CN104291345A - Precipitated silicon dioxide with low silanol, preparation method and use thereof - Google Patents
Precipitated silicon dioxide with low silanol, preparation method and use thereof Download PDFInfo
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- CN104291345A CN104291345A CN201410485999.3A CN201410485999A CN104291345A CN 104291345 A CN104291345 A CN 104291345A CN 201410485999 A CN201410485999 A CN 201410485999A CN 104291345 A CN104291345 A CN 104291345A
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Abstract
The invention relates to a novel method of precipitated silicon dioxide with low silanol and use thereof. The invention further relates to spherical microspherical silicon dioxide and granular pelletized silicon dioxide. The silanol density of the precipitated silicon dioxide is less than 4.0/nm<2>, the BET specific surface area is 100-235m<2>/g, the CTAB is 95-205m<2>/g, the pH value is 5.5-7.5, the pore volume is 1.65-2.25cm<3>/g, the ultrasonic grain size D50 is 1.0-10.0 microns, the water content is 4.0-8.0%, the conductivity is 800-1200 mu m/cm, and the water content is 4.0-8.0%. The precipitated silicon dioxide can be used as a rubber tire reinforcing agent.
Description
Technical field
The present invention relates to a kind of novel method of Low-silicone alcohol base precipitated silica.It also relates in spherical microballon silicon-dioxide and granular granulated silica.
Background technology
As you know, precipitated silica act as strengthening agent in rubber tyre, and particularly in green tire, its reduces the rolling resistance of tire, reduces heat-dissipating, improves wear resistance, thus reaches durable, energy-saving and cost-reducing object.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.
But, because silica sphere also exists the silanol base of some amount, when with compounding rubber, this silanol base is by the interaction such as liquid agent, promotor with rubber, thus reduce the dispersiveness of silicon-dioxide in rubber, the viscosity of rubber unvulcanizate can be added in addition and cause poor processability.
In order to obtain the object of best reinforcing effect and good processing characteristics by adding precipitated silica, improving production capacity and reducing energy consumption, the silanol base density of precipitated silica silicon face must be reduced.
Summary of the invention
For the problem of prior art, the invention provides and a kind ofly prepare the novel method with Low-silicone alcohol base precipitated silica, the precipitated silica adopting the method to obtain has good dispersiveness and processibility in rubber tyre, effectively can reduce rolling resistance and the heat-dissipating of green tire, improve wear resistance.
To achieve these goals, present invention employs following technical scheme:
A kind ofly prepare the method with Low-silicone alcohol base precipitated silica, described method comprises makes water glass and sulfuric acid 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) in water glass thinning tank, the water glass dissolved is added water and dilutes, be diluted to concentration with Na
2o is expressed as the water glass of 2.30 ~ 2.70N, the modulus of described water glass (SiO in water glass
2with Na
2the mol ratio of O) be 3.5 ~ 4.0;
(2) the initial bed material of precipitin reaction prepared by the water glass added in reactor after water and step (1) dilution, wherein initial bed material contains a part for the water glass total amount used in described precipitin reaction, steam is passed in reactor, the temperature controlling initial bed material is 75 ~ 98 DEG C, and to adjust in initial bed material concentration of sodium silicate with Na
2it is 8.0 ~ 11.0 that O is expressed as 0.04 ~ 0.08N or pH;
(3) in described initial bed material in 90 ~ 180 minutes, drip sulfuric acid and precipitin reaction excess water glass used simultaneously, make water glass and vitriol oil generation precipitin reaction, in whole process, ensure that the temperature of reaction medium and concentration of sodium silicate are with Na all the time
2o be expressed as 0.04 ~ 0.08N or pH be 8.0 ~ 11.0 stable;
(4), after dropping excess water glass and sulfuric acid terminate simultaneously, in reaction medium, sulfuric acid is dripped separately.
