CN104163451A - Method for producing nano tin-base material - Google Patents
Method for producing nano tin-base material Download PDFInfo
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- CN104163451A CN104163451A CN201410330702.6A CN201410330702A CN104163451A CN 104163451 A CN104163451 A CN 104163451A CN 201410330702 A CN201410330702 A CN 201410330702A CN 104163451 A CN104163451 A CN 104163451A
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Abstract
The invention relates to a method for producing a nano tin-base material, which takes stannous oxalate and a mixture of stannous oxalate as raw materials. The method comprises the following steps: reacting the raw materials and an oxidizing agent solution under 60-150 DEG C, wherein the solid-liquid mass ratio of the raw materials to a hydrogen peroxide solution is (5-50): (95-50), uniformly mixing a tin base material precursor produced by the reaction and a mixed solvent, drying the separated filter mud under 50-150 DEG C, and roasting the dried product for 0.5-3 hours under 600-1000 DEG C to prepare the nano tin-base material. The method uses the stannous oxalate which easily washing and removing chlorine as the raw material, the precursor of the tin-base material is produced through thermal decomposition in the hydrogen peroxide solution (beta-stannic acid and its dopant), and the beta-stannic acid is a non gelatinoid and enables difficult agglomeration. The produced nano stannic oxide, nano antimony-doped tin oxide (ATO), nano indium tin oxide (ITO) have uniform particle, diameter of the above products is less than 100 mm, the apparent density is little (0.3-0.6g/cm<3>), and the nano-material product has the advantages of high purity and excellent performance.
Description
Technical field
The technology of the present invention relates to a kind of method of producing nanometer tin sill.Especially taking the oxalate of mixture, stannous oxalate and the indium of stannous oxalate, stannous oxalate and antimony as a raw material, produce the method for nanometer tin sill.
Background technology
Stannous oxalate can obtain superfine oxide, antimony doped tin oxide, tin indium oxide product through decomposing, in hot oxygen-containing gas, after thermolysis, available ultra-fine tin-based material has a defect, be can remain simple substance carbon in product, removing residual carbon has increased intractability and cost, affects the quality of product.
Traditional liquid phase method is produced nanometer tin sill mostly taking tin tetrachloride as tinbase raw material, with in alkali and generate stannic hydroxide gelatinous precipitate, makes nanometer tin sill after removing chlorion through drying and roasting.This method dechlorination difficulty is very big, and causes the hard aggregation of nanometer product except not clean (the residual quantity >0.2% of chlorine), and the presoma that this method is produced is simultaneously alpha tin acid, and alpha tin acid is jelly, the easy hard aggregation of drying process.This is to be difficult on the market see the major reason that whole particle diameters are less than the tinbase nano material of 100nm.
Summary of the invention
In order to overcome the deficiency of existing production nanometer tin sill technology, the invention provides a kind of method of producing nanometer tin sill.
Technical scheme of the present invention is:
A kind of method 1 of producing nanometer tin sill: taking stannous oxalate as raw material, be to react with oxidizing agent solution under 60-150 DEG C of environment in temperature, the solid-liquid mass ratio of raw material and superoxol is (5-50): (95-50), the tinbase material presoma that reaction produces is for being β-stannic acid.Tin-based material presoma and mixed solvent are mixed even, after filtration or the filter mud separating after precipitation dry at 50-150 temperature, dry product makes nano tin oxide powder for 0.5-3 hours through 600-1000 DEG C of roastings.
A kind of method 2 of producing nanometer tin sill: superfine antimony power, antimonous oxide, antimony peroxide, antimony oxalate, antimony oxalate ammonium, at least one in the oxalate of indium, the mixture forming with stannous oxalate is raw material, be to react with oxidizing agent solution under 60-150 DEG C of environment in temperature, the solid-liquid mass ratio of raw material and superoxol is (5-50): (95-50), the tinbase material presoma that reaction produces is for being β-stannic acid and hotchpotch thereof, tin-based material presoma and mixed solvent are mixed even, after filtration or the filter mud separating after precipitation dry at the temperature of 50-150 DEG C, dry product obtains the base and doped material of nanometer tin for 0.5-3 hours through 600-1000 DEG C of roastings.
Oxidizing agent solution is at least one in hydrogen peroxide, nitric acid, alkali-metal peroxide solutions, and the mass percent concentration of oxidizing agent solution is 5-30%.When oxidizing agent solution is nitric acid, alkali-metal peroxide solutions, resultant of reaction will wash with water totally.
Mixed solvent is methyl alcohol, ethanol or propyl alcohol and liquid ester or alcohol ether-ether polyfunctional group solvent, and the volume ratio of methyl alcohol, ethanol or propyl alcohol and liquid ester or alcohol ether-ether polyfunctional group solvent is (20-80): (80-20).
Mixed solvent is ethanol and propylene glycol methyl ether acetate (PMA), is by volume (20-80): mix (80-20).
Mixture is at least one in superfine antimony power, antimonous oxide, antimony peroxide, antimony oxalate, antimony oxalate ammonium, mix composition with stannous oxalate, in mixture, the mass ratio of tin and antimony is (98-75): (2-25), gained nanometer tin sill is nano antimony doped tin oxide powder.
Mixture is that the oxalate of indium mixes composition with stannous oxalate, in mixture tin and indium mass ratio be (2-25): (98-75), the powder that gained nanometer tin sill is nano-indium stannum oxide.
The invention has the beneficial effects as follows: utilizing the stannous oxalate that is easy to wash except dechlorination is raw material, in superoxol, thermolysis generates the presoma (β-stannic acid and hotchpotch thereof) of tin-based material, and β-stannic acid is non-jelly, is difficult for reuniting.Nano-stannic oxide, nano antimony doped tin oxide (ATO), nano-indium stannum oxide (ITO) uniform particles of utilizing present method to produce, diameter is all less than the particle of 100mm, loose density little (0.3-0.6g/cm3), nano material product purity is high, excellent property.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1:
Hydrogen peroxide 100g is dissolved in 200 ml water, is heated to 100 DEG C, adds stannous oxalate 100g in stirring.After reaction, leave standstill cooling, the tinbase material presoma that reaction produces is for being β-stannic acid, in stirring, add methyl alcohol and propanedioic acid methyl ether acetate (PMA) mixing solutions 1000ml, the volume ratio of methyl alcohol and propylene glycol methyl ether acetate (PMA) is (5-1): (1.5-1), filter, filter mud is 100-120 DEG C of oven dry, and 600-900 DEG C of roastings 2 hours, obtain loose nano-stannic oxide.Nano-stannic oxide diameter is all less than the particle of 100mm, and loose density is 0.3-0.6g/cm3.
Embodiment 2:
Hydrogen peroxide 100g is dissolved in 200 ml water, is heated to 100 DEG C, adds stannous oxalate 100g in stirring.After reaction, leave standstill cooling, the tinbase material presoma that reaction produces is for being β-stannic acid, in stirring, add the mixing solutions 1000ml of ethanol or propyl alcohol and liquid ester or alcohol ether-ether polyfunctional group solvent, the volume ratio of ethanol or propyl alcohol and liquid ester or alcohol ether-ether polyfunctional group solvent is (5-1): (1.5-1), filter, filter mud is 100-120 DEG C of oven dry, and 600-900 DEG C of roastings 2 hours, obtain loose nano-stannic oxide.Nano-stannic oxide diameter is all less than the particle of 100mm, and loose density is 0.3-0.6g/cm3.
Embodiment 3:
Hydrogen peroxide 100g is dissolved in 150ml water, is heated to 80 DEG C, adds the mixture mixing by stannous oxalate 120g, antimonous oxide 10g in stirring.After reaction, leave standstill cooling, the tinbase material presoma that reaction produces is for being β-stannic acid hotchpotch, in stirring, add methyl alcohol and propylene glycol methyl ether acetate (PMA) mixing solutions 900ml, the volume ratio of methyl alcohol and propanedioic acid methyl ether acetate (PMA) is (0.8-1.0): (1.2-1.0), staticly settle 10 hours, the supernatant liquor that inclines, 110 DEG C of precipitation filter muds are dry, roasting 1-2 hours, obtains loose nano antimony doped tin oxide.Nano antimony doped tin oxide diameter is all less than the particle of 100mm, and loose density is 0.3-0.6g/cm3.
Embodiment 4:
Get stannous oxalate 120g, mix with at least one in superfine antimony power, antimony peroxide, antimony oxalate, antimony oxalate ammonium, it is (98-75) that blending ratio keeps the mass ratio of tin and antimony in mixture: (2-25), and for subsequent use.Get hydrogen peroxide 100g and be dissolved in 150ml water, be heated to 80 DEG C, in stirring, add mixture.After reaction, leave standstill cooling, the tinbase material presoma that reaction produces is for being β-stannic acid hotchpotch, in stirring, add the mixing solutions 900ml of ethanol or propyl alcohol and liquid ester or alcohol ether-ether polyfunctional group solvent, the volume ratio of ethanol or propyl alcohol and liquid ester or alcohol ether-ether polyfunctional group solvent is (0.8-1.0): (1.2-1.0), staticly settle 10 hours, the supernatant liquor that inclines, 110 DEG C of precipitation filter muds are dry, roasting 1-2 hours, obtains loose nano antimony doped tin oxide.Nano antimony doped tin oxide diameter is all less than the particle of 100mm, and loose density is 0.3-0.6g/cm3.
Embodiment 5:
Hydrogen peroxide 150g is dissolved in 150 ml water, is heated to 90 DEG C, adds the mixture mixing by oxalic acid indium 160g, stannous oxalate 13.8g in stirring.After reaction, leave standstill cooling, the tinbase material presoma that reaction produces is for being β-stannic acid hotchpotch, in stirring, add methyl alcohol and propylene glycol methyl ether acetate (PMA) mixing solutions 1100ml, the volume ratio of methyl alcohol and propanedioic acid methyl ether acetate (PMA) is 1:1, filtration stirs, 110 DEG C of filter muds are dry, and 850 DEG C of roastings 2 hours, obtain loose nano-indium stannum oxide.Nano-indium stannum oxide diameter is all less than the particle of 100mm, and loose density is 0.3-0.6g/cm3.
Embodiment 6:
Get mass percent concentration and be 5-30% at least one 150 ml in nitric acid, alkali-metal peroxide solutions, be heated to 90 DEG C, in stirring, add the mixture mixing by oxalic acid indium 160g, stannous oxalate 13.8g.After reaction, leave standstill cooling, the tinbase material presoma that reaction produces is for being β-stannic acid hotchpotch, tinbase material presoma washes with water totally, in stirring, add methyl alcohol and propylene glycol methyl ether acetate (PMA) mixing solutions 1100ml, the volume ratio of methyl alcohol and propanedioic acid methyl ether acetate (PMA) is 1:1, the filtration that stirs, and 110 DEG C of filter muds are dry, 850 DEG C of roastings 2 hours, obtain loose nano-indium stannum oxide.Nano-indium stannum oxide diameter is all less than the particle of 100mm, and loose density is 0.3-0.6g/cm3.
Claims (7)
1. produce the method for nanometer tin sill for one kind, it is characterized in that: taking stannous oxalate as raw material, be to react with oxidizing agent solution under 60-150 DEG C of environment in temperature, the solid-liquid mass ratio of raw material and superoxol is (5-50): (95-50), tin-based material presoma and mixed solvent that reaction produces are mixed even, separated filter mud is dry at 50-150 temperature, and dry product makes nano tin oxide powder for 0.5-3 hours through 600-1000 DEG C of roastings.
2. produce the method for nanometer tin sill for one kind, it is characterized in that: superfine antimony power, antimonous oxide, antimony peroxide, antimony oxalate, antimony oxalate ammonium, at least one in the oxalate of indium, the mixture forming with stannous oxalate is raw material, be to react with oxidizing agent solution under 60-150 DEG C of environment in temperature, the solid-liquid mass ratio of raw material and superoxol is (5-50): (95-50), tin-based material presoma and mixed solvent that reaction produces are mixed even, separated filter mud is dry at the temperature of 50-150 DEG C, dry product obtains mixed nanometer oxide compound for 0.5-3 hours through 600-1000 DEG C of roastings.
3. according to a kind of method of producing nanometer tin sill described in claim 1,2, it is characterized in that: oxidizing agent solution is at least one in hydrogen peroxide, nitric acid, alkali-metal peroxide solutions, the mass percent concentration of oxidizing agent solution is 5-30%.
4. according to a kind of method of producing nanometer tin sill described in claim 1,2, it is characterized in that: mixed solvent is the mixed solvent of methyl alcohol, ethanol or propyl alcohol and liquid ester or alcohol ether-ether polyfunctional group solvent, and the volume ratio of methyl alcohol, ethanol or propyl alcohol and liquid ester or alcohol ether-ether polyfunctional group solvent is (20-80): (80-20).
5. according to a kind of method of producing nanometer tin sill described in claim 1,2,4, it is characterized in that: mixed solvent is that ethanol is (20-80) with propylene glycol methyl ether acetate by volume: mix (80-20).
6. a kind of method of producing nanometer tin sill according to claim 2, it is characterized in that: mixture is at least one in superfine antimony power, antimonous oxide, antimony peroxide, antimony oxalate, antimony oxalate ammonium, mix composition with stannous oxalate, in mixture, the mass ratio of tin and antimony is (98-75): (2-25), gained nanometer tin sill is nano antimony doped tin oxide powder.
7. a kind of method of producing nanometer tin sill according to claim 2, it is characterized in that: the oxalate that mixture is indium mixes composition with stannous oxalate, in mixture tin and indium mass ratio be (2-25): (98-75), the powder that gained nanometer tin sill is nano-indium stannum oxide.
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| CN201410330702.6A CN104163451B (en) | 2014-07-14 | 2014-07-14 | Method for producing nano tin-base material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104843770A (en) * | 2015-03-30 | 2015-08-19 | 中国钢研科技集团有限公司 | Method of resource utilization of tin sludge |
| CN107614437A (en) * | 2015-05-19 | 2018-01-19 | 埃西勒国际通用光学公司 | The tin oxide colloidal suspension and methods for making them of witch culture |
| CN111389408A (en) * | 2020-04-17 | 2020-07-10 | 苏州庚泽新材料科技有限公司 | Catalyst, preparation method and application thereof |
| CN114606065A (en) * | 2022-03-25 | 2022-06-10 | 杭州临港化纤有限公司 | Nozzle cleaning agent and preparation method and cleaning process thereof |
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2014
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104843770A (en) * | 2015-03-30 | 2015-08-19 | 中国钢研科技集团有限公司 | Method of resource utilization of tin sludge |
| CN107614437A (en) * | 2015-05-19 | 2018-01-19 | 埃西勒国际通用光学公司 | The tin oxide colloidal suspension and methods for making them of witch culture |
| CN111389408A (en) * | 2020-04-17 | 2020-07-10 | 苏州庚泽新材料科技有限公司 | Catalyst, preparation method and application thereof |
| CN114606065A (en) * | 2022-03-25 | 2022-06-10 | 杭州临港化纤有限公司 | Nozzle cleaning agent and preparation method and cleaning process thereof |
| CN114606065B (en) * | 2022-03-25 | 2023-09-05 | 杭州临港化纤有限公司 | Nozzle cleaning agent and preparation method and cleaning process thereof |
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Effective date of registration: 20210310 Address after: 341100 No.28 torch Avenue, Hongjin Industrial Park, Ganzhou hi tech Industrial Park, Ganzhou City, Jiangxi Province Patentee after: Ganzhou New Material Co.,Ltd. Address before: 341100 No.28 torch Avenue, Ganzhou hi tech Zone, Ganxian County, Ganzhou City, Jiangxi Province Patentee before: GANZHOU RUIDE CHEMICAL Co.,Ltd. |