CN115090267A - Preparation method of copper ion imprinted cross-linked chitosan porous microspheres - Google Patents
Preparation method of copper ion imprinted cross-linked chitosan porous microspheres Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 202
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 93
- 239000004005 microsphere Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011324 bead Substances 0.000 claims abstract description 70
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000001509 sodium citrate Substances 0.000 claims abstract description 25
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 25
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 15
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 89
- 239000010949 copper Substances 0.000 claims description 47
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 25
- 150000004696 coordination complex Chemical class 0.000 claims description 24
- 238000004132 cross linking Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 5
- 230000006196 deacetylation Effects 0.000 claims description 3
- 238000003381 deacetylation reaction Methods 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 56
- 150000002500 ions Chemical class 0.000 abstract description 8
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000010382 chemical cross-linking Methods 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 24
- 238000004090 dissolution Methods 0.000 description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 18
- 239000003463 adsorbent Substances 0.000 description 15
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 10
- 239000001630 malic acid Substances 0.000 description 10
- 235000011090 malic acid Nutrition 0.000 description 10
- 238000011056 performance test Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010828 elution Methods 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
-
- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a preparation method of copper ion imprinted cross-linked chitosan porous microspheres, which comprises the following steps: taking hydrosol formed by acetic acid, chitosan powder and pore-forming agent polyethylene glycol as a dispersion phase, taking trisodium citrate solution as a continuous phase, and forming chitosan gel beads through chemical crosslinking; taking chitosan gel beads as a carrier, copper ions as template ions, trisodium citrate as a functional monomer for grafting modification, taking epichlorohydrin as a cross-linking agent, and eluting the copper ions through EDTA-2Na to prepare the copper ion imprinted cross-linked chitosan porous microspheres. The porous microspheres prepared by the method have high adsorption capacity and identification capacity on copper ions, and are good in adsorption regeneration performance and simple and easy to operate.
Description
Technical Field
The invention relates to the technical field of material science, in particular to a preparation method of copper ion imprinted cross-linked chitosan porous microspheres.
Background
With the vigorous mining of ores and the mass production of steel and electronic products, the discharge of industrial wastewater causes the heavy metal content in water quality and soil to rise straight, the ecological environment is seriously deteriorated, and the excessive copper metal causes heavy metal copper pollution. The copper element has close relationship with human life and development, has wide application field, and mainly belongs to the industries of electrical, mechanical manufacturing, light industry and the like. The copper content in natural water is extremely low, and the pollution discharge of industrial wastewater causes the copper ion content in water to be gradually increased, thus harming the health of aquatic organisms and human beings. Since heavy metal ions such as copper are difficult to biodegrade in the environment and gradually accumulate in their contents as the food chain progresses, various diseases are finally induced in the organism. Therefore, researchers pay attention to how to effectively remove heavy metal copper ions from wastewater. At present, an adsorption method is widely applied, but the problem of specifically removing copper ions in the presence of other interfering ions in wastewater is difficult to solve by using a common adsorbent. The ion imprinting technology can realize specific recognition and adsorption of target ions, has the characteristics of affinity, high efficiency, recoverability and the like, carries out graft modification on a matrix by various chemical means, and adds a cross-linking agent, an eluant and the like to fix an adsorption cavity, so that the selection of a proper imprinting carrier is very important.
The chitosan has the characteristics of biodegradability in natural environment, no harm to environment and other organisms, easy obtainment and the like, and is an ideal biological adsorbent. A plurality of active groups, namely amino and hydroxyl, exist on the branched chain of the chitosan molecule, and can be chelated with metal ions, so that the chitosan molecule has certain adsorption property. In addition, the amino groups on the chitosan molecules are easily protonated and softened under acidic conditions, and the mechanical strength of the chitosan molecules is low, so that the materials are easily lost in the adsorption process, which limits the application of chitosan.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a preparation method of copper ion imprinted cross-linked chitosan porous microspheres, and the porous microspheres prepared by the method have high-efficiency selective adsorption capacity on copper ions. According to the invention, chitosan is used as an imprinting carrier, a functional monomer is grafted on a molecular branch chain to improve the selective adsorption of the chitosan on copper ions, the mechanical strength is improved through cross-linking of a cross-linking agent, the molecular stability is enhanced, and a proper amount of pore-forming agent is added to form the copper ion imprinting chitosan-based porous microspheres, so that the adsorption capacity is enhanced.
The specific technical scheme is as follows:
a preparation method of copper ion imprinted cross-linked chitosan porous microspheres comprises the following steps:
(1) dissolving chitosan powder with acetic acid aqueous solution, adding a pore-forming agent, and mixing to obtain acetic acid-chitosan solution;
(2) slowly dripping the dispersed phase into the continuous phase by taking a trisodium citrate water solution as the continuous phase and an acetic acid-chitosan solution as the dispersed phase, soaking and solidifying to form citric acid modified chitosan porous gel beads, and washing with deionized water for several times;
(3) mixing the modified chitosan porous gel beads obtained in the step (2) with excessive copper ion solution, and carrying out imprinting reaction; adding epichlorohydrin and isopropanol into the solution to carry out crosslinking reaction to obtain modified chitosan metal complex pre-crosslinked porous microspheres;
(4) performing Cu on the modified chitosan metal complex pre-crosslinked porous microspheres obtained in the step (3) 2+ And (3) eluting, washing to be neutral, and freeze-drying to obtain the copper ion imprinted cross-linked chitosan porous microspheres.
Further, in the step (1), the molecular weight of the chitosan is 3-100 ten thousand, the viscosity is 200-400 mPa.s, and the deacetylation degree is 70-100%.
Further, in the acetic acid-chitosan solution in the step (1), the concentration of acetic acid is 1-5 wt%, and the concentration of chitosan is 1-4 wt%; the pore-forming agent is polyethylene glycol, the concentration is 1-2 wt%, and the molecular weight of the polyethylene glycol is 600-4000.
Further, in the step (2), the volume ratio of the acetic acid-chitosan solution to the trisodium citrate aqueous solution is 1: 2-5, and the concentration of the trisodium citrate aqueous solution is 8-12 wt%; the soaking and curing time is 20-48 h.
Further, in the step (2), the specific method for dropping the acetic acid-chitosan solution into the trisodium citrate aqueous solution is as follows: taking the acetic acid-chitosan solution by using a needle tube, adjusting the distance between a needle head and the liquid level of the trisodium citrate aqueous solution to be 10-20 cm, and dripping the acetic acid-chitosan solution into the trisodium citrate aqueous solution at the speed of 30-35 drops/min.
Further, in the step (3), the concentration of the copper ion solution is 64-100 mg/L, and the feeding ratio of the modified chitosan porous gel beads to the copper ion solution is 1 g: 4-7 mL; the dosage ratio of the modified chitosan porous gel beads to epichlorohydrin and isopropanol is 1 g: 2-5 mL: 0.5-1 mL, and the concentration of epoxy chloropropane is 0.5-0.8 mol/L; the temperature of the crosslinking reaction is 25-30 ℃, and the time is 24-26 h.
Further, in the step (4), Cu is eluted 2+ The specific method comprises the following steps: oscillating and eluting the modified chitosan metal complex pre-crosslinked porous microspheres by using 2.5mM EDTA-2Na aqueous solution until no Cu is detected in the eluent 2+ Until now.
Furthermore, the invention also provides a more specific preparation method of the lithium ion imprinting cross-linked chitosan porous microsphere, which comprises the following steps:
(1) dissolving chitosan powder by using 1-5 wt% of acetic acid aqueous solution, adding 1-2 wt% of polyethylene glycol serving as a pore-foaming agent, and mixing to obtain a dispersion phase (acetic acid-chitosan solution), wherein the concentration of chitosan is 1-4 wt%;
(2) taking a trisodium citrate aqueous solution as a continuous phase, controlling the volume ratio of the acetic acid-chitosan solution to the trisodium citrate aqueous solution to be 1: 2-5, controlling the concentration of the trisodium citrate aqueous solution to be 8-12 wt%, slowly dripping the dispersed phase into the continuous phase, and soaking and curing for 20-48 h to form chitosan porous gel beads;
(3) adding excess Cu to the vessel 2+ Adding the modified chitosan porous gel beads prepared in the step (2), placing the mixture in a constant temperature shaking table at 25 ℃ for blotting for 24 hours, adding epichlorohydrin and isopropanol, and performing blotting treatment at 25-30 DEG CCrosslinking for 24-26 h to obtain modified chitosan metal complex pre-crosslinked porous microspheres;
(4) carrying out Cu treatment on the modified chitosan metal complex crosslinked porous microspheres prepared in the step (3) 2+ Eluting, washing to neutrality, and freeze drying to obtain Cu 2+ Imprinting and crosslinking the chitosan porous microspheres.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts an ion imprinting technology, and gel beads formed by chitosan powder and acetic acid hydrosol in trisodium citrate aqueous solution, namely chitosan is used as a carrier, trisodium citrate is used as a functional monomer, and Cu is used as a functional monomer 2+ The method is used as template ions to fix the spatial position of a functional group on a chitosan molecular branched chain, then epoxy groups in epoxy chloropropane are utilized for cross-linking reaction, finally EDTA-2Na and copper ions are subjected to complexation to be eluted from materials, and after freeze drying, the copper ion imprinted cross-linked chitosan porous microspheres are obtained.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
(1) Taking 100 mL of acetic acid solution with the mass concentration of 4 percent into a beaker, adding 4 g of chitosan powder (the molecular weight is 50 ten thousand, the viscosity is 300 Pa.s, the deacetylation degree is 80 percent), and after complete ultrasonic dissolution, adding 2 g of polyethylene glycol (the molecular weight is 2000) for full dissolution to obtain acetic acid-chitosan solution;
(2) taking 10 mL of acetic acid-chitosan solution, taking the acetic acid-chitosan solution by using a No. 7 needle tube, adjusting the distance between a needle head and the liquid level of the trisodium citrate aqueous solution to be 15 cm, dripping 40 mL of trisodium citrate aqueous solution with the mass fraction of 10% at the speed of 30 drops/min, soaking and curing for 24 h, and placing formed gel beads in deionized water to wash for several times to obtain chitosan porous gel beads;
(3) weighing 20 g of the modified chitosan porous gel beads prepared in the step (2), adding 100 mL of copper ion solution with the concentration of 64 mg/L into the modified chitosan porous gel beads, placing the modified chitosan porous gel beads in a constant-temperature shaking table at 25 ℃ for imprinting reaction for 24 hours, adding 80 mL of 0.5 mol/L epoxy chloropropane and 20 mL of isopropanol, and crosslinking the mixture at 25 ℃ for 24 hours to obtain modified chitosan metal complex pre-crosslinked porous microspheres;
(4) the modified chitosan metal complex crosslinked porous microspheres prepared in the step (3) are subjected to Cu treatment by using 100 mL of EDTA-2Na solution with the concentration of 2.5mmol/L 2+ Elution (elution until no Cu was detected in the eluate) 2+ ) Washing with water to neutrality, and freeze drying to obtain Cu 2+ Imprinting crosslinking porous chitosan microsphere adsorbent.
Measurement of Cu 2+ The imprinted cross-linked chitosan porous microsphere adsorbent has the adsorption capacity on copper ions and selective identification performance on the copper ions, wherein the determination method of the copper ion adsorption test and the copper ion identification performance test is as follows:
(i) adsorption test of copper ion
0.1000g of the Cu obtained above was taken 2+ The imprinting cross-linked chitosan porous microsphere adsorbent is placed in 100 mL of copper solution with the concentration of 64 mg/L, and is subjected to oscillation adsorption for 24 hours at the temperature of 25 ℃ to achieve adsorption equilibrium. Measuring the absorbance of the copper solution before and after adsorption at the maximum absorption wavelength of 452 nm by using a visible spectrophotometer, and checking the Cu 2+ Calculating to obtain Cu according to the absorbance-concentration standard curve chart 2+ The maximum adsorption capacity of the imprinting cross-linked chitosan porous microsphere adsorbent to copper ions is 42.89 mg/g.
(ii) Copper ion recognition Performance test
0.1000g of Cu obtained as described above was taken 2+ Imprinting cross-linked chitosan porous microsphere adsorbent, placing in n (Cu) 2+ ）：n（Mg 2+ ) 100 mL of mixed solution of =1:10 (Cu) 2+ Concentration of 1 mmol/L), and adsorbing at 25 deg.C for 24 hr under shaking to reach adsorption equilibrium. Measuring the absorbance of the copper solution before and after adsorption at the maximum absorption wavelength of 452 nm by using a visible spectrophotometer, and checking the Cu 2+ Calculating to obtain Cu according to the absorbance-concentration standard curve chart 2+ The maximum adsorption capacity of the imprinted cross-linked chitosan porous microsphere adsorbent to lithium ions is 41.12 mg/g.
Comparative example 1
(1) Taking 100 mL of acetic acid solution with the mass concentration of 4% in a beaker, adding 4 g of chitosan powder, and after complete ultrasonic dissolution, adding 2 g of polyethylene glycol for full dissolution to obtain acetic acid-chitosan solution;
(2) taking 10 mL of acetic acid-chitosan solution, taking the acetic acid-chitosan solution by using a No. 7 needle tube, adjusting the distance between a needle head and the liquid surface to be 15 cm, dripping the acetic acid-chitosan solution into 40 mL of sodium hydroxide solution with the mass fraction of 10% at the speed of 30 drops/min, soaking and solidifying for 24 hours, and placing formed gel beads in deionized water for washing for several times to obtain the acetic acid modified chitosan porous gel beads.
(3) Weighing 20 g of the modified chitosan porous gel beads prepared in the step (2), adding 100 mL of copper ion solution with the concentration of 64 mg/L into the modified chitosan porous gel beads, placing the modified chitosan porous gel beads in a constant-temperature shaking table at 25 ℃ for imprinting reaction for 24 hours, adding 80 mL of 0.5 mol/L epoxy chloropropane and 20 mL of isopropanol, and crosslinking the mixture at 25 ℃ for 24 hours to obtain modified chitosan metal complex pre-crosslinked porous microspheres;
(4) adding 100 mL of EDTA-2Na solution with the concentration of 2.5mmol/L into the modified chitosan metal complex crosslinked porous microspheres prepared in the step (3) to carry out Cu 2+ Eluting, washing to neutrality, and freeze drying to obtain Cu 2+ Imprinting crosslinking porous chitosan microsphere adsorbent.
And (3) measuring the adsorption capacity of the acetic acid modified chitosan porous gel beads on copper ions and the selective recognition performance of the acetic acid modified chitosan porous gel beads on the copper ions, wherein the measuring method of the copper ion adsorption test and the copper ion recognition performance test is as in example 1.
The result shows that the chitosan acetate porous gel beads have the effects of adsorbing and identifying copper ions, the adsorption capacity is lower and reaches 18.56 mg/g, and the adsorption performance is reduced by the single carboxyl group in the grafted acetic acid.
Comparative example 2
(1) Adding 8.98g of Malic Acid (MA) powder and 4 g of chitosan powder into 100 mL of deionized water in a beaker, and adding 2 g of polyethylene glycol for full dissolution after complete ultrasonic dissolution to obtain a malic acid-chitosan solution;
(2) taking 10 mL of malic acid-chitosan solution, taking the malic acid-chitosan solution by using a No. 7 needle tube, adjusting the distance between a needle head and the liquid level to be 15 cm, dripping the malic acid-chitosan solution into 40 mL of sodium hydroxide solution with the mass fraction of 10% at the speed of 30 drops/min, soaking and curing for 24 hours, and placing gel beads in deionized water for washing for several times to obtain malic acid modified chitosan porous gel beads;
(3) weighing 20 g of the modified chitosan porous gel beads prepared in the step (2), adding 100 mL of copper ion solution with the concentration of 64 mg/L into the modified chitosan porous gel beads, carrying out imprinting reaction in a constant-temperature shaking table at 25 ℃ for 24 hours, adding 80 mL of 0.5 mol/L epoxy chloropropane and 20 mL of isopropanol, and crosslinking at 25 ℃ for 24 hours to obtain modified chitosan metal complex pre-crosslinked porous microspheres;
(4) adding 100 mL of EDTA-2Na solution with the concentration of 2.5mmol/L into the modified chitosan metal complex crosslinked porous microspheres prepared in the step (3) to carry out Cu 2+ Eluting, washing with water to neutrality, and freeze drying to obtain Cu 2+ Imprinting crosslinking porous chitosan microsphere adsorbent.
The adsorption capacity of the malic acid modified chitosan porous gel beads to copper ions and the selective identification performance of the malic acid modified chitosan porous gel beads to the copper ions are determined, wherein the determination method of the copper ion adsorption test and the copper ion identification performance test is as example 1.
The result shows that the malic acid modified chitosan porous gel beads have adsorption and recognition effects on copper ions, the adsorption capacity is low and reaches 27.88 mg/g, namely the adsorption performance is reduced by the dicarboxyl group in the grafted malic acid.
Comparative example 3
(1) Putting 100 mL of 4% acetic acid solution into a beaker, adding 4 g of chitosan powder and 4 g of thiourea powder, and after complete ultrasonic dissolution, adding 2 g of polyethylene glycol for full dissolution to obtain an acetic acid-thiourea-chitosan solution;
(2) taking 10 mL of acetic acid-chitosan solution, taking the acetic acid-chitosan solution by using a No. 7 needle tube, adjusting the distance between a needle head and the liquid surface to be 15 cm, dripping the acetic acid-chitosan solution into 40 mL of sodium hydroxide solution with the mass fraction of 10% at the speed of 30 drops/min, soaking and solidifying for 24 h, and placing gel beads in deionized water for washing for several times to obtain the acetic acid @ thiourea modified chitosan porous gel beads.
(3) Weighing 20 g of the modified chitosan porous gel beads prepared in the step (2), adding 100 mL of copper ion solution with the concentration of 64 mg/L into the modified chitosan porous gel beads, carrying out imprinting reaction in a constant-temperature shaking table at 25 ℃ for 24 hours, adding 80 mL of 0.5 mol/L epoxy chloropropane and 20 mL of isopropanol, and crosslinking at 25 ℃ for 24 hours to obtain modified chitosan metal complex pre-crosslinked porous microspheres;
(4) adding 100 mL of EDTA-2Na solution with the concentration of 2.5mmol/L into the modified chitosan metal complex crosslinked porous microspheres prepared in the step (3) to carry out Cu 2+ Eluting, washing to neutrality, and freeze drying to obtain Cu 2+ Imprinting crosslinking porous chitosan microsphere adsorbent.
The adsorption capacity of the acetic acid @ thiourea modified chitosan porous gel beads to copper ions and the selective recognition performance of the acetic acid @ thiourea modified chitosan porous gel beads to the copper ions are determined, wherein the determination method of the copper ion adsorption test and the copper ion recognition performance test is as in example 1.
The result shows that the acetic acid @ thiourea chitosan porous gel beads have adsorption and recognition effects on copper ions, the adsorption capacity is low and reaches 18.11 mg/g, and the sulfydryl of thiourea and the single carboxyl group of acetic acid do not have a synergistic adsorption effect.
Comparative example 4
(1) Adding 8.98g of Malic Acid (MA) powder, 4 g of chitosan powder and 4 g of thiourea into 100 mL of deionized water in a beaker, and adding 2 g of polyethylene glycol for full dissolution after complete ultrasonic dissolution to obtain a malic acid-thiourea-chitosan solution;
(2) taking 10 mL of malic acid-thiourea-chitosan solution, taking the malic acid-thiourea-chitosan solution by using a No. 7 needle tube, adjusting the distance between a needle head and the liquid level to be 15 cm, dripping 40 mL of sodium hydroxide solution with the mass fraction of 10% at the speed of 30 drops/min, soaking and curing for 24 h, and placing gel beads in deionized water for washing for several times to obtain malic acid @ thiourea modified chitosan porous gel beads;
(3) weighing 20 g of the modified chitosan porous gel beads prepared in the step (2), adding 100 mL of copper ion solution with the concentration of 64 mg/L into the modified chitosan porous gel beads, placing the modified chitosan porous gel beads in a constant-temperature shaking table at 25 ℃ for imprinting for 24 h, adding 80 mL of 0.5 mol/L epoxy chloropropane and 20 mL of isopropanol, and crosslinking at 25 ℃ for 24 h to obtain modified chitosan metal complex pre-crosslinked porous microspheres;
(4) adding 100 mL of EDTA-2Na solution with the concentration of 2.5mmol/L into the modified chitosan metal complex crosslinked porous microspheres prepared in the step (3) to carry out Cu 2+ Eluting, washing to neutrality, and freeze drying to obtain Cu 2+ Imprinting crosslinking porous chitosan microsphere adsorbent.
The adsorption capacity of the malic acid @ thiourea modified chitosan porous gel beads to copper ions and the selective recognition performance of the malic acid @ thiourea modified chitosan porous gel beads to the copper ions are determined, wherein the determination method of the copper ion adsorption test and the copper ion recognition performance test is as in example 1.
The result shows that the malic acid @ thiourea modified chitosan porous gel beads have adsorption and recognition effects on copper ions, the adsorption capacity is low and reaches 26.74 mg/g, and the sulfydryl of thiourea and the dicarboxyl group of malic acid do not have synergistic adsorption effect.
Comparative example 5
(1) Putting 100 mL of 4% acetic acid solution into a beaker, adding 4 g of chitosan powder and 4 g of thiourea, and after complete ultrasonic dissolution, adding 2 g of polyethylene glycol for full dissolution to obtain an acetic acid-thiourea-chitosan solution;
(2) taking 10 mL of acetic acid-chitosan solution, taking the acetic acid-chitosan solution by using a No. 7 needle tube, adjusting the distance between a needle head and the liquid level to be 15 cm, dripping 40 mL of trisodium citrate aqueous solution with the mass fraction of 10% at the speed of 30 drops/min, soaking and curing for 24 h, and placing gel beads in deionized water for washing for several times to obtain the citric acid @ thiourea modified chitosan porous gel beads;
(3) weighing 20 g of the modified chitosan porous gel beads prepared in the step (2), adding 100 mL of copper ion solution with the concentration of 64 mg/L into the modified chitosan porous gel beads, carrying out imprinting reaction in a constant-temperature shaking table at 25 ℃ for 24 hours, adding 80 mL of 0.5 mol/L epoxy chloropropane and 20 mL of isopropanol, and crosslinking at 25 ℃ for 24 hours to obtain modified chitosan metal complex pre-crosslinked porous microspheres;
(4) in step (b)Adding 100 mL of EDTA-2Na solution with the concentration of 2.5mmol/L into the modified chitosan metal complex crosslinked porous microspheres prepared in the step (3) to carry out Cu 2+ Eluting, washing to neutrality, and freeze drying to obtain Cu 2+ Imprinting crosslinking porous chitosan microsphere adsorbent.
The adsorption capacity of the citric acid @ thiourea modified chitosan porous gel beads on copper ions and the selective recognition performance of the citric acid @ thiourea modified chitosan porous gel beads on the copper ions are determined, wherein the determination method of the copper ion adsorption test and the copper ion recognition performance test is as in example 1.
The result shows that the citric acid @ thiourea modified chitosan porous gel beads have adsorption and recognition effects on copper ions, the adsorption capacity reaches 40.35 mg/g, and the sulfydryl of thiourea and the tricarboxyl group of citric acid do not have a synergistic adsorption effect.
Comparative example 6
(1) Taking 100 mL of 4% acetic acid solution, adding 4 g of chitosan powder into a beaker, and adding 2 g of polyethylene glycol for full dissolution after complete ultrasonic dissolution to obtain an acetic acid-chitosan solution;
(2) taking 10 mL of acetic acid-chitosan solution, taking the acetic acid-chitosan solution by using a No. 7 needle tube, adjusting the distance between a needle head and the liquid level to be 15 cm, dripping the acetic acid-chitosan solution into 40 mL of trisodium citrate aqueous solution with the mass fraction of 10% at the speed of 30 drops/min, soaking and solidifying for 24 hours, and placing gel beads in deionized water to wash for several times to obtain chitosan porous gel beads;
(3) weighing 20 g of the modified chitosan porous gel beads prepared in the step (2), adding 100 mL of copper ion solution with the concentration of 64 mg/L into the modified chitosan porous gel beads, and placing the modified chitosan porous gel beads in a constant-temperature shaking table at 25 ℃ for adsorption for 24 hours to obtain citric acid modified chitosan Cu-adsorbed solution 2+ Porous microspheres.
Determination of Cu adsorption of citric acid modified chitosan 2+ The porous microspheres have the adsorption capacity for copper ions and the selective identification performance for copper ions, wherein the determination method of the copper ion adsorption test and the copper ion identification performance test is as in example 1.
The result shows that the citric acid modified chitosan adsorbs Cu 2+ The adsorption capacity of the porous microspheres to copper ions is 42.11 Mg/g, but Mg is present 2+ Existing mixturesThe adsorption capacity of the competitive system to copper ions is 11.21 mg/g. Therefore, the citric acid modified chitosan adsorbs Cu 2+ The porous microspheres have poor identification properties. Due to the introduction of new functional groups, the adsorption performance of the copper ion imprinting material is improved, but imprinting, elution and other processes are not carried out on target ions, namely a specific cavity of the copper ion imprinting is not formed.
Comparative example 7
(1) Taking 100 mL of 4% acetic acid solution, adding 4 g of chitosan powder into a beaker, and adding 2 g of polyethylene glycol for full dissolution after complete ultrasonic dissolution to obtain an acetic acid-chitosan solution;
(2) taking 10 mL of acetic acid-chitosan solution, taking the acetic acid-chitosan solution by using a No. 7 needle tube, adjusting the distance between a needle head and the liquid level to be 15 cm, dripping 40 mL of trisodium citrate aqueous solution with the mass fraction of 10% at the speed of 30 drops/min, soaking and curing for 24 h, and placing gel beads in deionized water to wash for several times to obtain chitosan porous gel beads;
(3) weighing 20 g of the modified chitosan porous gel beads prepared in the step (2), adding 100 mL of copper ion solution with the concentration of 64 mg/L into the modified chitosan porous gel beads, placing the modified chitosan porous gel beads in a constant-temperature shaking table at 25 ℃ for imprinting for 24 h, adding 80 mL of 1mol/L glutaraldehyde and 20 mL of isopropanol, and crosslinking at 25 ℃ for 24 h to obtain modified chitosan metal complex pre-crosslinked porous microspheres;
(4) adding 100 mL of EDTA-2Na solution with the concentration of 2.5mmol/L into the modified chitosan metal complex crosslinked porous microspheres prepared in the step (3) to carry out Cu 2+ Eluting, washing to neutrality, and freeze drying to obtain Cu 2+ Imprinting crosslinking porous chitosan microsphere adsorbent.
And (3) determining the adsorption capacity of the copper ion imprinted cross-linked chitosan porous microspheres to copper ions and the selective recognition performance of the copper ions, wherein the determination method of the copper ion adsorption test and the copper ion recognition performance test is as in example 1.
The result shows that the adsorption capacity of the copper ion imprinting cross-linked chitosan porous microsphere on the copper ions is 35.26 mg/g, and the adsorption capacity on the copper ions in a mixed competition system is 32.91 mg/g. Therefore, the copper ion imprinted cross-linked chitosan porous microsphere adopts epichlorohydrin as a cross-linking agent in the preparation process.
Comparative example 8
(1) Taking 100 mL of 4% acetic acid solution, adding 4 g of chitosan powder into a beaker, and adding 2 g of polyethylene glycol for full dissolution after complete ultrasonic dissolution to obtain an acetic acid-chitosan solution;
(2) taking 10 mL of acetic acid-chitosan solution, taking the acetic acid-chitosan solution by using a No. 7 needle tube, adjusting the distance between a needle head and the liquid level to be 15 cm, dripping 40 mL of trisodium citrate aqueous solution with the mass fraction of 10% at the speed of 30 drops/min, soaking and curing for 24 h, and placing gel beads in deionized water to wash for several times to obtain chitosan porous gel beads;
(3) weighing 20 g of the modified chitosan porous gel beads prepared in the step (2), adding 100 mL of copper ion solution with the concentration of 64 mg/L into the modified chitosan porous gel beads, placing the modified chitosan porous gel beads in a constant-temperature shaking table at 25 ℃ for imprinting for 24 h, adding 80 mL of 0.5 mol/L epoxy chloropropane and 20 mL of isopropanol, and crosslinking at 25 ℃ for 24 h to obtain modified chitosan metal complex pre-crosslinked porous microspheres;
(4) adding 100 mL of HCl solution with the concentration of 1mol/L into the modified chitosan metal complex crosslinked porous microspheres prepared in the step (3) to carry out Cu 2+ Eluting, washing to neutrality, and freeze drying to obtain Cu 2+ Imprinting crosslinking porous chitosan microsphere adsorbent.
