CN103864127B - A kind of flower ball-shaped vaterite calcium carbonate and preparation method thereof - Google Patents
A kind of flower ball-shaped vaterite calcium carbonate and preparation method thereof Download PDFInfo
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- CN103864127B CN103864127B CN201410122443.8A CN201410122443A CN103864127B CN 103864127 B CN103864127 B CN 103864127B CN 201410122443 A CN201410122443 A CN 201410122443A CN 103864127 B CN103864127 B CN 103864127B
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- solution
- calcium carbonate
- carbon dioxide
- bubbled stone
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 81
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004575 stone Substances 0.000 claims abstract description 21
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000004062 sedimentation Methods 0.000 claims abstract description 9
- 239000001110 calcium chloride Substances 0.000 claims abstract description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical class [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001721 carbon Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 description 7
- 229960002713 calcium chloride Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 amine salt Chemical class 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 229940052299 calcium chloride dihydrate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Abstract
The invention provides a kind of preparation method of flower ball-shaped vaterite calcium carbonate, its technical scheme is: take calcium chloride as raw material, the certain density aqueous solution is mixed with deionized water or distilled water, then in this solution, pH electrode is inserted, with ammoniacal liquor regulator solution to 9.0 ~ 11.5, pass into the carbon dioxide after Bubbled stone is pre-dispersed again, when pH value of solution is down to 7.5, stop passing into carbon dioxide, finally add ethanol, by sedimentation and filtration and with after deionized water or distilled water wash, dry at 105 DEG C, obtain vaterite calcium carbonate.The product pattern that the present invention obtains is flower ball-shaped, and size is at 4 ~ 8 μm.
Description
Technical field
The present invention relates to a kind of flower ball-shaped vaterite calcium carbonate and preparation method thereof, belong to field of inorganic chemical engineering.
Background technology
Vaterite calcium carbonate monodispersity is good, not easily assemble, there is larger specific surface area, higher solvability and dispersing property and less proportion, thus compared with calcite, aragonite calcium carbonate, effectively can improve the coating property of paper and the fillibility of plastics, coating, ink, paper etc., improve the physicals of target product, glossiness, mobility and printing performance.Vaterite calcium carbonate also plays very important effect to the life and health of biology in addition.
At present, the preparation method of vaterite calcium carbonate mainly contains following several: (1) adds methyl alcohol (as US publication US5275651), water soluble acid (JP63103824 in calcium hydroxide aqeous suspension, CN1840479), organic amine salt (US5290353) or water-soluble natural polymer (as Japanese Laid-Open Patent JP3060427, CN101249977), then pass into carbon dioxide and obtain vaterite calcium carbonate; (2) in the alkaline calcium salt aqueous solution, add high-molecular polyamide-amine (JP2003-63819) or hyperbranched polyglycidyl ether (CN102583485), then add basic carbonate or supercarbonate reaction prepare vaterite calcium carbonate micron ball; (3) mixed gas passing into carbon dioxide or carbonic acid gas and nitrogen to alkaline calcium chloride water prepares vaterite calcium carbonate (G.Hadiko, Y.S.Han, M.Fuji, et.al.Synthesisofhollowcalciumcarbonateparticlesbythebub bletemplatingmethod [J] .Mater.Lett.2005,59 (19-20): 2519-2522; TatsuyaTomioka, MasayoshiFuji, MinoruTakahashi, et.al.HollowStructureFormationMechanismofCalciumCarbonat eParticlesSynthesizedbytheCO
2bubblingMethod [J] .CrystalGrowth & Design, 2012,12 (2): 771-776).The vaterite shape and appearance of calcium carbonate obtained has spherical, ellipsoid shape, plate-like, round pie, staple fibre shape etc.The invention provides a kind of preparation method of flower ball-shaped vaterite calcium carbonate, is obtained for passing in alkaline calcium chloride solution reaction after small bubbles again through Bubbled stone is pre-dispersed by carbon dioxide.
Summary of the invention
The invention reside in and a kind of flower ball-shaped vaterite calcium carbonate and preparation method thereof is provided.The technical scheme of this invention is as follows: take calcium chloride as raw material, the certain density aqueous solution is mixed with deionized water or distilled water, then in this solution, insert pH electrode, with ammoniacal liquor regulator solution to 9.0 ~ 11.5, then pass into the carbon dioxide after Bubbled stone is pre-dispersed, when pH value of solution is down to 7.5, stop passing into carbon dioxide, finally add ethanol, by sedimentation and filtration and with after deionized water or distilled water wash, dry at 105 DEG C, obtain monodisperse sphere aragonite calcium carbonate.The product pattern that the present invention obtains is flower ball-shaped, and size is at 4 ~ 8 μm.
Above-mentioned used calcium chloride is Calcium Chloride Powder Anhydrous (CaCl
2) or CALCIUM CHLORIDE DIHYDRATE (CaCl
2h
2o), the concentration of the calcium chloride solution of preparation is 0.05 ~ 1.0mol/L;
The flow of the above-mentioned carbon dioxide passed into is 0.1 ~ 3L/min;
Above-mentioned Bubbled stone is white fused alumina Bubbled stone or ore in sand form Bubbled stone or silicon carbide Bubbled stone or green carbon Bubbled stone.
The add-on of above-mentioned ethanol is 10% ~ 30% (volume ratio) of calcium chloride solution.
Present invention process is simple, and reaction conditions is gentle, and equipment is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
Accompanying drawing 1 is for preparing the experimental installation of flower ball-shaped vaterite calcium carbonate
Accompanying drawing 2 is the scanning electron microscope (SEM) photograph of prepared flower ball-shaped vaterite calcium carbonate
Accompanying drawing 3 is the XRD figure of prepared flower ball-shaped vaterite calcium carbonate
Embodiment
Embodiment 1 a volume be add in the reaction vessel of 2L in advance with deionized water preparation concentration be the calcium chloride solution of 0.05mol/L, then in this solution, pH electrode is inserted, with ammoniacal liquor regulator solution to pH=9.0, pass into the carbon dioxide after white fused alumina Bubbled stone Bubbled stone is pre-dispersed (controlling flow of carbon dioxide gas amount is 0.1L/min) again, when pH value of solution is down to 7.5, stop passing into carbon dioxide, finally add 0.1L ethanol, by sedimentation and filtration and with after deionized water wash, dry at 105 DEG C, obtain monodisperse sphere aragonite calcium carbonate.The product pattern that the present invention obtains is flower ball-shaped, and size is at 4 ~ 8 μm.
Embodiment 2 a volume be add in the reaction vessel of 2L in advance with deionized water preparation concentration be the calcium chloride solution of 0.5mol/L, then in this solution, pH electrode is inserted, with ammoniacal liquor regulator solution to pH=10.0, pass into the carbon dioxide after ore in sand form Bubbled stone is pre-dispersed (controlling flow of carbon dioxide gas amount is 1L/min) again, when pH value of solution is down to 7.5, stop passing into carbon dioxide, finally add 0.2L ethanol, by sedimentation and filtration and with after deionized water wash, dry at 105 DEG C, obtain monodisperse sphere aragonite calcium carbonate.The product pattern that the present invention obtains is flower ball-shaped, and size is at 4 ~ 8 μm.
Embodiment 3 a volume be add in the reaction vessel of 2L in advance with deionized water preparation concentration be the calcium chloride solution of 1.0mol/L, then in this solution, pH electrode is inserted, with ammoniacal liquor regulator solution to pH=9.0, pass into the carbon dioxide after silicon carbide Bubbled stone is pre-dispersed (controlling flow of carbon dioxide gas amount is 2L/min) again, when pH value of solution is down to 7.5, stop passing into carbon dioxide, finally add 0.3L ethanol, by sedimentation and filtration and with after deionized water wash, dry at 105 DEG C, obtain monodisperse sphere aragonite calcium carbonate.The product pattern that the present invention obtains is flower ball-shaped, and size is at 4 ~ 8 μm.
Embodiment 4 a volume be add in the reaction vessel of 2L in advance with distilled water preparation concentration be the calcium chloride solution of 0.1mol/L, then in this solution, pH electrode is inserted, with ammoniacal liquor regulator solution to pH=9.0, pass into the carbon dioxide after green carbon Bubbled stone is pre-dispersed (controlling flow of carbon dioxide gas amount is 0.5L/min) again, when pH value of solution is down to 7.5, stop passing into carbon dioxide, finally add 0.2L ethanol, by sedimentation and filtration and with after distilled water wash, dry at 105 DEG C, obtain monodisperse sphere aragonite calcium carbonate.The product pattern that the present invention obtains is flower ball-shaped, and size is at 4 ~ 8 μm.
