A method for removing antimony using zirconium-functionalized adsorption resin

Abstract

Provided is a method for removing antimony using a zirconium-functionalized adsorption resin, which belongs to the field of environmental protection. The method comprises the following steps: Step 1): adjusting the pH of a solution containing antimony ions to 1-11, then adding a zirconium-functionalized adsorption resin thereto to adsorb the antimony ions in the antimony-containing solution; Step 2): after the adsorption is completed, using a washing liquid to elute, concentrate, separate and regenerate the antimony loaded on the zirconium-functionalized adsorption resin to achieve the removal of antimony. The present invention improves the key reaction participants of the method and applies the zirconium-functionalized adsorption resin material to the recovery of antimony. The method can be particularly applied to the adsorption of low-content antimony in mine water, and can also remove highly toxic arsenic at the same time. The present invention is simple to operate and suitable for large-scale recovery of low-concentration antimony.

Description

Technical Field

[0001] The present invention belongs to the technical field of environmental protection, and in particular relates to a method for removing antimony by utilizing zirconium-functionalized adsorption resin. Based on this method, low-concentration antimony can be recovered from actual mine water. Background Art

[0002] Antimony is the fifth most important non-renewable strategic metal. Antimony and its compounds are widely used in ceramics, pigments, plastics, batteries, pyrotechnics, alloys, and flame retardants. Generally speaking, the toxicity of various antimony compounds is ranked as follows: Sb(III) > Sb(V) > organic antimony compounds. However, antimony has high cumulative toxicity and carcinogenicity to humans. Therefore, to protect human health, many countries and organizations have listed antimony as a priority pollutant.

[0003] According to existing literature, the treatment of antimony is mainly divided into membrane separation technology, ion exchange, coagulation / flocculation, electrochemical technology, adsorption, etc. Generally speaking, membrane separation technology and ion exchange technology can achieve high removal efficiency, but investment and operating costs hinder their development; coagulation technology and electrochemical technology are more practical, but there is also the risk of secondary pollution. Among them, adsorption is currently the best method for treating antimony due to its simple operation, safety, low cost and high efficiency. In addition, adsorption technology is suitable for the treatment of low concentrations of metal ions. The most critical part of the adsorption method is the adsorbent. In order to cope with the high demand for antimony in industrial production and reduce the environmental pollution caused by antimony, it is crucial to design efficient zirconium-functionalized adsorption resins to remove antimony.

[0004] The introduction of high-valent metal elements such as zirconium, iron and titanium can show good affinity for antimony. Many literatures have adopted similar ideas to achieve higher antimony adsorption than before modification. It is reported that some titanium-functionalized composite adsorbent materials will decompose under acidic conditions. At the same time, some ferrite-functionalized composite materials have low adsorption capacity and lack mechanical strength, which hinders the practical application of these materials. Zirconium, as an inorganic material, has the characteristics of non-toxicity, chemical inertness and insolubility in water, and has a higher affinity for antimony ions. This provides a theoretical basis for the use of zirconium-functionalized compound adsorbents to treat highly toxic antimony in water. Therefore, the development of zirconium-functionalized adsorption resins for efficient removal of antimony is of great significance to environmental protection and human health. Summary of the Invention

[0005] The technical problem solved by the present invention is to provide a method for removing antimony using a zirconium-functionalized adsorption resin. The purpose of the present invention is to use a zirconium-functionalized compound adsorbent to treat highly toxic antimony ions in water, and by modifying the surface of the substrate, the surface of the adsorption resin is zirconium-functionalized to the maximum extent, making it suitable for large-scale recovery of low-concentration antimony.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] A method for removing antimony using a zirconium-functionalized adsorption resin comprises the following steps:

[0008] Step 1): adjusting the pH of the solution containing antimony ions to 1-11, and then adding a zirconium-functionalized adsorption resin thereto to adsorb the antimony ions in the antimony ion-containing solution;

[0009] Step 2): After the adsorption is completed, the antimony loaded on the zirconium functionalized adsorption resin is eluted, concentrated, separated and regenerated using an eluent to achieve the removal of the antimony.

