CN104291345B - 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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- CN104291345B CN104291345B CN201410485999.3A CN201410485999A CN104291345B CN 104291345 B CN104291345 B CN 104291345B CN 201410485999 A CN201410485999 A CN 201410485999A CN 104291345 B CN104291345 B CN 104291345B
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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 new method of Low-silicone alcohol base precipitated silica.It further relates in spherical microballon titanium dioxide
Silicon and granular granulated silica.
Background technology
It is equally known that precipitated silica act as reinforcing agent in rubber tyre, particularly in green tire, it
Reducing the rolling resistance of tire, reduce heat, improving wearability, thus reaching durable, energy-saving purpose.With European Union's mark
The enforcement of label method and environment increasingly serious, usage amount in rubber tyre for the precipitated silica is increasing.With other
Any supporting material is the same, and on the one hand it is easy to process, and on the other hand it will be easy to and rubber mix.
But, because silica surface has a number of silanol base, when with compounding rubber, this silanol base will
Interacting with the fluidizing reagent of rubber, accelerator etc., thus reducing dispersibility in rubber for the silicon dioxide, in addition can increase
The viscosity of elastomeric compound and lead to poor processability.
In order to obtain the purpose of optimal reinforcing effect and good processing characteristics by adding precipitated silica, improve and produce
Can be with reducing energy consumption it is necessary to reduce the silanol base density of precipitated silica silicon face.
Content of the invention
For the problem of prior art, the invention provides a kind of prepare the new side with Low-silicone alcohol base precipitated silica
Method, the precipitated silica being obtained using the method has good dispersibility and processability in rubber tyre, can be effective
Reduce rolling resistance and the heat of green tire, improve wearability.
To achieve these goals, present invention employs following technical scheme:
A kind of prepare the method with Low-silicone alcohol base precipitated silica, methods described includes making waterglass to occur with sulphuric acid
Precipitation, thus obtaining the suspension of precipitated silica, afterwards through filter pressing and washing, slurrying process and this suspension is dried
Liquid, wherein, carries out precipitation as follows:
(1) in waterglass thinning tank, the waterglass having dissolved is added water and is diluted, be diluted to concentration with na2O represents
Waterglass for 2.30～2.70n, the modulus (sio in waterglass of described waterglass2With na2The mol ratio of o) it is 3.5～4.0；
(2) add the waterglass preparation precipitation initial bed charge after water and step (1) dilution in reactor, wherein just
Beginning bed material contains a part for waterglass total amount used in described precipitation, is passed through steam in reactor, controls just
The temperature of beginning bed material is 75～98 DEG C, and adjusts in initial bed charge concentration of sodium silicate with na2O is expressed as 0.04～0.08n or ph
For 8.0～11.0；
(3) in described initial bed charge in 90～180 minutes, it is simultaneously added dropwise the excess water used by sulphuric acid and precipitation
Glass, makes waterglass, with concentrated sulphuric acid, precipitation occur, is always ensured that temperature and the waterglass of reaction medium in whole process
Concentration is with na2It is 8.0～11.0 stablize that o is expressed as 0.04～0.08n or ph；
(4) it is simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, the independent Deca sulphuric acid in reaction medium.
In the present invention, the essential condition reducing precipitated silica surface silanol groups content includes: the water that reaction uses
Glass modulus 3.5～4.0 and the time 90-180 minute being simultaneously added dropwise sulphuric acid and surplus waterglass.
Preferably, the preparation method of the waterglass having dissolved in step (1) is:
By modulus be 3.5～4.0 solid water glass and water be added to dissolution kettle by weight ratio for 1.0:2.0
In, being then passed directly into steam to pressure is 0.30～0.50mpa, after reaching pressure, stops adding steam, starts to be incubated, protect
The warm time is 2.0～4.0 hours, solid water glass is dissolved into liquid soluble glass, obtains the waterglass having 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 of solid water glass and water is than for 1.0:2.0.
In the present invention, temperature retention time be 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 described concentration of sodium silicate having dissolved is calculated as 30～38be ° with Baume degrees, preferably 35be °.
In the present invention, waterglass Deca at twice, is to prepare reaction initial bed charge for the first time, only independent Deca waterglass
(not Deca acid) is it is therefore an objective to provide stable reaction condition (certain na for second step Deca2O concentration or ph value), really
Protect the na when being simultaneously added dropwise concentrated sulphuric acid and surplus waterglass for the second time2The concentration of o or the stability contorting of ph value.
In the present invention, in step (1), it is diluted to concentration with na2O be expressed as 2.30～2.70n (such as 2.35n,
2.40n, 2.47n, 2.55n, 2.60n, 2.65n or 2.70n.Waterglass, be preferably diluted to concentration with na2O is expressed as 2.40
The waterglass of～2.50n.
In the present invention, in step (1), the modulus of waterglass 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 charge 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) adjustment initial bed charge, concentration of sodium silicate is with na2O is expressed as 0.04～0.08n, for example
0.04n, 0.05n, 0.06n, 0.07n or 0.08n, ph is 8.0～11.0, 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 charge at 90～180 minutes (such as 90,120 minutes, 150 points
Clock or 180 minutes) in, in preferably 120～150 minutes, it is simultaneously added dropwise the surplus waterglass used by sulphuric acid and precipitation, preferably
In 120～150 minutes, it is simultaneously added dropwise the surplus waterglass used by sulphuric acid and precipitation.
In the present invention, be always ensured that in whole process in step (3) temperature of reaction medium and concentration of sodium silicate with
na2O is expressed as 0.04～0.08n (such as 0.04n, 0.05n, 0.06n, 0.07n or 0.08n) or ph for 8.0～11.0 (for example
8.0th, 8.5,9.0,9.5,10.0 or 10.5) stablize
In the present invention, the concentration of surplus waterglass is with na2O 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, it is simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, reaction is situated between
Matter be aged after independent Deca sulphuric acid again, 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.
In step (4) in reaction medium independent Deca sulphuric acid, remaining waterglass in neutralization reaction medium, be situated between to reaction
The ph of matter reaches 3.0～6.0, such as 3.6,4,4.4,5 or 5.6, and preferably 4.0～5.0.
Preferably, it is simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, with the drop rate list about half in step (3)
Solely Deca sulphuric acid, the ph to reaction medium reaches 3.0～6.0, such as 3.6,4.0,4.4,5.0 or 5.6, and preferably 4.0～5.0.
After the ph of question response medium reaches 3.0～6.0, stop independent Deca concentrated sulphuric acid, reaction medium is aged, the time of ageing
For 15～120 minutes, such as 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes or 105 minutes, preferably 30～90 points
Clock.
Described filter pressing and washing process include silica suspension precipitation being produced using membrane pressure filter
The filtration carrying out and washing operation, form filter cake.
The filter cake that described slurrying process is included using multi-stage stirrer and wet milk produce to filter pressing liquefies, and forms two
Oxidation silicon suspension, the solid content of this suspension is 20～24wt%, and ph is 5.50～6.50.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp.Its dry feed
Pressure is 16.0～50.0bar, preferably 18～40bar；The moisture of final dry products is 4.0～8.0%, preferably 5.0～
7.0%.
Described dry products subsequently can carry out briquetting and make graininess (pelletize) product.
In the present invention, described concentrated sulphuric acid refers to the sulphuric acid that mass fraction is 98%.
In the present invention, described " Low-silicone alcohol base " refers to, silanol 4.0/nm of base density ＜2, preferably 2.0/nm of ＜2.
The second object of the present invention is to provide and a kind of has Low-silicone alcohol base precipitation dioxy by what method as defined above obtained
SiClx, it
Silanol 4.0/nm of base density ＜2；
Bet specific surface area is 100～235m2/g；
Ctab is 95～205m2/g；
Ph value is 5.5～7.5；
Pore volume is 1.65～2.25cm3/g；
Ultrasonic particle size d50For 1.0～10.0 μm；
Moisture is 4.0～8.0%；
Electrical conductivity is 800～1200 μm/cm.
Preferably, 2.0/nm of silanol base density ＜2.
Preferably, ph value is 6.0～7.0.
Preferably, moisture is 5.0～7.0%.
Preferably, it is median d50At least 250 μm spherical.
Preferably, it is at least the graininess of 0.5mm for size, and pellet hardness is 10～45g, preferably 15～30g.
The third object of the present invention is to provide a kind of precipitated silica as above as the purposes of reinforcing agent, excellent
It is elected to be the purposes for rubber tyre reinforcing agent.
Compared with the prior art, the invention has the following beneficial effects:
What the present invention obtained is the precipitated silica with Low-silicone alcohol base density, and what it showed is tool in rubber tyre
There are good dispersibility and processability, can effectively reduce rolling resistance and the heat of green tire, improve wearability.
Specific embodiment
To further illustrate technical scheme below by specific embodiment.
