CN116332229A - Method for regulating particle size and particle size distribution of titanium dioxide by regulating oxygen content in calcination atmosphere - Google Patents
Method for regulating particle size and particle size distribution of titanium dioxide by regulating oxygen content in calcination atmosphere Download PDFInfo
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- CN116332229A CN116332229A CN202310217871.8A CN202310217871A CN116332229A CN 116332229 A CN116332229 A CN 116332229A CN 202310217871 A CN202310217871 A CN 202310217871A CN 116332229 A CN116332229 A CN 116332229A
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention relates to a method for regulating particle size and particle size distribution of titanium dioxide by regulating oxygen content in a calcining atmosphere in a sulfuric acid process for preparing rutile titanium dioxide. Taking a meta-titanic acid filter cake after salt treatment, calcining the meta-titanic acid filter cake from room temperature to 1015-1020 ℃, adjusting the flow of a calcining atmosphere to 300mL/min, controlling the oxygen concentration to 5-16%, and controlling the rutile conversion rate of titanium dioxide to be more than 98.5% at the end of calcining. Compared with the prior art, the invention can reduce anatase TiO by adjusting the oxygen concentration in the calcining atmosphere within a certain concentration range 2 Oxygen vacancies in the crystal lattice inhibit the phase transition to rutile type, thereby affecting the growth rate of rutile titanium white powder crystal and realizing the optimization of the particle size and particle size distribution of titanium white powder base material products (calcining kiln bottom). The invention relates to a simple process control method, which takes the synergistic regulation and control of the calcination atmosphere and the salt treating agent asOptimizing TiO 2 Has guiding significance for industrial production.
Description
Technical Field
The invention relates to the technical field of sulfuric acid process titanium dioxide production, in particular to a method for regulating and controlling the particle size and particle size distribution of titanium dioxide by regulating the oxygen content in a calcination atmosphere.
Background
The rutile type titanium dioxide has the characteristics of large covering power, high decolorizing power, good weather resistance, chemical stability and the like, and is widely applied to the fields of paint, plastics, papermaking, printing ink and the like.
The traditional process for producing titanium dioxide by the sulfuric acid method comprises the following steps:
(1) Acidolysis: acidolysis reaction is carried out on the titanium concentrate and sulfuric acid to obtain titanyl sulfate;
(2) Hydrolysis: the titanyl sulfate is subjected to hydrolysis reaction to obtain metatitanic acid slurry;
(3) And (3) primary water washing: washing the hydrolyzed metatitanic acid slurry with water;
(4) Bleaching and secondary water washing: bleaching the first water washed meta-titanic acid with calcined seed crystal, and carrying out secondary water washing to obtain qualified meta-titanic acid slurry;
(5) Salt treatment: performing salt treatment and filter pressing on the qualified water-washed meta-titanic acid to obtain a filter cake before a kiln;
(6) Calcining: delivering the filter cake before the kiln into a rotary kiln for calcination to obtain titanium dioxide;
(7) Post-treatment: and carrying out organic/inorganic coating and other process treatments on the titanium dioxide to obtain a titanium dioxide finished product.
In the conventional process for producing titanium pigment by a sulfuric acid method, in the calcining process of the step (6), the meta-titanic acid is dehydrated, desulfurized and anatase TiO in a crystal form 2 To rutile type TiO 2 Crystalline form transformation of (a) and rutile TiO 2 The particles grow in four stages to form the titanium white powder base material (calcining kiln bottom). In production practice, it is found that when the calcination raw material (the particle size of the primary particles of meta-titanic acid) is changed, the morphology and the particle size distribution of the titanium dioxide particles obtained by calcination are affected, and the pigment performance of the titanium dioxide finished product is further affected. In order to obtain calcining kiln bottom material with regular morphology and uniform granularity, the addition amount of calcining crystal seeds, the addition amount of salt treating agent, the calcining time, the calcining temperature and the like are generally changed to optimize the calcining process, butThe method has the advantages that due to the fact that influence factors are more, operation is complex, adjusting and controlling difficulty is increased, and production cost of products is increased.
In order to further effectively regulate the morphology and the particle size distribution of titanium dioxide base material particles (calcined kiln lower matters) and improve the quality of titanium dioxide products, a method for regulating the particle size and the particle size distribution of the titanium dioxide base material, which is simple and convenient to operate and is more efficient, is needed.
Chinese patent CN 108358238A discloses a modifier for producing rutile by using titanium-containing blast furnace slag, which relates to the technical field of metallurgy, and comprises a rutile phase reservation, wherein in the process of preparing rutile, the modifier is used as a center for enriching titanium, so that titanium is better and more rapidly enriched into the rutile phase, and rutile with concentrated particle size distribution and high quality is formed. Firstly mixing titanium-containing blast furnace slag with rutile titanium dioxide, then introducing oxygen-containing gas at 1500-1700 ℃ for oxidation, converting low-valence titanium into tetravalent titanium, then cooling to obtain rutile-phase coagulated slag with concentrated particle size distribution, crushing the coagulated slag, grinding and screening to obtain the synthetic rutile.
The raw material of the patent CN 108358238A is high titanium slag, the preparation process is that the high titanium slag is melted into liquid state at high temperature (1500-1700 ℃), then the black titanium stone is oxidized into rutile by oxygen (the oxygen content is 30-60%), the molten rutile is solidified into solid phase by cooling, and the solidified slag is crushed and ground and then is reselected to obtain the synthetic rutile. Oxygen is a reactant in the preparation process and is used for oxidizing low-valence titanium into high-valence titanium.
Disclosure of Invention
The invention provides a method for regulating and controlling the particle size and the particle size distribution of titanium dioxide by regulating the oxygen content in the calcining atmosphere, which aims to solve the problems of complex regulating and controlling process of the particle size and the particle size distribution of titanium dioxide finished products and wider particle size distribution of products in the existing sulfuric acid method titanium dioxide preparation technology.
The invention changes the anatase TiO by utilizing the change of the oxygen concentration in the calcination atmosphere 2 Oxygen vacancies in crystal lattice control the phase transition rate to rutile type, thereby influencing the growth rate of rutile titanium dioxide crystal and realizing titanium dioxideOptimization of particle size and particle size distribution of the powder base product (calciner trim). The control method is simple, can realize the synergistic regulation and control effect of the calcination atmosphere and the salt treatment agent, and efficiently optimizes the TiO 2 Particle size and distribution thereof.
The aim of the invention can be achieved by the following technical scheme:
the invention provides a method for regulating particle size and particle size distribution of titanium dioxide by regulating calcined oxygen content, wherein in the process of preparing rutile type titanium dioxide by a sulfuric acid method, a meta-titanic acid filter cake after salt treatment is taken and calcined from room temperature to 1015-1020 ℃, the oxygen concentration in the calcining atmosphere is regulated to be 5-16%, and the rutile conversion rate of the titanium dioxide obtained by calcining is more than 98.5%.
In one embodiment of the present invention, the oxygen concentration in the calcination atmosphere is preferably high in the early stage of calcination and low in the late stage of calcination.
In one embodiment of the invention, the method for adjusting the oxygen concentration in the calcination atmosphere during the calcination process is as follows: and introducing nitrogen to adjust the oxygen content.
In one embodiment of the invention, the rate of temperature increase during calcination is: it is heated from room temperature to 900 deg.c and then from 900 deg.c to 1015-1020 deg.c, with 90min being required to raise the temperature from room temperature to 900 deg.c and 110min being required to raise the temperature from 900 deg.c to 1015-1020 deg.c.
Further preferably, in the calcination process, the oxygen concentration in the calcination atmosphere is 10-16% in the section of room temperature to 900 ℃; the oxygen concentration in the calcining atmosphere is 5-10% in the section of 900-1015-1020 ℃.
Still more preferably, the oxygen concentration in the calcination atmosphere is 15% in the calcination process at a room temperature to 900 ℃; the oxygen concentration in the calcining atmosphere is 5% in the section between 900 ℃ and 1015-1020 ℃.
In one embodiment of the invention, the flow rate of the calcination atmosphere during calcination is 200 to 400mL/min, preferably 300mL/min.
In one embodiment of the invention, the calcination is carried out in a tube furnace.
In one embodiment of the invention, the method for obtaining the meta-titanic acid filter cake after salt treatment comprises the following steps:
A. taking a filter cake qualified by bleaching and washing, pulping the filter cake by deionized water, and keeping TiO in the slurry 2 The content is 250-300 g/L;
B. and (C) adding a salt treating agent into the slurry obtained in the step (A), stirring uniformly, and carrying out suction filtration to obtain the product.
