLE 1
Claims (6)
1. A particle electrode suitable for industrial wastewater treatment is characterized in that the overall structure of the particle electrode is Pt-SnO 2 /Fe 3 O 4 The carrier is Fe 3 O 4 In Fe 3 O 4 The carrier is provided with active ingredient SnO 2 And Pt, wherein the mole fraction content of each component is Fe:35-93%, sn:6.2-58%, pt:0.8-7%; the preparation process adopts a three-step method: fe (Fe) 3 O 4 Is prepared from SnO 2 /Fe 3 O 4 Preparation of (C) Pt-SnO 2 /Fe 3 O 4 Is prepared by the steps of (1);
the specific preparation process is as follows:
Fe 3 O 4 is prepared from the following steps: 50% hydrationPreparing a mixed solution of hydrazine, 0.5mol/L ferrous sulfate solution, 5mol/L sodium hydroxide solution and ethylene glycol according to a volume ratio of 2:2:1:20, then placing the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a volume of 80-500 ml, placing the hydrothermal reaction kettle into a muffle furnace for treatment at 200 ℃ for 24 hours, cooling, washing the hydrothermal reaction kettle with distilled water until the pH value is 7, and finally drying the hydrothermal reaction kettle in a vacuum drying oven at 40 ℃ for 6 hours to obtain large-particle magnetic Fe particles 3 O 4 Hexahedral nanoparticles as a carrier;
SnO 2 /Fe 3 O 4 is prepared from the following steps: dissolving tin chloride in glycol and deionized water in a volume ratio of 1:1 to prepare a solution A; preparing 2.5 mol/L sodium hydroxide solution as solution B, slowly adding the solution B into the solution A until white suspension appears, and then adding Fe prepared by the method 3 O 4 The carrier is stirred uniformly and then dispersed by ultrasonic, then the carrier is moved into a reaction kettle to be heated for 12 hours at 180 ℃, cooled and washed, finally dried for 4 hours in a vacuum drying oven at 60 ℃ to obtain the nano-scale metal composite oxide SnO 2 /Fe 3 O 4 The mole fraction content of each component of the particles is Fe:37.5-93.75%, sn:6.25-62.5%;
Pt-SnO 2 /Fe 3 O 4 is prepared from the following steps: preparing chloroplatinic acid and SnO with ice water (less than 5 ℃) 2 /Fe 3 O 4 The mixed solution with the molar ratio of 1:8 is dispersed for 30-50min by ultrasonic; preparing 0.1mol/L sodium borohydride solution by using ice water, and then adjusting the pH value of the sodium borohydride solution to be 12 by using 0.5mol/L NaOH solution, so as to prepare the sodium borohydride solution for use at present; slowly adding chloroplatinic acid and SnO into sodium borohydride solution under stirring 2 /Fe 3 O 4 Mixing the solution to obtain a mixture, placing the mixture in an ice bath for 3 hours, centrifuging the precipitate, washing the precipitate with ultrapure water and ethanol, drying the precipitate in a vacuum drying oven at 80 ℃ for 6 hours, and loading a high-activity noble metal catalyst Pt to SnO, wherein the molar ratio of sodium borohydride to chloroplatinic acid is 1:2 2 /Fe 3 O 4 On the surface, pt-SnO is prepared 2 /Fe 3 O 4 Particle electrodes.
2. The particle electrode of claim 1, wherein the Pt-SnO 2 /Fe 3 O 4 The particle electrode is hexahedral nano particles with magnetism, and the particle size is between 500 and 800 nm; snO (SnO) 2 And Pt as active components, are uniformly and firmly inlaid in Fe by means of Van der Waals force and mechanical force 3 O 4 On carrier particles; by adjusting the addition amount of each reactant, pt-SnO with different loading amounts can be prepared 2 /Fe 3 O 4 Particle electrodes.
