CN110538638A - Magnetic composite adsorption material and preparation method and application thereof - Google Patents
Magnetic composite adsorption material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a chitosan/Al 2O3/Fe3O4 magnetic composite material, a preparation method thereof and application thereof in water treatment, wherein the chitosan/Al 2O3/Fe3O4 magnetic composite material is used as an adsorption material for removing phenol red dye in water, and the adsorption removal rate is 85-99%; the Fe3O4 magnetic nano-ions as insoluble solid substances have the advantages of large specific surface area, quick magnetic separation and low toxicity, the chitosan has the advantages of no pollution and good biodegradability, amino, hydroxyl and aluminum oxide on the surface of the chitosan can provide hydrogen bond action to adsorb phenol red dye, and the three have synergistic adsorption effect on the adsorption removal of the phenol red dye.
Description
Technical Field
The invention relates to the technical field of magnetic nanoparticle preparation, in particular to a magnetic composite adsorption material and a preparation method and application thereof.
Background
It is well known that the discharge of waste water from textile, paper, carpet, leather, cosmetics and other industries into rivers causes many problems, mainly because the discharged industrial water contains a large amount of organic dyes and is highly toxic to aquatic organisms. Many organic dyes in industry are chemically stable, are resistant to oxidation and photo-heat, and are not easy to treat in waste water by common water treatment methods. Mixing with water can cause a number of problems such as increased Chemical Oxygen Demand (COD), reduced light penetration and visibility, so its discharge into the environment can cause serious environmental, aesthetic and health problems.
In view of economic competitiveness and efficiency, many chemical, physical, and biological technologies have been proposed to perform adsorption of dyes, however, general adsorption is accompanied by problems such as low adsorption capacity, poor selectivity, complicated preparation process, and difficulty in regeneration, and it is important to select an adsorption material having high adsorption capacity and high selectivity for dye molecules.
Chitosan (CS) is widely applied to the environmental protection industry, and a large amount of hydroxyl and amino components on a molecular chain of the Chitosan have good removal effects on pollutants such as heavy metals, dyes and the like. However, when chitosan is used as an adsorbent, the chitosan has the disadvantages of poor mechanical stability, easy secondary pollution, difficult regeneration and the like, and the application of chitosan in industry is limited. Therefore, it is very necessary to graft chitosan on the surface of insoluble solid substance in order to improve its mechanical strength, regeneration and separation properties.
Disclosure of Invention
In order to solve the technical problem of poor regeneration and separation performance when chitosan is used as an adsorbent, a magnetic composite adsorption material, a preparation method and application thereof are provided.
A preparation method of a magnetic composite adsorption material comprises the following steps:
(1) preparation of Fe3O 4: adding an iron source into a hydrochloric acid aqueous solution, introducing N2 to remove oxygen, continuously stirring in an N2 atmosphere, then dropwise adding a NaOH solution, continuously stirring, heating to 80 ℃ for reacting for 6 hours, collecting a product Fe3O4 nano particle by using a magnet after the reaction is finished, washing the product Fe3O4 nano particle to be neutral by using ethanol, and drying for later use;
(2) preparation of Al2O3/Fe3O4 core-shell spheres: ultrasonically dispersing Fe3O4 nano particles in aluminum isopropoxide and ethanol, dropwise adding a mixed solution of ethanol and water, stirring at 800-1000rpm for 60-90min, collecting a product after the reaction is finished, washing with ethanol, and drying for later use;
(3) Preparing a chitosan/Al 2O3/Fe3O4 magnetic composite material: ultrasonically dispersing Al2O3/Fe3O4 in a 3 wt% acetic acid solution of chitosan, adding a glutaraldehyde solution after uniformly dispersing for 15-30min, crosslinking to generate black gel, drying the obtained black gel, repeatedly washing the black gel with water and the acetic acid solution with the mass fraction of 2%, and drying to obtain the chitosan/Al 2O3/Fe3O4 magnetic composite material.
