CN108439414A - A kind of method that pH value swing method prepares high dispersive macropore appearance precipitated silica - Google Patents
A kind of method that pH value swing method prepares high dispersive macropore appearance precipitated silica Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/124—Preparation of adsorbing porous silica not in gel form and not finely divided, i.e. silicon skeletons, by acidic treatment of siliceous materials
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a kind of pH value swing methods to prepare the method that high dispersive macropore holds precipitated silica, and the dispersion grade that high dispersive macropore of the invention holds precipitated silica is 9.5 10；Mercury determining adsorption large pore volume is in equal to 1.7cm3/g.Preparation method is received with dilute sulfuric acid using liquid silicic acid as raw material, and control ph swings back and forth 5 times totally between 11 ± 1 to 5 ± 1, then carries out pressure filtration washing, spray drying, granulation, holds precipitated silica to which high dispersive macropore be made.Precipitated silica produced by the present invention holds with polymolecularity and with macropore.
Description
Technical field
The present invention relates to the preparation fields of precipitated silica, and in particular to a kind of high dispersive macropore appearance precipitated silica
Silicon and pH value swing method prepare the method that high dispersive macropore holds precipitated silica.
Background technology
Precipitated silica is a kind of novel fine chemical product of modern industry, is widely used in tire, rubber product, makes
Paper, feed addictive, food additives, plastics, building energy-saving heat-insulating material, toothpaste, pesticide, ink etc.；With science and technology into
Step, its performance are constantly realized, and purposes is constantly expanding, and especially in automobile tire product, is widely used.This be because
For as the requirement of, safety environmentally protective to tire, riding comfort is higher and higher, tire enterprise must just add in tire
Enter more precipitated silicas, especially dispersion performance more preferably and the precipitated silica of macropore appearance can just be met the requirements.
The high aggregation of mercury adsorptive value, branched structure is more and flourishing, has a higher structure, and when mixing is more because of hole, and sizing material is wherein
Infiltration is slower, has the more time to moisten, well dispersed；And the white carbon of low structure is combined comparatively fast with sizing material, and hard charcoal
Easily assemble again between black track producing particle, viscosity increases very fast, it is difficult to disperse.Conventional precipitation silica mercury adsorptive value generally exists
1.2cm3/g-1.5cm3Between/g；In tire tread glue, 20-30 parts of precipitated silicas can only be added, while 50-60 is added
The tire that conventional precipitation silica and carbon black make as the tread rubber of reinforcing agent is added as reinforcing agent in part carbon black,
The tire that its rolling resistance makes with full carbon black as the tread rubber of reinforcing agent does not reduce substantially；
Precipitated silica is held as reinforcing agent using high dispersive macropore, can be added in tread rubber it is 70-80 parts most,
5-10 parts of carbon black is added and only plays pigmentation；The tire made of the formula tread rubber, rolling resistance and full carbon black with
And the tire that a small amount of conventional precipitation silica makes as the tread rubber of reinforcement agent prescription, significantly reduce rolling resistance 15-
20%.Show that automobile fuel consumption reduces 3-5%.
In the prior art, the production method of precipitated silica has Physical and chemical method, to obtain active good, reinforcement
Property high Amorphous precipitated silica need to use chemical method.Chemical method is divided into two kinds of dry method pyrolysis and wet-precipitated.Dry method
Pyrolysis is divided into vapor phase method and arc process；Wet-precipitated is divided into sulfuric acid, hydrochloric acid, nitric acid and carbon dioxide precipitates method etc..Currently, precipitation
Silica production mainly uses vapor phase method and two kinds of sulfuric acid, hydrochloric acid precipitation method production technologies.
Fume colloidal silica is because its process units amount of investment is big, and set of device production capacity is generally at 5000 tons or less；In addition gas
The energy consumption and overall cost of phase method white carbon are too high, and powder application field is narrow, is mainly used for the fields such as ink, silicon rubber；
Due to being influenced by all many factors such as raw material, energy consumption, cost, application field, production capacity, technology, vapor phase method hard charcoal
Prepared by black powder have limitation.
And silica made from the precipitation method, usually because silanol group is contained on surface, cause the surface polarity of white carbon compared with
Greatly, it is easily flooded profit, and it is bad with the compatibility of organic matter, short Type of Collective object, it significantly reduces performance and uses model
It encloses, so usually needing to be modified it, modified white carbon black, to enhance its performance, expand its use scope, partial alternative gas is made
Phase method silica.
According to electron microscope observation, for the macrostructure of precipitated silica (hydrated SiO 2) as carbon black, particle is in ball
Shape, microstructure are divided into 3 levels, primary particle, aggregation and agglomerate.Primary particle is as independent particle appropriate
Analysis method under can identify.Under an electron microscope, the primary particle of precipitated silica is diameter in 2-20nm
Spheroidal particle.Aggregation is the chain or aggregate structure formed by primary particle agglomeration.Aggregation extent can be defined as：White carbon
The structure polymerizeing as one cannot be broken up structure for primary particle under any dispersing method and process.Agglomerate is poly-
The loose combination of collective, is combined together by Van der Waals force.It is poly- that agglomerate can be broken up under ideal dispersion technology
Collective.
By under different processes, precipitating and the parameter in mill processes, average grain diameter, dispersed particle size and aggregation etc.
Grade can have very big difference in a relatively wide range.In essence, the smallest particles in precipitated silica are poly-
Collective is not primary particle.
It is analyzed from the synthesis mechanism of existing precipitated silica, precipitated silica preparation process can be summarized as two
Class dynamic process:When the growth course of the nucleus of precipitated silica, second is that the growth accumulation process of nucleus.Currently, liquid phase
The production of precipitated silica is all made of the concentrated sulfuric acid at home or dilute sulfuric acid two-step method carries out：It is molten that first step reaction generates dilute silicon
Glue, parked curing a period of time, nucleus is gradually formed in dilute Ludox, the crystal seed as the second reaction；Second step is i.e. with containing
Mother liquor of the solution of crystal seed as aggregation growth adds waterglass and dilute sulfuric acid to carry out precipitation reaction by certain speed, and reaction is certain
After time, stop that sodium silicate solution is added, only plus dilute sulfuric acid carries out acidification, when reacting liquid pH value reaches certain value, stops
Acid adding is aged certain time, then filters and wash with water, and removes Na2SO4Afterwards, product is obtained after sending drying.
Existing this technique, since reaction process state modulator is unreasonable, the precipitate silica product caused
Dispersion performance is poor and Kong Rong little, cannot meet requirement of the green tire to high-end precipitated silica.
Invention content
To solve problems of the prior art, it is heavy that the present invention provides a kind of pH value swing method preparation high dispersive macropore appearance
The method of shallow lake silica.
The high dispersive macropore of the present invention holds precipitated silica, and dispersion grade is 9.5-10；Mercury determining adsorption large pore volume
In equal to 1.7cm3/g。
The present invention also provides a kind of pH value swing methods to prepare the side that high dispersive macropore as described above holds precipitated silica
Method comprising following step：
It is received with dilute sulfuric acid as raw material using liquid silicic acid, control ph swings back and forth 5 times totally between 11 ± 1 to 5 ± 1, so
Pressure filtration washing, spray drying, granulation are carried out afterwards, hold precipitated silica to which high dispersive macropore be made.
Wherein, the control ph swings back and forth between 11 ± 1 to 5 ± 1 and includes the following steps for totally 5 times:
A, material allocation:Preparation density is 1.10g/cm3-1.30g/cm3Sodium silicate solution, density 1.05g/cm3-
1.10g/cm3Sulfuric acid solution, density 1.02g/cm3-1.08g/cm3Metabisulfite solution it is spare；
B, the hot water for being 40 DEG C -60 DEG C with the sodium silicate solution, metabisulfite solution and temperature is allocated close in synthesis reactor
Degree is 1.01-1.04g/cm3, pH value be 11 ± 1 mixed liquor, and stir until reaction terminate, formed the first mixed solution；
C, 5-10 minutes are kept the temperature after first mixed solution being heated to 70 DEG C -95 DEG C；
D, sulfuric acid solution is added into reaction kettle and stirs, until it is molten to form the second mixing that pH value is 5 ± 1 in reaction kettle
Liquid；From pH11 ± 1 to pH5 ± 1, time control was at 2-10 minutes；The temperature of mixed liquor is maintained at 70 DEG C -95 DEG C in the process；
E, second mixed solution is maintained at 70 DEG C -95 DEG C and keeps the temperature 5-10 minutes；
F, sodium silicate solution is added into reaction kettle and stirs, until forming the third that pH value reaches 11 ± 1 in reaction kettle
Mixed liquor, the density domination of third mixed liquor is in 1.04-1.07g/cm3, from pH5 ± 1 to pH11 ± 1, time control is in 2-10
Minute；The temperature of mixed liquor is maintained at 70 DEG C -95 DEG C in the process；
Above-mentioned third mixed solution is maintained at 70 DEG C -95 DEG C and keeps the temperature 5-10 minutes by G；
H, sulfuric acid solution is added into reaction kettle and stirs, until it is molten to form the 4th mixing that pH value is 5 ± 1 in reaction kettle
Liquid；From pH11 ± 1 to pH5 ± 1, time control was at 2-10 minutes；The temperature of mixed liquor is maintained at 70 DEG C -95 DEG C in the process；
I, above-mentioned 4th mixed solution is maintained at 70 DEG C -95 DEG C and keeps the temperature 5-10 minutes；
J, sodium silicate solution is added into reaction kettle and stirs, until forming the pH value reaches 11 ± 1 the 5th in reaction kettle
Mixed liquor, the density domination of the 5th mixed liquor is in 1.07-1.10g/cm3, from pH5 ± 1 to pH11 ± 1, time control is in 2-10
Minute；The temperature of mixed liquor is maintained at 70 DEG C -95 DEG C in the process；
K, above-mentioned 5th mixed solution is maintained at 70 DEG C -95 DEG C and keeps the temperature 5-10 minutes；
L, sulfuric acid solution is added into reaction kettle and stirs, until it is molten to form the 6th mixing that pH value is 5 ± 1 in reaction kettle
Liquid；From pH11 ± 1 to pH5 ± 1, time control was at 2-10 minutes；The temperature of mixed liquor is maintained at 70 DEG C -95 DEG C in the process；
M, above-mentioned 6th mixed solution is maintained at 70 DEG C -95 DEG C and keeps the temperature 5-10 minutes.
In addition, in the step B- steps M, the speed of stirring is 25-100r/min.
In addition, the pressure filtration washing is the pulpous state of 22-26% precipitation dioxy to solid content is obtained by percentage to the quality
The slurry of SiClx.
In addition, the equipment that the press filtration step uses is diaphragm filter press.
In addition, the precipitated silica particles moisture after dry is 4%-8%, meso-position radius 250-400um.
In addition, the granulation includes that the slurry of pulpous state precipitated silica is carried out press atomization through positive displacement high-pressure pump,
And it is dried to obtain silica particles into drying tower.
In addition, spray drying hot wind into temperature when tower be 550-75 DEG C；Hot wind enters drying with material cocurrent from tower top
Tower.
In addition, the cycling utilization of wastewater obtained by the 6th mixed liquor press filtration be diluted obtained density to sodium sulphate solution being
1.02g/cm3-1.08g/cm3Metabisulfite solution.
In addition, with the molar ratio computing of silica/sodium oxide molybdena, the modulus of the sodium silicate is 3.2-3.6.
Product produced by the invention has good dispersibility in the polymer, can applied to green tire tread rubber
To reduce the rolling resistance of tire.
The beneficial effects of the invention are as follows:Using raw material identical with production conventional precipitation silica, joined using technique
Several regulation and control prepare the precipitated silica that high dispersive macropore holds, and especially meet the high-end precipitated silica of green tire needs
Silicon.The product of production has dispersion effect good, and product appearance microballon shape is uniform.Stable production process is, it can be achieved that large-scale production.
High dispersive macropore of the present invention holds precipitated silica and uses unique production technology, passes through pH value swing method, regulation and control
The generating process of the aggregation of product generates the special construction of precipitated silica, and aggregation, branched structure is more and flourishing, tool
There is a higher structure, because hole is more when mixing, sizing material permeates relatively slow wherein, has the more time to moisten, well dispersed；And
The white carbon of low structure is combined comparatively fast with sizing material, and is easily assembled again between hard charcoal black track producing particle, and viscosity increases very fast, it is difficult to point
It dissipates.
Conventional precipitation silica mercury adsorptive value is generally in 1.2cm3/g-1.5cm3Between/g；In tire tread glue, only
20-30 parts of precipitated silicas can be added, while 50-60 parts of carbon blacks are added as reinforcing agent, therefore conventional precipitation dioxy is added
The tire that SiClx and carbon black make as the tread rubber of reinforcing agent, rolling resistance and tread rubber system of the full carbon black as reinforcing agent
The tire of work does not reduce substantially.
High dispersive macropore using the present invention holds precipitated silica as reinforcing agent, can be added in tread rubber at most
70-80 parts, 5-10 parts of carbon black is added and only plays pigmentation；Using the formula tread rubber make tire, rolling resistance with
The tire that full carbon black and a small amount of conventional precipitation silica make as the tread rubber of reinforcement agent prescription, significantly reduces and rolls resistance
Power 15-20%.Show that automobile fuel consumption reduces 3-5%.
Specific implementation mode
Technical solution of the present invention is discussed in detail with reference to embodiment, but the present invention is not limited to these embodiments.
Embodiment 1
Prepare the technique that high dispersive macropore holds precipitated silica：
A, material allocation:Allotment density is 1.10g/cm3Sodium metasilicate (with the molar ratio computing of silica/sodium oxide molybdena, silicon
The modulus of sour sodium is in 3.2-3.6) solution, density is 1.05g/cm after dilution3Sulfuric acid solution, density is 1.02g/cm after dilution3
Metabisulfite solution it is spare；
B, it is 40 DEG C of hot water in synthesis reactor by sodium silicate solution, metabisulfite solution and the temperature of listed density in above-mentioned A
Inside it is allocated as 1.01g/cm3, pH value is controlled 11 ± 1, and stirs (speed 25r/min) until reaction terminates to form the first mixing
Solution；
C, it heats up:10 minutes are kept the temperature after above-mentioned first mixed solution is heated to 70 DEG C；
D, sulfuric acid solution deployed in step A is added in reaction kettle and is stirred (speed 25r/min), until reaction
The second mixed solution that pH value is 5 ± 1 is formed in kettle；From pH11 ± 1 to pH5 ± 1, time control was at 10 minutes；It mixes in the process
The temperature for closing liquid is maintained at 70 DEG C；
E, above-mentioned second mixed solution is maintained at 70 DEG C and keeps the temperature 5 minutes；
F, sodium silicate solution deployed in step A and stirring (speed 25r/min) is added simultaneously in a kettle, until
The third mixed liquor that pH value reaches 11 ± 1 is formed in reaction kettle, the density domination of third mixed liquor is in 1.04g/cm3, from pH5 ±
1 to pH11 ± 1, and time control was at 2 minutes；The temperature of mixed liquor is maintained at 70 DEG C DEG C in the process；
Above-mentioned third mixed solution is maintained at 70 DEG C DEG C and keeps the temperature 5 minutes by G；
H, sulfuric acid solution deployed in step A is added in reaction kettle and is stirred (speed 25r/min), until reaction
The 4th mixed solution that pH value is 5 ± 1 is formed in kettle；From pH11 ± 1 to pH5 ± 1, time control was at 2 minutes；It mixes in the process
The temperature of liquid is maintained at 70 DEG C DEG C；
Above-mentioned 4th mixed solution is maintained at 70 DEG C DEG C and keeps the temperature 5 minutes by I；
Sodium silicate solution deployed in step A and stirring (speed 25r/min) is added simultaneously in a kettle in J, until
The 5th mixed liquor that pH value reaches 11 ± 1 is formed in reaction kettle, the density domination of the 5th mixed liquor is in 1.07g/cm3, from pH5 ±
1 to pH11 ± 1, and time control was at 2 minutes；The temperature of mixed liquor is maintained at 70 DEG C DEG C in the process；
Above-mentioned 5th mixed solution is maintained at 70 DEG C DEG C and keeps the temperature 5 minutes by K；
Sulfuric acid solution deployed in step A is added in reaction kettle and is stirred (speed 25r/min) by L, until reaction
The 6th mixed solution that pH value is 5 ± 1 is formed in kettle；From pH11 ± 1 to pH5 ± 1, time control was at 2 minutes；It mixes in the process
The temperature of liquid is maintained at 70 DEG C；
Above-mentioned 6th mixed solution is maintained at 70 DEG C DEG C and keeps the temperature 5 minutes by M；
Diaphragm filter press is used to obtain solid content through pressure filtration washing, liquefaction as 22% (quality 100 the 6th mixed solution
Point ratio) pulpous state precipitated silica slurry.
