CN104291342A - Precipitated silicon dioxide, and preparation method and application thereof - Google Patents
Precipitated silicon dioxide, and preparation method and application thereof Download PDFInfo
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- CN104291342A CN104291342A CN201410487918.3A CN201410487918A CN104291342A CN 104291342 A CN104291342 A CN 104291342A CN 201410487918 A CN201410487918 A CN 201410487918A CN 104291342 A CN104291342 A CN 104291342A
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Abstract
The invention relates to a high-specific-area precipitated silicon dioxide used as a rubber tire reinforcing agent, and a preparation method and application thereof. The precipitated silicon dioxide is composed of spherical microbead silicon dioxide and granular granulated silicon dioxide. The BET specific area of the silicon dioxide is 185-235 m<2>/g, the CTAB is 165-205 m<2>/g, the pH value is 5.5-7.5, the pore volume is 1.65-2.25 cm<3>/g, the most probable pore size is 15-35nm, the ultrasonic particle size is 6.0-10.0 mu m, and the silicon dioxide can be used as a rubber tire reinforcing agent.
Description
Technical field
The present invention relates to a kind of novel method being used as the high-specific surface area precipitated silica of rubber tyre strengthening agent.It also relates in spherical microballon silicon-dioxide and granular granulated silica.
Background technology
Precipitated silica act as strengthening agent in rubber tyre, particularly green tire and load-carrying tire, in order to reduce the rolling resistance of tire, reduce heat-dissipating, improve wear resistance, precipitated silica is essential, and along with the enforcement of European Union's labeling acts and the increasingly serious of environment, the usage quantity of precipitated silica in rubber tyre is increasing.
The same with other any supporting materials, it will be easy to processing on the one hand, and it will be easy to and rubber mix on the other hand.
Add silicon-dioxide obtain the object of best reinforcing effect to be reached through, silicon-dioxide in rubber should be fine as much as possible and be uniformly distributed as much as possible.In order to meet this requirement, the binding ability of silicon-dioxide and rubber must be improved and disperses and be depolymerized to very thin powder, but also can be complete and homogeneous be dispersed in rubber.
Unfortunately, have the silicon-dioxide of relatively high-specific surface area, its wear resistance in rubber is fine, but poor processability and dispersiveness bad.
CN 1100001C discloses a kind of preparation method of precipitated silica, react comprising making silicate and souring agent, obtain the suspension of precipitated silica thus, be separated afterwards and this suspension dry, precipitate in such a way: (i) prepares Initial stock solutions, wherein containing the silicate total amount that uses in described reaction at least partially with at least one ionogen, in the concentration of described Initial stock solutions mesosilicic acid salt with SiO
2be expressed as 50 to 60g/l.(ii) in described stock solution, souring agent is added until the pH of reaction medium reaches 7 to 8.5, (iii) in reaction medium, souring agent is added, add the silicate of its surplus if desired simultaneously, described sepn process comprises the filtration and washing operation that use the strainer that pressurizing device is housed to carry out ,-by spraying the suspension of dry wherein solids content lower than 17wt%.But what the method adopted is diluted acid method, and the deficiency of diluted acid method has: (1) production capacity is low, and about low by 20%, unit consumption is high; (2) diluted acid is large to the corrodibility of e-quipment and pipe, and maintenance of equipment expense is high; (3) SiO is adopted
2control, analyze consuming time in actually operating, and control unstable; (4) pulp solid content is low, and dry energy consumption is high, product particle undercapacity.
Summary of the invention
For the problem of prior art, the invention provides a kind of novel method preparing high-specific surface area precipitated silica, the precipitated silica adopting the method to obtain has high comparison surface, and has the reinforcing property of excellent processing characteristics, dispersing property and excellence.
