CN102453187B - Polymer hydrogel for absorbing heavy metals and preparation method and application thereof - Google Patents

Polymer hydrogel for absorbing heavy metals and preparation method and application thereof Download PDF

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CN102453187B
CN102453187B CN2010105179490A CN201010517949A CN102453187B CN 102453187 B CN102453187 B CN 102453187B CN 2010105179490 A CN2010105179490 A CN 2010105179490A CN 201010517949 A CN201010517949 A CN 201010517949A CN 102453187 B CN102453187 B CN 102453187B
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hydrogel
heavy metal
water
absorption
acrylamide
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CN102453187A (en
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李正魁
王月明
吴凯
陈祈春
周莉
王易超
潘静赟
范念文
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Nanjing University
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Nanjing University
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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

Polyalcohol hydrogel of a kind of Adsorption of Heavy Metals and its preparation method and application
Technical field
The invention belongs to the sorbing material technical field, be specifically related to a kind of polymeric hydrogel and preparation method thereof and in the application in heavy metal ion adsorbed.
Background technology
In recent years, because the mankind are increasing to exploitation, smelting, processing and the business manufacturing activities of heavy metal, the heavy metal produced quantitatively with on kind all increases greatly, cause heavy metal to enter in a large number in soil, water body, not only cause serious environmental pollution and the wasting of resources, and the mankind healthy produced to very large threat.The method of processing heavy metal wastewater thereby is a lot, and the most frequently used method is chemical method at present, and it can remove the metal ion in waste water fast, and technological process is simple, but exists the water outlet metal concentration higher, easily produces secondary pollution, the shortcomings such as waste water recycling difficulty.And absorption method is simple because for the treatment of scheme, easy handling, be also the method that is widely used and studies in the heavy metal containing wastewater treatment technology.Sorbent material mainly contains gac, zeolite, ion exchange resin and resin (as publication number, being a kind of resin of CN1772386) etc., and relatively less as the research of sorbent material about hydrogel.
Hydrogel is water insoluble but at the three-dimensional network polymkeric substance of water camber swelling.It has low crosslinking degree, high swelling ratio, water-fast structure and performance characteristic; Have water-retaining capacity strong, good water-retaining property, even after water suction, pressurization is not dewatered yet, have the essential characteristic of general macromolecular compound simultaneously.In hydrogel, have a large amount of functional groups, the absorption to dyestuff and heavy metal receives much concern in recent years as new adsorbent.Many natural organic high-molecular polymkeric substance are owing to having on the studied adsorption treatment that is applied to heavy metal wastewater thereby of abundant functional groups, chitosan biolobic material material is exactly a typical representative, and the patent No. is that the polymeric adsorbent of CN101701042A is exactly to take the heavy metal adsorption material that chitosan is prepared into after chemically modified as matrix.In the structure of chitosan biolobic material material, contain a large amount of-NH and-the OH group, these groups have stronger complexing and sequestering action to heavy metal ion, and the micro heavy in water body is also had to removal effect preferably, and wide material sources, with low cost.But this class natural biologic material also have physical strength not high, easily be biodegradable, be subjected to pH to affect the shortcomings such as very large.Synthetic has the high molecular polymer gel of functional groups, also is used to the fractionation by adsorption of heavy metal wastewater thereby.The high molecular polymer hydrogel of existing synthetic comprises polyacrylic hydrogel etc., can be in conjunction with effective group of heavy metal ion owing to having carboxyl etc., to the ionic adsorption of heavy metal wastewater thereby with separate that also have must effect, but effect not bery remarkable.And the most route of synthesis relative complex of the high molecular polymer hydrogel of existing synthetic, operate cumbersomely, is also a large shortcoming.
Summary of the invention
The problem that the present invention need to solve is to provide polyalcohol hydrogel of a kind of Adsorption of Heavy Metals and its preparation method and application.
Technical scheme of the present invention is:
1 hydrogel of the present invention is water insoluble but, at the three-dimensional network polymkeric substance of water camber swelling, is generated by Hydroxyethyl acrylate (wetting ability vitreous state monomer) and two kinds of monomer radiation copolymerizations of 2-acrylamide-2-methylpro panesulfonic acid.It has low crosslinking degree, high swelling ratio, water-fast structure and performance characteristic; Have water-retaining capacity strong, good water-retaining property, even after water suction, pressurization is not dewatered yet, have the essential characteristic of general macromolecular compound simultaneously.
The preparation method of 2 heavy metal adsorption polyalcohol hydrogels, it mainly comprises the following steps:
(1) Hydroxyethyl acrylate (wetting ability vitreous state monomer), 2-acrylamide-2-methylpro panesulfonic acid and distilled water are mixed by a certain percentage;
(2) the 2-acrylamide-2-methylpro panesulfonic acid adds Hydroxyethyl acrylate: the volume ratio of water is (1 ~ 2): the mol ratio of 5,2-acrylamide-2-methylpro panesulfonic acid and Hydroxyethyl acrylate is 1:(1 ~ 9);
(3) mix after through 5 ~ 20min ultrasonication;
(4) in the mixture of (1), be filled with nitrogen, to guarantee anaerobic state;
(5) in-63～-95 ℃ of temperature, adopting radiation dose is 1 * 10 3～1 * 10 6The high-energy ray irradiation polymerization of Gy forms hydrogel.
The adsorption method of polyalcohol hydrogel to heavy metal ion, it mainly comprises the following steps:
The polyalcohol hydrogel that (1) will prepare is cut into 1cm * 1cm * 1cm fritter and is placed in triangular flask;
The polyalcohol hydrogel that (2) will be cut into small pieces repeatedly washs with deionized water;
(3) under 25 ℃ of conditions, different types of heavy metal ion is adsorbed.
3 the present invention compared with prior art its beneficial effect are:
The research of existing heavy metal adsorption hydrogel mainly is natural organic high molecular polymer, particularly take chitosan as research object the most common, but this class natural biologic material physical strength is not high, it is very large easily to be biodegradable, to be subjected to pH to affect.And the technology of preparing process more complicated of existing artificial planar water gel, loading capacity is not high.The present invention proposes a kind of method that application of radiation technology prepares the planar water gel, can prepare a kind of organic high molecular polymer with functional groups, can make the functional group active adsorption chelating heavy metal ion in polymkeric substance, the preparation method is simple, easy handling.And product has certain physical strength, can increase the service life.
The accompanying drawing explanation
Fig. 1 is the SEM figure of hydrogel.
Fig. 2 is the infrared spectrogram of hydrogel.
Fig. 3 is that hydrogel adsorbs Pb under different pH 2+Loading capacity figure.
Fig. 4 is that hydrogel adsorbs Cd under different pH 2+Loading capacity figure.
Fig. 5 is hydrogel Adsorption of Cu under different pH 2+Loading capacity figure.
Fig. 6 is that hydrogel adsorbs Cr under different pH 3+Loading capacity figure.
Fig. 7 is that hydrogel adsorbs Fe under different pH 3+Loading capacity figure.
Embodiment
The present invention is further described by embodiment, but the present invention is not limited to following examples.
Embodiment 1:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is 3:7(v/v by (A+B): C) mix, wherein A:B is 2:5 (mol/mol).Use ultrasonic wave to process and make to mix mixture;
2. after inflated with nitrogen, at the temperature of-78 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel;
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature;
4. product is carried out to the sign of structure and composition, comprise the composition that uses SEM to carry out the pore structure observation and use the Infrared spectroscopy product.The result of SEM shows, product has pore structure preferably.The infared spectrum contrast of the infared spectrum of product and two kinds of reactant monomer, shown that two keys of monomer become the new product of chain formation after opening after the energetic ray radiation.
Embodiment 2:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 1:5 mixes by (A+B): C, and wherein A:B is 2:3 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-63 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 137The Cs-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take five parts of the dried products of polyalcohol hydrogel 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Pb of 50ml 1g/L 2+, Cd 2+, Cr 3+, Cu 2+, Fe 3+Five kinds of single solution, be placed in triangular flask under 25 ℃ of constant temperature oscillators and carry out constant temperature absorption, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorbs with absorption after concentration.Measuring method is used atomic absorption method for dilution is rear.Concentration difference by ion before and after absorption, can calculate the loading capacity of this product to each ion.After measured, product is to Pb 2+, Cr 3+, Cd 2+, Cu 2+, Fe 3+The loading capacity of five metal ion species is respectively: 180mg/g, 130mg/g, 110mg/g, 70mg/g, 110mg/g.
