CN1128239A - Preparation process of active silica white by using water glass - Google Patents
Preparation process of active silica white by using water glass Download PDFInfo
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- CN1128239A CN1128239A CN 95111408 CN95111408A CN1128239A CN 1128239 A CN1128239 A CN 1128239A CN 95111408 CN95111408 CN 95111408 CN 95111408 A CN95111408 A CN 95111408A CN 1128239 A CN1128239 A CN 1128239A
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Abstract
The two-step process for preparing active silica white includes material selection, solution compounding, prepn of silicon sol, two -step reaction, filteration, washing, crushing and packing. All the water glass module material concentration and compounding ratio, pH value in reaction and reaction temp are optimized to obtain optimal parameters. The said method is suitable for preparing active silica white not only from water glass but also with kaolin, quartz sand or gangue as material.
Description
The present invention utilizes water glass and sulfuric acid to carry out the technology of two step prepared in reaction active carbon whites.Mostly be to utilize HCl and water glass prepared in reaction to go out active carbon white in the prior art, see " development of active carbon white " that " Guangxi chemical industry " nineteen ninety (2) He Qingfang writes.Also useful water glass and H
2SO
4Carry out the technology of two step prepared in reaction active carbon whites, for example Cai Yipeng, the article that Cai Jian writes " character of active carbon white, preparation and application " are published in " Sichuan chemical industry " 1991 (1).The technology of this article introduction is: the first step prepares silicon sol: add diluted acid in proper concn water glass, treat that the pH value of solution reaches at 8.5 o'clock, stopped reaction leaves standstill, and transparent jelly occurs infusing clearly.Second step reaction: at Na
2SO
4The silicon sol (dissolving the silicon sol after viscosity reduces through heating) that adds above preparation in the water glass solution under flocculation agent exists stirs, and adds HCl or H
2SO
4The PH of regulator solution is that 6-7 is terminal point.Insulation slaking 1 hour, filtration, washing, drying, pulverizing promptly get product.
When the weak point of this method is the preparation silicon sol acid is added in the water glass, the silicon gel that white when pH value is 8.5, occurs, be difficult for dissolving after such silicon gel heating, cause the reaction of second step restive, the white carbon black granularity of making is inhomogeneous, the easily hardening of dry back does not reach ideal activity.
Water glass is generally at high temperature reacted by quartz sand and soda ash and makes, also can be from kaolin, and coal gangue and soda ash reaction make.China abounds with quartz sand and kaolin, and kaolinic reserves account for global first place, and coal gangue is the waste residue of discharging in the colliery, a large amount of land occupations.According to statistics by 1991 the end of the year China's coal gangue output reached more than 2,200,000,000 tons, take up an area of 170,000 mu, existing annual spoil amount of discharging reaches more than 1.3 hundred million tons, takes up an area of about 10,000 mu, and contaminate environment.The objective of the invention is to:, proposed to go out the method for the high-quality active carbon white that granularity is little, specific surface area big, activity is good with water glass and two step of sulfuric acid prepared in reaction in order to make full use of these resources and the deficiency that overcomes above-mentioned existing preparation white carbon black technology.
Technical scheme of the present invention: promptly the technology with water glass and two step of sulfuric acid prepared in reaction active carbon white is to have passed through a large amount of experiments processing condition and parameter have been carried out the result who optimizes, as:
(1). the modulus of water glass is 3.1～3.4, and proportion is 40 ° of Be '～39 ° Be '.
(2). select H during the preparation silicon sol for use
2SO
4And do not select HCl for use, and be that water glass is added in the sulphuric acid soln during preparation, the pH value of regulator solution is 1.8～2.4, and the strict generation that prevents the silicon gel.
(3). add flocculation agent NaCl (or Na in the precipitin reaction
2SO
4) and tensio-active agent ethanol (or glycerol), and optimization NaCl and alcoholic acid optimal dose.The adding of NaCl makes SiO
2Simple particle accumulation becomes secondary particle to form precipitation loose, finely divided, white flocculent structure to separate out, and quality product is improved.Add ethanol and can improve product activity and improve dispersedly, so not only can increase the specific surface area of product but also can improve the color and luster and the luminance brightness of product.
