CN114906857B - Treatment method of coal gangue, and silicon oxide nano-sheet, porous silicate material and iron oxide red prepared from coal gangue - Google Patents

Treatment method of coal gangue, and silicon oxide nano-sheet, porous silicate material and iron oxide red prepared from coal gangue Download PDF

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CN114906857B
CN114906857B CN202210492204.6A CN202210492204A CN114906857B CN 114906857 B CN114906857 B CN 114906857B CN 202210492204 A CN202210492204 A CN 202210492204A CN 114906857 B CN114906857 B CN 114906857B
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CN114906857A (en
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王文波
赵文廷
郭芳
韩雷
张寰
何庆东
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Inner Mongolia University
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Abstract

The invention discloses a treatment method of coal gangue, which comprises the following steps of: crushing coal gangue, and calcining to obtain layered silicate minerals; dispersing the layered silicate mineral into an aqueous solution containing an acid and a dispersing agent according to the solid-liquid mass ratio of 1:5-20, and dissolving out metal ions in the layered silicate mineral by the acid to obtain a suspension; placing the suspension in a closed reaction vessel, and carrying out hydrothermal reaction for 2-24 h at the temperature of 100-240 ℃ and the pressure of 1-7 MPa to obtain a mixed product; separating the solid in the mixed product, washing, drying and crushing the solid to obtain a silicon oxide nano sheet; the method can prepare the white silica nano-sheet, the porous silicate material and the iron oxide red with high value and high performance through the coal gangue with low cost, and improves the added value of the coal gangue.

Description

Treatment method of coal gangue, and silicon oxide nano-sheet, porous silicate material and iron oxide red prepared from coal gangue
Technical Field
The invention relates to a non-metal mineral deep processing and nano material preparation technology, in particular to a treatment method of coal gangue, and a silicon oxide nano sheet, a porous silicate material and iron oxide red prepared from the coal gangue.
Background
Gangue is a large amount of solid waste generated in the coal production and coal washing processes, and accounts for 15% of the coal yield. According to incomplete statistics, the accumulated stacking amount of the coal gangue in China is over 60 hundred million tons, and the discharge amount of the coal gangue is increased year by about 5 hundred million to 8 hundred million tons per year. The stacking of the huge amount of solid waste of the coal gangue not only occupies land and wastes resources, but also endangers ecological environment and human health, brings serious environmental and potential safety hazards, and is urgent to develop a new technology for recycling the solid waste of the coal gangue.
From the perspective of mineralogy, coal gangue contains clay minerals (such as montmorillonite, illite, kaolinite, muscovite, quartz, feldspar and the like) represented by kaolinite, so the coal gangue is also a natural mineral resource with abundant reserves.
In recent years, extraction of valuable components from coal gangue to increase the added value thereof has been attracting attention. Among them, in the prior art for extracting silica from coal gangue, although silica is obtained, nano-scale silica nano-sheets with high whiteness cannot be obtained, the preparation process is complex, and a large amount of waste liquid is generated (the disposal and utilization of the waste liquid are not involved in the prior art). In addition, the waste liquid generated in the preparation of the silicon dioxide nano-sheet by using the coal gangue is used for synthesizing the porous silicate material and the iron oxide red, so that the full-component utilization of the coal gangue is realized, and no report and technical application precedent exists at present.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a treatment method of coal gangue, and a silicon oxide nano sheet, a porous silicate material and iron oxide red prepared from the coal gangue, wherein the nano silicon oxide nano sheet with high whiteness can be obtained.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the treatment method of the coal gangue comprises the following steps:
crushing coal gangue, and calcining to obtain layered silicate minerals;
dispersing the layered silicate mineral into an aqueous solution containing acid and a dispersing agent according to a solid-liquid mass ratio of 1:5-20 to obtain a suspension;
placing the suspension in a closed reaction container, and carrying out hydrothermal reaction for 2-24 hours at the temperature of 100-240 ℃ and the pressure of 1-7 MPa to dissolve out metal ions in the layered silicate mineral by acid in the reactant to obtain a mixed product;
and separating the solid in the mixed product, and washing, drying and crushing the solid to obtain the silicon oxide nano-sheet.
Preferably, the calcining temperature of the gangue is 400-800 ℃ and the calcining time is 2-12 h;
the acid is one or more than two of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfamic acid, oxalic acid, citric acid, ethylenediamine tetraacetic acid, tartaric acid, ascorbic acid and malic acid;
in the aqueous solution, the concentration of hydrogen ions of the acid is 0.25mol/L to 5mol/L;
the dispersing agent is one or more than two of nitrilotriacetic acid, sodium glutamate, ammonium citrate, sodium citrate and sodium hexametaphosphate;
in the aqueous solution, the mass of the dispersing agent is 0.1% -1% of the mass of the layered silicate mineral;
the mass percentage of kaolinite in the coal gangue is more than 70%.
