CN112547025A - Magnetic hydrogel glass bead composite adsorbent material and preparation method and application thereof - Google Patents

Magnetic hydrogel glass bead composite adsorbent material and preparation method and application thereof Download PDF

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CN112547025A
CN112547025A CN201910918906.4A CN201910918906A CN112547025A CN 112547025 A CN112547025 A CN 112547025A CN 201910918906 A CN201910918906 A CN 201910918906A CN 112547025 A CN112547025 A CN 112547025A
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杨桂生
吴建明
姚晨光
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Hefei Genius New Materials Co Ltd
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    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • 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
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The invention discloses a magnetic hydrogel glass bead composite adsorbent material, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) stirring and uniformly mixing polystyrene and caprolactam, adding ferroferric oxide and an initiator, and heating to obtain a mixed molten liquid; adding an activating agent for reaction to obtain a composite material; etching and drying to obtain magnetic nylon microspheres; (2) preparing PVA/CTS composite hydrogel, adding magnetic nylon microspheres and nano chitin solution, stirring and uniformly mixing to obtain composite colloid, and dropwise adding the composite colloid into a sodium hydroxide aqueous solution to obtain FPCC. The FPCC prepared by the invention has good adsorption effect on heavy metal ions, can be widely applied to sewage purification, has low preparation cost and simple preparation operation, can be used for large-scale industrial production, does not cause secondary pollution to the environment, is easy to recover, and is a potential heavy metal ion adsorption material.

Description

Magnetic hydrogel glass bead composite adsorbent material and preparation method and application thereof
Technical Field
The invention belongs to the field of water treatment agents and preparation thereof, and particularly relates to a magnetic hydrogel glass bead composite adsorbent material and a preparation method and application thereof.
Background
In recent years, due to the treatment of industrial pollution sources (such as heavy metal ions and toxic organic matters) without distinction, serious water pollution is caused, and great threat is caused to human health. Among these sources of contamination, high concentrations of heavy metal ions (e.g., copper ions, lead ions) in contaminated water can cause health problems to our body, including kidney, brain, liver and bladder damage, bowel disease, alzheimer's disease and parkinson's disease. Therefore, there is a need to find a method for effectively removing heavy metal ions from polluted water sources. At present, water pollution treatment methods are various and comprise a chemical method, an ion exchange method, a membrane filtration method and an adsorption method. Among them, the adsorption method is a very effective method because it has high anti-contamination efficiency, easy handling, low cost and recyclability. In this case, the key factor is to develop a highly efficient adsorbent which not only effectively removes the contaminants from the wastewater, but also can be easily separated from the treated wastewater.
The hydrogel is a three-dimensional (3D) structural material of a hydrophilic polymer containing abundant polar groups, and has strong adsorption capacity on heavy metal ions in sewage. Chitosan (CTS) is a product obtained after deacetylation of chitin, and contains a large amount of hydroxyl (-OH) and amino (-NH) on its molecular chain2) The active functional groups can form stable complexes with a plurality of heavy metal ions, and are known as excellent metal ion adsorbates.
Disclosure of Invention
The invention aims to provide a magnetic hydrogel glass bead composite adsorbent material, and a preparation method and application thereof, and aims to solve the problems that in the prior art, a sewage treatment agent is low in removal rate of heavy metal ions, high in cost and difficult to recover.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a magnetic hydrogel glass bead composite adsorbent material comprises the following steps:
(1) preparing magnetic nylon microspheres: stirring and uniformly mixing polystyrene and caprolactam at the temperature of 60-100 ℃, adding ferroferric oxide and an initiator, and heating to 130-170 ℃ under the vacuum or inert atmosphere condition to obtain a mixed molten liquid; adding an activating agent into the mixed molten liquid, and then placing the mixed molten liquid in an environment of 150-180 ℃ for reaction for 10-35 min to obtain a composite material; placing the composite material in tetrahydrofuran for etching, and drying to obtain magnetic nylon microspheres (FP);
(2) adding a polyvinyl alcohol (PVA) aqueous solution into chitosan hydrogel (CTS) to obtain composite hydrogel (PVA/CTS); then adding magnetic nylon microspheres (FP) and nano chitin solution (n-CT), stirring and mixing uniformly to obtain a composite colloid, and dropwise adding the composite colloid into a sodium hydroxide aqueous solution to prepare a target product, namely the magnetic hydrogel glass bead composite adsorbent material (FPCC).
In the step (2), the chitosan hydrogel is formed by dissolving chitosan in distilled water, adding acetic acid, and uniformly stirring.
Further, in the step (2), the mass ratio of polyvinyl alcohol to water in the polyvinyl alcohol aqueous solution is (1-3): (35-65).
In the step (1), the initiator is sodium hydroxide or potassium hydroxide, and the activator is toluene diisocyanate.
Further, in the step (1), the mass ratio of the polystyrene to the caprolactam (0.15-0.30) is as follows: 1.
further, in the step (2), the mass ratio of polyvinyl alcohol to chitosan in the composite hydrogel is (0.40-0.60): 1.
in the step (2), the concentration of the sodium hydroxide aqueous solution is 0.05-0.3 mol/L.
It is another object of the present invention to provide a magnetic hydrogel glass bead composite adsorbent material (FPCC) prepared by the above preparation method. The magnetic nylon microspheres FP in the FPCC and the adsorbent n-CT are uniformly distributed in the PVA/CTS three-dimensional network gel.
The third purpose of the invention is to provide the application of the magnetic hydrogel glass bead composite adsorbent material in heavy metal ion sewage treatment. Especially for treating Cu (II) sewage.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the magnetic nylon microspheres are used as magnetic separators, and the ferroferric oxide is wrapped by the nylon microspheres, so that the ferroferric oxide can be effectively prevented from falling off and separating from hydrogel glass beads due to small particle size, and the nylon can effectively improve the adsorption rate and the adsorption strength of the FPCC adsorbent to heavy metal ions; introduce the FPCC with magnetism nylon microballon, make the FPCC that the preparation obtained have magnetism, can separate FPCC from the aquatic through plus magnetic field after FPCC adsorbs finishing to realize FPCC's recovery and reuse, easy operation has greatly improved FPCC's utilization ratio, has reduced sewage treatment's input cost when the environment-friendly.
(2) The molecular chain of the nano chitin and chitosan contains a large amount of hydroxyl (-OH) and amino (-NH)2) The invention takes polyvinyl alcohol (PVA) enhanced Chitosan (CTS) composite hydrogel (PVA/CTS) as a matrix, nano chitin (n-CT) as an adsorption enhancer and magnetic nylon particles (FP) as a magnetic separator, and the surface of the prepared FPCC contains a large amount of amino (-NH)2) And active functional groups such as hydroxyl (-OH) and the like, can form stable complexes with a plurality of heavy metal ions, and has stronger adsorption capacity to the heavy metal ions in the sewage. Experiments prove that the FPCC prepared by the invention has good adsorption effect on heavy metal ions in an aqueous solution, and can be widely applied to industrial sewage treatment and domestic application water purification.
(3) The FPCC provided by the invention has low preparation cost and simple preparation operation, can be used for large-scale industrial production, does not cause secondary pollution to the environment, is easy to recover, and is a potential heavy metal ion adsorption material.
Drawings
FIG. 1 is an SEM and TEM image of magnetic nylon microspheres prepared in example 1;
FIG. 2 is a hysteresis loop diagram of the magnetic nylon microsphere prepared in example 1;
FIG. 3 is a graph showing a particle size distribution of FPCC obtained in example 1;
FIG. 4 is an SEM image of magnified n-CT, PC, FPCC and FPCC images;
FIG. 5 is a hysteresis loop plot of the FPCC prepared in example 1;
FIG. 6 optical photographs of the products prepared in example 1, comparative example 1 and comparative example 3 after adsorbing copper ions;
FIG. 7 is a FTIR plot of various substances;
FIG. 8 is a graph showing the adsorption strength of copper ions of the products obtained in example 1 and comparative examples 1 to 3.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The nano chitin solution (n-CT) used in the following examples or comparative examples was purchased from new materials ltd, guangham, hengyu; the solid content is 7.6 percent, the weight average molecular weight is 250kDa, the deacetylation degree is 70 percent, and the specific surface area is 260m2/g。
Example 1
(1) Preparing magnetic nylon microspheres: 20g of polystyrene microparticles and 80g of caprolactam were added to a 250mL three-necked flask, and thoroughly mixed and stirred at 80 ℃ for 12 hours. Then 2.0g of ferroferric oxide and 0.8g of sodium hydroxide are added thereto and the temperature is raised to 150 ℃ under vacuum. To accelerate the polymerization rate of caprolactam, 1mL of activator Toluene Diisocyanate (TDI) was added to the above melt and the melt was poured into a 160 ℃ template and polymerized for 20 min. And finally, etching the obtained composite material in tetrahydrofuran for 2 hours and fully drying to obtain the magnetic nylon microsphere (FP).
(2) Adding 4.0g of chitosan powder into 90mL of distilled water, adding 2mL of glacial acetic acid into the chitosan powder, and mechanically stirring the mixture for 1 hour to obtain chitosan hydrogel; 2.0g of PVA powder was added to 50mL of distilled water and heated to 70 ℃ with constant stirring for 15min to give an aqueous PVA solution. Adding 50mL of aqueous solution of LPVA, 2.0g of FP powder and 10mL of nano chitin solution (n-CT) into the chitosan hydrogel, and continuously mechanically stirring for 3 hours at the temperature of 40 ℃ to obtain the composite colloid. The obtained composite colloid is dropwise injected into 0.1mol/L sodium hydroxide aqueous solution by a syringe to obtain black hydrogel glass beads. Then fully washing the magnetic hydrogel glass bead composite adsorbent material to be neutral to obtain the magnetic hydrogel glass bead composite adsorbent material which is named as FPCC-10% (FPCC).
FIG. 1 is an SEM image (A) and a TEM image (B) of magnetic nylon microspheres (FP) prepared in example 1, from which FIG. 1 it can be seen that the FP microspheres have a diameter of about 5-10 μm and are Fe3O4The nanoparticles (black parts in the B diagram) are uniformly distributed inside the FP.
FIG. 2 is a hysteresis loop diagram of the magnetic nylon microsphere prepared in example 1, and from FIG. 2, the saturation hysteresis strength of FP magnetic particles is 11.2 emu/g.
FIG. 3 is a graph showing the distribution of the particle size of FPCC obtained in example 1, and it can be seen from FIG. 3 that the distribution of the diameters of the glass beads of the FPCC hydrogel is 2.6. + -. 0.17 cm.
Comparative example 1
The magnetic hydrogel glass bead composite adsorbent material was prepared in the same manner as in example 1, except that the nano chitin solution was not added in step (2), and the prepared product was named as FPCC-0% (FPC).
Comparative example 2
A material was prepared in the same manner as in step (2) in example (1) except that FP was not added, and the obtained product was designated PCC-10% (PCC).
Comparative example 3
4.0g of chitosan powder was added to 90mL of distilled water, and 2mL of glacial acetic acid was added thereto, and mechanically stirred for 1h to prepare a chitosan hydrogel. Then 50mL of distilled water was added to the chitosan hydrogel and mechanical stirring was continued at 40 ℃ for 3 h. The obtained composite chitosan colloid is dropwise injected into 0.1mol/L sodium hydroxide aqueous solution by using an injector to obtain hydrogel glass beads, and the hydrogel glass beads are fully washed to be neutral and named as PC-0% (PC).
Heavy metal ion adsorption test
0.17g (dry weight) of sorbent material was added to 100mL of 10mM CuNO3The resulting solution was adsorbed by shaking at 120rpm at 30 ℃ for 60min in an aqueous solution (pH 4.2) under a constant temperature water bath shaker (Lange instruments, Inc., Changzhou) at room temperature. The influence of the adsorption time (2.5-50min) and the n-CT content (0 and 10%) on the adsorption strength was investigated. Each set of experiments was repeated three times.
After the adsorption is finished, the hydrogel adsorbent is separated by an external magnetic field, and the initial concentration (C) of Cu (II) is measured by adopting an EDTA titration method0) And final concentration Ce(2.5 mM EDTA as standard solvent, 0.04 wt% xylenol orange as indicator). Equilibrium adsorption Strength (q)e) Calculated by equation 1.
Figure RE-GDA0002347510970000051
Wherein: q. q.se(mg/g) is the adsorption strength of the hydrogel to Cu (II) at adsorption equilibrium, C0And Ce(mol/L) is Cu (II) concentration at adsorption initiation and adsorption equilibrium, respectively, M (g) addition amount (dry weight) of adsorbent, M (g/mol) is Cu (II) relative atomic mass, and V (L) is solution volume.
FIG. 4 is an SEM image of an enlarged view of n-CT, PC, FPCC and FPCC, and it can be seen from FIG. 4 that the diameter of n-CT is about 50nm, while the PC hydrogel carrier has a regular porous structure with pores about 10 μm on one side. And the FP particles and the nano chitin (d) are uniformly distributed in the PC carrier.
FIG. 5 is a hysteresis loop diagram of FPCC prepared in example 1, and it can be seen from FIG. 5 that the saturation hysteresis strength of the glass beads of FPCC hydrogel is 3.5 emu/g.
FIG. 6 is an optical photograph of the products of example 1, comparative example 1 and comparative example 3, wherein PC (A), FPC (B) and FPCC (C) are respectively marked as PC-Cu (E), FPC-Cu (F) and FPCC-Cu (G) after absorbing copper ions, and it can be seen from FIG. 6 that the addition of FP particles blackens the color of the PC hydrogel which is originally snow white. After the hydrogel absorbs the copper ions, the color of the hydrogel turns blue, because the color of the copper ions is blue, and the FPCC hydrogel glass beads display deep blue after absorbing the copper ions, because the nano chitin contained in the FPCC hydrogel is caused by the super strong absorption of the copper ions.
FIG. 7 is a graph of FTIR for each species, wherein each graph represents the species: (A) fe3O4Nanoparticles; (B) n-CT; (C) PC hydrogel; (D) FPC hydrogel; (E) FPCC hydrogel and (F) FPCC-Cu (II) hydrogel, from FIG. 8, it can be seen that the length of the glass beads of the FPCC hydrogel and the glass beads of the FPCC hydrogel are 567cm-1The absorption peak shows that the glass beads of the FPC and the FPCC hydrogel have Fe3O4Magnetic nanoparticles. Furthermore, 1421cm-1(v CN) and 1258 cm-1The absorption peaks at the two positions of (v CN) appear to move to low frequency or disappear, and the reaction of Cu (II) and the amino on the chitosan is proved. And 2865cm-1(νasCH) and 2923cm-1(νsBlue-shift of the absorption peak at CH) again verifies the complexation of amino groups with copper ions on the hydrogel.
FIG. 8 is a graph showing the analysis of the adsorption strength of copper ions of the products obtained in example 1 and comparative examples 1 to 3, and it can be seen from FIG. 8 that PC, which is a material prepared from only chitosan, has the smallest adsorption strength of copper ions; after polyvinyl alcohol, FP and n-CT are added into chitosan, the adsorption strength and adsorption rate of the material to copper ions are obviously improved.
Example 2
(1) Preparing magnetic nylon microspheres: 15g of polystyrene microparticles and 85g of caprolactam were added to a 250mL three-necked flask, and the mixture was thoroughly mixed and stirred at 60 ℃ for 12 hours. Then 2.0g of ferroferric oxide and 0.8g of potassium hydroxide are added thereto and the temperature is raised to 170 ℃ under vacuum. To accelerate the polymerization rate of caprolactam, 1mL of activator Toluene Diisocyanate (TDI) was added to the above melt and the melt was poured into a 170 ℃ template and polymerized for 35 min. And finally, etching the obtained composite material in tetrahydrofuran for 2 hours and fully drying to obtain the magnetic nylon microsphere (FP).
(2) Adding 4.0g of chitosan powder into 90mL of distilled water, adding 2mL of glacial acetic acid into the chitosan powder, and mechanically stirring the mixture for 1 hour to obtain chitosan hydrogel; 1.0g of PVA powder was added to 35mL of distilled water and heated to 70 ℃ with constant stirring for 15min to give an aqueous PVA solution. Adding 50mL of PVA aqueous solution, 2.0g of FP powder and 10mL of nano chitin solution (n-CT) into the chitosan hydrogel, and continuously mechanically stirring for 3h at 40 ℃ to obtain the composite colloid. The obtained composite colloid is dropwise injected into 0.05mol/L sodium hydroxide aqueous solution by a syringe to obtain black hydrogel glass beads. And then fully washing the magnetic hydrogel glass bead composite adsorbent material to be neutral to obtain the magnetic hydrogel glass bead composite adsorbent material.
Example 3
(1) Preparing magnetic nylon microspheres: 23g of polystyrene microparticles and 77g of caprolactam were added to a 250mL three-necked flask, and thoroughly mixed and stirred at 100 ℃ for 12 hours. Then, 2.0g of ferroferric oxide and 0.8g of sodium hydroxide were added thereto and the temperature was raised to 130 ℃ under a nitrogen atmosphere. To accelerate the polymerization of caprolactam, 1mL of activator Toluene Diisocyanate (TDI) was added to the above melt and the melt was poured into a 150 ℃ template and polymerized for 10 min. And finally, etching the obtained composite material in tetrahydrofuran for 2 hours and fully drying to obtain the magnetic nylon microsphere (FP).
(2) Adding 4.0g of chitosan powder into 90mL of distilled water, adding 2mL of glacial acetic acid into the chitosan powder, and mechanically stirring the mixture for 1 hour to obtain chitosan hydrogel; 3.0g of PVA powder was added to 65mL of distilled water and heated to 70 ℃ with constant stirring for 15min to give an aqueous PVA solution. Adding 50mL of PVA aqueous solution, 2.0g of FP powder and 10mL of nano chitin solution (n-CT) into the chitosan hydrogel, and continuously mechanically stirring for 3h at 40 ℃ to obtain the composite colloid. The obtained composite colloid is dropwise injected into 0.3mol/L sodium hydroxide aqueous solution by a syringe to obtain black hydrogel glass beads. And then fully washing the magnetic hydrogel glass bead composite adsorbent material to be neutral to obtain the magnetic hydrogel glass bead composite adsorbent material.

Claims (9)

1. A preparation method of a magnetic hydrogel glass bead composite adsorbent material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing magnetic nylon microspheres: stirring and uniformly mixing polystyrene and caprolactam at the temperature of 60-100 ℃, adding ferroferric oxide and an initiator, and heating to 130-170 ℃ under the vacuum or inert atmosphere condition to obtain a mixed molten liquid; adding an activating agent into the mixed molten liquid, and then placing the mixed molten liquid in an environment of 150-180 ℃ for reaction for 10-35 min to obtain a composite material; placing the composite material in tetrahydrofuran for etching, and drying to obtain magnetic nylon microspheres;
(2) adding a polyvinyl alcohol aqueous solution into the chitosan hydrogel to obtain a composite hydrogel; then adding magnetic nylon microspheres and nano chitin solution, stirring and uniformly mixing to obtain a composite colloid, and dropwise adding the composite colloid into a sodium hydroxide aqueous solution to prepare the magnetic hydrogel glass bead composite adsorbent material.
2. The method of claim 1, wherein: in the step (2), the chitosan hydrogel is formed by dissolving chitosan in distilled water, adding acetic acid, and uniformly stirring.
3. The method of claim 1, wherein: in the step (2), the mass ratio of polyvinyl alcohol to water in the polyvinyl alcohol aqueous solution is (1-3): (35-65).
4. The method of claim 1, wherein: in the step (1), the initiator is sodium hydroxide or potassium hydroxide, and the activating agent is toluene diisocyanate.
5. The method of claim 1, wherein: in the step (1), the mass ratio of the polystyrene to the caprolactam is (0.15-0.30): 1.
6. the method of claim 1, wherein: in the step (2), the mass ratio of polyvinyl alcohol to chitosan in the composite hydrogel is (0.40-0.60): 1.
7. the method of claim 1, wherein: in the step (2), the concentration of the sodium hydroxide aqueous solution is 0.05-0.3 mol/L.
8. The magnetic hydrogel glass bead composite adsorbent material prepared by the preparation method according to any one of claims 1 to 7.
9. The use of the magnetic hydrogel glass bead composite adsorbent material of claim 8 in heavy metal ion wastewater treatment.
CN201910918906.4A 2019-09-26 2019-09-26 Magnetic hydrogel glass bead composite adsorbent material and preparation method and application thereof Withdrawn CN112547025A (en)

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