CN110776191A - Method for degrading industrial organic wastewater by ultrasonic ozone-micro-electrolysis coupling - Google Patents
Method for degrading industrial organic wastewater by ultrasonic ozone-micro-electrolysis coupling Download PDFInfo
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Abstract
The invention discloses a method for degrading industrial organic wastewater by ultrasonic ozone-microelectrolysis coupling, which adopts micro bubbles generated by ultrasonic oscillation and plasma ozone output by a gas distribution plate to carry out front-end treatment on the industrial organic wastewater, avoids the escape of ozone and improves the utilization rate of the ozone. Sponge iron and carbon molecular sieves, a small amount of catalyst and binder are used as a reinforced iron-carbon micro-electrolysis filler, sodium chloride is added into the catalyst to be used as a reaction electrolyte, so that the reaction efficiency is improved, and the binder with certain conductivity promotes the micro-electrolysis reaction to be stably carried out. The movable turbine turnover stirrer is added in the use process, so that the sufficient reaction time of the iron-carbon micro battery and the wastewater is ensured, and the problem of hardening of the micro-electrolysis filler is solved. The invention has high treatment efficiency, high utilization rate of raw materials, safety and reliability.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for degrading industrial organic wastewater by ultrasonic ozone-micro-electrolysis coupling.
Background
With the rapid development of industries such as petroleum, chemical industry, pharmacy and the like, a large amount of high-concentration organic industrial wastewater which is difficult to degrade is generated, the wastewater has the characteristics of high organic pollutant content, high chromaticity, high toxicity, difficult degradation and the like, and even if the wastewater is diluted by hundreds of times, microorganisms are still difficult to culture and can not be directly subjected to biochemical treatment. Aiming at the characteristic of poor biodegradability of the wastewater, a corresponding pretreatment method can be adopted to improve the biodegradability of the wastewater, so that the treatment effect of a subsequent biochemical system is ensured, and therefore, the selection of an applicable pretreatment method is the key for treating the wastewater. At present, the pretreatment methods for the high-concentration organic wastewater mainly comprise an electrolytic method, advanced oxidation, catalytic oxidation, wet oxidation and the like.
Advanced Oxidation processes (AOPs for short) overcomes the O existing in the common Oxidation process
3、H
2O
2And C
l2The oxidizing agents have the defects of weak oxidizing ability, selectivity and the like, and the special advantages of the oxidizing agents are increasingly paid more attention. The currently commonly used advanced oxidation technologies mainly comprise a Fenton method, an oxidation flocculation method, an ozone method, an ultrasonic degradation method, a photocatalysis method and an electrochemical method. However, a great deal of application research also shows that the oxidation rate and efficiency of a single oxidation technical means can not meet the requirement of degrading organic matters. For this reason, related combination techniques for improving oxidation efficiency have been developed in recent years. The method mainly comprises the following steps: a photoelectrocatalysis oxidation technology, an ultrasonic-electrocatalysis oxidation technology, an ozone electrocatalysis oxidation technology, an electrocatalysis-biological reaction technology and a membrane filtration electrocatalysis oxidation technology. Various combined electrocatalysis water treatment technologies have certain synergistic effect and respective advantages in the treatment of the organic wastewater difficult to degrade, and simultaneously can reduce the running cost of electrocatalysis oxidation to a certain extent. But the combined electrocatalytic oxidation water treatment technology cannot fundamentally solve the common problem faced by the electrocatalytic water treatment technology of low current efficiency and mass transfer limitation. The key to the advanced oxidation method for treating the high-concentration organic wastewater is to improve the treatment efficiency, shorten the treatment time and reduce the treatment cost.
Disclosure of Invention
Aiming at the technical problems, the invention mainly provides a method for degrading industrial organic wastewater by ultrasonic ozone-micro electrolysis coupling.
The technical scheme of the invention is as follows: a method for degrading industrial organic wastewater by ultrasonic ozone-micro electrolysis coupling comprises the following steps:
(1) ultrasonic ozone treatment: introducing high-concentration organic industrial wastewater into an ultrasonic reactor, starting an ultrasonic vibrator to perform vibration degradation on the wastewater, wherein the ultrasonic vibration frequency is 25-45KHZ, the strength is 8-15W/cm2, starting a plasma ozone generator after 1-3min, blowing plasma ozone mixed gas into the wastewater through an aeration device to perform aeration, the volume ratio of gas to water is 2-3:1, and closing the ultrasonic vibrator and the plasma ozone generator after 30-60min to obtain front-end treated wastewater;
(2) iron-carbon micro-electrolysis treatment: adjusting the pH value of the front-end treatment wastewater to 3-4 to obtain acidic wastewater, introducing the acidic wastewater into an iron-carbon micro-electrolysis reactor, and fully mixing and stirring the acidic wastewater and a reinforced micro-electrolysis filler by using an all-position mechanical stirring device according to a material-liquid ratio of 1:2-3, wherein the stirring speed is 20-80r/min, and the retention time of the acidic wastewater is 1-2h to obtain middle-end treatment wastewater;
(3) and (3) biodegradation treatment: introducing the middle-end treatment wastewater into an SBR reactor to carry out anaerobic-aerobic reaction, adjusting the pH to 5.5-7, adjusting the temperature to 30-32 ℃, introducing nitrogen into the anaerobic stage for aeration for 45-70min, introducing air into the aerobic stage for aeration for 60-100min, wherein the aeration flow rate of the two times is 0.08-0.10m3/h, adding 150-200mg/L of flocculant after the aerobic stage is finished, precipitating, standing, and carrying out solid-liquid separation to obtain a supernatant;
(4) wastewater purification treatment: sequentially feeding the supernatant into an adsorption filtration tower, stirring for 15-25min, sterilizing with microwave for 2-5min, and fine filtering with fine filtering equipment to obtain purified water.
Further, the plasma ozone mixed gas in the step (1) is formed by mixing plasma ozone and air, the plasma ozone comes from an oxygen cylinder, the volume percentage of the plasma ozone is 15-35%, the permeability of the plasma ozone is enhanced, and the utilization rate of the ozone can be improved by matching with micro bubbles generated by ultrasonic oscillation.
Further, the aeration device in the step (1) is an alumina ceramic aeration gas distribution plate, the alumina ceramic aeration gas distribution plate is positioned around the ultrasonic reactor, the aperture is 3-4mm, the porosity is 80-90%, and the gas distribution plate has dense pores, so that the time is saved.
Further, the reinforced micro-electrolysis filler in the step (2) comprises the following components in parts by weight: 400-450 parts of sponge iron, 350-400 parts of carbon molecular sieve, 50-60 parts of catalyst and 5-8 parts of adhesive, wherein the sponge iron has less impurities and a pore structure, and has a certain adsorption effect as the carbon molecular sieve, the iron-carbon micro-electrolysis reaction is easier due to the addition of the catalyst, and the sponge iron, the carbon molecular sieve and the catalyst can be tightly wrapped by the added adhesive, so that the iron-carbon micro-battery can be well operated.
Further, the preparation method of the reinforced micro-electrolysis filler in the step (2) comprises the following steps: firstly, preparing a binder colloid, dissolving the binder and water according to a feed liquid volume ratio of 1:30-50, wherein the dissolving step comprises the steps of firstly adding water into a container, rapidly stirring by using a stirrer, simultaneously slowly, uniformly, dispersing and adding the binder with the weight components in batches, and uniformly stirring after the water completely soaks the powder; secondly, soaking the sponge iron in 5% dilute sulfuric acid for 15-25min, repeatedly washing with clear water for 5-10min to obtain activated sponge iron, uniformly mixing the activated sponge iron, the carbon molecular sieve and the catalyst according to the weight components, and spraying the binder in batches and uniformly during the process; and thirdly, granulating the mixture of the components by adopting a 24-mesh wet method, drying the granules for 1-3 hours in a blowing manner at the temperature of 70-80 ℃, granulating the obtained dry granules by 20 meshes, and controlling the moisture of the granules to be less than 0.5% to obtain the reinforced micro-electrolysis filler.
Furthermore, the apparent density of the reinforced micro-electrolysis filler is 35-40%, the bulk density is 50-55%, and the reasonable apparent density and bulk density can improve the reaction efficiency of micro-electrolysis.
Furthermore, the adhesive preferably uses iron powder adhesive powder with the particle size of 80-100 meshes, the catalyst is mixed powder of sodium chloride and calcium compound in a mass ratio of 1:4-6, the particle size is 80-100 meshes, and chloride ions and sodium ions ionized by the sodium chloride when meeting water are good electrolytes, so that the effect of the catalyst can be better.
