CN115646468A - Chitosan composite material and preparation method and application thereof - Google Patents
Chitosan composite material and preparation method and application thereof Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 14
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000001514 detection method Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 40
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 34
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 25
- 239000011324 bead Substances 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 claims description 11
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 11
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
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- 239000003463 adsorbent Substances 0.000 abstract description 6
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- -1 amino, hydroxyl Chemical group 0.000 abstract description 2
- 230000009878 intermolecular interaction Effects 0.000 abstract description 2
- 239000004005 microsphere Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000011896 sensitive detection Methods 0.000 abstract description 2
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- 238000003756 stirring Methods 0.000 description 32
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 14
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Abstract
The invention provides a chitosan composite material and a preparation method and application thereof, belonging to the field of composite materials and the field of heavy metal pollution treatment. The raw material chitosan used in the invention is rich in amino, hydroxyl and other groups, and is a natural adsorbent. The chitosan and the polyvinyl alcohol have specific intermolecular interaction to form a three-dimensional gel network, and the problems of poor chemical stability and low mechanical strength of the chitosan are solved. The chitosan composite material realizes the detection and removal of chromium ions through the crosslinking of the magnetic gel microspheres and the synthesized product, and has great practical significance. The chitosan composite material can specifically identify chromium ions, presents different color reactions, can be identified by naked eyes without complex instruments, and is a simple and sensitive detection mode.
Description
Technical Field
The invention belongs to the field of composite materials and heavy metal pollution treatment, and particularly relates to a chitosan composite material and a preparation method and application thereof.
Background
Heavy metal ions are not biodegradable, remain after entering the environment and threaten ecological safety, and enter human bodies along with food chains to harm human health. Chromium ions are one of the most major harmful heavy metal ions, and can cause various symptoms and diseases including diarrhea, nausea, lung cancer and the like after entering a human body. Chromium contamination has become a significant problem and has attracted a great deal of attention.
At present, methods for treating heavy metal ions include a chemical precipitation method, a membrane filtration method, an ion exchange method and the like, but an adsorption method is still the most popular removal method at present. However, the general adsorbent has an adsorption effect on most metal ions, and cannot specifically recognize chromium ions. Therefore, it is necessary to design and prepare a novel adsorbent for effective detection and adsorption of chromium ions.
Chitosan is a low-cost natural adsorbent, and has the advantages of hydrophilicity, biodegradability, biocompatibility, nontoxicity and the like. The chitosan contains abundant amino and hydroxyl, and can be chelated with chromium ions. However, low mechanical strength, poor stability in acidic media and difficult recovery are serious disadvantages of chitosan.
Therefore, physical or chemical modification of chitosan to improve its adsorption performance has been the focus of research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a chitosan composite material and a preparation method and application thereof. The chitosan composite material provided by the invention is good in adsorption performance and convenient to recycle, and can improve the adsorption efficiency of chromium ions and realize the specific identification of the chromium ions.
The invention is realized by the following technical scheme:
the first purpose of the invention is to provide a preparation method of chitosan composite material, which comprises the following steps:
(1) Mixing and heating thiosemicarbazide and 2-naphthaldehyde in an alcohol solution to obtain functional thiourea; the adsorption capacity to chromium ions can be improved by introducing amino and sulfo groups. The obtained functional thiourea can provide a binding site of chromium ions, and performs specific coordination with the chromium ions to present color reaction;
(2) Mixing an alcoholic solution of chitosan with a polyvinyl alcohol solution, adding magnetic nanoparticles, and mixing and reacting in an alkaline solution to obtain magnetic gel beads;
(3) And (3) adding the functionalized thiourea obtained in the step (1) and the magnetic gel beads obtained in the step (2) into a cross-linking agent solution for heating reaction to obtain the chitosan composite material.
In one embodiment of the present invention, in the step (1), the molar ratio of the thiosemicarbazide to the 2-naphthaldehyde is 0.5 to 3:1.
in one embodiment of the invention, in the step (1), the heating temperature is 50 ℃ to 80 ℃ and the heating time is 1h to 6h.
In one embodiment of the present invention, in step (2), the magnetic nanoparticles are selected from Fe 3 O 4 Magnetic nanoparticles, fe 2 O 3 Magnetic nanoparticles or MFe 2 O 4 Magnetic nanoparticles; the MFe 2 O 4 M in the magnetic nanoparticles is selected from one or more of Co, mn, ni and Zn.
In one embodiment of the present invention, the Fe 3 O 4 The synthetic reagent of the magnetic nano particles is FeCl 2 ·4H 2 O and FeCl 3 ·6H 2 O solid, wherein the molar ratio of the O solid to the O solid is 1-3: 1.
in one embodiment of the invention, in the step (2), the mass ratio of the chitosan, the polyvinyl alcohol and the magnetic nanoparticles is 0.5-2.
In one embodiment of the invention, in the step (3), the volume ratio of the sum of the mass of the magnetic gel beads and the functionalized thiourea to the crosslinking agent is 1.5-6.
In one embodiment of the invention, in the step (3), the mass ratio of the magnetic gel beads to the functionalized thiourea is 1 to 4:0.5 to 2.
In one embodiment of the invention, in step (3), the cross-linking agent is chosen from glutaraldehyde and/or epichlorohydrin.
In one embodiment of the present invention, in the step (3), the heating reaction conditions are: the temperature is 40-80 ℃ and the time is 8-24 h.
In one embodiment of the present invention, in the step (3), the volume concentration of the crosslinking agent is 0.01% to 20%.
The second purpose of the invention is to provide the chitosan composite material obtained by the preparation method.
The third purpose of the invention is to provide the application of the chitosan composite material in detection and heavy metal adsorption.
In one embodiment of the present invention, the preparation method of the chitosan composite material comprises the following steps:
(1) Dissolving thiosemicarbazide and 2-naphthaldehyde in ethanol, mixing, refluxing and heating, and drying reactants in vacuum to obtain functional thiourea for later use; the specific reaction formula is as follows:
(2) Synthesizing ferroferric oxide magnetic nanoparticles under an alkaline condition: dissolving chitosan in 2% acetic acid, dissolving polyvinyl alcohol in ultrapure water, and mixing the two solutions after completely dissolving. Adding the obtained ferroferric oxide magnetic nanoparticles into the mixed solution, uniformly mixing, then dripping into a sodium hydroxide solution, stirring to form magnetic gel beads, and washing to be neutral for later use;
(3) Dissolving the product synthesized in the step (1) in ethanol, adding the magnetic gel beads and the ethanol solution of the product into a glutaraldehyde solution, and carrying out a crosslinking reaction under the conditions of heating and stirring. Washing the reactant with acetone, ethanol and deionized water to obtain the chitosan composite material.
The invention provides application of the chitosan composite material in removal and specific recognition of chromium ions.
In one embodiment of the present invention, a method for removing and specifically recognizing chromium ions from a chitosan composite material, comprises the following steps:
and (3) adding the chitosan composite material into different heavy metal ion solutions with certain concentrations, and observing the color change of the solutions. And oscillating and adsorbing for a certain time at a certain temperature, and measuring the concentration of heavy metal ions in the supernatant after adsorption is finished.
The technical scheme of the invention has the following advantages:
(1) The raw material chitosan used in the invention is rich in amino, hydroxyl and other groups, and is a natural adsorbent. Polyvinyl alcohol is an environmentally friendly and inexpensive polymer, and contains abundant hydroxyl groups. The chitosan and the polyvinyl alcohol have specific intermolecular interaction to form a three-dimensional gel network. Overcomes the problems of poor chemical stability and low mechanical strength of chitosan.
(2) The chitosan composite material can specifically identify chromium ions, presents different color reactions, can be identified by naked eyes without complex instruments, and is a simple and sensitive detection mode.
(3) The chitosan composite material realizes the detection and removal of chromium ions through the crosslinking of the magnetic gel microspheres and the synthesized product, and has great practical significance.
(4) The chitosan composite material of the invention introduces magnetic nano particles, thereby greatly improving the problem of difficult recovery of the adsorbent in the practical application process.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 is a diagram illustrating the recognition of different metal ions by the chitosan composite material prepared in example 1 of the present invention;
FIG. 2 is a graph showing the adsorption kinetics of Cr (VI) by the chitosan composite material prepared in example 1 of the present invention.
Detailed Description
The present invention is further described below in conjunction with the drawings and the embodiments so that those skilled in the art can better understand the present invention and can carry out the present invention, but the embodiments are not to be construed as limiting the present invention.
Example 1
(1) Dissolving 1.36g of thiosemicarbazide and 1.56g of 2-naphthaldehyde in 50mL of ethanol solution, refluxing and heating the mixed solution at 80 ℃ for 4h under the condition of magnetic stirring at 200rpm, cooling to room temperature, washing, and drying the product at 60 ℃ in vacuum to obtain the functionalized thiourea for later use.
(2)1.98g FeCl 2 ·4H 2 O and 1.35g FeCl 3 ·6H 2 O addition to 100mL H 2 In O, blowing N 2 Then sealing, under the condition of heating at 60 ℃, dropwise adding 20mL of 2mol/L NaOH, raising the temperature to 80 ℃ after dropwise adding, and continuously stirring and heating for 1h. Cooling to room temperature, washing to neutrality, and vacuum drying at 60 deg.c to obtain ferroferric oxide magnetic nanometer particle.
(3) 1g of chitosan was added to 50mL of 2% acetic acid, and dissolved by magnetic stirring to obtain an acetic acid solution containing chitosan. 1g of polyvinyl alcohol was added to 50mL of H 2 And (3) heating, stirring and dissolving in O, mixing with acetic acid solution containing chitosan after dissolving, adding 1g of the ferroferric oxide magnetic nanoparticles obtained in the step (2), stirring for 3 hours, dripping the obtained solution into 1mol/LNaOH solution by using an injector, and stirring for 2 hours at 100rpm to obtain the magnetic gel beads. Washing with ultrapure water to neutrality, and storing in water environment.
(4) Dissolving 1g of the functionalized thiourea obtained in the step (1) in 20mL of ethanol, adding the solution and 4g of magnetic gel beads into 100mL of 5% glutaraldehyde solution, and reacting for 12h under the conditions of heating and stirring at 50 ℃. And washing the obtained product with acetone, ethanol and deionized water respectively, and drying in a vacuum drying oven to obtain the chitosan composite material.
Example 2
(1) Dissolving 0.91g of thiosemicarbazide and 1.56g of 2-naphthaldehyde in 50mL of ethanol solution, refluxing and heating the mixed solution at 80 ℃ for 4h under the condition of magnetic stirring at 200rpm, cooling to room temperature, washing, and drying the product at 60 ℃ in vacuum to obtain the functionalized thiourea for later use.
(2)1.98g FeCl 2 ·4H 2 O and 1.35g FeCl 3 ·6H 2 O addition to 100mL H 2 In O, blowing N 2 Then sealing, under the condition of heating at 60 ℃, dropwise adding 20mL of 2mol/L NaOH, raising the temperature to 80 ℃ after dropwise adding, and continuously stirring and heating for 1h. Cooling to room temperature, washing to neutrality, and vacuum drying at 60 deg.c to obtain ferroferric oxide magnetic nanometer particle.
(3) 1g of chitosan was added to 50mL of 2% acetic acid, and dissolved by magnetic stirring to obtain an acetic acid solution containing chitosan. 1g of polyvinyl alcohol was added to 50mL of H 2 And (3) heating, stirring and dissolving in O, mixing with acetic acid solution containing chitosan after dissolving, adding 1g of the ferroferric oxide magnetic nanoparticles obtained in the step (2), stirring for 3 hours, dripping the obtained solution into 1mol/LNaOH solution by using an injector, and stirring for 2 hours at 100rpm to obtain the magnetic gel beads. Washing with ultrapure water to neutrality, and storing in water environment.
(4) Dissolving 1g of the functionalized thiourea obtained in the step (1) in 20mL of ethanol, adding the solution and 4g of magnetic gel beads into 100mL of 5% glutaraldehyde solution, and reacting for 12h under the conditions of heating and stirring at 50 ℃. And washing the obtained product with acetone, ethanol and deionized water respectively, and drying in a vacuum drying oven to obtain the chitosan composite material.
Example 3
(1) Dissolving 1.82g of thiosemicarbazide and 1.56g of 2-naphthaldehyde in 50mL of ethanol solution, refluxing and heating the mixed solution at 80 ℃ for 4h under the condition of magnetic stirring at 200rpm, cooling to room temperature, washing, and drying the product at 60 ℃ in vacuum to obtain the functionalized thiourea for later use.
(2)1.98g FeCl 2 ·4H 2 O and 1.35g FeCl 3 ·6H 2 O addition to 100mL H 2 In O, blowing N 2 Then sealing, under the condition of heating at 60 ℃, dropwise adding 20mL of 2mol/L NaOH, raising the temperature to 80 ℃ after dropwise adding, and continuously stirring and heating for 1h. Cooling to room temperatureThen washing to be neutral, and drying in vacuum at 60 ℃ to obtain the ferroferric oxide magnetic nanoparticles for later use.
(3) Chitosan (1 g) was added to 50mL of 2% acetic acid, and dissolved by magnetic stirring to obtain an acetic acid solution containing chitosan. 1g of polyvinyl alcohol was added to 50mL of H 2 And (3) heating, stirring and dissolving in O, mixing with acetic acid solution containing chitosan after dissolving, adding 1g of the ferroferric oxide magnetic nanoparticles obtained in the step (2), stirring for 3 hours, dripping the obtained solution into 1mol/LNaOH solution by using an injector, and stirring for 2 hours at 100rpm to obtain the magnetic gel beads. Washing with ultrapure water to neutrality, and storing in water environment.
(4) Dissolving 1g of the functionalized thiourea obtained in the step (1) in 20mL of ethanol, adding the solution and 4g of magnetic gel beads into 100mL of 5% glutaraldehyde solution, and reacting for 12h under the conditions of heating and stirring at 50 ℃. And washing the obtained product with acetone, ethanol and deionized water respectively, and drying in a vacuum drying oven to obtain the chitosan composite material.
Example 4
(1) Dissolving 1.36g of thiosemicarbazide and 1.56g of 2-naphthaldehyde in 50mL of ethanol solution, refluxing and heating the mixed solution at 80 ℃ for 4h under the condition of magnetic stirring at 200rpm, cooling to room temperature, washing, and drying the product at 60 ℃ in vacuum to obtain a product for later use.
(2)1.98g FeCl 2 ·4H 2 O and 1.35g FeCl 3 ·6H 2 O addition to 100mL H 2 In O, blowing N 2 Then sealing, under the condition of heating at 60 ℃, dropwise adding 20mL of 2mol/L NaOH, raising the temperature to 80 ℃ after dropwise adding, and continuously stirring and heating for 1h. Cooling to room temperature, washing to neutrality, and vacuum drying at 60 deg.c to obtain ferroferric oxide magnetic nanometer particle.
(3) Chitosan (1 g) was added to 50mL of 2% acetic acid, and dissolved by magnetic stirring to obtain an acetic acid solution containing chitosan. 1g of polyvinyl alcohol was added to 50mL of H 2 Heating, stirring and dissolving in O, mixing with acetic acid solution containing chitosan after dissolving, adding 1g of ferroferric oxide magnetic nanoparticles obtained in the step (2), stirring for 3h, dripping the obtained solution into 1mol/LNaOH solution by using an injector, stirring for 2h at 100rpm to obtain magnetic gelBeads. Washing with ultrapure water to neutrality, and storing in water environment.
(4) Dissolving 1.5g of the functionalized thiourea obtained in the step (1) in 20mL of ethanol, adding the solution and 4g of magnetic gel beads into 100mL of 5% glutaraldehyde solution, and reacting for 12h under the conditions of heating and stirring at 50 ℃. And washing the obtained product with acetone, ethanol and deionized water respectively, and drying in a vacuum drying oven to obtain the chitosan composite material.
Example 5
(1) Dissolving 1.36g of thiosemicarbazide and 1.56g of 2-naphthaldehyde in 50mL of ethanol solution, refluxing and heating the mixed solution at 80 ℃ for 4h under the condition of magnetic stirring at 200rpm, cooling to room temperature, washing, and drying the product at 60 ℃ in vacuum to obtain a product for later use.
(2)1.98g FeCl 2 ·4H 2 O and 1.35g FeCl 3 ·6H 2 O addition to 100mL H 2 In O, blowing N 2 Then sealing, under the condition of heating at 60 ℃, dropwise adding 20mL of 2mol/L NaOH, raising the temperature to 80 ℃ after dropwise adding, and continuously stirring and heating for 1h. Cooling to room temperature, washing to neutrality, and vacuum drying at 60 deg.c to obtain ferroferric oxide magnetic nanometer particle.
(3) 1g of chitosan was added to 50mL of 2% acetic acid, and dissolved by magnetic stirring to obtain an acetic acid solution containing chitosan. 1g of polyvinyl alcohol was added to 50mL of H 2 And (3) heating, stirring and dissolving in O, mixing with acetic acid solution containing chitosan after dissolving, adding 1g of the ferroferric oxide magnetic nanoparticles obtained in the step (2), stirring for 3 hours, dripping the obtained solution into 1mol/LNaOH solution by using an injector, and stirring for 2 hours at 100rpm to obtain the magnetic gel beads. Washing with ultrapure water to neutrality, and storing in water environment.
(4) Dissolving 0.5g of the functionalized thiourea obtained in the step (1) in 20mL of ethanol, adding the solution and 4g of magnetic gel beads into 100mL of 5% glutaraldehyde solution, and reacting for 12h under the conditions of heating and stirring at 50 ℃. And washing the obtained product with acetone, ethanol and deionized water respectively, and drying in a vacuum drying oven to obtain the chitosan composite material.
Example 6
(1) Dissolving 1.36g of thiosemicarbazide and 1.56g of 2-naphthaldehyde in 50mL of ethanol solution, refluxing and heating the mixed solution at 80 ℃ for 4h under the condition of magnetic stirring at 200rpm, cooling to room temperature, washing, and drying the product at 60 ℃ in vacuum to obtain a product for later use.
(2)1.98g FeCl 2 ·4H 2 O and 1.35g FeCl 3 ·6H 2 O addition to 100mL H 2 In O, blowing N 2 Then sealing, under the condition of heating at 60 ℃, dropwise adding 20mL of 2mol/L NaOH, raising the temperature to 80 ℃ after dropwise adding, and continuously stirring and heating for 1h. Cooling to room temperature, washing to neutrality, and vacuum drying at 60 deg.c to obtain ferroferric oxide magnetic nanometer particle.
(3) 1g of chitosan was added to 50mL of 2% acetic acid, and dissolved by magnetic stirring to obtain an acetic acid solution containing chitosan. 1g of polyvinyl alcohol was added to 50mL of H 2 And (3) heating, stirring and dissolving in O, mixing with acetic acid solution containing chitosan after dissolving, adding 1g of the ferroferric oxide magnetic nanoparticles obtained in the step (2), stirring for 3 hours, dripping the obtained solution into 1mol/LNaOH solution by using an injector, and stirring for 2 hours at 100rpm to obtain the magnetic gel beads. Washing with ultrapure water to neutrality, and storing in water environment.
(4) Dissolving 1g of the synthetic product in the step (1) in 20mL of ethanol, adding 4g of magnetic gel beads into 100mL of 1% glutaraldehyde solution, and reacting for 12h under the conditions of heating and stirring at 50 ℃. And washing the obtained product with acetone, ethanol and deionized water respectively, and drying in a vacuum drying oven to obtain the chitosan composite material.
Example 7
Respectively preparing Pb with the same concentration 2+ 、Fe 2+ 、Fe 3+ 、Co 2+ 、Zn 2+ 、Mn 2+ 、Cd 2+ 、Cr 3+ 、Cr 6+ And (3) adding the prepared chitosan composite material into the prepared heavy metal solution, and observing the color change of the solution as shown in figure 1. As can be seen from FIG. 1, the synthesized chitosan composite material can be used for treating Cr 3+ 、Cr 6+ And (4) carrying out specific recognition, wherein the solution color is changed into light yellow and yellow brown from colorless, and the other heavy metal solutions have no color change.
Example 8
Prepare an initial Cr (VI) solution with a concentration of 200mg/L, and adjust the pH of the solution to 2 with 0.1mol/L HCl and NaOH. 10mg of the chitosan composite material synthesized in example 1 was added to the above solution to perform an adsorption experiment, and samples were taken at different times (5 min, 10min, 15min, 20min, 30min, 45min, 60min, 120min, and 180 min) to measure the Cr (VI) concentration, and the adsorption amount was calculated, as shown in FIG. 2. The result shows that the removal rate of the modified magnetic chitosan composite material prepared in the embodiment to Cr (VI) is in an increasing trend along with the extension of the adsorption time, the removal rate can reach 90% in the first 1h, the balance is reached after about 3h, and the removal rate reaches 95%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Various other modifications and alterations will occur to those skilled in the art upon reading the foregoing description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The preparation method of the chitosan composite material is characterized by comprising the following steps:
(1) Mixing and heating thiosemicarbazide and 2-naphthaldehyde in an alcohol solution to obtain functional thiourea;
(2) Mixing an alcoholic solution of chitosan with a polyvinyl alcohol solution, adding magnetic nanoparticles, and mixing and reacting in an alkaline solution to obtain magnetic gel beads;
(3) And (3) adding the functionalized thiourea obtained in the step (1) and the magnetic gel beads obtained in the step (2) into a cross-linking agent solution for heating reaction to obtain the chitosan composite material.
2. The method according to claim 1, wherein in the step (1), the molar ratio of the thiosemicarbazide to the 2-naphthaldehyde is 0.5-3: 1.
3. the production method according to claim 1, wherein the heating temperature in the step (1) is 50 ℃ to 80 ℃.
4. The method according to claim 1, wherein in the step (2), the magnetic nanoparticles are selected from Fe 3 O 4 Magnetic nanoparticles, fe 2 O 3 Magnetic nanoparticles or MFe 2 O 4 Magnetic nanoparticles; the MFe 2 O 4 M in the magnetic nanoparticles is selected from one or more of Co, mn, ni and Zn.
5. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the chitosan to the polyvinyl alcohol to the magnetic nanoparticles is 0.5 to 2.
6. The preparation method according to claim 1, wherein in the step (3), the volume ratio of the sum of the masses of the magnetic gel beads and the functionalized thiourea to the crosslinking agent is 1.5-6.
7. The process according to claim 1, wherein in step (3), the crosslinking agent is chosen from glutaraldehyde and/or epichlorohydrin.
8. The method according to claim 1, wherein in the step (3), the volume concentration of the crosslinking agent is 0.01 to 20%.
9. A chitosan composite material obtained by the production method as set forth in any one of claims 1 to 8.
10. The use of the chitosan composite of claim 9 in the detection and adsorption of heavy metals.
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