CN116237023B - Chitosan-based defluorinating agent and preparation method thereof - Google Patents

Chitosan-based defluorinating agent and preparation method thereof Download PDF

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CN116237023B
CN116237023B CN202310523615.1A CN202310523615A CN116237023B CN 116237023 B CN116237023 B CN 116237023B CN 202310523615 A CN202310523615 A CN 202310523615A CN 116237023 B CN116237023 B CN 116237023B
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chitosan
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马吉松
陈治城
赵启豪
钮志远
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Qingyou Ecological Technology Shanghai Co ltd
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    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
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Abstract

The invention discloses a chitosan-based defluorinating agent and a preparation method thereof, and relates to the technical field of water treatment. When the chitosan-based defluorinating agent is prepared, urea is added into magnesium chloride solution to carry out hydrothermal reaction, and then the mixture is calcined to prepare porous magnesia powder; reacting polyethylene glycol and tetraethoxysilane to prepare an organosilicon additive; and (3) loading lanthanum ions on the porous magnesium oxide powder, mixing the porous magnesium oxide powder with an organosilicon additive and water glass, pelletizing, calcining to obtain the fluorine removing agent, and grafting a chitosan shell on the fluorine removing agent to obtain the chitosan-based fluorine removing agent. The chitosan-based fluorine removing agent prepared by the invention has excellent fluorine removing effect.

Description

Chitosan-based defluorinating agent and preparation method thereof
Technical Field
The invention relates to the technical field of water treatment, in particular to a chitosan-based fluorine removing agent and a preparation method thereof.
Background
Fluorine is one of the trace elements necessary for human life activities. The daily intake of fluoride ions in small amounts can prevent caries and promote bone development, but the excessive amount cannot be exceeded at a time, otherwise, gastrointestinal discomfort, shock, heart failure and other symptoms are likely to be caused. Chronic fluorosis can also be caused by long-time exposure to low-concentration fluoride, and light patients are prone to incurable diseases such as fluoplaque teeth, fluo-drosis disease and the like, and heavy patients induce cancers, liver injury, leucopenia and paralysis.
At present, the fluorine removal method in the domestic and foreign water treatment industry is classified into a precipitation method, an electric flocculation method, a membrane separation method, an adsorption method and the like according to the difference of fluorine removal mechanisms and methods. The precipitation method is simple in operation method, but the mass concentration of the fluoride ions after treatment is difficult to achieve the expected effect, and a large amount of sludge is generated, so that the risk of secondary pollution exists; the electric flocculation defluorination process has the problems of high energy consumption, polar plate polarization, difficult maintenance, high operation cost and the like; the membrane separation method has good effect of removing the fluoride ions in the sewage, but has high treatment cost, and is only suitable for places with higher requirements on the quality of the effluent and smaller scale; the adsorption method has the advantages of high efficiency, low cost, wide application range, high fluoride ion selectivity, environmental protection and the like, and is the most widely used method for treating fluorine-containing sewage. Along with the development of society, the demand of people for fluorine removal is higher and higher, and the fluorine removal effect of the existing fluorine removal agent is gradually behind. Therefore, improvements and optimizations for fluorine removal agents are needed to achieve better adsorption.
Disclosure of Invention
The invention aims to provide a chitosan-based defluorinating agent and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a chitosan-based fluorine removing agent is prepared by loading lanthanum ions on porous magnesium oxide powder, mixing the porous magnesium oxide powder with an organosilicon additive and water glass, pelletizing, calcining to obtain the fluorine removing agent, and grafting a chitosan shell on the fluorine removing agent.
Preferably, the porous magnesium oxide powder is prepared by adding urea into magnesium chloride solution for hydrothermal reaction and calcining.
The organosilicon additive is prepared by the reaction of polyethylene glycol PEG400 and tetraethoxysilane as optimization.
The preparation method of the chitosan-based defluorinating agent comprises the following preparation steps:
(1) Uniformly mixing porous magnesium oxide powder and a lanthanum nitrate solution with the mass fraction of 10-15% according to the mass ratio of 1:6-8, carrying out ultrasonic treatment at the temperature of 20-30 ℃ and the temperature of 25-35 kHz for 15-20 min, carrying out centrifugal separation, drying at the temperature of 90-100 ℃ for 3-4 h, immersing in a sodium hydroxide aqueous solution with the mass fraction of 10-15%, carrying out ultrasonic treatment at the temperature of 20-30 ℃ and the temperature of 25-35 kHz for 15-20 min, carrying out centrifugal separation, washing with pure water for 3-5 times, and drying at the temperature of 90-100 ℃ for 3-4 h to obtain rare earth loaded magnesium oxide powder;
(2) Uniformly mixing rare earth loaded magnesia powder, an organosilicon additive, water glass ZF-50A and pure water according to the mass ratio (12-14) of 1:1:1, and preparing a spherical blank with the diameter of 4-6 mm by a disc pelletizer; placing the spherical embryo body at 90-100 ℃ for 20-30 min, placing the spherical embryo body at 360-400 ℃ for 2-3 h, and cooling to room temperature to obtain a fluorine removing agent;
(3) Uniformly mixing a fluorine removing agent and silane hydrolysate according to the mass ratio of 1:6-8, stirring for 1-2 hours at the temperature of 20-30 ℃ and the speed of 300-500 r/min, centrifugally separating to obtain a solid, washing the solid with absolute ethyl alcohol for 3-5 times, drying the solid at the temperature of 60-70 ℃ for 6-8 hours, immersing the solid in glutaraldehyde solution with the mass of 20-30 times of the fluorine removing agent, carrying out ultrasonic reaction for 3-5 hours at the temperature of 75-85 ℃ and the speed of 25-35 kHz, naturally cooling the solid to the room temperature, centrifugally separating, washing the solid with absolute ethyl alcohol for 3-5 times at the temperature of 30-40 ℃ and the speed of 50-100 Pa for 6-8 hours, uniformly mixing the hydroformylation fluorine removing agent and chitosan solution according to the mass ratio of 1:100-120, carrying out ultrasonic reaction for 3-5 hours at the temperature of 75-85 ℃, naturally cooling the solid after centrifugal separation, immersing the solid in sodium hydroxide solution with the mass of 4-6% at the temperature of 10-30 ℃ and the speed of 25-35 kHz ultrasonic reaction for 15-20 minutes, centrifugally separating, washing the solid with absolute ethyl alcohol for 3-5 times, drying the solid at the temperature of 50-100 kHz and the speed of 50-100 Pa for 6 Pa to obtain the chitosan.
As an optimization, the preparation method of the porous magnesia powder in the step (1) comprises the following steps: uniformly mixing magnesium chloride hexahydrate, polyethylene glycol PEG400 and pure water according to the mass ratio of 1:0.1-0.2:4-6, stirring for 15-20 min at the temperature of 10-20 ℃ at the speed of 300-500 r/min, heating to 35-45 ℃ and adding urea with the mass of 0.2-0.4 times that of the magnesium chloride hexahydrate, continuously stirring for 8-10 min, placing in a high-pressure reaction kettle, reacting for 3-4 h at the temperature of 90-120 ℃, cooling to room temperature, centrifugally separating, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, drying for 3-4 h at the temperature of 90-100 ℃, calcining for 2-3 h at the temperature of 400-500 ℃, and cooling to room temperature.
As optimization, the preparation method of the organic silicon additive in the step (2) comprises the following steps: uniformly mixing polyethylene glycol PEG400, ethyl orthosilicate and p-toluenesulfonic acid according to the mass ratio of 5-6:1:0.01-0.02 in a nitrogen atmosphere, stirring and reacting at 90-100 ℃ for 20-30 min at 300-500 r/min, heating to 150-160 ℃ and continuously stirring and reacting for 6-8 h, cooling to room temperature, and standing at 50-60 ℃ at 10-20 Pa for 3-4 h to obtain the modified polyethylene glycol.
As optimization, the silane hydrolysate in the step (3) is prepared by uniformly mixing 3-aminopropyl triethoxysilane and an ethanol aqueous solution with the mass fraction of 70-80% according to the mass ratio of 1:10-12, and stirring at the temperature of 20-30 ℃ for 20-25 min at the speed of 600-800 r/min.
As optimization, the glutaraldehyde solution in the step (3) is prepared by uniformly mixing glutaraldehyde, acetic acid and absolute ethyl alcohol according to the mass ratio of 1:0.1-0.2:10-14.
As optimization, the chitosan solution in the step (3) is prepared by uniformly mixing chitosan, acetic acid, absolute ethyl alcohol and pure water according to a mass ratio of 1:3-4:80-120:200-300.
As optimization, the chitosan has the deacetylation degree of 88%, the molecular weight of 161kDa and the manufacturer is a limited group of national medicine group chemical reagents.
Compared with the prior art, the invention has the following beneficial effects:
when the chitosan-based fluorine removing agent is prepared, firstly, porous magnesium oxide powder is loaded with lanthanum ions, then, the porous magnesium oxide powder, an organosilicon additive and water glass are mixed, pelletized and calcined to prepare the fluorine removing agent, and a chitosan shell is grafted on the fluorine removing agent to prepare the chitosan-based fluorine removing agent.
Firstly, urea is added into magnesium chloride solution for hydrothermal reaction, and then the porous magnesium oxide powder is prepared by calcining, has higher specific surface area and can be subjected to ion exchange with fluorine ions, and after loading, coordination water on the loaded lanthanum ions is subjected to ion exchange with fluorine ions in an easy solution, so that the fluorine removal effect of the chitosan-based fluorine removal agent is improved.
