CN102850556A - Preparation method of modified hydrogel and application of modified hydrogel in heavy metal wastewater treatment - Google Patents
Preparation method of modified hydrogel and application of modified hydrogel in heavy metal wastewater treatment Download PDFInfo
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- 238000004065 wastewater treatment Methods 0.000 title description 2
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- 238000006243 chemical reaction Methods 0.000 claims description 21
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- 238000006116 polymerization reaction Methods 0.000 abstract description 13
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- 238000002156 mixing Methods 0.000 abstract description 3
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- 238000011049 filling Methods 0.000 abstract description 2
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- 150000002500 ions Chemical class 0.000 description 19
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 13
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- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
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- 238000004566 IR spectroscopy Methods 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
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- 241000233803 Nypa Species 0.000 description 1
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- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
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Abstract
The invention relates to a modified hydrogel. The preparation method of the modified hydrogel comprises the following steps of: (1) evenly mixing hydroxyethyl acrylate, vinyl formamide and deionized water, wherein the volume ratio of vinyl formamide and hydroxyethyl acrylate to the deionized water is (1:4)-(2:3), and the molar ratio of vinyl formamide to hydroxyethyl acrylate is (1:9)-(9:1), carrying out ultrasonic treatment for 10-30 minutes after mixing, filling inert gas into the mixture so that the oxygen-free state can be guaranteed, and carrying out the radiation polymerization with high energy ray to prepare the hydrogel; and (2) the preparation method of the modified polymer hydrogel comprises the following steps of: modifying the dried hydrogel and a 5g/L triethylene tetramine solution in a certain portion at the temperature of 25-80DEG C, so that the modified polymer hydrogel can be prepared. The modified hydrogel disclosed by the invention contains functional groups capable of adsorbing the heavy metals, and can well adsorb the heavy metals such as lead and cadmium, so that the modified hydrogel can be used for treating the water body which is mildly polluted by heavy metals.
Description
Technical field
The invention belongs to the sorbing material technical field, relate to the preparation of sorbing material and to the absorption property of heavy metal, specifically a kind of application for preparing novel modified polymer hydrogel and Adsorption of Heavy Metal Ions thereof.
Background technology
Heavy metal can produce harm to water surrounding and the whole ecosystem by modes such as water body accumulation, and can jeopardize the healthy of the mankind by direct contact or through food chain.In recent years, heavy metal pollution problem is on the rise, and is such as cadmium pollution event, Jiangsu blood lead event and the Shaanxi lead poisoning event etc. in Guangxi, therefore very important to the removal of heavy metal in water.Absorption method technique since its have with low cost, method is simple, and the characteristics of non-secondary pollution more and more come into one's own in heavy metal adsorption is processed.At present, sorbent material commonly used mainly contains gac, zeolite, ion exchange resin and resin etc., publication number be CN101225176 patent disclosure a kind of imidazolyl modified complex functional high-crosslinked adsorption resin and preparation method thereof, publication number be CN1772386 patent disclosure a kind of preparation method and application aspect heavy metal adsorption thereof of oxine type resin.
Polyalcohol hydrogel is a kind of through appropriately crosslinked and have the macromolecular material of three-dimensional net structure, and because of suction, water conservation and the bionical characteristic of its uniqueness, hydrogel is widely used in the fields such as industry, agricultural, medicine and biological engineering material.In recent years, hydrogel is subject to more and more many attention as a kind of sorbing material in the ambient water process field.Number of patent application be CN95194243 patent disclosure a kind of preparation method of aqueous gel of Adsorption of Heavy Metals, (the Journal of Functional Polymers such as Xie Jianjun, 2008, the preparation of Acrylic Acid Superabsorbent Resins via Inverse-Phase Suspension Polymerization and adsorptivity thereof) reported poly-(vinylformic acid/2-acrylamide-2-methylpro panesulfonic acid) hydrogel of employing via Inverse-Phase Suspension Polymerization preparation, and studied it to Cu
2+, Cr
3+Absorption property.(the environmental engineering journal, 2009, poly-(acrylic acid-acrylamide)/wilkinite/Sodium salts humic acids three-dimensional network gel adsorber was to Cd for Zheng Yian etc.
