CN1030565C - Producing method of hydrophobic white carbon - Google Patents
Producing method of hydrophobic white carbon Download PDFInfo
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- CN1030565C CN1030565C CN 92110674 CN92110674A CN1030565C CN 1030565 C CN1030565 C CN 1030565C CN 92110674 CN92110674 CN 92110674 CN 92110674 A CN92110674 A CN 92110674A CN 1030565 C CN1030565 C CN 1030565C
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- white carbon
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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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Abstract
The present invention relates to a preparation method of hydrophobic white carbon. The hydrophobic white carbon can be prepared by the following steps: silicon dioxide waste slag as a byproduct of normal calcium superphosphate preparation is adopted as a basic raw material, and is treated with the processes of neutralization with water soluble alkali, trash extraction, high temperature hydrophobic activation and grinding. The hydrophobic white carbon can also be prepared by the following steps: the silicon dioxide waste slag as the byproduct of normal calcium superphosphate preparation is adopted as the basic raw material, and processed with the processes of neutralization with water soluble alkali, trash extraction, addition of a hydrophobing agent, drying, coarse grinding, high temperature hydrophobic activation and fine grinding. The product with a better performance can be prepared by adding common white carbon black during adding a hydrophobing agent. The present invention has the advantages of wide resource of raw material for preparation and simple production process. The hydrophobic white carbon product has good performance, and the cost is lower than that of the product prepared from common white carbon black as raw materials.
Description
The invention belongs to the method for producing hydrophobic silicic aerogels, specifically some are said, the silica residue that the invention belongs to by-product in the normal superphosphate production is the method that basic raw material is produced hydrophobic silicic aerogels.
Usually said white carbon black is meant the hot tearing silicon-dioxide (being gas-phase silica) that hydrated SiO 2 (being precipitated silica) that the precipitator method make or vapor phase process make, and is referred to as the common white carbon black, and they all belong to amorphous silica.Existing hydrophobic silicic aerogels is basic raw material production with this two classes common white carbon black.Its production method has multiple, and main method has two kinds.A kind of is the steaming process (US4054689) that contacts and react with the exsiccant common white carbon black and the steam of organic hydrophobic treatment agent or inorganic hydrophobic treatment agent.Another kind is organic hydrophobizing agent of introducing in the FR2613708 patent of adding in the common white carbon black and the method for carrying out high-temperature high-voltage reaction in autoclave.The hydrophobic white carbon black product cost height that these methods are produced, complex manufacturing.
An object of the present invention is to provide a kind of silica residue with by-product in the normal superphosphate production is the method that basic raw material is produced hydrophobic silicic aerogels.
It is basic raw material that another object of the present invention provides a kind of silica residue with by-product in the normal superphosphate production, and the adding hydrophobizing agent is made hydrophobic treatment, perhaps, when the adding hydrophobizing agent is made hydrophobic treatment, add the common white carbon black, produce the method for hydrophobic silicic aerogels.
The silica residue that a further object of the present invention provides with by-product in the normal superphosphate production is the hydrophobic silicic aerogels series product that basic raw material is produced.
A further object of the invention provides a kind of method of recycling the silica residue of by-product in the normal superphosphate production.
The silicofluoric acid of the hole inside of the silica residue of by-product and outside surface absorption during normal superphosphate is produced is or/and hydrogen fluoride, at high temperature decomposes, volatilizing makes silica sphere hydrophilic radical hydrophobization, gives silicon-dioxide certain hydrophobic performance.The silicofluoric acid of these absorption is or/and hydrogen fluoride plays the effect of inorganic hydrophobizing agent.Unique distinction of the present invention effectively utilizes this point just.Do not see with this kind silica residue to be the method for raw material production hydrophobic silicic aerogels so far as yet.