(4). the pH value of reaction end is controlled to be 6～5, and keeping the temperature of solution in the reaction process is 70～80 ℃.
Specific embodiment of the present invention in turn includes the following steps:
1, the preparation of solution
(1) preparation of .10 ° of Be ' water glass and 5 ° of Be ' water glass solutions: the water glass of getting commercially available modulus and be 3.1～3.4 proportions and be 39 ° of Be '～40 ° Be ' is an amount of, thin up to 10 ° Be ', 10 ° of Be ' water glass solutions.Get the 10 ° of an amount of thin up to 5 of Be ' water glass ° Be ', get 5 ° of Be ' water glass solutions.
(2) .5.5～6.5mol/L H
2SO
4The preparation of solution: get 98% industrial H
2SO
4, add water by metering and be mixed with 5.5～6.5mol/L H
2SO
4Solution.
2, the preparation of single step reaction silicon sol: get 5.5～6.5mol/L H
2SO
40.25～130 liter of solution (130 liters is the consumption on producing, and it is the amplification number of 0.25 liter of lab scale consumption) adds 10 ° of Be ' water glass gradually, the limit edged stirs, and the pH value of regulator solution is 1.8～2.4, restir 20～30 minutes, prevent to generate the silicon gel, ageing 1～2 hour is standby.
3, the reaction of two steps: (1200 liters is the consumption on producing to get 2.5～1200 liters of 5 ° of Be ' water glass, it is the amplification number of 0.25 liter of lab scale consumption) in reactor, be warmed up to 70～80 ℃, adding weight is that the NaCl and the weight of 5 ° of Be ' water glass amounts 2～3% is 95% ethanol of 5 ° of Be ' water glass amounts 2～3%, stirred 10～20 minutes, keeping the temperature of reaction is 70～80 ℃, add the above-mentioned silicon sol solution for preparing, when the pH value of solution drops to 8, stirred 10～15 minutes, continuing to add silicon sol is 6～5 up to the pH value of solution, or under the situation that silicon sol adds, adds 6～3mol/L H again
2SO
4The pH value of regulator solution is 6～5, restir 20～30 minutes, and insulation ageing 20～30 minutes, it is precipitated as hydrated SiO 2.
4, filter, wash: with the sedimentation and filtration of above gained, precipitation is used distilled water wash 1～2 time again with tap water rinsing 2～3 times.
5, drying: be deposited in 120～130 ℃ of down oven dry 7～8 hours after will cleaning, controlling its moisture content (less can be in drying in oven as if product volume 6～8%, on producing, utilize commercially available high-efficient air heater, promptly utilize the steam of boiler to be converted into hot blast efficiently and regulate the baking chambers temp and dry).
6, pulverize, pack: it is 250～325 orders that the white carbon black after will drying is crushed to granularity.
If raw material is kaolin or quartz sand or coal gangue, earlier these feedstock production are become water glass, utilize " technology of preparation active carbon white from water glass " to be prepared as white carbon black again.
The present invention water glass and sulfuric acid two step method prepared in reaction active carbon white, water glass is selected middle modulus for use, and precipitation agent is selected H for use
2SO
4And do not use HCl, because of having volatility, HCl easily causes pollution to environment and H
2SO
4Acidity is bigger than HCl, the vitriolic consumption reduces during the preparation white carbon black, thereby reduced cost, the pH value that adds flocculation agent NaCl and tensio-active agent ethanol and two reactions of strict control in the reaction, the temperature of general producer baking white carbon black is controlled at 150 ℃ on drying technology, drying time needs 15～20 hours, the present invention adopts high-efficient air heater, promptly utilizes the steam of boiler to be converted into hot blast efficiently, and the temperature of regulating the baking chamber is 120 ℃～130 ℃, drying time only needs 7～8 hours, the amount of the white carbon black that this drying technology is handled is big, simple to operate, not polluted product and environment, energy-conservation, reduced cost.
The particle diameter of the product of gained of the present invention is very little, 12～20nm, and specific surface area is big, and the chemical physics performance is fine, and the reinforcing property in rubber is fine.This technology advanced person is reasonable, pollution-free, raw material is easy to get, cost is low, good product quality, and it is very stable, reaction is easy to control, and products obtained therefrom is through the check of carbon black mass inspection center of country of the Ministry of Chemical Industry, and all index reaches the index of State Standard of the People's Republic of China G1B-10517-89 and chemical industry standard HG/T2197-90 defined, and by the application test of Chongqing City one rubber plant, evidence can be promoted the use of.Its assay is as follows:
Survey report
| Sequence number | Interventions Requested | Standard value | Measured value |
| ????1 ????2 ????3 ????4 ????5 ????6 ????7 ????8 ????9 ????10 ????11 ????12 ????13 ????14 ????15 ????16 ????17 | Dioxide-containing silica % color weight loss on heating % burning decrement % DBP absorption value ml/gg nitrogen surface area m 2Total manganese content mg/Kg 45 μ m residue on sieve % pH value cure time minute hardness (Shao Er A) the breaking strength MPa elongation at break % of/g sum total total iron-holder mg/Kg of copper amount mgg/Kg 500% stretching strength MPa setafter break % | 〉=90 be better than equaling standard specimen 4.8-8.0≤7.0 2.00-3.50≤30≤1000≤50≤0.5 5.0-8.0--〉=17.0 〉=675 〉=6.3- | 90＞mark 7.7 6.4 2.22 1 49 1.2 938 8.4 0.2 6.2 7 10 73 74 25.9 25.8 752 740 9.6 9.7 16 14 |
The particle diameter of products obtained therefrom active carbon white verifies as 12～20nm with electron microscope.
Fig. 1 is a process flow sheet of the present invention
In Fig. 1: 1 one water glass, 2-water, 3-sulfuric acid, 4-acidic silicasol solution 5-flocculation agent and tensio-active agent 6-reaction, precipitation, ageing, acidifying 7-filtration, washing 8-water 9-drying, pulverizing 10-active carbon white
Embodiment 1:
The preparation of silicon sol: get 5.5～6.5mol/L H
2SO
40.25 rise, add 10 ° of Be ' water glass solutions, the limit edged stirs, and the regulator solution pH value is 1.8～2.4, stirs 20～30 minutes, and ageing 1～2 hour is standby.
Reaction: get 3 liters of 5 ° of Be ' water glass in a container, add NaCl solution (90gNaCl is dissolved in 0.4 premium on currency) and 0.11 liter of 95% ethanol, keeping solution temperature is 70～80 ℃, stirred 10 minutes, and the silicon sol of above preparation was slowly added, when solution PH is 8, stirred 10～15 minutes, continuing to add silicon sol is 6～5 until solution PH, perhaps under the situation that silicon sol adds, adds 6～3mol/L H
2SO
4Regulator solution PH is 6～5, stirs insulation ageing 30 minutes 30 minutes.
Filter, wash: with the filter pulp suction filtration, distilled water wash 1～2 time is used in filter cake water rinse 2～3 times at last again.
Oven dry, pulverizing: the precipitation that will clean places in the baking oven, dries 7～8 hours down in 120～130 ℃, and controlling its water content is 6～8%, and the precipitated powder after the oven dry is broken to granularity 250～325 orders, promptly gets the active carbon white product.
Embodiment 2:
In the colloidal sol still, put into 5.5～6.5mol/L H
2SO
4130 liters, add 10 ° of Be ' water glass, be 1.8～2.4 with the pH value of special pH test paper regulator solution, stop to add water glass, the consumption of record water glass.
