CN114349132A - Method for continuously treating organic matters in GMA high-salinity wastewater - Google Patents
Method for continuously treating organic matters in GMA high-salinity wastewater Download PDFInfo
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Abstract
The invention relates to a method for continuously treating organic matters in GMA high-salt wastewater, which is characterized in that a high-oxygen-evolution overpotential electrode is used in an electrochemical degradation device to enable the GMA high-salt wastewater to generate high-concentration hydroxyl radicals, and the radicals and the organic matters are subjected to oxidation reaction to effectively degrade the organic matters. The treatment method has simple device, changes intermittent treatment into continuous degradation, has low energy consumption, high degradation speed and extremely low organic matter residual quantity, and the degraded saline water can be directly used as a raw material in the chlor-alkali industry, thereby realizing the effective resource utilization of high-salinity wastewater and having extremely high industrial development prospect.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for continuously treating organic matters in GMA high-salt wastewater through electrochemical degradation.
Background
Glycidyl Methacrylate (GMA) is an important bifunctional acrylate and is mainly used for modifying thermosetting powder coatings, adhesives, plastics and fibers. The current GMA synthesis process mainly comprises a phase transfer method, an open-loop and closed-loop method, an ester exchange method, a biological fermentation method and the like. The ester exchange method and the biological fermentation method are laboratory research stages, and the phase transfer method and the open-loop closed-loop method have already realized industrial production.
In the current industrialized synthetic route, a large amount of high-salt high-COD wastewater which is difficult to treat is inevitably generated. If the direct incineration mode is adopted for treatment, great economic cost is required; if the multi-effect evaporation and solvent salt washing modes are adopted, the emission standard is difficult to reach.
Patent CN108341536A discloses a method for treating wastewater from epoxy resin production, which comprises removing large suspended impurities from the wastewater by a grid, and then refining the high-salt wastewater by coagulation, extraction, electrodialysis desalination, fenton oxidation, flash evaporation, decolorization, fine filtration and other steps for direct recycling. Although the scheme can directly recycle the brine, the process is complicated, and the equipment investment is huge.
Patent CN108558146A discloses a process method and a device for combining advanced oxidation and electrolytic catalysis of organic matters in high-salinity wastewater, wherein industrial wastewater after coarse filtration is sent into an advanced oxidizer, hydrogen peroxide and ozone are introduced, the wastewater after advanced oxidation is sent into an electrolytic catalytic oxidizer, 5-24V voltage is applied under the action of catalyst filler, and the organic matters in the wastewater are decomposed under the irradiation of ultraviolet light. The proposal can reduce the COD in the wastewater to the discharge index, but the price of the used palladium metal is extremely expensive in the implementation process, the operation flow is fussy, and the process cost is directly increased by the ultraviolet irradiation process which is particularly related.
Therefore, there is still a need for an efficient continuous process for the treatment of GMA high-salt high COD wastewater.
Disclosure of Invention
Aiming at the problems in the prior art, the invention degrades the organic matters to the maximum extent by an electrochemical degradation device and an electrolysis process adopting a high oxygen evolution overpotential electrode, and the existence of the high oxygen evolution overpotential electrode can enable hydroxyl free radicals to stably exist, so that the organic matters are effectively degraded.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for continuously treating organic matters in GMA high-salt wastewater comprises the steps of generating hydroxyl radicals in the GMA high-salt wastewater by using a high oxygen evolution overpotential electrode in an electrochemical degradation device, and carrying out oxidation reaction on the radicals and the organic matters to degrade the organic matters.
In a specific embodiment, the electrochemical degradation device comprises at least two electrochemical degradation tanks and a degradation reaction kettle which are sequentially connected in series, high-salt wastewater enters the first electrochemical degradation tank from a left lower port, flows out from a right upper port and then enters the next electrochemical degradation tank, the high-salt wastewater flows out from the right upper port of the last electrochemical degradation tank and then enters the degradation reaction kettle together with added hydrogen peroxide, the temperature and the residence time of the degradation reaction kettle are controlled to degrade organic matters, and the COD (chemical oxygen demand) of the salt water lower than 10mg/L is obtained at an outlet of the degradation reaction kettle.
In a specific embodiment, the electrochemical degradation device comprises two electrochemical degradation tanks and a degradation reaction kettle, high-salt wastewater enters the first electrochemical degradation tank from a left lower port, enters the second electrochemical degradation tank after flowing out from a right upper port, enters the degradation reaction kettle together with added hydrogen peroxide after flowing out from a right upper port of the second electrochemical degradation tank, the temperature and the residence time of the degradation reaction kettle are controlled to degrade organic matters, and the outlet of the degradation reaction kettle obtains saline water with COD lower than 10 mg/L.
In a specific embodiment, the electrochemical degradation device comprises three electrochemical degradation tanks and a degradation reaction kettle, high-salt wastewater enters the first electrochemical degradation tank from a left lower port, flows out from a right upper port and then enters the second electrochemical degradation tank, and sequentially enters the third electrochemical degradation tank, waste brine enters the degradation reaction kettle together with added hydrogen peroxide after flowing out from the right upper port of the third electrochemical degradation tank, the temperature and the residence time of the degradation reaction kettle are controlled to degrade organic matters, and the outlet of the degradation reaction kettle obtains brine with COD lower than 10 mg/L.
In a specific embodiment, the electrochemical degradation cell is a plate and frame cell, and the electrochemical degradation cell employs PbO2、SnO2And/or Sb2O4Mutually doped high oxygen evolution overpotential anode coatings; preferably, the mutually doped high oxygen evolution overpotential anode coating contains PbO based on the total mass of the metal oxide coating2Mass fractionNot less than 45%, preferably 55% to 80%; SnO2Or/and Sb2O4The mass fraction is 10-50%, preferably 20-45%.
In a specific embodiment, the temperature of the first electrochemical degradation tank is controlled to be more than 40 ℃, preferably 50-65 ℃; the temperature of the second electrochemical degradation tank is controlled to be greater than 55 ℃, and preferably 70-80 ℃; the temperature of the third electrochemical degradation tank is controlled to be higher than 70 ℃, and preferably 75-85 ℃; the temperature of the degradation reaction kettle is controlled to be more than 75 ℃, and is preferably 80-85 ℃.
In a specific embodiment, the current density in the first electrochemical degradation cell is maintained at 1000A/m2Above, preferably 1500 to 3000A/m2(ii) a The current density in the second electrochemical degradation tank is 600-1000A/m2Preferably 750 to 900A/m2(ii) a The current density in the third electrochemical degradation tank is 200-600A/m2Preferably 300 to 500A/m2。
In a specific embodiment, the mass of the hydrogen peroxide added into the stream withdrawn from the outlet of the electrochemical degradation tank to the degradation reaction kettle accounts for more than 3% of the total mass of the high-salinity wastewater, and is preferably 5-15%; preferably, the residence time of the high-salinity wastewater in the degradation reaction kettle is 1-5 h, preferably 2-3 h.
In a specific embodiment, the method for continuously treating organic matters in GMA high-salinity wastewater comprises the following steps:
1) starting an external circulation system, a heating system and a power supply, and circularly electrolyzing the high-salinity wastewater in the electrochemical degradation tank at a certain temperature and current density;
2) after circulating electrolysis for 15-60min, continuously extracting from the electrochemical degradation tank to the degradation reaction kettle, and simultaneously continuously feeding into the first electrochemical degradation tank, so that the feeding rate and the extraction rate in the electrochemical degradation tank are kept consistent; and adding hydrogen peroxide into the stream extracted to the degradation reaction kettle, controlling the residence time of the high-salinity wastewater in the degradation reaction kettle, and finally obtaining saline water with COD lower than 10mg/L at the outlet of the degradation reaction kettle.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, by designing at least one stage of electrochemical degradation device, especially two-stage and three-stage electrochemical degradation devices, organic matters are degraded to the maximum extent and back mixing is reduced by controlling different electrolysis conditions; the existence of the high oxygen evolution potential electrode can enable hydroxyl radicals to exist stably, and in addition, the electrochemical degradation device and the degradation reaction kettle are used together, the concentration of the hydroxyl radicals is improved by the mode of adding hydrogen peroxide, and then the hydroxyl radicals and organic matters are subjected to further oxidation reaction, so that the organic matters are effectively degraded. The method ensures that organic matters in the system are fully degraded, thereby effectively reducing COD in the system and directly recycling the salt-containing wastewater.
The device related to the method has the advantages of simple structure, low operation cost, no high-energy-consumption operation process, obvious energy-saving effect and industrial prospect.
Drawings
FIG. 1 is a schematic diagram of a system for continuously treating organic matters in GMA high-salinity wastewater.
FIG. 2 is a schematic diagram of another system for continuously treating organic matter in GMA high-salinity wastewater according to the present invention.
Wherein, 1 is a first electrochemical degradation tank, 2 second electrochemical degradation tanks, 3 third electrochemical degradation tanks, 4 degradation reaction kettles, 5 brine tanks and 6 waste water storage tanks.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
In one embodiment, as shown in fig. 1, a system for continuously treating organic matters in GMA high-salt wastewater according to the present invention includes a first electrochemical degradation tank 1, a second electrochemical degradation tank 2, a degradation reaction kettle 4, a brine tank 5, and a wastewater storage tank 6. GMA high salt waste water in waste water storage tank 6 is got into by left end opening at first electrochemistry degradation groove 1, get into second electrochemistry degradation groove 2 from the left end opening of second electrochemistry degradation groove 2 after the upper right mouth flows out, go into degradation reation kettle 4 after the upper right mouth flows out, add hydrogen peroxide solution in the waste water stream strand that the upper right mouth of second electrochemistry degradation groove 1 flows out simultaneously, the dwell time of control waste water in degradation reation kettle 4, it is less than 10mg/L saline water entering brine tank 5 to obtain COD at degradation reation kettle 4 export.
