CN116943629A - Deep defluorination synergistic Fenton catalytic material and preparation method thereof - Google Patents

Deep defluorination synergistic Fenton catalytic material and preparation method thereof Download PDF

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CN116943629A
CN116943629A CN202310826077.3A CN202310826077A CN116943629A CN 116943629 A CN116943629 A CN 116943629A CN 202310826077 A CN202310826077 A CN 202310826077A CN 116943629 A CN116943629 A CN 116943629A
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calcium
magnesium
catalytic material
defluorination
synergistic
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王胜凡
林娜
张彬彬
欧阳清华
夏玲
黄雷
赵双阳
曾竹
肖吉成
李海波
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Hynar Water Group Corp
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

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Abstract

The application relates to the technical field of sewage treatment, in particular to a deep defluorination synergistic Fenton catalytic material and a preparation method thereof, wherein the method comprises the following steps: preparing and obtaining a calcium doped aluminum hydroxide precursor by a precipitation method based on aluminum-containing metal salt, a pH value regulator, a dispersing agent and calcium chloride; preparing and obtaining a magnesium modified calcium doped alumina nano material by a mechanical ball milling method based on magnesium metal salt, a modifier and a calcium doped aluminum hydroxide precursor; based on magnesium modified calcium doped alumina nano material, ferrous ammonium sulfate, thiourea and a cross-linking agent, the deep defluorination synergistic Fenton catalytic material is prepared by a hydrothermal method. The aluminum, iron and magnesium metal elements in the synthesized deep defluorination synergistic Fenton catalytic material can efficiently adsorb fluoride ions in wastewater, and meanwhile, the metal elements can be used as Fenton reaction catalysts to catalyze and degrade organic matters in the wastewater, so that a large amount of sludge generated in the traditional Fenton reaction process is avoided, and the green and efficient deep defluorination of the wastewater is realized, and meanwhile, the organic pollutants are catalyzed and degraded.

Description

Deep defluorination synergistic Fenton catalytic material and preparation method thereof
[ field of technology ]
The application relates to the technical field of sewage treatment, in particular to a deep defluorination synergistic Fenton catalytic material and a preparation method thereof.
[ background Art ]
The fluoride pollution mainly originates from the industries of semiconductors, panels, new energy sources, chemical industry and the like, the fluorine-containing wastewater in each industry has large quantity, the fluorine concentration is as high as 400-2000mg/L, and the pollution to the ecological environment is greatly endangered. Under the age background of the 'double carbon' target, the newly-increased photovoltaic power generation grid-connected installed capacity of China reaches 3.06 hundred million kilowatts by the end of 2021, and the world is stably occupied for 7 years continuously. The crystalline silicon material of the solar cell inevitably generates a large amount of fluorine-containing wastewater in the production process. Lithium hexafluorophosphate has found large-scale application in lithium ion batteries as an electrolyte salt. Polyvinylidene fluoride is a special fluoropolymer, mainly used as a positive electrode binder in lithium batteries. With the rapid development of new energy industry, the emission of fluorine-containing wastewater is increased rapidly, and the traditional calcium salt precipitation method is adopted to remove fluorine, so that the fluorine removal effect is effective, namely lime, calcium chloride and the like are put into the fluorine-containing wastewater to generate fluoride precipitates, thereby achieving the purposes of solid-liquid separation and removing fluorine ions, but being limited by the reaction solubility product of calcium fluoride and the solid-liquid separation effect, the fluorine concentration of the effluent can only be reduced to 10-20 mg/L. The environment has lower and lower fluoride bearing capacity as 3 kinds of carcinogens, the original emission standard can not meet the environmental protection requirement, the current environmental protection policy in various places is tight, and the fluoride discharge requirement is gradually improved to below 1-1.5 mg/L. However, the traditional deep defluorination material is greatly interfered by organic pollutants in the practical application process, and is difficult to stabilize deep defluorination under the coexistence condition of organic matters. Thus, there is a need to develop new defluorination materials to realize stable deep defluorination under the condition of organic interference.
[ application ]
The embodiment of the application provides a deep defluorination synergistic Fenton catalytic material, a preparation method and application thereof, and aims to solve the technical problem that the traditional deep defluorination material is greatly interfered by organic pollutants in the actual application process and is difficult to stabilize deep defluorination under the coexistence condition of organic matters.
In a first aspect, the embodiment of the application provides a preparation method of a deep defluorination synergic Fenton catalytic material. The method comprises the following steps: preparing and obtaining a calcium doped aluminum hydroxide precursor by a precipitation method based on the first component; wherein the first component for preparing the calcium doped aluminum hydroxide precursor comprises: aluminum-containing metal salt, a pH regulator, a dispersing agent and calcium chloride; preparing and obtaining the magnesium modified calcium doped alumina nano material by a mechanical ball milling method based on the second component; wherein, the second component for preparing the magnesium modified calcium doped alumina nano material comprises: magnesium metal salt, modifier and the calcium doped aluminum hydroxide precursor; preparing the deep defluorination synergistic Fenton catalytic material by a hydrothermal method based on a third component; wherein, the third component for preparing the deep defluorination synergic Fenton catalytic material comprises the following components: the magnesium modified calcium doped alumina nano material, ferrous ammonium sulfate, thiourea and a cross-linking agent.
Optionally, the dispersant is selected from: one or more of sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate.
Optionally, the modifier is one or more of potassium ferrate, potassium permanganate and potassium superoxide.
Optionally, the cross-linking agent is one or more of cysteamine, tetra-vinyl pentylamine and polyoxypropylene diamine.
Optionally, the cross-linking agent is cysteamine.
Optionally, the preparation method of the calcium doped aluminum hydroxide precursor by a precipitation method based on the first component specifically comprises the following steps: dissolving aluminum metal salt with preset weight in deionized water to obtain aluminum metal salt solution; dropwise adding a pH value regulator into the aluminum metal salt solution under the stirring condition, and regulating the pH value to be 10-11; after the pH value is adjusted, adding a dispersant with preset weight, and dropwise adding a calcium chloride solution with preset volume to obtain a first mixture; stirring the first mixture for a preset first time at room temperature, and standing for a second time to obtain a first reactant; and purifying the first reactant to obtain the calcium-doped aluminum hydroxide precursor.
Optionally, the preset weight of aluminum metal salt is: 5-10 g of aluminum chloride; 50-100 ml of deionized water; the pH value regulator is ammonia water; the dispersant with preset weight is as follows: 2-5 g of sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate; the preset volume of calcium chloride solution is as follows: 20-50 ml of 5-10% calcium chloride solution.
Optionally, the preparation method of the magnesium modified calcium doped alumina nano material by a mechanical ball milling method based on the second component specifically comprises the following steps: uniformly mixing the calcium-doped aluminum hydroxide precursor, magnesium metal salt and modifier with preset weight to obtain a second mixture; placing the second mixture in a high-energy ball mill, and performing ball milling reaction for 1-4 hours under the condition of 2000-3000 r/min to obtain the magnesium modified calcium doped alumina nano material.
Optionally, the second mixture comprises the following components: 5-10 g of calcium doped aluminum hydroxide precursor; 2-5 g of magnesium chloride, magnesium sulfate or magnesium nitrate; 1-5 g of potassium ferrate, potassium permanganate or potassium superoxide.
Optionally, the deep defluorination synergistic Fenton catalytic material is prepared and obtained by a hydrothermal method based on a third component, and specifically comprises the following steps: adding a preset weight of magnesium modified calcium doped alumina nanomaterial to the ferrous ammonium sulfate solution, and adding a preset weight of thiourea to stir to form a third mixture; dropwise adding absolute ethanol in which the cross-linking agent is dissolved into the third mixture, and carrying out heating reaction under the water bath condition to obtain a second reactant; a two-step calcination method is adopted for the second reactant, so that the deep defluorination synergistic Fenton catalytic material is obtained; wherein the two-step calcination method comprises: calcining for 2 hours at a preset first temperature in a hydrogen reducing atmosphere; and carbonizing at a preset second temperature for 2 hours. Optionally, the magnesium-modified calcium-doped alumina nanomaterial of preset weight is: 5-10 g of magnesium modified calcium doped alumina nano material; the ferrous ammonium sulfate solution is as follows: 50-100 ml of 5-10% concentration ferrous ammonium sulfate solution; the thiourea with preset weight is as follows: 2-5 g of thiourea; the cross-linking agent is: 1-5 g of cross-linking agent cysteamine, tetra-vinyl pentylamine or polyoxypropylene diamine; the absolute ethyl alcohol is as follows: 20-50 ml; the heating reaction is as follows: reacting for 8-12 h at 95-98 ℃.