In the enamel reaction still of 4m3, add 1200 liters of 5 ° of Be ' water glass, open steam valve, add NaCl solution (12 kilograms of NaCl are dissolved in 240 premium on currency) and 25 liter of 95% ethanol, stir, open colloidal sol still bottom valve, silicon sol is flowed in the reactor, and the temperature of solution is 70～80 ℃ in the control reactor, when the pH value of solution drops to 8, stirred 10～15 minutes, continue adding silicon sol to the pH value of solution is 6～5, or silicon sol adds, uses 6～3mol/L H again
2SO
4The pH value of regulator solution is 6～5, stirred 0.5 hour, insulation ageing 0.5 hour, open the bottom valve of reactor, the storage pond is put in filter pulp, when cooling off one section, filter pulp squeezed in the plate-and-frame filter press with pump filter, use the tap water washing leaching cake, with the water coolant washing, press dry again, filter cake is emitted, be divided into thin piece, contain and place the baking chamber, dried 7-8 hour down at 120 ℃～130 ℃ with the aluminium dish, the content of control moisture content is 6-8%, it is 250～325 orders that the white carbon black of drying is crushed to granularity with Universalpulverizer, is packaged into bag with the two layers of plastic bag then, promptly gets the active carbon white product.
Claims (5)
1, a kind of active carbon white technology for preparing from water glass comprises and carries out the selection of raw material and the preparation of its solution successively, the first step prepared in reaction silicon sol, and second goes on foot reaction, and filtration, washing, drying, pulverizing, packing is characterized in that:
(1). the selection modulus is 3.1-3.4, and its solution proportion is the commercial water glass of 39 ° of Be '～40 ° Be ', and thin up to proportion is 10 ° of Be ' and 5 ° of Be ' water glass solutions; With concentration 98% commercially available H
2SO
4, add water and be mixed with 5.5-6.5mol/L H
2SO
4Solution;
(2). the preparation silicon sol:
Get 5.5～6.5mol/L H
2SO
40.25～130 liter of solution places container, adds 10 ° of Be ' water glass solutions gradually therein, and the limit edged stirs, and is 1.8-2.4 until the PH of this solution, restir 20～30 minutes, and ageing is 1～2 hour then;
(3). the reaction of second step is:
1). with 5 ° of Be ' moduluses is 3.1～3.4, and volume is that 2.5～1200 liters water glass places reactor, is warmed up to 70～80 ℃, and adding weight is that NaCl and the weight of 5 ° of Be ' water glass amount 2-3% is 95% ethanol of 5 ° of Be ' water glass amount 2-3%;
2). stirred 10～20 minutes, and the maintenance reaction humidity is 70～80 ℃;
3). add silicon sol solution, the limit edged stirs, and when the PH of solution drops to 8, stirs 10～15 minutes, and continuing to add silicon sol is 6～5 up to the PH of solution, perhaps under the situation that silicon sol adds, uses 3～6mol/L H again
2SO
4The PH of regulator solution is 6～5, restir 20～30 minutes, and insulation ageing 20～30 minutes, it is precipitated as hydrated SiO 2;
4). with the sedimentation and filtration of above gained, precipitation is used distilled water wash 1～2 time again with tap water rinsing 2～3 times;
5). be deposited in 120～130 ℃ of down oven dry 7～8 hours after will cleaning, the content of controlling its moisture content is 6～8%, and the precipitated powder after will drying is broken to 250～325 orders.
2, the white carbon black technique that from water glass, prepares according to claim 1, H when it is characterized in that preparing silicon sol in the first step reaction
2SO
4Optimum concn is 6mol/L.
3, a kind of technology for preparing active carbon white from water glass is characterized in that it is the feedstock production active carbon white that this technology is used for kaolin.
4, a kind of technology for preparing active carbon white from water glass is characterized in that it is the feedstock production active carbon white that this technology is used for quartz sand.
5, a kind of technology for preparing active carbon white from water glass is characterized in that it is the feedstock production active carbon white that this technology is used for the coal gangue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95111408 CN1128239A (en) | 1995-06-14 | 1995-06-14 | Preparation process of active silica white by using water glass |
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|---|---|---|---|
| CN 95111408 CN1128239A (en) | 1995-06-14 | 1995-06-14 | Preparation process of active silica white by using water glass |
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|---|---|
| CN1128239A true CN1128239A (en) | 1996-08-07 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006131065A1 (en) * | 2005-06-10 | 2006-12-14 | Degussa Wellink Silica (Nanping) Co. Ltd. | A process for producing silica, sodium sulfite and sodium hydrogen sulfite with sodium sulfate |
| CN1308234C (en) * | 2003-11-25 | 2007-04-04 | 广州大学 | Method and apparatus for continuously preparing white carbon black |
| CN101786633A (en) * | 2010-02-26 | 2010-07-28 | 无锡恒诚硅业有限公司 | Production technology of white microbead-shaped white carbon black |
| CN101367960B (en) * | 2008-09-12 | 2010-12-29 | 江苏工业学院 | Preparation method for composite material of nano-concave-convex stick stone/silicon dioxide |
| CN101094808B (en) * | 2004-12-30 | 2011-07-27 | 科学与工业研究委员会 | Process for preparing amorphous silica from kimberlite tailing |
| CN102249246A (en) * | 2011-05-31 | 2011-11-23 | 中昊晨光化工研究院 | Method for preparing white carbon black by precipitation method |
| CN102701222A (en) * | 2012-05-22 | 2012-10-03 | 韩钊武 | Method for producing white carbon black with coal gangue |
| WO2020168662A1 (en) * | 2019-02-22 | 2020-08-27 | 广州市飞雪材料科技有限公司 | Low-density colored silica particles having porous structure, and preparation thereof |
| CN111777800A (en) * | 2020-07-03 | 2020-10-16 | 确成硅化学股份有限公司 | Preparation method of white carbon black for green tire |
-
1995
- 1995-06-14 CN CN 95111408 patent/CN1128239A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308234C (en) * | 2003-11-25 | 2007-04-04 | 广州大学 | Method and apparatus for continuously preparing white carbon black |
| CN101094808B (en) * | 2004-12-30 | 2011-07-27 | 科学与工业研究委员会 | Process for preparing amorphous silica from kimberlite tailing |
| WO2006131065A1 (en) * | 2005-06-10 | 2006-12-14 | Degussa Wellink Silica (Nanping) Co. Ltd. | A process for producing silica, sodium sulfite and sodium hydrogen sulfite with sodium sulfate |
| CN101367960B (en) * | 2008-09-12 | 2010-12-29 | 江苏工业学院 | Preparation method for composite material of nano-concave-convex stick stone/silicon dioxide |
| CN101786633A (en) * | 2010-02-26 | 2010-07-28 | 无锡恒诚硅业有限公司 | Production technology of white microbead-shaped white carbon black |
| CN101786633B (en) * | 2010-02-26 | 2012-11-07 | 无锡恒诚硅业有限公司 | Production technology of white microbead-shaped white carbon black |
| CN102249246A (en) * | 2011-05-31 | 2011-11-23 | 中昊晨光化工研究院 | Method for preparing white carbon black by precipitation method |
| CN102249246B (en) * | 2011-05-31 | 2013-04-24 | 中昊晨光化工研究院 | Method for preparing white carbon black by precipitation method |
| CN102701222A (en) * | 2012-05-22 | 2012-10-03 | 韩钊武 | Method for producing white carbon black with coal gangue |
| WO2020168662A1 (en) * | 2019-02-22 | 2020-08-27 | 广州市飞雪材料科技有限公司 | Low-density colored silica particles having porous structure, and preparation thereof |
| CN111777800A (en) * | 2020-07-03 | 2020-10-16 | 确成硅化学股份有限公司 | Preparation method of white carbon black for green tire |
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