CN1438178A - Method for preparing nano active calcium carbonate - Google Patents
Method for preparing nano active calcium carbonate Download PDFInfo
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- CN1438178A CN1438178A CN 02160099 CN02160099A CN1438178A CN 1438178 A CN1438178 A CN 1438178A CN 02160099 CN02160099 CN 02160099 CN 02160099 A CN02160099 A CN 02160099A CN 1438178 A CN1438178 A CN 1438178A
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Abstract
The preparation method of nano active calcium carbonate is characterized by that it uses the carbide slag as raw material, which includes the following steps: adding water into calcium oxide obtained by cleaning carbide slag, digesting to obtain calcium hydroxide sturry liquor with a certain concentration, then introducing CO2 and at the same time adding additive to make carbonization reaction, and controlling a series of technological parameters to prepare nano calcium carbonate with a certain grain size, then adopting a certain surface treatment process to make the nano calcium carbonate undergo the process of organic surface modification and make it surface be oleophilic and have good dispersion property in oil phase.
Description
Technical Field
The invention relates to a preparation method of nano active calcium carbonate, belonging to the technical field of chemical compound preparation and the technical field of surface treatment.
Background
The calcium carbide is an important chemical raw material, is mainly used for producing acetylene gas, PVC, carbon black and the like, has a large using amount, but can discharge a large amount of calcium carbide waste slag which is difficult to dispose during production, not only occupies a large amount of land, but also causes great pollution to the environment, and is particularly important for developing a comprehensive utilization technology of the calcium carbide slag in order to protect the environment and change waste into valuable.
For example, chinese patents CN1058004A and CN1058005A propose methods for preparing high-purity industrial calcium carbonate and high-purity industrial calcium oxide from carbide slag, but these methods produce products with low added value and low economic benefit.
The nanometer level superfine calcium carbonate is one new kind of superfine material developed in the 80's 20 th century, and has grain size of 1-100nm, and owing to the superfine nanometer level calcium carbonate particle, its structure and surface electronic structure are changed to produce quantum size effect, small size effect, surface effect and macroscopic quantum effect not possessed by common calcium carbonate. When it is filled into rubber or plastic, it can make the surface of product have good gloss and mechanical property be improved, so that it is an excellent white reinforcing filler. The paint has the characteristics of good gloss, transparency, stability, quick drying and the like in high-grade paint. The nanometer grade superfine calcium carbonate has steric effect, can suspend the lithopone with larger density in the paint preparation, and has the function of preventing sedimentation; after the paint is prepared, the whiteness of a paint film is increased, the luster is high, and the covering power is not reduced.
There are several methods for preparing nano-grade superfine calcium carbonate. Chinese patent CN1194944A proposes a method for preparing nano calcium carbonate with a particle size of less than 50nm by reacting sodium carbonate with calcium chloride in the presence of a dispersant such as ethanol, and the like, and the method adopts a raw material with a high price. Chinese patent CN1104179A proposes that calcium carbonate is prepared by carbonization method, and the surface treatment is directly performed on calcium carbonate emulsion by using higher fatty acid mixed glyceride at 35 ℃, but the patent does not relate to the particle size control of nano active calcium carbonate. USP5811070 proposes the stepwise preparation of ultrafine calcium carbonate with the particle size of 0.1-1.0 μm. The main steps of the method are that carbon dioxide is introduced into calcium hydroxide suspension containing additives such as saccharides and sodium glutamate to prepare calcium carbonate particles with the average particle size of 0.4 mu m, calcium hydroxide is prepared into solution according to the proportion of 10-100g/100g CaCO3 and added into the prepared calcium carbonate solution, additives such as polyacrylate and the like are added and carbon dioxide is introduced to continue the reaction, but the particle size of the calcium carbonate prepared by the patent method does not reach the nanometer level.
Disclosure of Invention
The invention aims to provide a method for producing a nano-scale superfine active calcium carbonate material by using carbide slag as a raw material.
The present invention achieves the above objects by the following means and measures.
The invention is characterized by comprising the following preparation steps:
a. the calcium oxide powder is prepared from calcium carbide dregs through purifying, filtering and calcining, and is digested with water
Forming calcium hydroxide slurry with a certain concentration, and performing carbonization reaction with carbon dioxide
Adding a certain amount of additive such as dilute sulfuric acid, sodium polyphosphate or zinc sulfate to obtain the nano calcium carbonate powder.
