CN111686700A - Iron ion adsorption resin, preparation method and application in removing iron ions in solution - Google Patents

Abstract

The invention discloses an iron ion adsorption resin, a preparation method thereof and application thereof in removing iron ions in a solution. The invention firstly uses suspension polymerization to prepare styrene skeleton resin, and then uses the processes of chlorination, phosphorylation and sulfonation to prepare sulfonic acid resin with different phosphoric acid structures. The sulfonic acid resin prepared by the invention has stronger binding capacity to iron, has the advantages of high iron ion removal precision, complete analysis and the like, and can be used in a complex environment.

Description

Iron ion adsorption resin, preparation method and application of iron ion removal in solution

technical field

The invention belongs to the field of preparation and application of functional polymer materials, and relates to a method for preparing an iron ion adsorption resin and a method for removing iron ions in a solution.

Background technique

As one of the most abundant elements in the earth's crust, iron often exists in a large amount in various solution systems, such as coexisting with other non-ferrous metals in the ore body, which reduces the quality of non-ferrous metals. If it exists in the hydrometallurgical solution of nickel, cobalt, manganese, lithium, zinc, etc., it becomes a key impurity. If it is not removed, it will contaminate the target metal and cause difficulties in subsequent use. In addition, during the preparation of high-purity organic solvents such as electronic-grade reagents, they are often contaminated by iron ions, resulting in insufficient reagent purity.

Therefore, the removal of iron impurities is a necessary process step for the production of high-purity products.

There are many iron removal processes, and the patent CN 104451145A proposes a method for extracting iron from a chloride mixed solution. The extractant used in this method is N,N-bis(2-ethylhexyl)acetamide, which is a neutral extractant. Iron needs to be extracted in concentrated acid, and the hydrogen ion concentration is required to be higher than 2mol/L , suitable for the removal of iron in high chlorine content environment, but the extraction performance of sulfuric acid system or low chlorine and low acid system is not good, so its application range is greatly limited. Patent CN105016368A adopts strong base anion exchange resin to remove iron in solution containing aluminum chloride. The resin is suitable for removing iron in chlorination system, and also suitable for removing iron in concentrated hydrochloric acid solution, which requires high concentration of chloride salt solution. Iron ions are removed from the ferric chloride, and then water is used for desorption to obtain a desorption solution containing ferric chloride. But this method is not suitable for the removal of iron in sulfuric acid system.

Patent CN109133153A describes using an organic complexing agent such as sodium formate or tetrasodium iminodisuccinate and iron to precipitate after complexation, then extract with an extractant, and separate the organic complexing agent and iron after stripping to achieve iron removal. function. Although this method can remove iron, both precipitation and extraction are required in the process, and organic impurities are easily introduced into the solution, which affects post-processing or product purity. Patent CN102992387B uses metastannic acid as a precipitant, and the method of ferric precipitation can reduce iron ions to about 5ppm. This process uses stannic acid, which will introduce impurities and has a narrow scope of application. The patent CN106636651B adopts the iron-aluminum phosphate composite precipitation method mainly composed of aluminum phosphate, but the process needs to adjust the pH of the solution, and the introduction of phosphate has an impact on the process.

Patent CN 106636638 B carries out deep removal of iron in cobalt solution, adopts chelating resin as Monophos, removes iron from feed liquid through ion-exchange resin, and then feeds it into an electrowinning tank for electrowinning and purification to obtain 99.999% iron content less than 1ppm. % of high-purity cobalt products. Patent CN 102676814 B describes a method for removing trace amounts of iron from a strongly acidic nickel sulfate solution, and the method adopts a sulfonic acid-based phosphoric acid chelating resin to obtain a high-purity nickel sulfate solution. Both patents mention chelating resins and describe good results for iron removal.

SUMMARY OF THE INVENTION

The present invention aims to disclose a method for removing iron in a metal solution, and specifically adopts a resin adsorption method to remove iron in the solution.

In order to achieve the effect of removing iron in the solution, the resin used in the present invention is a styrene skeleton, and a phosphoric acid group and a sulfonic acid group are grafted to achieve a better iron removal effect. Its structure is:

wherein R is (CH ₂ ) _n , n=0, 1, 2, 3 . . .

The resin uses divinylbenzene as a cross-linking agent, and the structure is:

The preparation steps of this resin are:

(1) prepare oil phase and water phase respectively, adopt suspension polymerization mode to prepare resin-based balls by copolymerizing divinylbenzene and styrene;

(2) The resin-based ball is phosphorylated with phosphorylation reagents such as phosphorus trichloride, phosphorus pentachloride, phosphorous acid, etc. in the presence of aluminum trichloride, ferric chloride or zinc chloride, or halogenated first, then Phosphorylated resin intermediates are prepared by phosphorylation;

(3) Phosphorylated resin intermediates are sulfonated and washed to obtain iron ion adsorption resin.

More specifically, the resin-based ball can be directly phosphorylated with phosphorylation reagents such as phosphorous trichloride, phosphorous pentachloride, phosphorous acid and the like in the presence of aluminum trichloride, ferric chloride or zinc chloride without modification. , so that the phosphate functional group can be directly connected to the benzene ring.

The resin-based spheres can also be prepared as a phosphorylated resin intermediate by a halogenation reaction followed by a phosphorylation reaction. There are three ways of halogenation reaction: one is to use chlorosulfonic acid, paraformaldehyde and the obtained resin-based balls of the preparation step (1) to carry out chloromethylation reaction to obtain the chlorine balls; the other is to use halogenated alkyl alcohols for the resin-based balls, Such as 2-bromoethanol, 3-bromopropanol, etc., under the catalysis of anhydrous aluminum chloride, ferric chloride or zinc chloride, carry out Friedel-Crafts reaction grafting to obtain halogenated resin; thirdly, through Friedel-Crafts reaction, resin-based ball The halogenated alkane can be grafted by reacting with 1,2-dihaloethane, 1,3-dihalopropane, 1,4-dihalobutane or 1,5-dihalopentane to obtain a halogenated resin. Chlorine balls or halogenated resins are then reacted with phosphate compounds such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, or tributyl phosphite to obtain phosphorylation. resin intermediate.

In the preparation of the resin, the amount of the sulfonic acid group can be adjusted by adjusting the degree of phosphorylation. When the phosphoric acid group and the sulfonic acid group reach a certain ratio, the ability to bind iron ions will be enhanced.

After the phosphorylated resin intermediate is prepared, the difference between the sulfonation reaction process and the sulfonation reaction process for preparing common cation resin is that it needs to be carried out under stronger sulfonation conditions, such as using a high-concentration sulfuric acid solution, and the mass percentage concentration reaches At the same time, the sulfonation temperature is required to be higher, and the temperature needs to be raised to more than 140 ° C; chlorosulfonic acid can also be used as the raw material for sulfonation. And the sulfonation reaction process of preparing common cation resin can use sulfuric acid whose mass percentage concentration is more than 83%, because its sulfonation is the terminal position which is relatively easy to react on the benzene ring.

The sulfonated resin intermediate is washed with water step by step to obtain the iron ion adsorption resin product.

This product can be used for the removal of trace iron ions in solutions such as high concentration sulfuric acid, copper sulfate, nickel sulfate, cobalt sulfate, and zinc sulfate. This product is mainly used to purify high-concentration valuable metal solutions, and can remove iron pollution in high-purity chemical reagents; this product can also be used for the recovery of rare earth elements and the removal of iron in the recovery of lithium iron phosphate batteries.

The specific use method of the product is: flow the solution containing iron ions through the resin column containing the product at a flow rate of 0.1-20BV/h, after a period of adsorption, the resin reaches a saturated state, and the resin has a saturated adsorption capacity for iron ions. The resin can be regenerated at 2-30g/L; before regeneration, the resin is washed with water, and the valuable metal solution in the resin pores is washed to the original solution to recover the valuable metal; after washing, use at least 6mol/L hydrochloric acid solution Or use 0.1～100g/L EDTA solution to regenerate the resin, the regeneration flow rate can be controlled at 1～10BV/h, the total regeneration amount is 10BV, after regeneration, the resin can be used again after washing with 5BV water.

Described iron-containing solution can be sulfuric acid solution containing iron ion, nickel sulfate solution, copper sulfate solution, zinc sulfate solution, cobalt sulfate solution and other sulfuric acid and sulfate solution, also can be used for phosphoric acid solution containing iron ion and its salt. Solutions, such as zinc phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, can also be used for organic acids containing iron ions and organic acid aqueous solutions such as acetic acid solution, citric acid solution, malic acid solution, succinic acid solution , Adipic acid solution, etc.

This product has a good adsorption and chelation effect on ferric ions, and its regeneration needs to use a regenerating agent with stronger chelating ability with ferric ions, such as hydrochloric acid, which can form [FeCl ₄ ]-complex anion with ferric ions ^, Thereby destroying the chelate bond formed between the resin and the iron ion, and playing the role of regenerating and restoring the adsorption capacity of the resin; similar to sodium EDTA solution, potassium thiocyanate solution, hydrofluoric acid, hydrocyanic acid, Compounds such as thiocyanic acid can be used as regenerants.

The present invention has the following beneficial effects:

It has high adsorption selectivity for iron ions, and can enrich iron ions with a concentration of less than 50mg/L in high nickel solution to about 20g/L, with good removal ability; at the same time, it is easy to analyze, and the adsorbed iron ions are almost All can be parsed. To sum up, the iron ion adsorption resin prepared by the patent of the present invention has a good application effect, can remove and enrich the iron ions in the solution, and can be reused.

Detailed ways

Examples 1-5:

Different amounts of cross-linking agents are used to prepare different resin-based balls. The specific cross-linking doses are:

63%DVB/g 80%DVB/g Example 1 40 Example 2 55 Example 3 90 Example 4 85 Example 5 150

Other components of the oil phase: styrene: 740g, liquid paraffin: 320g, 200# gasoline: 165g, BPO: 9g, mix the above materials evenly for use;

Aqueous phase: tap water: 2500g, gelatin: 30g; add water to a 5000L three-necked flask, start stirring, heat up to 45°C, add gelatin, and keep at 45°C for 1 h to dissolve the gelatin;

Stop stirring, slowly pour the mixed oil phase into the three-necked flask, let it stand for 10 minutes, and replace the air in the upper space of the flask with nitrogen; turn on the stirring and adjust the stirring speed to make the particle size of the oil droplets between 0.3 and 0.8 mm. Begin to heat up, heat up to 70 °C for 2 hours, hold for 2 hours, then continue to heat up to 80 °C for 3 hours, and heat up to 95 °C for 8 hours; filter out spherical beads, wash with water, and wash with ethanol to obtain resin-based balls.

Put the above resin-based balls into an oven and dry at 80°C until the water content is lower than 0.5%, weigh 100 g and put it into a three-necked flask, add 50 g of ethylene dichloride, 28 g of paraformaldehyde, and 109 g of chlorosulfonic acid, turn on stirring, and control The reaction temperature is 40～50 ℃ for 8h, after the reaction, the solid base spheres are filtered out, washed with ethanol, and washed with water to obtain chloromethylated resin chlorine spheres for later use;

Weigh 100 g of the above resin chlorine balls, put it into a three-necked flask, add 500 ml of triethyl phosphite, heat up to 130 ° C and finish the reaction for 20 h. After cooling, filter out the resin, wash with ethanol, wash with water and dry until the water content is lower than 0.5%. That is, the phosphorylated resin intermediate is obtained;

Weigh 50g of the phosphorylated resin intermediate after drying, put it into the reaction kettle, add 50g of dichloroethane, soak for 30min, then add 300ml of 98% sulfuric acid, heat up to 80°C for 2h, react for 1h, and heat up to 100°C for 2h The reaction was carried out for 10 hours. After the reaction, the sulfuric acid was gradually diluted. Finally, the resin was washed with a large amount of water, and the final product was obtained after filtration.

