CN108383335B - High-concentration organic wastewater treatment system and method - Google Patents
High-concentration organic wastewater treatment system and method Download PDFInfo
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Abstract
The application discloses a high-concentration organic wastewater treatment system, which comprises an adjusting tank, a continuous hydrothermal oxidation system, an anaerobic reaction system, an aerobic reaction system and an activated carbon adsorption system which are sequentially communicated through liquid pipelines; the active carbon adsorption system is sequentially communicated with the aerobic reaction system, the intermittent wet oxidation system and the active carbon washing system through solid pipelines to form an active carbon circulating treatment loop; the effluent part of the activated carbon adsorption system is directly discharged, and part of the effluent part is led into an activated carbon washing system to be used as washing water; and the liquid generated by the activated carbon washing system and the intermittent wet oxidation system is directly led into the regulating tank through a liquid pipeline after being collected. The application also discloses a method for treating high-concentration organic wastewater by using the system. Through the whole process, the COD removal rate of the wastewater is more than 99.8%; the process can effectively realize the treatment of high-concentration organic wastewater, the partial recovery and disposal of the catalyst and the utilization of intermediate products, and ensures the safe water outlet and the stable disposal of sludge of the system.
Description
Technical Field
The application relates to a wastewater treatment technology, in particular to a high-concentration organic wastewater treatment system and a method.
Background
The high-concentration organic wastewater generally refers to wastewater containing higher-concentration organic matters discharged by industries such as food, papermaking, pesticide and the like, and the COD content of the wastewater is generally more than 2000 mg/L. These high concentration organic wastewater usually contains a large amount of carbohydrate, fat, fiber, etc., and some high concentration organic wastewater is even accompanied by strong biotoxicity, if the wastewater is not properly treated, serious damage to the ecological environment is easily caused, and the human health is threatened.
Wet air oxidation technology (Wet Air Oxidation, WAO) is a proposed hydrothermal oxidation process for effectively treating high-concentration, toxic and hazardous wastewater in the 50 s of the 20 th century. The process is to convert organic matters in the wastewater into H by utilizing air or oxygen (or oxydol, ozone and other oxidants) under the conditions of high temperature (125-350 ℃) and high pressure (0.5-20 MPa) 2 O、CO 2 And other small molecule organics. The wet oxidation process has wide treatment range, high removal rate and NO generation x And dioxin and the like, and the wet oxidation belongs to exothermic reaction, and the heat generated in the reaction process can effectively reduce the energy consumption. However, hydrothermal oxidation processes often do not completely remove organics from the wastewater, and often require the addition of a catalyst to the wet oxidation system in order to increase the removal of COD from the wastewater. Because heterogeneous catalysts are extremely easy to generate problems such as hardening and the like in the wet oxidation process, the conventional method is to add a homogeneous catalyst to improve the treatment efficiency of wastewater in the actual industrial application process of wet oxidation, but the homogeneous catalyst is effectively treated, so that potential threats to the water body are extremely easy to generate.
The activated carbon has strong adsorption universality and adsorption capacity, and is commonly used for adsorbing low-concentration substances in wastewater in the water treatment process. However, if the activated carbon saturated by adsorption cannot be recycled, the input cost of cleaning the activated carbon is increased, serious resource waste is caused, and secondary pollution is possibly caused. At present, the research on wastewater treatment by activated carbon is mainly focused on powdered activated carbon, and the later carbon-water separation is complicated.
Disclosure of Invention
The application aims to: aiming at the defects in the prior art, the application provides a high-concentration organic wastewater treatment system and a treatment method which can reduce catalyst pollution, are environment-friendly and have good treatment effect.
The technical scheme is as follows: the application relates to a high-concentration organic wastewater treatment system, which comprises an adjusting tank, a continuous hydrothermal oxidation system, an anaerobic reaction system, an aerobic reaction system and an activated carbon adsorption system which are sequentially communicated through liquid pipelines; the active carbon adsorption system is sequentially communicated with the aerobic reaction system, the intermittent wet oxidation system and the active carbon washing system through solid pipelines to form an active carbon circulating treatment loop; the effluent part of the activated carbon adsorption system is directly discharged, and part of the effluent part is led into an activated carbon washing system to be used as washing water; and the liquid generated by the activated carbon washing system and the intermittent wet oxidation system is directly led into the regulating tank through a liquid pipeline after being collected.
Further, the outlet of the regulating tank is communicated with the inlet of the continuous hydrothermal oxidation system, the outlet of the continuous hydrothermal oxidation system is connected with the inlet of the anaerobic reaction system, the outlet of the anaerobic reaction system is connected with the inlet of the aerobic reaction system, the outlet of the liquid of the aerobic reaction system is connected with the active carbon adsorption system, and the liquid of the active carbon adsorption system is connected with the water outlet; the solid outlet of the activated carbon adsorption system is connected with the solid inlet of the aerobic reaction system, the solid outlet of the aerobic reaction system is connected with the solid inlet of the intermittent wet oxidation system, the solid outlet of the intermittent wet oxidation system is connected with the solid inlet of the activated carbon washing system, and the solid outlet of the activated carbon washing system is connected with the solid inlet of the activated carbon adsorption system; the liquid phase generated by the intermittent wet oxidation system and the activated carbon washing system is directly led into the regulating tank through a pipeline. The gas generated in the system can be completely collected and guided into the incinerator for incineration treatment, for example, a continuous hydrothermal oxidation system, an anaerobic reaction system and an aerobic reaction system are respectively provided with corresponding exhaust ports.
When the system is operated, saturated activated carbon generated by the activated carbon adsorption system is led into the aerobic reaction system, residual activated carbon discharged by the aerobic reaction system is led into the intermittent wet oxidation system for regeneration treatment, and is led into the activated carbon washing system after the regeneration treatment, and clean activated carbon generated by the activated carbon washing system is led into the activated carbon adsorption system again for recycling.
And a stirring device is arranged in the regulating tank and is used for fully and uniformly mixing the mixed sewage generated by the intermittent wet oxidation system and the activated carbon washing system with untreated wastewater, and then guiding the mixed sewage into the continuous hydrothermal oxidation system for reaction.
And a drug adding device and a stirrer are connected in series on a pipeline between the regulating tank and the continuous hydrothermal oxidation system and are used for adding a catalyst and stirring.
Preferably, a pipeline connected to the feed inlet of the anaerobic reaction system is further arranged in the reaction zone of the anaerobic reaction system, and a water pump is connected in series on the pipeline and used for pumping out the mixture in the stable reaction of the anaerobic reaction system and mixing the mixture with the effluent of the continuous hydrothermal oxidation system and then leading the mixture into the anaerobic reaction system.
Further, an intermittent stirrer is arranged in the anaerobic reaction system.
Further, the anaerobic reaction system is an up-flow anaerobic sludge blanket; the aerobic reaction system is a biological aerated filter, wherein the filler is granular activated carbon.
In order to ensure that the system runs smoothly, a water pump can be connected in series on the pipeline as required. For example, sewage which is stably reacted between the regulating tank and the continuous hydrothermal oxidation system and in the anaerobic reaction system is pumped by a water pump to be mixed with water discharged by the continuous hydrothermal oxidation system, and the water discharged by the water pump is pumped to the regulating tank by an activated carbon washing system, the water discharged by the activated carbon washing system and the water discharged by the intermittent wet oxidation system.
A method for treating high-concentration organic wastewater by using the system comprises the following steps:
(1) Continuous hydrothermal oxidation: filtering the wastewater to be treated, removing slag, introducing the wastewater into an adjusting tank, uniformly stirring, and adjusting the pH to 7-9; then introducing the mixture into a continuous hydrothermal oxidation system, adding a catalyst, taking pure oxygen as an oxidant, and reacting for 1.5-2.5 h;
(2) Anaerobic reaction treatment: the liquid product after the reaction in the step (1) is subjected to heat exchange and temperature reduction, and then is led into an anaerobic reaction system to react for 2-4 days at the temperature of 30-35 ℃;
(3) And (3) aerobic reaction treatment: directly introducing the effluent treated in the step (2) into an aerobic reaction system, after staying for 1-3 days, directly introducing the effluent into an active carbon adsorption system, adsorbing and removing residual organic matters and heavy metal catalysts, and discharging; wherein the aerobic reaction system is a biological aerated filter, and the filler is granular activated carbon; (4) activated carbon cyclic treatment: introducing saturated activated carbon generated by the treatment of an activated carbon adsorption system into an aerobic reaction system, introducing residual activated carbon discharged by the aerobic reaction system into an intermittent wet oxidation system for regeneration treatment, introducing the regenerated activated carbon into an activated carbon washing system, introducing clean activated carbon generated by the activated carbon washing system into the activated carbon adsorption system for recycling, and directly discharging sludge residues; the effluent part of the activated carbon adsorption system is directly discharged, and the effluent part is led into an activated carbon washing system to be used as washing water after the pH is partially regulated to 8-9; and the liquid generated by the activated carbon washing system and the intermittent wet oxidation system is directly led into the regulating tank through a liquid pipeline after being collected.
