CN101460400A - Pelletized silica - Google Patents
Pelletized silica Download PDFInfo
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- CN101460400A CN101460400A CNA2007800205334A CN200780020533A CN101460400A CN 101460400 A CN101460400 A CN 101460400A CN A2007800205334 A CNA2007800205334 A CN A2007800205334A CN 200780020533 A CN200780020533 A CN 200780020533A CN 101460400 A CN101460400 A CN 101460400A
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/02—Pretreated ingredients
- C03C1/026—Pelletisation or prereacting of powdered raw materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3009—Physical treatment, e.g. grinding; treatment with ultrasonic vibrations
- C09C1/3036—Agglomeration, granulation, pelleting
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- 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
- C01P2006/12—Surface area
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- 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
- C01P2006/16—Pore diameter
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- 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
Abstract
Pelletized silica particles characterized by a round shape and a monomodal particle size distribution are produced by dispersing silica particles into water, adding water to the dispersion, mixing with alkoxisilane, pouring the mixture into an organic solvent, filtering and washing the silica particles obtained. The pelletized silica particles can be used to produce glass monoliths.
Description
Technical field
The present invention relates to pelletized silica particle, Preparation Method And The Use.
Background technology
Having known can be by preparing gel at specific pH hydrolyzable alkoxy TMOS, make the gel powdered, the described powder of calcining prepares quartz (silicon-dioxide) glass powder (Japanese Patent patent application (KOKA1) No.62-17 69 28 (1987)) after drying then.
Also know and can prepare the synthetic quartz glass powder by following step:
A) the hydrolyzable alkoxy TMOS is to form its gel
B) differentiation (dividing) described gel is dry then subtly, distinguish subtly behind the perhaps dry described gel to make it become powder, and
C) powder (US 5,516,350) of step calcining b).
It is 60 to 900 μ m that the granularity of the gel before calcining step is adjusted to diameter.The granularity of the not mentioned agglomerating quartz glass powder of reference and mobile feature thereof.
Also know by following step and prepare whole silica glass goods:
-in solution the hydrolysising silane oxycompound to form hydrating solution
-in described hydrating solution, add the pyrolytic silicon dioxide of effective quantity to form sol solution
The described sol solution of-gelation is to form gel
-dry described gel to be forming xerogel, and
The described xerogel of-calcining forms big whole silica glass goods (US 4,801,318) thus to form glass
This process can not prepare the free flowing powder of synthetic quartz.
Also know and can prepare spheric inorganic oxide substrate material by following step with basic unimodal distribution:
-form the colloidal sol of at least a inorganic oxide by the hydrolysis tetraalkoxysilane
-in described colloidal sol, add and the immiscible solvent of described colloidal sol
-two-phase mixture that is obtained is disperseed to become same diameter particulate dispersion subtly
-by conditional coalescent (limited coalescence) described particle is grown up, and make this dispersion (coalescent droplet) gelling by second solvent that adding contains jelling agent, and
-remove described solvent.
Under the situation of unimodal distribution, described sphere material shows that its diameter is in 1nm and 1, between the 000nm.It can be used for the carrier (EP 0 537850 A1) as the catalyzer of alefinically unsaturated compounds polymerization and copolymerization.
Also know and can prepare the preparing spherical SiO 2 particle by following step:
(A) under the situation that mineral acid or organic acid exist, by hydrolysising silane oxycompound in water-bearing media with preparation colloid silica solution
(B) choose wantonly in the colloid silica solution that obtains and disperse pyrolytic silicon dioxide
(C) in the organic medium of forming by simple function Fatty Alcohol(C12-C14 and C12-C18) R-OH or its mixture, mix pure (steps A) or blended (step B) silicon dioxide gel
(D) the resulting mixture of emulsification
(E) contact with alkaline solution by the emulsion that will before obtain, make described pure or described blended silicon dioxide gel gelation
(F) to the heat treated of the gel of gained
The preparing spherical SiO 2 particle has shown the particle diameter (EP 0 653 378 A1) in 10 to 100 micrometer ranges.
The transportation of powdered material, processing and storage largely are subjected to the influence of described particulate flowability and hardness, and therefore this also can have very big business impact to the quality of price and the finished product.Particularly, the mixing efficiency of powder can be pind down by uneven size-grade distribution, particle aggregation and agllutination problem consumingly.
