A coating-type impregnation resin, its preparation method and application

Abstract

This invention discloses a coated impregnating resin, its preparation method, and its application. The method includes: using styrene, divinylbenzene, diisooctyl phosphate, and tributyl phosphate as raw materials, a polymerization reaction is carried out in the presence of an initiator, dispersant, surfactant, pore-forming agent, and solvent to obtain an extractable impregnating resin; the extractable impregnating resin is mixed with a polyvinyl alcohol solution, subjected to a first shaking, followed by the addition of potassium chloride solution, a second shaking, and filtration; the resulting resin is placed in a sulfuric acid solution, subjected to a third shaking, and filtered; the resulting resin undergoes a glutaraldehyde crosslinking reaction in a closed vapor crosslinking device. This invention utilizes the synergistic extraction effect of P2O4 and TBP to improve resin selectivity and increase adsorption capacity; glutaraldehyde vapor crosslinking of polyvinyl alcohol reduces extractant loss and increases circulating adsorption capacity; and selective adsorption of calcium and magnesium ions is achieved by controlling the pH of the high-nickel solution, thus controlling nickel loss.

Description

Technical Field

[0001] This invention relates to the field of high-nickel solution treatment technology, specifically to a coating-type impregnation resin, its preparation method, and its application. Background Technology

[0002] Nickel sulfate, a key raw material for lithium-ion batteries, requires a nickel content exceeding 22%, while other impurities must be reduced to extremely low levels. This ensures high battery performance and safety, and is crucial for improving battery energy density and cycle life. Industrially produced nickel salts contain various metallic and non-metallic impurities, which can severely affect the performance of battery materials and the overall battery performance. Therefore, nickel purification technology plays a critical role in ensuring the quality of battery-grade nickel sulfate. High-concentration nickel sulfate solutions, upon entering the evaporation equipment, are prone to scaling due to calcium and magnesium ions, affecting heat transfer efficiency and ultimately impacting the final product's quality.

[0003] In traditional calcium and magnesium ion removal processes, solvent extraction and fluoride precipitation are two common techniques. Among them:

[0004] Solvent extraction: This method uses P204 (diisooctyl phosphate) as the extractant to remove impurities such as Ca and Mn from the solution. Subsequently, the raffinate from P204 is further separated using P507 to obtain nickel and cobalt. This process ultimately produces battery-grade nickel sulfate and cobalt sulfate products. However, solvent extraction has some drawbacks in removing calcium and magnesium ions. It requires the use of multiple extractants in large quantities, leading to a longer process flow, increased production costs, and reduced product yield.

[0005] Fluoride precipitation method: This method utilizes the extremely low solubility of MgF2 and CaF2, removing calcium and magnesium ions from solution by adding fluoride precipitants. The main problem with fluoride precipitation for removing calcium and magnesium ions is that, to achieve effective removal, excessive fluoride is usually added. This not only increases the consumption of fluoride salts and raw material costs but may also cause some nickel, cobalt, manganese, and lithium to precipitate as fluorides, thus reducing the yield of these valuable metals. Furthermore, it introduces fluorine into the system, affecting product purity and causing equipment corrosion.

[0006] In view of this, a new material and process have been developed that can be applied to the removal of calcium and magnesium ions in high-nickel sulfate solutions. Summary of the Invention

[0007] Therefore, embodiments of the present invention provide a coated impregnation resin, its preparation method, and its application.

[0008] To achieve the above objectives, the embodiments of the present invention provide the following technical solutions:

[0009] According to a first aspect of the present invention, the present invention provides a method for preparing a coated impregnating resin, the method comprising the following steps:

[0010] (1) Using styrene, divinylbenzene, diisooctyl phosphate (P204) and tributyl phosphate (TBP) as raw materials, a polymerization reaction is carried out in the presence of an initiator, a dispersant, a surfactant, a pore-forming agent and a solvent to obtain an extract impregnation resin;

[0011] (2) The resin impregnated by extraction is mixed with polyvinyl alcohol solution, subjected to a first shaking, potassium chloride solution is added, subjected to a second shaking, filtered, the resulting resin is placed in sulfuric acid solution, subjected to a third shaking, filtered, and the resulting resin is subjected to glutaraldehyde crosslinking reaction in a closed steam crosslinking device to obtain the coated impregnated resin.

