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CN-114031226-B - High-concentration organic wastewater treatment method and device

CN114031226BCN 114031226 BCN114031226 BCN 114031226BCN-114031226-B

Abstract

A high-concentration organic waste water treatment method and its apparatus, relate to the treatment technology of the high-concentration organic waste water, this method is through multiple steps such as water supply, micro-electrolysis treatment, fenton reaction, tertiary precipitation filtration, etc., couple micro-electrolysis, fenton oxidation, ozone catalytic oxidation, micro-flocculation filtration technology, make each reaction process supplement each other, synergistic, achieve the goal to raise treatment efficiency, reduce equipment and medicament input; the invention also discloses a treatment device for realizing the method, which mainly comprises a water supply device, a micro-electrolysis cell, a Fenton reactor and a three-stage precipitation and filtration device. The invention has high treatment efficiency, convenient operation, low running cost and good industrial application prospect, and can realize the efficient treatment of high-concentration organic wastewater.

Inventors

  • ZHAO JIN
  • CAO JUNRUI
  • MA YUHUI
  • JIANG TIANXIANG
  • XIE BAOLONG
  • WANG XUNLIANG

Assignees

  • 天津市海跃水处理高科技有限公司
  • 自然资源部天津海水淡化与综合利用研究所

Dates

Publication Date
20260512
Application Date
20211223

Claims (10)

  1. 1. The high-concentration organic wastewater treatment device used in the wastewater treatment method comprises a water supply device (100), wherein the water supply device is sequentially connected with a micro-electrolysis cell (200), a Fenton reactor (300) and a three-stage precipitation filtering device (400); The micro-electrolytic cell (200) is provided with a multi-stage filler layer track, the multi-stage filler layer track comprises a plurality of parallel inclined first baffle plates (202), water outlets on two sides of the first baffle plates are arranged in a left-right staggered mode, filler layers are arranged between adjacent first baffle plates, and iron-carbon fillers (203) are filled in the filler layers; or, the inner part of the packing layer of the multi-stage packing layer track is filled with iron-carbon packing (203) which is wrapped and fixed by a filtering steel mesh; the inclination angle of the inclined first baffle plate (202) and the horizontal line of the micro-electrolytic cell (200) is 30-45 degrees, and the highest position of the first baffle plate is lower than the water inlet (201) of the micro-electrolytic cell; the volume of the iron carbon filler (203) of the micro-electrolytic cell (200) accounts for 10% -25% of the effective volume of the micro-electrolytic cell (200); the volume of the interval between any two adjacent iron carbon filling (203) areas of each filling layer of the micro-electrolysis cell (200) is 30% -60% of the volume of each iron carbon filling (203); The method comprises the following steps: ① Water supply, namely regulating the pH value of the high-concentration organic wastewater, and then carrying out micro-electrolysis treatment; the high-concentration organic wastewater enters a water inlet pipeline through a lift pump (101), is quickly and uniformly mixed with sulfuric acid (H 2 SO 4 ) added by a sulfuric acid (H 2 SO 4 ) adding device (102) through a pipeline mixer (103), and is regulated to pH value of 2.0-3.0 and then enters a micro-electrolytic cell (200); ② Micro-electrolysis treatment, namely, the wastewater in the previous step passes through a multi-stage filler layer track, and the iron-carbon filler filled in the wastewater undergoes micro-electrolysis reaction to degrade organic matters in the wastewater; the wastewater from the previous step enters through a water inlet (201) of the micro-electrolysis cell and flows to a multistage packing layer track along an inclined first baffle (202) in a homeopathic manner; a plurality of iron-carbon fillers (203) which are mutually spaced and wrapped and fixed by a filtering steel mesh are arranged in the multistage filler layer; the bottom of the micro-electrolysis cell (200) is provided with a sludge discharge port (204) which can discharge the generated sludge periodically, and when the wastewater is subjected to micro-electrolysis treatment, the wastewater flows to the Fenton reactor (300); ③ Fenton reaction, namely generating hydroxyl free radicals (OH) with extremely strong oxidizing property by Fenton oxidation reaction of the wastewater in the previous step, and degrading organic matters in the wastewater by utilizing the strong oxidizing property of the hydroxyl free radicals (OH); The wastewater from the previous step enters a Fenton reactor (300) and forms a Fenton oxidation system with ferrous sulfate (FeSO 4 ) and hydrogen peroxide (H 2 O 2 ) pumped by a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306) on an internal circulation pipeline (304) respectively; The micro-nano aerator (301) is connected with the bottom of the Fenton reactor (300), and micro-nano bubble ozone O 3 (302) generated by the micro-nano aerator is sent into the Fenton reactor (300) through an air distribution hole (303); An inner circulation pipeline (304) connected with the outer side of the Fenton reactor (300) and used for re-entering the Fenton reactor through the inner circulation pipeline (304) under the action of an inner circulation pump (307) and mixing with inlet water and treating again; The wastewater treated by the Fenton reactor (300) overflows to a Fenton reactor water outlet (309) under the combined action of the buoyancy of the micro-nano bubble ozone O 3 (302) and the thrust of the internal circulating water flow, and enters a three-stage precipitation filtering device (400) under the action of a hydraulic pump (310); ④ Three-stage precipitation filtration, namely sequentially carrying out three-stage filtration on the wastewater in the previous step through anthracite, quartz sand and modified zeolite to finish the processes of micro flocculation, filtration, adsorption, interception and precipitation on the wastewater, thereby realizing the advanced treatment of the wastewater; The wastewater enters a water inlet (401) of a three-stage precipitation filtering device, is filtered by a filler filled in a first reaction zone, enters a next reaction zone through a water distribution hole (403) on a filter plate (402), and is subjected to three-stage filtration of anthracite, quartz sand and modified zeolite from top to bottom; After the wastewater is treated by the three-stage precipitation filtering device (400), the water quality of the discharged water reaches the standard, overflows through a water outlet pipe of the three-stage precipitation filtering device, and returns to the water inlet pipeline for recycling treatment through a return pipe at the bottom of the three-stage precipitation filtering device (400) when the water quality of the discharged water does not reach the standard.
  2. 2. The high-concentration organic wastewater treatment device used in the wastewater treatment method comprises a water supply device (100), wherein the water supply device is sequentially connected with a micro-electrolysis cell (200), a Fenton reactor (300) and a three-stage precipitation filtering device (400); The micro-electrolytic cell (200) is provided with a multi-stage filler layer track, the multi-stage filler layer track comprises a plurality of parallel inclined first baffle plates (202), water outlets on two sides of the first baffle plates are arranged in a left-right staggered mode, filler layers are arranged between adjacent first baffle plates, and iron-carbon fillers (203) are filled in the filler layers; or, the inner part of the packing layer of the multi-stage packing layer track is filled with iron-carbon packing (203) which is wrapped and fixed by a filtering steel mesh; the inclination angle of the inclined first baffle plate (202) and the horizontal line of the micro-electrolytic cell (200) is 30-45 degrees, and the highest position of the first baffle plate is lower than the water inlet (201) of the micro-electrolytic cell; the volume of the iron carbon filler (203) of the micro-electrolytic cell (200) accounts for 10% -25% of the effective volume of the micro-electrolytic cell (200); the volume of the interval between any two adjacent iron carbon filling (203) areas of each filling layer of the micro-electrolysis cell (200) is 30% -60% of the volume of each iron carbon filling (203); The method comprises the following steps: ① Water supply, namely regulating the pH value of the high-concentration organic wastewater, and then carrying out micro-electrolysis treatment; the high-concentration organic wastewater enters a water inlet pipeline through a lift pump (101), is quickly and uniformly mixed with sulfuric acid (H 2 SO 4 ) added by a sulfuric acid (H 2 SO 4 ) adding device (102) through a pipeline mixer (103), and is regulated to pH value of 2.0-3.0 and then enters a micro-electrolytic cell (200); ② Micro-electrolysis treatment, namely, the wastewater in the previous step passes through a multi-stage filler layer track, and the iron-carbon filler filled in the wastewater undergoes micro-electrolysis reaction to degrade organic matters in the wastewater; the wastewater from the previous step enters through a water inlet (201) of the micro-electrolysis cell and flows to a multistage packing layer track along an inclined first baffle (202) in a homeopathic manner; a plurality of iron-carbon fillers (203) which are mutually spaced and wrapped and fixed by a filtering steel mesh are arranged in the multistage filler layer; the bottom of the micro-electrolysis cell (200) is provided with a sludge discharge port (204) which can discharge the generated sludge periodically, and when the wastewater is subjected to micro-electrolysis treatment, the wastewater flows to the Fenton reactor (300); ③ Fenton reaction, namely generating hydroxyl free radicals (OH) with extremely strong oxidizing property by Fenton oxidation reaction of the wastewater in the previous step, and degrading organic matters in the wastewater by utilizing the strong oxidizing property of the hydroxyl free radicals (OH); The wastewater from the previous step enters a Fenton reactor (300) and forms a Fenton oxidation system with ferrous sulfate (FeSO 4 ) and hydrogen peroxide (H 2 O 2 ) pumped by a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306) on an internal circulation pipeline (304) respectively; The micro-nano aerator (301) is connected with the bottom of the Fenton reactor (300), and micro-nano bubble ozone O 3 (302) generated by the micro-nano aerator is sent into the Fenton reactor (300) through an air distribution hole (303); An inner circulation pipeline (304) connected with the outer side of the Fenton reactor (300) and used for re-entering the Fenton reactor through the inner circulation pipeline (304) under the action of an inner circulation pump (307) and mixing with inlet water and treating again; The wastewater treated by the Fenton reactor (300) overflows to a Fenton reactor water outlet (309) under the combined action of the buoyancy of the micro-nano bubble ozone O 3 (302) and the thrust of the internal circulating water flow, and enters a three-stage precipitation filtering device (400) under the action of a hydraulic pump (310); ④ Three-stage precipitation filtration, namely sequentially carrying out three-stage filtration on the wastewater in the previous step through anthracite, quartz sand and modified zeolite to finish the processes of micro flocculation, filtration, adsorption, interception and precipitation on the wastewater, thereby realizing the advanced treatment of the wastewater; The wastewater enters a water inlet (401) of a three-stage precipitation filtering device, is filtered by a filler filled in a first reaction zone, enters a next reaction zone through a water distribution hole (403) on a filter plate (402), and is subjected to three-stage filtration of anthracite, quartz sand and modified zeolite from top to bottom; After the wastewater is treated by the three-stage precipitation filtering device (400), the water quality of the discharged water reaches the standard, overflows through a water outlet pipe of the three-stage precipitation filtering device, and returns to the water inlet pipeline for recycling treatment through a return pipe at the bottom of the three-stage precipitation filtering device (400) when the water quality does not reach the standard; in step ②, the hydraulic retention time of the wastewater in the micro-electrolysis cell is 20-60min.
