CN114684827A - High-quality modified white carbon black and preparation method thereof - Google Patents
High-quality modified white carbon black and preparation method thereof Download PDFInfo
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- CN114684827A CN114684827A CN202210360086.3A CN202210360086A CN114684827A CN 114684827 A CN114684827 A CN 114684827A CN 202210360086 A CN202210360086 A CN 202210360086A CN 114684827 A CN114684827 A CN 114684827A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000006229 carbon black Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000011282 treatment Methods 0.000 claims abstract description 86
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 50
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 45
- 239000003607 modifier Substances 0.000 claims abstract description 41
- 239000002002 slurry Substances 0.000 claims abstract description 41
- 230000004048 modification Effects 0.000 claims abstract description 40
- 238000012986 modification Methods 0.000 claims abstract description 40
- 238000004537 pulping Methods 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000032683 aging Effects 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000012190 activator Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000007664 blowing Methods 0.000 claims abstract description 12
- 230000004913 activation Effects 0.000 claims abstract description 10
- 238000006011 modification reaction Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 31
- 239000012065 filter cake Substances 0.000 claims description 26
- 235000019353 potassium silicate Nutrition 0.000 claims description 18
- 239000008394 flocculating agent Substances 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 9
- 239000006148 magnetic separator Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 238000007885 magnetic separation Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- 238000000265 homogenisation Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 9
- 230000003213 activating effect Effects 0.000 description 8
- 238000010009 beating Methods 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Images
Classifications
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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
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
-
- 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
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/152—Preparation of hydrogels
- C01B33/154—Preparation of hydrogels by acidic treatment of aqueous silicate solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/19—Oil-absorption capacity, e.g. DBP values
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention provides high-quality modified white carbon black and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, preparing a sodium silicate solution; heating the sodium silicate solution to 70-90 ℃, adding a concentrated sulfuric acid solution, a first modifier and a first activator while stirring for primary modification, standing, and cooling to obtain slurry; then, carrying out aging treatment, filtering and washing treatment, pulping and drying treatment on the slurry to obtain first modified white carbon black powder; and finally, adding a second modifier into the first modified white carbon black powder after the first modified white carbon black powder is subjected to pre-activation treatment, performing fluidized bed modification reaction, and performing blowing and collection to obtain the high-quality modified white carbon black powder. According to the invention, the materials are primarily modified after being synthesized, and then the surfaces of the materials are modified again, so that the homogenization degree of material modification can be improved, the modification is more thorough, and various properties of the prepared modified white carbon black product are obviously improved. In addition, the consumption of the modifier in a single modification operation is low, and the waste of the modifier is not easy to cause.
Description
Technical Field
The invention relates to the technical field of white carbon black production, and in particular relates to high-quality modified white carbon black and a preparation method thereof.
Background
White charcoalBlack is a generic term for white powdered X-ray amorphous silicic acid and silicate products. White carbon black (commonly known as precipitated silica) is a porous material, and its composition can be SiO2·nH2And O represents. Wherein nH2O is present in the form of surface hydroxyl groups. White carbon black is a raw material for manufacturing glass, optical fibers, optical instruments, artware, refractory materials and feed additives, and is an important material for scientific research.
The surface modification of the white carbon black is to utilize certain chemical substances and enable hydrocarbon groups on the surface of the white carbon black to react with the chemical substances through a certain process method, so that silanol groups on the surface of the white carbon black are eliminated or reduced, and the purpose of surface modification is achieved. Most of the existing white carbon black modification processes adopt a dry method for improvement treatment, namely, crushing and surface modification of white carbon black powder. The dry modification process is simple and only needs one modification operation. However, the modifier is usually not uniformly distributed, the quality is not high, the modification effect is not ideal, and the defects of large modifier dosage, large energy consumption, serious dust pollution and the like exist.
Disclosure of Invention
The invention aims to provide high-quality modified white carbon black which is high in quality, good in phase quality, ideal in modification effect and remarkably improved in various performances.
