Black ceramic pigment and preparation method thereof

Abstract

The invention relates to the technical field of ceramic pigment preparation, in particular to a black ceramic pigment and a preparation method thereof. The preparation method comprises the following steps: S1, adding cobalt salt, nickel salt, ferric salt and manganese salt into deionized water, and uniformly stirring and mixing to obtain a mixed solution; s2, adjusting the pH value to obtain a precipitate; s3, drying and grinding the precipitate; s4, calcining to obtain a secondary black pigment; s5, carrying out surface treatment on the secondary black pigment; s6, performing wet grinding on the secondary black pigment and the modified mesoporous silica, and heating; and S7, carrying out alkali liquor treatment, and washing a filtered product with water to obtain the black ceramic pigment. The black ceramic pigment prepared by the invention has excellent blackness performance, and the preparation method is simple and suitable for popularization.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic pigment preparation, in particular to a black ceramic pigment and a preparation method thereof. Background Art

[0002] Ceramic pigments are a general term for pigments used in ceramic production. They impart a rich, vibrant luster and color to ceramics. Black ceramic pigments are a common type of ceramic pigment. Black can evoke multiple emotions, from tranquility and peace to elegance and passion. Therefore, black ceramic pigments have become widely used as functional pigments in the decoration of inorganic materials such as ceramics, enamel, and glass. Their primary function is to provide a stable, uniform black coloring effect on the substrate. With the continuous development of the ceramic industry, the demand for black ceramic pigments has also increased, often reflecting a demand for the purity of the black color.

[0003] Existing black ceramic pigments are typically composed of transition metal oxides (such as Fe, Co, Cr, Mn, and Cu) and synthesized through high-temperature solid-phase reactions. However, due to a lack of microstructural control during the solid-phase synthesis of existing transition metal oxide ceramic pigments, visible light absorption is incomplete, resulting in insufficient blackness. Therefore, to address some of the problems encountered in the aforementioned background art, the present invention improves the blackness of traditional black ceramic pigments by introducing a carbon material product calcined in an inert atmosphere of sucrose. Furthermore, the structure of the calcined product is microscopically controlled to improve the blackness of traditional black ceramic pigments. Summary of the Invention

[0004] The object of the present invention is to provide a black ceramic pigment and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0005] To achieve the above object, the present invention provides the following technical solutions: A method for preparing a black ceramic pigment comprises the following steps: S1. Add cobalt salt, nickel salt, iron salt and manganese salt to deionized water, and stir to mix well to obtain a mixed solution; S2. Add 0.2 mol / L sodium hydroxide solution dropwise to the mixed solution obtained in step S1, adjust the pH to 8-9, and filter to obtain a precipitate; S3, drying the precipitate obtained in step S2 at 90°C to constant weight, and then grinding it through a 200-500 mesh sieve; S4, placing the precipitate ground in step S3 into a muffle furnace and calcining it in an air atmosphere for 1-3 hours to obtain a calcined product at a calcination temperature of 1080-1200° C. to obtain a secondary black pigment; S5. Dispersing the secondary black pigment obtained in step S4 into a mixed solution of polyacrylic acid, deionized water, and diethylene glycol, heating the mixture to 100-160° C. for a continuous reaction of 1-4 hours, filtering the mixture after the reaction, washing the filtered product with sufficient deionized water, and drying the mixture at 60° C. to a constant weight; S6. Mixing the secondary black pigment treated in step S5 with the modified mesoporous silica, adding a mixed solution of deionized water and anhydrous ethanol, wet grinding for 2-4 hours, and then filtering. The filtered product is heated at 200-250° C. for 3-5 hours to obtain a mixture; S7, adding the mixture obtained in step S6 to a 2 mol / L sodium hydroxide solution and reacting at 60° C. for 4-8 hours, washing the filtered product with sufficient deionized water until neutral, and then drying at 100° C. to constant weight to obtain a black ceramic pigment; The preparation method of the modified mesoporous silica comprises the following steps: S101, dispersing mesoporous silica in a deionized water solution containing sucrose, then adding concentrated sulfuric acid dropwise, evaporating the deionized water at 80-150° C., and maintaining the temperature for 8-10 hours after the deionized water is completely evaporated to obtain a solid material; S102, calcining the mesoporous silica treated in step S101 at 850-950° C. for 4-8 hours under a nitrogen atmosphere; S103. Disperse the mesoporous silica treated in step S102 into a toluene solution containing γ-aminopropyltriethoxysilane, heat to 70°C, react for 4-8 hours, and then filter. Wash the filtered product with sufficient ethanol and vacuum dry it at 40°C to constant weight to obtain modified mesoporous silica.

