CN102671520A - Titanium factory tail gas treatment method, produced titanium dioxide from tail gas and production method - Google Patents
Titanium factory tail gas treatment method, produced titanium dioxide from tail gas and production method Download PDFInfo
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- CN102671520A CN102671520A CN2012101602184A CN201210160218A CN102671520A CN 102671520 A CN102671520 A CN 102671520A CN 2012101602184 A CN2012101602184 A CN 2012101602184A CN 201210160218 A CN201210160218 A CN 201210160218A CN 102671520 A CN102671520 A CN 102671520A
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Abstract
The invention relates to a method for preparing rutile titanium dioxide from tail gas of a titanium factory, which comprises the following steps of: (1) absorbing the tail gas of the titanium factory: absorbing the tail gas of the titanium factory by water to form a solution, stopping absorbing the tail gas by the solution when the concentration of H<+> in the solution is more than or equal to 8.0mol/L to obtain an absorption liquid, and continuously absorbing the tail gas by water; (2) filtering and purifying: carrying out solid-liquid separation on the absorption liquid of the step (1) to obtain solid and solution; (3) hydrolyzing: adding H2TiO3 crystal seed into the solution of the step (2) according to the proportion of 120-170L/m<3>, heating to 72-76DEG C to react, and heating to 90-95DEG C to react, to obtain slurry; (4) carrying out solid-liquid separation: cooling the slurry obtained in the step (3) to be less than 40DEG C, and carrying out the solid-liquid separation to obtain the solid; and (5) calcining the smashed rutile titanium dioxide product. The invention further relates to the rutile titanium dioxide prepared by the method, wherein the content of the titanium dioxide is larger than 99.90%, the content of Fe is less than 10.0ppm, and the D50 is less than 0.350 micrometers. The invention further relates to the titanium factory tail gas treatment method.
Description
Technical field
The present invention relates to pollutant comprehensive regulation field, particularly relate to a kind of product and preparation method who utilizes titanium factory tail gas recycle to prepare rutile titanium dioxide.
Background technology
Titanium is widely used in Aeronautics and Astronautics and multiple industrial circle, and titanium sponge is processed titanium tetrachloride by rutile or high titanium slag through chlorination and prepared through reduction.Chloride process produces more a large amount of chloride tail gas, and TiCl wherein
4Account for 60～80%; The external general NaOH of employing absorbs and handles; The multistage water counter-current absorption of domestic general employing is produced byproduct hydrochloric acid and is carried out environmental protection treatment, because impurity contents such as titanium are higher, the market seasonal demand of adding byproduct hydrochloric acid is comparatively obvious; Environmental protecting device can not keep long-term stable operation, becomes the ubiquitous common problem of domestic titanium sponge industry.
The rutile titanium chloride is mainly used in industries such as electronics, printing ink, fiber, coating, generally by chloridising or sulfuric acid process production, does not see that flue gas reclaims the report of preparation aspect at present as yet.
The multistage water of general at present employing absorbs preparation byproduct hydrochloric acid to be handled, because impurity contents such as Ti4+ are high, the application of byproduct hydrochloric acid is restricted, and does not utilize valuable titanium resource.
Barium chloride is large material, is mainly used in the electrolytic preparation industry, and conventional production method has barium sulphide---the salt acid system, brium carbonate---salt acid system etc. utilize flue gas HCl to prepare BaCl
22H
2O has advantage of low energy consumption.(barium sulphide method, barium carbonate method all need evaporate the moisture content of bringing among a large amount of HCl after adding hydrochloric acid, and energy consumption is high)
Summary of the invention
The technical problem that the present invention solves is that titanium factory tail gas is handled, and utilizes titanium factory tail gas to produce the method for rutile titanium dioxide simultaneously.
The present invention is through titanium factory tail gas is absorbed process for producing rutile titanium dioxide product.The present invention adopts pure water to absorb the chloride tail gas of titanium factory's chloride process; Through washing, purify and to add the crystal seed preparation rutile titanium dioxide that is hydrolyzed again; Hydrolytic process produces HCl gas and recycles, and for example can use brium carbonate to absorb, and produces the industrial chlorinating titanate product; Solve the environmental issue of the chloride tail gas of titanium factory, reclaimed valuable titanium resource simultaneously.
Specifically, the present invention solves the problems of the technologies described above through following technical scheme:
The present invention provides a kind of method of utilizing titanium factory tail gas to prepare rutile titanium dioxide, comprises the steps:
(1) titanium factory tail gas absorbs: water absorbs titanium factory tail gas and forms solution, [H in solution
+Stop during]>=8.0mol/L with this solution absorption tail gas liquid that is absorbed, preferably [H in solution
+] stop during for 8.0-10.0mol/L with this solution absorption tail gas liquid that is absorbed; Back water continues to absorb tail gas; Keep the absorption liquid temperature less than 40 ℃ in the preferred absorption process, preferably keeping temperature is 35-40 ℃;
(2) filtration, purification; Step (1) liquid that is absorbed is carried out Separation of Solid and Liquid and obtains solid and solution, and Ti in the solution is measured in control
4+Concentration be 1.000-2.000mol/L; Preferably in the absorption liquid that step (1) obtains, carry out Separation of Solid and Liquid behind the adding active carbon and obtain solid and solution;
(3) hydrolysis: in the solution that step (2) obtains according to 120～170L/m
3Ratio add concentration be the H of 0.126-0.198mol/L
2TiO
3Crystal seed, after be warming up to 72～76 ℃ of reactions, be warming up to 90～95 ℃ of reactions again, obtain slurry;
(4) Separation of Solid and Liquid: step (3) is obtained slurry be cooled to below 40 ℃, preferably be cooled to 30-40 ℃, back Separation of Solid and Liquid obtains solid and solution; And
(5) calcining is pulverized: the solid that step (4) is obtained calcines and pulverizing obtains the rutile titanium dioxide product.
Wherein, the described H of step (3)
2TiO
3Crystal seed is to prepare through following method: with TiCl
4Process Ti
4+Concentration is the solution of 1.80-2.20mol/L, this solution is joined according to the ratio of 70-90ml/L in 90～95 ℃ the water, stirs ageing; Preferred digestion time is 55-65 minute.
Wherein, Step (3) is said to be warming up to 72～76 ℃ of stirring reactions 60～80 minutes; Be warming up to 90～95 ℃ of stirring reactions again 120～150 minutes, the HCl gas that produces in the said temperature reaction process of preferred steps (3) absorbs with brium carbonate and is used to prepare barium chloride.
Wherein, in the step (2) according to 2～3kg/m
3Ratio joins active carbon in the absorption liquid; The preferred stirring reaction time is 30-60 minute.
Wherein, in step (1) the tail gas absorption process, the gas-liquid ratio is 10～12L/m
3
Wherein, the HCl gas that produces in step (3) and the step (5) absorbs with brium carbonate and is used to prepare barium chloride.
Wherein, the processing mode of solution is handled to pH value of solution 7.0～7.5 for adding alkali or basic anhydride in the step (4), preferably adds CaO to handle to pH value of solution 7.0～7.5; After carry out sedimentation and discharging.
The rutile titanium dioxide that the present invention also provides a kind of method of utilizing titanium factory tail gas to prepare rutile titanium dioxide to prepare.
Wherein, the content of titanium dioxide is greater than 99.90%, and Fe content is lower than 10.0ppm, D
50Be lower than 0.350 micron, D
10All greater than 0.170 micron, D
90All be lower than 0.870.
The present invention also provides the processing method of a kind of titanium factory tail gas, comprises the steps:
(1) titanium factory tail gas absorbs: water absorbs titanium factory tail gas and forms solution, [H in solution
+Stop during]>=8.0mol/L with this solution absorption tail gas liquid that is absorbed, preferably [H in solution
+] stop during for 8.0-10.0mol/L with this solution absorption tail gas liquid that is absorbed; Back water continues to absorb tail gas; Keep the absorption liquid temperature less than 40 ℃ in the preferred absorption process, preferably keeping temperature is 35-40 ℃;
(2) filtration, purification; Step (1) liquid that is absorbed is carried out Separation of Solid and Liquid and obtains solid and solution, measure Ti in the solution
4+Concentration be 1.000-2.000mol/L; Preferably in the absorption liquid that step (1) obtains, carry out Separation of Solid and Liquid behind the adding active carbon and obtain solid and solution;
(3) hydrolysis: in the solution that step (2) obtains according to 120～170L/m
3Ratio to add concentration be the H of 0.126-0.198mol/L
2TiO
3Seed-solution, after be warming up to 72～76 ℃ of reactions, be warming up to 90～95 ℃ of reactions again, obtain slurry;
(4) Separation of Solid and Liquid: step (3) is obtained slurry be cooled to below 40 ℃, preferably be cooled to 30-40 ℃, back Separation of Solid and Liquid obtains solid and solution; And
(5) calcining is pulverized: the solid that step (4) is obtained calcines and pulverizing obtains the rutile titanium dioxide product.
Wherein, at this exhaust gas treating method, wherein in step (1) the tail gas absorption process, the gas-liquid ratio is 10～12L/m
3
Wherein, the HCl gas that produces in step (3) and the step (5) absorbs with brium carbonate and is used to prepare barium chloride.
Beneficial effect of the present invention is following:
The present invention has avoided preparing TiO with the maturation process of chloridising and sulfuric acid process preparation
2The present invention utilizes the chloride tail gas of titanium factory to prepare rutile titanium dioxide, has reclaimed titanium resource, and solves titanium factory treating tail gas problem, and crystal seed induces Hydrolyze method to obtain high-purity sub-micron ball-type TiO
2Product.The content of titanium dioxide that obtains is very high, and impurity content wherein is lower.
The present invention's preparation utilizes the chloride tail gas of titanium factory to prepare rutile titanium dioxide, and the rutile titanium dioxide purity of preparation is higher, and particle diameter reaches sub-micron, and the titanium dioxide that obtains is subsphaeroidal.
Description of drawings:
Fig. 1: the course of reaction flow chart of one embodiment of the present invention;
Fig. 2: the course of reaction flow chart of preferred implementation of the present invention;
The specific embodiment
A kind of method of utilizing titanium factory tail gas to prepare rutile titanium dioxide comprises the steps:
(1) titanium factory tail gas absorbs: water absorbs titanium factory tail gas and forms solution, [H in solution
+Stop to absorb the liquid that is absorbed during]>=8.0mol/L, back water continues to absorb tail gas; Keep the absorption liquid temperature less than 40 ℃ in the preferred absorption process; Preferred maintenance temperature is 35-40 ℃; In the preferred tail gas absorption process, the gas-liquid ratio is 10～12L/m
3
The purpose of this step is that water absorbs titanium factory tail gas, obtains the absorption liquid of titaniferous, wherein through H in the control absorption process
+Stopping of absorbing of concentration control, the back uses new water that titanium factory tail gas is absorbed, the circulation liquid that is absorbed is used to prepare rutile titanium dioxide successively.Wherein the absorption liquid temperature is controlled at (as through methods such as heat exchanger cools off cooling) below 40 ℃, mainly is to prevent directly to generate H
2TiO
3, so that the control through condition generates the H that character such as purity meets the demands in follow-up step
2TiO
3Be 10～12L/m through control gas-liquid ratio in this step
3, can guarantee that water is comparatively complete to the absorption of titanium factory tail gas.
The reaction equation that this step takes place is following:
（TiCl
4、SiCl
4、HCl）+H
2O→Ti
4++H
4SiO
4+H
++Cl
-
(2) filtration, purification; In the absorption liquid that step (1) obtains, add adsorbent, carry out Separation of Solid and Liquid behind the stirring reaction and obtain solid and solution, Ti in the control solution
4+Concentration be 1.000-2.000mol/L; Preferably in the absorption liquid that step (1) obtains, carry out Separation of Solid and Liquid behind the adding active carbon and obtain solid and solution; Preferably according to 2～3kg/m
3Ratio joins active carbon in the absorption liquid; Preferred mixing time is 30-60 minute.
This step is to be used for adsorbing the H of absorption liquid through adding adsorbent such as active carbon, fiber filtering
4SiO
4, impurity such as tar, dust so that the impurity in the absorption liquid reduces, help obtaining the purity high product.Wherein, in this step to Ti in the solution
4+Concentration control Ti in solution
4+Concentration when being lower than 1.000mol/L, absorb Ti in the solution that obtains with other times
4+The higher relatively solution of concentration mixes, in like manner, and Ti in solution
4+Concentration when being higher than 2.000mol/L, absorb Ti in the solution that obtains with other times
4+The relatively low solution of concentration mixes, and also can make Ti through the mode that adds deionized water
4+Concentration less than 2.000mol/L.Through above-mentioned variety of way Ti the most at last
4+Concentration is controlled in the described scope.
(3) hydrolysis: in the solution that step (2) obtains according to 120～170L/m
3Ratio to add concentration be the H of 0.126-0.198mol/L
2TiO
3Seed-solution, after be warming up to 72～76 ℃ of reactions, be warming up to 90～95 ℃ of reactions again, obtain slurry.
Wherein, in a kind of specific embodiment, described H
2TiO
3Crystal seed is to prepare through following steps: with TiCl
4Process Ti
4+Concentration is the solution of 1.80-2.20mol/L, this solution is joined according to the ratio of 70-90ml/L in 90～95 ℃ the water, stirs ageing; Preferred digestion time is 55-65 minute; Preferably be warming up to 72～76 ℃ of stirring reactions 60～80 minutes, be warming up to 90～95 ℃ of stirring reactions again 120～150 minutes, the HCl gas that produces in the preferred temperature reaction process absorbs with brium carbonate and is used to prepare barium chloride.
(4) Separation of Solid and Liquid: step (3) is obtained slurry be cooled to below 40 ℃, back Separation of Solid and Liquid obtains solid and solution; Preferably the processing mode of solution is handled to pH value of solution 7.0～7.5 for adding alkali or basic anhydride, more preferably added CaO to handle to pH value of solution 7.0～7.5; After carry out sedimentation and discharging.
Above-mentioned two steps mainly are in the presence of crystal seed, absorption liquid to be carried out the heating hydrolysis prepared in reaction to obtain H
2TiO
3, wherein adopt to add H
2TiO
3Crystal seed mainly is the H that makes generation
2TiO
3Character such as purity reach requirement, be more prone to generate H simultaneously
2TiO
3Above-mentioned steps is also handled the waste gas that wherein produces etc.; The hydrogen chloride gas that step (3) is produced reclaims, and through handling the back discharging, makes the byproduct of technology of the present invention can be by reasonable use to the solution of step (4); Wherein said alkali can be NaOH, Ca (OH)
2, said basic anhydride also can be CaO, pollute through solution can not produced environment.
It is following that above-mentioned tail gas is received the reaction equation that takes place in the step:
（TiCl
4、SiCl
4、HCl）+H
2O→Ti
4++H
4SiO
4+H
++Cl
-
Specifically, the tail gas TiCl of titanium factory
4The reaction principle of using deionized water to absorb is:
TiCl
4+H
2O+HCl→Ti
4++H
++5Cl
-+H
2O
The tail gas SiCl of titanium factory
4The reaction principle of using deionized water to absorb is:
SiCl
4+4H
2O+HCl→H
4SiO
4+5H
++5Cl
-
Above-mentioned adding crystal seed posthydrolysis TiCl
4Reaction equation following:
Ti
4++H
2TiO
3+H
++4Cl
-+3H
2O→2H
2TiO
3+4HCl↑
(5) calcining is pulverized: the solid that step (4) is obtained calcines and pulverizing obtains the rutile titanium dioxide product; Preferred calcination process is earlier according to the speed rising temperature to 850 of 250 ℃/h ℃, under this temperature, keeps 0.5-1 hour, and the back is cooled to room temperature according to the speed of 300 ℃/h; Preferred grinding mode is that air-flow is pulverized.
This step is through the H to obtaining
2TiO
3Carry out heating and calcining and make it to be decomposed into titanium dioxide.In calcining and evaporation process, have hydrogen chloride gas and emit, this gas can utilize brium carbonate to absorb back preparation barium chloride and reclaim application, and this processing method is identical with the processing method of the HCl that produces in the above-mentioned step (3).
The reaction equation that above-mentioned steps takes place is following:
H
2TiO
3+H
++Cl
-→TiO
2+H
2O+HCl↑
About utilizing titanium factory tail gas to prepare in the process of rutile titanium dioxide among the present invention; A kind of embodiment is that the HCl that produces in step in the preparation process (3) and the step (5) is used through recovery; As prepare hydrochloric acid etc.; In other a kind of embodiment, the HCl that step (3) and step (5) are produced absorbs the preparation barium chloride with brium carbonate.About utilizing the method for the HCl gas generation barium chloride that titanium factory tail gas produces, the applicant has been to disclose in 201210090320.1 at the number of patent application of first to file, quotes in full to do reference here.In first to file, disclosing the method for utilizing titanium factory tail gas to produce barium chloride at this, is that 20～25% brium carbonate slip absorbs the [H in absorption liquid to the HCl in the tail gas through mass content wherein
+] reach 2.0mol/l and separate when above and obtain barium chloride.
Embodiment
Used determinator and assay method describes as follows when at first, the method for the rutile titanium dioxide that utilizes the tail gas production of titanium factory among the following embodiment and product being analyzed:
The flow of titanium factory chlorinated exhaust is 7000～10000m
3/ h (concentration expressed in percentage by volume %)
Titanium factory tail gas ingredient is following:
Mensuration about various constituent contents in the rutile titanium dioxide product analysis is inductively coupled plasma (ICP) the atomic emission spectrum mensuration through elemental analysis method.
Atomic Absorption SpectrophotometerICP: IRIS Intrepid II XSP type inductively coupled plasma atomic emission spectrometer, U.S. power & light company system.
The assay method of content of titanium dioxide is measured the content of titanium dioxide according to the content assaying method among the GB/T1706-2006.
The pH pH-value determination pH adopts PHS-3C type precision acidity meter, by Shanghai precision instrumentation manufactured.
The assay method of hydrogen ion and hydroxide ion concentration adopts conventional titration method to measure.
Ti
4+The mensuration of concentration adopts conventional oxidation-reduction method to measure.
Industry one-level TiCl
4: TiCl
4Content is 99.97%.
The mensuration of titanium dioxide product pattern: JSM-6490LV type SEM, NEC's corporate system.
Granularmetric analysis method: the particle diameter of the volume reference that records with the wet type laser method;
Particle diameter distribution tests device: 2000MU type particle diameter appearance, Britain Ma Erwen corporate system.
Embodiment 1
With reference to shown in Figure 1, utilize titanium factory tail gas to prepare the method for rutile titanium dioxide, comprise the steps:
(1) crystal seed is prepared
Get industrial one-level TiCl
470 kilograms, in cold bath, be made into Ti with deionized water
4+Concentration is the solution of 2.00mol/L, simultaneously with deionized water be heated to 93 ℃ subsequent use, under stirring condition, in the ratio of 80ml/L 2.00mol/L TiCl with preparation
4Solution is added in the subsequent use deionized water, and stir the back, and ageing obtained H in 60 minutes
2TiO
3Crystal seed is for use.
(2) tail gas absorbs
Place deionized water earlier in spray absorber, back ON cycle pump feeds titanium factory tail gas and in spray absorber, absorbs, and exhaust flow is 8000m
3/ h, control absorbs the gas-liquid ratio at 11L/m
3, control absorption liquid temperature is less than 40 ℃, when the absorption liquid temperature during greater than 40 ℃ through the heat exchanger cooling, in absorption process, monitor absorption liquid [H
+] concentration, treat [H
+Stop during]>=8.11mol/L absorbing, after tail gas switched with fresh deionized water absorb, absorption liquid gets into next-step operation.
(3) filtering and impurity removing
Powdered active carbon is pressed 2.5kg/m
3Ratio joins absorption liquid, and 45 fens kinds of stirring reaction are removed H after the filter press press filtration separates
4SiO
4With mechanical admixtures such as impurity such as tar and dust, measure [Ti with oxidation-reduction method
4+] be 1.318mol/L, abandon filter residue, clear filtrate gets into next-step operation.
(4) hydrolysis
The settled solution of a last step is pumped to wards off in the glass reactor, add the H of step (1) preparation according to every cubic metre of 130L ratio
2TiO
3Crystal seed is opened the chuck stirring and is warming up to 74 ℃ of hydrolysis 70 minutes, is warming up to 93 ℃ of stirring reactions again 135 minutes, and the HCl gas of generation is recycled.
(5) separate
Said hydrolyzed is accomplished the disposed slurry chuck and is cooled to below 35 ℃, and filter press separates, and filter cake gets into next-step operation, and CaO handles to pH value of solution 7.2 back sedimentations in the filtrating, and clear liquid discharging is abandoned residue.
(6) calcining, pulverizing
The filter cake that step (5) is obtained according to the programming rate rising temperature to 850 of 250 ℃/h ℃, kept 1 hour under this temperature earlier, and the back is cooled to room temperature according to the cooling rate of 300 ℃/h; The HCl gas that in calcination process, produces is recycled, and calcining materials obtains the rutile titanium dioxide product after air-flow is pulverized.To wherein content of titanium dioxide, various minor metallic element content and particle diameter distribute and measure, and measure the result and see table 1 to the titanium dioxide product that obtains.
Embodiment 2
With reference to shown in Figure 2, utilize titanium factory tail gas to prepare the method for rutile titanium dioxide, comprise the steps:
(1) crystal seed is prepared
Get industrial one-level TiCl
470 kilograms, in cold bath, be made into Ti with deionized water
4+Concentration is the solution of 2.00mol/L, simultaneously with deionized water be heated to 93 ℃ subsequent use, under stirring condition, in the ratio of 80ml/L 2.00mol/L TiCl with preparation
4Solution is added in the subsequent use deionized water, and stir the back, and ageing obtained H in 60 minutes
2TiO
3Crystal seed is for use.
(2) tail gas absorbs
Place deionized water earlier in spray absorber, back ON cycle pump feeds titanium factory tail gas and in spray absorber, absorbs, and exhaust flow is 8000m
3/ h, control absorbs the gas-liquid ratio at 11L/m
3, control absorption liquid temperature is less than 40 ℃, when the absorption liquid temperature during greater than 40 ℃ through the heat exchanger cooling, in absorption process, monitor absorption liquid [H
+] concentration, treat [H
+Stop during]>=9.48mol/L absorbing, after tail gas switched with fresh deionized water absorb, absorption liquid gets into next-step operation.
(3) filtering and impurity removing
Powdered active carbon is pressed 2.5kg/m
3Ratio joins absorption liquid, and 45 fens kinds of stirring reaction are removed H after the filter press press filtration separates
4SiO
4With mechanical admixtures such as impurity such as tar and dust, measure [Ti with oxidation-reduction method
4+] be 1.659mol/L, abandon filter residue, clear filtrate gets into next-step operation.
(4) hydrolysis
The settled solution of a last step is pumped to wards off in the glass reactor, add the H of step (1) preparation according to every cubic metre of 163L ratio
2TiO
3Crystal seed is opened the chuck stirring and is warming up to 74 ℃ of hydrolysis 70 minutes, is warming up to 93 ℃ of stirring reactions again 135 minutes, and the HCl gas of generation absorbs the preparation barium chloride with brium carbonate.
(5) separate
Said hydrolyzed is accomplished the disposed slurry chuck and is cooled to below 35 ℃, and filter press separates, and filter cake gets into next-step operation, and CaO handles to pH value of solution 7.2 back sedimentations in the filtrating, and clear liquid discharging is abandoned residue.
(6) calcining, pulverizing
The filter cake that step (5) is obtained according to the programming rate rising temperature to 850 of 250 ℃/h ℃, kept 1 hour under this temperature earlier, and the back is cooled to room temperature according to the cooling rate of 300 ℃/h; The HCl gas that in calcination process, produces is used BaCO
3Slurry absorbs preparation BaCl
22H
2O, calcining materials obtain the rutile titanium dioxide product after air-flow is pulverized.To wherein content of titanium dioxide, various minor metallic element content and particle diameter distribute and measure, and measure the result and see table 1 to the titanium dioxide product that obtains.
Embodiment 3
Utilize titanium factory tail gas to prepare the method for rutile titanium dioxide, comprise the steps:
(1) crystal seed is prepared
Get industrial one-level TiCl
470 kilograms, in cold bath, be made into Ti with deionized water
4+Concentration is the solution of 2.00mol/L, simultaneously with deionized water be heated to 93 ℃ subsequent use, under stirring condition, in the ratio of 80ml/L 2.00mol/L TiCl with preparation
4Solution is added in the subsequent use deionized water, and stir the back, and ageing obtained H in 60 minutes
2TiO
3Crystal seed is for use.
(2) tail gas absorbs
Place deionized water earlier in spray absorber, back ON cycle pump feeds titanium factory tail gas and in spray absorber, absorbs, and exhaust flow is 8000m
3/ h, control absorbs the gas-liquid ratio at 11L/m
3, control absorption liquid temperature is less than 40 ℃, when the absorption liquid temperature during greater than 40 ℃ through the heat exchanger cooling, in absorption process, monitor absorption liquid [H
+] concentration, treat [H
+Stop during]>=8.61mol/L absorbing, after tail gas switched with fresh deionized water absorb, absorption liquid gets into next-step operation.
(3) filtering and impurity removing
Powdered active carbon is pressed 2.5kg/m
3Ratio joins absorption liquid, and 45 fens kinds of stirring reaction are removed H after the filter press press filtration separates
4SiO
4With mechanical admixtures such as impurity such as tar and dust, measure [Ti with oxidation-reduction method
4+] be 1.507mol/L, abandon filter residue, clear filtrate gets into next-step operation.
(4) hydrolysis
The settled solution of a last step is pumped to wards off in the glass reactor, add the H of step (1) preparation according to every cubic metre of 163L ratio
2TiO
3Crystal seed is opened the chuck stirring and is warming up to 74 ℃ of hydrolysis 70 minutes, is warming up to 93 ℃ of stirring reactions again 135 minutes, and the HCl gas of generation absorbs the preparation barium chloride with brium carbonate.
(5) separate
Said hydrolyzed is accomplished the disposed slurry chuck and is cooled to below 35 ℃, and filter press separates, and filter cake gets into next-step operation, and CaO handles to pH value of solution 7.2 back sedimentations in the filtrating, and clear liquid discharging is abandoned residue.
(6) calcining, pulverizing
The filter cake that step (5) is obtained according to the programming rate rising temperature to 850 of 250 ℃/h ℃, kept 1 hour under this temperature earlier, and the back is cooled to room temperature according to the cooling rate of 300 ℃/h; The HCl gas that in calcination process, produces is used BaCO
3Slurry absorbs preparation BaCl
22H
2O, calcining materials obtain the rutile titanium dioxide product after air-flow is pulverized.To wherein content of titanium dioxide, various minor metallic element content and particle diameter distribute and measure, and measure the result and see table 1 to the titanium dioxide product that obtains.
Embodiment 4
Utilize titanium factory tail gas to prepare the method for rutile titanium dioxide, comprise the steps:
(1) crystal seed is prepared
Get industrial one-level TiCl
480 kilograms, in cold bath, be made into Ti with deionized water
4+Concentration is the solution of 1.80mol/L, simultaneously with deionized water be heated to 90 ℃ subsequent use, under stirring condition, in the ratio of 70ml/L 1.80mol/L TiCl with preparation
4Solution is added in the subsequent use deionized water, and stir the back, and ageing obtained H in 40 minutes
2TiO
3Crystal seed is for use.
(2) tail gas absorbs
Place deionized water earlier in spray absorber, back ON cycle pump feeds titanium factory tail gas and in spray absorber, absorbs, and exhaust flow is 7000m
3/ h, control absorbs the gas-liquid ratio at 10L/m
3, control absorption liquid temperature is monitored absorption liquid [H less than 35 ℃ in absorption process
+] concentration, treat [H
+Stop during]>=8.00mol/L absorbing, after tail gas switched with fresh deionized water absorb, absorption liquid gets into next-step operation.
(3) filtering and impurity removing
Powdered active carbon is pressed 2kg/m
3Ratio joins absorption liquid, and 30 fens kinds of stirring reaction are removed H after the filter press press filtration separates
4SiO
4With mechanical admixtures such as impurity such as tar and dust, measure [Ti with oxidation-reduction method
4+] be 1.000mol/L, abandon filter residue, clear filtrate gets into next-step operation.
(4) hydrolysis
The settled solution of a last step is pumped to wards off in the glass reactor, add the H of step (1) preparation according to every cubic metre of 120L ratio
2TiO
3Crystal seed is opened the chuck stirring and is warming up to 72 ℃ of hydrolysis 60 minutes, is warming up to 90 ℃ of stirring reactions again 120 minutes, and the HCl gas of generation absorbs the preparation barium chloride with brium carbonate.
(5) separate
Said hydrolyzed is accomplished the disposed slurry chuck and is cooled to below 30 ℃, and filter press separates, and filter cake gets into next-step operation, and CaO handles to pH value of solution 7.0 back sedimentations in the filtrating, and clear liquid discharging is abandoned residue.
(6) calcining, pulverizing
The filter cake that step (5) is obtained according to the programming rate rising temperature to 850 of 250 ℃/h ℃, kept 1 hour under this temperature earlier, and the back is cooled to room temperature according to the cooling rate of 300 ℃/h; The HCl gas that in calcination process, produces is used BaCO
3Slurry absorbs preparation BaCl
22H
2O, calcining materials obtain the rutile titanium dioxide product after air-flow is pulverized.To wherein content of titanium dioxide, various minor metallic element content and particle diameter distribute and measure, and measure the result and see table 1 to the titanium dioxide product that obtains.
Embodiment 5
(1) crystal seed is prepared
Get industrial one-level TiCl
4Double centner is made into Ti with deionized water in cold bath
4+Concentration is the solution of 2.20mol/L, simultaneously with deionized water be heated to 95 ℃ subsequent use, under stirring condition, in the ratio of 90ml/L 2.20mol/L TiCl with preparation
4Solution is added in the subsequent use deionized water, and stir the back, and ageing obtained H in 80 minutes
2TiO
3Crystal seed is for use.
(2) tail gas absorbs
Place deionized water earlier in spray absorber, back ON cycle pump feeds titanium factory tail gas and in spray absorber, absorbs, and exhaust flow is 10000m
3/ h, control absorbs the gas-liquid ratio at 12L/m
3, control absorption liquid temperature is less than 38 ℃, when the absorption liquid temperature during greater than 40 ℃ through the heat exchanger cooling, in absorption process, monitor absorption liquid [H
+] concentration, treat [H
+Stop during]>=10.00mol/L absorbing, after tail gas switched with fresh deionized water absorb, absorption liquid gets into next-step operation.
(3) filtering and impurity removing
Powdered active carbon is pressed 3kg/m
3Ratio joins absorption liquid, and 60 fens kinds of stirring reaction are removed H after the filter press press filtration separates
4SiO
4With mechanical admixtures such as impurity such as tar and dust, measure [Ti with oxidation-reduction method
4+] be 2.000mol/L, abandon filter residue, clear filtrate gets into next-step operation.
(4) hydrolysis
The settled solution of a last step is pumped to wards off in the glass reactor, add the H of step (1) preparation according to every cubic metre of 170L ratio
2TiO
3Crystal seed is opened the chuck stirring and is warming up to 76 ℃ of hydrolysis 80 minutes, is warming up to 95 ℃ of stirring reactions again 150 minutes, and the HCl gas of generation absorbs the preparation barium chloride with brium carbonate.
(5) separate
Said hydrolyzed is accomplished the disposed slurry chuck and is cooled to below 35 ℃, and filter press separates, and filter cake gets into next-step operation, and CaO handles to pH value of solution 7.5 back sedimentations in the filtrating, and clear liquid discharging is abandoned residue.
(6) calcining, pulverizing
The filter cake that step (5) is obtained according to the programming rate rising temperature to 850 of 250 ℃/h ℃, kept 1 hour under this temperature earlier, and the back is cooled to room temperature according to the cooling rate of 300 ℃/h; The HCl gas that in calcination process, produces is used BaCO
3Slurry absorbs preparation BaCl
22H
2O, calcining materials obtain the rutile titanium dioxide product after air-flow is pulverized.To wherein content of titanium dioxide, various minor metallic element content and particle diameter distribute and measure, and measure the result and see table 1 to the titanium dioxide product that obtains.
The rutile titanium dioxide product property that table 1 embodiment of the invention prepares is measured the result
| Project | 1 # | 2 # | 3 # | 4 # | 5 # |
| TiO 2% | 99.92 | 99.96 | 99.95 | 99.92 | 99.93 |
| K?ppm | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 |
| Na?ppm | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 |
| Ca?ppm | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 |
| Mg ppm | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 |
| Fe ppm | ＜10.0 | ＜10.0 | ＜10.0 | ＜10.0 | ＜10.0 |
| Si?ppm | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 |
| Al?ppm | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 |
| D 10μm | 0.172 | 0.177 | 0.174 | 0.175 | 0.176 |
| D 50μm | 0.331 | 0.341 | 0.337 | 0.331 | 0.340 |
| D 90μm | 0.872 | 0.864 | 0.866 | 0.860 | 0.870 |
| Pattern | Closely spherical | Closely spherical | Closely spherical | Closely spherical | Closely spherical |
Result through in the last table 1 shows; The content of the rutile titanium dioxide that the embodiment of the invention prepares is all greater than 99.2%; The product content that embodiment 2 and 3 obtains is more than 99.5%, and Na and K content are lower than 5.0ppm in the rutile titanium dioxide that embodiment 1-5 prepares, and Ca and Mg content are lower than 2.0ppm; Fe content is lower than 10.0ppm, and Si and Al content are lower than 2.0ppm; The particle diameter that embodiment 1-5 prepares rutile titanium dioxide distributes better D
50Be lower than 0.350 micron.D
10All greater than 0.170 micron, D
90All be lower than 0.870 D of part embodiment wherein
50Can reach between the 0.330-0.340 micron.Above-mentioned data show that the titanium dioxide purity of the present invention's preparation is higher, and impurity content is lower, the particle diameter narrow distribution.
Claims (12)
1. a method of utilizing titanium factory tail gas to prepare rutile titanium dioxide comprises the steps:
(1) titanium factory tail gas absorbs: water absorbs titanium factory tail gas and forms solution, [H in solution
+Stop during]>=8.0mol/L with this solution absorption tail gas liquid that is absorbed, preferably [H in solution
+] stop during for 8.0-10.0mol/L with this solution absorption tail gas liquid that is absorbed; Back water continues to absorb tail gas; Keep the absorption liquid temperature less than 40 ℃ in the preferred absorption process, preferably keeping temperature is 35-40 ℃;
(2) filtration, purification; Step (1) liquid that is absorbed is carried out Separation of Solid and Liquid and obtains solid and solution, Ti in the control solution
4+Concentration be 1.000-2.000mol/L; Preferably in the absorption liquid that step (1) obtains, carry out Separation of Solid and Liquid behind the adding active carbon and obtain solid and solution;
(3) hydrolysis: in the solution that step (2) obtains according to 120～170L/m
3Ratio to add concentration be the H of 0.126-0.198mol/L
2TiO
3Seed-solution, after be warming up to 72～76 ℃ of reactions, be warming up to 90～95 ℃ of reactions again, obtain slurry;
(4) Separation of Solid and Liquid: step (3) is obtained slurry be cooled to below 40 ℃, preferably be cooled to 30-40 ℃, back Separation of Solid and Liquid obtains solid and solution; And
(5) calcining is pulverized: the solid that step (4) is obtained calcines and pulverizing obtains the rutile titanium dioxide product.
2. the preparation method of rutile titanium dioxide according to claim 1, the wherein described H of step (3)
2TiO
3Crystal seed is to prepare through following method: with TiCl
4Process Ti
4+Concentration is the solution of 1.80-2.20mol/L, this solution is joined according to the ratio of 70-90ml/L in 90～95 ℃ the water, stirs ageing; Preferred digestion time is 55-65 minute.
3. the preparation method of rutile titanium dioxide according to claim 1 and 2, wherein step (3) is said was warming up to 72～76 ℃ of stirring reactions 60～80 minutes, was warming up to 90～95 ℃ of stirring reactions again 120～150 minutes.
4. according to the preparation method of each described rutile titanium dioxide of claim 1-3, wherein in the step (2) according to 2～3kg/m
3Ratio joins active carbon in the absorption liquid; The preferred stirring reaction time is 30-60 minute.
5. according to the preparation method of each described rutile titanium dioxide of claim 1-4, wherein in step (1) the tail gas absorption process, the gas-liquid ratio is 10～12L/m
3
6. according to the preparation method of each described rutile titanium dioxide of claim 1-5, the HCl gas that wherein produces in step (3) and the step (5) absorbs with brium carbonate and is used to prepare barium chloride.
7. according to the preparation method of each described rutile titanium dioxide of claim 1-6, wherein the processing mode of solution is handled to pH value of solution 7.0～7.5 for adding alkali or basic anhydride in the step (4), preferably adds CaO to handle to pH value of solution 7.0～7.5; After carry out sedimentation and discharging.
8. rutile titanium dioxide that each said method of utilizing titanium factory tail gas to prepare rutile titanium dioxide of claim 1-7 prepares.
9. rutile titanium dioxide according to claim 8, wherein the content of titanium dioxide is greater than 99.90%, and Fe content is lower than 10.0ppm, D
50Be lower than 0.350 micron, D
10All greater than 0.170 micron, D
90All be lower than 0.870.
10. the processing method of a titanium factory tail gas comprises the steps:
(1) titanium factory tail gas absorbs: water absorbs titanium factory tail gas and forms solution, [H in solution
+Stop during]>=8.0mol/L with this solution absorption tail gas liquid that is absorbed, preferably [H in solution
+] stop during for 8.0-10.0mol/L with this solution absorption tail gas liquid that is absorbed; Back water continues to absorb tail gas; Keep the absorption liquid temperature less than 40 ℃ in the preferred absorption process, preferably keeping temperature is 35-40 ℃;
(2) filtration, purification; Step (1) liquid that is absorbed is carried out Separation of Solid and Liquid and obtains solid and solution, measure Ti in the solution
4+Concentration be 1.000-2.000mol/L; Preferably in the absorption liquid that step (1) obtains, carry out Separation of Solid and Liquid behind the adding active carbon and obtain solid and solution;
(3) hydrolysis: in the solution that step (2) obtains according to 120～170L/m
3Ratio to add concentration be the H of 0.126-0.198mol/L
2TiO
3Seed-solution, after be warming up to 72～76 ℃ of reactions, be warming up to 90～95 ℃ of reactions again, obtain slurry;
(4) Separation of Solid and Liquid: step (3) is obtained slurry be cooled to below 40 ℃, preferably be cooled to 30-40 ℃, back Separation of Solid and Liquid obtains solid and solution; And
(5) calcining is pulverized: the solid that step (4) is obtained calcines and pulverizing obtains the rutile titanium dioxide product.
11. according to the processing method of the said titanium of claim 10 factory tail gas, wherein in step (1) the tail gas absorption process, the gas-liquid ratio is 10～12L/m
3
12. according to the processing method of claim 10 or 11 said titanium factory tail gas, the HCl gas that wherein produces in step (3) and the step (5) absorbs with brium carbonate and is used to prepare barium chloride.
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| CN113213529A (en) * | 2021-05-26 | 2021-08-06 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for producing titanium dioxide by sulfuric acid process and recycling metatitanic acid in titanium dioxide waste acid |
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