CN102976339A - Process for preparing high-dispersibility white carbon black through hydrochloric acid precipitation method - Google Patents
Process for preparing high-dispersibility white carbon black through hydrochloric acid precipitation method Download PDFInfo
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- CN102976339A CN102976339A CN2012104359601A CN201210435960A CN102976339A CN 102976339 A CN102976339 A CN 102976339A CN 2012104359601 A CN2012104359601 A CN 2012104359601A CN 201210435960 A CN201210435960 A CN 201210435960A CN 102976339 A CN102976339 A CN 102976339A
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Abstract
The invention discloses a process for preparing high-dispersibility white carbon black through a hydrochloric acid precipitation method, and relates to the technical field of white carbon black preparation in the chemical engineering field. The high-dispersibility white carbon black is prepared through treating sodium metasilicate as a raw material, deionized water as a reaction medium and hydrochloric acid as a precipitating agent and through adjusting the silicate radical hydrolysis rate and the silicic acidmolecule polymerization degree by adding a dispersant and by optimizing a reaction technology. The process has the advantages of easily available raw materials which are bulk chemicals common sold in the market, low production cost, simple technology, stable product quality, convenient enlarged production, and substantial social and economic benefits.
Description
Technical field:
The present invention relates to the technical field of chemical field white carbon black preparation, be specifically related to the method that a kind of salt acid precipitation method prepares the polymolecularity white carbon black.
Background technology:
White carbon black is lightweight hydrated SiO 2 material, exists with the micropore powder form of amorphous state, and be very widely important Chemicals of a kind of purposes.The white carbon black specific surface area is larger, usually greater than 130m
2/ g, powder particle has a large amount of microvoid structures, the rich surface hydroxyl, the characteristics such as good absorption, fire-retardant, insulation, suspension, thixotropy, thixotroping, scattering of light, surface graft modification are arranged, its remarkable strengthening action obtains important application at the rubber item manufacture field, in addition, white carbon black product also is widely used in the industries such as food, medicine, electronics, coating, papermaking, printing, catalyzer and daily-use chemical industry.
The preparation method of white carbon black mainly contains Physical and chemical method two large classes.It is high that Physical is produced the product foreign matter content, and more than micron order, class is not high greatly for product cut size, is difficult to satisfy industrial requirement, and therefore, white carbon black mainly adopts chemical method production.Chemical method production is divided into again number of ways and method because raw material is different with Technology, as the starting material of producing white carbon black have flower bulb alkali, water glass, the Starso that derives from the preparation of quartz sand and soda ash and come, the peridotites that derives from other nonmetalliferous ore, wollastonite, diatomite, attapulgite etc. are arranged, also derive from waste resource such as rice husk, flyash, yellow phosphorus furnace slag etc.; Production method has the precipitator method, sol-gel method, reversed phase micelle microemulsion method, vapour deposition process, hydrochloric acid pickling process etc.At present, white carbon black production mainly adopts the precipitator method and vapor phase process.Because vapor phase process is as raw material take HIGH-PURITY SILICON compound reagent such as silicon tetrachlorides, under high temperature (1200～1600 ℃) atmosphere of hydrogen, oxygen gas mixture burning generation water, be hydrolyzed, then obtain through aftertreatment technologys such as quenching, gathering, depicklings, although the product cut size that this method is produced is nano level, purity is higher, but this method investment of production is huge, reaction process is complicated, energy consumption is high, productive rate is low, valuable product, far can not satisfying the market to the demand of product of high quality and at a reasonable price.Comparatively speaking, it is basic raw material that the precipitator method adopt flower bulb alkali or water glass or Starso etc. more, prepare by the method with sour neutralization-precipitation reaction, this method has that facility investment is less, production technique is simple, starting material are cheap and easy to get, product yield and the higher advantage of cost performance, being conducive to expanded reproduction, is the universal method of the bulk product white carbon black of satisfying the market thriving demand.
The precipitator method are divided into sulfuric acid process and salt acid system usually according to the kind difference of adopt acid, wherein sulfuric acid process is the major way of production common white carbon black, for a long time, the sodium sulfate byproduct resource recovery that produces in the production process and discharge of wastewater and a caused environmental pollution difficult problem are perplexing sulfuric acid precipitation method white carbon black production industry always.The salt acid precipitation method is because the concentration of hydrochloric acid that adopts is lower than the vitriol oil, and early stage manufacturing enterprise only considers from the product carrying cost, fails to cause in a long time enough attention always.Now, along with the pay attention to day by day of the mankind to environmental problem, particularly people recognize that salt acid system production white carbon black byproduct in process sodium-chlor belongs to the outstanding advantages of safe and harmless property basically to environment, therefore, the Technology of salt acid system production precipitated silica more and more receives the concern of industry, and progressively replacing sulfuric acid process is important developing state.