In the present invention, the essential condition reducing precipitated silica surface silanol groups content comprises: the time 90-180 minute of the modulus of water glass 3.5 ~ 4.0 that reaction uses and simultaneously dropping sulfuric acid and excess water glass.
Preferably, the preparation method of the water glass dissolved in step (1) is:
By modulus be 3.5 ~ 4.0 solid water glass and water by weight joining in dissolution kettle for the ratio of 1.0:2.0, then directly passing into steam to pressure is 0.30 ~ 0.50MPa, after reaching pressure, stop adding steam, start insulation, soaking time is 2.0 ~ 4.0 hours, and solid water glass is dissolved into liquid soluble glass, obtains the water glass dissolved.
In the present invention, the modulus of solid water glass is 3.5 ~ 4.0, such as 3.60,3.70,3.80 or 3.90.
In the present invention, the weight ratio of solid water glass and water is 1.0:2.0.
In the present invention, soaking time is 2.0 ~ 4.0 hours, such as 2.0 hours, 2.5 hours, 3 hours, 3.5 hours, 4.0 hours, preferably 3.0 hours.
Preferably, the concentration of sodium silicate that described dissolving is good counts 30 ~ 38Be ° with degree Beaume, preferred 35Be °.
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), and object provides stable reaction conditions (certain Na for second step drips
2o concentration or pH value), guarantee the Na when second time drips the vitriol oil and excess water glass simultaneously
2the concentration of O or the stability contorting of pH value.
In the present invention, in step (1), concentration is diluted to Na
2o is expressed as 2.30 ~ 2.70N (such as 2.35N, 2.40N, 2.47N, 2.55N, 2.60N, 2.65N or 2.70N.Water glass, be preferably diluted to concentration with Na
2o is expressed as the water glass of 2.40 ~ 2.50N.
In the present invention, in step (1), the modulus of water glass is 3.5 ~ 4.0, such as 3.60,3.70,3.80 or 3.90.
In the present invention, the temperature controlling initial bed material in step (2) is 75 ~ 98 DEG C, such as 76 DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 84 DEG C, 86 DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 94 DEG C, 96 DEG C or 98 DEG C.
In the present invention, step (2) to adjust in initial bed material concentration of sodium silicate with Na
2o is expressed as 0.04 ~ 0.08N, such as 0.04N, 0.05N, 0.06N, 0.07N or 0.08N, and pH is 8.0 ~ 11.0, and such as 8.0,8.5,9.0,9.5,10.0 or 10.5.
In the present invention, step (3) in described initial bed material in 90 ~ 180 minutes (such as 90,120 minutes, 150 minutes or 180 minutes), preferably in 120 ~ 150 minutes, drip sulfuric acid and precipitin reaction excess water glass used simultaneously, preferably in 120 ~ 150 minutes, drip sulfuric acid and precipitin reaction excess water glass used simultaneously.
In the present invention, in whole process, ensure in step (3) that the temperature of reaction medium and concentration of sodium silicate are with Na all the time
2it is the stable of 8.0 ~ 11.0 (such as 8.0,8.5,9.0,9.5,10.0 or 10.5) that O is expressed as 0.04 ~ 0.08N (such as 0.04N, 0.05N, 0.06N, 0.07N or 0.08N) or pH
In the present invention, the concentration of excess water glass is with Na
2o is expressed as 2.30 ~ 2.70N, such as 2.35N, 2.40N, 2.47N, 2.55N, 2.60N, 2.65N or 2.70N.Preferably, after dropping excess water glass and sulfuric acid terminate simultaneously, drip sulfuric acid separately again after 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 or 105 minutes, preferably 30 ~ 90 minutes.
Step drips sulfuric acid separately in (4) in reaction medium, water glass remaining in neutralization reaction medium, and the pH to reaction medium reaches 3.0 ~ 6.0, and such as 3.6,4,4.4,5 or 5.6, preferably 4.0 ~ 5.0.
