Fluorine-free resin and method for producing the same

Abstract

The application provides a fluoride-removing resin and a preparation method thereof. The fluoride-removing resin comprises a first unit and a second unit, the structural formula of the first unit is and the structural formula of the second unit is wherein R1 and R2 are alkylene groups, R3 is an alkylene group or a single bond, R4 is an alkyl group or a hydrogen atom, M1 is an aluminum salt group or a manganese salt group, and M2 is an aluminum salt group or a manganese salt group. The fluoride-removing resin has excellent fluoride-removing effects in both acidic and alkaline environments, which is beneficial to its use.

Description

Technical Field

[0001] The present application relates to the field of fluorine removal technology, and in particular to a fluorine removal resin and a preparation method thereof. Background Art

[0002] Currently, defluorination resins are commonly used in waste battery recycling and high-fluorine industrial wastewater treatment to obtain higher-purity lithium-containing compounds and prevent wastewater pollution. However, commercial defluorination resins can be used in acidic environments but lack the ability to remove fluorine in alkaline environments, making them less suitable for fluoride removal. Summary of the Invention

[0003] In view of this, the present application provides a defluorination resin and a preparation method thereof, wherein the defluorination resin has excellent defluorination effect in both acidic and alkaline environments, which is beneficial for its use.

[0004] In the first aspect, the present application provides a defluorination resin, which comprises a first unit and a second unit, wherein the structural formula of the first unit is The structural formula of the second unit is Wherein, the R1 and the R2 are alkylene groups, the R3 is an alkylene group or a single bond, the R4 is an alkyl group or a hydrogen atom, the M1 is an aluminum salt group or a manganese salt group, and the M2 is an aluminum salt group or a manganese salt group.

[0005] Optionally, the defluorination resin further comprises a third unit, the structural formula of the third unit is Wherein, the R5 is an alkylene group, and the M3 is an aluminum salt group or a manganese salt group.

[0006] Optionally, the defluorination resin further comprises a fourth unit, the structural formula of the fourth unit being Wherein, the R6 is an alkylene group.

[0007] Optionally, the defluorination resin has a porous structure, and the pores of the defluorination resin have a diameter of 100 nm-10 μm.

[0008] Optionally, the saturated absorption capacity of the defluorination resin for fluoride ions is 0.1 mg / g-20 mg / g.

[0009] Optionally, in the fluorine-removing resin, the repetition number of the first unit is an integer between 20 and 1000, and the repetition number of the second unit is an integer between 20 and 1000.

[0010] Optionally, the number average molecular weight of the fluorine-removing resin is 100-350.

[0011] In a second aspect, the present application provides a method for preparing a fluorine-removing resin, comprising:

[0012] The first pretreated resin is mixed with an alkali liquor to obtain a second pretreated resin after a first reaction;

[0013] At least one of the aluminum salt solution and the manganese salt solution is mixed with the second pretreated resin to obtain the defluorination resin of the first aspect after a second reaction.

[0014] Optionally, the first pretreated resin comprises a second unit and a fifth unit, and the fifth unit has a structural formula of wherein the R7 and the R8 are alkyl groups.

[0015] Optionally, the first pretreated resin further comprises a sixth unit, and the sixth unit has a structural formula of wherein the R5 is an alkylene group, and the R9 is an alkyl group.

[0016] Optionally, the mass concentration of the alkali liquor is 1%-20%.

[0017] Optionally, the alkali liquor comprises at least one of a sodium hydroxide solution and a potassium hydroxide solution.

[0018] Optionally, the time of the first reaction is 3h-30h.

[0019] Optionally, the mass concentration of the aluminum salt solution is 1%-20%.

[0020] Optionally, the mass concentration of the manganese salt solution is 1%-20%.

[0021] Optionally, the time of the second reaction is 3h-8h.

[0022] Optionally, the temperature of the second reaction is 20℃-40℃.

[0023] The first unit of the defluorination resin of the present application contains an aluminum salt group and / or a manganese salt group and an imino phenyl boronic acid group, wherein the anion in the aluminum salt group and / or the manganese salt group can exchange with fluoride ions to form a weak acid root complex salt containing aluminum and / or manganese, thereby playing a defluorination effect. The weak acid root complex salt containing aluminum and / or manganese can exist stably under acidic conditions, while the second repeating unit contains an imino group, which improves the weak acid precipitation pH, so that the weak acid root complex salt containing aluminum and / or manganese is not easily dissolved under alkaline conditions, thereby making the defluorination resin can be used in alkaline environment, expanding the use scenarios of the defluorination resin. At the same time, the preparation method of the defluorination resin is simple and convenient to operate, and can be reused, which is conducive to the use of the defluorination resin. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to make the technical solutions in the embodiments of the present application or the prior art clearer, the accompanying drawings needed in the embodiments or prior art description will be briefly introduced. The specific embodiments described herein are only used to explain the present application, and are not used to limit the present application.

[0025] Figure 1 The preparation method flow chart of the defluorination resin provided for an embodiment of the present application. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work belong to the scope of protection of the present application. In the recycling of lithium carbonate from waste lithium batteries, fluorine in the electrolyte will be brought into the leaching solution, and lithium fluoride precipitate will be formed when alkali is added for precipitation, resulting in high fluorine content in the subsequent lithium carbonate product, which cannot meet the impurity requirements of battery-grade lithium carbonate. Currently, amino phosphonate resin treated with aluminum salt and quaternary amine alcohol resin treated with zirconium salt are used as defluorination resins; however, the quaternary amine alcohol resin treated with zirconium salt is suitable for treating acidic fluorine-containing liquid, and cannot treat alkaline fluorine-containing liquid. The amino phosphonate resin treated with aluminum salt still has strong phosphoric acid, and the complex salt formed after the aluminum salt is neutral or slightly alkaline, and can only treat weakly alkaline fluorine-containing liquid.

[0027] Therefore, the present application provides a defluorination resin which can be applied to acidic and alkaline environments. The defluorination resin comprises a first unit and a second unit, the structural formula of the first unit is The structural formula of the second unit is wherein R1 and R2 are alkylene groups, R3 is an alkylene group or a single bond, R4 is an alkyl group or a hydrogen atom, M1 is an aluminum salt group or a manganese salt group, and M2 is an aluminum salt group or a manganese salt group. The first unit contains an aluminum salt group and / or a manganese salt group, and an imino phenyl boronic acid group, wherein the imino phenyl boronic acid group is a weak acid group, the first unit contains a weak acid complex salt, and the anion in the aluminum salt group and / or the manganese salt group can exchange with fluoride ions to form a fluorine-containing weak acid complex salt containing aluminum and / or manganese, thereby achieving a defluorination effect. The fluorine-containing weak acid complex salt containing aluminum and / or manganese can exist stably under acidic conditions, and at the same time, the second repeating unit contains an imino group, which improves the precipitation pH of the weak acid, so that the fluorine-containing weak acid complex salt containing aluminum and / or manganese is not easily dissolved under alkaline conditions, thereby enabling the defluorination resin to be used in alkaline environments, expanding the use scenarios of the defluorination resin, and the defluorination resin can be reused, which is conducive to resource saving and more green and environmentally friendly.

[0028] The first unit in the defluorination resin of the present application enables the defluorination resin to adsorb fluoride ions and achieve the effect of defluorination, and enables the defluorination resin to be used in an acidic environment. M1 and M2 in the first unit can both be aluminum salt groups, both be manganese salt groups, or one be an aluminum salt group and the other be a manganese salt group. In an embodiment of the present application, the number of repetitions of the first unit in the defluorination resin is an integer from 20 to 1000, which is conducive to further improving the defluorination capacity of the defluorination resin and the defluorination effect in an acidic environment. Specifically, the number of repetitions of the first unit in the defluorination resin can be, but is not limited to, 20, 50, 80, 100, 300, 400, 500, 600, 700, 800, 900, or 1000, etc. In an embodiment of the present application, the number of repetitions of the first unit in the defluorination resin can be an integer from 50 to 500, which is conducive to improving the defluorination capacity of the defluorination resin, and also conducive to the preparation of the defluorination resin.

[0029] The second unit in the defluorination resin of the present application enables the defluorination resin to have a defluorination effect in an alkaline environment, thereby expanding the use scenarios of the defluorination resin. In an embodiment of the present application, the number of repetitions of the second unit in the defluorination resin is an integer from 20 to 1000, which is conducive to further improving the pH of the suitable use environment of the defluorination resin and further expanding the use range of the defluorination resin. Specifically, the number of repetitions of the second unit in the defluorination resin can be, but is not limited to, 20, 50, 80, 100, 300, 400, 500, 600, 700, 800, 900, or 1000, etc. In an embodiment of the present application, the number of repetitions of the second unit in the defluorination resin can be an integer from 50 to 500, which is conducive to improving the use range of the defluorination resin, and also conducive to the preparation of the defluorination resin.

[0030] In an embodiment of the present application, the ratio of the number of repetitions of the first unit to the number of repetitions of the second unit in the defluorination resin is from 1 to 100, which is conducive to further improving the defluorination capacity of the defluorination resin. Specifically, the ratio of the number of repetitions of the first unit to the number of repetitions of the second unit in the defluorination resin can be, but is not limited to, 2, 5, 10, 20, 35, 50, 75, 80, 90, or 100, etc. In an embodiment of the present application, the ratio of the number of repetitions of the first unit to the number of repetitions of the second unit in the defluorination resin can be from 2 to 20, which is conducive to further improving the performance of the defluorination resin.

[0031] In an embodiment of the present application, the defluorination resin further comprises a third unit, and the structural formula of the third unit is R5-M3-R5-NH-CH2-C6H3-COOH, wherein R5 is an alkylene group, and M3 is an aluminum salt group or a manganese salt group. The third unit containing the aluminum salt group and / or the manganese salt group and the imino phenylpropionic acid group can further reduce the pH of the environment suitable for use of the defluorination resin, so that the defluorination resin can be used in a more acidic environment, further expanding the use range of the defluorination resin. M3 and M1 in the third unit can both be aluminum salt groups, both be manganese salt groups, or one be an aluminum salt group and the other be a manganese salt group. M3 and M2 in the third unit can both be aluminum salt groups, both be manganese salt groups, or one be an aluminum salt group and the other be a manganese salt group.

[0032] In an embodiment of the present application, the number of repetitions of the third unit in the defluorination resin is an integer in the range of 20-1000, which is advantageous for further improving the defluorination ability of the defluorination resin and the defluorination effect in an acidic environment. Specifically, the number of repetitions of the third unit in the defluorination resin can be, but is not limited to, 20, 50, 80, 100, 300, 400, 500, 600, 700, 800, 900, or 1000, etc. In an embodiment of the present application, the number of repetitions of the third unit in the defluorination resin can be an integer in the range of 100-600, which is advantageous for improving the defluorination ability of the defluorination resin, while also being advantageous for the preparation of the defluorination resin.

[0033] In an embodiment of the present application, the ratio of the number of repetitions of the first unit to the number of repetitions of the third unit in the defluorination resin is in the range of 0.1-10, which is advantageous for further improving the defluorination ability of the defluorination resin and the applicable scenarios. Specifically, the ratio of the number of repetitions of the first unit to the number of repetitions of the third unit in the defluorination resin can be, but is not limited to, 0.5, 1, 3, 3.5, 5, 6, 8, or 10, etc. In an embodiment of the present application, the ratio of the number of repetitions of the first unit to the number of repetitions of the third unit in the defluorination resin can be in the range of 1-5, which is advantageous for further improving the performance of the defluorination resin.

[0034] In an embodiment of the present application, the defluorination resin further comprises a fourth unit, and the structural formula of the fourth unit is wherein R6 is an alkylene group. The fourth unit can improve the strength of the defluorination resin, which is advantageous for the use of the defluorination resin.

[0035] In an embodiment of the present application, the number of repetitions of the fourth unit in the defluorination resin is an integer in the range of 20-1000, which is advantageous for further improving the mechanical properties of the defluorination resin. Specifically, the number of repetitions of the fourth unit in the defluorination resin can be, but is not limited to, 20, 50, 80, 100, 300, 400, 500, 600, 700, 800, 900, or 1000, etc. In an embodiment of the present application, the number of repetitions of the fourth unit in the defluorination resin can be an integer in the range of 50-500, which is advantageous for improving the mechanical properties of the defluorination resin, while also being advantageous for the preparation of the defluorination resin. The number of repetitions of the first unit, the second unit, the third unit, and the fourth unit in the defluorination resin of the present application can be the same or different.

[0036] In an embodiment of the present application, the ratio of the number of repetitions of the first unit to the number of repetitions of the fourth unit in the fluorine-removing resin is 0.05-50, which is conducive to further improving the fluorine-removing ability and mechanical properties of the fluorine-removing resin. Specifically, the ratio of the number of repetitions of the first unit to the number of repetitions of the fourth unit in the fluorine-removing resin can be, but is not limited to, 0.1, 0.3, 0.5, 1, 2, 3.5, 5, 10, 20, 25, 30, 40, or 50, etc. In an embodiment of the present application, the ratio of the number of repetitions of the first unit to the number of repetitions of the fourth unit in the fluorine-removing resin can be 2-5, which is conducive to further improving the performance of the fluorine-removing resin.

[0037] In an embodiment of the present application, the alkyl group is an alkane molecule from which one hydrogen atom is removed, including linear alkyl groups and branched alkyl groups. The number of carbon atoms in the alkyl group is 1-8. Specifically, the number of carbon atoms in the alkyl group can be, but is not limited to, 1, 2, 3, 4, 5, 6, 7, or 8, etc. Exemplarily, the alkyl group can include, but is not limited to, at least one of methyl, ethyl, n-propyl, n-butyl, isobutyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, n-hexyl, heptyl, 2-methylhexyl, 5-methylpentyl, 2-ethylbutyl, 3-ethylbutyl, nonyl, and decyl.

[0038] In an embodiment of the present application, the alkylene group is a divalent saturated group formed by removing one hydrogen atom from an alkyl group, including linear alkylene groups and branched alkylene groups. The alkylene group can be a substituted alkylene group, or an unsubstituted alkylene group; specifically, the substituted alkylene group can be, but is not limited to, an alkylene group substituted with at least one of halogen, oxygen atom, sulfur atom, and nitrogen atom. The number of carbon atoms in the alkylene group is 1-8. Specifically, the number of carbon atoms in the alkylene group can be, but is not limited to, 1, 2, 3, 4, 5, 6, 7, or 8, etc. Exemplarily, the alkylene group can include, but is not limited to, at least one of methylene, ethylene, propylene, 2-propylene, butylene, and pentylene. In an embodiment of the present application, the alkylene group can be propylene. In another embodiment of the present application, the alkylene group can be butylene. In an embodiment of the present application, the alkylene group can be R 11 is an alkylene group, and R 12 is an alkyl group. The selection of the alkylene group and the alkyl group is as described above, and will not be repeated here. The alkylene group is selected from When R1, R2, R3, R5, and R6 are branched alkylene groups, it can be understood that R 12 is hydrogen, the alkylene group is a linear alkylene group. R1, R2, R3, R5, and R6 can be the same or different. For example, at least two of R1, R2, R3, R5, and R6 are branched alkylene groups. When R1, R2, R3, R5, and R6 are branched alkylene groups, it can be understood that R

[0039] In an embodiment of the present application, when R3 in the second unit is a single bond, the structure of the second unit is In an embodiment of the present application, when R4 in the second unit is a hydrogen atom, the structure of the second unit is In this way, the amino group is introduced into the fluorine-free resin.

[0040] In an embodiment of the present application, the aluminum salt group includes at least one of a chloride group of aluminum, a sulfate group of aluminum and a nitrate group of aluminum. In an embodiment of the present application, the manganese salt group includes at least one of a chloride group of manganese, a sulfate group of manganese and a nitrate group of manganese. It can be understood that M1, M2 and M3 can be the same or different. In an embodiment of the present application, when M1 and M2 are the chloride group of aluminum, the structure of the first unit can be In an embodiment of the present application, when M1 and M2 are the chloride group of manganese, the structure of the first unit can be In an embodiment of the present application, when M3 is the chloride group of aluminum, the structure of the third unit can be In an embodiment of the present application, when M3 is the chloride group of manganese, the structure of the third unit can be

[0041] When the fluorine-free resin includes the first unit, the second unit and the third unit, the connection order of the first unit, the second unit and the third unit can be selected as needed; when the fluorine-free resin includes the first unit, the second unit and the fourth unit, the connection order of the first unit, the second unit and the fourth unit can be selected as needed; when the fluorine-free resin includes the first unit, the second unit, the third unit and the fourth unit, the connection order of the first unit, the second unit, the third unit and the fourth unit can be selected as needed. In an embodiment of the present application, the structure of the fluorine-free resin can be wherein n1, n2, n3 and n4 are independently selected integers in the range of 20-1000. In an embodiment of the present application, the structure of the fluorine-free resin can be In an embodiment of the present application, the structure of the fluorine-free resin can be

[0042] In an embodiment of the present application, the number average molecular weight of the fluorine-free resin is 100-350. Specifically, the number average molecular weight of the fluorine-free resin can be, but is not limited to, 100, 120, 140, 150, 180, 200, 220, 250, 280, 300, 325, 340 or 350, etc. The number average molecular weight is detected by the following method: dissolving the sample to be detected in a solvent (benzene or chloroform) to form a solution, using an osmometer to test the osmotic pressure of the solution to the solvent, and then calculating the number average molecular weight of the sample to be detected by the osmotic pressure method.

[0043] In an embodiment of the present application, the fluorine-removing resin is in a porous structure. That is, the fluorine-removing resin has a plurality of pores, which is conducive to the sufficient removal of fluorine. In an embodiment of the present application, the pore size of the pores of the fluorine-removing resin is 100 nm-10 μm, which is conducive to the sufficient removal of fluorine and ensures the strength of the fluorine-removing resin. Specifically, the pore size of the pores of the fluorine-removing resin can be, but is not limited to, 100 nm, 500 nm, 800 nm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, etc.

[0044] In an embodiment of the present application, the saturated absorption amount of the fluorine-removing resin for fluorine ions is 0.1 mg / g-20 mg / g. That is, the saturated absorption amount of 1 g of the fluorine-removing resin for fluorine ions is 0.1 mg-20 mg. The fluorine-removing resin can effectively adsorb fluorine ions to achieve the effect of removing fluorine.

[0045] In an embodiment of the present application, the use pH of the fluorine-removing resin is 4-10. The fluorine-removing resin can be used to treat a solution to be defluorinated with a pH of 4-10, and the use scenario is wide. In an embodiment of the present application, the use pH of the fluorine-removing resin can be 5-10. In an embodiment, when the fluorine-removing resin comprises a first unit and a second unit, the use pH of the fluorine-removing resin can be 5-10. In another embodiment, when the fluorine-removing resin comprises a first unit, a second unit and a third unit, the use pH of the fluorine-removing resin can be 4-10.

[0046] Please refer to Figure 1 The preparation method flow chart of the fluorine-removing resin provided in an embodiment of the present application comprises:

[0047] S101: mixing the first pretreated resin with an alkali solution, and obtaining a second pretreated resin after a first reaction.

[0048] S102: mixing at least one of an aluminum salt solution and a manganese salt solution with the second pretreated resin, and obtaining the fluorine-removing resin after a second reaction.

[0049] The fluorine-removing resin in any of the above embodiments can be prepared by the above preparation method, which is simple to operate and convenient to prepare, and is conducive to the wide use of the fluorine-removing resin.

