Preparation method, material, application and device of free radical enhanced catalytic material

Abstract

The invention discloses a preparation method, a material, application and a device of a free radical enhanced catalytic material. The method comprises the following steps: continuously stirring a substrate material carrier in an organic solvent at room temperature to disperse to obtain a mixed solution; activating an interface of the mixed solution by using ultrasonic; further adding in-situ reaction raw materials to carry out in-situ reaction so as to load the amorphous iron oxyhydroxide AHIO on the surface of the substrate material, wherein the in-situ reaction raw materials comprise ferric chloride hexahydrate and ammonium bicarbonate; and then centrifuging for solid-liquid separation to obtain the free radical enhanced catalytic material AHIOO (at) MxOy-x spherical particles in a vacuum drying oven.

Description

Technical Field

[0001] The present invention relates to the field of catalytic technology, and particularly to a preparation method, a material, an application and a device of a free radical enhanced catalytic material. Background Art

[0002] As a classic advanced oxidation process, the core advantage of Fenton technology lies in the generation of hydroxyl radicals (·OH) by Fe 2+ catalyzing H2O2, whose redox potential is as high as 2.8V, capable of efficiently degrading various refractory organic compounds (such as phenol, dyes, etc.), thus having important application value in the field of industrial wastewater treatment. For example, Patent ZL201710861138.4 verified that the degradation rate of phenol in a homogeneous Fenton system can reach more than 90% within 60 minutes, highlighting the core advantage of its strong oxidation ability. However, the engineering application of this technology faces significant limitations: Firstly, the traditional Fenton reaction needs to operate under acidic conditions (pH 2-4) to maintain the solubility of Fe 2+ , while actual wastewater is often neutral or weakly alkaline, and additional acid needs to be added to adjust the pH, resulting in increased operating costs; Secondly, after the reaction, Fe 3+ is prone to form iron hydroxide colloid precipitation and deactivate, and a large amount of iron-containing sludge is generated, causing secondary pollution problems; In addition, the utilization rate of H2O2 is generally lower than 40%, and excessive dosing not only causes waste of oxidant, but also may inhibit the free radical generation efficiency.

[0003] To address the above problems, existing technologies have tried to break through the pH limit and reduce the generation of iron sludge through the design of heterogeneous catalysts. For example, Patent ZL201811001378.8 uses activated carbon loaded with iron oxide to reduce the generation of iron sludge through the synergistic effect of adsorption-catalysis. However, its preparation process requires high-temperature calcination (280°C), which may cause crystallization of iron oxide, reducing the density of surface active sites, and its catalytic efficiency under neutral conditions is still not ideal.

[0004] In recent years, amorphous metal hydroxides have become a research hotspot for heterogeneous Fenton catalysts due to their higher surface defect concentration and adsorption activity with long-range disordered structures. For example, Patent ZL202110914600.9 synthesizes an amorphous iron-based catalyst by the co-precipitation method, which can degrade organic pollutants under neutral conditions. However, it does not introduce a carrier material, resulting in easy agglomeration of the catalyst and insufficient cyclic stability. In addition, Patent ZL201910165722.5 designs a dual-effect photo-Fenton catalyst, which realizes a 97.5% pollutant degradation rate within 20 minutes through the synergistic effect of visible light excitation and persulfate activation. However, its preparation process involves complex multi-step loading and interface regulation, with relatively high large-scale production costs, and the catalytic activity after magnetic separation drops to 80% after the fifth cycle.

[0005] In summary, although the existing technologies have made certain progress in broadening the applicable pH range and reducing the production of iron sludge, they still face core problems such as crystallization of active components, complex preparation processes, and uncontrollable generation of free radicals. For example, Patent ZL202110455509.5 developed an iron / ceria bimetallic core-shell structure catalyst to enhance catalytic stability through cerium doping. However, it relies on the sodium borohydride reduction method for preparation, with harsh process conditions and potential environmental risks. Therefore, developing a new catalyst that can achieve controllable coating of amorphous active phases under mild conditions, has a highly catalytically active and stable interfacial structure, and has a directional catalytic function is still the key direction to solve the bottleneck of traditional Fenton technology.

[0006] The above information disclosed in the background art section is only used to enhance the understanding of the background of the present invention, and thus may include information that does not constitute the prior art known to those of ordinary skill in the art. Summary of the Invention

[0007] The present invention provides a preparation method, material, application, and device of a free radical enhanced catalytic material. An AHIO active layer is in-situ grown on the surface of an M x O y substrate material through a mild room temperature synthesis process, overcoming the dependence of traditional Fenton technology on acidic conditions, and solving the defects of easy crystallization of active components, weak interfacial binding, and high metal dissolution rate of existing supported catalysts. This catalyst has abundant surface active sites and a stable carrier-active phase interfacial structure, can efficiently activate H2O2 within the pH range of 3-9 to generate free radicals directionally and efficiently, realize the rapid mineralization of organic pollutants, and at the same time significantly reduce iron ion dissolution and sludge production, providing an efficient and low-cost solution for wastewater treatment with wide pH adaptability.