  3. 3. The high-concentration organic wastewater treatment device used in the wastewater treatment method comprises a water supply device (100), wherein the water supply device is sequentially connected with a micro-electrolysis cell (200), a Fenton reactor (300) and a three-stage precipitation filtering device (400); The micro-electrolytic cell (200) is provided with a multi-stage filler layer track, the multi-stage filler layer track comprises a plurality of parallel inclined first baffle plates (202), water outlets on two sides of the first baffle plates are arranged in a left-right staggered mode, filler layers are arranged between adjacent first baffle plates, and iron-carbon fillers (203) are filled in the filler layers; or, the inner part of the packing layer of the multi-stage packing layer track is filled with iron-carbon packing (203) which is wrapped and fixed by a filtering steel mesh; the inclination angle of the inclined first baffle plate (202) and the horizontal line of the micro-electrolytic cell (200) is 30-45 degrees, and the highest position of the first baffle plate is lower than the water inlet (201) of the micro-electrolytic cell; the volume of the iron carbon filler (203) of the micro-electrolytic cell (200) accounts for 10% -25% of the effective volume of the micro-electrolytic cell (200); the volume of the interval between any two adjacent iron carbon filling (203) areas of each filling layer of the micro-electrolysis cell (200) is 30% -60% of the volume of each iron carbon filling (203); The method comprises the following steps: ① Water supply, namely regulating the pH value of the high-concentration organic wastewater, and then carrying out micro-electrolysis treatment; the high-concentration organic wastewater enters a water inlet pipeline through a lift pump (101), is quickly and uniformly mixed with sulfuric acid (H 2 SO 4 ) added by a sulfuric acid (H 2 SO 4 ) adding device (102) through a pipeline mixer (103), and is regulated to pH value of 2.0-3.0 and then enters a micro-electrolytic cell (200); ② Micro-electrolysis treatment, namely, the wastewater in the previous step passes through a multi-stage filler layer track, and the iron-carbon filler filled in the wastewater undergoes micro-electrolysis reaction to degrade organic matters in the wastewater; the wastewater from the previous step enters through a water inlet (201) of the micro-electrolysis cell and flows to a multistage packing layer track along an inclined first baffle (202) in a homeopathic manner; a plurality of iron-carbon fillers (203) which are mutually spaced and wrapped and fixed by a filtering steel mesh are arranged in the multistage filler layer; the bottom of the micro-electrolysis cell (200) is provided with a sludge discharge port (204) which can discharge the generated sludge periodically, and when the wastewater is subjected to micro-electrolysis treatment, the wastewater flows to the Fenton reactor (300); ③ Fenton reaction, namely generating hydroxyl free radicals (OH) with extremely strong oxidizing property by Fenton oxidation reaction of the wastewater in the previous step, and degrading organic matters in the wastewater by utilizing the strong oxidizing property of the hydroxyl free radicals (OH); The wastewater from the previous step enters a Fenton reactor (300) and forms a Fenton oxidation system with ferrous sulfate (FeSO 4 ) and hydrogen peroxide (H 2 O 2 ) pumped by a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306) on an internal circulation pipeline (304) respectively; The micro-nano aerator (301) is connected with the bottom of the Fenton reactor (300), and micro-nano bubble ozone O 3 (302) generated by the micro-nano aerator is sent into the Fenton reactor (300) through an air distribution hole (303); An inner circulation pipeline (304) connected with the outer side of the Fenton reactor (300) and used for re-entering the Fenton reactor through the inner circulation pipeline (304) under the action of an inner circulation pump (307) and mixing with inlet water and treating again; The wastewater treated by the Fenton reactor (300) overflows to a Fenton reactor water outlet (309) under the combined action of the buoyancy of the micro-nano bubble ozone O 3 (302) and the thrust of the internal circulating water flow, and enters a three-stage precipitation filtering device (400) under the action of a hydraulic pump (310); ④ Three-stage precipitation filtration, namely sequentially carrying out three-stage filtration on the wastewater in the previous step through anthracite, quartz sand and modified zeolite to finish the processes of micro flocculation, filtration, adsorption, interception and precipitation on the wastewater, thereby realizing the advanced treatment of the wastewater; The wastewater enters a water inlet (401) of a three-stage precipitation filtering device, is filtered by a filler filled in a first reaction zone, enters a next reaction zone through a water distribution hole (403) on a filter plate (402), and is subjected to three-stage filtration of anthracite, quartz sand and modified zeolite from top to bottom; After the wastewater is treated by the three-stage precipitation filtering device (400), the water quality of the discharged water reaches the standard, overflows through a water outlet pipe of the three-stage precipitation filtering device, and returns to the water inlet pipeline for recycling treatment through a return pipe at the bottom of the three-stage precipitation filtering device (400) when the water quality does not reach the standard; In the step ②, the hydraulic retention time of the wastewater in the micro-electrolysis cell is 20-60min; In step ③, the pH of the inlet water to the Fenton reactor is controlled to be 3.0-5.0.
  4. 4. The high-concentration organic wastewater treatment device used in the wastewater treatment method comprises a water supply device (100), wherein the water supply device is sequentially connected with a micro-electrolysis cell (200), a Fenton reactor (300) and a three-stage precipitation filtering device (400); The micro-electrolytic cell (200) is provided with a multi-stage filler layer track, the multi-stage filler layer track comprises a plurality of parallel inclined first baffle plates (202), water outlets on two sides of the first baffle plates are arranged in a left-right staggered mode, filler layers are arranged between adjacent first baffle plates, and iron-carbon fillers (203) are filled in the filler layers; or, the inner part of the packing layer of the multi-stage packing layer track is filled with iron-carbon packing (203) which is wrapped and fixed by a filtering steel mesh; the inclination angle of the inclined first baffle plate (202) and the horizontal line of the micro-electrolytic cell (200) is 30-45 degrees, and the highest position of the first baffle plate is lower than the water inlet (201) of the micro-electrolytic cell; the volume of the iron carbon filler (203) of the micro-electrolytic cell (200) accounts for 10% -25% of the effective volume of the micro-electrolytic cell (200); the volume of the interval between any two adjacent iron carbon filling (203) areas of each filling layer of the micro-electrolysis cell (200) is 30% -60% of the volume of each iron carbon filling (203); The method comprises the following steps: ① Water supply, namely regulating the pH value of the high-concentration organic wastewater, and then carrying out micro-electrolysis treatment; the high-concentration organic wastewater enters a water inlet pipeline through a lift pump (101), is quickly and uniformly mixed with sulfuric acid (H 2 SO 4 ) added by a sulfuric acid (H 2 SO 4 ) adding device (102) through a pipeline mixer (103), and is regulated to pH value of 2.0-3.0 and then enters a micro-electrolytic cell (200); ② Micro-electrolysis treatment, namely, the wastewater in the previous step passes through a multi-stage filler layer track, and the iron-carbon filler filled in the wastewater undergoes micro-electrolysis reaction to degrade organic matters in the wastewater; the wastewater from the previous step enters through a water inlet (201) of the micro-electrolysis cell and flows to a multistage packing layer track along an inclined first baffle (202) in a homeopathic manner; a plurality of iron-carbon fillers (203) which are mutually spaced and wrapped and fixed by a filtering steel mesh are arranged in the multistage filler layer; the bottom of the micro-electrolysis cell (200) is provided with a sludge discharge port (204) which can discharge the generated sludge periodically, and when the wastewater is subjected to micro-electrolysis treatment, the wastewater flows to the Fenton reactor (300); ③ Fenton reaction, namely generating hydroxyl free radicals (OH) with extremely strong oxidizing property by Fenton oxidation reaction of the wastewater in the previous step, and degrading organic matters in the wastewater by utilizing the strong oxidizing property of the hydroxyl free radicals (OH); The wastewater from the previous step enters a Fenton reactor (300) and forms a Fenton oxidation system with ferrous sulfate (FeSO 4 ) and hydrogen peroxide (H 2 O 2 ) pumped by a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306) on an internal circulation pipeline (304) respectively; The micro-nano aerator (301) is connected with the bottom of the Fenton reactor (300), and micro-nano bubble ozone O 3 (302) generated by the micro-nano aerator is sent into the Fenton reactor (300) through an air distribution hole (303); An inner circulation pipeline (304) connected with the outer side of the Fenton reactor (300) and used for re-entering the Fenton reactor through the inner circulation pipeline (304) under the action of an inner circulation pump (307) and mixing with inlet water and treating again; The wastewater treated by the Fenton reactor (300) overflows to a Fenton reactor water outlet (309) under the combined action of the buoyancy of the micro-nano bubble ozone O 3 (302) and the thrust of the internal circulating water flow, and enters a three-stage precipitation filtering device (400) under the action of a hydraulic pump (310); ④ Three-stage precipitation filtration, namely sequentially carrying out three-stage filtration on the wastewater in the previous step through anthracite, quartz sand and modified zeolite to finish the processes of micro flocculation, filtration, adsorption, interception and precipitation on the wastewater, thereby realizing the advanced treatment of the wastewater; The wastewater enters a water inlet (401) of a three-stage precipitation filtering device, is filtered by a filler filled in a first reaction zone, enters a next reaction zone through a water distribution hole (403) on a filter plate (402), and is subjected to three-stage filtration of anthracite, quartz sand and modified zeolite from top to bottom; After the wastewater is treated by the three-stage precipitation filtering device (400), the water quality of the discharged water reaches the standard, overflows through a water outlet pipe of the three-stage precipitation filtering device, and returns to the water inlet pipeline for recycling treatment through a return pipe at the bottom of the three-stage precipitation filtering device (400) when the water quality does not reach the standard; In the step ②, the hydraulic retention time of the wastewater in the micro-electrolysis cell is 20-60min; In the step ③, the pH value of the inlet water of the Fenton reactor is controlled to be 3.0-5.0; In the step ③, the hydraulic retention time of the wastewater in the Fenton reactor is 20-60min; in the step ④, the hydraulic retention time of the wastewater in the three-stage precipitation filtering device is 20-60min.
  5. 5. The high-concentration organic wastewater treatment device used in the wastewater treatment method comprises a water supply device (100), wherein the water supply device is sequentially connected with a micro-electrolysis cell (200), a Fenton reactor (300) and a three-stage precipitation filtering device (400); The micro-electrolytic cell (200) is provided with a multi-stage filler layer track, the multi-stage filler layer track comprises a plurality of parallel inclined first baffle plates (202), water outlets on two sides of the first baffle plates are arranged in a left-right staggered mode, filler layers are arranged between adjacent first baffle plates, and iron-carbon fillers (203) are filled in the filler layers; or, the inner part of the packing layer of the multi-stage packing layer track is filled with iron-carbon packing (203) which is wrapped and fixed by a filtering steel mesh; the inclination angle of the inclined first baffle plate (202) and the horizontal line of the micro-electrolytic cell (200) is 30-45 degrees, and the highest position of the first baffle plate is lower than the water inlet (201) of the micro-electrolytic cell; the volume of the iron carbon filler (203) of the micro-electrolytic cell (200) accounts for 10% -25% of the effective volume of the micro-electrolytic cell (200); the volume of the interval between any two adjacent iron carbon filling (203) areas of each filling layer of the micro-electrolysis cell (200) is 30% -60% of the volume of each iron carbon filling (203); The method comprises the following steps: ① Water supply, namely regulating the pH value of the high-concentration organic wastewater, and then carrying out micro-electrolysis treatment; the high-concentration organic wastewater enters a water inlet pipeline through a lift pump (101), is quickly and uniformly mixed with sulfuric acid (H 2 SO 4 ) added by a sulfuric acid (H 2 SO 4 ) adding device (102) through a pipeline mixer (103), and is regulated to pH value of 2.0-3.0 and then enters a micro-electrolytic cell (200); ② Micro-electrolysis treatment, namely, the wastewater in the previous step passes through a multi-stage filler layer track, and the iron-carbon filler filled in the wastewater undergoes micro-electrolysis reaction to degrade organic matters in the wastewater; the wastewater from the previous step enters through a water inlet (201) of the micro-electrolysis cell and flows to a multistage packing layer track along an inclined first baffle (202) in a homeopathic manner; a plurality of iron-carbon fillers (203) which are mutually spaced and wrapped and fixed by a filtering steel mesh are arranged in the multistage filler layer; the bottom of the micro-electrolysis cell (200) is provided with a sludge discharge port (204) which can discharge the generated sludge periodically, and when the wastewater is subjected to micro-electrolysis treatment, the wastewater flows to the Fenton reactor (300); ③ Fenton reaction, namely generating hydroxyl free radicals (OH) with extremely strong oxidizing property by Fenton oxidation reaction of the wastewater in the previous step, and degrading organic matters in the wastewater by utilizing the strong oxidizing property of the hydroxyl free radicals (OH); The wastewater from the previous step enters a Fenton reactor (300) and forms a Fenton oxidation system with ferrous sulfate (FeSO 4 ) and hydrogen peroxide (H 2 O 2 ) pumped by a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306) on an internal circulation pipeline (304) respectively; The micro-nano aerator (301) is connected with the bottom of the Fenton reactor (300), and micro-nano bubble ozone O 3 (302) generated by the micro-nano aerator is sent into the Fenton reactor (300) through an air distribution hole (303); An inner circulation pipeline (304) connected with the outer side of the Fenton reactor (300) and used for re-entering the Fenton reactor through the inner circulation pipeline (304) under the action of an inner circulation pump (307) and mixing with inlet water and treating again; The wastewater treated by the Fenton reactor (300) overflows to a Fenton reactor water outlet (309) under the combined action of the buoyancy of the micro-nano bubble ozone O 3 (302) and the thrust of the internal circulating water flow, and enters a three-stage precipitation filtering device (400) under the action of a hydraulic pump (310); ④ Three-stage precipitation filtration, namely sequentially carrying out three-stage filtration on the wastewater in the previous step through anthracite, quartz sand and modified zeolite to finish the processes of micro flocculation, filtration, adsorption, interception and precipitation on the wastewater, thereby realizing the advanced treatment of the wastewater; The wastewater enters a water inlet (401) of a three-stage precipitation filtering device, is filtered by a filler filled in a first reaction zone, enters a next reaction zone through a water distribution hole (403) on a filter plate (402), and is subjected to three-stage filtration of anthracite, quartz sand and modified zeolite from top to bottom; After the wastewater is treated by the three-stage precipitation filtering device (400), the water quality of the discharged water reaches the standard, overflows through a water outlet pipe of the three-stage precipitation filtering device, and returns to the water inlet pipeline for recycling treatment through a return pipe at the bottom of the three-stage precipitation filtering device (400) when the water quality does not reach the standard; In the step ②, the hydraulic retention time of the wastewater in the micro-electrolysis cell is 20-60min; In the step ③, the pH value of the inlet water of the Fenton reactor is controlled to be 3.0-5.0; In the step ③, the hydraulic retention time of the wastewater in the Fenton reactor is 20-60min; In the step ④, the hydraulic retention time of the wastewater in the three-stage precipitation filtering device is 20-60min; In step ③, the ratio of the ventilation of the micro-nano aerator to the water volume of the Fenton reactor is 2:1-6:1; In the step ③, the mass concentration ratio of the hydrogen peroxide (H 2 O 2 ) added by a hydrogen peroxide (H 2 O 2 ) dosing device on the inner circulation pipeline of the Fenton reactor to the COD of the wastewater is 1:1-3:1; In the step ③, the flow ratio of the internal circulation reflux of the Fenton reactor to the inlet water of the Fenton reactor is 1:5-1:3.
  6. 6. A high concentration organic wastewater treatment device for the high concentration organic wastewater treatment method according to any one of claims 1 to 5, comprising a water supply device (100) which is sequentially connected with a micro-electrolytic cell (200), a Fenton reactor (300) and a three-stage precipitation filtration device (400), and is characterized in that: The water supply device (100) is provided with a sulfuric acid (H 2 SO 4 ) dosing device (102) which is used for adjusting the pH value of the high-concentration organic wastewater and then sending the high-concentration organic wastewater into the micro-electrolysis cell (200); The Fenton reactor (300) is provided with an inner circulation pipeline (304), the inner circulation pipeline (304) is provided with a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306), the top of the Fenton reactor (300) is provided with a Fenton reactor water outlet (309), and the Fenton reactor water outlet is connected with a three-stage precipitation filtering device (400) through a hydraulic pump (310); the three-stage precipitation filtering device (400) is provided with three reaction areas with the same structure, filter plates (402) are arranged between the reaction areas, water distribution holes (403) are formed in the filter plates (402), a plurality of parallel inclined second baffles (404) are arranged in each reaction area, and the filling materials filled in the three reaction areas are anthracite (405), quartz sand (406) and modified zeolite (407) from top to bottom.
  7. 7. A high concentration organic wastewater treatment device for the high concentration organic wastewater treatment method according to any one of claims 1 to 5, comprising a water supply device (100) which is sequentially connected with a micro-electrolytic cell (200), a Fenton reactor (300) and a three-stage precipitation filtration device (400), and is characterized in that: The water supply device (100) is provided with a sulfuric acid (H 2 SO 4 ) dosing device (102) which is used for adjusting the pH value of the high-concentration organic wastewater and then sending the high-concentration organic wastewater into the micro-electrolysis cell (200); The micro-electrolytic cell (200) is provided with a multi-stage filler layer track, the multi-stage filler layer track comprises a plurality of parallel inclined first baffle plates (202), water outlets on two sides of the first baffle plates are arranged in a left-right staggered mode, filler layers are arranged between adjacent first baffle plates, and iron-carbon fillers (203) are filled in the filler layers; The Fenton reactor (300) is provided with an inner circulation pipeline (304), the inner circulation pipeline (304) is provided with a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306), the top of the Fenton reactor (300) is provided with a Fenton reactor water outlet (309), and the Fenton reactor water outlet is connected with a three-stage precipitation filtering device (400) through a hydraulic pump (310); The three-stage precipitation filtering device (400) is provided with three reaction areas with the same structure, filter plates (402) are arranged between the reaction areas, water distribution holes (403) are formed in the filter plates (402), a plurality of parallel inclined second baffles (404) are arranged in each reaction area, and the filling materials filled in the three reaction areas are anthracite (405), quartz sand (406) and modified zeolite (407) from top to bottom in sequence; In addition, a chemical adding device (102) of sulfuric acid (H 2 SO 4 ) in the water supply device (100) is connected with a pipeline mixer (103) at one end, and is used for quickly and uniformly mixing the wastewater with sulfuric acid (H 2 SO 4 ), and a lifting pump (101) is connected at the other end; the micro-electrolytic cell (200) is characterized in that a micro-electrolytic cell water inlet (201) is arranged at the top and is connected with the multi-stage packing layer track, and a mud discharge port (204) is arranged at the bottom.
  8. 8. A high concentration organic wastewater treatment device for the high concentration organic wastewater treatment method according to any one of claims 1 to 5, comprising a water supply device (100) which is sequentially connected with a micro-electrolytic cell (200), a Fenton reactor (300) and a three-stage precipitation filtration device (400), and is characterized in that: The water supply device (100) is provided with a sulfuric acid (H 2 SO 4 ) dosing device (102) which is used for adjusting the pH value of the high-concentration organic wastewater and then sending the high-concentration organic wastewater into the micro-electrolysis cell (200); The micro-electrolytic cell (200) is provided with a multi-stage filler layer track, the multi-stage filler layer track comprises a plurality of parallel inclined first baffle plates (202), water outlets on two sides of the first baffle plates are arranged in a left-right staggered mode, filler layers are arranged between adjacent first baffle plates, and iron-carbon fillers (203) are filled in the filler layers; The Fenton reactor (300) is provided with an inner circulation pipeline (304), the inner circulation pipeline (304) is provided with a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306), the top of the Fenton reactor (300) is provided with a Fenton reactor water outlet (309), and the Fenton reactor water outlet is connected with a three-stage precipitation filtering device (400) through a hydraulic pump (310); The three-stage precipitation filtering device (400) is provided with three reaction areas with the same structure, filter plates (402) are arranged between the reaction areas, water distribution holes (403) are formed in the filter plates (402), a plurality of parallel inclined second baffles (404) are arranged in each reaction area, and the filling materials filled in the three reaction areas are anthracite (405), quartz sand (406) and modified zeolite (407) from top to bottom in sequence; The chemical adding device (102) of the sulfuric acid (H 2 SO 4 ) in the water supply device (100) is characterized in that one end of the chemical adding device is connected with a pipeline mixer (103) for quickly and uniformly mixing the wastewater with the sulfuric acid (H 2 SO 4 ), and the other end of the chemical adding device is connected with a lifting pump (101); The micro-electrolytic cell (200) is provided with a micro-electrolytic cell water inlet (201) at the top and is connected with the multi-stage filler layer track, and a mud discharge port (204) is arranged at the bottom; the micro-electrolytic cell (200) is characterized in that the multi-stage filler layer tracks are 3-stage or 4-stage or 5-stage parallel staggered tracks and are used for prolonging the filtering channels; The micro-nano bubble (302) generated by the micro-nano aerator (301) is sent into the Fenton reactor (300) through an air distribution hole (303) at the bottom of the Fenton reactor (300); The Fenton reactor (300) is characterized in that the internal circulation pipeline (304) is further provided with an internal circulation pump (307) and a valve (001) for regulating and controlling a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306) of the internal circulation pipeline (304).
  9. 9. A high concentration organic wastewater treatment device for the high concentration organic wastewater treatment method according to any one of claims 1 to 5, comprising a water supply device (100) which is sequentially connected with a micro-electrolytic cell (200), a Fenton reactor (300) and a three-stage precipitation filtration device (400), and is characterized in that: The water supply device (100) is provided with a sulfuric acid (H 2 SO 4 ) dosing device (102) which is used for adjusting the pH value of the high-concentration organic wastewater and then sending the high-concentration organic wastewater into the micro-electrolysis cell (200); The micro-electrolytic cell (200) is provided with a multi-stage filler layer track, the multi-stage filler layer track comprises a plurality of parallel inclined first baffle plates (202), water outlets on two sides of the first baffle plates are arranged in a left-right staggered mode, filler layers are arranged between adjacent first baffle plates, and iron-carbon fillers (203) are filled in the filler layers; The Fenton reactor (300) is provided with an inner circulation pipeline (304), the inner circulation pipeline (304) is provided with a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306), the top of the Fenton reactor (300) is provided with a Fenton reactor water outlet (309), and the Fenton reactor water outlet is connected with a three-stage precipitation filtering device (400) through a hydraulic pump (310); The three-stage precipitation filtering device (400) is provided with three reaction areas with the same structure, filter plates (402) are arranged between the reaction areas, water distribution holes (403) are formed in the filter plates (402), a plurality of parallel inclined second baffles (404) are arranged in each reaction area, and the filling materials filled in the three reaction areas are anthracite (405), quartz sand (406) and modified zeolite (407) from top to bottom in sequence; The chemical adding device (102) of the sulfuric acid (H 2 SO 4 ) in the water supply device (100) is characterized in that one end of the chemical adding device is connected with a pipeline mixer (103) for quickly and uniformly mixing the wastewater with the sulfuric acid (H 2 SO 4 ), and the other end of the chemical adding device is connected with a lifting pump (101); The micro-electrolytic cell (200) is provided with a micro-electrolytic cell water inlet (201) at the top and is connected with the multi-stage filler layer track, and a mud discharge port (204) is arranged at the bottom; the micro-electrolytic cell (200) comprises a multi-stage packing layer track, a filtering steel mesh and a filtering steel mesh, wherein the multi-stage packing layer track is a 3-stage or 4-stage or 5-stage parallel staggered track and is used for prolonging a filtering channel; The micro-nano bubble (302) generated by the micro-nano aerator (301) is sent into the Fenton reactor (300) through an air distribution hole (303) at the bottom of the Fenton reactor (300); The Fenton reactor (300) is characterized in that an internal circulation pump (307) and a valve (001) are further arranged on the internal circulation pipeline (304), and the internal circulation pump is used for regulating and controlling a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306) of the internal circulation pipeline (304); the inner circulation pipeline (304) is arranged outside the Fenton reactor (300), the upper end of the inner circulation pipeline (304) is connected with the upper part of the Fenton reactor (300), and the lower end of the inner circulation pipeline is connected with an inner circulation water inlet (308) at the bottom of the Fenton reactor (300); The three-stage precipitation filter device (400) is characterized in that a water inlet (401) of the three-stage precipitation filter device is arranged at the top, a water outlet pipe (408) of the three-stage precipitation filter device is arranged at the bottom, a return pipe (409) is arranged at the bottom, and a valve (001) is arranged on the return pipe (409).
  10. 10. A high concentration organic wastewater treatment device for the high concentration organic wastewater treatment method according to any one of claims 1 to 5, comprising a water supply device (100) which is sequentially connected with a micro-electrolytic cell (200), a Fenton reactor (300) and a three-stage precipitation filtration device (400), and is characterized in that: The water supply device (100) is provided with a sulfuric acid (H 2 SO 4 ) dosing device (102) which is used for adjusting the pH value of the high-concentration organic wastewater and then sending the high-concentration organic wastewater into the micro-electrolysis cell (200); The micro-electrolytic cell (200) is provided with a multi-stage filler layer track, the multi-stage filler layer track comprises a plurality of parallel inclined first baffle plates (202), water outlets on two sides of the first baffle plates are arranged in a left-right staggered mode, filler layers are arranged between adjacent first baffle plates, and iron-carbon fillers (203) are filled in the filler layers; The Fenton reactor (300) is provided with an inner circulation pipeline (304), the inner circulation pipeline (304) is provided with a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306), the top of the Fenton reactor (300) is provided with a Fenton reactor water outlet (309), and the Fenton reactor water outlet is connected with a three-stage precipitation filtering device (400) through a hydraulic pump (310); The three-stage precipitation filtering device (400) is provided with three reaction areas with the same structure, filter plates (402) are arranged between the reaction areas, water distribution holes (403) are formed in the filter plates (402), a plurality of parallel inclined second baffles (404) are arranged in each reaction area, and the filling materials filled in the three reaction areas are anthracite (405), quartz sand (406) and modified zeolite (407) from top to bottom in sequence; one end of the water supply device (100) and one end of the sulfuric acid (H 2 SO 4 ) dosing device (102) are connected with a lifting pump (101), and the other end of the water supply device is connected with a pipeline mixer (103) for quickly and uniformly mixing the wastewater with the sulfuric acid (H 2 SO 4 ); The micro-electrolytic cell (200) is provided with a micro-electrolytic cell water inlet (201) at the top, is connected with the multi-stage filler layer track, and is provided with a mud discharge port (204) at the bottom; the micro-electrolytic cell (200) comprises a multi-stage packing layer track, a filtering steel mesh and a filtering steel mesh, wherein the multi-stage packing layer track is a 3-stage or 4-stage or 5-stage parallel staggered track and is used for prolonging a filtering channel; The micro-nano bubble (302) generated by the