CN114349266A - Advanced sewage treatment device and method for in-situ generation of hydrogen peroxide and ozone - Google Patents

Advanced sewage treatment device and method for in-situ generation of hydrogen peroxide and ozone Download PDF

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Publication number
CN114349266A
CN114349266A CN202111527496.4A CN202111527496A CN114349266A CN 114349266 A CN114349266 A CN 114349266A CN 202111527496 A CN202111527496 A CN 202111527496A CN 114349266 A CN114349266 A CN 114349266A
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tank
hydrogen peroxide
ozone
water
gas
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Inventor
李武林
季献华
李宽
王辰
田聃
刘鼎
杨宏伟
汪文强
展巨宏
王玉珏
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Research Institute For Environmental Innovation (suzhou) Tsinghua
Jiangsu Jingyuan Environmental Protection Co ltd
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Research Institute For Environmental Innovation (suzhou) Tsinghua
Jiangsu Jingyuan Environmental Protection Co ltd
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Priority to CN202111527496.4A priority Critical patent/CN114349266A/en
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4612—Controlling or monitoring
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4619—Supplying gas to the electrolyte
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/78—Details relating to ozone treatment devices
    • C02F2201/782—Ozone generators
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention discloses a sewage advanced treatment device for in-situ generation of hydrogen peroxide and ozone and a method thereof. The invention adopts in-situ generated hydrogen peroxide and ozone, can be directly used for sewage treatment, does not need to prepare the hydrogen peroxide and the ozone additionally, is respectively provided with a special adding device, can improve the solubility of the hydrogen peroxide and the ozone in water, increases the contact probability of the hydrogen peroxide and the ozone, improves the generation rate of hydroxyl free radicals, can oxidize partial simple organic matters in water into water and carbon dioxide, can oxidize macromolecular substances which are difficult to be biodegraded in water, breaks molecular chains, oxidizes long-chain macromolecules into short-chain micromolecular organic matters, and can convert non-biodegradable organic matters into degradable organic matters.

Description

Advanced sewage treatment device and method for in-situ generation of hydrogen peroxide and ozone
Technical Field
The invention relates to a sewage treatment device and a method thereof, in particular to a sewage advanced treatment device and a method thereof for generating hydrogen peroxide and ozone in situ, belonging to the technical field of water treatment.
Background
Along with the gradual enhancement of the awareness of environmental protection, the national environment protection investment is more and more intense, and meanwhile, the national requirements and standards for the discharge control of polluted sewage are higher and higher. The treatment process adopted at present is a physicochemical and biochemical treatment method regardless of domestic sewage or industrial sewage, but for the current increasingly strict discharge standard, the method can not meet the requirements far away, and a subsequent advanced treatment process is required to be added.
The current advanced treatment processes comprise physical treatment, such as filtration and centrifugation, physical and chemical treatment, such as ion exchange, membrane separation and advanced oxidation, and biological treatment, such as a biological filter and biological activated carbon. The single treatment method can only remove partial pollutants in the sewage, or has high operation cost and complex process operation, and is difficult to completely meet the requirements of advanced treatment process. Therefore, various advanced treatment processes are combined, different treatment units have different treatment functions, and sewage is treated in a targeted manner in sections, so that the sewage treatment efficiency and capacity are improved, the treatment cost is reduced, and the high-efficiency and low-energy treatment effect is realized.
Ozone is obtained in situ by adopting an ozone generator device in the existing sewage treatment process by combining ozone and hydrogen peroxide, the hydrogen peroxide is obtained in a mode of storing in-situ ton barrels, the concentration of the hydrogen peroxide is generally 27.5%, the concentration of the hydrogen peroxide is higher than 8%, the hydrogen peroxide belongs to dangerous chemicals, certain risks exist in transportation and storage, the northern area is severe in weather in winter, the problem of untimely transportation and the like can exist, and the problem of no medicine available in the field is caused.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sewage advanced treatment device for generating hydrogen peroxide and ozone in situ and a method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the utility model provides an advanced wastewater treatment device for in situ generation of hydrogen peroxide and ozone, which is characterized in that: comprises a sand filter, a middle water tank, an EP oxidation tank, a biochemical regulating tank, a BAC tank and a clean water tank which are connected in sequence, wherein the EP oxidation tank is connected with a hydrogen peroxide generator, an ozone generator and an ozone tail gas destructor.