Embodiment 1
By modulus be 3.6 solid water glass and water be added in dissolution kettle by weight ratio for 1.0:2.0, then
Being passed directly into steam to pressure is 0.30mpa, after reaching pressure, stops adding steam, starts to be incubated, temperature retention time is little for 2.0
When, solid water glass is dissolved into liquid soluble glass, obtains the waterglass having dissolved；
In waterglass thinning tank, the waterglass having dissolved is added water and is diluted, be diluted to concentration with na2O is expressed as
The waterglass of 2.35n, the modulus of described waterglass is 3.6；
Add the waterglass preparation precipitation initial bed charge after water and dilution in reactor, wherein initial bed charge contains
A part for waterglass total amount used in described precipitation, is passed through steam in reactor, controls the temperature of initial bed charge
Spend for 75 DEG C, and adjust in initial bed charge concentration of sodium silicate with na2It is 8.0 that o is expressed as 0.05n or ph；
To in described initial bed charge in 120 minutes, it is simultaneously added dropwise the surplus waterglass used by sulphuric acid and precipitation, makes
There is precipitation in waterglass and concentrated sulphuric acid, be always ensured that in whole process the temperature of reaction medium and concentration of sodium silicate with
na2O is expressed as stablizing of 0.05n；
It is simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, in reaction medium with the drop rate list about aforementioned half
Solely Deca sulphuric acid, is 3.6 to reaction medium ph；
Described filter pressing and washing process include silica suspension precipitation being produced using membrane pressure filter
The filtration carrying out and washing operation, form filter cake.
The filter cake that described slurrying process is included using multi-stage stirrer and wet milk produce to filter pressing liquefies, and forms two
Oxidation silicon suspension, the solid content of this suspension is 20wt%, and ph is 5.50.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp, its dry feed
Pressure is 16.0bar.
By what method as defined above obtained, there is Low-silicone alcohol base precipitated silica, its 2.55/nm of silanol base2；bet
Specific surface area is 225m2/g；Ctab is 176m2/g；Ph value is 6.0；Pore volume is 1.70cm3/g；Ultrasonic particle size d50For 9.8 μ
m；Moisture 5.6 is %；Electrical conductivity is 1065 μm/cm.
Embodiment 2
By modulus be 4.0 solid water glass and water be added in dissolution kettle by weight ratio for 1.0:2.0, then
Being passed directly into steam to pressure is 0.50mpa, after reaching pressure, stops adding steam, starts to be incubated, temperature retention time is little for 4.0
When, solid water glass is dissolved into liquid soluble glass, obtains the waterglass having dissolved；
In waterglass thinning tank, the waterglass having dissolved is added water and is diluted, be diluted to concentration with na2O is expressed as
The waterglass of 2.47n, the modulus of described waterglass is 4.0；
Add the waterglass preparation precipitation initial bed charge after water and dilution in reactor, wherein initial bed charge contains
A part for waterglass total amount used in described precipitation, is passed through steam in reactor, controls the temperature of initial bed charge
Spend for 98 DEG C, and adjust in initial bed charge concentration of sodium silicate with na2O is expressed as 0.07n or ph10.0；
To in described initial bed charge in 120 minutes, it is simultaneously added dropwise the surplus waterglass used by sulphuric acid and precipitation, makes
There is precipitation in waterglass and concentrated sulphuric acid, be always ensured that in whole process the temperature of reaction medium and concentration of sodium silicate with
na2It is 10.0 stablize that o is expressed as 0.07n or ph；
It is simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, individually dripped with the drop rate of aforementioned half in reaction medium
Plus sulphuric acid independent Deca sulphuric acid, it is 4.0 to reaction medium ph；
Described filter pressing and washing process include silica suspension precipitation being produced using membrane pressure filter
The filtration carrying out and washing operation, form filter cake.
The filter cake that described slurrying process is included using multi-stage stirrer and wet milk produce to filter pressing liquefies, and forms two
Oxidation silicon suspension, the solid content of this suspension is 24wt%, and ph is 6.50.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp, its dry feed
Pressure is 50.0bar.
By what method as defined above obtained, there is Low-silicone alcohol base precipitated silica, its silanol based 1.5/nm2；bet
Specific surface area is 115m2/g；Ctab is 110m2/g；Ph value is 7.0；Pore volume is 2.20cm3/g；Ultrasonic particle size d50For 2.05
μm；Moisture is 6.2%；Electrical conductivity is 850 μm/cm.
