CN111689602A - Fenton oxidation reaction device - Google Patents
Fenton oxidation reaction device Download PDFInfo
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- CN111689602A CN111689602A CN201910178686.6A CN201910178686A CN111689602A CN 111689602 A CN111689602 A CN 111689602A CN 201910178686 A CN201910178686 A CN 201910178686A CN 111689602 A CN111689602 A CN 111689602A
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The invention provides a Fenton oxidation reaction device, which comprises a Fenton oxidation reaction tank for carrying out Fenton or Fenton-like oxidation reaction on wastewater and is characterized by also comprising a degassing tank for removing CO in water liquid after the wastewater is subjected to the Fenton or Fenton-like oxidation reaction2And the degassing tank is sleeved on the outer side of the Fenton oxidation reaction tank. The reactor disclosed by the invention is used for treating the biological effluent of the coking wastewater, so that the yield of dangerous waste iron mud during the deep treatment of the biological effluent of the coking wastewater is obviously reduced; the catalytic efficiency of hydrogen peroxide and the catalytic utilization rate of iron are improved, the contents of carbonate ions and iron ions in the treated effluent are obviously reduced, the dosage of alkali is obviously reduced when the pH of the wastewater is adjusted back after Fenton oxidation treatment, and the dosage of the alkali is obviously reducedThe cost of the process.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a Fenton oxidation reaction device.
Background
The coking wastewater is toxic and refractory industrial wastewater, the biological effluent of the coking wastewater still contains a large amount of refractory organic matters, and the conventional coagulation can not meet the existing discharge standard. The Fenton reaction is commonly used in the advanced treatment section of the coking wastewater because the Fenton reaction generates hydroxyl radicals with strong oxidation capability and better coagulation effect. The existing process is mostly a homogenizing pool, a reaction pool, an alkali adjusting pool and a sedimentation pool, and waste water is generatedThe water is firstly regulated to be acid, then enters a baffling type reaction area, ferrous sulfate and hydrogen peroxide are sequentially added, the pH value is adjusted back after the reaction, the obtained iron mud enters a secondary sedimentation tank for mud-water separation, the obtained iron mud is periodically discharged into a mud concentration tank, and the supernatant flows out from an overflow weir. Aiming at the actual engineering application process of the coking wastewater, the following technical defects are found: (1) due to Fe2+The presence of (2) produces a large amount of iron mud; (2) because Fe is not recycled, the catalytic utilization rate of Fe is low, and the catalytic efficiency of hydrogen peroxide is low; (3) the coking wastewater contains a large amount of carbonate ions and iron ions, and a large amount of alkali is consumed when the pH is adjusted back.
Based on the defects of the existing Fenton reaction, a Fenton oxidation reaction device capable of solving the problems needs to be developed so as to meet the engineering requirements.
Disclosure of Invention
In order to solve the technical problems, the invention provides a Fenton oxidation reaction device, which is used for treating effluent of coking wastewater after biological treatment (coking wastewater biological effluent for short), wherein the effluent of the coking wastewater after biological treatment contains a large amount of refractory organic matters and certain carbonate and bicarbonate radicals; the device is adopted to carry out Fenton oxidation treatment on the effluent of the coking wastewater after biodegradation, so that the yield of dangerous waste iron sludge during the deep treatment of the biological effluent of the coking wastewater is reduced; the catalytic efficiency of hydrogen peroxide and the catalytic utilization rate of iron are improved, the contents of carbonate ions and iron ions in the treated effluent are obviously reduced, and when the pH of the wastewater is adjusted back after Fenton oxidation treatment, the consumption of alkali is obviously reduced, so that the treatment cost of the wastewater is obviously reduced.
In order to achieve the purpose of the present invention, in one aspect, the present invention provides a fenton oxidation reaction apparatus, including a fenton oxidation reaction tank for performing a fenton or fenton-like oxidation reaction on wastewater, and further including a degassing tank for removing CO in an aqueous solution of the wastewater after the fenton or fenton-like oxidation reaction on the wastewater2And the degassing tank is sleeved on the outer side of the Fenton oxidation reaction tank.
Wherein, the degassing tank is sealed and connected with a vacuum pump for vacuumizing, and the air pressure in the degassing tank is reduced, so that the water in the degassing tank isCO dissolved in liquid2Overflow in the form of gas to remove CO2The purpose of (1).
In particular, the top of the degassing tank is flush with the top of the Fenton oxidation reaction tank.
In particular, the ratio of the height of the degassing tank to the height of the Fenton oxidation reaction tank is (50-100):100, preferably 75: 100.
The Fenton oxidation reaction tank comprises a Fenton reaction part, a solid-liquid separation part and a sludge discharge part, wherein the Fenton reaction part and the solid-liquid separation part are positioned at the upper part of the Fenton oxidation reaction tank; the sludge discharge part is positioned at the bottom of the reaction tank.
Particularly, the Fenton oxidation reaction tank is in a cylindrical shape, the bottom of the Fenton oxidation reaction tank is sealed, and the top of the Fenton oxidation reaction tank is open.
The Fenton reaction part is sleeved in the solid-liquid separation part and is positioned in the center of the Fenton oxidation reaction tank.
In particular, the fenton reaction section and the solid-liquid separation section are coaxial with the fenton oxidation reaction tank.