Embodiment 5 a volume be add in the reaction vessel of 2L in advance with distilled water preparation concentration be the calcium chloride solution of 0.5mol/L, then in this solution, pH electrode is inserted, with ammoniacal liquor regulator solution to pH=10.5, pass into the carbon dioxide after white fused alumina Bubbled stone is pre-dispersed (controlling flow of carbon dioxide gas amount is 3L/min) again, when pH value of solution is down to 7.5, stop passing into carbon dioxide, finally add 0.3L ethanol, by sedimentation and filtration and with after distilled water wash, dry at 105 DEG C, obtain monodisperse sphere aragonite calcium carbonate.The product pattern that the present invention obtains is flower ball-shaped, and size is at 4 ~ 8 μm.
Embodiment 6 a volume be add in the reaction vessel of 2L in advance with distilled water preparation concentration be the calcium chloride solution of 1.0mol/L, then in this solution, pH electrode is inserted, with ammoniacal liquor regulator solution to pH=11.5, pass into the carbon dioxide after silicon carbide Bubbled stone is pre-dispersed (controlling flow of carbon dioxide gas amount is 3L/min) again, when pH value of solution is down to 7.5, stop passing into carbon dioxide, finally add 0.3L ethanol, by sedimentation and filtration and with after distilled water wash, dry at 105 DEG C, obtain monodisperse sphere aragonite calcium carbonate.The product pattern that the present invention obtains is flower ball-shaped, and size is at 4 ~ 8 μm.
Claims (3)
1. the preparation method of a flower ball-shaped vaterite calcium carbonate, it is characterized in that: take calcium chloride as raw material, the certain density aqueous solution is mixed with deionized water or distilled water, then in this solution, pH electrode is inserted, with ammoniacal liquor regulator solution to 9.0 ~ 11.5, pass into the carbon dioxide after Bubbled stone is pre-dispersed again, when pH value of solution is down to 7.5, stop passing into carbon dioxide, finally add ethanol, by sedimentation and filtration and with after deionized water or distilled water wash, dry at 105 DEG C, obtain monodisperse sphere aragonite calcium carbonate.
2. preparation method according to claim 1, is characterized in that: the Bubbled stone adopted be white fused alumina series Bubbled stone or ore in sand form series Bubbled stone or silicon-carbide series Bubbled stone or green carbon series Bubbled stone.
3. preparation method according to claim 1, is characterized in that: the add-on of ethanol is 10% ~ 30% (volume ratio) of calcium chloride water.
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| CN201410122443.8A CN103864127B (en) | 2014-03-31 | 2014-03-31 | A kind of flower ball-shaped vaterite calcium carbonate and preparation method thereof |
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| CN103864127B true CN103864127B (en) | 2015-12-09 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104118895B (en) * | 2014-07-24 | 2015-12-09 | 北京化工大学 | A kind of acidolysis Wingdale prepares the method for homogeneous phase nanometer ball vaterite type calcium carbonate |
| CN105417564B (en) * | 2015-09-14 | 2017-12-15 | 广西大学 | A kind of preparation method of petal flaky calcium carbonate crystal |
| CN105858696A (en) * | 2016-03-28 | 2016-08-17 | 武汉工程大学 | Preparation method and application for micron vaterite type food-grade calcium carbonate |
| WO2019190163A1 (en) * | 2018-03-30 | 2019-10-03 | 한국해양대학교 산학협력단 | Method for manufacturing high-purity vaterite-type and calcite-type calcium carbonate by using indirect carbonation of seawater |
| CN111517352B (en) * | 2020-04-30 | 2023-04-28 | 广西大学 | Preparation method of high-purity vaterite type calcium carbonate microspheres |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225775A (en) * | 2011-05-13 | 2011-10-26 | 河北科技大学 | Process for producing magnesium hydroxide and calcium carbonate by dolomite conversion method |
| CN103553108A (en) * | 2013-11-14 | 2014-02-05 | 湖北工业大学 | Method and device for preparing vaterite-type calcium carbonate powder |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4889888B2 (en) * | 2001-08-27 | 2012-03-07 | 宇部日東化成株式会社 | Method for producing vaterite-type spherical calcium carbonate and vaterite-type spherical calcium carbonate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225775A (en) * | 2011-05-13 | 2011-10-26 | 河北科技大学 | Process for producing magnesium hydroxide and calcium carbonate by dolomite conversion method |
| CN103553108A (en) * | 2013-11-14 | 2014-02-05 | 湖北工业大学 | Method and device for preparing vaterite-type calcium carbonate powder |
Non-Patent Citations (1)
| Title |
|---|
| "Hollow Structure Formation Mechanism of Calcium Carbonate Particles Synthesized by the CO2 Bubbling Method";Tatsuya Tomioka et al.;《Cryst. Growth Des》;20111206;第12卷;第771-776页 * |
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