Statement in this specification " free flowing powder composition " be meant (by mill, micronize or similar techniques make) powder that wherein particle is made of above-mentioned composition and wherein particle can be not adhering to each other.The size of powder particle is expressed according to particle diameter.Usually, this size is next definite and irrelevant with described coating of particles by screening.
On the contrary, coherency powder (cohesive powder) is that the clinging power between the particle is very important (strengthwise) those powder.According to definition, free-pouring powder does not comprise fine powder (fines).
Conventionally spray-dried technology (wherein spray-dryer mixes hot gas and atomizing (spraying) liquid flow in container (kiln), to finish the free-pouring dry powder that evaporation and preparation have controlled mean particle size) can derive from for example SDS Spray Drying Limited.Adopting such spray-dryer can prepare the mean sizes with narrower size-grade distribution is 300 microns particle.
Make that micronized another better mode of metal oxide particle is that for example polymkeric substance or oil or wax carry out coating with chemical.In this case, significant variation takes place in the character of particulate thus, seldom reports in scientific literature.
Even reported the micronisation process of the metal oxide of a large amount of industrial level operation in the literature, for example still be subjected to commonly known problems affect along travelling belt or the mixing in the wind-force forwarder and transportation, for example:
A) segregation (segregation): mainly due to described particulate size difference, and less degree ground is because the difference of pellet density.More specifically, the reactive force that orders about described segregation is: Van der Waals force, electrostatic force, liquid bridge power (liquid bridge), solid matter bridge (solid matterbridge) and tangle.
B) diafiltration (percolation), in passing test, having undersized particle can little by little move under the bigger particle, and causes the different size particulate to separate thus.
With regard to particulate purity, the purity of silicon-dioxide is main.In fact, at present increasing to the demand of high purity rank silicon-dioxide in senior terminal applies, for example: the internal part of crucible, optical fiber and microelectronic element.Regrettably, because very high cost and very complicated production technique, product such on market is also few.
Summary of the invention
Theme of the present invention is the pelletized silica particle, it is characterized in that sphere and monomodal grit distribution.
Silica dioxide granule of the present invention has described silicon-dioxide as nuclear, is the SiO that obtains by the hydrolyzed liquid organoalkoxysilane on every side
2
Especially preferred silicon-dioxide can be the SiO as pyrolytic silicon dioxide or natural quartz
2Described natural quartz can be for example, to derive from JOTA 4 types of JOTA Corporation and the natural quartz that derives from Norwegian crystallites.
In a preferable feature of the present invention, the particulate inorganic oxides particulate is endorsed to be made up of natural quartz, and described natural quartz is on every side around the silicon-dioxide that obtains by the hydrolyzed liquid organoalkoxysilane.Described organoalkoxysilane can be preferably tetraalkoxysilane, for example tetraethoxysilane.
Described particulate inorganic oxides particle of the present invention is characterized by surface-area greater than 50m
2/ g.
Described particulate inorganic oxides particulate at least 90% has the size above 100 microns.At least 90% hole has the diameter between 50 and 1000 dusts.
In addition, organoalkoxysilane can mix with soluble salt, to obtain to be doped with the particulate inorganic oxides particle of metal.
According to Degussa GmbH exploitation and be published in the method for Technical Bulletin Fine ParticlesNumber 11 " Basic Characterisation of Aerosil Fumed Silica ", the scope of unrestricted flow value more preferably from 5 to 2.Powder with poor flowing property is labeled as 5, and the powder with extraordinary flowing property is labeled as 1.
The further target of the present invention is the pelletized silica particulate method that preparation has spherical and monomodal grit distribution.According to the present invention; it is characterized by: under agitation; the inorganic silicon dioxide that will carry out granulation joins in the container that sour water is housed; when dispersion obviously evenly and when not having piece, in mixture, add liquid organoalkoxysilane for example tetramethoxy-silicane and/or tetraethoxysilane very lentamente.Because thermopositive reaction, temperature rises.By pipeline for example the dispersion that is obtained is slowly changed under keeping violent stirring in the container that is equipped with in advance with ammonia derivative blended organic solvent or silicone oil then.The droplet of the silica dispersion that contacts with alkaline organic solution forms the gel particle, described gel particle concentrates on the bottom of reactor, be transported to then in the other container and wash with alcohol and/or ester (for example diox, propyl alcohol, acetone, ethanol or pure ethyl acetate), at last, with the described particle of washing with acetone.Organic solvent or silicone oil are used for other circulation then.With described particle filtration, then overcritical or extract solvent under the undercritical conditions slightly.Perhaps can be by the dry solvent of removing of (humidity percentage and temperature) control under the condition of control.Then under the high temperature aerobic calcining dry granules at least 1 hour from silica dioxide granule, to remove trace solvent.