[0050] In an embodiment of the present application, the first pretreated resin comprises a second unit and a fifth unit, and the structural formula of the second unit is The structural formula of the fifth unit is wherein R2 and R3 are alkylene, R4, R7 and R8 are alkyl. In the first pretreatment resin, the second unit becomes the second unit in the fluorine-removing resin after the above preparation process, and the fifth unit in the first pretreatment resin becomes the first unit in the fluorine-removing resin after the above preparation process. In an embodiment of the present application, the number of repetitions of the second unit in the first pretreatment resin is an integer from 20 to 1000. Specifically, the number of repetitions of the second unit in the first pretreatment resin can be, but is not limited to, 20, 50, 80, 100, 300, 400, 500, 600, 700, 800, 900 or 1000, etc. In an embodiment of the present application, the number of repetitions of the fifth unit in the first pretreatment resin is an integer from 20 to 1000. Specifically, the number of repetitions of the fifth unit in the first pretreatment resin can be, but is not limited to, 20, 50, 80, 100, 300, 400, 500, 600, 700, 800, 900 or 1000, etc.

[0051] In an embodiment of the present application, to obtain to obtain The reaction can form the first pretreatment resin, and at this time, the second unit in the first pretreatment resin is The structural formula of the fifth unit is R in the second unit and the fifth unit 12 may be the same or different. It can be understood that the above is one embodiment for preparing the first pretreatment resin, and the first pretreatment resin can also be prepared by other preparation methods, which are not limited in the present application.

[0052] In an embodiment of the present application, the first pretreatment resin further comprises a sixth unit, and the structural formula of the sixth unit is wherein R5 is alkylene, and R9 is alkyl. In the first pretreatment resin, the sixth unit becomes the third unit in the fluorine-removing resin after the above preparation process. In an embodiment of the present application, the number of repetitions of the sixth unit in the first pretreatment resin is an integer from 20 to 1000. Specifically, the number of repetitions of the sixth unit in the first pretreatment resin can be, but is not limited to, 20, 50, 80, 100, 300, 400, 500, 600, 700, 800, 900 or 1000, etc.

[0053] In an embodiment of the present application, the first pretreatment resin further comprises a fourth unit, and the structural formula of the fourth unit is wherein R6 is an alkylene group. The fourth unit in the first pretreatment resin becomes the fourth unit in the fluorine-removal resin after the above preparation process. In an embodiment of the present application, the number of repetitions of the fourth unit in the first pretreatment resin is an integer in the range of 20-1000. Specifically, the number of repetitions of the fourth unit in the first pretreatment resin can be, but is not limited to, 20, 50, 80, 100, 300, 400, 500, 600, 700, 800, 900 or 1000, etc.

[0054] The number of repetitions of the second unit, the fourth unit, the fifth unit and the sixth unit in the first pretreatment resin of the present application can be the same or different. When the first pretreatment resin comprises the second unit, the fifth unit and the fourth unit, the connection order of the second unit, the fifth unit and the fourth unit can be selected as required; when the fluorine-removal resin comprises the second unit, the fifth unit and the sixth unit, the connection order of the second unit, the fifth unit and the sixth unit can be selected as required; when the fluorine-removal resin comprises the second unit, the fourth unit, the fifth unit and the sixth unit, the connection order of the second unit, the fourth unit, the fifth unit and the sixth unit can be selected as required. In an embodiment of the present application, the structural formula of the first pretreatment resin can be wherein n1, n2, n3 and n4 are independently selected as an integer in the range of 20-1000.

[0055] In an embodiment of the present application, the number average molecular weight of the first pretreatment resin is in the range of 100-350. Specifically, the number average molecular weight of the first pretreatment resin can be, but is not limited to, 100, 120, 140, 150, 180, 200, 220, 250, 280, 300, 325, 340 or 350, etc.

[0056] In an embodiment of the present application, the first reaction time is in the range of 3h-30h, thereby ensuring sufficient reaction of the first pretreatment resin with the alkaline solution. Specifically, the first reaction time can be, but is not limited to, 3h, 5h, 8h, 10h, 12h, 15h, 18h, 20h, 25h or 30h, etc.

[0057] In an embodiment of the present application, the mass concentration of the alkaline solution is in the range of 1%-20%, thereby ensuring sufficient reaction of the first pretreatment resin with the alkaline solution. Specifically, the mass concentration of the alkaline solution can be, but is not limited to, 1%, 3%, 5%, 9%, 10%, 12%, 15%, 18% or 20%, etc.

[0058] In an embodiment of the present application, the alkaline solution comprises at least one of a sodium hydroxide solution and a potassium hydroxide solution. The sodium hydroxide and / or the potassium hydroxide reacts with the first pretreatment resin to form a sodium salt resin and / or a potassium salt resin. In an embodiment of the present application, when the alkaline solution is a sodium hydroxide solution, a second pretreatment resin is obtained after the first reaction, and the structural formula of the second pretreatment resin can be

[0059]

[0060] The at least one of the aluminum salt solution and the manganese salt solution is mixed with the second pretreated resin, the anion group in the second pretreated resin is a weak acid group, and the aluminum salt group and / or the manganese salt group replaces sodium and / or potassium in the second pretreated resin to form a weak acid complex salt of aluminum and / or manganese. Before the at least one of the aluminum salt solution and the manganese salt solution is mixed with the second pretreated resin, the second pretreated resin can also be washed with water, such as deionized water, to ensure the second reaction. When the at least one of the aluminum salt solution and the manganese salt solution reacts with the second pretreated resin, the second pretreated resin can be soaked in the at least one of the aluminum salt solution and the manganese salt solution, or the second pretreated resin can be fixed in a column, and the at least one of the aluminum salt solution and the manganese salt solution flows through the second pretreated resin column to react.

[0061] In an embodiment of the present application, the second reaction time is 3h-8h, so as to ensure sufficient reaction with the second pretreated resin. Specifically, the second reaction time can be, but is not limited to, 3h, 4h, 5h, 6h, 7h or 8h, etc.

[0062] In an embodiment of the present application, the second reaction temperature is 20℃-40℃, so as to ensure sufficient reaction with the second pretreated resin. Specifically, the second reaction temperature can be, but is not limited to, 20℃, 23℃, 25℃, 28℃, 30℃, 32℃, 35℃, 37℃ or 40℃, etc.

[0063] In an embodiment of the present application, the mass concentration of the aluminum salt solution is 1%-20%, so as to ensure sufficient reaction with the second pretreated resin. Specifically, the mass concentration of the aluminum salt solution can be, but is not limited to, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%, etc. The aluminum salt solution can be, but is not limited to, at least one of an aluminum chloride solution, an aluminum sulfate solution and an aluminum nitrate solution. In an embodiment of the present application, the aluminum chloride solution is mixed with the second pretreated resin, and the defluorinated resin is obtained after the second reaction, and the structural formula of the defluorinated resin can be

[0064] In an embodiment of the present application, the mass concentration of the manganese salt solution is 1-20%, so as to ensure sufficient reaction with the second pretreatment resin. Specifically, the mass concentration of the manganese salt solution can be, but is not limited to, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%, etc. The manganese salt solution can be, but is not limited to, at least one of a manganese chloride solution, a manganese sulfate solution and a manganese nitrate solution. In an embodiment of the present application, the manganese chloride solution is mixed with the second pretreatment resin, and after the second reaction, a defluorination resin is obtained, and the structural formula of the defluorination resin can be

[0065] In an embodiment of the present application, the second pretreatment resin is fixed in a column, and at least one of the aluminum salt solution and the manganese salt solution flows through the second pretreatment resin column to perform the second reaction. The flow rate of the aluminum salt solution and / or the manganese salt solution can be 1-20 BV / h, so as to ensure sufficient second reaction.

[0066] In the present application, the defluorination resin after the second reaction can be washed to remove residual reaction liquid or impurities. Specifically, the defluorination resin can be washed with three times the volume of water.

[0067] In the present application, the weak acid complex salt of aluminum and / or manganese in the defluorination resin can react with fluoride ions to generate a weak acid complex salt of aluminum and / or manganese containing fluoride. In an embodiment of the present application, the structural formula of the defluorination resin can be After reacting with the fluoride-containing treatment liquid, it can generate

[0068]

[0069] The defluorination resin provided in the present application can be used in waste battery recycling and can also be used in wastewater treatment. The defluorination resin after defluorination treatment can be reused after washing with hydrochloric acid.

[0070] The effects of the technical solutions of the present application are further described below through specific examples.

[0071] Example 1

[0072] 90g of 1-chloro-1-butene was weighed into 100g of dimethyl sulfoxide (DMSO), 165g of methyl p-aminobenzoate was added, 60g of sodium carbonate was added, and the temperature was raised to 60°C and heated to reflux for 10h. After filtration, vacuum distillation, filtration and column purification, ethyl vinyl aminobenzoic acid methyl ester was obtained.

[0073] Take 90g 1-chloro-1-butene into 100g DMSO, add 179g 3-amino benzenepropionic acid methyl ester, add 60g sodium carbonate, heat to 60℃ and reflux for 10h, after filtration, distillation under reduced pressure, filtration, column purification, ethyl vinyl amino benzenepropionic acid methyl ester is obtained.

[0074] Blend ethyl vinyl amino benzenepropionic acid methyl ester, ethyl vinyl amino benzenepropionic acid methyl ester, allyl ethylamine, styrene, add a certain amount of water, the mass ratio of ethyl vinyl amino benzenepropionic acid methyl ester, ethyl vinyl amino benzenepropionic acid methyl ester, allyl ethylamine, styrene is 10:11:2:2, then add 1% benzoyl peroxide, take xylene and heptane mixed solvent as porogen, the mass ratio of reaction and porogen is 1:10, after stirring, heat to 100℃ for copolymerization reaction (9h), then distillation, washing, drying, sieving to obtain ethyl vinyl amino benzenepropionic acid methyl ester-ethyl vinyl amino benzenepropionic acid methyl ester-allyl ethylamine-styrene copolymer, the repeating units of ethyl vinyl amino benzenepropionic acid methyl ester, ethyl vinyl amino benzenepropionic acid methyl ester, allyl ethylamine, styrene in ethyl vinyl amino benzenepropionic acid methyl ester-ethyl vinyl amino benzenepropionic acid methyl ester-allyl ethylamine-styrene copolymer are 40, 40, 20, 20 respectively. The repeating units of allyl ethylamine are 20.

[0075] The repeating units of styrene are 20. The repeating units of styrene are 20.

[0076] The above product is treated with 10% sodium hydroxide solution for 24h, then washed with 3 times volume of deionized water for standby. Aluminum chloride is dissolved in water to form a 10% mass fraction solution, the treated resin is added to the aluminum chloride solution, and reacted for 4h, then washed with 3 times volume of water to obtain a defluorinated resin.

[0077] Example 2

[0078] Take 90g 1-chloro-1-butene into 100g DMSO, add 179g 3-amino benzenepropionic acid methyl ester, add 60g sodium carbonate, heat to 60℃ and reflux for 10h, after filtration, distillation under reduced pressure, filtration, column purification, ethyl vinyl amino benzenepropionic acid methyl ester is obtained.

[0079] Take 90g 1-chloro-1-butene into 100g DMSO, add 179g 3-amino benzenepropionic acid methyl ester, add 60g sodium carbonate, heat to 60℃ and reflux for 10h, after filtration, distillation under reduced pressure, filtration, column purification, ethyl vinyl amino benzenepropionic acid methyl ester is obtained.

[0080] The methyl ethylvinylaminophenylboronic acid, methyl ethylvinylaminophenylpropionic acid, allyl ethylamine, styrene are blended, a certain amount of water is added, the mass ratio of the methyl ethylvinylaminophenylboronic acid, methyl ethylvinylaminophenylpropionic acid, allyl ethylamine, styrene is 10:11:1:2, then 1% of benzoyl peroxide is added, a mixed solvent of xylene and heptane with a mass ratio of 1:10 is used as a porogen, the mass ratio of the reactants to the porogen is controlled to be 1:10, after stirring, the temperature is raised to 100°C for copolymerization (9h), and then the methyl ethylvinylaminophenylboronic acid-methyl ethylvinylaminophenylpropionic acid-allyl ethylamine-styrene copolymer is prepared through distillation, washing, drying and sieving; the repeating numbers of the methyl ethylvinylaminophenylboronic acid repeating unit, the methyl ethylvinylaminophenylpropionic acid repeating unit, the allyl ethylamine repeating unit and the styrene repeating unit in the methyl ethylvinylaminophenylboronic acid-methyl ethylvinylaminophenylpropionic acid-allyl ethylamine-styrene copolymer are 40, 40, 10 and 20, respectively.

[0081] The above product is treated with a 10% sodium hydroxide solution for 24h, and then washed with 3 times the volume of deionized water for standby. Aluminum chloride is dissolved in water to prepare a 10% mass fraction solution, and the treated resin is added to the aluminum chloride solution, washed with 3 times the volume of water after reacting for 4h to obtain a fluorine-removed resin.

[0082] Example 3

[0083] 90g of 1-chloro-1-butene is weighed into 100g of dimethyl sulfoxide (DMSO), 165g of methyl p-aminobenzoate is added, 60g of sodium carbonate is added, the temperature is raised to 60°C and heated to reflux for 10h, and then the methyl ethylvinylaminophenylboronic acid is obtained after filtration, distillation under reduced pressure, filtration, and column purification.

[0084] 90g of 1-chloro-1-butene is weighed into 100g of dimethyl sulfoxide (DMSO), 179g of methyl 3-aminobenzoate is added, 60g of sodium carbonate is added, the temperature is raised to 60°C and heated to reflux for 10h, and then the methyl ethylvinylaminophenylpropionic acid is obtained after filtration, distillation under reduced pressure, filtration, and column purification.

[0085] The methyl ethylvinylaminophenylboronic acid, methyl ethylvinylaminophenylpropionic acid, allyl ethylamine, styrene are blended, a certain amount of water is added, the mass ratio of the methyl ethylvinylaminophenylboronic acid, methyl ethylvinylaminophenylpropionic acid, allyl ethylamine, styrene is 20:22:1:4, then 1% of benzoyl peroxide is added, a mixed solvent of xylene and heptane with a mass ratio of 1:10 is used as a porogen, the mass ratio of the reactants to the porogen is controlled to be 1:10, after stirring, the temperature is raised to 100°C for copolymerization (9h), and then the methyl ethylvinylaminophenylboronic acid-methyl ethylvinylaminophenylpropionic acid-allyl ethylamine-styrene copolymer is prepared through distillation, washing, drying and sieving; the repeating numbers of the methyl ethylvinylaminophenylboronic acid repeating unit, the methyl ethylvinylaminophenylpropionic acid repeating unit, the allyl ethylamine repeating unit and the styrene repeating unit in the methyl ethylvinylaminophenylboronic acid-methyl ethylvinylaminophenylpropionic acid-allyl ethylamine-styrene copolymer are 45, 45, 5 and 20, respectively.

[0086] The above product is treated with a 10% sodium hydroxide solution for 24h, and then washed with 3 times the volume of deionized water for standby. Aluminum chloride is dissolved in water to prepare a 10% mass fraction solution, and the treated resin is added to the aluminum chloride solution, washed with 3 times the volume of water after reacting for 4h to obtain a fluorine-removed resin.

[0087] Example 4

[0088] 90g of 1-chloro-1-butene is weighed into 100g of dimethyl sulfoxide (DMSO), 165g of methyl p-aminobenzoate is added, 60g of sodium carbonate is added, the temperature is raised to 60°C and heated to reflux for 10h, and then filtered, distilled under reduced pressure, filtered, and purified by column to obtain methyl ethylvinylaminophenylboronic acid.

[0089] 90g of 1-chloro-1-butene is weighed into 100g of dimethyl sulfoxide (DMSO), 179g of methyl 3-aminobenzoate is added, 60g of sodium carbonate is added, the temperature is raised to 60°C and heated to reflux for 10h, and then filtered, distilled under reduced pressure, filtered, and purified by column to obtain methyl ethylvinylaminophenylpropionic acid.

[0090] The methyl ethylvinylaminophenylboronic acid, methyl ethylvinylaminophenylpropionic acid, allyl ethylamine, styrene are blended, a certain amount of water is added, the mass ratio of the methyl ethylvinylaminophenylboronic acid, methyl ethylvinylaminophenylpropionic acid, allyl ethylamine, styrene is 30:11:1:4, then 1% of benzoyl peroxide is added, a mixed solvent of xylene and heptane with a mass ratio of 1:10 is used as a porogen, the mass ratio of the reactants to the porogen is controlled to be 1:10, after stirring, the temperature is raised to 100°C for copolymerization (9h), and then the methyl ethylvinylaminophenylboronic acid-methyl ethylvinylaminophenylpropionic acid-allyl ethylamine-styrene copolymer is prepared through distillation, washing, drying and sieving; the repeating numbers of the methyl ethylvinylaminophenylboronic acid repeating unit, the methyl ethylvinylaminophenylpropionic acid repeating unit, the allyl ethylamine repeating unit and the styrene repeating unit in the methyl ethylvinylaminophenylboronic acid-methyl ethylvinylaminophenylpropionic acid-allyl ethylamine-styrene copolymer are 70, 20, 5 and 20, respectively.

[0091] The above product is treated with a 10% sodium hydroxide solution for 24h, and then washed with 3 times the volume of deionized water for standby. Aluminum chloride is dissolved in water to prepare a 10% mass fraction solution, and the treated resin is added to the aluminum chloride solution, washed with 3 times the volume of water after reacting for 4h to obtain a fluorine-removed resin.

[0092] Example 5

[0093] 90g of 1-chloro-1-butene is weighed into 100g of dimethyl sulfoxide (DMSO), 165g of methyl p-aminobenzoate is added, 60g of sodium carbonate is added, the temperature is raised to 60°C and heated to reflux for 10h, and then filtered, distilled under reduced pressure, filtered, and purified by column to obtain methyl ethylvinylaminophenylboronic acid.

[0094] 90g of 1-chloro-1-butene is weighed into 100g of DMSO, 179g of 3-aminobenzoic acid methyl ester is added, 60g of sodium carbonate is added, the temperature is raised to 60°C and heated to reflux for 10h, and then filtered, distilled under reduced pressure, filtered, and purified by column to obtain methyl ethylvinylaminophenylpropionic acid.

[0095] The methyl ethylvinylaminophenylboronic acid, methyl ethylvinylaminophenylpropionic acid, allyl ethylamine and styrene are blended, and then added into a certain amount of water, the mass ratio of the methyl ethylvinylaminophenylboronic acid, methyl ethylvinylaminophenylpropionic acid, allyl ethylamine and styrene being 30:11:2:4, then 1% of benzoyl peroxide is added, a mixed solvent of xylene and heptane with a mass ratio of 1:10 is used as a porogen, the mass ratio of the reactants to the porogen is controlled to be 1:10, and then the copolymerization reaction is carried out at 100°C (9h) after stirring, and then the methyl ethylvinylaminophenylboronic acid-methyl ethylvinylaminophenylpropionic acid-allyl ethylamine-styrene copolymer is prepared through distillation, washing, drying and sieving, the repeating numbers of the methyl ethylvinylaminophenylboronic acid repeating unit, the methyl ethylvinylaminophenylpropionic acid repeating unit, the allyl ethylamine repeating unit and the styrene repeating unit in the methyl ethylvinylaminophenylboronic acid-methyl ethylvinylaminophenylpropionic acid-allyl ethylamine-styrene copolymer are 70, 20, 10 and 20 respectively.

[0096] The above product is treated with a 10% sodium hydroxide solution for 24h, and then washed with 3 times the volume of deionized water for standby use. Aluminum chloride is dissolved in water to prepare a 10% mass fraction solution, and the treated resin is added into the aluminum chloride solution, and then washed with 3 times the volume of water after 4h of reaction to obtain a fluorine-removed resin.

[0097] Example 6

[0098] 90g of 1-chloro-1-butene is added into 100g of DMSO, 165g of methyl p-aminobenzene boronic acid is added, 60g of anhydrous sodium carbonate is added, heated to 60°C and refluxed for 10h, filtered, distilled under reduced pressure, filtered, and purified by column to obtain methyl ethylvinylaminophenylboronic acid.

[0099] The methyl ethylvinylaminophenylboronic acid, allyl ethylamine and styrene are blended, and then added into a certain amount of water, the mass ratio of the methyl ethylvinylaminophenylboronic acid, allyl ethylamine and styrene being 10:2:2, then 1% of benzoyl peroxide is added, a mixed solvent of xylene and heptane with a mass ratio of 1:10 is used as a porogen, the mass ratio of the reactants to the porogen is controlled to be 1:10, and then the copolymerization reaction is carried out at 100°C (8h) after stirring, and then the methyl ethylvinylaminophenylboronic acid-allyl ethylamine-styrene copolymer is prepared through distillation, washing, drying and sieving, the repeating numbers of the methyl ethylvinylaminophenylboronic acid repeating unit, the allyl ethylamine repeating unit and the styrene repeating unit in the methyl ethylvinylaminophenylboronic acid-allyl ethylamine-styrene copolymer are 40, 20 and 20 respectively.

[0100] A certain amount of the above resin is treated with 10% sodium hydroxide solution for 24 hours, and then washed with three times the volume of deionized water for standby. A certain amount of aluminum oxide is dissolved in water to form a 10% mass fraction solution, and the treated resin is added to the aluminum chloride solution. After 4 hours of reaction, 3 times the volume of water is washed to obtain a fluoride removal resin.

[0101] Example 7

[0102] 90g of 1-chloro-1-butene is weighed into 100g of dimethyl sulfoxide (DMSO), 165g of methyl p-aminobenzoate is added, 60g of sodium carbonate is added, the temperature is raised to 60°C and heated to reflux for 10h. After filtration, vacuum distillation, filtration, column purification, methyl ethyl vinyl aminobenzoate is obtained.

[0103] 90g of 1-chloro-1-butene is weighed into 100g of DMSO, 179g of methyl 3-aminobenzoate is added, 60g of sodium carbonate is added, the temperature is raised to 60°C and heated to reflux for 10h. After filtration, vacuum distillation, filtration, column purification, methyl ethyl vinyl aminobenzoate is obtained.

[0104] The methyl ethyl vinyl aminobenzoate, methyl ethyl vinyl aminobenzoate, allyl ethylamine, styrene are blended in a certain amount of water, the mass ratio of methyl ethyl vinyl aminobenzoate, methyl ethyl vinyl aminobenzoate, allyl ethylamine, styrene is 10:11:2:2, then 1% benzoyl peroxide is added, xylene and heptane mixed solvent with a mass ratio of 1:10 is used as a pore former, the mass ratio of reactants to pore former is controlled at 1:10, after stirring, the temperature is raised to 100°C for copolymerization reaction (9h), then distilled, washed, dried, and sieved to obtain the methyl ethyl vinyl aminobenzoate-methyl ethyl vinyl aminobenzoate-allyl ethylamine-styrene copolymer, the repeating number of the methyl ethyl vinyl aminobenzoate repeating unit, the methyl ethyl vinyl aminobenzoate repeating unit, the allyl ethylamine repeating unit, and the styrene repeating unit in the methyl ethyl vinyl aminobenzoate-methyl ethyl vinyl aminobenzoate-allyl ethylamine-styrene copolymer is 40, 40, 20, and 20, respectively.

[0105] The above product is treated with 10% sodium hydroxide solution for 24 hours, and then washed with three times the volume of deionized water for standby. Manganese chloride is dissolved in water to form a 15% mass fraction solution, and the treated resin is added to the manganese chloride solution. After 4 hours of reaction, 3 times the volume of water is washed to obtain a fluoride removal resin.

[0106] Comparative Example 1

[0107] Take 148g 4-vinyl phenyl boronic acid, add to 100g DMSO, add 152g chloropropane, 120g sodium carbonate, heat to 40℃ and reflux for 10h, filter, distill under reduced pressure, filter, and purify by column to obtain propyl vinyl phenyl boronic acid.

[0108] Take p-bromophenylpropionic acid as raw material, exchange with Grignard reagent isopropyl magnesium chloride in solvent tetrahydrofuran to obtain p-bromophenylpropionic acid Grignard reagent, then add acetaldehyde dropwise to the synthesized Grignard reagent, after the reaction is completed, acidification and post-processing to obtain the intermediate product p-hydroxyethyl phenylpropionic acid, then dehydrate in DMSO with concentrated sulfuric acid to obtain p-vinyl phenylpropionic acid, then add chloropropane and reflux to obtain p-vinyl phenylpropionate.

[0109] Blend propyl vinyl phenyl boronic acid and p-vinyl phenylpropionic acid propyl ester with styrene, add a certain amount of water, the mass ratio of propyl vinyl phenyl boronic acid, p-vinyl phenylpropionic acid propyl ester and styrene is 10:11:2, then add 1% benzoyl peroxide, use the mixed solvent of xylene and heptane with a mass ratio of 1:10 as a pore former, adjust the mass ratio of reactants to pore former to 1:10, stir and heat to 100℃, then perform copolymerization reaction (9h), then distill, wash, dry, and sieve to obtain propyl vinyl phenyl boronic acid-p-vinyl phenylpropionic acid propyl ester-styrene copolymer, the repeating unit of propyl vinyl phenyl boronic acid in the propyl vinyl phenyl boronic acid-p-vinyl phenylpropionic acid propyl ester-styrene copolymer is The repeating unit of propyl vinyl phenylpropionic acid in the propyl vinyl phenyl boronic acid-p-vinyl phenylpropionic acid propyl ester-styrene copolymer is The repeating number of the repeating unit of styrene is 40, 50, and 20 in turn.

[0110] The above product is treated with 10% sodium hydroxide solution for 24h, then washed with 3 times the volume of deionized water for standby. Dissolve aluminum chloride in water to form a 10% mass fraction solution, add the treated resin to the aluminum chloride solution, react for 4h, then wash with 3 times the volume of water to obtain a fluorine-removed resin.

[0111] Comparative Example 2

[0112] Take 90g 1-chloro-1-butene and add to 100g DMSO, add 151g 4-aminobenzoic acid methyl ester, 60g anhydrous sodium carbonate, heat to 60℃ and reflux for 10h, filter, distill under reduced pressure, filter, and purify by column to obtain methyl vinyl aminobenzoate.

[0113] Methyl vinylamino benzoate and allyl ethylamine, styrene were blended, and a certain amount of water was added, the mass ratio of methyl vinylamino benzoate and allyl ethylamine, styrene was 10:2:2, then 1% benzoyl peroxide was added, a mixed solvent of xylene and heptane with a mass ratio of 1:10 was used as a porogen, the mass ratio of the reactants to the porogen was controlled to be 1:10, after stirring, the temperature was raised to 100°C, and a copolymerization reaction was carried out (9h), then distillation, washing, drying, and sieving were performed to obtain a methyl vinylamino benzoate-allyl ethylamine-styrene copolymer, the repeating number of the methyl vinylamino benzoate repeating unit in the methyl vinylamino benzoate-allyl ethylamine-styrene copolymer, the allyl ethylamine repeating unit, and the styrene repeating unit was 55, 20, and 20, respectively. The repeating number of the allyl ethylamine repeating unit and the styrene repeating unit was 55 and 20, respectively.

[0114] The above product was treated with a 10% sodium hydroxide solution for 24h, and then washed with 3 times the volume of deionized water for standby use. Aluminum chloride was dissolved in water to prepare a 10% mass fraction solution, the treated resin was added to the aluminum chloride solution, and after reacting for 4h, 3 times the volume of water was washed to obtain a fluorine-removed resin.

[0115] Comparative Example 3

[0116] 90g of 1-chloro-1-butene was added to 100g of DMSO, 151g of methyl 4-aminobenzoate and 60g of anhydrous sodium carbonate were added, the temperature was raised to 60°C, and heated to reflux for 10h, after filtration, distillation under reduced pressure, filtration, and column purification, methyl vinylamino benzoate was obtained.

[0117] Methyl vinylamino benzoate and styrene were blended, and a certain amount of water was added, the mass ratio of methyl vinylamino benzoate and styrene was 10:2, then 1% benzoyl peroxide was added, a mixed solvent of xylene and heptane with a mass ratio of 1:10 was used as a porogen, the mass ratio of the reactants to the porogen was controlled to be 1:10, after stirring, the temperature was raised to 100°C, and a copolymerization reaction was carried out (9h), then distillation, washing, drying, and sieving were performed to obtain a methyl vinylamino benzoate-styrene copolymer, the repeating number of the methyl vinylamino benzoate repeating unit in the methyl vinylamino benzoate-styrene copolymer, and the styrene repeating unit was 55 and 20, respectively.

[0118] The above product was treated with a 10% sodium hydroxide solution for 24h, and then washed with 3 times the volume of deionized water for standby use. Aluminum chloride was dissolved in water to prepare a 10% mass fraction solution, the treated resin was added to the aluminum chloride solution, and after reacting for 4h, 3 times the volume of water was washed to obtain a fluorine-removed resin.

[0119] Performance detection

[0120] Take 10 g of the fluorine removal resin prepared in the above examples and comparative examples, and add 1000 mL of a fluorine-containing liquid (pH varies) with a fluorine ion concentration of 200 ppm, mix the liquids in a shaker for 1 h, filter after the end, test the fluorine ion concentration in the filtrate, calculate the fluorine ion removal rate, removal rate (%) = (fluorine ion concentration in the fluorine-containing liquid - fluorine ion concentration in the filtrate) / fluorine ion concentration in the fluorine-containing liquid, and the results are shown in Table 1.

[0121] Table 1 Performance test results

[0122]

[0123]

[0124] It can be seen that the fluorine removal resin provided by the comparative example has poor fluorine removal effect in alkaline environment, that is, the fluorine removal resin is not suitable for alkaline environment; the fluorine removal resin provided by the examples of the present application has excellent fluorine removal effect in acidic environment, neutral environment and alkaline environment, compared with the comparative example, the fluorine removal resin provided by the examples of the present application has the first unit, which can improve the fluorine removal ability of the fluorine removal resin in alkaline environment, and is more conducive to the use of the fluorine removal resin in different scenes. Compared with example 6, the third unit is provided in other examples, so that the fluorine removal effect of the fluorine removal resin in the acidic environment is further improved, which is more conducive to the use of the fluorine removal resin.

[0125] The above is the preferred embodiment of the present application, but it cannot be interpreted as limiting the scope of the present application. It should be noted that for ordinary skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, which are also considered to be within the scope of protection of the present application.

Claims

1. A fluorine-removing resin, characterized in that: The defluorination resin comprises a first unit and a second unit, wherein the structural formula of the first unit is , the structural formula of the second unit is , the repetition number of the first unit is an integer between 20 and 1000, and the repetition number of the second unit is an integer between 20 and 1000, Wherein, the R1 and the R2 are alkylene groups, the R3 is an alkylene group or a single bond, the R4 is an alkyl group or a hydrogen atom, the M1 is an aluminum salt group or a manganese salt group, and the M2 is an aluminum salt group or a manganese salt group.

2. The fluorine-removing resin according to claim 1, wherein The defluorination resin further comprises a third unit, the structural formula of which is , Wherein, the R5 is an alkylene group, and the M3 is an aluminum salt group or a manganese salt group.

3. The fluorine-removing resin according to claim 1, wherein The defluorination resin further comprises a fourth unit, the structural formula of which is , Wherein, the R6 is an alkylene group.

4. The fluorine-removing resin according to claim 1, wherein The defluorination resin has a porous structure, and the pore diameter of the defluorination resin is 100 nm-10 μm.

5. The fluorine-removing resin according to claim 1, wherein The saturated absorption capacity of the defluorination resin for fluoride ions is 0.1 mg / g-20 mg / g.

6. A method for preparing a fluorine-removing resin, characterized in that: include: mixing the first pretreated resin with an alkaline solution to obtain a second pretreated resin after a first reaction; At least one of an aluminum salt solution and a manganese salt solution is mixed with a second pretreated resin, and after a second reaction, the defluorination resin according to any one of claims 1 to 5 is obtained, wherein the first pretreated resin comprises a second unit and a fifth unit, and the structural formula of the fifth unit is , Wherein, the R7 and the R8 are alkyl groups.

7. The preparation method according to claim 6, wherein The first pretreatment resin further includes a sixth unit, the structural formula of which is , Wherein, the R5 is an alkylene group, and the R9 is an alkyl group.

8. The preparation method according to claim 6, wherein The mass concentration of the alkali solution is 1%-20%; The alkali solution includes at least one of a sodium hydroxide solution and a potassium hydroxide solution; The time of the first reaction is 3h-30h; The mass concentration of the aluminum salt solution is 1%-20%; The mass concentration of the manganese salt solution is 1%-20%; The second reaction time is 3h-8h; The temperature of the second reaction is 20°C-40°C.

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