CN104163451B - Method for producing nano tin-base material - Google Patents
Method for producing nano tin-base material Download PDFInfo
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- CN104163451B CN104163451B CN201410330702.6A CN201410330702A CN104163451B CN 104163451 B CN104163451 B CN 104163451B CN 201410330702 A CN201410330702 A CN 201410330702A CN 104163451 B CN104163451 B CN 104163451B
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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 producing nanometer tin sill.A kind of with stannous oxalate, stannous oxalate and the mixture of antimony, stannous oxalate and indium oxalates as raw material, the method producing nanometer tin sill.
Background technology
Stannous oxalate can obtain superfine oxide, antimony doped tin oxide, tin indium oxide product through decomposing, in the oxygen-containing gas of heat, after thermal decomposition, available ultra-fine tin-based material has a defect, product i.e. can remain simple substance carbon, the carbon of residual to be removed adds intractability and cost, affects the quality of product.
Traditional liquid phase method produces nanometer tin sill mostly with butter of tin for tinbase raw material, with in alkali and generate stannic hydroxide gelatinous precipitate, prepares nanometer tin sill through drying and roasting after removing chloride ion.This method dechlorination difficulty is very big, and except clean (residual quantity of chlorine > 0.2%) causes the hard aggregation of nanometer product, the presoma that this method produces simultaneously is alpha tin acid, and alpha tin acid is jelly, the easy hard aggregation of dry run.This is the major reason being difficult to see the tinbase nano material that whole particle diameter is less than 100nm on the market.
Summary of the invention
In order to overcome the deficiency of existing production nanometer tin sill technology, the present invention provides a kind of method producing nanometer tin sill.
The technical scheme is that
A kind of method 1 producing nanometer tin sill: with stannous oxalate as raw material, react with oxidizing agent solution under temperature is 60 150 DEG C of environment, raw material is (5 50) with the solid-liquid mass ratio of hydrogenperoxide steam generator: (95 50), and the tinbase material presoma that reaction produces is β-stannic acid.Tin-based material presoma and mixed solvent are mixed even, and the filter mud through filtering or separate after precipitation is dried at a temperature of 50 150, and dry product is through 0.5 3 hours prepared nano tin oxide powders of 600 1000 DEG C of roastings.
A kind of method 2 producing nanometer tin sill: superfine antimony power, antimony oxide, antimony pentoxide, antimony oxalate, antimony oxalate ammonium, at least one in the oxalates of indium, it is raw material with the mixture of stannous oxalate composition, react with oxidizing agent solution under temperature is 60 150 DEG C of environment, raw material is (5 50) with the solid-liquid mass ratio of hydrogenperoxide steam generator: (95 50), the tinbase material presoma that reaction produces is β-stannic acid and alloy thereof, tin-based material presoma and mixed solvent are mixed even, filter mud through filtering or separate after precipitation is dried at a temperature of 50 150 DEG C, dry product i.e. 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, reaction product to wash with water totally.
Mixed solvent is that methanol, ethanol or propanol mix with liquid ester or alcohol ether-ether polyfunctional group solvent, and methanol, ethanol or propanol are (20 80) with the volume ratio of liquid ester or alcohol ether-ether polyfunctional group solvent: (80 20).
Mixed solvent is ethanol and propylene glycol methyl ether acetate (PMA), is by volume (20 80): (80 20) mix.
Mixture is at least one in superfine antimony power, antimony oxide, antimony pentoxide, antimony oxalate, antimony oxalate ammonium, composition is mixed with stannous oxalate, in mixture, stannum is (98 75) with the mass ratio of antimony: (2 25), gained nanometer tin sill is nano antimony doped tin oxide powder body.
Mixture is that the oxalates of indium mixes composition with stannous oxalate, in mixture stannum and indium mass ratio be (2 25): (98 75), gained nanometer tin sill is the powder body of nano-indium stannum oxide.
The invention has the beneficial effects as follows: utilizing the stannous oxalate being prone to washing removing chlorine is raw material, thermally decomposes to generate the presoma (β stannic acid and alloy thereof) of tin-based material in hydrogenperoxide steam generator, and β stannic acid is non-jelly, is difficult to reunite.Utilize nano-stannic oxide that this method produces, nano antimony doped tin oxide (ATO), nano-indium stannum oxide (ITO) granule uniform, the diameter granule all less than 100mm, apparent density little (0.3 0.6g/cm), nano material product purity is high, function admirable.
Detailed description of the invention
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.Cooling is stood after reaction, the tinbase material presoma that reaction produces is β-stannic acid, stirring adds methanol and malonic acid methyl ether acetate (PMA) mixed solution 1000ml, the volume ratio of methanol and propylene glycol methyl ether acetate (PMA) is (5 1): (1.5 1), filter, filter mud 100 120 DEG C of drying, 600 900 DEG C of roastings 2 hours, obtain loose nano-stannic oxide.The nano-stannic oxide diameter granule all less than 100mm, apparent density is 0.3 0.6g/cm.
Embodiment 2:
Hydrogen peroxide 100g is dissolved in 200 ml water, is heated to 100 DEG C, adds stannous oxalate 100g in stirring.Cooling is stood after reaction, the tinbase material presoma that reaction produces is β-stannic acid, stirring adds ethanol or propanol and liquid ester or the mixed solution 1000ml of alcohol ether-ether polyfunctional group solvent, the volume ratio of ethanol or propanol and liquid ester or alcohol ether-ether polyfunctional group solvent is (5 1): (1.5 1), filter, filter mud 100 120 DEG C of drying, 600 900 DEG C of roastings 2 hours, obtain loose nano-stannic oxide.The nano-stannic oxide diameter granule all less than 100mm, apparent density is 0.3 0.6g/cm.
Embodiment 3:
Hydrogen peroxide 100g is dissolved in 150ml water, is heated to 80 DEG C, adds and press stannous oxalate 120g, the mixture of antimonous oxide 10g mix homogeneously in stirring.Cooling is stood after reaction, the tinbase material presoma that reaction produces is β-stannic acid alloy, stirring adds methanol and propylene glycol methyl ether acetate (PMA) mixed solution 900ml, the volume ratio of methanol and malonic acid methyl ether acetate (PMA) is (0.8 1.0): (1.2 1.0), staticly settling 10 hours, incline supernatant, and precipitation filter mud 110 DEG C is dried, roasting 12 hours, obtains loose nano antimony doped tin oxide.The nano antimony doped tin oxide diameter granule all less than 100mm, apparent density is 0.3 0.6g/cm.
Embodiment 4:
Taking stannous oxalate 120g, mix with at least one in superfine antimony power, antimony pentoxide, antimony oxalate, antimony oxalate ammonium, mixed proportion keeps the mass ratio of stannum and antimony in mixture to be (98 75): (2 25), standby.Take hydrogen peroxide 100g to be dissolved in 150ml water, be heated to 80 DEG C, stirring adds mixture.Cooling is stood after reaction, the tinbase material presoma that reaction produces is β-stannic acid alloy, stirring adds ethanol or propanol and liquid ester or the mixed solution 900ml of alcohol ether-ether polyfunctional group solvent, the volume ratio of ethanol or propanol and liquid ester or alcohol ether-ether polyfunctional group solvent is (0.8 1.0): (1.2 1.0), staticly settling 10 hours, incline supernatant, and precipitation filter mud 110 DEG C is dried, roasting 12 hours, obtains loose nano antimony doped tin oxide.The nano antimony doped tin oxide diameter granule all less than 100mm, apparent density is 0.3 0.6g/cm.
Embodiment 5:
Hydrogen peroxide 150g is dissolved in 150 ml water, is heated to 90 DEG C, adds and press oxalic acid indium 160g, the mixture of stannous oxalate 13.8g mix homogeneously in stirring.Cooling is stood after reaction, the tinbase material presoma that reaction produces is β-stannic acid alloy, stirring adds methanol and propylene glycol methyl ether acetate (PMA) mixed solution 1100ml, the volume ratio of methanol and malonic acid methyl ether acetate (PMA) is 1:1, stir filtration, filter mud 110 DEG C is dried, 850 DEG C of roastings 2 hours, obtains loose nano-indium stannum oxide.The nano-indium stannum oxide diameter granule all less than 100mm, apparent density is 0.3 0.6g/cm.
Embodiment 6:
Taking mass percent concentration is 5 30% at least one 150 ml obtaining in nitric acid, alkali-metal peroxide solutions, is heated to 90 DEG C, adds and press oxalic acid indium 160g, the mixture of stannous oxalate 13.8g mix homogeneously in stirring.Cooling is stood after reaction, the tinbase material presoma that reaction produces is β-stannic acid alloy, tinbase material presoma washes with water totally, stirring adds methanol and propylene glycol methyl ether acetate (PMA) mixed solution 1100ml, the volume ratio of methanol and malonic acid methyl ether acetate (PMA) is 1:1, and stir filtration, and filter mud 110 DEG C is dried, 850 DEG C of roastings 2 hours, obtain loose nano-indium stannum oxide.The nano-indium stannum oxide diameter granule all less than 100mm, apparent density is 0.3 0.6g/cm.
Claims (10)
1. the method producing nanometer tin sill, it is characterised in that: with stannous oxalate as raw material, it is 60 150 in temperature
Reacting with oxidizing agent solution under DEG C environment, raw material be (5 50) with the solid-liquid mass ratio of oxidizing agent solution: (95 50), reacts
The tin-based material presoma produced is mixed even with mixed solvent, and separated filter mud is dried at a temperature of 50 150 DEG C, is dried
Product are through 0.5 3 hours prepared nano tin oxide powders of 600 1000 DEG C of roastings；Mixed solvent be methanol, ethanol or propanol with
Liquid ester or the mixed solvent of alcohol ether-ether polyfunctional group solvent.
2. the method producing nanometer tin sill, it is characterised in that: superfine antimony power, antimony oxide, antimony pentoxide, grass
Acid antimony, antimony oxalate ammonium, indium oxalates at least one, with stannous oxalate composition mixture be raw material, in temperature be
Reacting with oxidizing agent solution under 60 150 DEG C of environment, raw material is (5 50) with the solid-liquid mass ratio of oxidizing agent solution: (95
50), the tin-based material presoma that reaction produces is mixed even with mixed solvent, and separated filter mud is at a temperature of 50 150 DEG C
Being dried, dry product i.e. obtains mixed nanometer oxide in 0.5 3 hours through 600 1000 DEG C of roastings；Mixed solvent is methanol, ethanol
Or propanol and liquid ester or the mixed solvent of alcohol ether-ether polyfunctional group solvent.
A kind of method producing nanometer tin sill the most according to claim 1, it is characterised in that: oxidizing agent solution was
At least one in hydrogen oxide, nitric acid, alkali-metal peroxide solutions, the mass percent concentration of oxidizing agent solution is 5
30%。
A kind of method producing nanometer tin sill the most according to claim 1, it is characterised in that: methanol, ethanol or third
Alcohol is (20 80) with the volume ratio of liquid ester or alcohol ether-ether polyfunctional group solvent: (80 20).
A kind of method producing nanometer tin sill the most according to claim 4, it is characterised in that: mixed solvent is ethanol
With propylene glycol methyl ether acetate by volume for (20 80): (80 20) mix.
A kind of method producing nanometer tin sill the most according to claim 2, it is characterised in that: oxidizing agent solution was
At least one in hydrogen oxide, nitric acid, alkali-metal peroxide solutions, the mass percent concentration of oxidizing agent solution is 5
30%。
A kind of method producing nanometer tin sill the most according to claim 2, it is characterised in that: methanol, ethanol or third
Alcohol is (20 80) with the volume ratio of liquid ester or alcohol ether-ether polyfunctional group solvent: (80 20).
A kind of method producing nanometer tin sill the most according to claim 7, it is characterised in that: mixed solvent is ethanol
With propylene glycol methyl ether acetate by volume for (20 80): (80 20) mix.
A kind of method producing nanometer tin sill the most according to claim 2, it is characterised in that: mixture is ultra-fine antimony
At least one in powder, antimony oxide, antimony pentoxide, antimony oxalate, antimony oxalate ammonium, mixes composition with stannous oxalate, mixing
In thing, stannum is (98 75) with the mass ratio of antimony: (2 25), gained nanometer tin sill is nano antimony doped tin oxide powder body.
A kind of method producing nanometer tin sill the most according to claim 2, it is characterised in that: mixture is indium
Oxalates mixes composition with stannous oxalate, in mixture stannum and indium mass ratio be (2 25): (98 75), gained nanometer
Tin-based material is the powder body of nano-indium stannum oxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104843770B (en) * | 2015-03-30 | 2017-09-26 | 中国钢研科技集团有限公司 | A kind of method that tin mud resource is utilized |
| WO2016183801A1 (en) * | 2015-05-19 | 2016-11-24 | Essilor International (Compagnie Generale D'optique) | A tungsten-doped stannic oxide colloidal suspension and method for preparing the same |
| 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 |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528830A (en) * | 2003-10-21 | 2004-09-15 | 中国科学院上海硅酸盐研究所 | Antimony-doped tin anhydride inorganic nano conductive powder preparing method |
| CN1994965A (en) * | 2006-12-08 | 2007-07-11 | 中南大学 | Process for preparing antimony doped stannic oxide nano powder |
| CN102515260A (en) * | 2011-10-17 | 2012-06-27 | 易鹤翔 | Method for producing nanometer tin oxide doped with antimony |
| CN102583266A (en) * | 2012-02-13 | 2012-07-18 | 山东大学 | Preparation method of nanoscale stannic oxide hollow sphere |
-
2014
- 2014-07-14 CN CN201410330702.6A patent/CN104163451B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528830A (en) * | 2003-10-21 | 2004-09-15 | 中国科学院上海硅酸盐研究所 | Antimony-doped tin anhydride inorganic nano conductive powder preparing method |
| CN1994965A (en) * | 2006-12-08 | 2007-07-11 | 中南大学 | Process for preparing antimony doped stannic oxide nano powder |
| CN102515260A (en) * | 2011-10-17 | 2012-06-27 | 易鹤翔 | Method for producing nanometer tin oxide doped with antimony |
| CN102583266A (en) * | 2012-02-13 | 2012-07-18 | 山东大学 | Preparation method of nanoscale stannic oxide hollow sphere |
Non-Patent Citations (3)
| Title |
|---|
| Facile synthesis and electrochemical properties of porous SnO2 micro-tubes as anode material for lithium-ion battery;Minwei Xu等;《Materials Letters》;20100128;921-923页 * |
| Synthesis of flowerlike SnO2 quasi-square submicrotubes from tin(II) oxalate precursor;Hua Sun等;《Materials Letters》;20070119;4121–4123页 * |
| 水热法合成单分散性锑掺杂氧化锡纳米导电粉体;张建荣;《硅酸盐学报》;20060430;第34卷(第4期);417-421页 * |
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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. |