CN111686700A - Iron ion adsorption resin, preparation method and application in removing iron ions in solution - Google Patents
Iron ion adsorption resin, preparation method and application in removing iron ions in solution Download PDFInfo
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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
Technical Field
The invention belongs to the field of preparation and application of functional polymer materials, and relates to a method for preparing iron ion adsorption resin and removing iron ions in a solution.
Background
Iron, one of the most abundant elements in the earth's crust, is often present in large quantities in various solution systems, such as in coexistence with other non-ferrous metals in the ore body, reducing non-ferrous metal quality. Such as in the hydrometallurgical solutions of nickel, cobalt, manganese, lithium, zinc, etc., are critical impurities that, if not removed, would contaminate the target metal, making subsequent use difficult. In addition, organic solvents with high purity, such as electronic grade reagents, are often contaminated with iron ions during the preparation process, resulting in insufficient purity of the reagents.
Therefore, removal of iron impurities is an essential process step for producing high purity products.
There are many iron removal processes, and patent CN 104451145a proposes a method for removing iron from a chloride mixed solution by extraction. The extractant used in the method is N, N-di (2-ethylhexyl) acetamide, the extractant is a neutral extractant, iron needs to be extracted in concentrated acid, the concentration of hydrogen ions is required to be higher than 2mol/L, and the method is suitable for removing iron in the environment with high chlorine content, but the extraction performance of a sulfuric acid system or a low-chlorine low-acid system is poor, so the application range of the method is greatly limited. In patent CN105016368A, a strong base anion exchange resin is used to remove iron from an aluminum chloride-containing solution, which is suitable for removing iron in a chlorination system, and is also suitable for removing iron from a concentrated hydrochloric acid solution, and it is necessary to remove iron ions from a high-concentration chloride solution, and then desorption is performed with water to obtain a desorption solution containing iron chloride. However, this method is not suitable for iron removal in a sulfuric acid system.
Patent CN109133153A describes that iron is precipitated after complexing with an organic complexing agent such as sodium ferometalate or tetrasodium iminodisuccinate, then extracted with an extractant, and the iron is separated from the organic complexing agent after back extraction to achieve the iron removal function. Although the method can remove iron, the working procedure needs both precipitation and extraction, and organic impurities are easily introduced into the solution, thereby causing influence on post-treatment or product purity. Patent CN102992387B adopts metastannic acid as a precipitator, and a mode of precipitating ferric iron can reduce iron ions to about 5ppm, and the technology uses stannic acid, can introduce impurities and has a narrow application range. Patent CN106636651B adopts an iron phosphate aluminum complex precipitation method mainly using aluminum phosphate, but the process needs to adjust the pH of the solution, and the introduction of phosphate and the like has an influence on the process.
The patent CN 106636638B deeply removes iron in a cobalt solution, chelate resin is utilized as Monophos, feed liquid is subjected to iron removal through ion exchange resin, and then fed into an electrowinning tank for electro-winning impurity removal and purification, so that a high-purity cobalt product with the iron content of less than 1ppm and the purity of 99.999 percent can be obtained. Patent CN 102676814B describes a method for removing trace iron from strongly acidic nickel sulfate solution, which uses a sulfonic acid group phosphate chelating resin to obtain high-purity nickel sulfate solution. Both patents mention chelating resins and describe the good effect of iron removal.
Disclosure of Invention
The invention aims to disclose a method for removing iron in a metal solution, and particularly relates to a method for removing iron in the solution by adopting a resin adsorption method.
In order to achieve the effect of removing iron in the solution, the resin used by the invention is a styrene skeleton, and phosphate groups and sulfonic functional groups are grafted, so that the resin achieves a better iron removal effect, and the structure of the resin is as follows:
wherein R is (CH)2)n，n＝0，1，2，3……。
The resin adopts divinylbenzene as a cross-linking agent, and has the structure as follows:
the preparation steps of the resin are as follows:
(1) respectively preparing an oil phase and a water phase, and copolymerizing divinylbenzene and styrene by adopting a suspension polymerization mode to prepare a resin-based sphere;
(2) the resin-based sphere is subjected to phosphorylation reaction by using phosphorylation reagents such as phosphorus trichloride, phosphorus pentachloride, phosphorous acid and the like in the presence of aluminum trichloride, ferric chloride or zinc chloride, or a phosphorylation resin intermediate is prepared in a mode of halogenation and phosphorylation;
(3) and (3) carrying out sulfonation reaction and water washing on the phosphorylated resin intermediate to obtain the iron ion adsorption resin.
More specifically, the resin-based sphere may be directly subjected to phosphorylation reaction with a phosphorylation reagent such as phosphorus trichloride, phosphorus pentachloride, phosphorous acid or the like in the presence of aluminum trichloride, ferric chloride or zinc chloride without modification, so that the phosphate group functional group may be directly linked to the benzene ring.
The resin-based spheres can also be used to prepare phosphorylated resin intermediates by halogenation and subsequent phosphorylation reactions. The halogenation reaction is carried out in three ways: performing chloromethylation reaction on chlorosulfonic acid, paraformaldehyde and the resin-based ball obtained in the step (1) to obtain a chlorine ball; secondly, the resin-based sphere is grafted by Friedel-crafts reaction under the catalysis of anhydrous aluminum chloride, ferric chloride or zinc chloride by using halogenated alkyl alcohol such as 2-bromoethanol, 3-bromopropanol and the like to obtain halogenated resin; thirdly, the resin base ball reacts with 1, 2-dihaloethane, 1, 3-dihalopropane, 1, 4-dihalobutane or 1, 5-dihalopentane to graft halogenated alkane through Friedel-crafts reaction, so as to obtain halogenated resin. The chlorine ball or the halogenated resin is reacted with phosphate ester compound such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, etc. to obtain phosphorylated resin intermediate.
In the preparation of the resin, the amount of the sulfonic acid group can be adjusted by adjusting the phosphorylation degree, and after the phosphoric acid group and the sulfonic acid group reach a certain proportion, the iron ion binding capacity of the resin is 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 the sulfonation reaction process needs to be carried out under stronger sulfonation conditions, such as a high-concentration sulfuric acid solution is adopted, the mass percentage concentration reaches more than 98%, and meanwhile, the sulfonation temperature requirement is higher, and the temperature needs to be raised to more than 140 ℃; or the sulfonation can be carried out by adopting chlorosulfonic acid as a raw material. The sulfonation reaction process for preparing the common cation resin adopts sulfuric acid with the mass percentage concentration of more than 83 percent, because the sulfonation is the end position which is relatively easy to react on a benzene ring.
And (3) washing the sulfonated resin intermediate step by step with water to obtain the iron ion adsorption resin product.
The product can be used for removing trace iron ions in high-concentration sulfuric acid, copper sulfate, nickel sulfate, cobalt sulfate, zinc sulfate and other solutions. The product is mainly used for purifying high-concentration valuable metal solution, and can remove iron pollution in high-purity chemical reagents; the product can also be used for recovering rare earth elements and removing iron in the recovery of lithium iron phosphate batteries.
The specific using method of the product comprises the following steps: enabling the solution containing iron ions to flow through a resin column filled with the product at the flow rate of 0.1-20 BV/h, adsorbing for a period of time to enable the resin to reach a saturated state, enabling the saturated adsorption capacity of the resin to the iron ions to be 2-30 g/L, and regenerating the resin; before regeneration, washing the resin with water, and washing the valuable metal solution in the resin pore channel to a stock solution to recover valuable metals; after water washing, at least 6mol/L hydrochloric acid solution or 0.1-100 g/L EDTA solution is used for regenerating the resin, the regeneration flow rate can be controlled to be 1-10 BV/h, the total regeneration amount is 10BV, and after regeneration, the resin can be reused after 5BV water washing.
