CN111153411B - Preparation method of silicon dioxide - Google Patents
Preparation method of silicon dioxide Download PDFInfo
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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Abstract
The invention discloses a preparation method of silicon dioxide, which comprises the following steps: step 1: adding process hot water, adding citric acid and sodium citrate, controlling the molar concentration of the citric acid and the sodium citrate to be 0.1mol/L, stirring and heating to the reaction temperature; step 2: water glass according to the volume ratio: sulfuric acid: dilution water=15-18:1:5-10, adding water glass, sulfuric acid and dilution water for reaction; step 3: stopping adding water glass, and mixing sulfuric acid according to the volume ratio: dilution water: continuously adding sulfuric acid and dilution water into the sodium salt solution=1:5-10:50-70 for reaction; step 4: stopping adding the sodium salt solution, and mixing sulfuric acid according to the volume ratio: dilution water = 1:5-10 continuing to add sulfuric acid and dilution water; step 5: stopping adding sulfuric acid and dilution water after detecting the pH value to be 4.5-5 to obtain slurry; step 6: adding ethanol into the slurry, continuing the reaction, centrifugally separating, washing and drying. The beneficial effects of the invention are as follows: the silicon dioxide obtained by the preparation method has excellent dispersion performance.
Description
Technical Field
The invention relates to silicon dioxide, in particular to a preparation method of silicon dioxide.
Background
White carbon black, also known as hydrated silicic acid, light silica, chemical expression is generally written as mSiO 2 ·nH 2 O, the appearance is white highly dispersed amorphous powder and microbeads. White carbon black is widely applied to various industries such as rubber products, tires, feed additives, food additives, paint matting agents, papermaking, silicone rubber, toothpaste friction agents, printing ink and the like.
The white carbon black is used as an excellent reinforcing agent and a filler in rubber application, so that the physical properties of the rubber material can be greatly improved, and the hysteresis of the rubber material can be reduced. In the tire industry, the white carbon black can reduce the rolling resistance of the tire without losing the wet skid resistance, and compared with the common carbon black filled rubber, the white carbon black filled rubber can reduce the rolling resistance by 30 percent.
Chinese patent publication No. CN107697921a discloses a high-dispersibility white carbon black and a preparation method thereof. The preparation method of the white carbon black comprises the following steps: (1) Heating water, adding water glass, adding ethanol, and mixing to obtain a reaction base solution, wherein the temperature is unchanged in the whole process, and the concentration of the water glass is 0.01-1.00mol/L; the mass fraction of the ethanol is 0.1-5wt%; (2) Adding acid and water glass into the reaction base solution at the same time, and mixing to react to obtain white carbon black suspension; the reaction temperature is kept constant and the same as the reaction base solution, and the concentration of the water glass is kept constant and the same as the concentration of the reaction base solution; (3) Stopping adding water glass into the white carbon black suspension, adding acid independently, and regulating the pH value of a reaction system to 3.0-5.0 to obtain an acidified white carbon black suspension; (4) And (3) carrying out solid-liquid separation on the acidified white carbon black suspension to obtain a filter cake, thereby obtaining the white carbon black.
However, in this production method, when water glass is added to the base liquid, sodium silicate in the base liquid is already in a sufficiently dispersed state when acid is added. And the acid added will contact sodium silicate in the base solution to react. The sulfuric acid with the weight percent of 90-99 is adopted by the acid, so that the reaction of the acid and water glass is concentrated, the particle size distribution of the generated silicon dioxide particles is not uniform enough, and the dispersion performance of the white carbon black of the final product in rubber is affected, and the improvement is needed.
Disclosure of Invention
The invention aims to provide a preparation method of silicon dioxide. The silicon dioxide obtained by the preparation method has excellent dispersion performance.