In the processes of washing, purifying, filtering and calcining the carbide slag raw material, the calcining temperature of a filter cake is 800-900 DEG C
℃。
b. Coating alumina on the surface of nano calcium carbonate powder, and the method is to prepare the nano calcium carbonate powder
Adding Al to the slurry2(SO4)3Heating the solution to 70 ℃, dripping NaAc solution, keeping the temperature for 1 hour, and then heating
And keeping the temperature for 1.5 hours at 90 ℃, wherein the coating amount of the alumina is 3-5% of the solid calcium carbonate.
c. Then organically treating the nano calcium carbonate powder by using stearic acid and dodecyl benzene
Sodium sulfonate is organically treated, the dosage of stearic acid is 2-4%, and the dosage of sodium dodecyl benzene sulfonate is
1.5-2 percent of calcium carbonate as a percentage calculation standard, and adding the prepared surface treatment liquid into calcium carbonate dispersion
In the liquid, the organic surface treatment temperature is 70-80 ℃, the treatment time is 1-2 hours, then the filtration is carried out, and the filter cake is obtained
Drying and crushing to obtain the nanometer active calcium carbonate powder.
The invention is characterized in that the obtained nano calcium carbonate powder is further subjected to surface treatment to increase the surface activity. In the method, a proper amount of aluminum oxide is coated on the surface of the nano calcium carbonate powder, and then organic surface treatment is carried out, so that the nano calcium carbonate powder with higher activity is obtained.
The chemical reaction equation for preparing calcium carbonate in the invention is as follows:
(1)
(2)
(3)
(4)
(5)
the surface modified nano calcium carbonate powder with high activity prepared by the method can be used as a filler in rubber and plastics, is an excellent white reinforcing filler, can also be used in high-grade paint and paint industry, and can improve the performance of the high-grade paint and paint.
The nano active calcium carbonate prepared by the method has a calcite-type structure, is cubic, has the particle size of 30-50 nm, is completely lipophilic, and can be uniformly dispersed in an oil phase.
Detailed Description
The embodiments of the present invention will now be described in the following:
the first embodiment is as follows: the invention adopts carbide slag as raw material, firstly, preliminarily purifying the carbide slag, adding water to prepare carbide slag slurry, standing for a period of time, then removing supernatant, filtering the lowerlayer of carbide slag slurry, drying filter cake, taking 40 g, calcining at 800 ℃ to obtain calcium oxide, digesting with 200 ml of 80 ℃ hot water, adding water to dilute after 30 minutes until the calcium oxide is diluted toThe concentration of the calcium hydroxide solution is 4 percent; adding 0.18 g of sodium polyphosphate, stirring uniformly, then introducing carbon dioxide and air into a gas mixer, wherein the volume concentration of the carbon dioxide is 25%, and adding 0.18 m3The mixed gas was fed into the carbonization reactor at a flow rate of 2500 rpm while maintaining high-speed stirring. The reaction temperature is controlled to be 22-25 ℃ during the reaction. The end point of the reaction is determined by measuring the conductivity of the reaction solution. The electric conductivity will show a decreasing curve when the reaction starts, then suddenly rises to the highest electric conductivity, the electric conductivity rapidly decreases after a few minutes, and when the second curve valley is reached, the reaction end point is reached, and the pH value of the reaction liquid is 7-8. The reactant is white emulsion, and is sand-milled after being placed for 2 hours. Then transferring the nano calcium carbonate dispersion liquid into a surface treatment reactor, and adding 49 ml of Al with the concentration of 300 g/L2(SO4)3And (3) heating the solution to 70 ℃ under stirring, then dropwise adding 31 ml of NaAC solution with the concentration of 600 g/L into the reaction solution, keeping the temperature for reaction for 1 hour, then heating to 90 ℃ and keeping the temperature for 1.5 hours. Then weighing 1.62 g of stearic acid and 0.81 g of sodium dodecyl benzene sulfonate to prepare a mixed surface treatment liquid, adding the mixed surface treatment liquid into the calcium carbonate dispersion liquid, carrying out organic surface treatment at 80 ℃ for 2 hours, then filtering while hot, drying and crushing a filter cake to obtain about 45 g of nano activecalcium carbonate powder.
Claims (3)
1. The preparation method of the nano active calcium carbonate is characterized by comprising the following preparation steps:
a. calcium oxide powder particles obtained by purification, filtration and calcination are added with water and digested by carbide slag to prepare calcium hydroxide slurry with a certain concentration, and the calcium hydroxide slurry and carbon dioxide are subjected to carbonization reaction, and a certain amount of additives such as dilute sulfuric acid, sodium polyphosphate or zinc sulfate can be added in the carbonization reaction process to obtain nano calcium carbonate powder;
b. coating alumina on the surface of nano calcium carbonate powder by adding Al into the slurry prepared from the nano calcium carbonate powder2(SO4)3Heating the solution to 70 ℃, dropwise adding a NaAc solution, keeping the temperature for 1 hour, heating to 90 ℃, keeping the temperature for 1.5 hours, wherein the coating amount of alumina is 3-5% of theoretical calcium carbonate solid;
c. then, carrying out organic treatment on the nano calcium carbonate powder, wherein the method comprises the steps of carrying out organic treatment on calcium carbonate by using stearic acid and sodium dodecyl benzene sulfonate, wherein the dosage of the stearic acid is 2-4%, the dosage of the sodium dodecyl benzene sulfonate is 1.5-2%, the calcium carbonate is used as a percentage calculation reference, the prepared surface treatment liquid is added into the calcium carbonate dispersion liquid, the organic surface treatment temperature is 70-80 ℃, and the treatment time is 1-2 hours; then filtering, filtering the filter cake and then crushing to finally prepare the nano active calcium carbonate powder.
