CN104129813A - Method of using TiCl4 to prepare high-activity double-effect crystal seed and control titanium dioxide particle size - Google Patents
Method of using TiCl4 to prepare high-activity double-effect crystal seed and control titanium dioxide particle size Download PDFInfo
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- CN104129813A CN104129813A CN201410370858.7A CN201410370858A CN104129813A CN 104129813 A CN104129813 A CN 104129813A CN 201410370858 A CN201410370858 A CN 201410370858A CN 104129813 A CN104129813 A CN 104129813A
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Abstract
The invention provides a method of using TiCl4 to prepare a high-activity double-effect crystal seed and control titanium dioxide particle size. Specifically, the method employs TiCl4 as a raw material, a precipitate is prepared through a certain proportion and rapid neutralization of a dilute base solution, the precipitate is subjected to peptizing, curing and quenching and then is adjusted to have a proper pH value, then soluble salt compositions are removed through washing, so that the high-activity double-effect crystal seed, which is applied to hydrolysis process and calcining process of production of sulfuric-acid-process titanium dioxide, is prepared. The prepared crystal seed is uniform in particle size and high in activity, and also during application of hydrolysis of a titanium solution, by adjusting the addition amount of the seed crystal and cooperating with addition of a proper salt treating agent and control on calcining intensity, rutile type titanium dioxide with different particle sizes can be prepared, and thus the particle size demands on different products are satisfied. The preparation technology is simple, not high in equipment investment and high in operation controllability, and the prepared double-effect crystal seed is capable of producing titanium dioxide hydrate primary particles with uniform particle size, so that the uniformity of calcined product particle size is guaranteed, and optical performances and pigment performances of titanium dioxide are perfectly exhibited.
Description
Technical field
The present invention relates to titanium dioxide preparing technical field, particularly a kind of with TiCl
4for raw material preparation can facilitation of hydrolysis carrying out, the method for the conversion high reactivity double-effect seed crystal of crystal formation and the method for controlling titanium white particle diameter in the time of promoting to calcine again.
Technical background
In sulfate process titanium dioxide is produced, the hydrolysis of titanium liquid is one of production process of titanium pigment four large gordian techniquies, and hydrolysis process directly affects the quality of titanium dioxide, so hydrolysis process receives much concern.Hydrolysis process can be divided into automatic growing crystal species and the large type of plus seed two according to the generation type of crystal seed, and automatic growing crystal species or plus seed essence are all the same, before formal hydrolysis starts, must have crystal seed to exist.So-called automatic growing crystal species is that preheated dense titanium liquid is fashionable toward adding in preheated end water, formation and the preparation process that be crystal seed 2 ~ 4 minutes early stages, under the existence condition at a large amount of hot water, when dense hot titanium liquid adds fashionable generation diluting effect, make titanyl sulfate that hydrolysis formation hydrated titanium dioxide colloid occur, become later stage hydrolysis crystal seed.As for plus seed hydrolysis, colloidal tio 2 crystal seed is to prepare in advance, then joins in dense hot titanium liquid to be hydrolyzed.Therefore, the quality that the quality of crystal seed sole mass, hydrolytic process are controlled is all vital, so hydrolysis is one of gordian technique in sulfate process titanium dioxide production, and crystal seed preparation is the core technology of hydrolysis, crystal seed plays a part the nucleus (nucleus of crystal) of hydrated titanium dioxide when hydrolysis, it can not only accelerate hydrolysis reaction, and the particle diameter of hydrolytic precipitation thing, size distribution and end product quality are had to considerable influence, only have the crystal seed of high-quality performance just likely produce particle diameter evenly, the titanium white product of high optical property and high pigment performance.
Plus seed is prepared with several, domestic once used have fast in and crystal seed, in ammonia and crystal seed, in alkali and crystal seed, and the hot crystal seed being comparatively in fashion at present, these crystal seeds are in fact all with alkali or alkaline matter (such as ammoniacal liquor, sodium hydroxide, potassium hydroxide) in neutralisation of sulphuric acid titanium liquid the free acid of part to reduce titanium F value, make titanium hydrolysis generate required hydrolysis crystal seed, thisly take the crystal seed that titanium liquid prepared as raw material and tend to because itself existing a large amount of detrimental impurity (as iron in titanium liquid, chromium, manganese, vanadium etc.) pollute crystal seed, add the removal of these detrimental impurity inadequate, impurity can enter crystal seed lattice and reduce activity of crystal seed, in crystal seed making system, there is a large amount of SO simultaneously
4 2-because this dianion radius is large, the crystallite that hinders anatase titanium dioxide transforms to rutile-type, therefore these traditional crystal seeds do not have economic benefits and social benefits and (when hydrolysis, have strong facilitation of hydrolysis effect, in when calcining, there is the effect that impels unformed hydrated titanium dioxide to transform to the titanium dioxide of rutile-type again), can only in the calcination process of hydrated titanium dioxide, add again 3 ~ 5% calcining seeds and just can reach qualified rutile-type transformation efficiency.
