CN103213993B - A kind of method preparing high-purity nano silicon dioxide - Google Patents
A kind of method preparing high-purity nano silicon dioxide Download PDFInfo
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- CN103213993B CN103213993B CN201310131569.7A CN201310131569A CN103213993B CN 103213993 B CN103213993 B CN 103213993B CN 201310131569 A CN201310131569 A CN 201310131569A CN 103213993 B CN103213993 B CN 103213993B
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Abstract
The invention discloses a kind of method preparing high-purity nano silicon dioxide, it is characterised in that: comprising the following steps: SILICA FUME is dissolved in alkali liquor by (1), undissolved solid residue is removed in centrifugal or filtration；(2) supernatant is removed impurity with cation exchange resin and anion exchange resin respectively；(3) step (2) is processed the solution obtained to dry, namely obtain high-purity nano silicon dioxide, significantly improve the quality of product, and simplify processing step, reduce production cost.
Description
Technical field
The present invention relates to a kind of method preparing high-purity nano silicon dioxide.
Background technology
Monocrystal silicon is of paramount importance material in Solar use, and its production technology adopts native silicon dioxide and coke refining, and the oxygen removed in silicon dioxide obtains elemental metals silicon.This process can produce substantial amounts of by-product SILICA FUME.Along with the development of photovoltaic industry, the demand of metallic silicon is increasing, and the yield of by-product SILICA FUME is also increasing, has formed serious industrial solid thing and has polluted.Can be seen that SILICA FUME has two features according to standard GB/T/T21236-2007: one is that the content of silicon dioxide is very high, generally reaches more than 90%；Two is contain a small amount of impurity metallic elements all the time.So, the matter of utmost importance solved for the technique of raw material production silicon dioxide with SILICA FUME removes all of impurity element exactly, improves the purity of product.
Table 1, SILICA FUME ingredient standard (GB/T21236-2007).
The technique being raw material production silicon dioxide with SILICA FUME at present is mainly the sedimentation method.But, the disadvantage of the existing sedimentation method is just difficult to remove these impurity elements, because the sedimentation method first have to dissolve raw material, the procedure component of material dissolution is disperseed with molecularity, and impurity element is dissolution simultaneously also；And impurity removal process is also considerably complicated, adopt by adding different precipitant, the impurity element that precipitation is different targetedly.Obviously, the precipitant kind of use is more many, more complicated, and the by-product of generation is more many so that the separation purification more difficult of product.In addition, more seriously, in the process of clarification prime element, the concentration of metasilicic acid progressively increases, and causes the viscosity of solution to incrementally increase, and the granule of metasilicic acid precipitation is easily reunited, cause substantial amounts of impurity element parcel, be adsorbed on inside and the surface of granule, causing and cannot eliminate impurity, product purity is not high, causes that the quality of product silicon dioxide produced is not high.
Summary of the invention
The technical problem to be solved in the present invention: in prior art, SILICA FUME is the processing step complexity of raw material production silicon dioxide, the product silica purity obtained is not high, present invention employs the sedimentation method of ion exchange auxiliary, significantly improve the quality of product, and simplify processing step, reduce production cost.
The technical scheme of the employing of the present invention: the method for preparation high-purity nano silicon dioxide, comprises the following steps:
(1) SILICA FUME is dissolved in alkali liquor, is centrifuged or is filtered to remove undissolved solid residue；
(2) supernatant is removed impurity with cation exchange resin and anion exchange resin respectively；
(3) step (2) is processed the solution obtained to dry, namely obtain silicon dioxide.
The concentration of alkali liquor is 30%～60%.
Being dissolved in alkali liquor by SILICA FUME, its mass volume ratio is: 40%～80%(W/V).
Cation exchange resin is storng-acid cation exchange resin or strongly acidic styrene type cation exchange resin.
Dry employing in step (3): organic dissolution azeotropic drying or spray drying.
In conjunction with the step of the present invention, illustrate principles of the invention and beneficial effect.
(1) in SILICA FUME, SiO is mainly contained2, the lower SiO of heating2Can act on the corresponding metasilicate of generation lentamente with strong base solution, under low consistency conditions, metasilicate is dissolved in alkaline solution with molecularity, sees reaction equation (1).
SiO2+2NaOH=Na2SiO3+H2O(1)
Additionally, element silicon important chemical property is exactly the tendency forming macromole.Various atomic link or ring it is interconnected between atom, silicon atom alternates formation singly-bound macromole with singly-bound and oxygen atom, so dilute concentration not only contributes to the preparation of nano silicon, and all of impurity metallic elements can be dissolved out more fully from SILICA FUME, dispersion is in the solution, it is simple to remove.
(2) cationic resin is adopted to remove the metal ion being dissolved in alkali liquor.
Iron sesquioxide in SILICA FUME, aluminium oxide, calcium oxide, magnesium oxide have certain dissolubility at highly basic medium.Concrete equation is as follows:
Fe2O3+12NaOH=2Na3[Fe(OH)6]+3H2O(2)
Fe2O3+3SiO2+12NaOH=Fe2(SiO3)3+H2O(3)
Fe2O3+3H2SO4=Fe2(SO4)3+3H2O(4)
Al2O3+2NaOH=2NaAlO2+H2O(5)
Al2O3+3SiO2+8NaOH=Al2(SiO3)3+4H2O(6)
Al2O3+6HCl=2AlCl3+3H2O(7)
CaO+H2O=Ca(OH)2(8)
CaO+H2SO4=CaSO4+H2O(9)
MgO+H2O=Mg(OH)2(10)
MgO+H2SO4=MgSO4+H2O(11)
Except several elements above, SILICA FUME is also possible to the metallic element containing other, as: sodium, potassium, copper, manganese, phosphorus, zinc, hydrargyrum, lead and other elements, the constituent of silicon mineral raw material used when this is mainly by refining elemental silicon determines.Their dissolved form and ferrum, aluminum, calcium, magnesium are slightly different, but when different acid, alkali, have certain dissolving.
No matter it is metallic element, or metalloid anion root, as long as existing in solution with ionic condition, remove such as through ion exchange resin, the solution of ion exchange resin removing foreign metal ion mainly can occur the reaction of following reaction equation.
In formula, Resin is resin.
Reaction equation (12) be SILICA FUME prepare in silicon dioxide most important, the reaction of most critical, this reaction makes all of sodium silicate be completely converted into silicic acid.The silicic acid of free state, including metasilicic acid (H2SiO3), two silicic acid (H2Si2O5), acidity is very weak.The ionization equilibrium constant K of metasilicic acid1=2×10-10(room temperature), positive silicic acid is stable in the scope of pH=2-3, if but by oversaturated H4SiO4Solution is placed for a long time, has unbodied precipitation of silica, for milky white precipitate, and occurs with colloidal particle, precipitate or gel.Gel there is portion of water evaporate, the dry solid gel of a kind of porous, namely common silica dioxide gel can be obtained.
In the carrying out of reaction (12), owing to NaOH is excessive, after excessive sodium hydroxide and cation exchange resin react, the pH of reaction solution drops to about 3.Meanwhile, now impurity metallic elements is deposited in the solution with the ion of free state under this condition, and ion exchange resin and metal cation exchange, and are attached on ion exchange resin by metal ion, and the separated removing with resin and separating of reaction solution.
The reaction of iron ions:
Na2SO4+Resin-H+=2Resin-Na++H2SO4
Na3[Fe(OH)6]+H2SO4=Fe2(SO4)3+Na2SO4+H2O
Except aluminum ions reaction:
Na2SO4+Resin-H+=2Resin-Na++H2SO4
NaAlO2+H2SO4=Al2(SO4)3+Na2SO4+H2O
The removing reaction of other metal ions:
With M representation metal ion, such as calcium, magnesium, zinc, copper, manganese, phosphorus, hydrargyrum, lead, sodium, potassium etc.:
Na2SO4+Resin-H+=2Resin-Na++H2SO4
M(OH)n+H2SO4=MSO4+H2O
(3) resin anion (R.A.) is adopted to remove anion, containing larger amount of anion in SILICA FUME, mainly sulfate radical and a small amount of chlorate anions.Exchanging in decationizing process at ion, cation and ion exchange resin there occurs that exchange, adsorption of metal ions have been arrived and displaced hydrion H+ on resin.Hydrion and anion binding, make solution be in acidity.
The reaction that anion occurs with anion exchange resin:
Reacting it can be seen that product is all neutral from both the above, after being separated with reaction solution by the ion exchange resin of solid, solution is exactly water white neutral solution.
(4) dehydrate obtains high-purity nano silicon dioxide
The process of dehydration is to prepare the processing step that silica nanometer micropowder must carry out, because the existence of moisture will make silicon dioxide powder form moisture film in dry run, the capillarity of moisture film makes silicon dioxide powder reunion caking, causes producing unsuccessfully.
In the course of dissolution of SILICA FUME, the present invention uses the sodium hydrate aqueous solution of 30%～60%, and namely course of dissolution can bring substantial amounts of moisture into.Additionally, the product in above ion-exchange reactions formula has hydrone to generate, this is also the approach that moisture introduces.
In nano material preparation process, dehydration is a crucial step, and the method for employing is a lot.The synthesis aspect that simply prepared by material of nano material, and how obtaining these materials maintaining original synthesis shape and size is another hang-up in nano material preparation.The solvent of liquid phase method synthesis usually contains moisture, these moisture are always adsorbed on the surface of silicon dioxide colloid, along with the evaporation of solvent in dry run, contact with each other between granule and form intergranular water film, this layer of moisture film has the character of capillary water, surface tension is very big, thus mutually being furthered and caking of reuniting by microgranule.At present, the recovery of nano material of liquid phase method synthesis is had multiple method and is in the news, such as supercritical drying, freeze-drying, micro-wave drying method and azeotropic drying method.But, the present invention is found by substantial amounts of research, before three kinds of drying meanss be the reunion reducing synthetic material by reducing the surface tension of capillary water, azeotropic drying method is the method effectively avoiding synthetic material to reunite.
Spray drying is a kind of method that systematization technique is applied to dry materials.In hothouse by solvent or diluent after atomization, with in the contacting of hot-air, moisture rapid vaporization, namely obtain dry products.This method can directly make solution, emulsion be dried to powdery or particulate preparation, can economize the operation such as devaporation, pulverizing.
Spray drying tool heat transfer is fast, and rapidly, the feature of moment drying time, and good product quality, quality is crisp, and in aqueous solvent, dispersive property is good, can improve the dissolution rate of some preparation in moisture evaporation.
Spray drying process is applicable to the dry of all kinds of materials, it is possible to dry fine powder, micropowder, without dust powder and hollow bead agent.Can be divided three classes by material atomizing type: (1) air-blast atomization, utilize compression air or steam to make feed liquid be atomized；(2) pressure type atomization, extrudes feed liquid with high-pressure pump, is formed vaporific from nozzle at high speeds；(3) rotation type atomization, in the throwing disc (7000～20000r/min) being added in nebulizer high speed rotating by feed liquid, quickly throws away feed liquid and is atomized.The rotation type atomization seasoning that the present invention adopts is effective, and the time is short, and labor productivity is high, is favored by material circle.
The technical performance index adopting the nanometer grade silica product of the present invention is as shown in table 2:
The table 2 nanometer grade silica performance index of product technologies
Detailed description of the invention:
Embodiment 1
The present invention prepares the method for high-purity nano silicon dioxide, comprises the following steps:
(1) under 160 DEG C of conditions, being dissolved in the alkali liquor of 250ml60% by SILICA FUME 100g, stir after silicon dioxide dissolves, undissolved solid residue is removed in centrifugal or filtration；
(2) supernatant is removed impurity with 001 × 7 (732) storng-acid cation exchange resin (above sea water benefit resin company limited produces) and 201 × 7 (717) strong-basicity styrene series anion exchange resins (above sea water benefit resin company limited produces) respectively；
(3) step (2) is processed the solution organic solvent azeotropic seasoning obtained to dry, namely obtain lipophile high-purity nano silicon dioxide.
Table 3 embodiment 1 produces the nanometer grade silica performance index of product technologies obtained
Embodiment 2
The present invention prepares the method for high-purity nano silicon dioxide, comprises the following steps:
(1) under 160 DEG C of conditions, being dissolved in the alkali liquor of 160ml35% concentration by SILICA FUME 80g, stir after silicon dioxide dissolves, undissolved solid residue is removed in centrifugal or filtration；
(2) supernatant is removed impurity with 001 × 7 (732) strongly acidic styrene type cation exchange resin (production of Anhui Samsung resin Science and Technology Ltd.) and 201 × 7 (717) strong-basicity styrene series anion exchange resins (production of Anhui Samsung resin Science and Technology Ltd.) respectively；
(3) step (2) is processed the solution rotation type atomization seasoning obtained to dry, namely obtain hydrophilic high-purity nano silicon dioxide.
Table 4 embodiment 2 produces the nanometer grade silica performance index of product technologies obtained
Embodiment 3
The present invention prepares the method for high-purity nano silicon dioxide, comprises the following steps:
(1) under 160 DEG C of conditions, being dissolved in the alkali liquor of 120ml40% concentration by SILICA FUME 80g, stir after silicon dioxide dissolves, undissolved solid residue is removed in centrifugal or filtration；
(2) supernatant is removed impurity with 001 × 7 (732) strongly acidic styrene type cation exchange resin (production of Anhui Samsung resin Science and Technology Ltd.) and 201 × 7 (717) strong-basicity styrene series anion exchange resins (above sea water benefit resin company limited produces) respectively；
(3) step (2) is processed the solution rotation type atomization seasoning obtained to dry, namely obtain hydrophilic high-purity nano silicon dioxide.
Table 5 embodiment 3 produces the nanometer grade silica performance index of product technologies obtained
Embodiment 4
The present invention prepares the method for high-purity nano silicon dioxide, comprises the following steps:
(1) under 160 DEG C of conditions, being dissolved in the alkali liquor of 50ml30% concentration by SILICA FUME 40g, stir after silicon dioxide dissolves, undissolved solid residue is removed in centrifugal or filtration；
(2) supernatant is removed impurity with 001 × 7 (732) strongly acidic styrene type cation exchange resin (production of Anhui Samsung resin Science and Technology Ltd.) and 201 × 7 (717) strong-basicity styrene series anion exchange resins (production of Anhui Samsung resin Science and Technology Ltd.) respectively；
(3) step (2) is processed the solution organic solvent azeotropic seasoning obtained to dry, namely obtain lipophile high-purity nano silicon dioxide.
Table 6 embodiment 4 produces the nanometer grade silica performance index of product technologies obtained
Claims (3)
1. the method preparing high-purity nano silicon dioxide, it is characterised in that: it is prepared from by three below step:
(1) being dissolved in alkali liquor by SILICA FUME, undissolved solid residue is removed in centrifugal or filtration, mainly contains SiO in SILICA FUME2, the lower SiO of heating2Can act on the corresponding metasilicate of generation lentamente with strong base solution, under low consistency conditions, metasilicate is dissolved in alkaline solution with molecularity, sees reaction equation (1)；
SiO2+ 2NaOH=Na2SiO3+H2O(1)
(2) supernatant is removed impurity with cation exchange resin and anion exchange resin respectively, iron sesquioxide in SILICA FUME, aluminium oxide, calcium oxide, magnesium oxide has certain dissolubility in highly basic medium, except several elements above, possibly together with other metallic element in SILICA FUME, as: sodium, potassium, copper, manganese, phosphorus, zinc, hydrargyrum, lead element, the constituent of silicon mineral raw material used when this is mainly by refining elemental silicon determines, their dissolved form and ferrum, aluminum, calcium, magnesium is slightly different, but in different acid, when alkali, there is certain dissolving, no matter it is metallic element, or metalloid anion root, as long as existing in solution with ionic condition, remove such as through ion exchange resin；
Containing larger amount of anion in SILICA FUME, mainly sulfate radical and a small amount of chlorate anions, exchange in decationizing process at ion, cation and ion exchange resin there occurs that exchange, adsorption of metal ions have been arrived and displaced hydrion H on resin+, hydrion and anion binding, make solution be in acidity, after being separated with reaction solution by the ion exchange resin of solid, solution is exactly water white neutral solution；
(3) step (2) is processed the solution obtained to dry, namely obtain high-purity nano silicon dioxide；
The concentration of described alkali liquor is 30%～60%；
The w/v of described SILICA FUME and alkali liquor is: 40%～80%g/mL；
Described cation exchange resin is storng-acid cation exchange resin；
Described anion exchange resin is strong-basicity styrene series anion exchange resin；
Dry employing azeotropic drying method or spray drying method in described step (3).
2. a kind of method preparing high-purity nano silicon dioxide according to claim 1, it is characterised in that: azeotropic drying method is organic dissolution azeotropic drying method.
3. a kind of method preparing high-purity nano silicon dioxide according to claim 1, it is characterised in that: spray drying method is rotation type atomization method.
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| CN102066252A (en) * | 2008-02-12 | 2011-05-18 | 日产化学工业株式会社 | Colloidal silica particles, process for producing the same, and silica sol in organic solvent, silica sol in polymerizable compound, and silica sol in dicarboxylic anhydride each obtained from the same |
| CN102320615A (en) * | 2011-09-11 | 2012-01-18 | 中国科学院过程工程研究所 | Method for preparing precipitated silica by adopting micro-silica fume as raw material |
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| CN102066252A (en) * | 2008-02-12 | 2011-05-18 | 日产化学工业株式会社 | Colloidal silica particles, process for producing the same, and silica sol in organic solvent, silica sol in polymerizable compound, and silica sol in dicarboxylic anhydride each obtained from the same |
| CN102320615A (en) * | 2011-09-11 | 2012-01-18 | 中国科学院过程工程研究所 | Method for preparing precipitated silica by adopting micro-silica fume as raw material |
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