Embodiment 3
By modulus be 3.8 solid water glass and water be added in dissolution kettle by weight ratio for 1:2.0, Ran Houzhi
Connecting into steam to pressure is 0.40mpa, after reaching pressure, stops adding steam, starts to be incubated, temperature retention time is 3 hours, will
Solid water glass is dissolved into liquid soluble glass, obtains the waterglass having dissolved；
In waterglass thinning tank, the waterglass having dissolved is added water and is diluted, be diluted to concentration with na2O is expressed as
The waterglass of 2.50n, the modulus of described waterglass is 3.8；
Add the waterglass preparation precipitation initial bed charge after water and dilution in reactor, wherein initial bed charge contains
A part for waterglass total amount used in described precipitation, is passed through steam in reactor, controls the temperature of initial bed charge
Spend for 85 DEG C, and adjust in initial bed charge concentration of sodium silicate with na2It is 9.5 that o is expressed as 0.06n or ph；
To in described initial bed charge in 150 minutes, it is simultaneously added dropwise the surplus waterglass used by sulphuric acid and precipitation, makes
There is precipitation in waterglass and concentrated sulphuric acid, be always ensured that in whole process the temperature of reaction medium and concentration of sodium silicate with
na2It is 9.5 stablize that o is expressed as 0.06n or ph；
It is simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, in reaction medium with the drop rate list about aforementioned half
Solely Deca sulphuric acid, is 4.0 to reaction medium ph；
Described filter pressing and washing process include silica suspension precipitation being produced using membrane pressure filter
The filtration carrying out and washing operation, form filter cake.
The filter cake that described slurrying process is included using multi-stage stirrer and wet milk produce to filter pressing liquefies, and forms two
Oxidation silicon suspension, the solid content of this suspension is 22wt%, and ph is 6.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp, its dry feed
Pressure is 30bar.
By what method as defined above obtained, there is Low-silicone alcohol base precipitated silica, its 1.86/nm of silanol base2；bet
Specific surface area is 165m2/g；Ctab is 160m2/g；Ph value is 6.5；Pore volume is 1.98cm3/g；Ultrasonic particle size d50For 3.50
μm；Moisture is 5.9%；Electrical conductivity is 952 μm/cm.
Embodiment 4
By modulus be 3.6 solid water glass and water be added in dissolution kettle by weight ratio for 1.0:2.0, then
Being passed directly into steam to pressure is 0.30mpa, after reaching pressure, stops adding steam, starts to be incubated, temperature retention time is little for 2.0
When, solid water glass is dissolved into liquid soluble glass, obtains the waterglass having dissolved；
In waterglass thinning tank, the waterglass having dissolved is added water and is diluted, be diluted to concentration with na2O is expressed as
The waterglass of 2.45n, the modulus of described waterglass is 3.6；
Add the waterglass preparation precipitation initial bed charge after water and dilution in reactor, wherein initial bed charge contains
A part for waterglass total amount used in described precipitation, is passed through steam in reactor, controls the temperature of initial bed charge
Spend for 85 DEG C, and adjust in initial bed charge concentration of sodium silicate with na2It is 11.0 that o is expressed as 0.08n or ph；
To in described initial bed charge in 120 minutes, it is simultaneously added dropwise the surplus waterglass used by sulphuric acid and precipitation, makes
There is precipitation in waterglass and concentrated sulphuric acid, be always ensured that in whole process the temperature of reaction medium and concentration of sodium silicate with
na2O is expressed as stablizing of 0.08n；
It is simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, independent Deca sulphuric acid again after reaction medium is aged, old
The time changed is 30 minutes, the then independent Deca sulphuric acid in reaction medium, is 4.0 to reaction medium ph
Described filter pressing and washing process include silica suspension precipitation being produced using membrane pressure filter
The filtration carrying out and washing operation, form filter cake.
The filter cake that described slurrying process is included using multi-stage stirrer and wet milk produce to filter pressing liquefies, and forms two
Oxidation silicon suspension, the solid content of this suspension is 20wt%, and ph is 5.50.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp.Its dry feed
Pressure is 18.0bar
By what method as defined above obtained, there is Low-silicone alcohol base precipitated silica, its 1.72/nm of silanol base2；bet
Specific surface area is 168m2/g；Ctab is 162m2/g；Ph value is 6.0；Pore volume is 1.95cm3/g；Ultrasonic particle size d50For 3.5 μ
m；Moisture is 5.6%；Electrical conductivity is 1050 μm/cm.
Embodiment 5
By modulus be 3.9 solid water glass and water be added in dissolution kettle by weight ratio for 1.0:2.0, then
Being passed directly into steam to pressure is 0.30mpa, after reaching pressure, stops adding steam, starts to be incubated, temperature retention time is little for 2.0
When, solid water glass is dissolved into liquid soluble glass, obtains the waterglass having dissolved；
In waterglass thinning tank, the waterglass having dissolved is added water and is diluted, be diluted to concentration with na2O is expressed as
The waterglass of 2.47n, the modulus of described waterglass is 3.9；
Add the waterglass preparation precipitation initial bed charge after water and dilution in reactor, wherein initial bed charge contains
A part for waterglass total amount used in described precipitation, is passed through steam in reactor, controls the temperature of initial bed charge
Spend for 84 DEG C, and adjust in initial bed charge concentration of sodium silicate with na2It is 10.0 that o is expressed as 0.07n or ph；
To in described initial bed charge in 105 minutes, it is simultaneously added dropwise the surplus waterglass used by sulphuric acid and precipitation, makes
There is precipitation in waterglass and concentrated sulphuric acid, be always ensured that in whole process the temperature of reaction medium and concentration of sodium silicate with
na2O is expressed as stablizing of 0.07n；
It is simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, independent Deca sulphuric acid again after reaction medium is aged, old
The time changed is 30 minutes, the then independent Deca sulphuric acid in reaction medium, is 4.5 to reaction medium ph
Described filter pressing and washing process include silica suspension precipitation being produced using membrane pressure filter
The filtration carrying out and washing operation, form filter cake.
The filter cake that described slurrying process is included using multi-stage stirrer and wet milk produce to filter pressing liquefies, and forms two
Oxidation silicon suspension, the solid content of this suspension is 20wt%, and ph is 6.0.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp.Its dry feed
Pressure is 20.0bar.
By what method as defined above obtained, there is Low-silicone alcohol base precipitated silica, its 1.80/nm of silanol base2；bet
Specific surface area is 170m2/g；Ctab is 160m2/g；Ph value is 6.5；Pore volume is 2.15cm3/g；Ultrasonic particle size d50For 4.2 μ
m；Moisture is 5.6%；Electrical conductivity is 670 μm/cm.
Embodiment 6
What the present invention obtained is the precipitated silica with Low-silicone alcohol base, it show be have in rubber tyre good
Good dispersibility and processability, can effectively reduce rolling resistance and the heat of green tire, improve wearability.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, that is, do not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, the equivalence replacement to each raw material of product of the present invention and auxiliary element
Interpolation, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (23)
1. a kind of prepare the method with Low-silicone alcohol base precipitated silica, it is heavy that methods described includes making waterglass and sulphuric acid to occur
Form sediment reaction, thus obtaining the suspension of precipitated silica, afterwards through filter pressing and washing, slurrying process and this suspension is dried
Liquid, wherein, carries out precipitation as follows:
(1) in waterglass thinning tank, the waterglass having dissolved is added water and is diluted, be diluted to concentration with na2O is expressed as
The waterglass of 2.30～2.70n, the modulus of described waterglass is 3.5～4.0；
(2) the waterglass preparation precipitation initial bed charge after water and step (1) dilution, wherein initial bottom are added in reactor
A part containing waterglass total amount used in described precipitation for the material, is passed through steam in reactor, controls initial bottom
The temperature of material is 75～98 DEG C, and adjusts in initial bed charge concentration of sodium silicate with na2O is expressed as 0.04～0.08n, or ph is
8.0～11.0；
(3) in described initial bed charge in 90～180 minutes, it is simultaneously added dropwise the excess water glass used by sulphuric acid and precipitation
Glass, makes waterglass, with concentrated sulphuric acid, precipitation occur, is always ensured that the temperature of reaction medium and waterglass are dense in whole process
Degree is with na2It is 8.0～11.0 stablize that o is expressed as 0.04～0.08n or ph；
(4) it is simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, independent Deca sulphuric acid again after reaction medium is aged, ageing
Time be 15～120 minutes, the ph to reaction medium reaches 3.0～6.0；；
The filter cake that described slurrying process is included using multi-stage stirrer and wet milk produce to filter pressing liquefies, and forms titanium dioxide
Silicon suspension, the solid content of this suspension is 20～24wt%, and ph is 5.50～6.50；
Described " Low-silicone alcohol base " refers to, silanol 4.0/nm of base density ＜2.
2. the method for claim 1 is it is characterised in that the preparation method of the waterglass having dissolved in step (1) is:
By modulus be 3.5～4.0 solid water glass and water be added in dissolution kettle by weight ratio for 1.0:2.0, so
After be passed directly into steam to pressure be 0.30～0.50mpa, after reaching pressure, stop add steam, start be incubated, temperature retention time
For 2.0～4.0 hours, solid water glass is dissolved into liquid soluble glass, obtains the waterglass having dissolved.
3. method as claimed in claim 2 is it is characterised in that the modulus of solid water glass is 3.5～4.0.
4. method as claimed in claim 2 is it is characterised in that temperature retention time is 3.0 hours.
5. method as claimed in claim 2 it is characterised in that the good concentration of sodium silicate of described dissolving be calculated as 30 with Baume degrees～
38be°.
6. method as claimed in claim 2 is it is characterised in that the good concentration of sodium silicate of described dissolving is calculated as with Baume degrees
35be°.
7. the method for claim 1 is it is characterised in that in step (1), be diluted to concentration with na2O is expressed as 2.40
The waterglass of～2.50n.
8. the method for claim 1 is it is characterised in that step (3) is in 120～150 minutes, be simultaneously added dropwise sulphuric acid and
Surplus waterglass used by precipitation.
9. the method for claim 1, it is characterised in that being simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, will be reacted
Medium be aged after independent Deca sulphuric acid again, the time of ageing is 30～90 minutes.
10. the method for claim 1 is it is characterised in that be simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, with step
(3) drop rate of half independent Deca sulphuric acid in, the ph to reaction medium reaches 3.0～6.0.
11. methods as claimed in claim 10 are it is characterised in that be simultaneously added dropwise surplus waterglass and after sulphuric acid terminates, with step
Suddenly in (3) half drop rate independent Deca sulphuric acid, the ph to reaction medium reaches 4.0～5.0.
12. the method for claim 1 it is characterised in that in step (4) ph of question response medium reach 3.0～6.0
Afterwards, stop independent Deca concentrated sulphuric acid, reaction medium is aged, the time of ageing is 15～120 minutes.
13. the method for claim 1 it is characterised in that in step (4) ph of question response medium reach 3.0～6.0
Afterwards, stop independent Deca concentrated sulphuric acid, reaction medium is aged, the time of ageing is 30～90 minutes.
14. the method for claim 1 are it is characterised in that described filter pressing and washing process are included using diaphragm type filter pressing
Filtration and washing operation that machine is carried out to the silica suspension that precipitation produces, form filter cake.
15. the method for claim 1 are it is characterised in that described dry run is exactly to slurry by compression sprayer
Change the suspension producing to be dried, its dry feed pressure is 16.0～50.0bar.
16. methods as claimed in claim 15 are it is characterised in that described dry run is exactly to slurry by compression sprayer
Change the suspension producing to be dried, its dry feed pressure is 18～40bar.
17. the method for claim 1 it is characterised in that described have Low-silicone alcohol base precipitated silica, it:
Silanol 4.0/nm of base density ＜2；
Bet specific surface area is 100～235m2/g；
Ctab is 95～205m2/g；
Ph value is 5.5～7.5；
Pore volume is 1.65～2.25cm3/g；
Ultrasonic particle size d50For 1.0～10.0 μm；
Moisture is 4.0～8.0%；
Electrical conductivity is 800～1200 μm/cm.
18. methods as claimed in claim 17 are it is characterised in that silanol 2.0/nm of base density ＜2.
19. methods as claimed in claim 17 are it is characterised in that ph value is 6.0～7.0.
20. methods as claimed in claim 17 are it is characterised in that moisture is 5.0～7.0%.
21. methods as claimed in claim 17 are it is characterised in that described have Low-silicone alcohol base precipitated silica for middle position grain
Footpath d50At least 250 μm spherical.
22. methods as claimed in claim 17 are it is characterised in that described have Low-silicone alcohol base precipitated silica for size extremely
It is the graininess of 0.5mm less, pellet hardness is 10～45g.
23. methods as claimed in claim 22 are it is characterised in that described pellet hardness is 15～30g.
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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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN110156032B (en) * | 2019-07-01 | 2022-06-07 | 福建正盛无机材料股份有限公司 | Preparation method of white carbon black for high-yellowing-resistance silicone rubber |
| 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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| CN1148567A (en) * | 1995-07-26 | 1997-04-30 | 底古萨股份公司 | Precipitated silicon dioxide |
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