CN1371947A - Method for covering nano calcium carbonate on heavy mass calcium carbonate surface - Google Patents
Method for covering nano calcium carbonate on heavy mass calcium carbonate surface Download PDFInfo
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- CN1371947A CN1371947A CN 01104494 CN01104494A CN1371947A CN 1371947 A CN1371947 A CN 1371947A CN 01104494 CN01104494 CN 01104494 CN 01104494 A CN01104494 A CN 01104494A CN 1371947 A CN1371947 A CN 1371947A
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Abstract
The method for preparing nano calcium carbonate-heavy calcium carbonate composition nano material combines advantages of physical method and chemical method, and is characterized by that on the surface of heavy calcium carbonate made up by physical method a layer of nano calcium carbonate granules is deposited by means of chemical method. Said invented composite nano material can be extensively used in the fields of paper-making industry, plastics, rubber and paint industries.
Description
The present invention is the novel method of a kind of preparation nano-calcium carbonate-water-ground limestone composite nano materials.
The particulate preparation method mainly contains physics and two kinds of chemistry.Physics is that the particle cost of mechanical means preparation is low, and the particulate median size is bigger; The particle cost height of chemical method preparation, particle diameter is less.The water-ground limestone of prepared by physical method allows the higher amount of filling out that adds, and can increase economic efficiency thus; The particulate form helps the combination of fiber, helps the intensity of page; The maneuverability of paper machine is better, because the moisture of detention is less, drainability is better; Influence to applying glue is less.But whiteness and opaqueness are lower than the light calcium carbonate that adds the amount of filling out on an equal basis; Slimy water-ground limestone is transported in the user way will add dispersion agent, to prevent particles settling, has therefore increased cost; The hardness of natural heavy calcium carbonate is bigger, and the form of particle makes that the abrasion number is bigger, and wet end, paper machine parts are had bigger wearing and tearing.The light calcium carbonate of chemical method preparation can make page produce high opaqueness, whiteness and bulk; The abrasion number is low in the process of manufacturing paper with pulp, and alleviates the wearing and tearing to equipment; The electromotive force height of surface charge helps the distribution of particle in page like this., light calcium carbonate particulate specific surface area is big, has reduced applying glue efficient; The combination that little gap affects has been arranged between the fiber between particle has reduced the intensity of page thus; Light calcium carbonate than the detention of heavy lime carbonate more moisture, this means that the speed of a motor vehicle of paper machine will reduce; When adding, light calcium carbonate can produce the mass production problem when amount of filling out surpasses 15%.
Purpose of the present invention is exactly the particulate relative merits that comprehensive two kinds of methods are produced, and maximizes favourable factors and minimizes unfavourable ones, and explores a method for preparing nano-calcium carbonate-water-ground limestone composite particles.This composite particles had both been preserved addition that water-ground limestone particulate form can keep filler more greatly to reduce the cost, and its surface is again by the modification of the light calcium carbonate of nanometer institute simultaneously, reduced evil spirit than low strength and decreased thereby have.And the surface of water-ground limestone is had high whiteness and good dispersiveness by nanometer light calcium carbonate coating back as filler in application.Therefore this composite particles is a kind of type material with huge applications prospect.
The preparation of the nano-calcium carbonate among the present invention-water-ground limestone composite particles is in certain density aqua calcis, adds a certain amount of water-ground limestone and specific additive, is made into suspension under the whipping force effect.Feed carbonic acid gas then, calcium hydroxide is carried out carbonization.The nano-calcium carbonate that calcium hydroxide and carbon dioxide reaction generate in the regular hour at water-ground limestone surface forming core, grow up.Then filtration, drying, dispersion can obtain nano-calcium carbonate-water-ground limestone composite particles.
In the preparation process of the nano-calcium carbonate among the present invention-water-ground limestone composite particles there be controllable factor: the 1. concentration of calcium hydroxide; 2. the massfraction of carbonic acid gas; 3. the kind of additive, quantity and interpolation time.Consider from chemical reaction rate and lime carbonate mechanism of nucleation angle, have two controllable factors again: 4. stir speed (S.S.); 5. temperature of reaction.The median size of water-ground limestone also is an important factor in addition.