In the step (1), the continuous hydrothermal oxidation reaction conditions are as follows: the oxidation coefficient is 0.9-1.0, the temperature is 280-320 ℃, and the pressure is 7-9 MPa. The oxidation coefficient of the continuous wet oxidation reaction system is 0.9-1.0, and the reaction is in an anoxic state.
In the step (1), the catalyst is one or more selected from copper, iron, manganese, rhodium, ruthenium and palladium, and the mass concentration of the catalyst is maintained at 0.1-0.3%.
In the step (1), the oxygen is used for preparing high-purity oxygen on site by utilizing air separation equipment, and the purity of the oxygen is more than 90 percent.
In the step (2), the anaerobic reaction system is an up-flow anaerobic sludge blanket (UASB), and the sedimentation zone in the up-flow anaerobic sludge blanket accounts for 15-20% of the total volume.
In the step (2), an intermittent stirrer is arranged in the anaerobic reflecting system, the stirring interval is half an hour, and stirring is carried out for 10-15 minutes each time.
In the step (2), the mixture in the stable reaction of the anaerobic reaction system is pumped out and mixed with the effluent of the continuous hydrothermal oxidation system, and then the mixture is introduced into the anaerobic reaction system after the concentration of acetic acid is regulated to be 500-1500 mg/L, pH to be 6.5-7.5. The sewage mixture in the anaerobic reaction system which is operated stably in the step is the sewage mixture rich in methanogen of acetic acid, and the mixing can increase the number of anaerobic bacteria in the water.
In the step (3), the particle size of the granular activated carbon is 4-8 mm, and the layer height is 1.5-2 m.
In the step (4), the activated carbon used by the activated carbon adsorption system is granular activated carbon, and the grain diameter is 4-8 mm.
In the step (4), the intermittent wet oxidation reaction system adopts hydrogen peroxide and high-concentration oxygen as combined oxidants, the oxidation coefficient is kept at 1.5-2, the temperature is 260-300 ℃, the reaction time is 1.5-2 h, the volume fraction of the hydrogen peroxide is 10% -15%, and the activated carbon is regenerated by using Fenton reaction and wet oxidation.
After the continuous hydrothermal oxidation reaction in the step (1), the organic matters in the high-concentration organic wastewater are oxidized and decomposed into small molecular organic matters such as carbon dioxide, water, acetic acid, carboxylic acid and the like, and if the small molecular organic matters directly enter a subsequent aerobic reaction system, the treatment pressure of an aerobic reactor is greatly increased, and the recycling of the small molecular organic acids cannot be realized; in the application, in the step (2), effluent after continuous hydrothermal oxidation treatment is led into an anaerobic reaction system, micromolecular organic acid generated by the hydrothermal oxidation system is used for nutrient substances of methane bacteria, meanwhile, the treatment pressure of an aerobic reactor in the step (3) is reduced, organic matters with smaller molecular weight in wastewater after anaerobic biological treatment are treated by aerobic organisms and decomposed into inorganic matters, and then the inorganic matters are discharged into an activated carbon adsorption system, so that biological treatment effluent is adsorbed, and residual organic matters and heavy metal catalysts in the effluent are adsorbed and removed; and finally, the saturated activated carbon generated by the activated carbon adsorption system is guided to an aerobic reaction system for aerobic treatment through an activated carbon regeneration circulation system in the step (4), is used as a supplementary filler of an aerobic bioreactor, and is discharged into an intermittent wet oxidation system for regeneration, so that part of catalyst is recycled after being washed and returned to an adjusting tank, the catalyst is recycled after entering the system again, and the rest of catalyst is discharged along with residues after being solidified, so that the pollution of the catalyst to the environment is prevented.
The beneficial effects are that: the treatment method of the high-concentration wastewater provided by the application has the following advantages:
(1) The method combining the hydrothermal oxidation process, the biological treatment process and the activated carbon adsorption process can effectively reduce the residual organic pollutants, chromaticity and heavy metals in the effluent, and the COD removal rate of the wastewater is more than or equal to 99.8%;
(2) The traditional hydrothermal oxidation reaction has few recycling of the catalyst, the adsorption recycling and the repeated utilization of the catalyst are realized through the adsorption of the activated carbon, the recycling rate of the heavy metal catalyst is more than or equal to 90%, the catalyst use amount can be reduced under the condition that the system is stable in operation, the medicament cost is saved, and the pollution risk of heavy metal to the storage water body is reduced;
(3) The traditional hydrothermal oxidation treatment is difficult to realize thorough oxidation of organic matters, the high-concentration organic matters are usually decomposed into small molecular organic matters such as small molecular carboxylic acid after the hydrothermal oxidation treatment, and if the small molecular organic matters directly enter a subsequent aerobic reaction system, the treatment pressure of an aerobic reactor is greatly increased, and the recycling of the small molecular organic acids cannot be realized; the method comprises the steps of firstly, introducing effluent water after continuous hydrothermal oxidation treatment into an anaerobic reaction system, using micromolecular organic acid generated by the hydrothermal oxidation system for nutrient substances of methane bacteria, and simultaneously reducing the treatment pressure of an aerobic reactor;
(4) The traditional hydrothermal oxidation treatment active carbon process is mainly aimed at powdery active carbon, and the phenomena of difficult separation, easy blockage and the like of the active carbon are very easy to occur;
(5) The application returns the activated carbon with saturated adsorption to the aerobic treatment system, carries out aerobic treatment on the adsorbed organic matters, reduces the treatment pressure of the intermittent wet oxidation reactor, and is used for replacing the activated carbon in the aerobic reactor;
(6) The water used by the activated carbon washing system is sourced from the system water, the pH is adjusted to be alkaline by sodium hydroxide, the cleaning capacity is increased, and meanwhile, the generated alkaline water returns to the adjusting tank for adjusting the pH of raw water, so that the use amount of a medicament is saved, and the environment-friendly requirement is met;
(7) The excessive sludge generated by the system is effectively separated from the activated carbon by the washing system of the activated carbon, and the sludge is subjected to high-temperature treatment of the intermittent wet oxidation system, so that the sludge is highly concentrated, heavy metals are solidified in the sludge, and the reduction and harmless treatment of the sludge are realized.
Drawings
FIG. 1 is a schematic diagram of a high concentration organic wastewater treatment system according to the present application.
Detailed Description
The present application will be specifically described with reference to the following examples.
Example 1
The high-concentration organic wastewater treatment system shown in fig. 1 comprises an adjusting tank, a continuous hydrothermal oxidation system, an anaerobic reaction system, an aerobic reaction system and an activated carbon adsorption system which are sequentially communicated through liquid pipelines; the active carbon adsorption system is sequentially communicated with the aerobic reaction system, the intermittent wet oxidation system and the active carbon washing system through solid pipelines to form an active carbon circulating treatment loop; the effluent part of the activated carbon adsorption system is directly discharged, and part of the effluent part is led into an activated carbon washing system to be used as washing water; the liquid generated by the activated carbon washing system and the intermittent wet oxidation system is directly led into the regulating tank through a liquid pipeline after being collected. A drug adding device and a stirrer are connected in series on a pipeline between the regulating tank and the continuous hydrothermal oxidation system; a heat exchange and cooling device is connected in series between the continuous hydrothermal oxidation system and the anaerobic reaction system; the anaerobic reaction system is an up-flow anaerobic sludge bed; the aerobic reaction system is a biological aerated filter, wherein the used filler is granular activated carbon.
When the system is used, the liquid phase outlet of the aerobic reaction system is communicated with the inlet of the active carbon adsorption system, the solid phase outlet of the aerobic reaction system is directly communicated to the intermittent wet oxidation system through a pipeline, the effluent part of the active carbon adsorption system is directly discharged, part of the effluent part is used for washing water of the active carbon washing system, saturated active carbon generated by the active carbon adsorption system is led into the aerobic reaction system, clean active carbon generated by the active carbon washing system is led into the active carbon adsorption system, and liquid generated by the active carbon washing system and the intermittent wet oxidation system is directly led to the regulating tank through the pipeline after being collected. Meanwhile, a pipeline connected to a feed inlet of the anaerobic reaction system is also arranged in the reaction zone of the anaerobic reaction system and is used for extracting a mixture in the stable reaction of the anaerobic reaction system, mixing the mixture with the effluent of the continuous hydrothermal oxidation system and then leading the mixture into the anaerobic reaction system.
All the gases generated in the system are discharged into the atmosphere, for example, a continuous hydrothermal oxidation system, an anaerobic reaction system and an aerobic reaction system are respectively provided with an exhaust port. The mixing device is arranged in the regulating tank and is used for fully and uniformly mixing the mixed sewage generated by the intermittent wet oxidation system and the activated carbon washing system with untreated wastewater, and then guiding the mixed sewage into the continuous hydrothermal oxidation system for reaction. And a drug adding device and a stirrer are connected in series on a pipeline between the regulating tank and the continuous hydrothermal oxidation system and are used for adding and stirring the catalyst. An intermittent stirrer is arranged in the anaerobic reaction system. The anaerobic reaction system is an up-flow anaerobic sludge bed; the aerobic reaction system is a biological aerated filter, wherein the filler is granular activated carbon. In order to ensure that the system runs smoothly, a water pump can be connected in series on the pipeline as required.
Example 2
The method for treating high-concentration organic wastewater by using the system described in example 1:
the wastewater to be treated is: the pH value of the industrial wastewater of a certain chemical plant is 6.63, and the COD is 20800mg/L.
The processing steps are as follows: introducing wastewater to be treated into a regulating tank, adding 30% sodium hydroxide alkali liquor according to actual conditions, regulating the pH of the wastewater to 9, uniformly stirring, adding 2% copper nitrate solution according to requirements into a dosing stirrer on a pipeline between the regulating tank and a continuous hydrothermal oxidation system to keep the mass concentration of a catalyst at 0.1%, and introducing the catalyst into the continuous hydrothermal oxidation system; the continuous hydrothermal oxidation system controls the reaction temperature to 280 ℃, oxygen is used as an oxidant, the oxygen purity is 94%, the oxidation coefficient is 0.9, the reaction pressure is 7MPa, the reaction time is 1.5h, the COD conversion rate of the wastewater after being treated by the continuous hydrothermal oxidation system is 82.1%, the biodegradability of the effluent is 0.49, and the pH value is 7.2; the effluent is mixed with the sewage which is extracted from the reaction of the anaerobic reaction system and is rich in methanogen of acetic acid after heat exchange and cooling, the acetic acid is regulated to 500mg/L, the pH value is 7, and the mixture is discharged into the anaerobic reaction system, and the temperature is 30 ℃ and stays for 2 days; the effluent of the anaerobic reaction system is conveyed to an aerobic reaction system through a pipeline, granular activated carbon with the grain diameter of 5mm is filled in the anaerobic reaction system, the height of an activated carbon layer is 1.5m, the residence time is 1.5 days, and the COD removal rate of the wastewater after being treated by an anaerobic and aerobic process reaches 99.8%; introducing the effluent of the aerobic reaction system into an activated carbon adsorption system, wherein the activated carbon is granular activated carbon with the particle size of 5mm, the height of an activated carbon filter column is 5 meters, the COD removal rate of the effluent after treatment by an activated carbon filter process is more than 99.9%, and the residual amount of the metal catalyst is difficult to detect; the activated carbon with saturated adsorption is used for supplementing the activated carbon replaced by an aerobic reaction system, the excess activated carbon generated by the aerobic reaction system is led into an intermittent wet oxidation system in batches, the treatment volume of each intermittent reaction kettle is 100L, hydrogen peroxide and oxygen are used for mixed oxidation, the volume fraction of the hydrogen peroxide is 12%, the oxygen concentration is 94%, the reaction temperature is 260 ℃, and the reaction time is 2 hours; the mixture treated by the intermittent wet oxidation system is led into a washing system, and is washed and desorbed by sodium hydroxide alkali liquor with the pH value of 8, and the regeneration rate of the activated carbon reaches 97 percent.
Comparative example 1
This comparative example the wastewater to be treated is identical to example 2, and the specific operation differs from example 2 in that: only continuous wet oxidation treatment is performed, and biological treatment, activated carbon adsorption and batch wet oxidation treatment are not performed. The COD conversion rate of the wastewater after continuous wet oxidation is 82.1%, the biodegradability of the effluent is 0.49, and the pH value is 7.2, and the wastewater can not meet the three-level standard of integrated wastewater discharge Standard GB 8978-1996.
Comparative example 2
This comparative example the wastewater to be treated is identical to example 2, and the specific operation differs from example 2 in that: no catalyst is added in the continuous hydrothermal oxidation system. The COD conversion rate of wastewater after continuous wet oxidation is 54.2%, and the COD conversion rate of effluent after subsequent treatment is 76.4%, which cannot meet the three-level standard of integrated wastewater discharge Standard GB 8978-1996.
Comparative example 3
This comparative example the wastewater to be treated is identical to example 2, and the specific operation differs from example 2 in that: no activated carbon adsorption was performed. The COD conversion rate of the wastewater after continuous wet oxidation is 99.8%, and the copper ions in the effluent are monitored to be more than 5mg/L.
Comparative example 4
This comparative example the wastewater to be treated is identical to example 2, and the specific operation differs from example 2 in that: the concentration of acetic acid is not regulated in the anaerobic reaction process, and the concentration of acetic acid entering the anaerobic reactor is 2500mg/L. After anaerobic biological reaction and aerobic biological reaction, the COD of the effluent reaches 2900mg/L, and the effluent can not meet the three-level standard of GB 8978-1996.
Comparative example 5
This comparative example the wastewater to be treated is identical to example 2, and the specific operation differs from example 2 in that: the concentration of acetic acid is not regulated in the anaerobic reaction process, and the concentration of acetic acid entering the anaerobic reactor is 2500mg/L. After anaerobic biological reaction and aerobic biological reaction, the COD of the effluent reaches 2900mg/L, and the effluent can not meet the three-level standard of GB 8978-1996.
Example 3
The method for treating high-concentration organic wastewater by using the system described in example 1:
the wastewater to be treated is: the pH value of the industrial wastewater of a certain chemical plant is 9, and the COD is 41100mg/L.
The processing steps are as follows: introducing wastewater to be treated into a regulating tank, uniformly stirring, adding 2% copper nitrate solution into a dosing stirrer on a pipeline between the regulating tank and a continuous hydrothermal oxidation system according to requirements to keep the mass concentration of a catalyst at 0.2%, and introducing the catalyst into the continuous hydrothermal oxidation system; the continuous hydrothermal oxidation system controls the reaction temperature to 300 ℃, the oxygen purity to 94%, the oxidation coefficient to 0.95, the reaction pressure to 8MPa, the reaction time to 2h, the COD conversion rate of the wastewater after treatment by the continuous hydrothermal oxidation system to 83.7%, the biodegradability of the effluent to 0.5 and the pH to 7.9; the effluent is mixed with the sewage which is extracted from the reaction of the anaerobic reaction system and is rich in methanogen of acetic acid after heat exchange and cooling, the acetic acid is regulated to 1000mg/L, the pH value is 7, and the mixture is led into the anaerobic reaction system, the temperature is 35 ℃, and the mixture stays for 3 days; the effluent of the anaerobic reaction system is conveyed to an aerobic reaction system through a pipeline, granular activated carbon with the grain diameter of 5mm is filled in the anaerobic reaction system, the height of an activated carbon layer is 1.5m, the residence time is 1.5 days, and the COD removal rate of the wastewater after being treated by an anaerobic and aerobic process reaches 99.7%; introducing the effluent of the aerobic reaction system into an activated carbon adsorption system, wherein the activated carbon is granular activated carbon with the particle size of 5mm, the height of an activated carbon filter column is 5 meters, the COD (chemical oxygen demand) removal treatment rate of the effluent after treatment by an activated carbon filter process is more than 99.8%, and the residual amount of a metal catalyst is difficult to detect; the activated carbon with saturated adsorption is used for supplementing activated carbon replaced by an oxygen reaction system, the excess activated carbon generated by the aerobic reaction system is led into an intermittent wet oxidation system in batches, the treatment volume of each intermittent reaction kettle is 100L, hydrogen peroxide and oxygen are used for mixed oxidation, the volume fraction of the hydrogen peroxide is 13%, the oxygen concentration is 94%, the reaction temperature is 280 ℃, and the reaction time is 2 hours; the mixture treated by the intermittent wet oxidation system is led into a washing system, and is washed and desorbed by sodium hydroxide alkali liquor with the pH value of 8.5, and the regeneration rate of the activated carbon reaches 98 percent.
Example 4
The method for treating high-concentration organic wastewater by using the system described in example 1:
the wastewater to be treated is: the pH value of the industrial wastewater of a certain chemical plant is 8, and the COD is 30100mg/L.
The processing steps are as follows: introducing wastewater to be treated into a regulating tank, uniformly stirring, adding 2% copper nitrate and manganese nitrate solution into a dosing stirrer on a pipeline between the regulating tank and a continuous hydrothermal oxidation system according to requirements to keep the mass concentration of a catalyst at 0.3%, and introducing the catalyst into the continuous hydrothermal oxidation system; the continuous hydrothermal oxidation system controls the reaction temperature to 320 ℃, the oxygen purity to 94%, the oxidation coefficient to 1, the reaction pressure to 9MPa, the reaction time to 2.5h, the COD conversion rate of the wastewater after being treated by the continuous hydrothermal oxidation system to 85.2%, the biodegradability of the effluent to 0.54 and the pH to 7.1; the effluent is mixed with the sewage which is extracted from the reaction of the anaerobic reaction system and is rich in methanogen acetate, the acetic acid is controlled at 1500mh/L, the pH value is 7, the system temperature is 35 ℃, and the residence time is 4 days; the effluent of the anaerobic reaction system is conveyed to an aerobic reaction system through a pipeline, granular activated carbon with the grain diameter of 5mm is filled in the anaerobic reaction system, the height of an activated carbon layer is 1.5m, the residence time is 1.5 days, and the COD removal rate of the wastewater after being treated by an anaerobic and aerobic process reaches 99.8%; introducing the effluent of the aerobic reaction system into an activated carbon adsorption system, wherein the activated carbon is granular activated carbon with the particle size of 5mm, the activated carbon filter column is 5m high, the COD (chemical oxygen demand) removal treatment rate of the effluent after treatment by an activated carbon filter process is more than 99.9%, and the residual quantity of the metal catalyst is difficult to detect and reaches the three-level standard of Integrated wastewater discharge Standard GB 8978-1996; the activated carbon with saturated adsorption is used for supplementing activated carbon replaced by an oxygen reaction system, the excess activated carbon generated by the aerobic reaction system is led into an intermittent wet oxidation system in batches, the treatment volume of each intermittent reaction kettle is 100L, hydrogen peroxide and oxygen are used for mixed oxidation, the volume fraction of the hydrogen peroxide is 15%, the oxygen concentration is 94%, the reaction temperature is 300 ℃, and the reaction time is 2 hours; the mixture treated by the intermittent wet oxidation system is led into a washing system, and is washed and desorbed by sodium hydroxide alkali liquor with the pH value of 8.5, and the regeneration rate of the activated carbon reaches 98.5 percent.
Claims (4)
1. A high-concentration organic wastewater treatment system is characterized in that,
comprises an adjusting tank, a continuous hydrothermal oxidation system, an anaerobic reaction system, an aerobic reaction system and an activated carbon adsorption system which are sequentially communicated through a liquid pipeline;
the active carbon adsorption system is sequentially communicated with the aerobic reaction system, the intermittent wet oxidation system and the active carbon washing system through solid pipelines to form an active carbon circulating treatment loop, and residual organic matters and heavy metal catalysts in the effluent are adsorbed and removed;
the effluent part of the activated carbon adsorption system is directly discharged, and part of the effluent part is led into an activated carbon washing system to be used as washing water;
the liquid generated by the activated carbon washing system and the intermittent wet oxidation system is directly led into the regulating tank through a liquid pipeline after being collected; the reaction zone of the anaerobic reaction system is also provided with a pipeline connected to a feed inlet of the anaerobic reaction system, and the pipeline is used for extracting a mixture in the stable reaction of the anaerobic reaction system, mixing the mixture with the effluent of the continuous hydrothermal oxidation system and then introducing the mixture into the anaerobic reaction system;
the use method of the high-concentration organic wastewater treatment system comprises the following steps:
(1) Continuous hydrothermal oxidation: filtering the wastewater to be treated, removing slag, introducing the wastewater into an adjusting tank, uniformly stirring, and adjusting the pH to 7-9; then, introducing the mixture into a continuous hydrothermal oxidation system, adding a heavy metal catalyst, keeping the mass concentration of the catalyst at 0.1% -0.3%, and reacting for 1.5-2.5 hours by taking pure oxygen as an oxidant; wherein, the continuous hydrothermal oxidation reaction conditions are as follows: an oxidation coefficient of 0.9-1.0, a temperature of 280-320 ℃ and a pressure of 7-9 Mpa;
(2) Anaerobic reaction treatment: the liquid product after the reaction in the step (1) is subjected to heat exchange and temperature reduction, and then is led into an anaerobic reaction system to react for 2-4 days at the temperature of 30-35 ℃; extracting a mixture in the stable reaction of the anaerobic reaction system, mixing the extracted mixture with effluent of the continuous hydrothermal oxidation system, adjusting the concentration of acetic acid to be 500-1500 mg/L, pH to be 6.5-7.5, and then introducing the mixture into the anaerobic reaction system;
(3) And (3) aerobic reaction treatment: directly introducing the effluent treated in the step (2) into an aerobic reaction system, after staying for 1-3 days, directly introducing the effluent into an active carbon adsorption system, adsorbing and removing residual organic matters and heavy metal catalysts, and discharging; wherein the aerobic reaction system is a biological aerated filter, and the filler is granular activated carbon;
wherein the particle size of the filler particle active carbon in the biological aerated filter is 4-8 mm, and the layer height is 1.5-2 m;
(4) And (3) activated carbon cyclic treatment: introducing saturated activated carbon generated by the treatment of an activated carbon adsorption system into an aerobic reaction system, introducing residual activated carbon discharged by the aerobic reaction system into an intermittent wet oxidation system for regeneration treatment, introducing the regenerated activated carbon into an activated carbon washing system, introducing clean activated carbon generated by the activated carbon washing system into the activated carbon adsorption system for recycling, and discharging sludge residues; the effluent part of the activated carbon adsorption system is directly discharged, and the effluent part is led into an activated carbon washing system to serve as washing water after the pH is partially regulated to 8-9; the liquid generated by the activated carbon washing system and the intermittent wet oxidation system is directly led into the regulating tank through a liquid pipeline after being collected; the intermittent wet oxidation system adopts hydrogen peroxide and oxygen as combined oxidants, the oxidation coefficient is kept at 1.5-2, the temperature is 260-300 ℃, and the volume fraction of the hydrogen peroxide is 10% -15%.
2. The system of claim 1, wherein a batch agitator is provided within the anaerobic reaction system.
3. A method for treating high concentration organic wastewater by a system according to any of claims 1-2, comprising the steps of:
(1) Continuous hydrothermal oxidation: filtering the wastewater to be treated, removing slag, introducing the wastewater into an adjusting tank, uniformly stirring, and adjusting the pH to 7-9; then introducing a continuous hydrothermal oxidation system, adding a catalyst, taking pure oxygen as an oxidant, and reacting for 1.5-2.5 hours; wherein, the continuous hydrothermal oxidation reaction conditions are as follows: an oxidation coefficient of 0.9-1.0, a temperature of 280-320 ℃ and a pressure of 7-9 Mpa;
(2) Anaerobic reaction treatment: the liquid product after the reaction in the step (1) is subjected to heat exchange and temperature reduction, and then is led into an anaerobic reaction system to react for 2-4 days at the temperature of 30-35 ℃; extracting a mixture in the stable reaction of the anaerobic reaction system, mixing the extracted mixture with effluent of the continuous hydrothermal oxidation system, adjusting the concentration of acetic acid to be 500-1500 mg/L, pH to be 6.5-7.5, and then introducing the mixture into the anaerobic reaction system;
(3) And (3) aerobic reaction treatment: directly introducing the effluent treated in the step (2) into an aerobic reaction system, after staying for 1-3 days, directly introducing the effluent into an active carbon adsorption system, adsorbing and removing residual organic matters and heavy metal catalysts, and discharging; wherein the aerobic reaction system is a biological aerated filter, and the filler is granular activated carbon;
(4) And (3) activated carbon cyclic treatment: introducing saturated activated carbon generated by the treatment of an activated carbon adsorption system into an aerobic reaction system, introducing residual activated carbon discharged by the aerobic reaction system into an intermittent wet oxidation system for regeneration treatment, introducing the regenerated activated carbon into an activated carbon washing system, introducing clean activated carbon generated by the activated carbon washing system into the activated carbon adsorption system for recycling, and discharging sludge residues; the effluent part of the activated carbon adsorption system is directly discharged, and the effluent part is led into an activated carbon washing system to serve as washing water after the pH is partially regulated to 8-9; the liquid generated by the activated carbon washing system and the intermittent wet oxidation system is directly led into the regulating tank through a liquid pipeline after being collected; the intermittent wet oxidation system adopts hydrogen peroxide and oxygen as combined oxidants, the oxidation coefficient is kept at 1.5-2, the temperature is 260-300 ℃, and the volume fraction of the hydrogen peroxide is 10% -15%.
4. The method according to claim 3, wherein in the step (2), an intermittent stirrer is provided in the anaerobic reaction system, and stirring is performed for 10 to 15 minutes each time at a stirring interval of half an hour.
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