More specifically, the present invention relates to method by powdered preparation silica dioxide granule with wide distribution of sizes.Can use the sol-gel technique of part description in EP0 537 850 A to carry out granulating.
In a preferred theme of the present invention, described method can comprise following characteristics:
At room temperature add acid in the water in container up to reaching acid pH (2).Adding SiO 2 powder under violent stirring very lentamente, is liquid silane oxycompound such as TEOS (Dynasil A derives from DEGUSSA AG) then.Because the heat release hydrolysis reaction, temperature rises.Described then mixture keeps stirring at least 20 minutes.
After vigorous stirring, described solution is poured in the container that organic solvent is housed by pipeline.The Primene type that is for example provided by Rohm and Haas by adding amine makes pH raise, up to setting up the very condition of alkalescence, for example pH in 10% aqueous solution.Temperature further raises.From reactive tank, take out described particle continuously, and wash the particle that is obtained, to remove residual solvent with massive laundering.The material that obtains is calcined 6 ± 2 hours to remove residual solvent under 600 ± 150 ℃ in vertical furnace.
Handled particle has at least 90% particulate size greater than 100 microns size.By using tetraethoxysilane to obtain granulating as granulating agent.
When the natural quartz powder is carried out granulating, some difference of situation.At room temperature add acid in the water in container up to reaching acid pH (2).Under agitation in mixture, add liquid silane oxycompound such as TEOS (Dynasil A derives from DEGUSSA AG).Because the heat release hydrolysis reaction, temperature rises.In mixture, add the natural quartz powder then, keep again stirring at least 20 minutes.
After vigorous stirring, described solution under stirring, is poured in the container that organic solvent is housed intensive.The Primene type that is for example provided by Rohm and Haas by adding amine makes pH raise, up to setting up the very condition of alkalescence, for example pH in 10% the aqueous solution.Temperature further raises.From reactive tank, take out described particle continuously, and wash the particle that is obtained, to remove residual solvent with massive laundering.The material that obtains is calcined 6 ± 2 hours to remove residual solvent under 600 ± 150 ℃ in vertical furnace.
In addition, the present invention relates to a kind of free flowing powder composition, said composition comprises hydrolysising silane oxycompound for example TEOS and metal oxide and/or their mixture.
The particulate feature is to be subcontinuous phase between granulating agent (the silane oxycompound of hydrolysis is TEOS for example) and nuclear matter, and this is because described granulating agent can infiltrate in the inorganic oxide particles.
The glass particles that the method according to this invention obtains has the feature of following several respects: flowability, microporosity and distribution of sizes.In addition, when described inorganic oxide is silicon-dioxide or natural quartz, this method can obtain comparing with primary particles more highly purified final product.The increase of purity roughly is for example direct function of the usage quantity of TEOS of granulating agent silane oxycompound.
Initial pH with aqueous solution of inorganic oxide particles can be in 1 to 4 scope.
The liquid organoalkoxysilane can be tetramethoxy-silicane (CH
3O)
4Si and/or tetraethoxysilane (CH
3-CH
2-O)
4Si.
Organic solvent can be a kind of non-polar organic solvent, and its specific inductivity is lower than 60 under 20 ℃.
The salt that adds in order to obtain the doping silicon dioxide particle can be aluminum acetate, Tai-Ace S 150, Tai-Ace S 150 ammonia, lead acetate, boric acid, sulfuric acid aluminum fluoride, aluminum fluoride especially.
Described non-polar organic solvent can be that for example hexane, heptane, octane, nonane and alcohols be for example for liquid alkane: propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol and aromatic substance be toluene, benzene, oil of mirbane, chlorobenzene, dichlorobenzene, quinoline, naphthalane and/or their mixture for example.
Can also use silicone oil as organic solvent.Silicone oil can be the Dimethicone under Wacker AK 50 trade marks that polydimethylsiloxane fluid for example derives from Wacker Chemie AG.
Organic basic ammonia derivative can be cyclo-hexylamine, t-alkylamine.
PH after adding organic bases can be, is expressed as 10% aqueous solution, in from 8 to 13 the scope, and more preferably from 10 to 11.
Calcining temperature can be between 300 and 700 ℃, more preferably between 300 and 600 ℃.
Pelletized silica particulate feature is spherical and does not have fine powder basically.
Size-grade distribution is by Horiba LA-300 measuring apparatus.
Show that at the analysis of pelletized silica particulate the method according to this invention can obtain unimodal distribution.
The microporosity of material and surface-area are determined by the ASAP 2010 that derives from Micromeritics according to the method for DIN 66131; Be determined in the liquid nitrogen and carry out.
Before analysis, with material at 300 ℃ of down degassings 4 hours (P=1 * 10ex-6).
Flowability adopts the viscosity device of similar hourglass to determine by very simple but significant method.When this method of employing, the powder with good flow character still flows out Glass Containers (seeing Degussa Aerosil Silanes Technical Bulletin Fine particle, 56-57 page or leaf, 2005) by little relief outlet.When powder/granule only flows through very large container, think mark 5, and when powder/granule easily flows through very thin container, mark 1.
Being used for dispersion gel particulate solvent with the ammonia derivative in titration process is nonpolar, and its specific inductivity is not higher than 60.The list of proof solvent comprises: for example hexane, heptane, octane, nonane and alcohols be for example for alkane: propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol and aromatic substance be toluene, benzene, oil of mirbane, chlorobenzene, dichlorobenzene, quinoline and naphthalane for example.
Described pelletized silica particulate purity detects by ICP-MAS.
Amount by reducing fine powder also makes size distribution narrow, and pelletized silica particle of the present invention can improve the traffic capacity of material significantly.
Embodiment
Embodiment 1:
At room temperature (19 ℃), hydrochloric acid 37 weight % adding is equipped with in the 4L container of 900ml water, up to pH to 2.Under agitation add the 650g pyrolytic silicon dioxide, the Aerosil EG50 by Degussa provides carries out granulating very slowly.When dispersion is obviously even and does not have block, 650gTEOS (Dynasil 40, derive from DEGUSSA AG) is added in the mixture very slowly.Because the heat release hydrolysis reaction, temperature is increased to 24 ℃.After 1 hour vigorous stirring, by pipeline with solution slowly be added drop-wise to be equipped with tertiary amine (Primene JM-T (providing)) blended 15L silicone oil (Wacker AK 50 by Rohm and Haas, derive from Wacker Chemie) the 22L container in, described tertiary amine makes that pH is 11 (being expressed as 10% aqueous solution).Temperature further is increased to 31 ℃.Filtration contains gel particulate emulsion and thus obtained particle water/acetone soln is washed fully then, to remove residual silicone oil.Thus obtained material is calcined 8 hours then to remove residual solvent under 600 ℃ in vertical furnace.
Feature:
Granularity: the feature of this material is a unimodal size distribution
Mean diameter is 430 microns
The size of original material is 3.7 microns
Porousness: the aperture is 60 dusts, surface-area 99m
2/ g (this is almost 2 times of surface-area of original material)
Ultimate analysis:
Impurity in the original material (ppm)
Na 1.6
K 0.3
Li 3.8
Al 23
Ca 0.5
Fe 0.6
Ti 2.4
Co 0.01
Cu 0.01
Cr 0.02
Impurity (ppm) in the final material
Na 0.6
K 0.05
Li 3.0
Al 12
Ca 0.03
Fe 0.01
Ti 1.0
Co <0.01
Cu <0.01
Cr <0.01
Granulating significantly improved the particulate size with and distribute (unimodal distribution), and the purity of final material is more far better than the primary particles.
Mobile: original material is labeled as 5, and pelletized silica is labeled as 2, the unrestricted flow performance that this means the granulating process improving.
Embodiment 2:
Under room temperature (19 ℃), in being housed, the 4L container of 900ml water adds the hydrochloric acid of 37 weight % concentration up to pH2.Under violent stirring, in mixture, add 650g tetraethoxysilane (TEOS) (Dynasil 40, derive from DEGUSSA AG) very slowly.Because the heat release hydrolysis reaction, temperature rises to 22 ℃.After the vigorous stirring 1 hour, solution dropwise added under violent stirring be equipped with in the 22L container of 15L silicone oil (Wacker AK 50 derives from Wacker Chemie).By tertiary amine (Primene JM-T (providing by Rohm and Haas)) rising pH is provided, be 11 (10% aqueous solution) up to pH, this pH is equivalent to the pH of silicon oil solution that concentration is the Primene of 10%w/w.Temperature further is increased to 31 ℃.Liquid filters then and contains gel particulate emulsion and thus obtained particle water washs fully, to remove residual silicone oil.Thus obtained material is calcined 8 hours then to remove residual solvent under 600 ℃ in vertical furnace.
Feature:
Granularity: the feature of this material is a unimodal size distribution
Mean diameter is 500 microns
The size of original material is 5.7 microns porousness: surface-area 74m
2/ g (than the almost non-detectable low surface area of natural quartz)
Ultimate analysis:
Impurity in the original material (ppm)
Na 1.9
K 0.6
Li 3.8
Al 36.0
Ca 1.0
Fe 0.4
Ti 3.2
Co <0.001
Cu 0.009
Cr 0.03
Impurity (ppm) before the calcining in the final material
Na 2.0
K 0.78
Li 3.1
Al 20
Ca 1.7
Fe 0.51
Ti 3.2
Co <0.01
Cu <0.015
Cr 0.43
Impurity (ppm) in the final material in calcining back
Na 0.9
K 0.59
Li 2.01
Al 21.0
Ca 3.40
Fe 0.01
Ti 2.9
Co <0.01
Cu <0.01
Cr <0.02
Granulating significantly improved the particulate size with and distribute (unimodal distribution), and the purity of final material is more far better than the primary particles.
Mobile: original material is labeled as 5, and the granular natural quartz before the calcining process is labeled as 4, and being marked between 2 and 3 behind the calcining process, the unrestricted flow performance that this means the granulating process improving.
Embodiment 3
At room temperature (19 ℃), hydrochloric acid 37 weight % adding is equipped with in the 4L container of 900ml water, up to pH to 4.Dissolve 85gNH4F under violent stirring, under agitation add the 585g pyrolytic silicon dioxide then very slowly, the Aerosil EG50 by Degussa provides carries out granulating.When dispersion is obviously even and does not have block, 650g TEOS (Dynasil 40, derive from DEGUSSA AG) is added in the mixture very slowly.Because the heat release hydrolysis reaction, temperature is increased to 24 ℃.After 1 hour vigorous stirring, solution is added drop-wise to very slowly 15L silicone oil (Wacker AK 50 is housed, derive from Wacker Chemie) the 22L container in, the pH of silicone oil groove raises by tertiary amine (Primene JM-T (being provided by Rohm and Haas)) is provided, up to pH is 11 (being expressed as 10% aqueous solution), and this pH is equivalent to the pH of silicon oil solution that concentration is the Primene of 10%w/w.Temperature further is increased to 31 ℃.Filtration contains gel particulate emulsion and thus obtained particle is washed fully with acetone solution then, to remove residual silicone oil.Thus obtained material is calcined 8 hours then to remove residual solvent under 600 ℃ in vertical furnace.
Feature:
Granularity: the feature of this material is a unimodal size distribution
Mean diameter is 300 microns
The size of original material is 5.7 microns
Claims (21)
1, pelletized silica particle is characterized in that sphere and monomodal grit distribution.
2, a kind of preparation is according to the pelletized silica particulate method of claim 1, it is characterized in that, under agitation silica dioxide granule is dispersed in the acid pH water, add the liquid organoalkoxysilane then, under violent stirring, change over to the dispersion that is obtained in the container that organic solvent is housed, by adding organic bases ammonia derivative pH is raise then, the gel particle that obtains is washed with alcohol, mixture with alcohol and water washs then, filter described particle then, then at high temperature calcine at least 1 hour from inorganic oxide particles, to remove trace solvent.
3, method according to claim 2 is characterized in that, described silicon-dioxide is pyrolytic silicon dioxide.
4, method according to claim 2 is characterized in that, the scope of the initial pH of the aqueous solution of silica dioxide granule is 1 to 4.
5, method according to claim 2 is characterized in that, described silicon-dioxide is pyrolytic silicon dioxide.
6, method according to claim 2 is characterized in that, described liquid organoalkoxysilane is tetramethoxy-silicane and/or tetraethoxysilane.