Preferably, the treatment method of the coal gangue further comprises the following steps:
separating liquid in the mixed product, adding an alkaline metal compound into the liquid to adjust the pH value of the liquid to be 4-8, adding metal salt into the liquid to adjust the metal ion composition in the liquid, and adding soluble silicate and an organic amine auxiliary agent into the liquid to obtain a mixed liquid;
reflux heating the mixed solution at 60-120 ℃ for 2-12 h, and collecting solid products;
and carrying out heat treatment on the solid product at the temperature of 200-700 ℃ for 1-3 h to obtain the porous silicate material.
Preferably, the alkaline metal compound is selected from one or more of magnesium carbonate, magnesium hydroxide, magnesium oxide, basic magnesium carbonate, zinc oxide, zinc hydroxide, calcium oxide, calcium hydroxide, calcium carbonate and dolomite;
the added mass of the alkaline metal compound is 5-30% of the mass of the liquid;
the metal salt is selected from one or more of magnesium chloride, magnesium sulfate, magnesium nitrate, magnesium acetate, zinc chloride, zinc sulfate, zinc nitrate, calcium chloride and calcium nitrate;
the added mass of the metal salt is 20% -80% of the mass of the liquid;
the soluble silicate is selected from one or more than two of sodium metasilicate, sodium silicate, potassium metasilicate, potassium silicate, potassium sodium silicate and lithium silicate;
the added molar amount of the soluble silicate is 75-200% of the total molar amount of the added alkali metal compound and the metal salt;
the organic amine auxiliary agent is one or more than two selected from ethylenediamine, diethylenetriamine, triethylenetetramine, 1, 2-propylene diamine and formamide;
the molar amount of the organic amine auxiliary agent added is 0.5% -1.5% of the total molar amount of the alkaline metal compound and the metal salt added.
Preferably, the treatment method of the coal gangue further comprises the following steps:
separating liquid in the mixed product, adding iron powder and/or alkaline ferric salt into the liquid, and neutralizing residual acid in the liquid to obtain an iron ion-rich solution;
adding precipitator alkali into the solution rich in iron ions, adjusting the pH to 8-12, and heating at 30-80 ℃ for reaction for 5-10 h to obtain red solid;
and carrying out heat treatment on the red solid to obtain iron oxide red.
Preferably, the alkaline ferric salt is selected from one or more than two of ferric hydroxide, ferric carbonate, ferrous hydroxide and basic ferric carbonate;
the precipitator alkali is one or more than two of sodium hydroxide, sodium acetate, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate and potassium silicate;
the temperature of the iron oxide red heat treatment is 300-1000 ℃;
the added mass of the iron powder and/or the alkaline ferric salt is 10-80% of the mass of the liquid.
The invention also discloses the silicon oxide nano-sheet, the porous silicate material and the iron oxide red prepared by the method.
Preferably, the pore diameter of the porous silicate material is 2 nm-50 nm; the average pore diameter of the porous silicate material is 3 nm-15 nm; the average specific surface area of the porous silicate material is 100-800 m 2 /g。
The implementation of the embodiment of the invention has the following beneficial effects:
according to the embodiment of the invention, the layered silicate mineral is obtained by calcining the coal gangue, and then metal ions in the octahedral layer of the layered silicate mineral are dissolved out through acid corrosion treatment, so that the layered structure of the layered silicate mineral can be reserved, and the nano flaky silicon oxide is obtained; the silicon oxide nano-sheets with extremely small particles (average particle diameter of 1 nm-5 nm) can be obtained by using the dispersing agent to obtain the suspension, carrying out the hydrothermal reaction on the suspension and controlling the parameters of the hydrothermal reaction, and the experiment shows that the prepared silicon oxide nano-sheets have whiteness as high as 94.
The invention can further prepare the residual products of the prepared silicon oxide nano-sheets into porous silicate materials with high adsorption performance or iron oxide red with high redness through co-production, thereby not only improving the utilization value and high value-added conversion of the coal gangue, but also avoiding the environmental pollution caused by waste acid and the high cost of waste liquid treatment.
The invention adds soluble silicate, organic amine auxiliary agent and metal salt into the liquid from which the silicon oxide nano-sheet is separated, and adopts a reflux heating mode to form a novel porous silicate material, which has higher adsorption performance.
According to the invention, iron powder or alkaline ferric salt is added into the liquid from which the silicon oxide nano-sheets are separated, so that the liquid is rich in iron ions, and high-purity and high-redness iron oxide red can be precipitated from the liquid by controlling the parameters of heating reaction.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Wherein:
fig. 1 is SEM pictures of the gangue materials used in examples 1 to 6, the layered silicate minerals prepared in example 3, and the silica nanoplatelets prepared in example 3 under different magnifications, wherein a and d are the gangue materials, b and e are the layered silicate minerals, and c and f are the silica nanoplatelets.
Fig. 2 is a TEM photograph of the silicon oxide nanoplatelets prepared in example 3.
FIG. 3 is an SEM photograph of a porous silicate adsorbent prepared from calcined gangue acid-etched waste liquid at a low magnification (scale 1 μm) according to the porous silicate material prepared in example 3 of the present invention; b is an SEM image of a porous silicate adsorbent prepared from calcined gangue acid-etched waste liquid at high magnification (scale 200 nm).
FIG. 4 is a nitrogen adsorption-desorption isotherm of the porous silicate material produced in example 3 of the present invention.
