CN112110744A - Magnetic porous ceramic adsorption material and preparation method and application thereof - Google Patents
Magnetic porous ceramic adsorption material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a magnetic porous ceramic adsorption material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing the fly ash with auxiliary materials, and stirring and mixing the fly ash with a gel and a solvent to obtain fly ash slurry; (2) injecting the fly ash slurry obtained in the step (1) into a mould, standing for forming and drying to obtain a porous dry blank; (3) sintering the porous dry blank obtained in the step (2) to obtain a porous ceramic substrate; (4) and (4) preparing magnetic nanoparticles on the porous ceramic substrate prepared in the step (3) to obtain the magnetic porous ceramic adsorption material. The adsorption material prepared by the preparation method has a hierarchical pore structure and a high specific surface area, can be used for adsorption treatment of heavy metal ions in wastewater, is green and environment-friendly, is easy to implement, has a controllable production process, and can realize industrial utilization.
Description
Technical Field
The invention belongs to the field of sewage treatment materials, relates to a preparation method of an adsorption material, and particularly relates to a magnetic porous ceramic adsorption material, and a preparation method and application thereof.
Background
Fly ash is a byproduct of thermal power generation, and a large amount of fly ash is generated in China every year, but the reutilization rate is far lower than that of developed countries. The fly ash is stacked in the open air, which causes waste of land resources and increase of management cost, and simultaneously, the heavy metal ions are leached and seeped to cause underground water pollution. The united states Environmental Protection Agency (EPA) has recognized that recycling fly ash can yield environmental, economic and industrial products. Therefore, resource recycling of the fly ash becomes a new research trend and development direction.
Fly ash is a complex component, mainly consisting of silica and alumina, and also contains other metal oxides, unburned carbon, and the like. Due to factors such as particle size and specific surface area, the fly ash is widely used as an adsorbing material for removing pollutants, but the risk of directly using the fly ash is high, because the fly ash has small particle size and is easy to generate hydration reaction to cause difficult recovery, and the risk of secondary pollution also exists. In contrast, the porous adsorption material prepared from the fly ash has the characteristics of the fly ash, and meanwhile, the porous adsorption material has a larger specific surface area, so that the porous adsorption material has a more excellent pollutant adsorption effect. For example, CN 109569545 a discloses a method for preparing an aluminum-silicon porous material from fly ash, in which the aluminum-silicon porous material is obtained by performing acid treatment \ alkali treatment or leaching solution on the fly ash, and has rich pore structure and large specific surface area. CN 107930576A discloses a preparation method of a fly ash microbead porous material and the prepared porous material, the preparation method obtains the fly ash microbead porous material by concentrated sulfuric acid modification and roasting water bath, and the material can adsorb organic dye in wastewater. However, the material prepared by the method needs to be treated by acid or alkali, the waste liquid generated in the process of dissolving out the heavy metal salt solution still needs to be treated, the production process is not green enough, and the risk of secondary pollution exists.
The magnetic nano iron oxide has large specific surface area, strong adsorption capacity and certain oxidizability, is widely used as an adsorbent or a catalyst in the field of sewage treatment, and has good adsorption effect on radioactive elements and divalent heavy metal ions such as copper, zinc and the like. However, the magnetic nano iron oxide has fine particles and magnetism, and is easy to agglomerate in water, so that the separation and recovery are difficult. The method for effectively solving the problems is to load the magnetic nano ferric oxide on a large-size carrier. The fly ash-based porous adsorption material has poor adsorption effect when the concentration of pollutants is low. Therefore, the adsorption effect can be enhanced by loading the magnetic nano iron oxide on the magnetic porous adsorption material, so that the magnetic porous adsorption material is obtained, the problems existing in the independent application of the two materials are effectively avoided, and the requirements of practical application are met. CN 104261553A mixes fly ash and magnetic ferric oxide according to certain proportion directly and granulates again and obtains the magnetic fly ash haydite, is showing to improve the treatment effect to the waste water. However, the magnetic iron oxide and the fly ash are easy to separate in practical application only by physical adhesion, and the method needs strong magnetic field magnetization, so that the energy consumption is huge, and certain defects exist in practical application.
Disclosure of Invention
In order to solve the technical problems in the prior art, the application provides a preparation method of a magnetic porous ceramic adsorption material, the adsorption material prepared by the preparation method has a hierarchical pore structure and a high specific surface area, and can be used for adsorption treatment of heavy metal ions in wastewater, and the preparation method is green and environment-friendly, is easy to implement, has a controllable production process, and can realize industrial utilization.
In order to achieve the technical effect, the invention adopts the following technical scheme:
one purpose of the invention is to provide a preparation method of a magnetic porous ceramic adsorption material, which comprises the following steps:
(1) mixing the fly ash with auxiliary materials, and stirring and mixing the fly ash with a gel and a solvent to obtain fly ash slurry;
(2) injecting the fly ash slurry obtained in the step (1) into a mould, standing for forming and drying to obtain a porous dry blank;
(3) sintering the porous dry blank obtained in the step (2) to obtain a porous ceramic substrate;
(4) and (4) preparing magnetic nanoparticles on the porous ceramic substrate prepared in the step (3) to obtain the magnetic porous ceramic adsorption material.
In the present invention, the fly ash is dried before being mixed with the auxiliary materials, the drying temperature may be 80 to 150 ℃, such as 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or 140 ℃, and the drying time may be 1 to 3 hours, such as 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours or 2.8 hours, but is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.
As a preferable technical scheme of the invention, the auxiliary materials in the step (1) comprise kaolin, a dispersing agent and graphite.
Preferably, the mass ratio of the fly ash to the kaolin, the dispersant and the graphite is 10 (2-3): (0.5-1): 1-1.5), such as 10:2.1:0.6:1.1, 10:2.2:0.7:1.3, 10:2.3:0.8:1.5, 10:2.5:0.8:1.0 or 10:2.8:0.9:1.2, but not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
Preferably, the dispersant comprises ammonium citrate.
As a preferred technical scheme of the invention, the gel in the step (1) comprises gelatin.
Preferably, the gelatin is an aqueous gelatin solution, and the mass concentration of the aqueous gelatin solution is 4 to 8 wt%, such as 4.1%, 5.2%, 7.3%, 6.4%, 4.5%, 6.6%, 5.7%, 6.8%, or 7.9%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the solvent in step (1) is water.
Preferably, the stirring temperature in step (1) is 40-50 deg.C, such as 41 deg.C, 42 deg.C, 43 deg.C, 44 deg.C, 45 deg.C, 46 deg.C, 47 deg.C, 48 deg.C or 49 deg.C, and the stirring time is 20-30 min, such as 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min or 29min, but it is not limited to the recited values, and other values in the above-mentioned ranges are also applicable.
Preferably, the solid content of the fly ash slurry in step (1) is 50 to 60 wt%, such as 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt% or 59 wt%, but not limited to the recited values, and other non-recited values within the range are also applicable.
According to the invention, the fly ash porous adsorption material substrate is obtained by gel injection molding, and the preparation method has the advantages that ceramic parts with complex shapes and excellent performance can be prepared, inconvenience caused by machining is reduced to the maximum extent, and the preparation method is suitable for large-scale production and has wide application prospect and important popularization value.
In a preferred embodiment of the present invention, the temperature of the standing and molding in the step (2) is 5 to 10 ℃, for example, 5.5 ℃, 6 ℃, 6.5 ℃, 7 ℃, 7.5 ℃, 8 ℃, 8.5 ℃, 9 ℃ or 9.5 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the drying temperature in step (2) is 20 to 30 ℃, such as 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃ or 29 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying time in step (2) is not less than 24h, such as 28h, 32h, 36h, 40h, 44h or 48h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferred technical scheme of the invention, the sintering in the step (3) comprises a first-stage sintering and a second-stage sintering.
Preferably, the temperature of the first stage sintering is 500 to 600 ℃, such as 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃ or 590 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature rise rate of the first stage sintering is 5-8 ℃/min, such as 5.2 ℃/min, 5.5 ℃/min, 5.8 ℃/min, 6 ℃/min, 6.5 ℃/min, 7 ℃/min, 7.2 ℃/min, 7.5 ℃/min, or 7.8 ℃/min, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the sintering time is 1-2 h, such as 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, or 1.9h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the second stage sintering is 600 to 1250 ℃, such as 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 9500 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃ or 1240 ℃ and the like, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature rise rate of the second stage sintering is 5-6 ℃/min, such as 5.1 ℃/min, 5.2 ℃/min, 5.3 ℃/min, 5.4 ℃/min, 5.5 ℃/min, 5.6 ℃/min, 5.7 ℃/min, 5.8 ℃/min, or 5.9 ℃/min, but not limited to the enumerated values, and other non-enumerated values within the range of the enumerated values are also applicable.
Preferably, the time for the second sintering is 1 to 2 hours, such as 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the method for preparing the magnetic nanoparticles on the porous ceramic substrate in the step (4) comprises the following steps:
dissolving ferric salt and ferrous salt in nitrogen atmosphere to obtain a mixed solution, immersing the porous ceramic substrate into the mixed solution, gradually and slowly dripping ammonia water, stirring and then ultrasonically treating the solution until the solution turns black, adding citric acid solution, stirring and washing to obtain the magnetic porous ceramic adsorbing material.
According to the preferable technical scheme of the invention, the molar ratio of the ferric salt to the ferrous salt is 2-3: 1, such as 2:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1 or 2.9:1, etc., but is not limited to the recited values, and other unrecited values within the above numerical ranges are equally applicable.
Preferably, the ferric salt comprises ferric chloride hexahydrate and the ferrous salt comprises ferrous chloride tetrahydrate.
Preferably, the mass concentration of the ammonia water is 20 to 30%, such as 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, or 29%, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the volume ratio of the ammonia water to the mixed solution of the ferric salt and the ferrous salt is 1: 20-25, such as 1:21, 1:22, 1:23 or 1:24, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time for stirring before ultrasonic treatment is 8-15 min, such as 9min, 10min, 11min, 12min, 13min or 14min, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time of the ultrasound is 8-15 min, such as 9min, 10min, 11min, 12min, 13min or 14min, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the prepared citric acid solution is prepared by dissolving 1-2 g of citric acid in 10ml of water.
Preferably, the time for stirring after adding the citric acid is not less than 24 hours, such as 28 hours, 32 hours, 36 hours, 40 hours, 44 hours or 48 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the magnetic nano iron oxide is loaded on the porous ceramic substrate, and the nano particles increase the adsorption performance and the pollution resistance of the porous ceramic substrate, thereby forming a multifunctional material for adsorption filtration coupling.
As a preferred technical solution of the present invention, the preparation method of the magnetic porous ceramic adsorption material comprises the following steps:
(1) mixing fly ash, kaolin, a dispersant ammonium citrate and graphite, wherein the mass ratio of the fly ash to the kaolin to the dispersant ammonium citrate to the graphite is 10 (2-3) to (0.5-1) to (1-1.5), and stirring and mixing the fly ash, the kaolin to the dispersant ammonium citrate and the graphite with a gelatin solution with a mass concentration of 4-8 wt% and water at 40-50 ℃ for 20-30 min to obtain a fly ash slurry, wherein the solid content of the fly ash slurry is 40-50 wt%;
(2) injecting the fly ash slurry obtained in the step (1) into a mold, standing and molding at 5-10 ℃, and drying at 20-30 ℃ for not less than 24 hours to obtain a porous dry blank;
(3) sintering the porous dry blank obtained in the step (2) to obtain a porous ceramic substrate;
the sintering comprises first-stage sintering and second-stage sintering, wherein the temperature of the first-stage sintering is 500-600 ℃, the heating rate is 5-6 ℃/min, and the time is 0.5-1 h; the temperature of the two-stage sintering is 1150-1250 ℃, the heating rate is 5-6 ℃/min, and the time is 1-2 h;
(4) and (4) immersing the porous ceramic substrate prepared in the step (3) into a uniformly mixed solution in which a ferric salt and a ferrous salt with a certain molar ratio are dissolved at room temperature under a nitrogen atmosphere. The molar ratio of ferric chloride hexahydrate to ferrous chloride tetrahydrate is 2-3: 1; dropwise adding ammonia water, wherein the mass concentration of the ammonia water is 20-30%, and the volume ratio of the ammonia water to the mixed solution of the ferric salt and the ferrous salt is 1: 20-25; and (3) after the solution turns black, stirring for 8-15 min, then carrying out ultrasonic treatment for 8-15 min, adding citric acid, stirring for not less than 24h, dissolving 1.68g of citric acid in 10ml of water, and washing to obtain the magnetic porous ceramic adsorbing material.
The second purpose of the invention is to provide a magnetic porous ceramic adsorbing material, which is prepared by any one of the preparation methods.
The invention also aims to provide an application of the magnetic porous ceramic adsorbing material, and the magnetic porous ceramic adsorbing material is used for adsorbing divalent heavy metal ions in water.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention provides a magnetic porous ceramic adsorption material and a preparation method and application thereof, wherein the magnetic porous ceramic adsorption material has large specific surface area, developed and complex pore structure, excellent adsorption capacity and certain oxidation capacity, can effectively adsorb divalent heavy metal, and has a certain decolorizing effect on organic matters;
(2) the invention provides a magnetic porous ceramic adsorption material and a preparation method and application thereof, wherein the preparation method adopts a gel injection molding method to prepare a fly ash porous ceramic substrate, and uses natural gel as a gelling agent, so that a green manufacturing process is realized; in addition, the preparation method utilizes the characteristics of the fly ash particles, and realizes the preparation of the hierarchical pores through process regulation.
Drawings
FIG. 1 is a microscopic morphology of a magnetic porous ceramic adsorbent material prepared according to the present invention;
FIG. 2 is a macro-topography of the magnetic porous ceramic adsorption material prepared by the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
the chemical composition of the fly ash used in the embodiment of the present invention is shown in table 1.
TABLE 1
| Compound (I) | SiO2 | Al2O3 | Fe2O3 | CaO | TiO2 | K2O | SO3 | MgO |
| Mass content (%) | 47.902 | 39.104 | 4.035 | 3.941 | 1.551 | 0.942 | 0.781 | 0.443 |
Example 1
The embodiment provides a preparation method of a magnetic porous ceramic adsorption material, which comprises the following steps:
(1) mixing the dried fly ash with kaolin, ammonium citrate serving as a dispersing agent and graphite in a mass ratio of 10:2:0.5:1, and stirring and mixing the mixture with a gelatin solution with a mass concentration of 4.5 wt% and water at 45 ℃ for 30min to obtain a fly ash slurry, wherein the solid content of the fly ash slurry is 55 wt%;
(2) injecting the fly ash slurry obtained in the step (1) into a mould, standing and forming at 5 ℃, and drying at 25 ℃ for 24 hours to obtain a porous dry blank;
(3) sintering the porous dry blank obtained in the step (2) to obtain a porous ceramic substrate;
the sintering comprises first-stage sintering and second-stage sintering, wherein the temperature of the first-stage sintering is 500 ℃, the heating rate is 5 ℃/min, and the time is 1 h; the temperature of the second-stage sintering is 1200 ℃, the heating rate is 5 ℃/min, and the time is 2 h;
(4) immersing the porous ceramic substrate prepared in the step (3) into a mixed solution of ferric chloride hexahydrate and ferrous chloride tetrahydrate in a nitrogen atmosphere, wherein the mixed solution contains 4.1g of ferric chloride hexahydrate, 1.49g of ferrous chloride tetrahydrate and 150mL of water; dropwise adding 6.8mL of ammonia water, wherein the mass concentration of the ammonia water is 25%; and (3) after the solution turns black, stirring for 10min, then performing ultrasonic treatment for 10min, adding citric acid, stirring for not less than 24h, dissolving 1.68g of citric acid in 10ml of water, and washing to obtain the magnetic porous ceramic adsorbing material.
Example 2
The embodiment provides a preparation method of a magnetic porous ceramic adsorption material, which comprises the following steps:
(1) mixing fly ash, kaolin, a dispersant ammonium citrate and graphite, wherein the mass ratio of the fly ash to the kaolin to the dispersant ammonium citrate to the graphite is 10:3:1:1.5, and stirring and mixing the fly ash, the kaolin to the dispersant and the graphite with a gelatin solution with the mass concentration of 5 wt% and water at 40 ℃ for 30min to obtain fly ash slurry, wherein the solid content of the fly ash slurry is 40%;
(2) injecting the fly ash slurry obtained in the step (1) into a mould, standing and forming at 10 ℃, and drying at 30 ℃ for 24 hours to obtain a porous dry blank;
(3) sintering the porous dry blank obtained in the step (2) to obtain a porous ceramic substrate;
the sintering comprises first-stage sintering and second-stage sintering, wherein the temperature of the first-stage sintering is 600 ℃, the heating rate is 6 ℃/min, and the time is 0.5 h; the temperature of the two-stage sintering is 1250 ℃, the heating rate is 6 ℃/min, and the time is 1 h;
(4) immersing the porous ceramic substrate prepared in the step (3) into a mixed solution of ferric chloride hexahydrate and ferrous chloride tetrahydrate in a nitrogen atmosphere, wherein the adding amount of the ferric chloride hexahydrate is 4.1g, and the adding amount of the ferrous chloride tetrahydrate is 1.0 g; dropwise adding ammonia water, wherein the mass concentration of the ammonia water is 30%, the adding amount is 6.8ml, and the volume ratio of the ammonia water to the mixed solution of the ferric salt and the ferrous salt is 1: 25; and (3) after the solution turns black, stirring for 15min, then carrying out ultrasonic treatment for 15min, adding citric acid, stirring for 24h, wherein the addition amount of the citric acid is 1.68g, and washing to obtain the magnetic porous ceramic adsorbing material.
Example 3
The embodiment provides a preparation method of a magnetic porous ceramic adsorption material, which comprises the following steps:
(1) mixing fly ash, kaolin, a dispersant ammonium citrate and graphite, wherein the mass ratio of the fly ash to the kaolin to the dispersant ammonium citrate to the graphite is 10:2.5:0.8:1.5, and stirring and mixing the fly ash, the kaolin to the dispersant and the graphite with a gelatin solution with the mass concentration of 6 wt% and water at 50 ℃ for 20min to obtain fly ash slurry, wherein the solid content of the fly ash slurry is 50%;
(2) injecting the fly ash slurry obtained in the step (1) into a mould, standing and forming at the temperature of 8 ℃, and drying at the temperature of 20 ℃ for 36 hours to obtain a porous dry blank;
(3) sintering the porous dry blank obtained in the step (2) to obtain a porous ceramic substrate;
the sintering comprises first-stage sintering and second-stage sintering, wherein the temperature of the first-stage sintering is 550 ℃, the heating rate is 5.5 ℃/min, and the time is 0.8 h; the temperature of the second-stage sintering is 1150 ℃, the heating rate is 5.5 ℃/min, and the time is 1.5 h;
(4) immersing the porous ceramic substrate prepared in the step (3) into a mixed solution of ferric chloride hexahydrate and ferrous chloride tetrahydrate, wherein the ferric chloride hexahydrate is 4.1g, and the concentration of the ferrous chloride tetrahydrate is 1.2 g; dropwise adding ammonia water, wherein the mass concentration of the ammonia water is 20%, and the volume ratio of the ammonia water to the mixed solution of the ferric salt and the ferrous salt is 1: 20; and (3) after the solution turns black, stirring for 8min, then carrying out ultrasonic treatment for 8min, adding a citric acid solution, stirring for 24h, wherein the addition amount of the citric acid solution is 1.68g, and washing to obtain the magnetic porous ceramic adsorbing material.
Comparative example 1
This comparative example was carried out under the same conditions as in example 1, except that the magnetic nano iron oxide particles were not supported on the mesoporous ceramic substrate.
Application example 1
A piece of fly ash magnetic porous ceramic material prepared in examples 1 to 3 and comparative example 1, which had a mass of 1.0g, was placed in a conical flask and filled with 10ml of 100mg/l lead nitrate solution. The Erlenmeyer flask was placed on a constant temperature shaker at 25 ℃ with a shaking speed of 150 rpm. Sampling when the adsorption time is 10min, 20min, 30min, 40min, 50min, 60min, 70min and 80min, detecting by using an inductively coupled plasma atomic emission spectrometer (ICP), and calculating the removal rate of the magnetic porous ceramic material on the divalent lead ions, wherein the results are shown in Table 2.
TABLE 2
Application example 2
A piece of fly ash magnetic porous ceramic material prepared in examples 1 to 3 and comparative example 1, with the mass of 1.0g, was placed in a conical flask and filled with 10ml of 100mg/l copper sulfate solution. The Erlenmeyer flask was placed on a constant temperature shaker at 25 ℃ with a shaking speed of 150 rpm. Sampling when the adsorption time is 10min, 20min, 30min, 40min, 50min, 60min, 70min and 80min, and calculating the removal rate of the magnetic porous ceramic material on the divalent copper ions by adopting an inductively coupled plasma atomic emission spectrometer (ICP), wherein the results are shown in Table 3.
TABLE 3
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The preparation method of the magnetic porous ceramic adsorption material is characterized by comprising the following steps of:
(1) mixing the fly ash with auxiliary materials, and stirring and mixing the fly ash with a gel and a solvent to obtain fly ash slurry;
(2) injecting the fly ash slurry obtained in the step (1) into a mould, standing for forming and drying to obtain a porous dry blank;
(3) sintering the porous dry blank obtained in the step (2) to obtain a porous ceramic substrate;
(4) and (4) preparing magnetic nanoparticles on the porous ceramic substrate prepared in the step (3) to obtain the magnetic porous ceramic adsorption material.
2. The preparation method according to claim 1, wherein the auxiliary materials in step (1) comprise kaolin, a dispersing agent and graphite;
preferably, the mass ratio of the fly ash to the kaolin, the dispersing agent and the graphite is 10 (2-3) to (0.5-1) to (1-1.5);
preferably, the dispersant comprises ammonium citrate.
3. The method for preparing according to claim 1 or 2, wherein the gelling agent of step (1) comprises gelatin, xanthan gum, gellan gum, etc.;
preferably, the gelatin is a gelatin aqueous solution, and the mass concentration of the gelatin aqueous solution is 4-8 wt%;
preferably, the solvent of step (1) is water;
preferably, the stirring temperature in the step (1) is 40-50 ℃, and the time is 20-30 min;
preferably, the solid content of the fly ash slurry in the step (1) is 50-60 wt%.
4. The preparation method according to any one of claims 1 to 3, wherein the temperature of the standing and forming in the step (2) is 5 to 10 ℃;
preferably, the drying temperature after the molding in the step (2) is 20-30 ℃;
preferably, the drying time of the step (2) is not less than 24 h.
5. The production method according to any one of claims 1 to 4, wherein the sintering of step (3) includes one-stage sintering and two-stage sintering;
preferably, the temperature of the first-stage sintering is 500-600 ℃;
preferably, the temperature rise rate of the first-stage sintering is 5-8 ℃/min;
preferably, the time for the first-stage sintering is 1-2 h;
preferably, the temperature of the two-stage sintering is 600-1250 ℃;
preferably, the temperature rise rate of the two-stage sintering is 5-6 ℃/min;
preferably, the time of the second-stage sintering is 1-2 h.
6. The method for preparing magnetic nanoparticles according to any one of claims 1 to 5, wherein the method for preparing magnetic nanoparticles on the porous ceramic substrate in the step (4) comprises:
dissolving ferric salt and ferrous salt in nitrogen atmosphere to obtain a mixed solution, immersing the porous ceramic substrate into the mixed solution, gradually and slowly dripping ammonia water, stirring and then ultrasonically treating the solution until the solution turns black, adding citric acid solution, stirring and washing to obtain the magnetic porous ceramic adsorbing material.
7. The preparation method according to claim 6, wherein the molar ratio of the ferric salt to the ferrous salt in the mixed solution of the ferric salt and the ferrous salt is 2-3: 1;
preferably, the ferric salt comprises ferric chloride hexahydrate, and the ferrous salt comprises ferrous chloride tetrahydrate;
preferably, the mass concentration of the ammonia water is 20-30%;
preferably, the volume ratio of the ammonia water to the mixed solution of the ferric salt and the ferrous salt is 1: 20-25;
preferably, the stirring time before the ultrasonic treatment is 8-15 min;
preferably, the time of the ultrasonic treatment is 8-15 min;
preferably, the prepared citric acid solution is prepared by dissolving 1.0-2.0 g of citric acid in 10ml of water;
preferably, the time for stirring after adding the citric acid is not less than 24 h.
8. The method of any one of claims 1 to 7, comprising the steps of:
(1) mixing fly ash, kaolin, a dispersant ammonium citrate and graphite, wherein the mass ratio of the fly ash to the kaolin to the dispersant ammonium citrate to the graphite is 10 (2-3) to (0.5-1) to (1-1.5), and stirring and mixing the fly ash, the kaolin to the dispersant ammonium citrate and the graphite with a gelatin solution with a mass concentration of 4-8 wt% and water at 40-50 ℃ for 20-30 min to obtain a fly ash slurry, wherein the solid content of the fly ash slurry is 40-50 wt%;
(2) injecting the fly ash slurry obtained in the step (1) into a mold, standing and molding at 5-10 ℃, and drying at 20-30 ℃ for not less than 24 hours to obtain a porous dry blank;
(3) sintering the porous dry blank obtained in the step (2) to obtain a porous ceramic substrate;
the sintering comprises first-stage sintering and second-stage sintering, wherein the temperature of the first-stage sintering is 500-600 ℃, the heating rate is 5-8 ℃/min, and the time is 1-2 h; the temperature of the two-stage sintering is 600-1250 ℃, the heating rate is 5-6 ℃/min, and the time is 1-2 h;
(4) immersing the porous ceramic substrate prepared in the step (3) into a mixed solution obtained by dissolving ferric chloride hexahydrate and ferrous chloride tetrahydrate at room temperature in a nitrogen atmosphere, wherein the molar ratio of the ferric chloride hexahydrate to the ferrous chloride tetrahydrate is 2-3: 1; dropwise adding ammonia water, wherein the mass concentration of the ammonia water is 20-30%, and the volume ratio of the ammonia water to the mixed solution is 1: 20-25; and (3) after the solution turns black, stirring for 8-15 min, then carrying out ultrasonic treatment for 8-15 min, adding a citric acid solution, stirring for not less than 24h, wherein the citric acid solution is obtained by dissolving 1.0-2.0 g of citric acid in 10ml of water solution, and washing to obtain the magnetic porous ceramic adsorbing material.
9. A magnetic porous ceramic adsorbing material prepared by the preparation method of any one of claims 1 to 8.
10. The use of the magnetic porous ceramic adsorbent material according to claim 9, wherein the magnetic porous ceramic adsorbent material is used for adsorbing divalent heavy metal ions in water.
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