CN102198942B - Preparation method of silicon dioxide - Google Patents
Preparation method of silicon dioxide Download PDFInfo
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- CN102198942B CN102198942B CN 201110046356 CN201110046356A CN102198942B CN 102198942 B CN102198942 B CN 102198942B CN 201110046356 CN201110046356 CN 201110046356 CN 201110046356 A CN201110046356 A CN 201110046356A CN 102198942 B CN102198942 B CN 102198942B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 77
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 49
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 49
- 238000005406 washing Methods 0.000 claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 26
- 229960001866 silicon dioxide Drugs 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 238000001556 precipitation Methods 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 9
- 230000001186 cumulative effect Effects 0.000 claims description 7
- 241000282326 Felis catus Species 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000003483 aging Methods 0.000 claims description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical group [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 claims description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 229920002379 silicone rubber Polymers 0.000 abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004383 yellowing Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000012429 reaction media Substances 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- 239000002245 particle Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 15
- 229920001971 elastomer Polymers 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000260 silastic Polymers 0.000 description 6
- 238000003828 vacuum filtration Methods 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- KHDSWONFYIAAPE-UHFFFAOYSA-N silicon sulfide Chemical compound S=[Si]=S KHDSWONFYIAAPE-UHFFFAOYSA-N 0.000 description 4
- 241001504664 Crossocheilus latius Species 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention discloses a preparation method of silicon dioxide, which sequentially comprises the following steps of: 1, preparing a sodium silicate solution A; 2, sectionally adding a sodium silicate solution B with sodium silicate mass concentration of 22-26 percent in a reaction kettle containing the sodium silicate solution A at a variable speed, controlling and regulating the addition speed of concentrated sulfuric acid at each section so as to keep PH of a reaction medium constant; 3, stopping adding the sodium silicate solution B, continuously adding the concentrated sulfuric acid, regulating the pH of the material obtained from the steps 2 to be 3.0-4.0, and preparing a sediment silicon dioxide suspension; 4, adding an organic surfactant in the suspension obtained in the step 3, ageing; and 5, filtering, washing, drying, post-treating and crushing to prepare the silicon dioxide product. According to the invention, the defect of poor dispersity of silicon dioxide in high-temperature vulcanized silicon rubber is overcome, yellowing performance of the silicon dioxide is improved, filtering and washing efficiencies are increased, washing time is shortened and washing water is saved.
Description
Technical field
The present invention relates to a kind of preparation method of silicon-dioxide, relate in particular to the method that a kind of precipitator method prepare silicon-dioxide.
Background technology
Silicon rubber is a kind of specialty elastomer, and it has realized being the machinery of many industrial application requirements and the fabulous compromise of chemical property (for example, electric property, chemical-resistant, high-temperature stability, physiology inertia).
The physical strength of pure silicon rubber is very low, the tensile strength of its cross-linked rubber only has about 0.35MPa, and after sneaking into reinforced filling, the tensile strength of cross-linked rubber can be brought up to 14MPa by 0.35MPa, the reinforcement rate exceeds the reinforcement rate (1.4～10 times) that other rubber can reach far away up to 40 times.As seen, the use of filler has decisive meaning to the final performance of silicon rubber.
At present, preferentially as the silicon rubber reinforced filling mainly be synthetic silica-aerosil and precipitated silica.
As everyone knows, aerosil is that it is expensive by silicon tetrachloride (or other chlorosilanes) pyrohydrolysis preparation under the H2/O2 flame, and the performance of the silicon rubber that it makes and not always satisfactory.
The production method of precipitated silica mainly is by sodium silicate aqueous solution and sulfuric acid reaction, generates the SiO2 precipitation, after filtration, dry, grind and make, it is cheap, so precipitated silica is widely used in the production of silicon rubber.But in the production of silicon rubber, the silicon-dioxide that the precipitator method are produced is dispersed bad in high-temperature silicon disulfide rubber, easily xanthochromia.
For above shortcoming, technos has proposed a lot of schemes, for example publication number be CN101585539A this disclosure of the invention of Chinese patent application " silicon rubber with the preparation method of high resistance yellowish-white carbon black " a kind of silicon rubber with the yellowish-white carbon black preparation method of high resistance, operation steps comprises that the dissolving of solid water glass is with refining, liquid soluble glass and the vitriol oil carry out precipitin reaction under the organic surface active agent effect, after the building-up reactions, adopt the compound anti-yellowing dose of B of self-control that silica particle surface is carried out anti-yellowing processing, again through press filtration, washing, filter cake liquefaction, spraying drying and work in-process are collected, crushing and classification and product-collecting obtain being exclusively used in the high anti-yellowing heavy glue shallow lake white carbon black of silicon rubber.
But the method needs to use the organic reagents such as ethanol, propyl carbinol in process of production, has increased complicacy and the potential safety hazard of process, has also increased manufacturing cost.And its method is still added sodium silicate solution and acid based on traditional the time to the method for dilute sodium silicate solution, and its silicon-dioxide that makes is used for the preparation of high-temperature silicon disulfide rubber, and its effect is desirable not enough.
Summary of the invention
The technical problem that the present invention mainly solves provides a kind of production technique that can produce in high-temperature silicon disulfide rubber good dispersity and be difficult for the silicon-dioxide of xanthochromia.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of preparation method of silicon-dioxide is provided, may further comprise the steps successively:
Step 1. is with water glass, inorganic dispersant and water, and being formulated as pH is 7.5～10.5, and temperature is 75～95 ℃ sodium silicate solution A;
(the M value is modulus to step 2., i.e. SiO with M=3.40～3.60
2/ Na
2The O mol ratio), the water glass mass concentration is that 22～26% sodium silicate solution B and the vitriol oil join the reactor that is loaded with sodium silicate solution A simultaneously, with precipitated silica, add in batches and control the adding speed of the adding vitriol oil and sodium silicate solution B when adding sodium silicate solution B, specific as follows:
Step 2.1. adds speed with V1 and adds 20 ± 2% of sodium silicate solution B cumulative volume, and adds the vitriol oil;
Step 2.2. adds speed with V2 and adds 30 ± 2% of sodium silicate solution B cumulative volume, and adds the vitriol oil;
Step 2.3. adds speed with V3 and adds remaining sodium silicate solution B, and adds the vitriol oil;
V1＜V2≤V3 wherein, keeping the pH of material in the reactor in step 2 is 7.5～10.5, temperature is 75～95 ℃;
Step 3. continues to add the vitriol oil, and the pH to 3.0 of set-up procedure 2 gained materials～4.0 make precipitated silica suspension;
Step 4. adds organic surface active agent and ageing in step 3 gained suspension;
The precipitated silica suspension of step 5. filtration step 4 gained ageings obtains precipitation of silica;
Step 6. washing step 5 filters the precipitation of silica that obtains;
Step 7. is dry with the precipitation of silica that step 6 washing obtains, and makes silica product.
The invention has the beneficial effects as follows: be different from the precipitator method that prior art prepares silicon-dioxide, the present invention:
A. in the beginning solution A, add inorganic dispersant, its not only with raw material in impurity metal ion (such as the Fe) complexing of bringing into form soluble complexes, and this inorganic dispersant can make the precursor of generation be controlled in the close limit in reaction process, and stop its cohesion to generate gel, thereby improved the dispersed of product and improved the xanthochromia performance.
B. the sodium silicate solution B of suitable concentration adds simultaneously with acid, control sodium silicate solution B adds with the speed segmentation that changes, and keep the PH of reaction medium constant by the interpolation speed of regulating acid, thereby so that particle shape and the structure of expectation reach optimum balance.The sodium silicate solution in special process stage adds speed and mutual relationship, determines the Aggregate and agglomerate degree of silicon dioxide granule, the performance of final decision product.
C. control the adding speed of sodium silicate solution B, so that add about 20% of sodium silicate solution B total amount with V1 speed, its V1 is less than the adding speed of all the other sodium silicate solution B.
D. after the aging step, add organic surface active agent, itself and silica particle surface hydroxy combining have stoped between the silicon dioxide granule gel in conjunction with cohesion generation bad dispersibility, make the silicon dioxide granule flocculation accelerate settling velocity, thereby accelerated filtration velocity and the washing speed of suspension.The adding of organic surface active agent has also effectively prevented the further reunion of silicon dioxide granule in the drying process simultaneously, has guaranteed that particle distribution is even, thereby has improved its dispersiveness.
From the above mentioned, process experienced three stages of the present invention: primary particle forms, flocculation is condensed, agglomeration.
Find unexpectedly, concrete speed and volume at the adding sodium silicate solution B of each section setting have caused the formation of precipitated silica of the present invention.Volume at the sodium silicate solution B of each section adding is different, as follows:
Fs (precursor formation) adds sodium silicate solution B with V1 speed, and the volume of its adding is for adding 20 ± 2% of sodium silicate solution B cumulative volume.When just having begun, little precursor forms in reaction and since this moment precursor concentration lower, wide apart each other, its particle diameter several to tens nanometer range.
Subordinate phase (precursor flocculation and cohesion) adds sodium silicate solution B with V2 speed, and the volume of its adding is for adding 30 ± 2% of sodium silicate solution B cumulative volume.Carrying out along with reaction, the quantity of precursor increases, particle diameter increases, when its concentration enough high and spacing of particle from enough approaching when being in the same place (flocculation stage), react between the precursor, thus precursor and formation than macroparticle between form the aggregate (agglomeration phase) of Si-O-Si key.
Phase III (agglomeration and particle form) adds sodium silicate solution B with V3 speed, and the volume of its adding is for adding 50 ± 2% of sodium silicate solution B cumulative volume.Proceed with reaction process, the quantity of aggregate and big or small sustainable growth, if reached certain scope, aggregate enough approaches and forms agglomerate (agglomeration stage).The agglomerate that forms is connected with hydrogen bond by Van der Waals force, and the formation of agglomerate is reversible, can break mechanically.
After sodium silicate solution adds gradually, obtain precipitated silica of the present invention.At this, the adding speed of sodium silicate solution increases gradually: V1＜V2≤V3.
Wherein, described sodium silicate solution B, the modulus M=3.50 of its water glass, the mass concentration of water glass is 25%.
Wherein, described inorganic dispersant is Sodium hexametaphosphate 99 or tripoly phosphate sodium STPP.
Wherein, described organic surface active agent is nonionogenic tenside or cats product.
Wherein, described nonionogenic tenside is fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene.
Wherein, described cats product is quaternary amine type tensio-active agent.
Wherein, described cats product is palmityl trimethyl ammonium chloride.
Wherein, step 1 mesosilicic acid sodium solution A temperature is 75～95 ℃ and heats up by steam heating and to reach; The precipitation forms of precipitation of silica is filter cake in the step 5; Drying mode in the step 7 is spraying drying.
Wherein, the total duration of step 2 was more than or equal to 80 minutes.
Wherein, digestion time is 5～30 minutes in the technological process of described step 4.
Embodiment
By describing technology contents of the present invention in detail, being realized purpose and effect, give in detail explanation below in conjunction with embodiment.
Embodiment 1
Step 1.383ml water, 15ml water glass (M=3.60, concentration 25%) solution and 10g Sodium hexametaphosphate 99 add and are equipped with in the 1000ml glass flask of stirring, at water-bath heating temperature of charge to 90 ℃, and the pH=10.5 of solution ± 0.1;
Step 2.174ml sodium silicate solution (M=3.60, concentration 25%) joined in the above-mentioned material at 25 minutes, added simultaneously the vitriol oil (98%), the pH=10.5 of maintenance reaction mass ± 0.1;
Step 2.2111ml sodium silicate solution joined in the above-mentioned material at 25 minutes, added simultaneously the vitriol oil (98%), the pH=10.5 of maintenance reaction mass ± 0.1;
Step 2.3185ml sodium silicate solution joined in the above-mentioned material at 40 minutes, added simultaneously the vitriol oil (98%), the pH=10.5 of maintenance reaction mass ± 0.1;
Step 3. stops to add sodium silicate solution, and continuation adds the vitriol oil, the pH=3.0 of adjustment reaction mass～4.0, and the adding speed of the vitriol oil adds 50% calculating of speed by the vitriol oil of above-mentioned steps 2.3.
Step 4. adds the 0.1g palmityl trimethyl ammonium chloride, stirs ageing 30 minutes;
The above-mentioned suspension of step 5. Büchner funnel vacuum filtration, filtration time 15 minutes;
Step 6. precipitates washing time 60 minutes with 3000ml water wash step 5 gained;
The filter cake that step 7. obtains step 6 washing is put into baking oven and is dried to moisture content in 105 ℃ and is less than or equal to 5.0%, obtains the white powdery precipitated silica of efflorescence.
The specific conductivity 100 μ s/cm of product precipitated silica aqeous suspension.
The particle diameter of product precipitated silica (supersound process 2 minutes, laser particle analyzer is measured) 11 μ m.
White powdery precipitated silica and raw-silastic continuously are mixing, and range estimation xanthochromia after post cure is without xanthochromia.Film is without white point, i.e. good dispersity.
Embodiment 2
Repeat embodiment 1, only " palmityl trimethyl ammonium chloride " in embodiment 1 step 4 become fatty alcohol-polyoxyethylene ether.
Suspension Büchner funnel vacuum filtration, and use the 3000ml water washing.Filter cake is put into baking oven and is dried to moisture content in 105 ℃ and is less than or equal to 5.0%, and getting stone roller in one's hands is broken white powdery precipitated silica.
Filtration time 20 minutes, washing time 75 minutes.
The specific conductivity 180 μ s/cm of product precipitated silica aqeous suspension.
The particle diameter of product precipitated silica (supersound process 2 minutes, laser particle analyzer is measured) 14 μ m.
White precipitate silicon-dioxide and raw-silastic continuously are mixing, and range estimation xanthochromia after post cure is without xanthochromia.Film is without white point, i.e. good dispersity.
Embodiment 3
Repeat embodiment 1, only pH=10.5 ± 0.1 in embodiment 1 each step is adjusted into pH=9.0 ± 0.1.
Suspension Büchner funnel vacuum filtration, and use the 3000ml water washing.Filter cake is put into baking oven and is dried to moisture content in 105 ℃ and is less than or equal to 5.0%, and getting stone roller in one's hands is broken white powdery precipitated silica product.
Filtration time 15 minutes, washing time 65 minutes.
The specific conductivity 160 μ s/cm of product precipitated silica aqeous suspension.
The particle diameter of product precipitated silica (supersound process 2 minutes, laser particle analyzer is measured) 13 μ m.
White precipitate silicon-dioxide and raw-silastic continuously are mixing, and range estimation xanthochromia after post cure is without xanthochromia.Film is without white point, i.e. good dispersity.
Embodiment 4
Repeat embodiment 1, only pH=10.5 ± 0.1 in embodiment 1 each step is adjusted into pH=7.5 ± 0.1.
Suspension Büchner funnel vacuum filtration, and use the 3000ml water washing.Filter cake is put into baking oven and is dried to moisture content in 105 ℃ and is less than or equal to 5.0%, and getting stone roller in one's hands is broken white powdery precipitated silica product.
Filtration time 15 minutes, washing time 65 minutes.
The specific conductivity 160 μ s/cm of product precipitated silica aqeous suspension.
The particle diameter of product precipitated silica (supersound process 2 minutes, laser particle analyzer is measured) 14 μ m.
White precipitate silicon-dioxide and raw-silastic continuously are mixing, and range estimation xanthochromia after post cure is without xanthochromia.Film is without white point, i.e. good dispersity.
Embodiment 5:
Repeat embodiment 1, but cancelled " palmityl trimethyl ammonium chloride " in embodiment 1 step 4.
Suspension Büchner funnel vacuum filtration, and use the 3000ml water washing.Filter cake is put into baking oven and is dried to moisture content 5.0% in 105 ℃, and obtaining that slightly hard hand grinds is broken white precipitate silica product.
Filtration time 30 minutes, washing time 128 minutes.
The specific conductivity 200 μ s/cm of product precipitated silica aqeous suspension.
The particle diameter of product precipitated silica (supersound process 2 minutes, laser particle analyzer is measured) 15 μ m.
White precipitate silicon-dioxide and raw-silastic continuously are mixing, and the range estimation xanthochromia slightly has xanthochromia after twice sulfuration, and favorable dispersity, and film is without white point.
Comparative Examples
Prepare according to a conventional method precipitated silica.The sodium silicate solution B of 230ml water and 11ml embodiment 1 adds and is equipped with in the 1000ml glass flask of stirring, at water-bath heating temperature of charge to 90 ℃.
The sodium silicate solution B of 210ml embodiment 1 and the 68ml vitriol oil added in 90 minutes simultaneously, during keep 90 ℃ of temperature.
Stop to add sodium silicate solution B, continue to add the vitriol oil, transfer pH to 3.0～4.0.
Suspension Büchner funnel vacuum filtration, and use the 3000ml water washing.Filter cake is put into baking oven and is dried to moisture content in 105 ℃ and is less than or equal to 5.0%, obtains hard block white precipitate silica product.
Filtration time 65 minutes, washing time 346 minutes.
The specific conductivity 600 μ s/cm of product precipitated silica aqeous suspension.
The particle diameter of product precipitated silica (supersound process 2 minutes, laser particle analyzer is measured) 21 μ m.
White precipitate silicon-dioxide and raw-silastic continuously are mixing, range estimation xanthochromia after post cure, and xanthochromia is more serious.Film has more white point, bad dispersibility.
The present invention has better solved the problem of precipitated silica dispersed bad and easy xanthochromia in high-temperature silicon disulfide rubber, consumes the approach of providing for the filtration of improvement precipitated silica, detersive efficiency, reduction energy consumption and water simultaneously.
The above only is embodiments of the invention; be not so limit claim of the present invention; every equivalent flow process conversion that utilizes specification sheets of the present invention to do, or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (8)
1. the preparation method of a silicon-dioxide is characterized in that, may further comprise the steps successively:
Step 1. is with water glass, inorganic dispersant and water, and being formulated as pH is 7.5～10.5, and temperature is 75～95 ℃ sodium silicate solution A; Described inorganic dispersant is Sodium hexametaphosphate 99 or tripoly phosphate sodium STPP;
Step 2. is with M=3.40～3.60, the water glass mass concentration is that 22～26% sodium silicate solution B and the vitriol oil join the reactor that is loaded with sodium silicate solution A simultaneously, with precipitated silica, add in batches and control the adding speed of the adding vitriol oil and sodium silicate solution B when adding sodium silicate solution B, specific as follows:
Step 2.1. adds speed with V1 and adds 20 ± 2% of sodium silicate solution B cumulative volume, and adds the vitriol oil;
Step 2.2. adds speed with V2 and adds 30 ± 2% of sodium silicate solution B cumulative volume, and adds the vitriol oil;
Step 2.3. adds speed with V3 and adds remaining sodium silicate solution B, and adds the vitriol oil;
V1＜V2≤V3 wherein, keeping the pH of material in the reactor in step 2 is 7.5～10.5, temperature is 75～95 ℃;
Step 3. continues to add the vitriol oil, and the pH to 3.0 of set-up procedure 2 gained materials～4.0 make precipitated silica suspension;
Step 4. adds organic surface active agent and ageing in step 3 gained suspension; Described organic surface active agent is nonionogenic tenside or cats product;
The precipitated silica suspension of step 5. filtration step 4 gained ageings obtains precipitation of silica;
Step 6. washing step 5 filters the precipitation of silica that obtains;
Step 7. is dry with the precipitation of silica that step 6 washing obtains, and makes silica product.
2. the preparation method of silicon-dioxide according to claim 1 is characterized in that, described sodium silicate solution B, and the modulus M=3.50 of its water glass, the mass concentration of water glass is 25%.
3. the preparation method of silicon-dioxide according to claim 1 is characterized in that, described nonionogenic tenside is fatty alcohol-polyoxyethylene ether or alkylphenol polyoxyethylene.
4. the preparation method of silicon-dioxide according to claim 1 is characterized in that, described cats product is quaternary ammonium salt cationic surfactant.
5. the preparation method of silicon-dioxide according to claim 4 is characterized in that, described cats product is palmityl trimethyl ammonium chloride.
6. the preparation method of silicon-dioxide according to claim 1 is characterized in that, step 1 mesosilicic acid sodium solution A temperature is 75～95 ℃ and heats up by steam heating and to reach; The precipitation forms of precipitation of silica is filter cake in the step 5; Drying mode in the step 7 is spraying drying.
7. the preparation method of silicon-dioxide according to claim 1 is characterized in that, the total duration of step 2 was more than or equal to 80 minutes.
8. the preparation method of silicon-dioxide according to claim 1 is characterized in that, digestion time is 5～30 minutes in the technological process of described step 4.
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| CN103652503A (en) * | 2013-12-26 | 2014-03-26 | 福建龙岩精博化工科技有限公司 | Preparation method of environmentally friendly feed additive for aquaculture |
| JP6937111B2 (en) | 2016-05-16 | 2021-09-22 | ハリマ化成株式会社 | Tire fillers, tire rubber compositions, tires, and methods for manufacturing tire fillers. |
| CN107151350B (en) * | 2017-04-24 | 2019-06-07 | 确成硅化学股份有限公司 | A kind of preparation method of high fluidity silica |
| CN108164754B (en) * | 2017-12-28 | 2020-02-21 | 无锡恒诚硅业有限公司 | Preparation method of modified white carbon black and modified white carbon black prepared by same |
| CN109485054B (en) * | 2019-01-02 | 2019-10-01 | 广州市飞雪材料科技有限公司 | A kind of low oil factor high-specific surface area friction type silica and preparation method thereof |
| CN111747422B (en) * | 2020-06-22 | 2023-07-28 | 安徽龙泉硅材料有限公司 | Preparation method of ultrapure sodium silicate for silicon dioxide |
| CN113772684B (en) * | 2021-09-16 | 2023-04-25 | 安徽凤阳赛吉元无机材料有限公司 | Anti-yellowing white carbon black and preparation method thereof |
| CN113830773B (en) * | 2021-10-11 | 2023-10-24 | 福建正盛无机材料股份有限公司 | Preparation method of white carbon black by large pore volume precipitation method |
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| CN1418810A (en) * | 2002-12-18 | 2003-05-21 | 天津化工研究设计院 | Silicon dioxide produced by high-structure, low surface sedimentation method, and prepn. method for producing same |
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