CN101875003B - Preparation method of adsorbent resin with Cr ion cavities - Google Patents
Preparation method of adsorbent resin with Cr ion cavities Download PDFInfo
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- CN101875003B CN101875003B CN200910312497XA CN200910312497A CN101875003B CN 101875003 B CN101875003 B CN 101875003B CN 200910312497X A CN200910312497X A CN 200910312497XA CN 200910312497 A CN200910312497 A CN 200910312497A CN 101875003 B CN101875003 B CN 101875003B
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- polyethylene glycol
- ion
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- polymeric adsorbent
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Abstract
The invention relates to a preparation method of an adsorbent resin with Cr ion cavities, belonging to the technical field of water treatment. The method comprises the following steps of: firstly, adding chitosan in an aqueous solution with ethanol, simultaneously adding single-methacrylic acid-terminated polyethylene glycol macromonomer, dual-methacrylic acid-terminated polyethylene glycol macromonomer, and then stirring to obtain a solution; secondly, adding acrylic acid or methacrylic acid in the solution, then adding Cr<3+>, and irradiating by using ultraviolet light to obtain a solid product; and thirdly, soaking the solid product in hydrochloric acid, regulating the pH of the solid product to 7 by using ammonia water, and then drying to obtain the adsorbent resin with the Cr ion cavities. The adsorbent resin prepared in the method has high selectivity and adsorbability on Cr ions, is beneficial to the accurate collection of the Cr ions to achieve the purposes of removal and recovery, and can be repeatedly used.
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 of polymeric adsorbent of the Cr of having ion cavities.
Background technology
In the available freshwater resources in the whole world, underground water accounts for 95%.China's urban 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.Pollutant has heavy metal, metalloid ion (like AsO
3 -), organic matter and nitrate etc., and majority is a combined pollution.Cr particularly
6+As the property swallowed poisonous substance and imbedibility utmost point poisonous substance, the skin contact can cause allergy; More possibly cause the heredity gene defect, sucking maybe be carcinogenic, and environment is had lasting danger.It can pass through alimentary canal, respiratory tract, skin utmost point mucous membrane intrusion human body, very easily is absorbed by the body.Simultaneously, 10ppm Cr only
6+Just can lethal effect be arranged to aquatic organism.How to remove phreatic Cr
6+For the water safety that ensures people's lives, uplift the people's living standard, protect environment to have important practical significance.At present, the Cr in the removal underground water
6+Effective method is through adsorbing separation, and preparation adsorption efficiency excellence has selective absorption, enrichment performance and can reusable sorbing material be to improve ground water cleaning usefulness, reclaims Cr in the waste water
6+Basic assurance.
Molecular imprinting (Molecular Imprinting Technique; MIT) claim the molecular template technology again; Be to have combined subject knowledges such as polymer science, materialogy Chemical Engineering, be prepared in a kind of new technique of the cross-linked polymer that matees fully with template molecule or ion on space structure and the 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 cheap, obtained increasingly extensive application in fields such as the chromatographic isolation of chipal compounds, SPE, clinical drug analysis, film separation, biomimetic sensors, show 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 Cr in the underground water
6+In order to obtain at space structure and binding site and certain a part or ion) fully the coupling cross-linked polymer; Its preparation generally has the following step: the functionalized polymer monomer that at first will have complementary structure passes through covalently or non-covalently mode and template Cr ions bind; Next adds crosslinking agent and carries out cross-linked polymeric; At last after reaction is accomplished with Cr ion wash-out, obtain having and the single-minded three-dimensional hole that combines of Cr ion.It has high selectivity and high adsorption to the Cr ion, can accurately adsorb, enrichment Cr ion, reaches the purpose of removing and reclaiming.