Embodiment 3:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 1:5 mixes by (A+B): C, and wherein A:B is 1:1 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-63 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take five parts of the dried products of polyalcohol hydrogel 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Pb of 50ml 1g/L 2+, Cd 2+, Cr 3+, Cu 2+, Fe 3+Five kinds of single solution, be placed in triangular flask under 25 ℃ of constant temperature oscillators and carry out constant temperature absorption, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorbs with absorption after concentration.Measuring method is used atomic absorption method for dilution is rear.Concentration difference by ion before and after absorption, can calculate the loading capacity of this product to each ion.After measured, product is to Pb 2+, Cr 3+, Cd 2+, Cu 2+, Fe 3+The loading capacity of five metal ion species is respectively: 150mg/g, 130mg/g, 110mg/g, 70mg/g, 110mg/g.
Embodiment 4:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 2:5 mixes by (A+B): C, and wherein A:B is 1:5 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-78 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 137The Cs-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take five parts of the dried products of polyalcohol hydrogel 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Pb of 50ml 1g/L 2+, Cd 2+, Cr 3+, Cu 2+, Fe 3+Five kinds of single solution, be placed in triangular flask under 25 ℃ of constant temperature oscillators and carry out constant temperature absorption, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorbs with absorption after concentration.Measuring method is used atomic absorption method for dilution is rear.Concentration difference by ion before and after absorption, can calculate the loading capacity of this product to each ion.After measured, product is to Pb 2+, Cr 3+, Cd 2+, Cu 2+, Fe 3+The loading capacity of five metal ion species is respectively: 130mg/g, 80mg/g, 70mg/g, 60mg/g, 110mg/g.
Embodiment 5:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 2:5 mixes by (A+B): C, and wherein A:B is 2:3 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-78 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 137The Cs-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take five parts of the dried products of polyalcohol hydrogel 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Pb of 50ml 1g/L 2+, Cd 2+, Cr 3+, Cu 2+, Fe 3+Five kinds of single solution, be placed in triangular flask under 25 ℃ of constant temperature oscillators and carry out constant temperature absorption, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorbs with absorption after concentration.Measuring method is used atomic absorption method for dilution is rear.Concentration difference by ion before and after absorption, can calculate the loading capacity of this product to each ion.After measured, product is to Pb 2+, Cr 3+, Cd 2+, Cu 2+, Fe 3+The loading capacity of five metal ion species is respectively: 200mg/g, 120mg/g, 130mg/g, 100mg/g, 130mg/g.
Embodiment 6:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 1:9 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-95 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take five parts of the dried products of polyalcohol hydrogel 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Pb of 50ml 1g/L 2+, Cd 2+, Cr 3+, Cu 2+, Fe 3+Five kinds of single solution, be placed in triangular flask under 25 ℃ of constant temperature oscillators and carry out constant temperature absorption, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorbs with absorption after concentration.Measuring method is used atomic absorption method for dilution is rear.Concentration difference by ion before and after absorption, can calculate the loading capacity of this product to each ion.After measured, product is to Pb 2+, Cr 3+, Cd 2+, Cu 2+, Fe 3+The loading capacity of five metal ion species is respectively: 140mg/g, 60mg/g, 70mg/g, 80mg/g, 130mg/g.
Embodiment 7:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 1:5 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-95 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take five parts of the dried products of polyalcohol hydrogel 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Pb of 50ml 1g/L 2+, Cd 2+, Cr 3+, Cu 2+, Fe 3+Five kinds of single solution, be placed in triangular flask under 25 ℃ of constant temperature oscillators and carry out constant temperature absorption, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorbs with absorption after concentration.Measuring method is used atomic absorption method for dilution is rear.Concentration difference by ion before and after absorption, can calculate the loading capacity of this product to each ion.After measured, product is to Pb 2+, Cr 3+, Cd 2+, Cu 2+, Fe 3+The loading capacity of five metal ion species is respectively: 160mg/g, 80mg/g, 100mg/g, 80mg/g, 110mg/g.
Embodiment 8:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 2:3 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-95 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take five parts of the dried products of polyalcohol hydrogel 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Pb of 50ml 1g/L 2+, Cd 2+, Cr 3+, Cu 2+, Fe 3+Five kinds of single solution, be placed in triangular flask under 25 ℃ of constant temperature oscillators and carry out constant temperature absorption, after 48h fully adsorbs, measure respectively before each heavy metal ion solution absorbs with absorption after concentration.Measuring method is used atomic absorption method for dilution is rear.Concentration difference by ion before and after absorption, can calculate the loading capacity of this product to each ion.After measured, product is to Pb 2+, Cr 3+, Cd 2+, Cu 2+, Fe 3+The loading capacity of five metal ion species is respectively: 190mg/g, 120mg/g, 140mg/g, 80mg/g, 150mg/g.
Embodiment 9:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 1:9 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-78 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take each seven parts of desciccate 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Pb of the 2g/L under the 50ml certain pH 2+Solution.The pH of solution is respectively 1,2,3,4,5,6,7.Triangular flask is placed under 25 ℃ of constant temperature oscillators and carries out constant temperature absorption, after 48h fully adsorbs, measure respectively Pb under each pH 2+Before solution absorbs with absorption after Pb 2+Concentration.Measuring method is used atomic absorption method for dilution is rear.By Pb before and after absorption 2+Concentration difference, can calculate this product for Pb 2+Loading capacity.After measured, at pH, be 6 o'clock, hydrogel is to Pb 2+Adsorption effect best.Refer to accompanying drawing 3.
Embodiment 10:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 1:9 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-63 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take each seven parts of desciccate 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Cd of the 2g/L under the 50ml certain pH 2+Solution.The pH of solution is respectively 1,2,3,4,5,6,7.Triangular flask is placed under 25 ℃ of constant temperature oscillators and carries out constant temperature absorption, after 48h fully adsorbs, measure respectively Cd under each pH 2+Before solution absorbs with absorption after Cd 2+Concentration.Measuring method is used atomic absorption method for dilution is rear.By Cd before and after absorption 2+Concentration difference, can calculate this product for Cd 2+Loading capacity.After measured, at pH, be 6 o'clock, hydrogel is to Cd 2+Adsorption effect best.Refer to accompanying drawing 4.
Embodiment 11:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 1:9 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-78 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take each seven parts of desciccate 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Cu of the 2g/L under the 50ml certain pH 2+Solution.The pH of solution is respectively 1,2,3,4,5,6,7.Triangular flask is placed under 25 ℃ of constant temperature oscillators and carries out constant temperature absorption, after 48h fully adsorbs, measure respectively Cu under each pH 2+Before solution absorbs with absorption after Cu 2+Concentration.Measuring method is used atomic absorption method for dilution is rear.By Cu before and after absorption 2+Concentration difference, can calculate this product for Cu 2+Loading capacity.After measured, at pH, be 4 o'clock, hydrogel is to Cu 2+Adsorption effect best.Refer to accompanying drawing 5.
Embodiment 12:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 1:9 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-63 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take each seven parts of desciccate 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Cr of the 2g/L under the 50ml certain pH 3+Solution.The pH of solution is respectively 1,2,3,4,5,6,7.Triangular flask is placed under 25 ℃ of constant temperature oscillators and carries out constant temperature absorption, after 48h fully adsorbs, measure respectively Cr under each pH 3+Before solution absorbs with absorption after Cr 3+Concentration.Measuring method is used atomic absorption method for dilution is rear.By Cr before and after absorption 3+Concentration difference, can calculate this product for Cr 3+Loading capacity.After measured, at pH, be 7 o'clock, hydrogel is to Cr 3+Adsorption effect best.Refer to accompanying drawing 6.
Embodiment 13:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 1:9 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-63 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. take each seven parts of desciccate 0.1g and be placed in respectively the 100ml triangular flask, then add respectively the Fe of the 2g/L under the 50ml certain pH 3+Solution.The pH of solution is respectively 1,2,3,4,5,6,7.Triangular flask is placed under 25 ℃ of constant temperature oscillators and carries out constant temperature absorption, after 48h fully adsorbs, measure respectively Fe under each pH 3+Before solution absorbs with absorption after Fe 3+Concentration.Measuring method is used atomic absorption method for dilution is rear.By Fe before and after absorption 3+Concentration difference, can calculate this product for Fe 3+Loading capacity.After measured, at pH, be 2 o'clock, hydrogel is to Fe 3+Adsorption effect best.Refer to accompanying drawing 7.
Embodiment 14:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 2:3 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-78 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 137The Cs-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. certain sanitary sewage is received peripheral Cu 2+Pollution, Cu wherein 2+Content be about 10mg/L.After certain pre-treatment, adopt the polymer gel of preparation to process this sanitary sewage.In the waste water of 1L, add 2g gel drying product to process.After 24h, Cu in waste water 2+Adsorption rate is 60%.When the amount of increase jel product makes it to arrive 6g/L, Cu 2+Clearance can arrive more than 90%.
Embodiment 15:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 2:3 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-78 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 137The Cs-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. certain electroplating wastewater contains a large amount of heavy metal ion, wherein Cr 3+Content be about 500mg/L.After certain pre-treatment, adopt the polymer gel of preparation to process this electroplating wastewater.In the waste water of 1L, add 2g gel drying product to process.After 24h, Cr in waste water 3+Adsorption rate is 40%.When the amount of increase jel product makes it to arrive 10g/L, Cr 3+Clearance can arrive more than 90%.
Embodiment 16:
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 2:3 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-78 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 137The Cs-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. certain agriculture is filled with well water because of contiguous certain plumbous smeltery, is subject to Lead contamination,, Pb wherein 2+Content be about 4mg/L.By this well water collecting part water sample, after certain pre-treatment, adopt the polymer gel of preparation to process.The ratio of polymer gel with 2g/L added to water sample, after 24h absorption, the Pb in water sample 2+Be reduced to below 2mg/L.When dosage increases to 8mg/L, Pb in the water sample after processing 2+Density loss to 0.2mg/L, clearance reaches 95%.
Embodiment 16
1. take certain mass 2-acrylamide-2-methylpro panesulfonic acid monomer (being called for short AMPS) and be dissolved in deionized water, fully dissolve and mix as component A.Then, add a certain amount of Hydroxyethyl acrylate monomer (being called for short HEA) in above-mentioned solution, mix, as B component; Distilled water, as component C, is that 3:7 mixes by (A+B): C, and wherein A:B is 2:3 (mol/mol), uses ultrasonic wave to process and make to mix mixture.
2. after inflated with nitrogen, at the temperature of-78 ℃, control the radiation dose scope 1 * 10 3～1 * 10 6Gy, the employing energetic ray ( 137The Cs-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3., after hydrogel after radiation being cut into to 1cm * 1cm * 1cm fritter and being placed in triangular flask repeatedly washing, dry at 40 ℃ of temperature.
4. certain lake, due to entering of industrial sewage on every side, is subject to the pollution of certain heavy metal ion, wherein Cd 2+Content be about 1mg/L.By this lake water collecting part water sample, after certain pre-treatment, adopt the polymer gel of preparation to process.The ratio of polymer gel with 2g/L added to water sample, after 24h absorption, the Cd in water sample 2+Be reduced to below 0.5mg/L.When dosage increases to 8mg/L, Cd in the water sample after processing 2+Density loss to 0.03mg/L, clearance reaches more than 94%.

Claims (5)

1. the polyalcohol hydrogel of an Adsorption of Heavy Metal Ions, generated by Hydroxyethyl acrylate and two kinds of monomer radiation copolymerizations of 2-acrylamide-2-methylpro panesulfonic acid, and this hydrogel is characterised in that its preparation process consists of following steps:
(1) Hydroxyethyl acrylate, 2-acrylamide-2-methylpro panesulfonic acid and distilled water are mixed by a certain percentage;
(2) the 2-acrylamide-2-methylpro panesulfonic acid adds Hydroxyethyl acrylate: the volume ratio of water is 1～2:5, and the mol ratio of 2-acrylamide-2-methylpro panesulfonic acid and Hydroxyethyl acrylate is 1:1～9;
(3) mix after through 5～20min ultrasonication;
(4) in the mixture of (1), be filled with nitrogen, to guarantee anaerobic state;
(5) in-63～-95 ℃ of temperature, adopting radiation dose is 1 * 10 3～1 * 10 6The high-energy ray irradiation polymerization of Gy forms hydrogel, and energetic ray is 60The Co gamma-rays or 137The Cs gamma-rays.
The polyalcohol hydrogel of Adsorption of Heavy Metal Ions according to claim 1 under condition of different pH to the application in heavy metal ion adsorbed.
The polyalcohol hydrogel of Adsorption of Heavy Metal Ions according to claim 1 in processing trade effluent to the application in heavy metal ion adsorbed.
The polyalcohol hydrogel of Adsorption of Heavy Metal Ions according to claim 1 in processing sanitary sewage to the application in heavy metal ion adsorbed.
The polyalcohol hydrogel of Adsorption of Heavy Metal Ions according to claim 1 in processing natural water to the application in heavy metal ion adsorbed.
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