The technical aim of the invention is realized by the following technical scheme:
a method for preparing silica, comprising the steps of:
step 1: adding process hot water, adding citric acid and sodium citrate, controlling the molar concentration of the citric acid and the sodium citrate to be 0.1mol/L, stirring and heating to the reaction temperature;
step 2: adding water glass, sulfuric acid and dilution water according to the volume ratio of water glass to sulfuric acid to dilution water=15-18:1:5-10, and carrying out reaction while maintaining the stirring rate and the reaction temperature unchanged;
step 3: stopping adding water glass, continuously adding sulfuric acid and dilution water according to the volume ratio sulfuric acid to dilution water to sodium salt solution=1:5-10:50-70, and keeping the stirring rate and the reaction temperature unchanged for reaction;
step 4: stopping adding the sodium salt solution, and continuously adding sulfuric acid and dilution water according to the volume ratio sulfuric acid to dilution water=1:5-10, and keeping the stirring rate and the reaction temperature unchanged;
step 5: stopping adding sulfuric acid and dilution water after detecting the pH value to be 4.5-5 to obtain slurry;
step 6: adding ethanol into the slurry, maintaining the stirring rate and the reaction temperature unchanged, continuing the reaction, centrifugally separating, washing and drying.
The invention is further provided with: in the step 6, vinyltriethoxysilane, disodium edetate and cetyltrimethylammonium chloride are added for reaction.
The invention is further provided with: in the step 6, the volume ratio of the ethanol to the slurry is 0.5-0.8:1, and the mass ratio of the vinyltriethoxysilane to the slurry is 0.1-0.2:1; the mass ratio of the disodium ethylenediamine tetraacetate to the slurry is 0.001-0.002:1; the mass ratio of the cetyl trimethyl ammonium chloride to the slurry is 0.0015-0.003:1.
The invention is further provided with: the reaction time of the step 6 is 7-9h.
The invention is further provided with: the stirring speed of the step 1 is 30-50rad/min, and the reaction temperature is 80-95 ℃.
The invention is further provided with: the reaction time of the step 2 is 1-2h.
The invention is further provided with: the sodium salt in the step 3 is sodium sulfate.
The invention is further provided with: the concentration of the sodium salt solution in the step 3 is 13-17wt%.
The invention is further provided with: the reaction time of the step 3 is 5-15min.
In summary, the invention has the following beneficial effects:
1. in the step 1, only process hot water is added, but no water glass is added, so that after the water glass and sulfuric acid are added, sodium silicate and sulfuric acid are in a dispersed state, so that the particle size distribution of precipitated silica primary particles is uniform, and the binding force of the primary particles is weaker in the subsequent increasing process, so that the final particle size is smaller, and the dispersion into rubber is facilitated;
2. the addition of sodium sulfate can effectively prevent the silicon dioxide from tightly agglomerating, so that the final product has better dispersibility in rubber;
3. the addition of the ethanol can control the particle size of the silicon dioxide through the hydrogen bonding action of the silicon hydroxyl and the certain steric hindrance action of ethanol molecules;
4. the vinyl triethoxysilane can reduce the number of hydroxyl groups on the surface of a product, improve the hydrophobicity degree, reduce the aggregation degree and improve the dispersion performance;
5. disodium ethylenediamine tetraacetate is a good complexing agent, is dissolved in water and is weak acid, and can decompose carbonate to release carbon dioxide. In alkaline solution (pH > 11), all four acetic acid groups in the structure ionize into acetate groups;
6. cetyl trimethyl ammonium chloride is a surfactant with good performance and can form foam in the reaction system. When the oligomeric polysilicic acid reaches a saturation concentration, a large amount of precipitated silica nuclei form rapidly. When the rate of formation of the silica core crystal is greater than the rate of growth and aggregation thereof, the particle size of the resulting particles becomes smaller. Meanwhile, cetyl trimethyl ammonium chloride is used as a cationic dispersing agent, is easy to adsorb on the surfaces of silicon dioxide particles with a large amount of negative charges in alkaline solution, plays a role in surface coating, disperses the silicon dioxide particles to prevent further aggregation of the silicon dioxide particles, and thus the final particle size is smaller;
7. the citric acid contains a plurality of hydroxyl groups in the molecular structure, and can be in hydrogen bond action with silicon hydroxyl groups, so that the agglomeration of silicon dioxide particles is reduced, and the particle size of the silicon dioxide is controlled. Meanwhile, citric acid and sodium citrate form a buffer system, and the pH of the system is prevented from changing too fast in the sulfuric acid adding process, so that agglomeration of silica particles during the pH change too fast is avoided.