Secondly, polyethylene glycol and tetraethoxysilane are reacted to prepare an organosilicon additive, the organosilicon additive can play a certain role in bonding, polyethylene glycol chain segments in the organosilicon additive are cracked into small molecules to overflow to form pore channels at high temperature, the small molecules and porous magnesia powder form a multi-stage pore channel structure, the specific surface area is larger, and the cracked silicon chain segments reinforce the pore channel structure through silica bonds, so that the collapse of the pore channels is avoided, and the defluorination effect of the chitosan-based defluorinating agent is improved; after grafting chitosan on the fluorine removing agent, a porous chitosan surface layer is formed, and amino groups on the chitosan are positively charged, so that the fluorine removing agent has a good electrostatic adsorption effect on fluorine ions.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Uniformly mixing magnesium chloride hexahydrate, polyethylene glycol PEG400 and pure water according to the mass ratio of 1:0.1:4, stirring for 20min at 10 ℃ and 300r/min, heating to 35 ℃, adding urea with the mass 0.2 times of that of the magnesium chloride hexahydrate, continuously stirring for 10min, placing in a high-pressure reaction kettle, reacting for 4h at 90 ℃, cooling to room temperature, centrifugally separating, washing with pure water and absolute ethyl alcohol for 3 times respectively, drying for 4h at 90 ℃, calcining for 3h at 400 ℃, cooling to room temperature, and obtaining porous magnesium oxide powder; uniformly mixing porous magnesium oxide powder and a lanthanum nitrate solution with the mass fraction of 10% according to the mass ratio of 1:6, carrying out ultrasonic treatment at 20 ℃ and 25kHz for 20min, carrying out centrifugal separation, drying at 90 ℃ for 4h, immersing in a sodium hydroxide aqueous solution with the mass fraction of 10%, carrying out ultrasonic treatment at 20 ℃ and 25kHz for 15min, carrying out centrifugal separation, washing with pure water for 5 times, drying at 100 ℃ for 3h, calcining at 400 ℃ for 3h, and cooling to room temperature to obtain rare earth-loaded magnesium oxide powder;
(2) Uniformly mixing polyethylene glycol PEG400, ethyl orthosilicate and p-toluenesulfonic acid according to a mass ratio of 5:1:0.01 in a nitrogen atmosphere, stirring and reacting for 30min at 90 ℃ and 300r/min, heating to 150 ℃ and continuously stirring and reacting for 8h, cooling to room temperature, and standing for 4h at 10Pa at 50 ℃ to prepare the organosilicon additive; uniformly mixing rare earth loaded magnesia powder, an organosilicon additive, water glass ZF-50A and pure water according to a mass ratio of 12:1:1:1, and making the mixture into spherical embryo bodies with the diameter of 4mm by a disc pelletizer; placing the spherical embryo body at 90 ℃ for 30min, placing the spherical embryo body at 360 ℃ for 3h, and cooling to room temperature to obtain the fluorine removing agent;
(3) Uniformly mixing 3-aminopropyl triethoxysilane and 70% ethanol aqueous solution according to a mass ratio of 1:10, and stirring at 20 ℃ and 600r/min for 25min to prepare silane hydrolysate; uniformly mixing glutaraldehyde, acetic acid and absolute ethyl alcohol according to the mass ratio of 1:0.1:10 to prepare glutaraldehyde solution; uniformly mixing chitosan, acetic acid, absolute ethyl alcohol and pure water according to a mass ratio of 1:3:80:200 to prepare a chitosan solution; uniformly mixing a fluorine removing agent and silane hydrolysate according to the mass ratio of 1:6, stirring for 2 hours at 20 ℃ and 300r/min, centrifugally separating to obtain solid, washing the solid with absolute ethyl alcohol for 3 times, drying the solid at 60 ℃ for 8 hours, immersing the solid in glutaraldehyde solution with the mass of 20 times of the fluorine removing agent, performing ultrasonic reaction at 75 ℃ and 25kHz for 5 hours, naturally cooling the solid to room temperature, centrifugally separating the solid and washing the solid with absolute ethyl alcohol for 3 times, drying the solid at 30 ℃ and 50Pa for 8 hours, obtaining the hydroformylation fluorine removing agent, uniformly mixing the hydroformylation fluorine removing agent and chitosan solution according to the mass ratio of 1:100, performing ultrasonic reaction at 75 ℃ and 25kHz for 5 hours, naturally cooling the solid to room temperature, centrifugally separating the solid, immersing the solid in sodium hydroxide solution with the mass fraction of 4%, performing ultrasonic reaction at 10 ℃ and 25kHz for 20 minutes, washing the solid with absolute ethyl alcohol for 3 times, and drying the solid at 50Pa for 8 hours to obtain the chitosan-based fluorine removing agent.
Example 2
(1) Uniformly mixing magnesium chloride hexahydrate, polyethylene glycol PEG400 and pure water according to the mass ratio of 1:0.15:5, stirring for 18min at 15 ℃ and 400r/min, heating to 40 ℃, adding urea with the mass 0.3 times of that of the magnesium chloride hexahydrate, continuously stirring for 9min, placing in a high-pressure reaction kettle, reacting for 3.5h at 100 ℃, cooling to room temperature, centrifugally separating, washing with pure water and absolute ethyl alcohol for 4 times respectively, drying for 3.5h at 95 ℃, calcining for 2.5h at 450 ℃, cooling to room temperature, and obtaining porous magnesium oxide powder; uniformly mixing porous magnesium oxide powder and lanthanum nitrate solution with the mass fraction of 12% according to the mass ratio of 1:7, carrying out ultrasonic treatment at 25 ℃ and 30kHz for 18min, carrying out centrifugal separation, drying at 95 ℃ for 3.5h, immersing in sodium hydroxide aqueous solution with the mass fraction of 12%, carrying out ultrasonic treatment at 25 ℃ and 30kHz for 18min, carrying out centrifugal separation, washing with pure water for 4 times, drying at 95 ℃ for 3.5h, calcining at 450 ℃ for 2.5h, and cooling to room temperature to obtain rare earth loaded magnesium oxide powder;
(2) Uniformly mixing polyethylene glycol PEG400, ethyl orthosilicate and p-toluenesulfonic acid according to the mass ratio of 5.5:1:0.015 in a nitrogen atmosphere, stirring and reacting for 25min at 95 ℃ and 400r/min, heating to 155 ℃ and continuously stirring and reacting for 7h, cooling to room temperature, and standing for 3.5h at 55 ℃ and 15Pa to prepare the organosilicon additive; uniformly mixing rare earth loaded magnesia powder, an organosilicon additive, water glass ZF-50A and pure water according to a mass ratio of 13:1:1:1, and making the mixture into a spherical blank with a diameter of 5mm by a disc pelletizer; placing the spherical embryo body at 95 ℃ for 25min, placing at 380 ℃ for 2.5h, and cooling to room temperature to obtain the fluorine removing agent;
(3) Uniformly mixing 3-aminopropyl triethoxysilane and an ethanol aqueous solution with the mass fraction of 75% according to the mass ratio of 1:11, and stirring at 25 ℃ and 700r/min for 22min to prepare a silane hydrolysate; uniformly mixing glutaraldehyde, acetic acid and absolute ethyl alcohol according to the mass ratio of 1:0.15:12 to prepare glutaraldehyde solution; uniformly mixing chitosan, acetic acid, absolute ethyl alcohol and pure water according to the mass ratio of 1:3.5:100:250 to prepare a chitosan solution; uniformly mixing a fluorine removing agent and silane hydrolysate according to the mass ratio of 1:7, stirring for 1.5 hours at 25 ℃, carrying out centrifugal separation to obtain a solid, washing the solid with absolute ethyl alcohol for 4 times, drying the solid at 65 ℃ for 7 hours, immersing the solid in glutaraldehyde solution with the mass of 25 times of the fluorine removing agent, carrying out ultrasonic reaction at 80 ℃ for 4 hours at 30kHz, naturally cooling to room temperature, carrying out centrifugal separation, washing the solid with absolute ethyl alcohol for 4 times, drying the solid at 35 ℃ for 7 hours at 70Pa, obtaining an hydroformylation fluorine removing agent, uniformly mixing the hydroformylation fluorine removing agent and chitosan solution according to the mass ratio of 1:110, carrying out ultrasonic reaction at 80 ℃ for 4 hours at 30kHz, naturally cooling to room temperature, immersing the solid in sodium hydroxide solution with the mass fraction of 5% after centrifugal separation, carrying out ultrasonic treatment at 20 ℃ for 18 minutes at 30kHz, washing the solid with absolute ethyl alcohol for 4 times, and drying the solid at 80Pa for 7 hours at 35 ℃ to obtain the chitosan-based fluorine removing agent.
