CN113831760A - Preparation method of modified silica and modified silica - Google Patents
Preparation method of modified silica and modified silica Download PDFInfo
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- CN113831760A CN113831760A CN202111179179.8A CN202111179179A CN113831760A CN 113831760 A CN113831760 A CN 113831760A CN 202111179179 A CN202111179179 A CN 202111179179A CN 113831760 A CN113831760 A CN 113831760A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 348
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 115
- 238000000227 grinding Methods 0.000 claims abstract description 111
- 239000000843 powder Substances 0.000 claims abstract description 106
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002270 dispersing agent Substances 0.000 claims abstract description 45
- 239000002002 slurry Substances 0.000 claims abstract description 42
- 230000004048 modification Effects 0.000 claims abstract description 20
- 238000012986 modification Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 239000003607 modifier Substances 0.000 claims description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 17
- 230000008878 coupling Effects 0.000 claims description 17
- 238000010168 coupling process Methods 0.000 claims description 17
- 238000005859 coupling reaction Methods 0.000 claims description 17
- 229910000077 silane Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 30
- 238000001238 wet grinding Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229920005646 polycarboxylate Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000001694 spray drying Methods 0.000 description 9
- 238000005507 spraying Methods 0.000 description 8
- 229920002125 Sokalan® Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical group [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/19—Oil-absorption capacity, e.g. DBP values
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Abstract
The application relates to the field of inorganic powder, and particularly discloses a preparation method of modified silica powder, which comprises the following preparation steps: the modified silica is obtained by crude crushing of raw ore, preparation of water slurry, grinding of the water slurry, drying and modification of the water slurry, wherein the preparation of the water slurry is to disperse silica powder and a dispersing agent into water to form the water slurry, and then the wet grinding is carried out on the water slurry. The modified silica prepared by the preparation method realizes the peeling between layers, maintains the sheet structure and obtains the modified silica with low fineness and large specific surface area. The preparation method has the advantages that the grinding effect is good, and the silica powder is not easy to sink and agglomerate in water slurry.
Description
Technical Field
The application relates to the field of inorganic powder, in particular to a preparation method of modified silica and the modified silica.
Background
In order to improve the quality, characteristics and processability of plastic products and rubber products, auxiliary chemicals, namely processing aids, are added in the actual production process to endow the plastic products or the rubber products with characteristics.
Silica is a mineral aggregate mainly composed of quartz and containing a certain amount of argillaceous substances. The fine powder with a sheet structure is formed by crushing and processing the silica ore, and can be directly applied to the fields of ceramic calcination, glass production, rubber and plastic product preparation and the like as an inorganic filler.
When silica is used as a filler to be applied to a resin material, because the surface of the silica has hydrophilic groups, most of the resin material has hydrophobicity, and the compatibility between the resin material and the silica material is poor, the resin material, the silica raw material and a coupling agent are usually mixed at present, or a mode that the coupling agent firstly modifies the silica raw material and then mixes the modified silica with the resin material is adopted, so that the two materials with greatly different properties of the resin material and the silica raw material are mutually combined to improve the performance of a product.
In view of the above-mentioned related technologies, the inventors believe that before modifying the silica raw material with the coupling agent, the silica raw material generally needs to be crushed and ground to increase the specific surface area of the silica raw material so that the silica raw material can fully contact and react with the coupling agent, but excessive grinding causes agglomeration of silica raw material particles, and the specific surface area of the agglomerated silica raw material in a specific surface area-to-particle state is reduced, thereby affecting the modification degree of silica and the subsequent binding property with the resin material.
Disclosure of Invention
In order to solve the problem of particle agglomeration of silica, ensure that a silica raw material can fully contact and react with a coupling agent and improve the modification effect, the application provides a preparation method of modified silica and the modified silica.
In a first aspect, the present application provides a method for preparing modified silica, which adopts the following technical scheme:
a preparation method of modified silica comprises the following preparation steps:
s1, coarse crushing of raw ore: crushing, coarsely grinding and screening a silica raw material to obtain silica powder;
s2, preparing water slurry: dispersing a dispersing agent and silica powder into water, and uniformly stirring to obtain silica slurry;
s3, water slurry grinding: finely grinding the silica slurry;
s4, drying the water slurry: drying and granulating the finely ground silica slurry to obtain dry powder;
s5, preparing a finished product: dispersing the dried powder, and adding a silane coupling modifier for modification to obtain the modified silica.
By adopting the technical scheme, after the coarse grinding process is carried out on the silica raw material, the lamella of part of the silica raw material is peeled off, pores are formed in the silica powder particles, the silica powder particles have a loose state, the specific surface area of the powder is increased, and the viscosity of a dispersion system is reduced under the action of a dispersing agent, so that the silica slurry can keep high solid content and good fluidity, and the subsequent fine grinding operation is facilitated; the silica powder is dispersed in water, because the affinity between the silica powder interfaces is strong, the attraction energy is high, the aggregation among the silica powder particles is easy to be enlarged and even agglomerated, and the problem of aggregation among the silica powder particles can be improved by adding the dispersing agent, so that the system keeps the dispersion stability and the suspension effect.
Through fine grinding, the silica powder is further laminated and peeled, the volume of silica powder particles is increased, the specific surface area is increased, the silica with large thickness is thinned after grinding, the number of hydroxyl groups on the surface of the silica powder is increased, and the surface activity is increased. When the dry silica powder is contacted with the silane coupling modifier in a high specific surface area and high activity state, the modifier can be fully contacted with each surface of the dry silica powder, so that the grafting effect of the dry silica powder and modifier molecules is improved, the modification effect of the dry silica powder is improved, the modified silica has good surface activity, and can be better dispersed into a high polymer material to be combined with the high polymer material. And after the silane coupling modifier is combined with the dry powder, the modifier consumes hydroxyl on the surface of the dry powder of the lamella, and simultaneously introduces modifier molecules on the surface of the dry powder, thereby changing the surface structure and the chemical state of the dry powder, further reducing the agglomeration of the silica powder, and effectively improving the moisture absorption of the modified silica.
Preferably, in the step of preparing the S2 water slurry, the stirring speed is 15-35 r/min.
The low stirring speed of 15-35r/min can ensure that the powder does not sink in the preparation process of the water slurry, ensure that the powder can be uniformly dispersed in a water environment, and keep the suspension effect in the system, thereby being beneficial to the subsequent grinding operation.
Preferably, the weight ratio of the dispersing agent and the silica powder added in the step S2 is (0.2-0.5) wt%: (35-40) wt%.
Preferably, the dispersant is a polycarboxylate dispersant.
Preferably, the solid content of the polycarboxylate-type dispersant is 40-65%.
Preferably, the solid content of the silica slurry in the S2 is 50-70%.
By adopting the technical scheme, the polycarboxylate dispersant is used as organic acid and has more active groups, when the polycarboxylate dispersant and the silica powder are dispersed into water together, the polycarboxylate dispersant can be adsorbed on the surface of the silica powder due to the interaction of ionic bonds, covalent bonds, hydrogen bonds, van der waals force and the like, so that the silica powder particles are charged with negative charges, electrostatic repulsive force is formed around the silica powder particles which are originally easy to attract and agglomerate due to electrostatic adsorption, the silica powder particles which are close to each other are mutually repelled and separated, and the agglomeration of the silica powder particles is prevented, so that the dispersion system keeps the dispersion stability of the dispersion system, and the powder is not easy to settle; and through the adsorption effect of the dispersing agent, the silica powder can continuously keep good activity, is favorable for subsequent contact with a silane coupling modifier, and is favorable for improving the modification effect of the silica powder. And the polycarboxylate is removed simultaneously in the subsequent drying treatment, so that the subsequent treatment of the powder or the quality of the modified silica finished product is not influenced.
The polycarboxylate dispersant with the solid content of 40-65% is selected, so that the solid content of the silica slurry system can be improved, the solid content of the silica slurry can be kept at 50-70%, the dispersion efficiency is high, and the grinding efficiency is high. And because of the high activity, high solid content and high cost performance of the polycarboxylate dispersant, the dispersion effect and the dispersion efficiency of the silica powder in water can be greatly improved by a small amount of the dispersant.
