CN101735462B - Method for preparing absorbent resin with bivalent cadmium ion and bivalent lead ion cavities - Google Patents
Method for preparing absorbent resin with bivalent cadmium ion and bivalent lead ion cavities Download PDFInfo
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- CN101735462B CN101735462B CN2009103125012A CN200910312501A CN101735462B CN 101735462 B CN101735462 B CN 101735462B CN 2009103125012 A CN2009103125012 A CN 2009103125012A CN 200910312501 A CN200910312501 A CN 200910312501A CN 101735462 B CN101735462 B CN 101735462B
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- polyoxyethylene glycol
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- polymeric adsorbent
- aqueous solution
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Abstract
The invention relates to a method for preparing absorbent resin with bivalent cadmium ion and bivalent lead ion cavities, and belongs to the technical field of water treatment. The method comprises the following steps of: 1, adding chitosan, polyethylene glycol macromonomer mono-blocked by methacrylic acid, polyethylene glycol macromonomer double-blocked by crylic acid and photo initiator in aqueous solution of ethanol and stirring the mixture to obtain solution; 2, adding the crylic acid or the methacrylic acid into the solution, then adding Cd2+ and Pd2+ into the solution, and irradiating the solution by ultraviolet light to obtain a solid product; and 3, soaking the solid product with hydrochloric acid, adjusting the pH value to 7 with ammonia water, and drying to obtain the absorbent resin with the Cd2+ and Pb2+ cavities. The absorbent resin prepared by the method has high selectivity and high adsorbability for the Cd2+ and Pb2+, contributes to accurately enriching the Cd2+ and Pb2+, achieves the purposes of removing and recycling the Cd2+ and Pb2+, and can be used repeatedly.
Description
Technical field
The present invention relates to a kind of preparation method of water-treatment technology field, specifically is a kind of preparation method with the polymeric adsorbent in divalence cadmium ion and lead hole.
Background technology
Along with the fast development of economic construction, environmental problem has been subjected to the whole world and has paid close attention to, and underground water occupies an important position as important water resources.In the available Freshwater resources in the whole world, underground water accounts for 95%.China's town water total amount is heavy, and underground water accounts for 30%.North China, city, northwest utilize phreatic ratio respectively up to 72% and 66%.Nearly 50% urban groundwater suffers pollution in various degree at present.Pollutent has heavy metal, metalloid ion (as AsO
3 -), organism and nitrate etc., and majority is a combined pollution.Cd particularly
2+And Pb
2+As the necessary heavy metal ion of common and non-life,, all can cause them to poison even death in human body and other organism inner accumulated.How to remove phreatic Cd
2+And Pb
2+For the water safety that ensures people's lives, uplift the people's living standard, protect environment to have important practical significance.
Molecular imprinting (Molecular Imprinting Technique, MIT) claim the molecular template technology again, be to combine subject knowledges such as polymer science, materialogy chemical engineering, a kind of new technique of cross-linked polymer that preparation is mated fully with template molecule or ion on space structure and binding site.Because molecularly imprinted polymer has highly cross-linked structure, good stability, can in severe rugged environments such as high temperature, high pressure, organic solvent, acid, alkali, use, and it is cheap, obtain increasingly extensive application in fields such as the chromatographic separation of chipal compounds, Solid-Phase Extraction, clinical drug analysis, membrane sepn, Biomimic sensors, shown powerful growth momentum and application prospect.This new technique is applied to the underground water repair process, prepares more effective sorbing material, can effectively remove, reclaim the Cd in the underground water
2+And Pb
2+In order to obtain at space structure and binding site and certain a part or ion) cross-linked polymer of coupling fully, its preparation generally has the following step: the mode of the functionalized polymer monomer that at first will have a complementary structure by covalently or non-covalently is simultaneously and template Cd
2+And Pb
2+Ionic bond, next adds linking agent and carries out crosslinking polymerization, at last after reaction is finished with Cd
2+And Pb
2+The ion wash-out is had and Cd simultaneously
2+And Pb
2+The three-dimensional hole of the single-minded bonded of ion.It is not only to Cd
2+And to Pb
2+Ion all has highly selective and high absorbability, can accurately adsorb, enrichment Cd
2+And Pb
2+Ion reaches the purpose of removing and reclaiming.
Chitin is the main component in mushroom and the Crustacean isoreactivity organism crust.Acetamido on 2 is with Mierocrystalline cellulose is different, it has similar structure to Mierocrystalline cellulose, and reaches 10,000,000,000 tons in natural output every year, is only second to Mierocrystalline cellulose, coming second of natural polymer suboutput, is that a kind of standing stock are extremely enriched the organic regenerative resource.Chitosan (CTS) is a kind of chitin derivativ that partially or completely removes acetyl, it has the mixed cell of the 2-amino-2-deoxidation-β-D-glucosamine of the 2-ethanamide-2-deoxidation-β-D-glucose ring of chitin and chitosan, and it is unique alkaline polysaccharide that present nature is found.Their chemical structure as shown in Figure 1.In general, the chitin that reaches more than 75% of deacetylation is called chitosan.Chitin and chitosan and derivative thereof have nontoxic, tasteless, have biocompatibility and enzyme liberating in animal tissues.In recent decades, be used widely in biomedicine, ecotope and the industrial circle.Owing to have a large amount of amino on the chitosan molecule structure, it has obtained widespread use (spherical Ni at aspects such as heavy metal ion enrichments
2+The research of template chitosan resin absorption property transitivity, colleges and universities' chemical engineering journal, No1.Vol5.p23～28; Comparativeadsorption of Cu (II), Zn (II), and Pb (II) ions in aqueous solution on thecrosslinked chitosan with epichrolohydrin, Journal of hazardous materials, 154 (2008), 184～191)
Polyoxyethylene glycol is widely used in the synthesized polymer material of ion enrichment as a kind of nonionic surface active agent, owing to have the ring texture of the crooked similar crown ether of polyoxyethylene glycol energy of certain-length, metal ion is had great sequestering power.
Find that through literature search Shang Weijian is relevant " to have Cd to prior art
2+And Pb
2+The preparation method of the polymeric adsorbent of ion cavities " report.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method with the polymeric adsorbent in divalence cadmium ion and lead hole is provided.The polymeric adsorbent of method preparation of the present invention is to Cd
2+And Pb
2+Ion has highly selective and high absorbability, helps Cd
2+And Pb
2+The accurate enrichment of ion reaches the purpose of removing and reclaiming, and this polymeric adsorbent can use repeatedly.
The present invention realizes that by following technical scheme technical scheme of the present invention comprises the steps:
Step 1 adds chitosan in the alcoholic acid aqueous solution, add the big monomer of the end capped polyoxyethylene glycol of methacrylic acid list simultaneously, the two big monomers of end capped polyoxyethylene glycol of vinylformic acid, and light trigger stirs, and gets solution;
Step 2 adds acrylic or methacrylic acid in solution, add Cd afterwards
2+And Pb
2+, UV-irradiation gets solid product;
Step 3, with solid product salt acid soak, it is 7 that ammoniacal liquor is regulated its pH, oven dry obtains having Cd
2+And Pb
2+The polymeric adsorbent of ion cavities.
In the step 1, the massfraction of the described alcoholic acid aqueous solution is 50%.
In the step 1, in molar ratio, the ratio of big monomer of the end capped polyoxyethylene glycol of described list and chitosan is 1: (1～5).
In the step 1, in molar ratio, the described pair of poly-big monomer of ethylene glycol of end-blocking is 1.5: 1 with the big monomeric ratio of single end capped polyoxyethylene glycol.
In the step 1, light trigger is poly-big monomer of ethylene glycol of two end-blockings and 1～5% of the big monomer total mass of single end capped polyoxyethylene glycol.
In the step 1, described light trigger is a light trigger 1173.
In the step 2, described adding Cd
2+And Pb
2+Be specially: add solubility Cd
2+Salt and solubility Pb
2+The aqueous solution of salt, the described aqueous solution is specially, with solubility Cd
2+Salt and solubility Pb
2+Salt is solute, presses Cd
2+And Pb
2+Total mole number calculate 0＜Cd
2+Mole number account for ratio＜100% of total mole number; The preparation mass percent is 1%～15% the aqueous solution.
The mass percent of the described aqueous solution is 1%～5%.
Light trigger of the present invention is the material that the energy cracking generates living radical under action of ultraviolet light; The big monomer of the end capped polyoxyethylene glycol of methacrylic acid list is an adsorbate; The two big monomers of end capped polyoxyethylene glycol of vinylformic acid are linking agent; Chitosan can only be dissolved in the acidic solution, and acid commonly used has hydrochloric acid, acetate etc., but these acid mineral acids commonly used and organic acid can only play the effect of promotion chitosan dissolved in system.Select the acids of acrylic or methacrylic acid for use, can not only make the chitosan dissolving, in reaction process, also can participate in solidification process simultaneously, become a part of segment of polymer interpenetration network, promptly play active acid solvent action as regulation system pH value.After cross-linking and curing reaction is finished, with hydrochloric acid wash-out Cd
2+And Pb
2+Ion, the acid number pH=7 with the ammoniacal liquor regulation system makes the amino in the chitosan molecule dissociate out; The purpose of selecting for use ammoniacal liquor to regulate pH value simultaneously is that ammoniacal liquor not only can neutralize and washs the hydrochloric acid of usefulness, and can also with the acrylic or methacrylic acid-respons, generate transition metal intercalating agent acrylamide or Methacrylamide in the water commonly used, improved the loading capacity of polymeric adsorbent.
Compared with prior art, the present invention has following beneficial effect: the polymeric adsorbent of method preparation of the present invention is to Cd
2+And Pb
2+Ion has highly selective and high absorbability, helps Cd
2+And Pb
2+The accurate enrichment of ion reaches the purpose of removing and reclaiming, and this polymeric adsorbent can use repeatedly.
Embodiment
Present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1
Take by weighing following raw material:
Chitosan 0.05mol;
Get single end-blocking polyoxyethylene glycol-400 monomer greatly by the mol ratio of the big monomer of methacrylic acid list end-blocking polyoxyethylene glycol-400 and chitosan=1: 1;
By the big monomer of the two end-blocking polyoxyethylene glycol-400 of vinylformic acid and the big monomeric mol ratio of single end-blocking polyoxyethylene glycol-400=1.5: 1 get two end-blocking polyoxyethylene glycol-400 greatly monomer as linking agent.
The preparation method of present embodiment comprises the steps:
Step 1, it is in 50% the alcoholic acid aqueous solution that the chitosan of 0.05mol is dispersed in massfraction, add the light trigger 1173 of the big monomer of single end-blocking polyoxyethylene glycol-400, the big monomer of two end-blocking polyoxyethylene glycol-400 and above two reactive monomer total masses 1% subsequently, stir;
Step 2 with methacrylic acid-conditioning solution acidity, makes the dissolving of dispersive chitosan become the thickness homogeneous solution, adds 0.1% solubility Cd of the big monomer total mass of chitosan and single end-blocking polyoxyethylene glycol-400 then
2+Salt and solubility Pb
2+The aqueous solution of salt, the described aqueous solution is specially, with Cd (NO
3)
2And Pb (NO
3)
2Be solute, press Cd
2+And Pb
2+Total mole number calculate Cd
2+The mole number ratio that accounts for total mole number be 1%; The preparation mass percent is 1% the aqueous solution.Polymers soln is carried out trace; The above-mentioned solution that trace is good, polymerization under ultraviolet lamp;
Step 3, polymerisate washes secondary with redistilled water, soaks 24h with the 0.1M hydrochloric acid soln, removes the Cd that trace is used
2+And Pb
2+,, be immersed in the redistilled water with redistilled water flushing three times.No longer change to pH=7 with ammoniacal liquor regulator solution acid number is stable, when making amino in the chitosan dissociate out, also make acrylic or methacrylic acid be converted into corresponding acrylamide or Methacrylamide.With redistilled water flushing three times, to filter, oven dry obtains having Cd
2+And Pb
2+The polymeric adsorbent of ion cavities can be to Cd in the underground water
2+And Pb
2+Ion optionally adsorbs and enrichment.
Embodiment 2
Take by weighing following raw material:
Take by weighing chitosan 0.05mol;
Get the big monomer of single end-blocking polyoxyethylene glycol-1000 by chitosan and the big monomeric mol ratio of methacrylic acid list end-blocking polyoxyethylene glycol-1000=1: 2.5; By the big monomer of the two end-blocking polyoxyethylene glycol-1000 of vinylformic acid and the big monomeric mol ratio of single end-blocking polyoxyethylene glycol-1000=1.5: 1 get two end-blocking polyoxyethylene glycol-1000 greatly monomer as linking agent.
Step 1, it is in 50% the alcoholic acid aqueous solution that the chitosan of 0.05mol is dispersed in massfraction, add the light trigger 1173 of the big monomer of single end-blocking polyoxyethylene glycol-1000, the big monomer of two end-blocking polyoxyethylene glycol-1000 and above two reactive monomer total masses 1.8% subsequently, stir;
Step 2 with methacrylic acid-conditioning solution acidity, makes the dissolving of dispersive chitosan become the thickness homogeneous solution, adds 1.5% solubility Cd of the big monomer total mass of chitosan and single end-blocking polyoxyethylene glycol-400 then
2+Salt and solubility Pb
2+The aqueous solution of salt, the described aqueous solution is specially, with Cd (NO
3)
2And Pb (NO
3)
2Be solute, press Cd
2+And Pb
2+Total mole number calculate Cd
2+The mole number ratio that accounts for total mole number be 50%; The preparation mass percent is 5% the aqueous solution.Polymers soln is carried out trace; The above-mentioned solution that trace is good, polymerization under ultraviolet lamp;
Step 3, polymerisate washes secondary with redistilled water, soaks 24h with the 0.1M hydrochloric acid soln, removes the Cd that trace is used
2+And Pb
2+,, be immersed in the redistilled water with redistilled water flushing three times.No longer change to pH=7 with ammoniacal liquor regulator solution acid number is stable, when making amino in the chitosan dissociate out, also make acrylic or methacrylic acid be converted into corresponding acrylamide or Methacrylamide.With redistilled water flushing three times, to filter, oven dry obtains having Cd
2+And Pb
2+The polymeric adsorbent of ion cavities can be to Cd in the underground water
2+And Pb
2+Ion optionally adsorbs and enrichment.
Embodiment 3
Take by weighing following raw material:
Chitosan 0.05mol;
Get single end-blocking polyoxyethylene glycol-400 monomer greatly by the mol ratio of the big monomer of methacrylic acid list end-blocking polyoxyethylene glycol-400 and chitosan=1: 3;
By the big monomer of the two end-blocking polyoxyethylene glycol-1000 of vinylformic acid and the big monomeric mol ratio of single end-blocking polyoxyethylene glycol-400=1.5: 1 get two end-blocking polyoxyethylene glycol-1000 greatly monomer as linking agent.
Step 1, it is in 50% the alcoholic acid aqueous solution that the chitosan of 0.05mol is dispersed in massfraction, add the light trigger 1173 of the big monomer of single end-blocking polyoxyethylene glycol-400, the big monomer of two end-blocking polyoxyethylene glycol-1000 and above two reactive monomer total masses 3% subsequently, stir;
Step 2 with methacrylic acid-conditioning solution acidity, makes the dissolving of dispersive chitosan become the thickness homogeneous solution, adds 2% solubility Cd of the big monomer total mass of chitosan and single end-blocking polyoxyethylene glycol-400 then
2+Salt and solubility Pb
2+The aqueous solution of salt, the described aqueous solution is specially, with Cd (NO
3)
2And Pb (NO
3)
2Be solute, press Cd
2+And Pb
2+Total mole number calculate Cd
2+The mole number ratio that accounts for total mole number be 70%; The preparation mass percent is 3% the aqueous solution.Polymers soln is carried out trace; The above-mentioned solution that trace is good, polymerization under ultraviolet lamp;
Step 3, polymerisate washes secondary with redistilled water, soaks 24h with the 0.1M hydrochloric acid soln, removes the Cd that trace is used
2+And Pb
2+Ion with redistilled water flushing three times, is immersed in the redistilled water.No longer change to pH=7 with ammoniacal liquor regulator solution acid number is stable, when making amino in the chitosan dissociate out, also make acrylic or methacrylic acid be converted into corresponding acrylamide or Methacrylamide.With redistilled water flushing three times, to filter, oven dry obtains having Cd
2+And Pb
2+The polymeric adsorbent of ion cavities can be to Cd in the underground water
2+And Pb
2+Ion optionally adsorbs and enrichment.
Embodiment 4
Take by weighing following raw material:
Chitosan 0.05mol;
Get single end-blocking polyoxyethylene glycol-1000 monomer greatly by the mol ratio of the big monomer of methacrylic acid list end-blocking polyoxyethylene glycol-1000 and chitosan=1: 5;
By the big monomer of the two end-blocking polyoxyethylene glycol-400 of vinylformic acid and the big monomeric mol ratio of single end-blocking polyoxyethylene glycol-1000=1.5: 1 get two end-blocking polyoxyethylene glycol-400 greatly monomer as linking agent.
Step 1, it is in 50% the alcoholic acid aqueous solution that the chitosan of 0.05mol is dispersed in massfraction, add the light trigger 1173 of the big monomer of single end-blocking polyoxyethylene glycol-400, the big monomer of two end-blocking polyoxyethylene glycol-1000 and above two reactive monomer total masses 5% subsequently, stir;
Step 2 with methacrylic acid-conditioning solution acidity, makes the dissolving of dispersive chitosan become the thickness homogeneous solution, adds 4% solubility Cd of the big monomer total mass of chitosan and single end-blocking polyoxyethylene glycol-400 then
2+Salt and solubility Pb
2+The aqueous solution of salt, the described aqueous solution is specially, with Cd (NO
3)
2And Pb (NO
3)
2Be solute, press Cd
2+And Pb
2+Total mole number calculate Cd
2+The mole number ratio that accounts for total mole number be 95%; The preparation mass percent is 1% the aqueous solution.Polymers soln is carried out trace; The above-mentioned solution that trace is good, polymerization under ultraviolet lamp;
Step 3, polymerisate washes secondary with redistilled water, soaks 24h with the 0.1M hydrochloric acid soln, removes the Cd that trace is used
2+And Pb
2+Ion with redistilled water flushing three times, is immersed in the redistilled water.No longer change to pH=7 with ammoniacal liquor regulator solution acid number is stable, when making amino in the chitosan dissociate out, also make acrylic or methacrylic acid be converted into corresponding acrylamide or Methacrylamide.With redistilled water flushing three times, to filter, oven dry obtains having Cd
2+And Pb
2+The polymeric adsorbent of ion cavities can be to Cd in the underground water
2+And Pb
2+Ion optionally adsorbs and enrichment.
Claims (8)
1. one kind has Cd
2+And Pb
2+The preparation method of the polymeric adsorbent of ion cavities is characterized in that, comprises the steps:
Step 1 adds chitosan in the alcoholic acid aqueous solution, add the big monomer of the end capped polyoxyethylene glycol of methacrylic acid list, the two big monomers of end capped polyoxyethylene glycol of vinylformic acid, light trigger simultaneously, stirs, and gets solution;
Step 2 adds acrylic or methacrylic acid in solution, add Cd afterwards
2+And Pb
2+, UV-irradiation gets solid product;
Step 3, with solid product salt acid soak, it is 7 that ammoniacal liquor is regulated its pH, oven dry obtains having Cd
2+And Pb
2+The polymeric adsorbent of ion cavities.
2. according to claim 1 have a Cd
2+And Pb
2+The preparation method of the polymeric adsorbent of ion cavities is characterized in that, in the step 1, the massfraction of the described alcoholic acid aqueous solution is 50%.
3. according to claim 1 have a Cd
2+And Pb
2+The preparation method of the polymeric adsorbent of ion cavities is characterized in that, in the step 1, in molar ratio, the ratio of big monomer of the end capped polyoxyethylene glycol of described list and chitosan is 1: (1～5).
4. according to claim 1 have a Cd
2+And Pb
2+The preparation method of the polymeric adsorbent of ion cavities is characterized in that, in the step 1, in molar ratio, described two big monomers of end capped polyoxyethylene glycol are 1.5: 1 with the big monomeric ratio of single end capped polyoxyethylene glycol.
5. according to claim 1 have a Cd
2+And Pb
2+The preparation method of the polymeric adsorbent of ion cavities is characterized in that, in the step 1, light trigger is two big monomers of end capped polyoxyethylene glycol and 1～5% of the big monomer total mass of single end capped polyoxyethylene glycol.
6. describedly has a Cd according to claim 1 or 4
2+And Pb
2+The preparation method of the polymeric adsorbent of ion cavities is characterized in that, in the step 1, described light trigger is a light trigger 1173.
7. according to claim 1 have a Cd
2+And Pb
2+The preparation method of the polymeric adsorbent of ion cavities is characterized in that, in the step 2, and described adding Cd
2+And Pb
2+Be specially: add solubility Cd
2+Salt and solubility Pb
2+The aqueous solution of salt, the described aqueous solution is specially, with solubility Cd
2+Salt and solubility Pb
2+Salt is solute, presses Cd
2+And Pb
2+Total mole number calculate 0＜Cd
2+Mole number account for ratio＜100% of total mole number; The preparation mass percent is 1%～15% the aqueous solution.
8. according to claim 7 have a Cd
2+And Pb
2+The preparation method of the polymeric adsorbent of ion cavities is characterized in that, the mass percent of the described aqueous solution is 1%～5%.
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|---|---|---|---|
| CN2009103125012A CN101735462B (en) | 2009-12-29 | 2009-12-29 | Method for preparing absorbent resin with bivalent cadmium ion and bivalent lead ion cavities |
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|---|---|---|---|
| CN2009103125012A CN101735462B (en) | 2009-12-29 | 2009-12-29 | Method for preparing absorbent resin with bivalent cadmium ion and bivalent lead ion cavities |
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| Publication Number | Publication Date |
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| CN101735462B true CN101735462B (en) | 2011-07-27 |
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|---|---|---|---|---|
| CN102172514A (en) * | 2011-01-26 | 2011-09-07 | 上海交通大学 | Absorbent material for selectively absorbing As<+5> ions and preparation method thereof |
| CN102151554A (en) * | 2011-01-26 | 2011-08-17 | 上海交通大学 | Preparation method of composite adsorption resin having selectivity |
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