CN105602292A - Production method of special titanium dioxide pigment for automobile cathode electrophoresis coatings - Google Patents
Production method of special titanium dioxide pigment for automobile cathode electrophoresis coatings Download PDFInfo
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Abstract
The invention discloses a production method of a special titanium dioxide pigment for automobile cathode electrophoresis coatings. The method comprises the following steps: 1, preparing a slurry containing a titanium dioxide primary product; 2, diluting the slurry, and grading the diluted slurry; 3, heating the graded slurry; 4, adding an alkaline aluminum-containing compound; 5, adding an acidic aluminum-containing compound; and 6, slaking the obtained material, filtering the slaked material, washing the filtered material with water, drying the washed material, calcining the dried material, and crushing the calcined material. The sand milling and grading operations in the titanium dioxide production process are accurately controlled, and the surface of the dispersed titanium dioxide particles is coated with boehmite alumina and amorphous alumina, so the titanium dioxide pigment has good dispersibility and dispersion stability in the automobile cathode electrophoresis paints, the performances of the pigment completely meet high-grade cathode electrophoresis paints' special requirements on titanium dioxide pigments, and a technical gap of the domestic titanium dioxide pigment industry is filled.
Description
Technical field
The production technical field that the present invention relates to a kind of rutile titanium dioxide pigment, especially automobile cathode electrophoresis paint is specialBy the production method of TiO 2 pigment.
Background technology
TiO 2 pigment is best Chinese white, and it has, and whiteness is high, opacity is high, physicochemical properties are stable etc.Advantage, is widely used in the industries such as coating, plastics, papermaking. The method of commercially producing of TiO 2 pigment have sulfuric acid process andTwo kinds of techniques of chloridising, in the technique of Production By Sulfuric Acid Process TiO 2 pigment, are dissolved in ilmenite concentrate in sulfuric acid and generate with sulphurAcid oxygen titanium is main sulfate mixture, makes black titanium liquid remove the impurity such as iron in solution again through leaching, generates through hydrolysisInsoluble hydrated titanium dioxide, through further washing impurity-removing, in rotary calcining kiln, calcining generates anatase titanium dioxide or golden redStone type TiO 2 pigment. Produce in the technique of TiO 2 pigment dried titanium dioxide raw material and coke in chloridisingSend into together with chlorine in chlorination furnace, generate titanium tetrachloride, the refining titanic chloride after rectifying removal of impurities enters together with oxygenEnter in oxidation furnace, under 1100 DEG C～1500 DEG C high temperature, oxidation reaction occurs, generate rutile titanium dioxide pigment particle.
No matter be the TiO 2 pigment that sulfuric acid process or chloridising are produced, all need through surface treatment, to improve pigment grainSon in applied environment with the compatibility of resin, improve its dispersiveness, so show best covering power, gloss, whiteness,The performances such as smooth coating degree. The surface conditioning agent of TiO 2 pigment is generally divided into inorganic surface treatment agent and organic surface treatmentThe large class of agent two, inorganic surface treatment agent Main Function is dispersiveness and the weather resistance that improves TiO 2 pigment, conventional nothingMachine surface conditioning agent has aluminium oxide, zirconia, silica etc.; The Main Function of organic surface conditioning agent is to improve titanium dioxideThe affinity of titanium pigment and resin, gives the performances such as pigment is hydrophilic or hydrophobic.
Electrophoretic coating is a kind of dedicated water soluble paint that is only applicable to electrophoretic painting method, in water, can dissociate into charged waterInsoluble film forming polymer, and under DC electric field effect, swimming is separated out in its surface to opposite electrode (coated surface). According toThe difference of the electrically charged character of electrophoretic coating macromolecular resin used, electrophoretic coating is divided into anode electrophoresis dope and cathode electrophoresis dope,It is high that cathode electrophoresis dope has throwing power, and when application, coulombic efficiency is high, and film alkali resistance is strong, the advantages such as favorable anti-corrosion effect,Through becoming the paint for standard of auto industry anti-corrosion primer.
Contain the high molecular polymers such as hydroxyl, amino, ether, amide groups, through in organic acid and after form amine salt, and adopt, then be equipped with suitable pigment, fill in a form and auxiliary agent, solvent are made through grinding distribution as matrix resin with this type of amine salt resinCoating, dilute as solvent using water, form cationic aqueous solvent, nertralizer is organic acid, as formic acid, acetic acid,Lactic acid etc., to be coated with workpiece as negative electrode, to adopt the mode of electrophoretic painting to construct, thereby obtain fine and close film, shouldThe coating of kind is called cathode electrophoresis dope. The most frequently used cathode electrophoresis dope is epoxide resin type cathode electrophoresis dope, closely severalWhat year developed has epoxy acrylic, acrylic resin type cathode electrophoresis dope, and electrophoretic coating is with water as solvent, and resin majority isAlkalescent or faintly acid, so the pigment that the pigment that electrophoretic coating uses and solvent borne paint are used is different, electrophoretic coating is to faceRequiring of material is high.
The physical property of pigment, as relative density, Acidity of Aikalinity, polarity all can affect the character of cathode electrophoresis dope, is coated with at electrophoresisIn the manufacture process of material, if the physical property of pigment differs greatly, even if strong agitation also can only temporarily be dispersed in mill baseIn, long-time storage tends to occur the problems such as precipitation, loose colour, thus the pigment that electrophoretic coating is used, must be in aqueous mediumKeeping higher chemical stability. It is generally acknowledged partial hydrolysis and to isolate the pigment of divalence or polyvalent metal ion equalBe unsuitable for electrophoretic coating, it can make macromolecular resin Precipitation, after water-soluble electrolyte dissociation, compress surface of pigments existElectric double layer causes gathering, makes pigment produce precipitation, and electrolyte cell reaction aggravation also will cause electrophoresis time, causes paint filmProduce a large amount of pin holes, not only increased electrolysis, also reduced the throwing power of electrophoretic coating, meanwhile, electrolysis producesNascent oxygen also can accelerate to paint the aging of liquid. Because the solids content of electrophoretic coating tank liquor is lower, its viscosity is glutinous close to waterDegree, the corase particles in pigment easily cause tank liquor precipitation and film horizontal plane coarse, the granularity difference of pigment, electrophoretic coating existsDeposition in each plane is not identical yet, and especially the top and the bottom gap of horizontal plane is quite obvious, along with pigment granularity decentralizationImprove, the resistance of wet paint film also can improve greatly, thereby improves the throwing power of electrophoretic coating. The tree that cathode electrophoresis dope is usedFat majority is Polyamine Type, neutralizes and just can be dissolved in water with acid, so cathode electrodeposition paint can not use alkaline pigment,Or meet sour labile pigment.
Modern auto industry has high concentration, and the feature of production serialization, for the cathode electrophoresis dope of anti-corrosion functionConstruction height is continuous, and the volume of electrophoresis tank can reach more than 600 cubic metre, and the update cycle can reach more than 3 years, ifOccur quality problems, economic loss is very serious, for this reason for the requirement of automobile cathode electrophoresis paint titanium dioxide pigment specialBe close to harsh. Domestic TiO 2 pigment is produced and is started late, and product mainly concentrates on universal field, for automobile negative electrodeElectrophoretic coating field is less with the research of pigment, the domestic main dependence on import of the electrophoretic paint used TiO 2 pigment of automobile electric at present,There is the titanium dioxide pigment special trade mark for automobile cathode electrophoresis paint specially external large-scale titanium dioxide production commercial city, butThat its production Technology all holds in close confidence, at present about automobile cathode electrophoresis paint titanium dioxide pigment special aspect speciallyProfit does not have relevant report.
Summary of the invention
When granules of pigments is dispersed in liquid phase, its surface is with electric charge, and particle surface institute is electrically charged and pigment itself relevant, is also subject toThe impact of resin solution, different granules of pigments can be with different electric charges in same resin, and same pigment is at different resinsIn also can be with different electric charges. Cathode electrophoresis dope resin used is water-soluble epoxy resin, TiO 2 pigment surface electricalLotus character is most important for coating dispersion stabilization. The normally used silica of TiO 2 pigment surface treatment, at waterSurface negative charge in gonosome system, be not suitable for cathode electrophoresis dope field, and the present invention adopts the dioxy after alumina treatmentChange titanium pigment, within the scope of cathode electrophoresis dope pH value, have very strong positive charge, both met cathode electrophoresis dope to particle tableThe requirement of the positive negativity of surface charge, also can produce enough electrostatic repulsions, is conducive to the dispersion stabilization of pigment particles.
The dispersion stabilization of granules of pigments in liquid phase, except depending on the electrostatic repulsion between particle, also and pigmentIt is sterically hindered relevant that particle surface polymeric adsorbent and dispersant form, and the present invention adopts the TiO 2 pigment of alumina-coated,Surface aluminium oxide and coating resin have extremely strong affinity, pigment particles adsorption resin number, depend on surperficial hydroxylThe quantity of base, and the quantity of surface hydroxyl depends primarily on thickness and the cladding process of aluminium coating layer.
