CN110655094A - Method for preparing cobalt aluminate pigment with spinel structure by solution combustion method - Google Patents

Method for preparing cobalt aluminate pigment with spinel structure by solution combustion method Download PDF

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CN110655094A
CN110655094A CN201911084764.2A CN201911084764A CN110655094A CN 110655094 A CN110655094 A CN 110655094A CN 201911084764 A CN201911084764 A CN 201911084764A CN 110655094 A CN110655094 A CN 110655094A
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陈岩
张琪
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Jilin University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/046—Stabilisation of aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

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Abstract

The invention discloses a method for preparing cobalt aluminate pigment with a spinel structure by a solution combustion method, and belongs to the technical field of inorganic synthesis. By using solution combustion method, metal nitrate as raw material, organic amine as fuel and water are mixed into solution, and Co with different element proportions is selectively synthesized by controlling reaction temperature and raw material proportionxAl2O3+xThe (x ═ 0-1) series spinel structure cobalt blue powder pigment meets the preparation requirement of cobalt blue nano powder with high purity and high yield. The invention provides a new green and high-yield reaction route for the cobalt blue pigment, and has the advantages of low raw material cost, high yield, low energy consumption, no pollution, selective synthesis and the like.

Description

Method for preparing cobalt aluminate pigment with spinel structure by solution combustion method
Technical Field
The invention belongs to the technical field of inorganic synthesis. In particular to green, high-yield and controllable preparation of Co with different Co element contentsxAl2O3+x(x-0-1) solution combustion method of cobalt blue pigment.
Technical Field
Spinel aluminates are an important industrial material and are used as ceramics, pigments, optical materials, nanomaterials, catalysts, and the like. Wherein the cobalt blue CoAl2O4Is a nontoxic and environment-friendly inorganic pigment and has excellent covering power, tinting strength and dispersibility. Ultramarine Na with another common blue inorganic pigment6Al4Si6S4O20In contrast, because of cobaltThe blue has the structural characteristics of spinel, so free cobalt metal ions are not separated out, and the blue has stable chemical properties, high temperature resistance and acid and alkali resistance. The paint can be widely applied to the fields of high-temperature paint, engineering plastics, high-grade art paint, food packaging and containers, children toys and the like.
At present, the research on the preparation process of the cobalt blue pigment mainly focuses on synthesizing a nano-grade product with good dispersibility. The industrial preparation of the nano cobalt blue powder is mainly divided into a dry method and a wet method. The dry method is mainly to prepare large-particle cobalt blue dye by a high-temperature solid phase method, and then to crush the large particles by mechanical force by using a ball mill to obtain nano-scale powder. The preparation method is simple and suitable for large-scale production, but has the disadvantages of high energy consumption in the synthesis process, uneven particle size distribution of the product, unstable chemical distribution and easy agglomeration, and influences the performance of the dye. The main wet synthesis methods include precipitation, microemulsion and sol-gel methods. The wet method is easy to control the shape, granularity and chemical composition of the product compared with the dry method, but has high cost and complex operation, and is not beneficial to large-scale production. In addition, the gas phase method can also prepare the nano-scale cobalt blue, and the problems of high cost and complex operation are faced like the wet method, so that the scale production is difficult.
Although the cobalt blue has outstanding performance, the cobalt blue is expensive due to the cobalt contained in the component, and the application range of the high-quality pigment is severely limited. Thus, it is commercially valuable to develop new synthesis processes and new products that reduce the Co content of their components without affecting color appearance and performance. The invention can directly regulate and control the content of Co ions in the spinel structure by a simple synthesis method to reduce the production cost of cobalt blue.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the background technology, and utilizes a solution combustion method to prepare a solution by using metal nitrate as a raw material and organic amine as fuel and water, and selectively synthesize Co with different element proportions by controlling the reaction temperature and the raw material proportionxAl2O3+x(x is 0-1) series cobalt blue powder pigment with spinel structure, and high-purity and high-yield cobalt blue nano powder preparation is realizedAnd (5) preparing.
The specific technical scheme is as follows:
a method for preparing cobalt aluminate pigment with a spinel structure by a solution combustion method comprises the steps of taking cobalt nitrate or cobalt acetate as a cobalt source, aluminum nitrate as an aluminum source and organic amine as a combustion agent, wherein the molar ratio of cobalt element to aluminum element is 0-1: 2, and the molar ratio of the total amount of nitrate radicals in the cobalt source and the aluminum source to the total amount of amine radicals in the organic amine is 4: 6; mixing a cobalt source, an aluminum source and a combustion agent, adding distilled water for dissolving to obtain a reaction precursor solution, heating to 350-600 ℃ for reaction after the solution is clarified, quickly concentrating the solution, combusting to obtain a powdery product, and calcining the powdery product for 2-8 hours at 700-1200 ℃ to obtain the spinel-structure cobalt aluminate pigment Co with the yield of more than 95%xAl2O3+x(x＝0～1)。
In the solution combustion reaction process, the reaction conditions are preferably at 400 ℃ for 15 minutes; the calcination temperature is preferably 900 ℃ and the calcination time is preferably 4 hours.
When the reaction precursor is prepared, a combustion improver can be added to improve the crystallization degree of a sample during solution combustion, and the combustion improver can be citric acid (C)6H8O7) Or boric acid (H)3BO3) The mass ratio of the combustion improver to the combustion agent is preferably 2: 15.
In the present invention, the organic amine may be urea (CH)4N2O), glycine (C)2H5NO2) Beta-alanine (C)3H7NO2)；
The reaction equation for using urea as fuel is:
xCo(NO3)2+2Al(NO3)3+(x+5)CH4N2O→CoxAl2O3+x+(2x+10)H2O+(8+2x)N2+(x+5)CO2
the reaction equation for using glycine as fuel is:
xCo(NO3)2+2Al(NO3)3+(6+2x)C2H5NO2→CoxAl2O3+x+(15+5x)H2O+(6+2x)N2+(12+4x)CO2
the reaction equation for using beta-alanine as fuel is:
xCo(NO3)2+2Al(NO3)3+(2x/3+2)C3H7NO2→CoxAl2O3+x+(7x/3+7)H2O+(8x/3+8)N2+(2x+6)CO2
the invention is in the preparation of CoxAl2O3+x(x is 0 to 1) white Al when the sample is free from cobalt2O3The blue color of the sample gradually deepens with the increase of the content of the Co element in the composition. Powder X-ray analysis of the solid phase sample showed the product to be a pure phase spinel structure with no diffraction peaks of the hetero-phase being found. The scanning electron microscope shows that the sample is spongy porous powder formed by gathering nano-scale particles. In the experiment, the maximum yield of the sample obtained was 98% (mole percent). The sample loss is the artificial loss caused in the sample processing process.
Has the advantages that:
the invention is to prepare Co with controllable Co contentxAl2O3+xThe (x ═ 0-1) cobalt blue pigment provides a feasible reaction route and a green preparation method. The cobalt blue pigment has wide application, and the cobalt blue with controllable Co content has great potential advantages as an industrial pigment. The preparation method is green, high in efficiency and high in yield. Therefore, the present invention has important practical significance in terms of environmental protection and resource utilization efficiency.
Drawings
FIG. 1 shows the hydrothermal synthesis of Co in examples 1, 3, 5, 7, 9 and 11 of the present inventionxAl2O3+x(x ═ 0,0.2,0.4,0.6,0.8,1) digital photographs of the pigments.
FIG. 2 shows Al prepared in example 1 of the present invention2O3Scanning electron micrographs.
FIG. 3 shows Al prepared in example 1 of the present invention2O3Powder XRD diffractogram compared to standard lines.
FIG. 4 shows Co prepared in example 3 of the present invention0.2Al2O3.2Scanning electron micrographs.
FIG. 5 shows Co prepared in example 3 of the present invention0.2Al2O3.2Powder XRD diffractogram compared to standard lines.
FIG. 6 shows Co prepared in example 5 of the present invention0.4Al2O3.4Scanning electron micrographs.
FIG. 7 shows Co prepared in example 5 of the present invention0.4Al2O3.4Powder XRD diffractogram compared to standard lines.
FIG. 8 is Co prepared according to example 7 of the present invention0.6Al2O3.6Scanning electron micrographs.
FIG. 9 is Co prepared according to example 7 of the present invention0.6Al2O3.6Powder XRD diffractogram compared to standard lines.
FIG. 10 shows Co prepared in example 9 of the present invention0.8Al2O3.8Scanning electron micrographs.
FIG. 11 shows Co prepared in example 9 of the present invention0.8Al2O3.8Powder XRD diffractogram compared to standard lines.
FIG. 12 is a CoAl prepared in example 11 of the present invention2O4Scanning electron micrographs.
FIG. 13 is a CoAl prepared in example 11 of the present invention2O4Powder XRD diffractogram compared to standard lines.
Detailed Description
Example 1: spinel Al2O3Preparation of
0.7503g of Al (NO) were weighed out3)·9H2O (2mmol) and 0.1501g C2H5NO2(Glycine 2mmol) in a 100mL quartz beaker, 10mL of distilled water was added and stirred well to dissolve it completely. Adjusting the temperature of the flat furnace to 400 ℃, placing the prepared solution on the flat furnace, evaporating and concentrating the solution, and combusting the solution (about 5 minutes in the whole process) before generating gray foamAnd (4) driving the body. And (3) putting the precursor into a crucible, heating the precursor to 900 ℃ in a muffle furnace, calcining the precursor for 4 hours, cooling the precursor to room temperature to obtain a product which is white powder, wherein a physical photograph is shown in figure 1.
The scanning electron micrograph of the product of the example is shown in FIG. 2, the XRD diffraction pattern is shown in FIG. 3 in comparison with the standard spectral line, and the X-ray diffraction pattern is shown in the spinel structure of gamma-Al2O3The peak position and peak intensity of the sample ray diffraction simulation diagram are very good, and no hetero-phase diffraction peak exists. The product was determined to be spinel phase Al2O3The yield was 95.0%.
The elemental analysis results show that the reaction product components and Al2O3The fit is very good.
This example shows the preparation of spinel Al2O3The optimal raw material ratio and reaction conditions. When the reaction temperature is adjusted within the temperature range of 400 ℃ to 600 ℃, the synthesis result is also good. The amount of distilled water is preferably such that the reactants can be dissolved to form a solution, and the addition of an excessive amount of water to the reaction system increases the time for the solution to undergo a combustion reaction. After the using amount of the combustion agent is increased, carbon deposition on the surface of a product after combustion can be increased, and the product can be removed after calcination without influencing the structure and purity of the product. Also, urea or alanine may be used instead of glycine, and samples may be prepared successfully as well.
Example 2: spinel Co0.1Al2O3.1Preparation of
0.0291g of Co (NO) were weighed out3)2·6H2O(0.1mmol)，0.7503g Al(NO3)·9H2O (2mmol) and 0.1501g C2H5NO2(Glycine 2mmol) in a 100mL quartz beaker, 10mL of distilled water was added and stirred well to dissolve it completely. And (3) adjusting the temperature of the flat furnace to 400 ℃, placing the prepared solution on the flat furnace, evaporating and concentrating the solution, and combusting the solution (about 5 minutes in the whole process) to generate a gray foam precursor. And putting the precursor into a crucible, heating the precursor to 900 ℃ in a muffle furnace, calcining the precursor for 4 hours, and cooling the calcined precursor to room temperature to obtain light blue powder.
After the X-ray diffraction pattern of the product of this example was indexed, the unit cell parameters were consistent with the spinel structure, with no hetero-phase diffraction peak. The product was identified as spinel phase. The yield was 95.0%.
The elemental analysis results show that the reaction product components and Co0.1Al2O3.1The fit is very good.
This example shows the preparation of spinel Co0.1Al2O3.1The optimal raw material ratio and reaction conditions. When the reaction temperature is adjusted within the temperature range of 400 ℃ to 600 ℃, the synthesis result is also good. The amount of distilled water is preferably such that the reactants can be dissolved to form a solution, and the addition of an excessive amount of water to the reaction system increases the time for the solution to undergo a combustion reaction. After the using amount of the combustion agent is increased, carbon deposition on the surface of a product after combustion can be increased, and the product can be removed after calcination without influencing the structure and purity of the product. Also, urea or alanine may be used instead of glycine, and samples may be prepared successfully as well.
