CN100349653C - Preparation and performance of copper ion based chitin organic-inorganic hybridized silica gel carried selective adsorbing materials - Google Patents
Preparation and performance of copper ion based chitin organic-inorganic hybridized silica gel carried selective adsorbing materials Download PDFInfo
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- CN100349653C CN100349653C CNB2006100421523A CN200610042152A CN100349653C CN 100349653 C CN100349653 C CN 100349653C CN B2006100421523 A CNB2006100421523 A CN B2006100421523A CN 200610042152 A CN200610042152 A CN 200610042152A CN 100349653 C CN100349653 C CN 100349653C
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Abstract
The present invention discloses a new preparation method and the performances of chitosan organic-inorganic hybridized silica gel carried selective adsorbing materials based on copper ions. The present invention uses chitosan as organic functional molecules capable of gathering metal irons and uses gamma-epoxy propoxy propyl tri-methoxy silane containing epoxy groups and water solubility as an organic-inorganic hybridized inorganic source. The chitosan and the copper ions form complex compound and then carry out hybridization with the inorganic source. When the hydrolysis and condensation of silicon methoxy and the reaction of amino groups and epoxy groups in chitosan molecules form an organic-inorganic hybridized structure, the copper ions are embedded in the organic-inorganic hybridized structure. The elimination of the copper ions makes materials generate specific positive holes so that the materials have selective adsorbing capacity for the copper ions. The preparation process of the selective adsorbing mateirals of the present invention has the advantages of simplification, easy control to conditions and low production cost. The selective adsorbing materials have the advantages of good regeneration, repeatable use and no obvious change of the adsorption after regenerated.
Description
[technical field]
The present invention relates to a kind of preparation method and performance of copper ion selective absorbent, particularly a kind of preparation method and performance based on the organic-inorganic hybridized silica gel carried selective adsorbing materials of copper ion blotting chitosan.
[background technology]
Along with science and technology development, the material of single character can not satisfy people's needs.The function of two or more materials is compound, performance complement and optimization, the composite that processability is good is one of trend of modern material scientific development.By mix the organic-inorganic hybridized material that organic functional molecular obtains in inorganic network is a frontier of composite.The active force that organic-inorganic hybridized material two alternate existence are certain also forms interpenetrating networks, has the functional of high stability of inorganic material and organic material concurrently, has huge application potential.
High selectivity material with molecular recognition function is subjected to people's attention always.Molecular imprinting is one of main method of current preparation high selectivity material.Molecularly imprinted polymer according to this technology preparation shows predetermined, single-minded recognition performance owing to the stereochemical structure to microsphere has " memory " function, has broad application prospects in fields such as separation science, biosimulation science.Along with development of modern industry, human increasing to exploitation, smelting, processing and the commercial manufacturing activities of heavy metal, cause many heavy metals to enter atmosphere, water, soil environment, cause the serious environmental pollution.Preparation has the material of ion selectivity adsorption function, optionally removes or measure heavy metal element, has important practical significance.
Natural material forms the focus of studying into people owing to have excellent characteristic at aspects such as bio-compatibilities, and polysaccharide is one of them very active research field.Shitosan (β-(1,4)-2-amino-2-deoxy-D-glucose) is the product behind chitin (β-(1, the 4)-2-acetylaminohydroxyphenylarsonic acid 2-deoxy-D-glucose) deacetylation, and resource is very abundant.Contain a large amount of amino and hydroxyl in the chitosan molecule, can form stable chelate with heavy metal ion.In addition, shitosan has excellent biological compatibility, and is biodegradable at occurring in nature to people and biological nontoxic, is typical environment-friendly material.Therefore, shitosan and derivative thereof are very active as the research of metal ion adsorption material.Before carrying out ionic adsorption, adopt microemulsion polymerization method that shitosan is carried out the crosslinked crosslinked chitosan microsphere that makes to overcome its solubility in acid usually.The method need be used a large amount of organic solvents such as atoleine, and balling ratio is low, comprises comparatively difficulty of a large amount of surfactant extractings in the microballon that makes, and crosslinking agent commonly used such as glutaraldehyde, formaldehyde, epoxychloropropane etc. all have certain toxicity.In addition, the common mechanical strength of gained shitosan microballon is relatively poor, to the absorption non-selectivity of metal ion.Inorganic source being incorporated in the shitosan, forming organic-inorganic hybrid material, can have stability, the mechanical strength of the functional and inorganic structure of shitosan concurrently, is to substitute the novel and approach easily of shitosan conventional chemical cross-linking method.Simultaneously, the molecular engram effect by metal ion can realize specific recognition and the selective absorption of shitosan to metal ion.
The purpose of this invention is to provide a kind of novel preparation method based on the organic-inorganic hybridized silica gel carried selective adsorbing materials of copper ion blotting chitosan.Another object of the present invention is to investigate the performance of the selective absorbent of preparation.The present invention loads on the organic-inorganic hybridized thing of shitosan on the silica gel, with the nuclear of silica gel as the shitosan microballon, need not the shitosan granulation process, gained mechanical strength height.The present invention adopts and contains epoxide group, water miscible inorganic silane reagent γ-Huan Yangbingyangbingjisanjiayangjiguiwan as organic-inorganic hybridized inorganic source.The present invention carries out hydridization with inorganic source after making shitosan and copper ion form complex compound again.That the amino in the hydrolysis of silicon methoxyl group, condensation and the chitosan molecule and the reaction of epoxide group form is organic-inorganic hybrid structure the time, copper ion is embedded in the organic-inorganic hybridized structure.Removing of copper ion makes the specific hole of material production, and copper ion is had optionally adsorption capacity.The preparation process that the present invention is based on the organic-inorganic hybridized silica gel carried selective adsorbing materials of copper ion blotting chitosan is simple, and condition is easy to control, and production cost is low, and prepared imprinted material recognition performance in copper solution is good, reusable.
[summary of the invention]
At the problem that existing glycan substrate sorbing material exists, the invention provides that a kind of preparation process is simple, cheap, environmental friendliness, copper ion selective absorbent simple and easy to use.
Copper ion selective absorbent of the present invention is finished by following steps:
---a adds shitosan 2g, magnetic agitation 30min in 1mol/L 100mL acetum;
---b adds 6.38g Copper dichloride dihydrate, magnetic agitation 30min in solution;
---c adds γ-Huan Yangbingyangbingjisanjiayangjiguiwan 2mL, ultrasonic 40min in solution;
---d joins 50g 60-80 order silica gel in the solution behind the 1h 110 ℃ of activation, stirs, and suspension is poured in the culture dish, stirs, and room temperature leaves standstill 40 ℃ of oven dry behind the 48h;
---e soaks 15min with the gained blue solid in 0.5mol/L 100mL hydrochloric acid solution, solid is washed till neutrality with distilled water and is placed in the 0.01mol/L 100mL sodium hydroxide solution and soaks 30min, with distilled water solid is washed till neutrality, 40 ℃ of oven dry must be based on the organic-inorganic hybridized silica gel carried selective adsorbing materials of copper ion blotting chitosan.
The deacetylation of wherein said shitosan is 98%, molecular weight is 3.2 * 10
4G/mol.
Selective absorbent of the present invention is the organic-inorganic hybridized material of the shitosan of copper ions trace.But shitosan contains epoxide group, water miscible inorganic silane reagent γ-Huan Yangbingyangbingjisanjiayangjiguiwan as inorganic source as the organic functional molecular of chelated metal ions.The present invention carries out hydridization with inorganic source after making shitosan and copper ion form complex compound again.Hydrolysis, the condensation of the amino in the chitosan molecule and the reaction of epoxide group and silicon methoxyl group are carried out simultaneously, form organic-inorganic hybridized network structure.The hydroxyl, the amino that enrich in the chitosan molecule, the silanol groups that the inorganic silane component produces and the silanol groups on silica gel surface, all can provide a large amount of hydrogen bonds to form the site, make organic facies except that covalent bond, also have stronger hydrogen bond action between mutually, help obtaining the hybrid material of the tight homogeneous phase of organic-inorganic, molecular water sane level in the silica gel surface preparation with inorganic.Simultaneously, the chelation of shitosan makes copper ion also be embedded in the organic-inorganic hybridized structure.Copper ion removed make the gained material have specific hole, thereby copper ion is had selective adsorption capacity.The preparation process of copper ion selective absorbent of the present invention is simple, and condition is easy to control, and production cost is low.
Silica gel has high specific area and good mechanical strength.The present invention prepares selective absorbent with the organic-inorganic hybridized material load of the shitosan of copper ions trace on silica gel, during this sorbing material absorbing copper ion, the chitosan hybrid layer contact-making surface on copper ion in the solution and silica gel surface is big, makes that this selective absorbent adsorption rate is fast, mechanical strength is high.
The copper ion selective absorbent of the present invention's preparation, during the absorbing copper ion, simple to operate.Sorbing material can be used as the SPE material, by the dynamic absorbing copper ion of solid-phase extraction column; Also this selective absorbent directly can be added in the solution of copper ions, make solution fully contact the purpose that reaches the absorbing copper ion with sorbing material by stirring or shaking, sorbing material can be easily by depositing or centrifugal removing naturally.
With sorbing material to the absorption of copper ion and nickel ion coexistence down sorbing material be example to the selective absorption of copper ion, detect the absorption property of this patent sorbing material.The instrument that detects ion concentration be So1 AAR S2 type atomic absorption spectrophotometer (Thermo Electron Corporation, UK).
(1) this sorbing material is as the dynamic absorption of SPE material to copper ion
With this copper ion sorbing material homogenate method internal diameter of packing into is the glass chromatography column of 1.0cm, post height of bed 5cm.With the flow velocity of 1mL/min Cu by 100mg/L
2+Standard liquid (pH=5.0) flows out liquid and measures the content that flows out copper ion in the liquid with atomic absorption spectrophotometer, the leakage plot of record copper ion, calculating adsorbance behind the collection post.The result shows that this copper ion sorbing material dynamically adsorbs copper ion as the SPE material, and when pH=5.0, every gram sorbing material is to Cu
2+Adsorbance be 4.65mg.
(2) this sorbing material is to the vibration absorption of copper ion
Take by weighing the 1g sorbing material, the vinyon centrifuge tube of packing into is measured the Cu of certain volume 100mg/L
2+Standard liquid (pH=5.0) places this centrifuge tube, screws the centrifuge tube lid, the certain hour that vibrates in oscillator, the Cu before and after the absorption
2+Concentration records with atomic absorption spectrophotometer.To Cu
2+Concentration compared before and after standard liquid was crossed post, calculated the copper ion adsorbance according to following formula.
In the formula: Q is the adsorbance (mg/g) of every gram sorbing material to copper ion; C
0, C is respectively the initial concentration of copper ion in the solution and the equilibrium concentration (mg/L) after the absorption; V is the volume (mL) that is adsorbed copper ion solution; W is the dry weight (g) of sorbing material.
Experimental result shows that this copper ion sorbing material is to the vibration absorption of copper ion, and this sorbing material of every gram is to Cu during pH=5.0
2+Adsorbance be 4.78mg.
(3) Ni
2+This sorbing material is to the selection absorption property of copper ion during coexistence
With this copper ion selective absorbent homogenate method internal diameter of packing into is the glass chromatography column of 1.6cm, post height of bed 5cm.Flow velocity with 1mL/min passes through Cu
2+, Ni
2+Concentration be 100mg/L mixed solution, flow out liquid and measure the content that flows out the metal ion in the liquid, the leakage plot of record metal ion after collecting post with atomic absorption spectrophotometer.The result shows: behind the 50mL mixed liquor process solid-phase extraction column, and Ni
2+Begun behind post, to flow out, after about 80mL mixed liquor is crossed post, flowed out Ni in the liquid
2+Concentration reaches maximum (identical with original liquid concentration), flows out the Cu in the liquid this moment
2+Concentration has only 17% of original liquid concentration, thus confirm this sorbing material in the presence of the close heavy metal ion of character to Cu
2+Show higher selective adsorption capacity.
The regneration of adsorbent material that the present invention makes is convenient.The sorbing material of absorbing copper ion is soaked in the hydrochloric acid of 0.1mol/L behind the 1h, sorbing material is taken out be washed till neutrality, in the NaOH of 0.05mol/L, soak 10min then, dry after neutrality is washed in distillation with distilled water.Absorption property does not have significant change behind the regneration of adsorbent material, and is reusable.
The sorbing material that the present invention makes has good stable in acid, the acetum of usefulness 1mol/L does not detect shitosan after this sorbing material is shaken extracting 2h in the solution, illustrate that this sorbing material has good stable in acid.
Advantage of the present invention and effect:
1, selective absorbent of the present invention is the organic-inorganic hybridized material of shitosan of copper ions trace.The present invention carries out hydridization with inorganic source after making shitosan and copper ion form complex compound again.Organic facies exists covalent effect and hydrogen bond action with inorganic between mutually, and the gained sorbing material is solid solid particle, the tight homogeneous phase of organic-inorganic.After will being embedded into copper ion in the organic-inorganic hybridized structure and removing, the gained material has specific hole, and copper ion is had high selective adsorption capacity.The preparation process of copper ion selective absorbent of the present invention is simple, and condition is easy to control, and production cost is low.
2, the hydridization of shitosan of the present invention and inorganic source has been improved the shortcoming that glycan substrate acid is molten, matter is soft.
3, the present invention has overcome the shortcoming of shitosan granulation difficulty, gained sorbing material mechanical strength height with the organic-inorganic hybridized material load of the shitosan of copper ions trace on silica gel.
4, the copper ion selective absorbent of the present invention's preparation is during the absorbing copper ion, simple to operate.
5, the copper ion selective absorbent high adsorption capacity that makes of the present invention, the maximum adsorbable Cu of 1g sorbing material
2+4.78mg.
6, copper ion selective absorbent recognition performance in copper solution of making of the present invention is good, in the presence of the close heavy metal ion of character to Cu
2+Show higher selective adsorption capacity.
7, the copper ion selective absorbent regenerability that makes of the present invention is good, and regeneration back absorption property does not have significant change, and is reusable.
[specific embodiment]
With the room temperature cooling behind 110 ℃ of activation 1h of 50g 60-80 order silica gel.In 1mol/L 100mL acetum, add refining shitosan 2g, magnetic agitation 30min, filter cloth filters the back and removes insoluble residue; In filtrate, add the 6.38g Copper dichloride dihydrate, in solution, add 2mL inorganic silane reagent γ-Huan Yangbingyangbingjisanjiayangjiguiwan behind the magnetic agitation 30min, behind the ultrasonic 40min, in solution, add the silica gel that 50g has activated while stirring, after stirring suspension is poured in the culture dish, stir, room temperature leaves standstill 40 ℃ of oven dry behind the 48h; The gained blue solid is soaked 15min in 0.5mol/L 100mL hydrochloric acid solution, solid is washed till neutrality with distilled water and is placed in the 0.01mol/L 100mL sodium hydroxide solution and soaks 30min, with distilled water solid is washed till neutrality, 40 ℃ of oven dry must be based on the organic-inorganic hybridized silica gel carried selective adsorbing materials of copper ion blotting chitosan.
Claims (3)
1, a kind of preparation method based on the chitin organic-inorganic hybridized silica gel carried selective adsorbing materials of copper ion is characterized in that this selective absorbent prepares by following steps:
-a adds shitosan 2g, magnetic agitation 30min in the 1mol/L100mL acetum;
-b adds 6.38g Copper dichloride dihydrate, magnetic agitation 30min in solution;
-c adds γ-Huan Yangbingyangbingjisanjiayangjiguiwan 2mL, ultrasonic 40min in solution;
-d joins 50g 60-80 order silica gel in the solution behind the 1h 110 ℃ of activation, stirs, and suspension is poured in the culture dish, stirs, and room temperature leaves standstill 40 ℃ of oven dry behind the 48h;
-e soaks 15min with the gained blue solid in 0.5mol/L 100mL hydrochloric acid solution, solid is washed till neutrality with distilled water and is placed in the 0.01mol/L 100mL sodium hydroxide solution and soaks 30min, with distilled water solid is washed till neutrality, 40 ℃ of oven dry must be based on the chitin organic-inorganic hybridized silica gel carried selective adsorbing materials of copper ion.
2, the preparation method of selective absorbent according to claim 1, the deacetylation that it is characterized in that shitosan is 98%.
3, the preparation method of selective absorbent according to claim 1, the molecular weight that it is characterized in that shitosan is 3.2 * 10
4G/mol.
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| CN101745116B (en) * | 2008-12-17 | 2012-02-01 | 中国科学院大连化学物理研究所 | Preparation method for copper ion chelate adsorbing medium used for curing Wilson's disease |
| CN101711975B (en) * | 2009-11-03 | 2011-10-12 | 厦门大学 | Method for preparing iron ion imprinted silica gel |
| CN101724097B (en) * | 2009-12-14 | 2011-12-14 | 武汉理工大学 | Chitosan and metal copper ion complex protein-imprinted polymer and preparation method thereof |
| CN101869826B (en) * | 2010-06-13 | 2012-11-14 | 北京欧凯纳斯科技有限公司 | High-polymer compound chelated with heavy metal elements as well as preparation method and application thereof |
| CN102872808B (en) * | 2012-09-17 | 2014-02-19 | 工信华鑫科技有限公司 | Method for separating, enriching and purifying copper and nickel by using heavy metal adsorption material |
| CN102872807B (en) * | 2012-09-17 | 2014-02-19 | 工信华鑫科技有限公司 | Method for separating, enriching and purifying nickel and ferrous iron through heavy metal absorbing material |
| CN102815763B (en) * | 2012-09-17 | 2013-11-06 | 工信华鑫科技有限公司 | Method for implementing copper-cobalt separation, enrichment and purification by using heavy metal adsorbing material |
| CN105749879B (en) * | 2016-03-04 | 2018-08-10 | 江苏大学 | A kind of preparation method of duct filled-type molecular/ionic double site imprinted polymer |
| CN108212113B (en) * | 2018-02-08 | 2020-07-07 | 福州大学 | Method for preparing copper ion selective adsorbent by compounding sodium alginate/chitosan |
| CN109012639A (en) * | 2018-08-16 | 2018-12-18 | 辽宁大学 | Chitosan silicon based composite material of molybdenum trace and preparation method thereof and the application in recycling rhenium |
| CN112934199B (en) * | 2021-02-01 | 2022-09-23 | 南京大学 | Copper ion imprinted organic-inorganic hybrid monolithic column and preparation method and application thereof |
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