CN110422878A - One kind preparing anatase titanium dioxide TiO by ammonium titanium fluoride2The method of powder - Google Patents
One kind preparing anatase titanium dioxide TiO by ammonium titanium fluoride2The method of powder Download PDFInfo
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- CN110422878A CN110422878A CN201910859464.0A CN201910859464A CN110422878A CN 110422878 A CN110422878 A CN 110422878A CN 201910859464 A CN201910859464 A CN 201910859464A CN 110422878 A CN110422878 A CN 110422878A
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- C01—INORGANIC CHEMISTRY
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The invention discloses one kind to prepare anatase titanium dioxide TiO by ammonium titanium fluoride2The method of powder, comprising: (1) by (NH4)2TiF6Pyrohydrolysis reaction carried out on fluidized bed, carry out pyrohydrolysis at a set temperature, remove ammonium and fluorine element therein, pyrohydrolysis product is separated by cyclone separator, obtains TiO2Subparticle and NH3, HF gas；It is connected at the top of the fluidized bed and cyclone separator；(2) to TiO2Subparticle carries out calcining transformation, obtains anatase titanium dioxide TiO2Powder.Fluid bed heat hydrolysis can promote (NH4)2TiF6Particle comes into full contact with vapor, prevents material from reacting under stacking states and agglomeration is caused to cause to react insufficient and mutually bond between particle, the flow rates risen on fluidized bed by control can control the TiO carried secretly in vapor2Grain graininess reaches to TiO2The purpose of powder product granularity control；TiO after pyrohydrolysis2Product carries out calcining transformation under the high temperature conditions, makes TiO2Product form is thoroughly changed into anatase titanium dioxide TiO2, reach the standard for preparing anatase thpe white powder.
Description
Technical field
The invention belongs to field of inorganic chemical engineering, and in particular to one kind prepares anatase titanium dioxide TiO by ammonium titanium fluoride2The side of powder
Method.
Background technique
China's preservation a large amount of titanium resource, main Types have vanadium titano-magnetite, ilmenite placer and rutile ore etc.,
Middle Panxi Diqu preservation the whole nation 90.5% titanium resource, mainly based on vanadium titano-magnetite, reserves reach 96.6 hundred million tons.Mesh
Before, realize that industrialized titanium products preparation method mainly includes method for producing gtitanium dioxide with sulphuric acid, fluidizing chlorination method and fused salt chlorimation
Method prepares TiCl4, sulfuric acid process is big in the presence of acid consumption, waste acid quantity is big, the serious problem of environmental pollution；Fluidizing chlorination method requires raw material
Middle CaO < 0.2%, MgO < 1%, and chloride residue harmless treatment is difficult, China can be used for the high-quality titanium money of fluidizing chlorination method raw material
Source amount is few, it is high to climb western titanium resource calcium-magnesium content, it is difficult to prepare fluidizing chlorination furnace charge；Fused salt chlorimation method abraum salt amount is big, abraum salt processing
It is difficult.
Fluoride process titanium dioxide technique has adaptability to raw material wide, and leaching process can realize Selectively leaching titanium elements, calcium,
The elements such as magnesium, aluminium, which remain in, to be leached in waste residue, can be used as steel-making flux after waste residue harmless treatment, and leach, hydrolysing agent energy
It recycles, it can be achieved that be conducive to environmental protection without discharge, it can having as a kind of extraction and application titanium elements from Ti-containing slag
Efficacious prescriptions method.It is prepared in titanium dioxide technique in Ti-containing slag fluoride process, (the NH prepared after titanium hydrolysis after removal of impurities4)2TiF6As
TiO2Presoma, (NH4)2TiF6In contain a large amount of ammonium ion and fluorine element, if directly progress high-temperature calcination transition, forging
(NH during burning4)2TiF6A large amount of ammonia can be decomposited, and the autoignition temperature of ammonia is 651 DEG C, ammonia is aerial easily
Firing limting concentration is 15.5%~27%, if not deviating from (NH in advance4)2TiF6In ammonium ion, then during calcining transformation
The ammonia concentration decomposited is within the scope of flammability limit, and temperature be higher than ammonia autoignition temperature when, it may occur that ammonia it is quick-fried
Fried combustion reaction, increases the risk of calcination process.And (the NH in calcination process4)2TiF6In fluorine ion meeting and titanium elements
It is combined into TiF4Gas volatilizees with exhaust gas, and a large amount of titanium elements is caused to be lost, and can reduce fluoride process titanium dioxide while polluting environment
The titanium elements rate of recovery of technique.Other than impurity content, TiO2Powder granularity size and the uniformity are also to influence titanium dioxide quality
Key factor, (NH4)2TiF6The perishable rotary kiln of a large amount of fluorine-containing materials containing ammonia can be decomposited in rotary kiln pyrohydrolysis process
Inner wall, and rotary kiln pyrohydrolysis process is difficult to and controls material size and be classified, and easily causes product particle size uneven.Cause
This, develops a kind of do not lose under the premise of titanium elements from (NH4)2TiF6De- ammonium and fluorine, the uniform anatase titanium dioxide TiO of prepared sizes2Powder
Method prepared by the industrial applications of titanium dioxide technique to Ti-containing slag fluoride process and western titanium resource utilization rate is climbed in raising has weight
The meaning wanted.
Summary of the invention
For Ti-containing slag in the prior art when fluoride process prepares titanium dioxide, titanium hydrolysis is prepared after removal of impurities
(NH4)2TiF6As preparing anatase titanium dioxide TiO2Presoma, because of (NH4)2TiF6In contain a large amount of ammonium ion and fluorine ion, In
When high-temperature calcination makes the transition, (NH4)2TiF6In ammonium ion ammonia, the spontaneous combustion of ammonia can be decomposited in high-temperature calcination transformation process
Temperature is 651 DEG C, and aerial flammability limit concentration is 15.5%~27%, if not by (NH before calcining transformation4)2TiF6In ammonium ion removal, the ammonia concentration that calcination process generates be within the scope of flammability limit, and temperature is higher than ammonia
When autoignition temperature, it may occur that the explosive combustion reaction of ammonia increases the risk of calcination process；(NH4)2TiF6In it is a large amount of
Fluorine ion can produce TiF during calcining transformation in conjunction with titanium elements4Gas causes titanium elements to be lost tight with exhaust gas volatilization
Weight pollutes environment, and influences the titanium elements rate of recovery of fluoride process titanium white technique；Other than impurity content, TiO2Powder granularity is big
The small and uniformity is also to influence the key factor of titanium dioxide quality, (NH4)2TiF6It can be decomposited in rotary kiln pyrohydrolysis process
The perishable rotary kiln inner wall of a large amount of fluorine-containing materials containing ammonia, and rotary kiln pyrohydrolysis process is difficult to and controls material size and divide
Grade, easily causes the non-uniform problem of product particle size, the purpose of the present invention is to provide one kind by (NH4)2TiF6Prepare anatase titanium dioxide
TiO2The method of powder.
In order to achieve the above object, the present invention the following technical schemes are provided:
One kind of the invention prepares anatase titanium dioxide TiO by ammonium titanium fluoride2The method of powder, comprising the following steps:
(1) by (NH4)2TiF6Pyrohydrolysis reaction carried out on fluidized bed, carry out pyrohydrolysis at a set temperature, remove
Ammonium and fluorine element therein, pyrohydrolysis product are separated by cyclone separator, obtain TiO2Subparticle and NH3、HF
Gas；
It is connected at the top of the fluidized bed and cyclone separator, fluidized bed is used for (NH4)2TiF6Pyrohydrolysis reaction and grain
Degree classification, cyclone separator are used for the separation of pyrohydrolysis product；
(2) to the TiO of removing ammonium and fluorine2Subparticle carries out calcining transformation, obtains anatase titanium dioxide TiO2Powder.
Preferred scheme, in step (1), the pyrohydrolysis temperature is 200~600 DEG C, and the time is 30~180min, water
Vapor flow rate is 0.01~5m/s.
Preferred scheme, in step (2), the calcining transformation temperature is 600~900 DEG C, and the calcining transformation time is 30
~180min.
The principle of technical solution of the present invention are as follows:
The TiO that the present invention is prepared with Ti-containing slag fluoride process titanium hydrolysis2Presoma (NH4)2TiF6It is right first for raw material
It carries out pyrohydrolysis, and main purpose is to complete (NH under conditions of lower than ammonia autoignition temperature4)2TiF6De- ammonium and defluorinate, and
The regulation of product granularity is completed by control flow rates.Specific implementation process are as follows: the vapor stream of certain flow rate is from lower part
It is passed through, (NH4)2TiF6Raw material declines in upflowing vapor stream from top to bottom after fluidized bed is added, (NH4)2TiF6In decline process
In with the vapor of rising pyrohydrolysis occurs and reacts to be changed into TiO2, (NH4)2TiF6Bulky grain, which gradually decomposes, becomes subparticle,
Then the subparticle for reaching certain grade is risen by the vapor entrainment that certain flow rate rises and is sent to cyclone separator, micro-
Fine grained and gas separate in cyclone separator, and subparticle is discharged from cyclone separator lower part, and gas is from cyclone separator
Top discharge, as shown in Figure 1.
Vapor is added in this pyrohydrolysis process, it is therefore an objective to (NH during defluorinate deamination4)2TiF6It is anti-with vapor
TiO should be produced2, prevent (NH4)2TiF6In titanium elements TiF is formed in conjunction with fluorine element4Gas, cause titanium elements loss and
Pollute environment.The chemical reaction specifically occurred is as shown in reaction (1).
(NH4)2TiF6(s)+2H2O(g)=TiO2(s)+2NH3(g)+6HF(g) (1)
Fluid bed heat hydrolysis can promote (NH4)2TiF6Particle comes into full contact with vapor, prevents material in stacking states
Lower reaction causes agglomeration to cause to react insufficient and mutually bond between particle, the vapor risen on fluidized bed by control
Flow velocity can control the TiO carried secretly in vapor2Grain graininess reaches to TiO2The purpose of product granularity control.
TiO after pyrohydrolysis2Product carries out calcining transformation under the high temperature conditions, makes TiO2Product form thoroughly changes
For anatase titanium dioxide TiO2, and keep anatase crystal crystallization complete, reach the standard for preparing anatase thpe white powder.
Detailed description of the invention
Fig. 1 is the device connection schematic diagram of pyrohydrolysis reaction process of the present invention.
Specific embodiment
A specific embodiment of the invention, but a specific embodiment of the invention are further illustrated below by embodiment
It is not limited to following embodiment.
In embodiments of the present invention, unless otherwise instructed, the means of use are the means of this field routine, the examination of use
Agent can be obtained by conventional commercial sources.
Embodiment 1
(NH4)2TiF6Pyrohydrolysis in a fluidized bed, flow rates 0.10m/s, pyrohydrolysis temperature are 400 DEG C, hot water
The solution time is 30min.TiO after pyrohydrolysis2Product calcines 60min at 800 DEG C, obtains calcined product, forges through detection
Burn the TiO that the main chemical compositions of product are 99.83%2Powder, TiO2The rate of recovery is 100%, NH4 +It is 0 with F constituent content,
Main object is mutually anatase titanium dioxide TiO2, transformation of crystal rate is 95.2%, and average grain diameter is 0.29 μm.
Embodiment 2
(NH4)2TiF6Pyrohydrolysis in a fluidized bed, flow rates 0.13m/s, pyrohydrolysis temperature are 450 DEG C, hot water
The solution time is 45min.TiO after pyrohydrolysis2Product calcines 120min at 800 DEG C, obtains calcined product, forges through detection
Burn the TiO that the main chemical compositions of product are 99.83%2Powder, TiO2The rate of recovery is 100%, NH4 +It is 0 with F constituent content,
Main object is mutually anatase titanium dioxide TiO2, transformation of crystal rate is 98.6%, and average grain diameter is 0.30 μm.
Embodiment 3
(NH4)2TiF6Pyrohydrolysis in a fluidized bed, flow rates 0.15m/s, pyrohydrolysis temperature are 450 DEG C, hot water
The solution time is 60min.TiO after pyrohydrolysis2Product calcines 120min at 850 DEG C, obtains calcined product, forges through detection
Burn the TiO that the main chemical compositions of product are 99.88%2Powder, TiO2The rate of recovery is 100%, NH4 +It is 0 with F constituent content,
Main object is mutually anatase titanium dioxide TiO2, transformation of crystal rate is 99.1%, and average grain diameter is 0.32 μm.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.To those of ordinary skill in the art, obtained improvement and change in the case where not departing from the technology of the present invention concept thereof
It changes and also should be regarded as protection scope of the present invention.
Claims (3)
1. one kind prepares anatase titanium dioxide TiO by ammonium titanium fluoride2The method of powder, which comprises the following steps:
(1) by (NH4)2TiF6Pyrohydrolysis reaction carried out on fluidized bed, carry out pyrohydrolysis at a set temperature, removing is wherein
Ammonium and fluorine element, pyrohydrolysis product separated by cyclone separator, obtains TiO2Subparticle and NH3, HF gas；
It is connected at the top of the fluidized bed and cyclone separator, fluidized bed is used for (NH4)2TiF6Pyrohydrolysis reaction and granularity point
Grade, cyclone separator are used for the separation of pyrohydrolysis product；
(2) to the TiO of removing ammonium and fluorine2Subparticle carries out calcining transformation, obtains anatase titanium dioxide TiO2Powder.
2. according to claim 1 prepare anatase titanium dioxide TiO by ammonium titanium fluoride2The method of powder, which is characterized in that step (1)
In, the pyrohydrolysis temperature is 200~600 DEG C, and the time is 30~180min, and flow rates are 0.01~5m/s.
3. according to claim 1 prepare anatase titanium dioxide TiO by ammonium titanium fluoride2The method of powder, which is characterized in that step (2)
In, the calcining transformation temperature is 600~900 DEG C, and the calcining transformation time is 30~180min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114735747A (en) * | 2022-03-16 | 2022-07-12 | 中南大学 | Method for preparing fluidized chlorination furnace charge by using titanium slag |
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| CN101376112A (en) * | 2008-09-27 | 2009-03-04 | 东华大学 | Method for preparing anatase titanic oxide sol |
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| CN105209390A (en) * | 2013-03-15 | 2015-12-30 | 水晶无机化学瑞士有限公司 | Rutile titanium dioxide nanoparticles and ordered acicular aggregates of same |
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Cited By (1)
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| CN114735747A (en) * | 2022-03-16 | 2022-07-12 | 中南大学 | Method for preparing fluidized chlorination furnace charge by using titanium slag |
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