CN114229855B - Method for extracting mesoporous silica from fly ash by utilizing boron oxide circulating phase separation - Google Patents

Method for extracting mesoporous silica from fly ash by utilizing boron oxide circulating phase separation Download PDF

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CN114229855B
CN114229855B CN202210001487.XA CN202210001487A CN114229855B CN 114229855 B CN114229855 B CN 114229855B CN 202210001487 A CN202210001487 A CN 202210001487A CN 114229855 B CN114229855 B CN 114229855B
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fly ash
boron oxide
acid leaching
mesoporous silica
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CN114229855A (en
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李爱民
武静文
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Dalian University of Technology
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    • C01B33/113Silicon oxides; Hydrates thereof
    • C01B33/12Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103Solid 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
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid 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 surface properties or porosity
    • B01J20/28078Pore diameter
    • B01J20/28083Pore diameter being in the range 2-50 nm, i.e. mesopores
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08Silica
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Abstract

A method for extracting mesoporous silica from fly ash by utilizing boron oxide cyclic phase splitting belongs to the technical field of waste resource utilization. Mixing the fly ash and the boron oxide according to a proportion, and performing ball milling to uniformly mix the fly ash and the boron oxide; placing the mixed fly ash powder in a muffle furnace, and carrying out heating treatment under the condition of air or oxidizing atmosphere; crushing the obtained glassy solid product into powder; performing acid leaching treatment on the powder by using a nitric acid solution to obtain an acid leaching mixture; carrying out solid-liquid separation on the acid leaching mixture liquid by a centrifugation or filtration method to respectively obtain acid leaching liquid and solid residues, and washing and drying the obtained solid residues to obtain mesoporous silica with the purity of more than 90%; and recovering boric acid from the acid leaching solution by a crystallization technology, wherein the acid leaching solution is a high-concentration nitric acid solution, can be recycled, and is subjected to acid leaching for multiple times. Meanwhile, the method can rapidly and efficiently remove most of metal oxides in the fly ash, and the removal rate reaches over 90 percent.

Description

Method for extracting mesoporous silica from fly ash by utilizing boron oxide circulating phase separation
Technical Field
The invention belongs to the technical field of waste resource utilization, and particularly relates to a method for extracting mesoporous silica from fly ash by utilizing boron oxide cyclic phase separation.
Background
The fly ash is a main solid waste generated after coal combustion, the yield of the fly ash in China in 2019 is up to 6.55 hundred million tons, and the fly ash is single industrial solid waste with the largest yield. The main chemical composition of the fly ash is SiO 2 、Al 2 O 3 、Fe 2 O 3 CaO, etc., and also contains a small amount of heavy metal oxides such as lead, mercury, chromium, etc. The fly ash is not treated properly, and harmful elements in the fly ash can pollute soil, water and atmosphere and cause harm to human beings, animals and plants. The fly ash is mainly applied to building engineering, road engineering, ceramic industry, soil improvement and the like at present, the preparation of materials such as zeolite, adsorbent, microcrystalline glass and the like by utilizing the high added value of the fly ash still belongs to the research level at presentAnd (4) section.
At present, valuable substances in the fly ash are not fully and highly utilized in the main utilization mode of the fly ash, and the main utilization mode is a utilization mode with lower economy, while related researches on applying the fly ash to manufacture materials do not fully remove metal oxides in the fly ash, and silicon dioxide in the fly ash is not efficiently purified. The application of the phase separation method to the treatment of the fly ash mainly aims at preparing microcrystalline glass or porous glass, but metal oxides in the fly ash are not effectively removed but fixed in a glass material, and meanwhile, the experimental operation is relatively complex, the economic benefit is general, and large-scale industrial production is not realized. In addition, no application of boron oxide to promotion of phase splitting of the fly ash and realization of full removal of metal oxides in the fly ash and purification of silicon dioxide is found at present, so the method is a new way for resource utilization of the fly ash, the method is simple to operate, low in energy consumption, low in cost of the boron oxide additive, excellent in effect of removing the metal oxides, and capable of achieving removal rate of most of the metal oxides by more than 90%, and meanwhile, the final product is a mesoporous material with good performance, and high value-added utilization of the fly ash can be realized. The method of the invention applies glass phase splitting to the treatment of the fly ash, wherein the phase splitting is a phenomenon that certain components in silicate melt and glass are deflected to form different phases of chemical compositions in some areas, boron oxide is added and melted at high temperature, so that silicon dioxide and boron oxide in the fly ash can be deflected, the boron oxide can melt metal oxide, in the heat treatment process, the metal realizes the migration from a silicon-rich phase to a boron-rich phase, the boron oxide is easily dissolved in acid and can be completely dissolved in nitric acid solution, and therefore, the purposes of complete removal of the metal oxide in the fly ash and purification of the silicon dioxide are realized. The invention provides a new mode for the treatment and high-quality application of the fly ash, and realizes the resource utilization of the fly ash.
Disclosure of Invention
In view of the above problems and technical analyses, the present invention provides a method for extracting mesoporous silica from fly ash by using boron oxide cyclic phase separation, the method comprising: smelting oxidationThe method has the advantages of simple operation, obvious effect and better economy, and the prepared SiO has high purity of more than 90 percent 2 Has larger specific surface area and pore volume, concentrated pore size distribution and is a mesoporous material.
The invention adopts the following technical scheme:
a method for extracting mesoporous silica from fly ash by utilizing boron oxide cyclic phase separation comprises the following steps:
(1) Mixing fly ash and boron oxide according to a mass ratio of 1:0.17-0.54, and ball milling to mix evenly;
(2) Placing the mixed fly ash powder obtained in the step (1) in a muffle furnace, and performing heating treatment under the condition of air or oxidizing atmosphere, wherein the final temperature of the heating treatment is 800-1500 ℃, the temperature is kept for 0-4h at the current temperature after the temperature is raised, and the temperature is reduced at a slow speed after the heat treatment stage is finished;
(3) Crushing the glassy solid product obtained in the step (2) into powder;
(4) Performing acid leaching treatment on the powder in the step (3) by using a nitric acid solution to obtain an acid leaching mixture;
(5) Carrying out solid-liquid separation on the acid leaching mixture liquid obtained in the step (4) by a centrifugal or filtering method to respectively obtain acid leaching liquid and solid residues, and washing and drying the obtained solid residues to obtain mesoporous silica with the purity of more than 90%;
(6) And (5) recovering boric acid from the pickle liquor obtained in the step (5) by a crystallization technology, and drying the boric acid to obtain boron oxide for recycling. The acid leaching solution is a high-concentration nitric acid solution, acid and metal ions can be separated through a diffusion dialysis method, nitric acid is recycled, and acid leaching is carried out for multiple times. The metal ions are recovered by chemical precipitation, ion exchange techniques, and the like.
In the step (1), the boron oxide can be produced by chemical industry, or the boron oxide obtained by separation and extraction from solid waste boron slag can be adopted.
In the step (2), the heating rate is 5-10 ℃/min.
In the step (3), the particle size of the crushed powder is less than 0.15mm.
In the step (4), the concentration of the nitric acid solution is 0.5-8mol/L.
In the step (4), the temperature of acid leaching treatment is 20-90 ℃; the time of acid leaching treatment is 1.5-6h.
In the step (4), the volume ratio of the powder obtained in the step (3) to the nitric acid solution is 1:5-50.
The invention has the beneficial effects that: the method can rapidly and efficiently remove most of metal oxides in the fly ash, and the removal rate reaches over 90 percent. The purity of the silicon dioxide in the purified fly ash is up to more than 97%, and the obtained silicon dioxide powder is mesoporous silicon dioxide, has larger specific surface area and concentrated pore diameter, and can be applied to the application fields of mesoporous materials such as pollutant adsorption or catalyst carriers. The method has the advantages of simple process, short treatment time, low energy consumption, low additive cost and high product economic value, can be applied to large-scale industrial treatment, and provides a new way for high value-added utilization of the fly ash.
Drawings
FIG. 1 is a nitrogen adsorption-desorption curve and a pore size distribution diagram of the silica powder obtained by the present invention.
FIG. 2 is a scanning electron micrograph of the silica powder obtained according to the present invention.
Figure 3 is an XRD pattern of the acid leach product obtained in accordance with the present invention.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1:
uniformly mixing 75g of fly ash and 25g of boron oxide, uniformly mixing the fly ash and the boron oxide by using a ball mill, treating the mixture to 200 meshes, putting 10g of mixed fly ash powder into a muffle furnace, heating at a rate of 10 ℃/min, and carrying out high-temperature heat treatment at 1100 ℃ in an air atmosphere for 60min; naturally cooling to room temperature, and crushing the heat-treated blocky product to 200 meshes; adding the crushed product into a nitric acid solution of 7.4mol/L, wherein the volume ratio is 1:10, soaking for 5 hours at 90 ℃. And (3) centrifuging the acid leaching product, performing solid-liquid separation, washing the solid residue with water for 3 times, and drying at 105 ℃ for 10 hours to obtain high-purity silicon dioxide powder. . Condensing the acid leaching solution to separate out boric acid crystal, filtering and recovering.
XRF and XRD analysis shows that the solid residue after acid leaching is water washed and dried to obtain SiO as main component 2 (98.11%)、Al 2 O 3 (0.659%) and CaO (0.309%), diffraction peaks corresponding to SiO 2 Characteristic peak. The specific surface area of the silica powder was 364.2m 2 In the range of 3-6nm in micropore size. Na removing rate of metal oxide in fly ash 2 100% of O, 99.456% of MgO and Al 2 O 3 97.686%, caO 96.99%, and the removal rate of CuO, znO and SrO is 100%.
Example 2:
mixing fly ash and boron oxide according to a mass ratio of 1:0.18, uniformly mixing by using a ball mill, treating to 200 meshes, putting 20g of mixed fly ash powder into a muffle furnace, heating at a rate of 10 ℃/min, and carrying out high-temperature heat treatment at 1000 ℃ in an air atmosphere for 60min; naturally cooling to room temperature, and crushing the heat-treated blocky product to 200 meshes; adding the crushed product into a 5mol/L nitric acid solution, wherein the volume ratio is 1:10, soaking for 4 hours at 90 ℃. And (3) centrifuging the acid leaching product, performing solid-liquid separation, washing the solid residue with water for 3 times, and drying at 105 ℃ for 10 hours to obtain high-purity silicon dioxide powder. Condensing the acid leaching solution to separate out boric acid crystal, filtering and recovering.
XRF and XRD analysis shows that the solid residue after acid leaching is water washed and dried to obtain SiO as main component 2 (91.68%)、Al 2 O 3 (3.06%)、Fe 2 O 3 (1.63%) and CaO (1.06%), the diffraction peak is a bulge-shaped broad peak corresponding to amorphous SiO 2 . Removal rate Na of metal oxide in fly ash 2 97.76% of O, 90.49% of MgO and Al 2 O 3 The content was 88.9%.
Example 3:
mixing fly ash and boron oxide according to a mass ratio of 1:0.33, uniformly mixing by using a ball mill, treating to 200 meshes, putting 20g of mixed fly ash powder into a muffle furnace, heating at a rate of 10 ℃/min, and carrying out high-temperature heat treatment at 1100 ℃ in an air atmosphere for 120min; naturally cooling to room temperature, and crushing the heat-treated blocky product to 200 meshes; adding the crushed product into a 5mol/L nitric acid solution, wherein the volume ratio is 1:10, soaking for 4 hours at 90 ℃. And (3) centrifuging the acid leaching product, performing solid-liquid separation, washing solid residues for 3 times, and drying at 105 ℃ for 10 hours to obtain high-purity silicon dioxide powder.
After XRF and XRD analysis, the solid residue after acid leaching is washed and dried, and the main component is SiO 2 (97.3%)、Al 2 O 3 (0.611%)、Fe 2 O 3 (0.626%) and CaO (0.287%), the diffraction peak is a bulge-like broad peak corresponding to amorphous SiO 2 . Na removing rate of metal oxide in fly ash 2 100% of O, 99.6% of MgO and Al 2 O 3 97.8% by weight, K 2 99% of O and 97.2% of CaO.

Claims (10)

1. A method for extracting mesoporous silica from fly ash by utilizing boron oxide cyclic phase separation is characterized by comprising the following steps:
(1) Mixing fly ash and boron oxide according to a mass ratio of 1:0.17-0.54, and ball milling to mix evenly;
(2) Placing the mixed fly ash powder obtained in the step (1) in a muffle furnace, and performing heating treatment under the condition of air or oxidizing atmosphere, wherein the final temperature of the heating treatment is 800-1500 ℃, the temperature is kept for 0-4h at the current temperature after the temperature is raised, and the temperature is reduced at a slow speed after the heat treatment stage is finished;
(3) Crushing the glassy solid product obtained in the step (2) into powder;
(4) Performing acid leaching treatment on the powder in the step (3) by using a nitric acid solution to obtain an acid leaching mixture;
(5) Carrying out solid-liquid separation on the acid leaching mixture liquid obtained in the step (4) by a centrifugal or filtering method to respectively obtain acid leaching liquid and solid residues, and washing and drying the obtained solid residues to obtain mesoporous silica with the purity of more than 90%;
(6) Recovering boric acid from the pickle liquor obtained in the step (5) by a crystallization technology, and drying the boric acid to obtain boron oxide for recycling; the pickle liquor is a high-concentration nitric acid solution, can be recycled and is used for multiple acid leaching.
2. The method for extracting mesoporous silica from fly ash by using boron oxide cyclic phase separation as claimed in claim 1, wherein in the step (3), the particle size of the crushed powder is less than 0.15mm.
3. The method for extracting mesoporous silica from fly ash by using boron oxide cyclic phase separation as claimed in claim 1 or 2, wherein in the step (2), the temperature rise rate is 5-10 ℃/min.
4. The method for extracting mesoporous silica from fly ash by using boron oxide cyclic phase separation as claimed in claim 1 or 2, wherein in the step (4), the concentration of the nitric acid solution is 0.5-8mol/L.
5. The method for extracting mesoporous silica from fly ash by using boron oxide cyclic phase separation as claimed in claim 3, wherein in the step (4), the concentration of the nitric acid solution is 0.5-8mol/L.
6. The method for extracting mesoporous silica from fly ash by using boron oxide cyclic phase separation as claimed in claim 1, 2 or 5, wherein in the step (4), the temperature of acid leaching treatment is 20-90 ℃; the time of acid leaching treatment is 1.5-6h.
7. The method for extracting mesoporous silica from fly ash by using boron oxide circulating phase separation as claimed in claim 3, wherein in the step (4), the temperature of acid leaching treatment is 20-90 ℃; the time of acid leaching treatment is 1.5-6h.
8. The method for extracting mesoporous silica from fly ash by using boron oxide cyclic phase separation as claimed in claim 4, wherein in the step (4), the temperature of acid leaching treatment is 20-90 ℃; the time of acid leaching treatment is 1.5-6h.
9. The method for extracting mesoporous silica from fly ash by using boron oxide cyclic phase separation as claimed in claim 1, 2, 5, 7 or 8, wherein in the step (4), the volume ratio of the powder obtained in the step (3) to the nitric acid solution is 1:5-50.
10. The method for extracting mesoporous silica from fly ash by using boron oxide cyclic phase separation as claimed in claim 6, wherein in the step (4), the volume ratio of the powder obtained in the step (3) to the nitric acid solution is 1:5-50.
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