CN104291344B - Production method for white carbon black - Google Patents
Production method for white carbon black Download PDFInfo
- Publication number
- CN104291344B CN104291344B CN201410582351.8A CN201410582351A CN104291344B CN 104291344 B CN104291344 B CN 104291344B CN 201410582351 A CN201410582351 A CN 201410582351A CN 104291344 B CN104291344 B CN 104291344B
- Authority
- CN
- China
- Prior art keywords
- waterglass
- sulfuric acid
- value
- reaction
- steam
- 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.)
- Active
Links
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention relates to a production method for an inorganic powder material, in particular to a production method for white carbon black applied to high-elastic silicone rubber. The production method comprises the processes of dissolution and refining of water glass, synthesis reaction of the water glass and dilute sulphuric acid, pressure filtration, washing, pulping and drying; the reaction of the water glass and the dilute sulphuric acid comprises the following three steps: generating seed crystal, conducting synthesis reaction and adjusting integral pH value. According to the invention, the synthesis process of three steps is adopted; the specific surface area of the product is reduced by adding a sodium sulfate additive; reaction conditions are controlled strictly; the particle diameter of secondary particles of the product is controlled effectively; the characteristics of small specific surface area, low oil absorption value, high additive amount, high reinforcing performance and short mixing time during mixing with silicone rubber are provided; the raw materials are easy to obtain; the process is easy to control; no extra equipment is needed; the production can be conducted on an original production line.
Description
Technical field
The present invention relates to a kind of production method of inorganic powder material is and in particular to be applied to the high interpolation of high-elastic silicon rubber
The production method of amount white carbon.
Background technology
Precipitated silica is a kind of widely used inorganic functional powder body material, be mainly used in General Purpose Rubber, silicon rubber,
The fields such as coating, ink, agricultural chemicals, papermaking.It is mainly the precipitation method for high-elastic silicon rubber white carbon black production method.The existing precipitation method
White carbon black production method generally with liquid soluble glass, the concentrated sulfuric acid as raw material, through precipitation reaction, press filtration, slurrying, spray drying and make
, there is the problem that because leading to product surface hydroxyl hydrophily strong, particle specific surface area is big more, thus in high-elastic silicon rubber
Middle application seldom, with the upgrading of silicone rubber products, the increase in demand to high-elastic silicon rubber, high addition white carbon is to carrying
High product processing characteristics, reduces production cost, plays very big effect.
Content of the invention
The purpose of the present invention is to provide one kind to have particle slightly for above-mentioned deficiency, and oil factor is low, and specific surface area is little, makees
Production method for the high addition white carbon of high-elastic silicon rubber reinforcement and filler material.
The technical solution of the present invention is: a kind of production method of high addition white carbon, and its operating procedure includes water
The dissolving of glass with refined, waterglass and dilute sulfuric acid (mass fraction is the sulfuric acid of 15%-20%) carry out synthetic reaction, press filtration,
Washing, slurrying, drying process, it is characterized in that: waterglass and dilute sulfuric acid react point three-step approach to be carried out, first generate crystal seed, then carry out
Synthetic reaction, finally adjusts overall ph value, specifically comprises the following steps that
(1) refine water glass solution: solid water glass and water are added to static dissolving bucket according to the ratio of 1:1.5, close
It is honored as a queen and is passed through steam, stop being passed through steam when pressure rises to 0.4-0.5 mpa, pressurize expected to throw in material-compound tank after 3 hours, plus
Enter water, waterglass is configured to 1.075-1.095g/cm3, standby after plate-frame filtering；Configure sodium oxide content by technological requirement
(2.38-2.42%), ensure that liquid soluble glass is limpid, to ensure product quality after plate-frame filtering.
(2) precipitated silica synthetic reaction: waterglass is squeezed in reactor, adds the sulfuric acid that mass fraction is 15-20%
Sodium solution, the sodium sulfate quality of waterglass and 15-20% is than for 1:1；It is passed through steam, be warming up to and open stirring when 45-50 DEG C, continue
Continue and be warming up to 89-90 DEG C, the sulfuric acid that the mass fraction having configured is 15-20% adds reaction by 1.76-1.81m/h flow
In kettle, reaction generates crystallite kind, and the reaction time is 40 minutes, reacts to ph value between 10-11, second step, then by waterglass
It is simultaneously introduced in reactor according to 3.84-3.94 m/h flow with the dilute sulfuric acid of the flow of 18-18.5m/h and 15-20%, enter
Row synthetic reaction, the reaction time be 50 minutes, reaction temperature 89-90 DEG C, reaction controlling ph value between 10-11, the 3rd step, continue
The continuous sulfuric acid adding 15-20%, flow is that 3.85-3.95 m/h adjusts terminal ph value in 4-5, stops after continuing stirring 30 minutes
Stirring.