2. The method for preparing nano active calcium carbonate according to claim 1, wherein the calcium oxide is prepared from the carbide slag raw material through washing, purifying, filtering and calcining, and the calcining temperature of the filter cake is 800-900 ℃;
3. the method for preparing nano active calcium carbonate according to claim 1, wherein the concentration of the calcium hydroxide slurry is 4-10%, the carbon dioxide introduced in the carbonization reaction is brought by air, so that the carbon dioxide and air are mixed gas, wherein the volume concentration of the carbon dioxide is 15-30%, and the flow rate of the mixed gas is 0.12 m30.25 m/L3The carbonization reaction temperature is 20-30 ℃, the stirring speed is 1500-2500 rpm, the addition amount of the additive is 0.2-0.6%, and the weight percentage of the calcium carbonate powder is used as a reference.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021600996A CN100457632C (en) | 2002-12-31 | 2002-12-31 | Method for preparing nano active calcium carbonate |
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| CNB021600996A CN100457632C (en) | 2002-12-31 | 2002-12-31 | Method for preparing nano active calcium carbonate |
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| CN1438178A true CN1438178A (en) | 2003-08-27 |
| CN100457632C CN100457632C (en) | 2009-02-04 |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331754C (en) * | 2005-07-20 | 2007-08-15 | 哈尔滨工业大学 | Nanometer conductive calcium carbonate and its production thereof |
| CN100334166C (en) * | 2005-01-26 | 2007-08-29 | 上海大学 | Method for modifying nano calcium carbonate |
| CN100360417C (en) * | 2004-11-30 | 2008-01-09 | 上海耀华纳米科技有限公司 | Method for preparing crystal nucleus prefabricated nano calcium carbonate and special equipment |
| CN101805002A (en) * | 2010-04-16 | 2010-08-18 | 西安石油大学 | Preparation method of surface modification calcium oxide |
| CN101830494A (en) * | 2010-05-11 | 2010-09-15 | 安徽工业大学 | Method for preparing active calcium carbonate by taking gypsum as raw material |
| CN101856584A (en) * | 2010-04-10 | 2010-10-13 | 湖南新恒光科技有限公司 | Process for preparing super-fine calcium sulfate from recycled sulfur dioxide waste gas |
| CN101890333A (en) * | 2010-07-06 | 2010-11-24 | 浙江大学 | Alumina membrane coated activated carbon and preparation method thereof |
| CN101967001A (en) * | 2010-09-26 | 2011-02-09 | 河北科技大学 | Method for producing calcium carbonate by using calcium carbide slag and low concentration carbon dioxide-containing waste gas as raw materials |
| CN103087387A (en) * | 2013-01-23 | 2013-05-08 | 大连星海纳米技术开发应用有限公司 | Production method of plastic filling master batch using carbide slag |
| CN103450587A (en) * | 2013-01-24 | 2013-12-18 | 长春天成高新纳米复合材料有限公司 | Preparation method of special nanometer modifier for PVC (polyvinyl chloride) resin |
| CN104053728A (en) * | 2011-10-25 | 2014-09-17 | 伊梅里斯矿物有限公司 | Particulate fillers |
| CN105329928A (en) * | 2015-12-10 | 2016-02-17 | 湖南化工职业技术学院 | Activation method for nanometer calcium carbonate |
| CN106219586A (en) * | 2016-08-02 | 2016-12-14 | 王延军 | A kind of be raw material production nanometer grade calcium carbonate with carbide slag device and method |
| CN106395877A (en) * | 2016-08-30 | 2017-02-15 | 青岛食安生物工程有限公司 | Preparation process of pure natural nano-ultrafine calcium powders |
| CN110040757A (en) * | 2019-06-06 | 2019-07-23 | 长沙紫宸科技开发有限公司 | A method of precipitated calcium carbonate is prepared using carbide slag |
| CN110510650A (en) * | 2019-08-23 | 2019-11-29 | 上海蓝烷新材料科技有限公司 | The preparation method and nanometer calcium carbonate of nanometer calcium carbonate |
| CN114604883A (en) * | 2022-03-16 | 2022-06-10 | 郭立杰 | Method for purifying whitening calcium carbonate by using core-shell structure |
