CN101723388A - Silica granules prepared on basis of pyrolysis and preparation method and app {} lication thereof - Google Patents
Silica granules prepared on basis of pyrolysis and preparation method and app {} lication thereof Download PDFInfo
- Publication number
- CN101723388A CN101723388A CN200810177872A CN200810177872A CN101723388A CN 101723388 A CN101723388 A CN 101723388A CN 200810177872 A CN200810177872 A CN 200810177872A CN 200810177872 A CN200810177872 A CN 200810177872A CN 101723388 A CN101723388 A CN 101723388A
- Authority
- CN
- China
- Prior art keywords
- silicon
- preparation
- pore
- pyrolysis
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention relates to silica granules prepared on basis of pyrolysis and a preparation method and application thereof. Particularly, the invention relates to silica granule prepared on basis of pyrolysis, which has the following physicochemical property data: average granule diameter: 10-120 mu m; BET specific surface area: 40-400m2/g; pore volume: 0.5-2.5 ml/g; pore distribution: in the whole pore volume, the content of pore of which the pore diameter is smaller than 5 nm is less than 5%, and the balance mesopore and macropore compacted density: 220-1000g/l. The granularity is within the granularity range which is more than granularity distributed D10 value measured according to volume, and the numerical value content of granules containing tucks or sealed internal gaps is smaller than 35%. The granules are prepared with the following method: silica and one or a plurality of accessory ingredients are dispersed in liquid, preferably water; then, the dispersoid is atomized and dried; and if necessary, the granule is performed with heat treatment and/ or silanization. The granule can serve as a catalyst carrier.
Description
Technical field
The present invention relates to based on pyrolysis preparation silica granules and preparation method thereof and as the purposes of support of the catalyst.
Background technology
By high temperature or flame hydrolysis by SiCl
4Preparation preparation fumed silica or silicon-dioxide are known (Ullmanns
Der technischen Chemie, [Ullmanns Encyclopaedia ofIndustrial Chemistry], 4th edition, volume 21, page 464 (1982)).
The special character of pyrolytic silicon dioxide is very fine distribution (fine division), high specific surface area (BET), very high purity, spheroidal particle shape and does not have the hole.Because these character are more and more found the value (Dr.Koth et al., Chem.Ing.Techn.52,628 (1980)) of the silicon-dioxide of pyrolysis preparation as support of the catalyst.Use for this type of, the silicon-dioxide of pyrolysis preparation is by mechanical means, and for example tabletting machine comes moulding.
Making the silicon-dioxide of pyrolysis preparation be shaped into spraying granule by spraying drying also is known technology.US5776240 has described the particle of the pyrolytic silicon dioxide that obtains based on the aqeous suspension by the spraying drying pyrolytic silicon dioxide.Zhi Bei particulate defective has been surperficial tuck (forming cavity (amphore formation)), internal voids and distortion by this method.These effects are well-known (K.Masters, Spary Drying, 2 in spraying drying
NdEd., 1976, John Wiley ﹠amp; Sons, New York, p.329).These anomalads have disadvantageous effect in the application as support of the catalyst.Such as, in the olefinic polymerization, because print effect, the shape of support of the catalyst can be aggregated composition granule and duplicate.This causes generation space and distortion in polymkeric substance equally, and this can reduce volume density (reaching thereby reduce the turnout of polymerization equipment) or possibility inclusion monomer, and this brings disadvantageous effect for further processing.When being used as the carrier of other fluid catalyst, these defectives can cause wearing and tearing that increase and the catalyst attrition that therefore increases.
Summary of the invention
Therefore, purpose of the present invention is exactly the spraying granule of improvement of the silicon-dioxide of exploitation pyrolysis preparation, and it can be as the support of the catalyst of olefinic polymerization or other catalysis fluidized-bed process.Compared with prior art, to be wherein to have the particulate concentration in tuck and space lower for the difference part.