2+Study on adsorption properties) prepared a kind of poly-(acrylic acid-acrylamide)/wilkinite/Sodium salts humic acids three-dimensional network gel adsorber and investigated sorbent material to Cd
2+Absorption property.(the Journal of the Chinese Institute of Chemical Engineers such as Gaofeng Pan, 2008, Application of hydrogel for the removal of pollutant phenol in water) adopts NIPA and tributyl phosphate to prepare the mixing water gel, and study its Pyrogentisinic Acid's adsorption effect.(the Polymer Bulletin such as Nursel Pekel,, Separation of heavy metal ions by complexation on poly (N-vinyl imidazole) hydrogels in 2004) utilizes radiation method to prepare a kind of polyvinyl imidazol hydrogel sorbent material and investigated Cu
2+, Co
2+, Cd
2+And Pb
2+Absorption property.(the Industrial and Engineering Chemistry Research such as Selva Cavus, 2009, Noncompetitive Removal of Heavy Metal Ions from Aqueous Solutions by Poly[2-(acrylamido)-2-methyl-1-propanesulfonic acid-co-itaconic acid] Hydrogel) studied poly-(2-acrylamide-2-methyl propane sulfonic/methylene-succinic acid) hydrogel to Cu
2+, Co
2+, Cd
2+And Pb
2+Absorption behavior and mechanism.
Research finds, the modification that sorbent material is carried out polyamine compounds can improve the adsorptive power of former ABSORBENTS ABSORPTION metal greatly.(the material Leader: a research piece of writing such as Tang Hongxian,, the preparation of Polyamine Type resin and Study on adsorption properties in 2009) take vinylformic acid and vinylbenzene as comonomer, introduce the polyamines group, synthesize a series of Polyamine Type resins, and studied the absorption property of resin to nickel ion.Hasine
Deng (Polymer, 2003, Modified polyacrylamide hydrogels and their application in removal of heavy metal ions) adopt polyamine compounds that polyacrylamide hydrophilic gel is carried out modification, and after having studied modification hydrogel to Cu (II), the removal ability of Cd (II) and Pb (II).
Common hydrogel preparation method mainly contains Physical and chemical method.Physical mainly refers to adopt the radiation method preparation, and main source of radiation has
60Co-γ, electron beam etc.; Chemical method mainly comprises emulsion method, inverted emulsion method, inverse phase suspension and dispersion copolymerization method etc.But chemical method is easily introduced impurity because needing to add initiator, linking agent in the operating process, need not to add other materials in the radiation method operating process, and method comparatively cleans.And adopt radiation method both can prepare effective group that pure polyalcohol hydrogel can import the efficient adsorption heavy metal ion when the modification in conjunction with modification technology.
Summary of the invention
The present invention proposes a kind of application of radiation technology and prepares the new polymers hydrogel, and adopts triethylene tetramine (TETA) that the hydrogel that makes is carried out amination modifying, makes the method for new modified hydrogel.This modified water gel is a kind of large pore material with vesicular structure, capable of adsorbing heavy metal ions (Cd
2+And Pb
2+), the preparation method is simple, easy handling.And product has certain physical strength, can repeatedly reuse.