In one embodiment of the invention, the salt treatment agent is added in an amount such that K in the titanium pigment after calcination 2 The O content is 0.24-0.3%, P 2 O 5 The content is 0.16 to 0.22 percent, al 2 O 3 The content is 0.23-0.29%.
Preferably, the salt treatment agent is added in an amount such that K in the titanium pigment after calcination 2 O content is 0.27%, P 2 O 5 The content is 0.196 percent, al 2 O 3 The content is 0.260%.
In one embodiment of the present invention, the salt treatment agent is a salt of the formula P 2 O 5 Soluble phosphate reagent with mass fraction of 0.16-0.22% calculated by K 2 Soluble potassium salt reagent with mass percent of 0.24-0.3% calculated by O and Al 2 O 3 And the calculated mass fraction is 0.23-0.29% of soluble aluminum salt reagent.
In addition, the invention also relates to an operation and a method for detecting the particle size and the particle size distribution of the titanium dioxide.
In order to more conveniently control the stable product quality and reduce the influence of the meta-titanic acid base material on the calcined titanium dioxide product, the invention provides a method for realizing the regulation and control of the particle size and the particle size distribution of the titanium dioxide by adjusting the oxygen partial pressure in the calcined gas.
Unlike the scheme of patent CN 108358238A, the present invention relates to a sulfuric acid process for preparing rutile titania, and the process includes four steps of dewatering, desulfurizing, converting the meta-titanic acid as the material to form rutile titania and growing the grainsA solid phase reaction and a solid phase crystallization process, wherein the valence of titanium is not changed in the preparation process, and the anatase TiO is changed by the change of the oxygen concentration 2 The mode of action of the number of oxygen vacancies in the crystal lattice influences TiO 2 Oxygen in the present application is not a reactant, but is an influencing factor for the crystal growth rate.
At present, no report is made in the production of rutile titanium dioxide about the process of regulating the particle size and the particle size distribution of the titanium dioxide base material by regulating the oxygen concentration.
Compared with the prior art, the invention has the following advantages:
1. TiO is regulated and controlled by regulating the concentration of oxygen in the calcining atmosphere of different temperature sections in the calcining process 2 The crystal form conversion and the crystal growth rate, and the process operation is simple and convenient;
2. the addition of the salt treating agent and the addition of the calcining seed crystal can be properly reduced, so that the production cost is saved;
3. the invention adopts the synergistic regulation and control effect of the calcination atmosphere and the salt treatment agent, and has the effect of efficiently optimizing TiO 2 The particle size and the distribution thereof have guiding significance for industrial production.
Drawings
FIG. 1 is a graph showing the particle size distribution of titanium dioxide in different calcination atmospheres in examples and comparative examples.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1
The embodiment provides a method for regulating particle size and particle size distribution of titanium dioxide by regulating oxygen content in a calcination atmosphere, which comprises the following steps:
(1) Taking a bleached and secondarily washed qualified meta-titanic acid filter cake, adding deionized water, pulping the filter cake, and adjusting TiO (titanium dioxide) 2 The content is 280g/L;
(2) Adding soluble phosphate, potassium salt and aluminum salt for salt treatment, and then carrying out suction filtration to ensure K in the calcined titanium dioxide 2 O content is 0.270%, P 2 O 5 The content is 0.196%，Al 2 O 3 The content is 0.260%;
(3) Placing the filter cake in a tube furnace for calcination, and experimental calcination conditions: introducing nitrogen (oxygen content is 0) to ensure the gas flow rate to be 300ml/min; rate of temperature rise: the temperature is raised to 900 ℃ for 90min, then raised to 1020 ℃ for 110min, titanium white is obtained, the crystal form of the product is detected by XRD, and the conversion rate of rutile is calculated.
(4) The particle size and particle size distribution of the titanium dioxide powder were measured by a laser particle sizer, the measurement results are shown in Table 1, and the particle size distribution is shown in FIG. 1.
Example 2
The embodiment provides a method for regulating particle size and particle size distribution of titanium dioxide by regulating calcined oxygen content, which comprises the following steps:
(1) Taking a bleached and secondarily washed qualified meta-titanic acid filter cake, adding deionized water, pulping the filter cake, and adjusting TiO (titanium dioxide) 2 The content is 280g/L;
(2) Adding soluble phosphate, potassium salt and aluminum salt for salt treatment, and then carrying out suction filtration to ensure K in the calcined titanium dioxide 2 O content is 0.270%, P 2 O 5 The content is 0.196 percent, al 2 O 3 The content is 0.260%;
(3) Placing the filter cake into a tube furnace for calcination, and experimental calcination conditions: introducing mixed gas of oxygen and nitrogen, and ensuring the gas flow to be 300ml/min; rate of temperature rise: the temperature was raised to 900℃over a period of 90min and then to 1015℃over a period of 110min. The oxygen concentration is 5% in the room temperature-900 ℃; in the 900-1015 deg.c section, oxygen concentration is 5%. And (3) obtaining titanium dioxide, detecting the crystal form of the product by adopting XRD, and calculating the conversion rate of rutile.
(4) The particle size and particle size distribution of the titanium dioxide powder were measured by a laser particle sizer, the measurement results are shown in Table 1, and the particle size distribution is shown in FIG. 1.
Comparative example
The comparative example provides a method for regulating and controlling the particle size and the particle size distribution of titanium dioxide by regulating the content of calcined oxygen, which comprises the following steps:
(1) Taking bleached and secondarily washed qualified meta-titanic acid filter cakeDeionized water is added, the filter cake is pulped, and TiO is adjusted 2 The content is 280g/L;
(2) Adding soluble phosphate, potassium salt and aluminum salt for salt treatment, and then carrying out suction filtration to ensure K in the calcined titanium dioxide 2 O content is 0.270%, P 2 O 5 The content is 0.196 percent, al 2 O 3 The content is 0.260%;
(3) Placing the filter cake into a tube furnace for calcination, and experimental calcination conditions: introducing air and water vapor mixed gas, wherein the concentration of oxygen is about 20%, and ensuring the gas flow to be 300ml/min; rate of temperature rise: the temperature is raised to 900 ℃ for 90min, then the temperature is raised to 1015 ℃ for 110min, titanium white is obtained, the crystal form of the product is detected by XRD, and the conversion rate of rutile is calculated.
(4) The particle size and particle size distribution of the titanium dioxide base material are detected by a laser particle sizer, the detection results are shown in table 1, and the particle size distribution is shown in figure 1.
Example 3
Example 3 provides a method for preparing titanium dioxide, comprising the steps of:
(1) Taking a qualified meta-titanic acid filter cake subjected to bleaching and washing, adding deionized water, pulping the filter cake, and adjusting TiO (titanium dioxide) 2 The content is 280g/L;
(2) Adding soluble phosphate, potassium salt and aluminum salt for salt treatment, and then carrying out suction filtration to ensure K in the calcined titanium dioxide 2 O content is 0.250%, P 2 O 5 The content is 0.186%, al 2 O 3 The content is 0.240%;
(3) Placing the filter cake into a tube furnace for calcination, and experimental calcination conditions: introducing mixed gas of oxygen and nitrogen, and ensuring the gas flow to be 300ml/min; rate of temperature rise: the temperature was raised to 900℃over a period of 90min and then to 1015℃over a period of 110min. The oxygen concentration is 15% in the room temperature-900 ℃; in the 900-1015 deg.c section, oxygen concentration is 5%. And (3) obtaining titanium dioxide, detecting the crystal form of the product by adopting XRD, and calculating the conversion rate of rutile.
The particle size and particle size distribution of the titanium dioxide base material are detected by a laser particle sizer, the detection results are shown in table 1, and the particle size distribution is shown in figure 1.
Table 1 results of index detection of titanium pigment in examples and comparative examples
In table 1, the black pulp B value is a measure of whiteness, indicating the ability to appear white, which is related to the particle size distribution.
In table 1, the grain size was determined by malvern 2000.
In Table 1, the grain size distribution was measured by CSD, and the grain size distribution was characterized by (D90-D10)/D50.
The rutile conversion rate is calculated by XRD measurement and is a conventional technical means in the field.
