CN117164142A - Heterogeneous ozone catalytic oxidation system and application thereof in cultivation wastewater treatment - Google Patents

Heterogeneous ozone catalytic oxidation system and application thereof in cultivation wastewater treatment Download PDF

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Publication number
CN117164142A
CN117164142A CN202311029395.3A CN202311029395A CN117164142A CN 117164142 A CN117164142 A CN 117164142A CN 202311029395 A CN202311029395 A CN 202311029395A CN 117164142 A CN117164142 A CN 117164142A
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tower
catalytic oxidation
wastewater
ozone catalytic
ozone
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陈宏绣
焦翔翔
申妍颖
王花平
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Shanxi Zihuan Technology Co ltd
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Shanxi Zihuan Technology Co ltd
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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • 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
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/14—NH3-N
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Microbiology (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Biological Treatment Of Waste Water (AREA)

Abstract

The invention relates to a heterogeneous ozone catalytic oxidation system and a method for deeply treating aquaculture wastewater, wherein the system comprises a biological treatment reactor, a primary ozone catalytic oxidation tower, a secondary ozone catalytic oxidation tower and an aeration biological filtration tower (BAF tower), and the heights of the primary ozone catalytic oxidation tower, the secondary ozone catalytic oxidation tower and the BAF tower are gradually decreased. The invention effectively reduces the ozone consumption, improves the ozone utilization rate, can further reduce pollutants (COD, SS, antibiotics and chromaticity) in the effluent after biological treatment, has stable effluent quality and can reach the 'standard of water quality for farm irrigation' (GB 5084-2021).

Description

Heterogeneous ozone catalytic oxidation system and application thereof in cultivation wastewater treatment
Technical Field
The invention relates to the field of wastewater treatment, in particular to a heterogeneous ozone catalytic oxidation system and application thereof in cultivation wastewater treatment.
Background
The ozone catalytic oxidation technology combines the strong oxidizing property of ozone with the catalytic adsorptivity of a catalyst, and the OH produced by catalysis has strong oxidizing capability, can decompose most organic pollutants in the cultivation wastewater, and is a high-grade oxidation technology. The cultivation wastewater has the characteristics of poor biodegradability (high COD, low BOD), high suspended solids SS and the like, and is wastewater which is difficult to treat. The existing treatment method is to reuse farmlands after biological treatment such as oxidation ponds, MBBR, MBRs and the like, but the wastewater treated by the method still has the following problems: the method has the advantages that firstly, the concentration of pollutants (COD, BOD, SS) is still higher, the pollutants are directly recycled into the farmland, the soil volume weight is easily influenced, the salinization and hardening of the soil are caused, secondly, the phenomena of sludge expansion and falling, more foam and unstable water quality of effluent are easily caused in the operation process, thirdly, the treatment process is complex, the occupied area of a treatment device is large, the reaction time is long, the cost is high, and fourthly, the wastewater further meets the requirements of the farmland irrigation water quality standard (GB 5084-2021), so that the culture wastewater treated by a biological method is subjected to advanced treatment, such as ozone, ultraviolet and the like, so that the organic pollutants are further degraded, and pathogenic bacteria are disinfected and killed. But the ozone utilization rate is low, the reaction time is long, the cost is high, and the popularization and the application are difficult to realize. Therefore, researches on a method and a device for treating the aquaculture wastewater, which have higher degradation efficiency of wastewater pollutants, more stable system and simpler and more efficient treatment, are urgently needed in production.
Disclosure of Invention
The invention aims to provide a heterogeneous ozone catalytic oxidation system which comprises a primary ozone catalytic oxidation tower, a secondary ozone catalytic oxidation tower and an aeration biological filter tower (BAF tower); the heights of the first-stage ozone catalytic oxidation tower, the second-stage ozone catalytic oxidation tower and the BAF tower are gradually decreased;
the first-stage ozone catalytic oxidation tower comprises a first tower body, a first wastewater inlet pipe, a first water distributor, a first ozone inlet pipe, a first gas distribution pipe, a first silicon-aluminum-based catalyst, a first ultraviolet device, a first wastewater outlet pipe and a first tail oxygen collecting pipe;
the first wastewater inlet pipe is arranged on the side wall of the first tower body and is connected with a first water distributor at the bottom of the first tower body;
the first ozone inlet pipe is arranged on the side wall of the first tower body and is connected with a first gas distribution pipe at the bottom of the first tower body,
the first wastewater outlet pipe and the first tail oxygen collecting pipe are arranged at the top of the first tower body,
the first wastewater outlet pipe of the first-stage ozone catalytic oxidation tower is connected with the second wastewater inlet pipe of the second-stage ozone catalytic oxidation tower,
the second-stage ozone catalytic oxidation tower comprises a second tower body, a second wastewater inlet pipe, a second ozone inlet pipe, a second silicon-aluminum-based catalyst, a second ultraviolet device, a second wastewater outlet pipe and a second tail oxygen collecting pipe;
The second wastewater inlet pipe is arranged at the top of the second tower body and is connected with a spraying device at the upper part of the second tower body;
the second ozone inlet pipe is arranged on the side wall of the second tower body and is connected with a second gas distribution pipe at the bottom of the second tower body,
the second tail oxygen collecting pipe is arranged at the top of the second tower body,
the second wastewater outlet pipe of the second-stage ozone catalytic oxidation tower is arranged at the bottom of the second tower body and is connected with the water inlet of the BAF tower;
the middle parts of the two-stage ozone catalytic oxidation towers are provided with silicon-aluminum based catalysts which are supported and fixed in the towers by interception nets,
the two-stage ozone catalytic oxidation towers are provided with ultraviolet devices, the middle part of the tower body is alternately provided with an ultraviolet lamp tube every 50cm, the inside of the tower is separated by quartz glass, and the ultraviolet lamp tube can be pulled out from the side wall for replacement;
the BAF tower comprises a third tower body, a BAF tower water inlet, a third water distributor, a BAF tower air inlet, a third air distribution pipe, MBBR biological suspended filler and a BAF tower water outlet;
wherein the air inlet of the BAF tower is positioned at the lower part of the BAF tower and is connected with a third air distribution pipe, and the biological suspended filler of the MBBR is kept at the middle upper part of the BAF tower by a third interception net.
In a preferred embodiment of the present invention, the silica-alumina-based catalyst filler is selected from Mn-Fe-Ce/gamma-A l 2 O 3 、S iO2-A l 2 O 3 Any one or a combination thereof.
In the preferred technical scheme of the invention, the diameter of the ozone catalytic oxidation tower is 2-5m, and the height is 1-10m.
In the preferred technical scheme of the invention, the height of the filler in the ozone catalytic oxidation tower is 1-10m, preferably 4-6m.
In a preferred embodiment of the invention, the BAF tower has a diameter of 2-5m and a height of 1-10m.
In a preferred embodiment of the invention, the height of the packing in the BAF column is 1-10m, preferably 3-6m.
In the preferred technical scheme of the invention, a circulating water outlet is arranged in the middle of the side wall of the first-stage ozone catalytic oxidation tower, wastewater enters a venturi jet device on an ozone inlet pipe from the circulating water outlet through the action of a circulating pump, is quickly mixed with ozone gas and liquid, and enters the bottom of the first-stage ozone catalytic oxidation tower through an ozone inlet positioned at the lower part of the first-stage ozone catalytic oxidation tower together through a first gas distribution pipe.
In a preferred technical scheme of the invention, the system further comprises a biological treatment reactor, and the biological treatment reactor is connected with the first-stage ozone catalytic oxidation tower.
In the preferred technical scheme of the invention, the biological treatment reactor comprises an inner circular plate and an outer circular plate, wherein the inner circular plate and the outer circular plate are concentric circular plates, a central sedimentation tank is arranged at the inner side of the inner circular plate, an annular gap chamber is formed between the inner circular plate and the outer circular plate, and an MBBR anoxic zone, an MBBR aerobic zone, a contact oxidation anoxic zone, a contact oxidation aerobic zone, an MBR membrane reaction zone and an MBR membrane water production zone are arranged in the annular gap chamber in a separated manner, and each stage of treatment zone is separated by a separation plate;
The upper part of the MBBR anoxic zone is provided with a water inlet, the interior of the MBBR anoxic zone is provided with an MBBR biological suspension filler, and the side wall of the MBBR anoxic zone is provided with a submersible stirrer; the MBBR anoxic zone and the MBBR aerobic zone are separated by a first separation plate, and a first communication port is formed in the lower part of the first separation plate;
the MBBR biological suspended filler is arranged in the MBBR aerobic zone, the perforated aeration pipe is arranged at the bottom, the first water outlet pipeline is arranged at the upper part, and the central guide cylinder is communicated with the central sedimentation tank;
a central guide cylinder is arranged in the central sedimentation tank, a reflecting plate is arranged at the lower part of the central guide cylinder, a conical sludge settling hopper is arranged at the bottom of the central sedimentation tank, a triangular weir is arranged at the upper part of the central sedimentation tank, and a second water outlet pipeline is arranged on the triangular weir and communicated with the bottom of the contact oxidation anoxic zone;
biological rope filler is arranged in the contact oxidation anoxic zone, a submersible stirrer is arranged on the side wall of the contact oxidation anoxic zone, the contact oxidation anoxic zone and the contact oxidation aerobic zone are separated by a second partition plate, and a second communication port is formed in the upper part of the second partition plate;
biological rope filler is arranged in the contact oxidation aerobic zone, and a microporous aeration disc is arranged at the bottom of the contact oxidation aerobic zone; the contact oxidation aerobic zone and the MBR membrane reaction are separated by a third separation plate, and a third communication port is formed in the lower part of the third separation plate; the MBR membrane reaction zone is internally provided with a curtain type MBR hollow fiber membrane, the bottom of the MBR membrane reaction zone is provided with a microporous aeration device, and the upper part of the MBR membrane reaction zone is provided with a water suction pump and a third water outlet pipeline which are communicated with an MBR membrane water production zone;
And a water outlet is arranged in the MBR membrane water producing area.
In a preferred embodiment of the present invention, the MBBR bio-suspension filler is commercially available, preferably HDPE.
In a preferred embodiment of the present invention, the bio-rope filler is commercially available, preferably propylene fiber.
In a preferred technical scheme of the invention, the curtain type MBR hollow fiber membrane is commercially available, and is preferably an immersed type PVDF hollow fiber membrane.
Another object of the present invention is to provide a method for advanced treatment of aquaculture wastewater using a heterogeneous ozone catalytic oxidation system, comprising the steps of:
(1) The cultivation wastewater treated by the biological method enters the bottom of a first tower body from a wastewater inlet positioned on the side wall of a first-stage ozone catalytic oxidation tower through a first water distributor, passes through a silicon-aluminum-based catalyst positioned in the middle from bottom to top, and flows out from a first wastewater outlet pipe positioned on the side wall of the top after the combined action of ozone, the silicon-aluminum-based catalyst and ultraviolet light;
(2) The second-stage ozone catalytic oxidation tower is lower than the first-stage ozone catalytic oxidation tower, waste water flows out from a waste water outlet on the side wall of the top of the first-stage ozone catalytic oxidation tower, automatically flows into the upper part of the second-stage ozone catalytic oxidation tower by utilizing the height difference, uniformly distributes water in the second-stage ozone catalytic oxidation tower by adopting a spraying device, and flows from top to bottom through a silicon-aluminum-based catalyst positioned in the middle part, and flows out from a second waste water outlet pipe positioned on the side wall of the bottom after the combined action of ozone, the silicon-aluminum-based catalyst and ultraviolet light;
(3) The effluent of the second-stage ozone catalytic oxidation tower enters the tower from a water inlet of the BAF tower through a third water distributor at the upper part, and organic pollutants in the wastewater are further adsorbed, trapped and degraded through microorganisms attached to the MBBR biological suspended filler; at the same time, tail oxygen generated by the two-stage ozone catalytic oxidation towers is respectively converged from the top through pipelines, and then is introduced into the towers through the third gas distribution pipe by the gas inlet positioned on the side wall of the bottom of the BAF tower, so that aerobic environment is provided for microorganisms, and the microorganisms are ensured to fully and continuously decompose organic pollutants; and the wastewater is discharged from a water outlet at the bottom of the third tower body after being treated from top to bottom.
In the preferred technical scheme of the invention, a circulating water outlet is arranged in the middle of the side wall of the first-stage ozone catalytic oxidation tower, wastewater enters a venturi jet device on an ozone inlet pipe from the circulating water outlet through the action of a circulating pump, is quickly mixed with ozone gas and liquid, and enters the bottom of the first-stage ozone catalytic oxidation tower through an ozone inlet positioned at the lower part of the first-stage ozone catalytic oxidation tower together through a first gas distribution pipe.
In the preferred technical scheme of the invention, the venturi jet device is used in a manner that ozone is sucked into the wastewater through negative pressure generated at the throat of the venturi tube and is fully and uniformly mixed.
In the preferred technical scheme of the invention, the diameters of the primary ozone catalytic oxidation tower and the secondary ozone catalytic oxidation tower are 2-5m, and the heights are 1-10m.
In the preferred technical scheme of the invention, the residence time of the primary ozone catalytic oxidation tower and the secondary ozone catalytic oxidation tower is 1-10h.
In the preferable technical scheme of the invention, the generation amount of the ozone generator is 1-10kg/h.
In the preferred technical scheme of the invention, the heights of the fillers in the primary ozone catalytic oxidation tower and the secondary ozone catalytic oxidation tower are 1-10m, preferably 4-6m.
In the preferred technical scheme of the invention, the ultraviolet light provided by the ultraviolet device has the wavelength of 200-280nm and the ultraviolet light power of 75-350W.
In a preferred embodiment of the invention, the BAF tower has a diameter of 2-5m and a height of 1-10m.
In a preferred embodiment of the invention, the residence time of the BAF column is 1-10h.
In a preferred embodiment of the invention, the height of the packing in the BAF column is 1-10m, preferably 3-6m.
In the preferred technical scheme of the invention, the wastewater is the culture wastewater after biological treatment, the COD of the wastewater is less than 400mg/L, the BOD is less than 100mg/L, the total nitrogen is less than 100mg/L, the ammonia nitrogen is less than 10mg/L, the total phosphorus is less than 10mg/L, and the chromaticity is 2000-5000.
In the preferred technical scheme of the invention, the effluent quality reaches the standard discharge of the farmland irrigation water quality standard (GB 5084-2021), COD is less than 200mg/L, BOD is less than 100mg/L, total nitrogen is less than 100mg/L, ammonia nitrogen is less than 10mg/L, total phosphorus is less than 10mg/L, and chromaticity is less than 50.
In the preferred technical scheme of the invention, the wastewater is subjected to biological treatment by a biological treatment reactor and then is sent to ozone advanced treatment.
In the preferred technical scheme of the invention, the breeding wastewater is any one of cow breeding wastewater and pig breeding wastewater.
In a preferred embodiment of the present invention, the biological treatment comprises the steps of:
(1) The wastewater enters an MBBR anoxic zone through a water inlet, an MBBR biological suspended filler is arranged in the MBBR anoxic zone and is used as a carrier to attach anaerobic microorganisms, a submersible stirrer is arranged on the side wall, a large amount of bottom sludge is prevented from depositing at the bottom through strong stirring, and effluent automatically flows into an MBBR aerobic zone through a first communication port at the lower part of a first partition plate;
(2) The MBBR biological suspended filler is arranged in the MBBR aerobic zone, and microorganisms attached to the filler further remove degradable organic pollutants in the wastewater; simultaneously, a perforated aeration pipe is arranged at the bottom, and the gas is uniformly distributed;
(3) The effluent of the MBBR aerobic zone enters a central guide cylinder in a central sedimentation tank through an upper pipeline, waste water flows out from top to bottom in the central guide cylinder, flows upwards through a reflecting plate positioned at the lower part of the central guide cylinder, overflows along a water outlet triangular weir at the periphery of the upper part, flows into a second pipeline and flows into the bottom of a contact oxidation anoxic zone, and sludge is settled and discharged into a conical sludge settling hopper at the bottom of the tank;
(4) Biological rope filler is arranged in the contact oxidation anoxic zone and used for adsorbing sludge and microorganisms; the side wall of the contact oxidation anoxic zone is provided with a submersible stirrer, so that sludge deposition is avoided, and effluent overflows into the contact oxidation aerobic zone through an opening at the upper part of the second partition plate;
(5) Biological rope filler is arranged in the contact oxidation aerobic zone, and organic pollutants are degraded and purified through the combined action of a biological film and activated sludge; the bottom is provided with a micropore aeration disc, so that sufficient oxygen is provided for biochemical reaction, and activated sludge deposition is prevented; the effluent automatically flows into the MBR membrane reaction zone through a third communication port at the lower part of the third partition plate;
(6) The curtain type MBR hollow fiber membrane is arranged in the MBR membrane reaction zone, a microporous aeration device is arranged at the bottom of the MBR membrane reaction zone to avoid sludge deposition, and sludge-water separation is realized through the MBR hollow fiber membrane; and the effluent of the MBR membrane reaction zone is pumped into an MBR membrane water production zone by an upper water suction pump and is discharged through a water outlet.
In the preferred technical scheme of the invention, the wastewater is the culture wastewater after hydrolysis and acidification treatment, the COD of the wastewater is 10000-50000mg/L, the BOD is 5000-10000mg/L, the total nitrogen is 1000-5000mg/L, the ammonia nitrogen is 500-1000mg/L, and the total phosphorus is 100-500mg/L.
In the preferred technical scheme of the invention, the effluent quality reaches the standard discharge of the farmland irrigation water quality standard (GB 5084-2021), the COD is less than 200mg/L, the BOD is less than 100mg/L, the total nitrogen is less than 100mg/L, the ammonia nitrogen is less than 10mg/L, and the total phosphorus is less than 10mg/L.
In the preferable technical scheme of the invention, the residence time of the MBBR aerobic zone is 30-40h, and the dissolved oxygen is 1-4mg/L.
In the preferable technical scheme of the invention, the residence time of the wastewater in the MBBR anoxic zone is 10-20h.
In the preferred technical scheme of the invention, the retention time of the central sedimentation tank is 1-10h.
In a preferred technical scheme of the invention, the residence time of the contact oxidation anoxic zone is 20-30h.
In the preferable technical scheme of the invention, the retention time of the contact oxidation aerobic zone is 40-50h, and the dissolved oxygen is 1-4mg/L
In the preferred technical scheme of the invention, the residence time of the MBR membrane reaction zone is 1-10h.
In the preferred technical scheme of the invention, the residence time of the MBR membrane water producing area is 1-10h.
In a preferred technical scheme of the invention, the MBBR anoxic zone: the effective volume ratio of the MBBR aerobic zone is 1:1-5.
In a preferred embodiment of the invention, the contact oxidation anoxic zone: the effective volume ratio of the contact oxidation aerobic zone is 1:1-5.
In a preferred technical scheme of the invention, the MBR membrane reaction zone: the effective volume ratio of the MBR membrane water producing area is 1:1-5.
The invention aims to provide a biological treatment reactor which comprises an inner circular plate and an outer circular plate, wherein the inner circular plate and the outer circular plate are concentric circular plates, a central sedimentation tank is arranged on the inner side of the inner circular plate, an annular gap cavity is formed between the inner circular plate and the outer circular plate, an MBBR anoxic zone, an MBBR aerobic zone, a contact oxidation anoxic zone, a contact oxidation aerobic zone, an MBR membrane reaction zone and an MBR membrane water production zone are arranged in the annular gap cavity in a separated mode, and all stages of treatment zones are separated by separation plates;
the upper part of the MBBR anoxic zone is provided with a water inlet, the interior of the MBBR anoxic zone is provided with an MBBR biological suspension filler, and the side wall of the MBBR anoxic zone is provided with a submersible stirrer; the MBBR anoxic zone and the MBBR aerobic zone are separated by a first separation plate, and a first communication port is formed in the lower part of the first separation plate;
the MBBR biological suspended filler is arranged in the MBBR aerobic zone, the perforated aeration pipe is arranged at the bottom, the first water outlet pipeline is arranged at the upper part, and the central guide cylinder is communicated with the central sedimentation tank;
A central guide cylinder is arranged in the central sedimentation tank, a reflecting plate is arranged at the lower part of the central guide cylinder, a conical sludge settling hopper is arranged at the bottom of the central sedimentation tank, a triangular weir is arranged at the upper part of the central sedimentation tank, and a second water outlet pipeline is arranged on the triangular weir and communicated with the bottom of the contact oxidation anoxic zone;
biological rope filler is arranged in the contact oxidation anoxic zone, a submersible stirrer is arranged on the side wall of the contact oxidation anoxic zone, the contact oxidation anoxic zone and the contact oxidation aerobic zone are separated by a second partition plate, and a second communication port is formed in the upper part of the second partition plate;
biological rope filler is arranged in the contact oxidation aerobic zone, and a microporous aeration disc is arranged at the bottom of the contact oxidation aerobic zone; the contact oxidation aerobic zone and the MBR membrane reaction are separated by a third separation plate, and a third communication port is formed in the lower part of the third separation plate; the MBR membrane reaction zone is internally provided with a curtain type MBR hollow fiber membrane, the bottom of the MBR membrane reaction zone is provided with a microporous aeration device, and the upper part of the MBR membrane reaction zone is provided with a water suction pump and a third water outlet pipeline which are communicated with an MBR membrane water production zone;
and a water outlet is arranged in the MBR membrane water producing area.
In a preferred embodiment of the present invention, the MBBR bio-suspension filler is commercially available, preferably HDPE. In a preferred embodiment of the present invention, the bio-rope filler is commercially available, preferably propylene fiber.
In a preferred technical scheme of the invention, the curtain type MBR hollow fiber membrane is commercially available, and is preferably an immersed type PVDF hollow fiber membrane.
Another object of the present invention is to provide a method for treating aquaculture wastewater using the biological treatment reactor of the present invention, comprising the steps of:
(1) The wastewater enters an MBBR anoxic zone through a water inlet, an MBBR biological suspended filler is arranged in the MBBR anoxic zone and is used as a carrier to attach anaerobic microorganisms, a submersible stirrer is arranged on the side wall, a large amount of bottom sludge is prevented from depositing at the bottom through strong stirring, and effluent automatically flows into an MBBR aerobic zone through a first communication port at the lower part of a first partition plate;
(2) The MBBR biological suspended filler is arranged in the MBBR aerobic zone, and microorganisms attached to the filler further remove degradable organic pollutants in the wastewater; simultaneously, a perforated aeration pipe is arranged at the bottom, and the gas is uniformly distributed;
(3) The effluent of the MBBR aerobic zone enters a central guide cylinder in a central sedimentation tank through an upper pipeline, wastewater flows out from top to bottom in the central guide cylinder, flows upwards through a reflecting plate positioned at the lower part of the central guide cylinder, overflows along a water outlet triangular weir at the periphery of the upper part, and flows into a second pipeline to flow into the bottom of the contact oxidation anoxic zone;
(4) Biological rope filler is arranged in the contact oxidation anoxic zone and used for adsorbing sludge and microorganisms; the side wall of the contact oxidation anoxic zone is provided with a submersible stirrer, so that sludge deposition is avoided, and effluent overflows into the contact oxidation aerobic zone through an opening at the upper part of the second partition plate;
(5) Biological rope filler is arranged in the contact oxidation aerobic zone, and organic pollutants are degraded and purified through the combined action of a biological film and activated sludge; the bottom is provided with a micropore aeration disc, so that sufficient oxygen is provided for biochemical reaction, and activated sludge deposition is prevented; the effluent automatically flows into the MBR membrane reaction zone through a third communication port at the lower part of the third partition plate;
(6) The curtain type MBR hollow fiber membrane is arranged in the MBR membrane reaction zone, a microporous aeration device is arranged at the bottom of the MBR membrane reaction zone to avoid sludge deposition, and sludge-water separation is realized through the MBR hollow fiber membrane; and the effluent of the MBR membrane reaction zone is pumped into an MBR membrane water production zone by an upper water suction pump and is discharged through a water outlet.
In the preferred technical scheme of the invention, the wastewater is the culture wastewater after hydrolysis and acidification treatment, the COD of the wastewater is 10000-50000mg/L, the BOD is 5000-10000mg/L, the total nitrogen is 1000-5000mg/L, the ammonia nitrogen is 500-1000mg/L, and the total phosphorus is 100-500mg/L.
In the preferred technical scheme of the invention, the effluent quality meets the requirements of pollutant emission standards of livestock and poultry farming (GB 18596-2001), COD is less than 400mg/L, BOD is less than 100mg/L, total nitrogen is less than 100mg/L, ammonia nitrogen is less than 10mg/L, and total phosphorus is less than 10mg/L.
In the preferable technical scheme of the invention, the residence time of the MBBR aerobic zone is 30-40h, and the dissolved oxygen is 1-4mg/L.
In the preferable technical scheme of the invention, the residence time of the wastewater in the MBBR anoxic zone is 10-20h.
In the preferred technical scheme of the invention, the retention time of the central sedimentation tank is 1-10h.
In a preferred technical scheme of the invention, the residence time of the contact oxidation anoxic zone is 20-30h.
In the preferable technical scheme of the invention, the retention time of the contact oxidation aerobic zone is 40-50h, and the dissolved oxygen is 1-4mg/L
In the preferred technical scheme of the invention, the residence time of the MBR membrane reaction zone is 1-10h.
In the preferred technical scheme of the invention, the residence time of the MBR membrane water producing area is 1-10h.
In a preferred technical scheme of the invention, the MBBR anoxic zone: the effective volume ratio of the MBBR aerobic zone is 1:1-5.
In a preferred embodiment of the invention, the contact oxidation anoxic zone: the effective volume ratio of the contact oxidation aerobic zone is 1:1-5.
In a preferred technical scheme of the invention, the MBR membrane reaction zone: the effective volume ratio of the MBR membrane water producing area is 1:1-5.
Unless otherwise indicated, when the invention relates to a percentage between liquids, the percentages are volume/volume percentages; the invention relates to the percentage between liquid and solid, said percentage being volume/weight percentage; the invention relates to the percentage between solids and liquids, the percentage being weight/volume percentage; the balance being weight/weight percent.
Compared with the prior art, the invention has the following beneficial effects:
1. the heterogeneous ozone catalytic oxidation system of the invention effectively reduces ozone consumption, improves ozone utilization rate, can further reduce pollutants (COD, SS, antibiotics and chromaticity) in effluent after biological treatment, and ensures stable quality of the effluent, and can reach the 'standard of water quality for farm irrigation' (GB 5084-2021).
2. The biological treatment reactor provided by the invention effectively utilizes the combined arrangement of MBBR, contact oxidation and MBR, effectively reduces pollutants (COD, BOD, SS) in the cultivation wastewater, ensures that the effluent reaches the irrigation water discharge standard, solves the problem of sludge expansion in the traditional two-stage A/O, realizes the reduction of COD and BOD through sludge degradation under the facultative environment of low DO, realizes the reduction of ss through sludge adsorption, realizes sludge bubbling through spraying by a spraying device after sludge backflow, saves the use of defoamer, ensures that the A/O and the MBR further realize the degradation and adsorption of COD and ss, can effectively solve the problems of sludge expansion and blockage, does not need sludge backflow and does not need backwashing water. On one hand, the sludge expansion can be solved through reflux water pressure soaking, on the other hand, the secondary sedimentation tank is replaced through an MBR membrane reaction zone, sludge interception is carried out by using an MBR, and occupied area is saved.
3. The whole process adopts an integrated lotus-type structure, realizes partition utilization, has compact layout, saves occupied area, is convenient for incremental capacity expansion, reduces investment running cost, is simple to operate, and achieves the aim of efficiently treating high-concentration organic wastewater. The invention has simple operation, energy conservation and consumption reduction, effectively reduces the running cost of the system and ensures the treatment effect.
Drawings
FIG. 1 is a schematic top view of a biological treatment reactor according to the present invention;
fig. 2 is a schematic illustration of a partial connection of a heterogeneous ozone catalytic oxidation system according to the present invention.
Reference numerals:
100. a biological treatment reactor; 101. an inner circular plate; 102. an outer circular plate; 103. a central sedimentation tank; 104. an MBBR anoxic zone; 105. an MBBR aerobic zone; 106. contacting an oxidation anoxic zone; 107. contacting an oxidation aerobic zone; 108. an MBR membrane reaction zone; 109. an MBR membrane water producing area; 110. submersible agitators; 111. a first partition plate; 112. perforating the aeration pipe; 113. a second partition plate; 114. a microporous aeration disc; 115. curtain type MBR hollow fiber membrane; 116. a microporous aeration device; 117. a third divider plate, 118, a center guide shell; 119. a reflection plate; 120. triangular weir;
200. a first-stage ozone catalytic oxidation tower; 201. a first tower; 202. a first wastewater inlet pipe; 203. a first water distributor; 204. a first ozone inlet pipe; 205. a first air distribution pipe; 206. a first interception net; 207. a first wastewater outlet pipe; 208. a first tail oxygen collection tube; 209. a first ultraviolet device;
300. A second-stage ozone catalytic oxidation tower; 301. a second tower; 302. a second wastewater inlet pipe; 303. a spraying device; 304. a second ozone inlet pipe; 305. a second air distribution pipe; 306. a second interception net; 307. a second wastewater outlet pipe; 308. a second tail oxygen collection tube; 309. a second ultraviolet device;
400. a BAF column; 401. a BAF tower water inlet; 402. BAF column inlet; 403. a third interception net; 404. a third waste water outlet pipe; 405. a third water distribution pipe; 406. a third air distribution pipe; 407. a third tower;
500. a venturi jet device; 501. and a circulating water outlet.
Detailed Description
The invention is further illustrated by the following examples.
The cultivation wastewater to be treated is: collecting cow dung, cow urine and flushing water produced in a cow farm, and carrying out solid-liquid separation to obtain wastewater and waste residues; the wastewater is the culture wastewater to be treated after hydrolysis and acidification treatment, wherein COD 33100mg/L, total suspended matters ss 6250mg/L, BOD 8110mg/L, total nitrogen 1230mg/L, ammonia nitrogen 876mg/L and total phosphorus 363mg/L. Heavy metal total mercury 10.5mg/L, total arsenic 22.2mg/L, total cadmium 1.35mg/L, total chromium 33.3mg/L, total nickel 49.7mg/L, total lead 19.0mg/L, total salt 2.52X10 4 mg/L, pH 7.1.