[0010] Wherein, in the above step 1), the zirconium-functionalized adsorption resin is a zirconium-functionalized adsorption resin obtained by surface modification of a polymer substrate; the chemical structure of the zirconium-functionalized adsorption resin is: in, represents polymer substrate;

[0011] Specifically, the surface modification method of the zirconium-functionalized adsorption resin comprises the following steps:

[0012] Step (a): first grafting an unsaturated monomer containing an epoxy group or a halogen onto the surface of a polymer substrate to modify the substrate to form a functional intermediate I;

[0013] The mass ratio of the polymer substrate to the epoxy group or halogen unsaturated monomer emulsion is (1-2): (5-20), and the epoxy group or halogen unsaturated monomer emulsion contains 30% by mass of the epoxy group or halogen unsaturated monomer;

[0014] Step (b): further introducing a compound having sodium carboxylate on the surface of the functional intermediate I through an epoxy ring-opening reaction or a halogenation reaction to obtain a functional intermediate II;

[0015] Wherein, the mass ratio of the functional intermediate I to the compound having sodium carboxylate is (1-2): (10-20);

[0016] Step (c): Finally, a chelating reaction is carried out between the carboxyl group of the functional intermediate II and zirconium oxychloride ZrOCl2, thereby obtaining a zirconium functionalized adsorption resin for recovering antimony;

[0017] Wherein, the mass ratio of the functional intermediate II to zirconium oxychloride is (1-2): (10-20).

[0018] As a further preferred embodiment of the present invention, in the above step (a), the polymer substrate is selected from one of cellulose, lignin, chitosan or its derivatives, polyethylene, polypropylene, polystyrene, polystyrene-divinylbenzene copolymer, ethylene-vinyl alcohol copolymer, and polyamide;

[0019] The crystallinity of the cellulose or its derivative is above 80%.

[0020] As a further preference of the present invention, in the above step (a), the unsaturated monomer containing epoxy group or halogen is selected from one of glycidyl methacrylate GMA, allyl alcohol glycidyl ether, glycidyl acrylate, chloroethyl methacrylate, chloroethyl acrylate, and chloromethylstyrene.

[0021] As a further preferred embodiment of the present invention, in the above step (b), the compound having sodium carboxylate is one of sodium iminodiacetic acid, sodium aminoacetate, and sodium alanine.

[0022] As a further preferred embodiment of the present invention, in the above step (a), the grafting method for modifying the surface of the polymer substrate is specifically an ionizing radiation grafting method or a chemical grafting method;

[0023] The ionizing radiation grafting method is electron beam pre-radiation grafting, and the irradiation dose used in the electron beam pre-radiation grafting is preferably 10 to 100 kGy;

[0024] The chemical grafting method is grafting by using an initiator; the initiator is preferably an organic peroxide or an azo initiator, wherein the organic peroxide is preferably cyclohexanone peroxide, dibenzoyl peroxide or tert-butyl hydroperoxide; the azo initiator is preferably azobisisobutyronitrile or azobisisoheptanenitrile.

[0025] As a further preference of the present invention, in the above step (b), when a compound containing sodium carboxylate is further introduced onto the surface of the polymer substrate through an epoxy ring-opening reaction, it is specifically achieved through a solvothermal reaction; the solvent used in the solvothermal reaction is water, methanol, toluene, ethylene glycol or N,N-dimethylformamide, and the reaction temperature of the solvothermal reaction is 80-140°C.

[0026] As a further preferred embodiment of the present invention, in the above step (c), when zirconium functionalization is achieved by reacting sodium carboxylate and zirconium oxychloride, it is specifically achieved by a hydrothermal reaction; the concentration of the zirconium oxychloride solution used in the hydrothermal reaction is 10-20wt%, and the reaction temperature of the hydrothermal reaction is 80-120°C.

[0027] As a further preferred embodiment of the present invention, the polymer substrate is spherical, fibrous or film-shaped; accordingly, the obtained zirconium-functionalized adsorption resin is also spherical, fibrous or film-shaped;

[0028] Preferably, the average particle size of the spherical resin that can be used to fill the adsorption column is between 100 and 1000 μm.