The invention also aims to provide a preparation method of the high-quality modified white carbon black, which overcomes the defects of low quality, non-ideal modification effect and the like of the white carbon black prepared by the conventional white carbon black preparation method by modifying the synthesized material for multiple times and is suitable for industrial large-scale production.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a preparation method of high-quality modified white carbon black, which comprises the following steps:
s1, preparing a sodium silicate solution;
s2, heating the sodium silicate solution to 70-90 ℃, adding a concentrated sulfuric acid solution, a first modifier and a first activator while stirring for primary modification, standing, and cooling to obtain slurry;
s3, carrying out aging treatment, filtering and washing treatment, pulping and drying treatment on the slurry to obtain first modified white carbon black powder;
and S4, adding a second modifier to perform fluidized bed modification reaction after the first modified white carbon black powder is subjected to pre-activation treatment, and blowing and collecting to obtain the high-quality modified white carbon black powder.
The invention provides high-quality modified white carbon black which is prepared according to the method.
The high-quality modified white carbon black and the preparation method thereof have the beneficial effects that:
the method carries out primary modification on the material after the material is synthesized, and then carries out secondary modification on the surface of the material. The homogenization degree of material modification can be improved through multiple modification operations (namely, the combination of wet modification and dry modification), so that the modification is more thorough, and various properties of the prepared modified white carbon black product are remarkably improved. In addition, the consumption of the modifier in single modification operation is low, and the waste of the modifier is not easy to cause.
The modified white carbon black prepared by the method has high quality, good appearance and ideal modification effect. The high-quality modified white carbon black has high purity, small fineness, high oil absorption value, large specific surface area and good dispersity. The dispersity of the white clay can reach more than 89.5 percent, the whiteness is more than or equal to 92 percent, and the specific surface area can reach 320m2The DBP absorption value can reach 3.8mL/g, and the total iron (Fe) content is less than or equal to 200 mg/kg.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 is a flowchart of a preparation process of high-quality modified white carbon black according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The high-quality modified white carbon black and the preparation method thereof according to the embodiment of the invention are specifically described below.
Referring to fig. 1, a method for preparing high-quality modified white carbon black provided by an embodiment of the present invention includes the following steps:
s1, preparing a sodium silicate solution.
Further, in a preferred embodiment of the present invention, the step of preparing the sodium silicate solution is: and mixing the purified high-purity water glass solution with water, and adding the mixture into a reaction kettle to obtain the sodium silicate solution. Wherein the concentration of the sodium silicate solution is 0.4-2 mol/L, and the temperature is 50-60 ℃.
Specifically, the purification treatment comprises the following steps:
adding a flocculating agent and a filter aid into the water glass solution while stirring, filtering impurities precipitated from the water glass solution by using a plate-and-frame filter after stirring for 0.5-2 h, and obtaining a primary sodium silicate solution. Wherein the flocculating agent comprises inorganic salt flocculating agent such as polyaluminium sulfate, polysilicic acid or aluminum silicate and the like. The filter aid is activated carbon. The preparation concentration of the flocculant and the preparation concentration of the filter aid are both 0.1-0.2%. According to the invention, the flocculating agent and the filter aid are added into the sodium silicate solution, so that on one hand, insoluble silicate such as iron, aluminum, calcium, magnesium and the like in the sodium silicate solution can be flocculated into macromolecular particles by micromolecules, and the impurity content in the sodium silicate solution can be reduced after filtering, thereby improving the purity of the product. On the other hand, the filter cake layer can be deepened and loosened, the filtering resistance is reduced, and the filtering speed is improved. In addition, the activated carbon can also adsorb partial pigments and small molecular impurities, thereby greatly improving the phase of the product.
And carrying out magnetic separation treatment on the primary sodium silicate solution in a magnetic separator to obtain the high-purity water glass solution. Preferably, the magnetic separator may be a low-field magnetic separator. The magnetic separator is used for carrying out magnetic separation treatment on the primary sodium silicate solution, so that the concentration of magnetic metal in the solution, particularly the concentration of iron, is effectively reduced.
S2, heating the sodium silicate solution to 70-90 ℃, adding a concentrated sulfuric acid solution, a first modifier and a first activator while stirring for primary modification, standing, and cooling to obtain slurry. Wherein the concentration of the concentrated sulfuric acid is 50-70%. When the concentrated sulfuric acid is added, a large amount of heat can be released, so that the temperature of the reaction environment can be automatically raised to save energy. The surface of the synthesized white carbon black can be adjusted by adding the first activating agent, so that the synthesized white carbon black can easily adsorb the first modifying agent, and the modification effect of the first modifying agent is promoted, so that the high-quality white carbon black with high oil absorption value, large specific surface area and aerogel characteristic is obtained.
The specific steps of carrying out primary modification by adopting a first modifier and a first activating agent are as follows: the method comprises the steps of quickly heating a sodium silicate solution in a reaction kettle to 50-80 ℃, adding a concentrated sulfuric acid solution while stirring, simultaneously adding a certain amount of a first modifier and a first activator for reaction, stopping adding the sulfuric acid solution until the pH value of the reacted solution is 5.0-8.0, and finishing the reaction. Wherein, in the reaction liquid, the mass percent of the first modifier is 0.05-0.1%, and the mass percent of the first activator is 0.1-0.15%. And then quickly cooling the sodium silicate solution in the reaction kettle to 30-40 ℃, standing for a period of time, and obtaining a first slurry after the solution in the reaction kettle becomes gel. And carrying out primary aging treatment on the first slurry, wherein the aging time is 25-45 min. And then uniformly scattering the first slurry in the reaction kettle, rapidly heating to 70-90 ℃, adding a concentrated sulfuric acid solution with the concentration of 50-70% while stirring, simultaneously adding a certain amount of a first modifier and a first activator for reaction, stopping adding the sulfuric acid solution until the pH value of the reacted solution is 3-6, and finishing the reaction. Wherein, in the reaction liquid, the mass percent of the first modifier is 0.05-0.1%, and the mass percent of the first activator is 0.1-0.15%. And finally, quickly cooling the solution in the reaction kettle to 50-60 ℃, standing for a period of time, and obtaining the slurry (namely the final slurry) after the solution in the reaction kettle becomes gel.
Further, in the preferred embodiment of the present invention, the first modifier is selected from one or more of silane coupling agent si-69, silane coupling agent kh570, silane coupling agent kh550 or cetyl trimethyl ammonium bromide. The first activator is selected from one of ethanolamine, triethanolamine or hexamethyltetramine, and the amount of the first activator is 1-3% of the dry weight of the first modified white carbon black powder.
And S3, carrying out aging treatment, filtering and washing treatment, pulping and drying treatment on the slurry to obtain the first modified white carbon black powder.
Further, in the preferred embodiment of the present invention, the aging time is 1 to 3 hours. The steps of the filtration washing treatment and the pulping and drying treatment are as follows: and (3) putting the aged slurry into a squeezing plate frame for filter pressing and washing to obtain a filter cake. Wherein the content of soluble dissociated salt (such as sulfate) in the filter cake after filter pressing and washing treatment is below 1%, and the solid content of the filter cake is 30-50%. And then carrying out pulping treatment on the filter cake in a pulping machine, and finally conveying the filter cake to drying equipment for drying treatment to obtain first modified white carbon black powder. It should be noted that the first modified white carbon black powder of the present invention can also be collected and stored separately and sold according to market demand.
The pulping treatment comprises the following steps: and pulping the filter cake by using a pulping machine, and adding a water-soluble high-molecular stabilizer with the concentration of 0.1-0.2% in the pulping process to obtain liquid pulp. Wherein the water-soluble polymer stabilizer comprises polyacrylamide, sodium polyacrylate and the like. The viscosity of the slurry can be increased by adding the high molecular stabilizer, so that the particle strength of the product can be enhanced. Specifically, the beating process includes a three-stage beating process. Firstly, a filter cake is beaten into coarse slurry with large-particle agglomerates through a primary beater, and the rotation speed of the primary beater is 60-100 revolutions per minute. And then shearing the coarse pulp into fine pulp with fine particle agglomerates through a secondary pulping machine, wherein the rotating speed of the secondary pulping machine is 80-120 r/min. And finally, grinding the fine pulp into powder pulp by a three-stage beater, wherein the rotating speed of the three-stage beater is 100-150 r/min.