Technical solution of the present invention is, at first prepares polyalcohol hydrogel, again polyalcohol hydrogel carried out modification, it is characterized in that the preparation method may further comprise the steps:
(1) preparation process of polyalcohol hydrogel is as follows:
1) with Hydroxyethyl acrylate Hydroxyethyl methacrylate(HEA), vinyl formamide N-Vinylformamide(NVF) and deionized water mix; The volume ratio of vinyl formamide+Hydroxyethyl acrylate and deionized water is 1:4 ~ 2:3, and the mol ratio of vinyl formamide and Hydroxyethyl acrylate is 1:9 ~ 9:1;
2) mix after through the 10-30min ultrasonication;
3) in mixture, be filled with rare gas element (for example nitrogen, argon gas or helium), to guarantee anaerobic state; In-63～-95 ℃ of temperature, adopt energetic ray radiation (irradiation) polymerization to form hydrogel.Described energetic ray is preferably gamma-rays or electron beam, and more than MEV, gamma-rays is preferably electron beam by accelerator generation, energy
60The Co-gamma-rays or
137The Cs-gamma-rays, its radiation dose is preferably 1 * 10
3~ 1 * 10
6Gy;
(2) polymer-modified preparation of gels step is as follows:
1) polyalcohol hydrogel for preparing is cut into small pieces oven dry under 45 ± 5 ℃ after the washing repeatedly;
2) the triethylene tetramine solution of hydrogel and 5g/L is with certain proportion after the oven dry, and modification under 25 ~ 80 ℃ of temperature condition makes the novel modified polymer hydrogel.
The ratio of the polyalcohol hydrogel that makes and properties-correcting agent triethylene tetramine (g/mL) is 1:100-400; Modification temperature is 25 ℃ ~ 80 ℃; Modification time is 4h-6h.
Described modified water gel counterweight metal biosorption under different metal ion starting point concentration is used: the polyalcohol hydrogel p (HEA/NVF) for preparing is cut into 0.5cm * 0.5cm * 0.5cm fritter is placed in the container; The polyalcohol hydrogel that will be cut into small pieces repeatedly washs with deionized water; With the oven dry under 45 ℃ of the hydrogel after the washing.
The invention has the beneficial effects as follows that the new polymers hydrogel of preparation carries out amination modifying with triethylene tetramine (TETA) to the hydrogel that makes; This modified water gel is a kind of large pore material with vesicular structure, adsorbable especially heavier to harm heavy metal ion (Cd
2+And Pb
2+) effective, Pb
2+And Cd
2+The metal biosorption amount is respectively 0.3mmol/g or higher, and the residual quantity of the water body after the absorption is reduced greatly (can make when using the amount of modified water gel to account for water body 10% heavy metal content of water body up to standard), and preparation method of the present invention is simple, easy handling.And product has certain physical strength, repeatedly repeats more than ten times.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of polyalcohol hydrogel;
Fig. 2 is the infrared contrast spectrogram of modified water gel and polyalcohol hydrogel;
Fig. 3 is that modification front and back hydrogel is to the Pb of 1mmol/L
2+, Cd
2+The adsorptive capacity comparison diagram of solution;
Fig. 4 is that the modified water gel is to the Pb of different starting point concentrations
2+The absorption spirogram of solution;
Fig. 5 is that the modified water gel is to the Cd of different starting point concentrations
2+The absorption spirogram of solution.
Embodiment
The method of modifying of polyalcohol hydrogel, its key step is as follows:
(1) with Hydroxyethyl acrylate Hydroxyethyl methacrylate(HEA), vinyl formamide N-Vinylformamide(NVF) and deionized water mix; The volume ratio of vinyl formamide+Hydroxyethyl acrylate and deionized water is 1:4～2:3, and the mol ratio of vinyl formamide and Hydroxyethyl acrylate is 1:9～9:1;
(2) mix after through the 10-30min ultrasonication;
(3) in mixture, be filled with rare gas element (for example nitrogen, argon gas or helium), to guarantee anaerobic state; In-63～-95 ℃ of temperature, adopt the high-energy ray irradiation polymerization to form hydrogel.Described energetic ray is preferably gamma-rays or electron beam, and gamma-rays is preferably
60The Co-gamma-rays or
137The Cs-gamma-rays, its radiation dose is preferably 1 * 10
3~ 1 * 10
6Gy.
(4) in the 250ml Erlenmeyer flask, p (the HEA/NVF that adds oven dry, be called for short p (H/V, down together) triethylene tetramine Triethylenetetramine (TETA) solution of gel and 5g/L, both ratios (g/mL) are respectively (1:100,1:150,1:200,1:300 and 1:400);
(5) at 25 ℃ ~ 80 ℃ lower stirring reaction 4h or 6h.
(6) after reaction finishes, filter to get gel p (HEA/NVF)-TETA after the modification (be called for short p (H/V)-T, lower with), and remove for several times surface impurity with deionized water wash, 45 ℃ of lower dry for standby.
The present invention further specifies by embodiment, but the present invention is not limited to following examples.
Embodiment 1:
1. take by weighing certain volume vinyl formamide (NVF) and be dissolved in the deionized water, fully dissolving is rear as component A.Then, in mentioned solution, add a certain amount of Hydroxyethyl acrylate monomer (HEA), mix, as B component; Deionized water is 3:7(ml/ml as component C by (A+B): C) mix, wherein A:B is 3:7 (mol/mol).Carry out again supersound process 10min.
2. behind the inflated with nitrogen, under-78 ℃ temperature, control radiation dose scope is 1 * 10
3～1 * 10
6Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3. the hydrogel after the radiation is cut into 0.5cm * 0.5cm * 0.5cm fritter and is placed in the triangular flask, after deionized water repeatedly washs, place 45 ℃ of lower oven dry.
4. use scanning electronic microscope (SEM) to carry out the hydrogel surface morphology analysis to product, details as shown in Figure 1.Fig. 1-a and 1-b have shown respectively the SEM photo of 200 times and 1500 times of lower p (HEA/NVF).Can be found out that by Fig. 1-a p (HEA/NVF) has vesicular structure, surface arrangement the duct of all size.Can calculate according to the scale among Fig. 1-b between the aperture region of hydrogel p (HEA/NVF) and be distributed between 8 μ m ~ 30 μ m.
The ratio of the polyalcohol hydrogel that such scheme makes and properties-correcting agent triethylene tetramine (g/mL) is respectively 1:100,1:150,1:200,1:300 and 1:400; Modification temperature is respectively 25 ℃ ~ 80 ℃; Modification time is respectively 4h and 6h.The product that obtains is without remarkable difference.
Embodiment 2:
1. take by weighing certain volume vinyl formamide (NVF) and be dissolved in the deionized water, fully dissolving is rear as component A.Then, in mentioned solution, add a certain amount of Hydroxyethyl acrylate monomer (HEA), mix, as B component; Deionized water is 1:4(ml/ml as component C by (A+B): C) mix, wherein A:B is 9:1 (mol/mol).Carry out again supersound process 10min.
2. behind the inflated with nitrogen, under-78 ℃ temperature, control radiation dose scope is 1 * 10
3～1 * 10
6Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3. the hydrogel after the radiation is cut into 0.5cm * 0.5cm * 0.5cm fritter and is placed in the triangular flask, after deionized water repeatedly washs, place 45 ℃ of lower oven dry.
4. take by weighing the dried product of 1g hydrogel, add the TETA solution of 200ml, 5g/L, at 25 ℃ of lower stirring reaction 6h, after reaction finishes, filter to get gel p (H/V)-T after the modification, and remove for several times surface impurity with deionized water wash, 45 ℃ of lower dry for standby.
5. hydrogel before and after the modification is carried out Infrared spectroscopy, details as shown in Figure 2.Can find out 3363.3cm in the spectrogram from the infrared spectrum of p (HEA/NVF) hydrogel
-1Mainly corresponding on the HEA in the hydrogel-OH vibration peak and NVF in the N-H vibration peak, be the characteristic peak district of HEA; 1727.9cm
-1The place is representing in HEA and the NVF monomer-C=O key stretching vibration peak; 1662.4cm
-1Place and 1538.9cm
-1The place respectively representative be-stretching vibration peak of NH-CO-and N-H to be the characteristic peak district of NVF among the NVF; Therefore, Hydroxyethyl acrylate (HEA) and vinyl formamide (NVF) successfully aggregate into a Copolymeric Hydrogels.Contrast p (HEA/NVF) spectrogram, 3344cm in the infrared spectrum of hydrogel p (H/V)-T after the modification
-1Bond energy corresponding to place obviously weakens, and hydroxyl minimizing in the gel after the modification be described; 1538.9cm
-1The N-H peak at place moves to 1577.5cm
-1The place is representing among the TETA-NH
2The existence of vibration peak; 1727.9cm
-1Place-C=O key stretching vibration peak intensity reduces, and illustrates among p (H/V)-T-the C=O linkage content reduces, and its reason may be-among C=O key and the properties-correcting agent TETA-NH
2Reduction reaction has occured.Therefore contrast spectrogram as can be known, the TETA group successfully is access in p (HEA/NVF) gel.
Embodiment 3:
1. take by weighing certain volume vinyl formamide (NVF) and be dissolved in the deionized water, fully dissolving is rear as component A.Then, in mentioned solution, add a certain amount of Hydroxyethyl acrylate monomer (HEA), mix, as B component; Deionized water is 2:3(ml/ml as component C by (A+B): C) mix, wherein A:B is 3:7 (mol/mol).Carry out again supersound process 10min.
2. behind the inflated with nitrogen, under-63 ℃ temperature, control radiation dose scope is 1 * 10
3～1 * 10
6Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3. the hydrogel after the radiation is cut into 0.5cm * 0.5cm * 0.5cm fritter and is placed in the triangular flask, after deionized water repeatedly washs, place 45 ℃ of lower oven dry.
4. take by weighing the dried product of 1g hydrogel, add the TETA solution of 200ml, 5g/L, at 35 ℃ of lower stirring reaction 4h, after reaction finishes, filter to get gel p (H/V)-T after the modification, and remove for several times surface impurity with deionized water wash, 45 ℃ of lower dry for standby.
5. take by weighing respectively each 0.1g of the dried product of modification front and back hydrogel, place the 100ml triangular flask, add respectively the Pb of 50ml, 1mmol/L
2+, Cd
2+Single solution places triangular flask and carries out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 24h 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.As shown in Figure 3, front p (HEA/NVF) hydrogel of modification is to Pb
2+And Cd
2+Adsorptive capacity be respectively: 0.030mmol/g and 0.020mmol/g; P after the modification (H/V)-T hydrogel is to Pb
2+And Cd
2+Adsorptive capacity be respectively: 0.235mmol/g and 0.143mmol/g, to Pb
2+Adsorptive capacity increased by 700%, to Cd
2+Adsorptive capacity increased by 600%.
Embodiment 4:
1. take by weighing certain volume vinyl formamide (NVF) and be dissolved in the deionized water, fully dissolving is rear as component A.Then, in mentioned solution, add a certain amount of Hydroxyethyl acrylate monomer (HEA), mix, as B component; Deionized water is 3:7(ml/ml as component C by (A+B): C) mix, wherein A:B is 1:1 (mol/mol).Carry out again supersound process 10min.
2. behind the applying argon gas, under-63 ℃ temperature, control radiation dose scope is 1 * 10
3～1 * 10
6Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3. the hydrogel after the radiation is cut into 0.5cm * 0.5cm * 0.5cm fritter and is placed in the triangular flask, after deionized water repeatedly washs, place 45 ℃ of lower oven dry.
4. take by weighing respectively the dried product of 1g hydrogel, add respectively the TETA solution of 200ml, 5g/L, at 45 ℃ of lower stirring reaction 6h, after reaction finishes, filter to get gel after the modification, and remove for several times surface impurity with deionized water wash, 45 ℃ of lower dry for standby.
5. take by weighing after the 0.1g modification two parts of dried hydrogels, place respectively the 100ml triangular flask, then add respectively the Pb of 50ml, 1mmol/L
2+Or Cd
2+Solution places triangular flask and carries out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 24h 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.After measured, this modified water jel product is to Pb
2+And Cd
2+The metal biosorption amount is respectively 0.124mmol/g and 0.058mmol/g.
Embodiment 5:
1. take by weighing certain volume vinyl formamide (NVF) and be dissolved in the deionized water, fully dissolving is rear as component A.Then, in mentioned solution, add a certain amount of Hydroxyethyl acrylate monomer (HEA), mix, as B component; Deionized water is 1:4(ml/ml as component C by (A+B): C) mix, wherein A:B is 1:9 (mol/mol).Carry out again supersound process 10min.
2. behind the inflated with nitrogen, under-78 ℃ temperature, control radiation dose scope is 1 * 10
3～1 * 10
6Gy, the employing energetic ray (
137The Cs-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3. the hydrogel after the radiation is cut into 0.5cm * 0.5cm * 0.5cm fritter and is placed in the triangular flask, after deionized water repeatedly washs, place 45 ℃ of lower oven dry.
4. take by weighing respectively the dried product of 1g hydrogel, add respectively the TETA solution of 200ml, 5g/L, then at 60 ℃ of lower stirring reaction 6h, after reaction finishes, filter to get gel p (H/V)-T after the modification, and remove for several times surface impurity with deionized water wash, 45 ℃ of lower dry for standby.
5. take by weighing after the 0.1g modification two parts of dried hydrogels, place respectively the 100ml triangular flask, then add respectively the Pb of 50ml, 1mmol/L
2+Or Cd
2+Solution places triangular flask and carries out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 24h 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.After measured, this modified water jel product is to Pb
2+And Cd
2+The metal biosorption amount is respectively 0.133mmol/g and 0.104mmol/g.
Embodiment 6:
1. take by weighing certain volume vinyl formamide (NVF) and be dissolved in the deionized water, fully dissolving is rear as component A.Then, in mentioned solution, add a certain amount of Hydroxyethyl acrylate monomer (HEA), mix, as B component; Deionized water is 2:3(ml/ml as component C by (A+B): C) mix, wherein A:B is 3:7 (mol/mol).Carry out again supersound process 10min.
2. behind the inflated with nitrogen, under-78 ℃ temperature, control radiation dose scope is 1 * 10
3～1 * 10
6Gy, the employing energetic ray (
137The Cs-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3. the hydrogel after the radiation is cut into 0.5cm * 0.5cm * 0.5cm fritter and is placed in the triangular flask, after deionized water repeatedly washs, place 45 ℃ of lower oven dry.
4. take by weighing respectively the dried product of 1g hydrogel, add respectively the TETA solution of 100ml, 5g/L, at 75 ℃ of lower stirring reaction 4h, after reaction finishes, filter to get gel p (H/V)-T after the modification, and remove for several times surface impurity with deionized water wash, 45 ℃ of lower dry for standby.
5. take by weighing after the 0.1g modification two parts of dried hydrogels, place respectively the 100ml triangular flask, then add respectively the Pb of 50ml, 1mmol/L
2+Or Cd
2+Solution places triangular flask and carries out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 24h 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.After measured, this modified water jel product is to Pb
2+And Cd
2+The metal biosorption amount is respectively 0.360mmol/g and 0.178mmol/g.
Embodiment 7:
1. take by weighing certain volume vinyl formamide (NVF) and be dissolved in the deionized water, fully dissolving is rear as component A.Then, in mentioned solution, add a certain amount of Hydroxyethyl acrylate monomer (HEA), mix, as B component; Deionized water is 1:4(ml/ml as component C by (A+B): C) mix, wherein A:B is 3:7 (mol/mol).Carry out again supersound process 10min.
2. behind the inflated with nitrogen, under-95 ℃ temperature, control radiation dose scope is 1 * 10
3～1 * 10
6Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3. the hydrogel after the radiation is cut into 0.5cm * 0.5cm * 0.5cm fritter and is placed in the triangular flask, after deionized water repeatedly washs, place 45 ℃ of lower oven dry.
4. take by weighing respectively the dried product of 1g hydrogel, add respectively the TETA solution of 300ml, 5g/L, at 80 ℃ of lower stirring reaction 4h, after reaction finishes, filter to get gel p (H/V)-T after the modification, and remove for several times surface impurity with deionized water wash, 45 ℃ of lower dry for standby.
5. take by weighing after the 0.1g modification two parts of dried hydrogels, place respectively the 100ml triangular flask, then add respectively the Pb of 50ml, 1mmol/L
2+Or Cd
2+Solution places triangular flask and carries out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 24h 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.After measured, this modified water jel product is to Pb
2+And Cd
2+The metal biosorption amount is respectively 0.300mmol/g and 0.156mmol/g.
Embodiment 8:
1. take by weighing certain volume vinyl formamide (NVF) and be dissolved in the deionized water, fully dissolving is rear as component A.Then, in mentioned solution, add a certain amount of Hydroxyethyl acrylate monomer (HEA), mix, as B component; Deionized water is 3:7(ml/ml as component C by (A+B): C) mix, wherein A:B is 1:9 (mol/mol).Carry out again supersound process 10min.
2. after filling helium, under-63 ℃ temperature, control radiation dose scope is 1 * 10
3～1 * 10
6Gy, the employing energetic ray (
137The Cs-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3. the hydrogel after the radiation is cut into 0.5cm * 0.5cm * 0.5cm fritter and is placed in the triangular flask, after deionized water repeatedly washs, place 45 ℃ of lower oven dry.
4. take by weighing respectively the dried product of 1g hydrogel, add respectively the TETA solution of 500ml, 5g/L, at 60 ℃ of lower stirring reaction 6h, after reaction finishes, filter to get gel p (H/V)-T after the modification, and remove for several times surface impurity with deionized water wash, 45 ℃ of lower dry for standby.
5. take by weighing after the 0.1g modification two parts of dried hydrogels, place respectively the 100ml triangular flask, then add respectively the Pb of 50ml, 1mmol/L
2+Or Cd
2+Solution places triangular flask and carries out constant temperature absorption under 25 ℃ of the constant temperature oscillators, after 24h 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.After measured, this modified water jel product is to Pb
2+And Cd
2+The metal biosorption amount is respectively 0.354mmol/g and 0.156mmol/g.
Embodiment 9:
1. take by weighing certain volume vinyl formamide (NVF) and be dissolved in the deionized water, fully dissolving is rear as component A.Then, in mentioned solution, add a certain amount of Hydroxyethyl acrylate monomer (HEA), mix, as B component; Deionized water is 3:7(ml/ml as component C by (A+B): C) mix, wherein A:B is 3:7 (mol/mol).Carry out again supersound process 10min.
2. behind the inflated with nitrogen, under-78 ℃ temperature, control radiation dose scope is 1 * 10
3～1 * 10
6Gy, the employing energetic ray (
60The Co-gamma-rays) radiation polymerization forms polyalcohol hydrogel.
3. the hydrogel after the radiation is cut into 0.5cm * 0.5cm * 0.5cm fritter and is placed in the triangular flask, after deionized water repeatedly washs, place 45 ℃ of lower oven dry.
4. take by weighing respectively the dried product of 1g hydrogel, add respectively the TETA solution of 200ml, 5g/L, at 70 ℃ of lower stirring reaction 4h, after reaction finishes, filter to get gel p (H/V)-T after the modification, and remove for several times surface impurity with deionized water wash, 45 ℃ of lower dry for standby.
5. take by weighing after the 0.1g modification five parts of dried hydrogels and place respectively the 100ml triangular flask, then add respectively the Pb of 50ml, different starting point concentrations
2+Solution (0.2,0.4,0.6,0.8,1.0,1.2mmol/L) places triangular flask under 25 ℃ of the constant temperature oscillators and to carry out constant temperature absorption, after 24h 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 the absorption can calculate this product to the loading capacity of each ion.After measured, this modified water gel is to the Pb of different starting point concentrations
2+The solution absorbs amount is respectively: 0.072mmol/g, 0.145mmol/g, 0.181mmol/g, 0.230mmol/g, 0.255mmol/g and 0.287mmol/g.Specifically see Fig. 4.
Embodiment 10:
1. take by weighing certain volume vinyl formamide (NVF) and be dissolved in the deionized water, fully dissolving is rear as component A.Then, in mentioned solution, add a certain amount of Hydroxyethyl acrylate monomer (HEA), mix, as B component; Deionized water is 2:3(ml/ml as component C by (A+B): C) mix, wherein A:B is 3:7 (mol/mol).Carry out again supersound process 10min.
2. behind the inflated with nitrogen, under-78 ℃ temperature, adopt energetic ray (rumbatron, energy is more than MEV) radiation polymerization to form polyalcohol hydrogel.
3. the hydrogel after the radiation is cut into 0.5cm * 0.5cm * 0.5cm fritter and is placed in the triangular flask, after deionized water repeatedly washs, place 45 ℃ of lower oven dry.
4. take by weighing respectively the dried product of 1g hydrogel, add respectively the TETA solution of 200ml, 5g/L, at 55 ℃ of lower stirring reaction 4h, after reaction finishes, filter to get gel p (H/V)-T after the modification, and remove for several times surface impurity with deionized water wash, 45 ℃ of lower dry for standby.
5. take by weighing after the 0.1g modification five parts of dried hydrogels and place respectively the 100ml triangular flask, then add respectively the Cd of 50ml, different starting point concentrations
2+Solution (0.2,0.4,0.6,0.8,1.0,1.2mmol/L) places triangular flask under 25 ℃ of the constant temperature oscillators and to carry out constant temperature absorption, after 24h 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 the absorption can calculate this product to the loading capacity of each ion.After measured, this modified water gel is to the Pb of different starting point concentrations
2+The solution absorbs amount is respectively: 0.078mmol/g, 0.125mmol/g, 0.145mmol/g, 0.121mmol/g, 0.136mmol/g and 0.181mmol/g.Specifically see Fig. 5.
Claims (3)
1. polymer-modified hydrogel is characterized in that the preparation method may further comprise the steps:
(1) preparation process of polyalcohol hydrogel is as follows:
1) with Hydroxyethyl acrylate Hydroxyethyl methacrylate(HEA), vinyl formamide N-Vinylformamide(NVF) and deionized water mix; The volume ratio that vinyl formamide adds Hydroxyethyl acrylate and deionized water is 1:4 ~ 2:3, and the mol ratio of vinyl formamide and Hydroxyethyl acrylate is 1:9 ~ 9:1;
2) mix after through 10 ~ 30min ultrasonication;
3) in mixture, be filled with rare gas element, to guarantee anaerobic state;
4) energetic ray radiation, described energetic ray is preferably gamma-rays or electron beam, and more than MEV, gamma-rays is preferably electron beam by accelerator generation, energy
60The Co-gamma-rays or
137The Cs-gamma-rays, radiation dose is preferably 1 * 10
3～1 * 10
6Gy, radiated time are 10h; Temperature of reaction is-63 ℃ ~-95 ℃ during radiation.
(2) polymer-modified preparation of gels step is as follows:
1) polyalcohol hydrogel for preparing is cut into small pieces oven dry under 45 ± 5 ℃ after the washing repeatedly;
2) the triethylene tetramine solution of hydrogel and 5g/L is with certain proportion after the oven dry, and modification under 25 ~ 80 ℃ of temperature condition makes polymer-modified hydrogel.
2. by the described polymer-modified preparation of gels method of claim 1, it is characterized in that: the ratio (g/mL) of the polyalcohol hydrogel that makes and properties-correcting agent triethylene tetramine is 1:100 to 400; Modification temperature is 25 ℃ ~ 80 ℃; Modification time is 4 to 6h.
3. use such as the described modified water gel of one of claim 1-2 counterweight metal biosorption under different metal ion starting point concentration.
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