In one embodiment, as shown in fig. 2, the system for continuously treating organic matters in GMA high-salt wastewater of the present invention comprises a first electrochemical degradation tank 1, a second electrochemical degradation tank 2, a third electrochemical degradation tank 3, and a degradation reaction kettle 4; GMA high salt waste water in waste water storage tank 6 is got into by lower left mouthful at first electrochemistry degradation groove 1, get into in second electrochemistry degradation groove 2 after the upper right mouth flows out, get into in third electrochemistry degradation groove 3 in proper order, waste salt solution gets into in degradation reation kettle 4 after the upper right mouth of third electrochemistry degradation groove 3 flows out, hydrogen peroxide solution adds in the waste water stream of third electrochemistry degradation groove 3 export this moment, control degradation reation kettle temperature, dwell time makes the organic matter fully degrade, degradation reation kettle exit linkage brine tank 5.
Wherein, the three electrochemical degradation cells are basically in the form of plate-frame type electrolytic cells, preferably, the electrochemical degradation cells are in the form of diaphragm-free plate-frame type electrolytic cells, the liquid holdup of the three electrochemical degradation cells is consistent, and the liquid flows in each degradation cell in a downward-in-upward-out mode and is operated in a full liquid mode.
The high oxygen evolution overpotential anode used by the electrochemical degradation tank is PbO2Coating, SnO2Coating layer, Sb2O4A coating and high overpotential electrodes which are doped with each other; preferably, the high oxygen evolution overpotential anode has PbO2Coatings, or PbO2With SnO2And/or Sb2O4The composite coating of (1); more preferably, the mutually doped high overpotential electrode coating PbO is 100% by mass of the metal oxide coating2Mass fraction not less than 45%, preferably 55-80%, SnO2Or/and Sb2O410-50%, preferably 30-45% of the coating. The cathode of the electrochemical degradation cell of the invention is not particularly limited and may be one commonly used in electrolytic cells of the artThe cathode, such as carbon steel, may also be a conventional lead electrode.
In the treatment process of the electrochemical degradation tank, the control temperature of the first electrochemical degradation tank is higher than 40 ℃, and preferably 50-65 ℃; the current density in the first electrochemical degradation cell should be kept at 1000A/m2Above, preferably 1500 to 3000A/m2Including but not limited to 1500A/m2、1600A/m2、1700A/m2、1800A/m2、1900A/m2、2000A/m2、2100A/m2、2200A/m2、2300A/m2、2400A/m2、2500A/m2、2600A/m2、2700A/m2、2800A/m2、2900A/m2、3000A/m2。
The control temperature of the second electrochemical degradation tank is more than 55 ℃, and preferably 70-80 ℃; the current density in the second electrochemical degradation tank should be 600-1000A/m2For example, including but not limited to 600A/m2、650A/m2、700A/m2、750A/m2、800A/m2、850A/m2、900A/m2、950A/m2、1000A/m2Preferably 750 to 900A/m2。
The control temperature of the third electrochemical degradation tank is more than 70 ℃, and preferably 75-85 ℃; the temperature of the degradation reaction kettle is controlled to be more than 75 ℃, and preferably 80-85 ℃.
The current density in the third electrochemical degradation tank should be 200-600A/m2For example, including but not limited to 200A/m2、250A/m2、300A/m2、350A/m2、400A/m2、450A/m2、500A/m2、550A/m2、600A/m2Preferably 300 to 500A/m2。
In the working process, the waste brine in the electrochemical degradation tank is circularly conveyed by a pump, and the waste brine is continuously extracted from the outlet part of the last electrochemical degradation tank to the degradation reaction kettle. Meanwhile, the feeding flow and the extraction flow of the electrochemical degradation tank are ensured to be the same, so that the whole system is stably and continuously operated. In addition, hydrogen peroxide is added into a high-salinity wastewater stream which is extracted from an outlet of the last electrochemical degradation tank and enters the degradation reaction kettle, so as to further protect COD (chemical oxygen demand) after the high-salinity wastewater is treated, wherein the mass of the added hydrogen peroxide is more than 3% of the total amount of the extracted wastewater, preferably 5% -15%, the retention time of the waste saline in the degradation reaction kettle is controlled within 1-5 hours, preferably 2-3 hours, the waste saline is discharged into a saline tank after treatment, the COD in the high-salinity wastewater can be effectively reduced to be less than 10mg/L, and the high-salinity wastewater can be recycled as a chlor-alkali industrial raw material.