7, method according to claim 2 is characterized in that, described organic solvent be non-polar organic solvent and its specific inductivity under 20 ℃ less than 60.
8, method according to claim 2 is characterized in that, the described aqueous solution comprises the soluble salt as final particulate doping agent.
9, method according to claim 7, it is characterized in that, described non-polar organic solvent is for example hexane, heptane, octane, nonane or a silicone oil of liquid alkane, with alcohols for example toluene, benzene, oil of mirbane, chlorobenzene, dichlorobenzene, quinoline, naphthalane and/or their mixture of propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol and aromatic substance for example.
10, method according to claim 2 is characterized in that, described ammonia derivative is cyclohexyl ammonia, t-alkyl ammonia.
11, method according to claim 2 is characterized in that, adds pH behind the described organic bases in 8 to 12 scope, more preferably 10 to 12.
12, method according to claim 2 is characterized in that, described calcining temperature is between 300 and 800 ℃, more preferably between 300 and 600 ℃.
13, a kind of preparation is characterized in that according to the granular natural quartz particulate method of claim 1, under agitation adds the liquid organoalkoxysilane in the oxytropism pH water, adds the natural quartz powder then under violent stirring in solution; Under violent stirring, change over to the dispersion that is obtained in the container that organic solvent is housed, by adding organic bases ammonia derivative pH is raise then, the gel particle that obtains is washed with alcohol, mixture with alcohol and water washs then, filter described particle then, then calcining at high temperature is at least 1 hour, to remove trace solvent from inorganic oxide particles.
14, method according to claim 13 is characterized in that, the scope of the initial pH of the aqueous solution of silica dioxide granule is 1 to 4.
15, method according to claim 13 is characterized in that, described liquid organoalkoxysilane is tetramethoxy-silicane and/or tetraethoxysilane.
16, method according to claim 13 is characterized in that, described organic solvent be non-polar organic solvent and its specific inductivity under 20 ℃ less than 60.
17, method according to claim 13 is characterized in that, the described aqueous solution comprises the soluble salt as final particulate doping agent.
18, method according to claim 16, it is characterized in that, described non-polar organic solvent is for example hexane, heptane, octane, nonane or a silicone oil of liquid alkane, with alcohols for example toluene, benzene, oil of mirbane, chlorobenzene, dichlorobenzene, quinoline, naphthalane and/or their mixture of propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol and aromatic substance for example.
19, method according to claim 13 is characterized in that, described ammonia derivative is cyclohexyl ammonia, t-alkyl ammonia.
20, method according to claim 13 is characterized in that, adds pH behind the described organic bases in 8 to 12 scope, more preferably 10 to 12.
21, method according to claim 13 is characterized in that, described calcining temperature is between 300 and 800 ℃, more preferably between 300 and 600 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EPPCT/EP2006/062883 | 2006-06-02 | ||
| EP2006062883 | 2006-06-02 | ||
| PCT/EP2007/055365 WO2007141196A1 (en) | 2006-06-02 | 2007-05-31 | Pelletized silica |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101460400A true CN101460400A (en) | 2009-06-17 |
| CN101460400B CN101460400B (en) | 2011-09-14 |
Family
ID=37697918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800205334A Expired - Fee Related CN101460400B (en) | 2006-06-02 | 2007-05-31 | Pelletized silica |
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| Country | Link |
|---|---|
| JP (1) | JP2009538816A (en) |
| KR (1) | KR101089897B1 (en) |
| CN (1) | CN101460400B (en) |
| AU (1) | AU2007255488B2 (en) |
| CA (1) | CA2653155C (en) |
| NO (1) | NO20084294L (en) |
| TW (1) | TWI372139B (en) |