Preferably, in the step of fine grinding in S3, the grinding speed is kept at 80-130r/min, and the fine grinding time is 1.2-2.5h in total.
Preferably, in the step S3, the silica slurry is ground for a plurality of times, and the particle sizes of the grinding media during the plurality of times of grinding are sequentially decreased.
By adopting the technical scheme, due to the addition of the polycarboxylate dispersant, under the condition of low rotating speed of 80-130r/min, the polycarboxylate dispersant plays a role of a carrier and carries the powder to be adsorbed on the surface of the grinding medium, so that the opportunity of the grinding medium for capturing the powder is increased, and the energy of the grinding medium can be fully transmitted to the powder by combining multiple continuous grinding, so that the flaking of the powder is promoted; meanwhile, the polycarboxylate dispersant and the grinding medium are matched to play a good role in grinding aid and lubrication, so that the surface free energy of the powder is reduced, the possibility of powder agglomeration is reduced, the grinding efficiency of the silica powder is improved, the grinding time is greatly reduced, and the overall efficiency of modified silica preparation is improved.
The fine grinding is carried out by adopting a stirring mill stripping machine, and the grinding medium in the stirring mill stripping machine does integral multidimensional circulating motion and autorotation motion in the cylinder, and simultaneously generates shearing and friction action rather than impact action, and the shearing and friction action can enable laminated silica to generate the action between layers so as to strip the laminated silica, avoid the damage of the silica structure from the surface action of the silica and keep the laminated structure of the silica; and as the particle size of the grinding medium is reduced in sequence, the grinding medium is reduced in sequence along with the reduction of the particle size of the silica powder, so that the sufficient monomer dissociation strength can be maintained and the silica sheet structure can be fully protected.
Preferably, the preparation method of the silane coupling modifier comprises the following steps: uniformly mixing a silane coupling agent and an organic solvent to prepare a silane coupling modifier; wherein the silane coupling agent is one of KH550 and KH 560; the organic solvent is one of ethanol, methanol and isopropanol.
The organic solvent is used as a carrier, the organic solvent is sprayed to the surface of the silica with the silane coupling agent and is fully contacted with the silica for modification, the silane coupling modifier is grafted with active groups on the surface of the silica to achieve a modification effect, and the organic solvent can be quickly volatilized in the modification process to reduce the residue of the organic solvent on the surface of the silica.
In a second aspect, the application provides modified silica, which is prepared by the preparation method of the modified silica and can be applied to the fields of plastics, silicon rubber and the like.
By adopting the technical scheme, the obtained modified silica is distributed in a lamellar structure, has high specific surface area and high diameter-thickness ratio, and is favorable for improving the dispersion performance during downstream processing.
The silane coupling agent grafted on the surface of the modified silica is large in quantity, is convenient to disperse to keep the structural shape, the fineness and the diameter-thickness ratio through the grafting effect of the silane coupling agent, is beneficial to downstream processing,
to sum up, the application comprises the following beneficial technical effects:
1. the dispersing agent is added, so that the dispersing performance of the silica powder in the silica slurry is improved, the dispersion problem of the silica powder in the silica slurry in water slurry is improved, and the agglomeration problem of the silica powder in the water slurry is improved; and the grinding efficiency and the grinding effect of the silica powder can be improved by combining the dispersing agent and the water slurry grinding process, the laminated structure of the silica powder is fully stripped, and the silica powder with high specific surface area and high activity is obtained.
2. The polycarboxylate dispersant is preferably adopted in the method, so that the viscosity of the water slurry can be reduced, the fluidity of the system can be improved, the dispersing effect of the silica powder in the water slurry can be improved, and the subsequent grinding operation can be facilitated; further, the dispersant can bring silica into contact with a silane coupling agent in a state of high specific surface area and high activity, thereby sufficiently modifying silica.
3. The modified silica prepared by the method has a good sheet structure and a large diameter-thickness ratio, and can ensure the dispersibility of the modified silica powder in the processing process of high polymer materials and better physical properties of products.
Drawings
FIG. 1 is an SEM image of a silica feedstock at 1200 magnification;
FIG. 2 is an SEM image of example 7 at 1200 magnifications of modified silica.
Detailed Description
The sources of the raw materials used in the examples and comparative examples of the present application are shown in the following table.
The silica raw materials adopted by the application are all from silica ores of Zhangzhou, Fujian, of the company. In addition to the silica source, other materials are commercially available, and some of the sources are shown in the table below.
Table 1 table of sources of raw materials used in examples and comparative examples of the present application
Examples of preparation of modified silica
Example 1
A modified silica is prepared by the following steps:
s1, coarse crushing of raw ore: crushing and coarsely grinding the silica raw material, and then sieving the crushed silica raw material with a 325-mesh sieve to obtain silica powder;
s2, preparing water slurry: dispersing 0.02kg of Rohm and Haas dispersant ACUMER 9400 and 4.0kg of silica powder into water, and uniformly mixing under the condition of stirring speed of 15r/min to obtain silica slurry with solid content of 50%;
s3, water slurry grinding: feeding the silica slurry into a stripping machine for grinding, wherein a grinding medium in the stripping machine is steel balls with the particle size of 4.5mm, the rotating speed of the stripping machine is 80r/min, and the silica slurry is discharged after being ground in the stripping machine for 2.5 h;
s4, drying the water slurry: feeding the ground silica slurry into a spray drying tower for spray drying granulation to obtain dry powder, wherein the feeding speed of the silica slurry is 10 tons/hour, and the temperature in the spray drying tower is controlled at 370 ℃;
s5, preparation of a modifier: uniformly mixing 600gKH550 and 1L of ethanol to obtain a silane coupling modifier;
s6, preparing a finished product: and (3) sending the dried powder into a modification scattering machine for dispersion, and spraying a silane coupling modifier into the dried powder in the dispersion process for modification in a spraying manner to obtain the modified silica.
Example 2
A modified silica is prepared by the following steps:
s1, coarse crushing of raw ore: crushing and coarsely grinding the silica raw material, and then sieving the crushed silica raw material with a 325-mesh sieve to obtain silica powder;
s2, preparing water slurry: dispersing 0.03kg of Rohm and Haas dispersant ACUMER 9400 and 3.75kg of silica powder into water, and uniformly mixing under the condition that the stirring speed is 28r/min to obtain silica slurry with the solid content of 60%;
s3, water slurry grinding: introducing the silica slurry into a stripping machine for grinding, wherein a grinding medium in the stripping machine is a nano ceramic ball with the particle size of 6mm, the rotating speed of the stripping machine is 100r/min, and the silica slurry is ground in the stripping machine for 2 hours and then discharged;
s4, drying the water slurry: feeding the ground silica slurry into a spray drying tower for spray drying granulation to obtain dry powder, wherein the feeding speed of the silica slurry is 10 tons/hour, and the temperature in the spray drying tower is controlled at 370 ℃;
s5, preparation of a modifier: uniformly mixing 700gKH560 and 1L of ethanol to obtain a silane coupling modifier;
s6, preparing a finished product: and (3) sending the dried powder into a modification scattering machine for dispersion, and spraying a silane coupling modifier into the dried powder in the dispersion process for modification in a spraying manner to obtain the modified silica.
Example 3
A modified silica is prepared by the following steps:
s1, coarse crushing of raw ore: crushing and coarsely grinding the silica raw material, and then sieving the crushed silica raw material with a 325-mesh sieve to obtain silica powder;
s2, preparing water slurry: dispersing 0.05kg of Rohm and Haas dispersant ACUMER 9400 and 3.5kg of silica powder into water, and uniformly mixing under the condition that the stirring speed is 35r/min to obtain silica slurry with the solid content of 70 percent;
s3, water slurry grinding: introducing the silica slurry into a stripping machine for grinding, wherein a grinding medium in the stripping machine is zircon with the particle size of 2.5mm, the rotating speed of the stripping machine is 130r/min, and the silica slurry is discharged after being ground in the stripping machine for 1.8 min;
s4, drying the water slurry: feeding the ground silica slurry into a spray drying tower for spray drying granulation to obtain dry powder, wherein the feeding speed of the silica slurry is 10 tons/hour, and the temperature in the spray drying tower is controlled at 370 ℃;
s5, preparation of a modifier: uniformly mixing 650gKH560 and 1L of ethanol to obtain a silane coupling modifier;
s6, preparing a finished product: and (3) sending the dried powder into a modification scattering machine for dispersion, and spraying a silane coupling modifier into the dried powder in the dispersion process for modification in a spraying manner to obtain the modified silica.
