CN113578287B - Fluorine adsorbent and preparation and application thereof - Google Patents

Fluorine adsorbent and preparation and application thereof Download PDF

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CN113578287B
CN113578287B CN202110990384.6A CN202110990384A CN113578287B CN 113578287 B CN113578287 B CN 113578287B CN 202110990384 A CN202110990384 A CN 202110990384A CN 113578287 B CN113578287 B CN 113578287B
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fluorine
adsorbent
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fluorine adsorbent
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CN113578287A (en
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王明玉
廖志琴
赵士杰
谢渝
李析菘
湛菁
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Central South University
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    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/00—Nature of the contaminant
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Abstract

The invention discloses a fluorine adsorbent and a preparation and application method thereof, and the fluorine adsorbent which has large particles and large fluorine adsorption capacity and can be recycled can be prepared by the method; the fluorine adsorbent can dynamically remove fluorine in an ion exchange column mode, can also statically remove fluorine in a shaking table mode, can be used as a raw material for preparing fluoride, and has the advantages of simple process, convenience in operation and good fluorine removal effect in the whole application process.

Description

Fluorine adsorbent and preparation and application thereof
Technical Field
The invention belongs to the technical field of fluoride ion adsorption, and particularly relates to a fluoride adsorbent.
Background
Fluorine in the wastewater is a substance with a large toxic effect on human beings; the suitable fluorine content in domestic drinking water specified in China is 0.5-1.0 mg/L, and the maximum allowable discharge concentration of fluorine in industrial wastewater is 10 mg/L. If the concentration of fluorine exceeds a certain value in industrial production, the production can be seriously influenced, for example, zinc smelting enterprises have strict limits on the fluorine content in zinc electrolyte, the fluorine ion concentration is required to be not higher than 50mg/L, and nickel electrolysis systems, power battery wet extraction nickel-cobalt-manganese systems and the like also have corresponding fluorine content requirements.
At present, the method for removing fluorine in the solution at home and abroad mainly comprises a chemical precipitation method, a coagulating precipitation method, an ion exchange method, an adsorption method and the like. The chemical precipitation method is to remove fluorine by reacting fluorine in a solution with calcium salt, magnesium salt, aluminum salt and the like to generate a fluorine-containing compound which is difficult to dissolve, and then filtering and separating the fluorine-containing compound. The coagulating sedimentation method is also one of the most applied methods for treating fluorine-containing wastewater, and the basic principle of the method is that a coagulant is added into a fluorine-containing solution to form hydroxide colloid for adsorbing and removing fluorine under certain conditions; the coagulation sedimentation method is mainly used for wastewater treatment, impurity ions are introduced when the coagulation sedimentation method is applied to an industrial production system, and in addition, a large amount of fluorine-containing solid waste which is difficult to treat is generated. Ion exchange processes produce large amounts of wastewater and also cause secondary pollution to metallurgical extraction systems. At present, the adsorption method for removing fluorine is the method which is most used for deeply removing fluorine, and usually, a fluorine removing agent is added into a fluorine-containing solution, and then the solution is stirred and filtered for separation, so that the fluorine is removed, and common adsorbents mainly comprise activated alumina, fly ash, activated carbon, molecular sieves, silicates and the like; the adsorbents are usually only used for removing fluorine from near-neutral wastewater, and the adsorption capacity of the fluorine is smaller and is usually only 0.3-30 mg/g; in addition, the adsorbents are usually added in a powder form, so that solid-liquid separation is difficult, and in addition, the adsorbents are difficult to resolve, difficult to recycle and realize actual industrial large-scale use.
Disclosure of Invention
The invention aims to provide a brand-new preparation method of a fluorine adsorbent, aiming at overcoming the defects that the prior fluorine adsorbent is difficult to realize the adsorption capacity, the desorption (desorption) capacity, the cycle regeneration capacity and the adsorption selectivity, and the fluorine adsorbent which has good adsorption capacity, excellent desorption capacity, cycle regeneration capacity and ion adsorption selectivity is obtained by controlling the preparation method.
The second purpose of the invention is to provide the fluorine adsorbent prepared by the preparation method.
The third purpose of the invention is to provide the application of the fluorine adsorbent prepared by the preparation method in the selective adsorption of fluorine ions.
The existing fluorine adsorbent is mainly an ultrafine powder adsorbent, which has good adsorption capacity, but also has the defects of difficult solid-liquid separation, difficult analysis, difficult cyclic regeneration, unsatisfactory adsorption selectivity and the like, and is difficult to really realize industrial scale-up use. In view of the above problems, the present inventors have previously tried to bind particles by a polymerization crosslinking method in order to solve the problem that the solid-liquid separation of the adsorbent is difficult, but have found that the method has a certain effect in solving the solid-liquid separation, but has technical difficulties such as blocking of adsorption sites due to the polymerization binding method and unsatisfactory adsorption capacity, adsorption selectivity and desorption capacity, and have further studied and developed the following solutions in view of the technical difficulties:
a preparation method of a fluorine adsorbent comprises the following steps:
step (1): premixing a silicon source, an aluminum source, alkali and water to obtain slurry, placing the slurry and a rare earth source in a closed container, reacting at the temperature of more than or equal to 100 ℃, and then carrying out solid-liquid separation to obtain a rare earth aluminum-silicon product;
step (2): placing the rare earth aluminum-silicon product in a fluorine salt solution containing fluorine ions for fluorination treatment to obtain a fluorinated product;
and (3): mixing a fluorinated material with a alginic acid source and a crosslinking source, and performing crosslinking treatment to obtain a crosslinked product; wherein the weight ratio of the alginate to the fluorinated product is 0.5-10%;
and (4): and (3) treating the cross-linked product in alkali liquor to prepare the fluorine adsorbent.
In order to solve the technical problems of adsorption site closure, adsorption capacity, selectivity and desorption capacity which are caused by polymerization crosslinking, the research of the invention discovers that the coordination can be realized by innovatively doping the silicon structure with aluminum and rare earth and further matching with the fluorination treatment, controllable alginic acid crosslinking treatment and alkali treatment, so that the fluorine ion exchange adsorption can be effectively improved, the exchange adsorption capacity and the adsorption selectivity can be improved, in addition, the analysis capacity can be obviously improved, and the cyclic adsorption stability can be improved.
