CN103950965A - Method for preparing nano-calcium carbonate with different sizes by applying seed crystal method - Google Patents
Method for preparing nano-calcium carbonate with different sizes by applying seed crystal method Download PDFInfo
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- CN103950965A CN103950965A CN201410177981.7A CN201410177981A CN103950965A CN 103950965 A CN103950965 A CN 103950965A CN 201410177981 A CN201410177981 A CN 201410177981A CN 103950965 A CN103950965 A CN 103950965A
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- calcium carbonate
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- different size
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Abstract
The invention relates to a method for preparing nano-calcium carbonate with different sizes by applying a seed crystal method. The method comprises the steps of adding deionized water at the temperature of 80-85 DEG C into CaO, performing reaction under stirring for 20-30min, then aging at room temperature, screening and adding deionized water to obtain a Ca(OH)2 solution; adding a crystal form additive into the Ca(OH)2 solution under water bath conditions, stirring, dissolving, introducing carbon dioxide gas, stirring till pH of a reaction solution is 9.5-10.5, then aging, continuously introducing the carbon dioxide gas, stirring till the pH of the reaction solution is 7, washing, centrifugating and drying. The method provided by the invention has the characteristics of simplicity, convenience, good repeatability, low temperature requirements, mass production and low cost; prepared excellent nano-calcium carbonate particles have the advantages of controllable particle size, uniform distribution, regular appearance, good dispersion and good application prospects.
Description
Technical field
The invention belongs to the preparation field of Nano-Calcium Carbonate, particularly a kind of method of kind of brilliant legal system for different size nano-calcium carbonate of using.
Background technology
Calcium carbonate is a kind of important inorganic materials, and along with the development of nanotechnology, emerging nano-calcium carbonate is as the more excellent functional inorganic filling of a kind of character, and oneself is through starting to be widely used in multiple industrial circles such as rubber, plastics, papermaking, coating, weaving, ink, toothpaste, makeup, food, pharmacy.Nano-calcium carbonate is compared other fillers at aspects such as brightening, replace reduction polymkeric substance total cost outstanding advantage, its preparation process is relatively easily controlled realization simultaneously, be beneficial to suitability for industrialized production and processing, there is data to show, calcium carbonate consumption accounts for the more than 80% of polymer inorganic amount of filler at present, and wherein the ratio of the nano-calcium carbonate of excellent performance is also rising year by year.
Carborization is the main method of producing nano-calcium carbonate.By selected Wingdale ore calcining, obtain calcium oxide and kiln gas (CO
2).Add deionized water to make calcium oxide digestion, and the suspension calcium hydroxide of generation is pulverized under high shear, separate and remove degranulation and impurity with multistage spinning liquid, obtain certain density refining calcium hydroxide suspension; Then pass into carbon dioxide, add suitable chemical additives, carbonization to terminal, can obtain the calcium carbonate serosity of required crystal formation; Dewater again, be dried, a series of processes such as surface treatment, obtain nano-calcium carbonate calcium product.
Along with the development of calcium carbonate production technology and the raising to its application requiring, impel calcium carbonate production little towards narrow diameter distribution, particle diameter, there is the line of production development of new function.Meanwhile, because difference is big or small, the range of application difference of the Nano particles of calcium carbonate of pattern, the carborization of improvement also engenders.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of kind of brilliant legal system for different size nano-calcium carbonate of using, and the method is simple and convenient, reproducible, and temperature requirement is low, the feature can produce in a large number, cost being low; Prepare good nano-calcium carbonate particles, size is controlled, is evenly distributed, and pattern is regular, and good dispersity has a good application prospect.
A kind of method of kind of brilliant legal system for different size nano-calcium carbonate of using of the present invention, comprising:
(1) deionized water of 80-85 DEG C is added in CaO, stirring reaction 20-30min, then room temperature ageing, sieves, and adds deionized water, obtains Ca (OH)
2solution;
(2), under water bath condition, crystal formation additive is added to above-mentioned Ca (OH)
2in solution, stirring and dissolving, passes into carbon dioxide, and to be stirred to reaction soln pH be 9.5-10.5, and then ageing continues logical carbon dioxide, and being stirred to reaction soln pH is 7, washs centrifugally, dry, obtains nano-calcium carbonate; Wherein crystal formation additive is that mass ratio is sucrose and the NaHCO of 0.162:0.090-0.100
3.
The ratio of the deionized water of CaO and 80-85 DEG C is 6.05g:30ml in described step (1).
In described step (1), room temperature digestion time is 12-48h; Sieve order number is 200 orders.
Ca (OH) in described step (1)
2the mass percentage concentration of solution is 4-8%.
In described step (2), in crystal formation additive, sucrose add-on is 0.15% of theoretical calcium carbonate output, NaHCO
3add-on is 1%～10% of theoretical calcium carbonate output.
Preferably chemical additives is 0.162g sucrose and 0.0907g NaHCO
3, 0.162g sucrose and 0.272g NaHCO
3or 0.162g sucrose and 0.907g NaHCO
3.
In described step (2), the stirring and dissolving time is 5-10min.
In described step (2), pass into carbon dioxide and be 1.5L/min, maintenance bath temperature is 13-25 DEG C.
In described step (2), Aging Temperature is 65-70 DEG C, and digestion time is 10-16h.
In described step (2), washing centrifugal is that ethanol, deionized water alternately wash centrifugal, be specially: first use absolute ethanol washing, the centrifugal removal supernatant liquor of centrifugation 8-10min under 10000rpm, use again deionized water wash, under 10000rpm the centrifugal removal supernatant liquor of centrifugation 8-10min, finally use absolute ethanol washing, centrifugation 8-10min is centrifugal under 10000rpm.In described step (2), drying temperature is 80-85 DEG C.
In the present invention, at Ca (OH)
2in solution, add the NaHCO of different amounts
3, cause the CaCO that generates different amounts
3crystal seed, crystal seed is dispersed in suspension as crystallization nuclei, and the degree of supersaturation that has reduced particle contributes to the growth of crystal, adds crystal seed to solve low, big or small difficult this difficult problem of controlling of productive rate in the process of preparation, and by regulating NaHCO
3add-on and controlling add the reaction process parameter of crystal seed amount etc., can synthesize the particles of different sizes, save process costs thereby process cycle shortens.
beneficial effect
(1) the present invention is simple and convenient, reproducible, the feature that temperature requirement is low, can produce in a large number, cost is low;
(2) the present invention prepares good nano-calcium carbonate particles, and size is controlled, is evenly distributed, and pattern is regular, and good dispersity has a good application prospect.
Brief description of the drawings
Fig. 1 is the nano-calcium carbonate TEM figure of embodiment 1 gained;
Fig. 2 is the nano-calcium carbonate TEM figure of embodiment 2 gained;
Fig. 3 is the nano-calcium carbonate TEM figure of embodiment 3 gained;
Fig. 4 is the nano-calcium carbonate TEM figure of reference examples 1 gained;
Fig. 5 is the nano-calcium carbonate XRD figure of embodiment 3 gained.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
(1) take 6.05g CaO, add about 30ml85.0 DEG C deionized water, the about 30min of magnetic agitation.More than ageing 24h.
(2) add deionized water to 200ml, and by Ca (OH)
2solution is crossed 200 mesh sieve.
(3) water-bath magnetic agitation in room temperature water, adds sucrose 0.162g (theoretical calcium carbonate output 0.15%), 0.907gNaHCO
3(theoretical calcium carbonate mole output 10%), after 10min, logical CO
21.5L/min, in the time that pH drops to 9.5-10.5, stops and starting ageing 16h in 65 DEG C of water-bath.
(4) magnetic agitation, is down to room temperature.Continue logical CO
21.5L/min, in the time that pH is approximately 7, stopped reaction.
(5) reaction finishes, centrifuge washing.First use absolute ethanol washing, the centrifugal removal supernatant liquor of centrifugation 8min under 10000rpm, use again deionized water wash, the centrifugal removal supernatant liquor of centrifugation 8min under 10000rpm, so circulation 3 times, finally uses absolute ethanol washing, centrifugation 8min is centrifugal under 10000rpm.
(6) in 80.0 DEG C of drying in oven.
TEM by Fig. 1 schemes, and the length mean value that is estimated particle by figure is about 60.30nm, and the reaction times is 19min.
Embodiment 2
(1) take 6.05g CaO, add about 30ml85.0 DEG C deionized water, the about 30min of magnetic agitation.More than ageing 24h.
(2) add deionized water to 200ml, and by Ca (OH)
2solution is crossed 200 mesh sieve.
(3) water-bath magnetic agitation in room temperature water, adds sucrose 0.162g (theoretical calcium carbonate output 0.15%), 0.272gNaHCO
3(theoretical calcium carbonate mole output 3%), after 10min, logical CO
21.5L/min, in the time that pH drops to 9.5-10.5, stops and starting ageing 16h in 65 DEG C of water-bath.
(4) magnetic agitation, is down to room temperature.Continue logical CO
21.5L/min, in the time that pH is approximately 7, stopped reaction.
(5) reaction finishes, centrifuge washing.First use absolute ethanol washing, the centrifugal removal supernatant liquor of centrifugation 8min under 10000rpm, use again deionized water wash, the centrifugal removal supernatant liquor of centrifugation 8min under 10000rpm, so circulation 3 times, finally uses absolute ethanol washing, centrifugation 8min is centrifugal under 10000rpm.