micro-nano aerator (301) is sent into the Fenton reactor (300) through an air distribution hole (303) at the bottom of the Fenton reactor (300); The Fenton reactor (300) is characterized in that an internal circulation pump (307) and a valve (001) are further arranged on the internal circulation pipeline (304), and the internal circulation pump is used for regulating and controlling a ferrous sulfate (FeSO 4 ) dosing device (305) and a hydrogen peroxide (H 2 O 2 ) dosing device (306) of the internal circulation pipeline (304); The Fenton reactor (300) is characterized in that an inner circulation pipeline (304) is arranged outside the Fenton reactor (300), the upper end of the inner circulation pipeline (304) is connected with the upper part of the Fenton reactor (300), and the lower end of the inner circulation pipeline is connected with an inner circulation water inlet (308) at the bottom of the Fenton reactor (300); the three-stage sedimentation filter device (400) is characterized in that the top is provided with a water inlet (401) of the three-stage sedimentation filter device, the bottom is provided with a water outlet pipe (408) of the three-stage sedimentation filter device, and a return pipe (409), and the return pipe (409) is provided with a valve (001); The Fenton reactor (300) is characterized in that the air inlet of an aeration head of the micro-nano aerator (301) is ozone (O 3 ) and is used for generating micro-nano bubble ozone (O 3 ) so as to strengthen the generation of hydroxyl free radicals (OH) in the Fenton reaction process; The three-stage sediment filter (400) is characterized in that the inclined second baffle (404) and the horizontal line are inclined at an angle of 60-75 degrees; the three-stage precipitation filtering device (400) has the particle sizes of three fillers sequentially reduced from top to bottom, the anthracite particle size is 1.2-1.5mm, the quartz sand particle size is 0.8-1.0mm, the modified zeolite particle size is 0.4-0.6mm, and the non-uniformity coefficient is 2.

Description

High-concentration organic wastewater treatment method and device Technical Field The invention relates to the field of sewage treatment, in particular to a treatment technology of high-concentration organic wastewater. Background The high-concentration organic wastewater is always a recognized technical problem in the field of sewage treatment and mainly comes from industries such as coking, electroplating, pharmacy, printing and dyeing, leather, papermaking and the like. The organic matter concentration in the high-concentration organic wastewater is higher, the COD value is higher than 2000mg/L, the biological degradation is difficult, the BOD 5/COD value is lower than 0.3, and the biodegradability is poor. The wastewater has complex components, high concentration of organic matters, difficult biodegradation, strong toxicity and difficult obtaining of satisfactory treatment effect by a single physical method, chemical method or biological method, so that a plurality of types of process methods are required to be combined for treatment, and the emission standard can be achieved by synergy. Advanced oxidation methods (such as electrolytic oxidation, fenton oxidation, ozone oxidation, ultrasonic oxidation, photocatalytic oxidation, wet oxidation and the like) have become the most ideal technology for treating high-concentration organic wastewater due to the advantages of strong oxidizing capacity, high treatment efficiency, high reaction speed, easiness in control and the like. At present, related reports of treating high-concentration organic wastewater by adopting various advanced oxidation process combinations or combining with other processes exist, for example, an invention patent of a device and a method for purifying organic wastewater by nano-aeration iron-carbon micro-electrolysis (China patent number: CN 104230096B) discloses a device and a method for treating organic wastewater by combining a micro-electrolysis cell, an aerobic biomembrane reactor, a flocculation device and a backflushing screening device. The invention discloses an integrated toxic degradation-resistant wastewater treatment device and a treatment method thereof (Chinese patent number: CN 111908722A), and discloses a device and a method for treating toxic degradation-resistant wastewater by combining an adjusting tank, a primary micro-electrolysis reactor, a secondary Fenton reactor, a tertiary micro-electrolysis reactor, a coagulating sedimentation tank and a biochemical reaction tank. The prior art has the problems of complicated and lengthy process combination, large equipment occupation area, complex operation, certain popularization limitation, or unsatisfactory treatment effect on certain suspended matters and organic wastewater with higher chromaticity (such as printing and dyeing wastewater) due to the problems of easy hardening of filler, low medicament utilization rate, low reaction efficiency and the like. Therefore, it is urgent to develop a method and a device for treating high-concentration organic wastewater, which have high treatment efficiency, low running cost and simple operation. Disclosure of Invention The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a device and a method for efficiently treating high-concentration organic wastewater by integrating micro-electrolysis oxidation, fenton oxidation, ozone catalytic oxidation and micro-flocculation filtration technologies. In order to solve the technical problems, the technical conception of the invention is as follows: The high-concentration organic wastewater treatment device comprises a water supply device, a micro-electrolysis tank, a Fenton reactor and a three-stage precipitation filtration device, wherein the water supply device, the micro-electrolysis treatment, the Fenton oxidation, the ozone catalytic oxidation and the micro-flocculation filtration technology are coupled, the reaction processes complement each other, the synergistic effect is achieved, the purposes of improving the treatment efficiency and reducing the equipment and medicament investment are achieved, and the wastewater treatment method is achieved. Specifically, by optimizing the design process flow, the coupling technology of micro-electrolysis oxidation, fenton oxidation and ozone catalytic oxidation is formed, so that a plurality of oxidation technologies complement each other and synergistically increase, the dosage of the medicament is reduced, the high-efficiency removal of refractory organic matters is realized, ammonia nitrogen, fe 2+、Fe3+ and other impurities are further removed by combining with a micro-flocculation filtration technology, and finally the advanced treatment of high-concentration organic wastewater is realized. By designing the micro-electrolysis Chi Duoji packing layer track structure, the filtering channel is prolonged, the space utilization rate and the filtering efficiency are improved, the phenomenon