CN112090408A - Natural brown algae polysaccharide magnetic material and preparation method and application thereof - Google Patents
Natural brown algae polysaccharide magnetic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a natural brown algae polysaccharide magnetic material and a preparation method and application thereof, belonging to the technical field of wastewater treatment. The method selects natural brown alga polysaccharide Salg as a monomer, prepares a magnetic core material by soluble ferric salt and a silicon source, simply and quickly synthesizes the magnetic material MN-Salg of the natural brown alga polysaccharide through a one-step method under the auxiliary action of no crosslinking agent, the natural brown alga polysaccharide Salg is a natural polysaccharide, is nontoxic and good in biocompatibility, is rich in hydroxyl (-OH) and carboxyl (-COOH) on the surface, is rich in chemical adsorption sites, has rich binding sites based on the functional material MN-Salg synthesized by the brown alga polysaccharide, can adsorb organic phosphorus pesticide through the mutual action of hydrogen bonds, has a good removing effect on organic phosphorus residues in water, solves the problems of low efficiency, high cost and secondary environmental pollution in removing the organic phosphorus pesticide residues in water body by the traditional adsorbent, and has good application value and potential.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a natural brown algae polysaccharide magnetic material and a preparation method and application thereof.
Background
Organophosphorus pesticides are used in a large number to prevent and treat diseases and pests in agricultural production, and cause water to be polluted to different degrees. At present, the removal of organophosphorus pesticide residues in water becomes a hotspot of research and discussion in recent years, and new methods and new technologies are continuously emerging. Among them, the adsorption method has advantages of convenience, high efficiency, etc., and has been receiving much attention in recent years; but it is easily lost, difficult to separate and easily causes secondary pollution in the adsorption-separation-cycle process. The magnetic composite material has the advantages of high adsorption efficiency, easy separation and the like, and shows good adsorption effect and higher removal efficiency in the aspect of removing pollutants in water. Therefore, the development and improvement of magnetic adsorption materials are the hot spots and difficulties of current research.
At present, the magnetic sodium alginate composite material is used for treating pollutants such as dye, metal ions and the like in wastewater. The preparation method mainly uses gamma-Fe2O3And Fe3O4The magnetic sodium alginate material is prepared by modifying single or multiple functional monomers containing sodium alginate on the surface of magnetic core through the action of ionic cross-linking agent, electrostatic complexation and the like. For example, Ngomsik A F reported in the Journal of Hazardous Materials Journal of Co (II) removal by magnetic equivalent pads containing Cyanex 272 by mixing iron fluid (gamma-Fe)2O3) Mixing the solution, sodium alginate solution and diisooctyl dithiophosphinate solution, and dripping CaCl into the mixed solution with a syringe2Standing in the solution at room temperature for 16h, thenThen magnetic beads are removed from CaCl2Separating in the solution, repeatedly cleaning with water, and drying to obtain sodium alginate magnetic beads for adsorption of metal Co (II) in water environment; mohammadi et al published in the Journal of International Journal of Biological Macromolecules of Fast fresh green used novel super particulate-coated Fe3O4According to the nanoparticles, FeCl is firstly studied3And FeCl2Mixing the mixed solution with sodium alginate solution, and then dripping the mixed solution into NH under the protection of nitrogen3·H2And reacting the solution O under the protection of nitrogen. Then separating under the action of magnetic field to obtain Fe3O4-Alg nanoparticles and will be applied to the removal of malachite green dye in aqueous solution. The reported synthesis method has the problem of low adsorption efficiency.
Disclosure of Invention
In view of the above, the present invention aims to provide a natural brown algae polysaccharide magnetic material, and a preparation method and an application thereof. The natural brown algae polysaccharide magnetic material prepared by the invention has higher removal rate on organophosphorus pesticides in water.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a natural brown algae polysaccharide magnetic material, which comprises the following steps;
dissolving soluble iron salt and CH3Mixing COONa and an organic solvent to carry out hydrothermal reaction to obtain a magnetic matrix;
mixing the magnetic matrix, an alcohol solvent, water and concentrated ammonia water to obtain a mixed solution, wherein the mass concentration of the concentrated ammonia water is 22-25%;
mixing the mixed solution and a silicon source for reaction to obtain a magnetic core material;
and mixing the magnetic core material, the brown algae polysaccharide and water, and then carrying out magnetic separation to obtain the natural brown algae polysaccharide magnetic material.