To achieve these goals, present invention employs following technical scheme:
A kind of method preparing precipitated silica, described method comprises makes water glass and vitriol oil generation precipitin reaction, thus obtains the suspension of precipitated silica, afterwards through press filtration and washing, slurrying process this suspension dry, wherein, precipitin reaction is carried out as follows:
(1) prepare the initial bed material of precipitin reaction, the part wherein containing the water glass total amount used in described precipitin reaction, in described initial bed material, concentration of sodium silicate is with Na
2o is expressed as 0.05 ~ 0.15N, and pH is 6.0 ~ 12.0;
(2) in described initial bed material, drip the vitriol oil and excess water glass simultaneously, make water glass and vitriol oil generation precipitin reaction;
(3), after dropping excess water glass and the vitriol oil terminate simultaneously, in reaction medium, the vitriol oil is dripped separately;
Described press filtration and washing process comprise the filtration and washing operation that adopt membrane pressure filter to carry out the silica suspension that precipitin reaction is produced, formation filter cake;
Described slurrying process comprises employing multi-stage stirrer and wet wheeling machine liquefies to the filter cake that press filtration produces, form silica suspension, the solid content of this suspension is more than the 20wt% (advantage that solid content is high: (1) can reduce the energy consumption in drying process, reach energy-conservation object, often improve the solid content of 1%, can energy efficient about 5%.(2) intensity and the homogeneity of bead particles can be guaranteed, and ensure in use not broken, good flowing properties.(3) environmental protection in the mixing process of rubber, and the energy accurate measurement when feeding intake).
Adding electrolytical object in precipitin reaction process is pore volume (porosity) in order to improve white carbon black, is specially adapted to BET and is greater than 250m
2the white carbon black of/more than g.And the present invention does not adopt ionogen can reach identical pore volume yet, being applicable to BET is 185-235m
2the white carbon black of/g.
In the present invention, the essential condition obtaining silicon-dioxide superperformance comprises: concentration of sodium silicate, the pH value, simultaneously dropping excess water glass and the vitriol oil, employing membrane pressure filter of initial bed material carry out filtering and washing.Pressure filter due to this structure has water pressing function, can guarantee that obtained filter cake solid content is more than 24.0wt%.
In the present invention, step (1) first prepares the initial bed material of precipitin reaction, makes it contain a part for the water glass total amount required for precipitin reaction, and then drips the vitriol oil and excess water glass wherein simultaneously.
In the present invention, water glass drips at twice, is the initial bed material of preparation reaction for the first time, only drips separately water glass (not dripping acid), object provides a stable reaction conditions for second step drips, and guarantees the Na when second time drips the vitriol oil and excess water glass simultaneously
2the stability contorting of O.
In step (1), described concentration of sodium silicate is with Na
2o is expressed as 0.05 ~ 0.15N, such as 0.06N, 0.07N, 0.08N, 0.09N, 0.10N, 0.11N, 0.12N, 0.13N or 0.14N, preferably 0.06 ~ 0.08N.Described pH is 6 ~ 12, such as 6.5,7,7.5,8,8.5,9,9.5,10,10.5,11 or 11.5, preferably 9.0 ~ 11.0.
In the present invention, the described vitriol oil refers to that massfraction is the sulfuric acid of 98%.
In the present invention, described water glass refers to that modulus is the water glass of 3.10 ~ 3.60, and the modulus of described water glass is such as 3.15,3.25,3.35,3.45 or 3.55.
In the present invention, the time simultaneously dripping the vitriol oil and excess water glass in step (2) is 60 ~ 150 minutes, such as 65 minutes, 70 minutes, 75 minutes, 80 minutes, 85 minutes, 90 minutes, 95 minutes, 100 minutes, 105 minutes, 110 minutes, 115 minutes, 120 minutes, 125 minutes, 130 minutes, 135 minutes, 140 minutes or 145 minutes, preferably 90 ~ 120 minutes.
In the present invention, controlling temperature of reaction in step (2) is 60 ~ 90 DEG C, such as 63 DEG C, 66 DEG C, 69 DEG C, 72 DEG C, 75 DEG C, 78 DEG C, 81 DEG C, 84 DEG C or 87 DEG C, preferably 78 ~ 82 DEG C.
In addition, drip at the same time in the process of the vitriol oil and excess water glass, remain that concentration of sodium silicate in the constant and reaction medium of temperature of reaction is with Na
2it is the stable of 9.0 ~ 11.0 (such as 9.2,9.4,9.6,9.8,10,10.2,10.4,10.6 or 10.8) that O is expressed as 0.06 ~ 0.08N (such as 0.062N, 0.064N, 0.066N, 0.068N, 0.07N, 0.072N, 0.074N, 0.076N or 0.078N) or pH.
Drip at the same time in the process of the vitriol oil and excess water glass, first controlling temperature of reaction is 70 ~ 80 DEG C, such as 71 DEG C, 72 DEG C, 73 DEG C, 74 DEG C, 75 DEG C, 76 DEG C, 77 DEG C, 78 DEG C or 79 DEG C, after one hour, be warming up to 80 ~ 90 DEG C, such as 81 DEG C, 82 DEG C, 83 DEG C, 84 DEG C, 85 DEG C, 86 DEG C, 87 DEG C, 88 DEG C or 89 DEG C.The advantage of two step temperature methods is exactly: can the difference of effective control BET-CTAB, namely reduces the micropore in white carbon black, make white carbon black can better with compounding rubber, improve that it is dispersed.
In the present invention, the concentration of described excess water glass is with Na
2o is expressed as 2.30 ~ 2.70N, such as 2.35N, 2.40N, 2.45N, 2.50N, 2.55N, 2.60N, 2.65N, preferably 2.40 ~ 2.50N.
Exemplary method as: first the present invention prepares the water glass of above-mentioned concentration as raw material, adopts the initial bed material of reaction in this preparation of raw material step (1), then drips the water glass of the above-mentioned concentration of surplus in step (2) more simultaneously.
After dripping the vitriol oil and excess water glass simultaneously and terminating, start to carry out step (3).
In step (3), be that the drop rate of the half of vitriol oil drop rate in step (2) drips the vitriol oil separately with drop rate, with water glass remaining in neutralization reaction medium, pH to reaction medium reaches 5.0 ~ 9.0, such as 5.5,6.0,6.5,7.0,7.5,8.0,8.5,9.0, preferably 7.0 ~ 8.0.Preferably, now stop dripping the vitriol oil separately, reaction medium is carried out ageing, the time of ageing is 15 ~ 120 minutes, such as 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, preferably 30 ~ 90 minutes.
After aging step terminates, continue to add the vitriol oil separately, the pH to reaction medium reaches 3.0 ~ 6.0, and such as 3.5,4.0,4.5,5.0,5.5, preferably 4.0 ~ 5.0.According to the present invention, now reaction medium can also be carried out ageing, the time of ageing is 15 ~ 120 minutes, such as 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, preferably 30 ~ 90 minutes.
According to the present invention, the preferred back ageing of two step ageings, namely the pH of preferred reaction medium reaches the ageing after 5.0 ~ 9.0, effectively can improve pore volume and the aperture of white carbon black.
After step (3) terminates, obtain silica suspension, then carry out press filtration and washing.
In the present invention, adopt membrane pressure filter to carry out filtering and washing, the pressure filter due to this structure has water pressing function, can guarantee that obtained filter cake solid content is more than 24.0wt%.
The filter cake obtained after filtration washing carries out pulp by multi-stage stirrer and wet wheeling machine again, obtains the suspension that solid content is more than 20.0wt%, preferably 21.0 ~ 23.0wt%.
In the present invention, appropriate water or additive can be added in slurrying process, meet solid content and viscosity is the silica suspension of 1000 ~ 2000cp to obtain.
In addition, in slurrying process, pH to 5.0 ~ 7.0 that sulfuric acid adjusts this suspension can also be added, preferably 5.5 ~ 6.5.
Described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces.
The preferred essential condition obtaining silicon-dioxide superperformance comprises: the concentration of sodium silicate of initial bed material, pH value, simultaneously dropping excess water glass and the vitriol oil, temperature of reaction, reaction times, digestion time, filtration, pulp and drying mode.
According to the present invention, dry what adopt is that pressure type is dry, acquisition be spherical microballon silicon-dioxide, its median D
50be at least 250 μm.
Described drying products carries out briquetting subsequently and makes particulate state (granulation) product.The microballon shape silicon-dioxide that drying obtains, directly can obtain particulate state granulated silica by tablets press, its size is at least the particulate state of 0.5mm, and pellet hardness is 10 ~ 40g.
Two of object of the present invention is to provide a kind of precipitated silica obtained by method described above, and its BET specific surface area is 185 ~ 235m
2/ g, CTAB are 165 ~ 205m
2/ g, pH value is 5.5 ~ 7.5, and pore volume is 1.65 ~ 2.25cm
3/ g, most probable pore size is 15 ~ 35nm, ultrasonic wave particle diameter D
50it is 6.0 ~ 10.0 μm.
Preferably, BET specific surface area is 190 ~ 210m
2/ g.
Preferably, CTAB is 165 ~ 185m
2/ g.
Preferably, pH value is 6.0 ~ 6.5.
Preferably, it is median D
50be at least 250 μm spherical.
Preferably, it is at least the particulate state of 0.5mm for size, and pellet hardness is 10 ~ 40g, preferably 15 ~ 25g.
Three of object of the present invention is the purposes providing a kind of precipitated silica as above as the strengthening agent of rubber tyre.
Compared with the prior art, the present invention has following beneficial effect:
What the present invention obtained is the precipitated silica with high specific surface area, and it has good dispersiveness and processibility in rubber tyre, and has high-wearing feature, effectively can reduce rolling resistance and the heat-dissipating of green tire and load-carrying tire.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
Embodiment 1
A kind of method preparing precipitated silica, described method comprises makes water glass and vitriol oil generation precipitin reaction, thus obtains the suspension of precipitated silica, afterwards through press filtration and washing, slurrying process this suspension dry, wherein, precipitin reaction is carried out as follows:
(1) prepare the initial bed material of precipitin reaction, the part wherein containing the water glass total amount used in described precipitin reaction, in described initial bed material, concentration of sodium silicate is with Na
2o is expressed as 0.05N, and pH is 9.0; With steam, initial bed material temperature is risen to 80 DEG C simultaneously;
(2) in described initial bed material, drip the vitriol oil and excess water glass simultaneously, make water glass and vitriol oil generation precipitin reaction; Add the time is 90 minutes simultaneously, guarantees that temperature of reaction 80 DEG C and concentration of sodium silicate are with Na at the same time in adding procedure
2o is expressed as 0.05N, pH be 9.0 constant.
(3), after the dropping vitriol oil and excess water glass terminate simultaneously, in reaction medium, the vitriol oil is dripped separately; Until pH is 4.0 ± 0.2.
Described press filtration and washing process comprise the filtration and washing operation that adopt membrane pressure filter to carry out the silica suspension that precipitin reaction is produced, formation filter cake;
Described slurrying process comprises employing multi-stage stirrer and wet wheeling machine liquefies to the filter cake that press filtration produces, and form silica suspension, the solid content of this suspension is 22wt%; And pH5.8.
Described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces.
The precipitated silica obtained by method described above, its BET specific surface area is 205m
2/ g, CTAB are 175m
2/ g, pH value is 6.15, and pore volume is 1.80cm
3/ g, most probable pore size is 30nm, ultrasonic wave particle diameter D
50it is 8.5 μm.
It can be median D
50be at least 250 μm spherical, also obtain by granulation the particulate state that size is at least 0.5mm, pellet hardness is 20.5g.
Embodiment 2
A kind of method preparing precipitated silica, described method comprises makes water glass and vitriol oil generation precipitin reaction, thus obtains the suspension of precipitated silica, afterwards through press filtration and washing, slurrying process this suspension dry, wherein, precipitin reaction is carried out as follows:
(1) prepare the initial bed material of precipitin reaction, the part wherein containing the water glass total amount used in described precipitin reaction, in described initial bed material, concentration of sodium silicate is with Na
2o is expressed as 0.05NpH; 9.0;
(2) in described initial bed material, drip the vitriol oil and excess water glass simultaneously, make water glass and vitriol oil generation precipitin reaction; Controlling temperature of reaction is 80 DEG C, and the reaction times is 120 minutes.
(3), after the dropping vitriol oil and excess water glass terminate simultaneously, in reaction medium, the vitriol oil is dripped separately; Until pH is 4.0 ± 0.2;
Described press filtration and washing process comprise the filtration and washing operation that adopt membrane pressure filter to carry out the silica suspension that precipitin reaction is produced, formation filter cake;
Described slurrying process comprises employing multi-stage stirrer and wet wheeling machine liquefies to the filter cake that press filtration produces, and form silica suspension, the solid content of this suspension is 22.0wt%, pH is 5.90.
Described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces.
The precipitated silica obtained by method described above, its BET specific surface area is 195m
2/ g, CTAB are 170m
2/ g, pH value is 6.20, and pore volume is 1.87cm
3/ g, most probable pore size is 25.0nm, ultrasonic wave particle diameter D
50it is 7.8 μm.
It can be median D
50be at least 250 μm spherical, also obtain by granulation the particulate state that size is at least 0.5mm, pellet hardness is 20.8g.
Embodiment 3
A kind of method preparing precipitated silica, described method comprises makes water glass and vitriol oil generation precipitin reaction, thus obtains the suspension of precipitated silica, afterwards through press filtration and washing, slurrying process this suspension dry, wherein, precipitin reaction is carried out as follows:
(1) prepare the initial bed material of precipitin reaction, the part wherein containing the water glass total amount used in described precipitin reaction, in described initial bed material, concentration of sodium silicate is with Na
2o is expressed as 0.06N, and pH is 9.50;
(2) in described initial bed material, drip the vitriol oil and excess water glass in 90 minutes simultaneously, make water glass and vitriol oil generation precipitin reaction, wherein, in dropping process, control temperature of reaction is 80 DEG C; In addition, drip at the same time in the process of the vitriol oil and excess water glass, the pH remaining in the constant and reaction medium of temperature of reaction be 9.0 ~ 11.0 stable;
(3) after the dropping vitriol oil and excess water glass terminate simultaneously, be that drop rate about the half of vitriol oil drop rate in step (2) drips the vitriol oil separately with drop rate, with water glass remaining in neutralization reaction medium, pH to reaction medium reaches 5.0, now stops dripping the vitriol oil separately, and reaction medium is carried out ageing, the time of ageing is 30 minutes, after aging step terminates, continue to add the vitriol oil separately, the pH to reaction medium reaches 3.0;
Described press filtration and washing process comprise the filtration and washing operation that adopt membrane pressure filter to carry out the silica suspension that precipitin reaction is produced, formation filter cake;
Described slurrying process comprises employing multi-stage stirrer and wet wheeling machine liquefies to the filter cake that press filtration produces, and form silica suspension, the solid content of this suspension is 22.6wt%, pH is 6.0.
Described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces.
The precipitated silica obtained by method described above, its BET specific surface area is 196m
2/ g, CTAB are 172m
2/ g, pH value is 6.45, and pore volume is 2.05cm
3/ g, most probable pore size is 32nm, ultrasonic wave particle diameter D
50it is 6.10 μm.
It can be median D
50be at least 250 μm spherical, also obtain by granulation the particulate state that size is at least 0.5mm, pellet hardness is 22.0g.
Embodiment 4
A kind of method preparing precipitated silica, described method comprises makes water glass and vitriol oil generation precipitin reaction, thus obtains the suspension of precipitated silica, afterwards through press filtration and washing, slurrying process this suspension dry, wherein, precipitin reaction is carried out as follows:
(1) prepare the initial bed material of precipitin reaction, the part wherein containing the water glass total amount used in described precipitin reaction, in described initial bed material, concentration of sodium silicate is with Na
2o is expressed as 0.06N, and pH is 9.0;
(2) in described initial bed material, in 120 minutes, drip the vitriol oil and excess water glass simultaneously, make water glass and vitriol oil generation precipitin reaction, wherein, in dropping process, first control temperature of reaction be 76 DEG C after one hour, be warming up to 90 DEG C; In addition, drip at the same time in the process of the vitriol oil and excess water glass, the pH remaining in the constant and reaction medium of temperature of reaction be 9.0 ~ 11.0 stable;
(3) after the dropping vitriol oil and excess water glass terminate simultaneously, be that drop rate about the half of vitriol oil drop rate in step (2) drips the vitriol oil separately with drop rate, with water glass remaining in neutralization reaction medium, pH to reaction medium reaches 5.0, now stop dripping the vitriol oil separately, reaction medium is carried out ageing, and the time of ageing is 30 minutes.
Described press filtration and washing process comprise the filtration and washing operation that adopt membrane pressure filter to carry out the silica suspension that precipitin reaction is produced, formation filter cake;
Described slurrying process comprises employing multi-stage stirrer and wet wheeling machine liquefies to the filter cake that press filtration produces, and form silica suspension, the solid content of this suspension is 21.5%, pH is 6.25.
Described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces.
The precipitated silica obtained by method described above, its BET specific surface area is 195m
2/ g, CTAB are 170m
2/ g, pH value is 6.70, and pore volume is 1.75cm
3/ g, most probable pore size is 24.0nm, ultrasonic wave particle diameter D
50it is 6.8 μm.
It can be median D
50be at least 250 μm spherical, also obtain by granulation the particulate state that size is at least 0.5mm, pellet hardness is 18.0g.
Embodiment 5
A kind of method preparing precipitated silica, described method comprises makes water glass and vitriol oil generation precipitin reaction, thus obtains the suspension of precipitated silica, afterwards through press filtration and washing, slurrying process this suspension dry, wherein, precipitin reaction is carried out as follows:
(1) prepare the initial bed material of precipitin reaction, the part wherein containing the water glass total amount used in described precipitin reaction, in described initial bed material, concentration of sodium silicate is with Na
2o is expressed as 0.06N, and pH is 9.0;
(2) in described initial bed material, drip the vitriol oil and excess water glass in 90 minutes simultaneously, make water glass and vitriol oil generation precipitin reaction, wherein, in dropping process, first controlling temperature of reaction is that 75 DEG C, after one hour, are warming up to 86 DEG C; In addition, drip at the same time in the process of the vitriol oil and excess water glass, the pH remaining in the constant and reaction medium of temperature of reaction be 9.0 ~ 11.0 stable;
(3) after the dropping vitriol oil and excess water glass terminate simultaneously, be that drop rate about the half of vitriol oil drop rate in step (2) drips the vitriol oil separately with drop rate, with water glass remaining in neutralization reaction medium, pH to reaction medium reaches 9.0, now stop dripping the vitriol oil separately, reaction medium is carried out ageing, and the time of ageing is, 30 minutes.
Described press filtration and washing process comprise the filtration and washing operation that adopt membrane pressure filter to carry out the silica suspension that precipitin reaction is produced, formation filter cake;
Described slurrying process comprises employing multi-stage stirrer and wet wheeling machine liquefies to the filter cake that press filtration produces, and form silica suspension, the solid content of this suspension is; 22.5wt%, pH are 6.0.
Described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces.
The precipitated silica obtained by method described above, its BET specific surface area is 200m
2/ g, CTAB are 190m
2/ g, pH value is 6.30, and pore volume is 1.90cm
3/ g, most probable pore size is 30nm, ultrasonic wave particle diameter D
50it is 6.2 μm.
It can be median D
50be at least 250 μm spherical, also obtain by granulation the particulate state that size is at least 0.5mm, pellet hardness is 25.0g.
In above-described embodiment 1 ~ 5, the concentration of excess water glass is with Na
2o is expressed as 2.30 ~ 2.70N.
In above-described embodiment 1 ~ 5, alternatively, appropriate water or additive can be added in slurrying process, to obtain the silica suspension meeting solid content and viscosity requirement.In addition, alternatively, pH to 5.0 ~ 7.0 that sulfuric acid adjusts this suspension can also be added.
Embodiment 6
Precipitated silica of the present invention has good dispersiveness and processibility in rubber tyre, and has high-wearing feature, effectively can reduce rolling resistance and the heat-dissipating of green tire and load-carrying tire.
| Title material | Embodiment 1 precipitated silica | Embodiment 2 precipitated silica |
| SSBR | 69.00 | 69.00 |
| NR | 19.00 | 19.00 |
| BR | 12.00 | 12.00 |
| Silica | 56.00 | 56.00 |
| SI-69 | 4.98 | 4.98 |
| HP130 | 6.00 | 6.00 |
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. prepare the method for precipitated silica for one kind, described method comprises makes water glass and vitriol oil generation precipitin reaction, thus obtains the suspension of precipitated silica, afterwards through press filtration and washing, slurrying process this suspension dry, wherein, precipitin reaction is carried out as follows:
(1) prepare the initial bed material of precipitin reaction, the part wherein containing the water glass total amount used in described precipitin reaction, in described initial bed material, concentration of sodium silicate is with Na
2o is expressed as 0.05 ~ 0.15N, and pH is 6.0 ~ 12.0;
(2) in described initial bed material, drip the vitriol oil and excess water glass simultaneously, make water glass and vitriol oil generation precipitin reaction;
(3), after dropping excess water glass and the vitriol oil terminate simultaneously, in reaction medium, the vitriol oil is dripped separately;
Described press filtration and washing process comprise the filtration and washing operation that adopt membrane pressure filter to carry out the silica suspension that precipitin reaction is produced, formation filter cake;
Described slurrying process comprises employing multi-stage stirrer and wet wheeling machine liquefies to the filter cake that press filtration produces, and form silica suspension, the solid content of this suspension is more than 20wt%.
2. the method for claim 1, is characterized in that, in step (1), described concentration of sodium silicate is with Na
2o is expressed as 0.06 ~ 0.08N;
Preferably, described pH is 9.0 ~ 11.0;
Preferably, described water glass finger print number is the water glass of 3.10 ~ 3.60.
3. method as claimed in claim 1 or 2, it is characterized in that, the time simultaneously dripping the vitriol oil and excess water glass in step (2) is 60 ~ 150 minutes, preferably 90 ~ 120 minutes;
Preferably, controlling temperature of reaction in step (2) is 60 ~ 90 DEG C, preferably 78 ~ 82 DEG C;
Preferably, drip at the same time in the process of the vitriol oil and excess water glass, remain that concentration of sodium silicate in the constant and reaction medium of temperature of reaction is with Na
2o be expressed as 0.06 ~ 0.08N or pH be 9.0 ~ 11.0 stable.
4. the method as described in one of claim 1-3, is characterized in that, step (3) drips in the process of the vitriol oil and excess water glass at the same time, and first controlling temperature of reaction is 70 ~ 80 DEG C, after one hour, is warming up to 80 ~ 90 DEG C;
Preferably, the concentration of described excess water glass is with Na
2o is expressed as 2.30 ~ 2.70N, preferably 2.40 ~ 2.50N.
5. the method as described in one of claim 1-4, is characterized in that, drip the vitriol oil separately with the drop rate of half in step (2), the pH to reaction medium reaches 5.0 ~ 9.0;
Preferably, after the pH of question response medium reaches 5.0 ~ 9.0, stop dripping the vitriol oil separately, reaction medium is carried out ageing, and the time of ageing is 15 ~ 120 minutes, preferably 30 ~ 90 minutes.
6. method as claimed in claim 5, is characterized in that, after ageing terminates, continue to add the vitriol oil separately, the pH to reaction medium reaches 3.0 ~ 6.0, preferably 4.0 ~ 5.0;
Preferably, after the pH of question response medium reaches 3.0 ~ 6.0, reaction medium is carried out ageing, and the time of ageing is 15 ~ 120 minutes, preferably 30 ~ 90 minutes.
7. the method as described in one of claim 1-6, is characterized in that, the solid content of suspension is 21.0 ~ 23.0wt%;
Preferably, in slurrying process, add water or additive, meet solid content and viscosity is the silica suspension of 1000 ~ 2000cp to obtain;
Preferably, in slurrying process, add pH to 5.0 ~ 7.0 of sulfuric acid adjustment suspension, preferably 5.5 ~ 6.5;
Preferably, drying products carries out briquetting subsequently and makes granular product.
8. the precipitated silica obtained by method as described in one of claim 1-7, its BET specific surface area is 185 ~ 235m
2/ g, CTAB are 165 ~ 205m
2/ g, pH value is 5.5 ~ 7.5, and pore volume is 1.65 ~ 2.25cm
3/ g, most probable pore size is 15 ~ 35nm, ultrasonic wave particle diameter D
50it is 6.0 ~ 10.0 μm.
9. precipitated silica as claimed in claim 8, it is characterized in that, BET specific surface area is 190 ~ 210m
2/ g;
Preferably, CTAB is 165 ~ 185m
2/ g;
Preferably, pH value is 6.0 ~ 6.5;
Preferably, it is median D
50be at least 250 μm spherical;
Preferably, it is at least the particulate state of 0.5mm for size, and pellet hardness is 10 ~ 40g, preferably 15 ~ 25g.
10. a precipitated silica as claimed in claim 8 or 9 is as the purposes of rubber tyre strengthening agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN106829976A (en) * | 2017-03-16 | 2017-06-13 | 福建省三明同晟化工有限公司 | A kind of preparation method of bigger serface, high oil absorption value precipitated silica |
| CN106865557A (en) * | 2017-02-10 | 2017-06-20 | 福建正盛无机材料股份有限公司 | A kind of preparation method of Tire used in winter white carbon |
| CN107055557A (en) * | 2017-05-04 | 2017-08-18 | 无锡恒诚硅业有限公司 | A kind of preparation method of the white carbon of controllable CTAB specific surface areas |
| CN108928827A (en) * | 2018-06-22 | 2018-12-04 | 确成硅化学股份有限公司 | A method of improving white carbon black specific surface area and Kong Rong |
| CN111484024A (en) * | 2020-04-14 | 2020-08-04 | 广州市飞雪材料科技有限公司 | Preparation method of silicon dioxide with low oil absorption value and high specific surface area |
| CN114634186A (en) * | 2020-12-16 | 2022-06-17 | 安徽进化硅纳米材料科技有限公司 | Preparation method of nano silicon dioxide dispersion liquid |
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| CN107697921B (en) * | 2017-10-30 | 2020-05-05 | 无锡恒诚硅业有限公司 | High-dispersity white carbon black and preparation method thereof |
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| CN106865557A (en) * | 2017-02-10 | 2017-06-20 | 福建正盛无机材料股份有限公司 | A kind of preparation method of Tire used in winter white carbon |
| CN106829976A (en) * | 2017-03-16 | 2017-06-13 | 福建省三明同晟化工有限公司 | A kind of preparation method of bigger serface, high oil absorption value precipitated silica |
| CN107055557A (en) * | 2017-05-04 | 2017-08-18 | 无锡恒诚硅业有限公司 | A kind of preparation method of the white carbon of controllable CTAB specific surface areas |
| CN107055557B (en) * | 2017-05-04 | 2020-02-07 | 无锡恒诚硅业有限公司 | Preparation method of white carbon black with adjustable CTAB specific surface area |
| CN108928827A (en) * | 2018-06-22 | 2018-12-04 | 确成硅化学股份有限公司 | A method of improving white carbon black specific surface area and Kong Rong |
| CN111484024A (en) * | 2020-04-14 | 2020-08-04 | 广州市飞雪材料科技有限公司 | Preparation method of silicon dioxide with low oil absorption value and high specific surface area |
| CN111484024B (en) * | 2020-04-14 | 2021-01-15 | 广州市飞雪材料科技有限公司 | Preparation method of silicon dioxide with low oil absorption value and high specific surface area |
| CN114634186A (en) * | 2020-12-16 | 2022-06-17 | 安徽进化硅纳米材料科技有限公司 | Preparation method of nano silicon dioxide dispersion liquid |
| CN114632469A (en) * | 2020-12-16 | 2022-06-17 | 安徽进化硅纳米材料科技有限公司 | Silicon dioxide granulation method and device |
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