The most basic function of cathode electrophoresis dope is Corrosion Protection, very strict to the content control of chlorion, sodium ion,The anion of divalence and cation all can affect the stability of electrophoretic coating simultaneously, so electrophoretic coating is produced the ion to pigmentContent control is very strict, and the resistivity of pigment water slurry is commonly used to characterize this feature. General general purpose grade titanium dioxideThe resistivity of pigment is in 100 Europe rice left and right, electrophoretic coating with the resistivity of TiO 2 pigment be conventionally controlled at 200 Europe rice withUpper, more than even requiring to be greater than 300 Europe rice, high like this resistivity, the soluble ion content in product is extremely low. ForMeet this requirement, depend merely on extend wash time can have a strong impact on production efficiency, the inventor in long-term research work,The titania slurry of finding coated boehmite-type aluminium oxide is easy to washing, but finished product pigment in cathode electrodip painting pointLoose less stable, easily produces sedimentation, and the titania slurry of coated amorphous alumina is because clad is loose porousAnd material colloid thixotropy is very large, be difficult to washing, but because surface is more with the hydroxyl of resin-bonded, finished product pigment is at the moonDispersion stabilization in utmost point electrophoretic paint is better. For this reason, through repetition test, explored first at TiO 2 pigment surface bagCovering boehmite-type aluminium oxide provides between the space between basic weatherability and titanium dioxide primary granule for TiO 2 pigmentEvery, then be coated a small amount of amorphous alumina of one deck to improve the dispersion stabilization of TiO 2 pigment in cathode electrodip painting.
Principle based on above-mentioned and the deficiency of existing technique, the invention provides the special titanium dioxide of a kind of automobile cathode electrophoresis paintThe production method of titanium pigment, by the sand milling in accurate control titanium dioxide production process, classification process operations, coating placeManage dosage and the operating procedure of agent, prepare the method for the TiO 2 pigment that is applicable to automobile cathode electrophoresis paint, successfully solveDispersiveness, dispersion stabilization and the requirement to foreign ion of TiO 2 pigment in cathode electrophoresis dope.
In order to realize foregoing invention object, the technical solution used in the present invention is as follows:
A production method for automobile cathode electrophoresis paint titanium dioxide pigment special, comprises the steps:
(1) slurry that preparation comprises titanium dioxide first product: take 5～60kg deionized water, add dispersing aid, under agitationAdd the not rutile titanium dioxide first product of coating of 5～60kg, making concentration is 600～800gTiO2The titanium deoxide slurry of/LMaterial, then use sand mill sand milling, make titanium dioxide reach simple particle diameter;
(2) dilution, classification: use deionized water titania slurry concentration dilution to 300～400g/L qualified sand milling, thenWith hydroclone classification, the accepted stock of overflow is sent in coating groove;
(3) heating: in coating groove, the temperature of slurry is raised to 50～70 DEG C;
(4) add alkaline aluminum contained compound: adjusting slurry pH value with dilute sulfuric acid is 10.0～10.5, maintains 60～180 minutes,Add again the solution of alkaline aluminium compound in slurry, generate boehmite-type aluminium oxide coating layer, finally regulate slurry pH value extremely 5.0～8.0；
(5) add acid aluminum contained compound: adjusting slurry pH value with dilute sulfuric acid is 6.0～7.5, maintains 60～180 minutes,Add again the solution of acidic aluminum compound in slurry, generate knot amorphous alumina coating layer, then regulate slurry with sig waterPH value to 6.5～7.5;
(6) slaking, filtration, washing, dry and calcining, pulverize: through the coated titania slurry of above-mentioned steps at 50～70 DEG CStir lower slaking 60～100 minutes, after filtration, washing, then by filtration cakes torrefaction, steam flow is pulverized, and obtains automobile cathodeSwimming coating titanium dioxide pigment special.
Wherein, add dispersing aid to be selected from the one of sodium metasilicate or triethanolamine in described step (1), its addition is rutile0.1～0.4% of type titanium dioxide quality.
The concentration general control of slurry is at 600～800gTiO2In the scope of/L, so relatively high concentration is conducive to improve sandThe efficiency that grinding is poly-, and grind with depolymerization coarse granule wherein with sand mill, titanium dioxide is divided better in slurryLoose, reach nearly simple particle diameter;
The object of described step (2) is in the slurry after sand milling disperses, although titanium dioxide pigment particles is all pulverizedArrive the fineness of precursor, but wherein still contained a small amount of mechanical admixture and sintered body, needed further to remove to carryThe dispersiveness of high product.
Alkaline aluminum contained compound in described step (4) is selected from least one in sodium metaaluminate, potassium metaaluminate; Alkalescence calorizeThe solution concentration of compound is with Al2O3Count 80～120g/L, its addition is with Al2O3Quality meter, with the quality hundred of titanium dioxideProportion by subtraction is 1.0%～7.0%.
As preferably: the alkaline aluminum contained compound in described step (4) is sodium metaaluminate.
As preferably: described step (4) neutral and alkali aluminum contained compound addition is with Al2O3Quality meter, with the matter of titanium dioxideAmount percentage is 2.0%～5.0%.
As preferably: in described step (4), then add the solution of alkaline aluminium compound to generate boehmite-type oxidation in slurryAluminium coating layer, then regulate slurry pH value 6.5～7.5.
Acid aluminum contained compound in described step (5) is selected from least one in aluminum sulfate, aluminium chloride, aluminum nitrate etc.; AcidThe solution concentration of property aluminum contained compound is with Al2O3Count 80～120g/L, its addition is with Al2O3Quality meter, with titanium dioxideMass percent be 0.5%～3.0%.
As preferably: the aluminium compound in step (5) is aluminum sulfate; The addition of acid aluminum contained compound is with Al2O3QualityMeter, with the mass percent of titanium dioxide be 0.5%～2.0%.
Filtration, washing in step (6) can adopt the known washing equipment of industry technical staff as vane type filtration machineOr plate and frame filter press, through fully removing the solubility salt material in pigment, the resistivity of General Requirements filter cake is greater than 200 EuropeRice.
Beneficial effect
The present invention is by accurately controlling the operating procedure such as sand milling, classification operation in titanium dioxide production process, scatteredTitanium dioxide pigment particles surface has been coated the aluminium oxide of boehmite-type aluminium oxide and two kinds of forms of amorphous alumina, is dioxyChange titanium pigment provides good dispersiveness and dispersion stabilization in automobile cathode electrophoresis paint, adopts two after alumina treatmentTitanium oxide pigments has very strong positive charge within the scope of cathode electrophoresis dope pH value, has both met cathode electrophoresis dope to particleThe requirement of the positive negativity of surface charge, also can produce enough electrostatic repulsions, is conducive to the dispersion stabilization of pigment particles.The properties of product that adopt the inventive method to produce have met special to TiO 2 pigment of automobile high-grade cathode electrodip painting completelyRequirement, has filled up the technological gap of domestic titanium dioxide industry in this field.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail, but this should be interpreted as to the present invention is above-mentionedThe scope of theme only limits to following embodiment, without departing from the idea case in the present invention described above, and according to the common skill in this areaArt knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
Embodiment 1
(1) slurry that preparation comprises titanium dioxide first product: take 60kg deionized water, add containing 120gSiO2Sodium metasilicate moltenLiquid, under agitation add 60kg not the rutile titanium dioxide of coating to make concentration be 800gTiO2The titania slurry of/L,Use again sand mill sand milling, make titanium dioxide reach simple particle diameter;
(2) dilution, classification: with deionized water titania slurry concentration dilution qualified sand milling to 300gTiO2/ L, then useDiameter 1 inch hydrocyclone carries out classification, gets qualified overflow slurry and is transferred in coating groove, and it is measured with TiO2Count 50kg,
(3) heating: in coating groove, the temperature of slurry is raised to 50 DEG C by the mode of steam indirect;
(4) add alkaline aluminum contained compound: the pH value to 10.2 that regulates slurry with diluted acid or diluted alkaline; Maintain 60 minutes, add20L100gAl2O3The sodium aluminate solution of/L, adds rear Al2O3With TiO2Mass percent be 4.0%; Add again qualityPercent concentration is that 15% dilution heat of sulfuric acid is transferred to 6.8 the pH value of slurry;
(5) add acid aluminum contained compound: be under 6.0～7.5 condition maintain slurry pH value with sig water, maintain 60Minute, add 2.5L100gAl2O3The aluminum sulfate solution of/L, adds rear Al2O3With TiO2Mass percent be 0.5%, thenThe pH value of slurry is transferred to 6.8;
(6) slaking, filtration, washing, dry and calcining, pulverize: through the coated titania slurry of above-mentioned steps in insulation alsoStir lower slaking and filter after 60 minutes, be washed to filter cake resistivity 250 Europe rice; With the dry gained filter cake of electric drying oven with forced convection;After pulverizing with steam flow pulverizer again, get product.
Embodiment 2
(1) slurry that preparation comprises titanium dioxide first product: take 60kg deionized water, add the triethanolamine containing 120g,Under stirring, add 60kg not the rutile titanium dioxide of coating make concentration and be about 800gTiO2The titania slurry of/L, thenUse sand mill sand milling, make titanium dioxide reach simple particle diameter;
(2) dilution, classification: with deionized water titania slurry concentration dilution qualified sand milling to 300gTiO2/ L, then useDiameter 1 inch hydrocyclone carries out classification, gets qualified overflow slurry and is transferred in coating groove, and it is measured with TiO2Count 50kg,
(3) heating: in coating groove, the temperature of slurry is raised to 55 DEG C by the mode of steam indirect;
(4) add alkaline aluminum contained compound: regulate the pH value to 10.3 of slurry with diluted acid or diluted alkaline, maintain 80 minutes, then addEnter 17.5L100gAl2O3The potassium metaaluminate solution of/L; Add rear Al2O3With TiO2Mass percent be 3.5%, then addMass percent concentration is that 15% dilution heat of sulfuric acid is transferred to 6.9 the pH value of slurry;
(5) add acid aluminum contained compound: be about under 6.0～7.5 condition maintaining slurry pH value with sig water, maintain 80Minute, add 5L100gAl2O3The liquor alumini chloridi of/L, adds rear Al2O3With TiO2Mass percent be 1.0%, thenThe pH value of slurry is transferred to 6.8;
(6) slaking, filtration, washing, dry and calcining, pulverize: through the coated titania slurry of above-mentioned steps in insulation alsoStir lower slaking and filter after 60 minutes, be washed to filter cake resistivity 250 Europe rice; With the dry gained filter cake of electric drying oven with forced convection;After pulverizing with steam flow pulverizer, get product.
Embodiment 3
(1) slurry that preparation comprises titanium dioxide first product: take 60kg deionized water, add containing 120gSiO2Sodium metasilicate moltenLiquid, under agitation add 60kg not the rutile titanium dioxide of coating make concentration and be about 800gTiO2The titanium deoxide slurry of/LMaterial, then use sand mill sand milling, make titanium dioxide reach simple particle diameter;
(2) dilution, classification: with deionized water titania slurry concentration dilution qualified sand milling to 300gTiO2/ L, then useDiameter 1 inch hydrocyclone carries out classification, gets qualified overflow slurry and is transferred in coating groove, and it is measured with TiO2Count 50kg,
(3) heating: in coating groove, the temperature of slurry is raised to 55 DEG C by the mode of steam indirect;
(4) add alkaline aluminum contained compound: the pH value to 10.1 that regulates slurry with diluted acid or diluted alkaline; Maintain 100 minutes, addEnter 15L100gAl2O3The sodium aluminate solution of/L, adds rear Al2O3With TiO2Mass percent be 3.0%, then add matterThe dilution heat of sulfuric acid that amount percent concentration is 15% is transferred to 7.1 the pH value of slurry;
(5) add acid aluminum contained compound: be about under 6.0～7.5 condition maintaining slurry pH value with sig water, maintain 100Minute, add 7.5L100gAl2O3The aluminum nitrate solution of/L, adds rear Al2O3With TiO2Mass percent be 1.5%, thenThe pH value of slurry is transferred to 6.8;
(6) slaking, filtration, washing, dry and calcining, pulverize: through the coated titania slurry of above-mentioned steps in insulation alsoStir lower slaking and filter after 60 minutes, be washed to filter cake resistivity 250 Europe rice, with the dry gained filter cake of electric drying oven with forced convection;After pulverizing with steam flow pulverizer, get product.
Embodiment 4
(1) slurry that preparation comprises titanium dioxide first product: take 60kg deionized water, add containing 120gSiO2Sodium metasilicate moltenLiquid, under agitation add 60kg not the rutile titanium dioxide of coating make concentration and be about 800gTiO2The titanium deoxide slurry of/LMaterial, then use sand mill sand milling, make titanium dioxide reach simple particle diameter;
(2) dilution, classification: with deionized water titania slurry concentration dilution qualified sand milling to 300gTiO2/ L, then useDiameter 1 inch hydrocyclone carries out classification, and qualified overflow slurry is transferred in coating groove, and it is measured with TiO2Count 50kg,
(3) heating: the temperature of slurry is raised to 50 DEG C by the mode of steam indirect;
(4) add alkaline aluminum contained compound: the pH value to 10.4 that regulates slurry with diluted acid or diluted alkaline; Maintain 180 minutes, addEnter 12.5L100gAl2O3The sodium aluminate solution of/L; Add rear Al2O3With TiO2Mass percent be 2.0%, then addMass percent concentration is that 15% dilution heat of sulfuric acid is transferred to 6.8 the pH value of slurry;
(5) add acid aluminum contained compound: be about under 6.0～7.5 condition maintaining slurry pH value with sig water, maintain180 minutes, add 10L100gAl2O3The aluminum sulfate solution of/L, adds rear Al2O3With TiO2Mass percent be 2.0%,Again the pH value of slurry is transferred to 7.0;
(6) slaking, filtration, washing, dry and calcining, pulverize: through the coated titania slurry of above-mentioned steps in insulationAnd stir lower slaking and filter after 60 minutes, be washed to filter cake resistivity > 250 Europe rice; With the dry gained filter of electric drying oven with forced convectionCake; After pulverizing with steam flow pulverizer, get product.
In embodiment 5 the present embodiment, only add alkaline aluminum contained compound, do not add acid aluminum contained compound
(1) slurry that preparation comprises titanium dioxide first product: take 60kg deionized water, add containing 120gSiO2Sodium silicate solution,Under agitation add 60kg not the rutile titanium dioxide of coating make concentration and be about 800gTiO2The titania slurry of/L,Use again sand mill sand milling, make titanium dioxide reach simple particle diameter;
(2) dilution, classification: with deionized water titania slurry concentration dilution qualified sand milling to 300gTiO2/ L, then use straightFootpath 1 inch hydrocyclone carries out classification, gets qualified overflow slurry and is transferred in coating groove, and it is measured with TiO2Count 50kg;
(3) heating: in coating groove, the temperature of slurry is raised to 60 DEG C by the mode of steam indirect;
(4) add alkaline aluminum contained compound: regulate the pH value to 10.1 of slurry with diluted acid or diluted alkaline, maintain 160 minutes, add22.5L100gAl2O3The sodium aluminate solution of/L; Add rear Al2O3With TiO2Mass percent be 5.0%, then add qualityPercent concentration is that 15% dilution heat of sulfuric acid is transferred to 7.1 the pH value of slurry;
(5) slaking, filtration, washing, dry and calcining, pulverize: the titania slurry coated through above-mentioned steps is being incubated and stirringMix lower slaking and filter after 60 minutes, be washed to filter cake resistivity 250 Europe rice; With the dry gained filter cake of electric drying oven with forced convection;After pulverizing with steam flow pulverizer, get product.
In embodiment 6 the present embodiment, only add acid aluminum contained compound, do not add alkaline aluminum contained compound
(1) slurry that preparation comprises titanium dioxide first product: take 60kg deionized water, add containing 120gSiO2Sodium silicate solution,Under agitation add 60kg not the rutile titanium dioxide of coating make concentration and be about 800gTiO2The titania slurry of/L,Use again sand mill sand milling, make titanium dioxide reach simple particle diameter;
(2) dilution, classification: with deionized water titania slurry concentration dilution qualified sand milling to 300gTiO2/ L, then use straightFootpath 1 inch hydrocyclone carries out classification, and qualified overflow slurry is transferred in coating groove, and it is measured with TiO2Count 50kg;
(3) heating: in coating groove, the temperature of slurry is raised to 55 DEG C by the mode of steam indirect;
(4) add acid aluminum contained compound: regulate the pH value to 6.5 of slurry with diluted acid, maintain 140 minutes, add 22.5L100gAl2O3The aluminum sulfate solution of/L, adds rear Al2O3With TiO2Mass percent be 5.0%, then the pH value of slurry is transferred to7.0；
(5) slaking, filtration, washing, dry and calcining, pulverize: the titania slurry coated through above-mentioned steps is being incubated and stirringMix lower slaking and filter after 60 minutes, be washed to filter cake resistivity 250 Europe rice; With the dry gained filter cake of electric drying oven with forced convection;After pulverizing with steam flow pulverizer, get product.
Table 1 washs the 250 Europe rice times used of filter cake resistivity for above each embodiment tests slurry deionized water, andThe serviceability of products obtained therefrom in cathode electrodip painting sees the following form.
In an embodiment of the present invention, 5 of embodiment have used alkaline meta-aluminate by neutralization reaction production boehmite-typeAluminium oxide coating layer, be easy to resistivity to accomplish by washing 250 Europe rice of electrophoretic paint requirement at production process of titanium pigmentAbove, but the tank liquor dispersion stabilization in the mill base dispersion stabilization in electrophoretic paint process and use procedure can only reachMedium level, the flatness of film is also poor, has the thrust of 0.237um. And in embodiment 6, all use acidityAluminium salt generates amorphous alumina coating layer by neutralization reaction, and the look of product in electrophoretic paint process is by dispersion stabilizationAll reached top grade level with the tank liquor dispersion stabilization in use procedure, film layer is also very smooth, but this technique bagThe titanium dioxide of film in process of production, is washed very difficultly, and inefficiency, is unfavorable for follow-up dry and steam flow pulverizing processOperation continuously. The present invention is by being coated boehmite-type and amorphous alumina on TiO 2 pigment surface, and suitably controlThe ratio of the two, the water soluble salt when having solved cathode electrodip painting titanium dioxide pigment special and producing is removed the time and at electrophoretic paintIn the contradiction of dispersion stabilization aspect, successfully prepared and met the titanium dioxide of automobile by high-grade cathode electrodip painting particular/special requirementTitanium pigment.
Claims (9)
1. a production method for automobile cathode electrophoresis paint titanium dioxide pigment special, is characterized in that, under comprisingState step:
(1) slurry that preparation comprises titanium dioxide first product: take 5～60kg deionized water, add dispersing aid,Under agitation add the not rutile titanium dioxide first product of coating of 5～60kg, make concentration and be 600～800gTiO2The titania slurry of/L, then use sand mill sand milling, make titanium dioxide reach simple particle diameter;
(2) dilution, classification: with deionized water titania slurry concentration dilution to 300 qualified sand milling～400g/L, then use hydroclone classification, the accepted stock of overflow is sent in coating groove;
(3) heating: in coating groove, the temperature of slurry is raised to 50～70 DEG C;
(4) add alkaline aluminum contained compound: adjusting slurry pH value with dilute sulfuric acid is 10.0～10.5, maintain 60～180 minutes, then add the solution of alkaline aluminum contained compound in slurry, generate boehmite-type aluminium oxide coating layer,Finally regulate slurry pH value to 5.0～8.0;
(5) add acid aluminum contained compound: adjusting slurry pH value with dilute sulfuric acid is 6.0～7.5, maintains 60～180Minute, then add the solution of acid aluminum contained compound in slurry, generate knot amorphous alumina coating layer, thenWith sig water adjusting slurry pH value to 6.5～7.5;
(6) slaking, filtration, washing, dry and calcining, pulverize: through the coated titanium deoxide slurry of above-mentioned stepsMaterial slaking 60～100 minutes under 50～70 DEG C of stirrings, after filtration, washing, then by filtration cakes torrefaction, steam flow powderBroken, obtain automobile cathode electrophoresis paint titanium dioxide pigment special.
2. the production method of a kind of automobile cathode electrophoresis paint titanium dioxide pigment special according to claim 1,It is characterized in that, the dispersing aid in described step (1) is selected from the one in sodium metasilicate or triethanolamine,Its addition is 0.1～0.4% of rutile titanium dioxide quality.
3. the production method of a kind of automobile cathode electrophoresis paint titanium dioxide pigment special according to claim 1,It is characterized in that, the alkaline aluminum contained compound in described step (4) is selected from sodium metaaluminate, potassium metaaluminateAt least one; The solution concentration of alkalescence aluminium compound is with Al2O3Count 80～120g/L, its addition is with Al2O3Quality meter, with the mass percent of titanium dioxide be 1.0%～7.0%.
4. according to the production of a kind of automobile cathode electrophoresis paint titanium dioxide pigment special described in claim 1 or 3Method, is characterized in that, the alkaline aluminum contained compound in described step (4) is sodium metaaluminate.
5. the production method of a kind of automobile cathode electrophoresis paint titanium dioxide pigment special according to claim 3,It is characterized in that, described step (4) neutral and alkali aluminum contained compound addition is with Al2O3Quality meter, with dioxyThe mass percent of changing titanium is 2.0%～5.0%.
6. the production method of a kind of automobile cathode electrophoresis paint titanium dioxide pigment special according to claim 1,It is characterized in that, in described step (4), then add the solution of alkaline aluminium compound in slurry, generate vigorousNurse stone type aluminium oxide coating layer, finally regulates slurry pH value to 6.5～7.5.
7. the production method of a kind of automobile cathode electrophoresis paint titanium dioxide pigment special according to claim 1,It is characterized in that, the acid aluminum contained compound in step (5) is selected from aluminum sulfate, aluminium chloride, aluminum nitrate etc.At least one; The solution concentration of acid aluminum contained compound is with Al2O3Count 80～120g/L, its addition withAl2O3Quality meter, with the mass percent of titanium dioxide be 0.5%～3.0%.
8. according to the production of a kind of automobile cathode electrophoresis paint titanium dioxide pigment special described in claim 1 or 7Method, is characterized in that, the acid aluminum contained compound in step (5) is aluminum sulfate.
9. according to the production of a kind of automobile cathode electrophoresis paint titanium dioxide pigment special described in claim 1 or 7Method, is characterized in that, the addition of acid aluminum contained compound is with Al2O3Quality meter, with the matter of titanium dioxideAmount percentage is 0.5%～2.0%.
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| CN201510710714.6A CN105602292A (en) | 2015-10-28 | 2015-10-28 | Production method of special titanium dioxide pigment for automobile cathode electrophoresis coatings |
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Cited By (8)
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| CN106947295A (en) * | 2017-03-20 | 2017-07-14 | 云南冶金新立钛业有限公司 | The method for preparing Titanium dioxide slurry |
| CN107974107A (en) * | 2017-12-18 | 2018-05-01 | 四川龙蟒钛业股份有限公司 | A kind of TiO 2 pigment product pH value control method |
| CN108329719A (en) * | 2018-04-25 | 2018-07-27 | 四川龙蟒钛业股份有限公司 | A kind of titanium white production method with high glaze low oil absorption ferric |
| CN109467971A (en) * | 2018-11-08 | 2019-03-15 | 龙蟒佰利联集团股份有限公司 | A kind of preparation method of cathode electrodip painting titanium dioxide |
| CN109762372A (en) * | 2019-03-01 | 2019-05-17 | 河南佰利联新材料有限公司 | A kind of preparation method improving titanium dioxide weatherability |
| CN111548652A (en) * | 2020-05-27 | 2020-08-18 | 河南佰利联新材料有限公司 | Preparation method of titanium dioxide for aluminum electrophoretic coating paint |
| CN113088105A (en) * | 2021-03-22 | 2021-07-09 | 龙蟒佰利联集团股份有限公司 | High-weather-resistance titanium dioxide and preparation method thereof |
| CN116023806A (en) * | 2022-09-22 | 2023-04-28 | 攀枝花东方钛业有限公司 | Titanium dioxide for environment-friendly paint and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947295A (en) * | 2017-03-20 | 2017-07-14 | 云南冶金新立钛业有限公司 | The method for preparing Titanium dioxide slurry |
| CN107974107A (en) * | 2017-12-18 | 2018-05-01 | 四川龙蟒钛业股份有限公司 | A kind of TiO 2 pigment product pH value control method |
| CN108329719A (en) * | 2018-04-25 | 2018-07-27 | 四川龙蟒钛业股份有限公司 | A kind of titanium white production method with high glaze low oil absorption ferric |
| CN108329719B (en) * | 2018-04-25 | 2020-03-20 | 四川龙蟒钛业股份有限公司 | Production method of titanium dioxide with high gloss and low oil absorption |
| CN109467971A (en) * | 2018-11-08 | 2019-03-15 | 龙蟒佰利联集团股份有限公司 | A kind of preparation method of cathode electrodip painting titanium dioxide |
| CN109762372A (en) * | 2019-03-01 | 2019-05-17 | 河南佰利联新材料有限公司 | A kind of preparation method improving titanium dioxide weatherability |
| CN111548652A (en) * | 2020-05-27 | 2020-08-18 | 河南佰利联新材料有限公司 | Preparation method of titanium dioxide for aluminum electrophoretic coating paint |
| CN111548652B (en) * | 2020-05-27 | 2021-11-02 | 河南佰利联新材料有限公司 | Preparation method of titanium dioxide for aluminum electrophoretic coating paint |
| CN113088105A (en) * | 2021-03-22 | 2021-07-09 | 龙蟒佰利联集团股份有限公司 | High-weather-resistance titanium dioxide and preparation method thereof |
| CN113088105B (en) * | 2021-03-22 | 2022-05-24 | 龙佰集团股份有限公司 | High-weather-resistance titanium dioxide and preparation method thereof |
| CN116023806A (en) * | 2022-09-22 | 2023-04-28 | 攀枝花东方钛业有限公司 | Titanium dioxide for environment-friendly paint and preparation method thereof |
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