CN110028073A - A kind of preparation method of polymolecularity precipitated silica - Google Patents
A kind of preparation method of polymolecularity precipitated silica Download PDFInfo
- Publication number
- CN110028073A CN110028073A CN201811295415.0A CN201811295415A CN110028073A CN 110028073 A CN110028073 A CN 110028073A CN 201811295415 A CN201811295415 A CN 201811295415A CN 110028073 A CN110028073 A CN 110028073A
- Authority
- CN
- China
- Prior art keywords
- ammonium
- sulfuric acid
- added
- carbon black
- white carbon
- 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
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
Abstract
The present invention relates to a kind of preparation methods of polymolecularity precipitated silica, include the following steps: first to be pumped into certain density water glass solution into reaction kettle as bottom liquid, a certain amount of ammonium hydroxide-ammonium state salt buffer is added, temperature is risen to 200~220 DEG C under high pressure, then sulfuric acid solution is added under conditions of mechanical stirring, the high molecular polymer of certain mass is added simultaneously, precipitation reaction afterwards by processes such as washing, filtering, drying, crushing, finally obtains white carbon black product for a period of time.White carbon black specific surface area obtained by the present invention is 180~240m2/ g, no gel, is easily dispersed, good mechanical properties, can be used as the functional filler of automobile tire or silicon rubber, has a good application prospect.
Description
Technical field
The present invention relates to a kind of preparation methods of precipitated silica, are that a kind of stable polymolecularity of quality is heavy concretely
The preparation of shallow lake white carbon black, this white carbon black can be used as the functional filler of automobile tire or silicon rubber.
Background technique
White carbon black is broadly divided into fume colloidal silica and precipitated silica by production method.Under fume colloidal silica normality
For the cotton-shaped translucent solid colloidal nanoparticle of white-amorphous, but preparation process is complicated, expensive.Precipitated silica is
Refer to sulfuric acid, hydrochloric acid, CO2It is the silica of base stock production with waterglass, and solidifying using high-gravity technology, colloidal sol-
The silica of the specific process such as glue method, chemical crystal method, second-crystallized method or reverse micelle microemulsion liquid method production.
Country's precipitated silica is prepared using waterglass and sulfuric acid as raw material mostly at present, in traditional handicraft, the control of sulfuric acid
The pH value of reaction system is influenced, the acid too strong or pH value fluctuation in part is larger, it will product is caused more or less to form gel, shadow
Ring quality of white carbon black product.By acid for adjusting pH value, by 9~10 to 4~5, dispersing agent is added in Chinese patent 200510028053.5
Na2SO4, while controlling the generation that mixing speed carrys out pre- anti-gel.The quality stability of white carbon black product obtained by the method, dispersion
Property and specific surface area still need to further increase.
The dispersibility of white carbon black influences the service performance of product, easily reunites since the primary partial size of white carbon black is smaller, is easy
Cause that particle is larger, the problems such as being unevenly distributed.Chinese patent 201610395299.4 is by being added n-butanol and sodium chloride, together
When cationic surfactant is added partial size is small, main content is high white carbon black product is made.The auxiliary agent that the method is added is more, increases
Add the cost of product.
Summary of the invention
The purpose of the present invention is disclosing a kind of preparation method of polymolecularity precipitated silica, cost is relatively low, product quality
Stablize, dispersion performance is good.
A kind of preparation method of polymolecularity precipitated silica of the present invention includes the following steps: first to reaction kettle
In be pumped into certain density water glass solution as bottom liquid, a certain amount of ammonium hydroxide-ammonium state salt buffer is added, under high pressure will be warm
Degree rises to 200~220 DEG C, sulfuric acid solution is then added under conditions of mechanical stirring, while the macromolecule of certain mass is added
Polymer, precipitation reaction afterwards by processes such as washing, filtering, drying, crushing, finally obtain white carbon black product for a period of time.
In the water glass solution, the mass concentration of sodium metasilicate is 10%~30%, and the modulus of waterglass is 3.1~3.7.
In the sulfuric acid solution, the mass concentration of sulfuric acid is 20%~80%.
The sodium metasilicate of the addition and the mass ratio of sulfuric acid are 1:(0.3~0.6).