Further, the hydrochloric acid aqueous solution in the step (1) is a mixed solution of 12mol/L hydrochloric acid and water, and the mass ratio of the 12mol/L hydrochloric acid to the water is 1: 25; the iron source is FeSO4 and Fe2(SO4)3, and the molar ratio of Fe2+ in FeSO4 to Fe2+ in Fe2(SO4)3 is 1: 2; the mass ratio of the 12mol/L hydrochloric acid to Fe2(SO4)3 is 1: 4; the molar concentration of the NaOH solution is 1.5mol/L, and the volume ratio of the NaOH solution to water in the hydrochloric acid aqueous solution is 3: 1.
Further, the dropping speed of the NaOH solution in the step (1) is 2.5 mL/min.
Further, the mass ratio of the Fe3O4 nano particles to the mixed liquid of aluminum isopropoxide, ethanol and water in the step (2) is 0.1:1 (38-40: 1; the volume ratio of the ethanol to the water in the mixed solution of the ethanol and the water is 1: 5.
Further, in the step (3), the mass fraction of chitosan in the 3 wt% acetic acid solution of chitosan is 2%, the mass fraction of the glutaraldehyde solution is 25%, and the dosage of Al2O3/Fe3O4, the 3 wt% acetic acid solution of chitosan and the glutaraldehyde solution is 0.15g:10mL:0.135 mL.
Further, the drying stability in the steps (1) to (3) is 50-60 ℃, and the drying time is 2-18 h.
The invention also aims to provide the magnetic composite adsorbing material prepared by the method, and the magnetic composite adsorbing material is a chitosan/Al 2O3/Fe3O4 magnetic composite material.
The last purpose of the invention is to provide the application of the magnetic composite adsorbing material in water quality treatment, and the application is used for removing phenol red in water.
Further, the application method comprises the following steps: adding a chitosan/Al 2O3/Fe3O4 magnetic composite material into a phenol red aqueous solution, adjusting the pH value to be 6-8, oscillating for 45-60min at 40-50 ℃, magnetically separating the chitosan/Al 2O3/Fe3O4 magnetic composite material, and collecting supernatant to obtain the phenol red-removed aqueous solution.
Further, the mass concentration of the phenol red water solution is less than or equal to 100 ppm; the dosage of the chitosan/Al 2O3/Fe3O4 magnetic composite material in 10mL of phenol red water solution is 10mg, and the adsorption-removal rate of the chitosan/Al 2O3/Fe3O4 magnetic composite material to phenol red is 85-99%.
The beneficial technical effects are as follows: the invention relates to a chitosan/Al 2O3/Fe3O4 magnetic composite material and a preparation method thereof; the adsorbent is used as an adsorbing material for removing phenol red dye in water, and the adsorption removal rate is 85-99%; the Fe3O4 magnetic nano-ions as insoluble solid substances have the advantages of large specific surface area, quick magnetic separation and low toxicity, have certain physical adsorption effect on phenol red dyes, chitosan has the advantages of no pollution and good biodegradability, amino, hydroxyl and aluminum oxide on the surface of the chitosan can provide hydrogen bond effect to adsorb the phenol red dyes, and the three have synergistic adsorption effect on the adsorption removal of the phenol red dyes.
Drawings
FIG. 1 is SEM scanning electron micrographs of Fe3O4 nanoparticles, Al2O3/Fe3O4 core-shell spheres and chitosan/Al 2O3/Fe3O4 magnetic composite materials prepared in steps (1), (2) and (3) of example 1, wherein a is the SEM image of Fe3O4 nanoparticles, and the scale in the SEM image is 1 μm; b is an SEM image of an Al2O3/Fe3O4 core-shell sphere with a scale of 500 nm; SEM images of the magnetic composite material of c and d, namely chitosan/Al 2O3/Fe3O4, and scales of c and d are respectively 20 mu m and 200 nm.