[0006] Furthermore, in step S1, the molar ratio of the cobalt salt, the nickel salt, the iron salt and the manganese salt is (0.8-1.0):(0.1-0.3):(0.6-0.8):(0.4-0.6).

[0007] Furthermore, in step S1, the mass ratio of the sum of the masses of the cobalt salt, nickel salt, iron salt, and manganese salt to deionized water is 1:(15-20).

[0008] Furthermore, the mass ratio of the secondary black pigment, polyacrylic acid, deionized water and diethylene glycol used in step S5 is 1:(0.5-2):(30-50):(10-13).

[0009] Furthermore, the mass ratio between deionized water and anhydrous ethanol in step S6 is 1:1; the mass ratio between the sum of the mass of deionized water and anhydrous ethanol used in step S6, the secondary black pigment and the modified mesoporous silica is (4-8):(2-3):1.

[0010] Furthermore, the mass ratio between the sodium hydroxide solution used in step S7 and the modified mesoporous silica used in step S6 is 70:1.

[0011] Furthermore, in step S101, the mass ratio of concentrated sulfuric acid, sucrose, mesoporous silica and deionized water is 1:(10-15):(20-30):(100-200).

[0012] Furthermore, the mass ratio of mesoporous silica, γ-aminopropyltriethoxysilane and toluene used in step S103 is 1:0.2:8.

[0013] A black ceramic pigment is prepared by the above-mentioned preparation method of the black ceramic pigment.

[0014] Compared with the prior art, the present invention has the following beneficial effects: 1. This invention improves the blackness of black ceramic pigments by introducing a calcined sucrose product into the ceramic pigment. The sucrose is co-evaporated with mesoporous silica, introducing the sucrose into the pores of the mesoporous silica. Finally, an alkaline solution is used to remove the mesoporous silica template. The calcined sucrose product is constrained by the mesopores, and its structure is microscopically controlled. When introduced into the black ceramic pigment, the blackness of the black ceramic pigment is improved. 2. In the present invention, the carbon material follows the nano-silica into the secondary black pigment and is wet-milled together, thereby promoting the grinding and dispersion of the secondary black pigment. At the same time, by surface treating the secondary black pigment and the mesoporous silica, the bonding uniformity between the two is improved, the wet-milling effect is better exerted, and the blackness of the prepared black ceramic pigment is further improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a process flow chart for preparing black ceramic pigments according to the present invention; Figure 2 This is a process flow chart for preparing modified mesoporous silica according to the present invention. DETAILED DESCRIPTION

[0016] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0017] See also Figures 1 to 2 , the present invention provides:

[0018] Example 1 A method for preparing a black ceramic pigment comprises the following steps: S1, add 26.5g of cobalt salt, 4.5g of nickel salt, 27.6g of iron salt, and 12.5g of manganese salt to 1.28kg of deionized water, and stir to mix to obtain a mixed solution; S2. Add 0.2 mol / L sodium hydroxide solution dropwise to the mixed solution obtained in step S1, adjust the pH to 8.5, and filter to obtain a precipitate; S3, drying the precipitate obtained in step S2 at 90° C. to a constant weight, and then grinding it through a 300-mesh sieve; S4, placing the precipitate ground in step S3 into a muffle furnace and calcining it in air for 2.5 hours at a temperature of 1120° C. to obtain a calcined product, thereby obtaining a secondary black pigment; S5. Dispersing 11.2 g of the secondary black pigment obtained in step S4 into a mixed solution of polyacrylic acid, deionized water, and diethylene glycol, where the amounts of polyacrylic acid, deionized water, and diethylene glycol are 7.9 g, 425 g, and 136 g, respectively. The mixture is heated to 130° C. and reacted continuously for 3.6 h. After the reaction, the filtered product is washed with sufficient deionized water and dried at 60° C. to a constant weight. S6. Mix 10.6 g of the secondary black pigment treated in step S5 with 4.3 g of modified mesoporous silica, add a mixed solution of 13.2 g of deionized water and 13.2 g of anhydrous ethanol, wet grind for 2.5 hours, and then filter. Heat the filtered product at 230° C. for 4.5 hours to obtain a mixture; S7, adding the mixture obtained in step S6 to 301 g of 2 mol / L sodium hydroxide solution at 60° C. for 6.8 h, washing the filtered product with sufficient deionized water until neutral, and then drying at 100° C. to constant weight to obtain a black ceramic pigment; The preparation method of the modified mesoporous silica comprises the following steps: S101, dispersing 8.5 g of mesoporous silica into a deionized water solution containing sucrose, where the amounts of sucrose and deionized water are 4.2 g and 52.5 g, respectively; then adding dropwise 0.35 g of 98 wt % concentrated sulfuric acid; evaporating the deionized water at 125° C.; and maintaining the temperature for 8.6 h after the deionized water is completely evaporated, to obtain a solid material; S102, calcining the mesoporous silica treated in step S101 at 880° C. for 6 h under a nitrogen atmosphere; S103. Disperse 7.8 g of mesoporous silica treated in step S102 into a toluene solution containing γ-aminopropyltriethoxysilane, where the amounts of γ-aminopropyltriethoxysilane and toluene are 1.56 g and 62.4 g, respectively. Heat to 70°C, react for 4.5 hours, and then filter. Wash the filtered product with sufficient ethanol and vacuum dry it at 40°C to constant weight to obtain modified mesoporous silica.

[0019] Example 2 A method for preparing a black ceramic pigment comprises the following steps: S1, add 23.3g of cobalt salt, 2.9g of nickel salt, 24.2g of iron salt, and 10g of manganese salt to 906g of deionized water, and stir to mix to obtain a mixed solution; S2. Add 0.2 mol / L sodium hydroxide solution dropwise to the mixed solution obtained in step S1, adjust the pH to 8, and filter to obtain a precipitate; S3, drying the precipitate obtained in step S2 at 90° C. to a constant weight, and then grinding it through a 200-mesh sieve; S4, placing the precipitate ground in step S3 into a muffle furnace and calcining it in air for 1 hour at a temperature of 1080° C. to obtain a secondary black pigment; S5. Dispersing 8.6 g of the secondary black pigment obtained in step S4 into a mixed solution of polyacrylic acid, deionized water, and diethylene glycol, where the amounts of polyacrylic acid, deionized water, and diethylene glycol are 4.3 g, 258 g, and 86 g, respectively, the mixture is heated to 100° C. and reacted continuously for 1 hour. After the reaction, the mixture is filtered, and the filtered product is washed with sufficient deionized water and dried at 60° C. to a constant weight. S6. Mix 7.8 g of the secondary black pigment treated in step S5 with 3.9 g of modified mesoporous silica, add a mixed solution of 7.8 g of deionized water and 7.8 g of anhydrous ethanol, wet grind for 2 h, and then filter. Heat the filtered product at 200° C. for 3 h to obtain a mixture; S7, adding the mixture obtained in step S6 to 273 g of 2 mol / L sodium hydroxide solution and reacting at 60° C. for 4 h, washing the filtered product with sufficient deionized water until neutral, and then drying at 100° C. to constant weight to obtain a black ceramic pigment; The preparation method of the modified mesoporous silica comprises the following steps: S101, dispersing 8.5 g of mesoporous silica into a deionized water solution containing sucrose, where the amounts of sucrose and deionized water are 4.25 g and 42.5 g, respectively; then adding dropwise 0.425 g of 98 wt % concentrated sulfuric acid; evaporating the deionized water at 80° C.; and maintaining the temperature for 8 h after the deionized water is completely evaporated, to obtain a solid material; S102, calcining the mesoporous silica treated in step S101 at 850° C. for 4 h under a nitrogen atmosphere; S103. Disperse 7.8 g of mesoporous silica treated in step S102 into a toluene solution containing γ-aminopropyltriethoxysilane, where the amounts of γ-aminopropyltriethoxysilane and toluene are 1.56 g and 62.4 g, respectively. Heat to 70°C, react for 4 hours, and then filter. Wash the filtered product with sufficient ethanol and vacuum dry it at 40°C to constant weight to obtain modified mesoporous silica.

[0020] Example 3 A method for preparing a black ceramic pigment comprises the following steps: S1, add 29.1g of cobalt salt, 8.7g of nickel salt, 32.3g of iron salt, and 15.1g of manganese salt to 1.7kg of deionized water, and stir to mix to obtain a mixed solution; S2. Add 0.2 mol / L sodium hydroxide solution dropwise to the mixed solution obtained in step S1, adjust the pH to 9, and filter to obtain a precipitate; S3, drying the precipitate obtained in step S2 at 90° C. to a constant weight, and then grinding it through a 500-mesh sieve; S4, placing the precipitate ground in step S3 into a muffle furnace and calcining it in air for 3 hours at a temperature of 1200° C. to obtain a secondary black pigment; S5. Dispersing 12.4 g of the secondary black pigment obtained in step S4 into a mixed solution of polyacrylic acid, deionized water, and diethylene glycol, where the amounts of polyacrylic acid, deionized water, and diethylene glycol are 24.8 g, 620 g, and 124 g, respectively, the mixture is heated to 160° C. and reacted continuously for 4 h. After the reaction, the mixture is filtered, and the filtered product is washed with sufficient deionized water and dried at 60° C. to a constant weight. S6. Mix 10.8 g of the secondary black pigment treated in step S5 with 3.6 g of modified mesoporous silica, add a mixed solution of 14.4 g of deionized water and 14.4 g of anhydrous ethanol, wet grind for 4 h, and then filter. Heat the filtered product at 250° C. for 5 h to obtain a mixture; S7, adding the mixture obtained in step S6 to 252 g of 2 mol / L sodium hydroxide solution and reacting at 60° C. for 8 h, washing the filtered product with sufficient deionized water until neutral, and then drying at 100° C. to constant weight to obtain a black ceramic pigment; The preparation method of the modified mesoporous silica comprises the following steps: S101, dispersing 8.5 g of mesoporous silica into a deionized water solution containing sucrose, where the amounts of sucrose and deionized water are 4.2 g and 56 g, respectively; then adding dropwise 0.28 g of 98 wt % concentrated sulfuric acid; evaporating the deionized water at 150° C.; and maintaining the temperature for 10 hours after the deionized water is completely evaporated, to obtain a solid material; S102, calcining the mesoporous silica treated in step S101 at 950° C. for 8 h under a nitrogen atmosphere; S103. Disperse 7.8 g of mesoporous silica treated in step S102 into a toluene solution containing γ-aminopropyltriethoxysilane, where the amounts of γ-aminopropyltriethoxysilane and toluene are 1.56 g and 62.4 g, respectively. Heat to 70°C, react for 8 hours, and then filter. Wash the filtered product with sufficient ethanol and vacuum dry it at 40°C to constant weight to obtain modified mesoporous silica.

[0021] Example 4 A method for preparing a black ceramic pigment comprises the following steps: S1, add 26.7g of cobalt salt, 6.7g of nickel salt, 29.1g of iron salt, and 11.3g of manganese salt to 1.18kg of deionized water, and stir to mix to obtain a mixed solution; S2. Add 0.2 mol / L sodium hydroxide solution dropwise to the mixed solution obtained in step S1, adjust the pH to 9, and filter to obtain a precipitate; S3, drying the precipitate obtained in step S2 at 90° C. to a constant weight, and then grinding it through a 400-mesh sieve; S4, placing the precipitate ground in step S3 into a muffle furnace and calcining it in air for 2.8 hours at a temperature of 1150° C. to obtain a calcined product, thereby obtaining a secondary black pigment; S5. Dispersing 10.6 g of the secondary black pigment obtained in step S4 into a mixed solution of polyacrylic acid, deionized water, and diethylene glycol, where the amounts of polyacrylic acid, deionized water, and diethylene glycol are 9.6 g, 465 g, and 138 g, respectively, the mixture is heated to 120° C. and reacted continuously for 2.6 h. After the reaction, the mixture is filtered, and the filtered product is washed with sufficient deionized water and dried at 60° C. to a constant weight. S6. Mix 9.8 g of the secondary black pigment treated in step S5 with 3.8 g of modified mesoporous silica, add a mixed solution of 11.4 g of deionized water and 11.4 g of anhydrous ethanol, wet grind for 3.6 hours, and then filter. Heat the filtered product at 240° C. for 3.6 hours to obtain a mixture; S7, adding the mixture obtained in step S6 to 266 g of 2 mol / L sodium hydroxide solution and reacting at 60° C. for 7 h, washing the filtered product with sufficient deionized water until neutral, and then drying at 100° C. to constant weight to obtain a black ceramic pigment; The preparation method of the modified mesoporous silica comprises the following steps: S101, dispersing 8.5 g of mesoporous silica into a deionized water solution containing sucrose, where the amounts of sucrose and deionized water are 3.9 g and 58.6 g, respectively; then adding dropwise 0.33 g of 98 wt % concentrated sulfuric acid; evaporating the deionized water at 140° C.; and maintaining the temperature for 8.6 h after the deionized water is completely evaporated, to obtain a solid material; S102, calcining the mesoporous silica treated in step S101 at 900° C. for 6.8 h under a nitrogen atmosphere; S103. Disperse 7.8 g of mesoporous silica treated in step S102 into a toluene solution containing γ-aminopropyltriethoxysilane, where the amounts of γ-aminopropyltriethoxysilane and toluene are 1.56 g and 62.4 g, respectively. Heat to 70°C, react for 5 hours, and then filter. Wash the filtered product with sufficient ethanol and vacuum dry it at 40°C to constant weight to obtain modified mesoporous silica.

[0022] The cobalt salt, nickel salt, iron salt and manganese salt used in the above embodiment are Co(NO3)2·6H2O, Ni(NO3)2·6H2O, Fe(NO3)3·9H2O and Mn(NO3)2·4H2O respectively; In the above embodiment, during the wet grinding process in step S6, the rotation speed of the wet grinding is set to 300 r / min; The average particle size of the mesoporous silica used in step S101 in the above embodiment is 500 nm.

[0023] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that step S5 is completely eliminated, and the remaining steps are exactly the same as those in Example 1.

[0024] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that step S103 is completely eliminated in the preparation of modified mesoporous silica, and the remaining steps are exactly the same as those in Example 1.

[0025] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the preparation process of the modified mesoporous silica is changed, that is, the addition of concentrated sulfuric acid and sucrose in step S101 is cancelled, and the treatment of the mesoporous silica in steps S102 and S103 is retained (the mesoporous silica after this process is named pretreated mesoporous silica), 4.3 g of pretreated mesoporous silica is added for wet grinding in step S6, and a product of sucrose calcined at 850°C in a nitrogen atmosphere is also added in an amount of 0.32 g (accounting for 3% of the weight of the secondary black pigment 10.6 g). The remaining steps are exactly the same as in Example 1.

[0026] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that the preparation process of the modified mesoporous silica is changed, that is, the addition of concentrated sulfuric acid and sucrose in step S101 is cancelled, and the treatment of the mesoporous silica in steps S102 and S103 is retained (the mesoporous silica after this process is named pretreated mesoporous silica), 4.3 g of pretreated mesoporous silica is added in step S6 for wet grinding, and a product of sucrose calcined at 850°C in a nitrogen atmosphere is also added in an amount of 0.64 g (accounting for 6% of the weight of the secondary black pigment 10.6 g), and the remaining steps are exactly the same as in Example 1.

[0027] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that the preparation process of the modified mesoporous silica is changed, that is, the addition of concentrated sulfuric acid and sucrose in step S101 is cancelled, and the treatment of the mesoporous silica in steps S102 and S103 is retained (the mesoporous silica after this process is named pretreated mesoporous silica), 4.3 g of pretreated mesoporous silica is added in step S6 for wet grinding, and a product of sucrose calcined at 850°C in a nitrogen atmosphere is also added in an amount of 0.95 g (accounting for 9% of the weight of the secondary black pigment 10.6 g), and the remaining steps are exactly the same as in Example 1.

[0028] Comparative Example 6 The difference between Comparative Example 6 and Example 1 is that the modified mesoporous silica added in step S6 is replaced with unmodified mesoporous silica (i.e., the treatment of mesoporous silica through S101, S102 and S103 is cancelled), the amount of unmodified mesoporous silica used is 4.3 g, and the remaining steps are exactly the same as in Example 1.

[0029] Comparative Example 7 The difference between Comparative Example 7 and Example 1 is that steps S5, S6 and S7 are completely eliminated, and the remaining steps are exactly the same as those in Example 1.

[0030] A total of 11 groups of black ceramic pigments were prepared through Examples 1-4 and Comparative Examples 1-7. The CIE parameters of these 11 groups of black ceramic pigments were measured using a Tri-Tech NR110 colorimeter. The measurement results are shown in Table 1 below: Table 1: Chromaticity CIE parameter table of 11 groups of black ceramic pigments prepared in Examples 1-4 and Comparative Examples 1-7 L* a* b* Example 1 28.1 0.8 0.6 Example 2 29.3 0.9 0.7 Example 3 30.2 1.1 0.9 Example 4 27.4 0.6 1.3 Comparative Example 1 29.3 1.3 0.7 Comparative Example 2 28.9 1.1 0.8 Comparative Example 3 31.8 1.8 1.2 Comparative Example 4 31.6 1.2 0.9 Comparative Example 5 32.1 0.9 1.4 Comparative Example 6 32.5 1.4 2.4 Comparative Example 7 33.6 1.8 2.1 It can be seen from the data of Example 1 and Comparative Examples 1-2 in Table 1 above that in the present invention, the surface treatment of the secondary black pigment and mesoporous silica is carried out, which is conducive to the uniform combination of mesoporous silica and the secondary black pigment, improves the wet grinding effect, and improves the blackness of the black pigment; Comparative Examples 3-5 are carbon materials produced by directly adding sucrose calcined to the secondary black pigment. Compared with Comparative Example 6 (Comparative Example 6 does not add sucrose calcined carbon material at all), the blackness is improved, but relative to the carbon material produced by the template effect of mesoporous silica in Example 1, its blackness is reduced.

[0031] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a black ceramic pigment, characterized in that: The following steps are involved: S1. Add cobalt salt, nickel salt, iron salt and manganese salt to deionized water, and stir to mix well to obtain a mixed solution; S2. Add 0.2 mol / L sodium hydroxide solution dropwise to the mixed solution obtained in step S1, adjust the pH to 8-9, and filter to obtain a precipitate; S3, drying the precipitate obtained in step S2 at 90°C to constant weight, and then grinding it through a 200-500 mesh sieve; S4, placing the precipitate ground in step S3 into a muffle furnace and calcining it in an air atmosphere for 1-3 hours to obtain a calcined product at a calcination temperature of 1080-1200° C. to obtain a secondary black pigment; S5. Dispersing the secondary black pigment obtained in step S4 into a mixed solution of polyacrylic acid, deionized water, and diethylene glycol, heating the mixture to 100-160° C. for a continuous reaction of 1-4 hours, filtering the mixture after the reaction, washing the filtered product with sufficient deionized water, and drying the mixture at 60° C. to a constant weight; S6. Mixing the secondary black pigment treated in step S5 with the modified mesoporous silica, adding a mixed solution of deionized water and anhydrous ethanol, wet grinding for 2-4 hours, and then filtering. The filtered product is heated at 200-250° C. for 3-5 hours to obtain a mixture; S7, adding the mixture obtained in step S6 to a 2 mol / L sodium hydroxide solution and reacting at 60° C. for 4-8 hours, washing the filtered product with sufficient deionized water until neutral, and then drying at 100° C. to constant weight to obtain a black ceramic pigment; The preparation method of the modified mesoporous silica comprises the following steps: S101, dispersing mesoporous silica in a deionized water solution containing sucrose, then adding concentrated sulfuric acid dropwise, evaporating the deionized water at 80-150° C., and maintaining the temperature for 8-10 hours after the deionized water is completely evaporated to obtain a solid material; S102, calcining the mesoporous silica treated in step S101 at 850-950° C. for 4-8 hours under a nitrogen atmosphere; S103. Disperse the mesoporous silica treated in step S102 into a toluene solution containing γ-aminopropyltriethoxysilane, heat to 70°C, react for 4-8 hours, and then filter. Wash the filtered product with sufficient ethanol and vacuum dry it at 40°C to constant weight to obtain modified mesoporous silica.

2. The method for preparing black ceramic pigment according to claim 1, wherein: The molar ratio of the cobalt salt, the nickel salt, the iron salt and the manganese salt in step S1 is (0.8-1.0):(0.1-0.3):(0.6-0.8):(0.4-0.6).

3. The method for preparing black ceramic pigment according to claim 2, wherein: In step S1, the mass ratio of the sum of the masses of the cobalt salt, nickel salt, iron salt, and manganese salt to deionized water is 1:(15-20).

4. The method for preparing black ceramic pigment according to claim 1, wherein: The mass ratio of the secondary black pigment, polyacrylic acid, deionized water and diethylene glycol used in step S5 is 1:(0.5-2):(30-50):(10-13).

5. The method for preparing black ceramic pigment according to claim 1, wherein: The mass ratio between deionized water and anhydrous ethanol in step S6 is 1:1; the mass ratio between the sum of the mass of deionized water and anhydrous ethanol used in step S6, the secondary black pigment and the modified mesoporous silica is (4-8):(2-3):

1.

6. The method for preparing black ceramic pigment according to claim 1, wherein: The mass ratio of the sodium hydroxide solution used in step S7 to the modified mesoporous silica used in step S6 is 70:

1.

7. The method for preparing black ceramic pigment according to claim 1, wherein: In step S101, the mass ratio of concentrated sulfuric acid, sucrose, mesoporous silica and deionized water is 1:(10-15):(20-30):(100-200).

8. The method for preparing black ceramic pigment according to claim 1, wherein: The mass ratio of mesoporous silica, γ-aminopropyltriethoxysilane and toluene used in step S103 is 1:0.2:

8.

9. A black ceramic pigment, characterized in that: The black ceramic pigment is prepared by the preparation method of any one of claims 1 to 8.

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