CN113371886A - Multi-reaction-chamber Fenton fluidized bed reactor and wastewater treatment method thereof - Google Patents

Multi-reaction-chamber Fenton fluidized bed reactor and wastewater treatment method thereof Download PDF

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CN113371886A
CN113371886A CN202110783961.4A CN202110783961A CN113371886A CN 113371886 A CN113371886 A CN 113371886A CN 202110783961 A CN202110783961 A CN 202110783961A CN 113371886 A CN113371886 A CN 113371886A
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reaction chamber
wastewater
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fluidized bed
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CN113371886B (en
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姜笔存
贺雨舟
于伟华
屈晋云
谈政焱
司徒瑜霞
高泽楠
林加文
刘浩亮
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Nanjing Innovation Centre For Environmental Protection Industry Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention discloses a multi-reaction-chamber Fenton fluidized bed reactor and a wastewater treatment method thereof, belonging to the technical field of wastewater treatment. The reactor body is internally and properly provided with the first reaction chamber, the second reaction chamber and the clarifying chamber from inside to outside, and the first reaction chamber is filled with proper filler, so that the iron crystallization rate in the Fenton fluidized bed reactor is improved, the wastewater is ensured to carry out degradation reaction in the first reaction chamber with high-concentration filler crystals, then the degradation reaction is continuously carried out in the second reaction chamber with relatively low-concentration filler crystals, and liquid alkali is added for precipitation reaction, so that the detoxification capability of the reactor is improved, and the treatment effect of the Fenton reactor is improved.

Description

Multi-reaction-chamber Fenton fluidized bed reactor and wastewater treatment method thereof
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a multi-reaction-chamber Fenton fluidized bed reactor and a wastewater treatment method thereof.
Background
Fenton's advanced oxidation technology adopts Fenton's reagent mainly includes H2O2Oxidizing agent and Fe2+The catalyst and the waste water can react to generate hydroxyl radicals under certain conditions, and the high oxidation capacity of the hydroxyl radicals reacts with organic matters in the waste water to decompose and oxidize the organic matters and destroy generated carbon dioxide and water, thereby reducing the COD which is difficult to decompose by organisms in the waste water.
The existing traditional Fenton process generally has the problems that the utilization efficiency of a Fenton reagent added in the reaction process is low, the mixed reaction of an oxidant and a catalyst is not uniform, the medicament is wasted, and the treatment cost is increased; in addition, a large amount of iron sludge is generated in the reaction, solid-liquid separation is difficult, and the iron sludge needs to be treated.
The research shows that the Chinese patent application with the application publication number of CN107162158A on 2017, 9 and 15 discloses a fluidized bed Fenton reactor and a method, the reactor comprises a reaction tank body, the bottom of the reaction tank body is provided with a catalyst inlet for raw water and catalyst to enter and an oxidant inlet for raw water and oxidant to enter, the catalyst inlet is connected with a first water distribution head, the oxidant inlet is connected with a second water distribution head, a micropore aeration head is arranged on the side part of the first water distribution head in the reaction tank body, a main reaction area is arranged above the micropore aeration head in the reaction tank body, a filler is arranged in the main reaction area, and a three-phase separator is arranged above the main reaction area. The invention ensures the uniform water distribution through the arrangement of a plurality of water distribution heads, avoids the loss of crystals through the arrangement of a three-phase separator, and avoids the oxidation corrosion of pipe fittings and equipment caused by premature hydroxyl free radicals through the respective mixing of raw water and an oxidant and the respective mixing of the raw water and a catalyst in front of a main reaction zone. However, the method still has the problems of poor Fenton crystallization rate of the fluidized bed, weak detoxification capability of the Fenton reactor and the like when being applied to treating high-concentration wastewater.
In addition, the chinese utility model patent of grant No. CN204714580U, which is published on grant publication date 2015, 10 and 21 discloses an upflow fenton fluidized bed, which comprises a reaction tower with a reaction chamber and a water distributor installed at the lower part of the reaction chamber, wherein the reaction chamber is divided into a ferrous iron mixing zone, a middle reaction zone and a clarification zone, the top of the reaction tower is provided with a ferrous iron circulation zone, the hydrogen peroxide circulating area is communicated with the ferrous mixing area, and the hydrogen peroxide circulating area is communicated with the hydrogen peroxide mixing area. The fluidized bed is mainly designed in a water distribution mode of ferrous and hydrogen peroxide, and the mixing uniformity of the ferrous and the hydrogen peroxide is improved.