Detailed Description
In examples 1 to 5, the temperature of the process hot water was 80℃and the modulus of the water glass was 3.60, the molar concentration was 1.2mol/L and the sulfuric acid concentration was 98% by weight.
Example 1
A method for preparing silica, comprising the steps of:
step 1: adding process hot water, adding citric acid and sodium citrate, controlling the molar concentration of the citric acid and the sodium citrate to be 0.1mol/L, controlling the stirring speed to be 30rad/min, and stirring and heating to 80 ℃;
step 2: adding water glass, sulfuric acid and dilution water according to the volume ratio of water glass to sulfuric acid to dilution water=15:1:5, and carrying out reaction for 1h while maintaining the stirring rate and the reaction temperature unchanged;
step 3: stopping adding water glass, continuously adding sulfuric acid and dilution water according to the volume ratio of sulfuric acid to dilution water to sodium sulfate solution=1:5:50, keeping the stirring rate and the reaction temperature unchanged, and carrying out the reaction for 5min;
step 4: stopping adding the sodium salt solution, and continuously adding sulfuric acid and dilution water according to the volume ratio of sulfuric acid to dilution water=1:5, and keeping the stirring rate and the reaction temperature unchanged;
step 5: stopping adding sulfuric acid and dilution water after detecting the pH value to 4.5 to obtain slurry;
step 6: adding ethanol, vinyl triethoxysilane, disodium ethylenediamine tetraacetate and cetyltrimethylammonium chloride into the slurry, maintaining the stirring rate and the reaction temperature unchanged, continuing the reaction for 7 hours, centrifuging, washing and drying.
In the step 6, the volume ratio of the ethanol to the slurry is 0.5:1, and the mass ratio of the vinyltriethoxysilane to the slurry is 0.1:1; the mass ratio of the disodium ethylenediamine tetraacetate to the slurry is 0.001:1; the mass ratio of the cetyl trimethyl ammonium chloride to the slurry is 0.0015:1.
In step 3, the sodium sulfate solution concentration was 13wt%.
Example 2
A method for preparing silica, comprising the steps of:
step 1: adding process hot water, adding citric acid and sodium citrate, controlling the molar concentration of the citric acid and the sodium citrate to be 0.1mol/L, controlling the stirring speed to be 50rad/min, and stirring and heating to 95 ℃;
step 2: adding water glass, sulfuric acid and dilution water according to the volume ratio of water glass to sulfuric acid to dilution water=16:1:9, and carrying out reaction for 2h while maintaining the stirring rate and the reaction temperature unchanged;
step 3: stopping adding water glass, continuously adding sulfuric acid and dilution water according to the volume ratio of sulfuric acid to dilution water to sodium sulfate solution=1:8:60, keeping the stirring rate and the reaction temperature unchanged, and carrying out the reaction for 7min;
step 4: stopping adding the sodium salt solution, and continuously adding sulfuric acid and dilution water according to the volume ratio of sulfuric acid to dilution water=1:10, and keeping the stirring rate and the reaction temperature unchanged;
step 5: stopping adding sulfuric acid and dilution water after detecting the pH value to 5 to obtain slurry;
step 6: adding ethanol, vinyl triethoxysilane, disodium ethylenediamine tetraacetate and cetyltrimethylammonium chloride into the slurry, maintaining the stirring rate and the reaction temperature unchanged, continuing the reaction for 8 hours, centrifuging, washing and drying.
In the step 6, the volume ratio of the ethanol to the slurry is 0.6:1, and the mass ratio of the vinyltriethoxysilane to the slurry is 0.2:1; the mass ratio of the disodium ethylenediamine tetraacetate to the slurry is 0.002:1; the mass ratio of the cetyl trimethyl ammonium chloride to the slurry is 0.003:1.
In step 3, the sodium sulfate solution concentration was 14wt%.
Example 3
A method for preparing silica, comprising the steps of:
step 1: adding process hot water, adding citric acid and sodium citrate, controlling the molar concentration of the citric acid and the sodium citrate to be 0.1mol/L, controlling the stirring speed to be 35rad/min, and stirring and heating to 93 ℃;
step 2: adding water glass, sulfuric acid and dilution water according to the volume ratio of water glass to sulfuric acid to dilution water=18:1:10, and carrying out reaction for 1h while maintaining the stirring rate and the reaction temperature unchanged;
step 3: stopping adding water glass, continuously adding sulfuric acid and dilution water according to the volume ratio of sulfuric acid to dilution water to sodium sulfate solution=1:7:70, keeping the stirring rate and the reaction temperature unchanged, and carrying out the reaction for 10min;
step 4: stopping adding the sodium salt solution, and continuously adding sulfuric acid and dilution water according to the volume ratio of sulfuric acid to dilution water=1:6, and keeping the stirring rate and the reaction temperature unchanged;
step 5: stopping adding sulfuric acid and dilution water after detecting the pH value to 5 to obtain slurry;
step 6: adding ethanol, vinyl triethoxysilane, disodium ethylenediamine tetraacetate and cetyltrimethylammonium chloride into the slurry, maintaining the stirring rate and the reaction temperature unchanged, continuing the reaction for 9 hours, centrifuging, washing and drying.
In the step 6, the volume ratio of the ethanol to the slurry is 0.7:1, and the mass ratio of the vinyltriethoxysilane to the slurry is 0.1:1; the mass ratio of the disodium ethylenediamine tetraacetate to the slurry is 0.001:1; the mass ratio of the cetyl trimethyl ammonium chloride to the slurry is 0.002:1.
In step 3, the sodium sulfate solution concentration was 15wt%.
Example 4
A method for preparing silica, comprising the steps of:
step 1: adding process hot water, adding citric acid and sodium citrate, controlling the molar concentration of the citric acid and the sodium citrate to be 0.1mol/L, controlling the stirring speed to be 45rad/min, and stirring and heating to 90 ℃;
step 2: adding water glass, sulfuric acid and dilution water according to the volume ratio of water glass to sulfuric acid to dilution water=18:1:5, and carrying out reaction for 2h while maintaining the stirring rate and the reaction temperature unchanged;
step 3: stopping adding water glass, continuously adding sulfuric acid and dilution water according to the volume ratio of sulfuric acid to dilution water to sodium sulfate solution=1:10:55, keeping the stirring rate and the reaction temperature unchanged, and carrying out the reaction for 13min;
step 4: stopping adding the sodium salt solution, and continuously adding sulfuric acid and dilution water according to the volume ratio of sulfuric acid to dilution water=1:7, and keeping the stirring rate and the reaction temperature unchanged;
step 5: stopping adding sulfuric acid and dilution water after detecting the pH value to 4.5 to obtain slurry;
step 6: adding ethanol, vinyl triethoxysilane, disodium ethylenediamine tetraacetate and cetyltrimethylammonium chloride into the slurry, maintaining the stirring rate and the reaction temperature unchanged, continuing the reaction for 8 hours, centrifuging, washing and drying.
In the step 6, the volume ratio of the ethanol to the slurry is 0.8:1, and the mass ratio of the vinyltriethoxysilane to the slurry is 0.2:1; the mass ratio of the disodium ethylenediamine tetraacetate to the slurry is 0.002:1; the mass ratio of the cetyl trimethyl ammonium chloride to the slurry is 0.002:1.