3. A three-dimensional electrode wastewater treatment method with a recovery function by adopting the particle electrode as claimed in claim 1, which is characterized in that the method is firstly based on Pt-SnO 2 /Fe 3 O 4 And (3) electrolyzing the industrial wastewater by using the three-dimensional electrode of the particle electrode, and then adsorbing the particle electrode in the electrolyzed industrial wastewater by using a magnet.
4. An apparatus for carrying out the three-dimensional electrode wastewater treatment method with recovery function according to claim 3, characterized by comprising a three-dimensional electrode electrolysis device and a magnet recovery device, the output end of the former being connected with the input end of the latter;
the three-dimensional electrode electrolysis device consists of an electrolysis bath and an electrolysis bath cover plate arranged at the top of the electrolysis bath, wherein the electrolysis bath comprises a bath body, and a water sample inlet and a water injection pump are arranged at the upper part of the bath body; the lower part of the tank body is provided with a sampling valve, an electrolytic tank water outlet and an aeration device; an anode titanium rod, an anode plate, a cathode titanium rod and a cathode plate are arranged in the tank body, the upper end of the anode titanium rod and the upper end of the cathode titanium rod penetrate through the electrolytic tank cover plate and are respectively connected with the anode and the cathode of an electrolytic power supply, the lower part of the anode titanium rod is connected with the anode plate, and the lower part of the cathode titanium rod is connected with the cathode plate; a guide cylinder is arranged between the anode plate and the cathode plate, and water flow channels are reserved at the upper end and the lower end of the guide cylinder; an exhaust valve and a dosing port are arranged on the cover plate of the electrolytic tank.
5. The apparatus of claim 4, wherein the magnet recycling device comprises a recycling tank and a recycling cover plate arranged at the top end of the recycling tank, wherein the bottom of one side of the recycling tank is provided with a recycling tank inlet and is connected with the water outlet of the electrolytic tank through a transition pipe and a transition valve, and the upper part of the other side of the recycling tank is provided with a water sample outlet; the recovery cover plate is provided with a plurality of downwardly extending magnet grooves, and magnets are placed in the magnet grooves.
6. The apparatus of claim 5, wherein the recovery tank is made of transparent glass material, and the recovery cover plate is made of PC polycarbonate material; the recovery groove is cuboid, the number of the magnet grooves arranged on the recovery cover plate is three, two magnet grooves are symmetrically arranged near the inlet of the recovery groove, and the positions of the two magnets N, S are opposite, so that most of particle electrodes can be adsorbed; a magnet groove is arranged on the water sample outlet accessory to adsorb the residual particle electrode, so that a small amount of particle electrode is prevented from losing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810714591.7A CN108585129B (en) | 2018-07-03 | 2018-07-03 | Three-dimensional electrode wastewater treatment method and equipment with recovery function |
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| CN102616893A (en) * | 2012-04-01 | 2012-08-01 | 苏州大学 | Wastewater treatment system |
| JP2016144445A (en) * | 2015-01-28 | 2016-08-12 | ユニバーサル・バイオ・リサーチ株式会社 | Automatic bacteria detecting apparatus and method thereof |
| CN108178245A (en) * | 2017-11-30 | 2018-06-19 | 广西大学 | A kind of centralization air micro-electrolysis reactor and sewage water treatment method |
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| CN102616893A (en) * | 2012-04-01 | 2012-08-01 | 苏州大学 | Wastewater treatment system |
| JP2016144445A (en) * | 2015-01-28 | 2016-08-12 | ユニバーサル・バイオ・リサーチ株式会社 | Automatic bacteria detecting apparatus and method thereof |
| CN108178245A (en) * | 2017-11-30 | 2018-06-19 | 广西大学 | A kind of centralization air micro-electrolysis reactor and sewage water treatment method |
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| 基于SnO2/Fe3O4粒子电极的三维电极体系的电催化性能;张显峰 等;《材料导报》;第31卷(第4期);第25-30页 * |
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