CN113070025B - Magnetic fly ash adsorbing material and preparation method and application thereof - Google Patents
Magnetic fly ash adsorbing material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113070025B CN113070025B CN202110370066.XA CN202110370066A CN113070025B CN 113070025 B CN113070025 B CN 113070025B CN 202110370066 A CN202110370066 A CN 202110370066A CN 113070025 B CN113070025 B CN 113070025B
- Authority
- CN
- China
- Prior art keywords
- fly ash
- magnetic
- adsorbing material
- adsorbing
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/04—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
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
Abstract
The invention relates to a magnetic fly ash adsorbing material and a preparation method and application thereof, aiming at solving the technical problems that the existing process for preparing magnetic fly ash is uncontrollable, the obtained magnetic fly ash is a ferromagnetic material, does not have magnetic separability, is easy to agglomerate in an adsorbing liquid and causes the great reduction of the adsorption capacity. The invention takes the fly ash material subjected to surface physicochemical modification as a carrier, and obtains the fly ash/ferric oxide composite material through the controllable growth and the pyrolysis conversion of metal organic framework Materials (MOFs), wherein ferric oxide in the composite material is assembled and arranged on the surface of the fly ash through the interaction between particles, and the total radial thickness of the ferric oxide assembly is 50-80 nanometers. The synthetic method is simple, the controllability is good, the prepared magnetic fly ash adsorbing material is definite in structure and excellent in performance, has a super-paramagnetic characteristic, can guarantee the dispersibility of the material in the adsorbing process, has double characteristics of adsorption and magnetic separation, and can be applied to the field of water pollution treatment.
Description
Technical Field
The invention belongs to the technical field of adsorption materials, and particularly relates to a magnetic fly ash adsorption material and a preparation method and application thereof.
Background
The fly ash is one of main solid waste byproducts of coal combustion, the annual output is measured in tons, and the storage and the treatment of the fly ash cause great environmental problems, so that the fly ash becomes one of the concerns of the research on the recycling of the coal byproduct solid waste in recent years. The fly ash mainly comprises silicon and aluminum oxide and a small amount of metal compounds of iron, calcium and magnesium, has a large specific surface area, is formed at high temperature and high pressure, has a stable structure, and is a good adsorbing material. As an adsorption material, the fly ash is widely applied to adsorption treatment of organic pollutants and heavy metal ions in water through reasonable physicochemical treatment. However, in the current water treatment application process, the problems of high energy consumption and recycling of the adsorbed adsorption material separation exist, and the magnetic separation is one of the main methods for solving the problems by combining with the magnetic material. The research shows that the magnetic fly ash is prepared by combining the fly ash and a magnetic material, so that the adsorption and magnetic separation are realized, but the obtained magnetic fly ash is a ferromagnetic material and is easy to agglomerate in an adsorption liquid due to the uncontrollable property of the preparation process, so that the adsorption capacity is greatly reduced. Therefore, how to endow the fly ash with magnetic separation property without influencing adsorption property has important significance for application and development of the fly ash as an adsorption material.
Disclosure of Invention
The invention aims to solve the technical problems that the existing process for preparing magnetic fly ash is uncontrollable, the obtained magnetic fly ash is a ferromagnetic material, the obtained magnetic fly ash does not have magnetic separability and is easy to agglomerate in an adsorption liquid, so that the adsorption capacity is greatly reduced, and further provides a magnetic fly ash adsorption material and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of a magnetic fly ash adsorbing material comprises the following steps:
(1) pretreatment of fly ash
Acid modification: dispersing fly ash in hydrochloric acid solution with molar concentration of 0.2-2M, mechanically stirring for 20-50min at room temperature, filtering, washing to neutrality, ultrasonically dispersing in an ultrasonic cleaner, and freeze drying to obtain acid modified fly ash;
secondly, surface state modification: dispersing the acid-modified fly ash obtained in the first step in a PVP solution with the mass fraction of 0.1% -8%, performing ultrasonic treatment for 30min-50min, maintaining the temperature at 20 ℃ -50 ℃, mechanically stirring for 10-24h, and finally, centrifugally cleaning redundant PVP by using water to obtain a PVP-modified fly ash material;
(2) preparation of fly ash @ MIL-88B compound
Adding the PVP modified fly ash material obtained in the step (1) into Pluronic F127 aqueous solution with the mass concentration of 10-40mg/mL, uniformly mixing, then adding molten chloride hexahydrate with the molar concentration of 2-5mM, continuously adding acetic acid and uniformly mixing, finally adding amino terephthalic acid aqueous solution with the molar concentration of 5-20mM to form final total reaction mixed solution, stirring and mixing for 0.5-1.5h, transferring the total reaction mixed solution into a hydrothermal kettle, keeping for 12-24h at the temperature of 80-130 ℃, finally centrifugally cleaning for several times by using ethanol, and freeze-drying to obtain an @ MIL-88B composite;
(3) preparation of magnetic fly ash @ ferric oxide composite material
And (3) taking 0.5-3.0 g of the fly ash @ MIL-88B compound obtained in the step (2) to be put into a quartz boat, putting the quartz boat into a vacuum tube furnace, heating the quartz boat from room temperature to 500-700 ℃ at a heating rate of 3-8 ℃/min under an inert atmosphere condition maintained by argon, keeping the temperature for 0.5-3h for carrying out pyrolysis reaction, and cooling the quartz boat to room temperature at a speed of 1-4 ℃/min after the pyrolysis is finished to obtain the magnetic fly ash adsorbing material.