And S4, adding a second modifier to perform fluidized bed modification reaction after the first modified white carbon black powder is subjected to pre-activation treatment, and blowing and collecting to obtain the high-quality modified white carbon black powder. Wherein the mass ratio of the first modified white carbon black to the second modifier is 1000: 0.5 to 1.
Further, in a preferred embodiment of the present invention, the step of pre-activating treatment comprises: and (2) placing the first modified white carbon black in a three-phase reactor (such as a fluidized bed reactor), and heating to 400-500 ℃ for pre-activation treatment. Wherein the preactivation time is 3.2-4.2 h.
Further, in a preferred embodiment of the present invention, the second modifier is a silane coupling agent, a titanate coupling agent or a polyol coupling agent, and the temperature of the fluidized bed modification reaction is 250 to 300 ℃.
Further, in a preferred embodiment of the present invention, the step of purging and collecting includes: and (3) blowing the three-phase reactor by using inert gas, and collecting blown powder to obtain the high-quality modified white carbon black powder. The temperature of the purging airflow is 300-500 ℃.
The modified white carbon black prepared by the method has high quality, good appearance and ideal modification effect. The material is primarily modified after being synthesized, and then the surface of the material is modified again. The homogenization degree of material modification can be improved through multiple modification operations (namely, the combination of wet modification and dry modification), so that the modification is more thorough, and various properties of the prepared modified white carbon black product are remarkably improved. In addition, the consumption of the modifier in a single modification operation is low, and the waste of the modifier is not easy to cause.
The invention also provides high-quality modified white carbon black prepared by the preparation method. The high-quality modified white carbon black prepared by the preparation method has high purity, small fineness, high oil absorption value, large specific surface area and good dispersity. The dispersion degree can reach more than 89.5 percentThe whiteness is more than or equal to 92 percent, and the specific surface area can reach 320m2The DBP absorption value can reach 3.8mL/g, and the total iron (Fe) content is less than or equal to 200 mg/kg.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The high-quality modified white carbon black provided by the embodiment is prepared according to the following method:
(1) preparation before synthesis: mixing the purified high-purity water glass solution with water, adding the mixture into a reaction kettle to prepare a sodium silicate solution, and then heating the sodium silicate solution in the reaction kettle to 55 ℃. Wherein, the purification treatment method comprises the following steps: A. adding a flocculating agent with the preparation concentration of 0.15 percent and a filter aid into a water glass solution with the preparation concentration of 1.0mol/L while stirring the water glass solution, filtering impurities precipitated from the sodium silicate solution by using a plate-and-frame filter after stirring for 1h, and obtaining a primary sodium silicate solution. Wherein the mass ratio of the water glass solution, the flocculating agent and the filter aid is 1000:0.21: 0.16. B. And conveying the primary sodium silicate solution to a magnetic separator for magnetic separation treatment to obtain the high-purity water glass solution.
(2) Synthesis, primary modification treatment and cooling aging treatment: quickly heating the sodium silicate solution in the reaction kettle to 80 ℃, adding 60% concentrated sulfuric acid solution while stirring the sodium silicate solution, simultaneously adding a certain amount of silane coupling agent si-69 and ethanolamine for reaction, stopping adding the concentrated sulfuric acid solution until the pH value of the reacted solution is 5.0, and finishing the reaction. Wherein, in the reaction liquid, the mass percent of the first modifier is 0.06 percent, and the mass percent of the first activator is 0.12 percent. And then, quickly cooling the solution in the reaction kettle to 35 ℃, standing for a period of time, and obtaining first slurry when the solution in the reaction kettle becomes gel. And carrying out first aging treatment on the first slurry, wherein the first aging treatment time is 30 min. And then uniformly scattering the first slurry in the reaction kettle, rapidly heating to 85 ℃, adding 60% concentrated sulfuric acid solution while stirring the first slurry, simultaneously adding a certain amount of first modifier and first activator, stopping adding the sulfuric acid solution until the pH value of the solution after reaction reaches 5.0, and finishing the reaction. Wherein, in the reaction liquid, the mass percent of the first modifier is 0.08%, and the mass percent of the first activator is 0.12%. And finally, quickly cooling the solution in the reaction kettle to 55 ℃, standing for a period of time to enable the solution in the reaction kettle to become gel, and obtaining the final slurry. Wherein the dosage of the first activating agent is 2% of the dry weight of the first modified white carbon black powder. And then carrying out secondary aging treatment on the final slurry, wherein the secondary aging time is 90 minutes.