EXAMPLE 1 biological treatment reactor according to the invention
The biological treatment reactor comprises an inner circular plate 101 and an outer circular plate 102, wherein the inner circular plate 101 and the outer circular plate 102 are concentric circular plates, a central sedimentation tank 103 is arranged on the inner side of the inner circular plate 101, an annular gap chamber is formed between the inner circular plate 101 and the outer circular plate 102, and an MBBR anoxic zone 104, an MBBR aerobic zone 105, a contact oxidation anoxic zone 106, a contact oxidation aerobic zone 107, an MBR membrane reaction zone 108 and an MBR membrane water producing zone 109 are arranged in the annular gap chamber in a separated mode, and each stage of treatment zone is separated by a separation plate;
the upper part of the MBBR anoxic zone 104 is provided with a water inlet, the interior is provided with MBBR biological suspended filler, and the side wall is provided with a submersible stirrer 110; the MBBR anoxic zone 104 and the MBBR aerobic zone 105 are separated by a first partition plate 111, and a first communication port is formed in the lower part of the first partition plate 111;
the MBBR biological suspended filler is arranged in the MBBR aerobic zone 105, the perforated aeration pipe 112 is arranged at the bottom, the first water outlet pipeline is arranged at the upper part, and the first water outlet pipeline is communicated with the central guide cylinder of the central sedimentation tank 103;
the lower part of the center guide cylinder 118 is provided with a reflecting plate 119, the bottom of the center sedimentation tank is provided with a conical sludge sedimentation hopper, the upper part of the center sedimentation tank is provided with a triangular weir 120, and a second water outlet pipeline is arranged on the triangular weir and communicated with the bottom of the contact oxidation anoxic zone 106;
Biological rope filler is arranged in the contact oxidation anoxic zone 106, a submersible stirrer 110 is arranged on the side wall of the contact oxidation anoxic zone 109 and the contact oxidation aerobic zone 107 are separated by a second partition plate 113, and a second communication port is formed in the upper part of the second partition plate 113;
biological rope filler is arranged in the contact oxidation aerobic zone 107, and a microporous aeration disc 114 is arranged at the bottom; the contact oxidation aerobic zone 107 and the MBR membrane reaction zone 108 are separated by a third partition plate 117, and a third communication port is formed in the lower part of the third partition plate; a curtain type MBR hollow fiber membrane 115 is arranged in the MBR membrane reaction zone 108, a microporous aeration device 116 is arranged at the bottom, and a water suction pump and a third water outlet pipeline are arranged at the upper part and are communicated with an MBR membrane water production zone 109;
a water outlet is arranged in the MBR membrane water producing area 109.
The MBBR biological suspension filler is HDPE.
The biological rope filler is propylene fiber.
The curtain type MBR hollow fiber is an MBR hollow fiber membrane made of membrane immersed PVDF.
Example 2 cultivation wastewater depth Process
The cultivation wastewater treatment process comprises the following steps:
(1) The culture wastewater to be treated enters an MBBR anoxic zone 104 through a water inlet, MBBR biological suspended filler (commercial available, the adding amount is 30 percent of the volume of the anoxic zone) is arranged in the MBBR anoxic zone 104, anaerobic microorganisms are attached as carriers, a submersible stirrer 110 is arranged on the side wall, a large amount of bottom sludge is prevented from depositing by strong stirring, and the effective volume of the MBBR anoxic zone 104 is 878.23m 3 The residence time is 17.6h, and the effluent enters the MBBR aerobic zone 105 through a first communication port at the lower part of the first partition plate 111;
(2) The MBBR biological suspended filler is arranged in the MBBR aerobic zone 105, and microorganisms attached to the filler further remove degradable organic pollutants in the wastewater; simultaneously, a perforated aeration pipe 112 is arranged at the bottom, and gas is uniformly distributed; the effective volume of the MBBR aerobic zone 105 is 1811.16m 3 The retention time is 36.2h, and the dissolution is carried outOxygen decomposition is 2mg/L;
(3) The effluent of the MBBR aerobic zone 105 enters a central guide cylinder 118 in the central sedimentation tank 103 through an upper pipeline, the wastewater flows out from top to bottom in the central guide cylinder 118, and the effective volume of the central sedimentation tank 103 is 442.26m 3 The residence time is 8.8 hours; the wastewater flows upwards through the reflecting plate 119 positioned at the lower part of the central guide cylinder 118, overflows along the triangular water outlet weirs 120 at the periphery of the upper part, flows into the bottom of the contact oxidation anoxic zone 106 through the second pipeline, and the sludge is settled and discharged into the conical sludge settling hopper at the bottom of the tank;
(4) Biological rope fillers are arranged in the contact oxidation anoxic zone 106 and are used for adsorbing sludge and microorganisms; the side wall of the contact oxidation anoxic zone 106 is provided with a submersible stirrer 110 to avoid sludge deposition, and the effective volume of the contact oxidation anoxic zone 106 is 1091.34m 3 Residence time 21.8h; the effluent overflows into the contact oxidation aerobic zone 107 through the upper opening of the second partition plate 113;
(5) Biological rope filler is arranged in the contact oxidation aerobic zone 107, and organic pollutants are degraded and purified through the combined action of a biological film and activated sludge; the bottom is provided with a microporous aeration disc 114, so that sufficient oxygen is provided for biochemical reaction to prevent activated sludge deposition; the effective volume of the contact oxidation aerobic zone 107 is 2476.80m 3 The retention time is 49.5 hours, and the dissolved oxygen is 2mg/L; the effluent automatically flows into the MBR membrane reaction zone through a third communication port at the lower part of the third partition plate 117;
(6) The curtain type MBR hollow fiber membrane 115 is arranged in the MBR membrane reaction zone 108, the microporous aeration device 116 is arranged at the bottom to avoid sludge deposition, mud-water separation is realized through the MBR hollow fiber membrane 116, and the effective volume of the MBR membrane reaction zone 108 is 313.47m 3 The residence time is 6.3h; the effluent of the MBR membrane reaction zone 108 is pumped into an MBR membrane water producing zone 109 by an upper water pump, and the effective volume of the MBR membrane water producing zone 109 is 400.50m 3 The retention time is 8.0h, and the waste water is discharged through a water outlet. Through detection, COD 322mg/L, BOD 5mg/L, SS not detected, total nitrogen 40mg/L, ammonia nitrogen 5.75mg/L, total phosphorus 9.33mg/L, heavy metals total mercury, total arsenic, total cadmium, total chromium, total nickel and total lead are not detected, and the pH value is 8.3.
Comparative example 1
(1) Feeding the culture wastewater to be treated into an MBBR anoxic zone through a water inlet, wherein an MBBR biological suspended filler (the adding amount is 30% of the volume of the anoxic zone) is arranged in the MBBR anoxic zone, anaerobic microorganisms are attached to the MBBR biological suspended filler as carriers, a submerged stirrer is arranged on the side wall of the MBBR anoxic zone, a large amount of sediment is prevented from being deposited at the bottom of the MBBR anoxic zone through strong stirring, and the effective volume of the MBBR anoxic zone is 878.23m 3 The residence time is 17.6 hours, and the effluent automatically flows into the MBBR aerobic zone through a first communication port at the lower part of the first partition plate;
(2) The MBBR biological suspended filler is arranged in the MBBR aerobic zone, and microorganisms attached to the filler further remove degradable organic pollutants in the wastewater; simultaneously, a perforated aeration pipe is arranged at the bottom, and the gas is uniformly distributed; the effective volume of the MBBR aerobic zone is 1811.16m 3 The retention time is 36.2h, and the dissolved oxygen is 2mg/L;
(3) The effluent of the MBBR aerobic zone enters a central guide cylinder in a central sedimentation tank through an upper pipeline, the wastewater flows out from top to bottom in the central guide cylinder, and the effective volume of the central sedimentation tank is 442.26m 3 The residence time is 8.8 hours; the wastewater flows upwards through the reflecting plate positioned at the lower part of the central guide cylinder, overflows along the triangular weir for water outlet at the periphery of the upper part, and the water outlet is obtained. Through detection, COD 1562mg/L, BOD 539mg/L and SS 895mg/L in the effluent.