Furthermore, the granularity of the fly ash in the step (1) is 0.3-10 microns.
Further, in the process of the step (1), the mass concentration of the fly ash in the hydrochloric acid solution is 60-300 mg/mL.
Further, the mass concentration of the fly ash dispersed in the PVP solution in the step (1) is 0.6-3 mg/ml; the average molecular weight of PVP is Mw＝15000-35000。
Further, the acetic acid in the step (2): aqueous ferric chloride hexahydrate: aqueous solution of amino terephthalic acid: the volume ratio of Pluronic F127 aqueous solution is 1:10:10: 50.
Further, the mass concentration of the fly ash in the total reaction mixed liquid in the step (2) is 2-10 mg/mL.
The invention also provides a magnetic fly ash adsorbing material prepared by the method, the magnetic fly ash adsorbing material is a fly ash/ferric oxide composite material, ferric oxide is assembled and arranged on the surface of fly ash through interparticle interaction, and the total radial thickness of the ferric oxide assembly is 50-80 nanometers.
Furthermore, the magnetic fly ash adsorbing material has a superparamagnetic characteristic, and the saturation magnetization is greater than 40 emu/g.
The invention also provides an application of the magnetic fly ash adsorbing material prepared by the method, and the magnetic fly ash adsorbing material is used for adsorbing and separating water pollutants.
Compared with the prior art, the invention has the following advantages:
1. the invention combines the fly ash and metal organic framework Materials (MOFs) to prepare the magnetic adsorption material, has simple synthesis method and good controllability, effectively improves the adsorption capacity of the fly ash, endows the material with magnetic separation property, can realize the reutilization of adsorption separation, and can be applied to the field of water pollution treatment.
2. The magnetic fly ash adsorbing material prepared by the invention has a superparamagnetic characteristic, can ensure the dispersibility of the material in an adsorbing process, has double characteristics of adsorption and magnetic separation, and is beneficial to realizing desorption and regeneration of the material.
3. The preparation method has good controllability, and the prepared product has a definite structure and excellent performance. The target composite material is obtained by taking the fly ash material subjected to surface physicochemical modification as a carrier and performing controlled growth, pyrolysis and conversion on metal organic framework Materials (MOFs).
Drawings
FIG. 1 is an electron microscope image of the magnetic fly ash adsorbent prepared in example 1 of the present invention.
FIG. 2 is an electron microscope image of the magnetic fly ash adsorbent prepared in example 2 of the present invention.
FIG. 3 is an electron microscope image of the magnetic fly ash adsorbent prepared in example 3 of the present invention.
FIG. 4 is an electron microscope image of the magnetic fly ash adsorbent prepared in example 4 of the present invention.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1
(1) Pretreatment of fly ash
Acid modification: dispersing 40g of raw fly ash with the size of 5 microns in 200mL of hydrochloric acid solution with the molar concentration of 1M, mechanically stirring for 30min at room temperature, filtering, washing to be neutral, ultrasonically dispersing in an ultrasonic cleaner, and freeze-drying to obtain the acid modified fly ash.
Secondly, surface state modification: and (2) dispersing 0.5g of the acid modified fly ash powder obtained in the step (i) into 5 mass percent of 500ml PP (polyvinylpyrrolidone with molecular weight Mw of 20000) solution, performing ultrasonic treatment for 30min, maintaining the temperature at 30 ℃, mechanically stirring for 20h, and finally centrifugally cleaning redundant PVP surfactant with water to obtain the PVP modified fly ash material.
(2) Preparation of fly ash @ MIL-88B compound
Adding 0.5g of the fly ash material obtained in the step (1) into 100mL of Pluronic F127 aqueous solution with the mass concentration of 20mg/mL, uniformly mixing, then adding 20mL of molten iron chloride hexahydrate with the molar concentration of 3mM into the solution, after uniformly mixing, continuously adding 2mL of acetic acid into the mixed solution, uniformly mixing, finally adding 20mL of aminoterephthalic acid aqueous solution with the molar concentration of 6mM into the mixed solution to form a final reaction mixed solution, stirring and mixing for 1h, transferring the reaction mixed solution into a hydrothermal kettle, keeping the reaction for 20h at 110 ℃, finally carrying out centrifugal cleaning for several times by using ethanol, and carrying out freeze drying to obtain the fly ash @ MIL-88B compound.
(3) Preparation of magnetic fly ash @ ferric oxide composite material
And (3) taking 0.5g of the fly ash @ MIL-88B compound obtained in the step (2) to a quartz boat, putting the quartz boat into a vacuum tube furnace, heating the quartz boat to 580 ℃ from room temperature at a heating rate of 5 ℃/min under the inert atmosphere condition maintained by argon, keeping the temperature for 1.5 hours for carrying out pyrolysis reaction, and cooling the quartz boat to room temperature at a speed of 3 ℃/min after the pyrolysis is finished, thus obtaining the magnetic fly ash adsorbing material.
As shown in fig. 1, the magnetic fly ash adsorbing material prepared in this embodiment is a fly ash/iron oxide composite material, in which iron oxide forms iron oxide assemblies through interparticle interaction and is arranged on the surface of fly ash, and the total radial thickness of the iron oxide assembly layer is about 70 nm.
The material has a superparamagnetic characteristic, has good dispersibility in a target dispersion liquid, and has a saturation magnetization of about 50emu/g through measurement. The adsorption to methylene blue reaches about 98 percent, and the magnetic separation efficiency of nearly 100 percent is realized within 1 min.
Example 2
(1) Pretreatment of fly ash
Acid modification: dispersing 12g of raw fly ash with the size of 5 microns in 200mL of hydrochloric acid solution with the molar concentration of 1M, mechanically stirring for 20min at room temperature, filtering, washing to be neutral, ultrasonically dispersing in an ultrasonic cleaner, and freeze-drying to obtain the acid modified fly ash.
Secondly, surface state modification: and (2) dispersing 0.3g of the acid modified fly ash powder obtained in the step (i) in a solution of 500ml of PVP (polyvinylpyrrolidone) with the molecular weight of Mw (15000) with the mass fraction of 0.1%, carrying out ultrasonic treatment for 30min, maintaining the temperature at 20 ℃, mechanically stirring for 10h, and finally, centrifugally cleaning redundant PVP surfactant with water to obtain the PVP modified fly ash material.
(2) Preparation of fly ash @ MIL-88B compound
Adding 0.28g of the fly ash material obtained in the step (1) into 100mL of Pluronic F127 aqueous solution with the mass concentration of 10mg/mL, uniformly mixing, then adding 20mL of 2mM solution of ferric chloride hexahydrate into the solution, after uniform mixing, continuously adding 2mL of acetic acid into the mixed solution, uniformly mixing, finally adding 20mL of 5mM solution of amino terephthalic acid to form a final reaction mixed solution, stirring and mixing for 1h, transferring the reaction mixed solution into a hydrothermal kettle, keeping for 12h at the temperature of 80 ℃, finally carrying out centrifugal cleaning for several times by using ethanol, and carrying out freeze drying to obtain the fly ash @ MIL-88B compound.
(3) Preparation of magnetic fly ash @ ferric oxide composite material
And (3) taking 0.5g of the fly ash @ MIL-88B compound obtained in the step (2) to a quartz boat, putting the quartz boat into a vacuum tube furnace, heating the quartz boat to 500 ℃ from room temperature at a heating rate of 3 ℃/min under the inert atmosphere condition maintained by argon, keeping the temperature for 0.5h for carrying out pyrolysis reaction, and cooling the quartz boat to room temperature at a speed of 1 ℃/min after the pyrolysis is finished, thus obtaining the magnetic fly ash adsorbing material.
As shown in fig. 2, in order to prepare the magnetic fly ash adsorbing material, iron oxide is assembled and arranged on the surface of the fly ash through the interaction between particles, and the total radial thickness of the iron oxide assembly layer is about 50 nm.
The material has a superparamagnetic characteristic, has good dispersibility in a target dispersion liquid, and has a saturation magnetization of about 45emu/g through measurement. The adsorption to methylene blue reaches about 91%, and the magnetic separation efficiency of nearly 100% is realized within 5 min.
Example 3
(1) Pretreatment of fly ash
Acid modification: dispersing 35g of raw pulverized coal ash with the size of 10 microns in 200mL of hydrochloric acid solution with the molar concentration of 2M, mechanically stirring for 40min at room temperature, filtering, washing to be neutral, ultrasonically dispersing in an ultrasonic cleaner, and freeze-drying to obtain the acid-modified pulverized coal ash.
Surface state modification: and (2) dispersing 1g of the acid-modified fly ash powder obtained in the step (i) in a 5% PVP500mL (polyvinylpyrrolidone with a molecular weight of Mw (25000)) solution, performing ultrasonic treatment for 40min, mechanically stirring for 15h under the condition of maintaining the temperature of 40 ℃, and finally, centrifugally cleaning redundant PVP surfactant with water to obtain the PVP modified fly ash material.
(2) Preparation of fly ash @ MIL-88B compound
Adding 0.8g of the fly ash material obtained in the step (1) into 100mL of Pluronic F127 aqueous solution with the mass concentration of 25mg/mL, uniformly mixing, then adding 20mL of molten ferric chloride hexahydrate with the molar concentration of 3.5mM into the solution, after uniformly mixing, continuously adding 2mL of acetic acid into the mixed solution, uniformly mixing, finally adding 20mL of amino terephthalic acid aqueous solution with the molar concentration of 13mM into the mixed solution to form a final reaction mixed solution, stirring and mixing for 1h, transferring the reaction mixed solution into a hydrothermal kettle, keeping the temperature for 18h at 105 ℃, finally carrying out centrifugal cleaning for several times by using ethanol, and carrying out freeze drying to obtain the fly ash MIL-88B compound.
(3) Preparation of magnetic fly ash @ ferric oxide composite material
And (3) taking 0.5g of the fly ash @ MIL-88B compound obtained in the step (2) to a quartz boat, putting the quartz boat into a vacuum tube furnace, heating the quartz boat to 600 ℃ from room temperature at a heating rate of 5 ℃/min under the inert atmosphere condition maintained by argon, keeping the temperature for 1.5h for carrying out pyrolysis reaction, and cooling the quartz boat to room temperature at a speed of 2 ℃/min after the pyrolysis is finished, thus obtaining the magnetic fly ash adsorbing material.
As shown in fig. 3, in order to prepare the magnetic fly ash adsorbing material, iron oxide is assembled and arranged on the surface of the fly ash through the interaction between particles, and the total radial thickness of the iron oxide assembly layer is about 60 nm.
The material has a superparamagnetic characteristic, has good dispersibility in a target dispersion liquid, and has a saturation magnetization of about 53emu/g through measurement. The adsorption to methylene blue reaches about 93%, and the magnetic separation efficiency of nearly 100% is realized within 3 min.
Example 4
(1) Pretreatment of fly ash
Acid modification: 60g of raw pulverized coal ash with the size of 0.3 micron is dispersed in 200mL of hydrochloric acid solution with the molar concentration of 1M, mechanically stirred for 50min at room temperature, filtered, washed to be neutral, ultrasonically dispersed in an ultrasonic cleaner, and freeze-dried to obtain the acid-modified pulverized coal ash.
Secondly, surface state modification: and (2) dispersing 1.5g of the acid modified fly ash powder obtained in the step (i) in 500mL of PVP (polyvinylpyrrolidone with a molecular weight Mw of 35000) solution with a mass fraction of 8%, performing ultrasonic treatment for 50min, maintaining the temperature at 50 ℃, mechanically stirring for 24h, and finally, centrifugally cleaning redundant PVP surfactant with water to obtain the PVP modified fly ash material.
(2) Preparation of fly ash @ MIL-88B compound
Adding 1.4g of the fly ash material obtained in the step (1) into 100mL of Pluronic F127 aqueous solution with the mass concentration of 40mg/mL, uniformly mixing, then adding 20mL of ferric chloride hexahydrate aqueous solution with the molar concentration of 5mM into the solution, after uniformly mixing, continuously adding 2mL of acetic acid into the mixed solution, uniformly mixing, finally adding 20mL of amino terephthalic acid aqueous solution with the molar concentration of 20mM into the mixed solution to form a final reaction mixed solution, stirring and mixing for 1.5h, transferring the reaction mixed solution into a hydrothermal kettle, keeping the temperature for 24h at 130 ℃, finally carrying out centrifugal cleaning for several times by using ethanol, and carrying out freeze drying to obtain the fly ash MIL-88B compound.
(3) Preparation of magnetic fly ash @ iron oxide composite material
And (3) taking 0.5g of the fly ash @ MIL-88B compound obtained in the step (2) to a quartz boat, putting the quartz boat into a vacuum tube furnace, heating the quartz boat to 700 ℃ from room temperature at a heating rate of 8 ℃/min under the inert atmosphere condition maintained by argon, keeping the temperature for 3 hours for carrying out pyrolysis reaction, and cooling the quartz boat to room temperature at a speed of 4 ℃/min after the pyrolysis is finished, so as to obtain the magnetic fly ash adsorbing material.
As shown in fig. 4, in order to prepare the magnetic fly ash adsorbing material, iron oxide is assembled and arranged on the surface of the fly ash through the interaction between particles, and the total radial thickness of the iron oxide assembly layer is about 80 nm.
The material has a superparamagnetic characteristic, has good dispersibility in a target dispersion liquid, and has saturation magnetization of about 55emu/g through measurement. The adsorption to methylene blue reaches about 96%, and the magnetic separation efficiency of nearly 100% is realized within 2 min.
Comparative example 1
This comparative example 1 was conducted in the same manner as in example 1 except that the molar amounts of ferric chloride hexahydrate and aminoterephthalic acid were increased to 10mM and 30mM, respectively, in step (2), based on the preparation process of example 1.
The result shows that under the condition, the material obtained in the step (2) is not a composite of the fly ash @ MIL-88B, the two materials have phase separation phenomena, the MOFs material does not take the fly ash as a carrier to carry out nucleation and growth processes, the material prepared in the embodiment has the adsorption characteristic, but the magnetic separation effect is poor, the separation efficiency is only 10%, and the fly ash serving as an adsorption main body cannot realize magnetic separation.
Comparative example 2
This comparative example 2 was conducted in the same manner as in example 1 except that the mass concentration of Pluronic F127 was reduced to 2mg/mL in step (2) based on the preparation process of example 1.
The result shows that under the condition, the material obtained in the step (3) is a composite material of fly ash @ iron oxide, but the average particle size reaches 70 nanometers and no superparamagnetism exists due to the overlarge particle size of the iron oxide on the surface of the material, so that the obtained material is seriously agglomerated in a target adsorption solution, the adsorption efficiency is greatly reduced (60 percent), and the expected effect cannot be achieved.
Comparative example 3
This comparative example 3 was conducted in the same manner as in example 1 except that the sintering transformation temperature was increased to 750 ℃ in step (3) based on the preparation process of example 1.
The result shows that under the condition, the prepared material is the composite of the fly ash, the iron oxide and the porous carbon material, has better adsorption property and high adsorption performance on the methyl blue solution, but the iron oxide material on the surface is alpha crystal phase and has no magnetism, so that the material has no magnetic separation characteristic and can not achieve the expected effect.
Therefore, under the preparation condition of the invention, the prepared composite material has good adsorption capacity and magnetic separation property, can realize the reutilization of adsorption separation, and can be applied to the field of water pollution treatment.
Claims (6)
1. The preparation method of the magnetic fly ash adsorbing material is characterized by comprising the following steps of:
(1) pretreatment of fly ash
Acid modification: dispersing fly ash in hydrochloric acid solution with molar concentration of 0.2-2M, mechanically stirring for 20-50min at room temperature, filtering, washing to neutrality, ultrasonically dispersing in an ultrasonic cleaner, and freeze drying to obtain acid modified fly ash;
secondly, surface state modification: dispersing the acid modified fly ash obtained in the process I into a PVP solution with the mass fraction of 0.1% -8%, carrying out ultrasonic treatment for 30min-50min, maintaining the temperature at 20 ℃ -50 ℃, mechanically stirring for 10-24h, and finally, centrifugally cleaning redundant PVP by using water to obtain a PVP modified fly ash material; the mass concentration of the fly ash dispersed in the PVP solution is 0.6-3 mg/ml; the average molecular weight of PVP is Mw=15000-35000；
(2) Preparation of fly ash @ MIL-88B compound
Adding the PVP modified fly ash material obtained in the step (1) into Pluronic F127 aqueous solution with the mass concentration of 10-40mg/mL, uniformly mixing, adding molten chloride hexahydrate with the molar concentration of 2-5mM, continuously adding acetic acid and uniformly mixing after uniformly mixing, finally adding amino terephthalic acid aqueous solution with the molar concentration of 5-20mM to form final total reaction mixed solution, stirring and mixing for 0.5-1.5h, transferring the total reaction mixed solution into a hydrothermal kettle, keeping for 12-24h at the temperature of 80-130 ℃, finally carrying out centrifugal cleaning for several times by using ethanol, and carrying out freeze drying to obtain a fly ash @ MIL-88B compound;
(3) preparation of magnetic fly ash @ iron oxide composite material
Taking 0.5-3.0 g of the fly ash @ MIL-88B compound obtained in the step (2) into a quartz boat, putting the quartz boat into a vacuum tube furnace, heating the quartz boat from room temperature to 500-700 ℃ at a heating rate of 3-8 ℃/min under the inert atmosphere condition maintained by argon, keeping the temperature for 0.5-3h for carrying out pyrolysis reaction, and cooling the quartz boat to room temperature at a speed of 1-4 ℃/min after the pyrolysis is finished to prepare a magnetic fly ash adsorbing material;
the magnetic fly ash adsorbing material is a fly ash/ferric oxide composite material, the ferric oxide is assembled and arranged on the surface of the fly ash through the interaction between particles, and the total radial thickness of the ferric oxide assembly is 50-80 nanometers; the magnetic fly ash adsorbing material has a superparamagnetic characteristic, and the saturation magnetization is greater than 40 emu/g.
2. The method for preparing the magnetic fly ash adsorbing material according to claim 1, wherein the method comprises the following steps: in the step (1), the granularity of the fly ash is 0.3-10 microns.
3. The method for preparing the magnetic fly ash adsorbing material according to claim 1, wherein the method comprises the following steps: in the step (1), the mass concentration of the fly ash in the hydrochloric acid solution is 60-300 mg/mL.
4. The method for preparing the magnetic fly ash adsorbing material according to claim 1, wherein the method comprises the following steps: acetic acid in the step (2): aqueous ferric chloride hexahydrate: aqueous solution of amino terephthalic acid: the volume ratio of Pluronic F127 aqueous solution was 1:10:10: 50.
5. The method for preparing the magnetic fly ash adsorbing material according to claim 1, wherein the method comprises the following steps: in the step (2), the mass concentration of the fly ash in the total reaction mixed liquid is 2-10 mg/mL.