FIG. 2 is an X-ray diffraction diagram of the magnetic composite material of Fe3O4 nanoparticles and chitosan/Al 2O3/Fe3O4 prepared in steps (1) and (3) of example 1, wherein a represents Fe3O4 nanoparticles and b represents chitosan/Al 2O3/Fe3O 4.
FIG. 3 is an infrared spectrum of the magnetic composite material of Fe3O4 nanoparticles and chitosan/Al 2O3/Fe3O4 prepared in steps (1) and (3) of example 1, wherein a represents the Fe3O4 nanoparticles, and b represents the magnetic composite material of chitosan/Al 2O3/Fe3O 4.
FIG. 4 is a linear plot of concentration versus absorbance for the phenol red aqueous solution of example 3.
FIG. 5 is a graph showing the effect of the concentration of the phenol red aqueous solution on the adsorption effect in example 3.
FIG. 6 is a graph showing the effect of adsorption time on adsorption effect in example 3.
FIG. 7 shows the effect of pH on adsorption effect of phenol red aqueous solution in example 3.
FIG. 8 is a graph showing the effect of temperature on adsorption in example 3.
Detailed Description
The invention is further described below with reference to the figures and specific examples, without limiting the scope of the invention.
Example 1
A preparation method of a composite magnetic adsorption material comprises the following steps:
(1) Preparation of Fe3O 4: adding 2.78g of FeSO4 & 7H2O and 4.0g of Fe2(SO4)3 into 0.85mL of 12mol/L concentrated hydrochloric acid and 25mL of water, introducing N2 to remove oxygen for 30min, continuously stirring under the atmosphere of N2, then dropwise adding 75mL of 1.5mol/L NaOH solution at the speed of 2.5mL/min, heating to 80 ℃ under continuous stirring to react for 6 hours, after the reaction is finished, collecting a product Fe3O4 nano particle by using a magnet, washing to be neutral by using ethanol, and carrying out vacuum drying at 50 ℃ for 18 hours for later use;
(2) preparation of Al2O3/Fe3O4 core-shell spheres: ultrasonically dispersing 0.1g of Fe3O4 nano particles in 1g of aluminum isopropoxide and 50mL of ethanol, dropwise adding a mixed solution (volume ratio is 1:1) of 1g of ethanol and water, stirring at 1000rpm for 75min, collecting a product after the reaction is finished, washing the product with ethanol for multiple times, and drying in an oven at 60 ℃ for 2h for later use;
(3) Preparing a chitosan/Al 2O3/Fe3O4 magnetic composite material: ultrasonically dispersing 0.15g of Al2O3/Fe3O4 in 10mL of 3 wt% acetic acid solution with the mass fraction of 2% of chitosan, adding 135 mu L of 25% glutaraldehyde solution after uniformly dispersing for 20min, crosslinking to generate black gel, drying the obtained black gel at 60 ℃ for 12h, repeatedly washing the black gel with water and 2% acetic acid solution, and drying the black gel at 50 ℃ for 12h to obtain the chitosan/Al 2O3/Fe3O4 magnetic composite material.
SEM scanning electron micrographs of the Fe3O4 nanoparticles, Al2O3/Fe3O4 core-shell spheres and the chitosan/Al 2O3/Fe3O4 magnetic composite material prepared in steps (1), (2) and (3) of the example are shown in FIG. 1, wherein a is the SEM image of the Fe3O4 nanoparticles, and the scale in the SEM image is 1 μm; b is an SEM image of an Al2O3/Fe3O4 core-shell sphere with a scale of 500 nm; SEM images of the magnetic composite material of c and d, namely chitosan/Al 2O3/Fe3O4, and scales of c and d are respectively 20 mu m and 200 nm. It can be known from c and d in fig. 1 that after the glutaraldehyde crosslinking agent is added, amino groups of chitosan are crosslinked with glutaraldehyde on the surface of the Al2O3/Fe3O4 core-shell sphere to generate a polymer coating, and it can be clearly seen that the polymer coating is relatively uniform.
The Fe3O4 nanoparticles and the chitosan/Al 2O3/Fe3O4 magnetic composite material prepared in steps (1) and (3) of this example were subjected to X-ray diffraction, and the crystallinity and phase composition of the sample were measured, wherein the XRD pattern is shown in fig. 2, it can be seen from fig. 2 that the Fe3O4 nanoparticles represented by the b-curve have 6 diffraction peaks (2 θ ═ 32.2 °, 36.5 °, 43.2 °, 53.8 °, 57.3 ° and 62.7 °) according to the X-ray diffraction data of iron tetroxide that meet the standard, and the characteristic diffraction peak of the magnetite phase can be seen in the magnetic composite material represented by the a-curve, and the position of the diffraction peak of Fe3O4 of the a-curve is consistent, indicating that magnetite nanoparticles are present in the magnetic composite material. This indicates that the surface coating modification has no significant effect on the crystalline morphology of Fe3O 4.
FT-IR test was performed on the Fe3O4 nanoparticles and the chitosan/Al 2O3/Fe3O4 magnetic composite material prepared in steps (1) and (3) of this example, the infrared spectrogram is shown in FIG. 3, and in the infrared spectrogram of Fe3O4 nanoparticles represented by curve a, the peak at 560cm-1 is related to the stretching vibration of Fe-O bond in the crystal lattice of Fe3O 4; in the infrared spectrum of the chitosan/Al 2O3/Fe3O4 magnetic composite material represented by the curve b, the peak widths of overlapping peaks related to Fe-Al-O bonds and Fe-O bonds at 3453cm-1, 1572cm-1 and 560cm-1 are larger than that of Fe3O4 respectively; this confirms that the surface of the Fe3O4 nanoparticle is successfully coated with Al2O3 and chitosan; the band of the chitosan/Al 2O3/Fe3O4 magnetic composite material disappears at 1691cm-1, and a new C ═ N stretching vibration characteristic peak appears at 1837cm-1, which is related to the glutaraldehyde crosslinking reaction. On the other hand, broad peaks related to Fe-Al-O and Fe-O appear at 560cm < -1 >, which indicates that chitosan is successfully crosslinked on the surface of the Al2O3/Fe3O4 core-shell sphere by taking glutaraldehyde as a crosslinking agent. In addition, the chitosan/Al 2O3/Fe3O4 magnetic composite material is found to have a wider band at 1850-3400cm-1, which is caused by the stretching effect of hydroxyl (O-H).
Example 2
A preparation method of a composite magnetic adsorption material comprises the following steps:
(1) preparation of Fe3O 4: same as in step (1) of example 1;
(2) Preparation of Al2O3/Fe3O4 core-shell spheres: ultrasonically dispersing 0.1g of Fe3O4 nano particles in 1g of aluminum isopropoxide and 49mL of ethanol, dropwise adding a mixed solution (volume ratio is 1:1) of 1g of ethanol and water, stirring at 900rpm for 90min, collecting a product after the reaction is finished, washing the product with ethanol for multiple times, and drying in an oven at 60 ℃ for 2h for later use;
(3) Preparing a chitosan/Al 2O3/Fe3O4 magnetic composite material: ultrasonically dispersing 0.15g of Al2O3/Fe3O4 in 10mL of 3 wt% acetic acid solution with the mass fraction of 2% of chitosan, adding 135 mu L of 25% glutaraldehyde solution after uniformly dispersing for 30min, crosslinking to generate black gel, drying the obtained black gel at 60 ℃ for 12h, repeatedly washing the black gel with water and 2% acetic acid solution, and drying the black gel at 50 ℃ for 12h to obtain the chitosan/Al 2O3/Fe3O4 magnetic composite material.