Further, the all-position mechanical stirring device in the step (2) is a movable turbine turnover stirrer, the moving line of the walking turbine turnover stirrer is firstly 'Z' -shaped and transversely stirred from left to right, then 'Z' -shaped and longitudinally stirred from bottom to top after reaching the bottom, the moving speed is 1-2m/s, the working period is 30-40min, and an intermittent all-position stirring mode is adopted, so that the sufficient reaction time of the iron-carbon micro battery and the wastewater is ensured, and the problem of hardening of the micro-electrolysis filler is solved.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts the micro-bubbles generated by ultrasonic oscillation and the plasma ozone output by the gas distribution plate to carry out front-end treatment on the industrial organic wastewater, the micro-bubbles reduce the surface tension of the water, further strengthen the permeability of the plasma ozone, further avoid the escape of the ozone and improve the utilization rate of the ozone. The sponge iron and the carbon molecular sieve are used as reinforced iron-carbon micro-electrolysis fillers, the sodium chloride is added into the used catalyst to be used as reaction electrolyte, the reaction efficiency is improved, the binder with certain conductivity is used for mixing and granulating, the contact area and the strength of the sponge iron, the carbon molecular sieve and the catalyst are enhanced, and the micro-electrolysis reaction is promoted to be stably carried out. The movable turbine turnover stirrer is added in the using process, and an intermittent full-position stirring mode is adopted, so that the sufficient reaction time of the iron-carbon micro battery and the wastewater is ensured, and the problem of hardening of the micro-electrolysis filler is solved. The invention has high treatment efficiency, high utilization rate of raw materials, safety and reliability.
Detailed Description
For the understanding of the present invention, the following description will be further explained by taking specific examples as examples, which are not to be construed as limiting the embodiments of the present invention.
Example 1:
a method for degrading industrial organic wastewater by ultrasonic ozone-micro electrolysis coupling comprises the following steps:
(1) ultrasonic ozone treatment: introducing high-concentration organic industrial wastewater into an ultrasonic reactor, starting an ultrasonic vibrator to vibrate and degrade the wastewater, wherein the ultrasonic vibration frequency is 25KHZ, the strength is 8W/cm2, starting a plasma ozone generator after 1min, blowing plasma ozone mixed gas into the wastewater through an aeration device to aerate, wherein the volume ratio of gas to water is 2:1, and closing the ultrasonic vibrator and the plasma ozone generator after 30min to obtain front-end treated wastewater; the plasma ozone mixed gas is formed by mixing plasma ozone and air, the plasma ozone is from an oxygen cylinder, the volume percentage of the plasma ozone is 15-35%, the permeability of the plasma ozone is enhanced, and the utilization rate of the ozone can be improved by matching with micro bubbles generated by ultrasonic oscillation. Wherein, the aeration device is an alumina ceramic aeration gas distribution plate which is positioned around the ultrasonic reactor, the aperture is 3mm, the porosity is 80 percent, and the gas distribution plate has dense pores, thereby being beneficial to dispersion and saving time.
(2) Iron-carbon micro-electrolysis treatment: adjusting the pH value of the front-end treatment wastewater to 3 to obtain acidic wastewater, introducing the acidic wastewater into an iron-carbon micro-electrolysis reactor, and fully mixing and stirring the acidic wastewater and a reinforced micro-electrolysis filler by using an all-position mechanical stirring device according to a material-liquid ratio of 1:2, wherein the stirring speed is 20r/min, and the retention time of the acidic wastewater is 1h to obtain middle-end treatment wastewater; wherein the reinforced micro-electrolysis filler comprises the following components in parts by weight: 400 parts of sponge iron, 350 parts of carbon molecular sieve, 50 parts of catalyst and 5 parts of adhesive, wherein the sponge iron has less impurities and a pore structure, and has a certain adsorption effect as a carbon molecular sieve, the iron-carbon micro-electrolysis reaction is easier due to the addition of the catalyst, and the sponge iron, the carbon molecular sieve and the catalyst can be tightly wrapped by the added adhesive, so that the iron-carbon micro-battery can be well operated. The preparation method of the reinforced micro-electrolysis filler comprises the following steps: firstly, preparing a binder colloid, dissolving the binder and water according to the feed liquid volume ratio of 1:30, wherein the dissolving step comprises the steps of firstly adding water into a container, rapidly stirring by using a stirrer, simultaneously slowly, uniformly, dispersing and adding the binder with the weight components in batches, and uniformly stirring after the water completely soaks the powder; secondly, soaking the sponge iron in 5% dilute sulfuric acid for 15min, repeatedly washing with clear water for 5min to obtain activated sponge iron, uniformly mixing the activated sponge iron, the carbon molecular sieve and the catalyst according to the weight components, and spraying the binder in batches and uniformly during the process; and thirdly, granulating the mixture of the components by adopting a 24-mesh wet method, carrying out forced air drying on the granules for 1 hour at the temperature of 70 ℃, finishing the obtained dry granules by 20 meshes, and controlling the moisture of the granules to be less than 0.5% to obtain the reinforced micro-electrolysis filler. Wherein the apparent density of the reinforced micro-electrolysis filler is 35%, the bulk density is 50%, and the reasonable apparent density and bulk density can improve the reaction efficiency of micro-electrolysis. The iron powder adhesive powder is preferably used as the adhesive, the particle size is 80 meshes, the catalyst is mixed powder of sodium chloride and a calcium compound in a mass ratio of 1:4, the particle size is 80 meshes, and chloride ions and sodium ions ionized by the sodium chloride when meeting water are good electrolytes, so that the effect of the catalyst can be better. The all-position mechanical stirring device is a movable turbine overturning stirrer, the moving route of the walking turbine overturning stirrer is firstly 'Z' -shaped and transversely stirred from left to right, then 'Z' -shaped and longitudinally stirred from bottom to top after reaching the bottom, the moving speed is 1m/s, the working period is 30min, and an intermittent all-position stirring mode is adopted, so that the sufficient reaction time of the iron-carbon micro battery and wastewater is ensured, and the problem of hardening of a micro-electrolysis filler is solved.
(3) And (3) biodegradation treatment: introducing the middle-end treated wastewater into an SBR reactor for anaerobic-aerobic reaction, adjusting the pH to 5.5, controlling the temperature to be 30 ℃, introducing nitrogen gas for aeration for 45min in an anaerobic stage, introducing air for aeration for 60min in an aerobic stage, wherein the aeration flow rate of the two times is 0.08m
3After the aerobic stage is finished, adding 150mg/L of flocculating agent, precipitating and standing, and performing solid-liquid separation to obtain supernatant;
(4) wastewater purification treatment: and sequentially feeding the supernatant into an adsorption filtration tower, stirring for 15min in a rolling way, sterilizing for 2min by microwave, and finely filtering by fine filtration equipment to obtain purified water.
Example 2:
a method for degrading industrial organic wastewater by ultrasonic ozone-micro electrolysis coupling comprises the following steps:
(1) ultrasonic ozone treatment: introducing high-concentration organic industrial wastewater into an ultrasonic reactor, and turning on an ultrasonic vibrator to vibrate and reduce the wastewaterThe ultrasonic vibration frequency is 35KHZ, and the intensity is 11W/cm
2Opening a plasma ozone generator after 2min, blowing plasma ozone mixed gas into the wastewater through an aeration device for aeration, wherein the volume ratio of the gas to the water is 2.5:1, and closing the ultrasonic vibrator and the plasma ozone generator after 45min to obtain front-end treated wastewater; the plasma ozone mixed gas is formed by mixing plasma ozone and air, the plasma ozone is from an oxygen cylinder, the volume percentage of the plasma ozone is 25%, the permeability of the plasma ozone is enhanced, and the utilization rate of the ozone can be improved by matching with micro bubbles generated by ultrasonic oscillation. Wherein, the aeration device is an alumina ceramic aeration gas distribution plate which is positioned around the ultrasonic reactor, the aperture is 3mm, the porosity is 85 percent, and the gas distribution plate has dense pores, thus being beneficial to dispersion and saving time.