The particle size of the titanium dioxide obtained by the method is 0.318-0.349 mu m, and the particle size distribution of the obtained titanium dioxide is more concentrated. In particular, in the case of the embodiment of example 3, i.e. in the calcination, the oxygen concentration is 15% in the section from room temperature to 900 ℃; in the 900-1015 deg.c section with 5% oxygen concentration, in the first calcining stage (room temperature-900 deg.c), high 15% oxygen concentration is adopted to reduce anatase type TiO 2 Oxygen in the crystal lattice is empty, and phase transformation from the crystal lattice to the rutile type is inhibited, so that the ordered progress of crystal transformation is ensured; in the second stage of calcination (900-1015 ℃), the oxygen concentration is reduced to 5% to ensure TiO 2 The full completion of the crystal transformation to rutile type is realized, and meanwhile, the rutile TiO is reduced 2 The growth rate of the crystal can avoid sintering among particles caused by rapid growth of the crystal. Therefore, the obtained titanium dioxide kiln has concentrated grain size and better grain size distribution, and the rutile conversion rate of the product is 98.97% under the calcining condition, which is the highest conversion rate in the implementation.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. A method for regulating and controlling the particle size and particle size distribution of titanium dioxide by regulating the oxygen content in a calcination atmosphere is characterized in that in the process for preparing rutile type titanium dioxide by a sulfuric acid method, a meta-titanic acid filter cake after salt treatment is taken and calcined from room temperature to 1015-1020 ℃, the oxygen concentration is regulated to 5-16%, the calcination is carried out according to the set temperature and time, and the rutile conversion rate of the titanium dioxide is more than 98.5% after the calcination is finished.
2. The method for controlling the particle size and the particle size distribution of titanium dioxide by adjusting the content of calcined oxygen according to claim 1, wherein the oxygen concentration in the calcination atmosphere is high in the early stage of calcination and low in the later stage of calcination in the calcination process.
3. The method for regulating particle size and particle size distribution of titanium dioxide by regulating the content of calcined oxygen according to claim 1, wherein the method for regulating the concentration of oxygen in the calcining atmosphere during the calcining process is as follows: and introducing nitrogen to adjust the oxygen content in the calcination atmosphere.
4. The method for regulating particle size and particle size distribution of titanium dioxide by regulating the content of calcined oxygen according to claim 1, wherein the temperature rising rate in the calcination process is as follows: it is heated from room temperature to 900 deg.c and then from 900 deg.c to 1015-1020 deg.c, with 90min being required to raise the temperature from room temperature to 900 deg.c and 110min being required to raise the temperature from 900 deg.c to 1015-1020 deg.c.
5. The method for regulating particle size and particle size distribution of titanium dioxide by regulating the content of calcined oxygen according to claim 4, wherein the oxygen concentration in the calcining atmosphere is 10-16% in the segment of room temperature-900 ℃ in the calcining process; the oxygen concentration in the calcining atmosphere is 5-10% in the section of 900-1015-1020 ℃.
6. The method for regulating particle size and particle size distribution of titanium dioxide by regulating the content of calcined oxygen according to claim 5, wherein the oxygen concentration in the calcining atmosphere is 15% in the calcining process at room temperature to 900 ℃; the oxygen concentration in the calcining atmosphere is 5% in the section between 900 ℃ and 1015-1020 ℃.
7. The method for regulating and controlling the particle size and the particle size distribution of titanium dioxide by regulating the content of calcined oxygen according to claim 1, wherein the flow rate of the calcining atmosphere is 200-400 mL/min, preferably 300mL/min during the calcining process.
8. The method for controlling the particle size and the particle size distribution of titanium dioxide by adjusting the content of calcined oxygen according to claim 1, wherein the calcination is performed in a tube furnace.
9. The method for regulating and controlling the particle size and the particle size distribution of titanium dioxide by regulating the content of calcined oxygen according to claim 1, wherein the method for obtaining the meta-titanic acid filter cake after salt treatment is as follows:
A. taking a filter cake qualified by bleaching and washing, pulping the filter cake by deionized water, and keeping TiO in the slurry 2 The content is 250-300 g/L;
B. and (C) adding a salt treating agent into the slurry obtained in the step (A), uniformly stirring, and carrying out suction filtration and drying to obtain the product.
10. The method for controlling particle size and particle size distribution of titanium dioxide by adjusting content of calcined oxygen according to claim 9, wherein the salt treatment agent is added in an amount such that K in the titanium dioxide after calcination 2 The O content is 0.24-0.3%, P 2 O 5 The content is 0.16 to 0.22 percent, al 2 O 3 The content is 0.23-0.29%.
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