CN103880021A - Method for preparing white carbon black in reverse micro-emulsion system - Google Patents
Method for preparing white carbon black in reverse micro-emulsion system Download PDFInfo
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- CN103880021A CN103880021A CN201410132606.0A CN201410132606A CN103880021A CN 103880021 A CN103880021 A CN 103880021A CN 201410132606 A CN201410132606 A CN 201410132606A CN 103880021 A CN103880021 A CN 103880021A
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Abstract
The invention discloses a method for preparing white carbon black in a reverse micro-emulsion system and particularly for preparing high-dispersity white carbon black for rubber. The method is characterized by comprising the following steps: pre-preparing the reverse micro-emulsion system which takes an organic solvent (oil phase) as a continuous phase and a clear sodium silicate solution (water phase) as a disperse phase, introducing carbon dioxide to the reverse micro-emulsion system under a certain temperature condition, separating solid from liquid and drying to prepare a white carbon black product. In the method disclosed by the invention, the overall reaction process is performed in a nano-scale sodium silicate 'water nucleus' and can be completed within only 2-5 seconds, thus the production efficiency of the white carbon black is greatly improved; during the preparation process of the white carbon black, an inorganic acid is replaced by carbon dioxide, thus the requirements on environmental protection are met; during the reaction process, the organic solvent can be recycled, thus the economic benefit can be increased. The white carbon black produced by the method disclosed by the invention is small in particle size, large in specific surface area, uniform in distribution and regular in microstructure and has the characteristics of the high-dispersity white carbon black.
Description
Technical field
The present invention relates to prepare in a kind of anti-microemulsion system the method for white carbon black, especially prepare rubber polymolecularity white carbon black.The present invention adopts carbon dioxide process to prepare white carbon black in anti-microemulsion system, is swift in response, and efficiency is high and meet environmental protection demand.
Background technology
In recent years, along with the increase year by year of white carbon black consumption, it is extensive that white carbon black production is prepared prospect.Industrial, white carbon black is divided into precipitated silica and thermal silica.Wherein, precipitated silica is widely used because production technique is simple, cost is low, output is large.
Tradition precipitated silica is to be made by sodium silicate solution and acid-respons, can be divided into sulfuric acid process, nitrate method, salt acid system and carbonatation process according to sour kind difference.Carbonatation process is to prepare white carbon black by water glass and carbon dioxide reaction, and this method has been avoided the direct discharge of excessive strong acid and salt in technological process, can economic recovery utilization, and reduce and pollute.
200910175259,201110026112 patents have all been introduced carbonic acid gas in water and have been reacted the method for preparing white carbon black with water glass, although the two is having certain effect aspect waste reclaimation, economic environmental protection, long, terminal was difficult to the deficiencies such as control and was but completely exposed reaction time its.
Anti-microemulsion method is as a kind of novel nano particle preparation method, it is using oil phase as medium phase, reaction raw materials one is evenly dispersed into mutually numerous " water core ", each water core is all regarded as a microreactor, and size of particles that therefore reaction generates is little and be uniformly dispersed, microtexture is regular.Utilize this mechanism, anti-microemulsion method is used to produce nano silicon in recent years.
" the microemulsion method synthesis of nano silicon dioxide granule " of Wang Yukun, in He Xiaoxiao " the controlled nano SiO 2 particle preparation research of size based on reverse microemulsion process ", all introduce the method for preparing white carbon black take tetraethoxy as raw material in anti-microemulsion system, white carbon black size of particles that this method makes is little, be evenly distributed, but because raw material is very expensive, therefore this method only limits to scientific research, the more difficult suitability for industrialized production that realizes.
Summary of the invention
The present invention adopts in anti-microemulsion system and passes into the method that carbonic acid gas is prepared white carbon black, combines the advantage of preparing white carbon black in carbonic acid gas and anti-microemulsion system.
Test method involved in the present invention comprises the steps: the water glass solution of clarification to join in the anti-microemulsion of the butanone that contains tensio-active agent and cosurfactant, under 40-70 ℃ of temperature condition, pass into carbon dioxide and generate silica particles, solid-liquid separation, dries to obtain white carbon black finished product.
As preferably: modulus of water glass used is 2.4-3.2, and mass concentration is 5%-15%.
As preferably: the mass ratio of water glass solution and butanone is 1/6-1/3.
As preferably: the tensio-active agent using for main chain be 12 to 18 quaternary ammonium salt containing carbon number, itself and water glass solution amount ratio are 0.5%-2%.
As preferably: cosurfactant is propyl carbinol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, and tensio-active agent and cosurfactant amount ratio are 1.5%-3%.
Anti-microemulsion can recycle.
Beneficial effect
Method involved in the present invention is prepared its object of white carbon black and is to shorten reaction time, improves reaction efficiency; Organic phase can economic recovery recycle, and meets environmental protection demand; Raw material is simple, generate product size little, be evenly distributed, meet rubber white carbon black property indices; There is good economic benefit.
Accompanying drawing explanation
Fig. 1 is the high multiple SEM of the white carbon black Electronic Speculum figure that this method makes,
Fig. 2 is the high multiple SEM of Degussa VN3 type white carbon black Electronic Speculum figure.
Fig. 3 is the sub-1165 type polymolecularity white carbon blacks in French sieve ground.
Embodiment
Embodiment 1:
In beaker, adding successively 180g butanone, 30g mass content is that 15% modulus is 2.4 clarification sodium silicate solution, and adding 60g mass content is that 1% Trimethyllaurylammonium bromide and 40g propyl carbinol are made into anti-microemulsion system; The mixed solution preparing is transferred in round-bottomed flask, under 70 ℃ of temperature condition, passed into carbonic acid gas, generate white carbon black; Solid-liquid separation, dries and obtains white carbon black finished product; Anti-microemulsion system recycles.
Embodiment 2:
In beaker, adding successively 150g butanone, 30g mass content is that 12% modulus is 2.8 clarification sodium silicate solution, and adding 45g mass content is that 1% Tetradecyl Trimethyl Ammonium Bromide and 20g Pentyl alcohol are made into anti-microemulsion system; The mixed solution preparing is transferred in round-bottomed flask, under 60 ℃ of temperature condition, passed into carbonic acid gas, generate white carbon black; Solid-liquid separation, dries and obtains white carbon black finished product; Anti-microemulsion system recycles.
Embodiment 3:
In beaker, adding successively 160g butanone, 40g mass content is that 10% modulus is 2.8 clarification sodium silicate solution, and adding 40g mass content is that 1% cetyl trimethylammonium bromide and 15g n-hexyl alcohol are made into anti-microemulsion system; The mixed solution preparing is transferred in round-bottomed flask, under 50 ℃ of temperature condition, passed into carbonic acid gas, generate white carbon black; Solid-liquid separation, dries and obtains white carbon black finished product; Anti-microemulsion system recycles.
Embodiment 4:
In beaker, adding successively 160g butanone, 40g mass content is that 8% modulus is 2.8 clarification sodium silicate solution, and adding 20g mass content is that 1% cetyl trimethylammonium bromide and 10g n-Heptyl alcohol are made into anti-microemulsion system; The mixed solution preparing is transferred in round-bottomed flask, under 40 ℃ of temperature condition, passed into carbonic acid gas, generate white carbon black; Solid-liquid separation, dries and obtains white carbon black finished product; Anti-microemulsion system recycles.
Embodiment 5:
In beaker, adding successively 150g butanone, 50g mass content is that 5% modulus is 3.2 clarification sodium silicate solution, and adding 25g mass content is that 1% Cetyltrimethylammonium bromide and 10g n-Octanol are made into anti-microemulsion system; The mixed solution preparing is transferred in round-bottomed flask, under 60 ℃ of temperature condition, passed into carbonic acid gas, generate white carbon black; Solid-liquid separation, dries and obtains white carbon black finished product; Anti-microemulsion system recycles.
Embodiment 6:
In beaker, adding successively 160g butanone, 40g mass content is that 12% modulus is 2.4 clarification sodium silicate solution, and adding 40g mass content is that 1% Tetradecyl Trimethyl Ammonium Bromide and 20g propyl carbinol are made into anti-microemulsion system; The mixed solution preparing is transferred in round-bottomed flask, under 70 ℃ of temperature condition, passed into carbonic acid gas, generate white carbon black; Solid-liquid separation, dries and obtains white carbon black finished product; Anti-microemulsion system recycles.
Embodiment 7:
In beaker, adding successively 150g butanone, 30g mass content is that 15% modulus is 2.8 clarification sodium silicate solution, and adding 45g mass content is that 1% Trimethyllaurylammonium bromide and 15g propyl carbinol are made into anti-microemulsion system; The mixed solution preparing is transferred in round-bottomed flask, under 65 ℃ of temperature condition, passed into carbonic acid gas, generate white carbon black; Solid-liquid separation, dries and obtains white carbon black finished product; Anti-microemulsion system recycles.
Embodiment 8:
In beaker, adding successively 180g butanone, 30g mass content is that 10% modulus is 2.8 clarification sodium silicate solution, and adding 30g mass content is that 1% cetyl trimethylammonium bromide and 20g propyl carbinol are made into anti-microemulsion system; The mixed solution preparing is transferred in round-bottomed flask, under 60 ℃ of temperature condition, passed into carbonic acid gas, generate white carbon black; Solid-liquid separation, dries and obtains white carbon black finished product; Anti-microemulsion system recycles.
Embodiment 9:
In beaker, adding successively 150g butanone, 50g mass content is that 10% modulus is 3.2 clarification sodium silicate solution, and adding 50g mass content is that 1% Tetradecyl Trimethyl Ammonium Bromide and 20g propyl carbinol are made into anti-microemulsion system; The mixed solution preparing is transferred in round-bottomed flask, under 55 ℃ of temperature condition, passed into carbonic acid gas, generate white carbon black; Solid-liquid separation, dries and obtains white carbon black finished product; Anti-microemulsion system recycles.
Embodiment 10:
In beaker, adding successively 150g butanone, 30g mass content is that 15% modulus is 2.4 clarification sodium silicate solution, and adding 45g mass content is that 1% cetyl trimethylammonium bromide and 15g propyl carbinol are made into anti-microemulsion system; The mixed solution preparing is transferred in round-bottomed flask, under 50 ℃ of temperature condition, passed into carbonic acid gas, generate white carbon black; Solid-liquid separation, dries and obtains white carbon black finished product; Anti-microemulsion system recycles.
Embodiment 11:
In beaker, adding successively 160g butanone, 40g mass content is that 10% modulus is 2.8 clarification sodium silicate solution, and adding 40g mass content is that 1% cetyl trimethylammonium bromide and 20g propyl carbinol are made into anti-microemulsion system; The mixed solution preparing is transferred in round-bottomed flask, under 70 ℃ of temperature condition, passed into carbonic acid gas, generate white carbon black; Solid-liquid separation, dries and obtains white carbon black finished product; Anti-microemulsion system recycles.
White carbon black performance test results in table 1, embodiment
Claims (6)
1. in an anti-microemulsion system, prepare the method for white carbon black, it is characterized in that: the water glass solution of clarification is joined in the anti-microemulsion of the butanone that contains tensio-active agent and cosurfactant, 40 ?pass into carbon dioxide under 70 ℃ of temperature condition and generate silica particles, solid-liquid separation, dries to obtain white carbon black finished product.
2. method according to claim 1, is characterized in that: modulus of water glass used is 2.4-3.2, and mass concentration is 5%-15%.
3. method according to claim 1, is characterized in that: the mass ratio of water glass solution and butanone is 1/6-1/3.
4. method according to claim 1, is characterized in that: the tensio-active agent using for main chain be 12 to 18 quaternary ammonium salt containing carbon number, itself and water glass solution amount ratio are 0.5%-2%.
5. method according to claim 1, is characterized in that: cosurfactant is propyl carbinol, (Isosorbide-5-Nitrae) butyleneglycol, Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, and tensio-active agent and cosurfactant mass ratio are 1.5%-3%.
6. method according to claim 1, is characterized in that: anti-microemulsion recycle.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860320A (en) * | 2015-05-06 | 2015-08-26 | 杭州云界生物科技有限公司 | Method for preparing modified nanosilicon dioxide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104860320A (en) * | 2015-05-06 | 2015-08-26 | 杭州云界生物科技有限公司 | Method for preparing modified nanosilicon dioxide |
| CN104860320B (en) * | 2015-05-06 | 2017-07-04 | 杭州云界生物科技有限公司 | A kind of preparation method of modified manometer silicon dioxide |
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| CN103880021B (en) | 2016-03-30 |
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Effective date of registration: 20181212 Address after: 236400 Room 518 Xin'an Road, Jingjiu Office, Fuyang Development Zone, Anhui Province Patentee after: Anhui Evolutionary Silicon Nanomaterials Technology Co., Ltd. Address before: 100029, No. 15 East Third Ring Road, Chaoyang District, Beijing Patentee before: Beijing University of Chemical Technology |