CN112191233A - Three-dimensional net-shaped composite magnetic material for sewage treatment and preparation method thereof - Google Patents

Three-dimensional net-shaped composite magnetic material for sewage treatment and preparation method thereof Download PDF

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CN112191233A
CN112191233A CN202011014878.2A CN202011014878A CN112191233A CN 112191233 A CN112191233 A CN 112191233A CN 202011014878 A CN202011014878 A CN 202011014878A CN 112191233 A CN112191233 A CN 112191233A
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glass fiber
graphene oxide
chitosan
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司文彬
陈庆
曾军堂
白涛
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Chengdu New Keli Chemical Science Co Ltd
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Abstract

The invention provides a three-dimensional net-shaped composite magnetic material for sewage treatment and a preparation method thereof2+Iron salt and Fe3+Stirring and reacting in a mixed solution of iron salt. According to the ferroferric oxide/bacterial cellulose/glass fiber and graphene oxide/chitosan composite material provided by the invention, the addition of the glass fiber is improvedThe mechanical strength is improved, the formed three-dimensional porous structure has high-efficiency adsorption capacity and good stability, and can be used for sewage treatment for a long time.

Description

Three-dimensional net-shaped composite magnetic material for sewage treatment and preparation method thereof
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a three-dimensional reticular composite magnetic material for sewage treatment and a preparation method thereof.
Background
The problem of sewage treatment has become a global important environmental problem, and especially the pollution of industrial sewage is serious. The industrial sewage refers to sewage, sewage and waste liquid generated in the industrial production process, and contains industrial production materials, intermediate products and products which are lost along with water, and pollutants generated in the production process. With the rapid development of industry, the variety and the amount of sewage are rapidly increased, the pollution to water bodies is more and more extensive and serious, and the health and the safety of human beings are threatened. Therefore, the treatment of industrial sewage is more important than the treatment of municipal sewage for environmental protection.
The sewage treatment mode is a research hotspot in recent years, and compared with treatment modes such as electrodeposition, filtration and the like, physical adsorption has the advantages of low cost, simplicity in operation, no secondary pollution and the like. However, the traditional adsorbing materials including activated carbon, wood chips, coal slag, volcanic ash and the like generally have the defects of low adsorption efficiency, poor selective adsorption, difficult recovery and the like. The porous structure in the hydrogel endows the hydrogel with a huge specific surface area, and can provide a large number of attachment sites for pollutant adsorption. Therefore, the recognition of a good contaminant adsorbent material is being relied upon by numerous researchers.
Therefore, it becomes very important to prepare an ideal adsorbent for removing heavy metal ions, organic pollutants, dyes and the like in polluted water, which has high adsorption efficiency, high adsorption speed, large adsorption capacity, low price and easy recovery. Meanwhile, the method for preparing the novel material needs simple and effective process, and has the excellent characteristics of particle micro/nano, porosity, large specific surface area and the like, particularly can realize quick separation under the action of an external magnetic field, and can realize the recovery and cyclic utilization of the adsorption material and noble metal ions. However, the existing composite porous magnetic material for sewage treatment often has the defects of insufficient mechanical strength, easy breakage and the like, and has poor pollutant treatment effect and the like.
Chinese invention patent application no: 201410667432.8 discloses a three-dimensional graphene foam-nanogold composite material, a preparation method and application thereof; the composite material comprises a three-dimensional graphene foam substrate and nano-gold particles uniformly loaded on the substrate; preparation thereofThe method comprises the following steps: subjecting three-dimensional foam graphene materials to an oxidizing agent, such as HNO3And H2SO4After the mixed solution is treated, cleaning and modifying by using an organic polymer with positive charges; and finally, adding a nano-gold particle solution to react fully to obtain the three-dimensional graphene foam-nano-gold composite material. The Chinese invention patent application number 201110122714.6 discloses a magnetic three-dimensional filler for water purification treatment; the magnetic three-dimensional filler is prepared by uniformly mixing a plastic material, a magnetic material and an auxiliary agent, and then carrying out injection molding, wire drawing, magnetizing and forming processes.
In order to improve the mechanical strength of the composite porous material for sewage treatment and improve the treatment effect on pollutants in water, it is necessary to provide a novel composite porous material for sewage treatment, and further improve the sewage treatment capability and durability of the material.
Disclosure of Invention
Aiming at the defects that the existing composite porous material for sewage treatment, including a porous magnetic composite material, is often insufficient in mechanical strength, easy to break, not ideal in sewage treatment effect and the like, the invention provides a three-dimensional reticular composite magnetic material for sewage treatment and a preparation method thereof, so that the mechanical strength of the composite material is improved, and the composite material has good sewage treatment capability.
In order to solve the problems, the invention adopts the following technical scheme:
the invention relates to a preparation method of a three-dimensional reticular composite magnetic material for sewage treatment, wherein the composite magnetic material is prepared by modifying glass fiber by using an aminosilane coupling agent, mixing and hybridizing the glass fiber with graphene oxide, compounding the glass fiber with chitosan and bacterial cellulose in sequence to form a ternary composite porous material, and finally adding Fe into alkali liquor2+Iron salt and Fe3+The iron salt is prepared by stirring and reacting in a mixed solution of iron salt, and the preparation method comprises the following steps:
(1) adding glass fiber into deionized water, then adding an aminosilane coupling agent, fully stirring, filtering, washing and drying to obtain modified glass fiber;
(2) adding graphene oxide into deionized water, uniformly mixing to obtain graphene oxide aqueous dispersion, adding modified glass fiber into the graphene oxide aqueous dispersion under the mechanical stirring state, fully mixing and stirring, filtering, washing and drying to obtain glass fiber and graphene oxide hybrid material powder;
(3) adding chitosan into acetic acid, uniformly mixing to prepare a chitosan solution, then adding glass fiber and graphene oxide hybrid material powder under a stirring state, and rapidly stirring until the mixture is uniformly mixed to prepare a binary composite solution of the glass fiber and graphene oxide hybrid material/chitosan;
(4) dispersing bacterial cellulose in deionized water, performing ultrasonic dispersion uniformly to obtain a bacterial cellulose water dispersion system, then slowly adding a binary composite solution of glass fiber and graphene oxide hybrid material/chitosan under a high-speed stirring state, and fully stirring uniformly to obtain a ternary composite of the bacterial cellulose/glass fiber and the graphene oxide hybrid material/chitosan;
(5) shaping the obtained ternary composite into a plate with the thickness of 3mmd in a mould, and freeze-drying to obtain a bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan ternary composite porous material;
(6) adding Fe into the obtained ternary composite porous material2+Iron salt and Fe3+And adding alkali liquor into the mixed aqueous solution of the ferric salt, stirring for reaction, filtering, washing and drying after the reaction is finished, thus obtaining the ferroferric oxide/bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan composite magnetic material, namely the three-dimensional reticular composite magnetic material for sewage treatment.
Preferably, the aminosilane coupling agent is one or the combination of more than two of C-aminopropyl triethoxysilane, C-aminopropyl trimethoxysilane, phenylaminomethyl triethoxysilane and phenylaminomethyl trimethoxysilane.
Preferably, in the preparation of the modified glass fiber in the step (1), the mass ratio of the deionized water to the glass fiber to the aminosilane coupling agent is 100:30-50: 2-4.
Preferably, in the step (2), the mass ratio of the deionized water, the graphene oxide and the modified glass fiber is 100:30-50:20-40 in the preparation of the glass fiber and graphene oxide hybrid material powder.
Preferably, in the preparation of the binary composite solution in the step (3), the mass ratio of the deionized water, the chitosan, the glass fiber and the graphene oxide hybrid material powder is 100:20-30: 30-50.
Bacterial Cellulose (BC) is a generic term for cellulose synthesized by any of microorganisms belonging to the genera Acetobacter (Acetobacter), Agrobacterium (Agrobacterium), Rhizobium (Rhizobium), Sarcina (Sarcina), and the like under different conditions. The bacterial cellulose is a natural high molecular compound produced by partial bacteria, and compared with the cellulose extracted from plants, the bacterial cellulose has the advantages of good molecular orientation, high polymerization degree, uniform structure and single fiber form.
Preferably, in the preparation of the ternary complex in the step (4), the mass ratio of the deionized water, the bacterial cellulose, the glass fiber and the graphene oxide hybrid material/chitosan binary complex liquid is 100:20-30: 50-70.
Preferably, the alkali liquor is one of sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the mass concentration is 20-40%.
Preferably, said Fe2+The iron salt is one or the combination of more than two of ferrous chloride, ferrous nitrate and ferrous sulfate.
