CN100560657C - TiO 2Complex ore powder and preparation method - Google Patents
TiO 2Complex ore powder and preparation method Download PDFInfo
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- CN100560657C CN100560657C CNB2007101014849A CN200710101484A CN100560657C CN 100560657 C CN100560657 C CN 100560657C CN B2007101014849 A CNB2007101014849 A CN B2007101014849A CN 200710101484 A CN200710101484 A CN 200710101484A CN 100560657 C CN100560657 C CN 100560657C
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Abstract
The present invention relates to composite granule that is used in fields such as coating, plastics, papermaking and preparation method thereof with titanium dioxide character.The bag of powder of the present invention nuclear matrix by 30～50% superfine heavy calcium carbonate, forge 5～15% and burn kaolin or water-washed kaolines, and 5～10% barites mix and constitute, its coating thing is 25～60% titanium dioxide.Preparation method of the present invention mixes water-ground limestone, kaolin, barite earlier, add organic surface modifying agent and water and make slurry, the employing wet method stripping grinds, add inorganic surfaces properties-correcting agent again, grinding material is to suitable particle diameter again, adding is organic in titanium dioxide makes slurry with inorganic surfaces properties-correcting agent and water, titania slurry is mixed with the composite granule slurry, the composite granule slurry is ground to the fineness of requirement with wet method stripping, with slurry convection drying, pulverizing, be prepared into the titanium dioxide complex ore powder again.
Description
Technical field
The present invention relates to a kind of mineral powder and preparation method thereof, is composite granule with titanium dioxide character that is used in fields such as coating, plastics, papermaking and preparation method thereof exactly.This powder is also referred to as the dioxide composite titanium valve.Powder of the present invention constitutes bag nuclear matrix by water-ground limestone, kaolin or ground barium sulfate and forms for the coating thing with titanium dioxide.
Background technology
Titanium dioxide is a kind of white pigment that is widely used in fields such as coating, plastics, papermaking, has excellent thermotolerance, weathering resistance, chemical stability, easily disperses, and whiteness and opacifying power are good, are a kind of white pigments of excellence.But because the price of titanium dioxide is higher, especially in its some Application Areass such as products such as coating, plastics, under the pressure of the pressure of product cost, people are seeking the cost that some substitutes reduce product.
In recent years, investigators cause in the technological development of titanium dioxide surrogate in power, have occurred some in succession and have prepared the method for composite titanium dioxide pigment, useful wollastonite, TiO
2, oxide compound (ZnO, Al
2O
3) powder that is compounded to form of siloxanes coupling agent, as the disclosed content of Chinese patent CN1052127.More be to adopt TiCl in the prior art
4, TiOSO
4Hydrolysis is carried out liquid phase chemical deposition on wollastonite, kaolin surface, carries out the method for drying, rinsing, roasting then, for example the disclosed content of Chinese patent CN1206727, CN1464011.Though the liquid phase chemical deposition material cost is lower, production unit has high input, complex process (hydrolysis reaction control, washing, filtration, dry, roasting), and the manufacturing cost height is difficult to realize industrialization.Nearly 2 years,, occur preparing composite titanium dioxide pigment such as Chinese patent CN1724595 with the method for wet ultra-fine grinding along with the technology raising of machining equipment.The employed inner nuclear material of this patent is lime carbonate or calcined kaolin or kaolin or wollastonite or barite, itself and titanium dioxide powder is carried out compoundly again, carries out grain-grain coating modification by Mechanochemical Effect.But this patent is owing to adopt single mineral powder, and its effect is unsatisfactory.For example be bag nuclear matrix with the barite, excessive because of bar density, in coating, easily produce sedimentation; And the bag of single use wollastonite nuclear matrix, its alkalescence is higher; As being that the cost of composite pigment is descended not clearly with calcined kaolin, and the powder oil number that forms is bigger; Though lime carbonate is with low cost, the whiteness height, density is moderate, and its acid resistance is poor.
Summary of the invention
The invention provides a kind of insufficient complex ore powder material of prior art that overcomes, this preparation methods is provided simultaneously.
