CN105399128A - Micron spindle-fiber-like structure vaterite calcium carbonate preparation method - Google Patents
Micron spindle-fiber-like structure vaterite calcium carbonate preparation method Download PDFInfo
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Abstract
The present invention relates to a calcium carbonate inorganic mineral preparation method, particularly to a micron spindle-fiber-like structure vaterite calcium carbonate crystal preparation method, which comprises: 1) dissolving pluronic (F127) in a deionized water/ethanol system having a certain ratio (V/V); 2) adding a certain amount of sodium dodecyl sulfate (SDS) to the system; 3) preparing a calcium chloride aqueous solution with a certain concentration; 4) preparing a potassium carbonate aqueous solution with a certain concentration; 5) rapidly pouring the solution in the step 3) into the solution prepared in the step 2); 6) slowly adding the solution prepared in the step 4) into the solution in the step 5) in a dropwise manner, and aging at a certain temperature; and 7) carrying out centrifugation separation on the mixing solution obtained after the aging, and washing to obtain the micron spindle-fiber-like structure vaterite calcium carbonate crystal. According to the present invention, the prepared micron spindle-fiber-like structure vaterite calcium carbonate has characteristics of good purity, high yield and good monodisperse property, the preparation reaction conditions are easy to control, and the industrial production is easily achieved.
Description
Technical field
So the invention belongs to a kind of method about the special spindle of synthesis thread structural carbon acid calcium, be specifically related to the preparation method of calcium carbonate inorganic mineral, particularly relate to a kind of preparation method with the vaterite calcium carbonate crystal of spindle filamentary texture.
Background technology
In the past few decades, calcium carbonate causes the interest of numerous scientific research personnel, himself excellent, widely distributed, reliable biomineralization model can be provided for laboratory test.As everyone knows, calcium carbonate is present in nature with three kinds of forms: calcite, aragonite, vaterite.Calcite is crystalline phase the most stable on thermodynamics and kinetics, and vaterite is least stable crystalline phase, and it is easy to change other two kinds of crystalline phase [S.F.Chen into, S.H.Yu, J.Jiang, F.Q.Li, Y.K.Liu, Chem.Mater.18 (2006) 115.].
Nowadays, various self aggregation organic compound (table promoting agent second, Polymers-surfatant mixture) is used to the pattern and the crystalline phase [L.M.Qi that control calcium carbonate crystal, J.Li, J.M.Ma, Adv.Mater.14 (2002) 300.].But these experiments are mostly at room temperature complete.
Confirm through experiment, ethanol contributes to preventing the crystalline phase of calcium carbonate from being transformed to calcite by vaterite.The vaterite superstructure of cake shape controls ethanol and whose ratio simply, is successfully synthesized out [S.F.Chen, S.H.Yu, J.Jiang, F.Q.Li, Y.K.Liu, Chem.Mater.18 (2006) 115.] under 90 DEG C of conditions.The vaterite crystal of various pattern is in the system of water/ethylene glycol/sodium lauryl sulphate (SDS), be synthesized under 100 DEG C of microwave heating conditions [R.J.Qi, Y.J.Zhu, J.Phys.Chem., B110 (2006) 8302.].But, seldom there is report research temperature for the impact of calcium carbonate crystal.Based on current research, amphipathic non ionic polymer polymkeric substance, such as oxyethylene-propylene oxide-epoxyethane block copolymer (general stream Buddhist nun gram) is widely used in industrial production.The mixture of general stream Buddhist nun gram (P123) and cetyl trimethylammonium bromide (CTAB) has been employed successfully in and has controlled synthesis gold nano, micron order thin slice [L.Y.Wang, X.Chen, J.Zhan, Y.C.Chai, C.J.Yang, L.M.Xu, W.C.Zhuang, B.Jing, J.Phys.Chem., B109 (2005) 3189.].
Therefore, in this experiment, we add general stream Buddhist nun gram (F127) and SDS as additive in water/ethanol system, calcium carbonate crystal are carried out to the control of pattern and crystal formation, finally obtain micron order spindle filamentary texture vaterite calcium carbonate.
Summary of the invention
Primary technical problem to be solved by this invention is to provide the preparation method of the micron order spindle filamentary texture vaterite calcium carbonate crystal that a kind of technique is simple, operational safety, cost are low.
The present invention solves the problems of the technologies described above adopted technical scheme: the preparation method of micron spindle filamentary texture vaterite calcium carbonate, is characterized in that comprising the steps:
(1) general stream Buddhist nun gram (F127) is dissolved in certain proportion (V/V) deionized water/ethanol system, under being placed in 20 ~ 35 DEG C of environment, stirs the A liquid that 5 ~ 15min obtains clear.
(2) in the A liquid of clear, add sodium lauryl sulphate (SDS), continue maintenance 20 ~ 35 DEG C and be stirred to dissolving and mix, obtain clear solution B.
(3) by calcium chloride (CaCl
2) be dissolved in deionized water, under being placed in 20 ~ 35 DEG C of environment, stirring 5 ~ 15min and obtain clear transparent solutions C.
(4) by salt of wormwood (Ka
2cO
3) be dissolved in deionized water, under being placed in 20 ~ 35 DEG C of environment, stirring 5 ~ 15min and obtain clear transparent solutions D.
(5) C solution is joined in solution B fast, by this mixing solutions 30 ~ 90 DEG C of stirred in water bath 5 ~ 10 minutes.
(6) getting 1 ~ 10ml solution D is added drop-wise in above-mentioned mixing solutions, this mixed solution is placed in 30 ~ 100 DEG C of environment, ageing 1 ~ 12h.
(7) solution centrifugal will obtained after ageing, obtains white precipitate, by white precipitate distilled water wash 1 ~ 3 time, then uses nothing
Water-ethanol washing 1 ~ 3 time, obtains white precipitate and keeps 20 ~ 60 DEG C, dry 4 ~ 24h.
Compared with prior art, the invention has the advantages that: adopt simple hydrothermal method to obtain a micron technique for spindle filamentary texture vaterite calcium carbonate crystal: the method technique is simple, operational safety, cost are low, reproducible, suitability for scale production; Gained micron spindle filamentary texture vaterite calcium carbonate crystal good dispersity, distribution of sizes is homogeneous.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of micron spindle filamentary texture vaterite calcium carbonate crystal in embodiment 1;
Fig. 2 is the infrared picture of micron spindle filamentary texture vaterite calcium carbonate crystal in embodiment 1;
Embodiment:
Below in conjunction with accompanying drawing embodiment, the present invention is described in further detail "
Embodiment 1
1. general for 0.2g stream Buddhist nun gram (F127) is dissolved in the system of 25ml deionized water/ethanol=0.5, under being placed in 25 DEG C of environment, stirs the A liquid that 10min obtains clear.
2. in the A liquid of clear, add 0.312g sodium lauryl sulphate (SDS), continue maintenance 25 DEG C and be stirred to dissolving and mix, obtain clear solution B.
3. by 1.11g calcium chloride (CaCl
2) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions C.
4. by 1.06g salt of wormwood (Ka
2cO
3) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions D.
5. C solution is joined in solution B fast, by this mixing solutions 50 DEG C of stirred in water bath 5 minutes.
6. getting 5ml solution D is added drop-wise in above-mentioned mixing solutions, this mixed solution is placed in 80 DEG C of environment, ageing 2h.
7. the solution centrifugal will obtained after ageing, obtains white precipitate, by white precipitate distilled water wash 1 ~ 3 time, then uses absolute ethanol washing 1 ~ 3 time, obtains white precipitate and keep 50 DEG C, dry 12h.
Embodiment 2
1. general for 0.2g stream Buddhist nun gram (F127) is dissolved in the system of 25ml deionized water/ethanol=0, under being placed in 25 DEG C of environment, stirs the A liquid that 10min obtains clear.
2. in the A liquid of clear, add 0.312g sodium lauryl sulphate (SDS), continue maintenance 25 DEG C and be stirred to dissolving and mix, obtain clear solution B.
3. by 1.11g calcium chloride (CaCl
2) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions C.
4. by 1.06g salt of wormwood (Ka
2cO
3) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions D.
5. C solution is joined in solution B fast, by this mixing solutions 50 DEG C of stirred in water bath 5 minutes.
6. getting 5ml solution D is added drop-wise in above-mentioned mixing solutions, this mixed solution is placed in 80 DEG C of environment, ageing 2h.
7. the solution centrifugal will obtained after ageing, obtains white precipitate, by white precipitate distilled water wash 1 ~ 3 time, then uses absolute ethanol washing 1 ~ 3 time, obtains white precipitate and keep 50 DEG C, dry 12h.
Embodiment 3
1. general for 0.2g stream Buddhist nun gram (F127) is dissolved in the system of 25ml deionized water/ethanol=0.25, under being placed in 25 DEG C of environment, stirs the A liquid that 10min obtains clear.
2. in the A liquid of clear, add 0.312g sodium lauryl sulphate (SDS), continue maintenance 25 DEG C and be stirred to dissolving and mix, obtain clear solution B.
3. by 1.11g calcium chloride (CaCl
2) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions C.
4. by 1.06g salt of wormwood (Ka
2cO
3) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions D.
5. C solution is joined in solution B fast, by this mixing solutions 50 DEG C of stirred in water bath 5 minutes.
6. getting 5ml solution D is added drop-wise in above-mentioned mixing solutions, this mixed solution is placed in 80 DEG C of environment, ageing 2h.
7. the solution centrifugal will obtained after ageing, obtains white precipitate, by white precipitate distilled water wash 1 ~ 3 time, then uses absolute ethanol washing 1 ~ 3 time, obtains white precipitate and keep 50 DEG C, dry 12h.
Embodiment 4
1. general for 0.2g stream Buddhist nun gram (F127) is dissolved in the system of 25ml deionized water/ethanol=0.35, under being placed in 25 DEG C of environment, stirs the A liquid that 10min obtains clear.
2. in the A liquid of clear, add 0.312g sodium lauryl sulphate (SDS), continue maintenance 25 DEG C and be stirred to dissolving and mix, obtain clear solution B.
3. by 1.11g calcium chloride (CaCl
2) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions C.
4. by 1.06g salt of wormwood (Ka
2cO
3) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions D.
5. C solution is joined in solution B fast, by this mixing solutions 50 DEG C of stirred in water bath 5 minutes.
6. getting 5ml solution D is added drop-wise in above-mentioned mixing solutions, this mixed solution is placed in 80 DEG C of environment, ageing 2h.
7. the solution centrifugal will obtained after ageing, obtains white precipitate, by white precipitate distilled water wash 1 ~ 3 time, then uses absolute ethanol washing 1 ~ 3 time, obtains white precipitate and keep 50 DEG C, dry 12h.
Embodiment 5
1. general for 0.2g stream Buddhist nun gram (F127) is dissolved in the system of 25ml deionized water/ethanol=0.45, under being placed in 25 DEG C of environment, stirs the A liquid that 10min obtains clear.
2. in the A liquid of clear, add 0.312g sodium lauryl sulphate (SDS), continue maintenance 25 DEG C and be stirred to dissolving and mix, obtain clear solution B.
3. by 1.11g calcium chloride (CaCl
2) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions C.
4. by 1.06g salt of wormwood (Ka
2cO
3) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions D.
5. C solution is joined in solution B fast, by this mixing solutions 50 DEG C of stirred in water bath 5 minutes.
6. getting 5ml solution D is added drop-wise in above-mentioned mixing solutions, this mixed solution is placed in 80 DEG C of environment, ageing 2h.
7. the solution centrifugal will obtained after ageing, obtains white precipitate, by white precipitate distilled water wash 1 ~ 3 time, then uses absolute ethanol washing 1 ~ 3 time, obtains white precipitate and keep 50 DEG C, dry 12h.
Embodiment 6
1. general for 0.2g stream Buddhist nun gram (F127) is dissolved in the system of 25ml deionized water/ethanol=1.0, under being placed in 25 DEG C of environment, stirs the A liquid that 10min obtains clear.
2. in the A liquid of clear, add 0.312g sodium lauryl sulphate (SDS), continue maintenance 25 DEG C and be stirred to dissolving and mix, obtain clear solution B.
3. by 1.11g calcium chloride (CaCl
2) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions C.
4. by 1.06g salt of wormwood (Ka
2cO
3) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions D.
5. C solution is joined in solution B fast, by this mixing solutions 50 DEG C of stirred in water bath 5 minutes.
6. getting 5ml solution D is added drop-wise in above-mentioned mixing solutions, this mixed solution is placed in 80 DEG C of environment, ageing 2h.
7. the solution centrifugal will obtained after ageing, obtains white precipitate, by white precipitate distilled water wash 1 ~ 3 time, then uses absolute ethanol washing 1 ~ 3 time, obtains white precipitate and keep 50 DEG C, dry 12h.
Embodiment 7
1. general for 0.2g stream Buddhist nun gram (F127) is dissolved in the system of 25ml deionized water/ethanol=1.5, under being placed in 25 DEG C of environment, stirs the A liquid that 10min obtains clear.
2. in the A liquid of clear, add 0.312g sodium lauryl sulphate (SDS), continue maintenance 25 DEG C and be stirred to dissolving and mix, obtain clear solution B.
3. by 1.11g calcium chloride (CaCl
2) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions C.
4. by 1.06g salt of wormwood (Ka
2cO
3) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions D.
5. C solution is joined in solution B fast, by this mixing solutions 50 DEG C of stirred in water bath 5 minutes.
6. getting 5ml solution D is added drop-wise in above-mentioned mixing solutions, this mixed solution is placed in 80 DEG C of environment, ageing 2h.
7. the solution centrifugal will obtained after ageing, obtains white precipitate, by white precipitate distilled water wash 1 ~ 3 time, then uses absolute ethanol washing 1 ~ 3 time, obtains white precipitate and keep 50 DEG C, dry 12h.
Embodiment 8
1. general for 0.2g stream Buddhist nun gram (F127) is dissolved in the system of 25ml deionized water/ethanol=2.0, under being placed in 25 DEG C of environment, stirs the A liquid that 10min obtains clear.
2. in the A liquid of clear, add 0.312g sodium lauryl sulphate (SDS), continue maintenance 25 DEG C and be stirred to dissolving and mix, obtain clear solution B.
3. by 1.11g calcium chloride (CaCl
2) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions C.
4. by 1.06g salt of wormwood (Ka
2cO
3) be dissolved in 10ml deionized water, under being placed in 25 DEG C of environment, stirring 10min and obtain clear transparent solutions D.
5. C solution is joined in solution B fast, by this mixing solutions 50 DEG C of stirred in water bath 5 minutes.
6. getting 5ml solution D is added drop-wise in above-mentioned mixing solutions, this mixed solution is placed in 80 DEG C of environment, ageing 2h.
7. the solution centrifugal will obtained after ageing, obtains white precipitate, by white precipitate distilled water wash 1 ~ 3 time, then uses absolute ethanol washing 1 ~ 3 time, obtains white precipitate and keep 50 DEG C, dry 12h.
Claims (5)
1. a preparation method for micron spindle filamentary texture vaterite calcium carbonate, is characterized in that comprising the following steps:
(1) general stream Buddhist nun gram (F127) is dissolved in certain proportion (V/V) deionized water/ethanol system, under being placed in 20 ~ 35 DEG C of environment, stirs the A liquid that 5 ~ 15min obtains clear.
(2) in the A liquid of clear, add sodium lauryl sulphate (SDS), continue maintenance 20 ~ 35 DEG C and be stirred to dissolving and mix, obtain clear solution B.
(3) by calcium chloride (CaCl
2) be dissolved in deionized water, under being placed in 20 ~ 35 DEG C of environment, stirring 5 ~ 15min and obtain clear transparent solutions C.
(4) by salt of wormwood (Ka
2cO
3) be dissolved in deionized water, under being placed in 20 ~ 35 DEG C of environment, stirring 5 ~ 15min and obtain clear transparent solutions D.
(5) C solution is joined in solution B fast, by this mixing solutions 30 ~ 90 DEG C of stirred in water bath 5 ~ 10 minutes.
(6) getting 1 ~ 10ml solution D is added drop-wise in above-mentioned mixing solutions, this mixed solution is placed in 30 ~ 100 DEG C of environment, ageing 1 ~ 12h.
(7) solution centrifugal will obtained after ageing, obtains white precipitate, by white precipitate distilled water wash 1 ~ 3 time, then uses absolute ethanol washing 1 ~ 3 time, obtains white precipitate and keeps 20 ~ 60 DEG C, dry 4 ~ 24h.
2. by the preparation method of micron spindle filamentary texture vaterite calcium carbonate described in claim 1, it is characterized in that: in described step (1), deionized water/proportion of ethanol V/V is between 0 ~ 2.
3. by the preparation method of micron spindle filamentary texture vaterite calcium carbonate described in claim 1, it is characterized in that: the amount of the added SDS of described step (2) is at 0.1 ~ 2g.
4. by the preparation method of micron spindle filamentary texture vaterite calcium carbonate described in claim 1, it is characterized in that: in described step (3), the concentration of calcium chloride water is 0.05 ~ 1.0mol/L.
5. by the preparation method of micron spindle filamentary texture vaterite calcium carbonate described in claim 1, it is characterized in that: in described step (4), the concentration of wet chemical is 0.05 ~ 1.0mol/L.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107416882A (en) * | 2017-08-18 | 2017-12-01 | 湖北工业大学 | A kind of method that metastable state vaterite calcium carbonate is prepared based on ethylene glycol calcium method |
| CN107555459A (en) * | 2017-09-13 | 2018-01-09 | 泰兴市诚盛化工有限公司 | A kind of preparation method of nanometer of spindle winnofil |
| CN109650432A (en) * | 2019-01-15 | 2019-04-19 | 桂林电子科技大学 | A kind of preparation and its application of parents' calcite type calcium carbonate |
| CN110817923A (en) * | 2019-12-13 | 2020-02-21 | 贺州学院 | Preparation method of fusiform vaterite calcium carbonate |
-
2014
- 2014-09-09 CN CN201410458165.3A patent/CN105399128A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107416882A (en) * | 2017-08-18 | 2017-12-01 | 湖北工业大学 | A kind of method that metastable state vaterite calcium carbonate is prepared based on ethylene glycol calcium method |
| CN107555459A (en) * | 2017-09-13 | 2018-01-09 | 泰兴市诚盛化工有限公司 | A kind of preparation method of nanometer of spindle winnofil |
| CN109650432A (en) * | 2019-01-15 | 2019-04-19 | 桂林电子科技大学 | A kind of preparation and its application of parents' calcite type calcium carbonate |
| CN110817923A (en) * | 2019-12-13 | 2020-02-21 | 贺州学院 | Preparation method of fusiform vaterite calcium carbonate |
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Application publication date: 20160316 |