CN104291342B - 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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- CN104291342B CN104291342B CN201410487918.3A CN201410487918A CN104291342B CN 104291342 B CN104291342 B CN 104291342B CN 201410487918 A CN201410487918 A CN 201410487918A CN 104291342 B CN104291342 B CN 104291342B
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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 new method of the high-specific surface area precipitated silica as rubber tyre reinforcing agent.It is also
It is related in spherical microballon silicon dioxide and granular granulated silica.
Background technology
Precipitated silica act as reinforcing agent, particularly green tire and load-carrying tire, in order to drop in rubber tyre
The rolling resistance of low tire, reduces heat, improves wearability, precipitated silica is essential, with European Union's labeling acts
Enforcement and environment increasingly serious, usage amount in rubber tyre for the precipitated silica is increasing.
As other any supporting materials, on the one hand it is easy to process, and on the other hand it will be easy to and rubber mix.
In order to reach the purpose obtaining optimal reinforcing effect by adding silicon dioxide, silicon dioxide should use up in rubber
Possible fine and be uniformly distributed as far as possible.Require it is necessary to improve the combination energy of silicon dioxide and rubber to meet this
Power and dispersion and be depolymerized to very thin powder, but also can be complete and homogeneous be dispersed in rubber.
Unfortunately, there is the silicon dioxide of of a relatively high specific surface area, its wearability in rubber very well, but is processed
Poor performance and poor dispersion.
Cn 1100001c discloses a kind of preparation method of precipitated silica, including making silicate and acidulant
Reaction, is derived from the suspension of precipitated silica, separates afterwards and this suspension is dried, sunk in such a way
Form sediment: (i) prepares Initial stock solutions, wherein contain at least a portion and at least of silicate total amount used in described reaction
A kind of electrolyte, in described Initial stock solutions, the concentration of silicate is with sio2It is expressed as 50 to 60g/l.(ii) to described storage
Add acidulant till the ph of reaction medium reaches 7 to 8.5, (iii) adds acidifying in reaction medium in standby solution
Agent, adds the silicate of its surplus if necessary simultaneously, and described separation process includes carrying out using the filter equipped with pressue device
Filtration and washing operation ,-suspension that wherein solids content be less than 17wt% is dried by spraying.But, the method is adopted
It is diluted a cid method, the deficiency of diluted a cid method has: (1) production capacity is low, about low by 20%, unit consumption is high；(2) corruption to equipment and pipeline for the diluted acid
Corrosion is big, and maintenance of equipment expense is high；(3) adopt sio2Control, analyze time-consuming in practical operation, and control unstable；(4)
Pulp solid content is low, the high energy consumption being dried, and product particle intensity is not enough.
Content of the invention
For the problem of prior art, the invention provides a kind of new side preparing high-specific surface area precipitated silica
Method, has high comparison surface using the precipitated silica that the method obtains, and has excellent processing characteristics, dispersibility
Energy and excellent reinforcing property.
To achieve these goals, present invention employs following technical scheme:
A kind of method preparing precipitated silica, methods described includes making waterglass, with concentrated sulphuric acid, precipitation occur,
Thus obtaining the suspension of precipitated silica, afterwards through filter pressing and washing, slurrying process and this suspension is dried, wherein,
Carry out precipitation as follows:
(1) prepare precipitation initial bed charge, wherein contain one of waterglass total amount used in described precipitation
Part, in described initial bed charge, concentration of sodium silicate is with na2O is expressed as 0.05～0.15n, and ph is 6.0～12.0；
(2) it is simultaneously added dropwise concentrated sulphuric acid and surplus waterglass in described initial bed charge, so that waterglass and concentrated sulphuric acid is occurred heavy
Form sediment and react；
(3) it is simultaneously added dropwise surplus waterglass and after concentrated sulphuric acid terminates, the independent Deca concentrated sulphuric acid in reaction medium；
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 more than 20wt% (the high advantage of solid content: (1) can reduce dry run
In energy consumption, reach the purpose of energy-conservation, often improve 1% solid content, can energy efficient 5% about.(2) can ensure that bead particles
Intensity and homogeneity, and ensure not crush in use, good flowing properties.(3) environmental protection in the mixing process of rubber,
And the energy accurate measurement when feeding intake).
The purpose adding electrolyte during precipitation is to improve the pore volume of white carbon (porosity), especially suitable
It is more than 250m for bet2The white carbon of/more than g.And the present invention also not can reach identical pore volume using electrolyte, it is suitable for
It is 185-235m in bet2The white carbon of/g.
In the present invention, the essential condition obtaining silicon dioxide superperformance includes: the concentration of sodium silicate of initial bed charge, ph
Value, it is simultaneously added dropwise surplus waterglass and concentrated sulphuric acid, filtered using membrane pressure filter and wash.Filter pressing due to this structure
Machine has water pressing function it can be ensured that obtained filter cake solid content is more than 24.0wt%.
In the present invention, step (1) prepares precipitation initial bed charge first so as to containing the water required for precipitation
A part for glass total amount, is then simultaneously added dropwise concentrated sulphuric acid and surplus waterglass more thereto.
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 a stable reaction condition it is ensured that be simultaneously added dropwise dense sulfur for the second time for second step Deca
Na when acid and surplus waterglass2The stability contorting of o.
In step (1), described concentration of sodium silicate is with na2O 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, for example
6.5th, 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, described concentrated sulphuric acid refers to the sulphuric acid that mass fraction is 98%.
In the present invention, described waterglass refers to the waterglass that modulus is 3.10～3.60, the modulus example of described waterglass
As for 3.15,3.25,3.35,3.45 or 3.55.
In the present invention, being simultaneously added dropwise concentrated sulphuric acid and the time of surplus waterglass in step (2) is 60～150 minutes, example
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, in step (2) controlling reaction temperature be 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.
Additionally, at the same time during Deca concentrated sulphuric acid and surplus waterglass, remain that reaction temperature is constant and reaction
Concentration of sodium silicate in medium is with na2O be 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 be 9.0～11.0 (such as 9.2,9.4,9.6,9.8,10,
10.2nd, 10.4,10.6 or 10.8) stablize.
At the same time during Deca concentrated sulphuric acid and surplus waterglass, controlling reaction temperature is 70～80 DEG C first, for example
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 a hour, are warming up to 80～90 DEG C, example
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 effectively control
The difference of bet-ctab processed, that is, reduce the micropore in white carbon, enable white carbon preferably and compounding rubber, improve its point
Scattered property.
In the present invention, the concentration of described surplus waterglass is with na2O 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 is such as: the present invention prepares the waterglass of above-mentioned concentration first as raw material, using this preparation of raw material
Reaction initial bed charge in step (1), is then simultaneously added dropwise the waterglass of the above-mentioned concentration of surplus again in step (2).
After being simultaneously added dropwise concentrated sulphuric acid and surplus waterglass terminates, proceed by step (3).
In step (3), the independent Deca of the drop rate of the half of concentrated sulphuric acid drop rate in drop rate as step (2)
Concentrated sulphuric acid, with remaining waterglass in neutralization reaction medium, to reaction medium ph reach 5.0～9.0, such as 5.5,6.0,
6.5th, 7.0,7.5,8.0,8.5,9.0, preferably 7.0～8.0.Preferably, now stop independent Deca concentrated sulphuric acid, by reaction medium
It is aged, the time of ageing is 15～120 minutes, such as 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 points
Clock, 120 minutes, preferably 30～90 minutes.
After step to be aged terminates, continue individually to add concentrated sulphuric acid, the ph to reaction medium reaches 3.0～6.0, for example
3.5th, 4.0,4.5,5.0,5.5, preferably 4.0～5.0.According to the present invention, now reaction medium can also be aged, ageing
Time be 15～120 minutes, such as 30 minutes, 45 minutes, 60 minutes, 75 minutes, 90 minutes, 105 minutes, 120 minutes, excellent
Select 30～90 minutes.
According to the present invention, the preferred back ageing of two step ageings, after that is, the ph of preferably reaction medium reaches 5.0～9.0
Ageing, can effectively improve pore volume and the aperture of white carbon.
After step (3) terminates, obtain silica suspension, then carry out filter pressing and washing.
In the present invention, filtered using membrane pressure filter and washed, the pressure filter due to this structure is had hydraulic pressure
Squeeze function it can be ensured that obtained filter cake solid content is more than 24.0wt%.
The filter cake obtaining after filtration washing carries out pulp by multi-stage stirrer and wet milk again, obtains solid content and is
The suspension of 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 glue to obtain
Spend the silica suspension for 1000～2000cp.
