CN107902660B - Preparation of SiO from yellow phosphorus slag2Method for preparing ATO-based conductive powder material - Google Patents
Preparation of SiO from yellow phosphorus slag2Method for preparing ATO-based conductive powder material Download PDFInfo
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Abstract
The invention discloses a method for preparing SiO by using yellow phosphorus slag2The method for preparing the ATO-based conductive powder material adopts nitric acid solution to leach yellow phosphorus slag to obtain high-activity and porous SiO2Coating and compounding the powder carrier material by an impregnation method to obtain ATO/SiO with conductive performance2A powder material; the method has the advantages of simple process equipment, easy and safe operation and high utilization rate of yellow phosphorus slag resources, is a process technical route for producing products with high added values by using industrial wastes, and can achieve the purposes of secondary resource comprehensive utilization, cyclic economy, energy conservation and emission reduction.
Description
Technical Field
The invention belongs to the field of utilization of industrial solid wastes, and particularly relates to a method for preparing SiO by using yellow phosphorus slag2A method for preparing ATO-based conductive powder material.
Background
The antimony doped tin dioxide (ATO) powder material is a novel functional conductive material which is rapidly developed in recent years, has the advantages of good weather resistance, chemical stability, radiation resistance, infrared absorption and the like besides good conductive performance and optical performance, has wide application in the fields of antistatic plastics, chemical fibers, coatings, photoelectric display devices, transparent electrode materials, infrared absorption materials and the like, and has wide market prospect.
The key to obtain the ATO material with excellent photoelectric property is to synthesize the micro powder material with uniform particle size distribution and excellent monodispersity. The method for preparing the powdery ATO conductive material mainly comprises the following steps: solid phase methods, sol-gel methods, coprecipitation methods, hydrothermal methods, and the like.
The yellow phosphorus slag is a molten mass formed at the high temperature of 1400-1600 ℃ when the yellow phosphorus is produced by adopting phosphate ore, silica, coke and other raw materials by an electric furnace method, and is quenched by water to obtain amorphous and high-activity solid waste containing a large amount of SiO2And CaO. The yellow phosphorus slag is leached by acid to obtain porous amorphous SiO with high specific surface area2Thereby SiO2As matrix, by sol-gel method, with SnCl4And SbCl3Ethylene glycol or CO (NH)2)2The mixed solution is used as a starting material, and is subjected to coating, hydrolysis, high-temperature calcination and other treatments to generate antimony-doped tin dioxide particles (ATO), and SiO is utilized2The strong capillary effect in the carrier pore channel realizes the control of the morphology of the product in the chemical transformation process, so that the conductive oxide is uniformly attached to the surface of the carrier, and the ATO/SiO with good conductivity, oxidation resistance and corrosion resistance is obtained2A composite conductive material.
Disclosure of Invention
The invention aims to provide a method for preparing SiO by using yellow phosphorus slag2A process for preparing the electrically conductive ATO-based powder material features that the industrial waste is used to prepare the ATO/SiO powder material with high added value2The process route of the composite conductive material can achieve the purposes of comprehensive utilization of secondary resources and realization of circular economy, energy conservation and emission reduction.
The technical scheme of the invention is as follows: leaching the yellow phosphorus slag by using a nitric acid solution to obtain high-activity and porous SiO2The powder carrier material is coated and compounded by an impregnation method to obtain SiO with conductive performance2And an ATO conductive powder material.
The method for preparing the inorganic polymeric flocculant by using the fly ash comprises the following specific operations:
(1) adding yellow phosphorus slag into a nitric acid solution with the mass concentration of 10-20% according to the liquid-solid mass ratio of 5-10: 1, leaching for 0.5-1.0 h at room temperature under the stirring condition, separating to obtain a hydrated silicic acid solid-phase material and a leaching solution, and washing the hydrated silicic acid solid-phase material;
(2) preparing an ethylene glycol mixed solution of stannic chloride and antimony trichloride according to the molar ratio of antimony to tin of 0.10-0.15: 1, wherein the mass concentration of stannic chloride in the mixed solution is 10-15%;
(3) taking the ethylene glycol mixed solution obtained in the step (2), adding the hydrated silicic acid solid-phase material washed in the step (1) into the mixed solution at room temperature under stirring, stopping stirring after uniform mixing, and then placing the mixture under an ultrasonic condition for dispersion treatment for 1.0-2.0 hours to obtain a suspension, wherein the liquid-solid mass ratio of the ethylene glycol mixed solution to the yellow phosphorus slag in the step (1) is 1-3: 1;
(4) reacting the suspension obtained in the step (3) for 1.0-2.0 hours at room temperature under stirring, slowly adding an ammonia water solution with the mass concentration of 10-15% into the suspension, adjusting the pH value of the system to 6-9, continuously reacting for 0.5-3.0 hours at room temperature under stirring, standing and aging for 1.0-3.0 hours, separating to obtain a solid material and a filtrate, and washing the solid material;
(5) drying the solid material washed in the step (4) at 100-120 ℃ for 20-24 h, calcining at 200-400 ℃ for 1-2 h, and calcining at 600-800 ℃ for 2-4 h to obtain SiO2An ATO-based conductive powder material;
(6) SiO obtained in the step (5)2Adding the ethylene glycol mixed solution of tin tetrachloride and antimony trichloride prepared in the step (2) into an ATO conductive powder material according to a liquid-solid mass ratio of 1-2: 1, reacting for 1.0-3.0 hours under stirring at room temperature, slowly adding an ammonia water solution with the mass concentration of 10-15% into the reaction solution, adjusting the pH value of the system to 6-9, continuously reacting for 0.5-3.0 hours under stirring at room temperature, standing and aging for 1.0-3.0 hours, separating to obtain a solid material, washing the solid material, drying for 20-24 hours at 100-120 ℃, calcining for 1-2 hours at 200-400 ℃, calcining for 2-4 hours at 600-800 ℃ to obtain a secondary coated SiO2An ATO-based conductive powder material;
(7) the secondary coated SiO obtained in the step (6)2Repeating the treatment process of the step (6) based on the ATO conductive powder material to obtain the SiO coated for three times2An ATO-based conductive powder material;
(8) slowly adding the mass concentration into the leaching solution obtained by separation in the step (1) under the condition of stirring40-60% sulfuric acid solution, wherein Ca in the leaching solution2+With SO in sulfuric acid solution4 2-The molar ratio of the organic acid to the inorganic acid is 1: 1.0-1.2, stirring and reacting for 1-2 hours, separating to obtain a solid precipitate and a precipitate filtrate, washing the solid precipitate, and drying at 240-260 ℃ for 2.0-3.0 hours to obtain a calcium sulfate product.
And (3) returning the precipitate filtrate obtained by separation in the step (8) to the step (1) for preparing the nitric acid solution, and preparing the ammonia water solution from the filtrates obtained by separation in the steps (4), (6) and (7).
The stirring rotation speed in the steps (1), (3), (4) and (6) - (8) is 300-500 rpm.
The yellow phosphorus slag in the step (1) is solid waste produced in the process of producing industrial yellow phosphorus by taking phosphate ore, silica, coke and the like as raw materials in a high-temperature electric furnace, and the main component of the yellow phosphorus slag is SiO2And CaO, the content of the CaO and the CaO is 80-90%, and the CaO contains elements such as P, F, Fe, Al, Mg and the like.
The three-time coated SiO prepared in the step (7)2Compared with the powder materials in the step (5) and the step (6), the ATO-based conductive powder material has stronger conductivity.
The invention has the following advantages and effects:
(1) the invention effectively extracts and utilizes silicon dioxide and calcium oxide in the yellow phosphorus slag to prepare products with high added value, and provides a new process technology for utilizing the yellow phosphorus slag.
(2) In the process flow of the method, the calcium oxide is recovered to prepare a high-quality calcium sulfate (gypsum powder) product, and meanwhile, the leachate is converted into a nitric acid solution through calcium precipitation by sulfuric acid and returned to a system for recycling, so that the consumption of nitric acid is greatly reduced.
(3) The invention has the characteristics of simple process equipment, easy operation, safety and the like.
The invention utilizes the solid waste residue generated in the production of yellow phosphorus to prepare ATO/SiO with good conductivity2The composite conductive material can fully and reasonably utilize resources, change waste into valuable, reduce environmental pollution and save resourcesThe purpose of environmental protection is achieved, and the method has important significance for recycling resources.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the above-described examples.