Disclosure of Invention
1. Problems to be solved
The invention provides a multi-reaction-chamber Fenton fluidized bed reactor and a wastewater treatment method thereof, aiming at the problems of low Fenton crystallization rate, weak detoxification capability of the Fenton reactor and the like in the wastewater treatment process of the Fenton reactor in the prior art. According to the invention, the reactor structure is reasonably designed, the first reaction chamber, the second reaction chamber and the clarification chamber are sequentially arranged from inside to outside, and the first reaction chamber is filled with a suitable filler, so that the iron crystallization rate in the reaction chamber is improved, the iron crystallization catalytic degradation reaction can be utilized, the detoxification capability of the reactor is improved, and the Fenton treatment effect is improved.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention discloses a Fenton fluidized bed reactor with multiple reaction chambers, which comprises a reactor body, wherein a first reaction chamber, a second reaction chamber and a clarification chamber are arranged in the reactor body, the first reaction chamber is positioned at the central position in the reactor body, the second reaction chamber and the clarification chamber are positioned outside the first reaction chamber, and the second reaction chamber is positioned between the first reaction chamber and the clarification chamber;
wherein the top of the first reaction chamber is provided with a three-phase separator, the bottom of the first reaction chamber is provided with an aeration device and a water distributor, the aeration device is positioned above the water distributor, and the three-phase separator is connected with the aeration device through a pipeline; and the cross section of the top of the first reaction chamber is gradually increased from bottom to top, and the first reaction chamber is filled with a filler.
Preferably, the volume ratio among the first reaction chamber, the second reaction chamber and the clarification chamber is (0.8-1.2): (1.8-2.2): (2.8-3.2).
Preferably, the ratio of the lower cross-sectional area to the upper cross-sectional area of the top of the first reaction chamber ranges from 0.6 to 0.8.
Preferably, the filler filled in the first reaction chamber comprises one or two of anion exchange resin and high molecular water absorption resin.
Preferably, the multi-reaction-chamber Fenton fluidized bed reactor comprises an alkali adding port, wherein the alkali adding port is arranged at the height of 1/4-3/4 of the second reaction chamber.
Preferably, the multi-reaction-chamber Fenton fluidized bed reactor comprises a first dosing port and a second dosing port, wherein the first dosing port is positioned between the aeration device and the water distributor, and the second dosing port is positioned at a position 100 mm-1000 mm above the aeration device.
Preferably, the aeration device comprises a filter plate and an aeration head, wherein the filter plate is used for carrying out secondary water distribution on the wastewater, so that the water distribution uniformity is improved.
Preferably, the multi-reaction-chamber fenton fluidized bed reactor comprises a centrifugal fan and a sludge discharge device, wherein the centrifugal fan is arranged outside the reactor body and is arranged on a pipeline between the three-phase separator and the aeration device; the sludge discharge device is arranged at the bottom of the reactor body and is used for collecting precipitates in the reaction process.
The invention discloses a wastewater treatment method of a Fenton fluidized bed in multiple reaction chambers, which comprises the following steps:
s10, iron crystal forming stage: feeding the wastewater into a first reaction chamber, starting an aeration device, adding ferrous sulfate and hydrogen peroxide according to a first mass ratio, wherein under the action of aeration, a filler filled in the first reaction chamber forms a fluidized state, the hydrogen peroxide generates hydroxyl radicals under the catalysis of ferrous ions, the hydroxyl radicals and organic matters in the wastewater generate degradation reaction, and iron ions in the wastewater are attached to the surface of the filler to form crystals;
s20, iron crystallization catalysis stage: feeding the wastewater into a first reaction chamber, starting an aeration device, adding ferrous sulfate and hydrogen peroxide according to a second mass ratio, wherein under the action of aeration, a filler filled in the first reaction chamber forms a fluidized state, the hydrogen peroxide generates hydroxyl radicals under the catalysis of iron crystals generated in the step S10, and the hydroxyl radicals and organic matters in the wastewater undergo a degradation reaction;
s30, deep processing stage: and (4) sending the wastewater treated in the step S10 or S20 into a second reaction chamber, continuing to perform degradation reaction for a certain time, then adding liquid caustic soda into the second reaction chamber, performing neutralization and precipitation reaction, and enabling the wastewater after the neutralization and precipitation reaction to enter a clarification area for further mud-water separation treatment to obtain treated effluent.
Preferably, in the fenton fluidized bed wastewater treatment method for multiple reaction chambers, the filler filled in the first reaction chamber comprises one or two of anion exchange resin and high molecular water absorption resin.
Preferably, in step S10, the first mass ratio of ferrous sulfate to hydrogen peroxide is 1: 2-1: 5; in step S20, the second mass ratio of ferrous sulfate to hydrogen peroxide is 1: 5-1: 10.
and the reaction time for continuing the degradation reaction of the wastewater in the step S30 is 0.5-3 h.
Preferably, in steps S10 and S20, the mass ratio of the incoming water COD of hydrogen peroxide to wastewater is 1: 3-1: 0.5.
preferably, in step S10, the pH of the wastewater in the first reaction chamber is adjusted to 4-6; in step S20, the pH value of the wastewater in the first reaction chamber is adjusted to 2-4.
Preferably, in step S30, the pH of the wastewater in the second reaction chamber is adjusted to 7 to 9.
Preferably, in the step S10 or S20, the flow rate of the wastewater entering the first reaction chamber is 15-20 m/h, and the aeration rate is 0.8-1.5 m3/m2。
Preferably, the method for treating wastewater by a multi-reaction-chamber fenton fluidized bed further comprises the following steps of S40: the precipitates generated in the steps S10-S30 are collected in a sludge discharge device arranged at the bottom of the reactor body, and periodic sludge discharge is carried out.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the Fenton fluidized bed reactor with the multiple reaction chambers, the first reaction chamber, the second reaction chamber and the clarifying chamber are properly arranged in the reactor body from inside to outside, so that wastewater is firstly subjected to degradation reaction in the first reaction chamber with high-concentration filler crystals to improve the biodegradability, and then is subjected to degradation reaction for a period of time in the second reaction chamber with relatively low-concentration filler crystals to ensure that residual hydroxyl radicals and residual hydrogen peroxide in the wastewater are completely reacted with organic matters; adding liquid alkali for precipitation reaction to precipitate iron ions which are not attached to the filler, and simultaneously, the iron hydroxide precipitate can wrap part of complex organic matters in water, so that the treatment effect of the Fenton reactor is improved;
(2) according to the Fenton fluidized bed reactor with the multiple reaction chambers, the top of the first reaction chamber is provided with the three-phase separator, the bottom of the first reaction chamber is provided with the aeration device and the water distributor, the three-phase separator is connected with the aeration device through the pipeline, crystals formed by iron are retained in the first reaction chamber, and collected gas is recycled in the first reaction chamber to form a highly fluidized reaction environment;
(3) according to the multi-reaction-chamber Fenton fluidized bed reactor, the cross section of the top of the first reaction chamber is gradually increased from bottom to top, and when wastewater reaches the top area of the first reaction chamber, the ascending flow velocity is reduced, so that the pressure of a three-phase separator is smaller, and the interception effect of crystals and the clarity of effluent are improved;
(4) according to the method for treating wastewater in the Fenton fluidized bed of the multiple reaction chambers, in the iron crystallization forming stage, by utilizing the characteristics that a large number of hydroxyl groups exist on the surface of filled filler resin, the specific surface area is large and the like, more sites are provided for iron crystallization, the iron crystallization is easy to crystallize with iron hydrate, and the iron crystallization rate is improved, so that the formation of hydroxyl radicals is promoted, the detoxifying capacity of the first reaction chamber is improved, in the iron crystallization catalyzing stage, the formed iron crystallization is utilized to catalyze the generation of the hydroxyl radicals, organic matters in wastewater are effectively degraded, and the wastewater treatment effect is improved.
Drawings
FIG. 1 is a schematic diagram of a multi-reaction-chamber Fenton fluidized bed reactor according to the present invention;
in the figure:
100. a first reaction chamber; 101. an air inlet pipe; 102. a first medicine inlet pipe; 103. a water inlet pipe;
110. a three-phase separator; 120. an aeration device; 130. a water distributor; 140. a centrifugal fan;
200. a second reaction chamber; 210. adding an alkali port; 300. a clarification chamber; 310. a water outlet;
400. a sludge discharge device; 1010. a first dosing port; 1020. and a second medicine adding port.
Detailed Description
The invention is further described with reference to specific examples.
As shown in fig. 1, the multi-reaction-chamber fenton fluidized bed reactor of the present invention comprises a reactor body, wherein a first reaction chamber 100, a second reaction chamber 200 and a clarification chamber 300 are arranged in the reactor body, the first reaction chamber 100 is located at the central position inside the reactor body, the second reaction chamber 200 and the clarification chamber 300 are located outside the first reaction chamber 100, the second reaction chamber 200 is located between the first reaction chamber 100 and the clarification chamber 300, and the volume ratio among the first reaction chamber 100, the second reaction chamber 200 and the clarification chamber 300 is (0.8-1.2): (1.8-2.2): (2.8-3.2), the reactor body can be a cylinder, and the first reaction chamber 100 is a central cylinder in the reactor body.
The top of the first reaction chamber 100 is provided with a three-phase separator 110, the cross section of the top of the first reaction chamber 100 is gradually enlarged from bottom to top, and the ratio of the lower sectional area to the upper sectional area of the top of the first reaction chamber 100 is 0.6-0.8; the bottom of the first reaction chamber 100 is provided with an aeration device 120 and a water distributor 130, and the aeration device 120 is positioned above the water distributor 130; the first reaction chamber 100 is filled with a filler, and the filler includes one or two of anion exchange resin and high molecular water absorption resin. Anion exchange resins include, but are not limited to, types D201, D213, D202, and the like; the high molecular water-absorbing resin includes, but is not limited to, polymers formed by monomers such as polyacrylic acid, polypropylene glycol, polyacrylamide, polyvinyl alcohol, polyacrylonitrile, ethylene oxide, starch, carboxymethyl cellulose and the like.
The water distributor 130 may be a spiral-flow water distributor, the wastewater enters the water distributor 130 through the water inlet pipe 103, and then enters the first reaction chamber 100 under the action of the water distributor, the aeration device 120 is opened, the aeration device 120 may include a filter plate and an aeration head (not shown), the gas enters the aeration head of the aeration device 120 through the air inlet pipe 101, the wastewater is aerated, and the filter plate may be used for performing secondary water distribution on the wastewater entering the first reaction chamber 100, so as to improve the uniformity of water distribution. Under the action of aeration, the filler filled in the first reaction chamber 100 can be completely fluidized, and the wastewater is fully contacted with the filler.
A first dosing port 1010 is arranged between the aeration device 120 and the water distributor 130 and used for dosing medicaments (such as sulfuric acid and ferrous sulfate), and a second dosing port 1020 is arranged at a position 100-1000 mm above the aeration device 120 and used for dosing an oxidant (such as hydrogen peroxide). The wastewater enters the first reaction chamber, ferrous sulfate can be added into the wastewater through the first chemical feeding port 1010 through the first chemical feeding pipe 102 to be mixed with the wastewater, sulfuric acid can be added through the first chemical feeding port 1010 to adjust the pH value of the wastewater, and hydrogen peroxide is added into the wastewater through the second chemical feeding port 1020; wherein the flow rate of the wastewater entering the first reaction chamber is controlled to be 15-20 m/h, and the aeration amount is controlled to be 0.8-1.5 m3/m2。
It should be noted that, a large number of hydroxyl groups exist on the surface of the resin filler filled in the first reaction chamber 100, the surface is hydrophilic and has a large specific surface area, and when the wastewater contacts the filler, ferric ions in the wastewater are easy to attach to the surface of the filler and crystallize. The reaction mechanism of iron crystallization is as follows:
Figure BDA0003158050060000051
in addition, the hydrogen peroxide added through the second adding port 1020 can generate hydroxyl radicals under the catalysis of ferrous ions or iron crystals in the wastewater, the hydroxyl radicals react with organic pollutants in the wastewater to break rings and open chains, and macromolecular organic matters are degraded into micromolecular organic matters.
The gas generated during the reaction process is collected by the three-phase separator 110 disposed at the top of the first reaction chamber 100, and can be recycled into the first reaction chamber 100 by connecting to the aeration device 120 through a pipe via the centrifugal fan 140 outside the reactor body. In addition, since the cross-section of the top of the first reaction chamber 100 is gradually increased from bottom to top, when the wastewater reaches the top of the first reaction chamber 100, the ascending flow rate is decreased, and due to interception by the three-phase separator 110, crystals formed by the filler filled in the first reaction chamber 100 and iron are retained in the first reaction chamber 100, and the wastewater treated by the first reaction chamber 100 enters the second reaction chamber 200.
An alkali adding port 210 is arranged at the height of 1/4-3/4 of the second reaction chamber 200 and used for adding liquid alkali into the wastewater. It should be noted that the second reaction chamber 200 plays a role of: on one hand, the degradation reaction time is further provided, so that the residual hydroxyl radicals in the wastewater, the residual hydrogen peroxide and organic matters completely react, and the further degradation reaction time is generally 0.5 to 3 hours; on the other hand, liquid alkali is added through the alkali adding port 210 for neutralization and precipitation reaction, the pH value of the wastewater is adjusted to be 7-9, so that iron ions which are not attached to the filler in the wastewater react with the added liquid alkali to generate ferric hydroxide precipitate, and meanwhile, part of complex organic matters in the water can be wrapped by the ferric hydroxide to precipitate together.
The wastewater after the neutralization and precipitation reaction enters a clarification zone 300 for further mud-water separation treatment to obtain treated effluent, and the effluent is discharged out of the reactor body through a water outlet 310. Sludge generated from the first reaction chamber 100, the second reaction chamber 200 and the clarification chamber 300 may be collected in a sludge discharge device (e.g., a sludge discharge hopper) provided at the bottom of the reactor body for periodic sludge discharge.
The method for treating wastewater by using the multi-reaction-chamber Fenton fluidized bed reactor comprises the following steps of:
s10, an iron crystal forming stage, wherein the stage aims to provide an iron hydroxide supersaturation state in the wastewater and promote the formation of iron crystals, and the iron crystal forming stage comprises the following specific processes: feeding the wastewater into the first reaction chamber at a flow rate of 15-20 m/h, and starting the aeration device to aerate the wastewater at an aeration rate of 0.8-1.5 m3/m2In a first mass ratio of 1: 2-1: 5, adding ferrous sulfate and hydrogen peroxide, wherein the mass ratio of the hydrogen peroxide to the inflow COD of the wastewater is 1: 3-1: and 0.5, controlling the pH value of the wastewater to be 4-6, wherein the filler filled in the first reaction chamber forms a fluidized state under the action of aeration, and the wastewater is fully contacted with the filler.
The ferrous ions in the wastewater are unstable, the conversion between the ferrous ions and the ferric ions exists, and in the stage, the hydrogen peroxide mainly generates hydroxyl radicals under the catalytic action of the ferrous ions, and the hydroxyl radicals can perform degradation reaction with organic matters in the wastewater; and ferric ions existing in the wastewater are easy to attach to the surface of the filler and form crystals due to the characteristics of the filler;
s20, an iron crystallization catalysis stage, wherein the stage aims to utilize the formed iron crystallization to catalyze and form hydroxyl free radicals, so that the degradation reaction effect is improved, and the specific process is as follows: feeding the wastewater into a first reaction chamber, starting an aeration device, wherein the aeration amount is 0.8-1.5 m3/m2And the mass ratio of 1: 5-1: 10, adding ferrous sulfate and hydrogen peroxide, wherein the mass ratio of the hydrogen peroxide to the inflow COD of the wastewater is 1: 3-1: and 0.5, controlling the pH value of the wastewater to be 2-4, wherein the filler filled in the first reaction chamber forms a fluidized state under the action of aeration, and the wastewater is fully contacted with the filler.
In this stage, the ferrous ions in the wastewater are small, and the hydrogen peroxide mainly generates hydroxyl radicals under the catalysis of the iron crystals formed in step S10, thereby catalytically degrading the organic matters in the wastewater.
S30, deep processing stage: and (3) feeding the wastewater treated in the step S10 or S20 into a second reaction chamber, continuing to perform deep degradation reaction for 0.5-3 h, adding liquid alkali into the second reaction chamber, adjusting the pH value of the wastewater to 7-9, performing neutralization and precipitation reaction, allowing the wastewater after the neutralization and precipitation reaction to enter a clarification zone for full precipitation, and performing mud-water separation treatment to obtain treated effluent.
S40, sediment treatment stage: the precipitates generated in the steps S10-S30 are collected in a sludge discharge device arranged at the bottom of the reactor body, and periodic sludge discharge is carried out.
The wastewater fed into the first reaction chamber in step S20 may be direct wastewater or return wastewater after the treatment in step S10.
The COD removal rate of the wastewater treated by the multi-reaction chamber Fenton fluidized bed reactor can reach 60-80%, the B/C can be improved from 0.1 to 0.3-0.4, and the iron crystallization rate can reach 70-90%.
Example 1
The multi-reaction chamber fenton fluidized bed reactor of this example has a height of 8m (effective water depth of 7m), a diameter of 8m (wherein the first reaction chamber has a diameter of 4m, the second reaction chamber has a diameter of 6.8m, and the clarification chamber has a diameter of 9.5m), a total residence time of 7.08h (wherein the first reaction chamber has a residence time of 1.26h, the second reaction chamber has a residence time of 2.36h, and the clarification chamber has a residence time of 3.46h), and the volume ratio of the first reaction chamber, the second reaction chamber, and the clarification chamber is 1: 1.87: 2.74, the ratio of the lower cross-sectional area to the upper cross-sectional area of the first reaction chamber is 0.62; and the filler filled in the first reaction chamber is anion exchange resin and macromolecular water-absorbing resin (mass ratio is 1: 1), and the alkali adding port is positioned at the 1/4 height from top to bottom of the second reaction chamber.
The wastewater treatment method specifically comprises the following steps:
s10, iron crystal forming stage: wastewater is fed into the first reaction chamber at a feed water flow rate of 18m/h (feed water flow of 70 m)3H, COD is 38000mg/L, B/C ratio is 0.1), starting the aeration device, and aeration amount is 1.5m3/m2Adding sulfuric acid to adjust the pH value of the wastewater to be 5, and adding a first mass ratio of 1: 5, the mass ratio of hydrogen peroxide to water inlet COD is 1:2, under the action of aeration, the filler filled in the first reaction chamber is in a fluidized state, the wastewater is fully contacted with the filler, a large amount of ferrous ions are contained in the wastewater, partial ferrous ions catalyze hydrogen peroxide to generate hydroxyl radicals, partial ferrous ions are oxidized into ferric ions, the ferric ions form ferric hydroxide precipitation-dissolution supersaturation state in the water, the ferric hydroxide is combined with the hydroxyl on the surface of the filler, and the iron is fixed on the surface of the filler to form crystals. The iron crystallization forming stage is 2 months, and the iron crystallization rate reaches 70 percent.
S20, iron crystallization catalysis stage: wastewater is fed into the first reaction chamber at a feed water flow rate of 18m/h (feed water flow of 70 m)3H, COD is 38000mg/L, B/C ratio is 0.1), starting the aeration device, and aeration amount is 1.5m3/m2Adding sulfuric acid to adjust the pH value of the wastewater to be 3, and adding a second mass ratio of 1: 8 ferrous sulfate and hydrogen peroxide, the mass of hydrogen peroxide and influent CODThe quantity ratio is 1:2, under the action of aeration, the filler filled in the first reaction chamber forms a fluidized state, and the filler filled in the first reaction chamber forms iron crystals in the stage, the iron crystals on the surface of the filler in the first reaction chamber catalyze hydrogen peroxide to generate a large amount of hydroxyl radicals, a small amount of ferrous ions partially react with hydrogen peroxide to generate hydroxyl radicals, and part of the ferrous ions continuously crystallize. A large amount of hydroxyl free radicals react with organic pollutants in wastewater, a ring is broken, a macromolecule organic matter is degraded into a micromolecule organic matter, gas generated in the reaction process is collected through a three-phase separator and continuously enters a first reaction chamber through a centrifugal fan, and a filler in the first reaction chamber is intercepted by the three-phase separator and is reserved in the first reaction chamber.
S30, deep processing stage: the wastewater treated by the first reaction chamber enters a second reaction chamber, the wastewater continues to undergo deep degradation reaction for 0.6h in the second reaction chamber, liquid caustic soda is added to adjust the pH value of the wastewater to 7-9, the liquid caustic soda and residual iron ions undergo neutralization precipitation reaction to generate ferric hydroxide precipitate, the ferric hydroxide precipitate can adsorb a complex generated after other organic matters in the water react, the wastewater treated by the second reaction chamber enters a clarification zone, the precipitate moves downwards, the water body flows upwards, and mud and water are further separated, so that the treated clear effluent is obtained. The COD removal rate of the effluent reaches 60 percent, the B/C ratio is improved to 0.3, and specific treatment effect data are shown in the following table 1.
S40, sediment treatment stage: the precipitates generated in the steps S10-S30 are collected in a sludge discharge device provided at the bottom of the reactor body and periodically discharged.
Table 1 detailed parameter data for water inlet and outlet of example 1
Figure BDA0003158050060000081
Example 2
The basic contents of this embodiment are the same as embodiment 1, except that: the multi-reaction chamber fenton fluidized bed reactor of this example has a height of 7m (effective water depth of 6m), a diameter of 9m (wherein the first reaction chamber has a diameter of 4m, the second reaction chamber has a diameter of 6.5m, and the clarification chamber has a diameter of 9m), a total residence time of 7.6h (wherein the first reaction chamber has a residence time of 1.5h, the second reaction chamber has a residence time of 2.5h, and the clarification chamber has a residence time of 3.6h), and the volume ratio of the first reaction chamber, the second reaction chamber, and the clarification chamber is 1.2: 1.92: 2.88, the ratio of the lower cross-sectional area to the upper cross-sectional area of the first reaction chamber is 0.67; and the filler filled in the first reaction chamber is anion exchange resin and macromolecular water-absorbing resin (mass ratio is 1: 1.5), and the alkali adding port is positioned at the 2/3 height from top to bottom of the second reaction chamber.
In the treatment process, the water inflow of the wastewater is 50m3COD of 12000mg/L, B/C ratio of 0.1, and first mass ratio of ferrous sulfate to hydrogen peroxide of 1: 2.67, the second mass ratio of ferrous sulfate to hydrogen peroxide is 1: 5.3, the mass ratio of the hydrogen peroxide to the influent COD is 1: 2.67. and in the iron crystallization formation stage of 1 month, the iron crystallization rate reaches 70%, and the wastewater continues to carry out deep degradation reaction in the second reaction chamber for 1.67 h.
After the treatment of the multi-reaction chamber Fenton fluidized bed reactor of the embodiment, the COD removal rate of the effluent reaches 60 percent, and the B/C ratio is improved to 0.3. The details are given in table 2 below.
Table 2 detailed parameter data for water inlet and outlet of example 2
Figure BDA0003158050060000082
Figure BDA0003158050060000091
Example 3
The basic contents of this embodiment are the same as embodiment 1, except that: the multi-reaction chamber fenton fluidized bed reactor of this example has a height of 5m (effective water depth of 4m), a diameter of 5.3m (wherein the first reaction chamber has a diameter of 2.2m, the second reaction chamber has a diameter of 3.8m, and the clarification chamber has a diameter of 5.3m), a total residence time of 8.8h (wherein the first reaction chamber has a residence time of 1.52h, the second reaction chamber has a residence time of 3h, and the clarification chamber has a residence time of 4.28h), and the volume ratio of the first reaction chamber, the second reaction chamber, and the clarification chamber is 1: 1.97: 2.82, the ratio of the lower sectional area to the upper sectional area of the first reaction chamber is 0.63; and the filler filled in the first reaction chamber is anion exchange resin and macromolecular water-absorbing resin (mass ratio is 1.8: 1), and the alkali adding port is positioned at the 1/3 height from top to bottom of the second reaction chamber.
In the treatment process, the water inflow of the wastewater is 10m3A COD of 8000mg/L, a B/C ratio of 0.1, and a first mass ratio of ferrous sulfate to hydrogen peroxide of 1: and 5, the second mass ratio of the ferrous sulfate to the hydrogen peroxide is 1: 10; the mass ratio of the hydrogen peroxide to the influent COD is 1: 1. the iron crystallization forming stage is 1.5 months, the iron crystallization rate reaches 90%, and the wastewater continues to carry out deep degradation reaction in the second reaction chamber for 1 h.
After the treatment of the multi-reaction chamber Fenton fluidized bed reactor of the embodiment, the COD removal rate of the effluent reaches 80 percent, and the B/C ratio is improved to 0.4. The details are given in Table 3 below.
Table 3 detailed parameter data for inlet and outlet water of example 3
Figure BDA0003158050060000092
The present invention and its embodiments have been described above schematically, the description is not restrictive, the data used are only one of the embodiments of the present invention, and the actual data combination is not limited to this. Therefore, if the person skilled in the art receives the teaching, the embodiments and examples similar to the above technical solutions shall not be designed in an inventive manner without departing from the spirit of the present invention, and shall fall within the protection scope of the present invention.

Claims (10)

1. A multi-reaction chamber Fenton fluidized bed reactor is characterized in that: the reactor comprises a reactor body, wherein a first reaction chamber (100), a second reaction chamber (200) and a clarification chamber (300) are arranged in the reactor body, the first reaction chamber (100) is positioned at the center of the inside of the reactor body, the second reaction chamber (200) and the clarification chamber (300) are positioned outside the first reaction chamber (100), and the second reaction chamber (200) is positioned between the first reaction chamber (100) and the clarification chamber (300);
wherein the top of the first reaction chamber (100) is provided with a three-phase separator (110), the bottom of the first reaction chamber (100) is provided with an aeration device (120) and a water distributor (130), the aeration device (120) is positioned above the water distributor (130), and the three-phase separator (110) is connected with the aeration device (120) through a pipeline; and the cross section of the top of the first reaction chamber (100) is gradually increased from bottom to top, and the first reaction chamber (100) is filled with a filler.
2. A multiple reaction chamber fenton fluidized bed reactor according to claim 1, characterized in that: the volume ratio among the first reaction chamber (100), the second reaction chamber (200) and the clarifying chamber (300) is (0.8-1.2): (1.8-2.2): (2.8-3.2);
or the ratio of the lower cross-sectional area to the upper cross-sectional area at the top of the first reaction chamber (100) is 0.6-0.8.
3. A multiple reaction chamber fenton fluidized bed reactor according to claim 1, characterized in that: the filler filled in the first reaction chamber (100) comprises one or two of anion exchange resin and high-molecular water-absorbing resin.
4. A multiple reaction chamber fenton fluidized bed reactor according to claim 1, characterized in that: the device comprises an alkali adding port (210), wherein the alkali adding port (210) is arranged at the height of 1/4-3/4 of a second reaction chamber (200).
5. A multiple reaction chamber fenton fluidized bed reactor according to claim 1, characterized in that: comprises a first dosing port (1010) and a second dosing port (1020), wherein the first dosing port (1010) is positioned between the aeration device (120) and the water distributor (130), and the second dosing port (1020) is positioned at the position 100 mm-1000 mm above the aeration device (120).
6. A multi-reaction chamber Fenton fluidized bed wastewater treatment method is characterized by comprising the following steps:
s10, iron crystal forming stage: feeding the wastewater into a first reaction chamber, starting an aeration device, adding ferrous sulfate and hydrogen peroxide according to a first mass ratio, wherein under the action of aeration, a filler filled in the first reaction chamber forms a fluidized state, the hydrogen peroxide generates hydroxyl radicals under the catalysis of ferrous ions, the hydroxyl radicals and organic matters in the wastewater generate degradation reaction, and iron ions in the wastewater are attached to the surface of the filler to form crystals;
s20, iron crystallization catalysis stage: feeding the wastewater into a first reaction chamber, starting an aeration device, adding ferrous sulfate and hydrogen peroxide according to a second mass ratio, wherein under the action of aeration, a filler filled in the first reaction chamber forms a fluidized state, the hydrogen peroxide generates hydroxyl radicals under the catalysis of iron crystals generated in the step S10, and the hydroxyl radicals and organic matters in the wastewater undergo a degradation reaction;
s30, deep processing stage: and (4) sending the wastewater treated in the step S10 or S20 into a second reaction chamber, continuing to perform degradation reaction for a certain time, then adding liquid caustic soda into the second reaction chamber, performing neutralization and precipitation reaction, and enabling the wastewater after the neutralization and precipitation reaction to enter a clarification area for further mud-water separation treatment to obtain treated effluent.
7. The method of claim 6, wherein the wastewater treatment system comprises: in step S10, the first mass ratio of ferrous sulfate to hydrogen peroxide is 1: 2-1: 5; in step S20, the second mass ratio of ferrous sulfate to hydrogen peroxide is 1: 5-1: 10;
or the reaction time for the wastewater to continue the degradation reaction in the step S30 is 0.5 h-3 h.
8. The method of claim 6, wherein the wastewater treatment system comprises: in step S10, adjusting the pH value of the wastewater in the first reaction chamber to 4-6; in step S20, the pH value of the wastewater in the first reaction chamber is adjusted to 2-4.
9. According to claim 6The method for treating wastewater by the Fenton fluidized bed with the multiple reaction chambers is characterized by comprising the following steps: in step S10 or S20, the flow rate of the wastewater entering the first reaction chamber is 15-20 m/h, and the aeration rate is 0.8-1.5 m3/m2。
10. The method of claim 6, wherein the wastewater treatment system comprises: also comprises S40, and a precipitate treatment stage: the precipitates generated in the steps S10-S30 are collected in a sludge discharge device arranged at the bottom of the reactor body, and periodic sludge discharge is carried out.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435142A (en) * 2013-08-01 2013-12-11 南昌大学 General-purpose internal circulation fenton reactor treating difficult-to-degrade organic wastewater
CN103755007A (en) * 2014-02-19 2014-04-30 南京大学 Fenton fluidized bed treatment device and waste water treatment method thereof
CN203715410U (en) * 2014-01-24 2014-07-16 华南理工大学 Device for treating pulping wastewater via Fenton catalytic oxidation method
CN105084513A (en) * 2015-08-18 2015-11-25 无锡乐华自动化科技有限公司 Industrial wastewater circulating fluid bed automatic treatment device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103435142A (en) * 2013-08-01 2013-12-11 南昌大学 General-purpose internal circulation fenton reactor treating difficult-to-degrade organic wastewater
CN203715410U (en) * 2014-01-24 2014-07-16 华南理工大学 Device for treating pulping wastewater via Fenton catalytic oxidation method
CN103755007A (en) * 2014-02-19 2014-04-30 南京大学 Fenton fluidized bed treatment device and waste water treatment method thereof
CN105084513A (en) * 2015-08-18 2015-11-25 无锡乐华自动化科技有限公司 Industrial wastewater circulating fluid bed automatic treatment device

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