CN111017932B - Large-aperture white carbon black and preparation method and application thereof - Google Patents
Large-aperture white carbon black and preparation method and application thereof Download PDFInfo
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- CN111017932B CN111017932B CN201911400253.7A CN201911400253A CN111017932B CN 111017932 B CN111017932 B CN 111017932B CN 201911400253 A CN201911400253 A CN 201911400253A CN 111017932 B CN111017932 B CN 111017932B
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/126—Preparation of silica of undetermined type
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Abstract
The invention provides a large-aperture white carbon black and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Dripping a water glass solution and sulfuric acid into the reaction bottom material at the same time to enable the water glass and the sulfuric acid to have precipitation reaction, and then adjusting the pH value to be acidic to obtain a white carbon black suspension; (2) Carrying out filter pressing on the white carbon black suspension liquid obtained in the step (1), and sequentially washing, slurrying and drying the obtained filter cake to obtain the large-aperture white carbon black; the reaction substrate in the step (1) contains a carbonate additive. On the basis of the preparation process by the sulfuric acid precipitation method, the preparation process is optimized, and the formation and agglomeration processes of silicon dioxide particles are changed by selecting additives, so that the large-aperture white carbon black product with larger aperture and better dispersibility is obtained. The method can obtain the white carbon black with excellent performance while reducing the manufacturing cost, and has important significance for popularizing the industrial application of the precipitation method.
Description
Technical Field
The invention belongs to the technical field of material preparation, relates to white carbon black and a preparation method and application thereof, and particularly relates to large-aperture white carbon black and a preparation method and application thereof.
Background
White carbon black is a generic name for white powdery X-ray amorphous silicic acid and silicate products. The white carbon black is hydrated silicon dioxide (SiO) 2 ·nH 2 O), which is known for its white appearance and its reinforcing properties similar to those of carbon black in rubber. White carbon black is light, nontoxic, tasteless and insoluble in water, wherein nH 2 O exists in the form of surface hydroxyl groups, and easily absorbs water to form aggregates. The white carbon black has the advantages of small particle size, large specific surface area, high dispersibility, good chemical stability, high temperature resistance and good insulativity, so the white carbon black is widely applied to the fields of rubber, clinker, coating, printing ink, papermaking, agricultural and medical science, daily chemical industry and the like.
The white carbon black is a porous substance, and the pore size and the pore structure of the white carbon black are one of important factors influencing the physical and chemical properties of the white carbon black; generally speaking, the larger the pore size of the silica is, the more beneficial to expanding the application field of the silica, for example, the extinction performance of the macroporous silica is far better than that of the silica with the conventional pore size.
The most common method for preparing the large-aperture white carbon black in a laboratory is a sol-gel method. The sol-gel method uses organic silicon sources such as tetraethoxysilane and the like as raw materials, and can prepare products with large pore diameters through further hydrolysis, but the cost of the organic silicon sources such as tetraethoxysilane and the like is too high, so that the method cannot be popularized in a large scale in industry. Thus, although SiO is obtained by a vapor phase method 2 The product has high purity, good dispersity, small particle size, spherical shape, few surface hydroxyl groups and excellent reinforcing property, but the most conventional method for producing the white carbon black in the process is still a precipitation method due to complex process, high requirement on equipment, large energy consumption and high production cost.
The precipitation method uses acid and water glass as raw materials, the cost is low, the operation is simple, the aperture of the prepared white carbon black is far smaller than that of the white carbon black prepared by the sol-gel method, and the development trend of industrially preparing the white carbon black is determined by improving the precipitation method to increase the aperture of the prepared white carbon black.
CN 107892305A discloses a biochemical preparation method of macroporous white carbon black material, which comprises the following steps: mixing water glass with water at normal temperature and then uniformly stirring; uniformly mixing biological starch with water at normal temperature, and carrying out gelatinization treatment at a certain temperature; mixing a water glass solution and a biological starch solution, adding an inorganic acid catalyst, controlling the pH value, and heating to a certain temperature for hydrolysis and aging reaction; after the reaction is finished, removing sodium salt from the obtained gel through suction filtration and water washing; and adding the washed product into an aqueous solution containing a small amount of biological enzyme to remove the template agent starch, and drying to obtain the macroporous white carbon black material. The method needs to add a biological enzyme aqueous solution to remove the template agent, the enzymolysis condition is harsh, and a large amount of time is consumed for enzymolysis, which is not beneficial to large-scale production.
CN 105060307A discloses white carbon black with high specific surface area and a production method thereof, wherein the production method comprises the following steps: (1) Dissolving solid sodium silicate, introducing water vapor into the dissolved solution, and filtering out the precipitate to obtain transparent impurity-free concentrated liquid sodium silicate; (2) Diluting the concentrated liquid sodium silicate to obtain diluted liquid sodium silicate; (3) Mixing dilute liquid sodium silicate and sulfuric acid to perform precipitation reaction, and adjusting the pH value to 3.5-6.5 after the precipitation reaction is finished to obtain dilute silicon dioxide slurry; and (4) filtering, slurrying and drying to obtain a finished white carbon black product. The production method improves the aperture and the specific surface area of the white carbon black by controlling the synthesis conditions of the white carbon black, but more parameters need to be controlled, and the production method is complex.
Aiming at the defects in the prior art, the invention provides a method for preparing large-aperture white carbon black by using water glass as a silicon source and sulfuric acid as an acidifying agent. On the basis of the preparation process by the sulfuric acid precipitation method, the preparation process is optimized, and the formation and agglomeration processes of silicon dioxide particles are changed by selecting additives, so that the large-aperture white carbon black product with larger aperture and better dispersibility is obtained. The method can obtain the white carbon black with excellent performance while reducing the manufacturing cost, and has important significance for popularizing the industrial application of the precipitation method.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the large-aperture white carbon black and the preparation method and the application thereof. The method can obtain the white carbon black with excellent performance while reducing the manufacturing cost, and has important significance for popularizing the industrial application of the precipitation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of large-aperture white carbon black, which comprises the following steps:
(1) Simultaneously dripping a water glass solution and sulfuric acid into the reaction bottom material to enable the water glass and the sulfuric acid to have precipitation reaction, and then adjusting the pH value to be acidic to obtain a white carbon black suspension;
(2) Carrying out filter pressing on the white carbon black suspension obtained in the step (1), and sequentially washing, slurrying and drying the obtained filter cake to obtain the large-aperture white carbon black;
the reaction substrate in the step (1) contains a carbonate additive.
According to the preparation method, the formation and agglomeration processes of silicon dioxide particles are changed by adding the carbonate additive on the basis of a sulfuric acid precipitation method, and the large-aperture white carbon black product with larger aperture and better dispersibility is obtained.
The large-aperture white carbon black is white carbon black with the most probable aperture of more than 40 nm.
Preferably, the reaction substrate in the step (1) is a mixed aqueous solution of water glass and a carbonate additive.
Preferably, with Na 2 The concentration of water glass in the reaction substrate in the step (1) is 0.15 to 0.28mol/L, and may be, for example, 0.15mol/L, 0.18mol/L, 0.20mol/L, 0.21mol/L, 0.24mol/L, 0.25mol/L, 0.27mol/L or 0.28mol/L, but is not limited to the values listed, and other values not listed in the numerical ranges are also applicable.
Preferably, the water glass has a modulus of 1.5 to 3.5, which may be, for example, 1.5, 2, 2.5, 3 or 3.5, but is not limited to the values listed, and other values not listed in the numerical range are equally suitable.
Preferably, the amount of the carbonate additive added to the reaction base in step (1) is 3-8% of the theoretical mass of the obtained large pore size silica, and may be, for example, 3%, 4%, 5%, 6%, 7% or 8%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the carbonate additive is ammonium carbonate.
Preferably, with Na 2 O, the concentration of the water glass in the water glass solution in the step (1) is 0.5-1.6mol/L; for example, it may be 0.5mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, or 1.6mol/L, but is not limited to the recited values, ranges of valuesOther values not listed are equally applicable.
Preferably, the modulus of the water glass in the water glass solution in step (1) is 1.5-3.5, for example 1.5, 2, 2.5, 3 or 3.5, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
Preferably, the concentration of the sulfuric acid in step (1) is 2 to 3.5mol/L, and may be, for example, 2mol/L, 2.1mol/L, 2.4mol/L, 2.5mol/L, 2.7mol/L, 2.8mol/L, 3mol/L, 3.2mol/L or 3.5mol/L, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the weight ratio of water glass in the reaction bottom material in the step (1) to water glass in the water glass solution is 1 (3-15), and can be, for example, 1.
Preferably, the sulfuric acid is added dropwise in the step (1) in an amount such that the concentration of the water glass in the mixture of the reaction substrate, the water glass solution and the sulfuric acid is maintained at 0.15 to 0.28mol/L, for example, 0.15mol/L, 0.18mol/L, 0.20mol/L, 0.21mol/L, 0.24mol/L, 0.25mol/L, 0.27mol/L or 0.28mol/L, but the amount is not limited to the values listed, and other values not listed in the range of values are also applicable.
The term "concentration maintained at 0.15 to 0.28mol/L" as used herein means that the concentration of water glass in the mixed solution is the same as the concentration of water glass in the reaction substrate. For example, when the initial concentration of the water glass in the reaction substrate is 0.15mol/L, the concentration of the water glass in the mixed solution is kept constant at 0.15mol/L by controlling the dripping amount of the sulfuric acid during the dripping process of the water glass solution and the sulfuric acid; when the initial concentration of the water glass in the reaction bottom material is 0.28mol/L, the concentration of the water glass in the mixed solution is kept constant at 0.28mol/L by controlling the dripping amount of the sulfuric acid in the dripping process of the water glass solution and the sulfuric acid.
Preferably, the precipitation reaction of step (1) is carried out at a temperature of 70-85 ℃, for example 70 ℃, 72 ℃, 75 ℃, 77 ℃,80 ℃, 81 ℃ or 85 ℃, but not limited to the recited values, and other values not recited in the numerical range are equally applicable; the time is 50-120min, for example 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
The temperature of the precipitation reaction is 70-85 ℃, which means that the temperature of the reaction substrate is raised to 70-85 ℃ before simultaneously dripping the water glass solution and the sulfuric acid, and the temperature is kept unchanged in the process of dripping the water glass solution and performing the precipitation reaction.
Preferably, the pH value is adjusted to be acidic in the step (1), and the pH value is adjusted to be 3-5 by using sulfuric acid with the concentration of 2-3.5 mol/L; the concentration of the sulfuric acid is 2 to 3.5mol/L, and may be, for example, 2mol/L, 2.1mol/L, 2.4mol/L, 2.5mol/L, 2.7mol/L, 2.8mol/L, 3mol/L, 3.2mol/L or 3.5mol/L, but is not limited to the values listed, and other values not listed in the numerical range are also applicable; the pH after adjustment is 3 to 5, and may be, for example, 3, 3.5, 4, 4.5 or 5.
Preferably, siO in the filter cake in the step (2) 2 The mass fraction of (B) is 18 to 25wt%, and may be, for example, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt% or 25wt%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the step of slurrying of step (2) comprises: mixing the filter cake with water, and pulping to obtain a slurried suspension.
Preferably, the mixing of the filter cake with water is such that SiO is present in the mixture 2 The mass fraction of (B) is from 13 to 15% by weight, and may be, for example, 13%, 13.5%, 14%, 14.5% or 15% by weight, but is not limited to the values recited, and other values not recited in the numerical ranges are equally applicable.
Preferably, the stirring speed of the beating is 50-200rpm, for example, 50rpm, 80rpm, 100rpm, 120rpm, 150rpm, 180rpm or 200rpm, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable; the beating time is 60-120min, for example 60min, 70min, 80min, 90min, 100min, 110min or 120min, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the drying of step (2) is spray drying the resulting slurried suspension.
Preferably, the spray drying pressure is 15 to 40bar, for example 15bar, 20bar, 25bar, 30bar, 35bar or 40bar, but is not limited to the values recited, and other values within the ranges are equally applicable.
The spray drying is carried out by using a pressure type sprayer, and the pressure of the spray drying is the feeding pressure of the pressure type sprayer.
As a preferable technical solution of the preparation method of the first aspect of the present invention, the preparation method comprises the steps of:
(1) Dripping a water glass solution and sulfuric acid with the concentration of 2-3.5mol/L for 50-120min in the reaction substrate at the temperature of 70-85 ℃ to ensure that the water glass and the sulfuric acid have precipitation reaction, and then adjusting the pH value to 3-5 by using the sulfuric acid with the concentration of 2-3.5mol/L to obtain a white carbon black suspension;
(2) Carrying out filter pressing on the white carbon black suspension obtained in the step (1) to obtain SiO 2 Washing, slurrying and drying the obtained filter cake sequentially to obtain the large-aperture white carbon black, wherein the mass fraction of the filter cake is 18-25 wt%; the pulping is as follows: mixing the filter cake with water to form SiO 2 13-15wt%, pulping at 50-200rpm for 60-120min to obtain a pulping suspension; the drying is spray drying;
the reaction bottom material in the step (1) contains ammonium carbonate, and the addition amount of the ammonium carbonate is 3-8% of the theoretical mass of the obtained large-aperture white carbon black; with Na 2 O, the concentration of the water glass in the reaction bottom material in the step (1) is 0.15-0.28mol/L, and the modulus is 1.5-3.5; with Na 2 O, the concentration of the water glass in the water glass solution in the step (1) is 0.5-1.6mol/L, and the modulus is 1.5-3.5; the weight ratio of the water glass in the reaction bottom material in the step (1) to the water glass in the water glass solution is 1 (3-15); in the dropwise adding process in the step (1), the concentration of the water glass in the mixed solution of the reaction substrate, the water glass solution and the sulfuric acid is 0.15-0.28mol/L.
In a second aspect, the invention provides the white carbon black with large pore diameter prepared by the preparation method in the first aspect.
Preferably, the largest possible pore diameter of the large-pore-diameter white carbon black is more than 40nm, and the BET specific surface area is 100m 2 More than g, and a CTAB specific surface area of 113m 2 (ii) a degree of dispersion of 9 or more per gram.
In a third aspect, the invention provides an application of the large-aperture white carbon black in the second aspect in preparing a rubber reinforcing agent.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
on the basis of the preparation process by the sulfuric acid precipitation method, the preparation process is optimized, and the formation and agglomeration processes of silicon dioxide particles are changed by selecting additives, so that the large-aperture white carbon black product with larger aperture and better dispersibility is obtained. The method can obtain the white carbon black with excellent performance while reducing the manufacturing cost, and has important significance for popularizing the application of the precipitation method in industry.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a preparation method of large-aperture white carbon black, which comprises the following steps:
(1) Dripping a water glass solution and sulfuric acid with the concentration of 2.7mol/L for 80min in the reaction substrate at the temperature of 78 ℃ to ensure that the water glass and the sulfuric acid have precipitation reaction, and then adjusting the pH value to 4 by using the sulfuric acid with the concentration of 2.7mol/L to obtain white carbon black suspension;
(2) Carrying out filter pressing on the white carbon black suspension obtained in the step (1) to obtain SiO 2 Washing, slurrying and drying the obtained filter cake sequentially to obtain the large-aperture white carbon black, wherein the mass fraction of the filter cake is 21 wt%; the pulping is as follows: mixing the filter cake with waterMake SiO 2 The mass fraction of the slurry is 14wt%, and the slurry is beaten for 90min at 120rpm to obtain a slurried suspension; the drying is spray drying, and the pressure of the spray drying is 27bar;
the reaction bottom material in the step (1) contains ammonium carbonate, and the addition amount of the ammonium carbonate is 5% of the theoretical mass of the obtained large-aperture white carbon black; with Na 2 O, the concentration of water glass in the reaction bottom material in the step (1) is 0.21mol/L, and the modulus is 2.5; with Na 2 O, the concentration of the water glass in the water glass solution in the step (1) is 1mol/L, and the modulus is 2.5; the weight ratio of water glass in the reaction bed charge to water glass in the water glass solution in the step (1) is 1; in the dropwise adding process in the step (1), the concentration of the water glass in the mixed solution of the reaction substrate, the water glass solution and the sulfuric acid is 0.21mol/L.
Example 2
The embodiment provides a preparation method of large-aperture white carbon black, which comprises the following steps:
(1) Dripping a water glass solution and sulfuric acid with the concentration of 2.4mol/L for 60min in the reaction substrate at the temperature of 74 ℃ simultaneously to ensure that the water glass and the sulfuric acid have precipitation reaction, and then adjusting the pH value to 3.5 by using the sulfuric acid with the concentration of 3mol/L to obtain white carbon black suspension;
(2) Carrying out filter pressing on the white carbon black suspension obtained in the step (1) to obtain SiO 2 Washing, slurrying and drying the obtained filter cake sequentially to obtain the large-aperture white carbon black, wherein the mass fraction of the filter cake is 20 wt%; the pulping is as follows: mixing the filter cake with water to form SiO 2 The mass fraction of the slurry is 13.5wt%, and pulping for 105min at 80rpm to obtain a pulping suspension; the drying is spray drying, and the pressure of the spray drying is 21bar;
the reaction bottom material in the step (1) contains ammonium carbonate, and the addition amount of the ammonium carbonate is 4% of the theoretical mass of the obtained large-aperture white carbon black; with Na 2 O, the concentration of water glass in the reaction bottom material in the step (1) is 0.18mol/L, and the modulus is 3; with Na 2 O, the concentration of the water glass in the water glass solution in the step (1) is 0.8mol/L, and the modulus is 3; the weight ratio of water glass in the reaction bed charge to water glass in the water glass solution in the step (1) is 1; the step (1) of dropwise addingIn the process, the concentration of water glass in the mixed solution of the reaction substrate, the water glass solution and the sulfuric acid is 0.18mol/L.
Example 3
The embodiment provides a preparation method of large-aperture white carbon black, which comprises the following steps:
(1) Dripping a water glass solution and 3mol/L sulfuric acid into the reaction substrate at the same time for 100min at the temperature of 81 ℃ to ensure that the water glass and the sulfuric acid have precipitation reaction, and then regulating the pH value to 4.5 by using the 2.4mol/L sulfuric acid to obtain a white carbon black suspension;
(2) Carrying out filter pressing on the white carbon black suspension obtained in the step (1) to obtain SiO 2 Washing, slurrying and drying the obtained filter cake sequentially to obtain the large-aperture white carbon black, wherein the mass fraction of the filter cake is 23 wt%; the pulping is as follows: mixing the filter cake with water to form SiO 2 The mass fraction of the slurry is 14.5wt%, and pulping for 75min at 150rpm to obtain a pulping suspension; the drying is spray drying, and the pressure of the spray drying is 35bar;
the reaction bottom material in the step (1) contains ammonium carbonate, and the addition amount of the ammonium carbonate is 6% of the theoretical mass of the obtained large-aperture white carbon black; with Na 2 O, wherein the concentration of water glass in the reaction bottom material in the step (1) is 0.25mol/L, and the modulus is 2; with Na 2 O, the concentration of the water glass in the water glass solution in the step (1) is 1.2mol/L, and the modulus is 2; the weight ratio of water glass in the reaction bed charge to water glass in the water glass solution in the step (1) is 1; in the dropwise adding process in the step (1), the concentration of the water glass in the mixed solution of the reaction substrate, the water glass solution and the sulfuric acid is 0.25mol/L.
Example 4
The embodiment provides a preparation method of large-aperture white carbon black, which comprises the following steps:
(1) Dripping a water glass solution and sulfuric acid with the concentration of 2mol/L into the reaction substrate for 50min at the temperature of 70 ℃ to ensure that the water glass and the sulfuric acid have precipitation reaction, and then regulating the pH value to be 5 by using the sulfuric acid with the concentration of 2mol/L to obtain a white carbon black suspension;
(2) Carrying out filter pressing on the white carbon black suspension obtained in the step (1) to obtainTo SiO 2 Washing, slurrying and drying the obtained filter cake sequentially to obtain the large-aperture white carbon black, wherein the mass fraction of the filter cake is 25 wt%; the pulping is as follows: mixing the filter cake with water to form SiO 2 The mass fraction of the slurry is 15wt%, and pulping for 60min at 200rpm to obtain a pulping suspension; the drying is spray drying, and the pressure of the spray drying is 15bar;
the reaction bottom material in the step (1) contains ammonium carbonate, and the addition amount of the ammonium carbonate is 3% of the theoretical mass of the obtained large-aperture white carbon black; with Na 2 O, wherein the concentration of water glass in the reaction bottom material in the step (1) is 0.28mol/L, and the modulus is 1.5; with Na 2 O, the concentration of the water glass in the water glass solution in the step (1) is 0.5mol/L, and the modulus is 1.5; the weight ratio of the water glass in the reaction bottom material to the water glass in the water glass solution in the step (1) is 1; in the dropwise adding process in the step (1), the concentration of the water glass in the mixed solution of the reaction substrate, the water glass solution and the sulfuric acid is 0.28mol/L.
Example 5
The embodiment provides a preparation method of large-aperture white carbon black, which comprises the following steps:
(1) Dripping a water glass solution and 3.5mol/L sulfuric acid into the reaction substrate at the same time for 120min at the temperature of 85 ℃ to ensure that the water glass and the sulfuric acid have precipitation reaction, and then adjusting the pH value to 3 by using the 3.5mol/L sulfuric acid to obtain a white carbon black suspension;
(2) Carrying out filter pressing on the white carbon black suspension obtained in the step (1) to obtain SiO 2 Washing, slurrying and drying the obtained filter cake sequentially to obtain the large-aperture white carbon black, wherein the mass fraction of the filter cake is 18 wt%; the pulping is as follows: mixing the filter cake with water to form SiO 2 The mass fraction of the slurry is 13wt%, and pulping for 120min at 50rpm to obtain a pulping suspension; the drying is spray drying, and the pressure of the spray drying is 40bar;
the reaction bottom material in the step (1) contains ammonium carbonate, and the addition amount of the ammonium carbonate is 8% of the theoretical mass of the obtained large-aperture white carbon black; with Na 2 O, wherein the concentration of water glass in the reaction bottom material in the step (1) is 0.15mol/L, and the modulus is 3.5; with Na 2 O meter, step (1)) The concentration of the water glass in the water glass solution is 1.6mol/L, and the modulus is 3.5; the weight ratio of water glass in the reaction bed charge to water glass in the water glass solution in the step (1) is 1; in the dropwise adding process in the step (1), the concentration of the water glass in the mixed solution of the reaction substrate, the water glass solution and the sulfuric acid is 0.15mol/L.
Comparative example 1
The comparative example provides a preparation method of large-aperture white carbon black, and the method is the same as the method in the example 1 except that ammonium carbonate is not added in the reaction bottom material in the step (1).
The specific surface area (BET), external specific surface area (CTAB), most probable pore size, and degree of dispersion of the white carbon black prepared in examples 1 to 5 and comparative example 1 were measured.
Wherein, the specific surface area is measured according to HG/T3073-1991 method for measuring nitrogen adsorption on the surface of precipitated hydrated silica; the external specific surface area is measured according to GB/T23656-2016 CTAB method for measuring the specific surface area of the rubber compounding agent precipitated hydrated silicon dioxide; the dispersity is measured by GB/T6030-2006 Rapid comparison method for evaluation of dispersion of carbon black and carbon black silica in rubber; the most probable pore size was determined using a mercury porosimeter.
The results obtained are shown in table 1.
TABLE 1
As can be seen from Table 1, the largest possible pore diameter of the large-pore-diameter silica prepared by the present invention is 40nm or more, and the dispersion degree is 9 or more. As can be seen from comparative example 1, when no carbonate additive was added, the mode pore size was reduced from 46.3nm to 34.1nm, and the dispersity was reduced from 9.7 to 8.5.
In conclusion, on the basis of the preparation process by the sulfuric acid precipitation method, the preparation process is optimized, and the formation and agglomeration processes of silicon dioxide particles are changed by selecting the additive, so that the large-aperture white carbon black product with larger aperture and better dispersibility is obtained. The method can obtain the white carbon black with excellent performance while reducing the manufacturing cost, and has important significance for popularizing the application of the precipitation method in industry.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The preparation method of the large-aperture white carbon black is characterized by comprising the following steps:
(1) Dripping a water glass solution and sulfuric acid into the reaction bottom material at the same time to ensure that the water glass and the sulfuric acid with the concentration of 2-3.5mol/L are subjected to precipitation reaction, and then regulating the pH value to 3-5 by using the sulfuric acid with the concentration of 2-3.5mol/L to obtain a white carbon black suspension; the dripping amount of the sulfuric acid is to ensure that the concentration of the water glass in the mixed solution of the reaction bottom material, the water glass solution and the sulfuric acid is maintained to be 0.15-0.28mol/L; the concentration of the water glass in the reaction bottom material is 0.15-0.28mol/L; the modulus of the water glass is 1.5-3.5; the temperature of the precipitation reaction is 70-85 ℃, and the time is 50-120min;
(2) Carrying out filter pressing on the white carbon black suspension liquid obtained in the step (1), and sequentially washing, slurrying and drying the obtained filter cake to obtain the large-aperture white carbon black;
the weight ratio of the water glass in the reaction bottom material in the step (1) to the water glass in the water glass solution is 1 (3-15);
the reaction bottom material in the step (1) is a mixed aqueous solution of water glass and a carbonate additive; the addition amount of the carbonate additive in the reaction bottom material is 3-8% of the theoretical mass of the obtained large-aperture white carbon black; the carbonate additive is ammonium carbonate;
the large-aperture white carbon black is white carbon black with the most probable aperture of more than 40 nm.
2. The method according to claim 1, wherein Na is added 2 O is measured, and the water in the step (1)The concentration of the water glass in the glass solution is 0.5-1.6mol/L.
3. The method according to claim 1, wherein the modulus of the water glass in the water glass solution of step (1) is 1.5 to 3.5.
4. The method according to claim 1, wherein SiO in the filter cake in the step (2) 2 Is 18-25wt%.
5. The method of claim 1, wherein the step of slurrying in step (2) comprises: mixing the filter cake with water, and pulping to obtain a slurried suspension.
6. The method of claim 5, wherein the mixing the filter cake with water is performed such that SiO is present in the mixture 2 The mass fraction of (B) is 13-15wt%.
7. The method for preparing a compound according to claim 5, wherein the stirring speed of the beating is 50-200rpm, and the beating time is 60-120min.
8. The method according to claim 1, wherein the drying in step (2) is spray drying the slurry suspension.
9. The method of claim 8, wherein the spray drying pressure is 15-40bar.
10. The method of claim 1, comprising the steps of:
(1) Dripping a water glass solution and sulfuric acid with the concentration of 2-3.5mol/L for 50-120min in the reaction substrate at the temperature of 70-85 ℃ to ensure that the water glass and the sulfuric acid have precipitation reaction, and then adjusting the pH value to 3-5 by using the sulfuric acid with the concentration of 2-3.5mol/L to obtain a white carbon black suspension;
(2) Carrying out filter pressing on the white carbon black suspension obtained in the step (1) to obtain SiO 2 Washing, slurrying and drying the obtained filter cake sequentially to obtain the large-aperture white carbon black, wherein the mass fraction of the filter cake is 18-25 wt%; the pulping is as follows: mixing the filter cake with water to form SiO 2 13-15wt%, pulping at 50-200rpm for 60-120min to obtain a pulping suspension; the drying is spray drying;
the reaction bottom material in the step (1) contains ammonium carbonate, and the addition amount of the ammonium carbonate is 3-8% of the theoretical mass of the obtained large-aperture white carbon black; with Na 2 O, the concentration of the water glass in the reaction bottom material in the step (1) is 0.15-0.28mol/L, and the modulus is 1.5-3.5; with Na 2 O, the concentration of the water glass in the water glass solution in the step (1) is 0.5-1.6mol/L, and the modulus is 1.5-3.5; the weight ratio of the water glass in the reaction bottom material in the step (1) to the water glass in the water glass solution is 1 (3-15); in the dropwise adding process in the step (1), the concentration of the water glass in the mixed solution of the reaction substrate, the water glass solution and the sulfuric acid is 0.15-0.28mol/L.
11. The white carbon black with large aperture prepared by the preparation method according to any one of claims 1 to 10.
12. Use of the silica according to claim 11 for the preparation of a rubber reinforcement.
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| CN112573524B (en) * | 2020-12-29 | 2022-11-22 | 无锡恒诚硅业有限公司 | Precipitated silica, and preparation method and application thereof |
| CN113636564B (en) * | 2021-09-09 | 2022-11-22 | 无锡恒诚硅业有限公司 | Green preparation method of white carbon black |
| WO2023097541A1 (en) * | 2021-12-01 | 2023-06-08 | 无锡恒诚硅业有限公司 | Preparation method for hydrophilic white carbon black and application |
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