Example 4
The difference from example 3 is that the dispersant was replaced with a homogeneous mass of BYK-110.
Example 5
The difference from example 3 is that the dispersant was replaced with a homogeneous mass of BYK-163.
Example 6
The difference from example 5 is that:
s3, water slurry grinding: introducing the silica slurry into 2 stripping machines connected in series for grinding, wherein a grinding medium in the first stripping machine is a steel ball with the particle size of 6mm, the rotating speed of the first stripping machine is 80r/min, and the grinding time of the silica slurry in the first stripping machine is 1 h; the grinding medium in the second stripping machine is glass balls with the grain diameter of 4.5mm, the rotating speed of the second stripping machine is 100r/min, the grinding time of the silica slurry in the second stripping machine is 48min, and the silica slurry is discharged after the grinding in the second stripping machine is finished.
Example 7
The difference from example 2 is that:
s3, water slurry grinding: introducing the silica slurry into 3 stripping machines connected in series for grinding, wherein a grinding medium in the first stripping machine is a steel ball with the particle size of 6mm, the rotating speed of the first stripping machine is 80r/min, and the grinding time of the silica slurry in the first stripping machine is 40 min; grinding media in the second stripping machine are zirconium balls with the grain diameter of 4.5mm, the rotating speed of the second stripping machine is 100r/min, and the grinding time of the silica slurry in the second stripping machine is 30 min; grinding media in the third stripping machine are 2.5mm nano ceramic balls, the rotating speed of the third stripping machine is 100r/min, the grinding time of the silica slurry in the third stripping machine is 20min, and the silica slurry is discharged after the grinding in the third stripping machine is finished.
Example 8
The difference from example 2 is that:
s3, water slurry grinding: introducing the silica slurry into 5 stripping machines connected in series for grinding, wherein a grinding medium in the first stripping machine is a steel ball with the particle size of 8mm, the rotating speed of the first stripping machine is 80r/min, and the grinding time of the silica slurry in the first stripping machine is 20 min; grinding media in a second stripping machine are zirconium balls with the particle size of 6mm, the rotating speed of the second stripping machine is 100r/min, and the grinding time of the silica slurry in the second stripping machine is 15 min; grinding media in a third stripping machine are 4.5mm zirconium balls, the rotating speed of the third stripping machine is 120r/min, and the grinding time of the silica in the third stripping machine is 15 min; grinding media in a fourth stripping machine are zirconium balls with the grain diameter of 3.5mm, the rotating speed of the fourth stripping machine is 100r/min, and the grinding time of the silica in the fourth stripping machine is 12 min; grinding media in the fifth stripping machine are glass balls with the particle size of 2.5mm, the rotating speed of the fifth stripping machine is 80r/min, the grinding time of the silica slurry in the fifth stripping machine is 10min, and the silica slurry is discharged after the grinding in the fifth stripping machine is finished.
Comparative example 1
The difference from example 1 is that the preparation of modified silica comprises the following steps: s1, coarse crushing of raw ore: crushing and coarsely grinding the silica raw material, and then sieving the crushed silica raw material with a 325-mesh sieve to obtain silica powder;
s2, finely grinding silica: mixing the dried silica powder and sodium polyacrylate (grinding aid), and then, feeding the mixture into a stripping machine to grind for 2.5 hours, wherein the grinding medium in the stripping machine is zircon with the particle size of 6mm, and the rotating speed of the stripping machine is 60 r/min; wherein 1kg of sodium polyacrylate is added into each 100kg of silica powder;
s3, silica drying: placing the finely ground silica powder in a drying chamber to dry for 15min, wherein the drying temperature is 120 ℃, and controlling;
s4, preparation of a modifier: uniformly mixing 650gKH550 and 1L of ethanol to obtain a silane coupling modifier;
s5, preparing a finished product: and (3) sending the dried powder into a modification scattering machine for dispersion, and spraying a silane coupling modifier into the dried powder in the dispersion process for modification in a spraying manner to obtain the modified silica.
Comparative example 2
The difference from the example 1 is that the rotation speed of the stripping machine during the grinding in the step S3 is 65 r/min.
Comparative example 3
The difference from example 1 is that S2, water slurry preparation: 4.0kg of silica powder is dispersed in water and evenly mixed under the condition of stirring speed of 15r/min to obtain silica slurry with solid content of 50 percent.
Performance test oneSample preparation: the modified silicas prepared in examples 1-8 and comparative examples 1-3 were sampled and numbered as samples 1-11 in the order named.
The fineness and the oil absorption value of the samples 1-11 are detected by adopting the national standard GB/T14563-.
The radius-thickness ratio of the samples 1-11 is detected by adopting JC/T2063-2011 mica powder radius-thickness ratio measuring method as a building material industry standard, and specific detection results are shown in the following table.
TABLE 2 physical Properties test Table for samples 1-11
As can be seen from the comparison of the data of the samples in the table 2, the particle size of the modified silica prepared by the method is kept between 4.0 and 8.0 mu m, the diameter and the thickness are between 20 and 50, and the oil absorption value is above 40DOP g/100 g. The modified silica powder prepared by the scheme can be kept between 4.0 and 8.0 microns, the surface granular feeling is easily caused by the excessive thickness of the powder, the characteristics of downstream products are influenced, and the oil absorption value of the powder is improved if the powder is too thin, so that the processing difficulty of the downstream products is influenced.
As can be seen from comparison of the data of example 1 and comparative example 1 in Table 2, the modified silica obtained by dispersing silica powder and the Rohm and Haas dispersant ACUMER 9400 in water and grinding the dispersion in the state of water slurry had a fineness (D90) of 5.4 μm and a aspect ratio of 33; and the silica powder is ground by adopting the dry grinding process and the sodium polyacrylate grinding aid in the comparative example, and the obtained modified silica has the fineness (D90) of 15.3 mu m and the diameter-thickness ratio of 12. Therefore, the grinding is carried out by adopting the water slurry grinding process and matching with the Rohm and Haas dispersant ACUMER 9400, and due to the addition of the Rohm and Haas dispersant ACUMER 9400, the grinding aid not only has the effect of grinding aid in the grinding process, but also can keep the uniform dispersion degree of the silica powder in the water slurry, improve the sedimentation and aggregation problems of the silica powder in the water slurry and further improve the grinding effect; the silica powder has good grinding effect, low fineness, large specific surface area and large diameter-thickness ratio, so that the oil absorption value is high, the dispersion of the modified silica in a high polymer material is facilitated, and the bonding performance of the high polymer material and the modified silica powder is improved.
As can be seen from comparison of the data of example 1 and comparative example 2 in table 2, in the process of dispersing the dispersant and the silica raw material in water, the modified silica having a fineness D90 of 5.4 μm and a aspect ratio of 36 was obtained using a low stirring speed of 15 r/min; when the slurry was stirred at a stirring speed of 65r/min, the modified silica powder obtained had a D90 value of 11.2 μm and a aspect ratio of 4. The modified silica that this application was made is low in fineness, and specific surface area is big, and the footpath thickness ratio is big, and it is visible to adopt low stirring speed not only can ensure that dispersant and silica raw materials are abundant and homogeneous dispersion to the water thick liquid, and owing to stir at low stirring speed, the degree of collision is low among the granule in the water thick liquid, and the collision can be little, and the silica thick liquid is difficult for taking place the coagulation phenomenon after dispersing in the water thick liquid, also difficult the reunion takes place, can obtain good physical properties's modified silica after the fine grinding technology again.
As can be seen from the comparison of the data of example 1 and comparative example 3 in Table 2, the particle size was reduced from 13.6 μm to 5.4 μm and the aspect ratio was increased from 7 to 33 after the dispersant was added during the preparation of the aqueous slurry and the milling, indicating that the addition of the dispersant contributes to the milling of the silica slurry.
Further, as can be seen from the comparison of the data in examples 3 to 5, when the lumer 9400 dispersant was used in the preparation of aqueous slurry, the particle size of the obtained powder was 5.5 μm and the aspect ratio was 32; BYK-110 is used as a dispersing agent, and the particle size of the prepared powder is 7.5 mu m, and the diameter-thickness ratio is 23; BYK-163 is used as a dispersant, and the prepared powder has the particle size of 8 mu m and the diameter-thickness ratio of 21; the specific selection of the dispersing agent can influence the grinding effect of the silica powder particles in the water slurry grinding process, and the Rohm and Haas dispersing agent ACUMER 9400 is selected as the dispersing agent, so that the silica powder particles have better grinding effect.
According to the comparison of the data of the example 2 and the examples 5 to 8 in the table 2, the particle size of the prepared powder particles is reduced and the length-diameter ratio is increased by adopting the multiple grinding, and when the particle size of the grinding medium subjected to the subsequent grinding is smaller than that of the grinding medium subjected to the previous grinding, the interlaminar stripping effect of the silica powder in the fine grinding process is good, the specific surface area is increased, the silica powder is more fully contacted with the silane coupling modifier, the modification effect is improved, and the dispersibility of the modified silica in the high polymer material is further improved.
To further verify that the modified silica prepared according to the scheme of the present application has the above-mentioned excellent physical properties, SEM tests were performed on the silica raw material and the modified silica prepared according to example 7 in the present application, as shown in fig. 1 and 2.
As can be clearly seen from the diagram, the silica raw material in fig. 1 includes a massive structure with a large thickness and a sheet structure with a small thickness, wherein the massive structure with a large thickness is an agglomerated structure of amorphous silica, and the sheet structure with a small thickness is a silica structure; since the silica raw material is composed of quartz and clay, the quartz exists in nature in an amorphous structure, and the amorphous quartz structure is agglomerated in a natural state to form a massive structure. By combining the drawings of fig. 1 and fig. 2, the modified silica prepared by the technical scheme of the application comprises a lamellar structure with small thickness and a silicon dioxide structure similar to a sphere, and the modified silica prepared by the technical scheme is capable of grinding and peeling a thick lamellar structure to form a thin lamellar structure, crushing a blocky quartz structure, grinding and grinding edges and corners to form a silicon dioxide structure similar to a sphere and with small particle size, and has good grinding and peeling effects; by adopting the technical scheme of the application, the layered structure of the silica can be maintained, and the approximately spherical silica formed by grinding is arranged between the layered structures, so that the effect of improving the specific surface area of the modified silica is achieved.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The preparation method of the modified silica is characterized by comprising the following preparation steps:
s1, coarse crushing of raw ore: crushing, coarsely grinding and screening a silica raw material to obtain silica powder;
s2, preparing water slurry: dispersing a dispersing agent and silica powder into water, and uniformly stirring to obtain silica slurry;
s3, water slurry grinding: finely grinding the silica slurry;
s4, drying the water slurry: drying and granulating the finely ground silica slurry to obtain dry powder;
s5, preparing a finished product: dispersing the dried powder, and adding a silane coupling modifier for modification to obtain the modified silica.
2. The method for preparing modified silica according to claim 1, wherein in the step of preparing the slurry of S2, the stirring speed is 15 to 35 r/min.
3. The method for preparing modified silica according to claim 1, wherein the weight ratio of the dispersant to the silica powder added in the step S2 is (0.2 to 0.5) wt%: (35-40) wt%.
4. The method for producing modified silica according to claim 1, wherein the dispersant is a polycarboxylate-type dispersant.
5. The method according to claim 4, wherein the polycarboxylate-type dispersant has a solid content of 40 to 65%.
6. The method for preparing modified silica according to claim 1, wherein the silica slurry in S2 has a solid content of 50% to 70%.
7. The method of claim 1, wherein the grinding speed in the step of fine grinding in S3 is maintained at 80-130r/min, and the total time of fine grinding is 1.2-2.5 h.
8. The method according to claim 1, wherein in the step S3, the silica slurry is ground a plurality of times, and the particle sizes of the grinding media during the plurality of times of grinding are sequentially decreased.
9. A modified silica obtained by the process for producing a modified silica according to any one of claims 1 to 8.
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