FIG. 5 is a graph showing pore size distribution of the porous silicate material obtained in example 3 of the present invention.
FIG. 6 is an XRD plot of calcined coal gangue (i.e., layered silicate minerals), silica nanoplatelets, and porous silicate materials produced in example 3 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention discloses a treatment method of coal gangue, which comprises the following steps:
step 1: and crushing the gangue, and calcining to obtain the phyllosilicate mineral.
The gangue contains layered clay mineral represented by kaolinite and carbon, and the layered silicate mineral is obtained by calcining the gangue and controlling the parameters of calcination to remove the carbon in the gangue. The crystals of the layered silicate mineral mainly comprise silicon oxygen tetrahedra and metal oxygen octahedra (MO) such as Mg, al, fe and the like 6 ) A composition in which silicon oxygen tetrahedrons are connected in a two-dimensional direction in a manner of common vertex angles to form a grid layer of hexagonal arrangement, and the tip oxygen not shared by each silicon oxygen tetrahedron is directed to one side; the layered unit structure is formed by the silicon oxygen tetrahedral layer and the oxyoctahedron layer sharing the oxygen tip of the silicon oxygen tetrahedral layer.
Specifically, the calcining temperature of the gangue is 400-800 ℃ and the calcining time is 2-12 h.
Preferably, the mass percentage of the kaolinite in the gangue is not less than 70%, and the kaolinite is of a lamellar structure, so that the content of a calcined lamellar product is improved, and the silica nanosheet is further prepared.
Step 2: dispersing the layered silicate mineral into an aqueous solution containing acid and a dispersing agent according to the solid-liquid mass ratio of 1:5-20, wherein under the hydrothermal reaction condition, the acid can efficiently dissolve out metal ions in the layered silicate mineral to obtain a suspension rich in silicon oxide nano-sheets and octahedral metal ions; the metal ions are dissolved in the solution, the layered structure of the layered silicate mineral is preserved, and layered silica nanoplatelets are obtained by the "self-templating" effect of the layered silicate mineral.
In a specific embodiment, the acid may be one or more selected from hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfamic acid, oxalic acid, citric acid, ethylenediamine tetraacetic acid, tartaric acid, ascorbic acid, malic acid, and the like, and the concentration of hydrogen ions of the acid in the aqueous solution is 0.25mol/L to 5mol/L.
In a specific embodiment, the dispersing agent may be one or more selected from nitrilotriacetic acid, sodium glutamate, ammonium citrate, sodium citrate and sodium hexametaphosphate; in the aqueous solution, the mass of the dispersant may be 0.1% to 1% of the mass of the layered silicate mineral.
In this step, the large particles and quartz sand which are not dispersed in the suspension are filtered out, and specifically, the suspension can be passed through a 300-600 mesh vibrating screen to remove the large particles and quartz sand which are not dispersed, so as to obtain a uniform suspension.
Step 3: the suspension is put into a closed reaction vessel to carry out hydrothermal reaction for 2 to 24 hours at the temperature of 100 to 240 ℃ and the pressure of 1 to 7MPa, thus obtaining the mixed product. And separating the solid in the mixed product, washing, drying and crushing the solid to obtain the white silicon oxide nano-sheet.
In the step, the particle morphology of the formed solid product is controlled by controlling the parameters of the hydrothermal reaction, including the concentration, temperature, pressure, hydrothermal time and the like of each reactant, and under the condition of the parameters, the whiteness of the silicon oxide nano-sheet prepared by the method reaches more than 90. The invention solves the technical bottleneck problem of synthesizing the nano material by utilizing the gangue and opens up a new way for high-value, high-efficiency and comprehensive utilization of the gangue with rich reserves in China. In addition, the hydrothermal reaction adopted by the invention has simpler preparation process and low cost, and is convenient for large-scale mass production.
The silicon oxide nano-sheet obtained by the invention is a nano-material, has the whiteness reaching more than 90 and stable quality, and has wide application prospect in various aspects such as high polymer materials, flame retardants, composite coatings, paints, papermaking, battery diaphragm coatings, catalyst carriers, lubricating grease additives, separation membranes and the like.
Step 4: separating liquid in the mixed product, wherein abundant metal ions (aluminum ions, iron ions, magnesium ions and the like) are dissolved in the liquid, and utilizing the metal ions in the liquid and avoiding the influence of direct discharge of acidic liquid on environment protection; reflux heating the mixed solution at 60-120 deg.c for 2-12 hr to collect solid product; and carrying out heat treatment on the solid product at the temperature of 200-700 ℃ for 1-3 h to obtain the porous silicate material.
The metal ions in the porous silicate material can be adjusted by adding alkaline metal compounds, metal salts and soluble silicate, and specifically, the alkaline metal compounds can be one or more than two of magnesium carbonate, magnesium hydroxide, magnesium oxide, basic magnesium carbonate, zinc oxide, zinc hydroxide, calcium oxide, calcium hydroxide, calcium carbonate, dolomite and the like; the metal salt can be one or more selected from magnesium chloride, magnesium sulfate, magnesium nitrate, magnesium acetate, zinc chloride, zinc sulfate, zinc nitrate, calcium chloride, calcium nitrate, etc.; the soluble silicate is one or more selected from sodium metasilicate, sodium silicate, potassium metasilicate, potassium silicate, potassium sodium silicate and lithium silicate.
Further, the added mass of the alkaline metal compound can be 5-30% of the mass of the liquid; the added mass of the metal salt can be 20-80% of the mass of the liquid; the soluble silicate may be added in a molar amount of 75% to 200% of the total molar amount of the alkali metal compound and the metal salt added.
The organic amine auxiliary agent is used as a dispersing agent and also used as a pore-forming agent in the invention, firstly, the organic amine auxiliary agent helps soluble silicate, metal salt and the like to be fully dispersed in liquid in the form of tiny particles, namely, the particle size of a reactant is reduced, so that the nano material is formed, and secondly, the organic amine auxiliary agent volatilizes in the heating process, so that the mesoporous silicate material can be obtained, has a high specific surface area, and can provide high adsorption performance, high catalytic performance and the like.
In a specific embodiment, the organic amine auxiliary agent may be one or more selected from ethylenediamine, diethylenetriamine, triethylenetetramine, 1, 2-propylenediamine, formamide, etc.; the molar amount of the organic amine auxiliary added may be 0.5% to 1.5% of the total molar amount of the basic metal compound and the metal salt added.
The pore diameter of the porous silicate material prepared by the invention is 2 nm-50 nm, the average pore diameter is 3 nm-15 nm, and the average specific surface area is 100-800 m 2 /g。
Step 5: another method for separating liquid in the mixed product and utilizing metal ions in the liquid to avoid the influence of direct discharge of acidic liquid on environment protection is as follows: iron oxide red is prepared, specifically, iron powder and/or alkaline ferric salt can be added into the liquid to neutralize residual acid in the liquid, so as to obtain an iron ion-rich solution; adding precipitator alkali into the solution rich in iron ions, adjusting the pH value to 8-12, heating and reacting for 5-10 h at the temperature of 30-80 ℃ to obtain red solid, and performing heat treatment on the red solid to obtain iron oxide red.
In a specific embodiment, the iron powder and/or the alkaline iron salt is added in an amount of 10-80% by mass, preferably 50-80% by mass, of the liquid, so as to obtain an iron ion-rich solution, thereby obtaining iron oxide red with high purity (mass more than 90%).
In one embodiment, the temperature of the iron oxide red heat treatment is 300 ℃ to 1000 ℃.
In a specific embodiment, the alkaline ferric salt may be one or more selected from ferric hydroxide, ferric carbonate, ferrous hydroxide, basic ferric carbonate, and the like.
In a specific embodiment, the precipitant base may be one or more selected from sodium hydroxide, sodium acetate, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, etc., and the addition amount of the precipitant base is based on adjusting the pH of the solution to 8-12.
The invention adopts wet method to prepare iron oxide red, the prepared iron oxide red particles are tiny and soft, and are suitable for being used as pigment, the red value of the prepared iron oxide red reaches more than 30, the heat stability and acid and alkali resistance are good, and the invention has wide application in the fields of paint, coating, plastic and the like.
The following are specific examples.
Example 1
(1) Crushing gangue (the content of kaolinite is more than 70%) into powder, calcining at 400 ℃ for 12 hours, and removing residual organic carbon to obtain the layered silicate mineral.
(2) Dispersing 10kg of calcined layered silicate mineral into an aqueous solution containing 0.25mol/L hydrochloric acid and 0.1kg of sodium glutamate according to a solid-liquid mass ratio of 1:5, and then sieving the aqueous solution with a 300-mesh vibrating screen to remove undispersed large particles and quartz sand, thereby obtaining a uniform suspension;
(3) Transferring the obtained suspension into a closed reactor, and reacting for 24 hours at the temperature of 100 ℃ and the pressure of 7MPa to obtain a mixed product containing solid and liquid;
(4) Carrying out solid-liquid separation on the obtained mixed product to obtain white solid A and liquid B;
(5) Washing the white solid A with water, drying, crushing and sieving to obtain a silicon oxide nano sheet product with the whiteness of 93;
(6) The liquid B was divided into 2 equal parts, magnesium oxide (5% by mass of the solution B) was added to the first part of the solution B, the pH of the solution was adjusted to 4, and then magnesium chloride (20% by mass of the solution B) was added to adjust the ionic composition in the solution. Then adding soluble potassium silicate (accounting for 75 percent of the total molar weight of the alkaline metal compound and the metal salt) and ethylenediamine auxiliary agent (accounting for 0.5 percent of the total molar weight of the alkaline metal compound and the metal salt) into the solution, fully and uniformly stirring, reacting for 12 hours at the temperature of 60 ℃, collecting the obtained solid product, and performing heat treatment for 1 hour at the temperature of 700 ℃ to obtain a porous silicate material product;
(7) Adding iron powder or ferric hydroxide (accounting for 10% of the mass of the solution B) into the second solution B, and neutralizing residual acid in the solution to obtain a solution C rich in ferric ions;
(8) Adding precipitator sodium hydroxide into the solution C, adjusting the pH value to 8, heating at 80 ℃ for reaction for 5 hours, collecting the obtained red solid product, and calcining at 300 ℃ to obtain the iron oxide red pigment product.
Example 2
(1) Crushing gangue (the content of kaolinite is more than 70%) into powder, calcining at 800 ℃ for 2 hours, and removing residual organic carbon to obtain the layered silicate mineral.
(2) Dispersing 10kg of calcined layered silicate mineral into an aqueous solution containing 5mol/L hydrochloric acid and 0.01kg of sodium glutamate according to a solid-liquid mass ratio of 1:20, and then sieving the aqueous solution with a 300-mesh vibrating screen to remove undispersed large particles and quartz sand, thereby obtaining a uniform suspension;
(3) Transferring the obtained suspension into a closed reactor, and reacting for 2 hours at 240 ℃ and 5MPa to obtain a mixed product containing solid and liquid;
(4) Carrying out solid-liquid separation on the obtained mixed product to obtain white solid A and liquid B;
(5) Washing the white solid A with water, drying, crushing and sieving to obtain a silicon oxide nano sheet product with the whiteness of 92;
(6) The liquid B was divided into 2 equal parts, magnesium carbonate (30% by mass of the solution B) was added to the first part of the solution B, the pH of the solution was adjusted to 7, and then magnesium sulfate (80% by mass of the solution B) was added to adjust the ionic composition in the solution. Then adding soluble sodium metasilicate (accounting for 200 percent of the total mole of the alkaline metal compound and the metal salt) and diethylenetriamine auxiliary agent (accounting for 1.5 percent of the total mole of the alkaline metal compound and the metal salt) into the solution, fully and uniformly stirring, reacting for 2 hours at 120 ℃ under the condition of temperature (under the sealed condition), collecting the obtained solid product, and performing heat treatment for 3 hours at 200 ℃ to obtain a porous silicate material product;
(7) Adding iron powder or ferric hydroxide (accounting for 80% of the mass of the solution B) into the second solution B, and neutralizing residual acid in the solution to obtain a solution C rich in ferric ions;
(8) Adding a precipitator potassium hydroxide into the solution C, adjusting the pH value to 12, reacting for 10 hours at the temperature of 30 ℃, collecting the obtained red solid product, and calcining at the temperature of 1000 ℃ to obtain the iron oxide red pigment product.
Example 3
(1) Crushing gangue (the content of kaolinite is more than 70%) into powder, calcining for 6 hours at 500 ℃ and removing residual organic carbon to obtain layered silicate mineral;
(2) Dispersing 10kg of calcined layered silicate mineral into 1.5mol/L oxalic acid and 0.05kg of ammonium citrate aqueous solution according to a solid-liquid mass ratio of 1:15, and then sieving with a 500-mesh vibrating screen to remove undispersed large particles and quartz sand, thereby obtaining uniform suspension;
(3) Transferring the obtained suspension into a closed reactor, and reacting for 8 hours at 160 ℃ and 4MPa to obtain a mixed product containing solid and liquid;
(4) Carrying out solid-liquid separation on the obtained mixed product to obtain white solid A and liquid B;
(5) Washing the white solid A with water, drying, crushing and sieving to obtain a silicon oxide nano sheet product with the whiteness of 94;
(6) The liquid B was divided into 2 equal parts, magnesium hydroxide (20% by mass of the solution B) was added to the first part of the solution B, the pH of the solution was adjusted to 6.5, and then magnesium nitrate (40% by mass of the solution B) was added to adjust the composition of ions in the solution. Then adding soluble potassium sodium silicate (accounting for 80 percent of the total mole of the alkaline metal compound and the metal salt) and triethylene tetramine auxiliary agent (accounting for 0.7 percent of the total mole of the alkaline metal compound and the metal salt), fully and uniformly stirring, reacting for 6 hours at the temperature of 80 ℃, collecting the obtained solid product, and performing heat treatment for 2 hours at the temperature of 500 ℃ to obtain a porous silicate adsorbent product;
(7) Adding ferric carbonate (accounting for 20% of the mass of the solution B) into the second solution B, and neutralizing residual acid in the solution to obtain a solution C rich in ferric ions;
(8) Adding precipitator sodium acetate into the solution C, adjusting the pH value to 9, heating at 80 ℃ for reaction for 8 hours, collecting the obtained red solid product, and calcining at 700 ℃ to obtain the iron oxide red pigment product.
Example 4
(1) Crushing gangue (the content of kaolinite is more than 70%) into powder, calcining for 3 hours at 500 ℃ and removing residual organic carbon to obtain layered silicate mineral;
(2) Dispersing 10kg of calcined layered silicate mineral into an aqueous solution of 2.0mol/L sulfuric acid and 0.06g of sodium hexametaphosphate according to a solid-liquid mass ratio of 1:16, and then sieving the aqueous solution with a 400-mesh vibrating screen to remove undispersed large particles and quartz sand, thereby obtaining a uniform suspension;
(3) Transferring the obtained suspension into a closed reactor, and reacting for 6 hours at 180 ℃ and 3MPa to obtain a mixed product containing solid and liquid;
(4) Carrying out solid-liquid separation on the obtained mixed product to obtain white solid A and liquid B;
(5) Washing the white solid A with water, drying, crushing and sieving to obtain a silicon oxide nano sheet product with the whiteness of 93.5;
(6) The liquid B was divided into 2 equal parts, calcium hydroxide (20% by mass of the solution B) was added to the first part of the solution B, the pH of the solution was adjusted to 6, and then calcium chloride (30% by mass of the solution B) was added to adjust the composition of ions in the solution. Then adding soluble lithium silicate (accounting for 50 percent of the total mole of the alkaline metal compound and the metal salt) and formamide auxiliary agent (accounting for 0.7 percent of the total mole of the alkaline metal compound and the metal salt), fully and uniformly stirring, reacting for 6 hours at the temperature of 80 ℃, collecting the obtained solid product, and performing heat treatment for 2 hours at the temperature of 500 ℃ to obtain a porous silicate adsorbent product;
(7) Adding basic ferric carbonate (accounting for 18% of the mass of the solution B) into the second solution B, and neutralizing residual acid in the solution to obtain a solution C rich in ferric ions;
(8) Adding precipitator sodium silicate into the solution C, adjusting the pH value to 10, heating at 60 ℃ for reaction for 8 hours, collecting the obtained red solid product, and calcining at 700 ℃ to obtain the iron oxide red pigment product.
Example 5
(1) Crushing coal gangue (the content of kaolinite is more than 70%) into powder, calcining for 2 hours at 550 ℃ and removing residual organic carbon to obtain layered silicate mineral;
(2) Dispersing 10kg of calcined layered silicate mineral into an aqueous solution of 2.2mol/L phosphoric acid and 0.05kg of nitrilotriacetic acid according to a solid-liquid mass ratio of 1:14, and then sieving with a 400-mesh vibrating screen to remove undispersed large particles and quartz sand, thereby obtaining a uniform suspension;
(3) Transferring the obtained suspension into a closed reactor, and reacting for 8 hours at 160 ℃ and 6MPa to obtain a mixed product containing solid and liquid;
(4) Carrying out solid-liquid separation on the obtained mixed product to obtain white solid A and liquid B;
(5) Washing the white solid A with water, drying, crushing and sieving to obtain a silicon oxide nano sheet product with the whiteness of 91;
(6) The liquid B was divided into 2 equal parts, dolomite (25% of the mass of the solution B) was added to the first part of the solution B, the pH of the solution was adjusted to 6.8, and zinc sulfate (25% of the mass of the solution B) was added to adjust the composition of ions in the solution. Then adding soluble sodium silicate (accounting for 90 percent of the total mole of the alkaline metal compound and the metal salt) and 1, 2-propylene diamine auxiliary agent (accounting for 1.0 percent of the total mole of the alkaline metal compound and the metal salt), fully and uniformly stirring, reacting for 4 hours at the temperature of 80 ℃, collecting the obtained solid product, and performing heat treatment for 2 hours at the temperature of 600 ℃ to obtain a porous silicate adsorbent product;
(7) Adding ferrous hydroxide (accounting for 18% of the mass of the solution B) into the second solution B, and neutralizing residual acid in the solution to obtain a solution C rich in ferric ions;
(8) Adding precipitator potassium silicate into the solution C, adjusting the pH value to 10.5, heating at 60 ℃ for reaction for 8 hours, collecting the obtained red solid product, and calcining at 700 ℃ to obtain the iron oxide red pigment product.
Example 6
(1) Crushing coal gangue (the content of kaolinite is more than 70%) into powder, calcining for 2.5 hours at 700 ℃ and removing residual organic carbon to obtain layered silicate mineral;
(2) Dispersing 10kg of calcined layered silicate mineral into an aqueous solution of 2.5mol/L sulfamic acid and 0.06kg of sodium citrate according to a solid-liquid mass ratio of 1:12, and then sieving the aqueous solution with a 400-mesh vibrating screen to remove undispersed large particles and quartz sand, thereby obtaining a uniform suspension;
(3) Transferring the obtained suspension into a closed reactor, and reacting for 12 hours at 160 ℃ and 6MPa to obtain a mixed product containing solid and liquid;
(4) Carrying out solid-liquid separation on the obtained mixed product to obtain white solid A and liquid B;
(5) Washing the white solid A with water, drying, crushing and sieving to obtain a silicon oxide nano sheet product with the whiteness of 93;
(6) The liquid B was divided into 2 equal parts, calcium carbonate (15% of the mass of the solution B) was added to the first part of the solution B, the pH of the solution was adjusted to 6.6, and calcium oxide (25% of the mass of the solution B) was added to adjust the composition of ions in the solution. Then adding soluble sodium metasilicate (accounting for 125 percent of the total molar weight of the alkaline metal compound and the metal salt) and formamide auxiliary agent (accounting for 1.5 percent of the total molar weight of the alkaline metal compound and the metal salt), fully and uniformly stirring, reacting for 8 hours at the temperature of 100 ℃, collecting the obtained solid product, and performing heat treatment for 1.5 hours at the temperature of 500 ℃ to obtain a porous silicate adsorbent product;
(7) Adding 18% basic ferric carbonate (accounting for the mass of the solution B) into the second solution B, and neutralizing residual acid in the solution to obtain a solution C rich in ferric ions;
(8) Adding precipitator sodium hydroxide into the solution C, adjusting the pH value to 9.5, heating at 80 ℃ for reaction for 10 hours, collecting the obtained red solid product, and calcining at 700 ℃ to obtain the iron oxide red pigment product.
Comparative example 1
Comparative example 1 differs from example 3 only in that: the suspension was heated directly at 170 ℃, unpressurized and not placed in a closed vessel, the remaining parameters being the same as in example 3.
Comparative example 2
Comparative example 2 differs from example 3 only in that: no dispersant was added and the remaining parameters were the same.
Comparative example 3
Comparative example 3 differs from example 3 only in that: no organic amine auxiliary is added, and the other parameters are the same.
Test example 1
SEM scanning was performed on the gangue materials used in examples 1 to 6, the layered silicate minerals obtained by calcining the gangue materials obtained in example 3, and the silica nanoplatelets obtained in example 3, and the results are shown in fig. 1, and it can be seen from fig. 1: calcining the gangue to obtain layered silicate mineral, and carrying out acid dissolution treatment to obtain nano-sheet silicon dioxide, namely, the silicon oxide nano-sheet retains the layered skeleton of the layered silicate mineral. TEM scan was performed on the silica nanoplatelets prepared in example 3, and as shown in FIG. 2, it can be seen from FIG. 2 that the obtained product is silica nanoplatelets.
Referring to fig. 3, it can be seen from fig. 3 that: the porous silicate material prepared by the invention is in nano lamellar, nano cluster and nano flower shape, and has a porous structure. As can be seen from fig. 4: the porous silicate material has a pore structure mainly comprising mesopores, and has a pore size distribution range of 2 nm-50 nm and mainly concentration of 3 nm-15 nm.
Test example 2
Referring to fig. 4, the calculated results are shown in table 1.
Table 1: pore Structure parameters of the porous silicate Material obtained in example 3 of the present invention
Test example 3
The gangue raw material adopted in example 3, the prepared layered silicate mineral, the porous silicate material and the silicate material prepared in comparative example 3 are respectively subjected to dye adsorption and heavy metal adsorption tests, and the results are shown in Table 2, and as can be seen from Table 2, the porous silicate material prepared in the invention has an adsorption amount of 370.27mg/L for organic dye methylene blue, an adsorption amount of 253.86mg/L for heavy metal Cd (II), an adsorption amount of 412.31mg/L for heavy metal Pd (II) and an adsorption amount of 363.52mg/L for tetracycline, so that the porous silicate material prepared in the invention has high-efficiency adsorption performance and is effective in treating environmental pollutants.
Table 2: adsorption Properties of the porous silicate Material obtained in example 3 on dyes and heavy Metal ions
Test example 3
Whiteness of the silica nanoplatelets prepared in example 3 and comparative examples 1 to 2 were measured, respectively, and the results are shown in table 3, and it can be seen from table 3: the coal gangue is changed into gray from black through calcination, and the whiteness of the silicon oxide nano-sheet prepared by the method is more than 91.
Table 3: example 3 whiteness of silica nanosheets produced in comparative examples 1 to 2
Test example 4
The red value of the iron red produced in example 3 was measured, and the results are shown in Table 4, and it can be seen from Table 4: the red value of the iron oxide red prepared by the method reaches 36.12.
Table 4: red value of iron oxide Red produced in example 3
Test example 5
Referring to fig. 6, it can be seen from fig. 6 that: firstly, the crystal structures of the layered silicate mineral and the silicon dioxide nano-sheet prepared by the invention are basically consistent, which shows that the silicon dioxide nano-sheet retains the layered skeleton of the layered silicate mineral, and secondly, the porous silicate material prepared by the invention is a novel material formed by compounding.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. The treatment method of the coal gangue is characterized by comprising the following steps of:
crushing coal gangue, and calcining to obtain layered silicate minerals; the calcination temperature is 400-800 ℃ and the calcination time is 2-12 hours;
dispersing the layered silicate mineral into an aqueous solution containing acid and a dispersing agent according to a solid-liquid mass ratio of 1:5-20 to obtain a suspension; in the aqueous solution, the concentration of hydrogen ions of the acid is 0.25 mol/L-5 mol/L; in the aqueous solution, the mass of the dispersing agent is 0.1% -1% of the mass of the layered silicate mineral; the dispersing agent is one or more than two of nitrilotriacetic acid, sodium glutamate, ammonium citrate, sodium citrate and sodium hexametaphosphate;
placing the suspension in a closed reaction container, performing hydrothermal reaction for 2-24 hours at the temperature of 100-240 ℃ and the pressure of 1-7 MPa, and dissolving out metal ions in the layered silicate mineral by acid in a reactant to obtain a mixed product;
separating the solid in the mixed product, washing, drying and crushing the solid to obtain a silicon oxide nano sheet;
collecting liquid remained after solid products are separated, adding an alkaline metal compound into the liquid to adjust the pH value of the liquid to 4-8, adding metal salt into the liquid to adjust the metal ion composition in the liquid, and adding soluble silicate and an organic amine auxiliary agent into the liquid to obtain a mixed liquid;
carrying out reflux heating reaction on the mixed solution at the temperature of 60-120 ℃ for 2-12 hours, and collecting a solid product;
and carrying out heat treatment on the solid product at the temperature of 200-700 ℃ for 1-3 hours to obtain the porous silicate material.
2. The method for treating coal gangue according to claim 1, wherein the method comprises the steps of,
the acid is one or more than two of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfamic acid, oxalic acid, citric acid, ethylenediamine tetraacetic acid, tartaric acid, ascorbic acid and malic acid;
the mass percentage of kaolinite in the coal gangue is more than 70%.
3. The method for treating coal gangue according to claim 1, wherein the method comprises the steps of,
the alkaline metal compound is selected from one or more than two of magnesium carbonate, magnesium hydroxide, magnesium oxide, basic magnesium carbonate, zinc oxide, zinc hydroxide, calcium oxide, calcium hydroxide, calcium carbonate and dolomite;
the adding mass of the alkaline metal compound is 5% -30% of the mass of the liquid;
the metal salt is selected from one or more of magnesium chloride, magnesium sulfate, magnesium nitrate, magnesium acetate, zinc chloride, zinc sulfate, zinc nitrate, calcium chloride and calcium nitrate;
the added mass of the metal salt is 20% -80% of the mass of the liquid;
the soluble silicate is selected from one or more than two of sodium metasilicate, sodium silicate, potassium metasilicate, potassium silicate, potassium sodium silicate and lithium silicate;
the added molar quantity of the soluble silicate is 75% -200% of the total molar quantity of the added alkaline metal compound and the metal salt;
the organic amine auxiliary agent is one or more than two selected from ethylenediamine, diethylenetriamine, triethylenetetramine, 1, 2-propylene diamine and formamide;
the addition molar quantity of the organic amine auxiliary agent is 0.5% -1.5% of the total molar quantity of the added alkaline metal compound and the metal salt.
4. The treatment method of the coal gangue is characterized by comprising the following steps of:
crushing coal gangue, and calcining to obtain layered silicate minerals; the calcination temperature is 400-800 ℃ and the calcination time is 2-12 hours;
dispersing the layered silicate mineral into an aqueous solution containing acid and a dispersing agent according to a solid-liquid mass ratio of 1:5-20 to obtain a suspension; in the aqueous solution, the concentration of hydrogen ions of the acid is 0.25 mol/L-5 mol/L; in the aqueous solution, the mass of the dispersing agent is 0.1% -1% of the mass of the layered silicate mineral; the dispersing agent is one or more than two of nitrilotriacetic acid, sodium glutamate, ammonium citrate, sodium citrate and sodium hexametaphosphate;
placing the suspension in a closed reaction container, performing hydrothermal reaction for 2-24 hours at the temperature of 100-240 ℃ and the pressure of 1-7 MPa, and dissolving out metal ions in the layered silicate mineral by acid in a reactant to obtain a mixed product;
separating the solid in the mixed product, washing, drying and crushing the solid to obtain a silicon oxide nano sheet;
collecting liquid remained after separating solid products, adding iron powder and/or alkaline ferric salt into the liquid, and neutralizing residual acid in the liquid to obtain an iron ion-enriched solution;
adding precipitator alkali into the solution rich in iron ions, adjusting the pH to 8-12, and heating at 30-80 ℃ for reaction for 5-10 hours to obtain red solid;
and carrying out heat treatment on the red solid to obtain iron oxide red.
5. The method for treating coal gangue as claimed in claim 4, wherein,
the alkaline ferric salt is selected from one or more than two of ferric hydroxide, ferric carbonate, ferrous hydroxide and basic ferric carbonate;
the precipitator alkali is one or more than two of sodium hydroxide, sodium acetate, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate and potassium silicate;
the temperature of the iron oxide red heat treatment is 300-1000 ℃;
the added mass of the iron powder and/or the alkaline ferric salt is 10% -80% of the mass of the liquid.
6. The method for treating coal gangue as claimed in claim 4, wherein,
the acid is one or more than two of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfamic acid, oxalic acid, citric acid, ethylenediamine tetraacetic acid, tartaric acid, ascorbic acid and malic acid;
the mass percentage of kaolinite in the coal gangue is more than 70%.
7. A silica nanosheet produced by the treatment method of coal gangue as claimed in any one of claims 1 to 3 or 4 to 6.
8. A porous silicate material, characterized by being produced by the treatment method of coal gangue as claimed in any one of claims 1 to 3.
9. The porous silicate material according to claim 8, wherein the pore size of the porous silicate material is 2nm to 50nm; the average pore diameter of the porous silicate material is 3 nm-15 nm; the average specific surface area of the porous silicate material is 100 m 2 /g ~800 m 2 /g。
10. An iron oxide red produced by the treatment method of coal gangue as claimed in any one of claims 4 to 6.
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