The present invention mixes with water-ground limestone, kaolin and ground barium sulfate, form the bag nuclear matrix of composite granule, form for the coating thing with titanium dioxide again, the bag of its powder nuclear matrix by 30～50% superfine heavy calcium carbonate, forge 5～15% and burn kaolin or water-washed kaolines, and 5～10% barite mix to constitute, its coating thing is 25～60% titanium dioxide.
The used above-mentioned mineral powder of the present invention has different specific refractory poweres, density and oil number, and has difform grain pattern.As bar specific refractory power be 1.64, the specific refractory power of water-ground limestone is 1.65, their specific refractory power is higher relatively, and kaolinic specific refractory power is relatively low, is 1.56.They by aforesaid mixed, are ground through wet method stripping, add after organic and inorganic surface-modifying agent handles, can obtain good comprehensive properties white fine mineral kernel matrix powder, help the opacifying power of composite granule; The density difference of next each mineral powder, as: bar density is higher, is 4.47g/cm
3Though, be unfavorable for the anti-settling of composite granule, because of kaolinic laminated structure and relatively low density, its density is 2.60g/cm
3, but will help the suspension of composite granule after their mixing.In addition, the oil number difference of different minerals powder, as: bar oil number is 6～12%, and the oil number of water-ground limestone is 10～25%, and kaolinic oil number is 30～50%, and the oil number of titanium dioxide is 20～25%, to can make the oil number of composite granule be unlikely to too high after the multi mineral mixing, help dispersion and the need amount of resin of composite granule in coating less, be beneficial to the cost that reduces coating, can make its oil number relatively low simultaneously.
The preparation method of titanium dioxide complex ore powder of the present invention takes by weighing superfine heavy calcium carbonate by the powder proportion of composing, calcined kaolin or water-washed kaoline, barite, and titanium dioxide, earlier with water-ground limestone, calcined kaolin or water-washed kaoline, the barite thorough mixing, the organic surface modifying agent that adds the total amount 0.2～0.8% of mixed powder therein, add water and make the slurry of concentration 73～78%, adopt wet method stripping to be ground to material particular diameter less than 6-8 μ m, the inorganic surfaces properties-correcting agent that adds the powder mix scale of construction 1～10% again, continuing to be ground to material particular diameter is 4-6 μ m, in the titanium dioxide amount, add the organic surface modifying agent of titanium dioxide amount 0.3～0.8% and 1～5% inorganic surfaces properties-correcting agent, add water again and make 68～73% titania slurry, titania slurry is mixed with the composite granule slurry, the composite granule slurry is ground to the fineness of requirement with wet method stripping, again with the slurry convection drying, pulverize, be prepared into the titanium dioxide complex ore powder.
Used organic surface modifying agent is a water-soluble polymer dispersant among the preparation method of the present invention, for example polyacrylate or organotitanate coupling agent, used inorganic surfaces properties-correcting agent is the inorganic water-sol, as TiO 2 sol, or water glass, or silicon sol.
Organic surface modifying agent used in the present invention is a water-soluble polymer dispersant, as polyacrylate, organotitanate coupling agent the concentration of powdery pulp is reached more than 73%, this will help, and wet method stripping grinds and exsiccant technology is carried out, and polyacrylate, organotitanate coupling agent can make composite superfine powder have stability preferably simultaneously.The inorganic surfaces properties-correcting agent that the present invention is all is as TiO
2Colloidal sol, water glass, silicon sol etc. can react with the mineral powder surface, help TiO
2Carry out the particle coating reaction with the mineral powder surface.
Powder component of the present invention cooperates rationally, can obtain best effect, and preparation technology of the present invention is simple, and easy to operate, the production efficiency height is convenient to apply industrial.
Embodiment
Embodiment 1
Earlier particle diameter is mixed less than 325 purpose water-ground limestone 2400g, calcined kaolin (or water-washed kaoline) 600g, barite 600g, add about 1100g water, 12g polyacrylic acid dipersant, stir.Be ground to below the median size 6-8 μ m by the machine wet method stripping of delaminating then, add 100g water glass, continue to be ground to 4-6 μ m, the dilution heat of sulfuric acid with 5% transfers to slurry pH value below 10, and it is standby to make compound white fine mineral powder kernel matrix slurry.With anatase titanium dioxide TiO
22400g, add the about 1100g of entry, polyacrylic acid dipersant 12g, water glass 50g, fully be dispersed into TiO
2Slurry.Two kinds of slurries are mixed, be ground to below the median size 2 μ m by the machine wet method stripping of delaminating again, after drying is pulverized then, be composite granule pigment.The performance of this composite granule pigment is seen attached list.
Embodiment 2
Particle diameter is mixed less than 325 order water-ground limestone 2100g, calcined kaolin (or water-washed kaoline) 900g, barite 600g, add about 1100g water, 12g organotitanate coupling agent, stir.Be ground to below the median size 5-7 μ m by the machine wet method stripping of delaminating then, add the 120g silicon sol, continue to be ground to 3-5 μ m, it is standby to make compound white fine mineral powder kernel matrix slurry.With rutile TiO
22400g adds the about 1000g of entry, 10g organotitanate coupling agent, 60g silicon sol, fully is dispersed into TiO
2Slurry.Two kinds of slurries are mixed, be ground to below the median size 2 μ m by the machine wet method stripping of delaminating again, after drying is pulverized then, be composite granule pigment.The performance of this composite granule pigment is seen attached list.
Embodiment 3
Particle diameter is mixed less than 325 order water-ground limestone 3000g, calcined kaolin 900g, barite 600g, add about 1500g water, 20g organotitanate coupling agent, stir.Be ground to below the median size 6-8 μ m by the machine wet method stripping of delaminating then, add the TiOSO of 400g 50%
4The aqueous solution continues to be ground to 4-6 μ m, and it is standby to make compound white fine mineral powder kernel matrix slurry.With anatase titanium dioxide TiO
21500g adds the about 600g of entry, organotitanate coupling agent 10g, fully is dispersed into TiO
2Slurry.Two kinds of slurries are mixed, be ground to below the median size 2 μ m by the machine wet method stripping of delaminating again, after drying is pulverized then, be composite granule pigment.The performance of this composite granule pigment is seen attached list.
Embodiment 4
Particle diameter is mixed less than 325 purpose water-ground limestone 2400g, calcined kaolin 300g, barite 300g, add about 1000g water, 12g polyacrylic acid dipersant, stir.Be ground to below the median size 5-7 μ m by the machine wet method stripping of delaminating then, add the TiOSO of 300g 50%
4The aqueous solution (or silicon sol) continues to be ground to 3-5 μ m, and it is standby to make compound white fine mineral powder kernel matrix slurry.With rutile TiO
23000g adds the about 1200g of entry, polyacrylic acid dipersant 12g, fully is dispersed into TiO
2Slurry.Two kinds of slurries are mixed, be ground to below the median size 2 μ m by the machine wet method stripping of delaminating again, after drying is pulverized then, be composite granule pigment.The performance of this composite granule pigment is seen attached list.
Embodiment 5
Earlier particle diameter is mixed less than 325 purpose water-ground limestone 1800g, calcined kaolin 900g, barite 600g, add about 1000g water, 10g polyacrylic acid dipersant, stir.Be ground to below the median size 6-8 μ m by the machine wet method stripping of delaminating then, add 200g silicon sol (or TiOSO
4The aqueous solution), continue to be ground to 4-6 μ m, it is standby to make compound white fine mineral powder kernel matrix slurry.With anatase titanium dioxide TiO
22700g adds the about 1200g of entry, polyacrylic acid dipersant 18g, silicon sol 100g, fully is dispersed into TiO
2Slurry.Two kinds of slurries are mixed, be ground to below the median size 2 μ m by the machine wet method stripping of delaminating again, after drying is pulverized then, be composite granule pigment.The performance of this composite granule pigment is seen attached list.
Embodiment 6
Earlier particle diameter is mixed less than 325 purpose water-ground limestone 3000g, calcined kaolin 300g, barite 300g, add about 1100g water, 12g polyacrylic acid dipersant, stir.Be ground to below the median size 5-7 μ m by the machine wet method stripping of delaminating then, add 300g silicon sol (or TiOSO
4The aqueous solution), continue to be ground to 3-5 μ m, it is standby to make compound white fine mineral powder kernel matrix slurry.With rutile TiO
22400g adds the about 1100g of entry, polyacrylic acid dipersant 15g, silicon sol 100g, fully is dispersed into TiO
2Slurry.Two kinds of slurries are mixed, be ground to below the median size 2 μ m by the machine wet method stripping of delaminating again, after drying is pulverized then, be composite granule pigment.The performance of this composite granule pigment is seen attached list.
Embodiment 7
Particle diameter is mixed less than 325 purpose water-ground limestone 1800g, calcined kaolin 600g, barite 300g, add about 800g water, 12g organotitanate coupling agent, stir.Be ground to below the median size 5-7 μ m by the machine wet method stripping of delaminating then, add 200g silicon sol (or TiOSO
4The aqueous solution), continue to be ground to 3-5 μ m, it is standby to make compound white fine mineral powder kernel matrix slurry.With rutile TiO
23300g adds the about 1300g of entry, organotitanate coupling agent 15g, silicon sol 150g, fully is dispersed into TiO
2Slurry.Two kinds of slurries are mixed, be ground to below the median size 2 μ m by the machine wet method stripping of delaminating again, after drying is pulverized then, be composite granule pigment.The performance of this composite granule pigment is seen attached list.
Embodiment 8
Particle diameter is mixed less than 325 purpose water-ground limestone 1800g, calcined kaolin 300g, barite 300g, add about 800g water, 12g organotitanate coupling agent, stir.Be ground to below the median size 6-8 μ m by the machine wet method stripping of delaminating then, add the TiOSO of 200g 50%
4The aqueous solution (or silicon sol) continues to be ground to 4-6 μ m, and it is standby to make compound white fine mineral powder kernel matrix slurry.With anatase titanium dioxide TiO
23600g adds the about 1500g of entry, 12g organotitanate coupling agent, fully is dispersed into TiO
2Slurry.Two kinds of slurries are mixed, be ground to below the median size 2 μ m by the machine wet method stripping of delaminating again, after drying is pulverized then, be composite granule pigment.The performance of this composite granule pigment is seen attached list.
Subordinate list
By data that above embodiment surveys as seen, product performance of the present invention are very desirable.
Claims (2)
1, the preparation method of titanium dioxide complex ore powder, it is characterized in that taking by weighing respectively superfine heavy calcium carbonate, calcined kaolin or water-washed kaoline, the superfine heavy calcium carbonate of barite and four kinds of powder gross weights 30～50% of titanium dioxide, 5～15% calcined kaolins or water-washed kaoline, 5～10% barite, with 25～60% titanium dioxide, earlier with water-ground limestone, calcined kaolin or water-washed kaoline, the barite thorough mixing, add the polyacrylate of gross weight 0.2～0.8% of mixed powder or the organic surface modifying agent of organotitanate coupling agent therein, add water and make the slurry of concentration 73～78%, adopt wet method stripping to be ground to material particular diameter less than 6 μ m, add the TiO 2 sol of the powder mix scale of construction 1～10% or the inorganic surfaces properties-correcting agent of water glass or silicon sol again, continuing to be ground to material particular diameter is 4-6 μ m, in titanium dioxide, add the polyacrylate of titanium dioxide amount 0.3～0.8% or the water glass or the silicon sol of organotitanate coupling agent and 1～5%, add water again and make 68～73% titania slurry, titania slurry is mixed with the mixed powder slurry, slurry is ground to the fineness of requirement with wet method stripping, again with the slurry convection drying, pulverize, be prepared into the titanium dioxide complex ore powder, used TiO 2 sol is to contain 50% TiOSO
4The aqueous solution.
2, the titanium dioxide complex ore powder of the described method preparation of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101014849A CN100560657C (en) | 2007-04-23 | 2007-04-23 | TiO 2Complex ore powder and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101014849A CN100560657C (en) | 2007-04-23 | 2007-04-23 | TiO 2Complex ore powder and preparation method |
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|---|---|
| CN101041748A CN101041748A (en) | 2007-09-26 |
| CN100560657C true CN100560657C (en) | 2009-11-18 |
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| CNB2007101014849A Expired - Fee Related CN100560657C (en) | 2007-04-23 | 2007-04-23 | TiO 2Complex ore powder and preparation method |
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| CN101492575B (en) * | 2008-01-21 | 2011-11-23 | 河南佰利联化学股份有限公司 | Surface modified method for titanium dioxide for papermaking |
| CN101250337B (en) * | 2008-03-19 | 2010-08-25 | 中国高岭土公司 | Titania coating kaolinite compound powder and method for preparing same |
| CN102634240B (en) * | 2012-04-28 | 2014-06-18 | 安徽江东科技粉业有限公司 | Preparation method of calcium carbonate based reinforcing agent for PVC (polyvinyl chloride) advertising film |
| CN104098932B (en) * | 2013-04-15 | 2016-05-25 | 中国地质大学（北京） | A kind of preparation method of white mineral-titanium dioxide composite powder pigment |
| CN103351648B (en) * | 2013-05-31 | 2014-09-17 | 句容亿格纳米材料厂 | Composite titanium dioxide and processing method thereof |
| CN105001679A (en) * | 2014-11-26 | 2015-10-28 | 安徽池州博源非金属矿研发中心有限公司 | Composite titanium dioxide |
| CN105017812A (en) * | 2014-11-26 | 2015-11-04 | 安徽池州博源非金属矿研发中心有限公司 | Composite titanium dioxide |
| CN104785349B (en) * | 2015-04-29 | 2017-05-03 | 浙江冠旗纳米科技有限公司 | Efficient preparation method for nano-scale solid powder |
| CN105597718A (en) * | 2015-10-12 | 2016-05-25 | 福建师范大学泉港石化研究院 | Preparation method of inorganic mineral powder supported nano-TiO2 photocatalyst |
| CN105567044A (en) * | 2016-03-01 | 2016-05-11 | 安徽爱迪尔新材料科技有限公司 | Pure acrylic emulsion outer wall coating |
| CN105754378B (en) * | 2016-03-23 | 2018-11-09 | 河南鑫泰钙业有限公司 | A kind of calcium base titanium dioxide and its preparation process |
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| CN106479247B (en) * | 2016-08-18 | 2018-09-14 | 西藏亚吐克工贸有限公司 | The application of barium sulfate and titanium white compound powder on coating |
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| CN106590062A (en) * | 2016-12-06 | 2017-04-26 | 大连环球矿产股份有限公司 | Preparation method of composite titanium dioxide pigment with wollastonite coated with titanium dioxide |
| CN107163571B (en) * | 2017-05-17 | 2019-11-22 | 江苏金发科技新材料有限公司 | Laser welding long-life flat fiber modified polyamide composite material |
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| CN110482602B (en) * | 2019-09-18 | 2022-02-18 | 吉林大学 | Preparation method of TiO 2/wollastonite compound |
| CN110724427B (en) * | 2019-09-29 | 2021-09-21 | 深圳市亚仕德新材料有限公司 | Waterproof acid-resistant paint, preparation method thereof and waterproof acid-resistant coating |
| CN111663364B (en) * | 2020-06-17 | 2022-07-12 | 辽宁艾海滑石有限公司 | Preparation method of wet papermaking coating slurry liquid |
| CN111875990A (en) * | 2020-08-07 | 2020-11-03 | 江西广源化工有限责任公司 | Composite titanium dioxide and preparation method and application thereof |
| CN112876878A (en) * | 2021-01-26 | 2021-06-01 | 江西势通钙业有限公司 | Ultrahigh-whiteness pigment-grade core-shell structure type nano calcium carbonate and preparation method thereof |
| CN115247006B (en) * | 2021-11-12 | 2023-03-24 | 立邦涂料（中国）有限公司 | Light composite titanium dioxide and preparation method thereof |
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