Wherein the sum of the height of the Fenton reaction part and the height of the sludge discharge part is equal to the height of the Fenton oxidation reaction tank.
In particular, the top of the fenton reaction part is flush with the top of the fenton oxidation reaction tank, and the bottom of the fenton reaction part is spaced from the bottom of the fenton oxidation reaction tank by a predetermined distance and does not contact with each other.
In particular, the ratio of the height of the fenton reaction part to the height of the fenton oxidation reaction tank is 80 to 90: 100, preferably 85: 100, respectively; the ratio of the diameter of the Fenton reaction part to the diameter of the Fenton oxidation reaction tank is 1 (3-5), and preferably 1: 4.
The Fenton reaction part is a cylinder which is open up and down, at least 1 reaction part water outlet is arranged on the side wall of the upper part of the Fenton reaction part, the water outlet is fixedly connected with a muddy water discharge pipe arranged on the outer side of the side wall of the Fenton reaction part, the muddy water discharge pipe extends to the lower part of the solid-liquid separation part from top to bottom, and muddy water mixture subjected to the Fenton reaction or the Fenton-like reaction is discharged from the water outlet of the reaction part and flows into the muddy water discharge pipe, and the muddy water mixture is introduced into the solid-liquid separation part for solid-liquid separation.
Particularly, when a plurality of reaction part water outlets are formed in the upper side wall of the fenton reaction part, the reaction part water outlets are arranged at the same height and are radially distributed at the same axial height of the fenton reaction part.
Particularly, the distance between the water outlet of the reaction part and the top of the Fenton oxidation reaction tank is 10-15cm, and preferably 10 cm.
Particularly, a wastewater inlet and 3 dosing ports are respectively arranged on the side wall of the middle lower part of the Fenton reaction part and are respectively used for respectively introducing wastewater to be treated, reaction liquid medicine sulfuric acid, ferrous sulfate and hydrogen peroxide into the reaction tank.
Especially, 3 add medicine mouthful settings in the below of water inlet, be close to the water inlet, three add the highly uniform that sets up of medicine mouth, along radial distribution on the same axial height of fenton reaction cylinder.
Particularly, the muddy water discharge pipe extends from top to bottom, penetrates through the inclined plate separation assembly and extends to the bottom of the inclined plate separation assembly, and the lower end of the muddy water discharge pipe is positioned above the aeration assembly.
Wherein, the bottom of fenton reaction portion sets up the aeration subassembly, introduces the inside of fenton reaction portion with outside air through the intake pipe that is connected with the aeration subassembly, and gaseous stirring makes waste water and liquid medicine misce bene.
In particular, the aeration assembly is selected from microporous aeration membranes.
Particularly, a sewage disposal pipeline is arranged on the aeration assembly to prevent the aeration assembly from being blocked, and the sewage disposal pipeline is an air pumping pipeline connected with an external vacuum pumping vacuum pump.
Wherein the solid-liquid separation part is sleeved outside the Fenton reaction part, the outer diameter of the solid-liquid separation part is equal to the diameter of the Fenton oxidation reaction tank, and the inner diameter of the solid-liquid separation part is equal to the diameter of the Fenton reaction part.
In particular, the height of the solid-liquid separation section is the same as the height of the fenton reaction section; the ratio of the height of the solid-liquid separation part to the height of the reaction tank is 80-90: 100, preferably 85: 100.
the middle part of the solid-liquid separation part is provided with an inclined plate separation assembly consisting of a plurality of inclined and mutually parallel inclined plates, and the inclined plate separation assembly is used for solid-liquid separation and separating mud-water mixture discharged from a water outlet of the reaction part of the Fenton oxidation part.
Particularly, the inclined plate separation assembly is positioned at the lower part of the water outlet of the separation part, and the bottom of the inclined plate separation assembly is positioned above the bottom of the Fenton reaction part.
In particular, the ratio of the height of the inclined plate separation assembly to the height of the solid-liquid separation part is 60-70: 100, preferably 65: 100, respectively; the inclined plate inclination angle of the inclined plate separation assembly is 30-45 degrees, and preferably 45 degrees.
In particular, the ratio of the height of the inclined plate separation assembly to the height of the reaction tank is 50-60: 100, preferably 55: 100, respectively;
particularly, the muddy water discharge pipe extends from top to bottom, penetrates through the inclined plate separation assembly and extends to the lower part of the bottom of the inclined plate separation assembly, and the lower end of the muddy water discharge pipe is positioned above the aeration assembly.
The solid-liquid separation part is a hollow cylinder which is opened up and down, wherein the solid-liquid separation part is coaxial with the Fenton reaction cylinder and is sleeved outside the Fenton reaction cylinder.
Particularly, at least 1 separation part water outlet is arranged on the side wall of the upper part of the solid-liquid separation cylinder, faces the degassing pool, and is used for discharging supernatant clear liquid after solid-liquid separation into the degassing pool.
In particular, when a plurality of the separation section water outlets are provided in the upper side wall of the solid-liquid separation section, the separation section water outlets are provided at the same height and are radially distributed at the same axial height of the solid-liquid separation section.
Particularly, the distance between the water outlet of the separation part and the top of the Fenton oxidation reaction tank is 15-25cm, and preferably 20 cm.
Wherein, mud discharging part is including fixing at the reaction tank bottom, being the mud baffle of hourglass hopper-shaped and setting up the mud discharging port in mud baffle lateral wall lower part, and the mud discharging port is linked together with the mud pipe that passes fenton oxidation reaction tank lower part lateral wall, will deposit the iron mud discharge to fenton oxidation reaction tank bottom.
Particularly, the diameter of the upper bottom surface of the sludge baffle is the same as that of the Fenton oxidation reaction tank, and the upper edge of the sludge baffle is flush with the bottom of the Fenton reaction part.
Particularly, the inclination angle of the sludge baffle and the bottom of the Fenton oxidation reaction tank is 30-45 degrees, and preferably 30 degrees.
Particularly, the sludge discharge port is communicated with a sludge discharge pipe penetrating through the side wall of the lower part of the Fenton oxidation reaction tank, and the funnel-shaped sludge baffle plate is used for discharging iron sludge from the Fenton oxidation reaction tank through the sludge discharge port and the sludge discharge pipeline after solid-liquid separation and precipitation to the lower part of the Fenton oxidation reaction tank.
Particularly, the distance between the sludge discharge port and the bottom of the Fenton oxidation reaction tank is 5-10 cm.
Wherein, the degassing tank is sealed, the top of the degassing tank is provided with an extraction opening, the degassing tank is connected with a vacuum pump through a pipeline, the vacuum pump extracts air to reduce the air pressure in the degassing tank, and dissolved CO in water liquid in the degassing tank2The gas overflows to discharge CO in the water liquid2The purpose of (1).
Particularly, the degassing pool is a hollow cylinder with upper and lower sealing, and the ratio of the height of the degassing pool to the height of the Fenton oxidation reaction pool is 50-100: 100, preferably 75:100, respectively; the ratio of the outer diameter of the Fenton oxidation reaction tank to the diameter of the Fenton oxidation reaction tank is 1.5-2: 1, preferably 2: 1; the inner diameter of the reactor is equal to the diameter of the Fenton oxidation reaction tank.
Particularly, the top of the degassing pool is level with the top of the Fenton oxidation reaction pool, an air extraction opening is arranged on the top of the degassing pool and is connected with an external vacuum pump through an air extraction pipeline, and dissolved CO in water liquid is removed2And the like.
Particularly, at least 1 degassing tank water outlet is arranged at the upper part of the side wall of the degassing tank for removing CO2And discharging the water liquid after waiting for gas through a water outlet of the degassing tank.
Particularly, the distance between the water outlet of the degassing tank and the top of the degassing tank is 30-50 cm.
Particularly, the degassing pool is composed of a degassing pool cylindrical part with a hollow upper part and a degassing pool circular truncated cone part with a hollow lower part, and the cylindrical part on the upper part and the circular truncated cone part on the lower part are connected into a whole.
In particular, the ratio of the outer diameter of the cylindrical portion to the diameter of the fenton oxidation reaction tank is 1.5 to 2:1, preferably 2: 1; the inner diameter of the reactor is equal to the diameter of the Fenton oxidation reaction tank, and the ratio of the height of the reactor to the height of the Fenton oxidation reaction tank is 30-50: 100, preferably 40: 100. the ratio of the outer diameter of the upper bottom surface of the circular truncated cone body part to the diameter of the Fenton oxidation reaction tank is 1.5-2: 1, preferably 2: 1; the inner diameter of the reactor is equal to the diameter of the Fenton oxidation reaction tank; the diameter of the lower bottom surface of the circular truncated cone body part is equal to that of the Fenton oxidation reaction tank. The ratio of the height of the lower round platform body part to the height of the Fenton oxidation reaction tank is 20-40: 100, preferably 30: 100.
compared with the prior art, the invention has the following advantages and benefits:
1) the solid-liquid separation part of the Fenton oxidation reaction tank of the reaction device is sleeved outside the Fenton reaction part, the mud-water mixture after the Fenton oxidation reaction is directly subjected to solid-liquid separation, the iron mud after the solid-liquid separation flows back into the Fenton reaction part, the pH value of the water liquid is kept at the pH value required by the Fenton oxidation because the pH value of the water liquid is not adjusted back to be alkaline in the Fenton oxidation reaction tank, the iron mud settled to the bottom of the Fenton oxidation reaction tank can be recycled, and the iron is recycled in the reaction device, so that the catalytic effect and the utilization rate of the Fe are obviously improved, the yield of the iron mud subjected to Fenton or Fenton-like oxidation is obviously reduced, the utilization rate of a medicament is increased, and the efficiency of catalyzing hydrogen peroxide is increased.
After the existing Fenton oxidation and coagulation, a secondary sedimentation tank is arranged for sludge-water separation, and the pH of water liquid is adjusted back to be alkaline, so that the iron mud cannot be recycled, and the treatment cost of the medicament and the Fe mud is increased; the pH value of the water liquid is adjusted back to be alkaline without adjusting back the pH value of the water liquid after solid-liquid separation, so that the precipitated iron mud can be recycled, and the catalytic capability and the catalytic efficiency of Fe are improved.
2) Of the Fenton reaction part of the reaction apparatus of the present inventionThe bottom of the device is provided with an aeration component, external air is uniformly introduced into a Fenton reaction part of the device through an air inlet pipe, uniform aeration is carried out, and the wastewater and the liquid medicine of the Fenton oxidation reaction are uniformly mixed by stirring; moreover, because the pH value of the mixture in the Fenton reaction part is adjusted to about 3, the aeration accelerates the decomposition of carbonic acid in the wastewater and assists in removing part of CO2And the alkali addition amount for adjusting the pH value is reduced.
The invention adopts the aeration of the aeration component to replace the stirring of the conventional stirring paddle, so that the wastewater and the liquid medicine of the oxidation reaction are uniformly mixed, and the aeration is also used for assisting in removing the dissolved CO in the wastewater2Improving CO removal from wastewater2The efficiency of (c).
3) The aeration component of the reaction device is also provided with a pipeline for cleaning the aeration component, and when the aeration component is used for cleaning, the vacuum pump is started to pump air, so that the problem of blockage of an aeration hole caused by accumulation of sewage or sludge is avoided, and the service life of the aeration disc is greatly prolonged.
4) The Fenton oxidation reaction device is provided with the degassing tank, vacuumizes, reduces the air pressure in the degassing tank, and removes a large amount of CO in the treated waste liquid2Reduce CO in the effluent2The content of (3) avoids consuming a large amount of alkali when the pH of the water solution is adjusted back to be alkaline when a large amount of carbonate exists in the effluent, and reduces the cost of wastewater treatment.
5) The solid-liquid separation part of the reaction device for performing solid-liquid separation on mud water adopts the inclined plate for separation, the precipitated Fe mud is recycled, the concentration of the catalyst is increased, the Fenton and the similar Fenton are coupled, the decomposition efficiency of hydrogen peroxide is improved, and the final Fe yield is reduced.
Drawings
FIG. 1 is a schematic view of the structure of a Fenton oxidation reaction apparatus according to the present invention;
FIG. 2 is a schematic top view of a Fenton oxidation reaction apparatus according to the present invention;
FIG. 3 is a schematic plan view of a Fenton oxidation reaction tank of the Fenton oxidation reaction apparatus according to the present invention;
FIG. 4 is a schematic view showing the structure of a Fenton reaction section of the Fenton oxidation reaction apparatus according to the present invention;
FIG. 5 is a schematic bottom view of a Fenton reaction section of the Fenton oxidation apparatus according to the present invention;
FIG. 6 is a schematic view of a microporous aeration membrane of a Fenton reaction part of the Fenton oxidation reaction apparatus according to the present invention;
FIG. 7 is a schematic view of another structure of the Fenton oxidation reaction apparatus according to the present invention.
Description of reference numerals:
1. a Fenton oxidation reaction tank; 11. a Fenton reaction section; 111. a water outlet of the reaction part; 112. a water inlet of the reaction part; 113. adding a sulfuric acid port; 114. adding ferrous sulfate notch; 115. adding a hydrogen peroxide port; 116. an aeration assembly; 117. an air inlet pipe; 12. a solid-liquid separation section; 121. a water outlet of the separation part; 122. an inclined plate separation assembly; 13. a sludge discharge part; 131. a sludge baffle; 132. a sludge discharge port; 2. a degassing pool; 21. an air extraction opening; 22. an air extraction pipeline; 23. a water outlet of the degassing tank; 24. a degassing tank cylindrical portion; 25 degassing pool circular truncated cone part.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
The Fenton oxidation reaction apparatus of the present invention will be described in detail below with reference to the accompanying drawings.
Referring to fig. 1 and 2, the fenton oxidation reaction device for treating coking wastewater of the present invention comprises: fenton oxidation reaction pond 1 and degasification pond 2, the whole cylinder body that is of Fenton oxidation reaction pond, the bottom is sealed, and the top is open, and waste water carries out the fenton oxidation or the fenton-like oxidation effect in oxidation reaction pond, the organic matter in the degradation waste water. The degassing tank is sleeved outside the reaction tank and sealed, the top of the degassing tank is level with the top of the reaction tank, and supernatant which flows into the degassing tank and is subjected to Fenton oxidation reaction is subjected to removal of dissolved carbon dioxide in water under a vacuum-pumping condition, so that the alkali consumption during subsequent pH adjustment is reduced.
As shown in fig. 1, 2 and 3, the fenton oxidation reaction tank 1 is cylindrical, has a sealed bottom and an open top, and comprises a fenton reaction part 11, a solid-liquid separation part 12 and a sludge discharge part 13, wherein the fenton reaction part and the solid-liquid separation part are positioned at the upper part of the fenton oxidation reaction tank, and the fenton reaction part is positioned at the center of the fenton oxidation reaction tank and is coaxial with the fenton oxidation reaction tank; the sludge discharge part is positioned at the bottom of the reaction tank. Wherein: carrying out Fenton or Fenton-like oxidation reaction on the wastewater in a Fenton reaction part to oxidize and degrade organic matters in the wastewater; performing in-situ separation on the mud-water mixture subjected to the Fenton oxidation treatment in a solid-liquid separation part, and enabling the settled Fe mud to enter a Fenton reaction part again to repeatedly utilize Fe to catalyze hydrogen peroxide; the mud discharging part is used for collecting settled iron mud, and partial iron mud is discharged after the Fe mud is accumulated in a large quantity.
As shown in fig. 1 and 4, the fenton reaction part 11 is a cylindrical reaction cylinder (i.e., a fenton reaction cylinder) which is open at the top and bottom, i.e., the fenton reaction part is a cylinder which is open at the top and bottom and is not sealed at the top and bottom; the height of the Fenton reaction cylinder is smaller than that of the Fenton oxidation reaction tank, the top of the Fenton reaction cylinder is flush with the top of the Fenton oxidation reaction tank, and the bottom of the Fenton reaction cylinder is spaced from the bottom of the Fenton oxidation reaction tank by a certain distance and does not contact with the bottom of the Fenton oxidation reaction tank; the bottom of the Fenton reaction part is communicated with the bottom of the solid-liquid separation part, is flush with the top of the sludge discharge part, and is flush with the top of the sludge baffle 131 of the sludge discharge part.
The ratio of the diameter of the Fenton reaction part to the diameter of the Fenton oxidation reaction tank is 1/5-1/3, preferably 1/4, and the ratio of the height of the Fenton reaction cylinder to the height of the reaction tank is 80-90: 100, preferably 85: 100, respectively; the sum of the height of the Fenton reaction part and the height of the sludge discharge part is equal to the height of the Fenton oxidation reaction tank.
The Fenton reaction part, the solid-liquid separation part and the degassing tank are made of cast iron materials.
The upper cylindrical side wall of the fenton reaction part is provided with at least 1 reaction part water outlet 111 (in the embodiment of the present invention, 4 water outlets are provided, for example, as shown in fig. 1, 2, and 3), and the distance from the reaction part water outlet to the top of the fenton oxidation reaction tank is 10-15cm, preferably 10 cm. And the water outlet of each reaction part is respectively connected with a muddy water discharge pipe 118, the muddy water discharge pipes are positioned on the outer side of the cylinder wall of the Fenton reaction part and extend to the bottom of the Fenton reaction part from top to bottom, and the muddy water mixture after the Fenton oxidation reaction is introduced to the lower part of the solid-liquid separation part of the Fenton oxidation reaction tank from the water outlet at the upper part of the reaction part for solid-liquid separation.
The muddy water discharge pipe is a stainless steel pipe and is welded with the water outlet of the reaction part. The muddy water discharge pipe penetrates through the inclined plate separation assembly by punching on the inclined plate separation assembly and extends to the lower part of the inclined plate separation assembly.
If a plurality of reaction part water outlets are arranged, the reaction part water outlets are arranged at the same height and are distributed along the radial direction on the same axial height of the Fenton reaction cylinder.
The middle lower part of the Fenton reaction part is provided with a wastewater inlet 112 and 3 dosing ports, wherein the wastewater inlet is connected with a wastewater pipe (not shown in the figure) to introduce wastewater into the Fenton reaction part; 3 add the medicine mouth and set up in the below of water inlet, be close to the water inlet, three add the highly uniform that sets up of medicine mouth, along radial distribution on the same axial height of fenton reaction cylinder, as figure 4. The 3 medicine adding ports are respectively a sulfuric acid adding port 113, a ferrous sulfate adding port 114 and a hydrogen peroxide adding port 115, are respectively connected with a sulfuric acid solution, a ferrous sulfate solution and a hydrogen peroxide solution through pipelines, and introduce the solutions into a Fenton reaction part for a Fenton oxidation reaction. Which kind of liquid medicine is specifically introduced into the 3 medicine adding ports can be unfixed, and different kinds of liquid medicine are respectively added into each medicine adding port.
The three dosing ports in the Fenton reaction cylinder can also be uniformly distributed on the side wall of the Fenton reaction cylinder, and the included angle between every two adjacent dosing ports is 120 degrees.
As shown in fig. 5, an aeration unit 116 is provided at the bottom of the fenton reaction part, and external air is introduced into the fenton reaction cylinder through an air inlet pipe 117 connected to the aeration unit. The aeration component selects a microporous aeration membrane, the liquid medicine added by water in the Fenton reaction cylinder is uniformly mixed under the aeration action of the aeration component to carry out oxidation reaction, and the reacted slurry flows from bottom to top under the action of the aeration component, flows out from a water outlet at the upper part of the Fenton reaction part and enters the solid-liquid separation part.The aeration subassembly sets up in the bottom of fenton reaction portion, and the aeration stirring makes waste water and the liquid medicine intensive mixing that fenton or class fenton reaction used, and the misce bene, solution pH adjusts to about 3 because the reaction time simultaneously, and the aeration can accelerate the decomposition of carbonic acid, plays the assistance and blows off CO2The effect of (1).
The specific structure of the microporous aeration membrane is shown in figure 6, the microporous aeration membrane is arranged by adopting an annular or square aeration pipeline, and is provided with 4 air inlet main pipes (such as pipes a, b, c and d in figure 6, air is introduced from two ends), and the uniformity of aeration can be better ensured by adjusting valves, and the mixing of solution can be better ensured. In addition to circular or square aeration line arrangements, other configurations of aeration assemblies known in the art are also suitable for use in the present invention.
In order to prevent the aeration component from being blocked and improve the aeration efficiency, the aeration component is periodically cleaned, and a cleaning pipeline (not shown in the attached drawing) is arranged on the aeration component. One end of the sewage cleaning pipeline is connected with the aeration assembly, the other end of the sewage cleaning pipeline is connected with the vacuum pump, a valve is arranged on the sewage cleaning pipeline of the aeration assembly, when in sewage cleaning, after the air inlet pipe is closed, the valve on the sewage cleaning pipeline is opened, the sewage cleaning pipeline is communicated with the vacuum pump, the vacuum pumping is carried out, the air pressure in the pipeline is reduced, and due to the action of negative pressure, the muddy water mixture blocked in the aeration pipeline is pumped away, so that the functions of cleaning sewage and removing scale are achieved.
As shown in fig. 1 and 2, the solid-liquid separation section 12 is a hollow cylinder (i.e., a solid-liquid separation cylinder) which is open at the top and bottom, the solid-liquid separation cylinder is coaxial with the fenton reaction cylinder and is sleeved outside the fenton reaction cylinder, the outer diameter of the solid-liquid separation section is equal to the diameter of the fenton oxidation reaction tank, and the inner diameter of the solid-liquid separation section is equal to the diameter of the fenton reaction cylinder; the height of the separation part is the same as that of the reaction part. The ratio of the height of the solid-liquid separation part to the height of the reaction tank is 80-90: 100, preferably 85: 100, respectively; the sum of the height of the Fenton separation part and the height of the sludge discharge part is equal to the height of the Fenton oxidation reaction tank.
At least 1 separation part water outlet 121 (4 water outlets are provided in the embodiment of the present invention, as shown in fig. 1) is provided on the upper side wall of the solid-liquid separation cylinder, and the distance from the separation part water outlet to the top of the fenton oxidation reaction tank is 15-25cm, preferably 20 cm. After solid-liquid separationThe supernatant flows into a degassing pool 2 from the water outlet of the separation part, and CO in the water liquid is removed by vacuumizing2And the amount of alkali required for adjusting the pH value is reduced. If a plurality of separation part water outlets are arranged, the separation part water outlets are arranged at the same height and are distributed along the radial direction on the same axial height of the Fenton oxidation reaction tank.
The middle part of the solid-liquid separation part is provided with an inclined plate separation assembly 122 which consists of a plurality of inclined and mutually parallel inclined plates and is used for solid-liquid separation, and muddy water discharged from the water outlet of the reaction part of the Fenton oxidation part is separated by the inclined plate separation assembly. The inclined plate separation assembly is positioned at the lower part of the water outlet of the separation part, and the bottom of the inclined plate separation assembly is positioned above the bottom of the Fenton reaction part. The ratio of the height of the inclined plate separation component to the height of the solid-liquid separation part is 60-70: 100, preferably 65: 100, respectively; the ratio of the height of the inclined plate separation component to the height of the reaction tank is 50-60: 100, preferably 55: 100, respectively; the inclined plate inclination angle of the inclined plate separation assembly is 30-45 degrees, and preferably 45 degrees.
The muddy water discharge pipe extends from top to bottom, penetrates through the inclined plate separation assembly and extends to the bottom lower part of the inclined plate separation assembly, and the lower end of the muddy water discharge pipe is positioned above the aeration assembly. The mud-water mixture discharged from a water outlet above the Fenton reaction part is introduced to the bottom of the solid-liquid separation part from the mud-water discharge pipe, the mud-water mixture enters the solid-liquid separation part in a downward water feeding mode, iron mud is separated from mud (namely solid-liquid) through an inclined plate of the inclined plate separation assembly due to the fact that the density of the iron mud is higher than that of water under the action of gravity, the iron mud is precipitated downwards, and water flow is upward, so that the effect of mud-water separation is achieved. The settled iron mud after solid-liquid separation is collected to the bottom of the Fenton oxidation reaction tank through the sludge baffle plate, the iron mud collected to the bottom of the reaction tank is carried into the Fenton reaction part again under the disturbance of aeration due to the aeration effect of the aeration component at the bottom of the Fenton reaction part, and flows back from the bottom of the Fenton reaction part to continue catalyzing H in the reaction area2O2。
As shown in fig. 1, the sludge discharge portion 13 is located at the bottom of the fenton oxidation reaction tank, and includes a funnel-shaped sludge baffle 131 fixed at the bottom of the reaction tank and a sludge discharge port 132 disposed at the lower portion of the sidewall of the sludge baffle. The diameter of the upper bottom surface of the sludge baffle is the same as that of the Fenton oxidation reaction tank, and the upper edge (the upper bottom surface) of the sludge baffle is flush with the bottom of the Fenton reaction part. The inclination angle of the sludge baffle and the bottom of the Fenton oxidation reaction tank is 30-45 degrees, and preferably 30 degrees. The mud baffle encloses into along the bottom of fenton oxidation reaction pond and leaks hopper-shaped, promotes the iron mud after the sediment to fall back to the bottom of fenton reaction portion, simultaneously because the effect of aeration produces ascending rivers, makes the iron mud that the part falls back get into the fenton reaction portion again, utilizes Fe catalysis hydrogen peroxide solution repeatedly, through the catalytic efficiency and the utilization ratio of Fe.
The sludge discharge port is communicated with a sludge discharge pipe 133 which penetrates through the side wall of the lower part of the Fenton oxidation reaction tank, and the funnel-shaped sludge baffle plate is used for discharging the sludge from the Fenton oxidation reaction tank through the sludge discharge port after the sludge is collected from the sludge which is precipitated to the lower part of the Fenton oxidation reaction tank after solid-liquid separation.
Referring to fig. 1 and 2, a degassing tank 2 is sleeved on the outer side of the fenton oxidation reaction tank and fixed on the outer side wall of the oxidation reaction tank, the degassing tank is sealed, and the top of the degassing tank is provided with an air pumping port connected with a vacuum pump (not shown in the drawing), the vacuum pump pumps air to reduce the air pressure in the degassing tank, and gas (such as CO) dissolved in water in the degassing tank is dissolved in water2) Overflow to discharge CO in water2The purpose of reducing the acidity of the water solution and the dosage of alkali required when the pH of the water solution is adjusted back is achieved.
The degassing pool is a hollow cylinder with the upper part and the lower part sealed, and the ratio of the height of the degassing pool to the height of the Fenton oxidation reaction pool is 50-100: 100, preferably 75:100, respectively; the ratio of the outer diameter of the Fenton oxidation reaction tank to the diameter of the Fenton oxidation reaction tank is 1.5-2: 1, preferably 2: 1; the inner diameter of the reactor is equal to the diameter of the Fenton oxidation reaction tank. The top of the degassing pool is level with the top of the Fenton oxidation reaction pool, and the top is provided with an air suction port 21 which is connected with an external vacuum pump through an air suction pipeline 22 to remove CO in water liquid2And (2 pumping ports are provided in the embodiment of the present invention, as shown in fig. 1). The bottom of the degassing pool is sealed and is positioned above the sludge discharge part of the Fenton oxidation reaction pool. The upper part of the side wall of the degassing pool is provided with at least 1 degassing pool water outlet 23 for removing CO2And discharging the water liquid after waiting for gas through a water outlet of the degassing tank. Distance between water outlet of degassing tank30-50cm from the top.
As shown in fig. 7, the degassing tank of the fenton oxidation reaction apparatus of the present invention may be a degassing tank cylindrical portion 24 having a hollow upper portion and a degassing tank circular cylindrical portion 25 having a hollow lower portion. The cylinder body on upper portion is connected with the round platform body of lower part and is an organic whole, and the ratio of the external diameter of cylinder body and the diameter of fenton oxidation reaction pond is 1.5-2: 1, preferably 2: 1; the inner diameter of the reactor is equal to the diameter of the Fenton oxidation reaction tank, and the ratio of the height of the reactor to the height of the Fenton oxidation reaction tank is 30-50: 100, preferably 40: 100. the ratio of the outer diameter of the upper bottom surface of the circular truncated cone body part to the diameter of the Fenton oxidation reaction tank is 1.5-2: 1, preferably 2: 1; the inner diameter of the reactor is equal to the diameter of the Fenton oxidation reaction tank; the diameter of the lower bottom surface of the circular truncated cone body part is equal to that of the Fenton oxidation reaction tank. The ratio of the height of the lower round platform body part to the height of the Fenton oxidation reaction tank is 20-40: 100, preferably 30: 100.
the operation of the Fenton oxidation reaction apparatus according to the present invention will be described in detail with reference to FIGS. 1 to 7.
The Fenton oxidation reaction device is used for treating biological effluent of coking wastewater.
As shown in FIG. 1, the solid arrows indicate the flowing direction of the slurry-water mixture in the Fenton reaction; the direction indicated by the single arrow is the air flow direction of the air exhaust; the direction indicated by the double arrow is the direction of flow of the supernatant. Coking wastewater biological effluent is poured into the Fenton reaction part 11 of the Fenton oxidation reaction tank 1 from the reaction part water inlet 112, sulfuric acid, ferrous sulfate, hydrogen peroxide solution are respectively added through 3 dosing ports and are mixed with coking wastewater biological effluent, and meanwhile, the aeration component 116 at the bottom of the Fenton reaction part uniformly aerates through the air inlet of the air inlet pipe 117, so that wastewater and liquid medicine are uniformly mixed, the Fenton or similar Fenton oxidation reaction is carried out when the pH value is about 3, and organic matters in wastewater are degraded.