Furthermore, the intermediate water tank is connected with an acid dosing pipe and an alkali dosing pipe, and the biochemical regulating tank is also connected with the acid dosing pipe and the alkali dosing pipe.
Furthermore, a middle water tank water outlet pump is arranged on a connecting pipeline between the middle water tank and the EP oxidation tank, a biochemical regulating tank water outlet pump is arranged on a connecting pipeline between the biochemical regulating tank and the BAC tank, and a clean water tank water outlet pump is arranged at the bottom of the clean water tank.
Furthermore, a pipeline mixer is arranged on a connecting pipeline of the intermediate water tank and the EP oxidation tank, and a water outlet pipeline of the hydrogen peroxide generator is divided into two paths which are respectively connected with the pipeline mixer and the EP oxidation tank.
Furthermore, a circulating pipeline is arranged on the outer side of the EP oxidation pond, two ends of the circulating pipeline are respectively communicated with the EP oxidation pond, a gas-liquid mixing pump is arranged on the circulating pipeline, and the ozone generator is connected with the gas-liquid mixing pump.
Furthermore, a titanium plate aeration head is arranged at the bottom of the EP oxidation tank, and the ozone generator is connected with the titanium plate aeration head in the EP oxidation tank.
Further, the hydrogen peroxide generator comprises
The electrolytic system comprises an electrolytic cell and a direct current power supply, wherein an anode and a gas diffusion cathode are arranged in the electrolytic cell, a gas chamber communicated with the gas diffusion cathode is arranged on one side of the gas diffusion cathode away from the anode, and the anode and the cathode of the direct current power supply are respectively connected with the anode and the gas diffusion cathode;
the gas supply system supplies gas to the gas chamber;
and the liquid supply system is used for supplying electrolyte to the electrolytic cell, and the electrolyte is soluble sulfate solution.
Further, the gas supply system supplies gas such as air or oxygen.
Further, the soluble sulfate comprises one or a combination of sodium sulfate and potassium sulfate.
Further, the hydrogen peroxide generator also comprises
The automatic control system adjusts the gas supply of the gas supply system to the electrolytic cell based on the gas flow and/or the pressure signal of the gas chamber sent by the gas supply system, and adjusts the liquid supply system to supply liquid to the electrolytic cell based on the conductivity of the electrolyte in the electrolytic cell and/or the liquid flow signal of the liquid supply system;
H2alarm device for measuring gasH generated by diffusion cathode2Concentration of H in the measured2An alarm is given when the concentration exceeds a safety threshold;
H2O2a storage tank connected to the electrolyzer for receiving H produced by the electrolyzer2O2。
Further, the gas supply system comprises
A dryer for drying the gas;
and the flowmeter is used for controlling the gas flow of the dried gas.
Further, the liquid supply system comprises
The water softening equipment is used for removing alkaline earth metal ions in tap water, and is an ion exchange type water softener or a nanofiltration membrane water softener;
the water inlet of the electrolyte storage tank is connected with the water outlet of the water softening equipment, the feed inlet of the electrolyte storage tank is used for adding electrolyte into the electrolyte storage tank, the liquid outlet of the electrolyte storage tank is connected with the electrolytic bath to provide electrolyte for the electrolytic bath, and a stirrer is arranged in the electrolyte storage tank to stir to form electrolyte;
the reaction tank is provided with a precipitator adding port and a liquid inlet, the liquid inlet of the reaction tank is used for adding the crude sodium sulfate salt solution into the reaction tank, and the precipitator adding port of the reaction tank is used for adding a precipitator into the reaction tank to precipitate Ca in the crude sodium sulfate salt solution2+、Mg2+；
The clarifying tank is connected with the reaction tank to receive the reaction liquid from the reaction tank, and is also connected with a flocculating agent supply device to supply flocculating agent into the clarifying tank;
and the filtering device is connected with the clarifying tank to filter the liquid from the clarifying tank to obtain the primary refined soluble sulfate solution.
Further, the filtering device comprises
A sand filter, wherein the sand filter is connected with a clarifying tank, and liquid from the clarifying tank is subjected to rough filtration to obtain crude filtrate;
the alpha-cellulose filter aid is precoated with a carbon tube filter, and the alpha-cellulose filter aid precoated carbon tube filter is connected with a sand filter so as to carry out fine filtration on coarse filtrate from the sand filter to obtain a primary refined sodium sulfate solution.
Further, the liquid supply system further comprises a chelating resin tower, and the chelating resin tower is connected with the filtering device to carry out secondary refining on the primary refined soluble sulfate solution to obtain a secondary refined soluble sulfate solution.
Further, a cation exchange membrane is arranged in the electrolytic cell and is positioned between the anode and the gas diffusion cathode.
Further, the anode contains Ir oxide or a metal oxide mixture of Ir and one or more metals selected from Ru, Ta, Pt and Sn, and the gas diffusion electrode is loaded with a catalyst which is a noble metal catalyst or a carbon-based catalyst.
Further, the noble metal catalyst is one or more of Au-Ni-Pt, Au-Pd, Pt-Hg, Pd-Sn and Ag-Pt catalysts, and the carbon-based catalyst is one or more of graphite, activated carbon, carbon black, carbon nano tubes and graphene.
A treatment method of a sewage advanced treatment device for generating hydrogen peroxide and ozone in situ is characterized by comprising the following steps:
the sewage to be treated firstly enters a sand filter, the sewage filtered by quartz sand enters an intermediate water tank, then enters an EP oxidation tank under the lifting of an outlet water pump of the intermediate water tank, organic matters in the inlet water are subjected to oxidative degradation under the combined action of ozone and hydrogen peroxide generated by an ozone generator and a hydrogen peroxide generator, the outlet water enters a biochemical regulating tank, the sewage is lifted to a BAC tank under the action of an outlet water pump of the biochemical regulating tank, the sewage is subjected to active carbon filtration treatment, the organic matter concentration of the outlet water is further reduced, impurities and by-products partially generated by the ozone are simultaneously filtered and adsorbed, the filtered outlet water enters a clean water tank, and the sewage is discharged under the action of a clean water tank lifting pump.
Further, the unit yield of ozone in the ozone generator is 400-400 g/h, the unit yield of the hydrogen peroxide generator is 90-200/h, the design flow rate of the sand filter is 5-8m/h, the retention time of the EP aerobic pool is 140min, and the contact time of the BAC pool is 30-40 min.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention adopts in-situ generated hydrogen peroxide and ozone, can be directly used for sewage treatment, does not need to prepare the hydrogen peroxide and the ozone additionally, is respectively provided with a special adding device, can improve the solubility of the hydrogen peroxide and the ozone in water, increases the contact probability of the hydrogen peroxide and the ozone, improves the generation rate of hydroxyl free radicals, can oxidize partial simple organic matters in water into water and carbon dioxide, can oxidize macromolecular substances which are difficult to be biodegraded in water, breaks molecular chains, oxidizes long-chain macromolecules into short-chain micromolecular organic matters, and can convert non-biodegradable organic matters into degradable organic matters. Improves the molecular polarity and the hydrophilicity, improves the biodegradability, further increases the removal rate of organic pollutants in the sewage, and reduces the concentration of organic matters in the effluent.
(2) The invention adopts the BAC pool as a post-treatment stage, high iodine value active carbon is adopted to treat the effluent of the EP oxidation pool, the active carbon on the upper layer of the BAC pool adsorbs the ozone in the sewage to reduce the concentration of the ozone in the effluent, meanwhile, the adsorbed ozone can be decomposed to provide oxygen for the biodegradation process of the active carbon on the lower layer, thereby further reducing the organic matter content of the effluent, the active carbon rapidly adsorbs the organic matters dissolved in the water through the larger specific surface area of the active carbon, the microorganisms in the water are enriched, the adsorption of the organic matters and the oxidation of the microorganisms are sequentially carried out, the oxidative decomposition of the microorganisms recovers the adsorption capacity of the active carbon, the active carbon is regenerated, the microorganisms obtain rich nutrient substances through the adsorption of the active carbon, the decomposition of the ozone provides oxygen for the microorganisms, the three mutually promote to form a relatively stable state, a stable treatment effect is obtained, thereby the regeneration period of the active carbon is greatly prolonged, ensuring the stability of the water outlet. The nitrifying bacteria adsorbed on the activated carbon can oxidize ammonia nitrogen in water into nitrate nitrogen and nitrite nitrogen, so that the ammonia nitrogen concentration of the effluent is reduced.
(3) The acid and alkali adding devices are arranged in front of and behind the EP oxidation tank, the pH values of inlet water and outlet water of the EP oxidation tank can be changed according to needs, the device can adapt to sewage with different water qualities, and the adaptability of the device is improved.
(4) The components of the hydrogen peroxide generator are integrated in a rectangular container, so that the hydrogen peroxide generator can be flexibly transported, can be used after being assembled and quickly realize the functions.
(5) The invention adopts two ozone adding devices, namely titanium plate aeration adding and gas-liquid mixing adding, which can be selected according to different requirements, and the two adding devices are mutually standby, thereby avoiding the situation that the equipment cannot normally operate when one adding device has problems.
Drawings
FIG. 1 is a schematic view of an advanced wastewater treatment apparatus for in situ generation of hydrogen peroxide and ozone according to the present invention.
Fig. 2 is a schematic view of a continuous electrochemical synthesis system of the hydrogen peroxide generator of the present invention.
FIG. 3 is a schematic view of the liquid supply system of the hydrogen peroxide generator of the present invention.
Fig. 4 is a schematic view of an electrolytic cell of the hydrogen peroxide generator of the present invention.
Detailed Description
To elaborate on technical solutions adopted by the present invention to achieve predetermined technical objects, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, it is obvious that the described embodiments are only partial embodiments of the present invention, not all embodiments, and technical means or technical features in the embodiments of the present invention may be replaced without creative efforts, and the present invention will be described in detail below with reference to the drawings and in conjunction with the embodiments.
As shown in figure 1, the advanced wastewater treatment device for generating hydrogen peroxide and ozone in situ comprises a sand filter 1, an intermediate water tank 2, an EP oxidation tank 3, a biochemical regulating tank 17, a BAC tank 4 and a clean water tank 5 which are connected in sequence, wherein the EP oxidation tank 3 is connected with a hydrogen peroxide generator 11, an ozone generator 10 and an ozone tail gas destructor 12. Adopt normal position production hydrogen peroxide and ozone, can directly be used for sewage treatment, need not to prepare hydrogen peroxide and ozone in addition, hydrogen peroxide and ozone are furnished with special throwing feeder apparatus respectively, can improve both the solubility in aqueous, increase the contact probability of hydrogen peroxide and ozone, improve the production rate of hydroxyl radical, can be with the simple organic matter oxidation of aquatic part for water and carbon dioxide, the difficult biodegradable's of while still oxidizable aquatic macromolecular substance, break the molecular chain, with long chain macromolecule oxidation short chain micromolecule organic matter, still can turn into biodegradable organic matter with non biodegradable's organic matter simultaneously. Improves the molecular polarity and the hydrophilicity, improves the biodegradability, further increases the removal rate of organic pollutants in the sewage, and reduces the concentration of organic matters in the effluent. The invention adopts the BAC pool as a post-treatment stage, high iodine value active carbon is adopted to treat the effluent of the EP oxidation pool, the active carbon on the upper layer of the BAC pool adsorbs the ozone in the sewage to reduce the concentration of the ozone in the effluent, meanwhile, the adsorbed ozone can be decomposed to provide oxygen for the biodegradation process of the active carbon on the lower layer, thereby further reducing the organic matter content of the effluent, the active carbon rapidly adsorbs the organic matters dissolved in the water through the larger specific surface area of the active carbon, the microorganisms in the water are enriched, the adsorption of the organic matters and the oxidation of the microorganisms are sequentially carried out, the oxidative decomposition of the microorganisms recovers the adsorption capacity of the active carbon, the active carbon is regenerated, the microorganisms obtain rich nutrient substances through the adsorption of the active carbon, the decomposition of the ozone provides oxygen for the microorganisms, the three mutually promote to form a relatively stable state, a stable treatment effect is obtained, thereby the regeneration period of the active carbon is greatly prolonged, ensuring the stability of the water outlet. The nitrifying bacteria adsorbed on the activated carbon can oxidize ammonia nitrogen in water into nitrate nitrogen and nitrite nitrogen, so that the ammonia nitrogen concentration of the effluent is reduced.
The middle water tank 2 is connected with an acid dosing pipe 6 and an alkali dosing pipe 7, and the biochemical regulating tank 17 is also connected with the acid dosing pipe 6 and the alkali dosing pipe 7. Acid and alkali adding devices are arranged in front of and behind the EP oxidation tank, the pH values of inlet and outlet water of the EP oxidation tank can be changed as required, the device is suitable for sewage with different water qualities, and the adaptability of the device is improved.
An intermediate water tank water outlet pump 9 is arranged on a connecting pipeline of the intermediate water tank 2 and the EP oxidation tank 3, a biochemical regulating tank water outlet pump 13 is arranged on a connecting pipeline of the biochemical regulating tank 17 and the BAC tank 4, and a clean water tank water outlet pump 14 is arranged at the bottom of the clean water tank 5.
A pipeline mixer 8 is arranged on a connecting pipeline of the intermediate water tank 2 and the EP oxidation tank 3, and a water outlet pipeline of the hydrogen peroxide generator 11 is divided into two paths which are respectively connected with the pipeline mixer 8 and the EP oxidation tank 3.
A circulating pipeline with two ends respectively communicated with the EP oxidation pond 3 is arranged outside the EP oxidation pond 3, a gas-liquid mixing pump 15 is arranged on the circulating pipeline, and an ozone generator 10 is connected with the gas-liquid mixing pump 15. In this embodiment, two sets of ozone generators 10 are provided, and stable operation of the system is ensured by switching between main and standby. The bottom of the EP oxidation tank 3 is provided with a titanium plate aeration head 16, and the ozone generator 10 is connected with the titanium plate aeration head 16 in the EP oxidation tank 3. The invention adopts two ozone adding devices, namely titanium plate aeration adding and gas-liquid mixing adding, which can be selected according to different requirements, and the two adding devices are mutually standby, thereby avoiding the situation that the equipment cannot normally operate when one adding device has problems.
As shown in FIG. 2, the hydrogen peroxide generator comprises
The electrolytic system comprises an electrolytic cell and a direct current power supply, wherein an anode and a gas diffusion cathode are arranged in the electrolytic cell, a gas chamber communicated with the gas diffusion cathode is arranged on one side of the gas diffusion cathode away from the anode, and the anode and the cathode of the direct current power supply are respectively connected with the anode and the gas diffusion cathode;
the gas supply system supplies gas to the gas chamber; the gas supply system supplies gas which is air or oxygen. The gas supply system comprises a dryer used for drying gas; and the flowmeter is used for controlling the gas flow of the dried gas.
And the liquid supply system is used for supplying electrolyte to the electrolytic cell, and the electrolyte is soluble sulfate solution. The soluble sulfate comprises one or a combination of sodium sulfate and potassium sulfate.
The automatic control system adjusts the gas supply of the gas supply system to the electrolytic cell based on the gas flow and/or the pressure signal of the gas chamber sent by the gas supply system, and adjusts the liquid supply system to supply liquid to the electrolytic cell based on the conductivity of the electrolyte in the electrolytic cell and/or the liquid flow signal of the liquid supply system;
H2alarm device for measuring H generated by gas diffusion cathode2Concentration of H in the measured2An alarm is given when the concentration exceeds a safety threshold;
H2O2a storage tank connected to the electrolyzer for receiving H produced by the electrolyzer2O2。
The components of the hydrogen peroxide generator are integrated in a rectangular container, so that the hydrogen peroxide generator can be flexibly transported, can be used after being assembled and quickly realize the functions.
Wherein, as shown in FIG. 3, the liquid supply system comprises
The water softening equipment is used for removing alkaline earth metal ions in tap water, and is an ion exchange type water softener or a nanofiltration membrane water softener;
the water inlet of the electrolyte storage tank is connected with the water outlet of the water softening equipment, the feed inlet of the electrolyte storage tank is used for adding electrolyte into the electrolyte storage tank, the liquid outlet of the electrolyte storage tank is connected with the electrolytic bath to provide electrolyte for the electrolytic bath, and a stirrer is arranged in the electrolyte storage tank to stir to form electrolyte;
the reaction tank is provided with a precipitator adding port and a liquid inlet, the liquid inlet of the reaction tank is used for adding the crude sodium sulfate salt solution into the reaction tank, and the precipitator adding port of the reaction tank is used for adding a precipitator into the reaction tank to precipitate Ca in the crude sodium sulfate salt solution2+、Mg2+；
The clarifying tank is connected with the reaction tank to receive the reaction liquid from the reaction tank, and is also connected with a flocculating agent supply device to supply flocculating agent into the clarifying tank;
and the filtering device is connected with the clarifying tank to filter the liquid from the clarifying tank to obtain the primary refined soluble sulfate solution.
And the chelating resin tower is connected with the filtering device so as to carry out secondary refining on the primary refined soluble sulfate solution and obtain a secondary refined soluble sulfate solution.
Wherein the filtering device comprises
A sand filter, wherein the sand filter is connected with a clarifying tank, and liquid from the clarifying tank is subjected to rough filtration to obtain crude filtrate;
the alpha-cellulose filter aid is precoated with a carbon tube filter, and the alpha-cellulose filter aid precoated carbon tube filter is connected with a sand filter so as to carry out fine filtration on coarse filtrate from the sand filter to obtain a primary refined sodium sulfate solution.
As shown in fig. 4, a cation exchange membrane is provided in the electrolytic cell between the anode and the gas diffusion cathode. The anode contains Ir oxide or a metal oxide mixture of Ir and one or more metals selected from Ru, Ta, Pt and Sn, and the gas diffusion electrode is loaded with a catalyst which is a noble metal catalyst or a carbon-based catalyst. The noble metal catalyst is one or more of Au-Ni-Pt, Au-Pd, Pt-Hg, Pd-Sn and Ag-Pt catalysts, and the carbon-based catalyst is one or more of graphite, activated carbon, carbon black, carbon nano tubes and graphene.
A treatment method of a sewage advanced treatment device for generating hydrogen peroxide and ozone in situ comprises the following steps:
the sewage to be treated firstly enters a sand filter, the sewage filtered by quartz sand enters an intermediate water tank, then enters an EP oxidation tank under the lifting of an outlet water pump of the intermediate water tank, organic matters in the inlet water are subjected to oxidative degradation under the combined action of ozone and hydrogen peroxide generated by an ozone generator and a hydrogen peroxide generator, the outlet water enters a biochemical regulating tank, the sewage is lifted to a BAC tank under the action of an outlet water pump of the biochemical regulating tank, the sewage is subjected to active carbon filtration treatment, the organic matter concentration of the outlet water is further reduced, impurities and by-products partially generated by the ozone are simultaneously filtered and adsorbed, the filtered outlet water enters a clean water tank, and the sewage is discharged under the action of a clean water tank lifting pump.
Wherein the unit yield of ozone in the ozone generator is 100-400g/h, the unit yield of the hydrogen peroxide generator is 90-200/h, the design flow rate of the sand filter is 5-8m/h, the retention time of the EP aerobic pool is 100-140min, and the contact time of the BAC pool is 30-40 min.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (19)

1. The utility model provides an advanced wastewater treatment device for in situ generation of hydrogen peroxide and ozone, which is characterized in that: comprises a sand filter, a middle water tank, an EP oxidation tank, a biochemical regulating tank, a BAC tank and a clean water tank which are connected in sequence, wherein the EP oxidation tank is connected with a hydrogen peroxide generator, an ozone generator and an ozone tail gas destructor.
2. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 1, wherein: the middle water tank is connected with an acid dosing pipe and an alkali dosing pipe, and the biochemical regulating tank is also connected with the acid dosing pipe and the alkali dosing pipe.
3. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 1, wherein: and a middle water tank water outlet pump is arranged on a connecting pipeline between the middle water tank and the EP oxidation tank, a biochemical regulating tank water outlet pump is arranged on a connecting pipeline between the biochemical regulating tank and the BAC tank, and a clean water tank water outlet pump is arranged at the bottom of the clean water tank.
4. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 1, wherein: and a pipeline mixer is arranged on a connecting pipeline of the intermediate water tank and the EP oxidation tank, and a water outlet pipeline of the hydrogen peroxide generator is divided into two paths which are respectively connected with the pipeline mixer and the EP oxidation tank.
5. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 1, wherein: and a circulating pipeline with two ends respectively communicated with the EP oxidation pond is arranged outside the EP oxidation pond, a gas-liquid mixing pump is arranged on the circulating pipeline, and an ozone generator is connected with the gas-liquid mixing pump.
6. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 1, wherein: the bottom of the EP oxidation tank is provided with a titanium plate aeration head, and the ozone generator is connected with the titanium plate aeration head in the EP oxidation tank.
7. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 1, wherein: the hydrogen peroxide generator comprises
The electrolytic system comprises an electrolytic cell and a direct current power supply, wherein an anode and a gas diffusion cathode are arranged in the electrolytic cell, a gas chamber communicated with the gas diffusion cathode is arranged on one side of the gas diffusion cathode away from the anode, and the anode and the cathode of the direct current power supply are respectively connected with the anode and the gas diffusion cathode;
the gas supply system supplies gas to the gas chamber;
and the liquid supply system is used for supplying electrolyte to the electrolytic cell, and the electrolyte is soluble sulfate solution.
8. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 7, wherein: the gas supply system provides gas which is air or oxygen.
9. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 7, wherein: the soluble sulfate comprises one or the combination of two of sodium sulfate and potassium sulfate.
10. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 7, wherein: the hydrogen peroxide generator also comprises
The automatic control system adjusts the gas supply of the gas supply system to the electrolytic cell based on the gas flow and/or the pressure signal of the gas chamber sent by the gas supply system, and adjusts the liquid supply system to supply liquid to the electrolytic cell based on the conductivity of the electrolyte in the electrolytic cell and/or the liquid flow signal of the liquid supply system;
H2alarm device for measuring H generated by gas diffusion cathode2Concentration of H in the measured2An alarm is given when the concentration exceeds a safety threshold;
H2O2a storage tank connected to the electrolyzer for receiving H produced by the electrolyzer2O2。
11. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 7, wherein: the gas supply system comprises
A dryer for drying the gas;
and the flowmeter is used for controlling the gas flow of the dried gas.
12. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 7, wherein: the liquid supply system comprises
The water softening equipment is used for removing alkaline earth metal ions in tap water, and is an ion exchange type water softener or a nanofiltration membrane water softener;
the water inlet of the electrolyte storage tank is connected with the water outlet of the water softening equipment, the feed inlet of the electrolyte storage tank is used for adding electrolyte into the electrolyte storage tank, the liquid outlet of the electrolyte storage tank is connected with the electrolytic bath to provide electrolyte for the electrolytic bath, and a stirrer is arranged in the electrolyte storage tank to stir to form electrolyte;
the reaction tank is provided with a precipitator adding port and a liquid inlet, the liquid inlet of the reaction tank is used for adding the crude sodium sulfate salt solution into the reaction tank, and the precipitator adding port of the reaction tank is used for adding a precipitator into the reaction tank to precipitate Ca in the crude sodium sulfate salt solution2+、Mg2+；
The clarifying tank is connected with the reaction tank to receive the reaction liquid from the reaction tank, and is also connected with a flocculating agent supply device to supply flocculating agent into the clarifying tank;
and the filtering device is connected with the clarifying tank to filter the liquid from the clarifying tank to obtain the primary refined soluble sulfate solution.
13. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 12, wherein: the filtering device comprises
A sand filter, wherein the sand filter is connected with a clarifying tank, and liquid from the clarifying tank is subjected to rough filtration to obtain crude filtrate;
the alpha-cellulose filter aid is precoated with a carbon tube filter, and the alpha-cellulose filter aid precoated carbon tube filter is connected with a sand filter so as to carry out fine filtration on coarse filtrate from the sand filter to obtain a primary refined sodium sulfate solution.
14. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 12, wherein: the liquid supply system further comprises a chelating resin tower, and the chelating resin tower is connected with the filtering device to carry out secondary refining on the primary refined soluble sulfate solution to obtain a secondary refined soluble sulfate solution.
15. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 7, wherein: and a cation exchange membrane is arranged in the electrolytic cell and is positioned between the anode and the gas diffusion cathode.
16. The advanced wastewater treatment device for in-situ generation of hydrogen peroxide and ozone according to claim 7, wherein: the anode contains Ir oxide or a metal oxide mixture of Ir and one or more metals selected from Ru, Ta, Pt and Sn, and the gas diffusion electrode is loaded with a catalyst which is a noble metal catalyst or a carbon-based catalyst.
17. The advanced wastewater treatment plant for in situ generation of hydrogen peroxide and ozone as claimed in claim 16, wherein: the noble metal catalyst is one or more of Au-Ni-Pt, Au-Pd, Pt-Hg, Pd-Sn and Ag-Pt catalysts, and the carbon-based catalyst is one or more of graphite, activated carbon, carbon black, carbon nano tubes and graphene.
18. A method for treating a wastewater advanced treatment device for generating hydrogen peroxide and ozone in situ according to any one of claims 1 to 17, which comprises the following steps:
the sewage to be treated firstly enters a sand filter, the sewage filtered by quartz sand enters an intermediate water tank, then enters an EP oxidation tank under the lifting of an outlet water pump of the intermediate water tank, organic matters in the inlet water are subjected to oxidative degradation under the combined action of ozone and hydrogen peroxide generated by an ozone generator and a hydrogen peroxide generator, the outlet water enters a biochemical regulating tank, the sewage is lifted to a BAC tank under the action of an outlet water pump of the biochemical regulating tank, the sewage is subjected to active carbon filtration treatment, the organic matter concentration of the outlet water is further reduced, impurities and by-products partially generated by the ozone are simultaneously filtered and adsorbed, the filtered outlet water enters a clean water tank, and the sewage is discharged under the action of a clean water tank lifting pump.
19. The process of claim 18, wherein: the unit yield of ozone in the ozone generator is 100-400g/h, the unit yield of the hydrogen peroxide generator is 90-200/h, the design flow rate of the sand filter is 5-8m/h, the retention time of the EP aerobic pool is 100-140min, and the contact time of the BAC pool is 30-40 min.
CN202111527496.4A 2021-12-15 2021-12-15 Advanced sewage treatment device and method for in-situ generation of hydrogen peroxide and ozone Pending CN114349266A (en)

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