The concentration of calcium hydroxide can be 1～20% in the preparation process of the nano-calcium carbonate among the present invention-water-ground limestone composite particles.The concentration of calcium hydroxide is low more, and the nano-calcium carbonate particles particle diameter that carbonization obtains is more little.But concentration is low more, and power consumption is high more, and required equipment container volume increases.Water-ground limestone is a micron order, according to irregular the differing of different application background particle diameter.The massfraction of carbonic acid gas is 10～80%, and along with the increase of carbon dioxide content, the calcium carbonate granule particle diameter that carbonization generates increases.Stir speed (S.S.) is 1000～3000rpm, and under the constant prerequisite of other condition, along with the raising of rotating speed, the lime carbonate particle diameter that carbonization generates diminishes.The amount of additive is 0.01～3%, and the additive add-on increases, and the products obtained therefrom particle diameter reduces, and when being reduced to a certain degree, particle diameter will increase with the increase of additive amount.Add the calcium carbonate granule particle diameter minimum that additive obtains when general reaction begins, the time that adds additive in the reaction process is slow more, and the calcium carbonate granule particle diameter of generation is big more.The optional organic polyphosphate of additive types, sequestrant.Temperature of reaction can be controlled in 0～60 ℃.
The preparation of the nano-calcium carbonate among the present invention-water-ground limestone composite particles is in 1～20% aqua calcis, the organic polyphosphate additive that adds a certain amount of water-ground limestone and 0.01～3%, under the whipping force effect, be made into suspension, stirring velocity is 1500～3000rpm, and solution temperature is controlled at 0～30 ℃.Feed massfraction then and be 10～50% carbonic acid gas, calcium hydroxide is carried out carbonization.The nano-calcium carbonate that calcium hydroxide and carbon dioxide reaction generate in the regular hour at water-ground limestone surface forming core, grow up.Then filtration, drying, dispersion can obtain nano-calcium carbonate-water-ground limestone composite particles, and the median size of nano-calcium carbonate is 10～50nm, and clad ratio is more than 80%.
The preparation of the nano-calcium carbonate among the present invention-water-ground limestone composite particles is in 1～20% aqua calcis, the sequestrant additive that adds a certain amount of water-ground limestone and 0.01～3%, under the whipping force effect, be made into suspension, stirring velocity is 1000～3000rpm, and solution temperature is controlled at 0～60 ℃.Feed massfraction then and be 10～80% carbonic acid gas, calcium hydroxide is carried out carbonization.The nano-calcium carbonate that calcium hydroxide and carbon dioxide reaction generate in the regular hour at water-ground limestone surface forming core, grow up.Then filtration, drying, dispersion can obtain nano-calcium carbonate-water-ground limestone composite particles, and the median size of nano-calcium carbonate is 10～80nm, and clad ratio is more than 80%.
Method of the present invention can be applied to other particulate surface coated nano calcium carbonate particle equally.Mineral powder such as micron wollastonite, talcum for example.
Example one:
Adopt 2000g mechanical disintegration water-ground limestone particle, median size 5 μ m.Add 5000ml, in 8% aqua calcis, stirring velocity is 2500rpm, adds the organic polyphosphate additive of 5g again, and solution temperature is controlled at 10 ℃.Feed carbonic acid gas then, its massfraction is 30%, stops ventilation when the Ph value reaches 8.Refilter, dry, disperse nano-calcium carbonate-water-ground limestone composite particles, the nano-calcium carbonate median size is 40nm.
Example two:
Adopt 2000g mechanical disintegration water-ground limestone particle, median size 10 μ m.Add 5000ml, in 15% aqua calcis, stirring velocity is 2400rpm, adds the organic polyphosphate additive of 10g again, and solution temperature is controlled at 25 ℃.Feed carbonic acid gas then, its massfraction is 50%, stops ventilation when the Ph value reaches 8.Refilter, dry, disperse nano-calcium carbonate-water-ground limestone composite particles, the nano-calcium carbonate median size is 50nm.
Claims (6)
1. novel method for preparing nano-calcium carbonate-water-ground limestone composite nano materials is characterized in that the advantage of binding substances logos and two kinds of milling methods of chemical method, makes the composite particles of good characteristic.Its essential characteristic is:
1. adopt the mechanical-physical method to make water-ground limestone, particle diameter is in micron order or higher level;
2. join certain density aqua calcis, water-ground limestone and additive are added wherein, under the whipping force effect, make suspension;
3. in suspension, feed certain mass fractional carbonic acid gas, calcium hydroxide is carried out the carbonization certain hour;
4. to solution filter, dry, disperse to get final product nano-calcium carbonate-water-ground limestone composite particles.
2. according to the described method of claim 1, aqua calcis concentration is 1～20%, and the water-ground limestone median size is in the micron higher level.
3. according to the described method of claim 1, stirring velocity is in 1000～3000rpm scope.
4. according to the described method of claim 1, additive is organophosphate and sequestrant, and addition is in 0.01～3% scope, and the interpolation time is when carburizing reagent begins.
5. according to the described method of claim 1, the carbonic acid gas massfraction is 10～80%, and temperature of reaction is controlled at 0～60 ℃.
6. according to the described method of claim 1, can prepare other micron particle surface coated nano calcium carbonate particulate matrix material equally, as nano-calcium carbonate-wollastonite composite particles, nano-calcium carbonate---hydrotalcite compound particle etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01104494 CN1208399C (en) | 2001-02-27 | 2001-02-27 | Method for covering nano calcium carbonate on heavy mass calcium carbonate surface |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 01104494 CN1208399C (en) | 2001-02-27 | 2001-02-27 | Method for covering nano calcium carbonate on heavy mass calcium carbonate surface |
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| CN1371947A true CN1371947A (en) | 2002-10-02 |
| CN1208399C CN1208399C (en) | 2005-06-29 |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374515C (en) * | 2002-11-14 | 2008-03-12 | 中国乐凯胶片集团公司 | New pattern UV light solidifying powdery paints |
| CN101456969B (en) * | 2008-12-29 | 2011-11-09 | 南京协和化学有限公司 | Functional calcium carbonate and method for producing the same |
| CN102504617A (en) * | 2011-09-30 | 2012-06-20 | 广东轻工职业技术学院 | Kaolin composite material and preparation method thereof |
| CN102659159A (en) * | 2012-02-22 | 2012-09-12 | 常州碳酸钙有限公司 | Method for preparing micron-granule composite nano calcium carbonate |
| CN101560335B (en) * | 2009-05-25 | 2012-11-07 | 长兴清华粉体及新材料工程中心有限公司 | Method for preparing nanometer coating compound calcium carbonate |
| CN103756241A (en) * | 2013-12-31 | 2014-04-30 | 东莞市松燊塑料科技有限公司 | Environment-friendly ABS/PET (acrylonitrile-butadiene-styrene/polyethylene glycol terephthalate) alloy and preparation method thereof |
| CN104432470A (en) * | 2014-12-02 | 2015-03-25 | 云南中烟工业有限责任公司 | Preparation method of regenerated tobacco filler with paper-making process and application of regenerated tobacco filler |
| CN104705775A (en) * | 2015-01-30 | 2015-06-17 | 云南中烟工业有限责任公司 | Preparation and application for paper-making process reconstituted tobacco sizing agent coated with calcium carbonate |
| CN105646940A (en) * | 2015-12-28 | 2016-06-08 | 江南大学 | Method for coating surface of potassium titanate whisker with nanometer calcium carbonate |
| CN106349755A (en) * | 2016-08-19 | 2017-01-25 | 云南宏创新材料科技有限公司 | Preparation method of high-reinforcing nano calcium carbonate/one-dimensional mineral composite |
| CN109251557A (en) * | 2018-07-12 | 2019-01-22 | 广西华纳新材料科技有限公司 | A kind of preparation method of nuclear shell structured nano winnofil |
| CN110565432A (en) * | 2019-09-19 | 2019-12-13 | 泉州市东紫环保科技有限公司 | Modified heavy calcium carbonate powder used as neutral paper filler and preparation method thereof |
| CN113698793A (en) * | 2021-08-16 | 2021-11-26 | 浙江清大粉体材料有限公司 | Method and equipment for coating nano calcium carbonate on surface of heavy calcium carbonate |
| CN113697836A (en) * | 2021-08-16 | 2021-11-26 | 浙江清大粉体材料有限公司 | Method and equipment for preparing nano-coated composite calcium carbonate |
| CN113800547A (en) * | 2021-10-08 | 2021-12-17 | 滨州职业学院 | Digestion-carbonization device and calcium carbonate nano-coating process |
| CN113861725A (en) * | 2021-10-19 | 2021-12-31 | 中科乐美科技集团有限公司 | Preparation method of calcium carbonate/talcum powder composite material |
| CN114350180A (en) * | 2021-12-03 | 2022-04-15 | 广西大学 | Mechanical activation nano-modified heavy calcium carbonate and preparation method thereof |
| CN115521520A (en) * | 2022-10-21 | 2022-12-27 | 安徽电缆股份有限公司 | Termite-proof cable outer sheath material and preparation method thereof |
-
2001
- 2001-02-27 CN CN 01104494 patent/CN1208399C/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374515C (en) * | 2002-11-14 | 2008-03-12 | 中国乐凯胶片集团公司 | New pattern UV light solidifying powdery paints |
| CN101456969B (en) * | 2008-12-29 | 2011-11-09 | 南京协和化学有限公司 | Functional calcium carbonate and method for producing the same |
| CN101560335B (en) * | 2009-05-25 | 2012-11-07 | 长兴清华粉体及新材料工程中心有限公司 | Method for preparing nanometer coating compound calcium carbonate |
| CN102504617A (en) * | 2011-09-30 | 2012-06-20 | 广东轻工职业技术学院 | Kaolin composite material and preparation method thereof |
| CN102659159A (en) * | 2012-02-22 | 2012-09-12 | 常州碳酸钙有限公司 | Method for preparing micron-granule composite nano calcium carbonate |
| CN103756241A (en) * | 2013-12-31 | 2014-04-30 | 东莞市松燊塑料科技有限公司 | Environment-friendly ABS/PET (acrylonitrile-butadiene-styrene/polyethylene glycol terephthalate) alloy and preparation method thereof |
| CN103756241B (en) * | 2013-12-31 | 2016-06-29 | 东莞市松燊塑料科技有限公司 | A kind of environmental protection ABS/PET Alloy And Preparation Method |
| CN104432470A (en) * | 2014-12-02 | 2015-03-25 | 云南中烟工业有限责任公司 | Preparation method of regenerated tobacco filler with paper-making process and application of regenerated tobacco filler |
| CN104705775A (en) * | 2015-01-30 | 2015-06-17 | 云南中烟工业有限责任公司 | Preparation and application for paper-making process reconstituted tobacco sizing agent coated with calcium carbonate |
| CN105646940A (en) * | 2015-12-28 | 2016-06-08 | 江南大学 | Method for coating surface of potassium titanate whisker with nanometer calcium carbonate |
| CN106349755A (en) * | 2016-08-19 | 2017-01-25 | 云南宏创新材料科技有限公司 | Preparation method of high-reinforcing nano calcium carbonate/one-dimensional mineral composite |
| CN109251557A (en) * | 2018-07-12 | 2019-01-22 | 广西华纳新材料科技有限公司 | A kind of preparation method of nuclear shell structured nano winnofil |
| CN109251557B (en) * | 2018-07-12 | 2021-04-02 | 广西华纳新材料科技有限公司 | Preparation method of core-shell structure nano precipitated calcium carbonate |
| CN110565432A (en) * | 2019-09-19 | 2019-12-13 | 泉州市东紫环保科技有限公司 | Modified heavy calcium carbonate powder used as neutral paper filler and preparation method thereof |
| CN113698793A (en) * | 2021-08-16 | 2021-11-26 | 浙江清大粉体材料有限公司 | Method and equipment for coating nano calcium carbonate on surface of heavy calcium carbonate |
| CN113697836A (en) * | 2021-08-16 | 2021-11-26 | 浙江清大粉体材料有限公司 | Method and equipment for preparing nano-coated composite calcium carbonate |
| CN113800547A (en) * | 2021-10-08 | 2021-12-17 | 滨州职业学院 | Digestion-carbonization device and calcium carbonate nano-coating process |
| CN113861725A (en) * | 2021-10-19 | 2021-12-31 | 中科乐美科技集团有限公司 | Preparation method of calcium carbonate/talcum powder composite material |
| CN114350180A (en) * | 2021-12-03 | 2022-04-15 | 广西大学 | Mechanical activation nano-modified heavy calcium carbonate and preparation method thereof |
| CN115521520A (en) * | 2022-10-21 | 2022-12-27 | 安徽电缆股份有限公司 | Termite-proof cable outer sheath material and preparation method thereof |
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