Preferably, the temperature of the hydrothermal reaction is 180-210 ℃ and the time is 20-25 h.
Preferably, the mass ratio of the magnetic matrix to the silicon source is 0.6-0.9 g: 0.1-0.25 mL, wherein the silicon source is tetraethyl orthosilicate.
Preferably, the mass ratio of the brown algae polysaccharide to the magnetic core material is 2.5-10.0: 1.
preferably, the mixing temperature of the magnetic core material, the brown algae polysaccharide and the water is 25-40 ℃ and the time is 3-4 h.
Preferably, the magnetic separation further comprises washing the obtained solid product with water, washing with ethanol and drying in sequence.
Preferably, the drying temperature is 45-60 ℃ and the drying time is 12-16 h.
The invention also provides a natural brown algae polysaccharide magnetic material prepared by the preparation method in the technical scheme, which comprises the natural brown algae polysaccharide and a magnetic core material bonded with hydroxyl and carboxyl of the natural brown algae polysaccharide, wherein the magnetic core material is Fe3O4As a core, with SiO2The shell is formed by bonding silicon atoms in the magnetic core material.
The invention also provides application of the natural brown algae polysaccharide magnetic material in the technical scheme in removing organophosphorus pesticides in water.
Preferably, the organophosphorus pesticide contains one or more of cadusafos, triazophos, cadusafos, fenamiphos, sulfotep, disulfoton, fenthion, coumaphos, futhion, pirifolin, pirimiphos-methyl, profenofos, disulfoton, thioprofenofos and cyanophos.
The invention provides a preparation method of a natural brown algae polysaccharide magnetic material, which comprises the following steps; dissolving soluble iron salt and CH3Mixing COONa and an organic solvent to carry out hydrothermal reaction to obtain a magnetic matrix; mixing the magnetic matrix, an alcohol solvent, water and concentrated ammonia water to obtain a mixed solution, wherein the mass concentration of the concentrated ammonia water is 22-25%; mixing the mixed solution with a silicon source to obtain a magnetic core material; and mixing the magnetic core material, the brown algae polysaccharide and water, and then carrying out magnetic separation to obtain the natural brown algae polysaccharide magnetic material. The invention selects natural brown algae polysaccharide Salg as a monomer, prepares a magnetic nucleus material by soluble ferric salt and a silicon source, and passes through a magnetic nucleus material under the auxiliary action of a non-crosslinking agentThe method is simple and rapid to synthesize the functional magnetic material (natural brown algae polysaccharide magnetic material) MN-Salg, the natural brown algae polysaccharide Salg is a natural polysaccharide, is nontoxic and good in biocompatibility, the surface of the natural brown algae polysaccharide Salg is rich in hydroxyl (-OH) and carboxyl (-COOH), chemical adsorption sites are rich, the functional material MN-Salg synthesized based on the brown algae polysaccharide has rich binding sites, can adsorb organic phosphorus pesticides through hydrogen bond interaction, has a good removing effect on organic phosphorus residues in water, solves the problems of low efficiency, high cost and secondary environmental pollution of the traditional adsorbent for removing the organic phosphorus pesticides in water, has good application value and potential, can be rapidly separated and recycled through an external magnetic field after 15 organic phosphorus pesticides in water are removed, avoids the secondary pollution problem of the water, and does not need a centrifuge and other equipment for assistance in the whole process, the operation is simplified, and the operation time is saved.
Drawings
FIG. 1 is a flow chart showing the steps for synthesizing MN-Salg in EXAMPLE 1;
FIG. 2 is a transmission electron microscope image of the microstructure of MN-Salg obtained in example 1;
FIG. 3 is a hysteresis loop of MN-Salg obtained in example 1;
FIG. 4 is a graph showing Zeta potential characterization results of MN-Salg obtained in example 1;
FIG. 5 is a thermogravimetric analysis curve of MN-Salg obtained in example 1;
FIG. 6 shows the results of the adsorption performance test of MN-Salg obtained in example 1;
FIG. 7 shows the results of the adsorption performance test of MN-Salg prepared in examples 2 to 4.
Detailed Description
The invention provides a preparation method of a natural brown algae polysaccharide magnetic material (MN-Salg), which comprises the following steps;
dissolving soluble iron salt and CH3Mixing COONa and an organic solvent to carry out hydrothermal reaction to obtain a magnetic matrix;
mixing the magnetic matrix, an alcohol solvent, water and concentrated ammonia water to obtain a mixed solution, wherein the mass concentration of the concentrated ammonia water is 22-25%;
mixing the mixed solution and a silicon source for reaction to obtain a magnetic core material;
and mixing the magnetic core material, the brown algae polysaccharide and water, and then carrying out magnetic separation to obtain the natural brown algae polysaccharide magnetic material.
In the present invention, unless otherwise specified, all the raw materials used are commercially available products
The invention mixes soluble ferric salt and CH3COONa and an organic solvent are mixed for hydrothermal reaction to obtain a magnetic Matrix (MS). In the present invention, the soluble iron salt is preferably FeCl3·6H2O or Fe (NO)3)3·9H2And O. In the present invention, the soluble iron salt and CH3The mol ratio of COONa is preferably 0.5-0.6: 1.0 to 1.3.
In the present invention, the organic solvent is preferably ethylene glycol.
In the present invention, CH is preferably first selected3First mixing COONa and part of organic solvent to obtain CH3COONa solution, mixing soluble iron salt with the rest organic solvent to obtain soluble iron salt solution, and mixing the CH solution3And carrying out third mixing on the COONa solution and the soluble iron salt solution. In the present invention, the CH3The concentration of the COONa solution is preferably 1.0-1.3 mol/L, and the concentration of the soluble iron salt solution is preferably 0.5-0.6 mol/L. The specific manner of the first mixing, the second mixing and the third mixing is not particularly limited, and a manner known to those skilled in the art may be adopted, specifically, magnetic stirring is performed, and the time of the magnetic stirring is independently preferably 2 to 3 hours.
In the invention, the temperature of the hydrothermal reaction is preferably 180-210 ℃, more preferably 190-200 ℃, and the time is preferably 20-25 h, more preferably 22-24 h. In the present invention, Fe is obtained during the hydrothermal reaction3O4As a magnetic matrix.
After the magnetic matrix is obtained, the magnetic matrix, the alcohol solvent, water and concentrated ammonia water are mixed to obtain a mixed solution, wherein the mass concentration of the concentrated ammonia water is 22-25%.
In the invention, the dosage ratio of the magnetic matrix to the alcohol solvent is preferably 0.6-0.9 g: 28-35 mL. In the present invention, the alcohol solvent is preferably absolute ethanol or isopropanol.
In the invention, the dosage ratio of the magnetic matrix to water is preferably 0.6-0.9 g: 4-8 mL.
In the invention, the dosage ratio of the magnetic matrix to the concentrated ammonia water is preferably 0.6-0.9 g: 1-2 mL.
After the mixed solution is obtained, the mixed solution and a silicon source are mixed and react to obtain the magnetic core Material (MN).
In the invention, the mass ratio of the magnetic matrix to the silicon source is preferably 0.6-0.9 g: 0.1-0.25 mL, more preferably 0.8g:0.2mL, and the silicon source is preferably Tetraethoxysilane (TEOS). In the present invention, the silicon source is preferably tetraethyl orthosilicate (TEOS) or a sodium silicate solution. In the invention, the concentrated ammonia water in the mixed solution is used for catalyzing hydrolysis and condensation of the silicon source, and the alcohol solvent in the mixed solution is used for providing an alcohol medium required by the mixed reaction.
In the present invention, the mixing reaction is preferably performed by stirring at room temperature, the mixing reaction time is preferably 3 to 4 hours, and the rotation speed of the stirring is not particularly limited in the present invention. In the present invention, the magnetic core Material (MN) obtained is Fe3O4As a core, with SiO2Is a shell.
After the magnetic core material is obtained, the magnetic core material, the brown algae polysaccharide and water are mixed and then are subjected to magnetic separation, and the natural brown algae polysaccharide magnetic material is obtained.
In the invention, the mass ratio of the brown algae polysaccharide to the magnetic core material is preferably 2.5-10.0: 1, more preferably 5.0 to 7.5: 1.
in the present invention, the mixing preferably comprises: mixing the magnetic core material with water to obtain a magnetic core material dispersion liquid; and mixing the brown algae polysaccharide with water to obtain a brown algae polysaccharide solution. The invention has no special limit on the concentration of the magnetic core material dispersion liquid and the brown algae polysaccharide solution, and can ensure that the mass ratio of the brown algae polysaccharide to the magnetic core material is within the range.
In the invention, the mixing temperature is preferably 25-40 ℃, more preferably 30-35 ℃, and the time is preferably 3-4 h.
The present invention is not particularly limited with respect to the specific operation of the magnetic separation, and may be performed in a manner well known to those skilled in the art.
In the present invention, after the magnetic separation, it is preferable to further perform water washing, ethanol washing, and drying on the obtained solid product in sequence. The specific operation of the water washing and the ethanol washing is not particularly limited in the present invention, and a method well known to those skilled in the art may be adopted.
In the invention, the drying temperature is preferably 45-60 ℃, the drying time is preferably 12-16 h, and the drying is preferably carried out in an oven.
The invention also provides a natural brown algae polysaccharide magnetic material prepared by the preparation method in the technical scheme, which comprises the natural brown algae polysaccharide and a magnetic core material bonded with hydroxyl and carboxyl of the natural brown algae polysaccharide, wherein the magnetic core material is Fe3O4As a core, with SiO2The shell is formed by bonding silicon atoms in the magnetic core material. In the invention, the mass ratio of the natural brown algae polysaccharide to the magnetic core material is preferably 3-4: 1.
The invention also provides application of the natural brown algae polysaccharide magnetic material in the technical scheme in removing organophosphorus pesticides in water.
In the invention, the organophosphorus pesticide preferably contains one or more of cadusafos, triazophos, cadusafos, fenamiphos, sulfotep, disulfoton, fenthion, coumaphos, futhion, pirifolin, pirimiphos-methyl, profenofos, disulfoton, thioprofos and cyanophos.
In order to further illustrate the present invention, the following examples are given to describe the natural brown algae polysaccharide magnetic material and the preparation method and application thereof in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Firstly FeCl3·6H2O (0.5mol/L) and CH3COONa·3H20(1.0mol/L) of glycol solution, magnetically stirring for 3 hours, and then reacting the mixed solution at 180 ℃ for 25 hours by a hydrothermal method to obtain a magnetic Matrix (MS); then 0.6g MS is added into 28mL isopropanol, 4mL water and 1mL concentrated ammonia water, stirred for 20min to disperse the mixture evenly, and then tetraethyl orthosilicate is added into the mixture continuously, and stirred for 3h at room temperature to obtain the magnetic core material MN. And then uniformly mixing the Salg solution and the MN solution, wherein the mass ratio of the Salg to the MN is 2.5: stirring for 3h at the temperature of 1 and 25 ℃, then carrying out magnetic separation, pouring out upper-layer liquid, respectively washing with water and ethanol, and then putting the obtained product into an oven for drying for 16h at the temperature of 45 ℃ to obtain the functional material MN-Salg. The synthetic route is shown in figure 1, the polymerization degree n in figure 1 is 80-950, and the sphere in figure 1 represents a magnetic core MN.
Material characterization
The microscopic morphological characteristics of the synthesized MN-Salg were characterized by Transmission Electron Microscopy (TEM) and the characterization results are shown in FIG. 2. As can be seen from FIG. 2, the MN-Salg has uniform particle size and good dispersibility, the diameter of the magnetic core MN is 294-350 nm, and the diameter of the MN-Salg is 318-376 nm, which proves that the MN is successfully modified on the surface of the Salg. The magnetic properties of MN-Salg were characterized experimentally using a Vibrating Sample Magnetometer (VSM) technique (see FIG. 3). As shown in fig. 3, the hysteresis loops of MN-Salg are S-shaped curves, all pass through the magnetization zero point, and have smaller hysteresis, remanence and coercivity, indicating that they have superparamagnetism; the saturation magnetization value (Ms) of the magnetic MN-Salg was 75.0emu g-1The magnetic strength is high, and the experimental requirements can be met; the Zeta potential characterization results are shown in FIG. 4, from which it can be seen that the potential of MN-Salg is-50.4 mV. The material has better thermal stability as shown by thermogravimetric analysis of MN-Salg (see FIG. 5).
The material has the following operation process of removing organic phosphorus in water:
50mL (three parts are parallel) of mixed aqueous solution of cadusafos, triazophos, cadusafos, fenamiphos, sulfotep, disulfoton, fenthion, coumaphos, futhion, pirifop, pirimiphos-methyl, profenofos, disulfoton, thioprofos and cyanophos with the concentration of 500 mu g/L is prepared, 100mg of the magnetic material prepared in the embodiment 1 is accurately weighed and respectively put into the organophosphorus mixed solution, and the magnetic material is placed on a shaking table at the constant temperature of 25 ℃ to vibrate for 20min so that the material can fully adsorb organophosphorus. The magnetic material and aqueous solution were separated by the action of an applied magnetic field, and then 1mL of the supernatant was passed through a membrane for LC-MS/MS analysis, and the removal rate was calculated (according to equation 1).
Removal rate calculation formula:
wherein C is0Is the initial concentration of organic phosphorus (mg/L), CeThe concentration of organic phosphorus at equilibrium (mg/L) was determined.
FIG. 6 shows the effect of the magnetic material on removing 15 organophosphorus pesticides, the adsorption rate of the organophosphorus pesticide of the MN-Salg material is high, the concentration of the organophosphorus in the water body is rapidly reduced, and the adsorption balance is achieved in a short time. The removal rate of the magnetic MN-Salg to 15 organophosphorus is 83.9-100%, and the result shows that the material has ideal removal effect on 15 organophosphorus pesticides.
Example 2
As in example 1, the only difference was that the mass ratio of Salg to MN was 5.0: 1.
embodiment 3
As in example 1, the only difference was that the mass ratio of Salg to MN was 7.5: 1.
example 4
As in embodiment 1, the only difference is that the mass ratio of Salg to MN is 10: 1.
the adsorption performance of MN-Salg prepared in the embodiments 2 to 4 was tested, and the results are shown in FIG. 7. It is known that MN-Salg obtained from different amounts of raw materials have different adsorption properties.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A preparation method of natural brown algae polysaccharide magnetic material is characterized by comprising the following steps;
dissolving soluble iron salt and CH3Mixing COONa and an organic solvent to carry out hydrothermal reaction to obtain a magnetic matrix;
mixing the magnetic matrix, an alcohol solvent, water and concentrated ammonia water to obtain a mixed solution, wherein the mass concentration of the concentrated ammonia water is 22-25%;
mixing the mixed solution and a silicon source for reaction to obtain a magnetic core material;
and mixing the magnetic core material, the brown algae polysaccharide and water, and then carrying out magnetic separation to obtain the natural brown algae polysaccharide magnetic material.
2. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 180 to 210 ℃ for 20 to 25 hours.
3. The preparation method according to claim 1, wherein the mass ratio of the magnetic matrix to the silicon source is 0.6-0.9 g: 0.1-0.25 mL, wherein the silicon source is tetraethyl orthosilicate.
4. The preparation method of claim 1, wherein the mass ratio of the brown algae polysaccharide to the magnetic core material is 2.5-10.0: 1.
5. the preparation method of claim 1, wherein the mixing temperature of the magnetic core material, the brown algae polysaccharide and the water is 25-40 ℃ and the mixing time is 3-4 h.
6. The preparation method according to claim 1, wherein the magnetic separation further comprises washing the obtained solid product with water, washing with ethanol, and drying in sequence.
7. The preparation method according to claim 6, wherein the drying temperature is 45-60 ℃ and the drying time is 12-16 h.
8. The natural brown algae polysaccharide magnetic material prepared by the preparation method of any one of claims 1 to 7, which comprises natural brown algae polysaccharide and a magnetic core material bonded with hydroxyl and carboxyl of the natural brown algae polysaccharide, wherein the magnetic core material is Fe3O4As a core, with SiO2The shell is formed by bonding silicon atoms in the magnetic core material.
9. The use of the natural brown algae polysaccharide magnetic material of claim 8 for removing organophosphorus pesticides from water.
10. The use as claimed in claim 9, wherein the organophosphorus pesticide contains one or more of cadusafos, triazophos, cadusafos, fenamiphos, fenitrothion, fonofos, fenthion, coumaphos, futhion, pirifop, pirimiphos-methyl, profenofos, phosmet, thioprofos and cyanophos.
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| CN110343256A (en) * | 2019-06-13 | 2019-10-18 | 浙江省农业科学院 | A kind of magnetic COF-DpTpb and its preparation method and application for being enriched with organophosphorus insecticide |
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2020
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| CN108043363A (en) * | 2017-12-13 | 2018-05-18 | 武汉理工大学 | The preparation method of chitosan magnetic adsorbent |
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