| CN116023802A (en) * | 2022-12-27 | 2023-04-28 | 池州市贵兴非矿新材料有限公司 | Modified heavy calcium carbonate with low oil absorption value |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100190596B1 (en) * | 1996-05-03 | 1999-06-01 | 규 재 유 | METHOD OF MANUFACTURING 0.1-1.0º¡ CALCIUM CARBONATE |
| CN1194944A (en) * | 1997-03-31 | 1998-10-07 | 龚德和 | Oral superfine calcium carbonate for human calcium supplement and its producing method |
-
2002
- 2002-12-31 CN CNB021600996A patent/CN100457632C/en not_active Expired - Lifetime
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360417C (en) * | 2004-11-30 | 2008-01-09 | 上海耀华纳米科技有限公司 | Method for preparing crystal nucleus prefabricated nano calcium carbonate and special equipment |
| CN100334166C (en) * | 2005-01-26 | 2007-08-29 | 上海大学 | Method for modifying nano calcium carbonate |
| CN1331754C (en) * | 2005-07-20 | 2007-08-15 | 哈尔滨工业大学 | Nanometer conductive calcium carbonate and its production thereof |
| CN101856584A (en) * | 2010-04-10 | 2010-10-13 | 湖南新恒光科技有限公司 | Process for preparing super-fine calcium sulfate from recycled sulfur dioxide waste gas |
| CN101805002B (en) * | 2010-04-16 | 2012-01-11 | 西安石油大学 | Preparation method of surface modification calcium oxide |
| CN101805002A (en) * | 2010-04-16 | 2010-08-18 | 西安石油大学 | Preparation method of surface modification calcium oxide |
| CN101830494B (en) * | 2010-05-11 | 2013-08-21 | 安徽工业大学 | Method for preparing active calcium carbonate by taking gypsum as raw material |
| CN101830494A (en) * | 2010-05-11 | 2010-09-15 | 安徽工业大学 | Method for preparing active calcium carbonate by taking gypsum as raw material |
| CN101890333A (en) * | 2010-07-06 | 2010-11-24 | 浙江大学 | Alumina membrane coated activated carbon and preparation method thereof |
| CN101967001A (en) * | 2010-09-26 | 2011-02-09 | 河北科技大学 | Method for producing calcium carbonate by using calcium carbide slag and low concentration carbon dioxide-containing waste gas as raw materials |
| CN104053728B (en) * | 2011-10-25 | 2016-07-06 | 伊梅里斯矿物有限公司 | Granulated filler |
| CN104053728A (en) * | 2011-10-25 | 2014-09-17 | 伊梅里斯矿物有限公司 | Particulate fillers |
| CN103087387A (en) * | 2013-01-23 | 2013-05-08 | 大连星海纳米技术开发应用有限公司 | Production method of plastic filling master batch using carbide slag |
| CN103450587A (en) * | 2013-01-24 | 2013-12-18 | 长春天成高新纳米复合材料有限公司 | Preparation method of special nanometer modifier for PVC (polyvinyl chloride) resin |
| CN105329928A (en) * | 2015-12-10 | 2016-02-17 | 湖南化工职业技术学院 | Activation method for nanometer calcium carbonate |
| CN106219586A (en) * | 2016-08-02 | 2016-12-14 | 王延军 | A kind of be raw material production nanometer grade calcium carbonate with carbide slag device and method |
| CN106395877A (en) * | 2016-08-30 | 2017-02-15 | 青岛食安生物工程有限公司 | Preparation process of pure natural nano-ultrafine calcium powders |
| CN110040757A (en) * | 2019-06-06 | 2019-07-23 | 长沙紫宸科技开发有限公司 | A method of precipitated calcium carbonate is prepared using carbide slag |
| CN110510650A (en) * | 2019-08-23 | 2019-11-29 | 上海蓝烷新材料科技有限公司 | The preparation method and nanometer calcium carbonate of nanometer calcium carbonate |
| CN114604883A (en) * | 2022-03-16 | 2022-06-10 | 郭立杰 | Method for purifying whitening calcium carbonate by using core-shell structure |
| CN114604883B (en) * | 2022-03-16 | 2023-09-08 | 郭立杰 | Method for purifying and whitening calcium carbonate by core-shell structure |
| CN116023802A (en) * | 2022-12-27 | 2023-04-28 | 池州市贵兴非矿新材料有限公司 | Modified heavy calcium carbonate with low oil absorption value |
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| CN100457632C (en) | 2009-02-04 |
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