CN108816204A - A kind of preparation method of copper ion imprinted crosslinked chitosan microballoon - Google Patents
A kind of preparation method of copper ion imprinted crosslinked chitosan microballoon Download PDFInfo
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- CN108816204A CN108816204A CN201810746523.9A CN201810746523A CN108816204A CN 108816204 A CN108816204 A CN 108816204A CN 201810746523 A CN201810746523 A CN 201810746523A CN 108816204 A CN108816204 A CN 108816204A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
The invention discloses a kind of preparation methods of copper ion imprinted crosslinked chitosan microballoon, belong to materials science field.The present invention is, using chitosan as function monomer, using epoxychloropropane as crosslinking agent, to elute copper ion using copper ion as template ion by hydrochloric acid, prepare copper ion imprinted crosslinked chitosan microballoon.Microballoon prepared by the present invention to copper ion adsorption capacity with higher and adsorption selectivity, and adsorb, elution rate it is fast, operation is simple, renewable recycling.
Description
Technical field
The invention belongs to materials science fields, and in particular to a kind of preparation side of copper ion imprinted crosslinked chitosan microballoon
Method.
Background technique
It is more and more to contain Hg with China's industrial expansion2+、Ni2+、Cu2+、Pb2+、Cd2+Etc. heavy metal ion dirt
Water is discharged into environment water.Heavy metal have the characteristics that toxicity it is big, it is difficult to degrade, be easily enriched in vivo, and heavy metal
It is difficult to be degraded, is deposited in human body eventually by food chain, great harm is caused to ecological environment and human health.Copper
It is especially big with the affinity of tissues certain in human body, the activity of enzyme can be inhibited in conjunction with after, to generate toxic action to human body.Separately
Outside, copper is critically important valuable metal again, and being lost is also a kind of wasting of resources in sewage.Therefore it recycles valuable metal copper and goes
The copper polluted in water removal seems very necessary.Currently, the method for removing copper ion from waste water mainly has chemical precipitation method, ion
Exchange process, solvent extraction, membrane separation process etc..But these methods have the shortcomings that it is respective, if treatment effect is bad, processing cost
Height, process flow complexity etc..Absorption method efficiently separates technology as one kind, and, separation high, easy to operate with separative efficiency produces
The advantages that object is easily recycled is with a wide range of applications in terms of heavy mental treatment.
Molecular imprinting technology is to prepare the imprinted polymer technology for having specific selectivity to a certain specific target molecule.
Molecularly imprinted polymer has 3 big features：Precordainment, identity and practicability.Molecular engram, which also has, prepares simple, stability
By force, anti-adverse environment ability it is strong, can long-term preservation the advantages that, in chromatographic isolation, UF membrane, biomimetic sensor, selective catalysis
Etc. be widely used.Since amino and hydroxyl numerous on chitosan chain are that its structural modification and synthetic molecules trace are poly-
It closes object and provides possibility, therefore, be used for molecular engram material synthesis in recent years, carry out the polymerization with specific adsorption function
Object research becomes hot spot.
Chitosan as a kind of natural organic high-molecular flocculant, have Environmental compatibility it is good, renewable, resourceful with
And the advantages that height degradability, it include that the fields such as water process, cosmetics and pharmacy obtain in bioscience and multiple fields
To extensive use.Contain reactive group amino and hydroxyl in the strand of chitosan, will form cation in an acidic solution
Polyelectrolyte shows good flocculating property, can be with many metal ions（Hg2+、Ni2+、Cu2+、Pb2+、Cd2+、Ag+Deng）Shape
At stable chelate, and its special porous structure, make it have biggish specific surface area, the capacity of adsorbing metal ions
Greatly, but it is soluble in acid solution.In recent years, many scholars have studied the progress chemistry on the linear molecule chain of chitosan and change
Property, to improve its adsorbance or adsorptive selectivity etc., the common method using chemical crosslinking improves the acid-soluble of chitosan.
Cross-linked chitosan is to be modified under certain condition to chitosan progress intramolecular or intermolecular cross-linking, chitosan crosslinked
The adsorption capacity to heavy metal ion not only can be improved in product, and mechanical performance and the acid that also can obviously improve chitosan itself are molten
Property, anti-degradability is improved, stability of molecule is enhanced.Although cross-linking reaction solves mechanical strength of resin and reusable performance, but
The absorption property more uncrosslinked time difference is also resulted in, the main reason is that cross-linking reaction is frequently experienced on the higher amino of activity,
And after introducing other groups on amino, increase steric hindrance of the nitrogen-atoms with metallic ion coordination.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of copper ion imprinted crosslinked chitosan microballoon, it is intended to solve shell
The acid-soluble problem of glycan, improves the absorption property of cross-linked chitosan.
The technical scheme adopted by the invention is as follows：
A kind of preparation method of copper ion imprinted crosslinked chitosan microballoon, includes the following steps：
（1）Cu2+The preparation of blotting chitosan microballoon
Amount ratio according to acetic acid solution, chitosan, a water copper acetate is 100 mL: 1-3g: 0.25g, the second for being 3% by concentration
Acid solution is mixed with chitosan, after ultrasonic dissolution is complete, is added a water copper acetate and is sufficiently dissolved, obtain copper acetate-chitosan
Solution；
It is 1: 2 according to the volume ratio of copper acetate-chitosan solution and ammonia spirit, copper acetate-chitosan solution is added dropwise to body
Fraction is to impregnate solidification 24-28 h in the ammonia spirit of 12-12.5%, obtain Cu2+Blotting chitosan microballoon；If microballoon is set
Hygrometric state saves in deionized water, is hygrometric state Cu2+Blotting chitosan microballoon；If microballoon is dried at 45 DEG C, dry state Cu can be obtained2+
Blotting chitosan microballoon.
（2）Cu2+The preparation of imprinted crosslinked chitosan microballoon
Deionized water is added in beaker, step is then added（1）The Cu of preparation2+Blotting chitosan microballoon and epoxychloropropane,
The epoxychloropropane and step being added（1）In chitosan amount ratio be 1-3mL: 1-3g, the stirring crosslinking at 60-80 DEG C
Then 2-3 h carries out Cu to the microballoon after crosslinking2+Elution, until inspection does not measure Cu in eluent2+Until, then use deionized water
Washing obtains Cu to pH=62+Imprinted crosslinked chitosan microballoon.If microballoon is placed in hygrometric state in deionized water to save, for hygrometric state
Cu2+Imprinted crosslinked chitosan microballoon；If microballoon is dried at 45 DEG C, dry state Cu can be obtained2+Imprinted crosslinked chitosan microballoon.
Step（1）In, copper acetate-chitosan solution is added dropwise in ammonia spirit that the specific method is as follows：It is taken with No. 7 needle tubings
Copper acetate-chitosan solution, adjusting syringe needle and ammonium hydroxide liquid level distance is 15cm, is added dropwise to ammonium hydroxide with 28-32 drop/min speed
In solution.
Step（2）In, elute Cu2+The specific method is as follows：At 60 DEG C with 100mL concentration be 1moL/L dilute hydrochloric acid elution
Cu2+After 1h, it is 5.4g/L copper reagent that 1-2 drop concentration is added dropwise in eluent, and elution waste liquid is in dark brown and floccule occurs；
Microballoon is washed repeatedly with deionized water, adds 50mL dilute hydrochloric acid elution Cu2+After 0.5h, elution waste liquid is brown；Repetition is washed
Take off is colourless to elution waste liquid for several times, illustrates the template Cu in microballoon2+All elution, be then washed with deionized to pH=
6。
The invention adopts the above technical scheme, using chitosan as function monomer, using molecular imprinting technology, Cu2+Ion is made
It is fixed the spatial position of amino, hydroxyl for imprinted templates, recycles epoxychloropropane to carry out cross-linking reaction, finally by salt
Pickling is de- to make imprinted templates Cu2+It removes and makes-NH2It is released, so that being made has compared with high absorption capacity and choosing copper ion
Select the copper ion imprinted crosslinked chitosan microballoon of absorption property, and adsorb, elution rate it is fast, operation is simple, renewable to follow
Ring uses, and provides a kind of new technology for the high efficiente callback of copper, has important meaning to environmental pollution and resource recycling is solved
Justice.
Detailed description of the invention
Fig. 1 is the FT-IR spectrogram of the embodiment of the present invention 1,2 product of embodiment, and a is chitosan, b Cu2+Blotting chitosan,
C is Cu2+Imprinted crosslinked chitosan；
Fig. 2 is the XRD spectra of the embodiment of the present invention 1,2 product of embodiment, and a is chitosan, b Cu2+Blotting chitosan, c are
Cu2+Imprinted crosslinked chitosan；
Fig. 3 is the SEM figure of the embodiment of the present invention 1,2 product of embodiment, and a is chitosan, b Cu2+Blotting chitosan, c Cu2+
Imprinted crosslinked chitosan；
Fig. 4 is that the EDX of 1 product of the embodiment of the present invention schemes；
Fig. 5 is that the EDX of 2 product of the embodiment of the present invention schemes.
Specific embodiment
Below with reference to specific example, the present invention is furture elucidated.
A kind of preparation method of copper ion imprinted crosslinked chitosan microballoon, includes the following steps：
（1）Cu2+The preparation of blotting chitosan microballoon
Amount ratio according to acetic acid solution, chitosan, a water copper acetate is 100 mL: 1-3g: 0.25g, the second for being 3% by concentration
Acid solution is mixed with chitosan, after ultrasonic dissolution is complete, is added a water copper acetate and is sufficiently dissolved, obtain copper acetate-chitosan
Solution；
Copper acetate-chitosan solution is taken with No. 7 needle tubings, adjusting syringe needle and ammonium hydroxide liquid level distance is 15cm, with 28-32 drop/min
It is in 12-12.5% ammonia spirit that speed, which is added dropwise to volume fraction,（The volume ratio of copper acetate-chitosan solution and ammonia spirit is 1
:2）, solidification 24-28 h is impregnated, Cu is obtained2+Blotting chitosan microballoon；It is wet if microballoon is placed in hygrometric state in deionized water to save
State Cu2+Blotting chitosan microballoon；If microballoon is dried at 45 DEG C, dry state Cu can be obtained2+Blotting chitosan microballoon.
（2）Cu2+The preparation of imprinted crosslinked chitosan microballoon
Deionized water is added in beaker, step is then added（1）The Cu of preparation2+Blotting chitosan microballoon and epoxychloropropane,
The epoxychloropropane and step being added（1）In chitosan amount ratio be 1-3mL: 1-3g, the stirring crosslinking at 60-80 DEG C
Then 2-3 h carries out Cu to the microballoon after crosslinking2+Elution, until inspection does not measure Cu in eluent2+Until, then use deionized water
Washing obtains Cu to pH=62+Imprinted crosslinked chitosan microballoon.If microballoon is placed in hygrometric state in deionized water to save, for hygrometric state
Cu2+Imprinted crosslinked chitosan microballoon；If microballoon is dried at 45 DEG C, dry state Cu can be obtained2+Imprinted crosslinked chitosan microballoon.
Wherein, Cu is eluted2+The specific method is as follows：At 60 DEG C with 100mL concentration be 1moL/L dilute hydrochloric acid elution Cu2+
After 1h, it is 5.4g/L copper reagent that 1-2 drop concentration is added dropwise in eluent, and elution waste liquid is in dark brown and floccule occurs；It spends
Ionized water washs microballoon repeatedly, adds 50mL dilute hydrochloric acid elution Cu2+After 0.5h, elution waste liquid is brown；Repeat elution number
It is secondary to elution waste liquid be it is colourless, illustrate the template Cu in microballoon2+All elutions, are then washed with deionized to pH=6.
Embodiment 1
Cu2+The preparation of blotting chitosan microballoon
The acetic acid solution that 100mL concentration is 3% is measured in beaker, the Chitosan powder of 1.5g is added, after ultrasonic dissolution is complete,
It adds mono- water copper acetate of 0.25g sufficiently to dissolve, obtains copper acetate-chitosan solution；It is accurate to measure 20mL copper acetate-chitosan
Solution takes copper acetate-chitosan solution with No. 7 needle tubings, and adjusting syringe needle and liquid level distance is 15cm, with 30 drops/min speed drop
Enter in the dilute ammonia solution for being 12.5% to 40mL volume fraction, impregnate solidification for 24 hours, microballoon is placed in hygrometric state in deionized water and is protected
It deposits to get hygrometric state Cu2+Blotting chitosan microballoon.
Embodiment 2
Cu2+The preparation of imprinted crosslinked chitosan microballoon
The deionized water of 80mL is measured in beaker, Cu obtained in embodiment 1 is added2+Blotting chitosan microballoon, addition
2.5mL epoxychloropropane stirs 3h at 80 DEG C, carries out full cross-linked.Addition 100mL concentration is 1mol/L dilute hydrochloric acid solution,
Cu is eluted at 60 DEG C2+Repeatedly, Cu is not measured until examining in eluent2+Until, it is washed with deionized to pH=6, by microballoon
Hygrometric state in deionized water is placed in save to get hygrometric state Cu2+Imprinted crosslinked chitosan microballoon；If microballoon is dried at 45 DEG C, can obtain
Dry state Cu2+Imprinted crosslinked chitosan microballoon.
Embodiment 3
The Cu prepared using epoxychloropropane as crosslinking agent2+Adsorption effect of the imprinted crosslinked chitosan microballoon to copper ion
Weigh hygrometric state Cu made from 0.4075 g embodiment 22+Imprinted crosslinked chitosan microballoon, being placed in concentration is 338.7 mg/L
Copper solution in, at 30 DEG C oscillation absorption 24 h, to reach adsorption equilibrium.Using visible spectrophotometer in maximum absorption wavelength
The absorbance of measurement absorption front and back copper solution, looks into Cu at 452 nm2+Absorbance-concentration standard curve figure, is calculated Cu2+Print
Mark crosslinked chitosan microsphere is 73.4mg/g to the adsorbance of copper ion.
Comparative example 1
The Cu prepared using glyoxal as crosslinking agent2+Adsorption effect of the imprinted crosslinked chitosan microballoon to copper ion
（1）Using glyoxal as the Cu of crosslinking agent2+The preparation of imprinted crosslinked chitosan microballoon
The deionized water of 80mL is measured in beaker, Cu obtained in embodiment 1 is added2+Blotting chitosan microballoon, addition
2.5mL glyoxal stirs 3h at 80 DEG C, carries out full cross-linked.Addition 100mL concentration is 1mol/L dilute hydrochloric acid solution, 60
Cu is eluted at DEG C2+Repeatedly, Cu is not measured until examining in eluent2+Until, it is washed with deionized to pH=6, microballoon is placed in
Hygrometric state saves to get hygrometric state Cu in deionized water2+Imprinted crosslinked chitosan microballoon；If microballoon is dried at 45 DEG C, dry state can be obtained
Cu2+Imprinted crosslinked chitosan microballoon.
（2）Copper absorption test
Weigh 0.4075 g step（1）Hygrometric state Cu obtained2+Imprinted crosslinked chitosan microballoon, being placed in concentration is 338.7 mg/L
Copper solution in, at 30 DEG C oscillation absorption 24 h, to reach adsorption equilibrium.Using visible spectrophotometer in maximum absorption wavelength
The absorbance of measurement absorption front and back copper solution, looks into Cu at 452 nm2+Absorbance-concentration standard curve figure, is calculated Cu2+Print
Mark crosslinked chitosan microsphere is 56.40mg/g to the adsorbance of copper ion.
Comparative example 2
The Cu prepared with glutaraldehyde as cross linker2+Adsorption effect of the imprinted crosslinked chitosan microballoon to copper ion
（1）With the Cu of glutaraldehyde as cross linker2+The preparation of imprinted crosslinked chitosan microballoon
The deionized water of 80mL is measured in beaker, Cu obtained in embodiment 1 is added2+Blotting chitosan microballoon, addition
2.5mL glutaraldehyde stirs 3h at 80 DEG C, carries out full cross-linked.Addition 100mL concentration is 1mol/L dilute hydrochloric acid solution, 60
Cu is eluted at DEG C2+Repeatedly, Cu is not measured until examining in eluent2+Until, it is washed with deionized to pH=6, microballoon is placed in
Hygrometric state saves to get hygrometric state Cu in deionized water2+Imprinted crosslinked chitosan microballoon；If microballoon is dried at 45 DEG C, dry state can be obtained
Cu2+Imprinted crosslinked chitosan microballoon.
（2）Copper absorption test
Weigh 0.4075 g step（1）Hygrometric state Cu obtained2+Imprinted crosslinked chitosan microballoon, being placed in concentration is 338.7 mg/L
Copper solution in, at 30 DEG C oscillation absorption 24 h, to reach adsorption equilibrium.Using visible spectrophotometer in maximum absorption wavelength
The absorbance of measurement absorption front and back copper solution, looks into Cu at 452 nm2+Absorbance-concentration standard curve figure, is calculated Cu2+Print
Mark crosslinked chitosan microsphere is 30.48mg/g to the adsorbance of copper ion.
By embodiment 3, comparative example 1, comparative example 2 it is found that three kinds of epoxychloropropane, glyoxal and glutaraldehyde is respectively adopted not
Same crosslinking agent is compared adsorption effect, found under same adsorption conditions, the Cu prepared using epoxychloropropane as crosslinking agent2+Trace
The adsorbance highest of crosslinked chitosan microsphere, adsorption effect are best.This is because the amino in epoxy group and chitosan molecule
Reaction forms hydroxyl, is basically unchanged to the chelation of copper ion, adsorption site is not reduced, therefore adsorbance will not reduce.
And glyoxal, glutaraldehyde cross-linking agent are used, corresponding schiff bases is produced after the amino reaction of the carbonyl of aldehyde and chitosan, is lost pair
The chelation of copper ion, adsorption site are reduced, and will lead to adsorbance reduction.Therefore the application finally uses epoxychloropropane to make
Cu is prepared for crosslinking agent2+Imprinted crosslinked chitosan microballoon.
Claims (4)
1. a kind of preparation method of copper ion imprinted crosslinked chitosan microballoon, it is characterised in that：It includes the following steps：
（1）Cu2+The preparation of blotting chitosan microballoon
Amount ratio according to acetic acid solution, chitosan, a water copper acetate is 100 mL: 1-3g: 0.25g, the second for being 3% by concentration
Acid solution is mixed with chitosan, after ultrasonic dissolution is complete, is added a water copper acetate and is sufficiently dissolved, obtain copper acetate-chitosan
Solution；
It is 1: 2 according to the volume ratio of copper acetate-chitosan solution and ammonia spirit, copper acetate-chitosan solution is added dropwise to body
Fraction is to impregnate solidification 24-28 h in the ammonia spirit of 12-12.5%, obtain Cu2+Blotting chitosan microballoon；
（2）Cu2+The preparation of imprinted crosslinked chitosan microballoon
Deionized water is added in a reservoir, step is then added（1）The Cu of preparation2+Blotting chitosan microballoon and epoxychloropropane,
Then the stirring crosslinking 2-3 h at 60-80 DEG C carries out Cu to the microballoon after crosslinking2+Elution does not measure until examining in eluent
Cu2+Until, then be washed with deionized to pH=6, obtain Cu2+Imprinted crosslinked chitosan microballoon.
2. a kind of preparation method of copper ion imprinted crosslinked chitosan microballoon described in claim 1, it is characterised in that：Step
（2）The epoxychloropropane and step being added（1）In chitosan amount ratio be 1-3mL: 1-3g.
3. a kind of preparation method of copper ion imprinted crosslinked chitosan microballoon described in claim 1, it is characterised in that：Step
（1）In, copper acetate-chitosan solution is added dropwise in ammonia spirit that the specific method is as follows：Take copper acetate-shell poly- with No. 7 needle tubings
Sugar juice, adjusting syringe needle and ammonium hydroxide liquid level distance is 15cm, is added dropwise in ammonia spirit with 28-32 drop/min speed.
4. a kind of preparation method of copper ion imprinted crosslinked chitosan microballoon described in claim 1, it is characterised in that：Step
（2）In, elute Cu2+The specific method is as follows：At 60 DEG C with 100mL concentration be 1moL/L dilute hydrochloric acid elution Cu2+After 1h,
It is 5.4g/L copper reagent that 1-2 drop concentration is added dropwise in eluent, and elution waste liquid is in dark brown and floccule occurs；It will with deionized water
Microballoon washing repeatedly, adds 50mL dilute hydrochloric acid elution Cu2+After 0.5h, elution waste liquid is brown；Elution is repeated for several times to elution
Waste liquid be it is colourless, be then washed with deionized to pH=6.
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| CN110508259A (en) * | 2019-09-03 | 2019-11-29 | 晋江瑞碧科技有限公司 | A kind of preparation method of copper ion trace composite magnetic hollow microsphere |
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| CN113244895A (en) * | 2021-04-08 | 2021-08-13 | 浙江工业大学 | Preparation method of lithium ion imprinted cross-linked chitosan porous microspheres |
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| CN113959985A (en) * | 2021-11-17 | 2022-01-21 | 南昌航空大学 | Multi-channel heavy metal ion detection device based on ion imprinting micro-nano optical fiber interferometer |
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| CN113244895A (en) * | 2021-04-08 | 2021-08-13 | 浙江工业大学 | Preparation method of lithium ion imprinted cross-linked chitosan porous microspheres |
| CN113351187A (en) * | 2021-06-23 | 2021-09-07 | 中南林业科技大学 | Heavy metal ion imprinted hydrogel ball and preparation method and application thereof |
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