The iron-containing solution can be sulfuric acid and sulfate solutions such as sulfuric acid solution, nickel sulfate solution, copper sulfate solution, zinc sulfate solution, cobalt sulfate solution and the like containing iron ions, can also be used for phosphoric acid solution and salt solution thereof containing iron ions, such as zinc phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate and sodium dihydrogen phosphate, and can also be used for organic acid and organic acid aqueous solution containing iron ions, such as acetic acid solution, citric acid solution, malic acid solution, succinic acid solution, adipic acid solution and the like.
The product has good adsorption chelation effect on ferric ions, and the regeneration of the product needs to adopt a regenerant with stronger chelation capacity with the ferric ions, for example, hydrochloric acid can form [ FeCl ] with the ferric ions4]-The anion is complexed, so that a chelate bond formed between the resin and the iron ions is destroyed, and the effect of regenerating and recovering the adsorption capacity of the resin is achieved; similarly, compounds such as sodium ethylenediaminetetraacetate solution, potassium thiocyanate solution, hydrofluoric acid, hydrocyanic acid, and thiocyanic acid can be used as the regenerant.
The invention has the following beneficial effects:
the adsorbent has higher adsorption selectivity on iron ions, can enrich the iron ions with the concentration lower than 50mg/L in a high-nickel solution to about 20g/L, and has better removal capacity; meanwhile, the iron ions are easy to resolve, and almost all the adsorbed iron ions can be resolved. In conclusion, the iron ion adsorption resin prepared by the invention has a good application effect, can remove and enrich iron ions in a solution, and can be repeatedly used.
Detailed Description
Examples 1 to 5:
different amounts of cross-linking agents are adopted to prepare different resin-based spheres, and the specific cross-linking agent amounts are as follows:
| 63％DVB/g | 80％DVB/g | |
| example 1 | 40 | |
| Example 2 | 55 | |
| Example 3 | 90 | |
| Example 4 | 85 | |
| Example 5 | 150 |
Oil phase other composition: styrene: 740g, liquid paraffin: 320g, 200# gasoline: 165g, BPO: 9g, uniformly mixing the substances for later use;
water phase: tap water: 2500g, gelatin: 30g of the total weight of the mixture; adding water into a 5000L three-neck flask, stirring, heating to 45 ℃, adding gelatin, and keeping the temperature at 45 ℃ for 1h to dissolve the gelatin;
stopping stirring, slowly pouring the mixed oil phase into a three-neck flask, standing for 10min, and replacing air in the upper space of the flask with nitrogen; starting stirring, adjusting the stirring speed to enable the particle size of oil droplets to be 0.3-0.8 mm, starting heating, heating to 70 ℃ for 2h, keeping the temperature for 2h, then continuing heating to 80 ℃ and keeping the temperature for 3h, and heating to 95 ℃ and keeping the temperature for 8 h; filtering to obtain bead-shaped particles, washing with water, and washing with ethanol to obtain resin-based spheres.
Putting the resin base ball into an oven, drying at 80 ℃ until the water content is lower than 0.5%, weighing 100g, putting into a three-neck flask, adding 50g of dichloroethane, 28g of paraformaldehyde and 109g of chlorosulfonic acid, starting stirring, controlling the reaction temperature to be 40-50 ℃, reacting for 8h, filtering out the solid base ball after the reaction is finished, washing with ethanol, and washing with water to obtain a chloromethylated resin chlorine ball for later use;
weighing 100g of the resin chlorine ball, putting the resin chlorine ball into a three-neck flask, adding 500ml of triethyl phosphite, heating to 130 ℃, reacting for 20h, cooling, filtering out the resin, washing with ethanol, washing with water, and drying until the water content is lower than 0.5% to obtain a phosphorylated resin intermediate;
weighing 50g of the dried phosphorylated resin intermediate, putting the weighed phosphorylated resin intermediate into a reaction kettle, adding 50g of dichloroethane, soaking for 30min, then adding 300ml of 98% sulfuric acid, heating to 80 ℃ for 2h, reacting for 1h, heating to 100 ℃ for 2h, reacting for 10h, gradually diluting the sulfuric acid after the reaction is finished, finally washing the resin with a large amount of water, and filtering to obtain the final product.
Examples 6 to 10:
preparation of resin-based spheres was carried out by the method of example 2; putting the resin-based ball into an oven, and drying at 80 ℃ until the water content is below 0.5%; weighing 100g of dried resin-based ball, putting into a dried three-neck flask, adding 100g of aluminum trichloride, adding the substances in the table below respectively, and stirring and swelling 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 |
Heating to 60 ℃, keeping the temperature, reacting for 10 hours, filtering out resin, washing with ethanol, washing with water to obtain a hydroxylated resin intermediate, and drying in an oven at 80 ℃ until the water content is less than 0.5% for later use;
weighing 100g of dried hydroxylated resin intermediate, putting the weighed intermediate into a dry three-neck flask, adding 100g of dichloroethane, 200g of phosphorus pentachloride and 200g of phosphorous acid, heating to reflux reaction for 24 hours, filtering out resin, washing with ethanol, washing with water to obtain a phosphorylated resin intermediate, and drying the phosphorylated resin intermediate in a drying oven at 80 ℃ until the water content is less than 0.5% for later use;
weighing 50g of the dried phosphorylated resin intermediate, putting the weighed phosphorylated resin intermediate into a reaction kettle, adding 50g of dichloroethane, soaking for 30min, then adding 300ml of 98% sulfuric acid, heating to 80 ℃ for 2h, reacting for 1h, heating to 100 ℃ for 2h, reacting for 10h, gradually diluting the sulfuric acid after the reaction is finished, finally washing the resin with a large amount of water, and filtering to obtain the final product.
Examples 11 to 15:
preparation of resin-based spheres was carried out by the method of example 2; putting the resin-based ball into an oven, and drying at 80 ℃ until the water content is below 0.5%; weighing 100g of dried resin-based ball, putting into a dried three-neck flask, adding 400g of phosphorous acid and 50g of aluminum trichloride, respectively adding the substances listed in the following table, stirring and swelling for 120 min:
| phosphorus trichloride | Phosphorus pentachloride | |
| Example 11 | 100 | |
| Example 12 | 200 | |
| Example 13 | 300 | |
| Example 14 | 400 | |
| Example 15 | 500 |
Heating to 75 ℃, keeping the temperature, reacting for 10 hours, filtering out resin, washing with ethanol, washing with water to obtain a phosphorylated resin intermediate, and drying in an oven at 80 ℃ until the water content is less than 0.5% for later use;
weighing 50g of the dried phosphorylated resin intermediate, putting the weighed phosphorylated resin intermediate into a reaction kettle, adding 50g of dichloroethane, soaking for 30min, then adding 300ml of 98% sulfuric acid, heating to 80 ℃ for 2h, reacting for 1h, heating to 100 ℃ for 2h, reacting for 10h, gradually diluting the sulfuric acid after the reaction is finished, finally washing the resin with a large amount of water, and filtering to obtain the final product.
Examples 16 to 19:
preparation of resin-based spheres was carried out by the method of example 2; putting the resin-based ball into an oven, and drying at 80 ℃ until the water content is below 0.5%; weighing 100g of dried resin-based ball, putting into a dried three-neck flask, adding 50g of aluminum trichloride, adding the following substances according to the following table, stirring and swelling for 120min,
heating to 75 ℃, keeping the temperature, reacting for 10 hours, filtering out resin, washing with ethanol, washing with water to obtain chlorinated resin chlorine balls, and drying in an oven at 80 ℃ until the water content is less than 0.5% for later use;
weighing 100g of the resin chlorine ball, putting the resin chlorine ball into a three-neck flask, adding 500ml of tributyl phosphate, heating to 130 ℃, reacting for 20h, cooling, filtering out the resin, washing with ethanol, washing with water, and drying until the water content is lower than 0.5% to obtain a phosphorylated resin intermediate;
weighing 50g of the dried phosphorylated resin intermediate, putting the weighed phosphorylated resin intermediate into a reaction kettle, adding 50g of dichloroethane, soaking for 30min, then adding 300ml of 98% sulfuric acid, heating to 80 ℃ for 2h, reacting for 1h, heating to 100 ℃ for 2h, reacting for 10h, gradually diluting the sulfuric acid after the reaction is finished, finally washing a large amount of resin with water, and filtering to obtain a final product;
the resin prepared by the above example was evaluated for its properties using a nickel sulfate solution, wherein the nickel ion content was 100g/L and the iron ion content was 50 mg/L. Loading iron ion adsorption resin into an exchange column, allowing an iron-containing solution to flow through the resin column at a flow rate of 5BV/h, and measuring the concentration of iron ions at an outlet; stopping adsorption when the concentration of the iron ions at the outlet reaches more than 1mg/L, recording the treatment volume, and calculating the adsorption amount of the resin; then regenerating the resin by adopting a hydrochloric acid solution of 6mol/L and 10BV, testing the iron content in the regenerated liquid and calculating the resolution ratio; the specific data are as follows:
performance evaluation shows that the iron ion adsorption resin prepared by the method has higher adsorption selectivity on iron, can enrich iron ions with concentration lower than 50mg/L in a high nickel solution to about 20g/L, and has better removal performance; meanwhile, the desorption performance is better, and the adsorbed iron can be almost completely desorbed. In conclusion, the iron ion adsorption resin prepared by the invention has a good application effect, can remove and enrich iron in a solution, and can be repeatedly used.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (22)
1. The iron ion adsorption resin is characterized in that the resin is formed by crosslinking and copolymerizing a repeating unit A and a repeating unit B:
the chemical formula of the repeating unit A is:
the chemical formula of the repeating unit B is as follows:
wherein R is (CH)2)n，n＝0，1，2，3……。
2. The iron ion adsorption resin of claim 1, wherein the preparation method comprises the following steps:
respectively preparing an oil phase and a water phase, and copolymerizing divinylbenzene and styrene by adopting a suspension polymerization mode to prepare a resin-based sphere;
carrying out phosphorylation reaction on the resin-based spheres to obtain a phosphorylated resin intermediate;
and (3) carrying out sulfonation reaction on the phosphorylated resin intermediate.
3. The iron ion adsorption resin of claim 2, wherein in the preparation method, the phosphorylation reaction in the step (2) is directly reacted with the resin-based spheres by using a phosphorylation reagent under catalysis of aluminum chloride, ferric chloride or zinc chloride; the phosphorylation reagent comprises one or a mixture of more of phosphorus trichloride, phosphorus pentachloride and phosphorous acid.
4. The iron ion adsorption resin of claim 2, wherein in the step (2), the resin-based spheres are halogenated, and then a phosphorylating reagent is further used to react with the resin-based spheres.
5. The iron ion adsorption resin of claim 4, wherein in the preparation method, the halogenation reaction mode in the step (2) is as follows:
performing chloromethylation reaction on chlorosulfonic acid, paraformaldehyde and the resin-based ball obtained in the step (1) to obtain a chlorine ball;
or the resin-based ball and halogenated alkyl alcohol are grafted under Friedel-crafts reaction in the presence of anhydrous aluminum chloride, ferric chloride or zinc chloride catalysts to obtain halogenated resin;
or the resin base ball is reacted with 1, 2-dihaloethane, 1, 3-dihalopropane, 1, 4-dihalobutane or 1, 5-dihalopentane to graft halogenated alkane through Friedel-crafts reaction to obtain the halogenated resin.
6. The iron ion adsorption resin of claim 4, wherein in the preparation method, after the halogenation reaction in the step (2), the obtained halogenated resin is reacted with a phosphate compound, and then hydrolyzed to obtain a phosphorylated resin intermediate; the phosphate ester compound comprises trimethyl phosphate, triethyl phosphate, tributyl phosphate, trimethyl phosphite, triethyl phosphite or tributyl phosphite.
7. The iron ion adsorption resin of claim 2, wherein in the preparation method, the sulfonation reaction in step (3) is carried out by reacting concentrated sulfuric acid, fuming sulfuric acid or chlorosulfonic acid with a phosphorylated resin intermediate under heating.
8. The iron ion adsorption resin of claim 7, wherein in the step (3), the amount of the sulfonic acid group is adjusted by adjusting the degree of phosphorylation, and the iron ion binding ability of the phosphoric acid group and the sulfonic acid group is increased when the phosphoric acid group and the sulfonic acid group are in a certain ratio.
9. The iron ion adsorption resin of claim 7, wherein in the step (3), a high-concentration sulfuric acid solution is used, the mass percentage concentration is more than 98%, and the sulfonation temperature is raised to more than 140 ℃.
10. The iron ion adsorption resin of claim 2, wherein in the step (3), chlorosulfonic acid is also used as a raw material for sulfonation.
11. The iron ion adsorption resin of claim 2, wherein in the step (3), the sulfonated resin intermediate is washed with water step by step to obtain an iron ion adsorption resin product.
12. The iron ion adsorption resin of claim 2, wherein the preparation method comprises preparing the oil phase and the water phase according to the following formula and manner:
oil phase: 40g of 63% DVB, 740g of styrene, 320g of liquid paraffin, 165g of 200# gasoline and BPO9g, and uniformly mixing the substances for later use;
water phase: 2500g of water and 30g of gelatin; adding water into a 5000L three-neck flask, stirring, heating to 45 ℃, adding gelatin, and keeping the temperature at 45 ℃ for 1h to dissolve the gelatin;
stopping stirring, slowly pouring the mixed oil phase into a three-neck flask, standing for 10min, and replacing air in the upper space of the flask with nitrogen; starting stirring, adjusting the stirring speed to enable the particle size of oil droplets to be 0.3-0.8 mm, starting heating, heating to 70 ℃ for 2h, keeping the temperature for 2h, then continuing heating to 80 ℃ and keeping the temperature for 3h, and heating to 95 ℃ and keeping the temperature for 8 h; filtering to obtain bead-shaped particles, washing with water, and washing with ethanol to obtain resin-based spheres;
putting the resin base ball into an oven, drying at 80 ℃ until the water content is lower than 0.5%, weighing 100g, putting into a three-neck flask, adding 50g of dichloroethane, 28g of paraformaldehyde and 109g of chlorosulfonic acid, starting stirring, controlling the reaction temperature to be 40-50 ℃, reacting for 8h, filtering out the solid base ball after the reaction is finished, washing with ethanol, and washing with water to obtain a chloromethylated resin base ball for later use;
weighing 100g of resin-based spheres, putting the resin-based spheres into a three-neck flask, adding 500ml of triethyl phosphite, heating to 130 ℃, reacting for 20 hours, cooling, filtering out the resin, washing with ethanol, washing with water, and drying until the water content is lower than 0.5% to obtain a phosphorylated resin intermediate;
weighing 50g of the dried phosphorylated resin intermediate, putting the weighed phosphorylated resin intermediate into a reaction kettle, adding 50g of dichloroethane, soaking for 30min, then adding 300ml of 98% sulfuric acid, heating to 80 ℃ for 2h, reacting for 1h, heating to 100 ℃ for 2h, reacting for 10h, gradually diluting the sulfuric acid after the reaction is finished, finally washing the resin with a large amount of water, and filtering to obtain the final product.
13. The use of an iron ion adsorption resin according to any one of the preceding claims for removing iron ions from a solution, wherein the resin can be used for removing trace iron ions from a high-concentration sulfuric acid, copper sulfate, nickel sulfate, cobalt sulfate and zinc sulfate solution; the purifying agent is used for purifying high-concentration valuable metal solution, and can remove iron pollution in high-purity chemical reagents; the method is used for recovering the rare earth elements; the method is used for removing iron in the recovery of the lithium iron phosphate battery.
14. The use of an iron ion adsorbing resin according to any of the preceding claims to remove iron ions from a solution, wherein the method comprises the steps of:
filling iron ion adsorption resin into a column, and allowing a solution containing iron ions to pass through the column to adsorb the iron ions in the resin; after the resin is saturated in adsorption, chelating iron ions in the resin by using a regeneration reagent to regenerate the resin;
the solution containing iron ions can be sulfuric acid solution, sulfate solution, phosphoric acid solution, phosphate solution, organic acid or organic acid aqueous solution containing iron ions.
15. The use of the iron ion adsorbing resin to remove iron ions from a solution according to claim 14, wherein the sulfate solution includes but is not limited to nickel sulfate solution, copper sulfate solution, zinc sulfate solution, cobalt sulfate solution; the phosphate solutions include, but are not limited to, zinc phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate; the organic acid or aqueous organic acid solution includes, but is not limited to, acetic acid solution, citric acid solution, malic acid solution, succinic acid solution, adipic acid solution.
16. The use of an iron ion adsorbing resin according to any of claims 14 to 15 for removing iron ions from a solution, wherein the flow rate through the column is 0.1 to 20 BV/h.
17. The use of the iron ion adsorbing resin according to claim 16 for removing iron ions from a solution, wherein the flow rate through the column is 2-10 BV/h.
18. The use of the iron ion adsorbing resin to remove iron ions from a solution according to claim 17, wherein the flow rate through the column is 2-5 BV/h.
19. The use of an iron ion adsorbing resin to remove iron ions from a solution according to claim 14, wherein the resin is regenerated with a regenerating agent having a strong chelating ability for ferric ions after the resin is saturated by adsorption, and the resin is reused after regeneration.
20. The use of an iron ion-adsorbing resin according to claim 19 for removing iron ions from a solution, wherein the regeneration reagent is one or more of concentrated hydrochloric acid, sodium ethylenediaminetetraacetate solution, potassium thiocyanate solution, hydrofluoric acid, hydrocyanic acid, and thiocyanic acid.
21. The application of the iron ion adsorption resin to removal of iron ions in a solution according to claim 14, wherein the saturated adsorption capacity of the resin to iron is 2-30 g/L, and the resin can be regenerated; before regeneration, washing the resin with water, and washing the valuable metal solution in the resin pore channel to a stock solution to recover valuable metals; after water washing, at least 6mol/L hydrochloric acid solution or 0.1-100 g/L EDTA solution is used for regenerating the resin, the regeneration flow rate can be controlled to be 1-10 BV/h, the total regeneration amount is 10BV, and after regeneration, the resin can be reused after 5BV water washing.
22. The use of an iron ion adsorbing resin to remove iron ions from a solution according to claim 14, wherein the performance of the iron ion adsorbing resin is evaluated by using a nickel sulfate solution, wherein the nickel ion content is 100g/L, and the iron ion content is 50 mg/L; loading iron ion adsorption resin into an exchange column, allowing a solution containing iron ions to flow through the resin column at a flow rate of 5BV/h, and measuring the concentration of the iron ions at an outlet; stopping adsorption when the concentration of the iron ions at the outlet reaches more than 1 mg/L; then, the resin is regenerated by using 10BV of 6mol/L hydrochloric acid solution.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114261998B (en) * | 2021-12-28 | 2024-02-27 | 南城广德新材科技有限公司 | Preparation method of high-purity alkali type nickel carbonate |
| CN116120561A (en) * | 2022-12-26 | 2023-05-16 | 宁波争光树脂有限公司 | Phosphoric acid resin and preparation method thereof |
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