Above in three-step approach, the first step is that flow is low, and control material degree of neutralization, below 40%, adds sodium sulphate to guarantee
The structure of product, disclosure satisfy that the requirement of low specific surface area.Second step is to control reaction degree of neutralization 85% about, in crystal seed
On the basis of regrow, form big structure it is ensured that product meets the design objective that particle is thick, specific surface area is little, absorption value is low.
3rd step is that adjustment product ph value is stablized it is ensured that subsequently vulcanizing processing characteristics.
(3) press filtration of reacting slurry, washing: reacted slurries pass through plate and frame filter press and carry out solid, liquid separately, wash to
Electrical conductivity is less than 1000 μ s/cm.
(4) slurrying: filter cake delivers to making beating by belt conveyor, by high speed and two kinds of stir mode slurrying of low speed,
There is provided uniform slurries for being spray-dried.
(5) drying process: after the spray-dried tower of slurries is dried, then be crushed to particle diameter less than 20 μ through mechanical crusher
M, after collection, packaging and storage.
For realizing object above, the present invention adopts a kind of liquid soluble glass and the concentrated sulfuric acid in the effect of 15% metabisulfite solution
Under carry out precipitation reaction, obtain being exclusively used in high-elastic silicon rubber precipitated silica through press filtration, washing, slurrying, spray drying.
The invention has the advantage that 1, by improving to traditional precipitated silica production technology, by optimize technique
Parameter, the mode of preferred promoter reach the requirement improving product addition and low specific surface area, overcome ordinary precipitation process particle to add
Dosage is little, reinforcing difference, the shortcoming of mixing time length, and products application is in high elastic rubber product.2nd, three-step approach is adopted to synthesize
Technique, and add sodium sulphate auxiliary agent to reduce product specific surface area, strictly control reaction condition, can be secondary with effective control product
The particle diameter of particle, has that specific surface area is little, and oil factor is low, has addition big with mixing silicon rubber, reinforcing height, and mixing time is fast
Feature.3rd, raw material of the present invention is easy to get, and process is easily controlled it is not necessary to increase equipment, can give birth on original production line
Produce.
Below in conjunction with embodiment, embodiments of the present invention are described in further detail.
Specific embodiment
Embodiment 1
The production method of high addition white carbon:
1st, waterglass refines
The waterglass taking 40m to dissolve through steam, is configured to the waterglass that proportion is 1.080g/ cm, through plate-frame filtering,
Take clear liquid standby.
2nd, the synthesis of silica
Add the bed material of 15m in the reactor of 55m, be simultaneously introduced the sodium sulphate of equal in quality, be passed through steam and heat up,
Temperature opens stirring when rising to 50 DEG C, continue to heat up, and temperature starts when reaching 87 DEG C to drip sulfuric acid, and sulfuric acid drips 0.17m per hour
, react to ph value between 10-11, start second-stage reaction, be simultaneously added dropwise waterglass and sulfuric acid, waterglass drips 18m per hour
, sulfuric acid drips 0.37m per hour, reacts and stop dripping between 10-11 to ph value, proceeds by three sections of reactions, dropping sulphur
Acid, adjusts reaction end ph value, and flow is 0.38m per hour, adjusts to ph value between 4.0-5.0, synthetic reaction terminates,
Ageing 30 minutes.
3rd, reacting slurry press filtration, the slurries after washing reaction carry out solid, liquid by plate and frame filter press and separate, using electrical conductivity
Water washing for 100 μ s/cm is less than 1000 μ s/cm, sodium sulphate content ＜ 0.5% to electrical conductivity.
4th, slurrying
Filter cake delivers to making beating by belt conveyor, by high speed and two kinds of stir mode slurrying of low speed, dry for spraying
The uniform slurries of dry offer.
5th, drying process
After the spray-dried tower of slurries is dried, then it is crushed to particle diameter through mechanical crusher and is less than 20 μm, with pocket type pulsed
After deduster is collected, packaging and storage.
Embodiment 2
The production method of high addition white carbon:
1st, waterglass refines
The waterglass taking 50m to dissolve through steam, is configured to the waterglass that proportion is 1.085g/ cm, through plate-frame filtering,
Take clear liquid standby.
2nd, the synthesis of silica
Add the bed material of 12m in the reactor of 55m, be simultaneously introduced the sodium sulphate of equal in quality, be passed through steam and heat up,
Temperature opens stirring when rising to 45 DEG C, continue to heat up, and temperature starts when reaching 88 DEG C to drip sulfuric acid, and sulfuric acid drips 0.15m per hour
, react to ph value between 10-11, start second-stage reaction, be simultaneously added dropwise waterglass and sulfuric acid, waterglass drips per hour
17.5m, sulfuric acid drips 0.39m per hour, reacts and stops dripping between 10-11 to ph value, proceed by three sections of reactions, drips
Plus sulfuric acid, adjust reaction end ph value, flow is 0.35m per hour, adjusts to ph value between 4.0-5.0, and synthetic reaction is tied
Bundle, is aged 30 minutes.
3rd, reacting slurry press filtration, washing
Reacted slurries carry out solid, liquid by plate and frame filter press and separate, the water washing the use of electrical conductivity being 100 μ s/cm
It is less than 1000 μ s/cm, sodium sulphate content ＜ 0.5% to electrical conductivity.
4th, slurrying
Filter cake delivers to making beating by belt conveyor, by high speed and two kinds of stir mode slurrying of low speed, dry for spraying
The uniform slurries of dry offer.
5th, drying process
After the spray-dried tower of slurries is dried, then it is crushed to particle diameter through mechanical crusher and is less than 20 μm, with pocket type pulsed
After deduster is collected, packaging and storage.
Interpretation of result
The white carbon that both examples above is obtained and the performance indications of common white carbon contrast and are shown in Table one, table two:
The each product overall target of table one contrasts
The each product physical performance index of table two contrasts
Can be seen that the present invention from above-mentioned two example adopts three-stage to react, and adds sodium sulphate during the course of the reaction
Auxiliary agent, strictly controls reaction condition, can largely be reduced product and compared table with the particle diameter of effective control product offspring
With tradition white carbon, area, relatively has the characteristics that specific surface area is little, applies and high elastic rubber.Raw material of the present invention is easy to get, mistake
Journey is easily controlled it is not necessary to increase equipment, just can produce, products application is in high elastic rubber product on original production line
In.
Claims (2)
1. a kind of production method of white carbon, its operating procedure includes the dissolving of waterglass and refines, and waterglass is entered with dilute sulfuric acid
Row synthetic reaction, press filtration, washing, slurrying, drying process, it is characterized in that: waterglass and dilute sulfuric acid react point three-step approach to be carried out, first
Generate crystal seed, then carry out synthetic reaction, finally adjust overall ph value, specifically comprise the following steps that
(1) refine water glass solution: solid water glass and water are added to static dissolving bucket according to the ratio of 1:1.5, after sealing
It is passed through steam, stop being passed through steam when pressure rises to 0.4-0.5 mpa, pressurize expected to throw in material-compound tank after 3 hours, took 40m
Waterglass through steam dissolving, adds water, is configured to the waterglass that proportion is 1.080g/ cm, through plate-frame filtering, takes clear liquid standby
With；
(2) precipitated silica synthetic reaction: add the bed material of 15m in the reactor of 55m, be simultaneously introduced equal in quality
The metabisulfite solution of 15-20%, is passed through steam and heats up, temperature opens stirring when rising to 50 DEG C, continues to heat up, when temperature reaches 87 DEG C
Start to drip sulfuric acid, sulfuric acid drips 0.17m per hour, react to ph value between 10-11, start second-stage reaction, be simultaneously added dropwise
Waterglass and sulfuric acid, waterglass drips 18m per hour, and sulfuric acid drips 0.37m per hour, reacts to ph value between 10-11
Stop dropping, proceed by three sections of reactions, drip sulfuric acid, adjust reaction end ph value, flow is 0.38m per hour, adjust to
Between 4.0-5.0, synthetic reaction terminates ph value, is aged 30 minutes；
(3) press filtration of reacting slurry, washing: reacted slurries carry out solid, liquid by plate and frame filter press and separate, and wash to conductance
Rate is less than 1000 μ s/cm；
(4) slurrying: filter cake delivers to making beating by belt conveyor, by high speed and two kinds of stir mode slurrying of low speed, for spray
Mist is dried provides uniform slurries；
(5) drying process: after the spray-dried tower of slurries is dried, then be crushed to particle diameter less than 20 μm through mechanical crusher, receive
After collection, packaging and storage.
2. a kind of production method of white carbon, its operating procedure includes the dissolving of waterglass and refines, and waterglass is entered with dilute sulfuric acid
Row synthetic reaction, press filtration, washing, slurrying, drying process, it is characterized in that: waterglass and dilute sulfuric acid react point three-step approach to be carried out, first
Generate crystal seed, then carry out synthetic reaction, finally adjust overall ph value, specifically comprise the following steps that
(1) refine water glass solution: solid water glass and water are added to static dissolving bucket according to the ratio of 1:1.5, after sealing
It is passed through steam, stop being passed through steam when pressure rises to 0.4-0.5 mpa, pressurize expected to throw in material-compound tank after 3 hours, took 50m
Waterglass through steam dissolving, adds water, is configured to the waterglass that proportion is 1.085g/ cm, through plate-frame filtering, takes clear liquid standby
With；
(2) precipitated silica synthetic reaction: add the bed material of 12m in the reactor of 55m, be simultaneously introduced equal in quality
The metabisulfite solution of 15-20%, is passed through steam and heats up, temperature opens stirring when rising to 45 DEG C, continues to heat up, when temperature reaches 88 DEG C
Start to drip sulfuric acid, sulfuric acid drips 0.15m per hour, react to ph value between 10-11, start second-stage reaction, be simultaneously added dropwise
Waterglass and sulfuric acid, waterglass drips 17.5m per hour, and sulfuric acid drips 0.39m per hour, react to ph value 10-11 it
Between stop dropping, proceed by three sections of reactions, drip sulfuric acid, adjust reaction end ph value, flow is 0.35m per hour, regulation
To ph value between 4.0-5.0, synthetic reaction terminates, and is aged 30 minutes；
(3) press filtration of reacting slurry, washing: reacted slurries carry out solid, liquid by plate and frame filter press and separate, and wash to conductance
Rate is less than 1000 μ s/cm；
(4) slurrying: filter cake delivers to making beating by belt conveyor, by high speed and two kinds of stir mode slurrying of low speed, for spray
Mist is dried provides uniform slurries；
(5) drying process: after the spray-dried tower of slurries is dried, then be crushed to particle diameter less than 20 μm through mechanical crusher, receive
After collection, packaging and storage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410582351.8A CN104291344B (en) | 2014-10-28 | 2014-10-28 | Production method for white carbon black |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410582351.8A CN104291344B (en) | 2014-10-28 | 2014-10-28 | Production method for white carbon black |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104291344A CN104291344A (en) | 2015-01-21 |
| CN104291344B true CN104291344B (en) | 2017-01-18 |
Family
ID=52311338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410582351.8A Active CN104291344B (en) | 2014-10-28 | 2014-10-28 | Production method for white carbon black |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104291344B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106829967A (en) * | 2017-03-06 | 2017-06-13 | 福建省三明正元化工有限公司 | A kind of tire is formulated with high dispersive silicon dioxde reaction |
| CN107720762A (en) * | 2017-11-29 | 2018-02-23 | 通化双龙硅材料科技有限公司 | The production method of alkaline white carbon |
| CN107915232A (en) * | 2017-12-06 | 2018-04-17 | 安徽凤阳赛吉元无机材料有限公司 | A kind of white carbon black production technique without using fluorescent whitening agent |
| CN108455641B (en) * | 2018-05-28 | 2020-08-11 | 福建远翔新材料股份有限公司 | Preparation method of nano silicon dioxide for high-elasticity silicone rubber |
| CN108675307B (en) * | 2018-06-13 | 2019-03-29 | 广州市飞雪材料科技有限公司 | A kind of low refractive power high viscosity friction type silica and preparation method thereof |
| CN109368649B (en) * | 2018-11-02 | 2020-06-05 | 株洲兴隆新材料股份有限公司 | Method for preparing precipitated white carbon black by improved dropwise adding process |
| CN109626384A (en) * | 2018-12-27 | 2019-04-16 | 通化双龙硅材料科技有限公司 | A kind of preparation method of toothpaste precipitated silica rubbing agent |
| CN110330022B (en) * | 2019-07-08 | 2020-11-24 | 福建远翔新材料股份有限公司 | Preparation method of high-dispersion silicon dioxide for foaming silicone rubber sponge |
| CN110562991A (en) * | 2019-10-15 | 2019-12-13 | 龙星化工股份有限公司 | Production method of white carbon black for high-oil-absorption carrier |
| CN111634920B (en) * | 2020-06-16 | 2022-01-18 | 福建远翔新材料股份有限公司 | Preparation method of nano silicon dioxide for food anti-caking agent |
| CN112678838A (en) * | 2020-12-29 | 2021-04-20 | 无锡恒诚硅业有限公司 | Low rolling resistance precipitated silica, and preparation method and application thereof |
