CN101077777A - Method for preparing white carbon black from secondary carbon component - Google Patents
Method for preparing white carbon black from secondary carbon component Download PDFInfo
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- CN101077777A CN101077777A CN 200710062197 CN200710062197A CN101077777A CN 101077777 A CN101077777 A CN 101077777A CN 200710062197 CN200710062197 CN 200710062197 CN 200710062197 A CN200710062197 A CN 200710062197A CN 101077777 A CN101077777 A CN 101077777A
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- carbon black
- solution
- white carbon
- sodium silicate
- silicate solution
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Abstract
The twice carbon separating process for preparing silica white includes introducing CO2 gas to sodium silicate solution to lower the pH value to 9-10.5, solid-liquid separating, further introducing CO2 gas to the solution to lower the pH value to 7-8, solid-liquid separating, washing and stoving to obtain coarse silica while product, soaking or boiling in strong acid solution, washing and stoving to obtain silica while product. The present invention may have the sodium silicate solution obtained through soaking high silicon slag from producing aluminum sulfate, aluminum chloride, ferrous metal and non-ferrous metal and with high impurity content as the material, and the silica while product has high purity, fine granularity and high whiteness.
Description
Technical field
The present invention relates to a kind of Preparative Method of White Carbon Black, the Preparation of White Carbon Black method of particularly utilizing carbonic acid gas carbon to divide.The present invention can use the higher sodium silicate solution of foreign matter content to prepare white carbon black.
Background technology
White carbon black is exactly pure superfine silicon dioxide, and is acidproof, high temperature resistant, and chemical property is stable, is a kind of important Inorganic Chemicals, how as reinforced filling.Because the silica particles yardstick is little, specific surface area is big, surface silicon alcohol radical and reactive silane bond energy form the strong and weak hydrogen bonded that does not wait, thereby have properties such as good electric insulating quality, water absorbability, extinction and dispersiveness, in various fields such as rubber, coating, plastics, papermaking, printing ink, household chemicals, purposes is widely arranged.
Industrial production of white sooty method has the precipitator method, vapor phase process, hydrothermal synthesis method and gel method, and wherein the precipitator method are the major industry methods of producing white carbon black at present.In the precipitator method again because of in different sulfuric acid process, salt acid system, nitrate method and the carbonic acid gas carbon methods etc. of being divided into the employed medium of sodium silicate solution.
Use in the strong acid to prepare precipitated silica, require to use the higher sodium silicate solution of purity with sodium silicate solution, otherwise, must use excessive strong acid, technological process can produce a large amount of acid brine wastes, because can't economic recovery, directly discharging must cause great pollution to environment.Therefore seek pollution-free technology and just seem extremely important to substitute the strong acid neutralisation that generally adopts at present.
The carbonic acid gas carbon method is to be that raw material carries out carbon earlier and divides reaction with sodium silicate aqueous solution and carbonic acid gas, and steps such as acidified again, ageing, filtration, washing, drying, pulverizing obtain white carbon black.Though this method technology is simple, with low cost, the general particle of the white carbon black of producing is bigger, the SiO that separates out
2Small grains is easy to take place glomerocryst and grows up, and causes size-grade distribution inhomogeneous, and purity is not high, and then influences the use properties of product.Particularly the gas liquid reaction time of this method long, transformation efficiency is low." chemical industry of inorganic salt " 1998 the 2nd phases " engineering analysis of the white carbon black of carborization production " literary composition has been reported and carried out the reaction of carbon branch in being had the tank reactor of stirring, 200 rev/mins of stirring velocitys, reaction needed 6 hours, the pH value that reaction finishes back solution is 9～10, transformation efficiency is very low, have only 71.5%, if make transformation efficiency bring up to 95%, then the reaction times need extend to 95.6 hours.
No. 001322753 patent provides a kind of carburizing reagent to prepare the method for silicon-dioxide powdery, this method is to adopt supergravity reactor as carbonization reactor, reaction solution enters the rotating packed bed inner chamber of supergravity reactor through liquid inlet tube, through the shower nozzle sprinkle on the packed bed inner edge, reactant gases tangentially enters the packed bed outer rim through gas inlet tube, enter bed of packings by the packed bed outer rim, in carbonation reaction, reaction solution returns the liquid inlet again by liquid exit and enters rotating packed bed, forms uninterrupted circulating reaction.This method can shorten to the carburizing reagent time in 1 hour, enhances productivity.
Yet, above-mentioned the whole bag of tricks all requires the sodium silicate solution that uses purity higher, more than experiment is based on all that technical grade water glass raw material obtains, and when using the higher water glass of foreign matter content, original carbon method can't be produced qualified white carbon black product at all.
Summary of the invention
The method that the purpose of this invention is to provide a kind of preparing white carbon black from secondary carbon component, this method can use the higher sodium silicate solution of foreign matter content to produce qualified white carbon black product.
The method of preparing white carbon black from secondary carbon component of the present invention is to feed CO in sodium silicate solution
2Gas, intensification stirring reaction to the pH value of solution reduces to 9～10.5, stops the carbon branch, solid-liquid separation, solution for continuous feeds CO
2Gas carries out second time carbon and divides reaction, reduces to 7～8, stopped reaction to the pH value of solution value, solid-liquid separation, solid obtains white carbon black through washing, oven dry, and carbon divides isolated solid sediment to boil with strong acid immersion or heat for the first time, after impurity was removed in washing, oven dry obtained white carbon black.
The concrete steps of preparing white carbon black from secondary carbon component of the present invention are:
1. in being 8～15% sodium silicate solution, concentration feeds CO
2Gas, stirring reaction under 40～85 ℃ of temperature reduces to 9～10.5 to the pH value of solution value, stops the carbon branch, solid-liquid separation.
2. solution for continuous feeds CO
2Gas, stirring reaction under 40～85 ℃ of temperature carries out the carbon branch second time, reduces to 7～8, stopped reaction, solid-liquid separation once more to the pH value of solution value.
3. isolated solid sediment obtains the white carbon black product after washing, oven dry.
The first time carbon divide in the isolated solid sediment and add strong acid, soak or after heat boiled, impurity was removed in washing, oven dry obtains the white carbon black product.
The sodium silicate solution that the present invention uses can be the sodium silicate solution of technical grade, it also can be the higher non-pure sodium silicate solution of foreign matter content, so-called non-pure sodium silicate solution, be meant with aqueous alkali and leach the higher sodium silicate solution of foreign matter content that obtains behind the high silicon solid waste, these high silicon solid wastes comprise the waste behind production Tai-Ace S 150, the aluminum chloride, coal gangue, flyash, the high silicon waste residue that produces after kaolin, opal and black and the non-ferrous metal metallurgy etc.
No matter be commercially available technical grade water glass, or the higher sodium silicate solution of foreign matter content, all need its dilution or to be concentrated into water glass content be 8～15% scope.For the first time the carbon branch can make most impurity in the sodium silicate solution separate out and separate out a part of white carbon black (precipitate quality be about solution precipitate total amount 1～15%), after the solid-liquid separation, isolating solution through the second time carbon branch can prepare purity height, high-quality white carbon black that fineness is good.The solids that the first time, carbon analyzed is through strong acid (HCl, H
2SO
4, HNO
3) soak or after heat cooks off the removal of impurity, can produce out high-quality white carbon black equally.
Carbon branch of the present invention reaction can or be kept under the suitable positive pressure of reactor at normal pressure and feed CO in sodium silicate solution
2Gas carries out, the CO that the carbon timesharing is used
2Gas should guarantee CO
2Concentration 〉=30%, and do not contain can generate acid gas (as SO
2, Cl
2Deng), do not contain dust yet.
The present invention's remaining sodium carbonate solution after secondary carbon divides can adopt the spissated method of causticization to produce alkali lye, is used to handle high silicon solid waste and prepares sodium silicate solution, recycles, and realizes no discharging of waste liquid, the target of environmentally safe.
Preparing white carbon black from secondary carbon component method of the present invention can be eliminated in the strong acid and water glass produces a large amount of brine wastes, cause environmental pollution problems, the higher sodium silicate solution of foreign matter content that can make full use of high silicon solid waste preparation is again produced high-quality white carbon black, whole process of production does not have discharging of waste liquid, is a kind of eco-friendly preparation method.
Preparation of White Carbon Black method processing unit of the present invention is simple, easy to operate, and white carbon black product purity height, fine size, whiteness that production obtains are good.
Among the present invention, except as otherwise noted, all are meant mass percentage content with the component content that percentage ratio provides.
Embodiment
Embodiment 1
To contain 5.87g/L Fe
2O
3, 0.57g/L Al
2O
3, 9.79g/L TiO
221%Na
2SiO
3Solution dilution is 10% Na
2SiO
3Solution places carbon to divide still, is warming up to 75 ℃, feeds CO
2Gas imposes stirring, makes Na
2SiO
3The pH value of solution was reduced to 10.5 o'clock from＞14, stopped ventilation, and with the precipitate filtering separation in the solution, surplus liquid places carbon to divide still again, is warming up to 75 ℃, fed CO
2Gas continues the carbon branch, reduces to 8 o'clock to the pH value of solution, stops ventilation, refilters separation, and the solid isolate of acquisition obtains SiO after washing, oven dry
2Content 98.5%, mean particle size are the high-quality white carbon black of 10 μ m.
Add 20%HCl solution in the precipitate that the first time, carbon was told, after 80 ℃ of following heat were boiled 2 hours, washing, oven dry can obtain SiO
2Content 99.6%, the high-quality white carbon black of mean particle size 10 μ m.
Secondary carbon divides the back remaining Na
2CO
3Convert in the dilute solution with an amount of lime slurry, obtain the NaOH thin liquids, make the high alkali liquid of NaOH concentration＞50% again through evaporation concentration, capable of circulationly be used to leach high silicon waste residue with the preparation sodium silicate solution 80 ℃ of following causticizations.
Embodiment 2
General industry level water glass is diluted to 15% Na
2SiO
3Solution places carbon to divide still, is warming up to 60 ℃, feeds CO
2Gas also imposes stirring, treats that the pH value of solution was reduced at 9.5 o'clock, stops ventilation, filter to isolate precipitate, surplus liquid returns carbon again and divides and carry out the carbon branch second time in the still, reduces to 7.5 o'clock to the pH value of solution, stop ventilation, refilter separation, precipitate obtains SiO after washing, oven dry
2Content 99.5%, the high-quality white carbon black of mean particle size 10 μ m.
For the first time the precipitate told of carbon is with 40% H
2SO
4Solution boiled 2 hours in 100 ℃ of following heat, and insolubles is washed with water to neutrality, after the oven dry, can obtain SiO
2The high-quality white carbon black of content 99%.
Carbon divides surplus liquid after the causticization evaporation concentration, makes the NaOH high alkali liquid and reclaims.
Claims (6)
1, a kind of method of preparing white carbon black from secondary carbon component is to feed CO in 8～15% sodium silicate solution
2Gas reduces to 9～10.5 in 40～85 ℃ of stirring reactions to the pH value of solution value, solid-liquid separation, and solution for continuous feeds CO
2Gas reduces to 7～8 in 40～85 ℃ of stirring reactions to the pH value of solution value, solid-liquid separation, and solids wash, oven dry obtain white carbon black, and carbon divides isolated solid to boil with strong acid immersion or heat for the first time, and after impurity was removed in washing, oven dry obtained white carbon black.
2, the method for preparing white carbon black from secondary carbon component according to claim 1 is characterized in that described sodium silicate solution is the technical grade sodium silicate solution.
3, the method for preparing white carbon black from secondary carbon component according to claim 1 is characterized in that described sodium silicate solution is to leach the sodium silicate solution that obtains behind the high silicon solid waste with aqueous alkali.
4, the method for preparing white carbon black from secondary carbon component according to claim 3, it is characterized in that described high silicon solid waste is the waste behind production Tai-Ace S 150, the aluminum chloride, coal gangue, flyash, the high silicon waste residue that produces after kaolin, opal and black and the non-ferrous metal metallurgy.
5, the method for preparing white carbon black from secondary carbon component according to claim 1 is characterized in that CO
2Gas concentration 〉=30%.
6, the method for preparing white carbon black from secondary carbon component according to claim 1 is characterized in that secondary carbon divides remaining sodium carbonate solution to make sodium hydroxide solution after causticization concentrates.
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|---|---|---|---|
| CN2007100621971A CN101077777B (en) | 2007-06-21 | 2007-06-21 | Method for preparing white carbon black from secondary carbon component |
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|---|---|---|---|
| CN2007100621971A CN101077777B (en) | 2007-06-21 | 2007-06-21 | Method for preparing white carbon black from secondary carbon component |
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| CN101077777A true CN101077777A (en) | 2007-11-28 |
| CN101077777B CN101077777B (en) | 2010-09-08 |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993085A (en) * | 2010-11-29 | 2011-03-30 | 中煤平朔煤业有限责任公司 | Method for producing white carbon black for toothpaste from fly ash |
| CN101306819B (en) * | 2008-06-20 | 2011-05-25 | 北京世纪地和科技有限公司 | Process for abstracting white carbon black from fly ash or slag |
| CN102259874A (en) * | 2011-06-30 | 2011-11-30 | 中煤平朔煤业有限责任公司 | Method for preparing white carbon black by continuous carbon precipitation |
| CN102328931A (en) * | 2011-06-30 | 2012-01-25 | 中煤平朔煤业有限责任公司 | Method for continuously producing white carbon black by utilizing low-concentration sodium silicate solution |
| CN103086385A (en) * | 2013-02-27 | 2013-05-08 | 中煤平朔集团有限公司 | Method for preparing rubber-grade white carbon black by using fly ash |
| CN104176739A (en) * | 2014-08-18 | 2014-12-03 | 连云港市东海县宏伟石英制品有限公司 | Method for preparing high-purity silicon dioxide powder by using sodium silicate |
| CN104556056A (en) * | 2014-12-25 | 2015-04-29 | 东莞市高明企业服务有限公司 | Method for preparing white carbon black from high-silicon-content coal ash |
| CN106517222A (en) * | 2016-11-14 | 2017-03-22 | 清华大学 | Method for synthesizing ordered mesopore nano-silica through pulverous coal |
| CN108276808A (en) * | 2017-01-05 | 2018-07-13 | 神华集团有限责任公司 | A kind of reinforced filling and preparation method thereof |
| CN108516558A (en) * | 2018-04-27 | 2018-09-11 | 李乃罡 | A kind of production method of superfine white carbon black |
| CN110272053A (en) * | 2018-03-16 | 2019-09-24 | 国家能源投资集团有限责任公司 | The preparation method of high-purity waterglass, low iron white carbon black and ultra-clear glasses raw material |
| CN113353943A (en) * | 2021-07-14 | 2021-09-07 | 青岛君强新材料有限公司 | Method for simultaneously preparing white carbon black and high-modulus water glass by using metal silicon powder and white carbon black |
| CN113603100A (en) * | 2021-08-31 | 2021-11-05 | 江苏绿之蓝新材料科技有限公司 | Method for controlling carbon emission in metallurgical industry |
| CN113943006A (en) * | 2021-12-07 | 2022-01-18 | 安徽进化硅纳米材料科技有限公司 | High-reinforcement white carbon black and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1174168A (en) * | 1996-08-15 | 1998-02-25 | 鞠馥阳 | Production process of active silica white from gangue |
| CN1194044C (en) * | 2002-12-16 | 2005-03-23 | 同济大学 | Preparation of silica white from silicon sol |
-
2007
- 2007-06-21 CN CN2007100621971A patent/CN101077777B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306819B (en) * | 2008-06-20 | 2011-05-25 | 北京世纪地和科技有限公司 | Process for abstracting white carbon black from fly ash or slag |
| CN101993085A (en) * | 2010-11-29 | 2011-03-30 | 中煤平朔煤业有限责任公司 | Method for producing white carbon black for toothpaste from fly ash |
| CN101993085B (en) * | 2010-11-29 | 2012-10-03 | 中煤平朔煤业有限责任公司 | Method for producing white carbon black for toothpaste from fly ash |
| CN102259874A (en) * | 2011-06-30 | 2011-11-30 | 中煤平朔煤业有限责任公司 | Method for preparing white carbon black by continuous carbon precipitation |
| CN102328931A (en) * | 2011-06-30 | 2012-01-25 | 中煤平朔煤业有限责任公司 | Method for continuously producing white carbon black by utilizing low-concentration sodium silicate solution |
| CN102328931B (en) * | 2011-06-30 | 2012-11-21 | 中煤平朔煤业有限责任公司 | Method for continuously producing white carbon black by utilizing low-concentration sodium silicate solution |
| CN103086385A (en) * | 2013-02-27 | 2013-05-08 | 中煤平朔集团有限公司 | Method for preparing rubber-grade white carbon black by using fly ash |
| CN104176739A (en) * | 2014-08-18 | 2014-12-03 | 连云港市东海县宏伟石英制品有限公司 | Method for preparing high-purity silicon dioxide powder by using sodium silicate |
| CN104556056A (en) * | 2014-12-25 | 2015-04-29 | 东莞市高明企业服务有限公司 | Method for preparing white carbon black from high-silicon-content coal ash |
| CN106517222A (en) * | 2016-11-14 | 2017-03-22 | 清华大学 | Method for synthesizing ordered mesopore nano-silica through pulverous coal |
| CN108276808A (en) * | 2017-01-05 | 2018-07-13 | 神华集团有限责任公司 | A kind of reinforced filling and preparation method thereof |
| CN108276808B (en) * | 2017-01-05 | 2021-09-14 | 国家能源投资集团有限责任公司 | Reinforcing filler and preparation method thereof |
| CN110272053A (en) * | 2018-03-16 | 2019-09-24 | 国家能源投资集团有限责任公司 | The preparation method of high-purity waterglass, low iron white carbon black and ultra-clear glasses raw material |
| CN110272053B (en) * | 2018-03-16 | 2021-05-11 | 国家能源投资集团有限责任公司 | Preparation method of high-purity water glass, low-iron white carbon black and ultra-white glass raw materials |
| CN108516558A (en) * | 2018-04-27 | 2018-09-11 | 李乃罡 | A kind of production method of superfine white carbon black |
| CN113353943A (en) * | 2021-07-14 | 2021-09-07 | 青岛君强新材料有限公司 | Method for simultaneously preparing white carbon black and high-modulus water glass by using metal silicon powder and white carbon black |
| CN113603100A (en) * | 2021-08-31 | 2021-11-05 | 江苏绿之蓝新材料科技有限公司 | Method for controlling carbon emission in metallurgical industry |
| CN113943006A (en) * | 2021-12-07 | 2022-01-18 | 安徽进化硅纳米材料科技有限公司 | High-reinforcement white carbon black and preparation method and application thereof |
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