CN119158627A

CN119158627A - A Fenton catalyst and its preparation method and application

Info

Publication number: CN119158627A
Application number: CN202411583118.1A
Authority: CN
Inventors: 张澜; 沈煜鹏; 朱冬冬; 肖静; 杭小帅
Original assignee: Nanjing Institute of Environmental Sciences MEP
Current assignee: Nanjing Institute of Environmental Sciences MEP
Priority date: 2024-11-07
Filing date: 2024-11-07
Publication date: 2024-12-20
Anticipated expiration: 2044-11-07
Also published as: CN119158627B

Abstract

The invention discloses a Fenton catalyst and a preparation method and application thereof, and belongs to the technical field of wastewater treatment. According to the preparation method of the Fenton catalyst, a solution containing ferric trichloride hexahydrate, terephthalic acid and riboflavin (VB ₂) is subjected to a hydrothermal reaction to obtain the Fenton catalyst VB ₂ @MIL-101 (Fe), the temperature of the hydrothermal reaction is 110-150 ℃ and the time is 20-24 hours, the mole ratio of the ferric trichloride hexahydrate, the terephthalic acid and the riboflavin is 2:1 (0.1-0.6), and the prepared Fenton catalyst can be used for improving the circulation efficiency of Fe ³⁺/Fe²⁺.

Description

Fenton catalyst and preparation method and application thereof

Technical Field

The invention relates to the technical field of wastewater treatment, in particular to a Fenton catalyst and a preparation method and application thereof.

Background

The problem of abuse of antibiotics and effective treatment of antibiotic wastewater in livestock and poultry and aquaculture industry is increasingly attracting attention. Among them, various antibiotics such as enrofloxacin, florfenicol, sulfamethoxazole and the like are often used in the breeding industry for preventing and treating fish diseases and improving the yield. The medicines play an important role in preventing and treating bacterial diseases, erythro-fin diseases, enteritis and the like. However, the long-term use and improper handling of antibiotics can lead to serious environmental pollution and ecological risks. Antibiotics in the environment can enter a water body through surface runoff, exist in river sediment for a long time, inhibit the growth of certain organisms, and induce the generation of drug resistance bacteria and resistance genes.

The current common methods for removing antibiotics mainly comprise advanced oxidation treatment, biological treatment and ecological treatment. Advanced oxidation is often used for removing antibiotics in water, and a relatively high-efficiency removal effect can be achieved by regulating and controlling various catalytic conditions. The Fenton oxidation method utilizes hydrogen peroxide (H ₂O₂) and ferrous ions to generate hydroxyl free radicals with strong oxidability by mixing, so as to degrade pollutants in wastewater, and has the advantages of high efficiency, simplicity in operation and the like. Fe plays a role of a catalyst in Fenton oxidation, and hydrogen peroxide is circularly catalyzed by Fe ³⁺/Fe²⁺ to generate hydroxyl free radicals. In the traditional homogeneous Fenton degradation organic wastewater process, the optimal effect can be achieved only within the pH range of 2-4, the applicable range of the pH is narrower, and meanwhile, precipitation of Fe ³⁺ can occur in the process, so that a large amount of iron mud is generated.

The homogeneous Fenton technology which uses an iron-based solid catalyst to replace Fe ²⁺ in the homogeneous Fenton reaction has the advantages of high reaction speed, wide pH range, low iron mud amount and the like and is widely paid attention to. The iron-based Metal Organic Frameworks (MOFs), which are an advanced catalytic material, are composed of organic ligands and iron ions, form a pore structure with high specific surface area and multiple active sites, have a highly controllable structure, and also show excellent catalytic performance, and are ideal catalysts in heterogeneous Fenton oxidation processes. However, chinese patent publication No. CN118543364a discloses a preparation method and application of a NH ₂ -MIL-101 (Fe) -derived Fe-Cu bimetallic catalyst, in which a supramolecular self-assembly-hydrothermal process is adopted in the technical scheme, 2-amino terephthalic acid, ferric chloride hexahydrate, copper nitrate trihydrate, DMF and the like are used as raw materials, in the process of synthesizing a precursor of Fe-Cu bimetallic carbon material, amination modification of MIL-101 is synchronously implemented, and Fe and Cu active sites are exposed through a low-temperature carbonization process, so as to increase reactive active sites, but the cycle efficiency of Fe ³⁺/Fe²⁺ cannot be improved.

Disclosure of Invention

1. Technical problem to be solved by the invention

Aiming at the defect of low Fe ³⁺/Fe²⁺ circulation efficiency in the Fenton oxidation process in the prior art, the Fenton catalyst is provided, and a preparation method and application thereof are provided.

2. Technical proposal

In order to achieve the above purpose, the technical scheme provided by the invention is as follows:

the preparation method of the Fenton catalyst comprises the following steps:

Carrying out hydrothermal reaction on a solution containing ferric trichloride hexahydrate, terephthalic acid and riboflavin (VB ₂) to obtain a Fenton catalyst VB ₂ @MIL-101 (Fe);

The temperature of the hydrothermal reaction is 110-150 ℃ and the time is 20-24 hours;

The mole ratio of the ferric trichloride hexahydrate, the terephthalic acid and the riboflavin is 2:1 (0.1-0.6).

Preferably, the mole ratio of the ferric trichloride hexahydrate, the terephthalic acid and the riboflavin is 2:1 (0.2-0.3).

Further, the solvent of the solution includes N, N-Dimethylformamide (DMF).

Preferably, the solvent of the solution is N, N-dimethylformamide.

Further, in the solution, the ratio of ferric trichloride hexahydrate to the solvent is 5mmol (30-50 mL).

Further, the hydrothermal reaction further comprises centrifugation, washing, drying and grinding.

Further, the washing may be washing with DMF and ethanol.

For example, washing with DMF and ethanol is performed three times each.

Further, the drying temperature is 50-90 ℃ and the drying time is 6-12 hours.

Further, the grinding may be performed using an agate mortar.

Further, the solution containing ferric trichloride hexahydrate, terephthalic acid and riboflavin can be obtained by the following means:

s1, respectively dissolving ferric trichloride hexahydrate and terephthalic acid in DMF to obtain ferric chloride solution and terephthalic acid solution;

S2, stirring and mixing an iron chloride solution and a terephthalic acid solution for 30-120 min to obtain a mixed solution C;

s3, dissolving the riboflavin in the mixed solution C, and stirring and mixing for 30-120 min to obtain the solution containing ferric trichloride hexahydrate, terephthalic acid and riboflavin.

According to the solution containing ferric trichloride hexahydrate, terephthalic acid and riboflavin prepared by the method, reactants are mixed more uniformly, so that the hydrothermal reaction is facilitated, and the uniformity of the hydrothermal reaction is improved.

Furthermore, the invention also provides the Fenton catalyst prepared by the preparation method.

Further, the Fenton catalyst comprises MIL-101 (Fe), and riboflavin is loaded on the MIL-101 (Fe).

Further, the crystal structure of the Fenton catalyst is a regular octahedral structure.

Further, the particle size of the Fenton catalyst is 500-600 nm.

The invention also provides the Fenton catalyst prepared by the preparation method or the method for degrading florfenicol in water by using the Fenton catalyst.

Further, the Fenton catalyst is added into a water body containing florfenicol, hydrogen peroxide is added, and the oscillation reaction is carried out.

Further, the concentration of the florfenicol in the water body containing the florfenicol is 1-50 mg/L.

Further, the amount of Fenton catalyst is 0.2-0.5 g/L.

Further, the hydrogen peroxide is used in an amount of 10-30 mmol/L.

Further, after the oscillation reaction, the water after the reaction can be filtered by a filter membrane to recover the catalyst.

Further, the filter membrane may be a water-based filter membrane having a pore size of 0.45. Mu.m.

The invention also provides a heterogeneous Fenton reaction system,

Comprises a Fenton reaction tank and a reaction device,

A separation part is arranged in the Fenton reaction tank,

The separation part divides the Fenton reaction tank into a Fenton reaction zone and a water outlet sedimentation zone;

The Fenton reaction zone is provided with a water inlet and a medicine inlet;

The Fenton reaction zone is provided with a fixed component, a lifting component and a catalyst loading component which are connected in sequence,

The catalyst loading part is loaded with the Fenton catalyst prepared by the preparation method or the Fenton catalyst;

The water outlet sedimentation zone is provided with a mud outlet and a water outlet.

Further, the volume ratio of the Fenton reaction Chi Zhongfen ton reaction area to the effluent precipitation area is 4-2:1.

Further, the catalyst loading part is rotatably connected with the lifting part;

The catalyst supporting member is connected with a driving member.

Further, the effluent sedimentation zone is provided with a sludge collecting component,

The sludge collecting component is connected with the separating component, and the sludge collecting component is connected with the sludge outlet.

Further, the fixed part is a fixed rod, and two ends of the fixed rod are fixedly connected with the Fenton reaction tank.

Further, the device also comprises a weir, and the separation part is connected with the weir.

Further, the overflow weir is a round-corner overflow weir, and the angle of the weir mouth of the round-corner overflow weir is 60-80 degrees.

Further, the separation component is a separation plate, and the angle between the separation plate and the horizontal plane is 45-60 degrees.

Further comprises a water inlet tank and a medicament adding component,

The water inlet water tank is connected with a water inlet of the Fenton reaction zone;

the medicament adding component is connected with a medicament inlet of the Fenton reaction zone.

Further, a water outlet of the water outlet sedimentation area is connected with a water drain pipe.

3. Advantageous effects

Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:

(1) The Fenton catalyst provided by the invention is prepared by a hydrothermal method, the preparation method is simple, the used raw materials are cheap and easily available materials, and the preparation method is easy for mass production.

(2) The Fenton catalyst provided by the invention has the advantages that VB ₂ is loaded on MIL-101 (Fe), so that electron transfer can be promoted, the cycle efficiency of Fe ³⁺/Fe²⁺ is improved, more hydroxyl free radicals are promoted to be generated, the degradation efficiency of organic pollutants in pharmaceutical wastewater in a Fenton reaction is improved, the problems of low oxidation-reduction efficiency, substandard effluent quality and the like of the catalyst are effectively solved, and the Fenton catalyst has a wide application prospect.

(3) In the method for degrading florfenicol in the water body, the Fenton catalyst provided by the invention can effectively degrade florfenicol in the water body, the degradation rate can reach more than 95%, and the Fenton catalyst has a wide application prospect in the treatment of aquaculture tail water and antibiotic organic wastewater.

(4) The heterogeneous Fenton reaction system provided by the invention can control the addition of the Fenton catalyst and the start and stop of the Fenton reaction, and ensure that pollutants in wastewater are fully degraded in the Fenton reaction process.

Drawings

FIG. 1 is a SEM (scanning electron microscope) image of a modified iron-based MOFs material VB ₂ @MIL-101 (Fe) in example 1 of the invention;

FIG. 2 is an X-ray diffraction XRD pattern of modified iron-based MOFs material VB ₂ @MIL-101 (Fe) in example 1 of the present invention;

FIG. 3 is a schematic diagram showing degradation of modified iron-based MOFs material VB ₂ @MIL-101 (Fe) in application example 1 and unmodified iron-based MOFs material MIL-101 (Fe) in comparative example 1 containing a10 mg/L florfenicol drug solution;

FIG. 4 is a graph showing impedance tests of modified iron-based MOFs material VB ₂ @MIL-101 (Fe) in example 1 of the present invention and unmodified iron-based MOFs material MIL-101 (Fe) in comparative example 1;

FIG. 5 is a graph showing impedance measurements of modified iron-based MOFs materials VB ₂ @ MIL-101 (Fe) of examples 1-3 and comparative example 2 of the present invention;

FIG. 6 is a schematic diagram showing the perspective structure of a heterogeneous Fenton reaction system according to embodiment 4 of the present invention;

FIG. 7 is a schematic diagram of a heterogeneous Fenton reaction system according to embodiment 4 of the present invention;

FIG. 8 is a schematic diagram of an operation room in embodiment 4 of the present invention;

FIG. 9 is a schematic view of a partial cross-sectional structure of the weir of FIG. 6 according to the present invention.

Reference numerals in the schematic drawings illustrate:

100. Fenton reaction tank 110, fixing part 120, lifting part 130, driving part 140, catalyst loading part 150, overflow weir 151, supporting section 152, overflow section 153, buffer section 160, separating part 170, sludge collecting part 180, second liquid conveying part;

200. A water inlet tank 210, a first liquid delivery member;

300. The device comprises an operation room, a third liquid conveying component, a medicament adding component, a water sample collecting component, a fourth liquid conveying component and a reagent adding component.

Detailed Description

The present disclosure may be understood more readily by reference to the following description taken in conjunction with the examples, all of which form a part of this disclosure. It is to be understood that this disclosure is not limited to the particular products, methods, conditions, or parameters described and/or shown herein. Further, the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting unless otherwise indicated.

It is also to be appreciated that certain features of the disclosure may, for clarity, be described herein in the context of separate embodiments, but may also be provided in combination with each other in a single embodiment. That is, each separate embodiment is contemplated to be combinable with any other embodiment, and to be considered as representing a different embodiment, unless expressly incompatible or specifically excluded. Conversely, various features of the disclosure that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Finally, although a particular embodiment may be described as part of a series of steps or as part of a more general structure, each step or sub-structure itself may also be considered a separate embodiment.

Unless otherwise indicated, it should be understood that each individual element in the list and each combination of individual elements in the list are to be construed as different embodiments. For example, a list of embodiments denoted as "A, B or C" should be interpreted to include embodiments "a", "B", "C", "a or B", "a or C", "B or C" or "A, B or C".

In this disclosure, the singular forms "a," "an," and "the" also include the corresponding plural referents, and reference to a particular value includes at least the particular value unless the context clearly dictates otherwise. Thus, for example, reference to "a substance" is a reference to at least one of such a substance and equivalents thereof.

When the term "is used in conjunction. And/or when items are described by" etc., the description should be understood to include any one of the associated listed items, as well as all combinations of one or more of the items.

In general, the use of the term "about" refers to an approximation that may vary depending on the desired properties obtained by the disclosed subject matter, and will be interpreted in a context-dependent manner based on the function. Thus, one of ordinary skill in the art will be able to interpret a degree of variability on an individual case basis. In some cases, the number of significant digits used in expressing a particular value can be a representative technique for determining the variance allowed by the term "about. In other cases, a gradient in a series of values may be used to determine the range of differences permitted by the term "about". Further, all ranges in this disclosure are inclusive and combinable, and reference to a value in a range includes each value in the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains, and any and all combinations of one or more of the associated listed items.

The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The essential features and significant effects of the invention can be seen from the following examples, which are described as some, but not all, of which, therefore, are not limiting of the invention, and some of the insubstantial modifications and adaptations of the invention by those skilled in the art are within the scope of the invention.

Example 1

A preparation method of VB ₂ modified iron-based MOFs material comprises the following steps:

(1) 5mmol of ferric chloride hexahydrate (FeCl ₃·6H₂ O) and 2.5mmol of terephthalic acid (H ₂ BDC) were dissolved in 15mL of N, N-Dimethylformamide (DMF), respectively, to obtain ferric chloride solution and terephthalic acid solution;

(2) Pouring ferric chloride solution into terephthalic acid solution, mixing and stirring for 30min to obtain mixed solution C;

(3) Weighing 0.2mmol of riboflavin, dissolving in the mixed solution C, fully mixing and stirring for 60min to stir into a homogeneous solution;

(4) Transferring the obtained homogeneous phase solution into a 50mL polytetrafluoroethylene lining high-pressure reaction kettle, and then heating and reacting for 20h at 110 ℃;

(5) Centrifuging the reacted solution at 4000r/min for 15min, washing with DMF and ethanol for three times, drying at 60 ℃ for 12h, grinding and crushing with an agate mortar, and collecting to obtain a brown yellow solid, namely VB ₂ @MIL-101 (Fe) which is a modified iron-based MOFs material modified by VB ₂ and is marked as VB ₂ -20@MIL-101 (Fe).

Fig. 1 is a scanning electron microscope SEM image of a Fenton catalyst, which is a modified iron-based MOFs material VB ₂ @MIL-101 (Fe) prepared in this example. As can be seen from the figure 1, the VB ₂ modified iron-based MOFs material has a regular octahedral crystal structure in whole morphology and a particle size of 500-600 nm.

FIG. 2 is an X-ray diffraction XRD pattern of the modified iron-based MOFs material VB ₂ @MIL-101 (Fe) prepared in this example. As can be seen from FIG. 2, MIL-101 (Fe) exhibited characteristic diffraction peaks with high intensity at 2 theta angles of 9.02 DEG, 11.86 DEG, 17.34 DEG and 21.82 DEG, which indicates that MIL-101 (Fe) has higher crystallinity. In addition, the characteristic diffraction peak of MIL-101 (Fe) can be found in the X-ray diffraction pattern of VB ₂ @MIL-101 (Fe), and no other characteristic peak appears when 2 theta is at other angles, which can be used for explaining that when VB ₂ is used for modifying MIL-101 (Fe), the crystal structure of MIL-101 (Fe) is not damaged, and VB ₂ is grafted to the surface of the material. As can be seen, VB ₂ successfully modified MIL-101 (Fe).

Example 2

(3) Weighing 0.1mmol of riboflavin, dissolving in the mixed solution C, fully mixing and stirring for 60min to stir into a homogeneous solution;

(5) Centrifuging the reacted solution at 4000r/min for 15min, washing with DMF and ethanol for three times, drying at 60 ℃ for 12h, grinding and crushing with an agate mortar, and collecting to obtain a brown yellow solid, namely VB ₂ @MIL-101 (Fe) which is a modified iron-based MOFs material modified by VB ₂ and is marked as VB ₂ -10@MIL-101 (Fe).

Example 3

(3) Weighing 0.3mmol of riboflavin, dissolving in the mixed solution C, fully mixing and stirring for 60min to stir into a homogeneous solution;

(5) Centrifuging the reacted solution at 4000r/min for 15min, washing with DMF and ethanol for three times, drying at 60 ℃ for 12h, grinding and crushing with an agate mortar, and collecting to obtain a brown yellow solid, namely VB ₂ @MIL-101 (Fe) which is a modified iron-based MOFs material modified by VB ₂ and is marked as VB ₂ -30@MIL-101 (Fe).

Comparative example 1

A preparation method of an iron-based MOFs material comprises the following steps:

(3) Transferring the obtained homogeneous phase solution into a 50mL polytetrafluoroethylene lining high-pressure reaction kettle, and then heating and reacting for 20h at 110 ℃;

(4) Centrifuging the reacted solution at 4000r/min for 15min, washing with DMF and ethanol for three times, drying at 60 ℃ for 12h, grinding and crushing with an agate mortar, and collecting to obtain brown solid, namely the iron-based MOFs material MIL-101 (Fe).

Comparative example 2

(3) Weighing 0.05mmol of riboflavin, dissolving in the mixed solution C, fully mixing and stirring for 60min to stir into a homogeneous solution;

(5) Centrifuging the reacted solution at 4000r/min for 15min, washing with DMF and ethanol for three times, drying at 60 ℃ for 12h, grinding and crushing with an agate mortar, and collecting to obtain a brown yellow solid, namely VB ₂ @MIL-101 (Fe) which is a modified iron-based MOFs material modified by VB ₂, and marking as VB ₂ -5@MIL-101 (Fe).

FIG. 4 is a graph showing impedance tests, and the modified iron-based MOFs material VB ₂ -20@MIL-101 (Fe) prepared in example 1 has higher conductivity than the unmodified iron-based MOFs material MIL-101 (Fe), can effectively reduce the impedance of MIL-101 (Fe), is reduced from 179 Ω/cm ² to 136 Ω/cm ², and has conductivity improved by 16% compared with AQS (anthraquinone-2-sodium sulfonate) -MIL-101 (Fe). The preparation of AQS-MIL-101 (Fe) is the same as that of example 1 in the preparation method and application of modified iron-based MOFs in China patent document with publication number CN 117186426A.

Referring to FIG. 5, VB ₂ -30@MIL-101 (Fe) prepared in example 3 had the smallest impedance of 133 Ω/cm ². With the decrease of VB ₂ addition, the impedance of the prepared VB ₂ modified iron-based MOFs material is gradually increased.

The impedance test conditions are that a reference electrode is an Ag/saturated AgCl electrode, a counter electrode is a Pt electrode, a working electrode is a glassy carbon electrode glued with the prepared catalyst material by using Nafion, electrolyte is 0.1mol/L KCl aqueous solution of 5.0mmol/L K ₃[Fe(CN)₆ ], the frequency range is set to be 1-1 multiplied by 10 ⁶ Hz, and the voltage amplitude is set to be 5mV.

Application example

The VB ₂ -20@MIL-101 (Fe) prepared in the example 1 and the MIL-101 (Fe) prepared in the comparative example 1 are used as catalysts for degrading florfenicol in water, and the specific application is as follows:

(1) 0.04g of the catalyst was added to 100mL of a water body containing 10mg/L of florfenicol, and 10mmol/L of hydrogen peroxide (H ₂O₂) oxidant was added, and the Fenton reaction was started.

(2) The solution was subjected to a sufficient shaking reaction, water was sampled at 0, 0.5, 1, 1.5, 2, 2.5 and 3 hours, and the Fenton reaction was terminated by adding 0.2mol/L of a quencher sodium thiosulfate (Na ₂S₂O₃), and filtration was performed using a 0.45 μm aqueous filtration membrane.

(3) And (3) collecting the water sample obtained after filtration, filling the water sample into a brown liquid chromatography vial, detecting the concentration of the florfenicol in the water sample by using a High Performance Liquid Chromatograph (HPLC), and calculating the degradation rate of the florfenicol.

FIG. 3 is a schematic diagram showing degradation of VB ₂ modified iron-based MOFs material VB ₂ @MIL-101 (Fe) prepared in example 1 and MIL-101 (Fe) in comparative example 1 to a drug solution containing 10mg/L florfenicol. The horizontal axis represents reaction time, and the vertical axis represents degradation of florfenicol (florfenicol real-time concentration/florfenicol initial concentration). From the results, the degradation rate of the modified material added after 150min Fenton reaction is up to 98% +/-0.7%, and the degradation rate of the modified material added is only 83.5% +/-1.8%, so that the modified iron-based MOFs material has better catalytic effect than the unmodified iron-based MOFs material.

Example 4

The invention also provides a heterogeneous Fenton reaction system which comprises a Fenton reaction tank 100, wherein a separation part 160 is arranged in the Fenton reaction tank 100, the Fenton reaction tank 100 is divided into a Fenton reaction area and a water outlet sedimentation area by the separation part 160, the Fenton reaction area is provided with a water inlet and a medicine inlet, the Fenton reaction area is provided with a fixing part 110, a lifting part 120 and a catalyst loading part 140 which are sequentially connected, the Fenton catalyst loading part 140 is loaded with a Fenton catalyst, the Fenton catalyst can be the Fenton catalyst prepared in any one of the embodiments 1-3, and the water outlet sedimentation area is provided with a mud outlet and a water outlet. The waste water can be aquaculture tail water, pharmaceutical waste water or other waste water containing organic pollutants.

The wastewater and the Fenton reagent enter the Fenton reaction zone through the water inlet and the medicine inlet respectively, and the wastewater is treated by Fenton oxidation under the catalysis of the Fenton catalyst loaded on the catalyst loading part 140. The lifting member 120 may control the lifting of the catalyst supporting member 140, for example, when the wastewater is required to be subjected to Fenton oxidation treatment, the catalyst supporting member 140 may be lowered to be immersed in the wastewater, and Fenton catalyst on the catalyst supporting member 140 may exert a catalytic effect. When the Fenton oxidation treatment of the wastewater is completed, the catalyst-supporting member 140 may be lifted to be separated from the wastewater. The catalyst-supporting member 140 is also easily replaced after the removal of the waste water.

When the water level in the Fenton reaction zone exceeds the highest position of the partition 160, the treated wastewater flows into the effluent precipitation zone. The treated wastewater also contains sludge, which is precipitated in the effluent precipitation zone and is discharged out of the Fenton reaction tank 100 through a sludge outlet.

As an alternative embodiment, the fenton catalyst may be dispersed in the glue and then the glue mixed with the catalyst is applied to the catalyst supporting member 140, in which process the catalyst loading may be reasonably controlled.

Further, the volume ratio of the Fenton reaction zone to the effluent precipitation zone in the Fenton reaction tank 100 is 4-2:1, which is favorable for the wastewater to fully react in the Fenton reaction zone so as to reach the emission standard. As a preferred embodiment, the volume ratio of Fenton reaction zone to effluent precipitation zone is 4:1.

Further, the catalyst loading part 140 is rotatably connected with the lifting part 120, and the catalyst loading part 140 can rotate to make the Fenton catalyst fully contact with the wastewater, and the hydrogen peroxide can be fully and uniformly mixed, so that the Fenton reaction is more fully facilitated. On the other hand, the driving member 130 is connected to the catalyst supporting member 140, and the rotation of the catalyst supporting member 140 can be driven by the driving member 130. For example, the catalyst loading member 140 may be connected to the lifting member 120 by a rotation shaft, and the driving member 130 may drive the catalyst loading member 140 to rotate by the rotation shaft.

As an alternative embodiment, the effluent precipitation zone is provided with a sludge collecting member 170, the sludge collecting member 170 being connected with the partition member 160, the sludge collecting member 170 being connected with the sludge outlet. The sludge collecting member 170 is a sludge bucket, one side of which is connected to the partition member 160, and sludge may slide down from the partition member 160 into the sludge bucket and be discharged from the Fenton reaction tank 100 through the sludge outlet. As an alternative embodiment, the lower end of the partition member 160 is connected to the upper end of one side of the sludge collecting member 170 to divide the Fenton reaction tank 100 into a Fenton reaction zone and an effluent precipitation zone, and the inside structure of the Fenton reaction tank 100 is more compact.

Specifically, the fixing member 110 is a fixing rod, two ends of the fixing rod are fixedly connected with the Fenton reaction tank 100, the lifting member 120 may be a telescopic rod or an elevator, the driving member 130 may be a motor, the catalyst loading member 140 is a material plate made of corrosion-resistant material, such as polytetrafluoroethylene material, so as to prolong the service life of the catalyst loading member, and the shape of the catalyst loading member 140 may be rectangular, diamond-shaped or the like. The catalyst supporting member 140 may further be provided with a plurality of small holes, the diameter of which is less than 500nm, to increase the air permeability thereof, thereby being beneficial to improving the reaction efficiency and reducing the resistance during rotation. As a specific implementation mode, the upper end of the lifter is connected with the fixed rod, the lower end of the lifter is connected with the motor, the output shaft of the motor is connected with one side of the cuboid material plate, and the other side corresponding to the cuboid material plate can be connected with the motor through the fixed rod and the lifter. In addition, the rotational direction of the different material plates can be controlled individually by the motor to which they are connected.

Further, referring to fig. 9, the Fenton reaction zone further includes an overflow weir 150, and the overflow weir 150 is disposed within the Fenton reaction zone, and a partition member 160 is connected to the overflow weir 150 for overflowing the treated wastewater from the Fenton reaction zone to the effluent precipitation zone. Specifically, the overflow weir 150 includes a smooth buffer section 153 connected to the sludge collecting member 170 to allow sludge to enter the sludge collecting member 170 at a low speed, a support section 151 for supporting the overflow weir 150 on the other side, the support section 151 being fixedly connected to the Fenton reaction tank 100, and an overflow section 152 in the middle part, a weir mouth being provided at the top of the overflow section 152, the overflow section 152 further including a slope on which a partition member 160 is connected. As a specific embodiment, the overflow weir 150 is a rounded overflow weir 150, and the angle of the weir mouth of the rounded overflow weir 150 is 60 ° to 80 °, so that the sludge can slide down the partition member 160 to be precipitated to the effluent precipitation zone under the action of gravity. The partition member 160 is a partition made of corrosion-resistant material, for example, a partition made of polytetrafluoroethylene, and the angle between the partition and the horizontal plane is 45 ° to 60 °, which is also beneficial for the sludge to slide down along the partition under the action of gravity.

The heterogeneous Fenton reaction system further comprises a water inlet water tank 200 and a medicament adding component 320, the water inlet water tank 200 is connected with a water inlet of the Fenton reaction zone, the medicament adding component 320 is connected with a medicament inlet of the Fenton reaction zone, the collected wastewater is filled in the water inlet water tank 200, the Fenton medicament is filled in the medicament adding component 320, and the wastewater and the Fenton medicament can be respectively conveyed into the Fenton reaction zone through a first liquid conveying component 210 and a third liquid conveying component 310, for example, the metering pumps can be respectively used for conveying the wastewater and the Fenton medicament, and the conveying quantity can be controlled. Specifically, the medicament adding part 320 may be a medicament cartridge.

As an alternative embodiment, the water outlet of the water outlet sedimentation zone is connected with a water drain pipe, and a second liquid conveying component 180, such as a water pump such as a centrifugal pump, is arranged on the water drain pipe, so that the wastewater treated in the water outlet sedimentation zone can be pumped out and conveyed to the outside, such as a sewage pipe network. As an alternative embodiment, a drain pipe may be connected from above the effluent precipitation zone and transported to the outside through the second liquid transport member 180.

Further, the effluent precipitation zone is further provided with a detection port connected to the water sample collection member 330, and a fourth liquid delivery member 340, such as a metering pump, may be provided between the detection port and the water sample collection member 330 to extract a small amount of treated wastewater for detecting various water quality data. On the other hand, the water sample collection member 330 may be connected to a TOC-integrated cabinet, which may detect the quality of the treated wastewater in real time. In particular, the water sample collection member 330 may be a water sample cartridge.

The heterogeneous Fenton reaction system further comprises an intelligent operation platform, wherein the intelligent operation platform is electrically connected with the TOC integrated cabinet, the third liquid conveying component 310, the first liquid conveying component 210 and other liquid conveying components, and can automatically control the adding amount of Fenton medicament, the flow rate of wastewater and the like according to real-time detection data of the TOC integrated cabinet. Referring to fig. 8, for the convenience of integration of automatic control, the intelligent console, TOC integrated cabinet, water sample collection unit 330, chemical dosing unit 320, third liquid transport unit 310, and fourth liquid transport unit 340 may be integrated into the same operation room 300. In addition, fire-fighting equipment and the like may be provided in the operation room 300.

The invention and its embodiments have been described above by way of illustration and not limitation, and the invention is illustrated in the accompanying drawings and described in the drawings in which the actual structure is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the structural mode and the embodiments similar to the technical scheme are not creatively designed without departing from the gist of the present invention.

Claims

1.A preparation method of a Fenton catalyst is characterized by comprising the following steps of:

Carrying out hydrothermal reaction on a solution containing ferric trichloride hexahydrate, terephthalic acid and riboflavin to obtain a Fenton catalyst VB ₂ @MIL-101 (Fe);

2. The method for preparing the Fenton catalyst according to claim 1, wherein:

The mole ratio of the ferric trichloride hexahydrate, the terephthalic acid and the riboflavin is 2:1 (0.2-0.3).

3. A process for the preparation of a Fenton catalyst according to any one of claims 1 or 2, characterized in that:

the ratio of ferric trichloride hexahydrate to solvent in the solution is 5mmol (30-50) mL;

The solvent of the solution comprises N, N-dimethylformamide.

4. A Fenton catalyst prepared by the preparation method according to any one of claims 1 to 3, which is characterized in that:

The Fenton catalyst comprises MIL-101 (Fe), and riboflavin is loaded on the MIL-101 (Fe).

5. The Fenton catalyst according to claim 4, wherein:

the crystal structure of the Fenton catalyst is a regular octahedron structure;

The particle size of the Fenton catalyst is 500-600 nm.

6. A Fenton catalyst prepared by the preparation method according to any one of claims 1-3 or a method for degrading florfenicol in a water body by using the Fenton catalyst according to any one of claims 4-5, which is characterized in that:

and adding the Fenton catalyst into a water body containing florfenicol, adding hydrogen peroxide, and carrying out oscillation reaction.

7. The method for degrading florfenicol in a water body by using a Fenton catalyst according to claim 6, wherein the method comprises the following steps:

the dosage of the Fenton catalyst is 0.2-0.5 g/L;

The concentration of the florfenicol in the water body containing the florfenicol is 1-50 mg/L;

The dosage of the hydrogen peroxide is 10-30 mmol/L.

8. A heterogeneous Fenton reaction system, characterized in that:

the device comprises a Fenton reaction tank (100), wherein a separation part (160) is arranged in the Fenton reaction tank (100), and the Fenton reaction tank is divided into a Fenton reaction zone and an effluent precipitation zone by the separation part (160);

The Fenton reaction zone is provided with a water inlet and a medicine inlet;

The Fenton reaction zone is provided with a fixed component (110), a lifting component (120) and a catalyst loading component (140) which are connected in sequence,

The catalyst supporting member (130) supports a Fenton catalyst prepared by the preparation method according to any one of claims 1 to 3 or a Fenton catalyst according to any one of claims 4 to 5;

9. The heterogeneous Fenton reaction system according to claim 8, wherein:

The volume ratio of the Fenton reaction zone to the effluent precipitation zone is 4-2:1;

the catalyst loading part (140) is rotatably connected with the lifting part (120);

the catalyst supporting member (140) is connected to a driving member (130).

10. The heterogeneous Fenton reaction system according to claim 9, wherein:

the effluent precipitation zone is provided with a sludge collection member (170),

The sludge collecting component (170) is connected with the separation component (160), and the sludge collecting component (170) is connected with the sludge outlet;

And/or the number of the groups of groups,

Also included is a weir (150), and the partition member (160) is connected to the weir (150).