(3) And (3) filtering and washing treatment: and carrying out filter pressing and washing treatment on the final slurry through a pressing plate frame to obtain a filter cake. Wherein the content of soluble dissociation salt (such as sulfate) in the filter cake after filter pressing washing treatment is below 1%, and the solid content in the filter cake is 40%.
(4) Pulping and drying treatment: and pulping the filter cake by using a pulping machine, and adding a water-soluble high-molecular stabilizer with the concentration of 0.15% in the pulping process. And then conveying the first modified white carbon black powder into a drying device (such as a drying tower) for drying treatment to obtain the first modified white carbon black powder. Specifically, the beating treatment is a three-stage beating treatment. First, the filter cake was beaten into a coarse slurry with large particle agglomerates by a primary beater, the speed of which was controlled at 80 rpm. The brown stock is then sheared into a fine stock with fine particle agglomerates by a secondary beater, the secondary beater being controlled at 100 rpm. The fine pulp is finally ground to a powder pulp by means of a three-stage beater, such as a beater grinder, the rotation speed of which is controlled at 120 rpm.
(5) Pre-activation treatment: and (3) placing the first modified white carbon black powder into a three-phase reactor, heating the three-phase reactor to enable the internal temperature of the three-phase reactor to reach 450 ℃, and performing pre-activation treatment on the first modified white carbon black powder in the three-phase reactor, wherein the pre-activation time is 3.6 hours. Meanwhile, dry nitrogen with the flow rate of 50mL/min is introduced into the three-phase reactor to take away the water generated in the three-phase reactor.
(6) And (3) secondary modification treatment: and adding a second modifier into the three-phase reactor, introducing steam with the air flow velocity of 8m/s into the three-phase reactor, and controlling the temperature in the three-phase reactor to be 280 ℃ at the same time, so that the three-phase reactor is subjected to fluidized bed modification reaction to obtain high-quality modified white carbon black powder. The mass ratio of the first modified white carbon black to the second modifier is 1000: 0.8.
(7) purging and collecting: and (3) blowing the three-phase reactor by using inert gas, and blowing the high-quality modified white carbon black powder out of the three-phase reactor and collecting to obtain the high-quality modified white carbon black. The temperature of the purge gas stream was 400 ℃.
Example 2
The high-quality modified white carbon black provided by the embodiment is prepared according to the following method:
(1) preparation before synthesis: mixing the purified high-purity water glass solution with water, adding the mixture into a reaction kettle to prepare a sodium silicate solution, and then heating the sodium silicate solution in the reaction kettle to 55 ℃. Wherein, the purification treatment method comprises the following steps: A. adding a flocculating agent with the preparation concentration of 0.1% and a filter aid into a sodium silicate solution with the preparation concentration of 0.4mol/L while stirring the sodium silicate solution, and filtering out impurities precipitated from the sodium silicate solution by using a plate-and-frame filter after stirring for 0.5h to obtain a primary sodium silicate solution. Wherein the mass ratio of the water glass solution, the flocculating agent and the filter aid is 1000:0.2: 0.15. B. And conveying the primary sodium silicate solution to a magnetic separator for magnetic separation treatment to obtain the high-purity water glass solution.
(2) Synthesis, primary modification treatment and cooling aging treatment: quickly heating the sodium silicate solution in the reaction kettle to 50 ℃, adding 50% concentrated sulfuric acid solution while stirring the sodium silicate solution, simultaneously adding a certain amount of silane coupling agent kh570 and hexamethyltetramine for reaction, stopping adding the concentrated sulfuric acid solution until the pH value of the reacted solution is 5.0, and finishing the reaction. Wherein, in the reaction liquid, the mass percent of the first modifier is 0.05 percent, and the mass percent of the first activator is 0.1 percent. And then, quickly cooling the solution in the reaction kettle to 30 ℃ and standing for a period of time until the solution in the reaction kettle becomes gel-like, thereby obtaining the first slurry. And carrying out first aging treatment on the first slurry, wherein the first aging treatment time is 25 min. And then uniformly scattering the first slurry in the reaction kettle, quickly heating to 70 ℃, adding a concentrated sulfuric acid solution with the concentration of 50% while stirring the first slurry, simultaneously adding a certain amount of a first modifier and a first activator, stopping adding the sulfuric acid solution until the pH value of the solution after reaction reaches 3.0, and finishing the reaction. Wherein, in the reaction liquid, the mass percent of the first modifier is 0.05 percent, and the mass percent of the first activator is 0.1 percent. And finally, quickly cooling the solution in the reaction kettle to 50 ℃, standing for a period of time to enable the solution in the reaction kettle to become gel, and obtaining the final slurry. Wherein the dosage of the first activating agent is 1% of the dry weight of the first modified white carbon black powder. And then carrying out secondary aging treatment on the final slurry, wherein the secondary aging time is 60 minutes.
(3) And (3) filtering and washing treatment: and carrying out filter pressing and washing treatment on the final slurry through a pressing plate frame to obtain a filter cake. Wherein the content of soluble dissociation salt (such as sulfate) in the filter cake after filter pressing washing treatment is below 1%, and the solid content in the filter cake is 30%.
(4) Pulping and drying treatment: and pulping the filter cake by using a pulping machine, and adding a water-soluble high-molecular stabilizer with the concentration of 0.1% in the pulping process. And then conveying the mixture into drying equipment (such as a drying tower) for drying treatment to obtain first modified white carbon black powder. Specifically, the beating treatment is a three-stage beating treatment. First, the filter cake was beaten into a coarse slurry with large particle agglomerates by a primary beater, the speed of which was controlled at 60 rpm. The coarse pulp is then sheared into a fine pulp with fine particle agglomerates by a secondary beater, the secondary beater being controlled at 80 rpm. The fine pulp is finally ground to a powder pulp by means of a three-stage beater, such as a beater grinder, the rotation speed of which is controlled at 100 rpm.
(5) Pre-activation treatment: and (3) placing the first modified white carbon black powder into a three-phase reactor, heating the three-phase reactor to enable the internal temperature of the three-phase reactor to reach 400 ℃, and pre-activating the first modified white carbon black powder in the three-phase reactor for 4.2 hours. Meanwhile, dry nitrogen with the flow rate of 30mL/min is introduced into the three-phase reactor to take away the water generated in the three-phase reactor.
(6) And (3) secondary modification treatment: and adding a second modifier into the three-phase reactor, introducing steam with the air flow velocity of 6m/s into the three-phase reactor, and controlling the temperature in the three-phase reactor to be 300 ℃ at the same time, so that the three-phase reactor is subjected to fluidized bed modification reaction to obtain high-quality modified white carbon black powder. The mass ratio of the first modified white carbon black to the second modifier is 1000: 0.5.
(7) purging and collecting: and (3) blowing the three-phase reactor by using inert gas, and blowing the high-quality modified white carbon black powder out of the three-phase reactor and collecting to obtain the high-quality modified white carbon black. The temperature of the purge stream was 300 ℃.
Example 3
The high-quality modified white carbon black provided by the embodiment is prepared according to the following method:
(1) preparation before synthesis: mixing the purified high-purity water glass solution with water, adding the mixture into a reaction kettle to prepare a sodium silicate solution, and then heating the sodium silicate solution in the reaction kettle to 60 ℃. Wherein, the purification treatment method comprises the following steps: A. adding a flocculating agent with the preparation concentration of 0.2% and a filter aid into a sodium silicate solution with the preparation concentration of 2.0mol/L while stirring the sodium silicate solution, and filtering impurities precipitated from the sodium silicate solution by using a plate-and-frame filter after stirring for 2 hours to obtain a primary sodium silicate solution. Wherein the mass ratio of the water glass solution, the flocculating agent and the filter aid is 1000:0.19: 0.14. B. And conveying the primary sodium silicate solution to a magnetic separator for magnetic separation treatment to obtain the high-purity water glass solution.
(2) Synthesis, primary modification treatment and cooling aging treatment: quickly heating the sodium silicate solution in the reaction kettle to 80 ℃, adding 70% concentrated sulfuric acid solution while stirring the sodium silicate solution, simultaneously adding a certain amount of cetyl trimethyl ammonium bromide and triethanolamine to react, stopping adding the concentrated sulfuric acid solution until the pH value of the reacted solution is 8.0, and finishing the reaction. Wherein, in the reaction liquid, the mass percent of the first modifier is 0.1 percent, and the mass percent of the first activator is 0.15 percent. And then, quickly cooling the solution in the reaction kettle to 40 ℃, standing for a period of time, and obtaining first slurry when the solution in the reaction kettle becomes gel. And carrying out first aging treatment on the first slurry, wherein the first aging treatment time is 45 min. And then uniformly scattering the first slurry in the reaction kettle, rapidly heating to 90 ℃, adding a concentrated sulfuric acid solution with the concentration of 70% while stirring the first slurry, simultaneously adding a certain amount of a first modifier and a first activator, stopping adding the sulfuric acid solution until the pH value of the solution after reaction reaches 6.0, and finishing the reaction. Wherein, in the reaction liquid, the mass percent of the first modifier is 0.1 percent, and the mass percent of the first activator is 0.15 percent. And finally, rapidly cooling the solution in the reaction kettle to 60 ℃, standing for a period of time to enable the solution in the reaction kettle to become gel, and obtaining the final slurry, wherein the dosage of the first activating agent is 3% of the dry weight of the first modified white carbon black powder. The final slurry was then subjected to a second aging treatment for 135 minutes.
(3) And (3) filtering and washing treatment: and carrying out filter pressing and washing treatment on the final slurry through a pressing plate frame to obtain a filter cake. Wherein the content of soluble dissociation salt (such as sulfate) in the filter cake after filter pressing washing treatment is below 1%, and the solid content in the filter cake is 50%.
(4) Pulping and drying treatment: and pulping the filter cake by using a pulping machine, and adding a water-soluble high-molecular stabilizer with the concentration of 0.2% in the pulping process. And then conveying the mixture into drying equipment (such as a drying tower) for drying treatment to obtain first modified white carbon black powder. Specifically, the beating treatment is a three-stage beating treatment. First, the filter cake was beaten into a coarse slurry with large particle agglomerates by a primary beater, the speed of which was controlled at 100 rpm. The coarse pulp is then sheared into a fine pulp with fine particle agglomerates by a secondary beater, the secondary beater being controlled at 120 rpm. The fine pulp is finally ground to a powder pulp by means of a three-stage beater, such as a beater mill, the rotational speed of which is controlled at 150 rpm.
(5) Pre-activation treatment: and (3) placing the first modified white carbon black powder into a three-phase reactor, heating the three-phase reactor to enable the internal temperature of the three-phase reactor to reach 500 ℃, and pre-activating the first modified white carbon black powder in the three-phase reactor for 3.2 hours. Meanwhile, dry nitrogen with the flow rate of 60mL/min is introduced into the three-phase reactor to take away the water generated in the three-phase reactor.
(6) And (3) secondary modification treatment: and adding a second modifier into the three-phase reactor, introducing steam with the air flow velocity of 10m/s into the three-phase reactor, and controlling the temperature in the three-phase reactor to be 300 ℃ at the same time, so that the three-phase reactor is subjected to fluidized bed modification reaction to obtain high-quality modified white carbon black powder. The mass ratio of the first modified white carbon black to the second modifier is 1000: 1.
(7) purging and collecting: and (3) blowing the three-phase reactor by using inert gas, and blowing the high-quality modified white carbon black powder out of the three-phase reactor and collecting to obtain the high-quality modified white carbon black. The temperature of the purge stream was 500 ℃.
Test example 1
The dispersibility of the high-quality modified white carbon black of examples 1 to 3 was measured by using a carbon black dispersibility measuring instrument. The dispersion percentage of the vulcanized rubber containing the high-quality modified white carbon black of examples 1 to 3 was observed by an optical microscope. The specific method for measuring the dispersion coefficient comprises the following steps: the high-quality modified white carbon black prepared in examples 1 to 3 is applied to vulcanized rubber materials, and then different vulcanized rubber materials are cut into three groups of thin test pieces with smooth appearance, so as to observe and analyze the dispersion percentage of the white carbon black.
TABLE 1 test results of high quality modified white carbon black
The high-quality modified white carbon black prepared by the preparation method has the advantages of high purity, small fineness, high oil absorption value, large specific surface area and good dispersity. The dispersity can reach more than 89.5 percent, the whiteness is more than or equal to 92 percent, and the specific surface area can reach 320m2The DBP absorption value can reach 3.8mL/g, and the total iron (Fe) content is less than or equal to 200 mg/kg.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of the high-quality modified white carbon black is characterized by comprising the following steps:
s1, preparing a sodium silicate solution;
s2, heating the sodium silicate solution to 70-90 ℃, adding a concentrated sulfuric acid solution, a first modifier and a first activator while stirring for primary modification, standing, and cooling to obtain slurry;
s3, carrying out aging treatment, filtering and washing treatment, pulping and drying treatment on the slurry to obtain first modified white carbon black powder;
and S4, adding a second modifier to perform fluidized bed modification reaction after the first modified white carbon black powder is subjected to pre-activation treatment, and blowing and collecting to obtain the high-quality modified white carbon black powder.
2. The method for preparing high-quality modified white carbon black according to claim 1, wherein in step S1, the step of preparing the sodium silicate solution is as follows: mixing the purified high-purity water glass solution with water, and adding the mixture into a reaction kettle to obtain a sodium silicate solution, wherein the concentration of the sodium silicate solution is 0.4-2 mol/L, and the temperature of the sodium silicate solution is 50-60 ℃.
3. The preparation method of the high-quality modified white carbon black according to claim 2, wherein the purification treatment comprises the following steps:
adding a flocculating agent and a filter aid into the water glass solution while stirring, stirring for 0.5-2 h, and filtering to obtain a primary sodium silicate solution;
and carrying out magnetic separation treatment on the primary sodium silicate solution in a magnetic separator to obtain the high-purity water glass solution.
4. The method for preparing the high-quality modified white carbon black according to claim 3, wherein the flocculating agent comprises polyaluminium sulfate, polysilicic acid or aluminum silicate, the filter aid is activated carbon, and the preparation concentrations of the flocculating agent and the filter aid are both 0.1-0.2%.
5. The method for preparing high-quality modified white carbon black according to claim 1, wherein in step S2, the first modifier is one or more selected from silane coupling agent si-69, silane coupling agent kh570, silane coupling agent kh550 or cetyl trimethylammonium bromide, and the first activator is one selected from ethanolamine, triethanolamine or hexamethyltetramine.
6. The method for preparing high-quality modified white carbon black according to claim 1, wherein in step S3, the aging treatment time is 1-3 hours, and the steps of the filtering and washing treatment, the pulping treatment and the drying treatment are as follows: and performing filter pressing washing on the aged slurry in a pressing plate frame to obtain a filter cake, pulping the filter cake in a pulping machine, and finally conveying the filter cake to drying equipment to obtain first modified white carbon black powder.
7. The method for preparing high-quality modified white carbon black according to claim 1, wherein in step S4, the step of pre-activation treatment comprises: and (3) placing the first modified white carbon black in a three-phase reactor, and heating to 400-500 ℃ for pre-activation treatment, wherein the pre-activation time is 3.2-4.2 h.
8. The method for preparing high-quality modified white carbon black according to claim 1, wherein in step S4, the second modifier is a silane coupling agent, a titanate coupling agent or a polyol coupling agent, and the temperature of the fluidized bed modification reaction is 250-300 ℃.
9. The method for preparing high-quality modified white carbon black according to claim 1, wherein in step S4, the purging and collecting steps are as follows: and blowing the three-phase reactor by using inert gas, and collecting blown powder to obtain the high-quality modified white carbon black powder.
10. High-quality modified white carbon black, which is characterized by being prepared by the preparation method according to any one of claims 1 to 9.
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