CN102989429A - Preparation method of cadmium ion surface imprint adsorbing material - Google Patents
Preparation method of cadmium ion surface imprint adsorbing material Download PDFInfo
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Abstract
The invention relates to a preparation method of an adsorbing material of metal ions in a water system and particularly relates to a preparation method of a cadmium ion surface imprint adsorbing material. The preparation method comprises the steps of placing functional grafting particles HQ-PHEMA (Hydroxyquinoline-Poly Hydroxyethyl Methylacrylate)/SiO2 into a Cd<2+> ion water solution with the concentration of 0.01 mol/L; adjusting the pH (Potential of Hydrogen) value of a solution system to 5.5 with a sodium hydroxide solution; placing the solution into a constant-temperature oscillator to carry out constant-temperature oscillation; filtering the particles and drying in vacuum; placing the functional grafting particles which are adsorbed with Cd<2+> ions in a saturated manner into a water and ethanol mixed solvent containing the Cd<2+> ions; utilizing the sodium hydroxide solution to adjust the pH value of the system; taking dichloroether as a cross-linking agent to react under the condition that the temperature is 40-50 DEG C for 20-26 hours to form a cross-linking imprint; utilizing a hydrochloric acid solution to repeatedly wash the product to remove template ions, namely the Cd<2+> ions; and drying in vacuum to form the Cd<2+> ion surface imprint adsorbing material.
Description
Technical field
The present invention relates to metal biosorption material preparation method in the aqueous systems, be specifically related to the preparation method of the surface imprinted sorbing material of a kind of cadmium ion.
Background technology
Heavy metal cadmium is a kind of harmful environomental pollution source, it not only affects growing of crop, and can also be by biological concentration and final healthy by the food chain harm humans, the cadmium of long-term excess intake, can affect the absorption of other beneficial elements in the human body, cause the problems such as endocrinopathy, poor appetite, insomnia, blood pressure rising.Cadmium poisoning can cause osteoporosis, softening and make textured bone fracture even dead.In addition, cadmium also is a kind of carcinogen, and IARC (IARC) divides cadmium into I class carcinogenic substance, and U.S. poisonous substance administration committee classifies cadmium as the 6th and jeopardizes the noxious material of health.Therefore process cadmium wastewater and eliminate cadmium pollution, exploitation efficient metal ion adsorbent has caused human showing great attention to.
At present, separating has multiple with the method for removing cadmium ion in the aqueous medium, such as chemical precipitation method, chemical reduction method, ion-exchange, hyperfiltration, membrane separation process, biological treatment and absorption method, all methods are compared, absorption method because its operation operation is easy, cost is low, remove that efficient is high, adsorbent also renewable with recycle, therefore, be a kind of effective method.But without recognition capability, so suction-operated lacks selectively general solid absorbent, greatly limited the application of general absorption method to the object ion in the water body.And with ion imprinted polymer material (Ion Imprinted Polymers, when being heavy metal ion in the sorbent treatment aqueous medium IIPs), then not only adsorption capacity is high, and has special adsorptive selectivity, is a kind of efficient solid-liquid processing method.Application number is preparation method and the application that discloses sponge gourd chromium surface lead ion trace sorbing material in 201010293780.5 the patent, and sponge gourd chromium surface ion blotting sorbing material lead ion maximal absorptive capacity is 335mg/g, and high adsorption rate can reach 95%.[the Gulay Bayramoglu such as Gulay Bayramoglu, M. Yakup Arica. Journal of Hazardous Materials.2011,187 (1-3): 213] the ion surface imprinted material of Cr (VI) of preparation is 3.31 mmol/g to the maximum adsorption capacity of heavy metal Cr (VI), repeatedly uses adsorption capacity can not reduce.
Traditional imprinted polymer uses the investment preparation, and the required device of the method is simple, and universality is strong, but has following shortcoming: prepared is block imprinted polymer, and imprinting efficiency is not high; Pulverize, grind and sieve the process of acquisition imprinted polymer particulate, operate comparatively numerous and diverse; And much the trace holes are destroyed, and cause trace hole Limited Number in the particle, and are not high to the binding ability of template (molecule) ion; In addition, be the particulate that presoma obtains by block imprinted polymer, matrix is thicker, and the duct in hole is darker, and template (molecule) ion diffusional resistance is large, and mass transfer velocity is slower, is difficult for being combined with recognition site.