[0008] A preparation method of a free radical enhanced catalytic material includes:

[0009] Continuously stirring the substrate material carrier in an organic solvent at room temperature to obtain a mixed solution,

[0010] Ultrasonically activating the interface of the mixed solution;

[0011] Further adding in-situ reaction raw materials for in-situ reaction to load amorphous iron oxyhydroxide AHIO on the surface of the substrate material. The in-situ reaction raw materials include ferric chloride hexahydrate and ammonium bicarbonate;

[0012] Subsequently, centrifugation is carried out to separate the solid and liquid, and a free radical enhanced catalytic material AHIO@M x O y -x spherical particles are obtained in a vacuum drying oven, where x is the molar mass fraction of ferric chloride hexahydrate in the substrate material, and the range of x is 5%-50%.

[0013] In the described preparation method of a free radical enhanced catalytic material, the substrate material includes one or more of nano-alumina particles and nano-titanium dioxide particles.

[0014] In the described preparation method of a free radical enhanced catalytic material, the organic solvent is one or more of absolute ethanol and isopropanol.

[0015] In the described preparation method of a free radical enhanced catalytic material, the molar mass ratio of ferric chloride hexahydrate to ammonium bicarbonate is 1:3, the concentration of ferric chloride hexahydrate is 1 - 10 mM, the addition amount of ammonium bicarbonate is 3 - 30 mM, the stirring speed at room temperature is 300 - 700 r / min, and the stirring time is 7 - 9 h.

[0016] In the described preparation method of a free radical enhanced catalytic material, the mixed solution is placed in an ultrasonic cleaner for ultrasonic activation. The frequency of the ultrasonic cleaner is 80 - 120 Hz, and the ultrasonic treatment time is 10 - 30 min.

[0017] In the described preparation method of a free radical enhanced catalytic material, the temperature in the vacuum drying oven is 40 - 50 °C, the drying time is 6 - 12 h, and the vacuum pressure is 0.08 - 0.10 MPa.

[0018] A free radical enhanced catalytic material is prepared according to the described preparation method of a free radical enhanced catalytic material. The BET specific surface area of the spherical particles is 40 - 150 m 2 / g, and the particle size is 1 - 10 μm.

[0019] An application is the application of the described free radical enhanced catalytic material in activating H2O2 to degrade organic matter. Among them, the dosage of the free radical enhanced catalytic material is 0.1 - 1.5 g / L, and the dosage of H2O2 is 1 - 12 mM.

[0020] A water treatment reaction device includes,

[0021] A reaction tank, which is provided with the described free radical enhanced catalytic material, an oxidant and wastewater;

[0022] A peristaltic pump, which is connected to the reaction tank to pump in wastewater;

[0023] A pH probe, which is arranged in the reaction tank to monitor the pH of the reaction solution in real time;

[0024] A stirring device, which is arranged in the reaction tank to uniformly mix the described free radical enhanced catalytic material, the oxidant and the wastewater;

[0025] A sample collection device, which is connected to the reaction tank to collect wastewater samples at intervals.

[0026] Compared with the prior art, the present invention has the following advantages: The free radical enhanced catalytic material of AHIO-coated M x O y is prepared by an in-situ synthesis method, and the preparation method has the advantages of simple operation, safety, low energy consumption, low cost, etc.; the free radical enhanced catalytic material prepared by the present invention coats AHIO on the surface of the M x O y substrate material, and the obtained AHIO@M x O y -x composite catalyst has a specific surface area more than 3 times that of the original substrate material particles, and can realize the decomposition of H2O2 and the efficient and directional generation of hydroxyl radicals in a wide pH range without the addition of iron ions. The free radical enhanced catalytic material has high Fenton-like reaction activity for activating H2O2, can effectively activate H2O2 to degrade organic matter, and the degradation rate of hydroquinone reaches 91.15% within 30 minutes and the mineralization rate reaches 66.19% within 60 minutes without any external energy. In summary, the present invention couples the prepared AHIO-coated M x O y substrate material as a catalyst with the Fenton-like reaction system, and solves the technical problems of low removal rate of toxic organic matter, incomplete mineralization, high energy consumption, low and uncontrollable free radical generation efficiency in the prior art for organic wastewater; the present invention has the characteristics of simple material preparation method, low energy consumption, and easy productization; applying the AHIO@M x O y -x free radical enhanced catalytic material to the Fenton-like reaction system, this system has the advantages of high treatment efficiency, strong organic degradation ability, complete mineralization of organic matter, and easy popularization and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] By reading the detailed description of the preferred specific embodiments below, various other advantages and benefits of the present invention will become clear to those of ordinary skill in the art. The accompanying drawings in the specification are only for the purpose of showing the preferred embodiments and are not considered to be a limitation of the present invention. Obviously, the drawings described below are only some embodiments of the present invention, and those of ordinary skill in the art can obtain other drawings based on these drawings without creative efforts. Moreover, throughout the drawings, the same reference numerals are used to represent the same components.

[0028] In the drawings:

[0029] Figure 1 is the XRD pattern of the AHIO@M x O y -x free radical enhanced catalytic material prepared by the present invention, and its characteristic peaks can correspond one by one to the M x O y standard card;

[0030] Figure 2 Scanning electron microscope (SEM) image of the AHIO@Al2O3-20% composite catalyst prepared for the present invention;

[0031] Figure 3 Comparison chart of the effects of the AHIO@Al2O3-20% free radical enhanced catalytic material prepared by the present invention on the degradation of hydroquinone with the activation of H2O2 by Al2O3 alone, the activation of H2O2 by AHIO alone, and the degradation of hydroquinone by the physical mixture of Al2O3 and AHIO;

[0032] Figure 4 Comparison chart of the effects of the AHIO-coated Al2O3 composite catalyst prepared by the present invention on the mineralization of hydroquinone with unactivated H2O2, the activation of H2O2 by Al2O3, and the activation of H2O2 by AHIO alone;

[0033] Figure 5 For the AHIO@M prepared by applying the present invention x O y -x Schematic diagram of the water treatment system device of the free radical enhanced catalytic material;

[0034] Figure 6 Comparison chart of the effects of the Fenton-like system of AHIO@Al2O3-20% prepared by applying the present invention and the homogeneous Fenton system of Fe 2+ on the mineralization of hydroquinone.

[0035] The present invention will be further explained below in conjunction with the drawings and embodiments. Detailed Description of the Invention

[0036] The following will refer to the attached Figures 1 to 6 to describe the specific embodiments of the present invention in more detail. Although specific embodiments of the present invention are shown in the drawings, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein. On the contrary, these embodiments are provided so that the present invention can be more thoroughly understood and the scope of the present invention can be completely conveyed to those skilled in the art.

[0037] It should be noted that certain terms are used in the specification and claims to refer to specific components. Those skilled in the art should understand that technicians may use different nouns to refer to the same component. The specification and claims do not distinguish components by the difference in nouns, but by the difference in the functions of the components. As mentioned throughout the specification and claims, "comprising" or "including" is an open-ended term and should be interpreted as "including but not limited to". The subsequent description in the specification is the preferred embodiment for implementing the present invention, but the description is for the purpose of the general principles of the specification and is not intended to limit the scope of the present invention. The scope of protection of the present invention shall be subject to what is defined by the appended claims.

[0038] For the convenience of understanding the embodiments of the present invention, the following will further explain with specific embodiments in conjunction with the accompanying drawings, and the accompanying drawings do not constitute a limitation to the embodiments of the present invention.

[0039] As Figures 1 to 3 shown, the preparation method of the free radical enhanced catalytic material includes the following steps:

[0040] At room temperature, the substrate material carrier is continuously stirred in an organic solvent to obtain a mixed solution.

[0041] The interface of the mixed solution is activated by ultrasonic waves.

[0042] In-situ reaction raw materials are further added for in-situ reaction to load amorphous iron hydroxyoxide AHIO on the surface of the substrate material. The in-situ reaction raw materials include ferric chloride hexahydrate and ammonium bicarbonate.

[0043] Subsequently, centrifugation is carried out to separate the solid and liquid, and the free radical enhanced catalytic material AHIO@M x O y -x spherical particles are obtained in a vacuum drying oven, where x is the molar mass fraction of ferric chloride hexahydrate in the substrate material, and the range of x is 5% - 50%. M x O y refers to metal oxide.

[0044] In the preferred embodiment of the preparation method of the free radical enhanced catalytic material, the substrate material includes one or more of nano-alumina particles and nano-titanium dioxide particles.

[0045] In the preferred embodiment of the preparation method of the free radical enhanced catalytic material, the organic solvent is one or more of absolute ethanol and isopropanol.

[0046] In a preferred embodiment of the method for preparing a free radical enhanced catalytic material, the molar mass ratio of ferric chloride hexahydrate to ammonium bicarbonate is 1:3, the concentration of ferric chloride hexahydrate is 1-10 mM, the amount of ammonium bicarbonate added is 3-30 mM, the stirring speed at room temperature is 300-700 r / min, and the stirring is 7-9 hours.

[0047] In a preferred embodiment of the method for preparing a free radical enhanced catalytic material, the mixed solution is placed in an ultrasonic cleaning machine for ultrasonic activation.

[0048] In a preferred embodiment of the method for preparing a free radical enhanced catalytic material, the temperature in the vacuum drying oven is 40-50° C., the drying time is 6-12 hours, and the vacuum pressure is 0.08-0.10 MPa.

[0049] A free radical enhanced catalytic material, which is prepared according to the preparation method of a free radical enhanced catalytic material, and the BET specific surface area of ​​the spherical particles is 40-150m 2 / g, and the particle size is 1-10μm.