[0012] Further, in step (1), by weight, styrene is 70-90 parts, divinylbenzene is 75-95 parts, P204 is 40-50 parts, TBP is 15-35 parts, initiator is 0.1-50 parts, dispersant is 5-20 parts, surfactant is 40-70 parts, porogen is 90-120 parts and solvent is 800-1200 parts;

[0013] The polymerization process is as follows: a dispersant, surfactant, pore-forming agent and solvent are mixed to obtain an aqueous phase; styrene, divinylbenzene, diisooctyl phosphate and tributyl phosphate are mixed to obtain an oil phase; the aqueous phase and the oil phase are mixed to obtain a mixture; when the mixture is heated to 70~80℃, an initiator is added, the temperature is maintained for 1~2h, and then the temperature is raised to 90~95℃ to harden for 0.5~0.8h.

[0014] Furthermore, the initiator is selected from one or more of benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, and methyl ethyl ketone peroxide;

[0015] The dispersant is gelatin;

[0016] The surfactant is selected from one or more of liquid phosphate esters, fatty amines, tributylphosphine oxide, trioctylphosphine oxide, bis(2-ethylhexyl) phosphate, and sodium lignin naphthalene sulfonate;

[0017] The pore-forming agent is selected from one or more of polyvinyl acetate, polystyrene, polymethyl methacrylate, liquid paraffin, toluene, and cyclohexanone;

[0018] The solvent is deionized water.

[0019] Among them, liquid phosphate surfactants can be alkyl phosphates or fatty alcohol polyoxyethylene ether phosphates, and fatty amine surfactants can be primary amine salts, such as dodecyl primary amine salt; secondary amine salts, such as octadecyl secondary amine salt; and tertiary amine salts, such as hexadecyl tertiary amine salt.

[0020] Furthermore, the method further includes: performing solid-liquid separation on the product of the polymerization reaction, washing with deionized water until the effluent is clear, and then washing with sulfuric acid solution with pH 1-2 until the pH of the effluent is 3-4.

[0021] Further, in step (2), the mass concentration of the polyvinyl alcohol solution is 3~5%, the mass-volume ratio of the extracting impregnation resin to the polyvinyl alcohol solution is 1.0~10.0 g: 20~30 mL, and the conditions for the first shaking are: 25~35℃, 20~30 min;

[0022] The concentration of the potassium chloride solution is 1~5 mol / L, the mass-to-volume ratio of the extracting and impregnating resin to the potassium chloride solution is 1.0~5.0 g: 4~5 mL, and the conditions for the second shaking are: 25~35℃, 15~30 min;

[0023] The sulfuric acid solution has a mass concentration of 0.5-2%, the mass-to-volume ratio of the extracting and impregnating resin to the sulfuric acid solution is 1.0-5.0 g: 8-10 mL, and the conditions for the third shaking are: 25-35℃, 20-30 min;

[0024] The conditions for the glutaraldehyde crosslinking reaction are: temperature 70~90℃, time 40~90min.

[0025] According to a second aspect of the present invention, the present invention provides a coating impregnation resin, which is prepared by the preparation method described in any of the preceding claims.

[0026] According to a third aspect of the present invention, the present invention provides the use of the coated impregnation resin as described above in the removal of calcium and magnesium ions from high-nickel solutions.

[0027] According to a fourth aspect of the present invention, the present invention provides a method for removing calcium and magnesium ions from a high-nickel solution, the method comprising:

[0028] The pH of the feed solution is adjusted to 5-6 using dilute sulfuric acid or dilute sodium hydroxide solution, and then it flows through an exchange column filled with the coated impregnated resin as described above; or,

[0029] The pH of the feed solution is adjusted to 3-4 using dilute sulfuric acid or dilute sodium hydroxide solution, and then it flows through an exchange column filled with the coated impregnated resin as described above.