Summary of the invention
Technical problem to be solved by this invention is: provide a kind of preparation technology simple, can have to cadmium ion the preparation method of the surface imprinted sorbing material of cadmium ion of superelevation identification and adsorption capacity.
The technical solution adopted in the present invention is: the preparation method of the surface imprinted sorbing material of a kind of cadmium ion, as follows preparation:
Step 1, saturated adsorption: with function grafting particulate HQ-PHEMA/SiO
2 (Bonding has the poly hydroxy ethyl acrylate (PHEMA) of oxine (HQ)/SiO
2) to place concentration be the Cd of 0.01 mol/L
2+Deionized water solution, the pH value of sodium hydroxide solution regulator solution system is 5.5, places constant temperature oscillator, constant temperature oscillation, function grafting particulate HQ-PHEMA/SiO
2With cadmium ion (Cd
2+) between interaction after, filtering particles, vacuum drying obtains saturated adsorption Cd
2+The function grafting particulate of ion;
Step 3, template removal: with hydrochloric acid solution cyclic washing step 2 product, to remove template ion Cd
2+Ion, vacuum drying has stayed a large amount of Cd in the polymer foil of function grafting particulate
2+The ion blotting hole, thus Cd formed
2+Ion surface imprinted sorbing material.
As a kind of optimal way: function grafting particulate HQ-PHEMA/SiO in the step 1
2In the PHEMA grafting degree be 30%-40%, the bonding density of HQ is 1.75mmol/g-1.85mmol/g, the Cd of every 5L
2+Put into the function grafting particulate HQ-PHEMA/SiO of 1g in the deionized water solution
2 , the constant temperature oscillation time is 4 h.
As a kind of optimal way: in the step 2 during preparation of the mixed solvent of water and ethanol the volume ratio of water and ethanol be 7:3, be 4.5-5.5 with the pH value of sodium hydroxide solution regulation system.
As a kind of optimal way: use 0.1 molL in the step 3
-1Hydrochloric acid solution cyclic washing product particulate.
The invention has the beneficial effects as follows: the trace hole of the imprinted polymer of (1) the method preparation is positioned at the top layer of imprinted polymer, and is fast in conjunction with speed to cadmium ion, the identification selection superelevation, and elution efficiency is high.With Cu
2+And Pb
2+Thing as a comparison, imprinted material is to Cd
2+The selectivity factor of ion is respectively 25.52 and 22.91; And in preparation process, the hole is not damaged, binding capacity is high, can reach 0.44mmol/g.(2) preparation process of the present invention is that mechanical strength is large take silica gel as matrix, is applicable to the requirement of suitability for industrialized production.Preparation process is simple, and cost is low, is easy to control.
Description of drawings
Fig. 1 is the chemical reaction process of the surface imprinted sorbing material of cadmium ion;
Fig. 2 be IIP-HQ-PHEMA/SiO2 to three heavy metal species ions in conjunction with thermoisopleth.
The specific embodiment
Example 1: be 40 g/100 g with the grafting degree of the function grafting particulate HQ-PHEMA/SiO2(PHEMA of 0.1 g, the bonding density of HQ is 1.85mmol/g) to place 500 mL concentration be the Cd of 0.01 mol/L
2+ In the deionized water solution, the pH value with diluted sodium hydroxide solution regulator solution system makes pH=5.5, and mixed liquor is placed constant temperature oscillator, and constant temperature oscillation 4 h make function grafting particulate HQ-PHEMA/SiO
2To Cd
2+The absorption of ion reaches capacity, filtering particles, vacuum drying.With 0.5 g saturated adsorption Cd
2+The function grafting particulate of ion places and contains Cd
2+In the water of ion (concentration is 0.01mol/L) and the alcohol mixed solvent (volume ratio of water and ethanol is 7:3), pH value with rare NaOH solution regulation system, make pH=5.5, the dichloroether aqueous solution (1%) that adds 5 mL makes crosslinked trace reaction carry out 24 h 45 ℃ of lower stirrings.Reaction is used 0.1 molL after finishing
-1 Hydrochloric acid solution cyclic washing product particulate is to remove template ion Cd
2+ Ion, vacuum drying namely gets Cd
2+ Ion surface imprinted material IIP-HQP/SiO
2
Example 2: with the function grafting particulate HQ-PHEMA/SiO of 0.1 g
2 (The grafting degree of PHEMA is 30 g/100 g, and the bonding density of HQ is 1.75mmol/g) to place 500 mL concentration be the Cd of 0.01 mol/L
2+In the deionized water solution, the pH value with diluted sodium hydroxide solution regulator solution system makes pH=5.5, and mixed liquor is placed constant temperature oscillator, and constant temperature oscillation 4 h make function grafting particulate HQ-PHEMA/SiO
2 To Cd
2+ The absorption of ion reaches capacity, filtering particles, vacuum drying.With 0.5 g saturated adsorption Cd
2+ The function grafting particulate of ion places and contains Cd
2+ In the water of ion (concentration is 0.01mol/L) and the alcohol mixed solvent (volume ratio of water and ethanol is 7:3), pH value with rare NaOH solution regulation system, make pH=5, add the dichloroether aqueous solution (1%) of 4 mL, make crosslinked trace reaction carry out 20 h 40 ℃ of lower stirrings.Reaction is used 0.1 molL after finishing
-1Hydrochloric acid solution cyclic washing product particulate is to remove template ion Cd
2+Ion, vacuum drying namely gets Cd
2+Ion surface imprinted material IIP-HQP/SiO
2
Example 3: with the function grafting particulate HQ-PHEMA/SiO of 0.1 g
2 (The grafting degree of PHEMA is 35 g/100 g, and the bonding density of HQ is 1.8mmol/g) to place 500 mL concentration be the Cd of 0.01 mol/L
2+ In the deionized water solution, the pH value with diluted sodium hydroxide solution regulator solution system makes pH=5.5, and mixed liquor is placed constant temperature oscillator, and constant temperature oscillation 4 h make function grafting particulate HQ-PHEMA/SiO
2 To Cd
2+ The absorption of ion reaches capacity, filtering particles, vacuum drying.With 0.5 g saturated adsorption Cd
2+The functional particles of ion places and contains Cd
2+In the water of ion (concentration is 0.01mol/L) and the alcohol mixed solvent (volume of water and ethanol is 7:3), pH value with rare NaOH solution regulation system, make pH=4.5, the dichloroether aqueous solution (1%) that adds 6 mL makes crosslinked trace reaction carry out 26 h 50 ℃ of lower stirrings.Reaction is used 0.1 molL after finishing
-1Hydrochloric acid solution cyclic washing product particulate is to remove template ion Cd
2+Ion, vacuum drying namely gets Cd
2+Ion surface imprinted material IIP-HQP/SiO
2
Adsorption test
Embodiment 4: static method: under 25 ℃ steady temperature, with the Cd of 20mL concentration series variation
2+ Solion places respectively some tool plug conical flasks, transfers pH=5, adds the imprinted material IIP-HQP/SiO of the 0.05g of accurate weighing
2 , the 4h that vibrates in constant temperature oscillator makes in conjunction with reaching balance, adopts Cd in the EDTA complexometric titration supernatant
2+ The equilibrium concentration of ion is calculated IIP-HQP/SiO
2To Cd
2+The junction at equilibrium resultant of ion is 0.44mmol/g, and uses the same method in conjunction with Cu
2+And Pb
2+The junction at equilibrium resultant is only seen accompanying drawing 1 trace particulate IIP-HQP/SiO for 0.02mmol/g(
2To three heavy metal species ions in conjunction with thermoisopleth).As can be seen from Figure 1 the surface imprinted sorbing material of cadmium ion has the selective and good binding affinity of specific recognition to cadmium sorption.
Embodiment 5: dynamic method: with the trace particulate IIP-HQP/SiO of 1.5 g
2 Be contained in the glass tube that internal diameter is 10 mm, making the bed volume (Bed Volume, BV) of packed column is 2 mL.Making concentration is the Cd of 0.01 mol/L
2+ Solion (pH=5) passes through packed column with the flow velocity adverse current of 4 BV/h, collects efflux with the interval of 2 BV, measures Cd in the efflux
2+ The concentration of ion is drawn the dynamic bind curve of imprinted material, and utilizes concentration and the bed volume number of efflux, calculates IIP-HQP/SiO
2 To Cd
2+ The leakage binding capacity of ion and saturated binding capacity.Adopt same method, measure respectively and draw imprinted material IIP-HQP/SiO
2 To Cu
2+ And Pb
2+ The dynamic bind curve of ion.The result shows, Cd
2+ The leakage volume of solion is higher, is 30 BV, Cu
2+ And Pb
2+-The leakage volume of solion only is 1 BV; Cd
2+The leakage adsorbance of ion and saturated extent of adsorption are 0.32 mmol/g and 0.45 mmol/g; And Cu
2+ And Pb
2+-The leakage adsorbance of ion is almost nil, and the former only is 0.025mmol/g for saturated extent of adsorption, and the latter only is 0.007mmol/g.Show Cd
2+ Ion surface imprinted material IIP-HQP/SiO
2Special identification selection and good binding affinity.
Embodiment 6: competitive adsorption: prepare respectively Cd
2+/ Cu
2+ With Cd
2+/ Pb
2+Two kinds of binary ion mixed solution (the pH value of solution all transfers to 5) are used imprinted material IIP-HQP/SiO
2, carried out the competitive Adsorption experiment.With respect to Cu
2+ Ion, imprinted material is to Cd
2+The selectivity factor of ion is very high, is 25.52, shows Cd
2+Ion has special identification selection; With respect to Pb
2+Ion, imprinted material is to Cd
2+The selectivity factor of ion is also very high, for 22.91. further clearly reveals, and Cd
2+Ion surface imprinted material IIP-HQP/SiO
2To Cd
2+Ion has the recognition capability of selective, the good binding affinity of special combination and superelevation really.
Embodiment 7: desorption performance: be that the hydrochloric acid solution of 0.1 mol/L is as eluent, upstream by saturated in conjunction with Cd with concentration
2+ The imprinted material IIP-HQ-PHEMA/SiO of ion
2Packed column carries out dynamic desorption experiment, obtains in 17 bed volumes desorption efficiency and reaches that desorption efficiency can reach 99.52% in 97.75%, 23 bed volume.Show and be bonded to imprinted material IIP-HQ-PHEMA/SiO
2On Cd
2+ Ion can be made adsorption column can obtain soon regeneration by wash-out promptly, is convenient to recirculation and uses.
Claims (4)
1. the preparation method of the surface imprinted sorbing material of cadmium ion is characterized in that: as follows preparation:
Step 1, saturated adsorption: with function grafting particulate HQ-PHEMA/SiO
2 Placing concentration is the Cd of 0.01 mol/L
2+Deionized water solution, the pH value of sodium hydroxide solution regulator solution system is 5.5, places constant temperature oscillator, constant temperature oscillation, filtering particles, vacuum drying obtains saturated adsorption Cd
2+The function grafting particulate of ion;
Step 2, crosslinked trace: with the saturated adsorption Cd of step 1 preparation
2+The function grafting particulate of ion places and contains Cd
2+In the water and alcohol mixed solvent of ion, with the pH value of sodium hydroxide solution regulation system, take dichloroether as crosslinking agent, be under 40 ℃ of-50 ℃ of conditions in temperature, the chlorine groups at dichloroether molecule two ends and function grafting particulate HQ-PHEMA/SiO
2The quaternized 20-26 h that reacts between the quinoline N atom on the side chain forms crosslinked trace;
Step 3, template removal: with hydrochloric acid solution cyclic washing step 2 product, to remove template ion Cd
2+Ion, vacuum drying has stayed a large amount of Cd in the polymer foil of function grafting particulate
2+The ion blotting hole, thus Cd formed
2+Ion surface imprinted sorbing material.
2. the preparation method of the surface imprinted sorbing material of a kind of cadmium ion according to claim 1 is characterized in that: function grafting particulate HQ-PHEMA/SiO in the step 1
2In the PHEMA grafting degree be 30%-40%, the bonding density of HQ is 1.75mmol/g-1.85mmol/g, the Cd of every 5L
2+Put into the function grafting particulate HQ-PHEMA/SiO of 1g in the deionized water solution
2 , the constant temperature oscillation time is 4 h.
3. the preparation method of the surface imprinted sorbing material of a kind of cadmium ion according to claim 1, it is characterized in that: the volume ratio of the mixed solvent of water and ethanol when preparation water and ethanol is 7:3 in the step 2, is 4.5-5.5 with the pH value of sodium hydroxide solution regulation system.
4. the preparation method of the surface imprinted sorbing material of a kind of cadmium ion according to claim 1 is characterized in that: use 0.1 molL in the step 3
-1Hydrochloric acid solution cyclic washing product particulate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804571A (en) * | 2013-08-26 | 2014-05-21 | 中国科学院城市环境研究所 | Nuclear shell temperature and PH double hypersensitivity metallic ion printing nanometer gel and preparation method thereof |
| CN105669918A (en) * | 2016-02-25 | 2016-06-15 | 中北大学 | Preparation method of trypsin surface imprinted microspheres by taking methacrylic acid as monomer |
| CN105693951A (en) * | 2016-02-25 | 2016-06-22 | 中北大学 | Preparation method of trypsin imprinted microsphere using sodium p-styrenesulfonate type monomers |
| CN106582569A (en) * | 2016-12-05 | 2017-04-26 | 北京科技大学 | Ion imprinted impregnating resin and preparation method thereof |
| CN111514861A (en) * | 2020-05-13 | 2020-08-11 | 天津工业大学 | Preparation method and application of tridentate ligand heavy metal ion imprinting material |
| CN113952940A (en) * | 2021-10-11 | 2022-01-21 | 江苏嘉通能源有限公司 | Preparation method of surface imprinted microsphere adsorption material for selectively removing Sb ions |
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| CN101928404A (en) * | 2010-07-09 | 2010-12-29 | 广东海洋大学 | Preparation of imprinted crosslinked chitosan resin and application thereof in removal of cadmium from pinctada martensii homogenate |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103804571A (en) * | 2013-08-26 | 2014-05-21 | 中国科学院城市环境研究所 | Nuclear shell temperature and PH double hypersensitivity metallic ion printing nanometer gel and preparation method thereof |
| CN103804571B (en) * | 2013-08-26 | 2016-08-31 | 中国科学院城市环境研究所 | A kind of hud typed temperature and pH Lazer property metal ion trace nanogel and preparation method thereof |
| CN105669918A (en) * | 2016-02-25 | 2016-06-15 | 中北大学 | Preparation method of trypsin surface imprinted microspheres by taking methacrylic acid as monomer |
| CN105693951A (en) * | 2016-02-25 | 2016-06-22 | 中北大学 | Preparation method of trypsin imprinted microsphere using sodium p-styrenesulfonate type monomers |
| CN105693951B (en) * | 2016-02-25 | 2018-02-09 | 中北大学 | A kind of preparation method using sodium p styrene sulfonate as the trypsase trace microballoon of monomer |
| CN105669918B (en) * | 2016-02-25 | 2018-07-27 | 中北大学 | It is a kind of using methacrylic acid as the preparation method of the surface imprinted microballoon of the trypsase of monomer |
| CN106582569A (en) * | 2016-12-05 | 2017-04-26 | 北京科技大学 | Ion imprinted impregnating resin and preparation method thereof |
| CN111514861A (en) * | 2020-05-13 | 2020-08-11 | 天津工业大学 | Preparation method and application of tridentate ligand heavy metal ion imprinting material |
| CN111514861B (en) * | 2020-05-13 | 2022-07-05 | 天津工业大学 | Preparation method and application of tridentate ligand heavy metal ion imprinting material |
| CN113952940A (en) * | 2021-10-11 | 2022-01-21 | 江苏嘉通能源有限公司 | Preparation method of surface imprinted microsphere adsorption material for selectively removing Sb ions |
| CN113952940B (en) * | 2021-10-11 | 2023-11-14 | 江苏嘉通能源有限公司 | Preparation method of surface imprinting microsphere adsorption material for selectively removing Sb ions |
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Inventor after: Men Jiying Inventor after: Wang Ruixin Inventor after: Gao Baojiao Inventor after: Li Yanbin Inventor after: Lei Qingjuan Inventor before: Gao Baojiao Inventor before: Men Jiying Inventor before: Wang Ruixin Inventor before: Li Yanbin Inventor before: Lei Qingjuan |
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