It is further granulated, is specifically included:Pulpous state precipitated silica slurry carries out pressure spray through positive displacement high-pressure pump
Mist, and enter drying tower and dry, the precipitated silica particles moisture after control is dry is 4%-8%, meso-position radius 250-
400um, to obtain silica particles, properties measure as described in Table 1.
Table 1
Embodiment 2
Prepare the technique that high dispersive macropore holds precipitated silica：
A, material allocation:Allotment density is 1.30g/cm3Sodium metasilicate (with the molar ratio computing of silica/sodium oxide molybdena, silicon
The modulus of sour sodium is in 3.2-3.6) solution, density is 1.10g/cm after dilution3Sulfuric acid solution, density is 1.08g/cm after dilution3
Metabisulfite solution it is spare；
B, it is 60 DEG C of hot water in synthesis reactor by sodium silicate solution, metabisulfite solution and the temperature of listed density in above-mentioned A
Inside it is allocated as 1.04g/cm3, pH value is controlled 11 ± 1, and stirs (speed 100r/min) until reaction end formation first is mixed
Close solution；
C, it heats up:10 minutes are kept the temperature after above-mentioned first mixed solution is heated to 95 DEG C；
D, sulfuric acid solution deployed in step A is added in reaction kettle and is stirred (speed 100r/min), until anti-
Answer the second mixed solution for forming that pH value is 5 ± 1 in kettle；From pH11 ± 1 to pH5 ± 1, time control was at 10 minutes；In the process
The temperature of mixed liquor is maintained at 95 DEG C；
E, above-mentioned second mixed solution is maintained at 95 DEG C and keeps the temperature 10 minutes；
F, sodium silicate solution deployed in step A and stirring (speed 100r/min) is added simultaneously in a kettle, directly
The third mixed liquor that pH value reaches 11 ± 1 is formed in reaction kettle, the density domination of third mixed liquor is in 1.07g/cm3, from pH5
± 1 to pH11 ± 1, and time control was at 10 minutes；The temperature of mixed liquor is maintained at 95 DEG C in the process；
Above-mentioned third mixed solution is maintained at 95 DEG C and keeps the temperature 10 minutes by G；
H, sulfuric acid solution deployed in step A is added in reaction kettle and is stirred (speed 100r/min), until anti-
Answer the 4th mixed solution for forming that pH value is 5 ± 1 in kettle；From pH11 ± 1 to pH5 ± 1, time control was at 2 minutes；It mixes in the process
The temperature for closing liquid is maintained at 95 DEG C；
Above-mentioned 4th mixed solution is maintained at 95 DEG C and keeps the temperature 5 minutes by I；
Sodium silicate solution deployed in step A and stirring (speed 100r/min) is added simultaneously in a kettle in J, until
The 5th mixed liquor that pH value reaches 11 ± 1 is formed in reaction kettle, the density domination of the 5th mixed liquor is in 1.10g/cm3, from pH5 ±
1 to pH11 ± 1, and time control was at 10 minutes；The temperature of mixed liquor is maintained at 95 DEG C in the process；
Above-mentioned 5th mixed solution is maintained at 95 DEG C and keeps the temperature 10 minutes by K；
Sulfuric acid solution deployed in step A is added in reaction kettle and is stirred (speed 100r/min) by L, until reaction
The 6th mixed solution that pH value is 5 ± 1 is formed in kettle；From pH11 ± 1 to pH5 ± 1, time control was at 10 minutes；It mixes in the process
The temperature for closing liquid is maintained at 95 DEG C；
Above-mentioned 6th mixed solution is maintained at 95 DEG C and keeps the temperature 5 minutes by M；
Diaphragm filter press is used to obtain solid content through pressure filtration washing, liquefaction as 26% (quality 100 the 6th mixed solution
Point ratio) pulpous state precipitated silica slurry.
It is further granulated, is specifically included:Pulpous state precipitated silica slurry carries out pressure spray through positive displacement high-pressure pump
Mist, and enter drying tower and dry, the precipitated silica particles moisture after control is dry is 4%-8%, meso-position radius 250-
400um, to obtain silica particles, properties measure as described in Table 2.
Table 2
Claims (10)
1. a kind of high dispersive macropore holds precipitated silica, which is characterized in that the high dispersive macropore holds precipitated silica
Dispersion grade is 9.5-10；Mercury determining adsorption large pore volume is in equal to 1.7cm3/g。
2. a kind of pH value swing method prepares the method that high dispersive macropore as described in claim 1 holds precipitated silica, special
Sign is, includes the following steps：
Received with dilute sulfuric acid as raw material using liquid silicic acid, control ph swings back and forth 5 times totally between 11 ± 1 to 5 ± 1, then into
Row pressure filtration washing, spray drying, granulation hold precipitated silica to which high dispersive macropore be made.
3. according to the method described in claim 2, it is characterized in that, the control ph carrys out backswing between 11 ± 1 to 5 ± 1
It is dynamic to include the following steps for totally 5 times:
A, material allocation:Preparation density is 1.10g/cm3-1.30g/cm3Sodium silicate solution, density 1.05g/cm3-
1.10g/cm3Sulfuric acid solution, density 1.02g/cm3-1.08g/cm3Metabisulfite solution it is spare；
B, the hot water for being 40 DEG C -60 DEG C with the sodium silicate solution, metabisulfite solution and temperature allocates density in synthesis reactor and is
1.01-1.04g/cm3, pH value be 11 ± 1 mixed liquor, and stir until reaction terminate, formed the first mixed solution；
C, 5-10 minutes are kept the temperature after first mixed solution being heated to 70 DEG C -95 DEG C；
D, sulfuric acid solution is added into reaction kettle and stirs, until forming the second mixed solution that pH value is 5 ± 1 in reaction kettle；
From pH11 ± 1 to pH5 ± 1, time control was at 2-10 minutes；The temperature of mixed liquor is maintained at 70 DEG C -95 DEG C in the process；
E, second mixed solution is maintained at 70 DEG C -95 DEG C and keeps the temperature 5-10 minutes；
F, sodium silicate solution is added into reaction kettle and stirs, until forming the third mixing that pH value reaches 11 ± 1 in reaction kettle
Liquid, the density domination of third mixed liquor is in 1.04-1.07g/cm3, from pH5 ± 1 to pH11 ± 1, time control was at 2-10 minutes；
The temperature of mixed liquor is maintained at 70 DEG C -95 DEG C in the process；
Above-mentioned third mixed solution is maintained at 70 DEG C -95 DEG C and keeps the temperature 5-10 minutes by G；
H, sulfuric acid solution is added into reaction kettle and stirs, until forming the 4th mixed solution that pH value is 5 ± 1 in reaction kettle；
From pH11 ± 1 to pH5 ± 1, time control was at 2-10 minutes；The temperature of mixed liquor is maintained at 70 DEG C -95 DEG C in the process；
I, above-mentioned 4th mixed solution is maintained at 70 DEG C -95 DEG C and keeps the temperature 5-10 minutes；
J, sodium silicate solution is added into reaction kettle and stirs, until forming the 5th mixing that pH value reaches 11 ± 1 in reaction kettle
Liquid, the density domination of the 5th mixed liquor is in 1.07-1.10g/cm3, from pH5 ± 1 to pH11 ± 1, time control was at 2-10 minutes；
The temperature of mixed liquor is maintained at 70 DEG C -95 DEG C in the process；
K, above-mentioned 5th mixed solution is maintained at 70 DEG C -95 DEG C and keeps the temperature 5-10 minutes；
L, sulfuric acid solution is added into reaction kettle and stirs, until forming the 6th mixed solution that pH value is 5 ± 1 in reaction kettle；
From pH11 ± 1 to pH5 ± 1, time control was at 2-10 minutes；The temperature of mixed liquor is maintained at 70 DEG C -95 DEG C in the process；
M, above-mentioned 6th mixed solution is maintained at 70 DEG C -95 DEG C and keeps the temperature 5-10 minutes.
4. according to the method described in claim 3, it is characterized in that, in the step B- steps M, the speed of stirring is 25-
100r/min。
5. according to the method described in claim 2, it is characterized in that, the pressure filtration washing is to obtaining solid content with quality percentage
Slurry than the pulpous state precipitated silica for being calculated as 22-26%.
6. according to the method described in claim 2, it is characterized in that, the precipitated silica particles moisture after dry is 4%-
8%, meso-position radius 250-400um.
7. according to the method described in claim 2, it is characterized in that, described be granulated includes by the slurry of pulpous state precipitated silica
Press atomization is carried out through positive displacement high-pressure pump, and silica particles are dried to obtain into drying tower.
8. according to the method described in claim 2, it is characterized in that, spray drying hot wind into temperature when tower be 550-75 DEG C；
Hot wind enters drying tower with material cocurrent from tower top.
9. according to the method described in claim 2, it is characterized in that, by the cycling utilization of wastewater pair obtained by the 6th mixed liquor press filtration
It is 1.02g/cm that sodium sulphate solution, which is diluted obtained density,3-1.08g/cm3Metabisulfite solution.
10. according to the method described in claim 2, it is characterized in that, with the molar ratio computing of silica/sodium oxide molybdena, the silicon
The modulus that acid is received is 3.2-3.6.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054193A (en) * | 2019-06-05 | 2019-07-26 | 确成硅化学股份有限公司 | A kind of preparation method of high-dispersion high-thermal-conductivity white carbon black |
| CN110127709A (en) * | 2019-06-05 | 2019-08-16 | 确成硅化学股份有限公司 | A kind of method of gradient pH precipitation method preparation high dispersive silica |
| CN111825098A (en) * | 2020-07-15 | 2020-10-27 | 确成硅化学股份有限公司 | High-dispersion large-pore-volume narrow-pore-diameter-distribution hydrated silicon dioxide and preparation method thereof |
| CN111825097A (en) * | 2020-07-15 | 2020-10-27 | 确成硅化学股份有限公司 | Low-aluminum high-dispersion white carbon black and preparation method thereof |
| CN112299425A (en) * | 2020-10-30 | 2021-02-02 | 石家庄优士科电子科技有限公司 | Silica sol with convex colloid surface and preparation method and application thereof |
| CN114105153A (en) * | 2021-12-07 | 2022-03-01 | 无锡恒诚硅业有限公司 | Method for preparing rubber reinforced silicon dioxide |
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| CN110054193A (en) * | 2019-06-05 | 2019-07-26 | 确成硅化学股份有限公司 | A kind of preparation method of high-dispersion high-thermal-conductivity white carbon black |
| CN110127709A (en) * | 2019-06-05 | 2019-08-16 | 确成硅化学股份有限公司 | A kind of method of gradient pH precipitation method preparation high dispersive silica |
| WO2020244182A1 (en) * | 2019-06-05 | 2020-12-10 | 确成硅化学股份有限公司 | Method for preparing high-dispersion silica by gradient ph precipitation |
| WO2020244181A1 (en) * | 2019-06-05 | 2020-12-10 | 确成硅化学股份有限公司 | Method for preparing high dispersion and high thermal conductivity silica |
| CN110127709B (en) * | 2019-06-05 | 2021-09-28 | 确成硅化学股份有限公司 | Method for preparing high-dispersion silicon dioxide by gradient pH precipitation method |
| CN111825098A (en) * | 2020-07-15 | 2020-10-27 | 确成硅化学股份有限公司 | High-dispersion large-pore-volume narrow-pore-diameter-distribution hydrated silicon dioxide and preparation method thereof |
| CN111825097A (en) * | 2020-07-15 | 2020-10-27 | 确成硅化学股份有限公司 | Low-aluminum high-dispersion white carbon black and preparation method thereof |
| CN111825098B (en) * | 2020-07-15 | 2023-10-27 | 确成硅化学股份有限公司 | High-dispersion large-pore-volume pore-diameter narrow-distribution hydrated silicon dioxide and preparation method thereof |
| CN111825097B (en) * | 2020-07-15 | 2023-10-27 | 确成硅化学股份有限公司 | Low-aluminum high-dispersion white carbon black and preparation method thereof |
| CN112299425A (en) * | 2020-10-30 | 2021-02-02 | 石家庄优士科电子科技有限公司 | Silica sol with convex colloid surface and preparation method and application thereof |
| CN114105153A (en) * | 2021-12-07 | 2022-03-01 | 无锡恒诚硅业有限公司 | Method for preparing rubber reinforced silicon dioxide |
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