Examples 6-10:

The resin-based balls were prepared by the method of Example 2; the resin-based balls were placed in an oven and dried at 80° C. until the water content was below 0.5%; 100 g of the dried resin-based balls were weighed and put into the dried In the three-necked flask, 100 g of aluminum trichloride was added, the substances in the following table were added, and the mixture was stirred and swollen for 120 min.

Chloroethanol 3-Chloropropanol 1-Chloro-2-propanol 4-Chlorobutanol 5-Chloropentanol Example 6 150 Example 7 200 Example 8 260 Example 9 320 Example 10 400

The temperature is raised to 60°C for 10 hours, and the resin is filtered out, washed with ethanol, and washed with water to obtain a hydroxylated resin intermediate, which is dried in an oven at 80°C until the water content is less than 0.5% for later use;

Weigh 100 g of the dried hydroxylated resin intermediate, put it into a dry three-necked flask, add 100 g of dichloroethane, 200 g of phosphorus pentachloride, 200 g of phosphorous acid, heat up to reflux for 24 hours, filter out the resin, and wash with ethanol , after washing with water, a phosphorylated resin intermediate is obtained, which is dried in an oven at 80° C. until the water content is less than 0.5% for subsequent use;

Weigh 50g of the phosphorylated resin intermediate after drying, put it into the reaction kettle, add 50g of dichloroethane, soak for 30min, then add 300ml of 98% sulfuric acid, heat up to 80°C for 2h, react for 1h, and heat up to 100°C for 2h The reaction was carried out for 10 hours. After the reaction, the sulfuric acid was gradually diluted. Finally, the resin was washed with a large amount of water, and the final product was obtained after filtration.

Examples 11-15:

The resin-based balls were prepared by the method of Example 2; the resin-based balls were placed in an oven and dried at 80° C. until the water content was below 0.5%; 100 g of the dried resin-based balls were weighed and put into the dried In the three-necked flask, add 400 g of phosphorous acid and 50 g of aluminum trichloride, respectively add the substances listed in the following table, and stir and swell for 120 min:

Phosphorus Trichloride Phosphorus pentachloride Example 11 100 Example 12 200 Example 13 300 Example 14 400 Example 15 500

After the temperature is raised to 75°C for 10 hours, the resin is filtered out, washed with ethanol, and washed with water to obtain a phosphorylated resin intermediate, which is dried in an oven at 80°C until the water content is less than 0.5% for later use;

Weigh 50g of the phosphorylated resin intermediate after drying, put it into the reaction kettle, add 50g of dichloroethane, soak for 30min, then add 300ml of 98% sulfuric acid, heat up to 80°C for 2h, react for 1h, and heat up to 100°C for 2h The reaction was carried out for 10 hours. After the reaction, the sulfuric acid was gradually diluted. Finally, the resin was washed with a large amount of water, and the final product was obtained after filtration.

Examples 16-19:

The resin-based balls were prepared by the method of Example 2; the resin-based balls were placed in an oven and dried at 80° C. until the water content was below 0.5%; 100 g of the dried resin-based balls were weighed and put into the dried In the three-necked flask, add 50g of aluminum trichloride, then add the following substances according to the table below, stir and swell for 120min,

The temperature was raised to 75°C for 10 hours, and the resin was filtered out, washed with ethanol, and washed with water to obtain chlorinated resin chlorine balls, which were dried in an oven at 80°C until the water content was less than 0.5% for later use;

Weigh 100 g of the above resin chlorine ball, put it into a three-necked flask, add 500 ml of tributyl phosphate, heat up to 130 ° C and finish the reaction for 20 h. Obtain phosphorylated resin intermediate;

Weigh 50g of the phosphorylated resin intermediate after drying, put it into the reaction kettle, add 50g of dichloroethane, soak for 30min, then add 300ml of 98% sulfuric acid, heat up to 80°C for 2h, react for 1h, and heat up to 100°C for 2h The reaction was carried out for 10h, the sulfuric acid was gradually diluted after the reaction, and finally the resin was washed with a large amount of water, and the final product was obtained after filtration;

The properties of the resins prepared by the above examples were evaluated with a nickel sulfate solution, wherein the nickel ion content was 100 g/L and the iron ion content was 50 mg/L. The iron ion adsorption resin was loaded into the exchange column, and the iron-containing solution flowed through the resin column at a flow rate of 5BV/h, and the outlet iron ion concentration was measured; when the outlet iron ion concentration reached more than 1 mg/L, the adsorption was stopped, the treatment volume was recorded, and Calculate the adsorption capacity of the resin; then use 6mol/L hydrochloric acid solution 10BV to regenerate the resin, test the iron content in the regeneration solution, and calculate the resolution rate; the specific data are as follows:

The performance evaluation shows that the iron ion adsorption resins prepared by the above methods have high adsorption selectivity for iron, and can enrich the iron ions with a concentration of less than 50mg/L in the high nickel solution to about 20g/L, which has a relatively high adsorption rate. Good removal performance; at the same time, its analytical performance is also good, and almost all of the adsorbed iron can be resolved. To sum up, the iron ion adsorption resin prepared by the patent of the present invention has a good application effect, can remove and enrich the iron in the solution, and can be reused.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention in any form. Although the present invention is disclosed above with preferred embodiments, it is not intended to limit the present invention. Personnel, within the scope of the technical solution of the present invention, can make some changes or modifications to equivalent examples of equivalent changes by using the technical content disclosed above, provided that the content of the technical solution of the present invention is not deviated from, according to the Any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the technical solutions of the present invention.

Claims (22)

1. an iron ion adsorption resin, is characterized in that, described resin is that repeating unit A and repeating unit B are cross-linked and copolymerized to form: The chemical formula of repeating unit A is:

The chemical formula for repeating unit B is:

wherein R is (CH ₂ ) _n , n=0, 1, 2, 3 . . . 2. a kind of iron ion adsorption resin according to claim 1, is characterized in that, preparation method comprises the steps: Step (1) prepare oil phase and water phase respectively, adopt suspension polymerization mode to prepare resin-based balls by copolymerizing divinylbenzene and styrene; Step (2) phosphorylation of resin-based balls to obtain phosphorylated resin intermediate; Step (3) Phosphorylated resin intermediates are subjected to sulfonation reaction. 3. a kind of iron ion adsorption resin according to claim 2, is characterized in that, in the described preparation method, in step (2), phosphorylation reaction is under the catalysis of aluminium chloride, ferric chloride or zinc chloride , using a phosphorylation reagent to directly react with the resin-based ball; the phosphorylation reagent includes one or more of phosphorus trichloride, phosphorus pentachloride or phosphorous acid mixed. 4. a kind of iron ion adsorption resin according to claim 2, is characterized in that, in the described preparation method, in step (2), the resin-based ball is first carried out halogenation reaction, and then further uses phosphorylation reagent and resin-based ball response. 5. a kind of iron ion adsorption resin according to claim 4, is characterized in that, in described preparation method, the halogenation reaction mode in step (2) is: Chloromethylation is carried out using chlorosulfonic acid, paraformaldehyde and the obtained resin-based spheres of the preparation step (1) to obtain chlorine spheres; Or resin-based balls and halogenated alkyl alcohols are grafted by Friedel-Crafts reaction under anhydrous aluminum chloride, ferric chloride or zinc chloride catalyst to obtain halogenated resin; Alternatively, by Friedel-Crafts reaction, resin-based spheres are reacted with 1,2-dihaloethane, 1,3-dihalopropane, 1,4-dihalobutane or 1,5-dihalopentane to graft halogenated alkanes , to obtain halogenated resins. 6. a kind of iron ion adsorption resin according to claim 4 is characterized in that, in the described preparation method, after the halogenation reaction in step (2), the halogenated resin obtained is reacted with phosphoric acid ester compound again, and then After hydrolysis, a phosphorylated resin intermediate is obtained; the phosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite or tributyl phosphite. 7. a kind of iron ion adsorption resin according to claim 2, is characterized in that, in described preparation method, the sulfonation reaction described in step (3) is to adopt vitriol oil, oleum or chlorosulfonic acid Reacts with phosphorylated resin intermediates under heating conditions. 8. a kind of iron ion adsorption resin according to claim 7, is characterized in that, in described preparation method, in step (3), can regulate the amount of sulfonic acid group by regulating the degree of phosphorylation, when When the phosphoric acid group and the sulfonic acid group reach a certain ratio, their ability to bind iron ions will be enhanced. 9. a kind of iron ion adsorption resin according to claim 7, is characterized in that, in described preparation method, in step (3), adopts the sulfuric acid solution of high concentration, mass percentage concentration reaches more than 98%, simultaneously The sulfonation temperature was raised to above 140°C. 10 . The iron ion adsorption resin according to claim 2 , wherein, in the preparation method, in step (3), chlorosulfonic acid can also be used as a raw material for sulfonation. 11 . 11. a kind of iron ion adsorption resin according to claim 2, is characterized in that, in the described preparation method, in step (3), the resin intermediate after sulfonation, through stepwise washing, promptly obtains iron ion Adsorbent resin products. 12. a kind of iron ion adsorption resin according to claim 2, is characterized in that, described preparation method is, respectively prepare oil phase and water phase according to following formula and mode: Oil phase: 40g of 63% DVB, 740g of styrene, 320g of liquid paraffin, 165g of 200# gasoline, 9g of BPO, mix the above materials evenly and use for later use; Aqueous phase: water 2500g, gelatin 30g; add water to a 5000L three-necked flask, turn on stirring, heat up to 45°C, add gelatin, keep at 45°C for 1 h to dissolve the gelatin; Stop stirring, slowly pour the mixed oil phase into the three-necked flask, let it stand for 10 minutes, and replace the air in the upper space of the flask with nitrogen; turn on the stirring and adjust the stirring speed to make the particle size of the oil droplets between 0.3 and 0.8 mm. Begin to heat up, heat up to 70°C for 2h, hold for 2h, then continue to heat up to 80°C for 3h, and heat up to 95°C for 8h; filter out spherical beads, wash with water, and wash with ethanol to obtain resin-based balls; Put the above resin-based balls into an oven and dry at 80°C until the water content is lower than 0.5%, weigh 100 g and put it into a three-necked flask, add 50 g of ethylene dichloride, 28 g of paraformaldehyde, and 109 g of chlorosulfonic acid, turn on stirring, and control The reaction temperature is 40-50 °C for 8 hours. After the reaction is completed, the solid base balls are filtered out, washed with ethanol, and washed with water to obtain chloromethylated resin base balls for later use; Weigh 100 g of resin-based balls, put them into a three-necked flask, add 500 ml of triethyl phosphite, heat up to 130 ° C and finish the reaction for 20 h. After cooling, filter out the resin, wash with ethanol, wash with water and dry until the water content is less than 0.5%. Obtain phosphorylated resin intermediate; Weigh 50g of the phosphorylated resin intermediate after drying, put it into the reaction kettle, add 50g of dichloroethane, soak for 30min, then add 300ml of 98% sulfuric acid, heat up to 80°C for 2h, react for 1h, and heat up to 100°C for 2h The reaction was carried out for 10 hours. After the reaction, the sulfuric acid was gradually diluted. Finally, the resin was washed with a large amount of water, and the final product was obtained after filtration. 13. the application of a kind of iron ion adsorption resin according to any one of the above claims in removing iron ion in solution, it is characterized in that, can be used for trace in high concentration sulfuric acid, copper sulfate, nickel sulfate, cobalt sulfate, zinc sulfate solution Removal of iron ions; used to purify high-concentration valuable metal solutions, can remove iron pollution in high-purity chemical reagents; used for the recovery of rare earth elements; used for the removal of iron in the recovery of lithium iron phosphate batteries. 14. according to the application of a kind of iron ion adsorption resin removal solution of iron ion according to any one of the preceding claims, it is characterized in that, the method of application comprises the steps: The iron ion adsorption resin is packed into a column, and the iron ion-containing solution is passed through the column to make the iron ion adsorbed in the resin; when the resin is saturated with adsorption, the iron ion in the resin is chelated by a regeneration reagent to regenerate the resin; The iron ion-containing solution can be a sulfuric acid solution, a sulfate salt solution, a phosphoric acid solution, a phosphate solution, an organic acid or an organic acid aqueous solution containing iron ions. 15. the application of a kind of iron ion adsorption resin removing iron ion in solution according to claim 14, is characterized in that, described sulfate solution includes but not limited to nickel sulfate solution, copper sulfate solution, zinc sulfate solution, cobalt sulfate solution ; The phosphate solution includes but is not limited to zinc phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate; The organic acid or organic acid aqueous solution includes but is not limited to acetic acid solution, citric acid solution, malic acid solution , succinic acid solution, adipic acid solution. 16 . The application of an iron ion adsorption resin for removing iron ions in a solution according to any one of claims 14 to 15 , wherein the flow rate through the column is 0.1 to 20 BV/h. 17 . 17 . The application of an iron ion adsorption resin for removing iron ions in a solution according to claim 16 , wherein the flow rate through the column is 2-10 BV/h. 18 . 18. The application of an iron ion adsorption resin for removing iron ions in a solution according to claim 17, wherein the flow rate through the column is 2-5 BV/h. 19. a kind of iron ion adsorption resin according to claim 14 removes the application of iron ion in solution, it is characterized in that, after resin adsorption is saturated, adopt the regeneration reagent that has strong chelating ability with ferric ion to regenerate resin , after regeneration, the resin can be used again. 20. a kind of iron ion adsorption resin according to claim 19 removes the application of iron ion in solution, it is characterized in that, regeneration reagent is concentrated hydrochloric acid, sodium EDTA solution, potassium thiocyanate solution, hydrofluoric acid, One or more of hydrocyanic acid and thiocyanic acid. 21. The application of an iron ion adsorption resin for removing iron ions in a solution according to claim 14, wherein the resin has a saturated adsorption capacity of iron in the range of 2 to 30 g/L, and the resin can be regenerated; The resin is washed with water, and the valuable metal solution in the resin pores is washed to the original solution to recover the valuable metal; after washing, the resin is regenerated with a hydrochloric acid solution of at least 6 mol/L or an EDTA solution of 0.1 to 100 g/L, and the regeneration flow rate is It can be controlled at 1 ~ 10BV/h, and the total amount of regeneration is 10BV. After regeneration, the resin can be used again after washing with 5BV. 22. a kind of iron ion adsorption resin according to claim 14 removes the application of iron ion in solution, it is characterized in that, adopt nickel sulfate solution to evaluate its performance, wherein nickel ion content is 100g/L, and iron ion content is 50mg/L ; Load the iron ion adsorption resin into the exchange column, and the solution containing iron ions flows through the resin column at a flow rate of 5BV/h to measure the outlet iron ion concentration; when the outlet iron ion concentration reaches more than 1 mg/L, stop the adsorption; 6mol/L hydrochloric acid solution 10BV to regenerate the resin.