The result shows that the copper ion imprinted cross-linked chitosan porous microsphere eluted and regenerated microspheres are subjected to surface dissolution, the structure of the microspheres is damaged, and the adsorption and recognition performance is not achieved. Therefore, EDTA-2Na is used as an eluent in the preparation and elution processes of the copper ion imprinting cross-linked chitosan porous microspheres.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (7)
1. A preparation method of copper ion imprinted cross-linked chitosan porous microspheres is characterized by comprising the following steps:
(1) dissolving chitosan powder with acetic acid aqueous solution, adding a pore-forming agent, and mixing to obtain acetic acid-chitosan solution;
(2) slowly dripping the dispersed phase into the continuous phase by taking a trisodium citrate water solution as the continuous phase and an acetic acid-chitosan solution as the dispersed phase, soaking and solidifying to form citric acid modified chitosan porous gel beads, and washing with deionized water for several times;
(3) mixing the modified chitosan porous gel beads obtained in the step (2) with excessive copper ion solution, and carrying out imprinting reaction; adding epichlorohydrin and isopropanol into the solution to carry out crosslinking reaction to obtain modified chitosan metal complex pre-crosslinked porous microspheres;
(4) carrying out Cu on the modified chitosan metal complex pre-crosslinked porous microspheres obtained in the step (3) 2+ And (3) eluting, washing to be neutral, and freeze-drying to obtain the copper ion imprinted cross-linked chitosan porous microspheres.
2. The preparation method of the copper ion imprinted cross-linked chitosan porous microsphere as claimed in claim 1, wherein in the step (1), the chitosan has a molecular weight of 3 to 100 ten thousand, a viscosity of 200 to 400 mpa.s, and a deacetylation degree of 70 to 100%.
3. The preparation method of the copper ion imprinted cross-linked chitosan porous microsphere as claimed in claim 1, wherein in the acetic acid-chitosan solution of step (1), the concentration of acetic acid is 1-5 wt%, and the concentration of chitosan is 1-4 wt%; the pore-forming agent is polyethylene glycol, the concentration of the pore-forming agent is 1-2 wt%, and the molecular weight of the polyethylene glycol is 600-4000.
4. The preparation method of the copper ion imprinted crosslinked chitosan porous microsphere as claimed in claim 1, wherein in the step (2), the volume ratio of the acetic acid-chitosan solution to the trisodium citrate aqueous solution is 1: 2-5, and the concentration of the trisodium citrate aqueous solution is 8-12 wt%; the soaking and curing time is 20-48 h.
5. The method for preparing the copper ion imprinted cross-linked chitosan porous microspheres as claimed in claim 1, wherein in the step (2), the specific method for dropping the acetic acid-chitosan solution into the trisodium citrate aqueous solution is as follows: taking the acetic acid-chitosan solution by a needle tube, adjusting the distance between a needle head and the liquid level of the trisodium citrate aqueous solution to be 10-20 cm, and dripping the acetic acid-chitosan solution into the trisodium citrate aqueous solution at the speed of 30-35 drops/min.
6. The preparation method of the copper ion imprinted cross-linked chitosan porous microsphere as claimed in claim 1, wherein in the step (3), the concentration of the copper ion solution is 64-100 mg/L, and the feeding ratio of the modified chitosan porous gel beads to the copper ion solution is 1 g: 4-7 mL; the dosage ratio of the modified porous chitosan gel beads to the epichlorohydrin and the isopropanol is 1 g: 2-5 mL: 0.5-1 mL, and the concentration of epoxy chloropropane is 0.5-0.8 mol/L; the temperature of the crosslinking reaction is 25-30 ℃, and the time is 24-26 h.
7. The method for preparing the copper ion imprinted cross-linked chitosan porous microsphere as claimed in claim 1, wherein in the step (4), Cu is eluted 2+ The specific method comprises the following steps: oscillating and eluting the modified chitosan metal complex pre-crosslinked porous microspheres by using 2.5mM EDTA-2Na aqueous solution until no Cu is detected in the eluent 2+ Until now.
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| CN101347720A (en) * | 2008-09-04 | 2009-01-21 | 华南师范大学 | Method for preparing chitosan porous microsphere sorbent by metal ion imprinting and crosslinking methods as well as use |
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| CN101347720A (en) * | 2008-09-04 | 2009-01-21 | 华南师范大学 | Method for preparing chitosan porous microsphere sorbent by metal ion imprinting and crosslinking methods as well as use |
| CN106552590A (en) * | 2016-11-21 | 2017-04-05 | 西北矿冶研究院 | Preparation method of heavy metal ion imprinted magnetic chitosan adsorbent |
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