CN112044404B - Amidoxime group modified cyclodextrin/sodium alginate gel ball composite adsorption material and preparation method and application thereof - Google Patents

Amidoxime group modified cyclodextrin/sodium alginate gel ball composite adsorption material and preparation method and application thereof Download PDF

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CN112044404B
CN112044404B CN202010851699.8A CN202010851699A CN112044404B CN 112044404 B CN112044404 B CN 112044404B CN 202010851699 A CN202010851699 A CN 202010851699A CN 112044404 B CN112044404 B CN 112044404B
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sodium alginate
cyclodextrin
amidoxime
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diaminomaleonitrile
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CN112044404A (en
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王志宁
李楠
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Shandong University
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Abstract

The invention relates to an amidoxime group modified cyclodextrin/sodium alginate gel bead composite adsorption material, which is prepared by combining amidoxime-modified diaminomaleonitrile with oxygen-containing functional groups of sodium alginate and cyclodextrin, on one hand, amidoxime groups are introduced to increase adsorption sites in gel and greatly enhance the selective adsorption capacity of the composite material on hexavalent uranium, on the other hand, the mechanical properties of the material are enhanced by sodium alginate and cyclodextrin to obtain stronger mechanical properties, so that the material has good mechanical properties and can be repeatedly utilized, and is easy to separate from the water body, and simultaneously, the adsorption sites in the composite aerogel are increased, the enrichment rate for enriching hexavalent uranium is high, the adsorption time is short, and the seawater desalting device is not influenced by seawater salinity, is repeatedly utilized for multiple times, is easy to separate from a water body, and is easy to recover and recycle.

Description

Amidoxime group modified cyclodextrin/sodium alginate gel ball composite adsorption material and preparation method and application thereof
Technical Field
The invention relates to an amidoxime group modified cyclodextrin/sodium alginate gel ball composite adsorption material, and a preparation method and application thereof, and belongs to the technical field of chemistry and environment.
Background
With the rapid development of global economy, the demand for energy is increasing day by day. The limited fossil fuels and their combustion problems have led to an increasing interest in sustainable clean energy. Nuclear energy has received a great deal of attention as one of clean energy sources. With the gradual development of the nuclear industry, the demand of people for uranium resources which are main raw materials of the nuclear industry is gradually increased. The existing terrestrial uranium ore reserves are expected to be sufficient for human use for only about a hundred years. And about 45 hundred million tons of uranium exist in seawater, which is equivalent to one thousand times of the uranium mine on land, and the extraction of uranium from seawater is expected to become a feasible scheme for ensuring the sustainable development of nuclear energy. At present, methods for enriching hexavalent uranium in water mainly comprise reduction precipitation, membrane separation, extraction, electrolytic recovery, ion exchange, adsorption and the like. Among them, the adsorption method is considered as one of the most effective treatment methods. However, the concentration of uranium in seawater is very low, the salinity of seawater is high, and the enrichment of uranium from seawater is extremely challenging.
The amidoxime-based adsorbent has the characteristics of simple preparation, high stability, selective adsorption of uranium and the like. The practicability of the engineering is proved when the engineering is used for large-scale engineering experiments at the beginning of the 21 st century. Cyclodextrin is a green and biodegradable cyclic macromolecular compound, is composed of glucose, is non-toxic, harmless and free of side effects, and can be absorbed by human bodies. Beta-cyclodextrin is the most commonly used cyclodextrin, the outer edge of which is hydrophilic and the inner cavity of which is hydrophobic, and can form inclusion complex with pollutants such as heavy metals, organic matters and the like. And thus has been successfully applied to the treatment of heavy metal and organic pollutants. However, in practical applications, cyclodextrin still faces some problems, such as: (1) the chemical property is unstable and is easy to dissolve and lose; (2) the adsorption time is long and time is consumed; (3) the adsorption capacity to metal ions and organic pollutants is low; (4) difficult to separate; (5) the mechanical properties are poor. How to solve the problems determines the application prospect of the cyclodextrin in water treatment, and the modification of the cyclodextrin is a good solution.
