CN114410127A - Method for efficiently and cleanly preparing clay mineral hybrid bismuth yellow pigment - Google Patents
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0006—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black containing bismuth and vanadium
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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Abstract
The invention relates to a method for efficiently and cleanly preparing clay mineral hybrid bismuth yellow pigment, belonging to the preparation technology of nano hybrid pigment. Adding clay mineral, bismuth source and vanadium source into a double-screw extruder, preparing a precursor by using the double-screw extruder without adding or after adding a molybdenum source, and crystallizing the precursor at the high temperature of 500-900 ℃ for 30-180 min to obtain the clay mineral hybrid bismuth yellow pigment. The clay mineral hybrid bismuth yellow pigment is prepared by adopting a double-screw extruder, so that the technical problems of intermittent production and large energy consumption in a solid phase method are solved, and the defects of low yield, more wastes and complicated steps in a liquid phase method are overcome. The method disclosed by the invention is low in energy consumption, high in yield, green and clean, low in production cost and suitable for industrial continuous production.
Description
Technical Field
The invention relates to a method for preparing clay mineral hybrid bismuth yellow pigment for coloring and reinforcing polymer, belonging to the preparation technology of nano hybrid pigment.
Background
The bismuth yellow pigment is a high-performance environment-friendly inorganic pigment which takes bismuth vanadate as a main chromophoric component, has good light resistance, acid and alkali resistance and chemical stability resistance, does not bleed or migrate, has high tinting strength, can directly replace the traditional lead-cadmium yellow inorganic pigment, and is expected to fundamentally solve the toxicity in the pigment production and use processes. However, compared with the traditional lead-cadmium yellow inorganic pigment, the bismuth yellow pigment has higher production cost and poorer heat resistance in the inorganic pigment. Researches show that the introduction of clay mineral and other inorganic matrixes can effectively reduce the production cost of the bismuth yellow pigment and improve the color performance and the heat resistance of the bismuth yellow pigment. At present, the related preparation technology mainly comprises a solid phase method and a liquid phase method, wherein the solid phase method mainly adopts mechanical and chemical methods such as high-energy ball milling and the like, belongs to an intermittent preparation technology, and has high required energy consumption; the pigment prepared by the liquid phase method has small granularity, high purity, lower calcination temperature than that of a solid phase reaction and easy control, but the preparation process is complex, the preparation cost is higher, the pigment yield is lower, and a large amount of waste liquid is generated. The two methods are difficult to popularize on a large scale in industrial actual production.
Twin screw extrusion is a polymer processing technique that is widely used for reactive processing (including polymerization and grafting reactions), mixing and blending, devolatilization, and thermoplastic profile extrusion. The invention is based on the inspiration of the interaction between the filler and the polymer matrix in the double-screw extrusion process, and prepares the high-performance low-cost clay mineral hybrid cobalt blue pigment by utilizing the actions of shearing, rolling, kneading and the like generated in the double-screw extrusion process.
Disclosure of Invention
The invention aims to provide a method for efficiently and cleanly preparing clay mineral hybrid bismuth yellow pigment, which solves the technical defects of preparing cobalt blue pigment by a solid phase method and a liquid phase method and develops a novel efficient and clean preparation technology of inorganic pigment.
Method for efficiently and cleanly preparing clay mineral hybrid bismuth yellow pigment
The method for preparing the clay mineral hybrid bismuth yellow pigment comprises the steps of adding the clay mineral, a bismuth source and a vanadium source into a double-screw extruder, preparing a precursor in the double-screw extruder under the actions of shearing, rolling, kneading and the like generated in the double-screw extrusion process without adding or after adding a molybdenum source, and crystallizing the precursor at the high temperature of 500-900 ℃ for 30-180 min to obtain the clay mineral hybrid bismuth yellow pigment.
The double-screw extruder is one of a co-rotating double-screw extruder, a differential co-rotating double-screw extruder, a counter-rotating inner double-screw extruder and a double-stage double-screw extruder.
The clay mineral is at least one of serpentine-kaolinite family, talc-pyrophyllite family, mica family, sepiolite family, smectite family, illite family, vermiculite family, chlorite family and allophane.
The mass ratio of the bismuth source to the clay mineral is 1: 3-1: 0.05.
The vanadium source is at least one of ammonium metavanadate, sodium vanadate, potassium metavanadate, vanadium pentoxide and vanadium oxide, and the mass ratio of the vanadium source to the bismuth source is 1: 5-1: 1.
The molybdenum source is at least one of sodium molybdate, ammonium molybdate, potassium molybdate and sodium phosphomolybdate, and the mass ratio of the bismuth source to the molybdenum source is 1: 20-1: 0.25.
II, structural and performance characterization of clay mineral hybrid bismuth yellow pigment
1. X-ray diffraction spectrum of clay mineral hybrid bismuth yellow pigment
FIG. 1 is the X-ray diffraction pattern of clay mineral hybrid bismuth yellow pigment prepared in examples one, two, three, four and five. As shown in the figure, in2θMonoclinic scheelite-type BiVO appears at = 18.9 °, 29.0 °, 30.6 °, 34.5 °, 35.2 °, 39.9 °, 42.6 °, 46.8 °, 47.2 °, 53.2 °, 58.4 ° and 59.5 °4The characteristic diffraction peaks of (a) correspond to the (011), (121), (040), (200), (002), (211), (051), (060), (042), (-161), (-321) and (123) crystal planes, respectively. The contrast finds that other phase diffraction peaks appear in the X-ray diffraction spectrogram of the prepared bismuth yellow pigment, which shows that Al in the clay mineral after calcination treatment3+、Mg2+、Ca2+Is doped intoInto BiVO4The crystal lattice of the crystal.
2. Transmission electron microscope photo of clay mineral hybrid bismuth yellow pigment
FIG. 2 is a transmission electron micrograph of the clay mineral hybrid bismuth yellow pigment prepared in example one and example two. It can be found that the sample has a typical rod-like and sheet-like structure, and bismuth yellow nanoparticles with a particle size of about 5-10 nm are uniformly supported on the surface of the rod-like and sheet-like matrix, and no obvious agglomeration phenomenon is observed. Therefore, the clay mineral is introduced to prepare the bismuth yellow pigment, so that the agglomeration phenomenon of the bismuth yellow nano particles in the high-temperature crystallization process can be effectively prevented.
3. Color properties of clay mineral hybrid bismuth yellow pigments
CIE-L * a * b * A color parameter. As shown in Table 1, the bismuth yellow pigment obtained by the present invention is high in performanceb * Sum of value lowa * The value of the one or more of the one,b * the values all reached over 87, indicating that it had a higher yellow phase and a lower red phase, and the appearance of the sample appeared bright yellow. Comparing the maximum absorption edge Kubelka-munk plot (figure 3) and the UV-vis diffuse reflectance spectrum (inset) of the sample, the precursor prepared in the example is calcined, and Al in clay mineral is3+、Mg2+、Ca2+Plasma entry into BiVO4Causing the crystal lattice to be distorted and deformed to promote BiVO4The band gap energy changes. Therefore, the bismuth yellow pigment prepared by introducing the oxide changes the charge transfer between the conduction band and the valence band, and the oxide is a matrix material for supporting the bismuth yellow nanoparticles and a dopant for adjusting the color of the bismuth yellow pigment in the preparation process.
In summary, the invention aims to overcome the defects of the existing bismuth yellow pigment preparation technology and performance, and provides a method for efficiently, continuously and cleanly preparing clay mineral hybrid bismuth yellow pigment. Compared with the prior art, the method has the following advantages:
(1) the clay mineral hybridized bismuth yellow pigment is prepared by adopting a double-screw extruder, so that the technical problems of intermittent production and high energy consumption of a solid phase method are solved, and the defects of low yield and complicated steps of a liquid phase method are overcome.
(2) The method disclosed by the invention is low in energy consumption, high in yield, green and clean, and suitable for industrial continuous production.
(3) The invention utilizes the actions of shearing, rolling, kneading and the like generated in the process of double-screw extrusion to induce the bismuth source and the vanadium source to generate interaction on the molecular level and deposit the clay mineral surface in situ.
Drawings
FIG. 1 is an X-ray diffraction spectrum of clay mineral hybrid bismuth yellow pigment prepared in the first to fifth embodiments of the present invention;
FIG. 2 is a transmission electron micrograph of clay mineral hybrid bismuth yellow pigment prepared according to the first and second embodiments of the present invention;
FIG. 3 is a Kubelka-munk plot and a UV-vis diffuse reflection spectrum chart of the maximum absorption edge of the clay mineral hybrid bismuth yellow pigment prepared in the first to fifth embodiments of the invention.
Detailed Description
The technical solution of the present invention is further described below with reference to examples, but the scope of the present invention is not limited thereto.
Example one
60 g of attapulgite clay, 20.69 g of bismuth acetate and 10.65 g of potassium metavanadate are put into a differential co-rotating double-screw extruder to be extruded to prepare a precursor, and the precursor is crystallized at the high temperature of 500 ℃ for 120 min and then crushed to prepare the bismuth-based yellow hybrid pigment. The corresponding sample is marked S-1, whichL * 、a * 、b * The color values are shown in Table 1.
Example two
50 g of kaolinite, 121.27 g of bismuth nitrate, 75.24 g of bismuth sulfate, 64.37 g of sodium vanadate and 27.36 g of sodium molybdate are put into a double-stage double-screw extruder to be extruded to prepare a precursor, and the precursor is crystallized at the high temperature of 600 ℃ for 60 min and then crushed to prepare the bismuth yellow hybrid pigment. To pairThe sample is marked S-2, whichL * 、a * 、b * The color values are shown in Table 1.
EXAMPLE III
Putting 40 g of halloysite, 30 g of kaolinite, 93.19 g of bismuth oxide, 70.95 g of bismuth chloride and 143.30 g of ammonium metavanadate into an incongruous internal rotating double-screw extruder to extrude to obtain a precursor, crystallizing at the high temperature of 700 ℃ for 30 min, and crushing to obtain the bismuth yellow hybrid pigment. The corresponding sample is marked S-3, whichL * 、a * 、b * The color values are shown in Table 1.
Example four
30 g of illite, 25 g of montmorillonite, 48.5 g of bismuth nitrate, 23.30 g of bismuth oxide, 43.61 g of bismuth ammonium citrate, 18.29 g of sodium vanadate and 8.36 g of sodium phosphomolybdate are put into a differential homodromous rotating double-screw extruder to be extruded to prepare a precursor, and the precursor is crystallized at the high temperature of 650 ℃ for 120 min and then crushed to prepare the bismuth yellow hybrid pigment. The corresponding sample is labeled S-4, whichL * 、a * 、b * The color values are shown in Table 1.
EXAMPLE five
50 g of vermiculite, 63.07 g of bismuth chloride, 92.89 g of bismuth sulfate, 24.39 g of sodium metavanadate and 30.78 g of ammonium metavanadate are put into a double-stage double-screw extruder to be extruded to prepare a precursor, and the precursor is crystallized at the high temperature of 800 ℃ for 180min and then crushed to prepare the bismuth yellow hybrid pigment. The corresponding sample is marked S-5, whichL * 、a * 、b * The color values are shown in Table 1.
Claims (6)
1. A method for efficiently and cleanly preparing clay mineral hybrid bismuth yellow pigment comprises the steps of adding clay mineral, a bismuth source and a vanadium source into a double-screw extruder, preparing a precursor by adopting the double-screw extruder after the molybdenum source is not added or added, and crystallizing the precursor at the high temperature of 500-900 ℃ for 30-180 min to obtain the clay mineral hybrid bismuth yellow pigment.
2. The method for efficiently and cleanly preparing the clay mineral hybrid bismuth yellow pigment as claimed in claim 1, wherein the method comprises the following steps: the double-screw extruder is one of a co-rotating double-screw extruder, a differential co-rotating double-screw extruder, a counter-rotating inner double-screw extruder and a double-stage double-screw extruder.
3. The method for efficiently and cleanly preparing the clay mineral hybrid bismuth yellow pigment as claimed in claim 1, wherein the method comprises the following steps: the clay mineral is at least one of serpentine-kaolinite family, talc-pyrophyllite family, mica family, sepiolite family, smectite family, illite family, vermiculite family, chlorite family and allophane.
4. The method for efficiently and cleanly preparing the clay mineral hybrid bismuth yellow pigment as claimed in claim 1, wherein the method comprises the following steps: the bismuth source is at least one of bismuth nitrate, bismuth sulfate, bismuth chloride, bismuth acetate, bismuth oxide, sodium bismuthate, ammonium bismuth citrate, bismuth subnitrate and bismuth titanate, and the mass ratio of the bismuth source to the clay mineral is 1: 3-1: 0.05.
5. The method for efficiently and cleanly preparing the clay mineral hybrid bismuth yellow pigment as claimed in claim 1, wherein the method comprises the following steps: the vanadium source is at least one of ammonium metavanadate, sodium vanadate, potassium metavanadate, vanadium pentoxide and vanadium oxide, and the mass ratio of the bismuth source to the vanadium source is 1: 5-1: 1.
6. The method for efficiently and cleanly preparing the clay mineral hybrid bismuth yellow pigment as claimed in claim 1, wherein the method comprises the following steps: the molybdenum source is at least one of sodium molybdate, ammonium molybdate, potassium molybdate and sodium phosphomolybdate, and the mass ratio of the bismuth source to the molybdenum source is 1: 20-1: 0.25.
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| CN111662466A (en) * | 2020-06-23 | 2020-09-15 | 福建紫牛塑业科技有限责任公司 | Colorant pre-dispersion, preparation method and application thereof, and color master batch |
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- 2022-01-21 CN CN202210071218.0A patent/CN114410127A/en active Pending
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| US20070182053A1 (en) * | 2003-08-06 | 2007-08-09 | Volker Hoellein | Continuous method for the production of a pigment masterbatch |
| CN102372904A (en) * | 2010-08-13 | 2012-03-14 | 上海锦湖日丽塑料有限公司 | Preparation method for aesthetic resin for improving affinity of aluminum powder pigment |
| JP2014028947A (en) * | 2012-06-28 | 2014-02-13 | Toda Kogyo Corp | Thermal resistant yellow water-containing iron oxide pigment and manufacturing method thereof, coating material and resin composition using thermal resistant yellow water-containing iron oxide pigment |
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