Example 3
(1) Uniformly mixing magnesium chloride hexahydrate, polyethylene glycol PEG400 and pure water according to the mass ratio of 1:0.2:6, stirring for 15min at 20 ℃ at 500r/min, heating to 45 ℃ and adding urea with the mass 0.4 times that of the magnesium chloride hexahydrate, continuously stirring for 8min, placing in a high-pressure reaction kettle, reacting for 3h at 120 ℃, cooling to room temperature, centrifugally separating, washing with pure water and absolute ethyl alcohol for 5 times respectively, drying for 3h at 100 ℃, calcining for 2h at 500 ℃, cooling to room temperature, and obtaining porous magnesium oxide powder; uniformly mixing porous magnesium oxide powder and 15% lanthanum nitrate solution by mass according to a mass ratio of 1:8, carrying out ultrasonic treatment at 30 ℃ and 35kHz for 15min, carrying out centrifugal separation, drying at 100 ℃ for 3h, immersing in 15% sodium hydroxide aqueous solution by mass, carrying out ultrasonic treatment at 30 ℃ and 35kHz for 15min, carrying out centrifugal separation, washing with pure water for 5 times, drying at 100 ℃ for 3h, calcining at 500 ℃ for 2h, and cooling to room temperature to obtain rare earth loaded magnesium oxide powder;
(2) Uniformly mixing polyethylene glycol PEG400, tetraethoxysilane and p-toluenesulfonic acid according to a mass ratio of 6:1:0.02 in a nitrogen atmosphere, stirring at 100 ℃ for reaction for 20min at 500r/min, heating to 160 ℃ for continuous stirring for reaction for 6h, cooling to room temperature, and standing at 60 ℃ for 3h at 20Pa to prepare the organosilicon additive; uniformly mixing rare earth loaded magnesia powder, an organosilicon additive, water glass ZF-50A and pure water according to the mass ratio of 14:1:1:1, and preparing a spherical blank with the diameter of 6mm by a disc pelletizer; placing the spherical embryo body at 100deg.C for 20min, placing at 400deg.C for 2 hr, and cooling to room temperature to obtain defluorinating agent;
(3) Uniformly mixing 3-aminopropyl triethoxysilane and an ethanol aqueous solution with the mass fraction of 80% according to the mass ratio of 1:12, and stirring at 30 ℃ and 800r/min for 20min to prepare a silane hydrolysate; uniformly mixing glutaraldehyde, acetic acid and absolute ethyl alcohol according to the mass ratio of 1:0.2:14 to prepare glutaraldehyde solution; uniformly mixing chitosan, acetic acid, absolute ethyl alcohol and pure water according to a mass ratio of 1:4:120:300 to prepare a chitosan solution; uniformly mixing a fluorine removing agent and silane hydrolysate according to the mass ratio of 1:8, stirring for 1h at 30 ℃ and 500r/min, centrifugally separating to obtain solid, washing with absolute ethyl alcohol for 5 times, drying for 6h at 70 ℃, immersing in glutaraldehyde solution with the mass of 30 times of the fluorine removing agent, ultrasonically reacting for 3h at 85 ℃ and 35kHz, naturally cooling to room temperature, centrifugally separating, washing with absolute ethyl alcohol for 5 times, drying for 6h at 40 ℃ and 100Pa, obtaining an hydroformylation fluorine removing agent, uniformly mixing the hydroformylation fluorine removing agent and chitosan solution according to the mass ratio of 1:120, ultrasonically reacting for 3h at 85 ℃ and 35kHz, naturally cooling to room temperature, centrifugally separating, immersing in sodium hydroxide solution with the mass fraction of 6%, ultrasonically reacting for 15min at 30 ℃ and 35kHz, washing with absolute ethyl alcohol for 5 times, centrifugally separating, drying for 6h at 40 ℃ and 100Pa, and obtaining the chitosan-based fluorine removing agent.
Comparative example 1
(1) Uniformly mixing magnesium chloride hexahydrate, polyethylene glycol PEG400 and pure water according to the mass ratio of 1:0.15:5, stirring for 18min at 15 ℃ and 400r/min, heating to 40 ℃, adding urea with the mass 0.3 times of that of the magnesium chloride hexahydrate, continuously stirring for 9min, placing in a high-pressure reaction kettle, reacting for 3.5h at 100 ℃, cooling to room temperature, centrifugally separating, washing with pure water and absolute ethyl alcohol for 4 times respectively, drying for 3.5h at 95 ℃, calcining for 2.5h at 450 ℃, cooling to room temperature, and obtaining porous magnesium oxide powder;
(2) Uniformly mixing polyethylene glycol PEG400, ethyl orthosilicate and p-toluenesulfonic acid according to the mass ratio of 5.5:1:0.015 in a nitrogen atmosphere, stirring and reacting for 25min at 95 ℃ and 400r/min, heating to 155 ℃ and continuously stirring and reacting for 7h, cooling to room temperature, and standing for 3.5h at 55 ℃ and 15Pa to prepare the organosilicon additive; uniformly mixing magnesium oxide powder, an organosilicon additive, water glass ZF-50A and pure water according to a mass ratio of 13:1:1:1, and making the mixture into spherical embryo bodies with the diameter of 5mm by a disc pelletizer; placing the spherical embryo body at 95 ℃ for 25min, placing at 380 ℃ for 2.5h, and cooling to room temperature to obtain the fluorine removing agent;
(3) Uniformly mixing 3-aminopropyl triethoxysilane and an ethanol aqueous solution with the mass fraction of 75% according to the mass ratio of 1:11, and stirring at 25 ℃ and 700r/min for 22min to prepare a silane hydrolysate; uniformly mixing glutaraldehyde, acetic acid and absolute ethyl alcohol according to the mass ratio of 1:0.15:12 to prepare glutaraldehyde solution; uniformly mixing chitosan, acetic acid, absolute ethyl alcohol and pure water according to the mass ratio of 1:3.5:100:250 to prepare a chitosan solution; uniformly mixing a fluorine removing agent and silane hydrolysate according to the mass ratio of 1:7, stirring for 1.5 hours at 25 ℃, carrying out centrifugal separation to obtain a solid, washing the solid with absolute ethyl alcohol for 4 times, drying the solid at 65 ℃ for 7 hours, immersing the solid in glutaraldehyde solution with the mass of 25 times of the fluorine removing agent, carrying out ultrasonic reaction at 80 ℃ for 4 hours at 30kHz, naturally cooling to room temperature, carrying out centrifugal separation, washing the solid with absolute ethyl alcohol for 4 times, drying the solid at 35 ℃ for 7 hours at 70Pa, obtaining an hydroformylation fluorine removing agent, uniformly mixing the hydroformylation fluorine removing agent and chitosan solution according to the mass ratio of 1:110, carrying out ultrasonic reaction at 80 ℃ for 4 hours at 30kHz, naturally cooling to room temperature, immersing the solid in sodium hydroxide solution with the mass fraction of 5% after centrifugal separation, carrying out ultrasonic treatment at 20 ℃ for 18 minutes at 30kHz, washing the solid with absolute ethyl alcohol for 4 times, and drying the solid at 80Pa for 7 hours at 35 ℃ to obtain the chitosan-based fluorine removing agent.
Comparative example 2
(1) Uniformly mixing magnesium chloride hexahydrate, polyethylene glycol PEG400 and pure water according to the mass ratio of 1:0.15:5, stirring for 18min at 15 ℃ and 400r/min, heating to 40 ℃, adding urea with the mass 0.3 times of that of the magnesium chloride hexahydrate, continuously stirring for 9min, placing in a high-pressure reaction kettle, reacting for 3.5h at 100 ℃, cooling to room temperature, centrifugally separating, washing with pure water and absolute ethyl alcohol for 4 times respectively, drying for 3.5h at 95 ℃, calcining for 2.5h at 450 ℃, cooling to room temperature, and obtaining porous magnesium oxide powder; uniformly mixing porous magnesium oxide powder and lanthanum nitrate solution with the mass fraction of 12% according to the mass ratio of 1:7, carrying out ultrasonic treatment at 25 ℃ and 30kHz for 18min, carrying out centrifugal separation, drying at 95 ℃ for 3.5h, immersing in sodium hydroxide aqueous solution with the mass fraction of 12%, carrying out ultrasonic treatment at 25 ℃ and 30kHz for 18min, carrying out centrifugal separation, washing with pure water for 4 times, drying at 95 ℃ for 3.5h, calcining at 450 ℃ for 2.5h, and cooling to room temperature to obtain rare earth loaded magnesium oxide powder;
(2) Uniformly mixing rare earth loaded magnesia powder, water glass ZF-50A and pure water according to a mass ratio of 13:2:1, and making the mixture into a spherical blank with a diameter of 5mm by a disc pelletizer; placing the spherical embryo body at 95 ℃ for 25min, placing at 380 ℃ for 2.5h, and cooling to room temperature to obtain the fluorine removing agent;
(3) Uniformly mixing 3-aminopropyl triethoxysilane and an ethanol aqueous solution with the mass fraction of 75% according to the mass ratio of 1:11, and stirring at 25 ℃ and 700r/min for 22min to prepare a silane hydrolysate; uniformly mixing glutaraldehyde, acetic acid and absolute ethyl alcohol according to the mass ratio of 1:0.15:12 to prepare glutaraldehyde solution; uniformly mixing chitosan, acetic acid, absolute ethyl alcohol and pure water according to the mass ratio of 1:3.5:100:250 to prepare a chitosan solution; uniformly mixing a fluorine removing agent and silane hydrolysate according to the mass ratio of 1:7, stirring for 1.5 hours at 25 ℃, carrying out centrifugal separation to obtain a solid, washing the solid with absolute ethyl alcohol for 4 times, drying the solid at 65 ℃ for 7 hours, immersing the solid in glutaraldehyde solution with the mass of 25 times of the fluorine removing agent, carrying out ultrasonic reaction at 80 ℃ for 4 hours at 30kHz, naturally cooling to room temperature, carrying out centrifugal separation, washing the solid with absolute ethyl alcohol for 4 times, drying the solid at 35 ℃ for 7 hours at 70Pa, obtaining an hydroformylation fluorine removing agent, uniformly mixing the hydroformylation fluorine removing agent and chitosan solution according to the mass ratio of 1:110, carrying out ultrasonic reaction at 80 ℃ for 4 hours at 30kHz, naturally cooling to room temperature, immersing the solid in sodium hydroxide solution with the mass fraction of 5% after centrifugal separation, carrying out ultrasonic treatment at 20 ℃ for 18 minutes at 30kHz, washing the solid with absolute ethyl alcohol for 4 times, and drying the solid at 80Pa for 7 hours at 35 ℃ to obtain the chitosan-based fluorine removing agent.