Current, the precipitated silica product is mainly used in the rubber item industry and replaces traditional carbon black, because the autohemagglutination problem between the primary partical after the hydrolysis of the silicate in the production process is more serious, the powder particle granularity is wayward, product cut size is larger, several microns between the tens of micron, its dispersing property and the reinforcing property of rubber item etc. is a greater impact.
In order to significantly improve white carbon black product quality and performance, and constantly expand the Application Areas of white carbon black product, satisfying the market is to the thriving demand of white carbon black product of high quality and at a reasonable price, and the novel preparation method that bases oneself upon traditional precipitator method production technique emphasis exploitation salt acid system polymolecularity white carbon black product seems extremely important.
Summary of the invention:
There are the problems such as the polymerization degree is too high, particle diameter large, specific surface is less, bad dispersibility in the present invention for the white carbon black that solves existing common precipitator method explained hereafter, the problem of environmental pollution that the sodium sulfate wastewater discharging of avoiding simultaneously producing in the Production By Sulfuric Acid Process process causes provides a kind of novel preparation method of effective, the significant salt acid precipitation method of economic results in society polymolecularity white carbon black by further investigation.
Technical problem to be solved by this invention realizes by the following technical solutions:
A kind of salt acid precipitation method prepares the method for polymolecularity white carbon black, it is characterized in that, may further comprise the steps:
A, to get 1000ml weight part, concentration be 5～15% sodium metasilicate solution, adds the dispersion agent of 100～300 weight parts in sodium metasilicate solution, stirs and obtain mixed solution;
B, add mass concentration react greater than 10% hydrochloric acid in the mixed solution that obtains, the pH value that continues stirring until reaction system is to be precipitated thing at 4～9 o'clock;
C, with the throw out ageing 1～3h under 60～90 ℃ of conditions that obtains, then carry out press filtration, obtain filter cake;
D, the filter cake that obtains is washed, after the washing under 100～150 ℃ of conditions dry 2～4h, again through grinding the loose property white carbon black product that namely secures satisfactory grades.
Described dispersion agent is water-soluble good inorganic sodium, and described inorganic sodium is that SODIUMNITRATE or sylvite are saltpetre.
The stirring velocity of described sodium metasilicate solution and dispersion agent is 120～360 rev/mins.
The washing of described filter cake is deionized water wash, and the number of times of washing is 3～7 times.
The present invention is take Starso as raw material, take deionized water as reaction medium, utilizes hydrochloric acid to be precipitation agent, prepares the polymolecularity white carbon black by adding dispersion agent and the hydrolysis rate of optimization reaction process technical regulation silicate and the polymerization degree of silicic acid molecule.
The ultimate principle that the present invention produces white carbon black product is expressed as follows with chemical equation:
Na
2SiO
3+2HCl+2H
2O→2Na
++2Cl
-+H
4SiO
4↓
H
4SiO
4→SiO
2↓+2H
2O
n(SiO
2)→(SiO
2)
n↓
From above-mentioned chemical reaction as can be known, Starso at first under the hydrochloric acid effect wherein metasilicic acid radical ion hydrolysis occurs obtains the silicic acid molecule, the silicic acid molecule continues dehydration again and obtains silicon dioxide molecules, silicon dioxide molecules and then rapidly polymerization obtain the silicon dioxide granule of polymeric form.In the preparation process of white carbon black, the size from collecting process and the polymerization degree of silicic acid molecule has determined the size of particles of white carbon black product, more little more being easy to of product cut size disperseed, therefore, the gordian technique of preparation polymolecularity white carbon black is to control the autohemagglutination behavior of silicic acid molecule, makes the polymerization degree of silicon dioxide molecules be controlled at as far as possible rational scope.
Present Research analysis from current precipitated silica preparation, the factor of polymerization behavior that affects white carbon black product is much also very complicated, common influence factor the respond digestion time of use, system of temperature, feed way and the method for medium classification, reaction system, churned mechanically shearing action, tensio-active agent and dispersion agent and temperature etc.
The present invention passes through to introduce suitable dispersion agent on the technique basis of ordinary salt acid precipitation method, simultaneously, by the processing condition such as temperature, time, feed way method of regulation and control reaction system, effectively generate on the one hand the relative rate of silicic acid molecule in the control reaction system in metasilicic acid radical ion hydrolysis rate and the system; On the other hand, utilize the effect of churned mechanically shearing and dispersion agent, greatly reduce silicic acid molecule autohemagglutination probability each other, reduce the polymerization degree of silicic acid molecule, realize the purpose of regulation and control precipitated silica particle size, thereby prepare the tiny uniform polymolecularity white carbon black product of particle diameter.
