CN106865844B - A photoelectrocatalysis recovery processing device for high concentration phenol ammonia waste water - Google Patents

A photoelectrocatalysis recovery processing device for high concentration phenol ammonia waste water Download PDF

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CN106865844B
CN106865844B CN201710115970.XA CN201710115970A CN106865844B CN 106865844 B CN106865844 B CN 106865844B CN 201710115970 A CN201710115970 A CN 201710115970A CN 106865844 B CN106865844 B CN 106865844B
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phenol
ammonia
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CN106865844A (en
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杨慧敏
梁锦陶
刘宪
赵煜
简选
张二辉
梁镇海
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Taiyuan University of Technology
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
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    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
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    • C02F2201/46105—Details relating to the electrolytic devices
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    • C02F2201/461—Electrolysis apparatus
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    • C—CHEMISTRY; METALLURGY
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    • C02F2209/14—NH3-N
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Abstract

A photoelectrocatalysis recovery processing device for high-concentration phenol-ammonia wastewater comprises a high-concentration phenol-ammonia recovery device consisting of a ceramic membrane, an anode, a bipolar membrane diaphragm, an ammonia absorption device, a phenol extraction device and a phenol distillation device, and a low-concentration phenol-ammonia gradual photoelectrocatalysis oxidation processing device consisting of an anode chamber, the anode, the bipolar membrane diaphragm, a gas diffusion cathode and a cathode chamber. The invention carries out step-by-step treatment on the high-concentration phenol-ammonia wastewater, the recovery treatment rate of the phenol-ammonia wastewater reaches more than 99 percent, the concentration of discharged ammonia nitrogen is lower than 15 mg/L, and the concentration of phenol is lower than 0.5 mg/L, thus reaching the national first-level discharge standard; and the process is advanced, the investment is low, the by-products phenol and ammonia are recovered while the wastewater is purified, and the recycling of waste is realized.

Description

A photoelectrocatalysis recovery processing device for high concentration phenol ammonia waste water
Technical Field
The invention relates to a high-concentration phenol-ammonia wastewater recovery treatment device, in particular to a device for recovering and treating high-concentration phenol-ammonia wastewater step by utilizing photoelectrocatalysis of visible light.
Background
The coking wastewater is high-concentration wastewater generated in the coking and gas purification processes, and the pollutants comprise COD, phenol, polycyclic aromatic compounds, ammonia nitrogen, petroleum and the like. The waste water has the defects of complex quality, large chromaticity, pungent odor, high temperature and poor biodegradability, is one of industrial waste water which is extremely difficult to treat, and the improvement and the solution of the problem of environmental pollution caused by coking waste water are urgent. At present, the main methods for treating coking wastewater comprise a physical method, a chemical method, a biochemical method and the like, for example, Tang dynasty and the like research the application of the biological aerated filter in the deep treatment of coking wastewater, so that the removal rate of COD and ammonia nitrogen can reach 93-94% (Tang dynasty, research on deep treatment test of the biological aerated filter of coking wastewater [ D]Taiyuan, taiyuan university, 2008); yuan et alThe coking wastewater is treated by octane and cyclohexane extraction method, so that The removal rate of COD reaches 88.63 percent (Yuan Xiaooying, SunHuifang, Guo Dongsheng, The removal of COD from The coking wastewater using extraction-biodegradation coupling [ J]Desalinization, 2012, 289(15): 45-50). The invention discloses a phenol ammonia wastewater treatment device with publication No. CN 104926021A, which utilizes a three-section treatment device for degrading phenol ammonia wastewater by ozone oxidation, and can lead the removal rate of COD to reach about 60-70% after catalytic oxidation and coagulation reaction, but the coking wastewater treatment technology has higher investment, larger occupied area, higher operating cost and strict requirements on a purification section, and some processes also bring secondary pollution while removing pollutants. Publication No. CN 101486499B discloses a device for solar photoelectrocatalytic oxidation of organic matters in water, which utilizes visible light and ultraviolet light and Cu2O-Bi2O3-TiO2、Fe2O3The device treats 100mg/L of phenol aqueous solution with the phenol conversion rate close to 100% and the COD removal rate more than 90%, but the device is a single-chamber treatment device, can only treat the phenol-ammonia wastewater with low concentration, and cannot be used for recovering and treating the phenol-ammonia wastewater with high concentration.
Although the existing devices for treating the coking wastewater are numerous, the technical cost is high, the treatment effect hardly reaches the national discharge standard, the practical engineering application is limited, and a new device is urgently needed to be developed to solve the problem of recycling and treating the high-concentration phenol-ammonia wastewater.