Example 3: spinel Co0.2Al2O3.2Preparation of
0.0582g of Co (NO) were weighed out3)2·6H2O(0.2mmol)，0.7503g Al(NO3)·9H2O (2mmol) and 0.1501g C2H5NO2(Glycine 2mmol) in a 100mL quartz beaker, 10mL of distilled water was added and stirred well to dissolve it completely. And (3) adjusting the temperature of the flat furnace to 400 ℃, placing the prepared solution on the flat furnace, evaporating and concentrating the solution, and combusting the solution (about 5 minutes in the whole process) to generate a gray foam precursor. And putting the precursor into a crucible, heating the precursor to 900 ℃ in a muffle furnace, calcining the precursor for 4 hours, and cooling the calcined precursor to room temperature to obtain light blue powder. A physical photograph is shown in FIG. 1 (note: since the patent office does not support color drawings, the products in the photograph shown in FIG. 1 show different degrees of gray, with the actual exception of Al2O3White, the remaining products were blue to varying degrees).
The scanning electron micrograph of the product of this example is shown in fig. 4, the XRD diffraction pattern and the standard spectral line contrast pattern are shown in fig. 5, and after the X-ray diffraction pattern of the product of this example is indexed, the unit cell parameters are consistent with the spinel structure, and no hetero-phase diffraction peak exists. The product was identified as spinel phase. The yield was 95.0%.
The elemental analysis results show that the reaction product components and Co0.2Al2O3.2The fit is very good.
This example shows the preparation of spinel Co0.2Al2O3.2The optimal raw material ratio and reaction conditions. When the reaction temperature is adjusted within the temperature range of 400 ℃ to 600 ℃, the synthesis result is also good. The amount of distilled water is preferably such that the reactants can be dissolved to form a solution, and the addition of an excessive amount of water to the reaction system increases the time for the solution to undergo a combustion reaction. After the using amount of the combustion agent is increased, carbon deposition on the surface of a product after combustion can be increased, and the product can be removed after calcination without influencing the structure and purity of the product. Also, urea or alanine may be used instead of glycine, and samples may be prepared successfully as well.
Example 4: spinel Co0.3Al2O3.2Preparation of
Weigh 0.0873g Co (NO)3)2·6H2O(0.3mmol)，0.7503g Al(NO3)·9H2O (2mmol) and 0.1501g C2H5NO2(Glycine 2mmol) in a 100mL quartz beaker, 10mL of distilled water was added and stirred well to dissolve it completely. And (3) adjusting the temperature of the flat furnace to 400 ℃, placing the prepared solution on the flat furnace, evaporating and concentrating the solution, and combusting the solution (about 5 minutes in the whole process) to generate a gray foam precursor. And putting the precursor into a crucible, heating the precursor to 900 ℃ in a muffle furnace, calcining the precursor for 4 hours, and cooling the precursor to room temperature to obtain blue powder as a product.
After the X-ray diffraction pattern of the product of this example was indexed, the unit cell parameters were consistent with the spinel structure, with no hetero-phase diffraction peak. The product was identified as spinel phase. The yield was 95.0%.
The elemental analysis results show that the reaction product components and Co0.3Al2O3.3The fit is very good.
This example shows the preparation of spinel Co0.3Al2O3.3The optimal raw material ratio and reaction conditions. When the reaction temperature is in the temperature range of 400 ℃ to 600 DEG CThe synthesis result of the modulation is also good. The amount of distilled water is preferably such that the reactants can be dissolved to form a solution, and the addition of an excessive amount of water to the reaction system increases the time for the solution to undergo a combustion reaction. After the using amount of the combustion agent is increased, carbon deposition on the surface of a product after combustion can be increased, and the product can be removed after calcination without influencing the structure and purity of the product. Also, urea or alanine may be used instead of glycine, and samples may be prepared successfully as well.
Example 5: spinel Co0.4Al2O3.4Preparation of
0.1164g of Co (NO) were weighed out3)2·6H2O(0.4mmol)，0.7503g Al(NO3)·9H2O (2mmol) and 0.12g CH4N2O (urea 2mmol) was placed in a 100mL quartz beaker, then 10mL distilled water was added and stirred well to dissolve it completely. And (3) adjusting the temperature of the flat furnace to 400 ℃, placing the prepared solution on the flat furnace, evaporating and concentrating the solution, and combusting the solution (about 5 minutes in the whole process) to generate a gray foam precursor. And (3) putting the precursor into a crucible, heating the precursor to 900 ℃ in a muffle furnace, calcining the precursor for 4 hours, cooling the precursor to room temperature to obtain light blue powder, wherein the picture of the real object is shown in figure 1.
The scanning electron micrograph of the product of this example is shown in fig. 6, the XRD diffraction pattern and the standard spectral line contrast pattern are shown in fig. 7, and after the X-ray diffraction pattern of the product of this example is indexed, the unit cell parameters are consistent with the spinel structure, and no hetero-phase diffraction peak exists. The product was identified as spinel phase. The yield was 95.0%.
The elemental analysis results show that the reaction product components and Co0.4Al2O3.4The fit is very good.
This example shows the preparation of spinel Co0.4Al2O3.4The optimal raw material ratio and reaction conditions. When the reaction temperature is adjusted within the temperature range of 400 ℃ to 600 ℃, the synthesis result is also good. The amount of distilled water is preferably such that the reactants can be dissolved to form a solution, and the addition of an excessive amount of water to the reaction system increases the time for the solution to undergo a combustion reaction. After the using amount of the combustion agent is increased, the carbon deposit on the surface of the product after combustion is increased, and the carbon deposit can be removed after calcinationFurthermore, the structure and the purity of the product are not influenced. Also glycine or alanine can be used instead of urea, and samples can be prepared successfully as well.
Example 6: spinel Co0.5Al2O3.5Preparation of
0.1455g of Co (NO) were weighed out3)2·6H2O (0.5mmol) and 0.7503g Al (NO)3)3·9H2O (2mmol) and 0.1501g C2H5NO2(Glycine 2mmol) in a 100mL quartz beaker, then 20mL of distilled water was added and stirred well to dissolve it completely. Placing the prepared solution on a flat furnace, adjusting the flat furnace to heat to 400 ℃ until the glycine is completely combusted after the solution is completely evaporated to dryness, wherein the product is Co0.5Al2O3.5The powder precursor of (1). Mixing Co0.5Al2O3.5The precursor is put into a crucible, and then the crucible is put into a muffle furnace to be heated to 900 ℃ for calcining for 4 hours. The product was a bright blue powder.
After the X-ray diffraction pattern of the product of this example was indexed, the unit cell parameters were consistent with the spinel structure, with no hetero-phase diffraction peak. The product was identified as spinel phase. The yield was 95.0%.
The elemental analysis results show that the reaction product components and Co0.5Al2O3.5The fit is very good.
This example shows the preparation of spinel Co0.5Al2O3.5The optimal raw material ratio and reaction conditions. When the reaction temperature is adjusted within the temperature range of 400 ℃ to 600 ℃, the synthesis result is also good. The amount of distilled water is preferably such that the reactants can be dissolved to form a solution, and the addition of an excessive amount of water to the reaction system increases the time for the solution to undergo a combustion reaction. After the using amount of the combustion agent is increased, carbon deposition on the surface of a product after combustion can be increased, and the product can be removed after calcination without influencing the structure and purity of the product. Also glycine or alanine can be used instead of urea, and samples can be prepared successfully as well.
Example 7: spinel Co0.6Al2O3.6Preparation of
Weigh 0.1746g Co(NO3)2·6H2O (0.6mmol) and 0.7503g Al (NO)3)·9H2O (2mmol) and 0.1501g C2H5NO2(Glycine 2mmol) in a 100mL quartz beaker, then 20mL of distilled water was added and stirred well to dissolve it completely. Placing the prepared solution on a flat furnace, adjusting the flat furnace to heat to 400 ℃ until the glycine is completely combusted after the solution is completely evaporated to dryness, wherein the product is Co0.6Al2O3.6The crystallization of (2) is incomplete. Mixing Co0.6Al2O3.6The precursor is put into a crucible, and then the crucible is put into a muffle furnace to be heated to 900 ℃ for calcining for 4 hours. The product was a bright blue powder and the physical picture is shown in FIG. 1.
The scanning electron micrograph of the product of this example is shown in fig. 8, the XRD diffraction pattern and the standard spectral line contrast pattern are shown in fig. 9, and after the X-ray diffraction pattern of the product of this example is indexed, the unit cell parameters are consistent with the spinel structure, and no hetero-phase diffraction peak exists. The product was identified as spinel phase. The yield was 95.0%.
The elemental analysis results show that the reaction product components and Co0.5Al2O3.5The fit is very good.
This example shows the preparation of spinel Co0.5Al2O3.5The optimal raw material ratio and reaction conditions. When the reaction temperature is adjusted within the temperature range of 400 ℃ to 600 ℃, the synthesis result is also good. The amount of distilled water is preferably such that the reactants can be dissolved to form a solution, and the addition of an excessive amount of water to the reaction system increases the time for the solution to undergo a combustion reaction. After the using amount of the combustion agent is increased, carbon deposition on the surface of a product after combustion can be increased, and the product can be removed after calcination without influencing the structure and purity of the product. Also glycine or alanine can be used instead of urea, and samples can be prepared successfully as well.
Example 8: spinel Co0.7Al2O3.7Preparation of
0.2037g of Co (NO) were weighed out3)2·6H2O (0.7mmol) and 0.7503g Al (NO)3)·9H2O (2mmol) and 0.1501g C2H5NO2(Glycine 2mmol) in a 100mL quartz beaker, 0.02g H was added3BO3As a combustion improver, 20mL of distilled water was added thereto and sufficiently stirred to be completely dissolved. And (3) placing the prepared solution on a flat furnace, adjusting the flat furnace to heat to 500 ℃ until the glycine is completely combusted after the solution is completely evaporated to dryness, wherein the product is bright blue powder.
After the X-ray diffraction pattern of the product of this example was indexed, the unit cell parameters were consistent with the spinel structure, with no hetero-phase diffraction peak. The product was identified as spinel phase. The yield was 95.0%.
The elemental analysis results show that the reaction product components and Co0.7Al2O3.7The fit is very good.
This example shows the preparation of spinel Co0.7Al2O3.7The optimal raw material ratio and reaction conditions. When the reaction temperature is adjusted within the temperature range of 400 ℃ to 600 ℃, the synthesis result is also good. The amount of distilled water is preferably such that the reactants can be dissolved to form a solution, and the addition of an excessive amount of water to the reaction system increases the time for the solution to undergo a combustion reaction. After the using amount of the combustion agent is increased, carbon deposition on the surface of a product after combustion can be increased, and the product can be removed after calcination without influencing the structure and purity of the product. Also glycine or alanine can be used instead of urea, and samples can be prepared successfully as well.
Example 9: spinel Co0.8Al2O3.8Preparation of
0.2328g of Co (NO) were weighed out3)2·6H2O (0.8mmol) and 0.7503g Al (NO)3)·9H2O (2mmol) and 0.1501g C2H5NO2(Glycine 2mmol) in a 100mL quartz beaker, 0.02g of citric acid (C) was added6H8O7) As a combustion improver, 20mL of distilled water was added thereto and sufficiently stirred to be completely dissolved. And (3) placing the prepared solution on a flat furnace, adjusting the flat furnace to heat to 500 ℃ until the glycine is completely combusted after the solution is completely evaporated to dryness, wherein the product is blue-green powder, and a physical photograph is shown in figure 1.
The scanning electron micrograph of the product of this example is shown in fig. 10, the XRD diffraction pattern and the standard spectral line contrast pattern are shown in fig. 11, and after the X-ray diffraction pattern of the product of this example is indexed, the unit cell parameters are consistent with the spinel structure, and no hetero-phase diffraction peak exists. The product was identified as spinel phase. The yield was 95.0%.
The elemental analysis results show that the reaction product components and Co0.8Al2O3.8The fit is very good.
This example shows the preparation of spinel Co0.8Al2O3.8The optimal raw material ratio and reaction conditions. When the reaction temperature is adjusted within the temperature range of 400 ℃ to 600 ℃, the synthesis result is also good. The amount of distilled water is preferably such that the reactants can be dissolved to form a solution, and the addition of an excessive amount of water to the reaction system increases the time for the solution to undergo a combustion reaction. The combustion improver is used for increasing the combustion temperature and improving the crystallinity of the product, and the product does not need secondary calcination treatment. Also glycine or alanine can be used instead of urea, and samples can be prepared successfully as well.
Example 10: spinel Co0.9Al2O3.9Preparation of
0.2619g of Co (NO) were weighed out3)2·6H2O (0.9mmol) and 0.7503g Al (NO)3)·9H2O (2mmol) and 0.1501g C2H5NO2(Glycine 2mmol) in a 100mL quartz beaker, 0.02g of citric acid (C) was added6H8O7) As a combustion improver, 20mL of distilled water was added thereto and sufficiently stirred to be completely dissolved. And (3) placing the prepared solution on a flat furnace, adjusting the flat furnace to heat to 500 ℃ until the glycine is completely combusted after the solution is completely evaporated to dryness, wherein the product is blue-green powder.
After the X-ray diffraction pattern of the product of this example was indexed, the unit cell parameters were consistent with the spinel structure, with no hetero-phase diffraction peak. The product was identified as spinel phase. The yield was 95.0%.
The elemental analysis results show that the reaction product components and Co0.9Al2O3.9The fit is very good.
This example shows the preparation of spinel Co0.9Al2O3.9The optimal raw material ratio and reaction conditions. When the reaction temperature is adjusted within the temperature range of 400 ℃ to 600 ℃, the synthesis result is also good. The amount of distilled water is preferably such that the reactants can be dissolved to form a solution, and the addition of an excessive amount of water to the reaction system increases the time for the solution to undergo a combustion reaction. The combustion improver is used for increasing the combustion temperature and improving the crystallinity of the product, and the product does not need secondary calcination treatment. Also glycine or alanine can be used instead of urea, and samples can be prepared successfully as well.
Example 11: spinel CoAl2O4Preparation of
Weigh 0.291g Co (NO)3)2·6H2O (1mmol) and 0.7503g Al (NO)3)·9H2O (2mmol) and 0.1501g C2H5NO2(Glycine 2mmol) in a 100mL quartz beaker, then 20mL of distilled water was added and stirred well to dissolve it completely. And (3) placing the prepared solution on a flat furnace, adjusting the flat furnace to heat to 500 ℃ until the glycine is completely combusted after the solution is completely evaporated to dryness, wherein the product is blue-green powder, and a physical photograph is shown in figure 1.
The scanning electron micrograph of the product of this example is shown in fig. 12, the XRD diffraction pattern and the standard spectral line contrast pattern are shown in fig. 13, and after the X-ray diffraction pattern of the product of this example is indexed, the unit cell parameters are consistent with the spinel structure, and no hetero-phase diffraction peak exists. The product was identified as spinel phase. The yield was 95.0%.
The elemental analysis results showed the reaction product composition with CoAl2O4The fit is very good.
This example shows the preparation of spinel CoAl2O4The optimal raw material ratio and reaction conditions. When the reaction temperature is adjusted within the temperature range of 400 ℃ to 600 ℃, the synthesis result is also good. The amount of distilled water is preferably such that the reactants can be dissolved to form a solution, and the addition of an excessive amount of water to the reaction system increases the time for the solution to undergo a combustion reaction. After the using amount of the combustion agent is increased, carbon deposition on the surface of a product after combustion can be increased, and the product can be removed after calcination without influencing the structure and purity of the product. Can also useGlycine or alanine instead of urea also successfully prepared samples.

Claims (4)

1. A method for preparing cobalt aluminate pigment with a spinel structure by a solution combustion method comprises the steps of taking cobalt nitrate or cobalt acetate as a cobalt source, aluminum nitrate as an aluminum source and organic amine as a combustion agent, wherein the molar ratio of cobalt element to aluminum element is 0-1: 2, and the molar ratio of the total amount of nitrate radicals in the cobalt source and the aluminum source to the total amount of amine radicals in the organic amine is 4: 6; mixing a cobalt source, an aluminum source and a combustion agent, adding distilled water for dissolving to obtain a reaction precursor solution, heating to 350-600 ℃ for reaction after the solution is clarified, quickly concentrating the solution, combusting to generate a powdery product, and performing secondary calcination on the powdery product at 700-1200 ℃ for 2-8 hours to obtain the spinel-structure cobalt aluminate pigment with the yield of more than 95%.
2. The method for preparing spinel-structured cobalt aluminate pigment by solution combustion as claimed in claim 1, wherein, in the solution combustion reaction, the reaction conditions are a reaction at a temperature of 400 ℃ for 15 minutes; in the calcination process, the calcination temperature was 900 ℃ and the calcination time was 4 hours.
3. The method for preparing the cobalt aluminate pigment with the spinel structure by the solution combustion method according to claim 1, wherein a combustion improver is added to improve the crystallization degree of a sample during the combustion of the solution when a reaction precursor is prepared, wherein the combustion improver is citric acid or boric acid, and the mass ratio of the combustion improver to the combustion improver is 2: 15.
4. The method for preparing cobalt aluminate pigment with spinel structure by using solution combustion method according to any one of claims 1-3, characterized in that the organic amine is urea, glycine or beta-alanine.
CN201911084764.2A 2019-11-08 2019-11-08 Method for preparing cobalt aluminate pigment with spinel structure by solution combustion method Pending CN110655094A (en)

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