CN112759948B - Special titanium dioxide for road sign paint and preparation method thereof - Google Patents
Special titanium dioxide for road sign paint and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 242
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 107
- 239000003973 paint Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 75
- 239000002253 acid Substances 0.000 claims abstract description 61
- 238000000576 coating method Methods 0.000 claims abstract description 45
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 34
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 34
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 34
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 65
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 9
- 230000001276 controlling effect Effects 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000007888 film coating Substances 0.000 claims description 5
- 238000009501 film coating Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 16
- 238000002156 mixing Methods 0.000 abstract description 16
- 238000004383 yellowing Methods 0.000 abstract description 14
- 229910000329 aluminium sulfate Inorganic materials 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 73
- 239000000047 product Substances 0.000 description 14
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910008159 Zr(SO4)2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- MOVRNJGDXREIBM-UHFFFAOYSA-N aid-1 Chemical compound O=C1NC(=O)C(C)=CN1C1OC(COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)CO)C(O)C1 MOVRNJGDXREIBM-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C1/3623—Grinding
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C1/363—Drying, calcination
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C1/3638—Agglomeration, granulation, pelleting
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3669—Treatment with low-molecular organic compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3684—Treatment with organo-silicon compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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- C01—INORGANIC CHEMISTRY
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- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/62—L* (lightness axis)
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The invention provides a special titanium dioxide for road sign paint and a preparation method thereof, wherein the method comprises the following steps: mixing metatitanic acid, KOH and Al2(SO4)3Mixing with phosphoric acid, squeezing the obtained salt-treated metatitanic acid until the water content is lower than 50%, and calcining; crushing, dispersing and hydrocyclone separation of the obtained calcined product to obtain titanium dioxide slurry; heating the titanium dioxide slurry, adding a sodium hexametaphosphate solution, adjusting the pH value to 6.5-7.5, and adding Zr (SO)4)2Adjusting the pH value of the solution to 8.3-8.7, adding the sodium hexametaphosphate solution again, adjusting the pH value to 10.2-10.7, and adding NaAlO under the condition of maintaining the pH value2Adjusting the pH value of the solution to 5.8-6.2, and curing to obtain slurry for coating treatment; and (3) washing, drying and crushing the slurry subjected to the coating treatment, and mixing the slurry with an organic treating agent to obtain the special titanium dioxide for the road paint. The road marking paint titanium dioxide has excellent yellowing resistance and weather resistance.
Description
Technical Field
The invention belongs to the technical field of titanium dioxide, and particularly relates to special titanium dioxide for road sign paint and a preparation method thereof.
Background
Road sign paint, also known as road marking paint, is a coating for road marking and various traffic signs, and is widely applied to places such as driveways, pedestrian crossings, parking positions, parking lots and the like.
Titanium dioxide (TiO)2) Is an important inorganic chemical pigment and is widely applied to the industries of paint, printing ink, papermaking, plastics, rubber, chemical fiber, ceramics and the like.
When the titanium dioxide is applied to the road sign paint, the titanium dioxide is required to have higher brightness, super-strong weather resistance and wear resistance, and simultaneously, the titanium dioxide is required to overcome the high-temperature process environment in the spraying process of the road sign paint without yellowing. The existing road sign paint often yellows when being sprayed and printed on a road surface at high temperature, changes color within a period of time after being sprayed, has poor weather resistance, and can also change color along with the abrasion of the road surface.
Disclosure of Invention
In view of the above, the invention aims to provide the special titanium dioxide for the road sign paint and the preparation method thereof, and the titanium dioxide prepared by the method does not turn yellow after being sprayed at high temperature.
The invention provides a preparation method of special titanium dioxide for road sign paint, which comprises the following steps:
mixing metatitanic acid, KOH and Al2(SO4)3Mixing with phosphoric acid to obtain salt-treated metatitanic acid; with TiO2The concentration of the metatitanic acid is 90-110 g/L; the TiO is2、KOH、Al2(SO4)3The mass ratio of the phosphoric acid to the phosphoric acid is 1000: 4.17-5.48: 2.49-3.04: 11.41-12.42;
squeezing the metatitanic acid treated by the salt until the moisture content is lower than 50%, and calcining to obtain a calcined product;
crushing, dispersing and hydrocyclone separation of the calcined product to obtain titanium dioxide slurry;
heating the titanium dioxide slurry to 45-55 ℃, adding a sodium hexametaphosphate solution, adjusting the pH value to 6.5-7.5, and then adding Zr (SO)4)2Adjusting the pH value of the solution to 8.3-8.7, adding the sodium hexametaphosphate solution again, adjusting the pH value to 10.2-10.7, and adding the solution while maintaining the pH valueNaAlO2Adjusting the pH value of the solution to 5.8-6.2, and curing to obtain slurry for coating treatment;
and (3) washing, drying and crushing the slurry subjected to the coating treatment, and mixing the slurry with an organic treating agent to obtain the special titanium dioxide for the road paint.
