CN1067967C - Superfine titanium white surface cladding tech. and reactor thereof - Google Patents

Superfine titanium white surface cladding tech. and reactor thereof Download PDF

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CN1067967C
CN1067967C CN98117967A CN98117967A CN1067967C CN 1067967 C CN1067967 C CN 1067967C CN 98117967 A CN98117967 A CN 98117967A CN 98117967 A CN98117967 A CN 98117967A CN 1067967 C CN1067967 C CN 1067967C
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value
reactor
titanium dioxide
nozzle
exit end
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CN1213659A (en
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崔爱莉
王亭杰
金涌
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Tsinghua University
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Tsinghua University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/1066—Oxides, Hydroxides

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The present invention relates to a surface coating technology for ultrafine titanium dioxide and a reaction vessel thereof. In the technology, firstly, dispersing agents are added to titanium dioxide slurry, the titanium dioxide slurry is heated to a certain temperature, sodium silicate is added, the pH value is regulated by diluted sulfuric acid, and heat preservation is carried out; after ageing, a silicon membrane coating process is finished; sodium hydrate is added to regulate the pH value, and then aluminum sulfate is added to regulate the pH value; the product is obtained by filtering, water washing and drying. Nozzles are arranged on two side walls of the reaction vessel, and a feed port and a discharge port are respectively arranged on the upper part and the lower part of the reaction vessel. By using the technology and the reaction vessel of the present invention to coat the surface of titanium dioxide, uniform and compact inorganic membranes can be generated, the thixotropy of the product is lowered, and the chalking resistance and the weatherability are increased.

Description

Superfine titanium white surface cladding tech and reactor thereof
The present invention relates to a kind of superfine titanium white surface cladding tech and reactor thereof, belong to the material technology field.
The superfine titanic oxide particle grain size is generally 0.2～0.4 μ m.On the one hand, because the particle small specific surface is long-pending big, intergranular cohesive force strengthens, and particle is easily reunited, the dispersed reduction in resin.Therefore, before surface treatment, must make TiO 2The particle of reuniting in the slurries is dispersed into single particle.At present, domestic main dispersing apparatus is a ball mill, and there is following shortcoming in this dispersing method: 1, ball mill is owing to existing back-mixing, so the material particles size-grade distribution that grinds is wide, does not reach monodispersed requirement.2, ball mill is the method for inner dress sand grains mechanical friction, because sand grains and material (TiO 2) contact friction, can bring pollution, reduce TiO 2Purity.3, at present domestic ball mill power consumption is big, the cost height.On the other hand, if TiO 2Particle directly joins in coating, the paint and goes, and then exists weathering resistance poor, and resistance to chalking hangs down and waits detrimentally affect.Therefore; the purpose that inorganic coating is handled is to coat layer protecting film on the surface of titanium dioxide; make and set up barrier together between titanium dioxide surface and the surrounding medium; thereby reduce the photochemical activity of titanium dioxide, help improving dispersiveness, photostabilization, weathering resistance and the resistance to chalking of titanium dioxide.
Existing about TiO in United States Patent (USP) 3437502 2The report of coating method, its coating equipment are common stirring tanks, because the restriction of appointed condition and technology, the coating effect is bad, and coating is inhomogeneous, and independently SiO is arranged 2And Al 2O 3Particle self nucleation, the thixotropy that shows as product in the specific implementation process is big, and sad filter is with dried machine throughput to reduce, and causes every performance index of finished product not reach requirement.
The objective of the invention is to develop a kind of superfine titanium white surface cladding tech and reactor thereof, under the sol-gel theoretical direction, the evenly technology of bag silicon, alclad is proposed, and match with novel high field of turbulent flow coating device, make particle list dispersion process and film process integrated, and making whole technological operation easy, energy consumption is low, and is easy to the engineering amplification.The finished product thixotropy is low, and film forming is even.
The superfine titanium white surface cladding tech of the present invention's development comprises following each step:
(1) be to add dispersion agent Na in 10～30% the titanium dioxide aqueous slurry containing weight percent 2SiO 3, the pH value that makes solution is 8.0～9.0, stir about 15～20 minutes carries out pre-dispersed;
(2) above-mentioned solution is heated to 80 ℃～90 ℃, adds the water glass of 0.1～0.5mol/l, the weight percent that adds water glass is SiO 2: TiO 2=0.01～0.02: 1, be that the pH value of 10～20% dilute sulphuric acid regulator solution is 7.0～8.0 with weight percent, in 80 ℃～90 ℃ insulations 3～4 hours down, ageing;
(3) on the basis of the above-mentioned second step bag silicon fiml, make solution temperature remain on 70 ℃～80 ℃, add 0.1mol/l Tai-Ace S 150, adding the Tai-Ace S 150 stoichiometry is Al 2O 3: TiO 2=0.02～0.04: 1, use 0.1mol/l sodium hydroxide, the pH value of regulator solution is 6～7, stirs 10 minutes;
(4) transferring the pH value of above-mentioned slurries with 0.1mol/l～0.2mol/l Tai-Ace S 150 is 7.0, continues to stir 2～3 hours, filters, be washed to barium salt check sulfate radical-free ion, at last, drying is 4～5 hours under 110 ℃～120 ℃, promptly obtains the superfine titanium white with silicon oxide and aluminum oxide coating.
The present invention has designed the reactor that is specifically designed to the above-mentioned superfine titanium white of preparation, the top of reactor is provided with opening for feed, the bottom is provided with discharge port, on the two side of reactor nozzle is housed, the entrance end of nozzle is taper, and exit end is a cylindricality, and the top opening for feed communicates with the exit end of nozzle, the opening for feed cone angle of nozzle is 13 °～14 °, exit end diameter d and exit end body length L 1Ratio be d: L 1=1: 2.5～3, exit end column length L 1With the long L of entrance end awl 2Ratio be L 1: L 2=1: 2～4.
The cladding process that the present invention proposes coats layer protecting film on the surface of titanium dioxide, makes between the surperficial of titanium dioxide and its medium on every side and sets up barrier together, thereby reduce the photochemical activity of titanium dioxide.Wrap one deck Al again 2O 3Behind the film, form the silicon-aluminium binary coating, and this technology has realized the film forming coating and nucleation look film do not occurred.
The present invention has also designed special-purpose reactor, the reactor content import is designed to form of nozzle,, pressure can be gathered together by the contraction of nozzle endoporus cross section, and be converted into kinetic energy, form with high-speed jet outwards sprays at last, in order to material is disperseed or fragmentation, to generate even, fine and close mineral membrane, and control thickness, reduce the thixotropy of product, easily filter, thereby improved resistance to chalking and the weathering resistance of titanium dioxide in paint greatly.
Description of drawings:
Fig. 1 is the structural representation of the reactor that designs of the present invention.
Fig. 2 (a) and (b), (c), (d) prepare the electromicroscopic photograph of sample for the present invention.
Below in conjunction with accompanying drawing, introduce content of the present invention in detail.
Among Fig. 1, the 1st, reactor, 2 and 5 is nozzles, 3 and 4 is opening for feeds, the 6th, discharge port.
As shown in Figure 1, the present invention has designed the reactor that is specifically designed to the above-mentioned superfine titanium white of preparation, the top of reactor is provided with opening for feed 3 and 4, the bottom is provided with discharge port 6, and nozzle 2 and 5 are housed on the two side of reactor, and the entrance end of nozzle is taper, exit end is a cylindricality, the top opening for feed communicates with the exit end of nozzle, and the opening for feed cone angle of nozzle is 13 °～14 °, exit end diameter d and exit end body length L 1Ratio be d: L 1=1: 2.5～3, exit end column length L 1With the long L of entrance end awl 2Ratio be L 1: L 2=1: 2～4.The mechanism of reactor is to utilize the high field of turbulent flow of nozzle 2 and 5, makes the coating agent can carry out microcosmic fast before film forming and mixes, and produces a uniform concentration distribution, then equably at TiO 2Surface growth.Material TiO 2And H 2From 2,5 pairs of sprays of nozzle, (during bag silicon is Na to membrane-forming agent to O simultaneously with pump 2SiO 3And H 2SO 4, be NaOH and Al during alclad 2(SO 4) 3) enter spray nozzle front end through opening for feed 3,4 respectively and enter reactor together.In impact cavity, mix the back and change aging tank over to, carry out next step work from discharge port 6.
Introduce embodiments of the invention below.
Embodiment 1 adds the dispersion agent water glass in the slurries that contain 15% titanium dioxide, the pH value to 8 of regulator solution, and stirring is carried out pre-dispersed, is heated to 85 ℃, and the stoichiometry of water glass is controlled at SiO 2/ TiO 2=2%, with the pH value to 8 that 10% dilute sulphuric acid is transferred solution, the bag silicon fiml is finished in ageing.On the basis of bag silicon fiml, holding temperature adds the Tai-Ace S 150 of 0.1mol/l and 20% sodium hydroxide simultaneously at 80 ℃, and the stoichiometry of Tai-Ace S 150 is controlled at Al 2O 3/ TiO 2=2%, use the sodium hydroxide adjust pH, maintain pH=8, with the pH to 7.0 of Tai-Ace S 150 adjusting slurry, ageing is washed to no SO 4 2-,, obtain the titanium dioxide of silicon-aluminium binary coating with barium salt check, filtration, 120 ℃ of dryings.The gained sample is even, fine and close film.The TEM photo is seen Fig. 4 (a), surface composition analysis in table l.
Embodiment 2 experimental techniques are with implementing 1.Change the acidity of bag silicon fiml, the pH to 8.5 of regulator solution carries out pre-dispersed, and wraps silicon fiml under this acidity.The gained sample is the loose membrane of sponge shape, and the TEM photo is seen Fig. 4 (b), surface composition analysis in table 1.
Embodiment 3 experimental techniques are with embodiment 1.Change over the acid degree.Wrap silicon fiml under the pH=7 condition during bag silicon fiml.The gained sample is that nucleation coats, rather than film forming coats.The TEM photo is seen Fig. 4 (c), surface composition analytical table 1.
Embodiment 4 experimental techniques are with embodiment 1.Change over the consumption of film.SiO 2/ TiO 2=1～1.6%, Al 2O 3/ TiO 2The TEM of=2% gained sample sees Fig. 4 (d), surface composition analysis in table 1.

Claims (2)

1, a kind of superfine titanium white surface cladding tech is characterized in that, this technology comprises following each step:
(1) be to add dispersion agent Na in 10～30% the titanium dioxide aqueous slurry containing weight percent 2SiO 3, the pH value that makes solution is 8.0～9.0, stir about 15～20 minutes carries out pre-dispersed;
(2) above-mentioned solution is heated to 80 ℃～90 ℃, adds the water glass of 0.1～0.5mol/l, the weight percent that adds water glass is SiO 2: TiO 2=0.01～0.02: 1, be that the pH value of 10～20% dilute sulphuric acid regulator solution is 7.0～8.0 with weight percent, in 80 ℃～90 ℃ insulations 3～4 hours down, ageing;
(3) on the basis of the above-mentioned second step bag silicon fiml, make solution temperature remain on 70 ℃～80 ℃, add 0.1mol/l Tai-Ace S 150, add Tai-Ace S 150 weight percent Al 2O 3: TiO 2=0.02～0.04: 1, use 0.1mol/l sodium hydroxide, the pH value of regulator solution is 6～7, stirs 10 minutes;
(4) transferring the pH value of above-mentioned slurries with 0.1mol/l～0.2mol/l Tai-Ace S 150 is 7.0, continues to stir 2～3 hours, filters, be washed to barium salt check sulfate radical-free ion, at last, drying is 4～5 hours under 110 ℃～120 ℃, promptly obtains the superfine titanium white with silicon oxide and aluminum oxide coating.
2, a kind of reactor that is used to prepare above-mentioned superfine titanium white, it is characterized in that, the top of this reactor is provided with opening for feed, the bottom is provided with discharge port, on the two side of reactor nozzle is housed, and the entrance end of nozzle is taper, exit end is a cylindricality, the top opening for feed communicates with the exit end of nozzle, and the opening for feed cone angle of nozzle is 13 °～14 °, exit end diameter d and exit end body length L 1Ratio be d: L 1=1: 2.5～3, exit end column length L 1With the long L of entrance end awl 2Ratio be L 1: L 2=1: 2～4.
CN98117967A 1998-09-11 1998-09-11 Superfine titanium white surface cladding tech. and reactor thereof Expired - Fee Related CN1067967C (en)

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DE10332650A1 (en) * 2003-07-18 2005-02-10 Kronos International, Inc. Producing a surface-treated titanium dioxide pigment useful in decorative paper comprises adding aluminum and phosphorus components to an alkaline titanium dioxide suspension and lowering the pH
CN100506923C (en) * 2006-05-18 2009-07-01 攀钢集团攀枝花钢铁研究院 Method for producing high weathering resistance titanium dioxide pigment
CN100506922C (en) * 2006-05-18 2009-07-01 攀钢集团攀枝花钢铁研究院 Method for producing high covering power titanium dioxide pigment
CN100999621B (en) * 2006-12-20 2010-09-01 中国科学院山西煤炭化学研究所 Process for inorganic-organic coating on surface of titanium white powder
CN100439454C (en) * 2006-12-20 2008-12-03 中国科学院山西煤炭化学研究所 Titanium dioxide surface organic-inorganic modification method
CN102093758B (en) * 2009-12-10 2014-01-01 湖南金马硅业有限公司 Artificial composite pigment and preparation method thereof
CN102199367B (en) * 2011-03-30 2013-12-25 中国科学院宁波材料技术与工程研究所 Method for preparing titanium dioxide pigment with high-temperature resistance
CN103913431B (en) * 2014-04-21 2016-10-26 济南裕兴化工有限责任公司 The assay method of titanium dioxide acid solubility
CN104479417A (en) * 2014-12-23 2015-04-01 安徽助成信息科技有限公司 Preparation method of rutile titanium dioxide inorganic coating film
CN105013600B (en) * 2015-07-03 2018-11-13 攀钢集团钛业有限责任公司 For continuously detaching coarse grained device before titanium dioxide coating process
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CN105860592B (en) * 2016-05-05 2018-02-16 焦作市裕盛钛业有限公司 A kind of modified titanium for being coated with polyacrylic acid
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CN108635241A (en) * 2018-06-07 2018-10-12 上海蔻沣生物科技有限公司 One kind having thixotropic oiliness slurry and preparation method thereof
CN110451835B (en) * 2019-09-17 2022-03-01 安徽好思家涂料股份有限公司 High-wear-resistance low-temperature sintered artificial colored sand and preparation method thereof
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3437502A (en) * 1968-03-28 1969-04-08 Du Pont Titanium dioxide pigment coated with silica and alumina
CN85103475A (en) * 1985-04-30 1986-10-29 河南师范大学 Preparation of rutile type pigment titanium white by high activity crystal
CN86101534A (en) * 1986-08-07 1988-02-17 上海京华化工厂 The preparation method of water dispersing lide powder pigment
CN1120978A (en) * 1994-10-20 1996-04-24 中国科学院山西煤炭化学研究所 Method of preparing coated superfine powder with metal surfactant by phase transfer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3437502A (en) * 1968-03-28 1969-04-08 Du Pont Titanium dioxide pigment coated with silica and alumina
CN85103475A (en) * 1985-04-30 1986-10-29 河南师范大学 Preparation of rutile type pigment titanium white by high activity crystal
CN86101534A (en) * 1986-08-07 1988-02-17 上海京华化工厂 The preparation method of water dispersing lide powder pigment
CN1120978A (en) * 1994-10-20 1996-04-24 中国科学院山西煤炭化学研究所 Method of preparing coated superfine powder with metal surfactant by phase transfer

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