CN104743608A - Composite titanium dioxide green synthesis technology by taking barium sulfate as inner core and equipment thereof - Google Patents
Composite titanium dioxide green synthesis technology by taking barium sulfate as inner core and equipment thereof Download PDFInfo
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- CN104743608A CN104743608A CN201310725441.3A CN201310725441A CN104743608A CN 104743608 A CN104743608 A CN 104743608A CN 201310725441 A CN201310725441 A CN 201310725441A CN 104743608 A CN104743608 A CN 104743608A
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- barium sulfate
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Abstract
The invention discloses a composite titanium dioxide green synthesis technology by taking barium sulfate as inner core and equipment thereof. The method takes a barium chloride refine preparation obtained by absorbing acidic tail gas as a barium source, takes dilute sulfuric acid as a precipitating agent, so that the barium sulfate inner core is obtained, a titanium tetrachloride solution with seed is taken as a titanium source, dilute hydrochloric acid is taken as a medium for controlling the titanium hydrolysis, barium sulfate is coated, no three wastes is discharged during a whole process; a pipeline-type reaction apparatus is employed, the prepared barium sulfate inner core morphology and particle size batch stability can be good; a coating layer formed on the barium sulfate particle surface is calcinated under 500-800 DEG C, and composite titanium dioxide with rutile content being greater than or equal to 95% can be obtained.
Description
Technical field
The present invention relates to a kind of take barium sulfate as composite titanium dioxide green synthesis process and the equipment of kernel, belongs to inorganic functional material preparing technical field.
Background technology
Titanium factory can produce acid tail gas in the process of producing titanium tetrachloride or other titanium products.The improvement of this acid tail gas generally adopts alkaline matter, and as the method that calcium hydroxide absorbs, the waste residue added value produced after neutralization is lower, causes again the secondary pollution of solid waste.Adopt technical grade barium carbonate to be absorption agent, the hydrogen chloride gas after being separated by chlorine in tail gas absorbs, then supplies the required hydrochloric acid of dissolving, dissolves gained barium chloride solution and forms bariumchloride refined liquid through removal of impurities.This not only Shi Tai factory acid tail gas be able to fully effective utilization, solve the pollution problem of tail gas, solve again the secondary pollution problem of waste residue, the utilization of resources simultaneously in Shi Tai factory production process maximizes relatively.
Bariumchloride refined liquid can be applied to many aspects, and the preparation of composite titanium dioxide is exactly one side wherein.Utilize bariumchloride refined liquid to prepare barium sulfate kernel, then this basis utilizes the hydrolysis of titanium tetrachloride form composite titanium dioxide.
The meaning of composite titanium dioxide preparation and industrialization research is that micro-nano compound (coated) both can make full use of the performance of Nano titanium dioxide, the particularly excellent properties that has of nano material, again due to some relative moderate and the resource meeting the requirement of titanium dioxide application performance is kernel, greatly can save the use of this valuable source of titanium, the utilization of resources is maximized relatively.
The kernel that composite titanium dioxide adopts has many, comprises some natural fine ores such as wilkinite, agalmatolite, kaolin.Barium sulfate is exactly one of ideal kernel.Barium sulfate has comparatively soft and oil-absorption(number), nontoxic, of light color, whiteness is high, anti-soda acid, photostabilization and good dispersity, relative inexpensiveness, can meet the requirement of titanium dioxide in some Application Areas.
Be that the preparation method of the composite titanium dioxide of kernel also has many with barium sulfate.1992, Chinese patent CN1062125A, disclosed one " the titanium dioxide method for making of using sulphate to partly replace titanium white "; 2009, Chinese patent CN101475215A disclosed " a kind of composite titanium dioxide and preparation method thereof ".Above two patents solve emphatically the problem preparing composite titanium dioxide, but technique relative complex, and do not consider the relative maximization (green) that whole process resource utilizes; Control prepared by kernel still adopts conventional method, although the pattern of barium sulfate particle, particle diameter can be accomplished to meet the demands, the lot stability of product is relatively poor; In addition be exactly crystalline structure and the acquisition thereof of coating layer, in order to obtain the coated by titanium dioxide layer of rutile-type, the temperature of roasting is 900 DEG C, and coating layer easily chaps and even hardens.
Summary of the invention
Main purpose of the present invention is just the synthesis technique considering a kind of green, realize with barium sulfate be kernel composite titanium dioxide preparation process in the relative maximization of the utilization of resources.Meanwhile, the pattern of barium sulfate kernel, particle diameter etc. can be controlled preferably, the lot stability of enhancing product performance.
The object of the present invention is achieved like this, with the bariumchloride refined liquid obtained by titanium factory absorption acid tail gas for barium source, dilute sulphuric acid is precipitation agent, obtain barium sulfate kernel, to be with the titanium tetrachloride solution of crystal seed for titanium source, dilute hydrochloric acid is the hydrolysis that medium controls titanium, coated barium sulfate, whole process three-waste free discharge; Adopt duct type reaction unit, prepared barium sulfate kernel pattern and the lot stability of particle diameter better; The coating layer that titanium is formed on barium sulfate particle surface, in 500 ~ 800 DEG C of roastings, obtains the composite titanium dioxide of rutile content >=95%.
Above-mentioned technique first it is considered that the compound of which kind of barium is barium source, the selection of precipitation agent and coated time titanium tetrachloride hydrolysising condition.Barium source selective chlorination barium refined liquid, absorbs titanium factory acid tail gas for technical grade barium carbonate and adds hydrochloric acid soln, through removal of impurities gained; The excess sulfuric acid that the dilute hydrochloric acid mother liquor that process white produces is used up wherein through a small amount of bariumchloride refined liquid, dilute hydrochloric acid be used for titanium coated time the control of titanium tetrachloride hydrolysis acidity and the deficiency of acidity when preparing bariumchloride refined liquid, a small amount of barium sulfate precipitate enters ageing reactor and merges ageing; The dilute hydrochloric acid mother liquor produced when titanium tetrachloride hydrolysis is coated can be back to equally titanium coated time the control of titanium tetrachloride hydrolysis acidity and the preparation of bariumchloride refined liquid.
The second aspect that above-mentioned technique is considered is the realization of kernel barium sulfate pattern, size controlling.The precipitation of kernel barium sulfate utilizes the principle of " outburst nucleation ", adopts duct type reaction unit.Duct type reaction unit is made up of constant pressure addition device, pipeline reactor, ageing reactor, and the latter directly can adopt conventional uncovered or band end socket reactor.Pipeline reactor is a kind of tube type precipitation reactor with special structure, energy temperature adjustment; Can make two kinds react feed liquids all the time high density, mix instantaneously; The throw out formed can speed away reactor.A kind of tube type precipitation reactor is by buncher (1), reactor outer wall (2), reactor wall (3), feed liquid A import (4), liquor inlet B(5), quick runner (6), support and bearing (7), chuck (8), heating or cooling medium import and export A(9), heating or cooling medium import and export B(10), material outlet (11) composition.The rotating speed of quick runner is 1000 ~ 10000r/min.
The third aspect that above-mentioned technique is considered is the acquisition of rutile-type crystalline structure under relative low temperature.Titanium tetrachloride heating, stir and with crystal seed, acid barium sulfate suspension liquid in hydrolysis, coated, the maturing temperature of gained coating layer is lower than 900 DEG C.
The present invention compared with prior art, advantageously: the relative maximization taking into full account the utilization of resources, both the acid tail gas of titanium factory had incidentally been solved, be beneficial to environment, be beneficial to resource, achieve again with barium sulfate be kernel composite titanium dioxide preparation process in the relative maximization of the utilization of resources.Even if all available technical grade barium carbonate of sour water that a small amount of acid gas in process and washing produce absorbs or reuse.Secondly, the principle of " outburst nucleation " is applied to this technique, adopts tube type precipitation reactor, allow reaction mass be high density all the time, to mix instantaneously, accomplished that nucleation and growth separately, the lot stability of product pattern, particle diameter is relatively better as far as possible.Finally, technique not only reduces maturing temperature, saves the energy, has relatively good covered effect simultaneously.
Accompanying drawing explanation
Fig. 1 barium sulfate is the composite titanium dioxide production technological process of kernel.
Fig. 2 prepares the reaction unit (two constant pressure addition devices are not drawn) of barium sulfate kernel.
1. ageing reactor,
2. tube type precipitation reactor.
Fig. 3 tube type precipitation reactor sectional view.1. buncher, 2. reactor outer wall, 3. reactor wall, 4. liquor inlet A, 5. liquor inlet B, 6. quick runner, 7. support and bearing, 8. chuck, 9. heating or cooling medium imports and exports A, and 10. heating or cooling medium imports and exports B, 11. material outlets.
Fig. 4 tube type precipitation reactor vertical view.
The stereoscan photograph of Fig. 5 barium sulfate kernel.
Fig. 6 composite titanium dioxide X diffracting spectrum.
Embodiment
Following examples are for illustration of the present invention.
Embodiment 1
Put into end water in advance in ageing reactor and heat, starting stirring; Tube type precipitation reactor chuck temperature control 70 DEG C; H in constant pressure addition device
2sO
4the concentration of feed liquid is 1.2 mol/L, is first advanced in tube type precipitation reactor by opening for feed (4), starts impeller (7), and rotating speed is 1000r/min, simultaneously the BaCl of 1.45 mol/L in another constant pressure addition device
2refined liquid is entered by opening for feed (5) subsequently; The BaSO generated
4precipitation is discharged rapidly by uncovered (11) of reactor bottom; H in ageing reactor
2sO
4the excessive numerical control of feed liquid is built in 10%; Enter suspension liquid 80 DEG C of insulation ageings under the condition of heating, stirring of ageing reactor, reinforced complete continuation insulation 2h.Said process repeats 6 times, and degree of confidence gets 95%, and sampling records barium sulfate
d 50it is 0.53 ± 0.02 μm.
Embodiment 2
Put into end water in advance in ageing reactor and heat, starting stirring; Tube type precipitation reactor chuck temperature control 70 DEG C; H in constant pressure addition device
2sO
4the concentration of feed liquid is 1.2 mol/L, is first advanced in tube type precipitation reactor by opening for feed (4), starts impeller (7), and rotating speed is 3000r/min, simultaneously the BaCl of 1.43 mol/L in another constant pressure addition device
2refined liquid is entered by opening for feed (5) subsequently; The BaSO generated
4precipitation is discharged rapidly by uncovered (11) of reactor bottom; H in ageing reactor
2sO
4the excessive numerical control of feed liquid is built in 20%; Enter suspension liquid 80 DEG C of insulation ageings under the condition of heating, stirring of ageing reactor, reinforced complete continuation insulation 2h.
After solid-liquid separation, gained precipitation is modulated into BaSO
4suspension liquid, makes suspension liquid hydrogen ion concentration be 1.0 mol/L; A small amount of BaCl is added in dilute hydrochloric acid mother liquor
2refined liquid, gained throw out returns the ageing stage, and dilute hydrochloric acid is for subsequent use; Be the TiCl that 0.50 mol/L is with crystal seed by concentration
4solution is slowly added drop-wise to the BaSO constantly stirred
4in suspension liquid; Heating makes reaction system heat up, and is incubated 1 h in 80 DEG C under the condition of Keep agitation; Be separated after hydrolysis is covered to complete, wash; Dilute hydrochloric acid mother liquor after being hydrolyzed is back to BaCl
2the preparation of refined liquid.
By the composite Ti O after drying treatment
22 h are calcined at 700 DEG C.
Claims (6)
1. one kind take barium sulfate as composite titanium dioxide green synthesis process and the equipment of kernel, it is characterized in that: with the bariumchloride refined liquid obtained by titanium factory absorption acid tail gas for barium source, dilute sulphuric acid is precipitation agent, obtain barium sulfate kernel, to be with the titanium tetrachloride solution of crystal seed for titanium source, dilute hydrochloric acid is the hydrolysis that medium controls titanium, coated barium sulfate, whole process three-waste free discharge; Adopt duct type reaction unit, prepared barium sulfate kernel pattern and the lot stability of particle diameter better; The coating layer that titanium is formed on barium sulfate particle surface, in 500 ~ 800 DEG C of roastings, obtains the composite titanium dioxide of rutile content >=95%.
2. by technique described in claim 1, it is characterized in that, bariumchloride refined liquid is that technical grade barium carbonate absorbs titanium factory acid tail gas and adds hydrochloric acid soln, through removal of impurities gained; The excess sulfuric acid that the dilute hydrochloric acid mother liquor that process white produces is used up wherein through a small amount of bariumchloride refined liquid, dilute hydrochloric acid be used for titanium coated time the control of titanium tetrachloride hydrolysis acidity and the deficiency of acidity when preparing bariumchloride refined liquid, a small amount of barium sulfate precipitate enters ageing reactor and merges ageing; The dilute hydrochloric acid mother liquor produced when titanium tetrachloride hydrolysis is coated be back to equally titanium coated time the control of titanium tetrachloride hydrolysis acidity and the preparation of bariumchloride refined liquid.
3. by equipment described in claim 1, it is characterized in that, duct type reaction unit is made up of constant pressure addition device, pipeline reactor, ageing reactor, and the latter directly can adopt conventional uncovered or band end socket reactor.
4. by equipment described in claim 1,3, pipeline reactor is a kind of tube type precipitation reactor with special structure, energy temperature adjustment; Can make two kinds react feed liquids all the time high density, mix instantaneously; The throw out formed can speed away reactor.
5. by equipment described in claim 1,3,4, a kind of tube type precipitation reactor is by buncher (1), reactor outer wall (2), reactor wall (3), liquor inlet A(4), liquor inlet B(5), quick runner (6), support and bearing (7), chuck (8), heating or cooling medium import and export A(9), heating or cooling medium import and export B(10), material outlet (11) composition.
6., by equipment described in claim 1,3,4,5, the rotating speed of quick runner is 1000 ~ 10000r/min.
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| CN201310725441.3A CN104743608A (en) | 2013-12-25 | 2013-12-25 | Composite titanium dioxide green synthesis technology by taking barium sulfate as inner core and equipment thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822582A (en) * | 2018-07-05 | 2018-11-16 | 刘青 | A kind of preparation method of titanium dioxide-barium sulfate composite granule pigment |
| CN113462198A (en) * | 2021-08-12 | 2021-10-01 | 佛山集美精化科技有限公司 | Method for preparing composite titanium dioxide by barium sulfate coprecipitation method |
-
2013
- 2013-12-25 CN CN201310725441.3A patent/CN104743608A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108822582A (en) * | 2018-07-05 | 2018-11-16 | 刘青 | A kind of preparation method of titanium dioxide-barium sulfate composite granule pigment |
| CN113462198A (en) * | 2021-08-12 | 2021-10-01 | 佛山集美精化科技有限公司 | Method for preparing composite titanium dioxide by barium sulfate coprecipitation method |
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Application publication date: 20150701 |
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