6. The use of a magnetic fly ash adsorbent material prepared by the preparation method of any one of claims 1 to 5, characterized in that: the magnetic fly ash adsorbing material is used for adsorbing and separating water pollutants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110370066.XA CN113070025B (en) | 2021-04-07 | 2021-04-07 | Magnetic fly ash adsorbing material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110370066.XA CN113070025B (en) | 2021-04-07 | 2021-04-07 | Magnetic fly ash adsorbing material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113070025A CN113070025A (en) | 2021-07-06 |
| CN113070025B true CN113070025B (en) | 2022-07-19 |
Family
ID=76615158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110370066.XA Active CN113070025B (en) | 2021-04-07 | 2021-04-07 | Magnetic fly ash adsorbing material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113070025B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114657098A (en) * | 2022-03-28 | 2022-06-24 | 深圳大学 | Modified microorganism, modification method and application thereof, and antitumor drug |
| CN115228429B (en) * | 2022-08-31 | 2023-06-13 | 中南大学 | Magnetic fly ash adsorbent, preparation method and application |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9950311B2 (en) * | 2011-11-25 | 2018-04-24 | Council Of Scientific & Industrial Research | Process for the synthesis of magnetically recoverable, high surface area carbon-Fe3O4 nano-composite using metal organic framework (MOF) |
| CN104043394B (en) * | 2013-03-14 | 2018-04-17 | 安徽大学 | A kind of method that magnetic adsorptive material is prepared using ferrous metals organic backbone |
| CN108147959A (en) * | 2016-12-02 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of functionalized modification ferrous metal organic framework materials and preparation method thereof |
| EP3453450B1 (en) * | 2017-09-12 | 2021-06-30 | Centre National De La Recherche Scientifique | Use of metal organic frameworks for the capture of acetic acid |
| CN111111638B (en) * | 2019-12-05 | 2021-07-27 | 山西大学 | Preparation method of fly ash photocatalytic material |
| CN111774041A (en) * | 2020-07-03 | 2020-10-16 | 山西大学 | Nano superparamagnetic molecularly imprinted magnetic bead, preparation method and application |
-
2021
- 2021-04-07 CN CN202110370066.XA patent/CN113070025B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113070025A (en) | 2021-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113070025B (en) | Magnetic fly ash adsorbing material and preparation method and application thereof | |
| Zhu et al. | Novel multifunctional NiFe2O4/ZnO hybrids for dye removal by adsorption, photocatalysis and magnetic separation | |
| Chen et al. | Simple hydrothermal synthesis of magnetic MnFe2O4-sludge biochar composites for removal of aqueous Pb2+ | |
| CN113398936B (en) | Zinc oxide/ZnFe-LDH @ charcoal visible-light-driven photocatalyst and preparation method and application thereof | |
| CN108704610B (en) | Magnetic carbon modified magnesium-iron hydrotalcite composite material and preparation method and application thereof | |
| CN104944474B (en) | Method for preparing nanometer MnFe2O4/graphene composite material | |
| CN104117339B (en) | For preparation method and the application process thereof of the adsorbent of absorbing dye | |
| WO2022095565A1 (en) | Transition metal-doped carbon microsphere, preparation method therefor and application thereof | |
| Kang et al. | Functionalized MIL-53 and its derivatives modified Bi2WO6 as effective piezocatalysts and membranes for adsorption and decomposition of organic pollutants | |
| CN103638894A (en) | Preparation method of modified graphene-based iron oxide nano-composite material | |
| CN110127678A (en) | A kind of preparation method of magnetic graphene | |
| CN101336070B (en) | Nano composite alpha-Fe for wave-absorbing material and preparation method thereof | |
| CN114100578B (en) | Preparation method and application of porous biochar loaded nano lanthanum/iron compound particle composite material | |
| Guo et al. | MoO3-templated synthesis of TiO2@ C-Ni microtubes for efficient catalysis and protein adsorption | |
| CN108091838B (en) | Method for preparing core-shell structure nano α -Fe2O3@ C composite material in one step | |
| CN109439647B (en) | Magnetic immobilized enzyme carrier with core-shell structure and preparation method and application thereof | |
| Zhang et al. | AgBrO3/Few-Layer g-C3N4 Composites: A Visible-Light-Driven Photocatalyst for Tetracycline Degradation | |
| CN114588917B (en) | Preparation method and application of sulfur-doped carbon skeleton-coated octasulfide heptairon nanoparticle double-reaction-center Fenton-like catalyst | |
| CN106587326B (en) | A kind of preparation method of the graphene oxide of carried magnetic nano particle and conducting polymer Fenton gel | |
| CN113786838B (en) | Core-shell nanocomposite and preparation method and application thereof | |
| CN113856680B (en) | Magnetic carbon-doped spinel copper ferrite catalyst and preparation method and application thereof | |
| CN110193347B (en) | Nano carbon-coated cobaltous oxide and preparation method and application thereof | |
| CN114904534A (en) | Bismuth molybdate/ferric vanadate composite nanomaterial, preparation method thereof and application thereof in acousto-optic catalytic degradation of pollutants in water | |
| Su et al. | Preparation and Properties of CdS/Spherical g-C3N4 nn Heterojunction as a Visible-Light-Driven Photocatalyst for Tetracycline Degradation | |
| CN114774085A (en) | Bimetallic MOF (Metal organic framework) derived graphitized carbon-based photothermal composite phase change material as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |