CN107902660A - A kind of yellow phosphorus furnace slag prepares SiO2The method of base ATO conductive powder materials - Google Patents
A kind of yellow phosphorus furnace slag prepares SiO2The method of base ATO conductive powder materials Download PDFInfo
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- CN107902660A CN107902660A CN201711008623.3A CN201711008623A CN107902660A CN 107902660 A CN107902660 A CN 107902660A CN 201711008623 A CN201711008623 A CN 201711008623A CN 107902660 A CN107902660 A CN 107902660A
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- yellow phosphorus
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- 239000000463 material Substances 0.000 title claims abstract description 83
- 239000000843 powder Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 34
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000002893 slag Substances 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 33
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 33
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 33
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 53
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 40
- 239000000706 filtrate Substances 0.000 claims description 33
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 31
- 239000011343 solid material Substances 0.000 claims description 30
- 235000014121 butter Nutrition 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 18
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 17
- 239000007790 solid phase Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- 238000005253 cladding Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000012876 carrier material Substances 0.000 abstract description 2
- 238000001802 infusion Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 9
- 239000004567 concrete Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- -1 antimony trichloride ethylene glycol Chemical compound 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000002367 phosphate rock Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/004—Oxides; Hydroxides; Oxyacids
- C01G30/005—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a kind of yellow phosphorus furnace slag to prepare SiO2The method of base ATO conductive powder materials, this method leach yellow phosphorus furnace slag using salpeter solution, obtain high activity and porous SiO2Powder carrier material, then obtains the ATO/SiO of conductive energy by infusion process covered composite yarn2Powder body material；The method of the present invention process equipment is simple, easy, safety is operated, yellow phosphorus furnace slag resource utilization is high, is a kind of processing technology routine for utilizing trade waste production to have high value added product, secondary resource comprehensive utilization is can reach, realizes circular economy, energy-saving and emission-reduction purpose.
Description
Technical field
The invention belongs to industrial solid castoff to utilize field, and in particular to a kind of yellow phosphorus furnace slag prepares SiO2Base ATO is led
The method of electric powder body material.
Background technology
Stibium doping stannic oxide（ATO）Powder body material is a kind of new function conductive material developed rapidly in recent years, is removed
Outside with good electric conductivity and optical property, also with good weatherability, chemical stability and radioresistance, infrared suction
The advantages that receipts, lead in anti-static plastic, chemical fibre, coating, photoelectric display device, transparent electrode material and infrared absorbing material etc.
Domain is widely used, and has a vast market prospect.
It is synthesis even particle size distribution, single dispersing function admirable to obtain the key with excellent photoelectric properties ATO materials
Micropowder material.The method for preparing powder ATO conductive materials can be divided mainly into：Solid phase method, sol-gel method, coprecipitation, water
Hot method etc..
Yellow phosphorus furnace slag uses rock phosphate in powder, silica, coke when raw material produces yellow phosphorus for electric furnace process, in 1400~1600 DEG C of height
The lower molten mass formed of temperature, through having amorphous, high activity solid waste obtained by water quenching chilling, contains a large amount of SiO2With
CaO.Yellow phosphorus furnace slag uses acidleach, can obtain porous, high-specific surface area amorphous Si O2, with this SiO2For matrix, by molten
Glue-gel method, with SnCl4And SbCl3Ethylene glycol or CO (NH2)2Mixed solution is starting material, by coating, hydrolyzing, high temperature
The processing such as calcining, generates the stannic oxide particulate (ATO) of antimony dopant, utilizes SiO2Powerful capillary effect in carrier duct,
Realize the pattern that product is controlled in chemical transformation process, conductive oxide is uniformly adhered to carrier surface, obtain conductive
Property good, resistance to oxidation, corrosion resistant ATO/SiO2Composite conducting material.
The content of the invention
It is an object of the invention to provide a kind of yellow phosphorus furnace slag to prepare SiO2The method of base ATO conductive powder materials, the party
Method is to utilize ATO/SiO of the trade waste production with high added value2The process route of composite conducting material, can reach secondary
Comprehensive utilization of resources, realizes circular economy, energy-saving and emission-reduction purpose.
Technical scheme is as follows：Yellow phosphorus furnace slag is leached using salpeter solution, obtains high activity and porous SiO2
Powder carrier material, then obtains the SiO of conductive energy by infusion process covered composite yarn2Base ATO conductive powder materials.
For coal ash for manufacturing of the present invention for the method for inorganic polymer flocculant, concrete operations are as follows：
（1）By 5~10:1 liquid consolidates mass ratio, and yellow phosphorus furnace slag is added into the salpeter solution that mass concentration is 10~20%, in
0.5 ~ 1.0h, isolated silicate hydrate solid-phase material and leachate are leached under room temperature, stirring condition, and washs silicate hydrate and consolidates
Phase materials；
（2）It is 0.10 ~ 0.15 by antimony and tin molar ratio:1 ratio, the ethylene glycol mixing for preparing butter of tin and antimony trichloride are molten
The mass concentration of butter of tin is 10~15% in liquid, wherein mixed solution；
（3）Take step（2）Obtained ethylene glycol mixed solution, and under room temperature, stirring step is added into the mixed solution（1）
Silicate hydrate solid-phase material after washing, after mixing, stops stirring, and then mixture is placed under ultrasound condition and disperses place
1.0 ~ 2.0h is managed, obtains suspension, wherein ethylene glycol mixed solution and step（1）The liquid of yellow phosphorus furnace slag consolidates mass ratio as 1 ~ 3:1；
（4）By step（3）Obtained suspension, reacts 1.0 ~ 2.0h under room temperature, stirring, is then slowly added into suspension
Mass concentration is 10 ~ 15% ammonia spirit, and regulation system pH value continues at room temperature, stirring 0.5 ~ 3.0h of lower reaction to 6 ~ 9,
Then still aging 1.0 ~ 3.0h, isolated solid material and filtrate, and wash solid material；
（5）By step（4）Solid material after washing, dry 20 ~ 24h under the conditions of 100 ~ 120 DEG C, then at 200 ~ 400 DEG C
1 ~ 2h of lower calcining, 2 ~ 4h is calcined at 600 ~ 800 DEG C, obtains SiO2Base ATO conductive powder materials；
（6）By step（5）Obtained SiO2Base ATO conductive powder materials, by 1~2:1 liquid consolidates mass ratio, adds step（2）
The butter of tin of preparation and the ethylene glycol mixed solution of antimony trichloride, in room temperature, stirring 1.0 ~ 3.0h of lower reaction, then to reaction
The ammonia spirit that mass concentration is 10 ~ 15% is slowly added in liquid, regulation system pH value to 6 ~ 9, continues at room temperature, stirring condition
0.5 ~ 3.0h of lower reaction, then still aging 1.0 ~ 3.0h, isolated solid material, washs solid material, is subsequently placed in 100
Dry 20 ~ 24h under the conditions of ~ 120 DEG C, then 1 ~ 2h of calcining at 200 ~ 400 DEG C is placed in, 2 ~ 4h is calcined at 600 ~ 800 DEG C, is obtained secondary
The SiO of cladding2Base ATO conductive powder materials；
（7）By step（6）The SiO of obtained secondary cladding2Base ATO conductive powder materials, repeat step（6）Processing procedure,
The SiO coated three times2Base ATO conductive powder materials；
（8）Under agitation, to step（1）The sulphur that mass concentration is 40~60% is slowly added in isolated leachate
Ca in acid solution, wherein leachate2+With the SO in sulfuric acid solution4 2-Molar ratio be 1:1.0~1.2, then stirring reaction 1
~2h, isolated solid sediment and precipitation filtrates, wash solid sediment, then dry 2.0 at 240 ~ 260 DEG C ~
3.0h, obtains calcium sulfate product.
The step（8）Isolated precipitation filtrates, return to step（1）Prepare salpeter solution, step（4）、（6）、（7）
Isolated filtrate, prepares ammonia spirit.
The step（1）, step（3）, step（4）And step（6）~（8）In speed of agitator be 300~500rpm.
The step（1）In yellow phosphorus furnace slag refer to use rock phosphate in powder, silica, coke etc. in high-temperature electric resistance furnace for raw material,
The solid waste of output when producing industrial yellow phosphorus, its main ingredient is SiO2And CaO, the content of the two is 80~90%, at the same time
Contain the elements such as P, F, Fe, Al, Mg.
The step（7）The SiO coated three times prepared2Base ATO conductive powder materials are compared with step（5）And step（6）Powder
The electric conductivity of body material is strong.
The present invention has following advantages and effect：
（1）Silica and calcium oxide in effectively extraction and application yellow phosphorus furnace slag of the invention, prepare the production with high added value
Product, a new technology is provided for utilizing for yellow phosphorus furnace slag.
（2）In the method for the present invention technological process, the calcium sulfate of high-quality is prepared in recycling calcium oxide（Land plaster）Product
Meanwhile calcium is sunk by sulfuric acid leachate is converted into salpeter solution, return system recycles, and greatly reduces disappearing for nitric acid
Consumption.
（3）The present invention has the features such as process equipment is simple, and operation is easy, safe.
The solid slag that the present invention is produced using phosphorus production prepares the ATO/SiO with satisfactory electrical conductivity2Composite conducting
Material, can adequately and reasonably utilize resource, turn waste into wealth, reduce environmental pollution, economize on resources, achieve the purpose that it is environmentally protective,
Recycling to resource is of great significance.
Embodiment
The present invention is described in further detail below by embodiment, but the scope of the present invention is not limited in described
Hold.
Embodiment 1：Yellow phosphorus furnace slag prepares SiO2The method of base ATO conductive powder materials, concrete operations are as follows：
（1）1000 grams of the salpeter solution that mass concentration is 15% is added in beaker, by 7:1 liquid consolidates mass ratio, is added in solution
140 grams of yellow phosphorus furnace slag, leaches 1.0h under 24 DEG C, the stirring condition of 350rpm, be isolated to silicate hydrate solid-phase material and
Leachate, and wash silicate hydrate solid-phase material 3 times with 140 grams of water；
（2）By antimony and tin molar ratio 0.10:1 ratio, prepares the ethylene glycol mixed solution of butter of tin and antimony trichloride, wherein
The mass concentration of butter of tin is 15% in mixed solution；
（3）According to step（1）Yellow phosphorus furnace slag and step（2）The butter of tin of preparation and the ethylene glycol mixed solution of antimony trichloride
Solid-liquid mass ratio is 1:1 ratio, adds 140 grams of the ethylene glycol mixed solution of butter of tin and antimony trichloride in the reactor,
And under 24 DEG C, the stirring condition of 500rpm, add step（1）Silicate hydrate solid-phase material after washing, treats that material mixing is equal
After even, stop stirring, material is placed in decentralized processing 1.0h under ultrasound condition, obtains suspension；
（4）By step（3）Obtained suspension, reacts 1.5h under 24 DEG C, 400rpm stirrings, then slowly adds into reaction solution
Enter the ammonia spirit that mass concentration is 15%, regulation system pH value to 7, continues at 24 DEG C, reacts under the stirring condition of 400rpm
2.0h, then still aging 2.0h, isolated solid material and filtrate, filtrate continues to prepare ammonia spirit, isolated
Solid material, is washed 3 times with 140 grams of water；
（5）By step（4）Then solid material after washing, the dry 20h under the conditions of 120 DEG C calcine 1h in 400 DEG C, and 600
DEG C calcining 4h, obtain SiO2Base ATO conductive powder materials；
（6）By step（5）Obtained SiO2Base ATO conductive powder materials, by 1:1 liquid consolidates mass ratio, adds step（2）Prepare
Butter of tin and antimony trichloride ethylene glycol mixed solution, under conditions of 24 DEG C, 300rpm stirring reaction 3.0h, Ran Houxiang
It is slowly added to the ammonia spirit that mass concentration is 10% in reaction solution, regulation system pH value to 9, continues at 24 DEG C, 300rpm stirs
3.0h is reacted under the conditions of mixing, then still aging 1.0h, isolated solid material and filtrate, filtrate prepare ammonia spirit, use
This step SiO2The water of base ATO conductive powder materials quality 80% is washed 3 times, and washed solid material is under the conditions of 100 DEG C
Dry 24h, 1h is calcined at 400 DEG C, 800 DEG C of calcining 2h, obtain the SiO of secondary cladding2Base ATO conductive powder materials；
（7）By step（6）The SiO of obtained secondary cladding2Base ATO conductive powder materials, repeat step（6）Processing procedure,
The SiO coated three times2Base ATO conductive powder materials, the SiO coated three times after testing2The electricity of base ATO conductive powder materials
Resistance rate is 803 Ω cm；
（8）Under the conditions of room temperature, speed of agitator 450rpm, to step（1）It is dense that quality is slowly added in isolated leachate
Spend the sulfuric acid solution for 55%, wherein Ca in leachate2+With the SO in sulfuric acid solution4 2-Molar ratio be 1: 1.0, stirring speed
Spend under the conditions of 450rpm, 1h is reacted in stirring, through separating to obtain solid sediment and precipitation filtrates, isolated solid sediment
It is washed, in 250 DEG C of dry 2.5h, obtain calcium sulfate（Land plaster）Product, through analyzing calcium sulfate（Land plaster）Products C aSO4Contain
Measure as 99.24%, appearance is white, isolated precipitation filtrates return to step（1）Prepare salpeter solution.
Embodiment 2：Yellow phosphorus furnace slag prepares SiO2The method of base ATO conductive powder materials, concrete operations are as follows：
（1）1000 grams of the salpeter solution that mass concentration is 12% is added in beaker, by 9:1 liquid consolidates mass ratio, is added in solution
110 grams of yellow phosphorus furnace slag, leaches 0.75h under 25 DEG C, the stirring condition of 400rpm, be isolated to silicate hydrate solid-phase material and
Leachate, and wash silicate hydrate solid-phase material 3 times with 88 grams of water；
（2）By antimony and tin molar ratio 0.15:1 ratio, prepares the ethylene glycol mixed solution of butter of tin and antimony trichloride, wherein
The mass concentration of butter of tin is 10% in mixed solution；
（3）According to step（1）Yellow phosphorus furnace slag and step（2）The butter of tin of preparation and the ethylene glycol mixed solution of antimony trichloride
Solid-liquid mass ratio is 1:3 ratio, adds 330 grams of the ethylene glycol mixed solution of butter of tin and antimony trichloride in the reactor,
And under 25 DEG C, the stirring condition of 300rpm, add step（1）Silicate hydrate solid-phase material after washing, treats that material mixing is equal
After even, stop stirring, material is placed in decentralized processing 2.0h under ultrasound condition, obtains suspension；
（4）By step（3）Obtained suspension, reacts 1.0h under 25 DEG C, 500rpm stirrings, then slowly adds into reaction solution
Enter the ammonia spirit that mass concentration is 10%, regulation system pH value to 9, continues at 25 DEG C, reacts under the stirring condition of 500rpm
1.0h, then still aging 3.0h, isolated solid material and filtrate, filtrate continues to prepare ammonia spirit, isolated
Solid material, is washed 3 times with 88 grams of water；
（5）By step（4）Then solid material after washing, the dry 24h under the conditions of 100 DEG C calcine 2h in 200 DEG C, and 700
DEG C calcining 2.5h, obtain SiO2Base ATO conductive powder materials；
（6）By step（5）Obtained SiO2Base ATO conductive powder materials, by 2:1 liquid consolidates mass ratio, adds step（2）Prepare
Butter of tin and antimony trichloride ethylene glycol mixed solution, under conditions of 25 DEG C, 350rpm stirring reaction 2.5h, Ran Houxiang
It is slowly added to the ammonia spirit that mass concentration is 15% in reaction solution, regulation system pH value to 7, continues at 25 DEG C, 350rpm stirs
1.0h is reacted under the conditions of mixing, then still aging 3.0h, isolated solid material and filtrate, filtrate prepare ammonia spirit, use
This step SiO2The water of base ATO conductive powder materials quality 50% is washed 3 times, and washed solid material is under the conditions of 120 DEG C
Dry 20h, 1.5h is calcined at 300 DEG C, 600 DEG C of calcining 4h, obtain the SiO of secondary cladding2Base ATO conductive powder materials；
（7）By step（6）The SiO of obtained secondary cladding2Base ATO conductive powder materials, repeat step（6）Processing procedure,
The SiO coated three times2Base ATO conductive powder materials, the SiO coated three times after testing2The electricity of base ATO conductive powder materials
Resistance rate is 754 Ω cm；
（8）Under the conditions of 25 DEG C, speed of agitator 300rpm, to step（1）It is dense that quality is slowly added in isolated leachate
Spend the sulfuric acid solution for 40%, wherein Ca in leachate2+With the SO in sulfuric acid solution4 2-Molar ratio be 1:1.1, in stirring speed
Spend under the conditions of 300rpm, stirring reaction 2.0h, through separating to obtain solid sediment and precipitation filtrates, isolated solid precipitates
Thing is washed, in 240 DEG C of dry 3h, obtains calcium sulfate（Land plaster）Product, through analyzing calcium sulfate（Land plaster）Products C aSO4Contain
Measure as 98.84%, appearance is white, isolated precipitation filtrates return to step（1）Prepare salpeter solution.
Embodiment 3：Yellow phosphorus furnace slag prepares SiO2The method of base ATO conductive powder materials, concrete operations are as follows：
（1）1000 grams of the salpeter solution that mass concentration is 20% is added in beaker, by 5:1 liquid consolidates mass ratio, is added in solution
200 grams of yellow phosphorus furnace slag, leaches 1.0h under 25 DEG C, the stirring condition of 500rpm, be isolated to silicate hydrate solid-phase material and
Leachate, and wash silicate hydrate solid-phase material 3 times with 180 grams of water；
（2）By antimony and tin molar ratio 0.12:1 ratio, prepares the ethylene glycol mixed solution of butter of tin and antimony trichloride, wherein
The mass concentration of butter of tin is 12% in mixed solution；
（3）According to step（1）Yellow phosphorus furnace slag and step（2）The butter of tin of preparation and the ethylene glycol mixed solution of antimony trichloride
Solid-liquid mass ratio is 1:2.5 ratio, adds the ethylene glycol mixed solution 500 of butter of tin and antimony trichloride in the reactor
Gram, and under 25 DEG C, the stirring condition of 300rpm, add step（1）Silicate hydrate solid-phase material after washing, treats that material mixes
After uniformly, stop stirring, material is placed in decentralized processing 1.5h under ultrasound condition, obtains suspension；
（4）By step（3）Obtained suspension, reacts 2.0h under 25 DEG C, 300rpm stirrings, then slowly adds into reaction solution
Enter the ammonia spirit that mass concentration is 12%, regulation system pH value to 6, continues at 25 DEG C, reacts under the stirring condition of 300rpm
3.0h, then still aging 1.0h, isolated solid material and filtrate, filtrate continues to prepare ammonia spirit, isolated
Solid material, is washed 3 times with 180 grams of water；
（5）By step（4）Solid material after washing, dry 22h, then calcines 1.5h in 300 DEG C under the conditions of 110 DEG C,
800 DEG C of calcining 2h, obtain SiO2Base ATO conductive powder materials；
（6）By step（5）Obtained SiO2Base ATO conductive powder materials, by 1.5:1 liquid consolidates mass ratio, adds step（2）Match somebody with somebody
The butter of tin of system and the ethylene glycol mixed solution of antimony trichloride, the stirring reaction 2.0h under conditions of 25 DEG C, 400rpm, then
The ammonia spirit that mass concentration is 14% is slowly added into reaction solution, regulation system pH value to 6, continues at 25 DEG C, 400rpm
2.0h reacting under stirring condition, then still aging 2.0h, isolated solid material and filtrate, filtrate prepare ammonia spirit,
With this step SiO2The water of base ATO conductive powder materials quality 60% is washed 3 times, and washed solid material is in 110 DEG C of conditions
Lower dry 22h, 2h is calcined at 200 DEG C, 700 DEG C of calcining 3h, obtain the SiO of secondary cladding2Base ATO conductive powder materials；
（7）By step（6）The SiO of obtained secondary cladding2Base ATO conductive powder materials, repeat step（6）Processing procedure,
The SiO coated three times2Base ATO conductive powder materials, the SiO coated three times after testing2The electricity of base ATO conductive powder materials
Resistance rate is 862 Ω cm；
（8）Under the conditions of 25 DEG C, speed of agitator 400rpm, to step（1）It is dense that quality is slowly added in isolated leachate
Spend the sulfuric acid solution for 60%, wherein Ca in leachate2+With the SO in sulfuric acid solution4 2-Molar ratio be 1:1.0, in stirring speed
Spend under the conditions of 400rpm, stirring reaction 1.5h, through separating to obtain solid sediment and precipitation filtrates, isolated solid precipitates
Thing is washed, in 260 DEG C of dry 2h, obtains calcium sulfate（Land plaster）Product, through analyzing calcium sulfate（Land plaster）Products C aSO4Contain
Measure as 99.05%, appearance is white, isolated precipitation filtrates return to step（1）Prepare salpeter solution.
Embodiment 4：Yellow phosphorus furnace slag prepares SiO2The method of base ATO conductive powder materials, concrete operations are as follows：
（1）1000 grams of the salpeter solution that mass concentration is 10% is added in beaker, by 10:1 liquid consolidates mass ratio, in solution plus
Enter 100 grams of yellow phosphorus furnace slag, leach 0.5h under 25 DEG C, the stirring condition of 300rpm, be isolated to silicate hydrate solid-phase material
And leachate, and wash silicate hydrate solid-phase material 3 times with 100 grams of water；
（2）By antimony and tin molar ratio 0.14:1 ratio, prepares the ethylene glycol mixed solution of butter of tin and antimony trichloride, wherein
The mass concentration of butter of tin is 13% in mixed solution；
（3）According to step（1）Yellow phosphorus furnace slag and step（2）The butter of tin of preparation and the ethylene glycol mixed solution of antimony trichloride
Solid-liquid mass ratio is 1:2 ratio, adds 200 grams of the ethylene glycol mixed solution of butter of tin and antimony trichloride in the reactor,
And under 25 DEG C, the stirring condition of 400rpm, add step（1）Silicate hydrate solid-phase material after washing, treats that material mixing is equal
After even, stop stirring, material is placed in decentralized processing 1h under ultrasound condition, obtains suspension；
（4）By step（3）Obtained suspension, reacts 2.0h under 25 DEG C, 500rpm stirrings, then slowly adds into reaction solution
Enter the ammonia spirit that mass concentration is 10%, regulation system pH value to 8, continues at 25 DEG C, reacts under the stirring condition of 500rpm
0.5h, then still aging 3.0h, isolated solid material and filtrate, filtrate continues to prepare ammonia spirit, isolated
Solid material, is washed 3 times with 100 grams of water；
（5）By step（4）Then solid material after washing, the dry 20h under the conditions of 100 DEG C calcine 1h in 400 DEG C, and 650
DEG C calcining 3h, obtain SiO2Base ATO conductive powder materials；
（6）By step（5）Obtained SiO2Base ATO conductive powder materials, by 2:1 liquid consolidates mass ratio, adds step（2）Prepare
Butter of tin and antimony trichloride ethylene glycol mixed solution, under conditions of 25 DEG C, 500rpm stirring reaction 1.0h, Ran Houxiang
It is slowly added to the ammonia spirit that mass concentration is 12% in reaction solution, regulation system pH value to 8, continues at 25 DEG C, 500rpm stirs
0.5h is reacted under the conditions of mixing, then still aging 1.5h, isolated solid material and filtrate, filtrate prepare ammonia spirit, use
This step SiO2The water of base ATO conductive powder materials quality 70% is washed 3 times, and washed solid material is under the conditions of 120 DEG C
Dry 20h, 1.0h is calcined at 350 DEG C, 750 DEG C of calcining 2h, obtain the SiO of secondary cladding2Base ATO conductive powder materials；
（7）By step（6）The SiO of obtained secondary cladding2Base ATO conductive powder materials, repeat step（6）Processing procedure,
The SiO coated three times2Base ATO conductive powder materials, the SiO coated three times after testing2The electricity of base ATO conductive powder materials
Resistance rate is 728 Ω cm；
（8）Under the conditions of 25 DEG C, speed of agitator 500rpm, to step（1）It is dense that quality is slowly added in isolated leachate
Spend the sulfuric acid solution for 50%, wherein Ca in leachate2+With the SO in sulfuric acid solution4 2-Molar ratio be 1:1.2, in stirring speed
Spend under the conditions of 500rpm, 1h is reacted in stirring, through separating to obtain solid sediment and precipitation filtrates, isolated solid sediment
It is washed, in 250 DEG C of dry 3h, obtain calcium sulfate（Land plaster）Product, through analyzing calcium sulfate（Land plaster）Products C aSO4Content
For 98.73%, appearance is white, isolated precipitation filtrates return to step（1）Prepare salpeter solution.
Claims (3)
1. a kind of yellow phosphorus furnace slag prepares SiO2The method of base ATO conductive powder materials, it is characterised in that carry out according to the following steps：
（1）By 5~10:1 liquid consolidates mass ratio, and yellow phosphorus furnace slag is added into the salpeter solution that mass concentration is 10~20%, in
0.5 ~ 1.0h, isolated silicate hydrate solid-phase material and leachate are leached under room temperature, stirring condition, and washs silicate hydrate and consolidates
Phase materials；
（2）It is 0.10 ~ 0.15 by antimony and tin molar ratio:1 ratio, the ethylene glycol mixing for preparing butter of tin and antimony trichloride are molten
Butter of tin mass concentration is 10~15% in liquid, wherein mixed solution；
（3）Take step（2）Obtained ethylene glycol mixed solution, and under room temperature, stirring step is added into the mixed solution（1）
Silicate hydrate solid-phase material after washing, after mixing, stops stirring, and then mixture is placed under ultrasound condition and disperses place
1.0 ~ 2.0h is managed, obtains suspension, wherein ethylene glycol mixed solution and step（1）The liquid of yellow phosphorus furnace slag consolidates mass ratio as 1 ~ 3:1；
（4）By step（3）Obtained suspension, reacts 1.0 ~ 2.0h under room temperature, stirring, is then slowly added into reaction solution
Mass concentration is 10 ~ 15% ammonia spirit, and regulation system pH value continues at room temperature, stirring 0.5 ~ 3.0h of lower reaction to 6 ~ 9,
Then still aging 1.0 ~ 3.0h, isolated solid material and filtrate, and wash solid material；
（5）By step（4）Solid material after washing, dry 20 ~ 24h under the conditions of 100 ~ 120 DEG C, then at 200 ~ 400 DEG C
1 ~ 2h of lower calcining, 2 ~ 4h is calcined at 600 ~ 800 DEG C, obtains SiO2Base ATO conductive powder materials；
（6）By step（5）Obtained SiO2Base ATO conductive powder materials, by 1~2:1 liquid consolidates mass ratio, adds step（2）Match somebody with somebody
The butter of tin of system and the ethylene glycol mixed solution of antimony trichloride, in room temperature, stirring 1.0 ~ 3.0h of lower reaction, then to reaction solution
In be slowly added to mass concentration be 10 ~ 15% ammonia spirit, regulation system pH value to 6 ~ 9, continues under room temperature, stirring condition
0.5 ~ 3.0h is reacted, then still aging 1.0 ~ 3.0h, isolated solid material and filtrate, wash solid material, then put
Dry 20 ~ 24h under the conditions of 100 ~ 120 DEG C, then 1 ~ 2h of calcining at 200 ~ 400 DEG C is placed in, 2 ~ 4h is calcined at 600 ~ 800 DEG C, is obtained
To the SiO of secondary cladding2Base ATO conductive powder materials；
（7）By step（6）The SiO of obtained secondary cladding2Base ATO conductive powder materials, repeat step（6）Processing procedure, obtain
To the SiO coated three times2Base ATO conductive powder materials；
（8）Under room temperature, stirring condition, to step（1）Mass concentration is slowly added in isolated leachate as 40~60%
Sulfuric acid solution, the wherein Ca in leachate2+With the SO in sulfuric acid solution4 2-Molar ratio be 1:1.0~1.2, then stirring is anti-
Answer 1~2h, isolated solid sediment and precipitation filtrates, wash solid sediment, then dry 2.0 at 240 ~ 260 DEG C ~
3.0h, obtains calcium sulfate product.
2. yellow phosphorus furnace slag according to claim 1 prepares SiO2The method of base ATO conductive powder materials, it is characterised in that：Step
Suddenly（8）Isolated precipitation filtrates, return to step（1）Prepare salpeter solution, step（4）、（6）Isolated filtrate, matches somebody with somebody
Ammonia spirit processed.
3. yellow phosphorus furnace slag according to claim 1 prepares SiO2The method of base ATO conductive powder materials, it is characterised in that：Step
Suddenly（1）、（3）、（4）、（6）With（8）In speed of agitator be 300~500rpm.
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| CN116588941A (en) * | 2023-05-18 | 2023-08-15 | 昆明理工大学 | Method for comprehensively utilizing yellow phosphorus slag |
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