CN113087113B

CN113087113B - Efficient heterogeneous Fenton-like reactor for high-salt refractory wastewater and application

Info

Publication number: CN113087113B
Application number: CN202110342908.0A
Authority: CN
Inventors: 石群; 韩京龙; 王爱杰; 王鸿程
Original assignee: Shenzhen Graduate School Harbin Institute of Technology
Current assignee: Shenzhen Graduate School Harbin Institute of Technology
Priority date: 2021-03-30
Filing date: 2021-03-30
Publication date: 2022-11-01
Anticipated expiration: 2041-03-30
Also published as: CN113087113A

Abstract

The invention relates to a high-efficiency heterogeneous Fenton-like reactor for high-salt degradation-resistant wastewater and a high-salt degradation-resistant wastewater treatment method thereof. The reactor comprises: the system comprises a filter bed, a water inlet system, an oxidant adding system, an aeration system, heterogeneous Fenton solid catalyst particle packing and a temperature control system. The method has remarkable advantages for the advanced treatment of the refractory wastewater, particularly for the treatment of the refractory wastewater under the condition of high chlorine, the wastewater generates Fenton and Fenton-like reactions on the surfaces of heterogeneous solid catalyst particles and in a solution, and hydroxyl radicals are efficiently and continuously generated so as to remove refractory organic matters in the wastewater. The filter bed reactor and the treatment method have the advantages of good treatment effect, low operation cost, small influence of chloride ions, convenience in management and the like, and the medicament addition is reduced, and the application prospect is wide.

Description

Efficient heterogeneous Fenton-like reactor for high-salt refractory wastewater and application

Technical Field

The invention relates to a high-efficiency heterogeneous Fenton-like reactor and a high-salt degradation-resistant wastewater treatment method thereof, in particular to a deep purification treatment method of degradation-resistant industrial wastewater applied to high chloride ion concentration.

Background

At present, the discharge of more and more waste products is inevitable, and the discharge of various and complicated industrial waste water with huge total amount brings unbearable load to the environment where people are located. If not controlled, toxic and harmful substances are distributed from the discharged water through various earth circulations, which cannot be avoided in soil, underground water, animals and plants, air, rivers, lakes and seas, and thus, the environmental protection is a serious challenge.

For various industrial wastewater, the water quality characteristics of the industrial wastewater are very different from domestic wastewater, and the characteristics of various toxic components, high salinity, difficult biodegradation and the like make the traditional wastewater treatment process dark and discolored, so that the satisfactory effect is difficult to obtain directly in the industrial wastewater treatment. Therefore, other methods for treating industrial wastewater with better treatment effect must be adopted.

The industrial wastewater not only contains conventional index parts such as COD, ammonia nitrogen, phosphorus and the like, but also often contains heavy metals, grease, high-salt solution, refractory organic matters and the like. Industrial wastewater treatment processes include physical, chemical and biochemical processes and combinations thereof. However, these methods cannot meet the discharge standards when used for treating high salt and high concentration mother liquor in industrial wastewater. The high-salt and high-concentration or biological-concentration mother liquor often has toxic characteristic pollutants (such as nitrogen heterocycles, benzene rings, fused rings, amine compounds, derivatives and the like), most of the high-salt and high-concentration or biological-concentration mother liquor has the characteristics of stable chemical structure, strong hydrophobicity and strong biological toxicity, and is difficult to effectively degrade in the traditional wastewater treatment process. Taking high-salinity wastewater as an example, if the wastewater is improperly treated, the wastewater is discharged into a water body, and the following hazards are caused: (1) affecting the growth of crops and vegetation. The excessive salt content in the water body can cause soil hardening, change the acidity and alkalinity of the soil, change the properties of cultivated land and influence the normal growth of crops and vegetation. And (2) polluting surface water and underground water. The high-salt wastewater is discharged into a natural water body to cause the water body to be acidified, and part of the high-salt wastewater also contains high-concentration toxic and nondegradable substances, so that aquatic organisms die, the self-cleaning capacity of the water body is reduced, and the water quality condition is worsened more and more. (3) influencing the normal reproduction and growth of the microorganisms. The too high concentration of inorganic salt increases the cellular osmotic pressure of the microorganism, separates the cellular plasma, destroys the microbial enzyme structure, reduces the biological activity of the metabolic enzyme, thereby inhibiting the enzymatic action of the microorganism and influencing the normal growth of the microorganism. And (4) harming human health. After the high-salt wastewater is discharged into underground water and surface water, if surrounding residents use the high-salt wastewater as domestic water, a large amount of salt enters the human body, the original cellular metabolic balance of the human body is destroyed, and the physical function and health of the human body are seriously influenced. Meanwhile, the high-salinity wastewater contains a large amount of non-degradable toxic and harmful substances, and the high-salinity wastewater enters a human body along with a food chain, so that human diseases and even death can be caused. It is therefore essential to investigate the effective treatment of high salt and high concentration mother liquor.

Currently, these refractory wastewater can be treated by advanced oxidation techniques, including but not limited to (quasi) Fenton oxidation, ozone advanced oxidation, electrochemical oxidation, ultrasonic advanced oxidation, wet oxidation, photocatalytic oxidation, etc.

The homogeneous Fenton generates a large amount of hydroxyl radicals through the reaction of hydrogen peroxide and a ferrous solution, and utilizes the strong oxidizing property of the hydroxyl radicals to treat substances which are difficult to degrade in the wastewater. The requirement on pH is strict, the pH is about 3 in the reaction, a large amount of acid-base agents need to be added, the agent cost is increased, a large amount of iron mud is generated in the process that the pH is adjusted to be neutral by ferric ions generated after the reaction, the iron mud belongs to dangerous waste, the treatment cost is increased by the generation of the large amount of iron mud, and the catalyst cannot be recycled and reused due to the fact that an oxidant and the catalyst are dissolved in a solution in homogeneous Fenton, so that the waste of the catalyst is caused. Although the homogeneous Fenton reaction has various disadvantages, the homogeneous Fenton reaction is convenient to operate and has good removal effect on certain waste water, so that the homogeneous Fenton reaction is widely applied at present.

The Fenton oxidation technology is an important technology in the treatment process of refractory industrial wastewater, and is generally considered to remove refractory organic matters through oxidation and mineralization of refractory organic matters through catalytic generation of hydroxyl radicals (. OH). Therefore, the yield of hydroxyl radicals affects the efficiency of the process. For high salt wastewater, high concentration of anions has a great influence on the removal of organic matters in the advanced oxidation process. Chloride ion is a very strong hydroxyl radical quencher, and has a very large interference to the whole radical chain reaction which we want. The following formula shows that: the generated hydroxyl free radical reacts with chloride ion to generate ClOH^-，ClOH·^-Will react to produce chlorine radicals which will then continue to react to produce

The existence of chloride ions in the reaction system can greatly reduce the yield of hydroxyl radicals in the system, and the radicals in the system mainly comprise

The form exists. Proved by experiments, the pH value<3, under the condition that the concentration of chloride ions is more than or equal to 10mM,

can occupy 99% of the total concentration of free radicals. Although it is used for

The organic matter removing agent also has oxidation capacity, but the oxidation capacity is greatly weakened compared with that of hydroxyl free radicals, and the oxidation capacity of the organic matter removing agent for organic matter which is difficult to degrade in high-salt wastewater is not enough to oxidize or even mineralize the organic matter which is difficult to degrade, so that the organic matter removing efficiency is greatly reduced. Meanwhile, as is clear from the reaction (3), the lowering of pH is advantageous for the generation of chlorine radicals and for the generation of chlorine radicals

In the general homogeneous fenton process, the pH value in the reaction process is generally about 3, and the lower pH value also increases the quenching effect of chloride ions on hydroxyl radicals. However, in the homogeneous fenton process, the oxidation capacity of hydroxyl radicals also depends on the pH value, and the adjustment of the pH value can cause the weakening of the oxidation capacity of the hydroxyl radicals and the precipitation of ferric iron, so that the treatment of high-salt degradation-resistant wastewater by using the traditional homogeneous fenton technology is undoubtedly jumped into a dead cycle.

Furthermore, sulfate and chloride ions in the high-salinity wastewater not only compete with hydroxyl radicals, but also complex with Fe (III), and the complex in the form of the sulfate and chloride ions can compete with the complex of hydrogen peroxide and Fe (III), so that the generation of a hydrogen peroxide-ferric iron complex is inhibited, and the hydrogen peroxide-ferric iron complex can generate ferrous iron and HO again₂And O₂ ^-The generated ferrous iron can continue to carry out Fenton reaction, the chain reaction is complete, and the oxidation efficiency is higher. But the compounding of the chloride and the Fe (III) can not react, but also inhibit the generation of the hydrogen peroxide-ferric iron compound, so that the whole chain reaction is incomplete, sulfate has stronger compounding capability with the Fe (III), the generation inhibition effect on the hydrogen peroxide-ferric iron compound is more obvious, and the decomposition of the hydrogen peroxide by the Fe (III) can be obviously reduced only by the existence of milligram-level sulfate. Furthermore, the first and second electrodes are provided with,

and Cl · also consume divalent iron, and after the divalent iron is consumed, insufficient divalent iron reacts with hydrogen peroxide, and the progress of the original fenton reaction is also inhibited.

Cl^-+HO·→ClOH·^- K＝4.2×10⁹ (1)

ClOH·^-→Cl^-+HO· K＝6.0×10⁹ (2)

ClOH·^-+H⁺→Cl·+H₂O K＝2.4×10¹⁰ (3)

Cl·+H₂O→ClOH·^-+H⁺ K＝1.8×10⁵ (4)

Cl·+Cl^-→Cl₂-· K＝7.8×10⁹ (5)

Cl₂-·→Cl·+Cl- K＝5.7×10⁴ (6)

The improvement of pH in the reaction process or the implementation of the Fenton reaction process under neutral conditions by Fenton-like or other catalytic oxidation processes is expected to reduce the amount of Cl produced, but has a problem that the oxidation capacity of OH is pH-dependent, and the higher the pH, the lower the oxidation capacity of OH, resulting in an undesirable or even substantially ineffective oxidation and mineralization of refractory organic substances. The waste water can not be treated well or the treatment cost is too high, which directly restricts the improvement of the productivity of enterprises and influences the economic development. This requires that we find a method for increasing the OH ratio under acidic conditions in the treatment of high-chlorine wastewater.

Under the condition that the existing homogeneous Fenton technology is more and more widely applied to advanced treatment of refractory wastewater, a series of problems of homogeneous Fenton reaction are more and more obvious, the improvement of the treatment effect and the stability become the research direction on the existing process as few as possible, heterogeneous Fenton has mild action conditions, wide pH requirement range, less iron mud generation amount and recyclable catalyst, and particularly has good effect on treatment of high-chlorine wastewater, so that the heterogeneous Fenton has wide attention.

Disclosure of Invention

In view of the problems in the prior art, the invention provides a high-efficiency heterogeneous Fenton-like reactor for high-salt degradation-resistant wastewater and a degradation-resistant wastewater treatment method thereof, and aims to provide a new way for solving the technical problems.

In order to achieve the above objects, there is provided, as an aspect of the present invention, a high-efficiency heterogeneous fenton-like reactor for high-salt refractory wastewater, comprising:

(1) The filter bed comprises a cylindrical stainless steel filter bed body, a water outlet pipe, a sampling port, a stainless steel temperature-changing interlayer, an aeration head, a baffle plate and a sealing device, wherein the aeration head, the baffle plate and the sealing device are arranged at the lower part of the filter bed;

(2) The water inlet system is connected with the filter bed through a first water inlet pipe from the lower part of the reactor;

(3) The oxidant feeding system is connected with the filter bed through a second water inlet pipe from the lower part of the reactor;

(4) The aeration system is connected with the lower part of the reactor through an aeration pipe and is connected with an aeration head;

(5) Heterogeneous Fenton solid catalyst particle packing is arranged in the filter bed, and the particle size of the lower particle packing is larger than the aperture of the baffle;

(6) And the temperature control system is connected with the temperature-changing interlayer through a pipeline.

As a preferable technical scheme of the invention, the aeration head is a spherical aeration head.

As a preferred technical scheme of the invention, the sampling tube is connected with the sampling port, and a plurality of sampling tubes are uniformly distributed along the vertical direction of the filter bed.

Wherein, aeration pipe of the aeration system is connected to the lower part of the reactor, and the gas is dispersed into small bubbles through the spherical aeration head, thereby increasing the interface mass transfer effect.

The heterogeneous Fenton solid catalyst particle filler is arranged in the filter bed, the particle size of the lower part of the heterogeneous Fenton solid catalyst particle filler is larger than the aperture of the baffle, and particles are prevented from entering an aeration system.

The sampling tubes are uniformly distributed along the vertical direction of the filter bed and are used for judging the reaction progress conditions such as mixed mass transfer effect, organic matter removal effect, hydrogen peroxide residue, iron species form and the like.

The temperature control system achieves the temperature control effect by injecting additional circulating water into the interlayer.

And, the turbulence degree is increased by air agitation to strengthen the mass transfer and further enhance the oxidation degree of products oxidized by free radicals, thereby improving the treatment effect.

The invention further provides a method for treating high-salt degradation-resistant wastewater, and the method adopts the high-efficiency heterogeneous Fenton-like reactor for the high-salt degradation-resistant wastewater, and comprises the following steps:

(1) Adding heterogeneous catalyst particles into a filter bed in advance;

(2) The inlet water is added into the filter bed from the first water inlet 3 after being pre-acidified;

(3) Hydrogen peroxide is added into the filter bed from the second water inlet 3;

(4) After reacting for a certain time, aerating by the air inlet 2, and changing pumped gas into micro bubbles by the spherical aeration head 1 to enhance mass transfer; the solid-liquid mixing is enhanced, and the solid-liquid mixing and certain small molecular organic matters after reaction continue to react to improve the removal effect;

(5) A sample in the reaction process is analyzed at a sampling port 7;

(6) If necessary, the temperature is controlled by the temperature control water inlet and

outlet

7 and 8;

(7) After the reaction, the water is discharged from a water outlet 5 for subsequent treatment.

As a preferred technical scheme of the invention, the method comprises the following steps:

pre-acidifying the wastewater in the step (2), and adjusting the pH value to about 5;

continuously adding an oxidant hydrogen peroxide through a peristaltic pump in the step (3), wherein the adding amount of the oxidant hydrogen peroxide can be adjusted in the reaction process through the measurement result of the sampling tube in the step (6);

and (4) the aeration device is started after reacting in the filter bed for a certain time, the catalyst particles realize micro-expansion under the conditions of upward flow wastewater and aeration, and the particle size of the particles is not larger than 2mm at most. The catalyst particles realize micro-expansion under the conditions of upward flow wastewater and aeration, the solid-liquid mass transfer effect is enhanced, the specific particle size is influenced by the hydraulic retention time, but the maximum particle size is not more than 2mm, so that the micro-expansion is difficult to realize due to overlarge particle size.

As a preferred technical scheme of the invention, the mass concentration of the hydrogen peroxide in the step (3) is 30%, and the mass ratio of COD to H is₂O₂And (4) adding the materials according to the ratio of = 1.

As a preferred technical scheme of the invention, the hydrogen peroxide solution in the step (3) is continuously and quantitatively added through a peristaltic pump, the flow rate of a pump body is increased first and then decreased in the adding process, and the optimal removing effect is achieved through adjustment.

In a preferred embodiment of the present invention, the catalyst is prepared from cobalt phosphide, magnetite, ferrous sulfate powder, iron oxide powder and the like in a weight ratio of (0-0.05): (0 to 0.25): (0.35-1): (0-0.35) and mixing and processing.

As a preferable technical scheme of the invention, the particle diameter of the solid particle catalyst is 0.5-2 mm, and the bulk density is 0.40-0.44 g/ml.

As a preferred technical scheme of the invention, the high-efficiency heterogeneous Fenton-like filter bed reactor operates under the condition of high-chlorine wastewater, the concentration of chloride ions is more than 3000mg/L, and the high-efficiency heterogeneous Fenton-like filter bed reactor still can obtain a good treatment effect compared with the conventional homogeneous Fenton.

Based on the technical scheme and the background technology, compared with the prior art, the high-efficiency heterogeneous Fenton-like reactor and the high-salt degradation-resistant wastewater treatment method thereof have at least one of the following advantages:

1. the adopted high-efficiency heterogeneous Fenton catalyst is an iron-based catalyst, has a micro-nano structure, is a consumption type catalyst, has a manufacturing cost less than one fourth of that of a traditional transition metal catalyst, and solves the problems that the traditional millimeter-scale catalyst is large in dosage, the catalytic effect is reduced after the alpha hydroxyl ferric oxide on the surface catalytic active site is inactivated, the use cost is too high, the popularization is difficult, and the like. On the other hand, the micro-nano catalyst can be suspended in water, has small particle size and is in a fluidized bed form, so that the problem of deactivation caused by blockage of active sites after the traditional millimeter-scale catalyst is impacted by oil, SS and the like is solved.

2. The heterogeneous catalyst can adsorb organic matters on the surface of the catalyst in advance, hydroxyl radicals generated on the surface of the solid catalyst directly react with the organic matters adsorbed on the surface of the catalyst, the service life of the generated radicals is short, the probability of contact of the hydroxyl radicals and the organic matters is increased by the aid of the pre-adsorbed catalyst, and the treatment effect is enhanced.

3. Different from the traditional method that divalent iron and hydrogen peroxide rapidly react in a short time in homogeneous Fenton to generate hydroxyl radicals at one time, the high-efficiency heterogeneous catalyst can continuously react with oxidant hydrogen peroxide, so that the generation of the hydroxyl radicals is smoother, the process of the reaction of the hydroxyl radicals and organic matters is increased, the unnecessary consumption of the hydroxyl radicals caused by the reaction of the hydroxyl radicals and the hydrogen peroxide, mutual reaction among the radicals, collision reaction with container walls and the like is reduced, and the continuous reaction of divalent iron is continuously provided, so that the generated hydroxyl radicals are reduced

And Cl · consumed all ferrous ions.

4. The upward flow mode is adopted, the filter bed is slightly expanded through the flow velocity of the filter bed and the aeration operation, and the mass transfer effect is excellent.

5. And air aeration is adopted, so that the turbulence effect is improved, the mass transfer effect is enhanced, and meanwhile, products after free radical oxidation are further oxidized by aeration, the integral oxidation effect is improved, and the treatment effect is enhanced.

6. In the process of passing wastewater through the filter bed, the filter bed can intercept suspended substances in water through gaps of the filler, and a certain filtering effect is achieved.

7. The high-efficiency heterogeneous catalyst can be recycled and repeatedly used for multiple times, so that the use cost is reduced.

8. The dosage of the oxidant in the whole reaction process is adjusted in real time, so that the reaction is convenient to optimize.

9. The operation management is convenient, and the method is suitable for improving the existing homogeneous Fenton treatment system.

Drawings

FIG. 1 is a schematic diagram of a high-efficiency heterogeneous Fenton-like reactor for high-salt refractory wastewater, according to the present invention, wherein 1 is an aeration head; 2. -an air inlet; 3-a water inlet; 4-a sampling port; 5-water outlet; 6, fixing a plate; 7-temperature control water inlet; 8-temperature control water outlet; 9-catalyst filler particles.

FIG. 2 is a schematic diagram of the effluent results of the treatment method of example 3.

Fig. 3 is a schematic diagram of the removing effect of the treatment method in embodiment 3.

FIG. 4 is a schematic diagram of the effluent results of the treatment method of example 4.

Fig. 5 is a schematic diagram of the removal effect of the treatment method of embodiment 4.

Detailed Description

In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.

Example 1

An efficient heterogeneous Fenton-like reactor for high-salt refractory wastewater, comprising:

(1) The filter bed comprises a cylindrical stainless steel filter bed body, a water outlet pipe, a sampling port, a stainless steel temperature-changing interlayer, an aeration head, a baffle and a sealing device, wherein the aeration head, the baffle and the sealing device are arranged at the lower part of the filter bed;

(4) The aeration pipe is connected to the lower part of the reactor and is connected with the aeration head;

(6) And the temperature control system is connected with the variable temperature interlayer through a pipeline.

The aeration head is a spherical aeration head.

Wherein, the sampling tube is connected with the sample connection, evenly arranges a plurality of sampling tubes along the vertical of filter bed.

Example 2

With the reactor of example 1, the treatment process included:

(1) Heterogeneous catalyst particles are added into the filter bed in advance;

(2) The inlet water is added into the filter bed from the water inlet 3 after being pre-acidified;

(3) Hydrogen peroxide is added into the filter bed from the other water inlet 3;

(4) After reacting for a certain time, aerating by the air inlet 2, and changing pumped gas into micro bubbles by the spherical aeration head 1 to enhance mass transfer;

(5) A sample in the reaction process is analyzed at a sampling port 7;

(6) The temperature is controlled by the temperature control water inlet and

outlet

7 and 8 when necessary;

Example 3

The reactor of example 1 and the treatment method of example 2 were used to treat coking wastewater of Henan, which had COD =30000mg/L and a chloride ion content of 1500mg/L. The coking wastewater has complex components, the refractory organic matters are usually difficult to be utilized by microorganisms, the conventional biological treatment can not reach the treatment standard, and the treatment efficiency is greatly reduced due to the too high concentration of chloride ions in the traditional Fenton process. The method adopts a high-efficiency heterogeneous Fenton-like reactor for treatment, and comprises the following steps: pre-acidifying inlet water until the pH value is 4-5, setting the hydraulic retention time to be 5h, adding hydrogen peroxide in batches, carrying out aeration after reacting for twenty minutes, wherein the aeration rate is about 7L/min, and adding 800mg/L of polyferric oxide and 2mg/L of PAM after reacting. The different sets of schemes are referred to in table 1. In the table 1, "the amount of the catalyst added in the middle" and "the amount of the glucose added" are added after the reaction is carried out for 2.5 hours. The water outlet results and the removal effect are shown in fig. 1 and fig. 2. As can be seen from the analysis of fig. 1 and 2:

(1) under different conditions, the COD of the effluent is 2590-8150 mg/L, and the removal rate is 72-92%;

(2) as seen from

groups

3 and 4, the addition of glucose can enhance the COD removal effect;

(3) the concentration of the catalyst only needs to reach 50g/L to achieve the best removal effect;

(4) the one-time adding effect of the catalyst is better than that of adding the catalyst in batches;

(5) the best removal effect can be obtained by adopting the non-ionic PAM coagulating sedimentation.

TABLE 1

Example 4

By using the reactor of example 1 and the treatment method of example 2, the landfill leachate stock solution generated at a certain landfill site in Guangdong was treated, and the landfill leachate stock solution had COD =11000mg/L and a chloride ion content of 1200mg/L. The landfill leachate stock solution has complex components, wherein the refractory organic matters are usually difficult to be utilized by microorganisms, the conventional biological treatment can not reach the treatment standard, and the treatment efficiency is greatly reduced due to too high concentration of chloride ions in the traditional Fenton process. The high-efficiency heterogeneous Fenton-like reactor is adopted for treatment, and the process comprises the following steps: pre-acidifying inlet water until the pH value is 4-5, setting the hydraulic retention time to be 5h, adding hydrogen peroxide in batches, carrying out aeration after reacting for twenty minutes, wherein the aeration rate is about 7L/min, and adding 600mg/L polyferric oxide and 2mg/L PAM after reacting. The different sets of flows are referred to in table 2. In the table 2, "the amount of the catalyst added in the middle" and "the amount of the glucose added" are added after the reaction is carried out for 2.5 hours. The water results and removal results are shown in figures 3 and 4. As can be seen from the analysis of fig. 3 and 4:

(1) under different conditions, the COD of the effluent is 1600-2400 mg/L, and the removal rate is 75-86%;

(2) as seen from

groups

3 and 4, the addition of glucose can enhance the COD removal effect;

(3) the concentration of the catalyst only needs to reach 20g/L to achieve the best removal effect;

(4) the one-time addition effect of the catalyst is better than that of batch addition;

(5) the best removal effect can be obtained by adopting the anionic PAM coagulating sedimentation.

TABLE 2

The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and should not be construed as limiting the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for treating high-salt degradation-resistant wastewater is characterized in that a high-efficiency out-of-phase Fenton-like reactor for the high-salt degradation-resistant wastewater is adopted,

it comprises the following steps:

(5) Heterogeneous Fenton solid catalyst particles are arranged in the filter bed, and the particle size of the lower particles is larger than the aperture of the baffle;

(6) The temperature control system is connected with the variable-temperature interlayer through a pipeline;

the high-efficiency heterogeneous Fenton-like filter bed reactor operates under the condition of high-chlorine wastewater, the concentration of chloride ions is more than 3000mg/L, and the method comprises the following steps:

(1) Adding heterogeneous Fenton solid catalyst particles into a filter bed in advance;

(2) Adding the inlet water into a filter bed from a first water inlet after the inlet water is pre-acidified, and adjusting the pH value to 5 by acidification;

(3) Adding hydrogen peroxide into the filter bed from the second water inlet, wherein the mass concentration of the hydrogen peroxide is 30 percent, and the mass ratio of COD to H is₂O₂Adding the materials according to the ratio of 1;

(4) Aerating through an air inlet after reacting for a certain time, wherein pumped gas is changed into micro bubbles by a spherical aeration head to enhance mass transfer, an aeration device is opened after reacting for twenty minutes in a filter bed, micro expansion of heterogeneous Fenton solid catalyst particles is realized under the conditions of upflow wastewater and aeration, and the heterogeneous Fenton solid catalyst is prepared by mixing cobalt phosphide, magnetite, ferrous sulfate powder and ferric oxide powder according to the ratio of (0-0.05): (0 to 0.25): (0.35-1): (0-0.35), the heterogeneous Fenton solid catalyst particles have the particle size of 0.5-2 mm and the bulk density of 0.40-0.44 g/ml, wherein the aeration amount is 7L/min;

(5) Analyzing a sample in the reaction process at a sampling port;

(6) Controlling the temperature through a temperature control water inlet and outlet;

(7) After the reaction, water is discharged from a water outlet, and subsequent treatment is carried out, wherein 800mg/L of polyferric oxide, 2mg/L of PAM and 500mg/L of glucose are added after the reaction; or 600mg/L polyferric oxide, 2mg/L PAM and 500mg/L glucose are added after the reaction.

2. The treatment method according to claim 1, wherein the hydrogen peroxide solution in the step (3) is continuously and quantitatively added through a peristaltic pump, and the flow rate of a pump body is increased first and then decreased in the adding process.

3. The processing method according to claim 1, characterized by comprising: the sampling tube is connected with the sampling port, and a plurality of sampling tubes are uniformly arranged along the vertical direction of the filter bed.