In the invention, the aluminum source and the rare earth are innovatively used for assisting in high-temperature treatment, and the silicon can be subjected to lattice doping through the aluminum and the rare earth, so that the coordination with the subsequent fluorination, controllable crosslinking and alkali treatment processes is facilitated, and the problems of activity closure, adsorption performance, adsorption selectivity and poor cycle stability caused by crosslinking are improved.
Preferably, the silicon source is at least one of alkali metal silicate, metasilicate and silicate ester. In the present invention, the alkali metal is, for example, at least one of Na and K. The silicate is, for example, C1-C4 alkyl ester of ortho silicic acid, such as at least one of methyl orthosilicate and ethyl orthosilicate.
Preferably, the aluminum source is at least one of sodium aluminate, sodium metaaluminate, potassium aluminate and potassium metaaluminate;
preferably, the alkali is at least one of alkali metal hydroxide, carbonate and ammonia water.
Preferably, the silicon source, the aluminum source, the alkali and the water in the slurry are mixed according to the ratio of Si: al: OH (OH)-：H2The molar ratio of O is 2-50: 1: 2-25: 100-1000 (preferably 2-20: 1: 2-20: 100-400);
preferably, in the step (1), the temperature in the premixing stage is 10-100 ℃;
preferably, in step (1), the time for premixing is 5-60 min.
In the present invention, the rare earth source is a water-soluble salt of a rare earth element, and may be at least one of nitrate, sulfate and chloride, for example. Preferably, the rare earth source is a water-soluble salt of cerium and lanthanum; further preferably at least one of cerium nitrate, cerium sulfate, cerium chloride, lanthanum nitrate, lanthanum chloride and lanthanum sulfate;
preferably, the molar weight of the rare earth element in the rare earth source and the molar weight of the aluminum in the aluminum source are 0.3-5 times, preferably 3-5 times;
preferably, in the step (1), the reaction temperature is 100 to 200 ℃, and more preferably 150 to 200 ℃:
preferably, in the step (1), the reaction time is 3-48 h, and preferably 3-12 h.
In the invention, after the aluminum and rare earth crystal lattice hybridization treatment in the step (1), the subsequent fluorination transformation treatment is further matched, which is beneficial to further improving the adsorption capacity, selectivity and cycling stability.
In the step (2), the fluorine salt solution is an aqueous solution of water-soluble fluorine salt; the preferable fluorine salt is at least one of sodium fluoride, potassium fluoride and ammonium fluoride;
preferably, the concentration of the solute in the fluorine salt solution is 0.5-4 mol/L, preferably 2-4M;
preferably, the solid-liquid ratio of the rare earth aluminum silicon product to the fluorine salt solution is 1: 1.5-10 g/mL;
preferably, the temperature in the fluorination treatment process is 10-100 ℃;
preferably, the time of the fluorination treatment process is 10 to 60 min.
In the invention, on the basis of the treatment in the steps (1) and (2), the alginic acid crosslinking process and the combined control of the conditions are further combined, so that controllable crosslinking can be realized, and the adsorption capacity, the adsorption selectivity and the cycle stability of the adsorbent can be synergistically improved.
In the present invention, the fluorinated product may be preliminarily placed in an aqueous solution of a alginic acid source, and then a solution of a crosslinking source may be added thereto to effect crosslinking.
The alginic acid source is alginic acid and water-soluble salt thereof, such as sodium alginate;
in the invention, under the combined process, the control of the dosage of the alginic acid source is further matched, which is beneficial to further realizing controllable crosslinking and is more beneficial to the comprehensive performance of the adsorbing material.
Preferably, the weight ratio of the alginate to the fluorinated product is 0.5-5%.
The crosslinking source is a water-soluble salt capable of crosslinking and polymerizing the alginic acid source, such as a water-soluble salt of at least one element selected from calcium, nickel and cobalt; preferably at least one of calcium chloride, nickel chloride and cobalt chloride;
the solution of the crosslinking source is, for example, an aqueous solution in which the crosslinking source is dissolved, and the concentration thereof is not particularly limited; for example, it may be a saturated solution or a solution having a concentration lower than the saturated concentration, and the concentration thereof may preferably be 0.1 to 10 wt.% in view of cost.
The amount of the crosslinking source is not particularly limited, and the crosslinking of the alginic acid source may be achieved, for example, the amount of the crosslinking source is 0.2 to 0.6 times, preferably 0.2 to 0.4 times the weight of the alginic acid source.
Preferably, the temperature of the crosslinking reaction is 10-100 ℃, and the time of the crosslinking reaction is preferably 1-48 h.
In the present invention, the crosslinked product is treated in an alkali solution. The alkali solution has no special requirement, and the solution with ionized OH < - > and the pH value of more than 7 is only needed.
Preferably, in the step (4), the alkali solution is an alkaline solution containing OH-ions, and is preferably an aqueous solution of at least one of sodium hydroxide, potassium hydroxide and ammonia water;
preferably, the concentration of the solute in the alkali liquor is 0.5-3 mol/L;
preferably, the fluorination product is prepared in a weight ratio of 1: mixing the solid-liquid ratio of 1.5-15 g/mL with alkali liquor;
preferably, the temperature of the treatment stage is 10-100 ℃, and the time is preferably 10-60 min;
preferably, after the treatment is finished, solid-liquid separation is carried out, and then drying and screening are carried out to obtain the fluorine adsorbent.
The invention relates to a preferable preparation method, which is prepared by the following steps:
step (a), mixing silicon source, aluminum source, alkali 1 and water according to the molar ratio of silicon source, aluminum source, alkali 1 and water, namely Si: al: OH (OH)-：H2O is 2-50: 1: 2-25: 100-1000, and stirring for 5-60min at 10-100 ℃ to obtain slurry 1; the silicon source is at least one of alkali metal silicate, alkali metal metasilicate and tetraethoxysilane; the aluminum source is at least one of sodium aluminate, sodium metaaluminate, potassium aluminate and potassium metaaluminate; the alkali 1 is at least one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate and ammonia water;
mixing the slurry 1 and a rare earth source in a closed container, stirring and reacting for 3-48 h at 100-200 ℃, and filtering and separating to obtain a product 2; the rare earth source is at least one of cerium nitrate, cerium sulfate, cerium chloride, lanthanum nitrate, lanthanum chloride and lanthanum sulfate; the adding amount of the rare earth source is 0.3-5 times of the molar weight of aluminum in the aluminum source;
and (c) mixing the product 2 with 0.5-4 mol/L of villiaumite solution according to a solid-to-liquid ratio of 1: 1.5-10 g/mL of the mixture is stirred and reacted for 10-60min at 10-100 ℃, and a product 3 is obtained after filtration and separation; the fluorine salt is at least one of sodium fluoride, potassium fluoride and ammonium fluoride;
and (d) mixing the product 3 with a sodium alginate solution according to a solid-to-liquid ratio of 1: uniformly stirring 5-40 g/mL, dripping into a cross-linked salt solution, stirring and reacting for 1-48h at 10-100 ℃, and filtering and separating to obtain a product 4; the adding amount of the sodium alginate is 0.5-10% of the weight of the product 3; the cross-linked salt solution is a solution with the mass concentration of 0.5-10% obtained by dissolving at least one of calcium chloride, nickel chloride and cobalt chloride in water. The weight ratio of the addition amount of the cross-linked salt to the sodium alginate is 0.2-0.6: 1.
and (e) mixing the product 4 with 0.5-3 mol/L alkali 2 solution according to a solid-to-liquid ratio of 1: mixing 1.5-15 g/mL, carrying out oscillation reaction at 10-100 ℃ for 10-60min, filtering, separating, drying and screening to obtain a fluorine adsorbent; the alkali 2 is at least one of sodium hydroxide, potassium hydroxide and ammonia water;
the invention also provides a fluorine adsorbent prepared by the preparation method.
The preparation method can obtain a new material with a brand new phase and microcosmic characteristics through the combined cooperation of the preparation processes, and the new material has good adsorption capacity, adsorption selectivity, desorption capacity and cycling stability.
Preferably, the particle size of the fluorine adsorbent is 0.5-10 mm.
The invention also provides an application of the fluorine adsorbent, which is used for adsorbing fluorine ions.
In a preferred application of the present invention, the fluorine adsorbent is contacted with an aqueous solution containing fluorine ions (also referred to as fluorine-containing solution in the present invention) for adsorbing the fluorine ions therein.
In a preferred application of the invention, the fluorine adsorbent is contacted with an aqueous solution containing fluorine ions and hetero-ions for selectively adsorbing the fluorine ions therein.
Preferably, the hetero-ion is at least one of zinc ion, nickel ion, manganese ion, cobalt ion, sodium ion and lithium ion.
The application of the invention can carry out fluoride ion adsorption based on a dynamic or static mode;
for example, the static adsorption is performed by mixing the fluorine adsorbent with an aqueous solution containing fluorine ions. For example, the fluorine-containing solution is contacted with a fluorine adsorbent, and is shaken for 2-200 min at 10-70 ℃, and solid-liquid separation is carried out to obtain a loaded adsorbent and a liquid after fluorine removal. The loaded adsorbent is analyzed by 0.5-2 mol/L alkaline solution and recycled, and fluorine-containing analysis solution is used as a raw material for extracting villiaumite;
in another example, the dynamic adsorption is performed by packing an ion exchange column with the fluorine adsorbent and flowing an aqueous solution containing fluorine ions through the ion exchange column as a mobile phase. The specific steps are as follows: and (2) loading the fluorine adsorbent into an ion exchange column, and flowing the fluorine-containing solution through the ion exchange column at the temperature of 10-70 ℃, wherein the contact time of the solution and the adsorbent is 20-120 min. The loaded adsorbent is analyzed by 0.5-2 mol/L alkaline solution and recycled, and the fluorine-containing analysis solution is used as a raw material for extracting villiaumite.
The invention also provides a method for recovering fluorine ions in the fluorine-containing solution, wherein the fluorine adsorbent is adopted to adsorb the fluorine-containing solution to obtain a loaded adsorbent and a fluorine-removing solution, then the loaded adsorbent is desorbed by alkali liquor to recover a fluorine-containing desorption solution, and the desorbed fluorine adsorbent is recycled;
preferably, the fluorine adsorbent is filled into an ion exchange column, a fluorine-containing solution is adopted as a mobile phase to flow through the ion exchange column for adsorption, and a defluorination solution is obtained by collection; and then, adopting alkali liquor as a mobile phase to flow through the loaded ion exchange column for elution to obtain fluorine-containing desorption liquid, wherein the eluted ion exchange column is used for treating other batches of fluorine-containing solutions.
In the invention, the alkaline solution is formed by dissolving at least one of sodium hydroxide, potassium hydroxide and ammonia water in water.
Compared with the prior art, the invention has the following advantages and effects:
according to the invention, the aluminum-rare earth is used for carrying out high-temperature doping treatment on silicon, and further matched with subsequent fluorination treatment, alginic acid controllable crosslinking treatment and subsequent alkali treatment, so that the synergy can be generated, and the technical problems that the industrial application is difficult due to small particles of the existing adsorbing material and the adsorption capacity, adsorption selectivity, analysis and cycle performance are not ideal due to polymerization crosslinking can be effectively solved;
the fluorine adsorbent prepared by the method has large particles (the particle size is 0.5-10 mm), has large adsorption capacity (more than 40mg/g) for fluorine, and can be resolved and recycled; the prepared fluorine adsorbent can be used for dynamically removing fluorine in an ion exchange column mode, can also be used for statically removing fluorine in a shaking table mode, and fluorine desorption liquid can be used as a raw material for preparing fluoride.
Detailed Description
The following examples are intended to illustrate the invention without further limiting its scope.
Example 1
Taking 1000g of sodium metaaluminate, and then mixing the sodium metaaluminate with the following components in a molar ratio of Si: al: OH group-：H2O is 2: 1: 2: 100, adding sodium metasilicate, sodium hydroxide and water, stirring for 60min at 10 ℃, then adding cerium nitrate according to 5 times of the molar weight of aluminum in the sodium metaaluminate, placing the mixture in a closed container (the slurry filling amount is 40-60 v%), stirring and reacting for 3h at 200 ℃, and filtering and separating to obtain a solid product 1; mixing the solid product 1 with 4mol/L sodium fluoride solution according to a solid-liquid ratio of 1: 1.5g/mL of the mixture is stirred and processed for 60min at 10 ℃, and a solid product 2 is obtained by filtration and separation; and (3) mixing the solid product 2 with a sodium alginate solution according to a solid-to-liquid ratio of 1: stirring uniformly at 40g/mL (wherein the weight of sodium alginate is 10% of that of the solid product 2), dripping a calcium chloride solution with the mass concentration of 0.5% (wherein the weight ratio of calcium chloride to sodium alginate is 0.2: 1), stirring and reacting for 48h at 10 ℃, and filtering and separating to obtain a solid product 3; mixing the solid product 3 with 0.5mol/L sodium hydroxide solution according to the solid-liquid ratio of 1: mixing 15g/mL of the mixture, carrying out oscillation reaction at 100 ℃ for 10min, filtering, separating, drying and screening to obtain fluorine adsorption with the particle size of 0.5-10 mm.
Packing fluorine adsorbent into
Figure BDA0003232106570000071
Then a zinc electrolyte solution containing F158 mg/L, Zn 128g/L and pH 4.1 was flowed through the ion exchange column at room temperature, the solution and the adsorption were carried outThe contact time of the adsorbent is 60min, when the concentration of F in the solution after adsorption reaches 30mg/L, the zinc electrolyte is stopped to be added, and pure water with 4 times of the volume of the adsorbent is continuously passed (the adsorption capacity of the adsorbent to fluorine is 61.8 mg/g); the loaded adsorbent is resolved by 0.5mol/L sodium hydroxide solution to obtain regenerated adsorbent 1 and fluorine-containing resolving liquid, and the fluorine-containing resolving liquid is evaporated and crystallized to obtain sodium fluoride crystals. The following table shows the results of 5 cycles of the same operation as described above for regenerated adsorbent 1:
number of cycles 1 2 3 4 5
The fluorine adsorption amount of the adsorbent is mg/g 62.0 60.5 61.1 61.3 60.9
The zinc adsorption amount of the adsorbent is mg/g 30.2 32.9 31.4 29.8 32.7
As can be seen from example 1, the prepared material was able to successfully achieve column separation, and in addition, had excellent column separation adsorption stability and selective adsorption stability.
Comparative example 1
Compared with the example 1, the difference is that no aluminum source is added in the step (1), and other steps and conditions are the same as those in the example 1, specifically:
sodium metasilicate (1000g), sodium hydroxide and water were mixed in a molar ratio Si: OH group-：H2O is 2: 2: 100, stirring for 60min at 10 ℃, adding cerium nitrate, placing the mixture in a closed container (the slurry filling amount is 40-60 v%), stirring and reacting for 3h at 200 ℃, and filtering and separating to obtain a solid product 1; mixing the solid product 1 with 4mol/L sodium fluoride solution according to a solid-liquid ratio of 1: 1.5g/mL of the mixture is stirred and reacted for 60min at 10 ℃, and a solid product 2 is obtained by filtration and separation; and (3) mixing the solid product 2 with a sodium alginate solution according to a solid-to-liquid ratio of 1: stirring uniformly at 40g/mL (the adding amount of sodium alginate is 10% of the weight of the solid product 2), dripping into a calcium chloride solution with the mass concentration of 0.5%, stirring and reacting for 48h at 10 ℃, and filtering and separating to obtain a solid product 3; mixing the solid product 3 with 0.5mol/L sodium hydroxide solution according to the solid-liquid ratio of 1: mixing 15g/mL of the mixture, carrying out oscillation reaction at 100 ℃ for 10min, filtering, separating, drying and screening to obtain fluorine adsorption with the particle size of 0.5-10 mm.
Packing fluorine adsorbent into
Figure BDA0003232106570000081
The height of the adsorbent in the ion exchange column is 30cm, then zinc electrolyte containing F158 mg/L, Zn 128g/L and pH of 4.1 flows through the ion exchange column at room temperature, the contact time of the solution and the adsorbent is 60min, when the concentration of F in the solution after adsorption reaches 30mg/L, the zinc electrolyte is stopped to be added, and pure water with 4 times of the volume of the adsorbent is continuously passed (the adsorption capacity of the adsorbent to fluorine is 82.3 mg/g); the loaded adsorbent is resolved by 0.5mol/L sodium hydroxide solution to obtain regenerated adsorbent 1 and fluorine-containing resolving liquid.
The following table shows the results of 5 cycles of the same operation as described above for regenerated adsorbent 1:
number of cycles 1 2 3 4 5
The fluorine adsorption amount of the adsorbent is mg/g 40.0 24.5 10.1 8.4 5.9
Comparative example 2
Compared with the example 1, the difference is only that no rare earth source is added in the step (1), and other steps and conditions are the same as those in the example 1; the method specifically comprises the following steps:
taking 1000g of sodium metaaluminate, and then mixing the sodium metaaluminate with the following components in a molar ratio of Si: al: OH (OH)-：H2O is 2: 1: 2: 100, adding sodium metasilicate, sodium hydroxide and water, stirring for 60min at 10 ℃, then placing the mixture into a closed container (the slurry filling amount is 40-60 v%), stirring and reacting for 3h at 200 ℃, and filtering and separating to obtain a solid product 1; mixing the solid product 1 with 4mol/L sodium fluoride solution according to a solid-liquid ratio of 1: 1.5g/mL of the mixture is stirred and reacted for 60min at 10 ℃, and a solid product 2 is obtained by filtration and separation; will be fixedAnd mixing the state product 2 and the sodium alginate solution according to a solid-to-liquid ratio of 1: stirring uniformly at 40g/mL (the adding amount of sodium alginate is 10% of the weight of the solid product 2), dripping into a calcium chloride solution with the mass concentration of 0.5%, stirring and reacting for 48h at 10 ℃, and filtering and separating to obtain a solid product 3; mixing the solid product 3 with 0.5mol/L sodium hydroxide solution according to the solid-liquid ratio of 1: mixing 15g/mL of the fluorine adsorbent, performing oscillation reaction at 100 ℃ for 10min, filtering, separating, drying and screening to obtain fluorine adsorbent with the particle size of 0.5-10 mm.
Packing fluorine adsorbent into
Figure BDA0003232106570000082
The height of the adsorbent in the ion exchange column is 30cm, then zinc electrolyte containing F158 mg/L, Zn 128g/L and pH 4.1 flows through the ion exchange column at room temperature, the contact time of the solution and the adsorbent is 60min, when the concentration of F in the solution after adsorption reaches 30mg/L, the zinc electrolyte is stopped to be added, pure water with 4 times of the volume of the adsorbent is continuously passed, and the adsorption capacity of the adsorbent to fluorine is 6.5 mg/g.
Comparative example 3
Compared with the example 1, the difference is that the temperature of the step (1) is lower than 100 ℃ when the reaction is carried out in a closed container, specifically:
taking 1000g of sodium metaaluminate, and then mixing the sodium metaaluminate with the following components in a molar ratio of Si: al: OH group-：H2O is 2: 1: 2: 100, adding sodium metasilicate, sodium hydroxide and water, stirring for 60min at 10 ℃, then adding cerium nitrate according to 5 times of the molar weight of aluminum in the sodium metaaluminate, placing the mixture in a closed container (the slurry filling amount is 40-60 v%), stirring and reacting for 3h at 80 ℃, and filtering and separating to obtain a solid product 1; mixing the solid product 1 with 4mol/L sodium fluoride solution according to a solid-liquid ratio of 1: 1.5g/mL of the mixture is stirred and reacted for 60min at 10 ℃, and a solid product 2 is obtained by filtration and separation; and (3) mixing the solid product 2 with a sodium alginate solution according to a solid-to-liquid ratio of 1: stirring uniformly at 40g/mL (the adding amount of sodium alginate is 10% of the weight of the solid product 2), dripping into a calcium chloride solution with the mass concentration of 0.5%, stirring and reacting for 48h at 10 ℃, and filtering and separating to obtain a solid product 3; mixing the solid product 3 with 0.5mol/L sodium hydroxide solution according to the solid-liquid ratio of 1: mixing 15g/mL of the mixture, carrying out oscillation reaction at 100 ℃ for 10min, filtering, separating, drying and screening to obtain fluorine adsorption with the particle size of 0.5-10 mm。
Packing fluorine adsorbent into
Figure BDA0003232106570000091
The adsorbent in the ion exchange column is 30cm in height, then zinc electrolyte containing F158 mg/L, Zn 128g/L and pH 4.1 flows through the ion exchange column at room temperature, the contact time of the solution and the adsorbent is 60min, when the concentration of F in the solution after adsorption reaches 30mg/L, the zinc electrolyte is stopped to be added, and pure water with 4 times of the volume of the adsorbent is continuously passed (the adsorption capacity of the adsorbent to fluorine is 59.4 mg/g); the loaded adsorbent is resolved by 0.5mol/L sodium hydroxide solution to obtain regenerated adsorbent 1 and fluorine-containing resolving liquid.
The following table shows the results of 5 cycles of the same operation as described above for regenerated adsorbent 1:
number of cycles 1 2 3 4 5
The fluorine adsorption amount of the adsorbent is mg/g 38.2 30.4 21.3 16.7 10.4
Comparative example 4
Compared with example 1, the difference is that the solid product 1 is not reacted with the fluorine salt solution, specifically:
taking 1000g of sodium metaaluminate, and then mixing the sodium metaaluminate with the following components in a molar ratio of Si: al: OH group-：H2O is 2: 1: 2: 100, adding sodium metasilicate, sodium hydroxide and water, stirring for 60min at 10 ℃, then adding cerium nitrate according to 5 times of the molar weight of aluminum in the sodium metaaluminate, placing the mixture in a closed container (the slurry filling amount is 40-60 v%), stirring and reacting for 3h at 200 ℃, and filtering and separating to obtain a solid product 1; and (3) mixing the solid product 1 with a sodium alginate solution according to a solid-liquid ratio of 1: stirring uniformly at 40g/mL (the adding amount of sodium alginate is 10% of the weight of the solid product 2), dripping into a calcium chloride solution with the mass concentration of 0.5%, stirring and reacting for 48h at 10 ℃, and filtering and separating to obtain a solid product 3; mixing the solid product 3 with 0.5mol/L sodium hydroxide solution according to the solid-liquid ratio of 1: mixing 15g/mL of the mixture, carrying out oscillation reaction at 100 ℃ for 10min, filtering, separating, drying and screening to obtain fluorine adsorption with the particle size of 0.5-10 mm.
Packing fluorine adsorbent into
Figure BDA0003232106570000101
The height of the adsorbent in the ion exchange column is 30cm, then zinc electrolyte containing F158 mg/L, Zn 128g/L and pH of 4.1 flows through the ion exchange column at room temperature, the contact time of the solution and the adsorbent is 60min, when the concentration of F in the solution after adsorption reaches 30mg/L, the zinc electrolyte is stopped to be added, and pure water with 4 times of the volume of the adsorbent is continuously passed (the adsorption capacity of the adsorbent to fluorine is 39.9 mg/g); the loaded adsorbent is resolved by 0.5mol/L sodium hydroxide solution to obtain regenerated adsorbent 1 and fluorine-containing resolving liquid.
The following table shows the results of 5 cycles of the same operation as described above for regenerated adsorbent 1:
number of cycles 1 2 3 4 5
The fluorine adsorption amount of the adsorbent is mg/g 35.4 32.1 28.9 25.4 22.7
The zinc adsorption amount of the adsorbent is mg/g 145.2 180.1 194.3 167.5 175.6
Comparative example 5
Compared with the example 1, the difference is that the addition amount of alginate in the cross-linking treatment process is different, specifically:
taking 1000g of sodium metaaluminate, and then mixing the sodium metaaluminate with the following components in a molar ratio of Si: al: OH group-：H2O is 2: 1: 2: 100, adding sodium metasilicate, sodium hydroxide and water, stirring for 60min at 10 ℃, then adding cerium nitrate according to 5 times of the molar weight of aluminum in the sodium metaaluminate, placing the mixture in a closed container (the slurry filling amount is 40-60 v%), stirring and reacting for 3h at 200 ℃, and filtering and separating to obtain a solid product 1; dissolving the solid product 1 with 4mol/L sodium fluorideLiquid is mixed according to the solid-liquid ratio of 1: 1.5g/mL of the mixture is stirred and reacted for 60min at 10 ℃, and a solid product 2 is obtained by filtration and separation; and (3) mixing the solid product 2 with a sodium alginate solution according to a solid-to-liquid ratio of 1: stirring uniformly at 40g/mL (the adding amount of sodium alginate is 15% of the weight of the solid product 2%), dripping into a calcium chloride solution with the mass concentration of 0.5%, stirring and reacting for 48h at 10 ℃, and filtering and separating to obtain a solid product 3; mixing the solid product 3 with 0.5mol/L sodium hydroxide solution according to the solid-liquid ratio of 1: mixing 15g/mL of the mixture, carrying out oscillation reaction at 100 ℃ for 10min, filtering, separating, drying and screening to obtain fluorine adsorption with the particle size of 0.5-10 mm.
Packing fluorine adsorbent into
Figure BDA0003232106570000102
The height of the adsorbent in the ion exchange column is 30cm, then zinc electrolyte containing F158 mg/L, Zn 128g/L and pH of 4.1 flows through the ion exchange column at room temperature, the contact time of the solution and the adsorbent is 60min, when the concentration of F in the solution after adsorption reaches 30mg/L, the zinc electrolyte is stopped to be added, and pure water with 4 times of the volume of the adsorbent is continuously passed (the adsorption capacity of the adsorbent to fluorine is 62.1 mg/g); the loaded adsorbent is resolved by 0.5mol/L sodium hydroxide solution to obtain regenerated adsorbent 1 and fluorine-containing resolving liquid.
The following table shows the results of 5 cycles of the same operation as described above for regenerated adsorbent 1:
number of cycles 1 2 3 4 5
The fluorine adsorption amount of the adsorbent is mg/g 32.0 27.5 19.1 18.4 10.3
Example 2
Taking 1000g of potassium aluminate, and then mixing the potassium aluminate with the following components in a molar ratio of Si: al: OH group-：H2O is 50: 1: 25: adding ethyl orthosilicate, potassium hydroxide and water into the mixture 1000, stirring the mixture for 5min at 100 ℃, then adding lanthanum chloride according to 0.3 time of the molar weight of aluminum in potassium aluminate, placing the mixture into a closed container (the filling amount of slurry is 40-60 v%) and stirring the mixture for reaction at 100 ℃ for 48h, and filtering and separating the mixture to obtain a solid product 1; mixing the solid product 1 with 0.5mol/L potassium fluoride solution according to a solid-liquid ratio of 1: 10g/mL of the mixture is stirred and reacted for 10min at 100 ℃, and a solid product 2 is obtained by filtration and separation; and (3) mixing the solid product 2 with a sodium alginate aqueous solution according to a solid-to-liquid ratio of 1: stirring uniformly at 5g/mL (wherein sodium alginate is 0.5% of the weight of the solid product 2), dripping a nickel chloride solution with the mass concentration of 10% (wherein the weight ratio of nickel chloride to sodium alginate is 0.6: 1), stirring and reacting for 1h at 100 ℃, and filtering and separating to obtain a solid product 3; and mixing the solid product 3 with 3mol/L sodium carbonate solution according to a solid-liquid ratio of 1: mixing 1.5g/mL, oscillating and reacting at 10 ℃ for 60min, filtering, separating, drying and screening to obtain fluorine adsorption with the particle size of 0.5-10 mm.
Taking 1L (Co 37.4g/L, Ni 25.3g/L, Mn 31.2g/L, Li 5.3g/L, F78.9 mg/L, pH 0.5) of sulfuric acid leaching solution of the ternary battery anode material, and carrying out solid-to-liquid ratio of 1.5: adding 1g/L of fluorine to adsorb fluorine, shaking at 70 ℃ for 2min, and performing solid-liquid separation to obtain a load adsorbent and a defluorinated solution; the fluorine concentration in the liquid after the fluorine removal is reduced to 0.4mg/L, and the adsorption quantity of the adsorbent to the fluorine is 52.3 mg/g. The loaded adsorbent is resolved by 2mol/L ammonia water solution to obtain regenerated adsorbent 1 and fluorine-containing resolving liquid.
The following table shows the results of 5 cycles of the same operation as described above for regenerated adsorbent 1:
number of cycles 1 2 3 4 5
The fluorine adsorption amount of the adsorbent is mg/g 52.2 51.9 52.0 52.1 51.8
The adsorption capacity of the adsorbent nickel is mg/g 5.8 5.7 4.9 6.2 6.3
Cobalt adsorption amount of adsorbent mg/g 6.0 5.6 6.4 5.9 6.2
Manganese adsorption amount of adsorbent mg/g 8.3 8.6 8.0 7.9 8.4
The adsorption quantity of the adsorbent lithium is mg/g 0.6 0.7 0.5 0.4 0.4
Comparative example 6
Compared with the example 2, the difference is only that the crosslinking treatment in the step (3) is not carried out, and the specific steps are as follows:
taking 1000g of potassium aluminate, and then mixing the potassium aluminate with the following components in a molar ratio of Si: al: OH group-：H2O is 50: 1: 25: adding ethyl orthosilicate, potassium hydroxide and water into the mixture 1000, stirring the mixture for reaction for 5min at 100 ℃, then adding lanthanum chloride according to 0.3 time of the molar weight of aluminum in potassium aluminate, placing the mixture into a closed container (the slurry filling amount is 40-60 v%) and stirring the mixture for reaction for 48h at 100 ℃, and filtering and separating the mixture to obtain a solid product 1; mixing the solid product 1 with 0.5mol/L potassium fluoride solution according to a solid-liquid ratio of 1: mixing 10g/mL, stirring and reacting for 10min at 100 ℃, and filtering and separating to obtain a solid product 2; mixing the solid product 2 with 3mol/L sodium carbonate solution according to a solid-liquid ratio of 1: mixing 1.5g/mL, shaking at 10 deg.C for 60min, filtering, separating, and oven drying to obtain fluorine adsorption.
Taking 1L (Co 37.4g/L, Ni 25.3g/L, Mn 31.2g/L, Li 5.3g/L, F78.9 mg/L, pH 0.5) of sulfuric acid leaching solution of the ternary battery anode material, and mixing the three components according to a solid-to-liquid ratio of 1.5: adding 1g/L of fluorine to adsorb fluorine, shaking at 70 ℃ for 2min, and performing solid-liquid separation to obtain a load adsorbent and a defluorinated solution; after the fluorine removal, the fluorine concentration in the liquid is reduced to 8.5mg/L, and the fluorine adsorption amount of the adsorbent is 46.9 mg/g. The loaded adsorbent is resolved by 2mol/L ammonia water solution to obtain regenerated adsorbent 1 and fluorine-containing resolving liquid.
The following table shows the results of 5 cycles of the same operation as described above for regenerated adsorbent 1:
number of cycles 1 2 3 4 5
The fluorine adsorption amount of the adsorbent is mg/g 20.8 15.1 8.2 4.1 3.4
The adsorption capacity of the adsorbent nickel is mg/g 14.6 15.2 25.5 26.8 34.1
The adsorption capacity of the adsorbent cobalt is mg/g 8.4 16.1 28.7 30.1 31.7
Manganese adsorption amount of adsorbent mg/g 11.3 20.1 36.7 44.2 50.3
The adsorption quantity of the adsorbent lithium is mg/g 1.5 4.3 8.8 12.9 13.2
Example 3
Taking 1000g of sodium metaaluminate, and then mixing the sodium metaaluminate with the following components in a molar ratio of Si: al: OH group-：H2O is 20: 1: 20: 400, adding sodium metasilicate, sodium carbonate and water, stirring for 35min at 50 ℃, then adding cerium chloride according to 3 times of the molar weight of aluminum in the sodium metaaluminate, placing the mixture in a closed container (the slurry filling amount is 40-60 v%), stirring and reacting for 12h at 150 ℃, and filtering and separating to obtain a solid product 1; mixing the solid product 1 with 2mol/L ammonium fluoride solution according to a solid-liquid ratio of 1: 5g/mL of the mixture is stirred and reacted for 45min at 40 ℃, and a solid product 2 is obtained by filtration and separation; and (3) mixing the solid product 2 with a sodium alginate aqueous solution according to a solid-to-liquid ratio of 1: stirring uniformly by 20g/mL (wherein the weight of sodium alginate is 5% of that of the solid product 2), dripping cobalt chloride solution with the mass concentration of 4% (wherein the weight ratio of cobalt chloride to sodium alginate is 0.3: 1), stirring and reacting for 24h at 25 ℃, and filtering and separating to obtain a solid product 3; solid product 3 and 1mol/L ammonia water solutionAccording to the solid-liquid ratio of 1: mixing 7g/mL, oscillating and reacting at 25 ℃ for 30min, filtering, separating, drying and screening to obtain fluorine adsorption with the particle size of 0.5-10 mm.
Loading a fluorine adsorbent into an ion exchange column, then flowing underground water containing F8.1 mg/L at 70 ℃ through the ion exchange column, wherein the contact time of the solution and the adsorbent is 20min, stopping adding the underground water when the concentration of F in the solution after adsorption reaches 0.1mg/L, and continuously passing pure water with 4 times of the volume of the adsorbent (the adsorption capacity of the adsorbent to fluorine is 61.3 mg/g); the load adsorbent is resolved by adopting 1mol/L potassium hydroxide solution to obtain a regenerated adsorbent and fluorine-containing resolving liquid, and the fluorine resolving rate is over 99.2 percent.

Claims (42)

1. The preparation method of the fluorine adsorbent is characterized by comprising the following steps:
step (1): premixing a silicon source, an aluminum source, alkali and water to obtain slurry, placing the slurry and a rare earth source in a closed container, reacting at the temperature of more than or equal to 100 ℃, and then carrying out solid-liquid separation to obtain a rare earth aluminum-silicon product; in the slurry, a silicon source, an aluminum source, alkali and water are mixed according to the weight ratio of Si: al: OH group-：H2The molar ratio of O is 2-50: 1: 2-25: mixing at a ratio of 100-1000;
step (2): placing the rare earth aluminum-silicon product in a fluorine salt solution containing fluorine ions for fluorination treatment to obtain a fluorinated product;
and (3): mixing the fluorinated product with a alginic acid source and a crosslinking source, and performing crosslinking treatment to obtain a crosslinked product; wherein the weight ratio of the alginic acid source to the fluorinated product is 0.5-10%;
and (4): and (3) treating the cross-linked product in alkali liquor to prepare the fluorine adsorbent.
2. The method of claim 1, wherein in step (1), the silicon source is at least one of an alkali metal silicate, metasilicate, or silicate ester.
3. The method for preparing a fluorine adsorbent according to claim 1, wherein in the step (1), the aluminum source is at least one of sodium aluminate, sodium metaaluminate, potassium aluminate and potassium metaaluminate.
4. The method for preparing a fluorine adsorbent according to claim 1, wherein in the step (1), the base is at least one of an alkali metal hydroxide and ammonia water.
5. The method for preparing a fluorine adsorbent according to claim 1, wherein in the step (1), the temperature of the pre-mixing stage is 10 to 100 ℃.
6. The method for preparing a fluorine adsorbent according to claim 1, wherein in the step (1), the time for the premixing is 5 to 60 min.
7. The method of claim 1, wherein the rare earth source is a water-soluble salt of a rare earth element.
8. The method of claim 7, wherein the rare earth source is a water-soluble salt of cerium or lanthanum.
9. The method of claim 8, wherein the rare earth source is at least one of cerium nitrate, cerium sulfate, cerium chloride, lanthanum nitrate, lanthanum chloride, and lanthanum sulfate.
10. The method for preparing a fluorine adsorbent according to claim 1, wherein in the step (1), the reaction temperature is 100 to 200 ℃.
11. The method for preparing a fluorine adsorbent according to claim 1, wherein in the step (1), the reaction time is 3 to 48 hours.
12. The method for producing a fluorine adsorbent according to claim 1, wherein in the step (2), the fluorine salt solution is an aqueous solution of a water-soluble fluorine salt.
13. The method for preparing a fluorine adsorbent according to claim 12, wherein in the step (2), the fluorine salt in the fluorine salt solution is at least one of sodium fluoride, potassium fluoride and ammonium fluoride.
14. The method for producing a fluorine adsorbent according to claim 12, wherein a concentration of the solute in the fluorine salt solution is 0.5 to 4 mol/L.
15. The method for producing a fluorine adsorbent according to claim 1, wherein the ratio of the rare earth aluminum silicon product to the fluorine salt solution is 1: 1.5-10 g/mL.
16. The method for preparing a fluorine adsorbent according to claim 1, wherein the temperature during the fluorination treatment is 10 to 100 ℃.
17. The method for producing a fluorine adsorbent according to claim 1, wherein the time of the fluorination treatment process is 10 to 60 min.
18. The method of claim 1, wherein the alginic acid source is alginic acid or a water-soluble salt thereof.
19. The method of claim 18, wherein the source of alginic acid is sodium alginate.
20. The method of claim 1, wherein the crosslinking source is a water-soluble salt capable of cross-linking polymerization of the alginic acid source.
21. The method of claim 20, wherein the crosslinking source is a water-soluble salt of at least one element selected from the group consisting of calcium, nickel, and cobalt.
22. The method of claim 21, wherein the crosslinking source is at least one of calcium chloride, nickel chloride, and cobalt chloride.
23. The method for producing a fluorine adsorbent according to claim 1, wherein the temperature of the crosslinking reaction is 10 to 100 ℃.
24. The method of claim 1, wherein the crosslinking reaction is carried out for a period of time of 1 to 48 hours.
25. The method for preparing a fluorine adsorbent according to claim 1, wherein in the step (4), the alkali solution is an alkaline solution containing OH "ions.
26. The method for preparing a fluorine adsorbent according to claim 25, wherein in the step (4), the alkali solution is an aqueous solution of at least one of sodium hydroxide, potassium hydroxide and ammonia water.
27. The method for preparing a fluorine adsorbent according to claim 26, wherein in the step (4), the concentration of the solute in the alkali solution is 0.5 to 3 mol/L.
28. The method for producing a fluorine adsorbent according to claim 1, wherein in the step (4), the crosslinked product is prepared in a ratio of 1: mixing the solid-liquid ratio of 1.5-15 g/mL with alkali liquor.
29. The method for producing a fluorine adsorbent according to claim 1, wherein in the step (4), the temperature in the treatment stage is 10 to 100 ℃.
30. The method for producing a fluorine adsorbent according to claim 1, wherein in the step (4), the treatment period is 10 to 60 min.
31. The method for preparing a fluorine adsorbent according to claim 1, wherein in the step (4), after the completion of the treatment, solid-liquid separation is performed, followed by drying and sieving to obtain the fluorine adsorbent.
32. A fluorine adsorbent produced by the production method according to any one of claims 1 to 31.
33. The fluorine adsorbent of claim 32, wherein said fluorine adsorbent has a particle size of 0.5 to 10 mm.
34. Use of a fluorine adsorbent prepared by the method according to any one of claims 1 to 31 for adsorbing fluorine ions.
35. The use of claim 34 wherein said fluorine adsorbent is contacted with an aqueous solution containing fluorine ions for adsorbing fluorine ions therein.
36. The use of claim 35, wherein said fluorine adsorbent is contacted with an aqueous solution containing fluoride ions and hetero-ions for selective adsorption of fluoride ions therein.
37. The use of claim 36, wherein the hetero-ion is at least one of zinc ion, nickel ion, manganese ion, cobalt ion, sodium ion, and lithium ion.
38. Use of the fluorine adsorbent according to any one of claims 34 to 37, wherein the adsorption of fluorine ions is performed on a dynamic or static basis.
39. The use of the fluorine adsorbent of claim 38, wherein the static adsorption is static adsorption by mixing the fluorine adsorbent with an aqueous solution containing fluorine ions.
40. The use of the fluorine adsorbent of claim 38, wherein the dynamic adsorption is carried out by filling an ion exchange column with the fluorine adsorbent and flowing an aqueous solution containing fluorine ions as a mobile phase through the ion exchange column.
41. A method for recovering fluorine ions in a fluorine-containing solution is characterized in that a fluorine adsorbent prepared by the preparation method of any one of claims 1 to 31 is used for adsorbing the fluorine-containing solution to obtain a fluorine-removing solution and a loaded adsorbent, then the loaded adsorbent is desorbed by alkali liquor, a fluorine-containing desorption solution is recovered, and the desorbed fluorine adsorbent is recycled.
42. The method according to claim 41, wherein the fluorine adsorbent is packed in an ion exchange column, and the fluorine-containing solution is passed through the ion exchange column as a mobile phase to be adsorbed and collected to obtain a fluorine-removed solution; and then, adopting alkali liquor as a mobile phase to flow through the loaded ion exchange column for elution to obtain a fluorine-containing desorption solution, wherein the eluted ion exchange column is used for treating other batches of fluorine-containing solutions.
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