Composite zirconium-based fluorine removal agent resin as well as preparation method and application thereof

Abstract

The invention discloses composite zirconium-based fluorine removal agent resin as well as a preparation method and application thereof, and relates to the technical field of adsorbents. The zirconium-based fluorine removal agent resin is loaded on the carrier, the specific surface area of the adsorbent can be increased, compared with a powder zirconium-based fluorine removal agent, the loaded zirconium-based fluorine removal agent resin is more stable in structure, the fluorine removal effect can be improved, meanwhile, loss of active components can be reduced, zirconium ion dissolution can be remarkably reduced, and the good cyclic regeneration effect is achieved; the carbide slag is effectively utilized, the purpose of treating waste with waste is achieved, and the good market application prospect is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of adsorbents, and in particular, to a composite zirconium-based defluorinating agent resin, a preparation method thereof, and an application thereof. Background Art

[0002] Due to the advantages of high specific capacity, many cycle times, and safe performance, lithium-ion batteries have been widely used in civil and military application fields such as mobile phones, laptop computers, video cameras, digital cameras, etc. However, their service life is about 3 years, so a large number of lithium batteries are in the stage of scrapping and recycling. Due to the high price and shortage of lithium resources, the resource recycling of lithium has become one of the key research and development works in today's society.

[0003] At present, the black powder raw material in the lithium extraction process in the new energy industry comes from battery disassembly, and its main component is lithium nickel cobalt manganate. After processes such as mixing, roasting, and leaching, leaching lithium solution is obtained. Due to reasons such as electrolyte decomposition and binder residue, the leaching lithium solution inevitably contains more fluorine impurities. Without treatment, it is easy to cause the enrichment of fluorine elements, which will corrode the subsequent process equipment and affect the quality of the terminal product (such as lithium carbonate) at the same time.

[0004] At present, the existing defluorinating agents on the market are mainly zirconium-based adsorbents, whose adsorption capacity is relatively stable and has certain cycle regeneration performance. However, there is a problem of zirconium dissolution loss during the cycle, and the price is expensive.

[0005] In view of this, the present invention is specifically proposed. Summary of the Invention

[0006] The purpose of the present invention is to provide a composite zirconium-based defluorinating agent resin, a preparation method thereof, and an application thereof, aiming to improve the defluorination effect and prevent zirconium dissolution at the same time.

[0007] The present invention is implemented as follows:

[0008] In a first aspect, the present invention provides a composite zirconium-based defluorinating agent resin, including a carrier, on which a zirconium-based defluorinating agent resin is loaded;

[0009] Among them, the specific surface area of the carrier is greater than 100 m 3 / g, and the decomposition temperature is greater than 200 °C.

[0010] In an optional embodiment, the mass ratio of the carrier to the zirconium-based defluorinating agent resin is (0.8 - 1.5):(1.05 - 1.50);

[0011] Optionally, the zirconium-based defluorinating agent resin is formed by a powder zirconium-based defluorinating agent and a binder. During the preparation process, the raw material mass ratio of the powder zirconium-based defluorinating agent, the carrier, and the binder is controlled to be 1:(0.8 - 1.5):(0.1 - 0.6);

[0012] Optionally, the raw material mass ratio of the powdered zirconium-based defluorinating agent, the carrier, and the binder is 1:(1.0 - 1.2):(0.3 - 0.4).

[0013] In an alternative embodiment, the binder is selected from at least one of styrene-acrylate emulsion and polyvinyl chloride resin;

[0014] Optionally, the particle size of the powdered zirconium-based defluorinating agent is 0.5 μm - 1.0 μm, and the particle size of the carrier is 1.5 μm - 2.8 μm;

[0015] Optionally, the carrier is a porous carbon material;

[0016] Optionally, the carrier is carbide slag;

[0017] Optionally, by mass fraction, the composition of the carbide slag is as follows: Ni 0.16% - 0.22%, Co 0.05% - 0.10%, Mn 0.45% - 0.55%, Ca 0.5% - 0.6%, Mg 0.050% - 0.055%, Na 0.1% - 0.2%, Al 0.0060% - 0.0065%, Fe 0.017% - 0.022%, K 0.0017% - 0.0022%, Cu 0.0015% - 0.0020%, Zn 0.0015% - 0.0020%, Pb 0.004% - 0.006%, Si 0.0085% - 0.0095%, P 0.0040% - 0.0050%, F - 0.1% - 0.2%, SO4 2- 0.35% - 0.45%, Cl - 0.0085% - 0.0090% and Li 18% - 19%, with the balance being C.

[0018] In a second aspect, the present invention provides a method for preparing a composite zirconium-based defluorinating agent resin according to any one of the foregoing embodiments, comprising: loading a zirconium-based defluorinating agent resin on a carrier.

[0019] In an alternative embodiment, it includes: mixing and removing impurities from the powdered zirconium-based defluorinating agent and the carrier to obtain a composite slag material, mixing the composite slag material with a pore-forming agent and a binder to obtain a zirconium-based adsorbent resin, and drying the zirconium-based adsorbent resin to obtain a granular zirconium-based adsorbent resin;

[0020] Optionally, it further includes: washing and removing impurities from the obtained granular zirconium-based adsorbent resin.

[0021] In an alternative embodiment, the preparation process of the composite slag material includes: mixing the powdered zirconium-based defluorinating agent and carbide slag, impregnating them in an impregnating solution, taking them out, washing, and drying;

[0022] Among them, the impregnating solution contains stearic acid and sulfuric acid, the mass fraction of stearic acid is 0.05%-0.2%, and the mass fraction of sulfuric acid is 3%-8%.

[0023] In an optional embodiment, the preparation process of the zirconium-based adsorbent resin includes: grinding the composite slag to 0.3μm-1.0μm, and then mixing it evenly with a pore-forming agent and a binder;

[0024] Optionally, the binder is selected from at least one of styrene-acrylate emulsion and polyvinyl chloride resin;

[0025] Optionally, the pore-forming agent is selected from at least one of sodium sulfate and sodium chloride, and the mass ratio of the zirconium-based defluorinating agent in powder form to the pore-forming agent is 1:(0.2-0.4).

[0026] In an optional embodiment, by mass percentage, the raw materials of the styrene-acrylate emulsion include: 5%-15% of a silane hybrid-modified potassium silicate solution, 5%-15% of sodium vinyl sulfonate, 10%-25% of propyltrimethoxysilane, 5%-8% of a styrene-acrylic emulsion, 5%-10% of an initiator, and the balance is water; among them, the silane hybrid-modified potassium silicate solution is an aqueous solution with a mass fraction of 8%-15%;

[0027] Optionally, the initiator is selected from at least one of sodium persulfate and potassium persulfate;

[0028] Optionally, the preparation method of the styrene-acrylate emulsion includes: mixing the silane hybrid-modified potassium silicate solution, propyltrimethoxysilane, sodium vinyl sulfonate, water and the styrene-acrylic emulsion to obtain a styrene-acrylic pre-emulsion, and mixing the styrene-acrylic pre-emulsion and an aqueous solution of the initiator for a polymerization reaction;

[0029] Optionally, first dissolve sodium vinyl sulfonate in water, and then mix it with the silane hybrid-modified potassium silicate solution, propyltrimethoxysilane, water and the styrene-acrylic emulsion to obtain a styrene-acrylic pre-emulsion;

[0030] Optionally, during the polymerization reaction, control the reaction temperature at 70°C-80°C and the polymerization time at 200min-300min;

[0031] Optionally, after the polymerization reaction, cool down to below 30°C, adjust the pH value to 7.5-8.5, and then filter.

[0032] In an optional embodiment, by mass percentage, the raw materials of the polyvinyl chloride resin include: 5%-10% of an emulsifier, 5%-20% of isooctyl acrylate, 5%-15% of maleic acid, 10%-20% of an initiator, 5%-10% of a bio-ester plasticizer, 5%-8% of a PVC polymerization emulsion, and the balance is water;

[0033] Optionally, the bio - ester plasticizer is selected from at least one of di - isononyl phthalate, diphenyl carbonate, diethylene glycol dibenzoate, and di - isononyl 1,2 - cyclohexanedicarboxylate;

[0034] Optionally, the emulsifier includes an epoxy resin and a soft monomer. The mass ratio of the epoxy resin to the soft monomer is 1:1, and the soft monomer is selected from at least one of ethyl acrylate, butyl acrylate, and isooctyl acrylate;

[0035] Optionally, the relative molecular weight of the epoxy resin is less than 1000;

[0036] Optionally, the initiator is selected from at least one of sodium persulfate and potassium persulfate;

[0037] Optionally, the preparation method of the polyvinyl chloride resin includes: mixing the emulsifier, isooctyl acrylate, and maleic acid to obtain a first mixture; mixing the first mixture with an aqueous solution of the initiator and a buffer solution to make the pH value of the system 9 - 11, and then mixing with the bio - ester plasticizer to obtain a second mixture; emulsifying the second mixture with water; during the whole emulsification process, controlling the temperature at 50°C - 70°C, the heat - preservation time at 1h - 3h, then adding the PVC polymerization emulsion and cooling to 40°C - 60°C, adjusting the pH to 6.5 - 7.5, stirring for 30min - 100min, and then filtering;

[0038] Optionally, the preparation process of the buffer solution includes: mixing sodium carbonate, sodium bicarbonate, and water, and controlling the mass ratio of sodium carbonate to sodium bicarbonate at 1.5 - 2.5:1.

[0039] In the third aspect, the present invention provides the application of the composite zirconium - based defluorination agent resin in any of the foregoing embodiments or the composite zirconium - based defluorination agent resin prepared by the preparation method in any of the foregoing embodiments in treating fluoride - containing wastewater.

[0040] The present invention has the following beneficial effects: The present invention loads the zirconium - based defluorination agent resin on the carrier, which can increase the specific surface area of the adsorbent. Compared with the powder zirconium - based defluorination agent, the loaded zirconium - based defluorination agent resin has a more stable structure, can improve the defluorination effect while reducing the loss of active components, can significantly reduce the dissolution of zirconium ions, and has a good recycling and regeneration effect; it enables the effective utilization of carbide slag, realizes treating waste with waste, and has a very good market application prospect. Specific Embodiments

[0041] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Those not specified in the embodiments are carried out according to conventional conditions or conditions recommended by the manufacturer. Those reagents or instruments not specified by the manufacturer can be obtained as conventional products through commercial purchase.

[0042] An embodiment of the present invention provides a preparation method of a composite zirconium-based defluorination agent resin. By loading a zirconium-based defluorination agent resin on a carrier, a composite zirconium-based defluorination agent resin with excellent defluorination effect and cycling performance is obtained. The specific steps are as follows:

[0043] S1. Preparation of materials

[0044] The zirconium-based defluorination agent resin is formed by a powder zirconium-based defluorination agent and a binder. Therefore, accurate raw materials are required, including: a powder zirconium-based defluorination agent, a carrier, and a binder.

[0045] Among them, the powder zirconium-based defluorination agent can be a commercially available zirconium-based powder adsorbent with a zirconium hydroxide content ≥ 97% / 100g, purchased from West Asia Chemical Co., Ltd. in Shandong.

[0046] Among them, the carrier can be a commonly used carrier material, with a specific surface area greater than 100m 3 / g and a decomposition temperature greater than 200°C, having the characteristics of a large specific surface area and good stability.

[0047] In some embodiments, the carrier can be a porous carbon material, preferably carbonized slag. The raw materials of carbonized slag are easily available and have a porous morphology, which is suitable for being a carrier of the zirconium-based powder adsorbent.

[0048] Carbonized slag refers to the waste residue generated after further carbonization of the crude lithium carbonate obtained by adding sodium carbonate to lithium sulfate. The preparation process is as follows: The crude lithium carbonate obtained by adding sodium carbonate to lithium sulfate is subjected to a carbonization process and then treated by a filter press. The insoluble part is the carbonized slag. By mass fraction, the composition of the carrier is as follows: Ni 0.16% - 0.22%, Co 0.05% - 0.10%, Mn 0.45% - 0.55%, Ca 0.5% - 0.6%, Mg 0.050% - 0.055%, Na 0.1% - 0.2%, Al 0.0060% - 0.0065%, Fe 0.017% - 0.022%, K 0.0017% - 0.0022%, Cu 0.0015% - 0.0020%, Zn 0.0015% - 0.0020%, Pb 0.004% - 0.006%, Si 0.0085% - 0.0095%, P 0.0040% - 0.0050%, F - 0.1% - 0.2%, SO4 2- 0.35% - 0.45%, Cl - 0.0085% - 0.0090% and Li 18% - 19%, and the balance is C.

[0049] Among them, the binder is selected from at least one of styrene-acrylate emulsion and polyvinyl chloride resin, and can be any one or both of the above. It can be a commercially available raw material or can be synthesized independently. The formula and steps for independent synthesis are as follows:

[0050] (1) Synthesize styrene-acrylate emulsion

[0051] When independently synthesizing styrene-acrylate emulsion, the following formula can be adopted: calculated by mass percentage, the raw materials of styrene-acrylate emulsion include: 5%-15% of silane hybrid modified potassium silicate solution, 5%-15% of sodium vinyl sulfonate, 10%-25% of propyltrimethoxysilane, 5%-8% of styrene-acrylic emulsion, 5%-10% of initiator, and the balance is water; among them, the silane hybrid modified potassium silicate solution is an aqueous solution with a mass fraction of 8%-15%. Using this concentration of solution, the total amount of the solution is controlled to be 5%-15%.

[0052] Specifically, the silane hybrid modified potassium silicate solution can be a commercially available raw material, such as it can be purchased from Jinan Xinwang Chemical Co., Ltd.; the styrene-acrylic emulsion can be a commercially available raw material, such as it can be purchased from Langfang Bingxian New Building Materials Co., Ltd.

[0053] In some embodiments, the initiator is selected from at least one of sodium persulfate and potassium persulfate, and can be any one or several of the above.

[0054] In some embodiments, the preparation method of styrene-acrylate emulsion includes: mixing the silane hybrid modified potassium silicate solution, propyltrimethoxysilane, sodium vinyl sulfonate, water and styrene-acrylic emulsion to obtain a styrene-acrylic pre-emulsion, and mixing the styrene-acrylic pre-emulsion and an aqueous solution of the initiator for a polymerization reaction. To make the raw materials mix evenly, when preparing the styrene-acrylic pre-emulsion, sodium vinyl sulfonate can be first dissolved in water, and then stirred and mixed with the silane hybrid modified potassium silicate solution, propyltrimethoxysilane, water and styrene-acrylic emulsion to make each component fully mixed evenly into a milky white liquid, that is, the styrene-acrylic pre-emulsion is obtained, and the total amount of water meets the formula requirements.

[0055] Furthermore, during the polymerization reaction, the reaction temperature is controlled to be 70°C - 80°C, and the polymerization time is 200min - 300min. The polymerization time refers to the total time. In actual operation, it can be stirred for 150min - 200min first, and then kept warm for 50min - 100min. Specifically, the reaction temperature can be 70°C, 75°C, 80°C, etc., and the total polymerization time can be 200min, 250min, 300min, etc. After the polymerization reaction, the temperature is lowered to below 30°C, the pH value is adjusted to 7.5 - 8.5, stirred evenly and then filtered, and screen filtration can be used.

[0056] (2) Synthesize polyvinyl chloride resin

[0057] When synthesizing polyvinyl chloride resin independently, the following formula can be adopted: by mass percentage, the raw materials of polyvinyl chloride resin include: emulsifier 5%-10%, isooctyl acrylate 5%-20%, maleic acid 5%-15%, initiator 10%-20%, bio-ester plasticizer 5%-10%, PVC polymerization emulsion 5%-8%, and the balance is water. By introducing bio-ester plasticizer, the plasticization property can be increased, and the dissolution of zirconium can be further reduced.

[0058] In some embodiments, the emulsifier includes epoxy resin and soft monomer, the mass ratio of epoxy resin to soft monomer is 1:1, and the soft monomer is selected from at least one of ethyl acrylate, butyl acrylate, and isooctyl acrylate; the initiator is selected from at least one of sodium persulfate and potassium persulfate, and can be any one or several of the above.

[0059] In some embodiments, the relative molecular weight of the epoxy resin is less than 1000, and a low molecular weight epoxy resin is used, specifically it can be Cytec A-102.

[0060] In some embodiments, the bio-ester plasticizer is selected from at least one of diisononyl phthalate, diphenyl carbonate, diethylene glycol dibenzoate, and diisononyl 1,2-cyclohexanedicarboxylate, and can be any one or several of the above.

[0061] In some embodiments, the preparation method of polyvinyl chloride resin includes: mixing the emulsifier, isooctyl acrylate, and maleic acid to obtain a first mixed solution; mixing the first mixed solution with an aqueous solution of the initiator and a buffer solution to make the pH value of the system 9-11, and then mixing with the bio-ester plasticizer to obtain a second mixed solution; emulsifying the second mixed solution by mixing with water and sodium persulfate (polymerization); during the whole emulsification process, controlling the temperature at 50°C-70°C, the holding time at 1h-3h, then adding the PVC polymerization emulsion and cooling to 40°C-60°C, adjusting the pH to 6.5-7.5, stirring for 30min-100min, and then filtering.

[0062] In some embodiments, the preparation process of the buffer solution includes: mixing sodium carbonate, sodium bicarbonate, and water, and controlling the mass ratio of sodium carbonate to sodium bicarbonate to be 1.5-2.5:1, such as it can be 1.5:1, 2.0:1, 2.5:1, etc.

[0063] S2. Prepare the composite slag

[0064] Mix the powder zirconium-based defluorinating agent and the carrier and remove impurities to obtain the composite slag, and remove metal impurities such as nickel, cobalt, and manganese in the raw materials through impurity removal.

[0065] In some embodiments, impurities can be removed by impregnation. After mixing the powdered zirconium-based defluorinating agent and the carrier, they are impregnated in the impregnating solution, and then taken out for washing with water and drying. Among them, the impregnating solution contains stearic acid and sulfuric acid. The mass fraction of stearic acid is 0.05%-0.2% (such as 0.05%, 0.10%, 0.15%, 0.20%, etc.), and the mass fraction of sulfuric acid is 3%-8% (such as 3%, 4%, 5%, 6%, 7%, 8%, etc.). The impregnation process can be carried out in multiple times, and the drying temperature after washing with water is not limited and can be about 50°C.

[0066] S3. Prepare zirconium-based adsorbent resin

[0067] Mix the composite slag obtained in S2 with a pore-forming agent and a binder to obtain a zirconium-based adsorbent resin. The binder is any one or two of the two binders in S1. Curing is carried out using the binder to form a stable structure, thereby improving the defluorination effect and reducing the loss of active components. To make the raw materials mix evenly, in the actual operation process, the composite slag can be ground to 0.3μm - 1.0μm first, and then mixed evenly with the pore-forming agent and the binder.

[0068] Furthermore, during the preparation process, control the mass ratio of the raw materials of the powdered zirconium-based defluorinating agent, the carrier, and the binder to be 1:(0.8 - 1.5):(0.1 - 0.6), preferably 1:(1.0 - 1.2):(0.3 - 0.4). By controlling the dosage of each raw material, further improve the defluorination effect of the prepared defluorinating agent. Specifically, the mass ratio of the powdered zirconium-based defluorinating agent, the carrier, and the binder can be 1:0.8:0.1, 1:0.9:0.2, 1:1.0:0.3, 1:1.1:0.4, 1:1.2:0.4, 1:1.3:0.5, 1:1.4:0.5, 1:1.5:0.6, etc.

[0069] Furthermore, the pore-forming agent is selected from at least one of sodium sulfate and sodium chloride, and can be any one or several of the above. The mass ratio of the powdered zirconium-based defluorinating agent to the pore-forming agent is 1:(0.2 - 0.4). During the subsequent drying process of the pore-forming agent, sodium sulfate dissolves in water leaving holes, generating certain voids, so that the resin has a certain void structure.

[0070] S4. Prepare granular zirconium-based adsorbent resin

[0071] After drying and cooling the zirconium-based adsorbent resin, granular zirconium-based adsorbent resin is obtained. The drying temperature is not limited and can be 60°C - 80°C.

[0072] S5. Post-treatment

[0073] The obtained granular zirconium-based adsorbent resin is washed with water and purified to remove the water-soluble impurities introduced during the preparation process, and a composite zirconium-based defluorinating agent resin is obtained.

[0074] An embodiment of the present invention also provides a composite zirconium-based defluorinating agent resin, which includes a carrier, and a zirconium-based defluorinating agent resin is loaded on the carrier. The carbonized slag is used to ensure the effective specific surface area and pores on the surface of the resin material, form a stable active microporous structure, reduce the loss of the active component zirconium, accelerate its adsorption and desorption speed, shorten the adsorption and desorption time, extend the service life of the resin, and at the same time solve the problems of the shaping of the adsorbent and the zirconium dissolution loss. The composite zirconium-based defluorinating agent resin provided in this embodiment can be prepared by the above preparation method.

[0075] In some embodiments, the mass ratio of the carrier to the zirconium-based defluorinating agent resin is (0.8-1.5):(1.05-1.50), such as 0.80:1.05, 1.00:1.20, 1.20:1.30, 1.50:1.50, etc.

[0076] In some embodiments, the particle size of the powdered zirconium-based defluorinating agent is 0.5 μm - 1.0 μm, and the particle size of the carrier is 1.5 μm - 2.8 μm. The adsorbent with a smaller particle size can better adsorb fluoride ions.

[0077] It should be noted that the composite zirconium-based defluorinating agent resin provided in the embodiment of the present invention can be applied in the treatment of fluoride-containing wastewater, and has the advantages of short adsorption time and long service life during use.

[0078] The features and properties of the present invention will be further described in detail below in conjunction with embodiments.

[0079] It should be noted that the formulations and preparation processes of the styrene-acrylic emulsion hydrosol used in the following examples or comparative examples are as follows: By mass percentage, the raw materials of the styrene-acrylate emulsion include: 8% of a silane hybrid-modified potassium silicate solution, 10% of sodium vinylsulfonate, 20% of propyltrimethoxysilane, 8% of a styrene-acrylic emulsion, 5% of an initiator, and the balance is water; among them, the silane hybrid-modified potassium silicate solution is an aqueous solution with a mass fraction of 5% - 15%. The preparation process is as follows: (1) Pretreatment process, dissolve sodium vinylsulfonate in a certain amount of deionized water, and after dissolution, place it under the conditions of 40 - 50 °C and stir at a speed of 300 rpm; (2) Add deionized water, the silane hybrid-modified potassium silicate solution, propyltrimethoxysilane, and the above-prepared sodium vinylsulfonate to the styrene-acrylic emulsion, and stir at a speed of 300 rpm for 30 min to fully mix and homogenize all components into a milky white liquid, that is, obtain a styrene-acrylic pre-emulsion; (3) Polymerization stage, polymerize 5% of the styrene-acrylic pre-emulsion and an aqueous solution of potassium persulfate under the conditions of 70 - 80 °C, stir for 180 min, and then keep warm for 60 min; (4) Wait for the temperature to drop below 30 °C stably, adjust the pH to 7.5 - 8.5, stir evenly, and filter (screen filtration) to obtain a styrene-acrylate emulsion.

[0080] It should be noted that the formulations and preparation processes of the polyvinyl chloride resin used in the following examples or comparative examples are as follows: By mass percentage, the raw materials of the polyvinyl chloride resin include: 10% of an emulsifier, 10% of isooctyl acrylate, 10% of maleic acid, 10% of potassium persulfate, 8% of a bio-ester plasticizer, 6% of a PVC polymerization emulsion, and the balance is water. The emulsifier includes Cytec A-102 and ethyl acrylate (mass fraction of 5%), and the mass ratio of Cytec A-102 to ethyl acrylate is 1:1. The preparation process is as follows: (1) Pretreatment process, mix the emulsifier, isooctyl acrylate, and maleic acid in a mass ratio of 1:1:1 to obtain a mixed liquid B; (2) Add the mixed liquid B to an aqueous solution of potassium persulfate (initiator), and stir for 60 min under the buffering conditions of a buffer solution (a mixture of sodium carbonate and sodium bicarbonate with a mass ratio of 2:1) (pH value is 10), and finally add a bio-ester plasticizer to increase its plasticization; (3) Add the above solution, deionized water, and sodium persulfate to an open flask for high-speed emulsification and standby. The temperature of the whole emulsification process is maintained at 50 - 70 °C. After dropping and keeping warm for 2 hours, add the PVC polymerization emulsion and cool to 50 °C, adjust the pH value to about neutral with a pH buffer, stir for 60 min, filter through a 200-mesh screen cloth and discharge, and finally obtain a milky white polyvinyl chloride resin.

[0081] It should be noted that, by mass fraction, the carrier used in the following examples is carbide slag, and its composition is as follows: Ni 0.19%, Co 0.070%, Mn 0.51%, Ca 0.55%, Mg 0.052%, Na 0.15%, Al 0.0063%, Fe 0.019%, K 0.0019%, Cu 0.0017%, Zn 0.0018%, Pb 0.0050%, Si 0.0089%, P 0.0046%, F - 0.15%, SO4 2- 0.39%, Cl - 0.0087% and Li 18.40%, and the balance is C. The specific surface area is 200 - 250 m 3 / g, and the decomposition temperature is 200°C - 500°C.

[0082] Example 1

[0083] This example provides a preparation method of a composite zirconium-based defluorination agent resin, and the specific steps are as follows:

[0084] (1) Immerse 30 g of the carbide slag carrier in the impregnating solution, mix it with the powder zirconium-based defluorination agent and stir for 120 min. After taking it out, rinse it with deionized water and then dry it to obtain the powder adsorbent precursor impregnated with carbide slag. Among them, the impregnating solution is an aqueous solution formed by stearic acid and sulfuric acid. The mass fraction of stearic acid is 0.1%, and the mass fraction of sulfuric acid is 5%.

[0085] (2) Mix the above-prepared powder adsorbent precursor with the pore-forming agent (sodium sulfate), add styrene-acrylate emulsion. The mass ratio of the powder adsorbent precursor, the pore-forming agent and the styrene-acrylate emulsion is 1:0.2:0.4, and stir for 5 min (mix evenly multiple times) under the condition of the high-speed granulator speed of 1500 rpm to make it shaped, and then transfer it to an oven (80°C) for drying, cooling, water washing and curing to obtain the styrene-acrylic granular adsorbent.

[0086] Performance test: Wash the above-obtained styrene-acrylic granular adsorbent thoroughly with water and fill it into an adsorption column (170 mL). The fluorine concentration in the industrial fluorine-containing wastewater is 200.0 mg / L, and adjust the solution pH = 3. Perform cyclic adsorption with an adsorption rate of 2 Bv / h until it reaches saturated adsorption. The measured adsorption capacity is 20.0 mg / g. Use a 20.0 g / L liquid caustic solution for desorption with a desorption rate of 4 Bv / h and a desorption time of 8 h. The desorption rate reaches 90.5%. After 10 cycles of adsorption and desorption, the adsorption capacity is 18.8 mg / g (the adsorption capacity retention rate is 94%), and there is no zirconium dissolution loss.

[0087] Example 2

[0088] This embodiment provides a preparation method of a composite zirconium-based defluorinating agent resin, and the specific steps are as follows:

[0089] (1) Immerse 30 g of the carrier in the impregnating solution, mix it with the powdered zirconium-based defluorinating agent and stir for 120 min. After taking it out, rinse it with deionized water and then dry it to obtain the powdered adsorbent precursor impregnated with carbonized slag. Among them, the impregnating solution is an aqueous solution formed by stearic acid and sulfuric acid, the mass fraction of stearic acid is 0.1%, and the mass fraction of sulfuric acid is 5%.

[0090] (2) Mix the above-prepared powdered adsorbent precursor with the pore-forming agent (sodium sulfate), add styrene-acrylate emulsion. The mass ratio of the powdered adsorbent precursor, the pore-forming agent and the styrene-acrylate emulsion is 1:0.2:0.4, and stir for 5 min (mix evenly for multiple times) under the condition that the rotation speed of the high-speed granulator is 1500 rpm to make it shaped, and then transfer it to an oven (80 °C) for drying, cooling, water washing and curing to obtain the styrene-acrylic granular adsorbent.

[0091] Performance test: Thoroughly wash the above-obtained styrene-acrylic granular adsorbent and load it into an adsorption column (170 mL). The fluorine concentration in the industrial fluorine-containing wastewater is 200.0 mg / L, and adjust the solution pH = 3, and perform cyclic adsorption at an adsorption rate of 1 Bv / h until it reaches saturated adsorption. The measured adsorption capacity is 19.5 mg / g. Desorption is carried out using a 20.0 g / L caustic soda solution at a desorption rate of 4 Bv / h for 8 h, and the desorption rate reaches 89.9%. After 10 cycles of adsorption and desorption, the adsorption capacity is 17.9 mg / g (the adsorption capacity retention rate is 91.8%), and there is no zirconium dissolution loss.

[0092] Example 3

[0093] This embodiment provides a preparation method of a composite zirconium-based defluorinating agent resin, and the specific steps are as follows:

[0094] (1) Immerse 30 g of the carrier in the impregnating solution, mix it with the powdered zirconium-based defluorinating agent and stir for 120 min. After taking it out, rinse it with deionized water and then dry it to obtain the powdered adsorbent precursor impregnated with carbonized slag. Among them, the impregnating solution is an aqueous solution formed by stearic acid and sulfuric acid, the mass fraction of stearic acid is 0.1%, and the mass fraction of sulfuric acid is 5%.

[0095] (2) Mix the above-prepared powdered adsorbent precursor with the pore-forming agent (sodium sulfate), add polyvinyl chloride resin. The mass ratio of the powdered adsorbent precursor, the pore-forming agent and the polyvinyl chloride resin is 1:0.2:0.4, and stir for 5 min (mix evenly for multiple times) under the condition that the rotation speed of the high-speed granulator is 1500 rpm to make it shaped, and then transfer it to an oven (80 °C) for drying, cooling, water washing and curing to obtain the PVC granular adsorbent.

[0096] Performance test: The PVC granular adsorbent obtained above was washed with water and filled into an adsorption column (170 mL). The fluorine concentration in the industrial fluorine-containing wastewater was 200.0 mg / L, and the solution pH was adjusted to 3. It was circulated for adsorption at an adsorption rate of 2 Bv / h until saturated adsorption was achieved. The adsorption capacity was measured to be 17.8 mg / g. Desorption was carried out using a 20.0 g / L liquid caustic soda solution at a desorption rate of 4 Bv / h for 10 h, and the desorption rate reached 94.7%. It was found that after 10 adsorption-desorption cycles, the adsorption capacity still remained at 15.0 mg / g (the adsorption capacity retention rate was 84.3%), and there was no zirconium dissolution loss.

[0097] Example 4

[0098] This example provides a preparation method of a composite zirconium-based defluorinating agent resin, and the specific steps are as follows:

[0099] (1) Immerse 30 g of the carrier in the impregnating solution, mix it with the powder zirconium-based defluorinating agent and stir for 120 min. After taking it out, rinse it with deionized water and then dry it to obtain the precursor of the powder adsorbent impregnated with carbonized slag. Among them, the impregnating solution is an aqueous solution formed by stearic acid and sulfuric acid. The mass fraction of stearic acid is 0.1%, and the mass fraction of sulfuric acid is 5%.

[0100] (2) Mix the above-prepared precursor of the powder adsorbent with the pore-forming agent (sodium sulfate), add polyvinyl chloride resin. The mass ratio of the precursor of the powder adsorbent, the pore-forming agent and the polyvinyl chloride resin is 1:0.2:0.4, and stir for 5 min (mix evenly multiple times) under the condition of a high-speed granulator rotation speed of 1500 rpm to make it form, and then transfer it to an oven (80 °C) for drying, cooling, washing with water and curing to obtain the PVC granular adsorbent.

[0101] Performance test: The resin obtained above was washed with water and filled into an adsorption column (170 mL). The fluorine concentration in the industrial fluorine-containing wastewater was 200.0 mg / L, and the solution pH was adjusted to 3. It was circulated for adsorption at an adsorption rate of 1 Bv / h until saturated adsorption was achieved. The adsorption capacity was measured to be 17.1 mg / g. Desorption was carried out using a 20.0 g / L liquid caustic soda solution at a desorption rate of 4 Bv / h for 10 h, and the desorption rate reached 94.0%. It was found that after 10 adsorption-desorption cycles, the adsorption capacity still remained at 14.8 mg / g (the adsorption capacity retention rate was 86.5%), and there was no zirconium dissolution loss.

[0102] Comparative Example 1

[0103] This comparative example provides a preparation method of a composite zirconium-based defluorinating agent resin. The main difference between this comparative example and Example 1 is that it does not go through carrier loading, and the specific steps are as follows:

[0104] Mix the powdered zirconium-based defluorinating agent with a pore-forming agent (sodium sulfate), add styrene-acrylate emulsion. The mass ratio of the powdered zirconium-based defluorinating agent, the pore-forming agent, and the styrene-acrylate emulsion is 1:0.2:0.4. Stir for 5 min (mix evenly multiple times) under the condition that the rotation speed of the high-speed granulator is 1500 rpm to form it, and then transfer it to an oven (80 °C) for drying, cooling, washing with water, and curing to obtain the styrene-acrylic granular adsorbent.

[0105] Performance test: Wash the above-obtained styrene-acrylic granular adsorbent and load it into an adsorption column (170 mL). The fluorine concentration in the industrial fluorine-containing wastewater is 200.0 mg / L, and adjust the solution pH = 3. Perform cyclic adsorption at an adsorption rate of 2 Bv / h until saturated adsorption is achieved. Measure its adsorption capacity to be 12.8 mg / g. Desorb with a 20.0 g / L caustic soda solution at a desorption rate of 4 Bv / h for 18 h. The desorption rate reaches 84.6%. After 10 cycles of adsorption and desorption, the adsorption capacity is 6.4 mg / g (the adsorption capacity retention rate is 50%). The adsorption capacity is halved. As the number of cycles increases, the zirconium mass loss is 25 - 35%.

[0106] Comparative Example 2

[0107] This comparative example provides a preparation method of a composite zirconium-based defluorinating agent resin. The main difference between this comparative example and Example 2 is that it does not go through carrier loading. The specific steps are as follows:

[0108] Mix the powdered zirconium-based defluorinating agent with a pore-forming agent (sodium sulfate), add styrene-acrylate emulsion. The mass ratio of the powdered zirconium-based defluorinating agent, the pore-forming agent, and the styrene-acrylate emulsion is 1:0.2:0.4. Stir for 5 min (mix evenly multiple times) under the condition that the rotation speed of the high-speed granulator is 1500 rpm to form it, and then transfer it to an oven (80 °C) for drying, cooling, washing with water, and curing to obtain the styrene-acrylic granular adsorbent.

[0109] Performance test: Wash the above-obtained styrene-acrylic granular adsorbent and load it into an adsorption column (170 mL). The fluorine concentration in the industrial fluorine-containing wastewater is 200.0 mg / L, and adjust the solution pH = 3. Perform cyclic adsorption at an adsorption rate of 1 Bv / h until saturated adsorption is achieved. Measure its adsorption capacity to be 11.9 mg / g. Desorb with a 20.0 g / L caustic soda solution at a desorption rate of 4 Bv / h for 18 h. The desorption rate reaches 80.2%. After 10 cycles of adsorption and desorption, the adsorption capacity is 5.8 mg / g (the adsorption capacity retention rate is 48.7%). The adsorption capacity decreases, and as the number of cycles increases, the zirconium mass loss is 20 - 30%.

[0110] Comparative Example 3

[0111] This comparative example provides a method for preparing a composite zirconium-based defluorination agent resin. The main difference between this comparative example and Example 3 is that it does not undergo carrier loading. The specific steps are as follows:

[0112] Mix the powdered zirconium-based defluorination agent with a pore-forming agent (sodium sulfate), add polyvinyl chloride resin. The mass ratio of the powdered adsorbent precursor, pore-forming agent, and polyvinyl chloride resin is 1:0.2:0.4, and stir for 5 min (mix evenly multiple times) under the condition that the high-speed granulator rotates at 1500 rpm to form it, and then transfer it to an oven (80 °C) for drying, cooling, water washing, and curing to obtain a PVC granular adsorbent.