Preferably, said Fe3+The iron salt is one or the combination of more than two of ferric chloride, ferric nitrate and ferric sulfate.
Preferably, in the preparation of the composite magnetic material in the step (6), water, the ternary composite porous material and Fe2+Iron salt, Fe3+The mass ratio of the ferric salt to the alkali liquor is 100:40-50:10-15:10-15: 8-12.
The invention also provides the three-dimensional reticular composite magnetic material for sewage treatment, which is prepared by the preparation method.
The existing composite porous magnetic material for sewage treatment has the problems of insufficient mechanical strength, easiness in crushing, poor pollutant treatment effect and the like, and the application of the composite porous magnetic material is limited. In view of the above, the invention provides a three-dimensional mesh composite magnetic material for sewage treatment and a preparation method thereof, which comprises the steps of adding glass fibers into deionized water, adding an aminosilane coupling agent, stirring, filtering, washing and drying to obtain modified glass fibers; and preparing graphene oxide into graphene oxide aqueous dispersion, adding the modified glass fiber into the graphene oxide aqueous dispersion under the mechanical stirring state, filtering, washing and drying to obtain the glass fiber and graphene oxide hybrid material powder. Dissolving chitosan in acetic acid to prepare a chitosan solution; dissolving or dispersing the bacterial cellulose in deionized water, and uniformly dispersing by ultrasonic to obtain a bacterial cellulose aqueous solution or a water dispersion system; adding the glass fiber and the graphene oxide hybrid material powder into the chitosan solution under stirring, and quickly stirring until the glass fiber and the graphene oxide hybrid material powder are uniformly mixed to obtain a binary compound of the glass fiber and the graphene oxide hybrid material/chitosan; slowly adding binary composite liquid of glass fiber and graphene oxide hybrid material/chitosan into a bacterial cellulose aqueous solution or a water dispersion system thereof under high-speed stirring to obtain a ternary composite of the bacterial cellulose/glass fiber and the graphene oxide hybrid material/chitosan; freeze-drying the obtained ternary composite to obtain a bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan ternary composite porous material; finally, adding Fe into the obtained bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan ternary composite porous material2+Iron salt and Fe3+And adding alkali liquor into the mixed solution of the ferric salt, and reacting to obtain the ferroferric oxide/bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan composite magnetic material. According to the bacterial cellulose/glass fiber and graphene oxide/chitosan composite material provided by the invention, the mechanical strength is improved due to the addition of the glass fiber, a formed three-dimensional porous structure has high-efficiency adsorption capacity and good stability, and can be used for sewage treatment for a long time.
Compared with the prior art, the invention provides a three-dimensional reticular composite magnetic material for sewage treatment and a preparation method thereof, and the outstanding characteristics and excellent effects are as follows:
1. according to the invention, cellulose is used as a carrier, a hybrid material of glass fiber and graphene oxide and chitosan are loaded in a blending mode, three components can independently generate strong combination under the mutual acting force of covalent bonds, electrostatic attraction, hydrogen bonds and the like, the bacterial cellulose/graphene oxide/chitosan composite material obtained by freeze drying has a three-dimensional porous structure, and magnetic ferroferric oxide particles are loaded by the composite material, so that the magnetic ferroferric oxide particles are easy to recover and separate.
2. According to the invention, in the process of preparing the composite porous material, the glass fiber with high mechanical strength is added, so that the mechanical strength of the prepared porous material is greatly increased, the stability is good, the positive and negative charges on the surface are mutually attracted, the graphene oxide is coated on the surface of the modified glass fiber, the combination is firm, and the service durability of the composite material is good.
3. The invention utilizes the characteristics of porosity and large specific surface area of bacterial cellulose, contains a plurality of hydrophilic hydroxyls in molecules and has certain adsorption capacity on organic micromolecules.
4. The composite material prepared by the invention has high-efficiency adsorption capacity and good stability, and can be used for sewage treatment for a long time.
Drawings
FIG. 1 a: the color of congo red water was filtered using the material of example 1;
FIG. 1 b: the color of congo red water was filtered using the material of comparative example 1;
FIG. 1 c: the color of congo red water was filtered using the material of comparative example 3.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Adding glass fiber into deionized water, then adding an aminosilane coupling agent, fully stirring, filtering, washing and drying to obtain modified glass fiber; the amino silane coupling agent is phenylaminomethyl trimethoxy silane; in the preparation of the modified glass fiber, the mass ratio of deionized water to the glass fiber to the amino silane coupling agent is 100:38: 3;
(2) adding graphene oxide into deionized water, uniformly mixing to obtain graphene oxide aqueous dispersion, adding modified glass fiber into the graphene oxide aqueous dispersion under the mechanical stirring state, fully mixing and stirring, filtering, washing and drying to obtain glass fiber and graphene oxide hybrid material powder; in the preparation of the glass fiber and graphene oxide hybrid material powder, the mass ratio of deionized water, graphene oxide and modified glass fiber is 100:380: 24;
(3) adding chitosan into acetic acid, uniformly mixing to prepare a chitosan solution, then adding glass fiber and graphene oxide hybrid material powder under a stirring state, and rapidly stirring until the mixture is uniformly mixed to prepare a binary composite solution of the glass fiber and graphene oxide hybrid material/chitosan; in the preparation of the binary composite liquid, the mass ratio of the deionized water to the chitosan to the glass fiber to the graphene oxide hybrid material powder is 100:26: 38;
(4) dispersing bacterial cellulose in deionized water, performing ultrasonic dispersion uniformly to obtain a bacterial cellulose water dispersion system, then slowly adding a binary composite solution of glass fiber and graphene oxide hybrid material/chitosan under a high-speed stirring state, and fully stirring uniformly to obtain a ternary composite of the bacterial cellulose/glass fiber and the graphene oxide hybrid material/chitosan; in the preparation of the ternary compound, the mass ratio of deionized water, bacterial cellulose, glass fiber and graphene oxide hybrid material/chitosan binary compound liquid is 100:26: 58;
(5) shaping the obtained ternary composite into a plate with the thickness of 3mmd in a mould, and freeze-drying to obtain a bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan ternary composite porous material;
(6) adding Fe into the obtained ternary composite porous material2+Iron salt and Fe3+Adding alkali liquor into a mixed aqueous solution of ferric salt, stirring for reaction, filtering, washing and drying after the reaction is finished to prepare a ferroferric oxide/bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan composite magnetic material, namely a three-dimensional reticular composite magnetic material for sewage treatment; the alkali liquor is a sodium hydroxide solution with the mass concentration of 28 percent; fe2+The iron salt is ferrous chloride; fe3+The ferric salt is ferric chloride; in the preparation of the composite magnetic material, water, a ternary composite porous material and Fe2+Iron salt, Fe3+The mass ratio of the ferric salt to the alkali liquor is 100:45:12:13: 11.
Example 2
(1) Adding glass fiber into deionized water, then adding an aminosilane coupling agent, fully stirring, filtering, washing and drying to obtain modified glass fiber; the amino silane coupling agent is C-aminopropyl triethoxysilane; in the preparation of the modified glass fiber, the mass ratio of deionized water to the glass fiber to the amino silane coupling agent is 100:40: 3;
(2) adding graphene oxide into deionized water, uniformly mixing to obtain graphene oxide aqueous dispersion, adding modified glass fiber into the graphene oxide aqueous dispersion under the mechanical stirring state, fully mixing and stirring, filtering, washing and drying to obtain glass fiber and graphene oxide hybrid material powder; in the preparation of the glass fiber and graphene oxide hybrid material powder, the mass ratio of deionized water, graphene oxide and modified glass fiber is 100:40: 30;
(3) adding chitosan into acetic acid, uniformly mixing to prepare a chitosan solution, then adding glass fiber and graphene oxide hybrid material powder under a stirring state, and rapidly stirring until the mixture is uniformly mixed to prepare a binary composite solution of the glass fiber and graphene oxide hybrid material/chitosan; in the preparation of the binary composite liquid, the mass ratio of the deionized water, the chitosan, the glass fiber and the graphene oxide hybrid material powder is 100:25: 40;
(4) dispersing bacterial cellulose in deionized water, performing ultrasonic dispersion uniformly to obtain a bacterial cellulose water dispersion system, then slowly adding a binary composite solution of glass fiber and graphene oxide hybrid material/chitosan under a high-speed stirring state, and fully stirring uniformly to obtain a ternary composite of the bacterial cellulose/glass fiber and the graphene oxide hybrid material/chitosan; in the preparation of the ternary compound, the mass ratio of deionized water, bacterial cellulose, glass fiber and graphene oxide hybrid material/chitosan binary compound liquid is 100:25: 60;
(5) shaping the obtained ternary composite into a plate with the thickness of 3mmd in a mould, and freeze-drying to obtain a bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan ternary composite porous material;
(6) adding Fe into the obtained ternary composite porous material2+Iron salt and Fe3+Adding alkali liquor into a mixed aqueous solution of ferric salt, stirring for reaction, filtering, washing and drying after the reaction is finished to prepare a ferroferric oxide/bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan composite magnetic material, namely a three-dimensional reticular composite magnetic material for sewage treatment; the alkali liquor is a sodium hydroxide solution with the mass concentration of 30 percent; fe2+The iron salt is ferrous chloride; fe3+The ferric salt is ferric chloride; in the preparation of the composite magnetic material, water, a ternary composite porous material and Fe2+Iron salt, Fe3+The mass ratio of the ferric salt to the alkali liquor is 100:45:12:12: 10.