[0050] An application is the application of the free radical enhanced catalytic material in activating H2O2 to degrade organic matter, wherein the dosage of the free radical enhanced catalytic material is 0.1-1.5 g / L, and the dosage of H2O2 is 1-12 mM.

[0051] A water treatment reaction device comprises:

[0052] Reaction tank 3, in which the free radical enhanced catalytic material, oxidant and waste water are arranged;

[0053] A peristaltic pump 1 connected to the reaction tank 3 to pump wastewater;

[0054] A pH probe 2, which is arranged in the reaction tank 3 to monitor the pH of the reaction solution in real time;

[0055] A stirring device 4 is provided in the reaction tank 3 to uniformly mix the free radical enhanced catalytic material, the oxidant and the wastewater;

[0056] The sample collection device 5 is connected to the reaction tank 3 to collect wastewater samples at intervals.

[0057] In one embodiment, ferric chloride hexahydrate and the base powder are placed in a dispersion solvent and stirred thoroughly. x O y The x in -x is the molar mass fraction of ferric chloride hexahydrate in the base material, and the range of x is 5%-50%.

[0058] In one embodiment, the interfacial activation method is ultrasonic activation. The above mixed solution is placed in an ultrasonic cleaner and ultrasonically treated at 80 - 120 Hz for 10 - 30 min to fully disperse the carrier and expose the surface active sites.

[0059] In one embodiment, AHIO-coated M x O y - composite catalyst in the application of activating H2O2 to degrade organic matter. Any AHIO-coated M x O y The free radical enhanced catalytic material obtained by the preparation method of the composite catalyst, namely AHIO@M x O y -x, in the application of activating H2O2 to degrade organic matter. Among them, the catalyst dosage is 0.1 - 1.5 g / L, and the H2O2 dosage is 1 - 12 mM. The generation of free radicals is regulated by the proportion of the coating material.

[0060] In one embodiment, the device includes a peristaltic pump 1 for feeding wastewater and pumping the wastewater into a cylindrical reaction tank 3. A pH probe 2 is provided at the top of the reaction tank 3 for real-time monitoring of the pH of the reaction solution. A stirring device 4 is provided at the bottom of the reaction tank 3 for uniformly mixing the catalytic material, the oxidant, and the wastewater. Wastewater samples are collected at intervals through a sample collection device 5 for water quality analysis and monitoring.

[0061] In one embodiment, the free radical enhanced catalytic material is a spherical particle with a fluffy surface. The preparation method of the free radical enhanced catalytic material includes carrier dispersion, interfacial activation, in-situ synthesis, centrifugation, and vacuum drying to obtain the AHIO@M x O y -x free radical enhanced catalytic material. The application of the free radical enhanced catalytic material in a Fenton-like reaction system breaks through the acidic condition limitation of traditional Fenton technology, eliminates the need for external addition of iron ions, controls the rapid and directional generation of hydroxyl radicals with an amorphous structure and high-activity interface, and solves the technical problems of low removal rate of toxic organic matter, incomplete mineralization, and high energy consumption in the existing technology for organic wastewater. The present invention has the characteristics of simple material preparation method, low energy consumption, and easy productization. Applying the coated composite metal oxide material to the Fenton-like reaction system, this system has the advantages of high treatment efficiency, strong organic degradation ability, complete mineralization of organic matter, and easy popularization and application.

[0062] Example 1

[0063] An AHIO-coated M x O y material. The base material of the free radical enhanced catalytic material includes nano M x O yA base material and in-situ generated AHIO, and the composite catalyst is spherical particles with a rough surface. A preparation method of a free radical enhanced catalytic material includes the following steps:

[0064] At room temperature, disperse the nano-Al2O3 support in an anhydrous ethanol solvent, continuously stir magnetically during the process, activate the interface by ultrasonic wave at 80 Hz for 10 min, and generate AHIO by in-situ reaction to coat on the surface of Al2O3. The raw materials used in the in-situ reaction include: ferric chloride hexahydrate and ammonium bicarbonate, where the molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 1 and 3 mM respectively, the stirring speed at room temperature is 300 r / min, stir for 7 h, then use a centrifuge to separate the solid and liquid, and dry in a vacuum drying oven at 40 °C for 6 h under a vacuum pressure of 0.08 MPa to obtain spherical particles of AHIO@Al2O3-5%, that is, the free radical enhanced catalytic material.

[0065] Example 2

[0066] An AHIO-coated M x O y material, and the base material of this free radical enhanced catalytic material includes nano-M x O y A base material and in-situ generated AHIO, and the composite catalyst is spherical particles with a rough surface. A preparation method of a free radical enhanced catalytic material includes the following steps:

[0067] At room temperature, disperse the nano-Al2O3 support in an organic solvent of anhydrous ethanol: isopropanol = 1:1, continuously stir magnetically during the process, activate the interface by ultrasonic wave at 100 Hz for 20 min, and generate AHIO by in-situ reaction to coat on the surface of Al2O3. The raw materials used in the in-situ reaction include: ferric chloride hexahydrate and ammonium bicarbonate, where the molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 4 and 12 mM respectively, the stirring speed at room temperature is 500 r / min, stir for 8 h, then use a centrifuge to separate the solid and liquid, and dry in a vacuum drying oven at 45 °C for 9 h under a vacuum pressure of 0.09 MPa to obtain spherical particles of AHIO@Al2O3-20%, that is, the free radical enhanced catalytic material. When nano-aluminum oxide is used as the base, x = 20% is the optimal ratio for pollutant degradation. The comparison effect of the free radical concentration and components generated at this ratio for the most suitable pollutant degradation can be seen in the application examples in Examples 7 and 8.

[0068] Example 3

[0069] An AHIO-coated M x O y material, and the base material of this free radical enhanced catalytic material includes nano-M x O yA base material and in-situ generated AHIO, the composite catalyst being spherical particles with a rough surface. A preparation method of a free radical enhanced catalytic material, comprising the following steps:

[0070] At room temperature, disperse the nano-Al2O3 support in an isopropanol solvent, continuously stir magnetically during the process, activate the interface with 120 Hz ultrasound for 30 min, generate AHIO in-situ and coat it on the surface of Al2O3. The raw materials used in the in-situ reaction include: ferric chloride hexahydrate and ammonium bicarbonate, where the molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 10 and 30 mM respectively, the stirring speed at room temperature is 700 r / min, stir for 9 h, then use a centrifuge to separate the solid and liquid, and dry in a vacuum drying oven at 50 °C for 12 h under a vacuum pressure of 0.10 MPa to obtain AHIO@Al2O3-50% spherical particles, i.e., the free radical enhanced catalytic material. When nano-alumina is the base material, AHIO@Al2O3-30% is the optimal ratio for hydroxyl radical generation, while when nano-titanium dioxide is the base material, AHIO@TiO2-5% is the optimal ratio for superoxide radical generation. The best effect of free radical generation is brought about by the optimal balance of the active site density and the mass transfer efficiency. See the application example in Example 10 for the comparison effect.

[0071] Example 4

[0072] An AHIO-coated M x O y material, the base material of this free radical enhanced catalytic material includes nano-M x O y A base material and in-situ generated AHIO, the composite catalyst being spherical particles with a rough surface. A preparation method of a free radical enhanced catalytic material, comprising the following steps:

[0073] At room temperature, disperse the nano-TiO2 support in an anhydrous ethanol solvent, continuously stir magnetically during the process, activate the interface with 80 Hz ultrasound for 10 min, generate AHIO in-situ and coat it on the surface of TiO2. The raw materials used in the in-situ reaction include: ferric chloride hexahydrate and ammonium bicarbonate, where the molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 1 and 3 mM respectively, the stirring speed at room temperature is 300 r / min, stir for 7 h, then use a centrifuge to separate the solid and liquid, and dry in a vacuum drying oven at 40 °C for 6 h under a vacuum pressure of 0.08 MPa to obtain AHIO@TiO2-5% spherical particles, i.e., the free radical enhanced catalytic material.

[0074] Example 5

[0075] An AHIO-coated M x O y material, the base material of this free radical enhanced catalytic material includes nano-M x Oy A substrate material and in-situ generated AHIO, and the composite catalyst is a spherical particle with a rough surface. A preparation method of a free radical enhanced catalytic material includes the following steps:

[0076] At room temperature, disperse the nano-TiO2 support in an organic solvent with anhydrous ethanol: isopropanol = 1:1, continuously stir magnetically during the process, activate the interface by ultrasonic treatment at 100 Hz for 20 min, and use an in-situ reaction to generate AHIO coated on the surface of TiO2. The raw materials used in the in-situ reaction include: ferric chloride hexahydrate and ammonium bicarbonate, where the molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 4 and 12 mM respectively, the stirring speed at room temperature is 500 r / min, stir for 8 h, then use a centrifuge to separate the solid and liquid, and dry in a vacuum drying oven at 45 °C for 9 h under a vacuum pressure of 0.09 MPa to obtain AHIO@TiO2-20% spherical particles, that is, the free radical enhanced catalytic material.

[0077] Example 6

[0078] An AHIO-coated M x O y material, and the substrate material of the free radical enhanced catalytic material includes nano-M x O y A substrate material and in-situ generated AHIO, and the composite catalyst is a spherical particle with a rough surface. A preparation method of a free radical enhanced catalytic material includes the following steps:

[0079] At room temperature, disperse the nano-TiO2 support in isopropanol solvent, continuously stir magnetically during the process, activate the interface by ultrasonic treatment at 120 Hz for 30 min, and use an in-situ reaction to generate AHIO coated on the surface of TiO2. The raw materials used in the in-situ reaction include: ferric chloride hexahydrate and ammonium bicarbonate, where the molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 10 and 30 mM respectively, the stirring speed at room temperature is 700 r / min, stir for 9 h, then use a centrifuge to separate the solid and liquid, and dry in a vacuum drying oven at 50 °C for 12 h under a vacuum pressure of 0.10 MPa to obtain AHIO@TiO2-50% spherical particles, that is, the free radical enhanced catalytic material.

[0080] Example 7

[0081] An AHIO-coated M x O y material, and the substrate material of the free radical enhanced catalytic material includes nano-M x O y A substrate material and in-situ generated AHIO, and the composite catalyst is a spherical particle with a rough surface. A preparation method of a free radical enhanced catalytic material includes the following steps:

[0082] At room temperature, disperse the nano-Al2O3 support in an organic solvent with anhydrous ethanol: isopropanol = 1:1. During the process, continuously stir magnetically, activate the interface by ultrasonic wave at 100 Hz for 20 min, and use in-situ reaction to generate AHIO coated on the surface of Al2O3. The raw materials used in the in-situ reaction include ferric chloride hexahydrate and ammonium bicarbonate, where the molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 4 and 12 mM respectively. Stir at a rotation speed of 500 r / min at room temperature for 8 h. Then, use a centrifuge to separate the solid from the liquid, and dry it at 45 °C for 9 h in a vacuum drying oven with a vacuum pressure of 0.09 MPa. The vacuum pressure is 0.09 MPa to obtain AHIO@Al2O3-20% spherical particles, that is, the free radical enhanced catalytic material.

[0083] Figure 2 This is the scanning electron microscope image of the AHIO@Al2O3-20% particles prepared by the present invention, and its spherical structure can be seen.

[0084] Application Example

[0085] The AHIO@Al2O3-20% particles prepared in this example were used to activate H2O2 to degrade a 30 mg / L hydroquinone (HQ) solution. Without adding an external light source power supply, after adding the activation of this example, the degradation efficiency of HQ reached 91.15% within 30 min, which was 8.74 (10.43%) and 1.42 (64.14%) times the degradation efficiency of single Al2O3 and AHIO activating H2O2 respectively, as Figure 3 。

[0086] Example 8

[0087] A kind of material with AHIO coated on M x O y The substrate material of this free radical enhanced catalytic material includes nano-M x O y The substrate material and in-situ generated AHIO, and the composite catalyst is spherical particles with a rough surface. A preparation method of a free radical enhanced catalytic material includes the following steps:

[0088] Disperse the nano-Al2O3 support in an organic solvent of anhydrous ethanol: isopropanol = 1:1 at room temperature, continuously stir magnetically during the process, activate the interface by ultrasonic wave at 100 Hz for 20 min, and use in-situ reaction to generate AHIO coated on the surface of Al2O3. The raw materials used in the in-situ reaction include ferric chloride hexahydrate and ammonium bicarbonate, where the molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 4 and 12 mM respectively. Stir at 500 r / min at room temperature for 8 h, then use a centrifuge to separate the solid and liquid, and dry in a vacuum drying oven at 45 °C for 9 h under a vacuum pressure of 0.09 MPa to obtain AHIO@Al2O3-20% spherical particles, that is, the free radical enhanced catalytic material.

[0089] Application example

[0090] Use the AHIO@Al2O3-20% particles prepared in this example to activate H2O2 to degrade 30 mg / L of HQ solution. Without adding an external light source power supply, after adding the activation of this example, the TOC mineralization efficiency of HQ reaches 66.19% within 60 min, which is 15.39 (4.3%) and 1.76 (37.6%) times the TOC mineralization efficiency of single Al2O3 and AHIO activating H2O2 respectively, as Figure 4 。

[0091] Example 9

[0092] A kind of AHIO-coated M x O y material. The substrate material of this free radical enhanced catalytic material includes nano-M x O y substrate material and in-situ generated AHIO, and the composite catalyst is spherical particles with a rough surface. A preparation method of a free radical enhanced catalytic material includes the following steps:

[0093] Disperse the nano-Al2O3 support in an organic solvent of anhydrous ethanol: isopropanol = 1:1 at room temperature, continuously stir magnetically during the process, activate the interface by ultrasonic wave at 100 Hz for 20 min, and use in-situ reaction to generate AHIO coated on the surface of Al2O3. The raw materials used in the in-situ reaction include ferric chloride hexahydrate and ammonium bicarbonate, where the molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 4 and 12 mM respectively. Stir at 500 r / min at room temperature for 8 h, then use a centrifuge to separate the solid and liquid, and dry in a vacuum drying oven at 45 °C for 9 h under a vacuum pressure of 0.09 MPa to obtain AHIO@Al2O3-20% spherical particles, that is, the free radical enhanced catalytic material.

[0094] Comparative example

[0095] The AHIO@Al2O3-20% spherical particle-like Fenton system prepared by the present invention and homogeneous Fe2+ For comparison with the Fenton system, the experimental device is as Figure 5 shown, and the comparison test results are as Figure 6 shown. The specific implementation process includes:

[0096] In the comparative example, ferrous sulfate heptahydrate with the corresponding Fe 2+ ion concentration and 8 mM H2O2 were used to degrade 100 mL of 30 mg / L HQ solution. The total organic carbon removal rate was 20.3% at an initial pH of 6.0 for 60 min, and 30.4% at pH 4.0 for 60 min. When the AHIO@Al2O3-20% catalyst with the same relative iron content and 8 mM H2O2 were used to degrade 100 mL of 30 mg / L HQ solution, the total organic carbon removal rate was 66.2% at an initial pH of 6.0 for 60 min, and 67.2% at pH 4.0. The total organic carbon removal rate was significantly improved compared to the homogeneous Fenton system.

[0097] Example 10

[0098] An AHIO-coated M x O y material. The substrate material of this free radical enhanced catalytic material includes nano M x O y substrate material and in-situ generated AHIO. The composite catalyst is spherical particles with a rough surface. A preparation method of a free radical enhanced catalytic material includes the following steps:

[0099] At room temperature, disperse the nano-Al2O3 support in an anhydrous ethanol solvent, continuously stir magnetically during the process, activate the interface with 80 Hz ultrasound for 10 min, and use in-situ reaction to generate AHIO coated on the surface of Al2O3. The raw materials used in the in-situ reaction include ferric chloride hexahydrate and ammonium bicarbonate, where the molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 1 and 3 mM respectively. The stirring speed at room temperature is 300 r / min, and stir for 7 h. Then use a centrifuge to separate the solid and liquid, and dry in a vacuum drying oven at 40 °C for 6 h under a vacuum pressure of 0.08 MPa to obtain AHIO@Al2O3-5% spherical particles, that is, the free radical enhanced catalytic material.

[0100] At room temperature, disperse the nano-Al2O3 support in an organic solvent with anhydrous ethanol: isopropanol = 1:1. During the process, continuously stir magnetically, activate the interface by ultrasonic wave at 100 Hz for 20 min, and use in-situ reaction to generate AHIO coated on the surface of Al2O3. The raw materials used in the in-situ reaction include ferric chloride hexahydrate and ammonium bicarbonate. The molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 4 and 12 mM respectively. Stir at a speed of 500 r / min at room temperature for 8 h. Then, use a centrifuge to separate the solid from the liquid, and dry in a vacuum drying oven at 45 °C for 9 h under a vacuum pressure of 0.09 MPa to obtain AHIO@Al2O3-20% spherical particles, that is, the free radical enhanced catalytic material.

[0101] At room temperature, disperse the nano-Al2O3 support in isopropanol solvent. During the process, continuously stir magnetically, activate the interface by ultrasonic wave at 120 Hz for 30 min, and use in-situ reaction to generate AHIO coated on the surface of Al2O3. The raw materials used in the in-situ reaction include ferric chloride hexahydrate and ammonium bicarbonate. The molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 6 and 18 mM respectively. Stir at a speed of 700 r / min at room temperature for 9 h. Then, use a centrifuge to separate the solid from the liquid, and dry in a vacuum drying oven at 50 °C for 12 h under a vacuum pressure of 0.10 MPa to obtain AHIO@Al2O3-30% spherical particles, that is, the free radical enhanced catalytic material.

[0102] At room temperature, disperse the nano-TiO2 support in anhydrous ethanol solvent. During the process, continuously stir magnetically, activate the interface by ultrasonic wave at 80 Hz for 10 min, and use in-situ reaction to generate AHIO coated on the surface of TiO2. The raw materials used in the in-situ reaction include ferric chloride hexahydrate and ammonium bicarbonate. The molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 1 and 3 mM respectively. Stir at a speed of 300 r / min at room temperature for 7 h. Then, use a centrifuge to separate the solid from the liquid, and dry in a vacuum drying oven at 40 °C for 6 h under a vacuum pressure of 0.08 MPa to obtain AHIO@TiO2-5% spherical particles, that is, the free radical enhanced catalytic material.

[0103] At room temperature, disperse the nano-TiO2 support in an organic solvent with anhydrous ethanol: isopropanol = 1:1. During the process, continuously stir magnetically, activate the interface by ultrasonic wave at 100 Hz for 20 min, and use in-situ reaction to generate AHIO coated on the surface of TiO2. The raw materials used in the in-situ reaction include ferric chloride hexahydrate and ammonium bicarbonate. The molar masses of ferric chloride hexahydrate and ammonium bicarbonate are 4 and 12 mM respectively. Stir at a speed of 500 r / min at room temperature for 8 h. Then, use a centrifuge to separate the solid from the liquid, and dry in a vacuum drying oven at 45 °C for 9 h under a vacuum pressure of 0.09 MPa to obtain AHIO@TiO2-20% spherical particles, that is, the free radical enhanced catalytic material.

[0104] At room temperature, the nano-TiO2 support was dispersed in an isopropyl alcohol solvent, and magnetic stirring was continuously carried out during the process. The interface was activated by ultrasonic treatment at 120 Hz for 30 min, and AHIO was formed in-situ and coated on the surface of TiO2. The raw materials used in the in-situ reaction included ferric chloride hexahydrate and ammonium bicarbonate. The molar masses of ferric chloride hexahydrate and ammonium bicarbonate were 6 and 12 mM respectively. The stirring speed at room temperature was 700 r / min, and stirring was carried out for 9 h. Subsequently, centrifugation was used to separate the solid from the liquid, and drying was carried out at 50 °C for 12 h in a vacuum drying oven with a vacuum pressure of 0.10 MPa to obtain AHIO@TiO2-30% spherical particles, that is, the free radical enhanced catalytic material.

[0105] Application Example

[0106] The amount of hydroxyl radicals and superoxide radicals generated in the H2O2 system activated by the AHIO@M x O y -x free radical enhanced catalytic material prepared in this example was directionally selected and significantly improved. Among them, the amount of hydroxyl radicals generated by AHIO@Al2O3-30% within 30 min was 8.13 μM, which was much higher than that of the substrate material Al2O3 (0.54 μM). The amount of superoxide radicals generated by AHIO@TiO2-5% within 30 min was 1.81 μM, which was much higher than that of the substrate material TiO2 (0.10 μM), as shown in Table 1. The above results indicate that AHIO@Al2O3-30% and AHIO@TiO2-5% respectively correspond to the optimal ratios for the generation of hydroxyl radicals and superoxide radicals, and the best balance between the density of active sites and the mass transfer efficiency is achieved at this coating ratio.

[0107]

[0108] Although the embodiments of the present invention have been described above in conjunction with the accompanying drawings, the present invention is not limited to the above specific embodiments and application fields. The above specific embodiments are merely illustrative and guiding, rather than restrictive. Those of ordinary skill in the art can also make many forms under the inspiration of this specification and without departing from the scope protected by the claims of the present invention, and all of these fall within the scope of protection of the present invention.

Claims

1. A method for preparing a free radical enhanced catalytic material, characterized in that, It includes the following steps: At room temperature, continuously stir the substrate material carrier in an organic solvent to disperse and obtain a mixed solution. Use ultrasonic waves to activate the interface of the mixed solution. Further add in-situ reaction raw materials for in-situ reaction to load amorphous hydroxy iron oxide (AHIO) on the surface of the substrate material. The in-situ reaction raw materials include ferric chloride hexahydrate and ammonium bicarbonate. Subsequently, centrifugation is carried out to achieve solid-liquid separation, and the free radical-enhanced catalytic material AHIO@M is obtained in a vacuum drying oven. x O y -x spherical particles, where x is the molar mass fraction of ferric chloride hexahydrate in the substrate material, and the range of x is 5% - 50%.

2. The method for preparing a free radical enhanced catalytic material according to claim 1, characterized in that, The substrate material includes one or more of nano-aluminum oxide particles and nano-titanium dioxide particles.

3. The method for preparing a free radical enhanced catalytic material according to claim 1, characterized in that, The organic solvent is one or more of absolute ethanol and isopropanol.

4. The method for preparing a free radical enhanced catalytic material according to claim 1, characterized in that, The molar mass ratio of ferric chloride hexahydrate to ammonium bicarbonate is 1:

3. The concentration of ferric chloride hexahydrate is 1 - 10 mM, the addition amount of ammonium bicarbonate is 3 - 30 mM, the stirring speed at room temperature is 300 - 700 r / min, and the stirring time is 7 - 9 h.

5. The method for preparing a free radical enhanced catalytic material according to claim 1, characterized in that, Place the mixed solution in an ultrasonic cleaner for ultrasonic activation. The frequency of the ultrasonic cleaner is 80 - 120 Hz, and the ultrasonic treatment time is 10 - 30 min.

6. The method for preparing a free radical enhanced catalytic material according to claim 1, characterized in that, The temperature in the vacuum drying oven is 40 - 50 °C, the drying time is 6 - 12 h, and the vacuum pressure is 0.08 - 0.10 MPa.

7. A free radical enhanced catalytic material, characterized in that, It is prepared by the preparation method of a free radical enhanced catalytic material according to any one of claims 1-6, and the BET specific surface area of the spherical particles is 40-150m 2 / g, and the particle size is 1-10μm.

8. An application, characterized in that, It is the application of the free radical enhanced catalytic material according to claim 7 in activating H2O2 to degrade organic matter. Among them, the dosage of the free radical enhanced catalytic material is 0.1 - 1.5 g / L, and the dosage of H2O2 is 1 - 12 mM.

9. A water treatment reaction device, characterized in that, It includes: A reaction tank, which is provided with the free radical enhanced catalytic material, an oxidant and wastewater described in claim 7. A peristaltic pump, which is connected to the reaction tank to pump in wastewater. A pH probe, which is arranged in the reaction tank to monitor the pH of the reaction solution in real time. A stirring device, which is arranged in the reaction tank to uniformly mix the free radical enhanced catalytic material, the oxidant and the wastewater. A sample collection device, which is connected to the reaction tank to intermittently collect wastewater samples.

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