Preferably, the concentration of the salt-treated metatitanic acid is 290-310 g/L in terms of titanium dioxide.
Preferably, the calcining temperature is 1200-1500 ℃; the content of the rutile type titanium dioxide in the calcined product reaches more than 99 percent.
Preferably, the particle size of the titanium dioxide in the titanium dioxide slurry is 0.2-0.35 μm.
Preferably, the concentration of the sodium hexametaphosphate solution is 98-102 g/L, and the sodium hexametaphosphate solution accounts for 0.15-0.25% of the titanium dioxide slurry.
Preferably, said Zr (SO)4)2The concentration of the solution is 98-102 g/L, Zr (SO)4)2The solution accounts for 0.4-0.55% of the titanium dioxide slurry.
Preferably, the NaAlO2The concentration of the solution is 98-102 g/L, and NaAlO2The solution accounts for 2.6-3.0% of the titanium dioxide slurry.
Preferably, the organic treating agent is selected from one or more of trimethylolpropane, trimethylolethane and silicone.
Preferably, a sulfuric acid solution with the mass fraction of 10% or an alkali solution with the mass fraction of 10% is used for adjusting the pH value.
The invention provides titanium dioxide special for road sign paint, which is prepared by the preparation method in the technical scheme.
The invention provides a preparation method of special titanium dioxide for road sign paint, which comprises the following steps: mixing metatitanic acid, KOH and Al2(SO4)3Mixing with phosphoric acid to obtain salt-treated metatitanic acid; with TiO2The concentration of the metatitanic acid is 90-110 g/L; the TiO is2、KOH、Al2(SO4)3The mass ratio of the phosphoric acid to the phosphoric acid is 900-1100: 4.17-5.48: 2.49-3.04: 11.41-12.42; squeezing the salt-treated metatitanic acid to waterThe component content is lower than 50 percent, and a calcined product is obtained by calcining; crushing, dispersing and hydrocyclone separation of the calcined product to obtain titanium dioxide slurry; heating the titanium dioxide slurry to 45-55 ℃, adding a sodium hexametaphosphate solution, adjusting the pH value to 6.5-7.5, and then adding Zr (SO)4)2Adjusting the pH value of the solution to 8.3-8.7, adding the sodium hexametaphosphate solution again, adjusting the pH value to 10.2-10.7, and adding NaAlO under the condition of maintaining the pH value2Adjusting the pH value of the solution to 5.8-6.2, and curing to obtain slurry for coating treatment; and (3) washing, drying and crushing the slurry subjected to the coating treatment, and mixing the slurry with an organic treating agent to obtain the special titanium dioxide for the road paint. The road sign paint titanium dioxide prepared by the method can have good compatibility with other inorganic fillers and resin; the paint of the road sign does not turn yellow after being sprayed at high temperature; no color change after long-term use, super high weather resistance and long service life. The experimental results show that: compared with the coating sample which is not baked, the coating baked at 220 ℃ has yellowing resistance and color difference Delta E less than or equal to 0.3; the weather resistance color difference delta E is less than or equal to 0.3.
Drawings
FIG. 1 is a photograph of titanium dioxide prepared in example 1 of the present invention after yellowing resistance test;
FIG. 2 is a photograph of titanium dioxide prepared in example 2 of the present invention after yellowing resistance test;
FIG. 3 is a photograph of titanium dioxide prepared in example 3 of the present invention after yellowing resistance test.
Detailed Description
The invention provides a preparation method of special titanium dioxide for road sign paint, which comprises the following steps:
mixing metatitanic acid, KOH and Al2(SO4)3Mixing with phosphoric acid to obtain salt-treated metatitanic acid; with TiO2The concentration of the metatitanic acid is 90-110 g/L; the TiO is2、KOH、Al2(SO4)3The mass ratio of the phosphoric acid to the phosphoric acid is 1000: 4.17-5.48: 2.49-3.04: 11.41-12.42;
squeezing the metatitanic acid subjected to salt treatment until the moisture content is lower than 50%, and calcining to obtain a calcined product;
crushing, dispersing and hydrocyclone separation of the calcined product to obtain titanium dioxide slurry;
heating the titanium dioxide slurry to 45-55 ℃, adding a sodium hexametaphosphate solution, adjusting the pH value to 6.5-7.5, and then adding Zr (SO)4)2Adjusting the pH value of the solution to 8.3-8.7, adding the sodium hexametaphosphate solution again, adjusting the pH value to 10.2-10.7, and adding NaAlO under the condition of maintaining the pH value2Adjusting the pH value of the solution to 5.8-6.2, and curing to obtain slurry for coating treatment;
and (3) washing, drying and crushing the slurry subjected to the coating treatment, and mixing the slurry with an organic treating agent to obtain the special titanium dioxide for the road paint.
The road sign paint titanium dioxide prepared by the method can have good compatibility with other inorganic fillers and resin; the paint of the road sign does not turn yellow after being sprayed at high temperature; the color does not change after long-term use, and the weather resistance is super strong; the prepared pavement paint is wear-resistant and has long service life.
The invention uses metatitanic acid, KOH and Al2(SO4)3And phosphoric acid to obtain salt-treated metatitanic acid. In the invention, the metatitanic acid is preferably prepared from titanium concentrate through acidolysis, sedimentation, crystallization, ferrous separation, fine filtration, concentration and hydrolysis. With TiO2The concentration of the metatitanic acid is 90-110 g/L, preferably 95-105 g/L; in a specific embodiment, the concentration of the metatitanic acid is TiO2The weight is 100 g/L. The TiO is2、KOH、Al2(SO4)3The mass ratio of phosphoric acid to phosphoric acid is 900-1100: 4.17-5.48: 2.49-3.04: 11.41-12.42, and more preferably 1000:4.83:2.77: 11.92; or 1000:4.17:2.49: 12.42; or 1000: 5.48: 3.04: 12.42.
the salt treatment is carried out in a tank. Adding metatitanic acid into a reactor/kettle, stirring for 20-30 min, adding KOH, stirring for 18-22 min, and then adding Al2(SO4)3And fully stirring for 1-1.5 h to obtain the metatitanic acid treated by salt. The concentration of the metatitanic acid subjected to salt treatment is 290-310 g/L.
After obtaining the metatitanic acid treated by salt, the invention squeezes the metatitanic acid treated by salt until the moisture content is lower than 50%, and then calcinates to obtain a calcinated product. In the present invention, the concentration of the salt-treated metatitanic acid is preferably 290 to 310g/L, and more preferably 295 to 305 g/L. The present invention is preferably pressed using a membrane filter press known to those skilled in the art to a moisture content of less than 50%. The calcination temperature is preferably 1200-1500 ℃; the content of the rutile type titanium dioxide in the calcined product reaches more than 99 percent.
The invention crushes, disperses and hydrocyclone separates the calcinated product to obtain the titanium dioxide slurry. The invention preferably crushes the calcined product by roll milling, wet ball milling and sand mill grinding in sequence, disperses the crushed calcined product in water and carries out hydrocyclone separation to obtain titanium dioxide slurry. The particle size of the titanium dioxide in the titanium dioxide slurry is preferably 0.2-0.35 μm. The solid content of the titanium dioxide slurry is 280-320 g/L.
Heating the titanium dioxide slurry to 45-55 ℃, adding a sodium hexametaphosphate solution, adjusting the pH value to 6.5-7.5, and then adding Zr (SO)4)2Adjusting the pH value of the solution to 8.3-8.7, adding the sodium hexametaphosphate solution again, adjusting the pH value to 10.2-10.7, and adding NaAlO under the condition of maintaining the pH value2And (3) adjusting the pH value of the solution to 5.8-6.2, and curing to obtain slurry for coating treatment. And (4) coating the titanium dioxide slurry to obtain the slurry subjected to coating treatment. The coating is also called surface treatment, and the function of the coating is to carry out surface modification on the titanium dioxide. After the temperature of the titanium dioxide slurry is increased to 45-55 ℃, preferably within 30min, adding a metered sodium hexametaphosphate solution; the concentration of the sodium hexametaphosphate solution is 98-102 g/L, and the sodium hexametaphosphate solution preferably accounts for 0.15-0.25% of the titanium dioxide slurry. In a specific embodiment, the concentration of the sodium hexametaphosphate solution is 100 g/L. After the sodium hexametaphosphate solution is added, preferably stirring for 18-22 min, more preferably stirring for 20 min. According to the invention, the pH value is preferably adjusted to 6.5-7.5 by adopting a sulfuric acid solution with the mass fraction of 10%, and the pH adjustment is more preferably completed within 5 min. Stirring for 35-45 min after the pH value is 6.5-7.5, and stirring for 40min is more preferable.
The Zr (SO) is preferably added slowly in 60min4)2A solution; said Zr (SO)4)2The concentration of the solution is 98-102 g-L，Zr(SO4)2The solution accounts for 0.4-0.55% of the titanium dioxide slurry. Zr (SO)4)2After the solution is added, stirring is preferably carried out for 35-45 min, and stirring is more preferably carried out for 40 min. The pH value of the alkaline solution is preferably adjusted by 10 percent of the mass fraction; the lye is preferably a NaOH solution. After the pH value is adjusted to 8.3-8.7, the mixture is preferably stirred for 28-32 min, and more preferably stirred for 30 min.
The invention adds sodium hexametaphosphate solution again and then adjusts the pH value to 10.2-10.7. And adding the sodium hexametaphosphate solution again, wherein the mass of the sodium hexametaphosphate solution accounts for 0.15-0.25% of that of the titanium dioxide slurry. The invention preferably adopts 10 percent of alkali liquor by mass percent to complete the adjustment of the pH value within 10 min; and after the pH value is adjusted, preferably stirring for 28-32 min, and more preferably stirring for 30 min.
The invention adds NaAlO under the condition of maintaining the pH value2A solution; namely, the temperature is maintained at 10.2-10.7; the invention preferably adds NaAlO2And adding a sulfuric acid solution with the mass fraction of 10% to the solution at the same time to control the pH value. The NaAlO2The concentration of the solution is 98-102 g/L, and NaAlO2The solution accounts for 2.6-3.0% of the titanium dioxide slurry. Adding NaAlO2After the solution is finished, stirring is preferably carried out for 45-55 min, and stirring is more preferably carried out for 50 min.
According to the invention, the pH value is preferably adjusted back by adopting 10% of sulfuric acid by mass, and more preferably, the pH value of the slurry is adjusted back to 5.8-6.2 by adding the sulfuric acid within 30 min.
The invention preferably cures under the condition of slow stirring; the curing time is preferably 55-65 min, and more preferably 60 min.
After the slurry subjected to coating treatment is obtained, the slurry subjected to coating treatment is washed, dried, crushed and mixed with an organic treating agent to obtain the special titanium dioxide for the road paint. Some impurities in the coating process are removed through water washing treatment.
In the present invention, the organic treating agent is preferably selected from one or more of trimethylolpropane, trimethylolethane, and silicone; the organic treating agent preferably accounts for 0.30-0.50% of the mass of the slurry for coating treatment. The organic treating agent can improve the dispersibility of the titanium dioxide and can improve the high-temperature resistance of the titanium dioxide.
The invention provides special titanium dioxide for road sign paint, which is prepared by the preparation method of the technical scheme.
The invention adopts the following evaluation method to prepare the titanium dioxide into a paint film for yellowing resistance and weather resistance tests:
first, disperse
Desalting water: 25g of
Thickener HS3000 (1.5%): 15g of
Dispersant SN 5040: 1g
Defoamer a36:0.25g
Wetting agent PE 100: 0.05g
Preservatives LFM: 0.5g
100g of titanium dioxide
Adding the above materials into a container, stirring with a high speed disperser at 500rpm, wetting completely, adjusting to 1500rpm, and dispersing at high speed for 10 min.
Second, pulping
Desalting water: 40g of
Film-forming aid 1, 2-propylene glycol: 20g of
0.25g of antifoaming agent A36
And adding the above materials, and stirring with high speed disperser at 900rpm for 5 min.
Third, mixing paint
Slurry preparation: 50g
Pure acrylic emulsion: 190g of
Thickener HS3000 (2.5%): 8g
Leveling agent 3136: 2g
And adding the above characteristics respectively, and continuously stirring with a high-speed dispersion machine at the rotation speed of 800rpm for 20 min.
Fourthly, coating film
The prepared wire rod with the thickness of 100 mu m for paint coating is scraped onto a paperboard from bottom to obtain a paint film with the thickness of 100 mu m.
Fifth, test for yellowing resistance
After the paint is dried, measuring the values of L, a and b by using a CM-5 colorimeter, then putting the paint into a constant-temperature oven at 220 ℃ for 5min, and measuring the values of L ', a ' and b ' again according to a formula:
calculating to obtain Delta E, and representing the yellowing performance of the material. Delta E is less than or equal to 0.3, which indicates that the yellow is not easy to turn.
Sixth, weather resistance test
After the paint was dried, the values of L, a and b were measured with a CM-5 colorimeter, and then the resultant was put into a rapid aging analyzer (JIL-I type Taixing City aerospace instruments Co., Ltd.) to conduct a weather resistance test. Exposure time: 90min, working temperature: 40-55 ℃. Finally, the values of L ', a ' and b ' are measured by a CM-5 colorimeter according to the formula:
calculated as Δ E, the weather resistance is characterized, the smaller Δ E, the better the weather resistance.
For further illustration of the present invention, the following examples are provided to describe the titanium dioxide specially used for road marking paint and its preparation method in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
1. Salt treatment
Adding metatitanic acid into a reaction kettle, adjusting the concentration of metatitanic acid before adding metatitanic acid, and adding TiO2The actual addition amount of the metatitanic acid is 10L, which is calculated as 100 g/L;
② stirring for 30min, adding 4.17g KOH according to the proportion;
③ after KOH is added, stirring for 20min, adding 12.42g H3PO4Stirring for 30 min;
fourthly, 2.49g of Al is added after the stirring is finished2(SO4)3Fully stirring for 1-1.5 h to obtain metatitanic acid treated by salt;
2. press drying before calcination
The content of titanium dioxide metatitanic acid after salt treatment is about 300g/L generally, a large amount of water is contained, the titanium dioxide metatitanic acid is squeezed by a diaphragm filter press, and the water content after squeezing is controlled to be lower than 50%;
3. calcination of
The calcination has the function of dehydrating metatitanic acid after salt treatment and converting anatase titanium dioxide into rutile titanium dioxide, and the calcination temperature is controlled at 1200 ℃, so that the final rutile conversion rate is ensured to be more than 99%.
4. Pulverizing treatment
Grinding the rutile titanium dioxide crude product obtained by calcination by a roll mill, a wet ball mill and a sand mill for crushing and dispersion treatment, carrying out rotary liquid separation after treatment, carrying out coating treatment on the titanium dioxide with qualified particle size, returning the titanium dioxide with coarser particle size to the sand mill for grinding again to obtain carbon dioxide slurry, wherein the particle size of the titanium dioxide is 0.2-0.35 mu m, and the solid content is 280 g/L;
5. coating film
Firstly, adding metered qualified ground slurry after grinding treatment into a film coating tank, and heating the slurry to 50 +/-5 ℃.
② adding metered sodium hexametaphosphate solution within 30min, wherein the concentration of the sodium hexametaphosphate solution is 100g/L, the adding amount is 0.15 percent, and stirring for 20min after the addition is finished.
Thirdly, within 5min, using 10 percent dilute sulfuric acid to adjust the pH value, controlling the pH value of the slurry to be 7.0, and stirring for 40 min.
Fourthly, 100g/L of Zr (SO) is slowly added in 60min4)2The solution was added in an amount of 0.5% and stirred for 40min after the addition was complete.
Regulating pH with 10% dilute alkali solution within 10min, controlling pH of the slurry to 8.5, and stirring for 30 min.
Sixthly, repeating the operation of the second step, adding the sodium hexametaphosphate solution again with the concentration of 100g/L and the adding amount of 0.15 percent, and stirring for 20min after the addition is finished.
Seventhly, regulating the pH value to 10.2 again by using 10% sodium hydroxide solution within 10min, and stirring for 30 min.
Slowly adding NaAlO within 90min2，NaAlO2The solution is mixed with Na2The concentration of O is 100g/L, the adding amount is 2.6 percent, NaAlO is added2Adding H while adding the solution2SO4The pH was controlled to stabilize at 10.2 and after the addition was complete, stirring was carried out for 50 min.
Ninthly, adding dilute sulfuric acid within 30min, and adjusting the pH value of the slurry to 5.8.
Curing for 60min under slow stirring to complete the coating treatment.
5. Washing treatment
Transferring the slurry subjected to the coating treatment to a diaphragm filter press, and performing water washing treatment. Removing some soluble impurities in the coating process.
6. Flash drying and vapor powder treatment
And (3) carrying out flash evaporation drying on the titanium dioxide qualified by washing, transferring to a steam powder machine for steam flow crushing treatment, and adding 0.30% of organic silicon to obtain the special titanium dioxide for the road paint.
The performance of the special titanium dioxide for the road sign paint prepared in the embodiment 1 of the invention is tested by adopting the method, and the result is as follows: the color difference delta E measured by yellowing is 0.23;
TABLE 1 yellowing resistance test results for titanium dioxide prepared in examples 1-3
TABLE 2 weather resistance test results of titanium dioxide prepared in examples 1 to 3
Example 2
Adding metatitanic acid into a reaction kettle, adjusting the concentration of metatitanic acid before adding metatitanic acid, and adding TiO2The actual addition amount of the metatitanic acid is 10L, which is calculated as 100 g/L;
② stirring for 30min, and adding 4.83g KOH according to the proportion;
③ after KOH is added, stirring for 20min, adding 11.92g H3PO4Stirring for 30 min;
fourthly, 2.77g of Al is added after the stirring is finished2(SO4)3Fully stirring for 1-1.5 h to obtain metatitanic acid treated by salt;
2. press drying before calcination
The content of titanium dioxide metatitanic acid after salt treatment is about 300g/L generally, the titanium dioxide metatitanic acid contains a large amount of water, and the titanium dioxide is pressed by a diaphragm filter press, and the water content after pressing is controlled to be lower than 50%;
3. calcination of
The calcination has the function of dehydrating metatitanic acid after salt treatment and converting anatase titanium dioxide into rutile titanium dioxide, the calcination temperature is controlled at 1500 ℃, and the final rutile conversion rate is ensured to be more than 99%.
4. Pulverizing treatment
Grinding the rutile titanium dioxide crude product obtained by calcination by a roll mill, a wet ball mill and a sand mill for crushing and dispersion treatment, carrying out rotary liquid separation after treatment, carrying out coating treatment on titanium dioxide with qualified particle size, returning the titanium dioxide with coarser particle size to the sand mill for grinding again to obtain titanium dioxide slurry, wherein the particle size of the titanium dioxide is 0.2-0.35 mu m, and the solid content is 320 g/L;
5. coating film
Firstly, adding metered qualified ground slurry after grinding treatment into a film coating tank, and heating the slurry to 50 +/-5 ℃.
② adding metered sodium hexametaphosphate solution within 30min, wherein the concentration of the sodium hexametaphosphate solution is 100g/L, the adding amount is 0.25 percent, and stirring for 20min after the addition is finished.
Thirdly, within 5min, using 10 percent dilute sulfuric acid to adjust the pH value, controlling the pH value of the slurry to be 7.5, and stirring for 40 min.
Fourthly, 100g/L of Zr (SO) is slowly added in 60min4)2The solution was added in an amount of 0.55% and stirred for 40min after the addition was complete.
Regulating pH with 10% dilute alkali solution within 10min, controlling pH of the slurry to 8.7, and stirring for 30 min.
Sixthly, repeating the operation of the second step, adding the sodium hexametaphosphate solution again with the concentration of 100g/L and the adding amount of 0.25 percent, and stirring for 20min after the addition is finished.
Regulating pH to 10.7 with 10% concentration sodium hydroxide solution within 10min and stirring for 30 min.
Slowly adding NaAlO within 90min2，NaAlO2The solution is mixed with Na2The concentration of O is 100g/L, the adding amount is 3.0 percent, NaAlO is added2Adding H while adding the solution2SO4The pH was controlled to stabilize at 10.7 and after the addition was complete, stirring was carried out for 50 min.
Ninthly, adding dilute sulfuric acid within 30min, and adjusting the pH value of the slurry to 6.2.
Curing for 60min under slow stirring to complete the coating treatment.
6. Washing treatment
Transferring the slurry subjected to the coating treatment to a diaphragm filter press, and performing water washing treatment. Removing some soluble impurities in the coating process.
7. Flash drying and vapor powder treatment
And (3) carrying out flash evaporation drying on the titanium dioxide qualified by washing, transferring to a steam powder machine for steam flow crushing treatment, and adding 0.50% of organic silicon to obtain the special titanium dioxide for the road paint.
The performance of the titanium dioxide special for the road sign paint prepared in the embodiment 2 of the invention is tested by adopting the method, and the result is as follows: the color difference Δ E measured by yellowing was 0.16.
Example 3
Adding metatitanic acid into a reaction kettle, adjusting the concentration of metatitanic acid before adding metatitanic acid, and adding TiO2The actual addition amount of the metatitanic acid is 10L, which is calculated as 100 g/L;
② stirring for 25min, adding 5.48g KOH according to the proportion;
③ after KOH is added, stirring for 20min, adding 12.42g H3PO4Stirring for 30 min;
fourthly, 3.04g of Al is added after the stirring is finished2(SO4)3Fully stirring for 1-1.5 h to obtain metatitanic acid treated by salt;
2. press drying before calcination
The content of titanium dioxide metatitanic acid after salt treatment is about 300g/L generally, a large amount of water is contained, the titanium dioxide metatitanic acid is squeezed by a diaphragm filter press, and the water content after squeezing is controlled to be lower than 50%;
3. calcination of
The calcination has the function of dehydrating the metatitanic acid after salt treatment and converting the metatitanic acid into rutile type titanium dioxide from anatase type titanium dioxide, and the calcination temperature is controlled at 1300 ℃ to ensure that the final rutile conversion rate is over 99 percent.
4. Pulverizing treatment
Grinding the rutile titanium dioxide crude product obtained by calcination by a roll mill, a wet ball mill and a sand mill for crushing and dispersion treatment, carrying out rotary liquid separation after treatment, carrying out coating treatment on titanium dioxide with qualified particle size, returning the titanium dioxide with coarser particle size to the sand mill for grinding again to obtain titanium dioxide slurry, wherein the particle size of the titanium dioxide is 0.2-0.35 mu m, and the solid content is 300 g/L;
5. coating film
Firstly, adding metered qualified ground slurry after grinding treatment into a film coating tank, and heating the slurry to 50 +/-5 ℃.
② adding metered sodium hexametaphosphate solution within 30min, wherein the concentration of the sodium hexametaphosphate solution is 100g/L, the adding amount is 0.20 percent, and stirring for 20min after the addition is finished.
Thirdly, within 5min, using 10 percent dilute sulfuric acid to adjust the pH value, controlling the pH value of the slurry to be 7.0, and stirring for 40 min.
Fourthly, 100g/L of Zr (SO) is slowly added in 60min4)2The solution was added in an amount of 0.50% and stirred for 40min after the addition was complete.
Regulating pH with 10% dilute alkali solution within 10min, controlling pH of the slurry to 8.4, and stirring for 30 min.
Sixthly, repeating the operation of the second step, adding 100g/L sodium hexametaphosphate solution again, wherein the adding amount is 0.20 percent, and stirring for 20min after the adding is finished.
Seventhly, regulating the pH value to 10.4 again by using 10 percent NaOH solution within 10min, and stirring for 30 min.
Slowly adding NaAlO within 90min2，NaAlO2The solution is mixed with Na2The concentration of O is 100g/L, the adding amount is 2.8 percent, NaAlO is added2Adding H while adding the solution2SO4The pH was controlled to stabilize at 10.4 and after the addition was complete, stirring was carried out for 50 min.
Ninthly, adding dilute sulfuric acid within 30min, and adjusting the pH value of the slurry to 6.0.
Curing for 60min under slow stirring to complete the coating treatment.
5. Washing treatment
Transferring the slurry subjected to the coating treatment to a diaphragm filter press, and performing water washing treatment. Removing some soluble impurities in the coating process.
6. Flash drying and vapor powder treatment
And (3) carrying out flash evaporation drying on the titanium dioxide qualified by washing, transferring to a steam powder machine for steam flow crushing treatment, and adding 0.40% of organic silicon to obtain the special titanium dioxide for the road paint.
The performance of the special titanium dioxide for the road sign paint prepared in the embodiment 3 of the invention is tested by adopting the method, and the result is as follows: the color difference Δ E measured by yellowing was 0.29.
From the above embodiment, the invention provides a preparation method of special titanium dioxide for road sign paint, which comprises the following steps: mixing metatitanic acid, KOH and Al2(SO4)3Mixing with phosphoric acid to obtain salt-treated metatitanic acid; with TiO2The concentration of the metatitanic acid is 90-110 g/L; the TiO is2、KOH、Al2(SO4)3The mass ratio of the phosphoric acid to the phosphoric acid is 900-1100: 4.17-5.48: 2.49-3.04: 11.41-12.42; squeezing the metatitanic acid treated by the salt until the moisture content is lower than 50%, and calcining to obtain a calcined product; crushing, dispersing and hydrocyclone separation of the calcined product to obtain titanium dioxide slurry; heating the titanium dioxide slurry to 45-55 ℃, adding a sodium hexametaphosphate solution, adjusting the pH value to 6.5-7.5, and then adding Zr (SO)4)2Adjusting the pH value of the solution to 8.3-8.7, adding the sodium hexametaphosphate solution again, adjusting the pH value to 10.2-10.7, and adding NaAlO under the condition of maintaining the pH value2Adjusting the pH value of the solution to 5.8-6.2, and curing to obtain slurry for coating treatment; and (3) washing, drying and crushing the slurry subjected to the coating treatment, and mixing the slurry with an organic treating agent to obtain the special titanium dioxide for the road marking paint. The road sign paint titanium dioxide prepared by the method can have good compatibility with other inorganic fillers and resin; the paint of the road sign does not turn yellow after being sprayed at high temperature; the color does not change after long-term use, and the weather resistance is super strong; the prepared road surface paint is wear-resistant,the service time is long. The experimental results show that: compared with the coating sample which is not baked, the coating baked at 220 ℃ has yellowing resistance and color difference Delta E less than or equal to 0.3; the weather resistance color difference delta E is less than or equal to 0.3.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (2)
1. A preparation method of titanium dioxide for road sign paint comprises the following steps:
1) adding metatitanic acid into reactor, regulating the concentration of metatitanic acid before adding them, and adding TiO2The actual addition amount of the metatitanic acid is 10L, which is calculated as 100 g/L;
② stirring for 30min, and adding 4.83g KOH according to the proportion;
③ after KOH is added, stirring for 20min, adding 11.92g H3PO4Stirring for 30 min;
fourthly, 2.77g of Al is added after the stirring is finished2(SO4)3Fully stirring for 1-1.5 h to obtain metatitanic acid treated by salt;
2) press drying before calcining
The content of titanium dioxide metatitanic acid after salt treatment is 300g/L, squeezing by a membrane filter press is needed, and the water content after squeezing is controlled to be lower than 50%;
3) and calcining
The calcination has the functions of dehydrating metatitanic acid after salt treatment and converting anatase titanium dioxide into rutile titanium dioxide, wherein the calcination temperature is controlled at 1500 ℃, and the final rutile conversion rate is ensured to be more than 99%;
4) and pulverizing
Grinding the rutile type titanium dioxide crude product obtained by calcination by a roller mill, a wet ball mill and a sand mill for crushing and dispersing, carrying out liquid cyclone separation after treatment, coating the titanium dioxide with qualified granularity, returning the titanium dioxide with coarser granularity to the sand mill for grinding again to obtain titanium dioxide slurry, wherein the particle size of the titanium dioxide is 0.2-0.35 mu m, and the solid content is 320 g/L;
5) and a film coating
Adding metered qualified ground slurry subjected to grinding treatment into a film coating tank, and heating the slurry to 50 +/-5 ℃;
secondly, adding metered sodium hexametaphosphate solution within 30min, wherein the concentration of the sodium hexametaphosphate solution is 100g/L, the adding amount is 0.25 percent, and stirring for 20min after the addition is finished;
thirdly, regulating the pH value by using 10 percent dilute sulfuric acid within 5min, controlling the pH value of the slurry to be 7.5, and stirring for 40 min;
fourthly, 100g/L of Zr (SO) is slowly added in 60min4)2The adding amount of the solution is calculated according to 0.55 percent, and the solution is stirred for 40min after the addition is finished;
regulating pH with 10% dilute alkali solution within 10min, controlling pH of the slurry to 8.7, and stirring for 30 min;
sixthly, repeating the operation of the second step, adding the sodium hexametaphosphate solution again with the concentration of 100g/L and the adding amount of 0.25 percent, and stirring for 20min after the addition is finished;
seventhly, regulating the pH value to 10.7 within 10min by using a 10% sodium hydroxide solution again, and stirring for 30 min;
slowly adding NaAlO within 90min2，NaAlO2The solution is mixed with Na2The concentration of O is 100g/L, the adding amount is 3.0 percent, NaAlO is added2Adding H at the same time of the solution2SO4Controlling the pH value to be stable at 10.7, and stirring for 50min after the addition is finished;
ninthly, adding dilute sulfuric acid within 30min, and adjusting the pH value of the slurry to 6.2;
curing for 60min under slow stirring to complete the coating treatment;
6) washing with water
Transferring the slurry subjected to the coating treatment to a diaphragm filter press, and performing water washing treatment to remove soluble impurities in the coating process;
7) flash drying and vapor powder treatment
And (3) carrying out flash evaporation drying on the titanium dioxide qualified by washing, transferring to a steam powder machine for steam flow crushing treatment, and adding 0.50% of organic silicon to obtain the titanium dioxide for the road sign paint.
2. Titanium dioxide for road sign paint, which is prepared by the preparation method of claim 1.
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Denomination of invention: A special titanium dioxide powder for road sign paint and its preparation method Effective date of registration: 20231207 Granted publication date: 20220510 Pledgee: Agricultural Bank of China Limited Miyi County Branch Pledgor: PANZHIHUA DONGFANG TITANIUM INDUSTRY CO.,LTD. Registration number: Y2023980069498 |