The product index synopsis of the product of the present invention's preparation and the preparation of ordinary salt acid precipitation method is referring to table 1.
As can be seen from Table 1, the white carbon black product that the present invention makes is obviously all thin than the product cut size of ordinary salt acid system, more be conducive to realize the high dispersive performance of product, because the present invention continued to use salt acid precipitation method production unit substantially, be a kind ofly to need not to increase fixedly that production facility drops into the Perfected process that can realize that white carbon black product upgrades.
White carbon black and the ordinary salt acid precipitation method white carbon black product leading indicator of table 1 the present invention preparation
As optimization of the present invention, described dispersion agent is that the described dispersion agent of 100～300 weight parts is water-soluble good inorganic sodium such as SODIUMNITRATE or sylvite such as saltpetre etc.
The speed that stirs among the described step b is 120～360 rev/mins.
The washing of in the described steps d filter cake being carried out is deionized water wash 3～7 times.
The invention has the beneficial effects as follows: required raw material is commercially available common bulk chemical among the present invention, and raw material is easy to get, low production cost, and Technology is simple, and constant product quality is convenient to expanded reproduction, society and remarkable in economical benefits.
Embodiment:
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, further set forth the present invention below in conjunction with specific embodiment.
Embodiment 1:
A kind of salt acid precipitation method prepares the method for polymolecularity white carbon black, comprises that the following step poly-:
Be to add the 100.0g SODIUMNITRATE in 5% the sodium metasilicate solution in 1000ml concentration, stir and obtain mixed solution, in the mixed solution that obtains, slowly add concentration and be 10% hydrochloric acid and stir with 120 rev/mins speed, pH=4 to reaction system, be precipitated thing, then with the throw out press filtration behind ageing 3h under 60 ℃ of conditions that obtains, the filter cake that press filtration obtains deionized water wash 3 times, filter cake after the washing is again through 150 ℃ of dry 2h, get final product to get white carbon black 22.6g through grinding, product cut size is 153.3nm.
Embodiment 2:
A kind of salt acid precipitation method prepares the method for polymolecularity white carbon black, comprises that the following step poly-:
Be to add the 200.0g SODIUMNITRATE in 10% the sodium metasilicate solution in 1000ml concentration, stir and obtain mixed solution, in the mixed solution that obtains, slowly add concentration and be 20% hydrochloric acid and stir with 240 rev/mins speed, pH=7 to reaction system, be precipitated thing, then with the throw out press filtration behind ageing 1.5h under 80 ℃ of conditions that obtains, the filter cake that press filtration obtains deionized water wash 5 times, filter cake after the washing is again through 130 ℃ of dry 3h, get final product to get white carbon black 45.5g through grinding, product cut size is 127.4nm.
Embodiment 3:
A kind of salt acid precipitation method prepares the method for polymolecularity white carbon black, comprises that the following step poly-:
Be to add the 300.0g SODIUMNITRATE in 15% the sodium metasilicate solution in 1000ml concentration, stir and obtain mixed solution, in the mixed solution that obtains, slowly add concentration and be 30% hydrochloric acid and stir with 360 rev/mins speed, pH=9 to reaction system, be precipitated thing, then with the throw out press filtration behind ageing 1h under 90 ℃ of conditions that obtains, the filter cake that press filtration obtains deionized water wash 7 times, filter cake after the washing is again through 110 ℃ of dry 4h, get final product to get white carbon black 67.4g through grinding, product cut size is 136.2nm.
Embodiment 4:
A kind of salt acid precipitation method prepares the method for polymolecularity white carbon black, comprises that the following step poly-:
Be to add 300.0g saltpetre in 10% the sodium metasilicate solution in 1000ml concentration, stir and obtain mixed solution, in the mixed solution that obtains, slowly add concentration and be 30% hydrochloric acid and stir with 240 rev/mins speed, pH=7 to reaction system, be precipitated thing, then with the throw out press filtration behind ageing 1h under 80 ℃ of conditions that obtains, the filter cake that press filtration obtains deionized water wash 5 times, filter cake after the washing is again through 130 ℃ of dry 3h, get final product to get white carbon black 44.8g through grinding, product cut size is 122.6nm.
Embodiment 5:
A kind of salt acid precipitation method prepares the method for polymolecularity white carbon black, comprises that the following step poly-:
Be to add 200.0g saltpetre in 15% the sodium metasilicate solution in 1000ml concentration, stir and obtain mixed solution, in the mixed solution that obtains, slowly add concentration and be 20% hydrochloric acid and stir with 180 rev/mins speed, pH=4 to reaction system, be precipitated thing, then with the throw out press filtration behind ageing 2h under 60 ℃ of conditions that obtains, the filter cake that press filtration obtains deionized water wash 7 times, filter cake after the washing is again through 120 ℃ of dry 3h, get final product to get white carbon black 68.7g through grinding, product cut size is 134.8nm.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in above-described embodiment and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (4)
1. a salt acid precipitation method prepares the method for polymolecularity white carbon black, it is characterized in that, may further comprise the steps:
A, to get 1000 ml weight parts, concentration be 5～15% sodium metasilicate solution, adds the dispersion agent of 100～300 weight parts in sodium metasilicate solution, stirs and obtain mixed solution;
B, add mass concentration react greater than 10% hydrochloric acid in the mixed solution that obtains, the pH value that continues stirring until reaction system is to be precipitated thing at 4～9 o'clock;
C, with the throw out ageing 1～3h under 60～90 ℃ of conditions that obtains, then carry out press filtration, obtain filter cake;
D, the filter cake that obtains is washed, after the washing under 100～150 ℃ of conditions dry 2～4h, again through grinding the white carbon black product of the loose property that namely secures satisfactory grades.
2. a kind of salt acid precipitation method according to claim 1 prepares the method for polymolecularity white carbon black, it is characterized in that: described dispersion agent is water-soluble good inorganic sodium, and described inorganic sodium is that SODIUMNITRATE or sylvite are saltpetre.
3. a kind of salt acid precipitation method according to claim 1 prepares the method for polymolecularity white carbon black, it is characterized in that: the stirring velocity of described sodium metasilicate solution and dispersion agent is 120～360 rev/mins.
4. a kind of salt acid precipitation method according to claim 1 prepares the method for polymolecularity white carbon black, it is characterized in that: the washing of described filter cake is deionized water wash, and the number of times of washing is 3～7 times.
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Cited By (7)
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|---|---|---|---|---|
| CN103964447A (en) * | 2014-05-31 | 2014-08-06 | 苏州恒瑞生物医药科技有限公司 | Method for producing fluoride and white carbon black by accelerating hydrolysis of fluosilicate with ultrasonic waves |
| CN109678164A (en) * | 2018-12-25 | 2019-04-26 | 江西双龙硅材料科技有限公司 | A kind of environmentally protective white carbon black, caustic soda recycle combine production method |
| CN110156029A (en) * | 2019-04-28 | 2019-08-23 | 于拴全 | Red mud Chemical Physics integrated conduct method |
| 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 |
| CN112007610A (en) * | 2020-09-04 | 2020-12-01 | 桂林良物造日用品有限公司 | Preparation method of diatomite-coated nano white carbon material with high adsorption performance |
| CN113105762A (en) * | 2021-04-13 | 2021-07-13 | 云南云维飞虎化工有限公司 | Method for improving dispersibility of carbon black |
| CN115159529A (en) * | 2022-08-15 | 2022-10-11 | 锦洋高新材料股份有限公司 | Method for preparing white carbon black by taking industrial silicon dioxide solid waste as raw material through precipitation method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964447A (en) * | 2014-05-31 | 2014-08-06 | 苏州恒瑞生物医药科技有限公司 | Method for producing fluoride and white carbon black by accelerating hydrolysis of fluosilicate with ultrasonic waves |
| CN109678164A (en) * | 2018-12-25 | 2019-04-26 | 江西双龙硅材料科技有限公司 | A kind of environmentally protective white carbon black, caustic soda recycle combine production method |
| CN109678164B (en) * | 2018-12-25 | 2022-05-03 | 江西双龙硅材料科技有限公司 | Environment-friendly white carbon black and caustic soda circulating joint production method |
| CN110156029A (en) * | 2019-04-28 | 2019-08-23 | 于拴全 | Red mud Chemical Physics integrated conduct method |
| 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 |
| CN112007610A (en) * | 2020-09-04 | 2020-12-01 | 桂林良物造日用品有限公司 | Preparation method of diatomite-coated nano white carbon material with high adsorption performance |
| CN113105762A (en) * | 2021-04-13 | 2021-07-13 | 云南云维飞虎化工有限公司 | Method for improving dispersibility of carbon black |
| CN115159529A (en) * | 2022-08-15 | 2022-10-11 | 锦洋高新材料股份有限公司 | Method for preparing white carbon black by taking industrial silicon dioxide solid waste as raw material through precipitation method |
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Application publication date: 20130320 |