CN111514861B - Preparation method and application of tridentate ligand heavy metal ion imprinting material - Google Patents
Preparation method and application of tridentate ligand heavy metal ion imprinting material Download PDFInfo
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- CN111514861B CN111514861B CN202010406497.2A CN202010406497A CN111514861B CN 111514861 B CN111514861 B CN 111514861B CN 202010406497 A CN202010406497 A CN 202010406497A CN 111514861 B CN111514861 B CN 111514861B
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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
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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
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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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- 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 provides a preparation method and application of a tridentate ligand heavy metal ion imprinting material, wherein the preparation method comprises the following steps: soaking the fiber grafted with acrylic acid in a sodium silicate solution, then putting the fiber into a calcium chloride solution, crosslinking, putting the fiber into a hydrochloric acid solution for activation, then putting the fiber into a methanol solution of 3- (2-aminoethylamino) propyl trimethoxy silane, heating and refluxing the mixture, and after the reaction is finished; adding the material into chloroacetic acid solution, heating and refluxing, taking out the fiber after the reaction, washing the fiber with water to be neutral, drying, putting the fiber into a target heavy metal ion solution to enable the surface of the material to adsorb heavy metal ions, taking out the adsorbed material, adding epoxy solution, heating and refluxing for 4-24 hours at 40-80 ℃, eluting with nitric acid and EDTA solution after the reaction is finished, washing the material to be neutral, and drying to obtain the heavy metal ion imprinted polymer. The invention solves the problems of low adsorption capacity, poor selectivity, easy material loss and the like of the traditional ion imprinting material.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a preparation method and application of a tridentate ligand heavy metal ion imprinting material.
Background
With the acceleration of the industrialization and urbanization processes, a large amount of wastewater containing heavy metal ions is discharged into the environment through various ways, the heavy metal burden of the environment is increased, and serious water body heavy metal pollution is caused. The heavy metal can cause a plurality of environmental problems after being exposed in the heavy metal for a long time, and because the heavy metal can not be subjected to biodegradation and thermal degradation, the heavy metal has low clearance rate in a human body and can only be enriched in the organism, and then enters the human body through a food chain, so that the enrichment in the human body causes development disorder, organ damage and the like of the human body. At present, the treatment method of heavy metal ions in water mainly comprises the following steps: chemical precipitation, electrochemical, biological, membrane separation, adsorption, and the like. Among them, the adsorption method is considered to be an effective and simple method due to its simple operation, high efficiency, low energy consumption, no secondary pollution, and low investment cost.
The currently used adsorbents include activated carbon, mineral adsorbents, polymer adsorbents, biological adsorbents, industrial wastes, and the like, such as silica gel, activated alumina, molecular sieves, resins, fibers, porous media, silica, carbon nanotubes, magnetic nanoparticles, chitosan, clay, zeolite, montmorillonite, biochar, and the like. However, the main problems of the adsorbent are that the selectivity to metal ions is poor, the anti-interference capability is low, and heavy metals cannot be efficiently separated from a complex matrix. The ion imprinted polymer is a polymer with specific recognition property, and is widely used for extracting, enriching, concentrating and separating a target object from a complex matrix. At present, the metal ion surface imprinted material adsorbent has better research progress, but a plurality of problems are difficult to solve, such as low adsorption capacity, long adsorption and elution time, difficult separation and easy loss of the material after adsorption.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method and application of a tridentate ligand heavy metal ion imprinting material, and solves the problems of low adsorption capacity, poor selectivity, easy material loss and the like of the traditional ion imprinting material.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a tridentate ligand heavy metal ion imprinting material comprises the following steps:
a) soaking the fiber grafted with the acrylic acid in a sodium silicate solution, taking out, removing excessive solution, putting into a calcium chloride solution, crosslinking, washing off the uncrosslinked sodium silicate with deionized water, and putting into a hydrochloric acid solution for activation to obtain the grafted fiber with a mesoporous silica gel layer on the surface; preferably, the crosslinking time is 0.5-2 hours;
b) placing the grafted fiber with the mesoporous silica gel layer on the surface obtained in the step a) into a methanol solution of 3- (2-aminoethylamino) propyl trimethoxy silane, heating and refluxing, and obtaining a fiber-based polymer with aminated surface after the reaction is finished;
c) adding the fiber-based polymer with aminated surface obtained in the step b) into a chloroacetic acid solution, heating and refluxing, taking out the fiber after the reaction is finished, washing the fiber with water to be neutral, and drying to obtain the fiber-based polymer with the tridentate ligand;
d) putting the fiber-based polymer with the tridentate ligand obtained in the step c) into a target heavy metal ion solution to enable the surface of the material to adsorb heavy metal ions, taking out the adsorbed material, adding an epoxy group solution, heating and refluxing for 4-24 hours at 40-80 ℃, eluting with a nitric acid and EDTA solution after the reaction is finished, washing with water to be neutral, and drying to obtain the fiber-based heavy metal ion imprinted polymer with the tridentate ligand.
The fiber-based heavy metal ion imprinted polymer with the tridentate ligand prepared in the step d) is used for statically adsorbing 1-50mg/L of divalent mixed metal ions containing target heavy metal ions, the adsorption quantity of the target heavy metal ions in the solution can reach 100-200mg/g, the selectivity factor is 2-10, and the polymer can be repeatedly used for 10 times without influence after desorption.
Preferably, in the step a), the fiber is any one or a mixture of more than two of polypropylene, polyester, nylon, acrylon, spandex, polytetrafluoroethylene and polyvinyl formal; the mass fraction of the sodium silicate solution is 0.5-15%; the mass percentage concentration of the calcium chloride solution is 0.5-10%.
Preferably, in the step b), the mass fraction of the 3- (2-aminoethylamino) propyl trimethoxy silane in the methanol solution of the 3- (2-aminoethylamino) propyl trimethoxy silane is 0.5-10%; the heating reflux time is 8-24 hours. The heating reflux temperature is the boiling point of methanol.
Preferably, in the step c), the mass fraction of the chloroacetic acid solution is 0.5-10%; the heating reflux temperature is 60-100 ℃, and the heating reflux time is 4-10 hours.
Preferably, in the step d), the concentration of the target heavy metal ion solution is 100-200 mg/L.
Preferably, the target heavy metal ion is one of lead, cadmium, zinc, copper, nickel and cobalt ions, and the mixed ion is two or more metal ions containing the target heavy metal ion.
Preferably, in step d), the epoxy solution is one or a mixture of two or more of an epichlorohydrin solution, an epoxysilane solution and an epoxypropane solution.
Preferably, in the step d), the temperature of heating reflux is 40-80 ℃; the heating reflux time is 4-24 hours.
The invention also provides application of the tridentate ligand heavy metal ion imprinting material obtained by the preparation method in heavy metal ion adsorption.
Preferably, the tridentate ligand heavy metal ion imprinting material is used for carrying out static adsorption on 0.01-100 mg/L target heavy metal ions.
Compared with the prior art, the preparation method of the tridentate ligand heavy metal ion imprinting material has the following advantages:
according to the invention, a silica gel layer is loaded on the fiber, and the heavy metal ion imprinting adsorption material with a tridentate ligand structure is prepared through amination and crosslinking reaction, so that the specific surface area of the fiber is increased, the adsorption capacity is improved, imprinting sites are positioned on the surface of the silica gel, the mass transfer rate is higher, and the adsorption and elution rates are improved; the tridentate ligand aminodiacetic acid type compound is used as a functional ligand, the metal ions are used as template ions, the metal ions are complexed with carboxylic acid and imino in the ligand to form a complex, and after a crosslinking reaction is carried out to elute the metal ions, the ion imprinted polymer with a special space structure is formed, the target heavy metal ions can be identified better and selectively, and the fiber-based imprinted material is easy to separate and is not easy to lose after adsorption.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
A preparation method of a tridentate ligand heavy metal ion imprinted material comprises the following steps:
a) soaking the fiber grafted with the acrylic acid in a sodium silicate solution with the mass fraction of 5%, taking out the fiber and removing excessive solution, then putting the fiber into a calcium chloride solution with the mass percentage concentration of 5%, crosslinking for 0.5 hour, washing off the non-crosslinked sodium silicate with deionized water, and putting the fiber into a hydrochloric acid solution for activation to obtain the grafted fiber with the mesoporous silica gel layer on the surface.
b) Placing the grafted fiber with the mesoporous silica gel layer on the surface into a methanol solution of 3- (2-aminoethylamino) propyl trimethoxy silane with the mass fraction of 2%, heating and refluxing for 8 hours, and obtaining a fiber-based polymer with aminated surface after the reaction is finished;
c) adding the fiber-based polymer with aminated surface into chloroacetic acid solution with mass fraction of 1%, heating and refluxing for 10 hours at 100 ℃, taking out the fiber after the reaction is finished, washing the fiber with water to be neutral, and drying to obtain the fiber-based polymer with tridentate ligand;
d) putting the fiber-based polymer with the tridentate ligand into 200mg/L cadmium ion solution to enable the surface of the material to adsorb heavy metal ions, taking out the adsorbed material, adding epoxy chloropropane solution, heating and refluxing for 24 hours at 60 ℃, eluting with 1mol/L nitric acid and 0.1mol/L EDTA solution after the reaction is finished, washing with water to be neutral, and drying to obtain the fiber-based heavy metal ion imprinted polymer with the tridentate ligand;
using the fiber-based heavy metal ion imprinted polymer with tridentate ligand prepared in the step d), carrying out static adsorption on divalent mixed metal ions containing 10mg/L of cadmium and zinc (the adsorption is carried out under a binary system, in order to express selectivity), taking out the material after 2 hours of adsorption, measuring the concentration of cadmium and zinc ions in the solution, calculating the equilibrium adsorption quantity, calculating the selectivity coefficient by using the distribution coefficient ratio of the cadmium ions and the zinc ions in the imprinted material and the solution, wherein the selectivity coefficient is 5.56, desorbing by using 1mol/L nitric acid, slightly reducing the adsorption quantity after repeated use, and reducing the adsorption quantity to 92.1% after 10 times. The adsorption thermodynamic isotherm conforms to a Langmuir model, the maximum adsorption capacity of cadmium ions can reach 130mg/g, and the adsorption capacity of cadmium ions in the solution can reach 130 mg/g.
Example 2
A preparation method of a tridentate ligand heavy metal ion imprinted material comprises the following steps:
a) soaking the fiber grafted with the acrylic acid in a sodium silicate solution with the mass fraction of 10%, taking out the solution to remove excessive solution, putting the fiber into a calcium chloride solution with the mass percentage concentration of 10%, crosslinking for 2 hours, washing off the non-crosslinked sodium silicate with deionized water, and putting the fiber into a hydrochloric acid solution for activation to obtain the grafted fiber with the mesoporous silica gel layer on the surface.
b) Placing the grafted fiber with the mesoporous silica gel layer on the surface into a methanol solution of 3- (2-aminoethylamino) propyl trimethoxy silane with the mass fraction of 5%, heating and refluxing for 13 hours, and obtaining a fiber-based polymer with aminated surface after the reaction is finished;
c) adding the fiber-based polymer with aminated surface into chloroacetic acid solution with mass fraction of 2%, heating and refluxing for 4 hours at 80 ℃, taking out the fiber after the reaction is finished, washing the fiber with water to be neutral, and drying to obtain the fiber-based polymer with tridentate ligand;
d) putting the fiber-based polymer with the tridentate ligand into 200mg/L cadmium ion solution to enable the surface of the material to adsorb heavy metal ions, taking out the adsorbed material, adding epoxy chloropropane, heating and refluxing for 15 hours at 80 ℃, eluting with 1mol/L nitric acid and 0.1mol/L EDTA solution after the reaction is finished, washing with water to be neutral, and drying to obtain the fiber-based heavy metal ion imprinted polymer with the tridentate ligand;
and d), statically adsorbing 50mg/L of cadmium-copper mixed metal ions by using the fiber-based heavy metal ion imprinted polymer with the tridentate ligand prepared in the step d), taking out the material after adsorbing for 2 hours, measuring the concentrations of cadmium and copper ions in the solution, calculating the equilibrium adsorption capacity, calculating a selectivity coefficient by using the distribution coefficient ratio of the cadmium ions and the copper ions in the imprinted material and the solution, wherein the selectivity coefficient is 3.63, desorbing by using 1mol/L nitric acid, slightly reducing the adsorption capacity after repeated use, and reducing the adsorption capacity to 91.8 percent of the original adsorption capacity after 10 times. The adsorption thermodynamic isotherm conforms to the Langmuir model, and the maximum adsorption quantity of cadmium ions can reach 158 mg/g.
Example 3
A preparation method of a tridentate ligand heavy metal ion imprinted material comprises the following steps:
a) soaking the fiber grafted with the acrylic acid in a sodium silicate solution with the mass fraction of 15%, taking out the fiber and removing excessive solution, then putting the fiber into a calcium chloride solution with the mass percentage concentration of 15%, crosslinking for 1.5 hours, washing off the non-crosslinked sodium silicate with deionized water, and putting the fiber into a hydrochloric acid solution for activation to obtain the grafted fiber with the mesoporous silica gel layer on the surface.
b) Placing the grafted fiber with the mesoporous silica gel layer on the surface into a methanol solution of 3- (2-aminoethylamino) propyl trimethoxy silane with the mass fraction of 10%, heating and refluxing for 24 hours, and obtaining a fiber-based polymer with aminated surface after the reaction is finished;
c) adding the fiber-based polymer with aminated surface into chloroacetic acid solution with the mass fraction of 10%, heating and refluxing for 10 hours at 80 ℃, taking out the fiber after the reaction is finished, washing the fiber with water to be neutral, and drying to obtain the fiber-based polymer with the tridentate ligand;
d) putting the fiber-based polymer with the tridentate ligand into 100mg/L lead ion solution to enable the surface of the material to adsorb heavy metal ions, taking out the adsorbed material, adding epoxy solution, heating and refluxing for 10 hours at 60 ℃, eluting with 1mol/L nitric acid and 0.1mol/L EDTA solution after the reaction is finished, washing with water to be neutral, and drying to obtain the fiber-based heavy metal ion imprinted polymer with the tridentate ligand;
and d) statically adsorbing 50mg/L of lead and nickel mixed metal ions by using the fiber-based heavy metal ion imprinted polymer with the tridentate ligand prepared in the step d), taking out the material after adsorbing for 2 hours, measuring the concentrations of lead and nickel ions in the solution, calculating the equilibrium adsorption amount, calculating a selectivity coefficient by using the distribution coefficient ratio of the lead ions and the nickel ions in the imprinted material and the solution, wherein the selectivity coefficient is 7.26, desorbing by using 1mol/L nitric acid, slightly reducing the adsorption amount after repeated use, and reducing the adsorption amount to 90% of the original adsorption amount after 10 times. The adsorption thermodynamic isotherm conforms to the Langmuir model, and the maximum adsorption quantity of cadmium ions can reach 188 mg/g.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. A preparation method of a tridentate ligand heavy metal ion imprinting material is characterized by comprising the following steps:
a) soaking the fiber grafted with the acrylic acid in a sodium silicate solution, taking out, removing excessive solution, then putting into a calcium chloride solution, crosslinking, washing off the uncrosslinked sodium silicate with deionized water, and putting into a hydrochloric acid solution for activation to obtain the grafted fiber with a mesoporous silica gel layer on the surface; the crosslinking time is 0.5-2 hours; the concentration of the hydrochloric acid solution is 2-4 mol/L;
b) placing the grafted fiber with the mesoporous silica gel layer on the surface obtained in the step a) into a methanol solution of 3- (2-aminoethylamino) propyl trimethoxy silane, heating and refluxing, and obtaining a fiber-based polymer with aminated surface after the reaction is finished;
c) adding the fiber-based polymer with aminated surface obtained in the step b) into a chloroacetic acid solution, heating and refluxing, taking out the fiber after the reaction is finished, washing the fiber with water to be neutral, and drying to obtain the fiber-based polymer with the tridentate ligand;
d) putting the fiber-based polymer with the tridentate ligand obtained in the step c) into a target heavy metal ion solution to enable the surface of the material to adsorb heavy metal ions, taking out the adsorbed material, adding an epoxy group solution, heating and refluxing for 4-24 hours at 40-80 ℃, eluting with a nitric acid and EDTA solution after the reaction is finished, washing with water to be neutral, and drying to obtain the fiber-based heavy metal ion imprinted polymer with the tridentate ligand;
in the step a), the fiber is any one or a mixture of more than two of polypropylene, polyester, nylon, acrylic fiber, spandex, polytetrafluoroethylene and polyvinyl formal; the mass fraction of the sodium silicate solution is 0.5-15%; the mass percentage concentration of the calcium chloride solution is 0.5-10%;
in the step b), the mass fraction of the 3- (2-aminoethylamino) propyl trimethoxy silane in the methanol solution of the 3- (2-aminoethylamino) propyl trimethoxy silane is 0.5-10%; the heating reflux time is 8-24 hours;
in the step c), the mass fraction of the chloroacetic acid solution is 1-10%; the heating reflux temperature is 60-100 ℃, and the heating reflux time is 4-10 hours;
the target heavy metal ions are one or more than two of lead, cadmium, zinc, copper, nickel and cobalt ions;
in the step d), the epoxy group solution is any one or a mixture of more than two of an epoxy chloropropane solution, an epoxy silane solution and an epoxy propane solution.
2. The preparation method of the tridentate ligand heavy metal ion imprinted material according to claim 1, characterized in that: in the step d), the concentration of the target heavy metal ion solution is 100-200 mg/L.
3. The application of the tridentate ligand heavy metal ion imprinted material obtained by the preparation method according to any one of claims 1-2 in heavy metal ion adsorption.
4. Use according to claim 3, characterized in that: and (3) statically adsorbing 0.01-100 mg/L of target heavy metal ions by using the tridentate ligand heavy metal ion imprinting material.
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| CN113150296B (en) * | 2021-03-17 | 2022-08-16 | 重庆科技学院 | MOFs-based cobalt ion imprinted polymer adsorption material and preparation method and application thereof |
| CN114086392B (en) * | 2021-12-10 | 2023-06-20 | 新凤鸣集团股份有限公司 | Composite polyester fiber with specific molecular recognition function and preparation method and application thereof |
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