| WO (1) | WO2007141196A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479954A (en) * | 2019-08-19 | 2019-11-22 | 安徽省含山县兴建铸造厂 | A kind of model casting precision casting shell fire resistant covering material |
| CN111170344A (en) * | 2020-01-15 | 2020-05-19 | 珠海琴晟新材料有限公司 | Preparation method of ultra-pure nano material |
| CN111634915A (en) * | 2020-06-12 | 2020-09-08 | 将乐三晶新材料有限公司 | Atomization powder making process for molten metal silicon |
| CN111747417A (en) * | 2019-03-28 | 2020-10-09 | 福建通源硅业有限公司 | Preparation method of silicon dioxide particles |
| CN111868159A (en) * | 2020-02-17 | 2020-10-30 | 浙江三时纪新材科技有限公司 | Preparation method of spherical silicon dioxide powder filler, powder filler obtained by preparation method and application of powder filler |
| CN115974089A (en) * | 2023-02-17 | 2023-04-18 | 江苏海格新材料有限公司 | Production method of active silicon micropowder |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2559608A (en) * | 2017-02-13 | 2018-08-15 | Sibelco Nederland N V | Grains comprising silica and methods of forming grains comprising silica |
| US10343941B2 (en) * | 2017-06-16 | 2019-07-09 | Owens-Brockway Glass Container Inc. | Glass batch material and process for making glass |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62260712A (en) * | 1986-05-02 | 1987-11-13 | Toray Ind Inc | Production of silica particle |
| EP0725037B2 (en) * | 1995-02-04 | 2012-04-25 | Evonik Degussa GmbH | Granules on the basis of pyrogenic silica, process for their preparation and use thereof |
| JPH08281095A (en) * | 1995-02-14 | 1996-10-29 | Toyota Motor Corp | Dilatant liquid |
| DE10123950A1 (en) * | 2001-05-17 | 2002-11-28 | Degussa | Granules based on pyrogenic silicon dioxide doped with aluminum oxide by means of aerosol, process for their production and their use |
| DE10256267A1 (en) * | 2002-12-03 | 2004-06-24 | Degussa Ag | Dispersion, coating color and recording medium |
| DE102004011110A1 (en) * | 2004-03-08 | 2005-09-22 | Merck Patent Gmbh | Process for producing monodisperse SiO 2 particles |
-
2007
- 2007-05-30 TW TW096119361A patent/TWI372139B/en not_active IP Right Cessation
- 2007-05-31 CN CN2007800205334A patent/CN101460400B/en not_active Expired - Fee Related
- 2007-05-31 AU AU2007255488A patent/AU2007255488B2/en not_active Ceased
- 2007-05-31 WO PCT/EP2007/055365 patent/WO2007141196A1/en active Application Filing
- 2007-05-31 KR KR1020087029435A patent/KR101089897B1/en not_active IP Right Cessation
- 2007-05-31 CA CA2653155A patent/CA2653155C/en not_active Expired - Fee Related
- 2007-05-31 JP JP2009512608A patent/JP2009538816A/en active Pending
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2008
- 2008-10-14 NO NO20084294A patent/NO20084294L/en not_active Application Discontinuation
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111747417A (en) * | 2019-03-28 | 2020-10-09 | 福建通源硅业有限公司 | Preparation method of silicon dioxide particles |
| CN110479954A (en) * | 2019-08-19 | 2019-11-22 | 安徽省含山县兴建铸造厂 | A kind of model casting precision casting shell fire resistant covering material |
| CN111170344A (en) * | 2020-01-15 | 2020-05-19 | 珠海琴晟新材料有限公司 | Preparation method of ultra-pure nano material |
| CN111868159A (en) * | 2020-02-17 | 2020-10-30 | 浙江三时纪新材科技有限公司 | Preparation method of spherical silicon dioxide powder filler, powder filler obtained by preparation method and application of powder filler |
| CN111634915A (en) * | 2020-06-12 | 2020-09-08 | 将乐三晶新材料有限公司 | Atomization powder making process for molten metal silicon |
| CN115974089A (en) * | 2023-02-17 | 2023-04-18 | 江苏海格新材料有限公司 | Production method of active silicon micropowder |
| CN115974089B (en) * | 2023-02-17 | 2023-10-20 | 江苏海格新材料有限公司 | Production method of active silicon micropowder |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2007255488A1 (en) | 2007-12-13 |
| CA2653155C (en) | 2012-01-24 |
| AU2007255488B2 (en) | 2011-01-27 |
| CN101460400B (en) | 2011-09-14 |
| CA2653155A1 (en) | 2007-12-13 |
| TWI372139B (en) | 2012-09-11 |
| KR101089897B1 (en) | 2011-12-05 |
| KR20090009290A (en) | 2009-01-22 |
| TW200815284A (en) | 2008-04-01 |
| JP2009538816A (en) | 2009-11-12 |
| WO2007141196A1 (en) | 2007-12-13 |
| NO20084294L (en) | 2009-01-09 |
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