CN114058195B - Preparation method of ceramic pigment and ceramic pigment - Google Patents

Abstract

The invention discloses a preparation method of a ceramic coloring material and the ceramic coloring material. The method comprises: step 1, providing aluminum ash; step 2, adding water to the aluminum ash and stirring, and removing the supernatant after standing for a predetermined time liquid, adding alkali solution therein and carrying out solid-liquid separation after fully stirring to obtain a solid phase mixture; step 3, roasting the solid phase mixture to obtain a roasted product; step 4, adding dopant ions to the roasted product source, mineralizer and stabilizer, and high temperature solid phase synthesis to obtain the ceramic pigment. According to the method of the embodiment of the present invention, the secondary utilization of solid hazardous waste aluminum ash can be realized, and at the same time combined with the solid phase method, the harm to the environment can be reduced, and the resource utilization of aluminum ash in the field of ceramic pigments can be promoted at the same time , and the preparation method has the advantages of simple process, easy control, easy production, environmental friendliness, and greatly reduces production cost.

Description

Preparation method of ceramic pigment and ceramic pigment

technical field

The invention relates to the technical field of ceramics, in particular to a method for preparing a ceramic color material and the ceramic color material.

Background technique

Aluminum ash is a kind of solid waste produced during the production, use and recycling of electrolytic aluminum, cast aluminum and other aluminum industries. The composition of aluminum ash varies with the production raw materials and operating conditions of the enterprise. It is directly related to the pollutants contained in raw materials, covering agents, slagging agents, refining agents, etc., and is also related to the atmosphere in the casting furnace. The general components are metal aluminum, alumina and iron oxides, potassium, sodium, calcium and Magnesium chloride, etc.

At present, the processing methods of aluminum ash are mainly stockpiling or landfilling. The toxic and harmful ions in aluminum ash will seep into the ground and pollute the soil and groundwater. In addition, when the weather is hot and humid, aluminum nitride, aluminum carbide and other substances in aluminum ash react with water to generate ammonia, methane and other gases, which pollute the air. Therefore, the useful components in aluminum ash are converted into high value-added products to obtain raw materials, and at the same time, the pollution problem caused by hazardous waste landfills is solved.

Contents of the invention

In view of this, the present invention provides a method for preparing ceramic pigments. The method has a simple process and can utilize discarded aluminum ash to obtain ceramic pigments with higher added value.

The present invention adopts following technical scheme:

The preparation method of the ceramic pigment according to the embodiment of the present invention comprises the following steps:

Step 1, providing aluminum ash;

Step 2, adding water to the aluminum ash and stirring, then removing the supernatant after standing for a predetermined period of time, then adding an alkali solution to the aluminum ash and fully stirring, then performing solid-liquid separation to obtain a solid-phase mixture;

Step 3, roasting the solid-phase mixture to obtain a roasted product;

Step 4, adding dopant ion sources, mineralizers and stabilizers to the roasted product, and performing high-temperature solid-phase synthesis to obtain the ceramic colorant.

Preferably, relative to the total amount of the aluminum ash, the dopant ion source, the mineralizer and the stabilizer, the mass percentage of the aluminum ash is 30wt%-85wt%.

Preferably, in the step 2, the mass ratio of the aluminum ash to the water is 1:(1-7), and the mass ratio of the aluminum ash to the alkali solution is 1:(1-3).

Preferably, the alkaline solution is an aqueous sodium hydroxide solution, and the concentration of the aqueous sodium hydroxide solution is 0.5-40 wt%.

Preferably, in the step 3, the calcination temperature is 500-1100°C.

Preferably, in step 4, the high-temperature solid-phase synthesis temperature is 1000-1350°C

Preferably, in the step 4, the dopant ions contained in the dopant ion source are one or more of manganese ions, zinc ions, chromium ions and cobalt ions.

Preferably, the mass percentage of the mineralizer is 1-5wt%, and the mineralizer is one or more of the compounds sodium chloride, sodium fluoride and ammonium chloride.

Preferably, the weight percentage of the stabilizer is 1-10 wt%, and the stabilizer is one or more of boric acid, calcium carbonate, calcium chloride and dipotassium hydrogen phosphate.

The present invention also provides a ceramic color material, which is prepared by the preparation method of the ceramic color material in the above embodiment.

The technical solution of the present invention has at least one of the following effects:

According to the preparation method of the ceramic pigment of the present invention, it is converted into alumina or aluminum hydroxide by purifying the solid hazardous waste aluminum ash, then introducing doping ions, and adding a specific mineralizer to promote the progress of the solid phase reaction , adding a stabilizer to hide the interference of calcium, magnesium, silicon and other elements on the solid-phase reaction, adopting a solid-phase synthesis method to prepare ceramic pigments and methods thereof. This method realizes the resource utilization of aluminum ash in the field of ceramic pigments, avoids the harm to the environment caused by the random disposal of aluminum ash, and greatly reduces the production cost of traditional chemical processes. The process is simple and environmentally friendly, and meets the requirements of industrial production. .

Description of drawings:

Fig. 1 is the flow chart of the preparation method of the ceramic pigment of an embodiment of the present invention;

Fig. 2 is the X-ray diffraction figure of corresponding red pigment powder in an embodiment 1 of the present invention;

Fig. 3 is the physical appearance figure of the red pigment powder in an embodiment 1 of the present invention;

Fig. 4 is the X-ray diffraction pattern of corresponding pink pigment powder in an embodiment 2 of the present invention;

Fig. 5 is the physical appearance figure of the pink pigment powder in an embodiment 2 of the present invention;

Fig. 6 is the X-ray diffraction figure of corresponding blue pigment powder in an embodiment 3 of the present invention;

FIG. 7 is a physical appearance diagram of the blue colorant powder in Embodiment 3 of the present invention.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are some, not all, embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention belong to the protection scope of the present invention.

Ceramic pigment is an important part in the field of ceramic product decoration. It is an important component of ceramic product color decoration and enamel or blanks. Among them, aluminum-based pigments are widely used, mainly including manganese red and chrome-aluminum red. material, cobalt blue material, etc.

Aluminum ash mainly contains metal aluminum, aluminum oxide, aluminum hydroxide and other substances. The inventors found that aluminum oxide and aluminum hydroxide in aluminum ash can be used as raw materials to prepare ceramic pigments, especially the method of using solid harmful aluminum ash as raw materials to produce ceramic pigments can not only obtain high-value ceramic pigments, It can also make better use of aluminum ash slag.

The preparation method of the ceramic color material and the ceramic color material according to the embodiments of the present invention are described in detail below.

As shown in Figure 1, according to the preparation method of the ceramic pigment of the embodiment of the present invention, comprises the following steps:

S110, available in aluminum gray.

In one embodiment of the present application, the aluminum ash is made of aluminum ash slag. Preferably, the aluminum ash slag is pulverized and sieved, and the sieved mesh can be 80-325 mesh, more preferably 80-140 mesh, to obtain the aluminum ash that is the undersieve. In this way, impurities such as large pieces of metal aluminum are removed, and particles with uniform particle size are obtained, which is beneficial to improving the uniformity and stability of the colorant.

During the screening process, the screened dust and large pieces of metal aluminum can be further recovered.

S120, after adding water to the aluminum ash and stirring, removing the supernatant after standing for a predetermined time, adding an alkali solution therein and fully stirring, performing solid-liquid separation to obtain a solid-phase mixture.

That is to say, in this step, first add water and stir thoroughly, and let it stand for a certain period of time to allow the soluble salts therein to fully dissolve, and remove it by solid-liquid separation (that is, remove the supernatant). In an embodiment of the present invention, the ratio of aluminum ash to water may be 1:1 to 1:7 by mass, preferably 1:5. This ratio can effectively remove soluble salts in aluminum ash.

In aluminum ash, a certain amount of nitrogen is usually mixed in, and this part of nitrogen usually exists in the form of AlN. The presence of nitrogen will affect the subsequent solid-phase reaction, thereby affecting the stability of the colorant. In addition, some unreacted Al is also mixed in the aluminum ash.

For this purpose, after removal of soluble salts therein, the aluminum therein is also hydrolyzed on the one hand to form aluminum hydroxide by introducing an alkaline solution.

On the other hand, nitrogen can be effectively removed therein by adding an alkaline solution such as an aqueous sodium hydroxide solution. Its reaction mechanism is as follows:

AlN+ _H2O →Al(OH) ₃ + _NH3

AlN+NaOH+H ₂ O→NaAlO ₂ +NH ₃

In one embodiment of the present invention, the addition ratio of aluminum ash to alkali solution is 1:1 to 1:3 according to the mass ratio. Preferably, it can be 1:2. This ratio can achieve the optimal amount of alkali addition for nitrogen removal, and the nitrogen removal rate is as high as 94.19%.

In one embodiment of the present invention, the alkali solution may be sodium hydroxide solution, the concentration of which may be 0.5-40%, and this concentration can effectively remove the nitrogen element existing in the form of aluminum nitride in the aluminum ash.

In some embodiments, sodium hydroxide solution is slowly added to the aluminum ash from which the supernatant has been removed, and heated and stirred for a predetermined time, wherein the heating temperature is 50-125° C., and the predetermined time may be 2-4 hours. After heating and stirring for a predetermined time, solid-liquid separation is carried out to obtain a solid-phase mixture.

S130, roasting the solid-phase mixture to obtain a roasted product.

Roasting can, on the one hand, oxidize a small amount of residual metal aluminum and carbon impurities in the aluminum ash, and on the other hand, dehydrate part of the aluminum hydroxide.

In the first embodiment of the present invention, after low-temperature oxygen-enriched roasting, wherein the oxygen-enriched roasting temperature is 500-1100°C, preferably, the temperature can be between 500-850°C, and the roasted product is obtained after oxygen-enriched roasting. The calcined product is a mixture of alumina and aluminum hydroxide.

S140, adding a dopant ion source, a mineralizer and a stabilizer to the roasted product, and performing high-temperature solid-phase synthesis to obtain a ceramic colorant.

Among them, high-temperature solid-phase synthesis refers to the doping of dopant ions into the alumina lattice at high temperature to form a solid solution to form a stable ceramic colorant. In one embodiment of the present invention, the temperature of high-temperature solid-phase synthesis is between 1000-1350°C.

In one embodiment of the present invention, the doping ions in the doping ion source can be one or more of manganese ions, zinc ions, chromium ions and cobalt ions, and these manganese ions, chromium ions, zinc ions, cobalt ions Ions are used as doping elements or pigment formulation components. The dopant ions can be selected according to the color of the ceramic pigment to be formed, for example, a red pigment can be formed by introducing manganese ions, a pink pigment can be formed by the introduction of chromium ions, and a blue pigment can be formed by the introduction of cobalt ions. In addition, it is also possible to simultaneously introduce multiple dopant ions.

In one embodiment of the present invention, the mass percentage of the mineralizer can be 1-5wt%, and the mineralizer is one or more of the compounds sodium chloride, sodium fluoride and ammonium chloride.

In one embodiment of the present invention, the weight percentage of the stabilizer is 1-10 wt%, and the stabilizer is one or more of boric acid, calcium carbonate, calcium chloride and dipotassium hydrogen phosphate.

According to the preparation method of the ceramic pigment in the embodiment of the present invention, the secondary utilization of the solid hazardous waste aluminum ash can be combined with the solid phase method to reduce its harm to the environment, and at the same time promote the use of aluminum ash in the field of ceramic pigments. The utilization of resources makes the invention have the advantages of simple process, easy control, easy production, environmental friendliness and greatly reduced production cost.

In order to enable technical researchers in the field to better understand the technical solutions of the present invention, the present invention will be further described in detail below in conjunction with specific examples.

Example 1

1) Pass the aluminum ash slag (solid hazardous waste aluminum ash) through a 140-mesh sieve, then mix according to the water-cement ratio of 5:1, stir, stand still, and remove the supernatant;

2) According to the alkali-ash ratio of 2:1, add a 20% sodium hydroxide solution by mass fraction to the aluminum ash treated in 1) above, heat to 80° C., stir for 2 hours, and cool to obtain a solid-phase mixture;

3) Roasting the solid-phase mixture obtained above at 700° C. to obtain a mixture of alumina and aluminum hydroxide;

4) Add manganese carbonate, calcium chloride, sodium fluoride, and ammonium chloride to the mixture obtained in the above 3), wherein, in parts by mass, 87 parts of the mixture, 7 parts of manganese carbonate, 2 parts of sodium fluoride, 2 parts of chlorine 3 parts of calcium chloride, 1 part of ammonium chloride, high-temperature solid-phase synthesis at 1050 ° C to obtain red pigment powder.

The sample characterization results are shown in Table 1:

Table 1 Characterization results

The chromaticity value of the full-body ceramic brick sample with the addition of 5% red pigment after being calcined in a roller kiln is shown in Table 2:

Table 2 Chromaticity value table

Among them, L*, a*, and b* in the table are indicators for evaluating colorants, which respectively represent lightness value, red-green value, and yellow-blue value; the larger the value of L*, the brighter the colorant, and the value of a* is Positive indicates that the colorant is red, and negative is green; b* is positive, indicating that the colorant is yellow, and negative is blue; the a* value in the data is greater than b*, indicating that the sample is red; the a* value in the data , b* values are negative, and the absolute value of a* value is less than b* value, it means that the sample is blue. Thus, the scheme of the present invention can obtain brighter red ceramic tiles.

Figure 2 is the XRD pattern corresponding to the sample in Example 1. The XRD pattern of the manganese red material basically corresponds to the PDF card, indicating that manganese ions have been successfully doped into the alumina lattice. The physical picture can be seen in Figure 3.

Example 2

1) Pass the solid hazardous waste aluminum ash through a 140-mesh sieve, then mix with water according to the water-cement ratio of 5.0, stir, and let stand;

2) According to the alkali-ash ratio of 2.0, add 30% sodium hydroxide solution by mass fraction to the above-mentioned treated aluminum ash, heat to 100° C., stir for 3 hours, and cool to obtain a solid-phase mixture;

3) Carrying out the solid-phase mixture obtained above at 750° C. for low-temperature oxygen-rich roasting to obtain a mixture of alumina and aluminum hydroxide;

4) Add chromium oxide, zinc oxide, and boric acid to the mixture obtained above, wherein, in terms of parts by mass, 50 parts of the mixture, 7 parts of chromium oxide, 35 parts of zinc oxide, and 8 parts of boric acid are carried out at 1250° C. Synthesize to obtain pink pigment powder.

The sample characterization results are shown in Table 3:

Table 3 Characterization results

Among them, the XRD pattern of Example 2 can be seen in Figure 4, indicating that chromium ions are successfully doped into the alumina lattice, and the physical picture can be seen in Figure 5 below.

The chromaticity value of the full-body ceramic tile model with a pink pigment addition of 5% after being calcined in a roller kiln is shown in Table 4:

Table 4 Chromaticity value table

From Table 4, the scheme of the present invention can obtain the brighter pink ceramic brick of pigment.

Example 3

1) Pass the solid hazardous waste aluminum ash through a 140-mesh sieve, then mix according to the water-cement ratio of 5:1, stir, stand still, and set aside;

2) According to the soda-ash ratio of 2:1, add 40% sodium hydroxide solution by mass fraction to the above-mentioned treated aluminum ash, heat to 120°C, stir for 4 hours, and cool to obtain a solid-phase mixture;

3) Carrying out the solid-phase mixture obtained above at 850° C. for low-temperature oxygen-rich roasting to obtain a mixture of alumina and aluminum hydroxide;

4) Add cobalt oxide, calcium chloride, and boric acid to the mixture obtained above, wherein, in terms of parts by mass, 75 parts of the mixture, 20 parts of cobalt oxide, and 5 parts of boric acid are carried out at 1200° C. for high-temperature solid-phase synthesis to obtain Blue pigment powder.

The sample characterization results are shown in Table 5:

Table 5 Characterization Results

Among them, Fig. 6 shows the XRD pattern of Example 3, indicating that cobalt ions were successfully doped into the alumina lattice, and the physical diagram can be found in Fig. 7 below.

The chromaticity value of the full-body ceramic brick sample with the addition of 5% cobalt blue material after being calcined in a roller kiln is shown in Table 6:

Table 6 Chromaticity value table

From Table 6, the scheme of the present invention can obtain cobalt blue ceramic tiles.

Aluminum ash component analysis (XDF) is shown in Table 7 in the above-mentioned embodiment:

Table 7 Aluminum ash component analysis (XDF) results

The basic ceramics of the whole body ceramic tile sample plate in the above-mentioned embodiment is the ceramic formula commonly used in ceramic factories, and its component analysis (XDF) is shown in Table 8:

Table 8 Component analysis (XDF) results of whole body ceramic samples

While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that it will include all embodiments falling within the scope of the appended claims.

Claims (8)

1. A preparation method for ceramic pigment, characterized in that, comprising: Step 1, providing aluminum ash; Step 2, after adding water to the aluminum ash and stirring, then removing the supernatant after standing for a predetermined time, adding an alkali solution to it and fully stirring, then performing solid-liquid separation to obtain a solid-phase mixture, the alkali solution is Sodium aqueous solution, the concentration of the sodium hydroxide aqueous solution is 0.5-40wt%; Step 3, roasting the solid-phase mixture to obtain a roasted product; Step 4, adding dopant ion sources, mineralizers and stabilizers to the roasted product, and performing high-temperature solid-phase synthesis to obtain the ceramic colorant. 2. preparation method according to claim 1, is characterized in that, with respect to the total amount of described aluminum ash, described dopant ion source, described mineralizer and described stabilizing agent, the quality of described aluminum ash The percentage is 30wt%-85wt%. 3. the preparation method according to claim 1, is characterized in that, in described step 2, the mass ratio of described aluminum dust and described water is 1: (1-7), described aluminum dust and described alkali The mass ratio of the solution is 1:(1-3). 4. The preparation method according to any one of claims 1-3, characterized in that, in the step 3, the calcination temperature is 500-1100°C. 5. The preparation method according to any one of claims 1-3, characterized in that, in step 4, the high-temperature solid-phase synthesis temperature is 1000-1350°C. 6. preparation method according to claim 1 is characterized in that, in described step 4, the doping ion contained in the described doping ion source is one of manganese ion, zinc ion, chromium ion and cobalt ion one or more species. 7. preparation method according to claim 1, is characterized in that, the mass percentage of described mineralizer is 1-5wt%, and described mineralizer is compound sodium chloride, sodium fluoride and ammonium chloride one or more. 8. preparation method according to claim 1, is characterized in that, the weight percentage of described stabilizing agent 1-10wt%, described stabilizing agent is the one in boric acid, calcium carbonate, calcium chloride and dipotassium hydrogen phosphate or more.

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