CN1513764A - preparation method of cubic ultrafine precipitated calcium carbonate - Google Patents
preparation method of cubic ultrafine precipitated calcium carbonate Download PDFInfo
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- CN1513764A CN1513764A CNA031160468A CN03116046A CN1513764A CN 1513764 A CN1513764 A CN 1513764A CN A031160468 A CNA031160468 A CN A031160468A CN 03116046 A CN03116046 A CN 03116046A CN 1513764 A CN1513764 A CN 1513764A
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- Prior art keywords
- preparation
- lime carbonate
- ultra
- fine precipitates
- cube
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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 22
- 238000002360 preparation method Methods 0.000 title claims description 18
- 229940088417 precipitated calcium carbonate Drugs 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 230000032683 aging Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 4
- 239000004571 lime Substances 0.000 claims abstract description 4
- 239000008267 milk Substances 0.000 claims abstract 2
- 210000004080 milk Anatomy 0.000 claims abstract 2
- 235000013336 milk Nutrition 0.000 claims abstract 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 239000000138 intercalating agent Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000005255 carburizing Methods 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyoxyethylene Polymers 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002738 chelating agent Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003483 aging Methods 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 241000220317 Rosa Species 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 231100000956 nontoxicity Toxicity 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
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A process for preparing the deposited superfine cubic calcium carbonate particles includes ageing the lime milk for 48 hr, adding soluble composite chelating agent, introducing CO2, carbonifying reaction at 40-60 deg.C, adding disperser, filtering and drying. Its advantages are low cost and energy consumption, uniform granularity, and easy control of reaction.
Description
Technical field
The present invention relates to a kind of preparation method of cube ultra-fine precipitates lime carbonate of economy, affiliated technical field is preparation inorganic and that solid material is chemical.
Background technology
Lime carbonate is one of the widest Inorganic Chemicals of present purposes, because price is low, raw material is wide, and nontoxicity is widely used in industries such as rubber, plastics, coating, papermaking, daily-use chemical industry and does weighting agent and reinforcement, semi-reinforcing agent.Along with the progress of domestic miniaturization and process for treating surface, make calcium carbonate product to specialized, become more meticulous, the functionalization development, the Application Areas of lime carbonate has been expanded in arising at the historic moment of novel material calcium carbonate superfine powder product.
Produce with remaining of chemical process large-scale industrial production precipitated chalk in the world at present with carborization.Be about to the kiln gas (CO that calcined limestone produces
2) feeding the heterogeneous carburizing reagent of carrying out solid, liquid, gas in the certain density milk of lime slurry, this reaction is thermodynamic (al) exothermal reaction process.As allow carburizing reagent in opening wide reactor, carry out, to temperature if the words do not controlled, will cause the temperature of reaction system to continue to rise so, can rise until about 80 ℃ from room temperature, the precipitated chalk product crystalline form that obtains will be mainly spindle shape and amorphous etc., and wide in rangeization of particle diameter, end-use is restricted.Present suitability for industrialized production cube type ultra-fine precipitates calcium carbonate product, all under less than 25 ℃ of conditions, carry out, carburizing reagent need be cooled off temperature control and just can be carried out, the result is a subcooling process energy consumption height, prepared cube ultra-fine precipitates calcium carbonate product surface energy is also high, Intermolecular Forces is big, and then causes viscosity excessive.If be reflected at greater than carrying out carburizing reagent under 35 ℃ the constant temperature, do not carry out special chemistry, when physical technology is handled, then the crystalline form of product still be the fusiform product, be the product cut size scope become narrow controlled.Therefore, preparation cube type ultra-fine precipitates lime carbonate under high temperature (〉=40 ℃) condition is developed, the refrigerating apparatus of enterprise is reduced, power consumption reduces, thereby has saved the energy for the temperature control additive decrementation.
Chinese patent (publication number CN-1361063A) has been introduced the method that the one step carbonization of a kind of usefulness prepares cubic calcium carbonate, it is characterized in that with methyl polyoxy silane being that the compound crystal control agent of main body comes synthesis of cubic lime carbonate.
Chinese patent (publication number CN-1169955A) has been introduced a kind of method that is used to prepare the ultra-fine precipitates calcium carbonate granule, and this method divided for two steps carried out: the first step makes about 0.04 micron colloid lime carbonate with chemical method; The product of second step with the first step is crystal seed, crystal seed added carry out carburizing reagent in the milk of lime, and institute's synthetic lime carbonate is that particle diameter is 0.1～1 micron a cube product.
The precipitated chalk preparation method that above-mentioned patent is introduced all exists or control agent cost height, or the technology relative complex, and size distribution is the characteristics of narrow refinement inadequately.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of cube ultra-fine precipitates lime carbonate of economy.Method of the present invention has that cost, energy consumption are low, the narrow refinement of average particle size distribution and the more manageable characteristics of reaction process.
The invention provides the method for preparation cube ultra-fine precipitates lime carbonate, in 48 hours lime slurry of ageing, add the compound intercalating agent of handling through processable, feed the CO of desired flow
2Carry out carburizing reagent, temperature of reaction rises the back Controllable Temperature built in 40～60 ℃, follows the tracks of the reaction whole process with conductivity meter.Carbonation rate added organic dispersing agent until reacting completely at 50～80% o'clock.Product after filtration, after the drying, obtain the cubic-crystal precipitated chalk.
Above-mentioned compound intercalating agent is: disodium EDTA: sodium bicarbonate or Diethylenetriamine penta acetate: the intercalating agent of wherein two to three kinds of proportioning of sodium bicarbonate, described intercalating agent: sodium bicarbonate=0.01～10: 1 (w/w).
Above-mentioned compound chelant amount is 0.01～10wt%, is benchmark with the theoretical growing amount of lime carbonate.
Above-mentioned lime slurry is the suspension liquid of calcium hydroxide, and its concentration is controlled at 10～30wt%.Reaction is at room temperature carried out.
Above-mentioned being reflected under 1000～2000 rev/mins the violent stirring slowly adds the compound intercalating agent of handling through processable continuously, compound intercalating agent add finish after, further stir 3～40min.
Described organic dispersing agent is polyoxyethylene glycol or diethanolamine or sodium polyacrylate, and its add-on is 0.01～10wt% of the theoretical growing amount of lime carbonate.
The described carburizing reagent deadline is 20～300 minutes.
Above-mentioned reaction feeds 5～45% (v/v) CO
2Carry out carburizing reagent, after temperature of reaction rose, Controllable Temperature was carried out isothermal reaction built in certain point of 40～60 ℃.Carbonation rate added organic dispersing agent until reacting completely at 50～80% o'clock.Follow the tracks of the reaction whole process with conductivity meter.When final conductivity data rises slightly, show that this carburizing reagent finishes.Final product is through ageing, filtration, drying and other steps and obtain.
In the process of preparation provided by the present invention cube ultra-fine precipitates lime carbonate, compound intercalating agent has been carried out the solubility of water and handled.On the one hand compound intercalating agent can be rapidly mixes with milk of lime in the reaction system, reaches maximum point-to-point contact; Calcium ion huge legendary turtle in the reaction system is closed on the other hand, the lime carbonate crystal seed generates and heterogeneous reaction in the dynamic diffusion reaction, impel the crystalline process of growth controlled.
In the reaction system of preparation provided by the present invention cube ultra-fine precipitates lime carbonate, CO
2In carbonization process, obtained sufficient exchange, its CO
2Total flux is controlled at 1～100L/minKg Ca (OH)
2
The method of carburizing reagent preparation cube ultra-fine precipitates lime carbonate provided by the present invention, its advantage is: compound intercalating agent be easy to get and the energy consumption narrow refinement of average particle size distribution low, product cheap, reaction process and reaction process more easy to control, thereby adopt this method to carry out cube production of ultra-fine precipitates lime carbonate and can improve economic benefit of enterprises preferably.
Embodiment
Embodiment 1
At first, get and contain 10～30wt% milk of lime 500mL, under 1000～2000 rev/mins violent stirring, add the compound intercalating agent disodium EDTA of handling through processable: sodium bicarbonate or Diethylenetriamine penta acetate: the intercalating agent of wherein two to three kinds of proportioning of sodium bicarbonate, compound chelant amount are to be 0.01～10wt% of datum quantity with the theoretical growing amount of lime carbonate.After compound intercalating agent adding finishes, further stir 3～40min.Feed CO down at 20 ℃ then
2, CO
2Total flux is controlled at 1～5L/minKg Ca (OH)
2After temperature of reaction rose, Controllable Temperature was carried out isothermal reaction built in certain point of 40～60 ℃.Carbonation rate added organic dispersing agent until reacting completely at 50～80% o'clock.Follow the tracks of the reaction whole process with conductivity meter.When final conductivity data rose slightly, carburizing reagent finished.Product is obtained through ageing, filtration, drying etc.Every index to product is measured, and its crystalline form is a cubes, and laser particle analyzer records the product cut size scope at 0.8～1.5 micron.Scanning electronic microscope shows that its size is 0.1 micron, and size distribution is even.
Embodiment 2
With with embodiment 1 identical operations, difference be with starting temperature 27 ℃ begin the reaction.
Finally every index of product is measured, shown that its crystalline form is a cubes, laser particle analyzer records the product cut size scope at 1.8～2.0 μ m.Scanning electronic microscope shows that its size is 0.3 micron, and size distribution is even.
Embodiment 3
With with embodiment 1 identical operations, difference is CO
2Total flux increases to 6～100L/minKg Ca (OH)
2, outlet temperature is controlled at 40 ℃.
Its crystalline form of the calcium carbonate product that is obtained is a cubes, and scanning electronic microscope shows that its size is 80nm, and laser particle analyzer records the product cut size scope at 1.2～2.0 microns.The narrow refinement of average particle size distribution.
Claims (7)
1, the preparation method of a kind of cube of ultra-fine precipitates lime carbonate is characterized in that adding the compound intercalating agent of handling through processable in 48 hours milk of lime of ageing, feeds the CO of desired flow
2Carry out carburizing reagent, the temperature of reaction back temperature that rises is controlled at 40～60 ℃, follows the tracks of the reaction whole process with conductivity meter, and carbonation rate is at 50～80% o'clock, adds organic dispersing agent until reacting completely, and product after filtration, after the drying, obtain the cubic-crystal precipitated chalk.
According to the preparation method of described cube of ultra-fine precipitates lime carbonate of claim 1, it is characterized in that 2, described lime milk concentration is 10～30wt%.
3, according to the preparation method of described cube of ultra-fine precipitates lime carbonate of claim 1, it is characterized in that the described compound intercalating agent of handling through processable is: disodium EDTA: sodium bicarbonate and Diethylenetriamine penta acetate: two to three kinds of proportioning in the sodium bicarbonate.
4, according to the preparation method of described cube of ultra-fine precipitates lime carbonate of claim 3, it is characterized in that described intercalating agent: sodium bicarbonate=0.01～10: 1 (w/w).
5, according to the preparation method of described cube of ultra-fine precipitates lime carbonate of claim 1 or 3, it is characterized in that described compound chelant amount is 0.01～10wt%, is benchmark with the theoretical growing amount of lime carbonate.
6, according to the preparation method of described cube of ultra-fine precipitates lime carbonate of claim 1 or 3, it is characterized in that described organic dispersing agent is polyoxyethylene glycol or diethanolamine or sodium polyacrylate, its add-on is 0.01～10wt% of the theoretical growing amount of lime carbonate.
7, according to the preparation method of described cube of ultra-fine precipitates lime carbonate of claim 1 or 3, it is characterized in that the described carburizing reagent deadline is 20～300 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03116046 CN1218877C (en) | 2003-03-26 | 2003-03-26 | Preparation method of cubic ultrafine precipitated calcium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03116046 CN1218877C (en) | 2003-03-26 | 2003-03-26 | Preparation method of cubic ultrafine precipitated calcium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1513764A true CN1513764A (en) | 2004-07-21 |
| CN1218877C CN1218877C (en) | 2005-09-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03116046 Expired - Fee Related CN1218877C (en) | 2003-03-26 | 2003-03-26 | Preparation method of cubic ultrafine precipitated calcium carbonate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101512069B (en) * | 2006-08-17 | 2012-04-04 | 密执安特种矿石公司 | Improved uv varnish gloss performance using novel pigment and process for making same |
| CN103880058A (en) * | 2014-03-26 | 2014-06-25 | 河北工业大学 | Precipitated calcium carbonate production technology for reducing magnesium and increasing calcium |
| CN103897434B (en) * | 2014-04-19 | 2016-03-30 | 芮城新泰纳米材料有限公司 | The preparation method that plastic master batch is Nano calcium carbonate dedicated |
| CN109437273A (en) * | 2018-12-19 | 2019-03-08 | 广西合山市华纳新材料科技有限公司 | A kind of preparation method of monodisperse cube winnofil |
-
2003
- 2003-03-26 CN CN 03116046 patent/CN1218877C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101512069B (en) * | 2006-08-17 | 2012-04-04 | 密执安特种矿石公司 | Improved uv varnish gloss performance using novel pigment and process for making same |
| CN103880058A (en) * | 2014-03-26 | 2014-06-25 | 河北工业大学 | Precipitated calcium carbonate production technology for reducing magnesium and increasing calcium |
| CN103880058B (en) * | 2014-03-26 | 2016-01-20 | 河北工业大学 | A kind of precipitated chalk production technique of falling magnesium increasing calcium |
| CN103897434B (en) * | 2014-04-19 | 2016-03-30 | 芮城新泰纳米材料有限公司 | The preparation method that plastic master batch is Nano calcium carbonate dedicated |
| CN109437273A (en) * | 2018-12-19 | 2019-03-08 | 广西合山市华纳新材料科技有限公司 | A kind of preparation method of monodisperse cube winnofil |
| CN109437273B (en) * | 2018-12-19 | 2020-09-08 | 广西合山市华纳新材料科技有限公司 | Preparation method of monodisperse cubic precipitated calcium carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1218877C (en) | 2005-09-14 |
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