CN113371886B - 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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CN113371886B
CN113371886B CN202110783961.4A CN202110783961A CN113371886B CN 113371886 B CN113371886 B CN 113371886B CN 202110783961 A CN202110783961 A CN 202110783961A CN 113371886 B CN113371886 B CN 113371886B
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fluidized bed
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CN113371886A (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
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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
    • C02F2305/023—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 utility model discloses a Fenton fluidized bed reactor with multiple reaction chambers and a wastewater treatment method thereof, and belongs to the technical field of wastewater treatment. According to the utility model, the first reaction chamber, the second reaction chamber and the clarifying chamber are sequentially and properly arranged in the reactor body from inside to outside, and the first reaction chamber is filled with the proper filler, so that the iron crystallization rate in the Fenton fluidized bed reactor is improved, the degradation reaction of wastewater in the first reaction chamber with high-concentration filler crystals is ensured, the degradation reaction is continuously carried out in the second reaction chamber with relatively low-concentration filler crystals, and then the liquid alkali is added for precipitation reaction, so that the detoxification capacity 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 utility model belongs to the technical field of wastewater treatment, and particularly relates to a Fenton fluidized bed reactor with multiple reaction chambers and a wastewater treatment method thereof.
Background
Fenton reagent adopted by Fenton advanced oxidation technology mainly comprisesH 2 O 2 Oxidizing agent and Fe 2+ The catalyst can react under certain conditions to generate hydroxyl free radicals, and the high oxidation capacity of the hydroxyl free radicals reacts with organic matters in the wastewater to decompose and oxidize the organic matters and destroy and generate carbon dioxide and water, so that COD (chemical oxygen demand) which is difficult to decompose by organisms in the wastewater is reduced.
At present, the traditional Fenton technology generally has the defects that the utilization efficiency of Fenton reagent added in the reaction process is low, the mixing reaction of an oxidant and a catalyst is uneven, the waste of medicament is caused, and the treatment cost is increased; in addition, the reaction produces a large amount of iron sludge, the solid-liquid separation is difficult, and the iron sludge needs to be treated.
According to the search, the Chinese patent application of the application publication No. CN107162158A discloses a fluidized bed Fenton reactor and a method, wherein the fluidized bed Fenton reactor comprises a reaction tank body, a catalyst inlet for raw water and a catalyst to enter and an oxidant inlet for raw water and an oxidant to enter are arranged at the bottom of the reaction tank body, the catalyst inlet is connected with a first water distribution head, the oxidant inlet is connected with a second water distribution head, a microporous aeration head is arranged on the side part of the first water distribution head in the reaction tank body, a main reaction zone is arranged above the microporous aeration head in the reaction tank body, a filler is arranged in the main reaction zone, and a three-phase separator is arranged above the main reaction zone. The utility model ensures uniform water distribution through the arrangement of a plurality of water distribution heads, avoids crystal loss through the arrangement of the three-phase separator, and avoids oxidation corrosion of pipe fittings and equipment caused by hydroxyl radicals generated in advance before a main reaction zone through the respective mixing of raw water, oxidant, raw water and catalyst. However, the fluidized bed Fenton crystallization rate is poor and the Fenton reactor detoxification capacity is weak when the fluidized bed Fenton crystallization reactor is used for treating high-concentration wastewater.
In addition, the Chinese patent of the grant publication No. CN204714580U discloses an up-flow Fenton fluidized bed, which comprises a reaction tower with a reaction cavity and a water distributor arranged at the lower part of the reaction cavity, wherein the reaction cavity is divided into a ferrous mixing zone, a middle reaction zone and a clarification zone, the top of the reaction tower is provided with a ferrous circulation zone, a hydrogen peroxide circulation zone and a water outlet zone, the water distributor comprises a plurality of ferrous water distribution heads, a plurality of hydrogen peroxide water distribution heads and two partition boards which are arranged at intervals up and down, the plurality of ferrous water distribution heads and the plurality of hydrogen peroxide water distribution heads are uniformly arranged on the two partition boards at intervals, a hydrogen peroxide mixing zone is formed between the two partition boards, each ferrous water distribution head is communicated with the ferrous mixing zone and the middle reaction zone, each ferrous water distribution head is communicated with the hydrogen peroxide mixing zone, the hydrogen peroxide circulation zone is communicated with the ferrous mixing zone, and the hydrogen peroxide circulation zone is communicated with the hydrogen peroxide mixing zone. The design of the fluidized bed focuses on the water distribution mode of the ferrous iron and the hydrogen peroxide, and improves the uniformity of mixing of the ferrous iron and the hydrogen peroxide.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of low Fenton crystallization rate, weak Fenton reactor detoxification capacity and the like in the wastewater treatment process of a Fenton reactor in the prior art, the utility model provides a multi-reaction-chamber Fenton fluidized bed reactor and a wastewater treatment method thereof. According to the utility model, the reactor structure is reasonably designed, the first reaction chamber, the second reaction chamber and the clarifying chamber are sequentially arranged from inside to outside, and the first reaction chamber is filled with a proper filler, so that the crystallization rate of iron in the reaction chamber is improved, the catalytic degradation reaction of iron crystals can be utilized, the detoxification capacity of the reactor is improved, the Fenton treatment effect is improved, and the reactor has the advantage of high integration.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the utility model is as follows:
the utility model relates to a multi-reaction-chamber Fenton fluidized bed reactor, 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 inside 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;
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 wherein the cross section of the top of the first reaction chamber gradually increases from bottom to top, and the first reaction chamber is filled with a filler.
Preferably, the volume ratio between 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-absorbing resin.
Preferably, the Fenton fluidized bed reactor with multiple reaction chambers comprises an alkali adding port, wherein the alkali adding port is arranged at the 1/4-3/4 height 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 an aeration device and a water distributor, and the second dosing port is positioned at a position of 100-1000 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 wastewater, and the uniformity of water distribution 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 a reactor body, and the centrifugal fan is arranged on a pipeline between a three-phase separator and an aeration device; the mud discharging device is arranged at the bottom of the reactor body and is used for collecting sediment in the reaction process.
The utility model relates to a multi-reaction-chamber Fenton fluidized bed wastewater treatment method, which comprises the following steps:
s10, an 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, forming a fluidized state by filling the first reaction chamber with filler under the action of aeration, generating hydroxyl free radicals by the hydrogen peroxide under the catalysis of ferrous ions, degrading the hydroxyl free radicals with organic matters in the wastewater, and attaching iron ions in the wastewater on the surface of the filler to form crystals;
s20, iron crystallization catalysis: feeding the wastewater into a first reaction chamber, starting an aeration device, adding ferrous sulfate and hydrogen peroxide according to a second mass ratio, forming a fluidized state by filling the first reaction chamber with filler under the action of aeration, and generating hydroxyl free radicals by the hydrogen peroxide under the catalysis of iron crystals generated in the step S10, wherein the hydroxyl free radicals and organic matters in the wastewater undergo degradation reaction;
s30, advanced treatment stage: and (3) delivering the wastewater treated in the step (S10) or (S20) into a second reaction chamber, continuing to carry out degradation reaction for a certain time, then adding liquid alkali into the second reaction chamber, carrying out neutralization precipitation reaction, and delivering the wastewater after the neutralization precipitation reaction into a clarification area for further mud-water separation treatment to obtain treated effluent.
Preferably, in the multi-reaction-chamber Fenton fluidized bed wastewater treatment method, the filler filled in the first reaction chamber comprises one or two of anion exchange resin and high-molecular water-absorbing resin.
Preferably, in step S10, the first mass ratio of ferrous sulfate to hydrogen peroxide is 1: 2-1: 5, a step of; in step S20, the second mass ratio of ferrous sulfate to hydrogen peroxide is 1:5 to 1:10.
and (3) 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 hydrogen peroxide to COD of the wastewater is 1: 3-1: 0.5.
preferably, in step S10, the pH value of the wastewater in the first reaction chamber is adjusted to 4 to 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 into the first reaction chamber is 15-20 m/h, and the aeration rate is 0.8-1.5 m 3 /m 2 。
Preferably, the multi-reaction-chamber Fenton fluidized bed wastewater treatment method of the utility model further comprises S40 and a sediment treatment stage: and (3) collecting the sediment generated in the steps S10-S30 in a mud discharging device arranged at the bottom of the reactor body, and periodically discharging mud.
3. Advantageous effects
Compared with the prior art, the utility model has the beneficial effects that:
(1) According to the Fenton fluidized bed reactor with multiple reaction chambers, the first reaction chamber, the second reaction chamber and the clarifying chamber are sequentially and properly arranged in the reactor body from inside to outside, so that waste water is subjected to degradation reaction in the first reaction chamber with high-concentration filler crystals to improve biochemistry, and then the degradation reaction is continuously carried out in the second reaction chamber with relatively low-concentration filler crystals for a period of time to ensure that residual hydroxyl radicals in the waste water and residual hydrogen peroxide are thoroughly reacted with organic matters; adding liquid alkali to perform precipitation reaction, so that iron ions which are not attached to the filler are precipitated, and meanwhile, ferric hydroxide precipitation can be wrapped with partial complexing organic matters in water, thereby improving the treatment effect of the Fenton reactor;
(2) According to the Fenton fluidized bed reactor with multiple reaction chambers, the three-phase separator is arranged at the top of the first reaction chamber, the aeration device and the water distributor are arranged at the bottom of the first reaction chamber, the three-phase separator is connected with the aeration device through a pipeline, crystals formed by iron are reserved in the first reaction chamber, and collected gas is recycled into the first reaction chamber to form a highly fluidized reaction environment;
(3) According to the Fenton fluidized bed reactor with multiple reaction chambers, 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 rising flow rate is reduced, so that the pressure of the three-phase separator is smaller, and the interception effect of crystallization and the clarity of effluent are improved;
(4) According to the multi-reaction-chamber Fenton fluidized bed wastewater treatment method, in the stage of iron crystallization, a large number of hydroxyl groups exist on the surface of filled filler resin, the specific surface area is large, more sites are provided for iron crystallization, iron hydrate is easy to crystallize, the iron crystallization rate is improved, so that the formation of hydroxyl free radicals is promoted, the detoxification capacity of a first reaction chamber is improved, in the stage of iron crystallization catalysis, the formed iron crystallization is used for catalyzing the generation of hydroxyl free 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-chamber Fenton fluidized bed reactor according to the present utility model;
in the figure:
100. a first reaction chamber; 101. an air inlet pipe; 102. a first feeding tube; 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. an alkali adding port; 300. a clarification chamber; 310. a water outlet;
400. a mud discharging device; 1010. a first dosing port; 1020. and a second medicine adding port.
Detailed Description
The utility model is further described below in connection with specific embodiments.
As shown in fig. 1, the multi-reaction-chamber Fenton fluidized bed reactor of the present utility model 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 central position inside the reactor body, the second reaction chamber 200 and the clarification chamber 300 are positioned outside the first reaction chamber 100, the second reaction chamber 200 is positioned 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 may be cylindrical, and the first reaction chamber 100 is a central cylinder inside 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 increased from bottom to top, and the ratio of the lower cross section area to the upper cross section area of the top of the first reaction chamber 100 is in the range of 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 including one or both of an anion exchange resin and a high molecular absorbent resin. Anion exchange resins include, but are not limited to, model D201, D213, D202, etc.; the high molecular water-absorbing resin includes, but is not limited to, polymers formed from monomers such as polyacrylic acid, polyacrylate alcohol, polyacrylamide, polyvinyl alcohol, polyacrylonitrile, ethylene oxide, starch, carboxymethyl cellulose, and the like.
The water distributor 130 may be a cyclone water distributor, the wastewater enters the water distributor 130 through the water inlet pipe 103, then enters the first reaction chamber 100 under the action of the water distributor, the aeration device 120 is started, 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 subjected to aeration treatment, and the filter plate can be used for carrying out secondary water distribution on the wastewater entering the first reaction chamber 100 so as to improve the water distribution uniformity. Under the action of aeration, the filler filled in the first reaction chamber 100 can thoroughly form a fluidized state, and the wastewater is fully contacted with the filler.
A first dosing port 1010 for dosing a medicament (e.g., sulfuric acid, ferrous sulfate) is provided between the aeration device 120 and the water distributor 130, and a second dosing port 1020 for dosing an oxidizing agent (e.g., hydrogen peroxide) is provided at a position of 100-1000 mm above the aeration device 120. The wastewater enters the first reaction chamber, ferrous sulfate can be added into the wastewater through the first medicine inlet pipe 102 and the first medicine inlet 1010 so as to be mixed with the wastewater, sulfuric acid can be added through the first medicine inlet 1010, the pH value of the wastewater is regulated, and hydrogen peroxide is added into the wastewater through the second medicine inlet 1020; wherein, the flow rate of 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 m 3 /m 2 。
It should be noted that, the surface of the resin filler filled in the first reaction chamber 100 has a large number of hydroxyl groups, the surface is hydrophilic and has a large specific surface area, ferric ions in the wastewater are easy to adhere to the surface of the filler and crystallize when the wastewater contacts the filler, and compared with the prior art, the present utility model provides more sites for forming iron crystals by using the filler containing a large number of hydroxyl groups, so that the iron crystallization rate has a remarkable advantage. The reaction mechanism of iron crystallization is as follows:
Figure BDA0003158050060000051
and, hydrogen peroxide added through the second dosing port 1020 can generate hydroxyl radical under the catalysis of ferrous ions or iron crystals in the wastewater, and the hydroxyl radical reacts with organic pollutants in the wastewater to break the ring and open the chain, so that macromolecular organic matters are degraded into micromolecular organic matters.
The gas generated during the reaction is collected through the three-phase separator 110 provided at the top of the first reaction chamber 100 and can be circulated into the first reaction chamber 100 by being connected 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, the upward flow rate is reduced when the wastewater reaches the top of the first reaction chamber 100, and crystals formed by the filler filled in the first reaction chamber 100 and iron are retained in the first reaction chamber 100 due to interception of the three-phase separator 110, and the wastewater treated by the first reaction chamber 100 enters the second reaction chamber 200.
An alkali adding port 210 is provided at 1/4 to 3/4 of the height of the second reaction chamber 200 for adding liquid alkali to the wastewater. It should be noted that the second reaction chamber 200 plays the role of: on the one hand, the degradation reaction time is further provided, so that the residual hydroxyl free radicals in the wastewater, the residual hydrogen peroxide and organic matters completely react, and the time for the further degradation reaction is generally 0.5-3 h; on the other hand, the alkali adding port 210 is used for adding liquid alkali to perform neutralization precipitation reaction, the pH value of the wastewater is regulated to 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, the ferric hydroxide can be wrapped with water to partially complex organic matters to precipitate together.
The wastewater after the neutralization precipitation reaction then enters a clarification zone 300 for further mud-water separation treatment, and treated effluent is obtained and discharged out of the reactor body through a water outlet 310. The sludge generated in the first reaction chamber 100, the second reaction chamber 200, and the settling chamber 300 may be collected in a sludge discharge device (e.g., a sludge discharge hopper) provided at the bottom of the reactor body, to be periodically discharged.
A method for wastewater treatment by utilizing the Fenton fluidized bed reactor with multiple reaction chambers comprises the following steps:
s10, an iron crystallization forming stage, wherein the stage aims at providing supersaturation state of ferric hydroxide in wastewater to promote iron crystallization, and the specific process is as follows: delivering the wastewater into a first reaction chamber at a flow rate of 15-20 m/h, starting an aeration device, and enabling the aeration quantity to be 0.8-1.5 m 3 /m 2 In 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 COD of the wastewater is 1: 3-1: and 0.5, controlling the pH value of the wastewater to be between 4 and 6, and forming a fluidization state by filling the filler in the first reaction chamber under the action of aeration, wherein the wastewater is fully contacted with the filler.
Ferrous ions in the wastewater are unstable, conversion between ferrous ions and ferric ions exists, and in the stage, hydrogen peroxide mainly generates hydroxyl free radicals under the catalysis of the ferrous ions, and the hydroxyl free radicals can be subjected to 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 at catalyzing and forming hydroxyl free radicals by utilizing the formed iron crystals, 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, and enabling the aeration quantity to be 0.8-1.5 m 3 /m 2 In a second mass ratio of 1:5 to 1:10, ferrous sulfate and hydrogen peroxide are added, and the mass ratio of the hydrogen peroxide to the COD of the wastewater is 1: 3-1: and 0.5, controlling the pH value of the wastewater to be between 2 and 4, and forming a fluidization state by filling the filler in the first reaction chamber under the action of aeration, wherein the wastewater is fully contacted with the filler.
In this stage, the ferrous ions in the wastewater are small, and hydrogen peroxide mainly generates hydroxyl radicals under the catalysis of the iron crystals formed in step S10, thereby catalyzing and degrading organic matters in the wastewater.
S30, advanced treatment stage: and (3) delivering the wastewater treated in the step (S10) or (S20) into a second reaction chamber, continuing to carry out deep degradation reaction for 0.5-3 h, then adding liquid caustic soda into the second reaction chamber, adjusting the pH value of the wastewater to 7-9, carrying out neutralization precipitation reaction, and fully precipitating the wastewater after the neutralization precipitation reaction in a clarification area, and further carrying out mud-water separation treatment to obtain treated effluent.
S40, sediment treatment: and (3) collecting the sediment generated in the steps S10-S30 in a mud discharging device arranged at the bottom of the reactor body, and periodically discharging mud.
The wastewater fed into the first reaction chamber in step S20 may be direct wastewater or may be returned wastewater after the treatment in step S10.
The COD removal rate of the wastewater treated by the Fenton fluidized bed reactor with multiple reaction chambers can reach 60% -80%, the B/C can be increased 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 7 m), 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 settling chamber has a diameter of 9.5 m), 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 settling chamber has a residence time of 3.46 h), and a volume ratio among the first reaction chamber, the second reaction chamber, and the settling 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 macromolecule water absorption resin (the mass ratio is 1:1), and the alkali adding port is positioned at 1/4 height of the second reaction chamber from top to bottom.
The wastewater treatment method specifically comprises the following steps:
s10, an iron crystal forming stage: feeding the wastewater into the first reaction chamber at a water inflow rate of 18m/h (water inflow of 70m 3 /h, COD of 38000mg/L and B/C ratio of 0.1), opening the aeration device, and exposingThe gas flow is 1.5m 3 /m 2 Adding sulfuric acid to adjust the pH value of the wastewater to 5, and adding a first mass ratio of 1:5 ferrous sulfate and hydrogen peroxide, wherein the mass ratio of the hydrogen peroxide to COD of the inlet water is 1:2, the filler filled in the first reaction chamber forms a fluidized state under the action of aeration, the wastewater is fully contacted with the filler, the wastewater contains a large amount of ferrous ions, part of ferrous ions catalyze the hydrogen peroxide to generate hydroxyl free radicals, part of ferrous ions are oxidized into ferric ions, the ferric ions form ferric hydroxide precipitation-dissolution supersaturation state in the water, ferric hydroxide is combined with hydroxyl on the surface of the filler, and iron is fixed on the surface of the filler to form crystals. The iron crystallization stage is 2 months, and the iron crystallization rate reaches 70%.
S20, iron crystallization catalysis: feeding the wastewater into the first reaction chamber at a water inflow rate of 18m/h (water inflow of 70m 3 /h, COD of 38000mg/L, B/C ratio of 0.1), opening the aeration device, and aeration amount of 1.5m 3 /m 2 Adding sulfuric acid to adjust the pH value of the wastewater to 3, and adding a second mass ratio to 1:8, the mass ratio of the ferrous sulfate to the hydrogen peroxide to the COD of the inflow water is 1:2, under the action of aeration, the filler filled in the first reaction chamber forms a fluidized state, the filler filled in the first reaction chamber forms iron crystals, the iron crystals on the surface of the filler in the first reaction chamber catalyze the hydrogen peroxide to generate a large amount of hydroxyl free radicals, a small amount of ferrous ions partially react with the hydrogen peroxide to generate the hydroxyl free radicals, and the part of the hydroxyl free radicals continue to crystallize. A large number of hydroxyl radicals react with organic pollutants in the wastewater, the ring is broken, the chains are opened, macromolecular organic matters are degraded into micromolecular organic matters, 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 filler in the first reaction chamber is intercepted by the three-phase separator and remains in the first reaction chamber.
S30, advanced treatment stage: the wastewater treated by the first reaction chamber enters the second reaction chamber, the wastewater is subjected to deep degradation reaction for 0.6h in the second reaction chamber, then liquid alkali is added to adjust the pH value of the wastewater to 7-9, the liquid alkali and residual iron ions are subjected to neutralization precipitation reaction to generate ferric hydroxide precipitates, the complex generated after other organic matters in the water can be adsorbed in the ferric hydroxide precipitation process, the wastewater treated by the second reaction chamber enters a clarification area, the precipitates move downwards, the water body flows upwards, and further mud-water separation is carried out, so that the treated clear effluent is obtained. The COD removal rate of the effluent reaches 60%, the B/C ratio is improved to 0.3, and the specific treatment effect data are shown in the following table 1.
S40, sediment treatment: the precipitate produced in steps S10 to S30 is collected in a sludge discharge device provided at the bottom of the reactor body and periodically discharged.
Table 1 detailed water inlet and outlet parameter data for example 1
Figure BDA0003158050060000081
Example 2
The basic content of this embodiment is 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 6 m), 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 settling chamber has a diameter of 9 m), 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 settling chamber has a residence time of 3.6 h), and a volume ratio among the first reaction chamber, the second reaction chamber, and the settling 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 filling material in the first reaction chamber is anion exchange resin and macromolecule water absorption resin (the mass ratio is 1:1.5), and the alkali adding port is positioned at the 2/3 height of the second reaction chamber from top to bottom.
In the treatment process, the water inflow of the wastewater is 50m 3 The COD was 12000mg/L, the B/C ratio was 0.1, and the first mass ratio of ferrous sulfate to hydrogen peroxide was 1:2.67, the second mass ratio of ferrous sulfate to hydrogen peroxide is 1:5.3, the mass ratio of hydrogen peroxide to COD of the inlet water is 1:2.67. and in the iron crystallization forming stage for 1 month, the iron crystallization rate reaches 70%, and the wastewater is subjected to deep degradation reaction in the second reaction chamber for 1.67h.
After the treatment of the multi-reaction-chamber Fenton fluidized bed reactor in the embodiment, the COD removal rate of the effluent reaches 60%, and the B/C ratio is improved to 0.3. The detailed data are shown in Table 2 below.
Table 2 detailed water inlet and outlet parameter data for example 2
Figure BDA0003158050060000082
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Figure BDA0003158050060000091
Example 3
The basic content of this embodiment is 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 4 m), 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 settling chamber has a diameter of 5.3 m), 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 settling chamber has a residence time of 4.28 h), and a volume ratio among the first reaction chamber, the second reaction chamber, and the settling chamber is 1:1.97:2.82, the ratio of the lower cross-sectional area to the upper cross-sectional area of the first reaction chamber is 0.63; and the filler filled in the first reaction chamber is anion exchange resin and macromolecule water absorption resin (the mass ratio is 1.8:1), and the alkali adding port is positioned at 1/3 height of the second reaction chamber from top to bottom.
In the treatment process, the water inflow of the wastewater is 10m 3 And/h, COD is 8000mg/L, B/C ratio is 0.1, and first mass ratio of ferrous sulfate to hydrogen peroxide is 1:5, the second mass ratio of ferrous sulfate to hydrogen peroxide is 1:10; the mass ratio of hydrogen peroxide to COD of the inflow water is 1:1. and in the iron crystallization forming stage, the iron crystallization rate reaches 90% for 1.5 months, and the wastewater is subjected to deep degradation reaction in the second reaction chamber for 1h.
After the multi-reaction-chamber Fenton fluidized bed reactor treatment in the embodiment, the COD removal rate of the effluent reaches 80%, and the B/C ratio is improved to 0.4. The detailed data are shown in Table 3 below.
TABLE 3 Water in and out detail parameter data for example 3
Figure BDA0003158050060000092
The utility model and its embodiments have been described above schematically, without limitation, and the data used is only one of the embodiments of the utility model, and the actual data combination is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the utility model should not be construed as being limited to the embodiments and examples similar to the technical solutions without departing from the spirit of the utility model.

Claims (9)

1. A multi-reaction-chamber Fenton fluidized bed reactor, characterized in that: including the reactor body, be provided with first reaction chamber (100), second reaction chamber (200) and clarification chamber (300) in the reactor body, first reaction chamber (100) are located the inside central point of reactor body and put, second reaction chamber (200) and clarification chamber (300) are located the outside of first reaction chamber (100), and second reaction chamber (200) are located between first reaction chamber (100) and clarification chamber (300), the volume ratio between first reaction chamber (100), second reaction chamber (200) and clarification chamber (300) is (0.8 ~ 1.2): (1.8-2.2): (2.8-3.2);
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), the three-phase separator (110) is connected with the aeration device (120) through a pipeline, the first reaction chamber (100) is communicated with the upper part of the second reaction chamber (200) through the three-phase separator (110), the bottom of the second reaction chamber (200) is communicated with a clarification chamber (300), and the top of the clarification chamber (300) is provided with a water outlet (310); and is also provided with
A first dosing port (1010) is arranged between the aeration device (120) and the water distributor (130), the first dosing port (1010) is used for dosing medicament sulfuric acid or ferrous sulfate, a second dosing port (1020) is arranged at the position 100-1000 mm above the aeration device (120), and the second dosing port (1020) is used for dosing oxidant hydrogen peroxide; the cross section of the top of the first reaction chamber (100) gradually increases from bottom to top, and the first reaction chamber (100) is filled with filler.
2. A multi-reaction-chamber Fenton fluidized bed reactor according to claim 1, wherein: the ratio of the lower cross-sectional area to the upper cross-sectional area of the top of the first reaction chamber (100) ranges from 0.6 to 0.8.
3. A multi-reaction-chamber Fenton fluidized bed reactor according to claim 1, wherein: the filler filled in the first reaction chamber (100) comprises one or two of anion exchange resin and macromolecule water absorption resin.
4. A multi-reaction-chamber Fenton fluidized bed reactor according to claim 1, wherein: comprises an alkali adding port (210), wherein the alkali adding port (210) is arranged at the 1/4~3/4 height of the second reaction chamber (200).
5. A multi-reaction-chamber Fenton fluidized bed wastewater treatment method is characterized by comprising the following steps:
s10, an 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, forming a fluidized state by filling the first reaction chamber with filler under the action of aeration, generating hydroxyl free radicals by the hydrogen peroxide under the catalysis of ferrous ions, degrading the hydroxyl free radicals with organic matters in the wastewater, and attaching iron ions in the wastewater on the surface of the filler to form crystals;
s20, iron crystallization catalysis: feeding the wastewater into a first reaction chamber, starting an aeration device, adding ferrous sulfate and hydrogen peroxide according to a second mass ratio, forming a fluidized state by filling the first reaction chamber with filler under the action of aeration, and generating hydroxyl free radicals by the hydrogen peroxide under the catalysis of iron crystals generated in the step S10, wherein the hydroxyl free radicals and organic matters in the wastewater undergo degradation reaction;
s30, advanced treatment stage: delivering the wastewater treated in the step S10 or the step S20 into a second reaction chamber, continuing to carry out degradation reaction for a certain time, then adding liquid alkali into the second reaction chamber, carrying out neutralization precipitation reaction, and delivering the wastewater after the neutralization precipitation reaction into a clarification area for further mud-water separation treatment to obtain treated effluent;
in step S10, the first mass ratio of ferrous sulfate to hydrogen peroxide is 1: 2-1: 5, a step of; in step S20, the second mass ratio of ferrous sulfate to hydrogen peroxide is 1: 5-1: 10.
6. the multi-reaction-chamber Fenton fluidized bed wastewater treatment method according to claim 5, wherein: and (3) continuously carrying out degradation reaction on the wastewater in the step (S30) for 0.5-3 hours.
7. The multi-reaction-chamber Fenton fluidized bed wastewater treatment method according to claim 5, wherein: in the step S10, the pH value 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.
8. The multi-reaction-chamber Fenton fluidized bed wastewater treatment method according to claim 5, wherein: 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 m 3 /m 2 。
9. The multi-reaction-chamber Fenton fluidized bed wastewater treatment method according to claim 5, wherein: and S40, a sediment treatment stage: and (3) collecting the sediment generated in the steps S10-S30 in a mud discharging device arranged at the bottom of the reactor body, and periodically discharging mud.
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