The sludge-water mixture after the Fenton oxidation reaction is discharged from a water outlet 111 of the reaction part and flows into a sludge-water discharge pipe 118 communicated with the water outlet of the reaction part, the sludge-water mixture is introduced into the bottom of the solid-liquid separation part 12 of the Fenton oxidation reaction tank 1 through the sludge-water discharge pipe, the sludge-water mixture enters the solid-liquid separation part in a following water inflow mode, and the sludge-water mixture is settled by gravity (Fe sludge is dense)The degree is higher than that of water) is subjected to mud-water separation by the inclined plate, and the Fe mud is precipitated on the inclined plate and flows into the mud discharging part 13 along the inclined plate. The iron sludge settled to the sludge discharge part at the bottom of the Fenton oxidation reaction tank is collected by the sludge baffle 131, the iron sludge converged to the bottom of the Fenton reaction part 11 is disturbed by the air flow aerated by the aeration component 116, and the settled Fe sludge enters the Fenton reaction part again, continues to participate in the catalysis of hydrogen peroxide by utilizing the Fenton-like oxidation reaction principle, and oxidizes organic matters in the wastewater; the supernatant separated by the solid-liquid separation part flows into the degassing tank 2 through the water outlet 121 of the separation part, and the supernatant is vacuumized by a vacuum pump in the degassing tank to form negative pressure so as to remove CO in the water liquid2. The vacuum degree of the area is maintained by the degassing tank through the vacuum pump after the air pumping and the pressure reduction of the vacuum pump, and the dissolved CO in the wastewater is removed2The alkali adding amount of the effluent water of the Fenton oxidation reaction device with the pH adjusted back is reduced, and the wastewater treatment cost is saved. In addition, when the aeration stirring micropores of the aeration component at the bottom of the Fenton reaction part are blocked, the valve of the sewage cleaning pipeline of the aeration component is opened and communicated with an external vacuum pump, air is pumped out and decompressed, under the action of negative pressure, the muddy water mixture blocked in the aeration pipeline is pumped out, and the valve is closed after the muddy water mixture is cleaned up.
The above-described embodiments of the present invention are merely exemplary and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. The Fenton oxidation reaction device comprises a Fenton oxidation reaction tank for carrying out Fenton or Fenton-like oxidation reaction on wastewater, and is characterized by further comprising a degassing tank, wherein CO in water liquid after the Fenton or Fenton-like oxidation reaction on the wastewater is removed2And the degassing tank is sleeved on the outer side of the Fenton oxidation reaction tank.
2. A fenton oxidation reaction apparatus according to claim 1, wherein the fenton oxidation reaction tank comprises a fenton reaction section, a solid-liquid separation section and a sludge discharge section, wherein the fenton reaction section and the solid-liquid separation section are located at an upper portion of the fenton oxidation reaction tank; the sludge discharge part is positioned at the bottom of the reaction tank.
3. A Fenton oxidation reaction apparatus according to claim 2, wherein the Fenton reaction section is a cylinder which is open at the top and bottom, and at least 1 reaction section water outlet is provided in the upper side wall thereof, and the water outlet is fixedly connected to a sludge water discharge pipe provided outside the side wall of the Fenton reaction section, and the sludge water discharge pipe extends from the top to the bottom to the lower part of the solid-liquid separation section, and the sludge water mixture after the Fenton reaction or the Fenton-like reaction is discharged from the reaction section water outlet and flows into the sludge water discharge pipe, and the sludge water mixture is introduced into the solid-liquid separation section to be subjected to solid-liquid separation.
4. A fenton oxidation reaction apparatus according to claim 2, wherein an aeration unit is provided at a bottom of the fenton reaction section, external air is introduced into the interior of the fenton reaction section through an air inlet pipe connected to the aeration unit, and the gas is agitated to uniformly mix the wastewater and the chemical solution.
5. A Fenton oxidation reaction apparatus according to any one of claims 2 to 4, wherein the solid-liquid separation section is fitted to the outside of the Fenton reaction section, and wherein the solid-liquid separation section has an outer diameter equal to the diameter of the Fenton oxidation reaction tank and an inner diameter equal to the diameter of the Fenton reaction section.
6. A Fenton oxidation reaction device according to any one of claims 2 to 4, wherein the sludge discharge part comprises a funnel-shaped sludge baffle plate fixed at the bottom of the reaction tank and a sludge discharge port arranged at the lower part of the side wall of the sludge baffle plate, and the sludge discharge port is communicated with a sludge discharge pipe penetrating through the side wall of the lower part of the Fenton oxidation reaction tank to discharge the iron sludge precipitated at the bottom of the Fenton oxidation reaction tank.
7. A Fenton oxidation reaction apparatus according to claim 6, wherein the diameter of the upper bottom surface of the sludge baffle is the same as the diameter of the Fenton oxidation reaction tank, and the upper edge of the sludge baffle is flush with the bottom of the Fenton reaction section.
8. A Fenton oxidation reaction apparatus according to any one of claims 1 to 7, wherein said degassing vessel is sealed, and has an exhaust port at its top, and is connected to a vacuum pump through a pipe, and the vacuum pump exhausts air to lower the pressure in the degassing vessel, and CO dissolved in the water in the degassing vessel is dissolved2The gas overflows to discharge CO in the water liquid2The purpose of (1).
9. A Fenton's oxidation reaction apparatus according to any one of claims 1 to 7, wherein said degassing tank is a hollow cylinder sealed at the top and bottom, and the ratio of the height of said degassing tank to the height of said Fenton's oxidation reaction tank is 50 to 100: 100, preferably 75:100, respectively; the ratio of the outer diameter of the Fenton oxidation reaction tank to the diameter of the Fenton oxidation reaction tank is 1.5-2: 1, preferably 2: 1; the inner diameter of the reactor is equal to the diameter of the Fenton oxidation reaction tank.
10. A Fenton's oxidation reaction apparatus according to any one of claims 1 to 7, wherein said degassing tank is composed of a degassing tank cylindrical portion having a hollow upper portion and a degassing tank cylindrical portion having a hollow lower portion, and said upper cylindrical portion and said lower cylindrical portion are integrally connected.
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