Example 1: preparation of SiO from yellow phosphorus slag2The method for preparing the ATO-based conductive powder material specifically comprises the following operations:
(1) adding 1000 g of nitric acid solution with the mass concentration of 15% into a beaker, adding 140 g of yellow phosphorus slag into the solution according to the liquid-solid mass ratio of 7:1, leaching for 1.0h under the stirring condition of 24 ℃ and 350rpm, separating to obtain hydrated silicic acid solid-phase materials and leachate, and washing the hydrated silicic acid solid-phase materials for 3 times by using 140 g of water;
(2) preparing an ethylene glycol mixed solution of stannic chloride and antimony trichloride according to the molar ratio of antimony to tin of 0.10:1, wherein the mass concentration of stannic chloride in the mixed solution is 15%;
(3) adding 140 g of ethylene glycol mixed solution of tin tetrachloride and antimony trichloride into a reactor according to the solid-liquid mass ratio of 1:1 of the yellow phosphorus slag in the step (1) to the ethylene glycol mixed solution of tin tetrachloride and antimony trichloride prepared in the step (2), adding the hydrated silicic acid solid-phase material washed in the step (1) under the stirring condition of 24 ℃ and 500rpm, stopping stirring after the materials are uniformly mixed, and performing dispersion treatment on the material under the ultrasonic condition for 1.0h to obtain a suspension;
(4) reacting the suspension obtained in the step (3) for 1.5 hours under stirring at 24 ℃ and 400rpm, slowly adding an ammonia water solution with the mass concentration of 15% into the reaction solution, adjusting the pH value of the system to 7, continuing to react for 2.0 hours under the stirring condition at 24 ℃ and 400rpm, standing and aging for 2.0 hours, separating to obtain a solid material and a filtrate, continuing to prepare the ammonia water solution from the filtrate, separating to obtain the solid material, and washing for 3 times with 140 g of water;
(5) drying the solid material washed in the step (4) at 120 ℃ for 20h, then calcining at 400 ℃ for 1h, and calcining at 600 ℃ for 4h to obtain SiO2An ATO-based conductive powder material;
(6) SiO obtained in the step (5)2Adding the ethylene glycol mixed solution of tin tetrachloride and antimony trichloride prepared in the step (2) into an ATO (antimony trichloride) -based conductive powder material according to a liquid-solid mass ratio of 1:1, stirring and reacting for 3.0 hours at 24 ℃ and 300rpm, slowly adding an ammonia water solution with the mass concentration of 10% into the reaction solution, adjusting the pH value of the system to 9, continuing to react for 3.0 hours at 24 ℃ and 300rpm, standing and aging for 1.0 hour, separating to obtain a solid material and a filtrate, preparing the ammonia water solution from the filtrate, and preparing the SiO by using the step2Washing with water in an amount of 80% by mass of the ATO-based conductive powder material for 3 times, drying the washed solid material at 100 deg.C for 24h, calcining at 400 deg.C for 1h, and calcining at 800 deg.C for 2h to obtain secondarily-coated SiO2An ATO-based conductive powder material;
(7) the secondary coated SiO obtained in the step (6)2Repeating the treatment process of the step (6) based on the ATO conductive powder material to obtain the SiO coated for three times2Based on ATO conductive powder material, SiO coated for three times through detection2The resistivity of the ATO-based conductive powder material is 803 omega cm;
(8) slowly adding a sulfuric acid solution with the mass concentration of 55% into the leaching solution obtained by the separation in the step (1) at the room temperature and the stirring rotating speed of 450rpm, wherein Ca is contained in the leaching solution2+With SO in sulfuric acid solution4 2-The molar ratio of the raw materials is 1:1.0, the raw materials are stirred and reacted for 1h under the condition that the stirring speed is 450rpm, solid precipitates and precipitation filtrate are obtained through separation, the solid precipitates obtained through separation are washed and dried for 2.5h at the temperature of 250 ℃ to obtain calcium sulfate (gypsum powder) products, and the calcium sulfate (gypsum powder) products CaSO are analyzed4The content is 99.24%, the appearance is white, and the separated precipitation filtrate is returned to the step (1) for preparing the nitric acid solution.
Example 2: preparation of SiO from yellow phosphorus slag2The method for preparing the ATO-based conductive powder material specifically comprises the following operations:
(1) adding 1000 g of nitric acid solution with the mass concentration of 12% into a beaker, adding 110 g of yellow phosphorus slag into the solution according to the liquid-solid mass ratio of 9:1, leaching for 0.75h under the stirring condition of 25 ℃ and 400rpm, separating to obtain hydrated silicic acid solid-phase materials and leachate, and washing the hydrated silicic acid solid-phase materials for 3 times by using 88 g of water;
(2) preparing an ethylene glycol mixed solution of stannic chloride and antimony trichloride according to the molar ratio of antimony to tin of 0.15:1, wherein the mass concentration of stannic chloride in the mixed solution is 10%;
(3) according to the solid-liquid mass ratio of the yellow phosphorus slag in the step (1) to the ethylene glycol mixed solution of tin tetrachloride and antimony trichloride prepared in the step (2) being 1:3, adding 330 g of the ethylene glycol mixed solution of tin tetrachloride and antimony trichloride into a reactor, adding the hydrated silicic acid solid-phase material washed in the step (1) under the stirring condition of 25 ℃ and 300rpm, stopping stirring after the materials are uniformly mixed, and performing dispersion treatment on the material under the ultrasonic condition for 2.0h to obtain a suspension;
(4) reacting the suspension obtained in the step (3) for 1.0h under stirring at 25 ℃ and 500rpm, slowly adding an ammonia water solution with the mass concentration of 10% into the reaction solution, adjusting the pH value of the system to 9, continuing to react for 1.0h under the stirring condition at 25 ℃ and 500rpm, standing and aging for 3.0h, separating to obtain a solid material and a filtrate, continuing to prepare the ammonia water solution from the filtrate, separating to obtain the solid material, and washing for 3 times with 88 g of water;
(5) drying the solid material washed in the step (4) at 100 ℃ for 24h, then calcining at 200 ℃ for 2h, and calcining at 700 ℃ for 2.5h to obtain SiO2An ATO-based conductive powder material;
(6) SiO obtained in the step (5)2Adding the ethylene glycol mixed solution of tin tetrachloride and antimony trichloride prepared in the step (2) into an ATO (antimony trichloride) -based conductive powder material according to a liquid-solid mass ratio of 2:1, stirring and reacting for 2.5h at 25 ℃ and 350rpm, slowly adding an ammonia water solution with the mass concentration of 15% into the reaction solution, adjusting the pH value of the system to 7, continuously reacting for 1.0h at 25 ℃ and 350rpm, standing and aging for 3.0h, separating to obtain a solid material and a filtrate, preparing the ammonia water solution from the filtrate, and preparing the SiO by using the step2Washing with 50 wt% water for 3 times, and drying at 120 deg.CDrying for 20h, calcining at 300 ℃ for 1.5h and at 600 ℃ for 4h to obtain the secondary coated SiO2An ATO-based conductive powder material;
(7) the secondary coated SiO obtained in the step (6)2Repeating the treatment process of the step (6) based on the ATO conductive powder material to obtain the SiO coated for three times2Based on ATO conductive powder material, SiO coated for three times through detection2The resistivity of the ATO-based conductive powder material is 754 omega cm;
(8) slowly adding 40% sulfuric acid solution into the leachate obtained in the step (1) under the conditions of 25 ℃ and stirring speed of 300rpm, wherein Ca in the leachate is2+With SO in sulfuric acid solution4 2-The molar ratio of the components is 1:1.1, the reaction is carried out for 2.0 hours under the condition that the stirring speed is 300rpm, solid precipitate and precipitate filtrate are obtained through separation, the solid precipitate obtained through separation is washed and dried for 3 hours at the temperature of 240 ℃ to obtain a calcium sulfate (gypsum powder) product, and the calcium sulfate (gypsum powder) product CaSO is analyzed4The content is 98.84%, the appearance is white, and the separated precipitation filtrate is returned to the step (1) for preparing the nitric acid solution.
Example 3: preparation of SiO from yellow phosphorus slag2The method for preparing the ATO-based conductive powder material specifically comprises the following operations:
(1) adding 1000 g of 20% nitric acid solution into a beaker, adding 200 g of yellow phosphorus slag into the solution according to the liquid-solid mass ratio of 5:1, leaching for 1.0h under the stirring condition of 25 ℃ and 500rpm, separating to obtain hydrated silicic acid solid-phase materials and leachate, and washing the hydrated silicic acid solid-phase materials for 3 times by using 180 g of water;
(2) preparing an ethylene glycol mixed solution of stannic chloride and antimony trichloride according to the molar ratio of antimony to tin of 0.12:1, wherein the mass concentration of stannic chloride in the mixed solution is 12%;
(3) adding 500 g of ethylene glycol mixed solution of tin tetrachloride and antimony trichloride into a reactor according to the solid-liquid mass ratio of 1:2.5 of the yellow phosphorus slag in the step (1) to the ethylene glycol mixed solution of tin tetrachloride and antimony trichloride prepared in the step (2), adding the hydrated silicic acid solid-phase material washed in the step (1) under the stirring condition of 25 ℃ and 300rpm, stopping stirring after the materials are uniformly mixed, and performing dispersion treatment on the material under the ultrasonic condition for 1.5 hours to obtain a suspension;
(4) reacting the suspension obtained in the step (3) for 2.0h under stirring at 25 ℃ and 300rpm, slowly adding an ammonia water solution with the mass concentration of 12% into the reaction solution, adjusting the pH value of the system to 6, continuing to react for 3.0h under the stirring condition at 25 ℃ and 300rpm, standing and aging for 1.0h, separating to obtain a solid material and a filtrate, continuing to prepare the ammonia water solution from the filtrate, separating to obtain the solid material, and washing for 3 times with 180 g of water;
(5) drying the solid material washed in the step (4) at 110 ℃ for 22h, then calcining at 300 ℃ for 1.5h, and calcining at 800 ℃ for 2h to obtain SiO2An ATO-based conductive powder material;
(6) SiO obtained in the step (5)2Adding the ethylene glycol mixed solution of tin tetrachloride and antimony trichloride prepared in the step (2) into an ATO (antimony trichloride) -based conductive powder material according to a liquid-solid mass ratio of 1.5:1, stirring and reacting for 2.0h at 25 ℃ and 400rpm, slowly adding an ammonia water solution with the mass concentration of 14% into the reaction solution, adjusting the pH value of the system to 6, continuing to react for 2.0h at 25 ℃ and 400rpm, standing and aging for 2.0h, separating to obtain a solid material and a filtrate, preparing an ammonia water solution from the filtrate, and preparing the SiO by using the step2Washing with water 60% of the mass of ATO-based conductive powder material for 3 times, drying the washed solid material at 110 deg.C for 22h, calcining at 200 deg.C for 2h, and calcining at 700 deg.C for 3h to obtain secondary coated SiO2An ATO-based conductive powder material;
(7) the secondary coated SiO obtained in the step (6)2Repeating the treatment process of the step (6) based on the ATO conductive powder material to obtain the SiO coated for three times2Based on ATO conductive powder material, SiO coated for three times through detection2The resistivity of the ATO-based conductive powder material is 862 omega cm;
(8) slowly adding a sulfuric acid solution with the mass concentration of 60% into the leaching solution obtained by the separation in the step (1) at the temperature of 25 ℃ and the stirring rotating speed of 400rpm, wherein Ca in the leaching solution2+With SO in sulfuric acid solution4 2-The molar ratio of the components is 1:1.0, the reaction is carried out for 1.5h under the condition that the stirring speed is 400rpm, solid precipitate and precipitate filtrate are obtained through separation, the solid precipitate obtained through separation is washed and dried for 2h at 260 ℃ to obtain calcium sulfate (gypsum powder) product, and the calcium sulfate (gypsum powder) product CaSO is analyzed4The content is 99.05%, the appearance is white, and the separated precipitation filtrate is returned to the step (1) for preparing the nitric acid solution.
