CN102453187B - A kind of polymer hydrogel adsorbing heavy metal and its preparation method and application - Google Patents

Abstract

The invention belongs to the technical field of an absorption material, and particularly relates to polymer hydrogel and a preparation method and application in absorption of heavy metal ions. The polymer hydrogel is a three-dimensional network polymer which is not dissolved in water and is strongly swelled in the water, and is generated by radiation copolymerization of two monomers of hydroxyethyl acrylate (hydrophilic glass-state monomer) and 2-acrylamide-2-methylpropanesulfonic acid. The polymer hydrogel has the structural and property characteristics of low degree of cross linking, high swelling rate, property of not being dissolved in the water, strong water absorbing capability and good water-retaining property, can not be dehydrated under the condition of pressurization after absorbing the water, and simultaneously, has the basic characteristics of a general polymer compound. In the invention, the polymer hydrogel prepared by the radiation copolymerization contains multi-functional groups for absorbing the heavy metals, and has good absorption property to lead, cadmium and other heavy metals. In addition, the synthetic method is simple, the operation is simple, the reaction process is free from other impurities, and a product can be ensured to be pure.

Description

A kind of polymer hydrogel adsorbing heavy metal and its preparation method and application

technical field

The invention belongs to the technical field of adsorption materials, and in particular relates to a polymeric hydrogel, a preparation method thereof and an application in the adsorption of heavy metal ions.

Background technique

In recent years, due to the increasing mining, smelting, processing and commercial manufacturing activities of heavy metals, the amount and types of heavy metals produced have greatly increased, resulting in a large amount of heavy metals entering the soil and water bodies, not only causing serious environmental pollution and resource pollution. It is wasteful and poses a great threat to human health. There are many ways to treat heavy metal wastewater. The most commonly used method is chemical method, which can quickly remove metal ions in wastewater. The process is simple, but there are disadvantages such as high metal concentration in the effluent, easy to produce secondary pollution, and difficult to reuse wastewater. . The adsorption method is also widely used and researched in heavy metal wastewater treatment technology because of its simple treatment process and easy operation. Sorbent mainly contains activated carbon, zeolite, ion resin and chelating resin (such as a kind of chelating resin whose publication number is CN1772386), etc., and there are relatively few studies on hydrogel as sorbent.

Hydrogels are three-dimensional network polymers that are insoluble in water but highly swellable in water. It has the structure and performance characteristics of low cross-linking degree, high swelling rate, and insoluble in water; it has strong water absorption capacity, good water retention, and will not dehydrate even after water absorption, and has the basic characteristics of general polymer compounds. There are a large number of functional groups in the hydrogel, and the adsorption of dyes and heavy metals as a new adsorbent has attracted much attention in recent years. Many natural organic polymers have been studied and applied to the adsorption treatment of heavy metal wastewater due to their rich functional groups. Chitosan biomass materials are a typical representative. The adsorption resin with the patent number CN101701042A is based on chitosan Sugar is a heavy metal adsorption material prepared by chemically modifying the substrate. The structure of chitosan biomass material contains a large number of -NH and -OH groups, these groups have a strong complexation and chelation effect on heavy metal ions, and have a good removal effect on trace heavy metals in water , and the source is extensive and the cost is low. However, this kind of natural biomaterials also has disadvantages such as low mechanical strength, easy biodegradation, and great influence of pH. Artificially synthesized polymer gels with functional groups are also used for the adsorption and separation of heavy metal wastewater. Existing artificially synthesized high molecular polymer hydrogels include polyacrylic acid hydrogels, etc., because they have effective groups such as carboxyl groups that can bind heavy metal ions, they also have a certain effect on the ion adsorption and separation of heavy metal wastewater, but the effect is Not very noticeable. Moreover, most of the existing artificially synthesized polymer hydrogels have relatively complicated synthesis routes and cumbersome operations, which are also major disadvantages.

Contents of the invention

The problem to be solved by the present invention is to provide a polymer hydrogel for adsorbing heavy metals, its preparation method and application.