Disclosure of Invention
The invention provides a photoelectrocatalysis recovery processing device for high-concentration phenol-ammonia wastewater, which aims to fundamentally solve the pollution problem of phenol-ammonia wastewater in coking wastewater, and particularly relates to a device for recycling the coking wastewater first and then processing the coking wastewater step by utilizing a photoelectrocatalysis oxidation method, so that the discharge amount of ammonia nitrogen and phenol in the wastewater reaches the national first-level discharge standard, and the byproducts phenol and ammonia are recycled while the wastewater is purified.
The purpose of the invention is realized by the following technical scheme.
A photoelectrocatalysis recovery processing device for high-concentration phenol-ammonia wastewater comprises a three-level photoelectrocatalysis recovery processing electrolytic tank consisting of a first-level high-concentration phenol-ammonia recovery device and a two-level low-concentration phenol-ammonia gradual oxidation processing device; the method is characterized in that:
the first-level high-concentration phenol-ammonia recovery device is characterized in that the anode is surrounded by a cylindrical hollow ceramic membrane, the upper end interface is connected with an ammonia absorption device, the lower end interface is connected with a phenol extraction device and a phenol distillation device, and water is decomposed into OH by utilizing a bipolar membrane diaphragm under the action of light and an electric field-And H+，OH-And high-concentration ammonia nitrogen which is gathered in the anode chamber and enters from the water inletOH-Combine to form NH3The ammonia absorption device is used for recycling, meanwhile, the high-concentration phenol is enriched near the anode and then transferred to the phenol extraction device and the phenol distillation device for recycling, and the high-concentration phenol-ammonia wastewater with the total phenol content of 800-3000mg/L and the ammonia nitrogen content of 200-900mg/L is treated into the low-concentration phenol-ammonia wastewater with the total phenol content of 50-300mg/L and the ammonia nitrogen content of 20-180 mg/L;
the two-stage low-concentration phenol-ammonia wastewater treatment device is formed by combining two continuous groups of anode chambers, anodes, bipolar membrane diaphragms, gas diffusion cathodes and cathode chambers; and the low-concentration phenol-ammonia wastewater treated by the first-stage high-concentration phenol-ammonia recovery device is degraded step by utilizing a photoelectrocatalysis method at normal temperature and normal pressure, the anode chamber is used for carrying out anodic oxidation, and the cathode chamber is used for reducing oxygen in the air into a strong oxidant H at the cathode2O2Strong oxidizing agent H2O2Continuously oxidizing the untreated phenol-ammonia wastewater, and sequentially oxidizing and degrading step by step so as to reach the national first-level discharge standard;
the whole cyclic treatment process of the three-stage photoelectrocatalysis recovery treatment electrolytic tank is to carry out photoelectrocatalysis treatment on high-concentration phenol-ammonia wastewater entering from a water inlet and OH generated by modified bipolar membrane diaphragm photoelectrocatalysis decomposition water-The high-concentration phenol-ammonia wastewater is recovered and converted into low-concentration phenol-ammonia wastewater by combining the phenol-ammonia wastewater with the ammonia absorption device, the phenol extraction device and the phenol distillation device for recovery treatment, and then enters the primary photoelectric treatment deviceThe anode tank is subjected to anodic oxidation treatment, then flows into the anode tank of the secondary photoelectric treatment device through the pipeline, enters the anode tank of the tertiary photoelectric treatment device after oxidation treatment, then flows into the cathode tank of the tertiary treatment device, the gas diffusion cathode stores a large amount of air, and oxygen in the air is in H+Is reduced by the cathode to a strong oxidant H in the presence of2O2Strong oxidizing agent H2O2And continuously oxidizing and degrading the phenol and the ammonia nitrogen which are not completely treated in the cathode tank, sequentially entering the cathode tanks of the secondary treatment device and the primary treatment device to perform the same oxidation treatment, and finally discharging the phenol and the ammonia wastewater after being detected to be qualified by an ultraviolet spectrophotometry, thereby realizing the photoelectrocatalysis recovery treatment of the high-concentration phenol and ammonia wastewater.
Further specific technical features are as follows.
The injection amount of the phenol ammonia wastewater in the anode chamber is not more than two thirds of the total volume of the anode chamber.
The ceramic membrane is cylindrical and conical, the ratio of the outer diameter to the inner diameter of the ceramic membrane is 1.08: 1, the thickness of the ceramic membrane is not more than 3cm, and the ceramic membrane is made of starch and SiO2、Al2O3And acrylamide.
The length, width and thickness ratio of the anode is 6: 1: 0.1, the electrode material is a titanium-based oxide anode with an active layer or a binary metal oxide electrode, and the active layer of the titanium-based oxide anode is PbO2、MnO2And SnO2One or two of them mixed in different proportion, the binary metal oxide electrode is MnxCr1-xO3/2And CoxCr1-xO3/2One kind of (1).
The bipolar membrane diaphragm is prepared by mixing sodium carboxymethylcellulose and chitosan, and adding Cu with the mass ratio not more than 50% of the total mass of the bipolar membrane2O、g-C3N4One or more of graphene, carbon quantum dots and MOFs are modified, and OH generated by photoelectrocatalysis decomposition of water by the modified graphene, carbon quantum dots and MOFs is increased-And H+The efficiency of the adhesive is obtained by adopting a hot pressing method or a tape casting method, and the thickness range is 50-200 mu m.
The gas diffusion cathode is a hollow cylinder with the ratio of the outer diameter to the inner diameter to the height of 1:6 or a hollow cylinder with the ratio of the diameter to the height of 1:6, the solid cylinder is prepared by mixing one or more of porous carbon, graphite powder, carbon black, acetylene black and superconducting carbon black with graphene through a hot pressing method.
The distance between the anode and the gas diffusion cathode and the bipolar membrane diaphragm is not more than 20 cm.
Compared with the prior art, the invention has the following advantages: the technical scheme solves the technical problem of treating the high-concentration phenol-ammonia wastewater in the coal upgrading process, and avoids the situation that the development of coal chemical enterprises is restricted due to environmental problems. Meanwhile, the treated water reaches the national discharge standard, the environmental pollution caused by the discharge of waste water is avoided, the ecological environment is protected, the waste water is purified, and the byproducts phenol and ammonia are recycled, so that the method has important significance.
Drawings
FIG. 1 is a schematic diagram of the structure of the apparatus of the present invention.
In the figure: 1: a water inlet; 2: an anode chamber; 3: a ceramic membrane; 4: an anode; 5: a bipolar membrane separator; 6: a gas diffusion cathode; 7: a cathode chamber; 8: an ammonia absorption device; 9: a phenol extraction unit; 10: a phenol distillation device.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Detailed description of the preferred embodiment 1
The invention relates to a photoelectrocatalysis recovery processing device for high-concentration phenol-ammonia wastewater, which is composed of a first-stage high-concentration phenol-ammonia recovery device and a two-stage low-concentration phenol-ammonia gradual oxidation processing device to form a three-stage photoelectrocatalysis recovery processing electrolytic tank as shown in figure 1; wherein:
the first-stage high-concentration phenol ammonia recovery device is characterized in that an anode 4 is surrounded by a cylindrical conical hollow ceramic membrane 3, an upper end interface is connected with an ammonia absorption device 8, a lower end interface is connected with a phenol extraction device 9 and a phenol distillation device 10, and water is decomposed into OH by utilizing a modified bipolar membrane 5 under the action of light and an electric field-And H+，OH-OH-And H+，OH-And high-concentration ammonia nitrogen which is gathered in the anode chamber and enters from the water inletOH-Combine to form NH3The ammonia absorption device is used for recycling, meanwhile, the high-concentration phenol is enriched near the anode and then transferred to the phenol extraction device and the phenol distillation device for recycling, and the high-concentration phenol-ammonia wastewater with the total phenol content of 800-3000mg/L and the ammonia nitrogen content of 200-900mg/L is treated into the low-concentration phenol-ammonia wastewater with the total phenol content of 50-300mg/L and the ammonia nitrogen content of 20-180 mg/L;
the two-stage low-concentration phenol-ammonia wastewater treatment device is formed by combining two continuous groups of anode chambers, anodes, bipolar membrane diaphragms, gas diffusion cathodes and cathode chambers; and the low-concentration phenol-ammonia wastewater treated by the first-stage high-concentration phenol-ammonia recovery device is degraded step by utilizing a photoelectrocatalysis method at normal temperature and normal pressure, the anode chamber is used for carrying out anodic oxidation, and the cathode chamber is used for reducing oxygen in the air into a strong oxidant H at the cathode2O2Strong oxidizing agent H2O2Continuously oxidizing the untreated phenol-ammonia wastewater, and sequentially oxidizing and degrading step by step so as to reach the national first-level discharge standard;
the whole cyclic treatment process of the three-stage photoelectrocatalysis recovery treatment electrolytic tank is to carry out photoelectrocatalysis treatment on high-concentration phenol-ammonia wastewater entering from a water inlet and OH generated by modified bipolar membrane diaphragm photoelectrocatalysis decomposition water-Combine to get into ammonia absorbing device, phenol extraction device and phenol distillation plant carry out recovery processing, high concentration phenol ammonia waste water turns into low concentration phenol ammonia waste water through the recovery and then gets into the positive pole groove of one-level photoelectric processing device and carry out anodic oxidation and handle, then flow into the positive pole groove of second grade photoelectric processing device through the pipeline, reentrant tertiary photoelectric processing device's positive pole groove after oxidation, then flow into tertiary processing device's negative pole groove, gaseous diffusion negative pole has a large amount of air in storage, oxygen in the air is at H positive pole groove of tertiary processing device+Is reduced by the cathode to a strong oxidant H in the presence of2O2Strong oxidizing agent H2O2Continuously oxidizing and degrading the phenol and ammonia nitrogen which are not completely treated in the cathode slot, then sequentially entering the cathode slots of a secondary treatment device and a primary treatment device to carry out the same oxidation treatment, and finallyAnd the wastewater is discharged after being detected to be qualified by an ultraviolet spectrophotometry, so that the photoelectrocatalysis recovery treatment of the high-concentration phenol-ammonia wastewater is realized.
Further specific technical features are as follows.
The injection amount of the phenol ammonia wastewater in the anode chamber is not more than two thirds of the total volume of the anode chamber.
The ceramic membrane is cylindrical and conical, the ratio of the outer diameter to the inner diameter of the ceramic membrane is 1.08: 1, the thickness of the ceramic membrane is not more than 3cm, and the ceramic membrane is made of starch and SiO2、Al2O3And acrylamide.
The length, width and thickness ratio of the anode is 6: 1: 0.1, the electrode material is a titanium-based oxide anode with an active layer or a binary metal oxide electrode, and the active layer of the titanium-based oxide anode is PbO2、MnO2And SnO2One or two of them mixed in different proportion, the binary metal oxide electrode is MnxCr1-xO3/2And CoxCr1-xO3/2One kind of (1).
The bipolar membrane diaphragm is prepared by mixing sodium carboxymethylcellulose and chitosan, and adding Cu with the mass ratio not more than 50% of the total mass of the bipolar membrane2O、g-C3N4One or more of graphene, carbon quantum dots and MOFs are modified, and OH generated by photoelectrocatalysis decomposition of water by the modified graphene, carbon quantum dots and MOFs is increased-And H+The efficiency of the adhesive is obtained by adopting a hot pressing method or a tape casting method, and the thickness range is 50-200 mu m.
The gas diffusion cathode is a hollow cylinder with the ratio of the outer diameter to the inner diameter to the height of 1:6 or a hollow cylinder with the ratio of the diameter to the height of 1:6, the solid cylinder is prepared by mixing one or more of porous carbon, graphite powder, carbon black, acetylene black and superconducting carbon black with graphene through a hot pressing method.
The distance between the anode and the gas diffusion cathode and the bipolar membrane diaphragm is not more than 20 cm.
Compared with the prior art, the invention has the following advantages: the technical scheme solves the technical problem of treating the high-concentration phenol-ammonia wastewater in the coal upgrading process, and avoids the situation that the development of coal chemical enterprises is restricted due to environmental problems. Meanwhile, the treated water reaches the national discharge standard, the environmental pollution caused by the discharge of waste water is avoided, the ecological environment is protected, the waste water is purified, and the byproducts phenol and ammonia are recycled, so that the method has important significance.
Detailed description of the preferred embodiment 2
The invention relates to a photoelectrocatalysis recovery processing device for high-concentration phenol-ammonia wastewater, which is composed of a first-stage high-concentration phenol-ammonia recovery device and a two-stage low-concentration phenol-ammonia gradual oxidation processing device to form a three-stage photoelectrocatalysis recovery processing electrolytic tank as shown in figure 1; wherein:
the first-stage high-concentration phenol ammonia recovery device is characterized in that an anode 4 is surrounded by a cylindrical conical hollow ceramic membrane 3, an upper end interface is connected with an ammonia absorption device 8, a lower end interface is connected with a phenol extraction device 9 and a phenol distillation device 10, and water is decomposed into OH by utilizing a modified bipolar membrane 5 under the action of light and an electric field-And H+，OH-
High-concentration ammonia nitrogen and OH gathered in the anode chamber 2 and entering from the water inlet 1-Combine to form NH3The phenol-ammonia wastewater is gathered above the phenol-ammonia wastewater, recycled through an ammonia absorption device 8, simultaneously, high-concentration phenol permeates through a ceramic membrane to be enriched near an anode 4 and then is transferred to a phenol extraction device 9 and a phenol distillation device 10 for recycling, and the high-concentration phenol-ammonia wastewater with the total phenol content of 800-3000mg/L and the ammonia nitrogen content of 200-900mg/L is treated into low-concentration phenol-ammonia wastewater with the total phenol content of 50-300mg/L and the ammonia nitrogen content of 20-180 mg/L.
The two-stage low-concentration phenol-ammonia wastewater treatment device is formed by combining two groups of continuous anode chambers 2, anodes 4, bipolar membrane diaphragms 5, gas diffusion cathodes 6 and cathode chambers 7; and the low-concentration coking wastewater treated by the first-stage high-concentration phenol-ammonia recovery device is degraded step by utilizing a photoelectrocatalysis method at normal temperature and normal pressure, the anode chamber is used for carrying out anodic oxidation, and the cathode chamber is used for reducing oxygen in the air into a strong oxidant H at the cathode2O2Strong oxidizing agent H2O2Continuously oxidizing the untreated phenol-ammonia wastewater, and sequentially oxidizing and degrading step by step so as to reach the national first-level discharge standard.
The whole cyclic treatment process of the three-stage photoelectrocatalysis recovery treatment electrolytic tank is to treat high-concentration phenol ammonia wastewater entering from the water inlet 1 and OH generated by photoelectrocatalysis decomposition water of the modified bipolar membrane diaphragm 5-Combine to get into ammonia absorbing device 8, phenol extraction plant 9 and phenol distillation plant 10 carry out recovery processing, high concentration phenol ammonia waste water is retrieved and is turned into low concentration phenol ammonia waste water and reentrant one-level photoelectric processing device's anode tank and carry out anodic oxidation and handle, then flow into second grade photoelectric processing device's anode tank through the pipeline, reentrant tertiary photoelectric processing device's anode tank after oxidation, then flow into tertiary processing device's cathode tank, gaseous diffusion negative pole 6 stores a large amount of air, oxygen in the air is at H+Is reduced by the cathode to a strong oxidant H in the presence of2O2Strong oxidizing agent H2O2And continuously oxidizing and degrading the phenol and the ammonia nitrogen which are not completely treated in the cathode tank, sequentially entering the cathode tanks of the secondary treatment device and the primary treatment device to perform the same oxidation treatment, and finally discharging the phenol and the ammonia wastewater after being detected to be qualified by an ultraviolet spectrophotometry, thereby realizing the photoelectrocatalysis recovery treatment of the high-concentration phenol and ammonia wastewater.
In the above embodiment, the apparatus can also increase the low concentration phenol ammonia wastewater treatment apparatus to three or more stages according to the actual treatment situation, and the injection amount of phenol ammonia wastewater in the anode chamber 2 does not exceed two thirds of the total volume of the anode chamber when the wastewater is treated by photoelectrocatalysis recovery.
In the above embodiment, the ceramic membrane 3 is made into a cylindrical conical structure, the ratio of the outer diameter to the inner diameter is 1.08: 1, the thickness of the ceramic membrane is not more than 3cm, and the ceramic membrane is made of starch and SiO2、Al2O3And acrylamide were obtained using prior art techniques.
In the above embodiment, the anode 4 having a length, width and thickness ratio of 6: 1: 0.1 is used, the electrode material is a titanium-based oxide anode having an active layer prepared by an electrodeposition method or a binary metal oxide electrode prepared by a thermal decomposition method, and the active layer of the titanium-based oxide anode is PbO2、MnO2And SnO2One of them, or at different molesTwo of the components are mixed according to a ratio, wherein the mixing molar ratio ranges from 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 2:3, 2:5, 2:7, 3:5, 3:7, 4:3, 4:5 and 4: 7; the binary metal oxide electrode is MnxCr1-xO3/2And CoxCr1-xO3/2One kind of (1).
In the above embodiment, the bipolar membrane separator 5 is prepared by using sodium carboxymethylcellulose and chitosan as raw materials, and adding Cu with a mass ratio of not more than 50% of the total mass of the bipolar membrane2O、g-C3N4One or more of graphene, carbon quantum dots and MOFs are modified, and OH generated by photoelectrocatalysis decomposition of water by the modified graphene, carbon quantum dots and MOFs is increased-And H+The efficiency of the adhesive is obtained by adopting a hot pressing method or a tape casting method, and the thickness range is 50-200 mu m.
In the above embodiments, the gas diffusion cathode 6 is a hollow cylinder with a ratio of outer diameter, inner diameter, height of 1:6 or a hollow cylinder with a ratio of diameter, height of 1:6, mixing one or more of porous carbon, graphite powder, carbon black, acetylene black and superconducting carbon black with graphene according to a certain mass ratio, adding 5% of polytetrafluoroethylene dispersion and 5% of Nafion solution in a volume ratio of 1:1, mixing the mixed powder into paste, stirring for 2 hours, then carrying out ultrasonic treatment for 1 hour, then pouring into a grinding tool with a specific size, adding 40Kg of pressure for compaction, and carrying out 450 Kg pressure compactionoC, high-temperature hot-pressing and firing for 5 hours.
In the above embodiment, the anode 4 and the gas-diffusion cathode 6 are each located at a distance of not more than 20cm from the bipolar membrane separator 5.
The following will further illustrate the beneficial effects of the photoelectrocatalysis recovery processing device for high-concentration phenol-ammonia wastewater implemented by the invention through specific test examples.
Experimental example 1
The phenol-ammonia wastewater with the phenol content of 1200 mg/L and the ammonia nitrogen concentration of 300mg/L is treated by utilizing the specific implementation device.
The setting conditions are that the length, width and height of the cathode chamber and the anode chamber are all 30 cm, the distance between the cathode and the anode and the central bipolar membrane diaphragm is all 5cm, and the outer diameter of the ceramic membrane is13.5cm, an inner diameter of 12.5cm, a thickness of 1cm, SnO with a length of 60 cm, a width of 10 cm and a thickness of 1cm in a molar ratio of 1:42+pbO2Taking a titanium-based oxide electrode as an active layer as an anode, mixing reduced graphene, carbon powder and acetylene black powder according to the mass ratio of 1:2:1, adding 5% of polytetrafluoroethylene dispersion liquid and 5% of Nafion solution according to the volume ratio of 1:1, mixing the mixed powder into paste, stirring for 2 hours, then carrying out ultrasonic treatment for 1 hour, then pouring the paste into a grinding tool with a specific size, adding 40Kg of pressure for compaction, and carrying out 450 Kg of pressureoC, a solid cylindrical gas diffusion electrode which is prepared by hot-pressing and firing for 5 hours at a high temperature and has the diameter of 10 cm and the height of 60 cm is used as a cathode, a bipolar membrane which is prepared by a tape casting method of 0.5 g of BiOBr and has the thickness of 120 mu m is used as a diaphragm of a cathode chamber and an anode chamber, the recovery rate of phenol reaches 91.5 percent and the recovery rate of ammonia nitrogen reaches 87.6 percent after treatment for two hours, after gradual oxidative decomposition treatment, the content of ammonia nitrogen in the treated wastewater is measured at a water outlet and is 12.3 mg/L, the content of phenol is 0.3 mg/L, and the national first-level discharge standard is reached.
Experimental example 2
The phenol-ammonia wastewater with the phenol content of 968 mg/L and the ammonia nitrogen concentration of 250mg/L is treated by utilizing the specific implementation device.
The setting conditions are that the length, width and height of the cathode chamber and the anode chamber are 40 cm, the distance between the cathode and the anode and the central bipolar membrane is 10 cm, the outer diameter of the ceramic membrane is 27cm, the inner diameter is 25cm, the thickness is 2cm, Mn with the length of 60 cm, the width of 10 cm and the thickness of 1cm is selected0.4Cr0.6O3/2The binary metal oxide electrode is used as an anode and is prepared from the following components in a mass ratio of 1.8: 1: 2.4 mixing porous carbon, reduced graphene and superconducting carbon black powder, adding 5% of polytetrafluoroethylene dispersion and 5% of Nafion solution in a volume ratio of 1:1, mixing the mixed powder into paste, stirring for 2 hours, then carrying out ultrasonic treatment for 1 hour, then pouring the paste into a grinding tool with a specific size, adding 40Kg of pressure for compaction, and carrying out 450 Kg of compactionoC high-temperature hot-pressing and firing for 5 hours to obtain a hollow cylindrical gas diffusion electrode with the outer diameter of 10 cm, the inner diameter of 5cm and the height of 60 cm, and adding 0.3 g of Cu into the hollow cylindrical gas diffusion electrode as a cathode2The bipolar membrane with the thickness of 100 mu m prepared by the tape casting method of O is used as a diaphragm of a cathode chamber and an anode chamber and is treated for two hours,the recovery rate of phenol reaches 90.3%, the recovery rate of ammonia nitrogen reaches 88.6%, after the gradual oxidative decomposition treatment, the content of ammonia nitrogen in the treated wastewater is 10.4 mg/L and the content of phenol is 0.4 mg/L, which are measured at a water outlet and reach the national first-level discharge standard.
Experimental example 3
The phenol-ammonia wastewater with the phenol content of 1250 mg/L and the ammonia nitrogen concentration of 330 mg/L is treated by utilizing the specific implementation device.
The setting conditions are that the length, width and height of the cathode chamber and the anode chamber are all 30 cm, the distance between the cathode and the anode and the central bipolar membrane is 7cm, the outer diameter of the ceramic membrane is 13.5cm, the inner diameter is 12.5cm, the thickness is 1cm, Co with the length of 60 cm, the width of 10 cm and the thickness of 1cm is selected0.6Cr0.4O3/2The binary metal oxide electrode is used as an anode and is prepared from the following components in percentage by mass: 2.5: 1:4 mixing reduced graphene, porous carbon, acetylene black and superconducting carbon black powder, adding 5% of polytetrafluoroethylene dispersion and 5% of Nafion solution in a volume ratio of 1:1, mixing the mixed powder into paste, stirring for 2 hours, then carrying out ultrasonic treatment for 1 hour, then pouring the paste into a grinding tool with a specific size, adding 40Kg of pressure for compaction, and carrying out 450 Kg of pressure for compactionoC high-temperature hot-pressing and firing for 5 hours to obtain a hollow cylindrical gas diffusion electrode with the outer diameter of 10 cm, the inner diameter of 5cm and the height of 60 cm, and adding 0.3 g of Cu into the hollow cylindrical gas diffusion electrode as a cathode2O and 0.5 g g-C3N4The bipolar membrane with the thickness of 120 mu m prepared by the tape casting method is used as a diaphragm of a cathode chamber and an anode chamber, the recovery rate of phenol reaches 94.8 percent and the recovery rate of ammonia nitrogen reaches 91.1 percent after three-hour treatment, and after the step-by-step oxidative decomposition treatment, the content of ammonia nitrogen in the treated wastewater is measured at a water outlet and is 13.3 mg/L and the content of phenol is 0.4 mg/L, thus reaching the national first-level discharge standard.

Claims (7)

1. A photoelectrocatalysis recovery processing device for high-concentration phenol-ammonia wastewater comprises a three-level photoelectrocatalysis recovery processing electrolytic tank consisting of a first-level high-concentration phenol-ammonia recovery device and a two-level low-concentration phenol-ammonia gradual oxidation processing device; the method is characterized in that:
the first-stage high-concentration phenol-ammonia recovery device is characterized in that a cylindrical hollow ceramic membrane (3) surrounds an anode (4), an upper end interface is connected with an ammonia absorption device (8), a lower end interface is connected with a phenol extraction device (9) and a phenol distillation device (10), and a bipolar membrane diaphragm (5) is utilized to decompose water into water under the action of light and an electric field
Figure DEST_PATH_IMAGE001
And
Figure 711614DEST_PATH_IMAGE002
，
Figure 271908DEST_PATH_IMAGE001
high-concentration ammonia nitrogen gathered in the anode chamber (2) and entering from the water inlet (1) and
Figure 43555DEST_PATH_IMAGE001
bond formation
Figure DEST_PATH_IMAGE003
The ammonia absorption device (8) is used for recycling, meanwhile, the high-concentration phenol is enriched near the anode (4) and then transferred to the phenol extraction device (9) and the phenol distillation device (10) for recycling, and the high-concentration phenol-ammonia wastewater with the total phenol content of 800-3000mg/L and the ammonia nitrogen content of 200-900mg/L is treated into low-concentration phenol-ammonia wastewater with the total phenol content of 50-300mg/L and the ammonia nitrogen content of 20-180 mg/L;
the two-stage low-concentration phenol-ammonia wastewater treatment device is formed by combining two continuous groups of anode chambers (2), anodes (4), bipolar membrane diaphragms (5), gas diffusion cathodes (6) and cathode chambers (7); and the low-concentration phenol-ammonia wastewater treated by the first-stage high-concentration phenol-ammonia recovery device is degraded step by utilizing a photoelectrocatalysis method at normal temperature and normal pressure, the anode chamber is used for carrying out anodic oxidation, and the cathode chamber is used for reducing oxygen in the air into a strong oxidant H at the cathode2O2Strong oxidizing agent H2O2Continuously oxidizing the untreated phenol-ammonia wastewater, and sequentially oxidizing and degrading step by step to reach the first stateA class emission standard;
the whole circulating treatment process of the three-stage photoelectrocatalysis recovery treatment electrolytic tank is to carry out photoelectrocatalysis treatment on high-concentration phenol-ammonia wastewater entering from the water inlet (1) and OH generated by photoelectrocatalysis decomposition of water by the modified bipolar membrane diaphragm (5)-Combine to get into ammonia absorbing device (8), phenol extraction plant (9) and phenol distillation plant (10) carry out recovery processing, high concentration phenol ammonia waste water is retrieved and is turned into low concentration phenol ammonia waste water and reentrant one-level photoelectric processing apparatus's anode tank and carry out anodic oxidation and handle, then flow into second grade photoelectric processing apparatus's anode tank through the pipeline, reentrant tertiary photoelectric processing apparatus's anode tank after oxidation, then flow into tertiary processing apparatus's cathode cell, gaseous diffusion negative pole (6) store has a large amount of air, oxygen in the air is at H+Is reduced by the cathode to a strong oxidant H in the presence of2O2Strong oxidizing agent H2O2And continuously oxidizing and degrading the phenol and the ammonia nitrogen which are not completely treated in the cathode tank, sequentially entering the cathode tanks of the secondary treatment device and the primary treatment device to perform the same oxidation treatment, and finally discharging the phenol and the ammonia wastewater after being detected to be qualified by an ultraviolet spectrophotometry, thereby realizing the photoelectrocatalysis recovery treatment of the high-concentration phenol and ammonia wastewater.
2. The photoelectrocatalytic recovery processing device for high concentration phenol-ammonia wastewater as set forth in claim 1, wherein the injection amount of phenol-ammonia wastewater into the anode chamber (2) is not more than two thirds of the total volume of the anode chamber.
3. The photoelectrocatalytic recovery processing device for high-concentration phenol-ammonia wastewater as set forth in claim 1, wherein the ceramic membrane (3) is a cylindrical cone having an outer diameter to inner diameter ratio of 1.08: 1, has a thickness of not more than 3cm, and is made of starch, SiO2、Al2O3And acrylamide.
4. The photoelectrocatalytic recovery processing device for high-concentration phenol-ammonia wastewater as set forth in claim 1, wherein the length, width and thickness ratio of the anode (4) is 6: 1: 0.1, and the electrode material is activeTitanium-based oxide anode of the active layer or binary metal oxide electrode, the active layer of the titanium-based oxide anode is PbO2、MnO2And SnO2One or two of them mixed in different proportion, the binary metal oxide electrode is MnxCr1-xO3/2And CoxCr1-xO3/2One kind of (1).
5. The photoelectrocatalytic recovery processing device for high-concentration phenol-ammonia wastewater as set forth in claim 1, wherein the bipolar membrane separator (5) is made of sodium carboxymethylcellulose and chitosan, and Cu with a mass ratio of not more than 50% of the total mass of the bipolar membrane is added2O、g-C3N4One or more of graphene, carbon quantum dots and MOFs are modified, and OH generated by photoelectrocatalysis decomposition of water by the modified graphene, carbon quantum dots and MOFs is increased-And H+The efficiency of the adhesive is obtained by adopting a hot pressing method or a tape casting method, and the thickness range is 50-200 mu m.
6. The photoelectrocatalytic recovery processing device for high concentration phenol ammonia wastewater as set forth in claim 1, wherein the gas diffusion cathode (6) is a hollow cylinder with a ratio of outer diameter, inner diameter, height of 1:6 or a hollow cylinder with a ratio of diameter, height of 1:6, the solid cylinder is prepared by mixing one or more of porous carbon, graphite powder, carbon black, acetylene black and superconducting carbon black with graphene through a hot pressing method.
7. The photoelectrocatalytic recovery processing device for high-concentration phenol-ammonia wastewater as set forth in claim 1, wherein the distance between the anode (4) and the gas diffusion cathode (6) from the bipolar membrane separator (5) is not more than 20 cm.
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