Example 4: preparation of SiO from yellow phosphorus slag2The method for preparing the ATO-based conductive powder material specifically comprises the following operations:
(1) adding 1000 g of nitric acid solution with the mass concentration of 10% into a beaker, adding 100 g of yellow phosphorus slag into the solution according to the liquid-solid mass ratio of 10:1, leaching for 0.5h under the stirring condition of 25 ℃ and 300rpm, separating to obtain hydrated silicic acid solid-phase materials and leachate, and washing the hydrated silicic acid solid-phase materials for 3 times by using 100 g of water;
(2) preparing an ethylene glycol mixed solution of tin tetrachloride and antimony trichloride according to the molar ratio of antimony to tin of 0.14:1, wherein the mass concentration of the tin tetrachloride in the mixed solution is 13%;
(3) adding 200 g of mixed solution of tin tetrachloride and antimony trichloride glycol into a reactor according to the solid-liquid mass ratio of 1:2 of the yellow phosphorus slag in the step (1) to the mixed solution of tin tetrachloride and antimony trichloride glycol prepared in the step (2), adding the washed hydrated silicic acid solid-phase material in the step (1) under the stirring condition of 25 ℃ and 400rpm, stopping stirring after the materials are uniformly mixed, and performing dispersion treatment on the material under the ultrasonic condition for 1h to obtain a suspension;
(4) reacting the suspension obtained in the step (3) for 2.0h under stirring at 25 ℃ and 500rpm, slowly adding an ammonia water solution with the mass concentration of 10% into the reaction solution, adjusting the pH value of the system to 8, continuing to react for 0.5h under the stirring condition at 25 ℃ and 500rpm, standing and aging for 3.0h, separating to obtain a solid material and a filtrate, continuing to prepare the ammonia water solution from the filtrate, separating to obtain the solid material, and washing for 3 times with 100 g of water;
(5) will be provided withDrying the solid material washed in the step (4) at 100 ℃ for 20h, then calcining at 400 ℃ for 1h, and calcining at 650 ℃ for 3h to obtain SiO2An ATO-based conductive powder material;
(6) SiO obtained in the step (5)2Adding the ethylene glycol mixed solution of tin tetrachloride and antimony trichloride prepared in the step (2) into an ATO (antimony trichloride) -based conductive powder material according to a liquid-solid mass ratio of 2:1, stirring and reacting for 1.0h at 25 ℃ and 500rpm, slowly adding an ammonia water solution with the mass concentration of 12% into the reaction solution, adjusting the pH value of the system to 8, continuing to react for 0.5h at 25 ℃ and 500rpm, standing and aging for 1.5h, separating to obtain a solid material and a filtrate, preparing the ammonia water solution from the filtrate, and preparing the SiO by using the step2Washing with water in an amount of 70% by mass of the ATO-based conductive powder material for 3 times, drying the washed solid material at 120 deg.C for 20h, calcining at 350 deg.C for 1.0h, and calcining at 750 deg.C for 2h to obtain secondarily-coated SiO2An ATO-based conductive powder material;
(7) the secondary coated SiO obtained in the step (6)2Repeating the treatment process of the step (6) based on the ATO conductive powder material to obtain the SiO coated for three times2Based on ATO conductive powder material, SiO coated for three times through detection2The resistivity of the ATO-based conductive powder material is 728 omega cm;
(8) slowly adding 50% sulfuric acid solution into the leachate obtained in the step (1) under the conditions of 25 ℃ and stirring speed of 500rpm, wherein Ca in the leachate is2+With SO in sulfuric acid solution4 2-The molar ratio of the components is 1:1.2, the reaction is carried out for 1 hour under the condition that the stirring speed is 500rpm, solid precipitate and precipitate filtrate are obtained through separation, the solid precipitate obtained through separation is washed and dried for 3 hours at 250 ℃ to obtain calcium sulfate (gypsum powder) product, and the calcium sulfate (gypsum powder) product CaSO is analyzed4The content is 98.73%, the appearance is white, and the separated precipitation filtrate is returned to the step (1) for preparing the nitric acid solution.