| CN114804130B (en) * | 2021-06-17 | 2024-02-06 | 北京华夏建龙矿业科技有限公司 | Method for preparing water glass and white carbon black by using serpentine |
| CN113651332B (en) * | 2021-08-11 | 2023-10-27 | 常州大学 | Preparation method of high-performance white carbon black based on styrene-butadiene rubber reinforcement |
| CN115571886B (en) * | 2022-10-14 | 2023-12-05 | 福建正盛无机材料股份有限公司 | Preparation method of low-oil-absorption low-specific-surface-area silicon dioxide |
| CN117361547B (en) * | 2023-09-11 | 2024-04-30 | 金三江(肇庆)硅材料股份有限公司 | Silicon dioxide particles and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2678259B1 (en) * | 1991-06-26 | 1993-11-05 | Rhone Poulenc Chimie | NOVEL PRECIPITATED SILICA IN THE FORM OF GRANULES OR POWDERS, METHODS OF SYNTHESIS AND USE FOR REINFORCING ELASTOMERS. |
| CN101402457B (en) * | 2007-11-05 | 2011-04-13 | 通化双龙化工股份有限公司 | Process for producing deposition white carbon black for silicon rubber |
| CN101898776A (en) * | 2009-05-27 | 2010-12-01 | 北京紫光英力化工技术有限公司 | New process for co-producing ultra-fine white carbon black and calcium carbonate |
| CN101597065B (en) * | 2009-07-28 | 2011-01-26 | 通化双龙化工股份有限公司 | Method for preparing white carbon black of PE clapboard |
| CN102408115A (en) * | 2011-08-22 | 2012-04-11 | 通化双龙化工股份有限公司 | Method for controlling gel amount in white carbon black by using precipitation method |
-
2014
- 2014-10-28 CN CN201410582351.8A patent/CN104291344B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104291344A (en) | 2015-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104291344B (en) | Production method for white carbon black | |
| CN101979443B (en) | Method for producing modified white carbon black | |
| CN101544390B (en) | A method for preparing nano calcium carbonate | |
| CN107720762A (en) | The production method of alkaline white carbon | |
| CN106185956B (en) | A kind of preparation method of toothpaste precipitated silica thickener | |
| JP4537379B2 (en) | Process and apparatus for producing precipitated silica from rice husk ash | |
| CN104497634B (en) | Preparation method of nano calcium carbonate used for weather proofing silicone sealant | |
| JP5575800B2 (en) | Method for producing spherical barium sulfate by sulfuric acid method and use in copper foil substrate | |
| CN104016391A (en) | Method for preparing nanometer calcium carbonate for organic silicone electronic sealant by adopting continuous carbonization device | |
| CN104087029B (en) | A kind of preparation method of silicone sealant special active calcium carbonate | |
| CN105712361A (en) | Production method of food additive white carbon black | |
| CN101774591B (en) | Production technology of white microsphere high-strength white carbon black | |
| CN107324346A (en) | A kind of preparation method of high-specific surface area high oil absorption value silica | |
| CN103693650A (en) | Method for producing nano silicon dioxide and nano calcium carbonate by using rice hull ash and flue gas of biomass power plant | |
| CN106829975A (en) | A kind of preparation method of green tire high-dispersion white carbon black | |
| CN106829977A (en) | A kind of preparation method of high oil absorption high-dispersion white carbon black | |
| CN108439414A (en) | A kind of method that pH value swing method prepares high dispersive macropore appearance precipitated silica | |
| CN104386725B (en) | A kind of method that high white superfine aluminium hydroxide is prepared with Bayer process aluminium hydroxide | |
| CN102408115A (en) | Method for controlling gel amount in white carbon black by using precipitation method | |
| CN109824076B (en) | Process for preparing calcium carbonate by bubble membrane method and application thereof | |
| CN101914312B (en) | Preparation method of nano activated calcium carbonate for coating | |
| CN104418332B (en) | A kind of preparation method of silicon dioxide | |
| CN102502748B (en) | Microwave method for preparing rose-shaped calcium carbonate | |
| CN107033477A (en) | The CPE cable jacket materials and its manufacture method of a kind of high abrasion | |
| CN103880058A (en) | Precipitated calcium carbonate production technology for reducing magnesium and increasing calcium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20161221 Address after: 336100 Jiangxi city of Yichun province Wanzai County Industrial Park Applicant after: Jiangxi Shuanglong silicon Mstar Technology Ltd Address before: 134006 Tonghua City, Jilin province Erdaojiang District ironworks town Applicant before: Tonghua Shuanglong Chemical Co., Ltd. |
|
| TA01 | Transfer of patent application right | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |