CN104448936A - Method for preparing phosphoric acid-modified biological calcium carbonate - Google Patents
Method for preparing phosphoric acid-modified biological calcium carbonate Download PDFInfo
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- CN104448936A CN104448936A CN201410651873.9A CN201410651873A CN104448936A CN 104448936 A CN104448936 A CN 104448936A CN 201410651873 A CN201410651873 A CN 201410651873A CN 104448936 A CN104448936 A CN 104448936A
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- phosphoric acid
- calcium carbonate
- biological calcium
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- sea shell
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Abstract
The invention discloses a method for preparing phosphoric acid-modified biological calcium carbonate. The preparation method comprises the following steps: adding water to shell micro-powder at room temperature to obtain prepare shell micro-powder slurry, wherein the mass content of the prepared shell micro-powder slurry is 5-30%; slowly adding a dilute phosphoric acid solution to the shell micro-powder slurry at the ratio during stirring, wherein the mass of phosphoric acid in the dropwise added dilute phosphoric acid solution is 3.3-33.3% of that of the shell micro-powder; further stirring for 5-120 minutes after dropwise adding is ended, so as to enable the dilute phosphoric acid solution to fully react; and filtering, drying, and scattering after reaction is ended, so as to obtain the phosphoric acid-modified biological calcium carbonate. The method is mild in operation condition, wide in raw material source, simple, and low in equipment investment and energy consumption; the prepared phosphoric acid-modified biological calcium carbonate is good in surface activity, has the natural lipophilic-hydrophobic property and the excellent mechanical property, is good in compatibility with a base body matrix, and even when being dispersed in the base body, and has a wide application prospect.
Description
Technical field
The present invention relates to pearl filler preparing technical field, particularly relate to a kind of preparation method of phosphoric acid modification biological calcium carbonate.
Background technology
The application of organic polymer material is constantly expanded, and this has benefited from the development of organic polymer composite and coatings industry.Due to mineral filler and organic polymer material poor compatibility, between Presence of an interface in conjunction with problem, so a large amount of when dripping mineral filler in organic polymer material or coating, very big to the Effect on Mechanical Properties of organic polymer composite and film.Utilize lipid acid and its esters or coupling agent treatment mineral filler, again with organic polymer material or paint-based bottom resin blended, just be combined with organic polymer material at several points of inorganic filler surface, namely between them, interface cohesion is poor, have impact on the mechanical property of organic polymer composite, cause that its intensity is low, poor toughness.How solving mineral filler and the poor problem of organic polymer material interface compatibility is one of key issue of developing of organic polymer composite.
Calcium carbonate is a kind of very important mineral filler, is widely used in organic polymer material.The calcite type calcium carbonate of geology mineralising and organic polymer material poor compatibility, easily reunite in macromolecular material, disperse uneven.Although the dispersiveness of modified calcium carbonate in organic polymer material makes moderate progress, modified effect is still undesirable, affects the performance of material high performance.
China's shellfish culture annual production reaches 1,200 ten thousand tons, and in shellfish, the weight of shell accounts for about 75% of gross weight, and the fast development of shellfish culture creates a large amount of shell waste.For a long time, a large amount of shell resources in seashore, sandy beach, causes serious pollution as dump waste, and it is more and more serious to pile up the environmental problem that causes year by year, and the resource utilization of shell waste develops significant.
Shell is the biomineral material that a kind of biomineralization is formed, and in its chemical composition, calcium carbonate accounts for 95%, and all the other about 5% are organic substrate.Shell pearl layer is the canonical biometric mineral material be made up of nano-calcium carbonate and biomacromolecule, has unique microstructure and mechanical property that is high-strength, high-ductility.
Confirm that sea shell micropowder surface exists the functional groups such as amino, amide group and hydroxyl with x-ray photoelectron power spectrum (XPS) and infrared spectra (FT-IR) analysis.The surfactivity of filler is controlled by its surface functional group, and the character of surface functional group is surface modification, interface regulation and control and improve dispersed, so the excellent matrix material of controlled synthesis, film basis.According to practical application needs, fall a certain proportion of calcium carbonate in sea shell micropowder surface by dripping dilute phosphoric acid solution corrosion reaction in proportion, the functional groups such as the amino, amide group and the hydroxyl that allow sea shell micropowder surface exist are exposed more.This is direct or modified for filling organic polymer material and for significant in coating for exploitation sea shell micropowder filler.Improve significant to the preparation of mineral filler modification and mineral filler/organic polymer composite, film and performance.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of phosphoric acid modification biological calcium carbonate is provided.
The step of the preparation method of phosphoric acid modification biological calcium carbonate is as follows:
(1) sea shell micropowder is added water at normal temperatures be mixed with sea shell micropowder slurry.
(2) in sea shell micropowder slurry, slowly add dilute phosphoric acid solution while stirring in proportion, after dropwising, continue stirring 5 ~ 120 minutes, make it fully react.
(3) after reaction terminates, after filtration, dry, break up and obtain phosphoric acid modification biological calcium carbonate.
In described step (1), the mass content of obtained sea shell micropowder slurry is 5 ~ 30%.
In described step (2), in the dilute phosphoric acid solution dripped, the quality of phosphoric acid is 3.3 ~ 33.3% of sea shell micropowder quality.
In described step (2), the mass concentration of dilute phosphoric acid solution is 1 ~ 40%.
Operational condition of the present invention is gentle, and raw material sources are wide, and technique is simple, facility investment and energy consumption little; The phosphoric acid modification biological calcium carbonate good surface activity of preparation, has natural lipophilic-hydrophobic property and excellent mechanical property, good with matrix phase capacitive, is uniformly dispersed in the base, is with a wide range of applications.Promote the high value added utilization of waste shell, be conducive to reduction of discharging, environmental protection, there is good economic and social benefit.
Accompanying drawing explanation
Fig. 1 is phosphoric acid modification biological calcium carbonate morphology microstructure electron-microscope scanning;
Fig. 2 and Fig. 3 is monolithic phosphoric acid modification biological calcium carbonate morphology microstructure electron-microscope scanning.
Embodiment
The step of the preparation method of phosphoric acid modification biological calcium carbonate is as follows:
(1) sea shell micropowder is added water at normal temperatures be mixed with sea shell micropowder slurry.
(2) in sea shell micropowder slurry, slowly add dilute phosphoric acid solution while stirring in proportion, after dropwising, continue stirring 5 ~ 120 minutes, make it fully react.
(3) after reaction terminates, after filtration, dry, break up and obtain phosphoric acid modification biological calcium carbonate.
In described step (1), the mass content of obtained sea shell micropowder slurry is 5 ~ 30%.
In described step (2), in the dilute phosphoric acid solution dripped, the quality of phosphoric acid is 3.3 ~ 33.3% of sea shell micropowder quality.
In described step (2), the mass concentration of dilute phosphoric acid solution is 1 ~ 40%.
The present invention is further described in conjunction with following instance, but content of the present invention is not limited only to content involved in embodiment.
Embodiment 1:
(1) sea shell micropowder is added water at normal temperatures be mixed with the slurry that sea shell micropowder mass content is 5%.
(2) in sea shell micropowder slurry, slowly add the dilute phosphoric acid solution that mass concentration is 1%, in the dilute phosphoric acid solution dripped, the quality of phosphoric acid is 3.3% of sea shell micropowder quality, after dropwising, continues stirring 5 minutes, makes it fully react.
(3), after reaction terminates, filter, dry, break up to obtain phosphoric acid modification biological calcium carbonate.Fig. 1 is phosphoric acid modification biological calcium carbonate morphology microstructure electron-microscope scanning; Fig. 2 and Fig. 3 is monolithic phosphoric acid modification biological calcium carbonate morphology microstructure electron-microscope scanning.
Embodiment 2:
(1) sea shell micropowder is added water at normal temperatures be mixed with the slurry that sea shell micropowder mass content is 30%.
(2) in sea shell micropowder slurry, slowly add the dilute phosphoric acid solution that mass concentration is 40%, in the dilute phosphoric acid solution dripped, the quality of phosphoric acid is 33.3% of sea shell micropowder quality, after dropwising, continues stirring 120 minutes, makes it fully react.
(3), after reaction terminates, filter, dry, break up to obtain phosphoric acid modification biological calcium carbonate.
Embodiment 3:
(1) sea shell micropowder is added water at normal temperatures be mixed with the slurry that sea shell micropowder mass content is 10%.
(2) in sea shell micropowder slurry, slowly add the dilute phosphoric acid solution that mass concentration is 5%, in the dilute phosphoric acid solution dripped, the quality of phosphoric acid is 10% of sea shell micropowder quality, after dropwising, continues stirring 20 minutes, makes it fully react.
(3), after reaction terminates, filter, dry, break up to obtain phosphoric acid modification biological calcium carbonate.
Embodiment 4:
(1) sea shell micropowder is added water at normal temperatures be mixed with the slurry that sea shell micropowder mass content is 15%.
(2) in sea shell micropowder slurry, slowly add the dilute phosphoric acid solution that mass concentration is 15%, in the dilute phosphoric acid solution dripped, the quality of phosphoric acid is 15% of sea shell micropowder quality, after dropwising, continues stirring 30 minutes, makes it fully react.
(3), after reaction terminates, filter, dry, break up to obtain phosphoric acid modification biological calcium carbonate.
Embodiment 5:
(1) sea shell micropowder is added water at normal temperatures be mixed with the slurry that sea shell micropowder mass content is 20%.
(2) in sea shell micropowder slurry, slowly add the dilute phosphoric acid solution that mass concentration is 20%, in the dilute phosphoric acid solution dripped, the quality of phosphoric acid is 20% of sea shell micropowder quality, after dropwising, continues stirring 60 minutes, makes it fully react.
(3), after reaction terminates, filter, dry, break up to obtain phosphoric acid modification biological calcium carbonate.
Embodiment 6:
(1) sea shell micropowder is added water at normal temperatures be mixed with the slurry that sea shell micropowder mass content is 22.5%.
(2) in sea shell micropowder slurry, slowly add the dilute phosphoric acid solution that mass concentration is 25%, in the dilute phosphoric acid solution dripped, the quality of phosphoric acid is 25% of sea shell micropowder quality, after dropwising, continues stirring 80 minutes, makes it fully react.
(3), after reaction terminates, filter, dry, break up to obtain phosphoric acid modification biological calcium carbonate.
Embodiment 7:
(1) sea shell micropowder is added water at normal temperatures be mixed with the slurry that sea shell micropowder mass content is 25%.
(2) in sea shell micropowder slurry, slowly add the dilute phosphoric acid solution that mass concentration is 30%, in the dilute phosphoric acid solution dripped, the quality of phosphoric acid is 30% of sea shell micropowder quality, after dropwising, continues stirring 100 minutes, makes it fully react.
(3), after reaction terminates, filter, dry, break up to obtain phosphoric acid modification biological calcium carbonate.
Claims (4)
1. a preparation method for phosphoric acid modification biological calcium carbonate, is characterized in that its step is as follows:
(1) sea shell micropowder is added water at normal temperatures be mixed with sea shell micropowder slurry;
(2) in sea shell micropowder slurry, slowly add dilute phosphoric acid solution while stirring in proportion, after dropwising, continue stirring 5 ~ 120 minutes, make it fully react;
(3) after reaction terminates, after filtration, dry, break up and obtain phosphoric acid modification biological calcium carbonate.
2. the preparation method of a kind of phosphoric acid modification biological calcium carbonate as claimed in claim 1, is characterized in that in described step (1), and the mass content of obtained sea shell micropowder slurry is 5 ~ 30%.
3. the preparation method of a kind of phosphoric acid modification biological calcium carbonate as claimed in claim 1, is characterized in that in described step (2), in the dilute phosphoric acid solution dripped, the quality of phosphoric acid is 3.3 ~ 33.3% of sea shell micropowder quality.
4. the preparation method of a kind of phosphoric acid modification biological calcium carbonate as claimed in claim 1, is characterized in that, in described step (2), the mass concentration of dilute phosphoric acid solution is 1 ~ 40%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410651873.9A CN104448936A (en) | 2014-11-17 | 2014-11-17 | Method for preparing phosphoric acid-modified biological calcium carbonate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365190A (en) * | 2016-08-26 | 2017-02-01 | 石家庄市东升钙业有限公司 | Preparing method of medicine fermenting calcium carbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848408A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院海洋研究所 | Method for preparing calcium hydrogen phosphate by using shells |
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2014
- 2014-11-17 CN CN201410651873.9A patent/CN104448936A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848408A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院海洋研究所 | Method for preparing calcium hydrogen phosphate by using shells |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365190A (en) * | 2016-08-26 | 2017-02-01 | 石家庄市东升钙业有限公司 | Preparing method of medicine fermenting calcium carbonate |
| CN106365190B (en) * | 2016-08-26 | 2019-01-11 | 石家庄市东升钙业有限公司 | The preparation method of medicine fermentation calcium carbonate |
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Application publication date: 20150325 |