The sodium alginate is a natural high molecular compound consisting of beta-D-mannuronic acid and alpha-L-guluronic acid existing in brown algae, a molecular chain of the sodium alginate contains a large amount of-COOH and-OH, chelation can be performed under the action of divalent and above metal cations to form gel with a network structure, the sodium alginate has the characteristics of good hydrophilicity, gel property, no toxicity, degradability, high temperature resistance, easiness in recovery and the like, can be used as a carrier of beta-cyclodextrin to make up for the defects of the cyclodextrin, but the sodium alginate loaded with the cyclodextrin has poor uranium absorption capability and low mechanical strength, and cannot meet the requirement of high-efficiency uranium enrichment from seawater with high salinity.
Disclosure of Invention
Aiming at the defects of the prior art, particularly the problems that the prior composite material is poor in uranium absorption capacity and low in mechanical strength and cannot meet the requirement for high-efficiency uranium enrichment from seawater with high salinity, the invention provides an amidoxime group modified cyclodextrin/sodium alginate gel ball composite adsorption material and a preparation method and application thereof.
Summary of the invention:
the invention takes sodium alginate, calcium chloride, beta-cyclodextrin and amidoxime diaminomaleonitrile as raw materials, and the amidoxime modified cyclodextrin/sodium alginate gel bead composite adsorption material is prepared by one-step mixing and crosslinking after the raw materials are completely dissolved under the stirring at the constant temperature of 90 ℃.
Detailed description of the invention:
in order to solve the technical problems, the invention is realized by the following technical scheme:
the amidoxime group modified cyclodextrin/sodium alginate gel bead composite adsorbing material is gel beads with uniform size, is obtained by mixing and crosslinking cyclodextrin, amidoxime diaminomaleonitrile and sodium alginate in a one-step method, and combines amino of the amidoxime diaminomaleonitrile with oxygen-containing functional groups of the sodium alginate and oxygen-containing functional groups of the cyclodextrin.
A preparation method of amidoxime group modified cyclodextrin/sodium alginate gel ball composite adsorption material comprises the following steps:
adding sodium alginate, beta-cyclodextrin and amidoxime diaminomaleonitrile into deionized water, stirring at constant temperature to completely dissolve the sodium alginate, beta-cyclodextrin and amidoxime diaminomaleonitrile to obtain a mixed solution, dropwise adding the mixed solution into a calcium chloride solution, carrying out a crosslinking reaction, washing an obtained product, and freeze-drying to obtain the amidoxime group modified cyclodextrin/sodium alginate gel bead composite adsorbing material.
According to the invention, the constant-temperature stirring temperature is preferably 85-95 ℃, and the mass content of the sodium alginate in the mixed solution is 2-5 wt%.
Preferably, the mass content of the sodium alginate in the mixed solution is 2wt% to 4 wt%.
According to the invention, the beta-cyclodextrin content in the mixed solution is preferably 0.1 to 10 wt%.
Preferably, the mass content of the beta-cyclodextrin in the mixed solution is 1-4 wt%
According to the invention, the content by mass of the amidoximized diaminomaleonitrile in the mixed solution is preferably 0.1 to 10% by weight.
Preferably, the mass content of the amidoximated diaminomaleonitrile in the mixed solution is 1-2 wt%.
According to the invention, the preferred amidooximated diaminomaleonitrile is prepared as follows:
reacting NH2OH, HCl and K2CO3Dissolving in ethanol water solution to obtain mixed solution, adding diaminomaleonitrile, heating to 75-95 deg.C under nitrogen protection, reacting for 4-8h, centrifuging after reaction, collecting sample, washing with ethanol and water respectively, and freezingDrying to obtain the amidoxime diamino maleonitrile.
Preferred according to the invention, NH2OH, HCl and K2CO3The mass ratio of (1-2): (1-2).
According to the invention, the volume ratio of ethanol to water in the ethanol aqueous solution is: 9:1.
Preferred according to the invention, NH2The mass-volume ratio of OH & HCl to the ethanol water solution is as follows: 1: (120-160), unit, g/mL.
According to the invention, the mass-volume ratio of the added amount of the diaminomaleonitrile to the ethanol water solution is: (1-6): 1, unit, mg/mL.
According to the invention, the reaction temperature is preferably 80 ℃ and the reaction time is preferably 6 h.
According to the invention, the mass fraction of calcium chloride in the calcium chloride solution is preferably 2-5 wt%, and the crosslinking time is preferably 12-24 hours; the volume ratio of the mixed solution to the calcium chloride solution is 1: (10-50).
An application of amidoxime group modified cyclodextrin/sodium alginate gel sphere composite adsorption material for enriching hexavalent uranium in a water body.
According to the invention, the preferable specific application method is as follows: adding the composite adsorbing material into a water body for adsorption and enrichment of hexavalent uranium, wherein the adsorption time is 5-720min, the adding amount of the composite adsorbing material is 100-500 mg of the composite adsorbing material added into each liter of water body, the pH value of the water body is 2-9, and the adsorption temperature is 25-45 ℃.
The invention has the beneficial effects that:
1. according to the invention, amidoxime-oximated diaminomaleonitrile is selected to be combined with oxygen-containing functional groups of sodium alginate and cyclodextrin, so that amidoxime groups are introduced, adsorption sites in gel are increased, selective adsorption capacity of the composite material on hexavalent uranium is greatly enhanced, mechanical properties of the material are enhanced by sodium alginate and cyclodextrin, stronger mechanical properties are obtained, the material has good mechanical properties, can be repeatedly used, is easy to separate from a water body, and adsorption sites in the composite aerogel are increased.
2. The composite adsorption material has large specific surface area, has stronger adsorption capacity, is used for enriching hexavalent uranium, has high enrichment rate and short adsorption time, and is not influenced by the salinity of seawater.
3. The raw materials used in the invention are environment-friendly, nontoxic and harmless, have low cost and simple preparation method, and can prepare the high-performance adsorbing material under mild conditions; can be repeatedly used for many times, is easy to be separated from the water body and is easy to be recovered and recycled.
Drawings
FIG. 1 is a bar graph of the adsorption amount of hexavalent uranium by the adsorbing materials of examples 1 to 4 of the present invention and comparative examples 1 to 6;
FIG. 2 is a graph showing the change of the adsorption amount of the adsorbent prepared in example 2 of the present invention, and the change of the adsorption amount of the adsorbent prepared in comparative example 1, comparative example 2 and comparative example 6 with respect to adsorption time;
FIG. 3 is a graph showing the adsorption effect of the adsorption materials prepared in example 2 of the present invention, and the adsorption materials prepared in comparative examples 1, 2 and 6 on hexavalent uranium at different pH values;
fig. 4 is a bar chart of the adsorption amount of hexavalent uranium in solutions with different initial uranium concentrations by the adsorption material prepared in embodiment 2 of the present invention.
FIG. 5 is a graph showing the cycle regeneration performance of the adsorbent prepared in example 2 of the present invention.
FIG. 6 is a comparison graph of selective adsorption of different metal elements in real seawater by the adsorbing material prepared in example 2 of the present invention.
FIG. 7 is a photograph of the adsorbent materials of example 2 of the present invention, comparative example 1 and comparative example 2, wherein a is comparative example 1, b is comparative example 2, and c is example 2.
Detailed Description
The invention will be further illustrated by the following examples in conjunction with the accompanying drawings,
the starting materials used in the examples are all conventional commercial products.
Example 1
A preparation method of amidoxime group modified cyclodextrin/sodium alginate gel ball composite adsorption material comprises the following steps:
weighing 1.25g of sodium alginate, adding the sodium alginate into 60mL of deionized water, stirring at a constant temperature of 90 ℃ to completely dissolve the sodium alginate, adding amidoxime diaminomaleonitrile and 1.25g of beta-cyclodextrin to continuously dissolve the sodium alginate and the beta-cyclodextrin to obtain a mixed solution, wherein the mass fraction of the sodium alginate in the mixed solution is 2wt%, the mass fraction of the amidoxime diaminomaleonitrile is 1 wt%, and the mass fraction of the beta-cyclodextrin is 2 wt%;
and dropwise adding the mixed solution into a calcium chloride solution, carrying out a crosslinking reaction for 12 hours, then washing with deionized water, and then carrying out freeze drying to obtain the amidoxime group modified cyclodextrin/sodium alginate gel bead composite adsorbing material.
Example 2
The difference from the preparation method of the amidoxime group modified cyclodextrin/sodium alginate gel bead composite adsorption material described in example 1 is that: the mass fraction of amidoximated diaminomaleonitrile in the mixed solution was 2 wt%.
Example 3
The difference from the preparation method of the amidoxime group modified cyclodextrin/sodium alginate gel bead composite adsorption material described in example 1 is that: the mass fraction of amidoximated diaminomaleonitrile in the mixed solution was 4 wt%.
Example 4
The difference from the preparation method of the amidoxime group modified cyclodextrin/sodium alginate gel bead composite adsorption material described in example 1 is that: the mass fraction of amidoximated diaminomaleonitrile in the mixed solution was 10 wt%.
Comparative example 1
A preparation method of a gel ball composite adsorption material comprises the following steps:
weighing 1.25g of sodium alginate, adding the sodium alginate into 60mL of deionized water, stirring at a constant temperature of 90 ℃ to completely dissolve the sodium alginate, then adding 1.25g of beta-cyclodextrin, and continuously dissolving to obtain a mixed solution, wherein the mass fraction of the sodium alginate in the mixed solution is 2wt%, and the mass fraction of the beta-cyclodextrin is 2 wt%;
and dropwise adding the mixed solution into a calcium chloride solution, carrying out a crosslinking reaction for 12 hours, washing with deionized water, and freeze-drying to obtain the gel sphere composite adsorbing material.
Comparative example 2
The difference between the preparation method of the gel-ball composite adsorption material and the preparation method of the gel-ball composite adsorption material in the comparative example 1 is that:
the mass fraction of the sodium alginate in the mixed solution is 2wt%, and the mass fraction of the beta-cyclodextrin is 0 wt%. The rest of the operations and the amount are completely the same as the comparative example 1.
Comparative example 3
The difference between the preparation method of the gel-ball composite adsorption material and the preparation method of the gel-ball composite adsorption material in the comparative example 1 is that:
the mass fraction of the sodium alginate in the mixed solution is 2wt%, and the mass fraction of the beta-cyclodextrin is 1 wt%. The rest of the operations and the amount are completely the same as the comparative example 1.
Comparative example 4
The difference between the preparation method of the gel-ball composite adsorption material and the preparation method of the gel-ball composite adsorption material in the comparative example 1 is that:
the mass fraction of the sodium alginate in the mixed solution is 2wt%, and the mass fraction of the beta-cyclodextrin is 4 wt%. The rest of the operations and the amount are completely the same as the comparative example 1.
Comparative example 5
The difference between the preparation method of the gel-ball composite adsorption material and the preparation method of the gel-ball composite adsorption material in the comparative example 1 is that:
the mass fraction of the sodium alginate in the mixed solution is 2wt%, and the mass fraction of the beta-cyclodextrin is 10 wt%. The rest of the operations and the amount are completely the same as the comparative example 1.
Comparative example 6
The difference from the preparation method of the amidoxime group modified cyclodextrin/sodium alginate gel bead composite adsorption material described in example 2 is that:
the operation and the amount are completely the same as in example 2 without adding beta-cyclodextrin.
The characterization of the cyclodextrin/sodium alginate gel ball composite adsorption material synthesized under different conditions and the adsorption experiment of hexavalent uranium are as follows.
Experimental examples 1,
The adsorption experiment of hexavalent uranium was performed for examples 1 to 4 and comparative examples 1 to 6, and the adsorption result is shown in fig. 1.
Experimental examples 2,
The adsorption experiments of hexavalent uranium were performed for different periods of time on the adsorbing materials prepared in example 2 and comparative examples 1, 2 and 6, and the experimental results are shown in fig. 2.
Experimental examples 3,
The adsorption saturation experiments of hexavalent uranium under different pH values are performed on the adsorbing materials prepared in the example 2 and the adsorbing materials prepared in the comparative examples 1, 2 and 6, the experimental results are shown in figure 3, and it can be seen from figure 3 that the adsorption performance of the adsorbing material of the example 2 of the invention on hexavalent uranium is less influenced by pH.
Experimental examples 4,
The experiment results of the test in the hexavalent uranium solutions with different initial concentrations in the embodiment 2 are shown in fig. 4, and it can be seen from fig. 3 that the adsorbing material in the embodiment 2 of the present invention has a good adsorbing effect on the hexavalent uranium with low concentration and high concentration.
Experimental examples 5,
The cyclic regeneration experiment of the example 2 is performed, the adsorption effect of the hexavalent uranium after 5 cycles of cyclic regeneration is measured, the experimental result is shown in fig. 5, and it can be seen from fig. 5 that the adsorption material of the example 2 of the invention still has strong adsorption performance after 5 cycles of cyclic regeneration, which indicates that the composite adsorption material of the invention has high recycling rate.
Experimental examples 6,
A real seawater adsorption experiment was performed on example 2, and the adsorption effect of the seawater adsorption experiment on different metal elements was measured, and the experimental results are shown in fig. 6. As can be seen from FIG. 6, the adsorbing material of example 2 of the invention has unique and excellent adsorption performance on hexavalent uranium.

Claims (9)

1. The amidoxime group modified cyclodextrin/sodium alginate gel bead composite adsorbing material is gel beads with uniform size, is obtained by mixing and crosslinking cyclodextrin, amidoxime diaminomaleonitrile and sodium alginate in a one-step method, and combines amino of the amidoxime diaminomaleonitrile with oxygen-containing functional groups of the sodium alginate and oxygen-containing functional groups of the cyclodextrin.
2. A preparation method of amidoxime group modified cyclodextrin/sodium alginate gel ball composite adsorption material comprises the following steps:
adding sodium alginate, beta-cyclodextrin and amidoxime diaminomaleonitrile into deionized water, stirring at constant temperature to completely dissolve the sodium alginate, beta-cyclodextrin and amidoxime diaminomaleonitrile to obtain a mixed solution, dropwise adding the mixed solution into a calcium chloride solution, carrying out a crosslinking reaction, washing and freeze-drying an obtained product to obtain an amidoxime group modified cyclodextrin/sodium alginate gel bead composite adsorbing material;
the amidoxime-substituted diaminomaleonitrile is prepared by the following method:
reacting NH2OH ∙ HCl and K2CO3Dissolving in ethanol water solution to obtain mixed solution, adding diaminomaleonitrile into the mixed solution, heating to 75-95 ℃ under the protection of nitrogen, reacting for 4-8h, centrifuging after reaction, collecting samples, washing with ethanol and water respectively, and freeze-drying to obtain amidoxime diaminomaleonitrile.
3. The production method according to claim 2, wherein the stirring temperature at constant temperature is 85 to 95 ℃, and the mass content of sodium alginate in the mixed solution is 2 to 5 wt%.
4. The method according to claim 2, wherein the mass content of the β -cyclodextrin in the mixed solution is 0.1 to 10 wt%.
5. The process according to claim 2, wherein the mass content of the amidoximated diaminomaleonitrile in the mixed solution is 0.1 to 10% by weight.
6. The method of claim 2, wherein NH is2OH ∙ HCl and K2CO3The mass ratio of (1-2): (1-2), the volume ratio of ethanol to water in the ethanol aqueous solution is as follows: 9:1.
7. The method of claim 2, wherein NH is2The mass-volume ratio of OH ∙ HCl to the ethanol aqueous solution is as follows: 1: (120-160), wherein the unit is g/mL, and the mass-volume ratio of the adding amount of the diaminomaleonitrile to the ethanol water solution is as follows: (1-6): 1, unit, mg/mL.
8. The preparation method according to claim 2, characterized in that the reaction temperature is 80 ℃, the reaction time is 6 hours, the mass fraction of calcium chloride in the calcium chloride solution is 2wt% -5wt%, and the crosslinking time is 12-24 hours; the volume ratio of the mixed solution to the calcium chloride solution is 1: (10-50).
9. The application of the amidoxime group modified cyclodextrin/sodium alginate gel bead composite adsorption material of claim 1 in enrichment of hexavalent uranium in water; the specific application method is as follows: adding the composite adsorbing material into a water body for adsorption and enrichment of hexavalent uranium, wherein the adsorption time is 5-720min, the adding amount of the composite adsorbing material is 100-500 mg of the composite adsorbing material added into each liter of water body, the pH value of the water body is 2-9, and the adsorption temperature is 25-45 ℃.
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