CN103011227A - Preparation method of ultrafine coating light calcium carbonate - Google Patents
Preparation method of ultrafine coating light calcium carbonate Download PDFInfo
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- CN103011227A CN103011227A CN2012105878441A CN201210587844A CN103011227A CN 103011227 A CN103011227 A CN 103011227A CN 2012105878441 A CN2012105878441 A CN 2012105878441A CN 201210587844 A CN201210587844 A CN 201210587844A CN 103011227 A CN103011227 A CN 103011227A
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Abstract
The invention discloses a preparation method of ultrafine coating light calcium carbonate. The preparation method comprises the following steps of: adding a compound dispersant to calcium hydroxide water slurry, then grinding the slurry and simultaneously filling carbon dioxide gas to carry out carbonization so that grinding and carbonization are carried out at the same time, and carbonizing the slurry until the pH value of the calcium hydroxide slurry is 6.5-7.5, thus obtaining the slurry containing ultrafine light calcium carbonate, wherein the compound dispersant comprises mixed phosphate salt, sodium polyacrylate and citrate. The preparation method has the advantages that the prepared ultrafine light calcium carbonate is used as a paper coating pigment to replace expensive imported kaolin and calcined kaolin; the prepared ultrafine light calcium carbonate slurry is directly used for coating without drying, thus not only saving the cost but also avoiding the problem of flocculation of ultrafine grains in the drying process; the ultrafine light calcium carbonate produced by the method has a small grain size; the slurry prepared from the ultrafine light calcium carbonate has low viscosity; and used for coating paper, the ultrafine light calcium carbonate can improve the quality of paper and reduce the production cost.
Description
Technical field
The present invention relates to a kind of preparation method of ultra-fine coating fine particle calcium carbonate.
Background technology
Paper Coating speed has obtained surprising progress in recent years, and particularly machine is coated with outward, and its operation has reached 1700m/min, even surpasses 2000m/min.Under such high-speed coating condition, a lot of coating qualities and operation problem can appear.Particularly White Board intensity and glossiness are had relatively high expectations.
Light calcium carbonate is a kind of important Inorganic Chemicals, and generally about 400 orders, grain diameter is large for the light calcium carbonate powder fineness of producing with common carborization, and coacervation is serious between the particle, has affected the application of light calcium carbonate.
CN1884085A discloses a kind of preparation method of superfine light calcium carbonate, in this patent employing phosphate ester salt, sodium polyacrylate, trolamine, trisodium phosphate, sodium polyphosphate or the Sodium hexametaphosphate 99 one or more are as dispersion agent simultaneous grinding in the calcium hydroxide slurry carbonization process, the median size of the calcium carbonate superfine powder that obtains is 0.2-2.0 μ m, wherein accounts for the 80-100% of total particle number less than the particle of 2 μ m.Yet the disclosed technology of this patent is applied in the high-speed coating process, and its contribution to indexs such as paper strength and glossiness still remains further to be improved.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of preparation method of ultra-fine coating fine particle calcium carbonate, the defects that exists to overcome prior art.
Method of the present invention comprises the steps:
In the calcium hydroxide water slurry, add composite dispersing agent, then slurry is sent into grinding plant and ground, pass into carbon dioxide from the grinding plant bottom simultaneously and carry out carbonization, grinding and carbonization are carried out simultaneously;
Carbonization temperature is 10-70 ℃, and carbonization is 6.5-7.5 to the pH of calcium hydroxide slurry, i.e. acquisition contains the slurry of superfine light calcium carbonate;
Described composite dispersing agent is comprised of mixed phosphate ester salt, sodium polyacrylate and citrate.
Each constituent mass percentage composition is in the described composite dispersing agent: mixed phosphate ester salt 40-55%, sodium polyacrylate 30-40% and citrate 10-25%, and each component percentage composition sum is 100%;
The preferred acetylizad citrate of described citrate, preferably Triethyl citrate acetate or acetyl tributyl citrate;
The hydrophobic grouping of described mixed phosphate ester salt is the hydrocarbon structure that contains 12-18 carbon atom;
Preferably, described mixed phosphate ester salt is the mixture of monoalkyl phosphate and phosphate diester salt, and the mol ratio of described monoalkyl phosphate and phosphate diester salt is 1:2～5;
Described mixed phosphate ester salt is ammonium salt, sodium salt or the sylvite of mixed phosphate ester;
The weight concentration of described calcium hydroxide water slurry is 5-25%, and the adding weight of described composite dispersing agent is the 0.05-3% of calcium hydroxide dry weight;
Described grinding plant is sand mill or stirs mill, the grinding plant use of can connecting more than or two.
The median size of the superfine light calcium carbonate that obtains is 0.2-2.0 μ m, and wherein grain diameter accounts for the 95-100% of total particle number less than the particle of 2 μ m.
The contriver studies discovery, on the prior art basis, improve the dispersion agent prescription, compound a certain proportion of citrate, the superfine light calcium carbonate that grinding obtains is applied to Paper Coating, and the performances such as its paper smoothness, surface strength of paper, glossiness have remarkable enhancing.The prepared superfine light calcium carbonate of the present invention is used for paper making and cloth coating pigment.Be mainly used in the coating pigment of art paper, coated manila, ivory board, to replace expensive import kaolin and calcined kaolin.The prepared ultra-fine light calcium carbonate slurry of the present invention is directly used in coating and need not dries, and has not only saved cost, has also avoided the group wadding problem of ultra-fine grain in drying process.The superfine light calcium carbonate fine size that the method according to this invention is produced is made slurry viscosity low, is used for the quality that Paper Coating can improve paper, reduces production costs.
Embodiment
Among the embodiment, if no special instructions, the content of component all is weight percentage.
Embodiment 1
In weight concentration is 5% calcium hydroxide (median size is 5 μ m) water slurry; be incorporated as 0.08% composite dispersing agent of calcium hydroxide dry weight, described composite dispersing agent is comprised of 40% the mixed phosphate ester ammonium salt that contains 18 carbon atoms, 40% sodium polyacrylate and 20% Triethyl citrate acetate.The mixed phosphate ester ammonium salt is the mixture of phosphoric acid lauryl alcohol monoesters ammonium salt and phosphoric acid lauryl alcohol dibasic acid esters ammonium salt, and the mol ratio of monoesters and dibasic acid esters is 1:2.
Calcium hydroxide slurry is pumped into 300 liters of vertical grinding machines of two series connection with pneumatic diaphragm, feed rate is 15 liter/mins of clocks.From every logical pure carbon dioxide gas in sand mill bottom, the flow of carbonic acid gas is 90 liter/mins of clocks, opens sand mill, and grinding and carbonization are carried out simultaneously simultaneously.The slurry carbonization that goes out second sand mill is good, and the pH of slurry is 7.0, and carbonization temperature is 70 ℃, and the median size of the calcium carbonate superfine powder that obtains is 0.3 μ m, and wherein the particle less than 2 μ m accounts for 99% of total particle number.
Embodiment 2
In weight concentration is 15% calcium hydroxide (median size is 5 μ m) water slurry; be incorporated as 2% composite dispersing agent of calcium hydroxide dry weight, described composite dispersing agent is comprised of 45% the mixed phosphate ester sylvite, 30% sodium polyacrylate and 25% Triethyl citrate acetate that contain 15 carbon atoms.Be the mixture of phosphoric acid hexadecanol monoesters sylvite and phosphoric acid hexadecanol dibasic acid esters sylvite, wherein the mol ratio of monoesters and dibasic acid esters is 1:3.
Calcium hydroxide slurry sent in one 3 cubic metres the stirring mill, from stirring the mixed gas gas of the logical carbonated volumetric concentration 25% in mill bottom, open and stir mill, with 80 rev/mins of agitation grinding carbonizations 8 hours, the pH of water slurry is 6.7, carbonization temperature is 30 ℃, and the mixed gas gas flow is 300 liter/mins of clocks.The median size of the calcium carbonate superfine powder that obtains is 0.3 μ m, and wherein the particle less than 2 μ m accounts for 96% of total particle number.
Embodiment 3
In weight concentration is 20% calcium hydroxide (median size is 10 μ m) water slurry; be incorporated as 2% composite dispersing agent of calcium hydroxide dry weight, described composite dispersing agent is comprised of 55% the mixed phosphate ester ammonium salt that contains 12 carbon atoms, 30% sodium polyacrylate and 15% Triethyl citrate acetate.Be the mixture of phosphoric acid stearyl alcohol monoesters ammonium salt and phosphoric acid stearyl alcohol dibasic acid esters ammonium salt, the mol ratio of monoesters and dibasic acid esters is 1:5 in the mixed phosphate ester ammonium salt.
Calcium hydroxide slurry is pumped into 80 liters vertical grinding machine of 5 series connection with pneumatic diaphragm, feed rate is 8 liter/mins of clocks.From every logical pure carbon dioxide gas in sand mill bottom, the flow of carbonic acid gas is 50 liter/mins of clocks, opens sand mill, and grinding and carbonization are carried out simultaneously simultaneously.The slurry carbonization that goes out the 5th sand mill is good, and the pH of slurry is 6.9, and carbonization temperature is 45 ℃, and the median size of the calcium carbonate superfine powder that obtains is 0.2 μ m, and wherein the particle less than 2 μ m accounts for 100% of total particle number.
Comparative Examples 1
In weight concentration is 20% calcium hydroxide (median size is 10 μ m) water slurry, be incorporated as 1.5% the phosphoric acid ester ammonium salt that contains 12 carbon atoms of ultra-fine calcium hydroxide dry weight, be incorporated as simultaneously 0.5% sodium polyacrylate of calcium hydroxide dry weight, calcium hydroxide slurry is pumped into 80 liters vertical grinding machine of 5 series connection with pneumatic diaphragm, feed rate is 8 liter/mins of clocks.From every logical pure carbon dioxide gas in sand mill bottom, the flow of carbonic acid gas is 50 liter/mins of clocks, opens sand mill, and grinding and carbonization are carried out simultaneously simultaneously.The slurry carbonization that goes out the 5th sand mill is good, and the pH of slurry is 6.7, and carbonization temperature is 45 ℃, and the median size of the calcium carbonate superfine powder that obtains is 0.4 μ m, and wherein the particle less than 2 μ m accounts for 99% of total particle number.
Application Example
Be coated with in the prescription at 18# machine chromo board face, use above-described embodiment superfine light calcium carbonate sample to replace U.S.'s china clay and calcined kaolin partly, the performance variation situations such as the physical index of investigation coating pattern and printability.Face is coated with experiment and adopts band ivory board midway, uses linear spreading rod to carry out face and is coated with glue spread 10g/m
2Compare with the coating pattern of original formulation.Coating rolling condition: get respectively above-mentioned coating pattern with twice of the hard press polish of small-sized rolling press (0.3Mpa, 90 ℃).
Table 1 face is coated with face and is coated with prescription
Table 2 coating pattern detects data
From the result, to compare with Comparative Examples under the similarity condition, above-described embodiment superfine light calcium carbonate partly replaces U.S.'s china clay and calcined kaolin, and the smoothness of pattern, coating glossiness, surface strength all are significantly improved.
Claims (7)
1. the preparation method of ultra-fine coating fine particle calcium carbonate, it is characterized in that, comprise the steps: in the calcium hydroxide water slurry, to add composite dispersing agent, then slurry is ground, pass into simultaneously carbon dioxide and carry out carbonization, make and grind and carbonization is carried out simultaneously, carbonization to the pH of calcium hydroxide slurry be 6.5-7.5, namely obtain to contain the slurry of superfine light calcium carbonate, described composite dispersing agent is comprised of mixed phosphate ester salt, sodium polyacrylate and citrate.
2. method according to claim 1 is characterized in that, carbonization temperature is 10-70 ℃.
3. method according to claim 1 is characterized in that, each constituent mass percentage composition is in the described composite dispersing agent: mixed phosphate ester salt 40-55%, sodium polyacrylate 30-40% and citrate 10-25%, each component percentage composition sum is 100%.
4. method according to claim 3; it is characterized in that; described citrate is acetylizad citrate, and described mixed phosphate ester salt is the mixture of monoalkyl phosphate and phosphate diester salt, and the mol ratio of described monoalkyl phosphate and phosphate diester salt is 1:2～5.
5. method according to claim 4 is characterized in that, described mixed phosphate ester salt is ammonium salt, sodium salt or the sylvite of mixed phosphate ester; The hydrophobic grouping of mixed phosphate ester salt is the hydrocarbon structure that contains 12-18 carbon atom.
6. method according to claim 1 is characterized in that, the weight concentration of described calcium hydroxide water slurry is 5-25%, and the adding weight of described composite dispersing agent is the 0.05-3% of calcium hydroxide dry weight.
7. each described method is characterized in that according to claim 1～6, and described abradant equipment is sand mill or stirs mill, the grinding plant use of connecting more than or two.
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| CN2012105878441A CN103011227A (en) | 2012-12-28 | 2012-12-28 | Preparation method of ultrafine coating light calcium carbonate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565355A (en) * | 2014-10-13 | 2016-05-11 | 东升新材料（山东）有限公司 | Aragonite type light calcium carbonate used for paper coating and synthetic method thereof |
| EP3031778A1 (en) * | 2014-12-12 | 2016-06-15 | Omya International AG | Improved process for the production of precipitated calcium carbonate |
| CN106928753A (en) * | 2016-11-07 | 2017-07-07 | 广西民族大学 | A kind of preparation method for PVC automobile chassis stone-impact-proof paint modified calcium carbonates |
| CN109455750A (en) * | 2018-12-12 | 2019-03-12 | 东升新材料（山东）有限公司 | A kind of modified abrasive light calcium and preparation method thereof |
| CN111533150A (en) * | 2020-04-14 | 2020-08-14 | 安徽东方钙业有限公司 | Production process of superfine nano calcium carbonate |
| US10822442B2 (en) | 2017-07-17 | 2020-11-03 | Ecolab Usa Inc. | Rheology-modifying agents for slurries |
| CN115215339A (en) * | 2022-05-30 | 2022-10-21 | 湖北工业大学 | Method for preparing calcium carbonate carbonization crystal nucleus from carbide slag and carrying out solid waste and carbon fixation |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565355A (en) * | 2014-10-13 | 2016-05-11 | 东升新材料（山东）有限公司 | Aragonite type light calcium carbonate used for paper coating and synthetic method thereof |
| US10584038B2 (en) | 2014-12-12 | 2020-03-10 | Omya International Ag | Process for the production of precipitated calcium carbonate |
| EP3031778A1 (en) * | 2014-12-12 | 2016-06-15 | Omya International AG | Improved process for the production of precipitated calcium carbonate |
| WO2016091889A1 (en) * | 2014-12-12 | 2016-06-16 | Omya International Ag | Improved process for the production of precipitated calcium carbonate |
| JP2018501182A (en) * | 2014-12-12 | 2018-01-18 | オムヤ インターナショナル アーゲー | Improved process for producing precipitated calcium carbonate |
| CN106928753A (en) * | 2016-11-07 | 2017-07-07 | 广西民族大学 | A kind of preparation method for PVC automobile chassis stone-impact-proof paint modified calcium carbonates |
| CN106928753B (en) * | 2016-11-07 | 2018-11-09 | 广西民族大学 | A kind of preparation method for PVC automobile chassis stone-impact-proof paint modified calcium carbonates |
| US10822442B2 (en) | 2017-07-17 | 2020-11-03 | Ecolab Usa Inc. | Rheology-modifying agents for slurries |
| CN109455750A (en) * | 2018-12-12 | 2019-03-12 | 东升新材料（山东）有限公司 | A kind of modified abrasive light calcium and preparation method thereof |
| CN111533150A (en) * | 2020-04-14 | 2020-08-14 | 安徽东方钙业有限公司 | Production process of superfine nano calcium carbonate |
| CN111533150B (en) * | 2020-04-14 | 2022-08-26 | 安徽东方钙业有限公司 | Production process of superfine nano calcium carbonate |
| CN115215339A (en) * | 2022-05-30 | 2022-10-21 | 湖北工业大学 | Method for preparing calcium carbonate carbonization crystal nucleus from carbide slag and carrying out solid waste and carbon fixation |
| CN115215339B (en) * | 2022-05-30 | 2023-10-10 | 湖北工业大学 | Method for preparing calcium carbonate carbonization crystal nucleus from carbide slag and carrying out solid waste and carbon fixation |
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Application publication date: 20130403 |