CN111017994B - Preparation method of nano green-phase bismuth yellow vanadate powder - Google Patents
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Abstract
The invention discloses a method for preparing nano green-phase bismuth yellow vanadate powder, and a treatment fluid comprises Bi (NO)3)3·5H2O and NH4VO3The mass ratio of the substances is (1-1.2): 1, the solution concentration is 0.01-0.10 mol/L, and the organic solvent is0.5-4.0 ml/L of solvent, 2.0-8.0 g/L of surfactant, 2.0-10.0 ml/L of cosurfactant, 1.0-3.0 pH and 30-90 s of ultrasonic emulsification dispersion, wherein the synthesis reaction comprises the steps of mechanical stirring at the speed of 50-100 r/min, temperature of 50-80 ℃ and time of 3.0-4.5 h, cleaning for 5-6 times by using ethanol or acetone and distilled water, standing, separating and drying to obtain single-phase green-phase yellow nano bismuth vanadate powder. The method is simple and easy to operate, the prepared green-phase bismuth yellow vanadate powder particles are nano-sized, the particles are uniform, controllable and stable, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of an inorganic pigment, in particular to a preparation method of nano green-phase bismuth yellow vanadate powder.
Background
With the increasing health and environmental awareness, the application of the traditional toxic inorganic yellow pigments such as chrome yellow, cadmium yellow and other yellow pigments is greatly limited, and therefore, the search for the non-toxic inorganic yellow pigments is a demand for social development. A large number of researches show that the bismuth vanadate yellow pigment has excellent performances of no toxicity, good weather resistance, high tinting strength, high gloss, good covering power and the like, is a green environment-friendly pigment with good prospect, and can be used as a substitute of the traditional chrome yellow and cadmium yellow pigments.
At present BiVO4The preparation method mainly comprises a solid-phase reaction method, a sol-gel method, a chemical precipitation method, a hydrothermal synthesis method, a liquid-phase precipitation method, a gas-phase method and the like. Patent application numbers 201110398953.4, 201210228971.2, 201210457806.4, 201310013662.8, 201310343864.9, 201310344884.8 and other Chinese invention patents relate to some preparation methods of bismuth vanadate.
The preparation methods can prepare bright yellow BiVO4The pigment has a complex preparation process, or large pigment particles and uneven particle size distribution, or poor color and luster and temperature resistance, and has certain defects in application performance. Therefore, the development and operation of the preparation technology which is simple, fine in particles, uniform, controllable and stable in particles is of great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of nano green-phase bismuth yellow vanadate powder. The preparation method has simple process flow, the obtained bismuth vanadate powder is bright yellow (namely green-phase yellow), the average particle size of the powder is 110-130 nm, the particle size of the powder is less than 100nm and more than 40%, and the particle size of the powder is less than 200nm and more than 80%; the powder crystal structure is monoclinic.
The technical scheme of the invention is as follows: a method for preparing nano green-phase bismuth yellow vanadate powder comprises the following steps:
(1) weighing and taking NH4VO3Dissolving the mixture into deionized water, and stirring and dissolving the mixture by using a stirrer at 40-50 ℃, and marking the solution as A; weighing and taking Bi (NO)3)3﹒5H2Dissolving O in deionized water, and stirring and dissolving at 40-50 ℃ by using a stirrer to obtain a solution B;
(2) weighing, taking an organic solvent, a surfactant and a cosurfactant, putting into a beaker, stirring, mixing and dissolving, and marking as a solution C;
(3) mixing and stirring the solution C with the solutions A and B respectively, and marking as solutions A 'and B';
(4) mixing the A 'and B' solutions, and performing ultrasonic emulsification treatment to prepare a microemulsion; the synthesis reaction is mechanical stirring, and the PH value, the reaction time and the reaction temperature are adjusted;
(5) washing the powder finally obtained in the experiment with ethanol or acetone and distilled water for 5-6 times, fully and uniformly stirring each time of washing, standing for precipitation and layering, filtering off the upper-layer solution, and repeating the steps for 5-6 times;
(6) drying the filtered powder at the temperature of 80-85 ℃ for 10-12 h to obtain the nano BiVO4And (3) powder.
Preferably, NH prepared in the step (1)4VO3The concentration of the solution is 0.01-0.10 mol/L; prepared Bi (NO)3)3·5H2The concentration of the O solution is 0.01-0.10 mol/L.
Preferably, the step (1) is added with Bi (NO) inhibitor3)3·5H2The concentration of the dilute nitric acid obtained by O hydrolysis is 1.0-1.5 mol/L.
Preferably, the organic solvent in the step (2) is cyclohexane, and the addition amount is 0.5-4.0 ml/L.
Preferably, in the step (2), the surfactant is one or a mixture of more than one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfonate in any proportion, and the addition amount is 2.0-8.0 g/L.
Preferably, in the step (2), the cosurfactant is one or a mixture of more than one of glycerol, n-butanol and n-octanol in any proportion, and the addition amount is 2.0-10.0 ml/L.
Preferably, in the step (3), the solution C is mixed with the solutions A and B respectively by equal volume.
Preferably, the concentration of the mixed solution of the A 'solution and the B' solution in the step (3) is 0.01-0.05 mol/L, and Bi (NO) in the mixed solution3)3·5H2O and NH4VO3The mass ratio of the substances is (1-1.2): 1.
Preferably, in the step (4), the ultrasonic emulsification treatment of the mixed solution of the A 'and the B' is carried out at an ultrasonic frequency of 20KHZ for 30-90 s; and adjusting the pH value by adopting 10% NaOH solution or ammonia water, wherein the pH value is 1.0-3.0, the reaction temperature is 50-80 ℃, the stirring speed is 50-100 r/min, and the time is 3.0-4.5 h.
Preferably, BiVO prepared in the step (6)4The powder is bright yellow (green phase yellow), has average particle size of 110-130 nm, particle size of 100nm or less of 40% or more, particle size of 200nm or less of 80% or more, and powder crystalThe bulk structure being monoclinic
Compared with the prior art, the preparation method of the nano green-phase bismuth yellow vanadate powder has the following beneficial effects that:
1. the process for preparing the nano green-phase bismuth yellow vanadate powder is simple;
2. the nano green-phase bismuth yellow vanadate powder is bright yellow, the average particle size of the powder is 110-130 nm, the particle size of the powder is less than 100nm and more than 40%, and the particle size of the powder is less than 200nm and more than 80%;
3. the crystal structure of the nano green-phase bismuth yellow vanadate powder is a monoclinic system;
4. the nano green-phase bismuth yellow vanadate powder has no pollutant emission in the preparation process, is a green environment-friendly pigment with good prospect, and can be used as a substitute of the traditional chrome yellow and cadmium yellow lead-containing pigments.
Drawings
FIG. 1 is a macroscopic picture of the nano bismuth vanadate powder prepared in example 1 of the present invention.
FIG. 2 is an SEM photograph of bismuth vanadate powder prepared in example 1 of the present invention.
FIG. 3 is an EDS picture of bismuth vanadate powder prepared in example 1 of the present invention.
Curve 1 in FIG. 4 is a particle size distribution curve of the bismuth vanadate powder prepared in example 1 of the present invention.
Curve 2 of FIG. 4 is a particle size distribution curve of the bismuth vanadate powder prepared in example 2 of the present invention.
Curve 3 in FIG. 4 is a particle size distribution curve of the bismuth vanadate powder prepared in example 4 of the present invention.
FIG. 5 is an XRD picture of bismuth vanadate powder prepared in example 2 of the present invention.
FIG. 6 is an SEM photograph of bismuth vanadate powder prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A method for preparing nano green-phase bismuth yellow vanadate powder comprises the following steps:
1) weighing and taking NH4VO3Dissolving the mixture into deionized water, and stirring and dissolving the mixture by using a stirrer at 40-50 ℃, and marking the solution as A;
2) weighing and taking Bi (NO)3)3·5H2Dissolving O in deionized water, stirring and dissolving at 40-50 ℃ by using a stirrer, and adding a small amount of dilute nitric acid to prevent hydrolysis of bismuth nitrate pentahydrate, and marking as a solution B;
3) 2.0g of sodium dodecyl benzene sulfonate, 1.0ml/L of cyclohexane and 3.0ml/L of n-octanol are put into a beaker to be stirred, mixed and dissolved, and is marked as solution C;
4) dividing the solution C into two equal parts, mixing and stirring the solution C and the solution A and the solution B respectively to prepare microemulsion which is marked as solution A 'and solution B' respectively;
5) mixing the A 'and B' solutions to react, the concentration is 0.02mol/L, and Bi (NO) in the mixed solution3)3·5H2O and NH4VO3The mass ratio was 1: 1. Ultrasonic 20K HZ dispersion and emulsification treatment is carried out for 30 s. The synthesis reaction temperature is 50 ℃, the PH value is 3.0, the stirring speed is 50r/min, and the reaction time is 4.5 h;
6) washing the powder finally obtained in the experiment with ethanol or acetone and distilled water for 5-6 times, fully and uniformly stirring each time of washing, standing for precipitation and layering, filtering off the upper-layer solution, and repeating the steps for 5-6 times;
7) drying the filtered powder at 80 deg.C for 12h, and storing the dried powder.
The obtained bismuth vanadate powder is subjected to morphology, composition, particle size and other analysis by respectively adopting a camera, a scanning electron microscope, an energy spectrometer and a high-precision particle size analyzer, the macroscopic view of the obtained powder is shown in figure 1, the SEM view and the EDS view are shown in figures 2 and 3, and the particle size distribution curve is shown in figure 4, curve 1 and table 1. The powder is bright yellow and spherical, and mainly contains Bi and V, O elements. The average particle size of the powder is 110-130 nm, the powder particle size is more than 40% below 100nm, and the powder particle size is more than 80% below 200 nm.
TABLE 1 bismuth vanadate powder particle size distribution
Example 2
A method for preparing nano green-phase bismuth yellow vanadate powder comprises the following steps:
1) weighing and taking NH4VO3Dissolving the mixture into deionized water, and stirring and dissolving the mixture by using a stirrer at 40-50 ℃, and marking the solution as A;
2) weighing and taking Bi (NO)3)3·5H2Dissolving O in deionized water, stirring and dissolving at 40-50 ℃ by using a stirrer, and adding a small amount of dilute nitric acid to prevent hydrolysis of bismuth nitrate pentahydrate, and marking as a solution B;
3) putting 8.0g of sodium dodecyl benzene sulfonate, 7.0ml/L of cyclohexane and 10.0ml/L of n-octanol into a beaker, stirring, mixing and dissolving to obtain solution C;
4) dividing the solution C into two equal parts, mixing and stirring the solution C and the solution A and the solution B respectively to prepare microemulsion which is marked as solution A 'and solution B' respectively;
5) mixing the A 'and B' solutions to react, the concentration is 0.10mol/L, and Bi (NO) in the mixed solution3)3·5H2O and NH4VO3The mass ratio was 1.2: 1. Ultrasonic 20K HZ dispersion and emulsification treatment is carried out for 90 s. The synthesis reaction temperature is 80 ℃, the PH value is 1.0, the stirring speed is 100r/min, and the reaction time is 3.0 h;
6) washing the powder finally obtained in the experiment with ethanol or acetone and distilled water for 5-6 times, fully and uniformly stirring each time of washing, standing for precipitation and layering, filtering off the upper-layer solution, and repeating the steps for 5-6 times;
7) drying the filtered powder at 85 deg.C for 10h, and storing the dried powder.
The obtained bismuth vanadate powder is respectively subjected to a high-precision particle size analyzer and an X-ray diffractometer, the obtained particle size distribution curve chart is shown in figure 4 and an XRD (X-ray diffraction) chart is shown in figure 5, the average particle size of the powder is 110-130 nm, and the crystal structure of the powder is a monoclinic system.
Example 3
A method for preparing nano green-phase bismuth yellow vanadate powder comprises the following steps:
1) weighing and taking NH4VO3Dissolving the mixture into deionized water, and stirring and dissolving the mixture by using a stirrer at 40-50 ℃, and marking the solution as A;
2) weighing and taking Bi (NO)3)3·5H2Dissolving O in deionized water, stirring and dissolving at 40-50 ℃ by using a stirrer, and adding a small amount of dilute nitric acid to prevent hydrolysis of bismuth nitrate pentahydrate, and marking as a solution B;
3) placing 5.0g of sodium dodecyl benzene sulfonate, 4.0ml/L of cyclohexane and 6.0ml/L of n-octanol into a beaker, stirring, mixing and dissolving to obtain solution C;
4) dividing the solution C into two equal parts, mixing and stirring the solution C and the solution A and the solution B respectively to prepare microemulsion which is marked as solution A 'and solution B' respectively;
5) mixing the A 'and B' solutions to react, the concentration is 0.08mol/L, and Bi (NO) in the mixed solution3)3·5H2O and NH4VO3The mass ratio was 1.1: 1. Ultrasonic 20K HZ dispersion and emulsification treatment is carried out for 60 s. The synthesis reaction temperature is 70 ℃, the PH value is 2.0, the stirring speed is 80r/min, and the reaction time is 3.5 h;
6) washing the powder finally obtained in the experiment with ethanol or acetone and distilled water for 5-6 times, fully and uniformly stirring each time of washing, standing for precipitation and layering, filtering off the upper-layer solution, and repeating the steps for 5-6 times;
7) drying the filtered powder at 80 deg.C for 12h, and storing the dried powder.
The morphology of the obtained bismuth vanadate powder is observed by a scanning electron microscope, and an SEM image of the obtained powder is shown in FIG. 6. The powder is spherical, and the average particle size of the powder is 110-130 nm.
Example 4
A method for preparing nano green-phase bismuth yellow vanadate powder comprises the following steps:
1) weighing and taking NH4VO3Dissolving the mixture into deionized water, and stirring and dissolving the mixture by using a stirrer at 40-50 ℃, and marking the solution as A;
2) weighing and taking Bi (NO)3)3·5H2Dissolving O in deionized water, stirring and dissolving at 40-50 ℃ by using a stirrer, and adding a small amount of dilute nitric acid to prevent hydrolysis of bismuth nitrate pentahydrate, and marking as a solution B;
3) 4.0g of sodium dodecyl benzene sulfonate, 3.5ml/L of cyclohexane and 5.0ml/L of n-octanol are put into a beaker to be stirred, mixed and dissolved, and is marked as solution C;
4) dividing the solution C into two equal parts, mixing and stirring the solution C and the solution A and the solution B respectively to prepare microemulsion which is marked as solution A 'and solution B' respectively;
5) mixing the A 'and B' solutions to react, the concentration is 0.05mol/L, and Bi (NO) in the mixed solution3)3·5H2O and NH4VO3The mass ratio was 1.05: 1. Ultrasonic 20K HZ dispersion and emulsification treatment is carried out for 50 s. The synthesis reaction temperature is 75 ℃, the PH value is 2.5, the stirring speed is 60r/min, and the reaction time is 4.0 h;
6) washing the powder finally obtained in the experiment with ethanol or acetone and distilled water for 5-6 times, fully and uniformly stirring each time of washing, standing for precipitation and layering, filtering off the upper-layer solution, and repeating the steps for 5-6 times;
7) drying the filtered powder at 85 deg.C for 10h, and storing the dried powder.
The obtained bismuth vanadate powder is analyzed in morphology, composition, particle size and the like by a high-precision particle size analyzer, and a particle size distribution curve chart is shown as curve 3 in FIG. 4. The average particle size of the powder is 110-130 nm, the powder particle size is more than 40% below 100nm, and the powder particle size is more than 80% below 200 nm.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or simple substitutions which are not thought of through the inventive work should be included in the scope of the present invention.
Claims (3)
1. A preparation method of nano green-phase bismuth yellow vanadate powder is characterized by comprising the following steps:
(1) weighing NH4VO3Dissolving the mixture into deionized water, and stirring and dissolving the mixture by using a stirrer at 40-50 ℃, and marking the solution as A; weighing Bi (NO)3）3﹒5H2Dissolving O in deionized water, and stirring and dissolving at 40-50 ℃ by using a stirrer to obtain a solution B;
(2) weighing an organic solvent, a surfactant and a cosurfactant, putting the organic solvent, the surfactant and the cosurfactant into a beaker, stirring, mixing and dissolving the mixture, and marking the solution as a solution C;
(3) mixing and stirring the solution C with the solutions A and B respectively, and marking the mixture as A'，B'A solution;
(4) a is to be'，B'Mixing the two solutions, and performing ultrasonic emulsification treatment to prepare a microemulsion; the synthesis reaction is mechanical stirring, and the pH value, the reaction time and the reaction temperature are adjusted;
(5) washing the powder finally obtained in the experiment with ethanol or acetone and distilled water for 5-6 times, fully and uniformly stirring each time of washing, standing for precipitation and layering, filtering off the upper-layer solution, and repeating the steps for 5-6 times;
(6) drying the filtered powder at the temperature of 80-85 ℃ for 10-12 h to obtain the nano BiVO4Powder;
in the step (2), the organic solvent is cyclohexane, and the addition amount is 0.5-4.0 ml/L;
the surfactant in the step (2) is one or a mixture of more than one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfonate in any proportion, and the addition amount is 2.0-8.0 g/L;
the cosurfactant in the step (2) is one or a mixture of more than one of glycerol, n-butanol and n-octanol in any proportion, and the addition amount is 2.0-10.0 ml/L;
in the step (3), the solution C is mixed with the solutions A and B respectively by adopting equal volume;
a in the step (3)'，B'The concentration of the mixed solution of the two solutions is 0.01-0.05 mol/L, and Bi (NO) in the mixed solution3)3·5H2O and NH4VO3The mass ratio of the substances is (1-1.2) to 1;
in the step (4)A'，B'The ultrasonic emulsification treatment of the mixed solution of the two solutions is that the ultrasonic frequency is 20kHz, and the emulsification time is 30-90 s; adjusting the pH value by adopting 10% NaOH solution or ammonia water, wherein the pH value is 1.0-3.0, the reaction temperature is 50-80 ℃, the stirring speed is 50-100 r/min, and the time is 3.0-4.5 h;
the BiVO prepared in the step (6)4The powder is bright yellow, the average particle size of the powder is 110-130 nm, the particle size of the powder is less than 100nm and more than 40%, the particle size of the powder is less than 200nm and more than 80%, and the crystal structure of the powder is monoclinic.
2. The method for preparing nano green-phase bismuth yellow vanadate powder according to claim 1, wherein the method comprises the following steps: NH prepared in the step (1)4VO3The concentration of the solution is 0.01-0.10 mol/L; prepared Bi (NO)3）3·5H2The concentration of the O solution is 0.01-0.10 mol/L.
3. The method for preparing nano green-phase bismuth yellow vanadate powder according to claim 2, wherein the method comprises the following steps: in the step (1), Bi (NO) is also added3）3·5H2The concentration of the dilute nitric acid obtained by O hydrolysis is 1.0-1.5 mol/L.
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