[0030] In some specific embodiments, the mass concentration of dilute sulfuric acid is 1-2%, and the mass concentration of dilute sodium hydroxide solution is 2-4%.

[0031] Furthermore, the method also includes: using 1~2 mol / L hydrochloric acid to desorb and regenerate the resin adsorbed with calcium or magnesium ions.

[0032] This invention provides a coating-type impregnation resin, the preparation principle of which is as follows:

[0033] PVA-OH + GA→PVA-O-CH2-CH2-O-PVA

[0034] Polyvinyl alcohol (PVA) molecules contain numerous hydroxyl groups (-OH). Under sulfuric acid catalysis, these hydroxyl groups (-OH) on the PVA molecular chain can react with the aldehyde group (-CHO) of glutaraldehyde (GA) to form an unstable Schiff base intermediate. This Schiff base intermediate further reacts with the hydroxyl group of another PVA molecule to form a stable cross-linked structure. As the reaction proceeds, PVA molecular chains are linked by cross-linking bonds formed with GA, increasing the degree of polymerization and cross-linking, resulting in a three-dimensional network structure. Glutaraldehyde vapor reacts with the cross-linked network structure formed by the PVA film on the resin surface. Under these conditions, the resulting coated impregnated resin effectively reduces the loss of extractants (such as diisooctyl phosphate and tributyl phosphate), thereby improving the removal efficiency of calcium and magnesium ions in high-nickel solutions.

[0035] Instructions for use of the coating-type impregnation resin of this invention: Because under neutral or slightly acidic conditions, magnesium ions will react as Mg(OH)₂. + The nickel sulfate solution exists in a form that readily forms a complex with P2O4. P2O4 selectively extracts calcium ions between pH 3 and 4. Therefore, the feed solution needs to be adjusted to the corresponding pH during use. The resin is packed into a glass exchange column. The high-concentration nickel sulfate solution is adjusted to pH 5-6 using dilute sulfuric acid or dilute sodium hydroxide solution. The nickel sulfate solution containing calcium and magnesium impurities is then passed through the exchange column at a rate of 2 BV / h, allowing the resin to adsorb magnesium ions from the solution. When the magnesium content in the effluent exceeds 5 mg / L, the feeding into the exchange column is stopped. The magnesium-removed nickel sulfate solution is then adjusted to pH 3-4 using dilute sulfuric acid. The pH-adjusted nickel sulfate solution is then passed through the exchange column at a rate of 2 BV / h. When the calcium content in the effluent exceeds 5 mg / L, the operation is stopped. For desorption, 1-2 mol / L hydrochloric acid is passed through the exchange column at a rate of 5 BV / h to desorb calcium and magnesium from the resin.

[0036] The embodiments of the present invention have the following advantages:

[0037] 1. This invention combines the advantages of solvent extraction and ion exchange, utilizing the synergistic extraction effect of P204 and TBP to improve resin selectivity and increase adsorption capacity.

[0038] 2. Prepared by crosslinking polyvinyl alcohol (PVA) with glutaraldehyde vapor, used to reduce extractant loss and improve circulating adsorption capacity.

[0039] 3. By controlling the pH of the high-nickel solution, selective adsorption of calcium and magnesium ions can be achieved, thereby controlling nickel loss. Attached Figure Description

[0040] To more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely exemplary, and those skilled in the art can derive other embodiments based on the provided drawings without creative effort.

[0041] Figure 1 The magnesium adsorption capacity provided by this invention varies with the number of cycles;

[0042] Figure 2 The calcium adsorption capacity provided by this invention varies with the number of cycles. Detailed Implementation

[0043] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0044] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field, or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels.

[0045] Preparation of polyvinyl alcohol solution: Weigh a certain amount of polyvinyl alcohol powder and add it to a beaker containing deionized water to prepare a polyvinyl alcohol (molecular weight of 20,000 to 150,000) solution with a mass concentration of 3-5%. Then place the beaker in a water bath at 70-90°C or higher and heat and stir until the powder is completely dissolved. Allow it to cool naturally to room temperature and store for later use.

[0046] Example 1

[0047] This embodiment provides a coating-type impregnation resin, the preparation method of which includes the following steps:

[0048] (1) 1 L of deionized water, add 10 g of gelatin, 100 g of toluene and 50 g of tributylphosphine oxide and stir in a 60℃ water bath for 30 min to obtain an aqueous phase; mix 80 g of styrene, 80 g of divinylbenzene and 50 g of P2O4 and 25 g of TBP evenly and add to the aqueous phase to obtain a mixed solution; heat the mixed solution to 80℃ and add 0.5 g of benzoyl peroxide (BPO), keep warm for 1 h, then heat to 90℃ and harden for 0.5 h, filter, wash with deionized water until the effluent is clear, then wash with sulfuric acid solution with pH 2 until the pH of the effluent is 4, air dry for 12 h to obtain 10 g of extracting impregnation resin.

[0049] (2) Weigh 2g of the extracted impregnating resin and add it to 20 mL of a 3% polyvinyl alcohol solution. Shake at a constant temperature (25℃) for 30 min. Add 5 mL of a 1 mol / L potassium chloride solution and continue shaking for 20 min. Filter the solution. Then, suspend the resin in 10 mL of a 1% sulfuric acid solution and shake for 20 min. After filtration, place the resin particles on the filter screen of a steam crosslinking device and spread them evenly. Add glutaraldehyde (GA) solution to the bottom of the device. Then, place the device in an oil bath and heat it at 70℃. The glutaraldehyde vapor volatilizes and reacts with the polyvinyl alcohol film on the surface of the resin particles under acid catalysis. After the crosslinking reaction for 40 min, remove the resin, wash it with deionized water, and dry it in a 50℃ electric thermostatic drying oven for 8 h to obtain the coated impregnating resin.

[0050] Example 2

[0051] This embodiment provides a coating-type impregnation resin, the preparation method of which includes the following steps:

[0052] (1) 1 L of deionized water was mixed with 10 g of gelatin, 90 g of polystyrene and 50 g of tributylphosphine oxide in a 60 °C water bath for 30 min to obtain an aqueous phase; 75 g of styrene, 95 g of divinylbenzene and 50 g of P2O4 and 25 g of TBP were mixed evenly and added to the aqueous phase to obtain a mixed solution; after the mixed solution was heated to 80 °C, 0.6 g of dicumyl peroxide (DCP) was added, and the solution was kept at 80 °C for 1 h, and then heated to 90 °C for 0.5 h to harden. The solution was filtered, washed with deionized water until the effluent was clear, and then washed with sulfuric acid solution with pH 2 until the pH of the effluent was 4. The solution was air-dried for 12 h to obtain 9 g of extracting impregnation resin.

[0053] (2) Weigh 3g of the extracted impregnating resin and add it to 20 mL of a 4% polyvinyl alcohol solution. Shake at a constant temperature (30℃) for 20 min. Add 4 mL of a 1 mol / L potassium chloride solution and continue shaking for 15 min. Filter the solution. Then, suspend the resin in 10 mL of a 1% sulfuric acid solution and shake for 25 min. After filtration, place the resin particles on the filter screen of a steam crosslinking device and spread them evenly. Add glutaraldehyde (GA) solution to the bottom of the device. Then, place the device in an oil bath and heat it at 80℃. The glutaraldehyde vapor volatilizes and reacts with the polyvinyl alcohol film on the surface of the resin particles under acid catalysis. After 60 min of crosslinking reaction, remove the resin, wash it with deionized water, and dry it in a 40℃ electric thermostatic drying oven for 8 h to obtain the coated impregnating resin.

[0054] Example 3

[0055] This embodiment provides a coating-type impregnation resin, the preparation method of which includes the following steps:

[0056] (1) 1 L of deionized water, 10 g of gelatin, 110 g of liquid paraffin and 45 g of sodium lignin naphthalene sulfonate were added and stirred in a 55°C water bath for 35 min to obtain an aqueous phase; 85 g of styrene, 85 g of divinylbenzene and 50 g of P2O4 and 25 g of TBP were mixed evenly and added to the aqueous phase to obtain a mixed solution; after the mixed solution was heated to 80°C, 0.5 g of methyl ethyl ketone peroxide (MEKP) was added, and the solution was kept at the temperature for 1 h, and then heated to 90°C to harden for 0.5 h. The solution was washed with deionized water until the effluent was clear, and then washed with sulfuric acid solution with pH 1 until the pH of the effluent was 3. The solution was then filtered and air-dried for 12 h to obtain 9 g of extracting impregnation resin.

[0057] (2) Weigh 2g of the extracted impregnating resin and add it to 20 mL of a 5% polyvinyl alcohol solution. Shake at a constant temperature (25℃) for 30 min. Add 4 mL of a 1 mol / L potassium chloride solution and continue shaking for 30 min. Filter the solution. Then, suspend the resin in 10 mL of a 1.5% sulfuric acid solution and shake for 20 min. After filtration, place the resin particles on the filter screen of a steam crosslinking device and spread them evenly. Add glutaraldehyde (GA) solution to the bottom of the device. Then, place the device in an oil bath and heat it at 90℃. The glutaraldehyde vapor volatilizes and reacts with the polyvinyl alcohol film on the surface of the resin particles under acid catalysis. After the crosslinking reaction for 60 min, remove the resin, wash it with deionized water, and dry it in a 50℃ electric thermostatic drying oven for 10 h to obtain the coated impregnating resin.

[0058] Comparative Example 1

[0059] This comparative example provides a coating-type impregnation resin, which differs from Example 1 in that it does not use TBP. That is, the preparation method of this comparative example includes the following steps:

[0060] (1) 1 L of deionized water, add 10 g of gelatin, 100 g of toluene and 50 g of tributylphosphine oxide and stir in a 60℃ water bath for 30 min to obtain an aqueous phase; mix 80 g of styrene, 80 g of divinylbenzene and 50 g of P2O4 evenly and add to the aqueous phase to obtain a mixed solution; heat the mixed solution to 80℃ and add 0.5 g of benzoyl peroxide (BPO), keep it at the temperature for 1 h, then heat it to 90℃ to harden for 0.5 h, filter, wash with deionized water until the effluent is clear, then wash with sulfuric acid solution with pH 2 until the pH of the effluent is 4, and air dry for 12 h.

[0061] (2) Same as Example 1.

[0062] Comparative Example 2

[0063] This comparative example provides a coating-type impregnation resin, which differs from Example 1 in that it does not use P204. That is, the preparation method of this comparative example includes the following steps:

[0064] (1) 1 L of deionized water, add 10 g of gelatin, 100 g of toluene and 50 g of tributylphosphine oxide and stir in a 60℃ water bath for 30 min to obtain an aqueous phase; mix 80 g of styrene, 80 g of divinylbenzene and 25 g of TBP evenly and add to the aqueous phase to obtain a mixed solution; heat the mixed solution to 80℃ and add 0.5 g of benzoyl peroxide (BPO), keep it at the temperature for 1 h, then heat it to 90℃ and harden for 0.5 h, filter, wash with deionized water until the effluent is clear, then wash with sulfuric acid solution with pH 2 until the pH of the effluent is 4, and air dry for 12 h.

[0065] (2) Same as Example 1.