In the ammonium hydroxide-ammonium state salt buffer, ammonium state salt is ammonium chloride, ammonium sulfate, ammonium phosphate, diammonium hydrogen phosphate, phosphoric acid
One or more of ammonium dihydrogen.
In the ammonium hydroxide-ammonium state salt buffer, pH value is 6.5~9.5.
The ammonium hydroxide-ammonium state salt buffer additional amount is the 3~10.0% of sodium metasilicate.
The high molecular polymer is Sodium Polyacrylate, polyacrylate, polyvinyl alcohol, polyvinylpyrrolidone, rouge
One or more of fat alcohol polyoxyethylene ether, polycarboxylate.
The high molecular polymer additional amount is the 0.2~2.0% of sodium metasilicate quality.
The addition time of the sulfuric acid solution is 0.5~2.0h, and the time of precipitation reaction is 1.5~4.0h.
It is previously added a certain amount of ammonium hydroxide-ammonium state salt buffer in the present invention, is the play for avoiding pH value during charging
Strong variation, makes pH value be maintained at a metastable range, and the acute variation of pH value is easy to make shape between silicon dioxide granule
At gel, dispersibility of the white carbon black in application system is influenced, mechanical property is reduced, to influence downstream product quality.
High molecular polymer, which is added, mainly utilizes it in the powerful steric hindrance of the adsorbed film of silica particles
Repelling effect.The thickness of polymer adsorption film is generally up to tens nanometers, is formed with inorganic salts and small organic molecule dispersing agent
Electronic double layer repulsion effect is compared, and when silica dioxide granule is apart from each other, this steric hindrance repelling effect has just been showed,
Products obtained therefrom partial size is smaller, and specific surface area is bigger, easily disperses in products application system, good product performance.
The present invention is compared with traditional precipitated silica, and cost is relatively low, environmentally protective, simple process, using ammonium hydroxide-ammonium state
Salt buffer guarantees the stabilization of pH value in reaction process, macromolecule is added, polymer is divided to repel effect using its powerful steric hindrance
Should be made partial size it is small, easily disperse white carbon black product, specific surface area be 180~240m2/ g, is easily dispersed, good mechanical properties,
The functional filler that can be used as automobile tire or silicon rubber, has a good application prospect.
Present invention process step is simple, and obtained no gel high-dispersion white carbon black specific surface area is 180~240m2/ g,
Good mechanical properties can be used as the functional filler of automobile tire or silicon rubber, have a good application prospect.
Specific embodiment
In order to further elaborate the present invention, below in conjunction with example, the present invention will be described, but embodiment is only
Of the invention is preferred, and not all, to those skilled in the art, without departing from the principle of the present invention, is made
Several improvement, should be regarded as protection scope of the present invention.
White carbon black is measured according to HG/T3073-1999 " the measurement N2 adsorption method of precipitated hydrated silica specific surface area "
Specific surface area.
According to HG/T3072-2008 " measurement of precipitated hydrated silica dibutyl phthalate (DBP) absorption value "
Measure the oil factor of white carbon black.
White carbon black product rubber is carried out according to HG/T2404-2008 " identification of the precipitated hydrated silica in butadiene-styrene rubber "
Processing and the test of mechanical property.
Embodiment 1
It is 15% sodium silicate solution as bottom liquid that 667Kg mass concentration is first squeezed into reaction kettle, and pH value, which is added, is
7.5 ammonium hydroxide-ammonium chloride buffer 5Kg, rises to 200 DEG C for temperature under high pressure, then under conditions of strength mechanical stirring
Mass concentration is added and is 25% sulfuric acid solution 151Kg, while Sodium Polyacrylate 0.5Kg is added, the addition time of sulfuric acid solution
For 1.2h, by processes such as washing, filtering, drying, crushing after precipitation reaction 3.5h, white carbon black product 76Kg is finally obtained.
Gained white carbon black product performance and the test result of application performance are shown in Table 1.
Embodiment 2
It is 12% sodium silicate solution as bottom liquid that 1300Kg mass concentration is first squeezed into reaction kettle, and pH value, which is added, is
8.0 ammonium hydroxide-ammonium sulphate buffer 6.5Kg, rises to 210 DEG C for temperature under high pressure, then in the churned mechanically condition of strength
The lower mass concentration that is added is 35% sulfuric acid solution 168Kg, while polyvinyl alcohol 1.5Kg is added, the addition time of sulfuric acid solution
For 1.0h, by processes such as washing, filtering, drying, crushing after precipitation reaction 4.0h, white carbon black product 118Kg is finally obtained.
Gained white carbon black product performance and the test result of application performance are shown in Table 1.
Embodiment 3
It is 20% sodium silicate solution as bottom liquid that 675Kg mass concentration is first squeezed into reaction kettle, and pH value, which is added, is
8.5 ammonium hydroxide-ammonium phosphate buffer liquid 6.0Kg, rises to 220 DEG C for temperature under high pressure, then in the churned mechanically condition of strength
The lower mass concentration that is added is 40% sulfuric acid solution 127Kg, while polyvinylpyrrolidone 1.0Kg is added, and sulfuric acid solution adds
The angle of incidence is 1.5h, by processes such as washing, filtering, drying, crushing after precipitation reaction 3.0h, finally obtains white carbon black product
103Kg。
Gained white carbon black product performance and the test result of application performance are shown in Table 1.
Embodiment 4
It is 25% sodium silicate solution as bottom liquid that 384Kg mass concentration is first squeezed into reaction kettle, and pH value, which is added, is
7.0 ammonium hydroxide-diammonium hydrogen phosphate buffer 5.5Kg, rises to 215 DEG C for temperature under high pressure, then churned mechanically in strength
Under the conditions of the sulfuric acid solution 72.3Kg that mass concentration is 50% is added, while polyacrylate 1.2Kg is added, sulfuric acid solution plus
The angle of incidence is 1.3h, by processes such as washing, filtering, drying, crushing after precipitation reaction 3.0h, finally obtains white carbon black product
73Kg。
Gained white carbon black product performance and the test result of application performance are shown in Table 1.
In order to further demonstrate that meaning of the present invention, comparative example is implemented, is delayed in comparative example 1 without using ammonium hydroxide-ammonium state salt
Fliud flushing is added without high molecular polymer in comparative example 2.
Comparative example 1
It is 13% sodium silicate solution as bottom liquid that 1100Kg mass concentration is first squeezed into reaction kettle, under high pressure will be warm
Degree rises to 205 DEG C, the sulfuric acid solution 154Kg that mass concentration is 35% is then added under conditions of strength mechanical stirring, simultaneously
Be added polycarboxylate 1.3Kg, addition time of sulfuric acid solution is 1.0h, after precipitation reaction 3.5h by washing, filtering, drying,
The processes such as crushing, finally obtain white carbon black product 109Kg.
Gained white carbon black product performance and the test result of application performance are shown in Table 1.
Comparative example 2
It is 18% sodium silicate solution as bottom liquid that 733Kg mass concentration is first squeezed into reaction kettle, and pH value, which is added, is
7.5 ammonium hydroxide-ammonium sulphate buffer 7.0Kg, rises to 210 DEG C for temperature under high pressure, then in the churned mechanically condition of strength
The lower sulfuric acid solution 124Kg that mass concentration is added and is 40%, the addition time of sulfuric acid solution are 1.4h, are passed through after precipitation reaction 3.0h
The processes such as washing, filtering, drying, crushing are crossed, white carbon black product 100Kg is finally obtained.
Gained white carbon black product performance and the test result of application performance are shown in Table 1.
1 embodiment 1-4 of table and comparative example 1-2 properties of product test result
Remarks:
BET specific surface area, DBP dibutyl phthalate absorption.
Claims (10)
1. a kind of preparation method of polymolecularity precipitated silica, which comprises the steps of: first pumped into reaction kettle
Enter certain density water glass solution as bottom liquid, a certain amount of ammonium hydroxide-ammonium state salt buffer is added, under high pressure by temperature liter
To 200~220 DEG C, sulfuric acid solution is then added under conditions of mechanical stirring, while the high molecular polymerization of certain mass is added
Object, precipitation reaction afterwards by washing, filtering, drying, pulverizing process, finally obtain white carbon black product for a period of time.
2. the method according to claim 1, wherein in the water glass solution, the mass concentration of sodium metasilicate is
10%~30%, the modulus of waterglass is 3.1~3.7.
3. the method according to claim 1, wherein the mass concentration of sulfuric acid is 20% in the sulfuric acid solution
~80%.
4. the method according to claim 1, wherein the sodium metasilicate of the addition and the mass ratio of sulfuric acid are 1:
(0.3~0.6).
5. the method according to claim 1, wherein ammonium state salt is chlorination in the ammonium hydroxide-ammonium state salt buffer
One or more of ammonium, ammonium sulfate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate.
6. the method according to claim 1, wherein in the ammonium hydroxide-ammonium state salt buffer, pH value is 6.5~
9.5。
7. the method according to claim 1, wherein the ammonium hydroxide-ammonium state salt buffer additional amount is silicic acid
The 3~10.0% of sodium quality.
8. the method according to claim 1, wherein the high molecular polymer is Sodium Polyacrylate, poly- third
One or more of olefin(e) acid ester, polyvinyl alcohol, polyvinylpyrrolidone, fatty alcohol polyoxyethylene ether, polycarboxylate.
9. the method according to claim 1, wherein the high molecular polymer additional amount is sodium metasilicate quality
0.2~2.0%.
10. the method according to claim 1, wherein the addition time of the sulfuric acid solution be 0.5~
2.0h, the time of precipitation reaction are 1.5~4.0h.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810182987 | 2018-03-06 | ||
| CN2018101829871 | 2018-03-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110028073A true CN110028073A (en) | 2019-07-19 |
Family
ID=67234978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811295415.0A Pending CN110028073A (en) | 2018-03-06 | 2018-11-01 | A kind of preparation method of polymolecularity precipitated silica |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110028073A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111115641A (en) * | 2019-12-25 | 2020-05-08 | 江西双龙硅材料科技有限公司 | Preparation method of special white carbon black for thickening toothpaste |
| CN113023736A (en) * | 2021-04-01 | 2021-06-25 | 广州市飞雪材料科技有限公司 | Preparation method of silicon dioxide for high-oil-absorption low-viscosity toothpaste |
| CN113401914A (en) * | 2021-07-01 | 2021-09-17 | 确成硅化学股份有限公司 | Preparation method of high-dispersion white carbon black special for high-fatigue-resistance tire |
| CN114286799A (en) * | 2021-12-01 | 2022-04-05 | 无锡恒诚硅业有限公司 | Preparation method and application of white carbon black for improving rheological property |
| CN115159530A (en) * | 2022-08-08 | 2022-10-11 | 确成硅化学股份有限公司 | Synthesis process of large-pore-volume precipitated silica for coating flatting agent |
| CN115571881A (en) * | 2022-10-14 | 2023-01-06 | 西南交通大学 | Preparation and energy storage testing method of nano silicon and battery using nano silicon |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004007366A1 (en) * | 2002-07-10 | 2004-01-22 | Tokuyama Corporation | Cake of easily dispersible precipitated silica and process for producing the same |
| CN102320615A (en) * | 2011-09-11 | 2012-01-18 | 中国科学院过程工程研究所 | Method for preparing precipitated silica by adopting micro-silica fume as raw material |
| CN103145161A (en) * | 2013-01-08 | 2013-06-12 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Method for preparing pseudo-boehmite co-preparation white carbon black by coal gangue |
| CN104773740A (en) * | 2015-04-24 | 2015-07-15 | 西南科技大学 | Method for synchronously preparing type-A zeolite and white carbon black with fly ash |
-
2018
- 2018-11-01 CN CN201811295415.0A patent/CN110028073A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004007366A1 (en) * | 2002-07-10 | 2004-01-22 | Tokuyama Corporation | Cake of easily dispersible precipitated silica and process for producing the same |
| CN102320615A (en) * | 2011-09-11 | 2012-01-18 | 中国科学院过程工程研究所 | Method for preparing precipitated silica by adopting micro-silica fume as raw material |
| CN103145161A (en) * | 2013-01-08 | 2013-06-12 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Method for preparing pseudo-boehmite co-preparation white carbon black by coal gangue |
| CN104773740A (en) * | 2015-04-24 | 2015-07-15 | 西南科技大学 | Method for synchronously preparing type-A zeolite and white carbon black with fly ash |
Non-Patent Citations (2)
| Title |
|---|
| 李凯琦等: "《风化型高岭土深加工技术》", 30 June 2017, 中国建材工业出版社 * |
| 邓建成，童珏，刘希: "酸性硅溶胶沉淀法制备超微细活性白炭黑", 《湘潭大学自然科学学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111115641A (en) * | 2019-12-25 | 2020-05-08 | 江西双龙硅材料科技有限公司 | Preparation method of special white carbon black for thickening toothpaste |
| CN113023736A (en) * | 2021-04-01 | 2021-06-25 | 广州市飞雪材料科技有限公司 | Preparation method of silicon dioxide for high-oil-absorption low-viscosity toothpaste |
| CN113401914A (en) * | 2021-07-01 | 2021-09-17 | 确成硅化学股份有限公司 | Preparation method of high-dispersion white carbon black special for high-fatigue-resistance tire |
| CN114286799A (en) * | 2021-12-01 | 2022-04-05 | 无锡恒诚硅业有限公司 | Preparation method and application of white carbon black for improving rheological property |
| WO2023097548A1 (en) * | 2021-12-01 | 2023-06-08 | 无锡恒诚硅业有限公司 | Preparation method for and application of white carbon black for improving rheological properties |
| CN115159530A (en) * | 2022-08-08 | 2022-10-11 | 确成硅化学股份有限公司 | Synthesis process of large-pore-volume precipitated silica for coating flatting agent |
| CN115571881A (en) * | 2022-10-14 | 2023-01-06 | 西南交通大学 | Preparation and energy storage testing method of nano silicon and battery using nano silicon |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110028073A (en) | A kind of preparation method of polymolecularity precipitated silica | |
| CN103880020B (en) | Chirality mesoporous organic silica nanotube or core-shell type nanometer rod and preparation method thereof | |
| JP2012091943A (en) | Aerogel | |
| US2805955A (en) | Silica composition and production thereof | |
| KR0148692B1 (en) | Aqueous colloidal dispersion of fumed silica, acid and stabilizer | |
| US7700062B2 (en) | Methods for synthesizing precipitated silica and use thereof | |
| CN108101068A (en) | A kind of high degree of structuration, the preparation method of high-reinforcement white carbon black and white carbon therefrom | |
| CN106044790B (en) | A kind of method of preparing white carbon black by precipitation method | |
| US2588853A (en) | Method of producing silica powder | |
| CN111498859A (en) | Preparation method of high-transparency high-dispersibility white carbon black | |
| CN114604874B (en) | High-refraction macroporous precipitated silica for high-transparency silicone rubber and preparation method thereof | |
| CN108408732A (en) | A kind of preparation method of especially big specific surface area silica flatting silica | |
| CN112678838A (en) | Low rolling resistance precipitated silica, and preparation method and application thereof | |
| CN103848427B (en) | A kind of high dispersive precipitated silica and preparation method thereof | |
| JP2010155750A (en) | Method of producing surface sealed silica particles, surface sealed silica particles, and resin composition for encapsulating semiconductor constituted by mixing the particles | |
| JP3055334B2 (en) | Method for producing colloidal calcium carbonate | |
| US20130068139A1 (en) | Silica gel comprising guanidine carbonate | |
| US3152001A (en) | Process for the production of a filler | |
| CN110835110A (en) | Preparation method of precipitated hydrated silicon dioxide | |
| JP5519306B2 (en) | Method for producing rubber / silica composite and rubber / silica composite | |
| CN110591415A (en) | Preparation method of anti-agglomeration modified nano calcium carbonate | |
| JP4846193B2 (en) | Easily dispersible precipitated silica cake and method for producing the same | |
| JP6410574B2 (en) | Method for producing porous silica | |
| CN112978737A (en) | Preparation method of nano silicon oxide particles with uniform particle size | |
| CN106698494B (en) | A kind of preparation method of spherical shape micro/nano level calcium carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190719 |
|
| RJ01 | Rejection of invention patent application after publication |