Additionally, in slurrying process, the ph to 5.0～7.0 that sulphuric acid adjusts this suspension also can be added, preferably 5.5～6.5.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp.
The preferred essential condition obtaining silicon dioxide superperformance includes: the concentration of sodium silicate of initial bed charge, ph value, together
When Deca surplus waterglass and concentrated sulphuric acid, reaction temperature, response time, digestion time, filtration, pulp and drying mode.
According to the present invention, drying uses pressure type and is dried, and acquisition is spherical microballon silicon dioxide, its middle position grain
Footpath d50At least 250 μm.
Described dry products subsequently carry out briquetting and make graininess (pelletize) product.The microballon shape titanium dioxide being dried to obtain
Silicon, directly can obtain graininess granulated silica by comminutor, and its size is at least the graininess of 0.5mm, pellet hardness
For 10～40g.
The second object of the present invention is to provide a kind of precipitated silica being obtained by method as defined above, its bet
Specific surface area is 185～235m2/ g, ctab are 165～205m2/ g, ph value is 5.5～7.5, pore volume be 1.65～
2.25cm3/ g, most probable pore size is 15～35nm, ultrasonic particle size d50For 6.0～10.0 μm.
Preferably, bet specific surface area is 190～210m2/g.
Preferably, ctab is 165～185m2/g.
Preferably, ph value is 6.0～6.5.
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 10～40g, preferably 15～25g.
The third object of the present invention is to provide a kind of precipitated silica as above as the reinforcement of rubber tyre
The purposes of agent.
Compared with the prior art, the invention has the following beneficial effects:
What the present invention obtained is the precipitated silica with high specific surface area, and it has well in rubber tyre
Dispersibility and processability, and there is high-wearing feature, can effectively reduce rolling resistance and the life of green tire and load-carrying tire
Heat.
Specific embodiment
To further illustrate technical scheme below by specific embodiment.
Embodiment 1
A kind of method preparing precipitated silica, methods described includes making waterglass, with concentrated sulphuric acid, precipitation occur,
Thus obtaining the suspension of precipitated silica, afterwards through filter pressing and washing, slurrying process and this suspension is dried, wherein,
Carry out precipitation as follows:
(1) prepare precipitation initial bed charge, wherein contain one of waterglass total amount used in described precipitation
Part, in described initial bed charge, concentration of sodium silicate is with na2O is expressed as 0.05n, and ph is 9.0；Simultaneously will be initial with steam
Bed material temperature rises to 80 DEG C；
(2) it is simultaneously added dropwise concentrated sulphuric acid and surplus waterglass in described initial bed charge, so that waterglass and concentrated sulphuric acid is occurred heavy
Form sediment and react；Time of simultaneously adding is 90 minutes, guarantee in adding procedure at the same time 80 DEG C of reaction temperature and concentration of sodium silicate with
na2O is expressed as 0.05n, ph be 9.0 constant.
(3) it is simultaneously added dropwise concentrated sulphuric acid and after surplus waterglass terminates, the independent Deca concentrated sulphuric acid in reaction medium；Until ph
For 4.0 ± 0.2.
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 ph5.8.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp.
A kind of precipitated silica being obtained by method as defined above, its bet specific surface area is 205m2/ g, ctab are
175m2/ g, ph value is 6.15, and pore volume is 1.80cm3/ g, most probable pore size is 30nm, ultrasonic particle size d50For 8.5 μm.
It can be median d50At least 250 μm spherical, also can obtain size at least 0.5mm's by pelletize
Graininess, pellet hardness is 20.5g.
Embodiment 2
A kind of method preparing precipitated silica, methods described includes making waterglass, with concentrated sulphuric acid, precipitation occur,
Thus obtaining the suspension of precipitated silica, afterwards through filter pressing and washing, slurrying process and this suspension is dried, wherein,
Carry out precipitation as follows:
(1) prepare precipitation initial bed charge, wherein contain one of waterglass total amount used in described precipitation
Part, in described initial bed charge, concentration of sodium silicate is with na2O is expressed as 0.05nph；9.0；
(2) it is simultaneously added dropwise concentrated sulphuric acid and surplus waterglass in described initial bed charge, so that waterglass and concentrated sulphuric acid is occurred heavy
Form sediment and react；Controlling reaction temperature is 80 DEG C, and the response time is 120 minutes.
(3) it is simultaneously added dropwise concentrated sulphuric acid and after surplus waterglass terminates, the independent Deca concentrated sulphuric acid in reaction medium；Until ph
For 4.0 ± 0.2；
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 22.0wt%, and ph is 5.90.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp.
A kind of precipitated silica being obtained by method as defined above, its bet specific surface area is 195m2/ g, ctab are
170m2/ g, ph value is 6.20, and pore volume is 1.87cm3/ g, most probable pore size is 25.0nm, ultrasonic particle size d50For 7.8 μm.
It can be median d50At least 250 μm spherical, also can obtain size by pelletize and be at least 0.5mm
Graininess, pellet hardness be 20.8g.
Embodiment 3
A kind of method preparing precipitated silica, methods described includes making waterglass, with concentrated sulphuric acid, precipitation occur,
Thus obtaining the suspension of precipitated silica, afterwards through filter pressing and washing, slurrying process and this suspension is dried, wherein,
Carry out precipitation as follows:
(1) prepare precipitation initial bed charge, wherein contain one of waterglass total amount used in described precipitation
Part, in described initial bed charge, concentration of sodium silicate is with na2O is expressed as 0.06n, and ph is 9.50；
(2) be simultaneously added dropwise concentrated sulphuric acid and surplus waterglass in 90 minutes in described initial bed charge, make waterglass with
There is precipitation in concentrated sulphuric acid, wherein, during Deca, controlling reaction temperature is 80 DEG C；Additionally, Deca concentrated sulphuric acid at the same time
During surplus waterglass, remain that reaction temperature is constant and reaction medium in ph be 9.0～11.0 stablize；
(3) it is simultaneously added dropwise concentrated sulphuric acid and after surplus waterglass terminates, concentrated sulphuric acid Deca speed in drop rate as step (2)
Drop rate about the half of rate independent Deca concentrated sulphuric acid, with remaining waterglass in neutralization reaction medium, to reaction medium
Ph reach 5.0, now stop independent Deca concentrated sulphuric acid, reaction medium be aged, time of ageing is 30 minutes, treats old
After change step terminates, continue individually to add concentrated sulphuric acid, the ph to reaction medium reaches 3.0；
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 22.6wt%, and ph is 6.0.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp.
A kind of precipitated silica being obtained by method as defined above, its bet specific surface area is 196m2/ g, ctab are
172m2/ g, ph value is 6.45, and pore volume is 2.05cm3/ g, most probable pore size is 32nm, ultrasonic particle size d50For 6.10 μm.
It can be median d50At least 250 μm spherical, also can obtain size at least 0.5mm's by pelletize
Graininess, pellet hardness is 22.0g.
Embodiment 4
A kind of method preparing precipitated silica, methods described includes making waterglass, with concentrated sulphuric acid, precipitation occur,
Thus obtaining the suspension of precipitated silica, afterwards through filter pressing and washing, slurrying process and this suspension is dried, wherein,
Carry out precipitation as follows:
(1) prepare precipitation initial bed charge, wherein contain one of waterglass total amount used in described precipitation
Part, in described initial bed charge, concentration of sodium silicate is with na2O is expressed as 0.06n, and ph is 9.0；
(2) be simultaneously added dropwise concentrated sulphuric acid and surplus waterglass in 120 minutes in described initial bed charge, make waterglass with
There is precipitation in concentrated sulphuric acid, wherein, during Deca, controlling reaction temperature, for 76 DEG C after a hour, heats up first
To 90 DEG C；Additionally, at the same time during Deca concentrated sulphuric acid and surplus waterglass, remaining that reaction temperature is constant and reaction is situated between
Ph in matter is 9.0～11.0 stablizes；
(3) it is simultaneously added dropwise concentrated sulphuric acid and after surplus waterglass terminates, concentrated sulphuric acid Deca speed in drop rate as step (2)
Drop rate about the half of rate independent Deca concentrated sulphuric acid, with remaining waterglass in neutralization reaction medium, to reaction medium
Ph reach 5.0, now stop independent Deca concentrated sulphuric acid, reaction medium be aged, time of ageing is 30 minutes.
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 6.25 for 21.5%, ph.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp.
A kind of precipitated silica being obtained by method as defined above, its bet specific surface area is 195m2/ g, ctab are
170m2/ g, ph value is 6.70, and pore volume is 1.75cm3/ g, most probable pore size is 24.0nm, ultrasonic particle size d50For 6.8 μm.
It can be median d50At least 250 μm spherical, also can obtain size at least 0.5mm's by pelletize
Graininess, pellet hardness is 18.0g.
Embodiment 5
A kind of method preparing precipitated silica, methods described includes making waterglass, with concentrated sulphuric acid, precipitation occur,
Thus obtaining the suspension of precipitated silica, afterwards through filter pressing and washing, slurrying process and this suspension is dried, wherein,
Carry out precipitation as follows:
(1) prepare precipitation initial bed charge, wherein contain one of waterglass total amount used in described precipitation
Part, in described initial bed charge, concentration of sodium silicate is with na2O is expressed as 0.06n, and ph is 9.0；
(2) be simultaneously added dropwise concentrated sulphuric acid and surplus waterglass in 90 minutes in described initial bed charge, make waterglass with
There is precipitation in concentrated sulphuric acid, wherein, during Deca, controlling reaction temperature is first, and 75 DEG C, after a hour, heat up
To 86 DEG C；Additionally, at the same time during Deca concentrated sulphuric acid and surplus waterglass, remaining that reaction temperature is constant and reaction is situated between
Ph in matter is 9.0～11.0 stablizes；
(3) it is simultaneously added dropwise concentrated sulphuric acid and after surplus waterglass terminates, concentrated sulphuric acid Deca speed in drop rate as step (2)
Drop rate about the half of rate independent Deca concentrated sulphuric acid, with remaining waterglass in neutralization reaction medium, to reaction medium
Ph reach 9.0, now stop independent Deca concentrated sulphuric acid, reaction medium be aged, the time of ageing is, 30 minutes.
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
Aoxidize silicon suspension, the solid content of this suspension is；22.5wt%, ph are 6.0.
Described dry run is exactly to be dried by the suspension that compression sprayer produces to pulp.
A kind of precipitated silica being obtained by method as defined above, its bet specific surface area is 200m2/ g, ctab are
190m2/ g, ph value is 6.30, and pore volume is 1.90cm3/ g, most probable pore size is 30nm, ultrasonic particle size d50For 6.2 μm.
It can be median d50At least 250 μm spherical, also can obtain size at least 0.5mm's by pelletize
Graininess, pellet hardness is 25.0g.
In above-described embodiment 1～5, the concentration of surplus waterglass is with na2O 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
Meet the silica suspension of solid content and viscosity requirement.Optionally, in addition, also can add sulphuric acid and adjust the ph of this suspension extremely
5.0～7.0.
Embodiment 6
The precipitated silica of the present invention has good dispersibility and processability in rubber tyre, and has high resistance to
Mill property, can effectively reduce rolling resistance and the heat 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 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 (30)
1. a kind of method preparing precipitated silica, methods described includes making waterglass, with concentrated sulphuric acid, precipitation occur, from
And obtain the suspension of precipitated silica, afterwards through filter pressing and washing, slurrying process and this suspension is dried, wherein, press
Following method carries out precipitation:
(1) prepare precipitation initial bed charge, wherein contain a part for waterglass total amount used in described precipitation,
In described initial bed charge, concentration of sodium silicate is with na2O is expressed as 0.05～0.15n, and ph is 6.0～12.0；
(2) it is simultaneously added dropwise concentrated sulphuric acid and surplus waterglass in described initial bed charge, make waterglass and concentrated sulphuric acid occur precipitation anti-
Should；
(3) it is simultaneously added dropwise surplus waterglass and after concentrated sulphuric acid terminates, the independent Deca concentrated sulphuric acid in reaction medium；
At the same time during Deca concentrated sulphuric acid and surplus waterglass, remain that reaction temperature is constant and reaction medium in water
Glass concentration is with na2It is 9.0～11.0 stablize that o is expressed as 0.06～0.08n or ph；
Described filter pressing and washing process include using membrane pressure filter, the silica suspension that precipitation produces being carried out
Filtration and washing operation, formed 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 titanium dioxide
Silicon suspension, the solid content of this suspension is more than 20wt%.
2. the method for claim 1 is it is characterised in that in step (1), described concentration of sodium silicate is with na2O is expressed as
0.06～0.08n.
3. the method for claim 1 is it is characterised in that in step (1), described ph is 9.0～11.0.
4. the method for claim 1 is it is characterised in that described waterglass refers to the waterglass that modulus is 3.10～3.60.
5. the method for claim 1 is it is characterised in that be simultaneously added dropwise concentrated sulphuric acid and surplus waterglass in step (2)
Time is 60～150 minutes.
6. method as claimed in claim 5 is it is characterised in that be simultaneously added dropwise concentrated sulphuric acid and surplus waterglass in step (2)
Time is 90～120 minutes.
7. the method for claim 1 it is characterised in that in step (2) controlling reaction temperature be 60～90 DEG C.
8. method as claimed in claim 7 it is characterised in that in step (2) controlling reaction temperature be 78～82 DEG C.
9. the method for claim 1 is it is characterised in that step (3) Deca concentrated sulphuric acid and surplus waterglass at the same time
During, controlling reaction temperature is 70～80 DEG C first, after a hour, is warming up to 80～90 DEG C.
10. the method for claim 1 is it is characterised in that the concentration of described surplus waterglass is with na2O is expressed as 2.30～
2.70n.
11. methods as claimed in claim 10 are it is characterised in that the concentration of described surplus waterglass is with na2O is expressed as 2.40
～2.50n.
12. the method for claim 1 are it is characterised in that the dense sulfur of the independent Deca of drop rate with half in step (2)
Acid, the ph to reaction medium reaches 5.0～9.0.
13. methods as claimed in claim 12 are it is characterised in that after the ph of question response medium reaches 5.0～9.0, stop single
Solely Deca concentrated sulphuric acid, reaction medium is aged, and the time of ageing is 15～120 minutes.
14. methods as claimed in claim 13 are it is characterised in that the time of described ageing is 30～90 minutes.
15. methods as claimed in claim 13 it is characterised in that after end to be aged, continue individually to add concentrated sulphuric acid, to anti-
The ph answering medium reaches 3.0～6.0.
16. methods as claimed in claim 15 it is characterised in that after end to be aged, continue individually to add concentrated sulphuric acid, to anti-
The ph answering medium reaches 4.0～5.0.
17. methods as claimed in claim 15 will be it is characterised in that after the ph of question response medium reaches 3.0～6.0, will react
Medium is aged, and the time of ageing is 15～120 minutes.
18. methods as claimed in claim 17 are it is characterised in that the time of described ageing is 30～90 minutes.
19. the method for claim 1 are it is characterised in that the solid content of suspension is 21.0～23.0wt%.
20. the method for claim 1 are it is characterised in that add water or additive, to obtain satisfaction in slurrying process
Solid content and the silica suspension that viscosity is 1000～2000cp.
21. methods as claimed in claim 20 are it is characterised in that in slurrying process, plus sulphuric acid adjusts the ph of suspension extremely
5.0～7.0.
22. methods as claimed in claim 21 are it is characterised in that in slurrying process, plus sulphuric acid adjusts the ph of suspension extremely
5.5～6.5.
23. the method for claim 1 make granular product it is characterised in that dry products subsequently carry out briquetting.
24. the method for claim 1 it is characterised in that described precipitated silica bet specific surface area be 185～
235m2/ g, ctab are 165～205m2/ g, ph value is 5.5～7.5, and pore volume is 1.65～2.25cm3/ g, most probable pore size is
15～35nm, ultrasonic particle size d50For 6.0～10.0 μm.
25. methods as claimed in claim 24 are it is characterised in that bet specific surface area is 190～210m2/g.
26. methods as claimed in claim 24 are it is characterised in that ctab is 165～185m2/g.
27. methods as claimed in claim 24 are it is characterised in that ph value is 6.0～6.5.
28. methods as claimed in claim 24 are it is characterised in that described precipitated silica is median d50At least
250 μm spherical.
29. methods as claimed in claim 24 are it is characterised in that described precipitated silica is at least 0.5mm's for size
Graininess, pellet hardness is 10～40g.
30. methods as claimed in claim 29 are it is characterised in that described pellet hardness is 15～25g.
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| CN107697921A (en) * | 2017-10-30 | 2018-02-16 | 无锡恒诚硅业有限公司 | A kind of 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 |
| CN106829976B (en) * | 2017-03-16 | 2018-10-30 | 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 |
| 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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| 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 |
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