Comparative example 3
(1) Uniformly mixing magnesium chloride hexahydrate, polyethylene glycol PEG400 and pure water according to the mass ratio of 1:0.15:5, stirring for 18min at 15 ℃ and 400r/min, heating to 40 ℃, adding urea with the mass 0.3 times of that of the magnesium chloride hexahydrate, continuously stirring for 9min, placing in a high-pressure reaction kettle, reacting for 3.5h at 100 ℃, cooling to room temperature, centrifugally separating, washing with pure water and absolute ethyl alcohol for 4 times respectively, drying for 3.5h at 95 ℃, calcining for 2.5h at 450 ℃, cooling to room temperature, and obtaining porous magnesium oxide powder; uniformly mixing porous magnesium oxide powder and lanthanum nitrate solution with the mass fraction of 12% according to the mass ratio of 1:7, carrying out ultrasonic treatment at 25 ℃ and 30kHz for 18min, carrying out centrifugal separation, drying at 95 ℃ for 3.5h, immersing in sodium hydroxide aqueous solution with the mass fraction of 12%, carrying out ultrasonic treatment at 25 ℃ and 30kHz for 18min, carrying out centrifugal separation, washing with pure water for 4 times, drying at 95 ℃ for 3.5h, calcining at 450 ℃ for 2.5h, and cooling to room temperature to obtain rare earth loaded magnesium oxide powder;
(2) Uniformly mixing polyethylene glycol PEG400, ethyl orthosilicate and p-toluenesulfonic acid according to the mass ratio of 5.5:1:0.015 in a nitrogen atmosphere, stirring and reacting for 25min at 95 ℃ and 400r/min, heating to 155 ℃ and continuously stirring and reacting for 7h, cooling to room temperature, and standing for 3.5h at 55 ℃ and 15Pa to prepare the organosilicon additive; uniformly mixing rare earth loaded magnesia powder, an organosilicon additive, water glass ZF-50A and pure water according to a mass ratio of 13:1:1:1, and making the mixture into a spherical blank with a diameter of 5mm by a disc pelletizer; placing the spherical embryo body at 95 ℃ for 25min, placing at 380 ℃ for 2.5h, and cooling to room temperature to obtain the fluorine removing agent.
Experimental example 1
And F, fluorine removal effect test:
preparing a fluorine-containing aqueous solution with the mass fraction of fluorine ions of 5mg/L, adding 0.2g of the products of the examples and the comparative examples into 1L of the fluorine-containing aqueous solution respectively, adsorbing for 2 hours at 20 ℃, measuring the concentration of fluorine ions in the fluorine-containing aqueous solution by using a spectrophotometer, and calculating the removal rate R (%) of fluorine ions, wherein the calculation formula is as follows:
R=1-C/C 0
wherein C is the concentration of fluoride ions at adsorption equilibrium; c (C) 0 Is fluoride ionIs a starting concentration of (c). The results are shown in Table 1.
TABLE 1
Fluorine ion removal rate
Example 1 83.6%
Example 2 83.9%
Example 3 84.1%
Comparative example 1 73.2%
Comparative example 2 48.9%
Comparative example 3 67.4%
From comparison of experimental data of examples 1-3 and comparative examples 1-3 in Table 1, it can be found that the chitosan-based fluorine removing agent prepared by the invention has good fluorine removing effect.
From comparison of experimental data of examples 1, 2 and 3 and comparative example 1, it can be found that the fluorine ion removal rate of examples 1, 2 and 3 is higher than that of comparative example 1, which indicates that coordination water on lanthanum ions is exchanged with fluorine ions in easy solution, thereby improving the fluorine removal effect of chitosan-based fluorine removal agent; from comparison of experimental data of examples 1, 2 and 3 and comparative example 2, the examples 1, 2 and 3 have higher fluoride ion removal rate than comparative example 2, which shows that the addition of the organic additive in the pelletizing process not only plays a role in adhesion, but also cracks polyethylene glycol chain segments in the organic additive into small molecules to overflow to form pore channels at high temperature, and the porous magnesia powder forms a multi-stage pore channel structure, so that the porous structure has larger specific surface area, and the silicon chain segments formed after the cracking reinforce the pore channel structure through siloxane bonds, so that collapse of pore channels is avoided, and the defluorination effect of the chitosan-based defluorinating agent is improved; from comparison of experimental data of examples 1, 2 and 3 and comparative example 3, it can be found that the fluorine ion removal rate of examples 1, 2 and 3 is higher than that of comparative example 3, which shows that after chitosan is grafted on the surface, a porous chitosan surface layer is formed, and amino groups on chitosan are positively charged, so that the fluorine ion removal effect is improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (6)

1. The preparation method of the chitosan-based defluorinating agent is characterized by comprising the following preparation steps:
(1) Uniformly mixing porous magnesium oxide powder and a lanthanum nitrate solution with the mass fraction of 10-15% according to the mass ratio of 1:6-8, carrying out ultrasonic treatment at the temperature of 20-30 ℃ and the temperature of 25-35 kHz for 15-20 min, carrying out centrifugal separation, drying at the temperature of 90-100 ℃ for 3-4 h, immersing in a sodium hydroxide aqueous solution with the mass fraction of 10-15%, carrying out ultrasonic treatment at the temperature of 20-30 ℃ and the temperature of 25-35 kHz for 15-20 min, carrying out centrifugal separation, washing with pure water for 3-5 times, and drying at the temperature of 90-100 ℃ for 3-4 h to obtain rare earth loaded magnesium oxide powder;
(2) Uniformly mixing polyethylene glycol PEG400, ethyl orthosilicate and p-toluenesulfonic acid according to a mass ratio of 5-6:1:0.01-0.02 in a nitrogen atmosphere, stirring and reacting at 90-100 ℃ for 20-30 min at 300-500 r/min, heating to 150-160 ℃ and continuously stirring and reacting for 6-8 h, cooling to room temperature, and standing at 50-60 ℃ at 10-20 Pa for 3-4 h to obtain an organosilicon additive; uniformly mixing rare earth loaded magnesia powder, an organosilicon additive, water glass ZF-50A and pure water according to the mass ratio (12-14) of 1:1:1, and preparing a spherical blank with the diameter of 4-6 mm by a disc pelletizer; placing the spherical embryo body at 90-100 ℃ for 20-30 min, placing the spherical embryo body at 360-400 ℃ for 2-3 h, and cooling to room temperature to obtain a fluorine removing agent;
(3) Uniformly mixing a fluorine removing agent and silane hydrolysate according to the mass ratio of 1:6-8, stirring for 1-2 hours at the temperature of 20-30 ℃ and the speed of 300-500 r/min, centrifugally separating to obtain a solid, washing the solid with absolute ethyl alcohol for 3-5 times, drying the solid at the temperature of 60-70 ℃ for 6-8 hours, immersing the solid in glutaraldehyde solution with the mass of 20-30 times of the fluorine removing agent, carrying out ultrasonic reaction for 3-5 hours at the temperature of 75-85 ℃ and the speed of 25-35 kHz, naturally cooling the solid to the room temperature, centrifugally separating, washing the solid with absolute ethyl alcohol for 3-5 times at the temperature of 30-40 ℃ and the speed of 50-100 Pa for 6-8 hours, uniformly mixing the hydroformylation fluorine removing agent and chitosan solution according to the mass ratio of 1:100-120, carrying out ultrasonic reaction for 3-5 hours at the temperature of 75-85 ℃, naturally cooling the solid after centrifugal separation, immersing the solid in sodium hydroxide solution with the mass of 4-6% at the temperature of 10-30 ℃ and the speed of 25-35 kHz ultrasonic reaction for 15-20 minutes, centrifugally separating, washing the solid with absolute ethyl alcohol for 3-5 times, drying the solid at the temperature of 50-100 kHz and the speed of 50-100 Pa for 6 Pa to obtain the chitosan.
2. The method for preparing the chitosan-based defluorinating agent according to claim 1, wherein the method for preparing the porous magnesia powder in the step (1) comprises the following steps: uniformly mixing magnesium chloride hexahydrate, polyethylene glycol PEG400 and pure water according to the mass ratio of 1:0.1-0.2:4-6, stirring for 15-20 min at the temperature of 10-20 ℃ at the speed of 300-500 r/min, heating to 35-45 ℃ and adding urea with the mass of 0.2-0.4 times that of the magnesium chloride hexahydrate, continuously stirring for 8-10 min, placing in a high-pressure reaction kettle, reacting for 3-4 h at the temperature of 90-120 ℃, cooling to room temperature, centrifugally separating, washing with pure water and absolute ethyl alcohol for 3-5 times respectively, drying for 3-4 h at the temperature of 90-100 ℃, calcining for 2-3 h at the temperature of 400-500 ℃, and cooling to room temperature.
3. The preparation method of the chitosan-based fluorine removal agent according to claim 1, wherein the silane hydrolysate in the step (3) is prepared by uniformly mixing 3-aminopropyl triethoxysilane and an ethanol aqueous solution with the mass fraction of 70-80% according to the mass ratio of 1:10-12, and stirring at 20-30 ℃ for 20-25 min at 600-800 r/min.
4. The preparation method of the chitosan-based fluorine removal agent according to claim 1, wherein the glutaraldehyde solution in the step (3) is prepared by uniformly mixing glutaraldehyde, acetic acid and absolute ethyl alcohol according to a mass ratio of 1:0.1-0.2:10-14.
5. The preparation method of the chitosan-based fluorine removal agent according to claim 1, wherein the chitosan solution in the step (3) is prepared by uniformly mixing chitosan, acetic acid, absolute ethyl alcohol and pure water according to a mass ratio of 1:3-4:80-120:200-300.
6. The method for preparing a chitosan-based fluorine removing agent according to claim 1, wherein the chitosan has a deacetylation degree of 88% and a molecular weight of 161kDa, and the manufacturer is a limited group of chemical reagents of the national drug group.
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