Comparative example 2
(1) Feeding the culture wastewater to be treated into an MBBR anoxic zone through a water inlet, wherein an MBBR biological suspended filler (the adding amount is 30% of the volume of the anoxic zone) is arranged in the MBBR anoxic zone, anaerobic microorganisms are attached to the MBBR biological suspended filler as carriers, a submerged stirrer is arranged on the side wall of the MBBR anoxic zone, a large amount of sediment is prevented from being deposited at the bottom of the MBBR anoxic zone through strong stirring, and the effective volume of the MBBR anoxic zone is 878.23m 3 The residence time is 17.6 hours, and the effluent automatically flows into the MBBR aerobic zone through a first communication port at the lower part of the first partition plate;
(2) The MBBR biological suspended filler is arranged in the MBBR aerobic zone, and microorganisms attached to the filler further remove degradable organic pollutants in the wastewater; simultaneously, a perforated aeration pipe is arranged at the bottom, and the gas is uniformly distributed; the effective volume of the MBBR aerobic zone is 1811.16m 3 The retention time is 36.2h, and the dissolved oxygen is 2mg/L；
(3) The effluent of the MBBR aerobic zone enters a central guide cylinder in a central sedimentation tank through an upper pipeline, the wastewater flows out from top to bottom in the central guide cylinder, and the effective volume of the central sedimentation tank is 442.26m 3 The residence time is 8.8 hours; the wastewater flows upwards through a reflecting plate positioned at the lower part of the central guide cylinder, overflows along a triangular weir for water outlet at the periphery of the upper part, flows into a second pipeline and flows into an MBR membrane reaction area, and sludge is settled and discharged into a conical sludge settling hopper at the bottom of the tank;
(4) The curtain type MBR hollow fiber membrane is arranged in the MBR membrane reaction zone, a microporous aeration device is arranged at the bottom of the MBR membrane reaction zone to avoid sludge deposition, sludge-water separation is realized through the MBR hollow fiber membrane, and the effective volume of the MBR membrane reaction zone is 313.47m 3 The residence time is 6.3h; the effluent of the MBR membrane reaction zone is pumped into an MBR membrane water producing zone by an upper water suction pump, and the effective volume of the MBR membrane water producing zone is 400.50m 3 The retention time is 8.0h, and the water is discharged through the water outlet, thus obtaining the effluent. The COD 847mg/L and BOD 351mg/L in the water are detected and are not detected. MBR is easy to block and the effluent treatment effect is poor.
Comparative example 3
(1) Introducing the culture wastewater to be treated into a contact oxidation anoxic zone, wherein a biological rope filler is arranged in the contact oxidation anoxic zone and used for adsorbing sludge and microorganisms; the side wall of the contact oxidation anoxic zone is provided with a submersible stirrer to avoid sludge deposition, and the effective volume of the contact oxidation anoxic zone is 1091.34m 3 Residence time 21.8h; the effluent overflows into the contact oxidation aerobic zone through an opening at the upper part of the second partition plate;
(2) Biological rope filler is arranged in the contact oxidation aerobic zone, and organic pollutants are degraded and purified through the combined action of a biological film and activated sludge; the bottom is provided with a micropore aeration disc, so that sufficient oxygen is provided for biochemical reaction, and activated sludge deposition is prevented; the effective volume of the contact oxidation aerobic zone is 2476.80m 3 The retention time is 49.5 hours, and the dissolved oxygen is 2mg/L; the effluent automatically flows into the MBR membrane reaction zone through a third communication port at the lower part of the third partition plate;
(3) The curtain type MBR hollow fiber membrane is arranged in the MBR membrane reaction zone, and a microporous aeration device is arranged at the bottom of the MBR membrane reaction zone to avoid siltingMud deposition, realizing mud-water separation through MBR hollow fiber membrane, wherein the effective volume of the MBR membrane reaction zone is 313.47m 3 The residence time is 6.3h; the effluent of the MBR membrane reaction zone is pumped into an MBR membrane water producing zone by an upper water suction pump, and the effective volume of the MBR membrane water producing zone is 400.50m 3 The retention time is 8.0h, and the water is discharged through the water outlet, thus obtaining the effluent. The COD 1273mg/L and BOD 560mg/L in the water are detected and are not detected.
Example 3 heterogeneous ozone catalytic oxidation System
A heterogeneous ozone catalytic oxidation system, which comprises a primary ozone catalytic oxidation tower 200, a secondary ozone catalytic oxidation tower 300 and an aeration biological filter tower (BAF tower 400); the heights of the first-stage ozone catalytic oxidation tower 200, the second-stage ozone catalytic oxidation tower 300 and the BAF tower 400 are gradually decreased;
the first-stage ozone catalytic oxidation tower 200 comprises a first tower body 201, a first wastewater inlet pipe 202, a first water distributor 203, a first ozone inlet pipe 204, a first gas distribution pipe 205, a silicon-aluminum-based catalyst, a first ultraviolet device 209, a first wastewater outlet pipe 207 and a first tail oxygen collecting pipe 208;
The first wastewater inlet pipe 202 is arranged on the side wall of the first tower body 201 and is connected with a first water distributor 203 at the bottom of the first tower body 201;
the first ozone inlet pipe 204 is arranged on the side wall of the first tower body 201 and is connected with a first gas distribution pipe 205 at the bottom of the first tower body 201;
the first silicon-aluminum based catalyst is arranged in the middle of the first tower 201 and is supported and fixed in the first tower 201 by a first interception net 206;
a first wastewater outlet pipe 207 and a first tail oxygen collecting pipe 208 are arranged at the top of the first tower body 201;
the first wastewater outlet pipe 207 of the first-stage ozone catalytic oxidation tower 200 is connected with the second wastewater inlet pipe 302 of the second-stage ozone catalytic oxidation tower 300;
the second-stage ozone catalytic oxidation tower 300 comprises a second tower body 301, a second wastewater inlet pipe 302, a second water distributor (i.e. a spraying device 303), a second ozone inlet pipe 304, a second gas distribution pipe 305, a silicon-aluminum based catalyst, a second ultraviolet device 309, a second wastewater outlet pipe 307 and a second tail oxygen collecting pipe 308;
the second wastewater inlet pipe 301 is arranged at the top of the second tower 301 and is connected with the spraying device 302 at the upper part of the second tower 301;
the second ozone inlet pipe 304 is arranged on the side wall of the second tower body 301 and is connected with a second gas distribution pipe 305 at the bottom of the second tower body 301;
The second tail oxygen collecting pipe 308 is arranged at the top of the second tower 301;
the second wastewater outlet pipe 307 is arranged at the bottom of the second tower body 301;
the second wastewater outlet pipe 307 of the secondary ozone catalytic oxidation tower 300 is connected with the BAF tower water inlet 401;
the middle parts of the two-stage ozone catalytic oxidation towers are respectively provided with silicon-aluminum based catalysts, and the silicon-aluminum based catalysts are respectively supported and fixed in the first tower 201 and the second tower 301 by a first interception net 206 and a second interception net 306;
the two-stage ozone catalytic oxidation tower is respectively provided with a first ultraviolet device 209 and a second ultraviolet device 309, the middle part of the tower body is alternately provided with an ultraviolet lamp tube every 50cm, the inside of the tower is separated by quartz glass, and the ultraviolet lamp tube can be pulled out from the side wall for replacement;
the BAF tower 400 comprises a third tower body 407, a BAF tower water inlet 401, a third water distribution pipe 405, a BAF tower air inlet 402, a third air distribution pipe 406, MBBR biological suspended filler and a third waste water outlet pipe 404;
the BAF tower water inlet is positioned at the upper part of the third tower body 407 and is connected with the third water distribution pipe 405;
the BAF tower air inlet is positioned at the lower part of the third tower body 407 and is connected with a third air distribution pipe 406;
the MBBR biological suspended filler is kept at the middle upper part of the third tower body 407 by a third interception net 403;
the silica-alumina based catalyst filler is selected from Mn-Fe-Ce/gamma-A l 2 O 3 、S iO2-A l 2 O 3 Any one or a combination thereof;
the diameters of the primary ozone catalytic oxidation tower and the secondary ozone catalytic oxidation tower are 2-5m, and the heights are 1-10m;
the heights of the fillers in the primary ozone catalytic oxidation tower and the secondary ozone catalytic oxidation tower are 4-6m;
the diameter of the BAF tower is 2-5m, and the height is 1-10m;
the height of the packing in the BAF tower is 3-6m.
