CN102120582B - Reaction process for precipitating white carbon black through stirring and milling method - Google Patents
Reaction process for precipitating white carbon black through stirring and milling method Download PDFInfo
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- CN102120582B CN102120582B CN201110026103.1A CN201110026103A CN102120582B CN 102120582 B CN102120582 B CN 102120582B CN 201110026103 A CN201110026103 A CN 201110026103A CN 102120582 B CN102120582 B CN 102120582B
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Abstract
The invention discloses a reaction process for precipitating white carbon black through a stirring and milling method. Water glass is reacted with acid; and the reaction process comprises a reaction procedure and a curing procedure, wherein the reaction procedure is carried out in an acid and water neutralization stirred tank, and ceramic ball milling bodies are added into the acid and water neutralization stirred tank. In the reaction process, the stirring efficiency is greatly improved, and the generation of 'white spots' is radically stopped; moreover, the grain size is obviously reduced, so that the water glass with higher concentration can be reacted with the acid.
Description
Technical field
The present invention relates to a kind of reaction process that stirs mill method precipitated silica.
Background technology
White carbon black is a kind of important industrial chemicals, and main production has silicon tetrachloride flame hydrolysis and the large class of water glass acid precipitation method two, on water glass method basis, also derives sol method and carborization.The former quality better but cost is very high, the latter's cheapness but inferior quality often exists " white point (reunion silicon-dioxide) " to cause use properties significantly to decline in product.Domestic large white carbon black product is precipitated silica, if low-cost, solves white point problem, can increase substantially precipitated silica price.
The acid material that precipitated silica is mainly used has sulfuric acid, the strong acid such as hydrochloric acid, and bicarbonate of ammonia etc., bicarbonate of ammonia cost is low, and because acidity is low, and heat release generates that the amount of gel hydrated SiO 2 is less less, and corresponding " white point " is few, but nitrogenous effluent environmental protection pressure is large.Factory is mainly still used cheap high-concentration sulfuric acid for acid material at present.
In acid and water glass, with rear generation silicic acid, silicic acid continues polycondensation and becomes cotton-shaped hydrated SiO 2 and gel hydrated SiO 2, also can generate hard aggregation hydrated SiO 2 once in a while.When water glass density is high conventionally, product specific surface area is too small, and density low specific surface area is large but gel is many; When sulfuric acid concentration is too high, be difficult to stir, cause product structure poor, size-grade distribution is large, hard aggregation thing is many (also can form the thing of similar white point) also, crossing low production specific surface area reduces, the equal Gao Shiyin hard aggregation of both concentration particle cannot be produced qualified product too much, and high-speed stirring obviously reduces gel and generates quantity, reduces grain graininess.
Cotton-shaped hydrated SiO 2 after slaking ageing, washing squeezing is light-burned industrial white carbon black, gel hydrated SiO 2 and some hard aggregation particles generate manufacturer and do not wish " white point " seen.The generation of " white point " main and water glass and sulfuric acid concentration, mix and blend speed is relevant, because equipment stirring velocity can not infinitely improve, so at present domestic solution " white point " problem that is still difficult for, existing improvement technology---drop into crystal seed, filter the technology such as glue and just improve production quality, or screen out oarse-grained hydrated SiO 2, can not avoid the generation of gel hydrated SiO 2, and obviously increase production cost.
Summary of the invention
The object of the present invention is to provide a kind of reaction process that stirs mill method precipitated silica.Stirring efficiency of the present invention increases substantially, and stops the generation of " white point " completely, and particle diameter obviously reduces, so that water glass and the acid of available higher concentration are reacted.
In order to reach above-mentioned purpose, solution of the present invention is:
Stir a reaction process for mill method precipitated silica, adopt water glass and acid to react, comprise reaction process and curing step, described reaction process is in acid, water and carry out in stirring tank, and in acid, water and add Ceramic Balls mill in stirring tank.In reaction of the present invention, add Ceramic Balls mill that acid-base neutralisation is carried out in stirring mill, solution stirring efficiency increases substantially, and has avoided because reacting a large amount of generations of the too high gel hydrated SiO 2 causing of quick heat release and local acid concentration or hard aggregation particle; Simultaneously, it is loose by mill that the existence of ball milling generates gel hydrated SiO 2 or large-scale hard aggregation particle one, cannot form large-scale closely knit gel or stone, therefore use this technique can stop the generation of " white point " completely, the silicic acid simultaneously generating grinds because of brute force the particle diameter that is difficult to reunite obviously to be reduced, so that water glass and the acid of available higher concentration are reacted.
The outside surface of described Ceramic Balls mill is coated with high density polyethylene(HDPE), tetrafluoroethylene, a kind of plastic wraps layer in urethane.
Described Ceramic Balls mill density is preferably in 1.5-1.8kg/dm
3, outside surface is preferably coated with urethane; Outside surface is coated with above-mentioned plastic wraps layer can avoid polluting feed liquid; The sub-density of ball milling is preferably selected with feed liquid close, while kicking the beam, (as direct use baton round) ball milling floating, finds in pilot scale that Polycondensation Reactor and Esterification Reactor still exists a small amount of gel hydrated SiO 2 (lower concentration reaction) or hard aggregation hydrated SiO 2 (high density reaction); When overweight (as used alumina balls mill) stir more difficultly, and pilot scale finds that product structure is affected, in addition compared with the conventional precipitation method reaction times, the reaction times of this technique can be according to stirring that mill scale is amplified degree and correspondingly significantly shorten.
It is 1.05g/mL-1.3g/mL that water glass described in this technique adopts the rear density of dilution, the water glass of modulus 2.8-3.4; Described acid adopts the sulfuric acid that concentration is 30%-92%, has reacted pH general control between 7-10.
Described curing step also can and be carried out in stirring tank in acid, water; Not only further improve the quality of products, also can simplify technique.Certainly also can emit and expect slaking separately, but because material is denseer compared with conventional precipitation method, product performance can change to some extent during slaking separately, and the curing time is longer.PH after slaking during discharging is 3-6.
Beneficial effect of the present invention is: technique of the present invention can be continued to use existing white carbon black production technique, substantially without scrap build.Because of the grinding of ball milling, eliminated the reunion of gel hydrated SiO 2, make Granularity Distribution better, without " white point ".The silicic acid simultaneously generating grinds because of brute force the particle diameter that is difficult to reunite obviously to be reduced, so that water glass and the acid of available higher concentration are reacted.Secondly because stirring efficiency increases substantially, accelerated feed rate, thereby significantly offset ball milling, dropped into the stirring tank volume reducing problem causing after stirring tank, high density is reacted and is also made production efficiency substantially not decline.Because quality product rises, cause economic benefit significantly to improve on the contrary.Be to have simplified processing unit and step again, solved current reactor and often stopped up and the problem of the flushing of stopping work.
Embodiment
Embodiment 1
A kind of reaction process that stirs mill method precipitated silica of the present embodiment, adopt water glass and sulfuric acid to react, comprise reaction process and curing step, described reaction process is in the acid of 5 liters, water and carry out in stirring tank, in acid, in water and first add Ceramic Balls mill in stirring tank, the density of Ceramic Balls mill is 1.8kg/m
3, outside surface is coated with urethane plastic integument.Also can apply high density polyethylene(HDPE), a kind of plastic wraps layer in tetrafluoroethylene.Then do not add end liquid and drop into 1 liter to be diluted to density be 1.1g/mL, the water glass of modulus 3.2, starts stirring tank (increasing 10 times of powers of motor than original stirring tank motor), and mixing speed is 60 revs/min, in 5 minutes, evenly splashes into 30% sulfuric acid; Guarantee reaction solution terminal pH8-9.Then keeping carrying out curing step under stirring, the curing time is 5-10 minute, drips to regulate expect that pH is 4-5 in maturing process with 30% sulfuric acid.
Follow the tracks of reaction and find that feed temperature changes (frictional heating) because stirring velocity changes, the present embodiment belongs to pilot scale, do not need heating, 60 revs/min of 70-80 ℃ that can make curing temperature remain on normal production of rotating speed, reaction discharging is light oyster white glue body, scrapes board test and exists without the above size gel of 5 μ m silicon-dioxide.
Revision test can obtain; Keeping water glass density is 1.1g/mL, still can obtain the feed liquid of gel-free or large-scale particle when sulfuric acid concentration is increased to 92%.Keep sulfuric acid concentration 30%, water glass density is brought up to 1.3g/mL and also can be produced, the viscosity rise of now expecting, structural slightly poor, discharging is compared with stiff, but after product slaking washing calcining, performance is still slightly better than commercially available white carbon black and nothing " white point ", and therefore optimal reaction conditions is high sulfuric acid concentration, low concentration of sodium silicate.Next is to increase to stir the curing time, and in feed liquid, grain graininess further reduces, and feed liquid color bleaches, and product specific surface area is larger, still without " white point ".
The emphasis of the present embodiment is in acid---in water glass He in stirring tank, drop into ball milling, solution stirring efficiency is increased substantially, avoided because of lower concentration reaction and local acid concentration too high, the gel hydrated SiO 2 that heat releases cause in a large number obtains a large amount of generations of hard aggregation particle; Meanwhile, it is loose by mill that the existence of ball milling generates gel hydrated SiO 2 or large-scale hard aggregation particle one, cannot form large-scale closely knit gel or stone, uses this technique can stop the generation of " white point " completely.The silicic acid generating in addition grinds particle diameter because of brute force obviously to be reduced, so that water glass and the acid of available higher concentration are reacted.
Embodiment 2
A kind of reaction process that stirs mill method precipitated silica of the present embodiment, comprises reaction process and curing step, and its basic step is identical with embodiment 1, difference: the density of Ceramic Balls mill is 1.6kg/m
3, it is 1.3g/mL that water glass adopts density, the water glass of modulus 2.8; It is 30% sulfuric acid that described acid adopts concentration, reaction end pH7-8 in reaction process.And curing step not in acid, in water and carry out in stirring tank, after reaction, be blowing, in addition in other reactor, slaking at 80 ℃, scrape board test and find that product granularity has little ascendant trend, but finally make White Carbon black except specific surface area is less, also do not find " white point "; Find comparing with still curing step of conventional curing step and embodiment 1, curing temperature does not have impact clearly to the finished product specific surface in acid, water and in stirring tank, that is to say that the method for embodiment 1 has obviously been simplified production technique simultaneously.
Claims (3)
1. a reaction process that stirs mill method precipitated silica, adopt water glass and acid to react, comprise reaction process and curing step, it is characterized in that: described reaction process is in acid, in water and carry out in stirring tank, and in acid, water and add Ceramic Balls mill in stirring tank; The outside surface of described Ceramic Balls mill is coated with high density polyethylene(HDPE), tetrafluoroethylene, and a kind of plastic wraps layer in urethane, the sub-density of ball milling is 1.5-1.8kg/dm
3.
2. the reaction process of stirring mill method precipitated silica as claimed in claim 1, is characterized in that: it is 1.05g/mL-1.3g/mL that described water glass adopts density, the water glass of modulus 2.8-3.4; Described acid adopts the sulfuric acid that concentration is 30%-92%, has reacted pH and has been controlled between 7-10.
3. the reaction process of stirring as claimed in claim 1 mill method precipitated silica, is characterized in that: described curing step is in acid, water and carry out in stirring tank, and the pH after slaking during discharging is 3-6.
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| CN201110026103.1A CN102120582B (en) | 2011-01-25 | 2011-01-25 | Reaction process for precipitating white carbon black through stirring and milling method |
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| CN201110026103.1A CN102120582B (en) | 2011-01-25 | 2011-01-25 | Reaction process for precipitating white carbon black through stirring and milling method |
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| CN102120582B true CN102120582B (en) | 2014-09-10 |
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| CN110643206A (en) * | 2019-10-18 | 2020-01-03 | 江西黑猫炭黑股份有限公司 | Production method of high-dispersion white carbon black |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165113A (en) * | 1996-05-14 | 1997-11-19 | 汪承源 | Preparation method of secondary crystallization superfine white carbon black |
| CN101679050A (en) * | 2007-05-03 | 2010-03-24 | 科学与工业研究委员会 | A process for the preparation of finely divided precipitated silica |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20070224133A1 (en) * | 2006-03-23 | 2007-09-27 | Mcgill Patrick D | High-cleaning silica materials made via product morphology control under high shear conditions |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165113A (en) * | 1996-05-14 | 1997-11-19 | 汪承源 | Preparation method of secondary crystallization superfine white carbon black |
| CN101679050A (en) * | 2007-05-03 | 2010-03-24 | 科学与工业研究委员会 | A process for the preparation of finely divided precipitated silica |
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