Claims (3)
1. Preparation of SiO from yellow phosphorus slag2The method for preparing ATO-based conductive powder material is characterized in thatThe following steps are carried out:
(1) adding yellow phosphorus slag into a nitric acid solution with the mass concentration of 10-20% according to the liquid-solid mass ratio of 5-10: 1, leaching for 0.5-1.0 h at room temperature under the stirring condition, separating to obtain a hydrated silicic acid solid-phase material and a leaching solution, and washing the hydrated silicic acid solid-phase material;
(2) preparing an ethylene glycol mixed solution of stannic chloride and antimony trichloride according to the molar ratio of antimony to tin of 0.10-0.15: 1, wherein the mass concentration of stannic chloride in the mixed solution is 10-15%;
(3) taking the ethylene glycol mixed solution obtained in the step (2), adding the hydrated silicic acid solid-phase material washed in the step (1) into the mixed solution at room temperature under stirring, stopping stirring after uniform mixing, and then placing the mixture under an ultrasonic condition for dispersion treatment for 1.0-2.0 hours to obtain a suspension, wherein the liquid-solid mass ratio of the ethylene glycol mixed solution to the yellow phosphorus slag in the step (1) is 1-3: 1;
(4) reacting the suspension obtained in the step (3) for 1.0-2.0 hours at room temperature under stirring, slowly adding an ammonia water solution with the mass concentration of 10-15% into the reaction liquid, adjusting the pH value of the system to 6-9, continuously reacting for 0.5-3.0 hours at room temperature under stirring, standing and aging for 1.0-3.0 hours, separating to obtain a solid material and a filtrate, and washing the solid material;
(5) drying the solid material washed in the step (4) at 100-120 ℃ for 20-24 h, calcining at 200-400 ℃ for 1-2 h, and calcining at 600-800 ℃ for 2-4 h to obtain SiO2An ATO-based conductive powder material;
(6) SiO obtained in the step (5)2Adding the ethylene glycol mixed solution of tin tetrachloride and antimony trichloride prepared in the step (2) into an ATO conductive powder material according to a liquid-solid mass ratio of 1-2: 1, reacting for 1.0-3.0 hours under stirring at room temperature, slowly adding an ammonia water solution with the mass concentration of 10-15% into the reaction solution, adjusting the pH value of the system to 6-9, continuing to react for 0.5-3.0 hours under stirring at room temperature, standing and aging for 1.0-3.0 hours, separating to obtain a solid material and a filtrate, washing the solid material, drying for 20-24 hours at 100-120 ℃, calcining for 1-2 hours at 200-400 ℃, and 600-8 hoursCalcining for 2-4 h at 00 ℃ to obtain secondary coated SiO2An ATO-based conductive powder material;
(7) the secondary coated SiO obtained in the step (6)2Repeating the treatment process of the step (6) based on the ATO conductive powder material to obtain the SiO coated for three times2An ATO-based conductive powder material;
(8) slowly adding 40-60% sulfuric acid solution into the leachate obtained by separation in the step (1) at room temperature under the condition of stirring, wherein Ca in the leachate is2+With SO in sulfuric acid solution4 2-The molar ratio of the organic acid to the inorganic acid is 1: 1.0-1.2, stirring and reacting for 1-2 hours, separating to obtain a solid precipitate and a precipitate filtrate, washing the solid precipitate, and drying at 240-260 ℃ for 2.0-3.0 hours to obtain a calcium sulfate product.
2. The yellow phosphorus slag of claim 1 for preparing SiO2The method for preparing the ATO-based conductive powder material is characterized by comprising the following steps: and (4) returning the precipitate filtrate obtained by separation in the step (8) to the step (1) for preparing the nitric acid solution, and preparing an ammonia water solution from the filtrate obtained by separation in the steps (4) and (6).
3. The yellow phosphorus slag of claim 1 for preparing SiO2The method for preparing the ATO-based conductive powder material is characterized by comprising the following steps: the stirring rotation speed in the steps (1), (3), (4), (6) and (8) is 300-500 rpm.
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| CN101850979A (en) * | 2010-04-29 | 2010-10-06 | 昆明理工大学 | Comprehensive utilization method of yellow phosphorus furnace slag |
| CN103318951A (en) * | 2013-07-10 | 2013-09-25 | 赵宝勤 | Preparation method of ATO (Antimony doped Tin Oxide) nanopowder |
| CN105129805A (en) * | 2015-07-10 | 2015-12-09 | 上海纳旭实业有限公司 | Preparation method of silicon oxide/tin antimony oxide/zinc oxide ternary composite material |
| CN105702382A (en) * | 2016-01-18 | 2016-06-22 | 常州大学 | Method for preparing light-colored conductive potassium titanate powder |
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| KR20050020394A (en) * | 2003-08-22 | 2005-03-04 | 요업기술원 | Method of Coating transparent-conductive layer |
| CN101850979A (en) * | 2010-04-29 | 2010-10-06 | 昆明理工大学 | Comprehensive utilization method of yellow phosphorus furnace slag |
| CN103318951A (en) * | 2013-07-10 | 2013-09-25 | 赵宝勤 | Preparation method of ATO (Antimony doped Tin Oxide) nanopowder |
| CN105129805A (en) * | 2015-07-10 | 2015-12-09 | 上海纳旭实业有限公司 | Preparation method of silicon oxide/tin antimony oxide/zinc oxide ternary composite material |
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