(2) Iron-carbon micro-electrolysis treatment: adjusting the pH value of the front-end treatment wastewater to 3.5 to obtain acidic wastewater, introducing the acidic wastewater into an iron-carbon micro-electrolysis reactor, and fully mixing and stirring the acidic wastewater and a reinforced micro-electrolysis filler by using an all-position mechanical stirring device according to a material-liquid ratio of 1:2.5, wherein the stirring speed is 50r/min, and the retention time of the acidic wastewater is 1.5h to obtain middle-end treatment wastewater; wherein the reinforced micro-electrolysis filler comprises the following components in parts by weight: 420 parts of sponge iron, 370 parts of carbon molecular sieve, 55 parts of catalyst and 7 parts of adhesive, wherein the sponge iron has less impurities and a pore structure, and has a certain adsorption effect as a carbon molecular sieve, the iron-carbon micro-electrolysis reaction is easier due to the addition of the catalyst, and the sponge iron, the carbon molecular sieve and the catalyst can be tightly wrapped by the added adhesive, so that the iron-carbon micro-battery can be well operated. The preparation method of the reinforced micro-electrolysis filler comprises the following steps: firstly, preparing a binder colloid, dissolving the binder and water according to the feed liquid volume ratio of 1:30, wherein the dissolving step comprises the steps of firstly adding water into a container, rapidly stirring by using a stirrer, simultaneously slowly, uniformly, dispersing and adding the binder with the weight components in batches, and uniformly stirring after the water completely soaks the powder; secondly, soaking the sponge iron in 5% dilute sulfuric acid for 20min, repeatedly washing with clear water for 7min to obtain activated sponge iron, uniformly mixing the activated sponge iron, the carbon molecular sieve and the catalyst according to the weight components, and spraying the binder in batches and uniformly during the process; and thirdly, granulating the mixture of the components by adopting a 24-mesh wet method, carrying out forced air drying on the granules for 2 hours at the temperature of 75 ℃, finishing the obtained dry granules by 20 meshes, and controlling the moisture of the granules to be less than 0.5% to obtain the reinforced micro-electrolysis filler. Wherein the apparent density of the reinforced micro-electrolysis filler is 37%, the bulk density is 52%, and the reasonable apparent density and bulk density can improve the reaction efficiency of micro-electrolysis. The adhesive preferably uses iron powder adhesive powder with the particle size of 90 meshes, the catalyst is mixed powder of sodium chloride and a calcium compound in a mass ratio of 1:5, the particle size is 90 meshes, and chloride ions and sodium ions ionized by the sodium chloride when meeting water are good electrolytes, so that the effect of the catalyst is better. The all-position mechanical stirring device is a movable turbine overturning stirrer, the moving route of the walking turbine overturning stirrer is firstly 'Z' -shaped and transversely stirred from left to right, then 'Z' -shaped and longitudinally stirred from bottom to top after reaching the bottom, the moving speed is 1.5m/s, the working period is 35min, and an intermittent all-position stirring mode is adopted, so that the sufficient reaction time of the iron-carbon micro battery and the wastewater is ensured, and the problem of hardening of the micro-electrolysis filler is solved.
(3) And (3) biodegradation treatment: introducing the middle-end treated wastewater into an SBR reactor for anaerobic-aerobic reaction, adjusting the pH to 6.3, controlling the temperature to 31 ℃, introducing nitrogen gas for aeration for 60min in an anaerobic stage, introducing air for aeration for 80min in an aerobic stage, wherein the aeration flow rate of the two times is 0.09m
3After the aerobic stage is finished, adding 175mg/L of flocculating agent, precipitating and standing, and carrying out solid-liquid separation to obtain supernatant;
(4) wastewater purification treatment: and sequentially feeding the supernatant into an adsorption filtration tower, stirring for 20min in a rolling way, sterilizing for 3min by microwave, and finely filtering by fine filtration equipment to obtain purified water.
Example 3:
a method for degrading industrial organic wastewater by ultrasonic ozone-micro electrolysis coupling comprises the following steps:
(1) ultrasonic ozone treatment: introducing high-concentration organic industrial wastewater into an ultrasonic reactor, starting an ultrasonic vibrator to vibrate and degrade the wastewater, wherein the ultrasonic vibration frequency is 45KHZ, and the intensity is 15W/cm
2Opening a plasma ozone generator after 3min, and blowing plasma ozone mixed gas into the wastewater through an aeration device for aeration, wherein the volume ratio of the gas to the water is 3:1, and closing the ultrasonic vibrator and the plasma ozone generator after 60min to obtain front-end treated wastewater; the plasma ozone mixed gas is formed by mixing plasma ozone and air, the plasma ozone is from an oxygen cylinder, the volume percentage of the plasma ozone is 35%, the permeability of the plasma ozone is enhanced, and the utilization rate of the ozone can be improved by matching with micro bubbles generated by ultrasonic oscillation. The aeration device is an alumina ceramic aeration gas distribution plate, the alumina ceramic aeration gas distribution plate is positioned around the ultrasonic reactor, the aperture is 4mm, the porosity is 90%, and the gas distribution plate is dense in pores, so that the time is saved by dispersion.
(2) Iron-carbon micro-electrolysis treatment: adjusting the pH value of the front-end treatment wastewater to 4 to obtain acidic wastewater, introducing the acidic wastewater into an iron-carbon micro-electrolysis reactor, and fully mixing and stirring the acidic wastewater and a reinforced micro-electrolysis filler by using an all-position mechanical stirring device according to a material-liquid ratio of 1:3, wherein the stirring speed is 80r/min, and the retention time of the acidic wastewater is 2 hours to obtain middle-end treatment wastewater; wherein the reinforced micro-electrolysis filler comprises the following components in parts by weight: 450 parts of sponge iron, 400 parts of carbon molecular sieve, 60 parts of catalyst and 8 parts of adhesive, wherein the sponge iron has less impurities and a pore structure, and has a certain adsorption effect as a carbon molecular sieve, the iron-carbon micro-electrolysis reaction is easier due to the addition of the catalyst, and the sponge iron, the carbon molecular sieve and the catalyst can be tightly wrapped by the added adhesive, so that the iron-carbon micro-battery can be well operated. The preparation method of the reinforced micro-electrolysis filler comprises the following steps: firstly, preparing a binder colloid, dissolving the binder and water according to the feed liquid volume ratio of 1:30, wherein the dissolving step comprises the steps of firstly adding water into a container, rapidly stirring by using a stirrer, simultaneously slowly, uniformly, dispersing and adding the binder with the weight components in batches, and uniformly stirring after the water completely soaks the powder; secondly, soaking the sponge iron in 5% dilute sulfuric acid for 25min, repeatedly washing with clear water for 10min to obtain activated sponge iron, uniformly mixing the activated sponge iron, the carbon molecular sieve and the catalyst according to the weight components, and spraying the binder in batches and uniformly during the process; and thirdly, granulating the mixture of the components by adopting a 24-mesh wet method, carrying out forced air drying on the granules for 3 hours at the temperature of 80 ℃, finishing the obtained dry granules by 20 meshes, and controlling the moisture of the granules to be less than 0.5% to obtain the reinforced micro-electrolysis filler. Wherein the apparent density of the reinforced micro-electrolysis filler is 40%, the bulk density is 55%, and the reasonable apparent density and bulk density can improve the reaction efficiency of micro-electrolysis. The binder preferably uses iron powder binder powder with the particle size of 100 meshes, the catalyst is mixed powder of sodium chloride and a calcium compound in a mass ratio of 1:6, the particle size is 100 meshes, and chloride ions and sodium ions ionized by the sodium chloride when meeting water are good electrolytes, so that the effect of the catalyst is better. The all-position mechanical stirring device is a movable turbine overturning stirrer, the moving route of the walking turbine overturning stirrer is firstly 'Z' -shaped and transversely stirred from left to right, then 'Z' -shaped and longitudinally stirred from bottom to top after reaching the bottom, the moving speed is 2m/s, the working period is 40min, and an intermittent all-position stirring mode is adopted, so that the sufficient reaction time of the iron-carbon micro battery and wastewater is ensured, and the problem of hardening of a micro-electrolysis filler is solved.
(3) And (3) biodegradation treatment: introducing the middle-end treated wastewater into an SBR reactor for anaerobic-aerobic reaction, adjusting the pH to 7, the temperature to 32 ℃, introducing nitrogen gas for aeration for 70min in an anaerobic stage, introducing air for aeration for 100min in an aerobic stage, wherein the aeration flow rate of the two times is 0.10m
3After the aerobic stage is finished, adding 200mg/L of flocculating agent, precipitating and standing, and performing solid-liquid separation to obtain supernatant;
(4) wastewater purification treatment: and sequentially feeding the supernatant into an adsorption filtration tower, stirring for 25min in a rolling way, sterilizing for 5min by microwave, and finely filtering by fine filtration equipment to obtain purified water.
While the invention has been described and illustrated with reference to specific embodiments thereof, those skilled in the art will appreciate that various changes, modifications and substitutions can be made therein without departing from the spirit and scope of the invention. It is the intention, therefore, to be limited only as indicated by the scope of the claims which follow and that such claims be interpreted as broadly as is reasonable.
Claims (7)
1. A method for degrading industrial organic wastewater by ultrasonic ozone-micro electrolysis coupling is characterized by comprising the following steps:
(1) ultrasonic ozone treatment: introducing high-concentration organic industrial wastewater into an ultrasonic reactor, starting an ultrasonic vibrator to vibrate and degrade the wastewater, wherein the ultrasonic vibration frequency is 25-45KHZ, and the intensity is 8-15W/cm
2Opening the plasma ozone generator after 1-3min, blowing plasma ozone mixed gas into the wastewater through an aeration device for aeration, wherein the volume ratio of gas to water is 2-3:1, and closing the ultrasonic vibrator and the plasma ozone generator after 30-60min to obtain front-end treated wastewater;
(2) iron-carbon micro-electrolysis treatment: adjusting the pH value of the front-end treatment wastewater to 3-4 to obtain acidic wastewater, introducing the acidic wastewater into an iron-carbon micro-electrolysis reactor, and fully mixing and stirring the acidic wastewater and a reinforced micro-electrolysis filler by using an all-position mechanical stirring device according to a material-liquid ratio of 1:2-3, wherein the stirring speed is 20-80r/min, and the retention time of the acidic wastewater is 1-2h to obtain middle-end treatment wastewater;
(3) and (3) biodegradation treatment: introducing the middle-end treated wastewater into an SBR reactor to carry out anaerobic-aerobic reaction, adjusting the pH to 5.5-7, the temperature to be 30-32 ℃, introducing nitrogen gas into the anaerobic stage for aeration for 45-70min, introducing air into the aerobic stage for aeration for 60-100min, wherein the aeration flow rate of the two times is 0.08-0.10m
3After the aerobic stage is finished, adding 150-200mg/L flocculant, precipitating, standing, and performing solid-liquid separation to obtain a supernatant;
(4) wastewater purification treatment: sequentially feeding the supernatant into an adsorption filtration tower, stirring for 15-25min, sterilizing with microwave for 2-5min, and fine filtering with fine filtering equipment to obtain purified water.
2. The method for degrading industrial organic wastewater by ultrasonic ozone-micro electrolysis coupling according to claim 1, wherein the plasma ozone mixed gas in the step (1) is formed by mixing plasma ozone and air, the plasma ozone is derived from an oxygen cylinder, and the volume percentage of the plasma ozone is 15-35%.
3. The method for degrading industrial organic wastewater by ultrasonic ozone-microelectrolysis coupling according to claim 1, wherein the aeration device is an alumina ceramic aeration gas distribution plate, the alumina ceramic aeration gas distribution plate is positioned around the ultrasonic reactor, the pore diameter is 3-4mm, and the porosity is 80-90%.
4. The method for degrading industrial organic wastewater by ultrasonic ozone-micro electrolysis coupling according to claim 1, wherein the reinforced micro electrolysis filler in the step (2) is composed of the following components by weight: 400-450 parts of sponge iron, 350-400 parts of carbon molecular sieve, 50-60 parts of catalyst and 5-8 parts of adhesive.
5. The method for degrading industrial organic wastewater by ultrasonic ozone-micro electrolysis coupling according to claim 1, wherein the apparent density of the reinforced micro electrolysis filler is 35-40%, and the bulk density is 50-55%.
6. The method for degrading industrial organic wastewater by ultrasonic ozone-micro electrolysis coupling according to claim 1, wherein the adhesive is preferably iron powder adhesive powder with a particle size of 80-100 meshes, and the catalyst is mixed powder of sodium chloride and calcium compound with a mass ratio of 1:4-6, and the particle size is 80-100 meshes.
7. The method for degrading industrial organic wastewater by ultrasonic ozone-micro electrolysis coupling according to claim 1, wherein the all-position mechanical stirring device in the step (2) is a movable turbine turnover stirrer, the moving route of the walking turbine turnover stirrer is firstly zigzag-shaped, transversely stirring from left to right, then longitudinally stirring from bottom to top, the moving speed is 1-2m/s, and the working period is 30-40 min.
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