Example 3
(1) Adding glass fiber into deionized water, then adding an aminosilane coupling agent, fully stirring, filtering, washing and drying to obtain modified glass fiber; the amino silane coupling agent is C-aminopropyl trimethoxy silane; in the preparation of the modified glass fiber, the mass ratio of deionized water to the glass fiber to the amino silane coupling agent is 100:30: 2;
(2) adding graphene oxide into deionized water, uniformly mixing to obtain graphene oxide aqueous dispersion, adding modified glass fiber into the graphene oxide aqueous dispersion under the mechanical stirring state, fully mixing and stirring, filtering, washing and drying to obtain glass fiber and graphene oxide hybrid material powder; in the preparation of the glass fiber and graphene oxide hybrid material powder, the mass ratio of deionized water, graphene oxide and modified glass fiber is 100:30: 20;
(3) adding chitosan into acetic acid, uniformly mixing to prepare a chitosan solution, then adding glass fiber and graphene oxide hybrid material powder under a stirring state, and rapidly stirring until the mixture is uniformly mixed to prepare a binary composite solution of the glass fiber and graphene oxide hybrid material/chitosan; in the preparation of the binary composite liquid, the mass ratio of the deionized water, the chitosan, the glass fiber and the graphene oxide hybrid material powder is 100:20: 30;
(4) dispersing bacterial cellulose in deionized water, performing ultrasonic dispersion uniformly to obtain a bacterial cellulose water dispersion system, then slowly adding a binary composite solution of glass fiber and graphene oxide hybrid material/chitosan under a high-speed stirring state, and fully stirring uniformly to obtain a ternary composite of the bacterial cellulose/glass fiber and the graphene oxide hybrid material/chitosan; in the preparation of the ternary compound, the mass ratio of deionized water, bacterial cellulose, glass fiber and graphene oxide hybrid material/chitosan binary compound liquid is 100:20: 50;
(5) shaping the obtained ternary composite into a plate with the thickness of 3mmd in a mould, and freeze-drying to obtain a bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan ternary composite porous material;
(6) adding Fe into the obtained ternary composite porous material2+Iron salt and Fe3+Adding alkali liquor into a mixed aqueous solution of ferric salt, stirring for reaction, filtering, washing and drying after the reaction is finished to prepare a ferroferric oxide/bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan composite magnetic material, namely a three-dimensional reticular composite magnetic material for sewage treatment; alkali liquor with a mass concentration of 20% potassium hydroxide solution; fe2+The ferric salt is ferrous nitrate; fe3+The ferric salt is ferric nitrate; in the preparation of the composite magnetic material, water, a ternary composite porous material and Fe2+Iron salt, Fe3+The mass ratio of the ferric salt to the alkali liquor is 100:40:10:10: 8.