(6) in 80.0 DEG C of drying in oven.
TEM by Fig. 2 schemes, and the length mean value that is estimated particle by figure is about 66.73nm, and the reaction times is 24min.
Embodiment 3
(1) take 6.05g CaO, add about 30ml85.0 DEG C deionized water, the about 30min of magnetic agitation.More than ageing 24h.
(2) add deionized water to 200ml, and by Ca (OH)
2solution is crossed 200 mesh sieve.
(3) water-bath magnetic agitation in room temperature water, adds sucrose 0.162g (theoretical calcium carbonate output 0.15%), 0.0907gNaHCO
3(theoretical calcium carbonate mole output 1%), after 10min, logical CO
21.5L/min, in the time that pH drops to 9.5-10.5, stops and starting ageing 16h in 65 DEG C of water-bath.
(4) magnetic agitation, is down to room temperature.Continue logical CO
21.5L/min, in the time that pH is approximately 7, stopped reaction.
(5) reaction finishes, centrifuge washing.First use absolute ethanol washing, the centrifugal removal supernatant liquor of centrifugation 8min under 10000rpm, use again deionized water wash, the centrifugal removal supernatant liquor of centrifugation 8min under 10000rpm, so circulation 3 times, finally uses absolute ethanol washing, centrifugation 8min is centrifugal under 10000rpm.
(6) in 80.0 DEG C of drying in oven.
By the TEM figure of Fig. 3 and the XRD figure of Fig. 5, the mean value that is estimated particle length by figure is about 97.68nm, and the reaction times is 28min and is all the nano-calcium carbonate particles of calcite type.
Reference examples 1
(1) take 6.05g CaO, add about 30ml85.0 DEG C deionized water, the about 30min of magnetic agitation.More than ageing 24h.
(2) add deionized water to 200ml, and by Ca (OH)
2solution is crossed 200 mesh sieve.
(3) water-bath magnetic agitation in room temperature water, adds sucrose 0.162g (theoretical calcium carbonate output 0.15%), after 10min, and logical CO
21.5L/min, in the time that pH drops to 9.5-10.5, stops and starting ageing 16h in 65 DEG C of water-bath.
(4) magnetic agitation, is down to room temperature.Continue logical CO
21.5L/min, in the time that pH is approximately 7, stopped reaction.
(5) reaction finishes, centrifuge washing.First use absolute ethanol washing, the centrifugal removal supernatant liquor of centrifugation 8min under 10000rpm, use again deionized water wash, the centrifugal removal supernatant liquor of centrifugation 8min under 10000rpm, so circulation 3 times, finally uses absolute ethanol washing, centrifugation 8min is centrifugal under 10000rpm.
(6) in 80.0 DEG C of drying in oven.
TEM by Fig. 4 schemes, and the mean value that is estimated particle length by figure is about 131.7nm, and the reaction times is 32min.
Claims (9)
1. use the method for kind of brilliant legal system for different size nano-calcium carbonate, comprising:
(1) deionized water of 80-85 DEG C is added in CaO, stirring reaction 20-30min, then room temperature ageing, sieves, and adds deionized water, obtains Ca (OH)
2solution;
(2), under water bath condition, crystal formation additive is added to above-mentioned Ca (OH)
2in solution, stirring and dissolving, passes into carbon dioxide, and to be stirred to reaction soln pH be 9.5-10.5, and then ageing continues logical carbon dioxide, and being stirred to reaction soln pH is 7, washs centrifugally, dry, obtains nano-calcium carbonate; Wherein crystal formation additive is that mass ratio is sucrose and the NaHCO of 0.162:0.090-0.100
3.
2. a kind of method of kind of brilliant legal system for different size nano-calcium carbonate of using according to claim 1, is characterized in that: the ratio of the deionized water of CaO and 80-85 DEG C is 6.05g:30ml in described step (1).
3. a kind of method of kind of brilliant legal system for different size nano-calcium carbonate of using according to claim 1, is characterized in that: in described step (1), room temperature digestion time is 12-48h; Sieve order number is 200 orders.
4. a kind of method of kind of brilliant legal system for different size nano-calcium carbonate of using according to claim 1, is characterized in that: Ca (OH) in described step (1)
2the mass percentage concentration of solution is 4-8%.
5. a kind of method of kind of brilliant legal system for different size nano-calcium carbonate of using according to claim 1, is characterized in that: in described step (2), the stirring and dissolving time is 5-10min.
6. a kind of method of kind of brilliant legal system for different size nano-calcium carbonate of using according to claim 1, is characterized in that: in described step (2), pass into carbon dioxide and be 1.5L/min, bath temperature is 13-25 DEG C.
7. a kind of method of kind of brilliant legal system for different size nano-calcium carbonate of using according to claim 1, is characterized in that: in described step (2), Aging Temperature is 65-70 DEG C, and digestion time is 10-16h.