In the pertinent literature that sulfuric acid method titanium pigment is produced at home, be generally to adopt TiCl
4production nano material and titanium sponge, publication number CN132743A, name is called < < method > > who is prepared TiO 2 sol by titanium tetrachloride, and relating to field is to produce for nano-titanium.Adopt TiCl
4as the report of hydrolysis crystal seed, so far there are no, more there is no industrial applications case.Adopt TiCl
4preparing crystal seed reports more abroad, as US3560234, US3169074A1, US2571150A1 etc., these patents are mainly mentioned the preparation method of titanium tetrachloride crystal seed, also set forth the promoter action that titanium tetrachloride crystal seed transforms rutile simultaneously, but it also needs to add a certain amount of calcining seeds when calcining, and there is no to set forth the particle diameter that how to use titanium tetrachloride crystal seed control titanium white yet.
summary of the invention
The object of the present invention is to provide a kind of with TiCl
4for the method that raw material is prepared high reactivity double-effect seed crystal and titanium white particle diameter is controlled in Producing Titanium Dioxide, be applied in sulfate process titanium dioxide production in the operation of titanium hydrolysis and calcination process process, the high reactivity double-effect seed crystal that this inventive method makes can reach the uniform hydrated titanium dioxide precursor of particle diameter by hydrolysis, when calcining, can save adding of calcining seeds simultaneously, and can pass through the adjusting of crystal seed dosage, thereby the particle diameter of control titanium white precursor reaches the needs of dissimilar titanium white product.
Use TiCl
4the method of preparing high reactivity double-effect seed crystal, comprises the following steps:
(1) with TiCl
4for raw material, thin up preparation TiOCl
2strength of solution is that 180 ~ 220g/L(is with TiO
2meter), and with the concentration sig water that is 60 ~ 80g/L by TiO
2: sig water solute mass ratio is that the proportioning of 1 ︰ 0.5 ~ 0.7 neutralizes and makes throw out fast;
(2) throw out step (1) being obtained carries out peptization under 60 ~ 90 ℃ of conditions, and slaking insulation 15 ~ 60min, obtains crystal seed colloid;
(3) crystal seed colloid step (2) being obtained carries out chilling, and cooling temperature, below 40 ℃, obtains crystal seed work in-process;
(4) the crystal seed work in-process that step (3) obtained, readjustment PH=6 ~ 9, then the solubility salt that washing is removed more than 80% makes high reactivity double-effect seed crystal.
Preferably, preparation TiOCl in step (1)
2solution, concentration is with TiO
2meter 195 ~ 205g/L, sig water is NaOH, concentration is in Na OH 65 ~ 70g/L, TiOCl
2the mass ratio of solution and NaOH dilute solution is pressed TiO
2: NaOH counts 0.64 ~ 0.66.
Preferably, the time 5-30s of step (1) neutralization.
Preferably, the time 10 ~ 15s of step (1) neutralization.
Preferably, the peptization temperature in step (2) is controlled to 85 ℃, slaking soaking time is 40min, and the peptization heating-up time is in 1 hour.
Preferably, in step (3), add dilution water chilling, dilution water add-on and crystal seed colloid are to complete in 1 ︰ Isosorbide-5-Nitrae 0min in mass ratio.
Preferably, readjustment PH=7.0 in step (3); Time was controlled in 1 hour.
TiCl
4the neutralization reaction of diluent and NaOH
Through great many of experiments, find: before neutralization reaction, need two kinds of reactant dilutions to prepare to finite concentration, the concentration of this reactant determines speed of response, and speed of response determines resultant of reaction Ti (OH)
4the size of crystal grain and homogeneity, resultant of reaction Ti (OH)
4the size of crystal grain and homogeneity directly embody activity of crystal seed.In order to obtain highly active crystal seed, control reactant concn most important.This reaction is a thermopositive reaction, carry out at normal temperatures, during reaction according to a certain percentage by the TiCl preparing
4solution joins in NaOH solution fast, and requirement is that The faster the better, guarantees neutralization reaction resultant Ti (OH)
4the homogeneity of crystal grain.Design parameter of the present invention requires: 1, TiCl
4thin up preparation TiOCl
2solution, its concentration is 180 ~ 220g/L, take 195 ~ 205g/L as optimum is (with TiO
2meter); 2, can to adopt its concentration such as ammoniacal liquor, potassium hydroxide be 60 ~ 80g/L to alkali lye, and with NaOH, 65 ~ 70g/L(is in NaOH) optimum; 3, TiOCl
2solution and NaOH dilute solution neutralization ratio are TiO
2: NaOH=1 ︰ 0.5 ~ 0.7 is with 1 ︰ 0.64 ~ 0.66(mass ratio) optimum; 4, TiOCl
2solution joins in sig water, and joining day 5 ~ 30s is optimum with 10 ~ 15s.Reaction equation is as follows:,
Peptization, slaking
The Ti (OH) that neutralization generates
4, under mechanical stirring, utilize TiCl
4with in NaOH and time unreacted complete HCl carry out peptization and add thermomaturation, make part Ti (OH)
4micelle micritization and generate the TiO with certain electric charge
2+, be adsorbed on titanic acid surfaces and make it with positive charge, to be insoluble to diluted acid, prevent that crystal seed is by the danger of sulfuric acid dissolution free in titanium liquid, and improve its activity of crystal seed.Design parameter of the present invention requires: the Ti (OH) 1, neutralization being generated
4heating is at the uniform velocity warmed up to 60 ~ 90 ℃ with 85 ℃ of optimums, and temperature-rise period completed optimum in 1 hour; 2, slaking soaking time 30 ~ 60min.The peptization reaction formula of its positive metatitanic acid is as follows:
Ti(OH)
4+2HCl?=?TiOCl
2+3H
2O
TiOCl
2=TiO
2+?+2?Cl
-
Chilling
Crystal seed colloid after slaking has formed desirable crystal particle diameter, if maintaining for a long time, this crystal at high temperature can continue to grow up, affect activity of crystal seed, therefore need to be cooling fast to it, only have by cooling mode and just can make all crystal seed grain growth paces synchronously stop, thereby to guarantee that the homogeneity of crystal seed crystallite size realizes the high reactivity of crystal seed.Can adopt the type of cooling to be: it is cooling that 1, inside adds cold water dilution; 2, the outside heat exchange mode that adopts is cooling.Two kinds of modes are carried out simultaneously, and chilling successful adds the concentration and the viscosity that have reduced crystal seed after dilution water simultaneously, for readjustment and the crystal seed washing of the pH value of lower operation brings convenience.Design parameter of the present invention requires: cooling temperature, below 40 ℃, reaches 1:1 dilution with dilution water add-on and crystal seed colloid; .40min in, complete as optimum.
Readjustment PH
Through cooled crystal seed work in-process, by slowly adding sig water to adjust back pH value, the object of readjustment pH value is to stablize the crystal formation of crystal seed, guarantees its activity of crystal seed, is convenient to the washing of crystal seed simultaneously.Design parameter of the present invention requires: readjustment PH=6 ~ 9; With readjustment PH=7 readjustment process, in 30 ~ 60min, complete as optimum.
Crystal seed washing
In crystal seed slip after readjustment PH, there is a large amount of basic metal
+and Cl
-exist, only have by the mode of washing and remove most these foreign ions, prevent these contaminating impurity crystal seeds, embody the optimum activity of crystal seed.Design parameter of the present invention requires: more than 80% soluble salt is sloughed in washing.
A kind of method of controlling titanium white particle diameter
Comprise following steps:
(1) with TiCl
4for raw material, thin up preparation TiOCl
2strength of solution is that 180 ~ 220g/L(is with TiO
2meter), and with the concentration sig water that is 60 ~ 80g/L by TiO
2: sig water solute mass ratio is that the proportioning of 1 ︰ 0.5 ~ 0.7 neutralizes and makes throw out fast;
(2) throw out step (1) being obtained carries out peptization under 60 ~ 90 ℃ of conditions, and slaking insulation 15 ~ 60min, obtains crystal seed colloid;
(3) crystal seed colloid step (2) being obtained carries out chilling, and cooling temperature, below 40 ℃, obtains crystal seed work in-process;
(4) the crystal seed work in-process that step (3) obtained, readjustment PH=6 ~ 9, then the solubility salt that washing is removed more than 80% makes high reactivity double-effect seed crystal
(5) step (4) being made to crystal seed adds de-salted water dilution and is mixed with concentration with TiO
2quality meter 30 ~ 40g/L, solution;
(6) with TiO
2quality meter, obtains solution by being 0.8 ~ 4.0% to join and need in Hydrolysis of Titanium liquid with needing Hydrolysis of Titanium liquid mass ratio by step (5), and hydrolysis obtains calcining after metatitanic acid, obtains.
Preferably, in step (6) with TiO
2quality meter, it is 3.0 ~ 4.0% or 2.0 ~ 3.0% or 0.8 ~ 2.0% with needing Hydrolysis of Titanium liquid mass ratio that step (5) is obtained to solution.
Preferably, in step (5) strength of solution with TiO
2quality meter 32 ~ 34g/L.
Allotment seed concentration
Through washing qualified crystal seed, need allocate to finite concentration the dispersion of crystal seed in titanium liquid while being unfavorable for being hydrolyzed that concentration is too high, the concentration of concentration is too low can reduce hydrolysis time titanium liquid.Therefore the allotment of seed concentration is also the link that can not despise, and must be uniformly dispersed.Design parameter of the present invention requires: 30 ~ 40g/L is (with TiO for crystal seed allotment concentration
2meter).
In the hydrolyzing process of producing at sulfate process titanium dioxide, add the high reactivity double-effect seed crystal of above-mentioned preparation, by regulating crystal seed dosage 0.8-4.0% to realize the regulation and control to titanium white product initial size.
Produce large particle diameter titanium white
When titanium hydrolysis, the high reactivity double-effect seed crystal of getting above-mentioned preparation adds in titanium liquid, and seed load is that 0.8 ~ 2.0%(crystal seed dosage refers to TiO in crystal seed
2quality with need TiO in the titanium liquid of hydrolysis
2mass ratio) keeping hydrolysis under boiling state to make metatitanic acid, metatitanic acid adds salt treatment agent after purifying to be calcined and makes rutile titanium dioxide under 960 ~ 980 ℃ of temperature condition, through scanning electron microscope method, recording median size is 0.26 ~ 0.30um; The titanium white strong covering power that present method makes, can be used as the special-purpose Producing Titanium Dioxide base-material such as automobile finish, ink of high covering power requirement.
Production moderate particle diameter titanium white
In above-mentioned a on described method basis, changing crystal seed dosage is 2.0 ~ 3.0%, other processing condition are constant, making rutile titanium dioxide, through scanning electron microscope method, to record median size be 0.21 ~ 0.25um, the titanium white that present method makes has been taken into account opacifying power and whiteness, can be used as general purpose grade Producing Titanium Dioxide base-material.
Production small particle size titanium white
In above-mentioned a on described method basis, changing crystal seed dosage is 3.0 ~ 4.0%, and other processing condition are constant, and making rutile titanium dioxide, through scanning electron microscope method, to record median size be 0.18 ~ 0.21um; The titanium white whiteness that present method makes is high, and existing blue phase can be used as high whiteness, the special-purpose Producing Titanium Dioxide base-material of the high blue plastics that require mutually.
Beneficial effect of the present invention: TiCl of the present invention
4crystal seed is the TiCl with technical grade
4for raw material, it is much pure that titanium liquid prepared by the sulfuric acid process that compares is wanted, and the preparation of crystal seed is carried out always in pure system, and whole crystal seed is substantially introduced without dianion in preparation process simultaneously, only has univalent anion (Cl
-) exist, this univalent anion is because the little crystallite that can not hinder anatase titanium dioxide of radius transforms to rutile-type, therefore it has good economic benefits and social benefits, when this economic benefits and social benefits can be saved calcining, the production process of calcining seeds (being secondary seed crystal) is saved in the use of calcining seeds in sulfate process titanium dioxide production technique.More excellent, TiCl of the present invention
4crystal seed precursor particle diameter of titanium dioxide after formed hydrated titanium dioxide and calcining by can controlled hydrolysis to the adjusting of crystal seed dosage time, realizes thereby reach the object of controlling final titanium white particle diameter.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the titanium white electron-microscope scanning figure that traditional method makes.
Fig. 3 is the titanium white electron-microscope scanning figure that the embodiment of the present invention 4 makes.
Fig. 4 is the titanium white electron-microscope scanning figure that the embodiment of the present invention 5 makes.
Fig. 5 is the titanium white electron-microscope scanning figure that the embodiment of the present invention 6 makes.
Embodiment
Embodiment 1
Get technical grade TiCl
4solution (TiCl
4content is more than 99%), under the condition of ice-water bath, be slowly added to the water and dilute, and with good stirring, not occur that white solid formation is advisable, the HCl gas of release adopts alkaline liquid to absorb.Compound concentration 195g/L is (with TiO
2meter) diluent.Get 500ml diluent, join with in well-stirred 2351ml NaOH dilute solution (NaOH content 65g/L), add in the fashionable 15s of requirement and complete, at the uniform velocity will mix material and in 60min, be heated to 60 ℃, and be incubated 30min.The cold water that adds immediately 2811ml, and cool to below 40 ℃ by circulating cooling, be controlled at cooling time in 40min, slowly add sig water (NaOH:65g/L) readjustment PH=6.5.By washing, remove more than 80% soluble salt, then it is standby that crystal seed after washing is diluted to 31g/L.
Embodiment 2
Get technical grade TiCl
4solution (TiCl
4content is in 50% left and right), under the condition of ice-water bath, be slowly added to the water and dilute, and with good stirring, not occur that white solid formation is advisable, the HCl gas of release adopts alkaline liquid to absorb.Compound concentration 205g/L is (with TiO
2meter).Get 500ml diluent, join with in well-stirred 2213ml NaOH dilute solution (NaOH content 70g/L), add in the fashionable 15s of requirement and complete, at the uniform velocity will mix material and in 60min, be heated to 90 ℃, and be incubated 30min.The cold water that adds immediately 2811ml, and cool to below 40 ℃ by circulating cooling, be controlled at cooling time in 40min, slowly add sig water (NaOH:70g/L) readjustment PH=9.0.By washing, remove more than 80% soluble salt, then it is standby that crystal seed after washing is diluted to 35g/L.
Embodiment 3
Get technical grade TiCl
4solution (TiCl
4content is in 80% left and right), under the condition of ice-water bath, be slowly added to the water and dilute, and with good stirring, not occur that white solid formation is advisable, the HCl gas of release adopts alkaline liquid to absorb.Compound concentration 200g/L is (with TiO
2meter).Get the above-mentioned diluent of 500ml, join with in well-stirred 2311ml NaOH dilute solution (NaOH content 65g/L), add in the fashionable 15s of requirement and complete, at the uniform velocity will mix material and in 60min, be heated to 85 ℃, and be incubated 30min.The cold water that adds immediately 2811ml, and cool to below 40 ℃ by circulating cooling, be controlled at cooling time in 40min, slowly add sig water (NaOH:65g/L) readjustment PH=7.0.By washing, remove more than 80% soluble salt, then it is standby that crystal seed after washing is diluted to 33g/L.
Example 4
Get 2L titanium liquid (TiO
2: 200 ~ 240g/L; F value: 1.8 ~ 2.0; Fe/TiO
2=0.28 ~ 0.32) in 1 hour, be heated to 95 ℃, add embodiment 1 to make crystal seed, crystal seed dosage 1.5% (in TiO2), crystal seed joining day 13 ~ 15min, in 20min, constant-speed heating is to boiling.When ash change occurs, in 15min, add dilution water, dilution water dosage is to guarantee TiO in system
2concentration is that 185 ~ 188g/L is advisable, and keep adding dilution water for the second time after micro-boiling 2 hours, adding the 1.5 hours dilution water time for the second time, add-on guarantees that it is 160 ~ 175g/L that hydrolysis finishes rear hydrolysis pulp density, after adding dilution water, keep micro-30min of boiling, prepared by metatitanic acid again.The metatitanic acid that hydrolysis is made, through water washing cleaning (requiring Fe content in metatitanic acid to be less than 30ppm), adds salt treatment agent phosphoric acid (to be equivalent to P before calcining
2o
50.2%), KOH(is equivalent to K
2o0.26%) and Al
2(SO
4)
3(be equivalent to Al
2o
30.28%), 960 ~ 980 ℃ of calcinings, it is 0.264um that sample records titanium white average particle size through scanning electron microscope method, and opacifying power is excellent, can be used as the special-purpose Producing Titanium Dioxide base-material such as automobile finish, ink of high covering power requirement.
Example 5
Get 2L titanium liquid (TiO
2: 200 ~ 240g/L; F value: 1.8 ~ 2.0; Fe/TiO
2=0.28 ~ 0.32) in 1 hour, be heated to 95 ℃, add embodiment 2 crystal seeds, crystal seed dosage 2.5% (in TiO2), crystal seed joining day 13 ~ 15min, in 20min, constant-speed heating is to boiling.When ash change occurs, in 15min, add dilution water, dilution water dosage is to guarantee TiO in system
2concentration is that 185 ~ 188g/L is advisable, and keep adding dilution water for the second time after micro-boiling 2 hours, adding the 1.5 hours dilution water time for the second time, add-on guarantees that it is 160 ~ 175g/L that hydrolysis finishes rear hydrolysis pulp density, after adding dilution water, keep micro-30min of boiling, prepared by metatitanic acid again.The metatitanic acid that hydrolysis is made, through water washing cleaning (requiring Fe content in metatitanic acid to be less than 30ppm), adds salt treatment agent phosphoric acid (to be equivalent to P before calcining
2o
50.2%), KOH(is equivalent to K
2o0.26%) and Al
2(SO
4)
3(be equivalent to Al
2o
30.28%), 960 ~ 980 ℃ of calcinings, it is 0.232um that sample records titanium white average particle size through scanning electron microscope method, and opacifying power is good, can be used as general purpose grade Producing Titanium Dioxide base-material.
Example 6
Get 2L titanium liquid (TiO
2: 200 ~ 240g/L; F value: 1.8 ~ 2.0; Fe/TiO
2=0.28 ~ 0.32) in 1 hour, be heated to 95 ℃, add embodiment 3 crystal seeds, crystal seed dosage 3.5% (in TiO2), crystal seed joining day 13 ~ 15min, in 20min, constant-speed heating is to boiling.When ash change occurs, in 15min, add dilution water, dilution water dosage is to guarantee TiO in system
2concentration is that 185 ~ 188g/L is advisable, and keep adding dilution water for the second time after micro-boiling 2 hours, adding the 1.5 hours dilution water time for the second time, add-on guarantees that it is 160 ~ 175g/L that hydrolysis finishes rear hydrolysis pulp density, after adding dilution water, keep micro-30min of boiling, prepared by metatitanic acid again.The metatitanic acid that hydrolysis is made, through water washing cleaning (requiring Fe content in metatitanic acid to be less than 30ppm), adds salt treatment agent phosphoric acid (to be equivalent to P before calcining
2o
50.2%), KOH(is equivalent to K
2o0.26%) and Al
2(SO
4)
3(be equivalent to Al
2o
30.28%), 960 ~ 980 ℃ of calcinings, it is 0.198um that sample records titanium white average particle size through scanning electron microscope method, and opacifying power is general, but whiteness index is high, and existing blue phase can be used as high whiteness, the special-purpose Producing Titanium Dioxide base-material of the high blue plastics that require mutually.
Table 1: the detection data of example 4,5,6
Claims (10)
1. use TiCl
4the method of preparing high reactivity double-effect seed crystal, is characterized in that, comprises the following steps:
(1) with TiCl
4for raw material, thin up preparation TiOCl
2strength of solution is that 180 ~ 220g/L(is with TiO
2meter), and with the concentration sig water that is 60 ~ 80g/L by TiO
2: sig water solute mass ratio is that the proportioning of 1 ︰ 0.5 ~ 0.7 neutralizes and makes throw out fast;
(2) throw out step (1) being obtained carries out peptization under 60 ~ 90 ℃ of conditions, and slaking insulation 15 ~ 60min, obtains crystal seed colloid;
(3) crystal seed colloid step (2) being obtained carries out chilling, and cooling temperature, below 40 ℃, obtains crystal seed work in-process;
(4) the crystal seed work in-process that step (3) obtained, readjustment PH=6 ~ 9, then the solubility salt that washing is removed more than 80% makes high reactivity double-effect seed crystal.
2. use according to claim 1 TiCl
4the method of preparing high reactivity double-effect seed crystal, is characterized in that: preparation TiOCl in step (1)
2solution, concentration is with TiO
2meter 195 ~ 205g/L, described sig water is NaOH, concentration is in Na OH quality 65 ~ 70g/L, TiOCl
2the mass ratio of solution and NaOH dilute solution is pressed TiO
2: NaOH counts 1 ︰ 0.64 ~ 0.66.
3. use according to claim 1 TiCl
4the method of preparing high reactivity double-effect seed crystal, is characterized in that: the time 5-30s of step (1) neutralization.
4. use according to claim 3 TiCl
4the method of preparing high reactivity double-effect seed crystal, is characterized in that: the time 10 ~ 15s of step (1) neutralization.
5. use according to claim 1 TiCl
4the method of preparing high reactivity double-effect seed crystal, is characterized in that: the peptization temperature in step (2) is controlled to 85 ℃, and the peptization heating-up time, slaking soaking time was 40min in 1 hour.
6. use according to claim 1 TiCl
4the method of preparing high reactivity double-effect seed crystal, is characterized in that: in step (3), add dilution water chilling, dilution water add-on and crystal seed colloid are 1:1 in mass ratio, in 40min, complete.
7. use according to claim 1 TiCl
4the method of preparing high reactivity double-effect seed crystal, is characterized in that: readjustment PH=7.0 in step (4); Time was controlled in 1 hour.
8. the method that titanium white particle diameter is controlled, is characterized in that, comprises following steps:
(1) the arbitrary crystal seed that makes of claim 1-7 is added to de-salted water dilution and is mixed with concentration with TiO
2quality meter 30 ~ 40g/L, solution;
(2) with TiO
2quality meter, obtains solution by being 0.8 ~ 4.0% to join and need in Hydrolysis of Titanium liquid with needing Hydrolysis of Titanium liquid mass ratio by step (1), and hydrolysis obtains calcining after metatitanic acid, obtains.
9. the method that a kind of titanium white particle diameter according to claim 8 is controlled, is characterized in that, in step (2) with TiO
2quality meter, obtains solution by step (5) and titanium liquid mass ratio is 3.0 ~ 4.0% or 2.0 ~ 3.0% or 0.8 ~ 2.0%.
10. the method that a kind of titanium white particle diameter according to claim 8 is controlled, is characterized in that, strength of solution is with TiO in step (1)
2quality meter 32 ~ 34g/L.
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| CN109250753A (en) * | 2018-12-10 | 2019-01-22 | 攀钢集团攀枝花钢铁研究院有限公司 | The method for preparing nano-anatase mine-titanium oxide |
| CN109943103A (en) * | 2019-04-16 | 2019-06-28 | 正太新材料科技有限责任公司 | The preparation method and applications of rutile type titanium white |
| CN110028100A (en) * | 2019-05-21 | 2019-07-19 | 四川大学 | The preparation method of the method for Production By Sulfuric Acid Process rutile titanium white and double-effect seed crystal used |
| CN112850783A (en) * | 2021-02-22 | 2021-05-28 | 安徽英特力工业工程技术有限公司 | Method for continuously producing titanium tetrachloride crystal seeds |
| CN112850782A (en) * | 2021-02-22 | 2021-05-28 | 安徽英特力工业工程技术有限公司 | Preparation system of raw materials seed crystal for inorganic chemical pigment production |
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| CN110028100A (en) * | 2019-05-21 | 2019-07-19 | 四川大学 | The preparation method of the method for Production By Sulfuric Acid Process rutile titanium white and double-effect seed crystal used |
| CN110028100B (en) * | 2019-05-21 | 2021-11-12 | 四川大学 | Method for producing rutile titanium white by sulfuric acid process and preparation method of used double-effect seed crystal |
| CN112850783A (en) * | 2021-02-22 | 2021-05-28 | 安徽英特力工业工程技术有限公司 | Method for continuously producing titanium tetrachloride crystal seeds |
| CN112850782A (en) * | 2021-02-22 | 2021-05-28 | 安徽英特力工业工程技术有限公司 | Preparation system of raw materials seed crystal for inorganic chemical pigment production |
| CN112939071A (en) * | 2021-02-22 | 2021-06-11 | 安徽英特力工业工程技术有限公司 | Preparation and storage method of titanium tetrachloride crystal seed |
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