The middle part of the side wall of the primary ozone catalytic oxidation tower 200 is provided with a circulating water outlet 501, wastewater enters a venturi jet device 500 on an ozone inlet pipe from the circulating water outlet through the action of a circulating pump, and enters the bottom of the primary ozone catalytic oxidation tower 200 through a first gas distribution pipe 205 from an ozone inlet positioned at the lower part of the primary ozone catalytic oxidation tower 200 after being rapidly mixed with ozone.
Example 4 cultivation wastewater depth Process
(1) The effluent after biological treatment in example 3 enters the bottom of the tower from the wastewater inlet positioned on the side wall of the first-stage ozone catalytic oxidation tower through a water distributor, passes through a silicon-aluminum-based catalyst (the catalyst is a commercially available silicon-aluminum composite material of aluminum peroxide) positioned in the middle from bottom to top, has the volume of two thirds of the volume of the oxidation tower, and flows out from the wastewater outlet positioned on the side wall of the top after the combined action of ozone (ozone generating amount 5 kg/h), the silicon-aluminum-based catalyst and ultraviolet irradiation (wavelength 220nm and ultraviolet power 150W); the middle part of the side wall of the first-stage ozone catalytic oxidation tower is provided with a circulating water outlet, wastewater enters a venturi jet device on an ozone inlet pipe from the circulating water outlet through the action of a circulating pump, is quickly mixed with ozone gas and liquid, and enters the first-stage ozone catalytic oxidation tower through an ozone inlet positioned at the lower part of the first-stage ozone catalytic oxidation tower through a gas distribution pipe for recycling;
(2) After the wastewater flows out from the top of the first-stage ozone catalytic oxidation tower, the wastewater automatically flows into the upper part of the second-stage ozone catalytic oxidation tower through a pipeline connected with the top of the second-stage ozone catalytic oxidation tower by utilizing the height difference, uniformly distributes water through a spraying device, passes through a silicon-aluminum-based catalyst (the catalyst is a commercially available silicon-aluminum composite material of aluminum peroxide) positioned in the middle part from top to bottom, has the volume of two thirds of the volume of the oxidation tower, and flows out from a second wastewater outlet pipe positioned on the side wall of the bottom after the combined action of ozone (ozone generating amount is 5 kg/h), the silicon-aluminum-based catalyst and ultraviolet light (the wavelength is 220nm and the ultraviolet light power is 150W);
(3) The effluent of the secondary ozone catalytic oxidation tower enters the BAF tower from a water inlet of the BAF tower through a spray device and further adsorbs, intercepts and degrades organic pollutants in the wastewater through microorganisms attached to the MBBR biological suspended filler; at the same time, tail oxygen generated by the two-stage ozone catalytic oxidation towers is respectively converged from the top through pipelines, and then is introduced into the towers through air inlets positioned on the side walls of the bottoms of the BAF towers through air distribution pipes, so that aerobic environments are provided for microorganisms, and the microorganisms are ensured to fully and continuously decompose organic pollutants; the wastewater is discharged from the bottom of the BAF tower after being treated from top to bottom.
The diameters of the first-stage ozone catalytic oxidation tower and the second-stage ozone catalytic oxidation tower are 2m, the height is 7m, and the total volume is 20m 3 The retention time of the wastewater is 1h, and the filling height is 4.8m.
BAF tower diameter 2m, height 5m and total volume 14m 3 The retention time of the wastewater is 1h, and the filling height is 3m.
Through detection, COD in the effluent is 131mg/L, BOD is 4.3mg/L, total nitrogen is 28.2mg/L, ammonia nitrogen is 7.26mg/L, total phosphorus is 6.72mg/L, chroma is 30 times, ss is not detected, and total salt content is 3.24 multiplied by 10 3 mg/L。
Example 5
The effluent of example 3 and example 4 was used as irrigation water to irrigate tomatoes, respectively, and tomato samples were collected. The results showed that the pH, salt content, volume weight, antibiotic resistance genes in the soil were significantly reduced using the effluent of example 4 compared to the effluent of example 3. And the soil is reduced from strong alkalinity to alkalinity, the soil quality is improved, the soil hardening and the antibiotic enrichment are prevented, and the nutrient absorption of planted crops is facilitated.
The above description of the embodiments of the present invention is not intended to limit the present invention, and those skilled in the art can make various changes or modifications according to the present invention without departing from the spirit of the present invention, and shall fall within the scope of the claims of the present invention.

Claims (10)

1. A heterogeneous ozone catalytic oxidation system, which comprises a primary ozone catalytic oxidation tower, a secondary ozone catalytic oxidation tower and an aeration biological filtration tower (BAF tower); the heights of the first-stage ozone catalytic oxidation tower, the second-stage ozone catalytic oxidation tower and the BAF tower are gradually decreased;
The first-stage ozone catalytic oxidation tower comprises a first tower body, a first wastewater inlet pipe, a first water distributor, a first ozone inlet pipe, a first gas distribution pipe, a first silicon-aluminum-based catalyst, a first ultraviolet device, a first wastewater outlet pipe and a first tail oxygen collecting pipe; the first wastewater inlet pipe is arranged on the side wall of the first tower body and is connected with a first water distributor at the bottom of the first tower body; the first ozone inlet pipe is arranged on the side wall of the first tower body and connected with a first gas distribution pipe at the bottom of the first tower body, the first wastewater outlet pipe and the first tail oxygen collecting pipe are arranged at the top of the first tower body, the first wastewater outlet pipe of the first-stage ozone catalytic oxidation tower is connected with a second wastewater inlet pipe of the second-stage ozone catalytic oxidation tower,
the second-stage ozone catalytic oxidation tower comprises a second tower body, a second wastewater inlet pipe, a second ozone inlet pipe, a second silicon-aluminum-based catalyst, a second ultraviolet device, a second wastewater outlet pipe and a second tail oxygen collecting pipe; the second wastewater inlet pipe is arranged at the top of the second tower body and is connected with a spraying device at the upper part of the second tower body; the second ozone air inlet pipe is arranged on the side wall of the second tower body and is connected with a second air distribution pipe at the bottom of the second tower body, the second tail oxygen collecting pipe is arranged at the top of the second tower body, and a second wastewater outlet pipe of the second-stage ozone catalytic oxidation tower is arranged at the bottom of the second tower body and is connected with a BAF tower water inlet;
The middle part of the two-stage ozone catalytic oxidation tower body is provided with silicon-aluminum based catalysts which are supported and fixed in the tower body by interception nets, the two-stage ozone catalytic oxidation tower is provided with ultraviolet devices, the middle part of the tower body is alternately provided with an ultraviolet lamp tube every 50cm, the tower body is separated by quartz glass, and the ultraviolet lamp tubes can be pulled out from the side walls for replacement;
the BAF tower comprises a third tower body, a BAF tower water inlet, a third water distributor, a BAF tower air inlet, a third air distribution pipe, MBBR biological suspended filler and a BAF tower water outlet; wherein the air inlet of the BAF tower is positioned at the lower part of the BAF tower and is connected with a third air distribution pipe, and the biological suspended filler of the MBBR is kept at the middle upper part of the BAF tower by a third interception net.
2. The system of claim 1, wherein the middle part of the side wall of the primary ozone catalytic oxidation tower is provided with a circulating water outlet, and the wastewater enters the venturi jet device on the ozone inlet pipe from the circulating water outlet through the action of a circulating pump, and enters the bottom of the primary ozone catalytic oxidation tower through the first gas distribution pipe from the ozone inlet positioned at the lower part of the primary ozone catalytic oxidation tower after being rapidly mixed with ozone gas and liquid.
3. The system of any of claims 1-2, further comprising a biological treatment reactor coupled to the primary ozone catalytic oxidation column.
4. A method for advanced treatment of aquaculture wastewater using a heterogeneous ozone catalytic oxidation system according to any of claims 1-3, comprising the steps of:
(1) The cultivation wastewater treated by the biological method enters the bottom of a first tower body from a wastewater inlet positioned on the side wall of a first-stage ozone catalytic oxidation tower through a first water distributor, passes through a silicon-aluminum-based catalyst positioned in the middle from bottom to top, and flows out from a first wastewater outlet pipe positioned on the side wall of the top after the combined action of ozone, the silicon-aluminum-based catalyst and ultraviolet light;
(2) The second-stage ozone catalytic oxidation tower is lower than the first-stage ozone catalytic oxidation tower, waste water flows out from a waste water outlet on the side wall of the top of the first-stage ozone catalytic oxidation tower, automatically flows into the upper part of the second-stage ozone catalytic oxidation tower by utilizing the height difference, uniformly distributes water in the second-stage ozone catalytic oxidation tower by adopting a spraying device, and flows from top to bottom through a silicon-aluminum-based catalyst positioned in the middle part, and flows out from a second waste water outlet pipe positioned on the side wall of the bottom after the combined action of ozone, the silicon-aluminum-based catalyst and ultraviolet light;
(3) The effluent of the second-stage ozone catalytic oxidation tower enters the tower from the water inlet of the BAF tower through the upper third water distributor and passes through the microorganism attached to the MBBR biological suspended filler,
Further adsorbing, intercepting and degrading organic pollutants in the wastewater; at the same time, tail oxygen generated by the two-stage ozone catalytic oxidation towers is respectively converged from the top through pipelines, and then is introduced into the towers through the third gas distribution pipe by the gas inlet positioned on the side wall of the bottom of the BAF tower, so that aerobic environment is provided for microorganisms, and the microorganisms are ensured to fully and continuously decompose organic pollutants; and the wastewater is discharged from a water outlet at the bottom of the third tower body after being treated from top to bottom.
5. The method of claim 4, wherein the wastewater is biologically treated aquaculture wastewater, the COD of the wastewater is less than 400mg/L, the BOD is less than 100mg/L, the total nitrogen is less than 100mg/L, the ammonia nitrogen is less than 10mg/L, the total phosphorus is less than 10mg/L, and the chroma is 2000-5000.
6. The method according to any one of claims 4 to 5, wherein the effluent quality meets the standard discharge of farm irrigation water quality standard (GB 5084-2021), COD is less than 200mg/L, BOD is less than 100mg/L, total nitrogen is less than 100mg/L, ammonia nitrogen is less than 10mg/L, total phosphorus is less than 10mg/L, and chromaticity is less than 50.
7. The method of any one of claims 4-6, wherein the ozone generator occurs in an amount of 1-10kg/h.
8. The method according to any one of claims 4 to 7, wherein the packing height in the primary ozone catalytic oxidation column and the secondary ozone catalytic oxidation column is 1 to 10m, preferably 4 to 6m.
9. The method of any one of claims 4-8, wherein the ultraviolet device provides ultraviolet light having a wavelength of 200-280nm and an ultraviolet light power of 75-350W.
10. The method of any one of claims 4-9, wherein the wastewater is pretreated in a biological treatment reactor prior to being subjected to ozone further treatment.
CN202311029395.3A 2023-07-26 2023-08-15 Heterogeneous ozone catalytic oxidation system and application thereof in cultivation wastewater treatment Pending CN117164142A (en)

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Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1155976A (en) * 1982-02-17 1983-10-25 Ferdinand Besik Apparatus for anoxic-aerobic activated sludge process and treatment of waste waters
CN101602564B (en) * 2009-07-21 2011-07-20 南京大学 Method for treating coking wastewater
CN101774732B (en) * 2010-01-28 2011-07-27 同济大学 Integral air-lift circumfluent suspended filler dispersed sewage biological treatment device
CN102775003B (en) * 2011-05-12 2016-05-04 上海市政工程设计研究总院（集团）有限公司 A kind for the treatment of apparatus and treatment process of low concentration VC pharmacy waste water
CN206985961U (en) * 2017-05-26 2018-02-09 上海能辉科技股份有限公司 Buried integrated sewage processing unit for photovoltaic plant
CN108726681A (en) * 2018-07-26 2018-11-02 山东利源海达环境工程有限公司 Multiple-effect ecology intelligent bionic aquatic weed
CN109502762A (en) * 2018-11-27 2019-03-22 湖南沃邦环保科技有限公司 A kind of sewage disposal device and its workflow of efficient MBBR
CN109516559A (en) * 2018-12-21 2019-03-26 广东尚骏科技有限公司 Integrated sewage disposal equipment for reclaiming
CN110078214A (en) * 2019-05-21 2019-08-02 哈尔滨工业大学（威海） The method that carbon source couples denitrification integrated processing is done in a kind of fermentation of septic tank sludge
CN110104910A (en) * 2019-06-21 2019-08-09 安吉国千环境科技有限公司 A kind of sewage disposal technology method based on MBBR technique
CN110330193A (en) * 2019-08-13 2019-10-15 泸州市海之航环保设备有限公司 A method of utilizing microbiological treatment waste water
CN111410308A (en) * 2020-03-03 2020-07-14 广东新会中集特种运输设备有限公司 Two-stage AO integrated sewage treatment equipment
CN212425590U (en) * 2020-05-22 2021-01-29 济南尚方环保科技有限公司 Multistage AO-MBBR aerobic biological nitrogen and phosphorus removal system
CN218115119U (en) * 2022-06-15 2022-12-23 上海熊猫机械(集团)有限公司 Integrated system for treating sewage
CN218058599U (en) * 2022-10-14 2022-12-16 新疆格林诺斯环保科技有限公司 AO-MBBR integration sewage treatment unit
CN115893750A (en) * 2022-12-22 2023-04-04 湖南正泰水务有限公司 Zero emission approaching system and method for treating high-concentration organic industrial wastewater
CN116119885A (en) * 2023-03-28 2023-05-16 同济大学 Integrated device for deep denitrification of sewage containing ammonia and nitrogen and treatment method thereof

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