The product of this example was observed by scanning electron microscopy and the morphology was the same as in example 1.
the product of this example was subjected to X-ray diffraction, and the crystallinity and phase composition of the sample were measured, with the results being the same as in example 1.
The FT-IR test was performed on the product of this example, and the position of the peak of the product in the infrared spectrum was the same as that in example 1.
Example 3
adsorption-removal test of phenol red solution:
(1) A series of standard solutions of phenol red aqueous solutions were prepared to have a concentration of 5 to 100 μ g/mL, and absorbance at a wavelength of 431nm was measured at each corresponding concentration, and the measured absorbance was plotted as an abscissa and an ordinate, and then linear fitting was performed, as shown in fig. 4, from which fig. 4, it was found that beer's law (a-Kbc) was observed in a concentration range (0 to 50 μ g/mL), a straight line with a high regression coefficient value was obtained, and the degree of fitting R2-0.9913 and the linear relation Y-0.0593X +0.0422 were obtained.
(2) Influence of phenol red aqueous solution concentration on adsorption effect: 10mL of phenol red aqueous solution with the concentration of 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 and 100. mu.g/mL is transferred into a plurality of centrifuge tubes, 0.01g of the chitosan/Al 2O3/Fe3O4 magnetic composite material prepared in the example 1 is added as an adsorbent, the mixture is shaken for 50min at 25 ℃, kept stand and separated by a magnet, supernatant liquid is taken, the absorbance of the supernatant liquid is respectively measured by an ultraviolet-visible spectrophotometer, and the adsorption amount is calculated, and the result is shown in figure 5, and as the concentration of the phenol red in the aqueous solution increases, the adsorption amount of the chitosan/Al 2O3/Fe3O4 magnetic composite material of the invention to the phenol red basically tends to increase. The reason is that the input amount of the adsorbing material in the solution is unchanged, and before the balance is achieved, the concentration difference between the phenol red aqueous solution and the magnetic composite material is increased along with the increase of the concentration of the phenol red aqueous solution, so that the mass transfer driving force is increased, the diffusion speed of phenol red molecules is increased, the surface of the magnetic composite material is fully contacted with phenol red, active adsorption sites such as hydroxyl, amino and the like on the surface of the magnetic composite material are fully utilized, and a great promoting effect is achieved on the adsorption process.
(3) Influence of adsorption time on adsorption effect: transferring 10mL of phenol red aqueous solution with the concentration of 5 mug/mL into a plurality of centrifuge tubes, adding 0.01g of chitosan/Al 2O3/Fe3O4 magnetic composite material prepared in the embodiment 1 as an adsorbent, respectively oscillating for 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 60min, 80min, 100min and 120min, standing, separating by using a magnet, taking supernatant, measuring the absorbance of the supernatant by using ultraviolet-visible spectrophotometry, and calculating the adsorption quantity, wherein as shown in FIG. 6, the longer the enrichment time is, the better the interaction time between the chitosan/Al 2O3/Fe3O4 magnetic composite material and the phenol red aqueous solution is, the adsorption effect is better, but if the enrichment process time is too long, the enrichment effect is continuously prolonged after the enrichment is carried out to 60min, the enrichment effect changes little.
(4) Influence of the pH of the phenol red aqueous solution on the adsorption effect: weighing 9 parts of 0.01g of the chitosan/Al 2O3/Fe3O4 magnetic composite material prepared in example 1 as an adsorbent, sequentially adding 10mL of 5 mu g/mL phenol red solutions with different pH values (the pH values are respectively 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0 and 10.0), placing the mixture in a water bath constant-temperature oscillator at 45 ℃ for reaction for 60min, standing, separating by using a magnet, taking supernatant, measuring the absorbance of the supernatant by using an ultraviolet-visible spectrophotometer, and calculating the adsorption quantity, wherein the result is shown in FIG. 7, and 7 shows that the adsorption capacity of the chitosan/Al 2O 3/magnetic composite material to the phenol red changes little along with the increase of the pH value of the solution. The adsorption capacity of phenol red in the aqueous solution gradually becomes gentle from the beginning of the increase of the pH value of the solution above 3.0. Mainly because under strong acid condition, protonation is stronger, electrostatic repulsion is dominant, adsorption is lower, and with the rise of pH, electrostatic attraction is gradually strengthened, and adsorption capacity is increased. Neutral conditions of pH 7.0 were chosen.
(5) Influence of temperature on adsorption effect: the concentration of the phenol red aqueous solution was 5. mu.g/mL, the pH was 7.0, 0.01g of the chitosan/Al 2O3/Fe3O4 magnetic composite material prepared in example 1 was added to 10mL of the phenol red solution as an adsorbent, the mixture was shaken in a water bath constant temperature shaker at different temperatures (25 ℃, 35 ℃ and 45 ℃) for 60min, allowed to stand, separated with a magnet, and the supernatant was subjected to UV-visible spectrophotometry to measure the absorbance and calculate the amount of adsorption, and as shown in FIG. 8, it was found from FIG. 8 that the amount of adsorption of the chitosan/Al 2O3/Fe3O4 magnetic composite material to phenol red increased with the increase in the temperature of the solution. This is because the chitosan/Al 2O3/Fe3O4 magnetic composite material absorbs heat to adsorb phenol red, the temperature is increased, and the dye molecules can obtain enough energy to generate more and more interactions with the surface active center of the adsorbent.
Application example 1
10mg of the chitosan/Al 2O3/Fe3O4 magnetic composite material prepared in the embodiment 1 is added into 10mL of phenol red aqueous solution (the mass concentration of the phenol red aqueous solution is less than or equal to 100ppm), then the pH value is adjusted to 7, the mixture is oscillated for 60min at 45 ℃, the chitosan/Al 2O3/Fe3O4 magnetic composite material is magnetically separated, and the supernatant is collected to obtain the phenol red-removed aqueous solution, wherein the removal rate reaches 99%. The chitosan/Al 2O3/Fe3O4 magnetic composite material which is separated magnetically is recovered, 0.1mol/L HCl is used as a desorption agent, the recovered material is desorbed and reused, and the adsorption-removal rate of the recovered and reused chitosan/Al 2O3/Fe3O4 magnetic composite material to phenol red can still reach 99% according to the method and 3 times of parallel experiments.
10mg of the chitosan/Al 2O3/Fe3O4 magnetic composite material prepared in the example 2 is added into 10mL of phenol red aqueous solution (the mass concentration of the phenol red aqueous solution is less than or equal to 100ppm), then the pH value is adjusted to 6, the mixture is oscillated for 45min at 50 ℃, the chitosan/Al 2O3/Fe3O4 magnetic composite material is magnetically separated, and the supernatant is collected to obtain the phenol red-removed aqueous solution, wherein the removal rate reaches 85%. The chitosan/Al 2O3/Fe3O4 magnetic composite material separated by magnetism is recovered, 0.1mol/L HCl is used as a desorption agent, the recovered material is desorbed and reused, and the adsorption-removal rate of the recovered and reused chitosan/Al 2O3/Fe3O4 magnetic composite material to phenol red can still reach 85% according to the method and 3 times of parallel experiments.
Claims (10)
1. The preparation method of the magnetic composite adsorbing material is characterized by comprising the following steps of:
(1) Preparation of Fe3O 4: adding an iron source into a hydrochloric acid aqueous solution, introducing N2 to remove oxygen, continuously stirring in an N2 atmosphere, then dropwise adding a NaOH solution, continuously stirring, heating to 80 ℃ for reacting for 6 hours, collecting a product Fe3O4 nano particle by using a magnet after the reaction is finished, washing the product Fe3O4 nano particle to be neutral by using ethanol, and drying for later use;
(2) preparation of Al2O3/Fe3O4 core-shell spheres: ultrasonically dispersing Fe3O4 nano particles in aluminum isopropoxide and ethanol, dropwise adding a mixed solution of ethanol and water, stirring at 800-1000rpm for 60-90min, collecting a product after the reaction is finished, washing with ethanol, and drying for later use;
(3) Preparing a chitosan/Al 2O3/Fe3O4 magnetic composite material: ultrasonically dispersing Al2O3/Fe3O4 in a 3 wt% acetic acid solution of chitosan, adding a glutaraldehyde solution after uniformly dispersing for 15-30min, crosslinking to generate black gel, drying the obtained black gel, repeatedly washing the black gel with water and the acetic acid solution with the mass fraction of 2%, and drying to obtain the chitosan/Al 2O3/Fe3O4 magnetic composite material.
2. the method for preparing the magnetic composite adsorbing material according to claim 1, wherein the hydrochloric acid aqueous solution in the step (1) is a mixed solution of 12mol/L hydrochloric acid and water, and the mass ratio of the 12mol/L hydrochloric acid to the water is 1: 25; the iron source is FeSO4 and Fe2(SO4)3, and the molar ratio of Fe2+ in FeSO4 to Fe2+ in Fe2(SO4)3 is 1: 2; the mass ratio of the 12mol/L hydrochloric acid to Fe2(SO4)3 is 1: 4; the molar concentration of the NaOH solution is 1.5mol/L, and the volume ratio of the NaOH solution to water in the hydrochloric acid aqueous solution is 3: 1.
3. The method for preparing a magnetic composite adsorbing material according to claim 1, wherein the dropping speed of the NaOH solution in step (1) is 2.5 mL/min.
4. the preparation method of the magnetic composite adsorption material according to claim 1, wherein the mass ratio of the Fe3O4 nanoparticles to the mixed solution of aluminum isopropoxide, ethanol and water in the step (2) is 0.1:1 (38-40: 1; the volume ratio of the ethanol to the water in the mixed solution of the ethanol and the water is 1: 5.
5. The method for preparing the magnetic composite adsorption material according to claim 1, wherein the mass fraction of chitosan in the 3 wt% acetic acid solution of chitosan in the step (3) is 2%, the mass fraction of the glutaraldehyde solution is 25%, and the amounts of the Al2O3/Fe3O4, the 3 wt% acetic acid solution of chitosan and the glutaraldehyde solution are 0.15g:10mL:0.135 mL.
6. The method for preparing a magnetic composite adsorbing material according to claim 1, wherein the drying stability in the steps (1) to (3) is 50-60 ℃, and the drying time is 2-18 h.
7. The magnetic composite adsorbing material prepared by the preparation method according to any one of claims 1 to 6, wherein the magnetic composite adsorbing material is a chitosan/Al 2O3/Fe3O4 magnetic composite material.
8. use of the magnetic composite adsorbent material according to claim 7 in water treatment for removing phenol red from water.
9. the method for preparing the magnetic composite adsorbing material according to claim 8, wherein the method for applying is as follows: adding a chitosan/Al 2O3/Fe3O4 magnetic composite material into a phenol red water solution, adjusting the pH value to be 6-8, oscillating for 45-60min at 40-50 ℃, magnetically separating the chitosan/Al 2O3/Fe3O4 magnetic composite material, collecting supernatant to obtain the phenol red-removed water solution, wherein the adsorption-removal rate of the chitosan/Al 2O3/Fe3O4 magnetic composite material on phenol red is 85-99%.
10. The method for preparing the magnetic composite adsorption material according to claim 9, wherein the mass concentration of the phenol red aqueous solution is less than or equal to 100 ppm; the dosage of the chitosan/Al 2O3/Fe3O4 magnetic composite material in 10mL of phenol red water solution is 10 mg.
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