Technical scheme of the present invention is:

1 The hydrogel of the present invention is a three-dimensional network polymer that is insoluble in water but highly swellable in water, composed of hydroxyethyl acrylate (hydrophilic glassy monomer) and 2-acrylamide-2-methylpropanesulfonate The acid is produced by radiation copolymerization of two monomers. It has the structure and performance characteristics of low cross-linking degree, high swelling rate, and insoluble in water; it has strong water absorption capacity, good water retention, and will not dehydrate even after water absorption, and has the basic characteristics of general polymer compounds.

2. The preparation method of heavy metal adsorption polymer hydrogel, which mainly includes the following steps:

(1) Mix hydroxyethyl acrylate (hydrophilic glassy monomer), 2-acrylamido-2-methylpropanesulfonic acid and distilled water in a certain proportion;

(2) 2-acrylamido-2-methylpropanesulfonic acid plus hydroxyethyl acrylate: the volume ratio of water is (1~2): 5,2-acrylamido-2-methylpropanesulfonic acid and acrylic acid The molar ratio of hydroxyethyl ester is 1: (1~9);

(3) Ultrasonic treatment for 5~20min after mixing;

(4) Inflate nitrogen into the mixture of (1) to ensure anaerobic state;

(5) At a temperature of -63 to -95°C, a high-energy ray with a radiation dose of 1×10 ³ to 1×10 ⁶ Gy is used to irradiate and polymerize to form a hydrogel.

The polymer hydrogel is to the adsorption method of heavy metal ion, and it mainly comprises the following steps:

(1) Cut the prepared polymer hydrogel into small pieces of 1cm×1cm×1cm and put them in the triangular flask;

(2) Wash the polymer hydrogel cut into small pieces multiple times with deionized water;

(3) Adsorb different types of heavy metal ions at 25°C.

3 Compared with the prior art, the beneficial effects of the present invention are:

Existing research on heavy metal adsorption hydrogels mainly focuses on natural organic polymers, especially chitosan as the most common research object, but this kind of natural biomaterials has low mechanical strength, is easily biodegradable, and is affected by pH. very big. Moreover, the preparation process of the existing artificial adsorption hydrogel is relatively complicated, and the adsorption capacity is not high. The present invention proposes a method for preparing adsorption hydrogel by using radiation technology, which can prepare an organic high molecular polymer with functional groups, which can make the functional groups in the polymer effectively adsorb and chelate heavy metal ions, and prepare The method is simple and easy to operate. And the product has a certain mechanical strength, which can prolong the service life.

Description of drawings

Figure 1 is the SEM image of the hydrogel.

Figure 2 is the infrared spectrum of the hydrogel.

Figure 3 is a graph of the adsorption capacity of hydrogels adsorbing Pb ²⁺ at different pHs.

Figure 4 is a graph of the adsorption capacity of hydrogels adsorbing Cd ²⁺ at different pHs.

Fig. 5 is a graph of the adsorption capacity of hydrogels adsorbing Cu ²⁺ at different pHs.

Fig. 6 is a graph showing the adsorption capacity of Cr ³⁺ adsorbed by hydrogel at different pH.

Fig. 7 is a graph of the adsorption capacity of Fe ³⁺ adsorbed by hydrogel at different pH.

Detailed ways

The present invention is further illustrated by examples, but the present invention is not limited to the following examples.

Example 1:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, according to (A+B):C is 3:7 (v/v ) for mixing, where A:B is 2:5 (mol/mol). Use ultrasound to process the mixture to make the mixture uniform;

2. After filling with nitrogen, at a temperature of -78°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ⁶⁰ Co-γ rays) to irradiate and polymerize to form polymer hydrogels;

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask for several times, and then dry them at 40°C;

4. Characterize the structure and composition of the product, including using SEM to observe the pore structure and using infrared spectroscopy to analyze the composition of the product. The results of SEM showed that the product had a good pore structure. The infrared spectrum of the product is compared with the infrared spectrum of the two reactant monomers, which shows that the double bonds of the monomers are opened to form new products after being irradiated by high-energy rays.

