CN104559325A - Preparation technology of HP titanium dioxide - Google Patents
Preparation technology of HP titanium dioxide Download PDFInfo
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- CN104559325A CN104559325A CN201410817379.5A CN201410817379A CN104559325A CN 104559325 A CN104559325 A CN 104559325A CN 201410817379 A CN201410817379 A CN 201410817379A CN 104559325 A CN104559325 A CN 104559325A
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Abstract
The invention discloses a preparation technology of HP titanium dioxide. The preparation technology comprises the following steps: finely selecting coating particles; balling the coating particles and core particles; bonding and melting the coating particles and the core particles; fusing the coating particles and the core particles; improving the mobility of the coating particles and the core particles. According to the preparation technology of HP titanium dioxide, disclosed by the invention, the prepared HP titanium dioxide has the properties identical to that of titanium dioxide, and can be used for completely substituting the pigment-level titanium dioxide, so that the use cost of the raw material can be greatly lowered; the production process is free of environmental pollutiont; the preparation technology can be used for industrialized large-scale production.
Description
Technical field
The invention belongs to titanium white production technical field, specifically the preparation technology of HP titanium dioxide.
Background technology
Titanium dioxide has excellent optics and physical properties, possess that reducing power is strong, opacifying power be large, dispersed strong, good luster, physics and stable chemical performance, the performance such as nontoxic, harmless, has a wide range of applications in various fields such as coating, plastics, papermaking, ink and potteries.The links such as the manufacture of titanium dioxide, consumption and application all produce material impacts to the many aspects in Economic development and social life.
Because the production cost of titanium dioxide is high, cost differentials amplitude is large, and titanium ore resource is day by day in short supply, non-renewable, comprises its production process environmental pollution serious, the widespread use of titanium dioxide is restricted.Relevant titanium white consumption industry product cost increases, burden, and the development of these industries is subject to great restriction.The key addressed these problems reduces the consumption of titanium dioxide in goods, prepares the titanin substitute similar and with low cost to titanium white performance, and it is a kind of effective terms of settlement that whole or larger proportion replacement titanium dioxide is applied.Composite titanium dioxide by adopting cheap Inorganic nonmetal mineral as kernel, obtains at its Surface coating one deck TiO2 particle, with alternative titanium dioxide just.
Current, the making method of domestic and international composite titanium dioxide has eight kinds: simple and mechanical hybrid system, powerful mechanical milling method, grain-grain coating modification method, TiOSO4 hydrolysis method, TiCl4 hydrolysis method, fluorination method, microwave process for synthesizing, carbonation method.But because related process is limited, product performance are not good, generally can only replace 10% ~ 30% of titanium dioxide, and production process environmental pollution is serious, and most of method cannot carry out large-scale industrial production.Particular case is analyzed as follows:
1, simple and mechanical hybrid system: TiO2 is sticky on nonmetalliferous ore particulate top layer simply, this unordered Combination titanium dioxide composite pigment, because TiO2 is coated poor, therefore composite product can only the some properties of simple analog titanium dioxide within the specific limits, in use procedure, TiO2 and body are easy to peel off, can not meet the requirement of the bulk users such as coating, can only substitute titanium white be applied with lower ratio, its effect reducing product cost is very limited.
2, powerful mechanical milling method: be improve on " simple and mechanical hybrid system " basis, uses high-strength mechanical Ginding process, is bonded together after making two kinds of material activation.Due to technology and equipment, in production process, between titanium white and kernel, absorption is incomplete mutually, in probability distribution.Because titanium white is only physical adsorption to the coated of kernel, its intermolecular reactive force and electrostatic force more weak, titanium white easily comes off from the surface of kernel.Bag core titanium white can not bear high shear force in media as well and extrude power by force, thus the decline of composite titanium dioxide application performance is even lost.So the composite titanium dioxide quality extremely unstable produced, be difficult to be accepted by market and client.
3, grain-grain coating modification method: adopt white mineral powder wet ultra-fine grinding and white mineral powder and the blended grinding approach of crystallization TiO2 wet method, is prepared from by modes such as the segmentation refinement of solid particulate, surface hydroxylation is transformed and Mechanochemical Effect causes grain-grain coating modification reactions.Having that bonding force is strong, grain-grain is coated is carry out waiting deficiency on secondary agglomeration particle.
4, TiOSO4 hydrolysis method: owing to affecting by hydrolysis concentration and solid content, crystalline particle is thick, TiO2 and body material physico-chemical property difference greatly, are difficult to obtain pigment-level titanium white, can only obtain non-pigment level titanium white, cannot put into production.
5, TiCl4 hydrolysis method: because TiCl4 is expensive, price itself has exceeded pure titanium white, so industrialization is substantially impossible under current market condition.
6, fluorination method: the industrial consumption of raw materials used acid is little, and cost is too high, environmental issue is serious, and industrialized possibility is very little.
7, microwave process for synthesizing: this method is hydrolysis method in fact still, just its ageing process have employed microwave heating, and from scale operation, it is very little that microwave method will realize the industrialized possibility of composite titanium dioxide.
8, carbonation method: adopt CaCO3, TiO2 etc. to be raw material, replace TiO2 offspring kernel with CaCO3 particulate, reduce the ratio of TiO2 in this pigment particles, this composite composition use range is limited.
Summary of the invention
The object of this invention is to provide the preparation technology of HP titanium dioxide, the HP titanium dioxide of preparation possesses the performance identical with titanium dioxide, can realize the completely alternative of pigment-level titanium dioxide, can reduce raw-material use cost greatly.
The technical solution adopted in the present invention is:
The preparation technology of HP titanium dioxide, comprises the steps:
S1, selected coatingparticles
The performances such as selected construction profile and size-grade distribution are close with titanium dioxide, and surface has the inorganic powder of reactive behavior as coatingparticles;
S2, nodularization is carried out to coatingparticles, the sub-mixed powder of seed
After coatingparticles selected in step S1 is equipped with seed, first coatingparticles is done to the dispersion do not recovered, then carry out the nodularization of coatingparticles, the sub-mixed powder of seed;
S3, coatingparticles, seed are bondd, melted
By the mechanical stress that the coatingparticles of nodularization in step S2, seed utilize mechanofusion system to provide strong further, synchronously strong compression and shear-stress can be produced in coatingparticles, seed sub-mixed powder layer, for coatingparticles and seed provide the energy needed for bonding and fusing, the point of contact of coatingparticles and seed produce a kind of strongly contact energy, realize the bonding of coatingparticles and seed, fusing;
S4, coatingparticles, seed to be merged
By mechanical forces such as compression, shearing, shock actions in step S3, between coatingparticles and seed, produce strong motion and reactive force district, generate plasma zone, like this, combined by mechanochemical treatment between coatingparticles and seed.Seed is deposited in the surface of coatingparticles, forms the dense shell of seed in fusion process on coatingparticles, and seed embeds in organic powder macrobead, becomes membranization state;
S5, improve the mobility of coatingparticles, seed
By fusion, nano level seed attached bag is overlayed on micron-sized coatingparticles, make mobility that violent change occur, after fusion, increase clad ratio further, be finally prepared into HP titanium dioxide.
Further, in described step S4, comprise following step:
A, the polymerization completely realizing seed and coatingparticles and convergence, increase surface energy;
B, seed are bonded to coatingparticles surface, increase contact area, form chemical bridge, reduce surface energy by the distortion caused by compression, impact and shear-stress;
Seed of c, precipitation melts the dense shell formed around coatingparticles each other, reduces surface energy further;
D, to coatingparticles, seed imposes applicable stress that surface energy is reduced, and just can melt, and merges completely keeping the situation of particle bond to be issued to.
Further, in described step S5, comprise following step:
The arrangement of a, change coatingparticles and seed;
B, minimizing coatingparticles and the interparticle internal force of son;
The electrostatic force of c, change coatingparticles and seed.
Further, described seed is titanium dioxide powder.
The invention has the beneficial effects as follows,
The preparation technology of HP titanium dioxide disclosed by the invention, HP titanium dioxide is identical with the technical feature of titanium dioxide, can realize the completely alternative of pigment-level titanium dioxide, can reduce raw-material use cost greatly.Concrete advantage is as follows:
1, HP titanium dioxide possesses the performance identical with titanium dioxide, as: opacifying power, whiteness, oil number etc.;
2, HP titanium dioxide and titanium dioxide ratio, the granularity size distribution of product is better, the excellent properties of mixture and low density, makes product in coating system, have better dispersiveness, mobility and suitability;
3, production cost comparatively titanium dioxide significantly reduce, products production cost is lower than titanium dioxide about 50 percent;
4, HP titanium dioxide can merge the titanium dioxide of various model and function, wraps up, alternative, covering performance is excellent;
5, production process environmentally safe, can carry out industrialization scale operation, meet the industry policy of national sustainable development.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the present invention is further detailed explanation.Following examples only for technical scheme of the present invention is clearly described, and can not limit the scope of the invention with this.
Specific embodiments of the invention are,
The preparation technology of HP titanium dioxide, comprises the steps:
S1, selected coatingparticles
The performances such as selected construction profile and size-grade distribution are close with titanium dioxide, and surface has the inorganic powder of reactive behavior as coatingparticles, consider that seed will stick to after on coatingparticles, coatingparticles characteristic has decisive for fusing subsequently, so its particle shape will be considered when choosing, surface tissue, hardness and deformation characteristic, and notice that the material behavior of coatingparticles should have tackiness;
S2, nodularization is carried out to coatingparticles, the sub-mixed powder of seed
After coatingparticles selected in step S1 is equipped with seed, first coatingparticles is done to the dispersion do not recovered, then carry out the nodularization of coatingparticles, the sub-mixed powder of seed;
Utilizing nodularization system to produce centrifugal force makes mixed powder move to the inwall of high speed cydariform rotating cylinder, when a fixed stator head from mixed powder through out-of-date, the powder layer of this precompressed is subject to mechanically compress, be forced to through a narrow gap, simultaneously powder layer sliding-rolling each other in highly dense material layer, such mechanical energy is passed to the point of contact of coatingparticles, sub-particle granules, the rotation of rotating cylinder makes powder layer face toward chamber wall to be compressed, once powder layer have passed stator, just alleviate stress again, progressively realize coatingparticles, the sub-powder nodularization of seed.
S3, coatingparticles, seed are bondd, melted
By the mechanical stress that the coatingparticles of nodularization in step S2, seed utilize mechanofusion system to provide strong further, synchronously strong compression and shear-stress can be produced in coatingparticles, seed sub-mixed powder layer, for coatingparticles and seed provide the energy needed for bonding and fusing, the point of contact of coatingparticles and seed produce a kind of strongly contact energy, realize the bonding of coatingparticles and seed, fusing;
Being uniformly distributed of coatingparticles and seed to be realized in step S3, the pulverizing of single particle in mixing process, can not be caused.
Mechanofusion system synchronously can produce strong compression and shear-stress in coatingparticles, seed sub-mixed powder layer, to compress thus and friction can cause thermal spike that is very of short duration and local, this thermal spike can expand the burning method temperature range occurred at point of contact to, by reaching compression, shear-stress to the powder layer Repeated Compression in centrifugal field, produce plasma zone.
S4, coatingparticles, seed to be merged
By mechanical forces such as compression, shearing, shock actions in step S3, between coatingparticles and seed, produce strong motion and reactive force district, generate plasma zone, like this, combined by mechanochemical treatment between coatingparticles and seed.Seed is deposited in the surface of coatingparticles, forms the dense shell of seed in fusion process on coatingparticles, and seed embeds in organic powder macrobead, becomes membranization state;
S5, improve the mobility of coatingparticles, seed
By fusion, nano level seed attached bag is overlayed on micron-sized coatingparticles, make mobility that violent change occur, after fusion, increase clad ratio further, be finally prepared into HP titanium dioxide.
Further, in described step S4, comprise following step:
A, the polymerization completely realizing seed and coatingparticles and convergence, increase surface energy;
B, seed are bonded to coatingparticles surface, increase contact area, form chemical bridge, reduce surface energy by the distortion caused by compression, impact and shear-stress;
Seed of c, precipitation melts the dense shell formed around coatingparticles each other, reduces surface energy further;
D, to coatingparticles, seed imposes applicable stress that surface energy is reduced, and just can melt, and merges completely keeping the situation of particle bond to be issued to.
Further, in described step S5, comprise following step:
The arrangement of a, change coatingparticles and seed;
B, minimizing coatingparticles and the interparticle internal force of son;
The electrostatic force of c, change coatingparticles and seed.
Further, seed is titanium dioxide powder.
Embody rule of the present invention is as follows:
1, rubber, the plastics result of use of HP titanium dioxide
Be applied to after in rubber item, have higher insulation and resistance toheat, acid-and base-resisting erosion performance is good, and thermal expansivity is little.In rubber macromolecule chain, there is good dispersing property and distribution performance, good combination is produced with rubber, good wettability is had to rubber, the mechanical property of cross-linked rubber, ageing-resistant performance and bond properties can be improved simultaneously, product particle fineness is even, not volatile, odorless, tasteless, nontoxic, there is good package stability.Can be used for white, light color and colorful rubber product filler, pollution-free, nondiscoloration, effectively reduces the cost of rubber.
Be applied to after in plastics, the mobility of adjustable resin, improve the resistance toheat of product, greatly increase the tensile strength of plastics, flexural strength, shock strength, reduce the production cost of plastics simultaneously.
2, the result of use of HP titanium dioxide used for powder coating
HP titanium dioxide has and well shields photoextinction, can replace expensive titanium dioxide for powder coating, paint, can improve the uvioresistant of coating, and have good heat-insulating property.Application on powder coating, both can reduce operation, give Coating Durability again, had adapted to environmental requirement, simultaneously saved the energy again, and can the advantage of comprehensive various powder coating, improved the film performance of powder coating, met the needs of different field.
3, the latex coating result of use of HP titanium dioxide
HP titanium dioxide in latex coating not only plays the effect hiding and decorate, importantly can improve the physical and chemical performance of coating, strengthen chemical stability, improve opacifying power, reducing power, improve anticorrosion, fast light and weathering resistance, strengthen the physical strength of film and sticking power, prevent ultraviolet and moisture through etc.
Table 1 HP titanium dioxide physico-chemical property
| Whiteness (with standard ratio) | ≥98％ |
| Oil number (g/100g) | ≤12 |
| PH value | 7.0-9.5 |
| 105 DEG C of fugitive constituents (%) | ≤0.5 |
| Reducing power (with standard ratio) | ≥95％ |
| Opacifying power (g/m2) | ≤30 |
| Volume specific resistance | ≥80Ω.m |
| Dispersed | ≤20μ.m |
| Water-soluble (W%) | ≤0.5 |
| Boiling point | 2900℃ |
| Fusing point | 1740℃ |
Table 2 HP titanium dioxide and titanium dioxide Performance comparision
Can be found out by upper table, HP titanium dioxide is identical with titanium dioxide performance, can substitute the various model titanium dioxides in latex coating, enhance product performance.
Be noted that, the above embodiment is unrestricted to the explanation of technical solution of the present invention, the equivalent replacement of art those of ordinary skill or other amendments made according to prior art, as long as do not exceed thinking and the scope of technical solution of the present invention, all should be included within interest field of the presently claimed invention.
Claims (4)
- The preparation technology of 1.HP titanium dioxide, is characterized in that: comprise the steps:S1, selected coatingparticlesThe performances such as selected construction profile and size-grade distribution are close with titanium dioxide, and surface has the inorganic powder of reactive behavior as coatingparticles;S2, nodularization is carried out to coatingparticles, the sub-mixed powder of seedAfter coatingparticles selected in step S1 is equipped with seed, first coatingparticles is done to the dispersion do not recovered, then carry out the nodularization of coatingparticles, the sub-mixed powder of seed;S3, coatingparticles, seed are bondd, meltedBy the mechanical stress that the coatingparticles of nodularization in step S2, seed utilize mechanofusion system to provide strong further, synchronously strong compression and shear-stress can be produced in coatingparticles, seed sub-mixed powder layer, for coatingparticles and seed provide the energy needed for bonding and fusing, the point of contact of coatingparticles and seed produce a kind of strongly contact energy, realize the bonding of coatingparticles and seed, fusing;S4, coatingparticles, seed to be mergedBy mechanical forces such as compression, shearing, shock actions in step S3, between coatingparticles and seed, produce strong motion and reactive force district, generate plasma zone, like this, combined by mechanochemical treatment between coatingparticles and seed.Seed is deposited in the surface of coatingparticles, forms the dense shell of seed in fusion process on coatingparticles, and seed embeds in organic powder macrobead, becomes membranization state;S5, improve the mobility of coatingparticles, seedBy fusion, nano level seed attached bag is overlayed on micron-sized coatingparticles, make mobility that violent change occur, after fusion, increase clad ratio further, be finally prepared into HP titanium dioxide.
- 2. the preparation technology of HP titanium dioxide according to claim 1, is characterized in that: in described step S4, comprises following step:A, the polymerization completely realizing seed and coatingparticles and convergence, increase surface energy;B, seed are bonded to coatingparticles surface, increase contact area, form chemical bridge, reduce surface energy by the distortion caused by compression, impact and shear-stress;Seed of c, precipitation melts the dense shell formed around coatingparticles each other, reduces surface energy further;D, to coatingparticles, seed imposes applicable stress that surface energy is reduced, and just can melt, and merges completely keeping the situation of particle bond to be issued to.
- 3. the preparation technology of HP titanium dioxide according to claim 1, is characterized in that: in described step S5, comprises following step:The arrangement of a, change coatingparticles and seed;B, minimizing coatingparticles and the interparticle internal force of son;The electrostatic force of c, change coatingparticles and seed.
- 4. the preparation technology of HP titanium dioxide according to claim 1, is characterized in that: described seed is titanium dioxide powder.
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| US20080166156A1 (en) * | 2007-01-09 | 2008-07-10 | Sharp Kabushiki Kaisha | Toner and method of manufacturing the same, two-component developer, developing apparatus, and image forming apparatus |
| CN101896154A (en) * | 2007-12-12 | 2010-11-24 | 雅芳产品公司 | Use the macroscopic particles of handling to improve the method for skin appearance |
| CN102093758A (en) * | 2009-12-10 | 2011-06-15 | 湖南金马硅业有限公司 | Artificial composite pigment and preparation method thereof |
| CN103740139A (en) * | 2013-12-10 | 2014-04-23 | 辽宁亿龙矿业股份有限公司 | Composite titanium dioxide and preparation method thereof |
-
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- 2014-12-24 CN CN201410817379.5A patent/CN104559325A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1723086A (en) * | 2003-01-09 | 2006-01-18 | 昭和电工株式会社 | Composite particles and method for production thereof and use thereof |
| US20080166156A1 (en) * | 2007-01-09 | 2008-07-10 | Sharp Kabushiki Kaisha | Toner and method of manufacturing the same, two-component developer, developing apparatus, and image forming apparatus |
| CN101896154A (en) * | 2007-12-12 | 2010-11-24 | 雅芳产品公司 | Use the macroscopic particles of handling to improve the method for skin appearance |
| CN102093758A (en) * | 2009-12-10 | 2011-06-15 | 湖南金马硅业有限公司 | Artificial composite pigment and preparation method thereof |
| CN103740139A (en) * | 2013-12-10 | 2014-04-23 | 辽宁亿龙矿业股份有限公司 | Composite titanium dioxide and preparation method thereof |
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Application publication date: 20150429 |
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