CN114392722B - Biochar@five-membered metal oxide composite defluorination material as well as preparation and application thereof - Google Patents

Biochar@five-membered metal oxide composite defluorination material as well as preparation and application thereof Download PDF

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CN114392722B
CN114392722B CN202210105374.4A CN202210105374A CN114392722B CN 114392722 B CN114392722 B CN 114392722B CN 202210105374 A CN202210105374 A CN 202210105374A CN 114392722 B CN114392722 B CN 114392722B
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biochar
metal oxide
oxide composite
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membered
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CN114392722A (en
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郝江楠
黄琳
黄远平
周向清
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Hunan Xifu Environmental Protection Technology Co ltd
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    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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

Abstract

The invention relates to the field of defluorination materials, in particular to a preparation method of a biochar@five-membered metal oxide composite defluorination material, which comprises the steps of carrying out solvothermal treatment on a raw material solution containing biomass and alkali, and then carrying out solid-liquid separation to obtain an alkali treatment solution; wherein, in the raw material solution, the concentration of alkali is more than or equal to 2M; the temperature of the solvothermal is greater than or equal to 150 ℃; adding La, zr, al, ce and water-soluble metal salt of Sc into the alkali treatment liquid to react; carrying out microwave heat treatment on the reaction system to obtain the biochar@five-membered metal oxide composite defluorination material; wherein the temperature of the microwave heat treatment is 400-450 ℃. The invention also comprises the material prepared by the preparation method and the application of the material in fluorine removal. The method is simple in process and convenient to operate, the defluorination material is prepared by taking the biomass solid waste as a main raw material, and the prepared defluorination agent has ultrahigh fluorine adsorption capacity.

Description

Biochar@five-membered metal oxide composite defluorination material as well as preparation and application thereof
Technical Field
The invention belongs to the field of waste utilization and water treatment, and particularly relates to a method for preparing a fluorine removal material by using waste materials.
Background
The fluorine-containing wastewater in China has the characteristics of complex components, large water quantity, wide distribution and the like, and is mainly from industries such as fluorine chemical industry, steel production, aluminum electrolysis and aluminum processing, acid making and sulfur-containing fertilizer production, glass product manufacturing and processing, nonferrous metal smelting and the like, and meanwhile, the fluorine content in surface water and underground water in certain areas is severely out of standard. The existence of high fluorine in the water body causes great harm to the production and living environment of human beings.
In order to reduce the hazard of fluorine, various fluorine removal techniques have been developed, which mainly include a coagulation sedimentation method, an adsorption method, an ion exchange method, a membrane separation method, and the like. Although the technologies have positive effects in reducing the fluorine content in the water body, the defects of high treatment cost, high resource consumption for preparing the fluorine removing agent, large consumption caused by the fact that the fluorine adsorption capacity of the fluorine removing agent is generally less than 100mg/g, secondary pollution generation, no universality for treating water bodies with different pH values and the like still exist. The patent CN102259946A, CN102357357A and the patent CN104324684A can obtain good defluorination effect, but the defluorination materials have high cost and insufficient fluoride ion adsorption capacity due to the adoption of raw materials containing Ti, zr, ce and other elements, and are only suitable for treating neutral water; patent CN1966407a discloses a method for defluorination of an acidic zinc electrolyte with aluminum salts and phosphates, but this method results in a small loss of the valuable element zinc in the electrolyte.
On the other hand, china is a large-population country and is also a country with very rich biomass resources, so that a large amount of biomass waste is also generated. The biomass waste is mostly treated in the modes of landfill, incineration, composting and the like, which not only occupies a large amount of land resources, but also can produce secondary pollution, and more importantly, the waste is not utilized efficiently.
Disclosure of Invention
The first aim of the invention is to provide a preparation method of a biochar@five-membered metal oxide composite defluorination material (also called as defluorination material in the invention), which aims at preparing the defluorination material with high adsorption performance by using biomass waste.
The second aim of the invention is to provide the biochar@five-membered metal oxide composite defluorination material prepared by the preparation method.
A third object of the present invention is to provide the use of said defluorinating material.
The preparation method of the biochar@five-membered metal oxide composite defluorination material comprises the following steps:
step (1):
carrying out solvothermal treatment on a raw material solution containing biomass and alkali, and then carrying out solid-liquid separation to obtain an alkali treatment solution; wherein, in the raw material solution, the concentration of alkali is more than or equal to 2M; the temperature of the solvothermal is greater than or equal to 150 ℃;
step (2):
adding La, zr, al, ce and water-soluble metal salt of Sc into the alkali treatment liquid to react;
step (3):
carrying out microwave heat treatment on the reaction system in the step (2) to obtain the biochar@five-membered metal oxide composite defluorination material;
wherein the temperature of the microwave heat treatment is 400-450 ℃.
The research of the invention finds that the biomass component is complex, contains more fluorine adsorption active components, but does not have a great deal of irrelevant and toxic fluorine adsorption activity. Therefore, in order to successfully produce high-performance defluorinated materials from biomass, it is necessary to properly solve the problem of selectivity of biomass components. Therefore, the invention researches and discovers that the biomass of the type, the solvent heat treatment, the special five-element synergistic metal component, the microwave heat treatment and the parameter joint control are innovatively adopted, so that a synergistic effect can be generated, and a material with excellent fluorine adsorption capacity and adsorption stability can be prepared.
In the invention, the combination of biomass types, solvothermal process conditions, required five-membered metal components and a microwave heat treatment process is a key for synergistically regulating and controlling biomass components, synergistically improving component phases and structures and finally improving the fluorine adsorption performance of the defluorination material.
In the invention, the biomass is at least one of wood, straw, paper products, pine, grasses, rice hulls, bagasse, cotton, jute, flax, bamboo, sisal, abaca, straw and corncob; more preferably at least one of corncob and bamboo. The research shows that the material with the preferable material has better synergy with the whole process of the invention unexpectedly, and can be prepared into the material with better defluorination performance.
In the present invention, the biomass may be fresh or dehydrated and pulverized, for example, the biomass has a water content of less than 10% and a particle size of less than 1mm.
In the invention, the biomass and the alkali are subjected to the solvothermal reaction, so that micro-carbonization treatment can be realized, the components of substances can be regulated and controlled, the process is combined with subsequent five-element treatment and microwave heat treatment, and the adsorption performance of the prepared biochar-based defluorination material can be unexpectedly and synergistically improved.
The solvent in the raw material solution is a mixed solution of water and a water-organic solvent; the organic solvent is a solvent mixed with water, preferably an alcohol with C1-C4;
preferably, the alkali is at least one of alkali metal hydroxide, carbonate and bicarbonate;
preferably, the starting alkali concentration of the raw material solution is 2-4M.
Preferably, the weight ratio of biomass to alkali is 1:0.3-0.5.
Preferably, the temperature of the solvothermal is 150-250 ℃;
the research shows that under the condition of the alkali concentration and the temperature, the types of the biomass are further cooperated, so that the defluorination active ingredients in the biomass can be regulated and controlled with high selectivity, the subsequent five-membered treatment and microwave treatment process can be further cooperated, and the better defluorination performance can be further cooperated.
Preferably, the solvothermal time is 2-4 hours.
In the present invention, the solvothermal system may be subjected to solid-liquid separation by conventional means, for example, filtration.
In the invention, under the solvothermal assistance of the biomass and the alkali, the special five-membered composite metal is further matched, so that the coordination is further realized, and the adsorption effect of fluorine is improved.
In the invention, the water-soluble metal salt is sulfate, nitrate or chloride of the at least one metal element.
Preferably, the molar ratio of La, zr, al, ce to Sc is (1 to 3): (1-3): (1-3): (1-3): (1-3); further preferably (1 to 3): (1-3): (1-2): (1-3): (1-2).
Preferably, the weight ratio of the total water-soluble metal salt to the biomass is 0.5-5: 1.
preferably, the water-soluble metal salt is dissolved in water in advance, then alcohol with 1 to 4 carbon atoms is added to obtain water-soluble metal salt solution, and the solution is mixed with alkali treatment solution for reaction;
preferably, the alcohol accounts for 0.5-1.5% of the volume of water in the water-soluble metal salt solution. The invention researches find that the alcohol solution of the matching part is favorable for further synergistically improving the defluorination performance of the prepared material.
Preferably, the molar concentration of Al in the water-soluble metal salt solution is 0.1-0.5 mol/L;
preferably, in the step (2), the reaction time is 1-3 hours;
preferably, in step (2), the pH at the end of the reaction is controlled to 8.5.+ -. 0.5.
In the invention, the system reacted in the step (2) is subjected to heat treatment under the assistance of microwaves, so that the structure and the phase of the material can be further regulated and controlled, and the fluorine adsorption performance of the material can be improved.
In the present invention, the microwave power is not particularly required, and may be 500 to 1500W, for example;
preferably, the microwave heat treatment stage is carried out in a protective atmosphere;
preferably, the time of microwave heat treatment is 30-120 min;
preferably, the biochar@five-membered metal oxide composite defluorination material is prepared by water washing treatment after microwave heat treatment and subsequent drying.
More specific embodiments of the invention include the steps of:
the first step: preparation of alkali treatment liquid based on biomass solid waste
Weighing sodium hydroxide or potassium hydroxide accounting for 30-50% of the weight of the biomass waste, adding the sodium hydroxide or potassium hydroxide and the biomass waste into water together, enabling the alkali concentration in the solution to be 2-4mol/L, then placing the solution containing the biomass waste and the alkali into a closed reactor, treating the solution at 150-250 ℃ for 2-4 hours, cooling and filtering the solution to obtain an alkali treatment solution; the water content of the biomass solid waste adopted in the step is lower than 10%, and the granularity is smaller than 1mm.
And a second step of: preparation of precursor solution for preparing multi-metal oxide
Firstly, according to the mol ratio of La, zr, al, ce to Sc (1-3): (1-3): (1-3): (1-3): (1-3) respectively weighing soluble lanthanum salt, zirconium salt, aluminum salt, cerium salt and scandium salt, wherein the total weight of the five salts is 0.5-5 times of the biomass waste weighed in the first step; then preparing aluminum salt into solution with the molar concentration of aluminum ions of 0.1-0.5 mol/L by using deionized water, adding the weighed lanthanum salt, zirconium salt, cerium salt and scandium salt into the aluminum salt solution under the condition of stirring, and adding C1-C4 alcohol according to 0.5-1.5% of deionized water after all the weighed salts are dissolved, thus completing the preparation of the solution. The soluble lanthanum salt in the step refers to one of lanthanum sulfate, lanthanum chloride or lanthanum nitrate; the soluble zirconium salt refers to one of zirconium oxychloride or zirconyl nitrate; the soluble aluminum salt refers to any one of aluminum sulfate, aluminum nitrate or aluminum chloride; the soluble cerium salt refers to ceric sulfate; the soluble scandium salt refers to one of scandium chloride or scandium sulfate.
Thirdly, placing the solution obtained in the second step into a constant-temperature water bath with the temperature of 50-60 ℃, slowly adding the alkali treatment solution obtained in the first step into the solution obtained in the second step under the condition of continuous stirring, and adjusting the pH value of the solution to 8.5+/-0.5 by using sulfuric acid or sodium hydroxide after the addition is finished, and continuously stirring for 1-3 hours to obtain slurry;
fourthly, placing the slurry into a microwave heating furnace, preserving heat for 30-120 minutes at 400-450 ℃, and cooling to room temperature along with the furnace; and then washing the material with deionized water to a pH value of 7.0+/-0.2, and drying at 120 ℃ for 12-24 hours to obtain the fluorine removing agent.
The invention also provides the biochar@five-membered metal oxide composite defluorination material prepared by the preparation method.
In the invention, the special phase and microstructure of the prepared material can be endowed by the special preparation process, and the brand new material prepared by the preparation method has more excellent fluorine adsorption performance.
In the present invention, the particle size of the defluorination material is not required, and may be, for example, 100 mesh to 300 mesh.
The particle size of the metal oxide in the defluorinating material is, for example, 1-10um.
The invention also provides an application of the biochar@five-membered metal oxide composite defluorination material prepared by the preparation method, and the biochar@five-membered metal oxide composite defluorination material is used as the defluorination material.
The invention is preferably applied to the adsorption of fluoride ions in a solution system by using the fluorine-removing material;
preferably, the pH of the adsorption stage is between 5.0 and 9.0;
preferably, the biochar@five-membered metal oxide composite defluorination material in the adsorption process is used in an amount of 1-5 g/L.
The invention has the advantages that:
the invention innovatively adopts the biomass of the kind, is matched with the solvothermal treatment, the special five-membered synergistic metal component and the microwave thermal treatment, and can accidentally prepare the material with excellent fluorine adsorption capacity and adsorption stability.
The research shows that the fluorine adsorption capacity of the defluorination material can reach more than 240mg/g, and the defluorination material has excellent adsorption performance.
In the invention, biomass is subjected to solvothermal recombination in advance under the assistance of alkali, and then is matched with microwave heat treatment under the assistance of a special five-membered metal source, so that synergy can be realized, excellent mesoporous/microporous characteristics can be endowed to the material, in addition, the formation of oxide active nano particles of the five-membered metal element on the surface of the material is also facilitated, and the removal effect of fluorine can be synergistically improved through the synergistic combination of the structure and the active components.
The method is simple and convenient to operate.
Detailed Description
In the following cases, the water content of the biomass is less than 10%, and the particle size is less than 1mm;
in the following cases, the alkali and the ratio between metal and biomass refer to the ratio to the dry weight of biomass, and the dry weight refers to the water content of not more than 10%.
Example 1
Preparation of high-capacity fluorine-removing material with corncob as raw material and effect of preparing fluorine-containing water body with neutral treatment
The preparation steps of the defluorination material of the embodiment are as follows:
the first step: preparation of alkali treatment liquid for corncob
Weighing KOH accounting for 40% of the weight of the corncob, adding the KOH and the corncob into water together to enable the alkali concentration in the solution to be 4mol/L, heating the system to 200 ℃ for treatment for 3 hours, cooling, and filtering the system, thereby obtaining the biomass solid waste alkali treatment liquid.
And a second step of: preparation of precursor solution for preparing multi-metal oxide
First, according to the mol ratio of La, zr, al, ce to Sc of five elements of 3:3:1:2:1, respectively weighing lanthanum chloride, zirconium oxychloride, aluminum chloride, ceric sulfate and scandium chloride, wherein the total weight of the five salts is 1.5 times of that of corncob waste weighed in the first step; and then preparing aluminum salt into a solution with the molar concentration of aluminum ions of 0.2mol/L by using deionized water, adding the weighed lanthanum salt, zirconium salt, cerium salt and scandium salt into the aluminum salt solution under the condition of stirring, and adding absolute ethyl alcohol according to the adding amount of 1v% of deionized water after all the weighed salts are dissolved, thus completing the preparation of the solution.
Thirdly, placing the solution obtained in the second step in a constant-temperature water bath at 60 ℃, slowly adding the alkali treatment solution obtained in the first step into the solution obtained in the second step under the condition of continuous stirring, and adjusting the pH value of the solution to 8.5+/-0.5 by using sulfuric acid or sodium hydroxide after the addition is finished, and continuously stirring for 1h to obtain viscous slurry;
fourthly, the viscous slurry is put into a sealed tank, the sealed equipment is put into a microwave heating furnace, the temperature is kept for 30 minutes at 450 ℃, and the sealed equipment is cooled to room temperature along with the furnace; and then washing the material with deionized water to a pH value of 7.0+/-0.2, and drying at 120 ℃ for 12 hours to obtain the defluorination material.
Defluorination capacity of defluorination material prepared in this example:
taking 2g of the defluorination material prepared in the embodiment, putting 1000ml of water with pH value of about 6 (+ -0.5) and fluorine content of 485mg/L, stirring for 30min, filtering, and testing to find that the fluorine content in the water is reduced to 1mg/L; the fluorine adsorption capacity of the prepared defluorination material is about 242mg/g.
Example 2
Preparation of defluorination material with bamboo scraps as raw material and defluorination effect of electrolyte in zinc electrodeposition
The preparation steps of the defluorination material of the embodiment are as follows:
the first step: preparation of alkali treatment liquid for bamboo scraps
And (3) weighing 50% NaOH by weight of bamboo chips and adding the NaOH and biomass waste into water together to enable the alkali concentration in the solution to be 3mol/L, heating the system to 200 ℃ for 2h, cooling, and filtering the filtrate to obtain the bamboo chip alkali treatment liquid.
And a second step of: preparation of precursor solution for preparing multi-metal oxide
First, according to the mol ratio of La, zr, al, ce to Sc of five elements of 3:3:1:1:2, respectively weighing soluble lanthanum nitrate, zirconyl nitrate, aluminum nitrate, ceric sulfate and scandium sulfate, wherein the total weight of the five salts is 4 times of that of bamboo scraps weighed in the first step; and then preparing aluminum salt into a solution with the molar concentration of aluminum ions of 0.5mol/L by using deionized water, adding the weighed lanthanum salt, zirconium salt, cerium salt and scandium salt into the aluminum salt solution under the condition of stirring, and adding absolute ethyl alcohol according to the adding amount of 0.5v% of deionized water after all the weighed salts are dissolved, thus completing the preparation of the solution.
Thirdly, placing the solution obtained in the second step in a constant-temperature water bath at 50 ℃, slowly adding the alkali treatment solution obtained in the first step into the solution obtained in the second step under the condition of continuous stirring, adjusting the pH value of the solution to 8.5+/-0.5 after the addition is finished, and continuously stirring for 3 hours to obtain viscous slurry;
fourthly, the viscous slurry is put into a sealed tank, the sealed equipment is put into a microwave heating furnace, the temperature is kept at 400 ℃ for 120 minutes, and the sealed equipment is cooled to room temperature along with the furnace; and then washing the material with deionized water to a pH value of 7.0+/-0.2, and drying at 120 ℃ for 24 hours to obtain the fluorine removing agent.
The fluorine removal capacity of the fluorine removal material prepared in the embodiment is determined by the following steps:
2g of the defluorination material prepared in the embodiment is put into 1000ml of zinc sulfate electrolyte with pH value of about 5 (5-5.5) and fluorine content of 520mg/l from a certain zinc hydrometallurgy enterprise in Hunan, and is stirred for 60min and then filtered, and the fluorine content in the electrolyte is reduced to 20mg/l through test; the fluorine adsorption capacity of the prepared defluorination material is about 250mg/g.
Example 3
Preparation of high-capacity defluorination material with corncob as raw material and defluorination effect of electrolyte in zinc electrodeposition
The preparation steps of the defluorination material of the embodiment are as follows:
the first step: preparation of alkali treatment liquid for corncob
And (3) weighing NaOH accounting for 30% of the weight of the corncob, adding the NaOH and the corncob into water together to enable the alkali concentration in the solution to be 4mol/L, heating the system to 250 ℃ for treatment for 4 hours, cooling, and filtering the filtrate to obtain the biomass solid waste alkali treatment liquid.
And a second step of: preparation of precursor solution for preparing multi-metal oxide
First, according to the mol ratio of La, zr, al, ce to Sc of five elements of 1:1:1:1:1, respectively weighing lanthanum chloride, zirconium oxychloride, aluminum chloride, ceric sulfate and scandium chloride, wherein the total weight of the five salts is 0.5 times of that of corncob waste weighed in the first step; and then preparing aluminum salt into a solution with the molar concentration of aluminum ions of 0.1M by using deionized water, adding the weighed lanthanum salt, zirconium salt, cerium salt and scandium salt into the aluminum salt solution under the condition of stirring, and adding propanol according to 1v% of the deionized water after all the weighed salts are dissolved, thus completing the preparation of the solution.
Thirdly, placing the solution obtained in the second step in a constant-temperature water bath at 50 ℃, slowly adding the alkali treatment solution obtained in the first step into the solution obtained in the second step under the condition of continuous stirring, and adjusting the pH value of the solution to 8.5+/-0.5 by using sulfuric acid or sodium hydroxide after the addition is finished, and continuously stirring for 2 hours to obtain viscous slurry;
fourthly, the viscous slurry is put into a sealed tank, placed into a microwave heating furnace, kept at 400 ℃ for 120 minutes, and cooled to room temperature along with the furnace; and then washing the material with deionized water to a pH value of 7.0+/-0.2, and drying at 120 ℃ for 24 hours to obtain the defluorination material.
Defluorination capacity of defluorination material prepared in this example:
2g of the defluorination material prepared in the embodiment is put into 1000ml of zinc sulfate electrolyte with pH value of about 5 and fluorine content of 520mg/l from a certain zinc hydrometallurgy enterprise in Hunan, and is filtered after stirring for 60min, and the fluorine content in the electrolyte is reduced to 25mg/l through test; the fluorine adsorption capacity of the prepared defluorination material is about 245mg/g.
Example 4
Preparation of defluorination material using bamboo scraps as raw material and effect of defluorination material in treating neutral fluorine-containing water body
The preparation steps of the defluorination material of the embodiment are as follows:
the first step: preparation of alkali treatment liquid for bamboo scraps
And (3) weighing 50% of KOH by weight of bamboo chips and adding the KOH and biomass waste into water together to enable the alkali concentration in the solution to be 2mol/L, heating the system to 150 ℃ for 4 hours, cooling, and filtering the system to obtain the bamboo chip alkali treatment liquid.
And a second step of: preparation of precursor solution for preparing multi-metal oxide
First, according to the mol ratio of La, zr, al, ce to Sc of five elements of 2:1:1:3:1, respectively weighing soluble lanthanum nitrate, zirconyl nitrate, aluminum nitrate, ceric sulfate and scandium sulfate, wherein the total weight of the five salts is 5 times of that of bamboo scraps weighed in the first step; and then preparing aluminum salt into a solution with the molar concentration of aluminum ions of 0.5mol/L by using deionized water, adding the weighed lanthanum salt, zirconium salt, cerium salt and scandium salt into the aluminum salt solution under the condition of stirring, and adding methanol according to the addition amount of 1v% of the deionized water after all the weighed salts are dissolved, thus completing the preparation of the solution.
Thirdly, placing the solution obtained in the second step in a constant-temperature water bath at 50 ℃, slowly adding the alkali treatment solution obtained in the first step into the solution obtained in the second step under the condition of continuous stirring, adjusting the pH value of the solution to 8.5+/-0.5 after the addition is finished, and continuously stirring for 3 hours to obtain viscous slurry;
fourthly, the viscous slurry is put into a sealed tank, the sealed equipment is put into a microwave heating furnace, the temperature is kept at 400 ℃ for 60 minutes, and the sealed equipment is cooled to room temperature along with the furnace; and then washing the material with deionized water to a pH value of 7.0+/-0.2, and drying at 120 ℃ for 12 hours to obtain the fluorine removing agent.
Defluorination capacity of defluorination material prepared in this example:
taking 2g of the defluorination material prepared in the embodiment, putting 1000ml of water with pH value of about 6 and fluorine content of 485mg/L, stirring for 30min, filtering, and testing to find that the fluorine content in the water is reduced to 3mg/L; the fluorine adsorption capacity of the prepared defluorination material is about 241mg/g.
Example 5
The difference compared to example 1 is only that in the second step, no additional 1v% ethanol was added to the metal solution. Other parameters were the same as in example 1.
The fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity was 212mg/g.
Therefore, the process disclosed by the invention can be used for cooperating with the process disclosed by the invention, so that the adsorption capacity can be further improved.
Comparative example 1
Compared with example 1, the difference is only that in the second step, the molar ratio of La, zr, al, ce to Sc is 3:3:1:1:0.
the fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity was only 31mg/g.
Comparative example 2
Compared with example 1, the difference is only that the molar ratio of La, zr, al, ce to Sc in the second step is 0:3:1:1:2.
the fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity was only 32mg/g.
Comparative example 3
Compared with example 1, the difference is only that in the second step, the molar ratio of La, zr, al, ce to Sc is 3:0:1:1:2.
the fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity is only 28mg/g.
Comparative example 4
Compared with example 1, the difference is only that in the second step, the molar ratio of La, zr, al, ce to Sc is 3:3:1:0:2.
the fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity was only 26mg/g.
Comparative example 5
Compared with example 1, the difference is only that the molar ratio of La, zr, al, ce to Sc in the second step is 0:3:1:0:0.
the fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity is only 20mg/g.
Comparative example 6
Compared with the example 1, the difference is only that five elements of Mg, zr, ca, ce and Sc are adopted in the second step, and the molar ratio is 3:3:1:2:1 respectively weighing magnesium chloride, zirconium oxychloride, calcium chloride, ceric sulfate and scandium chloride.
The fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity was only 13mg/g.
Comparative example 7
The only difference compared to example 1 is that the hydrothermal temperature in step one is only 120 ℃.
The fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity was only 41mg/g.
Comparative example 8
The difference compared with example 1 is only that the alkali concentration in the first step is 1mol/L.
The fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity was only 52mg/g.
Comparative example 9
The difference compared with example 1 is only that the ordinary electric heating (resistance wire heating) is adopted in the fourth step.
The fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity was only 82mg/g.
Comparative example 10
The only difference compared to example 1 is that in step four, the heating temperature is 350 ℃.
The fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity was only 75mg/g.
Comparative example 11
The only difference compared to example 1 is that in step four, the heating temperature is 500 ℃.
The fluorine removal capacity was measured by the method of example 1, and the result was: the fluorine adsorption capacity was only 91mg/g.

Claims (27)

1. The preparation method of the biochar@five-membered metal oxide composite defluorination material is characterized by comprising the following steps of:
step (1):
carrying out solvothermal treatment on a raw material solution containing biomass and alkali, and then carrying out solid-liquid separation to obtain an alkali treatment solution; wherein, in the raw material solution, the concentration of alkali is more than or equal to 2M; the temperature of the solvothermal is greater than or equal to 150 ℃; the biomass is at least one of wood, straw, paper products, grasses, rice hulls, bagasse, cotton, jute, flax, bamboo, sisal, abaca, straw and corncob;
step (2):
adding La, zr, al, ce and water-soluble metal salt of Sc into the alkali treatment liquid to react;
step (3):
carrying out microwave heat treatment on the reaction system in the step (2) to obtain the biochar@five-membered metal oxide composite defluorination material;
wherein the temperature of the microwave heat treatment is 400-450 ℃.
2. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the biomass is at least one of corncob and bamboo.
3. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the water content of biomass is lower than 10%, and the granularity is smaller than 1mm.
4. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the solvent in the raw material solution is a mixed solution of water and a water-organic solvent; the organic solvent is a solvent mixed with water.
5. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 4, wherein the solvent is C1-C4 alcohol.
6. The method for preparing biochar @ five-membered metal oxide composite defluorination material according to claim 1, wherein the alkali is at least one of alkali metal hydroxide, carbonate and bicarbonate.
7. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the initial alkali concentration of the raw material solution is 2-4M.
8. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the weight ratio of biomass to alkali is 1:0.3-0.5.
9. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the solvothermal temperature is 150-250 ℃.
10. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the solvothermal time is 2-4h.
11. The method for preparing biochar @ five-membered metal oxide composite defluorinated material according to claim 1, wherein the water-soluble metal salt is a sulfate, nitrate or chloride salt of the at least one metal element.
12. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the molar ratio of La, zr, al, ce to Sc is (1-3): (1-3): (1-3): (1-3): (1-3).
13. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the weight ratio of total water-soluble metal salt to biomass is 0.5-5: 1.
14. the method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the water-soluble metal salt is dissolved in water in advance, then the alcohol of C1-C4 is added to obtain a water-soluble metal salt solution, and the solution is mixed with an alkali treatment solution for reaction.
15. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the alcohol accounts for 0.5-1.5% of the volume of water in the water-soluble metal salt solution.
16. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the molar concentration of Al metal in the water-soluble metal salt solution is 0.1-0.5 mol/L.
17. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein in the step (2), the reaction time is 1-3 h.
18. The method for producing a biochar @ five-membered metal oxide composite defluorinated material according to claim 1, wherein in step (2), the pH at the reaction end point is controlled to be 8.5±0.5.
19. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the microwave power is 500-1500W.
20. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the microwave heat treatment stage is carried out in a protective atmosphere.
21. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the time of microwave heat treatment is 30-120 min.
22. The method for preparing the biochar@five-membered metal oxide composite defluorination material according to claim 1, wherein the biochar@five-membered metal oxide composite defluorination material is prepared by performing water washing treatment after microwave heat treatment and then drying.
23. A biochar @ five-membered metal oxide composite defluorinated material prepared by the preparation method of any one of claims 1 to 22.
24. Use of the biochar @ five-membered metal oxide composite defluorinated material prepared by the preparation method according to any one of claims 1 to 22, as defluorinated material.
25. The application of the biochar@five-membered metal oxide composite fluorine removing material prepared by the preparation method according to claim 24, which is characterized in that the biochar@five-membered metal oxide composite fluorine removing material is used as a fluorine removing material for adsorbing fluorine ions in a solution system.
26. The biochar @ five-membered metal oxide composite defluorination material prepared by the preparation method of claim 25, wherein the pH of the adsorption stage is 5.0-9.0.
27. The application of the biochar@five-membered metal oxide composite defluorination material prepared by the preparation method according to claim 25, wherein the using amount of the biochar@five-membered metal oxide composite defluorination material in the adsorption process is 1-5 g/L.
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