In step 3, the sodium sulfate solution concentration was 17wt%.
Example 5
A method for preparing silica, comprising the steps of:
step 1: adding process hot water, adding citric acid and sodium citrate, controlling the molar concentration of the citric acid and the sodium citrate to be 0.1mol/L, controlling the stirring speed to be 40rad/min, and stirring and heating to 85 ℃;
step 2: adding water glass, sulfuric acid and dilution water according to the volume ratio of water glass to sulfuric acid to dilution water=17:1:8, and carrying out reaction for 1h while maintaining the stirring rate and the reaction temperature unchanged;
step 3: stopping adding water glass, continuously adding sulfuric acid and dilution water according to the volume ratio of sulfuric acid to dilution water to sodium sulfate solution=1:6:65, keeping the stirring rate and the reaction temperature unchanged, and carrying out the reaction for 15min;
step 4: stopping adding the sodium salt solution, and continuously adding sulfuric acid and dilution water according to the volume ratio of sulfuric acid to dilution water=1:9, and keeping the stirring rate and the reaction temperature unchanged;
step 5: stopping adding sulfuric acid and dilution water after detecting the pH value to 4.5 to obtain slurry;
step 6: adding ethanol, vinyl triethoxysilane, disodium ethylenediamine tetraacetate and cetyltrimethylammonium chloride into the slurry, maintaining the stirring rate and the reaction temperature unchanged, continuing the reaction for 7 hours, centrifuging, washing and drying.
In the step 6, the volume ratio of the ethanol to the slurry is 0.6:1, and the mass ratio of the vinyltriethoxysilane to the slurry is 0.1:1; the mass ratio of the disodium ethylenediamine tetraacetate to the slurry is 0.001:1; the mass ratio of the cetyl trimethyl ammonium chloride to the slurry is 0.003:1.
In step 3, the sodium sulfate solution concentration was 16wt%.
Examples 1 to 5 were tested and recorded in accordance with GB/T32678-2016 "high dispersion precipitated hydrated silica as rubber compounding agent".
Examples 1-5 silica test recording tables
| CTAB specific surface area (m 2 /g) | Oil absorption value (cm) 3 /g) | D50/μm | |
| Example 1 | 229 | 1.4 | 0.8 |
| Example 2 | 219 | 1.3 | 0.8 |
| Example 3 | 232 | 1.0 | 0.7 |
| Example 4 | 228 | 1.4 | 0.8 |
| Example 5 | 222 | 1.5 | 0.9 |
Silica filling test
In terms of parts by weight, 96.25 parts of SSBR and 30 parts of BR containing 26.25 parts were kneaded in an internal mixer at 60 ℃, and 3 parts of zinc oxide, 1 part of stearic acid, 1.5 parts of an antioxidant 4010NA and 1 part of paraffin wax were sequentially added. After mixing, 70 parts of silicon dioxide and 7 parts of a mixture of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide (Si 69) as a silane coupling agent are added in two equal parts at intervals of 3min, and after the addition, the mixture is mixed for 2-3min, and the temperature is controlled to be 150 ℃. Mixing at 70rad/min for 5min and removing the gum. After the sizing material is cooled, mixing is carried out on a two-roll open mill, and 1.5 parts of accelerator CZ, 2 parts of accelerator D and 1.4 parts of sulfur are added, and the mixing is carried out uniformly, thus obtaining the rubber compound. Vulcanizing the mixture at 150 ℃ by using a flat vulcanizing machine overnight to obtain the SSBR/BR conforming material.
Wherein silica was prepared according to examples 1-5.
The prepared SSBR/BR was subjected to the following experiment:
testing the mechanical properties of the vulcanized rubber by adopting an electronic universal testing machine;
the dynamic viscoelastic performance of vulcanized rubber is tested by adopting a dynamic thermo-mechanical analyzer, wherein an experimental mode is a stretching mode, the specification of a sample is cuboid with the thickness of 2mm to 15mm (10 to 15 mm) and the thickness of the sample is high, the stretching strain amplitude is 0.1 percent, the testing frequency is 10Hz, the temperature range is-70 to 70 ℃, and the heating rate is 3 ℃/min;
and (3) carrying out dynamic compression heat generation test on the sizing material by adopting a compression fatigue tester (YS-25), wherein the test time is 25min, the frequency is 30Hz, and the test temperature is 55 ℃.
