CN107694612B - Material for removing bromate and precursor thereof in water, and preparation method and application thereof - Google Patents

Material for removing bromate and precursor thereof in water, and preparation method and application thereof Download PDF

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CN107694612B
CN107694612B CN201710792868.3A CN201710792868A CN107694612B CN 107694612 B CN107694612 B CN 107694612B CN 201710792868 A CN201710792868 A CN 201710792868A CN 107694612 B CN107694612 B CN 107694612B
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resin
water
ethanol
mixed solution
fecl
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CN107694612A (en
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赵振刚
许争明
刘瑞海
扶雄
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South China University of Technology SCUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers

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Abstract

The invention discloses a material for removing bromate and a precursor thereof in water, and a preparation method and application thereof. The method comprises the following steps: (1) swelling the resin in FeCl under the protection of nitrogen3·6H2Adding FeCl into the ethanol-water mixed solution of O2·4H2Mixing the ethanol-water mixed solution of O under stirring, and performing ultrasonic treatment to obtain Fe3+And Fe2+The resin is uniformly distributed in macropores; (2) under the protection of nitrogen, dropwise adding a sodium hydroxide solution into the mixed solution obtained after the ultrasound in the step (1), stirring for reaction, and then heating to 60-65 ℃ for reaction; (3) after the reaction is finished, cooling to room temperature, filtering, washing and drying to obtain the magnetized resin, namely the material for removing the bromate and the precursor thereof in the water. The magnetized resin is applied to removing bromate and precursors thereof in water, and the method has the advantages of long-term recycling of materials, high removal efficiency, high separation speed and the like.

Description

Material for removing bromate and precursor thereof in water, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a material for removing bromate and a precursor thereof in water, and a preparation method and application thereof.
Background
With the promotion of industrialization and urbanization, the discharge of various industrial waste water and domestic sewage causes great harm to ground water sources, so that the quality of drinking water sources is deteriorated, and the problem of drinking water source pollution universally exists in the world. The drinking water safety problem caused by water pollution seriously threatens the physical health of people. With the use of ozone disinfection processes, it also has a negative impact on drinking water safety. Bromate generated by ozone advanced treatment of drinking water is determined as a grade 2B potential carcinogen by the international cancer research organization, and the limit value of the bromate is 10 mu g/L according to the sanitary Standard for Drinking Water (GB5749-2006) in China.
Currently, there are two main ways to control the bromate content in drinking water. The first is to control the formation of bromate during ozonation. Mainly by lowering pH, adding ammonia and adding H2O2Etc. to reduce the formation of bromate. However, these methods require the introduction of other materials, which increase costs and may cause secondary pollution or reduce ozonization effects. The second method is to remove bromate generated in water. The techniques for removing bromate include activated carbon adsorption removal method, membrane treatment method, ferrous ion reduction removal method, zero-valent iron reduction removal method, biological method, ultraviolet light degradation, Pd/Al 203Catalytic reduction, layered double hydroxide adsorption reduction, and the combination of activated carbon and electrodes to reduce bromate into non-toxic and harmless bromide ions. The methods have disadvantages, such as an activated carbon adsorption method, when natural organic matters and high-concentration other ions exist in water, the bromate removal capacity of the activated carbon is reduced, and when fresh activated carbon is converted into Biological Activated Carbon (BAC), the bromate removal rate tends to be weakened, the bromate removal effect is poor, and the like; the membrane treatment process is too costly; fe2+The zero-valent iron reduction method and the biological method have high removal efficiency of the bromate, but the removal efficiency of the bromate inevitably generates Fe3+、Fe2+And microbial metabolites, introduce secondary pollution, and the nanometer zero-valent iron is very easy to be oxidized in the air, and has poor stability; the ultraviolet light degradation method consumes too much energy; the layered double hydroxide adsorption reduction method has the disadvantages that the regeneration can not be realized when the layered double hydroxide is converted into alpha-FeOOH and amorphous aluminum hydroxide; Pd/Al 203The catalytic reduction method has the defect that the catalyst is difficult to recover and can cause secondary pollution in water.
Compared with the methods for removing bromate, the novel magnetic anion exchange resin has the advantages of high efficiency, low energy consumption, less material consumption, reproducibility and the like, and is a drinking water deep treatment process technology with wide development prospect.
Ion exchange resins are a class of particulate materials that have active functional groups and are capable of exchanging charged exchangeable ions with other ions in a medium (water, organic solvents, gases). The structure of the ion exchange resin consists of three parts: an insoluble three-dimensional space-network skeleton; a functional group attached to the backbone; exchangeable ions of opposite charge carried by the functional groups. Aqueous solutionIn which a functional group attached to a fixed skeleton of an anion exchange resin dissociates to form an exchangeable anion (e.g., Cl)-、OH-) The latter is free to move over a large range and can diffuse into the solution. At the same time, like-charged ions (e.g. Br) in solution-、BrO3 -) The ion exchange resin can also diffuse into the whole resin porous structure, the concentration difference between the two ions promotes the mutual exchange of the two ions, and the larger the concentration difference is, the faster the exchange speed is; and because certain functional groups carried on the ion exchange resin have different affinities with various ions, the exchangeable ions dissociated from the functional groups can be exchanged with the like-charged ions in the solution under the condition of artificial control.
Because the framework structure of the ion exchange resin is fixed and the ion exchange process is a reversible reaction, the ion exchange process is greatly influenced by the ion concentration, and the resin can be regenerated by utilizing the characteristic, so the resin can be used repeatedly for a long time in theory.
However, the traditional anion exchange resin is not easy to keep suspended when reacting with raw water under the stirring state, and the sedimentation speed is too slow, so the traditional resin is loaded with magnetic iron oxide to make the resin have magnetism, and the resin keeps the suspended state when in use, and the resin sedimentation can be accelerated due to the aggregation effect of the magnetism, thereby realizing the rapid separation of the resin and the water. The invention provides a novel method for removing trace bromate and precursors thereof in water by using resin-loaded magnetic iron oxide.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a material for removing bromate and a precursor thereof in water, and a preparation method and application thereof. The method has the advantages of long-term recycling of materials, high removal efficiency, high separation speed and the like.
The invention is realized by the following technical scheme.
A preparation method of a material for removing bromate and precursors thereof in water comprises the following steps:
(1) swelling the resin in FeCl under the protection of nitrogen3· 6H2Ethanol-water mixture of OAdding FeCl into the mixed solution2·4H2Mixing the ethanol-water mixed solution of O under stirring, and performing ultrasonic treatment to obtain Fe3+ And Fe2+The resin is uniformly distributed in macropores;
(2) under the protection of nitrogen, dropwise adding a sodium hydroxide solution into the mixed solution obtained after the ultrasound in the step (1), stirring for reaction for 1-2 h, heating to 60-65 ℃, and reacting for 2-3 h, wherein the reaction formula is as follows: 2Fe3+ + Fe2+ + 8OH— → Fe3O4 + 4H 2O; to ensure adequate reaction, the volume of the sodium hydroxide solution is greater than about theoretical.
(3) After the reaction is finished, cooling to room temperature, filtering, washing and drying to obtain the magnetized resin, namely the material for removing the bromate and the precursor thereof in the water.
Preferably, the resin in step (1) is a macroporous magnetic anionic resin, such as Amberlite FPA90Cl resin, D730 resin, Amberlite IRA958Cl and the like, and further preferably Amberlite FPA90Cl resin.
Preferably, the swelling in the step (1) is performed for 4-5 hours in a water bath at a constant temperature of 30-40 ℃.
Preferably, the FeCl used in step (1)3·6H2The concentration of the ethanol-water mixed solution of O is 2-3 mol/L, and the FeCl2·4H2The concentration of the ethanol-water mixed solution of O is 1-1.5 mol/L, wherein the volume ratio of ethanol to water is 1: 1-2.
Preferably, the FeCl used in step (1)3· 6H2Ethanol-water mixed solution of O and FeCl2·4H2The total volume of the ethanol-water mixed solution of O is 8-10 times of the volume of the resin.
Preferably, the FeCl used in step (1)2·4H2The volume of the ethanol-water mixed solution of O is larger than that of FeCl3·6H2Volume of ethanol-water mixed solution of O to prevent Fe2+Is oxidized.
Preferably, the concentration of the sodium hydroxide solution in the step (2) is 10-12 mol/L; the sodium hydroxide solution is added dropwise within 30-50 min.
Preferably, step (A)2) The dosage of the sodium hydroxide solution is FeCl3· 6H2The volume of the ethanol-water mixed solution of O is 0.8-1 time.
Preferably, the washing in the step (3) is to filter the product, wash the product with distilled water until the filtrate is neutral, and wash the product with absolute ethyl alcohol for 2-3 times.
Preferably, the drying in the step (3) is drying in a vacuum drying oven at 60 ℃ for 48 h.
The magnetized resin prepared by the preparation method is applied to removing bromate and precursors thereof in water.
Compared with the prior art, the invention has the following advantages:
1. the resin magnetized by the method is applied to removing bromate and precursors thereof in water, and has the advantages of long-term recycling of materials, high removal efficiency (> 90%), high separation speed and the like.
2. The magnetized resin can take out bromate with higher concentration to be less than 10 mu g in a shorter time under lower adding amount, and meets the requirements of sanitary standard of domestic application water.
3. The raw materials required by the invention, such as ferric chloride, ferrous chloride and sodium hydroxide, have wide sources, are cheap and easily available, have low industrial operation cost and can be widely applied.
4. The invention has wide application range, can be effectively carried out at the temperature of 15-55 ℃, and can smoothly carry out the reaction in a wide pH value range (4-9).
5. The resin after magnetization can be regenerated in a salt solution such as a sodium chloride solution after saturation adsorption, and the regenerated resin has high adsorption efficiency, namely strong regeneration capacity and simple regeneration process.
6. The invention has the advantages of simple process and low requirement on operation management.
Drawings
FIGS. 1a and 1b are SEM images of the FPA90Cl resin of example 1 before magnetization;
FIGS. 1c and 1d are SEM images of the FPA90Cl resin of example 1 after magnetization;
a, B in FIG. 2 are Fourier infrared spectra before and after magnetization of FPA90Cl resin in example 1;
FIG. 3 is a graph of the removal of bromate and bromide from magnetized FPA90Cl resin of example 1;
FIG. 4 is a graph of the removal of bromate and bromide from magnetized FPA90Cl resin of example 2;
FIG. 5 is a graph of the removal of bromate and bromide from magnetized FPA90Cl resin of example 3;
FIG. 6 is a graphical representation of the kinetic fit of magnetized FPA90Cl resin to remove bromate in examples 1, 2, and 3;
FIG. 7 is a graph of the effect of the magnetized resin of example 6 on bromate removal at different initial solution pH's.
Detailed Description
Specific embodiments of the present invention will be further described below with reference to the drawings and examples, but the present invention is not limited thereto.
Example 1
(1) In N2Under protection, 20 ml of FPA90Cl anion resin and 100ml of 2 mol/L FeCl3· 6H2Adding an ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 1) into a 500 ml three-neck flask, and swelling for 4 hours under the conditions of constant temperature of a water bath at 30 ℃ and continuous stirring; then 100ml of 1 mol/L FeCl is added2·4H2Mixing the ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 1) for 1 h under continuous stirring; then the obtained mixed solution is subjected to ultrasonic treatment for 2 hours to lead Fe3+ And Fe2+The distribution is uniform in the macropores of the resin.
(2) In N2And (2) under the protection, continuous stirring and ultrasonic assistance, dropwise adding 80 ml of 10 mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), continuously stirring for reacting for 1 h, heating to 65 ℃, and continuously reacting for 2 h.
(3) And cooling to room temperature after the reaction is finished, filtering the product, washing the product with distilled water until the filtrate is neutral, washing the product with absolute ethyl alcohol for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 48 hours to obtain the magnetized FPA90Cl anion resin. In the embodiment, as shown in fig. 1a and 1b, scanning electron microscope images of the FPA90Cl before resin magnetization are shown, it can be seen that the resin surface before magnetization is smooth, no attachments are present, the pore channels are clear, and the pores are hollow; the scanning electron microscope images of the magnetized FPA90Cl resin are shown in FIG. 1c and FIG. 1d, and it can be seen that the magnetized resin has a rough surface, iron oxide adheres to the resin, clear channels are not visible, and the resin is filled with the iron oxide. The infrared spectra of the resin before and after magnetization are shown as A, B in FIG. 2, and absorption peaks at 465 and 627 are observed as Fe-O bonds.
(4) At normal temperature, 500 ml of BrO is added into a 1000 ml beaker3 -And Br-Mixing the solution of BrO3 -The concentration is 50 mu g/L, Br-The concentration was 200. mu.g/L. 0.5000 g of magnetized FPA90Cl anion resin was added thereto, and the mixture was continuously stirred with a magnetic stirrer at 300 rpm for 60min, sampled at different time intervals, and the BrO in the solution was measured by ion chromatography (ICS-900; Dionex)3 -And Br-The concentration of (c).
In this example, the pH of the initial solution of the experiment was not adjusted to 6.19; as shown in figure 3, after the reaction time is 30 min, the bromate content is reduced to below 10 mu g/L, and the requirement of GB5749-2006 is met. The BrO in the reaction solution is measured after the reaction is carried out for 60min3 -The concentration is 3.40 mu g/L, Br-The concentration is 5.69 mug/L, and the removal rate of the resin is close to 95 percent.
Example 2
(1) In N2Under protection, 25ml of FPA90Cl anion resin and 3 mol/L FeCl3· 6H2Adding an ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 1) into a 500 ml three-neck flask, and swelling for 5 hours under the conditions of constant temperature of a water bath at 30 ℃ and continuous stirring; then 100ml of 1.5 mol/L FeCl is added2·4H2Mixing the ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 1) for 2 hours under continuous stirring; then the obtained mixed solution is subjected to ultrasonic treatment for 2 hours to lead Fe3+ And Fe2+The distribution is uniform in the macropores of the resin.
(2) In N2Protected, continuously stirred and ultrasonically assisted downAnd (2) dropwise adding 90 ml of 10 mol/L sodium hydroxide solution into the mixed solution obtained in the step (1), completing dropwise adding within 40 min, continuously stirring for reacting for 1 h, and then heating to 65 ℃ for continuously reacting for 3 h.
(3) And cooling to room temperature after the reaction is finished, filtering the product, washing the product with distilled water until the filtrate is neutral, washing the product with absolute ethyl alcohol for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 48 hours to obtain the magnetized FPA90Cl anion resin.
(4) At normal temperature, 500 ml of BrO is added into a 1000 ml beaker3 -And Br-Mixing the solution of BrO3 -The concentration is 100 mu g/L, Br-The concentration was 300. mu.g/L. 0.5000 g of magnetized FPA90Cl anion resin was added thereto, and the mixture was continuously stirred with a magnetic stirrer at 300 rpm for 120 min, sampled at different time intervals, and the BrO in the solution was measured by ion chromatography (ICS-900; Dionex)3 -And Br-The concentration of (c).
In this example, the pH of the initial solution of the experiment was not adjusted to 6.19; as shown in figure 4, after the reaction time is 60min, the bromate content is reduced to below 10 mu g/L, and the requirement of GB5749-2006 is met. The BrO in the reaction solution is measured after the reaction is carried out for 120 min3 -The concentration is 2.47 mu g/L, Br-The concentration is 3.41 mug/L, and the removal rate of the resin is close to 95 percent.
Example 3
(1) In N2Under protection, 25ml of FPA90Cl anion resin and 100ml of 2 mol/L FeCl3· 6H2Adding an ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 2) into a 500 ml three-neck flask, and swelling for 4 hours under the conditions of constant temperature of 35 ℃ water bath and continuous stirring; then 100ml of 1 mol/L FeCl is added2·4H2Mixing the ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 2) for 2 hours under continuous stirring; then the obtained mixed solution is subjected to ultrasonic treatment for 2 hours to lead Fe3+ And Fe2+The distribution is uniform in the macropores of the resin.
(2) In N2Dropping 100ml of 11 mol/L sodium hydroxide solution into the mixed solution obtained in the step (1) under the protection, continuous stirring and ultrasonic assistance, and adding the solution into the mixed solution at 5The dropwise addition is completed within 0min, the stirring reaction is continued for 2 h, and then the temperature is raised to 60 ℃ for further reaction for 2 h.
(3) And cooling to room temperature after the reaction is finished, filtering the product, washing the product with distilled water until the filtrate is neutral, washing the product with absolute ethyl alcohol for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 48 hours to obtain the magnetized FPA90Cl anion resin.
(4) At normal temperature, 500 ml of BrO is added into a 1000 ml beaker3 -And Br-Mixing the solution of BrO3 -The concentration is 200 mu g/L, Br-The concentration was 400. mu.g/L. 0.5000 g of magnetized FPA90Cl anion resin was added thereto, stirred continuously at 300 rpm for 180min, sampled at different time intervals, and BrO in solution was determined by ion chromatography (ICS-900; Dionex)3 -And Br-The concentration of (c).
In this example, the pH of the initial solution of the experiment was not adjusted to 6.19; as shown in figure 5, after 80min of reaction, the bromate content is reduced to below 10 μ g/L, which meets the requirement of GB 5749-2006. The BrO in the reaction solution is measured after the reaction is carried out for 180min3 -The concentration is 2.28 mu g/L, Br-The concentration is 3.41 mug/L, and the removal rate of the resin is close to 95 percent.
As shown in FIG. 6, the adsorption process of bromate in examples 1, 2 and 3 was in accordance with the first order kinetics equation.
Example 4
(1) In N2Under protection, 25ml of FPA90Cl anion resin and 100ml of 3 mol/L FeCl3· 6H2Adding an ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 1) into a 500 ml three-neck flask, and swelling for 4 hours under constant temperature of 40 ℃ water bath and continuous stirring; then 100ml of 1.5 mol/L FeCl is added2·4H2Mixing the ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 1) for 1 h under continuous stirring; then the obtained mixed solution is subjected to ultrasonic treatment for 2 hours to lead Fe3+ And Fe2+The distribution is uniform in the macropores of the resin.
(2) In N2Dropping the mixture obtained in the step (1) under the protection, continuous stirring and ultrasonic assistanceAdding 90 ml of 12 mol/L sodium hydroxide solution, dropwise adding within 40 min, continuously stirring for reacting for 2 h, heating to 60 ℃, and continuously reacting for 3 h.
(3) And cooling to room temperature after the reaction is finished, filtering the product, washing the product with distilled water until the filtrate is neutral, washing the product with absolute ethyl alcohol for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 48 hours to obtain the magnetized FPA90Cl anion resin.
(4) 500 ml of BrO was added to a 1000 ml beaker at 288K,298K,308K,318K and 328K, respectively3 -And Br-Mixing the solution of BrO3 -The concentration is 50 mu g/L, Br-The concentration was 100. mu.g/L. 0.5000 g of magnetized FPA90Cl anion resin was added thereto, and the mixture was continuously stirred with a magnetic stirrer at 300 rpm for 60min, sampled at different time intervals, and the BrO in the solution was measured by ion chromatography (ICS-900; Dionex)3 -And Br-The concentration of (c).
In this example, the pH of the initial solution of the experiment was not adjusted to 6.19; after the reaction was carried out for 60min, BrO in the reaction solution was determined at 288K,298K,308K,318K and 328K3 -The concentrations are respectively 4.02,3.40 and 2.00,<2.00,<2.00 μg/L，Br-the concentration is 6.68,5.70,3.74,3.08,2.00 mu g/L, and the resin pair BrO is in a larger temperature range3 -And Br-The removal rate is higher than 90%, and the residual bromate reaches the requirements of GB 5749-2006.
Example 5
(1) In N2Under protection, 30 ml of FPA90Cl anion resin and 100ml of 3 mol/L FeCl3· 6H2Adding an ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 1.5) into a 500 ml three-neck flask, and swelling for 5 hours in a water bath at the constant temperature of 40 ℃ under continuous stirring; then 100ml of 1.5 mol/L FeCl is added2·4H2Mixing the ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 1.5) for 1 h under continuous stirring; then the obtained mixed solution is subjected to ultrasonic treatment for 2 hours to lead Fe3+ And Fe2+The distribution is uniform in the macropores of the resin.
(2) In N2Protect and continuously stirAnd (2) dropping 100ml of 12 mol/L sodium hydroxide solution into the mixed solution obtained in the step (1) under the assistance of stirring and ultrasound, dropping within 50 min, continuously stirring for reaction for 2 h, and then heating to 65 ℃ for continuous reaction for 3 h.
(3) And cooling to room temperature after the reaction is finished, filtering the product, washing the product with distilled water until the filtrate is neutral, washing the product with absolute ethyl alcohol for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 48 hours to obtain the magnetized FPA90Cl anion resin.
(4) 500 ml of BrO is added into a 1000 ml beaker3 -And Br-Mixed solution of BrO3 -The concentration is 100 mu g/L, Br-The concentration was 300. mu.g/L. 0.1,0.2,0.3,0.4 and 0.5g of magnetized FPA90Cl anion resin were added thereto, respectively, and stirred continuously for 180min at 300 rpm with a magnetic stirrer, samples were taken at different time intervals, and BrO in solution was determined by ion chromatography (ICS-900; Dionex)3 -And Br-The concentration of (c).
In this example, the pH of the initial solution of the experiment was not adjusted to 6.19; when the amount of the resin used was 0.5g, the reaction reached equilibrium at 120 min, at which point BrO3 -The concentration is 2.47 mu g/L, Br-The concentration is 3.41 mug/L; when the amount of the resin used was 0.4 g, the reaction reached equilibrium at 120 min, at which point BrO3 -The concentration is 2.24 mu g/L, Br-The concentration is 3.74 mu g/L; when the amount of the resin used was 0.3g, the reaction reached equilibrium at 150 min, at which point BrO3 -The concentration is 2.47 mu g/L, Br-The concentration is 3.41 mug/L; when the amount of the resin used was 0.2g, the reaction reached equilibrium at 180min, at which point BrO3 -The concentration is 3.87 mu g/L, Br-The concentration is 5.70 mug/L; when the amount of the resin used was 0.1g, the reaction did not reach equilibrium for 180min, at which point BrO3 -The concentration is 9.91 mu g/L, Br-The concentration is 17.46 mu g/L; it is known that at higher concentrations, the resin pairs BrO3 -And Br-Still has higher removal rate, and the residual bromate reaches the requirements of GB 5749-2006.
Example 6
(1) In N2Under protection, 30 ml of FPA90Cl anion resin and 100ml of 3 mol/L FeCl3· 6H2Adding an ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 2) into a 500 ml three-neck flask, and swelling for 4 hours under the conditions of water bath constant temperature of 40 ℃ and magnetic stirring; then 100ml of 1.5 mol/L FeCl is added2·4H2Mixing the ethanol-water mixed solution of O (the volume ratio of ethanol to water is 1: 2) for 1 h under continuous stirring; then the obtained mixed solution is subjected to ultrasonic treatment for 2 hours to lead Fe3+ And Fe2+The distribution is uniform in the macropores of the resin.
(2) In N2And (2) dropwise adding 100ml of 10 mol/L sodium hydroxide solution into the mixed solution obtained in the step (1) under the protection, continuous stirring and ultrasonic assistance, continuously stirring for reacting for 2 hours, and then heating to 65 ℃ for continuously reacting for 3 hours.
(3) And cooling to room temperature after the reaction is finished, filtering the product, washing the product with distilled water until the filtrate is neutral, washing the product with absolute ethyl alcohol for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 48 hours to obtain the magnetized FPA90Cl anion resin.
(4) 500 ml of BrO is added into a 1000 ml beaker3 -Solution, BrO3 -The concentration was 200. mu.g/L. The initial pH of the solution was adjusted to 2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10.0,11.0 using HCl and NaOH solutions, respectively. 0.2g of magnetized FPA90Cl anion resin was added thereto, and the mixture was stirred continuously at 300 rpm for 12 hours with a magnetic stirrer until the adsorption was equilibrated, and BrO in the solution was measured by ion chromatography (ICS-900; Dionex)3 -The concentration of (c).
As shown in FIG. 7, the magnetic resin has a large adsorption rate to bromate at a large pH range (2.0-11.0); and when the pH of the initial solution is 4.0,5.0,6.0,7.0,8.0 and 9.0 respectively, BrO is balanced3 -The concentrations are respectively 7.74 mu g/L, 5.73 mu g/L, 2.78 mu g/L, 5.73 mu g/L, 9.60 mu g/L and 9.91 mu g/L; meets the requirements of GB 5749-2006. Resin to BrO especially under near neutral conditions3 -The removal rate of (2) is highest.

Claims (9)

1. A preparation method of a material for removing bromate and precursors thereof in water is characterized by comprising the following steps:
(1) swelling the resin in FeCl under the protection of nitrogen3· 6H2Adding FeCl into the ethanol-water mixed solution of O2·4H2Mixing the ethanol-water mixed solution of O under stirring, and performing ultrasonic treatment to obtain Fe3+ And Fe2+The resin is uniformly distributed in macropores;
(2) under the protection of nitrogen, dropwise adding a sodium hydroxide solution into the mixed solution obtained after the ultrasonic treatment in the step (1), stirring and reacting for 1-2 h, and then heating to 60-65 ℃ for reacting for 2-3 h;
(3) after the reaction is finished, cooling to room temperature, filtering, washing and drying to obtain magnetized resin, namely the material for removing bromate and precursor thereof in water;
the resin in the step (1) is Amberlite FPA90Cl resin.
2. The method according to claim 1, wherein the swelling in step (1) is carried out in a water bath at a constant temperature of 30 to 40 ℃ for 4 to 5 hours.
3. The method of claim 1, wherein the FeCl of step (1)3·6H2The concentration of the ethanol-water mixed solution of O is 2-3 mol/L, and the FeCl is2·4H2The concentration of the ethanol-water mixed solution of O is 1-1.5 mol/L, wherein the volume ratio of ethanol to water is 1: 1-2.
4. The method of claim 1, wherein the FeCl of step (1)3· 6H2Ethanol-water mixed solution of O and FeCl2·4H2The total volume of the ethanol-water mixed solution of O is 8 to 10 times of the volume of the resin.
5. The method of claim 1, wherein the FeCl of step (1)2·4H2The volume of the ethanol-water mixed solution of O is larger than that of FeCl3·6H2Volume of ethanol-water mixed solution of O.
6. The preparation method according to claim 1, wherein the concentration of the sodium hydroxide solution in the step (2) is 8-10 mol/L; the sodium hydroxide solution is added dropwise within 30-50 min.
7. The method according to claim 1, wherein the sodium hydroxide solution in step (2) is FeCl3· 6H2The volume of the ethanol-water mixed solution of O is 0.8-1 time.
8. A magnetized resin obtained by the method for preparing a material for removing bromate in water and a precursor thereof according to any one of claims 1 to 7.
9. The use of the magnetized resin of claim 8 for removing bromate and its precursors from water.
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