Example 2:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (HEA for short) to the above solution, mix evenly, as component B; distilled water as component C, mix according to (A+B):C ratio of 1:5, where A:B is 2:3 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -63°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ¹³⁷ Cs-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the polymer hydrogel and put five parts of the dried product into 100ml Erlenmeyer flasks, and then add 50ml of 1g/L Pb ²⁺ , Cd ²⁺ , Cr ³⁺ , Cu ²⁺ , Fe ³⁺ Five kinds of single solutions, put the triangular flask in a constant temperature oscillator at 25°C for constant temperature adsorption, after 48 hours of full adsorption, measure the concentration of each heavy metal ion solution before and after adsorption. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for each ion can be calculated by the concentration difference of ions before and after adsorption. It has been determined that the adsorption capacity of the product for five metal ions, Pb ²⁺ , Cr ³⁺ , Cd ²⁺ , Cu ²⁺ , and Fe ³⁺ , is 180mg/g, 130mg/g, 110mg/g, 70mg/g, 110mg/g.

Example 3:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (HEA for short) to the above solution, mix evenly, as component B; distilled water as component C, mix according to (A+B):C ratio of 1:5, where A:B is 1:1 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -63°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ⁶⁰ Co-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the polymer hydrogel and put five parts of the dried product into 100ml Erlenmeyer flasks, and then add 50ml of 1g/L Pb ²⁺ , Cd ²⁺ , Cr ³⁺ , Cu ²⁺ , Fe ³⁺ Five kinds of single solutions, put the triangular flask in a constant temperature oscillator at 25°C for constant temperature adsorption, after 48 hours of full adsorption, measure the concentration of each heavy metal ion solution before and after adsorption. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for each ion can be calculated by the concentration difference of ions before and after adsorption. It has been determined that the adsorption capacities of the product for five metal ions, Pb ²⁺ , Cr ³⁺ , Cd ²⁺ , Cu ²⁺ , and Fe ³⁺ , are: 150mg/g, 130mg/g, 110mg/g, 70mg/g, 110mg/g.

Example 4:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (HEA for short) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 2:5, where A:B is 1:5 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -78°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ¹³⁷ Cs-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the polymer hydrogel and put five parts of the dried product into 100ml Erlenmeyer flasks, and then add 50ml of 1g/L Pb ²⁺ , Cd ²⁺ , Cr ³⁺ , Cu ²⁺ , Fe ³⁺ Five kinds of single solutions, put the triangular flask in a constant temperature oscillator at 25°C for constant temperature adsorption, after 48 hours of full adsorption, measure the concentration of each heavy metal ion solution before and after adsorption. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for each ion can be calculated by the concentration difference of ions before and after adsorption. It has been determined that the adsorption capacity of the product for five metal ions, Pb ²⁺ , Cr ³⁺ , Cd ²⁺ , Cu ²⁺ , and Fe ³⁺ , are: 130mg/g, 80mg/g, 70mg/g, 60mg/g, 110mg/g.

Example 5:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (HEA for short) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 2:5, where A:B is 2:3 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -78°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ¹³⁷ Cs-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the polymer hydrogel and put five parts of the dried product into 100ml Erlenmeyer flasks, and then add 50ml of 1g/L Pb ²⁺ , Cd ²⁺ , Cr ³⁺ , Cu ²⁺ , Fe ³⁺ Five kinds of single solutions, put the triangular flask in a constant temperature oscillator at 25°C for constant temperature adsorption, after 48 hours of full adsorption, measure the concentration of each heavy metal ion solution before and after adsorption. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for each ion can be calculated by the concentration difference of ions before and after adsorption. It has been determined that the adsorption capacity of the product for five metal ions, Pb ²⁺ , Cr ³⁺ , Cd ²⁺ , Cu ²⁺ , and Fe ³⁺ , are: 200mg/g, 120mg/g, 130mg/g, 100mg/g, 130mg/g.

Example 6:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 1:9 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at -95°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ⁶⁰ Co-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the polymer hydrogel and put five parts of the dried product into 100ml Erlenmeyer flasks, and then add 50ml of 1g/L Pb ²⁺ , Cd ²⁺ , Cr ³⁺ , Cu ²⁺ , Fe ³⁺ Five kinds of single solutions, put the triangular flask in a constant temperature oscillator at 25°C for constant temperature adsorption, after 48 hours of full adsorption, measure the concentration of each heavy metal ion solution before and after adsorption. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for each ion can be calculated by the concentration difference of ions before and after adsorption. It has been determined that the adsorption capacity of the product for five metal ions, Pb ²⁺ , Cr ³⁺ , Cd ²⁺ , Cu ²⁺ , and Fe ³⁺ , is 140mg/g, 60mg/g, 70mg/g, 80mg/g, 130mg/g.

Example 7:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 1:5 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at -95°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ⁶⁰ Co-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the polymer hydrogel and put five parts of the dried product into 100ml Erlenmeyer flasks, and then add 50ml of 1g/L Pb ²⁺ , Cd ²⁺ , Cr ³⁺ , Cu ²⁺ , Fe ³⁺ Five kinds of single solutions, put the triangular flask in a constant temperature oscillator at 25°C for constant temperature adsorption, after 48 hours of full adsorption, measure the concentration of each heavy metal ion solution before and after adsorption. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for each ion can be calculated by the concentration difference of ions before and after adsorption. It has been determined that the adsorption capacity of the product to five metal ions, Pb ²⁺ , Cr ³⁺ , Cd ²⁺ , Cu ²⁺ , and Fe ³⁺ , are: 160mg/g, 80mg/g, 100mg/g, 80mg/g, 110mg/g.

Example 8:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 2:3 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at -95°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ⁶⁰ Co-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the polymer hydrogel and put five parts of the dried product into 100ml Erlenmeyer flasks, and then add 50ml of 1g/L Pb ²⁺ , Cd ²⁺ , Cr ³⁺ , Cu ²⁺ , Fe ³⁺ Five kinds of single solutions, put the triangular flask in a constant temperature oscillator at 25°C for constant temperature adsorption, after 48 hours of full adsorption, measure the concentration of each heavy metal ion solution before and after adsorption. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for each ion can be calculated by the concentration difference of ions before and after adsorption. It has been determined that the adsorption capacities of the product for five metal ions, Pb ²⁺ , Cr ³⁺ , Cd ²⁺ , Cu ²⁺ , and Fe ³⁺ , are: 190mg/g, 120mg/g, 140mg/g, 80mg/g, 150mg/g.

Example 9:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 1:9 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -78°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ⁶⁰ Co-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the dried product and place seven portions in 100ml Erlenmeyer flasks respectively, and then add 50ml of 2g/L Pb ²⁺ solution at a certain pH. The pH of the solution is 1, 2, 3, 4, 5, 6, 7, respectively. Place the Erlenmeyer flask in a constant temperature oscillator at 25°C for constant temperature adsorption. After fully adsorbed for 48 hours, measure the concentration of Pb ²⁺ in the Pb ²⁺ solution at each pH before and after adsorption. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for Pb ²⁺ can be calculated by the concentration difference of Pb ²⁺ before and after adsorption. It was determined that the hydrogel had the best adsorption effect on Pb ²⁺ when the pH was 6. See attached drawing 3 for details.

Example 10:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 1:9 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -63°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ⁶⁰ Co-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the dry product and put each seven portions into 100ml Erlenmeyer flasks, and then add 50ml of 2g/L Cd ²⁺ solution at a certain pH. The pH of the solution is 1, 2, 3, 4, 5, 6, 7, respectively. Place the Erlenmeyer flask in a constant temperature oscillator at 25°C for constant temperature adsorption. After fully adsorbed for 48 hours, measure the concentration of Cd ²⁺ in the Cd ²⁺ solution at each pH before and after adsorption. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for Cd ²⁺ can be calculated by the concentration difference of Cd ²⁺ before and after adsorption. It has been determined that the hydrogel has the best adsorption effect on Cd ²⁺ when the pH is 6. See attached drawing 4 for details.

Example 11:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 1:9 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -78°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ⁶⁰ Co-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the dried product and place seven portions in 100ml Erlenmeyer flasks respectively, and then add 50ml of 2g/L Cu ²⁺ solution at a certain pH. The pH of the solution is 1, 2, 3, 4, 5, 6, 7, respectively. Place the Erlenmeyer flask in a constant temperature oscillator at 25°C for constant temperature adsorption. After fully adsorbed for 48 hours, measure the concentration of Cu ²⁺ in the Cu ²⁺ solution at each pH before and after adsorption. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for Cu ²⁺ can be calculated by the concentration difference of Cu ²⁺ before and after adsorption. It was determined that the hydrogel had the best adsorption effect on Cu ²⁺ when the pH was 4. See attached drawing 5 for details.

Example 12:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 1:9 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -63°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ⁶⁰ Co-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the dried product and place seven portions in 100ml Erlenmeyer flasks respectively, and then add 50ml of 2g/L Cr ³⁺ solution at a certain pH. The pH of the solution is 1, 2, 3, 4, 5, 6, 7, respectively. Place the Erlenmeyer flask in a constant temperature oscillator at 25°C for constant temperature adsorption. After fully adsorbed for 48 hours, measure the concentration of Cr ³⁺ before and after adsorption of Cr ³⁺ solution at each pH. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for Cr ^{3+ can be calculated by the concentration difference of Cr 3+ before} and after adsorption. It has been determined that the hydrogel has the best adsorption effect on Cr ³⁺ when the pH is 7. See attached drawing 6 for details.

Example 13:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 1:9 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -63°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ⁶⁰ Co-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. Cut the irradiated hydrogel into small pieces of 1cm×1cm×1cm, put them in the Erlenmeyer flask and wash them several times, then dry them at 40°C.

4. Weigh 0.1g of the dry product and place seven portions in each of 100ml Erlenmeyer flasks, then add 50ml of 2g/L Fe ³⁺ solution at a certain pH. The pH of the solution is 1, 2, 3, 4, 5, 6, 7, respectively. Place the triangular flask in a constant temperature oscillator at 25°C for constant temperature adsorption. After fully adsorbing for 48 hours, measure the concentration of Fe ³⁺ in the Fe ³⁺ solution at each pH before and after adsorption. The measurement method is to use the atomic absorption method after dilution. The adsorption capacity of the product for Fe ³⁺ can be calculated by the concentration difference of Fe ³⁺ before and after adsorption. It was determined that the hydrogel had the best adsorption effect on Fe ³⁺ when the pH was 2. See attached drawing 7 for details.

Example 14:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 2:3 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -78°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ¹³⁷ Cs-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. The irradiated hydrogel was cut into small pieces of 1 cm×1 cm×1 cm, washed in a Erlenmeyer flask several times, and then dried at 40°C.

4. A certain domestic sewage is polluted by surrounding Cu ²⁺ , and the content of Cu ²⁺ is about 10mg/L. After a certain pretreatment, the domestic sewage is treated with the prepared polymer gel. In 1L of waste water, add 2g of gel-dried product for treatment. After 24h, the adsorption rate of Cu ²⁺ in wastewater was 60%. When increasing the amount of gel product to 6g/L, the removal rate of Cu ²⁺ can reach more than 90%.

Example 15:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 2:3 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -78°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ¹³⁷ Cs-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. The irradiated hydrogel was cut into small pieces of 1 cm×1 cm×1 cm, washed in a Erlenmeyer flask several times, and then dried at 40°C.

4. A certain electroplating wastewater contains a large amount of heavy metal ions, among which the content of Cr ³⁺ is about 500mg/L. After a certain pretreatment, the electroplating wastewater is treated with the prepared polymer gel. In 1L of waste water, add 2g of gel-dried product for treatment. After 24h, the adsorption rate of Cr ³⁺ in wastewater was 40%. When the amount of gel product is increased to 10g/L, the removal rate of Cr ³⁺ can reach more than 90%.

Example 16:

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 2:3 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -78°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ¹³⁷ Cs-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. The irradiated hydrogel was cut into small pieces of 1 cm×1 cm×1 cm, washed in a Erlenmeyer flask several times, and then dried at 40°C.

4. The well water of an agricultural irrigation is polluted by lead because it is adjacent to a lead smelting plant, and the Pb ²⁺ content in it is about 4mg/L. Part of the water samples were collected from the well, and after a certain pretreatment, they were treated with the prepared polymer gel. The polymer gel was added to the water sample at a ratio of 2g/L. After 24 hours of adsorption, the Pb ²⁺ in the water sample was reduced to below 2mg/L. When the dosage increased to 8mg/L, the concentration of Pb ²⁺ in the treated water samples dropped below 0.2mg/L, and the removal rate reached 95%.

Example 16

1. Weigh a certain mass of 2-acrylamido-2-methylpropanesulfonic acid monomer (AMPS for short) and dissolve it in deionized water, fully dissolve and mix evenly as component A. Then, add a certain amount of hydroxyethyl acrylate monomer (referred to as HEA) to the above solution, mix well, as component B; distilled water as component C, mix according to (A+B):C ratio of 3:7, where A:B is 2:3 (mol/mol), and the mixture is treated with ultrasonic waves to make the mixture uniform.

2. After filling with nitrogen, at a temperature of -78°C, control the radiation dose in the range of 1×10 ³ to 1×10 ⁶ Gy, and use high-energy rays ( ¹³⁷ Cs-γ rays) to irradiate and polymerize to form polymer hydrogels.

3. The irradiated hydrogel was cut into small pieces of 1 cm×1 cm×1 cm, washed in a Erlenmeyer flask several times, and then dried at 40°C.

4. Due to the discharge of surrounding industrial sewage, a certain lake was polluted by certain heavy metal ions, among which the content of Cd ²⁺ was about 1mg/L. Some water samples were collected from the lake, and after a certain pretreatment, they were treated with the prepared polymer gel. The polymer gel was added to the water sample at a ratio of 2g/L. After 24 hours of adsorption, the Cd ²⁺ in the water sample was reduced to below 0.5mg/L. When the dosage increased to 8mg/L, the concentration of Cd ²⁺ in the treated water samples dropped below 0.03mg/L, and the removal rate reached over 94%.

Claims (5)

1. A polymer hydrogel that absorbs heavy metal ions is generated by radiation copolymerization of two monomers, hydroxyethyl acrylate and 2-acrylamido-2-methylpropanesulfonic acid. The hydrogel is characterized in that it is prepared The process consists of the following steps: (1) Mix hydroxyethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid and distilled water in a certain proportion; (2) 2-acrylamido-2-methylpropanesulfonic acid plus hydroxyethyl acrylate: the volume ratio of water is 1 to 2:5, 2-acrylamido-2-methylpropanesulfonic acid and hydroxyethyl acrylate The molar ratio of ester is 1:1~9; (3) Ultrasonic treatment for 5 to 20 minutes after mixing; (4) charge nitrogen into the mixture of (1) to ensure anaerobic state; (5) At a temperature of -63 to -95°C, the hydrogel is irradiated and polymerized by high-energy rays with a radiation dose of 1×10 ³ to 1×10 ⁶ Gy, and the high-energy rays are ⁶⁰ Co gamma rays or ¹³⁷ Cs gamma rays. 2. The application of the polymer hydrogel adsorbing heavy metal ions according to claim 1 to the adsorption of heavy metal ions under different pH conditions. 3. the application of the polymer hydrogel adsorbing heavy metal ions according to claim 1 in the adsorption of heavy metal ions in the treatment of industrial wastewater. 4. The application of the polymer hydrogel adsorbing heavy metal ions according to claim 1 in the adsorption of heavy metal ions in the treatment of domestic sewage. 5. The application of the polymer hydrogel adsorbing heavy metal ions according to claim 1 in the adsorption of heavy metal ions in the treatment of natural water bodies.

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