The invention provides silica dioxide granule based on the pyrolysis preparation with following physicochemical property data:
Average particulate diameter: 10 to 120 μ m
The BET surface-area: 40 to 400m
2/ g
Pore volume: 0.5 to 2.5ml/g
Pore distribution: in the total pore volume median pore diameter less than the hole of 5nm
Content is less than 5%, and all the other are mesopore and macropore
Compacted density: 220 to 1000g/l
Granularity is in greater than the size range of the D10 value of the size-grade distribution of weighing according to volume and have the particulate numerical value content of the internal voids of tuck or sealing: less than 35%.
Particle of the present invention is to prepare by the following method: wherein, to be dispersed in by the silicon-dioxide that flame hydrolysis is made by volatile silicon compound in the liquid that contains one or more organic or inorganic auxiliary agents, in the preferably water, this dispersion of spraying drying is randomly heat-treated the particle that obtains and/or silanization under 150 to 1100 ℃ temperature then.
Halogenated silanes, organoalkoxysilane, silazane and/or siloxanes can be used for silanization.
Especially, following material can be used as halogenated silanes:
X
3Si (C
nH
2n+1) the halo organosilane of type, X=Cl, Br
n＝1-20
X
2(R ') Si (C
nH
2n+1) the halo organosilane of type, X=Cl, Br
R '=alkyl
n＝1-20
X (R ')
2Si (C
nH
2n+1) the halo organosilane of type, X=Cl, Br
R '=alkyl
n＝1-20
X
3Si (CH
2)
mThe halo organosilane of-R ' type
X＝Cl、Br
m＝0、1-20
R '=alkyl, aryl (as-C
6H
5)
-C
4F
9、-OCF
2-CHF-CF
3、-C
6F
13、-O-CF
2-CHF
2
-NH
2、-N
3、-SCN、-CH＝CH
2，
-OOC(CH
3)C＝CH
2
-OCH
2-CH(O)CH
2
-NH-CO-N-CO-(CH
2)
5
-NH-COO-CH
3、-NH-COO-CH
2-CH
3、-NH-(CH
2)
3Si(OR)
3、
-S
x-(CH
2)
3Si(OR)
3
(R) X
2Si (CH
2)
mThe halo organosilane of-R ' type
X＝Cl、Br
The R=alkyl
m＝0、1-20
R '=alkyl, aryl (as-C
6H
5)
-C
4F
9、-OCF
2-CHF-CF
3、-C
6F
13、-O-CF
2-CHF
2
-NH
2、-N
3、-SCN、-CH＝CH
2，
-OOC(CH
3)C＝CH
2
-OCH
2-CH(O)CH
2
-NH-CO-N-CO-(CH
2)
5
-NH-COO-CH
3、-NH-COO-CH
2-CH
3、-NH-(CH
2)
3Si(OR)
3、
-S
x-(CH
2)
3Si(OR)
3
(R)
2XSi (CH
2)
mThe halo organosilane of-R ' type
X＝Cl、Br
The R=alkyl
m＝0、1-20
R '=alkyl, aryl (as-C
6H
5)
-C
4F
9、-OCF
2-CHF-CF
3、-C
6F
13、-O-CF
2-CHF
2
-NH
2、-N
3、-SCN、-CH＝CH
2，
-OOC(CH
3)C＝CH
2
-OCH
2-CH(O)CH
2
-NH-CO-N-CO-(CH
2)
5
-NH-COO-CH
3、-NH-COO-CH
2-CH
3、-NH-(CH
2)
3Si(OR)
3、
-S
x-(CH
2)
3Si(OR)
3
Especially, following material can be used as organoalkoxysilane:
(RO)
3Si (C
nH
2n+1) the organosilane R=alkyl of type
n＝1-20
R '
X(RO)
ySi (C
nH
2n+1) the organosilane R=alkyl of type
R '=alkyl
n＝1-20
x+y＝3
x＝1，2
y＝1，2
(RO)
3Si (CH
2)
mThe organosilane of-R ' type
The R=alkyl
m＝0、1-20
R '=alkyl, aryl (as-C
6H
5)
-C
4F
9、-OCF
2-CHF-CF
3、-C
6F
13、-O-CF
2-CHF
2
-NH
2、-N
3、-SCN、-CH＝CH
2，
-OOC(CH
3)C＝CH
2
-OCH
2-CH(O)CH
2
-NH-CO-N-CO-(CH
2)
5
-NH-COO-CH
3、-NH-COO-CH
2-CH
3、-NH-(CH
2)
3Si(OR)
3、
-S
x-(CH
2)
3Si(OR)
3
(R ")
x(RO)
ySi (CH
2)
mThe organosilane of-R ' type
R "=alkyl x+y=2
x＝1、2
y＝1、2
R '=alkyl, aryl (as-C
6H
5)
-C
4F
9、-OCF
2-CHF-CF
3、-C
6F
13、-O-CF
2-CHF
2
-NH
2、-N
3、-SCN、-CH＝CH
2，
-OOC(CH
3)C＝CH
2
-OCH
2-CH(O)CH
2
-NH-CO-N-CO-(CH
2)
5
-NH-COO-CH
3、-NH-COO-CH
2-CH
3、-NH-(CH
2)
3Si(OR)
3、
-S
x-(CH
2)
3Si(OR)
3
Silane Si 108[(CH
3O)
3-Si-C
8H
17] Trimethoxyoctylsilane is preferably used as silanizing agent.