It should be noted that, because the hydrogen peroxide concentration in the hydrogen peroxide solution on the market is different, the concentration of the hydrogen peroxide solution is not limited in any way, and only the total amount of the hydrogen peroxide added into the system is limited.
In the use process of the actual electrochemical degradation tank, the electrochemical degradation tank is usually started to carry out external circulation, so that the electrochemical degradation tank reaches the temperature and current density required by the process, the electrochemical degradation tank can generate free radicals with sufficient concentration at the anode, and the electrolysis of organic matters in the high-salinity wastewater can be effectively realized.
Specifically, in one embodiment, the external circulation, the heating system and the power supply are started, and the high-salinity wastewater is circularly electrolyzed in the electrochemical degradation tank at a certain temperature and current density; the external circulation is that the high-salinity wastewater is circulated in at least one electrochemical degradation tank and is not extracted to the degradation reaction kettle. The control temperature and current density of the electrochemical degradation cell are also controlled at the same conditions as the normal process. After circulating electrolysis for 15-60min, continuously extracting from the electrochemical degradation tank to the degradation reaction kettle, and simultaneously continuously feeding into the first electrochemical degradation tank, so that the feeding rate and the extraction rate in the electrochemical degradation tank are kept consistent; and adding hydrogen peroxide into the stream extracted to the degradation reaction kettle, controlling the residence time of the high-salinity wastewater in the degradation reaction kettle, and finally obtaining saline water with COD lower than 10mg/L at the outlet of the degradation reaction kettle. The continuous treatment method can ensure no back mixing, ensure that the COD value of the finally treated high-salinity wastewater is stably lower than 10mg/L, and meet the discharge requirement.
The present invention is further illustrated by the following more specific examples, which are not to be construed as limiting in any way.
Information on main raw materials of the first, examples and comparative examples:
hydrogen peroxide: asahi Hydrogen peroxide Limited, wherein the concentration of hydrogen peroxide is 25%;
lead dioxide (PbO)2) Tin dioxide (SnO)2) Antimony oxide (Sb)2O4): shanghai Ji to Biochemical technology, Inc.;
plate and frame type electrolytic cell: bao Ji Ruichi titanium industries, Inc.;
electrode substrate used: jiangsu maple harbor titanium materials Equipment manufacturing Co.
Other raw materials are all common commercial products and the reagents are all analytically pure, unless otherwise specified.
Secondly, the analysis and test method adopted in the embodiment is as follows:
agilent gas chromatograph (chromatograph model GC2010 Plus): chromatography column DB-530 x 0.32 x 0.25; detector FID 2; the temperature of the vaporization chamber is 260 ℃ and the temperature of the detector is 300 ℃; temperature programming: at 50 ℃ for 2 min; 5 ℃/min to 80 ℃; then keeping the temperature at 15 ℃/min to 280 ℃ for 10 min.
Solution COD analysis method: putting 20.00ml of the uniformly mixed water sample into a 250ml ground reflux conical flask, accurately adding 10.00ml of potassium dichromate standard solution and a plurality of small glass beads or zeolite, connecting a ground reflux condenser tube, adding 30ml of sulfuric acid-silver sulfate solution from the upper opening of the condenser tube, slightly shaking the conical flask to uniformly mix the solution, and heating and refluxing for 2 hours (timing from the beginning of boiling). After cooling, the walls of the condenser tube were rinsed with 90ml of water and the flask removed. And after the solution is cooled again, adding 3 drops of ferroxyl indicator solution, titrating by using an ammonium ferrous sulfate standard solution, recording the use amount of the ammonium ferrous sulfate standard solution, and calculating the COD (chemical oxygen demand) by taking the end point that the color of the solution is changed from yellow to reddish brown from blue-green.
Example 1
Selecting three-stage electrochemical degradation tank shown in FIG. 2, and selecting titanium-based lead dioxide (PbO) as electrodes2) And tin dioxide (SnO)2) Mixed coating of PbO therein265% of SnO2The content is 35% (all based on the total mass of the coating). Get and waitAdding the treated wastewater (COD is 15000mg/L, NaCl concentration is 19.5%) into a storage tank, starting external circulation, and starting a heating system; the temperature of the first electrochemical degradation tank is controlled to be 50 ℃, the temperature of the second electrochemical degradation tank is controlled to be 70 ℃, the temperature of the third electrochemical degradation tank is controlled to be 75 ℃, and the temperature of the degradation reaction kettle is controlled to be 80 ℃.
