CN104211070A - Preparation method of nanometer silica - Google Patents
Preparation method of nanometer silica Download PDFInfo
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- CN104211070A CN104211070A CN201410243406.2A CN201410243406A CN104211070A CN 104211070 A CN104211070 A CN 104211070A CN 201410243406 A CN201410243406 A CN 201410243406A CN 104211070 A CN104211070 A CN 104211070A
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Abstract
The invention relates to a preparation method of nanometer silica. The method comprises the following steps: acidifying sodium silicate as a raw material, filtering, washing, adding an entrainer to form an azeotrope, distilling, precipitating, drying, calcining, sieving to obtain nanometer silica powder, adding the entrainer, and carrying out azeotropic treatment. The method has the advantages of low prices of experiment raw materials, and no need of any dispersant or surfactant, and the silica powder prepared through the method has a particle size of 1-100nm, has good dispersibility and no agglomeration phenomenon, and is suitable for industrialized production.
Description
Technical field
The present invention relates to the preparation method of silicon-dioxide powdery, be specifically related to a kind of preparation method of nanometer grade silica.
Background technology
The preparation method of current nanometer grade silica mainly contains vapor phase process, sol-gel method, microemulsion method and liquid-phase precipitation method.The silica product that wherein vapor phase process is prepared is that in ownership system Preparation Method, performance is the most excellent.The method ratio is easier to prepare crystalline state and amorphous nano particles, has clean, wall-less effect, even particle size distribution, without cohering, output is high, can continuous seepage and the advantage such as to be widely used.Technique is mainly silicon tetrachloride high-temp combustion in oxyhydrogen flame, obtains through deposition depickling.This technics comparing is ripe, has industrialization product, but its raw materials technology is expensive, and high to equipment requirements, Production Flow Chart is long, and energy consumption is large.And mainly contain liquid-phase precipitation method and microemulsion method with the preparation technology that water glass with low cost is raw material.
Microemulsion method is shown in patent CN100345755C, adopt alkalimetal silicate mix with tensio-active agent and cosurfactant be made into make water in oil Nano sol surpass increase roll into a ball a system solution, adding acidic precipitation agent makes reaction carry out in nanoscale, generates nanometer grade silica small-particle.The silica particles that the method prepares is evenly distributed, good dispersity, but the microemulsion system mesosilicic acid salts contg that microemulsion method is made into is low, and tensio-active agent and cosurfactant consumption greatly, are not suitable for suitability for industrialized production, and organism is difficult to remove.It is extensive, inexpensive that chemical precipitation method has raw material sources, and energy consumption is little, and technique is simple, is easy to the advantages such as industrialization, but also there is the problem that product cut size is large or distribution range is wider simultaneously.Liquid-phase precipitation method is shown in patent CN100341966C, and the method take water glass as raw material, and ammonium chloride is precipitation agent, and ethanol is dispersion agent, and adds silicoorganic compound precipitation is carried out to surface modification and prepared the nanometer grade silica product of particle diameter at 10-50nm.Patent CN102092721A take water glass as raw material, and sulfuric acid is precipitation agent, and adds organic surface active agent, low-carbon (LC) alcohols dispersion agent, has prepared the nano-scale white carbon black product that content is more than 96%.
Summary of the invention
The object of the invention is the defect for above-mentioned prior art, provides a kind of and compares the production method that existing document is easier to the nanometer grade silica of industrial prospect.To achieve these goals, technical scheme of the present invention provides a kind of preparation method of nanometer grade silica: be that raw material carries out acidification reaction with water glass, adds entrainer after filtration and carries out azeotropic process, precipitation drying after washing, calcining, sieves and obtains nanometer grade silica powder.
The preparation method of nanometer grade silica of the present invention comprises following steps:
1) sodium silicate solution acid adding is adjusted to pH3-6, after stirring, carries out ageing;
2) also washing precipitation is filtered;
3) by step 2) in filter gained filter cake and be dispersed in entrainer and form azeotropic mixture, distill the solvent eliminated in filter cake, filtered and recycled precipitates;
4) by step 3) middle precipitation drying, calcining, sieves, obtains nanometer grade silica powder.
In some embodiments, sodium silicate solution concentration of the present invention is 0.4-1.0mol/L.
In some embodiments, acid of the present invention is mineral acid.
In other embodiments, mineral acid of the present invention is mass concentration is 20%-30% sulphuric acid soln.
In some embodiments, the stirring velocity of stirring of the present invention is 500-800 rev/min, churning time >=0.5 hour, and the digestion time of ageing is 3-5 hour.
In some embodiments, entrainer of the present invention is selected from propyl carbinol, isopropylcarbinol, benzene, toluene, pyridine or its combination.
In other embodiments, entrainer of the present invention is propyl carbinol.
In some embodiments, step 4) described in calcining temperature be 400-600 DEG C, calcination time is 3 hours.
In some embodiments, the temperature of drying of the present invention is 70 DEG C, and time of drying is 12 hours.
In some embodiments, being filtered into described in the inventive method uses fast qualitative filter paper low pressure suction filtration, washing is washed till filtrate not containing the acid group impurity introduced with distilled water, concrete, when souring agent is sulfuric acid, should be washed till filtrate detects without white precipitate generation with barium chloride solution, when souring agent is hydrochloric acid, then adopts silver nitrate solution to detect filtrate without till white precipitate.
Detailed description of the present invention
Definition and general terms
The term " azeotropic mixture " that the present invention uses or " azeotrope " represent the homogeneous phase solution when two or more heterogeneities, during with a specific ratio mixing, under fixing pressure, only have a boiling point.Solvent in filter cake can be multiple, wherein common with water.
Term " entrainer " expression that the present invention uses and feed component generate the addO-on therapy of azeotropic mixture.In material to be desolventized, adding entrainer, utilize the characteristic of azeotropic mixture, can distill waiting to desolventize during distillation.
The term " filtration " that the present invention uses represents the operation be separated with nonfluid by fluid by medium under gravity or other External Force Actings, described medium includes but not limited to filter paper, gauze, filter core, semi-permeable membranes, filter screen etc., in theory, the material containing vesicular structure can become the medium of filtration; The equipment filtered includes but not limited to vacuum or reliever, pressurizing device, centrifugal device etc.
The term " drying " that the present invention uses represents borrows heat energy to make water or solvent gasification in material, and takes away the process of generated steam.Dry method includes but not limited to oven dry, vacuum-drying, lyophilize, air stream drying, microwave drying, ultra red ray drying and dielectric dry etc.
The raw material that method of the present invention adopts is easy to get and cheap, without the need to adding any dispersion agent and tensio-active agent again; The present invention utilizes azeotropic step, namely adds the solvent in organic entrainer and filter cake, and composition azeotropic mixture, can reduce the boiling point of solvent, azeotropic mixture is evaporated at a lower temperature, take the solvent in filter cake out of, can not cause reunion when drying.
Accompanying drawing explanation
Fig. 1 is embodiment 1 nano silicon product transmission electron microscope picture (TEM)
Fig. 2 is embodiment 2 nano silicon product transmission electron microscope picture (TEM)
Fig. 3 is embodiment 3 nano silicon product transmission electron microscope picture (TEM)
Fig. 4 is embodiment 4 nano silicon product transmission electron microscope picture (TEM)
Embodiment
The following stated be the preferred embodiment of the present invention, what the present invention protected is not limited to following preferred implementation.It should be pointed out that on the basis of conceiving in these innovation and creation for a person skilled in the art, the some distortion made and improvement, all belong to protection scope of the present invention.
Embodiment 1
Take 113.68g nine water water glass, add water and be mixed with the solution that sodium silicate silicate is 0.4mol/L, be placed in the there-necked flask of 2 liters, open and stir in 500 revs/min.The sulphuric acid soln of preparation 30%, slowly drops in sodium silicate solution under normal temperature state, until reaction soln pH=6 is for dripping terminal.Continue stirring 1 hour, stop stirring normal temperature ageing 3 hours.Molten for reaction gained gelatinous precipitate is carried out vacuum filtration, and with pure water, filtration, cyclical operation is until final filtrate produces without white precipitate with barium chloride solution detection.Filter cake evenly spreads in propyl carbinol and carries out azeotropic dehydration process in 120 DEG C, until moisture no longer distillates.Filtered and recycled propyl carbinol, is deposited in 70 DEG C of vacuum-dryings 12 hours, and be placed in 500 DEG C of retort furnace calcinings 3 hours, cross 120 mesh sieves, obtaining 20g particle diameter is 10-30nm silicon-dioxide powdery, and TEM figure is shown in Fig. 1.
Embodiment 2
Take 170.52g nine water water glass, add water and be mixed with the solution that sodium silicate silicate is 0.6mol/L, be placed in the there-necked flask of 2 liters, open and stir in 600 revs/min.The sulphuric acid soln of preparation 25%, slowly drops in sodium silicate solution under normal temperature state, until reaction soln pH=5 is for dripping terminal.Continue stirring 0.5 hour, stop stirring normal temperature ageing 4 hours.Molten for reaction gained gelatinous precipitate is carried out vacuum filtration, and with pure water, filtration, cyclical operation is until final filtrate produces without white precipitate with bariumchloride detection.Filter cake evenly spreads in propyl carbinol and carries out azeotropic dehydration process in 140 DEG C, until moisture no longer distillates.Filtered and recycled propyl carbinol, is deposited in 70 DEG C of vacuum-dryings 12 hours, and be placed in 500 DEG C of retort furnace calcinings 3 hours, cross 120 mesh sieves, obtaining 29g particle diameter is 30-50nm powder product, and TEM figure is shown in Fig. 2.
Embodiment 3
Take 227.36g nine water water glass, add water and be mixed with the solution that sodium silicate silicate is 0.8mol/L, be placed in the there-necked flask of 2 liters, open and stir in 700 revs/min.The sulphuric acid soln of preparation 25%, slowly drops in sodium silicate solution under normal temperature state, until reaction soln pH=4 is for dripping terminal.Continue stirring 1 hour, stop stirring normal temperature ageing 4 hours.Molten for reaction gained gelatinous precipitate is carried out vacuum filtration, and with pure water, filtration, cyclical operation is until final filtrate produces without white precipitate with bariumchloride detection.Filter cake evenly spreads in propyl carbinol and carries out azeotropic dehydration process in 140 DEG C, until moisture no longer distillates.Filtered and recycled propyl carbinol, is deposited in 70 DEG C of vacuum-dryings 12 hours, and be placed in 400 DEG C of retort furnace calcinings 3 hours, cross 120 mesh sieves, obtaining 41g particle diameter is 20-40nm silicon-dioxide powdery product, and TEM figure is shown in Fig. 3.
Embodiment 4
Take 284.6g nine water water glass, add water and be mixed with the solution that sodium silicate silicate is 1.0mol/L, be placed in the there-necked flask of 2 liters, open and stir in 800 revs/min.The sulphuric acid soln of preparation 20%, slowly drops in sodium silicate solution under normal temperature state, until reaction soln pH=3 is for dripping terminal.Continue stirring 0.5 hour, stop stirring normal temperature ageing 5 hours.Molten for reaction gained gelatinous precipitate is carried out vacuum filtration, and with pure water, filtration, cyclical operation is until final filtrate produces without white precipitate with bariumchloride detection.Filter cake evenly spreads in propyl carbinol and carries out azeotropic dehydration process in 130 DEG C, until moisture no longer distillates.Filtered and recycled propyl carbinol, is deposited in 70 DEG C of vacuum-dryings 12 hours, and be placed in retort furnace 600 DEG C calcining 3 hours, cross 120 mesh sieves, obtaining 52g particle diameter is 30-70nm silicon-dioxide powdery product, and TEM figure is shown in Fig. 4.
Claims (9)
1. a preparation method for nanometer grade silica, is characterized in that comprising following steps:
1) sodium silicate solution acid adding is adjusted to pH3-6, after stirring, carries out ageing;
2) also washing precipitation is filtered;
3) by step 2) in filter gained filter cake and be dispersed in entrainer and form azeotropic mixture, the solvent in distillation removing filter cake, filtered and recycled precipitates;
4) by step 3) middle precipitation drying, calcining, sieves, obtains nanometer grade silica powder.
2. preparation method according to claim 1, is characterized in that, described sodium silicate solution concentration is 0.4-1.0mol/L.
3. preparation method according to claim 1, is characterized in that, described acid is mineral acid.
4. preparation method according to claim 3, is characterized in that, described mineral acid is mass concentration is 20%-30% sulphuric acid soln.
5. preparation method according to claim 1, is characterized in that, step 1) stirring velocity of described stirring is 500-800 rev/min, churning time >=0.5 hour, the digestion time of ageing is 3-5 hour.
6. preparation method according to claim 1, is characterized in that, described entrainer is selected from propyl carbinol, isopropylcarbinol, benzene, toluene, pyridine or its combination.
7. preparation method according to claim 1, is characterized in that, described entrainer is propyl carbinol.
8. preparation method according to claim 1, is characterized in that, step 4) calcining temperature of described calcining is 400-600 DEG C, calcination time is 3 hours.
9. preparation method according to claim 1, is characterized in that, step 4) drying temperature of described drying is 70 DEG C, time of drying is 12 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110835096A (en) * | 2019-11-28 | 2020-02-25 | 江西赣锋锂业股份有限公司 | Method for preparing high-purity anhydrous lithium perchlorate by using battery-grade lithium hydroxide monohydrate |
| CN111017939A (en) * | 2020-01-14 | 2020-04-17 | 福建省三明正元化工有限公司 | Preparation method of high-dispersion silicon dioxide |
| CN112593098A (en) * | 2020-11-25 | 2021-04-02 | 中南大学 | Method for extracting tungsten from tungsten-containing raw material by using hydrous sodium silicate |
| CN114408930A (en) * | 2022-03-02 | 2022-04-29 | 南方科技大学 | Nano SiO2And preparation method thereof, CO2Adsorbent and method of use thereof |
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| CN101085881A (en) * | 2006-06-05 | 2007-12-12 | 北京化工大学 | Method for modifying ultra-fine silicon dioxide |
| CN101214963A (en) * | 2008-01-02 | 2008-07-09 | 吉林大学 | Method for preparing high pure nano silicon dioxide from oil shale slag |
| CN102633267A (en) * | 2012-04-19 | 2012-08-15 | 浙江宇达化工有限公司 | Preparation method of nano SiO2 |
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2014
- 2014-06-03 CN CN201410243406.2A patent/CN104211070A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085881A (en) * | 2006-06-05 | 2007-12-12 | 北京化工大学 | Method for modifying ultra-fine silicon dioxide |
| CN101214963A (en) * | 2008-01-02 | 2008-07-09 | 吉林大学 | Method for preparing high pure nano silicon dioxide from oil shale slag |
| CN102633267A (en) * | 2012-04-19 | 2012-08-15 | 浙江宇达化工有限公司 | Preparation method of nano SiO2 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110835096A (en) * | 2019-11-28 | 2020-02-25 | 江西赣锋锂业股份有限公司 | Method for preparing high-purity anhydrous lithium perchlorate by using battery-grade lithium hydroxide monohydrate |
| CN110835096B (en) * | 2019-11-28 | 2023-01-06 | 江西赣锋锂业股份有限公司 | Method for preparing high-purity anhydrous lithium perchlorate by using battery-grade lithium hydroxide monohydrate |
| CN111017939A (en) * | 2020-01-14 | 2020-04-17 | 福建省三明正元化工有限公司 | Preparation method of high-dispersion silicon dioxide |
| CN111017939B (en) * | 2020-01-14 | 2023-10-24 | 福建省三明正元化工有限公司 | Preparation method of high-dispersion silicon dioxide |
| CN112593098A (en) * | 2020-11-25 | 2021-04-02 | 中南大学 | Method for extracting tungsten from tungsten-containing raw material by using hydrous sodium silicate |
| CN112593098B (en) * | 2020-11-25 | 2022-04-26 | 中南大学 | Method for extracting tungsten from tungsten-containing raw material by using hydrous sodium silicate |
| CN114408930A (en) * | 2022-03-02 | 2022-04-29 | 南方科技大学 | Nano SiO2And preparation method thereof, CO2Adsorbent and method of use thereof |
| CN114408930B (en) * | 2022-03-02 | 2023-03-21 | 深碳科技(深圳)有限公司 | Nano SiO 2 And preparation method thereof, CO 2 Adsorbent and method of use thereof |
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Address after: No. 368 East Sunshine Science Park 523871 Guangdong city of Dongguan province Changan Zhen Sha Zhen'an Road Applicant after: DONGGUAN DONGYANG GUANGKE R & D CO., LTD. Address before: No. 368 East Sunshine Science Park 523871 Guangdong city of Dongguan province Changan Zhen Sha Zhen'an Road Applicant before: Dongyang, Dongguan City Chang'an light Aluminum research and development company limited |
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