Preferably, drip after excess water glass and sulfuric acid terminates, drip sulfuric acid separately with the drop rate about half in step (3), the pH to reaction medium reaches 3.0 ~ 6.0 simultaneously, and such as 3.6,4.0,4.4,5.0 or 5.6, preferably 4.0 ~ 5.0.After the pH of question response medium reaches 3.0 ~ 6.0, stop dripping the vitriol oil separately, reaction medium is carried out ageing, and the time of ageing is 15 ~ 120 minutes, such as 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes or 105 minutes, preferably 30 ~ 90 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 20 ~ 24wt%, pH is 5.50 ~ 6.50.
Described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces.Its dry feed pressure is 16.0 ~ 50.0bar, preferably 18 ~ 40bar; The moisture of final drying products is 4.0 ~ 8.0%, preferably 5.0 ~ 7.0%.
Described drying products can carry out briquetting subsequently and make particulate state (granulation) product.
In the present invention, the described vitriol oil refers to that massfraction is the sulfuric acid of 98%.
In the present invention, described " Low-silicone alcohol base " refers to, silanol base density < 4.0/nm
2, preferred < 2.0/nm
2.
Two of object of the present invention be to provide a kind of obtained by method described above there is Low-silicone alcohol base precipitated silica, it
Silanol base density < 4.0/nm
2;
BET specific surface area is 100 ~ 235m
2/ g;
CTAB is 95 ~ 205m
2/ g;
PH value is 5.5 ~ 7.5;
Pore volume is 1.65 ~ 2.25cm
3/ g;
Ultrasonic wave particle diameter D
50it is 1.0 ~ 10.0 μm;
Moisture is 4.0 ~ 8.0%;
Specific conductivity is 800 ~ 1200 μm/cm.
Preferably, silanol base density < 2.0/nm
2.
Preferably, pH value is 6.0 ~ 7.0.
Preferably, moisture is 5.0 ~ 7.0%.
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 ~ 45g, preferably 15 ~ 30g.
Three of object of the present invention is the purposes providing a kind of precipitated silica as above as strengthening agent, preferably as the purposes of rubber tyre strengthening agent.
Compared with the prior art, the present invention has following beneficial effect:
What the present invention obtained is the precipitated silica with Low-silicone alcohol base density, and what its showed is in rubber tyre, have good dispersiveness and processibility, effectively can reduce rolling resistance and the heat-dissipating of green tire, improves wear resistance.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
Embodiment 1
By modulus be 3.6 solid water glass and water by weight joining in dissolution kettle for the ratio of 1.0:2.0, then directly passing into steam to pressure is 0.30MPa, after reaching pressure, stop adding steam, start insulation, soaking time is 2.0 hours, and solid water glass is dissolved into liquid soluble glass, obtains the water glass dissolved;
In water glass thinning tank, the water glass dissolved is added water and dilutes, be diluted to concentration with Na
2o is expressed as the water glass of 2.35N, and the modulus of described water glass is 3.6;
The initial bed material of precipitin reaction prepared by the water glass added in reactor after water and dilution, wherein initial bed material contains a part for the water glass total amount used in described precipitin reaction, steam is passed in reactor, the temperature controlling initial bed material is 75 DEG C, and to adjust in initial bed material concentration of sodium silicate with Na
2it is 8.0 that O is expressed as 0.05N or pH;
In described initial bed material in 120 minutes, drip sulfuric acid and precipitin reaction excess water glass used simultaneously, make water glass and vitriol oil generation precipitin reaction, in whole process, ensure that the temperature of reaction medium and concentration of sodium silicate are with Na all the time
2o is expressed as the stable of 0.05N;
After dropping excess water glass and sulfuric acid terminate simultaneously, in reaction medium, drip sulfuric acid separately with the drop rate about aforementioned half, be 3.6 to reaction medium pH;
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 20wt%, pH is 5.50.
Described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces, and its dry feed pressure is 16.0bar.
What obtained by method described above has Low-silicone alcohol base precipitated silica, its silanol base 2.55/nm
2; BET specific surface area is 225m
2/ g; CTAB is 176m
2/ g; PH value is 6.0; Pore volume is 1.70cm
3/ g; Ultrasonic wave particle diameter D
50it is 9.8 μm; Moisture 5.6 is %; Specific conductivity is 1065 μm/cm.
Embodiment 2
By modulus be 4.0 solid water glass and water by weight joining in dissolution kettle for the ratio of 1.0:2.0, then directly passing into steam to pressure is 0.50MPa, after reaching pressure, stop adding steam, start insulation, soaking time is 4.0 hours, and solid water glass is dissolved into liquid soluble glass, obtains the water glass dissolved;
In water glass thinning tank, the water glass dissolved is added water and dilutes, be diluted to concentration with Na
2o is expressed as the water glass of 2.47N, and the modulus of described water glass is 4.0;
The initial bed material of precipitin reaction prepared by the water glass added in reactor after water and dilution, wherein initial bed material contains a part for the water glass total amount used in described precipitin reaction, steam is passed in reactor, the temperature controlling initial bed material is 98 DEG C, and to adjust in initial bed material concentration of sodium silicate with Na
2o is expressed as 0.07N or pH10.0;
In described initial bed material in 120 minutes, drip sulfuric acid and precipitin reaction excess water glass used simultaneously, make water glass and vitriol oil generation precipitin reaction, in whole process, ensure that the temperature of reaction medium and concentration of sodium silicate are with Na all the time
2o be expressed as 0.07N or pH be 10.0 stable;
After dropping excess water glass and sulfuric acid terminate simultaneously, in reaction medium, dripping separately sulfuric acid with the drop rate of aforementioned half drip sulfuric acid separately, is 4.0 to reaction medium pH;
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 24wt%, pH is 6.50.
Described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces, and its dry feed pressure is 50.0bar.
What obtained by method described above has Low-silicone alcohol base precipitated silica, its silanol based 1.5/nm
2; BET specific surface area is 115m
2/ g; CTAB is 110m
2/ g; PH value is 7.0; Pore volume is 2.20cm
3/ g; Ultrasonic wave particle diameter D
50it is 2.05 μm; Moisture is 6.2%; Specific conductivity is 850 μm/cm.
Embodiment 3
By modulus be 3.8 solid water glass and water by weight joining in dissolution kettle for the ratio of 1:2.0, then directly passing into steam to pressure is 0.40MPa, after reaching pressure, stop adding steam, start insulation, soaking time is 3 hours, and solid water glass is dissolved into liquid soluble glass, obtains the water glass dissolved;
In water glass thinning tank, the water glass dissolved is added water and dilutes, be diluted to concentration with Na
2o is expressed as the water glass of 2.50N, and the modulus of described water glass is 3.8;
The initial bed material of precipitin reaction prepared by the water glass added in reactor after water and dilution, wherein initial bed material contains a part for the water glass total amount used in described precipitin reaction, steam is passed in reactor, the temperature controlling initial bed material is 85 DEG C, and to adjust in initial bed material concentration of sodium silicate with Na
2it is 9.5 that O is expressed as 0.06N or pH;
In described initial bed material in 150 minutes, drip sulfuric acid and precipitin reaction excess water glass used simultaneously, make water glass and vitriol oil generation precipitin reaction, in whole process, ensure that the temperature of reaction medium and concentration of sodium silicate are with Na all the time
2o be expressed as 0.06N or pH be 9.5 stable;
After dropping excess water glass and sulfuric acid terminate simultaneously, in reaction medium, drip sulfuric acid separately with the drop rate about aforementioned half, be 4.0 to reaction medium pH;
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%, pH is 6.
Described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces, and its dry feed pressure is 30bar.
What obtained by method described above has Low-silicone alcohol base precipitated silica, its silanol base 1.86/nm
2; BET specific surface area is 165m
2/ g; CTAB is 160m
2/ g; PH value is 6.5; Pore volume is 1.98cm
3/ g; Ultrasonic wave particle diameter D
50it is 3.50 μm; Moisture is 5.9%; Specific conductivity is 952 μm/cm.
Embodiment 4
By modulus be 3.6 solid water glass and water by weight joining in dissolution kettle for the ratio of 1.0:2.0, then directly passing into steam to pressure is 0.30MPa, after reaching pressure, stop adding steam, start insulation, soaking time is 2.0 hours, and solid water glass is dissolved into liquid soluble glass, obtains the water glass dissolved;
In water glass thinning tank, the water glass dissolved is added water and dilutes, be diluted to concentration with Na
2o is expressed as the water glass of 2.45N, and the modulus of described water glass is 3.6;
The initial bed material of precipitin reaction prepared by the water glass added in reactor after water and dilution, wherein initial bed material contains a part for the water glass total amount used in described precipitin reaction, steam is passed in reactor, the temperature controlling initial bed material is 85 DEG C, and to adjust in initial bed material concentration of sodium silicate with Na
2it is 11.0 that O is expressed as 0.08N or pH;
In described initial bed material in 120 minutes, drip sulfuric acid and precipitin reaction excess water glass used simultaneously, make water glass and vitriol oil generation precipitin reaction, in whole process, ensure that the temperature of reaction medium and concentration of sodium silicate are with Na all the time
2o is expressed as the stable of 0.08N;
After dropping excess water glass and sulfuric acid terminate simultaneously, drip sulfuric acid separately again after reaction medium is carried out ageing, the time of ageing is 30 minutes, then in reaction medium, drips sulfuric acid separately, is 4.0 to reaction medium pH
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 20wt%, pH is 5.50.
Described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces.Its dry feed pressure is 18.0bar
What obtained by method described above has Low-silicone alcohol base precipitated silica, its silanol base 1.72/nm
2; BET specific surface area is 168m
2/ g; CTAB is 162m
2/ g; PH value is 6.0; Pore volume is 1.95cm
3/ g; Ultrasonic wave particle diameter D
50it is 3.5 μm; Moisture is 5.6%; Specific conductivity is 1050 μm/cm.
Embodiment 5
By modulus be 3.9 solid water glass and water by weight joining in dissolution kettle for the ratio of 1.0:2.0, then directly passing into steam to pressure is 0.30MPa, after reaching pressure, stop adding steam, start insulation, soaking time is 2.0 hours, and solid water glass is dissolved into liquid soluble glass, obtains the water glass dissolved;
In water glass thinning tank, the water glass dissolved is added water and dilutes, be diluted to concentration with Na
2o is expressed as the water glass of 2.47N, and the modulus of described water glass is 3.9;
The initial bed material of precipitin reaction prepared by the water glass added in reactor after water and dilution, wherein initial bed material contains a part for the water glass total amount used in described precipitin reaction, steam is passed in reactor, the temperature controlling initial bed material is 84 DEG C, and to adjust in initial bed material concentration of sodium silicate with Na
2it is 10.0 that O is expressed as 0.07N or pH;
In described initial bed material in 105 minutes, drip sulfuric acid and precipitin reaction excess water glass used simultaneously, make water glass and vitriol oil generation precipitin reaction, in whole process, ensure that the temperature of reaction medium and concentration of sodium silicate are with Na all the time
2o is expressed as the stable of 0.07N;
After dropping excess water glass and sulfuric acid terminate simultaneously, drip sulfuric acid separately again after reaction medium is carried out ageing, the time of ageing is 30 minutes, then in reaction medium, drips sulfuric acid separately, is 4.5 to reaction medium pH
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 20wt%, 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.Its dry feed pressure is 20.0bar.
What obtained by method described above has Low-silicone alcohol base precipitated silica, its silanol base 1.80/nm
2; BET specific surface area is 170m
2/ g; CTAB is 160m
2/ g; PH value is 6.5; Pore volume is 2.15cm
3/ g; Ultrasonic wave particle diameter D
50it is 4.2 μm; Moisture is 5.6%; Specific conductivity is 670 μm/cm.
Embodiment 6
What the present invention obtained is the precipitated silica with Low-silicone alcohol base, and what its showed is in rubber tyre, have good dispersiveness and processibility, effectively can reduce rolling resistance and the heat-dissipating of green tire, improves wear resistance.
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 with Low-silicone alcohol base precipitated silica for one kind, described method comprises makes water glass and sulfuric acid generation precipitin reaction, thus obtain 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) in water glass thinning tank, the water glass dissolved is added water and dilutes, be diluted to concentration with Na
2o is expressed as the water glass of 2.30 ~ 2.70N, and the modulus of described water glass is 3.5 ~ 4.0;
(2) the initial bed material of precipitin reaction prepared by the water glass added in reactor after water and step (1) dilution, wherein initial bed material contains a part for the water glass total amount used in described precipitin reaction, steam is passed in reactor, the temperature controlling initial bed material is 75 ~ 98 DEG C, and to adjust in initial bed material concentration of sodium silicate with Na
2o is expressed as 0.04 ~ 0.08N, or pH is 8.0 ~ 11.0;
(3) in described initial bed material in 90 ~ 180 minutes, drip sulfuric acid and precipitin reaction excess water glass used simultaneously, make water glass and vitriol oil generation precipitin reaction, in whole process, ensure that the temperature of reaction medium and concentration of sodium silicate are with Na all the time
2o be expressed as 0.04 ~ 0.08N or pH be 8.0 ~ 11.0 stable;
(4), after dropping excess water glass and sulfuric acid terminate simultaneously, in reaction medium, sulfuric acid is dripped separately.
2. the method for claim 1, is characterized in that, the preparation method of the water glass dissolved in step (1) is:
By modulus be 3.5 ~ 4.0 solid water glass and water by weight joining in dissolution kettle for the ratio of 1.0:2.0, then directly passing into steam to pressure is 0.30 ~ 0.50MPa, after reaching pressure, stop adding steam, start insulation, soaking time is 2.0 ~ 4.0 hours, and solid water glass is dissolved into liquid soluble glass, obtains the water glass dissolved.
3. method as claimed in claim 2, it is characterized in that, the modulus of solid water glass is 3.5 ~ 4.0;
Preferably, soaking time is 3.0 hours;
Preferably, the concentration of sodium silicate that described dissolving is good counts 30 ~ 38Be ° with degree Beaume, preferably 35 Be °.
4. the method as described in one of claim 1-3, is characterized in that, in step (1), is diluted to concentration with Na
2o is expressed as the water glass of 2.40 ~ 2.50N;
Preferably, in step (1), the modulus of water glass is 3.5 ~ 4.0;
Preferably, step (2) to adjust in initial bed material concentration of sodium silicate with Na
2it is 8.0 ~ 11.0 that O is expressed as 0.04 ~ 0.08N or pH.
5. the method as described in one of claim 1-4, is characterized in that, step (3), in 90 ~ 180 minutes, preferably in 120 ~ 150 minutes, drips sulfuric acid and precipitin reaction excess water glass used simultaneously;
Preferably, in whole process, ensure in step (3) that the temperature of reaction medium and concentration of sodium silicate are with Na all the time
2o be expressed as 0.04 ~ 0.08N or pH be 8.0 ~ 11.0 stable;
Preferably, after dropping excess water glass and sulfuric acid terminate simultaneously, drip sulfuric acid separately again after reaction medium is carried out ageing, the time of ageing is 15 ~ 120 minutes, preferably 30 ~ 90 minutes;
Preferably, step drips sulfuric acid separately in (4) in reaction medium, and the pH to reaction medium reaches 3.0 ~ 6.0, and preferably 4.0 ~ 5.0;
Preferably, drip after excess water glass and sulfuric acid terminates, drip sulfuric acid separately with the drop rate of half in step (3), the pH to reaction medium reaches 3.0 ~ 6.0 simultaneously, and preferably 4.0 ~ 5.0;
Preferably, after in step (4), the pH of question response medium reaches 3.0 ~ 6.0, 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. the method as described in one of claim 1-5, is characterized in that, 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;
Preferably, 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 20 ~ 24wt%, pH is 5.50 ~ 6.50;
Preferably, described drying process is exactly carry out drying by pressure-type spray day with fog to the suspension that pulp produces, and its dry feed pressure is 16.0 ~ 50.0bar, preferably 18 ~ 40bar.
7. what prepared by the described method of one of claim 1-6 has a Low-silicone alcohol base precipitated silica, it:
Silanol base density < 4.0/nm
2;
BET specific surface area is 100 ~ 235m
2/ g;
CTAB is 95 ~ 205m
2/ g;
PH value is 5.5 ~ 7.5;
Pore volume is 1.65 ~ 2.25cm
3/ g;
Ultrasonic wave particle diameter D
50it is 1.0 ~ 10.0 μm;
Moisture is 4.0 ~ 8.0%;
Specific conductivity is 800 ~ 1200 μm/cm.
8. precipitated silica as claimed in claim 7, is characterized in that, silanol base density < 2.0/nm
2.
Preferably, pH value is 6.0 ~ 7.0;
Preferably, moisture is 5.0 ~ 7.0%;
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 ~ 45g, preferably 15 ~ 30g.
9. a precipitated silica as claimed in claim 7 or 8 is as the purposes of strengthening agent.
10. purposes as claimed in claim 9, it is characterized in that, precipitated silica is as rubber tyre strengthening agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410485999.3A CN104291345B (en) | 2014-09-22 | 2014-09-22 | Precipitated silicon dioxide with low silanol, preparation method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410485999.3A CN104291345B (en) | 2014-09-22 | 2014-09-22 | Precipitated silicon dioxide with low silanol, preparation method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104291345A true CN104291345A (en) | 2015-01-21 |
| CN104291345B CN104291345B (en) | 2017-01-25 |
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| CN106829977A (en) * | 2017-03-30 | 2017-06-13 | 福建正盛无机材料股份有限公司 | A kind of preparation method of high oil absorption high-dispersion white carbon black |
| 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 |
| CN106986348A (en) * | 2017-05-04 | 2017-07-28 | 无锡恒诚硅业有限公司 | A kind of white carbon of low hydroxy radical content and preparation method thereof |
| 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 |
| CN108439414A (en) * | 2018-02-11 | 2018-08-24 | 确成硅化学股份有限公司 | A kind of method that pH value swing method prepares high dispersive macropore appearance precipitated silica |
| CN110156032A (en) * | 2019-07-01 | 2019-08-23 | 福建正盛无机材料股份有限公司 | A kind of preparation method of high yellowing-resistant silicon rubber white carbon black |
| CN110835110A (en) * | 2019-12-12 | 2020-02-25 | 通化双龙硅材料科技有限公司 | Preparation method of precipitated hydrated silicon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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| CN106986348A (en) * | 2017-05-04 | 2017-07-28 | 无锡恒诚硅业有限公司 | A kind of white carbon of low hydroxy radical content and preparation method thereof |
| 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 |
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| CN110156032A (en) * | 2019-07-01 | 2019-08-23 | 福建正盛无机材料股份有限公司 | A kind of preparation method of high yellowing-resistant silicon rubber white carbon black |
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| CN110835110A (en) * | 2019-12-12 | 2020-02-25 | 通化双龙硅材料科技有限公司 | Preparation method of precipitated hydrated silicon dioxide |
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