[0029] As a further preferred embodiment of the present invention, in the above step 1), the antimony-containing solution mainly comprises a leachate of stibnite, stibnite, antimony ochre, or antimony-containing groundwater;

[0030] As a further preferred embodiment of the present invention, in the above step 2), the eluent is a 1 mol / L to 3 mol / L sodium hydroxide solution.

[0031] The advantages of the present invention compared with the prior art are:

[0032] 1. To maximize zirconium functionalization on the adsorption resin surface, this scheme utilizes ionizing radiation grafting or chemical grafting methods in the adsorption material structure design. Unsaturated monomers containing epoxy groups or halogens are first introduced into the substrate. The grafted substrate is then modified with carboxylates. The zirconium compound is chelated and fixed to the adsorption resin surface via carboxyl groups to obtain a zirconium-functionalized adsorption resin, thereby providing a large number of active sites. The adsorption separation material obtained by this method is particularly suitable for the efficient adsorption of low-concentration antimony.

[0033] 2. The zirconium-functionalized adsorption resin synthesized in this scheme has its surface modified with abundant zirconium ions that have a high affinity for antimony ions. The zirconium oxychloride introduced onto the substrate by the adsorption resin can, on the one hand, undergo anion exchange with the antimony ions; on the other hand, it can coordinate with the antimony ions through the lone electron pair on the zirconium-oxygen double bond, thereby achieving efficient adsorption of antimony.

[0034] 3. This scheme improves the key reaction participants in the method and applies zirconium-functionalized adsorption resin materials to the recovery of antimony. It can be especially used for the adsorption of low-content antimony in mine water and can also remove highly toxic arsenic at the same time. It is simple to operate and suitable for large-scale recovery of low-concentration antimony. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The synthetic route of the zirconium-functionalized adsorption resin in the present invention is as follows;

[0036] Figure 2 Figure 2 shows the adsorption results of Sb(III) by the zirconium-functionalized adsorption resin at different pH values ​​in the embodiment of the present invention;

[0037] Figure 3 Figure 2 shows the adsorption results of Sb(V) by the zirconium-functionalized adsorption resin at different pH values ​​in an embodiment of the present invention;

[0038] Figure 4Figure 2 shows the adsorption results of different concentrations of Sb(III) by the zirconium-functionalized adsorption resin in the embodiment of the present invention;

[0039] Figure 5 Figure 2 shows the adsorption results of different concentrations of Sb(V) by the zirconium-functionalized adsorption resin in the embodiment of the present invention;

[0040] Figure 6 Figure 2 shows the experimental results of the reuse of antimony by zirconium-functionalized adsorption resin in an embodiment of the present invention;

[0041] Figure 7 Figure 1 shows the static adsorption experimental results of antimony in mine water by zirconium-functionalized adsorption resin in an embodiment of the present invention;

[0042] Figure 8 Figure 2 shows the results of a dynamic adsorption experiment on antimony in mine water by a zirconium-functionalized adsorption resin according to an embodiment of the present invention;

[0043] Figure 9 Figure 2 shows the experimental results of the dynamic elution of antimony from mine water by zirconium-functionalized adsorption resin in an embodiment of the present invention. DETAILED DESCRIPTION

[0044] In order to make the purpose, technical solutions and advantages of the present invention more clear, the following Figure 1-9 The present invention will be further described in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely intended to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other. In addition, after reading the contents of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims appended hereto.

[0045] The method of the present invention can be divided into an adsorption process and an elution process. Specifically, a zirconium-functionalized adsorption resin is added to a solution to adsorb antimony, or the antimony-containing solution is pumped through an adsorption column filled with a zirconium-functionalized adsorption resin material via a peristaltic pump. After adsorption is complete, the antimony loaded on the material is eluted and separated using a corresponding eluent.

[0046] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.

[0047] Example 1: Synthesis of zirconium-functionalized adsorption resin

[0048] The synthetic route of zirconium functionalized adsorption resin is as follows Figure 1As shown. 5.00g of microcrystalline cellulose microspheres (Celp) were vacuum sealed and passed through a 1MeV electron beam accelerator under dry ice cooling (irradiation dose rate of 10kGy / pass, irradiation dose of 10kGy). Then, the irradiated Celp was placed into 50g of GMA emulsion (30% GMA, 3% surfactant Tween 20) and reacted in a 50°C water bath for 2h. The product was washed with ethanol and vacuum dried at 60°C to obtain Celp-g-GMA. 1g of Celp-g-GMA was placed into a 20wt% aqueous solution of sodium iminodiacetic acid and reacted at 80°C for 12h. The reaction product was washed, filtered, and dried to obtain Celp-g-GMA-IDA. Then, 1 g of Celp-g-GMA-IDA was added to a 10 wt% zirconium oxychloride aqueous solution and reacted at 80°C for 12 h. The reaction product was washed, filtered, and dried to obtain the zirconium-functionalized adsorption resin Celp-g-GMA-IDA-ZrOCl2.

[0049] In Examples 2 to 9, Celp-g-GMA-IDA-ZrOCl2 zirconium-functionalized adsorption resin was used to explore the removal effect of this type of adsorption material on antimony.

[0050] Example 2: Adsorption of Sb(III) by zirconium-functionalized adsorption resin at different pH values

[0051] Static batch adsorption experiments were conducted by weighing 0.01 g of adsorption resin and placing it in 10 mL of an aqueous solution containing antimony at 30°C. The pH of the solution was adjusted to 1-11 using 0.1 mol / L HCl and NaOH, respectively, before adsorption was performed. After adsorption for a period of time, the supernatant was filtered and the metal ion concentration was determined by ICP-OES. The adsorption efficiency was then calculated.

[0052] The adsorption results of Sb(III) on zirconium functionalized adsorption resin at different pH are as follows: Figure 2 As shown in the figure, it can be seen that the adsorption of Sb(III) by the zirconium functionalized adsorption resin is almost unaffected by pH, indicating that the material can be used in a wide pH range.

[0053] Example 3: Adsorption of Sb(V) by zirconium-functionalized adsorption resin at different pH values

[0054] The zirconium-functionalized adsorption resin was used to adsorb Sb(V) using a similar adsorption procedure as in Example 2. After adsorption for a period of time, the supernatant was filtered out using a filter head, and the residual antimony concentration was measured by ICP-OES, and the adsorption efficiency was calculated.

[0055] The adsorption results of Sb(V) on zirconium functionalized adsorption resin at different pH are as follows: Figure 3As shown in the figure, the adsorption efficiency of the zirconium functionalized adsorption resin at different pH values ​​is similar to that of Sb(III), indicating that the material can be used in a wide pH range.

[0056] Example 4: Adsorption of Sb(III) at different concentrations by zirconium-functionalized adsorption resin

[0057] Static batch adsorption experiments were conducted by weighing 0.01 g of adsorption resin into 10 mL of Sb(III) solutions of varying concentrations at 30°C. After adsorption for a period of time, the supernatant was filtered, and the ion concentration was measured by ICP-OES, and the adsorption efficiency was calculated.

[0058] The adsorption results of zirconium functionalized adsorption resin for different concentrations of Sb(III) are as follows: Figure 4 As shown in the figure, the adsorption capacity of Sb(III) by the zirconium-functionalized adsorption resin gradually increases with increasing Sb(III) concentration. The adsorption isotherm data were fitted to the Langmuir and Freundlich models, revealing that the adsorption process for Sb(III) conforms to the Langmuir model, with a maximum adsorption capacity of 56.25 mg / g.

[0059] Example 5: Adsorption of Sb(V) at different concentrations by zirconium-functionalized adsorption resin

[0060] The zirconium-functionalized adsorption resin was used to adsorb Sb(V) at various concentrations using a similar adsorption procedure as in Example 4. After adsorption for a period of time, the supernatant was filtered out using a filter head, and the residual antimony concentration was measured by ICP-OES, and the adsorption efficiency was calculated.

[0061] The adsorption results of zirconium functionalized adsorption resin on different concentrations of Sb(V) are as follows: Figure 5 As shown in the figure, the adsorption capacity of Sb(V) by the zirconium-functionalized adsorption resin gradually increases with increasing Sb(V) concentration. The adsorption isotherm data were fitted to the Langmuir and Freundlich models, revealing that the adsorption process for Sb(V) conforms to the Langmuir model, with a maximum adsorption capacity of 240.96 mg / g.

[0062] Example 6: Experiment on the reuse of antimony by zirconium-functionalized adsorption resin

[0063] Weigh 0.01 g of adsorption resin and place it in 10 mL of an aqueous solution containing antimony at 30°C. After adsorption at natural pH for a period of time, filter the supernatant and measure the residual antimony concentration using ICP-OES to calculate the removal rate. The antimony-loaded resin is washed three times with deionized water and eluted with a 1 mol / L NaOH solution. For each adsorption experiment, wash the resin three times with deionized water before repeating the next cycle. Repeat this cycle five times.

[0064] The experimental results of the repeated use of antimony by zirconium functionalized adsorption resin are as follows: Figure 6 As shown in the figure, it can be concluded that after five cycles, the adsorption efficiency of zirconium functionalized adsorption resin for antimony remains basically unchanged, indicating that this adsorption material has good reusability in the process of removing antimony.

[0065] Example 7: Static adsorption experiment of antimony in mine water by zirconium functionalized adsorption resin

[0066] A static batch adsorption experiment was conducted by weighing 0.01 g of adsorption resin and adding it to 10 mL of antimony-containing mine water at 30°C. After a period of adsorption, the supernatant was filtered out using a filter, and the ion concentration was measured by ICP-OES, and the adsorption efficiency was calculated.

[0067] The adsorption results of zirconium functionalized adsorption resin on antimony in mine water are as follows: Figure 7 As shown in the figure, it can be concluded that the zirconium functionalized adsorption resin can not only efficiently adsorb antimony from groundwater, but also adsorb the toxic ion arsenic at the same time.

[0068] Example 8: Dynamic adsorption experiment of antimony in mine water by zirconium functionalized adsorption resin

[0069] Wet zirconium-functionalized adsorption resin was filled into an adsorption column, and antimony-containing groundwater was pumped into the column. Dynamic adsorption evaluation conditions: The adsorption column volume was 1 mL, and a certain amount of zirconium-functionalized adsorption resin was filled. The antimony-containing mine water had an antimony concentration of 10.16 mg / L.

[0070] According to the above experimental conditions, dynamic adsorption experiment evaluation was carried out, and the results were obtained by sampling and analyzing at specific time intervals. Figure 8 The results show that the zirconium-functionalized adsorption resin can effectively remove antimony from mine water, indicating that this zirconium-functionalized resin has the potential for large-scale industrial removal of antimony.

[0071] Example 9: Dynamic elution experiment of antimony from mine water using zirconium functionalized adsorption resin

[0072] 1 mol / L sodium hydroxide was used as the eluent to elute the zirconium functionalized adsorption resin loaded with antimony in Example 8. Figure 9It can be seen from the desorption experimental results that only 20BV of eluent is needed to achieve an elution rate of more than 99%.

[0073] It can be seen from the above examples that this method improves the key reaction participants and applies zirconium-functionalized adsorption resin materials to the recovery of antimony. It can be used in particular for the adsorption of low-content antimony in mine water and can also remove the highly toxic arsenic at the same time. It is simple to operate and suitable for large-scale recovery of low-concentration antimony.

[0074] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be included therein. Any reference sign in a claim should not be construed as limiting the claim to which it relates.