Example 4
(1) Adding glass fiber into deionized water, then adding an aminosilane coupling agent, fully stirring, filtering, washing and drying to obtain modified glass fiber; the amino silane coupling agent is phenylaminomethyl triethoxysilane; in the preparation of the modified glass fiber, the mass ratio of deionized water to the glass fiber to the amino silane coupling agent is 100:50: 4;
(2) adding graphene oxide into deionized water, uniformly mixing to obtain graphene oxide aqueous dispersion, adding modified glass fiber into the graphene oxide aqueous dispersion under the mechanical stirring state, fully mixing and stirring, filtering, washing and drying to obtain glass fiber and graphene oxide hybrid material powder; in the preparation of the glass fiber and graphene oxide hybrid material powder, the mass ratio of deionized water, graphene oxide and modified glass fiber is 100:50: 40;
(3) adding chitosan into acetic acid, uniformly mixing to prepare a chitosan solution, then adding glass fiber and graphene oxide hybrid material powder under a stirring state, and rapidly stirring until the mixture is uniformly mixed to prepare a binary composite solution of the glass fiber and graphene oxide hybrid material/chitosan; in the preparation of the binary composite liquid, the mass ratio of the deionized water, the chitosan, the glass fiber and the graphene oxide hybrid material powder is 100:30: 50;
(4) dispersing bacterial cellulose in deionized water, performing ultrasonic dispersion uniformly to obtain a bacterial cellulose water dispersion system, then slowly adding a binary composite solution of glass fiber and graphene oxide hybrid material/chitosan under a high-speed stirring state, and fully stirring uniformly to obtain a ternary composite of the bacterial cellulose/glass fiber and the graphene oxide hybrid material/chitosan; in the preparation of the ternary compound, the mass ratio of deionized water, bacterial cellulose, glass fiber and graphene oxide hybrid material/chitosan binary compound liquid is 100:30: 70;
(5) shaping the obtained ternary composite into a plate with the thickness of 3mmd in a mould, and freeze-drying to obtain a bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan ternary composite porous material;
(6) adding Fe into the obtained ternary composite porous material2+Iron salt and Fe3+Adding alkali liquor into a mixed aqueous solution of ferric salt, stirring for reaction, filtering, washing and drying after the reaction is finished to prepare a ferroferric oxide/bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan composite magnetic material, namely a three-dimensional reticular composite magnetic material for sewage treatment; the alkali liquor is sodium hydroxide solution with the mass concentration of 40%, potassium hydroxide solution and ammonia water; fe2+The iron salt is ferrous sulfate; fe3+The ferric salt is ferric sulfate; in the preparation of the composite magnetic material, water, a ternary composite porous material and Fe2+Iron salt, Fe3+The mass ratio of the ferric salt to the alkali liquor is 100:50: 15: 15: 12.
Comparative example 1
Comparative example 1 compared to example 1, no glass fibers were added.
Comparative example 2
(1) Adding glass fiber into deionized water, then adding an aminosilane coupling agent, fully stirring, filtering, washing and drying to obtain modified glass fiber; the amino silane coupling agent is phenylaminomethyl trimethoxy silane; in the preparation of the modified glass fiber, the mass ratio of deionized water to the glass fiber to the amino silane coupling agent is 100:38: 3;
(2) adding chitosan into acetic acid, uniformly mixing to prepare a chitosan solution, then adding modified glass fiber under a stirring state, and rapidly stirring until the mixture is uniformly mixed to prepare a glass fiber/chitosan binary composite solution; in the preparation of the binary composite liquid, the mass ratio of deionized water, chitosan and modified glass fiber is 100:26: 38;
(4) dispersing bacterial cellulose in deionized water, performing ultrasonic dispersion uniformly to obtain a bacterial cellulose water dispersion system, then slowly adding a glass fiber/chitosan binary composite solution under a high-speed stirring state, and fully stirring uniformly to obtain a bacterial cellulose/glass fiber/chitosan ternary composite; in the preparation of the ternary complex, the mass ratio of deionized water, bacterial cellulose and glass fiber/chitosan binary complex liquid is 100:26: 58;
(5) shaping the obtained ternary composite into a plate with the thickness of 3mmd in a mould, and freeze-drying to obtain the bacterial cellulose/glass fiber/chitosan ternary composite porous material;
(6) adding Fe into the obtained ternary composite porous material2+Iron salt and Fe3+Adding alkali liquor into the mixed aqueous solution of ferric salt, stirring for reaction, filtering, washing and drying after the reaction is finished to prepare the ferroferric oxide/bacterial cellulose/glass fiber/chitosan composite magnetic material, namely the three-dimensional reticular composite magnetic material for sewage treatment; the alkali liquor is a sodium hydroxide solution with the mass concentration of 28 percent; fe2+The iron salt is ferrous chloride; fe3+The ferric salt is ferric chloride; in the preparation of the composite magnetic material, water, a ternary composite porous material and Fe2+Iron salt, Fe3+The mass ratio of the ferric salt to the alkali liquor is 100:45:12:13: 11.
Comparative example 2 does not heterozygously compound glass fiber with graphene oxide, affecting adsorptivity.