In a second aspect, the embodiment of the application provides a deep defluorination cooperative Fenton catalytic material, which is prepared by the preparation method.
The aluminum, iron and magnesium metal elements in the deep defluorination synergistic Fenton catalytic material synthesized by the application can efficiently adsorb and capture fluorine ions in wastewater, and meanwhile, the metal elements can be used as Fenton reaction catalysts to catalyze and degrade organic matters in wastewater.
When the advanced defluorination and Fenton catalytic material is applied to a wastewater advanced treatment fluidized bed process as a fluidized bed carrier, defluorination and Fenton catalyst crystallization nuclei can be formed on the surface of the material in the fluidized bed fluidization process, the defluorination of the material does not need frequent regeneration, a large amount of sludge generated in the traditional Fenton reaction process is avoided, and the green and efficient advanced defluorination of the wastewater is realized while the catalytic degradation of organic pollutants is realized.
Further embodiments of the advantageous aspects of the above-described methods, devices and components are described in detail below. All of the disclosure herein is exemplary only, and suitable modifications may be readily made by those skilled in the art without departing from the spirit and scope of the application as disclosed and claimed.
[ description of the drawings ]
One or more embodiments are illustrated by way of example and not limitation in the figures of the accompanying drawings, in which like references indicate similar elements, and in which the figures of the drawings are not to be taken in a limiting sense, unless otherwise indicated.
Fig. 1 is a schematic flow chart of a preparation method according to an embodiment of the present application.
[ detailed description ] of the application
In order that the application may be readily understood, a more particular description thereof will be rendered by reference to specific embodiments that are illustrated in the appended drawings. It will be understood that when an element is referred to as being "fixed" to another element, it can be directly on the other element or one or more intervening elements may be present therebetween. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or one or more intervening elements may be present therebetween. The terms "upper," "lower," "inner," "outer," "bottom," and the like as used in this specification are used in an orientation or positional relationship based on that shown in the drawings, merely to facilitate the description of the application and to simplify the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the application. Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
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 application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items.
In addition, the technical features mentioned in the different embodiments of the application described below can be combined with one another as long as they do not conflict with one another.
The deep defluorination action mechanism of the defluorination agent is strong adsorption action and ion exchange action, and can be widely applied to wastewater treatment. However, the conventional defluorination material has the defects of large interference caused by organic pollutants, difficulty in stable defluorination and the like.
Therefore, the embodiment of the application provides the deep defluorination synergistic Fenton catalytic material which is convenient and can be prepared in a large scale. The method can be applied to the advanced wastewater treatment fluidized bed process and used as a fluidized bed carrier. In the fluidized bed fluidization process, the deep defluorination synergistic Fenton catalytic material provided by the application can form defluorination and Fenton catalyst crystallization nuclei on the surface of the material, and can catalyze and degrade organic matters in wastewater while defluorination. Therefore, the method can obtain the wastewater treatment wastewater without frequent regeneration, avoids the problem that a large amount of sludge is generated in the traditional Fenton reaction process, and has good application prospect and use advantage in wastewater treatment.
Fig. 1 is a schematic flow chart of a preparation method of a deep defluorination cooperative Fenton catalytic material provided by an embodiment of the application. As shown in fig. 1, the method includes:
and step 10, preparing and obtaining the calcium-doped aluminum hydroxide precursor by a precipitation method based on the first component.
Wherein the first component for preparing the calcium doped aluminum hydroxide precursor comprises: aluminum-containing metal salt, pH regulator, dispersant and calcium chloride. The dispersing agent can be one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate.
Specifically, step 10 includes: 5-10 g of aluminum chloride is weighed and dissolved in 50-100 ml of deionized water, ammonia water is added dropwise under stirring until the pH value is 10-11, then 2-5 g of dispersing agent sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate is added, and then 20-50 ml of 5-10% calcium chloride solution is added dropwise, so that a primary mixed reactant is obtained.
Stirring the preliminarily mixed reactants at room temperature for 2-6 h, standing and aging for 18-24 h to obtain a completely reacted intermediate product. And finally filtering the intermediate product, fully washing the intermediate product to be neutral by deionized water, and drying and grinding the intermediate product to obtain the calcium doped aluminum hydroxide precursor.
The step takes the alumina nanoflower as the inner core, and the dispersing agent is sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate, so that the agglomeration of aluminum atoms in the aging process is avoided. In addition, calcium ions can be combined with phosphate ions in the dispersing agent to generate calcium hydroxy phosphate under alkaline conditions, and the calcium hydroxy phosphate is doped between alumina nanoflowers, so that the adsorption capacity of the material on fluoride ions is improved.
And step 20, preparing the magnesium modified calcium doped alumina nano material by a mechanical ball milling method based on the second component.
Wherein, the second component for preparing the magnesium modified calcium doped alumina nano material comprises: magnesium metal salt, a modifier and the calcium doped aluminum hydroxide precursor. The modifier can be one or more of potassium ferrate, potassium permanganate or potassium superoxide.
Specifically, step 20 includes: mixing 5-10 g of calcium doped aluminum hydroxide precursor, 2-5 g of magnesium chloride, magnesium sulfate or magnesium nitrate, 1-5 g of modifier potassium ferrate, potassium permanganate or potassium superoxide uniformly and then placing the mixture in a high-energy ball mill. Ball milling reaction is carried out for 1-4 h at the speed of 2000 r/min-3000 r/min, and the obtained product is the magnesium modified calcium doped alumina nano material.
The potassium ferrate, potassium permanganate or potassium superoxide can react with metal magnesium salt in the high-speed ball milling process to promote the generation of magnesium peroxide in the calcium-doped aluminum hydroxide precursor crystal lattice, so as to form the magnesium-modified calcium-doped aluminum oxide nano material. The magnesium peroxide modified metal magnesium element can improve the stability and the adsorption performance of the material, and in addition, the magnesium peroxide can promote the Fenton reaction process to generate OH, so that the degradation capability of the material on organic pollutants is improved.
Step 30, preparing the deep defluorination synergistic Fenton catalytic material by a hydrothermal method based on the third component.
Wherein, the third component for preparing the deep defluorination synergic Fenton catalytic material comprises the following components: the magnesium modified calcium doped alumina nano material, ferrous ammonium sulfate, thiourea and a cross-linking agent.
Specifically, step 30 includes: weighing 5-10 g of magnesium modified calcium doped alumina nano material, adding the nano material into a three-mouth bottle filled with 50-100 ml of 5-10% ferrous ammonium sulfate solution, and then adding 2-5 g of thiourea and stirring to form a primary mixed solution. Then 1-5 g of cross-linking agent cysteamine, tetraethylenepentamine or polyoxypropylene diamine is dissolved in 20-50 ml of absolute ethyl alcohol and then added into the mixed solution drop by drop. And (3) reacting for 8-12 h at 95-98 ℃ under the condition of heating in water bath to obtain a target product, and filtering, washing and drying the target product. And finally, calcining the dried target product for 2 hours at 300 ℃ in a hydrogen reducing atmosphere by adopting a two-step calcining method, carbonizing for 2 hours at 600 ℃, cooling to room temperature, and grinding the obtained product, namely the deep defluorination synergistic Fenton catalytic material.
Here, thiourea can be complexed with ferrous ions, fe-S bonds are formed on the surface of the magnesium modified calcium doped alumina nano material, the process of Fenton reaction of the material on organic pollutants can be accelerated, in addition, the reduction effect can be exerted, and the electron transfer is accelerated to promote Fe 3+ To Fe 2+ Is transformed by the above method.
The cross-linking agent is added in the step, and the cross-linking agent is one or more of cysteamine, tetra-vinyl pentylamine and polyoxypropylene diamine. The molecular cross-linking agent has the advantages of small size, high cross-linking uniformity and capability of being flexibly adjusted in a small range to form a uniform network structure, so that the strength and the stability of the material are improved. The deep defluorination synergic Fenton catalytic material prepared by the cross-linking agent has larger specific surface area and porous structure, and improves the adsorption capacity of the material to fluoride ions and the free radical generation efficiency when degrading organic pollutants, thereby improving the pollutant removal effect of the material.
The defluorination synergic Fenton catalytic material is applied to a process of deeply treating wastewater by using the defluorination synergic Fenton catalytic material as a carrier of a fluidized bed, aluminum, calcium, magnesium and iron metal elements in the material can efficiently adsorb and capture fluorine ions in wastewater, a plurality of metal ions are synergic to adsorb, the adsorption capacity of the defluorination ions is large, and the maximum adsorption value can reach 50mg/g. And the material can form defluorination crystal nucleus on the surface of the material in the fluidized bed fluidization process. The material defluorination does not need frequent regeneration, and simultaneously, a large amount of sludge generated in the reaction process of the traditional process is avoided.
The defluorination synergistic Fenton catalytic material is applied to a process of deeply treating wastewater by using the defluorination synergistic Fenton catalytic material as a carrier of a fluidized bed, and metal elements in the material can be used as a Fenton reaction catalyst, and organic matters in the wastewater can be efficiently catalyzed and degraded by adding a small amount of Fenton reagent; and FeOOH crystals can be formed on the surface of the material in the fluidized bed fluidization process. The FeOOH crystal has a certain net capturing adsorption effect on fluoride ions, and can further serve as a Fenton-like reaction catalyst to degrade organic pollutants. Realize deep fluorine removal under the interference of high organic pollutant concentration.
The defluorination and Fenton-synergistic catalytic material is applied to a process of deeply treating wastewater by using the defluorination and Fenton-synergistic catalytic material as a carrier of a fluidized bed, and after crystallization nuclei with adsorbed fluorine on the surface of the material grow to be mature, the mature crystallization nuclei can be discharged from the fluidized bed, and high-fluorine-containing crystals on the surface of the material are recovered for recycling.
The method for preparing the deep defluorination cooperative Fenton catalytic material provided by the embodiment of the application is used for treating wastewater by combining specific embodiments.
Example 1
The preparation process of the deep defluorination synergistic Fenton catalytic material in the embodiment specifically comprises the following steps:
(1) Weighing 10g of aluminum chloride, dissolving in 100ml of deionized water, dropwise adding ammonia water to a pH value of 10 under stirring, then adding 5g of dispersant sodium tripolyphosphate, and then dropwise adding 50ml of 10% calcium chloride solution to obtain a primary mixed reactant;
(2) Stirring the reactants preliminarily mixed in the step (1) at room temperature for reaction for 6 hours, and standing and ageing for 18 hours to obtain an intermediate product with complete reaction;
(3) Filtering the intermediate product precipitate, fully washing with deionized water to neutrality, drying and grinding to obtain a calcium doped aluminum hydroxide precursor;
(4) Uniformly mixing 10g of calcium-doped aluminum hydroxide precursor, 5g of magnesium chloride and 2g of modifier potassium ferrate, and then placing the mixture in a high-energy ball mill, and performing ball milling reaction for 2 hours at 2000r/min to obtain a magnesium-modified calcium-doped aluminum oxide nano material;
(5) Weighing 10g of magnesium modified calcium doped alumina nano material, adding the nano material into a three-mouth bottle filled with 100ml of 10% concentration ferrous ammonium sulfate solution, and then adding 5g of thiourea and stirring to form a primary mixed solution;
(6) Then 50ml of absolute ethanol in which 2g of cysteamine as a crosslinking agent was dissolved was added dropwise to the mixture in (5). Then, after reacting for 8 hours at 95 ℃ under the condition of heating in water bath, filtering, washing and drying are carried out to obtain a target product;
(7) And (3) calcining the target product in the step (6) by adopting a two-step calcining method at 300 ℃ for 2 hours under a hydrogen reducing atmosphere, carbonizing at 600 ℃ for 2 hours, cooling to room temperature, and grinding to obtain the product, namely the deep defluorination synergistic Fenton catalytic material.
Example 2
The preparation process of the deep defluorination synergistic Fenton catalytic material in the embodiment specifically comprises the following steps:
(1) Weighing 10g of aluminum chloride, dissolving in 100ml of deionized water, dropwise adding ammonia water to a pH value of 10 under stirring, then adding 5g of dispersant sodium hexametaphosphate, and then dropwise adding 50ml of 10% calcium chloride solution to obtain a primary mixed reactant;
(2) Stirring the reactants preliminarily mixed in the step (1) at room temperature for reaction for 6 hours, and standing and ageing for 18 hours to obtain an intermediate product with complete reaction;
(3) Filtering the intermediate product precipitate, fully washing with deionized water to neutrality, drying and grinding to obtain a calcium doped aluminum hydroxide precursor;
(4) Uniformly mixing 10g of calcium-doped aluminum hydroxide precursor, 5g of magnesium chloride and 2g of modifier potassium permanganate, and then placing the mixture in a high-energy ball mill, and performing ball milling reaction for 1h at 2000r/min to obtain a magnesium-modified calcium-doped aluminum oxide nano material;
(5) Weighing 10g of magnesium modified calcium doped alumina nano material, adding the nano material into a three-mouth bottle filled with 100ml of 10% concentration ferrous ammonium sulfate solution, and then adding 5g of thiourea and stirring to form a primary mixed solution;
(6) Then 50ml of absolute ethanol in which 2g of the crosslinking agent of tetraethylenepentamine was dissolved was added dropwise to the mixture in (5). Then, after reacting for 8 hours at 95 ℃ under the condition of heating in water bath, filtering, washing and drying are carried out to obtain a target product;
(7) And (3) calcining the target product in the step (6) by adopting a two-step calcining method at 300 ℃ for 2 hours under a hydrogen reducing atmosphere, carbonizing at 600 ℃ for 2 hours, cooling to room temperature, and grinding to obtain the product, namely the deep defluorination synergistic Fenton catalytic material.
Example 3
The preparation process of the deep defluorination synergistic Fenton catalytic material in the embodiment specifically comprises the following steps:
(1) Weighing 10g of aluminum chloride, dissolving in 100ml of deionized water, dropwise adding ammonia water to a pH value of 10 under stirring, then adding 5g of dispersant sodium pyrophosphate, and then dropwise adding 50ml of 10% calcium chloride solution to obtain a primary mixed reactant;
(2) Stirring the reactants preliminarily mixed in the step (1) at room temperature for reaction for 6 hours, and standing and ageing for 18 hours to obtain an intermediate product with complete reaction;
(3) Filtering the intermediate product precipitate, fully washing with deionized water to neutrality, drying and grinding to obtain a calcium doped aluminum hydroxide precursor;
(4) Uniformly mixing 10g of calcium-doped aluminum hydroxide precursor, 5g of magnesium chloride and 2g of modifier potassium superoxide, and then placing the mixture in a high-energy ball mill, and performing ball milling reaction for 1h at 2000r/min to obtain a magnesium-modified calcium-doped aluminum oxide nano material;
(5) Weighing 10g of magnesium modified calcium doped alumina nano material, adding the nano material into a three-mouth bottle filled with 100ml of 10% concentration ferrous ammonium sulfate solution, and then adding 5g of thiourea and stirring to form a primary mixed solution;
(6) Then 50ml of absolute ethanol in which 2g of polyoxypropylene diamine as a crosslinking agent was dissolved was added dropwise to the mixture in (5). Then, after reacting for 8 hours at 95 ℃ under the condition of heating in water bath, filtering, washing and drying are carried out to obtain a target product;
(7) And (3) calcining the target product in the step (6) by adopting a two-step calcining method at 300 ℃ for 2 hours under a hydrogen reducing atmosphere, carbonizing at 600 ℃ for 2 hours, cooling to room temperature, and grinding to obtain the product, namely the deep defluorination synergistic Fenton catalytic material.
Example 4
The preparation process of the deep defluorination synergistic Fenton catalytic material in the embodiment specifically comprises the following steps:
(1) Weighing 10g of aluminum chloride, dissolving in 100ml of deionized water, dropwise adding ammonia water to a pH value of 9 under stirring, then adding 1g of dispersant sodium tripolyphosphate, and then dropwise adding 50ml of 10% calcium chloride solution to obtain a primary mixed reactant;
(2) Stirring the reactants preliminarily mixed in the step (1) at room temperature for reaction for 6 hours, and standing and ageing for 18 hours to obtain an intermediate product with complete reaction;
(3) Filtering the intermediate product precipitate, fully washing with deionized water to neutrality, drying and grinding to obtain a calcium doped aluminum hydroxide precursor;
(4) Uniformly mixing 10g of calcium-doped aluminum hydroxide precursor, 1g of magnesium chloride and 1g of modifier potassium ferrate, and then placing the mixture in a high-energy ball mill, and performing ball milling reaction for 0.5h at 1000r/min to obtain a magnesium-modified calcium-doped aluminum oxide nano material;
(5) Weighing 10g of magnesium modified calcium doped alumina nano material, adding the nano material into a three-mouth bottle filled with 100ml of 10% concentration ferrous ammonium sulfate solution, and then adding 1g of thiourea and stirring to form a primary mixed solution;
(6) Then 50ml of absolute ethanol in which 1g of cysteamine as a crosslinking agent was dissolved was added dropwise to the mixture in (5). Then, after reacting for 8 hours at 80 ℃ under the condition of water bath heating, filtering, washing and drying are carried out to obtain a target product;
(7) Carbonizing the target product in the step (6) for 2 hours at 600 ℃ in a hydrogen reducing atmosphere, cooling to room temperature, and grinding to obtain the product, namely the deep defluorination synergistic Fenton catalytic material.
Control experiment group
The control experimental group was prepared in substantially the same manner as in example 1, except that the dispersant was not added in step (1), the modifier was not added in step (3) and the crosslinking agent was not added in step (4).
Application effect contrast:
the actual fluorine-containing organic wastewater is taken from a certain industrial sewage treatment plant, is introduced into a fluidized bed wastewater treatment reactor, and is respectively added into the deep defluorination synergic Fenton catalytic materials synthesized by the preparation methods in the examples 1-4 and the control experiment group according to the addition amount of 5 g/L.
Then, the deep defluorination and Fenton catalysis material is in a fluidized state in the wastewater to be treated by aeration stirring, 50mg/L hydrogen peroxide is added for reaction for 1h, and the fluoride and COD (chemical oxygen demand) removal effects of the synthesized materials in examples 1-4 are shown in Table 1:
table 1: practical application effects of different embodiment materials
As shown in table 1 above, the deep defluorination co-fenton catalytic materials of examples 1 to 4 were better in fluoride and COD removal than the control experimental group. The reasons for this may be:
1) The addition of the dispersant avoids agglomeration of aluminum atoms during aging.
2) The modifier can react with metal magnesium salt in the high-speed ball milling process to promote the generation of magnesium peroxide in the calcium-doped aluminum hydroxide precursor crystal lattice, so as to form the magnesium modified calcium-doped aluminum oxide nano material.
3) The magnesium metal element after the modification of the magnesium peroxide can improve the stability and the adsorption performance of the material.
4) The magnesium peroxide can promote the Fenton reaction process to generate OH, and the degradation capability of the material on organic pollutants is improved.
5) The cross-linking agent improves the strength and stability of the material. The deep defluorination synergic Fenton catalytic material prepared by the cross-linking agent has larger specific surface area and porous structure, and improves the adsorption capacity of the material to fluoride ions and the free radical generation efficiency when degrading organic pollutants, thereby improving the pollutant removal effect of the material.
In addition, examples 1 to 3 were better in fluoride and COD removal effect than example 4, probably because the ratio of certain components in example 4 was not within the optimum ratio range, thereby affecting the properties of the prepared materials.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and are not limiting; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the application, the steps may be implemented in any order, and there are many other variations of the different aspects of the application as described above, which are not provided in detail for the sake of brevity; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.

Claims (10)

1. The preparation method of the deep defluorination synergistic Fenton catalytic material is characterized by comprising the following steps of:
preparing and obtaining a calcium doped aluminum hydroxide precursor by a precipitation method based on the first component;
wherein the first component for preparing the calcium doped aluminum hydroxide precursor comprises: aluminum-containing metal salt, a pH regulator, a dispersing agent and calcium chloride;
preparing and obtaining the magnesium modified calcium doped alumina nano material by a mechanical ball milling method based on the second component;
wherein, the second component for preparing the magnesium modified calcium doped alumina nano material comprises: magnesium metal salt, modifier and the calcium doped aluminum hydroxide precursor;
preparing the deep defluorination synergistic Fenton catalytic material by a hydrothermal method based on a third component;
wherein, the third component for preparing the deep defluorination synergic Fenton catalytic material comprises the following components: the magnesium modified calcium doped alumina nano material, ferrous ammonium sulfate, thiourea and a cross-linking agent.