Especially, following material can be used as silazane:
The R=alkyl
R '=alkyl, vinyl
Hexamethyldisilazane for example.
Especially, following material can be used as siloxanes:
The cyclic polysiloxanes of D3, D4, D5 type, for example octamethylcyclotetrasiloxane=D4
The polysiloxane of following type or silicone oil:
m＝0、1、2、3、...∞
n＝0、1、2、3、...∞
u＝0、1、2、3、...∞
Y＝CH
3、H、C
nH
2n+1，n＝1-20
Y＝Si(CH
3)
3、Si(CH
3)
2H
Si(CH
3)
2OH、Si(CH
3)
2(OCH
3)
Si(CH
3)
2(C
nH
2n+1)，n＝1-20
R=alkyl, aryl, (CH
2)
n-NH
2, H
R '=alkyl, aryl, (CH
2)
n-NH
2, H
R "=alkyl, aryl, (CH
2)
n-NH
2, H
R " '=alkyl, aryl, (CH
2)
n-NH
2, H
Particulate pore structure of the present invention mainly has mesopore and macropore.Based on the cumulative volume in hole, be no more than 5%. less than the content in the hole of 5nm
Particle also contains resistates and/or the silane components as residual additive material after the auxiliary material of second composition, the thermal treatment.The particulate carbon content can be 0 to 15 weight % according to the present invention.
The form of particulate size-grade distribution of the present invention make they have at least 80% volume content greater than the particle of 5 μ m and at least 80% particle less than 120 μ m.
The present invention also provides the preparation method based on the silica dioxide granule of pyrolysis method preparation, it is characterized in that silicon-dioxide with the pyrolysis preparation, the preferred silicon-dioxide that obtains by the flame hydrolysis silicon tetrachloride, be dispersed in the liquid that contains the organic or inorganic auxiliary material, the component of dispersion can be added with any required order, then described dispersion is carried out spraying drying, randomly the gained particle is heat-treated under 150 to 1100 ℃ of temperature, randomly particle is silylated and randomly particle is screened or sieves, and mentioned last three step process step can be implemented with required arbitrarily order.
Silica concentration is 5 to 40 weight % in the dispersion.Dispersion can be carried out continuously or off and on.
Can adopt the mixture of water, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, ethyl acetate or these materials to be for example dispersion medium.Preferably water is as dispersion medium.
Be used for spray-dired suitable auxiliary agents material, especially, organic additive material such as polymkeric substance, derivatived cellulose, polyoxyethylene glycol, wax, polyolefine, polyacrylic ester or polyvinyl alcohol are arranged for example, or organic acid, for example lactic acid or citric acid, or inorganic assistant agent material are as water glass, silicon sol, alumina sol or other oxide sol or tetraethyl orthosilicate.These auxiliary materials can be used alone or in combination, and have the effect of the particulate quantity minimizing of the internal voids that makes the profile of spraying granule more even, has tuck or sealing.
In addition, can randomly add and have the effect that reduces viscosity, thereby make other auxiliary material of filling dispersion of higher degree.The material that is suitable for this for example, acid, as formic acid, acetate, oxalic acid, hydrochloric acid or nitric acid, alkali is as the oxyhydroxide of ammonia, amine or basic metal, alkylammonium or alkaline-earth metal or have other material that can change discrete particles surface charge effect.
In order to make minimize contamination, based on the solids content in the dispersion, auxiliary material preferably is adopted as the low dose of 0.01 to 10 weight %.
Spraying drying is preferably in the inlet temperature of 180 to 700 ℃ dry air, and the air outlet temperature under 50 to 250 ℃ carries out.Here can use disc atomizer or nozzle atomization device.Required gas can be used as drying medium and uses preferred air or nitrogen arbitrarily.
The optional thermal treatment of particle can be carried out on static bed (as box-type furnace), agitated bed (as rotary tube furnace) or fluidized bed dryer or calcining furnace.
The silanization that can use halogenated silanes same as described above, organoalkoxysilane, silazane and/or siloxanes to choose wantonly, this silylating reagent can randomly be dissolved in organic solvent for example in the ethanol.
Silane Si 108[(CH
3O)
3-Si-C
8H
17], Trimethoxyoctylsilane can be preferably as silylating reagent.
Silanization can be undertaken by following technology: at room temperature with silylating reagent particle is sprayed, under 105 to 400 ℃ temperature mixture is heat-treated 1 to 6h then.
The other method of the grain silicon alkanisation that can adopt has following technology: the silylating reagent with the steam form is handled particle, under 50 to 800 ℃ temperature mixture is heat-treated 0.5 to 6h subsequently.
Thermal treatment randomly can for example be carried out in the nitrogen at rare gas element.
But silanization can carry out in heating mixer that possesses spraying equipment and moisture eliminator continuously or off and on.Suitable device is for example ploughshare mixer or dish, fluidized-bed or thermopnore (flow-bed) moisture eliminator.
In order preferably to isolate subparticle, in optional screening process, preferably adopt the air-flow screening washer.As selecting or in addition, using the sieving separating coarse particles.Can be after spraying drying any required moment of this method screen.The particulate fraction that is separated can randomly be mixed into the recirculation of initial dispersion body and be used.
By the condition during change initial substance and spraying, thermal treatment and the silanization, can in described restriction, change particulate the physical-chemical parameters, for example concentration of specific surface area, size-grade distribution, pore volume, compacted density and silanol group, pore distribution and pH.
Particle of the present invention can be used as support of the catalyst, particularly as the preparation of olefinic polymerization, Tetra hydro Phthalic anhydride, the preparation of vinyl acetate, the preparation or the Fischer-Tropsch synthetic support of the catalyst of aniline.
Particle advantageously have high purity, high thermal stability, less than the micro content of 5nm in total pore volume less than 5%, granularity in greater than the size range of the D10 value of the size-grade distribution of weighing according to volume and the particulate numerical value content with tuck or internal voids less than 35%.
The present invention also provides the purposes of described particle as support of the catalyst.
Embodiment
Embodiment
Employing has the silicon-dioxide of the silicon-dioxide of following physicochemical property data as the pyrolysis preparation:
Table 1
1) according to DIN 66131
2) according to DIN ISO 787/XI, JIS K 5101/18 (not sieving)
3) according to DIN ISO 787/II, ASTM D 280, JIS K 5101/21
4) according to DIN 55921, ASTM D 1208, JIS K 5101/23
5) according to DIN ISO 787/IX, ASTM D 1208, JIS K 5101/24
6) according to DIN ISO 787/XVIII, JIS K 5101/20
7) based on 2 hours material of drying under 105 ℃
8) based on the material that burnt 2 hours down at 1000 ℃
9) special packing is made moist preventing
10) water and ethanol are 1: 1
11) the HCl content in the composition of combustion loss
In order to prepare silicon-dioxide, be volatile silicon compound to be ejected in the hydrogen or oxygen gas flame of hydrogen and air make.In most cases, use silicon tetrachloride.This material is hydrolyzed to silicon-dioxide and hydrochloric acid under the effect of the water that hydrogen or oxygen gas formed between the reaction period.After leaving flame, silicon-dioxide enters so-called condensing zone, silica gel primary granule and elementary aggregate cohesion there.The product that exists with aerosol form in this step is followed separating substances with gas in cyclonic separator, carry out aftertreatment with damp-heat air then.
By this process, the content of residue hydrochloric acid is reduced to below 0.025%.Owing to when this end of processing, obtain the silicon-dioxide that volume density is approximately 15g/l, proceed vacuum debulk, can reach the about 50g/l of compacted density or bigger.
The granularity of silicon-dioxide can change according to reaction conditions, such as, the length of the content of flame temperature, hydrogen or oxygen, the amount of silicon tetrachloride, the residence time in flame or condensing zone.
Measure this BET area according to DIN 66 131 usefulness nitrogen.
The method that is pressed into (Hg forcing-in) according to mercury is measured pore volume.For this reason, sample, outgased under the room temperature in 100 ℃ times dry 15 hours then in a vacuum at loft drier.
(Halenda) method is estimated this and is measured micropore for de Boer and Barret, Joyner by drawing the N thermoisopleth and passing through BET.For this reason, with sample loft drier in 100 ℃ dry 15 hours down, then in the degassing 1 hour down of 200 ℃ in vacuum.
Measure particle size distribution with Cilas Granulameter 715 laser optics particle-size analyzers.Measure compacted density according to ASTM D 4164-88.
By counting mensuration on the SEM image that suitably amplifies tuck particulate content is arranged.Because particle is covered the estimation that causes uncertain+/-10% by tuck.Cross-section image can be used for detecting internal voids.In the particulate opening, its size is accounted for the 5%-90% of particle diameter, and to inner opening broadening at least the opening of minimum be evaluated as tuck.In order to get rid of the overexpression quantitatively of very thin particle, only consider the particle of diameter greater than the D10 value of the size-grade distribution of weighing according to volume.
Particulate preparation in embodiment 18 according to the present invention
In complete softening water, disperse the silicon-dioxide of pyrolysis preparation, mix specific auxiliary material.In this process, use dispersing apparatus according to the rotor/stator operate.With the suspensoid spraying drying that forms.Separate the finished product by strainer or cyclonic separator.
In retort furnace, spraying granule is heat-treated.
The particle of spraying drying and optional thermal treatment and/or screening is at first added the mixing tank that is used for silanization, and then optional at first water is used silane Si108 (Trimethoxyoctylsilane) or HMDS (hexamethyldisilazane) spraying then under violent stirring.After spraying is finished, carry out 15-30 minute back mixing again, then 100 to 400 ℃ of following heat treated 1 to 4 hour.
Can come water that acidifying adopts to pH value 7-1 with sour example hydrochloric acid.The silylating reagent that is adopted can be dissolved in solvent for example in the ethanol.
The relevant preparation of each particle embodiment and the details of character are listed in the table 2.As a comparison, prepared particle according to US5776240.
Description of drawings
Fig. 1-the 4th, particulate SEM image of the present invention.
The SEM image of Fig. 1 to Fig. 3 clearly illustrates that compared with prior art, the granule content with tuck obviously reduces.Shown the internal voids that does not have obvious amount among Fig. 4.
Claims (4)
1. based on the silica granules of pyrolysis preparation, described particle has following physicochemical property:
Average particulate diameter: 10 to 120 μ m
The BET surface-area: 40 to 400m
2/ g
Pore volume: 0.5 to 2.5ml/g
Pore distribution: in the total pore volume median pore diameter less than the content in the hole of 5nm less than 5%,
All the other are mesopore and macropore
Compacted density: 220 to 1000g/l
Granularity is in greater than the size range of the D10 value of the size-grade distribution of weighing according to volume and have the particulate numerical value content of the internal voids of tuck or sealing: less than 35%.
2. the particulate preparation method of claim 1, it is characterized in that, the silicon-dioxide of pyrolysis preparation is dispersed in the liquid that contains one or more auxiliary materials, in the preferably water, the component in the dispersion can be added in random order, then dispersion is carried out spraying drying, randomly with the thermal treatment under 150 to 1100 ℃ of temperature of gained particle, randomly with described grain silicon alkanisation, and/or randomly described particle is screened or sieve the randomly recycle of isolating particulate fraction; The thermal treatment of described optional existence, silanization and screening or the processing step that sieves can carry out in any order.
3. according to the method for claim 2, it is characterized in that, from one or more components of following material as described auxiliary material: polymkeric substance, as derivatived cellulose, polyoxyethylene glycol, wax, polyolefine, polyvinyl alcohol or polyacrylate(s); Acid is as formic acid, acetate, lactic acid, oxalic acid, nitric acid, hydrochloric acid or citric acid; Alkali, for example ammonia, amine or basic metal, alkylammonium or alkaline earth metal hydroxides; Colloidal sol is as the colloidal sol of silicon sol, alumina sol or other oxide compound; Water glass or silicon ester are as tetraethyl orthosilicate.
4. according to the method for claim 2, it is characterized in that one or more components that come from following material are as described auxiliary material: carboxymethyl cellulose, methylcellulose gum or with Mierocrystalline cellulose, water glass or the silicon sol of other pure etherificate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810177872A CN101723388A (en) | 2008-10-15 | 2008-10-15 | Silica granules prepared on basis of pyrolysis and preparation method and app {} lication thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810177872A CN101723388A (en) | 2008-10-15 | 2008-10-15 | Silica granules prepared on basis of pyrolysis and preparation method and app {} lication thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101723388A true CN101723388A (en) | 2010-06-09 |
Family
ID=42445045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810177872A Pending CN101723388A (en) | 2008-10-15 | 2008-10-15 | Silica granules prepared on basis of pyrolysis and preparation method and app {} lication thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101723388A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517221A (en) * | 2016-11-11 | 2017-03-22 | 江西德弘新材料有限公司 | Silicon dioxide with high dispersion stability as well as preparation method and application of silicon dioxide |
| CN108147417A (en) * | 2016-12-02 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation method of micron of spherical silica |
| CN108455620A (en) * | 2018-03-31 | 2018-08-28 | 蒋建华 | A kind of preparation method of nano silicon dioxide |
| CN108698885A (en) * | 2015-12-18 | 2018-10-23 | 贺利氏石英玻璃有限两合公司 | The promotion of silicone content in prepared by quartz glass |
| CN109833896A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst |
| US11053152B2 (en) | 2015-12-18 | 2021-07-06 | Heraeus Quarzglas Gmbh & Co. Kg | Spray granulation of silicon dioxide in the preparation of quartz glass |
| CN113477243A (en) * | 2015-03-31 | 2021-10-08 | 旭化成株式会社 | Method for producing oxide catalyst and method for producing unsaturated nitrile |
| US11236002B2 (en) | 2015-12-18 | 2022-02-01 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of an opaque quartz glass body |
| US11299417B2 (en) | 2015-12-18 | 2022-04-12 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of a quartz glass body in a melting crucible of refractory metal |
| US11339076B2 (en) | 2015-12-18 | 2022-05-24 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of carbon-doped silicon dioxide granulate as an intermediate in the preparation of quartz glass |
| US11492282B2 (en) | 2015-12-18 | 2022-11-08 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of quartz glass bodies with dew point monitoring in the melting oven |
| US11492285B2 (en) | 2015-12-18 | 2022-11-08 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of quartz glass bodies from silicon dioxide granulate |
| US11708290B2 (en) | 2015-12-18 | 2023-07-25 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of a quartz glass body in a multi-chamber oven |
-
2008
- 2008-10-15 CN CN200810177872A patent/CN101723388A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113477243A (en) * | 2015-03-31 | 2021-10-08 | 旭化成株式会社 | Method for producing oxide catalyst and method for producing unsaturated nitrile |
| US11492282B2 (en) | 2015-12-18 | 2022-11-08 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of quartz glass bodies with dew point monitoring in the melting oven |
| US11339076B2 (en) | 2015-12-18 | 2022-05-24 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of carbon-doped silicon dioxide granulate as an intermediate in the preparation of quartz glass |
| CN108698885A (en) * | 2015-12-18 | 2018-10-23 | 贺利氏石英玻璃有限两合公司 | The promotion of silicone content in prepared by quartz glass |
| US11952303B2 (en) | 2015-12-18 | 2024-04-09 | Heraeus Quarzglas Gmbh & Co. Kg | Increase in silicon content in the preparation of quartz glass |
| US11708290B2 (en) | 2015-12-18 | 2023-07-25 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of a quartz glass body in a multi-chamber oven |
| US11053152B2 (en) | 2015-12-18 | 2021-07-06 | Heraeus Quarzglas Gmbh & Co. Kg | Spray granulation of silicon dioxide in the preparation of quartz glass |
| US11492285B2 (en) | 2015-12-18 | 2022-11-08 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of quartz glass bodies from silicon dioxide granulate |
| US11299417B2 (en) | 2015-12-18 | 2022-04-12 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of a quartz glass body in a melting crucible of refractory metal |
| US11236002B2 (en) | 2015-12-18 | 2022-02-01 | Heraeus Quarzglas Gmbh & Co. Kg | Preparation of an opaque quartz glass body |
| CN106517221A (en) * | 2016-11-11 | 2017-03-22 | 江西德弘新材料有限公司 | Silicon dioxide with high dispersion stability as well as preparation method and application of silicon dioxide |
| CN108147417A (en) * | 2016-12-02 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation method of micron of spherical silica |
| CN108147417B (en) * | 2016-12-02 | 2021-02-02 | 中国科学院大连化学物理研究所 | Preparation method of micron spherical silicon oxide |
| CN109833896B (en) * | 2017-11-29 | 2022-04-12 | 中国科学院大连化学物理研究所 | Preparation method of high-dispersion noble metal slurry bed hydrogenation catalyst |
| CN109833896A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst |
| CN108455620A (en) * | 2018-03-31 | 2018-08-28 | 蒋建华 | A kind of preparation method of nano silicon dioxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101723388A (en) | Silica granules prepared on basis of pyrolysis and preparation method and app {} lication thereof | |
| CN1051528C (en) | Granules based on pyrogenically prepared silicon dioxide, method for their preparation and use thereof | |
| CN100360410C (en) | Granules based on pyrogenically produced aluminium oxide, their production process and use | |
| CN1914284B (en) | Surface-modified non-metal/metal oxides coated with silicon dioxide | |
| JP4828032B2 (en) | Hydrophobic silica powder and method for producing the same | |
| JP3891265B2 (en) | Hydrophobic silica fine powder and method for producing the same | |
| JP4359136B2 (en) | Toners, developers and emulsions containing partially hydrophobic silicic acid, additives to control the rheology of the system, and partially hydrophobic silicic acid | |
| WO2003054089A1 (en) | Granules based on pyrogenically prepared silicon dioxide, a process for their preparation and their use | |
| JP3581079B2 (en) | Granules based on titanium dioxide produced by pyrolysis and process for producing the same | |
| US20070003701A1 (en) | Process for producing hydrophobic silica powder | |
| JP2003081626A (en) | Grain based on silicon dioxide doped by aluminum oxide and produced by thermal decomposition, production method therefor, and its use | |
| EP1654197A1 (en) | Carrier based on granules produced from pyrogenically prepared silicon dioxides | |
| JP4888633B2 (en) | Method for producing hydrophobic silica powder | |
| JP5267758B2 (en) | Method for producing hydrophobic silica powder | |
| CN101796144A (en) | cyclic-treated metal oxide | |
| JPH0640714A (en) | High-oil-absorptive porous silica, production thereof and carrier | |
| JP2003171117A (en) | Hydrophobic silica fine powder and method for manufacturing the same | |
| JP2015229621A (en) | Hydrophobic aerogel powder, method of manufacturing thereof, and filler using thereof | |
| JP2008514543A (en) | Metals and oxides thereof and methods for producing them | |
| JP2020506141A (en) | Method for producing hydrophobic silica granules | |
| JP2010501464A (en) | Pyrolytic titanium dioxide compressed into slag | |
| KR20170132829A (en) | A hydrophobic airgel comprising a low occupancy mono-functional unit | |
| CN101896426A (en) | Flakes hydrophobic through-and-through and comprising pyrogenically prepared silicon dioxide | |
| JP2004250247A (en) | Alkali-resistant chemically modified silica gel | |
| JPH0222120A (en) | Spherical silica porous form and production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20100609 |