A kind of method of producing hydrophobic silicic aerogels of the present invention, be that silica residue with by-product in the normal superphosphate production is a basic raw material, with water-soluble alkali the by-product silica residue of normal superphosphate being neutralized to the pH value is 3～14, being preferably and being neutralized to the pH value is 5～12, neutralization reaction 10 minutes to 2 hours was preferably neutralization reaction 25 minutes to 1 hour; Remove hard gel and impurity in the neutralization reaction feed liquid, be filtered to weight in wet base, be preferably weight in wet base less than 75% less than 85%; Filter silicon-dioxide 80 ℃～500 ℃ following hydrophobic activations of temperature 0.5～5 hour, being preferably in temperature is 150 ℃～450 ℃ following hydrophobic activations 1～4 hour; The silicon-dioxide of high temperature hydrophobic activation is crushed to below the 74 μ m, is preferably and is crushed to below the 45 μ m, just obtain a kind of hydrophobic white carbon black product that the inventive method is produced.The hydrophobic silicic aerogels that makes like this has temporary transient hydrophobicity, can be used for the less demanding field of hydrophobicity, for example, as the lubricant of powder, anti-hard caking agent etc.
Second kind of method of producing hydrophobic silicic aerogels of the present invention, be that silica residue with by-product in the normal superphosphate production is a basic raw material, with water-soluble alkali the by-product silica residue of normal superphosphate being neutralized to the pH value is 3～14, being preferably and being neutralized to the pH value is 5～12, neutralization reaction 10 minutes to 2 hours was preferably neutralization reaction 25 minutes to 1 hour; Removing hard gel and impurity in this neutralization reaction feed liquid, be filtered to weight in wet base less than 85%, better is that weight in wet base is less than 75%; To filter silicon-dioxide in add and to account for hydrophobic white carbon black product weight 1～20% hydrophobizing agent, be preferably and add the hydrophobizing agent that accounts for hydrophobic white carbon black product weight 3～15%, the hydrophobizing agent useable solvents dilution that adds can not diluted yet, mix, and under 100 ℃～300 ℃ of temperature, be dried to weight in wet base less than 30%; The silicon-dioxide coarse reduction that drying is crossed, hydrophobic activation 0.5～5 hour under 80 ℃～500 ℃ temperature again is preferably 150～450 ℃ of following hydrophobic activations 1～4 hour; The work in-process silicon-dioxide that the high temperature hydrophobic activation is got is crushed to below the 74 μ m, is preferably to be crushed to below the 45 μ m, thereby obtains a series of products of hydrophobic silicic aerogels that the inventive method is produced.The performances such as hydrophobicity of the hydrophobic silicic aerogels of making like this are better than the hydrophobic white carbon black product that first method of the present invention makes, the lubricant and the anti-hard caking agent that both can be used for various meals, can be used for producing hydrophobic coating again, also can make the defoamer of the various aqueous solution and organic solvent etc.
Produce in the hydrophobic silicic aerogels method for second kind of the present invention, to filter silicon-dioxide in add the common white carbon black when adding hydrophobizing agent, promptly when adding hydrophobizing agent, add precipitated silica or gas-phase silica.In more detail, produce in the method for hydrophobic silicic aerogels at this adding hydrophobizing agent of the present invention, still the silica residue with by-product in the normal superphosphate production is a basic raw material, and with water-soluble alkali the by-product silica residue of normal superphosphate being neutralized to the pH value is 3～14.Being preferably and being neutralized to the pH value is 5～12, and neutralization reaction 10 minutes to 2 hours was preferably neutralization reaction 25 minutes to 1 hour; Remove hard gel and impurity in the neutralization reaction feed liquid, be filtered to weight in wet base, be preferably weight in wet base less than 75% less than 85%; To filter silicon-dioxide in add the hydrophobizing agent account for hydrophobic white carbon black product weight 1～20%, be preferably and add the hydrophobizing agent that accounts for hydrophobic white carbon black product weight 3～15%, the hydrophobizing agent useable solvents dilution that adds can not diluted yet, add the common white carbon black when adding hydrophobizing agent, the common white carbon black that adds accounts for 5～70% of hydrophobic white carbon black product weight, the common white carbon black that is preferably adding accounts for 10～50% of hydrophobic white carbon black product weight, mix, and under 100 ℃～300 ℃ of temperature, be dried to weight in wet base less than 30%; The silicon-dioxide coarse reduction that drying is crossed, hydrophobic activation 0.5～5 hour under 80 ℃～500 ℃ temperature again is preferably 150 ℃～450 ℃ following hydrophobic activations 1～4 hour; The work in-process silicon-dioxide that the high temperature hydrophobic activation is got is crushed to below the 74 μ m, is preferably to be crushed to below the 45 μ m, just obtains another series product of hydrophobic silicic aerogels that the inventive method is produced.The performances such as hydrophobicity of the hydrophobic silicic aerogels that makes like this are all better than the performance of aforesaid hydrophobic white carbon black product.Its purposes, except that preceding enumerated, can also make the filler of special synthetic rubber and strengthening agent, high molecular polymerization auxiliary agent, ink adhesion promoter or the like.
Being used in all methods of the present invention and the water-soluble alkali of the by-product silica residue of normal superphosphate, is NH
4Any among OH, NaOH, the KOH etc., it would be desirable and use NH
4The OH neutralization.
Employed hydrophobizing agent is any hydrophobic organic and their composition in the production method of the present invention.Comparatively it is desirable to fat virtue class, silicone oil, silicone resin class, the organic hydrophobizing agent of silane coupling agent class and their composition.Ideal is silicone oil, silicone resin class, the silane idol organic hydrophobizing agent of agent class and their composition.
Say that more properly it can be the silicone oil with following general structure that the present invention produces the organic hydrophobizing agent of the employed silicone oil of hydrophobic silicic aerogels:
R in this structural formula can be organic group identical or inequality or H, OH base.Difference according to R can have multiple silicone oil hydrophobizing agent.As: methyl-silicone oil, ethyl silicon oil, tolyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, ethyl containing hydrogen silicone oil, hydroxyl silicone oil, contain alkoxyl group silicone oil, contain acyloxy silicone oil, dibasic alcohol copolymerization silicone oil, higher alcohols modified silicon oil, fatty acid modified silicone oil, methyl alkyl silicone oil, chloromethyl silicone oil, chloro-phenyl-silicone oil, carboxyalkyl silicone oil, aminoalkyl silicone oil, fluoroalkyl silicone oil, silazane silicone oil, silmethylene bond silicone oil, silicon penylene silicone oil, silicon benzoyl support silicone oil or the like.
The present invention produces the various modified silicone resins that the organic hydrophobizing agent of the employed silicone resin class of hydrophobic silicic aerogels can be methyl silicon resin, phenyl polysiloxane, methyl phenyl silicone resin and the modification of use organic resin.
It can be the silane coupling agent with following general structure that the present invention produces the organic hydrophobizing agent of the employed silane coupling agent class of hydrophobic silicic aerogels:
Y in this structural formula, R, X can be groups identical or inequality.Different or identical Y, R, X can constitute plurality of silane coupling agents class hydrophobizing agent.For example: trimethylchlorosilane, trimethylammonium two TMOSs, dimethyldichlorosilane(DMCS), dimethyldiethoxysilane, diethylmethyl silane, METHYL TRICHLORO SILANE, methyl triacetoxysilane, phenylbenzene dihydroxyl silane, octamethylcyclotetrasiloxane, vinyl trichloro silane, vinyltriethoxysilane, vinyltrimethoxy silane, vinyl (second-methoxy ethoxy) silane, γ-An Bingjisanyiyangjiguiwan, methyl ethylene two TMOSs, methyl (gamma-methyl allyl acyloxypropyl) diethoxy silane, β-(3,4 oxirane ethyl) ethyl trimethoxy silane or the like.
It is any organic solvent that the present invention produces the solvent that is used to dilute hydrophobizing agent in the method for hydrophobic silicic aerogels, as benzene, dimethylbenzene, vinyl acetic monomer, acetone, ethanol, methyl alcohol or the like.
It is the hydrophobic silicic aerogels that basic raw material is produced that hydrophobic silicic aerogels production cost of the present invention is significantly less than with precipitated silica or gas-phase silica; The second, the main raw material of hydrophobic silicic aerogels of the present invention is the silica residue of by-product during normal superphosphate is produced, and this waste residue is Litter and quantity is many.Therefore, wide material sources, cost recovery is low; The 3rd, owing to be adsorbed with silicofluoric acid or/and hydrogen fluoride on the hole of the silica residue of by-product inside and the outside surface in the normal superphosphate production, the silicofluoric acid of these absorption or/and hydrogen fluoride in the hydrophobic treatment process, play natural hydrophobizing agent or help the hydrophobizing agent effect.Therefore, hydrophobic silicic aerogels of the present invention is compared with the hydrophobic silicic aerogels that with precipitated silica or gas-phase silica is basic raw material production, and organic hydrophobizing agent consumption that reach the same required interpolation of hydrophobic performance reduces; The 4th, hydrophobic silicic aerogels series of products hydrophobic performance excellence of the present invention, alternative in some fields is the hydrophobic silicic aerogels that basic raw material is produced with precipitated silica or gas-phase silica, and it is the hydrophobic silicic aerogels that basic raw material is produced that other field parts substitute with precipitated silica or gas-phase silica; The 5th, the production technique of hydrophobic silicic aerogels of the present invention is simple, is easy to industrialization.
Indefiniteness embodiment of the present invention:
Example one
(1) with the silica residue NH of by-product in the normal superphosphate production
4It is 8 that OH is neutralized to the pH value, neutralization reaction 35 minutes.
(2) remove hard gel and impurity in the above-mentioned neutralization reaction feed liquid, being filtered to weight in wet base is 80%.
(3) silicon-dioxide that filtration is obtained hydrophobic activation 3.5 hours under 350 ℃ temperature.
(4) the work in-process silicon-dioxide with the high temperature hydrophobic activation is crushed to below the 45 μ m, promptly gets one of hydrophobic silicic aerogels kind of the present invention's production.
These product performance are shown in the table 1.This product is listed in table 2 as the lubricant of preventing sodium bicarbonate dry-chemical fire extinguishing agent agent and the performance index of anti-hard caking agent.
Example two
(1) with the silica residue NH of by-product in the normal superphosphate production
4It is 8 that OH is neutralized to the pH value, neutralization reaction 35 minutes.
(2) remove hard gel and impurity in the above-mentioned neutralization reaction feed liquid, being filtered to weight in wet base is 80%.
(3) get above-mentioned filter residue 35kg, add the trimethylammonium two TMOS 1.5kg with acetone diluted, it is that to be dried to water ratio weight be 25% for 230 ℃ tray dryer that thorough mixing is put into temperature after evenly.
(4) exsiccant silicon-dioxide is carried out coarse reduction.
(5) the hydrophobic activation 3.5 hours under 400 ℃ of temperature of the silicon-dioxide after the coarse reduction.
(6) the work in-process silicon-dioxide with the high temperature hydrophobic activation is crushed to below the 45 μ m, promptly gets two of hydrophobic silicic aerogels kind that the present invention produces.
These product performance are shown in the table 1.This product is listed in table 2 as the lubricant of preventing sodium bicarbonate dry-chemical fire extinguishing agent agent and the performance index of anti-hard caking agent.
Example three
(1) with the silica residue NH of by-product in the Production of Single Superphosphate
4It is 8 that OH is neutralized to the pH value, neutralization reaction 35 minutes.
(2) remove hard gel and impurity in the above-mentioned neutralization reaction feed liquid, being filtered to weight in wet base is 70%.
(3) get the above-mentioned filter residue 35kg that crosses, add precipitated silica 2.5kg simultaneously and with the octamethylcyclotetrasiloxane 1.8kg of acetone diluted, putting into temperature after thorough mixing is even and be 230 ℃ tray dryer, to be dried to weight in wet base be 25%.
(4) exsiccant silicon-dioxide is carried out coarse reduction.
(5) the hydrophobic activation 3.5 hours under 400 ℃ of temperature of the silicon-dioxide after the coarse reduction.
(6) the work in-process silicon-dioxide with the high temperature hydrophobic activation is crushed to below the 45 μ m, promptly gets three of hydrophobic silicic aerogels kind that the present invention produces.
These product performance are shown in the table 1, and this product is listed in the table 2 as the lubricant and the anti-hard caking agent performance index of preventing sodium bicarbonate dry-chemical fire extinguishing agent agent.
Table 1 hydrophobic white carbon black product performance of the present invention
Example 1
Test event
Silicon-dioxide (butt)
(1), % 94 93 95
Weight loss on heating (105 ℃) % 0.3 0.4 0.2
Calcination loss (1000 ℃) % 4.2 8.3 9.4
The DBP absorption value, ml/g 1.84 1.78 1.92
45 μ m screenings (dry screen) % 0.1 0.2 0.1
The pH value
(2)3.0 4.5 5.2
Copper content, mg/kg 61 84 67
Iron level, mg/kg 466 573 506
Manganese content, mg/kg 132
Hydrophobic rate
(3), % 20 99.9 99.97
In the table 1:
(1) dioxide-containing silica of the hydrophobic white carbon black product produced of expression the present invention is to serve as to calculate reference data with the anhydride silica after the calcination loss;
(2) data of expression pH value are that the present invention produces hydrophobic silicic aerogels and measures in water and 1: 1 mixed solution of acetone;
(3) expression the present invention hydrophobic rate data of producing hydrophobic silicic aerogels are measured as follows.
In 250 milliliters of separating funnels, put into 100 ml distilled waters, take by weighing hydrophobic silicic aerogels sample 5 grams (claiming accurate) that the present invention produces to 0.001 gram, put into separating funnel, concussion is 15 minutes on 120 times/minute oscillator, leaves standstill 1 hour.The muddy liquid that silicon-dioxide is contained in the bottom moves into 4 of constant
#In the glass sand device, and under 105 ℃, dry to constant weight.Be calculated as follows the hydrophobic rate of hydrophobic silicic aerogels of the present invention:
Hydrophobic rate=(suspended substance heavy (gram) in the water)/(sample heavy (gram)) * 100%
Table 2, hydrophobic silicic aerogels of the present invention is as the lubricant of preventing sodium bicarbonate dry-chemical fire extinguishing agent agent and the The performance test results of anti-hard caking agent
Example 1
Test event
Loose density, g/cm
31.03 1.05 1.08
Specific surface area, cm
2/ g 2,871 3,250 3010
Water ratio, % 0.18 0.15 0.17
Rate of moisture absorption, % 1.14 0.85 1.02
Flowability, S 7.1 5.8 5.0
Caking penetration degree, mm 18 21 24
Trend is scolded the water characteristic, and S 2.5 2.0 2.0
Cold property, S 4.3 3.0 2.0
Grain 60 orders above 0.0 0.0 0.0
Degree 60～100 orders 3.5 0.8 2.1
Divide 100～200 orders 7.6 5.4 6.2
Cloth 200～325 orders 11.2 9.8 10.4
% chassis 77.7 84 81.3
The filling spray rate, % 93 95 96
Three tests of three tests of three tests of fire extinguishing effectiveness
Three fire extinguishings of three fire extinguishings of three fire extinguishings
Claims (7)
1, a kind of method of producing hydrophobic silicic aerogels, with the amorphous silica is raw material, it is characterized in that, by-product silica residue with normal superphosphate is a basic raw material, with water-soluble alkali the by-product silica residue of normal superphosphate being neutralized to the pH value is 3～14, being preferably and being neutralized to the pH value is 5～12, and neutralization reaction 10 minutes to 2 hours was preferably neutralization reaction 25 minutes to 1 hour; Remove hard gel and impurity in the neutralization reaction feed liquid, be filtered to weight in wet base, be preferably weight in wet base less than 75% less than 85%; Filter silicon-dioxide 80 ℃～500 ℃ following hydrophobic activations of temperature 0.5～1 hour, be preferably 150 ℃～450 ℃ following hydrophobic activations of temperature 1～4 hour; The silicon-dioxide of high temperature hydrophobic activation is crushed to below the 74 μ m, is preferably and is crushed to below the 45 μ m.
2, according to the method for the described production hydrophobic silicic aerogels of claim 1, wherein be used for and the water-soluble alkali of the by-product silica residue of normal superphosphate, be NH
4Any among OH, NaOH, the KOH etc. it would be desirable and use NH
4The OH neutralization.
3, a kind of method of producing hydrophobic silicic aerogels, with the amorphous silica is raw material, it is characterized in that, by-product silica residue with normal superphosphate is a basic raw material, with water-soluble alkali the by-product silica residue of normal superphosphate being neutralized to the pH value is 3～14, being preferably and being neutralized to the pH value is 5～12, and neutralization reaction 10 minutes to 2 hours was preferably neutralization reaction 25 minutes to 1 hour; Remove hard gel and impurity in the neutralization reaction feed liquid, be filtered to weight in wet base, be preferably weight in wet base less than 75% less than 85%; To filter silicon-dioxide in add the hydrophobizing agent account for hydrophobic white carbon black product weight 1～20%, better be to add the hydrophobizing agent that accounts for hydrophobic white carbon black product weight 3～15%, the hydrophobizing agent useable solvents dilution that adds can not diluted yet, mix, and under 100 ℃～300 ℃ of temperature, be dried to weight in wet base less than 30%; Here employed hydrophobizing agent is fat virtue class, silicone oil, silicone resin class, the organic hydrophobizing agent of silane coupling agent class and their composition, it would be desirable silicone oil, silicone resin class, the organic hydrophobizing agent of silane coupling agent class and their composition.The silicon-dioxide coarse reduction that drying is crossed, hydrophobic activation 0.5～5 hour under 80 ℃～500 ℃ temperature again; Be preferably 150 ℃～450 ℃ following hydrophobic activations 1～4 hour; The work in-process silicon-dioxide that the high temperature hydrophobic activation is got is crushed to below the 74 μ m, is preferably to be crushed to below the 45 μ m.
4, according to the method for the described production hydrophobic silicic aerogels of claim 3, wherein to filter silicon-dioxide in add the common white carbon black when adding hydrophobizing agent, the common white carbon black that adds accounts for 5～70% of hydrophobic white carbon black product weight, and the common white carbon black that is preferably adding accounts for 10～50% of hydrophobic white carbon black product weight.
5, according to the method for the described production hydrophobic silicic aerogels of claim 3, wherein be used for and the water-soluble alkali of the by-product silica residue of normal superphosphate, be NH
4Any among OH, NaOH, the KOH etc. it would be desirable and use NH
4The OH neutralization.
6, according to the method for the described production hydrophobic silicic aerogels of claim 3, the organic hydrophobizing agent of wherein employed silicone oil can be the silicone oil with following general structure,
R in this structural formula can be organic group identical or inequality or H, OH base, according to the difference of R multiple silicone oil hydrophobizing agent can be arranged;
The organic hydrophobizing agent of wherein employed silicone resin class can be the various modified silicone resins of methyl silicon resin, phenyl polysiloxane, methyl phenyl silicone resin and the modification of use organic resin;
The organic hydrophobizing agent of wherein employed silane coupling agent class can be the silane coupling agent with following general structure,
X
Y-R-Si-X
X
Y in this structural formula, R, X can be groups identical or inequality, and different or identical Y, R, X can constitute plurality of silane coupling agents class hydrophobizing agent.
7, according to the method for the described production hydrophobic silicic aerogels of claim 3, the solvent that wherein is used to dilute hydrophobizing agent is an organic solvent, for example benzene, dimethylbenzene, vinyl acetic monomer, acetone, ethanol and methyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110674 CN1030565C (en) | 1992-09-07 | 1992-09-07 | Producing method of hydrophobic white carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110674 CN1030565C (en) | 1992-09-07 | 1992-09-07 | Producing method of hydrophobic white carbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1070890A CN1070890A (en) | 1993-04-14 |
| CN1030565C true CN1030565C (en) | 1995-12-27 |
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| CN 92110674 Expired - Fee Related CN1030565C (en) | 1992-09-07 | 1992-09-07 | Producing method of hydrophobic white carbon |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075538C (en) * | 1998-12-18 | 2001-11-28 | 北京秦城灭火剂厂 | Process for preparing hydrophobic silica white |
| CN102259839B (en) * | 2011-06-17 | 2013-06-12 | 德化县新隆泰化工实业有限公司 | Anticaking agent special for potassium chlorate |
| CN106809835B (en) * | 2016-12-30 | 2019-03-26 | 常州碳星科技有限公司 | A method of preparing super-hydrophobic active carbon |
| CN110358304A (en) * | 2019-06-14 | 2019-10-22 | 东莞市天桉硅胶科技有限公司 | A kind of liquid silastic of the high grade of transparency and preparation method thereof |
| CN110395737B (en) * | 2019-08-21 | 2021-06-25 | 华东理工大学 | Modification method of precipitated white carbon black |
| CN112408403A (en) * | 2020-11-25 | 2021-02-26 | 中昊黑元化工研究设计院有限公司 | Method for preparing hydrophobic silicon dioxide by using micro silicon powder |
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