CN1056588C - Preparation of superfined silicon dioxine - Google Patents
Preparation of superfined silicon dioxine Download PDFInfo
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- CN1056588C CN1056588C CN96114245A CN96114245A CN1056588C CN 1056588 C CN1056588 C CN 1056588C CN 96114245 A CN96114245 A CN 96114245A CN 96114245 A CN96114245 A CN 96114245A CN 1056588 C CN1056588 C CN 1056588C
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Abstract
The present invention relates to a preparation method for superfine silicon dioxide. On the basis of the conventional souring precipitation method, hexamethylenetetramine, non-water-soluble organic solvents and small quantity of anionic surfactant are added, and the present invention especially uses a method for directly burning product without drying, and overcomes the disadvantage of easy adhesion of particles in the prior art. Superfine silicon dioxide can be prepared by the method of the present invention, the average diameters of primary particles are from 20 to 30 nm, and the average diameters of secondary particles are from 100 to 150 nm; the present invention has the advantages of narrow particle diameter distribution and good dispersibility.
Description
The present invention relates to a kind of preparation method of superfine silicon dioxide.
When the preparation high performance ceramic material, in order to improve the compactness of material, reduce firing temperature, increase the intensity and the toughness of material, one of its key is to realize ultra-fine, the ultrapure and homogenizing of powder stock.The method for preparing at present superfine silicon dioxide is a lot.Easier method is to be the method for the direct acid hydrolysis of raw material with the water glass, see 391 pages of 94 ' the Chinese material investigation proceedings low-dimensional materials, Chemical Industry Press (1994), but the granularity of the silicon-dioxide that this method makes is bigger than normal, and the primary particle particle diameter is generally at 100-500nm.Mentioned a kind of method that adds tetraethoxy on 43 pages of " silicate circular " the 3rd phases in 1992, make in the mixed solvent that is reflected at water and alcohol and carry out, obtain the silicon-dioxide that primary particle is 20-30nm behind the hydrolytic polymerization of process metal alkoxide, formation, Drying of gels and the calcining step of gel, but adhesion is serious.Day disclosure is speciallyyed permit flat 6-56148 and also this method is improved, and feed gas improving the adhesion of hydrolysis of alkoxide gained particle, but have little effect, and the costing an arm and a leg of tetraethoxy.Also useful spray method is made the aerosol method of hydrolysis in addition again with silicon sol, see M.Ocana, Ceramic International, 18 99 (1992), and be the method for the silicon dioxide granule of 20nm and narrow diameter distribution with arc process hydrous water refrigeration technique with preparation primary particle median size, see that a day disclosure speciallys permit clear 63-242906.But these two kinds of methods all need special equipment, complex process, cost height, and the easy adhesion of particle.
Purpose of the present invention: a kind of conventional equipment that utilizes is provided, and the easy method for preparing silicon-dioxide of technology makes the median size of silicon-dioxide primary particle about 20nm, and uniform particles, and size distribution is narrow, and particle is difficult for adhesion.
Main points of the present invention: the present invention adopts and adds the Acid precipitation method, comprises the following steps: successively
A. in the stirred reactor of routine, water glass and vulkacit H are added in the entry, water glass can be all kinds of hydrates of anhydrous sodium metasilicate and water glass, also can be the different all kinds of bubble flower alkali of sodium-silicon-rate; The addition of vulkacit H is the 30%-120% of silica volume by weight, add volume ratio to water again and be 0.7-1.8 with water-insoluble organic solvent and be the anion surfactant of organic solvent amount 0.05-3% by weight, fully stir and form water in oil emulsion.
B. in the emulsion of above-mentioned A, add dilute sulphuric acid, carry out precipitin reaction.
C. after the reaction product of above-mentioned B being filtered, drying directly at 500-800 ℃ of following calcination 2-5 hour, does not obtain superfine silicon dioxide.
Said organic solvent is selected from any in the halo derivatives of aliphatic hydrocarbon, aliphatic hydrocarbon, alicyclic hydro carbons and benzene and the derivative thereof.
Said anion surfactant is any in fatty group carboxylic acid and salt, fatty group sulfonic acid and salt thereof, fatty group sulfuric acid and the salt thereof.
The addition of said vulkacit H is preferably the 50-100% of silica volume by weight.
Said calcination temperature is preferably 600-700 ℃, and calcination time is preferably 3-4 hour.
Interpolation helps to form water in oil emulsion with water-insoluble organic solvent and a spot of anion surfactant, reaction is dispersed in many small unit carries out.
Great amount of hydroxy group is contained on the precipitated silica surface, because the bond energy of Si-O-Si key is very high, displaying or slowly being easy to take place polycondensation between the hydroxyl in the heat drying process, causes the primary particle adhesion agglomerating.Vulkacit H can be separated out plate crystal in the silica gel dehydration, intercept the polycondensation of silica gel particle, prevents that particle is agglomerating, when temperature is elevated to more than 260 ℃, and the vulkacit H effusion that can distil again, the purity of unlikely reduction product.
In addition, the present invention adopts direct calcination method, has shortened in the common drying process precipitation silica gel and has contacted with water for a long time, and the shortcoming of polycondensation takes place in a large number, and the adhesion of primary particle is reduced to a minimum.
The superfine silicon dioxide that adopts method of the present invention to make, the mean diameter of primary particle are 20-30nm, and the offspring mean diameter is 100-150nm, and narrow diameter distribution, good dispersion property.
The present invention is further elaborated below in conjunction with comparative example, embodiment and accompanying drawing:
Fig. 1: comparative example 1 products therefrom transmission electron micrograph, amplify 50,000 times
Fig. 2: comparative example 2 adds vulkacit H products therefrom transmission electron micrograph, amplifies 50,000 times
Fig. 3: adopt method products therefrom transmission electron micrograph of the present invention, amplify 50,000 times
Comparative example 1: take by weighing 3.5gNa
2SiO
39H
2O is dissolved in the 10ml water, adds 10ml benzene again, the 0.2g sodium stearate, fully stir and make emulsion, add 2mol/L dilute sulphuric acid precipitation, product filters, after the washing, 120 ℃ of down oven dry, 800 ℃ of following calcinations 4 hours in High Temperature Furnaces Heating Apparatus then, the electron photomicrograph of products therefrom is seen Fig. 1.As can be seen from the figure particle conglomerate in fact.
Comparative example 2: 0.6g vulkacit H and sodium silicate raw material is together soluble in water, and all the other are with comparative example 1.The electron photomicrograph of products therefrom is seen Fig. 2, and as can be seen from the figure the isolation effect of vulkacit H is very remarkable, but because the space of separating is bigger, the particle diameter of particle is bigger than normal.
Embodiment 1: take by weighing 4.7gNa
2SiO
39H
2O and 0.8g vulkacit H are dissolved in the 10ml water, add the 15ml tetracol phenixin again, 0.2g oleic acid, fully stirring and form emulsion, is that the dilute sulphuric acid of 2mol/L carries out precipitin reaction with concentration, products therefrom after filtration, after the washing without drying stage, direct calcination is 4 hours under 700 ℃, the electron photomicrograph of gained superfine silicon dioxide is seen Fig. 3, and as shown in Figure 3, the primary particle mean diameter of silicon-dioxide is 20nm, favorable dispersity, the mean diameter of its offspring are 100nm.
Embodiment 2: take by weighing 2.5g anhydrous sodium metasilicate and 1.2g vulkacit H, be dissolved in the 10ml water, add the 10ml hexanaphthene again, 0.1g Sodium dodecylbenzene sulfonate fully stirs and makes water in oil emulsion, is that the dilute sulphuric acid of 2mol/L carries out precipitin reaction with concentration, products therefrom is after washing, filtering, directly 650 ℃ of following calcinations 3 hours, the mean diameter of the silicon-dioxide primary particle that makes was 30nm, and the mean diameter of offspring is 100nm.
Embodiment 3: take by weighing the 5g sodium-silicon-rate and be 2.7 bubble flower alkali and 1g vulkacit H, be dissolved in the 10ml water, add the 10ml octane-iso again, 0.25g sodium lauryl sulphate fully stirs and makes water in oil emulsion, is that the dilute sulphuric acid of 2mol/L carries out precipitin reaction with concentration, products therefrom is after washing, filtering, directly 700 ℃ of following calcinations 3 hours, the mean diameter of the silicon-dioxide primary particle that makes was 20nm, and the mean diameter of offspring is 120nm.
Claims (5)
1. a method for preparing superfine silicon dioxide adopts to add the Acid precipitation method, comprises the following steps: successively
A. in water, add water glass and vulkacit H, the addition of vulkacit H is the 30%-120% of silica volume by weight, the volume ratio that adds again water is 0.7-1.8 and water-insoluble organic solvent and is the anion surfactant of organic solvent amount 0.05-3% by weight, stirs and forms water in oil emulsion;
B. in the emulsion of A, add dilute sulphuric acid, carry out precipitin reaction;
C. with the formed sedimentation and filtration of B, drying directly at 500-800 ℃ of following calcination 2-5 hour, does not obtain superfine silicon dioxide.
2. according to the method for claim 1, it is characterized in that: said and water-insoluble organic solvent is selected from any in the halo derivatives of aliphatic hydrocarbon, aliphatic hydrocarbon, alicyclic hydro carbons and benzene and the derivative thereof.
3. according to the method for claim 1, it is characterized in that: said anion surfactant is any in fatty group carboxylic acid and salt, fatty group sulfonic acid and salt thereof, fatty group sulfuric acid and the salt thereof.
4. according to the method for claim 1 or 2 or 3, it is characterized in that: the addition of vulkacit H is the 50-100% of silica volume by weight.
5. according to the method for claim 1 or 2 or 3 or 4, it is characterized in that: calcination temperature is 600-700 ℃, and calcination time is 3-4 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96114245A CN1056588C (en) | 1996-12-24 | 1996-12-24 | Preparation of superfined silicon dioxine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96114245A CN1056588C (en) | 1996-12-24 | 1996-12-24 | Preparation of superfined silicon dioxine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1186044A CN1186044A (en) | 1998-07-01 |
| CN1056588C true CN1056588C (en) | 2000-09-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96114245A Expired - Fee Related CN1056588C (en) | 1996-12-24 | 1996-12-24 | Preparation of superfined silicon dioxine |
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| CN (1) | CN1056588C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341956C (en) * | 2004-05-28 | 2007-10-10 | 河南大学 | Process for preparing nano silicon dioxide particles |
| CN101172608B (en) * | 2006-10-31 | 2010-10-06 | 中南大学 | Method of producing high-specific area nano-silicon dioxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047066A (en) * | 1989-05-03 | 1990-11-21 | 罗纳·布朗克化学公司 | Silica compatible with organic amines use in dentifrice compositions |
-
1996
- 1996-12-24 CN CN96114245A patent/CN1056588C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047066A (en) * | 1989-05-03 | 1990-11-21 | 罗纳·布朗克化学公司 | Silica compatible with organic amines use in dentifrice compositions |
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| CN1186044A (en) | 1998-07-01 |
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