Black ceramic pigment and method for preparing the same

Abstract

The present application relates to the technical field of ceramic pigment preparation, and particularly relates to a black ceramic pigment and a preparation method thereof. The preparation method comprises the following steps: S1, adding cobalt salt, nickel salt, iron salt and manganese salt into deionized water, stirring and uniformly mixing to obtain a mixed solution; S2, adjusting pH to obtain a precipitate; S3, drying and grinding the precipitate; S4, calcining to obtain a secondary black pigment; S5, performing surface treatment on the secondary black pigment; S6, wet grinding the secondary black pigment and modified mesoporous silica, and then heating; S7, performing alkali treatment on the heated secondary black pigment, filtering the product and washing with water to obtain the black ceramic pigment. The black ceramic pigment prepared by the method has excellent blackness performance, and the preparation method is simple and suitable for promotion.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic pigment preparation, and particularly relates to a black ceramic pigment and a preparation method thereof. BACKGROUND

[0002] Ceramic pigment is a general term for pigments used in ceramic production. Ceramic pigments bring rich luster and color to ceramics by coloring ceramics. Black ceramic pigment is a common type of ceramic pigment. Black can bring people multiple feelings. Black can bring people peace and tranquility, and can also symbolize elegance and passion. Therefore, black ceramic pigment has become a functional pigment widely used in the decoration of inorganic materials such as ceramics, enamel and glass. Its main function is to provide stable and uniform black coloring effect for the base body. With the continuous development of the ceramic industry, people's requirements for black ceramic pigments are also getting higher and higher, which are mainly reflected in the requirement for black purity.

[0003] Existing black ceramic pigments are usually composed of transition metal oxides (such as Fe, Co, Cr, Mn, Cu, etc.) and are synthesized by high-temperature solid-phase reaction. When synthesizing ceramic pigments from transition metal oxides by solid-phase reaction, the absorption of visible light is not complete due to the lack of microstructure regulation, resulting in insufficient blackness. Therefore, in view of the problems existing in the background art, the present application introduces a sucrose inert atmosphere calcined carbon material product into the traditional black ceramic pigment, and at the same time, the structure of the sucrose calcined product is micro-regulated, so as to improve the blackness of the traditional black ceramic pigment. SUMMARY

[0004] The present application aims to provide a black ceramic pigment and a preparation method thereof to solve the problems raised in the background art.

[0005] To achieve the above-mentioned purpose, the present application provides the following technical solution:

[0006] A preparation method of a black ceramic pigment, comprising the following steps:

[0007] S1, adding cobalt salt, nickel salt, iron salt and manganese salt into deionized water, stirring and mixing uniformly to obtain a mixed solution;

[0008] S2, adding 0.2 mol / L sodium hydroxide solution dropwise to the mixed solution obtained in step S1, adjusting the pH to 8-9, and filtering to obtain a precipitate;

[0009] S3, drying the precipitate obtained in step S2 at 90 DEG C to a constant weight, and then grinding through a 200-500 mesh sieve;

[0010] S4, putting the precipitate treated by step S3 into a muffle furnace to calcine under air atmosphere for 1-3 h to obtain a calcined product, the calcination temperature is 1080-1200℃, to obtain a secondary black pigment;

[0011] S5, dispersing the secondary black pigment obtained in step S4 into a mixed solution of polyacrylic acid, deionized water and diethylene glycol, heating to 100-160℃ for continuous reaction for 1-4 h, after reaction, filtering, and washing the filtered product with sufficient deionized water, drying at 60℃ to constant weight;

[0012] S6, mixing the secondary black pigment treated by step S5 with modified mesoporous silica, adding a mixed solution of deionized water and anhydrous ethanol, wet grinding for 2-4 h, filtering, and heating the filtered product at 200-250℃ for 3-5 h to obtain a mixture;

[0013] S7, adding the mixture obtained in step S6 into a 2 mol / L sodium hydroxide solution, reacting at 60℃ for 4-8 h, washing the filtered product with sufficient deionized water to neutral, and drying at 100℃ to constant weight to obtain a black ceramic pigment;

[0014] The preparation method of the modified mesoporous silica comprises the following steps:

[0015] S101, dispersing mesoporous silica into a deionized water solution containing sucrose, then adding concentrated sulfuric acid dropwise, evaporating the deionized water at 80-150℃, and continuing to maintain the temperature for 8-10 h after the deionized water is completely evaporated to obtain a solid material;

[0016] S102, calcining the mesoporous silica treated by step S101 under nitrogen atmosphere and at 850-950℃ for 4-8 h;

[0017] S103, dispersing the mesoporous silica treated by step S102 into a toluene solution containing γ-aminopropyl triethoxysilane, heating to 70℃, reacting for 4-8 h, filtering, washing the filtered product with sufficient ethanol, and vacuum drying at 40℃ to constant weight to obtain modified mesoporous silica.

[0018] Further, the molar ratio among the cobalt salt, nickel salt, iron salt and manganese salt in step S1 is (0.8-1.0):(0.1-0.3):(0.6-0.8):(0.4-0.6).

[0019] Further, the mass ratio between the sum of the mass of the cobalt salt, nickel salt, iron salt and manganese salt in step S1 and deionized water is 1:(15-20).

[0020] Further, the mass ratio between the secondary black pigment, polyacrylic acid, deionized water and diethylene glycol used in the step S5 is 1: (0.5-2): (30-50): (10-13).

[0021] Further, the mass ratio between the deionized water and anhydrous ethanol in the step S6 is 1:1; the mass ratio between the sum of the mass of the deionized water and the anhydrous ethanol used in the step S6, the secondary black pigment and the modified mesoporous silica is (4-8): (2-3): 1.

[0022] Further, the mass ratio between the sodium hydroxide solution used in the step S7 and the modified mesoporous silica used in the step S6 is 70:1.

[0023] Further, the mass ratio between the concentrated sulfuric acid, sucrose, mesoporous silica and deionized water in the step S101 is 1: (10-15): (20-30): (100-200).

[0024] Further, the mass ratio between the mesoporous silica, gamma-aminopropyl triethoxysilane and toluene used in the step S103 is 1:0.2:8.

[0025] A black ceramic pigment is prepared by the preparation method of the black ceramic pigment.

[0026] Compared with the prior art, the present application has the beneficial effects that:

[0027] 1. The present application improves the blackness of the black ceramic pigment by introducing the sucrose calcination product into the ceramic pigment. The sucrose is introduced into the pores of the mesoporous silica by co-evaporation with the mesoporous silica. Finally, the mesoporous silica template is removed by alkali liquor. The sucrose calcination product is constrained by the mesoporous silica, and its structure is micro-regulated. When it is introduced into the black ceramic pigment, it brings better blackness performance to the black ceramic pigment.

[0028] 2. In the present application, the carbon material enters the secondary black pigment together with the nano-silica and is wet ground, which promotes the grinding and dispersion of the secondary black pigment. At the same time, the surface treatment of the secondary black pigment and the mesoporous silica improves the uniformity of their combination and better plays the wet grinding effect, further improving the blackness of the prepared black ceramic pigment. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The process flow chart for preparing the black ceramic pigment of the present application is shown in the figure.

[0030] Figure 2 The process flow chart for preparing the modified mesoporous silica of the present application is shown in the figure. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0032] Please refer to Figures 1 to 2 The present application provides:

[0033] Embodiment 1

[0034] A preparation method of a black ceramic pigment, comprising the following steps:

[0035] S1, 26.5g of cobalt salt, 4.5g of nickel salt, 27.6g of iron salt, and 12.5g of manganese salt are added to 1.28kg of deionized water, and stirred and mixed uniformly to obtain a mixed solution;

[0036] S2, 0.2mol / L of sodium hydroxide solution is added dropwise to the mixed solution obtained in step S1, and the pH is adjusted to 8.5, and a precipitate is obtained by filtration;

[0037] S3, the precipitate obtained in step S2 is dried to a constant weight at 90℃, and then ground through a 300 mesh sieve;

[0038] S4, the precipitate treated by grinding in step S3 is placed in a muffle furnace and calcined in an air atmosphere for 2.5h to obtain a calcined product, and the calcination temperature is 1120℃, and a secondary black pigment is obtained;

[0039] S5, 11.2g of the secondary black pigment obtained in step S4 is dispersed in a mixed solution of polyacrylic acid, deionized water and diethylene glycol, and the amounts of polyacrylic acid, deionized water and diethylene glycol are 7.9g, 425g and 136g respectively, heated to 130℃ and continuously reacted for 3.6h, and after the reaction, the product is filtered, and the filtered product is washed with sufficient deionized water and dried to a constant weight at 60℃;

[0040] S6, 10.6g of the secondary black pigment treated in step S5 is mixed with 4.3g of modified mesoporous silica, and a mixed solution of 13.2g of deionized water and 13.2g of anhydrous ethanol is added, and after wet grinding for 2.5h, the product is filtered, and the filtered product is heated at 230℃ for 4.5h to obtain a mixture;

[0041] S7, the mixture obtained in step S6 is added to 301g of 2mol / L of sodium hydroxide solution and reacted at 60℃ for 6.8h, and the filtered product is washed with sufficient deionized water to neutralize, and then dried to a constant weight at 100℃ to obtain a black ceramic pigment;

[0042] The preparation method of the modified mesoporous silica includes the following steps:

[0043] S101, disperse 8.5g mesoporous silica into a deionized water solution containing sucrose, the use amount of sucrose and deionized water solution is 4.2g and 52.5g respectively, then add 0.35g concentrated sulfuric acid with a concentration of 98wt%, evaporate the deionized water at 125℃, continue to keep the temperature for 8.6h after the deionized water is completely evaporated, and obtain a solid material;

[0044] S102, calcine the mesoporous silica treated in step S101 under a nitrogen atmosphere and at 880℃ for 6h;

[0045] S103, disperse 7.8g mesoporous silica treated in step S102 into a toluene solution containing γ-aminopropyl triethoxysilane, the use amount of γ-aminopropyl triethoxysilane and toluene is 1.56g and 62.4g respectively, heat to 70℃, filter after reacting for 4.5h, clean the filtered product with sufficient ethanol, and vacuum dry at 40℃ to constant weight to obtain the modified mesoporous silica.

[0046] Example 2

[0047] A preparation method of a black ceramic pigment, including the following steps:

[0048] S1, add 23.3g cobalt salt, 2.9g nickel salt, 24.2g iron salt and 10g manganese salt into 906g deionized water, stir and mix uniformly to obtain a mixed solution;

[0049] S2, add 0.2mol / L sodium hydroxide solution dropwise to the mixed solution obtained in step S1, adjust the pH to 8, and filter to obtain a precipitate;

[0050] S3, dry the precipitate obtained in step S2 to constant weight at 90℃, and then grind through a 200 mesh sieve;

[0051] S4, put the precipitate treated by grinding in step S3 into a muffle furnace and calcine under an air atmosphere for 1h to obtain a calcined product, the calcination temperature is 1080℃, and a secondary black pigment is obtained;

[0052] S5, disperse 8.6g of the secondary black pigment obtained in step S4 into a mixed solution of polyacrylic acid, deionized water and diethylene glycol, the use amount of polyacrylic acid, deionized water and diethylene glycol is 4.3g, 258g and 86g respectively, heat to 100℃ and continuously react for 1h, filter after the reaction, clean the filtered product with sufficient deionized water, and dry to constant weight at 60℃;

[0053] S6, 7.8 g of the secondary black pigment treated in step S5 was mixed with 3.9 g of the modified mesoporous silica, 7.8 g of a mixed solution of deionized water and anhydrous ethanol was added, and after wet milling for 2 h, the filtered product was heated at 200°C for 3 h to obtain a mixture;

[0054] S7, the mixture obtained in step S6 was added to 273 g of a 2 mol / L sodium hydroxide solution and reacted at 60°C for 4 h, and the filtered product was washed to neutral with sufficient deionized water and dried at 100°C to a constant weight to obtain a black ceramic pigment;

[0055] The preparation method of the modified mesoporous silica comprises the following steps:

[0056] S101, 8.5 g of mesoporous silica was dispersed in a deionized water solution containing sucrose, the amounts of sucrose and deionized water were 4.25 g and 42.5 g respectively, then 0.425 g of concentrated sulfuric acid with a concentration of 98 wt% was added dropwise, and the deionized water was evaporated at 80°C, and the temperature was maintained for 8 h after the deionized water was completely evaporated to obtain a solid material;

[0057] S102, the mesoporous silica treated in step S101 was calcined at 850°C for 4 h under a nitrogen atmosphere;

[0058] S103, 7.8 g of the mesoporous silica treated in step S102 was dispersed in a toluene solution containing γ-aminopropyl triethoxysilane, the amounts of γ-aminopropyl triethoxysilane and toluene were 1.56 g and 62.4 g respectively, heated to 70°C, reacted for 4 h, then filtered, and the filtered product was washed with sufficient ethanol and dried to a constant weight under vacuum at 40°C to obtain the modified mesoporous silica.

[0059] Example 3

[0060] A preparation method of a black ceramic pigment, comprising the following steps:

[0061] S1, 29.1 g of a cobalt salt, 8.7 g of a nickel salt, 32.3 g of an iron salt, and 15.1 g of a manganese salt were added to 1.7 kg of deionized water, and stirred and mixed uniformly to obtain a mixed solution;

[0062] S2, 0.2 mol / L of a sodium hydroxide solution was added dropwise to the mixed solution obtained in step S1, and the pH was adjusted to 9, and a precipitate was obtained by filtration;

[0063] S3, the precipitate obtained in step S2 was dried to a constant weight at 90°C, and then ground through a 500 mesh sieve;

[0064] S4, put the precipitate treated by step S3 into a muffle furnace and calcine for 3h under air atmosphere to obtain a calcined product, the calcination temperature is 1200℃, to obtain a secondary black pigment;

[0065] S5, disperse 12.4g of the secondary black pigment obtained in step S4 into a mixed solution of polyacrylic acid, deionized water and diethylene glycol, the amounts of polyacrylic acid, deionized water and diethylene glycol are 24.8g, 620g and 124g respectively, heat to 160℃ and continuously react for 4h, after the reaction, filter, wash the filtered product with sufficient deionized water, and dry at 60℃ to constant weight;

[0066] S6, mix 10.8g of the secondary black pigment treated by step S5 with 3.6g of modified mesoporous silica, add a mixed solution of 14.4g of deionized water and 14.4g of anhydrous ethanol, wet mill for 4h and then filter, heat the filtered product at 250℃ for 5h to obtain a mixture;

[0067] S7, add the mixture obtained in step S6 to 252g of a 2mol / L sodium hydroxide solution and react at 60℃ for 8h, wash the filtered product with sufficient deionized water until neutral, and dry at 100℃ to constant weight to obtain a black ceramic pigment;

[0068] The preparation method of the modified mesoporous silica comprises the following steps:

[0069] S101, disperse 8.5g of mesoporous silica into a deionized water solution containing sucrose, the amounts of sucrose and deionized water are 4.2g and 56g respectively, then add 0.28g of concentrated sulfuric acid with a concentration of 98wt%, evaporate the deionized water at 150℃, and continue to maintain the temperature for 10h after the deionized water is completely evaporated to obtain a solid material;

[0070] S102, calcine the mesoporous silica treated by step S101 at 950℃ for 8h under nitrogen atmosphere;

[0071] S103, disperse 7.8g of the mesoporous silica treated by step S102 into a toluene solution containing γ-aminopropyl triethoxysilane, the amounts of γ-aminopropyl triethoxysilane and toluene are 1.56g and 62.4g respectively, heat to 70℃, react for 8h, filter, wash the filtered product with sufficient ethanol, and vacuum dry at 40℃ to constant weight to obtain the modified mesoporous silica.

[0072] Example 4

[0073] A preparation method of a black ceramic pigment, comprising the following steps:

[0074] S1, 26.7 g of cobalt salt, 6.7 g of nickel salt, 29.1 g of iron salt, and 11.3 g of manganese salt were added to 1.18 kg of deionized water, and stirred to obtain a mixed solution;

[0075] S2, 0.2 mol / L of sodium hydroxide solution was added dropwise to the mixed solution obtained in step S1, and the pH was adjusted to 9, and a precipitate was obtained by filtration;

[0076] S3, the precipitate obtained in step S2 was dried at 90°C to a constant weight, and then ground through a 400 mesh sieve;

[0077] S4, the precipitate treated by grinding in step S3 was calcined in a muffle furnace under an air atmosphere for 2.8 h to obtain a calcined product, and the calcination temperature was 1150°C, to obtain a secondary black pigment;

[0078] S5, 10.6 g of the secondary black pigment obtained in step S4 was dispersed in a mixed solution of polyacrylic acid, deionized water, and diethylene glycol, and the amounts of polyacrylic acid, deionized water, and diethylene glycol were 9.6 g, 465 g, and 138 g, respectively. The mixture was heated to 120°C and continuously reacted for 2.6 h. After the reaction, the mixture was filtered, and the filtered product was washed with sufficient deionized water and dried at 60°C to a constant weight;

[0079] S6, 9.8 g of the secondary black pigment treated in step S5 was mixed with 3.8 g of modified mesoporous silica, and 11.4 g of a mixed solution of deionized water and 11.4 g of anhydrous ethanol was added. After wet grinding for 3.6 h, the mixture was filtered, and the filtered product was heated at 240°C for 3.6 h to obtain a mixture;

[0080] S7, the mixture obtained in step S6 was added to 266 g of a 2 mol / L sodium hydroxide solution and reacted at 60°C for 7 h. The filtered product was washed with sufficient deionized water until it was neutral, and then dried at 100°C to a constant weight to obtain a black ceramic pigment;

[0081] The above method for preparing modified mesoporous silica includes the following steps:

[0082] S101, 8.5 g of mesoporous silica was dispersed in a deionized water solution containing sucrose, and the amounts of sucrose and deionized water were 3.9 g and 58.6 g, respectively. Then, 0.33 g of concentrated sulfuric acid with a concentration of 98 wt% was added dropwise. The deionized water was evaporated at 140°C, and the temperature was maintained for 8.6 h after the deionized water was completely evaporated to obtain a solid material;

[0083] S102, the mesoporous silica treated in step S101 was calcined under a nitrogen atmosphere at 900°C for 6.8 h;

[0084] S103, disperse the 7.8 g mesoporous silica treated in step S102 into a toluene solution containing γ-aminopropyl triethoxysilane, the amount of γ-aminopropyl triethoxysilane and toluene is 1.56 g and 62.4 g respectively, heat to 70℃, after 5 h of reaction, filter, wash the filtered product with sufficient amount of ethanol, and dry to constant weight under vacuum at 40℃ to obtain the modified mesoporous silica.

[0085] The cobalt salt, nickel salt, iron salt and manganese salt used in the above embodiments are Co(NO3)2·6H2O, Ni(NO3)2·6H2O, Fe(NO3)3·9H2O and Mn(NO3)2·4H2O respectively;

[0086] In the wet milling process in step S6 in the above embodiments, the rotation speed of wet milling is set to 300 r / min;

[0087] The average particle size of the mesoporous silica used in step S101 in the above embodiments is 500 nm.

[0088] Comparative Example 1

[0089] Comparative Example 1 differs from Example 1 in that step S5 is completely cancelled, and the remaining steps are exactly the same as Example 1.

[0090] Comparative Example 2

[0091] Comparative Example 2 differs from Example 1 in that step S103 in the preparation of modified mesoporous silica is completely cancelled, and the remaining steps are exactly the same as Example 1.

[0092] Comparative Example 3

[0093] Comparative Example 3 differs from Example 1 in that the preparation process of modified mesoporous silica is changed, i.e. the concentrated sulfuric acid and sucrose added in step S101 are cancelled, and the treatment of mesoporous silica in steps S102 and S103 is maintained (the mesoporous silica after this process is named as pretreated mesoporous silica), 4.3 g of pretreated mesoporous silica is added for wet milling in step S6, and the product of sucrose calcined at 850℃ in nitrogen atmosphere is also added, the amount is 0.32 g (3% of the weight of secondary black pigment 10.6 g), and the remaining steps are exactly the same as Example 1.

[0094] Comparative Example 4

[0095] The difference between Comparative Example 4 and Example 1 is that the preparation process of the modified mesoporous silica is changed, i.e. the concentrated sulfuric acid and sucrose added in step S101 are cancelled, and the treatment of the mesoporous silica in steps S102 and S103 is maintained (the mesoporous silica after this process is named as pretreated mesoporous silica), 4.3 g of the pretreated mesoporous silica is added for wet milling in step S6, and the product of sucrose calcined at 850°C in a nitrogen atmosphere is also added, with a usage of 0.64 g (6% of the weight of the secondary black pigment 10.6 g), and the remaining steps are the same as those in Example 1.

[0096] Comparative Example 5

[0097] The difference between Comparative Example 5 and Example 1 is that the preparation process of the modified mesoporous silica is changed, i.e. the concentrated sulfuric acid and sucrose added in step S101 are cancelled, and the treatment of the mesoporous silica in steps S102 and S103 is maintained (the mesoporous silica after this process is named as pretreated mesoporous silica), 4.3 g of the pretreated mesoporous silica is added for wet milling in step S6, and the product of sucrose calcined at 850°C in a nitrogen atmosphere is also added, with a usage of 0.95 g (9% of the weight of the secondary black pigment 10.6 g), and the remaining steps are the same as those in Example 1.

[0098] Comparative Example 6

[0099] The difference between Comparative Example 6 and Example 1 is that the modified mesoporous silica added in step S6 is changed to unmodified mesoporous silica (i.e. the treatment of the mesoporous silica by S101, S102 and S103 is cancelled), with a usage of 4.3 g, and the remaining steps are the same as those in Example 1.

[0100] Comparative Example 7

[0101] The difference between Comparative Example 7 and Example 1 is that steps S5, S6 and S7 are completely cancelled, and the remaining steps are the same as those in Example 1.

[0102] Eleven groups of black ceramic pigments are prepared through Examples 1-4 and Comparative Examples 1-7, and the CIE parameters of the eleven groups of black ceramic pigments are determined, the CIE parameters are determined by a Sinochron Technology NR110 color difference meter, and the determination results are shown in Table 1.

[0103] Table 1: Chromaticity CIE parameters of the eleven groups of black ceramic pigments prepared in Examples 1-4 and Comparative Examples 1-7

[0104] 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

[0105] As can be seen from the data of Example 1 and Comparative Examples 1-2 in Table 1 above, in the present application, by surface treatment of the secondary black pigment and mesoporous silica, the mesoporous silica and secondary black pigment are combined uniformly, the wet grinding effect is improved, and the blackness of the black pigment is improved; Comparative Examples 3-5 are carbon materials produced by directly adding sucrose to the secondary black pigment and calcining, and compared with Comparative Example 6 (Comparative Example 6 does not add carbon materials produced by calcining sucrose at all), the blackness is improved, but compared with Example 1, the carbon materials produced by the templating effect of mesoporous silica, the blackness is reduced.

[0106] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for producing a black ceramic pigment, characterized by, The method comprises the following steps: S1, adding cobalt salt, nickel salt, iron salt and manganese salt into deionized water, stirring and mixing uniformly to obtain a mixed solution; S2, adding 0.2 mol / L sodium hydroxide solution dropwise into the mixed solution obtained in step S1, adjusting pH to 8-9, and filtering to obtain a precipitate; S3, drying the precipitate obtained in step S2 at 90℃ to constant weight, and then grinding through a 200-500 mesh sieve; S4, placing the precipitate treated by grinding in step S3 into a muffle furnace for calcination under air atmosphere for 1-3 h to obtain a calcined product, and the calcination temperature is 1080-1200℃, thereby obtaining 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 to 100-160℃ for continuous reaction for 1-4 h, filtering after reaction, and washing the filtered product with sufficient deionized water, and drying at 60℃ to constant weight; S6, mixing the secondary black pigment treated by step S5 with modified mesoporous silica, adding a mixed solution of deionized water and anhydrous ethanol, filtering after wet grinding for 2-4 h, heating the filtered product at 200-250℃ for 3-5 h, and obtaining a mixture; S7, adding the mixture obtained in step S6 into 2 mol / L sodium hydroxide solution, reacting at 60℃ for 4-8 h, washing the filtered product with sufficient deionized water to neutral, and drying at 100℃ 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 into a deionized water solution containing sucrose, then adding concentrated sulfuric acid dropwise, evaporating the deionized water at 80-150℃, and continuing to maintain the temperature for 8-10 h after the deionized water is completely evaporated to obtain a solid material; S102, calcining the mesoporous silica treated by step S101 under nitrogen atmosphere and at 850-950℃ for 4-8 h; S103, dispersing the mesoporous silica treated by step S102 into a toluene solution containing γ-aminopropyl triethoxysilane, heating to 70℃, filtering after reacting for 4-8 h, washing the filtered product with sufficient ethanol, and vacuum drying at 40℃ to constant weight to obtain modified mesoporous silica.

2. The method for preparing a black ceramic pigment according to claim 1, characterized in that, The molar ratio of the cobalt salt, nickel salt, iron salt and 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 of claim 2, wherein the black ceramic pigment is prepared by mixing the black ceramic pigment with a binder and a solvent, and then coating the mixture on a surface of a substrate. The mass ratio of the sum of the mass of the cobalt salt, nickel salt, iron salt and manganese salt in step S1 to the deionized water is 1:(15-20).

4. The method of claim 1, wherein the black ceramic pigment is prepared by mixing the black ceramic pigment with a binder and a solvent. 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 of claim 1, wherein the black ceramic pigment is prepared by mixing the black ceramic pigment with a binder and a solvent, and then coating the mixture on a surface of a substrate. The mass ratio of the deionized water to the anhydrous ethanol in step S6 is 1:1; and the mass ratio of the sum of the mass of the deionized water and the 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, characterized in that, The mass ratio between the sodium hydroxide solution used in the step S7 and the modified mesoporous silica used in the step S6 is 70:

1.

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

8. The method for preparing black ceramic pigment according to claim 1, characterized in that, The mass ratio of the mesoporous silica, γ-aminopropyl triethoxysilane and toluene used in the 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 1-8. The mass ratio between the concentrated sulfuric acid, sucrose, mesoporous silica and deionized water in the step S101 is 1:(10-15):(20-30):(100-200). The mass ratio of the mesoporous silica, γ-aminopropyl triethoxysilane and toluene used in the step S103 is 1:0.2:

8. The black ceramic pigment is prepared by the preparation method of any one of claims 1-8.

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