[0075] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A method for removing antimony using a zirconium-functionalized adsorption resin, characterized in that: The following steps are involved: Step 1): adjusting the pH of a solution containing antimony ions to 1-11, and then adding a zirconium-functionalized adsorption resin thereto to adsorb the antimony ions in the antimony ion-containing solution; Step 2): After adsorption is completed, the antimony loaded on the zirconium functionalized adsorption resin is eluted, concentrated, separated and regenerated using an eluent to achieve removal of the antimony; In the above step 1), the zirconium-functionalized adsorption resin is a zirconium-functionalized adsorption resin obtained by surface modification of a polymer substrate; the chemical structure of the zirconium-functionalized adsorption resin is: ,in, represents polymer substrate; The surface modification method of the zirconium functionalized adsorption resin comprises the following steps: Step (a): firstly grafting an unsaturated monomer containing an epoxy group or a halogen onto the surface of a polymer substrate to modify the substrate to form a functional intermediate I; The mass ratio of the polymer substrate to the epoxy group or halogen unsaturated monomer emulsion is (1-2): (5-20), and the epoxy group or halogen unsaturated monomer emulsion contains 30% by mass of the epoxy group or halogen unsaturated monomer; Step (b): introducing a compound having sodium carboxylate on the surface of the functional intermediate I through an epoxy ring-opening reaction or a halogenation reaction to obtain a functional intermediate II; The mass ratio of the functional intermediate I to the compound having sodium carboxylate is (1-2): (10-20); Step (c): finally, a chelating reaction is carried out between the carboxyl group of the functional intermediate II and zirconium oxychloride ZrOCl2 to obtain a zirconium functionalized adsorption resin; Wherein, the mass ratio of the functional intermediate II to zirconium oxychloride is (1-2): (10-20); In the above step (a), the polymer substrate is selected from one of cellulose, lignin, chitosan or its derivatives, polyethylene, polypropylene, polystyrene, polystyrene-divinylbenzene copolymer, ethylene-vinyl alcohol copolymer, and polyamide; The crystallinity of the cellulose or its derivative is above 80%; In the above step 2), the eluent is a 1 mol / L to 3 mol / L sodium hydroxide solution.

2. The method for removing antimony using a zirconium-functionalized adsorption resin according to claim 1, wherein: In the above step (a), the unsaturated monomer containing epoxy group or halogen is selected from one of glycidyl methacrylate GMA, allyl alcohol glycidyl ether, glycidyl acrylate, chloroethyl methacrylate, chloroethyl acrylate, and chloromethylstyrene.

3. The method for removing antimony using a zirconium-functionalized adsorption resin according to claim 1, wherein: In the above step (b), the compound having sodium carboxylate is one of sodium iminodiacetic acid, sodium aminoacetate, and sodium alanine.

4. The method for removing antimony using a zirconium-functionalized adsorption resin according to claim 1, wherein: In the above step (a), the grafting method for modifying the surface of the polymer substrate is an ionizing radiation grafting method or a chemical grafting method; The ionizing radiation grafting method is electron beam pre-radiation grafting, and the irradiation dose used in the electron beam pre-radiation grafting is 10 to 100 kGy; The chemical grafting method is grafted by using an initiator; the initiator is an organic peroxide or an azo initiator, wherein the organic peroxide is one of cyclohexanone peroxide, dibenzoyl peroxide or tert-butyl hydroperoxide; the azo initiator is azobisisobutyronitrile or azobisisoheptanenitrile.

5. The method for removing antimony using a zirconium-functionalized adsorption resin according to claim 1, wherein: In the above step (b), when the compound containing sodium carboxylate is introduced onto the surface of the polymer substrate through the epoxy ring-opening reaction, it is specifically achieved through a solvothermal reaction; the solvent used in the solvothermal reaction is one of water, methanol, toluene, ethylene glycol or N,N-dimethylformamide, and the reaction temperature of the solvothermal reaction is 80-140°C.

6. The method for removing antimony using a zirconium-functionalized adsorption resin according to claim 1, wherein: In the above step (c), when zirconium functionalization is achieved by reacting sodium carboxylate and zirconium oxychloride, it is specifically achieved through a hydrothermal reaction; the concentration of the zirconium oxychloride solution used in the hydrothermal reaction is 10-20wt%, and the reaction temperature of the hydrothermal reaction is 80-120°C.

7. The method for removing antimony using a zirconium-functionalized adsorption resin according to claim 1, wherein: The polymer substrate is spherical, fibrous or film-shaped; accordingly, the obtained zirconium-functionalized adsorption resin is also spherical, fibrous or film-shaped; When the zirconium functionalized adsorption resin is a spherical resin, the average particle size of the spherical resin is 100-1000 μm.

8. The method for removing antimony using a zirconium-functionalized adsorption resin according to claim 1, wherein: In the above step 1), the antimony-containing solution mainly includes the leachate of stibnite, stibnite, antimony ochre, or antimony-containing groundwater.

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