2. The method of preparation according to claim 1, wherein the dispersant is selected from the group consisting of: one or more of sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate.
3. The method of claim 1, wherein the modifier is one or more of potassium ferrate, potassium permanganate, and potassium superoxide.
4. The method according to claim 1, wherein the crosslinking agent is one or more of cysteamine, tetra-vinyl pentylamine, polyoxypropylene diamine.
5. The method according to any one of claims 1 to 4, wherein the preparation of the calcium-doped aluminum hydroxide precursor by precipitation based on the first component comprises:
dissolving aluminum metal salt with preset weight in deionized water to obtain aluminum metal salt solution;
dropwise adding a pH value regulator into the aluminum metal salt solution under the stirring condition, and regulating the pH value to be 10-11;
after the pH value is adjusted, adding a dispersant with preset weight, and dropwise adding a calcium chloride solution with preset volume to obtain a first mixture;
stirring the first mixture for a preset first time at room temperature, and standing for a second time to obtain a first reactant;
and purifying the first reactant to obtain the calcium-doped aluminum hydroxide precursor.
6. The method of claim 5, wherein the predetermined weight of aluminum metal salt is: 5-10 g of aluminum chloride; 50-100 ml of deionized water; the pH value regulator is ammonia water; the dispersant with preset weight is as follows: 2-5 g of sodium tripolyphosphate, sodium hexametaphosphate or sodium pyrophosphate; the preset volume of calcium chloride solution is as follows: 20-50 ml of 5-10% calcium chloride solution.
7. The method according to any one of claims 1 to 4, wherein the preparation of the magnesium modified calcium doped alumina nanomaterial by mechanical ball milling based on the second component specifically comprises:
uniformly mixing the calcium-doped aluminum hydroxide precursor, magnesium metal salt and modifier with preset weight to obtain a second mixture;
placing the second mixture in a high-energy ball mill, and performing ball milling reaction for 1-4 hours under the condition of 2000-3000 r/min to obtain the magnesium modified calcium doped alumina nano material.
8. The preparation method according to any one of claims 1 to 4, wherein the deep defluorination synergic Fenton catalytic material is prepared by a hydrothermal method based on a third component, and specifically comprises the following steps:
adding a preset weight of magnesium modified calcium doped alumina nanomaterial to the ferrous ammonium sulfate solution, and adding a preset weight of thiourea to stir to form a third mixture;
dropwise adding absolute ethanol in which the cross-linking agent is dissolved into the third mixture, and carrying out heating reaction under the water bath condition to obtain a second reactant;
a two-step calcination method is adopted for the second reactant, so that the deep defluorination synergistic Fenton catalytic material is obtained;
wherein the two-step calcination method comprises:
calcining for 2 hours at a preset first temperature in a hydrogen reducing atmosphere; and
carbonizing at a preset second temperature for 2 hours.
9. The method of claim 8, wherein the predetermined weight of the magnesium-modified calcium-doped alumina nanomaterial is: 5-10 g of magnesium modified calcium doped alumina nano material; the ferrous ammonium sulfate solution is as follows: 50-100 ml of 5-10% concentration ferrous ammonium sulfate solution; the thiourea with preset weight is as follows: 2-5 g of thiourea;
the cross-linking agent is: 1-5 g of cross-linking agent cysteamine, tetra-vinyl pentylamine or polyoxypropylene diamine; the absolute ethyl alcohol is as follows: 20-50 ml; the heating reaction is as follows: reacting for 8-12 h at 95-98 ℃.
10. A deep defluorination co-fenton catalytic material, characterized in that it is prepared by the preparation method according to any one of claims 1-9.
CN202310826077.3A 2023-07-06 2023-07-06 Deep defluorination synergistic Fenton catalytic material and preparation method thereof Pending CN116943629A (en)

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