8. a kind of method of kind of brilliant legal system for different size nano-calcium carbonate of using according to claim 1, it is characterized in that: in described step (2), washing centrifugal is that ethanol, deionized water alternately wash centrifugal, be specially: first use absolute ethanol washing, the centrifugal removal supernatant liquor of centrifugation 8-10min under 10000rpm, use again deionized water wash, under 10000rpm the centrifugal removal supernatant liquor of centrifugation 8-10min, finally use absolute ethanol washing, centrifugation 8-10min is centrifugal under 10000rpm.
9. a kind of method of kind of brilliant legal system for different size nano-calcium carbonate of using according to claim 1, is characterized in that: in described step (2), drying temperature is 80-85 DEG C.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449732A (en) * | 2015-01-06 | 2015-03-25 | 东华大学 | A seed crystal method is used to prepare nanometer KYF4: yb3+, er3+materials |
| CN107555461A (en) * | 2017-09-30 | 2018-01-09 | 广西华洋矿源材料有限公司 | A kind of Nano calcium carbonate dedicated preparation method of plastics |
| CN110589865A (en) * | 2019-10-24 | 2019-12-20 | 长江师范学院 | Method for preparing loose porous calcite by using steel slag |
| CN110813059A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | Method for reducing regeneration energy consumption of carbon dioxide capture solvent |
| CN111252796A (en) * | 2020-03-31 | 2020-06-09 | 中国科学院过程工程研究所 | Method for preparing crystal form controllable high-purity rare earth carbonate |
| CN111874933A (en) * | 2020-08-14 | 2020-11-03 | 王权广 | Quick preparation process of rice-grain light calcium carbonate |
| CN112678839A (en) * | 2019-10-18 | 2021-04-20 | 中国科学院过程工程研究所 | Preparation method of calcium silicate with controllable particle size, calcium silicate prepared by preparation method and application of calcium silicate |
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| CN1657413A (en) * | 2004-12-03 | 2005-08-24 | 天津化工研究设计院 | Preparation method of lamellar crystal light calcium carbonate for paper making coating |
| CN102674425A (en) * | 2012-05-19 | 2012-09-19 | 祁阳建明化工有限责任公司 | Production technique of nano calcium carbonate by normal temperature method |
| CN103663527A (en) * | 2012-09-25 | 2014-03-26 | 上海华明高技术（集团）有限公司 | Preparation method of cubic ultra-fine calcium carbonate particles |
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| CN1583570A (en) * | 2004-06-14 | 2005-02-23 | 上海华明高技术（集团）有限公司 | Method for manufacturing super fine calcium carbonate dispersing particles |
| CN1657413A (en) * | 2004-12-03 | 2005-08-24 | 天津化工研究设计院 | Preparation method of lamellar crystal light calcium carbonate for paper making coating |
| CN102674425A (en) * | 2012-05-19 | 2012-09-19 | 祁阳建明化工有限责任公司 | Production technique of nano calcium carbonate by normal temperature method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449732A (en) * | 2015-01-06 | 2015-03-25 | 东华大学 | A seed crystal method is used to prepare nanometer KYF4: yb3+, er3+materials |
| CN104449732B (en) * | 2015-01-06 | 2016-08-24 | 东华大学 | An a kind of utilization kind crystallization prepares KYF4: Yb3+, Er3+the method of nano material |
| CN107555461A (en) * | 2017-09-30 | 2018-01-09 | 广西华洋矿源材料有限公司 | A kind of Nano calcium carbonate dedicated preparation method of plastics |
| CN110813059A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | Method for reducing regeneration energy consumption of carbon dioxide capture solvent |
| CN112678839A (en) * | 2019-10-18 | 2021-04-20 | 中国科学院过程工程研究所 | Preparation method of calcium silicate with controllable particle size, calcium silicate prepared by preparation method and application of calcium silicate |
| CN112678839B (en) * | 2019-10-18 | 2022-07-01 | 中国科学院过程工程研究所 | Preparation method of calcium silicate with controllable particle size, calcium silicate prepared by preparation method and application of calcium silicate |
| CN110589865A (en) * | 2019-10-24 | 2019-12-20 | 长江师范学院 | Method for preparing loose porous calcite by using steel slag |
| CN110589865B (en) * | 2019-10-24 | 2022-03-25 | 长江师范学院 | Method for preparing loose porous calcite by using steel slag |
| CN111252796A (en) * | 2020-03-31 | 2020-06-09 | 中国科学院过程工程研究所 | Method for preparing crystal form controllable high-purity rare earth carbonate |
| CN111874933A (en) * | 2020-08-14 | 2020-11-03 | 王权广 | Quick preparation process of rice-grain light calcium carbonate |
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