Slowly turning on a power supply, and controlling the current density in the first electrochemical degradation tank to be 1500A/m2Controlling the current density in the second electrochemical degradation tank to be 750A/m2Controlling the current density in the third electrochemical degradation tank to be 300A/m2。
After 30min of circulating electrolysis, continuously extracting the materials from the third electrochemical degradation tank to the degradation reaction kettle (effective volume is 1L), continuously feeding the materials into the first electrochemical degradation tank by the feeding storage tank, and keeping the feeding rate consistent with the extraction rate. And adding hydrogen peroxide into the stream extracted from the outlet of the third electrochemical degradation tank to the degradation reaction kettle at the extraction rate of 500g/h, wherein the dropping mass flow rate of the hydrogen peroxide is 25g/h, the retention time of the waste saline in the degradation reaction kettle is controlled to be about 2.1h, and the COD is 8mg/L by sampling and analyzing at the outlet of the degradation reaction kettle.
Example 2
The three-stage electrochemical degradation tank is selected, and the electrode is titanium-based lead dioxide (PbO)2) Tin dioxide (SnO)2) And antimony oxide (Sb)2O4) Mixed coating of PbO therein255% of SnO220% of Sb2O4The content is 25% (all based on the total mass of the coating). Adding wastewater to be treated (COD is 15000mg/L, NaCl concentration is 19.5%) into a storage tank, starting external circulation, and starting a heating system; the temperature of the first electrochemical degradation tank is controlled to be 55 ℃, the temperature of the second electrochemical degradation tank is controlled to be 75 ℃, the temperature of the third electrochemical degradation tank is controlled to be 80 ℃, and the temperature of the degradation reaction kettle is controlled to be 85 ℃.
Slowly turning on a power supply, and controlling the current density in the first electrochemical degradation tank to be 1700A/m2Controlling the current density in the second electrochemical degradation tank to be 900A/m2Controlling the current density in the third electrochemical degradation tank to be 450A/m2。
After 30min of circulating electrolysis, the wastewater is continuously extracted from the third electrochemical degradation tank into a degradation reaction kettle (effective volume is 1L). At the moment, the feeding storage tank continuously feeds the first electrochemical degradation tank, and the feeding rate and the production rate are kept consistent. And adding hydrogen peroxide into the stream extracted from the outlet of the third electrochemical degradation tank to the degradation reaction kettle at the extraction rate of 500g/h, wherein the dropping mass flow rate of the hydrogen peroxide is 25g/h, the retention time of the waste saline in the degradation reaction kettle is controlled to be about 2.1h, and the COD is 4mg/L by sampling and analyzing at the outlet of the degradation reaction kettle.
Example 3
The three-stage electrochemical degradation tank is selected, and the electrode is titanium-based lead dioxide (PbO)2) And antimony oxide (Sb)2O4) Mixed coating of PbO therein275% of Sb2O4The content is 25% (all based on the total mass of the coating). Adding wastewater to be treated (COD is 15000mg/L, NaCl concentration is 19.5%) into a storage tank, starting external circulation, and starting a heating system; the temperature of the first electrochemical degradation tank is controlled to be 60 ℃, the temperature of the second electrochemical degradation tank is controlled to be 70 ℃, the temperature of the third electrochemical degradation tank is controlled to be 80 ℃, and the temperature of the degradation reaction kettle is controlled to be 85 ℃.
Slowly turning on a power supply, and controlling the current density in the first electrochemical degradation tank to be 1600A/m2Controlling the current density in the second electrochemical degradation tank to be 850A/m2Controlling the current density in the third electrochemical degradation tank to be 400A/m2。
After 30min of circulating electrolysis, the wastewater is continuously extracted from the third electrochemical degradation tank into a degradation reaction kettle (effective volume is 1L). At the moment, the feeding storage tank continuously feeds the first electrochemical degradation tank, and the feeding rate and the production rate are kept consistent. And adding hydrogen peroxide into the stream extracted from the outlet of the third electrochemical degradation tank to the degradation reaction kettle at the extraction rate of 450g/h, wherein the dropping mass flow rate of the hydrogen peroxide is 40g/h, the retention time of the waste saline in the degradation reaction kettle is controlled to be about 2.5h, and the COD is 6mg/L by sampling and analyzing at the outlet of the degradation reaction kettle.
Example 4
The three-stage electrochemical degradation tank is selected, and the electrode is titanium-based lead dioxide (PbO)2) And (2) oxidation ofTin (SnO)2) And antimony oxide (Sb)2O4) Mixed coating of PbO therein265% of SnO215% of Sb2O4The content is 20 percent (based on the total mass of the coating). Adding wastewater to be treated (COD is 15000mg/L, NaCl concentration is 19.5%) into a storage tank, starting external circulation, and starting a heating system; the temperature of the first electrochemical degradation tank is controlled to be 55 ℃, the temperature of the second electrochemical degradation tank is controlled to be 70 ℃, the temperature of the third electrochemical degradation tank is controlled to be 80 ℃, and the temperature of the degradation reaction kettle is controlled to be 85 ℃.
Slowly turning on a power supply, and controlling the current density in the first electrochemical degradation tank to be 2500A/m2Controlling the current density in the second electrochemical degradation tank to be 900A/m2Controlling the current density in the third electrochemical degradation tank to be 500A/m2。
After 30min of circulating electrolysis, the wastewater is continuously extracted from the third electrochemical degradation tank into a degradation reaction kettle (effective volume is 1L). At the moment, the feeding storage tank continuously feeds the first electrochemical degradation tank, and the feeding rate and the production rate are kept consistent. And adding hydrogen peroxide into the stream extracted from the outlet of the third electrochemical degradation tank to the degradation reaction kettle at the extraction rate of 400g/h, wherein the dropping mass flow rate of the hydrogen peroxide is 30g/h, the retention time of the waste saline in the degradation reaction kettle is controlled to be about 2.6h, and the COD is 5mg/L by sampling and analyzing at the outlet of the degradation reaction kettle.
Example 5
The three-stage electrochemical degradation tank is selected, and the electrode is titanium-based lead dioxide (PbO)2) And tin dioxide (SnO)2) Mixed coating of PbO therein280% of SnO2The content is 20 percent (based on the total mass of the coating). Adding wastewater to be treated (COD is 15000mg/L, NaCl concentration is 19.5%) into a storage tank, starting external circulation, and starting a heating system; the temperature of the first electrochemical degradation tank is controlled to be 65 ℃, the temperature of the second electrochemical degradation tank is controlled to be 75 ℃, the temperature of the third electrochemical degradation tank is controlled to be 85 ℃, and the temperature of the degradation reaction kettle is controlled to be 85 ℃.
Slowly turning on a power supply, and controlling the current density in the first electrochemical degradation tank to be 2000A/m2Controlling current density in a second electrochemical degradation cellIs 800A/m2Controlling the current density in the third electrochemical degradation tank to be 450A/m2。
After 30min of circulating electrolysis, the wastewater is continuously extracted from the third electrochemical degradation tank into a degradation reaction kettle (effective volume is 1L). At the moment, the feeding storage tank continuously feeds the first electrochemical degradation tank, and the feeding rate and the production rate are kept consistent. And adding hydrogen peroxide into the stream extracted from the outlet of the third electrochemical degradation tank to the degradation reaction kettle at the extraction rate of 350g/h, wherein the dropping mass flow rate of the hydrogen peroxide is 35g/h, the retention time of the waste saline in the degradation reaction kettle is controlled to be about 2.6h, and the COD is 4mg/L by sampling and analyzing at the outlet of the degradation reaction kettle.
Example 6
The three-stage electrochemical degradation tank is selected, and the electrode is titanium-based lead dioxide (PbO)2) Tin dioxide (SnO)2) And antimony oxide (Sb)2O4) Mixed coating of PbO therein275% of SnO215% of Sb2O4The content is 10% (all based on the total mass of the coating). Adding wastewater to be treated (COD is 15000mg/L, NaCl concentration is 19.5%) into a storage tank, starting external circulation, and starting a heating system; the temperature of the first electrochemical degradation tank is controlled to be 55 ℃, the temperature of the second electrochemical degradation tank is controlled to be 70 ℃, the temperature of the third electrochemical degradation tank is controlled to be 80 ℃, and the temperature of the degradation reaction kettle is controlled to be 80 ℃.
Slowly turning on a power supply, and controlling the current density in the first electrochemical degradation tank to be 1800A/m2Controlling the current density in the second electrochemical degradation tank to be 850A/m2Controlling the current density in the third electrochemical degradation tank to be 500A/m2。
After 30min of circulating electrolysis, the wastewater is continuously extracted from the third electrochemical degradation tank into a degradation reaction kettle (effective volume is 1L). At the moment, the feeding storage tank continuously feeds the first electrochemical degradation tank, and the feeding rate and the production rate are kept consistent. And adding hydrogen peroxide into the stream extracted from the outlet of the third electrochemical degradation tank to the degradation reaction kettle, wherein the extraction rate is 300g/h, the dropping mass flow rate of the hydrogen peroxide is 30g/h, the retention time of the waste saline in the degradation reaction kettle is controlled to be about 3h, and the COD is 5mg/L measured by sampling analysis at the outlet of the degradation reaction kettle.
Example 7
Adopting the first and the second electrochemical degradation tanks, the electrode is titanium-based lead dioxide (PbO)2) Tin dioxide (SnO)2) And antimony oxide (Sb)2O4) Mixed coating of PbO therein255% of SnO220% of Sb2O4The content is 25% (all based on the total mass of the coating). Adding wastewater to be treated (COD is 15000mg/L, NaCl concentration is 19.5%) into a storage tank, starting external circulation, and starting a heating system; the temperature of the first electrochemical degradation tank is controlled to be 80 ℃, the temperature of the second electrochemical degradation tank is controlled to be 90 ℃, and the temperature of the degradation reaction kettle is controlled to be 90 ℃.
Slowly turning on a power supply, and controlling the current density in the first electrochemical degradation tank to be 2500A/m2The current density in the second electrochemical degradation tank is controlled to be 1500A/m2。
After 30min of circulating electrolysis, the wastewater is continuously extracted from the third electrochemical degradation tank into a degradation reaction kettle (effective volume is 1L). At the moment, the feeding storage tank continuously feeds the first electrochemical degradation tank, and the feeding rate and the production rate are kept consistent. And adding hydrogen peroxide into the stream extracted from the outlet of the second electrochemical degradation tank to the degradation reaction kettle at the extraction rate of 217g/h, wherein the dropping mass flow rate of the hydrogen peroxide is 11g/h, the retention time of the waste brine in the degradation reaction kettle is controlled to be about 4.8h, and the COD is 8mg/L by sampling and analyzing at the outlet of the degradation reaction kettle.
Comparative example 1
The preparation method of example 2 was adopted, and titanium-based lead dioxide (PbO) was used as the electrode2) Tin dioxide (SnO)2) And antimony oxide (Sb)2O4) Mixed coating of PbO therein255% of SnO220% of Sb2O4The content is 25% (all based on the total mass of the coating).
Adding wastewater to be treated (COD is 15000mg/L, NaCl concentration is 19.5%) into a storage tank, starting external circulation, only starting a heating system of a first electrochemical degradation tank, controlling the temperature of the first electrochemical degradation tank to be 55 ℃, and controlling current density in the first electrochemical degradation tankThe degree is 1700A/m2. And (3) directly connecting the outlet of the first electrochemical degradation tank with a degradation reaction kettle, and continuously extracting the wastewater from the first electrochemical degradation tank into the degradation reaction kettle (with the effective volume of 1L) after circulating electrolysis for 30min, wherein the temperature of the degradation reaction kettle is controlled to be 85 ℃. At the moment, the feeding storage tank continuously feeds the first electrochemical degradation tank, and the feeding rate and the production rate are kept consistent. Hydrogen peroxide is added into the stream from the outlet of the first electrochemical degradation tank to the degradation reaction kettle, the extraction rate is 500g/h, the dropping mass flow rate of the hydrogen peroxide is 25g/h (wherein the concentration of the hydrogen peroxide ranges from 30% to 70%), and the residence time of the waste brine in the degradation reaction kettle is controlled to be about 2.1 h. Sampling and analyzing at the outlet of the degradation reaction kettle to determine that the COD is 350 mg/L.
Comparative example 2
The preparation method of example 2 was adopted, and titanium-based lead dioxide (PbO) was used as the electrode2) Tin dioxide (SnO)2) And antimony oxide (Sb)2O4) Mixed coating of PbO therein255% of SnO220% of Sb2O4The content is 25% (all based on the total mass of the coating).
Adding wastewater to be treated (COD is 15000mg/L, NaCl concentration is 19.5%) into a storage tank, starting external circulation, only starting the heating systems of the second electrochemical degradation tank and the third electrochemical degradation tank, controlling the temperature of the second electrochemical degradation tank at 75 ℃ and the current density at 900A/m2Controlling the temperature of the third electrochemical degradation tank to be 80 ℃ and the current density to be 450A/m2. And directly connecting the outlet of the third electrochemical degradation tank with the degradation reaction kettle, and continuously extracting the wastewater from the third electrochemical degradation tank into the degradation reaction kettle (with the effective volume of 1L) after circulating electrolysis for 30min, wherein the temperature of the degradation reaction kettle is controlled to be 85 ℃. At the moment, the feeding storage tank continuously feeds materials to the second electrochemical degradation tank, and the feeding rate and the production rate are kept consistent. And (3) adding hydrogen peroxide into the stream from the outlet of the third electrochemical degradation tank to the degradation reaction kettle, wherein the extraction rate is 500g/h, the dropping mass flow rate of the hydrogen peroxide is 25g/h (the concentration of the hydrogen peroxide ranges from 30% to 70%), and the residence time of the waste brine in the degradation reaction kettle is controlled to be about 2.1 h. Sampling analysis at the outlet of the degradation reaction kettle and measuring that the COD is 46 mg/L.
Comparative example 3
The preparation method of example 2 was used, except that the mixed-coated electrode was changed to PbO2The single-coating electrode and other process conditions are completely the same as example 2, and finally COD is 45mg/L measured by sampling and analyzing at the outlet of the degradation reaction kettle.
Comparative example 4
The preparation method of example 2 was used, except that hydrogen peroxide was not added. Namely sampling and analyzing at the outlet of the third electrochemical degradation tank, wherein the COD in the system is 225 mg/L.
Comparative example 5
The preparation method of example 2 was used, except that the mixed coating electrode was changed to SnO2Single coated electrode, the remaining conditions were consistent. Sampling and analyzing at the outlet of the degradation reaction kettle to determine that the COD is 286 mg/L.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A method for continuously treating organic matters in GMA high-salt wastewater is characterized by comprising the steps of enabling the GMA high-salt wastewater to generate hydroxyl radicals by using a high oxygen evolution overpotential electrode in an electrochemical degradation device, and enabling the radicals to have oxidation reaction with the organic matters to degrade the organic matters.
2. The method according to claim 1, wherein the electrochemical degradation device comprises at least two electrochemical degradation tanks and a degradation reaction kettle which are sequentially connected in series, the high-salt wastewater enters the first electrochemical degradation tank from a lower left port, flows out from an upper right port and then enters the next electrochemical degradation tank, the high-salt wastewater enters the degradation reaction kettle together with added hydrogen peroxide after flowing out from an upper right port of the last electrochemical degradation tank, the temperature and the residence time of the degradation reaction kettle are controlled to degrade organic matters, and the brine with COD lower than 10mg/L is obtained at an outlet of the degradation reaction kettle.
3. The method according to claim 2, wherein the electrochemical degradation device comprises two electrochemical degradation tanks and a degradation reaction kettle, the high-salt wastewater enters the first electrochemical degradation tank from a left lower port, flows out from a right upper port and then enters the second electrochemical degradation tank, the high-salt wastewater flows out from the right upper port of the second electrochemical degradation tank and then enters the degradation reaction kettle together with the added hydrogen peroxide, the temperature and the residence time of the degradation reaction kettle are controlled to degrade the organic matters, and the COD of the brine at the outlet of the degradation reaction kettle is lower than 10 mg/L.
4. The method according to claim 3, wherein the electrochemical degradation device comprises three electrochemical degradation tanks and a degradation reaction kettle, the high-salt wastewater enters the first electrochemical degradation tank from a lower left port, the high-salt wastewater flows out from an upper right port and then enters the second electrochemical degradation tank, the high-salt wastewater sequentially enters the third electrochemical degradation tank, the waste brine flows out from an upper right port of the third electrochemical degradation tank and then enters the degradation reaction kettle together with the added hydrogen peroxide, the temperature and the residence time of the degradation reaction kettle are controlled to degrade the organic matters, and the COD (chemical oxygen demand) of the outlet of the degradation reaction kettle is lower than 10 mg/L.
5. The method according to any one of claims 1 to 4, wherein the electrochemical degradation tank is a plate and frame type electrolytic tank, and the electrochemical degradation tank adopts PbO2And SnO2And/or Sb2O4And the two layers are doped high oxygen evolution overpotential anode coatings.
6. The method of claim 5, wherein the mutually doped high oxygen evolution overpotential anode coating comprises PbO based on the total mass of the metal oxide coating2The mass fraction is not less than 45 percent, and is preferably 55 to 80 percent; SnO2Or/and Sb2O4The mass fraction is 10-50%, preferably 20-45%.
7. The method according to any one of claims 1 to 6, wherein the first electrochemical degradation cell is controlled at a temperature of greater than 40 ℃, preferably 50 to 65 ℃; the temperature of the second electrochemical degradation tank is controlled to be greater than 55 ℃, and preferably 70-80 ℃; the temperature of the third electrochemical degradation tank is controlled to be higher than 70 ℃, and preferably 75-85 ℃; the temperature of the degradation reaction kettle is controlled to be more than 75 ℃, and is preferably 80-85 ℃.
8. The method of any one of claims 1 to 7, wherein the current density in the first electrochemical degradation cell is maintained at 1000A/m2Above, preferably 1500 to 3000A/m2(ii) a The current density in the second electrochemical degradation tank is 600-1000A/m2Preferably 750 to 900A/m2(ii) a The current density in the third electrochemical degradation tank is 200-600A/m2Preferably 300 to 500A/m2。
9. The method according to any one of claims 1 to 8, wherein the mass of the hydrogen peroxide added to the stream withdrawn from the outlet of the electrochemical degradation tank to the degradation reaction kettle accounts for more than 3% of the total mass of the high-salinity wastewater withdrawn, and is preferably 5-15%; preferably, the residence time of the high-salinity wastewater in the degradation reaction kettle is 1-5 h, preferably 2-3 h.
10. The method according to any one of claims 1 to 9, comprising the steps of:
1) starting an external circulation system, a heating system and a power supply, and circularly electrolyzing the high-salinity wastewater in the electrochemical degradation tank at a certain temperature and current density;
2) after circulating electrolysis for 15-60min, continuously extracting from the electrochemical degradation tank to the degradation reaction kettle, and simultaneously continuously feeding into the first electrochemical degradation tank, so that the feeding rate and the extraction rate in the electrochemical degradation tank are kept consistent; and adding hydrogen peroxide into the stream extracted to the degradation reaction kettle, controlling the residence time of the high-salinity wastewater in the degradation reaction kettle, and finally obtaining saline water with COD lower than 10mg/L at the outlet of the degradation reaction kettle.
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