CN101580260B - Method for preparing amorphous calcium carbonate by microemulsion method - Google Patents
Method for preparing amorphous calcium carbonate by microemulsion method Download PDFInfo
- Publication number
- CN101580260B CN101580260B CN200910065055XA CN200910065055A CN101580260B CN 101580260 B CN101580260 B CN 101580260B CN 200910065055X A CN200910065055X A CN 200910065055XA CN 200910065055 A CN200910065055 A CN 200910065055A CN 101580260 B CN101580260 B CN 101580260B
- Authority
- CN
- China
- Prior art keywords
- calcium carbonate
- microemulsion
- amorphous calcium
- calcium chloride
- methylcarbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a method for preparing amorphous calcium carbonate by microemulsion method. Calcium chloride and dimethylcarbonate are dissolved in water to prepare microemulsion, then tricarboxylate is added and dissolved in microemulsion, finally amorphous calcium carbonate is produced on the action of sodium hydroxide. The method provided by the invention is much easier, the reaction time range is expanded, the reaction is better to control and convenient to use in industry; moreover, the purity of the produced amorphous calcium carbonate is high.
Description
(1) technical field
The invention belongs to the calcium carbonate material field, particularly a kind of method of preparing amorphous calcium carbonate by microemulsion method.
(2) background technology
Up to the present, result of study shows under the normal temperature and pressure that there are 6 kinds in nature and have identical component but the calcium carbonate mineral of different structure: and amorphous calcium carbonate (Amorphous calcium carbonate, ACC), single aqueous carbonate calcium, six aqueous carbonate calcium, vaterite, aragonite, calcite.These 6 kinds of lime carbonate thermodynamic stabilities increase successively, wherein all are crystal form except that ACC, and ball thunderclap stone, aragonite, calcite are water-free calcium carbonate crystals, and single aqueous carbonate calcium and six aqueous carbonate calcium are the crystal that contain crystal water.
Amorphous material extensively exists at nature, and plays an important role in biomineralization.These gel mineral materials comprise silicon-dioxide, amorphous calcium phosphate, amorphous calcium carbonate etc.These amorphous inorganic minerals and organism interact jointly and constitute biological sclerous tissues, as shell, bone, tooth etc.Amorphous calcium carbonate is a kind of metastable lime carbonate, has relatively large solubleness in water; Under certain conditions, it will transform into crystalline lime carbonate.It is more difficult that amorphous phase is studied relative crystal form, so the research of relevant lime carbonate amorphous phase is out in the cold for a long time.Yet nearest research discloses and amorphously to play a part more crucially in the regulation and control of biomineralization process, has participated in the orientation of crystal form and the control of arrangement in the phase transition process directly.Lime carbonate with respect to crystal form, amorphous calcium carbonate has isotropy and plastic characteristics, fashioned into biological needed different shape easily, be converted into the crystalline calcium carbonate of respective shapes then, the biomineral correspondence in different poses and with different expressions that this and occurring in nature are observed.By research to amorphous calcium carbonate, the secret of the meticulous control biomineralization of organism will further be untied, make the human functional materials with various complicated shapes of therefrom learning how to prepare, this has important use to fields such as biology, medical science, medicines and is worth.In view of unbodied plasticity-and controlled convertibility, people adopt the stable amorphous calcium carbonate of the whole bag of tricks control preparation, in the hope of further obtain having different size, the calcium carbonate product of different shape, crystal formation and surface property, reduce production costs, satisfy the different industrial requirement of various the sectors.The preparation method of amorphous calcium carbonate is more at present, but has the preparation process poor controllability mostly, the problem that the amorphous calcium carbonate purity for preparing has much room for improvement.
(3) summary of the invention
The object of the present invention is to provide a kind of method of preparing amorphous calcium carbonate by microemulsion method, the process controllability is good, the amorphous calcium carbonate purity height that makes.
The technical solution used in the present invention is as follows:
A kind of method of preparing amorphous calcium carbonate by microemulsion method with calcium chloride and the methylcarbonate microemulsion that is prepared into soluble in water, adds tricarboxylate then and is dissolved in the microemulsion, makes amorphous calcium carbonate afterwards under the effect of sodium hydroxide.
The tricarboxylate that adds is 0.2-2 with the amount of substance of calcium chloride ratio: 1, and the preferred tricarboxylate that adds is 1: 1 with the amount of substance ratio of calcium chloride.
Described tricarboxylate is Trisodium Citrate, equisetic acid sodium or trimesic acid sodium.
Calcium chloride, methylcarbonate are 1 with the ratio of the amount of substance that feeds intake of sodium hydroxide: 0.5-5: 1-5, preferably calcium chloride, methylcarbonate are 1: 1: 2 with the ratio of the amount of substance that feeds intake of sodium hydroxide.
Described preparation of microemulsion method is as follows: under 10-30 ℃ that calcium chloride and methylcarbonate is soluble in water, with the speed stirring formation microemulsion of 50-1200rpm, wherein calcium chloride is 1 with the amount of substance ratio of water: 1300-14000.
Further, calcium chloride and methylcarbonate is soluble in water under 25 ℃, stir with the speed of 500rpm and to form microemulsion, wherein calcium chloride is 1: 2778 with the amount of substance ratio of water.
Continue to stir 0.5-20min after adding NaOH, ageing 6min-9h then, aftertreatment promptly gets described amorphous calcium carbonate.
Further, continue to stir 2min, ageing 3h then behind the adding NaOH.
Aftertreatment finishes the back suction filtration and carries out drying in 10-40 ℃ for reaction.
Calcium chloride described in the present invention both can also can adopt the calcium chloride that contains crystal water for Calcium Chloride Powder Anhydrous.
The method of preparing amorphous calcium carbonate by microemulsion method provided by the invention, adopt calcium chloride as the calcium source, methylcarbonate is as carbonate source, and tricarboxylate adopts microemulsion method to finish reaction at the interface at water/oil as tensio-active agent stable amorphous lime carbonate behind the adding sodium hydroxide.The amorphous calcium carbonate of preparation is a non-crystal structure, and purity almost can reach 100%, and the reaction times of amorphous calcium carbonate is controlled in the 6min-9h scope.Initial reactant proportioning (Ca
2+: CO
3 2-) 1: the 0.5-5 scope is controlled, and the mol ratio of tricarboxylate and calcium chloride is at 0.2-2: 1 scope is controlled.Utilize X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) that resulting product is characterized.Characterization result shows that digestion time prepared lime carbonate within 6min-9h is amorphous state, and amorphous calcium carbonate is made up of a large amount of unordered nanoparticles that are deposited in together.The diameter of the nanoparticle of composition amorphous calcium carbonate is about 100nm.
The present invention has following advantage with respect to prior art:
The inventive method, not only more simple, and expanded reaction time range, help the control of reacting more, be convenient in industrial application; And the amorphous calcium carbonate purity height that makes.This is to utilizing unbodied plasticity-and controlled convertibility, for further obtain having different size, the calcium carbonate product of different shape, crystal formation and surface property provides presoma, have great significance to better meeting the various industrial requirement of the sector.
(4) description of drawings
Fig. 1 is the XRD figure spectrum of the product when digestion time is respectively 3h (a), 6h (b) and 9h (c) among the embodiment 1-3;
Fig. 2 is the SEM photo of embodiment 1 product;
Fig. 3 is the TEM image of embodiment 1 product;
Fig. 4 is high-res transmission electron microscope (HR-TEM) image of embodiment 1 product;
Fig. 5 is selected area electron diffraction (SAED) image of embodiment 1 product.
(5) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1
With CaCl
22H
2O powder and methylcarbonate were inserted and are contained and CaCl in 1: 1 in molar ratio
22H
2The mol ratio of O is in 2778: 1 the beaker of distilled water, makes it to be uniformly dispersed with the stirring velocity of 500rpm, forms microemulsion.Will with CaCl
22H
2The O mol ratio is 1: 1 Na
3C
6H
5O
72H
2The O powder adds aforesaid liquid, stirs down dissolving fully.Will with CaCl
22H
2The O mol ratio is that 2: 1 NaOH powder adds above-mentioned mixed solution, continues to stir 2min, and digestion time is 3h.At last, with turbid liquid suction filtration, 25 ℃ of dryings are collected white product.
Utilize X-ray diffractometer (XRD), field emission scanning electron microscope (SEM), a transmission Electronic Speculum (TEM) that resulting product is characterized.The XRD figure of product spectrum is seen Fig. 1, and product is the amorphous calcium carbonate structure when spectrogram is clear that digestion time is 3h.In addition, observation experiment finds that solution just begins muddiness to occur after digestion time is 6min, shows that digestion time is that the 6min postprecipitation just begins to generate gradually.The SEM photo of product is seen Fig. 2, and product is that amorphous nanoparticle accumulation forms from scheming as can be known.Fig. 3 is the TEM image of amorphous calcium carbonate, has proved that further product is that the diameter of nanoparticle is about 100nm by the unordered amorphous calcium carbonate structure that forms together that is deposited in of the nanoparticle of diameter homogeneous.Fig. 4 is the HR-TEM image of single amorphous calcium carbonate nanoparticle, proves that lime carbonate is in complete state of disarray, the direction of growth do not occur, is amorphous state really.Fig. 5 is the SAED figure of Fig. 4 correspondence, can distinguish diffracted signal hardly among the figure, proves that further product is an amorphous calcium carbonate.
Embodiment 2
With CaCl
22H
2O powder and methylcarbonate were inserted and are contained and CaCl in 1: 2 in molar ratio
22H
2The mol ratio of O is in 5556: 1 the beaker of distilled water, makes it to be uniformly dispersed with the stirring velocity of 1000rpm, forms microemulsion.Will with CaCl
22H
2The O mol ratio is that 2: 1 equisetic acid sodium adds aforesaid liquid, stirs down dissolving fully.Will with CaCl
22H
2The O mol ratio is that 2: 1 NaOH powder adds above-mentioned mixed solution, continues to stir 4min, and digestion time is 6h.At last, with turbid liquid suction filtration, 27 ℃ of dryings are collected white product.
Utilize X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) that resulting product is characterized.The XRD figure of product spectrum is seen Fig. 1, and product is the amorphous calcium carbonate structure when spectrogram is clear that digestion time is 6h.The diameter of forming the nanoparticle of amorphous calcium carbonate is about 105nm, and other is similar embodiment 1 as a result.
Embodiment 3
With CaCl
22H
2O powder and methylcarbonate were inserted and are contained and CaCl in 1: 3 in molar ratio
22H
2The mol ratio of O is in 8334: 1 the beaker of distilled water, makes it to be uniformly dispersed with the stirring velocity of 300rpm, forms microemulsion.Will with CaCl
22H
2The O mol ratio is that 1: 2 trimesic acid sodium adds aforesaid liquid, stirs down dissolving fully.Will with CaCl
22H
2The O mol ratio is that 2: 1 NaOH powder adds above-mentioned mixed solution, continues to stir 1min, and digestion time is 9h.At last, with turbid liquid suction filtration, 20 ℃ of dryings are collected white product.
Utilize X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) that resulting product is characterized.The XRD figure of product spectrum is seen Fig. 1, and product is the amorphous calcium carbonate structure when spectrogram is clear that digestion time is 9h.The diameter of forming the nanoparticle of amorphous calcium carbonate is about 90nm, and other is similar embodiment 1 as a result.
Embodiment 4
With CaCl
22H
2O powder and methylcarbonate were inserted and are contained and CaCl in 1: 4 in molar ratio
22H
2The mol ratio of O is in 13890: 1 the beaker of distilled water, makes it to be uniformly dispersed with the stirring velocity of 600rpm, forms microemulsion.Will with CaCl
22H
2The O mol ratio is 1: 4 Na
3C
6H
5O
72H
2The O powder adds aforesaid liquid, stirs down dissolving fully.Will with CaCl
22H
2The O mol ratio is that 3: 1 NaOH powder adds above-mentioned mixed solution, continues to stir 2.5min, and digestion time is 4h.At last, with turbid liquid suction filtration, 25 ℃ of dryings are collected white product.
Utilize X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) that resulting product is characterized.The diameter of forming the nanoparticle of amorphous calcium carbonate is about 103nm, and other is similar embodiment 1 as a result.
Embodiment 5
With CaCl
22H
2O powder and methylcarbonate were inserted and are contained and CaCl in 1: 1 in molar ratio
22H
2The mol ratio of O is in 1389: 1 the beaker of distilled water, makes it to be uniformly dispersed with the stirring velocity of 800rpm, forms microemulsion.Will with CaCl
22H
2The O mol ratio is that 1: 3 equisetic acid sodium adds aforesaid liquid, stirs down dissolving fully.Will with CaCl
22H
2The O mol ratio is that 5: 1 NaOH powder adds above-mentioned mixed solution, continues to stir 7min, and digestion time is 6h.At last, with turbid liquid suction filtration, 30 ℃ of dryings are collected white product.
Utilize X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) that resulting product is characterized.The diameter of forming the nanoparticle of amorphous calcium carbonate is about 95nm, and other is similar embodiment 1 as a result.
Embodiment 6
With CaCl
22H
2O powder and methylcarbonate were inserted and are contained and CaCl in 1: 5 in molar ratio
22H
2The mol ratio of O is in 13890: 1 the beaker of distilled water, makes it to be uniformly dispersed with the stirring velocity of 400rpm, forms microemulsion.Will with CaCl
22H
2The O mol ratio is that 1: 1 trimesic acid sodium adds aforesaid liquid, stirs down dissolving fully.Will with CaCl
22H
2The O mol ratio is that 4: 1 NaOH powder adds above-mentioned mixed solution, continues to stir 2min, and digestion time is 7h.At last, with turbid liquid suction filtration, 25 ℃ of dryings are collected white product.
Utilize X-ray diffractometer (XRD), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) that resulting product is characterized.The diameter of forming the nanoparticle of amorphous calcium carbonate is about 98nm, and other is similar embodiment 1 as a result.
Claims (7)
1. the method for a preparing amorphous calcium carbonate by microemulsion method, it is characterized in that, with calcium chloride and the methylcarbonate microemulsion that is prepared into soluble in water, add tricarboxylate then and be dissolved in the microemulsion, under the effect of sodium hydroxide, make amorphous calcium carbonate afterwards; Wherein, calcium chloride, methylcarbonate are 1 with the ratio of the amount of substance that feeds intake of sodium hydroxide: 0.5-5: 1-5; Described tricarboxylate is Trisodium Citrate, equisetic acid sodium or trimesic acid sodium, and the tricarboxylate of adding is 0.2-2 with the amount of substance of calcium chloride ratio: 1.
2. the method for preparing amorphous calcium carbonate by microemulsion method as claimed in claim 1 is characterized in that, calcium chloride, methylcarbonate are 1: 1: 2 with the ratio of the amount of substance that feeds intake of sodium hydroxide.
3. the method for preparing amorphous calcium carbonate by microemulsion method as claimed in claim 1, it is characterized in that, described preparation of microemulsion method is as follows: under 10-30 ℃ that calcium chloride and methylcarbonate is soluble in water, speed with 50-1200rpm stirs the formation microemulsion, and wherein calcium chloride is 1 with the amount of substance ratio of water: 1300-14000.
4. the method for preparing amorphous calcium carbonate by microemulsion method as claimed in claim 3, it is characterized in that, described preparation of microemulsion method is as follows: under 25 ℃ that calcium chloride and methylcarbonate is soluble in water, speed with 500rpm stirs the formation microemulsion, and wherein calcium chloride is 1: 2778 with the amount of substance ratio of water.
5. the method for preparing amorphous calcium carbonate by microemulsion method as claimed in claim 1 is characterized in that, continues to stir 0.5-20min after adding NaOH, ageing 6min-9h then, and aftertreatment promptly gets described amorphous calcium carbonate.
6. the method for preparing amorphous calcium carbonate by microemulsion method as claimed in claim 5 is characterized in that, continues to stir 2min, ageing 3h then behind the adding NaOH.
7. as the method for claim 5 or 6 described preparing amorphous calcium carbonate by microemulsion method, it is characterized in that aftertreatment finishes the back suction filtration and carries out drying in 10-40 ℃ for reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910065055XA CN101580260B (en) | 2009-05-31 | 2009-05-31 | Method for preparing amorphous calcium carbonate by microemulsion method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910065055XA CN101580260B (en) | 2009-05-31 | 2009-05-31 | Method for preparing amorphous calcium carbonate by microemulsion method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101580260A CN101580260A (en) | 2009-11-18 |
| CN101580260B true CN101580260B (en) | 2011-04-27 |
Family
ID=41362601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910065055XA Expired - Fee Related CN101580260B (en) | 2009-05-31 | 2009-05-31 | Method for preparing amorphous calcium carbonate by microemulsion method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101580260B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2637019C2 (en) | 2012-08-07 | 2017-11-29 | Аморфикал Лтд. | Method for producing stabilized amorphous calcium carbonate |
| CN103570051B (en) * | 2013-11-15 | 2015-04-15 | 河南省分析测试研究中心 | Method for preparing nano calcium carbonate quantum dot through microemulsion system |
| WO2016016893A1 (en) | 2014-07-31 | 2016-02-04 | Amorphical Ltd. | Encapsulated amorphous calcium carbonate compositions |
| CN104261450B (en) * | 2014-10-13 | 2016-03-02 | 中国科学技术大学 | A kind of synthetic method of amorphous cium carbonate nanoparticles of size tunable |
| EP3302505B1 (en) | 2015-06-04 | 2024-02-28 | Amorphical Ltd. | Amorphous calcium carbonate stabilized with polyphosphates |
| CN105948095B (en) * | 2016-07-25 | 2017-10-20 | 陕西师范大学 | The method that regular hexagon calcium carbonate nano crystal grain is prepared based on reverse microemulsion |
| EP3532074B1 (en) | 2016-10-25 | 2023-08-23 | Amorphical Ltd. | Amorphous calcium carbonate for use in a method of treating a leukemia |
| CN110482585A (en) * | 2019-08-05 | 2019-11-22 | 浙江工业大学 | A kind of synthetic method of amorphous calcium carbonate |
| CN114455620B (en) * | 2022-01-11 | 2023-10-27 | 兰州交通大学 | Preparation method of square and cluster symbiotic micron-sized calcium carbonate |
-
2009
- 2009-05-31 CN CN200910065055XA patent/CN101580260B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101580260A (en) | 2009-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101580260B (en) | Method for preparing amorphous calcium carbonate by microemulsion method | |
| Xu et al. | Stable amorphous CaCO3 microparticles with hollow spherical superstructures stabilized by phytic acid | |
| Bensalah et al. | Hydrothermal synthesis of nanocrystalline hydroxyapatite from phosphogypsum waste | |
| AU2011234483B2 (en) | Process for obtaining precipitated calcium carbonate | |
| Cheng et al. | Preparation of monodispersed cubic calcium carbonate particles via precipitation reaction | |
| Dhand et al. | The facile and low temperature synthesis of nanophase hydroxyapatite crystals using wet chemistry | |
| Tari et al. | Synthesis of hydroxyapatite particles in catanionic mixed surfactants template | |
| Ding et al. | Synthesis and characterization of nesquehonite (MgCO3· 3H2O) powders from natural talc | |
| Ding et al. | Controllable synthesis of all the anhydrous CaCO3 polymorphs with various morphologies in CaCl2-NH3-CO2 aqueous system | |
| Shen et al. | Hydrothermal synthesis of CeO2 nano-octahedrons | |
| Kim et al. | Bio-inspired mineralization of CO2 gas to hollow CaCO3 microspheres and bone hydroxyapatite/polymer composites | |
| Daryan et al. | Surface engineered hollow hydroxyapatite microspheres: Hydrothermal synthesis and growth mechanisms | |
| Xiao et al. | Bio-inspired synthesis: understanding and exploitation of the crystallization process from amorphous precursors | |
| Salarian et al. | Template-directed hydrothermal synthesis of dandelion-like hydroxyapatite in the presence of cetyltrimethylammonium bromide and polyethylene glycol | |
| Zhou et al. | Preparation of Chinese mystery snail shells derived hydroxyapatite with different morphology using condensed phosphate sources | |
| Sun et al. | Preparation of basic magnesium carbonate by simultaneous absorption of NH3 and CO2 into MgCl2 solution in an RPB | |
| Jiang et al. | Confined crystallization of polycrystalline high-magnesium calcite from compact Mg-ACC precursor tablets and its biological implications | |
| Song et al. | Synergetic effects of initial NH4+ and Ca2+ concentration on the formation vaterite using steamed ammonia liquid waste as a direct carbonation | |
| CN110482585A (en) | A kind of synthetic method of amorphous calcium carbonate | |
| Tas | Calcium metal to synthesize amorphous or cryptocrystalline calcium phosphates | |
| CN110284197A (en) | A kind of production method of crystal whisker of gypsum clean and environmental protection | |
| Zhang et al. | Synthesis of nanorod and needle-like hydroxyapatite crystal and role of pH adjustment | |
| Altiner et al. | Production of precipitated calcium carbonate particles with different morphologies from dolomite ore in the presence of various hydroxide additives | |
| Nassar et al. | Influence of the operating conditions on the morphology of CaCO3 nanoparticles prepared by modified co-precipitation with pulse mode feeding | |
| Han et al. | Sequential formation of calcium carbonate superstructure: From solid/hollow spheres to sponge-like/solid films |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110427 Termination date: 20150531 |
|
| EXPY | Termination of patent right or utility model |