[0113] Performance test: Wash the above-obtained PVC granular adsorbent and load it into an adsorption column (170 mL). The fluorine concentration in the industrial fluorine-containing wastewater is 200.0 mg / L, and adjust the solution pH = 3, and perform cyclic adsorption at an adsorption rate of 2 Bv / h until saturated adsorption is achieved. Measure its adsorption capacity to be 10.0 mg / g. Use a 20.0 g / L liquid caustic soda solution for desorption at a desorption rate of 4 Bv / h and a desorption time of 24 h. The desorption rate reaches 83.9%. It is found that after 10 cycles of adsorption and desorption, its adsorption capacity is 2.6 mg / g (the adsorption capacity retention rate is 26%), the adsorption capacity decreases significantly and the zirconium dissolution is serious. As the number of cycles increases, the zirconium mass loss is 40 - 50%.

[0114] Comparative Example 4

[0115] This comparative example provides a method for preparing a composite zirconium-based defluorination agent resin. The main difference between this comparative example and Example 4 is that it does not undergo carrier loading. The specific steps are as follows:

[0116] Mix the powdered zirconium-based defluorination agent with a pore-forming agent (sodium sulfate), add polyvinyl chloride resin. The mass ratio of the powdered adsorbent precursor, pore-forming agent, and polyvinyl chloride resin is 1:0.2:0.4, and stir for 5 min (mix evenly multiple times) under the condition that the high-speed granulator rotates at 1500 rpm to form it, and then transfer it to an oven (80 °C) for drying, cooling, water washing, and curing to obtain a PVC granular adsorbent.

[0117] Performance test: The obtained PVC granular adsorbent was washed with water and filled into an adsorption column (170 mL). The fluorine concentration in the industrial fluorine-containing wastewater was 200.0 mg / L, and the solution pH was adjusted to 3. It was subjected to cyclic adsorption at an adsorption rate of 1 Bv / h until saturated adsorption was achieved. The measured adsorption capacity was 8.9 mg / g. Desorption was carried out using a 20.0 g / L caustic soda solution at a desorption rate of 4 Bv / h for 24 h, and the desorption rate reached 81.7%. It was found that after 10 cycles of adsorption and desorption, the adsorption capacity was 2.46 mg / g (the adsorption capacity retention rate was 27.6%), the adsorption capacity decreased and there was zirconium dissolution loss. As the number of cycles increased, the zirconium mass loss was 30 - 42%.

[0118] It should be noted that through the comparison of the examples and comparative examples, it can be seen that: compared with the styrene / PVC resin without being loaded with carbonized slag, the defluorination effect of the loaded resin has increased significantly, and there is no zirconium dissolution loss, which proves that the loaded material has a good stable structure and reduces the loss of active components (zirconium).

[0119] Comparative Example 5

[0120] This comparative example provides a preparation method of an existing fluoride ion adsorbent, as shown in CN115722195A.

[0121] Using graphite in-situ loaded with manganese and aluminum oxides as adsorbent not only effectively increases the specific surface area of the adsorbent and improves the adsorption capacity, but also is conducive to the desorption operation and improves the regeneration capacity retention rate of the material. During the metal precipitation process, NaAlO2 is added, and its hydrolysis slowly releases aluminum, slowing down the sharp decrease in the content of aluminum ions in the solution, enabling aluminum to precipitate evenly with manganese ions on the graphite matrix and enhancing the stability of the material. The fluoride ion adsorbent prepared by the preparation method of this application has a good effect on adsorbing fluoride ions. After being washed and replaced with an alkali solution, it can be reused, and the adsorption capacity retention rate after 10 uses is 68%.

[0122] In summary, the preparation method of the composite zirconium-based defluorinating agent resin provided in the embodiments of the present invention has the following advantages:

[0123] (1) The operation is simple. The prepared zirconium-based defluorinating agent resin has a stable structure, less zirconium ion dissolution, and has a good cyclic regeneration effect. After 10 cycles of cyclic adsorption, its resin capacity can still be maintained at the same level. The adsorption capacity of the PVC granular adsorbent still maintains at 18.8 mg / g after 10 cycles of adsorption and desorption, and the adsorption capacity of the styrene granular adsorbent still maintains at 15.0 mg / g after 10 cycles of adsorption and desorption, which proves that the powdered adsorbent loaded with carbonized slag has good cyclic use performance.

[0124] (2) Using styrene-acrylic and PVC as the binder for the adsorbent, it does not require high-temperature sintering and can be completely cured within the oven temperature range. Moreover, the adsorption capacity of the two resins does not show a downward trend with the increase in the number of cycles and remains stable. This is because the active sites on the surface of the zirconium-based adsorbent have not been lost, demonstrating the dual curing ability of the carbide slag and the binder for the powder adsorbent.

[0125] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, various modifications and changes can be made to the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A composite zirconium-based defluorination agent resin, characterized in that, It includes a carrier on which a zirconium-based defluorination agent resin is loaded. Among them, the specific surface area of the carrier is greater than 100 m 3 / g, and the decomposition temperature is greater than 200 °C.

2. The composite zirconium-based defluorination agent resin according to claim 1, wherein The mass ratio of the carrier to the zirconium-based defluorination agent resin is (0.8 - 1.5):(1.05 - 1.50). Optionally, the zirconium-based defluorination agent resin is formed by a powder zirconium-based defluorination agent and a binder. During the preparation process, the raw material mass ratio of the powder zirconium-based defluorination agent, the carrier, and the binder is controlled to be 1:(0.8 - 1.5):(0.1 - 0.6). Optionally, the raw material mass ratio of the powder zirconium-based defluorination agent, the carrier, and the binder is 1:(1.0 - 1.2):(0.3 - 0.4).

3. The composite zirconium-based defluorination agent resin according to claim 2, wherein, The binder is selected from at least one of styrene-acrylate emulsion and polyvinyl chloride resin. Optionally, the particle size of the powder zirconium-based defluorination agent is 0.5μm - 1.0μm, and the particle size of the carrier is 1.5μm - 2.8μm. Optionally, the carrier is a porous carbon material. Optionally, the carrier is carbide slag. Optionally, by mass fraction, the composition of the carbonized slag is as follows: Ni 0.16%-0.22%, Co 0.05%-0.10%, Mn 0.45%-0.55%, Ca 0.5%-0.6%, Mg 0.050%-0.055%, Na 0.1%-0.2%, Al 0.0060%-0.0065%, Fe 0.017%-0.022%, K 0.0017%-0.0022%, Cu 0.0015%-0.0020%, Zn 0.0015%-0.0020%, Pb 0.004%-0.006%, Si 0.0085%-0.0095%, P 0.0040%-0.0050%, F - 0.1%-0.2%, SO4 2- 0.35%-0.45%, Cl - 0.0085%-0.0090% and Li 18%-19%, the balance being C.

4. A method for preparing the composite zirconium-based defluorination agent resin according to any one of claims 1-3, characterized in that, It includes: loading the zirconium-based defluorination agent resin on the carrier.

5. The preparation method according to claim 4, wherein It includes: Mixing the powder zirconium-based defluorination agent and the carrier to remove impurities to obtain a composite slag material, mixing the composite slag material with a pore-forming agent and a binder to obtain a zirconium-based adsorbent resin, and drying the zirconium-based adsorbent resin to obtain a granular zirconium-based adsorbent resin. Optionally, it further includes: washing and removing impurities from the obtained granular zirconium-based adsorbent resin.

6. The preparation method according to claim 5, wherein The preparation process of the composite slag material includes: mixing the powder zirconium-based defluorination agent and the carrier and then impregnating them in an impregnating solution, taking them out and then washing and drying. Among them, the impregnating solution contains stearic acid and sulfuric acid. The mass fraction of stearic acid is 0.05% - 0.2%, and the mass fraction of sulfuric acid is 3% - 8%.

7. The preparation method according to claim 5, characterized in that, The preparation process of the zirconium-based adsorbent resin includes: grinding the composite slag material to 0.3μm - 1.0μm and then mixing it evenly with the pore-forming agent and the binder. Optionally, the binder is selected from at least one of styrene-acrylate emulsion and polyvinyl chloride resin. Optionally, the pore-forming agent is selected from at least one of sodium sulfate and sodium chloride, and the mass ratio of the powder zirconium-based defluorination agent to the pore-forming agent is 1:(0.2 - 0.4).

8. The preparation method according to claim 7, characterized in that, By mass percentage, the raw materials of the styrene-acrylate emulsion include: 5% - 15% of a silane hybrid modified potassium silicate solution, 5% - 15% of sodium vinyl sulfonate, 10% - 25% of propyltrimethoxysilane, 5% - 8% of a styrene-acrylic emulsion, 5% - 10% of an initiator, and the balance is water; among them, the silane hybrid modified potassium silicate solution is an aqueous solution with a mass fraction of 8% - 15%. Optionally, the initiator is selected from at least one of sodium persulfate and potassium persulfate. Optionally, the preparation method of the styrene-acrylate emulsion includes: mixing the silane hybrid modified potassium silicate solution, propyltrimethoxysilane, sodium vinyl sulfonate, water, and the styrene-acrylic emulsion to obtain a styrene-acrylic pre-emulsion, and mixing the styrene-acrylic pre-emulsion and an aqueous solution of the initiator for a polymerization reaction. Optionally, first dissolve sodium vinyl sulfonate in water, and then mix it with the silane hybrid modified potassium silicate solution, propyltrimethoxysilane, water, and the styrene-acrylic emulsion to obtain the styrene-acrylic pre-emulsion. Optionally, during the polymerization reaction, the reaction temperature is controlled at 70°C - 80°C, and the polymerization time is 200 min - 300 min; Optionally, after the polymerization reaction, the temperature is lowered to below 30°C, the pH value is adjusted to 7.5 - 8.5, and then filtration is carried out.

9. The preparation method according to claim 7, characterized in that, By mass percentage, the raw materials of the polyvinyl chloride resin include: 5% - 10% emulsifier, 5% - 20% isooctyl acrylate, 5% - 15% maleic acid, 10% - 20% initiator, 5% - 10% bio - ester plasticizer, 5% - 8% PVC polymerization emulsion, and the balance is water; Optionally, the bio - ester plasticizer is selected from at least one of diisononyl phthalate, diphenyl carbonate, diethylene glycol dibenzoate, and diisononyl 1,2 - cyclohexanedicarboxylate; Optionally, the emulsifier includes epoxy resin and soft monomer, and the mass ratio of epoxy resin to soft monomer is 1:

1. The soft monomer is selected from at least one of ethyl acrylate, butyl acrylate, and isooctyl acrylate; Optionally, the relative molecular weight of the epoxy resin is less than 1000; Optionally, the initiator is selected from at least one of sodium persulfate and potassium persulfate; Optionally, the preparation method of the polyvinyl chloride resin includes: mixing the emulsifier, isooctyl acrylate, and maleic acid to obtain a first mixed solution; mixing the first mixed solution with an aqueous solution of the initiator and a buffer solution to make the pH value of the system 9 - 11, and then mixing with the bio - ester plasticizer to obtain a second mixed solution; emulsifying the second mixed solution with water; during the whole emulsification process, controlling the temperature at 50°C - 70°C, the heat - preservation time at 1 h - 3 h, then adding the PVC polymerization emulsion, lowering the temperature to 40°C - 60°C, adjusting the pH to 6.5 - 7.5, stirring for 30 min - 100 min, and then filtering; Optionally, the preparation process of the buffer solution includes: mixing sodium carbonate, sodium bicarbonate, and water, and controlling the mass ratio of sodium carbonate to sodium bicarbonate at 1.5 - 2.5:

1.

10. Application of the composite zirconium - based defluorination agent resin according to any one of claims 1 - 3 or the composite zirconium - based defluorination agent resin prepared by the preparation method according to any one of claims 4 - 9 in treating fluoride - containing wastewater.