A method for efficiently recovering persulfate from contaminated wastewater by using resin

Abstract

The application belongs to the field of water treatment, and particularly relates to a method for efficiently recovering persulfate from sewage and waste water by using resin. The method for efficiently recovering persulfate from sewage and waste water by using resin is characterized in that it comprises the following steps: S1, adding an acidic solution or an alkaline solution to sewage and waste water containing persulfate to adjust the pH of the sewage and waste water to 3-9; S2, after the pH adjustment is completed, adding resin to the sewage and waste water containing persulfate to adsorb the persulfate in the sewage and waste water; the adsorption capacity of the resin for adsorbing the persulfate is 60-100 mg / g. The application uses resin to adsorb the oxidant persulfate in sewage and waste water, has a relatively wide pH range, is less disturbed by temperature and water body matrix, and is suitable for recovering persulfate from various types of sewage and waste water.

Description

Technical Field

[0001] This invention belongs to the field of water treatment, specifically relating to a method for efficiently recovering persulfate from wastewater using resin. Background Technology

[0002] In recent years, persulfate has been widely used in water treatment due to its ability to generate strong oxidizing reactive oxides such as sulfate radicals through activation, thus removing recalcitrant pollutants. Current research focuses primarily on the generation pathways and oxidation characteristics of free radicals during persulfate activation. However, the utilization rate of the sulfate oxidant itself during the persulfate oxidation reaction is low (20%-60%), resulting in a large amount of persulfate remaining in wastewater. In wastewater, persulfate can react with aquatic substrates to generate sulfate ions, which are then converted into H2S by microorganisms under anaerobic conditions, posing a potential threat to the aquatic ecosystem. Despite this, sufficient attention remains to the recovery and reuse of persulfate after the wastewater oxidation reaction.

[0003] Resins are a class of high-molecular polymer materials characterized by their porous structure, high mechanical strength, strong ion exchange capacity, and resistance to acids and alkalis. They are commonly used to immobilize nano-metal oxides (such as iron oxides, zirconium oxides, and lanthanum oxides) to prepare resin-based environmental purification materials. Numerous studies have shown that resins can recover heavy metal ions and inorganic phosphorus pollutants from wastewater through ion exchange. However, there are no reports on the use of resins to recover persulfate from wastewater. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the objective of this invention can be achieved through the following technical solutions:

[0005] A method for efficiently recovering persulfate from wastewater using resin includes the following steps:

[0006] S1. Add acidic or alkaline solutions to the wastewater containing persulfate to adjust the pH of the wastewater to 3-9;

[0007] S2. After pH adjustment, resin is added to the wastewater containing persulfate to adsorb the persulfate in the wastewater. The adsorption capacity of the resin for persulfate is 60-100 mg / g.

[0008] Preferably, the acidic solution is either a sulfuric acid solution or a hydrochloric acid solution; the alkaline solution is either a sodium hydroxide solution or a sodium carbonate solution.

[0009] Preferably, the persulfate is at least one of permonosulfate or perdisulfate.

[0010] Preferably, the resin is at least one of styrene-divinylbenzene resin with quaternary ammonium groups, styrene-divinylbenzene resin with tertiary amine groups, and methyl acrylate copolymer crosslinking polymer resin.

[0011] Preferably, the wastewater is at least one of surface water, domestic sewage, aquaculture wastewater, dyeing and printing wastewater, photovoltaic wastewater, and electroplating wastewater.

[0012] The above-described method for efficiently recovering persulfate from wastewater using resin is applied in the field of degrading organic pollutants.

[0013] Preferably, the organic pollutant is at least one of amino acids, dyes, phenols, and antibiotics.

[0014] The beneficial effects of this invention are:

[0015] 1. This invention utilizes resin to adsorb the oxidant persulfate in wastewater. It has a wide pH range and is less affected by temperature and water matrix, making it suitable for recovering persulfate from various types of wastewater.

[0016] 2. This invention utilizes resin adsorption to recover persulfate, which can then be used as a solid oxidant. It can not only directly oxidize recalcitrant organic pollutants in water, but also be activated by transition metal ions to generate enhanced free radicals such as sulfate radicals, thereby achieving the removal of target pollutants. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of this disclosure or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, those skilled in the art can obtain other drawings based on these drawings without creative effort.

[0018] Figure 1 The effect of different initial concentrations of PMS on the adsorption of PMS by D201 resin;

[0019] Figure 2 The effect of pH on the adsorption of PMS by D201 resin;

[0020] Figure 3 The effect of temperature on the adsorption of PMS by D201 resin;

[0021] Figure 4 The effect of the water matrix on the adsorption of PMS by D201 resin;

[0022] Figure 5 The effect of different actual water bodies on the adsorption of PMS by D201 resin;

[0023] Figure 6It refers to the resin's ability to adsorb PMS and oxidize organic pollutants. Detailed Implementation

[0024] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] The styrene-divinylbenzene resin with quaternary ammonium groups is designated as D201;

[0026] Persulfate is PMS;

[0027] Persulfate is PDS.

[0028] Example 1

[0029] S1. Add sodium hydroxide solution to the wastewater containing persulfate (PMS) to adjust the pH of the wastewater to 9;

[0030] S2. After pH adjustment, D201 resin was added to the wastewater containing persulfate (PMS) to adsorb the persulfate in the wastewater. The adsorption capacity of the resin for persulfate was 60 mg / g. During the adsorption process, the experimental temperature was controlled at 20℃ using a constant temperature water bath.

[0031] This experiment was conducted in five separate experiments, with the concentrations of permonosulfate (PMS) in the wastewater being 0.4 mM, 0.6 mM, 0.8 mM, 1.0 mM, and 1.2 mM, respectively.

[0032] After the experiment began, 1 mL of the reaction solution was taken at pre-set sampling times, and the concentration of PMS in the solution was determined using iodometric titration. Figure 1 As shown, the adsorption capacity of D201 resin for PMS increases significantly with increasing initial PMS concentration. When the initial PMS concentration is 1.2 mM, the adsorption capacity of D201 resin is 90 mg / g.

[0033] Example 2

[0034] S1. Add sodium hydroxide solution or sulfuric acid solution to the wastewater containing permonosulfate (PMS) to adjust the pH of the wastewater;

[0035] S2. After pH adjustment, D201 resin was added to the wastewater containing persulfate (PMS) to adsorb the persulfate in the wastewater. The adsorption capacity of the resin for persulfate was 70 mg / g. During the adsorption process, the experimental temperature was controlled at 20℃ using a constant temperature water bath.

[0036] This experiment was conducted in six separate experiments, with the pH values ​​of the wastewater containing permonosulfate (PMS) being pH=1, pH=3, pH=5, pH=7, pH=9, and pH=11, respectively.

[0037] After the experiment began, at pre-set sampling times, 1 mL of the reaction solution was taken and the concentration of PMS in the solution was determined using iodometric titration. Figure 2 The data shows that the optimal pH range for D201 resin to adsorb persulfate (PMS) is 3-9.

[0038] Example 3

[0039] S1. Add sodium hydroxide solution to the wastewater containing persulfate (PMS) to adjust the pH of the wastewater to 9;

[0040] S2. After pH adjustment, D201 resin is added to the wastewater containing persulfate (PMS) to adsorb the persulfate in the wastewater. The adsorption capacity of D201 for persulfate is 60 mg / g.

[0041] This experiment was conducted in five separate experiments, in which the reaction temperature was controlled at 10℃, 20℃, 30℃, 40℃ and 50℃ respectively in a constant temperature water bath during the adsorption process.

[0042] After the experiment began, at pre-set sampling times, 1 mL of the reaction solution was taken and the concentration of PMS in the solution was determined using iodometric titration. Figure 3 The data shows that temperature has little effect on the adsorption of PMS by D201 resin, and the adsorption capacity of D201 resin for PMS is 70 mg / g.

[0043] Example 4

[0044] S1. Add sodium hydroxide solution to the wastewater containing persulfate (PMS) to adjust the pH of the wastewater to 9;

[0045] S2. After pH adjustment, D201 resin was added to the wastewater containing persulfate (PMS) to adsorb the persulfate in the wastewater. The adsorption capacity of D201 for persulfate is 80 mg / g. During the adsorption process, the experimental temperature was controlled at 20℃ using a constant temperature water bath.

[0046] This experiment was conducted in six separate experiments, each with a different water matrix in the wastewater, including those containing NO. 3- Wastewater containing SO4 2- Wastewater containing Cl - Wastewater containing HCO3 - Wastewater containing humic acid (HA), and clean water free of any impurities.

[0047] After the experiment began, 1 mL of the reaction solution was taken at pre-set sampling times, and the concentration of PMS in the solution was determined using iodometric titration. Figure 4 The data in the middle can show NO 3- SO4 2- Cl - HCO3 - Furthermore, humic acid (HA) has minimal interference with the adsorption of PMS by D201 resin.

[0048] Example 5

[0049] S1. Add sodium hydroxide solution to the wastewater containing persulfate (PMS) to adjust the pH of the wastewater to 9;

[0050] S2. After pH adjustment, D201 resin was added to the wastewater containing persulfate (PMS) to adsorb the persulfate in the wastewater. The adsorption capacity of D201 resin for persulfate is 80 mg / g. During the adsorption process, the experimental temperature was controlled at 20℃ using a constant temperature water bath.

[0051] This experiment was conducted in four separate experiments, each with a different source of wastewater, including tap water, river water, pure water, and sewage.

[0052] After the experiment began, 1 mL of the reaction solution was taken at pre-set sampling times, and the concentration of PMS in the solution was determined using iodometric titration. Figure 5 The data shows that, compared with the ultrapure water system, different wastewaters have virtually no impact on the adsorption of PMS by the D201 resin, and the adsorption capacity of the D201 resin for PMS remains at 70 mg / g.

[0053] Example 6

[0054] S1. Add sodium hydroxide solution to the wastewater containing permonosulfate (PMS) and the target pollutant to adjust the pH of the wastewater to 9;

[0055] S2. After pH adjustment, D201 resin was added to the wastewater containing persulfate (PMS) and the target pollutant to adsorb the persulfate in the wastewater. The adsorption capacity of D201 resin for persulfate is 8 mg / g. During the adsorption process, the experimental temperature was controlled at 20℃ using a constant temperature water bath.

[0056] This experiment was conducted in three separate experiments, each with a different target pollutant in the wastewater. The target pollutants in the wastewater of each experiment were carbamazepine, sulfamethoxazole, and 2,4,6-trichlorophenol, respectively.

[0057] After the experiment began, at pre-set sampling times, 1 mL of the reaction solution was taken at each time to determine the content of the target pollutant in the reaction solution. Figure 6 The data shows that the D201 resin, after adsorbing PMS, still retains the ability to oxidize pollutants.

[0058] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0059] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A method for efficiently recovering persulfate from wastewater using resin, characterized in that, Includes the following steps: S1. Add acidic or alkaline solutions to the wastewater containing persulfate to adjust the pH of the wastewater to 3-9; S2. After pH adjustment, resin is added to the wastewater containing persulfate to adsorb the persulfate in the wastewater. The adsorption capacity of the resin for persulfate is 60-100 mg / g. The resin is at least one of the following: styrene-divinylbenzene resin with quaternary ammonium groups, styrene-divinylbenzene resin with tertiary amine groups, and methyl acrylate copolymer crosslinking polymer resin.

2. The method for efficiently recovering persulfate from wastewater using resin according to claim 1, characterized in that, The acidic solution is either a sulfuric acid solution or a hydrochloric acid solution; the alkaline solution is either a sodium hydroxide solution or a sodium carbonate solution.

3. The method for efficiently recovering persulfate from wastewater using resin according to claim 1, characterized in that, The persulfate is at least one of permonosulfate or perdisulfate.

4. The method for efficiently recovering persulfate from wastewater using resin according to claim 1, characterized in that, The wastewater is at least one of the following: surface water, domestic sewage, aquaculture wastewater, printing and dyeing wastewater, photovoltaic wastewater, and electroplating wastewater.

5. The application of the method for efficiently recovering persulfate from wastewater using resin as described in any one of claims 1-4 in the field of degrading organic pollutants.

6. The application of the method for efficiently recovering persulfate from wastewater using resin as described in claim 5 in the field of organic pollutant degradation, characterized in that, The organic pollutant is at least one of amino acids, dyes, phenols, and antibiotics.

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