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| 100% stress/MPa | 2.81 | 2.95 | 3.04 | 2.96 | 2.91 |
| 300% stress/MPa | 14.1 | 15.3 | 16.1 | 15.1 | 14.7 |
| Enhancement ratio | 5.02 | 5.19 | 5.30 | 5.10 | 5.05 |
| tanδ(0℃) | 0.383 | 0.404 | 0.423 | 0.399 | 0.386 |
| tanδ(60℃) | 0.098 | 0.086 | 0.077 | 0.091 | 0.095 |
| Compression heat/°c | 16.5 | 16.3 | 15.8 | 16.4 | 16.4 |
Note that: the reinforcing ratio is the ratio of 300% stretching stress to 100% stretching stress, and the larger the ratio is, the better the reinforcing property is.
The present embodiment is merely illustrative of the present invention and is not intended to be limiting, and modifications thereof without creative contribution can be made by those skilled in the art after reading the present specification, as long as they are protected by patent laws within the scope of claims of the present invention.
Claims (7)
1. A preparation method of silicon dioxide is characterized in that: the method comprises the following steps:
step 1: adding process hot water, adding citric acid and sodium citrate, controlling the molar concentration of the citric acid and the sodium citrate to be 0.1mol/L, stirring and heating to the reaction temperature;
step 2: water glass according to the volume ratio: sulfuric acid: adding water glass, sulfuric acid and dilution water into the mixture in a ratio of (1:5-10) of dilution water to 15-18:1, and carrying out reaction while maintaining the stirring rate and the reaction temperature unchanged;
step 3: stopping adding water glass, and mixing sulfuric acid according to the volume ratio: dilution water: continuously adding sulfuric acid and dilution water into the sodium salt solution=1:5-10:50-70, and keeping the stirring rate and the reaction temperature unchanged for reaction;
step 4: stopping adding the sodium salt solution, and mixing sulfuric acid according to the volume ratio: dilution water=1:5-10 sulfuric acid and dilution water are continuously added, and the stirring rate and the reaction temperature are maintained unchanged;
step 5: stopping adding sulfuric acid and dilution water after detecting the pH value to be 4.5-5 to obtain slurry;
step 6: adding ethanol into the slurry, maintaining the stirring rate and the reaction temperature unchanged, continuing the reaction, centrifugally separating, washing and drying;
in the step 6, vinyl triethoxysilane, disodium ethylenediamine tetraacetate and cetyltrimethylammonium chloride are added for reaction;
the concentration of the sodium salt solution in the step 3 is 13-17wt%.
2. The method for preparing silica according to claim 1, wherein: in the step 6, the volume ratio of the ethanol to the slurry is 0.5-0.8:1, and the mass ratio of the vinyltriethoxysilane to the slurry is 0.1-0.2:1; the mass ratio of the disodium ethylenediamine tetraacetate to the slurry is 0.001-0.002:1; the mass ratio of the cetyl trimethyl ammonium chloride to the slurry is 0.0015-0.003:1.
3. The method for preparing silica according to claim 1, wherein: the reaction time of the step 6 is 7-9h.
4. The method for preparing silica according to claim 1, wherein: the stirring speed of the step 1 is 30-50rad/min, and the reaction temperature is 80-95 ℃.
5. The method for preparing silica according to claim 1, wherein: the reaction time of the step 2 is 1-2h.
6. The method for preparing silica according to claim 1, wherein: the sodium salt in the step 3 is sodium sulfate.
7. The method for preparing silica according to claim 1, wherein: the reaction time of the step 3 is 5-15min.
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