Comparative example 3
(1) Adding glass fiber into deionized water, then adding an aminosilane coupling agent, fully stirring, filtering, washing and drying to obtain modified glass fiber; the amino silane coupling agent is phenylaminomethyl trimethoxy silane; in the preparation of the modified glass fiber, the mass ratio of deionized water to the glass fiber to the amino silane coupling agent is 100:38: 3;
(2) adding graphene oxide into deionized water, uniformly mixing to obtain graphene oxide aqueous dispersion, adding modified glass fiber into the graphene oxide aqueous dispersion under the mechanical stirring state, fully mixing and stirring, filtering, washing and drying to obtain glass fiber and graphene oxide hybrid material powder; in the preparation of the glass fiber and graphene oxide hybrid material powder, the mass ratio of deionized water, graphene oxide and modified glass fiber is 100:380: 24;
(3) adding chitosan into acetic acid, uniformly mixing to prepare a chitosan solution, then adding glass fiber and graphene oxide hybrid material powder under a stirring state, and rapidly stirring until the mixture is uniformly mixed to prepare a binary composite solution of the glass fiber and graphene oxide hybrid material/chitosan; in the preparation of the binary composite liquid, the mass ratio of the deionized water to the chitosan to the glass fiber to the graphene oxide hybrid material powder is 100:26: 38;
(4) shaping the obtained binary composite liquid into a plate with the thickness of 3mmd in a mould, and freeze-drying to obtain a glass fiber and graphene oxide hybrid material/chitosan composite porous material;
(5) adding Fe into the obtained composite porous material2+Iron salt and Fe3+Adding alkali liquor into a mixed aqueous solution of ferric salt, stirring for reaction, filtering, washing and drying after the reaction is finished to prepare a ferroferric oxide/glass fiber and graphene oxide hybrid material/chitosan composite magnetic material, namely a three-dimensional reticular composite magnetic material for sewage treatment; the alkali liquor is a sodium hydroxide solution with the mass concentration of 28 percent; fe2+The iron salt is ferrous chloride; fe3+The ferric salt is ferric chloride; in the preparation of the composite magnetic material, water, a ternary composite porous material and Fe2+Iron salt, Fe3+The mass ratio of the ferric salt to the alkali liquor is 100:45:12:13: 11.
Comparative example 3 did not utilize bacterial cellulose treatment, affecting the adsorption performance on small molecule organic matter.
The test method comprises the following steps:
the prepared composite magnetic material is subjected to mechanical property test, the composite magnetic material is made into a strip with the side length of 2 multiplied by 10cm, the tensile strength is tested by referring to GB/T1040, the testing speed is 5mm/s, and the measured tensile breaking strength of the material is shown in Table 1.
Carrying out heavy metal adsorption on the prepared composite magnetic materialAdhesion test, 100mL each containing Pb2+、Cd2 +The concentration of the simulated heavy metal wastewater is about 100mg/L, 0.5g of the composite magnetic material prepared by the invention is respectively added, ultrasonic oscillation is carried out for 1h at 25 ℃, then the mixture is kept stand for 8h, supernatant is taken, the concentration of heavy metal ions is measured, the removal rate of the heavy metal ions is calculated according to the ratio of the difference of the concentrations before and after treatment to the initial concentration, and the obtained results are shown in Table 1.
The prepared composite magnetic material was subjected to Congo red adsorption performance test, 50mL of Congo red solution with an initial concentration of 100mg/L was subjected to primary filtration using the composite magnetic material, and the Congo red removal rate was as shown in Table 1. FIG. 1 is a schematic view showing the color of the filtered water immediately disappearing as shown in FIG. 1a in example 1; FIG. 1b is the color after filtration of water using comparative example 1, there being a visible color in the water; FIG. 1c shows the color of the water filtered in comparative example 3, which is more congo red in the filtered water due to lack of bacterial cellulose adsorption.
Table 1:
Figure 109661DEST_PATH_IMAGE002

Claims (10)

1. a preparation method of a three-dimensional reticular composite magnetic material for sewage treatment is characterized by comprising the following steps:
(1) adding glass fiber into deionized water, then adding an aminosilane coupling agent, fully stirring, filtering, washing and drying to obtain modified glass fiber;
(2) adding graphene oxide into deionized water, uniformly mixing to obtain graphene oxide aqueous dispersion, adding modified glass fiber into the graphene oxide aqueous dispersion under the mechanical stirring state, fully mixing and stirring, filtering, washing and drying to obtain glass fiber and graphene oxide hybrid material powder;
(3) adding chitosan into acetic acid, uniformly mixing to prepare a chitosan solution, then adding glass fiber and graphene oxide hybrid material powder under a stirring state, and rapidly stirring until the mixture is uniformly mixed to prepare a binary composite solution of the glass fiber and graphene oxide hybrid material/chitosan;
(4) dissolving and dispersing bacterial cellulose in deionized water, performing ultrasonic dispersion uniformly to obtain a bacterial cellulose water dispersion system, then slowly adding a binary composite solution of glass fiber and graphene oxide hybrid material/chitosan under a high-speed stirring state, and fully stirring uniformly to obtain a ternary composite of the bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan;
(5) shaping the obtained ternary composite into a plate with the thickness of 3mmd in a mould, and freeze-drying to obtain a bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan ternary composite porous material;
(6) adding Fe into the obtained ternary composite porous material2+Iron salt and Fe3+And adding alkali liquor into the mixed aqueous solution of the ferric salt, stirring for reaction, filtering, washing and drying after the reaction is finished, thus obtaining the ferroferric oxide/bacterial cellulose/glass fiber and graphene oxide hybrid material/chitosan composite magnetic material, namely the three-dimensional reticular composite magnetic material for sewage treatment.
2. The method for preparing the three-dimensional reticular composite magnetic material for sewage treatment according to claim 1, wherein the aminosilane coupling agent is one or a combination of more than two of C-aminopropyltriethoxysilane, C-aminopropyltrimethoxysilane, phenylaminomethyltriethoxysilane and phenylaminomethyltrimethoxysilane.
3. The preparation method of the three-dimensional reticular composite magnetic material for sewage treatment according to claim 1, wherein in the preparation of the modified glass fiber in the step (1), the mass ratio of deionized water to the glass fiber to the amino silane coupling agent is 100:30-50: 2-4.
4. The preparation method of the three-dimensional reticular composite magnetic material for sewage treatment according to claim 1, wherein in the preparation of the glass fiber and graphene oxide hybrid material powder in the step (2), the mass ratio of the deionized water, the graphene oxide and the modified glass fiber is 100:30-50: 20-40.
5. The preparation method of the three-dimensional reticular composite magnetic material for sewage treatment according to claim 1, wherein in the preparation of the binary composite liquid in the step (3), the mass ratio of the deionized water, the chitosan, the glass fiber and the graphene oxide hybrid material powder is 100:20-30: 30-50.
6. The preparation method of the three-dimensional reticular composite magnetic material for sewage treatment according to claim 1, wherein in the preparation of the ternary complex in the step (4), the mass ratio of the deionized water, the bacterial cellulose, the glass fiber and the graphene oxide hybrid material/chitosan binary complex liquid is 100:20-30: 50-70.
7. The method for preparing the three-dimensional reticular composite magnetic material for sewage treatment according to claim 1, wherein the alkali liquor is one of sodium hydroxide solution, potassium hydroxide solution and ammonia water, and the mass concentration is 20-40%.
8. The method for preparing the three-dimensional reticular composite magnetic material for sewage treatment according to claim 1, wherein the Fe2+The iron salt is one or more of ferrous chloride, ferrous nitrate and ferrous sulfate, and the Fe is3+The iron salt is one or the combination of more than two of ferric chloride, ferric nitrate and ferric sulfate.
9. The method for preparing three-dimensional net-shaped composite magnetic material for sewage treatment according to claim 1, wherein the composite magnetic material is prepared in the step (6)Water, ternary composite porous material, Fe2+Iron salt, Fe3+The mass ratio of the ferric salt to the alkali liquor is 100:40-50:10-15:10-15: 8-12.
10. A three-dimensional net-shaped composite magnetic material for sewage treatment prepared by the preparation method of any one of claims 1 to 9.
CN202011014878.2A 2020-09-24 2020-09-24 Three-dimensional net-shaped composite magnetic material for sewage treatment and preparation method thereof Withdrawn CN112191233A (en)

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CN113976087A (en) * 2021-11-29 2022-01-28 西南林业大学 Nylon 6/chitosan-Fe nano-fiber composite material for adsorbing organic pollutants in water
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CN113321423A (en) * 2021-05-24 2021-08-31 吴尚荣 Glass brick with magnetic adsorption effect and preparation method thereof
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