[0066] Comparative Example 3

[0067] This comparative example provides a resin that differs from Example 1 only in that step (2) is omitted. The preparation method of this comparative example is as follows:

[0068] 1 L of deionized water was mixed with 10 g of gelatin, 100 g of toluene, and 50 g of tributylphosphine oxide in a 60°C water bath for 30 min to obtain an aqueous phase. 80 g of styrene, 80 g of divinylbenzene, 50 g of P2O4, and 25 g of TBP were mixed thoroughly and added to the aqueous phase to obtain a mixed solution. The mixed solution was heated to 80°C and 0.5 g of benzoyl peroxide (BPO) was added. After holding at this temperature for 1 h, the temperature was raised to 90°C and hardened for 0.5 h. The solution was then filtered, washed with deionized water until the effluent was clear, and then washed with a sulfuric acid solution with a pH of 2 until the pH of the effluent was 4. The solution was then air-dried for 12 h.

[0069] Test Example 1

[0070] A waste battery recycling company produces nickel sulfate using a wet process. The nickel concentration in the process reaches 10 g / L, the calcium and magnesium concentrations are 54 ppm and 40 ppm respectively, and the pH of the solution is 5-6.

[0071] (1) Static adsorption test for magnesium removal:

[0072] Take 100 ml of nickel sulfate solution into a plastic vial, add a small amount of resin at a solid-liquid ratio of 1 g / L, shake at 240 r / min for 4 h, and then take a sample for analysis. Use inductively coupled plasma spectrometry to detect the concentration changes of nickel and magnesium in the solution, calculate the loss rate of nickel and the adsorption capacity of magnesium, and the results are shown in Table 1 below.

[0073] Table 1. Static adsorption results

[0074]

[0075] The used resin was washed with deionized water, then regenerated by desorption using 1 mol / L hydrochloric acid solution at a solid-liquid ratio of 100 g / L. After shaking at 200 rpm for 2 hours, solid-liquid separation was achieved, followed by rinsing with deionized water, and then the next round of adsorption was performed. After five rounds of adsorption, the change in resin adsorption capacity was calculated. The results are shown below. Figure 1 .

[0076] The results showed that after 5 cycles, the magnesium adsorption capacity of the resin in Example 1 decreased from 3.88 mg / g to 3.83 mg / g, with only a small decrease in adsorption capacity.

[0077] (2) Static adsorption test for calcium removal:

[0078] The pH of nickel sulfate was adjusted to between 3 and 4 using dilute sulfuric acid. Then, 100 ml of nickel sulfate solution was placed in a plastic vial. A small amount of resin was added at a solid-liquid ratio of 10 g / L. After shaking at 240 r / min for 4 h, samples were taken for analysis. The concentration changes of nickel and calcium in the solution were detected using inductively coupled plasma spectrometry. The loss rate of nickel, the removal effect of calcium, and the adsorption capacity of calcium were calculated. The results are shown in Table 2 below.

[0079] Table 2. Static adsorption results

[0080]

[0081] The used resin was washed with deionized water, then regenerated by desorption using 1 mol / L hydrochloric acid solution at a solid-liquid ratio of 100 g / L. After shaking at 200 rpm for 2 hours, solid-liquid separation was achieved, followed by rinsing with deionized water, and then the next round of adsorption was performed. After five rounds of adsorption, the change in resin adsorption capacity was calculated. The results are shown below. Figure 2 .

[0082] The results showed that after 5 cycles, the calcium adsorption capacity of the resin in Example 1 decreased from 5.16 mg / g to 4.89 mg / g, with only a small decrease in adsorption capacity.

[0083] Although the present invention has been described in detail above with general descriptions and specific embodiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a coating-type impregnating resin, characterized in that, The method includes the following steps: (1) Using styrene, divinylbenzene, diisooctyl phosphate and tributyl phosphate as raw materials, a polymerization reaction is carried out in the presence of an initiator, a dispersant, a surfactant, a pore-forming agent and a solvent to obtain an extract impregnation resin; (2) The resin impregnated by extraction is mixed with polyvinyl alcohol solution, subjected to a first shaking, potassium chloride solution is added, subjected to a second shaking, filtered, the resulting resin is placed in sulfuric acid solution, subjected to a third shaking, filtered, and the resulting resin is subjected to glutaraldehyde crosslinking reaction in a closed steam crosslinking device to obtain the coated impregnated resin.

2. The method for preparing the coated impregnating resin according to claim 1, characterized in that, In step (1), By weight, styrene comprises 70-90 parts, divinylbenzene 75-95 parts, diisooctyl phosphate 40-50 parts, tributyl phosphate 15-35 parts, initiator 0.1-50 parts, dispersant 5-20 parts, surfactant 40-70 parts, porogen 90-120 parts, and solvent 800-1200 parts; The polymerization process is as follows: a dispersant, surfactant, pore-forming agent and solvent are mixed to obtain an aqueous phase; styrene, divinylbenzene, diisooctyl phosphate and tributyl phosphate are mixed to obtain an oil phase; the aqueous phase and the oil phase are mixed to obtain a mixture; when the mixture is heated to 70~80℃, an initiator is added, the temperature is maintained for 1~2h, and then the temperature is raised to 90~95℃ to harden for 0.5~0.8h.

3. The method for preparing the coated impregnating resin according to claim 1, characterized in that, The initiator is selected from one or more of benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, and methyl ethyl ketone peroxide; The dispersant is gelatin; The surfactant is selected from one or more of liquid phosphate esters, fatty amines, tributylphosphine oxide, trioctylphosphine oxide, bis(2-ethylhexyl) phosphate, and sodium lignin naphthalene sulfonate; The pore-forming agent is selected from one or more of polyvinyl acetate, polystyrene, polymethyl methacrylate, liquid paraffin, toluene, and cyclohexanone; The solvent is deionized water.

4. The method for preparing the coated impregnating resin according to claim 1, characterized in that, The method further includes: performing solid-liquid separation on the product of the polymerization reaction, washing with deionized water until the effluent is clear, and then washing with sulfuric acid solution with pH 1-2 until the pH of the effluent is 3-4.

5. The method for preparing the coated impregnating resin according to claim 1, characterized in that, In step (2), The polyvinyl alcohol solution has a mass concentration of 3-5%, and the mass-to-volume ratio of the extracting and impregnating resin to the polyvinyl alcohol solution is 1.0-10.0 g: 20-30 mL. The conditions for the first shaking are: 25-35℃, 20-30 min. The concentration of the potassium chloride solution is 1~5 mol / L, the mass-to-volume ratio of the extracting and impregnating resin to the potassium chloride solution is 1.0~5.0 g: 4~5 mL, and the conditions for the second shaking are: 25~35℃, 15~30 min; The sulfuric acid solution has a mass concentration of 0.5-2%, the mass-to-volume ratio of the extracting and impregnating resin to the sulfuric acid solution is 1.0-5.0 g: 8-10 mL, and the conditions for the third shaking are: 25-35℃, 20-30 min; The conditions for the glutaraldehyde crosslinking reaction are: temperature 70~90℃, time 40~90min.

6. A coating-type impregnation resin, characterized in that, It is prepared by any one of claims 1-5.

7. The use of the coating-type impregnation resin according to claim 6 in removing calcium and magnesium ions from high-nickel solutions.

8. A method for removing calcium and magnesium ions from a high-nickel solution, characterized in that, The method includes: The pH of the feed solution is adjusted to 5-6 using dilute sulfuric acid or dilute sodium hydroxide solution, and then flows through an exchange column filled with the coated impregnated resin as described in claim 6; or, The pH of the feed solution is adjusted to 3-4 using dilute sulfuric acid or dilute sodium hydroxide solution, and then flows through an exchange column filled with the coated impregnated resin as described in claim 6.

9. The method for removing calcium and magnesium ions from a high-nickel solution according to claim 8, characterized in that, The method further includes: using 1~2 mol / L hydrochloric acid to desorb and regenerate the resin adsorbed with calcium or magnesium ions.

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