Chitin is the main component in mushroom and the shellfish isoreactivity organism crust.Acetamido on 2 is with cellulose is different; It has similar structure with cellulose, and reaches 10,000,000,000 tons in natural output every year, is only second to cellulose; Coming second of natural polymer suboutput, is that a kind of reserves are extremely enriched the organic regenerative resource.Shitosan (CTS) is a kind of chitin derivativ that partially or completely removes acetyl; It has the mixed cell of 2-amino-2-deoxidation-β-D-glucosamine of 2-acetamide-2-deoxidation-β-D-glucose ring and the shitosan of chitin, and it is unique alkaline polysaccharide that present nature is found.Their chemical constitution is as shown in Figure 1.In general, the chitin that reaches more than 75% of deacetylation is called shitosan.Chitin and shitosan and derivative thereof have nontoxic, tasteless, in animal tissue, have biocompatibility and enzyme degradability.In recent decades, be used widely in biomedicine, ecological environment and the industrial circle.Owing on shitosan, have a large amount of amino, it has obtained extensive 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.Comparative?adsorption?of?Cu(II)，Zn(II)，and?Pb(II)ions?in?aqueous?solution?on?the?crosslinked?chitosanwith?epichrolohydrin，ournal?of?hazardous?materials，154(2008)，184～191)。Polyethylene glycol is widely used in the synthesized polymer material of ion enrichment as a kind of nonionic surface active agent, owing to have the circulus of the crooked similar crown ether of polyethylene glycol ability of certain-length, metal ion is had great sequestering power.
Literature search through to prior art is found, the report of Shang Weijian relevant " preparation method with polymeric adsorbent of Cr ion cavities ".
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of absorption of the Cr of having ion cavities is provided
The preparation method of resin.The polymeric adsorbent of method preparation of the present invention has high selectivity and high adsorption to the Cr ion, helps Cr ion (Cr
6+, Cr
3+) accurately enrichment, reaching the purpose of removing and reclaiming, this polymeric adsorbent can use repeatedly.
The present invention realizes that through following technical scheme technical scheme of the present invention comprises the steps:
Step 1 adds shitosan in the aqueous solution of ethanol, add the big monomer of polyethylene glycol of methacrylic acid list end-blocking simultaneously, the big monomer of polyethylene glycol of the two end-blockings of acrylic acid, and light trigger stirs, and gets solution;
Step 2 adds acrylic or methacrylic acid in solution, add Cr afterwards
3+, UV-irradiation gets solid product;
Step 3 is used the salt soak with solid product, and it is 7 that ammoniacal liquor is regulated its pH, dries, and obtains having the polymeric adsorbent of Cr ion cavities.
In the step 1, the mass fraction of the aqueous solution of said ethanol is 50%.
In the step 1, in molar ratio, the ratio of big monomer of the polyethylene glycol of said single end-blocking and shitosan is 1: (1～5).
In the step 1, in molar ratio, the big monomer of ethylene glycol that the said pair of end-blocking gathers is 1.5: 1 with the ratio of the big monomer of polyethylene glycol of single end-blocking.
In the step 1,1～5% of the big monomer of ethylene glycol that light trigger gathers for two end-blockings and the big monomer gross mass of polyethylene glycol of single end-blocking.
In the step 1, said light trigger is a light trigger 1173.
In the step 2, said adding Cr
3+Be specially: the adding mass percent is 1%～15% solubility Cr
3+The aqueous solution of salt.
In the step 2, said adding Cr
3+Be specially: the adding mass percent is 1%～5% solubility Cr
3+The aqueous solution of salt.
In the step 2, said solubility Cr
3+Salt is CrCl
3Or Cr (NO
3)
3
Light trigger of the present invention is the material that the ability cracking generates living radical under action of ultraviolet light; The big monomer of polyethylene glycol of methacrylic acid list end-blocking is an adsorbate; The big monomer of polyethylene glycol of the two end-blockings of acrylic acid is a crosslinking agent; Shitosan can only be dissolved in the acid solution, and acid commonly used has hydrochloric acid, acetate etc., but these acid inorganic acids commonly used and organic acid can only play the effect that promotes the shitosan dissolving in system.Select the acids of acrylic or methacrylic acid for use, can not only make the shitosan dissolving, in course of reaction, 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.Cross-linking and curing reaction with hydrochloric acid wash-out Cr ion, with the acid number pH=7 of ammoniacal liquor regulation system, makes the amino in the chitosan molecule dissociate out after accomplishing; 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 reaction; Generate transition metal intercalating agent acrylamide or Methacrylamide in the water commonly used, improved the adsorption 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 Cr ion (Cr
6+, Cr
3+) have high selectivity and high adsorption, help the accurate enrichment of Cr ion, reach the purpose of removing and reclaiming, this polymeric adsorbent can use repeatedly.
The specific embodiment
Present embodiment provided detailed embodiment and process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.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:
Shitosan 0.05mol;
Get single end-blocking polyethylene glycol-400 monomer greatly by the mol ratio of the big monomer of methacrylic acid list end-blocking polyethylene glycol-400 and shitosan=1: 1;
By the mol ratio of the big monomer of the two end-blocking polyethylene glycol-400 of acrylic acid and the big monomer of single end-blocking polyethylene glycol-400=1.5: 1 get two end-blocking polyethylene glycol-400 greatly monomer as crosslinking agent.
The preparation method of present embodiment comprises the steps:
Step 1; The shitosan of 0.05mol is dispersed in the aqueous solution that mass fraction is 50% ethanol; Add the light trigger 1173 of the big monomer of single end-blocking polyethylene glycol-400, the big monomer of two end-blocking polyethylene glycol-400 and above two reactive monomer gross masses 1% subsequently, stir;
Step 2 with metering system acid-conditioning solution acidity, makes the shitosan dissolving of dispersion become the thickness homogeneous solution, and 0.1% the mass fraction that adds the big monomer gross mass of shitosan and single end-blocking polyethylene glycol-400 then is 15% Cr (NO
3)
3The aqueous solution, polymer solution is carried out trace; The above-mentioned solution that trace is good, polymerization under uviol lamp;
Step 3, polymerizate washes secondary with redistilled water, soaks 24h with the 0.1M hydrochloric acid solution, removes the Cr that trace is used
3+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 shitosan dissociate out, also make acrylic or methacrylic acid be converted into corresponding acrylamide or Methacrylamide.With redistilled water flushing three times, filter, dry, obtain having the polymeric adsorbent of Cr ion cavities, can be to Cr in the underground water
6+, Cr
3+Ion optionally adsorbs and enrichment.
Embodiment 2
Take by weighing following raw material:
Take by weighing shitosan 0.05mol;
Get the big monomer of single end-blocking polyethylene glycol-1000 by the mol ratio of the big monomer of shitosan and methacrylic acid list end-blocking polyethylene glycol-1000=1: 2.5;
By the mol ratio of the big monomer of the two end-blocking polyethylene glycol-1000 of acrylic acid and the big monomer of single end-blocking polyethylene glycol-1000=1.5: 1 get two end-blocking polyethylene glycol-1000 greatly monomer as crosslinking agent.
The preparation method of present embodiment comprises the steps:
Step 1; The shitosan of 0.05mol is dispersed in the aqueous solution that mass fraction is 50% ethanol; Add the light trigger 1173 of the big monomer of single end-blocking polyethylene glycol-1000, the big monomer of two end-blocking polyethylene glycol-1000 and above two reactive monomer gross masses 1.8% subsequently, stir;
Step 2 with acrylic acid regulator solution acidity, makes the shitosan dissolving of dispersion become the thickness homogeneous solution, and 1.8% the mass fraction that adds the big monomer gross mass of shitosan and single end-blocking polyethylene glycol-400 then is 5% CrCl
3The aqueous solution, polymer solution is carried out trace; The above-mentioned solution that trace is good, polymerization under uviol lamp;
Step 3, polymerizate washes secondary with redistilled water, soaks 24h with the 0.1M hydrochloric acid solution, removes the Cr that trace is used
3+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 shitosan dissociate out, also make acrylic or methacrylic acid be converted into corresponding acrylamide or Methacrylamide.With redistilled water flushing three times, filter, dry, obtain having the polymeric adsorbent of Cr ion cavities, can be to Cr in the underground water
6+, Cr
3+Ion optionally adsorbs and enrichment.
Embodiment 3
Take by weighing following raw material:
Shitosan 0.05mol;
Get single end-blocking polyethylene glycol-400 monomer greatly by the mol ratio of the big monomer of methacrylic acid list end-blocking polyethylene glycol-400 and shitosan=1: 3;
By the mol ratio of the big monomer of the two end-blocking polyethylene glycol-1000 of acrylic acid and the big monomer of single end-blocking polyethylene glycol-400=1.5: 1 get two end-blocking polyethylene glycol-1000 greatly monomer as crosslinking agent.
The preparation method of present embodiment comprises the steps:
Step 1; The shitosan of 0.05mol is dispersed in the aqueous solution that mass fraction is 50% ethanol; Add the light trigger 1173 of the big monomer of single end-blocking polyethylene glycol-400, the big monomer of two end-blocking polyethylene glycol-1000 and above two reactive monomer gross masses 3% subsequently, stir;
Step 2 with metering system acid-conditioning solution acidity, makes the shitosan dissolving of dispersion become the thickness homogeneous solution, and 3% the mass fraction that adds the big monomer gross mass of shitosan and single end-blocking polyethylene glycol-400 then is 3% Cr (NO
3)
3The aqueous solution, polymer solution is carried out trace; The above-mentioned solution that trace is good, polymerization under uviol lamp;
Step 3, polymerizate washes secondary with redistilled water, soaks 24h with the 0.1M hydrochloric acid solution, removes the Cr that trace is used
3+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 shitosan dissociate out, also make acrylic or methacrylic acid be converted into corresponding acrylamide or Methacrylamide.With redistilled water flushing three times, filter, dry, obtain having the polymeric adsorbent of Cr ion cavities, can be to Cr in the underground water
6+, Cr
3+Ion optionally adsorbs and enrichment.
Embodiment 4
Take by weighing following raw material:
Shitosan 0.05mol;
Get single end-blocking polyethylene glycol-1000 monomer greatly by the mol ratio of the big monomer of methacrylic acid list end-blocking polyethylene glycol-1000 and shitosan=1: 5;
By the mol ratio of the big monomer of the two end-blocking polyethylene glycol-400 of acrylic acid and the big monomer of single end-blocking polyethylene glycol-1000=1.5: 1 get two end-blocking polyethylene glycol-400 greatly monomer as crosslinking agent.
The preparation method of present embodiment comprises the steps:
Step 1; The shitosan of 0.05mol is dispersed in the aqueous solution that mass fraction is 50% ethanol; Add the light trigger 1173 of the big monomer of single end-blocking polyethylene glycol-400, the big monomer of two end-blocking polyethylene glycol-1000 and above two reactive monomer gross masses 5% subsequently, stir;
Step 2 with acrylic acid regulator solution acidity, makes the shitosan dissolving of dispersion become the thickness homogeneous solution, and 4% the mass fraction that adds the big monomer gross mass of shitosan and single end-blocking polyethylene glycol-400 then is 1% Cr (NO
3)
3The aqueous solution, polymer solution is carried out trace; The above-mentioned solution that trace is good, polymerization under uviol lamp;
Step 3, polymerizate washes secondary with redistilled water, soaks 24h with the 0.1M hydrochloric acid solution, removes the Cr that trace is used
3+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 shitosan dissociate out, also make acrylic or methacrylic acid be converted into corresponding acrylamide or Methacrylamide.With redistilled water flushing three times, filter, dry, obtain having the polymeric adsorbent of Cr ion cavities, can be to Cr in the underground water
6+, Cr
3+Ion optionally adsorbs and enrichment.
Claims (9)
1. the preparation method with polymeric adsorbent of Cr ion cavities is characterized in that, comprises the steps:
Step 1 adds shitosan in the aqueous solution of ethanol, add the big monomer of polyethylene glycol of methacrylic acid list end-blocking simultaneously, the big monomer of polyethylene glycol of the two end-blockings of acrylic acid, and light trigger stirs, and gets solution;
Step 2 adds acrylic or methacrylic acid in solution, add Cr afterwards
3+, UV-irradiation gets solid product;
Step 3 is used the salt soak with solid product, and it is 7 that ammoniacal liquor is regulated its pH, dries, and obtains having the polymeric adsorbent of Cr ion cavities.
2. the preparation method with polymeric adsorbent of Cr ion cavities according to claim 1 is characterized in that, in the step 1, the mass fraction of the aqueous solution of said ethanol is 50%.
3. according to the described preparation method of claim l, it is characterized in that in the step 1, in molar ratio, the ratio of big monomer of the polyethylene glycol of said single end-blocking and shitosan is 1: (1～5) with polymeric adsorbent of Cr ion cavities.
4. the preparation method with polymeric adsorbent of Cr ion cavities according to claim 1 is characterized in that, in the step 1, in molar ratio, the big monomer of the polyethylene glycol of said pair of end-blocking is 1.5:1 with the ratio of the big monomer of polyethylene glycol of single end-blocking.
5. the preparation method with polymeric adsorbent of Cr ion cavities according to claim 1 is characterized in that, in the step 1, light trigger be two end-blockings the big monomer of polyethylene glycol and single end-blocking the big monomer gross mass of polyethylene glycol 1～5%.
6. according to claim 1 or 5 described preparation methods, it is characterized in that in the step 1, said light trigger is a light trigger 1173 with polymeric adsorbent of Cr ion cavities.
7. the preparation method with polymeric adsorbent of Cr ion cavities according to claim 1 is characterized in that, in the step 2, and said adding Cr
3+Ion is specially: adding mass percent is the solubility Cr of 1%-15%
3+The aqueous solution of salt.
8. the preparation method with polymeric adsorbent of Cr ion cavities according to claim 1 is characterized in that, in the step 2, and said adding Cr
3+Be specially: the adding mass percent is 1%～5% solubility Cr
3+The aqueous solution of salt.
9. according to claim 7 or 8 described preparation methods, it is characterized in that with polymeric adsorbent of Cr ion cavities, in the step 2, said solubility Cr
3+Salt is CrC1
3Or Cr (NO
3)
3
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| CN102151554A (en) * | 2011-01-26 | 2011-08-17 | 上海交通大学 | Preparation method of composite adsorption resin having selectivity |
| 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 |
| CN111995030A (en) * | 2020-07-10 | 2020-11-27 | 广西夏阳环保科技有限公司 | Chromium, nickel, zinc and copper electroplating wastewater treatment agent and treatment method thereof |
| CN115140763B (en) * | 2022-08-04 | 2023-05-30 | 先导薄膜材料有限公司 | Method for removing impurities in ITO (indium tin oxide) tower cleaning powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101301604A (en) * | 2008-06-04 | 2008-11-12 | 哈尔滨工程大学 | Method for preparing magnetic powder heavy metal ion blotting chitosan compound adsorbing agent |
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2009
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101301604A (en) * | 2008-06-04 | 2008-11-12 | 哈尔滨工程大学 | Method for preparing magnetic powder heavy metal ion blotting chitosan compound adsorbing agent |
Non-Patent Citations (3)
| Title |
|---|
| 余宙等.新型交联壳聚糖材料对地下水重金属Zn2+的吸附性能.《生态环境学报》.2009,第18卷(第6期),第2103页左栏第3段. * |
| 贺小进等.球形Ni2+模板壳聚糖树脂吸附性能及物性研究.《高校化学工程学报》.2001,第15卷(第1期),第23页最后1段至第24页第2段. * |
| 黄晓佳等.模板交联壳聚糖对过渡金属离子吸附性能研究.《离子交换与吸附》.2000,第16卷(第3期),第263页第2-4段. * |
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