CN1490248A - Preparation method of chain superfine calcium carbonate - Google Patents
Preparation method of chain superfine calcium carbonate Download PDFInfo
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- CN1490248A CN1490248A CNA021311765A CN02131176A CN1490248A CN 1490248 A CN1490248 A CN 1490248A CN A021311765 A CNA021311765 A CN A021311765A CN 02131176 A CN02131176 A CN 02131176A CN 1490248 A CN1490248 A CN 1490248A
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- chain
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- cao
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title abstract description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 title abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 230000005587 bubbling Effects 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 claims description 2
- LWZFANDGMFTDAV-WYDSMHRWSA-N [2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC(O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-WYDSMHRWSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XGKPLOKHSA-N [2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XGKPLOKHSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- -1 papermaking Substances 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
- 150000003839 salts Chemical class 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本发明涉及一种链状形貌超细碳酸钙的制备方法。通过组合形貌控制剂，以间歇鼓泡炭化法，一步反应制备了分散效果良好的，轴向尺寸约20nm，长径比约11∶1的链状超细碳酸钙。本发明的晶形控制由三种助剂组合控制完成。炭化过程一步完成，具有原料无毒、操作安全、简便的优点，适合工业化生产。The invention relates to a preparation method of ultrafine calcium carbonate with a chain shape. By combining the morphology control agent and adopting the intermittent bubbling carbonization method, a chain-like ultrafine calcium carbonate with good dispersion effect, an axial size of about 20nm and an aspect ratio of about 11:1 was prepared. The control of the crystal form of the present invention is accomplished through the combined control of three additives. The carbonization process is completed in one step, and has the advantages of non-toxic raw materials, safe and simple operation, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of chain pattern calcium carbonate superfine powder.
Background technology
Chain superfine hydrofil is the nano-calcium carbonate calcium product with one dimension shape characteristic.Compare with fine particle calcium carbonate with traditional coarse whiting, chain superfine hydrofil has good strengthening action to natural rubber, synthetic rubber, can partly replace carbon black or white carbon black as reinforced filling, reduce cost greatly, and chain lime carbonate is during as the additive of coating, papermaking, plastics industry, show excellent performance equally, be with a wide range of applications.
Japanese Patent is more common in research about chain lime carbonate preparation technology, Japanese Patent (clear 45-31851, clear 47-22944, clear 50-33995) generally takes to add specific opportunity the method control shape and appearance of calcium carbonate of soluble salts such as sulfuric acid, sal epsom, calcium sulfate, the more about 30～40nm of the axial dimension of product in certain of carbonization process.Japanese Patent (clear 56-26613) adopts two step charrings, at first behind adding EDTA2Na or other organic acids, begins charing before reaction, stops charing when reaction proceeds to certain specified phase; Add a certain amount of soluble inorganic salt, behind the thorough mixing, continue to feed CO
2, beginning second charing stage finishes until charing.The length-to-diameter ratio of product increases, and axial dimension can be decreased to below the 20nm, but because carbonization process is finished in two steps, is unfavorable for the raising of production efficiency.
Summary of the invention
Purpose of the present invention is to adopt a step charring, is the morphology control agent with the combined additive of document different from the past, prepares and the similar chain superfine hydrofil product of Japanese Patent (clear 56-26613) effect.
Technical scheme of the present invention is: the CaO of doses ratio is prepared into lime slurry, behind the adding component A thorough mixing, under the certain temperature, feeds the CO of certain flow
2Gas adds an amount of B component and the agent of component C morphology control suitable opportunity at twice, logical continuously CO
2To the reaction end.Product after filtration, drying obtains chain superfine hydrofil.
Employed morphology control agent is in the above-mentioned technology: component A can be EDTA2Na, Ba Dousuan, toxilic acid, oxyacetic acid, phenylformic acid, B component can be AE0-3, PVP, Span20, Span40, Span60, DP-S81, Telo-70, and component C can be CaCl
2, CaSO
4, Ca (NO)
2, Ca
3(PO
4)
2, MgCl
2, MgSO
4, AlCl
3
Combined additive can together add, but component A adds before reaction, and B component and component C add effect respectively in reaction process best.
Temperature of reaction is controlled at 5～30 ℃, CO
2Flow is 12～24ml/min/g CaO, and lime milk concentration is 3～15g CaO/100ml H
2O.
Effect of the present invention: the present invention adopts combined additive, with intermittence the bubbling charring shape and appearance of calcium carbonate is controlled, carbonization process one step finishes, and has advantages of nontoxic raw materials, operational safety, easy advantage, is fit to suitability for industrialized production.From electromicroscopic photograph, the length-to-diameter ratio of this calcium carbonate product, and axial dimension suitable substantially with Japanese Patent (clear 56-26613).
Description of drawings
Fig. 1, the transmission electron microscope photo of the chain superfine hydrofil of embodiment 1.
Fig. 2, the transmission electron microscope photo of comparative example 1.
Fig. 3, the transmission electron microscope photo of comparative example 2.
Embodiment
Embodiment 1:
The preparation solid content is 5gCaO/100mlH
2The milk of lime 100ml of O, controlled temperature is 23 ℃, be reflected at beginning before, 0.34g EDTA2Na is dissolved in the 10ml water, add reaction system, stir that the flow with 65～70mL/min feeds CO behind the 40min
2Gas, the aqueous solution 4ml that adding contained 0.055g PVP dispersion agent when reaction proceeded to 15min add the CaCl of 0.025g/nL in reaction system when reaction proceeds to 40min
2Aqueous solution 2mL reacts some end to pH6～7.XRD analysis shows, gained CaCO
3Be the calcite phase.Obtain chain superfine hydrofil after 100 ℃ of dryings, transmission electron microscope photo as shown in Figure 1, its axial dimension is about 20nm, about 11: 1 of length-to-diameter ratio.
Comparative example 1:
Do not add PVP and CaCl
2, only adding EDTA2Na, other conditions are identical with embodiment 1, then lime carbonate still has the one dimension shape characteristic, transmission electron microscope photo as shown in Figure 2, its axial diameter is about 40～60nm, length-to-diameter ratio is about 6～7: 1, and axial dimension is big than embodiment 1, and major diameter comparing embodiment 1 is little.
Comparative example 2:
Only add EDTA2Na and CaCl
2, do not add PVP, other conditions are identical with embodiment 1, the transmission electron microscope photo of gained calcium carbonate product as shown in Figure 3, the about 30nm of its axial diameter, about 4: 1 of length-to-diameter ratio.Axial dimension is little than comparative example 1, reduces but length-to-diameter ratio is also corresponding.
Embodiment 2:
The preparation solid content is 5gCaO/100mlH
2The milk of lime 100ml of O, controlled temperature is 23 ℃, be reflected at beginning before, 0.34g EDTA2Na is dissolved in the 10ml water, add reaction system, stir that the flow with 65～70mL/min feeds CO behind the 40min
2Gas adds 1ml AE0-3 dispersion agent 1ml when reaction proceeds to 1 5min, add the CaCl of 0.025g/mL when reaction proceeds to 40min
2Aqueous solution 2mL reacts some end to pH6～7.Obtain chain superfine hydrofil after 100 ℃ of dryings, its axial dimension is about 30nm, about 10: 1 of length-to-diameter ratio, but its dispersion effect is not as good as embodiment 1.
Claims (4)
1, a kind of morphology control agent by combination, with intermittence the bubbling charring prepare the method for the good chain superfine hydrofil of dispersion effect.The CaO of doses ratio is prepared into lime slurry, under the certain temperature, feeds the CO of certain flow
2Gas adds an amount of morphology control agent suitable opportunity respectively, logical continuously CO
2To the reaction end.Product after filtration, drying obtains chain superfine hydrofil.It is characterized in that: carbonization process need not to interrupt, and a step finishes, and the shape characteristic of lime carbonate is realized by the Combination Control of three kinds of additives.
2, preparation method according to claim 1, it is characterized in that: crystal morphology is finished by the Combination Control of additive, this Combination Control agent is made of two or more component, component A can be EDTA2Na, Ba Dousuan, toxilic acid, oxyacetic acid, phenylformic acid, B component can be AE0-3, PVP, Span20, Span40, Span60, DP-S81, Telo-70, and component C can be CaCl
2, CaSO
4, Ca (NO
3)
2, Ca
3(PO
4)
2, MgCl
2, MgSO
4, AlCl
3
3, according to the described preparation method of claim 1, it is characterized in that: the Combination Control agent can be component A, B, a kind of among the C, two or three, wherein the add-on of component A is more than 0.5% of CaO, and the add-on of B component is more than 0.5% of CaO, and the add-on of component C is more than 0.5% of CaO.
4, preparation method according to claim 1 is characterized in that: combined additive can together add, but component A adds before reaction, and B component and component C add effect respectively in reaction process best.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021311765A CN1490248A (en) | 2002-10-15 | 2002-10-15 | Preparation method of chain superfine calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021311765A CN1490248A (en) | 2002-10-15 | 2002-10-15 | Preparation method of chain superfine calcium carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1490248A true CN1490248A (en) | 2004-04-21 |
Family
ID=34144819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA021311765A Pending CN1490248A (en) | 2002-10-15 | 2002-10-15 | Preparation method of chain superfine calcium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1490248A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668602A (en) * | 2016-04-07 | 2016-06-15 | 安徽江东科技粉业有限公司 | Preparation method for calcium carbonate superfine powder |
| CN105776301A (en) * | 2016-04-07 | 2016-07-20 | 安徽江东科技粉业有限公司 | Preparing method of porous calcium carbonate |
| CN105883881A (en) * | 2016-04-07 | 2016-08-24 | 安徽江东科技粉业有限公司 | Preparation method of superfine calcium carbonate for printing ink |
| CN108069452A (en) * | 2017-12-19 | 2018-05-25 | 安徽省宣城市华纳新材料科技有限公司 | A kind of preparation method of chain calcite type calcium carbonate |
| CN110980787A (en) * | 2019-12-25 | 2020-04-10 | 广西华纳新材料科技有限公司 | Preparation method of calcium carbonate-calcium sulfate nano composite chain material |
-
2002
- 2002-10-15 CN CNA021311765A patent/CN1490248A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668602A (en) * | 2016-04-07 | 2016-06-15 | 安徽江东科技粉业有限公司 | Preparation method for calcium carbonate superfine powder |
| CN105776301A (en) * | 2016-04-07 | 2016-07-20 | 安徽江东科技粉业有限公司 | Preparing method of porous calcium carbonate |
| CN105883881A (en) * | 2016-04-07 | 2016-08-24 | 安徽江东科技粉业有限公司 | Preparation method of superfine calcium carbonate for printing ink |
| CN108069452A (en) * | 2017-12-19 | 2018-05-25 | 安徽省宣城市华纳新材料科技有限公司 | A kind of preparation method of chain calcite type calcium carbonate |
| CN110980787A (en) * | 2019-12-25 | 2020-04-10 | 广西华纳新材料科技有限公司 | Preparation method of calcium carbonate-calcium sulfate nano composite chain material |
| CN110980787B (en) * | 2019-12-25 | 2022-07-19 | 广西华纳新材料股份有限公司 | Preparation method of calcium carbonate-calcium sulfate nano composite chain material |
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| PB01 | Publication | ||
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| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |