CN107760062B

CN107760062B - Bismuth yellow/2: 1 type silicate mineral hybrid pigment and preparation method thereof

Info

Publication number: CN107760062B
Application number: CN201711094955.8A
Authority: CN
Inventors: 牟斌; 王爱勤; 王晓雯; 汪琴; 王文波; 康玉茹; 宗莉; 朱永峰; 惠爱平
Original assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Current assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Priority date: 2017-11-09
Filing date: 2017-11-09
Publication date: 2020-11-10
Anticipated expiration: 2037-11-09
Also published as: CN107760062A

Abstract

The invention discloses a bismuth yellow/2: 1 type silicate mineral hybrid pigment and a preparation method thereof, bismuth salt is dissolved in nitric acid solution, 2:1 type silicate mineral is added, and the bismuth salt is uniformly stirred and dispersed to obtain bismuth solution containing silicate mineral; dissolving a vanadium source or/and a molybdenum source in a nitric acid aqueous solution or an alkali aqueous solution, then adding the solution into a bismuth solution containing silicate minerals, adjusting the pH = 2-9 of a reaction system, stirring and reacting at room temperature for 2-12 h to obtain yellow precipitates, filtering, washing, drying and calcining to obtain the bismuth yellow/silicate mineral hybrid pigment. According to the invention, by introducing silicate minerals, the particle size and the particle size distribution of bismuth yellow nanoparticles can be effectively controlled, and the formation of free aggregates is avoided; meanwhile, the production cost of the bismuth yellow pigment is greatly reduced, and the heat resistance of the bismuth yellow pigment is effectively improved, so that the wide application of the bismuth yellow pigment in the related fields of yellow automobile finish paint, industrial coating, plastic products, printing ink and the like is expanded.

Description

Bismuth yellow/2: 1 type silicate mineral hybrid pigment and preparation method thereof

Technical Field

The invention relates to preparation of a bismuth yellow hybrid pigment, in particular to a bismuth yellow/2: 1 type silicate mineral hybrid pigment and a preparation method thereof, belonging to the technical field of inorganic pigments.

Background

Soot, chalk, colored earth, natural iron oxide, etc. have been used as pigments since prehistoric times. Yellow is the medium-wavelength part of electromagnetic wave visible light, the wavelength of the yellow is about 570-585 nm, the spectrum is between green and orange, and the yellow is a highly visible color. Yellow pigments are therefore widely used in health and safety equipment and in danger signals, especially the traditional inorganic pigments of cadmium, chromium, lead yellow. However, in recent years, with the increasing strictness of the requirements of environmental regulations and the increasing awareness of the health and environmental protection of people, there is a need to improve the environmental safety level of inorganic pigments.

Bismuth yellow, also known as bismuth vanadate or bismuth molybdate, is a non-toxic, good-weatherability, bright-colored, high-performance, environment-friendly yellow inorganic pigment, has the same high reflectivity to light with a wavelength of 580 nm as that of yellow and chrome yellow, but has a yellow phase higher than that of chrome yellow, cadmium yellow, titanium-nickel yellow and iron oxide yellow, has excellent weather resistance, covering power and light-retaining property, and can directly replace cadmium yellow and chrome yellow without being mixed with organic pigments. Therefore, the toxic effect of the traditional yellow inorganic pigment in production and use can be fundamentally solved.

At present, the synthesis method of the bismuth yellow pigment mainly comprises a solid phase method (ZL 201310655215.2) and a chemical precipitation method (ZL 200710095910.2, ZL 201010232638.X, ZL 201210380018.X, ZL 201410014113.7). Wherein, the solid phase calcining method requires higher calcining temperature, longer reaction time and difficult control of the pigment grain diameter and the grain diameter distribution. In contrast, the chemical precipitation method overcomes the defects of the traditional solid-phase calcining method, the reactants are uniformly mixed, the prepared pigment has small particle size, and the industrial production is easy to realize. However, bismuth yellow pigments prepared by chemical precipitation methods are prone to form aggregates, which seriously affect the color properties of the pigments. In addition, compared with the traditional toxic yellow inorganic pigment, the bismuth yellow pigment has higher production cost. Therefore, the inherent defects of the existing preparation process and the production cost become bottleneck factors for restricting the development and the application of the bismuth yellow pigment. In recent years, the construction of matrix-type inorganic hybrid pigments using the principle of inorganic-inorganic hybridization has attracted much attention (CN 105199435A). In contrast, silicate minerals are the best carrier material for developing environment-friendly inorganic hybrid pigments due to the advantages of multiple types, large reserves, no toxicity, low price and the like. However, no bismuth yellow hybrid pigment is reported at present.

Disclosure of Invention

The invention aims to provide a bismuth yellow/2: 1 type silicate mineral hybrid pigment with excellent color performance and a preparation method thereof.

Mono-bismuth yellow/2: 1 type silicate mineral hybrid pigment

The preparation method of the bismuth yellow/2: 1 type silicate mineral hybrid pigment comprises the steps of dissolving bismuth salt in a nitric acid solution, adding 2:1 type silicate mineral, stirring and dispersing uniformly to obtain a bismuth solution containing the silicate mineral; dissolving a vanadium source or/and a molybdenum source in a nitric acid aqueous solution or an alkali aqueous solution, then adding the solution into a bismuth solution containing silicate minerals, adjusting the pH = 2-9 of a reaction system, stirring and reacting at room temperature for 2-12 h to obtain yellow precipitates, filtering, washing and drying to obtain the bismuth yellow/silicate mineral hybrid pigment.

In order to further adjust the hue of the obtained hybrid pigment, the bismuth yellow/silicate mineral hybrid pigment is calcined at 300-800 ℃ for 0.5-3 h.

The bismuth salt is at least one of bismuth nitrate, bismuth sulfate, bismuth chloride and bismuth acetate, and the mass of the bismuth salt is 0.5-20 times of that of the 2:1 type silicate mineral. The concentration of the nitric acid solution for dissolving the bismuth salt is too low to effectively prevent Bi³⁺Hydrolysis of (2); the concentration is too high, the acid consumption and the pollution are large, and meanwhile, the anticorrosive requirement on industrial equipment is high and the realization is difficult. Experiments show that the concentration of the nitric acid solution for dissolving the bismuth salt is 0.01-5 mol.L^-1Most preferably.

The 2:1 type silicate mineral is at least one of attapulgite, sepiolite, montmorillonite, mica, vermiculite, pyrophyllite, talc and chlorite. Wherein, the attapulgite-sepiolite group has a layered-chain transition structure, the layered silica backbone can be seen to be formed by connecting countless double chains (palygorskite) or triple chains (sepiolite) through oxygen sharing two sides, the tips of tetrahedra (active oxygen) on the adjacent chains respectively face upwards and downwards, and the attapulgite-sepiolite group has a unique pore channel structure and is filled with zeolite water, exchangeable cations and the like. Other 2:1 type phyllosilicate minerals are classified into dioctahedral type and trioctahedral type according to the valence state of the octahedral void-filling cation, and have exchangeable cations by connecting the layers by van der waals force or ionic bond. The unique pore channel structure or exchangeable cations can effectively improve the bismuth yellow loading capacity and control the particle size and the particle size distribution of bismuth yellow particles.

The vanadium source is any one of ammonium metavanadate, sodium metavanadate or sodium vanadate, and the mass ratio of the vanadium source to the bismuth salt is 1: 1-1: 5. The molybdenum source is any one of sodium molybdate, ammonium molybdate or potassium molybdate, and the quantity ratio of the molybdenum source to the bismuth salt is 1: 20-1: 0.25. The concentration of the nitric acid aqueous solution or alkali aqueous solution for dissolving the vanadium source or/and the molybdenum source is 0.1-5 mol.L^-1. Wherein the aqueous solution of alkali is aqueous solution of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate.

Structure of bismuth yellow/2: 1 type silicate mineral hybrid pigment

The structure of the bismuth yellow/2: 1 type silicate mineral hybrid pigment is characterized by taking a bismuth yellow/attapulgite hybrid pigment as an example through an infrared spectrum, a transmission electron microscope, an X-ray diffraction spectrum and the like.

1. Infrared spectrogram

FIG. 1 shows the IR spectra of the bismuth yellow/attapulgite hybrid pigment obtained in examples I and III. 3300-3700 cm^-1、900~1100 cm^-1And 468 cm^-1Typical attapulgite characteristic absorption bands appear. At 746 cm^-1Presents VO₄ ^3-Characteristic absorption peak of (1), in 1383 cm^-1The absorption peak is due to residual NO₃ ^-Characteristic absorption peak of (1). After the attapulgite is calcined for 2 hours at 700 ℃, the main characteristic absorption peaks of the hydroxyl of the attapulgite disappear due to the removal of water adsorbed on the surface, zeolite water, dehydroxylation reaction and the like. At the same time, NO is generated in the process of calcination₃ ^-Is pyrolyzed and is located at 1383 cm^-1The absorption peak also disappeared but was 746 cm^-1Position VO₄ ^3-The characteristic absorption peak of the bismuth yellow/attapulgite hybrid pigment is not obviously changed, which shows that the prepared bismuth yellow/attapulgite hybrid pigment has good thermal stability.

2. Transmission electron microscope

FIG. 2 is the transmission electron micrograph of the original attapulgite (a) and the bismuth yellow/attapulgite hybrid pigment prepared in examples I (b) and III (c) and d. As shown in FIG. 2a, the original attapulgite has a typical rod-like morphology and a smooth surface, and the diameter and length of the rod crystal are about 10-40 nm and 200 nm-1.5 μm, respectively. Without the introduction of attapulgite, bismuth yellow produced under the same conditions was in the form of micron-sized flakes (fig. 2 b). Compared with the figure 2a, after the bismuth yellow nanoparticles are introduced, the rod crystal surface becomes rough, the bismuth yellow nanoparticles are uniformly loaded on the surface of the attapulgite, the particle size is about 10-20 nm, and free nanoparticle aggregates are not found (figure 2 c). The introduction of attapulgite is shown to effectively avoid the agglomeration phenomenon of the bismuth yellow nano particles in the preparation process. After calcination is carried out for 2 h at 700 ℃, the morphology, the particle size and the distribution of the bismuth yellow nanoparticles are not obviously changed (fig. 2 d), which shows that the prepared hybrid pigment has excellent thermal stability. Meanwhile, the introduction of attapulgite also effectively prevents the bismuth yellow nano particles from agglomerating and enlarging the grain size in the heat treatment process.

3. X-ray diffraction spectrum

FIG. 3 is the X-ray diffraction pattern of the bismuth yellow/attapulgite hybrid pigment prepared in example I and example III. As shown in the figure, in2θMonoclinic phase BiVO at angles of = 18.46 °, 28.56 °, 39.62 °, 42.16 °, 45.60 °, 46.94 °, 49.98 °, 53.04 ° and 59.66 °₄The characteristic diffraction peaks of (a) and (b) respectively correspond to the (101), (103), (-211), (105), (213), (204), (-220), (-116), (-224), (101) and (101) crystal planes. At the same time2θThe characteristic diffraction peak of attapulgite also appears at the angle of 8.44 degrees, but BiVO is generated on the surface of the attapulgite₄The nanoparticles are coated so that the diffraction peak intensities are low. In contrast, after calcination at 700 ℃ for 2 h, the characteristic diffraction peak of the attapulgite disappears, but the monoclinic phase BiVO₄The position of the characteristic diffraction peak of the crystal is not obviously changed, and meanwhile, the relative intensity is greatly improved, which shows that the crystallinity of the crystal is improved.

Color properties of bismuth yellow/2: 1 type silicate mineral hybrid pigments

CIE-L*a*b*A color parameter. The results show that all bismuth yellow/2: 1 type silicate mineral hybrids prepared according to the inventionOf colouring pigmentsb*The values were all above 75 and appeared as yellow powders. Especially after calcination treatment, itb*Above a value of 80, the appearance appears as a bright yellow color. After calcination treatment, due to BiVO₄The crystal grain crystallinity is improved, and the hybridized ions are removed, so that the color performance of the bismuth yellow/silicate mineral hybridized pigment can be effectively improved.

In summary, the present invention has the following advantages over the prior art:

1. according to the invention, by introducing the 2:1 type silicate mineral, the particle size and the particle size distribution of the bismuth yellow nanoparticles can be effectively controlled, and the formation of free aggregates is avoided; after calcination treatment, due to BiVO₄The crystal grain crystallinity is improved, and the hybridized ions are removed, so that the color performance of the bismuth yellow/silicate mineral hybridized pigment can be effectively improved;

2. by introducing the 2:1 type silicate mineral, the invention effectively improves the heat resistance of the bismuth yellow pigment, and is expected to expand the wide application of the bismuth yellow pigment in the related fields of yellow automobile finish paint, industrial coating, plastic products, printing ink and the like;

3. according to the invention, the 2:1 type silicate mineral is introduced, so that the production cost of the bismuth yellow pigment is greatly reduced, the high-valued utilization of the 1:1 type silicate mineral resource is realized, and the application field of the bismuth yellow pigment is expanded.

Drawings

FIG. 1 is an infrared spectrum of a bismuth yellow/attapulgite hybrid pigment prepared by the present invention.

FIG. 2 is a transmission electron micrograph of the bismuth yellow/attapulgite hybrid pigment prepared by the invention.

FIG. 3 is the X-ray diffraction pattern of the bismuth yellow/attapulgite hybrid pigment prepared by the invention.

Detailed Description

The preparation and properties of the inventive hybrid bismuth yellow/2: 1 silicate mineral pigments are described in more detail below by way of examples.

Example one

48.5 g of bismuth nitrate was dissolved in 250 mL of 2 mol. L^-1Then 50 g of attapulgite is added into the nitric acid solution and stirred for 1 hour. Balance18.93g of sodium vanadate are dissolved in 50 mL of 2 mol.L^-1Adding the mixed solution into a bismuth nitrate solution dispersed with attapulgite under stirring, slowly adjusting the pH value of a reaction system to 6.5 by using sodium carbonate, stirring and reacting for 8 hours at room temperature to obtain yellow precipitate, filtering, washing and drying the yellow precipitate to obtain yellow powdery bismuth yellow/attapulgite hybrid pigment which is marked as BiVO₄Attapulgite, its L, a, b color numbers are shown in Table 1.

Example two

31.5 g of bismuth chloride was dissolved in 250 mL of 1 mol. L^-1Then 60 g of sepiolite is added and stirred for 1 hour. Weighing 12.19 g of sodium metavanadate and dissolving in 50 mL of 1 mol.L^-1Adding the mixture into a bismuth chloride solution dispersed with sepiolite under stirring, slowly adjusting the pH value of a reaction system to 8.0 by using ammonia water, stirring and reacting for 6 hours at room temperature to obtain yellow precipitate, filtering, washing and drying the yellow precipitate, and calcining the yellow precipitate in a muffle furnace at 500 ℃ for 1 hour to obtain a yellow powdery bismuth yellow/sepiolite hybrid pigment marked as BiVO₄The L, a and b color values of the sepiolite-500 are shown in the table 1.

EXAMPLE III

70.61 g of bismuth sulfate was dissolved in 250 mL of 0.1 mol. L^-1Then 50 g of attapulgite is added into the nitric acid solution and stirred for 2 hours. 18.93g of sodium vanadate was dissolved in 50 mL of 0.5 mol. L^-1Adding the mixed solution into a bismuth sulfate solution dispersed with attapulgite under stirring, slowly adjusting the pH value of a reaction system to 8.5 by using sodium bicarbonate, stirring and reacting for 8 hours at room temperature to obtain yellow precipitate, filtering, washing and drying the yellow precipitate, and calcining the yellow precipitate in a muffle furnace at 700 ℃ for 2 hours to obtain bright yellow powdery bismuth yellow/attapulgite hybrid pigment marked as BiVO₄Attapulgite-700, its L, a, b color values are shown in Table 1.

Example four

48.5 g of bismuth nitrate was dissolved in 250 mL of 0.5 mol. L^-1Then 25 g of mica was added thereto and stirred for 30 min. 11.70 g of ammonium metavanadate was weighed out and dissolved in 50 mL of 1 mol. L^-1Adding the mixture into a bismuth nitrate solution dispersed with mica under stirring, and slowly adjusting with sodium hydroxideThe pH value of the reaction system is 7.0, the mixture is stirred and reacted for 4 hours at room temperature to obtain yellow precipitate, the yellow precipitate is filtered, washed and dried, and then the yellow precipitate is placed in a muffle furnace to be calcined for 1 hour at 300 ℃ to obtain yellow powdery bismuth yellow/mica hybrid pigment which is marked as BiVO₄The L, a and b color values of the mica-300 are shown in Table 1.

EXAMPLE five

63.0 g of bismuth chloride was dissolved in 250 mL of 3 mol. L^-1Then 30 g of attapulgite and 30 g of mica are added into the nitric acid solution and stirred for 1.5 h. 37.86 g of sodium vanadate is weighed out and dissolved in 50 mL of 3 mol.L^-1Adding the mixture into a bismuth chloride solution in which attapulgite and mica are dispersed under stirring, slowly adjusting the pH value of a reaction system to 3.0 by using ammonia water, stirring and reacting for 12 hours at room temperature to obtain yellow precipitate, filtering, washing and drying the yellow precipitate, and calcining the yellow precipitate in a muffle furnace at 700 ℃ for 2 hours to obtain bright yellow powdery bismuth yellow/concave-cloud hybrid pigment marked as BiVO₄The color values of the concave-cloud-700 are shown in table 1.

EXAMPLE six

48.5 g of bismuth nitrate and 70.61 g of bismuth sulfate were dissolved in 300 mL of 4 mol. L^-1Then 50 g of montmorillonite was added thereto and stirred for 2 hours. Weighing 17.55 g of ammonium metavanadate and 12.10 g of sodium molybdate, dissolving the ammonium metavanadate and the sodium molybdate in 50 mL of ammonia water, adding the mixture into a bismuth nitrate solution dispersed with montmorillonite under stirring, slowly adjusting the pH value of a reaction system to be 4.5 by adopting potassium carbonate, stirring the mixture at room temperature for 8 hours to obtain yellow precipitate, filtering, washing and drying the yellow precipitate, and calcining the yellow precipitate in a muffle furnace at 750 ℃ for 3 hours to obtain the bright yellow powdery bismuth yellow/montmorillonite hybrid pigment which is marked as BiVO₄Montmorillonite-750, whose L, a, b color values are shown in Table 1.

Claims

1. A preparation method of bismuth yellow/2: 1 type silicate mineral hybrid pigment comprises dissolving bismuth salt in nitric acid solution, adding 2:1 type silicate mineral, stirring and dispersing uniformly to obtain bismuth solution containing silicate mineral; dissolving a vanadium source or/and a molybdenum source in a nitric acid aqueous solution or an alkali aqueous solution, then adding the solution into a bismuth solution containing silicate minerals, adjusting the pH = 2-9 of a reaction system, stirring and reacting at room temperature for 2-12 h to obtain yellow precipitates, filtering, washing and drying to obtain the bismuth yellow/silicate mineral hybrid pigment; calcining the obtained bismuth yellow/silicate mineral hybrid pigment at 300-800 ℃ for 0.5-3 h to obtain bismuth yellow/2: 1 type silicate mineral hybrid pigment;

the bismuth salt is at least one of bismuth nitrate, bismuth sulfate, bismuth chloride and bismuth acetate; the concentration of the nitric acid solution for dissolving the bismuth salt is 0.1-5 mol.L^-1；

The 2:1 type silicate mineral is sepiolite, mica, vermiculite, pyrophyllite, talc and chlorite; the mass of the bismuth salt is 0.5-20 times of that of the 2:1 type silicate mineral;

the ratio of the vanadium source to the bismuth salt is 1:1 to 1:5, and the ratio of the molybdenum source to the bismuth salt is 1:20 to 1: 0.25.

2. The process for preparing bismuth yellow/2: 1 type silicate mineral hybrid pigment according to claim 1, wherein: the vanadium source is any one of ammonium metavanadate, sodium metavanadate or sodium vanadate.

3. The process for preparing bismuth yellow/2: 1 type silicate mineral hybrid pigment according to claim 1, wherein: the molybdenum source is any one of sodium molybdate, ammonium molybdate or potassium molybdate.

4. The process for preparing bismuth yellow/2: 1 type silicate mineral hybrid pigment according to claim 1, wherein: the concentration of the nitric acid aqueous solution or alkali aqueous solution for dissolving the vanadium source or/and the molybdenum source is 0.1-5 mol.L^-1。

5. The process for preparing bismuth yellow/2: 1 type silicate mineral hybrid pigment according to claim 4, wherein: the aqueous solution of the alkali is aqueous solution of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate.